JPH09302267A - Photocurable composition for matt coating and synthetic resin article made by using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photocurable compsn. which is excellent in dispersion stability during aging and can form a cured matt coating film with a fine matt pattern and to provide a synthetic resin article made by using the same. SOLUTION: This compsn. contains a (meth)acrylic ester deriv. having at least one (meth)acryloyloxy group, a photopolymn. initator, and an agglomerate obtd. from ultrafine antimony pentaoxide particles dispersed in an org. solvent and an amine capable of agglomerating the particles. The compsn. is applied to the surface of a synthetic resin article and irradiated with an active energy ray to form a cured matt coating film on the surface.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a photocurable composition for forming a matt cured film and a synthetic resin molded article using the composition.

[0002]

2. Description of the Related Art In order to impart a matting property to the surface of a synthetic resin molded article, a matting paint is generally used. recent years,
As a matte coating, a photocurable composition for matte coating is used, which is irradiated with active energy rays to form a matte cured film on the surface. The photocurable composition for matte coating is prepared by dispersing and mixing a predetermined matting agent in the photocurable composition of the base material to obtain a matte appearance according to the purpose, that is, a matte degree. . 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 anhydride (silica) are used as inorganic matting agents, and fine powders such as polyethylene, polypropylene, and polycarbonate are used as organic matting agents. Are frequently used.

[0003]

The photocurable composition for mat coating using silica fine powder as a matting agent has poor dispersion stability over time. That is, if this product is stored for a long period of time, there is a problem that the silica fine powder settles and caking which cannot be redispersed occurs. Conventionally, as a silica fine powder capable of expressing matting, a particle having a particle diameter of several μm to several tens of μm has been used, but with this silica fine powder, it is necessary to obtain a matte cured coating having a fine pattern. It was difficult.

An object of the present invention is to solve the problems under the present circumstances and to form a matte cured coating which is excellent in dispersion stability over time and has a fine matte pattern. (EN) Provided are a photocurable composition capable of being produced, and a synthetic resin molded article using the composition.

[0005]

Means for Solving the Problems As a result of intensive studies for achieving the above-mentioned object, the present inventors have found that a (meth) acrylic acid ester derivative (a) having at least one (meth) acryloyloxy group in the molecule. ) [Hereinafter, referred to as (meth) acrylic acid ester derivative (a). ], A photopolymerization initiator (b), and ultrafine particles of antimony pentoxide (c) dispersed in an organic solvent [hereinafter, referred to as colloidal antimony pentoxide (c). ] And an amine compound capable of aggregating the ultrafine particles of antimony pentoxide [hereinafter referred to as amine compound (d)]. ] The photocurable composition containing an aggregate obtained from and is excellent in dispersion stability over time, the aggregate exhibits a function as a matting agent to impart matte to the cured coating, Moreover, it was found that a fine matte-pattern cured film can be obtained by appropriately selecting the types and amounts of the colloidal antimony pentoxide (c) and the amine compound (d).
The present invention has been completed.

That is, the present invention provides a (meth) acrylic acid ester derivative (a), a photopolymerization initiator (b), and an aggregate obtained from a colloidal antimony pentoxide (c) and an amine compound (d). A photocurable composition for matting coating characterized by containing, and after coating the photocurable composition for matting coating on a synthetic resin molded article, the surface is matted and cured by irradiating with active energy rays. The present invention relates to a synthetic resin molded product having a coating film formed thereon.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION The (meth) acrylate derivative (a) of the present invention is a (meth) acrylate monomer having one or more (meth) acryloyloxy groups in the molecule [hereinafter referred to as (meth) acrylate It is called a monomer. ], A (meth) acrylate oligomer having two or more (meth) acryloyloxy groups in the molecule [hereinafter,
(Meth) acrylate oligomer. At least one compound having a (meth) acryloyloxy group. The (meth) acryloyloxy group means an acryloyloxy group and a methacryloyloxy group, and the (meth) acrylate derivative means an acrylate derivative and a methacrylate derivative, and a (meth) acrylate monomer and a (meth) acrylate 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. ], 2 in the molecule
Difunctional (meth) acrylate monomers having two (meth) acryloyloxy groups [hereinafter referred to as bifunctional (meth) acrylate monomers]. And at least 3 in the molecule
Multifunctional (meth) acrylate monomer having a number of (meth) acryloyloxy groups [hereinafter, referred to as a polyfunctional (meth) acrylate monomer. ]. One or more (meth) acrylate monomers can be used.

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, ethyl carbitol (meth) acrylate, trimethylolpropane mono (meth) acrylate, pentaerythritol Mono (meth) acrylate, phenoxy polyethylene glycol (meth) acrylate, as well as carboxyl group-containing (meth) acrylate monomer, -(Meth) acryloyloxyethyl phthalic acid, 2- (meth) acryloyloxyethyl hexahydrophthalic acid, carboxyethyl (meth) acrylate, 2- (meth) acryloyloxyethyl succinic acid, N- (meth) acryloyloxy-N ', N'
-Dicarboxy-p-phenylenediamine, 4- (meth) acryloyloxyethyl trimellitic acid and the like. Further, the monofunctional (meth) acrylate monomer includes a vinyl group-containing monomer such as N-vinylpyrrolidone and a (meth) acryloylamino group-containing monomer such as 4- (meth) acryloylamino-1-carboxymethylpiperidine. Is done.

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 include (meth) acrylate, bisphenol A or bisphenol F alkylene oxide adduct di (meth) acrylates, and bisphenol A or bisphenol F epoxy di (meth) acrylates.
The present invention is not limited to these, and various types 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, neopentyl glycol di (meth) acrylate, trimethylolpropane di (meth) acrylate, pentaerythritol di (meth) acrylate, ditrimethylol propane 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, polypropylene glycol di (meth) acrylate, polytetramethylene glycol di (meth) acrylate, and silicon di ( (Meth) acrylate, hydroxypivalic acid ester neopentyl glycol di (meth) acrylate, 2,2-bis [4- (meth) acryloyloxyethoxyethoxyphenyl] propane,
2,2-bis [4- (meth) acryloyloxyethoxyethoxycyclohexyl] propane, 2,2-bis [4- (meth) acryloyloxyethoxyethoxyphenyl] methane, hydrogenated dicyclopentadienyldi (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)
Acrylates, silicon hexa (meth) acrylate, and the like.

The (meth) acrylate oligomer is a bifunctional or higher polyfunctional urethane (meth) acrylate oligomer [hereinafter referred to as a polyfunctional urethane (meth) acrylate oligomer. ] Bifunctional or higher functional polyfunctional polyester (meth) acrylate oligomer [hereinafter referred to as polyfunctional polyester (meth) acrylate oligomer]. ] Bifunctional or higher polyfunctional epoxy (meth) acrylate oligomer [hereinafter referred to as polyfunctional epoxy (meth) acrylate oligomer] And the like. One or more (meth) acrylate oligomers can be used.

As the polyfunctional urethane (meth) acrylate oligomer, a urethane-forming reaction product of a (meth) acrylate monomer having at least one (meth) acryloyloxy group and at least one hydroxyl group in one molecule and a polyisocyanate, and polyols. Examples of the urethanization reaction product include an isocyanate compound obtained by reacting with a polyisocyanate and a (meth) acrylate monomer having at least one (meth) acryloyloxy group and one hydroxyl group in one molecule.

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)
Acrylate and the like.

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 di- or tri-polyisocyanates such as triisocyanate and dimethylenetriphenyltriisocyanate, and polyisocyanates obtained by multiplying diisocyanate.

As the polyols used in the urethanization reaction, in general, aromatic, aliphatic and alicyclic polyols, polyester polyols and polyether polyols are used. Usually, aliphatic and alicyclic polyols include 1,4-butanediol, 1,6-hexanediol, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, neopentyl glycol, trimethylolethane,
Trimethylolpropane, ditrimethylolpropane,
Pentaerythritol, dipentaerythritol, dimethylolheptane, dimethylolpropionic acid, dimethylolbutyronic acid, glycerin, hydrogenated bisphenol A and the like can be mentioned.

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 acids include (anhydride) succinic acid, adipic acid, (anhydride) maleic acid, (anhydride) itaconic acid,
(Anhydrous) trimellitic acid, (anhydrous) pyromellitic acid, hexahydro (anhydride) phthalic acid, (anhydrous) phthalic acid, isophthalic acid, terephthalic acid and the like. Examples of the polyether polyol include a polyoxyalkylene glycol, and a polyoxyalkylene-modified polyol obtained by reacting the polyol or phenol with an alkylene oxide.

The polyfunctional polyester (meth) acrylate oligomer is obtained by a dehydration condensation reaction of (meth) acrylic acid, polybasic carboxylic acid (anhydride) and polyol. Examples of polybasic carboxylic acids (anhydrides) used in the dehydration condensation reaction include (anhydride) succinic acid, adipic acid, (anhydride) maleic acid, (anhydride) itaconic acid, (anhydride) trimellitic acid, and (anhydro) pyro. Examples include melitic acid, hexahydro (anhydride) phthalic acid, (phthalic anhydride), isophthalic acid, terephthalic acid, and the like. Further, as the polyol used in the dehydration condensation reaction, 1,4-butanediol, 1,6-hexanediol, ethylene glycol, diethylene glycol, triethylene glycol,
Propylene glycol, neopentyl glycol, trimethylolethane, trimethylolpropane, ditrimethylolpropane, pentaerythritol, dipentaerythritol, dimethylolheptane, dimethylolpropionic acid, dimethylolbutyrionic acid, glycerin,
And hydrogenated bisphenol A.

The polyfunctional epoxy (meth) acrylate oligomer is obtained by the addition reaction of polyglycidyl ether and (meth) acrylic acid. As 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 generally known photopolymerization initiators 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 include, but are not limited to, on, azobisisobutyronitrile, and benzoyl peroxide.

In the colloidal antimony pentoxide (c) of the present invention, the organic solvent that is a dispersion solvent is methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, ethylene glycol, ethylene glycol mono. Ethyl ether (hereinafter referred to as ethyl cellosolve), alcohol solvents such as ethylene glycol mono-n-propyl ether, aromatic hydrocarbons such as toluene and xylene,
Examples thereof include ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone, acetic acid esters such as ethyl acetate and butyl acetate, and dimethylacetamide, and alcohol solvents are particularly preferable. The organic solvent that is a dispersion solvent is
These 1 type (s) or 2 or more types can be used.

In the present invention, the colloidal antimony pentoxide (c) is not particularly limited in the particle size and concentration of the ultrafine particles of antimony pentoxide, and for example, in a dispersion liquid which is easily available as a commercial product. Those containing about 30 wt% of ultrafine particles of antimony pentoxide of about 50 mμ can be used. Examples of commercially available colloidal antimony pentoxide (c) include, for example, Sun Colloid AMT-130 [solid content: 30% by weight, manufactured by Nissan Chemical Industries, Ltd.] in which the organic solvent is methyl alcohol, and the organic solvent is toluene. Sun colloid ATL-130 [solid content: 30% by weight, manufactured by Nissan Chemical Industries, Ltd.], organic solvent is dimethylformamide Sun colloid ADM-130 [solid content: 30 weight%, manufactured by Nissan Chemical Industries, Ltd.] ], Sun colloid AME-130 [solid content: 30 wt%, manufactured by Nissan Chemical Industries, Ltd.] in which the organic solvent is methyl ethyl ketone, and the like. . The colloidal antimony pentoxide (c) may be used alone or in combination of two or more.

The amine compound (d) means a low molecular weight compound to a high molecular weight compound having a plurality of amine structures in the molecule. Examples of the amine structure include a primary amine structure, a secondary amine structure, and a tertiary amine structure. The plurality of amine structures of the amine compound (d) may be the same or different.

(1) Low molecular weight compound having a plurality of amine structures in a molecule A low molecular weight compound having a plurality of amine structures in a molecule has a molecular weight of about 60 to less than about 1000 It has two or more amine structures. Specific examples thereof include the following aliphatic polyamines, alicyclic polyamines, aromatic polyamines, and nitrogen-containing heterocyclic polyamines having a plurality of cyclic hindered amine structures in the molecule [hereinafter referred to as cyclic hindered amine compound (1)]
Say. And a nitrogen-containing heterocyclic polyamine other than the cyclic hindered amine compound (1).

Aliphatic polyamines ethylenediamine, propylenediamine, 1,3-diaminopropane, 1,4-diaminobutane, hexamethylenediamine, 2,5-diamino-2,5-dimethylhexane, 2,2,4-trimethylhexa Methylenediamine, N, N-dimethylaminopropylamine, N, N-
Aliphatic diamines such as diethylaminopropylamine and aminoethylethanolamine; diethylenetriamine;
Dipropylene triamine, 1,3,6-tri (methylamino) hexane, bis (hexamethylene) triamine,
N- (3-aminopropyl) -1,3-propanediamine, N- (3-aminopropyl) -N-methyl-1,3
-Aliphatic triamines such as propanediamine; aliphatic tetra- or pentaamines such as triethylenetetramine and tetraethylenepentamine; alkanoldiamines such as N- (aminoethyl) ethanolamine.

Alicyclic polyamine isophoronediamine, bis (4-amino-3-methyldicyclohexyl) methane, bis (4-aminocyclohexyl) methane, menthenediamine, bis (aminomethyl) cyclohexane, 3,9-bis (3 -Aminopropyl) -2,4,8,10-tetraoxaspiro (5,
5) Undecane and the like.

Aromatic polyamine m-phenylenediamine, p-phenylenediamine, m
-Xylylenediamine, bis (4-aminophenyl) methane, bis (4-aminophenyl) sulfone, bis (4
-Amino-3-ethylphenyl) methane and the like.

Cyclic hindered amine compound (1) The cyclic hindered amine structure has the general formula (A):

[0029]

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, a general formula (B):

[0030]

Embedded image (Wherein, R ¹ , R ² , R ³ and R ⁴ are the same as above), and the like. Specifically,
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-piperidindiyl group and the like. Preferred cyclic hindered amine structures include 2,2,6,6-tetramethyl-4-
Piperidyl group, 1,2,2,6,6-pentamethyl-4
-Piperidyl groups.

Specific examples of the cyclic hindered amine compound (1) include bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate [commercially available under the trade name Sumisorb 577, Sumitomo Chemical Co., Ltd.] Bis (1,2,2,6,6-pentamethyl-4-piperidyl) [manufactured by Sankyo LS-765 as a commercial product, manufactured by Sankyo Co., Ltd.], tetrakis (2,2,6) 6-tetramethyl-4-piperidyl) 1,2,3,4-butanetetracarboxylate [commercially available as ADK STAB LA-57, manufactured by Asahi Denka Kogyo KK], tetrakis (1,
2,2,6,6-pentamethyl-4-piperidyl) 1,
2,3,4-butanetetracarboxylate [commercially available as ADK STAB LA-52, manufactured by Asahi Denka Kogyo Co., Ltd.] (mixed 2,2,6,6-tetramethyl-4)
-Piperidyl / tridecyl) 1,2,3,4-butanetetracarboxylate [commercially available as ADK STAB LA-67, manufactured by Asahi Denka Kogyo Co., Ltd.]
2,2,6,6-pentamethyl-4-piperidyl / tridecyl) 1,2,3,4-butanetetracarboxylate [commercially available as ADK STAB LA-62, manufactured by Asahi Denka Kogyo KK], 8 -Acetyl-3-dodecyl-
7,7,9,9-Tetramethyl-1,3,8-triazaspiro [4.5] decane-2,4-dione [commercially available as Sanol LS-440, manufactured by Sankyo Co., Ltd.] And the like.

Other than the cyclic hindered amine compound (1)
Nitrogen-containing heterocyclic polyamine N-aminoethylpiperazine, 1,3-di (4-piperidyl) propane, 2-aminopyridine, 3-aminopyridine, 4-aminopyridine, 2,3-diaminopyridine, 2,5- Diaminopyridine, 2,6-diaminopyridine, 2-pyridinemethanamine, 3-pyridinemethanamine, 4-pyridinemethanamine, 4,4′-dipyridyl, 1,3-di (4-pyridyl) ethylene, vinylpyridine Telomers, vinyl pyridine oligomers and the like.

(2) A high molecular compound having a plurality of amine structures in a molecule A high molecular compound having a plurality of amine structures in a molecule has a molecular weight of 1,000 or more and has an average amine structure in the molecule. It refers to two or more nitrogen-containing oligomers or polymers (hereinafter collectively referred to simply as nitrogen-containing polymers). The nitrogen-containing polymer includes an oligomer type or polymer type light stabilizer having an average of two or more cyclic hindered amine structures as described above, and a polymerizable light stabilizer having one cyclic hindered amine structure in the molecule. Polymer [Hereinafter, these are collectively referred to as a cyclic hindered amine compound (2). ], A homopolymer of a polymerizable amine, a copolymer of two or more polymerizable amines, a monomer having one or more polymerizable amines and an olefinically unsaturated group (excluding the polymerizable amines). And the like.

As the cyclic hindered amine compound (2), a mixed {1,2,2,6,6-pentamethyl-4-piperidyl / β, β, β ′, β′-tetramethyl-3,9 having a molecular weight of about 2,000 -[2,4,8,10-tetraoxaspiro (5.5) undecane] diethyl} -1,2,2
3,4-butanetetracarboxylate [commercially available as ADK STAB LA-63 or 63P (trade name, manufactured by Asahi Denka Kogyo Co., Ltd.)]
6-tetramethyl-4-piperidyl / β, β, β ′,
β'-tetramethyl-3,9- [2,4,8,10-tetraoxaspiro (5.5) undecane] diethyl}-
1,2,3,4-butanetetracarboxylate [commercially available as ADK STAB LA-68LD, manufactured by Asahi Denka Kogyo KK], 2,2,6,6-tetramethyl-4-
Homopolymer of piperidyl methacrylate [commercially available as Adeka Stab LA-87, manufactured by Asahi Denka Co., Ltd.], 1,2,2,6,6-pentamethyl-4-piperidyl methacrylate [commercially available Trade name, ADEKA STAB LA-82, manufactured by Asahi Denka Kogyo Co., Ltd.] and the like.

The polymerizable amine is preferably a polymerizable monoamine such as a vinyl monomer having one amine structure in the molecule and an isopropenyl monomer having one amine structure in the molecule. Examples of the polymerizable monoamine include vinyl monomers having a primary amine structure in a molecule such as vinylamine and allylamine; vinyl monomers having a secondary amine structure in a molecule such as diallylamine, N-methylallylamine and N-ethylallylamine; Vinylpyridine such as 2-vinylpyridine, 3-vinylpyridine and 4-vinylpyridine, 2-methyl-5-vinylpyridine,
Vinyl monomers having a heteroaromatic ring having a nitrogen atom as a hetero atom such as alkyl-vinylpyridine such as -methyl-6-vinylpyridine and 5-methyl-2-vinylpyridine as a tertiary amine structure in the molecule; Vinyl having a non-aromatic heterocyclic ring having a heteroatom such as vinyl-2-pyrrolidone, N-vinylcarbazole or N-acryloylmorpholine as a nitrogen atom and the nitrogen atom having a substituent as a tertiary amine structure in the molecule Monomers: triallylamine, N-methyldiallylamine, N, N-dimethylallylamine,
N, N-dimethylaminoethyl (meth) acrylate,
N, N-dialkylaminoalkyl (meth) acrylates such as N, N-diethylaminoethyl (meth) acrylate, N, N-dimethylacrylamide, N, N-diethylacrylamide, N- [3- (dimethylamino) propyl] meth Examples include, but are not limited to, vinyl or isopropenyl monomers having an aliphatic tertiary amine structure in the molecule such as acrylamide.

As the monomer having an olefinically unsaturated group used for copolymerization with a polymerizable amine (excluding the polymerizable amine), 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) are used. ) Acrylate, hydroxyalkyl (meth) acrylate such as 2-hydroxybutyl (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, alkyl (meth) acrylate such as butyl (meth) acrylate, styrene, vinyl acetate, Examples thereof include, but are not limited to, acrylonitrile.

Preferred amine compounds (d) include cyclic hindered amine compounds (1) and (2), homopolymers or copolymers of vinyl monomers having a heteroaromatic ring having a nitrogen atom as a hetero atom in an amine structure in the molecule. Coalescing,
And a homopolymer of N, N-dialkylaminoalkyl (meth) acrylate and a copolymer of N, N-dialkylaminoalkyl (meth) acrylate with styrene or hydroxyalkyl (meth) acrylate.

The photocurable composition for matte coating of the present invention comprises
(Meth) acrylic acid ester derivative (a), photopolymerization initiator (b) and colloidal antimony pentoxide (c) are mixed, and then the amine compound (d) is added and mixed to obtain the mixture. You can Further, first, colloidal antimony pentoxide (c) and an amine compound (d) are mixed to produce an aggregate, and then the (meth) acrylic acid ester derivative (a) and the photopolymerization initiator (b) are added to this mixture. It can also be obtained by adding and mixing. The latter method is suitable when an amino group-containing (meth) acrylate is used as the (meth) acrylate derivative (a).

The amount of the photopolymerization initiator (b) used is (meth)
1 to 100 parts by weight of the acrylate derivative (a)
10 to 10 parts by weight, preferably 2 to 5 parts by weight. When the amount of the photopolymerization initiator used is more than 10 parts by weight, the cured coating is colored, and when it is less than 1 part by weight, a sufficient curing rate cannot be obtained.

The compounding ratio of the colloidal antimony pentoxide (c) and the amine compound (d) is usually such that ultrafine particles of antimony pentoxide 10 in the colloidal antimony pentoxide (c) are used.
The amount of the amine compound (d) is 0.5 to 60 parts by weight, preferably 1 to 50 parts by weight, based on 0 parts by weight. When the compounding amount of the amine compound (d) is more than 60 parts by weight, it becomes difficult to control agglomeration of the agglomerates obtained from the colloidal antimony pentoxide (c) and the amine compound (d), resulting in a cured film. It is difficult to obtain a matte-cured coating having a good appearance such as glossiness or scratches. If the amount of the amine compound (d) is less than 0.5 part by weight, it is difficult to obtain aggregates having a size capable of expressing matting.

The agglomerate of the present invention comprises 1 to 30 of ultrafine particles of colloidal antimony pentoxide (c) which form the agglomerate based on 100 parts by weight of the (meth) acrylic acid ester derivative (a). Parts by weight, preferably 2-20
It may be blended so as to be part by weight. If the weight of the ultrafine particles of antimony pentoxide is more than 30 parts by weight, it is difficult to obtain a matte-cured coating having a good appearance such as gloss or scratches on the cured coating. If the weight of the ultrafine particles of antimony pentoxide is less than 1 part by weight, matte tends not to appear.

The photocurable composition for matte coating of the present invention comprises
When a cyclic hindered amine compound is used as the amine compound (d), if the amount of the cyclic hindered amine compound used is within the above-mentioned range of use of the amine compound (d), the cyclic hindered amine compound exhibits its original properties as a light stabilizer. Then, a cured film having weather resistance is formed.

In the photocurable composition for matte coating of the present invention, ultrafine particle silica (hereinafter referred to as colloidal silica) dispersed in an organic solvent is used as a part of colloidal antimony pentoxide (c). You may. The colloidal silica forms an aggregate with the amine compound (d) like the colloidal antimony pentoxide (c), and exhibits a function as a matting agent.

Examples of the organic solvent which is a dispersion solvent for colloidal silica include the same as the dispersion solvent for the colloidal antimony pentoxide (c). The colloidal silica is not particularly limited in particle size and concentration of the ultrafine particle silica, and for example, those containing about 20 to 40% by weight of ultrafine particle silica in a dispersion liquid which is easily available as a commercial product can be used. . As commercially available colloidal silica, for example, a trade name of methanol silica sol in which the organic solvent is methyl alcohol [silica particle size: 10 to 15 m
μ, solid content: 30% by weight, manufactured by Nissan Chemical Industries, Ltd.], trade name MA-ST-M [silica particle size: 20 to 25 mμ, solid content: 40% by weight, manufactured by Nissan Chemical Industries, Ltd.] or Product name OSCAL1132 [Silica particle size: 10 to 20 m
μ, solid content: 30 to 31% by weight, Catalyst Kasei Kogyo Co., Ltd.
Product name] OSCA, in which the solvent is ethyl alcohol
L1232 [silica particle size: 10 to 20 mμ, solid content: 3
0 to 31% by weight, manufactured by Catalyst Kasei Kogyo Co., Ltd.], the solvent is n
Trade name OSCAL1332 which is propyl alcohol
[Silica particle size: 10 to 20 mμ, solid content: 30 to 31% by weight, manufactured by Catalysts & Chemicals Industry Co., Ltd.], trade name IPA-ST in which the solvent is isopropyl alcohol [silica particle size: 1
0 to 15 mμ, solid content: 30% by weight, manufactured by Nissan Chemical Industry Co., Ltd. or trade name OSCAL1432 [silica particle size: 10 to 20 mμ, solid content: 30 to 31% by weight, manufactured by Catalysts & Chemicals Industry Co., Ltd.], Trade name NBA-ST in which the solvent is n-butyl alcohol [silica particle size: 10 to 15 m
μ, solid content: 20% by weight, manufactured by Nissan Chemical Industries, Ltd.] or trade name OSCAL 1532 [silica particle size: 10 to 2]
0 mμ, solid content: 30 to 31% by weight, manufactured by Catalysts & Chemicals Industry Co., Ltd.], the solvent is ethylene glycol, trade name EG-ST [silica particle size: 10 to 15 mμ, solid content: 2
0 wt%, manufactured by Nissan Chemical Industry Co., Ltd.], the solvent is ethyl cellosolve under the trade name OSCAL1632 [silica particle size: 10 to 20 mμ, solid content: 30 to 31 wt%, manufactured by Catalysts & Chemicals Industry Co., Ltd.], Trade name NPC-ST [silica particle size: 10 to 15 mμ, solid content: 30 wt%, manufactured by Nissan Chemical Industries, Ltd.] or trade name NPC-ST-2 [wherein the solvent is ethylene glycol mono n-propyl ether]. Silica particle size: 400 to 500 mμ, solid content: 20% by weight,
Nissan Chemical Industry Co., Ltd.], trade name DMAC-ST in which the solvent is dimethylacetamide [silica particle size: 10 to 1
5 mμ, solid content: 20% by weight, manufactured by Nissan Chemical Industries, Ltd.]
Or, the trade name DMAC-ST-ZL [silica particle size: 7
0-100 mμ, solid content: 20% by weight, manufactured by Nissan Chemical Industries, Ltd.], and the solvent is a mixed solvent of xylene and n-butyl alcohol, trade name XBA-ST [silica particle size:
10-15 mμ, solid content: 30 wt%, manufactured by Nissan Chemical Industries, Ltd.], the solvent is methyl isobutyl ketone, trade name MIBK-ST [silica particle size: 10-15 mμ, solid content: 30 wt%, Nissan Chemical Industry Co., Ltd.] and the like. Colloidal silica can use these 1 type (s) or 2 or more types.

Further, the photocurable composition for matte coating of the present invention may contain hydrophobic silica. Examples of the hydrophobic silica include hydrophobic silica powder, and these may be obtained by any manufacturing method. For example, as the hydrophobic silica, a silanol group on the surface of hydrophilic silica powder is treated with an organic silicon compound.

Specific examples of the hydrophobic silica powder include Nipseal SS-50F (trade name) [average particle size: 1.0 μm,
Nippon Silica Industry Co., Ltd.], product name Nipseal SS-
50 [average particle size: 1.3 μ, Nippon Silica Industry Co., Ltd.
Manufactured], product name Silohobic 100 [average particle size:
1.4μ, manufactured by Fuji Silysia Chemical Ltd., trade name Nipseal SS-20 [average particle size: 1.7μ, manufactured by Nippon Silica Industry Co., Ltd.], trade name Silophobic 200 [average particle size: 1. 8μ, manufactured by Fuji Silysia Chemical Ltd., trade name Nipseal SS-15 [average particle size: 2.5μ, manufactured by Nippon Silica Industry Co., Ltd.], trade name Silohobic 70
2 [Average particle size: 2.5μ, Fuji Silysia Chemical Ltd.
Made], trade name Nipseal SS-50A [average particle size:
2.3μ, manufactured by Nippon Silica Industry Co., Ltd., trade name Nipseal SS-40 [average particle size: 2.5μ, manufactured by Nippon Silica Industry Co., Ltd.], tradename Nipseal SS-10 [average particle size: 2. 7μ, manufactured by Nippon Silica Industry Co., Ltd., trade name Silohobic 704 [average particle size: 3.5μ, manufactured by Fuji Silysia Chemical Ltd.], trade name Nipseal SS-70
[Average particle size: 4.1μ, manufactured by Nippon Silica Industry Co., Ltd.],
Product name Nipseal SS-30p [Average particle size: 8.6
μ, manufactured by Nippon Silica Industry Co., Ltd., etc., and one or more of these can be used.

The photocurable composition for matte coating of the present invention may contain a light stabilizer composed of a compound having one cyclic hindered amine structure in the molecule. Specifically, 4-benzoyloxy-2,2,6,6-tetramethylpiperidine [a commercially available product under the trade name SANOL LS-
744, manufactured by Sankyo Co., Ltd.], 1- [2- {3- (3,5-
Di-tert-butyl-4-hydroxyphenyl) propionyloxy {ethyl] -4- {3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxy}
-2,2,6,6-Tetramethylpiperidine [trade name: Sanol LS-2626, manufactured by Sankyo Co., Ltd.]
And the like.

The photocurable composition for matte coating of the present invention contains a solvent, various additives such as a thickener, an antioxidant,
An ultraviolet absorber may be added.

Examples of the solvent include alcohols such as ethyl alcohol, n-propyl alcohol, isopropyl alcohol and n-butyl alcohol, ethylene glycol monomethyl ether, ethyl cellosolve, ethylene glycol monobutyl ether, propylene glycol monomethyl ether and propylene glycol monobutyl ether. Alcohol-based solvents such as alkylene glycol monoalkyl ethers are colloidal antimony pentoxide (c)
Particularly preferred in terms of dispersion stability of an aggregate obtained from the compound and the amine compound (d), 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. Kinds and the like can also be used.

The photocurable composition for matte coating of the present invention comprises
Usually, after being mixed with an appropriate solvent and applied to a synthetic resin molded product, it is cured by irradiating ultraviolet rays. Curing can also be performed by irradiating active energy rays other than ultraviolet rays, for example, α rays, β rays, γ rays, electron beams, and the like.

As the base material of the synthetic resin molded article on which the photocurable composition for matte coating of the present invention is applied, a thermoplastic resin or a thermosetting resin can be used without distinction, and examples thereof include polymethylmethacrylate and polycarbonate. , Polyallyl diglycol carbonate resin, ABS resin, polystyrene, PVC, polyester resin, acetate resin and the like are used. Further, as the shape of the synthetic resin molded product, in addition to a general molded product, a sheet, a film and the like are also targeted.

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

[0053]

EXAMPLES The present invention will be described in more detail with reference to the following examples, which are illustrative only and the present invention is not limited to these examples. The (meth) acrylate derivative (a) used in the following Examples and Comparative Examples,
Abbreviations for the colloidal antimony pentoxide (c) and the amine compound (d) are as follows.

<(Meth) acrylic ester derivative (a)> A: Urethane acrylate oligomer (number average molecular weight: 450 to 550) obtained by the reaction of 88 parts by weight of pentaerythritol triacrylate and 12 parts by weight of hexamethylene diisocyanate. ) B: Aronix M-305 [pentaerythritol triacrylate, manufactured by Toagosei Co., Ltd.] C: DPHA [dipentaerythritol hexaacrylate, manufactured by Daicel UCB]

<Colloidal antimony pentoxide (c) or silica fine powder> a: Sun colloid AMT-130 [ultrafine particle antimony pentoxide dispersed in methyl alcohol, solid content 30% by weight, manufactured by Nissan Chemical Industries, Ltd.] b: Sylysia 450 [silica fine powder having an average particle size of 5.2 μ, manufactured by Fuji Silysia Chemical Ltd.] c: Sylysia 350 [silica fine powder having an average particle size of 1.8 μ, manufactured by Fuji Silysia Chemical Ltd.] d: Aerosil 200 [silica fine powder with an average primary particle size of 12 mμ, Nippon Aerosil Co., Ltd.]

<Amine compound (d)> e: ethylenediamine f: ADEKA STAB LA-63P [mixture with an average molecular weight of 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-butanetetracarboxylate, manufactured by Asahi Denka Co., Ltd.] g: ADEKA STAB LA-87 [ Asahi Denka Kogyo Co., Ltd. 2,2,6,6-tetramethyl-4-piperidyl methacrylate] homopolymer (average molecular weight: about 3000)

Examples 1 to 11 (meth) acrylic acid ester derivative (a) shown in Table 1,
A photocurable composition for matte coating was produced using the photopolymerization initiator (b), colloidal antimony pentoxide (c) and amine compound (d). That is, a (meth) acrylic acid ester derivative (a), a photopolymerization initiator (b), colloidal antimony pentoxide (c) and ethyl cellosolve are mixed, and then this mixture is mixed with an amine compound under stirring at 300 rpm. (D) was gradually added and mixed for 30 minutes to obtain a photocurable composition for matte coating containing aggregates. The photopolymerization initiator (b) is 1-
Hydroxycyclohexyl phenyl ketone was used.
Ethyl cellosolve was used in an amount such that the nonvolatile content of the obtained photocurable composition for matte coating was 40% by weight.
In Table 1, the blending amount is parts by weight, and the colloidal antimony pentoxide (c) is the parts by weight of ultrafine particles of antimony pentoxide.

The photocurable composition for matte coating thus obtained was placed on a methacrylic resin plate having a thickness of 2 mm [Sumipex # 000 manufactured by Sumitomo Chemical Co., Ltd.] with a bar No. Bar coating was carried out using a bar of No. 8 to form a coating.
After drying for one minute, the resin plate is placed in the air with a high-pressure mercury lamp [I-Cure UE021-403 manufactured by Eye Graphics Co., Ltd.]
C, 500 V, H02-L41 (2)].
The coating was cured by irradiating it with ultraviolet rays from a distance of mm for 80 W / cm for 5 seconds to form a cured coating on the methacrylic resin plate.

Table 2 shows the evaluation results of the dispersion stability over time of the photocurable composition for matte coating, and the matte pattern and physical property evaluation results of the cured film formed on the methacrylic resin plate.

The dispersion stability over time of the photocurable composition for matte coating, the matte pattern of the cured coating and the evaluation of physical properties were carried out as follows. 1) Time-dependent dispersion stability: Observation of the state of the photocurable composition for matte coating after leaving at 40 ° C. ◯: Even after left standing for 4 months or more, a uniform state was maintained. ×: Solid content settled one month after standing, and redispersion was impossible. 2) Matte pattern: Visual observation with 10x magnifying glass 3) Haze value (Haze): Measurement with haze computer 4) Glossiness: Measurement with gloss meter 60 ° 5) Abrasion resistance: With # 0000 steel wool Scratch test A: No scratch even with strong rubbing B: Slight scratch with strong rubbing C: Slight scratch with rubbing light D: Significant scratch with slight rubbing 6) Adhesion; Cross-cut cellophane Tape peeling test Eleven cutting lines that reach the substrate at 1 mm intervals were inserted into the cured film in 11 rows and 11 columns to make 100 1 mm intervals.
Stick cellophane tape on it and remove it abruptly. This cellophane tape operation is repeated three times at the same location, and is expressed by the number of stitches that have not been peeled off.

Comparative Examples 1 to 4 For comparison, photocurable compositions having the compositions shown in Table 1 were prepared. As the photopolymerization initiator (b), 1-hydroxycyclohexylphenyl ketone was used, and ethyl cellosolve was used in such an amount that the nonvolatile content of the obtained photocurable composition became 40% by weight. In Table 1, the blending amount is parts by weight, and the colloidal antimony pentoxide (c) is the parts by weight of ultrafine particles of antimony pentoxide. With respect to these photocurable compositions, evaluation of dispersion stability over time and matte pattern and physical properties of a cured film formed on a methacrylic resin plate were performed in the same manner as in Example 1. The results are shown in Table 2.

[0062]

[Table 1]

[0063]

[Table 2]

Claims (5)

[Claims] 1. Ultrafine particle pentoxide dispersed in a (meth) acrylic acid ester derivative (a) having at least one (meth) acryloyloxy group in the molecule, a photopolymerization initiator (b), and an organic solvent. A photocurable composition for matte coating, comprising an aggregate obtained from antimony (c) and an amine compound (d) capable of aggregating ultrafine particles of antimony pentoxide. 2. The composition according to claim 1, wherein the amine compound (d) capable of aggregating the ultrafine particles of antimony pentoxide is a light stabilizer having an average of two or more cyclic hindered amine structures in the molecule. 3. The composition according to claim 1, wherein 0.5 to 60 parts by weight of the amine compound (d) capable of aggregating the ultrafine particles of antimony pentoxide is used with respect to 100 parts by weight of the ultrafine particles of antimony pentoxide. Stuff. 4. A synthetic resin molding in which the photocurable composition for matte coating according to claim 1 is applied to a synthetic resin molded article and then irradiated with active energy rays to form a matte cured coating on the surface. Goods. 5. A synthetic resin molding in which the photocurable composition for matte coating according to claim 3 is applied to a synthetic resin molded article and then irradiated with active energy rays to form a matte cured coating on the surface. Goods.