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

Abstract

The present invention relates to a composition comprising a compound (A-1) comprising a repeating unit (A) having a specific structure and a structural unit (I) derived from a polyol having a specific structure. The content of the oxetane compound-derived structure (C) having a specific structure contained in the composition is 0.90-10.7 mol% relative to the total of the oxetane compound-derived structure (C), the diol-derived structure (D) having a specific structure, and the polyol-derived structure (E) having a specific structure.

Description

Technical Field

[0001] This disclosure relates to compositions and methods of manufacturing thereof, polyurethane resins, aqueous polyurethane resin dispersions, and coating agents. Background Technology

[0002] Like polyester polyols and polyether polyols, polycarbonate polyols can be used as raw materials to react with polyisocyanate compounds to produce polyurethane resins (also known as polyurethane resins), and can also be used as raw materials for adhesives, coatings, etc.

[0003] Because polyester polyols contain ester bonds, polyurethane resins derived from them suffer from poor hydrolysis resistance. Similarly, because polyether polyols contain ether bonds, polyurethane resins derived from them exhibit poor weather resistance and heat resistance. In contrast, polyurethane resins derived from polycarbonate polyols tend to exhibit superior durability (heat resistance, weather resistance, hydrolysis resistance, chemical resistance, etc.).

[0004] Polycarbonate polyols are typically produced by reacting carbonates with diols in the presence of an ester exchange catalyst (ester exchange reaction).

[0005] To date, polycarbonate polyols with various structures have been proposed for different purposes. For example, in Patent Documents 1 and 2, a polycarbonate polyol obtained by transesterification reaction of polycarbonate diol with triol and / or tetraol compounds has been proposed.

[0006] Existing technical documents

[0007] Patent documents

[0008] Patent Document 1: Japanese Patent Application Publication No. 3-220233

[0009] Patent Document 2: Japanese Patent Application Publication No. 2012-184380 Summary of the Invention

[0010] The problem the invention aims to solve

[0011] However, while the polycarbonate polyols in Patent Documents 1 and 2 exhibit good mechanical properties when used as raw materials for polyurethane resins, their operability is insufficient.

[0012] Therefore, one objective of this disclosure is to provide a composition that facilitates the formation of a polyurethane resin with high tensile strength and good workability, and a method for manufacturing the same. Another objective of this disclosure is to provide a polyurethane resin with high tensile strength, an aqueous polyurethane resin dispersion using the polyurethane resin, and a coating agent.

[0013] Solution for solving the problem

[0014] This disclosure provides the following methods.

[0015] [1] A composition comprising a compound (A-1), said compound (A-1) comprising a repeating unit (A) of formula (A), a structural unit (I) derived from a polyol of formula (I), a structure (C) derived from an oxetane compound of formula (C), and a terminal hydroxyl group, wherein the content of the structure (C) derived from an oxetane compound of formula (C) in the composition is 0.90 to 10.7 mol% relative to the sum of the structure (C) derived from an oxetane compound of formula (C), the structure (D) derived from a diol of formula (D), and the structure (E) derived from a polyol of formula (E) in the composition.

[0016]

[0017] In formula (A), R 1 Indicates alkanediyl group, *1-OR a -*2 or *1-R b -C(=O)-OR c -*2, R a R b and R c Each alkyl group is represented independently; *1 indicates the bonding site with the carbonyl group, and *2 indicates the bonding site with the oxygen atom.

[0018]

[0019] In formula (I), R 2 [The atoms are hydrogen atoms, alkyl groups, or hydroxyalkyl groups; * indicates a connecting bond]

[0020]

[0021] In formula (C), R 2 Synonymous with the above, * indicates a connector.

[0022]

[0023] In formula (D), R 3 It is a hydrogen atom or an alkyl group, * indicates a connecting bond, R 3 [Choose either the same or different from each other]

[0024]

[0025] In formula (E), R 2 Synonymous with the above, * indicates a connector.

[0026] [2] A composition comprising compound (A-1), said compound (A-1) comprising a repeating unit (A) of formula (A) and a structural unit (I) derived from a polyol of formula (I), wherein the content of the structure (C) derived from an oxetane compound of formula (C) is 2.80 to 28 mol% relative to the sum of the structural unit (I) derived from the polyol of formula (I) and the structure (C) derived from the oxetane compound.

[0027]

[0028] In formula (A), R 1 Indicates alkyldiyl, *1-OR a -*2 or *1-R b -C(=O)-OR c -*2, R a R b and R c Each alkyl group is represented independently; *1 indicates the bonding site with the carbonyl group, and *2 indicates the bonding site with the oxygen atom.

[0029]

[0030] In formula (I), R 2 [The atoms are hydrogen atoms, alkyl groups, or hydroxyalkyl groups; * indicates a connecting bond]

[0031]

[0032] In formula (C), R 2 Synonymous with the above, * indicates a connector.

[0033] [3] According to the composition described in [1], the content of the structure (C) derived from the oxetane compound is 2.80 to 28 mol% relative to the sum of the structural unit (I) derived from the polyol and the structure (C) derived from the oxetane compound.

[0034] [4] The composition according to any one of [1] to [3], wherein R 1 For *1-OR a -*2, R a All are straight-chain alkyl dimethyl groups.

[0035] [5] The composition according to any one of [1] to [3], wherein R 1 For *1-OR a -*2, R a At least one of them is a branched alkyl diester.

[0036] [6] The composition according to any one of [1] to [4], wherein R 1 For *1-OR a -*2, and contains two or more alkyl dienes as R a .

[0037] [7] The composition according to any one of [1] to [3], wherein R 1 Includes *1-OR a -*2, and contains alkyldiyl and / or *1-R b -C(=O)-OR c -*2.

[0038] [8] The composition according to any one of [1] to [3], wherein R 1 Includes *1-OR a -*2 and alkyldiyl groups.

[0039] [9] The composition according to any one of [1] to [8] further comprises a diol (d) of formula (d), a polyol (e) of formula (e), and an oxetane compound (F) of formula (f).

[0040] HO-R a -OH (d)

[0041] In formula (d), R a [Synonymous with the above]

[0042]

[0043] In equation (e), R 2 [Synonymous with the above]

[0044]

[0045] In equation (f), R 2 (Synonymous with the above).

[0046]

[10] The composition according to any one of [1] to [9] further comprises compound (A-2) of formula (A-2), compound (A-3) of formula (A-3), and compound (A-4) of formula (A-4).

[0047]

[0048] In formula (A-2), R 1 Synonymous with the above, n 2 R represents an integer greater than or equal to 1, and multiple existing R values. 1 [Choose either the same or different from each other]

[0049]

[0050] In formula (A-3), R 1 and R 2 Synonymous with the above, n 3 R represents an integer greater than or equal to 1, and multiple existing R values. 1 [Choose either the same or different from each other]

[0051]

[0052] In formula (A-4), R 1 and R 2 Synonymous with the above, n 4 R represents an integer greater than or equal to 1, and multiple existing R values. 2 Choose either the same or different from each other, R 1 In the case of multiple instances, they can be chosen to be the same or different from each other.

[0053]

[11] The composition according to any one of [1] to [3] further contains lithium acetylacetone.

[0054]

[12] A method for manufacturing a composition, which is a method for manufacturing any one of [1] to

[11] , comprising the following steps: heating a mixture containing a polyol (B1), a diol (D1), a carbonate and a transesterification catalyst, removing alcohols derived from the carbonate from the reaction system while performing a reflux reaction to obtain the composition.

[0055]

[13] A method for manufacturing a composition, which is a method for manufacturing the composition described in any one of [1] to

[12] , comprising the following reaction step: reacting the polycarbonate polyol (B2) with the polyester polyol (C2) in a mixture comprising a polycarbonate polyol (B2), a polyester polyol (C2), and a transesterification catalyst to obtain the compound (A-1), wherein at least one of the polycarbonate polyol (B2) and the polyester polyol (C2) comprises a group represented by the following formula (I), or the mixture further comprises a polyol (E2).

[0056]

[0057] In formula (I), R 2 Synonymous with the above, * indicates a connector.

[0058]

[14] According to the manufacturing method described in

[12] or

[13] , the content of the transesterification catalyst in the mixture is 0.001 to 0.050 parts by mass relative to the total amount of the polyol (B1), diol (D1) and carbonate in the mixture in 100 parts by mass.

[0059]

[15] The manufacturing method according to any one of

[12] to

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

[0060]

[16] The manufacturing method according to any one of

[12] to

[15] , wherein the transesterification catalyst comprises lithium acetylacetone.

[0061]

[17] A polyurethane resin, which is a condensation polymer or crosslinking of a polyol component and a polyisocyanate component, wherein the polyol component comprises any one of the compositions described in [1] to

[11] .

[0062]

[18] The polyurethane resin according to

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

[0063]

[19] An aqueous polyurethane resin dispersion comprising: an aqueous medium; and the polyurethane resin or its neutralization thereof dispersed in the aqueous medium as described in

[18] .

[0064]

[20] A coating agent comprising the polyurethane resin described in

[17] or

[18] .

[0065] The effects of the invention

[0066] According to one aspect of this disclosure, a composition and a method thereof that facilitate the formation of a polyurethane resin with high tensile strength and good workability can be provided. According to another aspect of this disclosure, a polyurethane resin with high tensile strength, an aqueous polyurethane resin dispersion using the polyurethane resin, and a coating agent can also be provided. Attached Figure Description

[0067] Figure 1 The composition containing polycarbonate polyol obtained in Example 1B 1 H-NMR spectrum.

[0068] Figure 2 The composition containing polycarbonate polyol obtained in Example 1C 1 H-NMR spectrum. Detailed Implementation

[0069] The embodiments of the various methods disclosed herein will be described in detail below. It should be noted that in this specification, the numerical range indicated by "~" represents a range that includes the values ​​before and after "~" as a minimum and maximum value, respectively. The minimum or maximum value of the numerical range indicated by "~" can be arbitrarily combined with the maximum or minimum value of other numerical ranges indicated by "~". Furthermore, the individually stated upper and lower limits can also be arbitrarily combined.

[0070] The compositions disclosed herein comprise compound (A-1), said compound (A-1) comprising a repeating unit (A) represented by the following formula (A) and a structural unit (I) derived from a polyol represented by the following formula (I).

[0071]

[0072] In formula (A), R 1 Indicates alkyldiyl, *1-OR a -*2 or *1-R b -C(=O)-OR c -*2, R a R b and R c Each alkyl group is represented independently; *1 indicates the bonding site with the carbonyl group, and *2 indicates the bonding site with the oxygen atom.

[0073]

[0074] In formula (I), R 2 [This represents a hydrogen atom, alkyl group, or hydroxyalkyl group; * indicates a linking bond.]

[0075] The composition of the first method is a composition in which the content of the structure (C) derived from the oxetane compound shown in the following formula (C) is 2.80 to 28 mol% relative to the sum of the structural unit (I) derived from the polyol and the structure (C) derived from the oxetane compound.

[0076]

[0077] In formula (C), R 2 Synonymous with the above, * indicates a connector.

[0078] The composition of the second aspect of the present invention is a composition in which the content of the structure (C) derived from the oxetane compound is 0.90 to 10.7 mol% relative to the sum of the structure (C) derived from the oxetane compound, the structure (D) derived from the diol shown in formula (D) below, and the structure (E) derived from the polyol shown in formula (E) below.

[0079]

[0080] In formula (D), R 3 It represents a hydrogen atom or an alkyl group; * indicates a linking bond. R 3 Choose either the same as or different from each other.

[0081]

[0082] In formula (E), R 2 Synonymous with the above, * indicates a connector.

[0083] <Compound (A-1)>

[0084] Compound (A-1) may comprise: a compound comprising the repeating unit (A) described above, the structural unit (I) derived from a polyol described above, the structure (C) derived from an oxetane compound described above, and a terminal hydroxyl group. Compound (A-1) may also comprise: a compound comprising the repeating unit (A) described above, the structure (C) derived from an oxetane compound described above, the structure (D) derived from a diol described above, and the structure (E) derived from a polyol described above.

[0085] R 1 The alkyl dienes shown can be straight-chain or branched. In R 1 When there are two or more types of alkyl dienes shown, they can all be straight-chain alkyl dienes or branched alkyl dienes, or some can be straight-chain alkyl dienes and the rest can be branched alkyl dienes.

[0086] By R 1 The number of carbon atoms in the alkyldiyl group can be, for example, 2 to 10. Specific examples of alkyldiyl groups include ethylenediyl, 1,2-propanediyl, 1,3-propanediyl, 1,2-butanediyl, 1,3-butanediyl, 1,4-butanediyl, 1,5-pentanediyl, 2,2-dimethyl-1,3-propanediyl, 1,6-hexanediyl, 3-methyl-1,5-pentanediyl, 1,8-octanediyl, 2-ethyl-1,6-hexanediyl, 1,9-nonadiyl, 2-methyloctane-1,8-diyl, 2-butyl-2-ethyl-1,3-propanediyl, etc. Among them, 1,4-butadiyl, 1,5-pentadiyl, 1,6-hexadiyl, 3-methyl-1,5-pentadiyl, 2-ethyl-1,6-hexadiyl, 1,9-nonadiyl, 2-methyloctane-1,8-diyl, etc. are preferred.

[0087] R a R b and R c The alkyl diene shown may be the same as the alkyl diene described above. R a R b and R c The number of carbon atoms in the alkyl diene shown can be, for example, 2 to 10. In R aWhen two or more alkyl dienes are present, they can all be straight-chain or branched-chain alkyl dienes, or a portion can be straight-chain alkyl dienes and the rest branched-chain alkyl dienes. In R b When two or more alkyl dienes are present, they can all be straight-chain or branched-chain alkyl dienes, or a portion can be straight-chain alkyl dienes and the rest branched-chain alkyl dienes. In R c When there are two or more types of alkyl dienes shown, they can all be straight-chain alkyl dienes or branched alkyl dienes, or some can be straight-chain alkyl dienes and the rest can be branched alkyl dienes.

[0088] Polycarbonate polyols containing two or more alkyl groups as R 1 R a R b Or R c In this case, it can be entirely composed of straight-chain alkyldiyl or branched-chain alkyldiyl, or part of it can be straight-chain alkyldiyl and the rest can be branched-chain alkyldiyl.

[0089] R 2 The alkyl and hydroxyalkyl groups shown can be straight-chain or branched. The number of carbon atoms in the alkyl and hydroxyalkyl groups can be, for example, 1–6, 2–5, or 3–4. Specific examples of alkyl and hydroxyalkyl groups include methyl, ethyl, propyl, isopropyl, butyl, pentyl, hexyl, hydroxymethyl, hydroxyethyl, hydroxypropyl, and hydroxybutyl. 2 Preferably, it is an alkyl or hydroxyalkyl group, and more preferably an alkyl or hydroxyalkyl group having 1 to 2 carbon atoms.

[0090] The number-average molecular weight of compound (A-1) can be, for example, 200–6000 g / mol. Here, the number-average molecular weight is the converted number-average molecular weight of a difunctional polyoxypropylene polyol as determined by GPC (Gel Permeation Chromatography).

[0091] The hydroxyl value of compound (A-1) can be, for example, 30–800 mg KOH / g. Here, the hydroxyl value refers to the number of milligrams (mg) of potassium hydroxide equivalent to the hydroxyl content in 1 g of compound (A-1), determined according to JIS K1557-1.

[0092] The following describes compound (A-1) in more detail through multiple embodiments (Embodiments 1 to 4).

[0093] (First Embodiment)

[0094] In the first embodiment, compound (A-1) contains only straight-chain alkyl dienes as R. 1 That is, R 1All are straight-chain alkyl dienes. Because compound (A-1) contains only straight-chain alkyl dienes as R... 1 Therefore, it easily becomes a solid at 25℃.

[0095] In the first embodiment, compound (A-1) preferably contains only one straight-chain alkyl diene as R. 1 Under these conditions, the tendency of compound (A-1) to become a solid at 25°C is increased.

[0096] The linear alkyl dienoyl group preferably has 2 to 10 carbon atoms, more preferably 2 to 9, and even more preferably 4 to 8. Preferred examples of linear alkyl dienoyl groups are 1,4-butadiyl, 1,5-pentadiyl, 1,6-hexadiyl, and 1,9-nonadiyl.

[0097] The number-average molecular weight of the compound (A-1) in the first embodiment is preferably 200 g / mol to 6000 g / mol, or it may be 300 g / mol to 5000 g / mol or 500 g / mol to 4000 g / mol.

[0098] The hydroxyl value of the compound (A-1) in the first embodiment is preferably 30 to 800 mg KOH / g, but may also be 40 to 700 mg KOH / g or 50 to 600 mg KOH / g.

[0099] (Second Implementation)

[0100] In the second embodiment, compound (A-1) contains two or more alkyl dienes as R. 1 Because compound (A-1) contains more than two alkyl dienes as R... 1 Therefore, it easily becomes a liquid at 25℃.

[0101] In the second embodiment, when used as a raw material for polyurethane resin, from the viewpoint of easily forming a polyurethane resin with good tensile strength, elongation, hand feel, and excellent durability, compound (A-1) preferably contains only a straight-chain alkyl diene as R. 1 A preferred example of a combination of alkyldiols is a combination of two or more alkyldiols having 2 to 10 carbon atoms. A more preferred combination of alkyldiols is a combination of 1,6-hexanediol with at least one selected from the group consisting of 1,4-butanediol, 1,5-pentanediol and 1,9-nonanediol.

[0102] In the second embodiment, when used as a raw material for polyurethane resin, from the viewpoint of easily forming a polyurethane resin with good tensile strength, elongation, hand feel, and excellent durability, the molar number of 1,6-hexamethylenediol relative to that of R in compound (A-1) is... 1The ratio of the total number of moles of alkyl diols contained 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).

[0103] The number-average molecular weight of the compound (A-1) in the second embodiment is preferably 200 g / mol to 6000 g / mol, but may also be 300 g / mol to 5000 g / mol or 500 g / mol to 4000 g / mol.

[0104] The hydroxyl value of the compound (A-1) in the second embodiment is preferably 30 to 800 mg KOH / g, but may also be 40 to 700 mg KOH / g or 50 to 600 mg KOH / g.

[0105] (Third Implementation)

[0106] In the third embodiment, compound (A-1) comprises a branched alkyl diene as R. 1 The compound (A-1) of the third embodiment contains a branched alkyl diyl group as R. 1 Therefore, it easily becomes a liquid at 25℃.

[0107] In the third embodiment, compound (A-1) may contain two or more alkyl dienes as R. 1 When two or more alkyl groups can all be branched alkyl groups, and when used as a raw material for polyurethane resin, from the viewpoint of easily forming a polyurethane resin with excellent workability, good elongation and feel, and excellent durability, it is preferable that some of the two or more alkyl groups are straight-chain alkyl groups. In this case, the molar number of branched alkyl groups relative to the number of alkyl groups used as R in compound (A-1) 1 The ratio of the total number of moles of alkyl diols contained therein is preferably 0.10 to 1.00, more preferably 0.20 to 0.90, even more preferably 0.30 to 0.70, and even more preferably 0.40 to 0.60.

[0108] The branched alkyl dienylate preferably has 2 to 10 carbon atoms, more preferably 3 to 9, and even more preferably 4 to 8. The main chain (the straight chain with the most carbon atoms) of the branched alkyl dienylate preferably has 2 to 9 carbon atoms, more preferably 3 to 8, and even more preferably 4 to 7. Preferred examples of branched alkyl dienylates are 3-methylpentane-1,5-diyl and 2-methyl-1,8-octadiyl.

[0109] The linear alkyl dienoyl group preferably has 2 to 10 carbon atoms, more preferably 3 to 9, and even more preferably 4 to 8. Preferred examples of linear alkyl dienoyl groups are 1,4-butadiyl, 1,5-pentadiyl, 1,6-hexadiyl, and 1,9-nonadiyl.

[0110] In the third embodiment, when used as a raw material for polyurethane resin, from the viewpoint of easily forming a polyurethane resin with excellent workability, good elongation and hand feel, and excellent durability, the molar number of 1,6-hexamethylenediol relative to that of R in compound (A-1) is... 1 The ratio of the total number of moles of alkyl diols contained 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), even more 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).

[0111] The number-average molecular weight of the compound (A-1) in the third embodiment is preferably 200 g / mol to 6000 g / mol, but may also be 300 g / mol to 5000 g / mol or 500 g / mol to 4000 g / mol.

[0112] The hydroxyl value of the compound (A-1) in the third embodiment is preferably 30 to 800 mg KOH / g, but may also be 40 to 700 mg KOH / g or 50 to 600 mg KOH / g.

[0113] (Fourth implementation)

[0114] In the fourth embodiment, compound (A-1) comprises *1-OR a -*2, and contains alkyldiyl and / or *1-R b -C(=O)-OR c -*2 as R 1 Because the compound (A-1) of the fourth embodiment contains *1-OR a -*2, and contains alkyldiyl and / or *1-R b -C(=O)-OR c -*2 as R 1 Therefore, it easily becomes a liquid at 25℃.

[0115] In the fourth embodiment, the properties of compound (A-1) are not particularly limited; it may be a solid or a liquid at 25°C. The properties of compound (A-1) can be determined based on the properties of R in compound (A-1). 1 R a R b or R c The composition of the alkyl diols varies (number of carbons, presence or absence of branches, etc.) and the hydroxyl value of the compound (A-1). For example, relative to the R group in compound (A-1)... 1 R a R b or R cWhen the total number of moles of alkyl dienes contained in compound (A-1) is 0.2 to 1.0, and when the hydroxyl value of compound (A-1) is high, compound (A-1) readily becomes liquid at 25°C.

[0116] In the fourth embodiment, when used as a raw material for polyurethane resin, from the viewpoint of easily forming a polyurethane resin with excellent durability such as heat resistance or resistance to damp heat / hot water, the compound (A-1) containing R is preferred. 1 It is an alkyldiyl and *1-OR a -*2.

[0117] Furthermore, in the fourth embodiment, when used as a raw material for polyurethane resin, from the viewpoint of easily forming a polyurethane resin with 100% modulus and excellent heat resistance, compound (A-1) is used as R. 1 Includes *1-OR a -*2 moles relative to R 1 Contains alkyldiyl, *1-OR a -*2 and *1-R b -C(=O)-OR c The total number of moles of -*2 is preferably 0.10 or more (e.g., 0.10 to 0.90), more preferably 0.20 or more (e.g., 0.20 to 0.80), even more preferably 0.30 or more (e.g., 0.30 to 0.70), and especially preferably 0.40 or more (e.g., 0.40 to 0.60).

[0118] The number-average molecular weight of the compound (A-1) in the fourth embodiment is preferably 200 g / mol to 6000 g / mol, but may also be 300 g / mol to 5000 g / mol or 500 g / mol to 4000 g / mol.

[0119] The hydroxyl value of the compound (A-1) in the fourth embodiment is preferably 30 to 800 mg KOH / g, but may also be 40 to 700 mg KOH / g or 50 to 600 mg KOH / g.

[0120] <Ingredients>

[0121] The polycarbonate polyol (compound (A-1)) described in embodiments 1 to 3 may be, for example, a reaction product of a polyol (hereinafter also referred to as "polyol (B1)") represented by formula (b), a diol (hereinafter also referred to as "diol (D1)") represented by formula (d), and a carbonate; or it may be a reaction product of a polyol (B1), a diol (D1), a carbonate, and an oxetane compound (hereinafter also referred to as "oxetane compound (F1)") represented by formula (f).

[0122]

[0123] In formula (b), R 2 It can be a hydrogen atom, an alkyl group, or a hydroxyalkyl group.

[0124] HO-R a -OH (d)

[0125] In formula (d), R a Synonymous with the above.

[0126]

[0127] In equation (f), R 2 Synonymous with the above.

[0128] Specific examples of polyols (B1) include trimethylolpropane, trimethylolethane, glycerol, and pentaerythritol. They can be used alone or in combination of two or more.

[0129] Specific examples of diols (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. They can be used alone or in combination of two or more.

[0130] Examples of carbonates include dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, dipropyl carbonate, dibutyl carbonate, diphenyl carbonate, ethylene carbonate, trimethylene carbonate, and 1,2-propylene carbonate. These can be used alone or in combination. From the viewpoint of ease of acquisition 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.

[0131] Examples of oxetane compounds (F1) include 3-ethyl-3-hydroxymethyloxetane, 3-methyl-3-hydroxymethyloxetane, and 3,3-dihydroxymethyloxetane. They can be used alone or in combination of two or more.

[0132] The compound (A-1) described in the fourth embodiment may, for example, be a reaction product of polycarbonate polyol (B2) and polyester polyol (C2). Alternatively, compound (A-1) may be a reaction product of polycarbonate polyol (B2), polyester polyol (C2), and oxetane compound (F2). Furthermore, compound (A-1) may also be a reaction product of polycarbonate polyol (B2), polyester polyol (C2), diol (D2), and / or polyol (E2). Additionally, compound (A-1) may also be a reaction product of polycarbonate polyol (B2), polyester polyol (C2), oxetane compound (F2), and diol (D2) and / or polyol (E2).

[0133] The polycarbonate polyol (B2) can be any polycarbonate polyol with 2 or more hydroxyl functional groups. It can be a polycarbonate polyol (B2-1) with 2 hydroxyl functional groups (i.e., polycarbonate diol), a polycarbonate polyol (B2-2) with more than 2 hydroxyl functional groups, or a combination of two or more polycarbonate polyols (B2-1) and polycarbonate polyol (B2-2).

[0134] As a polycarbonate polyol (B2-1), examples include those obtained by reacting carbonate with diol.

[0135] As the carbonate and diol that can be used in the reaction to obtain polycarbonate polyol (B2-1), examples include those that are the same as the carbonate and diol (D1) mentioned in the description of compound (A-1) of embodiments 1 to 3.

[0136] As a polycarbonate polyol (B2-2), examples include those obtained by reacting carbonate, diol and polyol with 3 or more hydroxyl functional groups.

[0137] As for the carbonate, diol, and polyol with 3 or more hydroxyl functional groups that can be used in the reaction to obtain polycarbonate polyol (B2-2), examples can be the same as those listed in the description of compound (A-1) of embodiments 1 to 3.

[0138] As a polyester polyol (C2), it can be any polyester polyol with 2 or more hydroxyl functional groups. It can be a polyester polyol with 2 hydroxyl functional groups (C2-1) (i.e., polyester diol), a polyester polyol with more than 2 hydroxyl functional groups (C2-2), or a combination of two or more polyester polyols (C2-1) and polyester polyol (C2-2).

[0139] Examples of polyester polyols (C2-1) include the following (α) to (β) polyester polyols, and any combination of two or more of them.

[0140] (α) Polyester polyols obtained by reacting a diol (C2-1-1) with a dicarboxylic acid and / or its anhydride (C2-1-2) (polyester polyol (α))

[0141] (β) Polyester polyols obtained by ring-opening addition polymerization of cyclic ester compounds (C2-1-4) such as lactones using diols (C2-1-1) as initiators (polyester polyol (β)).

[0142] Polyester polyols (β) can be referred to as ring-opening addition polymers of cyclic ester compounds initiated by diols.

[0143] As the diol (C2-1-1), examples can be the same as those described in the description of compound (A-1) of embodiments 1 to 3. 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 are preferred.

[0144] Examples of dicarboxylic acids and / or their anhydrides (C2-1-2) include, for example, 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, octanoic acid, sebacic acid, dodecanoic acid, hydrogenated dimer fatty acids, tartaric acid, their anhydrides, and any combination of two or more of them.

[0145] Examples of cyclic ester compounds (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-octyllactone, ε-octyllactone, ε-palmitolactone, and any combination of two or more thereof. From the viewpoint of stability and economy during polymerization, ring-opening addition polymers of ε-caprolactone using trimethylolpropane as an initiator are preferred.

[0146] Examples of polyester polyols (C2-2) include (α') to (β') polyester polyols and any combination of two or more of them.

[0147] (α') Polyester polyols (polyester polyols (α')) are obtained from diols (C2-2-1), dicarboxylic acids and / or their anhydrides (C2-2-2), and polyols with 3 or more hydroxyl functional groups (C2-2-3).

[0148] (β') Polyester polyols (β') are obtained by ring-opening addition polymerization of cyclic ester compounds (C2-2-4) such as lactones using polyols (C2-2-3) with 3 or more hydroxyl functional groups as initiators.

[0149] Polyester polyols (β') can be referred to as ring-opening addition polymers of cyclic ester compounds initiated by polyols with 3 or more hydroxyl functional groups.

[0150] As diols (C2-2-1) and polyols (C2-2-3) with 3 or more hydroxyl functional groups, examples can be the same as the diols (D1) and polyols (B1) mentioned in the description of compounds (A-1) of embodiments 1 to 3.

[0151] As dicarboxylic acids and / or their anhydrides (C2-2-2) and cyclic ester compounds (C2-2-4), examples can be made that are identical to those described in the description of dicarboxylic acids and / or their anhydrides (C2-1-2) and cyclic ester compounds (C2-1-4).

[0152] In the fourth embodiment, when used as a raw material for polyurethane resin, from the viewpoint of easily forming a polyurethane resin with excellent durability such as heat resistance or damp heat resistance, the polyester polyol (C2) preferably includes polyester polyol (β) and / or polyester polyol (β').

[0153] As a diol (D2), for example, the same diol (D1) as described in the description of compound (A-1) of embodiments 1 to 3 can be cited.

[0154] As a polyol (E2), for example, the same polyol (B1) mentioned in the description of the compound (A-1) of embodiments 1 to 3 can be cited.

[0155] As an oxetane compound (F2), for example, the same oxetane compound (F1) as described in the description of the compound (A-1) of embodiments 1 to 3 can be cited.

[0156] <diol(d)>

[0157] The composition may also contain a diol represented by the following formula (d) (hereinafter also referred to as "diol (d)").

[0158] HO-R a -OH (d)

[0159] In formula (d), R a Synonymous with the above.

[0160] Diol (d) is synonymous with the above, where R is used in diol (d). aThe alkyl diene it possesses can act as R in compound (A-1). a The alkyl diols contained are the same.

[0161] Diol (d) as R a The included alkyl diene can act as R in compound (A-1). a The alkyl diols contained are the same. The composition contains R a In the case of two or more compounds with different alkyl diols (A-1), the composition may contain R. a The diagram shows two or more diols (d) with different alkyl groups. In this case, among the various compounds equivalent to diol (d), R is... a The combination of included groups can be used as R in a variety of compounds equivalent to compound (A-1). a The combination of the groups contained is the same.

[0162] As a diol (d), for example, the same diol (D1) as described in the description of compound (A-1) of embodiments 1 to 3 can be cited.

[0163] <Polyols(e)>

[0164] The composition may also contain a polyol represented by the following formula (e) (hereinafter also referred to as "polyol (e)").

[0165]

[0166] In equation (e), R 2 Synonymous with the above.

[0167] Polyol (e) is synonymous with the above, where R is used in polyol (e). 2 The alkyl and / or hydroxyalkyl groups present can be used as R in compound (A-1). 2 It contains the same atoms or groups.

[0168] As R in polyols (e) 2 The contained atoms or groups can be used as R in compound (A-1). 2 The components contain the same atoms or groups. The composition contains R... 2 In the case of two or more compounds (A-1) representing different alkyl diols, the composition may contain compounds composed of R. 2 This refers to two or more polyols (e) with different alkyl diols. In this case, R is one of the various compounds corresponding to polyol (e). 2 The combination of included groups can be used as R in a variety of compounds equivalent to compound (A-1). 2 The combination of the groups contained is the same.

[0169] As a polyol (e), for example, the same polyol (B1) as described in the description of compound (A-1) in embodiments 1 to 3 can be cited.

[0170] <Oxycyclic butane compounds (F)>

[0171] The composition may also contain an oxetane compound represented by formula (f) below (hereinafter also referred to as "oxetane compound (F)").

[0172]

[0173] In equation (f), R 2 Synonymous with the above.

[0174] Oxycyclic butane compound (F) is synonymous with the above, where R is used in oxycyclic butane compound (F). 2 The alkyl and hydroxyalkyl groups present can act as R in compound (A-1). 2 It contains the same atoms or groups.

[0175] As R in oxacyclobutane compounds (F) 2 The contained atoms or groups can act as R in compound (A-1). 2 The atoms or groups contained are the same. The composition contains R 2 In the case of two or more compounds (A-1) with different alkyl diols, the composition may contain R 2 This refers to two or more oxetane compounds (F) with different alkyl dimethyl groups. In this case, R is one of the various compounds equivalent to oxetane compound (F). 2 The combination of contained groups can be used as R in a variety of compounds equivalent to compound (A-1). 2 The combination of the groups contained is the same.

[0176] As an oxetane compound (F), for example, the same oxetane compound (F1) as described in the description of compound (A-1) of embodiments 1 to 3 can be cited.

[0177] <Compound (A-2)>

[0178] The composition may also contain a polycarbonate compound represented by the following formula (A-2) (hereinafter referred to as "compound (A-2)").

[0179]

[0180] In formula (A-2), R 1 Synonymous with the above, n 2 Represents integers greater than or equal to 1. Multiple existing R... 1Choose either the same as or different from each other.

[0181] <Compound (A-3)>

[0182] The composition may also contain a polycarbonate compound represented by the following formula (A-3) (hereinafter referred to as "compound (A-3)").

[0183]

[0184] In formula (A-3), R 1 and R 2 Synonymous with the above, n 3 Represents integers greater than or equal to 1. There are multiple R's. 1 In the case of multiple existing R 1 Choose either the same as or different from each other.

[0185] <Compound (A-4)>

[0186] The composition may also contain a polycarbonate compound represented by the following formula (A-4) (hereinafter referred to as "compound (A-4)").

[0187]

[0188] In formula (A-4), R 1 and R 2 Synonymous with the above, n 4 Represents integers greater than or equal to 1. Multiple existing R... 2 Choose either the same as or different from each other. There are multiple R's. 1 In the case of R 1 Choose either the same as or different from each other.

[0189] In compounds (A-2) to (A-4), R is used as 1 The included groups can act as R in compound (A-1). 1 The compounds contain the same functional groups. Compound (A-1) contains two or more functional groups as R. 1 In the case of a group, compounds (A-2) to (A-4) may contain two or more groups as R. 1 The group. In this case, compounds (A-2) to (A-4) are represented by R. 1 Combinations containing two or more groups can act as R in compound (A-1). 1 The combination of two or more groups is the same.

[0190] In compounds (A-2) to (A-4), R is used as 2 The included groups can act as R in compound (A-1). 2The compounds contain the same functional groups. Compound (A-1) contains two or more functional groups as R. 2 In the case of a group, compounds (A-2) to (A-4) may contain two or more groups as R. 2 The group. In this case, compounds (A-2) to (A-4) are represented by R. 2 Combinations containing two or more groups can act as R in compound (A-1). 2 The combination of two or more groups is the same.

[0191] n 2 n 3 and n 4 The values ​​can be 1 to 65, 2 to 60, or 3 to 50.

[0192] The number-average molecular weight of compounds (A-2) to (A-4) is preferably 200 g / mol to 6000 g / mol, but can also be 300 g / mol to 5000 g / mol or 500 g / mol to 4000 g / mol.

[0193] The hydroxyl values ​​of compounds (A-2) to (A-4) are preferably 30 to 800 mg KOH / g, but can also be 40 to 700 mg KOH / g or 50 to 600 mg KOH / g.

[0194] The lower limit of the considered average number of hydroxyl functional groups in the composition can 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 considered average number of hydroxyl functional groups in the composition can 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 considered average number of hydroxyl functional groups in the composition can 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. If the considered average number of hydroxyl functional groups in the composition is 3.90 or less, the workability and elongation at break in the tensile test are further improved. If the considered average number of hydroxyl functional groups in the composition is 2.0 or more, the strength at break and softening temperature in the tensile test tend to be further improved.

[0195] In the following description, the sum of the total number of moles of the groups represented by formula (I) and the total number of moles of the groups represented by formula (C) in the composition is defined as C. T Let C be the total number of moles of the groups represented by the following formula (C) contained in the composition. C Let C be the total number of moles of the groups represented by the following formula (D) contained in the composition. D Let C be the total number of moles of the groups represented by the following formula (E) contained in the composition.E The content (in mol%) of structures derived from oxetane compounds relative to the sum of structural units (I) derived from polyols and structures derived from oxetane compounds (C) is expressed as "molar ratio (C)". C / C T ×100). The content (in mol%) of the structure (C) derived from oxetane compounds relative to the sum of the structures derived from oxetane compounds (C), diols (D), and polyols (E) is expressed as "molar ratio (C)". C / (C C +C D +C E )×100".

[0196]

[0197] In formula (I), R 2 Synonymous with the above, * indicates a connector.

[0198]

[0199] In formula (C), R 2 Synonymous with the above, * indicates a connector.

[0200]

[0201] In formula (D), R 3 It represents a hydrogen atom or an alkyl group; * indicates a linking bond. R 3 Choose either the same as or different from each other.

[0202]

[0203] In formula (E), R 2 Synonymous with the above, * indicates a connector.

[0204] molar ratio (C) C / C T (×100) can be 2.80~28.0. Molar ratio (C) C / (C C +C D +C E ()×100) can be 0.90~10.7. If the molar ratio (C) C / C T ×100) and molar ratio (C C / (C C +C D +C EIf the ranges are 100 and 100 respectively, then when the composition is used as a raw material for polyurethane resin, it tends to easily form a polyurethane resin that balances good workability and high tensile strength.

[0205] molar ratio (C) C / C T ×100) and molar ratio (C C / (C C +C D +C E (×100) For example, it can be based on a composition using deuterated chloroform as a solvent and tetramethylsilane as a reference substance. 1 H-NMR measurements, and the results obtained through these measurements 1 It is obtained by integrating the signal from the H-NMR spectrum. Specifically, for example, the molar ratio (C C / C T ×100) can be calculated based on equation (I) and equation (C) for R. 2 The integral value Δ of the signal (SI) of the terminal methyl group of (alkyl) SI The integral value Δ of the signal (SC) of the methylene group (3 mol parts of hydrogen atoms) and the methylene group located next to the oxygen atom of the oxobutyranyl group in formula (C) SC The molar ratio (C) is calculated based on the ratio of 4 mol of hydrogen atoms. C / (C C +C D +C E ()×100) can be calculated based on the integral value Δ of the above signal (SC). SC The integral value Δ of the signal (SD) of the methylene group next to the hydroxyl group in the group shown in formula (D) (4 mol parts of hydrogen atoms). SD The integral value Δ of the signal (SE) of the methylene group next to the hydroxyl group in the group shown in formula (E) (2 mol parts of hydrogen atoms). SE The molar ratio (C) is calculated based on the ratio of 4 mol parts of hydrogen atoms. In this case, the molar ratio (C) C / C T (×100) can also be called the integral value Δ of the signal (SI). SI The integral value Δ with respect to the signal (Sf) Sf The value of 0.75 times the ratio (0.75 × Δ) Sf / Δ SI ×100). Molar ratio (C) C / (C C +C D +C E The integral value Δ of the signal (SC) can also be called the integral value of 100. SC The integral value Δ of the signal (SD) SD The integral value Δ of the signal (SE)SE The sum and the integral value Δ of the signal (SC) SC The ratio of (Δ) SC / (Δ SC +2×Δ SD +Δ SE (×100).

[0206] The above composition will be described in more detail below through multiple embodiments (Embodiments 1 to 4).

[0207] In embodiments 1 and 2, deuterated chloroform was used as a solvent, and tetramethylsilane was used as a reference substance for the composition. 1 In the case of H-NMR measurement, for example in 1 The above signal (SC) was observed in the range of H-NMR spectra above 4.390 ppm and below 4.500 ppm. 1 The above signal (SD) was observed in the range of H-NMR spectra above 3.618 ppm and below 3.720 ppm. 1 The aforementioned signal (SE) was observed in the range of 3.590 ppm to 3.618 ppm in the H-NMR spectrum. Furthermore, in equations (I) and (C), R... 2 In the case of ethyl groups, the above-mentioned signal (SI) was observed in the range of 0.700 ppm to 1.000 ppm, and in the R of formulas (I) and (C) 2 In the case of methyl groups, the aforementioned signal (SI) was observed in the range of 0.700 ppm to 1.130 ppm. Therefore, in the first and second embodiments, the molar ratio (C) can be determined based on the ratio of the integral values ​​of these signals. C / C T ×100) and molar ratio (C C / (C C +C D +C E (×100).

[0208] In the third embodiment, deuterated chloroform is used as a solvent, and tetramethylsilane is used as a reference substance for the composition. 1 In the case of H-NMR measurement, for example, in 1 The above signal (SC) was observed in the range of H-NMR spectra above 4.390 ppm and below 4.500 ppm. 1 The above signal (SD) was observed in the range of H-NMR spectra above 3.618 ppm and below 3.720 ppm. 1The aforementioned signal (SE) was observed in the range of 3.590 ppm to 3.618 ppm in the H-NMR spectrum. Therefore, in the third embodiment, the molar ratio (C) can be determined based on the ratio of the integral values ​​of these signals. C / (C C +C D +C E (×100).

[0209] In the fourth embodiment, deuterated chloroform is used as a solvent, and tetramethylsilane is used as a reference substance for the composition. 1 In the case of H-NMR measurement, for example, in 1 The above signal (SC) was observed in the range of H-NMR spectra above 4.390 ppm and below 4.500 ppm. 1 The above signal (SD) was observed in the range of H-NMR spectra above 3.618 ppm and below 3.720 ppm. 1 The aforementioned signal (SE) was observed in the range of 3.550 ppm to 3.618 ppm in the H-NMR spectrum. Furthermore, the R values ​​in equations (I) and (C) were also observed. 2 In the case of ethyl groups, the above-mentioned signal (SI) was observed in the range of 0.700 ppm to 1.000 ppm, and in the R of formulas (I) and (C) 2 In the case of methyl groups, the aforementioned signal (SI) was observed in the range of 0.700 ppm to 1.130 ppm. Therefore, in the fourth embodiment, the molar ratio (C) can be determined based on the ratio of the integral values ​​of these signals. C / C T ×100) and molar ratio (C C / (C C +C D +C E (×100).

[0210] The molar ratio (C) in the compositions of embodiments 1 to 2 and embodiment 4 C / C T (×100) can be 2.80 or higher, 3.00 or higher, 3.20 or higher, 3.40 or higher, 3.60 or higher, 3.80 or higher, 5.00 or higher, 6.00 or higher, 7.00 or higher, 8.00 or higher, 9.00 or higher, or 10.0 or higher. If the molar ratio (C) C / C T If the molar ratio (×100) is 2.80 or higher, it tends to easily form polyurethane resins with excellent workability. C / C T×100) can be below 28.0, 26.0, 22.0, 20.0, 18.0, 16.0, 15.0, 14.0, 13.0, or 12.0. If the molar ratio (C) C / C T When the molar ratio (×100) is 28.0 or less, it tends to readily form polyurethane resins with excellent tensile strength. C / C T ×100) can be 2.0–30.0, 3.0–28.0, 3.2–26.0, 3.4–22.0, 3.8–20.0, 5.0–18.0, 6.0–16.0, 7.0–15.0, 8.0–14.0, 9.0–13.0, or 10.0–12.0. If the molar ratio (C) C / C T If the range is ×100), then when the composition is used as a raw material for polyurethane resin, it tends to easily form a polyurethane resin with good workability and tensile strength.

[0211] The molar ratio (C) of the compositions in embodiments 1 to 4 C / (C C +C D +C E ()×100) can be 0.90 or higher, 0.95 or higher, 1.00 or higher, 1.05 or higher, 1.10 or higher, 1.15 or higher, 1.20 or higher, 1.50 or higher, 1.80 or higher, 2.10 or higher, 2.40 or higher, 3.00 or higher, or 4.00 or higher. Molar ratio (C) C / (C C +C D +C E When the molar ratio (C × 100) is 0.90 or higher, it tends to easily form polyurethane resins with excellent workability. C / (C C +C D +C E ()×100) can be below 16.0, below 10.7, below 10.5, below 10.0, below 9.5, below 9.0, below 8.5, below 8.0, below 7.5, below 7.0, below 6.5, or below 6.0. If the molar ratio (C) C / (C C +C D +C E When the molar ratio (C × 100) is 16.0 or less, it tends to readily form polyurethane resins with excellent tensile strength. C / (C C +C D +C E()×100) can be 1.00~10.7, 1.05~10.5, 1.10~10.0, 1.15~9.5, 1.20~9.0, 1.30~8.0, 1.50~7.0 or 1.80~6.0. If the molar ratio (C) C / (C C +C D +C E If the range is 100 (×100), then when the composition is used as a raw material for polyurethane resin, it tends to easily form a polyurethane resin with good workability and tensile strength.

[0212] <Catalyst>

[0213] The compositions of embodiments 1 to 3 may be a reaction mixture of a polyol (B1), a diol (D1), a carbonate, and an oxetane compound (F1) added as desired. Lithium acetylacetonate is preferably used as the transesterification catalyst. The content of the transesterification catalyst, based on the total mass of the composition, may be 0.0001 to 0.100% by mass.

[0214] The composition of the fourth embodiment may be a reaction mixture of polycarbonate polyol (B2), polyester polyol (C2), and, if desired, diol (d), polyol (e), and / or oxetane compound (F2). The above reaction is typically carried out in the presence of a transesterification catalyst, therefore the composition may also contain a transesterification catalyst. Lithium acetylacetonate is preferably used as the transesterification catalyst. The content of the transesterification catalyst, based on the total mass of the composition, may be 0.0001 to 0.100% by mass.

[0215] The composition is not particularly limited in its physical properties; it may be a solid or a liquid at 25°C. The physical properties of the composition may be varied depending on the type and proportion of the components it contains (e.g., compounds (A-1) to (A-4), diols (d), polyols (e), and oxetane compounds (F)).

[0216] The number-average molecular weight of the composition can be, for example, 200 to 6000 g / mol. The lower limit of the number-average molecular weight of the composition can 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 can be, for example, below 6000 g / mol, below 5000 g / mol, below 4000 g / mol, below 3000 g / mol, below 2500 g / mol, below 2000 g / mol, below 1800 g / mol, below 1600 g / mol, below 1400 g / mol, below 1200 g / mol, below 1000 g / mol, or below 800 g / mol.

[0217] The number-average molecular weight of the composition is the converted number-average molecular weight of the difunctional polyoxypropylene polyol, measured using GPC (Gel Permeation Chromatography) with the entire composition as the test object.

[0218] The hydroxyl value of the composition may be, for example, 30 to 800 mg KOH / g. The lower limit of the hydroxyl value of the composition may be, for example, 30 mg KOH / g or more, 40 mg KOH / g or more, 50 mg KOH / g or more, 60 mg KOH / g or more, 70 mg KOH / g or more, 80 mg KOH / g or more, 90 mg KOH / g or more, 100 mg KOH / g or more, 120 mg KOH / g or more, 140 mg KOH / g or more, 160 mg KOH / g or more, or 180 mg KOH / g or more. The upper limit of the hydroxyl value of the composition may be, for example, below 800 mg KOH / g, below 700 mg KOH / g, below 600 mg KOH / g, below 500 mg KOH / g, below 400 mg KOH / g, below 300 mg KOH / g, below 250 mg KOH / g, below 200 mg KOH / g, below 180 mg KOH / g, below 160 mg KOH / g, below 140 mg KOH / g, below 120 mg KOH / g, below 100 mg KOH / g, or below 80 mg KOH / g.

[0219] According to this embodiment, a composition that facilitates the formation of a polyurethane resin with high tensile strength and good workability can be provided.

[0220] <Manufacturing Method>

[0221] In the method for producing compound (A-1) in embodiments 1 to 3, compound (A-1) can be obtained by heating a mixture containing polyol (B1), diol (D1), carbonate and transesterification catalyst, and performing a reflux reaction (transesterification reaction) while removing alcohol from carbonate in the reaction system. Alternatively, compound (A-1) can be obtained by heating a mixture containing polyol (B1), diol (D1), carbonate, oxetane compound (F1) and transesterification catalyst, and performing a reflux reaction (transesterification reaction) while removing alcohol from carbonate in the reaction system.

[0222] In the above method, the composition of the above embodiments can also be obtained in the form of a reaction mixture containing compound (A-1). Therefore, the above method can also be referred to as a method for manufacturing the composition of the above embodiments.

[0223] Details of polyols (B1), diols (D1), carbonates, and oxetane compounds (F1) are as described above, with preferred examples (R) 1 and R 2 (Preferred examples and preferred examples of combinations) also relate to the R of compound (A-1). 1 and R 2 The preferred examples and combinations are the same. Lithium acetylacetonate is preferred as a transesterification catalyst from the viewpoint of readily obtaining the desired compound (A-1).

[0224] When two or more types of diols (D1) are used as raw materials for polyurethane resins, from the viewpoint of easily forming polyurethane resins with good tensile strength, elongation, hand feel, and excellent durability, the ratio of the molar number of 1,6-hexanediol to the total molar number of diols (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).

[0225] The mixing ratio of polyol (B1) to diol (D1) (the content of diol (D1) in the mixture / the content of polyol (B1) in the mixture) is preferably 1 / 100 to 5 / 1, more preferably 1 / 80 to 3 / 1, even more preferably 1 / 50 to 2 / 1, and particularly preferably 1 / 20 to 1 / 1, in molar ratio. By setting the mixing ratio of diol to polyol within the above range, a composition containing compound (A-1) can be obtained efficiently. The above mixing ratio can be 1 / 5 to 60 / 1 or 1 / 1 to 40 / 1 in molar ratio.

[0226] The mixing ratio of carbonate to polyol (B1) and diol (D1) (the content of carbonate in the mixture / the total content of polyol (B1) and diol (D1) in the mixture) is preferably 1 / 3 to 3 / 1, more preferably 1 / 2.5 to 2.5 / 1, even more preferably 1 / 2 to 2 / 1, and particularly preferably 1 / 1.5 to 1.5 / 1, by setting the mixing ratio of carbonate to polyol (B1) and diol (D1) within the above range, a composition containing compound (A-1) can be obtained efficiently.

[0227] From the viewpoint of easily and appropriately controlling the reaction temperature and suppressing the increase in the color number of the reaction products, the content of the transesterification catalyst in the mixture of embodiments 1 to 3, relative to 100 parts by mass of the total amount of polyols, glycols, and carbonates in the mixture, can be 0.0001 to 0.1 parts by mass, or 0.0005 to 0.01 parts by mass. From the viewpoint of easily controlling the reactivity of the carbamate reaction, the lower the content of the transesterification catalyst, the better. If the content of the transesterification catalyst is increased, the reactivity of the carbamate reaction is easily improved. From the viewpoint of easily controlling the carbamate reaction, the content of the transesterification catalyst in the mixture, relative to 100 parts by mass of the total amount of polyols, glycols, and carbonates in the mixture, 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. From the viewpoint of suppressing the increase in the color number of the reaction products, the content of the transesterification catalyst in the mixture 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 polyols, glycols, and carbonates in the mixture. From these viewpoints, the content of the transesterification catalyst in the mixture 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 polyols, glycols, and carbonates in the mixture.

[0228] The heating temperature (reaction temperature) of the mixture in embodiments 1 to 3 can be, for example, 80 to 250°C or 100 to 220°C. If the reaction temperature is 80°C or higher, the transesterification reaction proceeds easily, and the desired compound (A-1) is readily obtained. If the reaction temperature is 250°C or lower, the color number of the obtained compound (A-1) and the polyol in the composition can be suppressed. Furthermore, the transesterification reaction can be carried out while maintaining a constant temperature, or it can be carried out while gradually increasing the temperature, either in stages or continuously, depending on the degree of reaction. From the viewpoint of easily obtaining the desired compound (A-1), it is preferable to heat at a temperature T1 that satisfies the relationship described in formula (α), followed by heating at a temperature T2 that satisfies the relationship described in formula (β). It should be noted that temperatures T1 and T2 preferably satisfy the relationship described in formula (γ). Additionally, the average temperature T1 of the first heating temperature is preferably... m The average temperature T2 of the second heating temperature m The following equation (δ) applies. Here, the extent of the reaction can be estimated based on the amount of distillate distilled off.

[0229] 120℃≤T1≤155℃(α)

[0230] 140℃≤T2≤155℃(β)

[0231] T1 <T2(γ)

[0232] T1 m <T2 m (δ)

[0233] The heating of the mixture in embodiments 1 to 3 can be carried out at atmospheric pressure or, in the latter half of the reaction, under reduced pressure (e.g., at a pressure of 101 to 0.1 kPa). This accelerates the distillation rate of the generated distillate and speeds up the reaction. It should be noted that, in this specification, atmospheric pressure refers to 101.325 kPa ± 20.000 kPa. From the viewpoint of easily obtaining the desired compound (A-1), the heating of the mixture preferably includes: heating at a pressure of 101.325 kPa ± 20.000 kPa (first heating), followed by heating under reduced pressure of 10.000 kPa or less (second heating). The temperature of the first heating is T1, which satisfies the relationship in equation (α) above, and the temperature of the second heating is T2, which satisfies the relationship in equation (β) above. More preferably, the temperatures of the first heating (T1) and the second heating (T2) satisfy the relationship in equation (γ) above. Furthermore, from the viewpoint of easily obtaining compound (A-1), it is preferable to remove the alcohol derived from the carbonate by distillation below 120°C from the reaction system.

[0234] The reaction time for the mixture in embodiments 1 to 3 can 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 shown in formula (C) above is generated through an intramolecular dehydration reaction of the polyol and / or an intramolecular decarboxylation reaction of the cyclic carbonate as a product of the reaction between the polyol and the carbonate. The intramolecular dehydration and decarboxylation reactions are irreversible, and the amount of structure (C) derived from the oxetane compound generated increases with reaction time. If the reaction time is 2 hours or more, the generation of the structure (C) derived from the oxetane compound can be promoted, and a molar ratio (C) can be easily obtained. C / C T ×100) and / or molar ratio (C C / (C C +C D +C E The composition satisfies the above numerical range (A-1) × 100. Furthermore, if the reaction time is less than 80 hours, the formation of the structure (C) derived from the oxobutane compound can be suppressed, and a composition containing the desired compound (A-1) can be easily obtained.

[0235] The compound (A-1) of the fourth embodiment can be obtained, for example, by a method comprising the following reaction step: reacting polycarbonate polyol (B2) with polyester polyol (C2) in a mixture comprising polycarbonate polyol (B2), polyester polyol (C2) and a transesterification catalyst (transesterification reaction) to obtain compound (A-1). In this method, at least one of polycarbonate polyol (B2) and polyester polyol (C2) comprises a group represented by formula (I) above, or the mixture may further comprise a polyol represented by formula (e). The mixture may further comprise an oxetane compound (F2). That is, the compound (A-1) of the fourth embodiment can also be obtained by a method comprising the following reaction step: reacting polycarbonate polyol with polyester polyol in a mixture comprising polycarbonate polyol (B2), polyester polyol (C2), transesterification catalyst and oxetane compound (F2) (transesterification reaction) to obtain compound (A-1).

[0236] In the above method, the composition of the above embodiments can also be obtained in the form of a reaction mixture containing compound (A-1). Therefore, the above method can also be referred to as a method for manufacturing the composition of the above embodiments.

[0237] The mixture of the fourth embodiment may contain diol (D2) and / or oxetane compound (F2) as optional components. Even when the above method is a method in which at least one of polycarbonate polyol (B2) and polyester polyol (C2) contains the group shown in formula (I) above, the mixture may also contain polyol (E2) as optional components. Details of polycarbonate polyol (B2) and polyester polyol (C2), diol (D2), polyol (E2) and oxetane compound (F2) are as described above, and they are preferably exemplified (R) 1 and R 2 (Preferred examples and preferred combinations) also have the R characteristic of compound (A-1) 1 and R 2 The preferred examples and combinations are the same. Lithium acetylacetonate is preferred as a transesterification catalyst from the viewpoint of readily obtaining the desired compound (A-1).

[0238] The mixing ratio of polycarbonate polyol (B2) to polyester polyol (C2) (content of polycarbonate polyol (B2) in the mixture / content of polyester polyol (C2) in the mixture) by weight is preferably 95 / 5 to 5 / 95, more preferably 90 / 10 to 10 / 90, even more preferably 80 / 20 to 20 / 80, and particularly preferably 70 / 30 to 30 / 70. By making the mixing ratio of polycarbonate polyol (B2) to polyester polyol (C2) within the above range, a composition containing compound (A-1) can be obtained efficiently.

[0239] The mixing ratio of polycarbonate polyol (B2) to polyester polyol (β) and / or polyester polyol (β') (the content of polycarbonate polyol (B2) in the mixture / the content of polyester polyol (β) and / or polyester polyol (β') in the mixture) by weight is preferably 95 / 5 to 5 / 95, more preferably 90 / 10 to 10 / 90, even more preferably 80 / 20 to 20 / 80, and particularly preferably 70 / 30 to 30 / 70. By making the mixing ratio of polycarbonate polyol (B2) to polyester polyol (β) and / or polyester polyol (β') within the above range, a composition containing compound (A-1) can be obtained efficiently.

[0240] From the viewpoint of easily and appropriately controlling the reaction temperature and suppressing the increase in the color number of the reaction products, the content of the transesterification catalyst in the mixture of the fourth embodiment can 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 polyol component in the mixture. From the viewpoint of easily controlling the reactivity of the carbamate esterification reaction, the lower the content of the transesterification catalyst, the better. If the content of the transesterification catalyst is increased, the reactivity of the carbamate esterification reaction is easily improved. From the viewpoint of easily controlling the carbamate esterification reaction, the content of the transesterification catalyst in the mixture 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 polyol component in the mixture. From the viewpoint of suppressing the increase in the color number of the reaction products, the content of the transesterification catalyst in the mixture 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 polyol content in the mixture. From these viewpoints, the content of the transesterification catalyst in the mixture 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 polyol content in the mixture. The total polyol content refers to the total amount of compounds with two or more hydroxyl groups (e.g., polycarbonate polyol (B2), polyester polyol (C2), polyol (E2), and diols (D2) of any added components) and oxetane compounds (F2) contained in the mixture.

[0241] In the reaction step of the fourth embodiment, the reaction can be carried out by heating the mixture or by not heating. The reaction temperature of the mixture is, for example, 0 to 250°C, or 100 to 220°C. If the reaction temperature is above 0°C, the transesterification reaction proceeds easily, and the desired compound (A-1) is readily obtained. Furthermore, if the reaction temperature is above 0°C, the formation of the structure (C) derived from oxetane of a polyol with three or more functions, which is a byproduct of the decarboxylation reaction of the carbonate group or the dehydration reaction between the terminal hydroxyl groups, can be promoted. If the reaction temperature is below 250°C, the color number of the obtained compound (A-1) and the composition (the composition containing the polyol) can be suppressed. Furthermore, if the reaction temperature is below 250°C, the formation of the structure (C) derived from oxetane of a polyol with three or more functions, which is a byproduct of the decarboxylation reaction of the carbonate group or the dehydration reaction between the terminal hydroxyl groups, can be suppressed. Furthermore, the transesterification reaction can be carried out at a constant temperature, or it can be carried out by gradually increasing the temperature, either in stages or continuously, depending on the extent of the reaction. From the viewpoint of easily obtaining the desired compound (A-1), it is preferable to heat at a temperature T1 that satisfies the relationship described in equation (α'), followed by heating at a temperature T2 that satisfies the relationship described in equation (β'). It should be noted that temperatures T1 and T2 preferably satisfy the relationship described in equation (γ'). Additionally, the average temperature T1 of the first heating is preferably... m The average temperature T2 of the second heating temperature m The following equation (δ') applies. Here, the extent of the reaction can be estimated based on the amount of feedstock consumed as obtained from the GPC chart.

[0242] 180℃≤T1≤200℃(α')

[0243] 190℃≤T2≤200℃(β')

[0244] T1 <T2(γ’)

[0245] T1 m <T2 m (δ')

[0246] The heating of the mixture in the fourth embodiment can be carried out under normal pressure or under reduced pressure (e.g., 101-1 kPa). This removes residual moisture from the mixture, accelerates the reaction, and suppresses coloration of the composition. It should be noted that, in this specification, normal pressure refers to 101.325 kPa ± 20.000 kPa. From the viewpoint of easily obtaining the desired compound (A-1), the heating of the mixture preferably includes: heating at a pressure of 101.325 kPa ± 20.000 kPa (first heating), and then heating under reduced pressure of 20.000 kPa or less (second heating). The temperature of the first heating is T1, which satisfies the above formula (α'), and the temperature of the second heating is preferably T2, which satisfies the above formula (β'). More preferably, the temperatures of the first heating (T1) and the second heating (T2) satisfy the above formula (γ').

[0247] The reaction time for the mixture in the fourth embodiment can be 1–40 hours, 2–30 hours, 3–20 hours, 4–15 hours, or 5–12 hours. The structure (C) derived from the oxetane compound shown in formula (C) above is generated through an intramolecular dehydration reaction of the polyol and / or an intramolecular decarboxylation reaction of the cyclic carbonate as a product of the reaction between the polyol and the carbonate. The intramolecular dehydration and decarboxylation reactions are irreversible, and the amount of structure (C) derived from the oxetane compound generated increases with reaction time. If the reaction time is 2 hours or more, the generation of the structure (C) derived from the oxetane compound can be promoted, and a molar ratio (C) can be easily obtained. C / C T ×100) and / or molar ratio (C C / (C C +C D +C E The composition satisfies the above numerical range (A-1) × 100. Furthermore, if the reaction time is less than 80 hours, the formation of the structure (C) derived from the oxobutane compound can be suppressed, and a composition containing the desired compound (A-1) can be easily obtained.

[0248] In the fourth embodiment, heating of the mixture can also be carried out while nitrogen gas is flowing in. This allows for the removal of moisture from the mixture and accelerates the reaction. Furthermore, nitrogen purging can suppress coloration of the composition. From the viewpoint of easily obtaining the desired compound (A-1), the nitrogen flow rate of the mixture is preferably 2 to 1000 ml / min / scale(kg), more preferably 5 to 200 ml / min / scale(kg).

[0249] In the manufacturing methods of embodiments 1 to 4, the obtained reaction mixture can be subjected to post-treatments such as distillation and drying. Alternatively, in the above manufacturing methods, after obtaining compound (A-1) or a composition containing it, components such as compounds (A-2) to (A-4), diol (d), polyol (e), and oxetane compound (F) can be added to prepare the mixture.

[0250] <Polyurethane Resins and Their Manufacturing Methods>

[0251] Polyurethane resin is a condensation polymer or cross-linked polymer of polyol and polyisocyanate components. Here, a cross-linked polymer refers to a polymer that is cross-linked with each other by chain extenders or the like.

[0252] (Polyol components)

[0253] The polyol component includes the aforementioned compound (A-1). The polyol component may include polyols (compounds having two or more terminal hydroxyl groups) or monools (compounds having one terminal hydroxyl group) other than compound (A-1). The polyol component may also include, for example, polyols (compounds (A-2), (A-3), (A-4), diols (d), polyols (e), oxetane compounds (F), etc.) that may be included in the above composition. The content ratio of these polyols may be the same as the content ratio of the polyols in the above composition (e.g., molar ratio (C)). C / C T ×100), molar ratio (C) C / (C C +C D +C E (×100) is the same. In other words, the polyol component may comprise a mixture of polyols from the above composition except for compounds other than polyols.

[0254] The polyol component may also contain polyols with acidic groups. In this case, the polyurethane resin contains acidic groups. Polyurethane resins with acidic groups are suitable for waterborne polyurethane resin dispersions. Waterborne polyurethane resin dispersions will be described later.

[0255] The acidic group is, for example, a functional group (hydrophilic group) that can impart hydrophilicity to isocyanate-terminated prepolymers obtained by reaction with isocyanates. Examples of polyols having such an acidic group include dimethylolpropionic acid (DMPA), dimethylolbutyric acid (DMBA), dimethylolvalerate, dimethylolnonanoic acid, and other dimethylolalkanoic acids.

[0256] (Polyisocyanates)

[0257] Examples of polyisocyanates include aromatic polyisocyanates, aromatic aliphatic polyisocyanates, aliphatic polyisocyanates, and alicyclic polyisocyanates. Modified polyisocyanates, which are modifiers of these, can also be used. Examples of modified polyisocyanates include isocyanurate-modified polyisocyanates (isocyanate trimers), allophanate-modified polyisocyanates, uretdione-modified polyisocyanates, carbamate-modified polyisocyanates, biuret-modified polyisocyanates, uretonimine-modified polyisocyanates, and acyl urea-modified polyisocyanates. These can be used alone or in combination of two or more.

[0258] Examples of aromatic isocyanates include 2,4-tolylenediisocyanate, 2,6-tolylenediisocyanate, mixtures of 2,4-tolylenediisocyanate and 2,6-tolylenediisocyanate, 4,4'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, mixtures of 2,4'-diphenylmethane diisocyanate and 4,4'-diphenylmethane diisocyanate, and xylylene diisocyanate. diisocyanate, p-xylene diisocyanate, 4,4'-diphenyl ether diisocyanate, 2-nitrodiphenyl-4,4'-diisocyanate, 2,2'-diphenylpropane-4,4'-diisocyanate, 3,3'-dimethyldiphenylmethane-4,4'-diisocyanate, 4,4'-diphenylpropane diisocyanate, isophenyl diisocyanate, p-phenyl diisocyanate, 1,4-naphthalene diisocyanate, 1,5-naphthalene diisocyanate, 3,3'-dimethoxydiphenyl-4,4'-diisocyanate, etc.

[0259] Examples of aromatic aliphatic isocyanates include, for example, 1,3-dimethyldiisocyanate, 1,4-dimethyldiisocyanate 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, etc.

[0260] Examples of aliphatic isocyanates include hexamethylene diisocyanate, pentamethylene diisocyanate, tetramethylene diisocyanate, 2-methylpentane-1,5-diisocyanate, 3-methylpentane-1,5-diisocyanate, and lysine diisocyanate. 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-diisocyanate-4-(isocyanate-methyl)octane (1,8-diisocyanate-4-(isocyanate-methyl)octane) yanato-4-(isocyanatomethyl)octane, 2,5,7-trimethyl-1,8-diisocyanato-5-isocyanatomethyl)octane, bis(isocyanatoethyl)carbonate, bis(isocyanatoethyl)ether, 1,4-butylene dipropyl ether-α,α'-diisocyanate Glycol dipropyl ether-α,α'-diisocyanate, lysine diisocyanatomethyl ester, 2-isocyanatoethyl-2,6-diisocyanatohexanoate, 2-isocyanatopropyl-2,6-diisocyanatohexanoate, etc.

[0261] Examples of alicyclic isocyanates include isophorone diisocyanate, cyclohexyl diisocyanate, bis(isocyanatomethyl)cyclohexane, dicyclohexylmethane diisocyanate, methylcyclohexyl diisocyanate, dicyclohexyl dimethylmethane diisocyanate, 2,2'-dimethyldicyclohexylmethane diisocyanate, bis(4-isocyanato-n-butylidene)pentaerythritol, and hydrogenated dimer acid diisocyanate. diisocyanate), 2-isocyanatomethyl-3-(3-isocyanatopropyl)-5-(isocyanatomethyl)bicyclo[2.2.1]heptane, 2-(isocyanatomethyl)-3-(3-isocyanatopropyl)-6-(isocyanatomethyl)bicyclo[2.2.1]heptane, 2-(isocyanatomethyl)-2-(3-isocyanatopropyl)-5-(isocyanatomethyl)bicyclo[2.2.1]heptane, 2-(isocyanatomethyl)-2-(3-isocyanatopropyl)-6-(isocyanatomethyl)bicyclo[2.2.1]heptane Heptane, 2-(isocyanate methyl)-3-(3-isocyanate propyl)-5-(2-isocyanate ethyl)bicyclo[2.2.1]heptane, 2-(isocyanate methyl)-3-(3-isocyanate propyl)-6-(2-isocyanate ethyl)bicyclo[2.2.1]heptane, 2-(isocyanate methyl)-2-(3-isocyanate propyl)-5-(2-isocyanate ethyl)bicyclo[2.2.1]heptane, 2-(isocyanate methyl)-2-(3-isocyanate propyl)-5-(2-isocyanate ethyl)bicyclo[2.2.1]heptane, 2-(isocyanate methyl)-2-(3-isocyanate propyl)-5-(2-isocyanate ethyl)bicyclo[2.2.1]heptane Cyclo[2.2.1]heptane, 2-(isocyanate methyl)-2-(3-isocyanate propyl)-6-(2-isocyanate ethyl)bicyclo[2.2.1]heptane, 2,5-bis(isocyanate methyl)bicyclo[2.2.1]heptane, hydrogenated diphenylmethane diisocyanate, norbornene diisocyanate, hydrogenated toluene diisocyanate, hydrogenated xylene diisocyanate, hydrogenated tetramethylxylene diisocyanate, etc.

[0262] (Polyol / Polyisocyanate ingredient ratio)

[0263] The optimal blending ratio of polyol to polyisocyanate components is 9:1 to 1:9, more preferably 6:4 to 4:6, where the active hydrogen in the polyol component is to the isocyanate group in the polyisocyanate component. Polyurethane resins within this range tend to exhibit better performance.

[0264] (Chain extender)

[0265] Chain extenders can be appropriately selected according to purpose and application. Examples of chain extenders that can be used include water; ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, neopentanediol, 1,10-decanediol, 1,1-cyclohexanediethanol, 1,4-cyclohexanediethanol, tricyclodecanediethanol, xylene glycol, bis(p-hydroxy)diphenyl, bis(p-hydroxyphenyl)propane, 2,2-bis[4-(2-hydroxyethoxy)phenyl]propane, bis[4-(2-hydroxyethoxy)phenyl]sulfone, 1 Low molecular weight polyols such as 1-bis[4-(2-hydroxyethoxy)phenyl]cyclohexane; high molecular weight polyols such as polyester polyols, polyesteramide polyols, polyether polyols, polyether ester polyols, polycarbonate polyols, and polyolefin polyols; polyamines such as ethylenediamine, isophorone diamine, 2-methyl-1,5-pentanediamine, aminoethylethanolamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, and pentaethylenehexamine. The amount of chain extender (the proportion of the polyurethane resin containing components derived from the chain extender structure) can be 0.1 to 50 parts by mass relative to 100 parts by mass of the total polyol and polyisocyanate components. It should be noted that when the chain extender is a polyol, the content of the polyol is calculated as included in both the chain extender and polyol components.

[0266] The aforementioned polyurethane resin can be obtained by reacting a polyol component, a polyisocyanate component, and a chain extender as needed (urethane esterification reaction). The urethane esterification reaction can be carried out at room temperature (e.g., 25°C) or under heating (e.g., 40–200°C).

[0267] In carbamate reactions, catalysts (carbamate catalysts) can be added to shorten reaction time and increase reaction rate. Examples of catalysts include tertiary amine catalysts such as triethylamine, triethylenediamine, tetramethylethylenediamine, tetramethylpropylenediamine, and tetramethylhexamethylenediamine, as well 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. Dibutyltin dilaurate is preferred. The amount of catalyst used can be 0.001 to 100 parts by mass relative to 100 parts by mass of the total polyol and polyisocyanate components.

[0268] When a catalyst is used in the carbamate reaction, a phosphorus compound is used for better catalyst handling. As phosphorus compounds, they are not specifically limited, but can include, for example, trimethyl phosphate, triethyl phosphate, tributyl phosphate, di-2-ethylhexyl phosphate, triphenyl phosphate, tricresyl phosphate, cresyl diphenyl phosphate, etc.; 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, isodecanyl acid phosphate, butoxyethyl acid phosphate, oleic acid phosphate, tetracosyl acid phosphate, ethylene glycol acid phosphate, 2-hydroxyethylmethacrylate acid phosphate, dibutyl phosphate, monobutyl phosphate, monoisodecyl phosphate, bis(2-ethylhexyl) phosphate, etc.; triphenyl phosphite, etc. phosphite), trinonylphenyl phosphite, tricresyl phosphite, triethyl phosphite, tri(2-ethylhexyl) phosphite, tridecyl phosphite, trilauryl phosphite, tri(tetrazyl) phosphite, trioleyl phosphite, diphenylmono(2-ethylhexyl) phosphite, diphenylmonodecyl phosphite, diphenyl(monodecyl) phosphite, trilauryl phosphite, diethylhydrogen phosphite, bis(2-ethylhexyl)hydrogenphosphite, dilauryl hydrogen phosphite, dioleyl hydrogen phosphite, diphenyl hydrogen phosphite, tetraphenyl dipropylene glycol diphosphite, bis(decyl)pentaerythritol diphosphite Phosphites such as diphosphite, tripistearyl phosphite, distearyl pentaerythritol diphosphite, and tris(2,4-di-tert-butylphenyl) phosphite; phosphoric acid, phosphorous acid, hypophosphite, etc. These can be used alone or in combination of two or more. Preferably, acidic phosphate esters are used, and more preferably, 2-ethylhexyl acidic phosphate ester. The amount of phosphorus compound used relative to 100 parts by weight of the catalyst can be 10 to 2000 parts by weight.

[0269] Carbamate esterification reactions can be carried out in the presence of a solvent. Examples of solvents that can be used 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 dimethyl sulfoxide; 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.

[0270] The polyurethane resins described above exhibit good elongation and hand feel, excellent durability, and good tensile strength, depending on the application. Therefore, these polyurethane resins are suitable for use in synthetic leather, artificial leather, coatings, etc.

[0271] <Coating Agent>

[0272] The coating agent in this embodiment comprises the polyurethane resin described above. The specific form of the polyurethane resin can be as described above.

[0273] As an example of coating application, in-mold coating using RIM (Reaction Injection Molding) can be cited. Specifically, in-mold coating using RIM involves molding a plastic substrate within an injection mold, and then forming a urethane coating film on the surface of the molded article within the mold. In this method, the mold volume is constant, ensuring stable density, thickness, and hardness of the urethane coating film, and faithfully reproducing the surface texture of the mold, resulting in a highly customizable appearance.

[0274] <Waterborne polyurethane resin dispersion>

[0275] The aqueous polyurethane resin dispersion contains an aqueous medium and a polyurethane resin or its neutralized form dispersed in the aqueous medium. The polyurethane resin is one of the aforementioned polyurethane resins that has acidic groups (the polyol component includes polyols with acidic groups).

[0276] As an aqueous medium, in addition to water, solutions containing emulsifiers, dispersants, etc., can also be used. The aqueous medium preferably contains water, and more preferably consists of only water.

[0277] When an aqueous polyurethane resin dispersion contains a neutralized polyurethane resin, the acidic groups of the polyurethane resin can be neutralized by a neutralizing agent. Examples of neutralizing agents 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 morpholines; alkali metals such as lithium, potassium, and sodium; and inorganic bases such as sodium hydroxide and potassium hydroxide. From the viewpoint of improving the durability and smoothness of the coating film, highly volatile neutralizing agents such as ammonia, trimethylamine, and triethylamine, which are easily dissociated by heating, are preferred. These neutralizing agents can be used alone or in combination of two or more.

[0278] When manufacturing waterborne polyurethane resin dispersions, compounds containing anionic polar groups can also be used. Examples of compounds containing anionic polar groups include those composed of an organic acid having one or more active hydrogen atoms and a neutralizing agent. Examples of organic acids include carboxylates, sulfonates, phosphates, phosphonates, hypophosphonates, and thiosulfonates. These anionic polar groups contained in the organic acid can be introduced individually or linked to metal ions in a chelating manner.

[0279] When manufacturing waterborne polyurethane resin dispersions, compounds containing cationic polar groups can also be used. Examples of compounds containing cationic polar groups include: tertiary amines having one or more active hydrogen atoms; and one of the group consisting of neutralizing agents for inorganic acids, neutralizing agents for organic acids, and quaternizing agents. Furthermore, cationic compounds such as primary amine salts, secondary amine salts, tertiary amine salts, and pyridinium salts can also be used as compounds containing cationic polar groups.

[0280] Examples of tertiary amines having one or more active hydrogen atoms 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, triisopropanolamine, N-methyl-bis(3-aminopropyl)-amine, and N-methyl-bis(2-aminopropyl)-amine. Alternatively, amines can be formed by the addition of primary amines such as ammonia and methylamine, or secondary amines such as dimethylamine, to alkylene oxides.

[0281] Examples of inorganic and organic acids include hydrochloric acid, acetic acid, lactic acid, cyanoacetic acid, phosphoric acid, and sulfuric acid.

[0282] Examples of quaternizing agents include dimethyl sulfate, benzyl chloride, bromoacetamide, and chloroacetamide. Additionally, halogenated alkanes such as bromoethane, bromopropane, and bromobutane can also be used.

[0283] Aqueous polyurethane resin dispersions are manufactured, for example, by sequentially performing the following steps: reacting a polyol component containing an acidic polyol with a polyisocyanate component in the presence or absence of a solvent to obtain 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. It should be noted that a catalyst may be used in each step as needed, thereby promoting the reaction and controlling the amount of byproducts.

[0284] The films formed by the waterborne polyurethane resin dispersions described above (e.g., films formed by coating a substrate with the waterborne polyurethane resin dispersion) exhibit excellent adhesion, softness, and tactile feel. Therefore, the aforementioned waterborne polyurethane resin dispersions are suitable for use in artificial leather, synthetic leather, exterior coatings, interior coatings, and coating agents.

[0285] <Two-component composition kit>

[0286] The polyol and polyisocyanate components used to form the polyurethane resin described above can be stored and handled in different containers as a two-component composition kit. The two-component composition kit comprises: a first component containing at least the aforementioned polyol component, and a second component containing at least the aforementioned polyisocyanate component. When using chain extenders, catalysts, solvents, etc., these can be included in the first and / or second components, or they can be formulated separately from the first and second components. The aforementioned two-component composition kit is applicable, for example, to coating agents, and also to the manufacture of artificial leather, synthetic leather, exterior coatings, interior coatings, etc. When the aforementioned two-component composition kit is used as a coating agent, for example, after mixing the first and second components, the resulting mixture is applied to a substrate and heated as appropriate, thereby forming a coating film (e.g., a cured film containing polyurethane resin).

[0287] As an example of using a two-component composition kit as a coating agent, this resin composition, which does not use organic solvents, can also be used in the manufacture of artificial leather, synthetic leather, etc., to form a polyurethane resin with excellent adhesion, softness, and feel.

[0288] Polyurethane resin forming compositions containing the aforementioned polyol and polyisocyanate components, as well as polyurethane resin compositions containing the aforementioned polyurethane resin, are preferably used as aqueous polyurethane resin emulsions, solvent-free synthesized polyurethane resins, or their precursors. Furthermore, by curing the aqueous polyurethane resin emulsion or solvent-free synthesized polyurethane resin, molded articles such as coatings and / or films with high toughness, 100% modulus reduction (good hand feel), and high softening temperature can be obtained, suitable for leather applications such as artificial leather and synthetic leather, and as surface treatment agents for leather. 100% modulus is one of the indicators for quantifying the moist, elastic, and high-quality feel when in contact with synthetic leather; if the value is within a certain range, it is considered a polyurethane resin with the aforementioned good properties.

[0289] <Applications>

[0290] The composition, polyurethane resin, aqueous polyurethane resin dispersion, and coating agent described in this embodiment can be used in coating compositions suitable for automotive exterior clear paint and automotive interior paint. Furthermore, the composition, polyurethane resin, aqueous polyurethane resin dispersion, and coating agent described in this embodiment are preferably used in home appliances, OA (office automation) products, leather surface treatment, and synthetic leather surface treatment.

[0291] Example

[0292] The following describes embodiments of the present invention, but the present invention is not limited to these embodiments.

[0293] [Synthesis Example 1: Synthesis of Polycarbonate Diol 1]

[0294] In a 2L double-necked glass reactor equipped with a stirrer, thermometer, heating device, distillation column filled with regularly packed material, and condenser, 826g of 1,6-hexanediol, 787g of diethyl carbonate, and 0.05g of tetrabutyl titanate were mixed and reacted at 100–190°C for 8 hours under normal pressure to remove low-boiling-point components. Then, the reaction temperature was set to 190°C, the pressure inside the flask was reduced to 1 kPa, and the reaction was continued for another 8 hours to obtain polycarbonate polyol (PCD-1).

[0295] [Table 1]

[0296]

[0297] Details of the raw materials used are as follows.

[0298] ·1,6-Hexanediol: manufactured by BASF-JAPAN

[0299] • Trimethylolpropane: manufactured by Sigma-Aldrich

[0300] Diethyl carbonate: manufactured by Sigma-Aldrich

[0301] Tetrabutyl titanate: manufactured by Tokyo Chemical Industry Co., Ltd.

[0302] <Example>

[0303] <First Embodiment>

[0304] (Example 1A)

[0305] In a 1L double-necked glass reactor (reactor A) equipped with a stirrer, thermometer, heating device, distillation column filled with regularly packed material, and condenser, 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 atmospheric pressure at 130–150°C (initial 130°C, final 150°C) for 1.5 hours to remove low-boiling components (alcohols derived from carbonates, etc.). The distillate temperature was above 77°C and below 79°C. Then, 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 at 0.5 kPa for 1.0 hour, thereby obtaining a composition (PCP-1A) containing compound (A-1).

[0306] (Example 2A)

[0307] Except for the addition of 1.43 g of 3-ethyl-3-hydroxymethyloxetane, a composition (PCP-2A) containing compound (A-1) was obtained in the same manner as in Example 1A.

[0308] (Example 3A)

[0309] Except for the addition of 2.14 g of 3-ethyl-3-hydroxymethyloxetane, a composition (PCP-3A) containing compound (A-1) was obtained in the same manner as in Example 1A.

[0310] (Example 4A)

[0311] Except for the addition of 2.85 g of 3-ethyl-3-hydroxymethyloxetane, a composition (PCP-4A) containing compound (A-1) was obtained in the same manner as in Example 1A.

[0312] (Example 5A)

[0313] Except for the addition of 5.70 g of 3-ethyl-3-hydroxymethyloxetane, a composition (PCP-5A) containing compound (A-1) was obtained in the same manner as in Example 1A.

[0314] (Example 6A)

[0315] In 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 resulting mixture was heated at atmospheric pressure at 130–150 °C (initial 130 °C, final 150 °C) for 1.5 hours to remove low-boiling components (alcohols derived from carbonates, etc.). The distillate temperature was above 77 °C and below 79 °C. Then, at a reaction temperature of 150 °C, the pressure in the flask was gradually reduced to 0.5 kPa over 0.5 hours, and the reaction was continued at 0.5 kPa for 35 hours, thereby obtaining a composition (PCP-6A) containing compound (A-1).

[0316] (Comparative Example 1A)

[0317] Except that 3-ethyl-3-hydroxymethyloxetane was set to 0 g, the same composition (PCP-7A) containing compound (A-1) was obtained as in Example 1A.

[0318] (Comparative Example 2A)

[0319] Except for the addition of 0.07 g of 3-ethyl-3-hydroxymethyloxetane, the composition (PCP-8A) containing compound (A-1) was obtained in the same manner as in Example 1A.

[0320] (Comparative Example 3A)

[0321] Except for the addition of 0.14 g of 3-ethyl-3-hydroxymethyloxetane, a composition (PCP-9A) containing compound (A-1) was obtained in the same manner as in Example 1A.

[0322] (Comparative Example 4A)

[0323] Except for the addition of 0.43 g of 3-ethyl-3-hydroxymethyloxetane, a composition (PCP-10A) containing compound (A-1) was obtained in the same manner as in Example 1A.

[0324] (Comparative Example 5A)

[0325] Except for the addition of 7.13 g of 3-ethyl-3-hydroxymethyloxetane, a composition (PCP-11A) containing compound (A-1) was obtained in the same manner as in Example 1A.

[0326] (Comparative Example 6A)

[0327] In 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 resulting mixture was heated at atmospheric pressure at 130–150 °C (initial 130 °C, final 150 °C) for 8 hours to remove low-boiling components (alcohols derived from carbonates). The distillate temperature was above 77 °C and below 79 °C. Then, the reaction temperature was set to 150 °C, the pressure in the flask was reduced to 1 kPa, and the reaction was carried out at 1 kPa for another 8 hours to obtain a composition (PCP-12A) containing compound (A-1).

[0328] (Analysis and Evaluation)

[0329] [Determination of number-average molecular weight]

[0330] The polycarbonate polyols and compositions obtained above were subjected to GPC analysis under the following conditions to determine the number-average molecular weight of the polycarbonate polyols and the number-average molecular weight of the compositions. The results are shown in Tables 1 and 2.

[0331] -condition-

[0332] (1) Measuring instrument: HLC-8420 (manufactured by Tosoh Corporation)

[0333] (2) Chromatographic column: TSKgel (manufactured by Tosoh Corporation)

[0334] ·G3000H-XL

[0335] ·G3000H-XL

[0336] G2000H-XL

[0337] G2000H-XL

[0338] (3) Mobile phase: THF (tetrahydrofuran)

[0339] (4) Detector: RI (Refractive Index) detector (HLC-8420 accessory)

[0340] (5) Temperature: 40℃

[0341] (6) Flow rate: 1.000 ml / min

[0342] (7) Standard curve: The standard curve was obtained using the following products (all of which are difunctional polyoxypropylene polyols manufactured by Sanyo Chemical Industries, Ltd.).

[0343] • "SANNIX PP-200" (Number average molecular weight = 200, average number of functional groups: 2)

[0344] • "SANNIX PP-400" (Number average molecular weight = 400, average number of functional groups: 2)

[0345] • "SANNIX PP-1000" (Number average molecular weight = 1000, average number of functional groups: 2)

[0346] • "SANNIX PP-2000" (Number average molecular weight = 2000, average number of functional groups: 2)

[0347] • "SANNIX PP-3000" (number average molecular weight = 3200, average number of functional groups: 2)

[0348] • "SANNIX PP-4000" (Number average molecular weight = 4160, average number of functional groups: 2)

[0349] (8) Approximate form of the standard curve: cubic form

[0350] (9) Sample solution concentration: 0.5% by mass THF solution

[0351] [Determination of hydroxyl value]

[0352] The hydroxyl values ​​of the polycarbonate polyols and the compositions obtained above were determined according to JIS K1557-1 using an acetylation reagent. The results are shown in Tables 1 and 2.

[0353] [Track Evaluation]

[0354] The above-obtained composition was used as a sample. The sample was heated at 80°C for 1 hour and then placed at 25°C for 3 days. The state of the sample after placement was visually confirmed; if it showed slight fluidity at the above temperature, it was classified as liquid; otherwise, it was classified as solid. The results are shown in Table 2.

[0355] <Calculation methods for each component>

[0356] (Considered as the average number of hydroxyl functional groups)

[0357] The perceived average number of hydroxyl functional groups in the composition is calculated from the number-average molecular weight and hydroxyl value obtained by GPC (Gel Permeation Chromatography). Originally, the average number of hydroxyl functional groups was calculated based on the actual number-average molecular weight and average hydroxyl value. However, since the actual number-average molecular weight of the composition is difficult to calculate, the number-average molecular weight converted from the PPG standard curve determined by GPC is defined as the perceived average number of hydroxyl functional groups. The perceived average number of hydroxyl functional groups is defined by the following formula.

[0358] The average number of hydroxyl functional groups is considered to be (average hydroxyl value of the composition (mgKOH / g) × number average molecular weight of the composition calculated from the PPG standard curve by GPC (g / mol)) / (56.11 (KOH g / mol) × 1000).

[0359] [Composition Analysis]

[0360] The composition analysis of the composition was performed in the following order.

[0361] First, the above-obtained composition (sample) was dissolved in deuterated chloroform (manufactured by FUJIFILM Wako PureChemical Co., Ltd.) to obtain a solution. Tetramethylsilane (TMS) was then added to this solution as a chemical shift reference to obtain a test solution. The test solution was measured using a JNM-ECX400 instrument manufactured by Nippon Egis Corporation. 1 H-NMR, with the TMS signal set to 0 ppm, yielded 1 H-NMR spectroscopy. Measurements were performed under the following conditions.

[0362] -condition-

[0363] • Resonant frequency: 400MHz

[0364] • Pulse amplitude: 45 degrees

[0365] Waiting time: 5 seconds

[0366] • Total number of times: 64

[0367] • Sample solution concentration (deuterated chloroform containing TMS): 3% by mass (vol%)

[0368] Next, based on the above... 1 Using H-NMR spectra, the integral value Δ of the signal (SC) of the methylene group next to the oxygen atom of the oxobutyric group shown in formula (C) above was determined. SC The integral value Δ of the signal (SD) of the methylene group next to the hydroxyl group in formula (D). SD The integral value Δ of the signal (SE) of the methylene group next to the hydroxyl group in the group shown in formula (E). SE Additionally, the R groups shown in formulas (I) and (C) 2 In the case of methyl or ethyl groups, calculate the integral value of the signal of their terminal methyl groups and use it as the integral value Δ of the signal (SI). SI .

[0369] Specifically, signals with a concentration of 4.390 ppm or higher and 4.500 ppm or lower are considered as signals (SC), signals with a concentration of 3.618 ppm or higher and 3.720 ppm or lower are considered as signals (SD), signals with a concentration of 3.590 ppm or higher and 3.618 ppm or lower are considered as signals (SE), and signals with a concentration of 0.700 ppm or higher and 1.130 ppm or lower are considered as R of the groups shown in formulas (I) and (C). 2 For the case where the polyol (e) is methyl (in the case where the polyol (e) is trimethylolethane), the signal (SI) is taken as the R of the group shown in formula (I) and formula (C) with a value of 0.700 ppm or more and 1.000 ppm or less. 2 The signal (SI) is for the case of ethyl (the case where the polyol (e) is trimethylolpropane).

[0370] It should be noted that the baseline for the integral value determination is set as the following straight line: a horizontally plotted line relative to the lowest spectral intensity within the specified spectral range, using this as a reference. The signal (SE) typically represents a single peak, but peak splitting can occur due to trace amounts of moisture. If a split peak is detected, it deviates from the aforementioned integration range, and the correct C value cannot be obtained. E Therefore, the integral value obtained from the signal (SE) is represented by a single peak.

[0371] The molar ratio (C) is calculated from the obtained integral value. C / C T ×100), and molar ratio (C) C / (C C +C D +C E (×100). The results are shown in Table 2.

[0372] [Table 2]

[0373]

[0374] In Table 2, the “Composition” (unit: g) of Examples 1A to 6A and Comparative Examples 1A to 6A represents the reaction raw materials.

[0375] (Physical property evaluation)

[0376] The following method was used to prepare a urethane-cured film coating (thin film), and the resulting film was used as a sample for evaluation of its physical properties (tensile properties, heat resistance, and low-temperature properties).

[0377] [Preparation of urethane-cured coating]

[0378] First, the above-obtained composition, polyisocyanate component (C-2612), urethane esterification catalyst, phosphorus compound (JP508), and diluent were mixed in a 200 mL glass bottle according to the formulations listed in Table 3 (unit: g). Immediately after mixing, the mixture was poured onto release paper and cast into a 200 μm thick film using a bar coater. Next, the cast film was cured by heating at 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).

[0379] [Tensive Properties 100% Modulus Evaluation]

[0380] According to JIS K6251, the tensile properties and 100% modulus properties of the obtained film were determined under the following conditions: (100% modulus, strength at break, elongation at break).

[0381] -condition-

[0382] • Test apparatus: Tensilon UTA-500 (manufactured by A&D)

[0383] • Measurement conditions: 25℃ × 50% RH

[0384] • Head speed: 200mm / minute

[0385] Dumbbell No. 4

[0386] [Softening Temperature]

[0387] After obtaining a test piece from the resulting film using a dumbbell, a 2cm mark is made on the test piece, and the thickness at the center of the mark is measured. A weight of a specified weight is installed on one side of the test piece's clamping part, while the other side is clamped with a double clamp. The test piece is then suspended in a dryer with the clamps on top, and the dryer is heated. The distance between the marks is observed, and the temperature at which the distance between the marks reaches 4cm is taken as the softening temperature.

[0388] • Processing unit: DRK633DA constant temperature air dryer (manufactured by Advantech)

[0389] • Weight of the weight: Thickness of the mark at its center (μm) × 0.05g

[0390] Dumbbell #2 (based on JIS K6251)

[0391] • Heating rate: 5℃ / minute

[0392] Glass transition temperature

[0393] After obtaining a test piece (0.4 cm wide, 2.5 cm long) from the obtained film using a dumbbell, the thickness at the center of the mark was measured (approximately 100–200 μm). The glass transition temperature is the peak temperature at which the loss modulus (E”) / storage modulus (E’) = tanδ is obtained.

[0394] -condition-

[0395] • Processing unit: RHEOVIBRON DDV-01GP Dynamic Viscoelastomeret (manufactured by ORIENTEC)

[0396] • Range: -50~40℃

[0397] • Heating rate: 3℃ / minute

[0398] • Frequency: 35Hz

[0399] • Amplitude: 16μm

[0400] Static tension: 5.00gf

[0401] [Evaluation Criteria]

[0402] The physical properties of 100% modulus, breaking strength, elongation at break, softening temperature and glass transition temperature are evaluated as A, B, C and D (A: very good, B: good, C: average, D: poor).

[0403] <100% Modulus>

[0404] A: Above 1.5MPa and below 2.0MPa

[0405] B: Less than 1.5 MPa

[0406] C: Exceeding 2.0 MPa

[0407] <Tension Strength>

[0408] A: Exceeding 19 MPa

[0409] B: Above 15MPa and below 19MPa

[0410] D: Less than 15MPa

[0411] Elongation at break

[0412] A: Over 350%

[0413] B: Below 350%

[0414] <Softening Temperature>

[0415] A: Over 240℃

[0416] B: Temperature above 230℃ and below 240℃

[0417] C: Below 230℃

[0418] Glass transition temperature

[0419] A: Below 1.5℃

[0420] B: Above 1.5℃

[0421] [Table 3]

[0422]

[0423] (Operational evaluation)

[0424] Isocyanate-terminated urethane prepolymers were prepared using the following method. The resulting isocyanate-terminated urethane prepolymers were then used as samples for evaluation of their operability (prepolymer viscosity).

[0425] [Preparation of isocyanate-terminated carbamate prepolymers]

[0426] In a 1L reactor equipped with a stirrer, thermometer, nitrogen-sealed tube, and condenser, the above-obtained composition, N-980N (Tosoh Corporation: number average molecular weight 2000; hydroxyl value 56.11 mgKOH / g; 1,6-hexanediol-based polycarbonate diol), 1,6-hexanediol, 2,2-dimethylolpropionic acid (hydrophilizing agent), isophorone diisocyanate (polyisocyanate), and methyl ethyl ketone (organic solvent) were added according to the formulation (unit: g) listed in Table 4. The mixture was heated to 78°C and stirred at the same temperature for 30 minutes. Then, 0.010 g of DOTDL (catalyst) was added, and the reaction was allowed to proceed for 2 hours. Next, 0.015 g of DOTDL was added, and the reaction was allowed to proceed for 2 hours. Then, another 0.010 g of DOTDL was added, and the reaction was allowed to proceed for another 2 hours. The reaction was stopped after the NCO content of the product confirmed that the hydroxyl groups of the polyol and the hydrophilizing agent had been completely consumed, yielding an isocyanate-terminated urethane prepolymer.

[0427] [Viscosity of isocyanate-terminated urethane prepolymer]

[0428] Approximately 2 g of the isocyanate-terminated urethane prepolymer was collected and sealed in a sample tube along with a 4.7 mm aluminum spherical probe. The viscosity at a stable state of 50 °C was measured using an EMS (Electro Magnetically Spinning) viscometer (Kyoto Electron Kogyo Co., Ltd.: EMS-1000). The results are shown in Table 4.

[0429] Measurement conditions

[0430] Temperature: 50℃

[0431] • Spherical probe: φ4.7mm

[0432] • Motor speed: 1000 rpm

[0433] • Measurement interval: 30 seconds

[0434] • Measurement time: 5 minutes

[0435] [Evaluation Criteria]

[0436] The viscosity of isocyanate-terminated urethane prepolymers was evaluated using A, B, C, and D (A: very good, B: good, C: average, D: poor).

[0437] Viscosity

[0438] A: Less than 1700 mPa·s

[0439] B: Above 1700 mPa·s and below 1800 mPa·s

[0440] D: Exceeding 1800 mPa·s

[0441] [Table 4]

[0442]

[0443] The composition was evaluated using a gradation system of A, B, C, and D (A: Very Good, B: Good, C: Average, D: Poor). The results are shown in Table 5.

[0444] <Overall Evaluation>

[0445] A: The evaluation of various physical properties and operability is only for A.

[0446] B: The evaluation of various physical properties and operability does not include D, but includes one of B or C.

[0447] C: Evaluations of various physical properties and operability do not include D, but include two or more of B or C.

[0448] D: Evaluation of various physical properties and operability includes D

[0449] [Table 5]

[0450]

[0451] Details of the materials used in the first embodiment are as follows.

[0452] ·1,6-Hexanediol: manufactured by BASF-JAPAN

[0453] • Trimethylolpropane: manufactured by Sigma-Aldrich

[0454] Diethyl carbonate: manufactured by Sigma-Aldrich

[0455] ·3-Ethyl-3-hydroxymethyloxetane: Produced by Tokyo Chemical Industry Co., Ltd.

[0456] • Lithium acetylacetonate: manufactured by Sigma-Aldrich

[0457] • C-2612: CORONATE 2612 (trade name), hexamethylene diisocyanate addition-modified polyisocyanate, isocyanate content = 17.2%, manufactured by Tosoh Corporation.

[0458] JP-508: Trade name, 2-ethylhexyl acid phosphate, manufactured by Chengbei Chemical Industry Co., Ltd.

[0459] • DOTDL: Dioctyltin dilaurate, manufactured by KISHIDA CHEMICAL INDUSTRY

[0460] Methyl ethyl ketone (MEK): Manufactured by Maruzen Petrochemical Co., Ltd.

[0461] Toluene: manufactured by FUJIFILM Wako Pure Chemical Co., Ltd.

[0462] BYK-331: Silicon-based surface conditioner, manufactured by BYK Corporation.

[0463] ·2,2-Dimethylolpropionic acid: manufactured by Tokyo Chemical Industry Co., Ltd.

[0464] • Isophorone diisocyanate: manufactured by Evonik

[0465] <Second Embodiment>

[0466] (Example 1B)

[0467] In reactor A, 15.8 g of trimethylolpropane, 99.5 g of 1,6-hexanediol, 75.9 g of 1,4-butanediol, 208.9 g of diethyl carbonate, 0.68 g of 3-ethyl-3-hydroxymethyloxetane, and 0.030 g of lithium acetylacetonate were mixed. The resulting mixture was heated at atmospheric pressure at 130–150 °C (initial 130 °C, final 150 °C) for 1.5 hours to remove low-boiling components (alcohols derived from carbonates, etc.). The distillate temperature was above 77 °C and below 79 °C. Then, at a reaction temperature of 150 °C, the pressure in the flask was reduced to 0.5 kPa over 0.5 hours, and the reaction was carried out at 0.5 kPa for 1.0 hour, thereby obtaining a composition (PCP-1B) containing compound (A-1).

[0468] (Example 2B)

[0469] Except for the addition of 1.36 g of 3-ethyl-3-hydroxymethyloxetane, a composition (PCP-2B) containing compound (A-1) was obtained in the same manner as in Example 1B.

[0470] (Example 3B)

[0471] Except for the addition of 2.73 g of 3-ethyl-3-hydroxymethyloxetane, a composition (PCP-3B) containing compound (A-1) was obtained in the same manner as in Example 1B.

[0472] (Comparative Example 1B)

[0473] Except that 3-ethyl-3-hydroxymethyloxetane was set to 0 g, the same composition (PCP-4B) containing compound (A-1) was obtained as in Example 1B.

[0474] (Comparative Example 2B)

[0475] Except that the amount of 3-ethyl-3-hydroxymethyloxetane was set to 6.82 g, the composition (PCP-5B) containing compound (A-1) was obtained in the same manner as in Example 1B.

[0476] (Example 4B)

[0477] Except for the addition of 0.60 g of 3-ethyl-3-hydroxymethyloxetane, a composition (PCP-6B) containing compound (A-1) was obtained in the same manner as in Example 1B.

[0478] (Example 5B)

[0479] Except for the addition of 2.73 g of 3-ethyl-3-hydroxymethyloxetane, the composition (PCP-7B) containing compound (A-1) was obtained in the same manner as in Example 1B.

[0480] (Example 6B)

[0481] Except for the addition of 4.80 g of 3-ethyl-3-hydroxymethyloxetane, a composition (PCP-8B) containing compound (A-1) was obtained in the same manner as in Example 1B.

[0482] (Comparative Example 3B)

[0483] Except for the addition of 0.34 g of 3-ethyl-3-hydroxymethyloxetane, the composition (PCP-9B) containing compound (A-1) was obtained in the same manner as in Example 1B.

[0484] (Comparative Example 4B)

[0485] Except for the addition of 0.50 g of 3-ethyl-3-hydroxymethyloxetane, a composition (PCP-10B) containing compound (A-1) was obtained in the same manner as in Example 1B.

[0486] (Comparative Example 5B)

[0487] Except for the addition of 8.20 g of 3-ethyl-3-hydroxymethyloxetane, the composition (PCP-11B) containing compound (A-1) was obtained in the same manner as in Example 1B.

[0488] (Comparative Example 6B)

[0489] In reactor A, 15.8 g of trimethylolpropane, 99.5 g of 1,6-hexanediol, 75.9 g of 1,4-butanediol, 208.9 g of diethyl carbonate, and 0.030 g of lithium acetylacetonate were mixed. The resulting mixture was heated at atmospheric pressure at 130–150 °C (initial 130 °C, final 150 °C) for 8 hours to remove low-boiling components (alcohols derived from carbonates, etc.). The distillate temperature was above 77 °C and below 79 °C. The reaction temperature was further set to 150 °C, the pressure in the flask was reduced to 1 kPa, and the reaction was carried out at 1 kPa for another 8 hours to obtain a composition (PCP-13B) containing compound (A-1).

[0490] (Analysis and Evaluation)

[0491] Similar to Example 1, the number-average molecular weight and hydroxyl value of the obtained compositions were determined, and property evaluation, calculation of the average number of hydroxyl functional groups, and compositional analysis were performed. In the compositional analysis, signals of 4.390 ppm or higher and 4.500 ppm or lower were used as signals (SC), signals of 3.618 ppm or higher and 3.720 ppm or lower were used as signals (SD), signals of 3.590 ppm or higher and 3.618 ppm or lower were used as signals (SE), and signals of 0.700 ppm or higher and 1.130 ppm or lower were used as R values ​​for the groups shown in Formulas (I) and (C). 2 For the case where the polyol (e) is methyl (in the case where the polyol (e) is trimethylolethane), the signal (SI) is taken as the R of the group shown in formula (I) and formula (C) with a value of 0.700 ppm or more and 1.000 ppm or less. 2 The signal (SI) is for the case of ethyl groups (where the polyol (e) is trimethylolpropane). The results are shown in Table 6. Figure 1 The composition obtained in Example 1B is shown. 1 H-NMR spectrum.

[0492] [Table 6]

[0493]

[0494] In Table 6, the “Composition” (unit: g) of Examples 1B to 6B and Comparative Examples 1B to 6B represents the reaction raw materials.

[0495] (Physical property evaluation)

[0496] In addition to mixing the above-obtained composition, polyisocyanate component (C-2612), urethane esterification catalyst, phosphate ester (JP508), and diluent as described in Table 7 (unit: g), a urethane-cured coating (film) was obtained in the same manner as in Example 1. The resulting film was then used as a sample, and its physical properties (tensile properties, hand feel, low-temperature properties) were evaluated in the same manner as in Example 1. The results are shown in Table 7.

[0497] [Evaluation Criteria]

[0498] The physical properties of 100% modulus, breaking strength, elongation at break, softening temperature, and glass transition temperature are evaluated as A, B, C, and D (A: very good, B: good, C: average, D: poor).

[0499] <100% Modulus>

[0500] A: Above 1.0 MPa and below 1.7 MPa

[0501] B: Exceeding 1.7 MPa

[0502] C: Less than 1.0

[0503] <Tension Strength>

[0504] A: Exceeding 19 MPa

[0505] B: Above 16MPa and below 19MPa

[0506] D: Less than 16MPa

[0507] Elongation at break

[0508] A: More than 410%

[0509] B: Less than 410%

[0510] <Softening Temperature>

[0511] A: Over 240℃

[0512] B: Below 240℃

[0513] Glass transition temperature

[0514] A: Below 4.5℃

[0515] B: Above 4.5℃

[0516] [Table 7]

[0517]

[0518] (Operational evaluation)

[0519] Except for the addition of the above-obtained composition, N-980N, 1,6-hexanediol, 2,2-dimethylolpropionic acid (hydrophilizing agent), isophorone diisocyanate (polyisocyanate), and methyl ethyl ketone (organic solvent) as described in Table 8 (unit: g), the operability (viscosity of isocyanate-terminated urethane prepolymer) was evaluated in the same manner as in Example 1. The results are shown in Table 8.

[0520] [Evaluation Criteria]

[0521] The viscosity of isocyanate-terminated urethane prepolymers was evaluated using A, B, C, and D (A: very good, B: good, C: average, D: poor).

[0522] Viscosity

[0523] A: Below 2500 mPa·s

[0524] D: Exceeding 2500 mPa·s

[0525] [Table 8]

[0526]

[0527] The composition was evaluated using a gradation system of A, B, C, and D (A: Very Good, B: Good, C: Average, D: Poor). The results are shown in Table 9.

[0528] <Overall Evaluation>

[0529] A: The evaluation of various physical properties and operability is only for A.

[0530] B: The evaluation of various physical properties and operability does not include D, but includes one of B or C.

[0531] C: Evaluations of various physical properties and operability do not include D, but include two or more of B or C.

[0532] D: Evaluation of various physical properties and operability includes D

[0533] [Table 9]

[0534]

[0535] Details of the materials used in the second embodiment are as follows.

[0536] ·1,6-Hexanediol: manufactured by BASF-JAPAN

[0537] ·1,4-Butanediol: Produced by Tokyo Chemical Industry Co., Ltd.

[0538] • Trimethylolpropane: manufactured by Sigma-Aldrich

[0539] Diethyl carbonate: manufactured by Sigma-Aldrich

[0540] ·3-Ethyl-3-hydroxymethyloxetane: Produced by Tokyo Chemical Industry Co., Ltd.

[0541] • Lithium acetylacetonate: manufactured by Sigma-Aldrich

[0542] • C-2612: CORONATE 2612 (trade name), hexamethylene diisocyanate addition-modified polyisocyanate, isocyanate content = 17.2%, manufactured by Tosoh Corporation.

[0543] JP-508: Trade name, 2-ethylhexyl acid phosphate, manufactured by Chengbei Chemical Industry Co., Ltd.

[0544] • DOTDL: Dioctyltin dilaurate, manufactured by KISHIDA CHEMICAL INDUSTRY

[0545] Methyl ethyl ketone (MEK): Manufactured by Maruzen Petrochemical Co., Ltd.

[0546] Toluene: manufactured by FUJIFILM Wako Pure Chemical Co., Ltd.

[0547] BYK-331: Silicon-based surface conditioner, manufactured by BYK Corporation.

[0548] ·2,2-Dimethylolpropionic acid: Tokyo Chemical Industry Co., Ltd.

[0549] • Isophorone diisocyanate: Evonik

[0550] <Third Embodiment>

[0551] (Example 1C)

[0552] In reactor A, 16.5 g of trimethylolpropane, 93.6 g of 1,6-hexanediol, 93.6 g of 3-methyl-1,5-pentanediol, 196.4 g of diethyl carbonate, 0.77 g of 3-ethyl-3-hydroxymethyloxetane, and 0.030 g of lithium acetylacetonate were mixed. The resulting mixture was heated at atmospheric pressure at 130–150 °C (initial 130 °C, final 150 °C) for 1.5 hours to remove low-boiling components (alcohols derived from carbonates, etc.). The distillate temperature was above 77 °C and below 79 °C. Then, at a reaction temperature of 150 °C, the pressure in the flask was reduced to 0.5 kPa over 0.5 hours, and the reaction was continued at 0.5 kPa for 1.0 hour, thereby obtaining a composition (PCP-1C) containing compound (A-1).

[0553] (Example 2C)

[0554] Except for the addition of 1.42 g of 3-ethyl-3-hydroxymethyloxetane, the composition (PCP-2C) containing compound (A-1) was obtained in the same manner as in Example 1C.

[0555] (Example 3C)

[0556] Except for the addition of 3.00 g of 3-ethyl-3-hydroxymethyloxetane, a composition (PCP-3C) containing compound (A-1) was obtained in the same manner as in Example 1C.

[0557] (Comparative Example 1C)

[0558] Except that 3-ethyl-3-hydroxymethyloxetane was set to 0g, the same composition (PCP-4C) containing compound (A-1) was obtained as in Example 1C.

[0559] (Comparative Example 2C)

[0560] Except that 3-ethyl-3-hydroxymethyloxetane was set at 0.17 g, the same composition (PCP-5C) containing compound (A-1) was obtained as in Example 1C.

[0561] (Comparative Example 3C)

[0562] Except that 7.30 g of 3-ethyl-3-hydroxymethyloxetane was used, the same composition (PCP-6C) containing compound (A-1) was obtained as in Example 1C.

[0563] (Example 4C)

[0564] Except for the addition of 2.20 g of 3-ethyl-3-hydroxymethyloxetane, a composition (PCP-7C) containing compound (A-1) was obtained in the same manner as in Example 1C.

[0565] (Example 5C)

[0566] Except for the addition of 3.85 g of 3-ethyl-3-hydroxymethyloxetane, a composition (PCP-8C) containing compound (A-1) was obtained in the same manner as in Example 1C.

[0567] (Example 6C)

[0568] Except for the addition of 6.50 g of 3-ethyl-3-hydroxymethyloxetane, a composition (PCP-9C) containing compound (A-1) was obtained in the same manner as in Example 1C.

[0569] (Example 7C)

[0570] In reactor A, 16.5 g of trimethylolpropane, 93.6 g of 1,6-hexanediol, 93.6 g of 3-methyl-1,5-pentanediol, 196.4 g of diethyl carbonate, and 0.030 g of lithium acetylacetonate were mixed. The resulting mixture was heated at atmospheric pressure at 130–150 °C (initial 130 °C, final 150 °C) for 1.5 hours to remove low-boiling components (alcohols derived from carbonates, etc.). The distillate temperature was set above 77 °C and below 79 °C. Then, at a reaction temperature of 150 °C, the pressure in the flask was gradually reduced to 0.5 kPa over 0.5 hours, and the reaction was continued at 0.5 kPa for 35 hours, thereby obtaining a composition (PCP-10C) containing compound (A-1).

[0571] (Comparative Example 4C)

[0572] Except that 3-ethyl-3-hydroxymethyloxetane was set at 0.55 g, the same composition (PCP-11C) containing compound (A-1) was obtained as in Example 1C.

[0573] (Analysis and Evaluation)

[0574] Similar to Example 1, the number-average molecular weight and hydroxyl value of the obtained compositions were determined, and property evaluation, calculation of the average number of hydroxyl functional groups, and compositional analysis were performed. In the compositional analysis, signals of 4.390 ppm or higher and 4.500 ppm or lower were used as signals (SC), signals of 3.618 ppm or higher and 3.720 ppm or lower were used as signals (SD), and signals of 3.590 ppm or higher and 3.618 ppm or lower were used as signals (SE). The results are shown in Table 10. Figure 2 The composition obtained in Example 1C is shown. 1 H-NMR spectrum.

[0575] [Table 10]

[0576]

[0577] In Table 10, the “Composition” (unit: g) of Examples 1C to 7C and Comparative Examples 1C to 4C represents the reaction raw materials.

[0578] (Physical property evaluation)

[0579] In addition to mixing the above-obtained composition, polyisocyanate component (C-2612), urethane esterification catalyst, phosphate ester (JP508), and diluent (unit: g) as described in Tables 8 and 9, a urethane-cured coating (film) was obtained in the same manner as in Example 1. The resulting film was then used as a sample, and its physical properties (tensile properties, hand feel, low-temperature properties) were evaluated in the same manner as in Example 1. The results are shown in Table 11.

[0580] [Evaluation Criteria]

[0581] The physical properties of 100% modulus, breaking strength, elongation at break, softening temperature and glass transition temperature are evaluated as A, B, C and D (A: very good, B: good, C: average, D: poor).

[0582] <100% Modulus>

[0583] A: Below 2.0MPa

[0584] B: Exceeding 2.0 MPa

[0585] <Tension Strength>

[0586] A: Exceeding 14.5 MPa

[0587] B: Above 13MPa and below 14.5MPa

[0588] D: Less than 13MPa

[0589] Elongation at break

[0590] A: More than 400%

[0591] B: Less than 400%

[0592] <Softening Temperature>

[0593] A: Above 230℃

[0594] B: Less than 230℃

[0595] Glass transition temperature

[0596] A: Below 4.0℃

[0597] B: Above 4.0℃

[0598] [Table 11]

[0599]

[0600] (Operational evaluation)

[0601] Except for the addition of the above-obtained composition, N-980N, 1,6-hexanediol, 2,2-dimethylolpropionic acid (hydrophilizing agent), isophorone diisocyanate (polyisocyanate), and methyl ethyl ketone (organic solvent) as described in Table 12 (unit: g), the operability (viscosity of isocyanate-terminated urethane prepolymer) was evaluated in the same manner as in Example 1. The results are shown in Table 12.

[0602] [Evaluation Criteria]

[0603] The viscosity of isocyanate-terminated urethane prepolymers was evaluated using A, B, C, and D (A: very good, B: good, C: average, D: poor).

[0604] Viscosity

[0605] A: Below 1400 mPa·s

[0606] D: Exceeding 1400 mPa·s

[0607] [Table 12]

[0608]

[0609] The composition was evaluated using a gradation system of A, B, C, and D (A: Very Good, B: Good, C: Average, D: Poor). The results are shown in Table 13.

[0610] <Overall Evaluation>

[0611] A: The evaluation of each physical property and operability is only A.

[0612] B: The evaluation of various physical properties and operability does not include D, but includes one B or C.

[0613] C: Evaluation of various physical properties and operability does not include D, but includes two or more of B or C.

[0614] D: Evaluation of various physical properties and operability includes D.

[0615] [Table 13]

[0616]

[0617] Details of the materials used in the third embodiment are as follows.

[0618] ·1,6-Hexanediol: manufactured by BASF-JAPAN

[0619] ·3-Methyl-1,5-pentanediol: manufactured by FUJIFILM Wako Pure Chemical Co., Ltd.

[0620] • Trimethylolpropane: manufactured by Sigma-Aldrich

[0621] Diethyl carbonate: manufactured by Sigma-Aldrich

[0622] ·3-Ethyl-3-hydroxymethyloxetane: Produced by Tokyo Chemical Industry Co., Ltd.

[0623] • Lithium acetylacetonate: manufactured by Sigma-Aldrich

[0624] • C-2612: CORONATE 2612 (trade name), hexamethylene diisocyanate addition-modified polyisocyanate, isocyanate content = 17.2%, manufactured by Tosoh Corporation.

[0625] JP-508: Trade name, 2-ethylhexyl acid phosphate, manufactured by Chengbei Chemical Industry Co., Ltd.

[0626] • DOTDL: Dioctyltin dilaurate, manufactured by KISHIDA CHEMICAL INDUSTRY

[0627] Methyl ethyl ketone (MEK): Manufactured by Maruzen Petrochemical Co., Ltd.

[0628] Toluene: manufactured by FUJIFILM Wako Pure Chemical Co., Ltd.

[0629] BYK-331: Silicon-based surface conditioner, manufactured by BYK Corporation.

[0630] ·2,2-Dimethylolpropionic acid: manufactured by Tokyo Chemical Industry Co., Ltd.

[0631] • Isophorone diisocyanate: manufactured by Evonik

[0632] (Fourth implementation)

[0633] (Example 1D)

[0634] In a 0.5L four-necked glass reactor (reactor B) equipped with a stirrer, thermometer, heating device, and condenser, 371.6g of PCD-1, 128.2g of PLACEL 305, 1.35g of 3-ethyl-3-hydroxymethyloxetane, and 0.08g of lithium acetylacetonate were mixed. The mixture was heated at 190°C under normal pressure for 6 hours to obtain a composition (PCP-1D) containing compound (A-1).

[0635] (Example 2D)

[0636] Except for the addition of 2.91 g of 3-ethyl-3-hydroxymethyloxetane, the composition (PCP-2D) containing compound (A-1) was obtained in the same manner as in Example 1D.

[0637] (Example 3D)

[0638] Except for the addition of 5.42 g of 3-ethyl-3-hydroxymethyloxetane, the composition (PCP-3D) containing compound (A-1) was obtained in the same manner as in Example 1D.

[0639] (Example 4D)

[0640] In reactor B, 371.6 g of PCD-1, 128.2 g of PLACEL 305, and 0.08 g of lithium acetylacetone were mixed. The mixture was heated at 190 °C under normal pressure for 35 hours to obtain a composition (PCP-4D) containing compound (A-1).

[0641] (Comparative Example 1D)

[0642] Except that 3-ethyl-3-hydroxymethyloxetane was set to 0 g, the same composition (PCP-5D) containing compound (A-1) was obtained as in Example 1D.

[0643] (Comparative Example 2D)

[0644] Except that 3-ethyl-3-hydroxymethyloxetane was set at 0.39 g, the composition (PCP-6D) containing compound (A-1) was obtained in the same manner as in Example 1D.

[0645] (Comparative Example 3D)

[0646] Except that 3-ethyl-3-hydroxymethyloxetane was set at 0.93 g, the composition (PCP-7D) containing compound (A-1) was obtained in the same manner as in Example 1D.

[0647] (Comparative Example 4D)

[0648] Except that 3-ethyl-3-hydroxymethyloxetane was set to 13.5 g, the composition (PCP-8D) containing compound (A-1) was obtained in the same manner as in Example 1D.

[0649] (Comparative Example 5D)

[0650] In reactor B, 371.6 g of PCD-1, 128.2 g of PLACEL 305, and 0.05 g of potassium bicarbonate were mixed. The mixture was heated at 190 °C under normal pressure for 5 hours to obtain a composition (PCP-9D) containing compound (A-1).

[0651] (Example 5D)

[0652] Except for the addition of 0.97 g of 3-ethyl-3-hydroxymethyloxetane, the composition (PCP-10D) containing compound (A-1) was obtained in the same manner as in Example 1D.

[0653] (Example 6D)

[0654] Except for the addition of 1.05 g of 3-ethyl-3-hydroxymethyloxetane, the composition (PCP-11D) containing compound (A-1) was obtained in the same manner as in Example 1D.

[0655] (Example 7D)

[0656] Except for the addition of 1.20 g of 3-ethyl-3-hydroxymethyloxetane, the composition (PCP-12D) containing compound (A-1) was obtained in the same manner as in Example 1D.

[0657] (Example 8D)

[0658] Except for the addition of 8.00 g of 3-ethyl-3-hydroxymethyloxetane, the composition (PCP-13D) containing compound (A-1) was obtained in the same manner as in Example 1D.

[0659] (Example 9D)

[0660] Except for the addition of 10.00 g of 3-ethyl-3-hydroxymethyloxetane, a composition (PCP-14D) containing compound (A-1) was obtained in the same manner as in Example 1D.

[0661] (Comparative Example 2D)

[0662] Except that 3-ethyl-3-hydroxymethyloxetane was set at 0.19 g, the composition (PCP-15D) containing compound (A-1) was obtained in the same manner as in Example 1D.

[0663] (Analysis and Evaluation)

[0664] Similar to Example 1, the number-average molecular weight and hydroxyl value of the obtained compositions were determined, and property evaluation, calculation of the average number of hydroxyl functional groups, and compositional analysis were performed. In the compositional analysis, signals of 4.390 ppm or higher and 4.500 ppm or lower were used as signals (SC), signals of 3.618 ppm or higher and 3.720 ppm or lower were used as signals (SD), signals of 3.550 ppm or higher and 3.618 ppm or lower were used as signals (SE), and signals of 0.700 ppm or higher and 1.130 ppm or lower were used as R values ​​for the groups represented by formulas (I) and (C). 2 For the case where the polyol (e) is methyl (in the case where the polyol (e) is trimethylolethane), the signal (SI) is set to 0.700 ppm or more and 1.000 ppm or less as R of the group shown in formula (I) and formula (C). 2 The signal (SI) is for the case of ethyl (the case where the polyol (e) is trimethylolpropane).

[0665] The results are shown in Table 14.

[0666] [Table 14]

[0667]

[0668] In Table 14, the “Composition” (unit: g) of Examples 1D to 9D and Comparative Examples 1D to 6D represents the reaction raw materials.

[0669] (Physical property evaluation)

[0670] Except for mixing the above-obtained composition, polyisocyanate component (C-2612), urethane esterification catalyst, phosphate ester (JP508), and diluent as described in Table 15 (unit: g), a urethane-cured coating (film) was obtained in the same manner as in Example 1. The obtained film was then used as a sample, and its physical properties (tensile properties, hand feel, low-temperature properties) were evaluated in the same manner as in Example 1. The results are shown in Table 15.

[0671] [Evaluation Criteria]

[0672] The physical properties of 100% modulus, breaking strength, elongation at break, softening temperature and glass transition temperature are evaluated as A, B, C and D (A: very good, B: good, C: average, D: poor).

[0673] <100% Modulus>

[0674] A: Below 2.0MPa

[0675] B: Exceeding 2.0 MPa

[0676] <Tension Strength>

[0677] A: Exceeding 16MPa

[0678] B: Below 16MPa and above 15MPa

[0679] D: Less than 15MPa

[0680] Elongation at break

[0681] A: More than 400%

[0682] B: Less than 400%

[0683] <Softening Temperature>

[0684] A: Above 250℃

[0685] B: Less than 250℃

[0686] Glass transition temperature

[0687] A: −; below 2℃

[0688] B: Exceeding -2℃

[0689] [Table 15]

[0690]

[0691] (Operational evaluation)

[0692] Except for the addition of the above-obtained composition, N-980N, 1,6-hexanediol, 2,2-dimethylolpropionic acid (hydrophilizing agent), isophorone diisocyanate (polyisocyanate), and methyl ethyl ketone (organic solvent) as described in Table 16 (unit: g), the operability (viscosity of isocyanate-terminated urethane prepolymer) was evaluated in the same manner as in Example 1. The results are shown in Table 16.

[0693] [Evaluation Criteria]

[0694] The viscosity of isocyanate-terminated urethane prepolymers was evaluated using A, B, C, and D (A: very good, B: good, C: average, D: poor).

[0695] Viscosity

[0696] A: Below 2600 mPa·s

[0697] D: Exceeding 2600 mPa·s

[0698] [Table 16]

[0699]

[0700] The composition was evaluated using a gradation system of A, B, C, and D (A: Very Good, B: Good, C: Average, D: Poor). The results are shown in Table 17.

[0701] <Overall Evaluation>

[0702] A: The evaluation of each physical property and operability is only A.

[0703] B: The evaluation of various physical properties and operability does not include D, but includes one B or C.

[0704] C: Evaluation of various physical properties and operability does not include D, but includes two or more of B or C.

[0705] D: Evaluation of various physical properties and operability includes D.

[0706] [Table 17]

[0707]

[0708] Details of the materials used in the fourth embodiment are as follows.

[0709] PLACEL 305: Polycaprolactone triol (number average molecular weight = 550, hydroxyl value = 305, number of functional groups = 3), manufactured by DAICEL.

[0710] ·3-Ethyl-3-hydroxymethyloxetane: Produced by Tokyo Chemical Industry Co., Ltd.

[0711] • Lithium acetylacetonate: manufactured by Sigma-Aldrich

[0712] Potassium bicarbonate: Manufactured by FUJIFILM Wako Pure Chemical Co., Ltd.

[0713] • C-2612: CORONATE 2612 (trade name), hexamethylene diisocyanate addition-modified polyisocyanate, isocyanate content = 17.2%, manufactured by Tosoh Corporation.

[0714] JP-508: Trade name, 2-ethylhexyl acid phosphate, manufactured by Chengbei Chemical Industry Co., Ltd.

[0715] • DOTDL: Dioctyltin dilaurate, manufactured by KISHIDA CHEMICAL INDUSTRY

[0716] Methyl ethyl ketone (MEK): Manufactured by Maruzen Petrochemical Co., Ltd.

[0717] Toluene: manufactured by FUJIFILM Wako Pure Chemical Co., Ltd.

[0718] BYK-331: Silicon-based surface conditioner, manufactured by BYK Corporation.

[0719] ·2,2-Dimethylolpropionic acid: manufactured by Tokyo Chemical Industry Co., Ltd.

[0720] • Isophorone diisocyanate: manufactured by Evonik

Claims

1. A composition comprising compound (A-1), said compound (A-1) comprising a repeating unit (A) of formula (A), a structural unit (I) derived from a polyol of formula (I), a structure (C) derived from an oxacyclobutane compound of formula (C), and a terminal hydroxyl group. The composition comprises a structure (C) derived from an oxetane compound, represented by formula (C), in an amount of 0.90–10.7 mol% relative to the sum of the structure (C) derived from the oxetane compound, the structure (D) derived from a diol, represented by formula (D), and the structure (E) derived from a polyol, represented by formula (E). In formula (A), R 1 Indicates alkyldiyl, *1-OR a -*2 or *1-R b -C(=O)-OR c -*2, R a R b and R c Each alkyl group is represented independently; *1 indicates the bonding site with the carbonyl group, and *2 indicates the bonding site with the oxygen atom. In equation (I), R 2 It consists of hydrogen atoms, alkyl groups, or hydroxyalkyl groups; * indicates a connecting bond. In equation (C), R 2 Synonymous with the above, * indicates a connector. In equation (D), R 3 It is a hydrogen atom or an alkyl group, * indicates a connecting bond, R 3 Choose either the same or different from each other. In equation (E), R 2 Synonymous with the above, * represents a connector key.

2. A composition comprising compound (A-1), said compound (A-1) comprising a repeating unit (A) of formula (A) and a structural unit (I) derived from a polyol of formula (I). The content of the structure (C) derived from the oxetane compound shown in formula (C) below is 2.80 to 28 mol% relative to the sum of the structural unit (I) derived from the polyol shown in formula (I) below and the structure (C) derived from the oxetane compound. In formula (A), R 1 Indicates alkyldiyl, *1-OR a -*2 or *1-R b -C(=O)-OR c -*2, R a R b and R c Each alkyl group is represented independently; *1 indicates the bonding site with the carbonyl group, and *2 indicates the bonding site with the oxygen atom. In equation (I), R 2 It consists of hydrogen atoms, alkyl groups, or hydroxyalkyl groups; * indicates a connecting bond. In equation (C), R 2 Synonymous with the above, * represents a connector key.

3. The composition according to claim 1, wherein, The content of the structure (C) derived from the oxetane compound is 2.80–28 mol relative to the sum of the structural unit (I) derived from the polyol and the structure (C) derived from the oxetane compound.

4. The composition according to any one of claims 1 to 3, wherein, R 1 For *1-OR a -*2, R a All are straight-chain alkyl dimethyl groups.

5. The composition according to any one of claims 1 to 3, wherein, R 1 For *1-OR a -*2, R a At least one of them is a branched alkyl diester.

6. The composition according to any one of claims 1 to 3, wherein, R 1 For *1-OR a -*2, and contains two or more alkyl dienes as R a .

7. The composition according to any one of claims 1 to 3, wherein, R 1 Includes *1-OR a -*2, and contains alkyldiyl and / or *1-R b -C(=O)-OR c -*2.

8. The composition according to any one of claims 1 to 3, wherein, R 1 Includes *1-OR a -*2 and alkyldiyl groups.

9. The composition according to any one of claims 1 to 3, further comprising a diol (d) of formula (d), a polyol (e) of formula (e), and an oxetane compound (F) of formula (f). HO-R a -OH (d) In equation (d), R a Synonymous with the above, In equation (e), R 2 Synonymous with the above, In equation (f), R 2 Synonymous with the above.

10. The composition according to any one of claims 1 to 3, further comprising compound (A-2) of formula (A-2), compound (A-3) of formula (A-3), and compound (A-4) of formula (A-4). In equation (A-2), R 1 Synonymous with the above, n 2 R represents an integer greater than or equal to 1, and multiple existing R values. 1 Choose either the same or different from each other. In equation (A-3), R 1 and R 2 Synonymous with the above, n 3 R represents an integer greater than or equal to 1, and multiple existing R values. 1 Choose either the same or different from each other. In equation (A-4), R 1 and R 2 Synonymous with the above, n 4 R represents an integer greater than or equal to 1, and multiple existing R values. 2 Choose either the same or different from each other, R 1 If multiple instances exist, they can be chosen to be the same or different from each other.

11. The composition according to any one of claims 1 to 3, further comprising lithium acetylacetone.

12. A method for manufacturing a composition, comprising the steps of heating a mixture containing a polyol (B1), a diol (D1), a carbonate and a transesterification catalyst, and performing a reflux reaction while removing alcohols derived from the carbonate from the reaction system, thereby obtaining the composition.

13. A method for manufacturing a composition, comprising the following reaction steps: reacting the polycarbonate polyol (B2) with the polyester polyol (C2) in a mixture comprising a polycarbonate polyol (B2), a polyester polyol (C2), and a transesterification catalyst to obtain the compound (A-1). At least one of the polycarbonate polyol (B2) and the polyester polyol (C2) comprises a group represented by formula (I) below, or the mixture further comprises a polyol (E2). In equation (I), R 2 Synonymous with the above, * represents a connector key.

14. The manufacturing method according to claim 12, wherein, The content of the transesterification catalyst in the mixture is 0.001 to 0.050 parts by mass relative to the total amount of the polyol (B1), the diol (D1), and the carbonate in the mixture (100 parts by mass).

15. The manufacturing method according to claim 12, wherein, The content of the transesterification catalyst in the mixture is 0.001 to 0.050 parts by mass relative to 100 parts by mass of the total amount of polycarbonate polyol (B2) and polyester polyol (C2).

16. The manufacturing method according to claim 13, wherein, The transesterification catalyst contains lithium acetylacetone.

17. A polyurethane resin, which is a condensation polymer of a polyol component and a polyisocyanate component, or a crosslinked thereof. The polyol component comprises the composition according to any one of claims 1 to 3.

18. The polyurethane resin according to claim 17, wherein, The polyol component also includes polyols having acidic groups.

19. An aqueous polyurethane resin dispersion comprising: an aqueous medium; and the polyurethane resin or a neutralized thereof of claim 18 dispersed in said aqueous medium.

20. A coating agent comprising the polyurethane resin of claim 17.

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