JPH05196804A - Coating liquid for high-refractive index plastic lens - Google Patents

Abstract

PURPOSE:To provide the coating compsn. adequate for obtaining a high- refractive index plastic lens having colorless transparency. CONSTITUTION:The coating compsn. is applied on the surface of the base plate of the high-refractive index plastic lens and contains the following components (A) and (B): (A) An org. silicon compd. expressed by general formula R<1> (R<3>)aSiO(OR<2>)3-ao (where R<1> denotes 4 to 14C org. group contg. an epoxy group; R<2> denotes 1 to 4C alkyl group or 1 to 4C acyl group; R<3> denotes 1 to 6C alkyl group (a) denotes an integer from 0 to 2) or its hydrolyzate. (B) At least one kind of the dyes selected from an anthraquinone violet oil-soluble dye and anthraquinone blue oil-soluble dye.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a composition for coating a high-refractive-index plastic lens used for various optical lenses such as spectacle lenses and camera lenses, to make the plastic lenses colorless and transparent. ..

[0002]

2. Description of the Related Art Recently, demand for plastic lenses, for example, as lenses for spectacles is increasing in Japan and overseas.
As a plastic lens used in recent years, diethylene glycol bisallyl carbonate (hereinafter referred to as DAC
(Hereinafter abbreviated as ") is generally used. The characteristics of DAC resin are that it is lighter than glass, is hard to break, and has excellent dyeability, and it can meet the current fashionable needs of combining color lenses with a large frame. However, since the DAC resin has a refractive index (hereinafter abbreviated as n _d ) of 1.500, which is lower than n _d 1.523 of a glass spectacle lens, the lens has to be thick especially when the lens power is strong. I'm not getting much favored by users.

On the other hand, n _d is 1.
A polyurethane lens is known as a plastic lens having a relatively high refractive index of 56 to 1.64. As this polyurethane lens, for example, JP-A-60-19901 is used.
No. 6 discloses a polyurethane lens made of a copolymer of polyisocyanate and polythiol.
This polyurethane lens is widely used as an optical lens such as an eyeglass lens.

[0004]

However, the polyurethane lens proposed in Japanese Patent Laid-Open No. 60-199016 and the like is generally more yellowish than the DAC resin, and compared with the conventional DAC resin spectacle lens. There was a problem that coloring was remarkable.

Other high-refractive-index plastic lenses are easily colored yellow or the like, and it has been desired to make these high-refractive-index plastic lenses colorless and transparent.

As a method for making a plastic lens colorless and transparent, JP-A-61-83212 discloses a method of adding a dye, a fluorescent brightening agent and the like together with a polymerization initiator to a monomer for a plastic lens, and then polymerizing the same. , A method of dyeing a plastic lens obtained by polymerization with a disperse dye is disclosed.

However, the former method has the drawback that the dye or the fluorescent whitening agent is decomposed by the polymerization initiator, and the latter method also has the drawback that the dye must be selected according to the plastic lens. It has the drawback that adjustment is difficult and color correction is necessary.

Therefore, it is an object of the present invention to solve the above-mentioned drawbacks of the prior art and to provide a coating composition suitable for obtaining a high refractive index plastic lens having colorless transparency.

[0009]

The present inventor has earnestly studied to achieve the above-mentioned object, and as a result, yellowing is likely to occur.
For example, when a coating composition containing the following components (A) and (B) is applied to the surface of a high refractive index plastic lens substrate such as a polyurethane lens and cured, it is found that the high refractive index plastic lens has colorless transparency,
The present invention has been completed.

(A) General formula R ¹ (R ³ ) _a Si (OR ² ) _3-a (wherein R ¹ is an organic group having 4 to 14 carbon atoms, including an epoxy group, and R ² is 1 to 1 carbon atoms). 4 alkyl groups or 1 carbon atom
To 4 acyl groups, R ³ is an alkyl group having 1 to 6 carbon atoms, a
Represents an integer of 0 or 1) or an organosilicon compound represented by the formula or a hydrolyzate thereof.

(B) At least one dye selected from anthraquinone violet oil-soluble dyes and anthraquinone blue oil-soluble dyes.

As described above, the present invention relates to a coating composition applied on the surface of a high refractive index plastic lens substrate, and as a material of the high refractive index plastic lens substrate on which the coating composition is applied. As long as it is a high-refractive-index plastic lens that tends to become yellow, its type is not particularly limited, but for example, a plastic lens or a polyurethane lens made of a polymer obtained by crosslinking a radically polymerizable polyfunctional organic vinyl monomer containing an aromatic ring is particularly preferable. preferable. Here, the polyurethane lens is obtained by casting polymerization of polyisocyanate and polythiol in, for example, a mold including a lens molding die and a resin gasket.

The polyisocyanate used as a monomer for producing a polyurethane lens is not particularly limited, but tolylene diisocyanate, diphenylmethane diisocyanate, polymeric diphenylmethane diisocyanate, naphthylene diisocyanate,
Hexamethylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, hydrogenated xylylene diisocyanate, hydrogenated diphenylmethane diisocyanate, lysine diisocyanate, triphenylmethane triisocyanate, tris (isocyanatophenyl) thiophosphate, trans-cyclohexane 1,4-diisocyanate, p- Phenylene diisocyanate, tetramethylene diisocyanate, 1,6,1
Polyisocyanate compounds such as 1-undecane triisocyanate, 1,8-diisocyanate-4-isocyanate methyloctane, lysine ester triisocyanate, 1,3,6-hexamethylene triisocyanate and bicycloheptane triisocyanate, and allophanate modification of those compounds Body, burette modified product, isocyanurate modified product, adduct modified product with polyol or polythiol, and the like, and may be used alone,
You may use as a mixture of 2 or more types as needed. Other known isocyanate compounds can be used, but the isocyanate compound as the main component must be bifunctional or higher. A halogen atom such as Cl or Br may be introduced into a known aromatic isocyanate compound. Particularly preferred isocyanate compounds include isocyanate compounds represented by xylylene diisocyanate, isophorone diisocyanate and hexamethylene diisocyanate.

The polythiol used for the reaction with the polyisocyanate for producing the polyurethane lens is not particularly limited, and known ones can be used. For example, ethanedithiol, propanedithiol, propanetrithiol, butanedithiol, pentanedithiol, hexanedithiol, heptanedithiol, octanedithiol, cyclohexanedithiol,
Examples thereof include cycloheptanedithiol, 2,5-dichlorobenzene-1,3-dithiol, pentaerythritol tetrakis-3-mercaptopropionate, pentaerythritol tetrakisthioglycolate, and the pentaerythritol derivative is particularly preferable.

The coating composition of the present invention applied to the surface of a high refractive index plastic lens substrate contains the following components (A) and (B).

(A) General formula R ¹ (R ³ ) _a Si (OR ² ) _3-a (wherein R ¹ is an organic group having an epoxy group and having 4 to 14 carbon atoms, and R ² is 1 to 1 carbon atoms). 4 alkyl groups or 1 carbon atom
To 4 acyl groups, R ³ is an alkyl group having 1 to 6 carbon atoms, a
Represents an integer of 0 or 1) or an organosilicon compound represented by the formula or a hydrolyzate thereof.

(B) At least one dye selected from anthraquinone violet oil-soluble dyes and anthraquinone blue oil-soluble dyes.

The organosilicon compound represented by the general formula R ¹ (R ³ ) _a Si (OR ² ) _{3- a} or its hydrolyzate used as the component (A) in the present invention is γ-glycidoxypropyl. Trimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropyldimethoxyethoxysilane, γ-glycidoxypropyltriacetoxysilane, β- (3,4-epoxycyclohexyl) ethyltriexisilane, γ Examples thereof include glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropyldimethylmonomethoxysilane and the like, and hydrolysates thereof, but are not limited to these.

The dye used as the component (B) in the present invention is selected from anthraquinone violet oil-soluble dyes and anthraquinone blue oil-soluble dyes. Examples of these oil-soluble dyes include violet-based or blue-based oil-soluble dyes obtained by reacting an anthraquinone compound with p-toluidine, and specifically, CI solvent violet 13, CI solvent violet 14, CI solvent blue 11 , CI Solvent Blue 12,
CI Solvent Blue 36 and the like are preferably used, but not limited to these. These oil-soluble dyes may be used alone or in combination of two or more.
When two or more oil-soluble dyes are used, these may be selected from the anthraquinone violet-based oil-soluble dye group, or may be selected from the anthraquinone blue-based oil-soluble dye group, and further, the anthraquinone violet-based oil-soluble dye group. And the anthraquinone blue oil-soluble dye group.

The amount of the oil-soluble dye used is 5 to 10 relative to the total weight of the composition containing the organosilicon compound and the oil-soluble dye.
It is preferably in the range of 0 ppm, particularly preferably in the range of 20 to 50 ppm. The reason is that if the amount of the oil-soluble dye is less than 5 ppm, the lens is insufficiently colorless and transparent, while if it exceeds 100 ppm, the lens is blue, which is not preferable.

Oil soluble dyes other than the oil soluble dyes of the above-mentioned component (B), for example, red oil soluble dyes, yellow oil soluble dyes, blue oil soluble dyes containing phthalocyanine compounds, monoazo blue oil soluble dyes. It is not preferable to use a dye or a triphenylmethane blue oil-soluble dye. The reason is that even if an oil-soluble dye other than the component (B) is added to the coating composition to form a coating film, the coating film is colored during the curing reaction of the coating composition and the polyurethane lens becomes colorless and transparent. Because it cannot be achieved. Further, it is not preferable to add a dye other than the oil-soluble dye, for example, a disperse dye, a cationic dye, an acid dye or the like.
The reason is that the above-mentioned dye has poor solubility, does not disperse uniformly, and causes problems such as coloring of the coating film during the curing reaction of the coating composition.

The coating composition of the present invention contains Al, T in order to reduce the generation of interference fringes due to the coating film.
It is provided on a fine particle inorganic substance made of an oxide of a metal such as i, Zr, Sn, Sb, a fine grain inorganic substance made of an oxide of a metal such as Si, or if necessary, on a coating film for improving scratch resistance. Epoxy compounds such as polyglycerol polyglycidyl ether, glycerol polyglycidyl ether, and diglycerol polyglycidyl ether can be added to improve the adhesion to the inorganic antireflection film. Further, an ultraviolet absorber, an antioxidant, a curing agent, etc. can also be used. Furthermore, the coating composition used in the present invention improves the flowability during application,
Various surfactants may be added for the purpose of improving the smoothness of the coating film. As a coating means, a commonly used method such as a dipping method, a spin method and a spray method can be applied, but the dipping method and the spin method are particularly preferable from the viewpoint of surface accuracy and the like.

[0023]

EXAMPLES The present invention will be described in detail below with reference to examples, but the present invention is not limited to these examples. All parts in the examples are based on weight. The physical properties of the high refractive index plastic lenses obtained in the examples and comparative examples were measured by the following measuring methods. (1) Total light transmittance The light transmittance (%) in the entire visible light range was examined. (2) Yellowness (YI value) It was measured according to JIS-K-7103. (3) Impact resistance 16 cm from a height of 127 cm at the center of a lens with a center thickness of 2 mm
The steel ball of g was dropped and examined for damage. (4) Appearance It was visually examined under a fluorescent lamp whether the lens was colored.

[Example 1] 1. Preparation of high refractive index polyurethane lens coated with coating composition of the present invention 100 parts by weight of m-xylylene diisocyanate, 142 parts by weight of pentaerythritol tetrakis-3-mercaptopropionate and phosphorus. 6 parts by weight of di-n-butyl acid, 0.25 parts by weight of dibutyltin dilaurate and 0.5 parts by weight of 2- (2'-hydroxy-5'-t-octylphenyl) benzotriazole as an ultraviolet absorber were mixed sufficiently. After stirring, degassing was performed under a vacuum of 1 mmHg for 60 minutes.

Then, the above-mentioned mixed solution is poured into a mold consisting of a glass lens-molding mold and a resin gasket, and 2
The temperature is continuously raised from 5 ° C to 120 ° C over 20 hours,
Then, the mixture was kept at 120 ° C. for 2 hours to carry out polymerization. After the polymerization, the gasket was removed and the lens mold was separated from the lens to obtain a high refractive index polyurethane lens with a center thickness of 2.0 mm and a power of 0.00D. The obtained lens has n _d = 1.592,
It had good optical properties of ν _d = 36.

2. Preparation of coating composition of the present invention To 212 parts by weight of γ-glycidoxypropyltrimethoxysilane, 54 parts by weight of 0.06N hydrochloric acid aqueous solution was added dropwise with stirring. After completion of dropping, stirring was carried out for 24 hours to obtain a hydrolyzate. Then, as an epoxy compound, Denacol EX
68 parts by weight of -521 (manufactured by Nagase Kasei Co., Ltd., polyglycerol polyglycidyl ether), 34 parts by weight of titanium-iso-propoxyoctylene glycolate as a curing agent, and Orient Oil Violet # as anthraquinone violet oil-soluble dye. 73
20 ppm (corresponding to CI Solvent Violet 13, manufactured by Orient Chemical Industry Co., Ltd.) was added and aged for 100 hours with stirring to obtain a coating composition of the present invention.

3. Formation of cured film The high-refractive-index polyurethane lens prepared by the above method 1 was immersed in a 10% aqueous solution of NaOH at 50 ° C. for 5 minutes to thoroughly wash it, and then prepared by the above method 2. Using the coating composition of the present invention thus prepared, coating was carried out by a dipping method (pulling rate: 12 cm / min) and heating was carried out at 120 ° C. for 1 hour to form a coating film, whereby a polyurethane lens with a coating film was obtained.

As shown in Table 1, the evaluation result of the polyurethane lens with the coating film was that the impact resistance was good, the total light transmittance was 90%, and the YI value showing yellowness was 0.8 and DA.
It has the same YI value of 0.8 as that of the C resin lens, and it has colorless transparency when visually observed under a fluorescent lamp, and the high refractive index plastic lens colorless effect of the coating composition of the present invention was confirmed. Was done.

Example 2 The same procedure as in Example 1 was carried out except that 40 ppm of Orient Oil Violet # 732 (corresponding to CI Solvent Violet 14 manufactured by Orient Chemical Industry Co., Ltd.) was used as the anthraquinone violet oil-soluble dye. Prepare a coating composition,
Using this, a polyurethane lens having a coating film was obtained. The obtained polyurethane lens with a coating film had excellent physical properties as in Example 1 as shown in Table 1, and the plastic lens colorless effect of the coating composition of the present invention was confirmed.

[Example 3] As an anthraquinone blue-based oil-soluble dye, DIARESON BLUE P (Mitsubishi Kasei Co., Ltd.)
Co., Ltd. (corresponding to CI Solvent Blue 36) was used to prepare a coating composition in the same manner as in Example 1 to obtain a polyurethane lens having a coating film. As shown in Table 1, the obtained polyurethane lens with a coating film had excellent physical properties as in Example 1, and the plastic lens colorless effect of the coating composition of the present invention was confirmed.

[Example 4] As anthraquinone blue oil-soluble dye, Sumiplast Blue G (Sumitomo Chemical Co., Ltd.)
A coating composition was prepared in the same manner as in Example 1 except that 10 ppm of CI Solvent Blue 11) was used, and a polyurethane lens having a coating film was obtained. As shown in Table 1, the obtained polyurethane lens with a coating film had excellent physical properties as in Example 1, and the plastic lens colorless effect of the coating composition of the present invention was confirmed.

[Comparative Example 1] Anthraquinone violet oil-soluble dye (Orient Oil Violet # 730, manufactured by Orient Chemical Industry Co., Ltd.) in Example 1
A coating composition was prepared in the same manner as in Example 1 except that 30 ppm of Eisenspirone Violet RH (manufactured by Hodogaya Chemical Co., Ltd.) was used as the monoazo violet oil soluble dye instead of 20 ppm, and coating was performed using this. A polyurethane lens having a film was obtained. The obtained polyurethane lens with a coating film had a YI value of 1.6 and its color tone was light brown, and the coating composition used had no plastic lens colorless effect. It became clear.

[Comparative Example 2] Victoria Blue F4R (BASF) as a triarylmethane blue oil-soluble dye
A coating composition was prepared in the same manner as in Example 1 except that 40 ppm was used, and a polyurethane lens having a coating film was obtained using the coating composition. The obtained polyurethane lens with a coating film was YI. The value was 1.7, the color tone was light brown, and it was confirmed that the coating composition used did not have a plastic lens colorless effect.

[Comparative Example 3] A coating composition was prepared in the same manner as in Example 1 except that 20 ppm of Aizen spirone blue GNH (Hodogaya Chemical Co., Ltd.) was used as the phthalocyanine blue oil-soluble dye. A polyurethane lens having a coating film was obtained using
The obtained polyurethane lens with a coating film is YI
The value was 1.5, the color tone was light brown, and it was confirmed that the coating composition used did not have a plastic lens colorless effect.

[0035]

[Table 1]

[0036]

As described above, according to the present invention, a coating composition for making a high refractive index plastic lens colorless is provided.

Claims (1)

[Claims] 1. A coating composition applied to the surface of a high refractive index plastic lens substrate, wherein the coating composition comprises the following components (A) and (B). (A) General formula R ¹ (R ³ ) _a Si (OR ² ) _3-a (wherein R ¹ is an organic group having an epoxy group and having 4 to 14 carbon atoms, and R ² is an alkyl group having 1 to 4 carbon atoms. Group or carbon number 1
To 4 acyl groups, R ³ is an alkyl group having 1 to 6 carbon atoms, a
Represents an integer of 0 or 1) or an organosilicon compound represented by the formula or a hydrolyzate thereof. (B) At least one selected from anthraquinone violet oil-soluble dyes and anthraquinone blue oil-soluble dyes
Seed dye.