Compound and production method of the same, composition, urethane resin, aqueous urethane resin dispersion, and coating agent

Abstract

To provide a novel compound useful as a raw material for a urethane resin and the like.SOLUTION: Provided is a compound represented by the following formula (A1-1). In formula (A1-1), R1 is a hydrogen atom, an alkyl group, or a hydroxyalkyl group, R2 is an alkanediyl group, R3 is an alkanediyl group, or *1-Ra-C(=O)-O-Rb-*2, R4 is an alkanediyl group, *1-O-Rc-*2, or *1-Ra-C(=O)-O-Rb-*2, Ra, Rb, and Rc are each independently an alkanediyl group, *1 is a binding site to a carbonyl group, *2 is a binding site to an oxygen atom, and n1 and m1 are each an integer of 0 or more. When there are multiple R4s, they may be the same or different.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a compound and a method for producing the same, a composition, a urethane resin, an aqueous urethane resin dispersion, and a coating agent. [Background technology]

[0002] Like polyester polyols, polyether polyols, and the like, polycarbonate polyols are useful as raw materials for producing urethane resins (also called polyurethane resins) by reacting them with polyisocyanate compounds, and are useful as raw materials for adhesives, paints, and the like.

[0003] Since polyester polyol has an ester bond, the urethane resin obtained from the polyester polyol has a disadvantage of being poor in hydrolysis resistance. Also, since polyether polyol has an ether bond, the urethane resin obtained from the polyether polyol has a disadvantage of being poor in weather resistance and heat resistance. In contrast, the urethane resin obtained from the polycarbonate polyol tends to be excellent in durability (heat resistance, weather resistance, hydrolysis resistance, chemical resistance, etc.).

[0004] Polycarbonate polyols are usually produced by reacting a carbonate ester with a diol in the presence of a transesterification catalyst (transesterification reaction).

[0005] To date, polycarbonate polyols having various structures have been proposed depending on the purpose. For example, Patent Documents 1 and 2 propose polycarbonate polyols obtained by transesterification of a polycarbonate diol with a triol compound and / or a tetraol compound. [Prior art documents] [Patent documents]

[0006] [Patent Document 1] Japanese Patent Application Publication No. 3-220233 [Patent Document 2] JP 2012-184380 A Summary of the Invention [Problem to be solved by the invention]

[0007] An object of the present invention is to provide a novel compound useful as a raw material for urethane resins and the like, a method for producing the compound, and a urethane resin made from the compound. Another object of the present invention is to provide a composition containing the compound, and a urethane resin made from the composition. Another object of the present invention is to provide an aqueous urethane resin dispersion containing the urethane resin having an acidic group. [Means for solving the problem]

[0008] The present invention provides the following inventions.

[0009] [1] A compound represented by the following formula (A1-1): [ka] [In formula (A1-1), R 1 represents a hydrogen atom, an alkyl group, or a hydroxyalkyl group; R 2 represents an alkanediyl group, and R 3 is an alkanediyl group, or *1-R a -C(=O)-OR b -*2, R 4 is an alkanediyl group, *1-OR c -*2 or *1-R a -C(=O)-OR b -*2, R a , R b , and R c each independently represents an alkanediyl group, *1 represents the bonding site with the carbonyl group, *2 represents the bonding site with the oxygen atom, and n 1 and m 1 Each represents an integer of 0 or more. 4When there are a plurality of, they may be the same or different. [2] A composition comprising the compound according to [1], a polycarbonate polyol represented by the following formula (A1-2), and a polyester polyol represented by the following formula (A1-3), wherein the total number of moles of the group represented by the following formula (a1-1) contained in the composition is C A1-1 The total number of moles of the group represented by the following formula (a1-2) contained in the composition is C A1-2 The total number of moles of the group represented by the following formula (a1-3) contained in the composition is represented by C A1-3 Then, the molar ratio (C A1-1 / (C A1-1 +C A1-2 +C A1-3 ) × 100) is 5.3 to 99. [ka] [In formula (A1-2), R 1 , R 2 and R 4 is as defined above, and n 2 and m 2 Each represents an integer greater than or equal to 0. 2 may be the same or different, R 4 When there are a plurality of, they may be the same or different. [ka] [In formula (A1-3), R 1 , R 3 and R 4 is as defined above, and n 3 and m 3 Each represents an integer greater than or equal to 0. 3 may be the same or different, R 4 When there are a plurality of, they may be the same or different. [ka] [In formula (a1-1), R 1has the same meaning as above, and * indicates a bond. [ka] [In formula (a1-2), R 1 has the same meaning as above, and * indicates a bond. [ka] [In formula (a1-3), R 1 has the same meaning as above, and * indicates a bond. [3] A composition further comprising a polycarbonate polyol represented by the following formula (A2-2) and a polyester polyol represented by the following formula (A2-3), wherein the total number of moles of the group represented by the following formula (a1-1) contained in the composition is C A1-1 The total number of moles of the group represented by the following formula (a1-2) contained in the composition is C A1-2 The total number of moles of the group represented by the following formula (a1-3) contained in the composition is represented by C A1-3 The total number of moles of the group represented by the following formula (a2-2) contained in the composition is C A2-2 The total number of moles of the group represented by the following formula (a2-3) contained in the composition is C A2-3 Then, the molar ratio ((C A2-2 +C A2-3 ) / (C A1-1 +C A1-2 +C A1-3 )) is 0.01 to 0.750. [ka] [In formula (A2-2), R 1 , R 2 and R 4 is as defined above, and n 4 R indicates an integer equal to or greater than 0. 4 When there are a plurality of, they may be the same or different. [ka] [In formula (A2-3), R 1 , R 3 and R 4 is as defined above, and n 5 R indicates an integer equal to or greater than 0. 4 When there are a plurality of, they may be the same or different. [ka] [In formula (a1-1), R 1 has the same meaning as above, and * indicates a bond. [ka] [In formula (a1-2), R 1 has the same meaning as above, and * indicates a bond. [ka] [In formula (a1-3), R 1 has the same meaning as above, and * indicates a bond. [ka] [In formula (a2-2), R 1 has the same meaning as above, and * indicates a bond. [ka] [In formula (a2-3), R 1 has the same meaning as above, and * indicates a bond. [4] The composition according to [2] or [3], further comprising a polycarbonate polyol represented by the following formula (A-3) and a polycarbonate diol represented by the following formula (A-4). [ka] [In formula (A-3), R 1 and R 4 is as defined above, and n 5 , m5 and p 5 Each R represents an integer of 1 or more. 4 may be the same or different.] [ka] [In formula (A-4), R 4 is as defined above, and n 6 indicates an integer of 1 or more. 4 may be the same or different.] [5] The total number of moles of the group represented by the following formula (a1-1) contained in the composition is C A1-1 The total number of moles of the group represented by the following formula (I) contained in the composition is C T Then, the molar ratio (C A1-1 / C T The composition according to any one of [2] to [4], wherein the ratio of the molecular weight of the polymer to the total molecular weight of the surface active agent is 0.02 to 0.99. [ka] [In formula (a1-1), R 1 has the same meaning as above, and * indicates a bond. [ka] [In formula (I), R 1 has the same meaning as above, and * indicates a bond. [6] The total number of moles of the group represented by the following formula (a1-2) contained in the composition is C A1-2 The total number of moles of the group represented by the following formula (I) contained in the composition is C T Then, the molar ratio (C A1-2 / C T The composition according to any one of [2] to [5], wherein the ratio of the molecular weight of the polymer to the total molecular weight of the solid is 0.001 to 0.99. [ka] [In formula (a1-2), R 1 has the same meaning as above, and * indicates a bond. [ka] [In formula (I), R 1 has the same meaning as above, and * indicates a bond. [7] The total number of moles of the group represented by the following formula (a1-3) contained in the composition is C A1-3 The total number of moles of the group represented by the following formula (I) contained in the composition is C T Then, the molar ratio (C A1-3 / C T The composition according to any one of [2] to [6], wherein the ratio of the molecular weight of the polymer to the molecular weight of the solid is 0.005 to 0.34. [ka] [In formula (a1-3), R 1 has the same meaning as above, and * indicates a bond. [ka] [In formula (I), R 1 has the same meaning as above, and * indicates a bond. [8] The total number of moles of the group represented by the following formula (a2-3) contained in the composition is C A2-3 The total number of moles of the group represented by the following formula (I) contained in the composition is C T Then, the molar ratio (C A2-3 / C T ) is 0.001 to 0.234. [ka] [In formula (a2-3), R 1 has the same meaning as above, and * indicates a bond. [ka] [In formula (I), R 1 has the same meaning as above, and * indicates a bond. [9] The total number of moles of the group represented by the following formula (d) contained in the composition is C D The total number of moles of the group represented by the following formula (a2-2) contained in the composition is C A2-2 The total number of moles of the group represented by the following formula (a2-3) contained in the composition is C A2-3 Then, the molar ratio (C A2-3 / (C A2-2 +C A2-3 +C D ) × 100) is 0.010 to 10.20. [ka] [In formula (d), R is a hydrogen atom or an alkanediyl group, and * indicates a bond. R may be the same or different.] [ka] [In formula (a2-2), R 1 has the same meaning as above, and * indicates a bond. [ka] [In formula (a2-3), R 1 has the same meaning as above, and * indicates a bond.

[10] The total number of moles of the group represented by the following formula (d) contained in the composition is C D The total number of moles of the group represented by the following formula (a2-2) contained in the composition is C A2-2 The total number of moles of the group represented by the following formula (a2-3) contained in the composition is C A2-3 Then, the molar ratio ((C A2-2 +C A2-3 ) / (C A2-2 +C A2-3 +C D ) × 100) is 0.100 to 12.00. [ka] [In formula (d), R is a hydrogen atom or an alkanediyl group, and * indicates a bond. R may be the same or different.] [ka] [In formula (a2-2), R 1 has the same meaning as above, and * indicates a bond. [ka] [In formula (a2-3), R 1 has the same meaning as above, and * indicates a bond.

[11] The total number of moles of the group represented by the following formula (f') contained in the composition is C F The total number of moles of the group represented by the following formula (I) contained in the composition is C T Then, the molar ratio (C F / C T × 100) is 1.70 to 45.0. [ka] [In formula (f'), R 1 has the same meaning as above, and * indicates a bond. [ka] [In formula (I), R 1 has the same meaning as above, and * indicates a bond.

[12] R 3 is an alkanediyl group, and the R 4 is an alkanediyl group, or *1-OR c -*2. The composition according to any one of [2] to

[11] .

[13] The composition according to any one of [2] to

[12] , which is a reaction product of a polycarbonate polyol (B) and a polyester polyol (C), wherein the polyester polyol (C) contains a polyester polyol (β) which is a ring-opening addition polymer of a cyclic ester compound using a diol as an initiator, and / or a polyester polyol (β') which is a ring-opening addition polymer of a cyclic ester compound using a polyhydric alcohol having three or more hydroxyl functional groups as an initiator.

[14] A method for producing the compound according to [1], comprising a reaction step of obtaining the compound by reacting a polycarbonate polyol with a polyester polyol in a mixed solution containing a polycarbonate polyol, a polyester polyol, and a transesterification catalyst, wherein at least one of the polycarbonate polyol and the polyester polyol contains a group represented by the following formula (I), or the mixed solution further contains a polyhydric alcohol represented by the following formula (e): [ka] [In formula (I), R 1 has the same meaning as above, and * indicates a bond. [ka] [In formula (e), R 1 has the same meaning as above.]

[15] The production method according to

[14] , wherein the content of the transesterification catalyst in the mixed solution is 0.001 to 0.050 parts by mass per 100 parts by mass of the total amount of the polyol components in the mixed solution.

[16] The method according to

[14] or

[15] , wherein the transesterification catalyst contains lithium acetylacetonate.

[17] A urethane resin which is a polycondensate of a polyol component and a polyisocyanate component or a crosslinked product thereof, wherein the polyol component contains the compound described in [1].

[18] The polyol component contains a polycarbonate polyol represented by the following formula (A1-2) and a polyester polyol represented by the following formula (A1-3), and the total number of moles of the group represented by the following formula (a1-1) contained in the polyol component is C A1-1 The total number of moles of the group represented by the following formula (a1-2) contained in the polyol component is represented by C A1-2 The total number of moles of the group represented by the following formula (a1-3) contained in the polyol component is represented by C A1-3 Then, the molar ratio (C A1-1 / (C A1-1 +C A1-2 +C A1-3 ) × 100) is 5.3 to 99. [ka] [In formula (A1-2), R 1 , R 2 and R 4 is as defined above, and n 2 and m 2 Each represents an integer greater than or equal to 0. 2 may be the same or different, R 4 When there are a plurality of, they may be the same or different. [ka] [In formula (A1-3), R 1 , R 3 and R 4 is as defined above, and n 3 and m 3 Each represents an integer greater than or equal to 0. 3 may be the same or different, R 4 When there are a plurality of, they may be the same or different. [ka] [In formula (a1-1), R 1 has the same meaning as above, and * indicates a bond. [ka] [In formula (a1-2), R 1 has the same meaning as above, and * indicates a bond. [ka] [In formula (a1-3), R 1 has the same meaning as above, and * indicates a bond.

[19] The polyol component further contains a polycarbonate polyol represented by the following formula (A2-2) and a polyester polyol represented by the following formula (A2-3), and the total number of moles of the group represented by the following formula (a1-1) contained in the polyol component is C A1-1 The total number of moles of the group represented by the following formula (a1-2) contained in the polyol component is represented by C A1-2 The total number of moles of the group represented by the following formula (a1-3) contained in the polyol component is represented by C A1-3 The total number of moles of the group represented by the following formula (a2-2) contained in the polyol component is represented by C A2-2 The total number of moles of the group represented by the following formula (a2-3) contained in the polyol component is represented by C A2-3 Then, the molar ratio ((C A2-2 +C A2-3 ) / (C A1-1 +C A1-2 +C A1-3 )) is 0.01 to 0.750. [ka] [In formula (A2-2), R 1 , R 2 and R 4 is as defined above, and n 4 R indicates an integer equal to or greater than 0. 4 When there are a plurality of, they may be the same or different. [ka] [In formula (A2-3), R 1 , R 3 and R 4 is as defined above, and n 5 R indicates an integer equal to or greater than 0. 4 When there are a plurality of, they may be the same or different. [ka] [In formula (a1-1), R 1 has the same meaning as above, and * indicates a bond. [ka] [In formula (a1-2), R 1 has the same meaning as above, and * indicates a bond. [ka] [In formula (a1-3), R 1 has the same meaning as above, and * indicates a bond. [ka] [In formula (a2-2), R 1 has the same meaning as above, and * indicates a bond. [ka] [In formula (a2-3), R 1 has the same meaning as above, and * indicates a bond.

[20] The urethane resin according to any one of

[17] to

[19] , wherein the polyol component further contains a polycarbonate polyol represented by the following formula (A-3) and a polycarbonate diol represented by the following formula (A-4). [ka] [In formula (A-3), R 1 and R4 is as defined above, and n 5 , m 5 and p 5 Each R represents an integer of 1 or more. 4 may be the same or different.] [ka] [In formula (A-4), R 4 is as defined above, and n 6 indicates an integer of 1 or more. 4 may be the same or different.]

[21] The total number of moles of the group represented by the following formula (a1-1) contained in the polyol component is C A1-1 The total number of moles of the group represented by the following formula (I) contained in the polyol component is C T Then, the molar ratio (C A1-1 / C T ) is 0.02 to 0.99. [ka] [In formula (a1-1), R 1 has the same meaning as above, and * indicates a bond. [ka] [In formula (I), R 1 has the same meaning as above, and * indicates a bond.

[22] The total number of moles of the group represented by the following formula (a1-2) contained in the polyol component is C A1-2 The total number of moles of the group represented by the following formula (I) contained in the polyol component is C T Then, the molar ratio (C A1-2 / C T ) is 0.001 to 0.99. [ka] [In formula (a1-2), R 1 has the same meaning as above, and * indicates a bond. [ka] [In formula (I), R 1 has the same meaning as above, and * indicates a bond.

[23] The total number of moles of the group represented by the following formula (a1-3) contained in the polyol component is C A1-3 The total number of moles of the group represented by the following formula (I) contained in the polyol component is C T Then, the molar ratio (C A1-3 / C T ) is 0.005 to 0.340. [ka] [In formula (a1-3), R 1 has the same meaning as above, and * indicates a bond. [ka] [In formula (I), R 1 has the same meaning as above, and * indicates a bond.

[24] The total number of moles of the group represented by the following formula (a2-3) contained in the polyol component is C A2-3 The total number of moles of the group represented by the following formula (I) contained in the polyol component is C T Then, the molar ratio (C A2-3 / C T ) is 0.001 to 0.234. [ka] [In formula (a2-3), R 1 has the same meaning as above, and * indicates a bond. [ka] [In formula (I), R 1 has the same meaning as above, and * indicates a bond.

[25] The total number of moles of the group represented by the following formula (d) contained in the polyol component is C D The total number of moles of the group represented by the following formula (a2-2) contained in the polyol component is represented by C A2-2 The total number of moles of the group represented by the following formula (a2-3) contained in the polyol component is represented by C A2-3 Then, the molar ratio (C A2-3 / (C A2-2 +C A2-3 +C D ) × 100) is 0.010 to 10.20. [ka] [In formula (d), R is a hydrogen atom or an alkanediyl group, and * indicates a bond. R may be the same or different.] [ka] [In formula (a2-2), R 1 has the same meaning as above, and * indicates a bond. [ka] [In formula (a2-3), R 1 has the same meaning as above, and * indicates a bond.

[26] The total number of moles of the group represented by the following formula (d) contained in the polyol component is C D The total number of moles of the group represented by the following formula (a2-2) contained in the polyol component is represented by C A2-2 In this case, the total number of moles of the group represented by the following formula (a2-3) contained in the polyol component is C A2-3 Then, the molar ratio ((C A2-2 +C A2-3 ) / (C A2-2 +C A2-3 +C D) × 100) is 0.100 to 12.00. [ka] [In formula (d), R is a hydrogen atom or an alkanediyl group, and * indicates a bond. R may be the same or different.] [ka] [In formula (a2-2), R 1 has the same meaning as above, and * indicates a bond. [ka] [In formula (a2-3), R 1 has the same meaning as above, and * indicates a bond.

[27] The total number of moles of the group represented by the following formula (f') contained in the polyol component is C F The total number of moles of the group represented by the following formula (I) contained in the polyol component is C T Then, the molar ratio (C F / C T × 100) is 1.70 to 45.0. [ka] [In formula (f'), R 1 has the same meaning as above, and * indicates a bond. [ka] [In formula (I), R 1 has the same meaning as above, and * indicates a bond.

[28] R 3 is an alkanediyl group, and the R 4 is an alkanediyl group, or *1-OR c -*2. The urethane resin according to any one of

[17] to

[28] .

[29] The urethane resin according to any one of

[17] to

[29] , wherein the polyol component is a reaction product of a polycarbonate polyol (B) and a polyester polyol (C), and the polyester polyol (C) contains a polyester polyol (β) which is a ring-opening addition polymer of a cyclic ester compound using a diol as an initiator, and / or a polyester polyol (β') which is a ring-opening addition polymer of a cyclic ester compound using a polyhydric alcohol having three or more hydroxyl functional groups as an initiator.

[30] The urethane resin according to any one of

[17] to

[29] , wherein the polyol component further contains a polyol having an acidic group.

[31] An aqueous urethane resin dispersion comprising an aqueous medium and the urethane resin or neutralized product thereof according to

[30] dispersed in the aqueous medium.

[32] A coating agent comprising the urethane resin according to any one of

[17] to

[30] . Effect of the Invention

[0010] According to the present invention, it is possible to provide a novel compound useful as a raw material for urethane resins and the like, a method for producing the compound, and a urethane resin made from the compound. According to the present invention, it is also possible to provide a composition containing the compound, and a urethane resin made from the composition. According to the present invention, it is also possible to provide an aqueous urethane resin dispersion containing the urethane resin having an acidic group. [Brief description of the drawings]

[0011] [Figure 1] FIG. 1 is a diagram showing a 1H-NMR spectrum of the composition containing the polycarbonate polyol obtained in Example 5. [Diagram 2] FIG. 2 is a 1H-NMR spectrum of the composition containing the polycarbonate polyol obtained in Example 5, showing an enlarged view of the range from 3.300 ppm to 3.800 ppm. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0012] Hereinafter, the embodiments of the present invention will be described in detail. In this specification, a numerical range indicated with "~" indicates a range including the numerical values ​​before and after "~" as the minimum and maximum values, respectively. The minimum or maximum value of a numerical range indicated with "~" can be arbitrarily combined with the maximum or minimum value of another numerical range indicated with "~". In addition, the upper and lower limit values ​​individually indicated can also be arbitrarily combined.

[0013] <Compound (A1-1)> The compound of this embodiment is a compound represented by the following formula (A1-1) (hereinafter also referred to as "compound (A1-1)"). [ka] [In formula (A1-1), R 1 represents a hydrogen atom, an alkyl group, or a hydroxyalkyl group; R 2 represents an alkanediyl group, and R 3 is an alkanediyl group, or *1-R a -C(=O)-OR b -*2, R 4 is an alkanediyl group, *1-OR c -*2 or *1-R a -C(=O)-OR b -*2, R a , R b , and R c each independently represents an alkanediyl group, *1 represents the bonding site with the carbonyl group, *2 represents the bonding site with the oxygen atom, and n 1 and m 1 Each represents an integer of 0 or more. 4 When there are a plurality of, they may be the same or different.

[0014] R 1The alkyl group and hydroxyalkyl group represented by the formula (I) may be linear or branched. The number of carbon atoms in the alkyl group and hydroxyalkyl group may be, for example, 1 to 6, 2 to 5, or 3 to 4. Specific examples of the alkyl group and hydroxyalkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a pentyl group, a hexyl group, a hydroxymethyl group, a hydroxyethyl group, a hydroxypropyl group, and a hydroxybutyl group. R 1 is preferably an alkyl group or a hydroxyalkyl group, and more preferably an alkyl group or a hydroxyalkyl group having 1 to 2 carbon atoms.

[0015] R 2 and R 3 The alkanediyl group represented by the formula R may be linear or branched. 2 and an alkanediyl group represented by R 3 may be the same as or different from the alkanediyl group represented by the following formula:

[0016] R 2 and R 3 The number of carbon atoms of the alkanediyl group represented by the formula (I) may be, for example, 2 to 10. Specific examples of the alkanediyl group include an ethanediyl group, a 1,2-propanediyl group, a 1,3-propanediyl group, a 1,2-butanediyl group, a 1,3-butanediyl group, a 1,4-butanediyl group, a 1,5-pentanediyl group, a 2,2-dimethyl-1,3-propanediyl group, a 1,6-hexanediyl group, a 3-methyl-1,5-pentanediyl group, a 1,8-octanediyl group, a 2-ethyl-1,6-hexanediyl group, a 1,9-nonanediyl group, a 2-methyloctane-1,8-diyl group, and a 2-butyl-2-ethyl-1,3-propanediyl group.

[0017] R 4 The alkanediyl group represented by the formula R may be linear or branched. 4When two or more types of alkanediyl groups represented by the following formula are present, all of them may be linear alkanediyl groups or branched alkanediyl groups, or some of them may be linear alkanediyl groups and the other part may be branched alkanediyl groups.

[0018] R 4 The number of carbon atoms in the alkanediyl group represented by R 2 and R 3 Among these, a 1,4-butanediyl group, a 1,5-pentanediyl group, a 1,6-hexanediyl group, a 3-methyl-1,5-pentanediyl group, a 2-ethyl-1,6-hexanediyl group, a 1,9-nonanediyl group, a 2-methyloctane-1,8-diyl group, and the like are preferred.

[0019] R a , R b , and R c The alkanediyl group represented by R may be the same as the alkanediyl group described above. a , R b , and R c The number of carbon atoms of the alkanediyl group represented by R may be, for example, 2 to 10. a When two or more types of alkanediyl groups represented by the formula (I) are present, all of them may be linear alkanediyl groups or branched alkanediyl groups, or some of them may be linear alkanediyl groups and the other may be branched alkanediyl groups. b When two or more types of alkanediyl groups represented by the formula (I) are present, all of them may be linear alkanediyl groups or branched alkanediyl groups, or some of them may be linear alkanediyl groups and the other may be branched alkanediyl groups. c When two or more types of alkanediyl groups represented by the following formula are present, all of them may be linear alkanediyl groups or branched alkanediyl groups, or some of them may be linear alkanediyl groups and the other part may be branched alkanediyl groups.

[0020] The compound (A1-1) is R 2 , R 3 , R 4 , Ra , R b or R c When the alkanediyl group contains two or more types of alkanediyl groups, all of them may be linear alkanediyl groups or branched alkanediyl groups, or some of them may be linear alkanediyl groups and the other parts may be branched alkanediyl groups.

[0021] n 1 and m 1 may each be 0 to 65, 1 to 60, or 2 to 50.

[0022] The number average molecular weight of the compound (A1-1) may be, for example, 200 to 6000 g / mol. Here, the number average molecular weight is the number average molecular weight in terms of a bifunctional polyoxypropylene polyol, measured by GPC (gel permeation chromatography).

[0023] The hydroxyl value of the compound (A1-1) may be, for example, 30 to 800 mgKOH / g, where the hydroxyl value means the number of milligrams (mg) of potassium hydroxide equivalent to the hydroxyl group in 1 g of the compound (A1-1), and is measured in accordance with JIS K1557-1.

[0024] The state of the compound (A1-1) is not particularly limited, and may be a solid at 25° C. or a liquid at 25° C. The state of the compound (A1-1) is determined by adding R 2 , R 3 , R 4 , R a , R b , or R c The types of alkanediyl groups contained as R (such as the number of carbon atoms and the presence or absence of branching) and the hydroxyl value of the compound (A1-1) can be varied. For example, when R 2 , R 3 , R 4 , R a , R b or R cWhen the total mole number of branched alkanediyl groups in compound (A1-1) relative to the total mole number of alkanediyl groups contained as a branched alkanediyl group is 0.2 to 1.0, and when compound (A1-1) has a high hydroxyl value, compound (A1-1) tends to become a liquid at 25°C.

[0025] In this embodiment, when used as a raw material for a urethane resin, a urethane resin having excellent durability such as heat resistance, moist heat resistance, and hot water resistance is easily formed. 3 is an alkanediyl group, and R 4 is an alkanediyl group, or *1-OR c -*2 is more preferable.

[0026] In the present embodiment, when the compound (A1-1) is used as a raw material for a urethane resin, a urethane resin having excellent 100% modulus and heat resistance is easily formed. 2 , R 3 and R 4 Alkanediyl groups included as *1-OR c -*2 and *1-R a -C(=O)-OR b -*2 and the total number of moles, R 2 Alkanediyl groups and R 4 Included as *1-OR c The ratio of the total number of moles to -*2 is preferably 0.10 or more (for example, 0.10 to 0.90), more preferably 0.20 or more (for example, 0.20 to 0.80), further preferably 0.30 or more (for example, 0.30 to 0.70), and particularly preferably 0.40 or more (for example, 0.40 to 0.60).

[0027] The compound (A1-1) described above may be, for example, a reaction product of polycarbonate polyol (B) and polyester polyol (C). The compound (A1-1) may also be a reaction product of polycarbonate polyol (B), polyester polyol (C), and diol (D) and / or polyhydric alcohol (E) represented by the following formula (e). The compound (A1-1) is a molecule in which, among the oxy groups (-O-) in the group represented by the following formula (I), one forms a carbonate bond derived from the polycarbonate polyol (B), one forms an ester bond derived from the polyester polyol (C), and one bonds with a hydrogen atom to form a hydroxyl group. [ka] [In formula (e), R 1 has the same meaning as above.] [ka] [In formula (I), R 1 has the same meaning as above.]

[0028] The polycarbonate polyol (B) may be any polycarbonate polyol having two or more hydroxyl functional groups, and may be a polycarbonate polyol (B-1) having two hydroxyl functional groups (i.e., a polycarbonate diol), a polycarbonate polyol (B-2) having more than two hydroxyl functional groups, or a combination of two or more selected from the polycarbonate polyol (B-1) and the polycarbonate polyol (B-2).

[0029] The polycarbonate polyol (B-1) may, for example, be one obtained by reacting a carbonate with a diol.

[0030] Examples of carbonates that can be used in the reaction to obtain the polycarbonate polyol (B-1) include dialkyl carbonates such as dimethyl carbonate and diethyl carbonate; alkylene carbonates such as ethylene carbonate and propylene carbonate; diaryl carbonates such as diphenyl carbonate, dinaphthyl carbonate, dianthryl carbonate, diphenanthryl carbonate, diindanyl carbonate and tetrahydronaphthyl carbonate; and the like, and combinations of any two or more of these.

[0031] Diols that can be used in the reaction to obtain the polycarbonate polyol (B-1) include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 2,2-dimethyl-1,3-propanediol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, 3,3-dimethylolheptane, diethylene glycol, and dipropylene glycol. , neopentyl glycol, cyclohexane-1,4-diol, cyclohexane-1,4-dimethanol, diol dimer acid, ethylene oxide or propylene oxide adduct of bisphenol A, bis(β-hydroxyethyl)benzene, xylylene glycol, 1,8-octanediol, 2-ethyl-1,6-hexanediol, 1,9-nonanediol, 2-methyloctane-1,8-diol, and 2-butyl-2-ethyl-1,3-propanediol. These may be used alone or in combination of two or more.

[0032] Examples of the polycarbonate polyol (B-2) include those obtained by reacting a carbonate, a diol, and a polyhydric alcohol having three or more hydroxyl functional groups.

[0033] Examples of carbonates that can be used in the reaction to obtain the polycarbonate polyol (B-2) include the same as those mentioned in the description of the polycarbonate polyol (B-1). Among them, dimethyl carbonate, diethyl carbonate, and ethylene carbonate are preferred.

[0034] Diols that can be used in the reaction to obtain the polycarbonate polyol (B-2) include the same diols as those mentioned in the explanation of the polycarbonate polyol (B-1). Among them, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,9-nonanediol, 3-methyl-1,5-pentanediol, and 2-methyl-1,8-octanediol are preferred.

[0035] Examples of polyhydric alcohols having three or more hydroxyl functional groups that can be used in the reaction to obtain the polycarbonate polyol (B-2) include trimethylolpropane, trimethylolethane, glycerin, pentaerythritol, sorbitol, and the like, and combinations of any two or more of these.

[0036] The polyester polyol (C) may be any polyester polyol having two or more hydroxyl functional groups, and may be a polyester polyol (C-1) having two hydroxyl functional groups (i.e., a polyester diol), a polyester polyol (C-2) having more than two hydroxyl functional groups, or a combination of two or more selected from the polyester polyols (C-1) and (C-2).

[0037] Examples of the polyester polyol (C-1) include the following polyester polyols (α) to (β) and any combination of two or more of these. (α) A polyester polyol (polyester polyol (α)) obtained from a diol (C-1-1) and a dicarboxylic acid and / or its anhydride (C-1-2). (β) A polyester polyol (polyester polyol (β)) obtained by ring-opening addition polymerization of a cyclic ester compound (C-1-4) such as a lactone using a diol (C-1-1) as an initiator. The polyester polyol (β) can be said to be a ring-opening addition polymer of a cyclic ester compound using a diol as an initiator.

[0038] Examples of the diol (C-1-1) include the same diols as those mentioned in the description of the polycarbonate polyol (B-1). Among them, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,9-nonanediol, 3-methyl-1,5-pentanediol, and 2-methyl-1,8-octanediol are preferred.

[0039] Examples of dicarboxylic acids and / or anhydrides thereof (C-1-2) include phthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, cyclohexanedicarboxylic acid, maleic acid, fumaric acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, sebacic acid, dodecanedioic acid, hydrogenated dimer fatty acid, and the like, tartaric acid, and anhydrides thereof, and combinations of any two or more thereof.

[0040] Examples of the cyclic ester compound (C-1-4) include β-propiolactone, β-butyrolactone, γ-butyrolactone, β-valerolactone, γ-valerolactone, δ-valerolactone, α-caprolactone, β-caprolactone, γ-caprolactone, δ-caprolactone, ε-caprolactone, α-methyl-ε-caprolactone, β-methyl-ε-caprolactone, 4-methylcaprolactone, γ-caprylolactone, ε-caprylolactone, ε-palmitolactone, and the like, and combinations of any two or more of these. Among these, the ring-opening addition polymer of ε-caprolactone using trimethylolpropane as an initiator is preferred from the viewpoints of stability during polymerization and economic efficiency.

[0041] Examples of the polyester polyol (C-2) include the following polyester polyols (α') to (β') and any combination of two or more of these. (α') A polyester polyol (polyester polyol (α')) obtained from a diol (C-2-1), a dicarboxylic acid and / or anhydride thereof (C-2-2), and a polyhydric alcohol having three or more hydroxyl functional groups (C-2-3). (β') A polyester polyol (polyester polyol (β')) obtained by ring-opening addition polymerization of a cyclic ester compound (C-2-4) such as a lactone using a polyhydric alcohol (C-2-3) having three or more hydroxyl functional groups as an initiator. The polyester polyol (β') can be said to be a ring-opening addition polymer of a cyclic ester compound using a polyhydric alcohol having three or more hydroxyl functional groups as an initiator.

[0042] Examples of the diol (C-2-1) include the same diols as those mentioned in the description of the polycarbonate polyol (B-1).

[0043] Examples of the dicarboxylic acid and / or anhydride thereof (C-2-2) include the same as those mentioned in the description of the dicarboxylic acid and / or anhydride thereof (C-1-2).

[0044] Examples of polyhydric alcohols (C-2-3) having three or more hydroxyl functional groups include trimethylolpropane, trimethylolethane, glycerin, pentaerythritol, sorbitol, and combinations of any two or more of these.

[0045] Examples of the cyclic ester compound (C-2-4) include the same compounds as those mentioned in the description of the cyclic ester compound (C-1-4).

[0046] In this embodiment, it is more preferable that the polyester polyol (C) contains polyester polyol (β) and / or polyester polyol (β'), from the viewpoint that when used as a raw material for a urethane resin, a urethane resin having excellent durability such as heat resistance or moist heat resistance is easily formed.

[0047] Specific examples of the diol (D) include the same diols as those mentioned in the description of the polycarbonate polyol (B-1), among which 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,9-nonanediol, 3-methyl-1,5-pentanediol, and 2-methyl-1,8-octanediol are preferred.

[0048] Specific examples of the polyhydric alcohol (E) include trimethylolpropane, trimethylolethane, glycerin and pentaerythritol. These may be used alone or in combination of two or more.

[0049] One of the hydroxy groups in the compound (A1-1) is, for example, a hydroxy group represented by the following formula (e): [ka] [In formula (e), R 1 has the same meaning as above.] The hydroxy group may be an unreacted hydroxy group in the compound represented by formula (e) derived from the compound represented by formula (e) above. The hydroxy group may be a hydroxy group derived from the compound represented by formula (e) above ... 2 , R 3 and / or R 4 In addition, the hydroxyl group derived from the compound represented by formula (e) tends to have a lower reactivity than the hydroxyl group bonded to the molecular chain containing 1 The length to the joint with R 2 , R 3 and / or R 4Since the length from the hydroxy group bonded to the molecular chain containing the hydroxy group to the branch is shorter than that of the hydroxy group, the urethane resin obtained by the reaction of the compound (A1-1) with an isocyanate compound tends to have higher rigidity. The compound (A1-1) is expected to be used as a raw material for various urethane resins by utilizing the reactivity of the hydroxy group and high rigidity due to the difference in the length from the hydroxy group to the branch. Furthermore, one of the bonds in the formula (I) in the compound (A1-1) is a carbonate bond and the other is an ester bond. The carbonate bond tends to contribute to improving heat resistance, and the ester bond tends to contribute to improving flexibility. The compound (A1-1) is expected to be used as a raw material for various urethane resins by utilizing the carbonate bond and ester bond.

[0050] <Composition> The composition of the present embodiment contains a compound (A1-1). The composition may further contain at least one of a polycarbonate polyol represented by the following formula (A1-2) (hereinafter referred to as "compound (A1-2)") and a polyester polyol represented by the following formula (A1-3) (hereinafter referred to as "compound (A1-3)"). [ka] [In formula (A1-2), R 1 , R 2 and R 4 is as defined above, and n 2 and m 2 Each represents an integer greater than or equal to 0. 2 may be the same or different, R 4 When there are a plurality of, they may be the same or different. [ka] [In formula (A1-3), R 1 , R 3 and R 4 is as defined above, and n 3 and m 3Each represents an integer greater than or equal to 0. 3 may be the same or different, R 4 When there are a plurality of, they may be the same or different.

[0051] Compound (A1-2) contains R 1 The atom or group contained as R in compound (A1-1). 1 Similarly, the atom or group contained in the compound (A1-3) may be the same as the atom or group contained in the compound (A1-3). 1 The atom or group contained as R in compound (A1-1). 1 The atom or group may be the same as that included in the composition as R 1 When the composition contains two or more compounds (A1-1) having different alkyl and / or hydroxyalkyl groups represented by R 1 and / or two or more compounds (A1-2) having different alkyl groups and / or hydroxyalkyl groups represented by R 1 In this case, the compound (A1-2) and / or the compound (A1-3) may contain two or more compounds having different alkyl groups and / or hydroxyalkyl groups represented by R 1 The combination of groups included as R 1 may be the same as the combination of groups included in

[0052] Compound (A1-2) contains R 2 The alkanediyl group contained as R 2 The alkanediyl group may be the same as the alkanediyl group contained as R 2 When the composition contains two or more compounds (A1-1) having different alkanediyl groups represented by R 2 In this case, the compound (A1-2) may contain two or more compounds having different alkanediyl groups represented by R 2 The combination of alkanediyl groups contained as R 2The combination of alkanediyl groups may be the same as that contained in the above formula (1).

[0053] Compound (A1-3) contains R 3 The group contained as R in compound (A1-1) 3 The composition may be the same as the group included as R 3 When the composition contains two or more compounds (A1-1) having different groups represented by R 3 In this case, the compound (A1-3) may include two or more compounds having different groups represented by R 3 The combination of groups included as R 3 may be the same as the combination of groups included in

[0054] Compound (A1-2) contains R 4 The group contained as R in compound (A1-1) 4 Similarly, R 4 The group contained as R in compound (A1-1) 4 The compound (A1-1) may be the same as the group included as R 4 When the compound (A1-2) and / or the compound (A1-3) contain two or more groups as R 4 In this case, the compound (A1-2) and / or the compound (A1-3) may contain two or more kinds of groups as R 4 The combination of groups included as R 4 may be the same as the combination of groups included in

[0055] m 2 , n 2 , m 3 and n 3 may each be 0 to 65, 1 to 60, or 2 to 50.

[0056] In the following description, the total number of moles of the group represented by the following formula (a1-1) contained in the composition is represented by C A1-1The total number of moles of the group represented by the following formula (a1-2) contained in the composition is C A1-2 The total number of moles of the group represented by the following formula (a1-3) contained in the composition is C A1-3 Let us assume that. [ka] [In formula (a1-1), R 1 is as defined above, and * indicates a bond. The bond represented by * is directly bonded to a carbon atom.] [ka] [In formula (a1-2), R 1 is as defined above, and * indicates a bond. The bond represented by * is directly bonded to a carbon atom.] [ka] [In formula (a1-3), R 1 is as defined above, and * indicates a bond. The bond represented by * is directly bonded to a carbon atom.]

[0057] Molar ratio (C A1-1 / (C A1-1 +C A1-2 +C A1-3 )×100) is preferably 5.3 or more, more preferably 7.0 or more, even more preferably 10.0 or more, and even more preferably 20.0 or more. A1-1 / (C A1-1 +C A1-2 +C A1-3 When the molar ratio (C )×100) is 5.3 or more, a polyurethane resin having excellent hot water resistance is easily formed. A1-1 / (C A1-1 +C A1-2 +C A1-3 ) × 100) is preferably 99 or less, more preferably 80 or less, even more preferably 70 or less, and particularly preferably 60 or less. A1-1 / (C A1-1 +CA1-2 +C A1-3 When the molar ratio (C)×100) is 99 or less, a polyurethane resin having excellent 100% modulus and heat resistance tends to be formed. A1-1 / (C A1-1 +C A1-2 +C A1-3 ) × 100) may be 5.3 to 99. A1-1 / (C A1-1 +C A1-2 +C A1-3 When the ratio (x)×100) is within the above range, when the composition is used as a raw material for a urethane resin, a polyurethane resin that is excellent in 100% modulus, heat resistance, and hot water resistance tends to be formed.

[0058] Molar ratio (C A1-1 / (C A1-1 +C A1-2 +C A1-3 )×100) is the average value of the composition using, for example, deuterated chloroform as the solvent and tetramethylsilane as the standard substance. 1 H-NMR measurement and the results obtained by the measurement 1 It can be determined from the integral value of the signal in the H-NMR spectrum. Specifically, for example, the integral value Δ S1-1 (2 mol of hydrogen atoms) and the integral value Δ of the methylene signal (S1-2) located next to the hydroxyl group of the group represented by formula (a1-2) S1-2 (2 mol of hydrogen atoms) and the integral value Δ of the methylene signal (S1-3) located next to the hydroxyl group of the group represented by formula (a1-3) S1-3 (2 mol of hydrogen atoms) and the molar ratio (C A1-1 / (C A1-1 +C A1-2 +C A1-3 ) × 100) can be calculated. In this case, the molar ratio (C A1-1 / (C A1-1 +C A1-2 +C A1-3 )×100) is the integral value of the signal (S1-1) Δ S1-1 and the integral value of the signal (S1-2) ΔS1-2 and the integral value of the signal (S1-3) Δ S1-3 The sum of and the integral value of the signal (S1-1) Δ S1-1 Ratio of (Δ S1-1 / (Δ S1-1 +Δ S1-2 +Δ S1-3 ) × 100).

[0059] The composition may further contain at least one of a polycarbonate polyol represented by the following formula (A2-2) (hereinafter referred to as "compound (A2-2)") and a polyester polyol represented by the following formula (A2-3) (hereinafter referred to as "compound (A2-3)"): [ka] [In formula (A2-2), R 1 , R 2 and R 4 is as defined above, and n 4 R indicates an integer equal to or greater than 0. 4 When there are a plurality of, they may be the same or different. [ka] [In formula (A2-3), R 1 , R 3 and R 4 is as defined above, and n 5 R indicates an integer equal to or greater than 0. 4 When there are a plurality of, they may be the same or different.

[0060] R to compound (A2-2) 1 The atom or group contained as R in compound (A1-1). 1 Similarly, the atom or group contained in the compound (A2-3) may be the same as the atom or group contained in the compound (A2-3). 1 The atom or group contained as R in compound (A1-1). 1 The atom or group may be the same as that included in the composition as R 1When the composition contains two or more compounds (A1-1) having different alkyl and / or hydroxyalkyl groups represented by R 1 and / or R 1 In this case, the compound (A2-2) and / or the compound (A2-3) may contain two or more compounds having different alkyl groups and / or hydroxyalkyl groups represented by R 1 The combination of groups included as R 1 may be the same as the combination of groups included in

[0061] R to compound (A2-2) 2 The alkanediyl group contained as R 2 The alkanediyl group may be the same as the alkanediyl group contained as R 2 When the composition contains two or more compounds (A1-1) having different alkanediyl groups represented by R 2 In this case, the compound (A2-2) may contain two or more compounds having different alkanediyl groups represented by R 2 The combination of alkanediyl groups contained as R 2 The combination of alkanediyl groups may be the same as that contained in the above formula (1).

[0062] R to compound (A2-3) 3 The group contained as R in compound (A1-1) 3 The composition may be the same as the group included as R 3 When the composition contains two or more compounds (A1-1) having different groups represented by R 3 In this case, the compound (A2-2) may include two or more compounds having different groups represented by R 3 The combination of groups included as R 3may be the same as the combination of groups included in

[0063] R to compound (A2-2) 4 The group contained as R in compound (A1-1) 4 Similarly, R 4 The group contained as R in compound (A1-1) 4 The compound (A1-1) may be the same as the group included as R 4 When R contains two or more groups, the compound (A2-2) and / or the compound (A2-3) also contains R 4 In this case, the compound (A2-2) and / or the compound (A2-3) may contain two or more types of groups as R 4 The combination of groups included as R 4 may be the same as the combination of groups included in

[0064] n 4 and n 5 may each be 0 to 65, 1 to 60, or 2 to 50.

[0065] In the following description, the total number of moles of the group represented by the following formula (a2-2) contained in the composition is represented by C A2-2 The total number of moles of the group represented by the following formula (a2-3) contained in the composition is C A2-3 Let us assume that. [ka] [In formula (a2-2), R 1 is as defined above, and * indicates a bond. The bond represented by * is directly bonded to a carbon atom.] [ka] [In formula (a2-3), R 1 is as defined above, and * indicates a bond. The bond represented by * is directly bonded to a carbon atom.]

[0066] Molar ratio ((C A2-2 +C A2-3 ) / (C A1-1 +C A1-2 +C A1-3 The molar ratio ((C)) may be 0.010 or more, 0.050 or more, 0.100 or more, 0.200 or more, or 0.300 or more. A2-2 +C A2-3 ) / (C A1-1 +C A1-2 +C A1-3 When the molar ratio ((C )) is 0.010 or more, a polyurethane resin that is particularly excellent in 100% modulus, breaking strength, glass transition temperature and elongation percentage tends to be formed. A2-2 +C A2-3 ) / (C A1-1 +C A1-2 +C A1-3 The molar ratio ((C A2-2 +C A2-3 ) / (C A1-1 +C A1-2 +C A1-3 When the molar ratio ((C )) is 0.750 or less, a polyurethane resin that is particularly excellent in hot water resistance and breaking strength tends to be formed. A2-2 +C A2-3 ) / (C A1-1 +C A1-2 +C A1-3 The molar ratio ((C A2-2 +C A2-3 ) / (C A1-1 +C A1-2 +C A1-3 When the composition is used as a raw material for a urethane resin, a polyurethane resin having good 100% modulus, heat resistance, breaking strength, elongation, glass transition temperature, and hot water resistance tends to be formed.

[0067] Molar ratio ((C A2-2 +C A2-3 ) / (C A1-1 +C A1-2 +C A1-3 )) can be expressed, for example, as the molar ratio (C A1-1 / (CA1-1 +C A1-2 +C A1-3 ) × 100), deuterated chloroform was used as the solvent and tetramethylsilane was used as the standard substance. 1 H-NMR measurement and the results obtained by the measurement 1 It can be determined from the integral value of the signal in the H-NMR spectrum. Specifically, for example, the integral value Δ S1-1 (2 mol of hydrogen atoms) and the integral value of the above signal (S1-2) Δ S1-2 (2 mol of hydrogen atoms) and the integral value of the above signal (S1-3) Δ S1-3 (2 mol of hydrogen atoms) and the integral value Δ of the methylene signal (S2-2) located next to the hydroxyl group of the group represented by formula (a2-2) S2-2 (4 mol of hydrogen atoms) and the integral value Δ of the methylene signal (S2-3) located next to the hydroxyl group of the group represented by formula (a2-3) S2-3 (4 mol of hydrogen atoms) and the molar ratio ((C A2-2 +C A2-3 ) / (C A1-1 +C A1-2 +C A1-3 In this case, the molar ratio ((C A2-2 +C A2-3 ) / (C A1-1 +C A1-2 +C A1-3 )) is the integral value of the signal (S1-1) Δ S1-1 and the integral value of the signal (S1-2) Δ S1-2 and the integral value of the signal (S1-3) Δ S1-3 The sum of and the integral value of the signal (S2-2) Δ S2-2 and the integral value of the signal (S2-3) Δ S2-3 The sum of and the ratio of (0.5×(Δ S2-2 +Δ S2-3 ) / (Δ S1-1 +Δ S1-2 +Δ S1-3 )) can be rephrased as follows.

[0068] The composition may further contain a polyhydric alcohol represented by the following formula (e) (hereinafter, also referred to as "polyhydric alcohol (E)"). Hereinafter, the total number of moles of the polyhydric alcohol represented by the following formula (e) is referred to as C E In addition, the signal of the methylene adjacent to the hydroxyl group of the polyhydric alcohol represented by formula (e) is represented by Se. [ka] [In formula (e), R 1 has the same meaning as above.]

[0069] The polyhydric alcohol (E) has the same meaning as described above, and the polyhydric alcohol (E) is R 1 The alkyl group and the hydroxyalkyl group represented by R 1 may be the same as the atom or group contained as

[0070] Polyhydric alcohol (E) to R 1 The atom or group contained as R in compound (A1-1). 1 The atom or group may be the same as that included in the composition as R 1 When the composition contains two or more compounds (A1-1) having different alkyl and / or hydroxyalkyl groups represented by R 1 In this case, the compound represented by the formula (E) may contain two or more polyhydric alcohols (E) having different alkyl and / or hydroxyalkyl groups represented by the formula (E). 1 The combination of groups included as R 1 may be the same as the combination of groups included in

[0071] The composition may further contain an oxetane compound represented by the following formula (f) (hereinafter also referred to as "oxetane compound (F)"). [ka] [In formula (f), R1 has the same meaning as above.]

[0072] The oxetane compound (F) has the same meaning as described above, and the oxetane compound (F) is R 1 The alkyl group and the hydroxyalkyl group represented by R 1 may be the same as the atom or group contained as

[0073] Oxetane compound (F) R 1 The atom or group contained as R in compound (A1-1). 1 The atom or group may be the same as that included in the composition as R 1 When the composition contains two or more compounds (A1-1) having different alkyl and / or hydroxyalkyl groups represented by R 1 In this case, the oxetane compound (F) may contain two or more kinds of oxetane compounds having different alkyl groups and / or hydroxyalkyl groups represented by R 1 The combination of groups included as R 1 may be the same as the combination of groups included in

[0074] Specific examples of the oxetane compound (F) include 3-ethyl-3-hydroxymethyloxetane, 3-methyl-3-hydroxymethyloxetane, and 3,3-dihydroxymethyloxetane. These may be used alone or in combination of two or more.

[0075] The composition may further contain a polycarbonate polyol represented by the following formula (A-3) (hereinafter referred to as "compound (A-3)"). [ka] [In formula (A-3), R 1 and R 4 is as defined above, and n 5 , m 5 and p 5Each R represents an integer of 1 or more. 4 may be the same or different.]

[0076] Compound (A-3) contains R 1 The atom or group contained as R in compound (A1-1). 1 The atom or group may be the same as that included in the composition as R 1 When the composition contains two or more compounds (A1-1) having different alkyl and / or hydroxyalkyl groups represented by R 1 In this case, the compound (A-3) may contain two or more compounds having different alkyl and / or hydroxyalkyl groups represented by R 1 The combination of groups included as R 1 may be the same as the combination of groups included in

[0077] Compound (A-3) contains R 4 The group contained as R in compound (A1-1) 4 The compound (A1-1) may be the same as the group included as R 4 When R contains two or more groups, the compound (A-3) also contains R 4 In this case, compound (A-3) may contain two or more types of groups as R 4 The combination of two or more groups contained as R 4 may be the same as a combination of two or more groups included in the formula:

[0078] n 5 , m 5 and p 5 may be 1 to 65, 2 to 60, or 3 to 50.

[0079] The composition may further contain a polycarbonate diol represented by the following formula (A-4) (hereinafter referred to as "compound (A-4)"). [ka] [In formula (A-4), R 4 is as defined above, and n 6 indicates an integer of 1 or more. 4 may be the same or different.]

[0080] Compound (A-4) contains R 4 The group contained as R in compound (A1-1) 4 The compound (A1-1) may be the same as the group included as R 4 When R contains two or more groups, the compound (A-4) also contains R 4 In this case, compound (A-4) may contain two or more types of groups as R 4 The combination of two or more groups contained as R 4 may be the same as a combination of two or more groups included in the formula:

[0081] n 6 may be 1 to 65, 2 to 60, or 3 to 50.

[0082] In the following description, the total number of moles of the group represented by the following formula (I) contained in the composition is represented by C T Let us assume that. [ka] [In formula (I), R 1 has the same meaning as above, and * indicates a bond. In formula (I), the bond represented by * is directly bonded to a carbon atom or a hydrogen atom.

[0083] Molar ratio (C A1-1 / C T ) may be 0.02 or more, 0.05 or more, or 0.1 or more. A1-1 / C T When the molar ratio (C) is 0.02 or more, a polyurethane resin having excellent hot water resistance is easily formed. A1-1 / C TThe molar ratio (C) may be 0.990 or less, 0.800 or less, or 0.700 or less. A1-1 / C T When the molar ratio (C) is 0.990 or less, a polyurethane resin having excellent 100% modulus and heat resistance is easily formed. A1-1 / C T The molar ratio (C A1-1 / C T ) within the above range, when the composition is used as a raw material for a urethane resin, a polyurethane resin that is excellent in 100% modulus, heat resistance, and hot water resistance tends to be formed.

[0084] Molar ratio (C A1-2 / C T The molar ratio (C) may be 0.001 or more, 0.010 or more, or 0.050 or more. A1-2 / C T When the molar ratio (C) is 0.001 or more, a polyurethane resin having excellent breaking strength and hot water resistance tends to be formed. A1-2 / C T The molar ratio (C) may be 0.990 or less, 0.400 or less, or 0.500 or less. A1-2 / C T The molar ratio (C A1-2 / C T ) within the above range, when the composition is used as a raw material for a urethane resin, a polyurethane resin that is good in all respects in 100% modulus, heat resistance, breaking strength, and hot water resistance tends to be formed.

[0085] Molar ratio (C A1-3 / C T ) may be 0.005 or more, 0.010 or more, 0.050 or more, 0.100 or more, 0.150 or more, 0.200 or more, 0.250 or more, or 0.300 or more. A1-3 / C T ) may be 0.340 or less, 0.250 or less, 0.200 or less, 0.150 or less, 0.100 or less, 0.050 or less, or 0.020 or less. A1-3 / CT When the molar ratio (C) is 0.340 or less, a polyurethane resin having excellent hot water resistance is easily formed. A1-3 / C T The molar ratio (C A1-3 / C T ) within the above range, when the composition is used as a raw material for a urethane resin, a polyurethane resin that is excellent in 100% modulus, heat resistance, and hot water resistance tends to be formed.

[0086] Molar ratio (C A2-3 / C T ) may be 0.001 or more, 0.005 or more, 0.010 or more, 0.050 or more, 0.100 or more, 0.150 or more, 0.200 or more, or 0.220 or more. A2-3 / C T When the molar ratio (C) is 0.001 or more, a polyurethane resin that is particularly excellent in 100% modulus, breaking strength, glass transition temperature and elongation percentage tends to be formed. A2-3 / C T ) may be 0.234 or less, 0.200 or less, 0.150 or less, 0.100 or less, 0.050 or less, or 0.015 or less. A2-3 / C T When the molar ratio (C) is 0.234 or less, a polyurethane resin having excellent hot water resistance and breaking strength is easily formed. A2-3 / C T The molar ratio (C A2-3 / C T ) within the above range, when the composition is used as a raw material for a urethane resin, a polyurethane resin that is good in all respects, including 100% modulus, heat resistance, hot water resistance, breaking strength, elongation, and glass transition temperature, tends to be formed.

[0087] Molar ratio (C A1-1 / C T ), molar ratio (C A1-2 / C T ), molar ratio (C A1-3 / C T ) and molar ratio (CA2-3 / C T ) are within the above ranges, when the composition is used as a raw material for a urethane resin, a polyurethane resin having both a 100% modulus and heat resistance that is even better tends to be formed.

[0088] Molar ratio (C A1-1 / C T ), molar ratio (C A1-2 / C T ), molar ratio (C A1-3 / C T ) and molar ratio (C A2-3 / C T ) is, for example, (C A1-1 / (C A1-1 +C A1-2 +C A1-3 ) × 100), deuterated chloroform was used as the solvent and tetramethylsilane was used as the standard substance. 1 H-NMR measurement and the results obtained by the measurement 1 It can be determined from the integral value of the signal in the H-NMR spectrum. Specifically, for example, the integral value Δ S1-1 (2 mol of hydrogen atoms) and the integral value of the above signal (S1-2) Δ S1-2 (2 mol of hydrogen atoms) and the integral value of the above signal (S1-3) Δ S1-3 (2 mol of hydrogen atoms) and the integral value of the above signal (S2-3) Δ S2-3 (4 mol of hydrogen atoms) and R 1 When R in formula (I) is a linear alkyl group, 1 (Alkyl group) terminal methyl signal (SI) integral value Δ SI (3 mol of hydrogen atoms) from the molar ratio (C A1-1 / C T ), molar ratio (C A1-2 / C T ), molar ratio (C A1-3 / C T ) and molar ratio (C A2-3 / C T In this case, the molar ratio (C A1-1 / C T ) is the integral value of the signal (S1-1) Δ S1-1and the integral value of the signal (SI) Δ SI 1.5 times the ratio (1.5 × Δ S1-1 / Δ SI ), molar ratio (C A1-2 / C T ) is the integral value of the signal (S1-2) Δ S1-2 and the integral value of the signal (SI) Δ SI 1.5 times the ratio (1.5 × Δ S1-2 / Δ SI ), molar ratio (C A1-3 / C T ) is the integral value of the signal (S1-3) Δ S1-3 and the integral value of the signal (SI) Δ SI 1.5 times the ratio (1.5 × Δ S1-3 / Δ SI ), molar ratio (C A2-3 / C T ) is the integral value of the signal (S2-3) Δ S2-3 and the integral value of the signal (SI) Δ SI 0.75 times the ratio (0.75 × Δ S2-3 / Δ SI ) can be rephrased as:

[0089] The composition may further contain a diol (D). The diol (D) has the same meaning as defined above.

[0090] In the following description, the total number of moles of the group represented by the following formula (d) contained in the composition is represented by C D Let us assume that. [ka] [In formula (d), R is a hydrogen atom or an alkanediyl group, and * indicates a bond. R may be the same or different.]

[0091] Molar ratio (C A2-3 / (C A2-2 +C A2-3 +C D ) × 100) may be 0.010 or more, 0.050 or more, 0.100 or more, 0.500 or more, 1.0 or more, 3.0 or more, 5.0 or more, 7.0 or more, 8.5 or more, or 9.5 or more.A2-3 / (C A2-2 +C A2-3 +C D When the molar ratio (C)×100) is 0.010 or more, a polyurethane resin having excellent heat resistance tends to be formed. A2-3 / (C A2-2 +C A2-3 +C D ) × 100) may be 10.20 or less, 9.0 or less, 5.0 or less, 3.0 or less, 1.0 or less, 0.900 or less, 0.600 or less, 0.300 or less, or 0.100 or less. A2-3 / (C A2-2 +C A2-3 +C D When the molar ratio (C)×100) is 10.20 or less, a polyurethane resin having excellent hot water resistance and breaking strength is easily formed. A2-3 / (C A2-2 +C A2-3 +C D ) × 100) may be 0.010 to 10.20. A2-3 / (C A2-2 +C A2-3 +C D When the ratio (x)×100) is within the above range, when the composition is used as a raw material for a urethane resin, a polyurethane resin that is good in 100% modulus, heat resistance, breaking strength, and hot water resistance tends to be formed.

[0092] Molar ratio ((C A2-2 +C A2-3 ) / (C A2-2 +C A2-3 +C D )×100) may be 0.100 or more, 0.300 or more, 0.600 or more, 1.00 or more, 3.00 or more, 5.00 or more, 7.00 or more, or 9.00 or more. A2-2 +C A2-3 ) / (C A2-2 +C A2-3 +C D When the molar ratio ((C )×100) is 0.100 or more, a polyurethane resin having excellent 100% modulus and heat resistance tends to be formed. A2-2 +C A2-3 ) / (CA2-2 +C A2-3 +C D )×100) may be 12.00 or less, 10.00 or less, 8.00 or less, 6.00 or less, 4.00 or less, 2.00 or less, or 1.000 or less. A2-2 +C A2-3 ) / (C A2-2 +C A2-3 +C D ) × 100) may be 0.100 to 12.00. A2-2 +C A2-3 ) / (C A2-2 +C A2-3 +C D When (x100)) is within the above range, when the composition is used as a raw material for a urethane resin, a polyurethane resin having both good 100% modulus and good heat resistance tends to be formed.

[0093] Molar ratio (C A2-3 / (C A2-2 +C A2-3 +C D ) × 100) and molar ratio ((C A2-2 +C A2-3 ) / (C A2-2 +C A2-3 +C D )×100) are both within the above ranges, when the composition is used as a raw material for a urethane resin, a polyurethane resin having both a 100% modulus and heat resistance that is even better tends to be formed.

[0094] Molar ratio (C A2-3 / (C A2-2 +C A2-3 +C D ) × 100) and molar ratio ((C A2-2 +C A2-3 ) / (C A2-2 +C A2-3 +C D ) × 100) is, for example, (C A1-1 / (C A1-1 +C A1-2 +C A1-3 ) × 100), deuterated chloroform was used as the solvent and tetramethylsilane was used as the standard substance. 1H-NMR measurement and the results obtained by the measurement 1 It can be determined from the integral value of the signal in the H-NMR spectrum. Specifically, for example, the integral value Δ S2-2 (4 mol of hydrogen atoms) and the integral value of the above signal (S2-3) Δ S2-3 (4 mol of hydrogen atoms) and the integral value Δ of the methylene signal (Sd) located next to the hydroxyl group of the group represented by formula (d) Sd (2 mol of hydrogen atoms) and the molar ratio (C A2-3 / (C A2-2 +C A2-3 +C D ) × 100) and molar ratio ((C A2-2 +C A2-3 ) / (C A2-2 +C A2-3 +C D ) × 100) can be calculated. In this case, the molar ratio (C A2-3 / (C A2-2 +C A2-3 +C D )×100) is the integral value of the signal (S2-2) Δ S2-2 and the integral value of the signal (S2-3) Δ S2-3 and the integral value of the signal (Sd) Δ Sd The sum of and the integral value of the signal (S2-3) Δ S2-3 and the ratio of ((Δ S2-3 ) / (Δ S2-2 +Δ S2-3 +2×Δ Sd ) × 100), and the molar ratio ((C A2-2 +C A2-3 ) / (C A2-2 +C A2-3 +C D )×100) is the integral value of the signal (S2-2) Δ S2-2 and the integral value of the signal (S2-3) Δ S2-3 and the integral value of the signal (Sd) Δ Sd The sum of and the integral value of the signal (S2-2) Δ S2-2 and the integral value of the signal (S2-3) Δ S2-3 The sum of and the ratio of ((Δ S2-2 +Δ S2-3 ) / (Δ S2-2 +Δ S2-3 +2×ΔSd ) × 100).

[0095] In the following description, the total number of moles of the group represented by the following formula (f') contained in the composition is represented by C F Let us assume that. [ka] [In formula (f'), R 1 has the same meaning as above, and * indicates a bond.

[0096] Molar ratio (C F / C T × 100) may be 1.70 or more, 1.80 or more, 2.00 or more, 3.00 or more, 4.00 or more, 5.00 or more, 6.00 or more, 7.00 or more, 8.00 or more, 9.00 or more, 10.00 or more, or 15.00 or more. F / C T When the molar ratio (C × 100) is 1.7 or more, the oxetane compound tends to self-crosslink to form a polyurethane resin that is particularly excellent in heat resistance and 100% modulus. F / C T ×100) may be 45.0 or less, 42.0 or less, 40.0 or less, 35.0 or less, 30.0 or less, 25.0 or less, 20.0 or less, 15.0 or less, or 10.0 or less. F / C T When the molar ratio (C × 100) is 45.0 or less, a polyurethane resin having excellent heat resistance is easily formed. F / C T × 100) may be 1.70 to 45.0, 1.80 to 42.0, 2.00 to 40.0, 3.00 to 30.0, 4.00 to 20.0, 5.00 to 15.0, or 6.00 to 10.0. F / C T × 100) within the above range, when the composition is used as a raw material for a urethane resin, a polyurethane resin having good 100% modulus and good heat resistance tends to be formed.

[0097] Molar ratio (CF / C T × 100), for example, (C A1-1 / (C A1-1 +C A1-2 +C A1-3 ) × 100), deuterated chloroform was used as the solvent and tetramethylsilane was used as the standard substance. 1 H-NMR measurement and the results obtained by the measurement 1 It can be determined from the integral value of the signal in the H-NMR spectrum. Specifically, for example, the integral value Δ SI (3 mol of hydrogen atoms) and the integral value Δ of the methylene signal (Sf) located next to the oxygen atom of the oxetane group in formula (f') Sf (4 mol of hydrogen atoms) and the molar ratio (C F / C T In this case, the molar ratio (C F / C T ×100) is the integral value of the signal (SI) Δ SI and the integral value of the signal (Sf) Δ Sf 0.75 times the ratio of and (0.75 × Δ Sf / Δ SI × 100).

[0098] The composition may be a reaction mixture of polycarbonate polyol (B), polyester polyol (C), and diol (D), polyhydric alcohol (E), and / or oxetane compound (F) added as needed. The above reaction is usually carried out in the presence of an ester exchange catalyst, so the composition may further contain an ester exchange catalyst. Lithium acetylacetonate is preferably used as the ester exchange catalyst. The content of the ester exchange catalyst may be 0.0001 to 0.100% by mass based on the total mass of the composition.

[0099] The properties of the composition are not particularly limited, and may be a solid or a liquid at 25° C. The properties of the composition can be changed depending on the types and content ratios of the components contained therein (e.g., compounds (A1-1) to (A1-3), compounds (A2-2) to (A2-3), compound (A-3), compound (A-4), and oxetane compound (F)).

[0100] The number average molecular weight of the composition may be, for example, 200 to 6000 g / mol. The lower limit of the number average molecular weight of the composition may be, for example, 200 g / mol or more, 400 g / mol or more, 600 g / mol or more, 800 g / mol or more, 1000 g / mol or more, 1200 g / mol or more, 1400 g / mol or more, 1600 g / mol or more, or 1800 g / mol or more. The upper limit of the number average molecular weight of the composition may be, for example, 6000 g / mol or less, 5000 g / mol or less, 4000 g / mol or less, 3000 g / mol or less, 2500 g / mol or less, 2000 g / mol or less, 1800 g / mol or less, 1600 g / mol or less, 1400 g / mol or less, 1200 g / mol or less, 1000 g / mol or less, or 800 g / mol or less.

[0101] The number average molecular weight of the composition is the number average molecular weight calculated as a difunctional polyoxypropylene polyol, measured by using GPC (gel permeation chromatography) with the entire composition as the measurement subject.

[0102] The hydroxyl value of the composition may be, for example, 30 to 800 mgKOH / g. The lower limit of the hydroxyl value of the composition may be, for example, 30 mgKOH / g or more, 40 mgKOH / g or more, 50 mgKOH / g or more, 60 mgKOH / g or more, 70 mgKOH / g or more, 80 mgKOH / g or more, 90 mgKOH / g or more, 100 mgKOH / g or more, 120 mgKOH / g or more, 140 mgKOH / g or more, 160 mgKOH / g or more, or 180 mgKOH / g or more. The upper limit of the hydroxyl value of the composition may be, for example, 800 mgKOH / g or less, 700 mgKOH / g or less, 600 mgKOH / g or less, 500 mgKOH / g or less, 400 mgKOH / g or less, 300 mgKOH / g or less, 250 mgKOH / g or less, 200 mgKOH / g or less, 180 mgKOH / g or less, 160 mgKOH / g or less, 140 mgKOH / g or less, 120 mgKOH / g or less, 100 mgKOH / g or less, or 80 mgKOH / g or less.

[0103] The hydroxyl value of a composition means the number of milligrams (mg) of potassium hydroxide equivalent to the hydroxyl group in 1 g of the composition, and is measured in accordance with JIS K1557-1.

[0104] The acid value of the composition may be, for example, 0.01 to 10.0 mgKOH / g. The lower limit of the acid value of the composition may be, for example, 0.01 mgKOH / g or more, 0.02 mgKOH / g or more, 0.03 mgKOH / g or more, 0.04 mgKOH / g or more, 0.05 mgKOH / g or more, 0.06 mgKOH / g or more, or 0.07 mgKOH / g or more. The upper limit of the acid value of the composition may be, for example, 10.0 mgKOH / g or less, 5.0 mgKOH / g or less, 3.0 mgKOH / g or less, 1.0 mgKOH / g or less, 0.5 mgKOH / g or less, 0.4 mgKOH / g or less, 0.3 mgKOH / g or less, or 0.2 mgKOH / g or less.

[0105] The acid value of a composition means the number of milligrams (mg) of potassium hydroxide equivalent to the hydroxyl group in 1 g of the composition, and is measured in accordance with JIS K1557-5.

[0106] In this embodiment, deuterated chloroform is used as a solvent, and tetramethylsilane is used as a reference material to measure the composition. 1 When H-NMR measurement is performed, for example, the above signal (S1-1) is 1 The signal (S1-2) is observed in the range of 3.435 ppm to 3.475 ppm in the H-NMR spectrum. 1 The signal (S1-3) is observed in the range of 3.475 ppm to 3.520 ppm in the H-NMR spectrum. 1 The signal (S2-2) is observed in the range of 3.400 ppm to 3.435 ppm in the H-NMR spectrum. 1 The signal (S2-3) is observed in the range of 3.595 ppm to 3.618 ppm in the H-NMR spectrum. 1 The signal (Sd) is observed in the range of 3.550 ppm to 3.595 ppm in the H-NMR spectrum. 1 H-NMR spectrum in the range of 3.618 ppm to 3.710 ppm, and in addition, the integral value Δ Se but, 1 The signal (Sf) is observed in the range of 3.710 ppm to 3.760 ppm in the H-NMR spectrum. 1 The R 1 is an ethyl group, the above signal (SI) is observed in the range of 0.700 ppm or more and 1.000 ppm or less, and R 1 When is a methyl group, the above signal (SI) is observed in the range of 0.700 ppm to 1.130 ppm. Therefore, in this embodiment, the molar ratio (C A1-1 / (C A1-1 +C A1-2 +C A1-3 ) × 100), molar ratio ((C A2-2 +C A2-3 ) / (C A1-1 +C A1-2 +C A1-3 )), molar ratio (CA1-1 / C T ), molar ratio (C A1-2 / C T ), molar ratio (C A1-3 / C T ), molar ratio (C A2-3 / C T ), molar ratio (C A2-3 / (C A2-2 +C A2-3 +C D ) × 100), molar ratio ((C A2-2 +C A2-3 ) / (C A2-2 +C A2-3 +C D ) × 100) and molar ratio (C F / C T × 100) can be calculated.

[0107] According to this embodiment, it is possible to provide a composition that contributes to the formation of a urethane resin having a low 100% modulus and a high softening temperature.

[0108] <Method of producing polycarbonate polyol and composition> The compound (A1-1) of the above embodiment can be obtained, for example, by a method including a reaction step of obtaining the compound (A1-1) by reacting a polycarbonate polyol with a polyester polyol (A1-1) (ester exchange reaction) in a mixed solution containing a polycarbonate polyol (B), a polyester polyol (C), and an ester exchange catalyst. In the method, at least one of the polycarbonate polyol and the polyester polyol contains a group represented by the above formula (I), or the mixed solution further contains a polyhydric alcohol represented by the above formula (e).

[0109] In the above method, the composition of the above embodiment can be obtained as a reaction mixture containing the compound (A1-1). Therefore, the above method can also be called a method for producing the composition of the above embodiment.

[0110] The mixed liquid may contain a diol (D) and / or an oxetane compound (F) as an optional component. Even when the above method is a method in which at least one of the polycarbonate polyol (B) and the polyester polyol (C) contains a group represented by the above formula (I), the mixed liquid may contain a polyhydric alcohol (E) as an optional component. The details of the polycarbonate polyol (B), the polyester polyol (C), the diol (D), the polyhydric alcohol (E) and the oxetane compound (F) are as described above, and preferred examples thereof (preferred R 1 , R 2 , R 3 , R 4 Examples of R and R, and examples of preferred combinations) also refer to R 1 , R 2 , R 3 , R 4 These are the same as the preferred examples and preferred combinations of R and R. As the transesterification catalyst, it is preferable to use lithium acetylacetonate, from the viewpoint of facilitating the production of the desired compound (A1-1).

[0111] The mixing ratio of the polycarbonate polyol (B) and the polyester polyol (C) (content of the polycarbonate polyol (B) in the mixed solution / content of the polyester polyol (C) in the mixed solution) is preferably 95 / 5 to 5 / 95 by weight, more preferably 90 / 10 to 10 / 90, further preferably 80 / 20 to 20 / 80, and particularly preferably 70 / 30 to 30 / 70. By setting the mixing ratio of the polycarbonate polyol (B) and the polyester polyol (C) in the above range, the compound (A-1) can be efficiently obtained.

[0112] The mixing ratio of the polycarbonate polyol (B) to the polyester polyol (β) and / or polyester polyol (β') (content of the polycarbonate polyol (B) in the mixed solution / content of the polyester polyol (β) and / or polyester polyol (β') in the mixed solution) is preferably 95 / 5 to 5 / 95 by weight, more preferably 90 / 10 to 10 / 90, further preferably 80 / 20 to 20 / 80, and particularly preferably 70 / 30 to 30 / 70. By setting the mixing ratio of the polycarbonate polyol (B) to the polyester polyol (β) and / or polyester polyol (β') in the above range, the compound (A-1) can be efficiently obtained.

[0113] The content of the transesterification catalyst in the mixed solution may be 0.0001 to 0.1 parts by mass, 0.001 to 0.050 parts by mass, or 0.005 to 0.01 parts by mass relative to 100 parts by mass of the total amount of the polyol components in the mixed solution, from the viewpoint of easily controlling the reaction temperature and suppressing an increase in the color number of the reaction product. The content of the transesterification catalyst is preferably as small as possible from the viewpoint of easily controlling the reactivity of the urethanization reaction. When the content of the transesterification catalyst is increased, the reactivity of the urethanization reaction tends to be high. The content of the transesterification catalyst in the mixed solution is preferably 0.001 parts by mass or more, more preferably 0.002 parts by mass or more, and even more preferably 0.003 parts by mass or more relative to 100 parts by mass of the total amount of the polyol components in the mixed solution, from the viewpoint of easily controlling the urethanization reaction. From the viewpoint of suppressing an increase in the color number of the reaction product, the content of the transesterification catalyst in the mixed liquid is preferably 0.050 parts by mass or less, more preferably 0.040 parts by mass or less, and even more preferably 0.030 parts by mass or less, relative to 100 parts by mass of the total amount of the polyol components in the mixed liquid. From these viewpoints, the content of the transesterification catalyst in the mixed liquid is preferably 0.001 to 0.050 parts by mass, more preferably 0.002 to 0.040 parts by mass, and even more preferably 0.003 to 0.030 parts by mass, relative to 100 parts by mass of the total amount of the polyol components in the mixed liquid. The total amount of the polyol components is the total amount of the compounds having two or more hydroxyl groups (for example, polycarbonate polyol (B), polyester polyol (C), polyhydric alcohol (E), and optional diol (D)) contained in the mixed liquid and the optional oxetane compound (F).

[0114] In the reaction step, the mixture may be heated to proceed with the reaction, or may be allowed to proceed without heating. The reaction temperature of the mixture is, for example, 0 to 250°C, and may be 100 to 220°C. When the reaction temperature is 0°C or higher, the transesterification reaction is likely to proceed, and the desired compound (A1-1) is likely to be obtained. When the reaction temperature is 250°C or lower, the color number of the obtained compound (A1-1) and composition (polyol-containing composition) is suppressed. Furthermore, when the reaction temperature is 250°C or lower, the oxetane compound and / or oxetane structure derived from a polyhydric alcohol having three or more functional groups, which is by-produced by the decarboxylation reaction of carbonate groups or the dehydration reaction between terminal hydroxyl groups, can be suppressed. In addition, the transesterification reaction may be carried out at a constant temperature, or may be carried out while increasing the temperature stepwise or continuously depending on the degree of reaction progress. From the viewpoint of facilitating the production of the desired compound (A1-1), it is preferable to carry out heating at a temperature T1 that satisfies the relationship of the following formula (α), and then to carry out heating at a temperature T2 that satisfies the relationship of the following formula (β). It is preferable that the temperatures T1 and T2 satisfy the relationship of the following formula (γ). In addition, the average temperature T1 of the first heating m and the average temperature T2 of the second heating temperature m It is preferable that the relationship of the following formula (δ) is satisfied: Here, the reaction progress can be estimated from the consumption amount of the raw material obtained from the GPC chart. 180℃≦T1≦200℃ (α) 190℃≦T2≦200℃ (β) T1 <T2 ···(γ) T1 m <T2 m (δ)

[0115] The mixture can be heated under normal pressure, but can also be heated under reduced pressure (for example, under a pressure of 101 to 1 kPa). This makes it possible to remove moisture remaining in the mixture, accelerate the progress of the reaction, and suppress coloration of the composition. Furthermore, the reduced pressure makes it possible to reduce the acid value of the composition. In this specification, normal pressure means a pressure of 101.325 kPa ± 20.000 kPa. From the viewpoint of facilitating the production of the desired compound (A1-1), the heating of the mixture preferably includes heating under a pressure of 101.325 kPa±20.000 kPa (first heating) and then heating under a reduced pressure of 20.000 kPa or less (second heating), and it is more preferable that the temperature of the first heating is a temperature T1 that satisfies the relationship of the above formula (α), and the temperature of the second heating is a temperature T2 that satisfies the relationship of the above formula (β), and it is even more preferable that the temperature of the first heating (temperature T1) and the temperature of the second heating (temperature T2) satisfy the relationship of the above formula (γ).

[0116] The mixture can be heated while flowing in nitrogen. This makes it possible to remove moisture from the mixture and accelerate the progress of the reaction. Furthermore, purging with nitrogen makes it possible to suppress coloration of the composition. From the viewpoint of facilitating the production of the desired compound (A1-1), the nitrogen flow rate of the mixture is preferably 2 to 1000 ml / min / scale (kg), and more preferably 5 to 200 ml / min / scale (kg).

[0117] In the above-mentioned production method, the obtained reaction mixture may be subjected to post-treatment such as distillation, drying, etc. In addition, in the above-mentioned production method, after obtaining the compound (A1-1) or a composition containing the same, components such as the polyhydric alcohol (E) and / or the oxetane compound (F) may be added to prepare the compound.

[0118] <Urethane resin and its manufacturing method> The urethane resin is a polycondensate of a polyol component and a polyisocyanate component, or a crosslinked product thereof. Here, the crosslinked product means a product in which polycondensates are crosslinked with each other by a chain extender or the like.

[0119] (Polyol component) The polyol component includes the compound (A1-1). The polyol component may include a polyol (a compound having two or more terminal hydroxyl groups) other than the compound (A1-1), or an oxetane compound (F) (a compound having one hydroxyl group). The polyol component may further include, for example, a polyol that may be included in the composition (compound (A1-2), compound (A1-3), compound (A2-2), compound (A2-3), compound (A-3), compound (A-4), polyhydric alcohol (E), diol (D), oxetane compound (F), etc.). The content ratio of these polyols is determined by the content ratio of the polyol in the composition (for example, the molar ratio (C A1-1 / (C A1-1 +C A1-2 +C A1-3 ) × 100), molar ratio ((C A2-2 +C A2-3 ) / (C A1-1 +C A1-2 +C A1-3 )), molar ratio (C A1-1 / C T ), molar ratio (C A1-2 / C T ), molar ratio (C A1-3 / C T ), molar ratio (C A2-3 / C T ), molar ratio (C A2-3 / (C A2-2 +C A2-3 +C D ) × 100), molar ratio ((C A2-2 +C A2-3 ) / (C A2-2 +C A2-3 +C D ) × 100) and molar ratio (C F / C T × 100). In other words, the polyol component may contain a polyol mixture obtained by excluding compounds other than the polyol from the above composition.

[0120] The polyol component may further contain a polyol having an acidic group. In this case, the urethane resin contains an acidic group. The urethane resin having an acidic group is preferably used in an aqueous urethane resin dispersion. The aqueous urethane resin dispersion will be described later.

[0121] The acidic group is, for example, a functional group (hydrophilic group) that can impart hydrophilicity to the isocyanate-terminated prepolymer obtained by reaction with isocyanate. Examples of polyols having such acidic groups include dimethylolalkanoic acids such as dimethylolpropionic acid (DMPA), dimethylolbutanoic acid (DMBA), dimethylolpentanoic acid, and dimethylolnonanoic acid.

[0122] (Polyisocyanate component) Examples of the polyisocyanate component include aromatic polyisocyanates, araliphatic polyisocyanates, aliphatic polyisocyanates, and alicyclic polyisocyanates. Modified polyisocyanates, which are modified versions of these, can also be used. Examples of modified polyisocyanates include isocyanurate-modified polyisocyanates (isocyanate trimers), allophanate-modified polyisocyanates, uretdione-modified polyisocyanates, urethane-modified polyisocyanates, biuret-modified polyisocyanates, uretonimine-modified polyisocyanates, and acylurea-modified polyisocyanates. These can be used alone or in combination of two or more.

[0123] Examples of aromatic isocyanates include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, a mixture of 2,4-tolylene diisocyanate and 2,6-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, a mixture of 2,4'-diphenylmethane diisocyanate and 4,4'-diphenylmethane diisocyanate, m-xylylene diisocyanate, p-xylylene diisocyanate, and 4,4'-diphenyl ether. Examples of the diisocyanates include phenyl diisocyanate, 2-nitrodiphenyl-4,4'-diisocyanate, 2,2'-diphenylpropane-4,4'-diisocyanate, 3,3'-dimethyldiphenylmethane-4,4'-diisocyanate, 4,4'-diphenylpropane diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate, naphthylene-1,4-diisocyanate, naphthylene-1,5-diisocyanate, and 3,3'-dimethoxydiphenyl-4,4'-diisocyanate.

[0124] Examples of aromatic aliphatic isocyanates include 1,3-xylylene diisocyanate, 1,4-xylylene diisocyanate, and mixtures thereof; 1,3-bis(1-isocyanato-1-methylethyl)benzene, 1,4-bis(1-isocyanato-1-methylethyl)benzene, and mixtures thereof; ω,ω'-diisocyanato-1,4-diethylbenzene, and the like.

[0125] Examples of aliphatic isocyanates include hexamethylene diisocyanate, pentamethylene diisocyanate, tetramethylene diisocyanate, 2-methylpentane-1,5-diisocyanate, 3-methylpentane-1,5-diisocyanate, lysine diisocyanate, trioxyethylene diisocyanate, ethylene diisocyanate, trimethylene diisocyanate, octamethylene diisocyanate, nonamethylene diisocyanate, 2,2'-dimethylpentane diisocyanate, 2,2,4-trimethylhexane diisocyanate, decamethylene diisocyanate, butene diisocyanate, 1,3-butadiene-1,4-diisocyanate, 2,4,4 -trimethylhexamethylene diisocyanate, 1,6,11-undecane triisocyanate, 1,3,6-hexamethylene triisocyanate, 1,8-diisocyanato-4-(isocyanatomethyl)octane, 2,5,7-trimethyl-1,8-diisocyanato-5-(isocyanatomethyl)octane, bis(isocyanatoethyl)carbonate, bis(isocyanatoethyl)ether, 1,4-butylene glycol dipropyl ether-α,α'-diisocyanate, lysine diisocyanatomethyl ester, 2-isocyanatoethyl-2,6-diisocyanatohexanoate, 2-isocyanatopropyl-2,6-diisocyanatohexanoate, and the like.

[0126] Examples of alicyclic isocyanates include isophorone diisocyanate, cyclohexyl diisocyanate, bis(isocyanatomethyl)cyclohexane, dicyclohexylmethane diisocyanate, methylcyclohexyl diisocyanate, dicyclohexyldimethylmethane diisocyanate, 2,2'-dimethyldicyclohexylmethane diisocyanate, bis(4-isocyanato-n-butylidene)pentaerythritol, and hydrogenated dimer acid diisocyanate. 2-isocyanatomethyl-3-(3-isocyanatopropyl)-5-(isocyanatomethyl)bicyclo[2.2.1]heptane, 2-(isocyanatomethyl)3-(3-isocyanatopropyl)-6-(isocyanatomethyl)-bicyclo[2.2.1]heptane, 2-(isocyanatomethyl)-2-(3-isocyanatopropyl)-5-(isocyanatomethyl)bicyclo[2.2.1]heptane, 2-(isocyanatomethyl)-2-(3-isocyanatopropyl)-5-(isocyanatomethyl)bicyclo[2.2.1]heptane, 2-(isocyanatomethyl)-2-(3-isocyanatopropyl)- 2-(isocyanatomethyl)-3-(3-isocyanatopropyl)-5-(2-isocyanatoethyl)bicyclo[2.2.1]heptane, 2-(isocyanatomethyl)-3-(3-isocyanatopropyl)-6-(2-isocyanatoethyl)bicyclo[2.2.1]heptane, 2-(isocyanatomethyl)-2-(3-isocyanatopropyl)-5-(2-isocyanatoethyl)bicyclo[2.2.1]heptane, Examples of such diisocyanates include cyclo[2.2.1]heptane, 2-(isocyanatomethyl)-2-(3-isocyanatopropyl)-6-(2-isocyanatoethyl)bicyclo[2.2.1]heptane, 2,5-bis(isocyanatomethyl)bicyclo[2.2.1]heptane, hydrogenated diphenylmethane diisocyanate, norbornane diisocyanate, hydrogenated tolylene diisocyanate, hydrogenated xylene diisocyanate, and hydrogenated tetramethylxylene diisocyanate.

[0127] (Polyol component / polyisocyanate component blend ratio) The blending ratio of the polyol component to the polyisocyanate component, expressed as the molar ratio of active hydrogen in the polyol component to isocyanate groups in the polyisocyanate component, is preferably 9:1 to 1:9, and more preferably 6:4 to 4:6. When the blending ratio is within this range, the urethane resin tends to have better performance.

[0128] (Chain extender) The chain extender can be appropriately selected depending on the purpose, use, etc. Examples of the chain extender include water, ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, 1,10-decanediol, 1,1-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, tricyclodecane dimethanol, xylylene glycol, bis(p-hydroxy)diphenyl, bis(p-hydroxyphenyl)propane, 2,2-bis[4-(2-hydroxyethoxy)phenyl]propane, and bis[4-(2-hydroxyethoxy)phenyl]sulfone. , 1,1-bis[4-(2-hydroxyethoxy)phenyl]cyclohexane and other low molecular weight polyols; polyester polyols, polyesteramide polyols, polyether polyols, polyether ester polyols, polycarbonate polyols, polyolefin polyols and other high molecular weight polyols; ethylene diamine, isophorone diamine, 2-methyl-1,5-pentanediamine, aminoethylethanolamine, diethylene triamine, triethylene tetramine, tetraethylene pentamine, pentaethylene hexamine and other polyamines can be used. The amount of the chain extender (the ratio of the structure derived from the chain extender contained in the urethane resin) may be 0.1 to 50 parts by mass relative to 100 parts by mass of the total amount of the polyol component and the polyisocyanate component. When the chain extender is a polyol, the content of the polyol is calculated assuming that it is included in both the chain extender and the polyol component.

[0129] The urethane resin can be obtained by reacting a polyol component, a polyisocyanate component, and optionally a chain extender (urethanization reaction). The urethane reaction may be carried out at room temperature (e.g., 25°C) or under heating (e.g., 40 to 200°C).

[0130] In the urethanization reaction, a catalyst (urethanization catalyst) can be added for the purpose of shortening the reaction time, improving the reaction rate, etc. Examples of the catalyst include tertiary amine catalysts such as triethylamine, triethylenediamine, tetramethylethylenediamine, tetramethylpropylenediamine, and tetramethylhexamethylenediamine, and metal catalysts such as tin-based catalysts such as stannous octoate, stannous oleate, and dibutyltin dilaurate. These can be used alone or in combination of two or more. Among these, dibutyltin dilaurate is preferably used. The amount of the catalyst used may be 0.001 to 100 parts by mass with respect to 100 parts by mass of the total amount of the polyol component and the polyisocyanate component.

[0131] When a catalyst is used in the urethanization reaction, it is preferable to use a phosphorus compound for treating the catalyst. The phosphorus compound is not particularly limited, and examples thereof include phosphate triesters such as trimethyl phosphate, triethyl phosphate, tributyl phosphate, di-2-ethylhexyl phosphate, triphenyl phosphate, tricresyl phosphate, and cresyl diphenyl phosphate; acid phosphate esters such as methyl acid phosphate, ethyl acid phosphate, propyl acid phosphate, isopropyl acid phosphate, butyl acid phosphate, lauryl acid phosphate, stearyl acid phosphate, 2-ethylhexyl acid phosphate, isodecyl acid phosphate, butoxyethyl acid phosphate, oleyl acid phosphate, tetracosyl acid phosphate, acetylene glycol acid phosphate, 2-hydroxyethyl methacrylate acid phosphate, dibutyl phosphate, monobutyl phosphate, monoisodecyl phosphate, and bis(2-ethylhexyl)phosphate; and triphenyl phosphate. phosphite, trisnonylphenyl phosphite, tricresyl phosphite, triethyl phosphite, tris(2-ethylhexyl) phosphite, tridecyl phosphite, trilauryl phosphite, tris(tridecyl) phosphite, trioleyl phosphite, diphenyl mono(2-ethylhexyl) phosphite, diphenyl monodecyl phosphite, diphenyl (monodecyl) phosphite, trilauryl phosphite, diethyl hydrogen phosphite, bis(2-ethylhexyl) Examples of such phosphite esters include bis(decyl)pentaerythritol diphosphite, tristearyl phosphite, distearyl pentaerythritol diphosphite, tris(2,4-di-tert-butylphenyl)phosphite, and other phosphite esters; phosphoric acid, phosphorous acid, and hypophosphorous acid. These may be used alone or in combination of two or more.Among these, acidic phosphoric acid esters are preferred, and 2-ethylhexyl acid phosphate is more preferred. The amount of the phosphorus compound used may be 10 to 2000 parts by mass based on 100 parts by mass of the catalyst.

[0132] The urethanization reaction can be carried out in the presence of a solvent. Examples of the solvent include esters such as ethyl acetate, butyl acetate, propyl acetate, γ-butyrolactone, δ-valerolactone, and ε-caprolactone; amides such as dimethylformamide, diethylformamide, and dimethylacetamide; sulfoxides such as dimethylsulfoxide; ethers such as tetrahydrofuran, dioxane, and 2-ethoxyethanol; ketones such as methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; and aromatic hydrocarbons such as benzene and toluene.

[0133] The urethane resin described above has good elongation and texture, excellent durability, and in some cases good breaking strength. Therefore, the urethane resin can be suitably used for synthetic leather, artificial leather, coating agents, etc.

[0134] <Coating agent> The coating agent of the present embodiment contains the above-mentioned urethane resin. Specific aspects of the urethane resin may be as described above.

[0135] One example of its use as a coating agent is the in-mold coating method that applies RIM (Reaction Injection Molding). Specifically, this method involves molding a plastic substrate inside an injection mold, and then forming a urethane coating on the surface of the molded product inside the mold. With this method, the internal volume of the mold is constant, and not only are the density, thickness, and hardness of the urethane coating stable, but it is also possible to faithfully reproduce the irregularities on the mold surface, resulting in a highly aesthetically pleasing appearance.

[0136] <Water-based urethane resin dispersion> The aqueous urethane resin dispersion contains an aqueous medium and a urethane resin or a neutralized product thereof dispersed in the aqueous medium. The urethane resin is one of the above-mentioned urethane resins having an acidic group (a polyol component containing a polyol having an acidic group).

[0137] As the aqueous medium, in addition to water, a solution containing an emulsifier, a dispersant, etc. can be used. The aqueous medium preferably contains water, and more preferably consists of only water.

[0138] When the aqueous urethane resin dispersion contains a neutralized product of the urethane resin, the acidic group of the urethane resin may be neutralized by a neutralizing agent. Examples of the neutralizing agent include organic amines such as ammonia, ethylamine, trimethylamine, triethylamine, triisopropylamine, tributylamine, triethanolamine, N-methyldiethanolamine, N-phenyldiethanolamine, monoethanolamine, dimethylethanolamine, diethylethanolamine, morpholine, N-methylmorpholine, 2-amino-2-ethyl-1-propanol, and higher alkyl-modified morpholine, alkali metals such as lithium, potassium, and sodium, and inorganic alkalis such as sodium hydroxide and potassium hydroxide. From the viewpoint of improving the durability and smoothness of the coating film, a highly volatile neutralizing agent that is easily dissociated by heating, such as ammonia, trimethylamine, and triethylamine, is preferably used. These neutralizing agents can be used alone or in combination of two or more.

[0139] In producing the aqueous urethane resin dispersion, an anionic polar group-containing compound can also be used. Examples of the anionic polar group-containing compound include those consisting of an organic acid having one or more active hydrogens and a neutralizing agent. Examples of the organic acid include carboxylates, sulfonates, phosphates, phosphonates, phosphinates, and thiosulfonates. These anionic polar groups contained in the organic acid may be introduced alone or may be associated with metal ions such as chelates.

[0140] In producing the aqueous urethane resin dispersion, a cationic polar group-containing compound can also be used. The cationic polar group-containing compound is, for example, a tertiary amine having one or more active hydrogens, and one selected from the group consisting of a neutralizer for inorganic acid, a neutralizer for organic acid, and a quaternizing agent. In addition, the cationic polar group-containing compound can also be a cationic compound such as a primary amine salt, a secondary amine salt, a tertiary amine salt, or a pyridinium salt.

[0141] Examples of tertiary amines having one or more active hydrogens include N,N-dimethylethanolamine, N,N-diethylethanolamine, N,N-dipropylethanolamine, N,N-diphenylethanolamine, N-methyl-N-ethylethanolamine, N-methyl-N-phenylethanolamine, N,N-dimethylpropanolamine, N-methyl-N-ethylpropanolamine, N-methyldiethanolamine, N-ethyldiethanolamine, N-methyldipropanolamine, N-phenyldiethanolamine, N-phenyldipropanolamine, N-hydroxyethyl-N-hydroxypropyl-methylamine, N,N'-dihydroxyethylpiperazine, triethanolamine, trisisopropanolamine, N-methyl-bis-(3-aminopropyl)-amine, N-methyl-bis-(2-aminopropyl)-amine, etc. Also usable are primary amines such as ammonia and methylamine, or secondary amines such as dimethylamine to which alkylene oxide is added.

[0142] Inorganic and organic acids include, for example, hydrochloric acid, acetic acid, lactic acid, cyanoacetic acid, phosphoric acid, and sulfuric acid.

[0143] Examples of the quaternizing agent include dimethyl sulfate, benzyl chloride, bromoacetamide, chloroacetamide, etc. Also usable are alkyl halides such as ethyl bromide, propyl bromide, and butyl bromide.

[0144] The aqueous urethane resin dispersion can be produced, for example, by sequentially carrying out the steps of reacting a polyol component containing a polyol having an acidic group with a polyisocyanate component in the presence or absence of a solvent to form a urethane prepolymer, neutralizing the acidic groups in the prepolymer with a neutralizing agent, dispersing the neutralized prepolymer in an aqueous medium, and reacting the prepolymer dispersed in the aqueous medium with a chain extender. In each step, a catalyst can be used as necessary to promote the reaction and control the amount of by-products.

[0145] A film formed by the aqueous urethane resin dispersion described above (for example, a film formed by coating the aqueous urethane resin dispersion on a substrate) is excellent in adhesion, flexibility, touch, etc. Therefore, the aqueous urethane resin dispersion can be suitably used for artificial leather, synthetic leather, and coating agents.

[0146] <Two-liquid composition set> The polyol component and the polyisocyanate component for forming the urethane resin may be stored, transported, etc., in separate containers as a two-liquid composition set. The two-liquid composition set includes a first liquid containing at least the polyol component and a second liquid containing at least the polyisocyanate component. When a chain extender, a catalyst, a solvent, etc. are used, they may be contained in the first liquid and / or the second liquid, or may be mixed separately from the first liquid and the second liquid. The two-liquid composition set can be suitably used, for example, as a coating agent, and can also be suitably used in the production of artificial leather, synthetic leather, etc. When the two-liquid composition set is used as a coating agent, for example, after mixing the first liquid and the second liquid, the resulting mixed liquid is applied to a substrate, and optionally heated to form a coating film (for example, a cured film containing a urethane resin).

[0147] As an example of the use of the two-liquid composition set as a coating agent, the set can be suitably used as a resin composition that does not use organic solvents in the production of artificial leather, synthetic leather, etc., and forms a polyurethane resin that has excellent adhesion, flexibility, touch, etc.

[0148] The urethane resin-forming composition containing the above-mentioned polyol component and the above-mentioned polyisocyanate component, and the polyurethane resin composition containing the above-mentioned urethane resin are preferably used as an aqueous polyurethane resin emulsion, a polyurethane resin synthesized without a solvent, or a precursor thereof. Then, by curing this aqueous polyurethane resin emulsion or the polyurethane resin synthesized without a solvent, a molded product such as a coating film or a film that is tough, has a reduced 100% modulus (good texture), and has a high softening temperature can be obtained, and can be suitably used for leather applications such as artificial leather and synthetic leather, or as a surface treatment agent for leather. The 100% modulus is one of the indicators that quantify the moist, elastic, and luxurious feeling when touching synthetic leather, and when the value is within a certain numerical range, the urethane resin has good properties.

[0149] <Application> The composition, urethane resin, aqueous urethane resin dispersion, and coating agent of the present embodiment described above can be used in a coating composition that is preferably used as a clear coating for automobile exteriors and a coating for automobile interiors. The composition, urethane resin, aqueous urethane resin dispersion, and coating agent of the present embodiment can also be preferably used in surface treatment of home appliances, OA (office automation) products, leather, and synthetic leather. EXAMPLES

[0150] Examples of the present invention will be described below, but the present invention is not limited to these examples.

[0151] [Synthesis Example 1: Synthesis of polycarbonate polyol (B) 1] 826g of 1,6-hexanediol, 787g of diethyl carbonate, and 0.05g of tetrabutyl titanate were mixed in a 2L two-necked glass reactor equipped with a stirrer, thermometer, heater, and cooler, and reacted at 100-190°C for 8 hours under normal pressure while removing low boiling point components. The reaction temperature was then increased to 190°C, the pressure in the flask was reduced to 1 kPa, and the reaction was continued for another 8 hours to obtain a polycarbonate polyol (PC-1).

[0152] [Synthesis Example 2: Synthesis of polycarbonate polyol (B) 2] 272.7g of trimethylolpropane, 266.2g of 1,6-hexanediol, 461.2g of diethyl carbonate, and 0.05g of potassium hydrogen carbonate were mixed in a 1L two-neck glass reactor equipped with a stirrer, thermometer, heater, and cooler, and reacted at 100-150°C for 8 hours under normal pressure while removing low boiling point components. The reaction temperature was then increased to 150°C, the pressure in the flask was reduced to 1 kPa, and the reaction was continued for another 8 hours to obtain a polycarbonate polyol (PC-2).

[0153] [Synthesis Example 3: Synthesis of polycarbonate polyol (B) 3] 174.1g of 1,4-butanediol, 225.9g of diethyl carbonate, and 0.02g of tetrabutyl titanate were mixed in a 2L two-necked glass reactor equipped with a stirrer, thermometer, heater, and cooler, and reacted at 100-190°C for 8 hours under normal pressure while removing low boiling point components. The reaction temperature was then increased to 190°C, the pressure in the flask was reduced to 1 kPa, and the reaction was continued for another 8 hours to obtain a polycarbonate polyol (PC-3).

[0154] [Synthesis Example 4: Synthesis of polycarbonate polyol (B) 4] 202.6g of 3-methyl-1,5-pentanediol, 197.5g of diethyl carbonate, and 0.02g of tetrabutyl titanate were mixed in a 2L two-necked glass reactor equipped with a stirrer, thermometer, heater, and cooler, and reacted at 100 to 190°C for 8 hours under normal pressure while removing low boiling point components. The reaction temperature was then increased to 190°C, the pressure in the flask was reduced to 1 kPa, and the reaction was continued for another 8 hours to obtain a polycarbonate polyol (PC-4).

[0155] <Example> Example 1 322g of N-980N, 140g of Plaxel 220, 13g of Plaxel 305, 24.6g of 1,6-hexanediol (HG), and 0.05g of lithium acetylacetonate were mixed in a 0.5L four-neck glass reactor (reactor A) equipped with a stirrer, thermometer, heater, and cooler. The mixture was heated at 180-200°C (initial 180°C, final 200°C) under normal pressure and reacted for 5 hours at a flow rate of 50ml / min under a nitrogen atmosphere. Furthermore, the pressure in the flask was reduced to 26.7kPa at a reaction temperature of 200°C, and the reaction was continued for another 5 hours to obtain a composition (PCP-1) containing polycarbonate polyol represented by the above formula (A1-1).

[0156] Example 2 A composition (PCP-2) containing the polycarbonate polyol represented by the above formula (A1-1) was obtained in the same manner as in Example 1, except that a mixed solution obtained by mixing 319 g of N-980N, 111 g of PLACCEL 220, 51 g of PLACCEL 305, 18.3 g of 1,6-hexanediol, and 0.05 g of lithium acetylacetonate was used in the reactor A.

[0157] Example 3 A composition (PCP-3) containing the polycarbonate polyol represented by the above formula (A1-1) was obtained in the same manner as in Example 1, except that a mixed liquid obtained by mixing 153 g of the polycarbonate polyol (PC-1) obtained in Synthesis Example 1, 259 g of N-980N, 66 g of Plaxel 305, 21.8 g of trimethylolpropane (TMP), and 0.05 g of lithium acetylacetonate was used in the reactor A.

[0158] Example 4 A composition (PCP-4) containing the polycarbonate polyol represented by the above formula (A1-1) was obtained in the same manner as in Example 1, except that a mixed solution obtained by mixing 3.0 g of the polycarbonate polyol (PC-1) obtained in Synthesis Example 1, 359 g of N-980N, 132 g of PLACCEL 305, 5.6 g of trimethylolpropane, and 0.05 g of lithium acetylacetonate was used in the reactor A.

[0159] Example 5 A composition (PCP-5) containing the polycarbonate polyol represented by the above formula (A1-1) was obtained in the same manner as in Example 1, except that a mixed solution obtained by mixing 300 g of the polycarbonate polyol (PC-1) obtained in Synthesis Example 1, 200 g of PLACCEL 305, and 0.05 g of lithium acetylacetonate was used in the reactor A.

[0160] Example 6 A composition (PCP-6) containing the polycarbonate polyol represented by the above formula (A1-1) was obtained in the same manner as in Example 1, except that a mixed solution obtained by mixing 212 g of N-980N, 149 g of PLACCEL 220, 134 g of PLACCEL 305, 5.3 g of trimethylolpropane, and 0.05 g of lithium acetylacetonate was used in the reactor A.

[0161] Example 7 A composition (PCP-7) containing the polycarbonate polyol represented by the above formula (A1-1) was obtained in the same manner as in Example 1, except that a mixed solution obtained by mixing 112 g of N-980N, 249 g of PLACCEL 220, 134 g of PLACCEL 305, 5.3 g of trimethylolpropane, and 0.05 g of lithium acetylacetonate was used in reactor A.

[0162] Example 8 A composition (PCP-8) containing the polycarbonate polyol represented by the above formula (A1-1) was obtained in the same manner as in Example 1, except that a mixed solution obtained by mixing 12 g of N-980N, 349 g of PLACCEL 220, 134 g of PLACCEL 305, 5.3 g of trimethylolpropane, and 0.05 g of lithium acetylacetonate was used in reactor A.

[0163] Example 9 A composition (PCP-9) containing the polycarbonate polyol represented by the above formula (A1-1) was obtained in the same manner as in Example 1, except that a mixed solution obtained by mixing 348 g of the polycarbonate polyol (PC-1) obtained in Synthesis Example 1, 47 g of N-980N, 98 g of PLACCEL 210, 6.9 g of PLACCEL 305, and 0.05 g of lithium acetylacetonate was used in the reactor A.

[0164] Example 10 A composition (PCP-10) containing the polycarbonate polyol represented by the above formula (A1-1) was obtained in the same manner as in Example 1, except that a mixed solution obtained by mixing 450 g of N-980N, 50 g of Plaxel 320, and 0.05 g of lithium acetylacetonate was used in the reactor A.

[0165] Example 11 A composition (PCP-11) containing the polycarbonate polyol represented by the above formula (A1-1) was obtained in the same manner as in Example 1, except that a mixed solution obtained by mixing 400 g of N-980N, 100 g of Plaxel 320, and 0.05 g of lithium acetylacetonate was used in the reactor A.

[0166] Example 12 A composition (PCP-12) containing the polycarbonate polyol represented by the above formula (A1-1) was obtained in the same manner as in Example 1, except that a mixed solution obtained by mixing 1356 g of the polycarbonate polyol (PC-1) obtained in Synthesis Example 1, 472 g of PLACCEL 210, 171 g of PLACCEL 305, and 0.20 g of lithium acetylacetonate was used in a 2 L four-neck glass reactor equipped with a stirrer, a thermometer, a heating device, and a cooler as the reactor A.

[0167] (Example 13) A composition (PCP-13) containing the polycarbonate polyol represented by the above formula (A1-1) was obtained in the same manner as in Example 1, except that a mixed solution obtained by mixing 250 g of the polycarbonate polyol (PC-1) obtained in Synthesis Example 1, 250 g of Plaxel 320, and 0.05 g of lithium acetylacetonate was used in the reactor A.

[0168] Example 14 A composition (PCP-14) containing the polycarbonate polyol represented by the above formula (A1-1) was obtained in the same manner as in Example 1, except that a mixed solution obtained by mixing 150 g of N-980N, 100 g of PLACCEL 220, 250 g of PLACCEL 320, and 0.05 g of lithium acetylacetonate was used in reactor A.

[0169] Example 15 A composition (PCP-15) containing the polycarbonate polyol represented by the above formula (A1-1) was obtained in the same manner as in Example 1, except that a mixed solution obtained by mixing 50 g of N-980N, 200 g of PLACCEL 220, 250 g of PLACCEL 320, and 0.05 g of lithium acetylacetonate was used in reactor A.

[0170] (Example 16) A composition (PCP-16) containing the polycarbonate polyol represented by the above formula (A1-1) was obtained in the same manner as in Example 1, except that a mixed solution obtained by mixing 250 g of N-980N, 250 g of Plaxel 320, and 0.05 g of lithium acetylacetonate was used in the reactor A.

[0171] (Example 17) In a reactor A, 90 g of the composition (PCP-13) obtained in Example 13 and 10 g of trimethylolpropane were mixed at 80°C to obtain a composition (PCP-17) containing the polycarbonate polyol represented by the above formula (A1-1).

[0172] (Example 18) A composition (PCP-18) containing the polycarbonate polyol represented by the above formula (A1-1) was obtained in the same manner as in Example 1, except that a mixed solution obtained by mixing 305 g of the polycarbonate polyol (PC-1) obtained in Synthesis Example 1, 45 g of the polycarbonate polyol (PC-2) obtained in Synthesis Example 2, 103 g of PLACCEL 220, 47 g of PLACCEL 210, and 0.05 g of lithium acetylacetonate was used in the reactor A.

[0173] (Example 19) A composition (PCP-19) containing the polycarbonate polyol represented by the above formula (A1-1) was obtained in the same manner as in Example 1, except that a mixed solution obtained by mixing 289 g of the polycarbonate polyol (PC-1) obtained in Synthesis Example 1, 126 g of the polycarbonate polyol (PC-2) obtained in Synthesis Example 2, 85 g of PLACCEL 220, and 0.05 g of lithium acetylacetonate was used in the reactor A.

[0174] (Example 20) A composition (PCP-20) containing the polycarbonate polyol represented by the above formula (A1-1) was obtained in the same manner as in Example 1, except that a mixed solution obtained by mixing 318 g of N-980N, 150 g of N-135, 32 g of trimethylolpropane, and 0.05 g of lithium acetylacetonate was used in the reactor A.

[0175] Example 21 A composition (PCP-21) containing the polycarbonate polyol represented by the above formula (A1-1) was obtained in the same manner as in Example 1, except that a mixed solution obtained by mixing 250 g of the polycarbonate polyol (PC-3) obtained in Synthesis Example 3, 250 g of Plaxel 320, and 0.05 g of lithium acetylacetonate was used in the reactor A.

[0176] Example 22 A composition (PCP-22) containing the polycarbonate polyol represented by the above formula (A1-1) was obtained in the same manner as in Example 1, except that a mixed solution obtained by mixing 250 g of the polycarbonate polyol (PC-4) obtained in Synthesis Example 4, 250 g of Plaxel 320, and 0.05 g of lithium acetylacetonate was used in the reactor A.

[0177] (Example 23) A composition (PCP-23) containing the polycarbonate polyol represented by the above formula (A1-1) was obtained in the same manner as in Example 1, except that a mixed solution obtained by mixing 250 g of N-980N, 250 g of Plaxel 320, 14.5 g of 3-ethyl-3-hydroxymethyloxetane, and 0.05 g of lithium acetylacetonate was used in the reactor A.

[0178] Comparative Example 1 50 g of N-982R and 50 g of trimethylolpropane were mixed at 80° C. to obtain a composition (PCD-1) containing polycarbonate diol.

[0179] Comparative Example 2 N-982R was heated to 80° C. to obtain a composition containing polycarbonate diol (PCD-2).

[0180] Comparative Example 3 N-980R was heated to 80° C. to obtain a composition containing polycarbonate diol (PCD-3).

[0181] Comparative Example 4 300 g of the polycarbonate polyol (PC-1) obtained in Synthesis Example 1, 200 g of Plaxel 305, and 0.05 g of tetrabutyl titanate were mixed in a reactor A. The mixture was heated at 190°C under normal pressure and reacted for 5 hours to obtain a composition (PCP-24) containing polycarbonate polyol.

[0182] Comparative Example 5 A composition (PCP-25) containing polycarbonate polyol was obtained in the same manner as in Comparative Example 4, except that a mixed solution obtained by mixing 300 g of the polycarbonate polyol (PC-1) obtained in Synthesis Example 1, 200 g of Plaxel 305, and 0.05 g of barium acetate was used in the reactor A.

[0183] (Analysis and Evaluation) [Measurement of number average molecular weight] The polycarbonate polyol obtained above and the composition obtained above were subjected to GPC analysis under the following conditions to measure the number average molecular weight of the polycarbonate polyol and the number average molecular weight of the composition. The results are shown in Tables 1, 3, 5 and 7. -conditions- (1) Measuring instrument: HLC-8420 (manufactured by Tosoh Corporation) (2) Column: TSKgel (Tosoh Corporation) G3000H-XL G3000H-XL G2000H-XL G2000H-XL (3) Mobile phase: THF (tetrahydrofuran) (4) Detector: RI (refractive index) detector (accessory for HLC-8420) (5) Temperature: 40℃ (6)Flow rate: 1.000ml / min (7) Calibration curve: A calibration curve was obtained using the following products (all bifunctional polyoxypropylene polyols manufactured by Sanyo Chemical Industries, Ltd.). "Sannix PP-200" (number average molecular weight = 200, average number of functional groups: 2) "Sannix PP-400" (number average molecular weight = 400, average number of functional groups: 2) "Sannix PP-1000" (number average molecular weight = 1000, average number of functional groups: 2) "Sannix PP-2000" (number average molecular weight = 2000, average number of functional groups: 2) "Sannix PP-3000" (number average molecular weight = 3200, average number of functional groups: 2) "Sannix PP-4000" (number average molecular weight = 4160, average number of functional groups: 2) (8) Approximation of calibration curve: Cubic equation (9) Sample solution concentration: 0.5% by mass in THF solution

[0184] [Hydroxyl value measurement] The hydroxyl value of the polycarbonate polyol obtained above and the hydroxyl value of the composition obtained above were measured by a method using an acetylation reagent in accordance with JIS K1557-1. The results are shown in Tables 1, 3, 5, and 7.

[0185] [Acid value measurement] The acid value of the composition obtained above was measured by a method using an acetylating agent in accordance with JIS K1557-5. The results are shown in Tables 3, 5, and 7.

[0186] [Characteristics evaluation] The composition obtained above was used as a sample, which was heated at 80°C for 1 hour and then left at 25°C for 3 days. The state of the sample after leaving it was visually confirmed, and if it had even a slight fluidity at the above temperature, it was classified as liquid, and if it had no fluidity, it was classified as solid. The results are shown in Tables 3, 5, and 7.

[0187] [Composition analysis] The composition was analyzed by the following procedure.

[0188] First, the composition (sample) obtained above was dissolved in deuterated chloroform (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) to obtain a solution. Tetramethylsilane (TMS) was added to the solution as a chemical shift standard to obtain a test solution. The obtained test solution was analyzed using JNM-ECX400 (manufactured by JEOL Ltd.). 1Measure H-NMR and set the TMS signal at 0 ppm. 1 For reference, the H-NMR spectrum of the composition obtained in Example 5 was 1 The H-NMR spectra are shown in Figures 1 and 2. The measurements were carried out under the following conditions. -conditions- ·Resonance frequency: 400MHz Pulse width: 45degree Waiting time: 5 seconds Number of times: 64 Sample solution concentration (TMS-containing deuterated chloroform): 3% by mass

[0189] Next, 1 From the H-NMR spectrum, the integral value Δ of the methylene signal (S1-1) located next to the hydroxyl group of the group represented by the above formula (a1-1) is S1-1 and the integral value Δ of the methylene signal (S1-2) located next to the hydroxyl group of the group represented by the above formula (a1-2) S1-2 and the integral value Δ of the methylene signal (S1-3) located next to the hydroxyl group of the group represented by the above formula (a1-3). S1-3 and the integral value Δ of the methylene signal (S2-2) located next to the hydroxyl group of the group represented by the above formula (a2-2) S2-2 and the integral value Δ of the methylene signal (S2-3) located next to the hydroxyl group of the group represented by the above formula (a2-3) S2-3 and the integral value Δ of the methylene signal (Sd) located next to the hydroxyl group of the group represented by the above formula (d). Sd and the integral value Δ of the methylene signal (Se) located next to the hydroxyl group of the group represented by the above formula (e). Se and the integral value Δ of the methylene signal (Sf) located next to the oxygen atom of the oxetane group of the group represented by the above formula (f'). Sf In addition, R of the group represented by formula (I) was calculated. 1 is a methyl group or an ethyl group, the integral values ​​of the terminal methyl signals are calculated and these are expressed as the integral value Δ SI It was decided.

[0190] Specifically, a signal from 3.435 ppm to 3.475 ppm is designated as signal (S1-1), a signal from 3.475 ppm to 3.520 ppm is designated as signal (S1-2), a signal from 3.400 ppm to 3.435 ppm is designated as signal (S1-3), a signal from 3.595 ppm to 3.618 ppm is designated as signal (S2-2), a signal from 3.550 ppm to 3.595 ppm is designated as signal (S2-3), a signal from 3.618 ppm to 3.710 ppm is designated as signal (Sd), a signal from 3.710 ppm to 3.760 ppm is designated as signal (Se), a signal from 4.390 ppm to 4.500 ppm is designated as signal (Sf), and a signal from 0.700 ppm to 1.130 ppm is designated as R of the group represented by formula (I). 1 is a methyl group (when the polyhydric alcohol (E) is trimethylolethane), and a signal between 0.700 ppm and 1.000 ppm is R of the group represented by formula (I). 1 is the signal (SI) when the polyhydric alcohol (E) is trimethylolpropane.

[0191] The baseline for the integral value measurement was a horizontal line drawn by comparing the spectral intensities in the specified spectral range and using the lowest spectral intensity as the reference. Signals (S1-1), (S1-2), (S2-2) and (Se) usually show single peaks, but may be affected by trace amounts of moisture and split into peaks. If a split peak is detected, it will deviate from the above integral range and an accurate C value cannot be obtained. A1-1 , C A1-2、 C A2-2 and C E Therefore, the integral value obtained from each signal is adopted when it shows a single peak.

[0192] From the integral obtained, the molar ratio (C A1-1 / (C A1-1 +C A1-2 +C A1-3) × 100), molar ratio ((C A2-2 +C A2-3 ) / (C A1-1 +C A1-2 +C A1-3 )), molar ratio (C A1-1 / C T ), molar ratio (C A1-2 / C T ), molar ratio (C A1-3 / C T ), molar ratio (C A2-3 / C T ), molar ratio (C A2-3 / (C A2-2 +C A2-3 +C D ) × 100), molar ratio ((C A2-2 +C A2-3 ) / (C A2-2 +C A2-3 +C D ) × 100) and molar ratio (C F / C T × 100) was calculated. The results are shown in Tables 3, 5 and 7.

[0193] In addition, the presence of the signal (S1-1) in PCP-1 to 23 suggested the presence of the compound (A1-1), whereas the signal (S1-1) was not observed in PCP-1 to 3 and PCP-24 to 25.

[0194] In addition, the total number of moles of groups in which all three bonds in formula (I) are bonds to a carbonyl group is represented by C A3 Then, C T is C A1-1 , C A1-2 , C A1-3、 C A2-2 , C A2-3 , C A3 , C E and C F In PCP-1 to 19, the integrals of the above signals (SI), (S1-1) to (S1-3), (S2-2) to (S2-3), (Se), and (Sf) give the following: C T From C A1-1 , C A1-2 , C A1-3、 C A2-2 , C A2-3 , C E and CF It was confirmed that the value obtained by subtracting 1 from 1 was positive, suggesting the presence of compound (A-3).

[0195] [Table 1]

[0196] [Table 2] [Table 3] [Table 4] [Table 5] [Table 6] [Table 7]

[0197] In Tables 2, 4, and 6, the "composition" (unit: g) of Examples 1 to 16, Examples 18 to 23, and Comparative Examples 4 to 5 indicates the reaction raw materials, and the "composition" (unit: g) of Example 17 and Comparative Examples 1 to 3 indicates the blended components.

[0198] (Physical property evaluation) A cured urethane coating (film) was prepared by the following method, and the physical properties (tensile properties, heat resistance, hot water resistance) of the obtained film were evaluated as a sample.

[0199] [Preparation of urethane hardened coating] First, the composition obtained above, a polyisocyanate component (C-2612), a urethane catalyst, a phosphorus compound (JP508), and a dilution solvent were mixed in a 200 mL glass bottle in the proportions (unit: g) shown in Tables 8, 9, and 10. Immediately after mixing, the mixed liquid was poured onto a release paper and cast into a film having a thickness of 200 μm using a bar coater. The cast film was then cured by heating under the conditions of 25° C. for 30 minutes, 50° C. for 30 minutes, 80° C. for 30 minutes, 120° C. for 1 hour, and 50° C. for 18 hours to obtain a urethane cured coating (film).

[0200] [100% tensile modulus evaluation] The tensile properties and 100% modulus properties of the obtained film were measured under the following conditions in accordance with JIS K6251. (100% modulus, strength at break, elongation at break) -conditions- Test equipment: Tensilon UTA-500 (manufactured by A&D) Measurement conditions: 25℃×50%RH Head speed: 200mm / min Dumbbell No. 4

[0201] [Softening temperature] A test piece was obtained from the obtained film using a dumbbell, a 2 cm mark was drawn on the test piece, and the thickness at the center of the mark was measured. A weight of a specified weight was attached to one grip of the test piece, and the other grip was clamped with a double clip, and the test piece was hung in a dryer with the clip on the upper side. The temperature inside the dryer was then increased and the distance between the marks was observed. The temperature at which the distance between the marks reached 4 cm was read as the softening temperature. Processing equipment: constant temperature blower dryer DRK633DA (manufactured by Advantec) Weight: thickness of center of gauge line (μm) x 0.05g Dumbbell No. 2 (JIS K6251 compliant) Heating rate: 5℃ / min

[0202] [Glass transition temperature] A test piece (width 0.4 cm, length 2.5 cm) was obtained from the obtained film using a dumbbell, and the thickness (approximately 100 to 200 μm) at the center of the gauge line was measured. The glass transition temperature was determined as the peak top temperature of the obtained loss modulus (E") / storage modulus (E') = tan δ. -conditions- Processing equipment: RHEOVIBRON DDV-01GP Dynamic Viscoelastomeret (manufactured by Orientec) Range: -50~40℃ Heating rate: 3℃ / min Frequency: 35Hz ·Amplitude: 16μm ·Static tension: 5.00gf

[0203] [Hot water resistance evaluation] The obtained film was left in a constant temperature incubator at 90°C for 28 days while immersed in water to prepare a test specimen. The appearance of each test specimen was then visually evaluated. An ESPEC CORP test device was used. The change in the appearance of the film after the test compared to the appearance before the test was evaluated as A, B, C, or D (A: no change, B: deformation, C: white, D: dissolution). If the polyurethane film is good, the film shape will be maintained even after the water resistance test. The water resistance test simultaneously promotes reorientation and decomposition of polyurethane. If there is any deformation in the appearance of the film after the water resistance test, it suggests that reorientation of polyurethane is progressing, and if reorientation progresses significantly, the film will whiten. In some cases, the film will also dissolve due to decomposition of carbonate bonds in the polyurethane.

[0204] [Evaluation Criteria] The physical properties of 100% modulus, breaking strength, breaking elongation, softening temperature, glass transition temperature, and hot water resistance (90°C water resistance) were rated as A, B, C, D, and E (A: very good, B: particularly good, C: good, D: average, E: poor). In addition, the overall rating was A, B, C, D, and E (A: very good, B: particularly good, C: good, D: average, E: poor). <100% modulus> A: 1.2MPa or more and 3.2MPa or less D: Less than 1.2MPa E: Over 3.2MPa <Breaking strength> A: Over 11MPa D: 11MPa or less <Elongation at break> A:300MPa or more B: Less than 300MPa <Softening temperature> A: Over 210℃ D: Above 190℃ and below 210℃ E: Less than 190℃ <Overall rating> A: Each physical property is rated A only B: The evaluation of each physical property does not include C, D, or E, but includes at least B. C: The evaluation of each physical property does not include D or E, but includes at least C. D: The evaluation of each physical property does not include E, but includes at least D. E: The evaluation of each physical property value includes E.

[0205] [Table 8] [Table 9] [Table 10]

[0206] Details of the materials used in the examples are as follows: 1,6-Hexanediol: BASF JAPAN 1,4-Butanediol: Tokyo Chemical Industry Co., Ltd. 3-Methyl-1,5-pentanediol: Fujifilm Wako Pure Chemical Industries, Ltd. Trimethylolpropane: Sigma-Aldrich Diethyl carbonate: Sigma-Aldrich Potassium bicarbonate: Fujifilm Wako Pure Chemical Industries, Ltd. Tetrabutyl titanate: Tokyo Chemical Industry Co., Ltd. N-980N, N-980R: Polycarbonate diol (number average molecular weight = 2000, hydroxyl value = 56.1, functionality = 2, 1,6-hexanediol-based polycarbonate diol) manufactured by Tosoh Corporation Plaxel 220: Polycaprolactone diol (number average molecular weight = 2000, hydroxyl value = 56.1, functionality = 2) manufactured by Daicel Corporation Plaxel 210: Polycaprolactone diol (number average molecular weight = 1000, hydroxyl value = 112, functionality = 2) manufactured by Daicel Corporation N-135: Polyester polyol (number average molecular weight = 2600, hydroxyl value = 43.1, functionality = 2, adipic acid / 1,4-butanediol polyester diol) manufactured by Tosoh Corporation Plaxel 320: Polycaprolactone triol (number average molecular weight = 2000, hydroxyl value = 84.2, functionality = 3) manufactured by Daicel Corporation Plaxel 305: Polycaprolactone triol (number average molecular weight = 550, hydroxyl value = 305, functionality = 3) manufactured by Daicel Corporation 3-Ethyl-3-hydroxymethyloxetane: manufactured by Tokyo Chemical Industry Co., Ltd. N-982R: Polycarbonate diol (number average molecular weight = 2000, hydroxyl value = 56.1, functionality = 2, 1,6-hexanediol / ester copolymer polycarbonate diol) manufactured by Tosoh Corporation Lithium acetylacetonate: Sigma-Aldrich Barium acetate: Fujifilm Wako Pure Chemical Industries, Ltd. JP-508: Product name, 2-ethylhexyl acid phosphate, manufactured by Johoku Chemical Industry Co., Ltd. C-2612: Coronate 2612 (trade name), hexamethylene diisocyanate adduct modified polyisocyanate, isocyanate content = 17.2%, manufactured by Tosoh Corporation DOTDL: Dioctyl + tin dilaurate, manufactured by Kishida Chemical Industry Co., Ltd. BYK-331: Silicone surface conditioner, manufactured by BYK Methyl ethyl ketone: Maruzen Petrochemical Co., Ltd. Toluene: Fujifilm Wako Pure Chemical Industries, Ltd.

Claims

1. A compound represented by the following formula (A1-1), A polycarbonate polyol represented by the following formula (A1-2), A composition containing a polyester polyol represented by the following formula (A1-3), Let C be the total number of moles of the group represented by the following formula (a1-1) contained in the above composition, Let C be the total number of moles of the group represented by the following formula (a1-2) contained in the above composition, If the total number of moles of the group represented by the following formula (a1-3) contained in the above composition is C A1-3, The molar ratio (C A1-1 / (C A1-1 + C A1-2 + C A1-3) × 100) is between 5.3 and 80. A composition having a hydroxyl group content of 30 to 200 mg KOH / g. 【Chemistry 1】 [In formula (A1-1), R1 represents a hydrogen atom, an alkyl group, or a hydroxyalkyl group. R2 represents an alkanediyl group. R3 represents an alkanediyl group, or *1-R a-C(=O)-O-R b-*2. R4 represents an alkanediyl group, *1-O-R c-*2, or *1-Ra a-C(=O)-O-R b-*2. Ra, Rb, and Rc each independently represent an alkanediyl group. *1 indicates the bonding site with the carbonyl group, and *2 indicates the bonding site with the oxygen atom. n1 and m1 each represent non-negative integers. If there are multiple instances of R4, they may be identical or different from one another. 【Chemistry 2】 [In formula (A1-2), R1, R2, and R4 are as defined above, and n2 and m2 each represent integers greater than or equal to 0. Multiple R2s may be identical or different from each other, and if multiple R4s exist, they may be identical or different from each other.] 【Transformation 3】 [In formula (A1-3), R1, R3, and R4 are as defined above, and n3 and m3 each represent integers greater than or equal to 0. Multiple R3s may be identical or different from each other, and if there are multiple R4s, they may be identical or different from each other.] 【Chemistry 4】 [In formula (a1-1), R1 is the same as above, and * indicates a coupling.] 【Transformation 5】 [In formula (a1-2), R1 is the same as above, and * indicates a coupling.] 【Transformation 6】 [In formula (a1-3), R1 is the same as above, and * indicates a coupling.]

2. A polycarbonate polyol represented by the following formula (A2-2), It further contains a polyester polyol represented by the following formula (A2-3), Let C be the total number of moles of the group represented by the following formula (a1-1) contained in the above composition, Let C be the total number of moles of the group represented by the following formula (a1-2) contained in the above composition, Let C be the total number of moles of the groups represented by the following formula (a1-3) contained in the above composition, Let C be the total number of moles of the group represented by the following formula (a2-2) contained in the above composition, If the total number of moles of the group represented by the following formula (a2-3) contained in the above composition is C A2-3, The composition according to claim 1, wherein the molar ratio ((C A2-2 + C A2-3) / (C A1-1 + C A1-2 + C A1-3)) is 0.01 to 0.

750. 【Transformation 7】 [In formula (A2-2), R1, R2, and R4 are as defined above, and n4 represents a non-negative integer. If there are multiple R4s, they may be the same or different.] 【Transformation 8】 [In formula (A2-3), R1, R3, and R4 are as defined above, and n5 represents an integer greater than or equal to 0. If there are multiple R4s, they may be the same or different from each other.] 【Chemistry 9】 [In formula (a1-1), R1 is the same as above, and * indicates a coupling.] 【Chemistry 10】 [In formula (a1-2), R1 is the same as above, and * indicates a coupling.] 【Chemistry 11】 [In formula (a1-3), R1 is the same as above, and * indicates a coupling.] 【Chemistry 12】 [In formula (a2-2), R1 is the same as above, and * indicates a coupling.] 【Chemistry 13】 [In formula (a2-3), R1 is the same as above, and * indicates a coupling.]

3. A polycarbonate polyol represented by the following formula (A-3), The composition according to claim 1 or 2, further comprising a polycarbonate diol represented by the following formula (A-4). 【Chemistry 14】 [In formula (A-3), R1 and R4 are as defined above, and n5, m5, and p5 each represent integers of 1 or greater. Multiple R4s may be the same or different from each other.] 【Chemistry 15】 [In equation (A-4), R4 is the same as above, and n6 represents an integer of 1 or greater. Multiple R4s may be the same or different from one another.]

4. The total number of moles of the group represented by the following formula (a1-1) contained in the composition is C A1-1, If the total number of moles of the group represented by the following formula (I) contained in the above composition is C T, The composition according to claim 1 or 2, wherein the molar ratio (CA1-1 / CT) is 0.02 to 0.

99. 【Chemistry 16】 [In formula (a1-1), R1 is the same as above, and * indicates a coupling.] 【Chemistry 17】 [In formula (I), R1 is the same as above, and * indicates a coupling.]

5. The total number of moles of the group represented by the following formula (a1-2) contained in the composition is C A1-2, If the total number of moles of the group represented by the following formula (I) contained in the above composition is C T, The composition according to claim 1 or 2, wherein the molar ratio (CA1-2 / CT) is 0.001 to 0.

99. [Chemistry 18] [In formula (a1-2), R1 is the same as above, and * indicates a coupling.] 【Chemistry 19】 [In formula (I), R1 is the same as above, and * indicates a coupling.]

6. The total number of moles of the groups represented by the following formula (a1-3) contained in the composition is C A1-3, If the total number of moles of the group represented by the following formula (I) contained in the above composition is C T, The composition according to claim 1 or 2, wherein the molar ratio (CA1-3 / CT) is 0.005 to 0.

34. 【Chemistry 20】 [In formula (a1-3), R1 is the same as above, and * indicates a coupling.] 【Chemistry 21】 [In formula (I), R1 is the same as above, and * indicates a coupling.]

7. The total number of moles of the group represented by the following formula (a2-3) contained in the composition is C A2-3, If the total number of moles of the group represented by the following formula (I) contained in the above composition is C T, The composition according to claim 2, wherein the molar ratio (C A2-3 / C T) is 0.001 to 0.

234. 【Chemistry 22】 [In formula (a2-3), R1 is the same as above, and * indicates a coupling.] 【Chemistry 23】 [In formula (I), R1 is the same as above, and * indicates a coupling.]

8. The total number of moles of the group represented by the following formula (d) contained in the composition is C and D, Let C be the total number of moles of the group represented by the following formula (a2-2) contained in the above composition, If the total number of moles of the group represented by the following formula (a2-3) contained in the above composition is C A2-3, The composition according to claim 2, wherein the molar ratio (C A2-3 / (C A2-2 + C A2-3 + C D) × 100) is 0.010 to 10.

20. 【Chemistry 24】 [In formula (d), R is a hydrogen atom or an alkanediyl group, and * indicates a bond. R may be the same or different from each other.] 【Chemistry 25】 [In formula (a2-2), R1 is the same as above, and * indicates a coupling.] 【Chemistry 26】 [In formula (a2-3), R1 is the same as above, and * indicates a coupling.]

9. The total number of moles of the group represented by the following formula (d) contained in the composition is C and D, Let C be the total number of moles of the group represented by the following formula (a2-2) contained in the above composition, If the total number of moles of the group represented by the following formula (a2-3) contained in the above composition is C A2-3, The composition according to claim 2, wherein the molar ratio ((C A2-2 + C A2-3) / (C A2-2 + C A2-3 + C D) × 100) is 0.100 to 12.

00. 【Chemistry 27】 [In formula (d), R is a hydrogen atom or an alkanediyl group, and * indicates a bond. R may be the same or different from each other.] 【Chemistry 28】 [In formula (a2-2), R1 is the same as above, and * indicates a coupling.] 【Chemistry 29】 [In formula (a2-3), R1 is the same as above, and * indicates a coupling.]

10. The total number of moles of the group represented by the following formula (f') contained in the composition is C F, If the total number of moles of the group represented by the following formula (I) contained in the above composition is C T, The composition according to claim 1 or 2, wherein the molar ratio (C F / C T × 100) is 1.70 to 45.

0. 【Transformation 30】 [In equation (f'), R 1 is the same as above, and * indicates a coupling.] 【Chemistry 31】 [In formula (I), R1 is the same as above, and * indicates a coupling.]

11. The R3 is an alkanediyl group, The composition according to claim 1 or 2, wherein R4 is an alkanediyl group or *1-O-R c-*2.

12. A reaction product of polycarbonate polyol (B) and polyester polyol (C), The composition according to claim 11, wherein the polyester polyol (C) comprises a polyester polyol (β) which is a ring-opening addition polymer of a cyclic ester compound initiated by a diol, and / or a polyester polyol (β') which is a ring-opening addition polymer of a cyclic ester compound initiated by a polyhydric alcohol having three or more hydroxyl functional groups.

13. A method for producing the compound described in Claim 1, The process includes a reaction step of obtaining the compound by reacting the polycarbonate polyol and the polyester polyol in a mixed solution containing a polycarbonate polyol, a polyester polyol, and a transesterification catalyst. At least one of the polycarbonate polyol and the polyester polyol contains a group represented by the following formula (I), or A method wherein the mixture further comprises a polyhydric alcohol represented by the following formula (e). 【Chemistry 32】 [In formula (I), R1 is the same as above, and * indicates a coupling.] 【Transformation 33】 [In equation (e), R1 is the same as described above.]

14. The production method according to claim 13, wherein the transesterification catalyst comprises lithium acetylacetonate.

15. A polycondensate or crosslinked product thereof of a polyol component and a polyisocyanate component, The polyol component contains a compound represented by the following formula (A1-1), a polycarbonate polyol represented by the following formula (A1-2), and a polyester polyol represented by the following formula (A1-3). Let C A1-1 be the total number of moles of the group represented by the following formula (a1-1) contained in the polyol component. Let C be the total number of moles of the group represented by the following formula (a1-2) contained in the polyol component, If the total number of moles of the groups represented by the following formula (a1-3) contained in the polyol component is C A1-3, The molar ratio (C A1-1 / (C A1-1 + C A1-2 + C A1-3) × 100) is between 5.3 and 80. A urethane resin having a polyol component with hydroxyl groups of 30 to 200 mg KOH / g. 【Transformation 34】 [In formula (A1-1), R1 represents a hydrogen atom, an alkyl group, or a hydroxyalkyl group. R2 represents an alkanediyl group. R3 represents an alkanediyl group, or *1-R a-C(=O)-O-R b-*2. R4 represents an alkanediyl group, *1-O-R c-*2, or *1-Ra a-C(=O)-O-R b-*2. Ra, Rb, and Rc each independently represent an alkanediyl group. *1 indicates the bonding site with the carbonyl group, and *2 indicates the bonding site with the oxygen atom. n1 and m1 each represent non-negative integers. If there are multiple instances of R4, they may be identical or different from one another. 【Chemistry 35】 [In formula (A1-2), R1, R2, and R4 are as defined above, and n2 and m2 each represent integers greater than or equal to 0. Multiple R2s may be identical or different from each other, and if multiple R4s exist, they may be identical or different from each other.] 【Transformation 36】 [In formula (A1-3), R1, R3, and R4 are as defined above, and n3 and m3 each represent integers greater than or equal to 0. Multiple R3s may be identical or different from each other, and if there are multiple R4s, they may be identical or different from each other.] 【Chemistry 37】 [In formula (a1-1), R1 is the same as above, and * indicates a coupling.] 【Transformation 38】 [In formula (a1-2), R1 is the same as above, and * indicates a coupling.] 【Chemistry 39】 [In formula (a1-3), R1 is the same as above, and * indicates a coupling.]

16. The urethane resin according to claim 15, further comprising a polyol having an acidic group as the polyol component.

17. An aqueous urethane resin dispersion comprising an aqueous medium and a urethane resin or a neutralized product thereof according to claim 15 or 16 dispersed in the aqueous medium.

18. A coating agent comprising the urethane resin according to claim 15 or 16.

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