CN113354968A

CN113354968A - Active energy ray-curable resin composition, cured product, laminate, and curing method

Info

Publication number: CN113354968A
Application number: CN202110222430.8A
Authority: CN
Inventors: 石嶋优树; 大江祐辅; 佐藤仁宣; 小谷野浩寿
Original assignee: Arakawa Chemical Industries Ltd
Current assignee: Arakawa Chemical Industries Ltd
Priority date: 2020-03-05
Filing date: 2021-02-25
Publication date: 2021-09-07
Also published as: JP2021138945A; JP7415980B2

Abstract

The present invention addresses the problem of providing an active energy ray-curable resin composition that can produce a cured product having a certain processability, pencil hardness, and scratch resistance, a cured product and a laminate containing the composition, and a curing method. The solution provided by the present invention is an active energy ray-curable resin composition comprising: a (meth) acrylic acid copolymer (A) which is a reaction product of a radical polymer (a1) containing a monomer component of an epoxy group-containing mono (meth) acrylate and an alpha, beta-unsaturated carboxylic acid (a2), and which has a hydroxyl group concentration of 2mmol/g or more, a polyfunctional (meth) acrylate (B) having at least three (meth) acryloyl groups, and a metal compound (C), and which has a hydroxyl group concentration of 400g/eq or less.

Description

Active energy ray-curable resin composition, cured product, laminate, and curing method

Technical Field

The present invention relates to an active energy ray-curable resin composition, a cured product, and a laminate.

Background

Various plastics have been used in various fields such as the main bodies of household electric appliances such as refrigerators, televisions, air conditioners, remote controllers thereof, housings and displays of information terminals such as mobile phones, smartphones, input boards, personal computers, automobile parts, and automobile interior materials. Plastics have advantages such as processability, transparency, lightweight property, and low cost, but have disadvantages such as softness and easy scratching compared to glass materials.

In order to improve these disadvantages, a hard coating agent is applied to the surface of the plastic material to improve the scratch resistance of the surface without impairing the advantages of the plastic material. As such a hard coating agent, silicone-based, acrylic-based, melamine-based resins, and the like can be used. Among these, from the viewpoint of curing time, raw material cost, and the like, active energy ray-curable resin compositions using acrylic resins curable by active energy rays such as ultraviolet rays have become the mainstream.

[ Prior art documents ]

[ patent document ]

[ patent document 1] Japanese patent laid-open No. 2004-

Disclosure of Invention

[ problems to be solved by the invention ]

In the case of using the active energy ray-curable resin composition, when the active energy ray-curable resin composition is applied before the molding of the plastic and is irradiated with an active energy ray to crosslink and cure the resin, the crosslinking density of the resin can be increased to improve the chemical resistance and the scratch resistance. On the other hand, the active energy ray-curable resin composition cross-cured in such a manner has poor processability. In order to cope with such a problem of processability, an active energy ray-curable resin composition is applied by coating or the like after the plastic is molded (patent document 1). However, the above method has problems that the number of coating steps is increased, uneven coating occurs on the curved surface portion of the processed product, and the yield is poor.

Therefore, a hard coating agent which can be applied before molding of a plastic or film and has coating film hardness such as processability and scratch resistance is required.

The present invention addresses the problem of providing an active energy ray-curable resin composition that can produce a cured product having a certain processability, pencil hardness, and scratch resistance, and a cured product and a laminate containing the composition.

[ means for solving problems ]

As a result of diligent research, the present inventors have found that the above problems can be solved by using a predetermined active energy ray-curable resin composition.

That is, the present invention relates to the following items 1 to 8.

(item 1)

An active energy ray-curable resin composition comprising:

a (meth) acrylic acid copolymer (A) which is a reaction product of a radical polymer (a1) containing a monomer component of an epoxy group-containing mono (meth) acrylate and an α, β -unsaturated carboxylic acid (a2), and which has a hydroxyl group concentration of 2mmol/g or more and a (meth) acrylic acid equivalent of 400g/eq or less;

a polyfunctional (meth) acrylate (B) having at least three (meth) acryloyl groups; and

a metal compound (C).

(item 2)

The active energy ray-curable resin composition according to item 1, wherein

(A) The hydroxyl group concentration of the component (B) is 2 to 5mmol/g,

(A) component (B) has a (meth) acrylic acid equivalent of 150 to 400g/eq, and

(B) the component (A) has 3 or more and 30 or less (meth) acryloyl groups.

(item 3)

The active energy ray-curable resin composition according to item 1 or 2, wherein the component (C) is at least one selected from the group consisting of aluminum chelate, zirconium chelate and titanium chelate.

(item 4)

The active energy ray-curable resin composition according to any one of items 1 to 3, wherein the content of the component (C) is 1% by mass or more and 15% by mass or less in terms of solid content, relative to 100% by mass of the total amount of the components (A) and (B).

(item 5)

A partially cured product obtained by heating the active energy ray curable resin composition according to any one of items 1 to 4, and having an elongation at break of 40% or more.

(item 6)

A cured product of the active energy ray-curable resin composition according to any one of items 1 to 4.

(item 7)

A laminate, comprising:

the partially cured product according to item 5 or the cured product according to item 6; and

a substrate.

(item 8)

A method of irradiating an active energy ray to a partially cured product obtained by heat treatment of the active energy ray-curable resin composition according to any one of items 1 to 4 to cure the resin composition.

[ Effect of the invention ]

The active energy ray-curable resin composition, and the cured product and laminate containing the same of the present invention have a certain processability, pencil hardness, and scratch resistance.

Detailed Description

In the entire disclosure, the ranges of numerical values such as the physical property values and the contents may be appropriately set (for example, selected from the upper limit and the lower limit described in the following items). Specifically, as for the numerical value α, when the lower limit of the numerical value α is exemplified by a1, a2, A3, and the like, and the upper limit of the numerical value α is exemplified by B1, B2, B3, and the like, the range of the numerical value α can be exemplified by a1 or more, a2 or more, A3 or more, B1 or less, B2 or less, B3 or less, a1 to B1, a1 to B2, a1 to B3, a2 to B1, a2 to B2, a2 to B3, A3 to B1, A3 to B2, A3 to B3, and the like. In the present disclosure, "to" is used to include numerical values described before and after the "to" as the lower limit value and the upper limit value.

The present invention relates to an active energy ray-curable resin composition (hereinafter also referred to as "resin composition") comprising: a (meth) acrylic acid copolymer (a) (hereinafter also referred to as "component (a)") which is a reaction product of a radical polymer (a1) (hereinafter also referred to as "component (a 1)") containing a monomer component of an epoxy group-containing mono (meth) acrylate and an α, β -unsaturated carboxylic acid (a2) (hereinafter also referred to as "component (a 2)") and has a hydroxyl group concentration of 2mmol/g or more and a (meth) acrylic acid equivalent of 400g/eq or less; a polyfunctional (meth) acrylate (B) having at least three (meth) acryloyl groups (hereinafter also referred to as "(B) component"); and a metal compound (C) (hereinafter also referred to as "component (C)"). Furthermore, (meth) acrylate refers to acrylate and/or methacrylate. Further, (meth) acrylic acid means acrylic acid and/or methacrylic acid. Further, (meth) acryloyl means acryloyl and/or methacryloyl.

< ingredient (A) >

(A) Component (b) is a (meth) acrylic acid copolymer which is a reaction product of component (a1) and component (a2), and has a hydroxyl group concentration of 2mmol/g or more and a (meth) acrylic acid equivalent of 400g/eq or less. As the component (A), two or more kinds of the copolymer may be used in combination.

< ingredient (a1) >

(a1) The component (A) is a radical polymer of a monomer component containing an epoxy group-containing mono (meth) acrylate. As the epoxy group-containing mono (meth) acrylate (hereinafter, also referred to as "component a 1-1"), various known ones can be used.

Examples of the component (a1-1) include glycidyl (meth) acrylate, glycidyl α -ethylacrylate, glycidyl α -n-propylacrylate, glycidyl α -n-butylacrylate, 4-hydroxybutyl (meth) acrylate glycidyl ether, and [ (3, 4-epoxycyclohexane) -1-yl ] methyl (meth) acrylate. The substances exemplified as the component (a1-1) and the substances known as the component (a1-1) may be used alone or in combination of two or more. The component (a1-1) is preferably glycidyl (meth) acrylate in terms of ease of obtaining and scratch resistance.

(a1) The constituent monomer of component (A) may contain a copolymerizable monomer having no epoxy group (hereinafter also referred to as "component (a 1-2)") in addition to component (a 1-1). As the component (a1-2), various known substances can be used.

Examples of the component (a1-2) include: aromatic mono (meth) acrylates such as styrene, α -methylstyrene, t-butylstyrene and dimethylstyrene; aliphatic unsaturated dicarboxylic acid anhydrides such as maleic anhydride, itaconic anhydride, citraconic anhydride, alkenylsuccinic anhydride and dienylsuccinic anhydride; (meth) acrylates such as methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, cyclohexyl (meth) acrylate, stearyl (meth) acrylate, benzyl (meth) acrylate, isobornyl (meth) acrylate, and dicyclopentadienyl (meth) acrylate; acrylonitrile, acrylamide, vinyl acetate, a macromonomer having one or more unsaturated double bonds at any one end and containing no epoxy group or carboxyl group, and the like. Examples of the macromonomer having one or more unsaturated double bonds at any one end and containing no epoxy group or carboxyl group include a (meth) acryloyl group-containing macromonomer, polysiloxane macromonomer, (meth) acrylate macromonomer, styrene macromonomer, (meth) acrylamide macromonomer, and acrylonitrile macromonomer. The substances exemplified as the component (a1-2) and the substances known as the component (a1-2) may be used alone or in combination of two or more. As the macromonomer, a commercially available product can also be used. The product is not particularly limited, and examples thereof include (meth) acryloyl group-containing macromonomers (product names "Macromonomer (Macromonomer) AA-6", "Macromonomer (Macromonomer) AB-6", manufactured by tokyo synthesis (stock)), polysiloxane macromonomers (product names "selaplane FM-0711", "selaplane FM-0721", manufactured by Jenzhi (JNC) (stock)), and (meth) acrylate macromonomers (product names "blanmomer PME-4000", "blanmomer PSE-1300", manufactured by solar oil (stock)), and the like.

< ingredient (a2) >

(a2) The component (B) is an alpha, beta-unsaturated carboxylic acid. In the present disclosure, an α, β -unsaturated carboxylic acid refers to a substance having an unsaturated bond between a carbon (α carbon) located beside a carboxyl group and a further adjacent carbon (β carbon).

The component (a2) is not particularly limited, and various known substances can be used. Examples of the component (a2) include α, β -unsaturated monocarboxylic acids, α, β -unsaturated dicarboxylic acids, and the like. Examples of the α, β -unsaturated monocarboxylic acid include (meth) acrylic acid. Examples of the α, β -unsaturated dicarboxylic acid include itaconic acid and maleic acid. The substances exemplified as the component (a2) and the substances known as the component (a2) may be used alone or in combination of two or more. The component (a2) is preferably an α, β -unsaturated monocarboxylic acid, and more preferably (meth) acrylic acid, from the viewpoint of satisfactory scratch resistance of a coating film (hereinafter also referred to as "cured product") obtained by completely curing the resin composition.

(a1) Examples of the upper limit of the mass ratio of the solid components of component (a2) to component (a2) ((a1)/(a2)) include 99/1, 95/5, 90/10, 85/15, 80/20, 75/25, 70/30, 65/35, 60/40, 50/50, 40/60, 30/70, 20/80, and examples of the lower limit thereof include 95/5, 90/10, 85/15, 80/20, 70/30, 60/40, 50/50, 40/60, 30/70, 20/80, 10/90. In one embodiment, the mass ratio of the solid components of component (a1) and component (a2) ((a1)/(a2)) is preferably about 10/90 to 99/1.

(A) The upper limit of the hydroxyl group concentration of the component (B) may be exemplified by 5mmol/g, 4.9mmol/g, 4.8mmol/g, 4.7mmol/g, 4.6mmol/g, 4.5mmol/g, 4.4mmol/g, 4.3mmol/g, 4.2mmol/g, 4.1mmol/g, 4mmol/g, 3.9mmol/g, 3.8mmol/g, 3.7mmol/g, 3.6mmol/g, 3.5mmol/g, 3.4mmol/g, 3.3mmol/g, 3.2mmol/g, 3.1mmol/g, 3mmol/g, 2.9mmol/g, 2.8mmol/g, 2.7mmol/g, 2.6mmol/g, 2.5mmol/g, 2.4mmol/g, 2.3mmol/g, 2.2mmol/g, 2.1mmol/g, 4.9mmol/g, 4.7mmol/g, 4.6mmol/g, 4mmol/g, 4.4mmol/g, 4.6mmol/g, 4.5mmol/g, 4.4mmol/g, 4.3mmol/g, 4.2mmol/g, 4.1mmol/g, 4mmol/g, 3.9mmol/g, 3.8mmol/g, 3.7mmol/g, 3.6mmol/g, 3.5mmol/g, 3.4mmol/g, 3.3mmol/g, 3.2mmol/g, 3.1mmol/g, 3mmol/g, 2.9mmol/g, 2.8mmol/g, 2.7mmol/g, 2.6mmol/g, 2.5mmol/g, 2.4mmol/g, 2.3mmol/g, 2.2mmol/g, 2.1mmol/g, 2mmol/g, etc. In one embodiment, the hydroxyl group concentration of the component (A) is preferably about 2 to 5 mmol/g. When the hydroxyl group concentration of the component (a) is not less than the lower limit, the scratch resistance of the cured product is favorable, and therefore, it is preferable. In the present disclosure, the hydroxyl group concentration indicates the proportion of hydroxyl groups contained in 1g of one or more components for which it is desired to calculate the hydroxyl group concentration, and can be calculated from "the number of hydroxyl groups/the molecular weight of one or more components".

(A) The upper limit of the (meth) acrylic acid equivalent of the component (A) may be 400g/eq, 390g/eq, 380g/eq, 370g/eq, 360g/eq, 350g/eq, 340g/eq, 330g/eq, 320g/eq, 310g/eq, 300g/eq, 290g/eq, 280g/eq, 270g/eq, 260g/eq, 250g/eq, 240g/eq, 230g/eq, 220g/eq, 210g/eq, 200g/eq, 190g/eq, 80g/eq, 170g/eq, 160g/eq, etc., and the lower limit may be 390g/eq, 380g/eq, 370g/eq, 360g/eq, 350g/eq, 340g/eq, 330g/eq, 320g/eq, or 180g/eq, etc, 310g/eq, 300g/eq, 290g/eq, 280g/eq, 270g/eq, 260g/eq, 250g/eq, 240g/eq, 230g/eq, 220g/eq, 210g/eq, 200g/eq, 190g/eq, 180g/eq, 170g/eq, 160g/eq, 150g/eq, etc. In one embodiment, the equivalent weight of (meth) acrylic acid in the component (A) is preferably about 150g/eq to 400 g/eq. When the (meth) acrylic acid equivalent of the component (a) is not more than the upper limit, the scratch resistance of the cured product is good, and therefore, it is preferable. In the present disclosure, the (meth) acrylic equivalent is represented by the molecular weight of each (meth) acrylic group, and can be calculated from "molecular weight/number of functional groups".

(A) The upper limit of the weight average molecular weight of the component (a) may be 200,000, 150,000, 100,000, 50,000, 30,000, 10,000, etc., and the lower limit may be 150,000, 100,000, 50,000, 30,000, 10,000, 5,000, etc. In one embodiment, the weight average molecular weight of the component (a) is preferably 5,000 or more and 200,000 or less. When the weight average molecular weight of the component (A) is within the above range, the cured product has excellent blocking resistance, and the resin composition has a preferred viscosity. In the present disclosure, the weight average molecular weight is a polystyrene conversion value obtained by gel permeation chromatography.

The upper limit of the content (in terms of solid content) of the component (a) may be 99 mass%, 95 mass%, 90 mass%, 85 mass%, 80 mass%, 70 mass%, 60 mass%, 50 mass%, 40 mass%, 30 mass%, 20 mass% or the like, and the lower limit may be 95 mass%, 90 mass%, 85 mass%, 80 mass%, 70 mass%, 60 mass%, 50 mass%, 40 mass%, 30 mass%, 20 mass%, 10 mass% or the like, with respect to 100 mass% of the total amount of the resin composition. In one embodiment, the content (in terms of solid content) of the component (a) is preferably about 10% by mass to 99% by mass based on 100% by mass of the total amount of the resin composition.

< Synthesis method of component (A) >

The method for synthesizing the component (a) is not particularly limited, and various known methods can be used. Examples of the method for synthesizing component (A) include a method in which component (a1) and component (a2) are reacted at 50 ℃ to 200 ℃ for 30 minutes to 12 hours.

< ingredient (B) >

(B) Component (A) is different from component (A) and has at least three (meth) acryloyl groups (H)₂And (C) CR-C (O) - (R is hydrogen or methyl)) are disclosed.

(B) The upper limit of the number of (meth) acryloyl groups in the component (a) may be 30, 25, 20, 18, 16, 15, 10, 8, 6, 5, 4, etc., and the lower limit may be 25, 20, 18, 16, 15, 10, 8, 6, 5, 4, 3, etc. In one embodiment, the number of (meth) acryloyl groups contained in the component (B) is preferably about 3 to 30. When the number of (meth) acryloyl groups in the component (B) is in the above range, the viscosity of the partially cured product, the scratch resistance of the cured product, and the pencil hardness tend to be excellent.

Examples of the component (B) include a polyfunctional (meth) acrylate having three (meth) acryloyl groups, a polyfunctional (meth) acrylate having four (meth) acryloyl groups, a polyfunctional (meth) acrylate having five (meth) acryloyl groups, and a polyfunctional (meth) acrylate having six (meth) acryloyl groups. Examples of the polyfunctional (meth) acrylate having three (meth) acryloyl groups include glycerol tri (meth) acrylate, sorbitol tri (meth) acrylate, tris 2-hydroxyethyl isocyanurate tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, Ethylene Oxide (EO) -modified trimethylolpropane tri (meth) acrylate, Propylene Oxide (PO) -modified trimethylolpropane tri (meth) acrylate, EO-modified phosphoric acid tri (meth) acrylate, trimethylolethane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol tri (meth) acrylate, and ethoxylated isocyanuric acid tri (meth) acrylate. Examples of the polyfunctional (meth) acrylate having four (meth) acryloyl groups include 1, 2, 3-cyclohexane tetra (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, and sorbitol tetra (meth) acrylate. Examples of the polyfunctional (meth) acrylate having five (meth) acryloyl groups include sorbitol penta (meth) acrylate, di-trimethylolpropane penta (meth) acrylate, dipentaerythritol penta (meth) acrylate, and the like. Examples of the polyfunctional (meth) acrylate having six (meth) acryloyl groups include ditrimethylolpropane hexa (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and caprolactone-modified dipentaerythritol hexa (meth) acrylate.

Examples of the other component (B) include polyurethane (meth) acrylate, polyester (meth) acrylate, and epoxy poly (meth) acrylate.

As a method for synthesizing the polyurethane (meth) acrylate, various known methods can be exemplified. Examples of known methods for synthesizing the polyurethane (meth) acrylate include:

(1) a method in which a hydroxyl group-containing (meth) acrylate is further subjected to a urethanization reaction with an isocyanate group-terminated prepolymer obtained by urethanizing a polyol and a polyisocyanate;

(2) a method of reacting an isocyanate group-containing (meth) acrylate with a hydroxyl-terminated prepolymer obtained by urethanizing a polyol and a polyisocyanate;

(3) a method of reacting a polyisocyanate with a hydroxyl group-containing (meth) acrylate, and the like.

In these methods, various known catalysts (e.g., dibutyltin dilaurate) can be suitably used as needed.

Examples of the polyol include polyether polyol, polyester polyol, polycarbonate polyol, acrylic polyol, polyolefin polyol, neopentyl glycol, 3-methyl-1, 5-pentanediol, ethylene glycol, propylene glycol, 1, 4-butanediol, 1, 6-hexanediol, trimethylolpropane, pentaerythritol, tricyclodecane dimethylol, bis- [ hydroxymethyl ] -cyclohexane, and the like. The polyhydric alcohol exemplified above and the polyhydric alcohol known per se can be used alone or in combination of two or more.

Examples of the polyether polyol include polyalkylene glycol (such as polyethylene glycol, polypropylene glycol, and polytetramethylene glycol). As the polyether polyol, commercially available products can also be used. Examples of the product include products such as "adi Polyether (ADEKA Polyether) P series", "adi Polyether (ADEKA Polyether) G series", "adi Polyether (ADEKA Polyether) EDP series" (manufactured by adi (ADEKA) (stock)), and the like.

Examples of the polyester polyol include those obtained by the reaction of a polyol with a polycarboxylic acid (succinic acid, phthalic acid, malonic acid, maleic acid, adipic acid, suberic acid, azelaic acid, sebacic acid, etc.), ring-opened polymers of cyclic esters (propiolactone, β -methyl- δ -valerolactone, e-caprolactone, etc.), and three-component reaction products of a polyol with a polycarboxylic acid and a cyclic ester. As the polyester polyol, a commercially available product can be used. Examples of the product include the product names "Colorado Polyol (Kuraray Polyol) P series", "Colorado Polyol (Kuraray Polyol) F series" (manufactured by Colorado (Kuraray) (Co., Ltd.), the product name "Placcel (Placcel) 205" (manufactured by Daicel (Daicel) (Co., Ltd.), and the product name "Polilet (Polylite) OD-X-2155" (manufactured by Di Egyo (DIC) (Co., Ltd.).

Examples of the polycarbonate polyol include a reaction product of a polyol and phosgene (phosgene), a ring-opened polymer of a cyclic carbonate (e.g., alkylene carbonate), and the like. Examples of the alkylene carbonate include ethylene carbonate, trimethylene carbonate, tetramethylene carbonate, and hexamethylene carbonate. As the polycarbonate polyol, a commercially available product can be used. The product may be named "kohler Polyol (Kuraray Polyol) C series" (manufactured by kohler corporation), for example.

Examples of the acrylic polyol include homopolymers or copolymers of acrylic monomers having one or more hydroxyl groups in one molecule, and copolymers obtained by copolymerizing these copolymers with other monomers. As the acrylic polyol, a commercially available product can be used. The product may be named "Yajiaofeng UH-2000 series" (manufactured by east Asia corporation), for example.

Examples of the polyolefin polyol include polybutadiene, hydrogenated polybutadiene, polyisoprene, hydrogenated polyisoprene, and chlorides thereof having two or more hydroxyl groups. As the polyolefin polyol, commercially available products can also be used. Examples of the product include "Nissan (NISSO) -PB GI series" (manufactured by Nissan Co., Ltd.).

Examples of the polyisocyanate include isophorone diisocyanate, hexamethylene diisocyanate, dicyclohexylmethane diisocyanate, tolylene diisocyanate, xylene diisocyanate, diphenylmethane-4, 4' -diisocyanate, 3-methyldiphenylmethane diisocyanate, 1, 5-naphthalene diisocyanate, and dicyclopentyl isocyanate. Examples of the other polyisocyanate include the above-mentioned exemplified polyisocyanates, adducts of various known polyisocyanates, and polymers of these isocyanates. Examples of such polyisocyanates include biuret, urethanate, adduct, allophanate (allophanate), and the like. Examples of the Biuret of the polyisocyanate include those having the names "Polydande (Duranate) 24A-100", "Biuret (Biuret) 22A-75P" and "Biuret (Biuret) 21S-75E" (all manufactured by Asahi chemical (Strand)). Examples of the uric acid ester of polyisocyanate include those having the trade names "crotonate HK" and "crotonate HXR" (all manufactured by tokoa (stock)). Examples of the adduct of polyisocyanate include "crotonate HL" (manufactured by tokyo (r) ") and the like. Examples of the allophanate of the polyisocyanate include "crotonate" 2770 "(manufactured by Tosoh corporation). The polyisocyanate of the present disclosure may have an average isocyanate number of about 3 to 10. The average number of isocyanate groups can be calculated by the following formula. Average isocyanate group number ═ (number average molecular weight (Mn) × isocyanate group concentration (%)/(42.02 × 100). The isocyanate group concentration (%) in the formula (I) is determined by the following method in accordance with Japanese Industrial Standards (JIS) K1603-1: 2007. The polyisocyanate exemplified above and the polyisocyanate known per se can be used alone or in combination of two or more.

Examples of the hydroxyl group-containing (meth) acrylate include: 1-hydroxymethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, hydroxycyclohexyl (meth) acrylate, methyl 4- (hydroxymethyl) cyclohexyl (meth) acrylate, 4- (hydroxymethyl) cyclohexylmethyl 2-hydroxypropionate, hydroxyphenyl (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, and the like. The hydroxyl group-containing (meth) acrylate exemplified above and the hydroxyl group-containing (meth) acrylate known per se may be used alone or in combination of two or more.

Examples of the isocyanate group-containing (meth) acrylate include 2-isocyanatoethyl (meth) acrylate and 1, 1- (bisacryloxymethyl) ethyl isocyanate. The isocyanate group-containing (meth) acrylate exemplified above and the isocyanate group-containing (meth) acrylate known in the art may be used alone or in combination of two or more.

Various known methods can be exemplified as a method for synthesizing the polyester (meth) acrylate. Examples of the various known synthetic methods for polyester (meth) acrylate include:

(1) a method of reacting a carboxyl group-containing (meth) acrylate (carboxyethyl (meth) acrylate, carboxypolycaprolactone mono (meth) acrylate, etc.) with a hydroxyl group-terminated polyester obtained by reacting a polycarboxylic acid with a polyhydric alcohol;

(2) a method of reacting a carboxyl-terminated polyester obtained by reacting a polycarboxylic acid with a polyhydric alcohol with a hydroxyl-containing (meth) acrylate.

In these methods, various known catalysts can be suitably used as needed.

Examples of the epoxy poly (meth) acrylate include those obtained by addition reaction of a carboxyl group-containing (meth) acrylate and an epoxy resin having at least two epoxy groups in one molecule (such as a bisphenol a type epoxy resin, a bisphenol F type epoxy resin, and a bisphenol type epoxy resin).

In these methods, various known catalysts can be suitably used as needed.

(B) Commercially available products can be used as the components. As the product, there can be exemplified: pentaerythritol triacrylate ((product name "a-TMM-3", "a-TMM-3L", manufactured by maizhou chemical industry (stock)), (product name "Miramer) M301", manufactured by Meiyuan (MIWON) corporation), (product name "arinexus (Aronix) M-309", manufactured by east asian synthesis (stock)), di-trimethylolpropane tetraacrylate (product name "arinexus (Aronix) M-408", manufactured by east asian synthesis (stock)), ethoxylated pentaerythritol tetra (meth) acrylate (product name "SR 494", manufactured by Sartomer), dipentaerythritol penta (meth) acrylate (product name "SR 399", manufactured by Sartomer), a mixture of dipentaerythritol poly (meth) acrylate (dipentaerythritol penta (meth) acrylate and dipentaerythritol hexa (meth) acrylate) ((product name "yakara (ka) DPHA", manufactured by Nippon Chemicals (Ltd.), (manufactured by "A-9550" manufactured by Nizhongmura chemical industry (Ltd.), (manufactured by "Aronix" M-403 "," Aronix (Aronix) M-400 "," Aronix (Aronix) M-402 "," Aronix (Aronix) M-404 "," Aronix (Aronix) M-405 "," Aronix (Aronix) M-406 ", manufactured by Toyo Synthesis (Ltd.)), Tripentaerythritol poly (meth) acrylate (manufactured by" Biscoat #802, Tripentaerythritol acrylate (TripeA) ", manufactured by Okakoku chemical industry (Ltd.), polyfunctional acrylate having a dendrimer structure (manufactured by" Sirius) -501 "," Subaku (BABA) -501 ", manufactured by" Okaka chemical industry (501) "), and ru manufactured by" Okaka chemical industry (501) ", manufactured by, Urethane (meth) acrylates ((product name "UV 1700B", "UV 7620 EA", "UV 7610B", "UV 7600B", "UV 7650B", manufactured by Mitsubishi Chemical Co., Ltd.), (product name "DPHA 40H", "UX 5003", manufactured by Nippon Chemical Co., Ltd.), (product name "BiAMSET (BEAMSET) 577", manufactured by Mitsuka Chemical industry Co., Ltd.), (product name "8 UX-015A", manufactured by Mitsubishi Chemical Co., Ltd.), (product name "U15 HA", manufactured by Xinzhongcun Chemical industry Co., Ltd.), (product name "Miramer) PU 610", manufactured by Miwon Specialty Chemical Co., Ltd., (product name "Etercure (Etercure) 6196-100", manufactured by Changxing Materials Co., Ltd.)) and the like).

The substances exemplified as the component (B) and the substances known as the component (B) may be used alone or in combination of two or more.

(B) Examples of the upper limit of the molecular weight of the component (a) include 50,000, 40,000, 30,000, 20,000, 10,000, 5,000, 1,000, 500, 250 and the like, and examples of the lower limit thereof include 40,000, 30,000, 20,000, 10,000, 5,000, 1,000, 500, 250, 100 and the like. In one embodiment, the molecular weight of the component (B) is preferably about 100 to 50,000.

(A) Examples of the upper limit of the solid content mass ratio ((a)/(B)) of the component (a) and the component (B) include 99/1, 95/5, 90/10, 85/15, 80/20, 75/25, 70/30, 60/40, 50/50, 40/60, 30/70, and 25/75, and examples of the lower limit thereof include 95/5, 90/10, 85/15, 80/20, 75/25, 70/30, 60/40, 50/50, 40/60, 30/70, 25/75, and 20/80. In one embodiment, the mass ratio ((a)/(B)) of the solid components of the component (a) and the component (B) is preferably about 20/80 to 99/1.

The upper limit of the content (in terms of solid content) of the component (B) may be, for example, 90 mass%, 80 mass%, 70 mass%, 60 mass%, 50 mass%, 40 mass%, 30 mass%, 20 mass%, 10 mass%, etc., and the lower limit may be, for example, 80 mass%, 70 mass%, 60 mass%, 50 mass%, 40 mass%, 30 mass%, 20 mass%, 10 mass%, 3 mass%, 1 mass%, etc., with respect to 100 mass% of the total amount of the resin composition. In one embodiment, the content (in terms of solid content) of the component (B) is preferably about 1 to 90% by mass based on 100% by mass of the total amount of the resin composition.

The upper limit of the total content (in terms of solid content) of the component (a) and the component (B) may be 99 mass%, 98 mass%, 97 mass%, 96 mass%, 95 mass%, 94 mass%, 93 mass%, 92 mass%, 91 mass%, 90 mass%, 85 mass%, 80 mass%, 75 mass%, 70 mass%, 65 mass%, 60 mass%, 55 mass% or the like, and the lower limit may be 98 mass%, 97 mass%, 96 mass%, 95 mass%, 94 mass%, 93 mass%, 92 mass%, 91 mass%, 90 mass%, 85 mass%, 80 mass%, 75 mass%, 70 mass%, 65 mass%, 60 mass%, 55 mass%, 50 mass% or the like, with respect to 100 mass% of the total amount of the resin composition. In one embodiment, the total content (in terms of solid content) of the component (a) and the component (B) is preferably about 50 to 99% by mass based on 100% by mass of the total amount of the resin composition.

< method for producing mixture of component (A) and component (B) >

(A) The mixture of the component (a) and the component (B) is usually obtained by mixing the component (a) and the component (B) at normal temperature.

< ingredient (C) >

(C) Component (C) is a metal compound having a coordinate bond capability. Examples of the metal compound include a metal chelate compound, a metal alkoxide compound, a metal acylate compound, and a metal-containing cyclic oligomer. Examples of the metal compound include aluminum, zirconium, titanium, magnesium, chromium, cobalt, copper, iron, nickel, vanadium, zinc, indium, calcium, manganese, and tin. The metal as the component (C) is preferably aluminum, zirconium, or titanium, from the viewpoint of easy availability.

Examples of the metal chelate compound include aluminum chelate, zirconium chelate, titanium chelate and the like. Examples of the aluminum chelate include aluminum ethyl triacetoacetate, aluminum triacetylacetonate, aluminum diacetylacetacetoacetate monoacetylacetonate, aluminum ethylacetoacetate diisopropylate, and aluminum alkylacetoacetate diisopropylate. Examples of the chelate zirconium include zirconium ethylacetoacetate, zirconium tributoxymetacetylacetonate, and zirconium tetraacetylacetonate. Examples of the chelate titanium include diisopropoxybis (acetylacetonato) titanium, tetraacetylacetonato titanium, diisopropoxybis (ethylacetoacetate) titanium, di-2-ethylhexyloxybis (2-ethyl-3-hydroxyhexaoxide) titanium, diisopropoxybis (triethanolaminated) titanium, 1, 3-propanedioxybis (ethylacetoacetate) titanium, aminoethylaminoethylaminoethylated titanium, and octanedionato titanium.

Examples of the metal alkoxide compound include aluminum alkoxide, zirconium alkoxide, and titanium alkoxide. Examples of the aluminum alkoxide include aluminum ethoxide, aluminum isopropoxide, aluminum sec-butoxide, and aluminum mono-butoxide diisopropyl acid. Examples of the zirconium alkoxide include zirconium tetra-n-propoxide and zirconium tetra-n-butoxide. Examples of the titanium alkoxide include titanium tetra-n-butoxide, titanium butoxide dimer, titanium tetra-2-ethylhexanoate, titanium tetraisopropoxide, titanium tetra-t-butoxide, and titanium tetra-stearyl titanate.

Examples of the metal acylate compound include aluminum acylate, zirconium acylate, and titanium acylate. Examples of the zirconium acylate include zirconium monopropyl tristearate, zirconium dipropyl distearate, zirconium tripropylmonostearate, zirconium monobutyloxytriastearate, zirconium dibutoxydisutearate, and zirconium tributoxybutyloxystearate. Examples of the titanium acylate include titanium isostearate and the like.

Examples of the metal-containing cyclic oligomer include an aluminum cyclic oligomer, a zirconium cyclic oligomer, and a titanium cyclic oligomer. Examples of the aluminum cyclic oligomer include cyclic isopropyl alumina, cyclic stearic acid alumina, and cyclic octanoic acid alumina.

The substances exemplified as the component (C) and the substances known as the component (C) may be used alone or in combination of two or more.

As the component (C), commercially available products can also be used. The product is not particularly limited, and examples thereof include: chelated aluminum (product name "ALCH", "ALCH-TR", "aluminum chelate (aluminum chelate) M", "aluminum chelate (aluminum chelate) D", "aluminum chelate (aluminum chelate) A", manufactured by Sichuan research and refining chemical industry (Strand), chelated zirconium (product name "AustagacKig (ORGATIX) ZC-150", "AustagacKig (ORGATIX) ZC-162", "AustagacKig (ORGATIX) ZC-540", "AustagacKig (ORGATIX) ZC-580", "AustagacKig (ORGATIX) ZC-700", manufactured by Songben refining chemical industry (Strand), chelated titanium (product name "AustagacKig (ORGATIX) TC-100", "AustagacKig (ORGATIX) TC-300", "AustagacKig (ORGATIX) TC-310", "AustagacKig (ORGATIX) TC-400", "TIX-100", "AustagacKig (ORGATIX) TC-245-750", "ORGATIX) TC-710-700", (ORGATIX) ZC-700 ", -60), manufactured by Songban Fine chemical industry (Strand), Aluminum alkoxides (product names "AMD", "ASBD", "AIPD", "PADM", "Aluminum Ethoxide (Aluminum Ethoxide)", manufactured by Chuan-Min Fine chemical industry (Strand)), and the like.

The component (C) is preferably at least one selected from the group consisting of aluminum chelate, zirconium chelate and titanium chelate, and more preferably at least one selected from the group consisting of zirconium chelate and titanium chelate, from the viewpoint of excellent scratch resistance, pencil hardness and the like.

(C) Examples of the upper limit of the molecular weight of the component (a) include 3,000, 2,000, 1,000, 900, 800, 700, 600, 500, 400, 300, 200, 100 and the like, and examples of the lower limit thereof include 2,000, 1,000, 900, 800, 700, 600, 500, 400, 300, 200, 100, 50 and the like. In one embodiment, the molecular weight of the component (C) is preferably about 50 to 3,000.

The upper limit of the content (in terms of solid content) of the component (C) may be 15 mass%, 14 mass%, 13 mass%, 12 mass%, 11 mass%, 10 mass%, 9 mass%, 8 mass%, 7 mass%, 6 mass%, 5 mass%, 4 mass%, 3 mass%, 2 mass% or the like, and the lower limit may be 14 mass%, 13 mass%, 12 mass%, 11 mass%, 10 mass%, 9 mass%, 8 mass%, 7 mass%, 6 mass%, 5 mass%, 4 mass%, 3 mass%, 2 mass%, 1 mass% or the like, with respect to 100 mass% of the total amount of the component (a) and the component (B). In one embodiment, the content (in terms of solid content) of the component (C) is preferably about 1 to 15% by mass relative to 100% by mass of the total amount of the components (a) and (B).

The upper limit of the content (in terms of solid content) of the component (C) may be 15 mass%, 14 mass%, 13 mass%, 12 mass%, 11 mass%, 10 mass%, 9 mass%, 8 mass%, 7 mass%, 6 mass%, 5 mass%, 4 mass%, 3 mass%, 2 mass% or the like, and the lower limit may be 14 mass%, 13 mass%, 12 mass%, 11 mass%, 10 mass%, 9 mass%, 8 mass%, 7 mass%, 6 mass%, 5 mass%, 4 mass%, 3 mass%, 2 mass%, 1 mass% or the like, with respect to 100 mass% of the total amount of the resin composition. In one embodiment, the content (in terms of solid content) of the component (C) is preferably about 1 to 15% by mass relative to 100% by mass of the total amount of the resin composition.

< method for producing resin composition >

The method for producing the resin composition is not particularly limited, and various known methods can be used. Examples of the method for producing the resin composition include a method of blending the components (a), (B) and (C) in appropriate amounts, preparing the mixture by dilution with an organic solvent for adjusting nonvolatile components, and uniformly mixing the prepared mixture.

< ingredient (D) >

The resin composition may further contain a photopolymerization initiator (D) (hereinafter also referred to as "component (D)"). By containing the component (D) in the resin composition, the resin composition has excellent curing performance (hereinafter, also referred to as "curability").

The component (D) is not particularly limited, and various known substances can be used. Examples of the component (D) include a radical photopolymerization initiator, a cationic photopolymerization initiator, and an anionic photopolymerization initiator.

Examples of the radical photopolymerization initiator include a phenylalkyl ketone type photopolymerization initiator, an acylphosphine oxide type photopolymerization initiator, a hydrogen abstraction type photopolymerization initiator, and an oxime ester type photopolymerization initiator.

Examples of the phenylalkyl ketone type photopolymerization initiator include benzyl dimethyl ketone such as 2, 2-dimethoxy-1, 2-diphenylethan-1-one; α -hydroxybenzylalkyl ketones such as 1- [4- (2-hydroxyethoxy) -phenyl ] -2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1- {4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl ] phenyl } -2-methyl-propan-1-one, and 1-hydroxy-cyclohexyl-phenyl-ketone; and α -aminophenylalkyl ketones such as 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -1-butanone, and 2- (dimethylamino) -2- [ (4-methylphenyl) methyl ] -1- [4- (4-morpholino) phenyl ] -1-butanone.

Examples of the acylphosphine oxide type photopolymerization initiator include 2, 4, 6-trimethylbenzoyl-diphenyl-phosphine oxide, bis (2, 4, 6-trimethylbenzoyl) -phenylphosphine oxide, and the like.

Examples of the hydrogen abstraction-type photopolymerization initiator include methyl phenylglyoxylate and the like.

Examples of the oxime ester type photopolymerization initiator include 1, 2-octanedione, 1- [4- (phenylthio) -, 2- (O-benzoyloxime) ], ethanone, 1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] -, 1- (O-acetyloxime), and the like.

Examples of the cationic photopolymerization initiator include a mixture of iodonium, (4-methylphenyl) [4- (2-methylpropyl) phenyl ] -hexafluorophosphate (1-) and propylene carbonate, triarylsulfonium hexafluorophosphate, triarylsulfonium tetrakis- (pentafluorophenyl) borate, and the like.

Examples of the anionic photopolymerization initiator include a cobalamin complex, o-nitrobenzyl alcohol carbamate, and oxime ester.

The substances exemplified as the component (D) and the substances known as the component (D) may be used alone or in combination of two or more.

The component (D) is preferably a radical photopolymerization initiator, more preferably a phenylalkyl ketone photopolymerization initiator, further preferably an α -hydroxybenzylalkyl ketone, particularly preferably 1- [4- (2-hydroxyethoxy) -phenyl ] -2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1- {4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl ] phenyl } -2-methyl-propan-1-one, and/or 1-hydroxy-cyclohexyl-phenyl-one, in order to provide particularly excellent curing properties.

As the component (D), commercially available products can also be used. The product is not particularly limited, and examples thereof include: 2, 2-dimethoxy-1, 2-diphenylethan-1-one (product name "ohm nidad (Omnirad) 651", manufactured by IGM Resins Co., Ltd.), 1- [4- (2-hydroxyethoxy) -phenyl ] -2-hydroxy-2-methyl-1-propan-1-one (product name "ohm nidad (Omnirad) 2959", manufactured by IGM Resins Co., Ltd.), 2-hydroxy-1- {4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl ] phenyl } -2-methyl-propan-1-one (product name "ohm nidad (Omnirad) 127", manufactured by IGM Resins Co., Ltd.), 1-hydroxy-cyclohexyl-phenyl ketone (product name "ohm nidad (Omnirad) 184", IGM resins, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one (product name "Omnirad (Omnirad) 907", IGM resins), 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -1-butanone (product name "Omnirad (Omnirad) 369E", IGM resins), 2- (dimethylamino) -2- [ (4-methylphenyl) methyl ] -1- [4- (4-morpholino) phenyl ] -1-butanone (product name "Omnirad (Omnirad)379 EG", IGM resins), 2, 4, 6-trimethylbenzoyl-diphenyl-phosphine oxide (product name "Omnirad (TPO H"), manufactured by IGM resin corporation), bis (2, 4, 6-trimethylbenzoyl) -phenylphosphine oxide (manufactured under the name "ohm-nidad (Omnirad) 819", manufactured by IGM resin corporation), phenylglyoxylic acid methyl ester (manufactured under the name "ohm-nidad (Omnirad) MBF", manufactured by IGM resin corporation), 1, 2-octanedione, 1- [4- (phenylthio) -, 2- (O-benzoyloxime) ] (manufactured under the name "brilliant good solid (IRGACURE) OXE 01", manufactured by BASF Japan (BASF Japan) (stock), ethanone, 1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] -, 1- (O-acetyloxime) (manufactured under the name "brilliant good solid (IRGACURE) OXE 02", manufactured by BASF (stock)), Iodonium, (4-methylphenyl) [4- (2-methylpropyl) phenyl ] -hexafluorophosphate (1-), and propylene carbonate (product name "ohm nikat (Omnicat) 250", manufactured by IGM resins Co., Ltd.), triaryl sulfonium hexafluorophosphate (product name "ohm nikat (Omnicat) 270", manufactured by IGM resins Co., Ltd.), triaryl sulfonium tetrakis- (pentafluorophenyl) borate (product name "Irgacure (IRGACURE) 290", manufactured by BASF (BASF) Co., Ltd.), and the like.

The upper limit of the content (in terms of solid content) of the component (D) may be 10 mass%, 9 mass%, 8 mass%, 7 mass%, 6 mass%, 5 mass%, 4 mass%, 3 mass%, 2 mass%, etc., with respect to 100 mass% of the total amount of the resin composition, and the lower limit may be 9 mass%, 8 mass%, 7 mass%, 6 mass%, 5 mass%, 4 mass%, 3 mass%, 2 mass%, 1 mass%, etc. In one embodiment, the content (in terms of solid content) of the component (D) is preferably about 1 to 10% by mass relative to 100% by mass of the total amount of the resin composition.

< ingredient (E) >

The resin composition may further contain a fluorine-containing compound (E) (hereinafter also referred to as "component (E)"). By containing the component (E) in the resin composition, the cured product is particularly excellent in scratch resistance, and further excellent in leveling property (coating property), water repellency, oil repellency, stain resistance and finger sliding property.

The component (E) is not particularly limited, and various known substances can be used. Examples of the component (E) include: perfluoroalkyl-containing compounds such as perfluoroalkyl-containing carboxylic acids or salts thereof, perfluoroalkyl-containing sulfonic acids or salts thereof, or perfluoroalkyl-containing phosphoric acids or phosphoric acid esters thereof, perfluoroalkenyl-containing compounds in which the perfluoroalkyl group is substituted with a perfluoroalkenyl group, perfluoroether-containing compounds in which the perfluoroalkyl group is substituted with a perfluoroether group, fluoro-lipophilic group-containing oligomers, fluoro-hydrophilic group-lipophilic group-carboxyl group-containing oligomers, fluoro-Ultraviolet (UV) -reactive group-containing oligomers, and the like.

The substances exemplified as the component (E) and the substances known as the component (E) may be used alone or in combination of two or more. In addition, these may use one kind of polymer each other or two or more kinds of polymers.

The component (E) is preferably an oligomer containing a fluorine-containing group-UV reactive group, because the cured product is excellent in scratch resistance, water repellency, oil repellency, stain resistance, and the like.

As the component (E), commercially available products can also be used. As the product, there can be exemplified: perfluorobutanesulfonate (product name "Meijia method (Megafac) F-114", manufactured by DIC (R)), carboxylate containing perfluoroalkyl group (product name "Meijia method (Megafac) F-410", manufactured by DIC (R)), phosphate ester containing perfluoroalkyl group-phosphoric acid group (product name "Meijia method (Megafac) F-510", manufactured by DIC (R)), modified perfluoropolyether (product name "OPTOOL (OPTOOL) DAC-HP", manufactured by Dajin industry (R)), (product names "KY-108", "KY-164", "X-71-195", "KY-1900", manufactured by shin-Etsu chemical industry (R)), oligomer containing fluoro group-lipophilic group (product name "Meijia method (Megafac) F-281", "Meijia method (Megafac) F-253", "Meijiafac (Megafac) F-251", the above-mentioned oligomer may be produced by DIC (Strand), the fluorine-containing hydrophilic group-containing oligomer (product name "Meijia method (Megafac) F-430", "Meijia method (Megafac) F-551", "Meijia method (Megafac) F-552", produced by DIC (Strand)), the fluorine-containing hydrophilic group-lipophilic group-containing oligomer (product name "Meijiafac method (Megafac) F-477", produced by DIC (Strand)), the fluorine-containing hydrophilic group-lipophilic group-carboxyl group-containing oligomer (product name "Meijiafac method (Megafac) F-570", produced by DIC (Strand)), the fluorine-containing UV reactive group-containing oligomer ((product name "Meijiafac method (Megafac) RS-56", "Meijiafac method (Megafac) RS-90", "Megafac method (Megafac) RS-75-A", produced by DIC (Strand), (product names "KY-1203", "KY-1207" and "KY-1211", manufactured by shin-Etsu chemical industries, Ltd.), and the like.

The upper limit of the content (in terms of solid content) of the component (E) may be 10 mass%, 9 mass%, 8 mass%, 7 mass%, 6 mass%, 5 mass%, 4 mass%, 3 mass%, 2 mass%, 1 mass%, 0.5 mass%, 0.2 mass%, 0.1 mass%, 0.05 mass%, etc., and the lower limit may be 9 mass%, 8 mass%, 7 mass%, 6 mass%, 5 mass%, 4 mass%, 3 mass%, 2 mass%, 1 mass%, 0.5 mass%, 0.2 mass%, 0.1 mass%, 0.05 mass%, 0.01 mass%, etc., with respect to 100 mass% of the total amount of the resin composition. In one embodiment, the content (in terms of solid content) of the component (E) is preferably about 0.01 to 10% by mass based on 100% by mass of the total amount of the resin composition.

< ingredient (F) >

The resin composition may further contain inorganic fine particles (F) (hereinafter also referred to as "component (F)"). By containing the component (F) in the resin composition, the cured product and the laminate are excellent in scratch resistance.

The component (F) is not particularly limited, and various known substances can be used. Examples of the component (F) include zinc oxide nanoparticles, silica nanoparticles, alumina nanoparticles, cerium oxide nanoparticles, iron oxide nanoparticles, titanium oxide nanoparticles, zirconium oxide nanoparticles, and cuprous oxide nanoparticles.

The substances exemplified as the component (F) and the substances known as the component (F) may be used alone or in combination of two or more.

The component (F) is preferably alumina nanoparticles, because the cured product has excellent scratch resistance.

As the component (F), commercially available products can also be used. As the product, there can be exemplified: silica nanoparticles (product names "nano bike (NANOBYK) -3650", "nano bike (NANOBYK) -3652", manufactured by bike Chemical (BYK-chemie)), alumina nanoparticles ((product names "nano bike (NANOBYK) -3603", "nano bike (NANOBYK) -3610", manufactured by bike Chemical), (product names "ALMIBK) -H06", manufactured by CIK nanotechnology (CIK nanotechn) (stock)), cerium oxide nanoparticles (product names "cerium (IV) oxide nanoparticles (10 nm)", manufactured by fuji film and photochemistry (FUJIFILM Wako Chemical) (stock)), iron oxide nanoparticles (product names "iron (II, III), magnetic nanoparticle solution", manufactured by SIGMA ALDRICH (SIGMA-ALDRICH), titanium oxide nanoparticles (product names "TTO-51 (a)", manufactured by, "TTO-55 (C)", manufactured by stone industries (stock), zirconia nanoparticles (product names "zekeleoneo (zircono) -Cp", "zekeleoneo (zircono) -Rp", "zekeleoneo (zircono) -Cw", "zekeleon (zircono) -Ck", manufactured by ITEC (stock)), cuprous oxide nanoparticles (product name "FRC-N10", manufactured by gulewa Chemicals (stock)), and the like.

The upper limit of the content (in terms of solid content) of the component (F) may be 10 mass%, 9 mass%, 8 mass%, 7 mass%, 6 mass%, 5 mass%, 4 mass%, 3 mass%, 2 mass%, etc., with respect to 100 mass% of the total amount of the resin composition, and the lower limit may be 9 mass%, 8 mass%, 7 mass%, 6 mass%, 5 mass%, 4 mass%, 3 mass%, 2 mass%, 1 mass%, etc. In one embodiment, the content (in terms of solid content) of the component (F) is preferably about 1 to 10% by mass relative to 100% by mass of the total amount of the resin composition.

< method for producing resin composition containing component (A), (B), (C), (D), (E) and (F) >

The method for producing the resin composition containing the component (a), the component (B), the component (C), the component (D), the component (E) and the component (F) is not particularly limited, and various known methods can be used. Examples of such a method include a method in which the component (A), the component (B), the component (C), the component (D), the component (E) and the component (F) are mixed in an appropriate amount, and the mixture is diluted with an organic solvent to adjust the nonvolatile content, and then uniformly mixed.

As the organic solvent, those exemplified below and those known as organic solvents can be used alone or in combination of two or more. Examples of the organic solvent include ketone solvents, aromatic solvents, alcohol solvents, glycol ether solvents, ester solvents, alkyl halide solvents, amide solvents, and other petroleum solvents.

Examples of the ketone solvent include methyl ethyl ketone, acetylacetone, methyl isobutyl ketone, cyclopentanone, and cyclohexanone.

Examples of the aromatic solvent include toluene, xylene, and the products "Tissol (T-SOL) 100" and "Tissol (T-SOL) 150" (both manufactured by JXTG energy Co., Ltd.).

Examples of the alcohol solvent include methanol, ethanol, n-propanol, isopropanol, butanol, benzyl alcohol, and cresol.

Examples of the glycol solvent include ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, polyethylene glycol, and polypropylene glycol.

Examples of the glycol ether solvent include ethylene glycol dimethyl ether, ethylene glycol diethyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, propylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-isopropyl ether, ethylene glycol mono-n-butyl ether, ethylene glycol mono-isobutyl ether, ethylene glycol mono-t-butyl ether, and bis (2-methoxyethyl) ether.

Examples of the ester solvent include ethyl acetate, butyl acetate, methyl cellosolve acetate, ethyl cellosolve acetate, and propylene glycol monomethyl ether acetate.

Examples of the alkyl halide solvent include chloroform.

Examples of the amide solvent include dimethylformamide, dimethylacetamide, N-methyl-2-pyrrolidone, and N-methylcaprolactam.

Examples of the other petroleum solvent include dimethyl sulfoxide and methylcyclohexane.

< other Agents that can be formulated >

The resin composition may further contain one or more agents selected from various known resins such as acrylic resins, epoxy resins, urethane resins, etc., reactive diluent monomers, ultraviolet absorbers, antioxidants, silicone additives (silicone or siloxane), silane compounds, antistatic agents, antifogging agents, rheology control agents, fillers, mold release agents, flame retardants, viscosity control agents, plasticizers, antibacterial agents, antifungal agents, antifoaming agents, colorants, stabilizers, pigments, surface control agents, various solvents, various catalysts, and photosensitizers.

In order to improve the viscosity of the partially cured product, a polyisocyanate may be formulated in the resin composition of the present disclosure. Examples of the polyisocyanate include the polyisocyanates described above. When the polyisocyanate is added to the resin composition, various known catalysts may be added at the same time, and the component (C) may or may not be added so far as it exerts a certain catalytic action. The upper limit of the content of the polyisocyanate may be 10 mass%, 9 mass%, 8 mass%, 7 mass%, 6 mass%, 5 mass%, 4 mass%, 3 mass%, 2 mass%, 1 mass%, 0.5 mass% or the like, and the lower limit may be 9 mass%, 8 mass%, 7 mass%, 6 mass%, 5 mass%, 4 mass%, 3 mass%, 2 mass%, 1 mass%, 0.5 mass%, 0.1 mass% or the like, with respect to 100 mass% of the total amount of the resin composition. In one embodiment, the content of the polyisocyanate is preferably about 0.1 to 10% by mass based on 100% by mass of the total amount of the resin composition.

Further, the resin composition of the present disclosure may contain a silane compound, but the cured product of the present disclosure has more excellent scratch resistance by not containing a silane compound in the resin composition of the present disclosure. Examples of the silane compound include aminosilanes, epoxysilanes, vinylsilanes, (meth) acrylic silanes, chlorosilanes, alkoxysilanes, silazanes, and the like used as a silane coupling agent.

< partially cured product >

A resin composition that is partially cured by heating (hereinafter, the treatment is also referred to as "heat treatment") is also one aspect of the present invention. The partially cured product of the present invention can be laminated on the surface of a molded product having a complicated shape such as deep drawing without causing cracks.

By heating the resin composition, the resin composition becomes a product of a thermal crosslinking reaction (also referred to as "partially cured product"). Since the thermal crosslinking reaction product is in a non-viscous state, it is easy to print another layer on the film-shaped thermal crosslinking reaction product or to wind the film. In the stage of the heating, the ethylenically unsaturated group contained in the resin composition is not crosslinked, and thus the resin composition is not completely crosslinked and hardened. In other words, the cured product is partially cured. Therefore, the film-like thermally crosslinked reaction product can be adapted to the curved surface of the molded article and has flexibility to such an extent that no crack is generated. Further, a film having a pad shape may be attached to the film-like product of the thermal crosslinking reaction to transfer the shape, or a protective film for preventing stains may be attached.

The upper limit of the thickness of the film-like thermal crosslinking reaction product may be, for example, 1,000. mu.m, 500. mu.m, 250. mu.m, 100. mu.m, 50. mu.m, 10. mu.m, 3. mu.m, etc., and the lower limit may be, for example, 250. mu.m, 100. mu.m, 50. mu.m, 10. mu.m, 3. mu.m, 1. mu.m, 0.5. mu.m, 0.1. mu.m, etc. In one embodiment, the thickness of the film-like thermal crosslinking reaction product is preferably 0.1 μm or more and 1,000 μm or less. By setting the thickness in the above range, the workability of the partially cured product and the scratch resistance of the cured product can be improved.

Examples of the method for applying the resin composition include bar coater coating, meyer bar coating, air knife coating, gravure coating, reverse gravure coating, offset printing, flexographic printing, screen printing, and flow coating. The upper limit of the coating amount (mass after drying) is 1,000g/m²、500g/m²、250g/m²、100g/m²、50g/m²、10g/m²、3g/m²Etc., the lower limit may be 500g/m²、250g/m²、100g/m²、50g/m²、10g/m²、3g/m²、1g/m²And the like. In one embodiment, the coating amount (mass after drying) is preferably 1g/m²Above and 1,000g/m²About the following.

As a method of heat treatment, various known methods can be used. As a method of the heat treatment step, a method of heating the resin composition at 80 ℃ to 150 ℃ for 1 minute to 30 minutes, or the like is preferably exemplified from the viewpoint of reactivity of the component (a) and the component (B) with the component (C).

The lower limit of the elongation at break of the film-like thermally crosslinked reaction product is, for example, 250%, 200%, 150%, 100%, 90%, 80%, 70%, 60%, 50%, 40%, etc. The film-like thermally crosslinked reaction product may not be broken even if it is elongated to more than the object to which the film is laminated, that is, to the limit. Therefore, the upper limit of the elongation at break of the film-like thermal crosslinking reaction product is not particularly limited, and examples thereof include 600%, 550%, 500%, 450%, 400%, 350%, 300%, 250%, 200%, and 150%.

In the present disclosure, the elongation at break of the film-shaped thermal crosslinking reaction product refers to the ratio of the length (cm) of the coating film that is elongated from 0% of the length (cm) of the coating film when the state before elongation of the film is 0%. Specifically, a commercially available tensile tester such as Tensilon Universal tester (product name "RTG-1250", manufactured by Anden (A & D) Inc.) is used to perform stretching at a speed of 100mm/min while heating at 150 ℃, and the length of the sample when a crack is visible and the length of the sample before stretching are used to calculate the tensile tester from the following formula.

Elongation at break (%) < 100 × ((L-Lo)/Lo)

Lo: length of specimen before stretching

L: length of specimen at which crack started to be visible

< cured product >

A cured product obtained by irradiating a partially cured product with an active energy ray such as ultraviolet ray is also one aspect of the present invention.

As a method for hardening by irradiation with an active energy ray, various known methods can be used. As a method of curing by ultraviolet rays in the irradiation with active energy rays, use of a material emitting 150nm to 450nm can be exemplifiedA high pressure mercury lamp, an ultra-high pressure mercury lamp, a carbon arc lamp, a metal halide lamp, a xenon lamp, a chemical lamp, an electrodeless discharge lamp, a light-emitting diode (LED), or the like, which irradiates light in a wavelength range of 10mJ/cm²Above and 10,000mJ/cm²The following methods and the like. When a high-pressure mercury lamp is used, a method of curing a lamp having a light quantity of usually 80W/cm to 160W/cm at a transport speed of 2 m/min to 50 m/min, and the like can be exemplified. Examples of the method of curing by an electron beam include a method of curing at a transport speed of 5 m/min to 50 m/min by using an electron beam accelerator usually having an acceleration voltage of 10kV to 300 kV.

< layered product >

The present invention also relates to a laminate comprising a partially cured product or cured product and a substrate. Examples of the laminate include a laminate obtained by applying a partially cured product to at least one surface of a substrate and then completely curing the partially cured product by irradiation with an active energy ray such as ultraviolet light. By completely hardening the partially hardened material, scratch difficulty can be given to the substrate.

Examples of the substrate include metal, plastic, glass, and other resins. Examples of the metal include iron, aluminum-plated steel sheet, tin-free steel sheet (TFS), stainless steel sheet, zinc phosphate-treated steel sheet, and treated steel sheet of zinc-zinc alloy-plated steel sheet (corrosion-resistant steel sheet). Examples of the plastic include thermoplastic substrates and thermosetting plastic substrates. Examples of the thermoplastic base material include general-purpose plastic base materials and engineering plastic base materials. Examples of the general-purpose plastic base material include olefin-based, polyester-based, acrylic-based, vinyl-based, and polystyrene-based materials. Examples of the olefin-based polymer include polyethylene, polypropylene, and norbornene. Examples of the polyester include polyethylene terephthalate (PET), polyethylene naphthalate (PEN), and the like. As the acrylic, polymethyl methacrylate (PMMA) and the like can be exemplified. Examples of the vinyl system include polyvinyl chloride, polyvinylidene chloride, and polyvinyl alcohol. Examples of polystyrenes include Polystyrene (PS) resin, styrene-Acrylonitrile (AS) resin, styrene-butadiene-Acrylonitrile (ABS) resin, and the like. Examples of the engineering plastic substrate include general-purpose engineering plastics and super engineering plastics. Examples of the general-purpose engineering plastic include polycarbonate, polyamide (nylon), and the like. Examples of the super engineering plastic include Polyetheretherketone (PEEK). Examples of the thermosetting plastic substrate include polyimide, epoxy resin, and melamine resin. As another plastic substrate, triacetyl cellulose resin and the like can be exemplified. The base material in the laminate of the present disclosure is preferably a thermoplastic base material, more preferably at least one selected from polyester-based, acrylic-based, and general-purpose engineering plastics, and even more preferably polyester-based, acrylic-based, and general-purpose engineering plastics.

The substrate may be a film. When the substrate is in the form of a film, the upper limit of the thickness thereof may be 1,000. mu.m, 750. mu.m, 500. mu.m, 300. mu.m, 100. mu.m, 50. mu.m, 25 μm, etc., and the lower limit thereof may be 750. mu.m, 500. mu.m, 300. mu.m, 100. mu.m, 50. mu.m, 25. mu.m, 10 μm, etc. In one embodiment, the film-like substrate preferably has a thickness of about 10 μm to 1,000. mu.m.

For the purpose of improving the adhesion and adhesion between the substrate and the cured product, the surface of the substrate may be subjected to various surface treatments such as corona treatment, plasma treatment, primer coating, degreasing treatment, and surface roughening treatment. In addition, another layer (for example, an easy adhesion layer, an adhesive layer, or the like) may be disposed between the substrate and the cured product for the purpose of improving the adhesion and the close contact between the substrate and the cured product.

As a specific example of the laminate of the present invention, a laminate having various layers in the following order can be exemplified. In addition, various known layers such as a pattern layer may be appropriately disposed before and after each layer.

(1) A cured product/substrate,

(2) Cured product/easy-to-adhere layer or adhesive layer/substrate,

(3) A partially cured product/substrate,

(4) Partially cured/easy-to-bond or adhesive/substrate

< molded article >

Examples of applications of the resin composition include forming a hard coat layer on various known articles.

As the article, various known articles can be exemplified. Examples of the articles include a main body of a home appliance such as a refrigerator, a television, or an air conditioner, a remote controller thereof, a housing and a display of an information terminal such as a mobile phone, a smartphone, an input board, or a personal computer, and a plastic molded article such as an automobile part or an automobile interior material.

[ examples ]

The present invention will be described more specifically below with reference to synthesis examples, comparative examples, evaluation examples and comparative evaluation examples, but the present invention is not limited to these examples. In the following description, parts and% are based on mass.

In this example, the weight average molecular weight (Mw) was measured by Gel Permeation Chromatography (GPC) under the following conditions.

(GPC measurement conditions)

The machine is as follows: the product name is "HLC-8220" (made by Tosoh)

Pipe column: the product name "TSK gel Super (TSKgel Super) HM-L" (manufactured by Tosoh corporation) × 3

Developing solvent: tetrahydrofuran (hereinafter also referred to as "THF")

< synthetic example 1: synthesis of component (A-1) >

In a reaction apparatus equipped with a stirrer, a cooling tube, a thermometer, and a nitrogen gas inlet tube, 32.6 parts of glycidyl methacrylate (hereinafter also referred to as "GMA"), 48.6 parts of butyl acetate, and 1.5 parts of azobisisobutyronitrile (hereinafter also referred to as "AIBN") were charged, and then the temperature was raised to about 100 ℃ under a nitrogen gas flow, and the mixture was held for 10 hours. After the reaction, the reaction mixture was cooled to 60 ℃ and charged with 16.6 parts of acrylic acid (hereinafter, also referred to as "AA"), 0.5 part of methoxyphenol and 0.1 part of triphenylphosphine, and the temperature was raised to 110 ℃ under bubbling of air to react for 9 hours, thereby obtaining a (meth) acrylic copolymer solution (hereinafter, also referred to as "component A-1") having a resin solid content of 50%. The obtained (meth) acrylic acid copolymer had a hydroxyl group concentration of 4.7mmol/g, an acrylic acid equivalent of 214g/eq, and a weight-average molecular weight (in terms of polystyrene obtained by GPC) of 30,000.

< synthetic example 2: synthesis of component (A-2) >

16.3 parts of GMA, 16.3 parts of methyl methacrylate, 48.6 parts of butyl acetate and 2.0 parts of AIBN were charged into a reaction apparatus equipped with a stirrer, a cooling tube, a thermometer and a nitrogen gas inlet tube, and then the temperature was raised to about 100 ℃ under a nitrogen gas stream, and the temperature was maintained for 10 hours. After the reaction, the reaction mixture was cooled to 60 ℃ and charged with 8.3 parts of AA, 0.5 part of methoxyphenol and 0.1 part of triphenylphosphine, and the temperature was raised to 110 ℃ under bubbling of air to carry out a reaction for 9 hours, thereby obtaining a (meth) acrylic copolymer solution (hereinafter, also referred to as "component A-2") having a resin solid content of 50%. The obtained (meth) acrylic acid copolymer had a hydroxyl group concentration of 2.8mmol/g, an acrylic acid equivalent of 356g/eq, and a weight-average molecular weight (calculated as polystyrene by GPC) of 10,000.

< synthetic example 3: synthesis of component (A-3) >

A reaction apparatus equipped with a stirrer, a cooling tube, a thermometer, and a nitrogen gas inlet tube was charged with 8.2 parts of GMA, 24.6 parts of methyl methacrylate, 48.6 parts of butyl acetate, and 2.0 parts of AIBN, and then the temperature was raised to about 100 ℃ under a nitrogen gas flow, and the temperature was maintained for 10 hours. After the reaction, the reaction mixture was cooled to 60 ℃ and charged with 4.2 parts of AA, 0.5 part of methoxyphenol and 0.1 part of triphenylphosphine, and the temperature was raised to 110 ℃ under bubbling of air to carry out a reaction for 9 hours, thereby obtaining a (meth) acrylic copolymer solution (hereinafter, also referred to as "component A-3") having a resin solid content of 50%. The obtained (meth) acrylic acid copolymer had a hydroxyl group concentration of 1.6mmol/g, an acrylic acid equivalent of 635g/eq, and a weight-average molecular weight (calculated as polystyrene by GPC) of 10,000.

< example 1: preparation of active energy ray-curable resin composition (1) >

In terms of solid content, 50.0 parts of dipentaerythritol poly (meth) acrylate (product name "Aronix (r) M-403", manufactured by east asia synthesis (r)), 5.0 parts of chelated aluminum (product name "ALCH", manufactured by kawa fine chemical (r)) and 5.0 parts of 1-hydroxy-cyclohexyl-phenyl ketone (product name "ohmic nidad (omni) 184", manufactured by IGM resins) as a photopolymerization initiator and 0.3 parts of a fluorine-containing compound (product name "meiafac (r) -90", manufactured by DIC (r) are mixed with 50.0 parts of component (a-1) by dilution with methyl ethyl ketone so that the nonvolatile content becomes 20%, and the resulting mixture is uniformly mixed to obtain an active energy ray-curable resin composition.

< example 2 to example 33: preparation of active energy ray-curable resin compositions (2) to (33)

Active energy ray-curable resin compositions (2) to (33) were prepared in the same manner as in example 1, except that the compositions shown in tables 1 to 3 were changed. The operation was carried out in the same manner as in example 1 except that in examples 6 to 11 and 31 to 33, the fluorine-containing compound was added, then the polyisocyanate or the alumina nanoparticles were added, and the composition was changed as shown in tables 1 to 3 below.

< comparative example 1 to 5: preparation of active energy ray-curable resin compositions (C1) to (C5)

By the same operation as in example 1 except that the compositions shown in table 4 below were changed, active energy ray-curable resin compositions (C1) to (C5) were prepared. In comparative example 5, the operation was performed in the same manner as in example 1 except that the fluorine-containing compound was added, then the isocyanate and the catalyst were added, and the composition was changed as shown in table 4 below.

< evaluation of Performance: processability >

The active energy ray-curable resin compositions (1) to (33) and the active energy ray-curable resin compositions (C1) to (C5) were applied to a PET film (COSMOSHINE) A4100; manufactured by Toyobo Co., Ltd., thickness 50 μm) in a thickness of about 5 μm, respectively, using a bar coater (type No. 24; manufactured by first physico-chemical (strand), and dried in a circulating air dryer at 100 ℃ for 5 minutes to form partially cured products (1) to (33) and partially cured products (C1) to (C5) by heating the active energy ray-curable resin compositions. A test piece obtained by cutting out the partially cured product (1) to the partially cured product (33) and the partially cured product (C1) to the partially cured product (C5) at a length of 13cm and a width of 1.5cm was stretched in a circulating air dryer at 150 ℃ to evaluate the elongation at break.

< evaluation of Performance: tackiness >

The active energy ray-curable resin compositions (1) to (33) and the active energy ray-curable resin compositions (C1) to (C5) were applied to the surface of a substrate (polymethyl methacrylate/polycarbonate two-layer sheet (product name "technoloy) C001", manufactured by sumitomo chemical (stock), thickness 0.5mm) in a film thickness of about 5 μm, respectively, using a bar coater (type "No. 24", manufactured by first physico-chemical (stock)), and dried in a circulating air dryer at 100 ℃ for 5 minutes to form partially cured products (1) to (33) and partially cured products (C1) to (C5) by heating the active energy ray-curable resin compositions. The partially cured products (1) to (33) and the partially cured products (C1) to (C5) were touched with a finger, and evaluated according to the following criteria.

O: no part of hardened material is adhered to finger

X: a part of hardened material is adhered on the finger

< evaluation of Performance: pencil hardness >

Using a high pressure mercury lamp (output: 120W/cm), the same partially cured products (1) to (33) and partially cured products (C1) to (C5) as those produced in the evaluation of the viscosity-related properties were irradiated at a distance of 15cm, a belt speed of 7m/min, and a cumulative dose of 300mJ/cm²Cured products (1) to (33) and cured products (C1) to (C5) were prepared by curing under the conditions of (1). The cured products (1) to (33) and the cured products (C1) to (C5) were measured according to JIS K5600-5-4.

< evaluation of Performance: scratch resistance >

The same cured products (1) to (33) and cured products (C1) to (C5) as those produced in the performance evaluation concerning the pencil hardness were set in a commercially available measuring apparatus (product name "flat abrasion tester", manufactured by honor scientific refiner production (stock)), and Steel Wool (Steel Wool) (count "# 0000", grade "ultra", manufactured by Japan Steel Wool (stock)) was used, and the surface of the cured product was repeatedly scratched 100 times with a load of 1 kg. The scratch of the cured product was observed and evaluated according to the following criteria.

AAA; without any scratch

AA; the number of scratches is more than 1 and less than 3

A: the number of scratches is more than 3 and less than 5

B: the number of scratches is more than 5 and less than 10

C: more than 10 scratches

The compositions of the active energy ray-curable resin compositions (1) to (33) (described as examples (1) to (33) in the tables) and the results of the performance evaluations are shown in tables 1 to 3. The compositions of the active energy ray-curable resin compositions (C1) to (C5) (shown as comparative examples (C1) to (C5)) and the results of the performance evaluations are shown in table 4.

[ Table 1]

[ Table 2]

[ Table 3]

[ Table 4]

The meanings of the terms in tables 1 to 4 are as follows.

(A-1): synthesis of the (meth) acrylic copolymer solution obtained in example 1 (hydroxyl group concentration 4.7mmol/g, acrylic acid equivalent 214g/eq)

(A-2): synthesis of the (meth) acrylic copolymer solution obtained in example 2 (hydroxyl group concentration 2.8mmol/g, acrylic acid equivalent 356g/eq)

(A-3): synthesis of the (meth) acrylic copolymer solution obtained in example 3 (hydroxyl group concentration 1.6mmol/g, acrylic acid equivalent 635g/eq)

Aronix (Aronix) M-403: dipentaerythritol poly (meth) acrylate (manufactured by TOYA SYNTHESIS (PULSE), 5-6-FUNCTIONAL)

Aronix (Aronix) M-402: dipentaerythritol poly (meth) acrylate (manufactured by TOYA SYNTHESIS (PULSE), 5-6-FUNCTIONAL)

Sirius-501: multifunctional acrylate having dendritic polymer structure (product name "Sirius-501", manufactured by Osaka organic chemical industry (jet), 16-20 functions)

Melamor (Miramer) PU 610: aliphatic urethane (meth) acrylate (6-functional, manufactured by Meiyuan Special chemical Co., Ltd.)

Melamor (Miramer) M222: dipropylene glycol diacrylate (2-functional, manufactured by Meiyuan Special chemical Co., Ltd.)

ALCH: aluminum diisopropyl acetoacetate (product name "ALCH", made by Chuanjian fine chemical industry)

ADM: aluminum single sec-butyl diisopropyl acid (product name "ADM", made by Chuanyan fine chemical industry)

ASBD: aluminum sec-butoxide (product name "ASBD", manufactured by Chuanjian Fine chemical industry (stock))

ZC-150: zirconium tetraacetylacetonate (product name "Ogaqi (ORGATIX) ZC-150", manufactured by Songban Fine chemical engineering (stock))

TC-401: titanium tetraacetylacetonate (product name "Ogaqi (ORGATIX) TC-401", manufactured by Songban Fine chemical engineering (stock))

Ohm nidad (Omnirad) 184: 1-hydroxy-cyclohexyl-phenyl ketone (product name "Omnirad) 184", manufactured by IGM resins Co.)

RS-90: fluorine-containing compound (product name "Meijia method (Megafac) RS-90", manufactured by DIC (stock Co Ltd.))

Nano bike (NANOBYK) 3610: alumina nanoparticles (product name "Nanobike (NANOBYK) -3610", manufactured by Bik chemical Co., Ltd.)

Crotamide (Coronate) HL: adduct of hexamethylene diisocyanate (product name "Crosstide (Konate) HL", manufactured by Tosoh)

Crotamide (Coronate) HK: uroacetate of hexamethylene diisocyanate (product name "Crosstide (Konate) HK", manufactured by Tosoh)

DOTL: dioctyltin dilaurate

Claims

1. An active energy ray-curable resin composition comprising: a (meth) acrylic acid copolymer (A) which is a reaction product of a radical polymer (a1) containing a monomer component of an epoxy group-containing mono (meth) acrylate and an α, β -unsaturated carboxylic acid (a2), and which has a hydroxyl group concentration of 2mmol/g or more and a (meth) acrylic acid equivalent of 400g/eq or less;

a metal compound (C).

2. The active energy ray-curable resin composition according to claim 1, wherein

(A) The hydroxyl group concentration of the component (B) is 2 to 5mmol/g,

(A) component (B) has a (meth) acrylic acid equivalent of 150 to 400g/eq, and

(B) the component (A) has 3 or more and 30 or less (meth) acryloyl groups.

3. The active energy ray-curable resin composition according to claim 1 or 2, wherein the component (C) is at least one selected from the group consisting of aluminum chelate, zirconium chelate and titanium chelate.

4. The active energy ray-curable resin composition according to any one of claims 1 to 3, wherein the content of the component (C) is 1% by mass or more and 15% by mass or less in terms of solid content, relative to 100% by mass of the total amount of the components (A) and (B).

5. A partially cured product obtained by heating the active energy ray curable resin composition according to any one of claims 1 to 4, and having an elongation at break of 40% or more.

6. A cured product of the active energy ray-curable resin composition according to any one of claims 1 to 4.

7. A laminate, comprising:

the partially hardened substance according to claim 5 or the hardened substance according to claim 6; and

a substrate.

8. A curing method in which a partially cured product obtained by heat treatment of the active energy ray-curable resin composition according to any one of claims 1 to 4 is cured by irradiation with an active energy ray.