Curable coating agent composition, cured product, and laminate

Abstract

The present invention provides a curing-type coating agent composition that provides a layer of cured material with light peeling ability and low silicone migration. [Solution] The present invention relates to a curable coating agent composition comprising a product (A) of a reaction component containing a polyisocyanate (a1) having three or more isocyanate groups, a polysiloxane (a2) having a hydroxyl group, and a photopolymerization initiator (a3) ​​having a hydroxyl group, and a poly(meth)acrylate (B); a cured product made from the composition; and a laminate having a layer of the cured product.

Description

[Technical Field]

[0001] The present invention relates to a curable coating agent composition, a cured product, and a laminate. [Background technology]

[0002] Curable coating compositions are applied to the surface of substrates such as release paper, glass, or plastic films (e.g., polyethylene terephthalate film, polyimide film, etc.), cured, and then the release paper is peeled off to form a cured product or a laminate with a cured layer on the substrate. These are used, for example, for bonding components of electrical and electronic materials such as smartphones and personal computers, or between display devices and components, as well as in process films and process tapes used in the manufacture of decorative panels and electrical and electronic materials. Furthermore, many curable coating compositions used in process films and process tapes contain polysiloxane. By forming a cured polysiloxane layer on the surface of plastic films such as polyethylene terephthalate, it becomes easier to achieve a light peeling force. However, polysiloxane often bleeds out onto the surface of the cured layer and migrates to the adherend such as the film (resulting in a large amount of silicone migration).

[0003] As a means of reducing the amount of silicone migration, for example, an active energy ray curable release agent composition is known in which the reaction product consists of a hydroxyl group-containing (meth)acrylate having an average of three or more (meth)acryloyl groups, an organic isocyanate having at least two or more isocyanate groups, and a linear dimethylorganopolysiloxane having at least one or more hydroxyl groups (Patent Document 1). However, although this composition can reduce the amount of silicone migration, it tends to impair light release power because it has multiple (meth)acryloyl groups in the molecule. [Prior art documents] [Patent Documents]

[0004] [Patent Document 1] Japanese Patent Publication No. 2010-265403 [Overview of the project] [Problems that the invention aims to solve]

[0005] The object of the present invention is to provide a curable coating agent composition that provides a cured layer having light peeling ability and low silicone migration. [Means for solving the problem]

[0006] The inventors of this invention have diligently studied and found a solution to the aforementioned problem. Specifically, the present invention relates to the following curable coating agent composition, cured product, and laminate.

[0007] (item) 1. A curable coating agent composition comprising a product (A) of a reaction component containing a polyisocyanate (a1) having three or more isocyanate groups, a polysiloxane (a2) having a hydroxyl group, and a photopolymerization initiator (a3) ​​having a hydroxyl group, and a poly(meth)acrylate (B). 2. The curable coating agent composition according to item 1, wherein the reaction component further comprises polyalkylene glycol monoalkyl ether (a4). 3. A cured product comprising the curable coating agent composition described in item 1 or 2 above. 4. A laminate having a layer of the cured material described in item 3 above on at least one side of the substrate. [Effects of the Invention]

[0008] The curable coating agent composition according to the present invention provides a cured layer that has low peelability and low silicone migration. [Modes for carrying out the invention]

[0009] The curable coating agent composition of the present invention contains a polyisocyanate (a1) having three or more isocyanate groups (hereinafter referred to as component (a1)), a polysiloxane (a2) having a hydroxy group (hereinafter referred to as component (a2)), and a photopolymerization initiator (a3) having a hydroxy group (hereinafter referred to as component (a3)), and is a product (A) of reaction components (hereinafter referred to as component (A)), and a poly(meth)acrylate (B) (hereinafter referred to as component (B)).

[0010] <Regarding component (A)> Regarding the product of component (A), each reaction component will be described.

[0011] Component (a1) is a polyisocyanate having three or more isocyanate groups. Examples of component (a1) include triisocyanates such as lysine triisocyanate and 4,4',4''-methylidynetris(isocyanatobenzene); the biuret form, isocyanurate form, allophanate form, adduct form of diisocyanate, and a complex obtained by reacting two or more selected from the group consisting of the biuret form, isocyanurate form, allophanate form, and adduct form; the biuret form, isocyanurate form, allophanate form, adduct form of polyisocyanate other than diisocyanate, and a complex obtained by reacting two or more selected from the group consisting of the biuret form, isocyanurate form, allophanate form, and adduct form. These may be used alone or in combination of two or more.

[0012] Examples of diisocyanate include linear aliphatic diisocyanate, branched aliphatic diisocyanate, alicyclic diisocyanate, and aromatic diisocyanate.

[0013] Examples of linear aliphatic diisocyanates include methylene diisocyanate, dimethyl diisocyanate, trimethylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, heptamethylene diisocyanate, octamethylene diisocyanate, nonamethylene diisocyanate, and decamethylene diisocyanate.

[0014] Examples of branched aliphatic diisocyanates include diethylpentylene diisocyanate, trimethylbutylene diisocyanate, trimethylpentylene diisocyanate, and trimethylhexamethylene diisocyanate.

[0015] Examples of alicyclic diisocyanates include isophorone diisocyanate, dicyclohexylmethane diisocyanate, cyclopentane diisocyanate, cyclohexane diisocyanate, cycloheptane diisocyanate, hydrogenated tolylene diisocyanate, hydrogenated diphenylmethane diisocyanate, hydrogenated xylylene diisocyanate, bicyclodecane diisocyanate, tricyclodecane diisocyanate, adamantane diisocyanate, norbornene diisocyanate, and the like. The position of the isocyanate group and other elements is not particularly limited.

[0016] Examples of aromatic diisocyanates include tolylene diisocyanate, diphenylmethane diisocyanate, xylylene diisocyanate, diphenyldimethylmethane diisocyanate, diphenyltetramethyl diisocyanate, dibenzyl diisocyanate, phenylene diisocyanate, and tetramethylxylylene diisocyanate. The position of the isocyanate group is not particularly limited.

[0017] The structures of the biuret, isocyanurate, allophanate, and adduct compounds are as described in Japanese Patent Publication No. 2022-042492 and Japanese Patent Publication No. 2023-083794.

[0018] Examples of commercially available biuret materials include "Duranate 24A-100," "Duranate 22A-75P," and "Duranate 21S-75E" (all manufactured by Asahi Kasei Corporation), and "Desmodule N3200A" (manufactured by Sumika Covestro Urethane Co., Ltd.).

[0019] Examples of commercially available isocyanurate compounds include "Duranate TPA-100," "Duranate TKA-100," "Duranate MFA-75B," and "Duranate MHG-80B" (all manufactured by Asahi Kasei Corporation), "Coronate HXR," "Coronate HX," "Coronate HK," and "Coronate 2037" (all manufactured by Tosoh Corporation), "Takenate D-127N," "Takenate D-131N," "Takenate D-132N," and "Takenate D-204EA-1" (all manufactured by Mitsui Chemicals, Inc.), and "VESTANAT T1890 / 100" (manufactured by Evonik Japan Ltd.).

[0020] Examples of commercially available allophanate compounds include "Coronate 2793" (manufactured by Tosoh Corporation) and "Takenate D-178N" (manufactured by Mitsui Chemicals, Inc.).

[0021] Examples of commercially available adduct bodies include "Duranate P301-75E" (manufactured by Asahi Kasei Corporation), "Takenate D110N", "Takenate D120N", and "Takenate D160N" (all manufactured by Mitsui Chemicals, Inc.), and "Coronate L" and "Coronate HL" (both manufactured by Tosoh Corporation).

[0022] Among these, isocyanurates of diisocyanates are preferred, isocyanurates of aliphatic diisocyanates are more preferred, and isocyanurates of linear aliphatic diisocyanates are even more preferred.

[0023] (a1) The NCO content (NCO%) of the nonvolatile components of component (a1) is preferably 10-50%, and more preferably 12-30%. When the NCO content is 50% or less, it becomes easier to reduce the amount of silicone migration in the cured layer.

[0024] Furthermore, the aforementioned diisocyanates (linear aliphatic diisocyanates, branched aliphatic diisocyanates, alicyclic diisocyanates, aromatic diisocyanates) can also be used in combination with the reaction components. The amount of diisocyanate used is preferably 20% by weight or less, more preferably 10% by weight or less, and even more preferably 5% by weight or less, based on 100% by weight of the total non-volatile content of component (a1) and the diisocyanate.

[0025] Component (a2) is a polysiloxane having a hydroxyl group. When a structure derived from component (a2) is incorporated into component (A), a slight peeling force can be imparted to the layer of the cured product.

[0026] (a2) Examples of components include polysiloxanes having a hydroxyl group at one end and polysiloxanes having hydroxyl groups at both ends. These may be used individually or in combination of two or more.

[0027] Examples of polysiloxanes having a hydroxyl group at one end include those represented by the structure of general formula (1) or (2).

[0028] [ka] (In general formula (1), R 1 , R 2 Each of these independently represents one of the following: a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, an s-butyl group, or a t-butyl group, R 3 (This represents an alkylene group or alkylene ether group.)

[0029] [ka] (In general formula (2), R 4 , R 5 , R 7 each independently represents any one of a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, an s-butyl group or a t-butyl group, and R 6 each independently represents an alkylene group or an alkylene ether group.)

[0030] In R 3 of general formula (1) or R 6 of (2), examples of the alkylene group include a methylene group, an ethylene group, an n-propylene group, an isopropyl group, a butylene group, etc.

[0031] In R 3 of general formula (1) or R 6 of (2), examples of the alkylene ether group include -CH2-O-CH2-, -C2H4-O-CH2-, -C2H4-O-C2H4-, -C3H6-O-CH2-, -C3H6-O-C2H4-, -C3H6-O-C3H6-, etc. When the alkylene groups respectively bonded to the O atoms of the ether are different, either end may be bonded to the Si atom.

[0032] Examples of commercially available polysiloxanes represented by the structure of general formula (1) include, for example, "X-22-170BX", "X-22-170DX" (both manufactured by Shin-Etsu Chemical Co., Ltd.), "Silaplane FM-0411", "Silaplane FM-0411P", "Silaplane FM-0421", "Silaplane FM-0425" (all manufactured by JNC Corporation), etc.

[0033] Examples of commercially available polysiloxanes represented by the structure of general formula (2) include, for example, "X-22-176DX", "X-22-176F", "X-22-176GX-A" (all manufactured by Shin-Etsu Chemical Co., Ltd.), "Silaplane FM-DA11", "Silaplane FM-DA21", "Silaplane FM-DA26" (all manufactured by JNC Corporation), etc.

[0034] Examples of polysiloxanes having hydroxyl groups at both ends include those represented by the structure of general formula (3).

[0035] [ka] (In general formula (2), R 8 R represents one of the following: methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, s-butyl group, or t-butyl group. 9 (This represents an alkylene group or alkylene ether group.)

[0036] R in general formula (3) 9 Examples of alkylene groups include methylene groups, ethylene groups, n-propylene groups, isopropylene groups, and butylene groups.

[0037] R in general formula (3) 9 Examples of alkylene ether groups include -CH2-O-CH2-, -C2H4-O-CH2-, -C2H4-O-C2H4-, -C3H6-O-CH2-, -C3H6-O-C2H4-, -C3H6-O-C3H6-, etc., and if the alkylene groups bonded to the O atom of the ether are different, any of the ends may be bonded to the Si atom.

[0038] Examples of commercially available polysiloxanes represented by the general formula (3) include "KF-9701", "X-21-5841", "KF-6000", "KF-6001", "KF-6002", and "KF-6003" (all manufactured by Shin-Etsu Chemical Co., Ltd.), and "Sylaplane FM-4411", "Sylaplane FM-4421", and "Sylaplane FM-4425" (all manufactured by JNC Corporation).

[0039] The aforementioned commercially available products can be used individually or in combination of two or more types.

[0040] In particular, polysiloxanes having a hydroxyl group at one end are preferred because they make the cured layer more likely to exhibit slight peeling force, and polysiloxanes represented by the structure of general formula (1) are more preferred.

[0041] (a2) In terms of the physical properties of component (a2), a number average molecular weight of 100 to 20,000 is preferred, 500 to 10,000 is more preferred, and 1,000 to 5,000 is even more preferred, in order to facilitate the cured layer exhibiting light peeling force. Note that the number average molecular weight refers to the value converted to polystyrene by gel permeation chromatography (GPC) (the same applies hereinafter).

[0042] Regarding the amount of component (a2) used, in order to make the cured layer more likely to exhibit light peeling force and to reduce the amount of silicone migration, it is preferable that the amount of hydroxyl groups of component (a2) be 0.01 to 0.7 moles, more preferably 0.015 to 0.6 moles, even more preferably 0.02 to 0.4 moles, and particularly preferably 0.03 to 0.3 moles, per mole of isocyanate groups of component (a1).

[0043] Here, the molar amount of isocyanate groups in component (a1) is expressed as the number of isocyanate groups contained in 1 mole of component (a1). For example, the molar amount of isocyanate groups in 1 mole of triisocyanate is 3 moles. Also, the molar amount of hydroxyl groups in component (a2) is expressed as the number of hydroxyl groups contained in 1 mole of component (a2). For example, the molar amount of hydroxyl groups in 1 mole of polysiloxane with a hydroxyl group at one end is 1 mole, and the molar amount of hydroxyl groups in 1 mole of polysiloxane with hydroxyl groups at both ends is 2 moles.

[0044] Component (a3) ​​is a photopolymerization initiator having a hydroxyl group. When a structure derived from component (a3) ​​is incorporated into component (A), it becomes easier to reduce the amount of silicone transferred.

[0045] Examples of such photopolymerization initiators include 1-hydroxycyclohexylphenyl ketone, 2-hydroxyacetophenone, 2-hydroxy-2-propiophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one (2-hydroxy-2-methylpropiophenone), 2-(2-hydroxyethoxy)ethyl oxyphenylacetic acid, 2-(2-hydroxyethoxy)ethyl oxyphenylacetic acid, and 2-(2-oxo-2-phenylacetoxyethoxy)ethyl oxyphenylacetic acid. Examples include photopolymerization initiators having one hydroxyl group, such as a mixture of (1-4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1-[4-{4-(2-hydroxy-2-methylpropionyl)-benzyl}phenyl]-2-methylpropan-1-one, and 2-isopropoxy-2-phenylacetophenone, which have two hydroxyl groups. These may be used individually or in combination of two or more.

[0046] (a3) Examples of commercially available products containing the component include "Omnirad184", "Omnirad1173", "Omnirad2959", "Omnirad127", and "Omnirad754" (all manufactured by IGM Resin), and "Lunacure100" and "Lunacure200" (both manufactured by DKSH Japan Co., Ltd.).

[0047] In particular, a mixture of 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2-hydroxy-4'-(2-hydroxyethoxy)-2-methylpropiophenone, 2-(2-hydroxyethoxy)ethyl oxyphenylacetic acid, 2-(2-hydroxyethoxy)ethyl oxyphenylacetic acid, and 2-(2-oxo-2-phenylacetoxyethoxy)ethyl oxyphenylacetic acid is preferred because it allows the cured layer to exhibit mild peelability and reduces the amount of silicone migration.

[0048] Regarding the amount of component (a3) ​​used, in order to minimize the amount of silicone migration in the cured layer, it is preferable that the amount of hydroxyl groups of component (a3) ​​be 0.3 to 0.99 moles, more preferably 0.4 to 0.985 moles, even more preferably 0.6 to 0.98 moles, and particularly preferably 0.7 to 0.97 moles, per mole of isocyanate groups of component (a1). When a mixture of photopolymerization initiators having hydroxyl groups and photopolymerization initiators not having hydroxyl groups (for example, Omnirad754, etc.) is used, the amount used is expressed in terms of the molar amount of photopolymerization initiator having hydroxyl groups.

[0049] Here, the molar amount of hydroxyl groups in component (a3) ​​is expressed as the number of hydroxyl groups in component (a3) ​​contained in 1 mole of component (a1). For example, 1 mole of 2-hydroxy-2-methyl-1-phenylpropan-1-one contains 1 mole of hydroxyl groups, and 1 mole of 2-hydroxy-4'-(2-hydroxyethoxy)-2-methylpropiophenone contains 2 moles of hydroxyl groups.

[0050] Furthermore, if component (a3) ​​remains unreacted in the reaction that produces component (A), the unreacted component (a3) ​​can be used as a photopolymerization initiator (C) as described later.

[0051] The reaction component may further contain polyalkylene glycol monoalkyl ether (a4) (hereinafter referred to as component (a4)). When a structure derived from component (a4) is incorporated into component (A), the curable coating agent composition becomes more easily dispersed in water, and an emulsion can be obtained.

[0052] (a4) Examples of components include polyethylene glycol monoalkyl ethers such as polyethylene glycol monomethyl ether, polyethylene glycol monoethyl ether, polyethylene glycol mono-n-propyl ether, polyethylene glycol isopropyl ether, polyethylene glycol mono-n-butyl ether, polyethylene glycol monoisobutyl ether, polyethylene glycol mono-n-pentyl glycol, polyethylene glycol mono-n-hexyl ether, polyethylene glycol monoisohexyl ether, polyethylene glycol mono-n-heptyl ether, polyethylene glycol mono-n-octyl ether, polyethylene glycol mono-n-nonyl ether, polyethylene glycol mono-n-decyl ether, etc. Polypropylene glycol monoalkyl ethers such as polypropylene glycol monomethyl ether, polypropylene glycol monoethyl ether, polypropylene glycol mono-n-propyl ether, polypropylene glycol isopropyl ether, polypropylene glycol mono-n-butyl ether, polypropylene glycol mono-isobutyl ether, polypropylene glycol mono-n-pentyl glycol, polypropylene glycol mono-n-hexyl ether, polypropylene glycol monoisohexyl ether, polypropylene glycol mono-n-heptyl ether, polypropylene glycol mono-n-octyl ether, polypropylene glycol mono-n-nonyl ether, and polypropylene glycol mono-n-decyl ether; Examples include polytetramethylene glycol monoalkyl ethers such as polytetramethylene glycol monomethyl ether, polytetramethylene glycol monoethyl ether, polytetramethylene glycol mono-n-propyl ether, polytetramethylene glycol isopropyl ether, polytetramethylene glycol mono-n-butyl ether, polytetramethylene glycol monoisobutyl ether, polytetramethylene glycol mono-n-pentyl glycol, polytetramethylene glycol mono-n-hexyl ether, polytetramethylene glycol monoisohexyl ether, polytetramethylene glycol mono-n-heptyl ether, polytetramethylene glycol mono-n-octyl ether, polytetramethylene glycol mono-n-nonyl ether, and polytetramethylene glycol mono-n-decyl ether. These may be used individually or in combination of two or more. Among these, polyethylene glycol monoalkyl ether is preferred, and polyethylene glycol monomethyl ether and polyethylene glycol monoethyl ether are more preferred.

[0053] (a4) Examples of commercially available products containing the component include "Uniox M-400", "Uniox M-550", "Uniox M-1000", "Uniox M-1500", "Uniox M-2000", "Uniox M-2500", "Uniox M-3000", and "Uniox M-4000" (all manufactured by NOF Corporation). These may be used individually or in combination of two or more types.

[0054] (a4) In terms of the physical properties of component (a4), a number average molecular weight of 100 to 5000 is preferred, 300 to 3000 is more preferred, and 400 to 1000 is even more preferred, since the hardened layer tends to exhibit slight peeling force.

[0055] Regarding the amount of component (a4) used, in order to make the cured layer more likely to exhibit light peeling force and to reduce the amount of silicone migration, it is preferable that the amount of hydroxyl groups of component (a4) be 0.6 moles or less, more preferably 0.5 moles or less, even more preferably 0.4 moles or less, and particularly preferably 0.3 moles or less, per mole of isocyanate groups of component (a1).

[0056] Component (A) is obtained by reacting components (a1), (a2), and (a3), and optionally (a4). The order and method of adding each component are not particularly limited; for example, each component may be added at once, or components (a1) and (a2) may be reacted first to obtain an intermediate, and then component (a3), and optionally (a4), may be added and reacted.

[0057] The reaction conditions described above typically involve a temperature of 50-100°C, preferably 60-90°C. The reaction time can also be freely adjusted according to the reactivity of the reactants.

[0058] Catalysts and organic solvents may be used in the above reaction as appropriate.

[0059] Examples of catalysts include amine-based catalysts such as triethylenediamine and 1,8-diazabicyclo-[5,4,0]-undecene-7; tin-based catalysts such as stannous octylate (2-ethylhexanoate stannous), dibutyltin dilaurate, and dioctyltin dilaurate; bismuth-based catalysts such as bismuth dioctylate, bismuth trioctylate, and bismuth trineodecanoate; lead-based catalysts such as lead dioctylate; and zirconium-based catalysts such as zirconium tetraacetylacetonate. These can be used individually or in combination of two or more. The amount of catalyst used is preferably 0.05 to 2 parts by weight, and more preferably 0.1 to 1 part by weight, per 100 parts by weight of the total reaction components.

[0060] Examples of organic solvents include amines such as N-methyl-2-pyrrolidone and diazabicycloundecene; Amides such as N,N-dimethylformamide, N,N-diethylformamide, N,N-dimethylacetamide, and N,N-diethylacetamide; Ketones such as methyl ethyl ketone, methyl-n-propyl ketone, methyl isopropyl ketone, n-butyl methyl ketone, isobutyl methyl ketone, diethyl ketone, ethyl-n-propyl ketone, ethyl isopropyl ketone, n-butyl ethyl ketone, di-n-propyl ketone, cyclopropyl methyl ketone, cyclobutanone, cyclobutyl methyl ketone, cyclopentanone, cyclohexanone, and methylcyclohexanone; Aliphatic carboxylic acid esters such as n-propyl formate, isopropyl formate, n-butyl formate, isobutyl formate, n-pentyl formate, isopentyl formate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, n-pentyl acetate, isopentyl acetate, methyl propionate, ethyl propionate, n-propyl propionate, isopropyl propionate, n-butyl propionate, and other aliphatic carboxylic acid esters; Alkyl carbonate esters such as dimethyl carbonate, ethylmethyl carbonate, and diethyl carbonate; Alicyclic carboxylic acid esters such as methyl cyclopropanecarboxylate, ethyl cyclopropanecarboxylate, and methyl cyclobutanecarboxylate; Aliphatic ethers such as ethyl-n-propyl ether, di-n-propyl ether, diisopropyl ether, 1,2-dimethoxyethane, 1,1-diethoxyethane, 1,2-diethoxyethane, 1,2-dimethoxypropane, 2,2-dimethoxypropane, 1,1-diethoxypropane, and 2,2-diethoxypropane; Cyclic ethers such as tetrahydrofuran and dioxane; Aliphatic hydrocarbons such as 2-methylpentane, 3-ethylpentane, n-hexane, 2-methylhexane, 3-methylhexane, 3-ethylhexane, n-heptane, 2-methylheptane, 3-methylheptane, 4-methylheptane, 3-ethylheptane, n-octane, 2-methyloctane, 3-methyloctane, and 4-methyloctane; Alicyclic hydrocarbons such as methylcyclopentane, ethylcyclopentane, n-propylcyclopentane, isopropylcyclopentane, n-butylcyclopentane, isobutylcyclopentane, cyclohexane, methylcyclohexane, ethylcyclohexane, 1,1-dimethylcyclohexane, 1-ethyl-3-methylcyclohexane, and cycloheptane; Aromatic hydrocarbons such as benzene, toluene, and xylene; dimethyl sulfoxides, etc. These may be used individually or in combination of two or more.

[0061] Furthermore, mono(meth)acrylates that do not have a hydroxyl group, as described later, can also be used as organic solvents (or diluent solvents). The content of the organic solvent should preferably be adjusted to a reaction concentration of 80% by weight or less, and more preferably 60% by weight or less.

[0062] (A) In terms of the content of component (A), in order to ensure that the cured layer exhibits a light peeling force, the weight ratio of nonvolatile content is preferably 0.1 to 30% by weight, more preferably 0.2 to 15% by weight, even more preferably 0.4 to 12.5% ​​by weight, and particularly preferably 0.7 to 10% by weight, based on 100% by weight of the curable coating agent composition. Herein, nonvolatile content refers to the components of the curable coating agent composition of the present invention excluding the organic solvent and water described later (the same applies hereinafter).

[0063] <(B) About component> The poly(meth)acrylate component (B) is described below. Component (B) is a compound having two or more (meth)acryloyl groups. By using component (B), the coating composition can be cured well, and the cured layer tends to exhibit light peeling strength and excellent scratch resistance. In the following, (meth)acrylate means methacrylate or acrylate, (meth)acryloyl means methacryloyl or acryloyl, and (meth)acrylic means methacrylic or acrylic.

[0064] (B) Component may include, for example, monoalkylene glycol di(meth)acrylates such as ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, tetramethylene glycol di(meth)acrylate, pentamethylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, hexamethylene glycol di(meth)acrylate, heptamethylene glycol di(meth)acrylate, octamethylene glycol di(meth)acrylate, etc. Polyalkylene glycol (meth)acrylates such as diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, and tripropylene glycol di(meth)acrylate; Pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, or mixtures thereof, which are pentaerythritol poly(meth)acrylates; Dipentaerythritol di(meth)acrylate, dipentaerythritol tri(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, or mixtures thereof, all dipentaerythritol (meth)polyacrylates; Tripentaerythritol tetra(meth)acrylate, tripentaerythritol penta(meth)acrylate, tripentaerythritol hexa(meth)acrylate, tripentaerythritol hepta(meth)acrylate, tripentaerythritol octa(meth)acrylate, or mixtures thereof of tripentaerythritol (meth)acrylates; Examples include trimethylolpropane poly(meth)acrylates such as trimethylolpropane di(meth)acrylate and trimethylolpropane tri(meth)acrylate. These may be used individually or in combination of two or more types. Among these, pentaerythritol poly(meth)acrylates and dipentaerythritol poly(meth)acrylates are preferred because the cured layer tends to exhibit mild peelability.

[0065] (B) In terms of the content of component (B), since the cured layer tends to exhibit mild peeling force, the weight ratio of nonvolatile matter is preferably 60 to 99.9% by weight, more preferably 75 to 99.8% by weight, even more preferably 80 to 99.6% by weight, and particularly preferably 85 to 99% by weight, based on 100% by weight of the curable coating agent composition.

[0066] The curable coating agent composition of the present invention may contain mono(meth)acrylate (B') (hereinafter referred to as component (B')).

[0067] (B') Component is classified into mono(meth)acrylates without a hydroxyl group and mono(meth)acrylates with a hydroxyl group.

[0068] Examples of mono(meth)acrylates that do not have a hydroxyl group include aliphatic mono(meth)acrylates such as methyl(meth)acrylate, ethyl(meth)acrylate, n-propyl(meth)acrylate, n-butyl(meth)acrylate, t-butyl(meth)acrylate, isobutyl(meth)acrylate, n-pentyl(meth)acrylate, n-hexyl(meth)acrylate, n-heptyl(meth)acrylate, n-octyl(meth)acrylate, 2-ethylhexyl(meth)acrylate, n-nonyl(meth)acrylate, n-decyl(meth)acrylate, isodecyl(meth)acrylate, tri-n-decyl(meth)acrylate, n-lauryl(meth)acrylate, n-myristyl(meth)acrylate, n-palmityl(meth)acrylate, n-stearyl(meth)acrylate, and isostearyl(meth)acrylate; Alicyclic mono(meth)acrylates such as cyclohexyl (meth)acrylate, norbornyl (meth)acrylate, isobornyl (meth)acrylate, norbornanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentanyloxyethyl (meth)acrylate, tricyclodecanedimethylol di(meth)acrylate, etc. Examples include aromatic mono(meth)acrylates such as phenyl(meth)acrylate, benzyl acrylate, 2-phenylethyl(meth)acrylate, nonylphenoxypolyethylene glycol(meth)acrylate, o-phenylphenoxyethyl(meth)acrylate, m-phenylphenoxyethyl(meth)acrylate, p-phenylphenoxyethyl(meth)acrylate, o-phenoxybenzyl(meth)acrylate, m-phenoxybenzyl(meth)acrylate, p-phenoxybenzyl(meth)acrylate, ethoxylated-o-phenylphenol(meth)acrylate, ethoxylated-m-phenylphenol(meth)acrylate, ethoxylated-p-phenylphenol(meth)acrylate, ethylene oxide-modified-o-cumylphenol(meth)acrylate, ethylene oxide-modified-m-cumylphenol(meth)acrylate, ethylene oxide-modified-p-cumylphenol(meth)acrylate, and triphenylmethyl(meth)acrylate.

[0069] Examples of mono(meth)acrylates having a hydroxyl group include aliphatic mono(meth)acrylates having one primary hydroxyl group, such as 2-hydroxyethyl(meth)acrylate, 3-hydroxypropyl(meth)acrylate, 4-hydroxybutyl(meth)acrylate, 5-hydroxypentyl(meth)acrylate, 6-hydroxyhexyl(meth)acrylate, 7-hydroxyheptyl(meth)acrylate, and 8-hydroxyoctyl(meth)acrylate; Aliphatic mono(meth)acrylates having one secondary hydroxyl group, such as 2-hydroxypropyl(meth)acrylate, 2-hydroxybutyl(meth)acrylate, 3-hydroxybutyl(meth)acrylate, 4-hydroxyhexyl(meth)acrylate, and 5-hydroxyhexyl(meth)acrylate; Aliphatic mono(meth)acrylates having two hydroxyl groups, such as 2,3-dihydroxypropyl(meth)acrylate, 3,4-dihydroxybutyl(meth)acrylate, glycerin mono(meth)acrylate, and 1,4-dihydroxyheptyl(meth)acrylate; Alicyclic mono(meth)acrylates having one hydroxyl group, such as 4-hydroxycyclohexyl(meth)acrylate and 3-hydroxy-1-adamantyl(meth)acrylate; Alicyclic mono(meth)acrylates having two hydroxyl groups, such as 1,4-cyclohexanedimethanol mono(meth)acrylate and 3,5-dihydroxyadamantyl(meth)acrylate; Examples include aromatic (meth)acrylates having one hydroxyl group, such as 2-hydroxy-3-phenoxypropyl (meth)acrylate.

[0070] These (B') components may be used individually or in combination of two or more types.

[0071] Regarding the content of component (B'), in order to ensure that the cured layer exhibits a light peeling force, it is preferable that the weight ratio of nonvolatile matter be 30% or less, more preferably 15% or less, and even more preferably 10% or less, based on 100% by weight of the curable coating agent composition.

[0072] <About other ingredients> The curable coating agent composition of the present invention may contain a photopolymerization initiator (C) (hereinafter referred to as component (C)).

[0073] (C) Component is, for example, the photopolymerization initiator exemplified in component (a3) ​​above; Acylphosphine oxides such as bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide and 2,4,6-trimethylbenzoyldiphenylphosphine oxide; Oxime esters such as 1,2-octanedione, 1-[4-(phenylthio)-2-(o-benzoyl oxime)], etanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-1-(o-acetyl oxime); Amino ketones such as 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropiophenone, 2-benzyl-2-(dimethylamino)-4'-morpholinobylophenone, and 2-(dimethylamino)-2-(4-methylbenzyl)-1-(4-morpholin-4-ylphenyl)butan-1-one; Bis(η) 5 Cationic photopolymerization initiators such as -2,4-cyclopentadiene-1-yl)-bis{2,6-difluoro-3-(1H-pyrrole-1-yl)-phenyl}titanium, 4-isobutylphenyl (4-methylphenyl)iodonium hexafluorophosphate, sulfonium hexafluorophosphate, and sulfonium tetrakis(pentafluorophenyl) borate; Benzyl ketals such as 2,2-dimethoxy-2-phenylacetophenone (2,2-dimethoxy-1,2-diphenylethane-1-one); Benzophenones such as benzophenone, 4-methylbenzophenone, methyl benzophenone-2-carboxylate (methyl 2-benzoyl benzoate), and 4,4-bis(dimethylamino)benzophenone; Thioxanthones such as 2,4-diethylthioxanthone and 2-isopropylthioxanthone; Examples include methylbenzoyl formate (methyl oxophenylacetate, 1-methoxy-2-phenyl-1,2-ethanedione, phenylglyoxylic acid methyl ester) and 2-(2-hydroxyethoxy)ethyl oxyphenylacetate. These may be used individually or in combination of two or more.

[0074] The content of component (C) is preferably 0.5 to 40% by weight, more preferably 1 to 30% by weight, and even more preferably 5 to 15% by weight, based on 100% by weight of the total of components (A) and (B) (or components (A), (B), and (B')), in terms of nonvolatile content. Here, the weight of nonvolatile content refers to the weight of the components excluding organic solvents and water, which will be described later, from the curable coating composition of the present invention.

[0075] The curable coating agent composition of the present invention may further contain solvents such as the aforementioned organic solvents and water; and additives such as surfactants, binder resins, antislip agents, antioxidants, defoaming agents, preservatives, rust inhibitors, thickeners, fillers, pH adjusters, pigments, dyes, lubricants, leveling agents, catalysts, and photosensitizers. These may be used individually or in combination of two or more.

[0076] Examples of water include tap water, purified water, ultrapure water, ion-exchanged water, and industrial water. These can be used individually or in combination of two or more types.

[0077] Examples of binder resins include acrylic resin, urethane resin, polyester resin, epoxy resin, and alkyd resin. These can be used individually or in combination of two or more types.

[0078] The solvent content is adjusted so that the non-volatile content of the curable coating agent composition is preferably 1 to 40% by weight, and more preferably 3 to 35% by weight.

[0079] Examples of the curable coating agent composition of the present invention include solutions, emulsions, and the like.

[0080] The curable coating agent composition of the present invention is obtained by blending component (A) and component (B), and optionally component (B'), component (C), the solvent, and the additive. The mixing order and method are not particularly limited, and the mixing may be carried out by heating or cooling as appropriate, or under pressure, normal pressure, or reduced pressure.

[0081] The cured product of the present invention consists of the curable coating agent composition described above.

[0082] The cured product of the present invention is obtained by coating the adhesive composition onto a substrate and then curing it with active energy rays or heat.

[0083] Examples of base materials include plastic and paper.

[0084] Examples of plastics include polyethylene, polypropylene, polybutene, polybutadiene, polymethylpentene, cycloolefins, and other olefin resins; Polyester resins such as polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polybutylene succinate (PBS), polybutylene succinate adipate (PBSA), polybutylene terephthalate (PBT), polybutylene adipate terephthalate (PBAT), polylactic acid, polyhydroxyalkanoic acid, and polycaprolactone; (Meth)acrylic resins such as polymethyl (meth)acrylate; Vinyl resins such as polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, and poly(ethylene-vinyl acetate); Styrene resins such as polystyrene, poly(styrene-acrylonitrile) (AS resin), and poly(styrene-butadiene-acrylonitrile) (ABS resin); Examples include polycarbonate, polyether ether ketone, polyamide, polyimide, epoxy resin, melamine resin, diacetylcellulose, triacetylcellulose, and fluororesin.

[0085] Examples of paper include bleached kraft paper, unbleached kraft paper, fine paper, medium-quality paper, lightly coated paper, coated paper, processed base paper, cardboard, white cardboard, liner paper, semi-glassine paper, glassine paper, parchment paper, and topcoat paper.

[0086] Other substrates that can be used include, for example, fabrics such as woven and nonwoven fabrics; foamed sheets such as foamed polyurethane and foamed polychloroprene rubber; rubbers such as natural rubber and butyl rubber; metals such as aluminum and copper; glass, ITO, etc.

[0087] Furthermore, the substrate may be one of these crosslinked films or laminated films, and may be untreated, lightly to heavily peelable, or equipped with an easy-adhesion layer or anchor layer.

[0088] Examples of coating methods include applicators, bar coaters, Meyer bar coaters, roll coaters, die coaters, comma coaters, knife coaters, gravure coaters, reverse gravure coaters, offset printing, flexographic printing, and screen printing. The amount of curable coating agent composition to be applied is preferably such that the thickness of the cured layer is 0.05 to 10 μm, more preferably 0.1 to 5 μm.

[0089] When curing is performed using active energy rays, examples of active energy rays include light rays such as ultraviolet rays, infrared rays, and visible light; electron beams, X-rays, alpha rays, beta rays, gamma rays, and neutron rays. In the present invention, light rays are preferred, and ultraviolet rays are more preferred.

[0090] Examples of ultraviolet light sources include high-pressure mercury lamps, ultra-high-pressure mercury lamps, xenon lamps, metal halide lamps, carbon arc lamps, LEDs, and UV-LEDs. The irradiation intensity of ultraviolet light is typically 50-2000 mW / cm². 2 The cumulative light intensity is typically 10 to 10,000 mJ / cm². 2 That is the case.

[0091] When curing with active energy rays, the material may be dried or partially cured with heat before irradiation, or completely cured with heat after treatment with active energy rays.

[0092] Examples of heat sources include circulating air dryers and heating furnaces. The heating temperature is preferably 40 to 150°C, and more preferably 50 to 120°C. Furthermore, the heating time is preferably 30 seconds to 3 hours, and more preferably 30 seconds to 1 hour.

[0093] When curing by heat, suitable heat sources include circulating air dryers and heating furnaces. The heating temperature is preferably 40-200°C, more preferably 60-180°C. Furthermore, the heating time is preferably 1-24 hours, more preferably 2-12 hours.

[0094] The laminate of the present invention has a layer of the cured material on at least one side of the substrate. The substrate used, coating method, curing conditions, etc., are the same as those described above. In addition, adhesive layers, easy-adhesion layers, adhesive layers, anchor layers, functional layers, etc., may be laminated in the laminate, and layers of the substrate and the cured material may be further provided.

[0095] The cured product or laminate of the present invention has easy peelability and low silicone migration, so the curable coating agent composition can be used as a release coating agent composition, and the cured product or laminate can be used as a release film. Furthermore, the release film can be applied to adhesive surfaces and protective films for adhesive surfaces such as adhesive tapes, double-sided tapes, adhesive labels, and seals, process films used in the manufacture of resin molded boards, decorative boards, electrical and electronic components, and process films or process tapes for the manufacture of electrical and electronic materials such as separators, carrier films, carrier tapes, transfer films, and protective tapes, and is particularly suitable for separators, carrier films, carrier tapes, transfer films, and protective tapes. Note that electrical and electronic materials refer to components of products that have electronic circuits, such as personal computers, smartphones, mobile phones, liquid crystal displays, refrigerators, and automobiles.

[0096] Furthermore, the curable coating agent composition of the present invention can be applied to various uses in which the above-mentioned effects can be achieved. [Examples]

[0097] The present invention will be specifically described below through examples and comparative examples. However, the technical scope of the present invention is not limited by these examples. Furthermore, unless otherwise specified, "parts" and "%" in the examples refer to weight.

[0098] Manufacturing Example 1 In a reactor equipped with a condenser, a stirrer, a nitrogen inlet tube, and a thermometer, 40.1 parts (30.1 parts by weight of non-volatile content) of isocyanurate hexamethylene diisocyanate (product name: "Duranate MFA-75B", NCO = 13.7%, non-volatile content concentration: 75%, manufactured by Asahi Kasei Corporation, hereinafter referred to as "MFA-75B") were added, along with a polysiloxane with a number average molecular weight of 1000 and a hydroxyl group at one end (product name: "Sylaplane FM-0411P", having the structure of general formula (1), R 1 = t-butyl group, R 2 =methyl group and R 3 =-C3H6-O-C2H4- polysiloxane, manufactured by JNC Corporation, hereinafter referred to as "FM-0411P".) 16.7 parts, polysiloxane with a number average molecular weight of 5000 and a hydroxyl group at one end (product name: "Cylaprene FM-0421", having the structure of general formula (1), R 1 = t-butyl group, R 2 =methyl group and R 335.7 parts of polysiloxane (-C3H6-O-C2H4-, manufactured by JNC Corporation, hereinafter referred to as "FM-0421"), 0.25 parts of stannous octylate (product name: "Stanoct", manufactured by Mitsubishi Chemical Corporation), and 591 parts of butyl acetate were charged, and the mixture was heated to 70°C and reacted for 1.5 hours. Next, 117.5 parts of a photopolymerization initiator containing a hydroxyl group (trade name: "Omnirad754", a mixture of 2-(2-hydroxyethoxy)ethyl oxyphenylacetic acid / 2-(2-oxo-2-phenylacetoxyethoxy)ethyl oxyphenylacetic acid = 42 / 58 (by weight), manufactured by IGM Resins, hereinafter referred to as "Omni754") (of which 49.4 parts were the component containing a hydroxyl group) and 0.25 parts of stannous octylate were charged and reacted at 70°C for 1.5 hours to obtain a solution containing product (A-1). For the reactants, Table 1 shows the weight charged, and Table 2 shows the molar amount of the reactants as functional groups (the same applies hereafter).

[0099] Manufacturing Examples 2-8, Comparative Manufacturing Examples 1-3 Using the reaction components and weights shown in Table 1, the procedure was carried out in the same manner as in Production Example 1 to obtain solutions containing products (A-2) to (A-8) and (A'-1) to (A'-3), respectively.

[0100] Manufacturing Example 9 In a reaction apparatus similar to that used in Production Example 1, 42.4 parts of MFA-75B (non-volatile content weight: 31.8 parts), 17.6 parts of FM-0411P, 37.7 parts of FM-0421, 5.0 parts of polyethylene glycol monomethyl ether with a number average molecular weight of 400 (product name: "Uniox M-400", manufactured by NOF Corporation, hereinafter referred to as "M-400"), 10.1 parts of polyethylene glycol monomethyl ether with a number average molecular weight of 1000 (product name: "Uniox M-1000", manufactured by NOF Corporation, hereinafter referred to as "M-1000"), 0.2 parts of stannous octyolate, 0.2 parts of methoquinone, 0.02 parts of phenothiazine, and 360 parts of butyl acetate were charged, and the mixture was heated to 70°C and reacted for 1.5 hours. Next, 97.7 parts of Omnirad754 (of which 41 parts were the component containing a hydroxyl group) and 0.2 parts of stannous octylate were charged and reacted at 70°C for 1.5 hours to obtain a solution containing product (A-9).

[0101] Manufacturing Example 10 In a reaction apparatus similar to that used in Production Example 1, 41.8 parts of Coronate HXR (non-volatile weight: 41.8 parts), 5.1 parts of FM-0411P, 10.9 parts of FM-0421, 14.5 parts of M-400, 29.0 parts of M-1000, 0.2 parts of stannous octyolate, 0.2 parts of methoquinone, 0.02 parts of phenothiazine, and 301 parts of isobornyl acrylate were charged, and the mixture was heated to 70°C and reacted for 1.5 hours. Then, 98.8 parts of Omnirad754 (of which 41.5 parts were the hydroxyl group component) and 0.2 parts of stannous octyolate were charged, and the mixture was reacted at 75°C for 1.5 hours to obtain a solution containing product (A-10).

[0102] Manufacturing Examples 11-12 Using the reaction components and weights shown in Table 1, the procedure was carried out in the same manner as in Production Example 10 to obtain solutions containing products (A-11) to (A-12), respectively.

[0103] Here, we will show, using Production Example 1 as an example, the calculation method for determining the molar amount of each reactive component as a functional group from the actual weight of each reactive component listed in Table 2. <(a1) Regarding the isocyanate group equivalent and molar amount of isocyanate groups of component> ((a1) equivalent amount of isocyanate group) =[{(a1) NCO%} / 100] / {Molecular weight of isocyanate group (42)}×1000=(13.7 / 100) / 42×1000≈3.262(mmol / g) ((a1) Molar amount of isocyanate group of component) ={(Isocyanate group equivalent of component (a1)) / 1000}×(Prepared weight of component (a1) in its present form) =3.262×40.1 / 1000≒0.1308(mol)...(calculation 1) <(a2) Regarding the hydroxyl group equivalent and molar amount of hydroxyl groups of component> ((a2) Hydroxyl group equivalent of component) = {1 / ((a2) Number-average molecular weight))} × 1000 (unit: mmol / g) ※1 *1: Using the above formula, the hydroxyl group equivalent of FM-0411P with a number average molecular weight of 1000 is 1.0, and the hydroxyl group equivalent of FM-0421 with a number average molecular weight of 5000 is 0.20. ((a2) Molar amount of hydroxyl group in component (a2)) = {((a2) hydroxyl group equivalent) / 1000} × ((a2) visibly prepared weight) ※2 *2: Since FM-0411P has a hydroxyl group equivalent of 1.0 and a batch weight of 16.7 parts, and FM-0421 has a hydroxyl group equivalent of 0.20 and a batch weight of 35.7 parts, the molar amounts of hydroxyl groups for each are as follows. (Molar amount of hydroxyl groups in FM-0411P) =(1.0 / 1000)×16.7≒0.0167(mol)...(Calculation 2-1) (Molar amount of hydroxyl groups in FM-0421) =(0.20 / 1000)×35.7≒0.00714(mol)...(Calculation 2-2) <(a4) Regarding the hydroxyl group equivalent and molar amount of hydroxyl groups of component> ((a4) Hydroxyl group equivalent of component) ={1 / ((a4) Number-average molecular weight))} × 1000 (unit: mmol / g)※1 *1: Using the above formula, the hydroxyl group equivalent of Uniox M-400, which has a number average molecular weight of 400, is 2.5, and the hydroxyl group equivalent of Uniox M-1000, which has a number average molecular weight of 1000, is 1.0. ((a4) Molar amount of hydroxyl group in component (a4)) ={((a4) component hydroxyl group equivalent) / 1000}×((a4) component in its present form during preparation) ※2 *2: Since the hydroxyl group equivalent of Uniox M-400 is 2.5 and the brewing weight is 0 parts, and the hydroxyl group equivalent of Uniox M-1000 is 1.0 and the brewing weight is 0 parts, the molar amounts of hydroxyl groups for each are as follows. (Molar amount of hydroxyl groups in Uniox M-400) =(2.5 / 1000)×0=0(mol)...(Calculation 3-1) (Molar amount of hydroxyl groups in Uniox M-1000) =(1.0 / 1000)×0≒0(mol)...(Calculation 3-2) <Regarding the weight of the component containing a hydroxyl group in component (a3) ​​that is necessary to react with all of the isocyanate groups of component (a1) remaining after the reaction with components (a1), (a2), and (a4) (here, 2-(2-hydroxyethoxy)ethyl oxyphenylacetate (weight-average molecular weight: 238.2) is used for this explanation.)> (Molar amount of component (a1) remaining as isocyanate groups after the above reaction) =(Calculation 1)-{(Calculation 2-1)+(Calculation 2-2)+(Calculation 3-1)+Calculation(3-2)} =0.1308-(0.0167+0.00714+0+0)≒0.10696(mol) (The weight of 2-(2-hydroxyethoxy)ethyl oxyphenylacetate required to react completely with the isocyanate group of component (a1) remaining after the above reaction.) = (Molar amount of isocyanate group of component (a1) remaining after the above reaction) × (Weight-average molecular weight of 2-(2-hydroxyethoxy)ethyl oxyphenylacetate) =0.10696×238.2≒25.48(parts) <Hydroxy group equivalents and molar amount of hydroxyl groups of 2-(2-hydroxyethoxy)ethyl oxyphenylacetate> (Hydroxy group equivalent of 2-(2-hydroxyethoxy)ethyl oxyphenylacetate) ={1 / (weight-average molecular weight of 2-(2-hydroxyethoxy)ethyl oxyphenylacetate))}×1000 =(1 / 238.2)×1000≒4.198(mmol / g) (Molar amount of hydroxyl groups in 2-(2-hydroxyethoxy)ethyl oxyphenylacetate) = {(Equivalent amount of hydroxyl groups in 2-(2-hydroxyethoxy)ethyl oxyphenylacetate) × (Weight of 2-(2-hydroxyethoxy)ethyl oxyphenylacetate required)} / 1000 =(4.198×25.48) / 1000≒0.107(mol) (calculation 4) Dividing the values ​​from (Calculation 1), (Calculation 2-1), (Calculation 2-2), (Calculation 3-1), (Calculation 3-2), and (Calculation 4) by the value of (Calculation 1) yields the same values ​​as in Table 2. (a1) component =(calculation 1) / (calculation 1)=0.1308 / 0.1308=1(mol) FM-0411P =(Calculation 2-1) / (Calculation 1)=0.0167 / 0.1308≒0.13(mol) FM-0421 =(Calculation 2-2) / (Calculation 1)=0.00714 / 0.1308≒0.05(mol) Uniox M-400 =(Calculation 3-1) / (Calculation 1)=0 / 0.1308=0(mol) Uniox M-1000 =(Calculation 3-2) / (Calculation 1)=0 / 0.1308=0(mol) (a3) Components (only components containing a hydroxyl group) =(Calculation 4) / (Calculation 1)=0.107 / 0.1308≒0.82(mol)

[0104] [Table 1] *1: The weight of each reaction component is shown as the weight of its non-volatile content, and the value in parentheses represents the weight in its actual form.

[0105] [Table 2] *2: Each reactive component is expressed in terms of the molar amount of the functional group (isocyanate group or hydroxyl group) in the component. *3: If the components containing hydroxyl groups are a mixture, the molar amount is shown as the value for the component containing hydroxyl groups only.

[0106] The abbreviations shown in Tables 1 and 2 represent the following compounds and products. <Polyisocyanate> • MFA-75B - isocyanurate derivative of hexamethylene diisocyanate, product name: "Duranate MFA-75B", NCO = 13.7%, non-volatile content: 75%, manufactured by Asahi Kasei Corporation. • HXR-hexamethylene diisocyanate isocyanurate, trade name: "Coronate HXR", NCO = 21.85%, manufactured by Tosoh Corporation. • HDI-Hexamethylene diisocyanate, NCO=50.1% <Polysiloxanes containing hydroxyl groups> ·FM-0411P - A polysiloxane having a hydroxyl group at one end, trade name: "Cylaprene FM-0411P", having the structure of general formula (1), R 1 = t-butyl group, R 2 =methyl group and R 3 Polysiloxane of the form -C3H6-O-C2H4-, number-average molecular weight: 1000, manufactured by JNC Corporation. ·FM-0421P - A polysiloxane having a hydroxyl group at one end, trade name: "Cylaprene FM-0421", having the structure of general formula (1), R 1 = t-butyl group, R 2 =methyl group and R 3 Polysiloxane of the form -C3H6-O-C2H4-, number-average molecular weight: 5000, manufactured by JNC Corporation. <Components containing a hydroxyl group> Omni754: A mixture of 2-(2-hydroxyethoxy)ethyl oxyphenylacetic acid and 2-(2-oxo-2-phenylacetoxyethoxy)ethyl oxyphenylacetic acid = 42 / 58 (by weight), trade name: "Omnirad754", manufactured by IGM Resins. • Omni1173: 2-hydroxy-2-methyl-1-phenylpropan-1-one, trade name: "Omnirad1173", manufactured by IGM Resins. • Omni2959: 2-Hydroxy-4'-(2-hydroxyethoxy)-2-methylpropiophenone, trade name: "Omnirad2959", manufactured by IGM Resin. IPA: Isopropyl alcohol • DPHA: A mixture of dipentaerythritol pentaacrylate / dipentaerythritol hexaacrylate = 45 / 55 (by weight), product name: "Aronics M-400", manufactured by Toagosei Co., Ltd. <Polyalkylene glycol monoalkyl ether> • M-400: Polyethylene glycol monomethyl ether, product name: "Uniox M-400", number average molecular weight: 400, manufactured by NOF Corporation. • M-1000: Polyethylene glycol monomethyl ether, product name: "Uniox M-1000", number average molecular weight: 1000, manufactured by NOF Corporation.

[0107] Furthermore, some mixtures containing product (A) may contain unreacted component (a3). The method for calculating the non-volatile content concentration of each is also shown using Production Example 1 as an example.

[0108] (Weight of non-volatile content in the mixture containing product (A-1)) = ((a1) component non-volatile content weight) + ((a2) component non-volatile content weight) + ((a3) component non-volatile content weight) + ((a4) component non-volatile content weight)) + (Stanoct component non-volatile content weight) + (Methoquinone non-volatile content weight) + (Phenothiazine non-volatile content weight) =40.1 × (75 / 100) + 16.7 + 35.7 + 117.5 + 0 + 0.5 + 0 + 0 ≒200.48 (parts by weight)

[0109] (Weight of non-volatile content of product (A) only) = ((a1) component non-volatile content weight) + ((a2) component non-volatile content weight) + ((a4) component non-volatile content weight (a3) ​​necessary to react with all of the isocyanate groups of (a1) remaining after the reaction with (a1), (a2), and (a4) (here, 2-(2-hydroxyethoxy)ethyl oxyphenylacetate is used as an example)) = 40.1 × (75 / 100) + 16.7 + 35.7 + 0 + 25.48 =107.96 (parts by weight) Therefore, the non-volatile content concentration of product (A) alone is as follows: (Non-volatile content concentration of product (A) only) = {(Weight of non-volatile content of product (A) only) / (Weight of non-volatile content in the mixture containing product (A))} × 100 =(107.96 / 200.48)×100≒53.85(weight%)...(calculation 5)

[0110] (Weight of unreacted (a3) ​​component non-volatile content) = (Weight of component (a3) ​​in non-volatile form) - (Weight of component (a3) ​​(here, 2-(2-hydroxyethoxy)ethyl oxyphenylacetate used for explanation) required to react with all of the isocyanate groups of component (a1) remaining after the reaction with components (a1), (a2), and (a4)) =117.5-25.48=92.02(g) Therefore, the non-volatile content concentration of the unreacted (a3) ​​component is as follows: (Concentration of unreacted non-volatile content of component (a3)) = {(Weight of unreacted (a3) ​​component nonvolatile content) / (Weight of nonvolatile content in the mixture containing product (A))} × 100 =(92.02 / 200.48)×100≒45.9(weight%)...(calculation 6)

[0111] Furthermore, in cases where component (B), such as isobornyl acrylate (hereinafter referred to as IBXA), is used as a diluent, as in production examples 10 to 12, the weight of the non-volatile content of the mixture containing product (A) is calculated by adding up the weights of the non-volatile content of component (B), and the non-volatile content of product (A) alone, the non-volatile content of the unreacted component (a3), and the non-volatile content of IBXA are calculated using the same method as described above. Table 3 shows the non-volatile content of product (A) alone, the unreacted component (a3), and IBXA in the mixtures containing the purified product (A) obtained in each production example.

[0112] [Table 3]

[0113] Example 1 1.3 parts (non-volatile content) of a mixture containing product (A-1) from Production Example 1 (product (A-1): 0.7 parts, Omnirad754: 0.6 parts) (each multiplied by the non-volatile content concentration listed in Table 3), 98.7 parts of a mixture of pentaerythritol triacrylate and pentaerythritol tetraacrylate (trade name: "Aronics M-305", manufactured by Toagosei Co., Ltd.), and 0.5 parts of 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropiophenone (trade name: "Omnirad907", manufactured by IGM Resins) were charged, methyl ethyl ketone was added and mixed to obtain curable coating agent compositions with a non-volatile content of 25%. Table 4 shows the charge weight of each component in terms of non-volatile content, and Table 5 shows the content of each component separately: product (A), (meth)acrylate, and photopolymerization initiator (C) (the same applies hereafter).

[0114] Examples 2-13, Examples 17-18, Examples 22-27, Comparative Examples 1-3 Each component was prepared to the extent shown in Table 4, and methyl ethyl ketone was added and mixed to obtain curable coating agent compositions with a non-volatile content of 25%.

[0115] Example 14 (A) 10.3 parts (non-volatile content) of a mixture containing product (A-10) (product (A-10): 2.8 parts, Omnirad754: 1.3 parts, isobornyl acrylate: 6.2 parts), and (B) 89.7 parts of Aronics M-305 and 5 parts of Omnirad907 were charged, and methyl ethyl ketone was added and mixed to obtain curable coating agent compositions with a non-volatile content of 25%.

[0116] Examples 15-16 Each component was prepared to the extent shown in Table 4, and methyl ethyl ketone was added and mixed to obtain curable coating agent compositions with a non-volatile content of 25%.

[0117] Example 19 The composition of Example 1 was further mixed with 0.6 parts of Omnirad754 to obtain a curable coating agent composition with a non-volatile content of 25%.

[0118] Example 20 In a reactor equipped with a condenser and a stirrer, 10.6 parts of a mixture containing product (A-11) and 37.5 parts of a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (product name: "Aronics M-400", manufactured by Toagosei Co., Ltd.) were added, the temperature was raised to 40°C, and the mixture was mixed for 30 minutes. Then, 6.3 parts (non-volatile weight: 1.9 parts) of a reactive surfactant (product name: "Aminoion RE-1000L", manufactured by Nippon Emulsifier Co., Ltd.) and 4.5 parts of water were added, and the mixture was kneaded at 40°C for 1 hour. After that, 41.1 parts of water were gradually added to emulsify the mixture. 1.1 parts of a leveling agent (product name: "Orfin EXP.4130", manufactured by Nisshin Chemical Industry Co., Ltd.) and 61.9 parts of water were added, and the mixture was mixed for 30 minutes to obtain a curable coating agent composition.

[0119] Example 21 In the same reaction apparatus as in Example 20, 34.2 parts of a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (trade name: "Aronics M-400", manufactured by Toagosei Co., Ltd.) and 3.4 parts of 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropiophenone (trade name: "OMNIRAD 907", manufactured by IGM Resins) were added, and the mixture was heated to 80°C and mixed for 1 hour. After cooling to 40°C, 10.65 parts of the mixture containing product (A-11) were added and stirred for 30 minutes. Then, 5.7 parts (non-volatile weight: 1.7 parts) of a reactive surfactant (trade name: "Aminoion RE-1000L", manufactured by Nippon Emulsifier Co., Ltd.) and 4.2 parts of water were added, and the mixture was kneaded at 40°C for 1 hour, after which 41.86 parts of water were gradually added to emulsify. 1.1 parts of a leveling agent (product name: "Orphine EXP.4130", manufactured by Nisshin Chemical Industry Co., Ltd.) and 61.9 parts of water were added and mixed for 30 minutes to obtain a curable coating agent composition.

[0120] Example 28 In the same reaction apparatus as in Example 20, 60.0 parts of a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (product name: "Aronics M-400", manufactured by Toagosei Co., Ltd.) were added, and the mixture was heated to 80°C and mixed for 1 hour. After cooling to 40°C, 40.0 parts of the mixture containing product (A-11) were added and stirred for 30 minutes. Then, 5.7 parts (non-volatile weight: 1.7 parts) of a reactive surfactant (product name: "Aminoion RE-1000L", manufactured by Nippon Emulsifier Co., Ltd.) and 4.2 parts of water were added, and the mixture was kneaded at 40°C for 1 hour, after which 41.86 parts of water were gradually added to emulsify. 1.1 parts of a leveling agent (product name: "Orfin EXP.4130", manufactured by Nisshin Chemical Industry Co., Ltd.) and 61.9 parts of water were added and mixed for 30 minutes to obtain a curable coating agent composition.

[0121] Example 29 In the same reaction apparatus as in Example 20, 50.0 parts of a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (product name: "Aronics M-400", manufactured by Toagosei Co., Ltd.) were added, and the mixture was heated to 80°C and mixed for 1 hour. After cooling to 40°C, 50.0 parts of the mixture containing product (A-11) were added and stirred for 30 minutes. Then, 5.7 parts (non-volatile weight: 1.7 parts) of a reactive surfactant (product name: "Aminoion RE-1000L", manufactured by Nippon Emulsifier Co., Ltd.) and 4.2 parts of water were added, and the mixture was kneaded at 40°C for 1 hour, after which 41.86 parts of water were gradually added to emulsify. 1.1 parts of a leveling agent (product name: "Orfin EXP.4130", manufactured by Nisshin Chemical Industry Co., Ltd.) and 61.9 parts of water were added and mixed for 30 minutes to obtain a curable coating agent composition.

[0122] (Fabrication of laminates) Each curable coating agent composition was applied to a polyethylene terephthalate film (thickness: 100 μm) using a bar coater so that the cured layer thickness after drying was 1 μm. After drying at 80°C for 1 minute, it was subjected to high-pressure mercury lamp (520 mW / cm²). 2 , 200 mJ / cm 2 After irradiating with ultraviolet light, the laminates were left overnight at room temperature to obtain each of the following materials.

[0123] (Peeling force) Polyester adhesive tape (product name: "No.31B", width: 20 mm, manufactured by Nitto Denko Corporation) was applied to the side of the cured layer of each laminate using a 2 kg roller, and left at 23°C for 30 minutes. Next, using a Tensilon universal testing machine (device name: "RTC-1250A", manufactured by A&D Co., Ltd.), the adhesive tape was pulled horizontally at an angle of 180° and a speed of 0.3 mm / min, and the peel force (mN / 20 mm) was measured. A value of 600 mN / 20 mm or less was considered good, and a smaller value indicates better peel force.

[0124] (Amount of silicone transfer) Polyester adhesive tape (product name: "No.31B", manufactured by Nitto Denko Corporation, 20 mm wide) was applied to the side of the cured layer of each laminate using a 2 kg roller under pressure, and left at 23°C for 30 minutes. Next, the polyester adhesive tape was peeled off, and the siloxane (Si atom) content of the surface that was in contact with the cured layer was measured using a scanning X-ray photoelectron spectroscopy analyzer (product name: "PHI5000VersaProbeIII", manufactured by ULVAC-PHI, Inc.). A value of 10% or less was considered good, and a smaller value indicated less silicone migration.

[0125] [Table 4]

[0126] [Table 5] *4: The content of the product and (meth)acrylate is expressed as a ratio when the total weight ratio of the non-volatile content of the product and (meth)acrylate is set to 100% by weight. The content of the photopolymerization initiator is expressed as a weight ratio to 100% by weight of the total non-volatile content of the product and (meth)acrylate. The weight ratio of component (A) is expressed as the value for component (A) alone.

[0127] The symbols shown in Tables 4 and 5 represent the following compounds. <product> Products of A-1 to A-12, A'-1 to A'-3 - Production Examples 1 to 12, and Comparative Production Examples 1 to 3 (in the same order for compound production) <(meth)acrylate> • A mixture of B-1-pentaerythritol triacrylate and pentaerythritol tetraacrylate, trade name: "Aronics M-305", manufactured by Toagosei Co., Ltd. A mixture of B-2-dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate, trade name: "Aronics M-400", manufactured by Toagosei Co., Ltd. B'-1-isobornyl acrylate <Photopolymerization initiator> Omni907-2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropiophenone, trade name: "Omnirad907", manufactured by IGM Resins. • A mixture of Omni754-oxyphenylacetic acid 2-(2-hydroxyethoxy)ethyl ester and oxyphenylacetic acid 2-(2-oxo-2-phenylacetoxyethoxy)ethyl ester, trade name: "Omnirad754", manufactured by IGM Resins.

Claims

1. A curable coating agent composition comprising a product (A) of a reaction component containing a polyisocyanate (a1) having three or more isocyanate groups, a polysiloxane (a2) having a hydroxyl group, and a photopolymerization initiator (a3) ​​having a hydroxyl group, and a poly(meth)acrylate (B).

2. The curable coating agent composition according to claim 1, wherein the reaction component further comprises a polyalkylene glycol monoalkyl ether (a4).

3. A cured product comprising the curable coating agent composition according to claim 1 or 2.

4. A laminate having a layer of the cured material described in claim 3 on at least one side of a substrate.

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