JPH11302598A - Coating material composition, coating material composition-coated molded product and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject composition capable of forming a coating film excellent in low shrinkage, crack resistance, dyeing property, durability, transparency and scratch resistance at relatively low temperature in a short time and useful for lens, etc., by including a vinyloxy-containing silane compound and an acid-generating polymerization initiator. SOLUTION: This coating composition comprises (A) a compound of the formula R<1> a R<2> b Si(OR<3> )4-(a+b) [R<1> is a vinyloxy-containing 4-14C organic group; R<2> is a 1-6C (halogenated)hydrocarbon group; R<3> is a 1-4C alkyl, alkoxyalkyl or acryl; (a) and (b) are each 1-3 or 0-2 and 1<=(a+b)<=3], (B) a polymerization initiator generating an acid by irradiation of active energy beam and further (c) fine particles having 1-100 μm particle diameter and comprising (composite) oxide of a metal which is Al, Si, Sn, Sb, Ta, Ce, La, Fe, Zn, W, Zr, In or Ti and (D) a thermosetting catalyst.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a coating composition which cures rapidly by short-time irradiation with active energy rays or a combination of short-time irradiation with active energy rays and heating for a short time, and a coating layer comprising the coating composition. And a method for producing the same.

[0002]

2. Description of the Related Art At present, plastic molded articles are used in large quantities because of their advantages such as light weight, easy processability and impact resistance. However, on the other hand, there are drawbacks such as insufficient hardness and susceptibility to scratching, susceptibility to solvent attack, electrification and adsorption of dust, insufficient heat resistance, etc. there were. In particular, when manufacturing a lens using a plastic material, these problems are important issues to be solved.

In order to improve the abrasion resistance of the surface of the molded plastic, it has been proposed to apply a protective coating layer such as a hard coat to the surface of the molded plastic. As a solution to the improvement of scratch resistance, it is common to form a hard coat layer on the surface of a molded article. Conventionally, such a hard coat layer is generally formed of a film mainly composed of a heat-curable resin (hereinafter referred to as a heat-curable hard coat). It has been widely used since it has an advantage that excellent abrasion resistance can be imparted to a molded article.

[0004] As a method of forming a hard coat layer, a coating liquid to be a hard coat layer is applied to the surface of a plastic molded body by, for example, a dipping method or a spin coating method, and then heat treatment is usually performed for several hours. It is a general method of curing by heating. On the other hand, as a protective coating layer that can be cured in a shorter time than a heat-curable hard coat or the like, recently, a protective coating layer mainly composed of an ultraviolet-curable resin (hereinafter, referred to as a “hard coat”)
UV-curable coat) has been developed and spread. The UV-curable coating is a method in which a coating liquid is applied to the surface of a substrate and then cured by irradiating the coating liquid with ultraviolet light to form a film. For example, Japanese Patent Publication No. 59-30170 discloses a coating solution containing a substance having an acryloyl group or a methacryloyl group as a main component, and Japanese Patent Publication No. 60-29753 discloses an unsaturated polyester resin as a component. A coating solution is disclosed.

[0005]

The present inventors formed a heat-curable hard coat on the surface of a plastic lens substrate as in the prior art in order to improve the abrasion resistance of the plastic lens substrate. However, when the substrate on which the hard coat was formed was observed, there was a problem that the lens substrate was deformed. This deformation includes a deformation that does not affect the optical performance, but must be solved in order to further improve the performance of the lens.

[0006] Further, the formation of the heat-curable hard coat requires a curing time of about 3 to 6 hours, so that it is necessary to further improve the production efficiency. Further, the present inventors formed an ultraviolet-curable coat mainly composed of the above-mentioned conventional material on the surface of the plastic lens substrate. However, the formed ultraviolet-curable coat has a problem that the scratch resistance is inferior to the heat-curable hard coat. Also recently
With respect to spectacle lenses, demands for highly durable lenses that can withstand use in various environments have been increasing, and solving the above problems has become important.

[0007]

Means for Solving the Problems The present inventors have searched for the cause of deformation occurring in the lens substrate when the above-mentioned thermosetting hard coat is formed. As a result, when a heat-curable hard coat is formed on a plastic lens substrate, a long-time heat treatment is performed to cure the hard coat, but the plastic substrate itself becomes hot during this heat treatment. It was found that deformation and discoloration occurred in a plastic substrate having low heat resistance.

Accordingly, in the present invention, the following component (a):
An active energy ray-curable coating agent composition comprising (b). (A) General formula (I): R ¹ aR ² bSi (OR ³ ) _{4- (a + b)} (wherein, R ¹ is an organic group having 4 to 14 carbon atoms having a vinyloxy group, R ² is a hydrocarbon group having 1 to 6 carbon atoms or a halogenated hydrocarbon group; R ³ is an alkyl group, an alkoxyalkyl group or an acyl group having 1 to 4 carbon atoms, and a is 1 or more and 3 or less. And b is an integer of 0, 1, or 2 and a + b is an integer of 1 or more and 3 or less.) (B) A polymerization initiator that generates an acid upon irradiation with active energy rays (Claim 1) ” I will provide a.

Second, the active energy ray-curable coating composition containing the components (a) and (b) contains the following component (c):
A coating composition as described. (C) Al, Si, Sn, Sb, Ta, Ce, La, F
e, a fine particle having a particle diameter of 1 to 100 millimicrons composed of an oxide of one or more metals selected from Zn, W, Zr, In, and Ti and / or a particle diameter composed of oxides of two or more metals. 1-100 millimicron composite particles or solid solutions or mixtures thereof (Claim 2).

[0010] Thirdly, "the coating composition contains the following component (d).
Or the coating composition according to 2. (D) a thermosetting catalyst (Claim 3) ". Fourth, "a coating composition containing a polymerization initiator containing an organosilicon compound represented by the following formula or a hydrolyzate thereof as a main component and generating an acid when irradiated with active energy rays is applied to a molded body. A method for producing a molded article, comprising: a coating step of applying a coating composition; and a film forming step of irradiating an active energy ray to the molded article coated with the coating composition to cure the coating composition.

General formula (I): R ¹ aR ² bSi (OR ³ ) _{4- (a + b)} (wherein, R ¹ is an organic group having 4 to 14 carbon atoms having a vinyloxy group, R ² is a hydrocarbon group having 1 to 6 carbon atoms or a halogenated hydrocarbon group; R ³ is an alkyl group, an alkoxyalkyl group or an acyl group having 1 to 4 carbon atoms, and a is 1 or more and 3 or less. And b is an integer of 0, 1, or 2, and a + b is an integer of 1 to 3. (Claim 4).

Fifthly, there is provided "a method of manufacturing a molded article according to claim 4, wherein the step of heating is performed together with the irradiation of active energy rays in the film forming step." Sixth, "the coating composition has a particle size of 1-100.
Millimicron Al, Si, Sn, Sb, Ta, Ce,
Includes oxides of one or more metals selected from La, Fe, Zn, W, Zr, In and Ti and / or composite particles or solid solutions composed of two or more metal oxides or mixtures thereof. 4. The method according to claim 1, wherein
The method for producing a molded article according to the above. (Claim 6) "is provided.

Seventhly, there is provided a "molded article characterized in that a coating containing a polymerization initiator which generates an acid upon irradiation with an active energy ray is formed on a plastic substrate".

[0014]

DESCRIPTION OF THE PREFERRED EMBODIMENTS It is essential that the coating composition of the present invention contains at least two components (a) and (b). (A), (b), (c) or (a),
(B) containing the three components (d) or (a),
(B), (c) and (d).

The polymerization reaction in the present invention is initiated by an acid generated from the polymerization initiator of the component (b). The generated acid reacts with the R1 group of the component (a) in the general formula (I). Hereinafter, each component will be described in detail. Description of the component (a): The component (a) usable in the present invention is represented by the following general formula (I). General formula (I): R ¹ aR ² bSi (OR ³ ) _{4- (a + b)} (wherein, R ¹ is an organic group having 4 to 14 carbon atoms having a vinyloxy group, and R ² is A hydrocarbon group having 1 to 6 carbon atoms or a halogenated hydrocarbon group, R ³ is an alkyl group having 1 to 4 carbon atoms, an alkoxyalkyl group or an acyl group, and a is an integer of 1 to 3; b is an integer of 0, 1, or 2, and a + b is an integer of 1 to 3. The organosilicon compound or a hydrolyzate thereof is a compound having an acryloxy group or a methacryloxy group. (When a in the above formula is an integer of 1 or more and 3 or less), and a compound having no acryloxy group and methacryloxy group (when a in the above formula is 0).

Specific examples include, for example, vinyloxymethoxysilane, vinyloxytriethoxysilane, vinyloxytrimethoxyethoxysilane, vinyloxytriacetoxysilane, vinyloxydiethoxymethylsilane, vinyloxydimethoxymethylsilane, vinyloxydisilane. Acetoxymethylsilane, vinyloxydimethoxyethylsilane,
Vinyloxydiethoxyethylsilane, vinyloxydimethoxyethoxyethylsilane, vinyloxydiacetoxyethylsilane, vinyloxydimethoxyisopropylsilane, vinyloxydiethoxyisopropylsilane, vinyloxydimethoxyethoxyisopropylsilane, vinyloxydiacetoxyisopropylsilane, vinyloxy Methoxydimethylsilane, vinyloxyethoxydimethylsilane, vinyloxymethoxyethoxydimethylsilane, vinyloxyacetoxydimethylsilane, vinyloxymethoxydiethylsilane, vinyloxyethoxydiethylsilane,
Vinyloxymethoxyethoxydiethylsilane, vinyloxyacetoxydiethylsilane, vinyloxymethoxydiisopropylsilane, vinyloxyethoxydiisopropylsilane, vinyloxymethoxyethoxydiisopropylsilane, vinyloxyacetoxydiisopropylsilane, vinyloxymethoxymethylsilane, vinyloxyacetoxymethoxymethylsilane , Vinyloxyacetoxyethoxymethylsilane, vinyloxymethylmethoxyethoxymethylsilane, vinyloxymethoxyethoxyethylsilane,
Vinyloxyacetoxymethoxyethylsilane, vinyloxyacetoxyethoxyethylsilane, vinyloxymethoxyethoxyisopropylsilane, vinyloxyacetoxymethoxyisopropylsilane, vinyloxyacetoxyethoxyisopropylsilane, vinyloxymethyltrimethoxysilane, vinyloxymethyltriethoxysilane, vinyl Roxyethyltrimethoxysilane, vinyloxypropyltrimethoxysilane, vinyloxypropyltriethoxysilane, vinyloxypropyltripropoxysilane,
Vinyloxypropyl tributoxy silane, vinyloxy propyl triphenoxy silane, vinyloxy butyl trimethoxy silane, vinyloxy butyl triethoxy silane,
Vinyloxymethoxymethylmethyldimethoxysilane, vinyloxymethylmethyldiethoxysilane, vinyloxyethylmethyldimethoxysilane, vinyloxyethylmethyldiethoxysilane, vinyloxypropylmethyldimethoxysilane, vinyloxypropylmethyldiethoxysilane, vinyloxypropyl Methyldipropoxysilane, vinyloxypropylmethyldibutoxysilane, vinyloxypropylmethyldibutoxysilane, vinyloxypropylmethyldimethoxyethoxysilane, vinyloxypropylmethyldiphenoxysilane, vinyloxypropylethyldiethoxysilane, vinyloxypropylethyldi Ethoxysilane, vinyloxypropylethyldipropoxysilane, vinyloxypropylvinyldimethoxysilane and the like can be mentioned.

These compounds of the general formula (I) may be used singly or in combination of two or more according to the purpose. Further, these compounds of the general formula (I)
It is also possible to use a mixture with a silane compound other than the general formula (I). Examples of silane compounds that can be mixed with the compounds of general formula (I) include many substances,
For example, methyltrimethoxysilane, methyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriacetoxysilane, vinyltrimethoxyethoxysilane, γ-methacryloxypropyltrimethoxysilane, aminomethyltrimethoxysilane, Aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, γ-chloropropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, 3,3,3-trifluoro Various trialkoxysilanes such as propyltrimethoxysilane, trisiloxysilane or trialkoxyalkoxysilane compounds, dimethyldimethoxysilane, diphenyldimethoxysilane, Ruch enyl dimethoxysilane,
Dialkoxysilane compounds such as methylvinyldimethoxysilane and dimethyldiethoxysilane, methyl silicate, ethyl silicate, isopropyl silicate, n-
4-functional silane compounds such as propyl silicate, n-butyl silicate, t-butyl silicate, sec-butyl silicate, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropyl Trimethoxyethoxysilane, γ-glycidoxypropyltriacetoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriethoxysilane, β- (3 4-epoxycyclohexyl) ethyltrimethoxyethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriacetoxysilane, γ-glycidoxypropyldimethoxymethylsilane, γ-glycidoxypropyldiethoxymethylsilane, γ-glycid Xypropyldimethoxyethoxymethylsilane, γ-glycidoxypropyldiacetoxymethylsilane, β- (3,4-epoxycyclohexyl) ethyldimethoxymethylsilane, β- (3
4-epoxycyclohexyl) ethyldiethoxymethylsilane, β- (3,4-epoxycyclohexyl) ethyldimethoxyethoxymethylsilane, β- (3,4-epoxycyclohexyl) ethyldiacetoxymethylsilane, γ-glycidoxypropyldimethoxy Ethyl silane, γ-glycidoxypropyldiethoxyethylsilane, γ-glycidoxypropyldimethoxyethoxyethylsilane, γ-glycidoxypropyldiacetoxyethylsilane, β- (3,4-epoxycyclohexyl) ethyldimethoxyethylsilane , Β- (3,4-epoxycyclohexyl) ethyldiethoxyethylsilane, β-
(3,4-epoxycyclohexyl) ethyldimethoxyethoxyethylsilane, β- (3,4-epoxycyclohexyl) ethyldiacetoxyethylsilane, γ-glycidoxypropyldimethoxyisopropylsilane, γ-
Glycidoxypropyldiethoxyisopropylsilane,
γ-glycidoxypropyldimethoxyethoxyisopropylsilane, γ-glycidoxypropyldiacetoxyisopropylsilane, β- (3,4-epoxycyclohexyl) ethyldimethoxyisopropylsilane, β-
(3,4-epoxycyclohexyl) ethyldiethoxyisopropylsilane, β- (3,4-epoxycyclohexyl) ethyldimethoxyethoxyisopropylsilane, β- (3,4-epoxycyclohexyl) ethyldiacetoxyisopropylsilane, γ-glycid Xypropylmethoxydimethylsilane, γ-glycidoxypropylethoxydimethylsilane, γ-glycidoxypropylmethoxyethoxydimethylsilane, γ-glycidoxypropylacetoxydimethylsilane, β- (3,4-epoxycyclohexyl) ethylmethoxydimethyl Silane,
β- (3,4-epoxycyclohexyl) ethylethoxydimethylsilane, β- (3,4-epoxycyclohexyl) ethylmethoxyethoxydimethylsilane, β-
(3,4-epoxycyclohexyl) ethylacetoxydimethylsilane, γ-glycidoxypropylmethoxydiethylsilane, γ-glycidoxypropylethoxydiethylsilane, γ-glycidoxypropylmethoxyethoxydiethylsilane, γ-glycidoxypropyl Acetoxydiethylsilane, β- (3,4-epoxycyclohexyl) ethylmethoxydiethylsilane, β- (3,4-
Epoxycyclohexyl) ethylethoxydiethylsilane, β- (3,4-epoxycyclohexyl) ethylmethoxyethoxydiethylsilane, β- (3,4-epoxycyclohexyl) ethylacetoxydiethylsilane,
γ-glycidoxypropylmethoxydiisopropylsilane, γ-glycidoxypropylethoxydiisopropylsilane, γ-glycidoxypropylmethoxyethoxydiisopropylsilane, γ-glycidoxypropylacetoxydiisopropylsilane, β- (3,4-epoxycyclohexyl) ) Ethylmethoxydiisopropylsilane,
β- (3,4-epoxycyclohexyl) ethylethoxydiisopropylsilane, β- (3,4-epoxycyclohexyl) ethylmethoxyethoxydiisopropylsilane, β- (3,4-epoxycyclohexyl) ethylacetoxydiisopropylsilane, γ-glycid Xypropylmethoxyethoxymethylsilane, γ-glycidoxypropylacetoxymethoxymethylsilane, γ-glycidoxypropylacetoxyethoxymethylsilane, β
-(3,4-epoxycyclohexyl) ethylmethoxyethoxymethylsilane, β- (3,4-epoxycyclohexyl) ethylmethoxyacetoxymethylsilane, β
-(3,4-epoxycyclohexyl) ethylethoxyacetoxymethylsilane, γ-glycidoxypropylmethoxyethoxyethylsilane, γ-glycidoxypropylacetoxymethoxyethylsilane, γ-glycidoxypropylacetoxyethoxyethylsilane, β- (3,
4-epoxycyclohexyl) ethylmethoxyethoxyethylsilane, β- (3,4-epoxycyclohexyl) ethylmethoxyacetoxyethylsilane, β-
(3,4-epoxycyclohexyl) ethylethoxyacetoxyethylsilane, γ-glycidoxypropylmethoxyethoxyisopropylsilane, γ-glycidoxypropylacetoxymethoxyisopropylsilane, γ-glycidoxypropylacetoxyethoxyisopropylsilane, β- ( 3,4-epoxycyclohexyl) ethylmethoxyethoxyisopropylsilane, β- (3,4-
Epoxycyclohexyl) ethylmethoxyacetoxyisopropylsilane, β- (3,4-epoxycyclohexyl) ethylethoxyacetoxyisopropylsilane,
Glycidoxymethyltrimethoxysilane, glycidoxymethyltriethoxysilane, α-glycidoxyethyltrimethoxysilane, α-glycidoxymethyltrimethoxysilane, β-glycidoxyethyltrimethoxysilane, β-glycid Xymethyltrimethoxysilane, α-
Glycidoxypropyltrimethoxysilane, α-glycidoxypropyltriethoxysilane, β-glycidoxypropyltrimethoxysilane, β-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltripropoxysilane, γ- Glycidoxypropyltributoxysilane, γ-glycidoxypropyltriphenoxysilane, α-glycidoxybutyltrimethoxysilane,
α-glycidoxybutyltriethoxysilane, β-glycidoxybutyltrimethoxysilane, β-glycidoxybutyltriethoxysilane, γ-glycidoxybutyltrimethoxysilane, γ-glycidoxybutyltriethoxysilane, (3,4-epoxycyclohexyl) methyltrimethoxysilane, (3,4-epoxycyclohexyl) methyltriethoxysilane, β- (3,4-epoxycyclohexyl) ethyltripropoxysilane, β-
(3,4-epoxycyclohexyl) ethyltributoxysilane, β- (3,4-epoxycyclohexyl) ethyltriphenoxysilane, γ- (3,4-epoxycyclohexyl) propyltrimethoxysilane, γ-
(3,4-epoxycyclohexyl) propyltriethoxysilane, δ- (3,4-epoxycyclohexyl)
Butyltrimethoxysilane, δ- (3,4-epoxycyclohexyl) butyltriethoxysilane, glycidoxymethylmethyldimethoxysilane, glycidoxymethylmethyldiethoxysilane, α-glycidoxyethylmethyldimethoxysilane, α-gly Sidoxyethylmethyldiethoxysilane, β-glycidoxyethylmethyldimethoxysilane, β-glycidoxyethylmethyldiethoxysilane, α-glycidoxypropylmethyldimethoxysilane, α-glycidoxypropylmethyldiethoxysilane, β-glycidoxypropylmethyldimethoxysilane, β-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropylmethyl Dipropoxysilane, γ-glycidoxypropylmethyldibutoxysilane, γ-glycidoxypropylmethyldimethoxyethoxysilane, γ-glycidoxypropylmethyldiphenoxysilane, γ-glycidoxypropylethyldimethoxysilane, γ-gly Epoxysilanes such as sidoxypropylethyldiethoxysilane, γ-glycidoxypropylethyldipropoxysilane, γ-glycidoxypropylvinyldimethoxysilane, γ-glycidoxypropylvinyldiethoxysilane, methyl silicate, ethyl silicate, Isopropyl silicate, n-propyl silicate, n-butyl silicate, t-butyl silicate, s
Examples include tetrafunctional silane compounds such as ec-butyl silicate.

The compound of the general formula (I) and the silane compound used by mixing the compound of the general formula (I) may be used as they are, or may be used as a hydrolyzate. When a plurality of substances are mixed and used, they may be mixed after hydrolysis or may be hydrolyzed after mixing. Upon hydrolysis, the alcohol HOR ³ is liberated, and the compound of general formula (I) has the corresponding silanol:

[0019]

Embedded image

## EQU1 ## Silanol is rapidly dehydrated and condensed to form an oligomer. Therefore, it may be left (cured) for 1 to 24 hours after hydrolysis so that this reaction proceeds sufficiently. Description of Component (b) The component (b) used in the present invention is a polymerization initiator that generates an acid by an active energy ray.

The active energy ray in the present invention means ultraviolet ray, visible ray, infrared ray, electron beam, radiation and the like. By the action of the acid generated by the irradiation of these active energy rays, the polycondensation reaction of the silane compound and the polymerization reaction of the methacryloxy group or the acryloxy group proceed, and the curing reaction proceeds. In the present invention, a composition containing a polymerization initiator that generates an acid upon irradiation with active energy rays is referred to as an active energy ray-curable coating composition.

Generates acid by irradiation with active energy rays
Some specific examples of the polymerization initiator are given below.
Is not limited to these. As a specific example,
R^Four _TwoI⁺X^- , R^Four _ThreeS⁺X^- , R^Four _TwoR^FiveS⁺X^- , R^FourR^Five _Two
S⁺X ^- , R^Four _ThreeSe⁺X^- , R^Four _FourP⁺X^- , R^FourN_Two ⁺X^- ,
R^Five _TwoI⁺X^-, R^Five _ThreeS⁺X^-, R^Five _TwoR⁶S⁺X^-, R^FiveR⁶ _TwoS⁺
X^-, R^Five _ThreeSe⁺X⁻, R^Five _FourP⁺X^-, R^FiveN_Two ⁺X^-(Where
R^FourIs an aryl group, R^FiveIs an alkyl group, X^-Is SbF₆ ^-,
AsF₆ ^-, PF₆ ^-, BF_Four ^-, HSO_Four ^-, ClO_Four ^-, Cl
^-, CF_ThreeSO_Three ^-, B (C₆F_Five)_Four ^-Anion)
Diaryl iodonium salt, triaryl sulfo
Salt, diarylmonoalkylsulfonium salt,
Noaryldialkylsulfonium salt, triarylse
Lenonium salt, tetraarylphosphonium salt, aryl
Rudiazonium salt, further, aromatic diazonium salt,
Aromatic sulfonium salt, aromatic iodonium salt, aromatic
Selenonium salts, aromatic phosphonium salts, and metalloses
Compounds, silicon compounds and aluminum chelate compounds
Can be used.

These active energy ray polymerization initiators (b)
It is appropriate to add 0.01 to 20 parts by weight based on 100 parts by weight of the total of the components (a) and (c).
If the amount is less than 0.01 part by weight, the curability becomes insufficient, and if it is more than 20 parts by weight, the surface state of the cured film is adversely affected, and cracks and the like may occur. (B)
Since the addition amount of the component is effective against the functional group of the component (a), the addition amount when the component (c) is not included as described above is the same as the above addition amount.

These active energy ray polymerization initiators may be used alone or in combination of two or more. Description of Component (c) The component (c) used in the present invention includes Al, Si, S
n, Sb, Ta, Ce, La, Fe, Zn, W, Zr,
It is composed of fine particles of an oxide of one or more metals selected from In and Ti and having a particle size of 1 to 100 mm. Or a particle size of 1 or more composed of two or more oxides of the metal
100 millimicron composite particles or solid solutions or mixtures thereof. These single oxide fine particles can be used in a state where they are present together with a mixture / and / or a composite particle and / or a solid solution.

Specific examples of the oxide include Al_TwoO_Three,
SiO_Two, SnO_Two, Sb_TwoO_Five, Ta _TwoO_Five, CeO_Two, L
a_TwoO_Three, Fe_TwoO_Three, FeO, ZnO, WO_Three, ZrO_Two,
In_TwoO_Three, TiO_TwoInorganic oxide fine particles such as
iO_Two, Al_TwoO_Three, SnO_Two, Sb_TwoO_Five, Ta_TwoO_Five, Ce
O_Two, La_TwoO_Three, Fe_TwoO_Three, FeO, ZnO, WO_Three, Z
rO_Two, In_TwoO_Three, TiO_TwoTwo or more inorganic oxides such as
Composite oxide fine particles or solid solution composed of
Can be fine particles of the mixture.

The composite oxide fine particles in the present invention are those in which two or more kinds of oxides are mixed while maintaining their respective structures. A solid solution is one in which two or more substances are mixed to form one crystal structure. These fine particles can be used by dispersing them in a dispersion medium such as water, an alcohol, or another organic solvent.

In order to further improve the dispersion stability in the coating liquid, it is possible to use those obtained by treating the surfaces of these fine particles with an organic silicon compound. As the organic silicon compound used at this time, there are monofunctional silane, difunctional silane, trifunctional silane, tetrafunctional silane and the like. In the treatment, the hydrolyzable group may be untreated or hydrolyzed. After the treatment, a state in which the hydrolyzable group has reacted with the —OH group of the fine particles is desirable, but there is no problem in stability even when a part remains. The amount of the organic silicon compound to be added is preferably in the range of about 1 to 15% based on the weight of the fine particles. In any case, the particle diameter is preferably about 1 to 300 mm.

The fine particle concentration of the coating composition of the present invention is desirably adjusted so that the solid content concentration is about 10 to 70% by weight. If the amount is less than 10% by weight, the scratch resistance of the coating film becomes insufficient. On the other hand, if it exceeds 70% by weight, appearance defects such as cracks occur in the coating film. (D) Description of the component In the present invention, it is sufficiently possible to form a coating film having a sufficient hardness only by irradiation with active energy rays. When the durability to the wire is not so strong, it is possible to use a thermosetting catalyst in addition to the active energy ray polymerization initiator. As a result, the curing time can be reduced, and the active energy dose to be irradiated can be reduced, and the effect of the active energy ray on the plastic substrate can be reduced. This is effective when a material that is adversely affected by irradiation with active energy rays is used.

The curing time can be further shortened by the combination of irradiation with active energy rays and heating. In the present invention, the following substances can be added as a thermosetting catalyst, but the thermosetting catalyst that can be used in the present invention is not limited to the following. (1) Various metal complex compounds: General formula: MXn Y _3-n (where X is OL (L is a lower alkyl group), and Y is general formula M ¹ COCH ₂ COM ² (M ¹ and M ² are A lower alkyl group) and a ligand derived from M ¹ COCH ₂ COOM ² , wherein n is 0, 1 or 2, and M is a metal.

Particularly useful chelate compounds include aluminum acetylacetonate, aluminum bisethylacetoacetate monoacetylacetonate, and aluminum-di-n from the viewpoints of solubility, stability, and catalyst curing.
-Butoxide-monoethylacetoacetate, aluminum-di-iso-propoxide-monomethylacetoacetate and the like.

In addition, chromium acetylacetonate, titanyl acetylacetonate, cobalt acetylacetonate, iron acetylacetonate, manganese acetylacetonate, nickel acetylacetonate, EDT
A, and also a complex compound of Al, Fe, Zn, Zr, and Ti. (2) Metal alkoxide: aluminum triethoxide, aluminum tri-n-propoxide, aluminum tri-n-butoxide, tetraethoxytitanium, tetra-n-butoxytitanium, tetra-i-propoxytitanium.

(3) Organic metal salts: sodium acetate, zinc naphthenate, cobalt naphthenate, zinc octylate, tin octylate. (4) Perchlorates: magnesium perchlorate, ammonium perchlorate. (5) Organic acids or anhydrides: malonic acid, succinic acid, tartaric acid, adipic acid, azelaic acid, maleic acid, o-phthalic acid, terephthalic acid, fumaric acid, itaconic acid, oxaloacetic acid, succinic anhydride, maleic anhydride Acid, itaconic anhydride, 1,2-dimethylmaleic anhydride, phthalic anhydride, hexahydrophthalic anhydride, naphthalic anhydride.

(6) Lewis acid: ferric chloride, aluminum chloride. (7) Metal halide: stannous chloride, stannic chloride,
Tin bromide, zinc chloride, zinc bromide, titanium tetrachloride, titanium bromide, thallium bromide, germanium chloride, hafnium chloride, lead chloride, lead bromide.

These catalysts may be used alone or in combination of two or more. Further, in order to improve the coating properties of the coating solution and the film performance after curing, a small amount of a surfactant, an antistatic agent, an antioxidant, a disperse dye, a fusible dye, a fluorescent dye, Dyes, pigments, photochromic compounds, hindered amines, light- and heat-resistant stabilizers such as hindered phenols and the like can also be added. Further, under conditions where the use of an organic solvent does not adversely affect the material, the material can be diluted with an organic solvent before use.

Thus, (a) as described above,
(B) component, or (a), (b), (c) component or (a), (b), (d) component, or (a),
The coating composition of the present invention can be obtained by adding and mixing the components (b), (c) and (d) as essential components. As the substrate on which the coating composition of the present invention can be coated, any type of resin such as a thermosetting resin, a thermoplastic resin, an ultraviolet curable resin, and a radiation curable resin can be used. Specific examples of usable plastic substrates include diethylene glycol bisallyl carbonate (CR39), styrene, α-methylstyrene, chlorostyrene, phenyl methacrylate, phenyl acrylate, benzyl methacrylate, benzyl acrylate, naphthyl methacrylate, naphthyl acrylate,
(Di) methacrylate of tetrabromobisphenol derivative, (di) acrylate of tetrabromobisphenol derivative, diallyl carbonate of tetrabromobisphenol derivative, methyl methacrylate, (di) ethylene glycol methacrylate, (di) ethylene glycol acrylate, vinylnaphthalene, divinylbenzene And the like, and 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, 3
-Hydroxypropyl methacrylate, 3-hydroxypropyl acrylate, 2,3-hydroxypropyl methacrylate, hydroxy methacrylate such as 2,3-hydroxypropyl acrylate or hydroxy acrylate and xylylene diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate,
A reaction product of a polyfunctional (poly) isocyanate such as a cyclic trimer of hexamethylene diisocyanate, and a di (2-
Mercaptoethyl) ether, 1,2-ethanedithiol, di (2-mercaptoethyl) sulfide, 2-mercaptoethanol, pentaerythritol tetrakis-
Reaction products of thiol compounds such as 3-mercaptopropionate and 4-mercaptomethyl-3,6-dithia-1,8-octanediol with polyfunctional (poly) isocyanate or polyfunctional (poly) ene and mixtures thereof ( Polycarbonate and the like), but are not limited thereto.

The coating composition of the present invention can be widely applied to synthetic fibers, inorganic fibers, metals, ceramics, glass materials and composite materials thereof, wood and the like. Means for applying the composition of the present invention to a substrate include brush coating, roll coating, gravure coating, wire doctor coating, spray coating, spin coating, dipping coating,
Any ordinary coating method such as flow coating can be used.

It is appropriate that the film thickness is 0.1 μm or more and 20 μm or less. When the film thickness is 0.1 μm or less, sufficient surface hardness cannot be given to the substrate. On the other hand, it is difficult to cure a coating layer having a thickness of 20 microns or more uniformly in a short time. Examples of the active energy ray source used when curing the coating film of the present invention include mercury arc lamps, high-pressure mercury lamps, low-pressure mercury lamps, metal halide lamps, halogen lamps, various electron beam sources, various radiation sources, and the like. it can.
When curing is performed using an electron beam source, the component (b) may not be present.

The heating temperature in the case where a heat curing catalyst is added and active energy ray irradiation and heating are used in combination is preferably about 30 ° C. or more and about 150 ° C. or less. When the temperature is lower than about 30 ° C., the effect of heating is not substantially observed, and when the temperature is higher than about 150 ° C., the heat resistance temperature of many plastic substrates is exceeded, which is not preferable. The heating can be performed before, during, or after the irradiation of the active energy ray.

The irradiation time of the active energy ray is preferably about 1 second or more and about 15 minutes or less. If the time is shorter than about 1 second, a problem that the curing reaction does not proceed sufficiently occurs. On the other hand, since the curing reaction is generally completed within about 15 minutes, no further irradiation is required. However, there is no problem even if the curing time is set to 15 minutes or more by setting some conditions. When the curing reaction requires 15 minutes or more, an irradiation time corresponding to the curing reaction is set.

Further, the hard coat layer according to the present invention can be formed after forming the primer layer on the surface of the substrate for the purpose of improving impact resistance and adhesion. Thereby, the adhesiveness and the impact resistance can be improved as well as the scratch resistance. As a material for forming the primer layer, a urethane-based material can be used. In particular, those comprising an active hydrogen-containing compound and a polyisocyanate are preferred.
As the active hydrogen compound, ethylene glycol, 1,2
-Propylene glycol, 1,3 butanediol, 1,
Examples thereof include alkylene glycols such as 6-hexanediol, neopentyl glycol, and diethylene glycol, poly (alkylene carbonate) s, and silicone polyols, and other active hydrogen-containing compounds can also be used.

As the polyisocyanate, tolylene diisocyanate, xylylene diisocyanate, 4,4
4'-diphenylmethane diisocyanate, 1,5-naphthalenediisocyanate, 3,3'-dimethyl-4,
4′-diphenyl diisocyanate, aromatic diisocyanate, 1,6-hexamethylene diisocyanate,
Examples include aliphatic diisocyanates such as isophorone diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, and trimethylhexamethylene diisocyanate. Block type polyisocyanates can also be used.

The urethane-based material made of such a material may be in the form of a solution in which the urethane-based material is added to a solvent such as water, or the urethane-based material may be used in the form of an aqueous emulsion. The thickness of the primer layer containing the urethane-based material is preferably 0.01 to 30 μm.

It is also possible to form the primer layer with a material containing a crosslinked polyvinyl acetal as a main component. This is a cross-linked polyvinyl acetal,
An organosilane compound or a hydrolyzate thereof, an alkoxide compound or alkoxide dikenate compound of aluminum or titanium, and a curing catalyst are dissolved. The coating is applied to the surface of a substrate and heated to form a film.

The polyvinyl acetal has the following general formula (I)
Those represented by I) can be preferably used. General formula (II)

[0045]

Embedded image

(Wherein, R ¹ is a hydrogen atom or carbon atom 1)
A is the composition of the repeating unit having an acetal group (fraction of the structural unit);
90 and b are the compositions of the repeating units having an OH group (fraction of constituent units), and 10 to 90; c are the compositions of the repeating units having an acetyl group (fraction of constituent units), and are 0 to 1;
0, and a + b + c + 100) As the polyvinyl acetal of the general formula (II), those having a short prime number of a saturated hydrocarbon group of an acetal portion of 0 to 20 can be used, and preferably 0 to 10. Further, the carbon chain of the saturated hydrocarbon portion may not have a straight-chain structure, and may have a branch. The degree of polymerization of polyvinyl acetal is 50
Although those having a value of 00 or less are good, those having a value of 100 to 3000 are more preferable.

The content of polyvinyl acetal in the composition to be a primer layer is preferably from 1 to 30% by weight, more preferably from 2 to 20% by weight. Further, it is possible to adjust the refractive index and the hardness by adding inorganic oxide fine particles to the primer layer. As the particulate inorganic oxide that can be used, those used as the component (c) of the present invention can be used.

The thickness of the primer layer containing polyvinyl acetal is preferably 0.05 to 5 μm. It is also possible to form an antireflection film on the film of the present invention. Materials constituting the antireflection film include silicon oxide,
Inorganic oxides such as aluminum oxide, titanium oxide, zirconium oxide, and zinc oxide are preferable, and are formed by a method such as a vacuum evaporation method or a sputtering method.

Further, it is possible to form a hard coat of the present invention on a plastic lens substrate dyed with a dye or a pigment, and it is possible to easily produce a molded article having excellent fashionability and excellent scratch resistance. Become. As a dyeing method, an immersion method, a vacuum evaporation method, a spray method, a brush coating method, or the like can be used. The hard coat of the present invention can also be formed on the surface of a photochromic lens in which a photochromic material is applied to the surface of a plastic substrate, and then only the vicinity of the substrate surface is impregnated with a photochromic compound.

It is also possible to disperse a dye or pigment in a hard coat liquid and apply it. Alternatively, a hard coat may be applied, and after curing, the hard coat may be dyed with a dye or a pigment. It is also possible to form a water-repellent film on the outermost layer. By forming the water-repellent film, an article having water repellency and scratch resistance can be obtained. As the substance forming the water-repellent film, an organic silicon compound containing a fluoride can be used. Preferably, a polymer obtained by polymerizing a perfluoroalkyl group-containing organic silicon compound is used. A substituent having an amino group and / or an alkoxy group can be used as a substituent relating to the bond. The substituent is bonded to the Si atom of the organosilicon compound, and the substituent is
Any of the functional ones or mixtures thereof are used. Furthermore, in order to impart high durability to the water-repellent film,
It is more preferable that the water-repellent film after film formation has a crosslinked structure.

Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples.

[0052]

Example 1 (1) Preparation of coating composition: A reaction vessel equipped with a rotor was charged with 120 parts by weight of vinyloxytrimethoxysilane as the component (a) and stirred vigorously using a magnetic stirrer. As a component (b), 1 part by weight of Adeka Optomer sp-170 (manufactured by Asahi Denka Kogyo KK), which is a triarylsulfonium salt-based material, was added to prepare a coating composition.

(2) Coating and curing: refractive index nd = 1.50
Diethylene glycol bisallyl carbonate (CR
39) is prepared, and the coating composition is applied to the substrate by a spin method (rotation speed: 1000 rpm / 10 seconds). Then, ultraviolet irradiation and heating (80 ° C.) are performed by an ultraviolet irradiation apparatus (manufactured by Mitsubishi Rayon Engineering Co., Ltd.). ) Was performed simultaneously for 30 seconds to cure the coating.

(3) Evaluation: The substrate with the cured coating film obtained in (2) was subjected to the following test to evaluate the performance of the coating film. (A) Friction resistance test The surface of the coating film was rubbed with steel wool # 0000, and the scratch resistance was examined. In addition, evaluation was performed as follows.

◎: No damage is caused by strong friction. …: Slightly scratched when rubbed quite strongly. ×: Scratches even with weak friction. Incidentally, the evaluation of the substrate without the coating film was x. (B) Adhesion After immersing the substrate having the cured coating film in hot water of 90 ° C. for 2 hours,
100 goban eyes were made by making cut lines in the vertical and horizontal directions every 1 mm with a knife on the coating surface, and then a cellophane adhesive tape (trade name "Cellotape" manufactured by Nichiban Co., Ltd.) was strongly adhered. The end of the tape was quickly peeled off in the direction of 90 degrees with the hand in hand, and the number of goban eyes of the coating film was examined. The number X of the eyes of the peeled goban is expressed as X / 100 with the numerator as the numerator. The smaller the X, the better the adhesion.

[0056]

Example 2 (1) Preparation of Preliminary Composition A: A reaction vessel equipped with a rotor was charged with 250 parts by weight of vinyloxytrimethoxysilane, and 0.05 N while stirring vigorously using a magnetic stirrer. Hydrochloric acid (41 parts by weight) was gradually added.

Immediately after the addition, the solution was heterogeneous, but it became a uniform, colorless and transparent solution while generating heat within a few minutes. Stirring was further continued for 1 hour to obtain a hydrolyzate corresponding to the component (a). After adding 56.6 parts by weight of ethanol and 53.4 parts by weight of ethylene glycol to the obtained hydrolyzate,
As a component (d), 4.7 parts by weight of aluminum acetylacetonate was added and sufficiently mixed and dissolved to prepare a preliminary composition A.

(2) Preparation of coating composition: 150 parts by weight of the preliminary composition A prepared in the above (1) was weighed in a glass container, and silica sol (methanol dispersion sol, average particle diameter, : 13 ± 1 mμ, solid content 20
% By weight) and then 0.4 part by weight of a silicone surfactant. Further, 3 parts by weight of Adeka Optomer sp-170 (manufactured by Asahi Denka Kogyo Co., Ltd.) was added as the component (b), and the mixture was sufficiently stirred and mixed to prepare a uniform, colorless and transparent coating composition.

(3) Coating and curing: A film was coated and cured in the same manner as in Example 1. (4) Evaluation: Evaluation was performed in the same manner as in Example 1.

[0060]

Example 3 (1) Preparation of Preliminary Composition B: 200 parts by weight of vinyloxytriethoxysilane was charged into a reaction vessel equipped with a rotor, and 0.05 N while stirring vigorously using a magnetic stirrer. 46 parts by weight of hydrochloric acid were gradually added.

Immediately after the addition, the solution was heterogeneous, but it became a uniform, colorless and transparent solution while generating heat within a few minutes. Stirring was further continued for 1 hour to obtain a hydrolyzate corresponding to the component (a). After adding 30 parts by weight of methanol to the obtained hydrolyzate, 3.5 parts by weight of aluminum acetylacetonate was added as the component (d), and the mixture was sufficiently mixed and dissolved.
Preparatory composition B was prepared.

(2) Preparation of coating composition: 100 parts by weight of the preliminary composition B prepared in the above (1) was weighed in a glass container, and silica sol (methanol dispersion sol, average particle diameter : 13 ± 1 mμ, solid content 20
%) And then 0.1 part by weight of a fluorosurfactant.
8 parts by weight, and 3 parts by weight of Adeka Optomer sp-150 (manufactured by Asahi Denka Kogyo Co., Ltd.) as the component (b), and thoroughly agitate and mix to obtain a uniform, colorless and transparent coating composition. Prepared.

(3) Coating and curing: A film was coated and cured in the same manner as in Example 1. (4) Evaluation was performed in the same manner as in Example 1.

[0064]

Example 4 The component (c) in Example 2 was replaced with commercially available colloidal particles of a composite of tin oxide and tungsten oxide (average particle diameter: 30 ± 1 μm, solid content 20%), and (b)
A coating composition of this example was prepared in the same manner as in Example 2 except that 5 parts by weight of UVI-6990 (manufactured by Union Carbide) was added as a component, and evaluation was performed after film formation.

[0065]

Example 5 In Example 3, a commercially available antimony pentoxide sol (average particle diameter: 15 mμ, solid content: 20%) was used in place of the silica sol as the component (c), and UVI-6950 was used as the component (b). A coating composition of this example was prepared and evaluated in the same manner as in Example 3, except that 5 parts by weight (manufactured by Union Carbide) was added.

[0066]

Example 6 (1) Preparation of Preliminary Composition C: A reaction vessel equipped with a rotor was charged with 250 parts by weight of vinyloxytrimethoxysilane and 0.05 N with vigorous stirring using a magnetic stirrer. Hydrochloric acid (41 parts by weight) was gradually added.

Immediately after the addition, the solution was a heterogeneous solution. However, the solution became homogeneous and colorless and transparent while generating heat within a few minutes. Stirring was further continued for 1 hour to obtain a hydrolyzate corresponding to the component (a). To the obtained hydrolyzate, 56.6 parts by weight of ethanol and 53.4 parts by weight of ethylene glycol were added to prepare Preparatory Composition C. (2) Preparation of coating composition: A coating composition of this example was prepared in the same manner as in Example 2.

(3) Coating and curing: A film was coated and cured in the same manner as in Example 1 except that heating was not performed during curing. (4) Evaluation was performed in the same manner as in Example 1. [Comparative Example 1] A coating composition of this example was prepared and evaluated in the same manner as in Example 2, except that the ADEKA OPTOMER sp-170 as the component (b) was not added.

[Comparative Example 2] A coating composition of this example was prepared and evaluated in the same manner as in Example 3, except that the ADEKA OPTOMER sp-150 as the component (b) was not added. . The results of the above evaluation are shown in Table 1 below.

[0070]

[Table 1]

As can be seen from Table 1, the evaluations of Examples 1 to 6 according to the present invention were excellent, and Comparative Examples 1 and 2 were inferior.

[0072]

The present invention has the following effects. (1) According to the present invention, since a film can be formed on a substrate without a heating step, the substrate is not heated, and has a high surface hardness even on a substrate made of a material having low heat resistance. A hard coat can be easily formed.

(2) According to the present invention, since the film can be cured by irradiating it with an active energy ray, a hard coating film can be formed in a short time and the production efficiency is improved. Further, by curing using both irradiation of active energy rays and heating, the curing time can be further shortened, and the production time and production cost can be reduced. (3) In the present invention, since a silane having a vinyloxy group is used as the component (a), it can be cured in a short time by irradiation with an active energy ray, and a film having a further small shrinkage can be obtained. Therefore, a molded body in which the substrate after film formation is unlikely to warp can be easily and efficiently manufactured in a short time. Particularly when the base material is thin, a remarkable effect is exhibited. For example, if a film is formed on a spectacle lens in which the lens thickness tends to become thinner as the refractive index increases, a high-refractive-index lens with less warpage can be easily obtained.

(4) The film of the present invention has a large film elongation,
Even if the base material is bent, a molded article having excellent durability without cracking of the film can be obtained. (5) Since the film of the present invention has a structure in which a disperse dye is more easily impregnated than a film cured by conventional heating, it can be easily dyed and a durable dyed lens can be easily obtained. It is.

(6) The film surface of the present invention has good sliding properties and a small coefficient of friction. Therefore, it is hard to be damaged, and is excellent in abrasion resistance and abrasion resistance. (7) The film of the present invention has excellent adhesion to a substrate, and is excellent in transparency, heat resistance and water resistance. In addition, a molded article having excellent antistatic properties and being hardly stained can be obtained.

Continued on the front page (72) Inventor Toru Nakamura 3-2-2, Marunouchi, Chiyoda-ku, Tokyo Nikon Corporation

Claims (7)

[Claims] An active energy ray-curable coating composition comprising the following components (a) and (b): (A) General formula (I): R ¹ aR ² bSi (OR ³ ) _{4- (a + b)} (wherein, R ¹ is an organic group having 4 to 14 carbon atoms having a vinyloxy group, R ² is a hydrocarbon group having 1 to 6 carbon atoms or a halogenated hydrocarbon group; R ₃ is an alkyl group, an alkoxyalkyl group or an acyl group having 1 to 4 carbon atoms, and a is 1 or more and 3 or less. Integer, b
Is an integer of 0, 1, or 2, and a + b is an integer of 1 or more and 3 or less. (B) a polymerization initiator that generates an acid upon irradiation with active energy rays 2. The coating composition according to claim 1, wherein the active energy ray-curable coating composition containing the components (a) and (b) contains the following component (c). (C) Al, Si, Sn, Sb, Ta, Ce, La, F
e, a fine particle having a particle diameter of 1 to 100 millimicrons composed of an oxide of one or more metals selected from Zn, W, Zr, In, and Ti and / or a particle diameter composed of oxides of two or more metals. 1-100 millimicron composite particles or solid solutions or mixtures thereof. 3. The coating composition according to claim 1, wherein the coating composition contains the following component (d). (D) Thermosetting catalyst 4. A molding composition comprising, as a main component, an organosilicon compound represented by the following formula or a hydrolyzate thereof, and a polymerization initiator which generates an acid when irradiated with an active energy ray. A method for producing a molded body, comprising: a coating step of applying the coating composition; and a film forming step of irradiating an active energy ray to the molded article coated with the coating composition to cure the coating composition. General formula (I): R ¹ aR ² bSi (OR ³ ) _{4- (a + b)} (wherein, R ¹ is an organic group having a vinyloxy group and having 4 to 14 carbon atoms, and R ² is A hydrocarbon group having 1 to 6 carbon atoms or a halogenated hydrocarbon group; R ³ is an alkyl group having 1 to 4 carbon atoms, an alkoxyalkyl group or an acyl group, and a is an integer of 1 to 3; b
Is an integer of 0, 1, or 2, and a + b is an integer of 1 or more and 3 or less. ) 5. The method according to claim 4, wherein in the film forming step, heating is performed together with irradiation of active energy rays. 6. The coating composition according to claim 1, wherein the particle size is 1 to 100.
Millimicron Al, Si, Sn, Sb, Ta, Ce,
Includes oxides of one or more metals selected from La, Fe, Zn, W, Zr, In and Ti and / or composite particles or solid solutions composed of two or more metal oxides or mixtures thereof. 4. The method according to claim 1, wherein
The method for producing a molded article according to the above. 7. A molded article characterized in that a coating containing a polymerization initiator which generates an acid upon irradiation with active energy rays is formed on a plastic substrate.