TW202010789A - Active energy ray-curable resin composition, cured product and laminate wherein the cured product has an excellent workability and viscosity, and is provided with scratch resistance - Google Patents

Abstract

The problem to be solved by the invention is to provide an active energy ray-curable resin composition, a cured product including the composition, and a laminate. The active energy ray-curable resin composition is capable of producing a cured product, which has excellent workability and viscosity and is provided with scratch resistance. To solve the problem, the invention provides an active energy ray-curable resin composition, which comprises: (meth) acrylic-based copolymer (A), which is a reactant of a free radical polymer (a1) of a monomer component and <alpha>,<beta>-unsaturated carboxylic acid (a2), and has a hydroxyl group concentration of 2 mmol/g or more and a (meth) acryloyl group equivalent of 400 eq/g or less, wherein the monomer component includes a mono(meth)acrylate containing epoxy group; poly-functional (meth)acrylate (B) having at least 3 (meth) acryloyl groups and a hydroxyl group concentration of 0.1 mmole/g or more; and poly-functional isocyanate (C).

Description

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

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

In order to impart excellent scratch resistance to the surface of molded products exemplified by communication equipment such as mobile phones, information equipment in automobiles, home appliances, etc., hard coatings are generally applied.

In the past, various plastics have been used in the following fields: refrigerators, televisions, air conditioners and other home appliances and their remote controls; mobile phones, smart phones, tablets, personal computers and other information terminal housings and displays; automobiles Parts, automotive interior materials, etc. Plastic has the advantages of processability, transparency, light weight, and low cost, but it is softer than glass materials and has the disadvantage of being easy to damage.

In order to improve these shortcomings, the hard coating agent is applied on the surface of the plastic to improve the scratch resistance of the surface without compromising the advantages of the plastic.

As such hard coating agent, silicone resin, acrylic resin, melamine resin, etc. are used. Among them, the active energy ray-curable resin composition obtained by using an acrylic resin can be cured by active energy rays such as ultraviolet rays. From the viewpoint of curing time and raw material cost, the active energy ray-curable resin composition has become the mainstream . [Prior Art Literature] (Patent Literature)

Patent Document 1: Japanese Patent Laid-Open No. 2004-1350

[Problems to be Solved by the Invention] When using an active energy ray-curable resin composition, if the active energy ray-curable resin composition is applied before plastic molding and irradiated with active energy rays to crosslink and harden it, then It is possible to increase the cross-linking density of the resin, thereby improving the chemical resistance and scratch resistance. On the other hand, the active energy ray-curable resin composition after crosslinking and curing in this way has poor processability. In order to cope with such a problem of workability, an active energy ray-curable resin composition is applied by coating or the like after plastic molding (Patent Document 1). However, in the aforementioned method, the following situation becomes a problem: the number of coating steps increases, uneven coating occurs on the curved surface portion of the processed product, or the yield is poor.

Therefore, there is a demand for a hard coating agent that can be applied before forming a plastic or film, and has both the processability and the scratch resistance of the coating film.

The problem to be solved by the present invention is to provide an active energy ray-curable resin composition, a cured product including the composition, and a laminate. The active energy ray-curable resin composition can produce a cured product and process the cured product It has excellent resistance and stickiness and has scratch resistance. [Technical means to solve the problem]

The inventors concentrated on research and found that the aforementioned problem can be solved by using an active energy ray-curable resin composition, which contains: (meth)acrylic copolymer (A), which It is a reaction product of a radical polymer (a1) with a monomer component and α,β-unsaturated carboxylic acid (a2), and the hydroxyl group concentration is 2 mmol/g or more, and the (meth)acryl acetyl equivalent is 400 eq/g or less , The monomer component contains an epoxy group-containing mono (meth) acrylate; multifunctional (meth) acrylate (B), which has at least 3 (meth) acryl acetyl groups, and the hydroxyl group concentration is 0.1 mmol/g or more; and, polyfunctional isocyanate (C).

That is, the present invention relates to the following items 1 to 11. (Item 1) An active energy ray-curable resin composition comprising: (meth)acrylic copolymer (A), which is a radical polymer (a1) of a monomer component and α,β-unsaturated carboxylic acid The reactant of acid (a2), and the hydroxyl group concentration is 2 mmol/g or more, and the (meth)acryl acetyl equivalent is 400 eq/g or less. The monomer component contains an epoxy group-containing mono(meth)acrylate; Multifunctional (meth)acrylate (B) having at least 3 (meth)acryloyl groups and a hydroxyl group concentration of 0.1 mmol/g or more; and, polyfunctional isocyanate (C). (Item 2) The active energy ray-curable resin composition according to item 1, wherein (A) component has a hydroxyl group concentration of 2 mmol/g or more and 5 mmol/g or less, and (A) component (meth)acrylonitrile The group equivalent is 150 g/eq or more and 400 g/eq or less, (B) component has 3 or more and 6 or less (meth)acryloyl groups, and (B) component has a hydroxyl group concentration of 0.1 mmol/g or more and 2 mmol /g or less. (Item 3) The active energy ray-curable resin composition according to item 1 or 2, wherein the mass ratio of the solid components of (A) component and (B) component is (A)/(B)=30/70 ~99/1. (Item 4) The active energy ray-curable resin composition according to any one of items 1 to 3, wherein the mass ratio of the solid components of (A) and (B) and (C) components is [( A)+(B)]/(C)=60/40～99/1. (Item 5) The active energy ray-curable resin composition according to any one of items 1 to 4, which contains a photopolymerization initiator (D). (Item 6) The active energy ray-curable resin composition according to any one of items 1 to 5, which contains a fluorine-containing compound (E). (Item 7) The active energy ray-curable resin composition according to any one of items 1 to 6, which contains inorganic fine particles (F). (Item 8) A partially cured product obtained by heating the active energy ray-curable resin composition according to any one of Items 1 to 7, and having an elongation at break of 40% or more and 300% or less. (Item 9) A cured product which is the cured product of the active energy ray-curable resin composition according to any one of items 1 to 7. (Item 10) A laminate having a partial hardened product according to item 8 or a hardened product according to item 9 on at least one surface of a substrate surface. (Item 11) A curing method that heats the active energy ray-curable resin composition according to any one of items 1 to 7 to partially cure it, and then irradiates the active energy ray to further cure. [Efficacy of invention]

The active energy ray-curable resin composition of the present invention, a cured product containing the composition, and a laminate have excellent workability and viscosity, and have scratch resistance.

The present invention relates to an active energy ray-curable resin composition (hereinafter also referred to as "resin composition"), which comprises: (meth)acrylic copolymer (A) (hereinafter also referred to as "(A) component") , Which is a monomer component of a radical polymer (a1) (hereinafter also referred to as "(a1) component") and α,β-unsaturated carboxylic acid (a2) (hereinafter also referred to as "(a2) component") Reactant, and the hydroxyl group concentration is 2mmol/g or more, and the (meth)acryloyl group equivalent is 400eq/g or less. The monomer component contains an epoxy group-containing mono(meth)acrylate; Group) acrylate (B) (hereinafter also referred to as "(B) component"), which has at least three (meth)acryloyl groups and has a hydroxyl group concentration of 0.1 mmol/g or more; and, polyfunctional isocyanate (C ) (Hereinafter also referred to as "(C) component"). Hereinafter, each component will be described in detail.

In addition, (meth)acrylate means acrylate and/or methacrylate. In addition, (meth)acrylic acid means acrylic acid and/or methacrylic acid. Furthermore, (meth)acryloyl group refers to acryloyl group and/or methacryloyl group.

<(A) component> (A) component is a (meth)acrylic copolymer which is a reactant of (a1) component and (a2) component, and a hydroxyl group concentration is 2 mmol/g or more, (methyl) The equivalent of propylene amide group is 400 eq/g or less. As the copolymer of the component (A), two or more types can be used in combination.

<(a1) component> The (a1) component is a radical polymer of a monomer component which contains an epoxy group-containing mono(meth)acrylate.

As the epoxy group-containing mono(meth)acrylate (hereinafter also referred to as "(a1-1) component"), various publicly known substances can be used. As the (a1-1) component, there can be exemplified: glycidyl (meth)acrylate, glycidyl α-ethyl (meth)acrylate, glycidyl α-n-propyl (meth)acrylate, α-normal Glycidyl butyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate glycidyl ether, (meth)acrylic acid [(3,4-epoxyepoxyhexane)-1-yl]methacrylate Ester etc. The substances exemplified as the component (a1-1) and the known substances as the component (a1-1) can be used alone or in combination of two or more kinds. The component (a1-1) is preferably glycidyl (meth)acrylate in terms of ease of acquisition and scratch resistance.

(a1) The constituent monomers of the component may include, in addition to the (a1-1) component, a monomer that does not contain an epoxy group and can be copolymerized (hereinafter referred to as (a1-2) component).

As the (a1-2) component, various publicly known products can be used. Examples of the component (a1-2) include: aromatic-containing mono(meth)acrylates such as styrene, α-methylstyrene, tertiary butylstyrene, and dimethylstyrene; maleic anhydride , Iconic anhydride, citraconic anhydride, alkenyl succinic anhydride, dienyl succinic anhydride and other aliphatic unsaturated dicarboxylic anhydride; methyl (meth)acrylate, ethyl (meth)acrylate, (meth)acrylic acid Butyl ester, amyl (meth)acrylate, hexyl (meth)acrylate, cyclohexyl (meth)acrylate, stearyl (meth)acrylate, benzyl (meth)acrylate, (meth) (Meth)acrylates such as isobornyl acrylate, dicyclopentadiene (meth)acrylate; acrylonitrile, acrylamido, vinyl acetate, having more than one unsaturated double bond at either end and no ring Oxygen and carboxyl macromonomer, etc. The substances exemplified as the (a1-2) component and the known substances as the (a1-2) component can be used alone or in combination of two or more kinds.

Examples of macromonomers having at least one unsaturated double bond at either end and containing no epoxy groups or carboxyl groups include: (meth)acryloyl group-containing macromonomers and polysiloxane-based macromonomers , (Meth)acrylate macromonomer, styrene macromonomer, (meth)acrylamide macromonomer, acrylonitrile macromonomer, etc.

As the above-mentioned macromonomer, commercially available products can be used. The product is not particularly limited, and examples include: (mon)acryloyl group-containing giant monomer (product name "MACROMONOMER AA-6", "MACROMONOMER AB-6", manufactured by East Asia Synthetic Co., Ltd.), poly Siloxane macromonomer (product name "Silaplane FM-0711", "Silaplane FM-0721", manufactured by JNC Corporation), (meth)acrylate macromonomer (product name "BLEMMER PME-4000" , "BLEMMER PSE-1300", manufactured by NOF Corporation), etc.

<(a2) component> (a2) component is an α,β-unsaturated carboxylic acid.

In this specification, α,β-unsaturated carboxylic acid refers to a substance having an unsaturated bond between the carbon (α carbon) located adjacent to the carboxyl group and the carbon (β carbon) further adjacent thereto.

The component (a2) is not particularly limited, and various publicly known products can be used. Examples of the component (a2) include α,β-unsaturated monocarboxylic acid, α,β-unsaturated dicarboxylic acid and the like.

As the α,β-unsaturated monocarboxylic acid, (meth)acrylic acid and the like can be exemplified. Examples of α,β-unsaturated dicarboxylic acids include itaconic acid and maleic acid. The substances exemplified as the (a2) component and the known substances as the (a2) component can be used alone or in combination of two or more types. From the viewpoint of good scratch resistance of the coating film obtained by completely curing the resin composition (hereinafter also referred to as "cured product"), the component (a2) is preferably α,β-unsaturated monocarboxylic acid, More preferably, it is (meth)acrylic acid.

The mass ratio of the solid content of (a1) component and (a2) component is not particularly limited, but it is usually (a1)/(a2)=about 10/90 to 90/10.

From the viewpoint of excellent processability and viscosity of the partially cured coating film, the hydroxyl group concentration of the component (A) is preferably 2 mmol/g or more, more preferably 2 mmol/g or more and 5 mmol/g or less. If it is also considered that the viscosity of the coating film after partial hardening is further excellent, the hydroxyl group concentration of the component (A) is further preferably 3 mmol/g or more and 5 mmol/g or less. When the hydroxyl group concentration of the component (A) is less than 2 mmol/g, although the detailed mechanism is not clear, the viscosity of the coating film after partial hardening becomes poor, which is not good.

In the present specification, the hydroxyl group concentration refers to the ratio of the hydroxyl group contained in 1 g of one or more components indicating the hydroxyl group concentration to be calculated, and can be calculated as “the molecular weight of the number of hydroxyl groups/1 component or more”.

From the viewpoint that the cured product and the laminate show high hardness and excellent scratch resistance, the (meth)acryl equivalence of the component (A) is preferably 400 g/eq or less, more preferably 150 g/eq or more Furthermore, 400 g/eq or less, further preferably 150 g/eq or more and 350 g/eq or less, and particularly preferably 200 g/eq or more and 350 g/eq or less. When the (meth)acryloyl equivalent of the component (A) exceeds 400 g/eq, although the detailed mechanism is unclear, the scratch resistance and pencil hardness of the hardened product and the laminate become poor, which is not good.

In the present specification, the (meth)acryloyl group equivalent is expressed in terms of molecular weight per (meth)acryloyl group, and can be calculated as "molecular weight/number of functional groups".

(A) The weight-average molecular weight of the component is not particularly limited, but from the viewpoint of excellent anti-caking properties of the cured product and the laminate and the resin composition exhibiting a better viscosity, it is preferably 10,000 or more and 200,000 or less.

In this specification, the weight average molecular weight is a value in terms of polystyrene in accordance with gel permeation chromatography.

<Method for synthesizing (A) component> The method for synthesizing (A) component is not particularly limited, and various well-known methods can be used. As a method of synthesizing the component (A), there can be exemplified a method of reacting the component (a1) with the component (a2) under the conditions of 30 minutes or more and 12 hours, 50°C or more and 200°C or less.

<(B) component> (B) component is a multifunctional (meth)acrylate having at least 3 (meth)acryloyl groups (H ₂ C=CR-C(=O)-(R is Hydrogen or methyl)), and the hydroxyl group concentration is 0.1 mmol/g or more.

The component (B) is not particularly limited, and various publicly known products can be used. As the (B) component, tri(meth)acrylate, tetra(meth)acrylate, penta(meth)acrylate, hexa(meth)acrylate, poly(meth)acrylate and the like can be exemplified.

As the tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, ethylene oxide modified trimethylolpropane tri(meth)acrylate, propylene oxide modified tri Hydroxymethylpropane tri(meth)acrylate, propylene oxide modified glycerin (meth)acrylate, pentaerythritol tri(meth)acrylate, etc.

Examples of tetra(meth)acrylates include pentaerythritol tetra(meth)acrylate, ethylene oxide-modified pentaerythritol tetra(meth)acrylate, and dipentaerythritol tetra(meth)acrylate.

Examples of penta(meth)acrylates include dipentaerythritol penta(meth)acrylates.

Examples of hexa(meth)acrylates include dipentaerythritol hexa(meth)acrylate, ethylene oxide-modified dipentaerythritol hexa(meth)acrylate, and the like.

Examples of poly(meth)acrylates include dipentaerythritol poly(meth)acrylates, tripentaerythritol poly(meth)acrylates, and the like.

In this specification, poly(meth)acrylate refers to a mixture of substances having three or more (meth)acryloyl groups.

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

From the viewpoint of excellent scratch resistance of the cured product and the laminate, the component (B) is preferably poly(meth)acrylate, and more preferably dipentaerythritol poly(meth)acrylate.

As the component (B), commercially available products can be used. The product is not particularly limited, and examples include: pentaerythritol triacrylate (product name "A-TMM-3", "A-TMM-3L", manufactured by Shin Nakamura Chemical Industry Co., Ltd.; product name "Miramer M301" , Manufactured by MIWON; product name "ARONIX M-309", manufactured by East Asia Synthetic Co., Ltd.), di-trimethylolpropane tetraacrylate (product name "ARONIX M-408", manufactured by East Asia Synthetic Co., Ltd.), Dipentaerythritol penta(meth)acrylate (product name "SR399", manufactured by Pakistan Industrial Co., Ltd.), dipentaerythritol poly(meth)acrylate (dipentaerythritol penta(meth)acrylate and dipentaerythritol hexa(meth)acrylate ) Mixture of acrylic esters: product name "KAYARAD DPHA", manufactured by Nippon Kayaku Co., Ltd.; product name "A-9550", manufactured by Shin Nakamura Chemical Industry Co., Ltd.; product names "ARONIX M-403", "ARONIX M -400", "ARONIX M-402", "ARONIX M-404", "ARONIX M-405", "ARONIX M-406", manufactured by East Asia Synthetic Co., Ltd.), tripentaerythritol poly(meth)acrylate ( Product name "Viscoat#802, TriPEA", manufactured by Osaka Organic Chemical Industry Co., Ltd.), etc.

From the viewpoint of excellent transparency of the cured product and the laminate, the hydroxyl group concentration of the component (B) is preferably 0.1 mmol/g or more, more preferably 0.1 mmol/g or more and 2 mmol/g or less, and still more preferably 1 mmol/g or more and 2 mmol/g or less, particularly preferably 1.5 mmol/g or more and 2 mmol/g or less.

The number of (meth)acryloyl groups of component (B) is at least 3, and more preferably 3 or more, from the viewpoint of excellent adhesion of the partially cured coating film and excellent scratch resistance of the cured product and the laminate And less than 6.

From the viewpoint of excellent viscosity and workability of the partially cured coating film, the mass ratio of the solid components of (A) and (B) components is preferably 30/70 to 99/1, more preferably 30 /70~97/3, further preferably 35/65~97/3.

The total content of (A) component and (B) component is not particularly limited, and from the viewpoint of excellent processability of the partially cured coating film, it is preferably converted to solid content relative to the total amount of the resin composition It is 60 mass% or less and 99 mass% or less, More preferably, it is 70 mass% or less and 99 mass% or less in solid content conversion.

<Method for preparing a mixture of (A) component and (B) component> A mixture of (A) component and (B) component is usually obtained by mixing (A) component and (B) component at room temperature.

<(C)component> (C)component is a polyfunctional isocyanate. Multifunctional isocyanate refers to a substance having more than 2 isocyanate groups (-N=C=O).

The component (C) is not particularly limited, and various publicly known materials can be used. Examples of the component (C) include linear aliphatic polyfunctional isocyanates, branched aliphatic polyfunctional isocyanates, alicyclic polyfunctional isocyanates, and aromatic polyfunctional isocyanates.

Examples of linear aliphatic polyfunctional isocyanates include: trimethylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, octamethylene diisocyanate, decamethylene Diisocyanate, amine triisocyanate, etc.

Examples of branched aliphatic polyfunctional isocyanates include methyl diisocyanatohexanoate, trimethylhexamethylene diisocyanate, and the like.

Examples of the alicyclic polyfunctional isocyanate include dicyclohexylmethane diisocyanate, isophorone diisocyanate, bis(isocyanatomethyl)cyclohexane, cyclohexanediyl dimethylene diisocyanate, and methyl alcohol. Cyclohexanediyl diisocyanate, norbornene methane diisocyanate, etc.

Examples of the aromatic polyfunctional isocyanate include toluene diisocyanate, methine ginseng (isocyanatobenzene), xylene diisocyanate, and diisocyanatonaphthalene.

The substance exemplified as the (C) component and the known substance as the (C) component can be used alone or in combination of two or more kinds. In addition, one kind or two or more kinds of polymers of these polyfunctional isocyanates can be used. As the polymer of the component (C), that is, polyisocyanate, isocyanurate, adduct, allophanate and the like can be exemplified.

From the viewpoint of excellent reactivity during partial curing, the component (C) is preferably a polymer of a linear aliphatic polyfunctional isocyanate, and more preferably a polymer of hexamethylene diisocyanate.

As the (C) component, commercially available products can be used. The product is not particularly limited, and examples include: hexamethylene diisocyanate (product model "H0324", manufactured by Tokyo Chemical Industry Co., Ltd.), trimethylhexamethylene diisocyanate (product model "T1176", Tokyo Chemical Industry Co., Ltd.), dicyclohexylmethane-4,4'-diisocyanate (product model "D2380", manufactured by Tokyo Chemical Industry Co., Ltd.), isophorone diisocyanate (product model "I0314", Tokyo Chemical Industry Co., Ltd.), 1,3-bis (isocyanatomethyl) cyclohexane (product model "B1538", Tokyo Chemical Industry Co., Ltd.), norbornene methane diisocyanate (product name "Norbornane dimethyleneisocyanate", manufactured by Hangzhou Brown Biomedical Technology Co., Ltd., toluene-2,4-diisocyanate (product model "T0263", manufactured by Tokyo Chemical Industry Co., Ltd.), xylene diisocyanate (product model "X0022", Tokyo Chemical Industry Co., Ltd.), diisocyanatonaphthalene (product model "N0168", Tokyo Chemical Industry Co., Ltd.), hexamethylene diisocyanate polyisocyanate (product name "CORONATE HXR", "CORONATE "HK", "CORONATE 2770", manufactured by Tosoh Corporation), 1,5-pentamethylene diisocyanate polyisocyanate (product name "STABiO PDI", manufactured by Mitsui Chemicals Co., Ltd.), etc.

The mass ratio of (A) component and (B) component to (C) component solid component ([(A) component + (B) component]/(C) component) is not particularly limited, and is partially cured From the viewpoint of excellent processability of the film, it is preferably [(A)+(B)]/(C)=60/40 to 99/1, more preferably 75/25 to 98/2.

<Method for producing resin composition> The method for producing the resin composition is not particularly limited, and various well-known methods can be used. As a method of preparing the resin composition, the following method can be exemplified: the appropriate amounts of (A) component, (B) component and (C) component are mixed, and diluted with an organic solvent to adjust the non-volatile component, and then uniformly mixing.

<(D)component> The resin composition may further contain a photopolymerization initiator (D) (hereinafter also referred to as "(D)component"). The component (D) is a compound that can generate free radicals by energy rays such as ultraviolet rays. By containing the component (D) in the resin composition, the resin composition has excellent hardening performance (hereinafter also referred to as "curability").

The component (D) is not particularly limited, and various publicly known products can be used. Examples of the component (D) include radical photopolymerization initiators, cationic photopolymerization initiators, anionic photopolymerization initiators, and the like.

As the radical photopolymerization initiator, there can be exemplified: alkyl phenyl ketone type photopolymerization initiator, acetylphosphine oxide type photopolymerization initiator, dehydrogenation type photopolymerization initiator, oxime ester type photopolymerization Starter, etc.

As an alkyl phenyl ketone type photopolymerization initiator, there can be exemplified: benzyl dimethyl ketals such as 2,2-dimethoxy-1,2-diphenylethane-1-one; 1 -[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1-{4-[4-(2-hydroxy Α-hydroxyalkyl phenyl ketones such as -2-methyl-propanyl)-benzyl]phenyl}-2-methyl-propan-1-one, 1-hydroxy-cyclohexyl-phenyl ketone, etc. , 2-methyl-1-(4-methylthiophenyl)-2-N-morpholinylpropan-1-one, 2-benzyl-2-dimethylamino-1-(4 -N-morpholinylphenyl)-1-butanone, 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholine Group) phenyl]-1-butanone and the like α-aminoalkyl phenyl ketone and the like.

As a phosphine oxide photopolymerization initiator, there can be exemplified: 2,4,6-trimethylbenzyl-diphenyl-phosphine oxide, bis(2,4,6-trimethylbenzyl amide) Group)-phenylphosphine oxide and so on.

As the dehydrogenation type photopolymerization initiator, methyl phenylglyoxylate and the like can be exemplified

As the oxime ester type photopolymerization initiator, 1-[4-(phenylthio)-1,2-octanedione 2-(O-benzoyl oxime)], 1-[9- Ethyl-6-(2-methylbenzyl)-9H-carbazol-3-yl]ethanone 1-(O-acetamide) and the like.

As a cationic photopolymerization initiator, a mixture of (1-)(4-methylphenyl)[4-(2-methylpropyl)phenyl]phosphonium hexafluorophosphate and propylene carbonate can be exemplified. Hexafluorophosphoric acid triaryl alkane, (pentafluorophenyl) boric acid triaryl alkane, etc.

Examples of the anionic photopolymerization initiator include cobaltamine complex, o-nitrobenzylcarbamate, oxime ester, and the like.

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

(D) The component, in particular, is excellent in curability, so it is preferably a radical photopolymerization initiator, more preferably an alkylphenyl ketone type photopolymerization initiator, and still more preferably α-hydroxyalkylphenyl 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 .

As the component (D), commercially available products can be used. The product is not particularly limited, and can be exemplified by 2,2-dimethoxy-1,2-diphenylethyl-1-one (product name "Omnirad (hereinafter also referred to as "Omnirad") 651", IGM Resins), 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one (product name "Omnirad 2959", IGM Resins (Manufactured by the company), 2-hydroxy-1-{4-[4-(2-hydroxy-2-methyl-propionyl)-benzyl]phenyl}-2-methyl-propan-1-one ( Product name "Omnirad127", manufactured by IGM Resins), 1-hydroxy-cyclohexyl-phenyl ketone (product name "Omnirad184", manufactured by IGM Resins), 2-methyl-1-(4-methylthiobenzene Group)-2-N-morpholinylpropan-1-one (product name "Omnirad907", manufactured by IGM Resins), 2-benzyl-2-dimethylamino-1-(4-N-? Phenylphenyl)-1-butanone (product name "Omnirad369E", manufactured by IGM Resins), 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1- [4-(4-morpholinyl)phenyl]-1-butanone (product name "Omnirad 379EG", manufactured by IGM Resins), 2,4,6-trimethylphenacyl-diphenyl-oxidation Phosphine (product name "Omnirad TPO H", manufactured by IGM Resins), bis(2,4,6-trimethylphenacyl)-phenylphosphine oxide (product name "Omnirad819", manufactured by IGM Resins), benzene Methyl glyoxylate (product name "Omnirad MBF", manufactured by IGM Resins), 1-[4-(phenylthio)-1,2-octanedione 2-(O-phenyl acetyl oxime)] (Product name "IRGACURE OXE 01", manufactured by BASF Corporation of Japan), 1-[9-ethyl-6-(2-methylphenacyl)-9H-carbazol-3-yl] ethyl ketone 1- (O-acetyl oxime) (product name "IRGACURE OXE 02", manufactured by BASF Corporation of Japan), hexafluorophosphoric acid (1-) (4-methylphenyl) (4-(2-methylpropyl) Phenyl] mixture of iodonium and propylene carbonate (product name "Omnicat (hereinafter also referred to as "Omnicat" 250), manufactured by IGM Resins), triaryl hexafluorophosphate (product name "Omnicat270", IGM Resins) (Manufactured), triaryl pentafluorobenzyl borate (product name "IRGACURE 290", manufactured by BASF Corporation of Japan), etc.

(D) The content of the component is not particularly limited, but from the viewpoint of excellent curability at the time of complete curing, it is preferably 0.1 mass% or more and 15 mass in terms of solid content relative to the total amount of the resin composition. % Or less, more preferably 0.2% by mass or more and 10% by mass or less in terms of solid content.

<(E) component> The resin composition may further contain a fluorine-containing compound (E) (hereinafter also referred to as "(E) component"). By containing the (E) component in the resin composition, in particular, the cured product and the laminate have excellent scratch resistance, and further excellent leveling properties (coatability), water repellency, oil repellency, antifouling properties and finger slip properties .

The component (E) is not particularly limited, and various publicly known materials can be used. Examples of the component (E) include perfluoroalkyl group-containing carboxylic acid or its salt, perfluoroalkyl group-containing sulfonic acid or its salt, or perfluoroalkyl group-containing phosphoric acid or its phosphate ester. Fluoroalkyl compounds; perfluoroalkenyl-containing compounds obtained by replacing the above perfluoroalkyl groups with perfluoroalkenyl groups; perfluoroether-containing compounds obtained by replacing the above perfluoroalkyl groups with perfluoroether groups; Oligomers containing fluorine-containing groups/lipophilic groups, oligomers containing fluorine-containing groups/hydrophilic groups, oligomers containing fluorine-containing groups/hydrophilic/lipophilic groups, containing fluorine-containing groups/hydrophilic/ Oligomers with lipophilic groups/carboxyl groups, oligomers containing fluorine groups/UV reactive groups, etc.

The substance exemplified as the (E) component and the known substance as the (E) component can be used alone or in combination of two or more kinds. In addition, one kind or two or more kinds of polymers of these fluorine-containing compounds can be used.

From the viewpoint of excellent scratch resistance, water repellency, oil repellency, and antifouling properties of the cured product, the component (E) is preferably an oligomer containing a fluorine-containing group/UV-reactive group.

As the (E) component, commercially available products can be used. Examples of this product include perfluorobutane sulfonate (product name "MEGAFAC F-114", manufactured by DIC Corporation), and perfluoroalkyl group-containing carboxylate (product name "MEGAFAC F-410", DIC Co., Ltd.), phosphate ester containing perfluoroalkyl/phosphate group (product name "MEGAFAC F-510", manufactured by DIC Corporation), modified perfluoropolyether (product name "Optool DAC-HP", Manufactured by Daikin Industries Co., Ltd.; product names "KY-108", "KY-164", "X-71-195", "KY-1900", manufactured by Shin-Etsu Chemical Industry Co., Ltd.), containing fluorine groups/ Lipophilic group oligomers (product name "MEGAFAC F-281", "MEGAFAC F-253", "MEGAFAC F-251"; the above is manufactured by DIC Corporation), low fluorine-containing groups / hydrophilic groups Polymers (product names "MEGAFAC F-430", "MEGAFAC F-551", "MEGAFAC F-552", manufactured by DIC Corporation), oligomers containing fluorine-containing groups/hydrophilic groups/lipophilic groups ( Product name "MEGAFAC F-477", manufactured by DIC Corporation), oligomer containing fluorine group/hydrophilic group/lipophilic group/carboxyl group (product name "MEGAFAC F-570", manufactured by DIC Corporation) 、Oligomer containing fluorine group/UV reactive group (product name "MEGAFAC RS-56", "MEGAFAC RS-90", "MEGAFAC RS-75", manufactured by DIC Corporation; product name "KY-1203 ", manufactured by Shin-Etsu Chemical Industry Co., Ltd.).

(E) The content of the component is not particularly limited. From the viewpoint of excellent scratch resistance of the cured product, it is preferably 0.05% by mass or more and 10% by mass in terms of solid content relative to the total amount of the resin composition. Below, it is more preferable that it is 0.1 mass% or more and 10 mass% or less in solid content conversion.

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

The component (F) is not particularly limited, and various publicly known products can be used. Examples of the component (F) include zinc oxide nanoparticles, silicon dioxide nanoparticles, aluminum oxide nanoparticles, cerium oxide nanoparticles, iron oxide nanoparticles, titanium oxide nanoparticles, and zirconium oxide nanoparticles. Particles, cuprous oxide nanoparticles, etc.

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

From the viewpoint of excellent scratch resistance of the cured product, the component (F) is preferably alumina nanoparticles.

As the (F) component, commercially available products can be used. Examples of the product include zinc oxide nanoparticles (product name "NANOBYK-3840", manufactured by BYK), and silicon dioxide nanoparticles (product names "NANOBYK-3650", "NANOBYK-3652", manufactured by BYK. ), alumina nanoparticles (product name "NANOBYK-3603", "NANOBYK-3610", manufactured by BYK), cerium oxide nanoparticles (product name "cerium (IV) nanoparticles (10nm)", FUJIFILM Wako Chemical Co., Ltd.), iron oxide nanoparticles (product name "iron oxide (II, III), magnetic nanoparticle solution", manufactured by SIGMA-ALDRICH)), titanium oxide nanoparticles (product name "TTO- 51(A)", "TTO-55(C)", manufactured by Ishihara Industries Co., Ltd.), zirconia nanoparticles (product name "Zirconeo-Cp", "Zirconeo-Rp", "Zirconeo-Cw", " "Zirconeo-Ck", manufactured by ITEC Corporation), cuprous oxide nanoparticles (product name "FRC-N10", manufactured by Furukawa Chemicals Corporation), etc.

(F) The content of the component is not particularly limited. From the viewpoint of excellent scratch resistance of the cured product, it is preferably 0.1% by mass or more and 20% by mass in terms of solid content relative to the total amount of the resin composition. Below, it is more preferable that it is 0.1 mass% or more and 10 mass% or less in solid content conversion.

<Production method of resin composition containing (A) component, (B) component, (C) component, (D) component, (E) component and (F) component> As (A) component and (B) component are contained The method for preparing the resin composition of (C) component, (D) component, (E) component and (F) component is not particularly limited, and various well-known methods can be used. As such a method, the following method may be exemplified: an appropriate amount of (A) component, (B) component, (C) component, (D) component, (E) component, and (F) component, and using an organic solvent to Dilute and mix to adjust the non-volatile components, and then mix evenly.

<Other blendable formulations> In the resin composition, one or more formulations selected from the following formulations can be further blended: various known resins such as acrylic resins, epoxy resins, or urethane resins; reactive dilution Monomers, UV absorbers, antioxidants, silicone additives, antistatic agents, anti-fogging agents, rheology modifiers, fillers, mold release agents, flame retardants, viscosity modifiers, plasticizers, antibacterial agents, Mildew agent, defoamer, colorant, stabilizer, pigment, surface modifier, various solvents, various catalysts and photosensitizers, etc.

<Coated Film after Partial Hardening> A coating film obtained by partially curing a resin composition by heating (hereinafter also referred to as a "heat treatment step") is also one of the inventions of the present invention. The partially cured coating film of the present invention can be laminated on the surface of a molded product having a complicated shape such as deep drawing without cracking.

By heating the film-like resin composition, the resin composition becomes a thermal crosslinking reaction product. This thermal cross-linking reaction product is in a non-tacky state, so it becomes easy to print other laminates on the film-like thermal cross-linking reaction product or it becomes easy to take up the film. At this stage where only heating is performed, the ethylenically unsaturated groups contained in the resin composition are not cross-linked, so the resin composition is not completely cross-linked and hardened. In other words, it is partially hardened. Therefore, the film-shaped thermal cross-linking reaction product can be applied to the curved surface of the molded product, and has flexibility that does not cause cracking. Also, a film having a square shape can be attached to the partially cured film to transfer the shape, or a protective film for anti-fouling can be attached.

The thickness of the coating film is not particularly limited, but it is preferably 1 μm or more and 1000 μm or less, and more preferably 3 μm or more and 500 μm or less. By setting the thickness to this range, the workability of the partially cured coating film and the scratch resistance of the cured product can be improved.

Examples of the coating method of the resin composition include bar coater coating, Meyer bar coating, air knife coating, gravure coating, reverse gravure coating, lithographic printing, flexographic printing, and screen printing. Printing method, etc. In addition, the coating amount is not particularly limited, but it is generally within a range of 1 g/m ² or more and 1000 g/m ² or less after drying, and preferably 3 g/m ² or more after drying. Within the range of 500g/m ² or less.

As a method of the heat treatment step, various well-known methods can be used. As a method of the heat treatment step, from the viewpoint of the reactivity of the components (A) and (B) and (C), the following method can be preferably exemplified: heating at 100° C. or more and 150° C. or less 1 More than 30 minutes and less than 30 minutes.

The elongation at break of the coating film obtained by hardening the resin composition by the heat treatment step is preferably 40% or more, more preferably 40% or more and 300% or less.

In the present invention, the elongation at break refers to the ratio of the length (cm) after extending from the length (cm) of the coating film of 0% when the state before stretching the coating film is set to 0%. Specifically, a commercially available tensile testing machine such as Tensilon universal testing machine (product name "RTG-1250", manufactured by A&D Co., Ltd.) is used, and the conditions are at a speed of 100 mm/min while heating at 150°C. After stretching, the length when the crack is observed on the sample and the length of the sample before stretching are used, and calculation is performed according to the following formula. Elongation at break (%) = 100 × (L-Lo)/Lo Lo: length of the sample before stretching L: length of the sample when cracking was initially observed

<Cured product> A cured product obtained by irradiating the coating film after the heat treatment step with active energy rays such as ultraviolet rays is also one of the inventions of the present invention.

As a method of curing by ultraviolet irradiation, various well-known methods can be used. As a method of curing by ultraviolet irradiation, the following method can be exemplified: a high-pressure mercury lamp, an ultra-high pressure mercury lamp, a carbon arc lamp, a metal halogen lamp, a xenon lamp, a chemical that can emit light in a wavelength region of 150 nm or more and 450 nm or less Lamps, electrodeless discharge lamps, light-emitting diodes (LEDs), etc., are irradiated at about 10 mJ/cm ² or more and 10,000 mJ/cm ² or less.

<Laminate> The present invention is also a laminate, which is obtained by attaching a coating film after a heat treatment step to at least one surface of a substrate, and further irradiating active energy rays such as ultraviolet rays to completely harden it. By completely curing the partially cured coating film, it is possible to impart a degree of less damage to the substrate.

<Molded article> As an application example of the resin composition, formation of a hard coat layer on various known articles can be exemplified.

As this article, various well-known articles can be exemplified. As the article, the following plastic molded products can be exemplified: the body of a home appliance such as a refrigerator, TV, or air conditioner, and its remote control; the housing and display of an information terminal such as a mobile phone, smartphone, tablet, or personal computer; and , Automotive parts or automotive interior materials, etc. In particular, it is expected to be used for the housing of an information terminal.

<Applicable substrate> The resin composition can be applied to various substrates such as metal, plastic, film, glass, etc.

As various substrates, various known materials can be used. Examples of various substrates include metals, plastics, films, glass, or other resins.

Examples of the metal include iron, aluminum, aluminized steel plate, tin-free steel plate (TFS), stainless steel plate, zinc phosphate-treated steel plate, and zinc-zinc alloy-plated steel plate (phosphate-treated steel plate).

Examples of plastics include acrylonitrile-butadiene-styrene (ABS), polycarbonate (PC), polyethylene (PE), polypropylene (PP), polystyrene (PS), and polyterephthalic acid Polyester (PE) such as ethylene glycol (PET); acrylics such as polymethyl methacrylate (PMMA); fiber-reinforced plastic (FRP), etc.

Examples of the film include PET and polyethylene naphthalate (PEN).

Examples of other resins include epoxy resins, melamine resins, triacetyl cellulose resins, ABS resins, acrylonitrile-styrene (AS) resins, and norbornene-based resins. [Example]

Hereinafter, the synthesis examples, examples, comparative examples, evaluation examples, and comparative evaluation examples will be listed to further specifically explain the present invention, but the present invention is not limited to these examples. In addition, in the following description, parts or% 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) Model: product name "HLC-8220" (manufactured by Tosoh Corporation) Tubular column: product name "TSKgel SuperHM-L" (manufactured by Tosoh Corporation) × 3 developing solvents: tetrahydrofuran (below (Also known as "THF")

<Synthesis Example 1: Synthesis of (A-1) component> 32.6 parts of glycidyl methacrylate (hereinafter also referred to as "GMA") was charged into a reaction device equipped with a stirring device, cooling tube, thermometer, and nitrogen introduction tube After 48.6 parts of butyl acetate and 1.5 parts of azobisisobutyronitrile (hereinafter also referred to as "AIBN"), the temperature was increased to 100°C under a nitrogen gas flow, and the temperature was maintained for 10 hours. After the reaction was completed, it was cooled to 60°C 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 then allowed to air bubbles The temperature was raised to 110° C., and the reaction was carried out for 9 hours to obtain a (meth)acrylic copolymer solution having a resin solid content of 50% (hereinafter also referred to as “(A-1) component”). The hydroxyl group concentration of the obtained (meth)acrylic copolymer was 4.7 mmol/g, the equivalent of acryloyl group was 214 g/eq, and the weight average molecular weight (polystyrene conversion value measured by GPC) was 30,000.

<Synthesis Example 2: Synthesis of (A-2) component> 16.3 parts of GMA, 16.3 parts of methyl methacrylate, and 48.6 parts of butyl acetate were charged into a reaction device equipped with a stirring device, a cooling tube, a thermometer, and a nitrogen introduction tube After 2.0 parts of AIBN, the temperature was increased to 100°C under a nitrogen gas flow, and the temperature was maintained for 10 hours. After the reaction is completed, cool to 60°C, charge 8.3 parts of AA, 0.5 parts of methoxyphenol, and 0.1 part of triphenylphosphine, and then raise the temperature to 110°C in the presence of air bubbles, and proceed to reaction 9 Hours, a (meth)acrylic copolymer solution having a resin solid content of 50% (hereinafter also referred to as "(A-2) component") is obtained. The hydroxyl concentration of the obtained (meth)acrylic copolymer was 2.8 mmol/g, the acrylic equivalent was 356 g/eq, and the weight average molecular weight (polystyrene conversion value measured by GPC) was 10,000.

<Synthesis Example 3: Synthesis of (A-3) component> In a reaction device equipped with a stirring device, a cooling tube, a thermometer, and a nitrogen introduction tube, 8.2 parts of GMA, 24.6 parts of methyl methacrylate, and 48.6 parts of butyl acetate were charged After 2.0 parts of AIBN, the temperature was increased to 100°C under a nitrogen gas flow, and the temperature was maintained for 10 hours. After the reaction was completed, it was cooled to 60°C, charged with 4.2 parts of AA, 0.5 parts of methoxyphenol, and 0.1 part of triphenylphosphine, and then heated to 110°C in the presence of air bubbles, and proceeded to reaction 9 Hours, a (meth)acrylic copolymer solution having a resin solid content of 50% (hereinafter also referred to as "(A-3) component") is obtained. The hydroxyl group concentration of the obtained (meth)acrylic copolymer was 1.6 mmol/g, the equivalent of acryloyl group was 635 g/eq, and the weight average molecular weight (polystyrene conversion value measured by GPC) was 10,000.

<Example 1: Preparation of resin composition (1)> 140.0 parts (A-1) component is blended with 30.0 parts of dipentaerythritol polyacrylate (product name "ARONIX M-403", manufactured by East Asia Synthetic Co., Ltd., hydroxyl group concentration 1.6mmol/g, a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate, hereinafter also referred to as "(B-1) ingredient"), 10.0 parts of polyisocyanate (product name "CORONATE HK", Tosoh Corporation Limited A polyisocyanate based on hexamethylene diisocyanate, also referred to as "(C-1) component"), 5.0 parts of 1-hydroxy-cyclohexyl-phenyl as a photopolymerization initiator Ketone (product name "Omnirad 184", manufactured by IGM Resins, hereinafter also referred to as "(D) component"), 2.0 parts of fluorine-containing compound (product name "MEGAFAC RS-90", manufactured by DIC Corporation, hereinafter also referred to as "(E) component"), 14.0 parts of alumina nanoparticles (product name "NANOBYK-3610", manufactured by BYK, hereinafter also referred to as "(F) component"), 0.02 parts of dilaurel as a catalyst Dioctyltin acid (hereinafter also referred to as "(G) component") is diluted with methyl ethyl ketone to make the non-volatile component 20%, and then uniformly mixed to obtain a resin composition.

<Examples 2 to 13: Preparation of resin compositions (2) to (13)> The composition was changed to the composition shown in Table 1 below, and the same procedure as in Example 1 was carried out to prepare resin compositions (2) to ( 13).

<Comparative Examples 1 to 6: Preparation of resin compositions (C1) to (C6)> The composition was changed to the composition shown in Table 2 below, and the resin composition (C1) to (C1) was prepared in the same manner as in Example 1. C6).

<Evaluation Example 1-1: Production of partially cured coating film (1)> Using a bar coater (model "No. 24", manufactured by Daiichi Chemical Co., Ltd.), the base material (polymethacrylic acid Made of ester, with a thickness of 0.400 mm), a resin composition (1) with a film thickness of about 5 μm is coated on the surface and dried in a circulating air dryer at 120° C. for 2 minutes to heat the resin composition, thereby forming a portion The cured coating (1).

<Evaluation Example 1-2: Production of a hardened product (1)> A high-pressure mercury lamp (120 W/cm output) was used under the conditions of an irradiation distance of 15 cm, a conveyor belt speed of 7 m/min, and a cumulative irradiation amount of 300 mJ/cm ² The partially cured coating film (1) is cured to produce a cured product (1).

<Evaluation Examples 2-1 to 13-1: Preparation of partially cured coating films (2) to (13)> The resin composition (1) was changed to the resin composition (2) to (13), and the evaluation In Example 1-1, the partially cured coating films (2) to (13) were produced in the same manner.

<Evaluation Examples 2-2 to 13-2: Production of cured products (2) to (13)> The partially cured coating film (1) was changed to partially cured coating film (2) to (13), in addition to The cured products (2) to (13) were produced in the same manner as in Evaluation Example 1-2.

<Comparative Evaluation Examples 1-1 to 6-1: Preparation of partially cured coating films (C1) to (C6)> The resin composition (1) was changed to the resin composition (C1) to (C6), and the Evaluation Example 1-1 was produced in the same manner as above to produce partially cured coating films (C1) to (C6).

<Comparative Evaluation Examples 1-2 to 6-2: Production of cured products (C1) to (C6)> The partially cured coating film (1) was changed to partially cured coating film (C1) to (C6), and In the same manner as in Evaluation Example 1-2, cured products (C1) to (C6) were produced.

<Performance evaluation: Scratch resistance> The hardened products (1) to (13) and (C1) to (C6) are installed in a commercially available measuring device (product name "Plane Abrasion Tester", Dairy Seiki Co., Ltd. Limited (Made by the company), and using steel wool (model "#0000", grade "very fine", manufactured by NIHON STEEL WOOL Co., Ltd.), the surface of the hardened object was scratched back and forth 100 times with a load of 1 kg. The scratch resistance of the laminate was evaluated according to the number of damages according to the following criteria. ○: Less than 3 damages △: More than 3 damages but less than 10 damages ×: More than 10 damages

<Performance Evaluation: Workability> The test piece was stretched in a circulating air dryer at 150° C. and the elongation at break was evaluated. The test piece was a partially cured coating film with a length of 13 cm and a width of 1.5 cm ( 1) ~ (13) and (C1) ~ (C6). ◎: Elongation at break is 100% or more but 300% or less ○: Elongation at break is 40% or more but less than 100% ×: Elongation at break is less than 40% or a thermosetting film cannot be produced

<Performance Evaluation: Viscosity> Touch the partially cured coating films (1) to (13) and (C1) to (C6) with your fingers, and evaluate the presence or absence of finger marks on the surface of the coating film. ○: No trace of fingers ×: No trace of fingers

<Performance evaluation: Transparency> Using a commercially available measuring device (product name "Haze Meter", model "HM-150", manufactured by Murakami Color Technology Research Institute Co., Ltd.), the hardened products (1) to (13) are measured And the haze values of (C1) to (C6), and the transparency of each cured product was evaluated. In addition, the haze value is measured based on Japanese Industrial Standards (JIS) K 7136:2000.

Table 1 shows the composition of the resin compositions (1) to (13) and the performance evaluation results. The composition of the resin compositions (C1) to (C6) and the results of the performance evaluation are shown in Table 2.

[Table 1]

[Table 2]

The meanings of the terms in Tables 1 to 2 are as follows. (A-1): (meth)acrylic copolymer solution obtained in Synthesis Example 1 (hydroxyl group concentration is 4.7 mmol/g, propylene acetyl equivalent is 214 g/eq) (A-2): Synthesis Example 2 The obtained (meth)acrylic copolymer solution (hydroxyl group concentration 2.8 mmol/g, acryl equivalent 356 g/eq) (A-3): (meth)acrylic copolymer obtained in Synthesis Example 3 Solution (hydroxyl group concentration is 1.6 mmol/g, propylene acetyl equivalent is 635 g/eq) (B-1): dipentaerythritol polyacrylate (product name "ARONIX M-403", manufactured by East Asia Synthetic Co., Ltd., hydroxyl group concentration 1.6 mmol/g, 5-6 functions) (B-2): Dipentaerythritol hexaacrylate (product name "Miramer M600", manufactured by TOYO CHEMICALS Co., Ltd., hydroxyl group concentration 0.08 mmol/g, 6 functions) (B -3): Dipropylene glycol diacrylate (product name "Miramer M222", manufactured by TOYO CHEMICALS Co., Ltd., hydroxyl group concentration 0.44 mmol/g, 2 functions) (C-1): isocyanurate of hexamethylene diisocyanate Ester (product name "CORONATE HK", manufactured by Tosoh Corporation) (C-2): adduct of hexamethylene diisocyanate (product name "CORONATE HL", manufactured by Tosoh Corporation) ( C-3): Allophanate of hexamethylene diisocyanate (product name "CORONATE 2770", manufactured by Tosoh Corporation)

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Claims (11)

An active energy ray-curable resin composition comprising: (meth)acrylic copolymer (A), which is a radical polymer of monomer component (a1) and α,β-unsaturated carboxylic acid (a2) Reactant with a hydroxyl group concentration of 2 mmol/g or more and a (meth)acryl acetyl equivalent of 400 eq/g or less. The monomer component contains an epoxy-containing mono(meth)acrylate; Group) acrylate (B), which has at least three (meth)acryloyl groups and has a hydroxyl group concentration of 0.1 mmol/g or more; and, a polyfunctional isocyanate (C). The active energy ray-curable resin composition according to claim 1, wherein the (A) component has a hydroxyl group concentration of 2 mmol/g or more and 5 mmol/g or less, and the (meth)acryloyl equivalent of the (A) component is 150g/eq or more and 400g/eq or less, (B) component has 3 or more and 6 or less (meth)acryloyl groups, and (B) component has a hydroxyl group concentration of 0.1mmol/g or more and 2mmol/g or less . The active energy ray-curable resin composition according to claim 1 or 2, wherein the mass ratio of the solid content of the component (A) to the component (B) is (A)/(B)=30/70 to 99/ 1. The active energy ray-curable resin composition according to any one of claims 1 to 3, wherein the mass ratio of the solid components of (A) and (B) to (C) is [(A)+ (B)]/(C) = 60/40 to 99/1. The active energy ray-curable resin composition according to any one of claims 1 to 4, which contains a photopolymerization initiator (D). The active energy ray-curable resin composition according to any one of claims 1 to 5, which contains a fluorine-containing compound (E). The active energy ray-curable resin composition according to any one of claims 1 to 6, which contains inorganic fine particles (F). A partially cured product obtained by heating the active energy ray-curable resin composition according to any one of claims 1 to 7 and having an elongation at break of 40% or more and 300% or less. A cured product which is the cured product of the active energy ray-curable resin composition according to any one of claims 1 to 7. A laminate having a partially hardened product according to claim 8 or a hardened product according to claim 9 on at least one surface of a substrate surface. A curing method in which the active energy ray-curable resin composition according to any one of claims 1 to 7 is partially cured by heating and then irradiated with active energy rays to further cure.