Active energy ray curable composition and laminate

Abstract

To provide an active energy ray-curable composition from which a cured product excellent in adhesion to substrate and scratch resistance can be obtained, and to provide a laminate covered with a cured product of said active energy ray-curable composition.SOLUTION: Provided is an active energy ray-curable composition comprising a polymer A of a vinyl-based monomer having an acid value of 10 or more and 100 or less, (meth)acrylate B having 4 or more and 6 or less (meth)acryloyl groups in the molecule, and (meth)acrylate C having 2 or more and 3 or less (meth)acryloyl groups in the molecule.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to an active energy ray curable composition suitable for coating a floor material, and a laminate having a cured product of the curable composition.

Background Art

[0002] Floor materials used for floors in fast food restaurants, convenience stores, department stores, gymnasiums, hospitals, offices, residences, factories, etc. include floor materials with a coating film provided on a base material such as a polymerization system material like vinyl chloride, a woody material like flooring, a ceramic material like porcelain tiles, a stone material like marble, a concrete system material like mortar, and a metal system material like an iron plate.

[0003] When providing a coating film on these base materials, an active energy ray curable composition for floors having good abrasion resistance, such as those described in Patent Documents 1 and 2, is used.

Prior Art Documents

Patent Documents

[0004]

Patent Document 1

Patent Document 2

Summary of the Invention

Problems to be Solved by the Invention

[0005] However, the compositions described in Patent Documents 1 and 2 have a problem of poor adhesion to the base material.

[0006] An object of the present invention is to provide an active energy ray curable composition capable of obtaining a cured product excellent in adhesion to a base material and abrasion resistance, and to provide a laminate coated with the cured product of the active energy ray curable composition.

Means for Solving the Problems

[0007] That is, the above object of the present invention can be solved by the following means [1] to

[12] .

[0008] [1] An active energy ray curable composition containing a polymer A of a vinyl monomer having an acid value of 10 or more and 100 or less, a (meth)acrylate B having 4 or more and 6 or less (meth)acryloyl groups in the molecule, and a (meth)acrylate C having 2 or more and 3 or less (meth)acryloyl groups in the molecule. [2] The active energy ray curable composition according to [1], wherein the polymer A is 1% by mass or more and 20% by mass or less based on the total amount of the active energy ray curable composition. [3] The active energy ray curable composition according to [1] or [2], wherein the (meth)acrylate B is 20% by mass or more and 60% by mass or less based on the total amount of the active energy ray curable composition. [4] The active energy ray curable composition according to any one of [1] to [3], wherein the (meth)acrylate B is a polyester (meth)acrylate. [5] The active energy ray curable composition according to any one of [1] to [4], wherein the (meth)acrylate C is 20% by mass or more and 60% by mass or less based on the total amount of the active energy ray curable composition. [6] The active energy ray curable composition according to any one of [1] to [5], wherein the (meth)acrylate C is at least one of epoxy (meth)acrylate and ethylene oxide modified (meth)acrylate. [7] The active energy ray curable composition according to any one of [1] to [6], further containing a (meth)acrylate D having one (meth)acryloyl group in the molecule. [8] The active energy ray curable composition according to any one of [1] to [7], wherein the (meth)acrylate D is 1% by mass or more and 20% by mass or less based on the total amount of the active energy ray curable composition. [9] The active energy ray curable composition according to any one of [1] to [8], further containing a photopolymerization initiator E.

[10] The active energy ray curable composition according to any one of [1] to [9], wherein the photoinitiator E is 1% by mass or more and 20% by mass or less based on the total amount of the active energy ray curable composition.

[11] The active energy ray curable composition according to any one of [1] to

[10] , wherein the viscosity of the active energy ray curable composition at 25 ° C is 500 mPa·s or more and 5000 mPa·s or less.

[12] The hardening of the active energy ray curable composition according to any one of [1] to

[11] A laminate containing the cured product.

Effect of the Invention

[0009] According to the present invention, it is possible to provide an active energy ray curable composition that can obtain a cured product excellent in adhesion to a substrate and scratch resistance, and a laminate coated with the cured product of the active energy ray curable composition.

Mode for Carrying Out the Invention

[0010] The active energy ray curable composition of the present invention contains a polymer A of a vinyl monomer having an acid value of 10 or more and 100 or less, a (meth)acrylate B having 4 or more and 6 or less (meth)acryloyl groups in the molecule, and a (meth)acrylate C having 2 or more and 3 or less (meth)acryloyl groups in the molecule.

[0011] <Polymer A> In the present invention, it is necessary to contain a polymer A of a vinyl monomer having an acid value of 10 or more and 100 or less.

[0012] The higher the acid value is, the more preferable it is from the viewpoint of adhesion to the substrate, and the lower the acid value is, the more preferable it is from the viewpoint of storage stability, and 15 or more and 80 or less is more preferable.

[0013] The content of the polymer A in the active energy ray curable composition of the present invention is preferably 1% by mass or more and 20% by mass or less based on the total amount of the curable composition from the viewpoint of adhesion. More preferably, it is 10% by mass or less from the viewpoint of scratch resistance.

[0014] The weight-average molecular weight of the polymer A determined by gel permeation chromatography is preferably 5000 or more, more preferably 10000 or more, from the viewpoint of coating workability. Further, it is preferably 300000 or less, more preferably 50000 or less.

[0015] The polymer A may be a polymer obtained by polymerizing a vinyl monomer alone or a copolymer obtained by polymerizing a mixture of vinyl monomers.

[0016] Specific examples of the vinyl monomer include, for example, alkyl (meth) acrylates such as methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, t-butyl (meth) acrylate, isobutyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-nonyl (meth) acrylate; cyclohexyl (meth) acrylate, dicyclopentanyl (meth) acrylate (Meth)acrylates having an alicyclic skeleton such as isobornyl (meth)acrylate, dicyclopentenyl (meth)acrylate, 2-dicyclopentenoxyethyl (meth)acrylate; alkoxyalkyl (meth)acrylates such as methoxyethyl (meth)acrylate, ethoxyethyl (meth)acrylate, butoxyethyl (meth)acrylate, methoxyethoxyethyl (meth)acrylate, ethoxyethoxyethyl (meth)acrylate; hydroxyalkyl (meth)acrylates such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate; (meth)acrylates having a benzene ring such as benzyl (meth)acrylate; other (meth)acrylates such as tetrahydrofurfuryl (meth)acrylate, an adduct of 2-hydroxyethyl (meth)acrylate and ethylene oxide, an adduct of 2-hydroxyethyl (meth)acrylate and propylene oxide, an adduct of 2-hydroxyethyl (meth)acrylate and ε-caprolactone; styrene or styrene derivatives such as styrene, α-methylstyrene, p-t-butylstyrene, vinyltoluene; amide group-containing compounds such as N,N-dimethyl (meth)acrylamide, N,N-diethyl (meth)acrylamide; unsaturated carboxylic acids such as (meth)acrylic acid, itaconic acid, maleic acid, fumaric acid; polymerizable unsaturated nitriles such as (meth)acrylonitrile; unsaturated carboxylic acid esters such as diethyl maleate, dibutyl maleate, dibutyl fumarate, diethyl itaconate, dibutyl itaconate; vinyl esters such as vinyl acetate, vinyl propionate, etc. are mentioned.

[0017] Among them, methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, styrene, and (meth)acrylic acid are preferable from the viewpoints of adhesion to the substrate, scratch resistance, and warpage.

[0018] These vinyl monomers may be used alone or in combination of two or more.

[0019] Here, “(meth)acrylate” means at least one of “acrylate” and “methacrylate”. “(meth)acryloyl” means at least one of “acryloyl” and “methacryloyl”. “(meth)acrylic acid” means at least one of “acrylic acid” and “methacrylic acid”. “(meth)acrylamide” means at least one of “acrylamide” and “methacrylamide”.

[0020] The polymer A can be obtained by using a solution polymerization method, a suspension polymerization method, a bulk polymerization method, an emulsion polymerization method, etc. in the presence of a radical polymerization initiator. Among these polymerization methods, the suspension polymerization method is preferable from the viewpoint of solvent-free.

[0021] (Meth)acrylate B having 4 or more and 6 or less (meth)acryloyl groups in the molecule (Meth)acrylate B having 4 or more and 6 or less (meth)acryloyl groups in the molecule contributes to the scratch resistance of the cured product of the active energy ray curable composition of the present invention. Further, since the (meth)acrylate B has good polymerization activity, it contributes to the curability of the active energy ray curable composition of the present invention.

[0022] The content of the (meth)acrylate B in the active energy ray curable composition of the present invention is preferably 20% by mass or more and 60% by mass or less based on the total amount of the active energy ray curable composition. The more the (meth)acrylate B is, the higher the scratch resistance becomes, and the less it is, the smaller the warpage becomes. From the viewpoint of the balance between scratch resistance and warpage, 25% by mass or more and 55% by mass or less are more preferable.

[0023] Specific examples of the (meth)acrylate B include pentaerythritol tetra(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate Examples include trimethylolpropane tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, dipentaerythritol hepta(meth)acrylate, dipentaerythritol octa(meth)acrylate, and the like. Further, urethane poly(meth)acrylates such as urethane hexa(meth)acrylate obtained by reacting isophorone diisocyanate with pentaerythritol tri(meth)acrylate, and polyesters such as polyester (meth)acrylate obtained by reacting trimethylolethane with succinic acid and ( poly(meth)acrylate obtained by reacting (meth)acrylic acid, etc. Examples of the poly(meth)acrylate include those described above.

[0024] Among them, as the (meth)acrylate B, a (meth)acrylate having four (meth)acryloyl groups in the molecule is preferable from the viewpoints of scratch resistance and warpage, and a polyester (meth)acrylate is more preferable from the viewpoint of antifouling property.

[0025] As the (meth)acrylate B, one kind of compound may be used alone, or two or more kinds of compounds may be used in combination.

[0026] <(meth)acrylate C having two or more and three or less (meth)acryloyl groups in the molecule> The (meth)acrylate C having two or more and three or less (meth)acryloyl groups in the molecule can suppress the viscosity of the curable composition and form a cured product having an excellent balance between scratch resistance and warpage.

[0027] In the active energy ray curable composition of the present invention, the content of the (meth)acrylate C is preferably 20% by mass or more and 60% by mass or less based on the total amount of the active energy ray curable composition. The more the (meth)acrylate C is, the higher the scratch resistance becomes, and the less the warpage becomes. From the viewpoint of the balance between scratch resistance and warpage, 25% by mass or more and 55% by mass or less is more preferable.

[0028] Specific examples of the above-mentioned (meth)acrylate C include 1,3-propylene glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,5-pentanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, diethylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, trimethylolethane di(meth)acrylate, tetraethylene glycol di(meth)acrylate, 2-butene-1,4-di(meth)acrylate, cyclohexane-1,4-dimethanol di(meth)acrylate, hydrogenated bisphenol A di(meth)acrylate, tricyclodecane dimethanol di(meth)acrylate, trimethylolpropane di(meth)acrylate, dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, 2,2-bis-(4-(meth)acryloyloxypropoxyphenyl)propane, 2,2-bis-(4-(meth)acryloyloxy(2-hydroxypropoxyphenyl))propane, bis-(2-methacryloyloxyethyl)phthalate and other difunctional (meth)acrylates; epoxy di(meth)acrylates such as epoxy di(meth)acrylate obtained by reacting bisphenol A type diepoxy with (meth)acrylic acid; urethane di(meth)acrylate obtained by reacting isophorone diisocyanate with 2-hydroxypropyl (meth)acrylate, urethane di(meth)acrylate obtained by reacting dicyclohexylmethane diisocyanate with 2-hydroxyethyl (meth)acrylate, dicyclohexylmethane diisocyanate and poly(n= ), urethane di(meth)acrylate obtained by reacting tolylene diisocyanate with 2-hydroxyethyl (meth)acrylate, and other urethane di(meth)acrylates; ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, butylene glycol di(meth)acrylate, hexylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, and other polyalkylene glycol di(meth)acrylates; glycerol tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, and other polyfunctional (meth)acrylates. As specific examples of the above (meth)acrylate C, 1,3-propylene glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,5-pentanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, diethylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, trimethylolethane di(meth)acrylate, tetraethylene glycol di(meth)acrylate, 2-butene-1,4-di(meth)acrylate, cyclohexane-1,4-dimethanol di(meth)acrylate, hydrogenated bisphenol A di(meth)acrylate, tricyclodecane dimethanol di(meth)acrylate, trimethylolpropane di(meth)acrylate, dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, 2,2-bis-(4-(meth)acryloyloxypropoxyphenyl)propane, 2,2-bis-(4-(meth)acryloyloxy(2-hydroxypropoxyphenyl))propane, bis-(2-methacryloyloxyethyl)phthalate and other difunctional (meth)acrylates; epoxy di(meth)acrylates such as epoxy di(meth)acrylate obtained by reacting bisphenol A type diepoxy with (meth)acrylic acid; urethane di(meth)acrylate obtained by reacting isophorone diisocyanate with 2-hydroxypropyl (meth)acrylate, urethane di(meth)acrylate obtained by reacting dicyclohexylmethane diisocyanate with 2-hydroxyethyl (meth)acrylate, dicyclohexylmethane diisocyanate and poly(n= ), urethane di(meth)acrylate obtained by reacting tolylene diisocyanate with 2-hydroxyethyl (meth)acrylate, and other urethane di(meth)acrylates; ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, butylene glycol di(meth)acrylate, hexylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, and other polyalkylene glycol di(meth)acrylates; glycerol tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, and other polyfunctional (meth)acrylates. As specific examples of the above (meth)acrylate C, 1,3-propylene glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,5-pentanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, diethylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, trimethylolethane di(meth)acrylate, tetraethylene glycol di(meth)acrylate, 2-butene-1,4-di(meth)acrylate, cyclohexane-1,4-dimethanol di(meth)acrylate, hydrogenated bisphenol A di(meth)acrylate, tricyclodecane dimethanol di(meth)acrylate, trimethylolpropane di(meth)acrylate, dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, 2,2-bis-(4-(meth)acryloyloxypropoxyphenyl)propane, 2,2-bis-(4-(meth)acryloyloxy(2-hydroxypropoxyphenyl))propane, bis-(2-methacryloyloxyethyl)phthalate and other difunctional (meth)acrylates; epoxy di(meth)acrylates such as epoxy di(meth)acrylate obtained by reacting bisphenol A type diepoxy with (meth)acrylic acid; urethane di(meth)acrylate obtained by reacting isophorone diisocyanate with 2-hydroxypropyl (meth)acrylate, urethane di(meth)acrylate obtained by reacting dicyclohexylmethane diisocyanate with 2-hydroxyethyl (meth)acrylate, dicyclohexylmethane diisocyanate and poly(n= ), urethane di(meth)acrylate obtained by reacting tolylene diisocyanate with 2-hydroxyethyl (meth)acrylate, and other urethane di(meth)acrylates; ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, butylene glycol di(meth)acrylate, hexylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, and other polyalkylene glycol di(meth)acrylates; glycerol tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, and other polyfunctional (meth)acrylates. As specific examples of the above (meth)acrylate C, 1,3-propylene glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,5-pentanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, diethylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, trimethylolethane di(meth)acrylate, tetraethylene glycol di(meth)acrylate, 2-butene-1,4-di(meth)acrylate, cyclohexane-1,4-dimethanol di(meth)acrylate, hydrogenated bisphenol A di(meth)acrylate, tricyclodecane dimethanol di(meth)acrylate, trimethylolpropane di(meth)acrylate, dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, 2,2-bis-(4-(meth)acryloyloxypropoxyphenyl)propane, 2,2-bis-(4-(meth)acryloyloxy(2-hydroxypropoxyphenyl))propane, bis-(2-methacryloyloxyethyl)phthalate and other difunctional (meth)acrylates; epoxy di(meth)acrylates such as epoxy di(meth)acrylate obtained by reacting bisphenol A type diepoxy with (meth)acrylic acid; urethane di(meth)acrylate obtained by reacting isophorone diisocyanate with 2-hydroxypropyl (meth)acrylate, urethane di(meth)acrylate obtained by reacting dicyclohexylmethane diisocyanate with 2-hydroxyethyl (meth)acrylate, dicyclohexylmethane diisocyanate and poly(n= 6 to 15) Urethane di(meth)acrylates such as urethane di(meth)acrylate obtained by reacting a urethanization reaction product of tetramethylene glycol with 2-hydroxyethyl (meth)acrylate; polyester di(meth)acrylates such as polyester di(meth)acrylate obtained by reacting polyethylene glycol with succinic acid and (meth)acrylic acid; trifunctional (meth)acrylates such as tris(2-(meth)acryloyloxyethyl) isocyanurate, trimethylolpropane tri(meth)acrylate, ethylene oxide-modified trimethylolpropane tri(meth)acrylate, caprolactone-modified trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, and ethylene oxide-modified pentaerythritol tri(meth)acrylate.

[0029] Among them, from the viewpoint of scratch resistance, epoxy (meth)acrylates such as epoxy di(meth)acrylate obtained by reacting bisphenol A type diepoxy with (meth)acrylic acid, and ethylene oxide-modified (meth)acrylates such as ethylene oxide-modified trimethylolpropane tri(meth)acrylate are preferable. The number of ethylene oxide modifications of ethylene oxide-modified trimethylolpropane tri(meth)acrylate is more preferably 1 mol or more and 10 mol or less.

[0030] As the (meth)acrylate C, one kind of compound may be used alone, or two or more kinds of compounds may be used in combination.

[0031] <(Meth)acrylate D having one (meth)acryloyl group in the molecule> The active energy ray-curable composition of the present invention preferably contains (meth)acrylate D having one (meth)acryloyl group in the molecule. The (meth)acrylate D can reduce the viscosity of the active energy ray-curable composition.

[0032] From the viewpoint of the balance between viscosity and scratch resistance, the content of the (meth)acrylate D in the active energy ray-curable composition of the present invention is preferably 1% by mass or more and 20% by mass or less, more preferably 3% by mass or more and 10% by mass or less, based on the total amount of the active energy ray-curable composition. The larger the amount of the (meth)acrylate D, the lower the viscosity, and the smaller the amount, the higher the scratch resistance.

[0033] Specific examples of the (meth)acrylate D include hydroxyalkyl (meth)acrylates such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate; alkyl (meth)acrylates such as methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isooctyl (meth)acrylate, isodecyl (meth)acrylate, lauryl (meth)acrylate, isomyristyl (meth)acrylate, stearyl (meth)acrylate, and isostearyl (meth)acrylate; (meth)acrylates having an alicyclic skeleton such as cyclohexyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentenyl oxyethyl (meth)acrylate, and isobornyl (meth)acrylate; polyalkylene glycol mono (meth)acrylates such as ethylene glycol mono (meth)acrylate and diethylene glycol mono (meth)acrylate; (meth)acrylates having a benzene ring such as benzyl (meth)acrylate and phenoxyethyl (meth)acrylate; (meth)acrylates having a phthalic acid ester such as 2-(meth)acryloyloxyethyl phthalate, 2-(meth)acryloyloxyethyl-2-hydroxyethyl phthalate, 2-(meth)acryloyloxyethyl hexahydrophthalate, and 2-(meth)acryloyloxypropyl phthalate; amino group-containing compounds such as acryloylmorpholine; (meth)acrylamide, isopropylacrylamide, diacetone a Amide group-containing compounds such as acrylamide, N-methylol acrylamide, N-n-butoxymethyl acrylamide; epoxy group-containing (meth)acrylates such as 4-hydroxybutyl (meth)acrylate glycidyl ether, glycidyl (meth)acrylate; alkoxysilyl group-containing (meth)acrylates such as 3-(meth)acryloyloxypropyltrimethoxysilane; tetrahydrofurfuryl (meth)acrylate, 2-methoxyethyl (meth)acrylate, butoxyethyl (meth)acrylate can be mentioned.

[0034] Among these, 4-hydroxybutyl acrylate is preferable from the viewpoints of viscosity, curability, and low skin irritation.

[0035] As the (meth)acrylate D, one kind of compound may be used alone, or two or more kinds of compounds may be used in combination.

[0036] <Photoinitiator E> The active energy ray-curable composition of the present invention may contain a photoinitiator. Since the photoinitiator generates radicals upon irradiation with active energy rays, it is blended for the purpose of efficiently obtaining a cured product of the active energy ray-curable composition.

[0037] From the viewpoints of the curability of the active energy ray-curable composition and the hardness of the cured product of the active energy ray-curable composition, the content of the photoinitiator is preferably 1% by mass or more and 20% by mass or less, more preferably 2% by mass or more and 15% by mass or less, based on the total amount of the active energy ray-curable composition.

[0038] Specific examples of the photoinitiator include, for example, benzophenones such as benzophenone, 4-methylbenzophenone, 2-methylbenzophenone, 4,4'-bis(diethylamino)benzophenone, 2,4,6-trimethylbenzophenone, 4-phenylbenzophenone; anthraquinones such as t-butylanthraquinone, 2-ethylanthraquinone; α-hydroxyacetophenones such as 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-hydroxycyclohexyl-phenylketone, 2-hydroxy-1-{4-[4-(2-hydroxy-2-methylpropionyl)benzyl]phenyl}-2-methylpropan-1-one; α-aminoacetophenones such as 2-benzyl-2-dimethylamino-4-morpholinobutyrophenone, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-(dimethylamino)-2-(4-methylbenzyl)-1-(4-morpholinophenyl)-butan-1-one; acylphosphine oxides such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide; benzoin alkyl ethers such as benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether; methyl orthobenzoylbenzoate, diethoxyacetophenone, benzyl dimethyl ketal, diethylthioxanthone, isopropylthioxanthone, methyl benzoylformate, oxy-phenyl-acetic acid 2-[2-oxo-2-phenyl-acetoxy-eth xy]ethyl ester, oxy-phenyl-acetic acid 2-[2-hydroxy] -ethoxy-ethyl ester, etc. can be mentioned.

[0039] <Other components> In addition, the active energy ray-curable composition of the present invention may contain, as other additives, a leveling agent, an antifoaming agent, an anti-settling agent, a lubricant, an abrasive, a rust inhibitor, an antistatic agent, a sensitizer, a light stabilizer, an ultraviolet absorber, a polymerization inhibitor, an antioxidant, an anti-clouding agent, a dispersant, a thickener, an anti-sagging agent, a desiccant, an adhesion promoter, a film modifier, a slip agent, a scratch inhibitor, a plasticizer, a matting agent, a low-shrinkage agent, an antibacterial agent, an antifungal agent, an antifouling agent, a flame retardant, a curing accelerator, a deterioration inhibitor, a photo-polymerization accelerator, a thermal initiator, a PP adhesion-imparting agent (chlorinated PP), a thixotropic agent, a dye, a pigment, fine particles, reactive fine particles, a bactericide, and various other additives can be added. From the viewpoints of preventing repellency and the smoothness of the coating film, it is preferable to add a leveling agent to the active energy ray-curable composition of the present invention. Examples of the leveling agent include fluorine-based, silicon-based, and acrylic-based ones. When laminating two or more layers of the cured product of the active energy ray-curable composition of the present invention, it is preferable to add an acrylic-based leveling agent that can enhance the adhesion between layers.

[0040] Furthermore, the active energy ray-curable composition of the present invention may contain a solvent that is a volatile component. From the viewpoints of shortening the drying time after coating and reducing the odor during coating, the content of the solvent is preferably 0.1% by mass or less, more preferably 0.05% by mass or less, and even more preferably 0.02% by mass or less, based on the total amount of the active energy ray-curable composition. Here, the solvent shall not contain ethylenically unsaturated compounds.

[0041] Examples of the method for producing the active energy ray-curable composition of the present invention include a method of mixing and stirring each component using a commonly used stirrer.

[0042] The active energy ray-curable composition of the present invention is preferably uniform without causing layer separation from the viewpoint of the smoothness of the coating film during coating.

[0043] <Viscosity> The viscosity of the active energy ray curable composition of the present invention is preferably 500 mPa·sec or more and 4000 mPa·sec or less, more preferably 1000 mPa·sec or more and 2000 mPa·sec or less, from the viewpoint of workability during coating. Here, the viscosity means a value measured using an E-type viscometer (TVE-20H type viscometer manufactured by Toki Sangyo Co., Ltd.) at 25°C in accordance with JIS K7117.

[0044] <Laminate> The laminate of the present invention is obtained by applying the active energy ray curable composition of the present invention to a substrate and curing it. The film thickness of the cured product of the active energy ray curable composition is preferably in the range of 1 μm or more and 150 μm or less. Examples of the active energy ray include ultraviolet rays and electron beams. For example, when irradiating ultraviolet rays using a high-pressure mercury lamp, the amount of ultraviolet energy irradiated is the integrated light amount of 25 mJ / cm 2 or more and 2000 mJ / cm 2 or less is preferable.

[0045] When the substrate is a floor material, examples of the material of the floor material include thermoplastic resins such as polyvinyl chloride-based resins, polyolefin-based resins, polystyrene-based resins, polyester-based resins, and acrylic-based resins, and thermosetting resins such as phenol resins, epoxy resins, urethane resins, urea resins, and melamine resins. Among these, thermoplastic resins are preferable, and vinyl chloride-based resins are more preferable, from the viewpoints of processability and ease of construction as a floor material.

[0046] In addition, in this laminate, two or more layers of the cured product of the curable composition of the present invention may be laminated on the floor material, and a layer such as WAX for the purpose of gloss or slip prevention may be provided on the surface of the cured product of the active energy ray curable composition of the laminate.

[0047] Examples of the method for applying the active energy ray curable composition of the present invention to the floor material include methods such as brush coating, roller coating, mutton coating, mop coating, roll coating, spray coating, spin coating, flow coating, dipping, electrostatic coating, and screen printing. Roll coating and flow coating are preferable from the viewpoint of workability.

Example

[0048] Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited thereto. In the examples, "parts" means "parts by mass". Further, the weight average molecular weight was measured by the following method, and the evaluation method of the obtained cured product is as follows. (Weight average molecular weight) After adjusting the polymer to a solution concentration of 0.4% by weight in tetrahydrofuran, it was injected into a gel permeation chromatography apparatus manufactured by Tosoh Corporation using columns manufactured by Tosoh Corporation (GE4000HXL and G2000HXL) (injection volume 100 μl), and the weight average molecular weight was measured by the gel permeation chromatography method at a flow rate of 1 ml / min (eluent tetrahydrofuran) and a column temperature of 40°C with reference to polystyrene.

[0049] (Storage stability of the active energy ray curable composition) The curable composition was placed in a 200 ml glass bottle, and the state after standing for 1 day in a temperature environment of 22°C was confirmed and evaluated according to the following evaluation criteria. "○": No separation is observed in the active energy ray curable composition after standing. "×": Separation is observed in the active energy ray curable composition after standing.

[0050] (Viscosity) In accordance with JIS K7117, the viscosity of the curable composition at 25°C was measured using an E-type viscometer (TVE-20H type viscometer manufactured by Toki Sangyo Co., Ltd.), and the viscosity was evaluated according to the following evaluation criteria.·Evaluation criteria "○": 1000 mPa·sec or more and less than 2100 mPa·sec. "×": 2100 mPa·sec or more and less than 4000 mPa·sec.

[0051] (Warpage of the cured product of the active energy ray curable composition) An active energy ray-curable composition was applied onto a polyester film Cosmo Shine (film thickness: 125 μm) manufactured by Toyobo Co., Ltd. (hereinafter, appropriately referred to as "PET film") using an applicator so that the film thickness after curing would be 20 μm, and then irradiated with ultraviolet rays having an integrated light quantity of 100 mJ / cm 2 in the wavelength range of 340 to 380 nm using a high-pressure mercury lamp in the air to effect curing. The laminate having the obtained cured product was cut into 5 cm × 5 cm, and the obtained sample was placed on a flat surface and pressed at the center with a load of 125 g / cm 2 , and the total value of the heights at the four corners was measured as the warp. The warp was evaluated according to the following evaluation criteria. · Evaluation criteria "○": The total value of the warp is 8 mm or less. "×": The total value of the warp exceeds 8 mm.

[0052] (Scratch resistance) An active energy ray-curable composition was applied onto a semi-rigid CT composition vinyl floor tile manufactured by Tajima Co., Ltd. (hereinafter, appropriately referred to as "PVC tile") using an applicator so that the film thickness after curing would be 20 μm, and then irradiated with ultraviolet rays having an integrated light quantity of 100 mJ / cm 2 in the wavelength range of 340 to 380 nm using a high-pressure mercury lamp in the air to effect curing. For the obtained cured product, a scratch resistance test was carried out under the following conditions using a planar friction tester manufactured by Coating Tester Co., Ltd. Load: 103 g / cm 2 Test method: Steel wool #3, 60 mm / sec, 100 reciprocations Using a color change gloss meter VG-7000 manufactured by Nippon Denshoku Industries Co., Ltd., the 60° reflectance of the cured product before and after the test was measured. The gloss retention rate was calculated by the following formula, and the scratch resistance was evaluated according to the following evaluation criteria based on the gloss retention rate. Gloss retention rate (%) = (60° reflectance after the test) / (60° reflectance before the test) × 100 · Evaluation criteria "○": The gloss retention rate is greater than 60%. "×": The gloss retention rate is 60% or less.

[0053] (Adhesion) An active energy ray-curable composition was applied onto a semi-rigid CT of a composition vinyl floor tile manufactured by Tajima Co., Ltd. (hereinafter, appropriately referred to as "PVC tile") using an applicator so that the film thickness after curing was 20 μm, and then irradiated with ultraviolet rays having an integrated light quantity of 100 mJ / cm2 at wavelengths of 340 to 380 nm using a high-pressure mercury lamp in the air to cure it. With respect to the obtained cured product, cuts were made in the shape of 1 mm square × 100 squares, and the adhesion when peeled off with cellophane (registered trademark) was confirmed, and the adhesion was evaluated according to the following evaluation criteria. ·Evaluation Criteria 「◎」: The number of squares remaining after the test is 80 or more 「○」: The number of squares remaining after the test is 70 or more and less than 80 「×」: The number of squares remaining after the test is less than 70

[0054] <Example 1> 3 parts of Polymer A (a polymer of methyl methacrylate / methacrylic acid = 89 / 11 (weight average molecular weight by GPC: 25,000, acid value: 21)), 40 parts of a tetrafunctional polyester acrylate (trade name: MIRAMER PS4140, manufactured by MIWON Co., Ltd.), 10 parts of a difunctional epoxy acrylate (trade name: MIRAMER PE210, manufactured by MIWON Co., Ltd.), 40 parts of ethylene oxide 3 mol-modified trimethylolpropane triacrylate (trade name: MIRAMER M3130, manufactured by MIWON Co., Ltd.), 7 parts of 4-hydroxybutyl acrylate (trade name: 4-HBA, manufactured by Osaka Organic Chemical Industry Co., Ltd.), 2 parts of benzophenone, 2 parts of methyl benzoyl formate (trade name SPEEDCURE MBF, manufactured by LAMBSON Co., Ltd.), 0.1 part of an acrylic leveling agent (trade name: BYK-350, manufactured by BYK-Chemie Japan Co., Ltd.), 0.2 part of a wetting dispersant Anti-Terra U-100 (trade name: ANTI-TERRA-U100, manufactured by BYK-Chemie Japan Co., Ltd.), 0.1 part of a polymerization system antifoaming agent (trade name: BYK-1790, manufactured by BYK-Chemie Japan Co., Ltd.), and 8 parts of a matting agent Silophobic 200 (trade name: SYLOPHOBIC200, manufactured by Fuji Silysia Chemical Ltd.) were mixed and stirred for 30 minutes to prepare a uniform liquid active energy ray-curable composition. The results of performing the above various evaluations on the obtained active energy ray-curable composition are shown in Table 1.

[0055] <Examples 2 to 5, Comparative Examples 1 to 3> An active energy ray-curable composition was prepared and evaluated in the same manner as in Example 1, except that the active energy ray-curable composition was prepared at the compounding ratios shown in Table 1. The evaluation results are shown in Table 1.

[0056]

Table 1

[0057] The abbreviations and names in Table 1 represent the following compounds. "Polymer A": A polymer of methyl methacrylate / methacrylic acid = 89 / 11 (weight average molecular weight by GPC: 25,000, acid value: 21). "Polymer B": A polymer of methyl methacrylate / ethyl acrylate / methacrylic acid = 84 / 13 / 3 (weight average molecular weight by GPC: 65,000, acid value: 19). "Polymer C": A polymer of methyl methacrylate / methacrylic acid = 98 / 2 (weight average molecular weight by GPC: 25,000, acid value: 11). "Polymer D": A polymer of methyl methacrylate / ethyl acrylate / methacrylic acid = 95 / 4 / 1 (weight average molecular weight by GPC: 85,000, acid value: 3). "Polymer E": A polymer of methyl methacrylate / butyl methacrylate / butyl acrylate / styrene / methacrylic acid = 32 / 15 / 15 / 15 / 23 (weight average molecular weight by GPC: 50,000, acid value: 150). "Tetrafunctional polyester acrylate": Tetrafunctional polyester acrylate (trade name: MIRAMER PS4140, manufactured by MIWON). "Hexafunctional urethane acrylate": Hexafunctional urethane acrylate (trade name: MIRAMER PU610, manufactured by MIWON). "Bifunctional epoxy acrylate": Bifunctional epoxy acrylate (trade name: MIRAMER PE210, manufactured by MIWON). "EO3mol modified TMPTA": Ethylene oxide 3mol modified trimethylolpropane triacrylate (trade name: MIRAMER M3130, manufactured by MIWON). "3-functional urethane acrylate": Aliphatic 3-functional urethane acrylate (trade name: MIRAMER PU340, manufactured by MIWON). "2-functional urethane acrylate": Aliphatic 2-functional urethane acrylate (trade name: MIRAMER PU2560, manufactured by MIWON). "4-HBA": 4-hydroxybutyl acrylate (trade name: 4-HBA, manufactured by Osaka Organic Chemical Industry Co., Ltd.). "BP": Benzophenone "MBF": Methyl benzoyl formate (trade name SPEEDCURE MBF, manufactured by LAMBSON). "BYK-350": Acrylic leveling agent (trade name: BYK-350, manufactured by BYK-Chemie Japan). "BYK-399": Surface-active polymerization system leveling agent (trade name: BYK-399, manufactured by BYK-Chemie Japan). "ANTI-TERRA U-100": Dispersant composed of a salt of unsaturated polyamide amide and low molecular weight polyester acid (trade name: ANTI-TERRA-U100, manufactured by BYK-Chemie Japan). "BYK-1790": Polymerization system defoaming agent (trade name: BYK-1790, manufactured by BYK-Chemie Japan). "SYLOPHOBIC 200": Hydrophobic micronized silica (trade name: SYLOPHOBIC200, manufactured by Fuji Silysia Chemical Ltd.). "CERAFLOUR 1000": Organically modified polymer (trade name: CERAFLOUR1000, manufactured by BYK-Chemie Japan).

[0058] As shown in Table 1, since the oxidation of the polymer A of the vinyl monomer in the composition of Comparative Example 1 was less than 10, the adhesion was poor. Since the composition of Comparative Example 2 did not contain a (meth)acrylate having 4 or more and 6 or less (meth)acryloyl groups in the molecule, the warpage, scratch resistance, and adhesion were poor. Since the composition of Comparative Example 3 used a polymer having an acid value greater than 100, the storage stability was poor.

Claims

1. An active energy ray-curable composition for coating a bedding material (excluding compositions containing urethane (meth)acrylate), comprising: a polymer A of a vinyl monomer having an acid value of 10 or more and 100 or less; a (meth)acrylate B having 4 or more and 6 or less (meth)acryloyl groups in the molecule; a (meth)acrylate C having 2 or more and 3 or less (meth)acryloyl groups in the molecule; and a (meth)acrylate D having 1 (meth)acryloyl group in the molecule, wherein the polymer A includes a copolymer of a mixture of vinyl monomers including methyl (meth)acrylate and (meth)acrylic acid, the (meth)acrylate B includes a polyester (meth)acrylate, the (meth)acrylate C includes at least one of epoxy (meth)acrylate and ethylene oxide-modified (meth)acrylate, the (meth)acrylate D includes 4-hydroxybutyl acrylate, and the polymer A is 1% by mass or more and 20% by mass or less, the (meth)acrylate B is 20% by mass or more and 60% by mass or less, the (meth)acrylate C is 20% by mass or more and 60% by mass or less, and the (meth)acrylate D is 1% by mass or more and 20% by mass or less, based on the total amount of the active energy ray-curable composition. An active energy ray-curable composition.

2. The active energy ray-curable composition according to claim 1, further comprising a photopolymerization initiator E.

3. The active energy ray-curable composition according to claim 2, wherein the photopolymerization initiator E is 1% by mass or more and 20% by mass or less based on the total amount of the active energy ray-curable composition.

4. The active energy ray-curable composition according to any one of claims 1 to 3, wherein the viscosity of the active energy ray-curable composition at 25°C is 500 mPa·s or more and 5000 mPa·s or less.

5. A laminate comprising a cured product of the active energy ray-curable composition according to any one of claims 1 to 4.

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