JPH1135886A - Coating composition and coated molded product and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject composition, capable of improving scuff resistance of a plastic lens substrate and useful for lenses of eyeglasses, etc., withstanding the use in various environments by including a specific organosilicon compound and a specified polymerization initiator therein. SOLUTION: This composition is obtained by including (A) an organosilicon compound represented by the formula, R<1> a R<2> b Si(OR<3> )4-(a+b) R<1> is a 4-14C organic group; R<2> is a 1-6C hydrocarbon group or the like; R<3> is a 1-4C alkyl, or the like: (a) is >=1; (b) is 0-2 and [(a+b)] is 1-3} (e.g. γ- glycidoxypropyltrimethoxysilane, etc.) or its hydrolyzate, (B) a polymerization initiator capable of generating an acid by irradiation with active energy rays, further (C) fine particles, composed of one or more metallic oxides selected from Al, Si, etc., and having 1-100 μ particle diameter and (D) a thermosetting catalyst. The amount of the component B is 0.01-20 pts.wt. based on 100 pts.wt. total amount of the components A and C.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a silicone coating composition which cures rapidly by short-time active energy ray irradiation or a combination of short-time active energy ray irradiation and short-time heating, and a protection comprising the coating composition. The present invention relates to a molded article having a coating layer 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, but on the other hand, the surface hardness is insufficient and scratches are generated. There are drawbacks such as easiness, susceptibility to solvent attack, electrification and adsorption of dust, and insufficient heat resistance, which may cause practical problems. In particular, when manufacturing a lens using a plastic material, these problems are important issues to be solved.

Therefore, it has been proposed to apply a protective coating layer such as a hard coat on the surface of a plastic molded article. For the purpose of improving scratch resistance, it is common to form a hard coat on the surface of a molded article. Conventionally, such a hard coat generally has a heat-curable resin as a main component (hereinafter referred to as a heat-curable hard coat), has a high hardness, and imparts excellent abrasion resistance to a plastic molded article. It has been widely used because of its advantages. As a film forming method, for example, a method of applying a coating liquid to be a hard coat to the surface of a plastic molded body by using a dipping method or a spin coating method, and then generally performing a heat treatment for several hours and curing the applied liquid. is there.

On the other hand, recently, as a protective coating layer which can be cured in a short time, a layer mainly composed of an ultraviolet-curable resin (hereinafter, referred to as an ultraviolet-curable coat) has been developed and spread. The UV-curable coat is formed by applying a coating liquid on the surface of a base material and then irradiating the coating liquid with ultraviolet light to cure the coating liquid. For example, Japanese Patent Publication No. Sho 59-30170 describes 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. 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 observing the substrate on which the hard coat was formed, 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, there was a problem that the formed ultraviolet-curable coat was inferior in scratch resistance as compared with the heat-curable hard coat.

In recent years, as for 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.

[0008]

Means for Solving the Problems The present inventors have searched for the cause of the deformation of the lens substrate which occurs 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 composition comprising (b). (A) General formula: R ¹ a R ² b Si (OR ³ ) _{4- (a + b)} (where R ¹ is an epoxy group-containing carbon number of 4 to 4)
14 organic groups, R ² is a hydrocarbon group having 1 to 6 carbon atoms or a halogenated hydrocarbon group, and R ³ is a 1-carbon group.
4 to 4 alkyl groups, alkoxyalkyl groups or acyl groups, a is 1 or more, b is 0 to 2, and a + b is
(B) a polymerization initiator (Claim 1) which generates an acid upon irradiation with active energy rays. Secondly, 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,
Particle diameter of 1 to 100 composed of oxide of one or more metals selected from Ce, La, Fe, Zn, W, Zr, In, and Ti
Composite fine particles or solid solutions having a particle diameter of 1 to 100 millimicrons, which are composed of fine particles of millimicrons and / or oxides of two or more metals, or a mixture thereof (Claim 2) "
I will provide a. Thirdly, "the coating composition containing the components (a) and (b) according to claim 1 or the components (a), (b) and (c) according to claim 2 contains the following component (d). Coating composition (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. And a film forming step of irradiating an active energy ray to the molded product coated with the coating composition to cure the coating composition.

General formula: R ¹ aR ² bSi (OR ³ ) _{4- (a + b)} (where R ¹ is an epoxy group-containing carbon number of 4 to 4).
14 organic groups, R ² is a hydrocarbon group having 1 to 6 carbon atoms or a halogenated hydrocarbon group, and R ³ is a 1-carbon group.
4 to 4 alkyl groups, alkoxyalkyl groups or acyl groups, a is 1 or more, b is 0 to 2, and a + b is
1-3) (Claim 4). Fifthly, the present invention provides "a method for producing a molded article according to claim 4, wherein in the film forming step, heating is carried out together with irradiation of active energy rays". Sixth, "the coating composition is made of Al, S having a particle size of 1 to 100 millimicrons.
i, Sn, Sb, Ta, Ce, La, Fe, Zn, W,
An oxide of one or more metals selected from Zr, In, and Ti and / or a composite particle or a solid solution composed of two or more metal oxides or a mixture thereof is contained. 4) and (5). Seventhly, there is provided 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 (claim 7)".

[0012]

DETAILED DESCRIPTION OF THE INVENTION The coating composition of the present invention comprises at least two components (a) and (b) or (a), (b), (c) or (a), (b), (D)
Or (a), (b), (c),
(D) Four components are included. Hereinafter, each component will be described in detail.

Description of the component (a) The component (a) usable in the present invention, that is, the general formula: R ¹ aR ² bSi (OR ³ ) _{4- (a + b)} (I) (wherein, R1 is an epoxy group having 4 to 4 carbon atoms
14 organic groups, R ² is a hydrocarbon group having 1 to 6 carbon atoms or a halogenated hydrocarbon group, and R ³ is a 1-carbon group.
4 to 4 alkyl groups, alkoxyalkyl groups or acyl groups, a is 1 or more, b is 0 to 2, and a + b is
1 to 3. The organic silicon compound represented by the formula (1) or a hydrolyzate thereof is a substance generally referred to as epoxysilane and a hydrolyzate thereof.

Specific examples of epoxysilane include, for example, γ-glycidoxypropyltrimethoxysilane, γ
-Glycidoxypropyltriethoxysilane, γ-glycidoxypropyltrimethoxyethoxysilane, 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-glycidoxypropyldimethoxyethoxymethylsilane, γ-glycidoxypropyldiacetoxy Methylsilane, β- (3,4-epoxycyclohexyl) ethyldimethoxymethylsilane, β- (3,4-epoxycyclohexyl) ethyldiethoxymethylsilane, β-
(3,4-epoxycyclohexyl) ethyldimethoxyethoxymethylsilane, β- (3,4-epoxycyclohexyl) ethyldiacetoxymethylsilane, γ-glycidoxypropyldimethoxyethylsilane, 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-epoxy Cyclohexyl) ethyldimethoxyethoxyisopropylsilane, β- (3,4-
Epoxycyclohexyl) ethyldiacetoxyisopropylsilane, γ-glycidoxypropylmethoxydimethylsilane, γ-glycidoxypropylethoxydimethylsilane, γ-glycidoxypropylmethoxyethoxydimethylsilane, γ-glycidoxypropylacetoxydimethylsilane, β- (3,4-epoxycyclohexyl) ethylmethoxydimethylsilane, β- (3,4-epoxycyclohexyl) ethylethoxydimethylsilane, β- (3,4-epoxycyclohexyl) ethylmethoxyethoxydimethylsilane, β- (3 , 4-epoxycyclohexyl) ethylacetoxydimethylsilane,
γ-glycidoxypropylmethoxydiethylsilane, γ
-Glycidoxypropylethoxydiethylsilane, γ-
Glycidoxypropylmethoxyethoxydiethylsilane, γ-glycidoxypropylacetoxydiethylsilane, β- (3,4-epoxycyclohexyl) ethylmethoxydiethylsilane, β- (3,4-epoxycyclohexyl) ethylethoxydiethylsilane, β -(3,
4-epoxycyclohexyl) ethylmethoxyethoxydiethylsilane, β- (3,4-epoxycyclohexyl) ethylacetoxydiethylsilane, γ-glycidoxypropylmethoxydiisopropyl silane, 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-glycidoxypropylmethoxyethoxymethylsilane, 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-glycidoxypropylmethoxyethoxyisopropyl Silane, 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-glycidoxymethyltrimethoxysilane, 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) ethyltryptoxysilane,
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-glycidoxyethylmethyldiethoxysilane, β-glycidoxyethylmethyl Dimethoxysilane,
β-glycidoxyethylmethyldiethoxysilane, α-
Glycidoxypropylmethyldimethoxysilane, α-glycidoxypropylmethyldiethoxysilane, β-glycidoxypropylmethyldimethoxysilane, β-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropylmethyldipropoxysilane, γ-glycidoxypropylmethyldibutoxysilane, γ-glycidoxypropylmethyldimethoxyethoxysilane, γ-glycidoxypropyl Methyldiphenoxysilane, γ-glycidoxypropylethyldimethoxysilane, γ-glycidoxypropylethyldiethoxysilane, γ-glycidoxypropylethyldipropoxysilane, γ-glycidoxypropylvinyldimethoxy Run, it may be mentioned γ- glycidoxypropyltrimethoxysilane vinyl diethoxy silane.

These compounds of the general formula (I) may be used alone or in combination of two or more according to the purpose. Further, these compounds of the general formula (I) can be used by mixing with a silane compound other than the general formula (I). Examples of the silane compound which can be mixed with the compound of the general formula (I) include many substances, for example, methyltrimethoxysilane, methyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriethoxysilane. Acetoxysilane, vinyltrimethoxyethoxysilane, γ-methacryloxypropyltrimethoxysilane, amenomethyltrimethoxysilane,
3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, γ-chloropropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, 3,3,3- Various trialkoxysilanes such as trifluoropropyltrimethoxysilane, trisiloxysilane or trialkoxyalkoxysilane compounds, dimethyldimethoxysilane, diphenyldimethoxysilane, methylphenyldimethoxysilane, methylvinyldimethoxysilane, and dimethyldiethoxysilane Alkoxysilane compound, methyl silicate,
Examples include tetrafunctional silane compounds such as ethyl silicate, isopropyl silicate, n-propyl silicate, n-butyl silicate, t-butyl silicate, and sec-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:

[0017]

Embedded image

## EQU1 ## Silanol is rapidly dehydrated and condensed to form an oligomer. Therefore, after hydrolysis, the reaction may be left (cured) for 1 to 24 hours 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 light ray, infrared ray, electron beam and radiation.
By the action of the acid generated by these active energy ray irradiations, the polycondensation reaction of the silane compound and the ring-opening polymerization reaction of the epoxy group proceed, and the curing reaction of the coating layer 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
And the like.

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).
When the amount is less than 0.01 part by weight, the curability becomes insufficient, and when the amount is more than 20 parts by weight, the surface state of the cured film is adversely affected, and cracks may be generated. Since the addition amount of the component (b) shows an effect on the functional group of the component (a), the addition amount when the component (c) is not contained as described above is the same as the above addition amount. .

These active energy ray polymerization initiators
May be used alone or as a mixture of two or more.
You may. Description of Component (c) The component (c) used in the present invention, namely, Al, Si, Sn,
Sb, Ta, Ce, La, Fe, Zn, W, Zr, I
consisting of an oxide of at least one metal selected from n and Ti
Fine particles having a particle size of 1 to 100 millimicrons and / or 2
Particle size of 1 to 10 composed of at least one kind of metal oxide
0 mm micron composite particles or solid solution or mixture thereof
Things. A specific example is Al_TwoO_Three, SiO_Two,
SnO_Two, Sb_TwoO_Five, Ta_TwoO_Five, CeO_Two, La_TwoO_Three, F
e_TwoO_Three, FeO, ZnO, WO_Three, ZrO_Two, In_TwoO_Three,
TiO_TwoSuch as inorganic oxide fine particles, or SiO_Two, A
l_TwoO _Three, SnO_Two, Sb_TwoO_Five, Ta_TwoO_Five, CeO_Two, La
_TwoO_Three, Fe_TwoO_Three, FeO, ZnO, WO_Three, ZrO_Two, I
n_TwoO_Three, TiO_TwoBy two or more inorganic oxides such as
Composite oxide fine particles or solid solution or a mixture thereof
Fine particles of the compound can be mentioned. In the present invention,
Composite oxide fine particles refer to two or more oxides having the respective structures.
Refers to the state of being mixed while maintaining the structure
You. A solid solution is a mixture of two or more substances,
One crystal structure is formed.

These fine particles can be used by dispersing them in a dispersion medium such as, for example, water, an alcohol or another organic solvent. Further, in order to enhance the dispersion stability in the coating liquid, it is also 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 may be 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 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. If it exceeds 70% by weight or more, poor appearance such as cracks will 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. If the durability to the radiation is not very strong, by using a heat curing catalyst in addition to the active energy ray polymerization initiator, the curing time can be shortened, and furthermore, the active energy dose to be irradiated can be reduced and the plastic substrate can be used. The effect of the active energy ray can be reduced. Further, it is also possible to realize curing in a shorter time by using both irradiation of active energy rays and heating. For example, the following substances can be added, 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: MX _n 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 , M ₂ is a lower alkyl group) and a ligand derived from M ₁ COCH ₂ COOM ₂ , and n is 0, 1 or 2, and M is a metal. Chelating compounds.

Particularly useful chelating 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 alkoxides: 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.

The above catalysts may be used alone or as a mixture of two or more. Further, the coating composition of the present invention may contain a small amount of a surfactant, an antistatic agent, an antioxidant, a disperse dye, a fusible dye, a fluorescent dye, a pigment, a photochromic compound, a hindered amine, a hindered phenol, etc., if necessary. The light- and heat-resistant stabilizers described above can be added to improve the applicability of the coating solution and the film performance after curing. When an organic solvent may be used, it can be used after being diluted with an organic solvent.

The coating composition of the present invention comprises the components (a) and (b) shown above, or (a), (b) and (c).
It is obtained by adding and mixing the components or the components (a), (b) and (d) or the components (a), (b), (c) and (d) as essential components. As a 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, and tetrabromobisphenol. Derivative (di) methacrylate, tetrabromobisphenol derivative (di) acrylate, tetrabromobisphenol derivative diallyl carbonate, methyl methacrylate, (di) ethylene glycol methacrylate, (di) ethylene glycol acrylate, vinylnaphthalene, divinylbenzene, and the like. It is possible,
Also, 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, 3-hydroxypropyl methacrylate, 3-hydroxypropyl acrylate,
2,3-hydroxypropyl methacrylate, 2,3-
Reaction products of hydroxy methacrylate such as hydroxypropyl acrylate or hydroxy acrylate and polyfunctional (poly) isocyanate such as xylylene diisocyanate, isophorone didiisocyanate, hexamethylene diisocyanate, cyclic trimer of hexamethylene diisocyanate, and di (2-mercapto) Ethyl) ether, 1,2-ethanedithiol, di (2-mercaptoethyl) sulfide, 2-mercaptoethanol, pentaerythritol tetrakis-3-mercaptopropionate, 4-mercaptomethyl-3,6-dithia-
Examples thereof include, but are not limited to, a reaction product of a thiol compound such as 1,8-octanediol and a polyfunctional (poly) isocyanate or a polyfunctional (poly) ene, and a mixture thereof (such as polycarbonate).

Further, 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 be 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 active energy ray sources used for curing the coating film of the present invention include mercury arc lamps, high-pressure mercury lamps, medium-pressure mercury lamps, low-pressure mercury lamps, metal halide lamps, halogen lamps, various electron beam sources, and various radiation sources. And the like. When curing using an electron beam source,
The component (b) may not be present.

When a thermosetting catalyst is added and active energy ray irradiation and heating are used in combination, the heating temperature is preferably 30 to 150 degrees Celsius. If the temperature is 30 degrees or less, the effect of heating is not substantially observed, and if it is 150 degrees or more, 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 1 second or more,
It is preferred that the time be 15 minutes or less. If less than 1 second, the curing reaction does not proceed sufficiently. On the other hand, the curing reaction is generally completed within 15 minutes, so that there is no need for further irradiation.
When the curing reaction requires 15 minutes or more, an irradiation time corresponding to the curing reaction is set. Further, in the present invention, the hard coat according to the present invention can be formed after forming the primer layer on the surface of the base material, and the adhesion and impact resistance can be improved as well as the scratch resistance. As a specific example of the 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. Examples of the active hydrogen compound include alkylene glycols such as ethylene glycol, 1,2-propylene glycol, 1,3 butanediol, 1,6-hexanediol, neopentyl glycol, and diethylene glycol or poly (alkylene carbonate), and silicon polyol. However, other active hydrogen-containing compounds can also be used.

The polyisocyanates include tolylene diisocyanate, xylylene diisocyanate, 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. Further, it is also possible to form the primer layer with a material containing a crosslinked polyvinyl acetal as a main component. This is obtained by dissolving a crosslinked polyvinyl acetal, an organosilane compound or a hydrolyzate thereof, an aluminum or titanium alkoxide compound or an alkoxide dikenate compound, and a curing catalyst. To form a film.

It is possible to adjust the refractive index and the hardness by adding a particulate inorganic oxide to these primer layers. The particulate inorganic oxide that can be used is (c) of the present invention.
What is used as an ingredient can be used. 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 the 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 excellent in fashionability and 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. Further, a water-repellent film can be formed on the outermost layer, and by forming the water-repellent film, an article having a water-repellent and hard coat 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 1 to
Any of the trifunctional ones or a mixture thereof is used. Further, in order to impart high durability to the water-repellent film, it is more preferable that the formed water-repellent film has a crosslinked structure.

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

[0042]

Example 1 (1) Preparation of coating composition: 100 parts by weight of γ-glycidoxypropylmethyldiethoxysilane was charged as a component (a) into a reaction vessel equipped with a rotor, and a magnetic stirrer was used. While stirring vigorously, 1 part by weight of Adeka Optomer sp-170 (manufactured by Asahi Denka Kogyo KK) was added as a component (b) to prepare a coating composition.

(2) Coating and curing: refractive index nd = 1.50
Diethylene glycol bisallyl carbonate (CR3
9) Prepare a substrate and apply it to the spin method (rotation speed 1000
After applying the above coating composition at (rpm / 10 seconds), ultraviolet irradiation and heating (80 degrees Celsius) were simultaneously performed for 30 seconds with an ultraviolet irradiation device (manufactured by Mitsubishi Rayon Engineering Co., Ltd.) to cure the coating film.

(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.

A: No damage is caused even 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.

[0046]

Example 2 (1) Preparation of Preliminary Composition A: γ-glycidoxypropylmethyldiethoxysilane 2 was placed in a reaction vessel equipped with a rotor.
48 parts by weight were charged, and 41 parts by weight of a 0.05 N hydrochloric acid aqueous solution were gradually added with vigorous stirring using a magnetic stirrer.

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: In a glass container, 150 parts by weight of the preliminary composition A prepared in the above (1) was weighed, and silica sol (methanol dispersed 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.

[0050]

Example 3 (1) Preparation of Preliminary Composition B: γ-glycidoxypropyltrimethoxysilane 200 was placed in a reaction vessel equipped with a rotor.
A part by weight was charged, and 46 parts by weight of a 0.05 N hydrochloric acid aqueous solution was gradually added while vigorously stirring using a magnetic stirrer.

Immediately after the addition, the solution was a heterogeneous solution, but became a 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 dispersed 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.

[0054]

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.

[0055]

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.

[0056]

Example 6 (1) Preparation of Preliminary Composition C: γ-glycidoxypropylmethyldiethoxysilane 2 in a reaction vessel equipped with a rotor
48 parts by weight were charged, and 41 parts by weight of a 0.05 N hydrochloric acid aqueous solution were gradually added with vigorous stirring using a magnetic stirrer.

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). Preliminary composition C was prepared by adding 56.6 parts by weight of ethanol and 53.4 parts by weight of ethylene glycol to the obtained hydrolyzate. (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.

[0060]

[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.

[0062]

The present invention has the following effects. (1) According to the present invention, since a heating step is not required when forming a film on a molded body, the substrate is not heated, and a high surface hardness is provided on a substrate made of a material having low heat resistance. Can easily be formed.

(2) Further, since the film is cured by irradiating active energy rays, a hard coating film can be formed in a short time, and the production efficiency is improved. In addition, by irradiating with active energy rays and curing in combination,
The curing time can be further reduced, and the production time and production cost can be reduced. (3) In the present invention, since epoxysilane is used as the component (a), it is cured in a short time by an active energy ray,
Further, a film having a small shrinkage can be obtained. for that reason,
It is possible to easily and efficiently manufacture a molded body in which the substrate after film formation is hardly warped. 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 low coefficient of friction. Therefore, it is hardly scratched, 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. (8) Since the film of the present invention has a high surface reflectivity, when used for decorative articles and the like, a molded article having excellent durability and excellent appearance can be obtained.

 ──────────────────────────────────────────────────の Continued on the front page (72) Inventor Toruuchi 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: R ¹ a R ² b Si (OR ³ ) _{4- (a + b)} (wherein, R ¹ is an organic group having an epoxy group and having 4 to 14 carbon atoms; 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, a is 1 or more and b Is 0
2, and a + b is from 1 to 3) or a hydrolyzate thereof (b) a polymerization initiator which 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,
Fine particles having a particle diameter of 1 to 100 millimicrons composed of an oxide of one or more metals selected from Fe, Zn, W, Zr, In, and Ti and / or particle diameters composed of oxides of two or more metals 1-100 millimicron composite fine particles or solid solutions or mixtures thereof. 3. A coating composition containing the components (a) and (b) according to the first aspect or the components (a), (b) and (c) according to the second aspect, comprising the following component (d). A coating composition comprising: (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 active energy rays. A method for producing a molded article, comprising: a coating step of applying the coating composition; and a film forming step of curing the coating composition by irradiating an active energy ray to the molded article coated with the coating composition. General formula: R ¹ aR ² bSi (OR ³ ) _{4- (a + b)} (wherein, R ¹ is an organic group having 4 to 14 carbon atoms having an epoxy group, and R ² is a carbon number having R ³ is an alkyl group, alkoxyalkyl group or acyl group having 1 to 4 carbon atoms, a is 1 or more, and b is 0 to
2, and a + b is 1-3) 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
A method for producing the 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.