COMPOSITION, PRODUCTION METHOD FOR COMPOSITION, AND PRODUCTION METHOD FOR UNSATURATED COMPOUND

Abstract

The invention is related to a composition excellent in stability during storage and excellent stability during utilization, and related to a method of producing the composition. The composition comprises a compound (A) represented by general formula (1) and a compound (B). The compound (B) is an oligomer in which two or more molecules of the compound (A) are bonded to each other by ethylenically unsaturated groups of each compound (A). The composition contains 0.00002 to 0.2 parts by mass of the compound (B) with respect to 100 parts by mass of the compound (A),

(R.sub.1—COO).sub.n—R.sub.2—(NCO).sub.m  (1)

wherein in general formula (1), R.sub.1 is an ethylenically unsaturated group having 2 to 7 carbon atoms; R.sub.2 is a (m+n)-valent hydrocarbon group having 1 to 7 carbon atoms and optionally contain an ether group; and n and in each represent an integer of one or two.

Claims

1. A composition comprising: a compound (A) represented by general formula (1) and a compound (B) wherein the compound (B) is an oligomer in which two or more molecules of the compounds (A) are bonded to each other by an ethylenically unsaturated group of each compound (A); and the composition comprises 0.00002 to 0.2 parts by mass of the compound (B) with respect to 100 parts by mass of the compound (A),
(R.sub.1—COO).sub.n—R.sub.2—(NCO).sub.m  (1) wherein in the general formula (1), R.sub.1 is an ethylenically unsaturated group having 2 to 7 carbon atoms; R.sub.2 is a (m+n)-valent hydrocarbon group having 1 to 7 carbon atoms and optionally comprises an ether group; and n and m each represent an integer of 1 or 2.

2. The composition according to claim 1, wherein the compound (A) is at least one compound selected from the group consisting of 2-methacryloyloxyethyl isocyanate, 2-(isocyanatoethyloxy) ethyl methacrylate, 2-acryloyloxyethyl isocyanate, 2-(isocyanatoethyloxy) ethyl acrylate, and 1,1-bis(acryloyloxymethyl)ethyl isocyanate.

3. The composition of claim 1, wherein a content of the compound (A) in the composition is 95.0% by mass or more.

4. A method of producing a composition, comprising steps of: producing a mixture comprising the compound (A) and the compound (B); and purifying the mixture by a distillation process at a reflux ratio of 2.0 to 4.0, a pressure of 1.0 to 10.0 kPa and a distillation temperature of 90 to 140° C., wherein the purifying step comprises: a vacuum breaking step of supplying a gas having a dew point of −30° C. or less in a distillation apparatus after distillation by the distillation process and returning the pressure in the distillation apparatus to atmospheric pressure, wherein the gas comprises nitrogen gas oxygen gas at an oxygen concentration of 1 vol % or more and less than the critical oxygen concentration of compound (A); and a filling step of storing the purified product in the distillation apparatus after distillation in a container and filling a gas phase portion in the container with air having a dew point of −30° C. or lower.

5. The method of producing a composition according to claim 4, wherein the mixture comprises more than 0.2 parts by mass of the compound (B) with respect to 100 parts by mass of the compound (A); and the purified product comprises 0.00002 to 0.2 parts by mass of the compound (B) with respect to 100 parts by mass of the compound (A).

6. A method of producing an unsaturated compound, comprising the steps of: mixing the composition according to claim 1 with a compound having active hydrogen; and reacting the compound (A) contained in the composition with the compound having active hydrogen to obtain a reaction product.

7. The method of producing an unsaturated compound according to claim 6, wherein the compound having the active hydrogen is an alcohol, a thiol, an amine or a carboxylic acid.

8. The method of producing the unsaturated compound according to claim 6, wherein the reaction product is an unsaturated urethane compound, an unsaturated thiourethane compound, an unsaturated urea compound, or an unsaturated amide compound.

9. The method of producing an unsaturated compound according to claim 6, wherein the reaction product is any one selected from the group consisting of 2-butanone oxime-O-(carbamoylethyl-2-methacrylate), 2-butanone oxime-O-(carbamoylethyl-2-acrylate), 2-[(3,5-dimethylpyrazolyl)carbonylamino]ethyl methacrylate, and 2-[(3,5-dimethylpyrazolyl) carbonylamino]ethyl acryl ate.

Description

EXAMPLES

[0137] The present invention will be specifically described below with reference to examples and comparative examples. The following examples are intended to facilitate understanding of the contents of the present invention, and the present invention is not limited to these examples alone. For example, in all examples, the content of compound (A) in the composition is 95.0% by mass or more. However, the present invention is not limited to these examples, and the content of the compound (A) in the composition may be, for example, less than 95.0% by mass.

[0138] Mixture 1 and Mixture 2 were prepared by the following methods.

[0139] <Mixture 1> (Synthesis of MOI)

[0140] In a 500 ml four-necked flask equipped with a stirrer, condenser, thermometer and inner tube, 250 ml of toluene and 25 g (0.41 mol) of 2-aminoethanol were added, heated to 90° C. and supplied with about 20 g of hydrogen chloride gas. Then, 44 g (0.42 mol) of methacrylic acid chloride was added dropwise, and the mixture was heated at 90° C. for 1 hour. Thereafter, 80 g (0.81 mol) of phosgene was supplied. 0.4 g of phenothiazine and 0.4 g of 2,6-bis-tert-butylhydroxytoluene were then added to remove dissolved phosgene and toluene.

[0141] By the above process, Mixture 1 containing the main product (the compound (A)) of 2-methacryloyloxyethyl isocyanate (MOI) 45 g (0.29 mol) (71% yield) and the by-product (the compound (B)) of 2-methacryloyloxyethyl isocyanate oligomer (Oligomer formed by reaction of double bond) (18034 ppm by mass) was obtained.

[0142] <Mixture 2> (Synthesis of AOI)

[0143] In a 500 mL four-necked flask equipped with a stirrer, condenser, thermometer and inner tube, 250 mL of toluene and 25 g (0.41 mol) of 2-aminoethanol were added, heated to 90° C. and supplied with about 20 g of hydrogen chloride gas. Then 56 g (0.44 mol) of 3-chloropropionic acid chloride was added dropwise over 90 minutes and heated at 90° C. for 1 hour. Thereafter, 80 g (0.81 mol) of phosgene was supplied. Dissolved phosgene was then removed by nitrogen gas bubbling. Subsequently, 0.4 g of phenothiazine and 0.4 g of 2,6-bis-t-butylhydroxytoluene were added, and 50 g of triethylamine (0.49 mol) was supplied, and the mixture was heated and stirred at 50° C. for 6 hours. Thereafter, the mixture was cooled to room temperature, the formed hydrochloride salt was filtered, and toluene was distilled off.

[0144] By the above process, Mixture 2 containing the main product (the compound (A)) of 2-acryloyloxyethyl isocyanate (AOI) 55 g (0.35 mol) (87% yield) and the by-product (the compound (B)) of 2-acryloyloxyethyl isocyanate oligomer (Oligomer formed by reaction of double bond) (27530 ppm by mass) was obtained.

Examples 1 to 6 and Comparative Examples 1 to 8

MOI

[0145] 50 g of Mixture 1 was distilled under the conditions shown in Tables 1 and 2 (reflux ratio (reflux/distillate), distillation temperature, distillation pressure). The liquid compositions of Examples 1 to 6 and Comparative Examples 1 to 8 housed in a container were obtained by carrying out a vacuum breaking step in which the gas shown in Tables 1 and 2 was supplied into the distillation apparatus after distillation to return the pressure in the distillation apparatus to atmospheric pressure; and a filling step in which the purified product in the distillation apparatus after distillation was housed in the containers shown in Tables 1 and 2 and the gas phase portion in the container was filled with the gas shown in Tables 1 and 2.

[0146] The critical oxygen concentration of 2-methacryloyloxyethyl isocyanate (MOI) is 8 vol %. The oxygen gas concentration in the gas supplied into the distillation apparatus in the vacuum breaking step was measured using a zirconia type oxygen concentration meter.

Examples 7 to 12 and Comparative Examples 9 to 16

AOI

[0147] 50 g of Mixture 2 was distilled under the conditions shown in Tables 3 and 4 (reflux ratio (reflux/distillate), distillation temperature, distillation pressure). The liquid composition of Examples 7 to 12 and Comparative Examples 9 to 16 accommodated in a container was obtained by carrying out a vacuum breaking step in which the gas shown in Tables 3 and 4 was supplied into the distillation apparatus after distillation to return the pressure in the distillation apparatus to atmospheric pressure; and a filling step in which the purified product in the distillation apparatus after distillation was accommodated in the containers shown in Tables 1 and 2 and the gas phase portion in the container was filled with the gas shown in Tables 3 and 4.

[0148] The critical oxygen concentration of 2-acryloyloxyethyl isocyanate (AM) is 7 vol %. The oxygen gas concentration in the gas supplied into the distillation apparatus in the vacuum breaking step was measured using a zirconia type oxygen concentration meter.

TABLE-US-00001 TABLE 1 Example 1 2 3 Distillation 110 115 90 temperature(° C.) Distillation 2.0 2.5 1.0 pressure (kPa) Reflux ratio 3.5 3.0 3.5 Gas supplied in the Dried nitrogen Dried nitrogen Dried nitrogen vacuum breaking Dilution air Dilution air Dilution air step (Dew point: −40° C.) (Dew point: −40° C.) (Dew point: −40° C.) (Oxygen: 3 vol %) (Oxygen: 4 vol %) (Oxygen: 3 vol %) Gas filled in the Dried air Dried air Dried air filling step (Dew point: −50° C.) (Dew point: −60° C.) (Dew point: −30° C.) Container Chemical drum Chemical drum Chemical drum with high-density with high-density with high-density PE inner bag PE inner bag PE inner bag Compound A 98.0 98.5 98.7 content (% by mass) Compound B 540 150 204 Content (×10.sup.−4 parts by mass) Yield (%) 85 87 90 Viscosity (mPa .Math. sec) 1.5 1.7 1.6 Appearance No change No change No change Example 4 5 6 Distillation 100 135 130 temperature(° C.) Distillation 1.5 6.0 6.0 pressure (kPa) Reflux ratio 2.5 2.0 4.0 Gas supplied in the Dried nitrogen Dried nitrogen Dried nitrogen vacuum breaking Dilution air Dilution air Dilution air step (Dew point: −50° C.) (Dew point: −40° C.) (Dew point: −30° C.) (Oxygen: 4 vol %) (Oxygen: 6 vol %) (Oxygen: 5 vol %) Gas filled in the Dried air Dried air Dried air filling step (Dew point: −30° C.) (Dew point: −50° C.) (Dew point: −60° C.) Container Chemical drum Chemical drum Chemical drum with high-density with high-density with high-density PE inner bag PE inner bag PE inner bag Compound A 98.2 99.2 99.4 content (% by mass) Compound B 560 360 450 Content (×10.sup.−4 parts by mass) Yield (%) 88 84 78 Viscosity (mPa .Math. sec) 1.7 1.7 1.6 Appearance No change No change No change

TABLE-US-00002 TABLE 2 Comparative Example 1 2 3 4 Distillation 90 110 135 110 temperature(° C.) Distillation 1.0 2.0 6.5 2.0 pressure (kPa) Reflux ratio 1.0 0.2 1.5 0.5 Gas supplied in the Dried nitrogen Dried nitrogen Dried nitrogen Dried nitrogen vacuum breaking Dilution air Dilution air Dilution air Dilution air step (Dew point: −40° C.) (Dew point: −50° C.) (Dew point: −50° C.) (Dew point: −60° C.) (Oxygen: 3 vol %) (Oxygen: 4 vol %) (Oxygen: 6 vol %) (Oxygen: 5 vol %) Gas filled in the Dried air Dried air Dried air Dried air filling step (Dew point: −50° C.) (Dew point: −60° C.) (Dew point: −40° C.) (Dew point: −40° C.) Container Chemical drum Chemical drum Chemical drum Chemical drum with high-density with high-density with high-density with high-density PE inner bag PE inner bag PE inner bag PE inner bag Compound A 97.5 97 97.8 96.3 content (% by mass) Compound B 2200 2650 3302 2813 Content (×10.sup.−4 parts by mass) Yield (%) 93 90 85 88 Viscosity (mPa .Math. sec) Not measurable Not measurable Not measurable Not measurable Appearance Syrup-like Solid Syrup-like Solid Comparative Example 5 6 7 8 Distillation 90 100 135 130 temperature(° C.) Distillation 1.0 1.5 6.0 6.0 pressure (kPa) Reflux ratio 3.5 2.5 2.0 4.5 Gas supplied in the Dried nitrogen Dried nitrogen Dried nitrogen Dried nitrogen vacuum breaking (Dew point: −30° C.) (Dew point: −50° C.) Dilution air (Dew point: −30° C.) step (Dew point: −40° C.) (Oxygen: 4 vol %) Gas filled in the Dried nitrogen Dried air Dried nitrogen Dried nitrogen filling step (Dew point: −40° C.) (Dew point: −30° C.) (Dew point: −50° C.) (Dew point: −60° C.) Container Chemical drum Chemical drum Chemical drum Chemical drum with high-density with high-density with high-density with high-density PE inner bag PE inner bag PE inner bag PE inner bag Compound A 98.2 97.7 98.7 98.9 content (% by mass) Compound B 4650 3362 4870 6897 Content (×10.sup.−4 parts by mass) Yield (%) 90 88 84 78 Viscosity (mPa .Math. sec) Not measurable Not measurable Not measurable Not measurable Appearance Syrup-like Solid Syrup-like Solid

TABLE-US-00003 TABLE 3 Example 7 8 9 Distillation 90 120 130 temperature(° C.) Distillation 1.5 3.5 6.5 pressure (kPa) Reflux ratio 3.5 2.0 3.5 Gas supplied in the Dried nitrogen Dried nitrogen Dried nitrogen vacuum breaking Dilution air Dilution air Dilution air step (Dew point: −50° C.) (Dew point: −60° C.) (Dew point: −40° C.) (Oxygen: 4 vol %) (Oxygen: 3 vol %) (Oxygen: 3 vol %) Gas filled in the Dried air Dried air Dried air filling step (Dew point: −40° C.) (Dew point: −30° C.) (Dew point: −50° C.) Container Chemical drum Chemical drum Chemical drum with high-density with high-density with high-density PE inner bag PE inner bag PE inner bag Compound A 98.6 98.5 99.4 content (% by mass) Compound B 542 1203 658 Content (×10.sup.−4 parts by mass) Yield (%) 88 82 80 Viscosity(mPa .Math. sec) 1.6 1.8 1.6 Appearance No change No change No change Example 10 11 12 Distillation 110 115 125 temperature(° C.) Distillation 2.5 3.0 4.5 pressure (kPa) Reflux ratio 2.5 2.0 4.0 Gas supplied in the Dried nitrogen Dried nitrogen Dried nitrogen vacuum breaking Dilution air Dilution air Dilution air step (Dew point: −30° C.) (Dew point: −40° C.) (Dew point: −40° C.) (Oxygen: 4 vol %) (Oxygen: 5 vol %) (Oxygen: 6 vol %) Gas filled in the Dried air Dried air Dried air filling step (Dew point: −40° C.) (Dew point: −50° C.) (Dew point: −60° C.) Container Chemical drum Chemical drum Chemical drum with high-density with high-density with high-density PE inner bag PE inner bag PE inner bag Compound A 98.2 99.2 99.6 content (% by mass) Compound B 897 1567 795 Content (×10.sup.−4 parts by mass) Yield (%) 86 84 72 Viscosity(mPa .Math. sec) 1.7 1.7 1.6 Appearance No change No change No change

TABLE-US-00004 TABLE 4 Comparative Example 9 10 11 12 Distillation 90 110 130 110 temperature(° C.) Distillation 1.5 2.5 6.5 2.5 pressure (kPa) Reflux ratio 1.0 0.2 1.5 0.5 Gas supplied in the Dried nitrogen Dried nitrogen Dried nitrogen Dried nitrogen vacuum breaking Dilution air Dilution air Dilution air Dilution air step (Dew point: −40° C.) (Dew point: −50° C.) (Dew point: −40° C.) (Dew point: −60° C.) (Oxygen: 3 vol %) (Oxygen: 4 vol %) (Oxygen: 6 vol %) (Oxygen: 5 vol %) Gas filled in the Dried air Dried air Dried air Dried air filling step (Dew point: −50° C.) (Dew point: −30° C.) (Dew point: −40° C.) (Dew point: −40° C.) Container Chemical drum Chemical drum Chemical drum Chemical drum with high-density with high-density with high-density with high-density PE inner bag PE inner bag PE inner bag PE inner bag Compound A 97.5 97 97.8 96.3 content (% by mass) Compound B 2680 3356 3865 2745 Content (×10.sup.−4 parts by mass) Yield (%) 91 90 81 88 Viscosity (mPa .Math. sec) Not measurable Not measurable Not measurable Not measurable Appearance Syrup-like Solid Syrup-like Solid Comparative Example 13 14 15 16 Distillation 130 110 115 125 temperature(° C.) Distillation 6.5 2.5 3.0 4.5 pressure (kPa) Reflux ratio 3.5 2.5 2.0 4.5 Gas supplied in the Dried nitrogen Dried nitrogen gas Dried nitrogen Dried nitrogen vacuum breaking (Dew point: −50° C.) (Dew point: −40° C.) Dilution air (Dew point: −50° C.) step (Dew point: −40° C.) (Oxygen: 4 vol %) Gas filled in the Dried nitrogen Dried air Dried nitrogen Dried nitrogen filling step (Dew point: −40° C.) (Dew point: −50° C.) (Dew point: −50° C.) (Dew point: −60° C.) Container Chemical drum Chemical drum Chemical drum Chemical drum with high-density with high-density with high-density with high-density PE inner bag PE inner bag PE inner bag PE inner bag Compound A 99.4 98.2 99.2 99.6 content (% by mass) Compound B 4557 3023 4754 5754 Content (×10.sup.−4 parts by mass) Yield (%) 80 86 84 72 Viscosity (mPa .Math. sec) Not measurable Not measurable Not measurable Not measurable Appearance Syrup-like Solid Syrup-like Solid

[0149] Next, regarding the compositions of Examples 1 to 12 and Comparative Examples 1 to 16, the compounds (A) and the compounds (B) in the compositions were determined quantitatively by the following method, and the contents (% by mass) of the compounds (A) in the compositions and the contents (×10.sup.−4 parts by mass) of the compounds (B) with respect to 100 parts by mass of the compounds (A) were determined. The results are shown in Tables 1 to 4.

[0150] <Quantification of Compound (A)>

[0151] The compositions were analyzed by gas chromatography (GC) under the following conditions.

[0152] Column: DB-1, Inlet Temperature: 300° C., Detection Temperature: 300° C.

[0153] Column temperature: 50° C. to 300° C. at 10° C/min

[0154] Column flow rate: 1.4 ml/min

[0155] Split ratio: 1/50

[0156] Detector: FID

[0157] <Quantification of compound (B)>

[0158] The composition was analyzed by liquid chromatography (LC) according to an internal standard method under the following conditions.

[0159] Column: Shodex (registered trademark) KF-801 (Product name: Manufactured by Showa Denko K.K.) x 4

[0160] Column temperature: 40° C.

[0161] Solvent: THF (tetrahydrofuran)

[0162] Flow rate: 0.8 ml/min

[0163] Detector: RI (differential refractometer)

[0164] The yields (distillation yield) of the compositions obtained from Mixtures 1 or Mixtures 2 of Examples 1 to 12 and Comparative Examples 1 to 16 were determined by the following formula. The results are shown in Tables 1 to 4.

Yield=(Composition Mass/Theoretical Yield of Compound A)×100 (%)

[0165] “Appearance Evaluation”

[0166] In Examples 1 to 12 and Comparative Examples 1 to 16, 100 g of the liquid compositions immediately after distillation were stored in a container in a sealed state at 25° C. for 30 days, and the appearance after storage was evaluated by the following method.

[0167] The container containing the composition was tilted several times at an angle of about 45 degrees and evaluated visually using the following criteria. The results are shown in Tables 1 to 4.

[0168] “Criteria”

[0169] No change: flowing in less than 30 seconds after tilting the container

[0170] Syrup-like: flowing down in 30 seconds or more and less than 180 seconds after tilting a container

[0171] Solid: not flowing in more than 180 seconds after tilting the container

[0172] “Method of Measuring Viscosity”

[0173] The viscosities of the compositions of Examples 1 to 12 and Comparative Examples 1 to 16 stored at 25° C. for 30 days in a sealed state were determined in accordance with JIS-Z 8803: 2011 by the following method. The results are shown in Tables 1 to 4.

[0174] The kinematic viscosity of each composition at 25° C. (cm.sup.3/sec) was measured using an Uberode viscometer. In Examples 1 to 6 and Comparative Examples 1 to 8, the measured kinematic viscosity was multiplied by the density of the following KarenzMOI (registered trademark) (manufactured by Showa Denko) to calculate the viscosity (mPa.Math.sec). In Examples 7 to 12 and Comparative Examples 9 to 16, the viscosity was calculated by multiplying the measured value of the kinematic viscosity by the density of the KarenzAOI (registered trademark) (manufactured by Showa Denko) shown below (mPa.Math.sec).

[0175] (Density of the KarenzMOI (registered trademark)) 1.096 g/cm.sup.3 (25° C.)

[0176] (Density of KarenzAOI (registered trademark)) 1.133 g/cm.sup.3 (25° C.)

[0177] As shown in Tables 1 to 4, the compositions of Examples 1 to 12, which contain 95.0 parts by mass of the compound (A) and which contain 0.00002 to 0.2 parts by mass of the compound (B) with respect to 100 parts by mass of the compound (A), had a sufficiently low viscosity after storage at 25° C. for 30 days, and the appearance evaluation were “No change”.

[0178] On the other hand, in the compositions of Comparative Examples 1 to 16, which contain more than 0.2 parts by mass of the compound (B) with respect to 100 parts by mass of the compound (A), the viscosity which became too high by storing at 25° C. for 30 days, and the viscosity could not be measured. In the composition of Comparative Examples 1 to 16, the appearance evaluation was “syrup-like” or “solid”.

[0179] (Unsaturated Compound)

Example 13

Reaction Product of (Poly)ol with MOI

[0180] In a 500 ml four-necked flask equipped with a stirrer, reflux condenser and thermometer, 165 g of polyethylene glycol (number-average molecular weight 660) and 77.5 g of the composition of Example 1 (The compound (A) is MOI.) were charged and reacted at 80° C. for 5 hours to synthesize an unsaturated urethane compound 1.

Comparative Example 17

Reaction Product of (Poly)ol with MOI

[0181] An unsaturated urethane compound 2 was synthesized in the same manner as in Example 13 except that the composition of Comparative Example 1 (The compound (A) is MOI.) was used in place of the composition of Example 1.

Comparative Example 18

Reaction Product of (Poly)ol with MOI

[0182] An unsaturated urethane compound 3 was synthesized in the same manner as in Example 13 except that the composition of Comparative Example 7 (The compound (A) is MOL) was used in place of the composition of Example 1.

Example 14

Reaction Product of (Poly)ol with AOI

[0183] In a 500 ml four-necked flask equipped with a stirrer, reflux condenser and thermometer, 165 g of polyethylene glycol (Number average molecular weight 660) and 70.5 g of the composition of Example 9 (The compound (A) is A01.) were charged and reacted at 80° C. for 5 hours to synthesize an unsaturated urethane compound 4.

Comparative Example 19

Reaction Product of (Poly)ol with AOI

[0184] An unsaturated urethane compound 5 was synthesized in the same manner as in Example 14 except that the composition of Comparative Example 12 (The compound (A) is AOI.) was used in place of the composition of Example 9.

Comparative Example 20

Reaction Product of (Poly)ol with AOI

[0185] An unsaturated urethane compound 6 was synthesized in the same manner as in Example 14 except that the composition of Comparative Example 16 (The compound (A) is AOL) was used in place of the composition of Example 9.

[0186] Viscosities of the reaction liquids containing the unsaturated urethane compounds 1 to 6, obtained in Examples 13 and 14 and Comparative Examples 17 to 20, were measured in accordance with JIS-Z 8803: 2011 at 25° C. using a tuning fork type vibrating viscometer (SV type viscometer manufactured by A & D Co., Ltd. (SV-10 Type)). The results are shown in Tables 5 and 6.

TABLE-US-00005 TABLE 5 Unsaturated Compound B Urethane Content (×10.sup.−4 Viscosity Compound Composition parts by mass) (mPa .Math. sec) Example 13 1 Example 1 540 0.16 Comparative 2 Comparative 2200 Gelation Example 17 Example 1 Comparative 3 Comparative 4847 Gelation Example 18 Example 7

TABLE-US-00006 TABLE 6 Unsaturated Compound B Urethane Content (×10.sup.−4 Viscosity Compound Composition parts by mass) (mPa .Math. sec) Example 14 4 Example 9 658 0.16 Comparative 5 Comparative 2745 Gelation Example 19 Example 12 Comparative 6 Comparative 6754 Gelation Example 20 Example 16

[0187] As shown in Table 5, in Example 13 in which the unsaturated urethane compounds were prepared by using the composition containing 95.0% by mass or more of the compound (A) and containing 0.00002 to 0.2 parts by mass of the compound (B) with respect to 100 parts by mass of the compound (A), the unsaturated urethane compound 1 having an appropriate viscosity was obtained, and the unsaturated urethane compound could be produced without problem.

[0188] On the other hand, in Comparative Examples 17 and 18 in which the unsaturated urethane compounds were prepared by using the composition containing more than 0.2 parts by mass of the compound (B) with respect to 100 parts by mass of the compound (A), the unsaturated urethane compounds 2 and 3 were gelatinized during the preparation of the unsaturated urethane compounds 2 and 3, although there was no problem in handling in the raw material stage.

[0189] As shown in Table 6, in Example 14 in which the unsaturated urethane compounds were prepared by using a composition containing 95.0% by mass or more of the compound (A) and containing 0.00002 to 0.2 parts by mass of the compound (B) with respect to 100 parts by mass of the compound (A), the unsaturated urethane compound 4 having an appropriate viscosity was obtained, and the unsaturated urethane compound could be produced without any problem.

[0190] On the other hand, in Comparative Examples 19 and 20 in which the unsaturated urethane compounds were prepared by using the composition containing more than 0.2 parts by mass of the compound (B) with respect to 100 parts by mass of the compound (A), the viscosity of the unsaturated urethane compounds 5 and 6 was high, and a part of them gelled during the preparation.

Example 15

Reaction Product of (Poly)amine with MOI

[0191] A 500 ml four-necked flask equipped with a stirrer, reflux condenser and thermometer was charged with 66.4 g of (2[(3,5-dimethylpyrazolyl)carbonylamino]ethyl methacrylate) (KarenzMOI-BP (registered trademark) manufactured by Showa Denko) and 77.4 g of 3,5-dimethylpyrazole, and 122.6 g of the composition of Example 2 (The compound (A) is MOI.) was supplied while the temperature was maintained at 35° C., and then reacted for 2 hours to synthesize an unsaturated urea compound 1.

Comparative Example 21

Reaction Product of (Poly)amine with MOI

[0192] An unsaturated urea compound 2 was synthesized in the same manner as in Example 15 except that the composition of Comparative Example 2 (The compound (A) is MOI.) was used in place of the composition of Example 2.

Comparative Example 22

Reaction Product of (Poly)amine with MOI

[0193] An unsaturated urea compound 3 was synthesized in the same manner as in Example 15 except that the composition of Comparative Example 5 (The compound (A) is MOI.) was used in place of the composition of Example 2.

Example 16

Reaction Product of (Poly)amine with AOI

[0194] In a 1000 ml four-necked flask equipped with a stirrer, reflux condenser and thermometer, 115.9 g of 3,5-dimethylpyrazole and 155.0 g of 2-acetoxy-1-methoxypropane were charged, 174.0 g of the composition of Example 8 (The compound (A) is AOI.) was fed while maintaining the temperature at 15° C., and then reacted for 30 minutes. Subsequently, 320.0 g of n-hexane was added and cooled to 0° C. to crystallize the unsaturated urea compound 4. The obtained crystals were recovered by filtration, washed with n-hexane, and dried under reduced pressure to isolate an unsaturated urea compound 4.

Comparative Example 23

Reaction Product of (Poly)amine with AOI

[0195] An unsaturated urea compound 5 was synthesized in the same manner as in Example 16 except that the composition of Comparative Example 10 (The compound (A) is AOI) was used in place of the composition of Example 8.

Comparative Example 24

Reaction Product of (Poly)amine with AOI

[0196] An unsaturated urea compound 6 was synthesized in the same manner as in Example 16 except that the composition of Comparative Example 15 (The compound (A) is AOI.) was used in place of the composition of Example 8.

[0197] Viscosities of the reaction liquids containing the unsaturated urea compounds 1 to 6 obtained in Examples 15 and 16 and Comparative Examples 21 to 24 (before addition of n-hexane) were measured in accordance with JIS-Z 8803: 2011 at 25° C. using a tuning fork type vibration type viscometer (SV type viscometer manufactured by A & D Co., Ltd. (SV-10 Type)). The results are shown in Tables 7 and 8.

TABLE-US-00007 TABLE 7 Unsaturated Compound B Urea Content (×10.sup.−4 Viscosity Compound Composition parts by mass) (mPa .Math. sec) Example 15 1 Example 2 150 0.18 Comparative 2 Comparative 2650 Gelation Example 21 Example 2 Comparative 3 Comparative 4650 Gelation Example 22 Example 5

TABLE-US-00008 TABLE 8 Unsaturated Compound B Urea Content (×10.sup.−4 Viscosity Compound Composition parts by mass) (mPa .Math. sec) Example 16 4 Example 8 1203 0.22 Comparative 5 Comparative 3356 Gelation Example 23 Example 10 Comparative 6 Comparative 4754 Gelation Example 24 Example 15

[0198] As shown in Table 7, in Example 15 in which unsaturated urea compounds were prepared by using the composition containing 95.0% by mass or more of the compound (A) and containing 0.00002 to 0.2 parts by mass of the compound (B) with respect to 100 parts by mass of the compound (A), the unsaturated urea compound 1 having an appropriate viscosity was obtained, and the unsaturated urea compound was successfully prepared.

[0199] On the other hand, in Comparative Examples 21 and 22 in which unsaturated urea compounds were prepared by using the composition containing more than 0.2 parts by mass of the compound (B) with respect to 100 parts by mass of the compound (A), the unsaturated urea compounds 2 and 3 were gelled during the preparation, although there was no problem in handling at the stage of raw material.

[0200] As shown in Table 8, in Example 16 in which unsaturated urea compounds were prepared by using a composition containing 95.0% by mass or more of the compound (A) and containing 0.00002 to 0.2 parts by mass of the compound (B) with respect to 100 parts by mass of the compound (A), the unsaturated urea compound 4 having a proper viscosity was obtained, and the unsaturated urea compound was successfully prepared.

[0201] On the other hand, in Comparative Examples 23 and 24 in which unsaturated urea compounds were prepared by using the composition containing more than 0.2 parts by mass of the compound (B) with respect to 100 parts by mass of the compound (A), the unsaturated urea compounds 5 and 6 were gelled during the preparation, although there was no problem in handling at the stage of raw material.

Example 17

Reaction Product of (Poly)carboxylic Acid with MOI

[0202] In a 500 ml four-necked flask equipped with a stirrer, reflux condenser and thermometer, 177.3 g of decanoic acid, 156.5 g of the composition of Example 3 (The compound (A) is MOI.) and 0.8 g of dibutyltin dilaurate were charged and reacted at 80° C. for 12 hours to synthesize an unsaturated amide compound 1.

Comparative Example 25

Reaction Product of (Poly)carboxylic Acid with MOI

[0203] An unsaturated amide compound 2 was synthesized in the same manner as in Example 17 except that the composition of Comparative Example 3 (The compound (A) is MOI.) was used in place of the composition of Example 3.

Comparative Example 26

Reaction Product of (Poly)carboxylic Acid with MOI

[0204] An unsaturated amide compound 3 was synthesized in the same manner as in Example 17 except that the composition of Comparative Example 8 (The compound (A) is MOI.) was used in place of the composition of Example 3.

Example 18

Reaction Product of (Poly)carboxylic Acid with AOI

[0205] In a 500 ml four-necked flask equipped with a stirrer, reflux condenser and thermometer, 177.3 g of decanoic acid, 142.4 g of the composition of Example 7 (The compound (A) is AOI.) and 0.8 g of dibutyltin dilaurate were charged and reacted at 80° C. for 12 hours to synthesize an unsaturated amide compound 4.

Comparative Example 27

Reaction Product of (Poly)carboxylic Acid with AOI

[0206] An unsaturated amide compound 5 was synthesized in the same manner as in Example 18 except that the composition of Comparative Example 11 (The compound (A) is AOI.) was used in place of the composition of Example 7.

Comparative Example 28

Reaction Product of (Poly)carboxylic Acid with AOI

[0207] An unsaturated amide compound 6 was synthesized in the same manner as in Example 18 except that the composition of Comparative Example 14 (The compound (A) is AOI.) was used in place of the composition of Example 7.

[0208] Viscosities of the reaction liquids containing the unsaturated amide compounds 1 to 6 obtained in Examples 17 and 18 and Comparative Example 25 to 28 were measured in accordance with JIS-Z 8803: 2011 at 25° C. using a tuning fork type vibrating viscometer (SV type viscometer manufactured by A & D Co., Ltd. (SV-10 Type)). The results are shown in Tables 9 and 10.

TABLE-US-00009 TABLE 9 Unsaturated Compound B Amide Content (×10.sup.−4 Viscosity Compound Composition parts by mass) (mPa .Math. sec) Example 17 1 Example 3 204 0.77 Comparative 2 Comparative 3302 Gelation Example 25 Example 3 Comparative 3 Comparative 6897 Gelation Example 26 Example 8

TABLE-US-00010 TABLE 10 Unsaturated Compound B Amide Content (×10.sup.−4 Viscosity Compound Composition parts by mass) (mPa .Math. sec) Example 18 4 Example 7 542 0.22 Comparative 5 Comparative 3865 Gelation Example 27 Example 1 Comparative 6 Comparative 3023 Gelation Example 28 Example 14

[0209] As shown in Table 9, in Example 17 in which unsaturated amide compounds were prepared by using the composition containing 95.0% by mass or more of the compound (A) and containing 0.00002 to 0.2 parts by mass of the compound (B) with respect to 100 parts by mass of the compound (A), the unsaturated amide compound 1 having a proper viscosity was obtained, and the unsaturated amide compound could be prepared without any problem.

[0210] On the other hand, in Comparative Examples 25 and 26 in which unsaturated amide compounds were prepared by using the composition containing more than 0.2 parts by mass of the compound (B) with respect to 100 parts by mass of the compound (A), although there was no problem in handling in the stage of raw material, they gelled during the preparation of the unsaturated amide compounds 2 and 3.

[0211] As shown in Table 10, in Example 18 in which unsaturated amide compounds were prepared by using the composition containing 95.0% by mass or more of the compound (A) and containing 0.00002 to 0.2 parts by mass of the compound (B) with respect to 100 parts by mass of the compound (A), the unsaturated amide compound 4 having a proper viscosity was obtained, and the unsaturated amide compound was successfully prepared.

[0212] On the other hand, in Comparative Examples 27 and 28 in which unsaturated amide compounds were prepared by using the composition containing more than 0.2 parts by mass of the compound (B) with respect to 100 parts by mass of the compound (A), although there was no problem in handling in the stage of raw material, they gelled during the preparation of the unsaturated amide compounds 5 and 6.

Example 19

Reaction Product of (Poly)thiol with MOI

[0213] In a 500 ml four-necked flask equipped with a stirrer, reflux condenser and thermometer, 177.3 g of 1-octanethiol and 184.3 g of the composition of Example 4 (The compound (A) is MOI.) were charged and reacted at 80° C. for 24 hours to synthesize an unsaturated thiourethane compound 1.

Comparative Example 29

Reaction Product of (Poly)thiol with MOI

[0214] An unsaturated thiourethane compound 2 was synthesized in the same manner as in Example 19 except that the composition of Comparative Example 4 (The compound (A) is MOI.) was used in place of the composition of Example 4.

Comparative Example 30

Reaction of (Poly)thiol with MOI

[0215] An unsaturated thiourethane compound 3 was synthesized in the same manner as in Example 19 except that the composition of Comparative Example 6 (The compound (A) is MOI.) was used in place of the composition of Example 4.

Example 20

Reaction Product of (Poly)thiol with AOI

[0216] In a 500 ml four-necked flask equipped with a stirrer, reflux condenser and thermometer, 177.3 g of 1-octanethiol and 167.7 g of the composition of Example 12 (The compound (A) is AOI.) were charged and reacted at 80° C. for 24 hours to synthesize an unsaturated thiourethane compound 4.

Comparative Example 31

Reaction Product of (Poly)thiol with AOI

[0217] An unsaturated thiourethane compound 5 was synthesized in the same manner as

[0218] Example 20 except that the composition of Comparative Example 9 (The compound (A) is AOI.) was used in place of the composition of Example 12.

Comparative Example 32

Reaction Product of (Poly)thiol with AOI

[0219] An unsaturated thiourethane compound 6 was synthesized in the same manner as in Example 20 except that the composition of Comparative Example 13 (The compound (A) is AOL) was used in place of the composition of Example 12.

[0220] Viscosities of the reaction liquids containing the unsaturated thiourethane compounds 1 to 6 obtained in Examples 19 and 20 and Comparative Examples 29 to 32 were measured in accordance with JIS-Z 8803: 2011 at 25° C. using a tuning fork type vibrating viscometer (SV type viscometer manufactured by A & D Co., Ltd. (SV-10 Type)). The results are shown in Tables 11 and 12.

TABLE-US-00011 TABLE 11 Unsaturated Compound B Thiourethane Content (×10.sup.−4 Viscosity Compound Composition parts by mass) (mPa .Math. sec) Example 19 1 Example 4 560 0.87 Comparative 2 Comparative 2813 Gelation Example 29 Example 4 Comparative 3 Comparative 3362 Gelation Example 30 Example 6

TABLE-US-00012 TABLE 12 Compound B Unsaturated Content Thiourethane (×lO−4.) Viscosity Compound Composition Weight Part (mPa .Math. sec) Example 20 4 Example 12 795 0.54 Comparative 5 Comparative 2680 Gelation Example 31 Example 9 Comparative 6 Comparative 4557 Gelation Example 32 Example 13

[0221] As shown in Table 11, in Example 19 in which unsaturated thiourethane compound was prepared by using the composition containing 95.0% by mass or more of the compound (A) and containing 0.00002 to 0.2 parts by mass of the compound (B) with respect to 100 parts by mass of the compound (A), the unsaturated thiourethane compound 1 having an appropriate viscosity was obtained, and the unsaturated thiourethane compound was successfully prepared.

[0222] On the other hand, in Comparative Examples 29 and 30 in which unsaturated thiourethane compounds were prepared by using the compositions containing more than 0.2 parts by mass of the compound (B) with respect to 100 parts by mass of the compound (A), although there was no problem in handling in the stage of raw material, the compound was gelled during the preparation of the unsaturated thiourethane compounds 2 and 3.

[0223] As shown in Table 12, in Example 20 in which unsaturated thiourethane compound was prepared by using the composition containing 95.0% by mass or more of the compound (A) and containing 0.00002 to 0.2 parts by mass of the compound (B) with respect to 100 parts by mass of the compound (A), the unsaturated thiourethane compound 4 having an appropriate viscosity was obtained, and the unsaturated thiourethane compound was successfully prepared.

[0224] On the other hand, in Comparative Examples 31 and 32 in which unsaturated thiourethane compounds were prepared by using the compositions containing more than 0.2 parts by mass of the compound (B) with respect to 100 parts by mass of the compound (A), the unsaturated thiourethane compounds 5 and 6 were gelatinized during the preparation of the unsaturated thiourethane compounds 5 and 6, although there was no problem in handling in the raw material stage.

21 Example 21

Reaction Product of Oxime Compound with MOI

[0225] In a 500 ml four-necked flask equipped with a stirrer, reflux condenser and thermometer, 167.0 g of 2-butanone oxime (hereinafter also referred to as “MEK oxime”) was charged, and while the temperature was maintained at 35° C., 293.1 g of the composition of Example 6 (The compound (A) is MOI.) was fed and allowed to react for 2 hours to synthesize MOI-BM (2-butanone oxime-O-(carbamoylethyl-2-methacrylate) as unsaturated butanone oxime compound 1. MOI-BM is a mixture of (2-butanone oxime-O-(E)-(carbamoylethyl-2-methacrylate) and 2-butanone oxime-O-(Z)-(carbamoylethyl-2-methacrylate).

Comparative Example 33

Reaction Product of Oxime Compound with MOI

[0226] An unsaturated butanone oxime compound 2 was synthesized in the same manner as in Example 21 except that the composition of Comparative Example 3 (The compound (A) is MOI.) was used in place of the composition of Example 6.

Comparative Example 34

Reaction Product of Oxime Compound with MOI

[0227] An unsaturated butanone oxime compound 3 was synthesized in the same manner as in Example 21 except that the composition of Comparative Example 7 (The compound (A) is MOI.) was used in place of the composition of Example 6.

Example 22

Reaction Product of Oxime Compound with AOI

[0228] To a 500 ml four-necked flask equipped with a stirrer, reflux condenser and thermometer, at 15° C., 167.0 g of 2-butanone oxime (MEK oxime) and 266.7 g of the composition of Example 10 (The compound (A) is AOI.) were fed at the same time and reacted for 1 hour to synthesize AOI-BM (2-butanone oxime-O-(carbamoylethyl-2-acrylate) as an unsaturated butanone oxime compound 4. AOI-BM is a mixture of 2-butanone oxime-O-(E)-(Carbamoylethyl-2-acrylate) and 2-butanone oxime-O-(Z)-(carbamoylethyl-2-acrylate).

Comparative Example 35

Reaction Product of Oxime Compound with AOI

[0229] An unsaturated butanone oxime compound 5 was synthesized in the same manner as in Example 22 except that the composition of Comparative Example 11 (The compound (A) is AOI.) was used in place of the composition of Example 10.

Comparative Example 36

Reaction Product of Oxime Compound with AOI

[0230] An unsaturated butanone oxime compound 6 was synthesized in the same manner as in Example 22 except that composition of Comparative Example 15 (The compound (A) is AOI.) was used in place of the composition of Example 10.

[0231] The viscosities of the reaction liquids containing the unsaturated butanone oxime compounds 1 to 6, obtained in Examples 21 and 22 and Comparative Examples 33 to 36, were measured in accordance with JIS-Z 8803: 2011 at 25° C. using a tuning-fork-type vibrating viscometer (SV type viscometer manufactured by A & D Co., Ltd. (SV-10 Type)). The results are shown in Tables 13 and 14.

TABLE-US-00013 TABLE 13 Unsaturated Butanone Compound B Oxime Content (×10.sup.−4 Viscosity Compound Composition parts by mass) (mPa .Math. sec) Example 21 1 Example 6 450 0.15 Comparative 2 Comparative 3302 Gelation Example 33 Example 3 Comparative 3 Comparative 4870 Gelation Example 34 Example 7

TABLE-US-00014 TABLE 14 Unsaturated Butanone Compound B Oxime Content (×10.sup.−4 Viscosity Compound Composition parts by mass) (mPa .Math. sec) Example 22 4 Example 10 897 0.22 Comparative 5 Comparative 3865 Gelation Example 35 Example 11 Comparative 6 Comparative 4754 Gelation Example 36 Example 15

[0232] As shown in Table 13, in Example 21, in which unsaturated butanone oxime compounds were prepared by using compositions which contain 95.0 parts by mass of the compound (A) and which contain 0.00002 to 2.0 parts by mass of the compound (B) with respect to 100 parts by mass of the compound (A), the unsaturated butanone oxime compound 1 having proper viscosity were obtained, and the unsaturated butanone oxime compounds were successfully prepared.

[0233] On the other hand, in Comparative Examples 33 and 34 in which an unsaturated butanone oxime compound was prepared by using a composition which contains more than 0.2 parts by mass of the compound (B) with respect to 100 parts by mass of the compound (A), although there was no problem in handling in the stage of raw material, the compound gelled during the preparation of the unsaturated butanone oxime compounds 2 and 3.

[0234] As shown in Table 14, in Example 22, in which unsaturated butanone oxime compounds were prepared by using compositions which contain 95.0 parts by mass of the compound (A) and which contain 0.00002 to 0.2 parts by mass of the compound (B) with respect to 100 parts by mass of the compound (A), the unsaturated butanone oxime compound 4 having the proper viscosity were obtained, and the unsaturated butanone oxime compounds were successfully prepared.

[0235] On the other hand, in Comparative Examples 35 and 36, in which an unsaturated butanone oxime compound was prepared by using a composition which contains more than 0.2 parts by mass of the compound (B) with respect to 100 parts by mass of the compound (A), although there was no problem in handling in the stage of raw material, the compound gelled during the preparation of the unsaturated butanone oxime compounds 5 and 6.

[0236] As shown in the above results, depending on whether or not the content of the compound (B) with respect to 100 parts by mass of the compound (A) was 0.00002 to 0.2 parts by mass, there was a large difference in the behavior of the composition during storage. The viscosity of the unsaturated compound obtained by reacting the composition with any one of (poly)ol, (poly)amine, (poly)carboxylic acid, (poly)thiol and oxime compound also differed greatly depending on whether or not the content of the compound (B) with respect to 100 parts by mass of the compound (A) in the composition was 0.00002 to 0.2 parts by mass.

[0237] From these results, it was confirmed that the concentration of compound (B) in the composition is useful as an index for determining the stability of the composition during storage and as an index for determining whether or not a rapid increase in viscosity and/or gelation occurs during production when the unsaturated compound is produced by using the composition as a raw material.