JP2001348515A - Curable composition and method for forming coating film of the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a curable composition capable of forming coating film having excellent curability. SOLUTION: The present invention discloses the curable composition having features comprising compounding (A) 10-100 pts.wt. of a reactive organic silicon compound represented by general formula (1) (wherein, R1, R2, R3 and R4 are each the same or different and a 1-4C alkyl; n is an integer of from 1 to 50), (B) 0-90 pts.wt. of a cationic reactive compound and (C) 0.05-25 pts.wt. of a cationic polymerization initiator.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a cation and a reactive composition of a cation and a radical, and more particularly, to a low viscosity, excellent coating workability, good surface curability, and high hardness. The present invention relates to a cured composition for forming a coating film and a method for forming the coating film.

[0002]

2. Description of the Related Art Heretofore, a curable composition which is cured by an active energy ray such as an ultraviolet ray or an electron beam or heat has been widely used for applications such as paints, inks, and adhesives.

[0003] The type of curing with active energy rays includes:
Usually, a radical polymerization type and a cationic polymerization type are generally used.

[0004] The radical type generally has a fast curing reaction, but has a disadvantage that the surface of the coating film is inferior in curability due to the influence of oxygen in the air and hardly hardened. In addition, the curing shrinkage is large, and the adhesion is poor.

On the other hand, the cationic polymerization type has good curability on the surface and good adhesion of the coating to the material, but the curability is slower than that of radicals, it is difficult to cure a thick film, and water, ions, etc. Disadvantages, such as susceptibility to contamination. The same can be said for the case of curing by heating.

[0006]

DISCLOSURE OF THE INVENTION The object of the present invention is to develop a cured composition which forms a coating film having a high surface hardness and excellent adhesion, chemical resistance, and weather resistance. It is.

The inventors of the present invention have conducted intensive studies to solve the above problems, and as a result, a curable composition containing a specific raw material has a high film hardness, high adhesion, chemical resistance, and high resistance. The present invention has been found to provide a heat-curable or active energy ray-cured coating excellent in abrasion resistance and weather resistance, and has completed the present invention.

That is, the present invention relates to: (A) a reactive organosilicon compound represented by the following general formula (1):

[0009]

Embedded image (In the above formula, R ₁ , R ₂ , R ₃ , and R ₄ are the same or different and each represents an alkyl group having 1 to 4 carbon atoms, and n represents an integer of 1 to 50.) 10 to 100 parts by weight ( (B) a curable composition comprising 0 to 90 parts by weight of a cation-reactive compound (C) 0.05 to 25 parts by weight of a cationic polymerization initiator; 10) -99.5 parts by weight (E) Radical reactive compound 0.5-90 parts by weight (C) Cationic polymerization initiator 0.05-25 parts by weight (D) Radical polymerization initiation 3. The curable composition according to the above item 1, wherein the curable composition comprises 0.05 to 25 parts by weight of an agent. 3. (A) The reactive organosilicon compound represented by the general formula (I). 98 parts by weight (B) 1 to 90 parts by weight of the cation-reactive compound (E) 1 to 90 parts by weight of a radical reactive compound (C) 0.05 to 25 parts by weight of a cationic polymerization initiator (D) 0.05 to 25 parts by weight of a radical polymerization initiator 4. The curable composition according to the above item 1, 4. The radical reactive compound (E) is a compound containing one or more (meth) acryloyl groups in one molecule. The curable composition according to any one of Items 1 to 4, wherein the curable composition according to any one of Items 1 to 4 is applied to an object to be coated and heated to obtain a cured coating film. 6. A film forming method, wherein the curable composition according to any one of the above 1 to 4 is applied to an object to be coated and irradiated with active energy rays to obtain a cured film. The forming method, 7, The method according to any one of the above 1 to 4 About film forming method characterized by obtaining a cured coating film during and / or by heating after irradiation is a reduction composition by irradiating an active energy ray is applied to the object to be coated.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION The general formula (I) used in the present invention
In the reactive organosilicon compound represented by the formula, when n exceeds 50, the viscosity increases and the coating workability deteriorates.

Examples of these reactive organic silicon compounds include, for example, tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane, dimethoxydiethoxysilane, and at least one compound selected from these compounds. And the like.

In the present invention, the cation-reactive compound (B) to be used is a cation-reactive group (for example,
Compounds having an epoxy group, a styryl group, an oxetane ring group, an alkoxysilyl group, a hydroxyl group, a carboxyl group, an acid anhydride group, a vinyl ether group, and the like. Specifically, for example, epoxy compounds, styrene compounds, and vinyl compounds , Vinyl ether compounds, spirooxoester compounds, bicyclooxoester compounds, spiroorthocarbonate compounds, cyclic ether compounds,
Examples include lactone compounds, oxazoline compounds, aziridine compounds, cyclosiloxane compounds, ketal compounds, cyclic acid anhydride compounds, lactam compounds, alkoxysilane compounds, and aryl dialdehyde compounds.

Representative examples of epoxy compounds include ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, 1,4- Butanediol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin diglycidyl ether, diglycerin tetraglycidyl ether, trimethylolpropane triglycidyl ether, 2,6-diglycidylphenyl ether, Sorbitol triglycidyl ether,
Triglycidyl isocyanurate, diglycidylamine, diglycidylbenzylamine, diglycidyl phthalate, bisphenol A diglycidyl ether,
Butadiene dioxide, dicyclopentadienedioxide, diester of 3,4-epoxycyclohexene carboxylic acid with ethylene glycol, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 3,4-epoxy-6 Methylcyclohexylmethyl-3,4-epoxy-6-methylcyclohexanecarboxylate, bis (3,4-epoxycyclohexylmethyl) adipate, dicyclopentadiene epoxide glycidyl ether, dipentenedionoxide, bisphenol A type epoxy resin and ethylene oxide Additive, Eporide GT300
(Tri-functional alicyclic epoxy compound, manufactured by Daicel Chemical Industries, Ltd.), Eporide GT400 (4-functional alicyclic epoxy compound, manufactured by Daicel Chemical Industries, Ltd.); Eporide GT301, GT302, GT303 (all of which are described above) Also manufactured by Daicel Chemical Industries, Ltd., ring-opened ε-caprolactone chain-containing trifunctional alicyclic epoxy compound);
T401, GT402, and GT403 (all of which are manufactured by Daicel Chemical Industries, Ltd., tetrafunctional alicyclic epoxy compound having a ring-opened ε-caprolactone chain), celloxide 2
021P (manufactured by Daicel Chemical Industries, Ltd.); Epicoat 8
28, 834, and 1001 (all of which are manufactured by Yuka Shell Epoxy Co., Ltd., bisphenol A type epoxy resin); Epicoat 154 (Yuka Shell Epoxy Co., Ltd.)
Cresol novolak type epoxy resin), celloxides 2081 and 2082 represented by the following formula (2):
2083 (both are Daicel Chemical Industries, Ltd.)
In the following formula, those having n = 1 are celloxide 20
81, n = 2 is celloxide 2082, n = 3 is celloxide 2083); and Denacol EX-411 (manufactured by Nagase Kasei Co., Ltd.) represented by the following formula (3). Equation (2)

[0014]

Embedded image In the above formula (2), n represents an integer of 1 to 3;

[0015]

Embedded image

The above epoxy compounds can be used alone or in combination of two or more. The content of the epoxy group in the epoxy compounds is not particularly limited, but usually, the epoxy equivalent is suitably in the range of 100 to 3,000, preferably 100 to 1,500.

The above-mentioned alkoxysilane compounds include:
Compounds containing two or more alkoxysilyl groups in one molecule, for example, dimethoxydimethylsilane, dimethoxydiethylsilane, dimethoxydiphenylsilane, diethoxydimethylsilane, trimethoxymethylsilane,
Alkoxylanes having no polymerizable unsaturated groups such as trimethoxyethylsilane, trimethoxypropylsilane, trimethoxyphenylsilane, tetramethoxysilane, tetraethoxysilane, tetrabutoxysilane, dimethoxydiethoxysilane, and γ-glycidoxy Propyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxytriethoxysilane, γ- (meth) acryloxypropyltrimethoxysilane , Γ- (meth) acryloxypropylmethyldiethoxysilane, γ- (meth) acryloxypropyltriethoxysilane and the like.

Examples of the acid anhydride compounds (hereinafter sometimes abbreviated as "polyanhydride") include, for example, pyromellitic anhydride, a condensate of 1 mol of ethylene glycol and 2 mol of trimellitic anhydride. [Ethylenebis (anhydrotrimellitate)], a condensate of 1 mol of glycerin and 3 mol of trimellitic anhydride [glycerin tris (anhydrotrimellitate)], etc .; adipic acid succinate, azelaic acid, sepasic acid, Dodecane diacid, dimer acid,
Linear or cyclic polyanhydrides obtained by intermolecular condensation of polybasic acids such as ethyl-octadecandioic acid, phenyl-hexadecandioic acid, and 1,4-cyclohexanedicarboxylic acid; maleic anhydride, tetrahydrophthalic anhydride, etc. Examples of the polymer include a polymerizable unsaturated acid anhydride as one monomer component.

The monomers other than the polymerizable unsaturated acid anhydride capable of forming the polymer include, for example, methyl (meth) acrylate, ethyl (meth) acrylate,
n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate,
Isobutyl (meth) acrylate, tert-butyl (meth) acrylate, 2-ethylhexyl acrylate,
n-octyl (meth) acrylate, lauryl (meth)
Acrylate, tridecyl (meth) acrylate, stearyl (meth) C _1-24 alkyl (meth) acrylates such as acrylates, acrylic acid, methacrylic acid, polymerizable unsaturated monocarboxylic acids such as crotonic acid; styrene, vinyl toluene, alpha- Vinyl aromatic compounds such as methylstyrene; acrylonitrile, methacrylonitrile, tricyclodecanyl (meth) acrylate, isobornyl (meth) acrylate, vinyl acetate, and beoba monomer (manufactured by Shell Chemical Company).

As the styrene compounds, styrene, α
Monomethylstyrene, P-methylstyrene, p-chloromethylstyrene and the like can be mentioned.

Examples of the vinyl compounds include N-vinylcarbazole and N-vinylpyrrolidone.

As the vinyl ether compounds, for example,
n- (or i-SO, t-) butyl vinyl ether, cyclohexyl vinyl ether, hydroxybutyl vinyl ether, 1,4-butanediol divinyl ether, ethylene glycol divinyl ether, ethylene glycol monovinyl ether, triethylene glycol divinyl ether, tetraethylene glycol divinyl Vinyl ether,
Propylene glycol divinyl ether, propylene glycol monovinyl ether, neopentyl glycol divinyl glycol, neopentyl glycol monovinyl glycol, glycerol divinyl ether, glycerol trivinyl ether, trimethylolpropane monovinyl ether, trimethylolpropane divinyl ether, trimethylolpropane trivinyl ether,
Diglycerol trivinyl ether, sorbitol tetravinyl ether, cyclohexane dimethanol divinyl ether, hydroxybutyl vinyl ether, dodecyl vinyl ether, 2,2-bis (4-cyclohexanol)
Alkyl vinyl ethers such as propane divinyl ether, 2,2-bis (4-cyclohexanol) triple olopropane divinyl ether, alkenyl vinyl ethers such as allyl vinyl ether, ethynyl vinyl ether, alkynyl vinyl ethers such as! -Methyl-2-proenyl vinyl ether , 4-vinyl ether styrene, hydroquinone divinyl ether, phenyl vinyl ether, p-methoxy phenyl vinyl ether, bisphenol A divinyl ether, tetrabromobisphenol A divinyl ether, bisphenol F divinyl ether, phenoxethylene vinyl ether, P-bromophenoxyethylene vinyl ether Aryl vinyl ethers such as 1,4-benzenedimethanol divinyl ether, Nm-chlorophenyl Aralkyl divinyl ethers such as diethanolamine divinyl ether, m one phenylenebis (ethylene glycol) divinyl ether, urethane polyvinyl ether (e.g., ALLIED-
SIGNAL, VECtomer2010).

The spiro orthoester compounds include:
1,4,6-trioxaspiro (4,4) nonane, 2-methyl-1,1
4,6-trioxaspiro (4,4) nonane, 1,4,6-trioxaspiro (4,5) decane, etc., as bicycloorthoesters, 1-phenyl-4-1-ethyl-2,6,7 Trioxabicyclo (2,2,2) octane, 11-ethyl-4-1-hydroxymethyl-2,6,7-trioxabicyclo (2,2,2) octane and the like, as spiroorthocarbonates,
And cyclic ethers such as 5,7,11-tetraoxaspiro (5,5) undecane and 3,9-dibenzyl-1,5,7,11-tetraoxaspiro (5,5) undecane.

Examples of the cyclic ether compounds include oxetanes such as oxetane and phenyloxetane; tetrahydrofurans such as tetrahydrofuran and 2-methyltetrahydrofuran; tetrahydrobilanes such as tetrahydrosilane and 3-propyltetrahydrosilane; trimethylene oxide; And trioxane.

Examples of the lactones include θ-propiolactone, γ-butyl lactone, δ-caprolactone, δ-valerolactone and the like.

Examples of the oxazoline compounds include oxazoline, 2-phenyloxazoline, and 2-decyloxazoline.

Examples of oxetane compounds include 3-ethyl-3-methoxymethyloxetane, 3-ethyl-3-ethoxymethyloxetane, 3-ethyl-3-butoxymethyloxetane, 3-ethyl-3-hexyloxymethyloxetane, 3-methyl-3-hydroxymethyloxetane, 3-ethyl-3-hydroxymethyloxetane, 3-ethyl-3-allyloxymethyloxetane, 3
Monoethyl-31- (2'-hydroxyethyl) oxymethyloxetane, 3-ethyl-31- (2'-phenoxydipropyl) oxymethyloxetane, 3-ethyl-3- (2'-hydroxy-3'-butoxydipropyl) oxy Methyl oxetane, 3-ethyl-3-1 (2'-one (2 ''-ethoxyethyl)
Oxymethyl) oxetane, 3-Ethyl-3- (2'-butoxyethyl) oxymethyloxetane, 3-Ethyl-3-besidyloxymethyloxetane, 3-Ethyl-3- (pt
ert 1-butylbenzyloxymethyl) oxetane, 3-ethyl-3--1- (phenoxymethyl) oxetane, 3-ethyl-
3- (2-Ethylhexyloxymethyl) oxetane, di [1-1-ethyl (3-oxigetanyl)] methyl ether, xylylenebisoxetane, adipatebisoxetane, cyclohexanedicarboxylate bisoxetane, terephthalate bisoxetane, carbonate bisoxetane, phthalate Bisoxetane, 3-Ethyl-3-hydroxymethyloxetane and hexanedi'ol-terminated bisoxetane, 3-Ethyl-3-hydroxymethyloxetane and neopentyl glycol-terminated bisoxetane, 3-ethyl-3-1-1 Bisoxetane telluride with hydroxyoxetane and propylene glycol, trisoxetane tellurium with 3-ethyl-3-hydroxymethyloxetane and trimethylolpropane, pentaerythritol and 3-ethyl-3-hydroxide Carboxymethyl tetrakis oxetane and Ageraru of Koichi ether product of the oxetane.

The aziridine compounds include aziridine, N-ethylaziridine and the like.

Examples of cyclosiloxane compounds include hexamethyltrisiloxane, otamethylcyclotetrasiloxane, and triphenyltrimethylcyclotrisiloxane.

Examples of ketal compounds include 1,3-dioxolane, 1,3-dioxane, 2,2-dimethyl-1,3-dioxane, 2-phenyl-1,3-dioxane, 2,2-dioctyl-1,3-dioxane. Dioxolan and the like.

Examples of the lactam compounds include β-propiolactam, γ-butyrolactam, δ-caprolactam and the like.

The aryl dialdehyde compounds include 1,2-benzenedicarboxaldehyde, 1,2-naphthalenedialdehyde and the like.

These may be used alone or in combination of two or more.

The cationic polymerization initiator (C) used in the present invention is a compound which causes a cationic polymerization reaction by light, heat, laser, electron beam or the like. For example, preferred are diazonium salts, iodonium salts, sulfonium salts, phosphonium salts, selenium salts, oxonium salts, ammonium salts and the like.

Specifically, in the case of a polymerization initiator which generates a cation by heating, a trade name such as, for example, Sun Aide S
I-45, same left SI-47, same left SI-60, same left SI
-60L, same left SI-80, same left SI-80L, same left S
I-100, same as SI-100L, same as left SI-145,
Same as left SI-150, same as left SI-160, same as left SI-11
0L, same as left SI-180L (products of Sanshin Chemical Industry Co., Ltd., trade name), CI-2921, CI-2920, CI
-2946, CI-3128, CI-2624, CI-
2639, CI-2064 (products of Nippon Soda Co., Ltd., product name), CP-66, CP-77 (product of Asahi Denka Kogyo Co., Ltd.), FC-520 (product of 3M Company, product name)
And the like.

Specific examples of the polymerization initiator which generates a cation by light include trade names such as Silacure UVI-6970, Silacure UVI-6974, Silacure UVI-6990, and Silacure UVI-6.
950 (the above, manufactured by Union Carbide Co., USA, trade name), Irgacure 261 (trade name, manufactured by Ciba Specialty Chemicals), SP-150, SP-170
(The above is a product of Asahi Denka Kogyo Co., Ltd., trade name), CG-24
-61 (manufactured by Ciba Specialty Chemicals, trade name), DAICATII (manufactured by Daicel Chemical Industries, Ltd.), UVAC1591 (manufactured by Daicel UCB Co., Ltd., trade name), CI-2732, CI-285
5, CI-2823, CI-2758 (all trade names, manufactured by Nippon Soda Co., Ltd.), PI-2074 (trade name, manufactured by Rhone Poulin Co., Ltd., pentafluorophenylborate tolylcumyl iodonium salt), FFC509 (3M) BBI-102, BBI-101 (trade name, manufactured by Midori Kagaku), CD-1012 (Sartom, USA)
er company, product name).

As the radical polymerization initiator (D) used in the present invention, conventionally known radical polymerization initiators can be used. Specifically, for example, as a thermal radical polymerization initiator, an azo-based polymerization initiator, for example, azobisisobutyronitrile, and as a peroxide-based compound, for example, isobutyryl peroxide, α, α 'Bis (neodecanoylperoxy) diisopropylbenzene, cumylperoxyneodecanoate, di-n-propylperoxydicarbonate, di-
sec-butyl peroxydicarbonate, 1,1,3
3-tetramethylbutyl peroxy neodecanoate,
Bis (4-butylcyclohexyl) peroxydicarbonate, 1-cyclohexyl-methylethylperoxyneodecanoate, di-2-ethoxyethylperoxydicarbonate, di (2-ethylhexylperoxy)
Dicarbonate, t-hexylperoxyneodecanate, di (3-methyl-3-methoxybutylperoxy)
Dicarbonate, t-butylperoxyneodecanate, t-hexylperoxypivalate, t-butylperoxypivalate, 3,5,5-trimethylhexanoyl peroxide, octanyl peroxide, lauroyl peroxide, stearoyl Peroxide, 1,1,3,3-tetramethylbutylperoxy 2
-Ethylhexanoate, succinic peroxide, 2,5-dimethyl-2,5-di (2-ethylhexanoylperoxy) hexane, 1-cyclohexyl-1
-Methylethyl peroxy-2-ethylhexanoate, t-hexylperoxy 2-ethylhexanoate, 4-methylbenzoyl peroxide, t-butylperoxy 2-ethylhexanoate, m-toluoyl
and benzoyl peroxide, benzoyl peroxide (Niper BW), 1,1-bis (t-butylperoxy) 2-methylcyclohexane, 1,1-bis (t
-Hexylperoxy) -3,3,5-trimethylcyclohexane, 1,1-bis (t-hexylperoxy)
Cyclohexane, 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane, 1,1
-Bis (t-butylperoxy) cyclohexane, 2,
2-bis (4,4-dibutylperoxycyclohexyl) propane, 1,1-bis (t-butylperoxy)
Cyclodecane, t-hexylperoxyisopropyl monocarbonate, t-butylperoxymaleic acid, t
-Butylperoxy-3,5,5-trimethylhexanoate, t-butylperoxylaurate, 2,5-dimethyl-2,5-di (m-toluoylperoxy) hexane, t-butylperoxyisopropyl Monocarbonate, t-butylperoxy 2-ethylhexyl monocarbonate, t-hexylperoxybenzoate,
2,5-dimethyl-2,5-di (benzoylperoxy) hexane, t-butylperoxyacetate,
2-bis (t-butylperoxy) butane, t-butylperoxybenzoate, n-butyl-4,4-bis (t-butylperoxy) valerate, di-t-butylperoxyisophthalate, α, α 'Bis (t-butylperoxy) diisopropybenzene, dicumyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, t-butylcumyl peroxide, di-t- Butyl peroxide, P-menthane hydroperoxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexyne-3, diisopropylbenzene hydroperoxide, t-butyltrimethylsilyl peroxide (perbutyl SM), 1,
1,3,3-tetramethylbutyl hydroperoxide, cumene hydroperoxide, t-hexyl hydroperoxide, t-butyl hydroperoxide, 2,3-di-methyl-2,3-diphenylbutane and the like. .

Examples of the photoradical polymerization initiator include, for example, 2,4-trichloromethyl- (4'-methoxyphenyl) -6-triazine, 2,4-trichloromethyl-
(4'-methoxynaphthyl) -6-triazine, 2,4
-Trichloromethyl- (piperonyl) -6-triazine, 2,4-trichloromethyl- (4'-methoxystyryl) -6-triazine, 2- [2- (5-methylfuran-2-yl) ethenyl] -4 , 6-Bis (trichloromethyl) -S-triazine, 2- [2- (furan-2-
Yl) ethenyl] -4,6-bis (trichloromethyl)
-S-triazine, 2- [2- (4-dimethylamino-
2-methylphenyl) ethenyl] -4,6-bis (trichloromethyl) -S-triazine, 2- [2-dimethylaminoethyl) amino] -4,6-bis (trichloromethyl) -S-triazine, 2- [2- (3,4-dimethoxyphenyl) ethenyl] -4,6-bis (trichloromethyl) -S-triazine, 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -S-triazine , 2-Methyl-4,6-bis (trichloromethyl)
Triazine compounds such as -S-triazine, 2,4,6-tris (trichloromethyl) -S-triazine, tris (chloromethyl) triazine, 4-phenoxydichloroacetophenone, 4-tert-butyl-dichloroacetophenone, 4- tert-butyl-trichloroacetophenone, diethoxyacetophenone, 2-hydroxy-2
-Methyl-1-phenylpropan-1-one, 1- (4
-Isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 1- (4-dodecylphenyl)
-2-hydroxy-2-methylpropan-1-one, 4
Such as-(2-hydroxyphenoxy) -phenyl (2-hydroxy-2-propyl) ketone, 1-hydroxycyclohexylphenylketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1 Acetophenone compounds, thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2,
Thioxanthone compounds such as 4-dimethylthioxanthone, 2,4-diethylthioxanthone, isopropylthioxanthone and 2,4-dichlorothioxanthone; benzoin compounds such as benzoin and benzoin methyl ether; dimethylbenzylketal, acylphosphine oxide and the like. . Examples of the acyl phosphide include Lucylin TPO (trade name, manufactured by BASF),
Irgacure 1700, Irgacure 149, Irgacure 1800, Irgacure 1850, Irgacure 8
19 (above, manufactured by Ciba Specialty Chemicals,
(Product name).

The radical reactive compound (E) used in the present invention has a molecular weight of 190 to 10,000, preferably 250 to 2,000, having one or more (meth) acryloyl groups in one molecule. It is an acrylic compound.

When the molecular weight is less than 190, the volatility is high, the odor is strong, and the physical properties of the coating film are reduced.
If it exceeds 0, the coating viscosity will be high and the coating workability will be poor.

Examples of the compound (E) include phenol polyethoxylate (meth) acrylate, phenol polypropoxy (meth) acrylate, nonylphenol monoethoxylate acrylate, 2-ethylhexyl carbitol acrylate, and paracumylphenol EO-modified (meth). Acrylate, isobonyl (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, Polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, butanediol di (meth) acryle DOO, hexanediol di (meth)
Acrylate, nonanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate,
Tricyclodecane dimethyloyl di (meth) acrylate, bisphenol FEO-modified di (meth) acrylate, bisphenol AEO-modified di (meth) acrylate, isocyanuric acid EO-modified di (meth) acrylate,
Trimethylolpropane tri (meth) acrylate, trimethylolpropane di (meth) acrylate, glycerin di (meth) acrylate, glycerin tri (meth)
Acrylate, pentaerythritol tri (meth) acrylate, trimethylolpropaneethoxytri (meth) acrylate, trimethylolpropane EO-modified (ethylene oxide) tri (meth) acrylate, trimethylolpropanepropoxytri (meth) acrylate, trimethylolpropane PO ( (Propylene oxide) modified tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, isocyanuric acid EO modified triacrylate, polyester diacrylate, bisphenol A -Diepoxyacrylic acid adducts, acrylic acrylates and the like.

In the present invention, the invention described in claim 1 is
10 to 100 parts by weight, preferably 20 parts by weight of the reactive organic silicon compound (alkyl silicate) (A) represented by the general formula (1)
To 80 parts by weight, 0 to 90 parts by weight, preferably 20 to 70 parts by weight, of the cation-reactive compound (B), 0.05 to 25 parts by weight, preferably 0.5 to 1 part by weight of the cationic polymerization initiator (C).
It is a curable composition containing 0 parts by weight.

When the amount of the component (A) is less than 10 parts by weight, the hardness of the coating film is poor. If the amount of the component (C) is less than 0.05 part by weight, the curability and the like will be poor, while if it exceeds 25 parts by weight, the weather resistance will be poor.

In the present invention, the invention of claim 2 is characterized in that the reactive organosilicon represented by the general formula (1) is 10 to 99.5 parts by weight, preferably 20 to 80 parts by weight, of the compound (A) represented by the formula (1). Radical-reactive compound (E) 0.5 to 90 parts by weight, preferably 20 to 70 parts by weight, cationic polymerization initiator (C) 0.05 to 25 parts by weight, preferably 0.5 to 10 parts by weight.
It is a curable composition which comprises 0.05 parts by weight, preferably 0.5 to 10 parts by weight of a radical polymerization initiator (D), preferably 0.5 to 10 parts by weight.

When the amount of the component (A) is less than 10 parts by weight, the hardness of the coating film is poor. If the amount of the component (E) is less than 0.5 part by weight, the curability inside the coating film is poor, while if it exceeds 90 parts by weight, the curability on the surface of the film is poor. If the amount of the component (C) is less than 0.05 part by weight, the curability will be poor, and if it exceeds 25 parts by weight, the weather resistance will deteriorate and the price will increase. (D) component is 0.0
If the amount is less than 5 parts by weight, the curability will be poor, while if it exceeds 25 parts by weight, the weather resistance will be poor.

In the present invention, the invention according to claim 3 is characterized in that 10 to 98 parts by weight, preferably 20 to 80 parts by weight of the compound (A) represented by the general formula (1),
90 parts by weight, preferably 20 to 70 parts by weight, 1 to 90 parts by weight of the radical reactive compound (E), preferably 20 to 7 parts by weight
0 parts by weight, a cationic polymerization initiator (C) 0.05 to 25 parts by weight, preferably 0.5 to 10 parts by weight, and a radical polymerization initiator (D) 0.05 to 25 parts by weight, preferably 0.5 to 5 parts by weight.
It is a composition comprising 10 parts by weight.

When the amount of the component (A) is less than 10 parts by weight, the hardness is inferior. If the component (B) exceeds 90 parts by weight, the curability and the like inside the coating film will be poor. If the amount of the component (E) is less than 1 part by weight, the curability inside the coating film is poor, while if it exceeds 90 parts by weight, the surface curability and the like are poor. If the amount of the component (C) is less than 0.05 part by weight, the curability will be poor, while if it exceeds 25 parts by weight, the weather resistance will be poor. If the amount of the component (D) is less than 0.05 part by weight, the curability will be poor, while if it exceeds 25 parts by weight, the weather resistance will be poor.

The composition of the present invention may contain, if necessary, a resin other than those described above and a photosensitizer (for example, anthracene-based compound, thioxanthone-based compound, anthraquinone-based compound, full-olefin-based compound, naphthalene-based compound, pyrene-based compound). Compounds), fillers, colorants, pigments, pigment dispersants, flow regulators, leveling agents, defoamers, ultraviolet absorbers, light stabilizers, antioxidants, gel particles, fine particles, etc. No problem.

Examples of the pigment to be added to the composition of the present invention as needed include, for example, inorganic coloring pigments such as titanium white, carbon black, red iron oxide and titanium yellow; quinacridone red, azo red, phthalocyanine blue, phthalocyanine green and organic yellow. Organic coloring pigments such as pigments; coloring pigments such as glittering pigments such as aluminum powder, glittering mica powder, and glittering graphite; extender pigments such as silica powder, calcium carbonate, barium sulfate, mica, clay, and talc; calcium ion exchange Examples include rust preventive pigments such as silica, phosphate rust preventive pigments and chromate pigments. The compounding amount of the pigment can be used within a range that does not inhibit a curing reaction based on a cation or radical reaction by light irradiation in the composition of the present invention. The amount of the pigment to be blended is usually within a range of usually 200 parts by weight or less, particularly 100 parts by weight or less based on 100 parts by weight of the total amount of the components of the clear film.

As the fluidity modifier, any fluidity modifier known per se in the field of paints can be used, for example, silica-based fine powder, bentonite-based regulator,
Examples include polyamide-based regulators, diurea-based regulators, and organic resin fine particles produced by aqueous emulsion polymerization or non-aqueous dispersion polymerization. Each of the organic resin fine particles may be crosslinked.

The composition of the present invention can be used for coating materials such as metals, cans, plastics, papers, wood materials, inorganic materials, electrodeposition coated plates, laminated plates, films of PET, polyolefins, etc. It can be applied as an ink material.

The coating can be performed by a conventionally known method, for example, a spray, roll coater, gravure coater, flexo, screen, spin coater, flow coater, electrostatic coating, or the like.

In the method for forming a coating film according to the present invention, the curable composition may be coated on the surface of the base material in an amount of 0.5 to 100 μm.
m, followed by heating or irradiation with active energy rays, or curing during or after irradiation with active energy rays.

The heating in the present invention includes, for example, a hot blast stove,
An electric furnace, infrared rays, an induction heating method and the like can be applied, and there is no particular limitation. The heating temperature can be in the range of 40 ° C. to 260 ° C., preferably in the range of 70 ° C. to 200 ° C.

The active energy ray referred to in the present invention is, for example, a low-pressure mercury lamp, a medium-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, an incandescent lamp, a xenon lamp, a halogen lamp, a carbon arc lamp, a metal halide lamp, a fluorescent lamp, a tungsten lamp , Gallium lamp, excimer, laser, electron beam, β-ray, γ-ray and the like can be used.

[0056]

Next, the present invention will be described in detail with reference to examples. In the examples, “parts” indicates “parts by weight”.

Example 1 80 parts of ethyl silicate 40 (manufactured by Colcoat Co., Ltd., average molecular weight: 745), 20 celloxite 2021P (manufactured by Daicel Chemical Industries, Ltd., alicyclic epoxy resin)
And CI-2758 (product of Nippon Soda Co., Ltd.) were mixed and dissolved to obtain a photocationically curable composition (I). The curable composition (I) was coated on a glass plate with a bar coater so as to have a thickness of 15 μm. This coated plate was cured by irradiating it with ultraviolet rays of 500 mJ / cm ² using a metal halide lamp. The resulting coating film had a pencil hardness of 5H and a gel fraction of 9
5%.

Example 2 50 parts of methyl silicate 51 (manufactured by Colcoat Co., Ltd., average molecular weight 470), 50 parts of neopentyl glycol diacrylate, PI-2074 (manufactured by Rhodia Co., Ltd.)
2 parts of a cationic photopolymerization initiator and 4 parts of Irgacure 184 (product of Ciba Specialty Chemicals) were mixed and dissolved to obtain a photocurable composition (II). This curable composition (II) was applied on a primer-treated aluminum plate by a roll coater so as to have a thickness of 10 μm. This painted plate is 300mJ by metal halide lamp.
/ cm ² of ultraviolet light. The pencil hardness of the obtained coating film is 4
At H, the finish was good.

Example 3 Ethylsilicate 48 (product of Colcoat Co., Ltd.) 35
Part, 3-acryloxypropyltrimethoxysilane 30
Part, neopentyl glycol diacrylate hydroxypivalate (Nippon Kayaku Co., Ltd. product, KAYARAD MANDA) 35
Parts, 3-2 parts of CI-2758 (product of Nippon Soda Co., Ltd.) and 4 parts of Irgacure 819 (product of Ciba Specialty Chemicals), mixed and dissolved to obtain a curable composition (III).
I got This composition (III) was applied to a glass plate so as to have a thickness of 20 μm.
Ultraviolet light of 0 mJ / cm ² was irradiated. The finished appearance of the obtained coating film was good, and the pencil hardness was 6H.

Example 4 Ethyl silicate 48 (product of Colcoat Co., Ltd.) 40
Parts, γ-glycidoxypropyltrimethoxysilane 40
Parts, 1,6 hexanediol diacrylate 20 parts, C
4 parts of I-2758 and 4 parts of Irgacure 184 were mixed and dissolved to obtain a curable composition (IV). This composition (IV) is coated on a corona-treated PET film with a thickness of 5 μm.
m and apply UV light to 300m with a high pressure mercury lamp.
J / cm ^{2 was} irradiated. The obtained coating film was coated with steel wool (# 0
000) for 10 reciprocations, but showed no scratches and good scratch resistance. Adhesion was also good.

Example 5 50 parts of ethyl silicate 48, Aronix M31
0, 35 parts, styrene and γ-methacryloxypropyltrimethoxysilane (product of Nippon Konica, trade name A-
174) (an average molecular weight of 400).
(0, 50% toluene solution) and 50 parts of titanium dioxide were added and mixed to obtain a white enamel. To 100 parts of the white enamel, 4 parts of CI-2946 (manufactured by Nippon Soda Co., Ltd., thermal cationic polymerization initiator), 2 parts of Perbutyl Z (manufactured by Nippon Oil & Fat Co., Ltd.), and 2 parts of Tinuvin 900 ultraviolet absorber were added.
Department (made by Ciba Specialty Chemicals, trade name)
Was added and mixed to obtain a curable composition (V). The composition (V) was applied to a thickness of 20 μm on a steel plate coated with electrodeposition, and was heated and cured at 140 ° C. for 20 minutes. The pencil hardness of the obtained coating film was 6H, and the adhesion and acid resistance were good.

Example 6 30 parts of ethyl silicate 48, 30 parts of neopentyl glycol diacrylate, and an unsaturated acrylic resin varnish obtained by adding acrylic acid to a copolymer of styrene / methyl methacrylate / butyl acrylate / glycidyl methacrylate (molecular weight 12,000; Unsaturation 1.0 mol / kg
40 parts, oxetane acrylate 15
, 5 parts of xylylene dioxetane, 3 parts of UAC1591 (trade name, manufactured by Daicel UCB), and 3 parts of Irgacure 819 were added, mixed and dissolved to obtain a curable composition (V
I got. The composition (VI) was applied to a top-coated steel sheet by spraying to a thickness of 30 μm. The coated product was irradiated with ultraviolet rays at 700 mJ / cm ² by a metal halide lamp to obtain a cured coating film. The hardness of the obtained coating film was 5H, and the finish was good.

Example 7 40 parts of ethyl silicate 40 (manufactured by Colcoat), 60 parts of the acrylic copolymer (50% solution) of Example 5,
10 parts of 3-acryloxypropyltrimethoxysilane,
Kayarad MANDA (product of Nippon Kayaku Co., Ltd.) 10 parts, 1,
6 hexanediol diacrylate 10 parts, CI-27
58 parts 4 parts, Irgacure 184 4 parts, Tinuvin 3
84-2 (Ciba Specialty Chemicals product)
Two parts were added and mixed to obtain a curable composition (VII). The curable composition (VII) is applied to a thickness of 20 μm on a coated plate obtained by applying an exterior coating to an inorganic material, and is applied to the sun for 30 minutes.
After a few minutes, a cured coating was obtained. The resulting coating film had a good finish and a pencil hardness of 4H.

[0064]

EFFECTS OF THE INVENTION The curable composition of the present invention, having the above-mentioned constitution, forms a film having particularly high surface hardness and excellent adhesion, chemical resistance and weather resistance.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification code FI Theme coat ゛ (Reference) C08K 5/14 C08K 5/14 5/23 5/23 C08L 83/02 C08L 83/02 C09D 5/00 C09D 5/00 C 183/02 183/02 F-term (reference) 4F073 AA07 BB01 BB02 CA41 CA42 CA45 EA63 EA64 EA65 FA03 FA08 GA01 4J002 BC022 BC092 BC112 BE042 BG042 BG052 CD052 CD062 CP031 ED026 ED036 E0E80H EK0008 EK038 EK048 EK058 EL036 EL046 EL066 EL126 EL136 EN137 EQ017 ET008 EU056 EU188 EV297 EW177 EX036 EZ007 FD010 FD090 GH01 4J038 DB001 DB002 DL021 DL022 FA011 FA012 FA041 FA042 FA061 FA062 FA111 FA112 FA231 GA031 FA031 FA031 FA031 JA33 JA66 JA68 JA75 JB11 JB16 JB23 JB26 JB36 JB37 JC17 JC18 JC29 JC32 KA03 NA03 NA04 NA11 NA12 NA24 PA17 PA19

Claims (7)

[Claims] (A) a reactive organosilicon compound represented by the following general formula (1): (In the above formula, R ₁ , R ₂ , R ₃ , and R ₄ are the same or different and each represents an alkyl group having 1 to 4 carbon atoms, and n represents an integer of 1 to 50.) 10 to 100 parts by weight ( B) A cation reactive compound 0 to 90 parts by weight (C) a cationic polymerization initiator 0.05 to 25 parts by weight. (A) 10 to 99.5 parts by weight of a reactive organic silicon compound represented by the above general formula (I) (E) 0.5 to 90 parts by weight of a radical reactive compound (C) Cationic polymerization initiator The curable composition according to claim 1, wherein 0.05 to 25 parts by weight of (D) a radical polymerization initiator is blended. (A) 10 to 98 parts by weight of a reactive organic silicon compound represented by the above general formula (I) (B) 1 to 90 parts by weight of a cation reactive compound (E) 1 to 90 parts by weight of a radical reactive compound The curable composition according to claim 1, wherein the curable composition comprises (C) 0.05 to 25 parts by weight of a cationic polymerization initiator and (D) 0.05 to 25 parts by weight of a radical polymerization initiator. 4. The curable composition according to claim 2, wherein the radical-reactive compound (E) is a compound having one or more (meth) acryloyl groups in one molecule. 5. A method for forming a film, comprising applying the curable composition according to any one of claims 1 to 4 to an object to be coated and heating to obtain a cured film. 6. A coating film obtained by applying the curable composition according to any one of claims 1 to 4 to an object to be coated and irradiating it with active energy rays. Forming method. 7. The composition is cured by applying the curable composition according to any one of claims 1 to 4 to an object to be coated and heating it during and / or after irradiation with active energy rays. A method for forming a coating film, comprising obtaining a coating film.