JPH10195334A - Photocurable composition for matte coating and synthetic resin molding coated therewith - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photocurable compsn. which is excellent in dispersion stability in aging, forms a cured matte coating film with a stable matte effect even when subject to a shearing force, and can form a cured coating film with a fine matte pattern and to provide a synthetic resin molding coated therewith. SOLUTION: This compsn. contains a (meth)acrylic ester deriv. having at least one (meth)acryloyloxy group in the molecule, a photopolymn. initiator, a fluocculate obtd. from 100 pts.wt. superfine-particle silica dispersed in an org. solvent and 0.5-60 pts.wt. amine compd. capable of flocculating the silica, and a hydrophilic silica. A synthetic resin molding is coated with the compsn. and irradiated with an active energy ray to form a cured matte coating film on the surface thereof.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photocurable composition for forming a matte 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 paint, a photocurable composition for matte coating, which forms a matte cured film on the surface by irradiating active energy rays, is used. The photocurable composition for matte coating is
It is prepared by dispersing and mixing a predetermined matting agent in the base photocurable composition in order to obtain a matte appearance, that is, a matte degree according to the purpose. The matting agent used for this is inorganic,
It is roughly divided into organic fine powder. 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.
Therefore, the present inventor has disclosed in Japanese Patent Application Laid-Open No. 8-231885 that a fine particle silica (hereinafter, referred to as colloidal silica) dispersed in an organic solvent and the ultra-fine particle silica as a matting agent capable of solving these problems. Aggregates obtained from a hindered amine-based light stabilizer which can be made to be formed, aggregates obtained from colloidal silica and a nitrogen-containing polymer which makes it possible to agglomerate colloidal silica and its ultrafine particle silica in Japanese Patent Application No. 7-239123, and the like. We have proposed photocurable compositions for matte coatings containing aggregates of the above.
Further study on the photocurable composition for matte coating, when applying a shearing force to the composition, the matte cured film, matte degree is considerably lower than when not subjected to shearing force It has been found that there is a disadvantage that it is not stable, and that the cause of this decrease is that the aggregates collapse due to shearing force. As described above, the photocurable composition for matte coating proposed by the present inventor is difficult to obtain a matte cured film having a desired matte degree by applying a shearing force. Not satisfactory for use in

[0004] An object of the present invention is to solve the above-mentioned problems at present, and to form a matte cured film having excellent dispersion stability over time and a stable matte degree even under a shearing force.
Moreover, an object of the present invention is to provide a photocurable composition capable of forming a cured film having a fine matte pattern, and a synthetic resin molded article using the photocurable composition.

[0005]

Means for Solving the Problems In order to achieve the above object, the present inventors have developed a (meth) acrylate derivative (a) having one or more (meth) acryloyloxy groups in the molecule [hereinafter, referred to as "a". (Meth) acrylate derivative (a). ], A photopolymerization initiator (b), ultrafine silica (c) dispersed in an organic solvent [hereinafter referred to as colloidal silica (c). And an amine compound (d) capable of coagulating the ultrafine silica particles [hereinafter referred to as amine compound (d)]. ], And a photocurable composition containing the hydrophilic silica (e). The photocurable composition has excellent dispersion stability over time and is affected by shearing force. The cured film was found to exhibit a stable matting degree. Furthermore, it has been found that a fine matte patterned cured film can be obtained by appropriately selecting the type and amount of the colloidal silica (c), the amine compound (d) and the hydrophilic silica (e).

That is, the present invention relates to a (meth) acrylate derivative (a), a photopolymerization initiator (b), an aggregate obtained from colloidal silica (c) and an amine compound (d), and a hydrophilic silica. (E) A photocurable composition for matte coating, characterized by containing: and the photocurable composition for matte coating is applied to a synthetic resin molded article, and then irradiated with active energy rays to obtain a surface. And a synthetic resin molded article having a matte cured film formed thereon.

In the photocurable composition for matte coating of the present invention, colloidal silica (c) and amine compound (d) are used.
And the hydrophilic silica (e) obtained from the above function as a matting agent, and it is considered that the above-mentioned effects can be obtained by these.

[0008]

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.

Examples of the bifunctional (meth) acrylate monomer include alkylene glycol di (meth) acrylates, polyoxyalkylene glycol di (meth) acrylates, halogen-substituted alkylene glycol di (meth) acrylates, and aliphatic polyol di (meth) acrylates. Representative examples include (meth) acrylates, di (meth) acrylates of an alkylene oxide adduct of bisphenol A or bisphenol F, and epoxy di (meth) acrylates of bisphenol A or bisphenol F.
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.

The polyfunctional (meth) acrylate monomers include glycerin tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, ditrimethylolpropane tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, and pentaerythritol tri Poly (3) or higher aliphatic polyol such as (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate (Meth) acrylate is a typical example, and poly (meth) acrylate of a halogen-substituted polyol having a valency of 3 or more, and alkylene oxide addition of glycerin are also used. 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.

As the (meth) acrylate oligomer, 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.

The polyfunctional urethane (meth) acrylate oligomer includes 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 with a polyisocyanate, and polyols. Is reacted with a polyisocyanate, and a urethanization reaction product of an isocyanate compound obtained with a (meth) acrylate monomer having at least one (meth) acryloyloxy group and at least one hydroxyl group in one molecule, and the like.

The (meth) acrylate monomer having at least one (meth) acryloyloxy group and hydroxyl group in one molecule used in the urethanization reaction includes 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.

The polyisocyanate used in the urethanization reaction includes 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, generally used are aromatic, aliphatic and alicyclic polyols, as well as polyester polyols and polyether polyols. 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,
Examples include pentaerythritol, dipentaerythritol, dimethylol heptane, dimethylol propionic acid, dimethylol butylic acid, glycerin, hydrogenated bisphenol A, and the like.

The polyester polyol is obtained by a dehydration condensation reaction between the above-mentioned 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, a polybasic carboxylic acid (anhydride) and a 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 an addition reaction between 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 silica (c) of the present invention, the organic solvent as a dispersing solvent includes methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, ethylene glycol, ethylene glycol monoethyl ether ( Hereinafter, referred to as ethyl cellosolve), alcohol solvents such as ethylene glycol mono n-propyl ether,
Aromatic hydrocarbons such as toluene and xylene, acetone,
Ketones such as methyl ethyl ketone and methyl isobutyl ketone; acetates such as ethyl acetate and butyl acetate; and dimethylacetamide.
More than species can be used.

In the present invention, the colloidal silica (c)
The particle size and concentration of the ultrafine silica are not particularly limited, and for example, those containing about 20 to 40% by weight of ultrafine silica in a dispersion which is easily available as a commercial product can be used. Examples of commercially available colloidal silica (c) include, for example, methanol silica sol (trade name) in which the organic solvent is methyl alcohol [silica particle size: 10 to 15 mμ,
Solid content: 30% by weight, manufactured by Nissan Chemical Industry Co., Ltd.], trade name MA-ST-M [silica particle size: 20 to 25 μm, solid content: 40% by weight, manufactured by Nissan Chemical Industry Co., Ltd.] or trade name OSCAL1132 [silica particle size: 10 to 20 mμ,
Solid content: 30 to 31% by weight, manufactured by Catalyst Chemical Industry Co., Ltd.]
OSCAL12 (trade name) wherein the solvent is ethyl alcohol
32 [silica particle size: 10 to 20 mμ, solid content: 30 to 3
1% by weight, manufactured by Catalyst Kasei Kogyo Co., Ltd.], OSCAL1332 (trade name: silica particle size: 10 to 20 μm, solid content: 30 to 31% by weight) in which the solvent is n-propyl alcohol.
Catalyst Kasei Kogyo Co., Ltd.], trade name IPA-ST wherein the solvent is isopropyl alcohol [silica particle size: 10 to 1
5 μm, solid content: 30% by weight, manufactured by Nissan Chemical Industries, Ltd.]
Or OSCAL1432 (trade name: silica particle size: 10
-20 mμ, solid content: 30-31 wt%, manufactured by Catalyst Chemical Industry Co., Ltd.], trade name NBA-ST in which the solvent is n-butyl alcohol [silica particle size: 10-15 mμ, solid content: 20 wt% Manufactured by Nissan Chemical Industry Co., Ltd.] or trade name OSCAL1532 [silica particle size: 10-20 μm,
Solid content: 30 to 31% by weight, manufactured by Catalyst Chemical Industry Co., Ltd.]
EG-ST (trade name) in which the solvent is ethylene glycol
[Silica particle size: 10 to 15 mμ, solid content: 20% by weight,
Nissan Chemical Industry Co., Ltd.], OSCAL1632 (trade name: silica particle size: 10 to 2), wherein the solvent is ethyl cellosolve
0 mμ, solid content: 30 to 31% by weight, manufactured by Catalyst Chemical Industry Co., Ltd.], and the solvent is ethylene glycol mono n-propyl ether, trade name NPC-ST [silica particle size:
10 to 15 mμ, solid content: 30% by weight, manufactured by Nissan Chemical Industry Co., Ltd.] or NPC-ST-2 [silica particle size: 400 to 500 mμ, solid content: 20% by weight, manufactured by Nissan Chemical Industry Co., Ltd.] ], The solvent is dimethylacetamide, trade name DMAC-ST [silica particle size: 10 to 15 m]
μ, solid content: 20% by weight, manufactured by Nissan Chemical Industry Co., Ltd.] or trade name DMAC-ST-ZL [silica particle size: 70 to
100mμ, solid content: 20% by weight, Nissan Chemical Industries, Ltd.
XBA-ST, wherein the solvent is a mixed solvent of xylene and n-butyl alcohol [silica particle size: 10 to
15mμ, solid content: 30% by weight, Nissan Chemical Industries, Ltd.
Trade name, wherein the solvent is methyl isobutyl ketone
IBK-ST [silica particle size: 10 to 15 mμ, solid content:
30% by weight, manufactured by Nissan Chemical Industry Co., Ltd.].
Colloidal silica (c) can be used alone or in combination of two or more.

The amine compound (d) means a compound ranging from a low molecular weight compound having a plurality of amine structures in a molecule to a high molecular weight compound. 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) A low-molecular compound having a plurality of amine structures in a molecule is a low-molecular compound having a plurality of amine structures in a molecule having a molecular weight of about 60 to less than about 1000 and It refers to those having 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)]
That. 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, mensendiamine, 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 is represented by the general formula (A):

[0030]

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):

[0031]

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 as Biosorb 04, manufactured by Kyodo Yakuhin Co., Ltd.] ], Bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate [commercially available as SANOL LS-765, 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 is a compound having a molecular weight of 1,000 or more and having 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 in the molecule as described above, and a polymerizable light stabilizer having one such cyclic hindered amine structure in the molecule. Polymer [Hereinafter, these are collectively referred to as 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 ADK STAB LA-87, manufactured by Asahi Denka Kogyo KK], 1,2,2,6,6-pentamethyl-4-piperidyl methacrylate [commercially available Homopolymers of trade name ADK STAB LA-82, manufactured by Asahi Denka Kogyo Co., Ltd.].

The polymerizable amine is preferably a polymerizable monoamine such as a vinyl monomer having one amine structure in a molecule and an isopropenyl monomer having one amine structure in a 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.

The monomers having an olefinically unsaturated group (excluding the polymerizable amine) used for copolymerization with the polymerizable amine include 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth). A) acrylate, hydroxyalkyl (meth) acrylate such as 2-hydroxybutyl (meth) acrylate, alkyl (meth) acrylate such as methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, styrene, vinyl acetate, Acrylonitrile and the like, but are not limited thereto.

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 heteroatom in the molecule as an amine structure. 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. Among homopolymers or copolymers of a vinyl monomer having a heteroaromatic ring having a nitrogen atom as a hetero atom in an amine structure in the molecule, homopolymers of vinyl pyridines such as vinyl pyridine and alkyl-vinyl pyridine; , N-dialkylaminoalkyl (meth) acrylate, styrene or a vinylpyridine-based polymer such as a copolymer of hydroxyalkyl (meth) acrylate and vinylpyridines is preferred.

Examples of the hydrophilic silica (e) of the present invention include hydrophilic silica powders, and these may be obtained by any production method. Specific examples of preferred hydrophilic silica powder include trade name thyricia 250
[Average particle size: 2.7μ, Fuji Silysia Chemical Ltd.]
Manufactured), Trade name: Sylysia 250N [Average particle size: 2.7
μ, manufactured by Fuji Silysia Chemical Ltd.]
10 [average particle diameter: 1.4μ, Fuji Silysia Chemical Ltd.]
Manufactured), trade name Sylysia 320 [average particle diameter: 1.6]
μ, manufactured by Fuji Silysia Chemical Ltd.]
50 [average particle size: 1.8μ, Fuji Silysia Chemical Ltd.]
Manufactured), trade name Sylysia 430 [average particle size: 2.5
μ, manufactured by Fuji Silysia Chemical Ltd.]
31 [Average particle size: 2.5μ, Fuji Silysia Chemical Ltd.]
Manufactured), trade name Sylysia 450 [average particle diameter: 5.2
μ, manufactured by Fuji Silysia Chemical Ltd.]
30 [average particle size: 1.9μ, Fuji Silysia Chemical Ltd.]
Manufactured by Sylysia 540 [average particle diameter: 2.3]
μ, manufactured by Fuji Silysia Chemical Ltd.]
50 [average particle size: 2.7 μ, Fuji Silysia Chemical Ltd.]
Manufactured), trade name: Sylysia 770 [average particle diameter: 6.0
μ, manufactured by Fuji Silysia Chemical Ltd.], Nipseal E-170 (trade name, 3.0 μm, manufactured by Nippon Silica Industry Co., Ltd.), Nipseal E-200 (trade name, 3.0 μm, Nippon Silica Kogyo Co., Ltd.], trade name Nip Seal E-220 [average particle size: 1.5 μm, Nippon Silica Kogyo Co., Ltd.], trade name Nip Seal E-200A
[Average particle diameter: 2.5 µ, manufactured by Nippon Silica Industry Co., Ltd.],
Brand name Nip Seal E-220A [Average particle size: 1.5
μ, manufactured by Nippon Silica Industry Co., Ltd.]
-250 [average particle diameter: 2.0 µ, manufactured by Nippon Silica Industry Co., Ltd.], trade name Nip Seal E-75 [average particle diameter: 2.0 µ, manufactured by Nippon Silica Industry Co., Ltd.], trade name Nip Seal E-743. [Average particle diameter: 1.5 µ, manufactured by Nippon Silica Industry Co., Ltd.], trade name Nip Seal E-74P [Average particle diameter: 2.5 µ, manufactured by Nippon Silica Industry Co., Ltd.], trade name Nip Seal G-300 [average Particle size: 2.0μ, manufactured by Nippon Silica Industry Co., Ltd.], trade name: NIPSEAL N-30
0A [Average particle size: 2.0μ, Nippon Silica Industry Co., Ltd.
Nip Seal HD [Average particle size: 2.0]
μ, manufactured by Nippon Silica Industry Co., Ltd.]
D-2 [Average particle size: 3.0 μ, Nippon Silica Industry Co., Ltd.
Commercially available products, and one or more of these can be used.

The photocurable composition for matte coating of the present invention comprises:
The (meth) acrylate derivative (a), the photopolymerization initiator (b), the colloidal silica (c) and the hydrophilic silica (e) are dispersed and mixed with a homomixer, and then the mixture is mixed with the amine compound (d). Can be obtained simply by adding and mixing.

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. If the amount of the photopolymerization initiator is more than the above range, the cured film is colored, and if the amount is less than the above range, a sufficient curing speed cannot be obtained.

The mixing ratio of the colloidal silica (c) and the amine compound (d) is usually the same as that of the colloidal silica (c).
The amine compound (d) is used in an amount of 0.5 to 60 parts by weight, preferably 1 to 50 parts by weight, based on 100 parts by weight of the ultrafine silica. If the compounding amount of the amine compound (d) is larger than the above range, it becomes difficult to control the aggregation of the aggregate obtained from the colloidal silica (c) and the amine compound (d), and the cured film has a glossy or uneven appearance. It is difficult to obtain a matte cured film having a good appearance such as occurrence of cracks. On the other hand, if the amount is less than the above range, it is difficult to obtain an aggregate having a size capable of expressing matting.

The amount of the hydrophilic silica (e) used is 1 to 100 parts by weight of the (meth) acrylate derivative (a).
-30 parts by weight, preferably 2-20 parts by weight.
When the weight of the hydrophilic silica (e) is more than 30 parts by weight,
It is difficult to obtain a matte cured film having a good appearance such as gloss blur or bumps on the cured film. If the weight of the hydrophilic silica (e) is less than the above range, it is difficult to obtain a cured film exhibiting a stable matting degree due to shearing force.

The mixing ratio of the ultrafine silica of the colloidal silica (c) of the present invention and the hydrophilic silica (e) is 10% by weight: 90% by weight to 90% by weight to 10% by weight, preferably 20% by weight: 80% by weight to 80% by weight: 20% by weight. 10 ultra fine colloidal silica (c)
If it is less than 10% by weight, the dispersion stability over time becomes poor,
If the content exceeds 90% by weight, an aggregate obtained from the colloidal silica (c) and the amine compound (d) is easily broken by a shearing force, which is not preferable.

In the photocurable composition for matte coating of the present invention, when a cyclic hindered amine compound is used as the amine compound (d), the amount of the cyclic hindered amine compound is within the above-mentioned range of the amine compound (d). If there is
The cyclic hindered amine compound expresses its inherent properties as a light stabilizer, and forms a cured film having weather resistance.

The photocurable composition for matte coating of the present invention may contain a light stabilizer comprising 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 [commercially available as 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, propylene glycol monobutyl ether and the like. Alcohol solvents such as alkylene glycol monoalkyl ethers are particularly preferred in view of the dispersion stability of aggregates obtained from colloidal silica (c) and amine compound (d), and aromatic hydrocarbons such as toluene and xylene; Acetates such as ethyl acetate and butyl acetate, and ketones such as acetone and methyl ethyl ketone 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 product on which the photocurable composition for matte coating of the present invention is applied on the surface, a thermoplastic resin and a thermosetting resin can be used irrespective of whether they are polymethyl methacrylate or polycarbonate. , Polyallyl diglycol carbonate resin, ABS resin, polystyrene, PVC, polyester resin, acetate resin and the like. 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, a known method such as curtain flow coating, spray coating, roll coating, and dipping may be used as appropriate. 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.

[0052]

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 silica (c), hydrophilic silica (e) and amine compound (d) are as follows.

<(Meth) acrylic ester derivative (a)> A: Urethane acrylate oligomer [number average molecular weight: 450 to 550] obtained by reacting 88 parts by weight of pentaerythritol triacrylate with 12 parts by weight of hexamethylene diisocyanate B: dipentaerythritol hexaacrylate

<Colloidal silica (c) or hydrophilic silica (e)> a: IPA-ST [30% by weight of isopropanol dispersion of silica having an average particle diameter of 10 to 15 μm, manufactured by Nissan Chemical Industries, Ltd.] b : Sylysia 350 [hydrophilic silica having an average particle size of 1.8 μm, manufactured by Fuji Silysia Chemical Ltd.] c: Thylysia 310 [hydrophilic silica having an average particle size of 1.4 μm, manufactured by Fuji Silysia Chemical Ltd.]

<Amine compound (d)> d: Adekastab LA-63P [mixture having an average molecular weight of 2,000 {1,2,2,6,6-pentamethyl-4-piperidyl / β, β, β ′, β′-tetra] Methyl-3,9-
[2,4,8,10-tetraoxaspiro (5.5) undecane] diethyl} -1,2,3,4-butanetetracarboxylate, manufactured by Asahi Denka Kogyo Co., Ltd. e: Biosorb 04 [sebacic acid] Screws (2, 2, 6,
6-tetramethyl-4-piperidyl), Kyodo Yakuhin Co., Ltd.
Made

Examples 1 to 13 (Meth) acrylate derivatives (a) shown in Table 1
A photocurable composition for matte coating was produced using colloidal silica (c), hydrophilic silica (e), photopolymerization initiator (b) and amine compound (d). That is, (meth) acrylate derivative (a), colloidal silica (c),
The hydrophilic silica (e), the photopolymerization initiator (b) and ethyl cellosolve were dispersed and mixed at 8000 rpm for 1 hour using a homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.), and then stirred under a three-one motor at 300 rpm. The mixture is mixed for 30 minutes while gradually adding the amine compound (d) to the mixture.
A matte coating photocurable composition containing aggregates was obtained.
1-hydroxycyclohexyl phenyl ketone was used as the photopolymerization initiator (b). 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 compounding amount is part by weight, and the colloidal silica (c) is the part by weight of ultrafine silica.

The photocurable composition for matte coating thus obtained was applied to a methacrylic resin plate [SUMIPEX # 000 manufactured by Sumitomo Chemical Co., Ltd.] having a thickness of 2 mm on a methacrylic resin plate. 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 is cured by irradiating ultraviolet light at a distance of 80 W / cm for 5 seconds from a distance of 5 mm to form a cured coating on a methacrylic resin plate [hereinafter referred to as a cured coating (I). ] Was formed.

Further, the photocurable composition for matte coating obtained above was stirred with a homomixer at 1000 rpm for 30 minutes to apply a shearing force, and then a cured film was formed on a methacrylic resin plate in the same manner as described above. It is called a cured film (II). ] Was formed.

Tables 2 and 3 show 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 evaluation of dispersion stability with time and coating stability, matte pattern and physical properties were carried out as follows. 1) Dispersion stability with time: Observation of the state of the photocurable composition for mat coating at 40 ° C. after standing 〇: Even after standing for 4 months or more, caking that cannot be redispersed did not occur. 2) Matte pattern: Visual observation with a 10-magnification loupe 3) Total light transmittance (%) and haze: Measurement with a haze computer 4) Gloss: Measurement with a gloss meter at 60 ° 5) Abrasion resistance: # Abrasion test with 0000 steel wool A: no damage even with strong rubbing B: slight damage with strong rubbing C: slight scratch with light rubbing D: significant scratching with light rubbing 6) Adhesion Properties: Cross-cut cellophane tape peeling test 11 cut lines of the cured film reaching the substrate at 1 mm intervals are inserted in each of 11 rows and 10 mm, and 100 cells of 1 mm are made, and a cellophane tape is stuck thereon and rapidly peeled off. 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 3 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 compounding amount is part by weight, and the colloidal silica (c) is the part by weight of ultrafine silica. 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 Tables 2 and 3.

[0062]

[Table 1]

[0063]

[Table 2]

[0064]

[Table 3]

Continued on the front page (51) Int.Cl. ⁶ Identification code FI C09D 7/12 C09D 7/12 Z

Claims (6)

[Claims] 1. A (meth) acrylate derivative (a) having one or more (meth) acryloyloxy groups in a molecule, a photopolymerization initiator (b), ultrafine silica (c) dispersed in an organic solvent ) And an amine compound (d) capable of coagulating the ultrafine silica
A photocurable composition for matte coating, comprising: an aggregate obtained from the above; and a hydrophilic silica (e). 2. The composition according to claim 1, wherein the amine compound (d) capable of coagulating the ultrafine silica particles is a light stabilizer having an average of two or more cyclic hindered amine structures in the molecule. 3. An amine compound (d) capable of coagulating ultrafine silica with respect to 100 parts by weight of ultrafine silica
3. The composition according to claim 1, wherein 0.5 to 60 parts by weight is used. 4. The mixing ratio of ultrafine silica and hydrophilic silica (e) is 10% by weight: 90% by weight to 90% by weight.
4. The composition according to claim 1, 2 or 3 in weight%. 5. A synthetic resin molding comprising the matte coating photocurable composition according to claim 1 applied to a synthetic resin molded product, and then irradiated with active energy rays to form a matte cured coating on the surface. Goods. 6. A synthetic resin molding having the matte coating photocurable composition according to claim 4 applied to a synthetic resin molded article, and then irradiated with active energy rays to form a matte cured coating on the surface. Goods.