Composition and method for producing same, urethane resin, aqueous urethane resin dispersion, and coating agent

Abstract

The present disclosure relates to a composition comprising a compound (A-1) containing a repeating unit (A) having a specific structure and a structural unit (I) derived from a polyhydric alcohol having a specific structure, wherein the content of the structure (C) derived from an oxetane compound having a specific structure contained in the composition is 0.90 to 10.7 mol % based on the total of the structure (C) derived from the oxetane compound, the structure (D) derived from a diol having a specific structure, and the structure (E) derived from a polyhydric alcohol having a specific structure.

Description

[Technical field]

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

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

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

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

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

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

[0007] However, although the polycarbonate polyols disclosed in Patent Documents 1 and 2 exhibit good mechanical properties when used as raw materials for urethane resins, they have insufficient handleability. Therefore, an object of one aspect of the present disclosure is to provide a composition that contributes to the formation of a urethane resin having high tensile strength and has good handleability, and a method for producing the same. Another object of the present disclosure is to provide a urethane resin having high tensile strength, and an aqueous urethane resin dispersion and a coating agent using the urethane resin. [Means for solving the problem]

[0008] The present disclosure provides the following aspects. [1] A composition comprising a compound (A-1) including a repeating unit (A) represented by the following formula (A), a structural unit (I) derived from a polyhydric alcohol represented by the following formula (I), a structure (C) derived from an oxetane compound represented by the following formula (C), and a terminal hydroxy group, wherein the content of the structure (C) derived from the oxetane compound represented by the following formula (C) contained in the composition is 0.90 to 10.7 mol % based on the total content of the structure (C) derived from the oxetane compound, the structure (D) derived from a diol represented by the following formula (D), and the structure (E) derived from a polyhydric alcohol represented by the following formula (E) contained in the composition. [ka] [In formula (A), R 1 is an alkanediyl group, *1-OR a -*2 or *1-R b -C(=O)-OR c -*2, R a , R b , and Rc each independently represents an alkanediyl group, *1 represents the bonding site with the carbonyl group, and *2 represents the bonding site with the oxygen atom.] [ka] [In formula (I), R 2 is a hydrogen atom, an alkyl group, or a hydroxyalkyl group, and * indicates a bond. [ka] [In formula (C), R 2 has the same meaning as above, and * indicates a bond. [ka] [In formula (D), R 3 is a hydrogen atom or an alkyl group, and * indicates a bond. 3 may be the same or different.] [ka] [In formula (E), R 2 has the same meaning as above, and * indicates a bond. [2] A composition comprising a compound (A-1) containing a repeating unit (A) represented by the following formula (A) and a structural unit (I) derived from a polyhydric alcohol represented by the following formula (I), wherein the content of the structure (C) derived from an oxetane compound represented by the following formula (C) is 2.80 to 28 mol % based on the total of the structural unit (I) derived from a polyhydric alcohol represented by the following formula (I) and the structure (C) derived from the oxetane compound. [ka] [In formula (A), R 1 is an alkanediyl group, *1-OR a -*2 or *1-R b -C(=O)-OR c -*2, R a , R b , and R ceach independently represents an alkanediyl group, *1 represents the bonding site with the carbonyl group, and *2 represents the bonding site with the oxygen atom.] [ka] [In formula (I), R 2 is a hydrogen atom, an alkyl group, or a hydroxyalkyl group, and * indicates a bond. [ka] [In formula (C), R 2 has the same meaning as above, and * indicates a bond. [3] The composition according to [1], wherein the content of the structure (C) derived from the oxetane compound is 2.80 to 28 mol % based on the total content of the structural unit (I) derived from the polyhydric alcohol and the structure (C) derived from the oxetane compound. [4] R 1 *1-OR a -*2, R a The composition according to any one of [1] to [3], wherein all of [5] R 1 *1-OR a -*2, R a The composition according to any one of [1] to [3], wherein at least one of the above is a branched alkanediyl group. [6] R 1 *1-OR a -*2, R a The composition according to any one of [1] to [4], which contains two or more types of alkanediyl groups as the alkyl group. [7] R 1 *1-OR a -*2 and an alkanediyl group and / or *1-R b -C(=O)-OR c -*2. The composition according to any one of [1] to [3]. [8] R 1 *1-OR a The composition according to any one of [1] to [3], comprising: *2 and an alkanediyl group. [9] The composition according to any one of [1] to [8], further comprising a diol (d) represented by the following formula (d), a polyhydric alcohol (e) represented by the following formula (e), and an oxetane compound (F) represented by the following formula (f): [ka] [In formula (d), R a has the same meaning as above.] [ka] [In formula (e), R 2 has the same meaning as above.] [ka] [In formula (f), R 2 has the same meaning as above.]

[10] The composition according to any one of [1] to [9], further comprising a compound (A-2) represented by the following formula (A-2), a compound (A-3) represented by the following formula (A-3), and a compound (A-4) represented by the following formula (A-4): [ka] [In formula (A-2), R 1 is as defined above, and n 2 indicates an integer of 1 or more. 1 may be the same or different.] [ka] [In formula (A-3), R 1 and R 2 is as defined above, and n 3 indicates an integer of 1 or more. 1 may be the same or different.] [ka] [In formula (A-4), R 1 and R 2 is as defined above, and n 4indicates an integer of 1 or more. 2 may be the same or different. 1 When there are multiple, they may be the same or different.

[11] The composition according to any one of [1] to [3], further containing lithium acetylacetonate.

[12] A method for producing the composition according to any one of [1] to

[11] , comprising the steps of heating a mixed liquid containing a polyhydric alcohol (B1), a diol (D1), a carbonate ester, and an ester exchange catalyst to perform a reflux reaction while removing an alcohol derived from the carbonate ester from the reaction system, thereby obtaining the composition.

[13] A method for producing the composition according to any one of [1] to

[12] , comprising a reaction step of obtaining the compound (A-1) by reacting the polycarbonate polyol (B2) with the polyester polyol (C2) in a mixed liquid containing the polycarbonate polyol (B2), a polyester polyol (C2), and a transesterification catalyst, wherein at least one of the polycarbonate polyol (B2) and the polyester polyol (C2) contains a group represented by the following formula (I), or the mixed liquid further contains a polyhydric alcohol (E2). [ka] [In formula (I), R 2 has the same meaning as above, and * indicates a bond.

[14] The method according to

[12] or

[13] , wherein the content of the transesterification catalyst in the mixed solution is 0.001 to 0.050 parts by mass per 100 parts by mass of the total amount of the polyhydric alcohol (B1), the diol (D1), and the carbonate ester in the mixed solution.

[15] The method according to any one of

[12] to

[14] , wherein the content of the transesterification catalyst in the mixed solution is 0.001 to 0.050 parts by mass per 100 parts by mass of the total amount of the polycarbonate polyol (B2) and the polyester polyol (C2).

[16] The method according to any one of

[12] to

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

[17] A urethane resin which is a polycondensate of a polyol component and a polyisocyanate component or a crosslinked product thereof, wherein the polyol component comprises the composition according to any one of [1] to

[11] .

[18] The urethane resin according to

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

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

[18] dispersed in the aqueous medium.

[20] A coating agent comprising the urethane resin according to

[17] or

[18] . Effect of the Invention

[0009] According to one aspect of the present disclosure, it is possible to provide a composition that contributes to the formation of a urethane resin having high tensile strength and has good handleability, and a method for producing the same. According to another aspect of the present disclosure, it is also possible to provide a urethane resin having high tensile strength, and an aqueous urethane resin dispersion and a coating agent using the urethane resin. [Brief description of the drawings]

[0010] [Figure 1] FIG. 1 is a diagram showing a 1H-NMR spectrum of the composition containing the polycarbonate polyol obtained in Example 1B.

[0011] [Diagram 2] FIG. 2 is a diagram showing the 1H-NMR spectrum of the composition containing the polycarbonate polyol obtained in Example 1C. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

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

[0013] The composition of the present disclosure contains a compound (A-1) that includes a repeating unit (A) represented by the following formula (A) and a structural unit (I) derived from a polyhydric alcohol represented by the following formula (I).

[0014] [ka]

[0015] [In formula (A), R 1 is an alkanediyl group, *1-OR a -*2 or *1-R b -C(=O)-OR c -*2, R a , R b , and R c each independently represents an alkanediyl group, *1 represents the bonding site with the carbonyl group, and *2 represents the bonding site with the oxygen atom.]

[0016] [ka]

[0017] [In formula (I), R 2 is a hydrogen atom, an alkyl group, or a hydroxyalkyl group, and * indicates a bond.

[0018] The composition according to the first embodiment is a composition in which the content of the structure (C) derived from an oxetane compound represented by the following formula (C) is 2.80 to 28 mol % based on the total of the structural unit (I) derived from a polyhydric alcohol and the structure (C) derived from an oxetane compound.

[0019] [ka]

[0020] [In formula (C), R 2 has the same meaning as above, and * indicates a bond.

[0021] The composition according to the second embodiment of the present disclosure is a composition in which the content of structure (C) derived from an oxetane compound is 0.90 to 10.7 mol % relative to the total content of structure (C) derived from an oxetane compound, structure (D) derived from a diol represented by formula (D) below, and structure (E) derived from a polyhydric alcohol represented by formula (E) below.

[0022] [ka]

[0023] [In formula (D), R 3 is a hydrogen atom or an alkyl group, and * indicates a bond. 3 may be the same or different.]

[0024] [ka]

[0025] [In formula (E), R 2 has the same meaning as above, and * indicates a bond.

[0026] <Compound (A-1)> The compound (A-1) may include a compound containing the repeating unit (A), the structural unit (I) derived from the polyhydric alcohol, the structure (C) derived from the oxetane compound, and a terminal hydroxyl group. The compound (A-1) may include a compound containing the repeating unit (A), the structure (C) derived from the oxetane compound, the structure (D) derived from the diol, and the structure (E) derived from the polyhydric alcohol.

[0027] R 1 The alkanediyl group represented by the formula R may be linear or branched. 1 When two or more types of alkanediyl groups represented by the following formula are present, all of them may be linear alkanediyl groups or branched alkanediyl groups, or some of them may be linear alkanediyl groups and the other part may be branched alkanediyl groups.

[0028] R 1 The number of carbon atoms of the alkanediyl group represented by the formula (I) may be, for example, 2 to 10. Specific examples of the alkanediyl group include an ethanediyl group, a 1,2-propanediyl group, a 1,3-propanediyl group, a 1,2-butanediyl group, a 1,3-butanediyl group, a 1,4-butanediyl group, a 1,5-pentanediyl group, a 2,2-dimethyl-1,3-propanediyl group, a 1,6-hexanediyl group, a 3-methyl-1,5-pentanediyl group, a 1,8-octanediyl group, a 2-ethyl-1,6-hexanediyl group, a 1,9-nonanediyl group, a 2-methyloctane-1,8-diyl group, and a 2-butyl-2-ethyl-1,3-propanediyl group. Among these, a 1,4-butanediyl group, a 1,5-pentanediyl group, a 1,6-hexanediyl group, a 3-methyl-1,5-pentanediyl group, a 2-ethyl-1,6-hexanediyl group, a 1,9-nonanediyl group, a 2-methyloctane-1,8-diyl group, and the like are preferable.

[0029] R a , R b , and R c The alkanediyl group represented by R may be the same as the alkanediyl group described above. a , R b , and R c The number of carbon atoms of the alkanediyl group represented by R may be, for example, 2 to 10. a When two or more types of alkanediyl groups represented by the formula (I) are present, all of them may be linear alkanediyl groups or branched alkanediyl groups, or some of them may be linear alkanediyl groups and the other may be branched alkanediyl groups. bWhen two or more types of alkanediyl groups represented by the formula (I) are present, all of them may be linear alkanediyl groups or branched alkanediyl groups, or some of them may be linear alkanediyl groups and the other may be branched alkanediyl groups. c When two or more types of alkanediyl groups represented by the following formula are present, all of them may be linear alkanediyl groups or branched alkanediyl groups, or some of them may be linear alkanediyl groups and the other part may be branched alkanediyl groups.

[0030] Polycarbonate polyol is R 1 , R a , R b or R c When the alkanediyl group contains two or more types of alkanediyl groups, all of them may be linear alkanediyl groups or branched alkanediyl groups, or some of them may be linear alkanediyl groups and the other parts may be branched alkanediyl groups.

[0031] R 2 The alkyl group and hydroxyalkyl group represented by the formula (I) may be linear or branched. The number of carbon atoms in the alkyl group and hydroxyalkyl group may be, for example, 1 to 6, 2 to 5, or 3 to 4. Specific examples of the alkyl group and hydroxyalkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a pentyl group, a hexyl group, a hydroxymethyl group, a hydroxyethyl group, a hydroxypropyl group, and a hydroxybutyl group. R 2 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.

[0032] The number average molecular weight of the compound (A-1) may be, for example, 200 to 6000 g / mol. Here, the number average molecular weight is the number average molecular weight calculated as a bifunctional polyoxypropylene polyol, measured by GPC (gel permeation chromatography).

[0033] The hydroxyl value of the compound (A-1) may be, for example, 30 to 800 mgKOH / g, where the hydroxyl value means the number of milligrams (mg) of potassium hydroxide equivalent to the hydroxyl group in 1 g of the compound (A-1), and is measured in accordance with JIS K1557-1.

[0034] Compound (A-1) will be described in more detail below, divided into a number of embodiments (first to fourth embodiments).

[0035] (First embodiment) In the first embodiment, the compound (A-1) is R 1 It contains only linear alkanediyl groups as R 1 are linear alkanediyl groups. Compound (A-1) is 1 Since it contains only linear alkanediyl groups as a carboxylic acid, it tends to become a solid at 25°C.

[0036] In the first embodiment, the compound (A-1) is R 1 It is preferred that the compound (A-1) contains only one type of linear alkanediyl group as the alkyl group. In this case, the compound (A-1) is more likely to become a solid at 25°C.

[0037] The number of carbon atoms in the linear alkanediyl group is preferably 2 to 10, more preferably 2 to 9, and further preferably 4 to 8. Preferred examples of the linear alkanediyl group include a 1,4-butanediyl group, a 1,5-pentanediyl group, a 1,6-hexanediyl group, and a 1,9-nonanediyl group.

[0038] The number average molecular weight of the compound (A-1) of the first embodiment is preferably 200 g / mol to 6000 g / mol, and may be 300 g / mol to 5000 g / mol or 500 g / mol to 4000 g / mol.

[0039] The hydroxyl value of the compound (A-1) of the first embodiment is preferably from 30 to 800 mgKOH / g, and may be from 40 to 700 mgKOH / g or from 50 to 600 mgKOH / g.

[0040] Second embodiment In a second embodiment, the compound (A-1) is R 1 Compound (A-1) contains two or more alkanediyl groups as R 1 Since it contains two or more types of alkanediyl groups, it tends to become liquid at 25°C.

[0041] In the second embodiment, from the viewpoint that a urethane resin having good tensile strength, elongation, and texture and excellent durability is easily formed when the compound (A-1) is used as a raw material for a urethane resin, the compound (A-1) is selected from the group consisting of R 1 It is preferable that the alkanediyl group contains only linear alkanediyl groups as the alkyl group. A preferable example of the combination of alkanediyl groups is a combination of two or more kinds of alkanediyl groups having 2 to 10 carbon atoms. A more preferable combination of alkanediyl groups is a combination of 1,6-hexanediol and at least one selected from the group consisting of 1,4-butanediol, 1,5-pentanediol, and 1,9-nonanediol.

[0042] In the second embodiment, from the viewpoint that a urethane resin having good tensile strength, elongation, and texture and excellent durability is easily formed when the compound (A-1) is used as a raw material for a urethane resin, R 1 The ratio of the number of moles of 1,6-hexanediyl groups to the total number of moles of alkanediyl groups contained as is preferably 0.20 or more (e.g., 0.20 to 0.95), more preferably 0.30 or more (e.g., 0.30 to 0.90), and even more preferably 0.40 or more (e.g., 0.40 to 0.70 or 0.50 to 0.60).

[0043] The number average molecular weight of the compound (A-1) of the second embodiment is preferably 200 g / mol to 6000 g / mol, and may be 300 g / mol to 5000 g / mol or 500 g / mol to 4000 g / mol.

[0044] The hydroxyl value of the compound (A-1) of the second embodiment is preferably from 30 to 800 mgKOH / g, and may be from 40 to 700 mgKOH / g or from 50 to 600 mgKOH / g.

[0045] Third embodiment In a third embodiment, the compound (A-1) is R 1 The compound (A-1) of the third embodiment contains a branched alkanediyl group as R 1 Since it contains a branched alkanediyl group as a carboxylic acid, it tends to become liquid at 25°C.

[0046] In a third embodiment, the compound (A-1) is R 1 The two or more alkanediyl groups may all be branched alkanediyl groups, but from the viewpoint of easily forming a urethane resin having excellent handleability, good elongation and texture, and excellent durability when used as a raw material for a urethane resin, it is preferable that some of the two or more alkanediyl groups are linear alkanediyl groups. In this case, compound (A-1) may contain R 1 The ratio of the number of moles of branched alkanediyl groups to the total number of moles of alkanediyl groups contained as is preferably 0.10 to 1.00, more preferably 0.20 to 0.90, even more preferably 0.30 to 0.70, and still more preferably 0.40 to 0.60.

[0047] The number of carbon atoms in the branched alkanediyl group is preferably 2 to 10, more preferably 3 to 9, and even more preferably 4 to 8. The number of carbon atoms in the main chain (straight chain having the largest number of carbon atoms) of the branched alkanediyl group is preferably 2 to 9, more preferably 3 to 8, and even more preferably 4 to 7. Preferred examples of the branched alkanediyl group are a 3-methylpentane-1,5-diyl group and a 2-methyl-1,8-octanediyl group.

[0048] The number of carbon atoms in the linear alkanediyl group is preferably 2 to 10, more preferably 3 to 9, and further preferably 4 to 8. Preferred examples of the linear alkanediyl group include a 1,4-butanediyl group, a 1,5-pentanediyl group, a 1,6-hexanediyl group, and a 1,9-nonanediyl group.

[0049] In the third embodiment, the compound (A-1) is added with R from the viewpoint that, when used as a raw material for a urethane resin, a urethane resin having excellent handling properties, good elongation and texture, and excellent durability is easily formed. 1 The ratio of the number of moles of 1,6-hexanediyl groups to the total number of moles of alkanediyl groups contained as is preferably 0.05 or more (e.g., 0.05 to 1.00), more preferably 0.10 or more (e.g., 0.10 to 0.90), further preferably 0.20 or more (e.g., 0.20 to 0.80), and particularly preferably 0.30 or more (e.g., 0.30 to 0.70 or 0.40 to 0.60).

[0050] The number average molecular weight of the compound (A-1) of the third embodiment is preferably 200 g / mol to 6000 g / mol, and may be 300 g / mol to 5000 g / mol or 500 g / mol to 4000 g / mol.

[0051] The hydroxyl value of the compound (A-1) of the third embodiment is preferably from 30 to 800 mgKOH / g, and may be from 40 to 700 mgKOH / g or from 50 to 600 mgKOH / g.

[0052] (Fourth embodiment) In a fourth embodiment, the compound (A-1) is R 1 As *1-OR a -*2 and an alkanediyl group and / or *1-R b -C(=O)-OR c The compound (A-1) of the fourth embodiment includes R 1 As *1-OR a -*2 and an alkanediyl group and / or *1-R b -C(=O)-ORc -*2 Because it contains, it tends to become liquid at 25°C.

[0053] In the fourth embodiment, the property of the compound (A-1) is not particularly limited, and the compound (A-1) may be a solid at 25° C. or a liquid at 25° C. The property of the compound (A-1) is determined by adding R 1 , R a , R b , or R c The types of alkanediyl groups contained as R (such as the number of carbon atoms and the presence or absence of branching) and the hydroxyl value of the compound (A-1) can be varied. For example, when R 1 , R a , R b or R c When the total mole number of branched alkanediyl groups in compound (A-1) relative to the total mole number of alkanediyl groups contained as a branched alkanediyl group is 0.2 to 1.0, and when compound (A-1) has a high hydroxyl value, compound (A-1) tends to become a liquid at 25°C.

[0054] In the fourth embodiment, when used as a raw material for a urethane resin, a urethane resin having excellent durability such as heat resistance, moist heat resistance, hot water resistance, etc. is easily formed. From this viewpoint, R 1 is an alkanediyl group, and *1-OR a -*2 is more preferable.

[0055] In the fourth embodiment, the compound (A-1) is added with R from the viewpoint that a urethane resin having excellent 100% modulus and heat resistance is easily formed when the compound (A-1) is used as a raw material for the urethane resin. 1 Alkanediyl groups included as *1-OR a -*2 and *1-R b -C(=O)-OR c -*2, the total number of moles, R 1 Included as *1-OR aThe ratio of the number of moles of -*2 is preferably 0.10 or more (for example, 0.10 to 0.90), more preferably 0.20 or more (for example, 0.20 to 0.80), further preferably 0.30 or more (for example, 0.30 to 0.70), and particularly preferably 0.40 or more (for example, 0.40 to 0.60).

[0056] The number average molecular weight of the compound (A-1) of the fourth embodiment is preferably 200 g / mol to 6000 g / mol, and may be 300 g / mol to 5000 g / mol or 500 g / mol to 4000 g / mol.

[0057] The hydroxyl value of the compound (A-1) of the fourth embodiment is preferably from 30 to 800 mgKOH / g, and may be from 40 to 700 mgKOH / g or from 50 to 600 mgKOH / g.

[0058] <Raw materials> The polycarbonate polyol (compound (A-1)) described in the first to third embodiments may be, for example, a reaction product of a polyhydric alcohol represented by the following formula (b) (hereinafter also referred to as "polyhydric alcohol (B1)"), a diol represented by the following formula (d) (hereinafter also referred to as "diol (D1)"), and a carbonate ester, or a reaction product of a polyhydric alcohol (B1), a diol (D1), a carbonate ester, and an oxetane compound represented by the following formula (f) (hereinafter also referred to as "oxetane compound (F1)").

[0059] [ka]

[0060] [In formula (b), R 2 is a hydrogen atom, an alkyl group, or a hydroxyalkyl group.

[0061] [ka]

[0062] [In formula (d), R a has the same meaning as above.]

[0063] [ka]

[0064] [In formula (f), R 2 has the same meaning as above.]

[0065] Specific examples of the polyhydric alcohol (B1) include trimethylolpropane, trimethylolethane, glycerin, and pentaerythritol. These may be used alone or in combination of two or more.

[0066] Specific examples of the diol (D1) 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, 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.

[0067] Examples of carbonate esters include dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, dipropyl carbonate, dibutyl carbonate, diphenyl carbonate, ethylene carbonate, trimethylene carbonate, and 1,2-propylene carbonate. These may be used alone or in combination of two or more. From the viewpoints of availability and ease of setting polymerization reaction conditions, it is preferable to use at least one selected from the group consisting of dimethyl carbonate, diethyl carbonate, diphenyl carbonate, dibutyl carbonate, and ethylene carbonate.

[0068] Examples of the oxetane compound (F1) include 3-ethyl-3-hydroxymethyloxetane, 3-methyl-3-hydroxymethyloxetane, and 3,3-dihydroxymethyloxetane. These may be used alone or in combination of two or more.

[0069] The compound (A-1) described in the fourth embodiment may be, for example, a reaction product of a polycarbonate polyol (B2) and a polyester polyol (C2). Also, the compound (A-1) may be a reaction product of a polycarbonate polyol (B2), a polyester polyol (C2), and an oxetane compound (F2). Furthermore, the compound (A-1) may be a reaction product of a polycarbonate polyol (B2), a polyester polyol (C2), a diol (D2) and / or a polyhydric alcohol (E2). In addition, the compound (A-1) may be a reaction product of a polycarbonate polyol (B2), a polyester polyol (C2), an oxetane compound (F2), a diol (D2) and / or a polyhydric alcohol (E2).

[0070] The polycarbonate polyol (B2) may be any polycarbonate polyol having two or more hydroxyl functional groups. It may be a polycarbonate polyol (B2-1) having two hydroxyl functional groups (i.e., a polycarbonate diol), a polycarbonate polyol (B2-2) having more than two hydroxyl functional groups, or a combination of two or more selected from the polycarbonate polyols (B2-1) and (B2-2).

[0071] The polycarbonate polyol (B2-1) may, for example, be one obtained by reacting a carbonate ester with a diol.

[0072] Examples of the carbonate ester and diol that can be used in the reaction to obtain the polycarbonate polyol (B2-1) include the same carbonate ester and diol (D1) as those described in the description of the compound (A-1) in the first to third embodiments.

[0073] The polycarbonate polyol (B2-2) may, for example, be one obtained by reacting a carbonate ester, a diol, and a polyhydric alcohol having three or more hydroxyl functional groups.

[0074] Examples of the carbonate ester, diol, and polyhydric alcohol having three or more hydroxyl functional groups that can be used in the reaction to obtain the polycarbonate polyol (B2-2) include the same carbonate ester, diol (D1), and polyhydric alcohol (B1) as those described in the description of the compound (A-1) in the first to third embodiments.

[0075] The polyester polyol (C2) may be any polyester polyol having two or more hydroxyl functional groups, and may be a polyester polyol (C2-1) having two hydroxyl functional groups (i.e., a polyester diol), a polyester polyol (C2-2) having more than two hydroxyl functional groups, or a combination of two or more selected from the polyester polyols (C2-1) and (C2-2).

[0076] Examples of the polyester polyol (C2-1) include the following polyester polyols (α) to (β) and any combination of two or more of these. (α) A polyester polyol (polyester polyol (α)) obtained from a diol (C2-1-1) and a dicarboxylic acid and / or anhydride thereof (C2-1-2). (β) A polyester polyol (polyester polyol (β)) obtained by ring-opening addition polymerization of a cyclic ester compound (C2-1-4) such as a lactone using a diol (C2-1-1) 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.

[0077] The diol (C2-1-1) may be the same as the diol (D1) described in the description of the compound (A-1) in the first to third embodiments. Among them, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,9-nonanediol, 3-methyl-1,5-pentanediol, or 2-methyl-1,8-octanediol is preferred.

[0078] Examples of dicarboxylic acids and / or anhydrides thereof (C2-1-2) include phthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, cyclohexanedicarboxylic acid, maleic acid, fumaric acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, sebacic acid, dodecanedioic acid, hydrogenated dimer fatty acid, and the like, tartaric acid, and anhydrides thereof, and combinations of any two or more thereof.

[0079] Examples of the cyclic ester compound (C2-1-4) include β-propiolactone, β-butyrolactone, γ-butyrolactone, β-valerolactone, γ-valerolactone, δ-valerolactone, α-caprolactone, β-caprolactone, γ-caprolactone, δ-caprolactone, ε-caprolactone, α-methyl-ε-caprolactone, β-methyl-ε-caprolactone, 4-methylcaprolactone, γ-caprylolactone, ε-caprylolactone, ε-palmitolactone, and the like, and combinations of any two or more of these. Among these, a ring-opening addition polymer of ε-caprolactone using trimethylolpropane as an initiator is preferred from the standpoint of stability during polymerization and economic efficiency.

[0080] Examples of the polyester polyol (C2-2) include the following polyester polyols (α') to (β') and any combination of two or more of these. (α') A polyester polyol (polyester polyol (α')) obtained from a diol (C2-2-1), a dicarboxylic acid and / or anhydride thereof (C2-2-2), and a polyhydric alcohol having three or more hydroxyl functional groups (C2-2-3). (β') A polyester polyol (polyester polyol (β')) obtained by ring-opening addition polymerization of a cyclic ester compound (C2-2-4) such as a lactone using a polyhydric alcohol (C2-2-3) having three or more hydroxyl functional groups as an initiator. The polyester polyol (β') can be said to be a ring-opening addition polymer of a cyclic ester compound using a polyhydric alcohol having three or more hydroxyl functional groups as an initiator.

[0081] Examples of the diol (C2-2-1) and the polyhydric alcohol (C2-2-3) having three or more hydroxyl functional groups include the same diol (D1) and polyhydric alcohol (B1) as those described in the description of the compound (A-1) in the first to third embodiments.

[0082] Examples of the dicarboxylic acid and / or its anhydride (C2-2-2) and the cyclic ester compound (C2-2-4) include the same as those mentioned in the description of the dicarboxylic acid and / or its anhydride (C2-1-2) and the cyclic ester compound (C2-1-4).

[0083] In the fourth embodiment, it is more preferable that the polyester polyol (C2) contains polyester polyol (β) and / or polyester polyol (β'), from the viewpoint that when used as a raw material for a urethane resin, a urethane resin having excellent durability such as heat resistance or moist heat resistance is easily formed.

[0084] Examples of the diol (D2) include the same diols (D1) as those mentioned in the description of the compound (A-1) in the first to third embodiments.

[0085] Examples of the polyhydric alcohol (E2) include the same polyhydric alcohols (B1) as those mentioned in the description of the compound (A-1) in the first to third embodiments.

[0086] Examples of the oxetane compound (F2) include the same oxetane compounds (F1) as those mentioned in the description of the compound (A-1) in the first to third embodiments.

[0087] <Diol (d)> The composition may further contain a diol represented by the following formula (d) (hereinafter also referred to as "diol (d)").

[0088] [ka]

[0089] [In formula (d), R a has the same meaning as above.]

[0090] The diol (d) has the same meaning as described above, and the diol (d) is R a The alkanediyl group represented by R a It may be the same as the alkanediyl group contained in the above formula (I).

[0091] Diol (d) to R a The alkanediyl group contained as R in compound (A-1) is a The alkanediyl group may be the same as the alkanediyl group contained as R a When the composition contains two or more compounds (A-1) having different alkanediyl groups represented by R a In this case, the compound represented by the formula (d) may contain two or more diols having different alkanediyl groups represented by the formula (d). a The combination of groups included as R is included in multiple compounds corresponding to compound (A-1). a may be the same as the combination of groups included in

[0092] Examples of the diol (d) include the same diols (D1) as those mentioned in the description of the compound (A-1) in the first to third embodiments.

[0093] <Polyhydric alcohol (e)> The composition may further contain a polyhydric alcohol represented by the following formula (e) (hereinafter also referred to as "polyhydric alcohol (e)").

[0094] [ka]

[0095] [In formula (e), R 2 has the same meaning as above.]

[0096] The polyhydric alcohol (e) has the same meaning as described above, and the polyhydric alcohol (e) is R 2 The alkyl group and / or hydroxyalkyl group represented by R 2 may be the same as the atom or group contained as

[0097] Polyhydric alcohol (e) with R 2 The atom or group contained as R in compound (A-1) 2 The atom or group may be the same as that included in the composition as R 2 When the composition contains two or more compounds (A-1) having different alkanediyl groups represented by R 2 In this case, the compound represented by the formula (e) may contain two or more polyhydric alcohols having different alkanediyl groups represented by the formula (e). 2 The combination of groups included as R is included in multiple compounds corresponding to compound (A-1). 2 may be the same as the combination of groups included in

[0098] Examples of the polyhydric alcohol (e) include the same polyhydric alcohols (B1) as those mentioned in the description of the compound (A-1) in the first to third embodiments.

[0099] <Oxetane Compounds (F)> The composition may further contain an oxetane compound represented by the following formula (f) (hereinafter also referred to as "oxetane compound (F)").

[0100] [ka]

[0101] [In formula (f), R 2 has the same meaning as above.]

[0102] The oxetane compound (F) has the same meaning as described above, and the oxetane compound (F) is R 2 The alkyl group and the hydroxyalkyl group represented by R 2 may be the same as the atom or group contained as

[0103] Oxetane compound (F) R 2 The atom or group contained as R in compound (A-1) 2 The atom or group may be the same as that included in the composition as R 2 When the composition contains two or more compounds (A-1) having different alkanediyl groups represented by R 2 In this case, the oxetane compound (F) may contain two or more kinds of oxetane compounds having different alkanediyl groups represented by R 2 The combination of groups included as R is included in multiple compounds corresponding to compound (A-1). 2 may be the same as the combination of groups included in

[0104] Examples of the oxetane compound (F) include the same oxetane compounds (F1) as those described in the description of the compound (A-1) in the first to third embodiments.

[0105] <Compound (A-2)> The composition may further contain a polycarbonate compound represented by the following formula (A-2) (hereinafter referred to as "compound (A-2)").

[0106] [ka]

[0107] [In formula (A-2), R 1 is as defined above, and n 2 indicates an integer of 1 or more. 1may be the same or different.]

[0108] <Compound (A-3)> The composition may further contain a polycarbonate compound represented by the following formula (A-3) (hereinafter referred to as "compound (A-3)").

[0109] [ka]

[0110] [In formula (A-3), R 1 and R 2 is as defined above, and n 3 R indicates an integer of 1 or more. 1 If there are multiple, there are multiple R 1 may be the same or different.]

[0111] <Compound (A-4)> The composition may further contain a polycarbonate compound represented by the following formula (A-4) (hereinafter referred to as "compound (A-4)").

[0112] [ka]

[0113] [In formula (A-4), R 1 and R 2 is as defined above, and n 4 indicates an integer of 1 or more. 2 may be the same or different. 1 If there are multiple, R 1 may be the same or different.]

[0114] Compound (A-2) to compound (A-4) are R 1 The group contained as R in compound (A-1) 1 The compound (A-1) may be the same as the group contained as R 1When R contains two or more groups, compounds (A-2) to (A-4) also contain R 1 In this case, the compound (A-2) to the compound (A-4) may contain two or more kinds of groups as R 1 The combination of two or more groups contained as R 1 may be the same as a combination of two or more groups included in the formula:

[0115] Compound (A-2) to compound (A-4) are R 2 The group contained as R in compound (A-1) 2 The compound (A-1) may be the same as the group contained as R 2 When R contains two or more groups, compounds (A-2) to (A-4) also contain R 2 In this case, the compound (A-2) to the compound (A-4) may contain two or more kinds of groups as R 2 The combination of two or more groups contained as R 2 may be the same as a combination of two or more groups included in the formula:

[0116] n 2 , n 3 , and n 4 may be 1 to 65, 2 to 60, or 3 to 50.

[0117] The number average molecular weight of the compounds (A-2) to (A-4) is preferably from 200 g / mol to 6000 g / mol, and may be from 300 g / mol to 5000 g / mol or from 500 g / mol to 4000 g / mol.

[0118] The hydroxyl value of the compounds (A-2) to (A-4) is preferably from 30 to 800 mgKOH / g, and may be from 40 to 700 mgKOH / g or from 50 to 600 mgKOH / g.

[0119] The lower limit of the deemed average hydroxyl functionality of the composition may be, for example, 2.0 or more, 2.1 or more, 2.2 or more, 2.3 or more, 2.4 or more, or 2.5 or more. The upper limit of the deemed average hydroxyl functionality of the composition may be, for example, 3.90 or less, 3.80 or less, 3.70 or less, 3.60 or less, 3.50 or less, or 3.40 or less. The deemed average hydroxyl functionality of the composition may be 2.0 to 3.90, for example, 2.1 to 3.80, 2.2 to 3.70, 2.3 to 3.50, or 2.5 to 3.40. When the deemed average hydroxyl functionality of the composition is 3.90 or less, the handling property and the elongation at break in the tensile test are further improved. When the deemed average hydroxyl functionality of the composition is 2.0 or more, the strength at break and the softening temperature in the tensile test tend to be further improved.

[0120] In the following description, the sum of the total number of moles of the group represented by the following formula (I) and the total number of moles of the group represented by the following formula (C) contained in the composition is defined as C T The total number of moles of the group represented by the following formula (C) contained in the composition is C C The total number of moles of the group represented by the following formula (D) contained in the composition is C D The total number of moles of the group represented by the following formula (E) contained in the composition is C E The content (unit: mol%) of the structure (C) derived from the oxetane compound relative to the total of the structural unit (I) derived from the polyhydric alcohol and the structure (C) derived from the oxetane compound is referred to as the "molar ratio (C C / C T The content (unit: mol%) of the structure (C) derived from the oxetane compound relative to the sum of the structure (C) derived from the oxetane compound, the structure (D) derived from the diol, and the structure (E) derived from the polyhydric alcohol is expressed as the "molar ratio (C C / (C C +C D +C E ) × 100).

[0121] [ka]

[0122] [In formula (I), R 2 has the same meaning as above, and * indicates a bond.

[0123] [ka]

[0124] [In formula (C), R 2 has the same meaning as above, and * indicates a bond.

[0125] [ka]

[0126] [In formula (D), R 3 is a hydrogen atom or an alkyl group, and * indicates a bond. 3 may be the same or different.]

[0127] [ka]

[0128] [In formula (E), R 2 has the same meaning as above, and * indicates a bond.

[0129] Molar ratio (C C / C T × 100) may be 2.80 to 28.0. C / (C C +C D +C E ) × 100) may be 0.90 to 10.7. C / C T × 100) and molar ratio (C C / (C C +C D +C E ) × 100) are each within the above range, when the composition is used as a raw material for a urethane resin, a urethane resin that has both good handleability and high tensile strength tends to be formed.

[0130] Molar ratio (C C / C T × 100), and molar ratio (C C / (C C +C D +C E )×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 molar ratio (C C / C T × 100) is the R 2 (Alkyl group) terminal methyl signal (SI) integral value Δ SI (3 mol of hydrogen atoms) and the integral value Δ of the methylene signal (SC) located next to the oxygen atom of the oxetane group in formula (C) SC (4 mol of hydrogen atoms) and the molar ratio (C C / (C C +C D +C E ) × 100) is the integral value of the above signal (SC) Δ SC (4 mol of hydrogen atoms) and the integral value Δ of the methylene signal (SD) located next to the hydroxyl group of the group represented by formula (D) SD (2 mol of hydrogen atoms) and the integral value Δ of the methylene signal (SE) located next to the hydroxyl group of the group represented by formula (E) SE (4 mol of hydrogen atoms) and the molar ratio (C C / C T ×100) is the integral value of the signal (SI) Δ SI and the integral value of the signal (Sf) Δ Sf 0.75 times the ratio of and (0.75 × Δ Sf / Δ SI × 100). C / (C C +C D +C E )×100) is the integral value of the signal (SC) Δ SCand the integral value of the signal (SD) Δ SD、 Signal (SE) integral Δ SE The sum of and the integral value of the signal (SC) Δ SC The ratio of (Δ SC / (Δ SC +2×Δ SD +Δ SE ) × 100).

[0131] The above composition will be described in more detail below, divided into a number of embodiments (first to fourth embodiments).

[0132] In the first and second embodiments, deuterated chloroform is used as a solvent, and tetramethylsilane is used as a reference substance to measure the composition. 1 When H-NMR measurement is performed, for example, the above signal (SC) is 1 The signal (SD) is observed in the range of 4.390 ppm to 4.500 ppm in the H-NMR spectrum. 1 The signal (SE) is observed in the range of 3.618 ppm to 3.720 ppm in the H-NMR spectrum. 1 The H-NMR spectrum is observed in the range of 3.590 ppm to 3.618 ppm. 2 is an ethyl group, the above signal (SI) is observed in the range of 0.700 ppm or more and 1.000 ppm or less, and R 2 When 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 the first and second embodiments, the molar ratio (C C / C T × 100), and molar ratio (C C / (C C +C D +C E ) × 100).

[0133] In the third embodiment, deuterated chloroform is used as a solvent and tetramethylsilane is used as a reference material to determine the composition. 1When H-NMR measurement is performed, for example, the above signal (SC) is 1 The signal (SD) is observed in the range of 4.390 ppm to 4.500 ppm in the H-NMR spectrum. 1 The signal (SE) is observed in the range of 3.618 ppm to 3.720 ppm in the H-NMR spectrum. 1 The H-NMR spectrum is observed in the range of 3.590 ppm to 3.618 ppm. Therefore, in the third embodiment, the molar ratio (C C / (C C +C D +C E ) × 100).

[0134] In the fourth embodiment, deuterated chloroform is used as a solvent and tetramethylsilane is used as a reference substance to measure the composition. 1 When H-NMR measurement is performed, for example, the above signal (SC) is 1 The signal (SD) is observed in the range of 4.390 ppm to 4.500 ppm in the H-NMR spectrum. 1 The signal (SE) is observed in the range of 3.618 ppm to 3.720 ppm in the H-NMR spectrum. 1 The H-NMR spectrum is observed in the range of 3.550 ppm to 3.618 ppm. 2 is an ethyl group, the above signal (SI) is observed in the range of 0.700 ppm or more and 1.000 ppm or less, and R 2 When is a methyl group, the above signal (SI) is observed in the range of 0.700 ppm to 1.130 ppm. Therefore, in the fourth embodiment, the molar ratio (C C / C T × 100), and molar ratio (C C / (C C +C D +C E ) × 100).

[0135] The molar ratio (C C / C T × 100) may be 2.80 or more, 3.00 or more, 3.20 or more, 3.40 or more, 3.60 or more, 3.80 or more, 5.00 or more, 6.00 or more, 7.00 or more, 8.00 or more, 9.00 or more, or 10.0 or more. C / C T When the molar ratio (C × 100) is 2.80 or more, a polyurethane resin having excellent handling properties tends to be formed. C / C T × 100) may be 28.0 or less, 26.0 or less, 22.0 or less, 20.0 or less, 18.0 or less, 16.0 or less, 15.0 or less, 14.0 or less, 13.0 or less, or 12.0 or less. C / C T When the molar ratio (C × 100) is 28.0 or less, a polyurethane resin having particularly excellent tensile strength tends to be formed. C / C T × 100) may be 2.0 to 30.0, 3.0 to 28.0, 3.2 to 26.0, 3.4 to 22.0, 3.8 to 20.0, 5.0 to 18.0, 6.0 to 16.0, 7.0 to 15.0, 8.0 to 14.0, 9.0 to 13.0, or 10.0 to 12.0. C / C T × 100) within the above range, when the composition is used as a raw material for a urethane resin, a polyurethane resin having both good handling properties and tensile strength tends to be formed.

[0136] The molar ratio (C C / (C C +C D +C E ) × 100) may be 0.90 or more, 0.95 or more, 1.00 or more, 1.05 or more, 1.10 or more, 1.15 or more, 1.20 or more, 1.50 or more, 1.80 or more, 2.10 or more, 2.40 or more, 3.00 or more, or 4.00 or more. C / (C C +C D +C EWhen the molar ratio (C)×100) is 0.90 or more, a polyurethane resin having excellent handling properties tends to be formed. C / (C C +C D +C E ) × 100) may be 16.0 or less, 10.7 or less, 10.5 or less, 10.0 or less, 9.5 or less, 9.0 or less, 8.5 or less, 8.0 or less, 7.5 or less, 7.0 or less, 6.5 or less, or 6.0 or less. C / (C C +C D +C E When the molar ratio (C)×100) is 16.0 or less, a polyurethane resin having particularly excellent tensile strength tends to be formed. C / (C C +C D +C E ) × 100) may be 1.00 to 10.7, 1.05 to 10.5, 1.10 to 10.0, 1.15 to 9.5, 1.20 to 9.0, 1.30 to 8.0, 1.50 to 7.0, or 1.80 to 6.0. C / (C C +C D +C E )×100) within the above range, when the composition is used as a raw material for a urethane resin, a polyurethane resin having both good handling properties and tensile strength tends to be formed.

[0137] <Catalyst> The compositions of the first to third embodiments may be a reaction mixture of a polyhydric alcohol (B1), a diol (D1), a carbonate ester, and an oxetane compound (F1) added as required. As the transesterification catalyst, lithium acetylacetonate is preferably used. The content of the transesterification catalyst may be 0.0001 to 0.100% by mass based on the total mass of the composition.

[0138] The composition of the fourth embodiment may be a reaction mixture of polycarbonate polyol (B2), polyester polyol (C2), and diol (d), polyhydric alcohol (e) and / or oxetane compound (F2) added as necessary. The above reaction is usually carried out in the presence of a transesterification catalyst, so 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.

[0139] The properties of the composition are not particularly limited, and may be a solid or a liquid at 25° C. The properties of the composition can be changed depending on the types and content ratios of the components contained (e.g., compounds (A-1) to (A-4), diol (d), polyhydric alcohol (e), and oxetane compound (F)).

[0140] 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.

[0141] The number average molecular weight of the composition is the number average molecular weight calculated as a difunctional polyoxypropylene polyol, measured by using GPC (gel permeation chromatography) with the entire composition as the measurement subject.

[0142] 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.

[0143] According to the present embodiment, a composition can be provided that contributes to the formation of a urethane resin having high tensile strength and also has good handleability.

[0144] <Manufacturing method> In the method for producing compound (A-1) of the first to third embodiments, a mixed liquid containing polyhydric alcohol (B1), diol (D1), carbonate, and an ester exchange catalyst may be heated to perform a reflux reaction (ester exchange reaction) while removing alcohol derived from the carbonate from the reaction system, thereby obtaining compound (A-1); or a mixed liquid containing polyhydric alcohol (B1), diol (D1), carbonate, oxetane compound (F1), and an ester exchange catalyst may be heated to perform a reflux reaction (ester exchange reaction) while removing alcohol derived from the carbonate from the reaction system, thereby obtaining compound (A-1).

[0145] In the above-mentioned method, the composition of the above-mentioned embodiment can be obtained as a reaction mixture containing the compound (A-1). Therefore, the above-mentioned method can also be said to be a method for producing the composition of the above-mentioned embodiment.

[0146] The details of the polyhydric alcohol (B1), the diol (D1), the carbonate ester, and the oxetane compound (F1) are as described above. 1 and R 2 Examples of the R groups contained in the compound (A-1) and examples of preferred combinations thereof are also shown. 1 and R 2 The preferred examples and preferred combinations are the same as those of the above. As the transesterification catalyst, it is preferable to use lithium acetylacetonate, from the viewpoint of facilitating the production of the desired compound (A-1).

[0147] When two or more kinds of diols (D1) are used, from the viewpoint that a urethane resin having good tensile strength, elongation and texture and excellent durability is likely to be formed when the diol (D1) is used as a raw material for the urethane resin, the ratio of the number of moles of 1,6-hexanediol to the total number of moles of diol (D1) is preferably 0.20 or more (e.g., 0.20 to 1.00), more preferably 0.30 or more (e.g., 0.30 to 0.90), and even more preferably 0.40 or more (e.g., 0.40 to 0.80 or 0.50 to 0.70).

[0148] The mixing ratio of the polyhydric alcohol (B1) and the diol (D1) (content of the diol (D1) in the mixed solution / content of the polyhydric alcohol (B1) in the mixed solution) is preferably 1 / 100 to 5 / 1, more preferably 1 / 80 to 3 / 1, further preferably 1 / 50 to 2 / 1, and particularly preferably 1 / 20 to 1 / 1, in molar ratio. By setting the mixing ratio of the diol and the polyhydric alcohol in the above range, a composition containing the compound (A-1) can be efficiently obtained. The above mixing ratio may be 1 / 5 to 60 / 1 or 1 / 1 to 40 / 1, in molar ratio.

[0149] The mixing ratio of the carbonate ester to the polyhydric alcohol (B1) and the diol (D1) (content of the carbonate ester in the mixed solution / total content of the polyhydric alcohol (B1) and the diol (D1) in the mixed solution) is preferably 1 / 3 to 3 / 1, more preferably 1 / 2.5 to 2.5 / 1, further preferably 1 / 2 to 2 / 1, and particularly preferably 1 / 1.5 to 1.5 / 1, by adjusting the mixing ratio of the carbonate ester to the polyhydric alcohol (B1) and the diol (D1) to be within the above range, a composition containing the compound (A-1) can be efficiently obtained.

[0150] The content of the transesterification catalyst in the mixed solution of the first to third embodiments may be 0.0001 to 0.1 parts by mass, or may be 0.0005 to 0.01 parts by mass, based on 100 parts by mass of the total amount of the polyhydric alcohol, diol, and carbonate ester in the mixed solution, from the viewpoint of easily controlling the reaction temperature and suppressing an increase in the color number of the reaction product. The content of the transesterification catalyst is preferably as small as possible, based on the viewpoint of easily controlling the reactivity of the urethanization reaction. When the content of the transesterification catalyst is increased, the reactivity of the urethanization reaction tends to be increased. The content of the transesterification catalyst in the mixed solution is preferably 0.001 parts by mass or more, more preferably 0.002 parts by mass or more, and even more preferably 0.003 parts by mass or more, based on 100 parts by mass of the total amount of the polyhydric alcohol, diol, and carbonate ester in the mixed solution, from the viewpoint of easily controlling the urethanization reaction. From the viewpoint of suppressing an increase in the color number of the reaction product, the content of the transesterification catalyst in the mixed liquid is preferably 0.050 parts by mass or less, more preferably 0.040 parts by mass or less, and even more preferably 0.030 parts by mass or less, relative to 100 parts by mass of the total amount of the polyhydric alcohol, diol, and carbonate ester in the mixed liquid. From these viewpoints, the content of the transesterification catalyst in the mixed liquid is preferably 0.001 to 0.050 parts by mass, more preferably 0.002 to 0.040 parts by mass, and even more preferably 0.003 to 0.030 parts by mass, relative to 100 parts by mass of the total amount of the polyhydric alcohol, diol, and carbonate ester in the mixed liquid.

[0151] The heating temperature (reaction temperature) of the mixed liquid in the first to third embodiments may be, for example, 80 to 250°C, or 100 to 220°C. When the reaction temperature is 80°C or higher, the transesterification reaction easily proceeds, and the desired compound (A-1) is easily obtained. When the reaction temperature is 250°C or lower, the color number of the obtained compound (A-1) and the composition polyol is suppressed. In addition, the transesterification reaction may be carried out while keeping the temperature constant, or may be carried out while increasing the temperature stepwise or continuously depending on the reaction progress. From the viewpoint of making it easier to obtain the desired compound (A-1), it is preferable to carry out heating at a temperature T1 that satisfies the relationship of the following formula (α), and then heating at a temperature T2 that satisfies the relationship of the following formula (β). It is preferable that the temperatures T1 and T2 satisfy the relationship of the following formula (γ). In addition, the average temperature T1 of the first heating temperature is preferably 100°C to 150°C. m and the average temperature T2 of the second heating temperature m It is preferable that the relationship of the following formula (δ) is satisfied: Here, the degree of reaction progress can be estimated from the amount of the distillate. 120℃≦T1≦155℃ (α) 140℃≦T2≦155℃ (β) T1 <T2 ···(γ) T1 m <T2 m (δ)

[0152] The mixture of the first to third embodiments can be heated under normal pressure, but in the latter half of the reaction, it can also be heated under reduced pressure (for example, under a pressure of 101 to 0.1 kPa). This can increase the distillation rate of the distillate produced, and can accelerate the progress of the reaction. In this specification, normal pressure means a pressure of 101.325 kPa ± 20.000 kPa. From the viewpoint of facilitating the production of the desired compound (A-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 10.000 kPa or less (second heating), the temperature of the first heating is more preferably a temperature T1 that satisfies the relationship of the above formula (α), the temperature of the second heating is more preferably a temperature T2 that satisfies the relationship of the above formula (β), and it is even more preferable that the temperature of the first heating (temperature T1) and the temperature of the second heating (temperature T2) satisfy the relationship of the above formula (γ). Furthermore, from the viewpoint of facilitating the production of the compound (A-1), it is preferable to remove the alcohol derived from the carbonate ester from the reaction system by distilling it at 120° C. or less.

[0153] The reaction time of the mixed solution of the first to third embodiments may be 2 to 80 hours, 3 to 60 hours, 4 to 50 hours, 5 to 40 hours, or 6 to 30 hours. The structure (C) derived from the oxetane compound represented by the above formula (C) is produced by an intramolecular dehydration reaction of a polyhydric alcohol and / or an intramolecular decarboxylation reaction of a cyclic carbonate, which is a reaction product of a polyhydric alcohol and a carbonate ester. The above intramolecular dehydration reaction and intramolecular decarboxylation reaction are irreversible reactions, and the amount of the structure (C) derived from the oxetane compound increases with reaction time. When the reaction time is 2 hours or more, it is possible to promote the production of the structure (C) derived from the oxetane compound, and the molar ratio (C C / C T × 100), and / or molar ratio (C C / (C C +C D +C E)×100) satisfies the above-mentioned numerical range. In addition, when the reaction time is less than 80 hours, it is possible to suppress the formation of the structure (C) derived from the oxetane compound, and it is easy to obtain a composition containing the desired compound (A-1).

[0154] The compound (A-1) of the fourth embodiment can be obtained, for example, by a method including a reaction step of obtaining the compound (A-1) by reacting (ester exchange reaction) the polycarbonate polyol (B2) with the polyester polyol (C2) in a mixed solution containing the polycarbonate polyol (B2), the polyester polyol (C2), and an ester exchange catalyst. In this method, at least one of the polycarbonate polyol (B2) and the polyester polyol (C2) may contain a group represented by the above formula (I), or the mixed solution may further contain a polyhydric alcohol represented by the above formula (e). The mixed solution may further contain an oxetane compound (F2). That is, the compound (A-1) of the fourth embodiment can also be obtained by a method including a reaction step of obtaining the compound (A-1) by reacting (ester exchange reaction) a polycarbonate polyol with a polyester polyol in a mixed liquid containing a polycarbonate polyol (B2), a polyester polyol (C2), an ester exchange catalyst, and an oxetane compound (F2).

[0155] In the above-mentioned method, the composition of the above-mentioned embodiment can be obtained as a reaction mixture containing the compound (A-1). Therefore, the above-mentioned method can also be said to be a method for producing the composition of the above-mentioned embodiment.

[0156] The mixed liquid of the fourth embodiment may contain a diol (D2) and / or an oxetane compound (F2) as an optional component. Even in the case where at least one of the polycarbonate polyol (B2) and the polyester polyol (C2) contains a group represented by the above formula (I) in the above method, the mixed liquid may contain a polyhydric alcohol (E2) as an optional component. The details of the polycarbonate polyol (B2), the polyester polyol (C2), the diol (D2), the polyhydric alcohol (E2) and the oxetane compound (F2) are as described above, and preferred examples thereof (preferable R 1 and R 2 Examples of the R groups contained in the compound (A-1) and examples of preferred combinations thereof are also shown. 1 and R 2 The preferred examples and preferred combinations are the same as those of the above. As the transesterification catalyst, it is preferable to use lithium acetylacetonate, from the viewpoint of facilitating the production of the desired compound (A-1).

[0157] The mixing ratio of the polycarbonate polyol (B2) and the polyester polyol (C2) (content of the polycarbonate polyol (B2) in the mixed solution / content of the polyester polyol (C2) in the mixed solution) is preferably 95 / 5 to 5 / 95 by weight, more preferably 90 / 10 to 10 / 90, further preferably 80 / 20 to 20 / 80, and particularly preferably 70 / 30 to 30 / 70. By setting the mixing ratio of the polycarbonate polyol (B2) and the polyester polyol (C2) in the above range, a composition containing the compound (A-1) can be efficiently obtained.

[0158] The mixing ratio of the polycarbonate polyol (B2) to the polyester polyol (β) and / or polyester polyol (β') (content of the polycarbonate polyol (B2) in the mixed solution / content of the polyester polyol (β) and / or polyester polyol (β') in the mixed solution) is preferably 95 / 5 to 5 / 95 by weight, more preferably 90 / 10 to 10 / 90, further preferably 80 / 20 to 20 / 80, and particularly preferably 70 / 30 to 30 / 70. By setting the mixing ratio of the polycarbonate polyol (B2) to the polyester polyol (β) and / or polyester polyol (β') in the above range, a composition containing the compound (A-1) can be efficiently obtained.

[0159] The content of the transesterification catalyst in the mixed solution of the fourth embodiment may be 0.0001 to 0.1 parts by mass, 0.001 to 0.050 parts by mass, or 0.005 to 0.01 parts by mass relative to 100 parts by mass of the total amount of the polyol components in the mixed solution, from the viewpoint of easily controlling the reaction temperature and suppressing an increase in the color number of the reaction product. The content of the transesterification catalyst is preferably as small as possible from the viewpoint of easily controlling the reactivity of the urethanization reaction. When the content of the transesterification catalyst is increased, the reactivity of the urethanization reaction tends to be high. The content of the transesterification catalyst in the mixed solution is preferably 0.001 parts by mass or more, more preferably 0.002 parts by mass or more, and even more preferably 0.003 parts by mass or more relative to 100 parts by mass of the total amount of the polyol components in the mixed solution, from the viewpoint of easily controlling the urethanization reaction. From the viewpoint of suppressing an increase in the color number of the reaction product, the content of the transesterification catalyst in the mixed solution is preferably 0.050 parts by mass or less, more preferably 0.040 parts by mass or less, and even more preferably 0.030 parts by mass or less, relative to 100 parts by mass of the total amount of the polyol components in the mixed solution. From these viewpoints, the content of the transesterification catalyst in the mixed solution is preferably 0.001 to 0.050 parts by mass, more preferably 0.002 to 0.040 parts by mass, and even more preferably 0.003 to 0.030 parts by mass, relative to 100 parts by mass of the total amount of the polyol components in the mixed solution. The total amount of the polyol components is the total amount of the compounds having two or more hydroxyl groups (for example, polycarbonate polyol (B2), polyester polyol (C2), polyhydric alcohol (E2), and optional diol (D2)) and the oxetane compound (F2) contained in the mixed solution.

[0160] In the reaction step of the fourth embodiment, the reaction may be progressed by heating the mixture, or may be progressed without heating. The reaction temperature of the mixture is, for example, 0 to 250°C, and may be 100 to 220°C. When the reaction temperature is 0°C or higher, the transesterification reaction is likely to proceed, and the desired compound (A-1) is likely to be obtained. Furthermore, when the reaction temperature is 0°C or higher, the formation of structure (C) derived from oxetane derived from polyhydric alcohol having three or more functional groups, which is a by-product of decarboxylation reaction of carbonate groups or dehydration reaction between terminal hydroxyl groups, can be promoted. When the reaction temperature is 250°C or lower, the color number of the obtained compound (A-1) and composition (polyol-containing composition) can be suppressed. Furthermore, when the reaction temperature is 250°C or lower, the formation of structure (C) derived from oxetane derived from polyhydric alcohol having three or more functional groups, which is a by-product of decarboxylation reaction of carbonate groups or dehydration reaction between terminal hydroxyl groups, can be suppressed. The transesterification reaction may be carried out while keeping the temperature constant, or may be carried out while increasing the temperature stepwise or continuously depending on the progress of the reaction. From the viewpoint of facilitating the production of the desired compound (A-1), it is preferable to carry out heating at a temperature T1 that satisfies the relationship of the following formula (α'), and then to carry out heating at a temperature T2 that satisfies the relationship of the following formula (β'). It is preferable that the temperatures T1 and T2 satisfy the relationship of the following formula (γ'). In addition, the average temperature T1 of the first heating temperature is m and the average temperature T2 of the second heating temperature m It is preferable that the relationship of the following formula (δ') is satisfied: Here, the reaction progress can be estimated from the consumption amount of the raw material obtained from the GPC chart. 180℃≦T1≦200℃ (α') 190℃≦T2≦200℃ (β') T1 <T2 ···(γ’) T1 m <T2 m (δ')

[0161] The heating of the mixture in the fourth embodiment can be performed under normal pressure, but can also be performed under reduced pressure (for example, under a pressure of 101 to 1 kPa). This makes it possible to remove moisture remaining in the mixture, accelerate the progress of the reaction, and suppress coloring of the composition. In this specification, normal pressure means a pressure of 101.325 kPa ± 20.000 kPa. From the viewpoint of making it easier to obtain the desired compound (A-1), the heating of the mixture preferably includes heating under a pressure of 101.325 kPa ± 20.000 kPa (first heating) and then heating under a reduced pressure of 20.000 kPa or less (second heating), and it is more preferable that the temperature of the first heating is a temperature T1 that satisfies the relationship of the above formula (α'), and the temperature of the second heating is a temperature T2 that satisfies the relationship of the above formula (β'), and it is even more preferable that the temperature of the first heating (temperature T1) and the temperature of the second heating (temperature T2) satisfy the relationship of the above formula (γ').

[0162] The reaction time of the mixed solution of the fourth embodiment may be 1 to 40 hours, 2 to 30 hours, 3 to 20 hours, 4 to 15 hours, or 5 to 12 hours. The structure (C) derived from the oxetane compound represented by the above formula (C) is produced by an intramolecular dehydration reaction of a polyhydric alcohol and / or an intramolecular decarboxylation reaction of a cyclic carbonate, which is a reaction product of a polyhydric alcohol and a carbonate ester. The above intramolecular dehydration reaction and intramolecular decarboxylation reaction are irreversible reactions, and the amount of the structure (C) derived from the oxetane compound produced increases with reaction time. When the reaction time is 2 hours or more, it is possible to promote the production of the structure (C) derived from the oxetane compound, and the molar ratio (C C / C T × 100), and / or molar ratio (C C / (C C +C D +C E )×100) satisfies the above-mentioned numerical range. In addition, when the reaction time is less than 80 hours, it is possible to suppress the formation of the structure (C) derived from the oxetane compound, and it is easy to obtain a composition containing the desired compound (A-1).

[0163] The mixture in the fourth embodiment can be heated while flowing in nitrogen. This makes it possible to remove moisture from the mixture and accelerate the progress of the reaction. Furthermore, purging with nitrogen makes it possible to suppress coloration of the composition. From the viewpoint of facilitating the production of the desired compound (A-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).

[0164] In the production methods of the first to fourth embodiments, the obtained reaction mixture may be subjected to post-treatment such as distillation, drying, etc. In addition, in the above production methods, after obtaining compound (A-1) or a composition containing it, components such as compound (A-2) to compound (A-4), diol (d), polyhydric alcohol (e), oxetane compound (F), etc. may be added to prepare the product.

[0165] <Urethane resin and its manufacturing method> The urethane resin is a polycondensate of a polyol component and a polyisocyanate component, or a crosslinked product thereof. Here, the crosslinked product means a product in which polycondensates are crosslinked with each other by a chain extender or the like.

[0166] (Polyol component) The polyol component includes the compound (A-1). The polyol component may include a polyol (a compound having two or more terminal hydroxyl groups) other than the compound (A-1), or a monol (a compound having one terminal hydroxyl group). The polyol component may further include, for example, a polyol (compound (A-2), compound (A-3), compound (A-4), diol (d), polyhydric alcohol (e), oxetane compound (F), etc.) that may be included in the composition. The content ratio of these polyols is determined by the content ratio of the polyol in the composition (for example, the molar ratio (C C / C T × 100), molar ratio (C C / (C C +C D +C E)×100)) In other words, the polyol component may contain a polyol mixture obtained by excluding compounds other than the polyol from the above composition.

[0167] The polyol component may further contain a polyol having an acidic group. In this case, the urethane resin contains an acidic group. The urethane resin having an acidic group is preferably used in an aqueous urethane resin dispersion. The aqueous urethane resin dispersion will be described later.

[0168] The acidic group is, for example, a functional group (hydrophilic group) that can impart hydrophilicity to the isocyanate-terminated prepolymer obtained by reaction with isocyanate. Examples of polyols having such acidic groups include dimethylolalkanoic acids such as dimethylolpropionic acid (DMPA), dimethylolbutanoic acid (DMBA), dimethylolpentanoic acid, and dimethylolnonanoic acid.

[0169] (Polyisocyanate) Examples of polyisocyanates include aromatic polyisocyanates, araliphatic polyisocyanates, aliphatic polyisocyanates, and alicyclic polyisocyanates. Modified polyisocyanates, which are modified versions of these, can also be used. Examples of modified polyisocyanates include isocyanurate-modified polyisocyanates (isocyanate trimers), allophanate-modified polyisocyanates, uretdione-modified polyisocyanates, urethane-modified polyisocyanates, biuret-modified polyisocyanates, uretonimine-modified polyisocyanates, and acylurea-modified polyisocyanates. These can be used alone or in combination of two or more.

[0170] Examples of aromatic isocyanates include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, a mixture of 2,4-tolylene diisocyanate and 2,6-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, a mixture of 2,4'-diphenylmethane diisocyanate and 4,4'-diphenylmethane diisocyanate, m-xylylene diisocyanate, p-xylylene diisocyanate, and 4,4'-diphenyl ether. Examples of the diisocyanates include phenyl diisocyanate, 2-nitrodiphenyl-4,4'-diisocyanate, 2,2'-diphenylpropane-4,4'-diisocyanate, 3,3'-dimethyldiphenylmethane-4,4'-diisocyanate, 4,4'-diphenylpropane diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate, naphthylene-1,4-diisocyanate, naphthylene-1,5-diisocyanate, and 3,3'-dimethoxydiphenyl-4,4'-diisocyanate.

[0171] 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.

[0172] Examples of aliphatic isocyanates include hexamethylene diisocyanate, pentamethylene diisocyanate, tetramethylene diisocyanate, 2-methylpentane-1,5-diisocyanate, 3-methylpentane-1,5-diisocyanate, lysine diisocyanate, trioxyethylene diisocyanate, ethylene diisocyanate, trimethylene diisocyanate, octamethylene diisocyanate, nonamethylene diisocyanate, 2,2'-dimethylpentane diisocyanate, 2,2,4-trimethylhexane diisocyanate, decamethylene diisocyanate, butene diisocyanate, 1,3-butadiene-1,4-diisocyanate, 2,4,4 -trimethylhexamethylene diisocyanate, 1,6,11-undecane triisocyanate, 1,3,6-hexamethylene triisocyanate, 1,8-diisocyanato-4-(isocyanatomethyl)octane, 2,5,7-trimethyl-1,8-diisocyanato-5-(isocyanatomethyl)octane, bis(isocyanatoethyl)carbonate, bis(isocyanatoethyl)ether, 1,4-butylene glycol dipropyl ether-α,α'-diisocyanate, lysine diisocyanatomethyl ester, 2-isocyanatoethyl-2,6-diisocyanatohexanoate, 2-isocyanatopropyl-2,6-diisocyanatohexanoate, and the like.

[0173] Examples of alicyclic isocyanates include isophorone diisocyanate, cyclohexyl diisocyanate, bis(isocyanatomethyl)cyclohexane, dicyclohexylmethane diisocyanate, methylcyclohexyl diisocyanate, dicyclohexyldimethylmethane diisocyanate, 2,2'-dimethyldicyclohexylmethane diisocyanate, bis(4-isocyanato-n-butylidene)pentaerythritol, and hydrogenated dimer acid diisocyanate. 2-isocyanatomethyl-3-(3-isocyanatopropyl)-5-(isocyanatomethyl)bicyclo[2.2.1]heptane, 2-(isocyanatomethyl)3-(3-isocyanatopropyl)-6-(isocyanatomethyl)-bicyclo[2.2.1]heptane, 2-(isocyanatomethyl)-2-(3-isocyanatopropyl)-5-(isocyanatomethyl)bicyclo[2.2.1]heptane, 2-(isocyanatomethyl)-2-(3-isocyanatopropyl)-5-(isocyanatomethyl)bicyclo[2.2.1]heptane, 2-(isocyanatomethyl)-2-(3-isocyanatopropyl)- 2-(isocyanatomethyl)-3-(3-isocyanatopropyl)-5-(2-isocyanatoethyl)bicyclo[2.2.1]heptane, 2-(isocyanatomethyl)-3-(3-isocyanatopropyl)-6-(2-isocyanatoethyl)bicyclo[2.2.1]heptane, 2-(isocyanatomethyl)-2-(3-isocyanatopropyl)-5-(2-isocyanatoethyl)bicyclo[2.2.1]heptane, Examples of such diisocyanates include cyclo[2.2.1]heptane, 2-(isocyanatomethyl)-2-(3-isocyanatopropyl)-6-(2-isocyanatoethyl)bicyclo[2.2.1]heptane, 2,5-bis(isocyanatomethyl)bicyclo[2.2.1]heptane, hydrogenated diphenylmethane diisocyanate, norbornane diisocyanate, hydrogenated tolylene diisocyanate, hydrogenated xylene diisocyanate, and hydrogenated tetramethylxylene diisocyanate.

[0174] (Polyol component / polyisocyanate component blend ratio) The blending ratio of the polyol component to the polyisocyanate component, expressed as the molar ratio of active hydrogen in the polyol component to isocyanate groups in the polyisocyanate component, is preferably 9:1 to 1:9, and more preferably 6:4 to 4:6. When the blending ratio is within this range, the urethane resin tends to have better performance.

[0175] (Chain extender) The chain extender can be appropriately selected depending on the purpose, use, etc. Examples of the chain extender include water, ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, 1,10-decanediol, 1,1-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, tricyclodecane dimethanol, xylylene glycol, bis(p-hydroxy)diphenyl, bis(p-hydroxyphenyl)propane, 2,2-bis[4-(2-hydroxyethoxy)phenyl]propane, and bis[4-(2-hydroxyethoxy)phenyl]sulfone. , 1,1-bis[4-(2-hydroxyethoxy)phenyl]cyclohexane and other low molecular weight polyols; polyester polyols, polyesteramide polyols, polyether polyols, polyether ester polyols, polycarbonate polyols, polyolefin polyols and other high molecular weight polyols; ethylene diamine, isophorone diamine, 2-methyl-1,5-pentanediamine, aminoethylethanolamine, diethylene triamine, triethylene tetramine, tetraethylene pentamine, pentaethylene hexamine and other polyamines can be used. The amount of the chain extender (the ratio of the structure derived from the chain extender contained in the urethane resin) may be 0.1 to 50 parts by mass relative to 100 parts by mass of the total amount of the polyol component and the polyisocyanate component. When the chain extender is a polyol, the content of the polyol is calculated assuming that it is included in both the chain extender and the polyol component.

[0176] The urethane resin can be obtained by reacting a polyol component, a polyisocyanate component, and optionally a chain extender (urethanization reaction). The urethane reaction may be carried out at room temperature (e.g., 25°C) or under heating (e.g., 40 to 200°C).

[0177] In the urethanization reaction, a catalyst (urethanization catalyst) can be added for the purpose of shortening the reaction time, improving the reaction rate, etc. Examples of the catalyst include tertiary amine catalysts such as triethylamine, triethylenediamine, tetramethylethylenediamine, tetramethylpropylenediamine, and tetramethylhexamethylenediamine, and metal catalysts such as tin-based catalysts such as stannous octoate, stannous oleate, and dibutyltin dilaurate. These can be used alone or in combination of two or more. Among these, dibutyltin dilaurate is preferably used. The amount of the catalyst used may be 0.001 to 100 parts by mass with respect to 100 parts by mass of the total amount of the polyol component and the polyisocyanate component.

[0178] When a catalyst is used in the urethanization reaction, it is preferable to use a phosphorus compound for treating the catalyst. The phosphorus compound is not particularly limited, and examples thereof include phosphate triesters such as trimethyl phosphate, triethyl phosphate, tributyl phosphate, di-2-ethylhexyl phosphate, triphenyl phosphate, tricresyl phosphate, and cresyl diphenyl phosphate; acid phosphate esters such as methyl acid phosphate, ethyl acid phosphate, propyl acid phosphate, isopropyl acid phosphate, butyl acid phosphate, lauryl acid phosphate, stearyl acid phosphate, 2-ethylhexyl acid phosphate, isodecyl acid phosphate, butoxyethyl acid phosphate, oleyl acid phosphate, tetracosyl acid phosphate, acetylene glycol acid phosphate, 2-hydroxyethyl methacrylate acid phosphate, dibutyl phosphate, monobutyl phosphate, monoisodecyl phosphate, and bis(2-ethylhexyl)phosphate; and triphenyl phosphate. phosphite, trisnonylphenyl phosphite, tricresyl phosphite, triethyl phosphite, tris(2-ethylhexyl) phosphite, tridecyl phosphite, trilauryl phosphite, tris(tridecyl) phosphite, trioleyl phosphite, diphenyl mono(2-ethylhexyl) phosphite, diphenyl monodecyl phosphite, diphenyl (monodecyl) phosphite, trilauryl phosphite, diethyl hydrogen phosphite, bis(2-ethylhexyl) Examples of such phosphite esters include bis(decyl)pentaerythritol diphosphite, tristearyl phosphite, distearyl pentaerythritol diphosphite, tris(2,4-di-tert-butylphenyl)phosphite, and other phosphite esters; phosphoric acid, phosphorous acid, and hypophosphorous acid. These may be used alone or in combination of two or more.Among these, acidic phosphoric acid esters are preferred, and 2-ethylhexyl acid phosphate is more preferred. The amount of the phosphorus compound used may be 10 to 2000 parts by mass based on 100 parts by mass of the catalyst.

[0179] The urethanization reaction can be carried out in the presence of a solvent. Examples of the solvent include esters such as ethyl acetate, butyl acetate, propyl acetate, γ-butyrolactone, δ-valerolactone, and ε-caprolactone; amides such as dimethylformamide, diethylformamide, and dimethylacetamide; sulfoxides such as dimethylsulfoxide; ethers such as tetrahydrofuran, dioxane, and 2-ethoxyethanol; ketones such as methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; and aromatic hydrocarbons such as benzene and toluene.

[0180] The urethane resin described above has good elongation and texture, excellent durability, and in some cases good breaking strength. Therefore, the urethane resin can be suitably used for synthetic leather, artificial leather, coating agents, etc.

[0181] <Coating agent> The coating agent of the present embodiment contains the above-mentioned urethane resin. Specific aspects of the urethane resin may be as described above.

[0182] One example of its use as a coating agent is the in-mold coating method that applies RIM (Reaction Injection Molding). Specifically, the in-mold coating method that applies RIM involves molding a plastic substrate inside an injection mold, and then forming a urethane coating on the surface of the molded product inside the mold. With this method, the internal volume of the mold is constant, and not only are the density, thickness, and hardness of the urethane coating stable, but it is also possible to faithfully reproduce the irregularities on the mold surface, resulting in a highly aesthetically pleasing appearance.

[0183] <Water-based urethane resin dispersion> The aqueous urethane resin dispersion contains an aqueous medium and a urethane resin or a neutralized product thereof dispersed in the aqueous medium. The urethane resin is one of the above-mentioned urethane resins having an acidic group (a polyol component containing a polyol having an acidic group).

[0184] As the aqueous medium, in addition to water, a solution containing an emulsifier, a dispersant, etc. can be used. The aqueous medium preferably contains water, and more preferably consists of only water.

[0185] When the aqueous urethane resin dispersion contains a neutralized product of the urethane resin, the acidic group of the urethane resin may be neutralized by a neutralizing agent. Examples of the neutralizing agent include organic amines such as ammonia, ethylamine, trimethylamine, triethylamine, triisopropylamine, tributylamine, triethanolamine, N-methyldiethanolamine, N-phenyldiethanolamine, monoethanolamine, dimethylethanolamine, diethylethanolamine, morpholine, N-methylmorpholine, 2-amino-2-ethyl-1-propanol, and higher alkyl-modified morpholine, alkali metals such as lithium, potassium, and sodium, and inorganic alkalis such as sodium hydroxide and potassium hydroxide. From the viewpoint of improving the durability and smoothness of the coating film, a highly volatile neutralizing agent that is easily dissociated by heating, such as ammonia, trimethylamine, and triethylamine, is preferably used. These neutralizing agents can be used alone or in combination of two or more.

[0186] In producing the aqueous urethane resin dispersion, an anionic polar group-containing compound can also be used. Examples of the anionic polar group-containing compound include those consisting of an organic acid having one or more active hydrogens and a neutralizing agent. Examples of the organic acid include carboxylates, sulfonates, phosphates, phosphonates, phosphinates, and thiosulfonates. These anionic polar groups contained in the organic acid may be introduced alone or may be associated with metal ions such as chelates.

[0187] In producing the aqueous urethane resin dispersion, a cationic polar group-containing compound can also be used. The cationic polar group-containing compound is, for example, a tertiary amine having one or more active hydrogens, and one selected from the group consisting of a neutralizer for inorganic acid, a neutralizer for organic acid, and a quaternizing agent. In addition, the cationic polar group-containing compound can also be a cationic compound such as a primary amine salt, a secondary amine salt, a tertiary amine salt, or a pyridinium salt.

[0188] Examples of tertiary amines having one or more active hydrogens include N,N-dimethylethanolamine, N,N-diethylethanolamine, N,N-dipropylethanolamine, N,N-diphenylethanolamine, N-methyl-N-ethylethanolamine, N-methyl-N-phenylethanolamine, N,N-dimethylpropanolamine, N-methyl-N-ethylpropanolamine, N-methyldiethanolamine, N-ethyldiethanolamine, N-methyldipropanolamine, N-phenyldiethanolamine, N-phenyldipropanolamine, N-hydroxyethyl-N-hydroxypropyl-methylamine, N,N'-dihydroxyethylpiperazine, triethanolamine, trisisopropanolamine, N-methyl-bis-(3-aminopropyl)-amine, N-methyl-bis-(2-aminopropyl)-amine, etc. Also usable are primary amines such as ammonia and methylamine, or secondary amines such as dimethylamine to which alkylene oxide is added.

[0189] Inorganic and organic acids include, for example, hydrochloric acid, acetic acid, lactic acid, cyanoacetic acid, phosphoric acid, and sulfuric acid.

[0190] Examples of the quaternizing agent include dimethyl sulfate, benzyl chloride, bromoacetamide, chloroacetamide, etc. Also usable are alkyl halides such as ethyl bromide, propyl bromide, and butyl bromide.

[0191] The aqueous urethane resin dispersion can be produced, for example, by sequentially carrying out the steps of reacting a polyol component containing a polyol having an acidic group with a polyisocyanate component in the presence or absence of a solvent to form a urethane prepolymer, neutralizing the acidic groups in the prepolymer with a neutralizing agent, dispersing the neutralized prepolymer in an aqueous medium, and reacting the prepolymer dispersed in the aqueous medium with a chain extender. In each step, a catalyst can be used as necessary to promote the reaction and control the amount of by-products.

[0192] A film formed by the aqueous urethane resin dispersion described above (for example, a film formed by coating the aqueous urethane resin dispersion on a substrate) is excellent in adhesion, flexibility, touch, etc. Therefore, the aqueous urethane resin dispersion can be suitably used for artificial leather, synthetic leather, exterior paint, interior paint, and coating agents.

[0193] <Two-liquid composition set> The polyol component and the polyisocyanate component for forming the urethane resin may be stored, transported, etc., in separate containers as a two-liquid composition set. The two-liquid composition set includes a first liquid containing at least the polyol component and a second liquid containing at least the polyisocyanate component. When a chain extender, a catalyst, a solvent, etc. are used, they may be contained in the first liquid and / or the second liquid, or may be mixed separately from the first liquid and the second liquid. The two-liquid composition set can be suitably used, for example, as a coating agent, and can also be suitably used in the production of artificial leather, synthetic leather, exterior paint, interior paint, etc. When the two-liquid composition set is used as a coating agent, for example, after mixing the first liquid and the second liquid, the resulting mixed liquid is applied to a substrate, and optionally heated to form a coating film (for example, a cured film containing a urethane resin).

[0194] As an example of the use of the two-liquid composition set as a coating agent, the set can be suitably used as a resin composition that does not use organic solvents in the production of artificial leather, synthetic leather, etc., and forms a polyurethane resin that has excellent adhesion, flexibility, touch, etc.

[0195] The urethane resin-forming composition containing the above-mentioned polyol component and the above-mentioned polyisocyanate component, and the polyurethane resin composition containing the above-mentioned urethane resin are preferably used as an aqueous polyurethane resin emulsion, a polyurethane resin synthesized without a solvent, or a precursor thereof. Then, by curing this aqueous polyurethane resin emulsion or the polyurethane resin synthesized without a solvent, a molded product such as a coating film or a film that is tough, has a reduced 100% modulus (good texture), and has a high softening temperature can be obtained, and can be suitably used for leather applications such as artificial leather and synthetic leather, or as a surface treatment agent for leather. The 100% modulus is one of the indicators that quantify the moist, elastic, and luxurious feeling when touching synthetic leather, and when the value is within a certain numerical range, the urethane resin has good properties.

[0196] <Application> The composition, urethane resin, aqueous urethane resin dispersion, and coating agent of the present embodiment described above can be used in a coating composition that is preferably used as a clear coating for automobile exteriors and a coating for automobile interiors. The composition, urethane resin, aqueous urethane resin dispersion, and coating agent of the present embodiment can also be preferably used in surface treatment of home appliances, OA (office automation) products, leather, and synthetic leather. EXAMPLES

[0197] Examples of the present invention will be described below, but the present invention is not limited to these examples.

[0198] [Synthesis Example 1: Synthesis of polycarbonate diol 1] 826g of 1,6-hexanediol, 787g of diethyl carbonate, and 0.05g of tetrabutyl titanate were mixed in a 2L two-necked glass reactor equipped with a stirrer, a thermometer, a heating device, a fractionator filled with structured packing, and a cooler, and reacted at 100 to 190°C for 8 hours under normal pressure while removing low boiling point components. The reaction temperature was then increased to 190°C, the pressure in the flask was reduced to 1 kPa, and the reaction was continued for another 8 hours to obtain a polycarbonate polyol (PCD-1).

[0199] [Table 1]

[0200] Details of the raw materials used are as follows: 1,6-Hexanediol: BASF JAPAN Trimethylolpropane: Sigma-Aldrich Diethyl carbonate: Sigma-Aldrich Tetrabutyl titanate: Tokyo Chemical Industry Co., Ltd.

[0201] <Example> <First Example> Example 1A In a 1L two-neck glass reactor (reactor A) equipped with a stirrer, a thermometer, a heating device, a rectification column filled with structured packing, and a cooler, 16.5g of trimethylolpropane, 187.1g of 1,6-hexanediol, 196.4g of diethyl carbonate, 0.71g of 3-ethyl-3-hydroxymethyloxetane, and 0.030g of lithium acetylacetonate were mixed. The resulting mixture was heated at 130-150°C (initial temperature 130°C, final temperature 150°C) under normal pressure, and reacted for 1.5 hours while removing low-boiling components (alcohol derived from carbonate ester, etc.). The distillate temperature was 77°C or higher and lower than 79°C. Furthermore, the pressure in the flask was gradually reduced to 0.5kPa over 0.5 hours at a reaction temperature of 150°C, and the reaction was continued for 1.0 hour at 0.5kPa to obtain a composition (PCP-1A) containing compound (A-1).

[0202] Example 2A A composition (PCP-2A) containing compound (A-1) was obtained in the same manner as in Example 1A, except that 1.43 g of 3-ethyl-3-hydroxymethyloxetane was added.

[0203] Example 3A A composition (PCP-3A) containing compound (A-1) was obtained in the same manner as in Example 1A, except that 2.14 g of 3-ethyl-3-hydroxymethyloxetane was added.

[0204] Example 4A A composition (PCP-4A) containing compound (A-1) was obtained in the same manner as in Example 1A, except that 2.85 g of 3-ethyl-3-hydroxymethyloxetane was added.

[0205] Example 5A A composition (PCP-5A) containing compound (A-1) was obtained in the same manner as in Example 1A, except that 5.70 g of 3-ethyl-3-hydroxymethyloxetane was added.

[0206] Example 6A In the reactor A, 16.5 g of trimethylolpropane, 187.1 g of 1,6-hexanediol, 196.4 g of diethyl carbonate, and 0.030 g of lithium acetylacetonate were mixed. The obtained mixture was heated at 130 to 150°C (initial temperature 130°C, final temperature 150°C) under normal pressure, and reacted for 1.5 hours while removing low-boiling components (such as alcohol derived from carbonate ester). The distillate temperature was 77°C or higher and lower than 79°C. Furthermore, the pressure in the flask was gradually reduced to 0.5 kPa over 0.5 hours at a reaction temperature of 150°C, and the reaction was continued for 35 hours at 0.5 kPa to obtain a composition (PCP-6A) containing compound (A-1).

[0207] Comparative Example 1A A composition (PCP-7A) containing compound (A-1) was obtained in the same manner as in Example 1A, except that the amount of 3-ethyl-3-hydroxymethyloxetane was 0 g.

[0208] (Comparative example 2A) A composition (PCP-8A) containing compound (A-1) was obtained in the same manner as in Example 1A, except that 0.07 g of 3-ethyl-3-hydroxymethyloxetane was added.

[0209] (Comparative example 3A) A composition (PCP-9A) containing compound (A-1) was obtained in the same manner as in Example 1A, except that 0.14 g of 3-ethyl-3-hydroxymethyloxetane was added.

[0210] (Comparative example 4A) A composition (PCP-10A) containing compound (A-1) was obtained in the same manner as in Example 1A, except that 0.43 g of 3-ethyl-3-hydroxymethyloxetane was added.

[0211] (Comparative example 5A) A composition (PCP-11A) containing compound (A-1) was obtained in the same manner as in Example 1A, except that 7.13 g of 3-ethyl-3-hydroxymethyloxetane was added.

[0212] Comparative Example 6A In the reactor A, 16.5 g of trimethylolpropane, 187.1 g of 1,6-hexanediol, 196.4 g of diethyl carbonate, and 0.020 g of lithium acetylacetonate were mixed. The obtained mixture was heated at 130 to 150°C (initial temperature 130°C, final temperature 150°C) under normal pressure, and reacted for 8 hours while removing low-boiling components (alcohol derived from carbonate ester, etc.). The distillate temperature was 77°C or higher and lower than 79°C. The reaction temperature was further increased to 150°C, the pressure in the flask was reduced to 1 kPa, and the reaction was continued for 8 hours at 1 kPa to obtain a composition (PCP-12A) containing compound (A-1).

[0213] (Analysis and Evaluation) [Measurement of number average molecular weight] The polycarbonate polyol obtained above and the composition obtained above were subjected to GPC analysis under the following conditions to measure the number average molecular weight of the polycarbonate polyol and the number average molecular weight of the composition. The results are shown in Tables 1 and 2. -conditions- (1) Measuring instrument: HLC-8420 (manufactured by Tosoh Corporation) (2) Column: TSKgel (Tosoh Corporation) G3000H-XL G3000H-XL G2000H-XL G2000H-XL (3) Mobile phase: THF (tetrahydrofuran) (4) Detector: RI (refractive index) detector (accessory for HLC-8420) (5) Temperature: 40℃ (6)Flow rate: 1.000ml / min (7) Calibration curve: A calibration curve was obtained using the following products (all bifunctional polyoxypropylene polyols manufactured by Sanyo Chemical Industries, Ltd.). "Sannix PP-200" (number average molecular weight = 200, average number of functional groups: 2) "Sannix PP-400" (number average molecular weight = 400, average number of functional groups: 2) "Sannix PP-1000" (number average molecular weight = 1000, average number of functional groups: 2) "Sannix PP-2000" (number average molecular weight = 2000, average number of functional groups: 2) "Sannix PP-3000" (number average molecular weight = 3200, average number of functional groups: 2) "Sannix PP-4000" (number average molecular weight = 4160, average number of functional groups: 2) (8) Approximation of calibration curve: Cubic equation (9) Sample solution concentration: 0.5% by mass in THF solution

[0214] [Hydroxyl value measurement] The hydroxyl value of the polycarbonate polyol obtained above and the hydroxyl value of the composition obtained above were measured by a method using an acetylation reagent in accordance with JIS K1557-1. The results are shown in Tables 1 and 2.

[0215] [Characteristics evaluation] The composition obtained above was used as a sample, which was heated at 80°C for 1 hour and then left at 25°C for 3 days. The state of the sample after leaving it was visually confirmed, and if it had even a slight fluidity at the above temperature, it was classified as liquid, and if it had no fluidity, it was classified as solid. The results are shown in Table 2.

[0216] <Calculation method for each composition> (Average number of hydroxyl groups) The deemed average hydroxyl functionality of the composition was calculated from the number average molecular weight and hydroxyl value obtained by GPC (Gel Permeation Chromatography) measurement. Normally, the average hydroxyl functionality is calculated from the true number average molecular weight and average hydroxyl value, but since it is difficult to calculate the true number average molecular weight of the composition, the number average molecular weight converted from the PPG calibration curve by GPC measurement is used and defined as the deemed average hydroxyl functionality. The deemed average hydroxyl functionality is defined by the following formula. Deemed average number of hydroxyl functional groups = (average hydroxyl value of composition (mgKOH / g) x number average molecular weight (g / mol) calculated from PPG calibration curve by GPC measurement of composition) / (56.11 (KOHg / mol) x 1000)

[0217] [Composition analysis] The composition was analyzed by the following procedure.

[0218] First, the composition (sample) obtained above was dissolved in deuterated chloroform (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) to obtain a solution. Tetramethylsilane (TMS) was added to the solution as a chemical shift standard to obtain a test solution. The obtained test solution was analyzed using JNM-ECX400 (manufactured by JEOL Ltd.). 1 Measure H-NMR and set the TMS signal at 0 ppm. 1 H-NMR spectrum was obtained under the following conditions: -conditions- ·Resonance frequency: 400MHz Pulse width: 45degree Waiting time: 5 seconds Number of times: 64 Sample solution concentration (TMS-containing deuterated chloroform): 3% by mass

[0219] Next, 1 From the H-NMR spectrum, the integral value Δ of the methylene signal (SC) located next to the oxygen atom of the oxetane group of the group represented by the above formula (C) is SC and the integral value Δ of the methylene signal (SD) located next to the hydroxyl group of the group represented by formula (D). SD and the integral value Δ of the methylene signal (SE) located next to the hydroxyl group of the group represented by formula (E). SE In addition, the R of the group represented by formula (I) and formula (C) was calculated. 2 is a methyl group or an ethyl group, the integral values ​​of the terminal methyl signals are calculated and these are expressed as the integral value Δ SI It was decided.

[0220] Specifically, the signal from 4.390 ppm to 4.500 ppm is defined as a signal (SC), the signal from 3.618 ppm to 3.720 ppm is defined as a signal (SD), the signal from 3.590 ppm to 3.618 ppm is defined as a signal (SE), and the signal from 0.700 ppm to 1.130 ppm is defined as a signal of R of the group represented by formula (I) and formula (C). 2 is a methyl group (when the polyhydric alcohol (e) is trimethylolethane), and the signals between 0.700 ppm and 1.000 ppm are R 2 is the signal (SI) when the polyhydric alcohol (e) is trimethylolpropane.

[0221] The baseline for the integral value measurement was a horizontal line drawn by comparing the spectral intensities in the specified spectral range and using the lowest spectral intensity as the reference. The signal (SE) usually shows a single peak, but it may be affected by a very small amount of moisture and split into two peaks. If a split peak is detected, it will deviate from the above integral range and an accurate C value cannot be obtained. E Therefore, the integral value obtained from the signal (SE) is adopted when it shows a single peak.

[0222] From the integral obtained, the molar ratio (C C / C T × 100), and molar ratio (C C / (C C +C D +C E ) × 100) was calculated. The results are shown in Table 2.

[0223] [Table 2]

[0224] In Table 2, the "composition" (unit: g) of Examples 1A to 6A and Comparative Examples 1A to 6A indicates the reaction raw materials.

[0225] (Physical property evaluation) A cured urethane coating (film) was prepared by the following method, and the physical properties (tensile properties, heat resistance, and low-temperature properties) of the obtained film were evaluated as a sample.

[0226] [Preparation of urethane hardened coating] First, the composition obtained above, a polyisocyanate component (C-2612), a urethane catalyst, a phosphorus compound (JP508), and a dilution solvent were mixed in a 200 mL glass bottle in the proportions (unit: g) shown in Table 3. Immediately after mixing, the mixed liquid was poured onto a release paper and cast into a film having a thickness of 200 μm using a bar coater. The cast film was then cured by heating under the conditions of 25° C. for 30 minutes, 50° C. for 30 minutes, 80° C. for 30 minutes, 120° C. for 1 hour, and 50° C. for 18 hours to obtain a urethane cured coating (film).

[0227] [100% tensile modulus evaluation] The tensile properties and 100% modulus properties of the obtained film were measured under the following conditions in accordance with JIS K6251. (100% modulus, strength at break, elongation at break) -conditions- Test equipment: Tensilon UTA-500 (manufactured by A&D) Measurement conditions: 25℃×50%RH Head speed: 200mm / min Dumbbell No. 4

[0228] [Softening temperature] A test piece was obtained from the obtained film using a dumbbell, a 2 cm mark was drawn on the test piece, and the thickness at the center of the mark was measured. A weight of a specified weight was attached to one grip of the test piece, and the other grip was clamped with a double clip, and the test piece was hung in a dryer with the clip on the upper side. The temperature inside the dryer was then increased and the distance between the marks was observed. The temperature at which the distance between the marks reached 4 cm was read as the softening temperature. Processing equipment: constant temperature blower dryer DRK633DA (manufactured by Advantec) Weight: thickness of center of gauge line (μm) x 0.05g Dumbbell No. 2 (JIS K6251 compliant) Heating rate: 5℃ / min

[0229] [Glass transition temperature] A test piece (width 0.4 cm, length 2.5 cm) was obtained from the obtained film using a dumbbell, and the thickness (approximately 100 to 200 μm) at the center of the gauge line was measured. The glass transition temperature was determined as the peak top temperature of the obtained loss modulus (E") / storage modulus (E') = tan δ. -conditions- Processing equipment: RHEOVIBRON DDV-01GP Dynamic Viscoelastomeret (manufactured by Orientec) Range: -50~40℃ Heating rate: 3℃ / min Frequency: 35Hz ·Amplitude: 16μm ·Static tension: 5.00gf

[0230] [Evaluation Criteria] The physical properties of 100% modulus, breaking strength, breaking elongation, softening temperature, and glass transition temperature were evaluated as A, B, C, and D (A: very good, B: good, C: fair, D: poor). <100% modulus> A: 1.5MPa or more and 2.0MPa or less B: Less than 1.5MPa C: Over 2.0MPa <Breaking strength> A: Over 19MPa B: 15MPa or more and 19MPa or less D: Less than 15MPa <Elongation at break> A: Over 350% B: 350% or less <Softening temperature> A: Over 240℃ B: Above 230℃ and below 240℃ C: Less than 230℃ <Glass transition temperature> A: 1.5℃ or less B: Over 1.5℃

[0231] [Table 3]

[0232] (Handling evaluation) An isocyanate-terminated urethane prepolymer was prepared by the following method, and the handleability (prepolymer viscosity) of the obtained isocyanate-terminated urethane prepolymer was evaluated as a sample.

[0233] [Preparation of isocyanate-terminated urethane prepolymer] The composition obtained above, N-980N (manufactured by Tosoh Corporation: number average molecular weight 2000; hydroxyl value 56.11 mgKOH / g; 1,6-hexanediol-based polycarbonate diol), 1,6-hexanediol, 2,2-dimethylolpropanoic acid (hydrophilizing agent), isophorone diisocyanate (polyisocyanate), and methyl ethyl ketone (organic solvent) were charged in the proportions (unit: g) shown in Table 4 into a 1 L reactor equipped with a stirrer, a thermometer, a nitrogen seal tube, and a cooler. The mixture was heated to 78°C and stirred at the same temperature for 30 minutes, after which 0.010 g of DOTDL (catalyst) was added and reacted for 2 hours. Next, 0.015 g of DOTDL was added and reacted for 2 hours, after which 0.010 g of DOTDL was added and reacted for another 2 hours. After it was confirmed from the NCO content of the product that the hydroxyl groups of the polyol and the hydrophilizing agent had been completely consumed, the reaction was stopped and an isocyanate-terminated urethane prepolymer was obtained.

[0234] [Viscosity of isocyanate-terminated urethane prepolymer] Approximately 2 g of the resulting isocyanate-terminated urethane prepolymer was sampled and placed in a sample tube together with a 4.7 mm aluminum spherical probe, and the viscosity in a steady state at 50°C was measured using an EMS (Electro Magnetically Spinning) viscometer (Kyoto Electronics Manufacturing Co., Ltd.: EMS-1000). The results are shown in Table 4. Measurement conditions ·Temperature: 50℃ Spherical probe: φ4.7mm Motor speed: 1000 rpm Measurement interval: 30 seconds Measurement time: 5 minutes

[0235] [Evaluation Criteria] The viscosity of the isocyanate-terminated urethane prepolymer was evaluated on a scale of A, B, C, and D (A: very good, B: good, C: fair, D: poor). <Viscosity> A: Less than 1700 mPa·s B: 1700mPa·s or more and 1800mPa·s or less D: More than 1800mPa·s

[0236] [Table 4]

[0237] The compositions were overall evaluated on a scale of A, B, C, and D (A: very good, B: good, C: average, D: poor). The results are shown in Table 5. <Overall rating> A: Only A ratings for each physical property and handling property B: The evaluation of each physical property and handling property does not include D, and includes one B or C. C: The evaluation of each physical property and handling property does not include D, and includes two or more B or C. D: Each physical property and handling evaluation includes D

[0238] [Table 5]

[0239] Details of the materials used in the first example are as follows: 1,6-Hexanediol: BASF JAPAN Trimethylolpropane: Sigma-Aldrich Diethyl carbonate: Sigma-Aldrich 3-Ethyl-3-hydroxymethyloxetane: manufactured by Tokyo Chemical Industry Co., Ltd. Lithium acetylacetonate: Sigma-Aldrich C-2612: Coronate 2612 (trade name), hexamethylene diisocyanate adduct modified polyisocyanate, isocyanate content = 17.2%, manufactured by Tosoh Corporation JP-508: Product name, 2-ethylhexyl acid phosphate, manufactured by Johoku Chemical Industry Co., Ltd. DOTDL: Dioctyltin dilaurate, manufactured by Kishida Chemical Industry Co., Ltd. Methyl ethyl ketone: Maruzen Petrochemical Co., Ltd. Toluene: Fujifilm Wako Pure Chemical Industries, Ltd. BYK-331: Silicone surface conditioner, manufactured by BYK 2,2-Dimethylolpropionic acid: Tokyo Chemical Industry Co., Ltd. Isophorone diisocyanate: Evonik

[0240] <Second Example> Example 1B In the reactor A, 15.8g of trimethylolpropane, 99.5g of 1,6-hexanediol, 75.9g of 1,4-butanediol, 208.9g of diethyl carbonate, 0.68g of 3-ethyl-3-hydroxymethyloxetane, and 0.030g of lithium acetylacetonate were mixed. The obtained mixture was heated at 130 to 150°C (initial temperature 130°C, final temperature 150°C) under normal pressure, and reacted for 1.5 hours while removing low-boiling components (alcohol derived from carbonate ester, etc.). The distillate temperature was 77°C or higher and lower than 79°C. Furthermore, the pressure in the flask was reduced to 0.5kPa over 0.5 hours at a reaction temperature of 150°C, and the reaction was further carried out at 0.5kPa for 1.0 hour to obtain a composition (PCP-1B) containing compound (A-1).

[0241] Example 2B A composition (PCP-2B) containing compound (A-1) was obtained in the same manner as in Example 1B, except that 1.36 g of 3-ethyl-3-hydroxymethyloxetane was added.

[0242] Example 3B A composition (PCP-3B) containing compound (A-1) was obtained in the same manner as in Example 1B, except that 2.73 g of 3-ethyl-3-hydroxymethyloxetane was added.

[0243] (Comparative example 1B) A composition (PCP-4B) containing the compound (A-1) was obtained in the same manner as in Example 1B, except that the amount of 3-ethyl-3-hydroxymethyloxetane was 0 g.

[0244] (Comparative Example 2B) A composition (PCP-5B) containing the compound (A-1) was obtained in the same manner as in Example 1B, except that the amount of 3-ethyl-3-hydroxymethyloxetane was 6.82 g.

[0245] Example 4B A composition (PCP-6B) containing compound (A-1) was obtained in the same manner as in Example 1B, except that 0.60 g of 3-ethyl-3-hydroxymethyloxetane was added.

[0246] Example 5B A composition (PCP-7B) containing compound (A-1) was obtained in the same manner as in Example 1B, except that 2.73 g of 3-ethyl-3-hydroxymethyloxetane was added.

[0247] Example 6B A composition (PCP-8B) containing compound (A-1) was obtained in the same manner as in Example 1B, except that 4.80 g of 3-ethyl-3-hydroxymethyloxetane was added.

[0248] (Comparative example 3B) A composition (PCP-9B) containing compound (A-1) was obtained in the same manner as in Example 1B, except that 0.34 g of 3-ethyl-3-hydroxymethyloxetane was added.

[0249] (Comparative example 4B) A composition (PCP-10B) containing compound (A-1) was obtained in the same manner as in Example 1B, except that 0.50 g of 3-ethyl-3-hydroxymethyloxetane was added.

[0250] Comparative Example 5B A composition (PCP-11B) containing compound (A-1) was obtained in the same manner as in Example 1B, except that 8.20 g of 3-ethyl-3-hydroxymethyloxetane was added.

[0251] (Comparative Example 6B) In the reactor A, 15.8g of trimethylolpropane, 99.5g of 1,6-hexanediol, 75.9g of 1,4-butanediol, 208.9g of diethyl carbonate, and 0.030g of lithium acetylacetonate were mixed. The obtained mixture was heated at 130 to 150°C (initial temperature 130°C, final temperature 150°C) under normal pressure, and reacted for 8 hours while removing low-boiling components (alcohol derived from carbonate ester, etc.). The distillate temperature was 77°C or higher and lower than 79°C. The reaction temperature was further increased to 150°C, the pressure in the flask was reduced to 1 kPa, and the reaction was continued for 8 hours at 1 kPa to obtain a composition (PCP-13B) containing compound (A-1).

[0252] (Analysis and Evaluation) In the same manner as in Example 1, the number average molecular weight and hydroxyl value of the composition obtained above were measured, and property evaluation, calculation of the assumed average number of hydroxyl functional groups, and composition analysis were performed. In the composition analysis, signals from 4.390 ppm to 4.500 ppm were designated as signals (SC), signals from 3.618 ppm to 3.720 ppm were designated as signals (SD), signals from 3.590 ppm to 3.618 ppm were designated as signals (SE), and signals from 0.700 ppm to 1.130 ppm were designated as signals representing the R groups represented by formula (I) and formula (C). 2 is a methyl group (when the polyhydric alcohol (e) is trimethylolethane), and the signals between 0.700 ppm and 1.000 ppm are R 2The signal (SI) was taken as the signal when the polyhydric alcohol (e) was an ethyl group (when the polyhydric alcohol (e) was trimethylolpropane). The results are shown in Table 6. FIG. 1 shows the composition obtained in Example 1B. 1 The H-NMR spectrum is shown.

[0253] [Table 6]

[0254] In Table 6, the "composition" (unit: g) of Examples 1B to 6B and Comparative Examples 1B to 6B indicates the reaction raw materials.

[0255] (Physical property evaluation) A urethane cured coating (film) was obtained in the same manner as in Example 1, except that the composition obtained above, a polyisocyanate component (C-2612), a urethane catalyst, a phosphoric ester (JP508), and a dilution solvent were mixed in the proportions (unit: g) shown in Table 7. The obtained film was then used as a sample to evaluate the physical properties (tensile properties, texture properties, low temperature properties) in the same manner as in Example 1. The results are shown in Table 7.

[0256] [Evaluation Criteria] The physical properties of 100% modulus, breaking strength, breaking elongation, softening temperature, and glass transition temperature were evaluated as A, B, C, and D (A: very good, B: good, C: fair, D: poor). <100% modulus> A: 1.0MPa or more and 1.7MPa or less B: Over 1.7MPa C: Less than 1.0 <Breaking strength> A: Over 19MPa B: 16MPa or more and 19MPa or less D: Less than 16MPa <Elongation at break> A: 410% or more B: Less than 410% <Softening temperature> A: Over 240℃ B: Below 240℃ <Glass transition temperature> A:4.5℃ or less B: Over 4.5℃

[0257] [Table 7]

[0258] (Handling evaluation) The handleability (viscosity of isocyanate-terminated urethane prepolymer) was evaluated in the same manner as in Example 1, except that the composition obtained above, N-980N, 1,6-hexanediol, 2,2-dimethylolpropanoic acid (hydrophilizing agent), isophorone diisocyanate (polyisocyanate), and methyl ethyl ketone (organic solvent) were charged in the amounts (unit: g) shown in Table 8. The results are shown in Table 8.

[0259] [Evaluation Criteria] The viscosity of the isocyanate-terminated urethane prepolymer was evaluated on a scale of A, B, C, and D (A: very good, B: good, C: fair, D: poor). <Viscosity> A: 2500mPa・s or less D: More than 2500mPa·s

[0260] [Table 8]

[0261] The overall evaluation of the composition was rated as A, B, C, or D (A: very good, B: good, C: average, D: poor). The results are shown in Table 9. <Overall rating> A: Only A ratings for each physical property and handling property B: The evaluation of each physical property and handling property does not include D, and includes one B or C. C: The evaluation of each physical property and handling property does not include D, and includes two or more B or C. D: Each physical property and handling evaluation includes D

[0262] [Table 9]

[0263] Details of the materials used in the second example are as follows: 1,6-Hexanediol: BASF JAPAN 1,4-Butanediol: Tokyo Chemical Industry Co., Ltd. Trimethylolpropane: Sigma-Aldrich Diethyl carbonate: Sigma-Aldrich 3-Ethyl-3-hydroxymethyloxetane: manufactured by Tokyo Chemical Industry Co., Ltd. Lithium acetylacetonate: Sigma-Aldrich C-2612: Coronate 2612 (trade name), hexamethylene diisocyanate adduct modified polyisocyanate, isocyanate content = 17.2%, manufactured by Tosoh Corporation JP-508: Product name, 2-ethylhexyl acid phosphate, manufactured by Johoku Chemical Industry Co., Ltd. DOTDL: Dioctyltin dilaurate, manufactured by Kishida Chemical Industry Co., Ltd. Methyl ethyl ketone: Maruzen Petrochemical Co., Ltd. Toluene: Fujifilm Wako Pure Chemical Industries, Ltd. BYK-331: Silicone surface conditioner, manufactured by BYK 2,2-Dimethylolpropionic acid: Tokyo Chemical Industry Co., Ltd. Isophorone diisocyanate: Evonik

[0264] <Third Example> Example 1C In the reactor A, 16.5g of trimethylolpropane, 93.6g of 1,6-hexanediol, 93.6g of 3-methyl-1,5-pentanediol, 196.4g of diethyl carbonate, 0.77g of 3-ethyl-3-hydroxymethyloxetane, and 0.030g of lithium acetylacetonate were mixed. The obtained mixture was heated at 130 to 150°C (initial temperature 130°C, final temperature 150°C) under normal pressure, and reacted for 1.5 hours while removing low-boiling components (alcohol derived from carbonate ester, etc.). The distillate temperature was 77°C or higher and lower than 79°C. Furthermore, the pressure in the flask was reduced to 0.5kPa over 0.5 hours at a reaction temperature of 150°C, and the reaction was further carried out at 0.5kPa for 1.0 hour to obtain a composition (PCP-1C) containing compound (A-1).

[0265] Example 2C A composition (PCP-2C) containing compound (A-1) was obtained in the same manner as in Example 1C, except that 1.42 g of 3-ethyl-3-hydroxymethyloxetane was added.

[0266] Example 3C A composition (PCP-3C) containing compound (A-1) was obtained in the same manner as in Example 1C, except that 3.00 g of 3-ethyl-3-hydroxymethyloxetane was added.

[0267] (Comparative example 1C) A composition (PCP-4C) containing the compound (A-1) was obtained in the same manner as in Example 1C, except that the amount of 3-ethyl-3-hydroxymethyloxetane was 0 g.

[0268] (Comparative Example 2C) A composition (PCP-5C) containing the compound (A-1) was obtained in the same manner as in Example 1C, except that the amount of 3-ethyl-3-hydroxymethyloxetane was 0.17 g.

[0269] (Comparative example 3C) A composition (PCP-6C) containing the compound (A-1) was obtained in the same manner as in Example 1C, except that the amount of 3-ethyl-3-hydroxymethyloxetane was 7.30 g.

[0270] Example 4C A composition (PCP-7C) containing compound (A-1) was obtained in the same manner as in Example 1C, except that 2.20 g of 3-ethyl-3-hydroxymethyloxetane was added.

[0271] Example 5C A composition (PCP-8C) containing compound (A-1) was obtained in the same manner as in Example 1C, except that 3.85 g of 3-ethyl-3-hydroxymethyloxetane was added.

[0272] Example 6C A composition (PCP-9C) containing compound (A-1) was obtained in the same manner as in Example 1C, except that 6.50 g of 3-ethyl-3-hydroxymethyloxetane was added.

[0273] Example 7C In the reactor A, 16.5g of trimethylolpropane, 93.6g of 1,6-hexanediol, 93.6g of 3-methyl-1,5-pentanediol, 196.4g of diethyl carbonate, and 0.030g of lithium acetylacetonate were mixed. The obtained mixture was heated at 130 to 150°C (initial temperature 130°C, final temperature 150°C) under normal pressure, and reacted for 1.5 hours while removing low-boiling components (alcohol derived from carbonate ester, etc.). The distillate temperature was 77°C or higher and lower than 79°C. Furthermore, the pressure in the flask was gradually reduced to 0.5 kPa over 0.5 hours at a reaction temperature of 150°C, and the reaction was further carried out at 0.5 kPa for 35 hours to obtain a composition (PCP-10C) containing compound (A-1).

[0274] (Comparative Example 4C) A composition (PCP-11C) containing the compound (A-1) was obtained in the same manner as in Example 1C, except that the amount of 3-ethyl-3-hydroxymethyloxetane was 0.55 g.

[0275] (Analysis and Evaluation) In the same manner as in Example 1, the number average molecular weight and hydroxyl value of the composition obtained above were measured, and property evaluation, calculation of the deemed average number of hydroxyl functional groups, and composition analysis were performed. In the composition analysis, a signal from 4.390 ppm to 4.500 ppm was designated as signal (SC), a signal from 3.618 ppm to 3.720 ppm was designated as signal (SD), and a signal from 3.590 ppm to 3.618 ppm was designated as signal (SE). The results are shown in Table 10. Figure 2 shows the composition obtained in Example 1C. 1 The H-NMR spectrum is shown.

[0276] [Table 10]

[0277] In Table 10, the "composition" (unit: g) for Examples 1C to 7C and Comparative Examples 1C to 4C indicates the reaction raw materials.

[0278] (Physical property evaluation) A urethane cured coating (film) was obtained in the same manner as in Example 1, except that the composition obtained above, a polyisocyanate component (C-2612), a urethane catalyst, a phosphoric ester (JP508), and a dilution solvent were mixed in the proportions (unit: g) shown in Tables 8 and 9. The obtained film was then used as a sample to evaluate the physical properties (tensile properties, texture properties, low-temperature properties) in the same manner as in Example 1. The results are shown in Table 11.

[0279] [Evaluation Criteria] The physical properties of 100% modulus, breaking strength, breaking elongation, softening temperature, and glass transition temperature were evaluated as A, B, C, and D (A: very good, B: good, C: fair, D: poor). <100% modulus> A: 2.0MPa or less B: Over 2.0MPa <Breaking strength> A: Over 14.5MPa B: 13MPa or more and 14.5MPa or less D: Less than 13MPa <Elongation at break> A: 400% or more B: Less than 400% <Softening temperature> A: 230℃ or higher B: Less than 230℃ <Glass transition temperature> A:4.0℃ or less B: Over 4.0℃

[0280] [Table 11]

[0281] (Handling evaluation) The handleability (viscosity of isocyanate-terminated urethane prepolymer) was evaluated in the same manner as in Example 1, except that the composition obtained above, N-980N, 1,6-hexanediol, 2,2-dimethylolpropanoic acid (hydrophilizing agent), isophorone diisocyanate (polyisocyanate), and methyl ethyl ketone (organic solvent) were charged in the amounts (unit: g) shown in Table 12. The results are shown in Table 12.

[0282] [Evaluation Criteria] The viscosity of the isocyanate-terminated urethane prepolymer was evaluated on a scale of A, B, C, and D (A: very good, B: good, C: fair, D: poor). <Viscosity> A: 1400mPa・s or less D: More than 1400mPa·s

[0283] [Table 12]

[0284] The overall evaluation of the composition was rated as A, B, C, or D (A: very good, B: good, C: average, D: poor). The results are shown in Table 13. <Overall rating> A: Only A ratings for each physical property and handling property B: The evaluation of each physical property and handling property does not include D, and includes one B or C. C: The evaluation of each physical property and handling property does not include D, and includes two or more B or C. D: Each physical property and handling evaluation includes D

[0285] [Table 13]

[0286] Details of the materials used in the third example are as follows: 1,6-Hexanediol: BASF JAPAN 3-Methyl-1,5-pentanediol: Fujifilm Wako Pure Chemical Industries, Ltd. Trimethylolpropane: Sigma-Aldrich Diethyl carbonate: Sigma-Aldrich 3-Ethyl-3-hydroxymethyloxetane: manufactured by Tokyo Chemical Industry Co., Ltd. Lithium acetylacetonate: Sigma-Aldrich C-2612: Coronate 2612 (trade name), hexamethylene diisocyanate adduct modified polyisocyanate, isocyanate content = 17.2%, manufactured by Tosoh Corporation JP-508: Product name, 2-ethylhexyl acid phosphate, manufactured by Johoku Chemical Industry Co., Ltd. DOTDL: Dioctyltin dilaurate, manufactured by Kishida Chemical Industry Co., Ltd. Methyl ethyl ketone: Maruzen Petrochemical Co., Ltd. Toluene: Fujifilm Wako Pure Chemical Industries, Ltd. BYK-331: Silicone surface conditioner, manufactured by BYK 2,2-Dimethylolpropionic acid: Tokyo Chemical Industry Co., Ltd. Isophorone diisocyanate: Evonik

[0287] (Fourth embodiment) Example 1D 371.6 g of PCD-1, 128.2 g of Plaxel 305, 1.35 g of 3-ethyl-3-hydroxymethyloxetane, and 0.08 g of lithium acetylacetonate were mixed in a 0.5 L four-neck glass reactor (reactor B) equipped with a stirrer, thermometer, heating device, and cooler. The mixture was heated at 190°C under normal pressure and reacted for 6 hours. A composition (PCP-1D) containing compound (A-1) was obtained.

[0288] Example 2D A composition (PCP-2D) containing compound (A-1) was obtained in the same manner as in Example 1D, except that 2.91 g of 3-ethyl-3-hydroxymethyloxetane was added.

[0289] Example 3D A composition (PCP-3D) containing compound (A-1) was obtained in the same manner as in Example 1D, except that 5.42 g of 3-ethyl-3-hydroxymethyloxetane was added.

[0290] Example 4D 371.6 g of PCD-1, 128.2 g of Plaxel 305, and 0.08 g of lithium acetylacetonate were mixed in a reactor B. The mixture was heated at 190° C. under normal pressure and reacted for 35 hours to obtain a composition (PCP-4D) containing compound (A-1).

[0291] Comparative Example 1D A composition (PCP-5D) containing compound (A-1) was obtained in the same manner as in Example 1D, except that the amount of 3-ethyl-3-hydroxymethyloxetane was 0 g.

[0292] (Comparative example 2D) A composition (PCP-6D) containing the compound (A-1) was obtained in the same manner as in Example 1D, except that the amount of 3-ethyl-3-hydroxymethyloxetane was 0.39 g.

[0293] (Comparative example 3D) A composition (PCP-7D) containing the compound (A-1) was obtained in the same manner as in Example 1D, except that the amount of 3-ethyl-3-hydroxymethyloxetane was 0.93 g.

[0294] (Comparative example 4D) A composition (PCP-8D) containing compound (A-1) was obtained in the same manner as in Example 1D, except that the amount of 3-ethyl-3-hydroxymethyloxetane was 13.5 g.

[0295] Comparative Example 5D 371.6 g of PCD-1, 128.2 g of Plaxel 305, and 0.05 g of potassium hydrogen carbonate were mixed in a reactor B. The mixture was heated at 190° C. under normal pressure and reacted for 5 hours. A composition (PCP-9D) containing the compound (A-1) was obtained.

[0296] Example 5D A composition (PCP-10D) containing compound (A-1) was obtained in the same manner as in Example 1D, except that 0.97 g of 3-ethyl-3-hydroxymethyloxetane was added.

[0297] Example 6D A composition (PCP-11D) containing compound (A-1) was obtained in the same manner as in Example 1D, except that 1.05 g of 3-ethyl-3-hydroxymethyloxetane was added.

[0298] Example 7D A composition (PCP-12D) containing compound (A-1) was obtained in the same manner as in Example 1D, except that 1.20 g of 3-ethyl-3-hydroxymethyloxetane was added.

[0299] Example 8D A composition (PCP-13D) containing compound (A-1) was obtained in the same manner as in Example 1D, except that 8.00 g of 3-ethyl-3-hydroxymethyloxetane was added.

[0300] Example 9D A composition (PCP-14D) containing compound (A-1) was obtained in the same manner as in Example 1D, except that 10.00 g of 3-ethyl-3-hydroxymethyloxetane was added.

[0301] (Comparative example 2D) A composition (PCP-15D) containing the compound (A-1) was obtained in the same manner as in Example 1D, except that the amount of 3-ethyl-3-hydroxymethyloxetane was 0.19 g.

[0302] (Analysis and Evaluation) In the same manner as in Example 1, the number average molecular weight and hydroxyl value of the composition obtained above were measured, and property evaluation, calculation of the assumed average number of hydroxyl functional groups, and composition analysis were performed. In the composition analysis, signals from 4.390 ppm to 4.500 ppm were designated as signals (SC), signals from 3.618 ppm to 3.720 ppm were designated as signals (SD), signals from 3.550 ppm to 3.618 ppm were designated as signals (SE), and signals from 0.700 ppm to 1.130 ppm were designated as signals R of the groups represented by formula (I) and formula (C). 2 is a methyl group (when the polyhydric alcohol (e) is trimethylolethane), and the signals between 0.700 ppm and 1.000 ppm are R 2 is the signal (SI) when the polyhydric alcohol (e) is trimethylolpropane. The results are shown in Table 14.

[0303] [Table 14]

[0304] In Table 14, the "composition" (unit: g) of Examples 1D to 9D and Comparative Examples 1D to 6D indicates the reaction raw materials.

[0305] (Physical property evaluation) A urethane cured coating (film) was obtained in the same manner as in Example 1, except that the composition obtained above, a polyisocyanate component (C-2612), a urethane catalyst, a phosphoric ester (JP508), and a dilution solvent were mixed in the proportions (unit: g) shown in Table 15. The obtained film was then used as a sample to evaluate the physical properties (tensile properties, texture properties, low temperature properties) in the same manner as in Example 1. The results are shown in Table 15.

[0306] [Evaluation Criteria] The physical properties of 100% modulus, breaking strength, breaking elongation, softening temperature, and glass transition temperature were evaluated as A, B, C, and D (A: very good, B: good, C: fair, D: poor). <100% modulus> A: 2.0MPa or less B: Over 2.0MPa <Breaking strength> A: Over 16MPa B: 16MPa or less 15MPa or more D: Less than 15MPa <Elongation at break> A: 400% or more B: Less than 400% <Softening temperature> A: 250℃ or higher B: Less than 250℃ <Glass transition temperature> A: -2℃ or less B: Over -2℃

[0307] [Table 15]

[0308] (Handling evaluation) The handleability (isocyanate group-terminated urethane prepolymer viscosity) was evaluated in the same manner as in Example 1, except that the composition obtained above, N-980N, 1,6-hexanediol, 2,2-dimethylolpropanoic acid (hydrophilizing agent), isophorone diisocyanate (polyisocyanate), and methyl ethyl ketone (organic solvent) were charged in the amounts (unit: g) shown in Table 16. The results are shown in Table 16.

[0309] [Evaluation Criteria] The viscosity of the isocyanate-terminated urethane prepolymer was evaluated on a scale of A, B, C, and D (A: very good, B: good, C: fair, D: poor). <Viscosity> A: 2600mPa・s or less D: Over 2600mPa·s

[0310] [Table 16]

[0311] The compositions were overall evaluated on a scale of A, B, C, and D (A: very good, B: good, C: average, D: poor). The results are shown in Table 17. <Overall rating> A: Only A ratings for each physical property and handling property B: The evaluation of each physical property and handling property does not include D, and includes one B or C. C: The evaluation of each physical property and handling property does not include D, and includes two or more B or C. D: Each physical property and handling evaluation includes D

[0312] [Table 17]

[0313] Details of the materials used in the fourth example are as follows: Plaxel 305: Polycaprolactone triol (number average molecular weight = 550, hydroxyl value = 305, functionality = 3) manufactured by Daicel Corporation 3-Ethyl-3-hydroxymethyloxetane: manufactured by Tokyo Chemical Industry Co., Ltd. Lithium acetylacetonate: Sigma-Aldrich Potassium bicarbonate: Fujifilm Wako Pure Chemical Industries, Ltd. C-2612: Coronate 2612 (trade name), hexamethylene diisocyanate adduct modified polyisocyanate, isocyanate content = 17.2%, manufactured by Tosoh Corporation JP-508: Product name, 2-ethylhexyl acid phosphate, manufactured by Johoku Chemical Industry Co., Ltd. DOTDL: Dioctyltin dilaurate, manufactured by Kishida Chemical Industry Co., Ltd. Methyl ethyl ketone: Maruzen Petrochemical Co., Ltd. Toluene: Fujifilm Wako Pure Chemical Industries, Ltd. BYK-331: Silicone surface conditioner, manufactured by BYK 2,2-Dimethylolpropionic acid: Tokyo Chemical Industry Co., Ltd. Isophorone diisocyanate: Evonik

Claims

1. A composition comprising a compound (A-1) including a repeating unit (A) represented by the following formula (A), a structural unit (I) derived from a polyhydric alcohol represented by the following formula (I), a structure (C) derived from an oxetane compound represented by the following formula (C), and a terminal hydroxyl group, A composition, wherein the content of structure (C) derived from an oxetane compound represented by formula (C) contained in the composition is 0.90 to 9.5 mol % based on the total content of structure (C) derived from the oxetane compound, structure (D) derived from a diol represented by formula (D) below, and structure (E) derived from a polyhydric alcohol represented by formula (E) below, which are contained in the composition: 【Chemistry 1】 [In formula (A), R １ is an alkanediyl group, *1-O-R ａ -*2, or *1-R ｂ -C(=O)-OR ｃ -*2, R 1 includes *1-O-R a -*2 and an alkanediyl group and / or *1-R b -C(═O)-O-R c -*2; R ａ , R ｂ , and R ｃ each independently represents an alkanediyl group, *1 represents a bonding site with a carbonyl group, and *2 represents a bonding site with an oxygen atom. 【Chemistry 2】 [In formula (I), R ２ represents a hydrogen atom, an alkyl group or a hydroxyalkyl group, and * represents a bond. 【Chemistry 3】 [In formula (C), R ２ has the same meaning as above, and * indicates a bond. 【Chemistry 4】 [In formula (D), R ３ is a hydrogen atom or an alkyl group, and * indicates a bond. ３ may be the same or different. 【Chemistry 5】 [In formula (E), R ２ has the same meaning as above, and * indicates a bond.

2. The present invention includes a compound (A-1) including a repeating unit (A) represented by the following formula (A) and a structural unit (I) derived from a polyhydric alcohol represented by the following formula (I), A composition, wherein the content of structure (C) derived from an oxetane compound represented by the following formula (C) is 2.80 to 28 mol % based on the total of structural unit (I) derived from a polyhydric alcohol represented by the following formula (I) and structure (C) derived from the oxetane compound. 【Chemistry 6】 [In formula (A), R １ is an alkanediyl group, *1-O-R ａ -*2, or *1-R ｂ -C(=O)-OR ｃ -*2, R 1 includes *1-O-R a -*2 and an alkanediyl group and / or *1-R b -C(═O)-O-R c -*2; R ａ , R ｂ , and R ｃ each independently represents an alkanediyl group, *1 represents a bonding site with a carbonyl group, and *2 represents a bonding site with an oxygen atom. 【Chemistry 7】 [In formula (I), R ２ represents a hydrogen atom, an alkyl group or a hydroxyalkyl group, and * represents a bond. 【Chemistry 8】 [In formula (C), R ２ has the same meaning as above, and * indicates a bond.

3. The composition according to claim 1, wherein the content of the structure (C) derived from the oxetane compound is 2.80 to 28 mol % based on the total of the structural unit (I) derived from the polyhydric alcohol and the structure (C) derived from the oxetane compound.

4. R ａ The composition according to any one of claims 1 to 3, wherein all of are linear alkanediyl groups.

5. R ａ The composition according to any one of claims 1 to 3, wherein at least one of the following is a branched alkanediyl group.

6. R ａ The composition according to any one of claims 1 to 3, comprising two or more alkanediyl groups as the alkyl group.

7. R １ is *1-O-R ａ The composition according to any one of claims 1 to 3, comprising -*2 and an alkanediyl group.

8. The composition according to any one of claims 1 to 3, further comprising a diol (d) represented by the following formula (d), a polyhydric alcohol (e) represented by the following formula (e), and an oxetane compound (F) represented by the following formula (f). 【Chemistry 9】 [In formula (d), R ａ has the same meaning as above.] 【Chemistry 10】 [In formula (e), R ２ has the same meaning as above.] 【Chemistry 11】 [In formula (f), R ２ has the same meaning as above.]

9. The composition according to any one of claims 1 to 3, further comprising a compound (A-2) represented by the following formula (A-2), a compound (A-3) represented by the following formula (A-3), and a compound (A-4) represented by the following formula (A-4): 【Chemistry 12】 [In formula (A-2), R １ is as defined above, and n ２ represents an integer of 1 or more. １ may be the same or different. 【Chemistry 13】 [In formula (A-3), R １ and R ２ is as defined above, and n ３ represents an integer of 1 or more. １ may be the same or different. 【Chemistry 14】 [In formula (A-4), R １ and R ２ is as defined above, and n ４ represents an integer of 1 or more. ２ may be the same or different. １ When there are a plurality of, they may be the same or different.

10. The composition according to any one of claims 1 to 3, further comprising lithium acetylacetonate.

11. A method for producing the composition according to any one of claims 1 to 3, comprising the steps of: A method for producing a composition, comprising: heating a mixed liquid containing a polyhydric alcohol (B1), a diol (D1), a carbonate ester, and an ester exchange catalyst to perform a reflux reaction while removing an alcohol derived from the carbonate ester from the reaction system, thereby obtaining the composition.

12. A method for producing the composition according to any one of claims 1 to 3, comprising the steps of: a reaction step of reacting the polycarbonate polyol (B2) with the polyester polyol (C2) in a mixed liquid containing the polycarbonate polyol (B2), a polyester polyol (C2), and a transesterification catalyst to obtain the compound (A-1), the polycarbonate polyol (B2) and / or the polyester polyol (C2) contains a group represented by the following formula (I), or the mixed liquid further contains a polyhydric alcohol (E2): 【Chemistry 15】 [In formula (I), R ２ has the same meaning as above, and * indicates a bond.

13. The production method according to claim 11, wherein the content of the transesterification catalyst in the mixed solution is 0.001 to 0.050 parts by mass relative to 100 parts by mass of the total amount of the polyhydric alcohol (B1), the diol (D1), and the carbonate ester in the mixed solution.

14. The content of the transesterification catalyst in the mixed solution is 0.001 to 0.050 parts by mass per 100 parts by mass of the total amount of the polycarbonate polyol (B2) and the polyester polyol (C2). The production method according to claim 12.

15. The process of claim 12, wherein the transesterification catalyst comprises lithium acetylacetonate.

16. A polycondensate of a polyol component and a polyisocyanate component or a crosslinked product thereof, A urethane resin, wherein the polyol component comprises the composition according to any one of claims 1 to 3.

17. The urethane resin according to claim 16 , wherein the polyol component further comprises a polyol having an acidic group.

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

19. A coating agent comprising the urethane resin according to claim 16.

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