JP2501162B2 - Fluorine-containing organic polysiloxane optical article - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a fluorine-containing organic polysiloxane optical article, and more particularly to a plastic optical article such as an optical element, for example, an optical lens such as an eyeglass lens or a camera lens. Is.

[0002]

2. Description of the Related Art When seeing an object through a transparent material, dust or dust adhered to an optical article such as a spectacle lens is often caused by static electricity and cannot be easily removed only by wiping.

For the purpose of preventing adhesion of dust and dust, an antistatic agent for coating using a surfactant or the like has recently been marketed, but it has only a temporary effect.

Regarding the antistatic property of plastic molded products, various methods have been known so far, for example, Japanese Patent Publication No. 55-15494 (coating with aminosilane compound) and Japanese Patent Publication No. 60-21628. (Coating with a composition consisting of epoxysilane and aminosilane), but its antistatic property was insufficient.

[0005]

SUMMARY OF THE INVENTION It is an object of the present invention to provide an optical article which is excellent in antistatic property and prevents adhesion of dust and dust.

[0006]

In order to achieve the above object, the present invention has the following constitution.

"The weight ratio of fluorine to silicon is 0.
02 above, Ru der 10 or less fluorine-containing organic polysiloxane
Optical system optical article, further comprising:
The weight ratio of fluorine to iodine is
A fluorine-containing organic polysiloxane-based optical article, which is less than 80% by weight . The fluorine-containing organic polysiloxane-based optical article referred to in the present invention has a weight ratio of fluorine to silicon (F / Si) of 0.02 or more,
It is 10 or less. When it is less than 0.02, the strength of the article is insufficient, and when it exceeds 10, the oxygen permeability is lowered. Examples of the fluorine-containing organic polysiloxane optical article include articles obtained by curing a fluorine-containing organosilicon compound represented by the following general formula (I) and / or a hydrolyzate thereof.

(R ¹ Q) SiX _a Y _3-a (I) (wherein R ¹ is a fluorine-containing alkyl group having 1 to 20 carbon atoms and contains at least one ether bond or ester bond. Q is a divalent organic group, X is a lower alkyl group, Y is a halogen, an alkoxy group, or RCOO.
^- group (wherein, R represents a hydrogen atom or a lower alkyl group), a
Represents an integer of 0 or 1. ) Specific examples of these fluorine-containing organic compounds include 3,3,3-trifluoropropyltrialkoxysilane,
3,3,3-trifluoropropylmethyldialkoxysilane,
3-trifluoroacetoxypropyltrialkoxysilane and the like can be mentioned.

The above-mentioned fluorine-containing organic polysiloxane-based optical article has one kind for the purpose of improving abrasion resistance, abrasion resistance, impact resistance, chemical resistance, flexibility, light resistance, weather resistance and the like. Alternatively, it is also preferable to use two or more kinds of other organic silicon compounds in combination.

A typical organosilicon compound and / or its hydrolyzate is shown in formula (II). R ³ _b R ⁴ _c SiZ _{4- (b + c)} (II) (wherein R ³ and R ⁴ are each an alkyl group, alkenyl group, aryl group or halogen group, epoxy group, glycidoxy group, amino group, mercapto Group, a hydrocarbon group having a methacryloxy group or a cyano group, Z is a hydrolyzable group, and b and c are 0 or 1.) Specific examples of these organosilicon compounds are:
Methyl silicate, ethyl silicate, n-propyl silicate, i-propyl silicate, n-butyl silicate,
Tetraalkoxysilanes such as sec-butyl silicate and t-butyl silicate, and their hydrolysates, further methyltrimethoxysilane, methyltriethoxysilane, methyltrimethoxyethoxysilane, methyltriacetoxysilane, methyltripropoxysilane, methyl Tributoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, vinyltrimethoxysilane,
Vinyltriethoxysilane, vinyltriacetoxysilane, vinyltrimethoxyethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltriacetoxysilane, γ-chloropropyltrimethoxysilane, γ-chloropropyltriethoxysilane,
γ-chloropropyltriacetoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, N
-Β- (aminoethyl) -γ-aminopropyltrimethoxysilane, β-cyanoethyltriethoxysilane, methyltriphenoxysilane, chloromethyltrimethoxysilane, chloromethyltriethoxysilane, glycidoxymethyltrimethoxysilane, glycid Xymethyltriethoxysilane, α-glycidoxyethyltrimethoxysilane, α-glycidoxyethyltriethoxysilane,
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) methyl Triethoxysilane, 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-
Trialkoxysilanes such as (3,4-epoxycyclohexyl) butyltriethoxysilane, triacyloxysilanes or triphenoxysilanes or their hydrolysates, and dimethyldimethoxysilane, phenylmethyldimethoxysilane, dimethyldiethoxysilane, phenylmethyldiethoxy. Silane, γ-chloropropylmethyldimethoxysilane, γ-chloropropylmethyldiethoxysilane, dimethyldiacetoxysilane, γ-methacryloxypropylmethyldimethoxysilane, γ-methacryloxypropylmethyldiethoxysilane, γ-mercaptopropylmethyldimethoxysilane , Γ-mercaptopropylmethyldiethoxysilane, γ-aminopropylmethyldimethoxysilane, γ-aminopropylmethyldiethoxysilane, methyl Nyldimethoxysilane, methylvinyldiethoxysilane, 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-glycidoxypropyl Methyldiphenoxysilane, γ-glycidoxypropylmethyldiacetoxysilane, γ-glycidoxypropylethyldimethoxysilane, γ-glycidoxypropylethyldiethoxysilane, γ-glycidoxypropylvinyldimethoxy Orchid, γ-glycidoxypropylvinyldiethoxysilane, γ-glycidoxypropylphenyldimethoxysilane, γ-glycidoxypropylphenyldiethoxysilane, etc. dialkoxysilane, diphenoxysilane or diacyloxysilanes or their hydrolysis The thing is an example.

Especially for the purpose of imparting dyeability, an epoxy group,
The use of organosilicon compounds containing glycidoxy groups is preferred.

The above-mentioned fluorine-containing organosilicon compound or a mixture of these organosilicon compounds is preferably used after being hydrolyzed in order to lower the curing temperature and further accelerate the curing.

The hydrolyzate is produced by adding pure water or an acidic aqueous solution such as hydrochloric acid, acetic acid or sulfuric acid and stirring. Furthermore, the degree of hydrolysis can be easily controlled by adjusting the amount of pure water or acidic aqueous solution added. When hydrolyzing,
It is particularly preferable to add pure water or an acidic aqueous solution that is at least equimolar and at most 3 times the molar amount of the -Y group of formula (I) from the viewpoint of promoting curing.

Since alcohol and the like are generated during the hydrolysis, it is possible to perform the hydrolysis without a solvent. However, for the purpose of performing the hydrolysis more uniformly, after mixing the organic silicon compound and the solvent, the hydrolysis is performed. It is also possible to disassemble. It is also possible to remove an appropriate amount of alcohol after hydrolysis under heating and / or reduced pressure for use depending on the purpose, and to add an appropriate solvent after that.

Examples of these solvents include alcohols, esters, ethers, ketones, halogenated hydrocarbons, and aromatic hydrocarbons such as toluene and xylene. Further, these solvents can be used as a mixed solvent of two or more kinds, if necessary. Further, depending on the purpose, it is possible to accelerate the hydrolysis reaction and further heat it to room temperature or higher in order to proceed the reaction such as precondensation, or to lower the hydrolysis temperature to room temperature or lower in order to suppress precondensation. It is also possible to do. Further, it is possible to easily disperse the dyes and pigments and the filler, dissolve the organic polymer to color it, and improve the practicality by improving the physical properties.

Further, it is possible to easily add an ultraviolet absorber for the purpose of improving weather resistance and an antioxidant as a method for improving heat deterioration resistance.

Further, in the surface layer of the above-mentioned fluorine-containing organic polysiloxane optical article (here, the surface layer means a layer within a range measurable by ESCA (X-ray photoelectron spectroscopy) from the surface), F The / Si weight ratio is preferably less than 80% of the same weight ratio of the entire fluorine-containing organic polysiloxane optical article. Antistatic exceeds 80% you decrease.

The fluorine-containing organic polysiloxane optical article of the present invention can be obtained by treating with an activated gas.
Here, the activated gas treatment is a treatment with ions, electrons or excited gas generated under normal pressure or reduced pressure. As a method of generating these activated gases, for example, a method by corona discharge, high-voltage discharge by direct current under reduced pressure, low frequency, high frequency or microwave is used. In particular, treatment with low temperature plasma obtained by high frequency discharge under reduced pressure or corona discharge treatment is suitable.

The gas used here is not particularly limited, but specific examples are oxygen, nitrogen, hydrogen, carbon dioxide, sulfur dioxide, helium, neon, argon, freon, water vapor, ammonia, carbon monoxide. , Chlorine, nitric oxide, and nitrogen dioxide.

These may be used not only in one kind but also in a mixture of two or more kinds. Among the above, preferable gases include those containing oxygen, and those existing in nature such as air may be used.

As a specific example of the measurement of the weight ratio analysis of fluorine / silicon in the present invention, X-ray photoelectron spectroscopy (E
SCA) or the like is used.

The optical article obtained by the present invention has a durable and high hardness surface, has dyeability, and has antistatic property, so that it can be used not only for sunglasses and corrective lenses but also for cameras, binoculars, It can be preferably used for lenses such as contacts. The following examples are given to clarify the characteristics of the present invention, but the present invention is not limited to these examples.

[0023]

Examples Example 1 and Comparative Example 1 (1) Preparation of Composition for Manufacturing Optical Article (a) Preparation of Hydrolyzate Methyltrimethoxysilane 4.9 g, 3,3 in a reactor equipped with a rotor. 3.5 g of 3,3-trifluoropropyltrimethoxysilane was charged, the liquid temperature was kept at 10 ° C., 2.8 g of 0.01N hydrochloric acid aqueous solution was gradually added while stirring with a magnetic stirrer, and cooling was stopped after the addition was completed. A hydrolyzate was obtained.

(B) Preparation of stock solution n-propyl alcohol 56.0 was added to the silane hydrolyzate.
g, distilled water 24.0 g, and ethyl cellosolve 7.5 g were added to a silicone-based surfactant 1.0 g prepared beforehand with n-propyl alcohol to 5% and aluminum acetylacetonate 0.24 g. After thoroughly stirring, the solution was made into a stock solution.

(2) Preparation of optical article 50 g of the undiluted solution prepared in the above (1) and (b) was heated at 82 ° C. for 1 hour.
It was pre-cured for 2 minutes and then heated and cured at 93 ° C. for 4 hours to obtain an optical article.

(3) Antistatic Development Treatment The optical article obtained in (2) above was treated by the following method.

Using a plasma apparatus for surface treatment (PR501A manufactured by Yamato Scientific Co., Ltd.), the treatment was carried out for 3 minutes at an oxygen flow rate of 100 ml / min and an output of 50 W.

The fluorine / silicon (F / Si) element content in the surface layer of the obtained article was 0.04 / 1 by weight.
Met. The weight ratio of fluorine / silicon of the whole article was 0.08 / 1.

Further, in the evaluation of antistatic property, the half-life of the charged voltage was 1 second or less, and in the punch scrap test, punch scrap did not adhere from the beginning.

Regarding the article (Comparative Example 1) obtained in the same manner as in Example 1 except that the antistatic development treatment was not carried out, fluorine / silicon (F /
The elemental content of Si) was 0.08 / 1 by weight.
Further, the half-life of the charged voltage was 121 seconds, and the punch scrap test was 25, indicating that the antistatic property was poor. The evaluation method is based on the following.

(A) Half-life of electrification voltage The half-life of electrification voltage when charged at 10 kv and 1000 rpm was measured under static conditions of 20 ° C. and 65% RH.

(B) Punch scrap test At 20 ° C. to 25 ° C. and 50 to 70% RH, the optical article is wiped with deer skin to generate static electricity, and the punch scraps scattered on the desk are reduced to about 1 to 2 cm. Bring the punch scraps close together. It was left still for 30 seconds, and the remaining punch scraps were counted without dropping.

Example 2, Comparative Example 2 As a stock solution for a fluorine-containing organic polysiloxane optical article, 50 parts by weight of methyltrimethoxysilane and 50 parts by weight of 3,3,3-trifluoropropyltrimethoxysilane were used. Except for the above, in the same manner as in Example 1, an optical article subjected to antistatic development treatment was obtained. The elemental content of fluorine / silicon (F / Si) in the surface layer of the obtained article was 0.
It was 04/1. The weight ratio of fluorine / silicon of the whole article was 0.08 / 1.

Further, in the evaluation of antistatic property, the half-life of the charged voltage was 1 second or less, and in the punch scrap test, punch scrap did not adhere from the beginning.

Regarding the article (Comparative Example 2) obtained in the same manner as in Example 2 except that the antistatic development treatment was not carried out, the fluorine / silicon (F /
The elemental content of Si) was 0.08 / 1 by weight.
Further, the half-life of the charged voltage was 360 seconds, and the punch scrap test was 30, indicating that the antistatic property was poor.

[0036]

The optical article obtained by the present invention has the following features.

(1) It has excellent durability.

(2) The dyeing speed is fast and the appearance after dyeing is good.

(3) The surface slipperiness is good, and scratches are practically unlikely to occur.

(4) Dirt is inconspicuous and easy to remove.

(5) It has an antistatic property and does not adhere to dust and dirt.

Continuation of front page (51) Int.Cl. ⁶ Identification number Reference number within the agency FI Technical display location G02B 1/10 G02C 7/02 G02C 7/02 B29K 83:00 // B29K 83:00 105: 32 105: 32 G02B 1/10 Z

Claims (1)

(57) [Claims] 1. The weight ratio of fluorine to silicon is 0.0.
2 above, Ru der 10 or less fluorine-containing organopolysiloxane
System optical article, further comprising:
The weight ratio of fluorine to element is such that
A fluorine-containing organic polysiloxane-based optical article, which is less than 80% by weight .