Composition, urethane resin, and coating film

Abstract

To provide a composition and a urethane resin that are useful for forming a coating film having high tensile strength and elongation at break, and to provide a coating film having high tensile strength and elongation at break.SOLUTION: The present invention provides a composition comprising a compound (A-2) represented by formula (A-2) having a specific structure, and a compound having a specific oxetane structure at one or both terminals of the compound (A-2), wherein the content of the structure derived from the oxetane compound having a specific structure is 2.20 to 20 mol% relative to the total of the structure derived from the oxetane compound and a terminal OH group.SELECTED DRAWING: Figure 1

Description

[Technical field]

[0001] The present disclosure relates to a composition, a urethane resin, and a coating film. [Background technology]

[0002] Compounds having an oxetane structure can be used as curable monomers. Resins obtained by curing such curable monomers are promising raw materials for coating materials, adhesives, and the like.

[0003] Here, Patent Document 1 discloses a hardener composition containing a polycarbonate having a specific structure having an oxetane structure at both ends of the molecule, and a hardener. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] JP 2012-36377 A Summary of the Invention [Problem to be solved by the invention]

[0005] However, in recent years, market demands have become higher, and there is a demand for a higher level of compatibility between tensile strength and elongation at break. For this reason, there is a demand for even higher quality for the curing agent composition disclosed in Patent Document 1. In view of the above, an object of one aspect of the present disclosure is to provide a composition and a urethane resin that contribute to the formation of a coating film having high tensile strength and breaking elongation.An object of another aspect of the present disclosure is to provide a coating film having high tensile strength and breaking elongation. [Means for solving the problem]

[0006] The present disclosure provides the following aspects. [1] A compound (A-2) represented by the following formula (A-2): The composition contains a compound (A-3) represented by the following formula (A-3) and / or a compound (A-4) represented by the following formula (A-4), A composition, wherein the content of structure (B) derived from an oxetane compound represented by the following formula (B) is 2.20 to 20 mol % based on the total content of structure (B) derived from the oxetane compound and structure (C) represented by the following formula (C):

[0007] [ka]

[0008] [In formula (A-2), R 1 is *1-OR a -CH2-*2, *1-R b -C(=O)-OR c -CH2-*2 or *1-R d -CH2-*2, R a , R b , R c , and R d each independently represents an alkanediyl group, *1 indicates the bond site with the carbonyl group. *2 indicates the bond site with the oxygen atom; n 2 indicates an integer equal to or greater than 1; Multiple R's 1 may be the same or different.]

[0009] [ka]

[0010] [In formula (A-3), R 1 is as defined above, R 2 is a hydrogen atom, an alkyl group or a hydroxyalkyl group, n 3 indicates an integer of 1 or more, Multiple R's 1may be the same or different.]

[0011] [ka]

[0012] [In formula (A-4), R 1 and R 2 is as defined above, and n 4 indicates an integer of 1 or more. 2 may be the same or different. 1 When there are multiple, they may be the same or different.

[0013] [ka]

[0014] [In formula (B), R 2 is as defined above, * indicates a bond.]

[0015] [ka]

[0016] [In formula (C), * indicates a bond, R 3 are hydrogen atoms or alkyl groups, and may be the same or different.

[0017] [2] The composition according to [1], further comprising a diol (d) represented by the following formula (d) and an oxetane compound (F) represented by the following formula (f):

[0018] [ka]

[0019] [In formula (d), R ahas the same meaning as above.]

[0020] [ka]

[0021] [In formula (f), R 2 has the same meaning as above.]

[0022] [3] The composition according to [1] or [2], further comprising lithium acetylacetonate.

[0023] [4] A polycondensate of a polyol component and a polyisocyanate component or a crosslinked product thereof, The polyol component comprises the composition according to any one of [1] to [3].

[0024] [5] A coating film comprising the urethane resin described in [4]. Effect of the Invention

[0025] According to one aspect of the present disclosure, a composition and a urethane resin that contribute to the formation of a coating film having high tensile strength and breaking elongation can be provided. According to another aspect of the present disclosure, a coating film having high tensile strength and breaking elongation can be provided. [Brief description of the drawings]

[0026] [Figure 1] FIG. 1 shows a 1H-NMR spectrum of the composition containing the polycarbonate diol obtained in Example 4A. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0027] Hereinafter, the embodiments of each aspect of the present disclosure will be described in detail. In this specification, a numerical range indicated with "~" indicates a range including the numerical values ​​before and after "~" as the minimum and maximum values, respectively. The minimum or maximum value of a numerical range indicated with "~" can be arbitrarily combined with the maximum or minimum value of another numerical range indicated with "~". In addition, the upper and lower limit values ​​individually indicated can also be arbitrarily combined.

[0028] [Composition] A composition according to one embodiment of the present disclosure comprises: A compound (A-2) represented by the following formula (A-2), The composition contains a compound (A-3) represented by the following formula (A-3) and / or a compound (A-4) represented by the following formula (A-4), The content of the structure (B) derived from an oxetane compound represented by the following formula (B) is 2.20 to 20 mol % based on the total content of the structure (B) derived from the oxetane compound and the structure (C) represented by the following formula (C).

[0029] [ka]

[0030] [In formula (A-2), R 1 is *1-OR a -CH2-*2, *1-R b -C(=O)-OR c -CH2-*2 or *1-R d -CH2-*2, R a , R b , R c , and R d each independently represents an alkanediyl group, *1 indicates the bond site with the carbonyl group. *2 indicates the bond site with the oxygen atom; n 2 indicates an integer equal to or greater than 1; Multiple R's 1may be the same or different.]

[0031] [ka]

[0032] [In formula (A-3), R 1 is as defined above, R 2 is a hydrogen atom, an alkyl group or a hydroxyalkyl group, n 3 indicates an integer of 1 or more, Multiple R's 1 may be the same or different.]

[0033] [ka]

[0034] [In formula (A-4), R 1 and R 2 is as defined above, and n 4 indicates an integer of 1 or more. 2 may be the same or different. 1 When there are multiple, they may be the same or different.

[0035] [ka]

[0036] [In formula (B), R 2 is as defined above, * indicates a bond.]

[0037] [ka]

[0038] [In formula (C), * indicates a bond, R 3 are hydrogen atoms or alkyl groups, and may be the same or different.

[0039] The compound (A-2) represented by the formula (A-2) is a polycarbonate diol. Therefore, the composition according to one embodiment of the present disclosure may be a polycarbonate diol composition. In addition, the compound (A-3) represented by formula (A-3) is a polycarbonate monool, and the compound (A-4) represented by formula (A-4) is a polycarbonate compound. Therefore, the composition according to one embodiment of the present disclosure may be a polycarbonate diol composition including a polycarbonate diol, a polycarbonate monool, and a polycarbonate compound.

[0040] -R d The alkanediyl group represented by -CH2- may be linear or branched. d When there are two or more types of alkanediyl groups represented by -CH2-, all of them may be linear alkanediyl groups or branched alkanediyl groups, or some of them may be linear alkanediyl groups and the other parts may be branched alkanediyl groups.

[0041] -R dThe number of carbon atoms in the alkanediyl group represented by -CH2- may be, for example, 2 to 10. Specific examples of the alkanediyl group include an ethanediyl group, a 1,2-propanediyl group, a 1,3-propanediyl group, a 1,2-butanediyl group, a 1,3-butanediyl group, a 1,4-butanediyl group, a 1,5-pentanediyl group, a 2,2-dimethyl-1,3-propanediyl group, a 1,6-hexanediyl group, a 3-methyl-1,5-pentanediyl group, a 1,8-octanediyl group, a 2-ethyl-1,6-hexanediyl group, a 1,9-nonanediyl group, a 2-methyloctane-1,8-diyl group, and a 2-butyl-2-ethyl-1,3-propanediyl group. Among these, a 1,4-butanediyl group, a 1,5-pentanediyl group, a 1,6-hexanediyl group, a 3-methyl-1,5-pentanediyl group, a 2-ethyl-1,6-hexanediyl group, a 1,9-nonanediyl group, a 2-methyloctane-1,8-diyl group, and the like are preferable.

[0042] R a -CH2-, R b , and R c The alkanediyl groups represented by -CH- each independently represent the above-mentioned -R d R may be the same as an alkanediyl group represented by -CH2-. a , R b , and R c The number of carbon atoms of the alkanediyl group represented by R may be, for example, 2 to 10. a When two or more types of alkanediyl groups represented by the formula (I) are present, all of them may be linear alkanediyl groups or branched alkanediyl groups, or some of them may be linear alkanediyl groups and the other may be branched alkanediyl groups. b When two or more types of alkanediyl groups represented by the formula (I) are present, all of them may be linear alkanediyl groups or branched alkanediyl groups, or some of them may be linear alkanediyl groups and the other may be branched alkanediyl groups. c When two or more types of alkanediyl groups represented by the following formula are present, all of them may be linear alkanediyl groups or branched alkanediyl groups, or some of them may be linear alkanediyl groups and the other part may be branched alkanediyl groups.

[0043] The polycarbonate polyol is -R d -CH2-, R a -CH2-, R b or R c When two or more types of alkanediyl groups are contained as -CH2-, all of them may be linear alkanediyl groups or branched alkanediyl groups, or some of them may be linear alkanediyl groups and the other part may be branched alkanediyl groups.

[0044] R 2 The alkyl group and hydroxyalkyl group represented by the formula (I) may be linear or branched. The number of carbon atoms in the alkyl group and hydroxyalkyl group may be, for example, 1 to 6, 2 to 5, or 3 to 4. Specific examples of the alkyl group and hydroxyalkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a pentyl group, a hexyl group, a hydroxymethyl group, a hydroxyethyl group, a hydroxypropyl group, and a hydroxybutyl group. R 2 is preferably an alkyl group or a hydroxyalkyl group, and more preferably an alkyl group or a hydroxyalkyl group having 1 to 2 carbon atoms.

[0045] R 3 The alkyl group represented by the formula may be any alkyl group. For example, the above-mentioned -R d Alkanediyl groups represented by -CH2- and -C(R 3 )2-CH2- may have the same meaning as an alkanediyl group. However, R 3 does not form a ring structure with other atoms. That is, R 3 cannot be part of a ring structure.

[0046] Compound (A-2) to compound (A-4) are R 1 The groups contained as R may be the same. 1 In this case, each of the compounds (A-2) to (A-4) may contain two or more types of groups as R1 The combination of two or more groups contained as R 1 may be the same as a combination of two or more groups included in the formula:

[0047] Compound (A-2) to compound (A-4) are R 2 The groups contained as R may be the same. 2 In this case, each of the compounds (A-2) to (A-4) may contain two or more types of groups as R 2 The combination of two or more groups contained as R 2 may be the same as a combination of two or more groups included in the formula:

[0048] n 2 , n 3 , and n 4 may be 1 to 65, 2 to 60, or 3 to 50.

[0049] The composition containing the compound (A-2) and the compound (A-3) will be described in more detail below, divided into a number of embodiments (first to fourth embodiments).

[0050] (First embodiment) In the first embodiment, the compounds (A-2) to (A-4) each include -R d -CH2- contains only linear alkanediyl groups. That is, -R d All of the -CH2- groups are linear alkanediyl groups. d Since the -CH2- contains only linear alkanediyl groups, the composition tends to be solid at 25°C.

[0051] In the first embodiment, the compounds (A-2) to (A-4) each include -R d It is preferred that the -CH2- group contains only one type of linear alkanediyl group, as this increases the tendency of the composition to become a solid at 25°C.

[0052] The number of carbon atoms in the linear alkanediyl group is preferably 2 to 10, more preferably 2 to 9, and further preferably 4 to 8. Preferred examples of the linear alkanediyl group include a 1,4-butanediyl group, a 1,5-pentanediyl group, a 1,6-hexanediyl group, and a 1,9-nonanediyl group.

[0053] Second embodiment In the second embodiment, the compounds (A-2) to (A-4) each include -R d Compounds (A-2) to (A-4) each contain two or more alkanediyl groups as -CH2-. d Since the composition contains two or more alkanediyl groups as -CH2-, it tends to become liquid at 25°C.

[0054] In the second embodiment, from the viewpoint that a urethane resin having at least one of durability, tensile strength, elongation, and texture is easily formed when used as a raw material for a urethane resin, the compounds (A-2) to (A-4) are each selected from the group consisting of -R d It is preferable that only linear alkanediyl groups are contained as -CH2-. A preferable example of a combination of alkanediyl groups is a combination of two or more kinds of alkanediyl groups having 2 to 10 carbon atoms. A more preferable combination of alkanediyl groups is a combination of 1,6-hexanediol and at least one selected from the group consisting of 1,4-butanediol, 1,5-pentanediol, and 1,9-nonanediol.

[0055] In the second embodiment, the compounds (A-2) to (A-4) each contain -R from the viewpoint that, when used as a raw material for a urethane resin, a urethane resin having at least one of durability, tensile strength, elongation, and texture is easily formed. d The ratio of the number of moles of 1,6-hexanediyl groups to the total number of moles of alkanediyl groups contained as -CH2- 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).

[0056] Third embodiment In the third embodiment, the compounds (A-2) to (A-4) each include -R d The compound (A-2) to the compound (A-4) of the third embodiment each contain a branched alkanediyl group as -CH2-. d Since the composition contains a branched alkanediyl group as -CH2-, it tends to be liquid at 25°C.

[0057] In the third embodiment, the compounds (A-2) to (A-4) each include -R d The compound (A-4) may contain two or more types of alkanediyl groups as -CH2-. The two or more types of alkanediyl groups may all be branched alkanediyl groups, but it is preferable that some of them are linear alkanediyl groups, from the viewpoint that when the compound (A-4) is used as a raw material for a urethane resin, a urethane resin having better handling properties, durability, elongation, and texture is easily formed. In this case, the compound (A-4) may contain -R d The ratio of the number of moles of branched alkanediyl groups to the total number of moles of alkanediyl groups contained as -CH2- is preferably 0.10 to 1.00, more preferably 0.20 to 0.90, even more preferably 0.30 to 0.70, and still more preferably 0.40 to 0.60.

[0058] The number of carbon atoms in the branched alkanediyl group is preferably 2 to 10, more preferably 3 to 9, and even more preferably 4 to 8. The number of carbon atoms in the main chain (straight chain having the largest number of carbon atoms) of the branched alkanediyl group is preferably 2 to 9, more preferably 3 to 8, and even more preferably 4 to 7. Preferred examples of the branched alkanediyl group are a 3-methylpentane-1,5-diyl group and a 2-methyl-1,8-octanediyl group.

[0059] The number of carbon atoms in the linear alkanediyl group is preferably 2 to 10, more preferably 3 to 9, and further preferably 4 to 8. Preferred examples of the linear alkanediyl group include a 1,4-butanediyl group, a 1,5-pentanediyl group, a 1,6-hexanediyl group, and a 1,9-nonanediyl group.

[0060] In the third embodiment, the compounds (A-2) to (A-4) each contain -R from the viewpoint that, when used as a raw material for a urethane resin, a urethane resin having at least one of better handling properties, durability, elongation, and texture is easily formed. d The ratio of the number of moles of 1,6-hexanediyl groups to the total number of moles of alkanediyl groups contained as -CH2- 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).

[0061] (Fourth embodiment) In the fourth embodiment, the compounds (A-2) to (A-4) are each R 1 *1-OR a -CH2-*2 and *1-R d -CH2-*2 and / or *1-R b -C(=O)-OR c The compounds (A-2) to (A-4) of the fourth embodiment each include R 1 *1-OR a -CH2-*2 and *1-R d -CH2-*2 and / or *1-R b -C(=O)-OR c Since the composition contains -CH2-*2, it tends to become liquid at 25°C.

[0062] In the fourth embodiment, the property of the composition is not particularly limited, and may be a solid at 25° C. or a liquid at 25° C. The property of the composition is such that the compound (A-2) to the compound (A-4) each have -R d-CH2-, R a -CH2-, R b , or R c The type of alkanediyl group contained as -CH2- (the number of carbon atoms, the presence or absence of branching, etc.) and the hydroxyl value of the compound (A-2) and the compound (A-3) can be changed. For example, in the compound (A-2) to the compound (A-4), -R d -CH2-, R a -CH2-, R b or R c When the total number of moles of branched alkanediyl groups in compounds (A-2) to (A-4) relative to the total number of moles of alkanediyl groups contained as -CH2- is 0.2 to 1.0, and when the hydroxyl values ​​of compounds (A-2) and (A-3) are high, the composition tends to become a liquid at 25°C.

[0063] In the fourth embodiment, from the viewpoint that a urethane resin excellent in durability such as heat resistance, moist heat resistance, hot water resistance, etc. is easily formed when used as a raw material for a urethane resin, R 1 *1-R d -CH2-*2 and *1-OR a It is more preferred that it is -CH2-*2.

[0064] In the fourth embodiment, the compounds (A-2) to (A-4) each contain -R from the viewpoint that, when used as a raw material for a urethane resin, a urethane resin having at least one of 100% modulus and heat resistance that is more excellent is easily formed. d Alkanediyl groups included as -CH2- and *1-OR a -CH2-*2 and *1-R b -C(=O)-OR c R relative to the total number of moles of -CH2-*2 1 Included as *1-OR aThe ratio of the number of moles of -CH2-*2 is preferably 0.10 or more (for example, 0.10 to 0.90), more preferably 0.20 or more (for example, 0.20 to 0.80), further preferably 0.30 or more (for example, 0.30 to 0.70), and particularly preferably 0.40 or more (for example, 0.40 to 0.60).

[0065] <Raw materials> Compound (A-2) to compound (A-4) described in the first to third embodiments may be, for example, a reaction product of a diol represented by the following formula (d) (hereinafter also referred to as "diol (D1)"), a carbonate ester, and an oxetane compound represented by the following formula (f) (hereinafter also referred to as "oxetane compound (F1)").

[0066] [ka]

[0067] [In formula (d), R a has the same meaning as above.]

[0068] [ka]

[0069] [In formula (f), R 2 has the same meaning as above.]

[0070] Specific examples of the diol (D1) include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 2,2-dimethyl-1,3-propanediol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, 1,8-octanediol, 2-ethyl-1,6-hexanediol, 1,9-nonanediol, 2-methyloctane-1,8-diol, and 2-butyl-2-ethyl-1,3-propanediol. These may be used alone or in combination of two or more.

[0071] Examples of carbonate esters include dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, dipropyl carbonate, dibutyl carbonate, diphenyl carbonate, ethylene carbonate, trimethylene carbonate, and 1,2-propylene carbonate. These may be used alone or in combination of two or more. From the viewpoints of availability and ease of setting polymerization reaction conditions, it is preferable to use at least one selected from the group consisting of dimethyl carbonate, diethyl carbonate, diphenyl carbonate, dibutyl carbonate, and ethylene carbonate.

[0072] Examples of the oxetane compound (F1) include 3-ethyl-3-hydroxymethyloxetane, 3-methyl-3-hydroxymethyloxetane, and 3,3-dihydroxymethyloxetane. These may be used alone or in combination of two or more.

[0073] The compounds (A-2) to (A-4) described in the fourth embodiment may be, for example, a reaction product of a polycarbonate diol (B2-1) and a polyester diol (C2-1). They may also be a reaction product of a polycarbonate diol (B2-1), a polyester diol (C2-1), and an oxetane compound (F2). Furthermore, the compounds (A-2) to (A-4) may be a reaction product of a polycarbonate diol (B2-1), a polyester diol (C2-1), a diol (D2) and / or a polyhydric alcohol (E2). In addition, they may be a reaction product of a polycarbonate diol (B2-1), a polyester polyol diol (C2-1), an oxetane compound (F2), a diol (D2) and / or a polyhydric alcohol (E2).

[0074] The polycarbonate diol (B2-1) may be used alone or in combination of two or more kinds.

[0075] The polycarbonate polyol (B2-1) may, for example, be one obtained by reacting a carbonate ester with a diol.

[0076] Examples of the carbonate ester and diol that can be used in the reaction to obtain the polycarbonate polyol (B2-1) include the same carbonate ester and diol (D1) as those described in the description of the compound (A-3) and the compound (A-4) in the first to third embodiments.

[0077] The polyester diol (C2-1) may be one type alone or a combination of two or more types.

[0078] Examples of the polyester diol (C2-1) include the following polyester polyols (α) to (β) and any combination of two or more of these. (α) A polyester polyol (polyester polyol (α)) obtained from a diol (C2-1-1) and a dicarboxylic acid and / or anhydride thereof (C2-1-2). (β) A polyester polyol (polyester polyol (β)) obtained by ring-opening addition polymerization of a cyclic ester compound (C2-1-4) such as a lactone using a diol (C2-1-1) as an initiator. The polyester polyol (β) can be said to be a ring-opening addition polymer of a cyclic ester compound using a diol as an initiator.

[0079] The diol (C2-1-1) may be the same as the diol (D1) described in the description of the compound (A-3) and the compound (A-4) in the first to third embodiments. Among them, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,9-nonanediol, 3-methyl-1,5-pentanediol, and 2-methyl-1,8-octanediol are preferred.

[0080] Examples of dicarboxylic acids and / or anhydrides thereof (C2-1-2) include phthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, cyclohexanedicarboxylic acid, maleic acid, fumaric acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, sebacic acid, dodecanedioic acid, hydrogenated dimer fatty acid, and the like, tartaric acid, and anhydrides thereof, and combinations of any two or more thereof.

[0081] Examples of the cyclic ester compound (C2-1-4) include β-propiolactone, β-butyrolactone, γ-butyrolactone, β-valerolactone, γ-valerolactone, δ-valerolactone, α-caprolactone, β-caprolactone, γ-caprolactone, δ-caprolactone, ε-caprolactone, α-methyl-ε-caprolactone, β-methyl-ε-caprolactone, 4-methylcaprolactone, γ-caprylolactone, ε-caprylolactone, ε-palmitolactone, and the like, and combinations of any two or more of these. Among these, a ring-opening addition polymer of ε-caprolactone using trimethylolpropane as an initiator is preferred from the standpoint of stability during polymerization and economic efficiency.

[0082] In the fourth embodiment, it is more preferable that the polyester diol (C2-1) contains a polyester polyol (β), from the viewpoint that when used as a raw material for a urethane resin, a urethane resin having excellent durability such as heat resistance or moist heat resistance is easily formed.

[0083] Examples of the diol (D2) include the same diols (D1) as those mentioned in the description of the compounds (A-3) and (A-4) in the first to third embodiments.

[0084] An example of the polyhydric alcohol (E2) is a polyhydric alcohol represented by the following formula (b) (hereinafter, also referred to as "polyhydric alcohol (E2)").

[0085] [ka]

[0086] [In formula (b), R 2 is a hydrogen atom, an alkyl group, or a hydroxyalkyl group.

[0087] Specific examples of the polyhydric alcohol (E2) include trimethylolpropane, trimethylolethane, glycerin, pentaerythritol, and sorbitol. These may be used alone or in combination of two or more.

[0088] Examples of the oxetane compound (F2) include the same oxetane compounds (F1) as those mentioned in the description of the compounds (A-3) and (A-4) in the first to third embodiments.

[0089] <Other ingredients> <Diol (d)> The composition of the present embodiment includes compounds (A-2) to (A-4). The composition may further include a diol represented by the following formula (d) (hereinafter, also referred to as "diol (d)").

[0090] [ka]

[0091] [In formula (d), R a has the same meaning as above.]

[0092] The diol (d) has the same meaning as the diol (D1) described above, and the diol (d) is R a The alkanediyl group having as —CH2— is R a It may be the same as an alkanediyl group contained as -CH2-.

[0093] Diol (d) to R a The alkanediyl group contained as -CH2- is R in the compound (A-1) -CH2-. aThe alkanediyl group may be the same as the alkanediyl group contained as R a When the composition contains two or more compounds (A-2) to (A-4) each having a different alkanediyl group represented by —CH—, the composition is a The compound may contain two or more diols (d) having different alkanediyl groups represented by -CH2-. In this case, the compound corresponding to the diol (d) may have R a The combination of groups contained as -CH2- is R in multiple compounds corresponding to compounds (A-2) to (A-4). a It may be the same as the combination of groups contained in -CH2-.

[0094] Examples of the diol (d) include the same diols (D1) as those mentioned in the description of the compounds (A-2) to (A-4) in the first to third embodiments.

[0095] <Oxetane Compounds (F)> The composition may further contain an oxetane compound represented by the following formula (f) (hereinafter also referred to as "oxetane compound (F)").

[0096] [ka]

[0097] [In formula (f), R 2 has the same meaning as above.]

[0098] The oxetane compound (F) has the same meaning as described above, and the oxetane compound (F) is R 2 The alkyl group and the hydroxyalkyl group represented by R 2 may be the same as the atom or group contained as

[0099] Oxetane compound (F) R 2 The atoms or groups contained as R in the compounds (A-2) to (A-4). 2 The atom or group may be the same as that included as R2 When the composition contains two or more compounds (A-2) to (A-4) having different alkanediyl groups represented by R 2 In this case, the oxetane compound (F) may contain two or more kinds of oxetane compounds having different alkanediyl groups represented by R 2 The combination of groups included as R is included in multiple compounds corresponding to compounds (A-2) to (A-4). 2 may be the same as the combination of groups included in

[0100] Examples of the oxetane compound (F) include the same oxetane compound (F1) as described in the description of the compounds (A-2) to (A-4) in the first to third embodiments.

[0101] In the following description, the total number of moles of the group represented by the following formula (B) contained in the composition is represented by C B The total number of moles of the group represented by the following formula (C) is C C Let us assume that.

[0102] [ka]

[0103] [In formula (B), R 2 is a hydrogen atom, an alkyl group or a hydroxyalkyl group, * indicates a bond.]

[0104] [ka]

[0105] [In formula (C), * indicates a bond, R 3 are hydrogen atoms or alkyl groups, and may be the same or different.

[0106] The total number of moles of the group represented by the above formula (B) contained in the composition is CB The total number of moles of the group represented by the above formula (C) contained in the composition is C C Then, the molar ratio (C B / (C B +C C ) × 100) may be 2.20 to 20.0. Hereinafter, "molar ratio (C B / (C B +C C ) × 100) is sometimes referred to as "molar ratio α." When the molar ratio α is within the above range, when the composition is used as a raw material for a urethane resin, a urethane resin that has both good elongation at break and high tensile strength tends to be formed.

[0107] The lower limit of the molar ratio α may be, for example, 2.50 or more, 3.50 or more, 4.50 or more, 6.00 or more, 7.00 or more, 8.00 or more, 10.00 or more, 12.00 or more, or 14.00 or more. The upper limit of the molar ratio α may be, for example, 18.00 or less, 16.00 or less, 15.00 or less, 13.00 or less, 11.50 or less, 10.00 or less, 8.00 or less, 6.50 or less, 5.00 or less, 4.00 or less, or 3.00 or less.

[0108] The molar ratio α is, for example, the ratio of the composition of deuterated chloroform to the standard substance. 1 H-NMR measurement and the results obtained by the measurement 1 It can be determined from the integral value of the signal in the H-NMR spectrum. Specifically, for example, the integral value Δ SB (4 mol of hydrogen atoms) and the integral value Δ of the methylene signal (SC) located next to the hydroxyl group of the group represented by formula (C) SC (2 mol of hydrogen atoms) and the molar ratio (C B / (C B +C C ) × 100) can be calculated. In this case, the molar ratio α is the integral value Δ SB and the integral value of the signal (SC), Δ SC Using (ΔSB / Δ SB +2Δ SC × 100).

[0109] In the first to fourth embodiments, deuterated chloroform is used as a solvent, and tetramethylsilane is used as a reference substance to measure the composition. 1 When H-NMR measurement is performed, for example, the above signal (SB) is 1 The signal (SC) is observed in the range of 4.390 ppm to 4.500 ppm in the H-NMR spectrum. 1 It is observed in the range of 3.580 ppm or more and 3.710 ppm or less in the H-NMR spectrum. Therefore, in the first to fourth embodiments, the molar ratio α can be obtained from the ratio of the integral values ​​of these signals.

[0110] <Catalyst> The composition may further contain a catalyst. Lithium acetylacetonate is preferably used as the catalyst. The content of the catalyst may be 0.0001 to 0.100% by mass based on the total mass of the composition.

[0111] The properties of the composition are not particularly limited, and may be a solid or a liquid at 25° C. The properties of the composition can be changed depending on the types and content ratios of the components contained (e.g., compounds (A-2) to (A-4), diol (d), polyhydric alcohol (E2), and oxetane compound (F)).

[0112] The number average molecular weight of the composition may be, for example, 200 to 6000 g / mol. The lower limit of the number average molecular weight of the composition may be, for example, 200 g / mol or more, 400 g / mol or more, 600 g / mol or more, 800 g / mol or more, 1000 g / mol or more, 1200 g / mol or more, 1400 g / mol or more, 1600 g / mol or more, or 1800 g / mol or more. The upper limit of the number average molecular weight of the composition may be, for example, 6000 g / mol or less, 5000 g / mol or less, 4000 g / mol or less, 3000 g / mol or less, 2500 g / mol or less, 2000 g / mol or less, 1800 g / mol or less, 1600 g / mol or less, 1400 g / mol or less, 1200 g / mol or less, 1000 g / mol or less, or 800 g / mol or less.

[0113] The number average molecular weight of the composition is the number average molecular weight calculated as a difunctional polyoxypropylene polyol, measured by using GPC (gel permeation chromatography) with the entire composition as the measurement subject.

[0114] The deemed hydroxyl value of the composition may be, for example, 30 to 400 mgKOH / g. The lower limit of the deemed hydroxyl value of the composition may be, for example, 30 mgKOH / g or more, 40 mgKOH / g or more, 50 mgKOH / g or more, 60 mgKOH / g or more, or 70 mgKOH / g or more. The upper limit of the deemed hydroxyl value of the composition may be, for example, 300 mgKOH / g or less, 200 mgKOH / g or less, 100 mgKOH / g or less, or 80 mgKOH / g or less.

[0115] According to this embodiment, it is possible to provide a composition that contributes to the formation of a coating film having high tensile strength and breaking elongation.

[0116] <Urethane resin and its manufacturing method> The urethane resin is a polycondensate of a polyol component and a polyisocyanate component, or a crosslinked product thereof. Here, the crosslinked product means a product in which polycondensates are crosslinked with each other by a chain extender, etc. Here, the polyol component includes the above-mentioned composition.

[0117] (Polyisocyanate) Examples of polyisocyanates include aromatic polyisocyanates, araliphatic polyisocyanates, aliphatic polyisocyanates, and alicyclic polyisocyanates. Modified polyisocyanates, which are modified versions of these, can also be used. Examples of modified polyisocyanates include isocyanurate-modified polyisocyanates (isocyanate trimers), allophanate-modified polyisocyanates, uretdione-modified polyisocyanates, urethane-modified polyisocyanates, biuret-modified polyisocyanates, uretonimine-modified polyisocyanates, and acylurea-modified polyisocyanates. These can be used alone or in combination of two or more.

[0118] Examples of aromatic isocyanates include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, a mixture of 2,4-tolylene diisocyanate and 2,6-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, a mixture of 2,4'-diphenylmethane diisocyanate and 4,4'-diphenylmethane diisocyanate, m-xylylene diisocyanate, p-xylylene diisocyanate, and 4,4'-diphenyl ether. Examples of the diisocyanates include phenyl diisocyanate, 2-nitrodiphenyl-4,4'-diisocyanate, 2,2'-diphenylpropane-4,4'-diisocyanate, 3,3'-dimethyldiphenylmethane-4,4'-diisocyanate, 4,4'-diphenylpropane diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate, naphthylene-1,4-diisocyanate, naphthylene-1,5-diisocyanate, and 3,3'-dimethoxydiphenyl-4,4'-diisocyanate.

[0119] Examples of aromatic aliphatic isocyanates include 1,3-xylylene diisocyanate, 1,4-xylylene diisocyanate, and mixtures thereof; 1,3-bis(1-isocyanato-1-methylethyl)benzene, 1,4-bis(1-isocyanato-1-methylethyl)benzene, and mixtures thereof; ω,ω'-diisocyanato-1,4-diethylbenzene, and the like.

[0120] Examples of aliphatic isocyanates include hexamethylene diisocyanate, pentamethylene diisocyanate, tetramethylene diisocyanate, 2-methylpentane-1,5-diisocyanate, 3-methylpentane-1,5-diisocyanate, lysine diisocyanate, trioxyethylene diisocyanate, ethylene diisocyanate, trimethylene diisocyanate, octamethylene diisocyanate, nonamethylene diisocyanate, 2,2'-dimethylpentane diisocyanate, 2,2,4-trimethylhexane diisocyanate, decamethylene diisocyanate, butene diisocyanate, 1,3-butadiene-1,4-diisocyanate, 2,4,4 -trimethylhexamethylene diisocyanate, 1,6,11-undecane triisocyanate, 1,3,6-hexamethylene triisocyanate, 1,8-diisocyanato-4-(isocyanatomethyl)octane, 2,5,7-trimethyl-1,8-diisocyanato-5-(isocyanatomethyl)octane, bis(isocyanatoethyl)carbonate, bis(isocyanatoethyl)ether, 1,4-butylene glycol dipropyl ether-α,α'-diisocyanate, lysine diisocyanatomethyl ester, 2-isocyanatoethyl-2,6-diisocyanatohexanoate, 2-isocyanatopropyl-2,6-diisocyanatohexanoate, and the like.

[0121] Examples of alicyclic isocyanates include isophorone diisocyanate, cyclohexyl diisocyanate, bis(isocyanatomethyl)cyclohexane, dicyclohexylmethane diisocyanate, methylcyclohexyl diisocyanate, dicyclohexyldimethylmethane diisocyanate, 2,2'-dimethyldicyclohexylmethane diisocyanate, bis(4-isocyanato-n-butylidene)pentaerythritol, and hydrogenated dimer acid diisocyanate. 2-isocyanatomethyl-3-(3-isocyanatopropyl)-5-(isocyanatomethyl)bicyclo[2.2.1]heptane, 2-(isocyanatomethyl)3-(3-isocyanatopropyl)-6-(isocyanatomethyl)-bicyclo[2.2.1]heptane, 2-(isocyanatomethyl)-2-(3-isocyanatopropyl)-5-(isocyanatomethyl)bicyclo[2.2.1]heptane, 2-(isocyanatomethyl)-2-(3-isocyanatopropyl)-5-(isocyanatomethyl)bicyclo[2.2.1]heptane, 2-(isocyanatomethyl)-2-(3-isocyanatopropyl)- 2-(isocyanatomethyl)-3-(3-isocyanatopropyl)-5-(2-isocyanatoethyl)bicyclo[2.2.1]heptane, 2-(isocyanatomethyl)-3-(3-isocyanatopropyl)-6-(2-isocyanatoethyl)bicyclo[2.2.1]heptane, 2-(isocyanatomethyl)-2-(3-isocyanatopropyl)-5-(2-isocyanatoethyl)bicyclo[2.2.1]heptane, Examples of such diisocyanates include cyclo[2.2.1]heptane, 2-(isocyanatomethyl)-2-(3-isocyanatopropyl)-6-(2-isocyanatoethyl)bicyclo[2.2.1]heptane, 2,5-bis(isocyanatomethyl)bicyclo[2.2.1]heptane, hydrogenated diphenylmethane diisocyanate, norbornane diisocyanate, hydrogenated tolylene diisocyanate, hydrogenated xylene diisocyanate, and hydrogenated tetramethylxylene diisocyanate.

[0122] (Polyol component / polyisocyanate component blend ratio) The blending ratio of the polyol component to the polyisocyanate component, expressed as the molar ratio of active hydrogen in the polyol component to isocyanate groups in the polyisocyanate component, is preferably 9:1 to 1:9, and more preferably 6:4 to 4:6. When the blending ratio is within this range, the urethane resin tends to have better performance.

[0123] (Chain extender) The chain extender can be appropriately selected depending on the purpose, use, etc. Examples of the chain extender include water, ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, 1,10-decanediol, 1,1-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, tricyclodecane dimethanol, xylylene glycol, bis(p-hydroxy)diphenyl, bis(p-hydroxyphenyl)propane, 2,2-bis[4-(2-hydroxyethoxy)phenyl]propane, and bis[4-(2-hydroxyethoxy)phenyl]sulfone. , 1,1-bis[4-(2-hydroxyethoxy)phenyl]cyclohexane and other low molecular weight polyols; polyester polyols, polyesteramide polyols, polyether polyols, polyether ester polyols, polycarbonate polyols, polyolefin polyols and other high molecular weight polyols; ethylene diamine, isophorone diamine, 2-methyl-1,5-pentanediamine, aminoethylethanolamine, diethylene triamine, triethylene tetramine, tetraethylene pentamine, pentaethylene hexamine and other polyamines can be used. The amount of the chain extender (the ratio of the structure derived from the chain extender contained in the urethane resin) may be 0.1 to 50 parts by mass relative to 100 parts by mass of the total amount of the polyol component and the polyisocyanate component. When the chain extender is a polyol, the content of the polyol is calculated assuming that it is included in both the chain extender and the polyol component.

[0124] The urethane resin can be obtained by reacting a polyol component, a polyisocyanate component, and optionally a chain extender (urethanization reaction). The urethane reaction may be carried out at room temperature (e.g., 25°C) or under heating (e.g., 40 to 200°C).

[0125] In the urethanization reaction, a catalyst (urethanization catalyst) can be added for the purpose of shortening the reaction time, improving the reaction rate, etc. Examples of the catalyst include tertiary amine catalysts such as triethylamine, triethylenediamine, tetramethylethylenediamine, tetramethylpropylenediamine, and tetramethylhexamethylenediamine, and metal catalysts such as tin-based catalysts such as stannous octoate, stannous oleate, and dibutyltin dilaurate. These can be used alone or in combination of two or more. Among these, dibutyltin dilaurate is preferably used. The amount of the catalyst used may be 0.001 to 100 parts by mass with respect to 100 parts by mass of the total amount of the polyol component and the polyisocyanate component.

[0126] When a catalyst is used in the urethanization reaction, it is preferable to use a phosphorus compound for treating the catalyst. The phosphorus compound is not particularly limited, and examples thereof include phosphate triesters such as trimethyl phosphate, triethyl phosphate, tributyl phosphate, di-2-ethylhexyl phosphate, triphenyl phosphate, tricresyl phosphate, and cresyl diphenyl phosphate; acid phosphate esters such as methyl acid phosphate, ethyl acid phosphate, propyl acid phosphate, isopropyl acid phosphate, butyl acid phosphate, lauryl acid phosphate, stearyl acid phosphate, 2-ethylhexyl acid phosphate, isodecyl acid phosphate, butoxyethyl acid phosphate, oleyl acid phosphate, tetracosyl acid phosphate, acetylene glycol acid phosphate, 2-hydroxyethyl methacrylate acid phosphate, dibutyl phosphate, monobutyl phosphate, monoisodecyl phosphate, and bis(2-ethylhexyl)phosphate; and triphenyl phosphate. phosphite, trisnonylphenyl phosphite, tricresyl phosphite, triethyl phosphite, tris(2-ethylhexyl) phosphite, tridecyl phosphite, trilauryl phosphite, tris(tridecyl) phosphite, trioleyl phosphite, diphenyl mono(2-ethylhexyl) phosphite, diphenyl monodecyl phosphite, diphenyl (monodecyl) phosphite, trilauryl phosphite, diethyl hydrogen phosphite, bis(2-ethylhexyl) Examples of such phosphite esters include bis(decyl)pentaerythritol diphosphite, tristearyl phosphite, distearyl pentaerythritol diphosphite, tris(2,4-di-tert-butylphenyl)phosphite, and other phosphite esters; phosphoric acid, phosphorous acid, and hypophosphorous acid. These may be used alone or in combination of two or more.Among these, acidic phosphoric acid esters are preferred, and 2-ethylhexyl acid phosphate is more preferred. The amount of the phosphorus compound used may be 10 to 2000 parts by mass based on 100 parts by mass of the catalyst.

[0127] The urethanization reaction can be carried out in the presence of a solvent. Examples of the solvent include esters such as ethyl acetate, butyl acetate, propyl acetate, γ-butyrolactone, δ-valerolactone, and ε-caprolactone; amides such as dimethylformamide, diethylformamide, and dimethylacetamide; sulfoxides such as dimethylsulfoxide; ethers such as tetrahydrofuran, dioxane, and 2-ethoxyethanol; ketones such as methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; and aromatic hydrocarbons such as benzene and toluene.

[0128] The urethane resin described above has good elongation and texture, excellent durability, and in some cases good breaking strength. Therefore, the urethane resin can be suitably used for synthetic leather, artificial leather, coating agents, etc.

[0129] <Coating film> The coating film of the present embodiment contains the above-mentioned urethane resin. Specific aspects of the urethane resin may be as described above.

[0130] <Two-liquid composition set> The polyol component and the polyisocyanate component for forming the urethane resin may be stored, transported, etc., in separate containers as a two-liquid composition set. The two-liquid composition set includes a first liquid containing at least the polyol component and a second liquid containing at least the polyisocyanate component. When a chain extender, a catalyst, a solvent, etc. are used, they may be contained in the first liquid and / or the second liquid, or may be mixed separately from the first liquid and the second liquid. The two-liquid composition set can be suitably used, for example, as a coating agent, and can also be suitably used in the production of artificial leather, synthetic leather, exterior paint, interior paint, etc. When the two-liquid composition set is used as a coating agent, for example, after mixing the first liquid and the second liquid, the resulting mixed liquid is applied to a substrate, and optionally heated to form a coating film (for example, a cured film containing a urethane resin).

[0131] <Application> The composition and urethane resin of the present embodiment described above can be used in a coating composition that is preferably used as a clear coating for automobile exteriors and a coating for automobile interiors. The coating film of the present embodiment described above can be preferably used as a clear coating film for automobile exteriors and a coating film for automobile interiors. The composition, urethane resin, and coating film of this embodiment can be preferably used in the surface treatment of home appliances, OA (office automation) products, leather, synthetic leather, and the like. EXAMPLES

[0132] Examples of the present invention will be described below, but the present invention is not limited to these examples.

[0133] <Example> <<First Example>> Details of the materials used in the examples shown below are as follows: N-980N: Nipolan 980N (product name), polycarbonate diol, manufactured by Tosoh Corporation 1,6-Hexanediol: BASF JAPAN 3-Ethyl-3-hydroxymethyloxetane: manufactured by Tokyo Chemical Industry Co., Ltd. Lithium acetylacetonate: Sigma-Aldrich C-2612: Coronate 2612 (trade name), hexamethylene diisocyanate adduct modified polyisocyanate, isocyanate content = 17.2%, manufactured by Tosoh Corporation JP-508: Product name, 2-ethylhexyl acid phosphate, manufactured by Johoku Chemical Industry Co., Ltd. DOTDL: Dioctyltin dilaurate, manufactured by Kishida Chemical Industry Co., Ltd. Methyl ethyl ketone: Maruzen Petrochemical Co., Ltd. Toluene: Fujifilm Wako Pure Chemical Industries, Ltd. BYK-331: Silicone surface conditioner, manufactured by BYK

[0134] Example 1A 289.9g of N-980N, 8.0g of 1,6-hexanediol, 2.06g of 3-ethyl-3-hydroxymethyloxetane, and 0.015g of lithium acetylacetonate were mixed in a 1L two-neck glass reactor equipped with a stirrer, a thermometer, a heating device, a fractionator filled with structured packing, and a cooler. The resulting mixture was reacted for 5 hours while heating at 150°C under normal pressure to obtain a composition (PCD-1A) containing compounds (A-2) to (A-4).

[0135] Example 2A A composition (PCD-2A) containing compounds (A-2) to (A-4) was obtained in the same manner as in Example 1A, except that 7.1 g of 1,6-hexanediol and 3.03 g of 3-ethyl-3-hydroxymethyloxetane were added.

[0136] Example 3A A composition (PCD-3A) containing compounds (A-2) to (A-4) was obtained in the same manner as in Example 1A, except that 6.6 g of 1,6-hexanediol and 3.51 g of 3-ethyl-3-hydroxymethyloxetane were added.

[0137] Example 4A A composition (PCD-4A) containing compounds (A-2) to (A-4) was obtained in the same manner as in Example 1A, except that 6.1 g of 1,6-hexanediol and 3.97 g of 3-ethyl-3-hydroxymethyloxetane were added.

[0138] Example 5A A composition (PCD-5A) containing compounds (A-2) to (A-4) was obtained in the same manner as in Example 1A, except that 5.2 g of 1,6-hexanediol and 4.87 g of 3-ethyl-3-hydroxymethyloxetane were added.

[0139] Example 6A A composition (PCD-6A) containing compounds (A-2) to (A-4) was obtained in the same manner as in Example 1A, except that 290.0 g of N-980N, 1.0 g of 1,6-hexanediol, and 8.94 g of 3-ethyl-3-hydroxymethyloxetane were added.

[0140] Comparative Example 1A N-980N was used as is (PCD-7A).

[0141] (Comparative example 2A) A composition (PCD-8A) containing compounds (A-2) to (A-4) was obtained in the same manner as in Example 1A, except that 9.1 g of 1,6-hexanediol and 1.05 g of 3-ethyl-3-hydroxymethyloxetane were added.

[0142] (Comparative example 3A) A composition (PCD-9A) containing compounds (A-2) to (A-4) was obtained in the same manner as in Example 1A, except that 284.9 g of N-980N, 0.5 g of 1,6-hexanediol, and 14.6 g of 3-ethyl-3-hydroxymethyloxetane were added.

[0143] (Comparative example 4A) A composition (PCD-10A) containing compounds (A-2) to (A-4) was obtained in the same manner as in Example 1A, except that 277.4 g of N-980N, 0.5 g of 1,6-hexanediol, and 22.1 g of 3-ethyl-3-hydroxymethyloxetane were added.

[0144] (Analysis and Evaluation) [Measurement of number average molecular weight] The composition obtained above was subjected to GPC analysis under the following conditions to measure the number average molecular weight of the polycarbonate diol and the number average molecular weight of the composition. The results are shown in Table 1A. -conditions- (1) Measuring instrument: HLC-8420 (manufactured by Tosoh Corporation) (2) Column: TSKgel (Tosoh Corporation) G3000H-XL G3000H-XL G2000H-XL G2000H-XL (3) Mobile phase: THF (tetrahydrofuran) (4) Detector: RI (refractive index) detector (accessory for HLC-8420) (5) Temperature: 40℃ (6)Flow rate: 1.000ml / min (7) Calibration curve: A calibration curve was obtained using the following products (all bifunctional polyoxypropylene polyols manufactured by Sanyo Chemical Industries, Ltd.). "Sannix PP-200" (number average molecular weight = 200, average number of functional groups: 2) "Sannix PP-400" (number average molecular weight = 400, average number of functional groups: 2) "Sannix PP-1000" (number average molecular weight = 1000, average number of functional groups: 2) "Sannix PP-2000" (number average molecular weight = 2000, average number of functional groups: 2) "Sannix PP-3000" (number average molecular weight = 3200, average number of functional groups: 2) "Sannix PP-4000" (number average molecular weight = 4160, average number of functional groups: 2) (8) Approximation of calibration curve: Cubic equation (9) Sample solution concentration: 0.5% by mass in THF solution

[0145] [Measurement of complete acetylation] The composition was acetylated for 2 hours using an acetylating agent according to JIS K1557-1, and then the hydroxyl value of the composition was measured. The results are shown in Table 1A.

[0146] [Calculation of deemed hydroxyl value] The complete acetylation number obtained above was multiplied by a correction factor to calculate the assumed hydroxyl value. The correction factor is, for example, the hydroxyl value of the composition using deuterated chloroform as a solvent and tetramethylsilane as a standard substance. 1 H-NMR measurement and the results obtained by the measurement 1 It can be determined from the integral value of the signal in the H-NMR spectrum. Specifically, for example, the integral value Δ SB (4 mol of hydrogen atoms) and the integral value Δ of the methylene signal (SC) located next to the hydroxyl group of the group represented by formula (C) SC (2 mol of hydrogen atoms) and the correction factor can be calculated using the integral value Δ SB and the integral value of the signal (SC), Δ SC Using ((Δ SB +2Δ SC ) / (3Δ SB +2Δ SC ) × 100). The results are shown in Table 1A.

[0147] [Composition analysis] The composition (sample) obtained above was dissolved in deuterated chloroform (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) to obtain a solution. Tetramethylsilane (TMS) was added to the solution as a chemical shift standard to obtain a test solution. The obtained test solution was analyzed using a JNM-ECX400 manufactured by JEOL Ltd. 1 Measure H-NMR and set the TMS signal at 0 ppm. 1 For reference, the H-NMR spectrum of the composition obtained in Example 4A was 1The H-NMR spectrum is shown in Figure 1. The measurement was carried out under the following conditions.

[0148] -conditions- ·Resonance frequency: 400MHz Pulse width: 45degree Waiting time: 5 seconds Number of times: 64 Sample solution concentration (TMS-containing deuterated chloroform): 3% by mass

[0149] Next, 1 From the H-NMR spectrum, the integral value Δ of the methylene signal (SB) located next to the oxygen atom of the oxetane group of the group represented by the above formula (B) is SB and the integral value Δ of the methylene signal (SC) located next to the hydroxyl group of the group represented by formula (C) SC He asked.

[0150] Specifically, a signal between 4.390 ppm and 4.500 ppm was defined as signal (SB), and a signal between 3.580 ppm and 3.710 ppm was defined as signal (SC). In the second and third examples described later, the signal (SC) was defined as 3.580 ppm or more and 3.760 ppm or less in order to calculate the value accurately. The baseline for the integral value measurement was a horizontal line drawn by comparing the spectral intensities in a specified spectral range and using the lowest spectral intensity as the standard. From the obtained integral value, the molar ratio (C B / (C B +C C ) × 100) was calculated. The results are shown in Table 1A.

[0151] [Table 1A]

[0152] In Table 1A, the "mixture" (unit: g) for Examples 1A to 6A and Comparative Examples 1A to 4A indicates the reaction raw materials.

[0153] (Physical property evaluation) A cured urethane coating (film) was prepared by the following method, and the physical properties (breaking strength, breaking elongation, softening temperature) of the obtained film were evaluated as a sample.

[0154] [Preparation of urethane hardened coating] First, the composition obtained above, a polyisocyanate component (C-2612), a urethane catalyst, a phosphorus compound (JP-508), and a dilution solvent were mixed in a 200 mL glass bottle in the proportions (unit: g) shown in Table 2A. Immediately after mixing, the mixed liquid was poured onto a release paper and cast into a film having a thickness of 200 μm using a bar coater. The cast film was then cured by heating under the conditions of 25° C. for 30 minutes, 50° C. for 30 minutes, 80° C. for 30 minutes, 120° C. for 1 hour, and 50° C. for 12 hours to obtain a urethane cured coating (film).

[0155] [100% tensile modulus evaluation] The tensile properties of the obtained film were measured under the following conditions in accordance with JIS K6251. (Strength at break, elongation at break) -conditions- Test equipment: Tensilon UTA-500 (manufactured by A&D) Measurement conditions: 25℃×50%RH Head speed: 200mm / min Dumbbell No. 4

[0156] [Softening temperature] A test piece was obtained from the obtained film using a dumbbell, a 2 cm mark was drawn on the test piece, and the thickness at the center of the mark was measured. A weight of a specified weight was attached to one grip of the test piece, and the other grip was clamped with a double clip, and the test piece was hung in a dryer with the clip on the upper side. The temperature inside the dryer was then increased and the distance between the marks was observed. The temperature at which the distance between the marks reached 4 cm was read as the softening temperature. Processing equipment: constant temperature blower dryer DRK633DA (manufactured by Advantec) Weight: thickness of center of gauge line (μm) x 0.05g Dumbbell No. 2 (JIS K6251 compliant) Heating rate: 5℃ / min

[0157] [Evaluation Criteria] The breaking strength, breaking elongation, and softening temperature were evaluated on a scale of A, B, and C (A: good, B: fair, C: poor). <Breaking strength> A: 30.0MPa or more B: 26.5MPa or more and less than 30.0MPa D: Less than 26.5MPa <Elongation at break> A: 550% or more B: 500% or more but less than 550% C: Less than 500% <Softening temperature> A: 200℃ or higher C: Less than 200℃

[0158] [Table 2A]

[0159] The overall evaluation of the composition was rated as A, B, or C (A: good, B: fair, C: poor). The results are shown in Table 3A. <Overall rating> A: Each physical property is rated A only B: The evaluation of each physical property does not include C, and includes one or more Bs. C: Each physical property has a C rating

[0160] [Table 3A]

[0161] <<Second Example>> Details of the materials used in the examples shown below are as follows: G4672: Polycarbonate diol, manufactured by Asahi Kasei Corporation 1,6-Hexanediol: BASF JAPAN 3-Ethyl-3-hydroxymethyloxetane: manufactured by Tokyo Chemical Industry Co., Ltd. Lithium acetylacetonate: Sigma-Aldrich C-2612: Coronate 2612 (trade name), hexamethylene diisocyanate adduct modified polyisocyanate, isocyanate content = 17.2%, manufactured by Tosoh Corporation JP-508: Product name, 2-ethylhexyl acid phosphate, manufactured by Johoku Chemical Industry Co., Ltd. DOTDL: Dioctyltin dilaurate, manufactured by Kishida Chemical Industry Co., Ltd. Methyl ethyl ketone: Maruzen Petrochemical Co., Ltd. Toluene: Fujifilm Wako Pure Chemical Industries, Ltd. BYK-331: Silicone surface conditioner, manufactured by BYK

[0162] Example 1B 289.9g of G4672, 8.0g of 1,6-hexanediol, 2.06g of 3-ethyl-3-hydroxymethyloxetane, and 0.015g of lithium acetylacetonate were mixed in a 1L two-neck glass reactor equipped with a stirrer, a thermometer, a heating device, a fractionator filled with structured packing, and a cooler. The resulting mixture was reacted for 5 hours while heating at 150°C under normal pressure to obtain a composition (PCD-1B) containing compounds (A-2) to (A-4).

[0163] Example 2B A composition (PCD-2B) containing compounds (A-2) to (A-4) was obtained in the same manner as in Example 1B, except that 7.1 g of 1,6-hexanediol and 3.03 g of 3-ethyl-3-hydroxymethyloxetane were added.

[0164] Example 3B A composition (PCD-3B) containing compounds (A-2) to (A-4) was obtained in the same manner as in Example 1B, except that 5.2 g of 1,6-hexanediol and 4.87 g of 3-ethyl-3-hydroxymethyloxetane were added.

[0165] Example 4B A composition (PCD-4B) containing compounds (A-2) to (A-4) was obtained in the same manner as in Example 1B, except that 290.0 g of G4672, 1.0 g of 1,6-hexanediol, and 8.94 g of 3-ethyl-3-hydroxymethyloxetane were added.

[0166] (Comparative example 1B) G4672 was used as is (PCD-5B).

[0167] (Comparative Example 2B) A composition (PCD-6B) containing compounds (A-2) to (A-4) was obtained in the same manner as in Example 1B, except that 9.1 g of 1,6-hexanediol and 1.05 g of 3-ethyl-3-hydroxymethyloxetane were added.

[0168] (Comparative example 3B) A composition (PCD-7B) containing compounds (A-2) to (A-4) was obtained in the same manner as in Example 1B, except that 284.9 g of G4672, 0.5 g of 1,6-hexanediol, and 14.6 g of 3-ethyl-3-hydroxymethyloxetane were added.

[0169] (Analysis and Evaluation) In the same manner as in Example 1, the composition obtained above was 1 H-NMR, number average molecular weight and complete acetylation number were measured, and properties were evaluated, the deemed hydroxyl value was calculated and the composition was analyzed. The results are shown in Table 1B.

[0170] [Table 1B]

[0171] In Table 1B, the "mixture" (unit: g) of Examples 1B to 4B and Comparative Examples 1B to 3B indicates the reaction raw materials.

[0172] (Physical property evaluation) A urethane cured film (film) was obtained in the same manner as in Example 1, except that the composition obtained above, a polyisocyanate component (C-2612), a urethane catalyst, a phosphoric ester (JP508), and a dilution solvent were mixed in the proportions (unit: g) shown in Table 2B. The obtained film was then used as a sample to evaluate the physical properties (breaking strength, breaking elongation, softening temperature) in the same manner as in Example 1. The results are shown in Table 2B.

[0173] [Evaluation Criteria] The breaking strength, breaking elongation, and softening temperature were evaluated on a scale of A, B, and C (A: good, B: fair, C: poor). <Breaking strength> A: 20.0MPa or more B: 15.0MPa or more and less than 20.0MPa D: Less than 15.0MPa <Elongation at break> A: 590% or more B: 560% or more but less than 590% C: Less than 560% <Softening temperature> A: 180℃ or higher C: Less than 180℃

[0174] [Table 2B]

[0175] The overall evaluation of the composition was rated as A, B, or C (A: good, B: fair, C: poor). The results are shown in Table 3B. <Overall rating> A: Each physical property is rated A only B: The evaluation of each physical property does not include C, and includes one or more Bs. C: Each physical property has a C rating

[0176] [Table 3B]

[0177] <<Third Example>> Details of the materials used in the examples shown below are as follows: N-964: Nipolan 964 (product name), polycarbonate diol, manufactured by Tosoh Corporation 1,6-Hexanediol: BASF JAPAN 3-Ethyl-3-hydroxymethyloxetane: manufactured by Tokyo Chemical Industry Co., Ltd. Lithium acetylacetonate: Sigma-Aldrich C-2612: Coronate 2612 (trade name), hexamethylene diisocyanate adduct modified polyisocyanate, isocyanate content = 17.2%, manufactured by Tosoh Corporation JP-508: Product name, 2-ethylhexyl acid phosphate, manufactured by Johoku Chemical Industry Co., Ltd. DOTDL: Dioctyltin dilaurate, manufactured by Kishida Chemical Industry Co., Ltd. Methyl ethyl ketone: Maruzen Petrochemical Co., Ltd. Toluene: Fujifilm Wako Pure Chemical Industries, Ltd. BYK-331: Silicone surface conditioner, manufactured by BYK

[0178] Example 1C 289.9g of N-964, 8.0g of 1,6-hexanediol, 2.06g of 3-ethyl-3-hydroxymethyloxetane, and 0.015g of lithium acetylacetonate were mixed in a 1L two-neck glass reactor equipped with a stirrer, a thermometer, a heating device, a fractionator filled with structured packing, and a cooler. The resulting mixture was reacted for 5 hours while heating at 150°C under normal pressure to obtain a composition (PCD-1C) containing compounds (A-2) to (A-4).

[0179] Example 2C A composition (PCD-2C) containing compounds (A-2) to (A-4) was obtained in the same manner as in Example 1C, except that 7.1 g of 1,6-hexanediol and 3.03 g of 3-ethyl-3-hydroxymethyloxetane were added.

[0180] Example 3C A composition (PCD-3C) containing compounds (A-2) to (A-4) was obtained in the same manner as in Example 1C, except that 5.2 g of 1,6-hexanediol and 4.87 g of 3-ethyl-3-hydroxymethyloxetane were added.

[0181] Example 4C A composition (PCD-4C) containing compounds (A-2) to (A-4) was obtained in the same manner as in Example 1C, except that 290.0 g of N-964, 1.0 g of 1,6-hexanediol, and 8.94 g of 3-ethyl-3-hydroxymethyloxetane were added.

[0182] (Comparative example 1C) N-964 was used as is (PCD-5C).

[0183] (Comparative Example 2C) A composition (PCD-6C) containing compounds (A-2) to (A-4) was obtained in the same manner as in Example 1C, except that 9.1 g of 1,6-hexanediol and 1.05 g of 3-ethyl-3-hydroxymethyloxetane were added.

[0184] (Comparative example 3C) A composition (PCD-7C) containing compounds (A-2) to (A-4) was obtained in the same manner as in Example 1C, except that 284.9 g of N-964, 0.5 g of 1,6-hexanediol, and 14.6 g of 3-ethyl-3-hydroxymethyloxetane were added.

[0185] (Analysis and Evaluation) In the same manner as in Example 1, the composition obtained above was 1 H-NMR, number average molecular weight and complete acetylation number were measured, and properties were evaluated, the assumed hydroxyl value was calculated and the composition was analyzed. The results are shown in Table 1C.

[0186] [Table 1C]

[0187] In Table 1C, the "mixture" (unit: g) for Examples 1C to 4C and Comparative Examples 1C to 3C indicates the reaction raw materials.

[0188] (Physical property evaluation) A urethane cured film (film) was obtained in the same manner as in Example 1, except that the composition obtained above, a polyisocyanate component (C-2612), a urethane catalyst, a phosphoric ester (JP508), and a dilution solvent were mixed in the proportions (unit: g) shown in Table 2C. The obtained film was then used as a sample to evaluate the physical properties (breaking strength, breaking elongation, softening temperature) in the same manner as in Example 1. The results are shown in Table 2C.

[0189] [Evaluation Criteria] The breaking strength, breaking elongation, and softening temperature were evaluated on a scale of A, B, and C (A: good, B: fair, C: poor). <Breaking strength> A: 18.0MPa or more B: 10.0MPa or more and less than 18.0MPa D: Less than 10.0 MPa <Elongation at break> A: 760% or more B: 730% or more but less than 760% C: Less than 730% <Softening temperature> A: 100℃ or higher C: Less than 100℃

[0190] [Table 2C]

[0191] The overall evaluation of the composition was rated as A, B, or C (A: good, B: fair, C: poor). The results are shown in Table 3C. <Overall rating> A: Each physical property is rated A only B: The evaluation of each physical property does not include C, and includes one or more Bs. C: Each physical property has a C rating

[0192] [Table 3C]

[0193] <<Fourth Example>> Details of the materials used in the examples shown below are as follows: N-980N: Nipolan 980N (product name), polycarbonate diol, manufactured by Tosoh Corporation PCL-220: Polycaprolactone diol, manufactured by Daicel Corporation 1,6-Hexanediol: BASF JAPAN 3-Ethyl-3-hydroxymethyloxetane: manufactured by Tokyo Chemical Industry Co., Ltd. Lithium acetylacetonate: Sigma-Aldrich C-2612: Coronate 2612 (trade name), hexamethylene diisocyanate adduct modified polyisocyanate, isocyanate content = 17.2%, manufactured by Tosoh Corporation JP-508: Product name, 2-ethylhexyl acid phosphate, manufactured by Johoku Chemical Industry Co., Ltd. DOTDL: Dioctyltin dilaurate, manufactured by Kishida Chemical Industry Co., Ltd. Methyl ethyl ketone: Maruzen Petrochemical Co., Ltd. Toluene: Fujifilm Wako Pure Chemical Industries, Ltd. BYK-331: Silicone surface conditioner, manufactured by BYK

[0194] Example 1D In a 1L two-neck glass reactor equipped with a stirrer, a thermometer, a heating device, a rectification column filled with structured packing, and a cooler, 202.9g of N-980N, 87.0g of PCL-220, 8.0g of 1,6-hexanediol, 2.06g of 3-ethyl-3-hydroxymethyloxetane, and 0.015g of lithium acetylacetonate were mixed. The mixture obtained was reacted for 5 hours while heating at 150°C under normal pressure to obtain a composition (PCD-1D) containing compounds (A-2) to (A-4).

[0195] Example 2D A composition (PCD-2D) containing compounds (A-2) to (A-4) was obtained in the same manner as in Example 1D, except that 7.1 g of 1,6-hexanediol and 3.03 g of 3-ethyl-3-hydroxymethyloxetane were added.

[0196] Example 3D A composition (PCD-3D) containing compounds (A-2) to (A-4) was obtained in the same manner as in Example 1D, except that 203.0 g of N-980N, 5.2 g of 1,6-hexanediol, and 4.87 g of 3-ethyl-3-hydroxymethyloxetane were added.

[0197] Example 4D A composition (PCD-4D) containing compounds (A-2) to (A-4) was obtained in the same manner as in Example 1D, except that 203.0 g of N-980N, 1.0 g of 1,6-hexanediol, and 8.94 g of 3-ethyl-3-hydroxymethyloxetane were added.

[0198] Comparative Example 1D A mixture of N-980N and PCL-220 was used as is (PCD-5D).

[0199] (Comparative example 2D) A composition (PCD-6D) containing compounds (A-2) to (A-4) was obtained in the same manner as in Example 1D, except that 9.1 g of 1,6-hexanediol and 1.05 g of 3-ethyl-3-hydroxymethyloxetane were added.

[0200] (Comparative example 3D) A composition (PCD-7D) containing compounds (A-2) to (A-4) was obtained in the same manner as in Example 1D, except that 199.4 g of N-980N, 85.5 g of PCL-220, 0.5 g of 1,6-hexanediol, and 14.6 g of 3-ethyl-3-hydroxymethyloxetane were added.

[0201] (Analysis and Evaluation) In the same manner as in Example 1, the composition obtained above was 1H-NMR, number average molecular weight and complete acetylation number were measured, and properties were evaluated, the assumed hydroxyl value was calculated and the composition was analyzed. The results are shown in Table 1D.

[0202] [Table 1D]

[0203] In Table 1D, the "mixture" (unit: g) of Examples 1D to 4D and Comparative Examples 1D to 3D indicates the reaction raw materials.

[0204] (Physical property evaluation) A urethane cured film (film) was obtained in the same manner as in Example 1, except that the composition obtained above, a polyisocyanate component (C-2612), a urethane catalyst, a phosphoric ester (JP508), and a dilution solvent were mixed in the proportions (unit: g) shown in Table 2D. The obtained film was then used as a sample to evaluate the physical properties (breaking strength, breaking elongation, softening temperature) in the same manner as in Example 1. The results are shown in Table 2D.

[0205] [Evaluation Criteria] The breaking strength, breaking elongation, and softening temperature were evaluated on a scale of A, B, and C (A: good, B: fair, C: poor). <Breaking strength> A: 19.0MPa or more B: 14.0MPa or more and less than 19.0MPa D: Less than 14.0 MPa <Elongation at break> A: 650% or more B: 580% or more but less than 650% C: Less than 580% <Softening temperature> A: 180℃ or higher C: Less than 180℃

[0206] [Table 2D]

[0207] The overall evaluation of the composition was rated as A, B, or C (A: good, B: fair, C: poor). The results are shown in Table 3C. <Overall rating> A: Each physical property is rated A only B: The evaluation of each physical property does not include C, and includes one or more Bs. C: Each physical property has a C rating

[0208] [Table 3D]

Claims

1. A compound (A-2) represented by the following formula (A-2), The composition contains a compound (A-3) represented by the following formula (A-3) and / or a compound (A-4) represented by the following formula (A-4), A composition, wherein the content of structure (B) derived from an oxetane compound represented by the following formula (B) is 2.20 to 20 mol % based on the total content of structure (B) derived from the oxetane compound and structure (C) represented by the following formula (C): 【Chemistry 1】 [In formula (A-2), R １ is *1-O-R ａ -CH ２ -*2, *1-R ｂ -C(=O)-OR ｃ -CH ２ -*2, or *1-R ｄ -CH ２ - indicates *2, R ａ , R ｂ , R ｃ , and R ｄ each independently represents an alkanediyl group, *1 indicates the bonding site with the carbonyl group, *2 indicates the bonding site with the oxygen atom; n ２ represents an integer of 1 or more; Multiple R's １ may be the same or different. 【Chemistry 2】 [In formula (A-3), R １ is as defined above, R ２ is a hydrogen atom, an alkyl group or a hydroxyalkyl group, n ３ represents an integer of 1 or more, Multiple R's １ may be the same or different. 【Chemistry 3】 [In formula (A-4), R １ and R ２ is as defined above, and n ４ represents an integer of 1 or more. ２ may be the same or different. １ When there are a plurality of, they may be the same or different. 【Chemistry 4】 [In formula (B), R ２ is as defined above, * indicates a bond. 【Chemistry 5】 [In formula (C), * indicates a bond, R ３ are hydrogen atoms or alkyl groups, and may be the same or different.

2. The composition according to claim 1, further comprising a diol (d) represented by the following formula (d) and an oxetane compound (F) represented by the following formula (f). 【Chemistry 6】 [In formula (d), R ａ has the same meaning as above.] 【Chemistry 7】 [In formula (f), R ２ has the same meaning as above.]

3. 3. The composition of claim 1 or 2, further comprising lithium acetylacetonate.

4. A polycondensate of a polyol component and a polyisocyanate component or a crosslinked product thereof, A urethane resin, wherein the polyol component comprises the composition of claim 1 or 2.

5. A coating film comprising the urethane resin according to claim 4.

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