JPH08325474A - Coating composition - Google Patents

Abstract

PURPOSE: To obtain an active-energy-ray-curable coating compsn. which forms a coating film excellent in adhesion to plastic substrates, clarity, antistatic properties, etc., by compounding a specific polyacrylate with a silicate compd. and a photopolymn. initiator. CONSTITUTION: This compsn. contains 100 pts.wt. polyacrylate contg. 35-100wt.% carboxylated polyacrylate, 20-50 pts.wt. silicate compd. obtd. by the polycondensation and transesterification of polymethoxysiloxane having a degree of polymn. of 3-8 in water and an alcohol, and 0.1-3 pts.wt. photopolymn. initiator. Pref. the compsn. is prepd. by compounding 100 pts.wt. polyacrylate with 20-499.9 pts.wt. above silicate compd., 0.1-3 pts.wt. photopolymn. initiator, and 0.1-100 pts.wt. silica sol, the sum of the silica compd. and the silica sol being 500 pts.wt. or lower.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to an active energy which is cured by irradiation with an active energy ray to form a coating film excellent in adhesion to a plastic substrate, transparency, abrasion resistance and antistatic property. The present invention relates to a radiation curable coating composition.

[0002]

2. Description of the Related Art Generally, plastic products such as polycarbonate, polymethylmethacrylate, polyethylene terephthalate, polybutylene terephthalate, nylon 6, nylon 66, vinyl chloride resin, ABS resin, and cellulose acetate are light in weight and easy to process. Since it has excellent impact resistance, it is used in various applications such as panels, sideboards, containers, disk substrates, and bearings.

However, since the surface hardness of these plastic products is low, the surface thereof is easily scratched, which makes it difficult to use the plastic products in the field requiring abrasion resistance. Therefore, an active energy ray-curable hard coat material that imparts abrasion resistance to these plastic products is required. Cured films of commercially available active energy ray-curable hard coat materials have the major drawback of having a high surface resistivity and being prone to generate static electricity. The generation of static electricity promotes dust adhesion and It causes a loss of aesthetics and transparency. In order to avoid such drawbacks, there is a demand for an active energy ray-curable coating agent that gives a cured film satisfying the required performances of both abrasion resistance and antistatic property to the surface of plastic products.

For example, as an active energy ray-curable hard coating agent, a polymerizable compound having two or more acryloyloxy groups and / or methacryloyloxy groups in a molecule and an oligomer having a silica skeleton-forming ability are colloidal silica. There is known a hard coating agent composed of a silica-based polycondensation polymer obtained by polycondensation in the presence (JP-A-5-302041). However, since this hard coat agent does not have antistatic property, an antistatic property-imparting agent, for example, quaternary ammonium salt (see JP-A-5-17916).
No. 0) or metal thiocyanate (Japanese Patent Laid-Open No. 6-2555).
No. 5) is added to this hard coat agent to provide antistatic properties.

However, in the method of adding the antistatic property-imparting agent, when the amount of the antistatic property-imparting agent added is small, the abrasion resistance is excellent, but the antistatic property is insufficient. Further, there is a practical problem that the transparency, the adhesion and the abrasion resistance are reduced as the amount of the antistatic property-imparting agent added is increased.

[0006]

DISCLOSURE OF THE INVENTION The present invention provides an active energy ray-curable coating composition which forms a coating film excellent in adhesion to a plastic substrate, transparency, abrasion resistance and antistatic property. For the purpose of provision.

[0007]

The first aspect of the present invention is (a) a polyfunctional acrylate containing 35 to 100% by weight of a carboxyl group-containing polyfunctional acrylate, and (b) a polymerization degree of 3 to.
A coating composition comprising a silicate compound obtained by polycondensation and transesterification of polymethoxysiloxane of 8 in the presence of water and alcohol, and (c) a photopolymerization initiator, comprising: The compounding amount of the silicate compound of the component (b) is 20 to 500 parts by weight relative to 100 parts by weight of the polyfunctional acrylate, and the component (c) is 0.1 to 3% by weight of the polyfunctional acrylate of the component (a). The present invention provides a coating composition characterized by being compounded.

In the second aspect of the present invention, (a) a polyfunctional acrylate containing 35 to 100% by weight of a carboxyl group-containing polyfunctional acrylate, and (b) a polymethoxysiloxane having a degree of polymerization of 3 to 8 in the presence of water and alcohol. A coating composition containing a silicate compound obtained by polycondensation and transesterification in (1), (c) a photopolymerization initiator, and (d) a silica sol, wherein (a) is 100 parts by weight of a polyfunctional acrylate ( The compounding amount of the silicate compound of the component b) is 20 to 499.9 parts by weight, the component (c) is 0.1 to 3% by weight of the polyfunctional acrylate of the component (a),
The coating composition is characterized in that the silica sol of the component (d) is blended in a proportion of 0.1 to 100 parts by weight with respect to 100 parts by weight of the polyfunctional acrylate of the component (a) (however, (b)). And the sum of the component (d) is 500 parts by weight or less per 100 parts by weight of the component (a)).

[0009]

By combining a carboxyl group-containing polyfunctional acrylate in the component (a), which does not exhibit antistatic performance alone, with a silicate compound of the component (b), which also does not exhibit antistatic performance alone, abrasion resistance is improved. It is possible to obtain a cured film that exhibits antistatic properties without lowering.

The present invention will be described in more detail below. Component (a): The component (a) is a polyfunctional acrylate containing 35 to 100% by weight of a carboxyl group-containing polyfunctional acrylate. The carboxyl group-containing polyfunctional acrylate is a compound having one or more acid anhydride groups in the molecule,
It can be obtained by reacting a hydroxyl group-containing polyfunctional acrylate having a hydroxyl group and three or more acryloyl groups in the molecule.

Specific examples of the compound having one or more acid anhydride groups in the molecule include succinic anhydride, 1-dodecenylsuccinic anhydride, maleic anhydride, glutaric anhydride, itaconic anhydride, phthalic anhydride and hexahydro. Phthalic anhydride, methylhexahydrophthalic anhydride, tetramethylene maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride, methylendomethylenetetrahydrophthalic anhydride, tetrachlorophthalic anhydride, anhydrous Compounds having one acid anhydride group such as tetrabromophthalic acid, chlorendic anhydride, trimellitic anhydride, and pyromellitic dianhydride, 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride, 4,4'-Biphthalic anhydride, 4,4'-oxo Phthalic anhydride, 4,4'-
(Hexafluoroisopropylidene) diphthalic anhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 5- (2,5-dioxotetrahydrofuryl) -3-methyl-3-cyclohexene-1 , 2-Dicarboxylic acid anhydride, 4- (2,5-dioxotetrahydrofuran-3-yl) -tetralin-1,2-dicarboxylic acid anhydride, 3,4,9,10-perylenetetracarboxylic acid dianhydride A compound having two acid anhydride groups such as bicyclo [2.2.2] oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, and a mixture of two or more thereof. To be

Of these, when a compound having two acid anhydride groups is used, the resulting carboxyl group-containing polyfunctional acrylate has an acryloyl group of 3 to 1 in the same molecule.
It will contain 0 and 2-3 carboxyl groups,
It is particularly desirable in terms of wear resistance and adhesion. Next, specific examples of the hydroxyl group-containing polyfunctional acrylate having a hydroxyl group and three or more acryloyl groups in the molecule include pentaerythritol triacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, and mixtures thereof. Can be mentioned.

The reaction of a compound having one or more acid anhydride groups in the molecule with a hydroxyl group-containing polyfunctional acrylate having a hydroxyl group and three or more acryloyl groups in the molecule is carried out by a hydroxyl group-containing polyfunctional acrylate / anhydride. The compound having a group is mixed at a molar ratio of 1 or more and mixed at 60 to 110 ° C. to 1
It is performed by stirring for 20 hours.

In order to prevent polymerization due to the acryloyl group during the reaction, it is desirable to use a polymerization inhibitor such as hydroquinone, hydroquinone monomethyl ether, catechol, pt-butylcatechol, phenothiazine, etc. , 0.01 for the reaction mixture
˜1 wt%, preferably 0.05 to 0.5 wt%.

In order to accelerate the reaction, for example, N, N
-A catalyst such as dimethylbenzylamine, triethylamine, tributylamine, triethylenediamine, benzyltrimethylammonium chloride, benzyltriethylammonium bromide, tetramethylammonium bromide, cetyltrimethylammonium bromide or zinc oxide can be used. The amount used is 0.01 to 5% by weight with respect to the reaction mixture, preferably 0.1.
It is from 05 to 2% by weight.

When carrying out these reactions, an organic solvent having no active hydrogen can be used. Specifically, toluene, aromatic hydrocarbons such as xylene, esters such as ethyl acetate, propyl acetate, butyl acetate, acetone, methyl ethyl ketone, methyl isobutyl ketone,
Examples include ketones such as cyclohexanone, and mixtures of two or more thereof.

The component (a) may contain, in addition to the carboxyl group-containing polyfunctional acrylate, 65% by weight or less of a carboxyl group-free polyfunctional acrylate. In particular, it is preferable to use them together.

The polyfunctional acrylate having no carboxyl group is a polyfunctional acrylate having three or more acryloyl groups from the viewpoint of abrasion resistance. Specifically, trimethylolpropane triacrylate, ethylene oxide-modified trimethylolpropane triacrylate, propylene oxide-modified trimethylolpropane triacrylate, tris (acryloxyethyl) isocyanurate, caprolactone-modified tris (acryloxyethyl).
Isocyanurate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, alkyl modified dipentaerythritol triacrylate, alkyl modified dipentaerythritol tetraacrylate, alkyl modified diacrylate Examples include pentaerythritol pentaacrylate, caprolactone-modified dipentaerythritol hexaacrylate, and a mixture of two or more thereof.

The component (a) is prepared, for example, by using a commercially available mixture of pentaerythritol triacrylate and pentaerythritol tetraacrylate, or a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate, and an acid anhydride. It can also be prepared by reacting. Of course, the carboxyl group-containing polyfunctional acrylate may be mixed with a carboxyl group-free polyfunctional acrylate.

(B) Silicate compound General formula (I) of the raw material of the silicate compound of the component (b)

[0021]

Embedded image

[In the formula, n is an integer of 2 to 7. The polymethoxysiloxane having a degree of polymerization of 3 to 8 is obtained by using tetramethylsiloxane with an acid and a methoxy group (OCH).
_It is obtained by partially hydrolyzing 40 to 70%, preferably 50% of ₃ ). The silicate compound as the component (b) is polycondensed and transesterified by blending the polymethoxysiloxane represented by the general formula (I) with alcohol, water and a hydrolysis catalyst and aging at room temperature for 1 to 7 days. Occurs, and the silicate compound of the component (b) is obtained. The degree of polymerization of this silicate compound is 6 to 24.
It is about 6 to 16, preferably about 6 to 16.

In carrying out this hydrolysis, in addition to alcohol, for example, aromatic hydrocarbons such as toluene and xylene, esters such as ethyl acetate, propyl acetate and butyl acetate, acetone, methyl ethyl ketone, methyl isobutyl ketone, An organic solvent such as ketones such as cyclohexanone may be added. Specific examples of the alcohol include aliphatic alcohols having 1 to 8 carbon atoms, specifically, methyl alcohol, ethyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, octyl alcohol, and mixtures thereof. Can be mentioned. The amount of alcohol used is 50 to 400 parts by weight, preferably 100 to 250 parts by weight, based on 100 parts by weight of polymethoxysiloxane.

The amount of water added may be such that the polymethoxysiloxane can theoretically hydrolyze 100% or more,
100-300% equivalent amount, preferably 100-200%
Add a considerable amount. As the hydrolysis catalyst, for example, acetylacetone aluminum, boric acid butoxide, acetic acid, hydrochloric acid, maleic acid, oxalic acid, fumaric acid, dibutyltin dilaurate, dibutyltin dioctate, P-toluenesulfonic acid and mixtures thereof can be used. it can. The amount used is polymethoxysiloxane 10
0.1 to 10 parts by weight, preferably 0.
5 to 5 parts by weight.

Polymethoxysiloxane as a raw material of the silicate compound as the component (b) is available from, for example, Mitsubishi Chemical Corporation under the trade name of "MKC silicate MS51". Further, the silicate compound of the component (b) has the formula (I)
Polymethoxysiloxane represented by, alcohol, water,
It can also be obtained by adding silica sol (d) to a hydrolysis catalyst and hydrolyzing it. Examples of the silica sol include water, methyl alcohol, isopropyl alcohol,
n-butyl alcohol, isobutyl alcohol, ethylene glycol, ethyl cellosolve, dimethylacetamide, xylene and a mixed solvent thereof are used as a dispersion medium, and the silica has a particle size of 5 to 30 nm and a solid content of 10 to 40% by weight. Can be mentioned. Among these dispersion media,
Silica sol using methyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, and a mixed solvent thereof is preferable from the viewpoint of stability of the silicate composition.

Silica sol (d) is used in a proportion of 0.1 to 100% by weight of polymethoxysiloxane in solid-formation. With respect to 100 parts by weight of the polyfunctional acrylate of the component (a), the silicate compound of the component (b) is 20 to 500 parts by weight, preferably 3 parts by weight in terms of the solid content of the silicate compound.
It is used in a proportion of 5 to 250 parts by weight. When the amount of the silicate compound (b) is less than 20 parts by weight, the antistatic performance of the obtained cured film is low and it is not practical. When it exceeds 500 parts by weight, the crosslink density due to the acryloyl group of the component (a) decreases, so that the wear resistance of the obtained cured film decreases.

Photopolymerization Initiator (c) Examples of the photopolymerization initiator (c) include benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin butyl ether, diethoxyacetophenone, benzyl dimethyl ketal and 2-hydroxy-2-methyl. Propiophenone, 1-hydroxycyclohexyl phenyl ketone, benzophenone, 2,
4,6-Trimethylbenzoindiphenylphosphine oxide, 2-methyl- [4- (methylthio) phenyl] -2-morpholino-1-propanone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl)- Butan-1-one, Michler's ketone, N, N
Examples include isoamyl dimethylaminobenzoate, 2-chlorothioxanthone, and 2,4-diethylthioxanthone. These photopolymerization initiators may be used in combination of two or more kinds as appropriate. The photopolymerization initiator is 0.1 to 3 parts by weight with respect to 100 parts by weight of the polyfunctional acrylate of the component (a),
It is preferably used in a proportion of 0.5 to 2 parts by weight.

[0028] The silica sol (d) silica sol (d), as was described above silica (SiO ₂₎
With a particle size of 5 to 30 nm, and is mixed for the purpose of improving the transparency and scratch resistance of the cured film obtained. Silica sol (d) is 0.1 to 100 parts by weight in terms of SiO ₂ solid content based on 100 parts by weight of the polyfunctional acrylate of component (a),
It is preferably used in a proportion of 20 to 60 parts by weight.

Preparation of coating composition The coating composition of the present invention is prepared by mixing the above-mentioned components (a), (b) and (c), and optionally (d). Usually, (a) component and (b)
The organic solvent described above is used in the production of the components. The organic solvent is 0.1 to 1000 parts by weight, based on 100 parts by weight of the total solid content of the components (a) and (b),
It is preferably used in a proportion of 30 to 300 parts by weight. This organic solvent preferably has a boiling point of 50 to 160 ° C. from the viewpoint of the drying property of the coating composition.

The active energy ray-curable coating composition of the present invention contains an ultraviolet absorber (for example, a benzotriazole type, a benzophenone type, a salicylic acid type, a cyanoacrylate type ultraviolet absorber), an ultraviolet ray for the purpose of improving the physical properties of the coating film. Stabilizers (eg hindered amine UV stabilizers),
Various additives such as antioxidants (for example, phenol-based, sulfur-based, phosphorus-based antioxidants), anti-blocking agents, slip agents, leveling agents and the like which are compounded in this type of composition can be added.

Cured film Examples of the substrate to which the coating composition of the present invention can be applied include polycarbonate, polymethylmethacrylate, polyethylene terephthalate, polybutylene terephthalate, nylon 6, nylon 66, vinyl chloride resin, AB.
Examples include S resins, plastics such as cellulose acetate, metals such as iron, stainless steel and aluminum, wood, cement and the like. Among these, it is preferable to apply the coating composition of the present invention to a plastic substrate which is particularly required to have abrasion resistance and antistatic properties.

The coating composition of the present invention is applied to a substrate by a dipping method, a flow coating method, a spraying method, a bar coating method, and a coating machine such as a gravure coating, a roll coating, a blade coating and an air knife coating. 0.1 to 50 μm, preferably 1 to 10 μm on the surface of the plastic substrate after drying the solvent and irradiating with active energy rays by the working method.
It can be applied under the condition that the hard coat layer can be obtained.

As a means for cross-linking and hardening the hard coat layer applied on the substrate to obtain a film, it is possible to emit from a light source such as a xenon lamp, a low pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a metal halide lamp, a carbon arc lamp or a tungsten lamp. Ultraviolet rays or usually 20-2000
An electron beam extracted from the keV electron beam accelerator, an α-ray,
Active energy rays such as β rays and γ rays can be used. The thickness of the film is 0.1 to 50 μm, preferably 1 to
10 μm and surface resistivity of 1 × 10 ¹⁰ to 1 × 10
¹² Ω / cm, abrasion resistance ΔH% is 5% or less, and transparency (cloudiness value) is 5% or less.

[0034]

EXAMPLES The present invention will be described in more detail with reference to synthesis examples and examples. The parts and% in the examples mean parts by weight and% by weight, respectively. Production of polyfunctional acrylate:

Synthesis Example 1 A mixture of 67 mol% of dipentaerythritol pentaacrylate and 33 mol% of dipentaerythritol hexaacrylate ["Kayarad DPHA" manufactured by Nippon Kayaku Co., Ltd.].
(Trade name), hydroxyl value of 69 mgKOH / g], and pyromellitic dianhydride, 163 parts of mixture and pyromellitic dianhydride 21 such that the molar ratio of dipentaerythritol pentaacrylate / pyromellitic dianhydride is 2. 8 parts in a flask, 100 parts of methyl ethyl ketone, 0.1 part of hydroquinone monomethyl ether and N, N
-1 part of dimethylbenzylamine was added and reacted at 80 ° C for 8 hours. The obtained mixture (I) of carboxyl group-containing polyfunctional acrylate and dipentaerythritol hexaacrylate had a solid content of 65.0%, and the carboxyl group-containing polyfunctional acrylate and dipentaerythritol hexaacrylate were 44.3% and 20. It contained 4%.

Synthesis Example 2 A mixture of 73 mol% of pentaerythritol triacrylate and 27 mol% of pentaerythritol tetraacrylate [“Viscoat 300” manufactured by Osaka Organic Chemical Industry Co., Ltd.]
(Trade name), hydroxyl value 131 mgKOH / g] and pyromellitic dianhydride 86 parts of mixture and pyromellitic dianhydride 21. so that the molar ratio of pentaerythritol triacrylate / pyromellitic dianhydride is 2. 8 parts were put in a flask, 100 parts of methyl ethyl ketone, 0.1 part of hydroquinone monomethyl ether and 1 part of N, N-dimethylbenzylamine were added, and the mixture was reacted at 80 ° C. for 8 hours. The resulting mixture (II) has a solid content of 52.1%.
The content of the carboxyl group-containing polyfunctional acrylate and that of pentaerythritol tetraacrylate were 39.0% and 12.6%, respectively.

Synthesis Example 3 A mixture of 67 mol% of dipentaerythritol pentaacrylate and 33 mol% of dipentaerythritol hexaacrylate (“Kayarad DPH manufactured by Nippon Kayaku Co., Ltd.”).
A ″, a hydroxyl value of 69 mgKOH / g] and trimellitic anhydride, and 163 parts of the mixture and 38.4 parts of trimellitic anhydride were added to a flask so that the molar ratio of dipentaerythritol pentaacrylate / trimellitic anhydride was 1. 100 parts of methyl ethyl ketone, 0.1 part of hydroquinone monomethyl ether and 1 part of N, N-dimethylbenzylamine were added, and the mixture was reacted at 80 ° C. for 8 hours.
The mixture (III) thus obtained had a solid content of 66.9% and contained 47.3% and 1% of a carboxyl group-containing polyfunctional acrylate and dipentaerythritol hexaacrylate, respectively.
It contained 9.2%.

Production of Silicate Compound (b): Synthesis Example 4 Formula (II)

[0039]

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Polymethoxysiloxane [MKC silicate MS51 (trade name) manufactured by Mitsubishi Chemical Corporation] 1
To 200 parts of ethyl alcohol, 200 parts of ethyl alcohol, 1 part of acetylacetone aluminum and 22 parts of water were added, and the mixture was stirred at room temperature for 1 hour and then left to stand for 2 days for aging to obtain a solid content of 22.
0% of the silicate composition (b ₁ ) was obtained. The solid content was determined by placing 1 g of the silicate composition in an aluminum dish and drying at 100 ° C. for 5 minutes, and then measuring the solid content. (Note that the amount of water added was 117% with respect to the amount by which 100% of the theoretical amount of polymethoxysiloxane could be hydrolyzed.)

Synthesis Example 5 A silicate composition (b ₂ ) having a solid content of 21.8% was obtained in the same manner as in Synthesis Example 4 except that maleic acid was used instead of acetylacetone aluminum.

Synthesis Example 6 To 100 parts of polymethoxysiloxane (MKC silicate MS51 manufactured by Mitsubishi Chemical Corporation), 20 parts of ethyl alcohol were added.
Solid content of 0 parts, 1 part of acetylacetone aluminum, 22 parts of water and isopropyl alcohol as a dispersion medium
% Colloidal silica (manufactured by Nissan Chemical Industries: IPA-S
T) (170 parts) was added, the mixture was stirred at room temperature for 1 hour, and then left standing for 2 days for aging to obtain a silicate composition (b) having a solid content of 26.0%.
₃ ) Got it.

Synthesis Example 7 100 parts of polyethoxysiloxane [silicate 45 (trade name) manufactured by Tama Chemical Industry Co., Ltd.] and 20 parts of ethyl alcohol
0 part, 1 part of acetylacetone aluminum and 17 parts of water were added, and the mixture was stirred at room temperature for 1 hour and left for 2 days for aging to obtain a polyethoxysilane condensation polymer having a solid content of 19.5%.

Synthesis Example 8 To 156 parts of tetraethoxysilane, 150 parts of colloidal silica (IPA-ST manufactured by Nissan Chemical Industries, Ltd.) having a solid content of 30% as a dispersion medium, and 5 parts of water.
4 parts and 0.5 part of 36% hydrochloric acid were added, and the mixture was heated at 80 ° C. for 1 hour with stirring to obtain a tetraethoxysilane condensation polymer having a solid content of 29.7%.

Example 1 100 parts of the mixture (I) obtained in Synthesis Example 1 and the silicate composition (b ₁ ) obtained in Synthesis Example 4 and having a solid content of 22.0%.
401.9 parts and 1 part of benzyl dimethyl ketal were mixed to prepare an active energy ray-curable coating composition (A) having the composition shown in Table 2.

This active energy ray-curable coating composition (A) was applied to a transparent polyethylene terephthalate film having a thickness of 0.1 mm by using a bar coater, and 60
It was heated and dried at 0 ° C. for 2 minutes to volatilize methyl ethyl ketone and ethyl alcohol to obtain a film having a thickness of 3 μm. Output of this product installed vertically to the sample passage direction 7.5k
w, using a high-pressure mercury lamp with an output density of 120 w / cm, and irradiating ultraviolet rays at a position of 10 cm under the light source at a conveyor speed of 2 m / min to perform ultraviolet curing to obtain a hard coat film.

The adhesiveness between the hardened hard coat layer formed on the polyethylene terephthalate film and the polyethylene terephthalate film is determined by making 100 squares in the hard coat layer with a cutter knife at intervals of 1 mm to make Nichiban adhesive tape "Cellotape". When the (trade name) was pressure-bonded and strongly peeled off and evaluated, the cross-section of the film remaining on the film was 100 and good adhesion was obtained (cross-cut tape method JISK5400).

The transparency of the obtained polyethylene terephthalate film having a hard coat layer was evaluated by the haze value (%), and it was 4.1%, and the transparency was good. 0.1mm before applying the hard coat agent
The haze value of the thick polyethylene terephthalate film was 3.7%. (Cloudy value = Td / Tt × 100,
Td: scattered light transmittance, Tt: total light transmittance JIS
K7105).

The wear resistance is CS from Calibrase
Using a theory of wear of -10F, a 100-rotation Taber abrasion test was performed under a load of 500 g, and the difference ΔH between the haze value after the Taber abrasion test and the haze value before the Taber abrasion test was measured and found to be 2.4%. The sex was good. In addition,
A 0.1 mm thick polyethylene terephthalate film not subjected to the hard coat treatment was subjected to the same Taber abrasion test to obtain ΔH of 23.1% (Taber abrasion test method ASTM D1044). Next, the antistatic property was 5.6 × 10 ¹⁰ when the surface resistivity was measured after being left in a thermostatic chamber at 23 ° C. and 60% relative humidity for 1 week.
Ω / cm, and the antistatic property was good.

Examples 2 to 10 Active energy ray-curable coating compositions (A) to (E)
Are the mixture (I) obtained in Synthesis Example 1 and Synthesis Examples 4 to 6
The resulting silicate composition with _{(b 1) ~ (b 3} ), and was prepared by blending benzyl dimethyl ketal. The coating compositions (F) and (G) were the mixture (II) obtained in Synthesis Example 2, the silicate compositions (b ₁ ) and (b ₃ ) obtained in Synthesis Examples 4 and 6, and benzyl. It was prepared by blending dimethyl ketal. The coating compositions (H) and (J) are the composition (III) obtained in Synthesis Example 3 and the silicate composition (b ₁ ) obtained in Synthesis Examples 4 and 6.
(B ₃ ) and benzyl dimethyl ketal were mixed and prepared. The composition of each coating composition is shown in Table 1.

Using the obtained active energy ray-curable coating compositions B to J, a polycarbonate plate having a hard code layer and a polyethylene terephthalate film were obtained in the same manner as in Example 1. The 2 mm thick polycarbonate plate used as the substrate in Example 2 had a haze value of 0.4% and an abrasion resistance (ΔH) of 46.7%. When a polycarbonate plate having a hardened hard coat layer and a polyethylene terephthalate film were evaluated, good results were obtained in terms of adhesion, transparency, abrasion resistance and surface resistivity. Table 2 shows the evaluation results.

Comparative Examples 1-5 An active energy ray-curable coating composition (K) prepared by blending the mixture (I) obtained in Synthesis Example 1 with benzyl dimethyl ketal, and Synthesis Example 7 for this composition. The polyethoxysiloxane polycondensation product obtained in 1., the tetraethoxysilane polycondensation product obtained in Synthesis Example 8, and a silica sol having a solid content of 30% using isopropyl alcohol as a dispersion medium (manufactured by Nissan Chemical Industries: IPA-ST) Active energy ray-curable coating compositions (L), (M), respectively added and prepared.
(N), and a mixture of 67 mol% of dipentaerythritol pentaacrylate and 33 mol% of dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd .: Kayarad DPHA, hydroxyl value 69 mgKOH / g) and obtained in Synthesis Example 4. An active energy ray-curable coating composition (O) obtained by blending the silicate composition (b ₁ ) and benzyl dimethyl ketal was prepared.

Table 3 shows the composition of each coating composition.
Using these compositions, a polyethylene terephthalate film having a hard coat layer cured in the same manner as in Example 1 was produced. Among them, the active energy ray-curable coating composition (L) remains sticky even after UV curing,
The hard coat layer could not be obtained. Other polyethylene terephthalate films having hard coat layers were evaluated, but their antistatic properties were insufficient. Table 4 shows the evaluation results.

Comparative Example 6 Using the silicate composition (b ₁ ) obtained in Synthesis Example 4,
Application and drying were carried out in the same manner as in Example 1 to produce a polyethylene terephthalate film having a silicate layer. Since this composition is not UV curable, UV irradiation was not performed. The polyethylene terephthalate film obtained was evaluated, but no antistatic property was observed and the abrasion resistance was insufficient. Table 4 shows the evaluation results.

[0055]

[Table 1]

[0056]

[Table 2]

[0057]

[Table 3]

[0058]

[Table 4]

[0059]

EFFECTS OF THE INVENTION A cured film having excellent antistatic properties, transparency and abrasion resistance can be obtained.

Claims (5)

[Claims] 1. Polycondensation and transesterification of (a) a polyfunctional acrylate containing 35 to 100% by weight of a carboxyl group-containing polyfunctional acrylate and (b) a polymethoxysiloxane having a degree of polymerization of 3 to 8 in water and alcohol. A coating composition containing the silicate compound obtained by the reaction and (c) a photopolymerization initiator, wherein the amount of the silicate compound as the component (b) is 100 parts by weight of the polyfunctional acrylate as the component (a). 20 to 500 parts by weight,
Component (c) is 0.1% of the polyfunctional acrylate of component (a).
The coating composition is blended in a proportion of 3 wt%. 2. A polyfunctional acrylate containing (a) a polyfunctional acrylate containing a carboxyl group in an amount of 35 to 100% by weight, and (b) a polymethoxysiloxane having a degree of polymerization of 3 to 8 in the presence of water and an alcohol. A coating composition containing a silicate compound obtained by a transesterification reaction, (c) a photopolymerization initiator, and (d) a silica sol,
The compounding amount of the silicate compound of the component (b) is 20 to 49 relative to 100 parts by weight of the polyfunctional acrylate of the component (a).
9.9 parts by weight, the component (c) is 0.1 to 3% by weight of the polyfunctional acrylate of the component (a), and the silica sol of the component (d) is 100 parts of the polyfunctional acrylate of the component (a).
The coating composition is blended in a proportion of 0.1 to 100 parts by weight with respect to parts by weight (however, the sum of the components (b) and (d) is 100 parts by weight of the component (a)). Against 5
00 parts by weight or less). 3. When obtaining the silicate compound of the component (b), polycondensation and transesterification reaction of polymethoxysiloxane in water and alcohol in the presence of the silica sol of the component (d) are carried out to prepare the silicate compound. The coating composition according to claim 2, which is characterized. 4. A compound in which the carboxyl group-containing polyfunctional acrylate in the component (a) has at least one acid anhydride group in the molecule, and at least one hydroxyl group and at least three acryloyl groups in the molecule. It is obtained by reacting with a hydroxyl group-containing polyfunctional acrylate having
Or the coating composition according to 2. 5. The compound having an acid anhydride group is selected from pyromellitic dianhydride and trimellitic acid anhydride, and the hydroxyl group-containing polyfunctional acrylate is pentaerythritol triacrylate, dipentaerythritol pentaacrylate, The coating composition according to claim 4, which is selected from the following.