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, a method for producing the same, a composition, a urethane resin, an aqueous urethane resin dispersion, and a coating agent.

Background Art

[0002] Polycarbonate polyol, like polyester polyol, polyether polyol, etc., is useful as a raw material for producing a urethane resin (also called a polyurethane resin) by reacting with a polyisocyanate compound, and is useful as a raw material for adhesives, paints, etc.

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

[0004] Polycarbonate polyol is usually produced by reacting a carbonic ester and a diol in the presence of a transesterification catalyst (transesterification reaction).

[0005] So far, polycarbonate polyols having various structures have been proposed according to the purpose. For example, in Patent Documents 1 and 2, polycarbonate polyols obtained by a transesterification reaction of a polycarbonate diol and a triol compound and / or a tetraol compound have been proposed.

Prior Art Documents

Patent Documents

[0006]

Patent Document 1

[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 same, and a urethane resin using the compound as a raw material. Another object of the present invention is to provide a composition containing the compound and a urethane resin using the composition as a raw material. 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 Problems]

[0008] The present invention provides the following inventions.

[0009] [1] A compound represented by the following formula (A1-1). [Chemical Formula] [In formula (A1-1), R 1 represents a hydrogen atom, an alkyl group or a hydroxyalkyl group, R 2 represents an alkanediyl group, R 3 represents an alkanediyl group, or *1-R a -C(=O)-O-R b -*2, R 4 represents an alkanediyl group, *1-O-R c -*2, or *1-R a -C(=O)-O-R b -*2, R a , R b , and R c each independently represent an alkanediyl group, *1 represents a bonding site with a carbonyl group, *2 represents a bonding site with an oxygen atom, n 1 and m 1 each represent an integer of 0 or more. R 4When there are a plurality of them, they may be the same as or different from each other. [2] A composition containing 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 is defined as C A1-2 for the total number of moles of the group represented by the following formula (a1-2) contained in the composition, and C A1-3 is defined as C A1-1 for the total number of moles of the group represented by the following formula (a1-3) contained in the composition. Then, the molar ratio (C A1-1 / (C A1-2 +C A1-3 )×100) is 5.3 to 99.

Chemical formula

Chemical formula

Chemical formula

Chem.

Chem.

Chem.

Chem.

Chemical formula

Chemical formula

Chemical formula

Chemical formula

Chemical formula

Chemical formula

[10] Let the total number of moles of the group represented by the following formula (d) contained in the composition be C D and let the total number of moles of the group represented by the following formula (a2-2) contained in the composition be C A2-2 and let the total number of moles of the group represented by the following formula (a2-3) contained in the composition be C A2-3 Then, the composition according to any one of [2] to [9], 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. [Chemical formula] [In formula (d), R is a hydrogen atom or an alkanediyl group, and * represents a bond. The Rs may be the same as or different from each other.] [Chemical formula] [In formula (a2-2), R 1 has the same meaning as described above, and * represents a bond.] [Chemical formula] [In formula (a2-3), R 1 has the same meaning as described above, and * represents a bond.]

[11] Let the total number of moles of the group represented by the following formula (f’) contained in the composition be C F and the total number of moles of the group represented by the following formula (I) contained in the composition be C T . Then, the molar ratio (C F / C T ×100) is 1.70 to 45.0, and the composition according to any one of [2] to

[10] . [Chemical formula] [In formula (f’), R 1 has the same meaning as described above, and * represents a bond.] [Chemical formula] [In formula (I), R 1 has the same meaning as described above, and * represents a bond.]

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

[11] , wherein the R 3 is an alkanediyl group, the R 4 is an alkanediyl group, or *1-O-R c -*2.

[13] It is a reaction product of polycarbonate polyol (B) and polyester polyol (C), and the polyester polyol (C) is 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 3 or more hydroxyl functional groups as an initiator. The composition according to any one of [2] to

[12] .

[14] A method for producing the compound according to [1], comprising a reaction step of obtaining the compound by reacting the polycarbonate polyol and the polyester polyol in a mixed liquid containing the polycarbonate polyol, the 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 liquid further contains a polyhydric alcohol represented by the following formula (e). [Chemical formula] [In formula (I), R 1 is as defined above, and * represents a bond.] [Chemical formula] [In formula (e), R 1 is as defined above.]

[15] The production method according to

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

[16] The production 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, and the polyol component contains the compound according to [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 groups represented by the following formula (a1-1) contained in the polyol component is C A1-1 is defined as C A1-2 for the total number of moles of the groups represented by the following formula (a1-2) contained in the polyol component, and C A1-3 is defined as C A1-1 for the total number of moles of the groups represented by the following formula (a1-3) contained in the polyol component. Then, the molar ratio (C A1-1 / (C A1-2 +C A1-3 )×100) is 5.3 to 99, and the urethane resin according to

[17] .

Chemical formula

Chemical formula

Chemical formula

[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 groups represented by the following formula (a1-1) contained in the polyol component is C A1-1 Let it be, and the total number of moles of the groups represented by the following formula (a1-2) contained in the polyol component is C A1-2 Let it be, and the total number of moles of the groups represented by the following formula (a1-3) contained in the polyol component is C A1-3 Let it be, and the total number of moles of the groups represented by the following formula (a2-2) contained in the polyol component is C A2-2 Let it be, and the total number of moles of the groups represented by the following formula (a2-3) contained in the polyol component is C A2-3 Let it be, 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, the urethane resin according to

[17] or

[18] . [Chemical formula] [In formula (A2-2), R 1 , R 2 and R 4 have the same meaning as described above, and n 4 represents an integer of 0 or more. When there are a plurality of R 4 they may be the same or different from each other.] [Chemical formula] [In formula (A2-3), R 1 , R 3 and R 4 are as defined above, and n 5 represents an integer of 0 or more. When there are a plurality of Rs 4 they may be the same as or different from each other.] [Chemical formula] [In formula (a1-1), R 1 is as defined above, and * represents a bond.] [Chemical formula] [In formula (a1-2), R 1 is as defined above, and * represents a bond.] [Chemical formula] [In formula (a1-3), R 1 is as defined above, and * represents a bond.] [Chemical formula] [In formula (a2-2), R 1 is as defined above, and * represents a bond.] [Chemical formula] [In formula (a2-3), R 1 is as defined above, and * represents 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). [Chemical formula] [In formula (A-3), R 1 and R4 is synonymous with the above, and n 5 , m 5 and p 5 each represent an integer of 1 or more. When there are a plurality of Rs 4 , they may be the same as or different from each other.]

Chemical formula

[21] Let the total number of moles of the group represented by the following formula (a1-1) contained in the polyol component be C A1-1 , and let the total number of moles of the group represented by the following formula (I) contained in the polyol component be C T . Then, the urethane resin according to any one of

[17] to

[20] in which the molar ratio (C A1-1 / C T ) is 0.02 to 0.99.

Chemical formula

Chemical formula

[22] Let the total number of moles of the group represented by the following formula (a1-2) contained in the polyol component be C A1-2 , and let the total number of moles of the group represented by the following formula (I) contained in the polyol component be C T . Then, the urethane resin according to any one of

[17] to

[21] in which the molar ratio (C A1-2 / C T ) is 0.001 to 0.99.

Chemical formula

Chemical formula

[23] Let the total number of moles of the group represented by the following formula (a1-3) contained in the polyol component be C A1-3 , and let the total number of moles of the group represented by the following formula (I) contained in the polyol component be C T . Then, for the urethane resin according to any one of

[17] to

[22] , the molar ratio (C A1-3 / C T ) is 0.005 to 0.340.

Chemical formula

Chemical formula

[24] Let the total number of moles of the group represented by the following formula (a2-3) contained in the polyol component be C A2-3 , and let the total number of moles of the group represented by the following formula (I) contained in the polyol component be C T . Then, for the urethane resin according to any one of

[17] to

[23] , the molar ratio (C A2-3 / C T ) is 0.001 to 0.234.

Chemical formula

Chemical formula

[25] Let the total number of moles of the group represented by the following formula (d) contained in the polyol component be C D , and let the total number of moles of the group represented by the following formula (a2-2) contained in the polyol component be C A2-2 , and let the total number of moles of the group represented by the following formula (a2-3) contained in the polyol component be C A2-3 . Then, the urethane resin according to any one of

[17] to

[24] , wherein the molar ratio (C A2-3 / (C A2-2 + C A2-3 + C D ) × 100) is 0.010 to 10.20.

Chemical formula

Chemical formula

Chemical formula

[26] Let the total number of moles of the group represented by the following formula (d) contained in the polyol component be C D , and let the total number of moles of the group represented by the following formula (a2-2) contained in the polyol component be C A2-2 . Then, let the total number of moles of the group represented by the following formula (a2-3) contained in the polyol component be 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, the urethane resin according to any one of

[17] to

[25] .

Chemical formula

Chemical formula

Chemical formula

[27] Let the total number of moles of the group represented by the following formula (f’) contained in the polyol component be C F and let the total number of moles of the group represented by the following formula (I) contained in the polyol component be C T Then, the molar ratio (C F / C T × 100) is 1.70 to 45.0, the urethane resin according to any one of

[17] to

[26] .

Chemical formula

Chemical formula

[28] Wherein R 3 is an alkanediyl group, and R 4 is an alkanediyl group, or *1 - O - R 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) is 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 3 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 containing an aqueous medium and the urethane resin according to

[30] or a neutralized product thereof dispersed in the aqueous medium.

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

[17] to

[30] . [Advantages of the Invention]

[0010] According to the present invention, it is possible to provide a novel compound and a method for producing the same, which are useful as raw materials for urethane resins and the like, and a urethane resin using the compound as a raw material. According to the present invention, it is also possible to provide a composition containing the compound and a urethane resin using the composition as a raw material. According to the present invention, it is also possible to provide an aqueous urethane resin dispersion containing the above urethane resin having an acidic group. [Brief Description of the Drawings]

[0011]

Figure 1

Figure 2

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

Chemical formula

[0014] R 1The alkyl group and hydroxyalkyl group represented by [alkyl group and hydroxyalkyl group] may be linear or branched. The number of carbon atoms of the alkyl group and hydroxyalkyl group may be, for example, 1 to 6, and may also be 2 to 5 or 3 to 4. Specific examples of the alkyl group and hydroxyalkyl group include methyl group, ethyl group, propyl group, isopropyl group, butyl group, pentyl group, hexyl group, hydroxymethyl group, hydroxyethyl group, hydroxypropyl group, hydroxybutyl group, etc. 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 [alkanediyl group] may be linear or branched. R 2 The alkanediyl group represented by [alkanediyl group] and the alkanediyl group represented by R 3 may be the same or different.

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

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

[0018] R 4 The number of carbon atoms of the alkandiyl group represented by is the same as those of the alkandiyl groups mentioned in the description of R 2 and R 3 Among them, 1,4-butanediyl group, 1,5-pentanediyl group, 1,6-hexanediyl group, 3-methyl-1,5-pentanediyl group, 2-ethyl-1,6-hexanediyl group, 1,9-nonanediyl group, 2-methyloctane-1,8-diyl group, etc. are preferable.

[0019] R a R b and R c The alkandiyl group represented by may be the same as the above-mentioned alkandiyl groups. The alkandiyl group represented by R a R b and R c The number of carbon atoms of the alkandiyl group represented by may be, for example, 2 to 10. When there are two or more alkandiyl groups represented by R a all of them may be linear alkandiyl groups or branched alkandiyl groups, and some may be linear alkandiyl groups while the other part may be branched alkandiyl groups. When there are two or more alkandiyl groups represented by R b all of them may be linear alkandiyl groups or branched alkandiyl groups, and some may be linear alkandiyl groups while the other part may be branched alkandiyl groups. When there are two or more alkandiyl groups represented by R c all of them may be linear alkandiyl groups or branched alkandiyl groups, and some may be linear alkandiyl groups while the other part may be branched alkandiyl groups.

[0020] Compound (A1-1) is R 2 R 3 R 4 Ra 、 R b or R c When two or more alkandiyl groups are included as R

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

[0022] The number average molecular weight of the compound (A1-1) may be, for example, from 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 using GPC (Gel Permeation Chromatography).

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

[0024] The properties of the compound (A1-1) are not particularly limited, and it may be solid at 25°C or may be liquid at 25°C. The properties of the compound (A1-1) can be changed depending on the type of alkandiyl group (number of carbon atoms, presence or absence of branching, etc.) included as R 2 、 R 3 、 R 4 、 R a 、 R b 、 or R c in the compound (A1-1), and further depending on the hydroxyl value of the compound (A1-1), etc. For example, when R 2 、 R 3 、 R 4 、 R a 、 R b or R cWhen the total molar number of the branched alkanediyl groups in the compound (A1-1) is 0.2 to 1.0 with respect to the total molar number of the alkanediyl groups contained therein, and when the hydroxyl value of the compound (A1-1) is high, the compound (A1-1) tends to be liquid at 25°C.

[0025] In the present embodiment, from the viewpoint that a urethane resin excellent in durability such as heat resistance or heat and moisture resistance / heat and water resistance is likely to be formed when used as a raw material of the urethane resin, R contained in the compound (A1-1) 3 is an alkanediyl group, and R 4 is an alkanediyl group, or *1-O-R c -*2 is more preferable.

[0026] Further, in the present embodiment, from the viewpoint that a urethane resin excellent in 100% modulus and heat resistance is likely to be formed when used as a raw material of the urethane resin, R in the compound (A1-1) 2 , R 3 and R 4 The ratio of the total molar number of the alkanediyl group contained as, *1-O-R c -*2, and *1-R a -C(=O)-O-R b -*2 to the total molar number of the alkanediyl group contained as R 2 and the total molar number of *1-O-R 4 -*2 contained as R c -*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), still more 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 a polycarbonate polyol (B) and a polyester polyol (C). Further, the compound (A1-1) may be a reaction product of a polycarbonate polyol (B), a polyester polyol (C), a diol (D) and / or a polyhydric alcohol (E) represented by the following formula (e). In the compound (A1-1), 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 is bonded to a hydrogen atom to form a hydroxy group.

Chemical formula

Chemical formula

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

[0029] Examples of the polycarbonate polyol (B-1) include those obtained by the reaction of carbonates and diols.

[0030] Examples of carbonates that can be used in the reaction to obtain 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 any combination of two or more of these.

[0031] Examples of diols that can be used in the reaction to obtain 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, dipropylene glycol, neopentyl glycol, cyclohexane-1,4-diol, cyclohexane-1,4-dimethanol, dimer acid diol, ethylene oxide or propylene oxide adducts 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 polycarbonate polyol (B-2) include those obtained by the reaction of carbonates, diols, and polyhydric alcohols having 3 or more hydroxyl functional groups.

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

[0034] Examples of the diols that can be used in the reaction for obtaining the polycarbonate polyol (B-2) include the same ones as those described for 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 the polyhydric alcohols having 3 or more hydroxyl functional groups that can be used in the reaction for obtaining the polycarbonate polyol (B-2) include, for example, trimethylolpropane, trimethylolethane, glycerin, pentaerythritol, sorbitol, etc., and any combination of two or more of these.

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

[0037] Examples of the polyester polyol (C-1) include, for example, 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 described for 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 the dicarboxylic acid and / or its anhydride (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, etc., tartaric acid, and their anhydrides, and any combination of two or more of these.

[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, etc., and any combination of two or more of these. Among them, the ring-opening addition polymer of ε-caprolactone using trimethylolpropane as an initiator is preferred from the viewpoints of polymerization stability and economy.

[0041] Examples of the polyester polyol (C-2) include, for example, the following polyester polyols (α’) to (β’), and any combination of two or more thereof. (α’) A polyester polyol (polyester polyol (α’)) obtained from a diol (C-2-1), a dicarboxylic acid and / or its anhydride (C-2-2), and a polyhydric alcohol having 3 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 such as lactones (C-2-4) using a polyhydric alcohol having 3 or more hydroxyl functional groups (C-2-3) 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 3 or more hydroxyl functional groups as an initiator.

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

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

[0044] Examples of the polyhydric alcohol having 3 or more hydroxyl functional groups (C-2-3) include, for example, trimethylolpropane, trimethylolethane, glycerin, pentaerythritol, sorbitol, etc., and any combination of two or more thereof.

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

[0046] In the present embodiment, from the viewpoint that a urethane resin excellent in durability such as heat resistance or heat and humidity resistance is likely to be formed when used as a raw material of the urethane resin, it is more preferable that the polyester polyol (C) contains the polyester polyol (β) and / or the polyester polyol (β’).

[0047] Specific examples of the diol (D) include the same diols as those described 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 preferable.

[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 of the above compound (A1-1) may be, for example, the following formula (e):

Chemical formula

[0050] <Composition> The composition of this embodiment contains the 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)").

Chemical formula

Chemical formula

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

[0052] 1 1

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

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

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

[0055] m 2 , n 2 , m 3 and n 3 may each be from 0 to 65, or may be from 1 to 60 or from 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 C A1-1Let C be the total number of moles of the group represented by the following formula (a1-2) contained in the composition A1-2 Let C be the total number of moles of the group represented by the following formula (a1-3) contained in the composition A1-3 Do so. [Chemical formula] [In formula (a1-1), R 1 has the same meaning as described above, and * represents a bond. The bond represented by * is directly bonded to a carbon atom.] [Chemical formula] [In formula (a1-2), R 1 has the same meaning as described above, and * represents a bond. The bond represented by * is directly bonded to a carbon atom.] [Chemical formula] [In formula (a1-3), R 1 has the same meaning as described above, and * represents a bond. The bond represented by * is directly bonded to a carbon atom.]

[0057] The 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, still more preferably 10.0 or more, and even more preferably 20.0 or more. When the molar ratio (C A1-1 / (C A1-1 + C A1-2 + C A1-3 ) × 100) is 5.3 or more, there is a tendency that a polyurethane resin excellent in heat and water resistance is likely to be formed. The molar ratio (C A1-1 / (C A1-1 + C A1-2 + C A1-3 ) × 100) is preferably 99 or less, more preferably 80 or less, still more preferably 70 or less, and particularly preferably 60 or less. The molar ratio (C 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 Δ of the signal (S1-3) S1-3 and the sum with the integral value Δ of the signal (S1-1) S1-1 and the ratio of (Δ S1-1 / (Δ S1-1 + Δ S1-2 + Δ S1-3 )) × 100) can be alternatively referred to as.

[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)").

Chemical formula

Chemical formula

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

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

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

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

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

[0065] In the following description, let the total number of moles of the group represented by the following formula (a2-2) contained in the composition be C A2-2 and let the total number of moles of the group represented by the following formula (a2-3) contained in the composition be C A2-3 for the sake of simplicity. [Chemical formula] [In formula (a2-2), R 1 has the same meaning as described above, and * represents a bond. The bond represented by * is directly bonded to a carbon atom.] [Chemical formula] [In formula (a2-3), R 1 has the same meaning as described above, and * represents a bond. The bond represented by * is directly bonded to a carbon atom.]

[0066] The molar ratio ((C A2-2 + C A2-3 ) / (C A1-1 + C A1-2 + C A1-3 )) may be 0.010 or more, 0.050 or more, 0.100 or more, 0.200 or more, or 0.300 or more. When the molar ratio ((C A2-2 + C A2-3 ) / (C A1-1 + C A1-2 + C A1-3 )) is 0.010 or more, there is a tendency that a polyurethane resin excellent in particularly 100% modulus, breaking strength, glass transition temperature, and elongation rate is easily formed. The molar ratio ((C A2-2 + C A2-3 ) / (C A1-1 + C A1-2 + C A1-3 )) may be 0.750 or less, 0.700 or less, 0.650 or less, or 0.600 or less. When the molar ratio ((C A2-2 + C A2-3 ) / (C A1-1 + C A1-2 + C A1-3 )) is 0.750 or less, there is a tendency that a polyurethane resin excellent in particularly heat water resistance and breaking strength is easily formed. The molar ratio ((C A2-2 + C A2-3 ) / (C A1-1 + C A1-2 + C A1-3 )) may be 0.010 to 0.750. When the molar ratio ((C A2-2 + C A2-3 ) / (C A1-1 + C A1-2 + C A1-3 )) is within the above range, when the composition is used as a raw material for a urethane resin, there is a tendency that a polyurethane resin having good 100% modulus, heat resistance, breaking strength, elongation rate, glass transition temperature, and heat water resistance is easily formed.

[0067] The molar ratio ((C A2-2 + C A2-3 ) / (C A1-1 + C A1-2 + C A1-3 )) is, for example, the molar ratio (C A1-1 / (CA1-1 +C A1-2 +C A1-3 )×100), using deuterated chloroform as a solvent and tetramethylsilane as a reference substance, the 1 1H-NMR measurement of the composition and the 1 1H-NMR spectrum can be determined from the integral values of the signals. Specifically, for example, the integral value Δ S1-1 (2 mol of hydrogen atoms) of the above signal (S1-1), the integral value Δ S1-2 (2 mol of hydrogen atoms) of the above signal (S1-2), the integral value Δ S1-3 (2 mol of hydrogen atoms) of the above signal (S1-3), and the integral value Δ S2-2 (4 mol of hydrogen atoms) of the methylene signal (S2-2) located adjacent to the hydroxy group of the group represented by the formula (a2-2), and the integral value Δ S2-3 (4 mol of hydrogen atoms) of the methylene signal (S2-3) located adjacent to the hydroxy group of the group represented by the formula (a2-3), the molar ratio ((C A2-2 +C A2-3 ) / (C A1-1 +C A1-2 +C A1-3 )) can be calculated. In this case, the molar ratio ((C A2-2 +C A2-3 ) / (C A1-1 +C A1-2 +C A1-3 )) is 0.5 times the ratio of the sum of the integral value Δ S1-1 of the signal (S1-1), the integral value Δ S1-2 of the signal (S1-2), and the integral value Δ S1-3 of the signal (S1-3) to the sum of the integral value Δ S2-2 of the signal (S2-2) and the integral value Δ S2-3 of the signal (S2-3) (0.5×(Δ S2-2 +Δ S2-3 ) / (Δ S1-1 +Δ S1-2 +Δ S1-3 )) and can be rephrased as such.

[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 C E is defined as such. Also, let Se be the signal of the methylene adjacent to the hydroxy group of the polyhydric alcohol represented by formula (e).

Chemical formula

[0069] The polyhydric alcohol (E) is as defined above, and the alkyl group and hydroxyalkyl group that the polyhydric alcohol (E) has as R 1 may be the same as the atoms or groups included as R 1 in the compound (A1-1).

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

[0071] The composition may further contain an oxetane compound represented by the following formula (f) (hereinafter also referred to as "oxetane compound (F)").

Chemical formula

[0072] The oxetane compound (F) is synonymous with those described above, and the alkyl group and hydroxyalkyl group that the oxetane compound (F) has as R 1 may be the same as the atoms or groups contained as R in the compound (A1-1). 1

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

[0074] Specific examples of the oxetane compound (F) include, for example, 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)").

Chemical formula

[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 represents an integer of 1 or more. When there are a plurality of R's 4 they may be the same as or different from each other.]

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

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

[0082] In the following description, let the total number of moles of the group represented by the following formula (I) contained in the composition be C T . [Chemical formula] [In formula (I), R 1 is as defined above, and * represents a bond.] In formula (I), the bond represented by * is directly bonded to a carbon atom or a hydrogen atom.

[0083] The molar ratio (C A1-1 / C T ) may be 0.02 or more, 0.05 or more, or 0.1 or more. When the molar ratio (C A1-1 / C T ) is 0.02 or more, a polyurethane resin particularly excellent in heat and water resistance tends to be easily formed. The molar ratio (C A1-1 / C T) may be 0.990 or less, 0.800 or less, or 0.700 or less. When the molar ratio (C A1-1 / C T ) is 0.990 or less, a polyurethane resin particularly excellent in 100% modulus and heat resistance tends to be easily formed. The molar ratio (C A1-1 / C T ) may be 0.02 to 0.99. When the molar ratio (C A1-1 / C T ) is within the above range, when the composition is used as a raw material for a urethane resin, a polyurethane resin having good 100% modulus, heat resistance, and hot water resistance tends to be easily formed.

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

[0085] The 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. The molar ratio (C 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. The molar ratio (C A1-3 / CT ) is 0.340 or less, there is a tendency that a polyurethane resin particularly excellent in hot water resistance is easily formed. The molar ratio (C A1-3 / C T ) may be 0.005 to 0.340. When the molar ratio (C A1-3 / C T ) is within the above range, when the composition is used as a raw material for a urethane resin, there is a tendency that a polyurethane resin having both good 100% modulus, heat resistance and hot water resistance is easily formed.

[0086] The 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. When the molar ratio (C A2-3 / C T ) is 0.001 or more, there is a tendency that a polyurethane resin particularly excellent in 100% modulus, breaking strength, glass transition temperature and elongation rate is easily formed. The molar ratio (C 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. When the molar ratio (C A2-3 / C T ) is 0.234 or less, there is a tendency that a polyurethane resin particularly excellent in hot water resistance and breaking strength is easily formed. The molar ratio (C A2-3 / C T ) may be 0.001 to 0.234. When the molar ratio (C A2-3 / C T ) is within the above range, when the composition is used as a raw material for a urethane resin, there is a tendency that a polyurethane resin having good 100% modulus, heat resistance, hot water resistance, breaking strength, elongation rate and glass transition temperature is easily formed.

[0087] The molar ratio (C A1-1 / C T ), the molar ratio (C A1-2 / C T ), the molar ratio (C A1-3 / C T ) and the molar ratio (CA2-3 / C T ) are all within the above ranges, when the composition is used as a raw material for a urethane resin, a polyurethane resin with better 100% modulus and heat resistance tends to be more easily 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 ) can be determined, for example, in the same way as (C A1-1 / (C A1-1 +C A1-2 +C A1-3 )×100), using deuterated chloroform as a solvent and tetramethylsilane as a reference substance, from the 1 1H-NMR measurement of the composition and the integral values of the signals of the 1 1H-NMR spectrum obtained by the measurement. Specifically, for example, the integral value Δ S1-1 (2 mol of hydrogen atoms) of the above signal (S1-1), the integral value Δ S1-2 (2 mol of hydrogen atoms) of the above signal (S1-2), the integral value Δ S1-3 (2 mol of hydrogen atoms) of the above signal (S1-3), the integral value Δ S2-3 (4 mol of hydrogen atoms) of the above signal (S2-3), and when R 1 in formula (I) is a linear alkyl group, from the ratio with the integral value Δ 1 (3 mol of hydrogen atoms) of the signal (SI) of the terminal methyl of R SI (alkyl group) in formula (I), the molar ratios (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 ) can be calculated. In this case, the molar ratio (C A1-1 / C T ) is the integral value Δ S1-1and the integrated value Δ of the signal (SI) SI 1.5 times the ratio to (1.5 × Δ S1-1 / Δ SI ), the molar ratio (C A1-2 / C T ) is the integrated value Δ of the signal (S1-2) S1-2 and the integrated value Δ of the signal (SI) SI 1.5 times the ratio to (1.5 × Δ S1-2 / Δ SI ), the molar ratio (C A1-3 / C T ) is the integrated value Δ of the signal (S1-3) S1-3 and the integrated value Δ of the signal (SI) SI 1.5 times the ratio to (1.5 × Δ S1-3 / Δ SI ), the molar ratio (C A2-3 / C T ) is the integrated value Δ of the signal (S2-3) S2-3 and the integrated value Δ of the signal (SI) SI 0.75 times the ratio to (0.75 × Δ S2-3 / Δ SI ) and can be rephrased as such.

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

[0090] In the following description, let the total number of moles of the group represented by the following formula (d) contained in the composition be C D . [Chemical formula] [In formula (d), R is a hydrogen atom or an alkanediyl group, and * represents a bond. R may be the same or different from each other.]

[0091] The 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. The molar ratio (CA2-3 / (C A2-2 +C A2-3 +C D ) × 100) is 0.010 or more, a polyurethane resin with particularly excellent heat resistance tends to be easily formed. The molar ratio (C 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. When the molar ratio (C A2-3 / (C A2-2 +C A2-3 +C D ) × 100) is 10.20 or less, a polyurethane resin with particularly excellent heat water resistance and breaking strength tends to be easily formed. The molar ratio (C A2-3 / (C A2-2 +C A2-3 +C D ) × 100) may be 0.010 to 10.20. When the molar ratio (C A2-3 / (C A2-2 +C A2-3 +C D ) × 100) is within the above range, when the composition is used as a raw material for a urethane resin, a polyurethane resin with good 100% modulus, heat resistance, breaking strength, and heat water resistance tends to be easily formed.

[0092] The 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. When the molar ratio ((C A2-2 +C A2-3 ) / (C A2-2 +C A2-3 +C D ) × 100) is 0.100 or more, a polyurethane resin with particularly excellent 100% modulus and heat resistance tends to be easily formed. The molar ratio ((C 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. The molar ratio ((C A2-2 +C A2-3 ) / (C A2-2 +C A2-3 +C D ) × 100) may be 0.100 to 12.00. When the molar ratio ((C A2-2 +C A2-3 ) / (C A2-2 +C A2-3 +C D ) × 100) is within the above range, when the composition is used as a raw material for a urethane resin, a polyurethane resin with both good 100% modulus and heat resistance tends to be easily formed.

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

[0094] The molar ratio (C A2-3 / (C A2-2 +C A2-3 +C D ) × 100) and the molar ratio ((C A2-2 +C A2-3 ) / (C A2-2 +C A2-3 +C D ) × 100) are, for example, like (C A1-1 / (C A1-1 +C A1-2 +C A1-3 ) × 100), using deuterated chloroform as a solvent and tetramethylsilane as a reference substance, of the composition 1It can be determined from the integral value of the signal in the 1H-NMR measurement and the 1H-NMR spectrum obtained by the measurement. Specifically, for example, the integral value Δ 1 of the above signal (S2-2) (4 mol of hydrogen atoms), the integral value Δ S2-2 of the above signal (S2-3) (4 mol of hydrogen atoms), and the integral value Δ S2-3 of the signal (Sd) of the methylene adjacent to the hydroxy group of the group represented by the formula (d) (2 mol of hydrogen atoms), the molar ratios (C Sd / (C A2-3 +C A2-2 +C A2-3 +C D )×100) and ((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 ratio of the integral value Δ S2-2 of the signal (S2-2), the integral value Δ S2-3 of the signal (S2-3), and the integral value Δ Sd of the signal (Sd) to the sum of the integral value Δ S2-3 of the signal (S2-3), that is, ((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 ratio of the sum of the integral value Δ S2-2 of the signal (S2-2), the integral value Δ S2-3 of the signal (S2-3), and the integral value Δ Sd of the signal (Sd) to the sum of the integral value Δ S2-2 of the signal (S2-2) and the integral value Δ S2-3 of the signal (S2-3), that is, ((Δ S2-2 +Δ S2-3 ) / (Δ S2-2 +Δ S2-3 +2×ΔSd ) × 100) can be rewritten as

[0095] In the following description, let the total number of moles of the group represented by the following formula (f’) contained in the composition be C F .

Chemical formula

[0096] The 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. When the molar ratio (C F / C T × 100) is 1.7 or more, a polyurethane resin excellent in heat resistance and 100% modulus is likely to be formed by self-crosslinking of the oxetane compound. The molar ratio (C 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. When the molar ratio (C F / C T × 100) is 45.0 or less, a polyurethane resin excellent in heat resistance is likely to be formed. The molar ratio (C 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. When the molar ratio (C F / C T × 100) is within the above range, when the composition is used as a raw material for a urethane resin, a polyurethane resin with good 100% modulus and heat resistance is likely to be formed.

[0097] The molar ratio (CF / C T ×100) is, for example, (C A1-1 / (C A1-1 +C A1-2 +C A1-3 )×100). Using deuterated chloroform as a solvent and tetramethylsilane as a reference substance, the 1 1H-NMR measurement of the composition and the 1 1H-NMR spectrum obtained by the measurement can be determined from the integral values of the signals. Specifically, for example, the integral value Δ SI (for 3 mol of hydrogen atoms) of the signal (SI) and the integral value Δ Sf (for 4 mol of hydrogen atoms) of the signal (Sf) of the methylene located adjacent to the oxygen atom of the oxetane group of formula (f’), the molar ratio (C F / C T ×100) can be calculated. In this case, the molar ratio (C F / C T ×100) can be rephrased as 0.75 times the ratio of the integral value Δ SI of the signal (SI) to the integral value Δ Sf of the signal (Sf) (0.75×Δ Sf / Δ SI ×100).

[0098] The composition may be a reaction mixture of a polycarbonate polyol (B), a polyester polyol (C), and a diol (D), a polyhydric alcohol (E) and / or an oxetane compound (F) added as necessary. Since the above reaction is usually carried out in the presence of a transesterification catalyst, the composition may further contain a transesterification catalyst. Lithium acetylacetonate is preferably used as the transesterification catalyst. The content of the transesterification 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 solid at 25°C or may be liquid at 25°C. The properties of the composition can be changed depending on the types and content ratios of the components contained (for example, 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 in terms of a difunctional polyoxypropylene polyol, which is measured using GPC (Gel Permeation Chromatography) with the entire composition as the measurement target.

[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 the composition means the number of milligrams (mg) of potassium hydroxide equivalent to the hydroxyl groups 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 the composition means the number of milligrams (mg) of potassium hydroxide equivalent to the hydroxyl groups 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 substance. When performing 1 1H-NMR measurement on the composition, for example, the above signal (S1-1) is observed in the range of 3.435 ppm or more and 3.475 ppm or less in the 1 1H-NMR spectrum, and the above signal (S1-2) is observed in the range of 3.475 ppm or more and 3.520 ppm or less in the 1 1H-NMR spectrum, and the above signal (S1-3) is observed in the range of 3.400 ppm or more and 3.435 ppm or less in the 1 1H-NMR spectrum, and the above signal (S2-2) is observed in the range of 3.595 ppm or more and 3.618 ppm or less in the 1 1H-NMR spectrum, and the above signal (S2-3) is observed in the range of 3.550 ppm or more and 3.595 ppm or less in the 1 1H-NMR spectrum, and the above signal (Sd) is observed in the range of 3.618 ppm or more and 3.710 ppm or less in the 1 1H-NMR spectrum. In addition, the integral value Δ of the signal (Se) of methylene located adjacent to the hydroxy group of the polyhydric alcohol (E) Se is 1 observed in the range of 3.710 ppm or more and 3.760 ppm or less in the 1H-NMR spectrum, and the above signal (Sf) is 1 observed in the range of 4.390 ppm or more and 4.500 ppm or less in the 1H-NMR spectrum. Further, when R in the formula (I) 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 when R in the formula (I) 1 is a methyl group, the above signal (SI) is observed in the range of 0.700 ppm or more and 1.130 ppm or less. Therefore, in this embodiment, from the ratio of the integral values of these signals, the molar ratio (C A1-1 / (C A1-1 +C A1-2 +C A1-3 )×100), the molar ratio ((C A2-2 +C A2-3 ) / (C A1-1 +C A1-2 +C A1-3 ), the 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 determined.

[0107] According to this embodiment, a composition can be provided that contributes to the formation of a urethane resin having a low 100% modulus and a high softening temperature.

[0108] <Method for 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 reacting a polycarbonate polyol and a polyester polyol (transesterification reaction) in a mixed solution containing a polycarbonate polyol (B), a polyester polyol (C), and a transesterification catalyst. In this 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 also be obtained as a reaction mixture containing the compound (A1-1). Therefore, the above method can also be referred to as a method for producing the composition of the above embodiment.

[0110] The mixture may contain a diol (D) and / or an oxetane compound (F) as optional components. Even when the above method is such that at least one of the polycarbonate polyol (B) and the polyester polyol (C) contains a group represented by the above formula (I), the mixture 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 the preferred examples (preferred R 1 、R 2 、R 3 、R 4 and examples of R, and examples of preferred combinations) are also the same as the preferred examples and examples of preferred combinations of R 1 、R 2 、R 3 、R 4 and R of the compound (A1-1). From the viewpoint of easily obtaining the desired compound (A1-1), it is preferable to use lithium acetylacetonate as the transesterification catalyst.

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

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

[0113] From the perspective of facilitating appropriate control of the reaction temperature and suppressing an increase in the color number of the reaction product, the content of the transesterification catalyst in the mixed liquid may be 0.0001 to 0.1 part by mass, may be 0.001 to 0.050 part by mass, or may be 0.005 to 0.01 part by mass with respect to 100 parts by mass of the total amount of the polyol components in the mixed liquid. From the perspective of facilitating control of the reactivity of the urethanization reaction, the lower the content of the transesterification catalyst, the more preferable. When the content of the transesterification catalyst increases, the reactivity of the urethanization reaction tends to increase. From the perspective of facilitating control of the urethanization reaction, the content of the transesterification catalyst in the mixed liquid is preferably 0.001 part by mass or more, more preferably 0.002 part by mass or more, and still more preferably 0.003 part by mass or more with respect to 100 parts by mass of the total amount of the polyol components in the mixed liquid. From the perspective 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 part by mass or less, more preferably 0.040 part by mass or less, and still more preferably 0.030 part by mass or less with respect to 100 parts by mass of the total amount of the polyol components in the mixed liquid. From these perspectives, the content of the transesterification catalyst in the mixed liquid is preferably 0.001 to 0.050 part by mass, more preferably 0.002 to 0.040 part by mass, and still more preferably 0.003 to 0.030 part by mass with respect to 100 parts by mass of the total amount of the polyol components in the mixed liquid. The total amount of the polyol components refers to the total amount of compounds having two or more hydroxy groups contained in the mixed liquid (for example, polycarbonate polyol (B), polyester polyol (C), polyhydric alcohol (E), and diol (D) of optional additive components), and oxetane compound (F) of optional additive components).

[0114] In the reaction process, the mixed solution may be heated to allow the reaction to proceed, or the reaction may proceed without heating. The reaction temperature of the mixed solution is, for example, 0 to 250°C, and may also be 100 to 220°C. When the reaction temperature is 0°C or higher, the transesterification reaction easily proceeds, and the desired compound (A1-1) is easily obtained. When the reaction temperature is 250°C or lower, the color number of the obtained compound (A1-1) and the composition (polyol-containing composition) can be suppressed. Further, when the reaction temperature is 250°C or lower, the decarboxylation reaction of the carbonate group or the dehydration reaction between the terminal hydroxyl groups, which are by-produced, of the oxetane compound and / or the oxetane structure derived from a polyhydric alcohol having three or more functional groups can be suppressed. Also, the transesterification reaction may be carried out while maintaining a constant temperature, or may be carried out while raising the temperature stepwise or continuously according to the progress of the reaction. From the viewpoint of easily obtaining the desired compound (A1-1), it is preferable to carry out heating at a temperature T1 satisfying the following formula (α), and then carry out heating at a temperature T2 satisfying the following formula (β). Note that the temperature T1 and the temperature T2 preferably satisfy the relationship of the following formula (γ). Also, the average temperature T1 of the temperature of the first heating m and the average temperature T2 of the temperature of the second heating m preferably satisfy the relationship of the following formula (δ). Here, the progress of the reaction can be estimated from the consumption amount of the raw material obtained from the GPC chart. 180°C ≤ T1 ≤ 200°C ···(α) 190°C ≤ T2 ≤ 200°C ···(β) T1 < T2 ···(γ) T1 m < T2 m ···(δ)

[0115] The heating of the mixture can be carried out under normal pressure, but it can also be carried out under reduced pressure (for example, under a pressure of 101 to 1 kPa). This makes it possible to remove the moisture remaining in the mixture, accelerate the progress of the reaction, and suppress the coloring of the composition. Furthermore, under reduced pressure, it becomes 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 obtaining 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). It is more preferable that the temperature of the first heating is the temperature T1 satisfying the relationship of the above formula (α), the temperature of the second heating is the temperature T2 satisfying 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 heating of the mixture can also be carried out while introducing nitrogen. This makes it possible to remove moisture from the mixture and accelerate the progress of the reaction. Furthermore, by purging with nitrogen, it becomes possible to suppress the coloring of the composition. From the viewpoint of facilitating the obtaining 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 production method, post-treatments such as distillation and drying may be performed on the obtained reaction mixture. Also, in the above production method, after obtaining the compound (A1-1) or a composition containing the same, components such as a polyhydric alcohol (E) and / or an oxetane compound (F) may be added and prepared.

[0118] <Urethane Resin and Its Production 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 by a chain extender or the like.

[0119] (Polyol component) The polyol component contains the above compound (A1-1). The polyol component may contain a polyol other than the compound (A1-1) (a compound having two or more terminal hydroxyl groups) or an oxetane compound (F) (a compound having one hydroxyl group). The polyol component may further contain, for example, polyols that can be contained in the above 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 may be the same as the content ratio of polyols in the above composition (for example, 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 removing compounds other than polyols from the above composition.

[0120] The polyol component may further contain a polyol having an acidic group. In this case, the urethane resin will contain an acidic group. The urethane resin having an acidic group is suitably used for 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) capable of imparting hydrophilicity to an isocyanate group-terminated prepolymer obtained by reaction with an isocyanate. Examples of such a polyol having an acidic group 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. Also, modified polyisocyanates which are modified products of these can be used. Examples of the modified polyisocyanate include isocyanurate-modified polyisocyanates (trimers of isocyanates), allophanate-modified polyisocyanates, uretdione-modified polyisocyanates, urethane-modified polyisocyanates, biuret-modified polyisocyanates, uretonimine-modified polyisocyanates, acylurea-modified polyisocyanates, and the like. 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, 2,4-tolylene diisocyanate / 2,6-tolylene diisocyanate mixture, 4,4'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate / 4,4'-diphenylmethane diisocyanate mixture, m-xylylene diisocyanate, p-xylylene diisocyanate, 4,4'-diphenyl ether 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, 3,3'-dimethoxydiphenyl-4,4'-diisocyanate, and the like.

[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 isocyanatomethyl ester, 2-isocyanatoethyl-2,6-diisocyanatohexanoate, 2-isocyanatopropyl-2,6-diisocyanatohexanoate, etc.

[0126] Examples of alicyclic isocyanates include isophorone diisocyanate, cyclohexyl diisocyanate, bis(isocyanatomethyl)cyclohexane, dicyclohexylmethane diisocyanate, methylcyclohexyl diisocyanate, dicyclohexyldimethylmethane diisocyanate, 2,2'-dimethyl dicyclohexylmethane diisocyanate, bis(4-isocyanato-n-butylidene) pentaerythritol, 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)-6-(isocyanatomethyl)bicyclo[2.2.1]heptane, 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, 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, hydrogenated tetramethylxylene diisocyanate, and the like.

[0127] (Polyol component / Polyisocyanate component mixing ratio) The mixing ratio of the polyol component and the polyisocyanate component is preferably such that the molar ratio of the active hydrogen in the polyol component to the isocyanate group in the polyisocyanate component is 9:1 to 1:9, and more preferably 6:4 to 4:6. When the mixing ratio is within this range, the urethane resin tends to have more excellent performance.

[0128] (Chain extender) The chain extender can be appropriately selected according to the purpose, application, etc. Examples of the chain extender include water; low molecular weight polyols such as 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, tricyclodecanedimethanol, xylylene glycol, bis(p-hydroxy)diphenyl, bis(p-hydroxyphenyl)propane, 2,2-bis[4-(2-hydroxyethoxy)phenyl]propane, bis[4-(2-hydroxyethoxy)phenyl]sulfone, 1,1-bis[4-(2-hydroxyethoxy)phenyl]cyclohexane; high molecular weight polyols such as polyester polyol, polyester amide polyol, polyether polyol, polyether ester polyol, polycarbonate polyol, polyolefin polyol; polyamines such as ethylenediamine, isophoronediamine, 2-methyl-1,5-pentanediamine, aminoethyl ethanolamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, etc. The blending 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 with respect 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 as being included in both the chain extender and the polyol component.

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

[0130] During the urethane-forming reaction, a catalyst (urethane-forming 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 typified by 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 based on 100 parts by mass of the total amount of the polyol component and the polyisocyanate component.

[0131] When using a catalyst during the urethanization reaction, it is preferable to use a phosphorus compound for the treatment of the catalyst. The phosphorus compound is not particularly limited. For example, triester phosphates such as trimethyl phosphate, triethyl phosphate, tributyl phosphate, di-2-ethylhexyl phosphate, triphenyl phosphate, tricresyl phosphate, cresyl diphenyl phosphate, etc.; acidic phosphoric acid 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, atylene glycol acid phosphate, 2-hydroxyethyl methacrylate acid phosphate, dibutyl phosphate, monobutyl phosphate, monoisodecyl phosphate, bis(2-ethylhexyl) phosphate, etc.; phosphite esters such as triphenyl 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) hydrogen phosphite, dilauryl hydrogen phosphite, dioleyl hydrogen phosphite, diphenyl hydrogen phosphite, tetraphenyldipropylene glycol diphosphite, bis(decyl)pentaerythritol diphosphite, tristearyl phosphite, distearyl pentaerythritol diphosphite, tris(2,4-di-tert-butylphenyl) phosphite, etc.; phosphoric acid, phosphorous acid, hypophosphorous acid, etc. These can be used alone or in combination of two or more.Among these, acidic phosphate 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 with respect to 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, ε-caprolactone; amides such as dimethylformamide, diethylformamide, dimethylacetamide; sulfoxides such as dimethyl sulfoxide; ethers such as tetrahydrofuran, dioxane, 2-ethoxyethanol; ketones such as methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone; aromatic hydrocarbons such as benzene and toluene, etc. can be used.

[0133] The urethane resin described above has good elongation and texture, excellent durability, and in some cases, good breaking strength. Therefore, the above 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 urethane resin described above. The specific embodiment of the urethane resin may be as described above.

[0135] As an example of the case of using as a coating agent, an in-mold coating method applying RIM (Reaction Injection Moldind) can be mentioned. Specifically, it is a method of molding a plastic substrate in an injection mold and further forming a urethane coating film on the surface of the molded product in the mold. In this method, the internal volume of the mold is constant, not only the density, thickness, and hardness of the urethane coating film are stabilized, but also the unevenness on the mold surface can be faithfully reproduced to obtain a highly designed appearance.

[0136] <Aqueous urethane resin dispersion> The aqueous urethane resin dispersion contains an aqueous medium and a urethane resin or its neutralized product dispersed in the aqueous medium. The urethane resin is one of the above-described urethane resins that has an acidic group (including those containing a polyol having an acidic group as a polyol component).

[0137] As the aqueous medium, in addition to water, solutions 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 possessed by 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, smoothness, etc. of the coating film, volatile neutralizing agents that are easily dissociated by heating, such as ammonia, trimethylamine, and triethylamine, are 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 anionically polar group-containing compound can also be used. Examples of the anionically polar group-containing compound include those composed 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 anionically polar groups contained in the organic acid may be introduced alone or may be associated with metal ions like a chelate.

[0140] When producing an aqueous urethane resin dispersion, a cationic polar group-containing compound can also be used. The cationic polar group-containing compound consists of, for example, a tertiary amine having one or more active hydrogens and one selected from the group consisting of neutralizing agents for inorganic acids, neutralizing agents for organic acids, and quaternizing agents. Also, as the cationic polar group-containing compound, cationic compounds such as primary amine salts, secondary amine salts, tertiary amine salts, and pyridinium salts can also be used.

[0141] Examples of the tertiary amine 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, tris(isopropanol)amine, N-methyl-bis-(3-aminopropyl)-amine, N-methyl-bis-(2-aminopropyl)-amine, etc. Also, those obtained by adding an alkylene oxide to a primary amine such as ammonia or methylamine, or a secondary amine such as dimethylamine can also be used.

[0142] Examples of the inorganic acid and organic acid include 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, alkyl halides such as ethyl bromide, propyl bromide, and butyl bromide can be used.

[0144] An aqueous urethane resin dispersion can be produced by sequentially performing the steps of reacting a polyol component containing a polyol having an acidic group and a polyisocyanate component in the presence or absence of a solvent to form a urethane prepolymer, neutralizing the acidic group 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 needed to accelerate the reaction and control the amount of by-products.

[0145] The 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 feeling, etc. Therefore, the above aqueous urethane resin dispersion can be suitably used for artificial leather, synthetic leather, and coating agents.

[0146] <Two-component composition set> The polyol component and the polyisocyanate component for forming the above urethane resin may be stored and transported in separate containers as a two-component composition set. The two-component composition set includes a first liquid containing at least the above polyol component and a second liquid containing at least the above polyisocyanate component. When using a chain extender, a catalyst, a solvent, etc., these may be contained in the first liquid and / or the second liquid, or may be blended separately from the first liquid and the second liquid. The above two-component 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 using the above two-component composition set as a coating agent, for example, after mixing the first liquid and the second liquid, the resulting mixed liquid is applied onto 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 case where the two-liquid composition set is used as a coating agent, it can be preferably used also in the production of artificial leather, synthetic leather, etc. as a resin composition that does not use an organic solvent, and forms a polyurethane resin excellent in adhesion, flexibility, touch feeling, etc.

[0148] The urethane resin-forming composition containing the above-described polyol component and the above-described polyisocyanate component, and the polyurethane resin composition containing the above-described urethane resin are preferably used as an aqueous polyurethane resin emulsion, a polyurethane resin synthesized under solvent-free conditions, or a precursor thereof. And, by curing this aqueous polyurethane resin emulsion or the polyurethane resin synthesized under solvent-free conditions, a tough molded body such as a coating film or a film having a reduced 100% modulus (good texture) and a high softening temperature can be obtained, and it can be preferably used for leather applications such as artificial leather and synthetic leather, and as a surface treatment agent for leather. The 100% modulus is one of the indexes for quantifying the moist, elastic and high-class feeling when touching synthetic leather, and when the numerical value is within a certain numerical range, it becomes a urethane resin having good above characteristics.

[0149] <Use> The composition, urethane resin, aqueous urethane resin dispersion and coating agent of the present embodiment described above can be used in a coating composition preferably used as an automotive exterior clear paint and an automotive interior paint. Further, the composition, urethane resin, aqueous urethane resin dispersion and coating agent of the present embodiment can be preferably used for home appliances, OA (Office Automation) products, surface treatment of leather, surface treatment of synthetic leather, etc.

Example

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

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

[0152] [Synthesis Example 2: Synthesis of Polycarbonate Polyol (B) 2] In a 1 L two-necked glass reactor equipped with a stirrer, a thermometer, a heating device, and a cooler, 272.7 g of trimethylolpropane, 266.2 g of 1,6-hexanediol, 461.2 g of diethyl carbonate, and 0.05 g of potassium hydrogen carbonate were mixed, and the mixture was reacted at 100 to 150 °C for 8 hours while removing low-boiling components under normal pressure. Further, the reaction temperature was set to 150 °C, the pressure in the flask was reduced to 1 kPa, and the reaction was carried out for another 8 hours to obtain a polycarbonate polyol (PC-2).

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

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

[0155] <Example> (Example 1) In a 0.5 L four-necked glass reactor (Reactor A) equipped with a stirrer, a thermometer, a heating device, and a cooler, 322 g of N-980N, 140 g of Placcel 220, 13 g of Placcel 305, 24.6 g of 1,6-hexanediol (HG), and 0.05 g of lithium acetylacetonate were mixed. Under normal pressure, the mixture was heated at 180 to 200 °C (180 °C at the beginning and 200 °C at the end) and reacted for 5 hours at a flow rate of 50 ml / min under a nitrogen atmosphere. Further, the pressure in the flask was reduced to 26.7 kPa at a reaction temperature of 200 °C, and the reaction was carried out for another 5 hours to obtain a composition (PCP-1) containing the 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 the 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 in Reactor A was used.

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

[0158] (Example 4) Into reactor A, 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. Otherwise, in the same manner as in Example 1, a composition (PCP-4) containing the polycarbonate polyol represented by the above formula (A1-1) was obtained.

[0159] (Example 5) Into reactor A, 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. Otherwise, in the same manner as in Example 1, a composition (PCP-5) containing the polycarbonate polyol represented by the above formula (A1-1) was obtained.

[0160] (Example 6) Into reactor A, 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. Otherwise, in the same manner as in Example 1, a composition (PCP-6) containing the polycarbonate polyol represented by the above formula (A1-1) was obtained.

[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 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 Placcel 320, and 0.05 g of lithium acetylacetonate was used in 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 Placcel 320, and 0.05 g of lithium acetylacetonate was used in Reactor A.

[0166] (Example 12) Into reactor A, a 2 L four-necked glass reactor equipped with a stirrer, a thermometer, a heating device, and a cooler, 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 were mixed. 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 the obtained mixed solution was used.

[0167] (Example 13) Into reactor A, a mixed solution obtained by mixing 250 g of the polycarbonate polyol (PC-1) obtained in Synthesis Example 1, 250 g of Placcel 320, and 0.05 g of lithium acetylacetonate was used. 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 for this.

[0168] (Example 14) Into reactor A, 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. 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 for this.

[0169] (Example 15) Into reactor A, 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. 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 for this.

[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 Placcel 320, and 0.05 g of lithium acetylacetonate was used in Reactor A.

[0171] (Example 17) 90 g of the composition (PCP-13) obtained in Example 13 and 10 g of trimethylolpropane were mixed in Reactor A 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 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 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 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 Placcel 320, and 0.05 g of lithium acetylacetonate was used in 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 Placcel 320, and 0.05 g of lithium acetylacetonate was used in 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 Placcel 320, 14.5 g of 3-ethyl-3-hydroxymethyloxetane, and 0.05 g of lithium acetylacetonate was used in 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 (PCD-2) containing polycarbonate diol.

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

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

[0182] (Comparative Example 5) A composition (PCP-25) containing the 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 Placcel 305, and 0.05 g of barium acetate was used in reactor A.

[0183] (Analysis and Evaluation) [Measurement of Number-Average Molecular Weight] Under the following conditions, GPC analysis of the polycarbonate polyol obtained above and the composition obtained above was performed 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 (manufactured by Tosoh Corporation) · G3000H-XL · G3000H-XL · G2000H-XL · G2000H-XL (3) Mobile phase: THF (tetrahydrofuran) (4) Detector: RI (refractive index) detector (accessory of HLC-8420) (5) Temperature: 40 °C (6) Flow rate: 1.000 ml / min (7) Calibration curve: A calibration curve was obtained using the following products (all bifunctional polyoxypropylene polyols manufactured by Sanyo Chemical Industries, Ltd.). · "Sun Nix PP-200" (number-average molecular weight = 200, average number of functional groups: 2) · "Sun Nix PP-400" (number-average molecular weight = 400, average number of functional groups: 2) · "Sunnex PP-1000" (number average molecular weight = 1000, average number of functional groups: 2) · "Sunnex PP-2000" (number average molecular weight = 2000, average number of functional groups: 2) · "Sunnex PP-3000" (number average molecular weight = 3200, average number of functional groups: 2) · "Sunnex PP-4000" (number average molecular weight = 4160, average number of functional groups: 2) (8) Approximation formula of calibration curve: Cubic equation (9) Concentration of sample solution: 0.5 mass% THF solution

[0184] [Measurement of hydroxyl value] In accordance with JIS K1557-1, 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 acetylating reagent. The results are shown in Tables 1, 3, 5 and 7.

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

[0186] [Property evaluation] Using the composition obtained above as a sample, the sample was heated at 80 °C for 1 hour and then left at 25 °C for 3 days. The state of the sample after standing was visually confirmed. If there was any fluidity at the above temperature, it was regarded as liquid, and if there was no fluidity, it was regarded as solid. The results are shown in Tables 3, 5 and 7.

[0187] [Composition analysis] The composition analysis of the composition was carried out by the following procedure.

[0188] First, the composition (sample) obtained above was dissolved in deuterated chloroform (manufactured by Fujifilm Wako Pure Chemical Corporation) to obtain a solution. Tetramethylsilane (TMS) was added to the solution as a chemical shift standard to obtain a test solution. For the obtained test solution, using JNM-ECX400 manufactured by JEOL Ltd. 11H-NMR was measured with the TMS signal set at 0 ppm. 1 A 1H-NMR spectrum was obtained. For reference, the 1 1H-NMR spectrum of the composition obtained in Example 5 is shown in FIGS. 1 and 2. The measurement was carried out under the following conditions. -Conditions- ·Resonance frequency: 400 MHz ·Pulse width: 45 degrees ·Waiting time: 5 seconds ·Number of integrations: 64 ·Sample solution concentration (TMS-containing deuterated chloroform): 3 mass vol%

[0189] Next, from the 1 1H-NMR spectrum obtained above, the integration value Δ of the signal (S1-1) of the methylene adjacent to the hydroxy group of the group represented by the above formula (a1-1) S1-1 and the integration value Δ of the signal (S1-2) of the methylene adjacent to the hydroxy group of the group represented by the above formula (a1-2) S1-2 and the integration value Δ of the signal (S1-3) of the methylene adjacent to the hydroxy group of the group represented by the above formula (a1-3) S1-3 and the integration value Δ of the signal (S2-2) of the methylene adjacent to the hydroxy group of the group represented by the above formula (a2-2) S2-2 and the integration value Δ of the signal (S2-3) of the methylene adjacent to the hydroxy group of the group represented by the above formula (a2-3) S2-3 and the integration value Δ of the signal (Sd) of the methylene adjacent to the hydroxy group of the group represented by the above formula (d) Sd and the integration value Δ of the signal (Se) of the methylene adjacent to the hydroxy group of the group represented by the above formula (e) Se and the integration value Δ of the signal (Sf) of the methylene adjacent to the oxygen atom of the oxetane group of the group represented by the above formula (f') Sf were determined. Also, when R 1 of the group represented by formula (I) is a methyl group or an ethyl group, the integration values of the signals of these terminal methyls were determined and these were taken as the integration value Δ of the signal (SI) SI .

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

[0191] Note that the baseline for integral value measurement was a straight line drawn horizontally with reference to the lowest spectral intensity by comparing the spectral intensities within the specified spectral range. Signals (S1-1), (S1-2), (S2-2), and (Se) usually show single peaks, but may be affected by trace amounts of moisture and the peaks may split. If detected as split peaks, they deviate from the above integral range and accurate C A1-1 , C A1-2、 C A2-2 and C E cannot be obtained. Therefore, the integral values obtained from each signal are those when showing single peaks.

[0192] From the obtained integral values, 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) were calculated. The results are shown in Tables 3, 5, and 7.

[0193] In addition, in PCP-1 to 23, the presence of compound (A1-1) was suggested from the presence of signal (S1-1). On the other hand, in PCD-1 to 3 and PCP-24 to 25, signal (S1-1) was not confirmed.

[0194] Also, if the total number of moles of the groups in which all three bonds in formula (I) are bonds to carbonyl groups is C A3 , then C T is equal to the sum of 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, from the integration values of the above signals (SI), (S1-1) to (S1-3), (S2-2) to (S2-3), (Se), and (Sf), from C T to C A1-1 , C A1-2 , C A1-3、 C A2-2 , C A2-3 , C E , and CF Since it was confirmed that the value obtained by subtracting was positive, the presence of compound (A-3) was suggested.

[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 compounding components.

[0198] (Physical Property Evaluation) A urethane cured film (film) was produced by the following method, and the obtained film was used as a sample to evaluate the physical properties (tensile properties, heat resistance, and hot water resistance).

[0199] [Production of Urethane Cured Coating] First, the composition obtained above, a polyisocyanate component (C-2612), a urethanization catalyst, a phosphorus compound (JP508), and a diluting solvent were mixed in the formulations (unit: g) described in Tables 8, 9, and 10 in a 200 mL glass bottle. Immediately after mixing, the mixed solution was poured onto a release paper and cast with a bar coater to form a film with a thickness of 200 μm. Subsequently, the cast film was 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 film (film).

[0200] [Tensile property 100% 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 apparatus: Tensilon UTA-500 (manufactured by A&D Company, Limited) ·Measurement conditions: 25°C × 50% RH ·Head speed: 200 mm / min ·Dumbbell No. 4

[0201] [Softening temperature] After obtaining a test piece from the obtained film using a dumbbell, a 2 cm scale line was marked on the test piece, and the thickness at the center of the scale line was measured. A weight of a predetermined weight was attached to one gripping part of the test piece, the other gripping part was clamped with a double clip, and after suspending it in a dryer with the clip on the upper side, the temperature inside the dryer was raised, the distance between the scale lines was observed, and the temperature when the distance between the scale lines became 4 cm was read as the softening temperature. ·Processing apparatus: Forced air constant temperature dryer DRK633DA (manufactured by Advantec) ·Weight of weight: Thickness at the center of the scale line (μm) × 0.05 g ·Dumbbell No. 2 (conforming to JIS K6251) ·Temperature rising rate: 5°C / min

[0202] [Glass transition temperature] After obtaining test specimens (width 0.4 cm, length 2.5 cm) from the resulting film using dumbbells, the thickness (about 100 - 200 μm) at the center of the gauge marks was measured. The glass transition temperature was defined as the temperature at the peak top of the loss modulus (E”) / storage modulus (E’) = tanδ obtained. - Conditions - · Processing apparatus: RHEOVIBRON DDV - 01GP Dynamic Viscoelastomeret (manufactured by Orientec Co., Ltd.) · Range: -50 to 40 °C · Heating rate: 3 °C / min · Frequency: 35 Hz · Amplitude: 16 μm · Static tension: 5.00 gf

[0203] [Evaluation of hydrolysis resistance] The resulting film was immersed in water and left in a thermostat at 90 °C for 28 days to obtain test specimens. Thereafter, the appearance of each test specimen was visually evaluated. As the test apparatus, ESPEC CORP (manufactured by Espec Corporation) was used. The change in the film appearance after the test with respect to the film appearance before the test was evaluated as A, B, C, and D (A: no change, B: deformation, C: white, D: dissolution). In the case of a good polyurethane film, the film shape is maintained even after the hydrolysis test. In the hydrolysis test, the reorientation and decomposition of polyurethane are promoted simultaneously. If there is deformation in the film appearance after the hydrolysis test, it suggests the progress of polyurethane reorientation, and when the reorientation progresses significantly, the film turns white. Also, the film may dissolve due to the decomposition of carbonate bonds in polyurethane.

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

[0205]

Table 8

Table 9

Table 10

[0206] The details of the materials used in the examples are as follows. · 1,6 - Hexanediol: Manufactured by BASF-JAPAN · 1,4 - Butanediol: Manufactured by Tokyo Chemical Industry Co., Ltd. · 3 - Methyl 1,5 - pentanediol: Manufactured by FUJIFILM Wako Pure Chemical Corporation · Trimethylolpropane: Manufactured by Sigma-Aldrich · Diethyl carbonate: Manufactured by Sigma-Aldrich · Potassium hydrogen carbonate: Manufactured by FUJIFILM Wako Pure Chemical Corporation ·Tetrabutyl titanate: manufactured by Tokyo Chemical Industry Co., Ltd. ·N-980N, N-980R: Polycarbonate diol (number average molecular weight = 2000, hydroxyl value = 56.1, number of functional groups = 2, 1,6-hexanediol-based polycarbonate diol), manufactured by Tosoh Corporation ·Placcel 220: Polycaprolactone diol (number average molecular weight = 2000, hydroxyl value = 56.1, number of functional groups = 2), manufactured by Daicel Corporation ·Placcel 210: Polycaprolactone diol (number average molecular weight = 1000, hydroxyl value = 112, number of functional groups = 2), manufactured by Daicel Corporation ·N-135: Polyester polyol (number average molecular weight = 2600, hydroxyl value = 43.1, number of functional groups = 2, adipic acid / 1,4-butanediol-based polyester diol), manufactured by Tosoh Corporation ·Placcel 320: Polycaprolactone triol (number average molecular weight = 2000, hydroxyl value = 84.2, number of functional groups = 3), manufactured by Daicel Corporation ·Placcel 305: Polycaprolactone triol (number average molecular weight = 550, hydroxyl value = 305, number of functional groups = 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, number of functional groups = 2, 1,6-hexanediol / ester copolymer-based polycarbonate diol), manufactured by Tosoh Corporation ·Lithium acetylacetonate: manufactured by Sigma-Aldrich ·Barium acetate: manufactured by Fujifilm Wako Pure Chemical Corporation ·JP-508: Trade 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: Dioctyltin dilaurate, manufactured by Kishida Chemical Co., Ltd. ·BYK-331: Silicon-based surface conditioner, manufactured by BYK ·Methyl ethyl ketone: manufactured by Maruzen Petrochemical Co., Ltd. · Toluene: Manufactured by FUJIFILM Wako Pure Chemical Corporation

Claims

1. A compound represented by the following formula (A1-1), A polycarbonate polyol represented by the following formula (A1-2), A polyester polyol represented by the following formula (A1-3), A polycarbonate polyol represented by the following formula (A2-2), It 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 molar ratio ((C A2-2 + C A2-3) / (C A1-1 + C A1-2 + C A1-3)) is between 0.01 and 0.

750. A composition having a molar ratio (C A1-1 / (C A1-1 + C A1-2 + C A1-3) × 100) of 80 or less. 【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 (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 5】 [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.] 【Transformation 6】 [In formula (a1-1), R1 is the same as above, and * indicates a coupling.] 【Transformation 7】 [In formula (a1-2), R1 is the same as above, and * indicates a coupling.] 【Transformation 8】 [In formula (a1-3), R1 is the same as above, and * indicates a coupling.] 【Chemistry 9】 [In formula (a2-2), R1 is the same as above, and * indicates a coupling.] 【Chemistry 10】 [In formula (a2-3), R1 is the same as above, and * indicates a coupling.]

2. The composition according to claim 1, wherein the molar ratio (C A1-1 / (C A1-1 + C A1-2 + C A1-3) × 100) is 5.3 to 80.

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 11】 [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 12】 [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 13】 [In formula (a1-1), R1 is the same as above, and * indicates a coupling.] 【Chemistry 14】 [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 15】 [In formula (a1-2), R1 is the same as above, and * indicates a coupling.] 【Chemistry 16】 [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 17】 [In formula (a1-3), R1 is the same as above, and * indicates a coupling.] [Chemistry 18] [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 1 or 2, wherein the molar ratio (CA2-3 / CT) is 0.001 to 0.

234. 【Chemistry 19】 [In formula (a2-3), R1 is the same as above, and * indicates a coupling.] 【Chemistry 20】 [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 1 or 2, wherein the molar ratio (C A2-3 / (C A2-2 + C A2-3 + C D) × 100) is 0.010 to 10.

20. 【Chemistry 21】 [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 22】 [In formula (a2-2), R1 is the same as above, and * indicates a coupling.] 【Chemistry 23】 [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 1 or 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 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.]

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. 【Chemistry 27】 [In equation (f'), R 1 is the same as above, and * indicates a coupling.] 【Chemistry 28】 [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 composition described in Claim 1 or 2, 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 29】 [In formula (I), R1 is the same as above, and * indicates a coupling.] 【Transformation 30】 [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), a polyester polyol represented by the following formula (A1-3), a polycarbonate polyol represented by the following formula (A2-2), and 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 molar ratio ((C A2-2 + C A2-3) / (C A1-1 + C A1-2 + C A1-3)) is between 0.01 and 0.

750. A urethane resin having a molar ratio (C A1-1 / (C A1-1 + C A1-2 + C A1-3) × 100) of 80 or less. 【Chemistry 31】 [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 32】 [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 33】 [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.] 【Transformation 34】 [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.] 【Chemistry 35】 [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.] 【Transformation 36】 [In formula (a1-1), R1 is the same as above, and * indicates a coupling.] 【Chemistry 37】 [In formula (a1-2), R1 is the same as above, and * indicates a coupling.] 【Transformation 38】 [In formula (a1-3), R1 is the same as above, and * indicates a coupling.] 【Chemistry 39】 [In formula (a2-2), R1 is the same as above, and * indicates a coupling.] 【Chemistry 40】 [In formula (a2-3), 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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