JPH10332903A - Water-repellent optical member and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an optical member low in cost and having a hardened film excellent in water repellency, film hardness, adhesion property and transparency by applying a fluorinated porous thin film on the surface of a plastic substrate on which the hardened film is formed. SOLUTION: After a hardened film is formed on a plastic material, a hydrolysate of an alcohol soln. containing an org. silicone compd. expressed by formula (R<3> )b Si(OR<4> )4-b , an org. polymer compd. and a hardening agent is applied and hardened by heating. Then the org. polymer compd. in the hardened film is removed by using a polar solvent to form a porous thin film. Then the surface of the porous thin film is subjected to fluoridation with a fluoroalkylsilane compd. soln. In the formula, R<3> is 1 to 10C alkyl group, 2 to 10C alkenyl group, etc., R<4> is 1 to 10C alkyl group, 2 to 10C acyl group, etc., and b is an integer of 0 to 2.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a water-repellent optical member and a method for producing the same, and more particularly, to a plastic optical member having a cured film having excellent water-repellency, film hardness, adhesion and transparency, and a plastic optical member. The present invention relates to a method for efficiently manufacturing.

[0002]

2. Description of the Related Art In order to form a water-repellent film on a substrate, various methods have been used so far, for example, a method of applying a fluorine-based silane coupling agent, a method of applying a fluorocarbon-based resin, and a method of coating a solid surface. Attempts have been made to increase the water repellency by a structural treatment such as making the surface uneven.

Specifically, (1) a method of performing a water-repellent treatment on a glass substrate with a fluorine-based silane coupling agent (JP-A-8-319136 and JP-A-8-231247), and (2) a fluorocarbon (Japanese Unexamined Patent Publication No. 8-239242), (3) A method of increasing the water repellency by making the solid surface uneven (Japanese Unexamined Patent Publication No. 7-20)
No. 6475) has been proposed.

However, the method of (1) for making the glass surface water-repellent does not provide adhesion to the substrate surface when applied to a plastic substrate, and also has a hardening temperature for the water-repellent treatment. Is higher than 200 ° C., there arises a problem that the substrate itself cannot withstand this processing method.
In the method (2) of treating with a fluorocarbon resin, the water repellency is good, but the adhesion to the plastic substrate surface and the film hardness are not obtained, and the optical transparency is high. However, it has disadvantages such as impairment. On the other hand, the method of (3) for making the solid surface uneven, requires the use of photolithography, which requires a complicated and large-scale process, inevitably increases the cost, and is sufficient for a plastic optical member. There is a drawback that adhesion cannot be obtained.

[0005]

SUMMARY OF THE INVENTION The present invention overcomes the drawbacks of the prior art and has an inexpensive plastic optical material having a cured film having excellent water repellency, film hardness, adhesion and transparency. An object is to provide a member.

[0006]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to develop a plastic optical member having the above-mentioned excellent characteristics, and as a result, a plastic substrate having a specific cured film has a specific surface. After applying and curing a hydrolyzate of a solution containing an organosilicon compound and an organic polymer compound having a structure, the organic polymer compound in the cured film is removed using a solvent to form a porous thin film, and furthermore, The present inventors have found that an optical member obtained by treating the surface with a specific fluorine compound is suitable for the purpose, and have completed the present invention based on this finding.

That is, the present invention provides a water-repellent optical member comprising a fluorinated porous thin film on the surface of a plastic substrate on which a cured film is formed.

According to the invention, the water-repellent optical member is provided on the surface of the plastic substrate on which the cured film is formed.
(A) General formula (II) (R ³ ) _b Si (OR ⁴ ) _4-b (II) (wherein, R ³ is an alkyl group having 1 to 10 carbon atoms, 2 carbon atoms)
10 alkenyl group, an aryl group or an aralkyl group having 7 to 10 carbon atoms having 6 to 10 carbon atoms, R ⁴ is 1 to carbon atoms
It represents an alkyl group having 10 carbon atoms, an acyl group having 2 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms or an aralkyl group having 7 to 10 carbon atoms, and b represents an integer of 0 to 2. If there are a plurality of R ^3, a plurality of R ³ may be the same with or different from each other, and a plurality of OR ⁴ may be the same with or different from each other. ), A hydrolyzate of an alcohol solution containing (b) an organic polymer compound and (c) a curing accelerator is applied, cured by heating, and then cured in a cured film using a polar solvent. The organic polymer compound is removed to form a porous thin film, and then the surface of the porous thin film is fluorinated with a solution containing a fluoroalkylsilane-based compound.

[0009]

DESCRIPTION OF THE PREFERRED EMBODIMENTS In the water-repellent optical member of the present invention, a plastic substrate having a cured film formed thereon is used as the substrate. As the plastic substrate, those having optical transparency, for example, methyl methacrylate homopolymer, a copolymer of methyl methacrylate and one other monomer, diethylene glycol bisallyl carbonate homopolymer, diethylene glycol bisallyl carbonate and other Examples include, but are not limited to, copolymers with one or more monomers, polycarbonate, polystyrene, polyvinyl chloride, unsaturated polyester, polyethylene terephthalate, polyurethane, and polythiourethane.

As the cured film provided on the surface of the plastic substrate, a metal oxide for improving film hardness and adhesion to the porous thin film and an organosilicon compound for improving adhesion to the substrate are used.

Usually, metal oxide colloid particles are preferably used as the metal oxide. As the metal oxide colloid particles used at this time, for example, tungsten oxide (W
O ₃ ), zinc oxide (ZnO), silicon oxide (SiO ₂ ),
Aluminum oxide (Al ₂ O ₃ ), titanium oxide (Ti
O ₂ ), zirconium oxide (ZnO ₂ ), tin oxide (Sn
Colloid particles such as O ₂ ), beryllium oxide (BeO), and antimony oxide (Sb ₂ O ₅ ). These colloid particles may be used alone or in combination of two or more.

On the other hand, as the organosilicon compound, a compound represented by the general formula (I) (R ¹ ) _a Si (OR ² ) _4-a (I) is preferably used.

In the general formula (I), R ¹ is an alkyl group having 1 to 10 carbon atoms, and the alkyl group has 1 to 10 carbon atoms.
A substituted alkyl group, an alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms or an aralkyl group having 7 to 10 carbon atoms. Here, the alkyl group having 1 to 10 carbon atoms may be linear, branched, or cyclic, and specific examples include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, and an n-butyl group. , Isobutyl, sec-butyl, tert-butyl, pentyl, hexyl, cyclopentyl, cyclohexyl and the like. The alkyl group of the substituted alkyl group having 1 to 10 carbon atoms in the alkyl group may be linear, branched or cyclic, and examples thereof include the alkyl groups exemplified above. Examples of the substituent introduced into these alkyl groups include a halogen group, a glycidoxy group, an epoxycyclohexyl group, an amino group, a substituted amino group, a mercapto group, a cyano group, and a methacryloxy group. The alkenyl group having 2 to 10 carbon atoms may be linear or branched, and specific examples include a vinyl group, a propenyl group, and an allyl group. Examples of the aryl group having 6 to 10 carbon atoms include a phenyl group, a tolyl group, and a naphthyl group, and examples of the aralkyl group having 7 to 10 carbon atoms include a benzyl group and a phenethyl group.

On the other hand, R ² represents an alkyl group having 1 to 10 carbon atoms, an acyl group having 2 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms or an aralkyl group having 7 to 10 carbon atoms. Among these groups, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms and an aralkyl group having 7 to 10 carbon atoms are the same as those described for R ¹ . 2 carbon atoms
The acyl group of 10 may be linear or branched, and specific examples include an acetyl group, a propion group, and a butyryl group. , A is an integer of 0 to 2, if R ¹ is plural, a plurality of R ¹ may be the same with or different from each other, and a plurality of OR ² may be the same with or different from each other .

Examples of the organosilicon compound represented by the general formula (I) include methyl silicate, ethyl silicate, n-propyl silicate, i-propyl silicate, n-butyl silicate, sec-butyl silicate,
t-butyl silicate, tetraacetoxysilane, methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, methyltriacetoxysilane, methyltributoxysilane, methyltripropoxysilane, methyltriamyloxysilane, methyltriphenoxysilane, Methyltribenzyloxysilane, methyltriphenethyloxysilane, glycidoxymethyltrimethoxysilane, glycidoxymethyltriethoxysilane, α-glycidoxyethyltriethoxysilane, β
-Glycidoxyethyltrimethoxysilane, β-glycidoxyethyltriethoxysilane, α-glycidoxypropyltrimethoxysilane, α-glycidoxypropyltriethoxysilane, β-glycidoxypropyltrimethoxysilane, β -Glycidoxypropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ
-Glycidoxypropyltripropoxysilane, γ-glycidoxypropyltributoxysilane, 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-glycidoxypropylmethyldiethoxysila β-glycidoxypropylmethyldimethoxysilane, β -Glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropylmethyldipropoxysilane, γ-glycidoxypropylmethyldisilane Butoxysilane, γ-glycidoxypropylmethyldiphenoxysilane, γ-glycidoxypropylethyldimethoxysilane, γ-glycidoxypropylethyldiethoxysilane, γ-glycidoxypropylvinyldimethoxysilane, γ-glycid Xypropylvinyldiethoxysila γ-glycidoxypropylphenyldimethoxysilane, γ-glycidoxypropylphenyldiethoxysilane,

Ethyltrimethoxysilane, ethyltriethoxysilavinyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxyethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltriacetoxysilane, γ-chloropropyltrimethoxysilane , Γ-chloropropyltriethoxysilane, γ-chloropropyltriacetoxysilane,
3,3,3-trifluoropropyltrimethoxysilane,
γ-methacryloxypropyltrimethoxysilane, γ
-Mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, β-cyanoethyltriethoxysilane, chloromethyltrimethoxysilane,
Chloromethyltriethoxysilane, N- (β-aminoethyl) γ-aminopropyltrimethoxysilane, N-
(Β-aminoethyl) γ-aminopropylmethyldimethoxysilane, γ-aminopropylmethyldimethoxysilane, N- (β-aminoethyl) γ-aminopropyltriethoxysilane, N- (β-aminoethyl) γ-aminopropyl Methyldiethoxysilane, dimethyldimethoxysilane, phenylmethyldimethoxysilane, dimethyldiethoxysilane, phenylmethyldiethoxysilane, γ
-Chloropropylmethyldimethoxysilane, γ-chloropropylmethyldiethoxysilane, dimethyldiacetoxysilane, γ-methacryloxypropylmethyldimethoxysilane, γ-methacryloxypropylmethyldiethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ- Mercaptopropylmethyldiethoxysilane, methylvinyldimethoxysilane, methylvinyldiethoxysilane and the like can be mentioned. These may be used alone or in combination of two or more.

In order to form a cured film containing a metal oxide on a plastic substrate, the metal oxide colloid particles and the organosilicon compound represented by the general formula (I) are mixed in a solvent such as a lower alcohol. Is added usually in a weight ratio of 1: 100 to 10: 1, and further, an appropriate amount of an acid and, if desired, a curing accelerator or a surfactant are added to prepare a coating solution, and then the solution is applied onto a substrate. And harden.

At this time, as a curing accelerator optionally used, for example, amines such as allylamine and ethylamine, and various salts or bases including Lewis acids and Lewis bases, such as organic carboxylic acids, chromic acids and hypochlorous acids , Boric acid, perchloric acid, bromic acid, selenous acid, thiosulfuric acid, salts containing orthosilicic acid, thiocyanic acid, nitrous acid, aluminate, carbonic acid, or metal salts, and also metals containing aluminum, zirconium, and titanium Alkoxides or metal chelate compounds thereof are exemplified.

As a method of coating on a substrate, a dipping method, a spin method, a spray method or the like is generally applied.
The spin method is preferred. Before coating and curing the coating liquid on the substrate, the plastic substrate is subjected to a chemical treatment with an acid, an alkali, and various organic solvents, a physical treatment with plasma, ultraviolet light, and the like, a cleaning treatment with various detergents, and a variety of resins. The used primer treatment can also be performed.

Further, the curing treatment after the application of the coating liquid on the substrate can be carried out by hot-air drying or irradiation of activation energy rays. Curing by hot air drying is suitably performed in hot air at 90 to 150 ° C, and preferably in hot air at 100 to 120 ° C. Examples of the activation energy ray include far infrared rays, and curing by irradiation with the activation energy ray has an advantage that damage due to heat can be suppressed to a low level.

The thickness of the cured film is usually 0.1 to 10
μm, preferably in the range of 1 to 5 μm.

The water-repellent optical member of the present invention is obtained by providing a fluorinated porous thin film on a plastic substrate having a cured film containing a metal oxide formed in this manner. The fluorinated porous thin film is
Although not limited thereto, it is preferably formed by a method using components (a), (b) and (c) and a fluoroalkylsilane-based compound as described below. The water-repellent optical member preferably has a surface whose contact angle with water is 150 degrees or more.

The method for producing the water-repellent optical member of the present invention is not particularly limited. According to the method of the present invention described below, a desired water-repellent optical member can be efficiently produced.

In the method of the present invention, (a) an organosilicon compound, (b) an organic polymer compound and (c)
A coating solution comprising a hydrolyzate of an alcohol solution containing a curing accelerator is prepared, and the coating solution is applied on a plastic substrate having a cured film containing the metal oxide obtained as described above, and cured by heating. To form a cured film.

As the organosilicon compound of the component (a), a compound represented by the general formula (II) (R ³ ) _b Si (OR ⁴ ) _4-b (II) is preferably used.

In the above general formula (II), R ³ represents an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms or a 7 to 10 carbon atoms.
R ⁴ represents an alkyl group having 1 to 10 carbon atoms, an acyl group having 2 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, or an aralkyl group having 7 to 10 carbon atoms.
Specific examples of these groups include R ¹ in the above general formula (I).
And R ² are as described above.

B represents an integer of 0 to 2. If there are a plurality of R ^3, a plurality of R ³ may be the same with or different from each other, and a plurality of OR ⁴ may be the same with or different from each other.

Examples of the organosilicon compound represented by the general formula (II) include, for example, methyl silicate, ethyl silicate, n-propyl silicate, i-propyl silicate, n-butyl silicate, sec-butyl silicate,
t-butyl silicate, tetraacetoxysilane, methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, methyltriacetoxysilane, methyltributoxysilane, methyltripropoxysilane, methyltriamyloxysilane, methyltriphenoxysilane, Methyltribenzyloxysilane, methyltriphenethyloxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, vinyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxyethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltriethoxysilane Acetoxysilane, dimethyldimethoxysilane, phenylmethyldimethoxysilane, dimethyldiethoxysilane, phenylmethyldiethoxy Such as emissions, and the like. These may be used alone or in combination of two or more.

Examples of the organic polymer compound as the component (b) include polyacrylic acid, sodium polystyrene sulfonate, and polyethylene glycol.
These may be used alone or in combination of two or more. In the present invention, the organosilicon compound of the component (a) and the organic polymer compound of the component (b) are
The organic polymer compound / organosilicon compound weight ratio is 0.01
It is desirable to use it so as to be in the range of 5 to 5. If the weight ratio is less than 0.01, the effect of making porous may not be sufficiently exhibited, and if it exceeds 5, the cured coating tends to whiten.

Further, as the curing accelerator of the component (c), for example, amines such as allylamine and ethylamine;
Lewis acids, various salts or bases including Lewis bases, such as organic carboxylic acids, chromic acid, hypochlorous acid, boric acid,
Perchloric acid, bromic acid, selenous acid, thiosulfuric acid, orthosilicic acid, thiocyanic acid, nitrous acid, aluminate, a salt having carbonic acid, or a metal salt, and further a metal alkoxide having aluminum, zirconium, titanium or a metal alkoxide thereof Metal chelate compounds and the like. These may be used alone or in combination of two or more. The amount used is appropriately selected according to the type and amount of the organosilicon compound as the component (a).

The components (a), (b) and (c)
The preparation of a coating solution comprising a hydrolyzate of an alcohol solution containing the components is carried out, for example, by preparing the above-mentioned organosilicon compound as the component (a), the organic polymer compound as the component (b), and (c) in a suitable alcohol-based solvent. The reaction is carried out by adding a curing accelerator of a component and, if desired, a surfactant, and further adding an appropriate amount of an acid, followed by hydrolysis at room temperature for about 5 to 30 hours. If the hydrolysis treatment time is less than 5 hours, the hydrolysis of the organosilicon compound is insufficient,
There is a possibility that sufficient film hardness may not be obtained, and a film that takes more than 30 hours tends to be whitened.

In the method of the present invention, the coating liquid thus prepared is applied to a plastic substrate on which a cured film containing a metal oxide has been formed, and cured by heating to form a cured film. As a method of coating the substrate, a dipping method, a spin method, a spray method or the like is applied as a usual method, but a dipping method and a spin method are preferable in terms of surface accuracy. The curing treatment is preferably performed at a temperature of 150 ° C. or lower by hot air drying or activation energy ray irradiation. The curing treatment by hot air drying is suitably performed in hot air at 90 to 150 ° C, preferably in hot air at 100 to 120 ° C. If the temperature is lower than 90 ° C., curing is not sufficiently performed, and 1
If the temperature is higher than 50 ° C., the plastic substrate and the cured film thereon may be damaged. Examples of the activation energy ray include far infrared rays, and curing by irradiation with the activation energy ray has an advantage that damage due to heat can be suppressed to a low level.

Next, a porous thin film is formed by removing the organic polymer compound in the cured film thus formed using a polar solvent. Examples of the polar solvent used at this time include alcohols such as methanol, ethanol, and isopropyl alcohol, ketones such as acetone, and water.

The removal of the organic polymer compound from the cured film can be achieved by simply immersing the substrate on which the cured film has been formed in the above-described polar solvent. It is effectively removed and a porous thin film is formed. The thickness of the porous thin film is usually in the range of 0.01 to 5 μm, preferably 0.1 to 1 μm.

In the method of the present invention, the surface of the porous thin film thus formed is fluorinated using a solution containing a fluoroalkylsilane compound. On this occasion,
The fluoroalkylsilane compound to be used is not particularly limited, but for example, CF ₃ CH ₂ CH ₂ Si (OCH ₃ )
₃ , CF ₃ (CF ₂ ) ₅ CH ₂ CH ₂ Si (OCH ₃ ) ₃ , CF
₃ (CF ₂ ) ₇ CH ₂ CH ₂ Si (OCH ₃ ) ₃ , CF ₃ CH ₂
CH ₂ SiCl ₃ , CF ₃ (CF ₂ ) ₅ CH ₂ CH ₂ SiC
_{l 3, CF 3 (CF 2} ) 7 CH 2 CH 2 SiCl 3 , and the like. These may be used alone or in combination of two or more. As the solvent, a fluorinated organic solvent is preferable from the viewpoint of the solubility of the above compound.

When the surface of the porous thin film is subjected to the fluorination treatment, it is desirable to form the film as a single layer as possible. If it is too thick, the effect of making the film porous is reduced, and the water repellency is not significantly improved. In order to approach a single-layer film, it is preferable to remove excess fluoroalkylsilane-based compound adhering to the surface using a fluorine-based organic solvent.

Specifically, the substrate provided with the porous thin film is immersed in a fluorine-based organic solvent solution containing a fluoroalkylsilane-based compound for an appropriate time, taken out, cured by heating, and then cured with a fluorine-containing organic solvent. A method of immersion in the substrate and ultrasonic cleaning is preferably used.

As described above, the plastic optical member of the present invention having a cured film having excellent water repellency, film hardness, adhesion and transparency can be obtained efficiently.

[0040]

EXAMPLES 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 plastic substrate having the water-repellent cured film were evaluated according to the following procedures.

(1) Scratch resistance test The plastic surface was rubbed with steel wool # 0000, and the scratch resistance was visually determined. The criteria were as follows. A: Hardly scratched even when strongly rubbed B: Scratched considerably when strongly rubbed C: Scratched as well as plastic substrate (2) Adhesion test 100 cross-cuts at 1 mm intervals, adhesive tape [trade name] "Cellotape, Nichiban Co., Ltd.] was strongly adhered and quickly peeled off, and the presence or absence of peeling of the cured film was examined. (3) Appearance Transparency and surface properties were examined indoors and visually. (4) Contact angle measurement The contact angle was measured with a K12 automatic surface tensiometer (manufactured by KRUESS) using the Wilhelmy method.

Example 1 First, 250 parts by weight of methanol-dispersed colloidal silica (solid content: 30% by weight, average particle size: 15 millimicrons) was charged into a glass container equipped with a magnetic stirrer, and γ- 100 parts by weight of glycidoxypropylmethoxysilane was added dropwise. After completion of the dropping, 20 parts by weight of 1 N hydrochloric acid, and 0.1% of a silicone surfactant are further added.
After adding 3 parts by weight of aluminum acetylacetonate as a curing accelerator and sufficiently stirring, the mixture was filtered to prepare a coating solution (1).

The diethylene bisallyl carbonate homopolymer was immersed in a 10% by weight aqueous solution of sodium hydroxide at 45 ° C. for 5 minutes to dry sufficiently, and then the coating liquid (1) prepared by the above method was used. Then, coating was performed by a dipping method (with a pulling rate of 15 cm / min), followed by heating and curing at 120 ° C. for 2 hours to obtain a cured film-carrying substrate.

Next, 100 parts by weight of ethyl silicate, 300 parts by weight of ethanol and 100 parts by weight of ethylene glycol were charged into a glass container equipped with a magnetic stirrer, and 30 parts of polyacrylic acid (average molecular weight: 2,000) was added with stirring. 1 part by weight of a silicone-based surfactant, and 5 parts by weight of aluminum acetylacetonate as a curing accelerator.
70 parts by weight of 0.1 N hydrochloric acid was added dropwise and reacted at 20 ° C. for 15 hours. After completion of the reaction, the mixture was filtered to obtain a coating liquid (2).

The plastic substrate carrying the cured film was treated with the coating liquid (2) by dipping (with a pulling rate of 10 cm / min) to obtain
C. for 2 hours. Treated substrate in ethanol 3
Ultrasonic cleaning was performed in distilled water for 30 minutes and finally in isopropyl alcohol for 30 minutes to remove the polyacrylic acid in the cured film, thereby obtaining a porous silica thin film-carrying plastic substrate.

A glass container equipped with a magnetic stirrer was charged with 10 parts by weight of CF ₃ (CF ₂ ) ₇ CH ₂ CH ₂ SiCl _{3 and} 100 parts by weight of m-xylene hexafluoride. The porous silica thin film-carrying substrate was immersed in the solution for 1 hour. After one hour, the substrate was taken out and heated and cured at 100 ° C. for 30 minutes. Finally, ultrasonic cleaning was performed in m-xylene hexafluoride for 15 minutes to obtain a plastic substrate carrying a water-repellent film. As shown in Table 1, the obtained cured film was a cured film which was excellent in film hardness, adhesion and transparency and exhibited water repellency with a contact angle of 150 ° or more.

COMPARATIVE EXAMPLE 1 The same procedure as in Example 1 was carried out except that polyacrylic acid was not added to the coating liquid (2) of Example 1. The resulting coating was not a porous thin film,
As shown in Table 2, the cured film had a contact angle of 120 degrees.

Comparative Example 2 The procedure of Example 1 was repeated, except that the plastic substrate was not treated with the coating liquid (1). As shown in Table 1, the obtained coating film had insufficient film hardness and adhesion to the substrate.

[0050]

[Table 1]

[0051]

According to the present invention, a plastic optical member having a cured film excellent in water repellency, film hardness, adhesion and transparency can be efficiently obtained. The optical member of the present invention,
For example, it can be used for eyeglass lenses, camera lenses, optical filters attached to personal computer displays, and the like.

Claims (7)

[Claims] 1. A water-repellent optical member comprising a fluorinated porous thin film on a surface of a plastic substrate on which a cured film is formed. 2. The cured coating is composed of a metal oxide colloid particle and a compound represented by the following general formula (I) (R ¹ ) _a Si (OR ² ) _4-a (I) (wherein R ¹ has 1 to 10 carbon atoms) An alkyl group, a substituted alkyl group having 1 to 10 carbon atoms in the alkyl group, and 2 to 1 carbon atoms
An alkenyl group having 0, an aryl group having 6 to 10 carbon atoms or an aralkyl group having 7 to 10 carbon atoms, and R ² has 1 to 10 carbon atoms.
Alkyl group, acyl group having 2 to 10 carbon atoms, 6 to
It represents 10 aryl groups or aralkyl groups having 7 to 10 carbon atoms, and a represents an integer of 0 to 2. When R ¹ is a plurality, the plurality of R ¹ may be the same with or different from each other, and a plurality of OR ² may be the same with or different from each other. The water-repellent optical member according to claim 1, comprising an organosilicon compound represented by the formula: 3. A plastic thin film having a cured film containing a metal oxide on a surface of a plastic substrate, wherein (a) a general formula (II) (R ³ ) _b Si (OR ⁴ ) _4-b (II) ( In the formula, R ³ is an alkyl group having 1 to 10 carbon atoms, 2 carbon atoms.
10 alkenyl group, an aryl group or an aralkyl group having 7 to 10 carbon atoms having 6 to 10 carbon atoms, R ⁴ is 1 to carbon atoms
It represents an alkyl group having 10 carbon atoms, an acyl group having 2 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms or an aralkyl group having 7 to 10 carbon atoms, and b represents an integer of 0 to 2. If there are a plurality of R ^3, a plurality of R ³ may be the same with or different from each other, and a plurality of OR ⁴ may be the same with or different from each other. ), A hydrolyzate of an alcohol solution containing (b) an organic polymer compound and (c) a curing accelerator is applied, cured by heating, and then cured in a cured film using a polar solvent. The water-repellent optical member according to claim 1, wherein the water-repellent optical member is formed by removing the organic polymer compound. 4. The water-repellent optical member according to claim 1, wherein the fluorination treatment is performed using a fluoroalkylsilane-based compound. 5. The water-repellent optical member according to claim 1, wherein a contact angle of the surface with water is 150 degrees or more. 6. A plastic substrate surface to form a cured coating film, (a) the general formula _{^{(II) (R 3) b}} Si (OR 4) 4-b (II) ( wherein, R ³ is 1 to carbon atoms 10 alkyl groups, 2 carbon atoms
10 alkenyl group, an aryl group or an aralkyl group having 7 to 10 carbon atoms having 6 to 10 carbon atoms, R ⁴ is 1 to carbon atoms
It represents an alkyl group having 10 carbon atoms, an acyl group having 2 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms or an aralkyl group having 7 to 10 carbon atoms, and b represents an integer of 0 to 2. If there are a plurality of R ^3, a plurality of R ³ may be the same with or different from each other, and a plurality of OR ⁴ may be the same with or different from each other. ), A hydrolyzate of an alcohol solution containing (b) an organic polymer compound and (c) a curing accelerator is applied, cured by heating, and then cured in a cured film using a polar solvent. A method for producing a water-repellent optical member, comprising: removing the organic polymer compound of (1) to form a porous thin film; and then fluorinating the surface of the porous thin film with a solution containing a fluoroalkylsilane-based compound. 7. The cured film is composed of metal oxide colloid particles and a compound represented by the following general formula (I) (R ¹ ) _a Si (OR ² ) _4-a (I) (wherein R ¹ has 1 to 10 carbon atoms) An alkyl group, a substituted alkyl group having 1 to 10 carbon atoms in the alkyl group, and 2 to 1 carbon atoms
An alkenyl group having 0, an aryl group having 6 to 10 carbon atoms or an aralkyl group having 7 to 10 carbon atoms, and R ² has 1 to 10 carbon atoms.
Alkyl group, acyl group having 2 to 10 carbon atoms, 6 to
It represents 10 aryl groups or aralkyl groups having 7 to 10 carbon atoms, and a represents an integer of 0 to 2. When R ¹ is a plurality, the plurality of R ¹ may be the same with or different from each other, and a plurality of OR ² may be the same with or different from each other. 7. The method for producing a water-repellent optical member according to claim 6, comprising an organosilicon compound represented by the formula: