Curing agent composition and its use

Abstract

To provide a hardener composition that contains a polyisocyanate compound and a metal compound and has high storage stability.SOLUTION: A hardener composition contains a polyisocyanate compound (A), a specific aluminum compound (B), and a solvent (C) in specific amounts, and optionally contains a dehydrant (D) and a stabilizer (E).SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a curing agent composition. The present invention also relates to a multi-component curable resin composition, a multi-component coating composition, and a cured product using the curing agent composition. [Background technology]

[0002] In paints used in a wide range of industries such as construction, home appliances, and automobiles, two-component acrylic urethane paints are commonly used, employing acrylic polyol as the main component and polyisocyanate as the curing agent. There is a method of using metal compounds (e.g., aluminum, tin, iron, titanium, zinc, etc.) as curing agents in addition to two-component acrylic urethane paints to improve the properties of the paint film (for example, Patent Document 1). [Prior art documents] [Patent Documents]

[0003] [Patent Document 1] Japanese Patent Publication No. 2018-115336 [Overview of the project] [Problems that the invention aims to solve]

[0004] However, as mentioned above, when using a metal compound and a polyisocyanate compound together as a curing agent, it is necessary for the mixture to have storage stability for commercialization. However, since the metal compound also acts as a polymerization catalyst for the polyisocyanate, the polyisocyanate compound becomes highly molecular weight during storage, leading to a problem of poor storage stability.

[0005] Therefore, one aspect of the present invention aims to provide a curing agent composition comprising a polyisocyanate compound and a metal compound, wherein the curing agent composition has improved storage stability. [Means for solving the problem]

[0006] As a result of diligent research to solve the above problems, the present inventors have discovered for the first time that a curing agent composition with excellent storage stability can be obtained by using a specific aluminum compound as the metal compound in a curing agent composition containing a polyisocyanate compound, a metal compound, and a solvent, and have completed the present invention.

[0007] Accordingly, one aspect of the present invention is a curing agent composition comprising a polyisocyanate compound (A), an aluminum compound (B), a solvent (C), an optional dehydrating agent (D), and a stabilizer (E), wherein the aluminum compound (B) (i) does not have alkyl and alkoxy groups directly bonded to aluminum, and (ii) has a β-dicarbonyl compound directly bonded to aluminum, and the curing agent composition contains 10 to 50% by weight of the polyisocyanate compound (A), 1 to 15% by weight of the aluminum compound (B), and 30 to 80% by weight of the solvent (C) based on 100% by weight of the total amount of components (A) to (E). [Effects of the Invention]

[0008] According to one aspect of the present invention, a curing agent composition comprising a polyisocyanate compound and a metal compound, and exhibiting excellent storage stability, can be provided. [Modes for carrying out the invention]

[0009] One embodiment of the present invention will be described in detail below. Unless otherwise specified herein, "A to B" representing a numerical range means "greater than or equal to A and less than or equal to B". Furthermore, in this specification, "(meth)acrylic" means "acrylic" and / or "methacrylic". In addition, all references cited herein are incorporated herein by reference.

[0010] [1. Outline of the present invention] A curing agent composition according to one embodiment of the present invention (hereinafter referred to as "this curing agent composition") is a curing agent composition comprising a polyisocyanate compound (A), an aluminum compound (B), a solvent (C), and optionally a dehydrating agent (D) and a stabilizer (E), wherein the aluminum compound (B) (i) does not have alkyl groups and alkoxy groups directly bonded to aluminum, and (ii) has a β-dicarbonyl compound directly bonded to aluminum, and is characterized in that, based on 100% by weight of the total amount of components (A) to (E), it contains 10 to 50% by weight of the polyisocyanate compound (A), 1 to 15% by weight of the aluminum compound (B), and 30 to 80% by weight of the solvent (C).

[0011] As described above, in multi-component curable resin compositions such as two-component acrylic urethane paints, when a curing agent composition containing a polyisocyanate compound and a metal compound is used as the second component, there is a problem in that the polyisocyanate compound becomes high molecular weight during storage due to the catalytic action of the metal compound, resulting in poor storage stability.

[0012] As a result of diligent research to solve the above problems, the inventors of this invention have succeeded in obtaining the following findings. In a curing agent composition containing a polyisocyanate compound, a metal compound, and a solvent, a curing agent composition with excellent storage stability can be obtained by using a specific aluminum compound as the metal compound. • Further addition of a dehydrating agent and / or a stabilizer to the above curing agent composition improves storage stability. The cured product obtained by curing a curable resin composition containing the above curing agent composition exhibits excellent adhesion, scratch resistance, and chemical resistance. By setting the amounts of the polyisocyanate compound, aluminum compound, and solvent in the curing agent composition to a specific ratio, a multi-component curable resin composition containing the curing agent composition can be efficiently cured.

[0013] The storage stability in a curing agent composition containing a polyisocyanate compound and a metal compound is important for commercializing a two-component paint composition such as a two-component acrylic urethane paint using the curing agent composition. Therefore, this curing agent composition is extremely useful.

[0014] Also, regarding a curing agent composition containing a polyisocyanate compound and a metal compound, in Patent Document 1, a method for improving storage stability by using a blocked polyisocyanate as the polyisocyanate compound has been proposed. However, a curing agent composition containing a blocked polyisocyanate needs to be heated at a high temperature (for example, 100°C or higher) when obtaining a cured product, which is difficult to apply to a substrate with low heat resistance such as plastic, and also has a large energy cost. This curing agent composition can achieve excellent storage stability without using a blocked polyisocyanate, so there is no need to heat at a high temperature during curing. Therefore, the curable resin composition containing this curing agent composition can be suitably used for a substrate with low heat resistance and is also useful in terms of low energy cost.

[0015] [2. Curing Agent Composition] This curing agent composition contains a polyisocyanate compound (A), an aluminum compound (B), and a solvent (C), and contains the polyisocyanate compound (A), the aluminum compound (B), and the solvent (C) in specific ratios, and further optionally contains a dehydrating agent (D) and a stabilizer (E). Due to having the above configuration, this curing agent composition can provide a curing agent composition with improved storage stability among curing agent compositions containing a polyisocyanate compound and an aluminum compound.

[0016] In this specification, the storage stability of the curing agent composition can be evaluated by the molecular weight change rate. Here, the molecular weight change rate is the ratio of the difference in the number average molecular weight (Mn) or weight average molecular weight (Mw) of the curing agent composition before and after storage, and more specifically, it is a value represented by the following formula (a) or (b). Molecular weight change rate (Mn) (%) = { (Molecular weight (Mn) of the curing agent composition after storage - Molecular weight (Mn) of the curing agent composition before storage) / Molecular weight (Mn) of the curing agent composition before storage} × 100 ··· (a) Molecular weight change rate (Mw) (%) = { (Molecular weight (Mw) of the curing agent composition after storage - Molecular weight (Mw) of the curing agent composition before storage) / Molecular weight (Mw) of the curing agent composition before storage} × 100 ··· (b) In this specification, "the curing agent composition has excellent storage stability" means that both the molecular weight change rate (Mn) and the molecular weight change rate (Mw) when the curing agent composition is stored at 50°C for 1 week are 50% or less, and it is intended that gelation does not occur. Therefore, in this curing agent composition, it is preferable that both the molecular weight change rate (Mn) and the molecular weight change rate (Mw) when the curing agent composition is stored at 50°C for 1 week are 50% or less, and both the molecular weight change rate (Mn) and the molecular weight change rate (Mw) when stored at 50°C for 2 weeks are less than 30%, and more preferably both the molecular weight change rate (Mn) and the molecular weight change rate (Mw) when stored at 50°C for 4 weeks are less than 30%.

[0017] Incidentally, when this curing agent composition is used as a component of a two - component curable resin composition, it corresponds to the second component (curing agent).

[0018] (Polyisocyanate compound (A)) This curing agent composition contains a polyisocyanate compound (A). Hereinafter, "polyisocyanate compound (A)" may be referred to as "component (A)".

[0019] In this specification, "polyisocyanate compound" means a compound having two or more isocyanate groups in one molecule. That is, component (A) has two or more isocyanate groups in one molecule.

[0020] The number of isocyanate groups in component (A) is not particularly limited as long as there are two or more per molecule, but it is preferably 2.1 or more, more preferably 2.3 or more, and even more preferably 2.5 or more. The upper limit of the number of isocyanate groups in component (A) is not particularly limited, but for example, it is preferably 20 or less, more preferably 10 or less, and particularly preferably 5 or less. If the number of isocyanate groups in component (A) is 20 or less, (i) it has excellent compatibility with the resin component described later (e.g., acrylic polyol), and (ii) there is no risk of steric repulsion of the isocyanate groups, so a curing agent composition with excellent reactivity can be obtained.

[0021] The number-average molecular weight (Mn) of component (A) is not particularly limited, but is preferably 150 to 1000, more preferably 200 to 800, and even more preferably 300 to 700, as this results in good compatibility and reactivity. The number-average molecular weight (Mn) of component (A) is calculated using GPC on a polystyrene basis.

[0022] As component (A), conventionally known polyisocyanate compounds can be used. Examples of such polyisocyanate compounds include aliphatic polyisocyanate compounds, alicyclic polyisocyanate compounds, aromatic aliphatic polyisocyanate compounds, aromatic polyisocyanate compounds, and the like.

[0023] Examples of aliphatic polyisocyanate compounds include trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, pentamethylene diisocyanate, 1,2-propylene diisocyanate, 1,2-butylene diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene diisocyanate, 2,4,4- or 2,2,4-trimethylhexamethylene diisocyanate, and 2,6-diisocyanate. Examples include diisocyanate compounds such as methyl caproate; compounds having three or more isocyanate groups, such as lysine ester triisocyanate, 1,4,8-triisocyanate octane, 1,6,11-triisocyanate undecane, 1,8-diisocyanate-4-isocyanate methyl octane, 1,3,6-triisocyanate hexane, and 2,5,7-trimethyl-1,8-diisocyanate-5-isocyanate methyl octane.

[0024] Examples of alicyclic polyisocyanate compounds include 1,3-cyclopentene diisocyanate, 1,4-cyclohexane diisocyanate, 1,3-cyclohexane diisocyanate, 3-isocyanate methyl-3,5,5-trimethylcyclohexyl isocyanate, 4,4′-methylenebis(cyclohexyl isocyanate), methyl-2,4-cyclohexane diisocyanate, methyl-2,6-cyclohexane diisocyanate, and 1,3 -Diisocyanate compounds such as bis(isocyanate methyl)cyclohexane, 1,4-bis(isocyanate methyl)cyclohexane, isophorone diisocyanate; 1,3,5-triisocyanate cyclohexane, 1,3,5-trimethylisocyanate cyclohexane, 3-isocyanate methyl-3,3,5-trimethylcyclohexyl isocyanate, 2-(3-isocyanate propyl)-2,5-di(isocyanate methyl)-bis(isocyanate methyl) Chlo[2,2,1]heptane, 2-(3-isocyanatetopropyl)-2,6-di(isocyanatemethyl)-bicyclo[2,2,1]heptane, 3-(3-isocyanatetopropyl)-2,5-di(isocyanatemethyl)-bicyclo[2,2,1]heptane, 5-(2-isocyanateethyl)-2-isocyanatemethyl-3-(3-isocyanatetopropyl)-bicyclo[2,2,1]heptane, 6-(2-isocyanateethyl)-2-i Examples include compounds having three or more isocyanate groups, such as socyanatemethyl-3-(3-isocyanatetopropyl)-bicyclo[2,2,1]heptane, 5-(2-isocyanateethyl)-2-isocyanatemethyl-2-(3-isocyanatetopropyl)-bicyclo[2,2,1]heptane, and 6-(2-isocyanateethyl)-2-isocyanatemethyl-2-(3-isocyanatetopropyl)-bicyclo[2,2,1]heptane.

[0025] Examples of aromatic aliphatic polyisocyanate compounds include diisocyanate compounds such as 1,3- or 1,4-xylylene diisocyanate or mixtures thereof, ω,ω′-diisocyanate-1,4-diethylbenzene, 1,3- or 1,4-bis(1-isocyanate-1-methylethyl)benzene or mixtures thereof; and compounds having three or more isocyanate groups, such as 1,3,5-triisocyanatemethylbenzene.

[0026] Examples of aromatic polyisocyanate compounds include diisocyanate compounds such as m-phenylenediisocyanate, p-phenylenediisocyanate, 4,4′-diphenyldiisocyanate, 1,5-naphthalenediisocyanate, 4,4′-diphenylmethanediisocyanate, 2,4- or 2,6-tolylenediisocyanate, 4,4′-toluidinediisocyanate, and 4,4′-diphenyletherdiisocyanate; and compounds having three or more isocyanate groups such as triphenylmethane-4,4′,4″-triisocyanate, 1,3,5-triisocyanatebenzene, 2,4,6-triisocyanatetoluene, 4,4′-diphenylmethane-2,2′,5,5′-tetraisocyanate, and polymethylene polyphenyl polyisocyanate (polymeric MDI).

[0027] In one embodiment of the present invention, various modified polyisocyanate compounds may be used as component (A). Examples of such modified compounds include allophanate modified compounds, biuret modified compounds, isocyanurate modified compounds, and the like.

[0028] Component (A) is preferably a polyisocyanate having a cyclic, linear, or branched structure, and is more preferably one or more selected from the group consisting of aromatic polyisocyanates, alicyclic polyisocyanates, and aromatic aliphatic polyisocyanates. Polyisocyanates having a cyclic structure in the molecule, such as alicyclic polyisocyanate compounds, aromatic aliphatic polyisocyanate compounds, and aromatic polyisocyanate compounds, are more preferred because they significantly improve the physical properties (adhesion, toughness, impact resistance) of the resulting cured product. Among these, aromatic polyisocyanates are even more preferred, and 4,4′-diphenylmethane diisocyanate, 2,4- or 2,6-tolylene diisocyanate, and polymethylene polyphenyl polyisocyanate (polymeric MDI) are particularly preferred because the resulting curable resin composition has excellent adhesion.

[0029] Aliphatic polyisocyanate compounds and alicyclic polyisocyanate compounds are preferred because the resulting cured products exhibit excellent weather resistance. In particular, hexamethylene diisocyanate, isophorone diisocyanate, and their isocyanurate-modified derivatives are preferred.

[0030] When yellowing is a problem when using these polyisocyanate compounds, it is preferable to use aliphatic, alicyclic, or aromatic aliphatic polyisocyanates, with aliphatic or alicyclic polyisocyanates being more preferable.

[0031] In one embodiment of the present invention, component (A) may also be a blocked isocyanate obtained by masking the isocyanate group with a blocking agent and inactivating it at room temperature. Examples of blocking agents include alcohols, phenols, oximes, triazoles, caprolactams, and the like.

[0032] In one embodiment of the present invention, the polyisocyanate compound (A) is preferably a polyisocyanate compound in which the isocyanate groups are not masked by a blocking agent (hereinafter also referred to as "unblocked polyisocyanate compound"). In this embodiment, a curing agent composition with excellent storage stability and low cost can be provided without using a polyisocyanate compound in which the isocyanate groups are masked by a blocking agent (hereinafter also referred to as "blocked polyisocyanate compound"), which is generally considered to have superior storage stability compared to unblocked polyisocyanate compounds. Furthermore, when an unblocked polyisocyanate compound is included, it is not necessary to heat the cured product at a high temperature (e.g., 100°C or higher), and it can be suitably used on substrates with low heat resistance, such as plastics.

[0033] In the case of blocked polyisocyanate compounds, storage stability problems are generally less likely to occur. However, for example, if the water content in the curing agent composition is high, even if a blocked polyisocyanate compound is included, gelation may occur, leading to a problem of reduced storage stability. Therefore, in another embodiment of the present invention, the polyisocyanate compound (A) may be a polyisocyanate compound in which the isocyanate groups are masked by a blocking agent.

[0034] The content of component (A) in this curing agent composition is preferably 10 to 50% by weight, more preferably 15 to 45% by weight, more preferably 20 to 45% by weight, even more preferably 25 to 45% by weight, and particularly preferably 30 to 40% by weight, based on 100% by weight of the total amount of components (A) to (E). When the content of component (A) in this curing agent composition is 10% by weight or more, a cured product with excellent elastic modulus can be provided. Furthermore, when the content of component (A) in this curing agent composition is 50% by weight or less, a cured product with sufficient toughness can be provided.

[0035] In addition, in one embodiment of the present invention, the content of component (A) in the present curing agent composition preferably contains 70 to 95% by weight, more preferably 72 to 94% by weight, and even more preferably 74 to 93% by weight with respect to 100% by weight of the total amount of component (A) and component (B) described below. When the content of component (A) in the present curing agent composition is 70% by weight or more with respect to 100% by weight of the total amount of component (A) and component (B), a cured product excellent in elastic modulus can be provided. Further, when the content of component (A) in the present curing agent composition is 95% by weight or less with respect to 100% by weight of the total amount of component (A) and component (B), a cured product having sufficient toughness can be provided.

[0036] (aluminum compound (B)) The present curing agent composition contains an aluminum compound (B) which (i) does not have an alkyl group and an alkoxy group directly bonded to an aluminum atom and (ii) has a β-dicarbonyl compound directly bonded to the aluminum atom. Hereinafter, the "aluminum compound (B)" may be referred to as "component (B)".

[0037] In the present specification, component (B) is intended to be a compound represented by the following general formula (I): [Chemical formula]

[0039] (In the formula, R 2 , 3 , 1 , 3 , 1 , 2 , , R 2 and R [[ID=2)] 3 at least one of which is a β-dicarbonyl compound, and all of the functional groups that are not β-dicarbonyl compounds among R 1 , R 2 and R 3 are not alkyl groups and alkoxy groups.) In the formula (I), R 1 , R 2 and R 3This includes embodiments in which at least one is a β-dicarbonyl compound, two are β-dicarbonyl compounds, and all are β-dicarbonyl compounds. Preferably, R 1 , R 2 and R 3 These are all β-dicarbonyl compounds. Here, a β-dicarbonyl compound is a compound having a structure in which two carbonyl groups are bonded to one carbon atom. There are no particular limitations on β-dicarbonyl compounds, but examples include alkyl acetates such as ethyl acetate and methyl acetate, acetyl acetonate, and dimethyl malonate. Among these, ethyl acetate is preferred because of its excellent solubility in organic solvents and organic resins.

[0040] Furthermore, in equation (I) above, R 1 , R 2 and R 3 Of these, all functional groups that are not β-dicarbonyl compounds are neither alkyl groups nor alkoxy groups.

[0041] Furthermore, in equation (I) above, R 1 , R 2 and R 3 These may be the same or they may be different.

[0042] Component (B) is not particularly limited as long as it is a compound represented by the above formula (I), but examples include aluminum tris(ethyl acetate), aluminum tris(acetylacetonate), aluminum ethyl acetate(diacetylacetonate), and aluminum diethyl acetate(acetylacetonate). Among these, aluminum tris(ethyl acetate) is preferred because it is readily available, inexpensive, and has excellent solubility in organic solvents and organic resins. Component (B) may be used individually or in combination of multiple types.

[0043] The content of component (B) in this curing agent composition is 1 to 15% by weight, preferably 3 to 13% by weight, more preferably 5 to 11% by weight, and even more preferably 7 to 9% by weight, based on 100% by weight of the total amount of components (A) to (E). When the content of component (B) in this curing agent composition is 1% by weight or more, curing proceeds at a moderate rate. Furthermore, when the content of component (B) in this curing agent composition is 15% by weight or less, it is possible to avoid curing that is too fast and makes handling difficult.

[0044] Furthermore, in one embodiment of the present invention, the content of component (B) in the curing agent composition is preferably 2 to 15% by weight, more preferably 2.5 to 13% by weight, and even more preferably 3 to 10% by weight, based on 100% by weight of the total amount of component (A), component (B), and component (C) described later. When the content of component (B) in the curing agent composition is 2% by weight or more based on 100% by weight of the total amount of component (A), component (B), and component (C), curing proceeds at a moderate rate. Also, when the content of component (B) in the curing agent composition is 15% by weight or less based on 100% by weight of the total amount of component (A), component (B), and component (C), it is possible to avoid curing that is too fast and makes handling difficult.

[0045] (Solvent (C)) This curing agent composition contains solvent (C). Hereinafter, "solvent (C)" may be referred to as "component (C)".

[0046] Component (C) is not particularly limited and various compounds can be used. More specifically, examples of solvents (C) include hydrocarbon solvents such as toluene, xylene, heptane, hexane, and petroleum solvents; halogen solvents such as trichloroethylene; ester solvents such as ethyl acetate, butyl acetate, isobutyl acetate (IBAC), and methoxypropyl acetate; ketone solvents such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; ether solvents such as dibutyl ether, dipentinyl ether, diethylene glycol monomethyl ether, propylene glycol monomethyl ether, propylene glycol methyl ether acetate (PMA), and diethylene glycol monoethyl ether; and silicone solvents such as hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, and decamethylcyclopentasiloxane. Among these, ester solvents and ether solvents are preferred due to their availability, solubility, and drying properties, with isobutyl acetate, methoxypropyl acetate, and propylene glycol methyl ether acetate being particularly preferred. These solvents may be used individually or in combination of two or more.

[0047] The content of component (C) in this curing agent composition is 30 to 80% by weight, preferably 35 to 80% by weight, more preferably 40 to 80% by weight, and even more preferably 45 to 75% by weight, based on 100% by weight of the total amount of components (A) to (E). When the content of component (C) in this curing agent composition is 30% by weight or more, a curing agent composition with low viscosity, high thixotropy, and excellent workability can be obtained. Furthermore, when the content of component (C) in this curing agent composition is 80% by weight or less, there is no risk of excessive environmental pollution.

[0048] (Dehydrating agent (D)) The curing agent composition preferably further contains a dehydrating agent (D) in addition to a polyisocyanate compound (A), an aluminum compound (B), and a solvent (C). When the curing agent composition contains a dehydrating agent (D), it exhibits excellent storage stability, particularly storage stability when stored for a long period of time.

[0049] The dehydrating agent (D) is not particularly limited, but examples include tosyl isocyanate, vinyltrimethoxysilane, calcium oxide, zeolite, p-toluenesulfonyl isocyanate, 3-ethyl-2-methyl-2-(3-methylbutyl)-1,3-oxazolidine, trimethyl orthoformate, triethyl orthoformate, trimethyl orthoacetate, and triethyl orthoacetate. These dehydrating agents may be used alone or in combination of two or more. Among these dehydrating agents, tosyl isocyanate and / or trimethyl orthoacetate are preferred because they are highly reactive and have the advantage of not generating substances that adversely affect the coating performance after the dehydration reaction.

[0050] The content of the dehydrating agent (D) in this curing agent composition is, for example, 0.5 to 10% by weight, preferably 0.75 to 7.0% by weight, and more preferably 1.0 to 5.0% by weight, based on 100% by weight of the total amount of components (A) to (E). When the content of the dehydrating agent (D) in this curing agent composition is 0.5% by weight or more, the increase in molecular weight of isocyanate due to moisture can be suppressed. Furthermore, when the content of the dehydrating agent (D) in this curing agent composition is 10% by weight or less, it does not remain as a plasticizer in the film when a cured product (coating film) is obtained, so there is no risk of impairing the physical properties of the coating film, and it is also economically advantageous.

[0051] Furthermore, in one embodiment of the present invention, the content of component (D) in the curing agent composition is preferably 0.1% to 5% by weight, more preferably more than 0.5% and 4% or less by weight, and even more preferably more than 1.0% and 3% or less by weight, based on 100% by weight of the total amount of components (A) to (D). When the content of component (D) in the curing agent composition is 0.1% or more by weight based on 100% by weight of the total amount of components (A) to (D), it has the advantage of suppressing the increase in molecular weight of isocyanate due to moisture. Also, when the content of component (D) in the curing agent composition is 3% or less by weight based on 100% by weight of the total amount of components (A) to (D), it does not remain as a plasticizer in the film when a cured product (coating film) is obtained, so there is no risk of impairing the physical properties of the coating film, and it is also economically advantageous.

[0052] (Stabilizer (E)) The curing agent composition preferably further contains a dehydrating agent (D) in addition to a polyisocyanate compound (A), an aluminum compound (B), and a solvent (C). In one embodiment of the present invention, the curing agent composition may contain both a dehydrating agent (D) and a stabilizer (E). When the curing agent composition contains a stabilizer (E), it is possible to provide a cured product with superior coating film performance such as adhesion, scratch resistance, and chemical resistance. In particular, by including a stabilizer (E), the cured product can be used without impairing its curability even after storage, thus providing an excellent cured product.

[0053] The stabilizer (E) is not particularly limited, but examples include acetylacetone, dimedone, meldrumic acid, 1,3-cyclohexanedione, ethyl acetacetate, methyl acetacetate, dimethyl malonate, and diethyl malonate. These stabilizers may be used individually or in combination of two or more.

[0054] The content of stabilizer (E) in this curing agent composition is, for example, 0.5 to 10% by weight, preferably 0.75 to 7.0% by weight, and more preferably 1.0 to 5.0% by weight, based on 100% by weight of the total amount of components (A) to (E). When the content of stabilizer (E) in this curing agent composition is 0.5% by weight or more, a curing agent composition with excellent storage stability can be provided. Furthermore, when the content of stabilizer (E) in this curing agent composition is 10% by weight or less, it has the advantage of not easily inhibiting curing reactivity.

[0055] Furthermore, in one embodiment of the present invention, the content of component (E) in the curing agent composition is preferably 0.1% to 5% by weight, more preferably 0.5% to 4% by weight, and even more preferably 1.0% to 3% by weight, based on 100% by weight of the total amount of components (A) to (D). When the content of component (E) in the curing agent composition is 0.1% by weight or more based on 100% by weight of the total amount of components (A) to (D), the curing properties after storage are well maintained. In addition, when the content of component (E) in the curing agent composition is 5% by weight or less based on 100% by weight of the total amount of components (A) to (D), it has the advantage of not inhibiting the curing reaction.

[0056] (Other ingredients) The curing agent composition may contain additives commonly used in the art, to the extent that it achieves the effects of the present invention. Examples of such additives include flame retardants, dispersants, defoamers, plasticizers, tackifiers, leveling agents, thixotropic agents, epoxy resins, antioxidants, light stabilizers, UV absorbers, silane coupling agents, hydrolysis stabilizers, titanate coupling agents, aluminate coupling agents, mold release agents, antistatic agents, lubricants, low shrinkage agents, silicone surfactants, and water. The composition may contain only one or more additives. The amounts of these additives can be appropriately determined by those skilled in the art depending on their intended use. Furthermore, these additives can be added to the curing agent composition at any time; for example, they may be added when mixing components (A) to (E), or they may be added immediately before using the curing agent composition.

[0057] In one embodiment of the present invention, the content of components other than the polyisocyanate compound (A), the aluminum compound (B), the solvent (C), the dehydrating agent (D), and the stabilizer (E) in the curing agent composition (i.e., the content of the other components mentioned above) is preferably 10% by weight or less, more preferably 5% by weight or less, and even more preferably 3% by weight or less, based on 100% by weight of the total amount of components (A) to (E). When the content of the other components is 10% by weight or less, there is no risk of impairing the various physical properties (adhesion, scratch resistance, chemical resistance, etc.) of the resulting cured product (coating film).

[0058] <Flame retardant> This curing agent composition may contain a flame retardant. The flame retardant is not particularly limited, but examples include ammonium polyphosphate, phosphorus-based plasticizers such as tricresyl phosphate, aluminum hydroxide, magnesium hydroxide, and thermally expandable graphite. These flame retardants may be used individually or in combination of two or more.

[0059] A wide range of conventionally known ammonium polyphosphates can be used as the aforementioned ammonium polyphosphate. Among these, from the viewpoint of water resistance, surface-treated ammonium polyphosphates such as ammonium polyphosphate coated with resin and microencapsulated, or surface-modified ammonium polyphosphate, are preferred, and those whose surface is coated with melamine formaldehyde resin are even more preferred.

[0060] The flame retardant content in this curing agent composition is, for example, 0 to 3% by weight, preferably 0 to 2.5% by weight, and more preferably 0 to 2% by weight, based on 100% by weight of the total amount of components (A) to (E).

[0061] <Dispersant> This curing agent composition may contain a dispersant. As a dispersant, a pigment dispersion paste obtained by mixing and dispersing a pigment and a dispersant according to a known method can be incorporated and used. Commercially available dispersants can also be used. For example, ANTI-TERRA(registered trademark)-U, ANTI-TERRA(registered trademark)-U100, ANTI-TERRA(registered trademark)-204, ANTI-TERRA(registered trademark)-205, DISPERBYK(registered trademark)-101, DISPERBYK(registered trademark)-102, DISPERBYK(registered trademark)-103, DISPERBYK(registered trademark)-106, DISPERBYK(registered trademark)-108, DISPERBYK(registered trademark)-109, DISPERBYK(registered trademark) Trademark)-110, DISPERBYK(Registered Trademark)-111, DISPERBYK(Registered Trademark)-112, DISPERBYK(Registered Trademark)-116, DISPERBYK(Registered Trademark)-130, DISPERBYK(Registered Trademark)-140, DISPERBYK(Registered Trademark)-142, DISPERBYK(Registered Trademark)-145, DISPERBYK(Registered Trademark)-161, DISPERBYK(Registered Trademark)-162, DISPERBYK(Registered Trademark)-163, DISPERBYK(Registered Trademark) Registered Trademark)-164, DISPERBYK(Registered Trademark)-166, DISPERBYK(Registered Trademark)-167, DISPERBYK(Registered Trademark)-168, DISPERBYK(Registered Trademark)-170, DISPERBYK(Registered Trademark)-171, DISPERBYK(Registered Trademark)-174, DISPERBYK(Registered Trademark)-180, DISPERBYK(Registered Trademark)-182, DISPERBYK(Registered Trademark)-183, DISPERBYK(Registered Trademark)-184, DISPERBYK( Registered Trademark)-185, DISPERBYK(Registered Trademark)-2000, DISPERBYK(Registered Trademark)-2001, DISPERBYK(Registered Trademark)-2008, DISPERBYK(Registered Trademark)-2009, DISPERBYK(Registered Trademark)-2022, DISPERBYK(Registered Trademark)-2025, DISPERBYK(Registered Trademark)-2050, DISPERBYK(Registered Trademark)-2070, DISPERBYK(Registered Trademark)-2096, DISPERBYK(Registered Trademark)-2150,DISPERBYK(registered trademark)-2155, DISPERBYK(registered trademark)-2163, DISPERBYK(registered trademark)-2164, BYK(registered trademark)-P104, BYK(registered trademark)-P104S, BYK(registered trademark)-P105, BYK(registered trademark)-9076, BYK(registered trademark)-9077, BYK(registered trademark)-220S, ANTI-TERRA(registered trademark)-250, DISPERBYK(registered trademark)-187, DISPERBYK(registered trademark)-190, DISPERBYK(registered trademark)-191 DISPERBYK(registered trademark)-192, DISPERBYK(registered trademark)-193, DISPERBYK(registered trademark)-194, DISPERBYK(registered trademark)-198, DISPERBYK(registered trademark)-2010, DISPERBYK(registered trademark)-2012, DISPERBYK(registered trademark)-2015, DISPERBYK(registered trademark)-2090, DISPERBYK(registered trademark)-2091, DISPERBYK(registered trademark)-2095 (all manufactured by Big Chemie), DISPARLON(registered trademark) )2150, DISPARLON(registered trademark)KS-860, DISPARLON(registered trademark)KS-873N, DISPARLON(registered trademark)7004, DISPARLON(registered trademark)1831, DISPARLON(registered trademark)1850, DISPARLON(registered trademark)1860, DISPARLON(registered trademark)DA-1401, DISPARLON(registered trademark)PW-36, DISPARLON(registered trademark)DA-1200, DISPARLON(registered trademark)DA-550, DISPARLON(registered trademark) Examples include DA-703-50, DISPARLON® DA-7301, DISPARLON® DN-900, DISPARLON® DA-325, DISPARLON® DA-375, DISPARLON® DA-234 (all manufactured by Kusumoto Kasei Co., Ltd.), EFKA POLYMER 4550 (manufactured by EFKA), Solspers® 27000, Solspers® 41000, Solspers® 53095 (all manufactured by Abyssia).

[0062] The number-average molecular weight of the dispersant is preferably 1,000 to 100,000, preferably 2,000 to 50,000, and more preferably 4,000 to 50,000. If the number-average molecular weight of the dispersant is 1000 or more, sufficient dispersion stability can be obtained, and if it is 100,000 or less, there is no risk of the composition becoming too viscous, resulting in a composition with excellent handling properties.

[0063] The dispersant content in this curing agent composition is, for example, 0 to 3% by weight, preferably 0 to 2.5% by weight, and more preferably 0 to 2% by weight, based on 100% by weight of the total amount of components (A) to (E).

[0064] <Antifoaming agent> This curing agent composition may contain an antifoaming agent. The antifoaming agent is not particularly limited, but commercially available ones can be used. Examples of such commercially available antifoaming agents include BYK(registered trademark)-051, BYK(registered trademark)-052, BYK(registered trademark)-053, BYK(registered trademark)-054, BYK(registered trademark)-055, BYK(registered trademark)-057, BYK(registered trademark)-1752, BYK(registered trademark)-1790, BYK(registered trademark)-060N, BYK(registered trademark)-063, BYK(registered trademark)-065, BYK(registered trademark)-066N, BYK(registered trademark)-067A, BYK(registered trademark)-077, and BYK(registered trademark). -088, BYK(registered trademark)-141, BYK(registered trademark)-354, BYK(registered trademark)-392, BYK(registered trademark)-011, BYK(registered trademark)-012, BYK(registered trademark)-017, BYK(registered trademark)-018, BYK(registered trademark)-019, BYK(registered trademark)-020, BYK(registered trademark)-021, BYK(registered trademark)-022, BYK(registered trademark)-023, BYK(registered trademark)-024, BYK(registered trademark)-025, BYK(registered trademark)-028, BYK(registered trademark)-038, BY Antifoaming agents such as K(registered trademark)-044, BYK(registered trademark)-093, BYK(registered trademark)-094, BYK(registered trademark)-1610, BYK(registered trademark)-1615, BYK(registered trademark)-1650, BYK(registered trademark)-1730, BYK(registered trademark)-1770 (all manufactured by Big Chemie Co., Ltd.), and DISPARLON(registered trademark)OX-880EF, DISPARLON(registered trademark)OX-881, DISPARLON(registered trademark)OX-883, DISPARLON(registered trademark)OX-883HF, DI Acrylic defoamers such as SPARLON(registered trademark) OX-70, DISPARLON(registered trademark) OX-77EF, DISPARLON(registered trademark) OX-60, DISPARLON(registered trademark) OX-710, DISPARLON(registered trademark) OX-720, DISPARLON(registered trademark) OX-720EF, DISPARLON(registered trademark) OX-750HF, DISPARLON(registered trademark) LAP-10, DISPARLON(registered trademark) LAP-20, DISPARLON(registered trademark) LAP-30, etc.Examples include silicone-acrylic composite defoamers such as DISPARLON® OX-66 and DISPARLON® OX-715, vinyl-based defoamers such as DISPARLON® 1950, DISPARLON® 1951, DISPARLON® 1952, DISPARLON® P-410EF, DISPARLON® P-420, DISPARLON® P-450, DISPARLON® P-425, and DISPARLON® PD-7, and silicone-based defoamers such as DISPARLON® 1930N and DISPARLON® 1934 (all manufactured by Kusumoto Kasei Co., Ltd.).

[0065] The amount of the defoaming agent in this curing agent composition is, for example, 0 to 3% by weight, preferably 0 to 2.5% by weight, and more preferably 0 to 2% by weight, based on 100% by weight of the total amount of components (A) to (E).

[0066] <Tackifier> This curing agent composition may contain a tackifier. The tackifier is not particularly limited, and any tackifier commonly used at room temperature, whether solid or liquid, can be used. Specifically, examples include styrene-based block copolymers such as styrene-butadiene-styrene block copolymer (SBS), styrene-isoprene-styrene block copolymer (SIS), styrene-ethylenebutylene-styrene block copolymer (SEBS), styrene-ethylenepropylene-styrene block copolymer (SEPS), and styrene-isobutylene-styrene block copolymer (SIBS), as well as their hydrogenated derivatives, phenol resins, modified phenol resins (e.g., cashew oil-modified phenol resin, tall oil-modified phenol resin, etc.), terpene phenol resins, xylene-phenol resins, cyclopentadiene-phenol resins, coumarone indene resins, rosin-based resins, rosin ester resins, hydrogenated rosin ester resins, xylene resins, low molecular weight polystyrene-based resins, styrene copolymer resins, petroleum resins (e.g., C5 hydrocarbon resins, C9 hydrocarbon resins, C5C9 hydrocarbon copolymer resins, etc.), hydrogenated petroleum resins, terpene-based resins, DCPD resins, and petroleum resins. The above tackifiers may be used individually or in combination of two or more types.

[0067] The content of the tackifier in this curing agent composition is, for example, 0 to 3% by weight, preferably 0 to 2.5% by weight, and more preferably 0 to 2% by weight, based on 100% by weight of the total amount of components (A) to (E).

[0068] <Leveling agent> This curing agent composition may contain a leveling agent. The leveling agent is not particularly limited, but commercially available ones can be used. Examples of such commercially available leveling agents include BYKETOL®-OK, BYKETOL®-SPECIAL, BYKETOL®-AQ, BYKETOL®-WS (all manufactured by BYKETOL®), DISPARLON® 1970, DISPARLON® 230, DISPARLON® LF-1980, DISPARLON® LF-1982, DISPARLON® LF-1983, DISPARLON® LF-1984, and DISPARLON® LF-1985 (all manufactured by Kusumoto Chemical Co., Ltd.).

[0069] The leveling agent content in this curing agent composition is, for example, 0 to 3% by weight, preferably 0 to 2.5% by weight, and more preferably 0 to 2% by weight, based on 100% by weight of the total amount of components (A) to (E).

[0070] <Thixotropic agent> This curing agent composition may contain a thixotropic agent (anti-sagging agent). While not particularly limited, examples of anti-sagging agents include polyamide waxes, hydrogenated castor oil derivatives, and metal soaps such as calcium stearate, aluminum stearate, and barium stearate. The fumed silica mentioned above as a filler can also be used as a thixotropic agent. Furthermore, using rubber powder with a particle size of 10-500 μm, as described in Japanese Patent Publication No. 11-349916, or organic fibers, as described in Japanese Patent Publication No. 2003-155389, can yield a composition with high thixotropy and good workability. These thixotropic agents (anti-sagging agents) may be used individually or in combination of two or more.

[0071] The content of the thixotropic agent in this curing agent composition is, for example, 0 to 3% by weight, preferably 0 to 2.5% by weight, and more preferably 0 to 2% by weight, based on 100% by weight of the total amount of components (A) to (E).

[0072] <Thermoplastic resin> This curing agent composition may contain a thermoplastic resin. The thermoplastic resin is not particularly limited, but examples include polyolefin resins, polystyrene resins, acrylonitrile-styrene copolymer resins, epoxy resins, acrylic resins without hydroxyl groups, polycarbonate resins, and polyether resins. More specifically, examples of epoxy resins include aromatic epoxides, alicyclic epoxides, and aliphatic epoxides.

[0073] Examples of aromatic epoxides include glycidyl ethers of monovalent or polyvalent phenols (phenol, bisphenol A, phenol novolac, and alkylene oxide adducts thereof) having at least one aromatic ring.

[0074] Examples of alicyclic epoxides include 3,4-epoxycyclohexylmethyl-3',4'-epoxycyclohexanecarboxylate (e.g., manufactured by Daicel Chemical Industries, Ltd.: product name "Celoxide 2021P"), hydrogenated bisphenol A diglycidyl ether (e.g., manufactured by Kyoeisha Chemical Co., Ltd.: product name "Epolite 4000"), epsilon-caprolactone-modified 3,4-epoxycyclohexylmethyl-3',4'-epoxycyclohexanecarboxylate (e.g., manufactured by Daicel Chemical Industries, Ltd.: product name "Celoxide 2081"), and 1,2,8,9-diepoxylimonene (e.g., manufactured by Daicel Chemical Industries, Ltd.: product name "Celoxide 3000"). Examples of alicyclic epoxy compounds include vinylcyclohexene monooxide 1,2-epoxy-4-vinylcyclohexane (e.g., manufactured by Daicel Chemical Industries, Ltd.: trade name "Celoxide 2000"), 1,2-epoxy-4-(2-oxyranyl)cyclohexane adduct of 2,2-bis(hydroxymethyl)-1-butanol (e.g., manufactured by Daicel Chemical Industries, Ltd.: trade name "EHPE-3150"), bis-(3,4-epoxycyclohexyl) adipate, epoxy compounds in which epoxy is directly or via hydrocarbons is added to cyclic aliphatic hydrocarbons, and alicyclic epoxides such as heterocyclic epoxy compounds such as triglycidyl isocyanurate. Among these, epoxy compounds having an epoxycyclohexyl group are preferred, and 3,4-epoxycyclohexylmethyl-3',4'-epoxycyclohexane carboxylate and hydrogenated bisphenol A diglycidyl ether are more preferred.

[0075] Examples of aliphatic epoxides include polyglycidyl ethers of aliphatic polyhydric alcohols or alkylene oxide adducts thereof (e.g., 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether), polyglycidyl esters of aliphatic polybasic acids (e.g., diglycidyl tetrahydrophthalate), and epoxidized products of long-chain unsaturated compounds (e.g., epoxidized soybean oil and epoxidized polybutadiene).

[0076] The content of thermoplastic resin in this curing agent composition is, for example, 0 to 3% by weight, preferably 0 to 2.5% by weight, and more preferably 0 to 2% by weight, based on 100% by weight of the total amount of components (A) to (E).

[0077] <Antioxidant> This curing agent composition may contain an antioxidant (anti-aging agent). When the composition contains an antioxidant, the heat resistance of the resulting cured product can be improved. The antioxidant is not particularly limited, but examples include hindered phenols, monophenols, bisphenols, and polyphenols. Among these, hindered phenols are preferred. In one embodiment of the present invention, as an antioxidant, hindered amine-based photostabilizers such as Chinuvin® 622LD, Chinuvin® 144, CHIMASSORB® 944LD, CHIMASSORB® 119FL (all manufactured by Ciba Specialty Chemicals Co., Ltd.); MARKLA-57, MARKLA-62, MARKLA-67, MARKLA-63, MARKLA-68 (all manufactured by Asahi Denka Kogyo Co., Ltd.); Sanol® LS-770, Sanol® LS-765, Sanol® LS-292, Sanol® LS-2626, Sanol® LS-1114, Sanol® LS-744 (all manufactured by Sankyo Co., Ltd.) may also be used.

[0078] The antioxidant content in this curing agent composition is, for example, 0 to 3% by weight, preferably 0 to 2.5% by weight, and more preferably 0 to 2% by weight, based on 100% by weight of the total amount of components (A) to (E).

[0079] <Light stabilizer> This curing agent composition may contain a light stabilizer. When the composition contains a light stabilizer, photo-oxidative degradation of the resulting cured product can be prevented. The light stabilizer is not particularly limited, but examples include benzotriazole, hindered amine, and benzoate compounds. Among these, hindered amine compounds are preferred. In particular, tertiary amine-containing hindered amine light stabilizers are preferred because they can improve the storage stability of the composition. More specifically, examples of tertiary amine-containing hindered amine light stabilizers include CHINUVIN® 622LD, CHINUVIN® 144, CHIMASSORB® 119FL (all manufactured by BASF); MARK LA-57, LA-62, LA-67, LA-63 (all manufactured by ADEKA Corporation); and SANOL® LS-765, LS-292, LS-2626, LS-1114, LS-744 (all manufactured by Sankyo Co., Ltd.).

[0080] The amount of light stabilizer in this curing agent composition is, for example, 0 to 3% by weight, preferably 0 to 2.5% by weight, and more preferably 0 to 2% by weight, based on 100% by weight of the total amount of components (A) to (E).

[0081] <UV absorber> This curing agent composition may contain an ultraviolet absorber. When the composition contains an ultraviolet absorber, the surface weather resistance of the resulting cured product can be improved. The ultraviolet absorber is not particularly limited, but examples include benzophenone-based, benzotriazole-based, salicylate-based, substituted tolyl-based, and metal chelate compounds, with benzotriazole-based compounds being particularly preferred.

[0082] In one embodiment of the present invention, it is particularly preferable to use a mixture of a phenol-based or hindered phenol-based antioxidant, a hindered amine-based light stabilizer, and a benzotriazole-based ultraviolet absorber.

[0083] The amount of ultraviolet absorber in this curing agent composition is, for example, 00 to 3% by weight, preferably 0 to 2.5% by weight, and more preferably 0 to 2% by weight, based on 100% by weight of the total amount of components (A) to (E).

[0084] <Silane coupling agent> This curing agent composition may contain a silane coupling agent. When the composition contains a silane coupling agent, adhesion can be improved. The silane coupling agent is not particularly limited, but examples include isocyanate group-containing silanes such as γ-isocyanatetopropyltrimethoxysilane, γ-isocyanatetopropyltriethoxysilane, γ-isocyanatetopropylmethyldiethoxysilane, γ-isocyanatetopropylmethyldimethoxysilane, (isocyanatemethyl)trimethoxysilane, (isocyanatemethyl)dimethoxymethylsilane, (isocyanatemethyl)triethoxysilane, and (isocyanatemethyl)diethoxymethylsilane; γ-aminopropyltrimethoxysilane, γ-aminopropyltriisopropoxysilane, γ-aminopropylmethyldimethoxysilane, γ-aminopropylmethyldiethoxysilane, γ-(2-aminoethyl)aminopropyltrimethoxysilane, and γ-(2-aminoethyl)aminopropylmethyl Dimethoxysilane, γ-(2-aminoethyl)aminopropyltriethoxysilane, γ-(2-aminoethyl)aminopropylmethyldiethoxysilane, γ-(2-aminoethyl)aminopropyltriisopropoxysilane, γ-(6-aminohexyl)aminopropyltrimethoxysilane, 3-(N-ethylamino)-2-methylpropyltrimethoxysilane, γ-ureidopropyltrimethoxysilane, γ-ureidopropyltriethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, N-benzyl-γ-aminopropyltrimethoxysilane, N-vinylbenzyl-γ-aminopropyltriethoxysilane, N-cyclohexylaminomethyltriethoxysilane, N-cyclohexylaminomethyldiethoxymethylsilane, N-phenylaminomethyltrimethoxysilane, (2-aminoethyl)aminomethyltrimethoxysilane, N,N T-Silanes containing amino groups such as bis[3-(trimexysilyl)propyl]ethylenediamine; Ketimine-type silanes such as N-(1,3-dimethylbutylidene)-3-(triethoxysilyl)-1-propanamine; Silanes containing mercapto groups such as γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropylmethyldiethoxysilane, mercaptomethyltrimethoxysilane, mercaptomethyltriethoxysilane; γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, β-(3,4- Examples include epoxy group-containing silanes such as epoxycyclohexyl(ethyltriethoxysilane); carboxysilanes such as β-carboxyethyltriethoxysilane, β-carboxyethylphenylbis(2-methoxyethoxy)silane, and N-β-(carboxymethyl)aminoethyl-γ-aminopropyltrimethoxysilane; vinyl-type unsaturated group-containing silanes such as vinyltrimethoxysilane, vinyltriethoxysilane, γ-methacryloyloxypropylmethyldimethoxysilane, γ-acryloyloxypropyltriethoxysilane, and methacryloyloxymethyltrimethoxysilane; halogen-containing silanes such as γ-chloropropyltrimethoxysilane; and isocyanurate silanes such as tris(3-trimethoxysilylpropyl)isocyanurate. Furthermore, derivatives obtained by modifying these, such as amino-modified silyl polymers, silylated amino polymers, unsaturated aminosilane complexes, phenylamino long-chain alkyl silanes, aminosilylated silicones, and silylated polyesters, can also be used as silane coupling agents.

[0085] The content of the silane coupling agent in this curing agent composition is, for example, 0 to 3% by weight, preferably 0 to 2.5% by weight, and more preferably 0 to 2% by weight, based on 100% by weight of the total amount of components (A) to (E).

[0086] This curing agent composition may contain moisture derived from the above-mentioned components and other components. If the curing agent composition contains moisture, the storage stability of the curing agent composition may be impaired. Therefore, the moisture content in this curing agent composition is preferably 0.3% by weight or less, more preferably 0.1% by weight or less, and more preferably 0.05% by weight or less, based on 100% by weight of the total amount of components (A) to (E). The lower limit is not particularly limited and may be 0% by weight.

[0087] (Filler) The curing agent composition may further contain a filler. The filler is not particularly limited, but examples include reinforcing fillers such as fumed silica, precipitated silica, crystalline silica, fused silica, dolomite, anhydrous silicic acid, hydrated silicic acid, and carbon black; powdered fillers such as heavy calcium carbonate, colloidal calcium carbonate, magnesium carbonate, barium carbonate, barium sulfate, diatomaceous earth, calcined clay, clay, talc, barite, anhydrous gypsum, titanium dioxide, bentonite, organic bentonite, ferric oxide, aluminum powder, flint powder, zinc oxide, activated zinc oxide, mica, zinc oxide, lead white, lithopone, zinc sulfide, shirasu balloons, glass microballoons, organic microballoons of phenolic resin or vinylidene chloride resin, PVC powder, PMMA powder, etc.; and fibrous fillers such as asbestos, glass fibers, and filaments. In addition to the above, other coloring pigments such as titanium dioxide, lead chromate, chromium oxide, ultramarine, cobalt blue, cyanine blue, cyanine green, lake red, and quinacridone red can also be used.

[0088] The filler content in this curing agent composition is, for example, 0 to 100% by weight, preferably 0 to 50% by weight, and more preferably 0 to 30% by weight, based on 100% by weight of the total amount of components (A) to (E).

[0089] (Method for manufacturing the curing agent composition) The curing agent composition can be manufactured by mixing the above-mentioned components (polyisocyanate compound (A), aluminum compound (B), solvent (C), dehydrating agent (D), stabilizer (E), and other components as needed) by known methods. The mixing method is not particularly limited, but examples include using a mixing machine such as a mixing tank with agitator blades such as propeller type / oar type, a planetary mixer, a kneader, a hobbalt mixer, a high-speed mixer, a line mixer, a roll mill, a sand mill, an attritor, or a twin-screw mixer.

[0090] In the method for producing this curing agent composition, the above-mentioned components may be mixed simultaneously, or each component may be added, mixed, and homogenized sequentially. It is preferable to add each component, mix, and homogenize sequentially, as this yields a more uniformly mixed composition.

[0091] [3. Multi-component curable resin composition, multi-component coating composition] In one embodiment of the present invention, a multi-component curable resin composition (hereinafter referred to as "the curable resin composition") is provided, comprising a first liquid containing a (meth)acrylic polyol and a second liquid containing the curing agent composition. Because the curable resin composition contains the curing agent composition as a curing agent, it exhibits excellent storage stability despite containing a polyisocyanate compound and an aluminum compound. The curable resin composition can also be described as a multi-component curable resin composition comprising a resin component and the curing agent composition.

[0092] This curable resin composition is a multi-component curable resin composition. A multi-component curable resin composition can be prepared by separately manufacturing and storing a first liquid containing resin components and a second liquid containing a curing agent, and then mixing the first liquid and the second liquid immediately before use to provide a cured product.

[0093] (1st liquid) The first liquid contains a (meth)acrylic polyol. In a multi-component curable resin composition, the first liquid functions as the main component. The first liquid may contain only one type of (meth)acrylic polyol, or it may contain two or more types of (meth)acrylic polyols.

[0094] In this specification, "(meth)acrylic polyol" refers to a (meth)acrylic resin having two or more hydroxyl groups in its molecule. A (meth)acrylic polyol can also be described as a copolymer containing a (meth)acrylic monomer and a monomer having hydroxyl groups.

[0095] The hydroxyl value of (meth)acrylic polyol is, for example, 30 to 300 mgKOH / g, preferably 50 to 250 mgKOH / g, and more preferably 80 to 200 mgKOH / g. If the hydroxyl value of (meth)acrylic polyol is 20 to 300 mgKOH / g, a curable resin composition with high crosslinking density and excellent scratch resistance and chemical resistance can be obtained. In this specification, the hydroxyl value is the value measured according to the standard of JIS K 1557-1.

[0096] The number of hydroxyl groups contained in the molecule of (meth)acrylic polyol is, for example, 3 or more, preferably 5 or more, and more preferably 7 or more. If the number of hydroxyl groups contained in the molecule of component (B) is 3 or more, a dense crosslinked structure is formed, and a cured product (coating film) with excellent durability can be obtained. Furthermore, there is no particular upper limit to the number of hydroxyl groups contained in the molecule of component (B), but for example, it is 50 or less, preferably 40 or less. If the number of hydroxyl groups contained in the molecule of component (B) is 50 or less, the number of hydroxyl groups remaining in the cured product (coating film) after the curing reaction is reduced, and a cured product (coating film) with excellent water resistance can be obtained.

[0097] The (meth)acrylic monomers contained in (meth)acrylic polyols are not particularly limited, but examples include C1-C20 alkyl (meth)acrylates such as methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, t-butyl (meth)acrylate, and 2-ethylhexyl (meth)acrylate; C4-C20 cycloalkyl (meth)acrylates such as cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, and dicyclopentanyl (meth)acrylate; C3-C20 aralkyl (meth)acrylates such as allyl (meth)acrylate, dicyclopentenyl (meth)acrylate, and benzyl (meth)acrylate. The (meth)acrylic polyol may contain only one of these acrylic monomers, or it may contain two or more.

[0098] The monomers containing hydroxyl groups in (meth)acrylic polyols are not particularly limited, but examples include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, glycerol mono(meth)acrylate, cyclohexanedimethanol mono(meth)acrylate, 2-hydroxyethyl vinyl ether, N-methylol (meth)acrylamide, 4-hydroxystyrene vinyltoluene, and other hydroxyl group-containing vinyl monomers; Plac Examples include modified lactones or polyesters having polymerizable carbon-carbon double bonds at their termini, such as elFA-1, PlacelFA-4, PlacelFM-1, and PlacelFM-4 (all manufactured by Daicel Chemical Corporation); and polyoxyalkylenes having polymerizable carbon-carbon double bonds at their termini, such as the Bremmer PP series, Bremmer PE series, and Bremmer PEP series (all manufactured by NOF Corporation), A-30, MA-50, MA-100, MA-150, RA-1120, RA-2614, RMA-564, RMA-568, RMA-1114, and MPG130-MA (all manufactured by Nippon Emulsifier Co., Ltd.). (Meth)acrylic polyols may contain only one of these monomers having hydroxyl groups, or two or more.

[0099] Furthermore, (meth)acrylic polyols may contain monomers other than the (meth)acrylic monomers and monomers having hydroxyl groups described above (other monomers). Examples of other monomers are not particularly limited, but include olefin monomers such as ethylene and propylene, styrene monomers, monomers having reactive silicon groups, maleic acid monomers, fumaric acid monomers, itaconic acid monomers, etc. (meth)acrylic polyols may contain only one of these other monomers, or two or more.

[0100] The content of other monomers in the (meth)acrylic polyol is not particularly limited, but is preferably 0 to 5 mol%, more preferably 0 to 3 mol%, and even more preferably 0 to 2 mol%, relative to 100 mol% of the total amount of monomers contained in the (meth)acrylic polyol. A content of other monomers in the (meth)acrylic polyol of 0 to 5 mol% has the advantage that it does not impair the physical properties of the cured product (coating film).

[0101] The number-average molecular weight of the (meth)acrylic polyol is preferably 500 to 10000, more preferably 1000 to 8000, even more preferably 2000 to 7000, and particularly preferably 2500 to 6000. If the number-average molecular weight of the (meth)acrylic polyol is 500 or more, the (meth)acrylic polyol will not volatilize or bleed during the curing process or after curing. If it is 10000 or less, a cured product with excellent toughness and adhesion can be obtained.

[0102] The method for producing (meth)acrylic polyols is not particularly limited, but (meth)acrylic polyols can be produced by polymerizing the monomer having a (meth)acrylic group, a monomer having a hydroxyl group, and optionally other monomers by a known method (for example, by heating in the presence of a polymerization initiator).

[0103] In one embodiment of the present invention, the first liquid may contain other resin components in addition to the (meth)acrylic polyol. Such resin components are not particularly limited and include, for example, aliphatic alcohols, aromatic alcohols, polyether polyols, polyester polyols, polyolefin polyols, acrylic resins, graft-polymerized polysiloxane resins, polysiloxane resins having epoxy groups, and other polysiloxane resins.

[0104] Among these other resin components, polysiloxane resins are preferred because they exhibit excellent curability and co-crosslinking properties, as well as excellent scratch resistance and chemical resistance, and polysiloxane resins having epoxy groups are more preferred. The epoxy groups in the polysiloxane resin having epoxy groups are not particularly limited, but examples include glycidyloxy groups and epoxycyclohexyl groups. However, from the viewpoint of achieving both scratch resistance and chemical resistance, it is preferable to have both glycidyloxy groups and epoxycyclohexyl groups. In other words, it is preferable that the first liquid contains a polysiloxane resin having both glycidyloxy groups and epoxycyclohexyl groups as another resin component.

[0105] The first liquid may contain, in addition to the resin components described above, additives commonly used in the art. Examples of such additives include solvents, stabilizers, UV absorbers, antioxidants, hindered amines, fillers, and pigments. Only one of these additives may be included, or two or more may be included. The amount of these additives can be appropriately determined by those skilled in the art depending on the intended use.

[0106] (2nd liquid) The second liquid contains the curing agent composition. The second liquid functions as a curing agent in a multi-component curable resin composition.

[0107] In one embodiment of the present invention, the second liquid may contain other components in addition to the curing agent composition.

[0108] (Multi-component curable resin composition) As described above, this curable resin composition can be prepared by separately manufacturing and storing a first liquid containing resin components and a second liquid containing this curing agent composition, and then mixing the first liquid and the second liquid immediately before use to provide a cured product.

[0109] The mixing ratio of the acrylic polyol in the first liquid and the polyisocyanate compound in the second liquid in this curable resin composition can be appropriately adjusted depending on the application. The mixing ratio of the acrylic polyol in the first liquid and the polyisocyanate compound in the second liquid in this curable resin composition is preferably 80:20 to 50:50, more preferably 75:25 to 55:45, and even more preferably 70:30 to 60:40.

[0110] In one embodiment of the present invention, the curable resin composition can be further enhanced by adding a colorant, for example, when mixing the first liquid and the second liquid. This offers advantages such as providing a wide range of sealing materials in various colors to match the color of siding boards, even from a limited selection of curable resin compositions. Therefore, multi-component curable resin compositions can easily meet market demands for multi-color options and are suitable for low-rise building applications. For example, a paste made by mixing a pigment, a plasticizer, and a filler as needed is preferable due to its high workability.

[0111] Furthermore, in multi-component curable resin compositions, a retarder can be added during the mixing of the multi-component components. This allows for fine-tuning of the curing speed at the work site.

[0112] Furthermore, in one embodiment of the present invention, a multi-component coating composition containing the curable resin composition (hereinafter referred to as "the multi-component coating composition") is provided. The multi-component coating composition comprises a resin component containing (meth)acrylic polyol as the first liquid and the curable resin composition as the second liquid. In another embodiment of the present invention, the multi-component coating composition may also include, as a third liquid, other metal catalysts (for example, organometallic acid catalysts such as organotin compounds, organozinc compounds, organotitanium compounds, and organoiron compounds).

[0113] [4. Cured product] In one embodiment of the present invention, a cured product (hereinafter referred to as "the cured product") is provided, which is obtained by curing the curable resin composition or the multi-component paint composition. The cured product can also be described as a cured product obtained by curing a mixture of a first liquid containing (meth)acrylic polyol and a second liquid containing the curing agent composition.

[0114] The cured product is formed by curing the curable resin composition or the multi-component paint composition. Preferably, the cured product is formed by mixing a first liquid (main component) containing (meth)acrylic polyol and a second liquid (curing agent) containing the curing agent composition, and then heating and curing the resulting mixture.

[0115] The heating temperature when curing the mixture or this multi-component coating composition is not particularly limited, but is usually 50 to 200°C, but is preferably 60 to 120°C, more preferably 70 to 110°C, and even more preferably 80 to 100°C. The cured product can have excellent scratch resistance even when formed at relatively low temperatures such as 60 to 120°C.

[0116] The heating time for curing the mixture or the multi-component paint composition is not particularly limited, but from the viewpoint of balancing cost and the progress of the curing reaction, 10 to 120 minutes is preferred, 15 to 100 minutes is more preferred, and 30 to 60 minutes is even more preferred.

[0117] The thickness of the cured product is not particularly limited, but is preferably 1 to 100 μm. If the thickness of the cured product is 1 μm or more, the scratch resistance and water resistance of the cured coating film (cured product) will be good. If the thickness of the cured product is 100 μm or less, cracks due to curing shrinkage are less likely to occur. More preferably, it is 5 to 50 μm, and even more preferably 10 to 40 μm.

[0118] (Application) This curable resin composition, this multi-component coating composition, and this cured product can be used in a variety of applications. For example, transparent materials, optical materials, optical lenses, optical films, optical sheets, adhesives for optical components, optical adhesives for optical waveguide coupling, adhesives for fixing peripheral components of optical waveguides, adhesives for bonding DVDs, adhesives, dicing tapes, electronic materials, insulating materials (including printed circuit boards, wire coatings, etc.), high-voltage insulating materials, interlayer insulating films, insulating packings, insulating coatings, adhesives, high-heat-resistant adhesives, high-heat-dissipation adhesives, optical adhesives, adhesives for LED elements, adhesives for various substrates, adhesives for heat sinks, paints, inks, colored inks, coating materials (including hard coats, sheets, films, coatings for optical discs, coatings for optical fibers, etc.), molding materials (sheets, films, FRP) It can be applied to sealing materials, potting materials, encapsulating materials, encapsulating materials for light-emitting diodes, reflectors and reflectors for light-emitting diodes, optoelectronic semiconductor encapsulating materials, liquid crystal sealants, sealants for display devices, encapsulating materials for electrical materials, encapsulating materials for solar cells, high heat-resistant sealants, resist materials, liquid resist materials, colored resists, dry film resist materials, solder resist materials, materials for color filters, materials for photopolymerization, materials for electronic paper, materials for holograms, materials for solar cells, materials for fuel cells, display materials, recording materials, vibration-damping materials, waterproofing materials, moisture-proofing materials, heat-shrinkable rubber tubes, O-rings, photosensitive drums for copiers, solid electrolytes for batteries, and gas separation membranes. In addition, it can be applied to concrete protective materials, linings, soil injection agents, thermal storage materials, sealants for sterilization equipment, contact lenses, oxygen enrichment membranes, and as an additive to other resins, etc.

[0119] Furthermore, by mixing the first and second liquids of this curable resin composition, applying the resulting mixture, or this multi-component paint composition, to a substrate, and curing the mixture using a heat source to form a cured coating film, a laminate containing this cured material can be obtained. This laminate can be suitably used for front panels of personal computers, smartphones, tablets, etc., windows of automobiles, protective materials for lamps of automobiles, films, and the like.

[0120] The substrate is not particularly limited and may be, for example, metal (e.g., aluminum, stainless steel, copper, iron, etc.), ceramics, glass, cement, ceramic substrates, stone, plastics (e.g., polycarbonate (PC), acrylic, ABS, PC-ABS alloy, polyethylene terephthalate (PET), etc.), wood, paper, fibers, etc. The substrate may also be a film or a sheet. This curable resin composition can be suitably used for coating automobiles, buildings, home appliances, industrial equipment, etc. Since this curable resin composition and this multi-component paint composition harden upon heating, they are particularly suitable for forming a coating film on the surface of substrates with complex shapes. Furthermore, as described above, this curable resin composition and this multi-component paint composition can achieve excellent scratch resistance even when cured at relatively low temperatures of 60 to 120°C. Therefore, even if the substrate is an organic substrate, damage to the substrate due to heating during curing can be suppressed, which is an advantage as it can be suitably used on organic substrates as well.

[0121] The present invention is not limited to the embodiments described above, and various modifications are possible within the scope of the claims. Embodiments obtained by appropriately combining the technical means disclosed in different embodiments are also included in the technical scope of the present invention.

[0122] In other words, one aspect of the present invention includes the following: <1> Polyisocyanate compound (A) and, Aluminum compound (B) and, Solvent (C) and, Optionally, dehydrating agent (D) and A curing agent composition comprising a stabilizer (E), The aforementioned aluminum compound (B) is (i) It does not have alkyl or alkoxy groups directly bonded to aluminum, (ii) Having a β-dicarbonyl compound directly bonded to aluminum, With respect to 100% by weight of the total amount of the above components (A) to (E), The above polyisocyanate compound (A) is contained in an amount of 10 to 50% by weight. The aluminum compound (B) contains 1 to 15% by weight, A curing agent composition containing 30 to 80% by weight of the solvent (C). <2> The dehydrating agent (D) is included in an amount of 0.5 to 10% by weight relative to 100% by weight of the total amount of components (A) to (E). <1> The curing agent composition described above. <3> The stabilizer (E) is contained in an amount of 0.5 to 10% by weight relative to 100% by weight of the total amount of components (A) to (E). <1> or <2> The curing agent composition described above. <4> The polyisocyanate compound (A) is a polyisocyanate compound in which the isocyanate group is not masked by a blocking agent. <1> ~ <3> A curing agent composition as described in any of the following. <5> The content of components other than the polyisocyanate compound (A), the aluminum compound (B), the solvent (C), the dehydrating agent (D), and the stabilizer (E) is 10% by weight or less relative to the total amount of components (A) to (E) (100% by weight). <3> or <4> The curing agent composition described above. <6> A first liquid containing (meth)acrylic polyol, <1> ~ <5> A second liquid comprising the curing agent composition described in any of the above, A multi-component curable resin composition containing [the specified ingredient]. <7> <6> A multi-component coating composition comprising the multi-component curable resin composition described in [reference]. <8> <6> The multi-component curable resin composition described above, or <7> A cured product obtained by curing the multi-component paint composition described above. [Examples]

[0123] The present invention will be described in more detail below based on examples, but the present invention is not limited to these examples.

[0124] 〔material〕 The following materials were used in the examples and comparative examples. <Polyisocyanate compound (A)> Isocyanurate-modified hexamethylene diisocyanate: "Sumijoule N3300" manufactured by Covestro. <Aluminum compound (B)> Aluminum (trisethylacetate): "ALCH-TR" manufactured by Kawaken Fine Chemical Co., Ltd. <Solvent (C)> Isobutyl acetate (abbreviated as "IBAC"): "Isobutyl acetate" manufactured by Daishin Chemical Co., Ltd. <Dehydrating agent (D)> Tosyl isocyanate: "Tosyl isocyanate" manufactured by Tokyo Chemical Co., Ltd. Trimethyl orthoacetate: MOA manufactured by Nippo Chemical Co., Ltd. <Stabilizer (E)> Acetylacetone: "Acetylacetone" manufactured by Daicel Corporation. <(meth)acrylic polyol> ((meth)acrylic monomers) Methyl methacrylate (abbreviated as "MMA"): Manufactured by Mitsubishi Gas Chemical Company, Inc. Butyl acrylate (abbreviated as "BA"): Manufactured by Nippon Shokubai Co., Ltd. (Monomers containing hydroxyl groups) 2-Hydroxypropyl methacrylate (abbreviated as "HPMA"): Manufactured by Nippon Shokubai Co., Ltd. (Other monomers) Styrene (abbreviated as "St"): Manufactured by Mitsubishi Chemical Corporation (Polymerization catalyst) 2,2′-Azobis(2-methylbutyronitrile): (V59, manufactured by Wako Pure Chemical Industries, Ltd., molecular weight 192.3) (Chain transfer agent) n-Dodecyl mercaptan (abbreviation "nDM", molecular weight 202): Manufactured by Wako Pure Chemical Industries, Ltd. t-Dodecyl mercaptan (abbreviation "tDM", molecular weight 202): Manufactured by Wako Pure Chemical Industries, Ltd. 2-ethylhexyl thioglycolate (abbreviation "M-8", molecular weight 204): Manufactured by Wako Pure Chemical Industries, Ltd. n-Octyl mercaptan (abbreviation "M-14", molecular weight 146): Manufactured by Wako Pure Chemical Industries, Ltd. (solvent) Propylene glycol methyl ether acetate (abbreviated as "PMA"): (Manufactured by Tokyo Chemical Industry Co., Ltd., molecular weight 132.2) (Stabilizer) Acetylacetone (abbreviated as "AcAc"): (Manufactured by Tokyo Chemical Industry Co., Ltd., molecular weight 100.1) <Polysiloxane resin containing epoxy groups> (Alkoxysilane compound (a1)) 3-Glycidyloxypropyltrimethoxysilane (abbreviated as "Ge"): (OFS-6040 manufactured by Dow Toray Industries, Ltd., molecular weight 236.3) (Alkoxysilane compound (a2)) Methyltrimethoxysilane (abbreviated as "Me"): (OFS-6070 manufactured by Dow Toray Industries, Ltd.; molecular weight 136.2) 2-(3,4-Epoxycyclohexyl)ethyltrimethoxysilane (abbreviated as "EC"): (also manufactured by Shin-Etsu Chemical Co., Ltd. as "KBM-303", molecular weight 246.3) Phenyltrimexilane (abbreviated as "Ph"): ("Z-6124" manufactured by Dow Toray Corporation, molecular weight 198.3) (Condensation catalyst) Magnesium chloride hexahydrate (abbreviated as "MgCl2") (manufactured by Tokyo Chemical Industry Co., Ltd., molecular weight 203.3) (solvent) Propylene glycol methyl ether acetate (abbreviated as "PMA"): (Manufactured by Tokyo Chemical Industry Co., Ltd., molecular weight 132.2) (Stabilizer) Acetylacetone (abbreviated as "AcAc"): (Manufactured by Tokyo Chemical Industry Co., Ltd., molecular weight 100.1) (Other components (thermoplastic resin)) Stylec T8701 (abbreviated as "T8701"): (Manufactured by Asahi Kasei Corporation, acrylonitrile-styrene copolymer resin) <Other aluminum compounds> Aluminum (tris-t-butoxide): "ASBD" manufactured by Kawaken Fine Chemical Co., Ltd. Aluminum (ethyl acetate) diisopropoxide: "ALCH" manufactured by Kawaken Fine Chemical Co., Ltd.

[0125] [Measurement and evaluation methods] Measurements and evaluations in the examples and comparative examples were performed using the following methods.

[0126] (Storage stability) The storage stability of the curing agent composition was evaluated by the rate of change in molecular weight (weight-average molecular weight (Mw) and number-average molecular weight (Mn)) of the curing agent composition before and after the storage stability test described later. Here, Mw and Mn are values ​​measured by GPC. GPC was performed using a Tosoh Corporation HLC-8320GPC as the liquid delivery system, a Tosoh Corporation TSK-GEL H-type column, and THF as the solvent, and the calculations were made in polystyrene equivalent. The rate of change in molecular weight was calculated using the following formulas (a) and (b): Molecular weight change rate (Mn) (%) = {(Molecular weight of curing agent composition after storage (Mn) - Molecular weight of curing agent composition before storage (Mn)) / Molecular weight of curing agent composition before storage (Mn)} × 100 ... (a) Molecular weight change rate (Mw) (%) = {(Molecular weight of curing agent composition after storage (Mw) - Molecular weight of curing agent composition before storage (Mw)) / Molecular weight of curing agent composition before storage (Mw)} × 100 ... (b) A (Excellent): The molecular weight change rate (Mn) and molecular weight change rate (Mw) after a 4-week test at 50°C are both less than 30%. B (Good): The molecular weight change rate (Mn) and molecular weight change rate (Mw) after 2 weeks at 50°C are both less than 30%, but the molecular weight change rate (Mn) and / or molecular weight change rate (Mw) after 4 weeks at 50°C are greater than 30%. C (Poor): After testing at 50°C for one week, the molecular weight change rate (Mn) and / or molecular weight change rate (Mw) is greater than 50%, or gelation has occurred.

[0127] (Adhesion) The obtained cured material (coating) was cut with a cutter to form 10x10 grid squares at 1mm intervals. Nichiban cellophane tape (registered trademark) was applied to the cuts and peeled off quickly at a 90° angle upwards. The adhesion of the cured material was visually observed to see if it peeled off from the substrate. One point was assigned for each grid square where the resin did not peel off, and the adhesion of the cured material was measured (peelability evaluation). A score of 100 was assigned when the material was completely adhered (i.e., no grid squares where the resin peeled off), and a score of 0 was assigned when all the resin peeled off completely. The adhesion of the cured material was evaluated based on the following criteria: A (Good): Delamination evaluation score of 95 points or higher B (Poor): Peeling evaluation score below 95 points.

[0128] (Scratch resistance) Using an eraser abrasion tester (manufactured by Mitsumoto Seisakusho Co., Ltd.), 500 g / cm³ of steel wool #0000 was applied to the resulting hardened product (coating). 2 The gloss retention rate of the cured coating was measured after applying a load and moving the surface of the coating back and forth 10 times with a stroke length of 10 cm. Here, the gloss retention rate of the coating was measured using a BYK Microtrigloss. The scratch resistance of the cured material was evaluated based on the following criteria: A (Excellent): Gloss retention rate of 80% or higher B (Good): Gloss retention rate is 50% or more, but less than 80%. C (Fairly Good): Gloss retention rate is 30% or more, but less than 50%.

[0129] (Chemical resistance) To the resulting cured product (coating), 0.2 g of a 10% lactic acid aqueous solution was spotted onto the coating and left to stand for 1 hour in a hot air dryer adjusted to 80°C. Afterward, the color and smoothness changes of the coating were visually inspected, and the chemical resistance of the cured product was evaluated based on the following criteria: A (Excellent): No color change, only faint spot marks remain. The surface of the paint film is smooth and there is no wrinkling. B (Good): Spot marks show slight whitening, and slight wrinkling occurs on the surface of the paint film. C (Fairly Good): Spot marks are whiter than in B, and the paint film surface is more wrinkled than in B.

[0130] [Example 1] (Preparation of curing agent composition) A curing agent composition was prepared by mixing each component according to the types and amounts listed in Table 1. Specifically, ALCH-TR was dissolved in IBAC in the amounts listed in Table 1, and after dissolution, Sumijoule N3300 was mixed and homogenized to prepare the curing agent composition. The non-volatile component content (NV) of the obtained curing agent composition was 30%. Each component was added sequentially to a mixture containing IBAC and ALCH-TR, mixed and homogenized, and then the next component was added, and this process was repeated.

[0131] The storage stability of the obtained curing agent compositions was evaluated by measuring (Mn) and (Mw) for both the curing agent composition immediately after preparation and the curing agent composition after being sealed in a glass container and left to stand for 1 week, 2 weeks, and 4 weeks in a hot air dryer set to 50°C (after the storage stability test). The results are shown in Table 1.

[0132] [Examples 2-6] A curing agent composition was prepared using the same procedure as in Example 1, except that the types and amounts of each component were changed as shown in Table 1.

[0133] The storage stability of the obtained curing agent compositions was evaluated by measuring (Mn) and (Mw) for both the curing agent composition immediately after preparation and the curing agent composition after being sealed in a glass container and left to stand for 1 week, 2 weeks, and 4 weeks in a hot air dryer set to 50°C (after the storage stability test). The results are shown in Table 1.

[0134] [Table 1]

[0135] [Comparative Examples 1-8] A curing agent composition was prepared using the same procedure as in Example 1, except that the types and amounts of each component were changed as shown in Table 2.

[0136] The storage stability of the obtained curing agent compositions was evaluated by measuring (Mn) and (Mw) for both the curing agent composition immediately after preparation and the curing agent composition after being sealed in a glass container and left to stand for 1 week, 2 weeks, and 4 weeks in a hot air dryer set to 50°C (after the storage stability test). The results are shown in Table 2.

[0137] All of the resulting curing agent compositions gelled after storage stability testing, and it was not possible to obtain curable resin compositions or cured products.

[0138] [Table 2]

[0139] [Example 7] (Manufacturing Example 1: Preparation of (meth)acrylic polyol) A nitrogen inlet tube, condenser, and thermometer were installed in a four-necked flask, and the apparatus was assembled under slightly pressurized, reflux conditions. An oil bath was set up to maintain an internal temperature of 110°C while nitrogen flow was being introduced, 234.8g of PMA was added, and the mixture was heated until it reached 110°C.

[0140] Separately from the four-necked flask mentioned above, a monomer solution for pump addition was prepared by adding 268.3g of HPMA, 167.7g of St, 67.1g of MMA, 167.7g of BA, 5.37g of V59, 6.71g of nDM, 6.71g of tDM, 6.71g of M-8, 6.71g of M-14, and 25.5g of PMA to a brown bottle. The prepared monomer solution was then added dropwise to the four-necked flask using a diaphragm pump over a period of 5 hours.

[0141] After sorting, 1.34 g of V59 and 34.7 g of PMA were added to a brown bottle to prepare a solution, which was then added dropwise to the reaction mixture in the four-necked flask over 1 hour using a pump. After the addition was complete, the mixture was heated for a further 1.5 hours to obtain (meth)acrylic polyol. The obtained (meth)acrylic polyol had a solids content (SC) of 70.0%, a hydroxyl value of 155 mgKOH / g, and a weight-average molecular weight of 7900. SC represents the weight percentage of the components that did not volatilize when the entire amount of the obtained (meth)acrylic polyol was heated to 105°C, relative to the total amount of (meth)acrylic polyol.

[0142] (Manufacturing Example 2: Preparation of polysiloxane resin containing epoxy groups) In a 2L four-necked flask, 1.4g of Me, 24.6g of Ge, 38.4g of EC, 0.355g of MgCl, and 136.5g of pure water (62.5 mol% relative to the total alkoxysilyl groups) were placed and heated in an oil bath set to 90°C for 6 hours. Then, 78.9g of PMA was added to the reaction system, and atmospheric distillation was performed using an evaporator and an oil bath set to 140°C to remove a total of 470g of methanol and residual water. Subsequently, 14.2g of AcAc was added as a stabilizer, and 20.6g of PMA was added for SC adjustment to obtain approximately 1000g of organopolysiloxane (polysiloxane resin with epoxy groups). The resulting polysiloxane resin with epoxy groups had an SC of 70%, a weight-average molecular weight of 4600, and a condensation rate of 85%.

[0143] To the obtained epoxy-group-containing polysiloxane resin, 21.3 g of AcAc was added, and then 13.5 g of PMA was added as a solvent to adjust the SC to 70.0%, thereby obtaining a solution containing the epoxy-group-containing polysiloxane resin.

[0144] (Preparation of curable resin composition) A multi-component curable resin composition was prepared by blending the first liquid, which is a resin component (a mixture of the (meth)acrylic polyol from Production Example 1 and the epoxy group-containing polysiloxane resin from Production Example 2), with the second liquid, which is the curing agent composition from Examples 1 to 6 immediately after preparation, and IBAC.

[0145] (Preparation of cured material (coating film)) The prepared multi-component curable resin composition was applied to a 50 × 150 × 2 mm ABS substrate using a No. 40 bar coater. The substrate was then placed in a hot air dryer set to 80°C for 30 minutes to remove the solvent and cure the applied multi-component curable resin composition, resulting in a dry cured product (coating) with a thickness of approximately 0.030 mm. The adhesion, scratch resistance, and chemical resistance of the obtained cured product were evaluated. The results are shown in Table 3.

[0146] [Examples 8-19] A multi-component curable resin composition was prepared using the same procedure as in Example 7, except that the types and amounts of each component were changed as shown in Table 3. Then, a cured product was prepared using the same procedure as in Example 7. As shown in Table 3, in Examples 13 to 19, the curing agent compositions of Examples 1 to 6, which had been stored (left to stand) for 4 weeks in a hot air dryer set at 50°C, were used as the second liquid.

[0147] The adhesion, scratch resistance, and chemical resistance of the resulting cured material were evaluated. The results are shown in Table 3.

[0148] [Table 3]

[0149] 〔result〕 Table 1 shows that the curing agent compositions of Examples 1 to 6 did not gel even after storage stability testing, demonstrating excellent storage stability. In other words, it was shown that a curing agent composition containing a polyisocyanate compound (A) and an aluminum compound (B) can be provided with improved storage stability.

[0150] Furthermore, as shown in Table 3, the cured products obtained by curing the multi-component curable resin compositions containing the curing agent compositions of Examples 1 to 6 (Examples 7 to 19) exhibited excellent adhesion, scratch resistance, and chemical resistance, and these effects could be maintained even when the curing agent compositions were stored for a long period of time. In particular, it was found that the cured products using the curing agent compositions of Examples 4 to 6 exhibited the above-mentioned excellent physical properties (Examples 16 to 18).

[0151] On the other hand, as shown in Table 2, all of the compositions of Comparative Examples 1 to 8 gelled after the storage stability test. In other words, it was shown that if the curing agent composition does not satisfy the composition of the curing agent composition, the storage stability will be poor. [Industrial applicability]

[0152] According to the present invention, a curing agent composition comprising a polyisocyanate compound and a metal compound, and exhibiting excellent storage stability, can be provided. Furthermore, a curable resin composition containing this curing agent composition can be suitably used as a coating agent and the like.

Claims

1. Polyisocyanate compound (A) and, Aluminum compound (B) and Solvent (C) and Optionally, dehydrating agent (D) and A curing agent composition for a multi-component curable resin composition, comprising a stabilizer (E), The aforementioned aluminum compound (B) is (i) It does not have alkyl and alkoxy groups directly bonded to aluminum, (ii) Having a β-dicarbonyl compound directly bonded to aluminum, With respect to 100% by weight of the total amount of the above components (A) to (E), The above polyisocyanate compound (A) is contained in an amount of 10 to 50% by weight, The aluminum compound (B) contains 1 to 15% by weight, The solvent (C) contains 30 to 80% by weight, The polyisocyanate compound (A) is a polyisocyanate compound in which the isocyanate group is not masked by a blocking agent. The curing agent composition for a multi-component curable resin composition is wherein the stabilizer (E) is one or more selected from acetylacetone, dimedone, meldrumic acid, 1,3-cyclohexanedione, ethyl acetacetate, methyl acetacetate, dimethyl malonate, and diethyl malonate.

2. A curing agent composition for a multi-component curable resin composition according to claim 1, comprising 0.5 to 10% by weight of a dehydrating agent (D) based on 100% by weight of the total amount of components (A) to (E).

3. A curing agent composition for a multi-component curable resin composition according to claim 1 or 2, comprising 0.5 to 10% by weight of a stabilizer (E) based on 100% by weight of the total amount of components (A) to (E).

4. A curing agent composition for a multi-component curable resin composition according to claim 3, wherein the content of components other than the polyisocyanate compound (A), the aluminum compound (B), the solvent (C), the dehydrating agent (D), and the stabilizer (E) is 10% by weight or less with respect to 100% by weight of the total amount of components (A) to (E).

5. A first liquid containing (meth)acrylic polyol, A second liquid comprising a curing agent composition for a multi-component curable resin composition according to any one of claims 1 to 4, A multi-component curable resin composition containing [the specified ingredient].

6. A multi-component coating composition comprising the multi-component curable resin composition described in claim 5.

7. A cured product obtained by curing the multi-component curable resin composition described in claim 5, or the multi-component paint composition described in claim 6.

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