JPH0723430B2 - Surface-treated plastic molded product - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial field of application) The present invention is excellent in chemical resistance, light transmission, heat resistance, flexibility, scratch resistance, and adhesion, as well as moisture resistance and surface smoothness. Surface-treated plastic molded article.

(Prior Art) Liquid crystal display cells are widely used for watches, desk-top electronic calculators, measuring instruments, word processors, small televisions, etc. because of their low power consumption, thin shape, light-receiving type display, and easy viewing and little eye fatigue. Conventionally, liquid crystal display cells have a transparent glass substrate on which a transparent conductive film mainly composed of isodium oxide or tin oxide is vapor-deposited, and a pattern is formed by sputtering or coating.
An alignment film of organic silane, polyimide, linear polyamide, etc. is formed, or SiO ₂ etc. is formed by oblique vapor deposition or rubbing, and the panel substrates that have been subjected to the alignment treatment are bonded with a sealant, and an azoxy-based liquid crystal, biphenyl-based It is produced by encapsulating a liquid crystal compound such as liquid crystal, cyclohexane-phenyl liquid crystal, or cyclohexane-biphenyl liquid crystal. However, when the glass plate is used as the substrate, the mechanical strength of the glass is greatly restricted, and thus it is not possible to cope with the thinning of the liquid crystal display cell, which is currently strongly demanded by the industry. There is also a defect that it is unsuitable for continuous production (lengthening of the film), which is essential for improving productivity. In addition, the brittleness against impact has been pointed out again, easy workability, lightweight,
Attention has been focused on a liquid crystal display cell using a plastic film as a substrate, which can be made thin and has excellent flexibility. By the way, when such a plastic film is used as a substrate, since the plastic has a low surface hardness and a low resistance to friction, contact with other objects during the manufacturing process,
The surface is damaged by scratches, collisions, etc., and the optical properties are lost, which significantly reduces the commercial value. Further, there are drawbacks such as deterioration due to organic chemicals that come into contact when forming the pattern of the transparent electrode, liquid crystal to be encapsulated, and deformation due to heat. For the purpose of improving such defects, a surface treatment method for imparting chemical resistance, heat resistance, scratch resistance and the like of a plastic film has been studied.

In addition, plastic products molded from transparent plastics such as polymethylmethacrylate and polycarbonate have various properties such as transparency, impact resistance, good moldability, and low cost in the field where glass products have been conventionally used. Since it has the advantage of, it has come to be used in large amounts as a substitute for glass in the fields of optical and magneto-optical disks, lenses, plates, molded articles and the like. Generally, optical discs typified by digital audio discs are made of metal such as silver or aluminum on a polymethylmethacrylate resin substrate or a polycarbonate resin substrate on which signals are written by injection molding or photopolymer (2P method). Is manufactured by forming a thin film by a method such as sputtering or vapor deposition. However, plastics such as polymethylmethacrylate and polycarbonate have low surface hardness and low resistance to abrasion, so the surface is damaged by contact with other objects, scratches, collisions, etc. There was a fatal defect that the characteristics were lost. For the purpose of improving such defects, various thermosetting and ultraviolet-curing surface treatment methods have been proposed which increase the surface hardness of the plastic product and impart abrasion resistance.

(Problems to be solved by the invention) However, in the thermosetting surface treatment, high temperature and long time are required for curing, so plastic molded products of various shapes such as plastic film are deformed, and if the curing temperature is lowered, the production becomes difficult. There are drawbacks such as deterioration in sex. In addition, UV curable surface treatment has low adhesiveness and flexibility, and there is nothing that satisfies chemical resistance, so it is rarely used in general and it has not yet been put into practical use. is there.

The present inventors have already found a surface treatment agent for plastics in which the above-mentioned drawbacks have been improved, and proposed it (Japanese Patent Application No. 60-173912).
((JP-A-62-34926)). The plastic moldings surface-treated by using the UV-curable surface treatment agent previously proposed by the present inventors were very excellent in scratch resistance, surface smoothness, adhesion and light transmission. However, it was found in the subsequent research that the moisture resistance was not always sufficient. That is, in the cross-cut cellophane tape peeling test under high temperature and high humidity, the cellophane tape peeling test is passed under the condition of 65 ° C. and 95% RH for 200 hours, but the cellophane tape peeling test after the presser-cooker test (6 hours at 120 ° C.) When it was carried out, it was found that the pass rate was not sufficient. From such a situation, chemical resistance and light transmission as well as adhesion,
There has been a strong demand from the industry for the development of a surface treatment method having excellent flexibility, heat resistance, scratch resistance, surface smoothness, and moisture resistance. An object of the present invention is to provide a plastic molded product that solves the above problems.

(Means for Solving Problems) As a result of intensive studies to solve the drawbacks of the surface treatment of the plastic molded product, the present inventors have found that the plastic molded product has (a) two or more acryloyl groups in the molecule. / And an epoxy acrylate resin having a methacryloyl group, (b) three or more acryloyl groups in the molecule, or /
And a photopolymerizable compound having a methacryloyl group,
It has been found that the above-mentioned drawbacks of the Plastic molded article can be solved by surface-treating with (c) a photoinitiator and (d) an ultraviolet-curable surface-treating agent containing a silane compound containing an amino group. The invention was reached.

That is, the present invention provides a plastic molded article, (a) an epoxy acrylate resin having two or more acryloyl groups and / or methacryloyl groups in the molecule, (b)
A photopolymerizable compound having three or more acryloyl groups or / and methacryloyl groups in the molecule, (c) a photoinitiator, and (d) a silane compound containing an amino group, and optionally (e) a fluorine-based interface. A surface-treated plastic molded article characterized by being surface-treated with an ultraviolet-curable surface treatment agent containing an activator.

The surface-treated plastic molded product of the present invention is not only excellent in chemical resistance, light transmission, and gloss, but also excellent in adhesion, heat resistance, scratch resistance, surface smoothness and moisture resistance, and the molded product is In the case of a film, it is a plastic film having excellent flexibility.

Examples of the plastic molded article used in the present invention include celluloses such as cellulose diacetate, cellulose triacetate, cellulose butyrate, acetic acid / cellulose butyrate, polycarbonate, polystyrene, polymethylmethacrylate, polyvinyl chloride, polyether sulfone, polysulfone. Well-known plastic moldings such as epoxy resin, polyethylene terephthalate, and polyamide can be used. In particular, the features of the present invention are exerted when applied to a transparent plastic molded product. As the form of plastic molded products, sheets,
There are films, disks, lenses, panels, and three-dimensional molded products. There are various methods for producing a molded product, such as extrusion molding, injection molding, cast molding, and pressure molding, but there is no particular limitation.

The epoxy acrylate resin having two or more acryloyl groups and / or methacryloyl groups in the molecule (a) used in the present invention is a (meth) acrylated compound of an epoxy compound having two or more epoxy groups in one molecule ( Methacrylate compound and acrylate compound, which will be abbreviated hereinafter), and the epoxy equivalent of the starting epoxy compound is 100 to 4,000, preferably 100 to 1,000.

Representative photopolymerizable epoxy (meth) acrylate resins include (i) (meth) acrylate compounds of polyglycidyl ethers of polyhydric phenols having a valence of 2 or more, such as bisphenol A, bisphenol F, halogenated bisphenol A, and the like. (Ii) Polyglycidyl of dihydric or higher polyhydric alcohols, such as (meth) acrylate compounds of polyglycidyl ethers such as bisphenol-type epoxy resins which are diglycidyl ethers, and novolac-type epoxy resins such as phenol novolac and cresol novolac (Meth) acrylate compounds of ether,
For example, (meth) acrylate compounds of polyglycidyl ethers of dihydric or higher aliphatic alcohols such as ethylene glycol, propylene glycol, neopentyl glycol, 1,4-butanediol, 1,6-hexanediol, and trimethylolpropane. (Iii) (meth) acrylate compounds of polyglycidyl ester of divalent or higher polyvalent carboxylic acids such as phthalic acid, isophthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, adipic acid, (iv) aniline, isocyanuric (Meth) acrylate compounds of polyglycidyl ether in which active hydrogen bonded to a nitrogen atom of an acid or the like is substituted with a glycidyl group, (v) vinylcyclohexane diepoxide obtained by epoxidizing an olefin bond in a molecule, 3,4- Epoxy cyclohexylmethyl-3,4 (Meth) acrylate compounds of alicyclic polyepoxy compounds such as epoxycyclohexanecarboxylate, 2- (3,4-epoxy) cyclohexyl-5,5-spiro (3,4-epoxy) cyclohexane-m-dioxane, ( vi) N, N, N ′, N′−
Tetraglycidyl metaxylenediamine, N, N, N ', N'
-Meta of aminopolyepoxy compounds such as tetraglycidyl-1,3-bis (aminomethyl) cyclohexane
There are acrylate compounds. These epoxy acrylate resins are used alone or in combination of two or more.

Among these, preferred epoxy acrylate resins include diglycidyl ether of bisphenol A, phenol novolac type polyepoxy compounds, cresol novolac type polyepoxy compounds, and polymethacrylate compounds (meth) acrylate compounds of polyhydric alcohols.

Further, (meth) acrylate compounds of epoxy compounds having one epoxy group in the molecule such as allyl glycidyl ether and phenyl glycidyl ether can also be used in combination.

Examples of the photopolymerizable compound (b) having three or more acryloyl groups or / and methacryloyl groups in the molecule used in the present invention include (i) trimethylolpropane tri (meth) acrylate and trimethylolethanetri ( Poly (meth) acrylates of trivalent or more aliphatic polyhydric alcohol such as (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, trivalent or more Halogen-substituted aliphatic polyhydric alcohol poly (meth) acrylates, tris (meth) acryloyloxyethyl isocyanurate, tris (meth) acryloyloxypropyl isocyanurate, tris (meth) acryloyloxybutyl isocyanate Rate and the like tris (meth) acryloyl alkyl isocyanurates such.

These trifunctional or higher functional (meth) acrylate compounds may be used alone or in combination of two or more. If necessary, other various oligomers and polymers and difunctional or lower (meth) acrylate monomers can be used in combination.

The epoxy acrylate (a) of the present invention and 3 in the molecule
The photopolymerizable compound (b) having one or more acryloyl groups and / or methacryloyl groups is (a) / (b) = 60.
A mixing ratio of / 40 to 5/95 (weight ratio) is preferable. (A) is 6
If it exceeds 0 parts by weight, the adhesion will decrease, and if it is less than 5 parts by weight, the light transmittance and weather resistance will decrease.

Examples of the (c) photoinitiator that accelerates the photopolymerization reaction of the ultraviolet curable resin of the present invention include ketals such as benzyl dimethyl ketal, benzoin methyl ether, and the like.
Benzoins such as benzoin ethyl ether, benzoin-1-propyl ether, benzoin and α-methylbenzoin, anthraquinones such as 9,10-anthraquinone, 1-chloroanthraquinone, 2-chloroanthraquinone and 2-ethylanthraquinone, benzophenone,
Benzophenones such as p-chlorobenzophenone and p-dimethylaminobenzophenone, 2-hydroxy-2
-Propiophenones such as methylpropiophenone and 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropiophenone, suberones such as dibenzosuberone, diphenyldisulfide, tetramethylthiuram disulfide, thioxanthone, etc. And the dyes such as methylene blue, eosin and fluorescein. These photoinitiators may be used alone or in combination of two or more.

The amount of the photoinitiator added is 0.1 to 20% by weight, preferably 0.5 to 10% by weight, based on the resin component of the ultraviolet curable resin.

Examples of the (d) amino group-containing silane compound used in the present invention include aminomethyltrimethoxysilane, aminomethyltriethoxysilane, aminomethyltri-n-propoxysilane, aminomethyltri-n-butoxysilane, and aminoethyltrisilane. Methoxysilane, aminoethyltriethoxysilane, aminoethyltri-n-propoxysilane, aminoethyltri-n-butoxysilane, amino-n-propyltrimethoxysilane, amino-n-propyltriethoxysilane, amino-n-propyl Tri-n-propoxysilane, amino-n-propyltri-
n-Butoxysilane, N-aminomethyl-aminomethyltrimethoxysilane, N-aminomethyl-aminomethyltriethoxysilane, N-aminomethyl-aminomethyltri-n-propoxysilane, N-aminomethyl-aminomethyltri- n-butoxysilane, N-β-aminoethyl-β-aminoethyltrimethoxysilane, N-β-
Aminoethyl-β-aminoethyltriethoxysilane,
N-β-aminoethyl-β-aminoethyl-n-propoxysilane, N-β-aminoethyl-β-aminoethyltri-n-butoxysilane, N-γ-amino-n-propyl-γ-amino-n -Propyltrimethoxysilane,
N-γ-amino-n-propyl-γ-amino-n-propyltriethoxysilane, N-γ-amino-n-propyl-γ-amino-n-propyltri-n-propoxysilane, N-γ-amino -N-propyl-γ-amino-n
-Propyltributoxysilane, N-aminomethyl-β
-Aminoethyltrimethoxysilane, N-aminomethyl-β-aminoethyltri-n-butoxysilane, N-aminoethyl-γ-amino-n-propyltrimethoxysilane, N-aminomethyl-γ-amino-n- Propyltri-n-butoxysilane, N-β-aminoethyl-aminomethyltrimethoxysilane, N-β-aminoethyl-
Aminomethyltri-n-butoxysilane, N-aminomethyl-γ-amino-n-propyltrimethoxysilane,
N-aminothymel-γ-amino-n-propyltri-n
-Butoxysilane, N-γ-amino-n-propyl-aminomethyltrimethoxysilane, N-γ-amino-n-
Propyl-aminomethyltri-n-butoxysilane, N
-Γ-amino-n-propyl-β-aminoethyltrimethoxysilane, N-γ-amino-n-propyl-β-aminoethyltri-n-butoxysilane, N-β-aminoethyl-γ-amino-n -Propyltrimethoxysilane, N-β-aminoethyl-γ-amino-n-propyltri-n-butoxysilane, N-β-aminoethyl-γ
-Aminopropylmethyldimethoxysilane and the like. Among them, particularly preferred is N-β-aminoethyl-
γ-amino-n-propyltrimethoxysilane, N-β
-Aminoethyl-γ-aminopropyl-methyldimethoxysilane, amino-n-propyltriethoxysilane and the like.

The addition amount of the silane compound containing an amino group in the present invention is 0.05 with respect to the resin component of the ultraviolet curable resin of the present invention.
-20% by weight, preferably 0.1-10% by weight. When the addition amount of the silane compound having an amino group exceeds 20% by weight, the storage stability of the coating agent decreases, and the scratch resistance and surface hardness also decrease. Adhesion is not sufficient, which is not preferable.

(E) Fluorine-based surfactants optionally used in the present invention include perfluorocarbonyl fluoride (C ₇ F ₁₅ COF) and perfluorosulfonyl fluoride (C ₈ F ₁₇ SO ₂ ) obtained by electrolytic fluorination. derivative as a starting material and F), and methanol and tetrafluoroethylene obtained by telomerization of ethylene w-H- perfluoro alcohol _{(H (CH 2 CF 2)} nCH 2 OH) or perfluoro iodides such as the starting material Examples thereof include derivatives and fluorine-based surfactants derived from perfluoroalkene monomers. In particular (N is an integer and Rf is a fluoroalkane) A fluorine-based surfactant which is a copolymer with (m is an integer) is preferable. The amount of fluorine-based surfactant added is 0.001 to 20.
%, Preferably 0.01 to 10% by weight.

The surface treating agent of the present invention can also be used by diluting each with a compatible organic solvent, and examples of such a diluent include alcohol-based, ether-based, ester-based,
There are solvents such as ketone type, aromatic hydrocarbon type, chlorine type hydrocarbon type and polyhydric alcohol derivative type. The diluent may be used alone or in combination of two or more. Further, if necessary, various additives such as an antistatic agent and a defoaming agent may be added to the surface treatment agent of the present invention.

In the present invention, before the plastic molded article is treated, it is generally subjected to pretreatment such as spraying with a clean blow, solvent cleaning, ultrasonic cleaning with a surfactant aqueous solution or ion-exchanged water, and solvent vapor cleaning.

The UV-curable surface treatment agent can be applied to plastic molded articles by any ordinary method such as dipping, spraying, spin coating, roll coating, reverse coating, bar coating, and gravure coating. it can. The application surface can be applied to one side or both sides of the plastic molded product. In some cases, it may be applied in a multilayer structure of two or more layers. In the case of a plastic film for liquid crystal display, it is common to apply it on both sides of the plastic film. Particularly in the case of an optical disc, the spin coating method and the dipping method are preferable.

The thickness of the coating layer is 0.1 to 50 μm, preferably 0.5 to 30 μm. If it is less than 0.1 μm, the chemical resistance becomes insufficient, and if it exceeds 50 μm, the flexibility is lowered and cracks are likely to occur in the coating film, which is not preferable.

In order to cure the applied ultraviolet curable surface treatment agent of the present invention, a method of irradiating with ultraviolet light in the wavelength range of 200 to 400 nm is used. When the coating film is cured by irradiation with ultraviolet rays, it can be irradiated in air, but it is preferably cured by irradiation in an inert gas atmosphere such as nitrogen gas or carbon dioxide gas.

(Effects of the Invention) The surface treatment of the present invention not only provides excellent light transmission and chemical resistance, but also heat resistance, adhesion, flexibility, scratch resistance, surface smoothness, and moisture resistance. An excellent plastic molded product can be obtained.

On the other hand, since it is cured by ultraviolet rays, it can be cured at a low temperature, so that the plastic molded product is not deformed or distorted by heat, and the curing time is greatly shortened, and the productivity can be greatly improved.

(Examples) Hereinafter, the present invention will be further described with reference to Examples, but the present invention is not limited to these Examples. The measuring method in the examples was according to the following method.

Adhesion test (JIS D0202): 120 ° C of surface-treated plastic moldings using a pressure cooker tester
After 6 hours of testing, the surface treatment surface was scratched in 11 mm intervals at 11 mm intervals (cross cut L), cellophane tape was adhered to it, and then strongly peeled in the 45 ° direction to prevent peeling. The number was measured.

Light transmission: Surface-treated plastic moldings with a double beam spectrophotometer ("Hitachi") at wavelengths of 500-8
The light transmittance in the 00 nm region was measured.

Chemical resistance: The surface-treated plastic molded product was immersed in cyclohexanone at 90 ° C, and the appearance change of the molded product was measured.

Flexibility: The minimum diameter of the metal round bar was measured so that the coating film did not crack when the surface-treated plastic film was wound on the metal round bar.

Heat resistance: 40mm wide x 40mm long surface-treated plastic film, as shown in Fig. 1, 10 from the edge in the length direction
Place the glass plate up to the position of mm with two glass plates, place it horizontally on a support, and put the film with a width of 10 mm and a length of 30 mm in 160 mm.
After leaving in the atmosphere at 0 ° C. for 2 hours, the sag distance A of the film was measured.

Surface smoothness (Ra): The center line average roughness was measured using a surface roughness meter (“Tokyo Seimitsu”).

Moisture resistance: The surface-treated plastic molded product was tested for 6 hours at 120 ° C. using a pressure cooker tester, and then an adhesion test was carried out to measure the number of unpeeled eyes. In the examples and comparative examples, “parts” means “parts by weight”.

Example 1 On one side of a transparent polycarbonate film having a thickness of 0.1 mm, 10 parts of bisphenol A type epoxy acrylate resin Lipoxy SP-1509 (manufactured by "Showa High Polymer"), 40 parts of pentaerythritol tetraacrylate, N-β-amino. Ethyl-γ-amino-n-propyltrimethoxysilane 0.
A coating thickness of 2 parts of an ultraviolet curable treatment agent consisting of 5 parts, 1.5 parts of α-hydroxycyclophenyl ketone, 30 parts of methyl cellosolve, 10 parts of toluene and 10 parts of isopropyl alcohol.
It was applied by bar coating so as to have a thickness of .mu.m, dried at 40.degree. C. for 5 minutes, and then irradiated and cured under an inert gas atmosphere at a distance of 15 cm under a water-cooled high-pressure mercury lamp of 80 w / cm for 40 seconds to be cured. Next, the back surface was similarly surface-treated. The measurement results of the polycarbonate film whose both surfaces were surface-treated were as follows.

Adhesion: 100/100 Light transmittance: 90% Flexibility: 3 mmφ Heat resistance: 3 mm Chemical resistance: 1 hour No change Example 2 In Example 1, lipoxy SP-1509 which is a bisphenol A type epoxy acrylate resin (previously In the same manner as in Example 1 except that a phenol novolac type epoxy acrylate Lipoxy SP-4010 (manufactured by "Showa High Polymer") is used in place of the above), both surfaces of a 0.1 mm thick transparent polycarbonate film are surface-treated. did. The measurement results of the surface-treated polycarbonate film were as follows.

Adhesion: 100/100 Light transmittance: 89% Flexibility: 4 mmφ Heat resistance: 3 mm Chemical resistance: No change for 1 hour Example 3 N-β-aminoethyl-γ-amino-in Example 1
A thickness of 0.1 mm was obtained in the same manner as in Example 1 except that N-β-aminoethyl-γ-aminopropyl-methyldimethoxysilane was used instead of n-propyltrimethoxysilane.
Both surfaces of the transparent polycarbonate film of No. 2 were surface-treated. The measurement results of this surface-treated polycarbonate film were as follows.

Adhesion: 100/100 Light transmittance: 90% Flexibility: 3 mmφ Heat resistance: 3 mm Chemical resistance: 1 hour unchanged Example 4 In Example 1, N-β-aminoethyl-γ-amino-
amino-n instead of n-propyltrimethoxysilane
Both sides of a 0.1 mm thick transparent polycarbonate film were surface-treated in the same manner as in Example 1 except that propyltriethoxysilane was used. The measurement results of this surface-treated polycarbonate film were as follows.

Adhesion: 100/100 Light transmittance: 90% Flexibility: 3 mmφ Heat resistance: 3 mm Chemical resistance: 1 hour No change Example 5 The same as Example 1 except that the thickness of the coating film was 5 μm. Both sides of a 0.1 mm thick transparent polycarbonate film were surface treated. The measurement results of this surface-treated polycarbonate film were as follows.

Adhesion: 100/100 Light transmittance: 90% Flexibility: 6mmφ Heat resistance: 3mm Chemical resistance: No change for 2 hours Comparative example 1 Bisphenol A type epoxy acrylate resin on one side of transparent polycarbonate film of 0.1mm thickness 50 parts of lipoxy SP-1509 (described above), 1.5 parts of α-hydroxycyclophenyl ketone, 0.5 part of N-β-aminoethyl-γ-amino-n-propyltrimethoxysilane, 30 parts of methyl cellosolve, 10 parts of toluene. UV-curable surface treatment agent consisting of 10 parts of isopropyl alcohol and 5 μm
Was coated with a bar coat so as to be 5 times, dried at 40 ° C. for 5 minutes, and then cured by irradiation for 40 seconds at a distance of 15 cm under a water-cooled high pressure mercury lamp of 80 w / cm ² in an inert gas atmosphere. Next, the same surface treatment was performed on the back surface. The measurement results of the polycarbonate film whose both surfaces were surface-treated were as follows.

Adhesion: 0/100 Light transmittance: 90% Flexibility: 2 mm Heat resistance: 10 mm Chemical resistance: 0.5 hours No change Comparative Example 2 In Comparative Example 1, Lipoxy SP-1509 which is a bisphenol A type epoxy acrylate resin (previously Both surfaces of a 0.1 mm thick transparent polycarbonate film were surface-treated in the same manner as in Comparative Example 1 except that pentaerythritol tetraacrylate was used instead of the above. The measurement results of this surface-treated polycarbonate film were as follows.

Adhesion: 100/100 Light transmittance: 90% Flexibility: 10 mmφ Heat resistance: 3 mm Chemical resistance: Dissolved in 15 minutes Comparative Example 3 N-β-aminoethyl-γ-amino-in Example 1
A transparent polycarbonate having a thickness of 0.1 mm was prepared in the same manner as in Example 1 except that n-propyltrimethoxysilane was not used.
Both sides of the film were surface treated. The measurement results of this surface-treated polycarbonate film were as follows.

Adhesion: 0/100. Light transmittance: 90% Flexibility: 3mm Heat resistance: 3mm Chemical resistance: No change for 2 hours Example 6 A transparent polycarbonate plate with a thickness of 1.5mm and bisphenol A type epoxy acrylate resin Lipoxy SP1509
(Made by "Showa High Polymer") 10 parts, pentaerythritol tetraacrylate 40 parts, methyl cellosolve 30 parts, toluene
10 parts, isopropyl alcohol 10 parts, α-hydroxycyclophenyl ketone 1.5 parts, fluorosurfactant Surflon S-381 (manufactured by “Asahi Glass”) 0.2 parts and N-β-aminoethyl-γ-amino-n-propyltri Apply a UV-curable surface treatment agent consisting of 0.5 parts of methoxysilane with a spinner and dry at 40 ° C for 5 minutes, then in an inert gas atmosphere.
An 80 w / cm water-cooled high-pressure mercury lamp was irradiated at a distance of 15 cm for 40 seconds to cure. Table 1 shows the measurement results of the surface-treated polycarbonate plate.

Example 7 A transparent polymethylmethacrylate plate was surface-treated in the same manner as in Example 6 except that a transparent polymethylmethacrylate plate was used in place of the transparent polycarbonate plate. The measurement results of the surface-treated polymethylmethacrylate plate are shown in Table 1.

Example 8 Example 6 is repeated except that Lipoxy SP4010 (manufactured by “Showa Polymer”) which is a phenol novolac type epoxy acrylate resin is used in place of Lipoxy SP1509 (above-mentioned) which is a bisphenol A type epoxy acrylate resin. The polycarbonate plate was surface-treated in the same manner as in. Table 1 shows the measurement results of the surface-treated polycarbonate plate.
It was the street.

Example 9 In Example 6, N-β-aminoethyl-γ-amino-
A polycarbonate plate was surface-treated in the same manner as in Example 6 except that N-β-aminoethyl-γ-aminopropyl-methyldimethoxysilane was used instead of n-propyltrimethoxysilane. The measurement results of the surface-treated polycarbonate plate are shown in Table 1.

Example 10 In Example 6, N-β-aminoethyl-γ-amino-
Amino-n instead of n-propyltrimethoxysilane
A polycarbonate plate was surface-treated in the same manner as in Example 6 except that -propyltriethoxysilane was used. The measurement results of the surface-treated polycarbonate plate are shown in Table 1.

Comparative Example 4 Visfetru A on a transparent polycarbonate plate with a thickness of 1.5 mm
Type epoxy acrylate resin Lipoxy SP1509
(“Previously”) 50 parts, methyl cellosolve 30 parts, toluene 10
Parts, isopropyl alcohol 10 parts, α-hydroxycyclophenyl ketone 1.5 parts and N-β-aminoethyl-
Apply a UV-curable surface treatment agent consisting of 0.2 part of γ-amino-n-propyltrimethoxysilane with a spinner,
After drying at 5 ° C. for 5 minutes, an 80 w / cm water-cooled high pressure mercury lamp was irradiated at a distance of 15 cm for 40 seconds in an inert gas atmosphere to cure. Table 1 shows the measurement results of the surface-treated polycarbonate plate.
It was the street.

Comparative Example 5 A polycarbonate plate was surface-treated in the same manner as in Comparative Example 4 except that pentaerythritol tetraacrylate was used in place of Lipoxy SP1509 (previously described) which is a bisphenol A type epoxy acrylate resin in Comparative Example 4.
The measurement results of the surface-treated polycarbonate plate are shown in Table 1.

Comparative Example 6 The fluorosurfactant Surflon S-38 in Example 6 was used.
A polycarbonate plate was surface-treated in the same manner as in Example 1 except that 1 (supra) was not added. The measurement results of the surface-treated polycarbonate plate are shown in Table 1.

Comparative Example 7 N-β-aminoethyl-γ-amino-in Example 6
A polycarbonate plate was surface-treated in the same manner as in Example 6 except that n-propyltrimethoxysilane was not added. Table 1 shows the measurement results of the surface-treated polycarbonate plate.
It was the street.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 shows a method for measuring heat resistance.

Claims (2)

[Claims] 1. A plastic molded article is (a) an epoxy acrylate resin having two or more acryloyl groups and / or methacryloyl groups in the molecule, and (b) 3 in the molecule.
A photopolymerizable compound having one or more acryloyl groups and / or methacryloyl groups, (c) a photoinitiator, and
(D) A surface-treated plastic molded article, which is surface-treated with an ultraviolet-curable surface-treating agent containing a silane compound having an amino group. 2. An ultraviolet-curable surface treatment agent further comprises (e)
The surface-treated plastic molded article according to claim 1, which contains a fluorine-based surfactant.