Method for manufacturing a matte coating film, and excimer laser photocurable matte coating agent

Abstract

The present invention provides a method for manufacturing a matte coating film in which the matting agent does not fall off even if the coating film deteriorates. [Solution] A method for producing a matte coating film comprising the steps of (I) forming a coating film of an excimer laser photocurable matte coating agent on a substrate, (II) irradiating the coating film with ultraviolet light, (III) irradiating the coating film with excimer laser light, and (IV) irradiating the coating film with ultraviolet light or an electron beam, wherein the excimer laser photocurable matte coating agent contains (meth)acrylate, a photopolymerization initiator, and particles A having an average particle size of 1 nm to 10.0 μm, and the particles A are contained in an amount of 0.1 to 5% by mass relative to the nonvolatile components of the coating agent; and a matte coating agent used in the production method.

Description

Technical Field

[0001] The present invention relates to a method for producing a matte coating film and an excimer laser curable matte coating agent.

Background Art

[0002] Generally, for the purpose of imparting aesthetics such as matte finish (sometimes also referred to as low gloss), a coating agent containing an electron beam curable (sometimes also referred to as EB curable) or ultraviolet curable (sometimes also referred to as UV curable) matte agent is applied onto a substrate. (See, for example, Patent Documents 1 and 2). These are, for example, an active energy ray curable coating agent obtained by adding 5 to 20% by mass of inorganic fine particles, organic fine particles, etc., referred to as a matte agent, based on the total mass of the active energy ray curable compound (see Patent Document 1, paragraph 0025), or an active energy ray curable coating agent obtained by adding 0.5 to 50% by mass of a matte agent having an average particle size of 25 μm or less in terms of the non-volatile component of the total amount of the coating agent (see Patent Document 2, paragraphs 0033 to 0038). This is a method of obtaining a matte effect by curing with ultraviolet rays or electron beams, and it is an excellent method that achieves both a desired matte effect and effects such as scratch resistance and stain resistance.

[0003] Conventionally, matte designs have been mainly used in the field of interior decoration of building materials such as furniture, walls, ceilings, and floors. However, recently, there has been an increasing demand in the field of exterior decoration of building materials. The methods described in Patent Documents 1 and 2 are excellent methods that achieve both a matte effect and effects such as scratch resistance and stain resistance. However, they are mainly assumed for the field of interior decoration of building materials, and sometimes problems occur in the exterior field where high weather resistance against sunlight is required. In particular, when the matte agent is located near the surface of the coating film, the matte agent may fall off due to deterioration of the coating film, and defects and cracks may occur on the surface of the coating film. These defects and cracks can be confirmed as whitening with the naked eye, and furthermore, they can induce the progress of deterioration inside the coating film.

Prior Art Documents

Patent Documents

[0004] [Patent Document 1] WO2022 / 224830 [Patent Document 2] Japanese Patent Publication No. 2023-154507 [Overview of the Initiative] [Problems that the invention aims to solve]

[0005] The object of the present invention is to provide a method for manufacturing a matte coating film in which the matting agent does not fall off even if the coating film deteriorates, and a matte coating agent used in said manufacturing method. [Means for solving the problem]

[0006] In other words, the present invention comprises the steps of (I) forming a coating film of an excimer laser photocurable matte coating agent on a substrate, The process involves irradiating the coating film with ultraviolet light (II), The process involves irradiating the coating film with excimer laser light (III), The process includes, in this order, a step (IV) of irradiating the coating film with ultraviolet light or an electron beam, The present invention provides a method for producing a matte coating film, wherein the excimer laser photocurable matte coating agent contains (meth)acrylate, a photopolymerization initiator, and particles A having an average particle size of 1 nm to 10.0 μm, and the particles A are present in an amount of 0.1 to 5% by mass relative to the nonvolatile components of the coating agent.

[0007] The present invention also provides a method for producing the matte coating film described above, wherein the particles A are fine particles composed of silica and / or alumina with an average particle size of 1 nm to 10.0 μm.

[0008] Furthermore, the present invention relates to a particle A having an average particle size of 1 nm to 10.0 μm and a BET specific surface area of ​​25 to 400 m². 2The present invention provides a method for producing the matte coating film described above, comprising fine particles composed of silica and / or alumina, having a weight of / g, a heat loss of 0-7%, and a pH of 3-8.

[0009] The present invention also provides a method for producing the matte coating film described above, wherein the (meth)acrylate is at least one (meth)acrylate monomer selected from the group consisting of ethoxyethoxyethyl acrylate, ethoxyethoxyethanol acrylic acid polymer ester, ethylene oxide-modified 1,6-hexanediol di(meth)acrylate, tripropylene glycol di(meth)acrylate, neopentyl glycol diacrylate hydroxypivalate, di(meth)acrylate of a triol obtained by adding 3 moles or more of ethylene oxide or propylene oxide to 1 mole of trimethylolpropane, and tri(meth)acrylate of a triol obtained by adding 3 moles or more of ethylene oxide or propylene oxide to 1 mole of trimethylolpropane.

[0010] The present invention also provides an excimer laser photocurable matte coating agent for use in the method of manufacturing a matte coating film as described in item 1 above, which contains (meth)acrylate, a photopolymerization initiator, and particles A having an average particle size of 1 nm to 10.0 μm, wherein the particles A are present in an amount of 0.1 to 5% by mass relative to the non-volatile components of the coating agent. [Effects of the Invention]

[0011] The present invention provides a method for manufacturing a matte coating film in which the matting agent does not fall off even if the coating film deteriorates, and a matte coating agent used in the manufacturing method. [Modes for carrying out the invention]

[0012] ((meth)acrylate) The (meth)acrylate used in the excimer laser photocurable matte coating agent of the present invention includes known (meth)acrylate resins, (meth)acrylate monomers, (meth)acrylate oligomers, etc., that have a (meth)acryloyl group. In this invention, "(meth)acrylate" refers to either or both acrylate and methacrylate, and "(meth)acryloyl group" refers to either or both an acryloyl group and a methacryloyl group. (Meth)acrylate may also be referred to as a compound having a (meth)acryloyl group.

[0013] ((meth)acrylate monomer) Examples of (meth)acrylate monomers and monofunctional (meth)acrylates include ethyl (meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, nonyl (meth)acrylate, lauryl (meth)acrylate, tridecyl (meth)acrylate, hexadecyl (meth)acrylate, octadecyl (meth)acrylate, isoamyl (meth)acrylate, isodecyl (meth)acrylate, isostearyl (meth)acrylate, cyclohexyl (meth)acrylate, benzyl (meth)acrylate, methoxyethyl (meth)acrylate, butoxyethyl (meth)acrylate, phenoxyethyl (meth)acrylate, phenoxydiethylene glycol (meth)acrylate, and nonyl Examples include phenoxyethyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, glycidyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, 3-chloro-2-hydroxypropyl (meth)acrylate, diethylaminoethyl (meth)acrylate, nonylphenoxyethyl tetrahydrofurfuryl (meth)acrylate, caprolactone-modified tetrahydrofurfuryl (meth)acrylate, isobornyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, ethoxyethoxyethyl acrylate, and ethoxyethoxyethanol acrylic acid polymer esters.

[0014] Examples of difunctional (meth)acrylates include 1,4-butanediol di(meth)acrylate, 3-methyl-1,5-pentanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, ethylene oxide (sometimes abbreviated as EO)-modified 1,6-hexanediol diacrylate, hydroxypivalate neopentyl glycol diacrylate, neopentyl glycol di(meth)acrylate, 2-methyl-1,8-octanediol di(meth)acrylate, 2-butyl-2-ethyl-1,3-propanediol di(meth)acrylate, tricyclodecanedimethanol di(meth)acrylate, ethylene glycol di(meth)acrylate, and diethylene glycol di(meth)acrylate. Examples include di(meth)acrylates of dihydric alcohols such as triethylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, tris(2-hydroxyethyl) isocyanurate di(meth)acrylate, di(meth)acrylate of diols obtained by adding 4 moles or more of ethylene oxide or propylene oxide to 1 mole of neopentyl glycol, and di(meth)acrylates of diols obtained by adding 2 moles of ethylene oxide or propylene oxide to 1 mole of bisphenol A.

[0015] Examples of (meth)acrylates with three or more functions include poly(meth)acrylates of polyhydric alcohols with three or more functions, such as trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, and dipentaerythritol poly(meth)acrylate; tri(meth)acrylates of triols obtained by adding 3 or more moles of ethylene oxide or propylene oxide to 1 mole of glycerin; di(meth)acrylates of triols obtained by adding 3 or more moles of ethylene oxide or propylene oxide to 1 mole of trimethylolpropane; and poly(meth)acrylates of polyoxyalkylene polyols, such as di(meth)acrylates of diols obtained by adding 4 or more moles of ethylene oxide or propylene oxide to 1 mole of bisphenol A.

[0016] Furthermore, other (meth)acrylates with two or more functions, such as a mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate (sometimes abbreviated as DPHA), ditrimethylolpropane tetraacrylate (sometimes abbreviated as DTMPTA), and trimethylolpropane ethylene oxide adduct tri(meth)acrylate, which is a triol tri(meth)acrylate obtained by adding 3 or more moles of ethylene oxide to 1 mole of trimethylolpropane, may also be used. Typical examples of the aforementioned trimethylolpropane ethylene oxide adduct tri(meth)acrylate include trimethylolpropane ethylene oxide (hereafter, ethylene oxide may be referred to as "EO") modified (n≒3) triacrylate.

[0017] (Meth)acrylate monomers include, among others, phenol EO-modified acrylate, EO-modified 1,6-hexanediol diacrylate, EO-modified bisphenol A diacrylate, EO-modified trimethylolpropane triacrylate, pentaerythritol alkoxytetraacrylate, 1,6-hexanediol diacrylate, 1,6-hexanediol dimethacrylate, trimethylolpropane tri(meth)acrylate, DPHA, etc., which are preferred.

[0018] The above (meth)acrylate monomer is preferably contained in the range of 0 to 100% by mass, more preferably in the range of 20 to 80% by mass, based on the total amount of (meth)acrylate in the excimer laser curable matte coating agent of the present invention.

[0019] Among others, the (meth)acrylate is at least one (meth)acrylate monomer selected from the group consisting of ethoxyethoxyethyl acrylate, ethoxyethoxyethanol acrylic acid multimer ester, ethylene oxide-modified 1,6-hexanediol di(meth)acrylate, tripropylene glycol di(meth)acrylate, hydroxypivalic acid neopentyl glycol diacrylate, di(meth)acrylate of triol obtained by adding 3 moles or more of ethylene oxide or propylene oxide to 1 mole of trimethylolpropane, and tri(meth)acrylate of triol obtained by adding 3 moles or more of ethylene oxide or propylene oxide to 1 mole of trimethylolpropane.

[0020] ((Meth)acrylate oligomer) (Meth)acrylate oligomers include urethane (meth)acrylate, epoxy (meth)acrylate, polyacryl (meth)acrylate, polyester (meth)acrylate, polyether (meth)acrylate, polyolefin (meth)acrylate, polystyrene (meth)acrylate, amine-modified polyether acrylate, amine-modified epoxy acrylate, amine-modified aliphatic acrylate, amine-modified polyester acrylate, amine-modified acrylate such as amino (meth)acrylate, and the like. Among them, urethane (meth)acrylate, epoxy (meth)acrylate, and polyacryl (meth)acrylate are more preferable in that they can have a coating-applicable viscosity, low gloss, stain resistance, and scratch resistance.

[0021] (Urethane (meth)acrylate) The urethane (meth)acrylate used in the present invention has a (meth)acryloyl group, and for example, those obtained by reacting diisocyanate with (meth)acrylates having a hydroxyl group, those obtained by reacting a polyol and a polyisocyanate under conditions of an excess of isocyanate groups to obtain an isocyanate group-containing urethane prepolymer and then reacting it with (meth)acrylates having a hydroxyl group, and the like. Alternatively, it can also be obtained by reacting a hydroxyl group-containing urethane prepolymer obtained by reacting a polyol and a polyisocyanate under conditions of an excess of hydroxyl groups with (meth)acrylates having an isocyanate group.

[0022] Specifically, for example, urethane (meth)acrylate, which is a reaction product of a hydroxyl group-containing (meth)acrylate, an isocyanate compound, and various polyols as required, can be used.

[0023] Examples of the hydroxyl group-containing (meth)acrylates that can be used include hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, hydroxybutyl acrylate, hydroxybutyl methacrylate, 1,4-cyclohexanedimethanol monoacrylate, polyethylene glycol monoacrylate, polyethylene glycol monomethacrylate, trimethylolpropane diacrylate, trimethylolpropane dimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, glycidyl acrylate, and glycidyl methacrylate.

[0024] Examples of isocyanate compounds include aromatic isocyanates such as 4,4′-diphenylmethane diisocyanate, 2,4-tolylene diisocyanate, 1,5-naphthalene diisocyanate, n-isocyanate phenylsulfonyl isocyanate, o-isocyanate phenylsulfonyl isocyanate, and p-isocyanate phenylsulfonyl isocyanate; aliphatic isocyanates such as 1,6-hexamethylene diisocyanate; alicyclic isocyanates such as isophorone diisocyanate, hydrogenated xylylene diisocyanate, and hydrogenated diphenylmethane diisocyanate, as well as adducts and polymers thereof, which can be used alone or in combination of two or more.

[0025] In particular, from the viewpoint of weather resistance, a caprolactone-based urethane (meth)acrylate having a caprolactone skeleton is preferred. Caprolactone-based urethane (meth)acrylates can usually be obtained by reacting a caprolactone-based polyol with an isocyanate compound and a hydroxyl group-containing (meth)acrylate. A preferred synthesis method involves reacting a polycaprolactone-based polyol with a diisocyanate compound to produce a polyurethane prepolymer containing -NCO groups (isocyanate groups) at both ends, followed by reaction with a hydroxyl group-containing (meth)acrylate. The reaction conditions can follow conventional methods.

[0026] As the caprolactone-based polyol, commercially available polyols can be used, preferably those having two hydroxyl groups and a number-average molecular weight of preferably 500 to 3000, more preferably 750 to 2000. In addition, polyols other than caprolactone-based polyols, such as ethylene glycol, diethylene glycol, 1,4-butanediol, and 1,6-hexanediol, can be used by mixing one or more of them in any proportion.

[0027] In the present invention, when a caprolactone-based polyol is included, the caprolactone-based urethane (meth)acrylate is preferably a caprolactone diol-based urethane (meth)acrylate. A caprolactone diol-based urethane (meth)acrylate is a type of caprolactone-based urethane (meth)acrylate in which the terminal end is diethylene glycol. By using a caprolactone diol-based urethane (meth)acrylate, a decorative sheet can be obtained that does not crack or whiten, in particular.

[0028] Other polyols that can be reacted include glycols such as 1,2-propanediol, 2-methyl-1,3-propanediol, and 3-methyl-1,5-pentanediol; and aliphatic diols such as ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, dimethylbutanediol, butylethylpropanediol, 2,2,4-trimethyl-1,3-pentanediol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, bishydroxyethoxybenzene, 1,4-cyclohexanediol, and 1,4-cyclohexanedimethanol.

[0029] Ether glycols such as polyoxyethylene glycol and polyoxypropylene glycol; modified polyetherdiols obtained by ring-opening polymerization of aliphatic diols with various cyclic ether-containing compounds such as ethylene oxide, propylene oxide, tetrahydrofuran, ethyl glycidyl ether, propyl glycidyl ether, butyl glycidyl ether, phenyl glycidyl ether, and allyl glycidyl ether;

[0030] Examples include bisphenols such as bisphenol A and bisphenol F; alkylene oxide adducts of bisphenols obtained by adding ethylene oxide, propylene oxide, etc., to bisphenols such as bisphenol A and bisphenol F; and polycarbonate polyols.

[0031] The urethane (meth)acrylate is preferably contained in an amount of 0 to 100% by mass relative to the total amount of (meth)acrylate in the excimer laser photocurable matte coating agent of the present invention, and more preferably in an amount of 20 to 80% by mass.

[0032] (Epoxy (meth)acrylate) Examples of epoxy (meth)acrylates used in the present invention include addition reaction products of an oxirane ring-containing compound and a carboxyl group-containing (meth)acrylate. Examples of the oxirane ring-containing compound include aromatic epoxy compounds such as bisphenol-type epoxy, aliphatic epoxy compounds such as diglycidyl ethers of diols having 2 to 20 carbon atoms, and alicyclic epoxy compounds. Examples of the carboxyl group-containing (meth)acrylate include (meth)acrylic acid, β-carboxyethyl (meth)acrylate, mono(2-acryloyloxyethyl) succinate, mono(2-methacryloyloxyethyl) succinate, (meth)acrylate dimer, and caprolactam-modified (meth)acrylate.

[0033] Specific examples of the epoxy (meth)acrylate include, for example, bisphenol-type epoxy acrylate, novolac-type epoxy acrylate, aliphatic-type epoxy acrylate, and glycidyl ester-type acrylate. These compounds may be used individually or in combination of two or more, or polymers thereof may be used.

[0034] The epoxy (meth)acrylate is preferably contained in an amount of 0 to 100% by mass, and more preferably in an amount of 20 to 80% by mass, relative to the total amount of (meth)acrylate in the excimer laser photocurable matte coating agent of the present invention.

[0035] (Polyacrylic (meth)acrylate) The polyacrylic (meth)acrylate used in the present invention can be, for example, a polymer obtained by attaching acryloyl groups to a copolymerized acrylic polymer obtained by polymerizing acrylic monomers or vinyl monomers. Specific examples of polyacrylic acrylate include, for example, a polymer obtained by polymerizing (meth)acrylic acid ester and epoxy group-containing (meth)acrylate, to which (meth)acrylic acid is added, or a polymer obtained by polymerizing (meth)acrylic acid ester and (meth)acrylic acid, to which epoxy group-containing (meth)acrylate is added.

[0036] In particular, it is preferable to use a (meth)acrylate with two or more functionalities, and it is also preferable to use a (meth)acrylate monomer or (meth)acrylate oligomer with two or more functionalities.

[0037] The polyacrylic (meth)acrylate is preferably contained in an amount of 0 to 100% by mass, and more preferably in an amount of 20 to 80% by mass, relative to the total amount of (meth)acrylate in the excimer laser photocurable matte coating agent of the present invention.

[0038] The (meth)acrylate oligomer is preferably contained in an amount of 0 to 100% by mass, and more preferably in an amount of 20 to 80% by mass, relative to the total amount of (meth)acrylate in the excimer laser photocurable matte coating agent of the present invention.

[0039] The total amount of (meth)acrylate, that is, the total amount of the (meth)acrylate monomer and the (meth)acrylate oligomer, is preferably in the range of 50 to 99.8% by mass, and more preferably in the range of 75 to 99% by mass, relative to the total amount of nonvolatile components of the excimer laser photocurable matte coating agent of the present invention.

[0040] The molecular weight of the (meth)acrylate is preferably in the range of 150 to 100,000 as a number average molecular weight, and more preferably in the range of 200 to 10,000 as a number average molecular weight.

[0041] (Photopolymerization initiator) The excimer laser photocurable matte coating agent of the present invention requires a photopolymerization initiator for the "step (II) of irradiating the coating film with ultraviolet light" described later. Furthermore, in the excimer laser photocurable matte coating agent of the present invention, when an electron beam is used in the "step (IV) of irradiating the coating film with ultraviolet light or an electron beam" described later, the use of a photopolymerization initiator is not required for this step, but when ultraviolet light is used, a photopolymerization initiator may be added. For the steps of "irradiating the coating film with ultraviolet light (II)" and "irradiating the coating film with ultraviolet light or an electron beam (IV)", known photopolymerization initiators that match the ultraviolet wavelength used in each step may be used.

[0042] Among these, radical polymerization type photopolymerization initiators are preferred, and α-hydroxyalkyl ketone-based photopolymerization initiators that do not color the dissolution solution when active energy ray curable compounds are dissolved and show little yellowing over time are particularly preferred. Examples of α-hydroxyalkyl ketone-based photopolymerization initiators include 1-phenyl-2-hydroxy-2-methylpropan-1-one, 1-(4-i-propylphenyl)-2-hydroxy-2-methylpropan-1-one, 4-(2-hydroxyethoxy)phenyl-(2-hydroxy-2-propyl)ketone, and 1-hydroxycyclohexylphenyl ketone. Furthermore, phenylglyoxolate-based photopolymerization initiators are also preferred. Examples of phenylglyoxolate-based photopolymerization initiators include methylbenzoyl formate. Among these, 1-hydroxycyclohexylphenyl ketone is preferred.

[0043] Furthermore, other radical polymerization type photopolymerization initiators that have absorption wavelengths in the long-wavelength region of ultraviolet light may be used, such as monoacylphosphine oxide-based photopolymerization initiators and bisacylphosphine oxide-based photopolymerization initiators. Examples of monoacylphosphine oxide-based photopolymerization initiators include monoacylphosphine oxides such as 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, ethyl(2,4,6-trimethylbenzoyl)-phenylphosphinate, 2,6-dimethoxybenzoyl-diphenylphosphine oxide, 2,6-dichlorobenzoyl-diphenylphosphine oxide, 2,4,6-trimethylbenzoyl-phenylphosphinate methyl ester, 2-methylbenzoyl-diphenylphosphine oxide, and pivaloylphenylphosphinate isopropyl ester. Examples of bisacylphosphine oxide-based photopolymerization initiators include bis-(2,6-dichlorobenzoyl)phenylphosphine oxide, bis-(2,6-dichlorobenzoyl)-2,5-dimethylphenylphosphine oxide, bis-(2,6-dichlorobenzoyl)-4-propylphenylphosphine oxide, bis-(2,6-dichlorobenzoyl)-1-naphthylphosphine oxide, bis-(2,6-dimethoxybenzoyl)phenylphosphine oxide, bis-(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide, bis-(2,6-dimethoxybenzoyl)-2,5-dimethylphenylphosphine oxide, bis-(2,4,6-trimethylbenzoyl)phenylphosphine oxide, and (2,5,6-trimethylbenzoyl)-2,4,4-trimethylpentylphosphine oxide. In particular, among these, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide and bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide are more preferable because they have UV absorption wavelengths that match the emission wavelength range of UV-LEDs having emission wavelengths of 385 nm and 395 nm, respectively, resulting in a suitable curing type and less yellowing of the cured film.

[0044] The aforementioned photopolymerization initiators may be used individually or in combination of two or more. The total amount of the photopolymerization initiators added is preferably in the range of 0.01% to 30% by mass relative to the total mass of the non-volatile components of the coating agent. More preferably, it is in the range of 0.1% to 25% by mass relative to the total amount of the coating agent.

[0045] (Particle A) Particle A, which is composed of silica and / or alumina with an average particle size of 1 nm to 10.0 μm used in the present invention, specifically includes, for example, amorphous silica, alumina particles (aluminum oxide), silica-alumina, etc. Among amorphous silicas, synthetic amorphous silica such as dry silica, wet silica, and silica gel can be used. Among alumina particles, α-alumina, γ-alumina, etc. can be used. Particle A may also be surface-treated. There are no particular restrictions on the method of surface treatment of the particles, and any known method is acceptable. Examples include surface treatment with wax or silane coupling agent. Multiple particles, both surface-treated and unsurface-treated, may be mixed and used.

[0046] The particles A are preferably contained in an amount of 0.1 to 5% by mass, more preferably 0.1 to 2% by mass, and even more preferably 0.1 to 1% by mass, relative to the total amount of nonvolatile components of the excimer laser photocurable matte coating agent of the present invention. Furthermore, the average particle diameter is preferably 1 nm to 10.0 μm, more preferably 1 nm to 5.0 μm, and even more preferably 1 nm to 3.0 μm. In this invention, the average particle diameter is the value measured by the Coulter counter method for particles of 0.1 μm or larger, and the value measured by a scanning electron microscope (SEM) for particles smaller than 0.1 μm. Furthermore, the BET specific surface area is 25-400m². 2 It is preferable that the value be / g, and more preferably 50 to 350m 2 It is / g. Furthermore, a heat loss of 0-7% is preferable. Furthermore, the pH is preferably 3 to 8, and more preferably 5 to 8.

[0047] Particle A used in this invention is presumed to play a role in stabilizing wrinkles generated when an excimer laser is irradiated. As mentioned above, particle A is contained in an amount of 0.1 to 5% by mass relative to the total amount of nonvolatile components of the excimer laser photocurable matte coating agent. However, it is difficult to stably produce a matte finish using the conventional method of irradiating with active energy rays. By combining it with excimer laser light, a stably matte finish can be produced.

[0048] (Weather-resistant additive) The excimer laser photocurable matte coating agent of the present invention can achieve high weather resistance (whitening resistance) without the addition of weather-resistant additives, but it is preferable to add weather-resistant additives such as ultraviolet absorbers, light stabilizers, and antioxidants to obtain even higher weather resistance. Among the weather-resistant additives, hydroxyphenyltriazine-based ultraviolet absorbers, hindered amine-based light stabilizers, and hindered phenol-based antioxidants are preferred for obtaining higher weather resistance. Weather-resistant additives having reactive functional groups such as hydroxyl groups and (meth)acrylate groups are also preferred for obtaining higher weather resistance. Weather-resistant additives without reactive functional groups can move with a high degree of freedom in the active energy ray curable coating film, while weather-resistant additives with reactive functional groups can exhibit longer-term functionality by being fixed in the active energy ray curable coating film, so it is most preferable to use both in combination.

[0049] The weather-resistant additive is preferably contained in an amount of 0.5 to 15% by mass, and more preferably 1 to 10% by mass, relative to the total mass of the non-volatile components of the excimer laser photocurable matte coating agent. Furthermore, if the weather-resistant additive is an ultraviolet absorber, it is preferably contained in an amount of 0.5 to 15% by mass, and more preferably 1 to 10% by mass, relative to the total mass of the nonvolatile components of the excimer laser photocurable matte coating agent. Furthermore, if the weather-resistant additive is a light stabilizer, it is preferably contained in an amount of 0.5 to 15% by mass, and more preferably 1 to 10% by mass, relative to the total mass of the nonvolatile components of the excimer laser photocurable matte coating agent. Furthermore, if the weather-resistant additive is an antioxidant, it is preferably contained in an amount of 0.5 to 10% by mass, and more preferably 0.5 to 5% by mass, relative to the total mass of the non-volatile components of the excimer laser photocurable matte coating agent.

[0050] (Matte agent) In the present invention, a so-called matting agent, as used in the prior art, may be included, but it is preferable to keep the amount as small as possible, as this may impair the effects of the present invention. In the present invention, a sufficient matte finish can be obtained without using a matting agent. When using a matting agent, it is preferable to use it in an amount of less than 15% by mass, less than 10% by mass, less than 5% by mass, and most preferably less than 3% by mass, relative to the total mass of the nonvolatile components of the excimer laser photocurable matting coating agent of the present invention. In this invention, "matting agent" specifically refers to a layer that may contain a matting agent, i.e., particles having an average particle diameter that is greater than 100% of the thickness of the matting agent and greater than 30 μm, whichever is smaller, as the lower limit, from the viewpoint of forming a convex portion by the effect of protruding the surface, as described above.

[0051] (wax) The excimer laser photocurable matte coating agent of the present invention preferably contains a wax to obtain scratch resistance. For example, polyolefin wax can be used as the wax. Among these, polyethylene wax is preferred because it provides higher scratch resistance. The amount of wax added is preferably 0.5 to 5% by mass, and more preferably 1 to 3% by mass, relative to the total mass of the nonvolatile components of the excimer laser photocurable matte coating agent.

[0052] (Non-reactive resin) The excimer laser photocurable matte coating agent of the present invention can also be used in combination with a non-reactive binder resin that does not harden with active energy rays. Examples include vinyl chloride-vinyl acetate copolymer resin, vinyl chloride-vinyl isobutyl ether copolymer resin, acrylic resin, rosin-based resin, polyurethane resin, polyamide-based resin, chlorinated polypropylene resin, ethylene-vinyl acetate copolymer resin, vinyl acetate resin, polyvinyl chloride resin and other vinyl chloride-based resins, polyester resin, alkyd resin, ketone resin, cycloplastic rubber, chlorinated rubber, butyral, petroleum resin, and the like.

[0053] (Organic solvents) The excimer laser photocurable matte coating agent of the present invention may also be diluted with an organic solvent as needed. Any organic solvent that can dissolve the compound containing the (meth)acryloyl group used can be used. Examples include aromatic hydrocarbons such as toluene and xylene, aliphatic or alicyclic hydrocarbons such as n-hexane, cyclohexane, methylcyclohexane, and ethylcyclohexane, esters such as ethyl acetate, butyl acetate, and propyl acetate, alcohols such as methanol, ethanol, isopropyl alcohol, and n-butanol, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone, alkylene glycol monoalkyl ethers such as ethylene glycol monoethyl ether and propylene glycol monomethyl ether, and ether esters such as propylene glycol monomethyl ether acetate. These may also be used in mixtures. However, if the purpose is to thoroughly reduce the amount of organic solvent evaporated into the atmosphere, i.e., to reduce volatile organic compounds (VOCs), it is more preferable to use a solvent that does not contain the above-mentioned organic solvents.

[0054] From the viewpoint of coatability, the excimer laser photocurable matte coating agent of the present invention is preferably adjusted to a viscosity that allows it to be coated in the method for producing the active energy ray curable coating film of the present invention, as described later. The viscosity is preferably adjusted to 30 to 3000 mPa·s. In particular, when using a high molecular weight polymer with high viscosity in combination, the viscosity can be adjusted to this level by diluting with an organic solvent or heating as necessary.

[0055] (Other additives) The excimer laser photocurable matte coating agent of the present invention may also contain polymerization inhibitors, leveling agents, thixotropic agents, drying agents, thickeners, anti-sagging agents, plasticizers, dispersants, anti-settling agents, and defoaming agents.

[0056] (base material) The substrate used in this invention is not particularly limited. For example, if it is a decorative sheet for building materials, a general-purpose base sheet used for decorative sheets can be used as the base material. There are no particular limitations on the base sheet; general decorative sheets, sheets made of general-purpose thermoplastic resin (sometimes called films), or paper can be used. Examples of sheets (films) formed from thermoplastic resins include polyolefin resins such as polyethylene, ethylene-α-olefin copolymer, polypropylene, polymethylpentene, polybutene, ethylene-propylene copolymer, propylene-butene copolymer, ethylene-vinyl acetate copolymer, ethylene-vinyl acetate copolymer saponified, ethylene-(meth)acrylic acid copolymer, and ethylene-(meth)acrylic acid ester copolymer; polyvinyl chloride, polyethylene terephthalate (PET), polybutylene terephthalate, polyamide, polycarbonate, polyethylene naphthalate, ionomer, acrylic acid ester polymer, and methacrylic acid ester polymer. The base sheet may be formed by using these resins individually or in combination of two or more.

[0057] The base sheet may be colored, and may contain various additives as needed, such as fillers, matting agents, foaming agents, flame retardants, lubricants, antistatic agents, antioxidants, UV absorbers, and light stabilizers. The thickness of the base sheet can be set appropriately depending on the application and method of use of the final product, but is generally preferred to be 20 to 300 μm.

[0058] One or both sides of the base sheet may be subjected to surface treatments such as corona discharge treatment, ozone treatment, plasma treatment, ionizing radiation treatment, or dichromate treatment, as needed. For example, when performing corona discharge treatment, the surface tension of the base sheet surface should be 30 dyne or more, preferably 40 dyne or more. Surface treatments should be carried out according to the standard methods for each treatment.

[0059] Examples of paper substrates for decorative sheets include tissue paper, regular paper, reinforced paper, resin-impregnated paper, titanium paper, and other paper-based sheets.

[0060] Alternatively, wood-based decorative panels commonly used for decorative panels may be used as the base material. Examples of wood-based base materials for wood-based decorative panels include plywood, particleboard, hardboard, and MDF, which have been conventionally used as wood-based base materials for decorative panels, furniture, and building materials. Furthermore, the manufacturing method by which these known base materials are obtained is irrelevant. Furthermore, examples of non-combustible materials that can be used as base materials include perforated board building materials made from materials such as gypsum board, gypsum board, and calcium silicate board; ceramic sheets such as pottery, porcelain, stoneware, earthenware, glass, and enamel; and metal sheets such as iron sheets, galvanized steel sheets, polyvinyl chloride sol coated steel sheets, aluminum sheets, and copper sheets.

[0061] (Method for manufacturing an excimer laser photocurable matte coating agent) The excimer laser photocurable matte coating agent of the present invention can be manufactured by mixing and dispersing the (meth)acrylate, the photopolymerization initiator, particles A with an average particle size of 1 nm to 10.0 μm, and, if necessary, weather-resistant additives, matting agents, organic solvents, and various other additives. A commonly used disperser, such as a roller mill, ball mill, pebble mill, attritor, or sand mill, can be used, and the size of the grinding media, the filling rate of the grinding media, and the dispersion processing time can be appropriately adjusted. If air bubbles or unexpectedly large particles are contained in the coating agent, it is preferable to remove them by filtration or the like, as this will degrade the quality of the coated product. Conventional known filters can be used.

[0062] (Method for manufacturing a matte coating film) To achieve a more optimal matte finish, the coating film using the excimer laser photocurable matte coating agent of the present invention is preferably manufactured by the following steps (I) to (IV). That is, Step (I) of forming a coating film of an excimer laser photocurable matte coating agent on a substrate, The process involves irradiating the coating film with ultraviolet light (II), The process involves irradiating the coating film with excimer laser light (III), (IV) A step of irradiating the coating film with ultraviolet light or an electron beam, This is the method in this order.

[0063] (Process (I)) In step (I), the coating film can be formed using any known coating or printing method without any particular limitations. Specific coating methods that can be appropriately employed include, for example, roll coaters, gravure coaters, gravure offset coaters, flexo coaters, air doctor coaters, blade coaters, air knife coaters, squeeze coaters, impregnation coaters, transfer roll coaters, kiss coaters, curtain coaters, cast coaters, spray coaters, die coaters, offset printing presses, screen printing presses, etc. If the coating agent used contains an organic solvent, the formed coating film can be dried in a drying oven or the like to remove the solvent.

[0064] (Step (II)) Step (II) is the step of irradiating the coating film with ultraviolet light after creating the coating film using the method described above. Ultraviolet irradiation can be carried out by known methods. For example, ultraviolet light can be emitted from light sources such as germicidal lamps, ultraviolet fluorescent lamps, ultraviolet light-emitting diodes (UV-LEDs), carbon arcs, metal halide lamps, xenon lamps, chemical lamps, low-pressure mercury lamps, high-pressure mercury lamps for copying, medium-pressure or high-pressure mercury lamps, ultra-high-pressure mercury lamps, electrodeless lamps, metal halide lamps, and natural light.

[0065] (Process (III)) Step (III) is the process of irradiating with excimer laser light after irradiating with ultraviolet light in step (II). The medium for an excimer laser can be any known medium (discharge gas) as long as it has energy capable of cleaving at least one of the carbonyl bond and carbon-carbon bond. As the discharge gas, noble gases such as Xe, Ar, Kr, and Ne, or noble gas halide gases such as ArBr, ArF, KrCl, XeI, XeCl, XeBr, KrBr, and KrF, or mixtures thereof can be used. The wavelength (center wavelength) of an excimer laser varies depending on the medium, and has wavelengths such as approximately 172 nm (Xe), approximately 126 nm (Ar), approximately 146 nm (Kr), approximately 165 nm (ArBr), approximately 193 nm (ArF), approximately 222 nm (KrCl), approximately 253 nm (XeI), approximately 308 nm (XeCl), approximately 283 nm (XeBr), approximately 207 nm (KrBr), and approximately 248 nm (KrF). Discharge lamps that emit excimer light (ultraviolet light) are also called "excimer lamps." Regarding wavelength, it is preferable to use light with shorter wavelengths, with medium-wavelength ultraviolet light (wavelength: 280-320 nm) being more preferable, short-wavelength ultraviolet light (wavelength: 280 nm or less) being more preferable, and short-wavelength ultraviolet light being even more preferable. In the present invention, it is most preferable that the medium is Xe and the wavelength is approximately 172 nm. Furthermore, the oxygen concentration when irradiating with excimer light is preferably lower, preferably 1000 ppm or less, more preferably 750 ppm or less, even more preferably 500 ppm or less, and even more preferably 300 ppm or less.

[0066] (Step (IV)) Step (IV) is the step in which, after irradiating with excimer laser light in step (III), ultraviolet light or an electron beam is irradiated. Ultraviolet irradiation can be carried out in the same manner as in step (II) above. To obtain higher curability, it is preferable to perform ultraviolet irradiation under a nitrogen atmosphere. In this case, the oxygen concentration is preferably lower, preferably 2% or less. When using an electron beam, an electron beam irradiation device should be used. The acceleration voltage is preferably 200kV or less. The irradiation dose is preferably around 10 to 230kGy, and more preferably around 10 to 100kGy. In the case of electron beam irradiation, the atmosphere should preferably have an oxygen concentration of 2% or less.

[0067] The thickness of the coating film obtained in this way is preferably in the range of 0.1 to 100 μm, and most preferably in the range of 0.5 to 50 μm. This thickness range allows the effects of the present invention to be maximized.

[0068] Furthermore, the manufacturing method of the present invention can be widely applied not only to the aforementioned building materials such as decorative sheets, but also to surface coating applications for furniture, musical instruments, office supplies, sporting goods, toys, and the like. [Examples]

[0069] The present invention will be described in more detail below with reference to examples. In the following examples, parts and parts by mass refer to mass percent.

[0070] In this invention, the weight-average molecular weight and the number-average molecular weight are values ​​measured by the following method. Measuring device; HLC-8220, manufactured by Tosoh Corporation. Column; Guard Column HXL-H manufactured by Tosoh Corporation + TSKgel G5000HXL manufactured by Tosoh Corporation + TSKgel G4000HXL manufactured by Tosoh Corporation + TSKgel G3000HXL manufactured by Tosoh Corporation + TSKgel G2000HXL manufactured by Tosoh Corporation Detector; RI (Differential Refractometer) Data processing: Tosoh Corporation SC-8010 Measurement conditions: Column temperature 40°C Solvent: tetrahydrofuran Flow rate 1.0ml / min Standard; polystyrene Sample: 100 μl of a tetrahydrofuran solution containing 0.4% by mass (based on resin solids content) filtered through a microfilter. Furthermore, the average particle diameter of silica is measured using the Coulter counter method in accordance with JIS Z8832:2010 "Method for measuring particle size distribution - Electrical detection band method" for particles 0.1 μm or larger, and measured using SEM in accordance with JIS Z8827 "Particle size analysis - Image analysis method" for particles smaller than 0.1 μm.

[0071] (Preparation of excimer laser photocurable matte coating agent) [Example 1] 45.3 parts by mass of MIRAMER M202, 30.2 parts by mass of MIRAMER M220, 15.1 parts by mass of MIRAMER M3130, 1.0 part by mass of NIP GEL AZ-204, 0.5 parts by mass of OMNIRAD819, 4.5 parts by mass of hydroxyphenyltriazine-based ultraviolet absorber, 1.0 part by mass of hindered amine-based light stabilizer, 1.5 parts by mass of reactive hindered amine-based light stabilizer, and 1.0 part by mass of hindered phenol-based antioxidant were added to a total of 100.0 parts by mass and thoroughly stirred with a stirrer to prepare an excimer laser photocurable matte coating agent (1).

[0072] [Examples 2-32, Comparative Examples 1-7] Each excimer laser-curable matte coating agent was prepared according to the formulations shown in Tables 1-4, using the same procedure as in Example 1.

[0073] <Formation of coating film by process (I)> An excimer laser photocurable matte coating agent prepared in the above example or comparative example was applied to the substrate using a bar coater to a thickness of approximately 7 μm to form a coating film. The following two types of base materials were used: PET film: Polyester film (A4100, film thickness 50 μm, manufactured by Toyobo Co., Ltd.) Olefin sheet: A sheet (film thickness 150 μm) on which a printing ink layer, adhesive layer, polypropylene sheet, and primer layer are provided in this order on a polypropylene sheet.

[0074] <Irradiation with ultraviolet light by process (II)> On the coating film formed in step (I) above, a light irradiation device (IST Laboratory-Unit M-32-1-MZ+37,5-1-EXI+40-1-MBS3-Tr-N2, manufactured by IST Corporation) is used, and an LEDCure MZ,320-395 lamp is used to irradiate the coating film with a peak illuminance of 3.0 W / cm². 2 The coating film was partially cured by irradiating it with ultraviolet light at a wavelength of 395 nm at a conveyor speed of 50 m / min.

[0075] <Irradiation with excimer laser light by process (III)> On the semi-cured coating film formed in step (II) above, an excimer laser beam with a wavelength of 172 nm was irradiated using an excimer lamp module with an excimer lamp module (IST Laboratory-Unit M-32-1-MZ+37,5-1-EXI+40-1-MBS3-Tr-N2 manufactured by IST Corporation) at an output of 4.0 W / cm, a conveyor speed of 50 m / min, and a nitrogen atmosphere (oxygen concentration of 200 ppm or less) to form a matte finish on the coating film.

[0076] <Irradiation with ultraviolet or electron beam by process (IV)> The matte semi-cured coating film formed in step (III) above was cured by irradiating it with an electron beam using a curtain-type electron beam irradiation device (Iwasaki Electric Co., Ltd. "Electro Curtain EC250 / 15 / 180L") at an acceleration voltage of 125kV and an irradiation dose of 50kGy. Alternatively, the matte semi-cured coating film formed in step (III) above was cured by irradiating it with ultraviolet light using a light irradiation device (IST Corporation "IST Laboratory-Unit M-32-1-MZ+37,5-1-EXI+40-1-MBS3-Tr-N2") with a Minicure lamp module at an output of 200W / cm, a conveyor speed of 50m / min, and in an atmospheric or nitrogen atmosphere (oxygen concentration of 2% or less).

[0077] For the excimer laser photocurable matte coating films that were fabricated, those using PET film as a substrate were evaluated for their "gloss value." Those using olefin sheets as a substrate were evaluated for their "weather resistance (whitening resistance)" and "weather resistance (collapsibility resistance)."

[0078] (Evaluation item 1: Gloss value) The gloss value of the coating film, which was prepared using PET film as a substrate, was measured using a gloss meter (Konica Minolta "MULTI GLOSS 268A") in accordance with JIS Z8741. The measurement conditions for the gloss value were an incident angle of 60° and a reflection angle of 60°. The obtained gloss values ​​were evaluated using a three-level standard. A value of ○ or higher was considered acceptable. (Evaluation Criteria) ◎: 20 or less (good low-gloss appearance) ○: 25 or less (sufficient low-gloss finish) ×: Greater than 25

[0079] (Evaluation item 2: Weather resistance (resistance to whitening)) The coating film, prepared using an olefin sheet as a substrate, was irradiated with ultraviolet light using a Super UV Weathering Accelerated Tester (iSuper UV Tester SUV-W261, manufactured by Iwasaki Electric) with settings of illuminance 60mW, irradiation temperature 63℃, rest temperature 50℃, irradiation humidity 50%, rest humidity 50%, irradiation time 20 hours, dew time 4 hours, rest time 6 minutes, and shower 10 seconds. Evaluation was performed when the total test time reached 1000 hours. For the cured coating film before and after the test, the whitening of the coating film was evaluated by tracking the color difference (Δ(delta)E) before and after ultraviolet irradiation using a Konica Minolta CM-700d spectrophotometer. The smaller the color difference value, the higher the resistance to whitening. The obtained ΔE values ​​were evaluated using a three-stage criterion. ○ or higher was considered a pass. (Evaluation Criteria) ◎: 1.5 or less (No whitening can be observed visually.) ○: 3 or less (Very slight whitening occurs, but no significant changes.) ×: Greater than 3 (Albinism can be confirmed by visual observation.)

[0080] (Evaluation item 3: Weather resistance (resistance to collapse)) The coating film, prepared using an olefin sheet as the substrate, was irradiated with ultraviolet light using a Super UV weathering acceleration tester (iSuper UV Tester SUV-W261, manufactured by Iwasaki Electric) with the following settings: irradiance 60mW, irradiation temperature 63℃, rest temperature 50℃, irradiation humidity 50%, rest humidity 50%, irradiation time 20 hours, dew time 4 hours, rest time 6 minutes, and shower 10 seconds. The test time at which a portion of the test piece peeled off and the coating film disintegrated was noted, and evaluation was performed using a three-stage criterion. A score of ○ or higher was considered a pass. (Evaluation Criteria) ◎: Over 1500 hours ○: Over 1200 hours ×: Less than 1000 hours

[0081] Tables 1-5 show the composition of each excimer laser-curable matte coating agent and the evaluation results of the prepared coating films. All values ​​in the tables are in parts by mass or mass%, and blank spaces indicate that the agent was not included. Furthermore, all values ​​except for organic solvents are calculated on a solids basis.

[0082] The abbreviations used in the table are explained below. Note that particle A is shown in Table 6. • MIRAMER M202: Manufactured by MIWON, a bifunctional acrylate monomer. • MIRAMER M220: Manufactured by MIWON, a bifunctional acrylate monomer. • MIRAMER M3130: Manufactured by MIWON, a trifunctional acrylate monomer. • MIRAMER M3190: Manufactured by MIWON, a trifunctional acrylate monomer. • MIRAMER M210: Manufactured by MIWON, a bifunctional acrylate monomer. • MIRAMER M170: Monofunctional acrylate monomer manufactured by MIWON. • Viscoat #190D: Manufactured by Osaka Organic Chemical Industry Co., Ltd., monofunctional acrylate monomer • OMNIRAD 819: Manufactured by IGM Resins BV, photopolymerization initiator. • OMNIRAD TPO H: IGM Resins BV, photopolymerization initiator ·OMNIRAD TPO-L:IGM Resins BV Production, Light Overlap Starter ·OMNIRAD 184D:IGM Resins BV Production, Light Overlap Starter ·OMNIRAD 2959: IGM Resins BV Production, Light Overlap Starts to Renew

[0083] Table 1

[0084] Table 2

[0085] Table 3

[0086] Table 4

[0087] Table 5

[0088] Table 6

Claims

1. Step (I) of forming a coating film of an excimer laser photocurable matte coating agent on a substrate, The process involves irradiating the coating film with ultraviolet light (II), The process involves irradiating the coating film with excimer laser light (III), The process includes, in this order, a step (IV) of irradiating the coating film with ultraviolet light or an electron beam, A method for producing a matte coating film, characterized in that the excimer laser photocurable matte coating agent contains (meth)acrylate, a photopolymerization initiator, and particles A having an average particle size of 1 nm to 10.0 μm, wherein the particles A are present in an amount of 0.1 to 5% by mass relative to the nonvolatile components of the coating agent.

2. The method for producing a matte coating film according to claim 1, wherein the particle A is a fine particle composed of silica and / or alumina having an average particle size of 1 nm to 10.0 μm.

3. The aforementioned particle A has an average particle size of 1 nm to 10.0 μm and a BET specific surface area of ​​25 to 400 m². ２ A method for producing a matte coating film according to claim 1, wherein the fine particles are composed of silica and / or alumina, have a density of / g, a heat loss of 0-7%, and a pH of 3-8.

4. The method for producing a matte coating film according to claim 1, wherein the (meth)acrylate is at least one (meth)acrylate monomer selected from the group consisting of ethoxyethoxyethyl acrylate, ethoxyethoxyethanol acrylic acid polymer ester, ethylene oxide-modified 1,6-hexanediol di(meth)acrylate, tripropylene glycol di(meth)acrylate, neopentyl glycol diacrylate hydroxypivalate, triol di(meth)acrylate obtained by adding 3 moles or more of ethylene oxide or propylene oxide to 1 mole of trimethylolpropane, and triol tri(meth)acrylate obtained by adding 3 moles or more of ethylene oxide or propylene oxide to 1 mole of trimethylolpropane.

5. An excimer laser photocurable matte coating agent for use in a method for manufacturing a matte coating film according to any one of claims 1 to 4, characterized in that it contains (meth)acrylate, a photopolymerization initiator, and particles A having an average particle size of 1 nm to 10.0 μm, wherein the particles A are contained in an amount of 0.1 to 5% by mass relative to the nonvolatile components of the coating agent.

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