JPH07223301A - Film article - Google Patents

Abstract

PURPOSE:To provide a coating composition applying a protective coating which has sufficient adhesion and is excellent in wear resistance to a film consisting mainly of polyvinyl alcohol (PVA). CONSTITUTION:This film article is obtained by curing (1) colloidal silica, (2) an organic silicon compound or its partial hydrolysate having a polymerizable functional group (an acrylic group and epoxy group), (3) a polymerizable compound which is multifunctional and other than an acrylic group and (4) a coating composition of a cation photopolymerization initiator after their application to a film consisting mainly of PVA. Then a film article is obtained by curing further (5) a composition to be obtained by adding a polymerizable compound which is multifunctional and has an acrylic group or further (6) a composition to be obtained by adding a radical photopolymerization initiator after their application to the film.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a film article obtained by applying a coating composition for forming a protective film to a film containing polyvinyl alcohol as a main component.

[0002]

2. Description of the Related Art It is common practice to provide a protective coating as one of the methods for improving the abrasion resistance, solvent resistance and weather resistance of plastic substrates. In particular, the method of curing the coating film for protective coating using radiation is an excellent method because a cured film can be obtained in a short time. An acrylic resin is used as a composition for obtaining the protective coating by such a method. However, since acrylic resins have a limit in hardness, silicon-based paints in which colloidal silica or an organic silicon compound is introduced into acrylic resins have also been developed (for example, US Pat.
79836, JP-A-3-56514).
In addition, acrylic monomers or oligomers and non-acrylic monomers (vinyl ether, epoxy compounds, etc.)
It is also known about systems that use
See JP-A-2-269777). On the other hand, various transparent plastics are used for equipment related to liquid crystal display devices, for example, protective films for polarizing films. Among transparent plastics, a film containing polyvinyl alcohol (PVA) as a main component has excellent physical properties such as optical performance and weather resistance,
Moreover, the manufacturing method does not pollute the environment. For these reasons, it can be expected that the PVA film will be increasingly used in optical equipment such as equipment related to liquid crystal display devices.

[0003]

However, a conventional protective coating film using an acrylic resin paint or a silicone paint excellent in performance such as abrasion resistance may not have sufficient adhesion to a polyvinyl alcohol film. It was Even in the above-mentioned JP-A-2-269777, there is no suggestion of adhesion to a polyvinyl alcohol film. Therefore, an object of the present invention is to provide a coating composition for applying a protective coating excellent in abrasion resistance and the like having sufficient adhesiveness to a film containing polyvinyl alcohol as a main component. Another object of the present invention is to provide an article made of a film containing polyvinyl alcohol as a main component, which is provided with a protective coating having excellent abrasion resistance.

[0004]

The above objects of the present invention can be achieved by the following constitutions. That is, (1) colloidal silica, (2) an organosilicon compound having a polymerizable functional group or a partial hydrolyzate thereof, (3) a polyfunctional compound having a polymerizable functional group other than an acrylic group, and (4) A film article obtained by applying a coating composition comprising a cationic photopolymerization initiator to a film containing polyvinyl alcohol as a main component and curing the film, or (1)
Colloidal silica, (2) Organosilicon compound having a polymerizable functional group or a partial hydrolyzate thereof, (3) Polyfunctional compound having a polymerizable functional group other than an acrylic group, (4) Polyfunctional acrylic group A film article obtained by applying a coating composition comprising a polymerizable compound having the formula (5) and a cationic photopolymerization initiator to a film containing polyvinyl alcohol as a main component and curing the composition, or
1) colloidal silica, (2) organosilicon compound having a polymerizable functional group or a partial hydrolyzate thereof, (3)
A polyfunctional compound having a polymerizable functional group other than an acrylic group, (4) a polyfunctional polymerizable compound having an acrylic group, (5) a cationic photopolymerization initiator and (6) a radical photopolymerization initiator It is a film article obtained by applying the coating composition to a film containing polyvinyl alcohol as a main component and then curing the film.

(1) The colloidal silica as the first component of the present invention uses an aqueous or other solvent dispersion system of submicron-sized silica particles. For example, Nalco1057
(Trade name of Nalco, average particle size 20 nm, solid content 3
0%, prepoxy ethanol dispersion), Snowtex O
-40 (trade name of Nissan Kagaku Co., Ltd., average particle size 20 nm,
Solid content 40%, water dispersion), IPA-ST (trade name, manufactured by Nissan Kagaku KK, average particle size 20 nm, solid content 30%, isopropyl alcohol dispersion) and the like are used. Colloidal silica is about 25 to about 25% of total solids in the coating composition.
It is used at 80% by weight, preferably about 30-70% by weight.
If the colloidal silica is less than about 25% by weight of the total solids in the coating composition, the abrasion resistance is lowered to the extent that it does not fall within a practical range, and the colloidal silica is about 25% by weight or less. If it exceeds 80% by weight, there is a problem that cracks occur.

(2) As the second component of the present invention, the organosilicon compound having a polymerizable functional group or a partial hydrolyzate thereof, the organosilicon compound having an acrylic group or an epoxy group or a partial hydrolyzate thereof is as described above. Any organosilicon compound having a functional group or a partial hydrolyzate thereof can be used, but an acryloxysilane having the following general formula (A) or a glycidoxysilane having the general formula (B) or a partial hydrolysis thereof. It is preferable to use a decomposition product or a mixture of the above-mentioned acryloxysilane or glycidoxysilane or a partial hydrolysis product thereof.

[0007]

[Chemical 1] Here, R ³ and R ⁴ are the same or different monovalent hydrocarbon groups, and also include the halogen-substituted monovalent hydrocarbon groups and unsaturated groups. R ³ and R ⁴ represent lower alkyl having 1 to 8 carbon atoms such as methyl, ethyl and propyl, vinyl and aryl. R ⁵ is a divalent hydrocarbon group having 2 to 8 carbon atoms,
R ⁶ represents hydrogen or a monovalent hydrocarbon group, b = 1,
2,3, c = 0,1,2, d = 4-bc, and often b = 3, c = 0, d = 1. General formula (A)
The acryloxysilane having is, for example, 3-methacryloxypropyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, 2-methacryloxyethyltrimethoxysilane, 2-acryloxyethyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane. Ethoxysilane, 3-acryloxypropyltriethoxysilane, 2-methacryloxyethyltriethoxysilane, 2
Such as acryloxyethyltriethoxysilane.

[0008]

[Chemical 2] Here, R ⁷ and R ⁸ are the same or different monovalent hydrocarbon groups, and also include the halogen-substituted monovalent hydrocarbon groups and unsaturated groups. R ⁷ and R ⁸ represent, for example, methyl, ethyl, propyl, vinyl or acryl. Further, R ⁹ has 2 to 2 carbon atoms.
8 is a divalent hydrocarbon group, and e = 1, 2, 3, f =
0, 1, 2, g = 4-ef, and often e =
3, f = 0 and g = 1. The glycidoxysilane of the general formula (B) is, for example, 3-glycidoxypropyltrimethoxysilane, 2-glycidoxyethyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane,
2-glycidoxyethyltriethoxysilane and the like. The second component of the present invention is 0.05 to 1.5 times the weight of the solid content of colloidal silica, preferably 0.1 to 1.5 times.
Used at 0.5 times.

(3) As the polyfunctional compound having a polymerizable functional group other than an acrylic group, which is the third component of the present invention, for example, glycidyl ether, allyl ether, vinyl ether and alicyclic polyepoxide are used. More specifically, for example, trimethylolpropane triglycidyl ether, ethylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, bisphenol A diglycidyl ether, glycidyl methacrylate, glycidyl ether, Trimethylolpropane triglycidyl ether, ethylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, vinyl Glycidyl ethers such as phenol A diglycidyl ether, 1,1,2,2-tetraallyloxyethane, triallyl cyanurate, diethylene glycol diallyl ether, maleic acid diallyl ether, adipic acid diallyl ether, diethylene glycol bisallyl carbonate, allyl Allyl ether such as glycidyl ether, diethylene glycol divinyl ether, reethylene glycol divinyl ether, tetraethylene glycol divinyl ether,
Vinyl ethers such as dipropylene glycol divinyl ether, tripropylene glycol divinyl ether, 1,4-divinyloxybutane, 1,6-hexanediol divinyl ether and cyclohexanedimethanol divinyl ether, 3,4-epoxycyclohexylmethyl-3,4- Examples thereof include alicyclic diepoxides such as epoxycyclohexanecarboxylate and bis- (3,4-epoxycyclohexyl) adipate. This third component is used in an amount of 0.1 to 2 times, preferably 0.2 to 1.5 times the weight of the solid content of colloidal silica.

(4) The polyfunctional polymerizable compound having an acrylic group, which is sometimes used as the fourth component of the present invention, is
For example, trimethylol propane triacrylate, trimethylol propane triethoxy triacrylate,
Trimethylolpropane trimethacrylate, di-trimethylolpropane tetraacrylate, pentaerythritol monohydroxytriacrylate, pentaerythritol tetraacrylate, dipentaerythritol (monohydroxy) pentaacrylate, 1,6-hexanediol diacrylate, 1,4-butane Diol diacrylate, ethylene glycol diacrylate, diethylene glycol diacrylate, tetraethylene glycol diacrylate, tripropylene glycol diacrylate, neopentyl glycol diacrylate, poly (butanediol) diacrylate, polyethylene glycol diacrylate, polypropylene glycol diacrylate, 1 , 6-hexanediol dimethacrylate, 1 4-butanediol dimethacrylate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, tripropylene glycol dimethacrylate, neopentyl glycol dimethacrylate, poly (butanediol) dimethacrylate, polyethylene glycol dimethacrylate, polypropylene glycol di Examples thereof include methacrylate and bisphenol A diacrylate. The fourth component is used in an amount of 0 to 3 times, preferably 0.2 to 2 times the weight of the solid content of colloidal silica.

[0011] (5) a cationic photopolymerization initiator which is the fifth component of the present invention the following formula ^{_{(R 10 -C 6 H 4)}} n X + MQ h - the compound is used. Here, X is a radical selected from iodine (I), phosphorus (P), and sulfur (S), and M
Is a metal or metalloid, Q is a halogen radical selected from fluorine (F), chlorine (Cl), bromine (Br) and iodine (I), and R ¹⁰ is hydrogen or a carbon number of 1 to 1.
12 monovalent hydrocarbon groups, h = 4, 5, 6, n =
A few. For example, as MQ _h ⁻ , various kinds of ion species can be used, but SbF ₆ ⁻ , AsF ₆ ⁻ , B
Those selected from F ₄ ⁻ and PF ₆ ⁻ are preferable. The cationic photopolymerization initiator of the present invention is, for example, a diphenyliodonium salt of tetrafluoroborate, hexafluorophosphate, hexafluoroarsenate and hexafluoroantimonate, tetrafluoroborate, hexafluorophosphate, hexafluoroarsenate and hexafluoro. Antimonate triphenylsulfonium salt, etc., commercially available products such as Irgacure
261 {(1-6-η-cumene) (η-cyclopentadienyl) iron (1+) hexafluorophosphate (1-) product name manufactured by Nippon Ciba-Geigy Co., Ltd.} or Cylacure UV
I-6970 {4 manufactured by Union Carbide Japan Co., Ltd.
-4'bis [di (β-hydroxyethoxy) phenylsulfonio] phenylsulfide-bis-hexafluoroantimonate (trade name) or SP-150 {Asahi Denka Kogyo's 4-4'bis [di] (Β-Hydroxyethoxy) phenylsulfonyl] phenyl sulfide-
Bis-hexafluorophosphate} and the like are preferably used. The fifth component is 0.1 with respect to the solution solid content.
-6% by weight, but preferably 0.3-4% by weight. The cationic photopolymerization initiator which is the fifth component of the present invention is effective as an initiator for a crosslinking reaction by ultraviolet rays. Further, the cationic photopolymerization initiator that produces an effect of imparting adhesiveness to the substrate cures the polymerizable compound by using electron beam irradiation even if the polymerizable compound is present in the composition of the present invention. In this case, the following sixth component can be used alone without using it.

(6) The radical photopolymerization initiator which is the sixth component of the present invention is an organosilicon compound which is the second component, a polyfunctional polymerizable compound having a non-acrylic group or a fourth component which is the third component. When a polymerizable compound is present in the composition as in the case of using a polyfunctional polymerizable compound having an acrylic group, it is a compound useful for adding or crosslinking a polymerizable free radical group. . The radical photopolymerization initiator which is the sixth component of the present invention can improve the hardness of the film article. Examples of the cationic photopolymerization initiator of the present invention include benzophenone, 1-hydroxycyclohexyl phenyl ketone, 2,2-dimethoxy-2-phenylacetophenone, 2-hydroxy-2.
-Methyl-1-phenylpropan-1-one, 2,4
6-trimethylbenzoyldiphenyl-phosphine oxide, 2,2-diethoxyacetophenone 3,
3 ', 4,4'-Tetra- (t-butylperoxycarbonyl) benzophenone is preferably used. More specifically, Darocur 1173 (2-hydroxy-2-methyl-1-phenylpropan-1-one manufactured by Ciba-Geigy Co., Ltd.) is used. The sixth component is added in an amount of 0 to 10% by weight based on the solid content of the solution, but is preferably used in an amount of 0.3 to 6 times. The cationic photopolymerization initiator as the fifth component is used in an amount of 10 to 1 in the photopolymerization initiator.
It is preferable to use it in an amount of 00% by weight, and to add the rest to the radical photopolymerization initiator of the sixth component to use in combination with these photopolymerization initiators.

(7) Further, in the composition of the present invention, in order to improve abrasion resistance and adhesiveness as an optional component, a monofunctional acrylic group, glycidyl group, allyl group or vinyl group is polymerizable. Compounds can also be added. For example, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, tetrahydrofurfuryl acrylate, tetrahydrofurfuryl methacrylate, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate. , Propyl methacrylate,
Glycidyl methacrylate, n-butyl glycidyl ether, phenyl glycidyl ether, allyl alcohol, allyl cinnamate, allyl cyclohexane, phenyl allyl ether, vinyl acetate, 4-hydroxybutyl vinyl ether, dodecyl vinyl ether, propenyl ether propylene carbonate, vinyl acid acrylate, etc. are used. To be This seventh component is added in an amount of 0 to 20% by weight based on the solid content of the solution, but preferably used in an amount of 0 to 10 times.

In the composition of the present invention, either a leveling agent for a cured coating, a polyoxyalkylene / polydimethylsiloxane copolymer or a polyoxyalkylene / fluorocarbon copolymer is used as a lubricity imparting agent. It can also be used. The amount of the component used is 0.01 to 7 parts by weight based on the total amount of the film-forming components. Further, well-known antioxidants, weather resistance imparting agents, ultraviolet absorbers, matting agents, surfactants, coupling agents, thixotropic agents may be added. The composition of the present invention can be cured by radiation such as ultraviolet rays or electron beams to form a transparent protective film having abrasion resistance on a film mainly composed of PVA. Further, it can be coated as a direct protective film of a polarizing film mainly composed of PVA to which a disperse dye or a dichroic dye, for example, an anthraquinone type, an azo type, a dye compound such as an iodine molecule is added.

In the practice of the present invention, the photocurable coating composition preferably comprises first forming a hydrolysis product of silane mixed with a sufficient amount of water of the colloidal silica and the silane, which is the colloidal silica. Adjust by ensuring that the reaction of the silane with the silane is promoted.
The mixture is allowed to react at room temperature for a time sufficient to complete the reaction of the colloidal silica with the silane, typically from about 1 to about 20.
Stir for hours. Then, a compound having a polymerizable functional group other than a polyfunctional acrylic group or a mixture thereof, other polymerizable compounds, a radiation-sensitive initiator, and optionally any other above-mentioned additives are added, The mixture is generally well agitated to prepare a homogeneous coating composition. In addition, organic solvents such as alcohols may optionally be included in the formulation if desired to reduce the viscosity of the coating composition. The composition of the present invention is applied onto at least one surface of a PVA-based film by a coating method such as a flow method, a brush coating method, a spray method, a dipping method, a spin coating method, a bar coating method, a roll coating method, or the like. .

Further, the above composition is applied to a film containing PVA as a main component and then cured. The following curing method can be used. For example, heat treatment may be performed in advance to evaporate the solvent, and then the curing treatment may be performed. Alternatively, after the curing treatment, post-curing to which heat is applied, or light curing treatment and heat treatment may be performed at the same time. The curing treatment can be performed by irradiation with light such as ultraviolet rays and electron beams. Light irradiation is performed, for example, by irradiating a metal halide lamp from a position of 10 cm, but is not limited to this, as long as it can be cured by a mercury lamp,
The light source wavelength is not limited.

As the film mainly composed of PVA, polyvinyl alcohol alone, ethylene / vinyl alcohol resin, ethylene / vinyl acetate / vinyl alcohol resin,
Thermosetting resin containing polyvinyl alcohol / polyvinyl chloride mixture, polyvinyl alcohol / vinyl acetate mixture, polyvinyl alcohol / acrylic ester modified product, and other initial condensation products of urea, melamine, phenol, etc. In addition to the combination products, modified products can be used to improve various performances. As an additive for the film, an article containing a plasticizer, a defoaming agent, a water resistant agent, and a bulking agent, specific examples of which are described in the polyvinyl alcohol manufacturer's catalog. The PVA content in the film mainly composed of PVA is 50% to 100%, preferably 70% to 100%. PVA content is 5
If it is less than 0%, the excellent physical properties of PVA (transparency, heat resistance, chemical resistance, oxygen impermeability, mechanical properties) cannot be utilized. Although various grades of PVA-based films are commercially available, film-forming property, film strength,
Considering adhesiveness and the like, it is preferable to use PVA within the following range. Average degree of polymerization of PVA 200 to 2500 Viscosity of 4% aqueous solution / 3 to 150 cps at 20 ° C. Saponification value 70 to 99.9% Further, the film may be uniaxially stretched or biaxially stretched.

[0018]

According to the present invention, the organosilicon compound having a polymerizable functional group is partially hydrolyzed in the presence of water, and the resulting silanol group reacts with the silanol group on the surface of the colloidal silica. Since the polymerizable functional group is compatible with the organic component, the colloidal silica can be stably present in the coating liquid or in the coating film obtained by curing. Furthermore, the OH group on the surface of polyvinyl alcohol is a functional group of an organosilicon compound having a polymerizable functional group or a functional group of a partial hydrolyzate thereof or a silanol group or a compound having a polymerizable functional group other than an acryl group ( (Glycidyl group, vinyl group, allyl group) react in the presence of a cationic photopolymerization initiator to obtain adhesiveness, which contributes to the improvement of adhesion between the film and the coating film, and also radical photopolymerization initiation It is considered that, in the presence of the agent, the compound having a polyfunctional acrylic group was polymerized and crosslinked to obtain a coating film having excellent pencil hardness.

[0019]

EXAMPLE An example of the present invention will be described below. Example 1 30 g of Nalco1057, 2 g of 3-methacryloxypropyltrimethoxysilane (A-174) and 1.3 g of distilled water were mixed and stirred for 1 hour. While stirring the mixed solution, 3.4 g of trimethylolpropane triacrylate (# 295) and 1.2 g of tetraallyloxyethane were added and stirred for 1 hour. Next, Darocur 1
173 0.6 g, Syracure UVI 6970 0.2 g, Flowrad FC430 as a leveling agent
(Fluorine-based alkyl ester surfactant manufactured by 3M) was added in an amount of 0.2 g, and the mixture was further stirred for 1 hour in a light-shielded state. The above mixture was aged at room temperature for 48 hours. Commercially available film containing polyvinyl alcohol as a main component {Kuraray Poval; manufactured by Kuraray Co., Ltd .; PVA-HC film (thickness 50 μm); volatile content 8.5% or less, sodium acetate 2.5% or less, saponification degree 99.85 mol% or more, viscosity 25.0 ± 3.5 cps (4% 20 ° C.), PVA content 90.0%} with a bar coater, the above mixed solution is applied to a metal halide lamp (160 W / cm). 10c
It was irradiated and cured from the position m. The conveyor speed at this time is 80 cm / min. The appearance of the obtained coating film was colorless and transparent. The adhesion was 100/100 and the pencil hardness was 4H.

The cross-hatch test (Goban eye test J
Adhesion test according to ISK5400) was performed after cross-cutting the coating film, and then using Nichiban Co., Ltd. Cellotape T
A cross-hatch test was carried out using -240 (trade name), and it was judged from the adhesion state of the coating film. The pencil hardness was tested according to JIS standard (1 kg load). Hereinafter, experiments on Examples 2 to 17 and Comparative Examples 1 to 4 were conducted in the same manner, and the results are shown in Tables 1 to 4.

[0021]

[Table 1]

[0022]

[Table 2]

[0023]

[Table 3]

[0024]

[Table 4]

The abbreviations in Tables 1 to 4 are as follows. 1057: Colloidal silica, 30%
Solid content, dispersion solvent propoxyethanol (NALCO
Made) 0-40: colloidal silica, 40%
Solid content, dispersion solvent water (manufactured by Nissan Chemical Industries, Ltd.) A-174: 3-methacryloxypropyltrimethoxysilane (manufactured by Nippon Unicar Co., Ltd.) A-187: 3-glycidoxypropyltrimethoxysilane (manufactured by Nippon Unicar) Tetraallyloxyethane: manufactured by Tokyo Chemical Industry Co., Ltd. triallyl cyanurate: manufactured by Tokyo Chemical Industry Co., Ltd. TRIAM-501: diethylene glycol diallyl ether (manufactured by Wako Pure Chemical Industries, Ltd.) CR-39: Diethylene glycol bisallyl carbonate (manufactured by Tokuyama Soda Co., Ltd.) Diallyl adipate: manufactured by Tokyo Chemical Industry Co., Ltd. Diallyl maleate: manufactured by Tokyo Chemical Industry Co., Ltd. Allyl glycidyl ether: manufactured by Tokyo Chemical Industry Co., Ltd. TMP-TG: tri Methylolpropane triglycidyl ether (Sakamoto Yakuhin Kogyo Co., Ltd.) 40E : Ethylene glycol diglycidyl ether (manufactured by Kyoeisha Chemical Co., Ltd.) CHVE: Cyclohexanedimethanol divinyl ether (ISP Japan Co., Ltd.)
DVE-3: triethylene glycol divinyl ether (manufactured by Ispy Japan Co., Ltd.) # 295: trimethylolpropane triacrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd.) AD-TMP: di-trimethylolpropane tetraacrylate (Manufactured by Shin-Nakamura Chemical Co., Ltd.) M-360: trimethylolpropane E
O-modified (n-2) triacrylate (manufactured by Toagosei Chemical Industry Co., Ltd.) M-350: trimethylolpropane E
O-modified (n-1) triacrylate (manufactured by Toagosei Chemical Industry Co., Ltd.) M-310: trimethylolpropane P
O-modified (n-1) triacrylate (manufactured by Toagosei Chemical Industry Co., Ltd.) 4160: neopentyl glycol alkoxydiacrylate (manufactured by San Nopco Co., Ltd.) Vinyl acetate: DenroCure 1173: 2-hydroxy manufactured by Denki Kagaku Kogyo Co., Ltd. 2-Methyl-1-phenylpropan-1-one (manufactured by Japan Ciba-Geigy Co., Ltd.) UV16970: 4-4 ′ bis [di (βhydroxyethoxy) phenylsulfonio] phenylsulfide-bis-hexafluoroantimonate ( Union Carbide Japan Co., Ltd. SP-150: 4-4 ′ Bis [di (βhydroxyethoxy) phenylsulfonio] phenylsulfide-bis-hexafluorophosphate (Asahi Denka Kogyo KK) Irgacure 261: (1-6-η-cumene)
(Η-Cyclopentadienyl) iron (1+) hexafluorophosphate (1-) (manufactured by Nippon Ciba Geigy)

As can be seen from the results of Examples and Comparative Examples, when there is no non-acrylic compound of the component (3) of the present invention (Comparative Example 1), there is no cationic photopolymerization initiator of the component (5) of the present invention. In comparison with the case (Comparative Example 2), the case without the acrylic compound of the component (4) of the present invention (Comparative Example 3) and the case without the silane of the component (2) of the present invention (Comparative Example 4), The examples show excellent coating performance.

[0027]

EFFECT OF THE INVENTION A coating film having excellent adhesion to a film containing polyvinyl alcohol as a main component and excellent pencil hardness was obtained.

Claims (3)

[Claims] 1. A colloidal silica, (2) an organosilicon compound having a polymerizable functional group or a partial hydrolyzate thereof, (3) a polyfunctional compound having a polymerizable functional group other than an acrylic group, and (4) A film article obtained by applying a coating composition comprising a cationic photopolymerization initiator to a film containing polyvinyl alcohol as a main component and curing the composition. 2. (1) Colloidal silica, (2) Organosilicon compound having a polymerizable functional group or a partial hydrolyzate thereof, (3) Polyfunctional compound having a polymerizable functional group other than an acrylic group, It is obtained by applying a coating composition comprising (4) a polyfunctional polymerizable compound having an acrylic group and (5) a cationic photopolymerization initiator to a film containing polyvinyl alcohol as a main component and then curing the composition. And film products. 3. (1) Colloidal silica, (2) Organosilicon compound having a polymerizable functional group or a partial hydrolyzate thereof, (3) Polyfunctional compound having a polymerizable functional group other than an acrylic group, After applying a coating composition comprising (4) a polyfunctional polymerizable compound having an acrylic group, (5) a cationic photopolymerization initiator and (6) a radical photopolymerization initiator to a film containing polyvinyl alcohol as a main component. A film article obtained by curing.