JPH11148048A - Coating composition and plastic formed product - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject composition capable of giving a plastic formed product having high durability and dyeability by including an organic silicone compound, a metal complex compound, a perchloric salt and an aluminum chelate compound. SOLUTION: This composition contains (A) an organic silicone compound, (B) a metal complex compound, (C) a perchloric salt (preferably, magnesium perchlorate) and (D) an aluminum chelate compound, and is used as a hardening layer of a plastic formed product. The component A is a silane compound having a polymerizable reactive group such as a vinyl group, an allyl group or a (meth)acrylic group, and examples of the compound include vinyltrimethoxysilane. The component B is, for example, iron ethylenediaminetetraacetate or aluminum ethylenediaminetetraacetate, and this is preferably used in an amount of 0.0001-40 pts.wt. based on 100 pts.wt. of the component A. Further, the component C and the component D are each used preferably in an amount of 0.01-10 pts.wt. based on 100 pts.wt. of the component A.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a coating composition applied to a plastic material and a molded product having a cured layer of the composition.

[0002]

2. Description of the Related Art In recent years, plastic materials have been used as optical materials instead of conventional glasses.
Moldings made of plastic materials are lightweight, easy to process,
Despite its advantages such as excellent impact resistance, it has problems such as insufficient hardness and easy to be scratched, easy to be eroded by solvent, easy to be charged and adsorb dust, and insufficient heat resistance. there were.

As a means for improving the problem of the abrasion of these plastic materials, it has been proposed to apply a protective coat called a hard coat layer on a substrate. Many coating compositions used for the coat have been proposed,
Japanese Patent Application Laid-Open No. 52-11261 proposes to use a coating composition containing an organosilicon compound or a hydrolyzate thereof as a main component (resin component or coating film component).
JP-A-53-111336 proposes a coating composition to which a silica sol dispersed in a colloidal form is further added. In order to further improve the performance of these coating films, JP-A-5-339541 discloses a metal complex compound represented by the general formula: M [CH ₂ N (CH ₂ COO) ₂ ] ₂ Na _c (wherein , M is Zn,
Mn, Mg, Fe, Cu, Co, Ca, Bi, Al, and c is 1 or 2. ) Has been proposed.

[0004]

SUMMARY OF THE INVENTION The present inventors have reported that a coating composition such as an epoxy-containing alkoxysilane and colloidal silica having the general formula: M [CH ₂ N (CH ₂ COO) ₂ ] ₂ Na a metal complex compound represented by _c (where M is Zn,
Mn, Mg, Fe, Cu, Co, Ca, Bi, Al, and c is 1 or 2. Using a coating composed of a thermosetting resin whose main component is a), the coating was applied onto a transparent plastic material and cured to form a hard coat layer. The lens on which the hard coat layer was formed was dyed by a dip dyeing method using a dye such as a disperse dye, a reactive dye, a basic dye, or an acid dye.

As a result of examining the properties of the plastic optical parts obtained as described above, the plastic optical parts were found to be excellent in scratch resistance and adhesion and durability between the plastic substrate and the coating film, but were satisfactory in hot water resistance. No chemical resistance could be obtained. Further, even in an optical component in which an inorganic oxide such as silicon oxide is deposited on the hard coat layer of the plastic optical component by a vacuum deposition method to form an antireflection film, satisfactory chemical resistance cannot be obtained. was there.

[0006]

The present inventors have studied the composition of the coating composition in order to solve these problems and obtain a plastic molded article having high durability and high dyeability. Therefore, the present inventors have developed the properties of the coating film such as scratch resistance, surface hardness, abrasion resistance, flexibility, transparency, antistatic property, dyeability, heat resistance, water resistance, and chemical resistance. Improved and long-life coating compositions have been found.

Therefore, the present invention firstly provides "a coating composition comprising an organosilicon compound and a metal complex compound, and a perchlorate and an aluminum chelate compound, and a plastic molded article having a cured layer of the composition (claim 1)". I will provide a. Second, "at least the following components (A),
A coating composition comprising (B) and (C).

(A) General formula: R ¹ aR ² bSi (OR ³ ) _{4- (a + b)} (formula 1) (wherein, R ¹ is a functional group or the number of carbon atoms having an unsaturated double bond) 4 to 14 organic groups, and R ² has 1 to 6 carbon atoms.
R ³ is an alkyl group having 1 to 4 carbon atoms, an alkoxyalkyl group or an acyl group, a is 0 or 1, b is 0 to 2, and a + b is 1 or 2. Or a hydrolyzate thereof (B) a metal complex compound represented by the general formula: M [CH ₂ N (CH ₂ COO) ₂ ] ₂ Na _c (Formula 2) M is Zn,
Mn, Mg, Fe, Cu, Co, Ca, Bi, Al, and c is 1 or 2. ) (C) at least one compound selected from the following group 1) perchlorate 2) _{formula; Al · X n · Y 3} -n ( aluminum chelate compound represented by the formula 3) (wherein, Where:
X is a lower alkoxy group; Y is a ligand (M ₁ , M ₂ , M ₃ and M ₄ is a lower alkyl group) derived from a compound selected from the group consisting of M ₁ COCH ₂ COM ₂ and M ₃ COCH ₂ COOM ₄ ), N is 0, 1 or 2. ) (Claim 2) "
I will provide a. Thirdly, there is provided "a coating composition wherein the component (C) of the coating composition according to claim 1 is a perchlorate (claim 3)". Fourthly, the present invention provides "a coating composition according to claim 1, 2, or 3, which comprises the following components. (D) inorganic oxide fine particles (claim 4)". Fifth, "the component (C) is magnesium perchlorate,"
Or 2 or 3 or 4 (claim 5). " Sixthly, there is provided "a plastic molded article characterized by having a cured layer of the coating composition according to claim 1 or 2 or 3 or 4 or 5 on a plastic substrate (claim 6)".

[0009]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The structure of the present invention will be described below in order. The component (A) that can be used in the present invention is a silane compound having a polymerizable reactive group such as a vinyl group, an allyl group, an acryl group, a methacryl group, an epoxy group, a mercapto group, a cyano group, an isocyano group, and an amino group. Yes, specific examples include vinyltrimethoxysilane, vinyltriethoxysilane, and vinyltris (β-methoxyethoxy).
Silane, vinyldimethylethoxysilane, allyltriethoxysilane, allyltrimethoxysilane, γ-acryloxypropylmethyldimethoxysilane, γ-acryloxypropyltrimethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, γ-methacryloxypropyltri Methoxysilane, γ-methacryloxypropylmethyldiethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-methacryloxypropyldimethylethoxysilane, γ-methacryloxypropyldimethylmethoxysilane, γ-methacryloxypropyltrismethoxyethoxysilane, Glycidoxymethyltrimethoxysilane, glycidoxymethyltriethoxysilane, α-glycidoxyethyltrimethoxysilane, α-glycidoxyethyl Triethoxysilane, β
-Glycidoxyethyltrimethoxysilane, β-glycidoxyethyltriethoxysilane, α-glycidoxypropyltrimethoxysilane, α-glycidoxypropyltriethoxysilane, β-glycidoxypropyltrimethoxysilane, β -Glycidoxypropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ
-Glycidoxypropyltripropoxysilane, γ-glycidoxypropyltributoxysilane, γ-glycidoxypropyltrimethoxyethoxysilane, γ-glycidoxypropyltriphenoxysilane, α-glycidoxybutyltrimethoxysilane , Α-glycidoxybutyltriethoxysilane, β-glycidoxybutyltrimethoxysilane, β-glycidoxybutyltriethoxysilane, γ-glycidoxybutyltrimethoxysilane, γ
-Glycidoxybutyltriethoxysilane, δ-glycidoxybutyltrimethoxysilane, δ-glycidoxybutyltriethoxysilane, (3,4-epoxycyclohexyl) methyltrimethoxysilane, (3,4-epoxycyclohexyl) Methyltriethoxysilane, β-
(3,4-epoxycyclohexyl) ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriethoxysilane, β- (3,4-epoxycyclohexyl) ethyltripropoxysilane, β- (3
4-epoxycyclohexyl) ethyltributoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxyethoxysilane, 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-glycidoxyethylmethyldimethoxysilane, β-glycidoxyethylmethyldiethoxysilane, α-glycidoxypropylmethyldimethoxysilane, α-glycidoxypropylmethyldiethoxysilane, β-glycidoxypropylmethyldimethoxysilane, β-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropylmethyldipropoxysilane, γ-glycidoxypropylmethyldibutoxysilane, γ-glycidoxypropylmethyldimethoxyethoxysilane, γ-glycidoxypropylmethyldiphenoxysilane, γ-glycidoxysilane Cypropylethyldimethoxysilane, γ-glycidoxypropylethyldiethoxysilane, γ-glycidoxypropylethyldipropoxysilane, γ-glycidoxypropylvinyldimethoxysilane, γ-glycidoxypropylvinyldiethoxysilane,
γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, mercaptomethyldimethylethoxysilane, mercaptomethylmethyldiethoxysilane, γ-mercaptopropylmethyldimethoxysilane, N-β (aminoethyl) γ-aminopropylmethyldimethoxy Silane, N-β (aminoethyl) γ-
Aminopropyltrimethoxysilane, N-β (aminoethyl) γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, δ -Aminobutyldimethylmethoxysilane, δ-aminobutyltriethoxysilane, γ
-Aminopropyldimethylethoxysilane, γ-aminopropylmethyldiethoxysilane and the like. They are,
It is also possible to use a mixture of two or more kinds. Alternatively, the film may be used after hydrolysis, or the film may be subjected to an acid treatment after curing.

The component (B) has an action of polymerizing the component (A), and specific examples thereof include iron ethylenediaminetetraacetate, aluminum ethylenediaminetetraacetate, zinc ethylenediaminetetraacetate, manganese ethylenediaminetetraacetate, magnesium ethylenediaminetetraacetate, Examples include copper ethylenediaminetetraacetate, cobalt ethylenediaminetetraacetate, calcium ethylenediaminetetraacetate, and bismuth ethylenediaminetetraacetate. These can be used as a mixture of two or more kinds. Component (B) is preferably used in an amount of 0.0001 to 40 parts by weight (solid content) per 100 parts by weight (solid content) of component (A).

The component (C) is used for improving chemical resistance. Specific examples of 1) include magnesium perchlorate, aluminum perchlorate, zinc perchlorate, zinc ammonium chloride, and the like, with magnesium perchlorate being particularly preferred. These can be used in combination of two or more. The amount of perchlorate used is (A) component 100
It is preferable to use 0.01 to 10 parts by weight (solid content) per part by weight (solid content).

As specific examples of 2), aluminum acetylacetonate, aluminum ethyl acetoacetate bisacetylacetonate, aluminum bisethylacetoacetate acetylacetonate, aluminum di-n-butoxide monoethylacetoacetate, aluminum di-i- And propoxide monomethyl acetoacetate. These may be used in combination of two or more. It is preferable to use 0.01 to 10 parts by weight (solid content) per 100 parts by weight (solid content) of the component (A).

In order to further improve the hardness of the present invention,
(D) Inorganic fine particles may be added as a component. (D)
Minutes are inorganic oxide fine particles having an average particle diameter of 1 to 300 nm.
Yes, a specific example is Al_TwoO_Three, TiO_Two, Zr
O_Two, Fe_TwoO_Two, Sb_TwoO_Five, BeO, ZnO, SnO_Two,
CeO_Two, SiO_Two, WO_ThreeAnd the like. These fine
Particles may be used alone or mixed with multiple fine particles
You may use it. Furthermore, a plurality of fine particles are
It is also effective to use them. Composite oxide used here
Means that two or more types of inorganic oxides are mixed in the fine particle manufacturing stage.
It is a combination. For example, CeO_TwoAnd TiO_Two, SiO
_TwoAnd CeO_TwoAnd TiO_Two, ZrO_TwoAnd TiO_TwoComplex oxidation with
Fine particles. Also oxidized as inorganic fine particles
Complexes of metal salts or inorganic oxide particles and metal oxide salts
Alternatively, a compound may be used. As the metal oxide salt, Zn
OSnO_Two, BaOSnO_Two, SrOSnO_Two, CaOS
nO_Two, MgOSnO_Two, RaOSnO_Two, ZnOSb_TwoO
_Five, BaOSb_TwoO_Five, SrOSb _TwoO_Five, CaOSb
_TwoO_Five, MgOSb_TwoO_Five, RaOSb_TwoO_Five, ZnOTiO
_Two, BaOTiO_Two, SrOTiO_Two, CaOTiO_Two, M
gOTiO_Two, RaOTiO_Two, ZnOZrO_Two, BaO
ZrO_Two, SrOZrO_Two, CaOZrO_Two, MgOZr
O_Two, RaOZrO_Two, CoOFe_TwoO_Three, MnOFe
_TwoO_Three, ZnOFe_TwoO_Three, NiOFe_TwoO_ThreeEtc.
You. These metal oxide salts may be used alone or in combination of two or more.
It is also possible to use them in combination. Also those metal oxides
The salt is Al_TwoO_Three, TiO_Two, ZrO_Two, Fe_TwoO_Three, Sb_Two
O_Five, BeO, ZnO, SnO_Two, CeO_Two, SiO_Two, W
O_ThreeCan be used as a composite with metal fine particles such as
Noh. Further, a solid solution of a plurality of oxides may be used. these
Is appropriately selected and used depending on the purpose of use, refractive index, and the like. Further
Composite oxides and fine particles or composite oxides of fine particles
To silicon oxide and organosilicon compounds and organometallic compounds
And fine particles obtained by the above treatment. By silicon oxide
Treatment is, on the surface of the fine particles in a dispersion medium containing the fine particles,
Growing silicon oxide fine particles by a known method.

In use, fine particle powder may be used directly, or may be used in the form of a colloid previously dispersed in water, alcohol, or another organic solvent. The treatment with an organosilicon compound or an organometallic compound is a method in which a compound is added in a dispersion medium containing the fine particles, and the mixture is heated and stirred. The amount of the component (D) used is preferably 10 to 400 parts by weight (solid content) per 100 parts by weight (solid content) of the component (A).

The coating composition thus obtained can be used after being diluted with a solvent, if necessary. As the solvent, a solvent such as water, alcohols, esters, ketones, ethers, dimethylformamide, and aromatics is used, and a mixed solvent can be used if necessary. In addition, in order to improve the defects on the coating surface, leveling agents such as silicon-based surfactants, fluorine-based surfactants, and nonionic surfactants, or ultraviolet absorbers and antioxidants to improve weather resistance Alternatively, a pH adjuster can be added to stabilize the solution. The method for applying the cured film in the present invention is not particularly limited as long as it is a known method such as a dipping method, a spray method, and a spin coating method. Further, the surface of the plastic molded product can be subjected to pretreatment such as alkali treatment, plasma treatment, and ultraviolet treatment as necessary.

The plastic substrate, especially the spectacle lens substrate, used in the present invention may be any of those conventionally known, such as polymethyl methacrylate and its copolymer, acrylonitrile-styrene copolymer, polycarbonate, Examples thereof include plastic lens molded articles made of cellulose acetate, polyvinyl chloride, polyethylene terephthalate, epoxy resin, unsaturated polyester resin, polyurethane resin, diethylene glycol bisallyl carbonate polymer, and the like.

It is also possible to use an ultraviolet-curing resin or a resin having both ultraviolet-curing and thermosetting properties. As the ultraviolet curable resin used in the present invention, an ultraviolet curable resin which is polymerized by irradiation with ultraviolet light as described below is used. When both ultraviolet curing and thermal curing are used as described above, a polymerization initiator that starts polymerization by ultraviolet light and a polymerization initiator that starts polymerization by heat are added to the monomer.

As the ultraviolet polymerization reaction system, a photopolymerization radical initiator which generates radicals upon irradiation with ultraviolet light, a monomer or oligomer or a prepolymer which undergoes radical polymerization are required, and in addition, a sensitizer, a storage stabilizer, and a polymerization stabilizer are required. Inhibitors, polymers and coloring materials depending on the purpose may be blended. In addition, a cationic photopolymerization system is appropriately used.

The photo-radical initiator is not particularly limited and known ones can be used. Representative examples thereof include biacetyl, acetophenone, benzophenone, Michler's ketone, benzyl, benzoin, benzoin isobutyl ether, Benzyldimethyl ketal, tetramethylthiuram sulfide, azobisisobutylnitrile, 1-hydroxycyclohexylphenone, methyl ketone peroxide, acetylacetone peroxide, t-butyl peroxide, cumene hydroperoxide, α, α′-bis (t-butyl Peroxyisopropyl) benzene, t-butylperoxyisopropylcarbonate, benzoyl peroxide, di (t-butylperoxy) isophthalate, t-
Butyl peroxybenzoate, 3,3 ', 4,4'-
And tetra (t-butylperoxycarbonyl) benzophenone.

A radically polymerizable oligomer is used to efficiently cure the photoradical species, and a polymerizable monomer is appropriately added for the purpose of adjusting the viscosity. There are various types of photopolymerized oligomers, but there are unsaturated polyester / styrene type, epoxy / Lewis acid type, polyene / thiol type and acrylate. An acrylic group is frequently used as a polymerizable unit other than the unsaturated polyester. Acrylic oligomers are broadly classified into polyester acrylate, polyurethane acrylate, epoxy acrylate, polyether acrylate, oligo acrylate, alkyd acrylate, and polyol acrylate according to their basic structure. Is possible. The important thing in this is
Polyester, epoxy, urethane, and polyol acrylates. Main photopolymerizable monomers include monofunctional: uryl acrylate, 2-ethylhexyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 1,6-hexanediol monoacrylate, dicyclopentadiene acrylate, and the like. . Bifunctional: 1,3 butanediol diacrylate, 1,4 butanediol diacrylate, 1,6 hexanediol diacrylate, diethylene glycol diacrylate, tripropylene glycol diacrylate, neopentyl glycol diacrylate, polyethylene glycol 400 diacrylate ,
Hydroxypivalic acid ester neopentyl glycol diacrylate; Furthermore, trifunctional or more: trimethylolpropane triacrylate, pentaerythritol triacrylate, dipentaerythritol hexaacrylate.

Examples of the sensitizer include amines, ureas, sulfur compounds, nitriles, phosphorus compounds, other nitrogen compounds and chlorine compounds. Examples of the storage stabilizer include quaternary ammonium chloride, diethylhydroxyamine, cyclic amide, nitrile compound, substituted urea, benzothiazole, hydroquinone, hydroquinone monomethyl ether, and organic acids such as lactic acid, oxalic acid, and benzoic acid.

A coating layer comprising the coating composition of the present invention may be provided directly on the plastic substrate, or a primer layer may be formed between the substrate and the coating layer. By forming the primer layer, it is possible to improve the adhesion between the coat layer formed thereon and the substrate, and it is also possible to improve the impact resistance.

Materials used for the primer layer include:
A urethane-based material can be preferably used. The composition of the primer layer comprising a urethane-based material comprises an active hydrogen-containing compound and a polyisocyanate. Here, the active hydrogen-containing compound includes alkylene glycols such as ethylene glycol, 1,2-propylene glycol, 1,3-butanediol, 1,6 hexanediol, neopentyl glycol, dipropylene glycol and diethylene glycol; polypropylene glycol Polyalkylene glycols such as poly (ethylene glycol), polyethylene glycol and polytetramethylene glycol; polyalkylene adipates such as poly (diethylene adipate), poly (tetramethylene adipate), poly (hexamethylene adipate) and poly (neopenthylene adipate); poly -Ε-caprolactone; poly (1,4-butanediene) glycol, poly (1,2-butanediene)
Examples thereof include polybutadiene glycols such as glycol; poly (alkylene carbonate) s such as poly (hexamethylene carbonate); and silicone polyols. Other known active hydrogen-containing compounds can also be used.

Examples of the polyisocyanate 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, isophorone diisocyanate, 4,4′-dicyclohexylmethane diisocyanate, 1,3-bis (isocyanatomethyl) cyclohexane, trimethylhexamethylene diisocyanate, etc. Aliphatic diisocyanates are exemplified. Further, as the polyisocyanate, a block type polyisocyanate can be used.

Also, a mixture of an active hydrogen-containing compound and a polyisocyanate can be used, or a polymer may be used. Such a urethane-based material may be a solution made of a urethane-based material or a material in which particles made of a urethane-based material are dispersed in a solvent such as water. Further, it is also possible to form the primer layer from a material made of crosslinked polyvinyl acetal, in addition to a urethane-based material. The primer layer made of polyvinyl acetal dissolves polyvinyl acetal as a main component, a hydrolyzable organosilane compound or a hydrolysis condensate thereof, an aluminum or titanium alkoxide compound or an aluminum or titanium alkoxide diketonate compound, and a curing catalyst. It can be formed by applying the primer composition thus obtained to the surface of a plastic lens and subjecting it to heat treatment.

The primer composition composed of polyvinyl acetal applied to the present invention comprises at least a fraction (a) of a structural unit having an acetal group in the general formula (the fraction means the total amount of a specific structural unit in a polymer). A polymer (D) in which the ratio (b) of the number of structural units having an OH group is 10 to 90, and a + b ≦ 100, and (E) _{^{wherein; R 5 dR 6 eSiZ 1 4-}} (a + b) ( formula 4) (wherein, R ^5, R ⁶ is a substituted or unsubstituted hydrocarbon group having 1 to 8 carbon atoms, Z ¹ Is a hydrolyzate group, and d and e are integers from 0 to 3.) or a hydrolyzate thereof, or a general formula; Z ² _(3-f) R ⁸ fSiR ⁷ SiR ⁹ gZ ² _(3-g) (Formula 5) (wherein, R ⁷ is an organic group having 2 to 8 carbon atoms,
R ⁸ and R ⁹ are a substituted or unsubstituted hydrocarbon group having 1 to 8 carbon atoms, Z ² is a hydrolyzate group, and f and g are integers from 0 to 2. hydrolyzable organosilane compound or hydrolyzate thereof, or the general formula; HCO-R ¹⁰ -CHO (formula 6) (wherein, R ¹⁰ is the number of carbon atoms of the substituted or unsubstituted 1
Dialdehyde compounds represented by a is) 6 hydrocarbon group or glyoxal, or the general ^{formula; (R 12 O) CH-} R 11 -CH (OR 12) 2 ( Equation 7) (wherein, R ¹¹ Is a substituted or unsubstituted carbon atom 1
And at least one cross-linking agent selected from dialdehyde acetal compounds represented by the following formula: (F ¹² to R 6 is a saturated hydrocarbon group having 1 to 4 carbon atoms). A) a primer composition comprising an organic solvent and water, wherein the content of the component (D) is 1 to 30% by weight and the content of the crosslinking agent as the component (E) is 0.01 to 3% by weight;
0% by weight.

Preferably, a polyvinyl acetal of the following general formula is used.

[0028]

Embedded image

(Wherein R ¹³ is a hydrogen atom or a saturated hydrocarbon group having 1 to 20 carbon atoms, a is a fraction of a structural unit having an acetal group, 10 to 90, and b has an OH group. The fraction of the constituent units is 10 to 90, and c is the fraction of the constituent units having an acetyl group, 0 to 10, and a + b
+ C = 100. ) The hydrolyzable group in the organosilane compound is hydrolyzed to generate a silanol group, which reacts with the organometallic alkoxide compound.

Then, a hydroxyl group in the polyvinyl acetal is further dehydrated and condensed by the action of the catalyst and heat, and cross-linking is performed between or within the molecules. The molecule participating in the crosslinking is a hydrolyzate of an organosilane compound or a condensate thereof. The organosilane compound may be added as it is, or a compound that has been hydrolyzed in advance may be added. Further, one kind of organosilane compound may be used alone, or two or more kinds of organosilane compounds may be used in combination.

Examples of the organosilane compound include halosilane compounds in which the hydrolyzable group is a halogen atom, alkoxysilane compounds in which the hydrolyzable group is an alkoxy group, carboxysilane compounds in which the hydrolyzable group is a carboxy group, and hydrolyzable compounds. Ketoxime silane compounds in which the group is a ketoxime group can be used, but alkoxy silane compounds are preferred.

Specific examples of the hydrolyzable organosilane compound represented by the formula (4) include dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, phenylmethyldimethoxysilane, and phenylmethyldimethoxysilane. Ethoxysilane,
γ-chloropropylmethyldimethoxysilane, γ-chloropropylmethyldiethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, γ-methacryloxypropylmethyldiethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropylmethyldi Ethoxysilane, γ-aminopropylmethyldimethoxysilane, γ-aminopropylmethyldiethoxysilane, methylvinyldimethoxysilane, methylvinyldiethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropylmethyldiethoxy Silane, methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, methyltributoxysilane, methyltris (2-methoxyethoxy) silane, ethyl Limethoxysilane, ethyltriethoxysilane, ethyltripropoxysilane, ethyltributoxysilane, ethyltris (2-methoxyethoxy) silane, propyltrimethoxysilane, propyltriethoxysilane, butyltrimethoxysilane, butyltriethoxysilane, hexyltri Methoxysilane, hexyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2
-Methoxyethoxy) silane, phenyltrimethoxysilane, phenyltriethoxysilane, γ-chloropropyltrimethoxysilane, γ-chloropropyltriethoxysilane, 3,3,3-trifluoropropyltrimethoxysilane, 3,3,3 -Trifluoropropyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, chloromethyltrimethoxysilane, chloromethyltriethoxysilane, N-β-aminoethyl) -γ-aminopropyltrimethoxysilane, N-β
-Aminoethyl) -γ-aminopropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane,
γ-glycidoxypropyltriethoxysilane, (3,
4-epoxycyclohexylmethyl) trimethoxysilane, (3,4-epoxycyclohexylmethyl) triethoxysilane, β- (3,4-epoxycyclohexylethyl) trimethoxysilane, β- (3,4-epoxycyclohexylethyl) trimethoxysilane Examples include ethoxysilane, tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane, and the like.

Specific examples of the hydrolyzable organosilane compound represented by the formula (5) include 1,1-bis (trimethoxysilyl) ethane, 1,1-bis (triethoxysilyl) ethane, 1,2-bis (trimethoxysilyl) ethane, 1,2-bis (triethoxysilyl) ethane, 1,3-bis (trimethoxysilyl) propane,
1,3-bis (triethoxysilyl) propane, 2,2
-Bis (trimethoxysilyl) propane, 2,2-bis (triethoxysilyl) propane, and the like.

The addition amount of the organosilane compound in the primer composition is 0.01 to 10% by weight, preferably 0.1 to 5% by weight. A dialdehyde compound of the formula (6) or an acetal compound of a dialdehyde of the formula (7) is also used as a crosslinking agent. The dialdehyde compound and the acetal compound of dialdehyde may be used alone,
Two or more compounds may be mixed.

(Specific examples of the dialdehyde compound represented by the formula 6 include glutaraldehyde, hexanedial, 2-hydroxyhexanedial, and the like.
As the dialdehyde acetal compound represented by (Formula 7), malonaldehyde tetramethyl acetal, malonaldehyde tetraethyl acetal, glutaraldehyde tetramethyl acetal, or the like can be used. The addition amount of the dialdehyde compound or acetal compound in the primer composition is preferably 0.011 to 30% by weight.

As the organometallic alkoxide compound, aluminum or titanium alkoxide or alkoxide diketonate compound is used. These may be used alone or as a mixture of two or more compounds. The organometallic alkoxide compound easily reacts with the organosilane compound or its hydrolytic condensate, and the product reacts with hydroxyl groups in the polyvinyl acetal by the action of a catalyst and heat. The organometallic alkoxide compound has a function as a catalyst for promoting a dehydration condensation reaction between a silanol group in the organosilane compound generated by hydrolysis and a hydroxyl group in the polyvinyl acetal, and as a crosslinking agent for hydrolytic condensation with the organosilane compound. It is thought that there is an effect of.

Specific examples of the organometallic alkoxide compound include aluminum trimethoxide, aluminum triethoxide, aluminum tripropoxide, aluminum tributoxide, titanium tetramethoxide, titanium tetraethoxide, titanium tetrapropoxide, and titanium. Tetrabutoxide, aluminum dipropoxide acetylacetonate, aluminum dipropoxide ethyl acetoacetate, aluminum dibutoxide acetylacetonate, aluminum dibutoxide ethyl acetoacetate, titanium dimethoxide bis (acetylacetonate), titanium diethoxide bis (acetyl) Acetonate), titanium dipropoxide bis (acetylacetonate), titanium dibutoxide bis (acetyl Cetyl acetonate), titanium dipropoxide Sid bis (ethylacetoacetate), titanium dibutoxide bis (ethylacetoacetate)
And so on. Of these, titanium alkoxide is particularly preferred.

The addition amount of the organometallic alkoxide compound in the primer composition is 0.01 to 10% by weight, preferably 0.1 to 3% by weight, but is preferably 50% by mole or less of the organosilane compound. The amount of the organometallic alkoxide compound is 50 times the amount of the organosilane compound.
If it exceeds mol%, the impact resistance is reduced.

The curing catalyst is not particularly limited as long as it promotes the dehydration condensation between the hydrolysis condensate of the organosilane compound and the organometallic alkoxide compound and the hydroxyl group in the polyvinyl acetal, and the dehydration condensation reaction between the silanol groups. Absent. Specifically, organic tin compounds such as dibutyltin dilaurate, dibutyltin dioctate, dibutyltin diacetate, propylamine, butylamine,
Dipropylamine, dibutylamine, triethanolamine, tetramethylguanidine, methylimidazole,
Organic amines such as dicyandiamide, and organic metal complexes such as aluminum acetylacetonate and iron acetylacetonate can be used. Of these, organotin compounds are particularly preferred. These may be used alone or as a mixture of two or more kinds of catalysts.

The amount of the curing catalyst added to the primer composition is 0.002 to 1% by weight, preferably 0.005% by weight.
１1% by weight. As the organic solvent in the primer composition, hydrocarbons, halogenated hydrocarbons, alcohols, ketones, esters, ethers and other known solvents, polyvinyl acetal well dissolved, and inorganic oxide fine particles Those that disperse well can be used. Particularly preferred are methanol, ethanol, propanol, butanol, hexanol, methyl cellosolve and ethyl cellosolve, but these may be used alone or as a mixture of two or more organic solvents.

Water in the primer composition is added in an amount of 0.1 to 20% by weight as a component required for hydrolysis of the organosilane compound. If the amount of water is too large, the smoothness of the primer-coated surface is lost, and if the amount of water is too small, the usable time of the primer solution is shortened. The primer composition further enhances the film performance by various leveling agents for the purpose of improving coatability or ultraviolet absorbers and antioxidants for the purpose of improving weather resistance, as well as dyes and pigments, photochromic dyes and photochromic pigments, and the like. A known additive for adding a function can be used in combination.

The method of applying the primer composition on the plastic optical component in the present invention is not particularly limited as long as it is a known method such as a spin coating method and a dipping method.
In addition, it is preferable that the surface of the plastic optical component be subjected to a pretreatment such as an alkali treatment, a plasma treatment, or an ultraviolet treatment as necessary. The cured film thickness of the primer layer is 0.1 to 5 μm, preferably 0.2 to 3 μm. If the thickness of the primer layer is less than 0.1 μm, the impact resistance is not sufficiently improved, and if it is more than 5 μm, there is no problem in terms of the impact resistance, but the heat resistance and surface accuracy are reduced.

In the primer solution, it is possible to mix fine inorganic oxides mixed in the hard coat layer as described above. By mixing the fine particles, effects such as adjustment of refractive index and improvement of hardness can be provided. As these fine particles, commercially available fine particles dispersed in water or an organic solvent can be used as they are.

The average particle size of the finely divided inorganic oxide or the composite of these fine particles is from 1 to 300 nm, preferably from 1 to 50 nm. If the average particle diameter exceeds 300 nm, fogging of the lens occurs due to light scattering. The addition amount of the fine particles in the primer composition is 0.1 to
Although it is 30% by weight, the type and amount of the inorganic oxide fine particles are adjusted so that the refractive index of the cured primer layer matches or very close to the refractive index of the plastic lens.

In the case of a high-refractive-index plastic lens substrate having a refractive index of 1.60 or more, titanium oxide, zirconium oxide, iron oxide, antimony oxide, and oxide having a high refractive index are used for 1 part by weight of polyvinyl acetal. It is preferable to add 1 to 5 parts by weight of fine particles of tin, cerium oxide, tungsten oxide, or the like, or a composite thereof, or a mixture thereof. These inorganic fine particles can be added to a primer layer made of a urethane-based material.

The thickness of the primer layer is 0.01 to 30 μm.
m is preferred. Particularly preferably, 1 to 20 μm
It is. As a method of applying the resin to be the primer layer,
The method may be appropriately selected from known methods such as a spinner method, a dipping method, and a spray method, and may be formed by a dry method such as a CVD method or a vacuum evaporation method.

When the coating layer of the present invention is used as a hard coat layer, an antireflection film made of an inorganic oxide can be formed thereon. The film is formed by a dry method such as a vacuum evaporation method, a sputtering method, and a CVD method. Naturally, the antireflection film can have both a single-layer structure and a multilayer structure. On the antireflection film, a film for preventing water burn can be formed. As the material, an organic polysiloxane polymer or a polymer obtained by polymerizing a perfluoroalkyl group-containing compound is generally used. In particular, aminosilane-based and alkoxysilane-based compounds can be preferably used. As a forming method, a film can be formed by making the above-mentioned material into a liquid state and immersing a plastic substrate in the liquid. Alternatively, a vacuum deposition method may be used in which a material such as steel wool is impregnated with a liquid material, and the material is deposited in a vacuum to deposit the material on the surface of a plastic substrate.

When dyeing the coating layer of the present invention, usable dyes include disperse dyes, reactive dyes, basic dyes and acid dyes. These dyes are contained in a part near the surface of the coating layer, in the entire coating layer or in the plastic substrate. Further, the coating layer of the present invention can be formed after forming a layer containing a photochromic substance on the surface of the base material. Further, a photochromic substance is attached to the surface of a coating layer comprising the coating composition of the present invention by a vacuum deposition method, and the photochromic substance is infiltrated into the coating layer and the plastic substrate by heating, thereby producing a photochromic plastic lens. Is possible.

[0049]

Embodiment 1 Embodiments of the present invention will be described below, but the present invention is not limited to these embodiments. (1) Plastic molding A plastic lens substrate for CR-39 spectacles having a refractive index of 1.498 was used. (2) Preparation of Coating Solution To 200 parts by weight of β- (3,4 epoxycyclohexyl) ethyltrimethoxysilane, 0.4 parts by weight of 0.1 N HCl was added, and hydrolysis was performed while stirring for several hours.
To the above mixture, 600 parts of a methanol-dispersed silica sol (manufactured by Nissan Chemical Co., Ltd., solid content: 30%), 5.0 parts by weight of iron ethylenediaminetetraacetate as a curing catalyst, and 2.0 parts by weight of magnesium perchlorate were leveled. L7 as an agent
001 (a silicone-based surfactant manufactured by Nippon Unicar Co., Ltd.) was added in an amount of 2.0 parts by weight. (3) Coating film and curing A spin coating method (1000 rpm 20) was applied on the plastic lens of (1) which had been subjected to an alkali treatment as a pretreatment.
Secondly, the coating liquid obtained in (2) was applied, and the applied plastic lens was heated at 100 ° C. for 180 minutes to be cured. The cured film thus obtained was excellent in transparency. (4) Test and Evaluation Results The obtained lens (hereinafter, H lens) was tested by the following method, and the results are shown in Table 1. (A) Adhesion test of film In order to evaluate the adhesion of the film, a cross hatch tape test was performed by the following method. A 1 mm square goban eye was put on the surface of the coating layer with a cutter knife, and 100 squares of 1 mm 2 were formed. After strongly attaching cellophane adhesive tape (trade name "Cellotape" manufactured by Nichiban Co., Ltd.), hold one end of the tape and peel it off vigorously in the direction of 90 ° from the surface. Examined. Using the number X of the peeled goban eyes as the numerator, X /
Represented by 100. In this case, the larger the value of X, the better the adhesion. That is, if the result of the cross hatch tape test is “100/100”, it indicates that the film was not peeled at all. (B) Scratch resistance test The lens surface was rubbed with steel wool # 0000, and the scratch resistance was examined. The evaluation was performed as follows. ◎: No damage even if rubbed quite strongly. 少 し: Slightly damaged when rubbed quite strongly. ×: Scratched even with weak friction. Evaluation of plastic lens without cured paint is x. (C) Dyeing property In 1 liter of pure water at 90 ° C., 7 g of Nikon Light Dye Brown, our eyeglass dye, was dispersed to prepare a dyeing solution. It was immersed in this dyeing solution for 10 minutes for dyeing. A sample having no unevenness in dyeing and having a luminous transmittance of 50% or more before and after dyeing was regarded as good. (D) Heat resistance After being left in a constant temperature oven at 100 ° C. for 10 minutes, it was taken out under a normal temperature environment, and the presence or absence of cracks at that time was examined. Those that did not crack were considered good. (E) Chemical resistance After immersion in a sodium hydroxide aqueous solution having a pH of 12 for 10 hours, a material whose surface was not damaged was evaluated as good. (F) Pot life After storing the adjusted coating solution for one month, it is applied and cured in the same manner as in the initial stage. Those that did not are good.

[0050]

Embodiment 2 An anti-reflection deposited film was formed on each of the H lenses obtained in Embodiment 1 by the following method. (1) Formation of antireflection film After cleaning the H lens, an antireflection film composed of five layers of SiO2 / TiO2 was formed by vacuum evaporation. (2) Test and Evaluation Results The lenses thus obtained were evaluated for test items other than (c) dyeability in Example 1, and the results are shown in Table 1.

[0051]

Example 3 (1) Plastic molded article A plastic lens substrate for spectacles having a refractive index of 1.56 was used. (2) Preparation of coating liquid γ-glycidoxypropyltrimethoxysisilane 200
0.4 parts by weight of 0.1 N HCl was added to parts by weight, and hydrolysis was performed while stirring for several hours.

The above mixture was mixed with 600 parts by weight of methanol-dispersed silica sol (manufactured by Nissan Chemical Co., Ltd., solid content: 30%),
Aluminum ethylenediaminetetraacetate 5 as curing catalyst
Parts by weight of aluminum acetylacetonate, 1.0 part by weight of aluminum acetylacetonate, 2.0 parts by weight of Florado FC430 (a fluorosurfactant manufactured by Sumitomo 3M Ltd.) as a leveling agent and 400 parts by weight of methanol are added, followed by sufficient stirring. Thereafter, it was aged one day and night to obtain a coating solution. (3) Coating and curing On the plastic lens of (1), which was subjected to alkali treatment as a pretreatment, by dipping (3 mm / sec) (2)
Was applied, and the applied plastic lens was heat-treated at 100 ° C. for 180 minutes to be cured, and the cured film obtained was excellent in transparency. The lens thus obtained was tested in the same manner as in Example 1, and the results are shown in Table 1.

[0053]

Embodiment 4 (1) Formation of Antireflection Film The H lens obtained in Example 3 was formed with an antireflection film in the same manner as in Example 2. (2) Test and Evaluation Results The H lens thus obtained was tested in the same manner as in Example 2, and Table 1 shows the results.

[0054]

Example 5 (1) Plastic molded article A plastic lens substrate for spectacles having a refractive index of 1.60 was used. (2) Preparation of coating liquid γ-glycidoxypropylmethyldimethoxysilane 2
0.4 parts by weight of 0.1N HCl was added to 00 parts by weight,
The hydrolysis was performed while stirring for several hours.

The above mixture was mixed with a methanol sol having SnO2 / WO2 composite fine particles dispersed therein (manufactured by Nissan Chemical Industries, Ltd., solid content 30).
%) 600 parts by weight, 15 parts by weight of iron ethylenediaminetetraacetate and 2.0 parts by weight of magnesium perchlorate as a curing catalyst, and L7001 (a silicone surfactant manufactured by Nippon Unicar Co., Ltd.) as a leveling agent. Was added, and the mixture was thoroughly stirred and aged all day and night to obtain a coating solution. (3)
A spin coating method (1) is applied on the plastic lens of (1) which has been subjected to an alkali treatment as a coating film and a curing pretreatment.
2,000 rpm for 20 seconds), and the coated plastic lens is applied at 100 ° C. for 18 hours.
The cured film obtained by curing by heat treatment for 0 minutes was excellent in transparency. The H lens thus obtained was tested in the same manner as in Example 1, and the results are shown in Table 1.

[0056]

Embodiment 6 (1) Formation of Antireflection Film The H lens obtained in Example 5 was formed with an antireflection film in the same manner as in Example 2. (2) Test and Evaluation Results The lens thus obtained was subjected to a test in the same manner as in Example 2, and Table 1 shows the results.

[0057]

Example 7 (1) Plastic molded article A plastic lens substrate for spectacles having a refractive index of 1.66 was used. (2) Preparation of coating liquid γ-glycidoxypropylmethyldimethoxysilane 2
0.4 parts by weight of 0.1N HCl was added to 00 parts by weight,
The hydrolysis was performed while stirring for several hours.

The above mixture was mixed with TiO2 /
600 parts of a ZrO2 composite fine particle-dispersed methanol sol (manufactured by Catalyst Chemicals, Inc., solid content: 20%), 10 parts by weight of aluminum ethylenediaminetetraacetate and 3.0 parts by weight of magnesium perchlorate as a curing catalyst, and L7001 as a leveling agent 2.0 parts by weight of a silicone surfactant (manufactured by Nippon Unicar Co., Ltd.) was added, and the mixture was thoroughly stirred and aged for 24 hours to give a coating liquid. (3) Coating film and curing A spin coating method (1000 rpm 20) was applied on the plastic lens of (1) which had been subjected to an alkali treatment as a pretreatment.
Second), the coating liquid obtained in (2) was applied, and the applied plastic lens was heat-treated at 100 ° C. for 180 minutes to be cured, and the cured film obtained was excellent in transparency. The H lens thus obtained was tested in the same manner as in Example 1, and the results are shown in Table 1.

[0059]

Example 8 (1) Formation of Anti-Reflection Film An H-reflection film was formed on the H lens obtained in Example 7 in the same manner as in Example 2. (2) Test and Evaluation Results The lens thus obtained was subjected to a test in the same manner as in Example 2, and Table 1 shows the results.

Comparative Example 1 A coating film and a curing were performed in the same manner as in Example 1 except that magnesium perchlorate was not added. The lens thus obtained was tested in the same manner as in Example 1, and the results are shown in Table 1. Comparative Example 2 The H lens obtained in Comparative Example 1 was subjected to formation and evaluation of an antireflection film in the same manner as in Example 2, and the results are shown in Table 1.

Comparative Example 3 A coating film and a coating were prepared in the same manner as in Example 3 except that aluminum acetylacetonate was not added. The H lens thus obtained was tested in the same manner as in Example 1, and the results are shown in Table 1. [Comparative Example 4] An antireflection film was formed and evaluated on the lens obtained in Comparative Example 3 in the same manner as in Example 2, and the results are shown in Table 1.

Comparative Example 5 A coating film and a coating were prepared in the same manner as in Example 3, except that aluminum ethylenediaminetetraacetate was not added. The H lens thus obtained was tested in the same manner as in Example 1, and the results are shown in Table 1. Comparative Example 6 An antireflection film was formed and evaluated on the lens obtained in Comparative Example 3 in the same manner as in Example 2, and the results are shown in Table 1.

[0063]

[Table 1]

[0064]

According to the present invention, excellent transparency, dyeability,
A plastic molded article having durability and excellent adhesion can be obtained. Further, the use period of the coating composition is as long as one month or more, and the productivity is good and the production cost can be reduced. That is, it is possible to produce a plastic molded product having more excellent properties without losing the characteristics of the plastic material with good productivity. As a result, it has become possible to obtain plastic molded products that can withstand a wide variety of use conditions, such as various lenses such as glasses, cameras, and binoculars, and transparent plastics for optical applications such as display covers.

Claims (6)

[Claims] 1. A coating composition comprising an organosilicon compound, a metal complex compound, a perchlorate and an aluminum chelate compound, and a plastic molded article having a cured layer of the composition. 2. At least the following components (A), (B),
A coating composition comprising (C). (A) General formula: R ¹ aR ² bSi (OR ³ ) _{4- (a + b)} (Formula 1) (wherein, R ¹ represents a functional group or an unsaturated double bond having 4 to 14 carbon atoms. And R ² has 1 to 6 carbon atoms.
R ³ is an alkyl group having 1 to 4 carbon atoms, an alkoxyalkyl group or an acyl group, a is 0 or 1, b is 0 to 2, and a + b is 1 or 2. Or a hydrolyzate thereof (B) a metal complex compound represented by the general formula: M [CH ₂ N (CH ₂ COO) ₂ ] ₂ Na _c (Formula 2) M is Zn,
Mn, Mg, Fe, Cu, Co, Ca, Bi, Al, and c is 1 or 2. ) (C) at least one compound selected from the following group 1) perchlorate 2) _{formula; Al · X n · Y 3} -n ( aluminum chelate compound represented by the formula 3) (wherein, Where:
X is a lower alkoxy group; Y is a ligand (M ₁ , M ₂ , M ₃ and M ₄ is a lower alkyl group) derived from a compound selected from the group consisting of M ₁ COCH ₂ COM ₂ and M ₃ COCH ₂ COOM ₄ ), N is 0, 1 or 2. ) 3. The coating composition according to claim 1, wherein component (C) of the coating composition is a perchlorate. 4. The composition according to claim 1, further comprising the following components:
Or the coating composition according to 2 or 3. (D) Inorganic oxide fine particles 5. The coating composition according to claim 1, wherein component (C) is magnesium perchlorate. 6. A plastic molded article having a cured layer of the coating composition according to claim 1, 2 or 3 or 4 or 5 on a plastic substrate.