JPH07286116A - Abrasion resistant coating composition - Google Patents

Abstract

(57) [Summary] [Purpose] A coating film is formed when the solvent is dried, and can be processed such as molding, printing, and transfer before irradiation with active energy rays. It forms a coating film with excellent abrasion resistance. An active energy ray-curable coating composition is provided. [Structure] (a) a tetracarboxylic dianhydride and a hydroxyl group-containing polyfunctional acrylate having a hydroxyl group and three or more acryloyl groups in the molecule, wherein the ratio of acid anhydride group / hydroxyl group is 1.2 to 2. And a polyfunctional acrylate containing a carboxyl group obtained by reacting with epoxy acrylate, (b) a polyfunctional acrylate having three or more acryloyl groups in the molecule, (c) an organic solvent, and optionally (d). ) A composition comprising a photopolymerization initiator. Furthermore, the composition which added (e) colloidal metal oxide to the said component.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to an active energy ray-curable resist which forms a coating film which is cured by irradiation with an active energy ray and has excellent adhesion to a plastic substrate, transparency and abrasion resistance. It relates to an abradable coating composition. More specifically, the present invention forms a coating film at the time of drying the solvent, enables processing such as molding, printing, and transfer before irradiation with active energy rays, and has excellent abrasion resistance after irradiation with active energy rays. The present invention relates to an active energy ray curable abrasion resistant coating composition which forms a coating film.

[0002]

BACKGROUND OF THE INVENTION Generally, plastic products,
For example, polycarbonate, polymethylmethacrylate, polyethylene terephthalate, vinyl chloride resin, A
BS resins, cellulose acetate and the like are used in various applications because of their excellent lightness, easy processability and impact resistance. However, since these plastic products have low surface hardness, the surface is likely to be scratched, which makes it difficult to use the plastic products in fields requiring abrasion resistance. Therefore, an active energy ray-curable hard coat material that imparts abrasion resistance to these plastic products is required. Furthermore, when a hard coat treatment is applied to the surface of these plastic products, the hard coat agent is not directly applied to the surface of the plastic product because printing or molding is performed before curing with active energy rays. Apply to other substrates, print if necessary,
After processing such as coating the adhesive layer, the hard coat layer is transferred to the surface of plastic products, so a coating film can be formed when the solvent is dried, and active energy ray curing with excellent abrasion resistance Resin is required.

As the active energy ray-curable hard coating agent, a hard coating agent using a polyfunctional (meth) acrylate having three or more functional groups is disclosed in JP-B-53-43553 and JP-B-57-20968. . Further, in order to improve the wear resistance of these hard coat agents, it is recommended to add a fine powdery inorganic filler or colloidal silica in JP-A-59-41366 and JP-A-63-63.
It is disclosed in Japanese Patent No. 92675. These active energy ray-curable hard coating agents have excellent abrasion resistance,
Since not only solvent-free systems but also those containing solvents do not have film-forming properties when the solvent is dried, processing such as molding, printing and transfer could not be performed before irradiation with active energy rays. . In order to impart a film forming property to these hard coating agents, it is conceivable to add a thermoplastic resin such as a (meth) acrylic acid ester copolymer, which dissolves in the hard coating agent, but it is sufficient. Simply adding an amount sufficient to impart film-forming properties would significantly reduce the abrasion resistance originally required as a hard coating agent, and both film-forming properties and abrasion resistance were excellent. The hard coat agent has not been obtained yet.

[0004]

As a result of earnest studies, the present inventors were able to solve the above-mentioned conventional problems. That is, the present invention provides (a) a tetracarboxylic dianhydride and a hydroxyl group-containing polyfunctional acrylate having a hydroxyl group and three or more acryloyl groups in the molecule, and an acid anhydride group / hydroxyl group ratio of 1.2 to After reacting at a ratio of 2, a carboxyl group-containing polyfunctional acrylate obtained by reacting with an epoxy acrylate, (b) a polyfunctional acrylate having three or more acryloyl groups in the molecule, (c) an organic solvent, and optionally Accordingly, the present invention provides an active energy ray-curable abrasion-resistant coating composition comprising (d) a photopolymerization initiator. Furthermore, the present invention provides an active energy ray-curable abrasion-resistant coating composition, characterized in that it further comprises (e) a colloidal metal oxide in addition to the components of the above composition. is there. These compositions form a coating film when the solvent is dried,
Processing such as molding, printing, and transfer are possible, and a coating film having excellent abrasion resistance can be formed after irradiation with active energy rays.

The present invention will be described in more detail below. Component (a) : Component (a) is tetracarboxylic dianhydride,
Carboxyl obtained by reacting a hydroxyl group-containing polyfunctional acrylate having a hydroxyl group and three or more acryloyl groups in the molecule with an acid anhydride group / hydroxyl group ratio of 1.2 to 2 and then reacting with an epoxy acrylate. It is a group-containing polyfunctional acrylate. When tetracarboxylic dianhydride and a hydroxyl group-containing polyfunctional acrylate having a hydroxyl group and three or more acryloyl groups in the molecule are reacted at an acid anhydride group / hydroxyl group ratio of 1.2 to 2, unreacted A carboxyl group-containing polyfunctional acrylate having an acid anhydride group is obtained. Then, the unreacted acid anhydride group reacts with the hydroxyl group of the epoxy acrylate to obtain a carboxyl group-containing polyfunctional acrylate which is the component (a). Specific examples of the tetracarboxylic dianhydride include pyromellitic dianhydride, 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride, 4.4′-biphthalic anhydride,
4,4'-oxodiphthalic anhydride, 4,4 '-(hexafluoroisopropylidene) diphthalic anhydride, 1,
2,3,4-Cyclopentanetetracarboxylic dianhydride, 5- (2,3-dioxotetrahydrofuryl) -3
-Methyl-3-cyclohexene-1,2-dicarboxylic acid anhydride, 4- (2,5-dioxotetrahydrofuran-
3-yl) -tetralin-1,2-dicarboxylic anhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, bicyclo [2.2.2] oct-7-ene-2,
3,5,6-tetracarboxylic dianhydride, and mixtures of two or more thereof. 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 tetracarboxylic dianhydride and a hydroxyl group-containing polyfunctional acrylate having a hydroxyl group and three or more acryloyl groups in the molecule is mixed at a ratio of acid anhydride group / hydroxyl group of 1.2 to 2, It is carried out by stirring at 60 to 110 ° C. for 1 to 20 hours. This reaction is a polyfunctional acrylate having 3 or more acryloyl groups in the molecule of the component (b),
It can be carried out in the presence of an organic solvent having no active hydrogen among the organic solvents of the component (c). In order to prevent polymerization due to an acryloyl group during the reaction, for example, hydroquinone, hydroquinone monomethyl ether, catechol,
It is desirable to use a polymerization inhibitor such as p-t-butylcatechol and phenothiazine, and the amount thereof is 0.01 to 1% by weight, preferably 0.05 to 5% by weight, based on the reaction mixture.
It is 0.5% by weight. In order to promote these reactions, for example, N, N-dimethylbenzylamine, triethylamine, tributylamine, triethylenediamine, benzyltrimethylammonium chloride, benzyltriethylammonium bromide, tetramethylammonium bromide, cetyltrimethylammonium bromide, oxidation A catalyst such as zinc can be used. The amount used is 0.01-5 with respect to the reaction mixture.
%, Preferably 0.05 to 2% by weight. The obtained carboxyl group-containing polyfunctional acrylate having an unreacted acid anhydride group is then reacted with an epoxy acrylate. The epoxy acrylate used here is
It is obtained by mixing an epoxy resin and acrylic acid at a ratio of epoxy group / carboxyl group = 1 and reacting at 90 to 120 ° C. for 5 to 20 hours. Specific examples of the epoxy resin include bisphenol type diglycidyl ether, bisphenol F type diglycidyl ether, bisphenol S type diglycidyl ether, bisphenol type epoxy resin such as hexahydrobisphenol A type diglycidyl ether, phenol novolac type epoxy resin, Orthocresol novolac type epoxy resins and other novolac type epoxy resins, triglycidyl-p-aminophenol, triglycidyl isocyanurate, tetraglycidyl metaxylene diamine, tetraglycidyl diaminodiphenylmethane, tetraglycidyl-1,3-bisaminomethylcyclohexane and the like. Polyfunctional glycidyl amine type epoxy resin, tetraphenyl glycidyl ether ethane, triphenyl glycidyl ether methane, ,
4'-bis (2,3-epoxypropoxy) -3,
Examples thereof include polyfunctional glycidyl ether type epoxy resins such as 3 ′, 5,5′-tetramethylbiphenyl, brominated bisphenol A type epoxy resins, and brominated epoxy resins such as brominated phenol novolac type epoxy resins. Among these, medium molecular weight bisphenol A diglycidyl ether, bisphenol S diglycidyl ether, orthocresol novolac type epoxy resin, triglycidyl isocyanurate, tetraglycidyl diaminodiphenylmethane, tetraphenylglycidyl ether ethane, triphenylglycidyl ether methane, 4,4'-bis (2,3-epoxypropoxy)
Solid epoxy resins such as -3,3 ', 5,5'-tetramethylbiphenyl and brominated bisphenol A type epoxy resins are particularly preferable from the viewpoint of film-forming properties of the final product, a carboxyl group-containing polyfunctional acrylate. desirable. The reaction between the carboxyl group-containing polyfunctional acrylate having an unreacted acid anhydride group and the epoxy acrylate is performed by mixing at a ratio of acid anhydride group / hydroxyl group of 1 or less, and 60 to 110.
It is carried out by stirring at 1 ° C. for 1 to 10 hours. Also in this reaction, a polyfunctional acrylate having three or more acryloyl groups in the molecule of the component (b), an organic solvent having no active hydrogen among the organic solvents of the component (c), the above-mentioned polymerization inhibitor,
It can be carried out in the presence of a catalyst. Since the obtained carboxyl group-containing polyfunctional acrylate has no solvent and has a film-forming property and contains 5 or more acryloyl groups in the same molecule, even if mixed with the polyfunctional acrylate of component (b). A hard coat agent having excellent abrasion resistance can be obtained without decreasing the acryloyl group density.

Component (b) : The component (b) is a polyfunctional acrylate having three or more acryloyl groups in the molecule, specifically, trimethylolpropane triacrylate, EO-modified trimethylolpropane triacrylate, PO-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 diacrylate Examples thereof include pentaerythritol tetraacrylate, alkyl-modified dipentaerythritol pentaacrylate, caprolactone-modified dipentaerythritol hexaacrylate, and a mixture of two or more thereof. Among these, dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate, and mixtures thereof are particularly desirable from the viewpoint of abrasion resistance. The weight ratio of component (b) / component (a) is 1 or less, preferably 0.01 to 1,
It is more preferably 0.1 to 1. If it is less than 0.01, it is not practical because it is difficult to obtain the raw material of the component (a). On the other hand, if it exceeds 1, sufficient film formability cannot be obtained.

Component (c) : As an organic solvent, aromatic hydrocarbons such as triene and xylene, esters such as ethyl acetate, propyl acetate and butyl acetate, methyl alcohol, ethyl alcohol, n-propyl alcohol, is
Alcohols such as o-propyl alcohol and n-butyl alcohol, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone, 2-
Ethers such as methoxyethanol, 2-ethoxyethanol, 2-butoxyethanol, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, 2-methoxyethyl acetate, 2-ethoxyethyl acetate, 2-butoxyethyl acetate, etc. And the like, and these can be used as a mixture. These organic solvents are used for the purpose of adjusting the viscosity of the present active energy ray-curable coating composition, and among these organic solvents, the organic solvent having no active hydrogen is also used as a solvent for producing the component (a). To be

Component (d) : When ultraviolet rays are used as the active energy rays, a photopolymerization initiator is used in addition to the components (a) to (c). As the photopolymerization initiator, benzoin methyl ether, benzoin ethyl ether,
Benzoin isopropyl ether, benzoin butyl ether, diethoxyacetophenone, benzyl dimethyl ketal, 2-hydroxy-2-methyl propiophenone, 1-hydroxycyclohexyl phenyl ketone, benzophenone, 2,4,6-trimethylbenzoin diphenylphosphine oxide, 2-methyl -[4- (Methylthio) phenyl] -2-morpholino-1-propanone, 2-benzyl-2-dimethylamino-1- (4-
Morpholinophenyl) -butan-1-one, Michler's ketone, isoamyl N, N-dimethylaminobenzoate, 2-chlorothioxanthone, 2,4 diethylthioxanthone, and the like, and two or more of these photopolymerization initiators are appropriately used. Can also be used in combination. The photopolymerization initiator is
The total amount of the components (a) and (b) is 0.1 to 10 parts by weight, preferably 1 to 5 parts by weight, based on 100 parts by weight.

Component (e) : Abrasion resistance is obtained by adding a colloidal metal oxide, which is the component (e), to the active energy ray-curable wear-resistant coating composition comprising the above components (a) to (d). An active energy ray-curable abrasion-resistant coating composition having further improved properties and film forming properties can be obtained. The colloidal metal oxide is preferably a colloidal metal oxide having an average particle size of 1 to 100 nm, particularly 3 to 20 nm, which is obtained by dispersing the metal oxide in an organic solvent or water. From the aspect of compatibility in the system, a colloidal metal oxide dispersed and stabilized in an organic solvent is preferably used. If a colloidal metal oxide having an average particle diameter of less than 1 nm is used, it may not be possible to increase the surface hardness, and if it exceeds 100 nm, the transparency of the coating film may be lost. Specific examples of such colloidal metal oxides include one or more of colloidal silica, colloidal titanium oxide, colloidal antimony oxide, colloidal zinc oxide, colloidal tin oxide, colloidal tungsten oxide and the like. Can be used.
Further, a mixed crystal sol such as antimony oxide / silica sol, titanium oxide / silica sol, cerium oxide / titanium oxide sol, iron oxide / titanium oxide sol, antimony oxide / titanium oxide sol, and tungsten oxide / tin oxide sol can be used. When adding component (e), component (e) /
The weight ratio of {(a) component + (b) component} is 10 or less, preferably 5 or less. If the weight ratio exceeds 10, the crosslink density due to the acryloyl groups of the component (a) and the component (b) will decrease, and the abrasion resistance will decrease, which is not desirable.

The active energy ray-curable abrasion-resistant coating composition of the present invention contains an ultraviolet absorber (eg, benzotriazole-based, benzophenone-based, salicylic acid-based, cyanoacrylate-based ultraviolet absorber for the purpose of improving the physical properties of the coating film. ), UV stabilizers (eg hindered amine UV stabilizers), antioxidants (eg phenolic, sulfur, phosphorus antioxidants), antiblocking agents, slip agents, leveling agents, etc. Various additives to be blended can be blended. In addition, a compound having a (meth) acryloyl group in the side chain of a (meth) acrylic acid ester polymer or copolymer, a (meth) acrylic acid ester polymer or copolymer, as long as the abrasion resistance is not impaired. An acrylic resin such as a (meth) acrylic acid ester copolymer having a polyorganosiloxane unit, an acrylic silicone resin having an alkoxysilyl group, an acrylic silicone resin having an alkoxysilyl group and a polyorganosiloxane unit can be added. .

The coating composition of the present invention is applied to a plastic substrate such as polycarbonate, polymethylmethacrylate, polyethylene terephthalate, vinyl chloride resin, ABS resin, cellulose acetate, etc. by dipping method, flow coating method, spraying method, bar coating method. 1 to 50 on the surface of the plastic substrate after solvent drying and irradiation with active energy rays by a coating method using a coating machine such as a coating method, gravure coating, roll coating, blade coating and air knife coating.
It can be applied under the condition that a hard coat layer having a thickness of μm, preferably 2 to 20 μm can be obtained. After the solvent is dried, processing such as molding, printing, and transfer is performed if necessary. Molding, for example, after heating the base material coated with a hard coating agent to an appropriate temperature, vacuum molding, vacuum pressure molding, pressure molding, matte molding, etc., including the substrate, or
Examples include molding of only the hard coat layer such as emboss molding on a hard coat agent such as duplication of a CD or record having uneven shapes such as interference fringes. Printing is carried out on the dried hard coat agent using an ordinary printing machine. For the transfer, for example, after applying the hard coating agent of the present invention to a substrate such as a polyethylene terephthalate film and drying, the above-mentioned printing or embossing molding is performed if necessary,
After applying the adhesive layer, it is transferred to another substrate. Then, in order to crosslink and cure the applied hard coat layer, ultraviolet rays emitted from a light source such as a xenon lamp, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high pressure mercury lamp, a metal halide lamp, a carbon arc lamp, or a tungsten lamp, or 2
An active energy ray such as an electron ray, α ray, β ray, γ ray extracted from an electron beam accelerator of 0 to 2000 kV can be used.

[0012]

EXAMPLES The present invention will be described in more detail with reference to examples below, but the present invention is not limited to these examples. The parts and% in the examples mean parts by weight and% by weight, respectively. Example 1 Ortho-cresol novolac type epoxy resin (Eika Shell Epoxy Co .: E180S75, epoxy equivalent 215)
g / eq.) 215 parts with methyl isobutyl ketone 123
After dissolving in 100 parts by weight, 72 parts of acrylic acid, 0.2 parts of hydroquinone monomethyl ether and 1 part of N, N-dimethylbenzylamine were added, and the mixture was reacted at 110 ° C. for 8 hours. The acid value of the obtained epoxy acrylate (EA1) is 3.1.
It was mgKOH / g. 67 mol% of pyromellitic dianhydride and dipentaerythritol pentaacrylate
Mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate contained (manufactured by Nippon Kayaku Co., Ltd .: Kayarad DPHA, hydroxyl value 69
mgKOH / g), 21.8 parts and 90.3 parts of acid anhydride group / hydroxyl group = 1.8, respectively, were placed in a flask, and 50 parts of methyl ethyl ketone, 0.05 part of hydroquinone monomethyl ether and N, N were added. -Dimethylbenzylamine (0.5 part) was added, and the mixture was reacted at 80 ° C for 8 hours to obtain a carboxyl group-containing polyfunctional acrylate having an unreacted acid anhydride group. Next, 130 parts of the epoxy acrylate (EA1) obtained above was added to this, and the unreacted acid anhydride group and the hydroxyl group of the epoxy acrylate were mixed at 80 ° C.
And reacted for 4 hours. The composition (I) obtained has a solid content of 6
The content was 9.5%, and the polyfunctional acrylate containing a carboxyl group and dipentaerythritol hexaacrylate were contained at 58.5% and 11.0%, respectively.

To 100 parts of the composition (I) obtained above,
40 parts of toluene and 1.5 parts of benzyl dimethyl ketal were mixed to prepare an active energy ray-curable coating composition (A). This active energy ray-curable coating composition (A)
Was applied to a transparent 2 mm-thick polycarbonate plate using a bar coater so that the thickness of the coating film after drying would be 8 μm, and heat-dried at 100 ° C. for 10 minutes. The surface of the polycarbonate plate after drying had no tack, and it was confirmed that the coating composition (A) had a film-forming property. Using a high-pressure mercury lamp with an output of 7.5 kW and an output density of 120 w / cm, which was installed perpendicularly to the sample passage direction, the
At the position of cm, ultraviolet rays were applied at a conveyor speed of 2 m / min to perform ultraviolet curing.

The adhesion of the hard coat layer formed on the polycarbonate plate to the polycarbonate plate was evaluated by making 100 crosses at 1 mm intervals with a cutter knife on the hard coat layer and crimping a Nichiban cellophane tape to strongly peel it off. However, a good adhesion was obtained at 100/100 (cross-cut tape JIS K5400). The transparency of the obtained hard-coated polycarbonate plate was evaluated by the haze value (%), and it was 0.4%, and the transparency was good. The haze value of the 2 mm-thick polycarbonate plate before the hard coat treatment was 0.4% (haze value = Td / Tt × 100, Td: scattered light transmittance,
Tt: Total light transmittance JISK7105). Next, as for wear resistance, a 100 rotation taper wear test with a load of 500 g was performed using a wear wheel of Caliberase CS-10F, and the difference between the haze value after the Taber wear test and the haze value before the Taber wear test was ΔH. Was 6.4%, and the abrasion resistance was good. The ΔH obtained by performing the same Taber abrasion test on a polycarbonate plate having a thickness of 2 mm and not subjected to the hard coat treatment was 46.7% (Taber abrasion test method ASTM D1044).

Example 2 The 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 so that the film thickness after drying was 8 μm. Heat dried at 80 ° C. for 5 minutes. The surface of the polyethylene terephthalate film after drying had no tack, and it was confirmed that this coating composition (A) had a film-forming property. Then, this was processed in the same manner as in Example 1 to obtain a hard coat-treated polyethylene terephthalate film. The adhesion between the hard coat layer formed on the polyethylene terephthalate film and the polyethylene terephthalate film was evaluated to be 100/10.
When 0, good adhesion was obtained. The transparency of the obtained hard coat-treated polyethylene terephthalate film was evaluated by the haze value (%) to be 3.8%, and the transparency was good. In addition, 0.1 before hard coat treatment
The haze value of the mm-thick polyethylene terephthalate film was 3.7%. Next, when the abrasion resistance was evaluated, ΔH was 6.6% and the abrasion resistance was good. The ΔH obtained by performing the same Taber abrasion test on a polyethylene terephthalate film having a thickness of 0.1 mm which was not subjected to the hard coat treatment was 23.1%.

Example 3 4,4'-Bis (2.3-epoxypropoxy) -3.
3 ', 5,5'-Tetramethylbiphenyl (Okaka Shell Epoxy Co., Ltd .: YX-4000, epoxy equivalent 192 g
/ Eq.) 192 parts were dissolved in 113 parts of methyl isobutyl ketone, 72 parts of acrylic acid, 0.2 part of hydroquinone monomethyl ether and 1 part of N, N-dimethylbenzylamine were added, and the mixture was reacted at 110 ° C. for 6 hours. The acid value of the obtained epoxy acrylate (EA2) is 2.8 m.
It was gKOH / g. Mixture of 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride, pentaerythritol tetraacrylate and pentaerythritol triacrylate containing 73 mol% of pentaerythritol triacrylate (Osaka Organic Chemical Industry Co., Ltd .: Viscoat 300 , Hydroxyl value 131mgKOH /
32.2 parts and 50.4 parts of g) were placed in a flask so that acid anhydride group / hydroxyl group = 1.7, and 50 parts of methyl ethyl ketone and 0.1 parts of hydroquinone monomethyl ether were added.
04 parts and 0.4 parts of N, N- dimethylbenzylamine were added, and it reacted at 80 degreeC for 8 hours. Then to this was added the epoxy acrylate (EA2) 72 obtained above.
Parts were added and reacted at 80 ° C. for 4 hours. The composition (II) thus obtained had a solid content of 65.0% and contained 57.5% and 7.5% of carboxyl group-containing polyfunctional acrylate and pentaerythritol tetraacrylate, respectively. 100 parts of the composition (II) obtained above was mixed with 10 parts of the same Kayarad DPHA used in Example 1, 50 parts of toluene, and 1.5 parts of benzyl dimethyl ketal to prepare an active energy ray-curable coating composition ( B) was obtained. A hard coat-treated polycarbonate plate was obtained in the same manner as in Example 1 except that this active energy ray-curable coating composition (B) was used. The surface of the polycarbonate plate after drying had no tack, and it was confirmed that this coating composition (B) had a film-forming property. Adhesion, transparency, and abrasion resistance were evaluated in the same manner as in Example 1. Adhesion: 100/100, haze value: 0.6%, ΔH: 7.5%, and good results were obtained. Was obtained.

Example 4 Tetrabromobisphenol A type epoxy resin (Yukaka Shell Epoxy Co .: E5050, epoxy equivalent 394 g)
/ Eq.) 394 parts were dissolved in 116 parts of toluene,
Acrylic acid (72 parts), hydroquinone monomethyl ether (0.4 parts) and N, N-dimethylbenzylamine (2 parts) were added, and the mixture was reacted at 110 ° C for 8 hours. The acid value of the obtained epoxy acrylate (EA3) was 3.0 mgKOH / g. Pyromellitic dianhydride and the same Kayarad DPHA used in Example 1 were used as an acid anhydride group / hydroxyl group =
21.8 parts and 85.6 parts respectively were put in a flask so that it became 1.9, and 50 parts of methyl ethyl ketone, 0.05 part of hydroquinone monomethyl ether and 0.5 part of N, N-dimethylbenzylamine were added, and the mixture was heated to 80 ° C. And reacted for 8 hours. Then, 85.6 parts of the epoxy acrylate (EA3) obtained above was added to this, and the mixture was reacted at 80 ° C. for 4 hours. The resulting composition (III) has a solid content of 72.3%,
Carboxyl group-containing polyfunctional acrylate and dipentaerythritol hexaacrylate 59.8% and 12.
It contained 5%. Composition (III) 10 obtained above
0 part of colloidal silica with isopropyl alcohol as a dispersion medium and a solid content of 30% (manufactured by Nissan Chemical Industries: IPA
-ST) 200 parts and benzyl dimethyl ketal 1.5 parts were mixed to obtain an active energy ray-curable coating composition (C). A hard coat-treated polyethylene terephthalate film was obtained in the same manner as in Example 2 except that this active energy ray-curable coating composition (C) was used. The surface of the polyethylene terephthalate film after drying had no tack, and it was confirmed that this coating composition (C) had a film-forming property. When the adhesiveness, transparency and abrasion resistance were evaluated in the same manner as in Example 1, the adhesiveness was 10
Good results were obtained with 0/100, haze value: 3.9%, and ΔH: 5.9%.

Example 5 Bisphenol A type epoxy resin (Okaka Shell Epoxy Co., Ltd .: E1001, epoxy equivalent 472 g / eq.) 4
After dissolving 72 parts in 136 parts of methyl isobutyl ketone, 72 parts of acrylic acid, 0.5 part of hydroquinone monomethyl ether and N, N-dimethylbenzylamine 2.
5 parts was added, and the mixture was reacted at 110 ° C. for 7 hours. The acid value of the obtained epoxy acrylate (EA4) is 2.6 mgKOH.
/ G. 21.8 parts and 90.3 parts of pyromellitic dianhydride and the same Kayarad DPHA used in Example 1 were placed in a flask so that acid anhydride group / hydroxyl group = 1.8, and methyl ethyl ketone was added. 50 parts, hydroquinone monomethyl ether 0.05 parts and N, N-dimethylbenzylamine 0.5 parts were added and reacted at 80 ° C. for 8 hours. Then, 62.5 parts of the epoxy acrylate (EA4) obtained above was added to this, and the mixture was reacted at 80 ° C. for 4 hours. The composition (IV) obtained had a solid content of 72.2%.
And 57.9% each of polyfunctional acrylate containing carboxyl group and dipentaerythritol hexaacrylate,
The content was 14.3%. Composition (IV) obtained above
100 parts of 200 parts of colloidal antimony oxide (AME-130, manufactured by Nissan Chemical Industries, Ltd.) having a solid content of 30% in which methyl ethyl ketone is used as a dispersion medium, and 1.5 parts of benzyl dimethyl ketal are mixed to form an active energy ray-curable coating. A composition (D) was obtained. This active energy ray-curable coating composition (D) was applied to a transparent 0.1 mm thick triacetyl cellulose film using a bar coater so that the coating film thickness after drying would be 5 μm, and at 60 ° C. Heat dried for 2 minutes. The surface of the triacetyl cellulose film after drying had no tack, and it was confirmed that this coating composition (D) had a film-forming property. Then, this was treated in the same manner as in Example 1 to obtain a hard coat-treated triacetyl cellulose film. When the adhesion between the hard coat layer formed on the triacetyl cellulose film and the triacetyl cellulose film was evaluated, it was 100/1.
A good adhesion was obtained at 00. The transparency of the obtained hard coat-treated triacetylcellulose film was evaluated by the haze value (%), and it was 0.4%, which was good. 0.1m before hard coat treatment
The haze value of the m-thick triacetyl cellulose film was 0.2%. Next, when the wear resistance was evaluated,
H was 6.4% and the wear resistance was good. In addition, ΔH obtained by performing the same Taber abrasion test on a 0.1 mm-thick triacetyl cellulose film not subjected to the hard coat treatment was 32.5%.

Example 6 An active energy ray-curable coating composition (E) was obtained by mixing in the same manner as in Example 4 except that the amount of colloidal silica having a solid content of 30% was 700 parts in Example 4. A hard coat-treated triacetyl cellulose film was obtained in the same manner as in Example 5. The surface of the triacetyl cellulose film after drying had no tack, and it was confirmed that this coating composition (E) had a film-forming property. When the adhesion, transparency and abrasion resistance were evaluated in the same manner as in Example 1, the adhesion was 10
0/100, haze value: 0.4%, ΔH: 6.8%, and good results were obtained.

Example 7 100 parts of the composition (I) obtained in Example 1 and 100 parts of colloidal silica (IPA-ST manufactured by Nissan Chemical Industries, Ltd.) having a solid content of 30% and containing isopropyl alcohol as a dispersion medium are mixed. Then, an active energy ray-curable coating composition (F) was obtained. This active energy ray-curable coating composition (F)
A transparent polyethylene terephthalate film with a thickness of 0.1 mm has a coating thickness of 8 μm after drying with a bar coater.
And was heated and dried at 80 ° C. for 5 minutes. The surface of the polyethylene terephthalate film after drying had no tack, and it was confirmed that this coating composition (F) had a film-forming property. Electron beam acceleration voltage 175k
V, 5M electron beam under conditions of conveyor speed 10m / min
It was irradiated with rad and cured by electron beam. Adhesion, transparency and abrasion resistance were evaluated in the same manner as in Example 1. Adhesion: 100/100, haze value: 3.7%, ΔH: 6.1
%, Which is a good result.

Application Example 1 The active energy ray-curable coating composition (A) obtained in Example 1 was coated on offset coated paper using a bar coater to give a coating film thickness of 10 μm after drying. The coating was applied as described above, dried by heating at 80 ° C. for 3 minutes, embossed, and then irradiated with ultraviolet rays under the same conditions as in Example 1 to form a transparent relief layer on the coated paper surface. As a result, a printed matter having a three-dimensional effect was obtained. The coating composition (A) not only provides an excellent wear resistant surface, but also has excellent embossability.

Application Example 2 The active energy ray-curable coating composition (C) obtained in Example 4 was applied to a transparent polyethylene terephthalate film having a thickness of 0.1 mm to give a coating film thickness after drying using a bar coater. It is applied to a thickness of 8 μm, heated and dried at 80 ° C. for 5 minutes, then a pattern is printed on it by the gravure printing method, and an acrylic adhesive for hot sealing (hot stamping agent)
Was applied. Thermal transfer was performed on the plywood from the film surface side with the acrylic adhesive surface facing down, using a heat roll. Next, the film was peeled off, and ultraviolet rays were irradiated under the same conditions as in Example 1 to cure the active energy ray-curable coating composition (C) for the surface layer. This can be used as a wall material. The coating composition (C) not only provides a smooth abrasion resistant surface, but is also excellent in pattern printing and film peeling processability.

Comparative Example 1 Epoxy acrylate (EA1) 1 obtained in Example 1
40 parts of toluene and 1.5 parts of benzyl dimethyl ketal were mixed with 00 parts to prepare an active energy ray-curable coating composition (G). A hard-coated polycarbonate plate was obtained in the same manner as in Example 1 except that this active energy ray-curable coating composition (G) was used. The surface of the polycarbonate plate after drying had no tack, and it was confirmed that this coating composition (G) had a film-forming property. When the adhesion, transparency and abrasion resistance were evaluated in the same manner as in Example 1, the haze value: 0.5% was good, but the adhesion: 0/100, ΔH: 17.5% The adhesiveness and wear resistance were insufficient.

Comparative Example 2 Pyromellitic dianhydride and the same Kayarad DPHA used in Example 1 were used in an amount of 21.8 parts and 90.3 parts, respectively, so that acid anhydride group / hydroxyl group = 1.8. In a flask,
Methyl ethyl ketone (50 parts), hydroquinone monomethyl ether (0.05 parts) and N, N-dimethylbenzylamine (0.5 parts) were added, and the mixture was reacted at 80 ° C. for 8 hours. The composition (V) thus obtained had a solid content of 69.2% and contained 49.4% each of a polyfunctional acrylate containing an acid anhydride group and a carboxyl group and dipentaerythritol hexaacrylate.
The content was 19.8%. Composition (V) obtained above
40 parts of toluene and 1.5 parts of benzyl dimethyl ketal were mixed with 100 parts to prepare an active energy ray-curable coating composition (H). This active energy ray-curable coating composition (H) was applied to a transparent polycarbonate plate having a thickness of 2 mm using a bar coater so that the coating film thickness after drying would be 8 μm, and dried by heating at 100 ° C. for 10 minutes. However,
There was tack on the surface of the polycarbonate plate after drying, and no coating film forming property was observed in this coating composition (H).

Comparative Example 3 87.2 parts and 51.6 parts of pyromellitic dianhydride and 2-hydroxyethyl acrylate were placed in a flask so that acid anhydride group / hydroxyl group = 1.8, and methyl ethyl ketone 50 was added. Part, hydroquinone monomethyl ether 0.
05 parts and 0.5 parts of N, N-dimethylbenzylamine were added and reacted at 80 ° C. for 8 hours. Then, the epoxy acrylate (EA obtained in Example 1) (EA
1) 62.5 parts was added and reacted at 80 ° C. for 4 hours. The composition (VI) thus obtained was a acrylate containing a carboxyl group having a solid content of 72.6%. The composition (V
The active energy ray-curable coating composition (J) was prepared by mixing 100 parts of I) with 15 parts of the same Kayarad DPHA as used in Example 1, 60 parts of toluene, and 1.8 parts of benzyl dimethyl ketal. In the same manner as in Example 1 except that this active energy ray-curable coating composition (J) was used,
A hard coat-treated polycarbonate plate was obtained. The surface of the polycarbonate plate after drying had no tack, and it was confirmed that this coating composition (J) had a film-forming property.
Adhesion, transparency, and abrasion resistance were evaluated in the same manner as in Example 1. Adhesion: 100/100, haze value:
0.6% was good, but ΔH was 16.3% and wear resistance was not sufficient.

[0026]

EFFECTS OF THE INVENTION Since the present invention is constructed as described above, it is a coating which is cured by irradiation with active energy rays to form a coating film excellent in adhesion to a plastic substrate, transparency and abrasion resistance. A composition can be provided. Furthermore, it is also possible to form a film when the solvent is dried, and after this is subjected to processing such as molding, printing and transfer, it is irradiated with active energy rays to form a coating film excellent in abrasion resistance. Various applications are possible.

Claims (4)

[Claims] 1. A tetracarboxylic dianhydride (a) and a hydroxyl group-containing polyfunctional acrylate having a hydroxyl group and three or more acryloyl groups in the molecule, wherein the acid anhydride group / hydroxy group ratio is 1.2 to 2. A polyfunctional acrylate containing a carboxyl group obtained by reacting with an epoxy acrylate after reacting at a ratio of (b), a polyfunctional acrylate having (b) three or more acryloyl groups in the molecule, (c) an organic solvent, and if necessary. (D) An active energy ray-curable abrasion-resistant coating composition, which comprises a photopolymerization initiator. 2. The composition according to claim 1, wherein the weight ratio of component (b) / component (a) is 1 or less. 3. In addition to the component of claim 1, (e)
Contains colloidal metal oxide and (e) component /
A weight ratio of {(a) component + (b) component} is 10 or less, an active energy ray-curable abrasion resistant coating composition. 4. The composition according to any one of claims 1 to 3, wherein the component (b) is selected from dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate and mixtures thereof.