Blocked polyisocyanate composition, curable resin composition comprising same, and cured product

Abstract

Provided are: a blocked polyisocyanate composition having excellent storage stability; a curable resin composition containing the blocked polyisocyanate composition; and a cured product. A blocked polyisocyanate composition containing: a blocked polyisocyanate compound in which the isocyanate group of a polyisocyanate compound is blocked with a secondary amine compound represented by formula (1); and an amine compound represented by at least one formula selected from the group consisting of formula (2-1), formula (2-2), formula (2-3), and formula (2-4).

Description

Technical Field

[0001] This invention relates to end-capped polyisocyanate compositions, curable resin compositions comprising the compositions, and cured products. Background Technology

[0002] Terminally capped polyisocyanate compounds are compounds obtained by reacting a polyisocyanate compound with a capping agent having an active hydrogen group capable of reacting with the isocyanate group. Terminally capped polyisocyanate compounds possess the following properties: the isocyanate group of the polyisocyanate is sealed by the capping agent, thus rendering it inactive at room temperature; heating causes the capping agent to dissociate, regenerating the isocyanate group. Due to these properties, terminally capped polyisocyanate compounds are widely used in coatings and other applications as one-component coating compositions, often mixed with polyols and curing catalysts.

[0003] For example, Patent Document 1 describes a capped isocyanate composition comprising a capped isocyanate compound obtained by a triisocyanate compound represented by formula (I) and at least two capping agents, as described in claim 1 of the international publication, and a one-component coating composition comprising the capped isocyanate composition and a polyol.

[0004] In addition, it is described that as two types of end-capping agents, including amine compounds and pyrazole compounds, as catalysts for curing promotion, they may contain metal salts such as dibutyltin dilaurate and tertiary amines.

[0005] Furthermore, the invention described in Patent Document 1 provides a capped isocyanate composition with low viscosity and low crystallinity, excellent low-temperature curing properties and excellent storage stability of the coating.

[0006] Additionally, for example, Patent Document 2 describes: a capped isocyanate composition comprising a triisocyanate compound represented by formula (I) and a capped isocyanate derived from a capping agent containing an amine compound, as described in claim 1 of the publication, and a coating composition comprising the capped isocyanate composition and an active hydrogen compound.

[0007] In addition, as an amine compound, it is described as a secondary amine compound, which can contain curing-promoting catalysts such as amine compounds.

[0008] Moreover, the invention described in Patent Document 2 provides a capped isocyanate composition that maintains good sealing resistance while exhibiting excellent curability and excellent gloss and image clarity when the coating is formed.

[0009] Existing technical documents Patent documents Patent Document 1: International Publication No. 2018 / 235896 Patent Document 2: Japanese Patent Application Publication No. 2022-041366 Summary of the Invention

[0010] The technical problem that the invention aims to solve In the aforementioned prior art, even when storing a capped polyisocyanate composition containing a capped isocyanate compound, a polyol, and a curing catalyst at room temperature, the capped polyisocyanate composition may still solidify during storage. Therefore, there is a need for a capped polyisocyanate composition that prevents solidification of the capped polyisocyanate compound during storage and exhibits excellent storage stability.

[0011] Therefore, the technical problem to be solved by the present invention is to improve the storage stability of the end-capped polyisocyanate composition and the curable resin composition containing the composition, to provide the end-capped polyisocyanate composition and the curable resin composition containing the composition with excellent storage stability, and to provide the cured product obtained by curing the curable resin composition.

[0012] Technical solutions for solving technical problems The inventors of this application conducted in-depth research and found that the present invention can solve the above-mentioned technical problems, thereby completing the present invention.

[0013] That is, the present invention provides the following end-capped polyisocyanate compositions [1] to [3], curable resin compositions [4] to [6], and cured products [7].

[0014] [1] A capped polyisocyanate composition comprising: a capped polyisocyanate compound formed by capping the isocyanate group of a polyisocyanate compound with a secondary amine compound of formula (1) below, and an amine compound selected from at least one of formulas (2-1), (2-2), (2-3) and (2-4) below.

[0015] Equation (1): [Chemistry 1]

[0016] (where R is in the formula) 1 R 2 R 3 R 4 and R 5 Each is independent. R 1 R 2 and R 3 R represents a hydrocarbon group with 1 to 20 carbon atoms that can be replaced by heteroatoms. 4 and R 5 This indicates a hydrocarbon group or hydrogen atom with 1 to 20 carbon atoms that can be replaced by heteroatoms. R 1 R 2 R 3R 4 and R 5 They can form ring structures together with the carbon atoms they are bonded to. Equation (2-1): [Chemistry 2]

[0017] (R 6 and R 7 Each is independent. R 6 and R 7 R represents a hydrocarbon group with 1 to 20 carbon atoms that can be replaced by heteroatoms. 6 and R 7 They can form ring structures together with the nitrogen atoms they are bonded to. Equation (2-2): [Chemistry 3]

[0018] (R 8 R 9 R 10 R 11 and R 12 Each is independent. R 8 R 9 R 10 R 11 and R 12 Represents a hydrogen atom or a hydrocarbon group. In R... 8 R 9 R 10 R 11 and R 12 In the case of a hydrocarbon group, which is a hydrocarbon group with 1 to 20 carbon atoms that can be replaced by heteroatoms, it can form a ring structure together with the carbon atoms it is bonded to. Equation (2-3): [Chemistry 4]

[0019] (R 13 R 14 R 15 and R 16 Each is independent. R 13 R 14 R 15 and R 16 Represents a hydrogen atom or a hydrocarbon group. In R... 13 R 14 R 15 and R 16 In the case of a hydrocarbon group, which is a hydrocarbon group with 1 to 20 carbon atoms that can be replaced by heteroatoms, it can form a ring structure together with the carbon atoms it is bonded to. Equation (2-4): [Chemistry 5]

[0020] (R 17 R 18 R 19 and R 20 Each is independent. R 17 R 18 R 19 and R 20 Represents a hydrogen atom or a hydrocarbon group. In R... 17 R 18 R 19 and R 20 In the case of a hydrocarbon group, which is a hydrocarbon group with 1 to 20 carbon atoms that can be replaced by heteroatoms, it can form a ring structure together with the carbon atom and / or nitrogen atom to which it is bonded.

[0021] [2] The end-capped polyisocyanate composition according to [1], wherein the polyisocyanate compound is at least one polyisocyanate selected from aliphatic polyisocyanates, alicyclic polyisocyanates, aromatic polyisocyanates and aromatic aliphatic polyisocyanates, or a modified polyisocyanate formed from at least one polyisocyanate selected from aliphatic polyisocyanates, alicyclic polyisocyanates, aromatic polyisocyanates and aromatic aliphatic polyisocyanates.

[0022] [3] According to the capped polyisocyanate composition of [1], wherein the R of the secondary amine compound represented by formula (1) 1 R 2 and R 3 R is a hydrocarbon group with 1 to 2 carbon atoms. 4 and R 5 It consists of a hydrocarbon group or hydrogen atom with 1 to 2 carbon atoms.

[0023] [4] A curable resin composition comprising any one of [1] to [3] a capped polyisocyanate composition and a compound having isocyanate reactive groups.

[0024] [5] The curable resin composition according to [4], wherein the compound having isocyanate reactive groups is a polyol compound or a polyamine compound.

[0025] [6] A curable resin composition comprising the curable resin composition described in [4] and a curing catalyst.

[0026] [7] A cured product which is formed by curing the curable resin composition described in [6].

[0027] Invention Effects According to the present invention, it is possible to provide a capped polyisocyanate composition with excellent storage stability, a curable resin composition comprising the composition, and a cured product. Detailed Implementation

[0028] <Terminated Polyisocyanate Compositions> The capped polyisocyanate composition of the present invention comprises: a capped polyisocyanate compound formed by capping the isocyanate group of a polyisocyanate compound with a secondary amine compound of formula (1), and an amine compound selected from at least one of formulas (2-1), (2-2), (2-3) and (2-4).

[0029] <Terminated polyisocyanate compounds> The terminated polyisocyanate compounds are described below. Examples of terminated polyisocyanate compounds include those that react a polyisocyanate compound with a terminating agent, thereby sealing the isocyanate groups in the polyisocyanate compound using the terminating agent. The terminated polyisocyanate compounds can be used alone or in mixtures of two or more.

[0030] <Polyisocyanate compounds> There are no particular limitations on the polyisocyanate compounds that constitute end-capped polyisocyanate compounds, as long as they have two or more isocyanate groups. The following polyisocyanate compounds can be cited as examples.

[0031] (i) Aliphatic polyisocyanates (ii) Alicyclic polyisocyanates (iii) Aromatic polyisocyanates (iv) Aromatic aliphatic polyisocyanates (v) A modified polyisocyanate formed from at least one of aliphatic polyisocyanates, alicyclic polyisocyanates, aromatic polyisocyanates and aromatic aliphatic polyisocyanates.

[0032] Examples of (i) aliphatic polyisocyanates include, for example, 1,4-tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, lysine diisocyanate, dimer acid diisocyanate, etc.

[0033] Examples of (ii) alicyclic polyisocyanates include: 1,3-bis(isocyanate methyl)cyclohexane, 1,4-bis(isocyanate methyl)cyclohexane, 3-isocyanate methyl-3,3,5-trimethylcyclohexane (isophorone diisocyanate (IPDI)), bis-(4-isocyanate cyclohexyl)methane, norbornane diisocyanate, etc.

[0034] Examples of (iii) aromatic polyisocyanates include: 2,4′-diphenylmethane diisocyanate, 4,4′-diphenylmethane diisocyanate, crude diphenylmethane diisocyanate, 1,4-phenylene diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, 3,3′-dimethyl-4,4′-diisocyanate-biphenyl, 3,3′-dimethyl-4,4′-diisocyanate-diphenylmethane, 1,5-naphthalene diisocyanate, etc.

[0035] Examples of (iv) aromatic aliphatic polyisocyanates include: 1,3-xylene diisocyanate, 1,4-xylene diisocyanate, α , α , α ′, α ′-Tetramethylxylene diisocyanate, etc.

[0036] Examples of (v) modified polyisocyanates include: isocyanate-terminated compounds obtained by reacting the above-mentioned polyisocyanate compounds with compounds having active hydrogen groups, polyisocyanate compounds and / or reactants of such isocyanate-terminated compounds (e.g., adduct-type polyisocyanates; isocyanate modified products obtained by urea-formylation, carbodiimideation, ureidyl-diketation, isocyanurate esterification, uretonimideation, biuretization, etc.), preferably adduct-type polyisocyanates, polyisocyanates modified by isocyanurate esterification (polyisocyanates having isocyanurate bonds), polyisocyanates modified by biuretization (polyisocyanates having biuret bonds), and polyisocyanates modified by carbamate esterification (polyisocyanates having carbamate bonds).

[0037] [Polyisocyanates with biuret bonds] Polyisocyanates with biuret bonds are obtained by reacting water, tert-butanol, urea, or other so-called biuretizing agents with polyisocyanates at a molar ratio of biuretizing agent / polyisocyanate isocyanate group of about 1 / 2 to about 1 / 100, and then removing and purifying the unreacted polyisocyanates.

[0038] Examples of polyisocyanates having biuret bonds include, for example, biuret-modified 1,6-hexamethylene diisocyanate (HDI) as shown in formula (1a) below, biuret-modified isophorone diisocyanate (IPDI), and biuret-modified toluene diisocyanate (TDI). Commercially available products include Desmodur N75, Desmodur N100, and Desmodur N3200 manufactured by Sumika Covestro Urethane Co., Ltd., and Durnate 24A-100, Durnate 22A-75P, and Durnate 21S-75E manufactured by Asahi Kasei Corporation.

[0039] Equation (1a): [Chemistry 6]

[0040] [Polyisocyanates containing isocyanurate bonds] Polyisocyanates containing isocyanurate bonds undergo a cyclic 3-membered reaction, for example, using a catalyst, and the reaction is stopped when the conversion reaches about 5% to about 80% by mass. The unreacted polyisocyanates are then removed and purified to obtain the product. At this point, it is possible to use 1- to 6-membered alcohol compounds.

[0041] As a catalyst for the above-mentioned isocyanurate esterification reaction, a basic catalyst is generally preferred. Examples of such catalysts include: (1) Hydroxides of tetramethylammonium, tetraethylammonium, trimethylbenzylammonium, etc., and organic weak acid salts such as acetic acid and decanoic acid. (2) Hydroxides of hydroxyalkylammonium such as trimethylhydroxypropylammonium, trimethylhydroxyethylammonium, triethylhydroxypropylammonium, and triethylhydroxyethylammonium, and organic weak acid salts such as acetic acid and decanoic acid. (3) Metal salts of alkyl carboxylic acids, such as tin, zinc, and lead. (4) Sodium, potassium and other metal alkoxides (5) Compounds containing aminosilyl groups, such as hexamethyldisilazane. (6) Mannich bases (7) The combined use of tertiary amines and epoxides, (8) Phosphorus compounds such as tributylphosphine You can also use two or more at the same time.

[0042] In cases where the aforementioned catalyst may adversely affect the properties of the coating or film, the catalyst can be neutralized using acidic compounds. Examples of such acidic compounds include: inorganic acids such as hydrochloric acid, phosphorous acid, and phosphoric acid; sulfonic acids or their derivatives such as methanesulfonic acid, p-toluenesulfonic acid, methyl p-toluenesulfonate, and ethyl p-toluenesulfonate; ethyl phosphate, diethyl phosphate, isopropyl phosphate, diisopropyl phosphate, butyl phosphate, dibutyl phosphate, 2-ethylhexyl phosphate, di(2-ethylhexyl) phosphate, isodecanyl phosphate, diisodecyl phosphate, oleyl acid phosphate, tetracosyl phosphate, glycolic acid phosphate, butyl pyrophosphate, and butyl phosphite; two or more of these compounds may also be used in combination.

[0043] Polyisocyanates having isocyanurate bonds include, for example, isocyanurate modified HDI, isocyanurate modified IPDI, and isocyanurate modified TDI as shown in formula (1b) below. Commercially available products include: Sumidur N3300, Desmodur 3900, Desmodur Z4470BA, Desmodur XP2763, Desmodur IL 1351BA, and Desmodur HLBA manufactured by Sumika Covestro Urethane Co., Ltd., and Durnate TPA-100, Durnate MFA-75B, Durnate TUL-100, and Durnate TSA-100 manufactured by Asahi Kasei Corporation.

[0044] Equation (1b): [Chemistry 7]

[0045] [Polyisocyanates with carbamate bonds] Polyisocyanates containing carbamate bonds, for example, are obtained by reacting a 2- to 6-membered alcohol compound such as trimethylolpropane (hereinafter referred to as TMP) with a diisocyanate at a molar ratio of the hydroxyl group of the alcohol compound to the isocyanate group of the polyisocyanate of the diisocyanate of about 1 / 2 to about 1 / 100, followed by purification to remove unreacted polyisocyanates. Purification to remove unreacted polyisocyanates is not necessarily required.

[0046] Polyisocyanates containing urethane bonds, for example, are reactants of HDI and TMP, reactants of IPDI and TMP, and reactants of TDI and TMP. Commercially available products include: Sumidur N3300, Desmodur 3900, Desmodur Z4470BA, Desmodur XP2763, Desmodur IL 1351BA, and Desmodur HLBA manufactured by Sumika Covestro Urethane Co., Ltd., and Durnate TPA-100, Durnate MFA-75B, Durnate TUL-100, and Durnate TSA-100 manufactured by Asahi Kasei Corporation.

[0047] In one embodiment, examples of polyisocyanates include the polyisocyanate shown in formula (3) below, or the modified polyisocyanate shown in formula (3) below.

[0048] Equation (3): [Chemistry 9]

[0049] (In the formula, A represents a residue obtained by removing an isocyanate group from at least one polyisocyanate selected from aliphatic polyisocyanates, alicyclic polyisocyanates, aromatic polyisocyanates, and aromatic aliphatic polyisocyanates, or a residue obtained by removing an isocyanate group from a modified polyisocyanate formed from at least one of aliphatic polyisocyanates, alicyclic polyisocyanates, aromatic polyisocyanates, and aromatic aliphatic polyisocyanates. x is an integer of 2 or more and less than 20.) As the polyisocyanate represented by formula (3), it is preferably (i) an aliphatic polyisocyanate or (ii) an alicyclic polyisocyanate.

[0050] As the modified polyisocyanate shown in formula (3), (v) is preferably a modified polyisocyanate formed from at least one selected from aliphatic polyisocyanates, alicyclic polyisocyanates, aromatic polyisocyanates and aromatic aliphatic polyisocyanates.

[0051] These polyisocyanates can be used alone or in combination of two or more.

[0052] <End-capping agent> In this invention, the end-capping agent that seals a portion of the isocyanate group of the above-mentioned polyisocyanate or modified polyisocyanate is a secondary amine compound represented by the following formula (1).

[0053] Equation (1): [Chemistry 10]

[0054] (where R is in the formula) 1 R 2 R 3 R 4 and R 5 Each is independent. R 1 R 2 and R 3 R represents a hydrocarbon group with 1 to 20 carbon atoms that can be replaced by heteroatoms. 4 and R 5 This indicates a hydrocarbon group or hydrogen atom with 1 to 20 carbon atoms that can be replaced by heteroatoms. R 1 R 2 R 3 R 4 and R 5 They can form ring structures together with the carbon atoms they are bonded to. In equation (1), R 1 R 2 R 3 R 4 and R 5 Each is independent.

[0055] In equation (1), R 1 R 2 and R 3 The hydrocarbon group is a hydrocarbon group with 1 to 20 carbon atoms that can be replaced by heteroatoms, preferably a hydrocarbon group with 1 to 12 carbon atoms that can be replaced by heteroatoms, more preferably a hydrocarbon group with 1 to 6 carbon atoms that can be replaced by heteroatoms, even more preferably a hydrocarbon group with 1 to 4 carbon atoms that can be replaced by heteroatoms, particularly preferably a hydrocarbon group with 1 to 2 carbon atoms that can be replaced by heteroatoms, and most preferably a hydrocarbon group with 1 to 2 carbon atoms.

[0056] In equation (1), R 4 and R 5 It consists of 1 to 20 hydrocarbon groups or hydrogen atoms that can be replaced by heteroatoms.

[0057] In R 4 and R 5 When the hydrocarbon group is a hydrocarbon group with 1 to 20 carbon atoms that can be replaced by heteroatoms, it is preferably a hydrocarbon group with 1 to 12 carbon atoms that can be replaced by heteroatoms, more preferably a hydrocarbon group with 1 to 6 carbon atoms that can be replaced by heteroatoms, and even more preferably a hydrocarbon group with 1 to 4 carbon atoms that can be replaced by heteroatoms.

[0058] R 4 and R 5 Particularly preferred are hydrocarbon groups or hydrogen atoms with 1 to 2 carbon atoms that can be replaced by heteroatoms, and most preferably hydrocarbon groups or hydrogen atoms with 1 to 2 carbon atoms.

[0059] R 1 R 2 R 3 R 4 and R 5 Examples of hydrocarbon groups that are not substituted by heteroatoms include methyl, ethyl, propyl, n-butyl, sec-butyl, tert-butyl, pentyl, neopentyl, hexyl, octyl, benzyl, and phenyl, with methyl, ethyl, neopentyl, and phenyl being preferred, and methyl and ethyl being more preferred.

[0060] Additionally, R 1 R 2 R 3 R 4 and R 5 As a hydrocarbon group substituted by a heteroatom, it is at least one of the -CH2- that constitutes the hydrocarbon group, for example, a hydrocarbon group substituted by at least one of -O-, -NH-, -N(R)- (R represents a hydrocarbon group), -S-, -SO2-, etc.

[0061] Additionally, R 1 R 2 R 3 R 4 and R 5 They can form ring structures together with the carbon atoms they are bonded to.

[0062] Examples of secondary amine compounds represented by formula (1) include: tert-butyl-ethylamine, tert-butyl-n-propylamine, tert-butyl-isopropylamine, tert-butyl-n-butylamine, tert-butyl-sec-butylamine, tert-butyl-n-octylamine, tert-butyl-2-ethylhexylamine, tert-pentyl-ethylamine, tert-pentyl-n-propylamine, tert-pentyl-isopropylamine, tert-pentyl-sec-butylamine, 1,1,3,3-tetramethylbutyl-ethylamine, 1,1,3,3-tetramethylbutyl-n-propylamine, 1,1,3,3-tetramethylbutyl-isopropylamine, 1,1,3,3-tetramethylbutyl-n-butylamine, 1,1,3,3-tetramethylbutyl-sec-butylamine, 1,1,3,3-tetramethylbutyl-n-octylamine, 1,1,3,3-tetramethylbutyl-2-ethylhexylamine, etc.

[0063] <Amine compounds> The amine compound contained in the capped polyisocyanate composition of the present invention is an amine compound selected from at least one of the formulas (2-1), (2-2), (2-3) and (2-4).

[0064] [The amine compound shown in formula (2-1)] Equation (2-1): [Chemistry 11]

[0065] (R 6 and R7 Each is independent. R 6 and R 7 R represents a hydrocarbon group with 1 to 20 carbon atoms that can be replaced by heteroatoms. 6 and R 7 They can form ring structures together with the nitrogen atoms they are bonded to. In equation (2-1), R 6 and R 7 Each is independent.

[0066] In equation (2-1), R 6 and R 7 The hydrocarbon group is a hydrocarbon group with 1 to 20 carbon atoms that can be replaced by heteroatoms, preferably a hydrocarbon group with 1 to 12 carbon atoms that can be replaced by heteroatoms, more preferably a hydrocarbon group with 1 to 8 carbon atoms that can be replaced by heteroatoms, even more preferably a hydrocarbon group with 1 to 6 carbon atoms that can be replaced by heteroatoms, and even more preferably a hydrocarbon group with 1 to 4 carbon atoms that can be replaced by heteroatoms.

[0067] R 6 and R 7 Examples of hydrocarbon groups that are not substituted by heteroatoms include methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, pentyl, neopentyl, hexyl, octyl, benzyl, and phenyl. Methyl, ethyl, neopentyl, and phenyl are preferred, methyl, ethyl, isopropyl, and tert-butyl are more preferred, and ethyl, isopropyl, and tert-butyl are even more preferred.

[0068] Additionally, R 6 and R 7 As a hydrocarbon group substituted by a heteroatom, it is at least one of the -CH2- that constitutes the hydrocarbon group, for example, a hydrocarbon group substituted by at least one of -O-, -NH-, -N(R)- (R represents a hydrocarbon group), -S-, -SO2-, etc.

[0069] Additionally, R 6 and R 7 They can form ring structures together with the nitrogen atoms they are bonded to.

[0070] Examples of amine compounds represented by formula (2-1) include: tert-butylmethylamine, tert-butylethylamine, tert-butylpropylamine, tert-butylisopropylamine, tert-butylbutylamine, tert-butylsec-butylamine, di(tert-butyl)amine, tert-butylaniline, tert-butylbenzylamine, etc.

[0071] [Amine compounds represented by formula (2-2)] Equation (2-2): [Chemistry 12]

[0072] (R 8 R9 R 10 R 11 and R 12 Each is independent. R 8 R 9 R 10 R 11 and R 12 Represents a hydrogen atom or a hydrocarbon group. In R... 8 R 9 R 10 R 11 and R 12 In the case of a hydrocarbon group, which is a hydrocarbon group with 1 to 20 carbon atoms that can be replaced by heteroatoms, it can form a ring structure together with the carbon atoms it is bonded to. In equation (2-2), R 8 R 9 R 10 R 11 and R 12 Each is independent.

[0073] R 8 R 9 R 10 R 11 and R 12 It consists of hydrogen atoms or hydrocarbon groups.

[0074] In R 8 R 9 R 10 R 11 and R 12 When the hydrocarbon group is used, it is a hydrocarbon group with 1 to 20 carbon atoms that can be replaced by heteroatoms, preferably a hydrocarbon group with 1 to 12 carbon atoms that can be replaced by heteroatoms, more preferably a hydrocarbon group with 1 to 6 carbon atoms that can be replaced by heteroatoms, even more preferably a hydrocarbon group with 1 to 4 carbon atoms that can be replaced by heteroatoms, and even more preferably a hydrocarbon group with 1 to 2 carbon atoms that can be replaced by heteroatoms.

[0075] R 8 R 9 R 10 R 11 and R 12 Examples of hydrocarbon groups that are not substituted by heteroatoms include methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, pentyl, neopentyl, hexyl, octyl, benzyl, and phenyl, with methyl, ethyl, neopentyl, and phenyl being preferred, and methyl and ethyl being more preferred.

[0076] Additionally, R 8 R 9 R 10 R 11 and R12 As a hydrocarbon group substituted by a heteroatom, it is at least one of the -CH2- that constitutes the hydrocarbon group, for example, a hydrocarbon group substituted by at least one of -O-, -NH-, -N(R)- (R represents a hydrocarbon group), -S-, -SO2-, etc.

[0077] Additionally, R 8 R 9 R 10 R 11 and R 12 They can form ring structures together with the carbon atoms they are bonded to.

[0078] As R 8 R 9 R 10 R 11 and R 12 The preferred atoms are hydrogen atoms, methyl groups, and ethyl groups.

[0079] Examples of amine compounds represented by formula (2-2) include piperidine, 4-methylpiperidine, 4-ethylpiperidine, 4-isopropylpiperidine, 4-(tert-butyl)piperidine, 2,6-dimethylpiperidine, 2,6-diethylpiperidine, 2,6-diisopropylpiperidine, 2,6-di(tert-butyl)piperidine, 3,5-dimethylpiperidine, 3,5-diethylpiperidine, 3,5-diisopropylpiperidine, 3,5-di(tert-butyl)piperidine, etc.

[0080] [Amine compounds represented by formula (2-3)] Equation (2-3): [Chemistry 13]

[0081] (R 13 R 14 R 15 and R 16 Each is independent. R 13 R 14 R 15 and R 16 Represents a hydrogen atom or a hydrocarbon group. In R... 8 R 9 R 10 R 11 and R 12 In the case of a hydrocarbon group, which is a hydrocarbon group with 1 to 20 carbon atoms that can be replaced by heteroatoms, it can form a ring structure together with the carbon atoms it is bonded to. In equation (2-3), R 13 R 14 R 15 and R 16 Each is independent.

[0082] R 13 R 14 R 15 and R 16 It consists of hydrogen atoms or hydrocarbon groups.

[0083] In R 13 R 14 R 15 and R 16 When the hydrocarbon group is used, it is a hydrocarbon group with 1 to 20 carbon atoms that can be replaced by heteroatoms, preferably a hydrocarbon group with 1 to 12 carbon atoms that can be replaced by heteroatoms, more preferably a hydrocarbon group with 1 to 6 carbon atoms that can be replaced by heteroatoms, even more preferably a hydrocarbon group with 1 to 4 carbon atoms that can be replaced by heteroatoms, and even more preferably a hydrocarbon group with 1 to 2 carbon atoms that can be replaced by heteroatoms.

[0084] R 13 R 14 R 15 and R 16 Examples of hydrocarbon groups that are not substituted by heteroatoms include methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, pentyl, neopentyl, hexyl, octyl, benzyl, and phenyl, with methyl, ethyl, neopentyl, and phenyl being preferred, and methyl and ethyl being more preferred.

[0085] Additionally, R 13 R 14 R 15 and R 16 As a hydrocarbon group substituted by a heteroatom, it is at least one of the -CH2- that constitutes the hydrocarbon group, for example, a hydrocarbon group substituted by at least one of -O-, -NH-, -N(R)- (R represents a hydrocarbon group), -S-, -SO2-, etc.

[0086] Additionally, R 13 R 14 R 15 and R 16 They can form ring structures together with the carbon atoms they are bonded to.

[0087] As R 13 R 14 R 15 and R 16 The preferred atoms are hydrogen atoms, methyl groups, and ethyl groups.

[0088] Examples of amine compounds represented by formulas (2-3) include piperazine, 2,6-dimethylpiperazine, 2,6-diethylpiperazine, 2,6-diisopropylpiperazine, 2,6-di(tert-butyl)piperazine, 2,6-diphenylpiperazine, 2,6-dibenzylpiperazine, 3,5-dimethylpiperazine, 3,5-diethylpiperazine, 3,5-diisopropylpiperazine, 3,5-di(tert-butyl)piperazine, 3,5-diphenylpiperazine, 3,5-dibenzyl-piperazine, etc.

[0089] [Amine compounds represented by formula (2-4)] Equation (2-4): [Chemistry 14]

[0090] (R 17 R 18 R 19 and R 20 Each is independent. R 17 R 18 R 19 and R 20 Represents a hydrogen atom or a hydrocarbon group. In R... 17 R 18 R 19 and R 20 In the case of a hydrocarbon group, which is a hydrocarbon group with 1 to 20 carbon atoms that can be replaced by heteroatoms, it can form a ring structure together with the carbon atoms and / or nitrogen atoms to which it is bonded. In equation (2-4), R 17 R 18 R 19 and R 20 Each is independent.

[0091] R 17 R 18 R 19 and R 20 It consists of hydrogen atoms or hydrocarbon groups.

[0092] In R 17 R 18 R 19 and R 20 When the hydrocarbon group is used, it is a hydrocarbon group with 1 to 20 carbon atoms that can be replaced by heteroatoms, preferably a hydrocarbon group with 1 to 12 carbon atoms that can be replaced by heteroatoms, more preferably a hydrocarbon group with 1 to 6 carbon atoms that can be replaced by heteroatoms, even more preferably a hydrocarbon group with 1 to 4 carbon atoms that can be replaced by heteroatoms, and particularly preferably a hydrocarbon group with 1 to 2 carbon atoms that can be replaced by heteroatoms.

[0093] R 17 R 18 R 19and R 20 Examples of hydrocarbon groups that are not substituted by heteroatoms include methyl, ethyl, propyl, n-butyl, sec-butyl, tert-butyl, pentyl, neopentyl, hexyl, octyl, benzyl, and phenyl, with methyl, ethyl, neopentyl, and phenyl being preferred, and methyl and ethyl being more preferred.

[0094] Additionally, R 17 R 18 R 19 and R 20 As a hydrocarbon group substituted by a heteroatom, it is at least one of the -CH2- that constitutes the hydrocarbon group, for example, a hydrocarbon group substituted by at least one of -O-, -NH-, -N(R)- (R represents a hydrocarbon group), -S-, -SO2-, etc.

[0095] Additionally, R 17 R 18 R 19 and R 20 They can form ring structures together with the carbon and / or nitrogen atoms they are bonded to.

[0096] As with R 17 R 18 R 19 and R 20 The ring structure formed by the bonded carbon atoms and / or nitrogen atoms is composed of R 18 and R 18 The bonded nitrogen atom and R 19 and R 19 The bonded carbon atoms form a 6- to 8-membered ring structure; composed of R 17 and R 17 The bonded nitrogen atom, R 19 The bonded carbon atom and R 20 and R 20 The 5- to 7-membered ring structure formed by the bonded nitrogen atoms; and the R 18 and R 18 The bonded nitrogen atom and R 19 and R 19 The 6- to 8-membered rings formed by the bonded carbon atoms, and the R 17 and R 17 The bonded nitrogen atom, R 19 The bonded carbon atom and R 20 and R 20 Ring structures formed by the condensation of 5- to 7-membered rings formed by the bonded nitrogen atoms, etc.

[0097] As R 17 R 18 R 19 and R 20 The preferred atoms are hydrogen atoms, methyl groups, and ethyl groups.

[0098] Additionally, as with R 17 R 18 R 19 and R 20 The ring structure formed by the bonded carbon atoms and / or nitrogen atoms is preferably composed of R 18 and R 18 The bonded nitrogen atom and R 19 and R 19 The 7-membered ring formed by the bonded carbon atoms, composed of R 17 and R 17 The bonded nitrogen atom, R 19 The bonded carbon atom and R 20 and R 20 The ring structure is formed by the condensation of a 6-membered ring formed by the bonded nitrogen atoms.

[0099] Examples of amine compounds represented by formulas (2-4) include imidazole, 1-methylimidazolium, 2-methylimidazolium, 4-methylimidazolium, diazabicycloundecene (1,8-diazabicyclo[5.4.0]-7-undecene), 1,5-diazabicyclo[4.3.0]-5-nonene, etc.

[0100] In the capped polyisocyanate compositions of the present invention, the amount of the amine compound represented by formulas (2-1) to (2-4) relative to the capped polyisocyanate compound is determined according to the required physical properties and is not particularly limited. Generally, the [amount of effective isocyanate groups of the capped polyisocyanate compound] is set to 100 mol, and relative to this 100 mol, it is in the range of 5 to 25 mol%, preferably in the range of 10 to 20 mol%, and more preferably in the range of 13 to 18 mol%. It should be noted that the effective isocyanate groups of the capped polyisocyanate compound refer to the isocyanate groups that are regenerated when the capping agent dissociates from the capped polyisocyanate compound.

[0101] <Curing Resin Composition> The curable resin composition of the present invention comprises the end-capped polyisocyanate composition of the present invention and a compound having isocyanate reactive groups.

[0102] <Compounds with isocyanate reactive groups> Examples of compounds containing isocyanate reactive groups include polyols, polyamines, and alkanolamines, which have two or more active hydrogen groups. These compounds containing isocyanate reactive groups can be mixtures of two or more types.

[0103] As a compound having isocyanate reactive groups, polyols or polyamines are preferred.

[0104] [Polyols] In this invention, the polyol is a compound having two or more hydroxyl groups. Examples include polyester polyols, polyether polyols, acrylic polyols, polyolefin polyols, and fluorinated polyols. Among these, acrylic polyols are preferred from the viewpoints of weather resistance, chemical resistance, and hardness. Alternatively, polyester polyols are preferred from the viewpoints of mechanical strength and oil resistance. These polyols can be mixtures of two or more.

[0105] [Polyester polyols] Polyester polyols can be obtained, for example, by condensing a dicarboxylic acid alone or in a mixture of two or more with a polyol alone or in a mixture of two or more.

[0106] Examples of dicarboxylic acids used in polyester polyols include succinic acid, adipic acid, dimer acid, maleic anhydride, phthalic anhydride, isophthalic acid, terephthalic acid, and carboxylic acids such as 1,4-cyclohexanedicarboxylic acid.

[0107] Examples of polyols used in polyester polyols include: ethylene glycol, propylene glycol, diethylene glycol, 1,4-butanediol, neopentyl glycol, 1,6-hexanediol, trimethylpentanediol, cyclohexanediol, trimethylolpropane, glycerol, pentaerythritol, 2-hydroxymethylpropanediol, ethoxylated trimethylolpropane, etc.

[0108] As a specific method for manufacturing polyester polyols, for example, the aforementioned diacid and polyol can be mixed and heated at approximately 160–220°C to carry out a condensation reaction. Alternatively, for example, the polyol can be used to... e Polycaprolactones, obtained by ring-opening polymerization of lactones such as caprolactone, can also be used as polyester polyols. These polyester polyols can be modified with aromatic diisocyanates, aliphatic diisocyanates, alicyclic diisocyanates, and polyisocyanates derived from them. Among these, from the viewpoints of weather resistance and yellowing resistance, polyester polyols are preferably modified with aliphatic diisocyanates, alicyclic diisocyanates, and polyisocyanates derived from them.

[0109] When the curable resin composition of the present invention is used as a water-based base coating, a portion of the carboxylic acid, such as dicarboxylic acid, from the polyester polyol is left as a residue beforehand and neutralized by alkalis such as amines and ammonia, thereby enabling the polyester polyol to become a water-soluble or water-dispersible resin.

[0110] [Polyether polyols] Examples of polyether polyols include: aliphatic amine polyols, aromatic amine polyols, Mannich polyols, polyols, polyphenols, bisphenols, and other active hydrogen compounds, as well as compounds obtained by adding epoxides to them. These polyether polyols can be mixtures of two or more types.

[0111] Examples of aliphatic amine polyols include alkylene diamine polyols and alkanolamine polyols. These polyol compounds are polyfunctional polyols formed by ring-opening addition of at least one cyclic ether such as ethylene oxide or propylene oxide using alkylene diamines or alkanolamines as initiators, resulting in terminal hydroxyl groups. Known compounds can be used without limitation as the alkylene diamine. Specifically, alkylene diamines with 2 to 8 carbon atoms, such as ethylenediamine, propylenediamine, butanediamine, hexamethylenediamine, and neopentyldiamine, are preferred. These aliphatic amine polyols can be mixtures of two or more.

[0112] Aromatic amine polyols are polyfunctional polyether polyol compounds with terminal hydroxyl groups formed by ring-opening addition of at least one of cyclic ethers such as ethylene oxide and propylene oxide using an aromatic diamine as an initiator. Known aromatic diamines can be used without limitation as initiators. Specifically, examples include 2,4-toluenediamine, 2,6-toluenediamine, diethyltoluenediamine, 4,4′-diaminodiphenylmethane, p-phenylenediamine, o-phenylenediamine, and naphthylenediamine. The use of toluenediamine (2,4-toluenediamine, 2,6-toluenediamine, or mixtures thereof) is particularly preferred. These aromatic amine polyols can be mixtures of two or more.

[0113] Mannich polyols are active hydrogen compounds obtained by the Mannich reaction of phenol and / or its alkyl-substituted derivatives, formaldehyde, and alkanolamines, or by ring-opening addition polymerization of the compound with at least one of ethylene oxide and propylene oxide. These Mannich polyols may be mixtures of two or more.

[0114] Examples of polyols include diols (such as ethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol, diethylene glycol, triethylene glycol, dipropylene glycol, neopentyl glycol, etc.) and alcohols with three or more components (such as glycerol, trimethylolpropane, pentaerythritol, methyl glucoside, sorbitol, sucrose, etc.). These polyols can be mixtures of two or more components.

[0115] Examples of polyphenols include pyrogallol and hydroquinone. These polyphenols can be mixtures of two or more.

[0116] Examples of bisphenols include bisphenol A, bisphenol S, bisphenol F, and low-condensity condensates of phenol and formaldehyde. These bisphenols can be mixtures of two or more types.

[0117] As a method for manufacturing polyether polyols, for example, any one of the following manufacturing methods 1 to 3 can be used.

[0118] Manufacturing Method 1: A method of randomly or block adding epoxide alone or in mixtures to polyhydroxy compounds alone or in mixtures using a catalyst to obtain polyether polyols.

[0119] Examples of catalysts used in manufacturing method 1 include: hydroxides (lithium, sodium, potassium, etc.), strongly basic catalysts (alkoxides, alkylamines, etc.), and complex metal cyanide complexes (metal porphyrins, zinc hexacyanocobaltate complexes, etc.).

[0120] Examples of epoxides used in manufacturing method 1 include ethylene oxide, propylene oxide, butane oxide, cyclohexane oxide, and styrene oxide.

[0121] Examples of polyhydroxy compounds used in manufacturing method 1 include the following polyhydroxy compounds (i) to (vi).

[0122] (i) Diglycerides, bis(trimethylolpropane), pentaerythritol, dipentaerythritol, etc.

[0123] (ii) Sugar alcohol compounds such as erythritol, D-threitol, L-arabinitol, ribitol, xylitol, sorbitol, mannitol, galactitol, and rhamnitol.

[0124] (iii) Monosaccharides such as arabinose, ribose, xylose, glucose, mannose, galactose, fructose, sorbose, rhamnose, fucose, and deoxyribose.

[0125] (iv) Disaccharides such as trehalose, sucrose, maltose, cellobiose, gentiobiose, lactose, and melibiose.

[0126] (v) Trisaccharides such as raffinose, gentiotriose, and pinotriose.

[0127] (vi) Stachyose and other four sugars.

[0128] Manufacturing method 2: A method of reacting polyamine compounds with epoxides to obtain polyether polyols.

[0129] Examples of polyamine compounds used in manufacturing method 2 include ethylenediamines.

[0130] As an epoxide used in manufacturing method 2, an epoxide identical to the one exemplified in manufacturing method 1 can be cited.

[0131] Manufacturing method 3: A method of polymerizing acrylamide and the like using polyether polyols obtained in manufacturing method 1 or manufacturing method 2 as a medium to obtain so-called polymer polyols.

[0132] [Acrylic polyols] Acrylic polyols can be obtained, for example, by polymerizing a polymerizable monomer having one or more active hydrogen atoms in one molecule, or by copolymerizing a polymerizable monomer having one or more active hydrogen atoms in one molecule with other monomers that can copolymerize with the polymerizable monomer as needed.

[0133] Examples of polymerizable monomers having one or more active hydrogen atoms in a molecule include the monomers listed below (i) to (vi). They can be used alone or in combination of two or more.

[0134] (i) Acrylates with active hydrogen, such as 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, and 2-hydroxybutyl acrylate.

[0135] (ii) Methacrylates with active hydrogen, such as 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 2-hydroxybutyl methacrylate, 3-hydroxypropyl methacrylate, and 4-hydroxybutyl methacrylate.

[0136] (iii) (meth)acrylates containing multiple active hydrogens, such as mono-meth)acrylates of triols such as glycerol and trimethylolpropane.

[0137] (iv) Polyether polyols (e.g., polyethylene glycol, polypropylene glycol, polybutylene glycol, etc.) and monoethers of the above-mentioned (meth)acrylates with active hydrogen.

[0138] (v) Additions of glycidyl methacrylate with monocarboxylic acids (e.g., acetic acid, propionic acid, p-tert-butylbenzoic acid, etc.).

[0139] (vi) By making lactones (e.g., e -Caprolactam, c Additives obtained by ring-opening polymerization of (meth)acrylates with active hydrogen, such as valproic acid lactone, with the active hydrogen of the above-mentioned (meth)acrylates.

[0140] Other monomers that can copolymerize with the polymerizable monomer include, for example, the monomers listed below (i) to (iv). They can be used alone or in combination of two or more.

[0141] (i) Methyl acrylate, ethyl acrylate, isopropyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, n-hexyl methacrylate, cyclohexyl methacrylate, lauryl methacrylate, glycidyl methacrylate, and other (meth)acrylates.

[0142] (ii) Acrylic acid, methacrylic acid, maleic acid, itaconic acid, etc., and unsaturated amides (acrylamide, N-hydroxymethylacrylamide, diacetone acrylamide, etc., unsaturated carboxylic acids).

[0143] (iii) Vinyltrimethoxysilane, vinylmethyldimethoxysilane, c Vinyl monomers with hydrolyzable silanes, such as (meth)acryloylpropyltrimethoxysilane.

[0144] (iv) Other polymerizable monomers such as styrene, vinyltoluene, vinyl acetate, acrylonitrile, and dibutyl fumarate.

[0145] Specific methods for manufacturing acrylic polyols include, for example, solution polymerization of the aforementioned monomer components in the presence of known free radical polymerization initiators such as peroxides or azo compounds, followed by dilution with organic solvents as needed, thereby obtaining acrylic polyols.

[0146] When the curable resin composition of the present invention is used as a water-based base coating, a water-based acrylic polyol can be manufactured by using known methods such as solution polymerization of the above-mentioned monomer components to convert them into an aqueous layer, emulsion polymerization, etc. In this case, by using amines or ammonia to neutralize the acidic portion of acrylic acid, methacrylic acid, or sulfonic acid monomers, water solubility or water dispersibility can be imparted to the acrylic polyol.

[0147] [Polyolefin polyols] Examples of polyolefin polyols include polybutadiene having two or more hydroxyl groups, hydrogenated polybutadiene having two or more hydroxyl groups, and hydrogenated polyisoprene having two or more hydroxyl groups.

[0148] Furthermore, in polyolefin polyols, the number of hydroxyl groups is preferably three, from the perspective of obtaining higher coating strength.

[0149] [Fluoropolyols] In this invention, "fluorinated polyol" refers to a polyol containing fluorine in its molecule. Specifically, examples of fluorinated polyols include copolymers of fluoroolefins, cyclovinyl ethers, hydroxyalkyl vinyl ethers, and vinyl monocarboxylatees disclosed in Japanese Patent Application Publication No. 57-34107 and Japanese Patent Application Publication No. 61-275311.

[0150] [Hydroxy value and acid value of polyols] The lower limit of the hydroxyl value of the polyol is preferably 10 mg KOH / g or more, more preferably 20 mg KOH / g or more, and even more preferably 30 mg KOH / g or more.

[0151] On the other hand, there is no particular upper limit on the hydroxyl value of polyols, for example, it can be below 300 mg KOH / g.

[0152] That is, the hydroxyl value of the polyol is preferably 10 mg KOH / g or more and 300 mg KOH / g or less, more preferably 20 mg KOH / g or more and 300 mg KOH / g or less, and even more preferably 30 mg KOH / g or more and 300 mg KOH / g or less.

[0153] In addition, the acid value of the polyol is preferably above 0 mg KOH / g and below 30 mg KOH / g.

[0154] Hydroxyl value and acid value can be determined according to JIS K1557.

[0155] The molar equivalent ratio (NCO / OH) of the isocyanate group to the hydroxyl group of the polyol in the above-mentioned capped polyisocyanate composition is preferably 0.2 or more and 5.0 or less, more preferably 0.4 or more and 3.0 or less, and even more preferably 0.5 or more and 2.0 or less.

[0156] [Polyamines] As the polyamine used in this invention, examples include polyamines having two or more primary or secondary amino groups in one molecule, wherein, preferably, polyamines having three or more primary or secondary amino groups in one molecule.

[0157] Specific examples of polyamines used in this invention include: diamines such as ethylenediamine, propylenediamine, butanediamine, triethylenediamine, hexamethylenediamine, 4,4′-diaminodicyclohexylmethane, piperazine, 2-methylpiperazine, and isophoronediamine; chain polyamines having three or more amino groups such as bis(hexamethylene)triamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentamethylenehexamine, and tetrapropylenepentamine; and cyclic polyamines such as 1,4,7,10,13,16-hexaazacyclooctadecane, 1,4,7,10-tetraazacyclodecane, 1,4,8,12-tetraazacyclopentadecane, and 1,4,8,11-tetraazacyclotetradecane.

[0158] [Alkylamine] The alkanolamines used in this invention refer to compounds having an amino group and a hydroxyl group in one molecule. Examples of alkanolamines include: monoethanolamine, diethanolamine, aminoethylethanolamine, N-(2-hydroxypropyl)ethylenediamine, mono-, di-(n- or iso-)propanolamine, ethylene glycol-bis-propylamine, neopentyl alcoholamine, methylethanolamine, etc.

[0159] [The ratio of the capped polyisocyanate composition to the compound having isocyanate reactive groups] In the curable resin composition of the present invention, the mixing ratio of the capped polyisocyanate composition to the compound having isocyanate reactive groups is determined according to the required physical properties and is not particularly limited. Generally, the ratio of [the amount of effective isocyanate groups of the capped polyisocyanate compound in the capped polyisocyanate composition (mol)] to [the amount of active hydrogen groups of the compound having isocyanate reactive groups (mol)] is in the range of 0.2 to 5, preferably in the range of 0.5 to 3. It should be noted that the effective isocyanate groups of the capped polyisocyanate compound refer to the isocyanate groups that are regenerated when the capping agent dissociates from the capped polyisocyanate compound.

[0160] [Cure catalyst] The curable resin composition of the present invention can further contain a curing catalyst in the end-capped polyisocyanate composition and the compound having isocyanate reactive groups.

[0161] As a curing catalyst, there are no particular limitations; examples include: dibutyltin dilaurate, dibutyltin di-2-ethylhexanoate, dioctyltin dilaurate, dibutyltin diacetate, dibutyltin dioxide, dioctyltin dioxide, tin acetylacetonate, tin acetate, tin octanoate, tin laurate, and other tin compounds; bismuth compounds such as bismuth octanoate, bismuth 2-ethylhexanoate, bismuth naphthenate, and bismuth acetylacetonate; tetrabutyl titanate and tetraisopropyl titanate. Titanium compounds such as titanium terephthalate; triethylamine, N,N,N′,N′-tetramethylethylenediamine, N,N,N′,N′-tetramethylpropanediamine, N,N,N′,N′′,N′′-pentamethyldiethylenetriamine, N,N,N′,N′′,N′′-pentamethyldipropylenetriamine, N,N,N′,N′-tetramethylguanidine, 1,3,5-tris(N,N-dimethylaminopropyl)hexahydro-pyridine, Tertiary amine compounds such as 1,4-diazabicyclo[2.2.2]octane (DABCO), 1,8-diazabicyclo[5.4.0]undec-7-ene, triethylenediamine, N,N,N′,N′-tetramethylhexamethylenediamine, N-methyl-N′-(2-dimethylaminoethyl)piperazine, N,N′-dimethylpiperazine, dimethylcyclohexylamine, N-methylmorpholine, N-ethylmorpholine, bis(2-dimethylaminoethyl) ether, 1-methylimidazolium, 1,2-dimethylimidazolium, 1-isobutyl-2-methylimidazolium, 1-dimethylaminopropylimidazolium; tetraalkylammonium halides such as tetramethylammonium chloride; tetraalkylammonium hydroxides such as tetramethylammonium hydroxide; tetraalkylammonium-2-ethylhexanoate, 2-hydroxypropyltrimethylammonium formate, 2-hydroxypropyltrimethylammonium-2-ethylhexanoate, and other tetraalkylammonium organic acid salts and other quaternary ammonium salts.

[0162] The preferred curing catalysts are dibutyltin dilaurate or bismuth 2-ethylhexanoate.

[0163] In addition, the curable resin composition of the present invention may contain melamine-based curing agents such as fully alkyl, hydroxymethyl, and alkylamino alkyl types as needed.

[0164] The content of the curing catalyst in the curable resin composition of the present invention is preferably 0.01 to 20% by weight, more preferably 0.1 to 10% by weight, relative to the end-capped polyisocyanate.

[0165] The terminated isocyanate composition and curable resin composition of the present invention may contain organic solvents.

[0166] The preferred organic solvent is one that is compatible with the end-capped polyisocyanate composition and the curable resin composition of the present invention.

[0167] As organic solvents, examples include: hydrocarbons such as benzene, toluene, xylene, cyclohexane, mineral oil, and naphtha; ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; esters such as ethyl acetate, butyl acetate, and acetic acid cellosol; alcohols such as methanol, ethanol, 2-propanol, butanol, 2-methoxyethanol, 2-ethoxyethanol, and 2-butoxyethanol; polyols such as ethylene glycol, propylene glycol, diethylene glycol, polyethylene glycol, and glycerol; and water. These solvents can be used alone or in combination of two or more.

[0168] Furthermore, the curable resin composition of the present invention can be used as an aqueous thermosetting resin composition dissolved or dispersed in water. When the curable resin composition of the present invention is used as an aqueous thermosetting resin composition, in order to improve the compatibility of the curable resin composition with water, solvents that show a tendency to mix with surfactants and water can be used, compared with the end-capped polyisocyanate composition of the present invention.

[0169] Examples of surfactants include: anionic surfactants such as fatty soaps, rosin acid soaps, alkyl sulfonates, dialkyl aryl sulfonates, alkyl sulfosuccinates, polyoxyethylene alkyl sulfates, and polyoxyethylene alkyl aryl sulfates; and nonionic surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene alkyl aryl ethers, and polyoxyethylene oxypropylene block copolymers.

[0170] Examples of solvents that exhibit a tendency to mix with water include: diethylene glycol dimethyl ether, diethylene glycol diethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, propylene glycol dimethyl ether, dipropylene glycol dimethyl ether, isobutanol, butyl ethylene glycol, N-methylpyrrolidone, butyl diethylene glycol, or butyl diethylene glycol acetate.

[0171] Among the solvents mentioned above, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, propylene glycol monomethyl ether, propylene glycol dimethyl ether, dipropylene glycol dimethyl ether, isobutanol, butylethylene glycol, N-methylpyrrolidone, and butyl diethylene glycol are preferred, and diethylene glycol dimethyl ether, diethylene glycol diethyl ether, propylene glycol dimethyl ether, and dipropylene glycol dimethyl ether are more preferred. These solvents can be used alone or in combination of two or more.

[0172] It should be noted that when the curable resin composition of the present invention is used as an aqueous thermosetting resin composition, ester solvents such as ethyl acetate, n-butyl acetate, and acetic acid cellosolve may sometimes undergo hydrolysis during storage, which is therefore not preferred.

[0173] In the end-capped polyisocyanate composition and curable resin composition of the present invention, known additives, pigments, etc. commonly used in the art can be used as needed. In addition, they can also be used in combination with known end-capped polyisocyanates.

[0174] As additives, there are no particular limitations, but examples include: ultraviolet absorbers, anti-coloring agents, antioxidants, leveling agents, defoamers, rheology control agents, thixotropic agents, thickeners, light stabilizers, plasticizers, surfactants, coupling agents, flame retardants, rust inhibitors, fluorescent whitening agents, pigment dispersants, and various other additives.

[0175] For example, hindered amine, benzotriazole, and benzophenone-based UV absorbers can be cited as examples. Perchlorate and hydroxylamine-based anti-staining agents can be cited as examples. Furthermore, hindered phenol, phosphorus, sulfur, and hydrazide-based antioxidants can be cited as examples.

[0176] As pigments, there are no particular limitations; examples include: organic pigments, inorganic pigments, carbon-based pigments, metallic foil pigments, and rust-preventive pigments.

[0177] For example, examples of organic pigments include quinacridone-based, azo-based, and phthalocyanine-based organic pigments. Examples of inorganic pigments include titanium dioxide, barium sulfate, calcium carbonate, and silicon dioxide.

[0178] As known end-capped polyisocyanates, examples include end-capped polyisocyanates prepared by reacting polyisocyanates with known end-capping agents. Known end-capping agents include, for example, phenolic compounds such as phenol, thiophenol, methyl thiophenol, xylenol, cresol, resorcinol, nitrophenol, and chlorophenol; oxime compounds such as acetone oxime, methyl ethyl ketone oxime, and cyclohexanone oxime; alcohol compounds such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, tert-butanol, tert-amyl alcohol, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monoethyl ether, propylene glycol monomethyl ether, and benzyl alcohol; pyrazole compounds such as 3,5-dimethylpyrazole and 1,2-pyrazole; triazole compounds such as 1,2,4-triazole; and halogenated alcohol compounds such as ethylene chlorohydrin and 1,3-dichloro-2-propanol. e -Caprolactam, d -valerol, c -butyrolactam, β - Proprolactam and other lactam compounds; active methylene compounds such as methyl acetoacetate, ethyl acetoacetate, acetylacetone, methyl malonate, and ethyl malonate; in addition, imide compounds, thiol compounds, imine compounds, urea compounds, and diaryl compounds can also be cited.

[0179] [Storage Method] The end-capped polyisocyanate composition and curable resin composition of the present invention can be stored at 0°C to 40°C.

[0180] [Curing Method] The curing method of the curable resin composition of the present invention is a method of heating a curable resin composition containing the end-capped polyisocyanate composition of the present invention and a compound having isocyanate reactive groups, or a curable resin composition further containing a curing catalyst.

[0181] The heating temperature varies depending on the end-capped polyisocyanate compound and amine compound (formulas (2-1) to (2-4)) in the end-capped polyisocyanate composition used, and can be around 60 to 250°C, preferably around 80 to 200°C. The reaction time can be set to around 30 seconds to 5 hours, preferably around 1 minute to 60 minutes.

[0182] The cured product of the present invention can be manufactured by curing the curable resin composition of the present invention using the above-described curing method.

[0183] [use] The terminated polyisocyanate composition, curable resin composition and cured product of the present invention can be used in coatings, coating materials, inks, adhesives, sealants, sealing materials, molding materials, etc.

[0184] For example, as a coating, it can be used in automobiles, buildings, metal products such as steel furniture, wood products such as musical instruments, machinery and vehicles such as construction machinery, building materials such as window frames, and electrical appliances such as office equipment.

[0185] In addition, it can be used as a coating material for artificial leather and rubber rollers, as a sealing material for electronic components, as a sealing material for automobiles and buildings, and as a molding material for 3D printers.

[0186] Example The invention is described in more detail using manufacturing examples and embodiments, but the invention is not limited to these embodiments.

[0187] (1) Infrared spectrophotometry conditions Device: FT-IR-6600 manufactured by JASCO Corporation Measurement method: Total internal reflection measurement (crystal: germanium) Points earned: 16 times (2) Gas chromatography Device: Shimadzu GC-2030 Detector: FID Column: DB-624 / inner diameter: 0.32mm, film thickness: 1.80 m m, Length: 30.0m, Oven temperature: 50℃ (10 minutes) → 10℃ / minute → 250℃ (5 minutes) INJ: 150℃ DET: 260℃ Carrier gas: Helium Linear velocity: 48.5 cm / sec Flow split ratio: 50.0 Injection volume: 1.0 m L Method for calculating the effective NCO content (%) The effective NCO group content (%) here refers to the quantification of the amount of capped isocyanate groups present in the capped polyisocyanate compound that can react with isocyanate reactive groups, expressed as the mass (%) of isocyanate groups, and calculated by the following mathematical formula.

[0188] Effective NCO group content (%) = {(Solid content (mass (%) of the capped polyisocyanate compound) × (Mass of the polyisocyanate compound used in the reaction × NCO group content (%) of the polyisocyanate compound used in the reaction)} / (Mass of the capped polyisocyanate compound) / {Solid content (%)}. It should be noted that if dilution is performed using solvents, the value at dilution should be recorded.

[0189] Methods for calculating solid composition An absolute standard curve for methyl isobutyl ketone (hereinafter referred to as MIBK) is prepared using gas chromatography. The content of MIBK in the sample is determined, and the solid content (%) after removing MIBK from the total amount is calculated.

[0190] Composition of curable resin composition The capped polyisocyanate compound, the compound with isocyanate reactive groups, the curing catalyst, and the amine compound are added in a ratio of effective NCO groups (mol): hydroxyl groups (mol): curing catalyst (mol): amine compound (mol) = 1.00:0.95:0 to 0.10:0.15. MIBK is added in a ratio of solid content of the capped polyisocyanate compound (g): solvent (g) = 1.0:1.0. It should be noted that the solvent here refers to the solvent used in the dilution containing the capped polyisocyanate compound. The effective NCO groups (mol) and hydroxyl groups (mol) are calculated using the following mathematical formula.

[0191] Effective NCO groups (mol) = Amount of end-capped polyisocyanate compound (g) × Effective NCO group content of end-capped polyisocyanate compound (%) ÷ 4202 Hydroxyl group (mol) = Amount of polyol added (g) × Hydroxyl value of polyol (mgKOH / g) ÷ 56.1 Example 1: Synthesis of MIBK solution (A-1) of the biuret-type HDI tert-butylethylamine (hereinafter referred to as tBEA) end-capped form. In a 2L, three-necked reactor after nitrogen replacement, 500.0g of biuret-type HDI (Desmodur N3200A, NCO group content: 22.8%, manufactured by Sumika Covestro Urethane Co., Ltd., NCO group content: 22.8%) and 50.0g of MIBK3 were added. Then, 274.0g (2.71mol) of tBEA (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise at 25°C, and the mixture was stirred at 25°C for 2 hours. The isocyanate group was confirmed at 2270 cm⁻¹ by infrared spectroscopy. -1The nearby infrared absorption peaks disappeared. The resulting reaction solution was concentrated under reduced pressure to remove tBEA and a portion of MIBK, yielding 1040.39 g of a MIBK solution (A-1) of the tBEA-terminated biuret-type HDI. The obtained tBEA-terminated biuret-type HDI (A-1) had a solid content of 72% and an effective NCO group content of 10%.

[0192] Example 1 The curable resin composition was prepared by adding 5.00 g of the tBEA end-capping agent (A-1) of the biuret-type HDI obtained in Manufacturing Example 1, 13.6 g of acrylic polyol (ACRIT6AN 6000, manufactured by TAISEI FINE CHEMICAL Co., Ltd.), 0.387 g of dibutyltin dilaurate (manufactured by Tokyo Chemical Industry Co., Ltd.), and 0.180 g of tBEA (manufactured by Tokyo Chemical Industry Co., Ltd.) in a ratio of effective NCO groups (mol): hydroxyl groups (mol): curing catalyst (mol): amine compound (mol) = 1.00:0.95:0.01:0.15. Then, 2.20 g of MIBK was added in a ratio of 1.0 times the weight of the end-capping polyisocyanate compound, and the mixture was stirred for 30 minutes to prepare the curable resin composition.

[0193] The prepared curable resin composition was filled to 80% capacity in a 4 mL spiral tube and stored under a nitrogen atmosphere for one week. After one week, if the curable resin composition solidified, it was considered to have no storage stability; if it remained liquid, it was considered to have storage stability. The results are shown in Table 1. In the evaluation results, those with storage stability are indicated by "○", and those without storage stability are indicated by "×".

[0194] Examples 2-5, Comparative Examples 1-4 In Example 1, the polyol compound, curing catalyst, and amine compound were replaced with the substances shown in Table 1. Otherwise, the curable resin composition was prepared in the same manner as in Example 1. Furthermore, in Examples 4 and 5 and Comparative Examples 3 and 4, the storage temperature and storage time were changed to the storage temperatures and storage times shown in Table 1. Otherwise, the storage stability was evaluated in the same manner as in Example 1. The results are shown in Table 1.

[0195] [Table 1]

[0196] A-1: tBEA end-capped form of biuret-type HDI obtained in Example 1 B-1: Acrylic polyol (ACRIT6AN 6000, manufactured by TAISEI FINE CHEMICAL Co., Ltd.) B-2: Polyester polyol (P510, manufactured by Kuraray Corporation) C-1: Dibutyltin dilaurate C-2: Bismuth 2-ethylhexanoate D-1: tBEA D-2: Diisopropylamine As can be seen from the results of Examples 1-5 and Comparative Examples 1-4, the curable resin compositions containing the end-capped polyisocyanate compounds and amine compounds of the present invention exhibit superior storage stability for 1 week to 1 month under the same storage conditions compared to the curable resin compositions without amine compounds.

Claims

1. An end-capped polyisocyanate composition characterized in that, The capped polyisocyanate compound contains a secondary amine compound represented by the following formula (1) capping isocyanate groups of a polyisocyanate compound, and an amine compound represented by at least one of the following formulae (2-1), (2-2), (2-3), and (2-4), Formula (1): ; In formula (1), R 1 , R 2 , R 3 , R 4 , and R 5 are each independently, R 1 , R 2 , and R 3 represent a hydrocarbon group having 1 to 20 carbon atoms which is substituted or unsubstituted with a heteroatom, R 4 and R 5 represent a hydrocarbon group having 1 to 20 carbon atoms which is substituted or unsubstituted with a heteroatom or a hydrogen atom, R 1 , R 2 , R 3 , R 4 , and R 5 together with the carbon atom to which they are bonded form a ring structure or do not form a ring structure, Formula (2-1): ; In formula (2-1), R 6 and R 7 are each independently, R 6 and R 7 represent a hydrocarbon group having 1 to 20 carbon atoms which is or is not substituted with a heteroatom, R 6 and R 7 together with the nitrogen atom to which they are bonded form a ring structure or do not form a ring structure, Formula (2-2): ; In formula (2-2), R 8 , R 9 , R 10 , R 11 , and R 12 are each independently R 8 , R 9 , R 10 , R 11 , and R 12 represent a hydrogen atom or a hydrocarbon group, and in the case where R 8 , R 9 , R 10 , R 11 , and R 12 are hydrocarbon groups, are a hydrocarbon group having 1 to 20 carbon atoms which is substituted or unsubstituted with a heteroatom, form a ring structure or do not form a ring structure together with the carbon atom to which they are bonded, Formula (2-3): ; In formula (2-3), R 13 , R 14 , R 15 , and R 16 are each independently R 13 , R 14 , R 15 , and R 16 represent a hydrogen atom or a hydrocarbon group, and in the case where R 13 , R 14 , R 15 , and R 16 are hydrocarbon groups, are a hydrocarbon group having 1 to 20 carbon atoms which is substituted or unsubstituted with a heteroatom, form a ring structure or do not form a ring structure together with the carbon atom to which they are bonded, Formula (2-4): ; In formula (2-4), R 17 , R 18 , R 19 , and R 20 are each independently R 17 , R 18 , R 19 , and R 20 represent a hydrogen atom or a hydrocarbon group, and in the case where R 17 , R 18 , R 19 , and R 20 are hydrocarbon groups, are a hydrocarbon group having 1 to 20 carbon atoms which is substituted or unsubstituted with a heteroatom, form a ring structure or do not form a ring structure together with the carbon atom and / or nitrogen atom to which they are bonded.

2. The blocked polyisocyanate composition of claim 1, wherein, The polyisocyanate compound is at least one polyisocyanate selected from the group consisting of an aliphatic polyisocyanate, an alicyclic polyisocyanate, an aromatic polyisocyanate, and an aromatic-aliphatic polyisocyanate, or is a modified polyisocyanate formed from at least one polyisocyanate selected from the group consisting of an aliphatic polyisocyanate, an alicyclic polyisocyanate, an aromatic polyisocyanate, and an aromatic-aliphatic polyisocyanate.

3. The blocked polyisocyanate composition of claim 1, wherein, R 1 , R 2 , and R 3 are hydrocarbon groups having 1 to 2 carbon atoms, R 4 and R 5 are hydrocarbon groups having 1 to 2 carbon atoms or hydrogen atoms. R 1 , R 2 , and R 3 are hydrocarbon groups having 1 to 2 carbon atoms, R 4 and R 5 are hydrocarbon groups having 1 to 2 carbon atoms or hydrogen atoms.

4. A curable resin composition, characterized by comprising: The capped polyisocyanate composition of any one of claims 1 to 3 and a compound having an isocyanate-reactive group.

5. The curable resin composition according to claim 4, wherein, The compound having an isocyanate-reactive group is a polyol compound or a polyamine compound.

6. A curable resin composition, characterized by comprising: The curable resin composition of claim 4 and a curing catalyst.

7. A cured product, characterized by, The cured product is obtained by curing the curable resin composition of claim 6.

Images