Self-crosslinkable polyhydroxy polyurethane resin, resinaceous material that contains the resin, process for production of the resin, and imitation leather, surfacing material and weatherstrip material, using the resin

Abstract

Provided are a self-crosslinking polyhydroxy polyurethane resin derived from a reaction of a 5-membered cyclic carbonate compound and an amine compound and having masked isocyanate groups in its structure; a process for producing the resin; an imitation leather composed of a base fabric and a resin composition composed of the resin as its principal component and impregnated in or laminated on the base fabric; as kin material made of a thermoplastic polyolefin resin, said skin material including a thermoplastic polyolefin resin sheet and a top coat layer formed directly or via a primer layer on the sheet, wherein the top coat layer has been formed with a resin composition composed of the resin as its principal component; and a weather strip material composed, as its principal components, of the resin and a specific diorganopolysiloxane and/or a silicone oil.

Claims

1. A self-crosslinking polyhydroxy polyurethane resin, wherein the self-crosslinking polyhydroxy polyurethane resin comprises in a structure thereof: a polyhydroxy polyurethane consisting of a reaction product consisting of a 5-membered cyclic carbonate compound and a diamine compound as reactants, where the diamine compound is a compound selected from the group consisting of a diamine compound having only two primary amine groups as amine groups, aminoethylethanolamine, hydroxyethylaminopropylamine, and mixtures thereof; a modifier; and at least one masked isocyanate group, the self-crosslinking polyhydroxy polyurethane resin consists of the polyhydroxy polyurethane having been modified with the modifier, as polyurethane, and a modification ratio of the self-crosslinking polyhydroxy polyurethane resin modified with the modifier is in a range from 2% to 60%, wherein the modifier has at least one free isocyanate group and the at least one masked isocyanate group before the modification of the polyhydroxy polyurethane, and the modification ratio of the self-crosslinking polyhydroxy polyurethane resin is obtained by a following formula:
modification ratio (%)={1-(hydroxyl groups in the polyhydroxy polyurethane in the self-crosslinking polyhydroxy polyurethane resin after modification/hydroxyl groups in the polyhydroxy polyurethane before modification)}100.

2. The self-crosslinking polyhydroxy polyurethane resin according to claim 1, wherein the 5-membered cyclic carbonate compound is a reaction product of an epoxy compound and carbon dioxide, and contains, in a structure of the 5-membered cyclic carbonate compound, a OC(O) group derived from the carbon dioxide in a range from 1 to 25 mass %.

3. The self-crosslinking polyhydroxy polyurethane resin according to claim 1, wherein the masked isocyanate groups are reaction products of organic polyisocyanate groups and a masking agent, the self-crosslinking polyhydroxy polyurethane resin is capable of self-crosslinking, when the self-crosslinking polyhydroxy polyurethane resin is subjected to a heat treatment, the masked isocyanate groups are demasked and form isocyanate groups, and the isocyanate groups react with hydroxyl groups in the structure of the self-crosslinking polyhydroxy polyurethane resin, so that the self-crosslinking polyhydroxy polyurethane resin undergoes self-crosslinking.

4. A process for producing the self-crosslinking polyhydroxy polyurethane resin according to claim 1, the process comprising: reacting the at least one free isocyanate group of the modifier, with hydroxyl groups in the polyhydroxy polyurethane, so as to obtain the self-crosslinking polyhydroxy polyurethane resin having been modified with the modifier and having the masked isocyanate groups in the structure thereof.

5. The process according to claim 4, wherein the 5-membered cyclic carbonate compound is a reaction product of an epoxy compound and carbon dioxide, and the carbon dioxide is contained in a range from 1 to 25 mass % in the self-crosslinking polyhydroxy polyurethane resin.

6. The process according to claim 4, wherein the modifier is a reaction product of an organic polyisocyanate compound and a masking agent.

7. A resin material comprising: the self-crosslinking polyhydroxy polyurethane resin according to claim 1; and another binder resin blended therewith.

8. An imitation leather comprising: a base fabric; and a resin composition comprising, as a principal component, the self-crosslinking polyhydroxy polyurethane resin according to claim 1, where the resin composition is impregnated in or laminated on the base fabric.

9. A skin material made of a thermoplastic polyolefin resin, comprising: a thermoplastic polyolefin resin sheet; and a top coat layer formed directly or via a primer layer on the sheet, wherein the top coat layer has been formed with a resin composition comprising, as a principal component, the self-crosslinking polyhydroxy polyurethane resin according to claim 1.

10. The skin material according to claim 9, wherein the self-crosslinking polyhydroxy polyurethane resin has been obtained by modifying, with the modifier, the polyhydroxy polyurethane resin, which is derived from the reaction of the 5-membered cyclic carbonate compound and the diamine compound, which is at least one compound selected from the group consisting of a diamine compound having only two primary amine groups as amine groups, aminoethylethanolamine, and hydroxyethylaminopropylamine.

11. The skin material according to claim 9, wherein the resin composition with which the top coat layer is formed further comprises a material, which comprises one fine powder or a combination of two or more fine powders selected from the group consisting of organic fine powders and inorganic fine powders, and which is added to the resin composition as a matting agent in a range from 1 to 150 parts by mass relative to 100 parts by mass of the self-crosslinking polyhydroxy polyurethane resin.

12. A weather strip material for coating and/or impregnating a high-molecular elastomer material to form a surface treatment layer at a slide contact portion that is brought into sliding contact with another part, wherein the weather strip material is a resin composition comprising: the self-crosslinking polyhydroxy polyurethane resin according to claim 1; and a material selected from the group consisting of a diorganopolysiloxane having an average polymerization degree in a range from 5,000 to 10,000, a silicone oil having a kinematic viscosity in a range from 100 to 10,000 CS, and a mixture thereof.

13. The weather strip material according to claim 12, wherein the self-crosslinking polyhydroxy polyurethane resin has been obtained by modifying, with the modifier, the polyhydroxy polyurethane derived from the reaction of the 5-membered cyclic carbonate compound and the diamine compound, which is at least one compound selected from the group consisting of a diamine compound having only two primary amine groups as amine groups, aminoethylethanolamine, and hydroxyethylaminopropylamine.

14. The weather strip material according to claim 12, wherein the resin composition comprises the self-crosslinking polyhydroxy polyurethane resin and the material ratio of the material in a range from 1 to 100 parts by mass relative to 100 parts by mass of the self-crosslinking polyhydroxy polyurethane resin.

15. The weather strip material according to claim 12, wherein the resin composition further comprises an additive comprising one fine powder or a combination of two or more fine powders selected from the group consisting of organic fine powders and inorganic fine powders, and the additive is added in a range from 1 to 150 parts by mass relative to 100 parts by mass of the self-crosslinking polyhydroxy polyurethane resin.

16. The resin according to claim 1, wherein the modifier is a reaction product of a masking agent and an organic polyisocyanate compound, the organic polyisocyanate compound is an aliphatic or aromatic polyisocyanate compound or an adduct of an aliphatic or aromatic polyisocyanate compound with other compound, the masking agent is at least one compound selected from the group consisting of alcohol-based compounds, phenol-based compounds, active methylene-based compounds, acid amide-based compounds, imidazole-based compounds, urea-based compounds, oxime-based compounds, and pyridine-based compounds.

Description

EXAMPLES

(1) The present invention will next be described in further detail based on specific production examples, examples and comparative examples, although the present invention shall not be limited to these examples. It is to be noted that the terms parts and % in the following examples are on a mass basis unless otherwise specifically indicated.

Production Example 1 (Production of Modifier)

(2) While thoroughly stirring a 1:3 adduct of trimethylolpropane and hexamethylene diisocyanate (COLONATE HL, trade name, product of Nippon Polyurethane Industry Co., Ltd.; NCO: 12.9%, solids content: 75%) (100 parts) and ethyl acetate (24.5 parts) at 100 C., -caprolactam (25.5 parts) was added, followed by a reaction for 5 hours. According to an infrared absorption spectrum (by FT-720, HORIBA Ltd.) of the resulting modifier, an absorption of free isocyanate groups remained at 2,270 cm.sup.1. Upon quantification of those free isocyanate groups, they were found to amount to 1.8% at a solids content of 50% (cf. calculated value: 2.1%).

(3) The structure of a principal compound in the modifier obtained as described above is presumed to be represented by the following formula.

(4) ##STR00006##

Production Example 2 (Production of Modifier)

(5) While thoroughly stirring an adduct of hexamethylene diisocyanate and water (DURANATE 24A-100, trade name, product of Asahi Kasei Corporation; NCO: 23.0%) (100 parts) and ethyl acetate (132 parts) at 80 C., methyl ethyl ketoxime (32 parts) was added, followed by a reaction for 5 hours. According to an infrared absorption spectrum of the resulting modifier, an absorption of free isocyanate groups remained at 2,270 cm.sup.1. Upon quantification of those free isocyanate groups, they were found to amount to 2.6% at a solids content of 50% (cf. calculated value: 2.9%).

(6) The structure of a principal compound in the modifier obtained as described above is presumed to be represented by the following formula.

(7) ##STR00007##

Production Example 3 (Production of Modifier)

(8) While thoroughly stirring a 1:3 adduct of trimethylolpropane and tolylene diisocyanate (COLONATE L, trade name, product of Nippon Polyurethane Industry Co., Ltd.; NCO: 12.5%, solids content: 75%) (100 parts) and ethyl acetate (67.3 parts) at 80 C., methyl ethyl ketoxime (17.3 parts) was added, followed by a reaction for 5 hours. According to an infrared absorption spectrum of the resulting modifier, an absorption of free isocyanate groups remained at 2,270 cm.sup.1. Upon quantification of those free isocyanate groups, they were found to amount to 2.0% at a solids content of 50% (cf. calculated value: 2.3%).

(9) The structure of a principal compound in the modifier obtained as described above is presumed to be represented by the following formula.

(10) ##STR00008##

Production Example 4 (Production of 5-Membered Cyclic Carbonate Compound)

(11) To a reaction vessel equipped with a stirrer, thermometer, gas inlet tube and reflux condenser, a divalent epoxy compound represented by the below-described formula (A) (EPICOAT 828, trade name, product of Japan Epoxy Resin Co., Ltd.; epoxy equivalent: 187 g/mol) (100 parts), N-methylpyrrolidone (100 parts) and sodium iodide (1.5 parts) were added, followed by dissolution into a homogeneous solution.

(12) ##STR00009##

(13) Subsequently, the solution was stirred under heating at 80 C. for 30 hours while bubbling carbon dioxide gas at a rate of 0.5 L/min. After completion of a reaction, the resultant reaction mixture was gradually added into n-hexane (300 parts) while stirring the latter at a high speed of 300 rpm. The resulting powdery reaction product was collected by a filter, and then washed with methanol to eliminate N-methylpyrrolidone and sodium iodide. The powder was dried in a drier to obtain, as a white powder, a 5-membered cyclic carbonate compound (1-A) (118 parts, yield: 95%).

(14) In an infrared absorption spectrum (by FT-720, HORIBA, Ltd.) of the thus-obtained reaction product (1-A), a peak around 910 cm.sup.1, which is attributable to the epoxy groups in the raw material, practically disappeared with respect to the reaction product, but an absorption of carbonyl groups in a cyclic carbonate group, which did not exist in any raw material, was confirmed around 1,800 cm.sup.1. The number average molecular weight of the reaction product was 414 (polystyrene equivalent; by GPC-8220, Tosoh Corporation). In the thus-obtained 5-membered cyclic carbonate compound (1-A), carbon dioxide was fixed as much as 19%.

Production Example 5 (Production of 5-Membered Cyclic Carbonate Compound))

(15) Using a divalent epoxy compound represented by the below-described formula (B) (YDF-170, trade name, product of Tohto Kasei Co., Ltd.; epoxy equivalent: 172 g/mol) in place of the divalent epoxy compound (A) used in Production Example 4, a reaction was conducted as in Production Example 4 to obtain, as a white powder, a 5-membered cyclic carbonate compound (1-B) (121 parts, yield: 96%).

(16) ##STR00010##

(17) The reaction product was identified by infrared absorption spectroscopy, GPC and NMR as in Production Example 4. In the thus-obtained 5-membered cyclic carbonate compound (1-B), carbon dioxide was fixed as much as 20.3%.

Production Example 6 (Production of 5-Membered Cyclic Carbonate Compound)

(18) Using EX-212 of the below-described formula (C) (trade name, product of Nagase ChemteX Corporation; epoxy equivalent: 151 g/mol) in place of the divalent epoxy compound (A) used in Production Example 4, a reaction was conducted as in Production Example 4 to obtain, as a colorless clear liquid, a 5-membered cyclic carbonate compound (1-C) (111 parts, yield: 86%).

(19) ##STR00011##

(20) The reaction product was identified by infrared absorption spectroscopy, GPC and NMR as in Production Example 4. In the thus-obtained 5-membered cyclic carbonate compound (1-C), carbon dioxide was fixed as much as 22.5%.

Example 1 (Production of Self-Crosslinking Polyhydroxy Polyurethane Resin Solution)

(21) A reaction vessel equipped with a stirrer, thermometer, gas inlet tube and reflux condenser was purged with nitrogen. To the reaction vessel, the 5-membered cyclic carbonate compound (100 parts) obtained in Production Example 4 was added, and further, N-methylpyrrolidone was added to adjust the solids content to 35%, followed by dissolution into a homogeneous solution. Hexamethylenediamine (27.1 parts) was then added, and the resulting mixture was stirred at a temperature of 90 C. for 10 hours so that a reaction was conducted until hexamethylenediamine became no longer detectable. The modifier of Production Example 1 was next added as much as 20 parts (solids content: 50%), followed by a reaction at 90 C. for 3 hours. Upon confirmation of disappearance of an absorption of isocyanate groups in an infrared absorption spectrum, the self-crosslinking polyhydroxy polyurethane resin solution of this example was obtained.

Examples 2 to 6 (Production of Self-Crosslinking Polyhydroxy Polyurethane Resin Solutions)

(22) Similar to Example 1, the 5-membered cyclic carbonate compounds, polyamine compounds and modifiers shown in Table 1 were then combined and reacted, respectively, in a similar manner as in Example 1 to obtain the self-crosslinking polyhydroxy polyurethane resin solutions of Examples 2 to 6 described in Table 1.

Comparative Example 1 (Production of Polyhydroxy Polyurethane Resin)

(23) A polyhydroxy polyurethane resin solution was used as in Example 1 except that the modifier of Production Example 1, which was employed in Example 1, was not used.

(24) TABLE-US-00001 TABLE 1 Compositions and Physical Properties of Self-crosslinking Polyhydroxy Polyurethane Resins Example 1 Example 2 Example 3 Example 4 Comp. Ex. 1 Carbonate compound (i) 1-A 1-A 1-B 1-B 1-A Amine compound (ii) HMDA.sup.1) HMDA HMDA HMDA HMDA Molar ratio (i/ii) 1.0 1.0 1.0 1.0 1.0 Modifier Production Production Production Production Example 1 Example 2 Example 2 Example 3 Solids content ratio 100/10 100/15 100/10 100/15 (resin/modifier) Solution viscosity (35% conc., MPa .Math. s) 1.8 2.1 1.9 2.2 1.3 Number average molecular weight 43,000 75,000 46,000 78,000 35,000 Hydroxyl number (mgKOH/g) 185 172 196 190 214 Fixed amount of carbon dioxide (%).sup.2) 13.8 13.2 15.5 14.8 15.2 Example 5 Example 6 Carbonate compound (i) 1-C 1-C Amine compound (ii) HMDA.sup.1) HMDA Molar ratio (i/ii) 1.0 1.0 Modifier Production Production Example 2 Example 3 Solids content ratio 100/10 100/15 (resin/modifier) Solution viscosity (35% conc., MPa .Math. s) 1.4 2.0 Number average molecular weight 41,000 72,000 Hydroxyl number (mgKOH/g) 208 191 Fixed amount of carbon dioxide (%).sup.2) 16.7 15.3 .sup.1)Hexamethylenediamine .sup.2)Calculated value

Comparative Example 2-1 (Production of Polyester Polyurethane Resin)

(25) A polyester polyurethane resin for use in this Comparative Example was synthesized as will be described below. A reaction vessel equipped with a stirrer, thermometer, gas inlet tube and reflux condenser was purged with nitrogen. In the reaction vessel, polybutylene adipate (average molecular weight: approx. 2,000) (150 parts) and 1,4-butanediol (15 parts) were dissolved in a mixed organic solvent consisting of methyl ethyl ketone (200 parts) and dimethylformamide (50 parts). Subsequently, under thorough stirring at 60 C., a solution of hydrogenated MDI (methylene bis(1,4-cyclohexane)-diisocyanate) (62 parts) in dimethylformamide (171 parts) was gradually added dropwise, and after completion of the dropwise addition, a reaction was conducted at 80 C. for 6 hours. The reaction mixture had a viscosity of 3.2 MPa.Math.s (25 C.) at a solids content of 35%.

Comparative Example 2-2 (Production of Polyester Polyurethane Resin)

(26) A polyester polyurethane resin for use in this Comparative Example was synthesized as will be described below. A reaction vessel equipped with a stirrer, thermometer, gas inlet tube and reflux condenser was purged with nitrogen. In the reaction vessel, polybutylene adipate (average molecular weight: approx. 2,000) (150 parts) and 1,4-butanediol (15 parts) were dissolved in dimethylformamide (250 parts). Subsequently, under thorough stirring at 60 C., a solution of hydrogenated MDI (methylene bis(1,4-cyclohexane)-diisocyanate) (62 parts) in dimethylformamide (171 parts) was gradually added dropwise, and after completion of the dropwise addition, a reaction was conducted at 80 C. for 6 hours. The reaction mixture had a viscosity of 3.2 MPa.Math.s (25 C.) at a solids content of 35%. A film obtained from the reaction mixture had a breaking strength of 45 MPa, a breaking extension of 480%, and a thermal softening temperature of 110 C.

Comparative Example 3-1 (Production of Polycarbonate Polyurethane Resin)

(27) Similar to Comparative Example 2-1, polycarbonate diol (product of UBE INDUSTRIES, LTD.; average molecular weight: approx. 2,000) (150 parts) and 1,4-butanediol (15 parts) were dissolved in a mixed organic solvent consisting of methyl ethyl ketone (200 parts) and dimethylformamide (50 parts). Subsequently, under thorough stirring at 60 C., a solution of hydrogenated MDI (62 parts) in dimethylformamide (171 parts) was gradually added dropwise, and after completion of the dropwise addition, a reaction was conducted at 80 C. for 6 hours. The reaction mixture had a viscosity of 1.6 MPa.Math.s (25 C.) at a solids content of 35%. A film obtained from the reaction mixture had a breaking strength of 21 MPa, a breaking extension of 250%, and a thermal softening temperature of 135 C.

Comparative Example 3-2 (Polycarbonate Polyurethane Resin)

(28) A polycarbonate polyurethane resin for use in this Comparative Example was synthesized as will be described below. Similar to Comparative Example 2-2, polycarbonate diol (product of UBE INDUSTRIES, LTD.; average molecular weight: approx. 2,000) (150 parts) and 1,4-butanediol (15 parts) were dissolved in dimethylformamide (250 parts). Subsequently, under thorough stirring at 60 C., a solution of hydrogenated MDI (62 parts) in dimethylformamide (171 parts) was gradually added dropwise, and after completion of the dropwise addition, a reaction was conducted at 80 C. for 6 hours. The reaction mixture had a viscosity of 1.6 MPa.Math.s (25 C.) at a solids content of 35%. A film obtained from the reaction mixture had a breaking strength of 21 MPa, a breaking extension of 250%, and a thermal softening temperature of 135 C.

(29) Evaluation

(30) Using the respective resin solutions of Examples 1 to 4, Comparative Example 1, and Comparative Example 2-1, films were produced by the casting method. With respect to each film so obtained, the below-described properties were determined by the below-described methods to rank the properties of the self-crosslinking polyhydroxy polyurethane resins. As casting conditions, after having been dried at 100 C. for 3 minutes, heat treatment was conducted at 160 C. for 30 minutes.

(31) (Mechanical Properties) Tensile Strength, Elongation

(32) With respect to each film, its mechanical properties (tensile strength, elongation) were ranked following JIS K7311. The results are shown in Table 2.

(33) (Thermal Softening Temperature)

(34) With respect to each film, its thermal softening temperature was ranked following JIS K7206 (Vicat softening temperature measuring method). The results are shown in Table 2.

(35) (Abrasion Resistance)

(36) With respect to each film, its abrasion resistance was ranked following JIS K7311. The results are shown in Table 2.

(37) (Solvent Resistance)

(38) Following JIS K5600-6-1, each film was observed for any change in external appearance after immersion for 10 minutes in toluene controlled at 50 C., whereby its solvent resistance was ranked. The results are shown in Table 2.

(39) (Environmental Responsiveness)

(40) The environmental responsiveness of each film was ranked A or B depending on whether or not carbon dioxide was fixed in it. The results are shown in Table 2.

(41) TABLE-US-00002 TABLE 2 Ranking Results of Resins Comp. Comp. Ex. 1 Ex. 2 Ex. 3 Ex. 4 Ex. 1 Ex. 2-1 Tensile 52 61 48 55 21 45.0 strength (MPa) Elongation (%) 9 6 7 5 15 480 Thermal 200 210 204 210 98 110 softening temperature Abrasion 20 11 17 8 85 55 resistance (mg) Solvent No No No No Swollen Swollen resistance change change change change Environmental A A A A A B responsiveness

(42) As shown in Table 2, sufficient crosslinking was confirmed to have proceeded in the films obtained using the resins of Examples 1 to 4. Further, the self-crosslinking polyhydroxy polyurethane resins of Examples 1 to 4 were confirmed to show equal or better performance on the above-described test items compared with the conventional polyester polyurethane resin of Comparative Example 2-1.

Examples 7 to 14 & Comparative Examples 4 to 9 (Production of Imitation Leathers)

(43) Separately using the resin solutions of Example 1, Example 2, Example 5, Example 6, Comparative Example 1, Comparative Example 2-2 and Comparative Example 3-2 prepared above, coating formulations for imitation leathers were prepared. Using those coating formulations, imitation leathers were produced, and were ranked by methods to be described subsequently herein. The compositions and ranking results are shown in Tables 3-1 and 3-2.

(44) (Artificial Leathers)

(45) The resin solutions obtained in Examples 1, 2, 5 and 6 and Comparative Examples 1, 2-2 and 3-2 were applied onto nonwoven fabrics made of polystyrene-polyester fibers to give a thickness of 1 mm, respectively. The thus-coated non-woven fabrics were immersed in a 10% aqueous solution of DMF controlled at 25 C., so that the resins were solidified. After washing, drying was conducted under heat (150 C./10 minutes) to obtain artificial leathers having porous layers as sheets.

(46) (Synthetic Leathers)

(47) A base material sheet for imitation leathers was prepared by coating and drying under heat a solution of a polyurethane-based resin (LETHAMINE UD-602S, trade name, product of Dainichiseika Color & Chemicals Mfg., Co., Ltd.) as an adhesive layer on a woven fabric to give a dry coat thickness of 10 m. On the other hand, the resin solutions obtained in Examples 1, 2, 5 and 6 and Comparative Examples 1, 2-2 and 3-2 were separately coated on sheets of release paper and dried under heat (150 C./10 minutes) to form films of approx. 15 m thickness, respectively. The thus-obtained films were bonded to cut pieces of the above-obtained base material sheet to obtain synthetic leathers, respectively.

(48) Evaluation

(49) Using the respective imitation leathers obtained as artificial leathers and synthetic leathers as described above, ranking was performed by the below-described methods and standards.

(50) (Hand Feeling)

(51) The hand feeling of each imitation leather was ranked, based on a hand touch feeling, in accordance with the following standards. The results are shown in Table 3-1 and Table 3-2. A: Soft B: A little hard C: Hard
(Chemical Resistance)

(52) Onto the surface of each synthetic leather obtained as described above, toluene was dropped. For allowing the surface to always remain in a wet state, the solvent was additionally dropped. One hour later, the solvent was wiped off. The chemical resistance of the synthetic leather was ranked in accordance with the following standards, and the results are shown in Table 3-2. A: No trace of dropping was observed at all on the coated surface. B: A change such as a slight trace of dropping or swelling was recognized, but it was not noticeable. C: A change in surface conditions (swelling or the like) was clearly recognized.
(Surface Abrasion Resistance)

(53) Using a plane abrasion tester, each synthetic leather obtained as described above was rubbed by reciprocating No. 6 canvas under a load of 1 kgf. The number of reciprocations until occurrence of a scratch was counted. The surface abrasion resistance of the synthetic leather was ranked in accordance with the following standards, and the results are shown in Table 3-2. A: 5,000 reciprocations or more B: 2,000 reciprocations or more, but less than 5,000 reciprocations C: Less than 2,000 reciprocations
(Thermal Softening Temperature)

(54) The thermal softening temperature of the film, which had been obtained by conducting coating on a sheet of release paper and heating under heat (150 C./10 minutes) upon production of each of the above-described synthetic leathers, was measured following JIS K7206 (Vicat softening temperature measuring method). The results are shown in Table 3-2.

(55) (Environmental Responsiveness)

(56) The environmental responsiveness of each imitation leather was ranked A or B depending on whether or not carbon dioxide was fixed in the used resin. The results are shown in Table 3-1 and Table 3-2.

(57) TABLE-US-00003 TABLE 3-1 Compositions of Coating Formulations for Imitation Leathers and Ranking Results (Artificial Leathers) Used resin Examples Comparative Examples solutions 7 8 9 10 4 5 6 Example 1 100 Example 2 100 Example 5 100 Example 6 100 Comparative 100 Example 1 Comparative 100 Example 2-2 Comparative 100 Example 3-2 Hand feeling B B A A B A A Environmental A A A A A B B responsiveness

(58) TABLE-US-00004 TABLE 3-2 Compositions of Coating Formulations for Imitation Leathers and Ranking Results (Synthetic Leathers) Used resin Examples Comparative Examples solutions 11 12 13 14 7 8 9 Example 1 100 Example 2 100 Example 5 100 Example 6 100 Comparative 100 Example 1 Comparative 100 Example 2-2 Comparative 100 Example 3-2 Hand feeling B B A A B A A Chemical A A A A C C C resistance Surface abrasion A A A A C C B resistance Thermal softening 200 210 193 210 98 110 135 point ( C.) Environmental A A A A A B B responsiveness

Examples 15 to 22 & Comparative Examples 10 to 15 (Production of Skin Materials)

(59) Separately using the resin solutions of Examples 1 to 4, Comparative Example 1, Comparative Example 2-1 and Comparative Example 3-1, coating formulations for forming top coat layers, the compositions of which are described in Tables 4 and 5, were prepared. Evaluation sheets of skin materials, which had the top coat layers on the surfaces thereof, were then formed by a method to be described subsequently herein. Using those evaluation sheets, they were ranked for moldability, gloss value, adhesiveness, scratch resistance, oil resistance, chemical resistance, surface abrasion resistance, and environmental responsiveness by the below-described methods.

(60) (Formation Method of Top Coat Layers)

(61) Employed was a base material sheet of a thermoplastic polyolefin, which had been subjected to corona discharge treatment to activate its surface to a wetting index of 45 dyn/cm. Onto the resulting base material sheet, chlorinated polypropylene (SUPERCHLON, trade name, product of Nippon Paper Chemicals Co., Ltd.) was coated by a 120-mesh gravure roll to give a dry coat thickness of 3 m, followed by drying at 100 C. for 2 minutes to form a primer layer. Onto cut pieces of the thus-formed coating film, the coating formulations for forming top coat layers as described in Table 2 were applied, respectively, by a 120-mesh gravure roll to give a dry coat thickness of 5 m. The coating formulations so applied were dried at 150 C. for 3 minutes, and subsequent to aging at 80 C. for 24 hours, the resulting skin materials were molded by a vacuum molding machine equipped with a convex mold controlled at 160 C. at a surface thereof, whereby molded products (skin materials) with the top coat layers formed on the surfaces thereof were obtained, respectively. Using the thus-obtained molded products, evaluation was performed in accordance with the below-described standards. The results are collectively shown in Table 4 and Table 5.

(62) Evaluation

(63) (Moldability)

(64) The surface of each sheet after its vacuum molding was visually observed and ranked. A: Good (No molding cracking or whitening phenomenon) B: Bad (Either molding cracking or whitening phenomenon was observed)
(Gloss Value)

(65) Following JIS K5600, the surface of each sheet after its vacuum molding was measured by a gloss meter. One having a gloss value of 1.2 or smaller (standard value required in the relevant business field) was set to pass.

(66) (Adhesiveness)

(67) On the surface of each coating film as a skin after the vacuum molding, a cross-cut cellophane tape peeling test was conducted to rank its adhesiveness. A: Good (No peeled portion in the coated surface) B: Bad (Peeled area at the coated surface)
(Scratch Resistance)

(68) The surface of each coating film as a skin after the vacuum molding was rubbed with a nail. By visually observing whether or not a trace of scratch or whitening had occurred, the scratch resistance of the sheet was ranked. A: Good (Nail scratch or whitening was hardly noticeable at the coated surface) B: Bad (Nail scratch or a trace of whitening was clearly noticeable at the coated surface)
(Oil Resistance)

(69) The surface of each coating film as a skin was coated over a radius of 2 cm with beef tallow (Nacalai Tesque, Inc.), and the coating film so coated was left over for 5 days in an atmosphere controlled at 80 C. Subsequently, the beef tallow was removed. On the coated surface, a cross-cut cellophane tape peeling test was conducted to rank the oil resistance of the coating film in accordance with the same standards as in the case of scratch resistance.

(70) (Chemical Resistance)

(71) Onto the surface of each coating film as a skin, ethanol was dropped. For allowing the surface to always remain in a wet state, the solvent was additionally dropped. One hour later, the solvent was wiped off. A: No trace of dropping was observed at all on the coated surface. B: A slight trace of dropping was recognized, but it was not noticeable. C: A clear trace of dropping was recognized.
(Surface Abrasion Resistance)

(72) Using a plane abrasion tester, the surface of each coating film as a skin was rubbed by reciprocating No. 6 canvas under a load of 1 kgf. The number of reciprocations until occurrence of a scratch was counted. A: 5,000 reciprocations or more B: 2,000 reciprocations or more, but less than 5,000 reciprocations C: Less than 2,000 reciprocations
(Environmental Responsiveness)

(73) The environmental responsiveness of each coating film as a skin was ranked A or B depending on whether or not carbon dioxide was fixed in the used resin.

(74) TABLE-US-00005 TABLE 4 Compositions of Coating Formulations for Forming Top Coat Layers and Ranking Results Examples 15 16 17 18 19 20 21 22 Primer Chlorinated polypropylene Resin solution of Example 1 100 100 Resin solution of Example 2 100 100 Resin solution of Example 3 100 100 Resin solution of Example 4 100 100 Matting Resin particles.sup.a) 35 25 35 25 35 25 35 25 agents Silica.sup.b) 10 10 10 10 Moldability A A A A A A A A Gloss value 0.9 0.7 0.9 0.7 1.0 0.9 0.9 0.7 Adhesiveness A A A A A A A A Scratch resistance A A A A A A A A Oil resistance A A A A A A A A Chemical resistance A A A A A A A A Surface abrasion resistance A A A A A A A A Environmental responsiveness A A A A A A A A .sup.a)FINE POLYURETHANE PARTICLES (product of Dainichiseika Color & Chemicals Mfg., Co., Ltd., average particle size: 5 m) .sup.b)NIPSIL (product of Nippon Silica Industry Co., Ltd.)

(75) TABLE-US-00006 TABLE 5 Compositions of Coating Formulations for Forming Top Coat Layers and Ranking Results Comparative Examples 10 11 12 13 14 15 Primer layer material Chlorinated polypropylene Resin solution of Comp. Ex. 1 100 100 Resin solution of Comp. Ex. 2-1 100 100 Resin solution of Comp. Ex. 3-1 100 100 Matting Resin particles.sup.a) 35 25 35 25 35 25 agents Silica.sup.b) 10 10 10 Moldability A A A A A A Gloss value 0.9 0.7 0.9 0.7 1.0 0.9 Adhesiveness A B B C B C Scratch resistance B C B C B C Oil resistance B B B B B B Chemical resistance C C C C C C Surface abrasion resistance B C B C B C Environmental responsiveness A A B B B B .sup.a)FINE POLYURETHANE PARTICLES (product of Dainichiseika Color & Chemicals Mfg., Co., Ltd., average particle size: 5 m) .sup.b)NIPSIL (product of Nippon Silica Industry Co., Ltd.)

Examples 23 to 30 & Comparative Examples 16 to 21 (Production of Weather Strip Materials)

(76) Using the resin solutions (coating formulations) of Examples 1 to 4, Comparative Example 1, Comparative Example 2-1 and Comparative Example 3-1, coating formulations of the compositions described in Tables 6 and 7 were prepared. Those coating formulations were then applied by an air spray gun onto EPDM rubber sheets, followed by drying at 140 C. for 10 minutes to form films of 20 m on the sheets, respectively. The EPDM rubber sheets, which had been obtained as described above and had the films, were provided as measurement samples for the ranking of the surface treatment layers (films) formed with the respective weather strip materials.

(77) Evaluation

(78) The weather strip materials (coating formulations) obtained as described above and the above-described respective measurement samples were measured for coefficient of static friction, coefficient of kinetic friction, contact angle, adhesiveness, abrasion durability, weatherability and the like by the below-described methods, and the materials of the examples and comparative examples were ranked. Ranking results are collectively shown in Tables 6 and 7.

(79) (Coefficient of Static Friction, Coefficient of Kinetic Friction)

(80) The coefficient of static friction and coefficient of kinetic friction of each weather strip material (coating formulation) against a glass member were measured by a surface property tester (manufacture by Shinto Scientific Co., Ltd.).

(81) (Contact Angle)

(82) The contact angle to water at the film portion of each measurement sample obtained as described above was measured by a contact angle meter (manufactured by Kyowa Interface Science Co., Ltd.), and was recorded as the contact angle of the film, which was formed by using the corresponding weather strip material, to water.

(83) (Adhesiveness)

(84) On the film portion of each measurement sample obtained as described above, a peeling test was conducted by the cross-cut cellophane tape peeling test. The adhesiveness of the surface of the film formed from the corresponding weather strip material was ranked in accordance with the following standards. A: Good (No peeled portion in the film surface) B: Bad (Peeled area on the film surface)
(Abrasion Durability)

(85) A glass plate was brought under a load of 9.8 N into contact with the film portion of each measurement sample obtained as described above, and the glass plate was reciprocated. The number of reciprocations until occurrence of a tear or the like in the film was counted by the surface property tester (manufacture by Shinto Scientific Co., Ltd.). Based on the number of the reciprocations so counted, the abrasion durability of the surface of the film formed from the corresponding weather strip material was ranked.

(86) (Weatherability Test)

(87) Using a SUNSHINE CARBON ARC WEATHER METER (Suga Test Instruments Co., Ltd.), the film portion of each measurement sample obtained as described above was exposed to light at a panel temperature of 83 C. for 200 hours. The conditions of the surface of the film were then visually observed, and the weatherability of the surface of the film formed from the corresponding weather strip material was ranked in accordance with the following standards.

(88) 3: No changes in surface conditions

(89) 2: Some changes in surface conditions

(90) 1: Significant changes and whitening phenomenon

(91) (Environmental Responsiveness)

(92) The environmental responsiveness of each weather strip material was ranked A or B depending on whether or not carbon dioxide was fixed in the resin contained in the weather strip material (coating formulation).

(93) TABLE-US-00007 TABLE 6 Compositions of Weather Strip Materials and Their Ranking Examples 23 24 25 26 27 28 29 30 Resin Example 1 100 100 solutions Example 2 100 100 Example 3 100 100 Example 4 100 100 Matting Resin particles.sup.a) 25 25 25 25 agents Silica.sup.b) 10 10 10 10 Diorganopolysiloxane.sup.c) 20 20 20 20 20 20 20 20 Coefficient of static friction 0.48 0.35 0.45 0.32 0.52 0.38 0.50 0.32 Coefficient of kinetic friction 0.17 0.15 0.17 0.15 0.17 0.15 0.17 0.16 Contact angle () 107 114 108 115 108 112 108 114 Adhesiveness A A A A A A A A Abrasion durability (10.sup.4 12 15 13 16 13 15 12 14 reciprocations) Weatherability test 3 3 3 3 3 3 3 3 Environmental responsiveness A A A A A A A A .sup.a)FINE POLYURETHANE PARTICLES (product of Dainichiseika Color & Chemicals Mfg., Co., Ltd., average particle size: 5 m) .sup.b)NIPSIL (product of Nippon Silica Industry Co., Ltd.) .sup.c)KF96H-10,000 cs (product of Shin-Etsu Chemical Co., Ltd.)

(94) TABLE-US-00008 TABLE 7 Compositions of Weather Strip Materials and Their Ranking Comparative Examples 16 17 18 19 20 21 Resin Comp. Ex. 1 100 100 solutions Comp. Ex. 2-1 100 100 Comp. Ex. 3-1 100 100 Matting Resin particles.sup.a) 25 25 25 agents Silica.sup.b) 10 10 10 Diorganopolysiloxane.sup.c) 20 20 20 20 20 20 Coefficient of static friction 0.52 0.42 0.63 0.55 0.57 0.50 Coefficient of kinetic friction 0.17 0.15 0.17 0.15 0.17 0.15 Contact angle () 108 114 108 115 108 112 Adhesiveness A A B B B B Abrasion durability (10.sup.4 7 9 5 8 7 10 reciprocations) Weatherability test 3 3 1 1 2 2 Environmental responsiveness A A B B B B .sup.a)FINE POLYURETHANE PARTICLES (product of Dainichiseika Color & Chemicals Mfg., Co., Ltd., average particle size: 5 m) .sup.b)NIPSIL (product of Nippon Silica Industry Co., Ltd.) .sup.c)KF96H-10,000 cs (product of Shin-Etsu Chemical Co., Ltd.)

INDUSTRIAL APPLICABILITY

(95) According to the present invention, it becomes possible to provide a polyhydroxy polyurethane resin, the development of applications of which has not moved ahead although it is considered to contribute to the resolution of problems such as global warming and resource depletion, as a self-crosslinking polyhydroxy polyurethane resin effectively usable for industrial applications. Owing to the use of the self-crosslinking polyhydroxy polyurethane resin according to the present invention, formed products can be also sufficiently satisfactory in performance such as heat resistance, chemical resistance and abrasion resistance although they are environment-responsive products which contain carbon dioxide incorporated therein and can contribute to the reduction of warming gas. Therefore, the self-crosslinking polyhydroxy polyurethane resin is also expected to find active utility from the standpoint of the conservation of the global environment.

(96) The imitation leather according to the present invention is provided with excellent scratch resistance, abrasion resistance, chemical resistance and heat resistance, because owing to the use of the resin composition composed as a principal component of the above-described self-crosslinking polyhydroxy polyurethane resin, the masked isocyanate groups, which are contained in the structure of the resin and are demasked by heat, and the hydroxyl groups in the polyhydroxy polyurethane resin in the resin react to form a crosslinked resin. As a result, it becomes possible to provide an imitation leather product, which is responsive to environmental conservation and has not been realized with conventional products. Consequently, it is possible to contribute to the resolution of problems, such as global warming and resource depletion, which has become a worldwide issue in recent years.

(97) The skin material according to the present invention, which is made of a thermoplastic polyolefin resin, is excellent in scratch resistance, abrasion resistance, chemical resistance and heat resistance, and further, is also excellent in uniform matting effect, because the top coat layer on the thermoplastic olefin resin sheet has been formed with the resin composition composed, as a principal component, of the self-crosslinking polyhydroxy polyurethane resin and has been formed as a self-crosslinked film by the demasking of the masked isocyanate groups in the resin under heat and the reaction of the demasked isocyanate groups and the free hydroxyl groups in the polyhydroxy polyurethane resin. As a result, it becomes possible to provide a skin material responsive to environmental conservation, the provision of which has not been realized with conventional products. The use of skin materials can hence be enlarged, thereby making it possible to contribute to the resolution of problems such as global warming and resource depletion, which has become a worldwide issue in recent years.

(98) The weather strip material according to the present invention is excellent in lubricity, abrasion resistance, heat resistance and weatherability, and further, is also excellent in uniform matting effect, because the weather strip material is a resin composition containing the self-crosslinking polyhydroxy polyurethane resin and one or more additives and the masked isocyanate groups, which are contained in the structure of the resin and are demasked by heat, and the hydroxyl groups in the resin react to form a crosslinked resin. As a result, the surface treatment layer formed by using the weather strip material is excellent in performance. As the self-crosslinking polyhydroxy polyurethane resin for use in the present invention is a useful material which contains carbon dioxide incorporated and fixed therein and contributes to the resolution of problems such as global warming and resource depletion, the weather strip material which is obtained by using the material can also provide products responsive to environmental conservation, the provision of which has not been realized with conventional products. The use of the weather strip material is, therefore, expected to expand from this respect.