JP2001174602A - Optical member with hardened film and method for producing same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an optical member obtained by disposing a hardened film on an optical substrate with good adhesion without subjecting the substrate to pretreatment for improving adhesion. SOLUTION: A hardened film obtained from a coating composition containing (A) colloidal metal oxide particles, (B) an organosilicon compound and (C) an adhesion improver comprising a metallic salt of perchloric acid is disposed on an optical substrate not subjected to pretreatment for improving adhesion to obtain the objective optical member.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to an optical member having a cured film and a method for manufacturing the same. More specifically, the present invention provides a cured film for imparting various functions such as abrasion resistance and aesthetics on the optical substrate without performing a pretreatment for improving the adhesiveness on the optical substrate with good adhesion. The present invention relates to an optical member provided and a method for efficiently manufacturing the optical member.

[0002]

2. Description of the Related Art Conventionally, as a method for imparting various functions such as abrasion resistance and esthetics to a plastic optical member, a cured film is usually provided on the surface of a plastic optical substrate. However, the adhesion between the cured film and the plastic optical substrate is generally often insufficient. Therefore, in order to improve the adhesion, for example, a plasma, a corona flame,
Physical treatment such as ultraviolet rays, or acid, alkali,
Attempts have been made to perform pretreatments such as chemical treatments with various organic solvents. However, such a pretreatment method for a base material has disadvantages that the operation is complicated, requires expensive equipment, and the production cost of the objective optical member is unavoidably high. I have.

[0003]

SUMMARY OF THE INVENTION Under the above circumstances, the present invention provides an optical substrate surface having a scratch resistance and a scratch resistance without performing a pretreatment requiring complicated operations and expensive equipment. It is an object of the present invention to provide an optical member in which a cured film for imparting various functions such as aesthetics is provided with good adhesion.

[0004]

Means for Solving the Problems The inventors of the present invention have intensively studied to develop an optical member in which a cured film having good adhesion is provided without performing a pretreatment for improving the adhesion to the optical substrate. As a result of the above, the purpose is achieved by using a coating composition containing metal oxide colloid particles, an organosilicon compound, and a metal salt of perchlorate as an adhesion improver for forming a cured film. The inventors have found that the present invention can be performed, and have completed the present invention based on this finding.

That is, the present invention provides an optical member having an optical base material and a cured film provided thereon, wherein the cured film comprises (A) metal oxide colloid particles,
An optical member having a cured film characterized by being obtained from a coating composition containing (B) an organosilicon compound and (C) metal perchlorate as an adhesion improver. It is. Further, according to the present invention, the optical member is manufactured by applying the coating composition on an optical base material that has not been subjected to a pretreatment for improving adhesion and then performing a curing treatment. Can be.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION In a coating composition for forming a cured film in an optical member having a cured film of the present invention (hereinafter sometimes simply referred to as “optical member of the present invention”), component (A) is used as a component. And metal oxide colloid particles are used. As the metal oxide colloid particles,
There is no particular limitation, and conventionally known ones can be used. Examples of the metal oxide colloid particles include colloid particles of aluminum oxide, iron oxide, tin oxide, zirconium oxide, silicon oxide, titanium oxide, antimony oxide, cerium oxide, tungsten oxide, and the like, and colloid particles of a composite thereof. No. As the colloid particles of the composite, for example, tin oxide-zirconium oxide-tungsten oxide composite fine particles disclosed in JP-A-6-25603, JP-A-3-217230
Patent Document 1: Tin oxide-tungsten oxide composite fine particles disclosed in Japanese Patent Application Laid-Open No. H08-113760, and titanium oxide, cerium oxide, and silicon oxide composite fine particles disclosed in Japanese Patent Application Laid-Open No. 8-113760. Composite fine particles of titanium oxide-zirconium oxide-tin oxide disclosed in JP-A-9-21901, composite fine particles of titanium oxide-zirconium oxide-silicon oxide disclosed in JP-A-9-21901, and stannic oxide-zirconium oxide Composite fine particles of tungsten oxide;

The particle diameter of these metal oxide colloid particles is preferably in the range of 1 to 500 nm. The metal oxide colloid particles of the component (A) may be used alone or in combination of two or more.

[0008] In the coating composition of the present invention, an organosilicon compound is used as the component (B). Examples of the organosilicon compound include compounds represented by the following general formula (I): R ¹ _m Si (OR ² ) _{4 -m} (I) wherein R ¹ is a monovalent monovalent compound having or not having a functional group having 1 to 20 carbon atoms. R ² represents a monovalent hydrocarbon group having 1 to 8 carbon atoms or an acyl group having 1 to 8 carbon atoms, m represents 0, 1 or 2, and when there are a plurality of R ¹ , ¹
Each may be the same or different, and multiple OR
² may be the same or different. A) a compound represented by the general formula (II)

[0009]

Embedded image

Wherein R ³ and R ⁴ are each independently an alkyl group having 1 to 4 carbon atoms or an acyl group having 1 to 4 carbon atoms, and R ⁵ and R ⁶ are each independently a functional group. Or a monovalent hydrocarbon group having 1 to 5 carbon atoms not having Y,
Is a divalent hydrocarbon group having 2 to 20 carbon atoms, a and b are
Each represents 0 or 1, and a plurality of OR ³ may be the same or different, and a plurality of OR ⁴ may be the same or different. ), A compound represented by
And at least one selected from hydrolysates thereof.

In the general formula (I), the monovalent hydrocarbon group having 1 to 20 carbon atoms represented by R ¹ may be a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, Examples thereof include a linear, branched, or cyclic alkenyl group having 2 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and an aralkyl group having 7 to 20 carbon atoms. Here, the alkyl group having 1 to 20 carbon atoms is preferably an alkyl group having 1 to 10 carbon atoms,
Examples include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a pentyl group, a hexyl group, an octyl group, a cyclopentyl group, and a cyclohexyl group. Can be The alkenyl group having 2 to 20 carbon atoms is preferably an alkenyl group having 2 to 10 carbon atoms, and examples thereof include a vinyl group, an allyl group, a butenyl group, a hexenyl group and an octenyl group. The aryl group having 6 to 20 carbon atoms is preferably an aryl group having 6 to 10 carbon atoms, and examples thereof include a phenyl group, a tolyl group, a xylyl group, and a naphthyl group. The aralkyl group having 7 to 20 carbon atoms is preferably an aralkyl group having 7 to 10 carbon atoms, and examples thereof include a benzyl group, a phenethyl group, a phenylpropyl group, and a naphthylmethyl group.

A functional group may be introduced into these hydrocarbon groups. Examples of the functional group include a halogen atom, a glycidoxy group, an epoxy group, an amino group, a mercapto group, a cyano group and a (meth) acryloyloxy group. And the like. As the hydrocarbon group having such a functional group, an alkyl group having 1 to 10 carbon atoms having the functional group is preferable, for example, γ-chloropropyl group, 3,3,3-trichloropropyl group, chloromethyl group, Sidoxymethyl group, α-glycidoxyethyl group, β-glycidoxyethyl group, α-glycidoxypropyl group, β-glycidoxypropyl group, γ-glycidoxypropyl group, α-glycidoxy Butyl group, β-glycidoxybutyl group, γ-
Glycidoxybutyl group, δ-glycidoxybutyl group,
(3,4-epoxycyclohexyl) methyl group, β-
(3,4-epoxycyclohexyl) ethyl group, γ-
(3,4-epoxycyclohexyl) propyl group, δ-
(3,4-epoxycyclohexyl) butyl group, N-
(Β-aminoethyl) -γ-aminopropyl group, γ-aminopropyl group, γ-mercaptopropyl group, β-cyanoethyl group, γ-methacryloyloxypropyl group, γ
An acryloyloxypropyl group.

On the other hand, examples of the monovalent hydrocarbon group having 1 to 8 carbon atoms in R ² include a linear, branched,
Examples thereof include a cyclic alkyl group, an aryl group having 6 to 8 carbon atoms, and an aralkyl group having 7 to 8 carbon atoms. here,
Examples of the alkyl group include a methyl group, an ethyl group, and n-
A propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a pentyl group, a hexyl group, a cyclopentyl group, a cyclohexyl group, and the like; examples of the aryl group include a phenyl group and a tolyl group; And an aralkyl group such as a benzyl group and a phenethyl group. Examples of the acyl group having 1 to 8 carbon atoms include an acetyl group. m is 0, 1 or 2, when R ¹ is a plurality, the plurality of R ¹ may be the mutually the same or different, and plural OR
² may be the same or different.

Examples of the compound represented by the general formula (I) include methyl silicate, ethyl silicate, n-propyl silicate, isopropyl silicate, n-butyl silicate, sec-butyl silicate and tert-butyl silicate.
Butyl silicate, tetraacetoxysilane, methyltrimethoxysilane, methyltripropoxysilane, methyltriacetoxysilane, methyltributoxysilane,
Methyltripropoxysilane, methyltriamyloxysilane, methyltrifunoxysilane, methyltribenzyloxysilane, methyltriphenethyloxysilane, glycidoxymethyltrimethoxysilane, glycidoxymethyltriethoxysilane, α-glycidoxy Ethyltrimethoxysilane, α-glycidoxyethyltriethoxysilane, β-glycidoxyethyltriethoxysilane,
α-glycidoxypropyltrimethoxysilane, α-glycidoxypropyltriethoxysilane, β-glycidoxypropyltrimethoxysilane, β-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltripropoxysilane, 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) 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, α-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropylmethyldipropoxysilane, γ-glycidoxypropylmethoxy Silane, γ-glycidoxypropylmethyldiphenoxysilane, γ-glycidoxypropylethyldimethoxysilane, γ-glycidoxypropylethyldiethoxysilane, γ-glycidoxypropylvinyldimethoxysilane, γ-glycidoxy Propylvinyldiethoxysilane, γ-glycidoxypropylphenyldimethoxysilane, γ-glycidoxypropylphenyldiethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, vinyltrimethoxysilane, vinyltriacetoxysilane, vinyltriethoxy Silane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltriacetoxysilane, γ-chloropropyltrimethoxysilane, γ-chloropropyltriacetoxycin,

3,3,3-trifluoropropyltrimethoxysilane, γ-methacryloyloxypropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, β
-Cyanoethyltriethoxysilane, chloromethyltrimethoxysilane, chloromethyltriethoxysilane, N
-(Β-aminoethyl) -γ-aminopropyltrimethoxysilane, N- (β-aminoethyl) -γ-aminopropylmethyldimethoxysilane, γ-aminopropylmethyldimethoxysilane, N- (β-aminoethyl)- γ
-Aminopropylmethyldimethoxysilane, N- (β-
Aminoethyl) -γ-aminopropylmethyldiethoxysilane, dimethyldimethoxysilane, phenylmethyldimethoxysilane, dimethyldiethoxysilane, phenylmethyldiethoxysilane, γ-chloropropylmethyldimethoxysilane, γ-chloropropylmethyldiethoxysilane, Dimethyldiacetoxysilane, γ-methacryloyloxypropylmethyldimethoxysilane, γ-methacryloyloxypropylmethyldiethoxysilane, γ
-Mercaptopropylmethyldimethoxysilane, γ-mercaptopropylmethyldiethoxysilane, methylvinyldimethoxysilane, methylvinyldiethoxysilane and the like.

On the other hand, in the general formula (II), the alkyl group having 1 to 4 carbon atoms among R ³ and R ⁴ is
Methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group,
A tert-butyl group is exemplified, and an acyl group having 1 to 4 carbon atoms is preferably an acetyl group. This R
³ and R ⁴ may be the same or different. Further, the carbon number represented by R ⁵ and R ⁶ is 1 to
5 monovalent hydrocarbon groups include an alkyl group having 1 to 5 carbon atoms and an alkenyl group having 2 to 5 carbon atoms.
These may be linear or branched, and examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group and a tert-butyl group. Group, pentyl group and the like,
Examples of the alkenyl group include a vinyl group, an allyl group, and a butenyl group.

A functional group may be introduced into these hydrocarbon groups. Examples of the functional group and the hydrocarbon group having a functional group include those exemplified in the description of R ^{1 in} the general formula (I). The same can be mentioned. R ⁵ and R ⁶ may be the same or different. As the divalent hydrocarbon group having 2 to 20 carbon atoms represented by Y, an alkylene group and an alkylidene group having 2 to 10 carbon atoms are preferable, for example, a methylene group, an ethylene group,
Examples include a propylene group, a butylene group, an ethylidene group, and a propylidene group. a and b each represent 0 or 1, and a plurality of OR ³ may be the same or different, and a plurality of OR ⁴ may be the same or different.

Examples of the compound represented by the general formula (II) include methylenebis (methyldimethoxysilane), ethylenebis (ethyldimethoxysilane), propylenebis (ethyldiethoxysilane), and butylenebis (methyldiethoxysilane). And the like.

In the coating composition of the present invention, as the organosilicon compound as the component (B), one kind is appropriately selected from the compounds represented by the general formulas (I) and (II) and a hydrolyzate thereof. They may be used, or two or more kinds may be selected and used in combination. The hydrolyzate is obtained by adding a basic aqueous solution such as an aqueous solution of sodium hydroxide or ammonia, or an acidic aqueous solution such as an aqueous solution of acetic acid or citric acid to the organosilicon compound represented by the general formula (I) or (II). Then, it can be prepared by stirring.

Next, in the coating composition of the present invention, metal perchlorate is used as the component (C). This metal perchlorate serves as an agent for improving the adhesion between the optical substrate and the cured film, and is, for example, represented by the general formula (III) M (ClO ₄ ) _n (III) M represents a metal atom, and n represents the valence of the metal atom M.) or a hydrate thereof.

Examples of such metal perchlorates include:
Zinc perchlorate hexahydrate, potassium perchlorate, silver (I) perchlorate, mercury (II) perchlorate n hydrate, iron perchlorate (II)
I) hexahydrate, copper (II) perchlorate hexahydrate, sodium perchlorate hydrate, lead (III) perchlorate trihydrate, nickel (II) perchlorate hydrate, Barium perchlorate trihydrate,
Magnesium perchlorate, lithium perchlorate (anhydrous), lithium perchlorate trihydrate, aluminum perchlorate hexahydrate, aluminum perchlorate nonahydrate, and the like. Iron (III) chlorate hexahydrate, sodium perchlorate hydrate, nickel (II) perchlorate hydrate, magnesium perchlorate, lithium perchlorate (anhydrous), lithium perchlorate trihydrate Preferred are hydrates, aluminum perchlorate hexahydrate and aluminum perchlorate nonahydrate. These may be used alone or in combination of two or more.

The content ratio of each component in the coating composition of the present invention is not particularly limited and is appropriately selected depending on the situation. However, in consideration of the performance of the cured film, the adhesion to the optical substrate, and the like, The metal oxide colloid particles of the component (A) are preferably contained in a proportion of 1 to 500 parts by weight, more preferably 10 to 200 parts by weight, as solids, per 100 parts by weight of the organosilicon compound of the component (B). It is advantageous to contain the adhesion improver comprising the metal perchlorate salt of component (C) in an amount of preferably 0.01 to 10 parts by weight, more preferably 0.1 to 5 parts by weight.

The coating composition may optionally contain a curing agent to promote the reaction. Examples of the curing agent include amines such as allylamine and ethylamine, and various acids and bases including Lewis acids and Lewis bases, such as organic carboxylic acids, chromic acid, hypochlorous acid, boric acid, perchloric acid, and bromine. Salts or metal salts having an acid, selenous acid, thiosulfuric acid, orthosilicic acid, thiocyanic acid, nitrous acid, aluminate, carbonic acid, and the like, and metal alkoxides having aluminum, zirconium, and titanium, or metal chelate compounds thereof. .

The coating composition may contain various organic solvents and surfactants, if desired, for the purpose of improving wettability at the time of application and improving smoothness of the cured film. Further, ultraviolet absorbers, antioxidants, light stabilizers and the like can be added as long as they do not affect the physical properties of the cured film.

The optical substrate used in the optical member of the present invention includes, for example, methyl methacrylate homopolymer, a copolymer containing methyl methacrylate and one or more other monomers as monomer components, diethylene glycol bisallyl. Carbonate homopolymer, copolymer containing diethylene glycol bisallyl carbonate and one or more other monomers as monomer components, sulfur-containing copolymer, halogen-containing copolymer, polycarbonate, polystyrene, polyvinyl chloride, unsaturated polyester And plastic substrates such as polyethylene terephthalate, polyurethane and polythiourethane.

As a method for producing an optical member of the present invention in which a cured film is formed on such an optical substrate, for example, an optical member which has not been subjected to a pretreatment for improving adhesion by applying the coating composition described above. After coating on a substrate, a method of curing is used. As a coating method, a commonly used method such as a dipping method, a spin coating method, and a spray method can be applied, but the dipping method and the spin coating method are particularly desirable from the viewpoint of surface accuracy. The curing treatment is usually performed by hot air drying or active energy ray irradiation, and the curing condition is preferably performed in hot air at 70 to 200 ° C, particularly preferably 90 to 150 ° C. Note that the active energy rays include far infrared rays and the like, and damage due to heat can be suppressed low. In the present invention, sufficient adhesion between the optical substrate and the cured film can be obtained without performing physical or chemical pretreatment for improving the adhesion to the optical substrate.

Although it has been known that metal perchlorate is used as a curing agent in a coating composition, no function has been known for improving the adhesion between a substrate and a cured film. The present invention has found a remarkable effect by using this metal perchlorate as an adhesion improver, and has completed the present invention.

In the optical member of the present invention, an antireflection film made of an inorganic oxide vapor-deposited film can be provided on the cured film formed as described above, if desired.
The anti-reflection film is not particularly limited, and a single-layer or multi-layer anti-reflection film made of a conventionally known inorganic oxide vapor-deposited film can be used. Examples of the antireflection film include, for example, JP-A-2-262104,
An antireflection film described in JP-A-6-116003 is exemplified.

The cured film comprising the coating composition of the present invention can be used as a high-refractive-index film for a reflective film, and can be used as a multifunctional film by adding functions such as anti-fogging, photochromic and anti-fouling. can do.

[0031]

Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.

The physical properties of the optical member having the cured film obtained in each example were measured by the following methods. (A) Adhesion evaluation 100 crosscuts were made on the cured film at 1.5 mm intervals.
After strongly attaching an adhesive tape (trade name: Cellotape Nichiban Co., Ltd.) to this cross-cut, the presence or absence of peeling of the cured film after rapidly peeling off the adhesive tape was examined. In the crosshatch test, those obtained 100/100 were evaluated as ○, and the others were evaluated as x.

(B) Evaluation of abrasion resistance The surface of the cured film was rubbed back and forth with steel wool # 0000 for 20 reciprocations under a load of 2 kg, and the scratch resistance was visually determined. The criteria are as follows. ◎: almost no scratches ○: less than 5 scratches △: 5 to less than 10 scratches ×: 10 to more scratches equivalent to optical substrate

(C) Evaluation of Transparency The cured film was visually inspected under a fluorescent lamp in a dark room to determine whether there was any haze. The criteria are as follows. ◎ …… No fogging is observed ○ ……… Fog is hardly visible △ ……… Slightly visible × ……… Large visible

(D) Moisture Resistance Test After leaving the optical member in a constant temperature and constant humidity tester (manufactured by Yamato Engineering Co., Ltd.) at 40 ° C. and 90% RH for a week,
The evaluation (a) described above was performed.

Production Example 1 Modified stannic oxide-zirconium oxide
<Preparation of stannic oxide sol > Specific gravity 1.4 obtained by reaction of tin metal powder, aqueous hydrochloric acid solution and aqueous hydrogen peroxide solution
20, pH 0.40, viscosity 32 mPa · s immediately after stirring,
SnO ₂ content: 33.0% by weight, HCl content: 2.56% by weight, spindle-shaped colloidal particle diameter of 10 nm or less measured by an electron microscope, specific surface area of particles measured by BET method: 120 m ² / g, converted particle diameter from this specific surface area: 7. 2 nm, a dynamic light scattering method particle diameter 107nm by US Coulter N ₄ device,
1200 g of a pale yellow transparent stannic oxide aqueous sol was added to water 10
After dispersion in 800 g, 4.8 g of isopropylamine was added thereto, and the resulting solution was passed through a column filled with a hydroxyl-type anion exchange resin, to obtain 13440 g of an aqueous stannic oxide aqueous sol. This sol
Stable, colloidal color, but very high transparency, specific gravity 1.029, pH 9.80, viscosity 1.4m
Pa · s, the SnO ₂ content was 2.95% by weight, and the isopropylamine content was 0.036% by weight.

[0037] (a) Zirconium oxychloride step reagent (ZrOCl ₂ · 8H
3043 g of an aqueous solution of zirconium oxychloride (2.0% by weight as ZrO ₂ ) prepared by dissolving ₂ O) in water (Z
It contains 60.87 g as rO ₂ . ), 10791 g (409.5 g of SnO ₂ ) of the above prepared alkaline stannic oxide aqueous sol was added at room temperature under stirring, and stirring was continued for 2 hours. The mixture is ZrO ₂ / SnO ₂
This was a sol having a good transparency with a colloidal color at a weight ratio of 0.15 and a pH of 1.50.

Step (b) (Preparation of a stannic oxide-zirconium oxide composite sol) The mixture prepared in the step (a) is subjected to a heat treatment at 90 ° C. for 5 hours with stirring to obtain a mixture of stannic oxide and zirconium oxide. 13,834 g of a zirconium oxide composite sol was obtained. This sol contained 2.96% by weight of SnO ₂ , 0.44% by weight of ZrO ₂ ,
3.40% by weight as nO ₂ + ZrO ₂ , pH 1.45
The particles had a particle size of 9.0 nm and a colloidal color, but had good transparency.

Step (c) (Preparation of Tungsten Oxide-Tannous Oxide-Silicon Dioxide Composite Sol) 113 g of No. 3 silicate (containing 29.0% by weight as SiO ₂ ) was dissolved in 2353.7 g of water. and then (containing 71 wt% as WO _3.) sodium tungstate _{Na 2 WO 4 · 2H 2 O} 33.3g and sodium stannate NaSnO ₃ · H ₂ O (as SnO ₂ containing 55% by weight.) 42. Dissolve 45 g. Then, this is passed through a column of a hydrogen-type cation exchange resin to obtain an acidic tungsten oxide-stannic oxide-silicon dioxide composite sol (pH 2.1, 0.75% by weight as WO ₃ ,
It contains 0.75% by weight as nO _{2 and} 1.00% by weight as SiO ₂ , and has a WO ₃ / SnO ₂ weight ratio of 1.0 and SiO ₂
/ SnO ₂ weight ratio was 1.33 and the particle size was 2.5 nm. ) 3150 g were obtained.

Step (d) 3150 g of the tungsten oxide-stannic oxide-silicon dioxide composite sol prepared in step (c) (WO ₃ + SnO ₂
It contains 78.83 g as + SiO ₂ . ), Stannic oxide-zirconium oxide composite sol 11592.6 g (ZrO ₂ + S) prepared in step (b) at room temperature with stirring.
It contains 394.1 g as nO ₂ . ) Was added over 20 minutes and stirring was continued for 30 minutes. The obtained mixed solution was composed of a stannic oxide-zirconium oxide composite colloid (ZrO _2).
+ SnO ₂ ) and tungsten oxide-stannic oxide-silicon dioxide composite colloid (WO ₃ + SnO ₂ + SiO ₂ )
Is (WO ₃ + SnO ₂ + SiO ₂ ) / (ZrO ₂ + Sn
O ₂ ) The weight ratio was 0.20, the pH was 2.26, and the total metal oxide was 3.2% by weight.

Step (e) (Preparation of a modified stannic oxide-zirconium oxide composite sol) To 14742.6 g of the mixture obtained in step (d), 9.5 g of diisobutylamine was added, and then hydroxyl-type anion exchange. The solution was passed through a column filled with a resin (Amberlite 410) at room temperature, and then heated and aged at 80 ° C. for 1 hour to obtain 16288 g of a modified stannic oxide-zirconium oxide composite aqueous sol (dilute solution). This sol had a total metal oxide content of 2.90% by weight and a pH of 10.43, had a colloidal color, but had good transparency.

The modified stannic oxide obtained in step (e)
The zirconium oxide composite aqueous sol (dilute solution) is concentrated at room temperature by a filtration device using an ultrafiltration membrane having a molecular weight cutoff of 50,000.
2,182 g of a modified stannic oxide-zirconium oxide composite aqueous sol having a high concentration was obtained. This sol had a pH of 8.71 and all metal oxides (ZrO ₂ + SnO ₂ + WO ₃ + SiO ₂ ) 1
It was stable at 8.3% by weight.

At room temperature, 4.0 g of tartaric acid, 6.0 g of diisobutylamine, and an antifoaming agent (SN Deformer 483 manufactured by San Nopco) were added to 2,182 g of the above-mentioned aqueous sol of modified stannic oxide-zirconium oxide complex at a high concentration. ) 1 drop was added and stirred for 1 hour. This sol was removed in a reaction flask equipped with a stirrer under normal pressure while adding 20 liters of methanol little by little, and water was distilled off, whereby 1,171 g of a modified stannic oxide-zirconium oxide composite methanol sol in which water in the aqueous sol was replaced with methanol. I got This sol had a specific gravity of 1.124, a pH of 7.45 (an equal weight mixture with water), a viscosity of 2.3 mPa · s, and a total metal oxide (ZrO ₂ + SnO _2).
+ WO ₃ + SiO ₂ ) 32.7% by weight, moisture 0.47% by weight, and the particle size as observed by electron microscope observation was 10 to 15 nm. This sol had a colloidal color, was highly transparent, and was stable without any formation of sediment, turbidity, thickening, etc. after standing at room temperature for 3 months. The dried product of this sol had a refractive index of 1.76.

Example 1 (1) Preparation of coating composition (a) Preparation of modified stannic oxide-zirconium oxide silicon composite sol In a reactor equipped with a rotor, γ-glycidoxypropyltrimethoxysilane 15 was added. Parts by weight and 49 parts by weight of the modified stannic oxide-zirconium oxide composite methanol sol obtained in Production Example 1 were charged, and the mixture was stirred at 4 ° C. for 3 hours.
3.5 parts by weight of hydrochloric acid having a concentration of 0.001 mol / liter was gradually dropped into the reactor, and stirred at 4 ° C. for 48 hours to prepare a modified stannic oxide-zirconium silicon oxide composite sol.

(B) Preparation of coating composition 30 parts by weight of propylene glycol monomethyl ether and 0.04 part by weight of silicone surfactant were added to the modified stannic oxide-zirconium silicon silicon composite sol obtained in (a) above. After stirring at 4 ° C. for 3 hours, 0.60 parts by weight of aluminum acetylacetonate and 0.0 of aluminum perchlorate (manufactured by Aldrich) were added.
5 parts by weight were added and mixed. After stirring at 4 ° C for 3 days,
The coating composition was prepared by allowing to stand at 4 ° C. for 2 days.

(2) Formation and Evaluation of Cured Film A plastic lens substrate (HOYA CORPORATION, plastic lens for spectacles, without any pre-treatment of a conventionally known adhesion improving treatment such as alkali, acid, plasma treatment, etc.) A plastic lens having a refractive index of 1.60) was immersed in the coating composition prepared by the method (b) for 5 seconds for 5 seconds.
An optical member was produced by heating at 1 ° C. for 1 hour to form a cured film. Table 1 shows the evaluation results of the physical properties and operability of this optical member.

Example 2 In preparing the coating composition of Example 1,
Example 1 was repeated except that aluminum perchlorate hexahydrate (manufactured by Soekawa Chemical Co., Ltd.) was used instead of aluminum perchlorate.
An optical member was produced in the same manner as described above. Table 1 shows the evaluation results of the physical properties and operability of the optical member.

Example 3 In preparing the coating composition in Example 1,
An optical member was produced in the same manner as in Example 1, except that anhydrous lithium perchlorate (manufactured by Wako Pure Chemical Industries, Ltd.) was used instead of aluminum perchlorate. Table 1 shows the evaluation results of the physical properties and operability of the optical member.

Example 4 In preparing the coating composition in Example 1,
Instead of the modified stannic oxide-zirconium oxide complex methanol sol, the same amount of colloidal silica as solids was used, and instead of aluminum perchlorate, aluminum perchlorate nonahydrate was used. An optical member was manufactured in the same manner as in Example 1. Table 1 shows the evaluation results of the physical properties and operability of the optical member.

Example 5 In the preparation of the coating composition in Example 1,
An optical member was produced in the same manner as in Example 1, except that aluminum perchlorate nonahydrate was used instead of aluminum perchlorate. Table 1 shows the evaluation results of the physical properties and operability of the optical member.

Comparative Example 1 In the preparation of the coating composition in Example 1,
An optical member was produced in the same manner as in Example 1, except that perchloric acid (manufactured by Wako Pure Chemical Industries, Ltd.) was used instead of aluminum perchlorate. Table 1 shows the evaluation results of the physical properties and operability of the optical member. In this case, sufficient adhesion could not be obtained.

Comparative Example 2 In the preparation of the coating composition in Example 1,
An optical member was produced in the same manner as in Example 1, except that the lens substrate was surface-treated with a 10% by weight aqueous solution of sodium hydroxide without using aluminum perchlorate and before applying the cured film. Table 1 shows the evaluation results of the physical properties and operability of the optical member. In this case, the physical properties of the optical member are the same as those of the embodiment, but the operation is complicated because the lens substrate is pretreated with an alkali.

Comparative Example 3 In the preparation of the coating composition in Example 1,
An optical member was produced in the same manner as in Example 1, except that aluminum perchlorate was not used. Table 1 shows the evaluation results of the physical properties and operability of the optical member. In this case, sufficient adhesion could not be obtained.

Comparative Example 4 In the preparation of the coating composition in Example 1,
Example 1 except that the lens substrate was plasma-treated without using aluminum perchlorate and before applying the cured coating.
An optical member was produced in the same manner as described above. Table 1 shows the evaluation results of the physical properties and operability of the optical member. in this case,
The physical properties of the optical member are the same as those of the embodiment, but the operation is complicated because the lens substrate is subjected to plasma processing.

[0055]

[Table 1]

As can be seen from the above results, Examples 1 to
The cured film of No. 5 has good adhesion to the optical base material without performing pretreatment on the optical base material. On the other hand, in the case of Comparative Examples 2 and 4, the optical base material is subjected to the pretreatment in order to develop the adhesion, and as a result, the operation is complicated. The cured films of Comparative Examples 1 and 3 did not exhibit adhesion.

[0057]

The optical member of the present invention does not require various pretreatments for improving the adhesion to the optical substrate, and is formed by forming a cured film having excellent adhesion to the optical substrate. . Further, the addition of the adhesion improver does not cause a decrease in the physical properties of the cured film.

Claims (10)

[Claims] 1. An optical member having an optical base material and a cured film provided thereon, wherein the cured film comprises:
It is obtained from a coating composition containing (A) metal oxide colloid particles, (B) an organosilicon compound, and (C) a metal perchlorate as an adhesion promoter. An optical member having a cured film. 2. The optical member having a cured film according to claim 1, wherein the coating composition contains a curing agent. 3. The colloidal particles of metal oxide (A) are colloidal particles of aluminum oxide, iron oxide, tin oxide, zirconium oxide, silicon oxide, titanium oxide, antimony oxide, cerium oxide, tungsten oxide, and composites thereof. The optical member having a cured coating according to claim 1, wherein the optical member is at least one member selected from body colloid particles. 4. The organic silicon compound of the component (B) is a compound represented by the following general formula (I): R ¹ _m Si (OR ² ) _4-m (I) wherein R ¹ is a carbon having or not having a functional group. C 1 -C 20 monovalent hydrocarbon group, R ² is a monovalent hydrocarbon group or an acyl group having 1 to 8 carbon atoms having 1 to 8 carbon atoms, m represents a 0, 1 or 2, R ¹ is If there are multiple, multiple R ¹
Each may be the same or different, and multiple OR
² may be the same or different. A compound represented by general formula (II): (Wherein, R ³ and R ⁴ each independently represent a carbon number of 1 to 4)
Is an alkyl group or an acyl group having 1 to 4 carbon atoms, R ⁵ and R ⁶ are each independently a monovalent hydrocarbon group having 1 to 5 carbon atoms having or not having a functional group, and Y is a carbon atom having 2 carbon atoms.
20 to 20 divalent hydrocarbon groups, a and b each represent 0
Or 1 and a plurality of OR ³ may be the same or different, and a plurality of OR ⁴ may be the same or different. 4. The optical member having a cured film according to claim 1, which is at least one member selected from the group consisting of a compound represented by the formula (1) and a hydrolyzate thereof. 5. The adhesiveness improver comprising a metal perchlorate salt of the component (C) is represented by the following general formula (III): M (ClO ₄ ) _n (III) (wherein M is a metal atom and n is a metal An optical member having a cured film according to any one of claims 1 to 4, which is a compound represented by the following formula: 6. A coating composition comprising 1 to 500 parts by weight of a metal oxide colloid particle of the component (A) as a solid content per 100 parts by weight of the organosilicon compound of the component (B), and (C) 6. The optical member having a cured film according to claim 1, wherein the optical member comprises 0.01 to 10 parts by weight of an adhesiveness improver comprising a component metal perchlorate. 7. An optical member having the cured film according to claim 1, further comprising an antireflection film on the cured film. 8. An optical base material that has not been subjected to a pretreatment for improving adhesion, comprising: (A) metal oxide colloid particles;
A method for producing an optical member having a cured coating, comprising applying a coating composition containing (B) an organosilicon compound and (C) an adhesion improver comprising a metal perchlorate, followed by curing treatment. . 9. The method according to claim 8, wherein the curing treatment is performed by heating with hot air or irradiation with active energy rays. 10. A coating composition containing (A) metal oxide colloid particles and (B) an organosilicon compound for forming a cured film on an optical substrate, thereby improving the adhesion of the coating composition. A method using (C) metal perchlorate as an agent.