JPH08231885A - Photocurable resin composition for matt coating, its manufacture, and synthetic resin molded product using the same - Google Patents

Abstract

PURPOSE: To provide a photocurable resin composition excellent in long-term dispersion stability and capable of forming a matt cured coating by mixing a (meth)acrylic ester derivative, a photopolymerization initiator, superfine silica, and a hindered amine light stabilizer. CONSTITUTION: This composition is obtained by mixing a mixture of (a) a (meth)acrylic ester derivative having one or more (meth)acryloyloxy groups in the molecule, (b) a photopolymerization initiator, and (c) superfine silica dispersed in an organic solvent, with (d) a hindered amine light stabilizer capable of cohering the superfine silica. This composition is a photocurable resin composition for matt coating that contains aggregates obtained from the component (a), the component (b), the component (c), and the component (d). Generally, this resin composition will be mixed with a suitable solvent to be applied to a synthetic resin molded product, followed by irradiation with ultraviolet light to cure the composition. The composition can be cured with actinic radiation, such as an α ray, a β ray, a γ ray, and an electron ray, besides ultraviolet light.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photocurable resin composition for forming a matt cured film, a method for producing the same, and a synthetic resin molded article using the composition. The present invention relates to a photocurable resin composition that forms a matt cured film, a method for producing the same, and a synthetic resin molded article using the composition.

[0002]

2. Description of the Related Art Matte paints are generally used to impart matte properties to the surface of synthetic resin moldings. recent years,
As a matte coating, a photocurable resin composition for matte coating, which is irradiated with active energy rays to form a matte cured coating on the surface, is used. The photocurable resin composition for matte coating is prepared by dispersing and mixing a predetermined matting agent in the photocurable resin composition of the base material in order to obtain a matte appearance according to the purpose, that is, a matte degree. There is. The matting agents used for this purpose are roughly classified into inorganic and organic fine powders. Fine powders such as talc, barium sulfate, and silicic acid anhydride (silica) are used as the inorganic matting agent, and fine powders such as polyethylene, polypropylene, and polycarbonate are used as the organic matting agent. Among them, silica is used. The fine powder of is often used.

[0003]

The photocurable resin composition for matte coating containing fine silica powder as a matting agent has poor dispersion stability over time, that is, when it is stored for a long period of time, There is a problem that fine silica powder settles and caking occurs which cannot be redispersed. Conventionally, fine silica powder having a particle size of several mμ to tens of μ has been used as a fine silica powder capable of exhibiting a matte surface, but it is difficult to obtain a matte cured coating having a fine pattern with this fine silica powder. is there. The object of the present invention is to solve the problems under the present circumstances and to form a matte cured coating having excellent dispersion stability over time, and capable of forming a cured coating having a fine matte pattern. It is intended to provide a curable resin composition and a method for producing the same, and a synthetic resin molded article using the photocurable resin composition.

[0004]

[Means for Solving the Problems] In order to achieve the above-mentioned object, the inventors of the present invention have a (meth) acrylic acid ester derivative (a) having one or more (meth) acryloyloxy groups in the molecule (hereinafter, referred to as Photocuring containing (meth) acrylic acid ester derivative (a), photopolymerization initiator (b) and ultrafine particle silica (c) dispersed in an organic solvent (hereinafter referred to as colloidal silica (c)) When the functional resin composition was examined, the composition was excellent in dispersion stability over time, but the cured film was transparent and did not exhibit matte. Further investigation, when a hindered amine light stabilizer is added to the above resin composition, some of the stabilizers may aggregate ultrafine silica particles of colloidal silica (c) to form aggregates. Found. Then, a synthetic resin molded article was coated with a photocurable resin composition containing a (meth) acrylic acid ester derivative (a), a photopolymerization initiator (b) and the agglomerate, and then irradiated with active energy rays. However, a hindered amine light stabilizer (d) (hereinafter referred to as a hindered amine light stabilizer (d)) that can act as a matting agent to impart a matte effect to the cured film and agglomerate ultrafine silica particles It was found that a fine cured coating film having a matte pattern can be obtained by appropriately selecting the type and amount of the above) and that the photocurable resin composition has excellent dispersion stability over time.

That is, the present invention contains a (meth) acrylic acid ester derivative (a), a photopolymerization initiator (b), and an aggregate obtained from colloidal silica (c) and a hindered amine light stabilizer (d). A photocurable resin composition for matte coating, a (meth) acrylic acid ester derivative (a) having at least one (meth) acryloyloxy group in the molecule, and a photopolymerization initiator (b) And a mixture of ultrafine silica (c) dispersed in an organic solvent, and a hindered amine light stabilizer (d) capable of aggregating the ultrafine silica. And a synthetic resin molded article in which the photocurable resin composition for coating is applied to a synthetic resin molded article, and then a matte cured film is formed on the surface by irradiation with active energy rays. It is.

Further, the photocurable resin composition for matte coating was examined, and when the ultrafine silica of colloidal silica (c) was agglomerated by the hindered amine light stabilizer (d), one When a light stabilizer (e) having a cyclic hindered amine structure (hereinafter referred to as a hindered amine light stabilizer (e)) is present, the obtained aggregates are larger than those obtained when the hindered amine light stabilizer (e) is not used. It was found to have a small particle size. Then, a photocurable resin composition containing the aggregate, the (meth) acrylic acid ester derivative (a) and the photopolymerization initiator (b) was applied to a synthetic resin molded article and then irradiated with active energy rays. The agglomerate acts as a matting agent to form a matte on the cured film, and the matte pattern is finer, and the photocurable resin composition has excellent dispersion stability over time. I found that there is. Moreover, the suitable manufacturing method of the photocurable resin composition which forms a finer matte pattern cured film was also discovered.

That is, the present invention provides a colloidal silica (c) and a hindered amine-based compound in the presence of a (meth) acrylic acid ester derivative (a), a photopolymerization initiator (b), and a hindered amine-based light stabilizer (e). A photocurable resin composition for matte coating, which comprises an aggregate obtained from a light stabilizer (d), and after applying the photocurable resin composition for coating to a synthetic resin molded article, Synthetic resin molded article having a matte cured film formed on the surface by irradiation with active energy rays, and (meth) acrylic acid ester derivative (a), photopolymerization initiator (b), colloidal silica (c) and hindered amine system The present invention also relates to a method for producing the photocurable resin composition for coating, which comprises mixing the mixture of the light stabilizer (e) and the hindered amine light stabilizer (d).

The (meth) acrylic acid ester derivative (a) of the present invention means a (meth) acrylate monomer having one or more (meth) acryloyloxy groups in the molecule (hereinafter referred to as (meth) acrylate monomer), It is at least one kind of a (meth) acryloyloxy group-containing compound such as a (meth) acrylate oligomer having two or more acryloyloxy groups in the molecule (hereinafter referred to as (meth) acrylate oligomer). In addition, a (meth) acryloyloxy group means an acryloyloxy group and a methacryloyloxy group, and a (meth) acrylic acid ester derivative means an acrylic acid ester derivative and a methacrylic acid ester derivative, and a (meth) acrylate monomer and (meth) The same applies to the acrylate oligomer.

As the (meth) acrylate monomer,
Monofunctional (meth) acrylate monomer having one (meth) acryloyloxy group in the molecule (hereinafter referred to as monofunctional (meth) acrylate monomer), bifunctional having two (meth) acryloyloxy groups in the molecule (Meth) acrylate monomer (hereinafter referred to as bifunctional (meth) acrylate monomer) and polyfunctional (meth) acrylate monomer having at least three (meth) acryloyloxy groups in the molecule (hereinafter referred to as polyfunctional (meth) acrylate monomer) That is). The (meth) acrylate monomer may be used alone or in combination of two or more.

Specific examples of the monofunctional (meth) acrylate monomer include tetrahydrofurfuryl (meth) acrylate, 2-hydroxyethyl (meth) acrylate,
Hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-hydroxy-3
-Phenoxypropyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, dicyclopentenyl (meth) acrylate, benzyl (meth) acrylate, Isobornyl (meth) acrylate, phenoxyethyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, ethylcarbitol (meth) acrylate, trimethylolpropane mono (meth) acrylate, pentaerythritol Mono (meth) acrylate, phenoxy polyethylene glycol (meth) acrylate, N- (meth) acryloylmorpholine,
As the carboxyl group-containing (meth) acrylate monomer, 2- (meth) acryloyloxyethyl phthalic acid, 2- (meth) acryloyloxyethyl hexahydrophthalic acid, carboxylethyl (meth) acrylate, 2- (meth) acryloyloxyethyl Succinic acid,
Examples thereof include N- (meth) acryloyloxy-N ', N'-dicarboxy-p-phenylenediamine and 4- (meth) acryloyloxyethyltrimellitic acid.
Further, the monofunctional (meth) acrylate monomer includes N-
Vinyl group-containing monomers such as vinylpyrrolidone and 4
Included are (meth) acryloylamino group-containing monomers such as-(meth) acryloylamino-1-carboxymethylpiperidine.

As the bifunctional (meth) acrylate monomer, alkylene glycol di (meth) acrylates, polyoxyalkylene glycol di (meth) acrylates, halogen-substituted alkylene glycol di (meth) acrylates, and aliphatic polyol di ( Typical examples are (meth) acrylates, di (meth) acrylates of alkylene oxide adducts of bisphenol A, and epoxy di (meth) acrylates of bisphenol A. Can be used. Specific examples of the bifunctional (meth) acrylate monomer include ethylene glycol di (meth) acrylate, 1,3-butanediol di (meth) acrylate, 1,4-butanediol di (meth) acrylate,
1,6-hexanediol di (meth) acrylate,
1,9-nonanediol di (meth) acrylate, isobornyl di (meth) acrylate, neopentyl glycol di (meth) acrylate, trimethylolpropane di (meth) acrylate, pentaerythritol di (meth) acrylate, ditrimethylolpropane di (meth) ) Acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate,
In addition to polypropylene glycol di (meth) acrylate and polytetramethylene glycol di (meth) acrylate, hydroxypivalate neopentyl glycol di (meth) acrylate, 2,2-bis [4- (meth) acryloyloxyethoxyethoxyphenyl] Propane, 2,2-bis [4- (meth) acryloyloxyethoxyethoxycyclohexyl] propane, 2,2
Examples include -bis [4- (meth) acryloyloxyethoxyethoxyphenyl] methane, hydrogenated dicyclopentadienyl di (meth) acrylate, and tris (hydroxyethyl) isocyanurate di (meth) acrylate.

Examples of polyfunctional (meth) acrylate monomers include glycerin tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, ditrimethylolpropane tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, pentaerythritol triacrylate. Polyfunctional trivalent or higher aliphatic polyol such as (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate Typical examples are (meth) acrylates, and poly (meth) acrylates of trivalent or higher valent halogen-substituted polyols and alkylene oxide addition of glycerin. Birds of tri (meth) acrylate, alkylene oxide adducts of trimethylolpropane (meth) acrylate, 1,1,1-tris [(meth)
Acryloyloxyethoxyethoxy] propane, tris (hydroxyethyl) isocyanurate tri (meth)
Acrylate etc. are mentioned.

As the (meth) acrylate oligomer, a bifunctional or higher polyfunctional urethane (meth) acrylate oligomer (hereinafter referred to as a polyfunctional urethane (meth) acrylate oligomer), a bifunctional or higher polyfunctional polyester (meth) acrylate oligomer ( Hereinafter, referred to as a polyfunctional polyester (meth) acrylate oligomer), 2
A polyfunctional epoxy (meth) acrylate oligomer having a functionality or higher (hereinafter referred to as a polyfunctional epoxy (meth) acrylate oligomer) can be used. The (meth) acrylate oligomer can be one kind or two or more kinds.

As the polyfunctional urethane (meth) acrylate oligomer, at least one (meth) acrylate is included in one molecule.
Examples thereof include a urethanization reaction product of a (meth) acrylate monomer having an acryloyloxy group and a hydroxyl group and polyisocyanate. The polyfunctional urethane (meth) acrylate oligomer comprises an isocyanate compound obtained by reacting a polyol with a polyisocyanate, and a (meth) acrylate monomer having at least one (meth) acryloyloxy group and a hydroxyl group in one molecule. Examples thereof include urethanization reaction products.

The (meth) acrylate monomer having at least one (meth) acryloyloxy group and hydroxyl group in one molecule used for the urethanization reaction is 2
-Hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, glycerin di (meth) acrylate, trimethylolpropanedi (Meth) acrylate, pentaerythritol tri (meth)
Acrylate, dipentaerythritol penta (meth)
An acrylate is mentioned.

As the polyisocyanate used for the urethanization reaction, hexamethylene diisocyanate, lysine diisocyanate, isophorone diisocyanate,
Dicyclohexylmethane diisocyanate, tolylene diisocyanate, xylylene diisocyanate, diisocyanates obtained by hydrogenating aromatic isocyanates among these diisocyanates (for example, diisocyanates such as hydrogenated tolylene diisocyanate and hydrogenated xylylene diisocyanate), triphenylmethane Examples thereof include diisocyanate polyisocyanates such as triisocyanate and dimethylenetriphenyltriisocyanate, and polyisocyanates obtained by polymerizing diisocyanates.

As the polyols used in the urethanization reaction, in general, in addition to aromatic, aliphatic and alicyclic polyols, polyester polyols, polyether polyols and the like are used. Usually, as aliphatic and alicyclic polyols, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, ethylene glycol, propylene glycol, trimethylolethane,
Examples thereof include trimethylolpropane, dimethylolheptane, dimethylolpropionic acid, dimethylolbutyronic acid, glycerin and hydrogenated bisphenol A.

The polyester polyol is obtained by a dehydration condensation reaction between the above polyols and a polybasic carboxylic acid (anhydride). Specific compounds of polybasic carboxylic acid include (anhydrous) succinic acid, adipic acid, (anhydrous) maleic acid, (anhydrous) trimellitic acid, hexahydro (anhydrous) phthalic acid, (anhydrous) phthalic acid, isophthalic acid, Examples include terephthalic acid. In addition to the polyalkylene glycol, examples of the polyether polyol include a polyoxyalkylene-modified polyol obtained by reacting the above-mentioned polyol or phenols with an alkylene oxide.

The polyfunctional polyester (meth) acrylate oligomer can be obtained by a dehydration condensation reaction of (meth) acrylic acid, polybasic carboxylic acid (anhydride) and polyol. The polybasic carboxylic acid (anhydride) used in the dehydration condensation reaction is (anhydrous) succinic acid, adipic acid, (anhydrous) maleic acid, (anhydrous) itaconic acid, (anhydrous) trimellitic acid, (anhydrous) pyromellitic acid. Acid, hexahydro (anhydrous) phthalic acid, (anhydrous) phthalic acid, isophthalic acid, terephthalic acid and the like can be mentioned. As the polyol used in the dehydration condensation reaction, 1,4-butanediol, 1,6-hexanediol, diethylene glycol, triethylene glycol, propylene glycol, neopentyl glycol, dimethylolheptane,
Examples thereof include dimethylolpropionic acid, dimethylolbutyronic acid, trimethylolpropane, ditrimethylolpropane, pentaerythritol, and dipentaerythritol.

The polyfunctional epoxy (meth) acrylate oligomer can be obtained by an addition reaction of polyglycidyl ether and (meth) acrylic acid. As the polyglycidyl ether, ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether,
Tripropylene glycol diglycidyl ether, 1,
Examples thereof include 6-hexanediol diglycidyl ether and bisphenol A diglycidyl ether.

The photopolymerization initiator (b) of the present invention initiates curing of the composition of the present invention by irradiation with active energy rays, and a generally known photopolymerization initiator can be used. Specifically, benzoin, benzophenone, benzoin ethyl ether, benzoin isopropyl ether, 2,2-dimethoxy-2-phenylacetophenone, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropane-1- Examples thereof include, but are not limited to, on, azobisisobutyronitrile, and benzoyl peroxide.

The amount of the photopolymerization initiator (b) used is (meth)
1 to 100 parts by weight of the acrylic ester derivative (a)
-10 parts by weight, preferably 2-5 parts by weight are used. If the amount of the photopolymerization initiator used is more than the above range, the cured film will be colored, and if it is less than the above range, a sufficient curing rate cannot be obtained.

The aggregate obtained from the colloidal silica (c) and the hindered amine light stabilizer (d) in the photocurable resin composition for matte coating of the present invention contains the hindered amine light stabilizer (e). It can be obtained simply by adding and mixing the hindered amine light stabilizer (d) to the colloidal silica (c) at room temperature under or without it.

In the colloidal silica (c) of the present invention, as an organic solvent which is a dispersion solvent, methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, ethylene glycol, ethylene glycol monoethyl ether ( Hereinafter, referred to as ethyl cellosolve), an alcohol solvent such as ethylene glycol mono n-propyl ether,
Aromatic hydrocarbons such as toluene and xylene, acetone,
Examples thereof include ketones such as methyl ethyl ketone and methyl isobutyl ketone, acetic acid esters such as ethyl acetate and butyl acetate, and dimethylacetamide.
More than one seed can be used. Of these, alcohol organic solvents are particularly preferable.

In the present invention, colloidal silica (c)
The particle size and concentration of the ultrafine particle silica are not particularly limited, and for example, those containing about 20 to 30% by weight of ultrafine particle silica in a dispersion liquid which is easily available as a commercial product can be used. The colloidal silica (c) may contain two or more kinds of ultrafine particle silica having different particle sizes, for example, ultrafine particle silica having a particle size of 10 to 20 mμ and a particle size of 50 to 50 μm.
Examples include those in which 600 mμ of ultrafine silica particles are dispersed in an organic solvent.

Examples of commercially available colloidal silica (c) include, for example, methanol silica sol whose organic solvent is methyl alcohol [silica particle size: 10 to 15 mμ, solid content: 30% by weight, manufactured by Nissan Chemical Industries, Ltd.], MA-ST
-M [silica particle size: 20 to 25 mμ, solid content: 40% by weight, manufactured by Nissan Chemical Industries, Ltd.] or OSCAL113
2 [silica particle size: 10 to 20 mμ, solid content: 30 to 31
% By weight, manufactured by Catalysts & Chemicals Industry Co., Ltd., OSCAL 1232 in which the solvent is ethyl alcohol [silica particle size: 10
20 mμ, solid content: 30 to 31% by weight, manufactured by Catalyst Kasei Kogyo Co., Ltd.], and the solvent is n-propyl alcohol O
SCAL1332 [silica particle size: 10 to 20 mμ, solid content: 30 to 31% by weight, manufactured by Catalysts & Chemicals Industry Co., Ltd.], IPA-ST in which the solvent is isopropyl alcohol [silica particle size: 10 to 15 mμ, solid content: 30 wt%, manufactured by Nissan Chemical Industries, Ltd.] or OSCAL1432 [silica particle size: 10 to 20 mμ, solid content: 30 to 31 wt%, manufactured by Catalysts & Chemicals Industry Co., Ltd.], and the solvent is n-butyl alcohol. NBA-ST [silica particle size: 10 to 15 mμ, solid content: 20% by weight, manufactured by Nissan Chemical Industries, Ltd.] or O
SCAL1532 [silica particle size: 10 to 20 mμ, solid content: 30 to 31% by weight, manufactured by Catalysts & Chemicals Industry Co., Ltd.], EG-ST in which the solvent is ethylene glycol [silica particle size: 10 to 15 mμ, solid content: 20 wt%, manufactured by Nissan Chemical Industries, Ltd.] or EG-ST-ZL [silica particle size:
70 to 100 mμ, solid content: 20% by weight, manufactured by Nissan Chemical Industries, Ltd.], OSCA in which the solvent is ethyl cellosolve
L1632 [silica particle size: 10 to 20 mμ, solid content: 3
0 to 31% by weight, manufactured by Catalysts & Chemicals Industry Co., Ltd.], and the solvent is ethylene glycol mono-n-propyl ether NP
C-ST [silica particle size: 10 to 15 mμ, solid content: 30
% By weight, manufactured by Nissan Chemical Industries, Ltd.] or NPC-ST
-2 [silica particle size: 400 to 500 mμ, solid content: 20
Wt%, manufactured by Nissan Chemical Industries, Ltd.], the solvent is dimethylacetamide DMAC-ST [silica particle size: 10
15mμ, solid content: 20% by weight, Nissan Chemical Industries, Ltd.
Manufactured] or DMAC-ST-ZL [silica particle size: 7
0 to 100 mμ, solid content: 20% by weight, manufactured by Nissan Chemical Industries, Ltd.], XBA-ST [silica particle size: 10] in which the solvent is a mixed solvent of xylene and n-butyl alcohol.
15mμ, solid content: 30% by weight, Nissan Chemical Industries, Ltd.
Manufactured], MIBK in which the solvent is methyl isobutyl ketone
-ST [silica particle size: 10 to 15 mμ, solid content: 30% by weight, manufactured by Nissan Chemical Industries, Ltd.] and the like. The colloidal silica (c) may be used alone or in combination of two or more.

[0027] Two or more kinds of colloidal silica (c) are used in combination
If the particle size is 10 to 20 mμ dispersed in an organic solvent,
Fine particle silica (hereinafter referred to as colloidal silica (c1)
U) and a particle size of 50-600mμ dispersed in an organic solvent
Fine particle silica (hereinafter referred to as colloidal silica (c2)
U) is preferably used in combination.

The mixing ratio of the colloidal silica (c1) and the colloidal silica (c2) is such that the (meth) acrylic acid derivative (a) to be used and the base material to which the photocurable resin composition for matte coating of the present invention is applied. 5 to 100 parts by weight, preferably 10 to 60 parts by weight, in terms of the ultrafine particle silica pure content, based on 100 parts by weight of the ultrafine particle silica pure content of the colloidal silica (c1). Is. A matte cured coating can be obtained even if the mixing ratio of the colloidal silica (c1) and the colloidal silica (c2) is outside the above range, but in order to obtain a finer cured coating with a matte pattern, it is necessary to mix in the above range. Good.

Representative examples of the hindered amine light stabilizer (d) of the present invention include a light stabilizer comprising a compound having an average of two or more cyclic hindered amine structures in the molecule. The cyclic hindered amine structure has the general formula (1):

Embedded image (In the formula, R ¹ , R ² , R ³ and R ⁴ are the same or different and each represents an alkyl group. R ⁵ represents a hydrogen atom, an alkyl group, an acetyl group or an alkoxy group.) A divalent group obtained by removing R ⁵ or a hydrogen atom at the 4-position of the piperidine ring from the monovalent group, the general formula (2):

Embedded image (In the formula, R ¹ , R ² , R ³ , and R ⁴ are the same as above.) And the like. Specifically 2,
2,6,6-tetramethylpiperidyl group, 1,2,2
6,6-pentamethylpiperidyl group, 4-hydroxy-
2,2,6,6-tetramethyl-1-piperidyl group,
2,2,6,6-tetramethyl-1,4-piperidinediyl group and the like can be mentioned. A preferable cyclic hindered amine structure is 2,2,6,6-tetramethyl-4-
Piperidyl group, 1,2,2,6,6-pentamethyl-4
A piperidyl group.

Specific examples of the hindered amine light stabilizer (d) include bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate (commercially available trade name: Sumisorb 577, Sumitomo Chemical Co., Ltd. Co., Ltd.), bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate (trade name: SANOL LS-76 as a commercial product)
5, manufactured by Sankyo Co., Ltd., tetrakis (2,2,6,6-tetramethyl-4-piperidyl) 1,2,3,4-butanetetracarboxylic xylate (trade name: ADEKA STAB LA-57 as a commercial product) , Asahi Denka Kogyo Co., Ltd., Tetrakis (1,2,2,6,6-pentamethyl-4-piperidyl) 1,2,3,4-butanetetracarboxylic xylate (trade name Adekastab LA as a commercial product) -52, manufactured by Asahi Denka Kogyo Co., Ltd., (mixed 2,2,6,6-tetramethyl-4-piperidyl / tridecyl) 1,2,3,4-butanetetracarboxylic xylate (commercially available product Name ADEKA STAB LA-67, manufactured by Asahi Denka Co., Ltd., (mixed 1,2,2,6,6-pentamethyl-4-piperidyl / tridecyl) 1,2,3,4-butanetetracarboxylic xylate (commercially available The trade names ADK STAB LA-
62, manufactured by Asahi Denka Co., Ltd., 8-acetyl-3-dodecyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro [4.5] decane-2,4-dione ( As a commercial product, the product name is SANOL LS-440, Sankyo Co., Ltd.
Manufactured) and the like.

As the hindered amine light stabilizer (d), oligomer type or polymer type light stabilizers having an average of two or more cyclic hindered amine structures in the molecule can also be used. As such a light stabilizer, a mixture having a molecular weight of about 2000 {1,2,2,6,6-pentamethyl-4-piperidyl / β, β, β ′, β′-tetramethyl-3,9- [2,4 , 8,10-Tetraoxaspiro (5.5) undecane] diethyl} -1,2,3,4-
Butane tetracarboxylic xylate (commercially available product name: ADEKA STAB LA-63 or 63P, manufactured by Asahi Denka Co., Ltd.), mixed with a molecular weight of about 1900 {2, 2, 6, 6
-Tetramethyl-4-piperidyl / β, β, β ′, β ′
-Tetramethyl-3,9- [2,4,8,10-tetraoxaspiro (5.5) undecane] diethyl} -1,
2,3,4-Butane tetracarboxylic xylate (Adeka Stab LA-68LD as a commercial product, Asahi Denka Kogyo Co., Ltd.)
Manufactured) and the like.

The mixing ratio of the colloidal silica (c) and the hindered amine light stabilizer (d) is usually such that the hindered amine light stabilizer (d) is added to 100 parts by weight of the pure silica in the colloidal silica (c). 0.5-60 parts by weight,
It is preferably 1 to 50 parts by weight. If the content of the hindered amine light stabilizer (d) is more than the above range, it is difficult to control the aggregation, and the particle diameter of the aggregate becomes non-uniform, so that the cured film may have glossiness or spots. It is difficult to obtain a matt cured coating having a good appearance. On the other hand, if the amount is less than the above range, it is difficult to obtain agglomerates up to a size capable of expressing matting.

In the aggregate of the present invention, the colloidal silica (c) is contained in an amount of 0.1 to 15 parts by weight, preferably 0 to 0 parts by weight, based on 100 parts by weight of the (meth) acrylic acid ester derivative (a). It may be added in an amount of 0.5 to 10 parts by weight. If the weight of pure silica is more than the above range,
It is difficult to obtain a matte cured coating having a good appearance such that the particle diameter of the agglomerates becomes non-uniform and the cured coating has blurring or scratches. When the weight of the pure silica component is less than the above range, matte tends not to appear.

In the present invention, the colloidal silica (c) is added in the presence of the hindered amine light stabilizer (e).
It is preferable that the hindered amine light stabilizer (d) is added to and mixed with to prepare an aggregate. When the hindered amine light stabilizer (e) is present, the particle size of the agglomerates can be made smaller than in the case of using the hindered amine light stabilizer (d) alone, so that a finer matte pattern cured film can be obtained. It is effective in obtaining a composition that can be formed.

The hindered amine-based light stabilizer (e) of the present invention cannot agglomerate the ultrafine particle silica in the colloidal silica (c) by itself.
Typical examples of the hindered amine light stabilizer (e) include a light stabilizer composed of a compound having one cyclic hindered amine structure in the molecule. Examples of the cyclic hindered amine structure include those described above for the hindered amine light stabilizer (d).

Specific hindered amine light stabilizers (e) include 4-benzoyloxy-2,2,6,6.
6-Tetramethylpiperidine (commercial name: Sanol LS-744, manufactured by Sankyo Co., Ltd.), 1- [2- {3
-(3,5-Di-t-butyl-4-hydroxyphenyl) propionyloxy} ethyl] -4- {3- (3,
5-di-t-butyl-4-hydroxyphenyl) propionyloxy} -2,2,6,6-tetramethylpiperidine (commercially available as trade name Sanol LS-2626,
Sankyo Co., Ltd.), 1,2,2,6,6-pentamethyl-
4-piperidyl methacrylate (commercially available as ADEKA STAB LA-82, manufactured by Asahi Denka Co., Ltd.), 2,
2,6,6-Tetramethyl-4-piperidyl methacrylate (commercially available product name: ADEKA STAB LA-87,
Asahi Denka Kogyo Co., Ltd. and the like.

The amount of the hindered amine light stabilizer (e) used varies depending on the kind of the light stabilizer, but, for example, 2,2,6,6-
When tetramethyl-4-piperidyl methacrylate (commercially available product name: ADEKA STAB LA-87) is used, ultrafine particle silica in colloidal silica (c) 1
It is usually 1 to 12 parts by weight, preferably 3 to 10 parts by weight, relative to 00 parts by weight. When a hindered amine-based light stabilizer (e) other than the above is used, the above 2,2,6,6-tetramethyl-4-piperidyl methacrylate is added to 100 parts by weight of the ultrafine particle silica in the colloidal silica (c). The amount to be used may be determined so that the same number of cyclic hindered amine structural units as those used are present.

When the hindered amine light stabilizer (e) is not used, the photocurable resin composition for matte coating of the present invention is usually a (meth) acrylic acid ester derivative (a), a photopolymerization initiator. It can be produced by mixing (b) and colloidal silica (c), and then adding and mixing the hindered amine light stabilizer (d) to this mixture.

When the hindered amine light stabilizer (e) is used, the particle size of the agglomerates is reduced, and a photocurable resin composition for matte coating capable of forming a finer matte pattern cured film. To obtain the product, (meth) acrylic acid ester derivative (a), photopolymerization initiator (b), colloidal silica (c) and hindered amine light stabilizer (e)
Is preferably mixed, and then the hindered amine light stabilizer (d) is added to and mixed with the mixture to produce the composition. That is, (meth) acrylic acid ester derivative (a), photopolymerization initiator (b), colloidal silica (c)
And the hindered amine-based light stabilizer (d) and the hindered amine-based light stabilizer (e) are mixed, the resulting photocurable resin composition for matting coating has a finer matte pattern. Difficult to form a cured film.

The photocurable resin composition for matte coating of the present invention, which is obtained by any of the above-mentioned production methods, should be such that the amount of the hindered amine light stabilizer (d) used is within the above-mentioned range. For example, the hindered amine-based light stabilizer (d) develops its original property as a light stabilizer, and forms a cured film having weather resistance. Further, when the hindered amine light stabilizer (d) is used in an amount of 12 parts by weight or more with respect to 100 parts by weight of the ultrafine particle silica in the colloidal silica (c), deterioration of water resistance of the cured film due to silica is prevented,
On the contrary, water resistance can be improved.

The photocurable resin composition for matte coating of the present invention may be blended with a solvent and various additives such as a thickener, an antioxidant and an ultraviolet absorber. Examples of the solvent include alcohols such as ethyl alcohol, n-propyl alcohol, isopropyl alcohol and n-butyl alcohol, alkylene glycol monoethyl ether such as ethylene glycol monomethyl ether, ethyl cellosolve, ethylene glycol monobutyl ether, propylene glycol monomethyl ether and propylene glycol monobutyl ether. Alcohol-based solvents such as alkyl ethers are particularly preferable in terms of dispersion stability of aggregates, aromatic hydrocarbons such as toluene and xylene, acetic acid esters such as ethyl acetate and butyl acetate, ketones such as acetone and methyl ethyl ketone. Can also be used.

The photocurable resin composition for matte coating of the present invention is usually mixed with an appropriate solvent and applied to a synthetic resin molded article, and then irradiated with ultraviolet rays to be cured. It can also be cured by irradiating with active energy rays other than ultraviolet rays, for example, α rays, β rays, γ rays, electron rays and the like.

A thermoplastic resin or a thermosetting resin can be used without distinction as a base material of a synthetic resin molded article on which the photocurable resin composition for matte coating of the present invention is applied.
Polymethyl methacrylate, polycarbonate, polyallyl diglycol carbonate, ABS resin, polystyrene, PVC, polyester resin, acetal resin and the like are used. In addition, as the shape of the synthetic resin molded product,
In addition to general molded products, sheets, films, etc. are also applicable.

As a coating method, known methods such as curtain flow coating, spray coating, roll coating and dipping may be appropriately used. The point is that any method can be used as long as a desired uniform thickness and a smooth surface can be obtained, and can be appropriately selected according to the shape of the object to be coated. The thickness of the coating is usually 0.5 to 20 µ, preferably 1.0 to 10 µ.

[0045]

EXAMPLES The present invention will be specifically described below with reference to examples, but these are merely examples and the present invention is not limited to these.

In the following Examples and Comparative Examples, the compounding amounts are parts by weight, and the colloidal silica (c) is parts by weight of pure silica. The abbreviations for the (meth) acrylic acid ester derivative (a), the colloidal silica (c) or the silica powder, and the hindered amine light stabilizers (d) and (e) in each example and each comparative example are as follows. Is.

<(Meth) acrylic ester derivative (a)> A: dipentaerythritol hexaacrylate B: urethane acrylate oligomer obtained by reaction of pentaerythritol triacrylate and dicyclohexylmethane diisocyanate C: pentaerythritol triacrylate and hexamethylene Urethane acrylate oligomer obtained by reaction with diisocyanate D: Urethane acrylate oligomer obtained by reaction of pentaerythritol triacrylate and isophorone diisocyanate E: Aronix M-8030 (polyester acrylate) [Toagosei Chemical Industry Co., Ltd.] F: Polyethylene glycol diacrylate [Shin Nakamura Chemical Co., Ltd. A-400] G: Aronix M-8100 ( Li ester acrylate) [manufactured by Toa Synthetic Chemical Industry Co., Ltd.]

<Colloidal silica (c) or silica powder> a: Silica sol IPA-ST (average particle size 10 to 15 mμ)
Dispersion of 30% by weight of silica in isopropanol)
[Manufactured by Nissan Chemical Industries, Ltd.] b: Syloid 404 (silica powder having an average particle size of 5.2μ) [manufactured by Fuji Devison Chemical Co., Ltd.] c: Syloid 244 (silica powder having an average particle size of 1.8μ) [Fuji Devison Chemical Co., Ltd.] d: Aerosil 200 (silica powder having an average particle size of 12 mμ) [Japan Aerosil Co., Ltd.] e: Silica sol NPC-ST-2 (average particle size 400 to 5)
20 wt% ethylene glycol mono-n-propyl ether dispersion of 00 mμ silica) [NISSAN CHEMICAL INDUSTRIES, LTD.]
Made]

<Hindered Amine Light Stabilizer> Hindered Amine Light Stabilizer (d) S-577: Sumisorb 577 [Sumitomo Chemical Co., Ltd.] LA-62: ADEKA STAB LA-62 [Asahi Denka Kogyo Co., Ltd.] LA-63P: ADEKA STAB LA-63P [manufactured by Asahi Denka Kogyo KK] Hindered amine light stabilizer (e) LA-87: ADEKA STAB LA-87 [manufactured by Asahi Denka Kogyo]

Examples 1 to 11 and Comparative Examples 1 to 7 (meth) acrylic acid ester derivative (a) shown in Table 1,
A photocurable resin composition for matte coating was produced using colloidal silica (c) or silica powder, a photopolymerization initiator (b) and a hindered amine light stabilizer (d). That is, a (meth) acrylic acid ester derivative (a), colloidal silica (c) or silica powder, a photopolymerization initiator (b) and ethyl cellosolve are mixed, and then a hindered amine light stabilizer (d) is gradually added to this mixture. The mixture was added and mixed to obtain a photocurable resin composition for a matte coating containing aggregates. 1-Hydroxycyclohexyl phenyl ketone was used as a photopolymerization initiator. Further, the amount of ethyl cellosolve used was such that the nonvolatile component of the resulting photocurable resin composition for matte coating was 37.5% by weight.

The photocurable resin composition for matte coating thus obtained was applied to a methacrylic resin plate having a thickness of 2 mm (SUMIPEX # 000 manufactured by Sumitomo Chemical Co., Ltd.) to form a coating film. 30 minutes at room temperature, then 5 at 60 ° C
After drying for a minute, the resin plate was put in the air into a high pressure mercury lamp (manufactured by Eye Graphics, eye cure UE021-403).
150 with C, 500V, H02-L41 (2))
The coating was cured by irradiating with ultraviolet light for 80 seconds at 80 W / cm from a distance of mm. Table 2 shows the evaluation results of the dispersion stability over time of the photocurable resin composition for matte coating, and the matte and physical property evaluation results of the cured coating formed on the methacrylic resin plate.

The evaluation of dispersion stability over time, the matte pattern and the evaluation of physical properties were carried out as follows (the same applies hereinafter). 1) Time-dependent dispersion stability: Observation of the state of the photocurable resin composition for matte coating after leaving at 40 ° C. ◯: A uniform state was maintained even after standing for 4 months or more. X: The silica that settled one month after standing was not redispersible. 2) Matte pattern: visual observation with a magnifying power of 10 3) Total light transmittance (%) and haze value: measured by haze computer 4) Gloss: measured by gloss meter 60 ° 5) Abrasion resistance: # Abrasion test with 0000 steel wool A: No scratch even if rubbed hard B: Slight scratch when rubbed strongly 6) Adhesion: Cross-cut cellophane tape peeling test Coating cutting line that reaches the substrate at 1 mm intervals 11 pieces are put in each of the vertical and horizontal directions to make 100 pieces of 1 mm, and cellophane tape is stuck on them to be rapidly peeled off. This cellophane tape operation was repeated 3 times at the same location, and the number of unpeeled cells is shown.

[0053]

[Table 1]

[0054]

[Table 2]

1) Clear means that the cured film is transparent,
It means that it did not have a matte appearance. (The same shall apply hereinafter.) 2) Since cracks occurred in the cured coatings of Comparative Examples 2 and 4, wear resistance and adhesion were not measured.

Examples 12 to 17 (meth) acrylic acid ester derivative (a) shown in Table 3,
A photocurable resin composition for matte coating was produced using colloidal silica (c), photopolymerization initiator (b), hindered amine light stabilizer (d) and hindered amine light stabilizer (e). That is, a (meth) acrylic acid ester derivative (a), colloidal silica (c), a photopolymerization initiator (b) and ethyl cellosolve are mixed, and a hindered amine light stabilizer (e) is first added to this mixture and mixed. Then, the hindered amine light stabilizer (d) was gradually added and mixed to obtain a photocurable resin composition for a matte coating containing aggregates. 1-as a photopolymerization initiator
Hydroxycyclohexyl phenyl ketone was used.
Further, the amount of ethyl cellosolve used was such that the nonvolatile component of the resulting photocurable resin composition for matte coating was 37.5% by weight.

The photocurable resin composition for matte coating thus obtained was formed into a cured film on a methacrylic resin plate in the same manner as in Example 1. Table 4 shows the evaluation results of the temporal dispersion stability of the photocurable resin composition for matte coating, and the matte and physical property evaluation results of the cured coating.

[0058]

[Table 3]

[0059]

[Table 4]

Examples 18 to 23 and Comparative Examples 8 to 12 (meth) acrylic acid ester derivative (a) shown in Table 5,
A photocurable resin composition for matte coating was produced using colloidal silica (c) or silica powder, a photopolymerization initiator (b) and a hindered amine light stabilizer (d). That is, a (meth) acrylic acid ester derivative (a), colloidal silica (c) or silica powder, a photopolymerization initiator (b) and ethyl cellosolve are mixed, and then a hindered amine light stabilizer (d) is gradually added to this mixture. The mixture was added and mixed to obtain a photocurable resin composition for a matte coating containing aggregates. 1-Hydroxycyclohexyl phenyl ketone was used as a photopolymerization initiator. Further, the amount of ethyl cellosolve used was such that the nonvolatile component of the resulting photocurable resin composition for matte coating was 37.5% by weight.

The photocurable resin composition for matte coating thus obtained was draped on a polycarbonate plate having a thickness of 2 mm (manufactured by Taiyu Equipment Co., Ltd.) to form a film, and the film was formed at room temperature for 30 minutes. Then, after drying at 70 ° C. for 5 minutes, the plate was subjected to a high pressure mercury lamp in the air (manufactured by Eye Graphics Co., Ltd., Eye Cure UE021-403C, 500V, H02-L4.
80 (W / c) from a distance of 150mm using 1 (2))
The coating was cured by irradiating ultraviolet rays for 5 seconds. Table 6 shows the evaluation results of the temporal dispersion stability of the photocurable resin composition for matte coating, and the matte and physical property evaluation results of the cured coating formed on the polycarbonate plate.

[0062]

[Table 5]

[0063]

[Table 6]

Examples 24-27 Mixing (meth) acrylic acid ester derivative (a), colloidal silica (c1), colloidal silica (c2), photopolymerization initiator (b) and ethyl cellosolve, and then mixing this mixture with a hindered amine. The light stabilizer (d) was gradually added and mixed to obtain a photocurable resin composition for matte coating containing aggregates. As the (meth) acrylic acid ester derivative (a), B: a urethane acrylate oligomer obtained by the reaction of pentaerythritol triacrylate and dicyclohexylmethane diisocyanate, G: Aronix M-8100 (polyester acrylate) [manufactured by Toagosei Co., Ltd.] And F: polyethylene glycol diacrylate [Shin Nakamura Chemical Co., Ltd. A-
400] as the photopolymerization initiator (b)
Hydroxycyclohexyl phenyl ketone is used as a hindered amine light stabilizer (d) in ADEKA STAB LA-
62 (manufactured by Asahi Denka Kogyo Co., Ltd.) and the colloidal silica (c1) and colloidal silica (c2) shown in Table 7 were used. In addition, the amount of ethyl cellosolve used was such that the non-volatile content of the resulting photocurable resin composition for matte coating was 37.5% by weight.

The photocurable resin composition for matte coating thus obtained was draped on a polycarbonate plate having a thickness of 2 mm [manufactured by Taikyu Equipment Co., Ltd.] to form a coating film, and 70
After drying at 5 ° C. for 5 minutes, the plate was put in the air into a high-pressure mercury lamp [I-Cure-UE021-40, manufactured by Eye Graphics Co., Ltd.].
3C, 500V, H02-L41 (2)] 15
The coating was cured by irradiating with ultraviolet light for 5 seconds at 80 W / cm from a distance of 0 mm.

Table 8 shows the results of evaluation of the temporal dispersion stability of the photocurable resin composition for matte coating, and the results of matte pattern evaluation and physical property evaluation of the cured coating formed on the polycarbonate plate.

Comparative Example 13 A photocurable resin composition was obtained in the same manner as in Example 24 except that the hindered amine light stabilizer (d) was not added. Using the photocurable resin composition thus obtained, a cured film was formed on a polycarbonate plate in the same manner as in Example 24. The cured coating was transparent and did not have a matte appearance. Evaluation of temporal dispersion stability of the photocurable resin composition,
The physical properties of the cured coating formed on the polycarbonate plate were evaluated in the same manner as in Example 24. Table 8 shows the results.

Comparative Examples 14 to 16 Colloidal silica (c1) and colloidal silica (c
A photocurable resin composition was obtained in the same manner as in Comparative Example 13 except that silica fine powder shown in Table 7 was used instead of 2). Using the photocurable resin composition thus obtained, a cured film was formed on a polycarbonate plate in the same manner as in Example 24. The evaluation of dispersion stability over time of the photocurable resin composition, and the matte pattern evaluation and physical property evaluation of the cured coating formed on the polycarbonate plate were performed in the same manner as in Example 24. Table 8 shows the results.

[0069]

[Table 7]

[0070]

[Table 8]

Examples 28 to 35 B and G as (meth) acrylic acid ester derivative (a)
D: a urethane acrylate oligomer obtained by the reaction of pentaerythritol triacrylate and isophorone diisocyanate is used instead of the mixture of F and colloidal silica (c1) and colloidal silica (c2) shown in Table 9, and A matte coating photocurable resin composition containing an agglomerate was obtained in the same manner as in Example 24 except that the amount of the hindered amine light stabilizer (d) was changed to the amount shown in Table 9.

The photocurable resin composition for matte coating thus obtained was draped on a methacrylic resin plate having a thickness of 2 mm [SUMIPEX # 000 manufactured by Sumitomo Chemical Co., Ltd.] to form a film. 30 minutes at room temperature, then 5 at 60 ° C
After the drying for a minute, the resin plate was placed in the air and the high pressure mercury lamp [manufactured by Eye Graphics Co., Ltd., Eye Cure-UE021-403
C, 500V, H02-L41 (2)] and 150
The coating was cured by irradiating with ultraviolet light for 80 seconds at 80 W / cm from a distance of mm. The evaluation of the dispersion stability over time of the photocurable resin composition for matte coating, the matte pattern evaluation and the physical property evaluation of the cured coating formed on the methacrylic resin plate were carried out in the same manner as in Example 24. The results are shown in Table 10.

Comparative Examples 17 to 22 Colloidal silica (c1) and colloidal silica (c
A photocurable resin composition was obtained in the same manner as in Example 28 except that the silica fine powder shown in Table 9 was used instead of 2) and the hindered amine light stabilizer (d) was not added.
Using the photocurable resin composition thus obtained, a cured film was formed on a methacrylic resin plate in the same manner as in Example 28. Evaluation of dispersion stability over time of the photocurable resin composition, and matte pattern evaluation and physical property evaluation of the cured coating formed on the methacrylic resin plate were performed in the same manner as in Example 24.
The results are shown in Table 10.

[0074]

[Table 9]

[0075]

[Table 10]

Examples 36 to 39 B and G as the (meth) acrylic acid ester derivative (a)
Instead of the mixture of C and P, a urethane acrylate oligomer obtained by the reaction of C: pentaerythritol triacrylate and hexamethylene diisocyanate is used, and colloidal silica (c1) and colloidal silica (c2) shown in Table 11 are used, A matte coating photocurable resin composition containing an aggregate was obtained in the same manner as in Example 24 except that the amount of the hindered amine light stabilizer (d) was changed to 0.4 part by weight. Example 28 was carried out using the photocurable resin composition for matte coating thus obtained.
A cured coating was formed on the methacrylic resin plate in the same manner as in. Evaluation of dispersion stability over time of the photocurable resin composition, and matte pattern evaluation and physical property evaluation of the cured coating formed on the methacrylic resin plate were performed in the same manner as in Example 24. The results are shown in Table 12.

[0077]

[Table 11]

[0078]

[Table 12]

The embodiments of the present invention include: (1) Aggregation obtained from polyfunctional urethane (meth) acrylate oligomer, photopolymerization initiator (b) and colloidal silica (c), and hindered amine light stabilizer (d). A photocurable resin composition for matte coating, which comprises a substance. (2) The photocurable resin composition for matte coating according to (1) above, wherein the polyfunctional urethane (meth) acrylate oligomer is obtained by a urethanization reaction of a (meth) acrylate monomer having a hydroxyl group and a diisocyanate. (3) The photocurable resin composition for matte coating according to (1), wherein the (meth) acrylate monomer having a hydroxyl group is pentaerythritol triacrylate. (4) Obtained from a colloidal silica (c) and a hindered amine light stabilizer (d) in the presence of a polyfunctional urethane (meth) acrylate oligomer, a photopolymerization initiator (b) and a hindered amine light stabilizer (e). A photocurable resin composition for matte coating, which comprises an aggregate. (5) The photocurable resin composition for matte coating according to (4) above, wherein the polyfunctional urethane (meth) acrylate oligomer is obtained by a urethanization reaction of a (meth) acrylate monomer having a hydroxyl group and a diisocyanate. (6) The photocurable resin composition for matte coating according to (4), wherein the (meth) acrylate monomer having a hydroxyl group is pentaerythritol triacrylate. Is mentioned.

As another embodiment of the photocurable resin composition for matte coating of the present invention, 100 parts by weight of (meth) acrylic acid ester derivative (a), 1 to 1 of photopolymerization initiator (b) 10 parts by weight, colloidal silica (c1), colloidal silica (c2), and colloidal silica (c1) and colloidal silica (c2) having an ultrafine silica content of 5 to 100 parts by weight per 100 parts by weight of ultrafine silica. 0.1 to 15 parts by weight of an aggregate obtained from 0.5 to 60 parts by weight of the hindered amine light stabilizer (d) based on 100 parts by weight of the total ultrafine silica particles together with c2). And a photocurable resin composition for matting coating.

[0081]

INDUSTRIAL APPLICABILITY The photocurable resin composition for matte coating of the present invention is excellent in dispersion stability over time, and when the composition is applied to a synthetic resin molded article and irradiated with active energy rays, colloidal The aggregate obtained from silica (c) and the hindered amine light stabilizer (d) can form a matt cured film on the surface of the synthetic resin molded article. And, by selecting the kind and amount of the hindered amine light stabilizer (d), it is difficult to obtain a fine luster that is difficult to obtain with a conventional photocurable resin composition for coating using a matting agent of silica fine powder. It is possible to form a matte cured coating having an eraser pattern.

Further, the photocurable resin composition for matte coating of the present invention can be obtained from colloidal silica (c) and hindered amine light stabilizer (d) in the presence of hindered amine light stabilizer (e). When it contains agglomerates, a finer matte-patterned matte-cured coating can be formed.

Further, when the photocurable resin composition for matte coating of the present invention is a combination of colloidal silica (c1) and colloidal silica (c2) as colloidal silica (c), these hindered amine-based compounds are used. By the aggregate obtained from the light stabilizer (d), it is possible to form a matte cured coating having fine matte patterns on the surface of the synthetic resin molded article.

Claims (22)

[Claims] 1. A (meth) acrylic acid ester derivative (a) having at least one (meth) acryloyloxy group in the molecule, a photopolymerization initiator (b), and ultrafine particle silica dispersed in an organic solvent ( A photocurable resin composition for matte coating, comprising an aggregate obtained from c) and a hindered amine-based light stabilizer (d) capable of aggregating the ultrafine particle silica. 2. The composition according to claim 1, wherein the hindered amine-based light stabilizer (d) capable of aggregating the ultrafine particle silica is a light stabilizer having an average of two or more cyclic hindered amine structures in the molecule. 3. The hindered amine light stabilizer (d) capable of aggregating the ultrafine silica particles is used in an amount of 0.5 to 60 parts by weight based on 100 parts by weight of the ultrafine silica particles.
Or the composition according to 2. 4. The composition according to claim 1, wherein the organic solvent is an alcohol solvent. 5. A (meth) acrylic acid ester derivative (a) having at least one (meth) acryloyloxy group in the molecule, a photopolymerization initiator (b) and ultrafine silica particles (c) dispersed in an organic solvent. 2. The method for producing a composition according to claim 1, wherein the mixture of 1) is mixed with a hindered amine light stabilizer (d) capable of aggregating ultrafine silica particles. 6. The method according to claim 5, wherein the organic solvent is an alcohol solvent. 7. A (meth) acrylic acid ester derivative (a) having at least one (meth) acryloyloxy group in the molecule, a photopolymerization initiator (b), and one cyclic hindered amine structure in the molecule. In the presence of the light stabilizer (e) having, the aggregate obtained from the ultrafine particle silica (c) dispersed in an organic solvent and the hindered amine light stabilizer (d) capable of aggregating the ultrafine particle silica is formed. A photocurable resin composition for matte coating, characterized by containing. 8. The composition according to claim 7, wherein the organic solvent is an alcohol solvent. 9. A (meth) acrylic acid ester derivative (a) having at least one (meth) acryloyloxy group in the molecule, a photopolymerization initiator (b), and ultrafine silica particles (c) dispersed in an organic solvent. ) And a light stabilizer (e) having one cyclic hindered amine structure in the molecule, and a hindered amine light stabilizer (d) capable of aggregating ultrafine silica particles are mixed. Item 7. A method for producing the composition according to Item 7. 10. The method according to claim 9, wherein the organic solvent is an alcohol solvent. 11. A synthetic resin obtained by applying the photocurable resin composition for matte coating according to claim 1 to a synthetic resin molded article and then irradiating it with active energy rays to form a matte cured film on the surface. Molding. 12. A synthetic resin in which the photocurable resin composition for matte coating according to claim 4 is applied to a synthetic resin molded article and then irradiated with active energy rays to form a matte cured film on the surface. Molding. 13. A synthetic resin obtained by applying the photocurable resin composition for matte coating according to claim 7 to a synthetic resin molded article and then irradiating it with active energy rays to form a matte cured film on the surface. Molding. 14. A synthetic resin in which the photocurable resin composition for matte coating according to claim 8 is applied to a synthetic resin molded article and then irradiated with active energy rays to form a matte cured film on the surface. Molding. 15. The ultrafine particle silica (c) dispersed in an organic solvent comprises ultrafine particle silica having a particle size of 10 to 20 mμ and ultrafine particle silica having a particle size of 50 to 600 mμ dispersed in an organic solvent. The composition of claim 1 which comprises: 16. Ultrafine silica particles (c) having an ultrafine particle size (c) dispersed in an organic solvent and having a particle size of 10 to 20 mμ and a particle size range of 50 to 600 dispersed in an organic solvent.
The composition according to claim 1, which comprises mμ ultrafine silica. 17. A hindered amine light stabilizer (d) capable of agglomerating ultrafine silica particles has an average of 2 in the molecule.
The composition according to claim 15 or 16, which is a light stabilizer having one or more cyclic hindered amine structures. 18. The ultrafine particle silica having a particle size of 10 to 20 mμ is 100 parts by weight, and the ultrafine particle silica having a particle size of 50 to 600 mμ is 5 to 100 parts by weight.
The composition according to 5 or 16. 19. A total amount 1 of ultrafine particle silica having a particle size of 10 to 20 mμ and ultrafine particle silica having a particle size of 50 to 600 mμ.
The composition according to claim 15, 16 or 17, wherein 0.5 to 60 parts by weight of a hindered amine-based light stabilizer (d) capable of coagulating ultrafine silica particles is used with respect to 00 parts by weight. 20. The composition according to claim 15, 16, 17 or 18, wherein the organic solvent is an alcohol solvent. 21. A synthetic resin obtained by applying the photocurable resin composition for matte coating according to claim 16 to a synthetic resin molded article and then irradiating it with active energy rays to form a matte cured film on the surface. Molding. 22. A synthetic resin obtained by applying the photocurable resin composition for matte coating according to claim 19 to a synthetic resin molded article and then irradiating it with active energy rays to form a matte cured film on the surface. Molding.