Epoxycyclohexane dicarboxylic acid diester, plasticizer, stabilizer and resin composition

Abstract

The purpose of the present invention is to provide a novel compound which is useful as a plasticizer that has improved heat resistance and cold resistance, while having good inherent plasticization performance as a plasticizer, or which is useful as a stabilizer for chlorine-containing resins. The inventors have found that a novel epoxycyclohexane dicarboxylic acid diester having a specific structure, which has an epoxy group in the molecular structure and has improved cold resistance and heat resistance, enables the achievement of the above-described purpose, and have been able to achieve a novel compound that is useful as a plasticizer and as a stabilizer.

Claims

1. An epoxycyclohexane dicarboxylic acid diester comprising a 4,5-epoxycyclohexane-1,2-dicarboxylic acid diester represented by the following general formula (1), wherein the molar ratio of the linear-chain alkyl group with respect to the total amount of the alkyl groups constituting the dicarboxylic acid diester is 50 to 99%: ##STR00011## wherein R1 and R2 are the same or different and each represents a linear or branched-chain alkyl group having 7 to 13 carbon atoms, wherein the molar ratio of cis isomer to trans isomer of the oxirane ring and the alkyloxycarbonyl group via the cyclohexane ring measured by proton nuclear magnetic resonance spectroscopy is 5/95 to 35/65.

2. The epoxycyclohexane dicarboxylic acid diester according to claim 1, wherein (i) the alkyl group is composed of 90% or more of an alkyl group having 9 to 11 carbon atoms, in which the molar ratio of alkyl group having 9 carbon atoms/alkyl group having 10 carbon atoms/alkyl group having 11 carbon atoms is in the range of 10 to 25/35 to 50/30 to 45, or (ii) the alkyl group contains an alkyl group having 9 carbon atoms in an amount of 90% or more molar ratio with respect to the total amount of the alkyl groups constituting the dicarboxylic acid diester.

3. The epoxycyclohexane dicarboxylic acid diester according to claim 1, wherein the molar ratio of the linear-chain alkyl group in the alkyl groups is 55 to 95%.

4. A plasticizer for vinyl chloride-based resins, comprising the epoxycyclohexane dicarboxylic acid diester according to claim 1.

5. A vinyl chloride-based resin composition comprising a vinyl chloride-based resin and the plasticizer for vinyl chloride-based resins according to claim 4.

6. The vinyl chloride-based resin composition according to claim 5, wherein the content of the plasticizer for vinyl chloride-based resins is 1 to 200 parts by weight with respect to 100 parts by weight of the vinyl chloride-based resin.

7. A vinyl chloride-based molded body obtained from the vinyl chloride-based resin composition according to claim 5.

8. A stabilizer for chlorine-containing resins, comprising the epoxycyclohexane dicarboxylic acid diester according to claim 1.

9. A chlorine-containing resin composition comprising a chlorine-containing resin and the stabilizer according to claim 8.

10. The chlorine-containing resin composition according to claim 9, wherein the content of the stabilizer is 1 to 30 parts by weight with respect to 100 parts by weight of the chlorine-containing resin.

11. The chlorine-containing resin composition according to claim 9, further comprising a plasticizer.

12. A chlorine-containing resin molded body obtained from the chlorine-containing resin composition according to claim 9.

13. A vinyl chloride-based resin composition for automotive interior, comprising a vinyl chloride-based resin and the epoxycyclohexane dicarboxylic acid diester according to claim 1.

14. An automotive interior material comprising the vinyl chloride-based resin composition for automotive interior according to claim 13.

15. A medical vinyl chloride-based resin composition comprising a vinyl chloride-based resin and the epoxycyclohexane dicarboxylic acid diester according to claim 1.

16. The medical vinyl chloride-based resin composition according to claim 15, further comprising a fatty acid calcium salt and/or a fatty acid zinc salt.

17. The medical vinyl chloride-based resin composition according to claim 15, further comprising a silane compound.

18. A medical material comprising the medical vinyl chloride-based resin composition according to claim 15.

19. A method for stabilizing a chlorine-containing resin by containing an epoxycyclohexane dicarboxylic acid diester comprising a 4,5-epoxycyclohexane-1,2-dicarboxylic acid diester represented by the following general formula (1), wherein the molar ratio of the linear-chain alkyl group with respect to the total amount of the alkyl groups constituting the dicarboxylic acid diester is 50 to 99%: ##STR00012## wherein R1 and R2 are the same or different and each represents a linear or branched-chain alkyl group having 7 to 13 carbon atoms, wherein the molar ratio of cis isomer to trans isomer of the oxirane ring and the alkyloxycarbonyl group via the cyclohexane ring measured by proton nuclear magnetic resonance spectroscopy is 5/95 to 35/65.

Description

MODE FOR CARRYING OUT THE INVENTION

(1) <Epoxycyclohexane Dicarboxylic Acid Diester>

(2) The epoxycyclohexane dicarboxylic acid diester of the present invention is characterized by being a 4,5-epoxycyclohexane-1,2-dicarboxylic acid diester represented by the following general formula (1).

(3) ##STR00009##

(4) In the formula, R.sup.1 and R.sup.2 are the same or different and each represents a linear or branched-chain alkyl group having 7 to 13 carbon atoms, preferably 8 to 12 carbon atoms, and the ratio (molar ratio) of the linear-chain alkyl group with respect to the total amount of the alkyl groups represented by R.sup.1 and R.sup.2 in the formula is from 50 to 99%, preferably from 55 to 98%, more preferably from 55 to 95%, even more preferably from 60 to 95%, particularly preferably from 70 to 95%. Please note that satisfying this ratio means to include the case where the epoxycyclohexane dicarboxylic acid diester of the present invention is a mixture of 4,5-epoxycyclohexane-1,2-dicarboxylic acid diesters. The ratio in the case of the mixture means the ratio (molar ratio) of the linear-chain alkyl group with respect to the total amount of the alkyl groups of the whole mixture.

(5) As a preferable embodiment, there is recommended an embodiment such that the alkyl group is preferably composed mainly of an alkyl group having 9 to 11 carbon atoms, and the ratio (molar ratio) of alkyl group having 9 carbon atoms/alkyl group having 10 carbon atoms/alkyl group having 11 carbon atoms is in the range of 10 to 25/35 to 50/30 to 45, or an embodiment such that an alkyl group having 9 carbon atoms occupies 90% or more (molar ratio) with respect to the total amount of the alkyl groups constituting the epoxycyclohexane dicarboxylic acid diester.

(6) In the 4,5-epoxycyclohexane-1,2-dicarboxylic acid diesters, stereoisomers may exist in the cyclohexane ring (chair conformation, boat conformation), the oxirane ring (cis form, transform) to the cyclohexane ring, the alkyloxycarbonyl group (cis form, trans form) to the cyclohexane ring, and the oxirane ring and the alkyloxycarbonyl group (cis form, trans form) via the cyclohexane ring, respectively. In the present invention, there is no particular limitation to such stereoisomers as long as the desired performance can be obtained, and either cis form alone, trans form alone, or a mixture of cis form and trans form can be used. As described below, in general, in the production by esterification with 4-cyclohexene-1,2-dicarboxylic anhydride as a starting material at a reaction temperature lower than the reaction temperature around 210 C., followed by epoxidation, the isomeric structure of the alkyloxycarbonyl group to the cyclohexane ring is dominant in the cis form.

(7) There is recommended an embodiment of a mixture of a cis form and a trans form, wherein the isomer structure of the oxirane ring and the alkyloxycarbonyl group via the cyclohexane ring has an isomer ratio (cis form/trans form, molar ratio) measured by proton nuclear magnetic resonance spectroscopy in the range of preferably 5/95 to 35/65, more preferably 10/90 to 30/70, particularly preferably 15/85 to 25/75.

(8) Please note that the isomer structure of the oxirane ring and the alkyloxycarbonyl group via the cyclohexane ring as referred to herein means that the cis form exists in such a case where the oxirane ring and the alkyloxycarbonyl group are located to the cyclohexane ring in the same direction as shown in the following structural formula (2), and the trans form exists when the oxirane ring and the alkyloxycarbonyl group are located to the cyclohexane ring in the different direction as shown in the structural formula (3). Its isomer ratio, that is, the isomer ratio of cis form and trans form, can be obtained from the results of nuclear magnetic resonance spectroscopic analysis (.sup.1H-NMR). The measurement can be easily carried out, for example, by dissolving the sample in deuterated chloroform solvent or the like and using a versatile nuclear magnetic resonance spectrometer. Further, among the two peaks attributed to the methine hydrogen at the oxirane ring site existing in the vicinity of 3.2 ppm of the analysis chart obtained by the above measurement, the peak shifted to the lower magnetic field side is assigned to as the peak of the trans form and the peak not shifted to the low magnetic field side is assigned to as the peak of the cis form, and the isomer ratio is calculated from the integral value of each peak using the following formula.
Isomer ratio of cis form/trans form=[{Integral value of cis form/(Integral value of cis form+Integral value of trans form)}100]/[{Integral value of trans form/(Integral value of cis form+Integral value of trans form)100]}

(9) ##STR00010##

(10) The above isomer structure can be isomerized to the desired isomer structure, i.e., isomer ratio, by heat or chemical agents depending on the purpose.

(11) The 4,5-epoxycyclohexane-1,2-dicarboxylic acid diester (hereinafter referred to as present diester in some cases) according to the present invention is not particularly limited by the production method thereof as long as the present diester has the above-mentioned specific structure. However, the 4,5-epoxycyclohexane-1,2-dicarboxylic acid diester can be easily obtained, for example, by esterifying a 4-cyclohexene-1,2-dicarboxylic acid or an acid anhydride thereof with a saturated aliphatic alcohol having a specific structure and epoxidizing the obtained 4-cyclohexene-1,2-dicarboxylic acid diester (hereinafter sometimes referred to as the raw material ester) under predetermined conditions. Alternatively, the 4,5-epoxycyclohexane-1,2-dicarboxylic acid diester can be obtained by a method of esterification between the obtained 4,5-epoxycyclohexane-1,2-dicarboxylic acid or an acid anhydride thereof and a saturated aliphatic alcohol having a specific structure after epoxidation of 4-cyclohexene-1,2-dicarboxylic acid or an acid anhydride thereof. Depending on the type of the saturated aliphatic alcohol, there is also a method in which a lower alcohol having about 1 to 6 carbon atoms is esterified in advance and then the saturated aliphatic alcohol is added for carrying out the transesterification to obtain the 4,5-epoxycyclohexane-1,2-dicarboxylic acid diester. From the viewpoint of convenience and practical utility, the method of epoxidation after esterification is most preferable.

(12) That is, the 4,5-epoxycyclohexane-1,2-dicarboxylic acid diester according to the present invention is characterized by having a structure formed by epoxidation of the unsaturated bond on the cyclohexene ring in the 4-cyclohexene-1,2-dicarboxylic acid diester which is obtained by esterification reaction between 4-cyclohexene-1,2-dicarboxylic acid or an acid anhydride thereof and a saturated aliphatic alcohol.

(13) [Saturated Aliphatic Alcohol]

(14) The saturated aliphatic alcohol used for the above esterification reaction or transesterification reaction is a linear or branched-chain saturated aliphatic alcohol having 7 to 13 carbon atoms, preferably 8 to 12 carbon atoms, more preferably 9 to 11 carbon atoms, and is particularly preferably (i) a linear or branched-chain saturated aliphatic alcohol containing a saturated aliphatic alcohol having 9 carbon atoms in a ratio (molar ratio) of 90% or more, more preferably 95% or more, or (ii) a saturated aliphatic alcohol composed mainly of a saturated aliphatic alcohol having 9 to 11 carbon atoms, wherein the ratio (molar ratio) of alkyl group having 9 carbon atoms/alkyl group having 10 carbon atoms/alkyl group having 11 carbon atoms is in the range of 10 to 25/35 to 50/30 to 45. The above mainly means that the ratio (molar ratio) of the saturated aliphatic alcohol having 9 to 11 carbon atoms in the whole saturated aliphatic alcohol is 90% or more, preferably 95% or more. The saturated aliphatic alcohol is a raw material alcohol to be a saturated aliphatic alkyl group constituting the 4,5-epoxycyclohexane-1,2-dicarboxylic acid diester represented by the general formula (1), that is, the explanation of such alcohol is synonymous with the explanation of the alkyl group.

(15) In addition, the saturated aliphatic alcohol is characterized in that the ratio (molar ratio) of the linear-chain saturated aliphatic alcohol in the saturated aliphatic alcohol is from 50 to 99%, preferably from 55 to 98%, more preferably from 55 to 95%, even more preferably 60 to 95%, particularly preferably 70 to 95%.

(16) Details of preferred embodiments of the saturated aliphatic alcohol include (i) a linear or branched-chain saturated aliphatic alcohol having 7 to 13 carbon atoms, wherein the ratio (molar ratio) of the saturated aliphatic alcohol having 9 carbon atoms is 90% or more, preferably 95% or more, and the ratio (molar ratio) of the linear-chain saturated aliphatic alcohol is from 50 to 99%, preferably from 55 to 98%, more preferably from 55 to 95%, even more preferably from 60 to 95%, particularly preferably from 70 to 95%, or (ii) a mixture of linear or branched-chain saturated aliphatic alcohols having 7 to 13 carbon atoms, composed mainly of saturated aliphatic alcohols having 9 to 11 carbon atoms, wherein the ratio (molar ratio) occupied by each alcohol having 9, 10 or 11 carbon atoms is in the range of 10 to 25/35 to 50/30 to 45, and the ratio (molar ratio) occupied by the linear-chain saturated aliphatic alcohol is from 50 to 99%, preferably from 55 to 98%, more preferably from 55 to 95%, even more preferably from 60 to 95%, particularly preferably from 70 to 95%. These embodiments are recommended.

(17) If a saturated aliphatic alcohol having less than 7 carbon atoms is contained, not only it is difficult to obtain a sufficient cold resistance or stabilizing effect but also the volatility resistance is lowered and problems such as fogging may occur. In addition, if a saturated aliphatic alcohol having more than 13 carbon atoms is contained, the compatibility with the resin tends to be poor, resulting in the deterioration of processability or plasticization efficiency, and uneven mixing with the resin occurs. As a result, there is a concern that variations may occur in the stabilizing effect, which is not desirable. Similarly, when the ratio of the linear-chain saturated aliphatic alcohol is less than 50%, the cold resistance or volatility resistance tends to be lowered, and when the ratio of the linear-chain saturated aliphatic alcohol exceeds 99%, the compatibility with the resin becomes worse and there are concerns that the plasticization efficiency or the like is lowered or the effect of stabilization varies, which is not desirable either.

(18) The saturated aliphatic alcohol containing 90% or more of a saturated aliphatic alcohol having 9 carbon atoms and having a ratio of linear-chain saturated aliphatic alcohol of from 50 to 99% can be produced by a production method including (1) a step of producing an aldehyde having 9 carbon atoms by a hydroformylation reaction of 1-octene, carbon monoxide, and hydrogen, and (2) a step of reducing the aldehyde having 9 carbon atoms to an alcohol by hydrogenation. The saturated aliphatic alcohol can be employed by directly using the saturated aliphatic alcohol obtained in the production method, or by formulating the saturated aliphatic alcohol obtained in the production method.

(19) In the hydroformylation reaction in the step (1), an aldehyde having 9 carbon atoms can be produced, for example, by reacting 1-octene, carbon monoxide, and hydrogen in the presence of a cobalt catalyst or a rhodium catalyst.

(20) In the hydrogenation of the step (2), an aldehyde having 9 carbon atoms can be reduced to an alcohol by hydrogenation under hydrogen pressure in the presence of a noble metal catalyst such as a nickel catalyst or a palladium catalyst. Specific examples of commercially available products include LINEVOL 9 manufactured by Shell Chemicals Co., Ltd. and n-Nonanol manufactured by Oxea Corporation.

(21) Likewise, the saturated aliphatic alcohol containing mainly a saturated aliphatic alcohol having 9 to 11 carbon atoms and having a ratio (molar ratio) of alkyl group having 9 carbon atoms/alkyl group having 10 carbon atoms/alkyl group having 11 carbon atoms in the range of 10 to 25/35 to 50/30 to 45, wherein the ratio of a linear-chain saturated aliphatic alcohol is from 50 to 99%, can be produced by a production method including (1) a step of producing an aldehyde having 9 to 11 carbon atoms by a hydroformylation reaction of 1-octene, 1-nonene, 1-decene, carbon monoxide, and hydrogen and (2) a step of reducing the aldehyde having 9 to 11 carbon atoms to an alcohol by hydrogenation. The saturated aliphatic alcohol can be employed by directly using the saturated aliphatic alcohol obtained in the production method, or by formulating the saturated aliphatic alcohol obtained in the production method.

(22) The hydroformylation reaction in the step (1) can be carried out, for example, by reacting 1-octene, 1-nonene, 1-decene, carbon monoxide, and hydrogen in the presence of a cobalt catalyst or a rhodium catalyst to obtain an aldehyde having 9 to 11 carbon atoms.

(23) In the hydrogenation of the step (2), the aldehyde having 9 to 11 carbon atoms can be reduced to an alcohol by hydrogenation under hydrogen pressure in the presence of a noble metal catalyst such as a nickel catalyst or a palladium catalyst. Specific examples of commercially available products include NEODOL 911 manufactured by Shell Chemicals Co., Ltd. and the like.

(24) [Esterification Reaction]

(25) The esterification reaction as used herein means an esterification reaction between the raw material alcohol and 4-cyclohexene-1,2-dicarboxylic acid or an acid anhydride thereof to obtain a 4-cyclohexene-1,2-dicarboxylic acid diester (raw material ester) which is a raw material in the epoxidation reaction for obtaining the present diester. In performing the esterification reaction, the raw material alcohol is recommended to be used in an amount of, for example, preferably from 2.00 moles to 5.00 moles, more preferably 2.01 moles to 3.00 moles, especially from 2.02 moles to 2.50 moles, with respect to 1 mole of the 4-cyclohexene-1,2-dicarboxylic acid or an acid anhydride thereof.

(26) In the case of using a catalyst for the esterification reaction, examples of the catalyst include a mineral acid, an organic acid, a Lewis acid, and the like. More specifically, examples of the mineral acid include sulfuric acid, hydrochloric acid, phosphoric acid, and the like. Examples of the organic acid include p-toluenesulfonic acid, methanesulfonic acid, and the like. Examples of the Lewis acid include an aluminum derivative, a tin derivative, a titanium derivative, a lead derivative, a zinc derivative, and the like, and one or two or more kinds of these can be used singly or in combination.

(27) Among them, p-toluenesulfonic acid, tetraalkyl titanate having 3 to 8 carbon atoms, titanium oxide, titanium hydroxide, tin fatty acid having 3 to 12 carbon atoms, tin oxide, tin hydroxide, zinc oxide, zinc hydroxide, lead oxide, lead hydroxide, aluminum oxide, and aluminum hydroxide are particularly preferable. The amount of the catalyst to be used is recommended to be preferably from 0.01% by weight to 5.0% by weight, more preferably from 0.02% by weight to 4.0% by weight, particularly preferably from 0.03% by weight to 3.0% by weight, with respect to the total weight of the acid component and the alcohol component which are each a raw material for synthesizing the ester.

(28) The esterification temperature is exemplified by 100 C. to 230 C., and the reaction is usually completed within 3 hours to 30 hours.

(29) The 4-cyclohexene-1,2-dicarboxylic acid or its acid anhydride, which is a raw material for the starting ester, is not particularly limited, and those produced by known methods, commercially available products, available reagents, and the like can be used. For example, RIKACID TH (trade name, manufactured by New Japan Chemical Co., Ltd.) and the like are exemplified as a commercially available product. The 4-cyclohexene-1,2-dicarboxylic anhydride is usually obtained by Diels-Alder reaction of maleic anhydride and 1,3-butadiene. From the viewpoint of esterification reaction, 4-cyclohexene-1,2-dicarboxylic anhydride is recommended to be used.

(30) In the esterification reaction, a water entraining agent such as benzene, toluene, xylene, and cyclohexane can be used to accelerate the distillation of water produced by the reaction.

(31) When an oxygen-containing organic compound such as an oxide, a peroxide, and a carbonyl compound is produced due to oxidative deterioration of the raw material, the produced ester and the organic solvent (water entraining agent) during the esterification reaction, the oxygen-containing organic compound exerts an adverse effect on heat resistance, light resistance, and the like. Thus, it is desirable to carry out the reaction in an inert gas atmosphere such as nitrogen gas or in an inert gas stream at normal pressure or under reduced pressure. After completion of the esterification reaction, it is recommended to distill off the excess alcohol or the raw material alcohol under reduced pressure or atmospheric pressure.

(32) The raw material ester obtained by the esterification method may be subsequently purified by base treatment (neutralization treatment).fwdarw.water washing treatment, liquid-liquid extraction, distillation (depressurization, dehydration treatment), adsorption treatment and the like as needed.

(33) The base used in the base treatment is not particularly limited as long as the base is a basic compound, and examples thereof include sodium hydroxide, sodium carbonate, and the like.

(34) Examples of the adsorbent used in the adsorption treatment include activated carbon, activated clay, activated alumina, hydrotalcite, silica gel, silica alumina, zeolite, magnesia, calcia, diatomaceous earth, and the like. These adsorbents can be used singly or in appropriate combination of two or more kinds thereof.

(35) The purification treatment after the esterification may be carried out at normal temperature, but the purification treatment may also be carried out by heating at about 40 to 90 C.

(36) [Epoxidation Reaction]

(37) The epoxidation reaction as used herein means an epoxidation reaction of an unsaturated bond on the cyclohexene ring in the raw material ester for obtaining the present diester and is usually carried out easily by a method described in Yuki Gosei Kagaku (Synthetic Organic Chemistry) Vol. 23, No. 7, pp 612-619 (1985) or the like. For example, there are exemplified by (i) a method in which an organic peracid such as peracetic acid and performic acid is used as the epoxidizing agent and (ii) a method in which hydrogen peroxide is used as the epoxidizing agent.

(38) More specifically, in the case of the method (i), the reaction is completed, for example, by adding peracetic acid obtained by reacting hydrogen peroxide with acetic anhydride or acetic acid in the presence of a strong acid such as sulfuric acid as a catalyst to the raw material ester, stirring the mixture at 20 to 30 C. for several hours, gradually raising the temperature to reach the temperature of 50 to 60 C., and maintaining the temperature for 2 to 3 hours. As the organic peracid, monoperphthalic acid, m-chloroperbenzoic acid, trifluoroperacetic acid and the like can also be used in addition to the above peracids.

(39) In the case of the method (ii), the epoxidation can be carried out, for example, by reacting hydrogen peroxide with a raw material ester in the co-presence of an oxygen carrier such as formic acid and a strong acid catalyst such as sulfuric acid. More specifically, using acetic acid or formic acid in a small amount of 0.5 moles or less and sulfuric acid as a catalyst in a small amount of 0.05 moles or less with respect to 1 mole of hydrogen peroxide, the reaction is carried out by maintaining the mixture at 40 to 70 C. for 2 to 15 hours. Thereby, the raw material ester can be easily epoxidized. As the catalyst, phosphoric acid, hydrochloric acid, nitric acid, boric acid, or salts thereof are well known in addition to the above catalysts, and sulfonic acid type strongly acidic cation exchange resins, aluminum oxides, and the like are also effective.

(40) The present diester obtained by the epoxidation method may be subsequently purified by aqueous phase removal, water washing treatment, liquid-liquid extraction, dehydration treatment, vacuum distillation, adsorption treatment or the like as needed.

(41) Examples of the adsorbent used in the adsorption treatment include activated carbon, activated clay, activated alumina, hydrotalcite, silica gel, silica alumina, zeolite, magnesia, calcia, diatomaceous earth and the like. These adsorbents can be used singly or in appropriate combination of two or more kinds thereof.

(42) The purification treatment after the epoxidation may be carried out at normal temperature, but such purification may also be carried out by heating to about 40 to 100 C.

(43) It has been confirmed from the results of proton nuclear magnetic resonance spectroscopy that most of compounds having the isomer structure of the alkyloxycarbonyl group with respect to the cyclohexane ring of the present diester obtained within the above-mentioned method and conditions exist in the cis form.

(44) <Use as Plasticizer>

(45) The present diester can be suitably used as a plasticizer, particularly as a plasticizer for vinyl chloride-based resins. That is, the plasticizer is characterized by comprising the epoxycyclohexane dicarboxylic acid diester having a specific structure according to the present invention. As a preferred embodiment, it is recommended to use, as a plasticizer, an epoxycyclohexane dicarboxylic acid diester compound having an isomer ratio (cis form/trans form, molar ratio) of the oxirane ring and the alkyloxycarbonyl group via the cyclohexane ring of from 5/95 to 35/65 measured by proton nuclear magnetic resonance spectroscopy.

(46) <Use as Stabilizer for Chlorine-Containing Resins>

(47) The present diester can be suitably used as a stabilizer for chlorine-containing resins. That is, the stabilizer is characterized by containing the epoxycyclohexane dicarboxylic acid diester having a specific structure according to the present invention. In a preferred embodiment, it is recommended to use an epoxycyclohexane dicarboxylic acid diester compound as the stabilizer having an isomer ratio (cis form/trans form, molar ratio) of the oxirane ring site of from 5/95 to 35/65 measured by proton nuclear magnetic resonance spectroscopy.

(48) The resin composition containing the epoxycyclohexane dicarboxylic acid diester having a specific structure according to the present invention and the molded body thereof can be suitably used for automobile mountings (e.g. automobile underbody coat, instrument panel, console, door sheet, under carpet, trunk sheet, door trim, etc.), various leathers, decorative sheets, agricultural films, films for food packaging, electric wire coating, various foam products, hoses, medical tubes, tubes for food materials, gaskets for refrigerators, packings, wallpaper, flooring materials, boots, curtains, shoe soles, gloves, water sealing plates, toys, decorative boards, blood bags, infusion bags, tarpaulins, mats, sealing materials, waterproof sheets, civil engineering sheets, roofing, waterproof sheets, insulating sheets, industrial tapes, glass films, erasing of letters, and the like.

(49) <Vinyl Chloride-Based Resin Composition>

(50) The vinyl chloride-based resin composition of the present invention can be obtained by blending the present diester as a plasticizer or as a stabilizer with a vinyl chloride-based resin. The content of the present diester in the vinyl chloride-based resin composition according to the present invention is appropriately selected depending on the applications, but is preferably 1 to 200 parts by weight with respect to 100 parts by weight of the vinyl chloride-based resin.

(51) [Vinyl Chloride-Based Resin]

(52) The vinyl chloride-based resin used in the present invention is a homopolymer of vinyl chloride or vinylidene chloride, and a copolymer of vinyl chloride or vinylidene chloride, and the production method thereof is carried out by a conventionally known polymerization method. For example, in the case of a versatile vinyl chloride-based resin, a method of suspension polymerization in the presence of an oil-soluble polymerization catalyst and the like can be mentioned. In the case of a vinyl chloride paste resin, a method of emulsion polymerization in an aqueous medium in the presence of a water-soluble polymerization catalyst and the like can be mentioned. The degree of polymerization of these vinyl chloride-based resins is usually from 300 to 5000, preferably from 400 to 3500, even more preferably from 700 to 3000. If the degree of polymerization is too low, the heat resistance and the like are deteriorated, whereas if the degree of polymerization is too high, the molding processability tends to decrease.

(53) In the case of a copolymer, examples thereof include copolymers of a vinyl chloride monomer and an -olefin having 2 to 30 carbon atoms (e.g. ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene, etc.), acrylic acid or esters thereof, methacrylic acid and esters thereof, maleic acid and esters thereof, a vinyl compound (e.g. vinyl acetate, vinyl propionate, alkyl vinyl ether, etc.), a polyfunctional monomer (e.g. diallyl phthalate, etc.), or a mixture thereof; ethylene-acrylate ester copolymers (e.g. ethylene-ethyl acrylate copolymer, etc.); ethylene-methacrylate ester copolymers; ethylene-vinyl acetate copolymers (EVA); chlorinated polyethylene; butyl rubber; crosslinked acrylic rubber; polyurethane; butadiene-styrene-methyl methacrylate copolymers (MBS); butadiene-acrylonitrile-(-methyl) styrene copolymers (ABS); styrene-butadiene copolymers; and graft copolymers obtained by grafting a vinyl chloride monomer to polyethylene, polymethyl methacrylate or a mixture thereof; and the like.

(54) <Soft Vinyl Chloride-Based Resin Composition>

(55) The soft vinyl chloride-based resin composition of the present invention can be obtained by blending the present diester as the plasticizer with the vinyl chloride-based resin. The content of the present diester of the present invention in the soft vinyl chloride-based resin composition is appropriately selected depending on the applications, but the content is preferably from 20 to 200 parts by weight, more preferably from 30 to 150 parts by weight, with respect to 100 parts by weight of the vinyl chloride-based resin. When the content of the present diester is 20 parts by weight or more, sufficient flexibility can be obtained even in the applications requiring flexibility, and in the applications requiring much more flexibility, flexibility is imparted by appropriately adjusting the blended amount. In the applications in which bleeding or the like to the surface of a molded product is feared, if the content of the present diester is 200 parts by weight or less, there is no fear of bleeding or the like, and the present diester can be preferably used. However, when a filler or the like is added to the vinyl chloride-based resin composition, the filler itself may absorb oil, so that the plasticizer may be blended beyond the above range. For example, when 100 parts by weight of calcium carbonate is blended as a filler with respect to 100 parts by weight of the vinyl chloride-based resin, the plasticizer may be blended up to about 500 parts by weight.

(56) For the vinyl chloride-based resin composition or the soft vinyl chloride-based resin composition, other known plasticizers may be used together with the present diester. In addition, if necessary, additives such as a flame retardant, a stabilizer, a stabilizing aid, a coloring agent, a processing aid, a filler, an antioxidant (an aging inhibitor), an ultraviolet absorber, a light stabilizer (e.g. a hindered amine, etc.), a lubricant, or an antistatic agent or the like is appropriately blended and used in many cases.

(57) Other plasticizers and additives other than the present diester may be used singly or in combination of two or more kinds thereof together with the present diester.

(58) As other plasticizers that can be used in combination with the present diester, known plasticizers conventionally used in the technical field can be used and include, for example, benzoic acid esters (e.g. diethylene glycol dibenzoate, etc.); phthalic acid esters (e.g. dibutyl phthalate (DBP), di-2-ethylhexyl phthalate (DOP), diisononyl phthalate (DINP), diisodecyl phthalate (DIDP), di(2-propylheptyl) phthalate (DPHP), diundecyl phthalate (DUP), ditridecyl phthalate (DTDP), bis(2-ethylhexyl) terephthalate (DOTP), bis(2-ethylhexyl) isophthalate (DOIP), etc.); cyclohexane dicarboxylic acid esters (e.g. bis(2-ethylhexyl) cyclohexane-1,2-dicarboxylate (DOCH), diisononyl cyclohexane-1,2-dicarboxylate (DINCH), etc.); alicyclic dibasic acid esters such as tetrahydrophthalic acid esters (e.g. bis(2-ethylhexyl) 4-cyclohexene-1,2-dicarboxylate (DOTH), etc.); aliphatic dibasic acid esters (e.g. di-2-ethylhexyl adipate (DOA), diisononyl adipate (DINA), diisodecyl adipate (DIDA), di-2-ethylhexyl sebacate (DOS), diisononyl sebacate (DINS), etc.); trimellitic acid esters (e.g. tri-2-ethylhexyl trimellitate (TOTM), triisononyl trimellitate (TINTM), triisodecyl trimellitate (TIDTM), tri-n-alkyl(C8, C10) trimellitate (TRIMEX N-08), trimellitic acid triesters of a saturated aliphatic alcohol containing 90% or more of a saturated aliphatic alcohol having 9 carbon atoms wherein the ratio of the linear-chain saturated aliphatic alcohol is from 50 to 99% (trinonyl trimellitate (branched and linear chain), TL9TM); pyromellitic acid esters (e.g. tetra-2-ethylhexyl pyromellitate (TOPM), etc.); phosphoric acid esters (e.g. tri-2-ethylhexyl phosphate (TOP), tricresyl phosphate (TCP), etc.); alkyl esters of polyhydric alcohols such as pentaerythritol; polyesters having a molecular weight of from 800 to 4000 synthesized by polyesterification of a dibasic acid (e.g. adipic acid, etc.) and a glycol; polyethers; epoxidized esters (e.g. epoxidized soybean oil, epoxidized linseed oil, etc.); fatty acid glycol esters (e.g. 1,4-butanediol dicaprate, etc.); citric acid esters (e.g. acetyl tributyl citrate (ATBC), acetyl trihexyl citrate (ATHC), acetyl triethylhexyl citrate (ATEHC), butyryl trihexyl citrate (BTHC), etc.); isosorbide diesters; chlorinated paraffins obtained by chlorinating paraffin wax or n-paraffin; chlorinated fatty acid esters (e.g. chlorinated stearic acid ester, etc.); higher fatty acid esters (e.g. butyl oleate, etc.); and the like. In the case of blending other plasticizers that can be used in combination, the blending amount is appropriately selected within the range not to impair the effect of the plasticizer of the present invention, and is recommended to be usually about 1 to 100 parts by weight with respect to 100 parts by weight of the vinyl chloride-based resin.

(59) Examples of the flame retardant include inorganic compounds such as aluminum hydroxide, antimony trioxide, magnesium hydroxide, and zinc borate; phosphorus compounds such as cresyl diphenyl phosphate, trischloroethyl phosphate, trischloropropyl phosphate, and trisdichloropropyl phosphate; halogen compounds such as chlorinated paraffin, and the like. When the flame retardant is blended, the blending amount is recommended to be about 0.1 to 20 parts by weight with respect to 100 parts by weight of the vinyl chloride-based resin.

(60) Examples of the stabilizer include metal soap compounds of an organic acid compound containing a metal, such as lithium stearate, magnesium stearate, magnesium laurate, calcium ricinoleate, calcium stearate, barium laurate, barium ricinoleate, barium stearate, zinc octoate, zinc laurate, zinc ricinoleate, and zinc stearate; metal soap compounds of an organic acid compound containing a composite metal, such as barium-zinc stearate, barium-zinc laurate, barium-zinc ricinoleate, barium-zinc octoate, calcium-zinc stearate, calcium-zinc laurate, calcium-zinc ricinoleate, and calcium-zinc octoate; organotin-based compounds such as dimethyltin bis(2-ethylhexyl thioglycolate), dibutyltin maleate, dibutyltin bis(butyl maleate), and dibutyltin dilaurate; antimony mercaptide compounds; epoxy compounds other than the present diester, such as epoxidized soybean oil, epoxidized linseed oil, and epoxy resin; and the like. When the stabilizer is blended, the blending amount is recommended to be about 0.1 to 20 parts by weight with respect to 100 parts by weight of the vinyl chloride-based resin.

(61) Examples of the stabilizing aid include phosphite-based compounds such as triphenyl phosphite, monooctyl diphenyl phosphite, and tridecyl phosphite; beta-diketone compounds such as acetylacetone and benzoylacetone; polyol compounds such as glycerin, sorbitol, pentaerythritol, and polyethylene glycol; perchlorate compounds such as barium perchlorate and sodium perchlorate; hydrotalcite compounds; zeolites; and the like. When a stabilizing aid is blended, the blending amount is recommended to be about 0.1 to 20 parts by weight with respect to 100 parts by weight of the vinyl chloride-based resin.

(62) Examples of the coloring agent include carbon black, lead sulfide, white carbon, titanium white, lithopone, red oxide, antimony sulfide, chrome yellow, chrome green, phthalocyanine green, cobalt blue, phthalocyanine blue, and molybdenum orange. When a coloring agent is blended, the blending amount is recommended to be about from 1 to 100 parts by weight per 100 parts by weight of the vinyl chloride-based resin.

(63) Examples of the processing aid include liquid paraffin, polyethylene wax, stearic acid, stearic acid amide, ethylene bis(stearic acid amide), butyl stearate, and calcium stearate. When a processing aid is blended, the blending amount is recommended to be about from 0.1 to 20 parts by weight with respect to 100 parts by weight of the vinyl chloride-based resin.

(64) Examples of the filler include metal oxides such as calcium carbonate, silica, alumina, clay, talc, diatomaceous earth, and ferrite; fibers and powders of glass, carbon, metal, or the like; glass beads; graphite; aluminum hydroxide; barium sulfate; magnesium oxide; magnesium carbonate; magnesium silicate; calcium silicate; and the like. When a filler is blended, the blending amount is recommended to be about from 1 to 100 parts by weight with respect to 100 parts by weight of the vinyl chloride-based resin.

(65) Examples of the antioxidant include phenol-based compounds (e.g. 2,6-di-tert-butylphenol, tetrakis[methylene-3-(3,5-tert-butyl-4-hydroxyphenol) propionate]methane, 2-hydroxy-4-methoxybenzophenone, etc.); sulfur compounds (e.g. alkyl disulfides, thiodipropionate esters, benzothiazoles, etc.); phosphate-based compounds (e.g. tris(nonylphenyl) phosphite, diphenyl isodecyl phosphite, triphenyl phosphite, tris(2,4-di-t-butylphenyl) phosphite, etc.); organometallic compounds (e.g. zinc dialkyl dithiophosphate, zinc diaryl dithiophosphate, etc.); and the like. When an antioxidant is blended, the blending amount is recommended to be about from 0.2 to 20 parts by weight with respect to 100 parts by weight of the vinyl chloride-based resin.

(66) Examples of the ultraviolet absorber include salicylate-based compounds such as phenyl salicylate and p-tert-butylphenyl salicylate; benzophenone-based compounds such as 2-hydroxy-4-n-octoxybenzophenone and 2-hydroxy-4-methoxybenzophenone; benzotriazole-based compounds such as 5-methyl-1H-benzotriazole, 1-dioctylaminomethyl-benzotriazole; cyanoacrylate-based compounds; and the like. When an ultraviolet absorber is blended, the blending amount is recommended to be about from 0.1 to 10 parts by weight with respect to 100 parts by weight of the vinyl chloride-based resin.

(67) Examples of the hindered amine-based light stabilizer include bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis(1,2,2,6,6-pentamethyl-4-piperidyl) sebacate and 1,2,2,6,6-pentamethyl-4-piperidyl sebacate (mixture), bis(1,2,2,6,6-pentamethyl-4-piperidyl) [[3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl]methyl]butyl malonate, decanedioic acid bis(2,2,6,6-tetramethyl-1(octyloxy)-4-piperidyl)ester, and a reaction product of 1,1-dimethylethyl hydroperoxide and octane, 4-benzoyloxy-2,2,6,6-tetramethylpiperidine, an ester mixture of 2,2,6,6-tetramethyl-4-piperidinol and a higher fatty acid, tetrakis(2,2,6,6-tetramethyl-4-piperidyl)-1,2,3,4-butanetetracarboxylate, tetrakis(1,2,2,6,6-pentamethyl-4-piperidyl)-1,2,3,4-butanetetracarboxylate, a polycondensation product of dimethyl succinate and 4-hydroxy-2,2,6,6-tetramethyl-1-piperidine ethanol, poly[{(6-(1,1,3,3-tetramethylbutyl)amino-1,3,5-triazine-2,4-diyl){(2,2,6,6-tetramethyl-4-piperidyl)imino)hexamethylene {(2,2,6,6-tetramethyl-4-piperidyl)imino}}, a polycondensation product of dibutylamine/1,3,5-triazine/N,N-bis(2,2,6,6-tetramethyl-4-piperidyl-1,6-hexamethylenediamine and N-(2,2,6,6-tetramethyl-4-piperidyl)butylamine, N,N,N,N-tetrakis-(4,6-bis-(butyl-(N-methyl-2,2,6,6-tetramethylpiperidine-4-yl)amino)-triazine-2-yl)-4,7-diazadecane-1,10-diamine, and the like. When a light stabilizer is blended, the blending amount is recommended to be about from 0.1 to 10 parts by weight with respect to 100 parts by weight of the vinyl chloride-based resin.

(68) Examples of the lubricant include silicone; liquid paraffin; paraffin wax; fatty acid metal salts such as metal stearate and metal laurate; fatty acid amide; fatty acid wax; and higher fatty acid wax. When a lubricant is blended, the blending amount is recommended to be about from 0.1 to 10 parts by weight with respect to 100 parts by weight of the vinyl chloride-based resin.

(69) Examples of the antistatic agent include anionic antistatic agents such as alkyl sulfonate antistatic agents, alkyl ether carboxylic acid antistatic agents, or dialkyl sulfosuccinate antistatic agents; nonionic antistatic agents such as polyethylene glycol derivatives, sorbitan derivatives or diethanolamine derivatives; quaternary ammonium salts such as alkylamide amine antistatic agents or alkyl dimethylbenzyl antistatic agents; cationic antistatic agents such as alkyl pyridinium organic acid salt or hydrochloride; and amphoteric antistatic agents such as alkylbetaine antistatic agents or alkylimidazoline antistatic agents. When an antistatic agent is blended, the blending amount is recommended to be about from 0.1 to 10 parts by weight with respect to 100 parts by weight of the vinyl chloride-based resin.

(70) The vinyl chloride-based resin composition or the soft vinyl chloride-based resin composition of the present invention can be converted into a mixed powder by mixing and stirring the present diester, the vinyl chloride-based resin, and if necessary, various additives, using a stirrer such as a mortar mixer, a Henschel mixer, a Banbury mixer, or a ribbon blender.

(71) The present diester, the vinyl chloride-based resin, and if necessary, various additives can be subjected to melt molding using a kneading machine such as a conical twin screw extruder, a parallel twin screw extruder, a single screw extruder, a co-kneader type kneading machine, a roll kneader, etc, thereby to obtain a pellet form of the vinyl chloride-based resin composition or the soft vinyl chloride-based resin composition.

(72) In addition, the present diester, a vinyl chloride-based paste resin, and if necessary, other plasticizers other than the present diester, and various additives are mixed homogeneously by a pony mixer, a butterfly mixer, a planetary mixer, a ribbon blender, a kneader, a dissolver, a twin screw mixer, a Henschel mixer, a triple roll mill, and the like, and defoaming treatment is optionally carried out under reduced pressure to be able to obtain a pasty soft vinyl chloride-based resin composition.

(73) [Vinyl Chloride-Based Molded Body]

(74) The vinyl chloride-based resin composition or the soft vinyl chloride-based resin composition (powder formulation or pellet formulation) according to the present invention can be molded into a desired shape by melt-molding using a conventionally known method such as vacuum molding, compression molding, extrusion molding, injection molding, calender molding, press molding, blow molding, and powder molding.

(75) On the other hand, the pasty soft vinyl chloride-based resin composition can be formed into a desired shape by molding processing using a conventionally known method such as spread molding, dipping molding, gravure molding, slush molding, and screen processing.

(76) The shape of the molded body is not particularly limited, and examples thereof include rod shape, sheet shape, film shape, plate shape, cylindrical shape, round shape, elliptical shape, or particular shapes of toys, ornaments, and the like (for example, star shape or polygon shape).

(77) <Chlorine-Containing Resin Composition>

(78) The stabilized chlorine-containing resin composition of the present invention is obtained by blending the present diester as a stabilizer into a chlorine-containing resin.

(79) [Chlorine-Containing Resin]

(80) The chlorine-containing resin used in the present invention is not particularly limited as long as it is a resin containing chlorine in the structure thereof, and examples thereof include homopolymers such as polyvinyl chloride, polyvinylidene chloride, chlorinated polyolefins (e.g. chlorinated polyethylene, chlorinated polypropylene), chlorinated polyvinyl chloride, and further copolymers such as vinyl chloride-ethylene copolymer, vinyl chloride-propylene copolymer, vinyl chloride-vinyl acetate copolymer, vinyl chloride-styrene copolymer, vinyl chloride-isobutylene copolymer, vinyl chloride-butadiene copolymer, vinyl chloride-vinylidene chloride copolymer, vinyl chloride-chlorinated propylene copolymer, vinyl chloride-maleic acid ester copolymer, allyl chloride copolymer, vinyl chloride-methacrylic acid ester copolymer, ethylene-vinyl acetate-vinyl chloride copolymer, vinyl chloride-styrene-maleic anhydride terpolymer, vinyl chloride-styrene-acrylonitrile copolymer, vinyl chloride-isoprene copolymer, vinyl chloride-vinylidene chloride-vinyl acetate terpolymer, vinyl chloride-acrylonitrile copolymer, and vinyl chloride-various vinyl ethers copolymer.

(81) The stabilizer according to the present invention can also be used in a system of chloroprene-based synthetic rubber, epichlorohydrin rubber and copolymer thereof, and a chlorine-containing rubber or elastomer such as hydrochloric acid rubber and chlorinated rubber.

(82) The chlorine-containing resin may be a single type or a blend type with another compatible resin, for example, with a resin such as polyester resin, acrylic resin, urethane resin, and acrylonitrile-styrene-butadiene copolymer.

(83) Among them, the vinyl chloride-based resin is a chlorine-containing resin that is easy to process, excellent in characteristics of the obtained molded body, and is widely used.

(84) Since the vinyl chloride-based resin is as described above, its explanation will be omitted.

(85) [Chlorine-Containing Resin Composition]

(86) The content of the present diester in the stabilized chlorine-containing resin composition according to the present invention is appropriately selected depending on the type of the resin to be blended and the application to be used, but the content is preferably from 1 to 30 parts by weight, more preferably from 1 part by weight or more but less than 20 parts by weight, particularly preferably 5 parts by weight or more but less than 20 parts by weight, with respect to 100 parts by weight of the chlorine-containing resin. If the content is 1 part by weight or more, it is possible to obtain a more favorable stabilizing effect, and such a content is advantageous particularly in view of long-term stabilizing effect. If the content is 30 parts by weight or less, there are less concerns about various problems such as bleeding to the surface of the molded article even in any use environment, migration to the laminated resin or to the oil to be contacted, and furthermore the occurrence of fogging due to volatilization, and thus the content in the above range of the present diester is preferred.

(87) For the chlorine-containing resin composition, other known stabilizers may be used in combination with the present diester. Further, if necessary, additives such as a stabilizing aid, an antioxidant (an aging inhibitor), an ultraviolet absorber, a light stabilizer such as a hindered amine, a plasticizer, a flame retardant, a coloring agent, a processing aid, a filler, a lubricant or an antistatic agent is appropriately blended and frequently used.

(88) Other stabilizers other than the present diesters, and additives may be blended singly or in combination of two or more kinds thereof together with the present diester.

(89) As the stabilizer that can be used in combination with the present diester, the above-mentioned ones are exemplified. Among them, the combined use of the metal soap compound shows an effect of amplifying the stabilizing effect of the present diester due to a synergistic effect, so that such combination use is particularly preferable. In the case of blending other stabilizers that can be used in combination, the blending amount thereof is appropriately selected within the range not to impair the effect of the stabilizing agent according to the present invention, and is usually recommended to use about 0.1 to 20 parts by weight with respect to 100 parts by weight of the chlorine-containing resin.

(90) Combination use of a stabilizing aid is also effective as a method of making the effect of the present diester more effective. As the stabilizing aid, the above-mentioned ones are exemplified. When a stabilizing aid is blended, the blending amount is appropriately selected within the range not to impair the effect of the stabilizing agent of the present invention, and is usually recommended to use about 0.1 to 20 parts by weight with respect to 100 parts by weight of the chlorine-containing resin.

(91) It is also effective as a method of making the effect of the present diester more effective to use an antioxidant, an ultraviolet absorber antioxidant, a light stabilizer and the like in combination with the present diester. As the antioxidant, the above-mentioned ones are exemplified. When blending an antioxidant, the blending amount is recommended to be about 0.2 to 20 parts by weight with respect to 100 parts by weight of the chlorine-containing resin.

(92) As the ultraviolet absorber, the above-mentioned ones are exemplified. When blending an ultraviolet absorber, the blending amount is recommended to be about 0.1 to 10 parts by weight with respect to 100 parts by weight of the chlorine-containing resin.

(93) As the hindered amine-based light stabilizer, the above-mentioned ones are exemplified. When blending a light stabilizer, the blending amount is recommended to be about 0.1 to 10 parts by weight with respect to 100 parts by weight of the chlorine-containing resin.

(94) As the plasticizer, known plasticizers that have been conventionally used can be used, and the above-mentioned ones are exemplified.

(95) Among them, there are exemplified aromatic polycarboxylic acid esters such as phthalic acid esters and trimellitic acid esters; alicyclic polycarboxylic acid esters such as alicyclic dibasic acid esters; polyesters; polyethers; and the like. More specifically, phthalic acid esters, trimellitic acid esters, cyclohexanedicarboxylic acid esters and the like are exemplified as particularly preferable plasticizers. Specific examples of the preferable plasticizer include diisodecyl phthalate (DIDP), di(2-propylheptyl) phthalate (DPHP), diundecyl phthalate, dialkyl(C9 to C11) phthalate (PL-200), dialkyl(C10 to C13) phthalate (VINYCIZER 124), ditridecyl phthalate (VINYCIZER 20), tri-2-ethylhexyl trimellitate (TOTM), tri-n-octyl trimellitate (TRIMEX New NSK), triisonyl trimellitate (TINTM), triisodecyl trimellitate (TIDTM), tri-n-alkyl(C8, C10) trimellitate (TRIMEX N-08), trinonyl trinellitate (branched and linear chain) (TL9TM), and the like.

(96) In the case where the plasticizer is contained, its content is appropriately selected according to the hardness required for the application to be used, but 1 to 200 parts by weight, preferably about 5 to 150 parts by weight, with respect to 100 parts by weight of the chlorine-containing resin is usually recommended.

(97) The stabilizer for chlorine-containing resins according to the present invention and the plasticizer may be separately added to the chlorine-containing resin, but it is more preferable to add them after mixing in advance, to the chlorine-containing resin. By premixing, compatibilization of a plasticizer having poor compatibility with a resin (that is, an addition effect of improving plasticization efficiency of the plasticizer having poor plasticization efficiency), or improvement in the uniformity of the stabilizer in the resin when the content of the stabilizer is small, that is, an effect of preventing unevenness of stabilizing effect of the stabilizer and the like is expected.

(98) As the flame retardant, the above-mentioned ones are exemplified. When blending a flame retardant, the blending amount is recommended to be about 0.1 to 20 parts by weight with respect to 100 parts by weight of the chlorine-containing resin.

(99) As the coloring agent, the above-mentioned ones are exemplified. When blending a coloring agent, the blending amount is recommended to be about 1 to 100 parts by weight with respect to 100 parts by weight of the chlorine-containing resin.

(100) As the processing aid, the above-mentioned ones are exemplified. When blending a processing aid, the blending amount is recommended to be about 0.1 to 20 parts by weight with respect to 100 parts by weight of the chlorine-containing resin.

(101) As the filler, the above-mentioned ones are exemplified. When blending a filler, the blending amount is recommended to be about 1 to 100 parts by weight with respect to 100 parts by weight of the chlorine-containing resin.

(102) As the lubricant, the above-mentioned ones are exemplified. When blending a lubricant, the blending amount is recommended to be about 0.1 to 10 parts by weight with respect to 100 parts by weight of the chlorine-containing resin.

(103) As the antistatic agent, the above-mentioned ones are exemplified. When blending an antistatic agent, the blending amount is recommended to be about 0.1 to 10 parts by weight with respect to 100 parts by weight of the chlorine-containing resin.

(104) The chlorine-containing resin composition of the present invention can be converted into a mixed powder by stirring and mixing the present diester, the chlorine-containing resin, and if necessary, various additives, using a stirrer such as a mortar mixer, a Henschel mixer, a Banbury mixer, and a ribbon blender.

(105) The present diester, a chlorine-containing resin, and if necessary, various additives can be subjected to melt molding with use of a kneader such as a conical twin screw extruder, a parallel twin-screw extruder, a single screw extruder, a co-kneader type kneading machine, and a roll kneader, so that a pelletized chlorine-containing resin composition can be obtained.

(106) In addition, the present diester, a plasticizer, a vinyl chloride-based paste resin, and if necessary, various additives are mixed homogeneously by a mixer such as a pony mixer, a butterfly mixer, a planetary mixer, a ribbon blender, a kneader, a dissolver, a twin screw mixer, a Henschel mixer, a triple roll mill, and the like, and defoaming treatment is optionally carried out under reduced pressure to be able to obtain a pasty vinyl chloride-based resin composition.

(107) [Chlorine-Containing Resin Molded Body]

(108) The chlorine-containing resin composition (powder formulation or pellet formulation) can be molded into a desired shape by melt-molding processing using a conventionally known method such as vacuum molding, compression molding, extrusion molding, injection molding, calender molding, press molding, blow molding, and powder molding.

(109) On the other hand, the pasty chlorine-containing resin composition can be formed into a desired shape by molding processing using a conventionally known method such as spread molding, dipping molding, gravure molding, slush molding, and screen processing.

(110) The shape of the molded body is not particularly limited, and examples thereof include rod shape, sheet shape, film shape, plate shape, cylindrical shape, round shape, elliptical shape; and particular shapes of toys, ornaments, and the like, such as star shape or polygon shape.

(111) <Vinyl Chloride-Based Resin Composition for Automotive Interior>

(112) The greatest feature of the vinyl chloride-based resin composition for automotive interior of the present invention resides in that the resin contains the above-mentioned diester as a plasticizing component (plasticizer) or a stabilizing component (stabilizer), and such composition can be obtained by blending the present diester as a plasticizer or as a stabilizer with a vinyl chloride-based resin.

(113) [Vinyl Chloride-Based Resin]

(114) Since the vinyl chloride-based resin used in the present invention is as described above, its explanation will be omitted.

(115) [Vinyl Chloride-Based Resin Composition for Automotive Interior]

(116) The content of the present diester in the vinyl chloride-based resin composition for automotive interior of the present invention is appropriately selected according to its use, but is preferably from 1 to 200 parts by weight, more preferably 5 to 150 parts by weight, with respect to 100 parts by weight of the vinyl chloride-based resin. The present diester has also an effect as a plasticizer as well as an effect as a stabilizer regardless of its blending amount. More specifically, when an effect as a plasticizer is desired, the blending amount is preferably from 20 to 200 parts by weight, more preferably from 30 to 150 parts by weight. When a stabilizer effect is mainly desired, the blending amount as a stabilizer is preferably from 1 to 30 parts by weight, more preferably from 5 to 20 parts by weight.

(117) When the content of the present diester is 1 part by weight or more with respect to 100 parts by weight of the vinyl chloride-based resin, the effect as the stabilizer of the present diester can be sufficiently exerted, and if the content of the present diester is 200 parts by weight or less, there is no concern about bleeding to the surface of the molded article when used. Thus, such molded article can be used with confidence.

(118) In addition, when the present diester is desired to have an effect as a plasticizer, sufficient flexibility can be obtained according to the purpose of use if the content is 20 parts by weight or more with respect to 100 parts by weight of the vinyl chloride-based resin.

(119) Further, in the case where an effect as a stabilizer (stabilizing effect) is mainly desired, if the content is 1 part by weight or more with respect to 100 parts by weight of the vinyl chloride-based resin, sufficient stabilizing effect, especially long-term stabilization effect can be obtained. In addition, if the content is 30 parts by weight or less, the stabilizing effect becomes dominant over the effect as a plasticizer, so that it is also possible to maintain the target hardness for inherently intended use without becoming soft.

(120) For the vinyl chloride-based resin composition for automotive interior material according to the present invention, other known plasticizers or stabilizers can be used in combination with the present diester, and such combination use is recommended from the viewpoint of plasticizing effect and stabilizing effect. From the viewpoint of the stabilizing effect, it is also recommended that if necessary, a stabilizing aid, an antioxidant (an aging inhibitor), an ultraviolet absorber, a light stabilizer such as a hindered amine, and the like be used in combination. Further, in many cases, additives such as a flame retardant, a coloring agent, a processing aid, a filler, a lubricant, or an antistatic agent are appropriately blended and used frequently according to the intended use.

(121) Other plasticizers and stabilizers except for the present diester, and other additives may be blended singly or in combination of two or more kinds thereof together with the present diester.

(122) As other plasticizers that can be used in combination with the present diester, known plasticizers conventionally used in the state of the art can be used, and include the above-mentioned ones. In the case of blending other plasticizer that can be used in combination, the blending amount is appropriately selected within the range not to impair the effect of the plasticizer according to the present invention, and about 1 to 100 parts by weight with respect to 100 parts by weight of the vinyl chloride-based resin is usually recommended.

(123) Among them, aromatic polycarboxylic acid esters such as phthalic acid esters and trimellitic acid esters; alicyclic polycarboxylic acid esters such as alicyclic dibasic acid esters; polyesters; and polyethers are exemplified as preferable plasticizers. Further, phthalic acid esters, trimellitic acid esters, cyclohexane dicarboxylic acid esters and the like are exemplified as particularly preferable plasticizers. Specific examples of the particularly preferable plasticizers include diisodecyl phthalate (DIDP), di(2-propylheptyl) phthalate (DPHP), diundecyl phthalate, dialkyl(C9 to C11) phthalate (PL-200), dialkyl(C10 to C13) phthalate (VINYCIZER 124), ditridecyl phthalate (VINYCIZER 20), tri-2-ethylhexyl trimellitate (TOTM), tri-n-octyl trimellitate (TRIMEX New NSK), triisonyl trimellitate (TINTM), triisodecyl trimellitate (TIDTM), tri-n-alkyl(C8, C10) trimellitate (TRIMEX N-08), a trimellitic acid triester of a saturated aliphatic alcohol containing 90% or more of a saturated aliphatic alcohol having 9 carbon atoms and having a ratio of linear-chain saturated aliphatic alcohol of from 50 to 99% (trinonyl trimellitate (branched and linear chain), TL9TM), and the like.

(124) When the plasticizer is used in combination, the content thereof is appropriately selected according to the hardness required for the intended use, but the recommended blending content is usually from 1 to 200 parts by weight, preferably 5 to 150 parts by weight, with respect to 100 parts by weight of the vinyl chloride-based resin.

(125) The present diester and the plasticizer according to the present invention may be separately added to the vinyl chloride-based resin, but it is more preferable to add the present diester and the plasticizer to the vinyl chloride-based resin after mixing together in advance. By premixing, it becomes easy to obtain a compatibilization effect of the plasticizer having poor compatibility with the resin (that is, a plasticizer having poor plasticization efficiency), namely to obtain an improving effect of plasticization efficiency, or it becomes easy to obtain a preventive effect of unevenness in the stabilizing effect of the stabilizer as a result of maintaining the uniformity in the resin when the present diester is used as the stabilizer even if the content is small.

(126) As the stabilizer that can be used in combination with the present diester, the above-mentioned ones are exemplified. Among them, the combination use of the above-mentioned metal soap compound shows an effect of amplifying the stabilizing effect of the present diester due to a synergistic effect, and is therefore particularly preferable. In the case of blending other stabilizer that can be used in combination, the blending amount is appropriately selected within the range not to impair the effect of the stabilizer of the present invention, and about 0.1 to 20 parts by weight is usually recommended with respect to 100 parts by weight of the vinyl chloride-based resin.

(127) Combination use of a stabilizing aid is also effective as a method of making the effect of the present diester more effective. As the stabilizing aid, the above-mentioned ones are exemplified. When a stabilizing aid is blended, the blending amount is appropriately selected within the range not to impair the effect of the stabilizer according to the present invention, and about 0.1 to 20 parts by weight is usually recommended with respect to 100 parts by weight of the vinyl chloride-based resin.

(128) Combination use of an antioxidant, an ultraviolet absorber antioxidant, a light stabilizer, and the like is also effective as a method of making the effect of the present diester more effective. As the antioxidant, the above-mentioned ones are exemplified. When an antioxidant is blended, the blending amount is recommended to be about 0.2 to 20 parts by weight with respect to 100 parts by weight of the vinyl chloride-based resin.

(129) As the ultraviolet absorber, the above-mentioned ones are exemplified. When blending an ultraviolet absorber, the blending amount is recommended to be about 0.1 to 10 parts by weight with respect to 100 parts by weight of the vinyl chloride-based resin.

(130) As the hindered amine-based light stabilizer, the above-mentioned ones are exemplified. When blending a light stabilizer, the blending amount is recommended to be about 0.1 to 10 parts by weight with respect to 100 parts by weight of the vinyl chloride-based resin.

(131) As the flame retardant, the above-mentioned ones are exemplified. When blending a flame retardant, the blending amount is recommended to be about 0.1 to 20 parts by weight with respect to 100 parts by weight of the vinyl chloride-based resin.

(132) As the coloring agent, the above-mentioned ones are exemplified. When blending a coloring agent, the blending amount is recommended to be about 1 to 100 parts by weight with respect to 100 parts by weight of the vinyl chloride-based resin.

(133) As the processing aid, the above-mentioned ones are exemplified. When blending a processing aid, the blending amount is recommended to be about 0.1 to 20 parts by weight with respect to 100 parts by weight of the vinyl chloride-based resin.

(134) As the filler, the above-mentioned ones are exemplified. When blending a filler, the blending amount is recommended to be about 1 to 100 parts by weight with respect to 100 parts by weight of the vinyl chloride-based resin.

(135) As the lubricant, the above-mentioned ones are exemplified. When blending a lubricant, the blending amount is recommended to be about 0.1 to 10 parts by weight with respect to 100 parts by weight of the vinyl chloride-based resin.

(136) As the antistatic agent, the above-mentioned ones are exemplified. When blending an antistatic agent, the blending amount is recommended to be about 0.1 to 10 parts by weight with respect to 100 parts by weight of the vinyl chloride-based resin.

(137) The vinyl chloride-based resin composition for automotive interior materials of the present invention can be converted into a mixed powder of the vinyl chloride-based resin composition for automotive interior materials by stirring and mixing the present diester, the vinyl chloride-based resin, and various additives as needed, using a stirrer such as a mortar mixer, a Henschel mixer, a Banbury mixer, and a ribbon blender.

(138) The present diester, a vinyl chloride-based resin, and if necessary, various additives can be melt-molded into a pelletized vinyl chloride-based resin composition for automotive interior by a kneading machine such as a conical twin-screw extruder, a parallel twin-screw extruder, a single screw extruder, a co-kneader kneading machine, and a roll kneader.

(139) Further, the present diester, a pasty vinyl chloride-based resin, and if necessary, various additives can be mixed homogenously with each other by a mixer such as a pony mixer, a butterfly mixer, a planetary mixer, a ribbon blender, a kneader, a dissolver, a twin screw mixer, a Henschel mixer, and a triple roll mill, and defoaming treatment is optionally carried out under reduced pressure to be able to obtain a pasty vinyl chloride-based resin composition for automotive interior.

(140) [Automotive Interior Material]

(141) The vinyl chloride-based resin composition (powder formulation or pellet formulation) for automotive interiors according to the present invention can be melt-molded into a desired shape of an automotive interior material by using a conventionally known method such as vacuum molding, compression molding, extrusion molding, injection molding, calender molding, press molding, blow molding, and powder molding.

(142) On the other hand, the above pasty vinyl chloride-based resin composition for automotive interior can be molded into a desired shape of an automotive interior material by using a conventionally known method such as spread molding, dipping molding, gravure molding, slush molding, and screen processing.

(143) The automotive interior material thus obtained can be suitably used as an interior material for automobiles, such as instrument panel, door trim, trunk trim, seat sheet, pillar cover, ceiling material, rear tray, console box, airbag cover, armrest, headrest, meter cover, crash pad, and floor carpet.

(144) <Medical Vinyl Chloride-Based Resin Composition>

(145) The greatest feature of the vinyl chloride-based resin composition of the present invention resides in that it contains the present diester as a plasticizing component (plasticizer) or a stabilizing component (stabilizer), and the vinyl chloride-based resin composition can be obtained by blending the present diester with a vinyl chloride-based resin.

(146) [Vinyl Chloride-Based Resin]

(147) Since the vinyl chloride-based resin used in the present invention is as described above, its explanation will be omitted.

(148) [Medical Vinyl Chloride-Based Resin Composition]

(149) The content of the present diester in the medical vinyl chloride-based resin composition of the present invention is appropriately selected according to the applications, but the content of the present diester is usually 5 to 200 parts by weight, preferably 5 to 100 parts by weight, with respect to 100 parts by weight of the vinyl chloride-based resin. Even when the content of the present diester is in the above range, the content of the present diester is recommended to be preferably in the range of 30 to 200 parts by weight, more preferably in the range of 30 to 150 parts by weight, particularly preferably in the range of 40 to 100 parts by weight, depending on the method of use (application) of the medical vinyl chloride-based resin composition of the present invention, for example, in the case of the composition used as a soft material. When the medical vinyl chloride-based resin composition is used as a semi-hard material, the recommended content of the present diester is preferably in the range of 5 parts by weight or more but less than 30 parts by weight, more preferably in the range of 5 parts by weight or more but less than 20 parts by weight. If the content of the present diester is less than 5 parts by weight, the mechanical properties and the deterioration preventing effect at the time of sterilization and disinfection may be insufficient in some cases. When the present diester is added in an amount exceeding 200 parts by weight, bleeding to the surface of the molded article is severe. Both cases may be undesirable. When a filler or the like is added to the vinyl chloride-based resin composition, the filler itself absorbs oil, so that the present diester can be added beyond the above-mentioned range. For example, when 100 parts by weight of calcium carbonate is blended as a filler with respect to 100 parts by weight of the vinyl chloride-based resin, the plasticizer may be blended in an amount of about 5 to 500 parts by weight.

(150) In order to much more suppress deterioration after sterilization and disinfection treatment, inclusion of only the present diester may be sufficient for such purpose, but further inclusion of a stabilizer such as a metal soap compound and a radiation-resistant material of a silane compound type is much better for such suppression.

(151) As the stabilizer, the above-mentioned ones are exemplified. When blending a stabilizer, the blending amount is recommended to be about 0.1 to 20 parts by weight with respect to 100 parts by weight of the vinyl chloride-based resin. The metal soap compound may exert a function as a processing aid or as a lubricant together with a function as a stabilizer in some cases.

(152) Among the stabilizers, a combination of calcium stearate and zinc stearate is most preferably used from the viewpoint of safety and the like. Further, the total blending amount is recommended to be about 0.1 to 10 parts by weight, preferably about 0.2 to 6 parts by weight, and the blending ratio is not particularly limited as long as such blending ratio is in a range capable of showing a stabilization effect, but such combination is usually used in the range of 5:1 to 1:5 in many cases.

(153) Examples of the silane compound-based radiation-resistant material include monoalkoxysilane compounds such as trimethylmethoxysilane, trimethylethoxysilane, triethylmethoxysilane, and triethylethoxysilane; dialkoxysilane compounds such as dimethyldimethoxysilane, diethyldimethoxysilane, dimethyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, methylaminoethoxypropyldialkoxysilane, N-(-aminoethyl)--aminopropylmethyldimethoxysilane, -glycidoxypropylmethyldimethoxysilane, and -methacryloxypropylmethyldimethoxysilane; trialkoxysilane compounds such as methyltrimethoxysilane, methyltriethoxysilane, hexyltrimethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, -chloropropyltrimethoxysilane, -aminopropyltriethoxysilane, N-(-aminoethyl)--aminopropyltrimethoxysilane, N-(phenyl)--aminopropyltrimethoxysilane, -glycidoxypropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, -mercaptopropyltrimethoxysilane, -(polyethyleneamino)propyltrimethoxysilane, -ureidopropyltriethoxysilane, heptadecafluorodecyltrimethoxysilane, tridecafluorooctyltrimethoxysilane, vinyltris(-methoxyethoxy)silane, and -(3,4-epoxycyclohexyl)ethyltrimethoxysilane; tetraalkoxysilane compounds such as tetramethoxysilane and tetraethoxysilane; acetoxysilane compounds such as vinyltriacetoxysilane; chlorosilane compounds such as trimethylchlorosilane, dimethyldichlorosilane, methyltrichlorosilane, vinyltrichlorosilane, and -chloropropylmethyldichlorosilane; organosilane compounds such as triisopropylsilane, triisopropylsilyl acrylate, allyltrimethylsilane, and methyl trimethylsilylacetate; and the like. When blending a radiation resistant material, the blending amount is recommended to be about 0.1 to 15 parts by weight with respect to 100 parts by weight of the vinyl chloride-based resin.

(154) In the medical vinyl chloride-based resin composition of the present invention, other known plasticizers can be used together with the present diester. In addition, it is also possible to blend, if necessary, additives such as stabilizing aid, antioxidants (aging inhibitors), ultraviolet absorbers, hindered amine-based light stabilizers, fillers, diluents, viscosity reducing agents, thickeners, processing aids, lubricants, antistatic agents, flame retardants, foaming agents, adhesives, and coloring agents.

(155) Other plasticizers other than the above diester, and additives may be blended singly or in combination of two or more kinds thereof in appropriate combination with the present diester.

(156) As the known plasticizer that can be used in combination with the present diester, the above-mentioned ones are exemplified. When blending a plasticizer that can be used in combination, the blending amount is recommended to be about 1 to 100 parts by weight with respect to 100 parts by weight of the vinyl chloride-based resin.

(157) As the stabilizing aid, the above-mentioned ones are exemplified. When blending a stabilizing aid, the blending amount is recommended to be about 0.1 to 20 parts by weight with respect to 100 parts by weight of the vinyl chloride-based resin.

(158) As the antioxidant, the above-mentioned ones are exemplified. When blending an antioxidant, the blending amount is recommended to be about 0.2 to 20 parts by weight with respect to 100 parts by weight of the vinyl chloride-based resin.

(159) As the ultraviolet absorber, the above-mentioned ones are exemplified. When blending an ultraviolet absorber, the blending amount is recommended to be about 0.1 to 10 parts by weight with respect to 100 parts by weight of the vinyl chloride-based resin.

(160) As the hindered amine-based light stabilizer, the above-mentioned ones are exemplified. When blending a light stabilizer, the blending amount is recommended to be about 0.1 to 10 parts by weight with respect to 100 parts by weight of the vinyl chloride-based resin.

(161) As the filler, the above-mentioned ones are exemplified. When blending a filler, the blending amount is recommended to be about 1 to 100 parts by weight with respect to 100 parts by weight of the vinyl chloride-based resin.

(162) Examples of the diluent include 2,2,4-trimethyl-1,3-pentanediol diisobutyrate, and aliphatic or aromatic hydrocarbons having a low boiling point. When blending a diluent, the blending amount is recommended to be about 1 to 50 parts by weight with respect to 100 parts by weight of the vinyl chloride-based resin.

(163) Examples of the viscosity reducing agent include various non-ionic surfactants, sulfosuccinate-based anionic surfactants, silicone-based compounds having surface activity, soybean oil lecithin, monohydric alcohols, glycol ethers, polyethylene glycols, and the like. When blending a viscosity reducing agent, the blending amount is recommended to be about 0.1 to 20 parts by weight with respect to 100 parts by weight of the vinyl chloride-based resin.

(164) Examples of the thickener include synthetic fine powder silica-based thickeners, bentonite-based thickeners, superfine precipitated calcium carbonates, metal soap-based thickeners, hydrogenated castor oil, polyamide wax, polyethylene oxide-based thickeners, vegetable oil-based thickeners, sulfate-based surfactants, non-ionic surfactants, and the like. When blending a thickener, the blending amount is recommended to be about 1 to 50 parts by weight with respect to 100 parts by weight of the vinyl chloride-based resin.

(165) As the processing aid, the above-mentioned ones are exemplified. When blending a processing aid, the blending amount is recommended to be about 0.1 to 20 parts by weight with respect to 100 parts by weight of the vinyl chloride-based resin.

(166) As the lubricant, the above-mentioned ones are exemplified. When blending a lubricant is, the blending amount is recommended to be about 0.1 to 10 parts by weight with respect to 100 parts by weight of the vinyl chloride-based resin.

(167) As the antistatic agent, the above-mentioned ones are exemplified. When blending an antistatic agent, the blending amount is recommended to be about 0.1 to 10 parts by weight with respect to 100 parts by weight of the vinyl chloride-based resin.

(168) As the flame retardant, the above-mentioned ones are exemplified. When blending a flame retardant, the blending amount is recommended to be about 0.1 to 20 parts by weight with respect to 100 parts by weight of the vinyl chloride-based resin.

(169) Examples of the foaming agent include organic foaming agents such as azodicarbonamide and oxybisbenzenesulfonyl hydrazide, and inorganic foaming agents such as sodium bicarbonate. When blending a foaming agent, the blending amount is recommended to be about 0.1 to 30 parts by weight with respect to 100 parts by weight of the vinyl chloride-based resin.

(170) As the coloring agent, the above-mentioned ones are exemplified. When blending a coloring agent, the blending amount is recommended to be about 1 to 20 parts by weight with respect to 100 parts by weight of the vinyl chloride-based resin.

(171) The medical vinyl chloride-based resin composition of the present invention can be converted into a powder form, a pellet form or a paste form, for example, by mixing the present diester, the vinyl chloride-based resin, the stabilizer, the silane compound, and as necessary, various additives by hand, depending on purpose of use and applications, or by stirring/mixing them or melt mixing them using an agitation mixer such as a pony mixer, a butterfly mixer, a planetary mixer, a dissolver, a biaxial mixer, a three-roll mill, a mortar mixer, a Henschel mixer, a Banbury mixer, and a ribbon blender, or using a kneader such as a conical twin-screw extruder, a parallel twin-screw extruder, a single screw extruder, a co-kneader, and a roll kneader.

(172) [Medical Material]

(173) The medical vinyl chloride-based resin composition according to the present invention can be molded into a medical material that is a molded body having a desired shape, by molding process using a conventionally known method such as vacuum molding, compression molding, extrusion molding, injection molding, calender molding, press molding, blow molding, powder molding, spread coating, dip coating, spray coating, paper casting, extrusion coating, gravure printing, screen printing, slush molding, rotational molding, casting, dip molding, and welding.

(174) The shape of the molded body that is a medical material is not particularly limited, but may include, for example, a rod shape, a sheet shape, a film shape, a plate shape, a cylindrical shape, a circular shape, an elliptical shape or the like or a special shape such as a star shape and a polygonal shape.

(175) The molded body thus obtained, which is a material for medical use, is very useful as a medical material such as tubes (e.g. chest tubes, dialysis tubes, artificial respiration tubes, endotracheal tubes, respiration apparatus tubes, nutrition tubes, extension tubes, etc.); catheters (e.g. urinary catheters, suction catheters, intravenous injection catheters, digestive tract catheters, etc.); bags (e.g. blood bags, transfusion bags, liquid medicine bags, drain bags, etc.); circuit apparatus parts (e.g. blood component separators, hemodialysis circuits, peritoneal dialysis circuits, artificial heart-lung circuits, etc.); connector members (e.g. connection members, branch valves, speed adjusting members, etc.); medical materials (e.g. transfusion sets, blood transfusion sets, intravenous injection sets, cardiopulmonary bypasses, surgical gloves, packaging materials for pharmaceutical products, medical films, sanitary materials, respiration masks, etc.).

EXAMPLES

(176) Examples are shown below to more specifically explain the present invention. The present invention is not limited to these examples. Abbreviations of the compounds and measurements of the respective characteristics in examples and application examples are shown below.

First Embodiment of the Present Invention

(177) (1) Number of Carbon Atoms of Alkyl Group and Ratio of Linear-Chain Alkyl Group

(178) As to the number of carbon atoms of the alkyl group and the ratio of the linear-chain alkyl group in the 4-cyclohexene-1,2-dicarboxylic acid diester and the 4,5-epoxycyclohexane dicarboxylic acid diester used in examples and application examples, composition in the raw material alcohol used for the production of such diester compound was measured by gas chromatography (hereinafter abbreviated as GC) and the results were defined as the number of carbon atoms of the alkyl group and the ratio of the linear-chain alkyl group in the raw material ester or in the present diester. The method of measuring the raw material alcohol by GC is as follows.

(179) <<GC Measurement Conditions>>

(180) Apparatus: Gas chromatograph GC-17A (manufactured by Shimadzu Corporation)

(181) Detector: FID

(182) Column: Capillary column ZB-1 30 m

(183) Column temperature: raised from 60 C. to 290 C., temperature rise rate: 13 C./min

(184) Carrier gas: Helium

(185) Sample: 50% acetone solution

(186) Injection volume: 1 L

(187) Quantitative determination: Quantitative determination was performed using n-propyl benzoate as an internal standard substance.

(188) In selecting the internal standard substance, it has been confirmed in advance that n-propyl benzoate in the raw material alcohol is below the detection limit by GC.

(189) In the above-mentioned esterification reaction, there is no difference in reactivity depending on the structure of the raw material alcohol within the scope of the present invention, and it has been confirmed beforehand that there is no difference between the composition ratio of the raw material alcohol used and the composition ratio of the alkyl group in the raw material ester and in the present diester.

(190) (2) Analysis of Raw Material Ester and Diester

(191) The present diester obtained in the following examples was analyzed by the following method. For the raw material ester as the intermediate material, the following analysis method was also applied.

(192) Element Analysis

(193) <Carbon/Hydrogen>

(194) Organic element analyzer: trade name CHN Coder MT-5, manufactured by Yanako Bunseki Kogyo KK

(195) Sample amount: 2 mg

(196) Burning furnace temperature: 970 C.

(197) Oxidizing furnace temperature: 850 C.

(198) Reducing furnace temperature: 590 C.

(199) Gas flow rate during combustion: He gas 200 ml/min.

(200) O.sub.2 gas 20 ml/min.

(201) <Oxygen>

(202) Organic element analyzer: trade name Element Analyzer JM-10, manufactured by J-Science Lab Co., Ltd.

(203) Sample amount: 2 mg

(204) Burning furnace temperature: 950 C.

(205) Oxidizing furnace temperature: 850 C.

(206) Reducing furnace temperature: 550 C.

(207) Gas flow ratio during combustion: He gas 200 ml/min.

(208) O.sub.2 gas 20 ml/min.

(209) Nuclear Magnetic Resonance Spectroscopic Analysis (NMR Analysis)

(210) NMR analyzer: trade name DRX-500, manufactured by Bruker

(211) Solvent: deuterated chloroform (CDCl.sub.3)

(212) Internal standard substance: tetramethylsilane (TMS)

(213) Sample tube: 5 mm

(214) .sup.1H-NMR: resonance frequency: 500.1 MHz, number of integrations 4 times

(215) .sup.13C-NMR resonance frequency: 125.8 MHz, number of integrations 71 times

(216) The measurement sample was prepared by diluting 20 mg of the sample with 0.8 ml of the solvent.

(217) Infrared Spectroscopic Analysis (IR Analysis)

(218) FT-IR device: trade name Spectrum One, manufactured by Perkin Elmer Co. Ltd., measurement range: 650 to 4000 cm.sup.1, measurement method: ATR method, number of integrations: 4 times, resolution: 4.00 cm.sup.1

(219) For the measurement, the sample was dropped directly onto the cell of the apparatus and then analyzed.

(220) Chemical Analysis

(221) Ester value: measured according to JIS K-0070 (1992).

(222) Acid value: measured according to JIS K-0070 (1992).

(223) Iodine value: measured according to JIS K-0070 (1992).

(224) Oxirane oxygen: measured according to Method for Determination of Oxirane Oxygen (Part 1) of Standard Fat Analysis Test Method 2.3.7.1-2013.

(225) Hue: measured according to JIS K-0071 (1998) to obtain a Hazen unit color number.

Example 1

(226) Esterification Reaction

(227) A 2 L four-necked flask equipped with a thermometer, a decanter, a stirring blade and a reflux condenser was charged with 182.6 g (1.2 moles) of 4-cyclohexene-1,2-dicarboxylic anhydride (RICACID TH, manufactured by New Japan Chemical Co., Ltd.), 416 g (2.9 moles) of a saturated aliphatic alcohol containing 85.1% by weight of a linear-chain saturated aliphatic alcohol having 9 carbon atoms and 11.7% of a branched chain saturated aliphatic alcohol having 9 carbon atoms (LINEVOL 9, manufactured by Shell Chemicals Co., Ltd.: linear chain ratio (molar ratio): 85%), and 0.24 g of tetraisopropyl titanate as an esterification catalyst, and the esterification reaction was carried out at a reaction temperature of 200 C. The reaction was carried out until the acid value of the reaction solution became 0.5 mg KOH/g while removing the produced water out of the system by refluxing the alcohol under reduced pressure. After completion of the reaction, the unreacted alcohol was distilled out of the system under reduced pressure, and the system was neutralized, washed with water, and dehydrated according to a conventional method, thereby to obtain 449 g of an objective 4-cyclohexene-1,2-dicarboxylic acid diester (hereinafter referred to as raw material ester 1).

(228) The raw material ester 1 thus obtained had an ester value of 262 mg KOH/g, an acid value of 0.04 mg KOH/g, and a hue of 15.

(229) Epoxidation Reaction

(230) Then, 423 g (1.0 mole) of the raw material ester 1 was charged into a 1 L four-necked flask equipped with a thermometer, a stirring blade and a cooling tube, and the temperature was raised to 60 to 70 C. After the temperature was raised, 76.6 g (1.35 moles) of 60% hydrogen peroxide water, 18.3 g (0.30 moles) of 76% formic acid, and 1.47 g (0.01 moles) of 75% phosphoric acid were slowly added dropwise over a period of 2.25 hours. After completion of the dropwise addition, the above temperature was maintained for further 4 hours, and the reaction was completed by aging. After completion of the reaction, the aqueous phase was removed to the outside of the system, followed by washing with water and dehydration in a conventional manner to obtain 397 g of an objective 4,5-epoxycyclohexane-1,2-dicarboxylic acid diester (hereinafter referred to as the diester 1).

(231) The obtained diester 1 was a transparent liquid and had an ester value of 256 mg KOH/g, an acid value of 0.06 mg KOH/g, an iodine value of 2.5 g I.sub.2/100 g, an oxirane oxygen content of 3.5%, and a hue of 10.

(232) Elemental analysis, NMR analysis, and IR analysis were carried out on the obtained diester 1, and the results were summarized in Table 1.

(233) The isomer ratio (cis form/trans form, molar ratio) of the oxirane ring site of the present diester 1 calculated from the results of .sup.1H-NMR analysis in Table 1 was 20/80.

Example 2

(234) In the same manner as in Example 1 except that 400 g (2.5 moles) of a saturated aliphatic alcohol having 9 to 11 carbon atoms wherein the ratio (molar ratio) of 9 carbon atoms/10 carbon atoms/11 carbon atoms was 18:42:38 and the overall linear chain ratio was 84% (NEODOL 911, manufactured by Shell Chemicals Co., Ltd.) was added instead of 416 g of the saturated aliphatic alcohol (LINEVOL 9, manufactured by Shell Chemicals Co., Ltd.), 404 g of 4,5-epoxycyclohexane dicarboxylic acid diester (hereinafter referred to as the diester 2) was obtained.

(235) The obtained diester 2 had an ester value of 242 mg KOH/g, an acid value of 0.04 mg KOH/g, an iodine value of 1.9 g I.sub.2/100 g, an oxirane oxygen content of 3.1%, and a hue of 10.

(236) Elemental analysis, NMR analysis, and IR analysis were carried out on the obtained diester 2, and the results were summarized in Table 1.

(237) The isomer ratio (cis form/trans form, molar ratio) of the oxirane ring site of the present diester 2 calculated from the results of .sup.1H-NMR analysis in Table 1 was 20/80.

(238) TABLE-US-00001 TABLE 1 Element Characteristic Characteristic nuclear magnetic resonance absorption (ppm) Ex- analysis (%) infrared .sup.1H-NMR(CDCl.sub.3) .sup.13C-NMR(CDCl.sub.3) ample Calcd. Found absorption (cm.sup.1) 500.1 MHz 125.8 MHz 1 C: 71.12 C: 71.46 1178 Absorption of 0.89(t, CH3) Proton of terminal 14.1(CH3) Carbon of terminal H: 10.56 H: 9.81 oxirane ring methyl of ester-bonded methyl of ester-bonded O: 18.22 O: 17.88 and alkyl group alkyl group ester group 1.27-1.30 Proton of methylene of 22.7, 24.8, 25.9, Carbon of methylene (m, CH2) ester-bonded alkyl 28.5, 29.2, 29.2, of ester-bonded alkyl group 29.5(OCH2) group 1353- Absorption of 1.62(t, Proton of -methylene 31.8(CyCH2) Carbon of methylene of 1466 alkane bound OCH2CH2) of ester-bonded alkyl cyclohexane ring to ester and group cyclohexane 2.19-2.30 Proton of methylene of 37.7(CyCH) Carbon of cyclohexane ring (m, CyCH2) cyclohexane ring ring at -position of carbonyl group 1732 Absorption of 2.90(t, CyCH) Proton of cyclohexane 50.9(HCOCH) Carbon of methine of ester group ring at -position of oxirane ring (cis form) carbonyl group 3.16 Proton of oxirane ring 51.6(HCOCH) Carbon of methine of (s, HCOCH) methine (cis form) oxirane ring (trans form) 2855- Absorption of 3.24 Proton of oxirane ring 65.1 Carbon of -methylene 2955 alkane bound (s, HCOCH) methine (trans form) (OCH2CH2) of ester-bonded to ester and alkyl group cyclohexane 4.06(t, Proton of -methylene 173.0(CO) Carbon of carbonyl ring OCH2CH2) of ester-bonded alkyl group group 2 C: 72.13 C: 72.38 1178 Absorption of 0.86-0.92 Proton of terminal 14.1, 14.1(CH3) Carbon of terminal H: 10.82 H: 10.31 oxirane ring (m, CH3) methyl of ester-bonded methyl of ester-bonded O: 17.05 O: 16.67 and ester alkyl group alkyl group group 1.26-1.30 Proton of methylene of 22.7, 24.8, 25.9, Carbon of methylene (m, CH2) ester-bonded alkyl 28.5, 29.3, 29.3, of ester-bonded alkyl group 29.5, 29.5, group 29.6(OCH2) 1377- Absorption of 1.60(t, Proton of -methylene 31.8(CyCH2) Carbon of methylene 1466 alkane bound OCH2CH2) of ester-bonded alkyl of cyclohexane ring to ester and group cyclohexane 2.10-2.29 Proton of methylene 37.7(CyCH) Carbon of cyclohexane ring (m, CyCH2) of cyclohexane ring ring at -position of carbonyl group 1732 Absorption of 2.74(t, CyCH) Proton of cyclohexane 50.9(HCOCH) Carbon of methine of ester group ring at -position of oxirane ring (cis form) carbonyl group 3.16(s, Proton of oxirane ring 51.6(HCOCH) Carbon of methine of HCOCH) methine (cis form) oxirane ring (trans form) 2854- Absorption of 3.24(S, Proton of oxirane ring 65.11 Carbon of -methylene 2955 alkane bound HCOCH) methine (trans form) (OCH2CH2) of ester-bonded alkyl to ester and group cyclohexane 4.06(t, Proton of -methylene 173.0(CO) Carbon of carbonyl ring OCH2CH2) of ester-bonded alkyl group group

Application Example 1

(239) To 100 parts by weight of a versatile vinyl chloride-based resin (trade name Zest 1000z, manufactured by Shin Dai-Ichi Vinyl Corporation) were respectively added 0.3 parts by weight of calcium stearate (manufactured by Nacalai Tesque, Inc.) and 0.2 parts by weight of zinc stearate (manufactured by Nacalai Tesque, Inc.), and the mixture was stirred and mixed with a mortar mixer, and then 50 parts by weight of the diester 1 obtained in Example 1 or the diester 2 obtained in Example 2 was added. The mixture was further mixed until uniform to obtain a vinyl chloride-based resin composition. This resin composition was melt-kneaded at 160 to 166 C. for 4 minutes using a 512 inches twin roll to prepare a roll sheet, followed by press molding at 162 to 168 C.10 minutes to prepare a press sheet having a thickness of about 1 mm.

(240) Subsequently, a versatile di-2-ethylhexyl phthalate (hereinafter referred to as DOP) instead of the diester according to the present invention, diisononyl 1,2-cyclohexanedicarboxylate (hereinafter referred to as DINCH) that is a cyclohexane dicarboxylic acid diester containing no epoxy group in the molecular structure, and di-2-ethylhexyl 4,5-epoxycyclohexane dicarboxylate (hereinafter referred to as E-DEHTH) having a structure outside the scope of the present invention were added in the same manner as above to prepare a vinyl chloride sheet (press sheet).

(241) Using the vinyl chloride sheet obtained above, a tensile test, a cold resistance test, and a heat resistance test were carried out to compare physical properties between the vinyl chloride sheet blended with the diester according to the present invention and the vinyl chloride sheet blended with DOP, DINCH, or E-DEHTH outside the scope of the present invention.

(242) The vinyl chloride sheet blended with the diester according to the present invention was confirmed to be excellent in plasticizer performances because it has very excellent properties as shown by 100% modulus and elongation of the tensile test results, such as flexibility and plasticizing performance equivalent to or better than those of the vinyl chloride sheet blended with other plasticizers.

(243) Further, from the cold resistance test results, it was confirmed that the vinyl chloride sheet blended with the diester of the present invention was very excellent in cold resistance because the sheet has the softening temperature that was lower by 10 C. or more than that of the vinyl chloride sheet blended with other plasticizers such as E-DEHTH, etc.

(244) Further, from the results of the heat resistance test, the volatile loss at 170 C. of the vinyl chloride sheet blended with the diester of the present invention is reduced to to 1/7 as compared with the vinyl chloride sheet blended with other plasticizer, and the vinyl chloride sheet of the present invention was confirmed to be very excellent in heat resistance.

(245) At the same time, when the discoloration of the vinyl chloride sheet in the above heat resistance test was examined, the vinyl chloride sheet blended with other plasticizer markedly colored in about 1 hour, whereas the vinyl chloride sheet blended with the diester of the present invention was hardly colored, and thus the diester of the present invention was confirmed to acts as a plasticizer and as a stabilizer at the same time.

Application Example 2

(246) To 100 parts by weight of a versatile vinyl chloride-based resin (trade name Zest 1000z, manufactured by Shin Dai-Ichi Vinyl Corporation) was added 19 parts by weight of the diester 1 obtained in Example 1 or 10 parts by weight of the diester 2 obtained in Example 2, and then 3.0 parts by weight of a calcium-zinc complex stabilizer were further added thereto. The mixture was stirred and mixed with a mortar mixer to prepare a vinyl chloride-based resin composition. This resin composition was melt-kneaded at 170 to 176 C. for 4 minutes using a 512 inches twin roll to prepare a roll sheet, followed by press molding at 172 to 178 C.10 minutes to prepare a press sheet having a thickness of about 0.5 mm.

(247) Using the vinyl chloride sheet obtained above, a tensile test and a heat resistance test were carried out to compare the physical properties between the vinyl chloride sheet blended with the diester of the present invention and the vinyl chloride sheet being not blended with the diester, which is outside the scope of the present invention.

(248) The vinyl chloride sheet not blended with the diester of the present invention begins to be colored in about 30 minutes at a high temperature of 170 C. and becomes markedly colored in about 1 hour, whereas the vinyl chloride sheet blended with the diester of the present invention had little discoloration even after 1 hour under such condition and the diester of the present invention was confirmed to effectively act as a stabilizer, too.

(249) From the above results, it is clear that the diester of the present invention is very useful as a plasticizer and also as a stabilizer.

Second Embodiment of the Present Invention

(250) (1) Number of Carbon Atoms of Alkyl Group, and Ratio of Linear-Chain Alkyl Group

(251) The number of carbon atoms of alkyl group and the ratio of the linear-chain alkyl group in the plasticizer used in the examples and comparative examples of the present invention were determined by gas chromatography (hereinafter abbreviated as GC) of the composition in the raw material alcohol used for the production. The result was defined as the number of carbon atoms of alkyl group and the ratio of the linear-chain alkyl group in the plasticizer. The method of measuring the raw material alcohol by GC is the same as above.

(252) (2) Evaluation of Physical Properties of Present Diester

(253) The ester value, acid value, iodine value, oxirane oxygen, and hue of the diester obtained in the following production examples were analyzed in the same manner as described above.

(254) (3) Molding Processability

(255) Approximately 0.01 g of a sample obtained by mixing 10 g of a plasticizer with 2 g of a vinyl chloride-based resin (straight, polymerization degree 1050, trade name Zest 1000Z, manufactured by Shin Dai-Ichi Vinyl Corporation) was dropped onto a slide glass. A cover glass was covered on the slide glass, and set to a melting point apparatus for micro-quantity of a sample. The temperature was raised at a rate of 5 C./min, and changes in the state of the particles of the vinyl chloride-based resin by heating were observed. The temperature at which the particles of the vinyl chloride-based resin start melting and the temperature at which the particles become transparent were defined as the gelation initiation temperature and the gelation termination temperature, respectively, and the average value of them was defined as the gelation temperature. The lower the gelation temperature, the faster the absorption rate of the plasticizer as well as the better the processability.

(256) (4) Preparation of Vinyl Chloride Sheet (Sheet for Tensile Properties Test, Cold Resistance Test, and Heat Resistance Test)

(257) To 100 parts by weight of a vinyl chloride resin (straight, degree of polymerization 1050, trade name Zest 1000Z) were respectively added 0.3 parts by weight of calcium stearate (manufactured by Nacalai Tesque Co., Ltd.) and 0.2 parts by weight of zinc stearate (manufactured by Nacalai Tesque Co., Ltd.) as a stabilizer. The mixture was stirred and mixed with a mortar mixer, then 50 parts by weight of a plasticizer were added and mixed by hand until homogeneous to obtain a vinyl chloride-based resin composition. This resin composition was melt-kneaded at 160 to 166 C. for 4 minutes using a 512 inches twin roll to prepare a roll sheet. Subsequently, press molding of the roll sheet was performed at 162 to 168 C. for 10 minutes to prepare a press sheet having a thickness of about 1 mm.

(258) [Evaluation of Physical Properties of Resin]

(259) (5) Tensile Characteristics: The 100% modulus, the breaking strength and the breaking elongation of the press sheet were measured according to JIS K-6723 (1995). The measurement demonstrated that the smaller the 100% modulus, the more desirable the flexibility. The breaking strength and the breaking elongation are indications of the practical strength of the material. Generally, it can be said that the greater these values, the more superior the practical strength.
(6) Cold Resistance: The cold resistance was measured according to JIS K-6773(1999) using a Clash-Berg tester. The lower the softening temperature ( C.), the more superior the cold resistance. The softening temperature here means the temperature of the low-temperature limit at which a predetermined torsional rigidity rate (3.1710.sup.3 kg/cm.sup.2) is obtained in the above measurement.
(7) Heat Resistance: The heat resistance was evaluated based on volatile loss and sheet discoloration.
a) Volatile loss: The roll sheet was heated in a gear oven at 170 C. for 60 minutes and 120 minutes, and a change in the weight was measured; then, the volatile loss (%) was calculated according to the following equation. The smaller the value of volatile loss, the higher the heat resistance.
Volatile loss (%)=((Weight before testWeight after test)/Weight before test)100
b) Sheet discoloration: The roll sheet was heated in a gear oven at 170 C. for 30 minutes and 60 minutes; thereafter, the intensity of discoloration of each roll sheet was visually evaluated on a six-level scale.
: Discoloration was not observed.
: Slight discoloration was observed.
: Insignificant discoloration was observed.
: Discoloration was observed.
x: Strong discoloration was observed.
xx: Significant discoloration was observed.

Production Example 1

(260) Esterification Reaction

(261) A 2 L four-necked flask equipped with a thermometer, a decanter, a stirring blade and a reflux condenser was charged with 182.6 g of 4-cyclohexene-1,2-dicarboxylic anhydride (1.2 moles, RICACIDTH, manufactured by New Japan Chemical Co., Ltd.), 416 g (2.9 moles) of a saturated aliphatic alcohol containing 85.1% by weight of a linear-chain saturated aliphatic alcohol having 9 carbon atoms and 11.7% of a branched-chain saturated aliphatic alcohol having 9 carbon atoms (LINEVOL 9, manufactured by Shell Chemicals Co., Ltd.), and 0.24 g of tetraisopropyl titanate as an esterification catalyst, and then the esterification reaction was carried out at a reaction temperature of 200 C. The reaction was carried out until the acid value of the reaction solution became 0.5 mg KOH/g while removing the produced water out of the system by refluxing the alcohol under reduced pressure. After completion of the reaction, the unreacted alcohol was distilled out of the system under reduced pressure, and the system was neutralized, washed, and dehydrated according to a conventional method to obtain 449 g of an objective 4-cyclohexene-1,2-dicarboxylic acid diester (hereinafter referred to as ester 1).

(262) The ester 1 thus obtained had an ester value of 254 mg KOH/g, an acid value of 0.04 mg KOH/g, and a hue of 15.

(263) Epoxidation Reaction

(264) Then, 423 g (1.0 mole) of the ester 1 obtained in the above esterification reaction was charged into a 1 L four-necked flask equipped with a thermometer, a stirring blade and a cooling tube, and the temperature was raised to 60 to 70 C. After the temperature rise, 76.6 g (1.35 moles) of 60% hydrogen peroxide water, 18.3 g (0.30 moles) of 76% formic acid, and 1.47 g (0.01 moles) of 75% phosphoric acid were slowly added dropwise over a period of 2.25 hours. After completion of the dropwise addition, the above temperature was maintained for further 4 hours, and the reaction was completed by aging. After completion of the reaction, the aqueous phase was removed to the outside of the system, followed by washing with water and dehydration in a conventional manner to obtain 397 g of an objective 4,5-epoxycyclohexane dicarboxylic acid diester (hereinafter referred to as epoxy 1).

(265) The epoxy 1 thus obtained had an ester value of 256 mg KOH/g, an acid value of 0.06 mg KOH/g, an iodine value of 2.5 g I.sub.2/100 g, an oxirane oxygen content of 3.5%, and a hue of 10.

Production Example 2

(266) In the same manner as in Production Example 1 except that 400 g (2.5 moles) of mixed saturated aliphatic alcohols having 9 to 11 carbon atoms (NEODOL 911, manufactured by Shell Chemicals Co., Ltd.) wherein the ratio of 9 carbon atoms/10 carbon atoms/11 carbon atoms is 19:43:38 and the overall linear chain ratio was 84% was added instead of 416 g of the saturated aliphatic alcohol (LINEVOL 9, manufactured by Shell Chemicals Co., Ltd.), 404 g of a 4,5-epoxycyclohexane dicarboxylic acid diester (hereinafter referred to as epoxy 2) was obtained.

(267) The epoxy 2 thus obtained had an ester value of 242 mg KOH/g, an acid value of 0.04 mg KOH/g, an iodine value of 1.9 g I.sub.2/100 g, an oxirane oxygen content of 3.1%, and a hue of 10.

Production Example 3

(268) In the same manner as in Production Example 1 except that 251 g (1.7 moles) of n-nonyl alcohol and 167 g (1.2 moles) of isononyl alcohol were added instead of 416 g of the saturated aliphatic alcohol (LINEVOL 9, manufactured by Shell Chemicals Co., Ltd.), 390 g of 4,5-epoxycyclohexane dicarboxylic acid diester (hereinafter referred to as epoxy 3) was obtained.

(269) The epoxy 3 thus obtained had an ester value of 250 mg KOH/g, an acid value of 0.02 mg KOH/g, an iodine value of 1.9 g I.sub.2/100 g, an oxirane oxygen content of 3.3%, and a hue of 10.

Production Example 4

(270) In the same manner as in Production Example 1 except that 374 g (2.9 moles) of 2-ethylhexanol was added instead of 416 g of the saturated aliphatic alcohol (LINEVOL 9, manufactured by Shell Chemicals Co., Ltd.), 390 g of 4,5-epoxycyclohexane dicarboxylic acid diester (hereinafter referred to as epoxy 4) was obtained.

(271) The epoxy 4 thus obtained had an ester value of 273 mg KOH/g, an acid value of 0.04 mg KOH/g, an iodine value of 3.3 g I.sub.2/100 g, an oxirane oxygen content of 3.5%, and a hue of 10.

Production Example 5

(272) In the same manner as in Production Example 1 except that 416 g (2.9 moles) of isononyl alcohol was added instead of 416 g of the saturated aliphatic alcohol (LINEVOL 9, manufactured by Shell Chemicals Co., Ltd.), 379 g of 4,5-epoxycyclohexane dicarboxylic acid diester (hereinafter referred to as epoxy 5) was obtained.

(273) The epoxy 5 thus obtained had an ester value of 255 mg KOH/g, an acid value of 0.05 mg KOH/g, an iodine value of 1.6 g I.sub.2/100 g, an oxirane oxygen content of 3.4%, and a hue of 10.

Production Example 6

(274) In the same manner as in Production Example 1 except that 459 g (2.9 moles) of isodecyl alcohol was added instead of 416 g of the saturated aliphatic alcohol (LINEVOL 9, manufactured by Shell Chemicals Co., Ltd.), 410 g of 4,5-epoxycyclohexane dicarboxylic acid diester (hereinafter referred to as epoxy 6) was obtained.

(275) The epoxy 6 thus obtained had an ester value of 239 mg KOH/g, an acid value of 0.05 mg KOH/g, an iodine value of 2.0 g I.sub.2/100 g, an oxirane oxygen content of 3.1%, and a hue of 10.

Example 1

(276) According to the method described in (3) Molding Processability above, the molding processability (gelation temperature) was measured using the epoxycyclohexane dicarboxylic acid diester (epoxy 1) obtained in Production Example 1. The obtained results were shown in Table 2.

(277) Subsequently, as described in (4) Preparation of Vinyl Chloride Sheet, a soft vinyl chloride-based resin composition was prepared by using the epoxy 1 as a plasticizer, and from the obtained soft vinyl chloride-based resin composition, a vinyl chloride sheet was prepared. The sheet was subjected to a tensile test, a cold resistance test and a heat resistance test. The obtained results were summarized in Table 2.

Example 2

(278) In the same manner as in Example 1 except that the epoxy 2 was used instead of the epoxy 1, the molding processability was measured, and then a soft vinyl chloride-based resin composition was prepared. From the obtained soft vinyl chloride-based resin composition, a vinyl chloride sheet was prepared and subjected to a tensile test, a cold resistance test, and a heat resistance test. The obtained results were summarized in Table 2.

Example 3

(279) In the same manner as in Example 1 except that the epoxy 3 was used instead of the epoxy 1, the molding processability was measured, and then a soft vinyl chloride-based resin composition was prepared. From the obtained soft vinyl chloride-based resin composition, a vinyl chloride sheet was prepared and subjected to a tensile test, a cold resistance test, and a heat resistance test. The obtained results were summarized in Table 2.

Comparative Example 1

(280) In the same manner as in Example 1 except that the epoxy 4 was used instead of the epoxy 1, the molding processability was measured, and then a soft vinyl chloride-based resin composition was prepared. From the obtained soft vinyl chloride-based resin composition, a vinyl chloride sheet was prepared and subjected to a tensile test, a cold resistance test, and a heat resistance test. The obtained results were summarized in Table 2.

Comparative Example 2

(281) In the same manner as in Example 1 except that the epoxy 5 was used instead of the epoxy 1, the molding processability was measured, and then a soft vinyl chloride-based resin composition was prepared. From the obtained soft vinyl chloride-based resin composition, a vinyl chloride sheet was prepared and subjected to a tensile test, a cold resistance test, and a heat resistance test. The obtained results were summarized in Table 2.

Comparative Example 3

(282) In the same manner as in Example 1 except that the epoxy 6 was used instead of the epoxy 1, the molding processability was measured, and then a soft vinyl chloride-based resin composition was prepared. From the obtained soft vinyl chloride-based resin composition, a vinyl chloride sheet was prepared and subjected to a tensile test, a cold resistance test, and a heat resistance test. The obtained results were summarized in Table 2.

Comparative Example 4

(283) In the same manner as in Example 1 except that di-2-ethylhexyl phthalate (SANSO CIZER DOP, manufactured by New Japan Chemical Co., Ltd.) was used instead of the epoxy 1, the molding processability was measured, and then a soft vinyl chloride-based resin composition was prepared. From the obtained soft vinyl chloride-based resin composition, a vinyl chloride sheet was prepared and subjected to a tensile test, a cold resistance test and a heat resistance test. The obtained results were summarized in Table 2.

Comparative Example 5

(284) In the same manner as in Example 1 except that diisononyl phthalate (SANSO CIZER DINP, manufactured by New Japan Chemical Co., Ltd.) was used instead of the epoxy 1, the molding processability was measured, and then a soft vinyl chloride-based resin composition was prepared. From the obtained soft vinyl chloride-based resin composition, a vinyl chloride sheet was prepared and subjected to a tensile test, a cold resistance test and a heat resistance test. The obtained results were summarized in Table 2.

Comparative Example 6

(285) In the same manner as in Example 1 except that commercially available tri-2-ethylhexyl trimellitate (TOTM) was used instead of the epoxy 1, the molding processability was measured, and then a soft vinyl chloride-based resin composition was prepared. From the obtained soft vinyl chloride-based resin composition, a vinyl chloride sheet was prepared and subjected to a tensile test, a cold resistance test and a heat resistance test. The obtained results were summarized in Table 2.

(286) TABLE-US-00002 TABLE 2 Example Comparative Example Test items Unit (condition) 1 2 3 1 2 3 4 5 6 Plasticizer Kind Epoxy 1 Epoxy 2 Epoxy 3 Epoxy 4 Epoxy 5 Epoxy 6 DOP DINP TOTM Ratio of linear-chain alkyl group 87 84 60 0 5 0 0 5 0 (%) Molding Gelation C. 118 122 118 105 120 128 112 118 135 processability temperature Tensile 100% modulus MPa 9.9 10.5 10.3 9.8 10.6 11.6 9.4 10.2 13.1 characteristics Strength MPa 21.4 22.2 22.6 22.4 22.1 23.5 21.4 20.1 24.0 Elongation % 324 340 336 318 319 345 320 320 330 Cold resistance Softening C. 25 27 23 15 18 14 24 27 17 temperature Heat resistance Volatile loss % (170 C., 60 min) 2.1 1.0 2.4 7.9 3.4 2.6 8.8 3.9 0.6 % (170 C., 120 min) 4.0 2.1 4.7 13.0 6.0 4.9 15.1 8.5 1.2 Sheet (170 C., 30 min) discoloration (170 C., 60 min) XX XX X

(287) The results of Table 2 revealed that by using the 4,5-epoxycyclohexane dicarboxylic acid diester of the present invention (Examples 1 to 3) as a plasticizer, the heat resistance, particularly heat discoloration property can be largely improved while maintaining molding processability, flexibility, and cold resistance equivalent to those of the phthalate diester which is currently the most frequently used plasticizer (Comparative Examples 4 and 5). Furthermore, although the volatility resistance is somewhat inferior as compared with the trimellitic acid ester (Comparative Example 6) which is frequently used as a heat resistant plasticizer, the heat resistant discoloration property is greatly improved in the 4,5-epoxycyclohexane dicarboxylic acid diester of the present invention and when considering excellent molding processability, flexibility and cold resistance, usefulness of such a diester is obvious. Also, the results in Table 2 revealed that by using the 4,5-epoxycyclohexane dicarboxylic acid diester of the present invention (Examples 1 and 3) as a plasticizer, the cold resistance and heat resistance are greatly improved while maintaining equivalent molding processability and flexibility, when compared with the case in which the conventional 4,5-epoxycyclohexane dicarboxylic acid diester (Comparative Example 1) is used. In addition, such effect is clear as compared with the case of using the 4,5-epoxycyclohexane dicarboxylic acid diester (Comparative Examples 2 and 3) outside the scope of the present invention. Similarly, when the 4,5-epoxycyclohexane dicarboxylic acid diester of the present invention (Example 2) is used as a plasticizer, the molding processability equal to or higher than that of phthalic acid diester which is a versatile plasticizer is exhibited, and its cold resistance and heat resistance are further improved. Thus, it is understood that the 4,5-epoxycyclohexane dicarboxylic acid diester of the present invention is particularly useful when used in a more severe environment.

Third Embodiment of the Present Invention

(288) (1) Number of Carbon Atoms of Alkyl Group and Ratio of Linear-Chain Alkyl Group

(289) The number of carbon atoms of alkyl group and the ratio of the linear-chain alkyl group in the stabilizer used in examples and comparative examples of the present invention were determined by gas chromatography (hereinafter abbreviated as GC) of the composition of the raw material alcohol used for the production. The results were defined as the number of carbon atoms of alkyl group and the ratio of the linear-chain alkyl group in the stabilizer. The method of measuring the raw material alcohol by GC is the same as above.

(290) (2) Evaluation of Physical Properties of Raw Material Ester and Present Diester

(291) The ester value, acid value, iodine value, oxirane oxygen, and hue of the raw material ester and the present diester obtained in the following production examples were analyzed in the same manner as described above.

(292) (3) Preparation of Vinyl Chloride Sheet

(293) [Method 1: Hard and Semi-Hard Vinyl Chloride Sheet]

(294) A prescribed amount of the stabilizer according to the present invention as shown in Table 3 was blended with 100 parts by weight of a vinyl chloride-based resin (straight, polymerization degree 1050, trade name Zest 1000Z, manufactured by Shin Dai-Ichi Vinyl Corporation), and 3.0 parts by weight of a calcium-zinc composite stabilizer as a stabilizer outside the scope of the present invention was added thereto. The mixture was stirred and mixed with a mortar mixer to obtain a vinyl chloride-based resin composition. This resin composition was melt-kneaded at 170 to 176 C. for 4 minutes using a 512 inches twin roll to prepare a roll sheet. Subsequently, press molding of the roll sheet was carried out at 172 to 178 C. for 10 minutes to prepare a press sheet having a thickness of about 0.5 mm.

(295) [Method 2: Soft Vinyl Chloride Sheet]

(296) A prescribed amount of the stabilizer according to the present invention as shown in Table 4 was blended with 100 parts by weight of a vinyl chloride-based resin (straight, polymerization degree 1050, trade name Zest 1000Z, manufactured by Shin Dai-Ichi Vinyl Corporation), and 0.3 parts by weight of calcium stearate (manufactured by Nacalai Tesque Co., Ltd.) and 0.2 parts by weight of zinc stearate (manufactured by Nacalai Tesque Co., Ltd.) were respectively added thereto as a stabilizer outside the scope of the present invention, and stirred and mixed in a mortar mixer to obtain a vinyl chloride-based resin composition. Subsequently, after stirring and mixing with a mortar mixer, 30 parts by weight of a plasticizer was further added and mixed by hand until uniform, thereby obtaining a soft vinyl chloride-based resin composition. This resin composition was melt-kneaded at 160 to 166 C. for 4 minutes using a 512 inches twin roll to prepare a roll sheet. Subsequently, press molding was performed at 162 to 168 C. for 10 minutes to prepare a press sheet having a thickness of about 1 mm.

(297) [Evaluation of Physical Properties of Resin]

(298) (4) Tensile Characteristics: Elastic modulus or 100% modulus, breaking strength, and breaking elongation of the press sheet were measured according to JIS K-6723 (1995). The smaller the elastic modulus or the 100% modulus, the better the flexibility. The breaking strength and breaking elongation are indications of the practical strength of the material. Generally, it can be said that the greater these values, the more superior the practical strength.
(5) Heat Resistance: The heat resistance was evaluated based on volatile loss and sheet discoloration.
a) Volatile loss: A roll sheet was heated in a gear oven at 170 C. for 30 minutes and 60 minutes, and the volatile loss (%) was calculated according to the following formula.

(299) It can be said that the smaller the value, the more excellent the heat resistance, resulting in little reduction in the effect as a stabilizer.
Volatile loss (%)=((Weight before testWeight after test)/Weight before test)100
b) Sheet discoloration: A roll sheet was heated in a gear oven at 170 C. for 30 minutes and 60 minutes; thereafter, the intensity of discoloration of each roll sheet was visually evaluated on a six-level scale.

(300) Although sheet discoloration is an evaluation of heat resistance, it is also an index of the effect (stabilization effect) as a stabilizer against heat. That is, it can be said that the less the discoloration, the more effectively the added stabilizer acts as a stabilizer resistant to heat, leading to suppression of such discoloration.

(301) : Discoloration was not observed.

(302) : Slight discoloration was observed.

(303) : Insignificant discoloration was observed.

(304) : Discoloration was observed.

(305) x: Strong discoloration was observed.

(306) xx: Significant discoloration was observed.

(307) (6) Heat resistance (aging property): According to JIS K-6723 (1995), a tensile test was conducted after heating at 120 C.120 hours. The results were shown as a 100% modulus residual ratio (%) and a breaking elongation residual ratio (%) of the press sheet compared with a normal state.

(308) The closer the result value is to 100, the less the change in physical properties after heating, and thus it can be said that the press sheet is excellent in heat aging resistance. Moreover, this test is not only a heat resistance test but also an index of the effect (stabilizing effect) as a stabilizer against heat. That is, it is thought that as the result value approaches 100, the added stabilizer effectively acts as a stabilizer against heat and suppresses aging.
100% modulus residual ratio %=(1(100% modulus after heating100% modulus before heating/100% modulus before heating))100
Elongation residual ratio %=(breaking elongation after heating/breaking elongation before heating)100
(7) Fogging Resistance

(309) A press sheet (4 g) was placed in a glass-made sample bottle, and the bottle was set in a fogging tester adjusted to 100 C. Further, a glass plate lid was placed on the sample bottle, and a cooling plate with a cooling water flow adjusted to 20 C. was placed thereon, and a heat treatment was performed at 100 C. for 3 hours. After the heat treatment, the fogging degree (Haze) (%) of the glass plate was measured using a haze meter (Haze Guard II: manufactured by Toyo Seiki Seisakusho KK).

(310) The smaller the haze value, the more superior the fogging resistance.

Production Example 1

(311) Esterification Reaction

(312) A 2 L four-necked flask equipped with a thermometer, a decanter, a stirring blade and a reflux condenser was charged with 182.6 g of 4-cyclohexene-1,2-dicarboxylic anhydride (1.2 moles, RICACIDTH, manufactured by New Japan Chemical Co., Ltd.), 416 g (2.9 moles) of a saturated aliphatic alcohol containing 85.1% by weight of a linear-chain saturated aliphatic alcohol having 9 carbon atoms and 11.7% of a branched-chain saturated aliphatic alcohol having 9 carbon atoms (LINEVOL 9, manufactured by Shell Chemicals Co., Ltd.: linear chain ratio (molar ratio): 85%), and 0.24 g of tetraisopropyl titanate as an esterification catalyst, and then the esterification reaction was carried out at a reaction temperature of 200 C. The reaction was carried out until the acid value of the reaction solution became 0.5 mg KOH/g while removing the produced water out of the system by refluxing the alcohol under reduced pressure. After completion of the reaction, the unreacted alcohol was distilled out of the system under reduced pressure, and the system was neutralized, washed, and dehydrated according to a conventional method to obtain 449 g of an objective 4-cyclohexene-1,2-dicarboxylic acid diester (hereinafter referred to as ester 1).

(313) The ester 1 thus obtained had an ester value of 262 mg KOH/g, an acid value of 0.04 mg KOH/g, and a hue of 15.

(314) Epoxidation Reaction

(315) Then, 423 g (1.0 mole) of the ester 1 obtained in the above esterification reaction was charged into a 1 L four-necked flask equipped with a thermometer, a stirring blade and a cooling tube, and the temperature was raised to 60 to 70 C. After the temperature rise, 76.6 g (1.35 moles) of 60% hydrogen peroxide water, 18.3 g (0.30 moles) of 76% formic acid, and 1.47 g (0.01 moles) of 75% phosphoric acid were slowly added dropwise over a period of 2.25 hours. After completion of the dropwise addition, the above temperature was maintained for further 4 hours, and the reaction was completed by aging. After completion of the reaction, the aqueous phase was removed to the outside of the system, followed by washing with water and dehydration in a conventional manner to obtain 397 g of an objective 4,5-epoxycyclohexane dicarboxylic acid diester (hereinafter referred to as epoxy 1).

(316) The epoxy 1 thus obtained had an ester value of 256 mg KOH/g, an acid value of 0.06 mg KOH/g, an iodine value of 2.5 g I.sub.2/100 g, an oxirane oxygen content of 3.5%, and a hue of 10.

Production Example 2

(317) In the same manner as in Production Example 1 except that 400 g (2.5 moles) of mixed saturated aliphatic alcohols having 9 to 11 carbon atoms (NEODOL 911, manufactured by Shell Chemicals Co., Ltd.) wherein the ratio (molar ratio) of 9 carbon atoms/10 carbon atoms/11 carbon atoms is 18:42:38 and the overall linear chain ratio was 84% was added instead of 416 g of the saturated aliphatic alcohol (LINEVOL 9, manufactured by Shell Chemicals Co., Ltd.), 404 g of a 4,5-epoxycyclohexane dicarboxylic acid diester (hereinafter referred to as epoxy 2) was obtained.

(318) The epoxy 2 thus obtained had an ester value of 242 mg KOH/g, an acid value of 0.04 mg KOH/g, an iodine value of 1.9 g I.sub.2/100 g, an oxirane oxygen content of 3.1%, and a hue of 10.

Production Example 3

(319) In the same manner as in Production Example 1 except that 374 g (2.9 moles) of 2-ethylhexanol was added instead of 416 g of the saturated aliphatic alcohol (LINEVOL 9, manufactured by Shell Chemicals Co., Ltd.), 390 g of 4,5-epoxycyclohexane dicarboxylic acid diester (hereinafter referred to as epoxy 3) was obtained.

(320) The epoxy 3 thus obtained had an ester value of 273 mg KOH/g, an acid value of 0.04 mg KOH/g, an iodine value of 3.3 g I.sub.2/100 g, an oxirane oxygen content of 3.5%, and a hue of 10.

Example 1

(321) According to the method described in Method 1: Hard and Semi-Hard Vinyl Chloride Sheet of (3) Preparation of Vinyl Chloride Sheet, a vinyl chloride-based resin composition was prepared using 19 parts by weight of the epoxycyclohexane dicarboxylic acid diester (epoxy 1) as a stabilizer, and a vinyl chloride sheet was prepared from the obtained vinyl chloride-based resin composition. Then, the vinyl chloride sheet was subjected to a tensile test, a heat resistance test, and a fogging resistance test. The obtained results were summarized in Table 3.

(322) The vinyl chloride sheet prepared above showed no signs of bleeding or the like at all even if left for 1 month at room temperature.

Example 2

(323) A vinyl chloride-based resin composition was prepared in the same manner as in Example 1 except that 10 parts by weight of the epoxy 2 was used as a stabilizer instead of 19 parts by weight of the epoxy 1 to prepare a vinyl chloride-based resin composition. From the resin composition obtained, a vinyl chloride sheet was prepared and subjected to a tensile test, a heat resistance test, and a fogging resistance test. The obtained results were summarized in Table 3.

(324) The vinyl chloride sheet prepared above showed no signs of bleeding or the like at all even if left for 1 month at room temperature.

Example 3

(325) According to the method described in Method 2: Soft Vinyl Chloride Sheet of (3) Preparation of Vinyl Chloride Sheet, a vinyl chloride-based resin composition was prepared using 19 parts by weight of the epoxycyclohexane dicarboxylic acid diester (epoxy 1) as a stabilizer and tri-2-ethylhexyl trimellitate (TOTM) as a plasticizer, and a vinyl chloride sheet was prepared from the obtained vinyl chloride-based resin composition. Then, the vinyl chloride sheet was subjected to a tensile test, a heat resistance test, and a fogging resistance test. The obtained results were summarized in Table 4.

Example 4

(326) A vinyl chloride-based resin composition was prepared in the same manner as in Example 3 except that the epoxy 2 was used instead of the epoxy 1, and a vinyl chloride sheet was prepared from the obtained vinyl chloride-based resin composition, and subjected to a tensile test, a heat resistance test, and a fogging resistance test. The obtained results were summarized in Table 4.

Example 5

(327) A vinyl chloride-based resin composition was prepared in the same manner as in Example 3 except that a trimellitic acid triester (TL9TM) of the saturated aliphatic alcohol (LINEVOL 9) was used instead of TOTM, and a vinyl chloride sheet was prepared from the obtained vinyl chloride-based resin composition. The vinyl chloride sheet was subjected to a tensile test, a heat resistance test, and a fogging resistance test. The obtained results were summarized in Table 4.

Comparative Example 1

(328) A vinyl chloride-based resin composition was prepared in the same manner as in Example 1 except that the epoxy 1 was not added. Then, a vinyl chloride sheet was prepared from the obtained vinyl chloride-based resin composition, and subjected to a tensile test, a heat resistance test, and a fogging resistance test. The obtained results were summarized in Table 3.

Comparative Example 2

(329) A vinyl chloride-based resin composition was prepared in the same manner as in Example 1 except that the epoxy 3 was used instead of the epoxy 1. Then, a vinyl chloride sheet was prepared from the obtained vinyl chloride-based resin composition, and subjected to a tensile test, a heat resistance test, and a fogging resistance test. The obtained results were summarized in Table 3.

Comparative Example 3

(330) A vinyl chloride-based resin composition was prepared in the same manner as in Example 3 except that the epoxy 1 was not added. Then, a vinyl chloride sheet was prepared from the obtained vinyl chloride-based resin composition, and subjected to a tensile test, a heat resistance test, and a fogging resistance test. The obtained results were summarized in Table 4.

Comparative Example 4

(331) A vinyl chloride-based resin composition was prepared in the same manner as in Example 3 except that the epoxy 3 was used instead of the epoxy 1. Then, a vinyl chloride sheet was prepared from the obtained vinyl chloride-based resin composition, and subjected to a tensile test, a heat resistance test, and a fogging resistance test. The obtained results were summarized in Table 4.

(332) TABLE-US-00003 TABLE 3 Example Comparative Example Test items Unit (Condition) 1 2 1 2 Stabilizer Kind Epoxy 1 Epoxy 2 Epoxy 3 Blending amount (Parts by weight) 19 10 19 Tensile Elastic MPa 2080 2630 3270 2370 characteristics modulus Strength MPa 39.6 48.6 61.3 50.0 Elongation % 221 120 44 67 Heat resistance Sheet (170 C., 30 minutes) discoloration (170 C., 60 minutes) X Volatile loss (170 C., 30 minutes) 0.8 0.6 0.1 2.9 (170 C., 60 minutes) 1.6 1.2 0.2 4.5 Elongation % 99 100 79 83 residual ratio Fogging (100 C., 3 hours) 0.6 0.5 0.3 8.9 resistance

(333) TABLE-US-00004 TABLE 4 Comparative Example Example Test items Unit (Condition) 3 4 5 3 4 Plasticizer Kind TOTM TOTM TL9TM TOTM TOTM Stabilizer Kind Epoxy 1 Epoxy 2 Epoxy 1 Epoxy 3 Blending amount (Parts by weight) 19 19 19 19 Tensile 100% modulus MPa 11.9 12.4 11.6 22.4 12.5 characteristics Strength MPa 22.8 22.7 23.5 29.9 23.1 Elongation % 329 316 354 270 320 Heat resistance Sheet (170 C., 30 minutes) discoloration (170 C., 60 minutes) X Volatile loss (170 C., 30 minutes) 0.5 0.3 0.5 0.3 1.3 (170 C., 60 minutes) 1.0 0.6 0.9 0.6 2.2 100% modulus % 101 100 101 100 130 residual ratio Elongation % 98 99 98 81 84 residual ratio Fogging (100 C., 3 hours) 0.5 0.3 0.3 0.2 6.7 resistance

(334) The results in Tables 3 and 4 revealed that by blending the epoxycyclohexane dicarboxylic acid diester of the present invention (Examples 1 to 5), discoloration due to heat and deterioration in physical properties due to heat, that is, thermal deterioration is remarkably reduced, compared with the case (Comparative Examples 1 and 3) wherein the diester was not blended. When a conventional epoxycyclohexane dicarboxylic acid diester, that is, an epoxycyclohexane dicarboxylic acid diester outside the scope of the present invention (Comparative Examples 2 and 4) is blended, a tendency to decrease the fogging property is observed, whereas when the epoxycyclohexane dicarboxylic acid diester (Examples 1 to 5) within the scope of the present invention is blended, almost no deterioration in fogging property is recognized. These tendencies are exactly the same as those observed from the hard composition to the soft composition to which a heat resistant plasticizer is added. From the above results, it is understood that the epoxycyclohexane dicarboxylic acid diester according to the present invention is widely useful as a very excellent stabilizer from hard applications to semi-hard or soft applications.

Fourth Embodiment of the Present Invention

(335) (1) Number of Carbon Atoms of Alkyl Group and Ratio of Linear-Chain Alkyl Group

(336) The number of carbon atoms of alkyl group and the ratio of the linear-chain alkyl group in the plasticizer used in examples and comparative examples of the present invention were determined by gas chromatography (hereinafter abbreviated as GC) of the composition in the raw material alcohol used for the production. The result was defined as the number of carbon atoms of alkyl group and the ratio of the linear-chain alkyl group in the plasticizer. The method of measuring the raw material alcohol by GC is the same as above.

(337) (2) Evaluation of Physical Properties of Raw Material Ester and Present Diester

(338) The ester value, acid value, iodine value, oxirane oxygen, and hue of the raw material ester and the present ester obtained in the following production examples were analyzed in the same manner as described above.

(339) (3) Preparation of Vinyl Chloride Sheet

(340) To 100 parts by weight of a vinyl chloride-based resin (straight, polymerization degree 1050, trade name Zest 1000Z, manufactured by Shin Dai-Ichi Vinyl Corporation) were respectively added 0.3 parts by weight of calcium stearate (manufactured by Nacalai Tesque, Inc.) and 0.2 parts by weight of zinc stearate as a stabilizer other than the stabilizer outside the scope of the present invention, and the mixture was stirred and mixed with a mortar mixer to obtain a vinyl chloride-based resin composition. After stirring and mixing with a mortar mixer, a predetermined amount of the diester of the present invention as shown in Table 5 was added and mixed by hand until uniform, thereby obtaining a vinyl chloride-based resin composition. This resin composition was melt-kneaded at 160 to 166 C. for 4 minutes using a 512 inches twin roll to prepare a roll sheet. Subsequently, press molding was performed at 162 to 168 C. for 10 minutes to prepare a press sheet having a thickness of about 1 mm.

(341) [Evaluation of Physical Properties of Resin]

(342) (4) Tensile Characteristics: The 100% modulus, the breaking strength and the breaking elongation of the press sheet were measured according to JIS K-6723 (1995). The measurement demonstrated that the smaller the 100% modulus, the more desirable the flexibility. The breaking strength and the breaking elongation are indications of the practical strength of the material. Generally, it can be said that the greater these values, the more superior the practical strength.
(5) Cold Resistance: The softening temperature ( C.) of the press sheet was measured according to JIS K-6773 (1999) using a Clash-Berg tester. The lower the softening temperature ( C.), the more superior the cold resistance. The softening temperature here refers to a low temperature limit indicating a predetermined torsional rigidity rate (3.1710.sup.3 kg/cm.sup.2) in the above measurement.
(6) Heat Resistance (Volatility, Discoloration): The heat resistance was determined according to evaluation of volatile loss and sheet discoloration after heating.
a) Volatile loss: The roll sheet was heated in a gear oven at 170 C. for 60 minutes and 120 minutes, and a change in the weight was measured; then, the volatile loss (%) was calculated according to the following equation. The smaller the value of volatile loss, the higher the heat resistance.
Volatile loss (%)=((Weight before testWeight after test)/Weight before test)100
b) Sheet discoloration: The roll sheet was heated in a gear oven at 170 C. for 30 minutes and 60 minutes; thereafter, the intensity of discoloration of each roll sheet was visually evaluated on a six-level scale.
: Discoloration was not observed.
: Slight discoloration was observed.
A: Insignificant discoloration was observed.
: Discoloration was observed.
x: Strong discoloration was observed.
xx: Significant discoloration was observed.
(7) Fogging Resistance

(343) A press sheet (4 g) was placed in a glass-made sample bottle, and the bottle was set in a fogging tester adjusted to 100 C. Further, a glass plate lid was placed on the sample bottle, and a cooling plate with a cooling water flow adjusted to 20 C. was placed thereon, and a heat treatment was performed at 100 C. for 3 hours. After the heat treatment, the degree of fogging on the surface of the glass plate was visually observed and evaluated on the basis of four grades. The haze (%) of the glass plate was measured using a haze meter (HAZE GUARD II, manufactured by Toyo Seiki Seisakusho). The smaller the haze value, the more excellent the fogging resistance.

(344) [Four-Grade Evaluation by Visual Observation]

(345) : No fogging occurred at all, and there was no influence on the field of view beyond the glass plate.

(346) : Slight fogging occurred, which was not so much as to affect the field of view beyond the glass plate.

(347) : Fogging obviously occurred, and visibility beyond the glass plate was slightly affected.

(348) x: The degree of fogging on the surface of the glass plate was so severe that the field of view beyond the glass plate has decreased.

(349) (8) Heat-Aging Resistance: A tensile test was performed on the press sheet after heating under the conditions of 100 C. for 120 hours according to JIS K-6723 (1995). The results were shown as a 100% modulus residual ratio (%) and a breaking elongation residual ratio (%) of the press sheet after testing in a normal state. The closer the value is to 100%, the better the heat aging resistance.
100% modulus residual ratio (%)=(100% modulus of press sheet in tensile test after heating)/(100% modulus of press sheet in tensile test before heating)100
Breaking elongation residual ratio=(breaking elongation of press sheet in tensile test after heating)/(breaking elongation of press sheet in tensile test before heating)100
(9) Light Resistance: Yellow index (YI) after 200 hours irradiation test by a xenon weather meter (Suga Test Instruments Co., Ltd.) was measured.

Production Example 1

(350) Esterification Reaction

(351) A 2 L four-necked flask equipped with a thermometer, a decanter, a stirring blade and a reflux condenser was charged with 182.6 g of 4-cyclohexene-1,2-dicarboxylic anhydride (1.2 moles, RICACIDTH, manufactured by New Japan Chemical Co., Ltd.), 416 g (2.9 moles) of a saturated aliphatic alcohol containing 85.1% by weight of a linear-chain saturated aliphatic alcohol having 9 carbon atoms and 11.7% of a branched-chain saturated aliphatic alcohol having 9 carbon atoms (LINEVOL 9, the ratio of the linear-chain saturated aliphatic alcohol: 87%, manufactured by Shell Chemicals Co., Ltd.), and 0.24 g of tetraisopropyl titanate as an esterification catalyst, and then the esterification reaction was carried out at a reaction temperature of 200 C. The reaction was carried out until the acid value of the reaction solution became 0.5 mg KOH/g while removing the produced water out of the system by refluxing the alcohol under reduced pressure. After completion of the reaction, the unreacted alcohol was distilled out of the system under reduced pressure, and the system was neutralized, washed, and dehydrated according to a conventional method to obtain 449 g of an objective 4-cyclohexene-1,2-dicarboxylic acid diester (hereinafter referred to as ester 1).

(352) The ester 1 thus obtained had an ester value of 254 mg KOH/g, an acid value of 0.04 mg KOH/g, and a hue of 15.

(353) Epoxidation Reaction

(354) Then, 423 g (1.0 mole) of the ester 1 obtained in the above esterification reaction was charged into a 1 L four-necked flask equipped with a thermometer, a stirring blade and a cooling tube, and the temperature was raised to 60 to 70 C. After the temperature rise, 76.6 g (1.35 moles) of 60% hydrogen peroxide water, 18.3 g (0.30 moles) of 76% formic acid, and 1.47 g (0.01 moles) of 75% phosphoric acid were slowly added dropwise over a period of 2.25 hours. After completion of the dropwise addition, the above temperature was maintained for further 4 hours, and the reaction was completed by aging. After completion of the reaction, the aqueous phase was removed to the outside of the system, followed by washing with water and dehydration in a conventional manner to obtain 397 g of an objective 4,5-epoxycyclohexane dicarboxylic acid diester (hereinafter referred to as epoxy 1).

(355) The epoxy 1 thus obtained had an ester value of 256 mg KOH/g, an acid value of 0.06 mg KOH/g, an iodine value of 2.5 g I.sub.2/100 g, an oxirane oxygen content of 3.5%, and a hue of 10.

Production Example 2

(356) In the same manner as in Production Example 1 except that 400 g (2.5 moles) of mixed saturated aliphatic alcohols having 9 to 11 carbon atoms (NEODOL 911, manufactured by Shell Chemicals Co., Ltd.) wherein the ratio of 9 carbon atoms/10 carbon atoms/11 carbon atoms is 19:43:38 and the ratio of the linear-chain saturated aliphatic alcohol was 84% was added instead of 416 g of the saturated aliphatic alcohol (LINEVOL 9, manufactured by Shell Chemicals Co., Ltd.), 404 g of a 4,5-epoxycyclohexane dicarboxylic acid diester (hereinafter referred to as epoxy 2) was obtained.

(357) The epoxy 2 thus obtained had an ester value of 242 mg KOH/g, an acid value of 0.04 mg KOH/g, an iodine value of 1.9 g I.sub.2/100 g, an oxirane oxygen content of 3.1%, and a hue of 10.

Production Example 3

(358) In the same manner as in Production Example 1 except that 198 g (1.4 moles) of n-nonyl alcohol and 162 g (1.1 moles) of isononyl alcohol were added instead of 416 g of the saturated aliphatic alcohol (LINEVOL 9, manufactured by Shell Chemicals Co., Ltd.), 390 g of 4,5-epoxycyclohexane dicarboxylic acid diester (hereinafter referred to as epoxy 3) was obtained. The ratio of the linear-chain saturated aliphatic alcohol was 60%.

(359) The epoxy 3 thus obtained had an ester value of 256 mg KOH/g, an acid value of 0.05 mg KOH/g, an iodine value of 2.5 g I.sub.2/100 g, an oxirane oxygen content of 3.5%, and a hue of 10.

Production Example 4

(360) In the same manner as in Production Example 1 except that 374 g (2.9 moles) of 2-ethylhexanol was added instead of 416 g of the saturated aliphatic alcohol (LINEVOL 9, manufactured by Shell Chemicals Co., Ltd.), 390 g of 4,5-epoxycyclohexane dicarboxylic acid diester (hereinafter referred to as epoxy 4) was obtained.

(361) The epoxy 4 thus obtained had an ester value of 273 mg KOH/g, an acid value of 0.04 mg KOH/g, an iodine value of 3.3 g I.sub.2/100 g, an oxirane oxygen content of 3.5%, and a hue of 10.

Production Example 5

(362) In the same manner as in Production Example 1 except that 416 g (2.9 moles) of isononyl alcohol was added instead of 416 g of the saturated aliphatic alcohol (LINEVOL 9, manufactured by Shell Chemicals Co., Ltd.), 379 g of 4,5-epoxycyclohexane dicarboxylic acid diester (hereinafter referred to as epoxy 5) was obtained.

(363) The epoxy 5 thus obtained had an ester value of 255 mg KOH/g, an acid value of 0.05 mg KOH/g, an iodine value of 1.6 g I.sub.2/100 g, an oxirane oxygen content of 3.4%, and a hue of 10.

Production Example 6

(364) In the same manner as in Production Example 1 except that 459 g (2.9 moles) of isodecyl alcohol was added instead of 416 g of the saturated aliphatic alcohol (LINEVOL 9, manufactured by Shell Chemicals Co., Ltd.), 410 g of 4,5-epoxycyclohexane dicarboxylic acid diester (hereinafter referred to as epoxy 6) was obtained.

(365) The epoxy 6 thus obtained had an ester value of 239 mg KOH/g, an acid value of 0.05 mg KOH/g, an iodine value of 2.0 g I.sub.2/100 g, an oxirane oxygen content of 3.1%, and a hue of 10.

Example 1

(366) According to the method described in (3) Preparation of Vinyl Chloride Sheet, a vinyl chloride-based resin composition was prepared by using a predetermined amount as shown in Table 5 of the epoxycyclohexane dicarboxylic acid diester (epoxy 1) obtained in Production Example 1. From the obtained vinyl chloride-based resin composition, a vinyl chloride sheet was prepared and then subjected to a tensile test, a cold resistance test, a heat resistance test, a light resistance test, and a fogging resistance test. The obtained results were summarized in Table 5.

Example 2

(367) A vinyl chloride-based resin composition was prepared in the same manner as in Example 1 except that the epoxy 2 was used instead of the epoxy 1, and a vinyl chloride sheet was prepared from the obtained vinyl chloride-based resin composition. The vinyl chloride sheet was subjected to a tensile test, a cold resistance test, a heat resistance test, a light resistance test, and a fogging resistance test. The obtained results were summarized in Table 5.

Example 3

(368) A vinyl chloride-based resin composition was prepared in the same manner as in Example 1 except that the epoxy 3 was used instead of the epoxy 1, and a vinyl chloride sheet was prepared from the obtained vinyl chloride-based resin composition. The vinyl chloride sheet was subjected to a tensile test, a cold resistance test, a heat resistance test, a light resistance test, and a fogging resistance test. The obtained results were summarized in Table 5.

Example 4

(369) A vinyl chloride-based resin composition was prepared in the same manner as in Example 1 except that the blending amount of the epoxy 1 was reduced to 10 parts, and 40 parts of diisononyl 1,2-cyclohexane dicarboxylate (HEXAMOLL DINCH, manufactured by BASF) was used. A vinyl chloride sheet was prepared from the obtained vinyl chloride-based resin composition and subjected to a tensile test, a cold resistance test, a heat resistance test, a light resistance test, and a fogging resistance test. The obtained results were summarized in Table 5.

Example 5

(370) A vinyl chloride-based resin composition was prepared in the same manner as in Example 2 except that the blending amount of the epoxy 2 was reduced to 10 parts, and 40 parts of diisononyl 1,2-cyclohexane dicarboxylate (HEXAMOLL DINCH, manufactured by BASF) was used. A vinyl chloride sheet was prepared from the obtained vinyl chloride-based resin composition and subjected to a tensile test, a cold resistance test, a heat resistance test, a light resistance test, and a fogging resistance test. The obtained results were summarized in Table 5.

Example 6

(371) A vinyl chloride-based resin composition was prepared in the same manner as in Example 1 except that the blending amount of the epoxy 1 was reduced to 10 parts, and 40 parts of tri-2-ethylhexyl trimellitate (TOTM) was used. A vinyl chloride sheet was prepared from the obtained vinyl chloride-based resin composition and subjected to a tensile test, a cold resistance test, a heat resistance test, a light resistance test, and a fogging resistance test. The obtained results were summarized in Table 5.

Comparative Example 1

(372) A vinyl chloride-based resin composition outside the scope of the present invention was prepared in the same manner as in Example 1 except that the epoxy 4 was used instead of the epoxy 1, and a vinyl chloride sheet was prepared from the obtained vinyl chloride-based resin composition. The vinyl chloride sheet was subjected to a tensile test, a cold resistance test, a heat resistance test, a light resistance test, and a fogging resistance test. The obtained results were summarized in Table 5.

Comparative Example 2

(373) A vinyl chloride-based resin composition outside the scope of the present invention was prepared in the same manner as in Example 1 except that the epoxy 5 was used instead of the epoxy 1, and a vinyl chloride sheet was prepared from the obtained vinyl chloride-based resin composition. The vinyl chloride sheet was subjected to a tensile test, a cold resistance test, a heat resistance test, a light resistance test, and a fogging resistance test. The obtained results were summarized in Table 5.

Comparative Example 3

(374) A vinyl chloride-based resin composition outside the scope of the present invention was prepared in the same manner as in Example 1 except that the epoxy 6 was used instead of the epoxy 1, and a vinyl chloride sheet was prepared from the obtained vinyl chloride-based resin composition. The vinyl chloride sheet was subjected to a tensile test, a cold resistance test, a heat resistance test, a light resistance test, and a fogging resistance test. The obtained results were summarized in Table 5.

Comparative Example 4

(375) A vinyl chloride-based resin composition outside the scope of the present invention was prepared in the same manner as in Example 1 except that diisononyl 1,2-cyclohexane dicarboxylate (HEXAMOLL DINCH, manufactured by BASF) was used instead of the epoxy 1, and a vinyl chloride sheet was prepared from the obtained vinyl chloride-based resin composition. The vinyl chloride sheet was subjected to a tensile test, a cold resistance test, a heat resistance test, a light resistance test, and a fogging resistance test. The obtained results were summarized in Table 5.

Comparative Example 5

(376) A vinyl chloride-based resin composition outside the scope of the present invention was prepared in the same manner as in Example 1 except that commercially available tri-2-ethylhexyl trimellitate (TOTM) was used instead of the epoxy 1, and a vinyl chloride sheet was prepared from the obtained vinyl chloride-based resin composition. The vinyl chloride sheet was subjected to a tensile test, a cold resistance test, a heat resistance test, a light resistance test, and a fogging resistance test. The obtained results were summarized in Table 5.

Comparative Example 6

(377) A vinyl chloride-based resin composition outside the scope of the present invention was prepared in the same manner as in Example 1 except that commercially available diisononyl phthalate (SANSO CIZER DINP, manufactured by New Japan Chemical Co., Ltd.) was used instead of the epoxy 1, and a vinyl chloride sheet was prepared from the obtained vinyl chloride-based resin composition. The vinyl chloride sheet was subjected to a tensile test, a cold resistance test, a heat resistance test, a light resistance test, and a fogging resistance test. The obtained results were summarized in Table 5.

(378) TABLE-US-00005 TABLE 5 Example Test items Unit 1 2 3 4 5 6 Epoxy Kind Epoxy 1 Epoxy 2 Epoxy 3 Epoxy 1 Epoxy 2 Epoxy 1 compound Blending amount 50 50 50 10 10 10 (Parts by weight) Tensile 100% modulus MPa 9.9 10.5 10.3 10.3 10.5 12.6 characteristics Strength MPa 21.4 22.2 22.6 22.2 21.8 22.4 Elongation % 324 340 336 373 347 323 Cold Softening C. 25 27 23 27 30 19 resistance temperature Heat Volatile 60 % 2.1 1.0 2.8 6.8 6.3 0.8 resistance loss minutes (volatilization) 120 % 4.0 2.1 5.2 12.1 11.4 1.8 minutes Heat Sheet 30 resistance dis- minutes (discoloration) coloration 60 minutes Fogging Visual evaluation - resistance Haze value % 1 0 1 5 3 1 Heat 100% modulus % 108 109 105 119 117 94 resistance residual ratio (aging) Elongation % 100 99 98 60 65 100 residual ratio Light Sheet 200 h 6.7 6.8 6.9 9.4 9.0 10.5 resistance dis- (discoloration) coloration Comparative Example Test items Unit 1 2 3 4 5 6 Epoxy Kind Epoxy 4 Epoxy 5 Epoxy 6 DINCH TOTM DINP compound Blending amount 50 50 50 50 50 50 (Parts by weight) Tensile 100% modulus MPa 9.8 10.6 11.6 10.8 13.1 10.2 characteristics Strength MPa 22.4 22.1 23.5 22.1 24.0 20.1 Elongation % 318 319 345 361 330 320 Cold Softening C. 15 19 15 29 17 27 resistance temperature Heat Volatile 60 % 7.9 3.4 2.6 7.7 0.6 3.9 resistance loss minutes (volatilization) 120 % 13.0 6.0 4.9 14.0 1.2 7.5 minutes Heat Sheet 30 resistance dis- minutes (discoloration) coloration 60 X XX minutes Fogging Visual evaluation X X X resistance Haze value % 12 2 1 6 1 8 Heat 100% modulus % 151 109 110 120 92 114 resistance residual ratio (aging) Elongation % 85 95 86 45 90 62 residual ratio Light Sheet 200 h 7.0 7.4 8.0 15.7 16.0 11.1 resistance dis- (discoloration) coloration

(379) The results in Table 5 revealed that by using the 4,5-epoxycyclohexane dicarboxylic acid diester (Examples 1 to 3) of the present invention as a plasticizer, heat resistance, particularly discoloration can be greatly improved while maintaining an equivalent level of molding processability, flexibility, and cold resistance, compared with the case using DINCH (Comparative Example 5) and DINP (Comparative Example 7) which are currently widely used. Furthermore, even when compared with the trimellitic acid ester (Comparative Example 6) which is frequently used as a heat resistant plasticizer, there is no significant difference in fogging resistance, but heat resistance, particularly discoloration is greatly improved. Considering excellent molding processability, flexibility, and cold resistance, it is apparent that the sheet of the present invention is useful as an automotive interior material. From the results in Table 5, it is understood that by using the 4,5-epoxycyclohexane dicarboxylic acid diester of the present invention (Examples 1 to 3) as a plasticizer, the cold resistance and the heat resistance are greatly improved while maintaining an equivalent level of molding processability and flexibility, when compared with the case using the conventional 4,5-epoxycyclohexane dicarboxylic acid diester (Comparative Example 1). Further, from the results of Examples 4 to 6, it is found that heat resistance, particularly discoloration can be greatly improved by adding the 4,5-epoxycyclohexane dicarboxylic acid diester of the present invention to DINCH or TOTM which is currently widely used. From the above results, it is found that the vinyl chloride-based resin composition for automotive interior containing the epoxycyclohexane dicarboxylic acid diester according to the present invention is particularly useful as interior materials of automobiles for cold district specifications and overseas specifications used in more severe environments.

Fifth Embodiment of the Present Invention

(380) (1) Number of Carbon Atoms of Alkyl Group and Ratio of Linear-Chain Alkyl Group

(381) The number of carbon atoms of alkyl group and the ratio of the linear-chain alkyl group in the plasticizer used in examples and comparative examples of the present invention were determined by gas chromatography (hereinafter abbreviated as GC) of the composition in the raw material alcohol used for the production. The result was defined as the number of carbon atoms of alkyl group and the ratio of the linear-chain alkyl group in the plasticizer. The method of measuring the raw material alcohol by GC is the same as above.

(382) (2) Evaluation of Physical Properties of Raw Material Ester and Present Diester

(383) The ester value, acid value, iodine value, oxirane oxygen, and hue of the raw material ester and the present ester obtained in the following production examples were analyzed in the same manner as described above.

(384) (3) Molding Processability

(385) Approximately 0.01 g of a sample obtained by mixing 10 g of a plasticizer with 2 g of a vinyl chloride-based resin (straight, polymerization degree 1050, trade name Zest 1000Z, manufactured by Shin Dai-Ichi Vinyl Corporation) was dropped onto a slide glass. A cover glass was covered on the slide glass, and the sample was set to an optical microscope. The temperature was raised at a rate of 5 C./min, and changes in the state of the particles of the vinyl chloride-based resin by the temperature rise due to heating were observed. The temperature at which the particles of the vinyl chloride-based resin started melting and the temperature at which the particles became transparent were defined as the gelation initiation temperature and the gelation termination temperature, respectively, and the average value of them was defined as the gelation temperature. The lower the gelation temperature, the faster the absorption rate of the plasticizer and the better the processability.

(386) (4) Preparation of Vinyl Chloride Sheet

(387) To 100 parts by weight of a vinyl chloride resin (straight, polymerization degree 1050, trade name Zest 1000Z, manufactured by Shin Dai-Ichi Vinyl Corporation) were respectively added 0.3 parts by weight of calcium stearate (manufactured by Nacalai Tesque, Inc.) and 0.2 parts by weight of zinc stearate (manufactured by Nacalai Tesque, Inc.) as a stabilizer, and the mixture was stirred and mixed with a mortar mixer to obtain a vinyl chloride-based resin composition. After stirring and mixing with a mortar mixer, 50 parts by weight of the diester of the present invention was added and mixed by hand until uniform, thereby obtaining a vinyl chloride-based resin for medical use. This resin composition was melt-kneaded at 160 to 166 C. for 4 minutes using a 512 inches twin roll to prepare a roll sheet. Subsequently, press molding was performed at 162 to 168 C. for 10 minutes to prepare a press sheet having a thickness of about 1 mm.

(388) [Evaluation of Physical Properties of Resin]

(389) (5) Tensile Characteristics: The 100% modulus, the breaking strength and the breaking elongation of the press sheet were measured according to JIS K-6723 (1995). The measurement demonstrated that the smaller the 100% modulus, the more desirable the flexibility. The breaking strength and the breaking elongation are indications of the practical strength of the material. Generally, it can be said that the greater these values, the more superior the practical strength.
(6) Cold Resistance: The softening temperature ( C.) of the press sheet was measured according to JIS K-6773 (1999) using a Clash-Berg tester. The lower the softening temperature ( C.), the more superior the cold resistance. The softening temperature here refers to a low temperature limit indicating a predetermined torsional rigidity rate (3.1710.sup.3 kg/cm.sup.2) in the above measurement.
(7) Heat Resistance (Volatility, Discoloration): The heat resistance was determined according to evaluation of volatile loss and sheet discoloration after heating.
a) Volatile loss: The roll sheet was heated in a gear oven at 170 C. for 60 minutes and 120 minutes, and a change in the weight was measured; then, the volatile loss (%) was calculated according to the following equation. The smaller the value of volatile loss, the higher the heat resistance.
Volatile loss (%)=((Weight before testWeight after test)/Weight before test)100
b) Sheet discoloration: The roll sheet was heated in a gear oven at 170 C. for 30 minutes and 60 minutes; thereafter, the intensity of discoloration of each roll sheet was visually evaluated on a five-level scale.
: Discoloration was not observed.
: Slight discoloration was observed.
: Discoloration was observed.
x: Strong discoloration was observed.
xx: Significant discoloration was observed.
(8) Ultraviolet Irradiation Test

(390) Yellow index (YI) of the press sheet was measured after 200 hours of measurement conditions (irradiance 120 W/m.sup.2, temperature 63 C., humidity 50%) using a xenon weather meter manufactured by Suga Test Instruments Co., Ltd.

Production Example 1

(391) Esterification Reaction

(392) A 2 L four-necked flask equipped with a thermometer, a decanter, a stirring blade and a reflux condenser was charged with 182.6 g of 4-cyclohexene-1,2-dicarboxylic anhydride (1.2 moles, RICACIDTH, manufactured by New Japan Chemical Co., Ltd.), 416 g (2.9 moles) of a saturated aliphatic alcohol containing 85.1% by weight of a linear-chain saturated aliphatic alcohol having 9 carbon atoms and 11.7% of a branched-chain saturated aliphatic alcohol having 9 carbon atoms (LINEVOL 9, manufactured by Shell Chemicals Co., Ltd.), and 0.24 g of tetraisopropyl titanate as an esterification catalyst, and then the esterification reaction was carried out at a reaction temperature of 200 C. The reaction was carried out until the acid value of the reaction solution became 0.5 mg KOH/g while removing the produced water out of the system by refluxing the alcohol under reduced pressure. After completion of the reaction, the unreacted alcohol was distilled out of the system under reduced pressure, and the system was neutralized, washed, and dehydrated according to a conventional method to obtain 449 g of an objective 4-cyclohexene-1,2-dicarboxylic acid diester (hereinafter referred to as ester 1).

(393) The ester 1 thus obtained had an ester value of 262 mg KOH/g, an acid value of 0.04 mg KOH/g, and a hue of 20.

(394) Epoxidation Reaction

(395) Then, 423 g (1.0 mole) of the ester 1 obtained in the above esterification reaction was charged into a 1 L four-necked flask equipped with a thermometer, a stirring blade and a cooling tube, and the temperature was raised to 60 to 70 C. After the temperature rise, 76.6 g (1.35 moles) of 60% hydrogen peroxide water, 18.3 g (0.30 moles) of 76% formic acid, and 1.47 g (0.01 moles) of 75% phosphoric acid were slowly added dropwise over a period of 2.25 hours. After completion of the dropwise addition, the above temperature was maintained for further 4 hours, and the reaction was completed by aging. After completion of the reaction, the aqueous phase was removed to the outside of the system, followed by washing with water and dehydration in a conventional manner to obtain 397 g of an objective 4,5-epoxycyclohexane dicarboxylic acid diester (hereinafter referred to as epoxy 1).

(396) The epoxy 1 thus obtained had an ester value of 256 mg KOH/g, an acid value of 0.06 mg KOH/g, an iodine value of 1.7 g I.sub.2/100 g, an oxirane oxygen content of 3.5%, and a hue of 10.

Production Example 2

(397) In the same manner as in Production Example 1 except that 464 g (2.9 moles) of saturated aliphatic alcohols having 9 to 11 carbon atoms (NEODOL 911, manufactured by Shell Chemicals Co., Ltd.) wherein the ratio of 9 carbon atoms/10 carbon atoms/11 carbon atoms is 19:43:38 and the overall linear chain ratio was 84% was added instead of 416 g of the saturated aliphatic alcohol (LINEVOL 9, manufactured by Shell Chemicals Co., Ltd.), 404 g of a 4,5-epoxycyclohexane dicarboxylic acid diester (hereinafter referred to as epoxy 2) was obtained.

(398) The epoxy 2 thus obtained had an ester value of 242 mg KOH/g, an acid value of 0.04 mg KOH/g, an iodine value of 1.7 g I.sub.2/100 g, an oxirane oxygen content of 3.1%, and a hue of 10.

Production Example 3

(399) In the same manner as in Production Example 1 except that 251 g (1.7 moles) of n-nonyl alcohol and 167 g (1.2 moles) of isononyl alcohol were added instead of 416 g of the saturated aliphatic alcohol (LINEVOL 9, manufactured by Shell Chemicals Co., Ltd.), 390 g of 4,5-epoxycyclohexane dicarboxylic acid diester (hereinafter referred to as epoxy 3) was obtained.

(400) The epoxy 3 thus obtained had an ester value of 250 mg KOH/g, an acid value of 0.02 mg KOH/g, an iodine value of 1.9 g I.sub.2/100 g, an oxirane oxygen content of 3.3%, and a hue of 10.

Production Example 4

(401) In the same manner as in Production Example 1 except that 378 g (2.9 moles) of 2-ethylhexanol was added instead of 416 g of the saturated aliphatic alcohol (LINEVOL 9, manufactured by Shell Chemicals Co., Ltd.), 390 g of 4,5-epoxycyclohexane dicarboxylic acid diester (hereinafter referred to as epoxy 4) was obtained.

(402) The epoxy 4 thus obtained had an ester value of 273 mg KOH/g, an acid value of 0.04 mg KOH/g, an iodine value of 2.6 g I.sub.2/100 g, an oxirane oxygen content of 3.7%, and a hue of 10.

Production Example 5

(403) In the same manner as in Production Example 1 except that 167 g (1.2 moles) of n-nonyl alcohol and 251 g (1.7 moles) of isononyl alcohol were added instead of 416 g of the saturated aliphatic alcohol (LINEVOL 9, manufactured by Shell Chemicals Co., Ltd.), 340 g of 4,5-epoxycyclohexane dicarboxylic acid diester (hereinafter referred to as epoxy 5) was obtained.

(404) The epoxy 5 thus obtained had an ester value of 257 mg KOH/g, an acid value of 0.06 mg KOH/g, an iodine value of 2.5 g I.sub.2/100 g, an oxirane oxygen content of 3.3%, and a hue of 10.

Example 1

(405) According to the method described in (3) Molding Processability above, the molding processability (gelation temperature) was measured using the epoxycyclohexane dicarboxylic acid diester (epoxy 1) obtained in Production Example 1. The obtained results were shown in Table 6.

(406) Subsequently, as described in (4) Preparation of Vinyl Chloride Sheet, the epoxy 1 was used as a plasticizer to prepare a soft vinyl chloride-based resin composition for medical (namely, medical vinyl chloride-based resin composition for use in soft materials), and a vinyl chloride sheet was prepared from the obtained soft vinyl chloride-based resin composition. The obtained sheet was subjected to a tensile test, a cold resistance test, a heat resistance test, and an ultraviolet irradiation test. The obtained results were shown in Table 6.

Example 2

(407) In the same manner as in Example 1 except that the epoxy 2 was used instead of the epoxy 1, the molding processability was measured, and then a soft vinyl chloride-based resin composition for medical was prepared. From the obtained soft vinyl chloride-based resin composition, a vinyl chloride sheet was prepared and subjected to a tensile test, a cold resistance test, a heat resistance test, and an ultraviolet irradiation test. The obtained results were summarized in Table 6.

Example 3

(408) In the same manner as in Example 1 except that the epoxy 3 was used instead of the epoxy 1, the molding processability was measured, and then a soft vinyl chloride-based resin composition for medical was prepared. From the obtained soft vinyl chloride-based resin composition, a vinyl chloride sheet was prepared and subjected to a tensile test, a cold resistance test, a heat resistance test, and an ultraviolet irradiation test. The obtained results were summarized in Table 6.

Comparative Example 1

(409) In the same manner as in Example 1 except that the epoxy 4 was used instead of the epoxy 1, the molding processability was measured, and then a soft vinyl chloride-based resin composition was prepared. From the obtained soft vinyl chloride-based resin composition, a vinyl chloride sheet was prepared and subjected to a tensile test, a cold resistance test, a heat resistance test, and an ultraviolet irradiation test. The obtained results were summarized in Table 6.

Comparative Example 2

(410) In the same manner as in Example 1 except that the epoxy 5 was used instead of the epoxy 1, the molding processability was measured, and then a soft vinyl chloride-based resin composition was prepared. From the obtained soft vinyl chloride-based resin composition, a vinyl chloride sheet was prepared and subjected to a tensile test, a cold resistance test, a heat resistance test, and an ultraviolet irradiation test. The obtained results were summarized in Table 6.

Comparative Example 3

(411) In the same manner as in Example 1 except that diisononyl 1,2-cyclohexane dicarboxylate (HEXAMOLL DINCH, manufactured by BASF) was used instead of the epoxy 1, the molding processability was measured, and then a soft vinyl chloride-based resin composition was prepared. From the obtained soft vinyl chloride-based resin composition, a vinyl chloride sheet was prepared and subjected to a tensile test, a cold resistance test, a heat resistance test, and an ultraviolet irradiation test. The obtained results were summarized in Table 6.

Comparative Example 4

(412) In the same manner as in Example 1 except that di-2-ethylhexyl phthalate (SANSO CIZER DOP, manufactured by New Japan Chemical Co., Ltd.) was used instead of the epoxy 1, the molding processability was measured, and then a vinyl chloride-based resin composition for soft materials was prepared. From the obtained vinyl chloride-based resin composition for soft materials, a vinyl chloride sheet was prepared and subjected to a tensile test, a cold resistance test, a heat resistance test, and an ultraviolet irradiation test. The obtained results were summarized in Table 6.

Comparative Example 5

(413) In the same manner as in Example 1 except that commercially available tri-2-ethylhexyl trimellitate was used instead of the epoxy 1, the molding processability was measured, and then a vinyl chloride-based resin composition for soft materials was prepared. From the obtained vinyl chloride-based resin composition for soft materials, a vinyl chloride sheet was prepared and subjected to a tensile test, a cold resistance test, a heat resistance test, and an ultraviolet irradiation test. The obtained results were summarized in Table 6.

(414) TABLE-US-00006 TABLE 6 Example Comparative Example Test items Unit (Condition) 1 2 3 1 2 3 4 5 Plasticizer Kind Epoxy 1 Epoxy 2 Epoxy 3 Epoxy 4 Epoxy 5 DINCH DOP TOTM Ratio of linear-chain alkyl group (%) 87 83 60 0 40 10 0 0 Molding Gelation C. 118 122 118 105 118 136 112 135 processability temperature Tensile 100% modulus MPa 9.9 10.5 10.3 9.8 10.6 10.8 9.4 13.1 characteristics Strength MPa 21.4 22.2 22.6 22.4 22.7 22.1 21.4 24.0 Elongation % 324 340 336 318 337 361 320 330 Cold resistance Softening C. 25 27 23 15 22 29 24 17 temperature Heat resistance Volatile loss % (170 C., 60 min.) 2.2 0.9 2.4 7.9 2.8 7.9 8.8 0.6 % (170 C., 120 mm.) 4.2 2.1 4.7 13.0 5.3 13.8 15.1 1.2 Sheet (170 C., 30 min.) discoloration (170 C., 60 min.) XX XX X UV irradiation Sheet (200 hours) 6.7 6.8 6.9 7.0 6.9 10.8 10.9 15.7 test discoloration

(415) The results of Table 6 clearly revealed that the vinyl chloride-based resin compositions for medical (Examples 1 to 3) in which the epoxycyclohexane dicarboxylic acid diester of the present invention was blended showed very small discoloration after the ultraviolet irradiation test as compared with the resin composition (Comparative Example 4) in which DOP was blended as a phthalic acid ester-type plasticizer that was currently most commonly used. Generally, discoloration of a molded body obtained from the vinyl chloride resin composition is due to formation of conjugated polyene by dehydrochlorination reaction of the vinyl chloride resin. Thus, irradiation with ultraviolet rays or radiation promotes such discoloration, so that it is known that discoloration occurs during sterilization or disinfection treatment. From the above results, it can be said that the same effect on discoloration may be exerted in not only ultraviolet irradiation but also in sterilization or disinfection treatment by various radiation irradiation which is thought to cause discoloration with the same mechanism.

(416) In addition, in comparison with the resin composition (Comparative Example 4) blended with a phthalate ester type plasticizer which is currently most widely used, the medical vinyl chloride-based resin compositions (Examples 1 to 3) also containing the epoxycyclohexane dicarboxylic acid diester of the present invention has less volatile loss and no discoloration by heat, and has reduced concerns regarding deterioration of flexibility due to volatilization of the plasticizer as well as degradation such as discoloration at the time of sterilization or disinfection treatment accompanied by heating such as boiling or heating in autoclave. Thus, these properties are found to be extremely useful.

(417) Next, even when compared with the resin composition (Comparative Example 5) in which TOTM, namely a trimellitate ester type plasticizer that is beginning to be used recently as an excellent heat resistant one, is blended, it is understood that the discoloration of the vinyl chloride-based resin composition containing the epoxycyclohexane dicarboxylic acid diester after the UV irradiation test is very small.

(418) In addition, by using the epoxycyclohexane dicarboxylic acid diester according to the present invention, the flexibility and cold resistance at the time of use are equal to or higher than the resin composition (Comparative Examples 1 and 2) blended with the epoxycyclohexane dicarboxylic acid diester outside the scope of the present invention. Furthermore, it is revealed that the composition of the invention is very useful because it has less volatile loss as well as has reduced concerns regarding deterioration of flexibility due to volatilization of the plasticizer at the time of sterilization or disinfection treatment accompanied by heating such as boiling or autoclave heating.

INDUSTRIAL APPLICABILITY

(419) The novel epoxycyclohexane dicarboxylic acid diester having an epoxy group in the molecular structure according to the present invention is excellent in plasticizing performance inherent in plasticizer for thermoplastic resin and rubber, is also excellent in heat resistance and cold resistance, and is therefore an excellent plasticizer capable of coping with demands for cold resistance and heat resistance which becomes increasingly severer in recent years, or is very useful as a stabilizer in a chlorine-containing resin. In particular, the epoxycyclohexane dicarboxylic acid diester of the present invention can be used as a plasticizer having also properties as a stabilizer in a chlorine-containing resin typified by vinyl chloride, and also can be used as a stabilizer in various material systems such as hard materials, semi-hard materials, and soft materials blended with other plasticizers. The resin composition blended with the epoxycyclohexane dicarboxylic acid diester having such performances and the resin molded body can be used in applications for electric wire covering and automobile parts, pipes such as water pipes, fittings for pipes, gutters such as rain gutters, window frame siding materials, flat plate, corrugated sheet, general film sheet applications (laminate, packaging, vehicle, miscellaneous goods, etc.), agricultural film applications, leather applications, compound applications, floor material applications, wallpaper applications, footwear applications, sealing material applications, fiber applications, hose applications, gasket applications, building material applications, paint applications, adhesive applications, paste applications, medical applications, and the like.