JPH05164902A - Synthetic resin lens - Google Patents

Abstract

PURPOSE:To prevent the generation of interference fringes and to obtain high surface hardness and durability by providing a hard coating film having the refractive index approximately equal to the refractive index of a base material lens on the high-refractive index synthetic resin lens. CONSTITUTION:A coating compsn. essentially consisting of a component A, component B and component C is applied on the base material having about 1.60 refractive index and is cured The component A is a colloidal dispersion of composite particulates of 1 to 30mum formed by treating the composite particulates constituted of inorg. oxides of Ce, Ti and Si by an org. silicon compd. The component B is an org. silicon compd. expressed by formula I or the hydrolyzate thereof. The component C is an org. silicon compd. expressed by formula II or the hydrolyzate thereof. In the formulas I and II, R<1> denotes 1 to 6C hydrocarbon group, vinyl group, mercapto group, etc.; R<2> denotes 1 to 4C hydrocarbon group; R denotes 1 to 8C hydrocarbon group, alkoxyalkyl group, etc., (a) denotes 0 or 1.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION The present invention relates to a synthetic resin lens surface having a refractive index of about 1.60 or more, which has wear resistance, chemical resistance, and hot water resistance having a refractive index similar to that of a base material. The present invention relates to a synthetic resin lens having a transparent coating excellent in durability such as heat resistance, heat resistance, and weather resistance. Further, the present invention relates to a synthetic resin lens in which an antireflection film made of an inorganic substance is provided on the transparent film.

[0002]

2. Description of the Related Art Synthetic resin lenses, particularly diethylene glycol bis (allyl carbonate) resin lenses, are superior to glass lenses in safety, workability, fashionability, etc., and in recent years, antireflection technology,
It is rapidly spreading due to the development of hard coat technology and hard coat + antireflection technology. However, the refractive index of diethylene glycol bis (allyl carbonate) resin is 1.
Since it is 50, which is smaller than that of the glass lens, it has a drawback that the outer peripheral portion is thicker than the glass lens. For this reason, the use of plastic spectacle lenses has increased the demand for thin plastic lenses made of high refractive index resin materials. As technical proposals therefor, JP-A-59-133211, JP-A-63-46213, and JP-A-2-27.
A high-refractive-index resin material having a refractive index of around 1.60 or higher, such as that of Japanese Patent No. 0859, has been proposed.

On the other hand, the plastic spectacle lens has a drawback that it is easily scratched. Therefore, a method of coating the surface of the plastic lens with a silicon type hard coat film is generally used. However, when the same method is applied to a high-refractive index resin lens having a refractive index of around 1.60 or higher, interference fringes are generated due to the difference in the refractive index between the resin lens and the coating film, which causes poor appearance. Cause. As a technical proposal for solving this problem, a colloidal dispersion of fine particles of silicon dioxide used in a silicon-based coating composition as disclosed in JP-B-61-54331 and JP-B-63-37142 is proposed. A coating technique of replacing with a colloidal dispersion of inorganic oxide fine particles of Al, Ti, Zr, Sn, and Sb having a refractive index is disclosed. In addition, JP-A-1-3015
JP-A No. 2-264 discloses a method for producing a composite sol of titanium dioxide and cerium dioxide.
No. 902, a composite inorganic oxide fine particle of Ti and Ce,
In JP-A-3-68901, Ti, Ce and Si are disclosed.
There is disclosed a technique of using fine particles obtained by treating the complex inorganic oxide of (1) with an organic silicon compound in a coating composition.

[0004]

However, among the above-mentioned coating techniques, the coating compositions disclosed in JP-B-61-54331 and JP-B-63-37142 are
It had the following problems. For example, Al, Zr,
When a colloidal dispersion of fine particles of inorganic oxides of Sn and Sb is used as a coating composition for high refractive index resin lenses having a refractive index of about 1.60 or more, coating and curing are performed as compared with a silicone-based coating composition. The degree of subsequent interference fringes can be improved. However, when fine particles of inorganic oxides of Al and Sb are used, it is impossible to completely suppress the interference fringes because the refractive index of the coating film is limited. This is because the inorganic oxide fine particles alone have a high refractive index of 1.60 or more, but when used as a coating material, a silicon-based coupling agent, an epoxy resin, etc. are generally mixed, so that the refractive index of the coating film itself. Is lower than the base lens. Further, in the case of using the inorganic oxide fine particles of Zr and Sn, the dispersibility thereof is unstable, so that a transparent film cannot be obtained. on the other hand,
When a colloidal dispersion of fine particles of an inorganic oxide of Ti is used as a coating composition, TiO ₂ itself has a higher refractive index than the inorganic oxide, and thus the formed film has a thickness of about 1.60. Furthermore, there is an advantage that a higher refractive index layer is provided, and at the same time, the range of selection of the refractive index of the coating is widened. However, since TiO ₂ has extremely poor weather resistance, a coating formed from TiO ₂ and a silicon-based coupling agent decomposes the organic component of the silicon-based coupling agent in the coating, and further the coating on the surface of the resin substrate. Deteriorated and there was a problem in its durability.

Further, the coating composition using composite fine particles of titanium dioxide and cerium dioxide disclosed in JP-A-2-264902 has poor dispersion stability of fine particles and poor transparency of the coating film. Furthermore, in the coating composition disclosed in JP-A-3-68901, when colloidal silica is used for adjusting the refractive index, the compatibility with the composite fine particles is poor and the coating becomes cloudy, so that the ratio of the silane coupling agent and the like in the solid content is reduced. It was necessary to adjust the refractive indexes of the base material and the coating film by increasing the refractive index.
This composition has a problem that the adhesiveness of the antireflection film is deteriorated because the resin component is increased. Further, the liquid composition in the examples was unsuitable for a base material such as a sulfur-containing urethane resin lens from which a dyeing agent is easily removed because the curing speed of the coating liquid is slow.

Therefore, the present invention is intended to solve these problems, and its object is to obtain a refractive index of 1,6.
For thin spectacles with high surface hardness and durability that prevent the occurrence of interference fringes by providing a hard coat film having a refractive index of about 0 or more and a high refractive index synthetic resin lens with the same refractive index as the base lens. It is to provide a synthetic resin lens.

[0007]

In order to achieve the above object, the synthetic resin lens of the present invention has a refractive index of 1. The coating composition containing the following components A, B and C as main components. It is obtained by coating and curing on a substrate of about 60 or more.

A. Colloidal dispersion of composite fine particles having a particle diameter of 1 to 300 mμ, which is obtained by treating composite fine particles composed of an inorganic oxide of Ce, Ti and Si with an organic silicon compound. An organosilicon compound represented by the general formula R ¹ R ² _a Si (OR ³ ) _3-a , or a hydrolyzate thereof. C. An organosilicon compound represented by the general formula Si (OR ³ ) ₄ or a hydrolyzate thereof.
(Here, R ¹ is an organic group having a hydrocarbon group having 1 to 6 carbon atoms, a vinyl group, a methacryloxy group, a mercapto group, an amino group, or an epoxy group, and R ² is an organic group having 1 to 4 carbon atoms.
Hydrocarbon group of R ³ , R ³ is a hydrocarbon group having 1 to 8 carbon atoms,
The alkoxyalkyl group, the acyl group and a represent 0 or 1. ) Hereinafter, the synthetic resin lens of the present invention will be described in detail.

The component A used in the coating composition according to claim 1 of the present invention is a composite fine particle of cerium dioxide, titanium dioxide and silicon dioxide treated with an organosilicon compound and having a particle diameter of 1 to 300 mμ. The composite fine particles are dispersed in water or an organic solvent in a colloidal form. Titanium dioxide has a crystal structure of 2.2 to
It is an inorganic oxide having a refractive index of 2.7 and higher than that of Al, Zr, Sn, and Sb. However, a coating obtained by applying and curing a colloidal dispersion of fine particles of titanium dioxide and a coating liquid containing a silicon-based coupling agent as a main component has poor weather resistance, and the adhesion between the base material and the coating is reduced or The degradation of the film occurs due to the decomposition of the vehicle components inside. It is considered that this occurs because titanium dioxide absorbs and activates ultraviolet light of 280 to 320 nm. Therefore, by compounding titanium dioxide and cerium dioxide, cerium dioxide absorbs ultraviolet light from a wavelength range higher than that of titanium dioxide, and activation of titanium dioxide can be prevented. The mixing ratio of cerium dioxide for improving the weather resistance of titanium dioxide in the two types of composite is C
It is necessary that eO ₂ / TiO ₂ (weight ratio) is 0.1 or more. Further, if the amount of cerium dioxide is too much, the yellow tint becomes strong, so it is preferable to use it at 1.0 or less.

Further, by combining these two kinds of fine particles with fine particles of silicon dioxide, the dispersion stability in water or an organic solvent can be enhanced. The mixing ratio of the silicon dioxide fine particles is 5% by weight to 3% based on the total solid content of the sol.
It is preferably in the range of 0% by weight, and when it is 5% by weight or less, the effect of the dispersion stability is insufficient. It is necessary to prepare a state dispersion. Although the stability of fine particles in various solvents is improved by compounding with silicon dioxide, in order to ensure the dispersion stability of the fine particles when used as a coating liquid, the composite fine particles are further treated with an organosilicon compound. There is a need to. As the organosilicon compound used at this time,
R ₃ SiX (R is an alkyl group, a phenyl group, a vinyl group,
Examples include monofunctional silanes represented by methacryloxy group, mercapto group, amino group, organic group having epoxy group, X is a hydrolyzable group, such as trimethylsilane, dimethylphenylsilane, and dimethylvinylsilane. Alternatively, a bifunctional silane represented by R ₂ SiX ₂ , such as dimethylsilane and diphenylsilane, a trifunctional silane represented by RSiX ₃ , such as methylsilane and phenylsilane, and a tetrafunctional represented by SiX _4. Silanes such as tetraalkoxysilane. In the treatment, the hydrolyzable group may be untreated or may be hydrolyzed. Further, after the treatment, it is preferable that the hydrolyzable group reacts with the -OH group of the fine particles, but there is no problem in stability even if it remains partially. The addition amount of these organosilicon compounds is 1 to 15% based on the weight of the composite fine particles.
It needs to be added within a certain range. The organic silane-treated composite fine particles are present in the solvent in a state where three kinds of metal oxide fine particles are aggregated and / or three kinds of metal oxides are chemically bonded to form one fine particle. is there. The particle size of the composite fine particles is preferably about 1 to 300 mμ, and if the particle size is too small, it is difficult to produce,
Since the cost is high and it is not practical, and if it is too large, the transparency is deteriorated, the above range is preferable. As the dispersion medium of the composite fine particles, water, hydrocarbons, esters, ketones, alcohols, cellosolves, amines, organic carboxylic acids, etc. can be used. Also, these dispersion media can be used as a mixture of two or more kinds.

Furthermore, the refractive index, the adhesion, and the
In order to optimize the dyeability, heat resistance, etc. depending on the type of the base lens, fine particles of inorganic oxide such as Al, Zr, Sn, Sb, Ta, La and In are compounded or mixed with the fine particles of Ce-Ti-Si. Can also be used. The proportion of the above-mentioned inorganic oxide fine particles in the cured film is appropriately 10% by weight to 90% by weight, and it is necessary to adjust the coating composition to fall within this range. When the content is less than 10% by weight, the hardness is insufficient, and when the content is more than 90% by weight, the adhesion between the substrate and the coating is deteriorated, and cracks are generated in the coating after curing. Use is preferred.

The organosilicon compound represented by the general formula R ¹ R ² _a Si (OR ³ ) _3-a , which is the component B of the present invention, or a hydrolyzate thereof is methyltrimethoxysilane or ethyltriethoxysilane. , Methyltriethoxysilane, phenyltriethoxysilane, dimethyldimethoxysilane, phenylmethyldimethoxysilane, vinyltriethoxysilane, vinyltrimethoxysilane, vinyltris (β-methoxyethoxy) silane, γ-glycidoxypropyltrimethoxysilane, γ -Glycidoxypropyltriethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, β- (3.4-epoxycyclohexyl) ethyltrimethoxysilane, γ-methacryloxypropyl Trimetoki Silane, N-beta (aminoethyl) .gamma.-aminopropyltrimethoxysilane, N-beta (aminoethyl) .gamma.
Examples thereof include aminopropylmethyldimethoxysilane, γ-aminopropyltriethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane and γ-mercaptopropyltrimethoxysilane. These may be used alone or in combination of two or more. Further, these are preferably used by hydrolyzing in an organic solvent such as alcohol in the presence of an acid. Even if they are hydrolyzed alone and mixed with a colloidal dispersion of inorganic oxide fine particles, or an inorganic oxide is used. It may be hydrolyzed after being mixed with the colloidal dispersion. The proportion of the coating component derived from the organosilicon compound of component B or its hydrolyzate in the cured coating is preferably 10% by weight to 90% by weight. If it is 10% by weight or less, the adhesion between the base material and the coating is lowered, which is not preferable, and if it is 90% by weight or more, the refractive index of the coating is lowered and interference fringes are likely to occur, and further it is composed of an inorganic substance. It is preferable to prepare the coating composition within this range because the adhesion of the antireflection film is lowered.

Next, the C component of the present invention, which is an organosilicon compound represented by the general formula Si (OR ³ ) ₄ or a hydrolyzate thereof, has a refractive index of the formed film while maintaining the transparency of the film. It is used for the purpose of adjusting and further accelerating the curing speed of the coating film after the coating liquid is applied. The colloidal dispersion of the composite fine particles of the component A of the present invention has a refractive index of 1.8-2.0 in the composition ratio of stable fine particles, so that the refractive index of the coating film is matched with the refractive index of the base material. In this case, it is necessary to reduce the content of the composite metal oxide in the coating film. However, in such a composition system, the adhesion of the antireflection film made of an inorganic substance cannot be obtained. When colloidal silica is used in the coating composition in order to adjust the refractive index without reducing the ratio of the total inorganic oxides, the dispersion stability of the colloidal dispersion of the composite fine particles deteriorates, and the particles agglomerate after curing. There is a problem that the coating becomes cloudy. By using the component C of the present invention, the refractive index of the coating after curing can be appropriately changed according to the refractive index of the base lens, and even if the content of the composite inorganic oxide decreases, the adhesion of the antireflection film can be improved. It is possible to obtain the sex. Further, by using the tetrafunctional silane compound represented by the component C as a coating composition, the curing speed after coating is increased, and a coating film is formed on a base material such as a sulfur-containing urethane resin in which a dyeing agent is easily removed. In some cases, the amount of dropout can be suppressed and the change in color tone of the dyed lens before and after the film formation can be reduced. As the tetrafunctional silane compound, tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetraisopropoxysilane, tetrabutoxysilane, tetraphenoxysilane, tetraacetoxysilane, tetraallyloxysilane, tetrakis (2-methoxyethoxy)
Silane, tetrakis (2-ethylbutoxy) silane, tetrakis (2-ethylhexyloxy) silane, etc. can be used. Incidentally, the organosilicon compounds of the component B and the component C can be cured without the presence of a catalyst, but various curing catalysts can be used to further accelerate the curing. For example, amines such as n-butylamine, triethylamine, guanidine and biguanide, amino acids such as glycine, aluminum acetylacetonate, chromium acetylacetonate, titanylacetylacetonate, metal acetylacetonate such as cobalt acetylacetonate, sodium acetate. , Zinc naphthenate, cobalt naphthenate, zinc octylate, organic acid metal salts such as tin octylate, perchloric acid, ammonium perchlorate, perchlorates such as magnesium perchlorate or salts thereof, hydrochloric acid, phosphoric acid, Nitric acid, acids such as paratoluenesulfonic acid, or SnCl ₂ , AlCl ₃ , FeCl ₃ ,
A metal chloride which is a Lewis acid such as TiCl ₄ , ZnCl ₃ or SbCl ₃ can be used.

The coating composition of the present invention also comprises
Use one or more selected from polyfunctional epoxy compounds, polyhydric alcohols, polycarboxylic acids, or polycarboxylic anhydrides for the purpose of improving the dyeability of the formed film or improving various durability. can do. As the polyfunctional epoxy compound, (poly) ethylene glycol,
Diglycidyl ether of difunctional alcohol such as (poly) propylene glycol, neopentyl glycol, catechol, resorcinol, alkylene glycol,
Alternatively, di- or triglycidyl ethers of trifunctional alcohols such as glycerin and trimethylolpropane may be used. Examples of the polyhydric alcohol include difunctional alcohols such as (poly) ethylene glycol, (poly) propylene glycol, neopentyl glycol, catechol, resorcinol, and alkylene glycol, trifunctional alcohols such as glycerin and trimethylolpropane, or polyvinyl. Examples include alcohol. Examples of the polycarboxylic acid include malonic acid, succinic acid, adipic acid, azelaic acid, maleic acid, orthophthalic acid, terephthalic acid, fumaric acid, itaconic acid and oxaloacetic acid. As the polycarboxylic acid anhydride,
Succinic anhydride, maleic anhydride, itaconic anhydride, 1.
Examples thereof include 2-dimethylmaleic anhydride, phthalic anhydride, hexahydrophthalic anhydride, naphthalic anhydride and the like.

The coating composition of the present invention is used by adjusting the solid content concentration by adding a solvent such as alcohols, ketones, cellosolves and carboxylic acids, alone or in a mixture. Further, if necessary, a small amount of a surfactant, an antistatic agent, an ultraviolet absorber, a disperse dye / oil soluble dye / pigment may be added to improve the coating property of the coating liquid and the film performance after curing.

Further, in applying the coating composition of the present invention, the surface of the substrate is previously treated with an alkali, an acid, a surfactant, an inorganic or organic substance for the purpose of improving the adhesion between the substrate lens and the coating. It is effective to carry out polishing treatment with fine particles, primer treatment or plasma treatment.

As a coating / curing method, a coating solution is uniformly applied by a dipping method, a spinner method, a spray method or a flow method, and then 40 to 200.
A coating can be formed by heating and drying at a temperature of ° C for several hours. In particular, for a substrate having a heat distortion temperature of less than 100 ° C., a spinner method that does not require fixing the lens with a jig is suitable. The film thickness of the film is preferably 1 to 30 μm. When the film thickness is less than 1 μm, the scratch resistance of the obtained film is insufficient, and when it exceeds 30 μm, the film is apt to crack.

The cured film of the present invention formed by the above method has a function of protecting the base lens from ultraviolet rays because titanium dioxide and cerium dioxide have ultraviolet ray absorbing ability.
This not only improves the yellowing resistance of the base lens due to light, but also prevents the deterioration of the adhesion between the base material and the coating in the weather resistance test when plasma treatment is used as the pretreatment of the base lens. it can.

Next, a synthetic resin lens substrate which is a coating substrate of the coating composition of the present invention will be described. As publicly known, there are numerous published patent publications as technical proposals for obtaining a synthetic resin lens having a high refractive index. The material useful as a thin spectacle lens for the purpose of the present invention preferably has a refractive index of about 1.60 or more, and further has transparency, dyeability, heat resistance, water absorption, bending strength,
As the base lens capable of satisfying desired properties in terms of impact resistance, weather resistance, processability, etc., the sulfur-containing urethane resin lens according to claim 2 and the (meth) acrylic resin according to claim 3. Lenses are preferred. Below, the manufacturing method of these base material lenses is demonstrated.

The sulfur-containing urethane type resin lens described in claim 2 has a polyisocyanate compound and a general formula:

[0021]

[Chemical 5]

4-mercaptomethyl-3,6 represented by
-Dithio-1,8-octanedithiol or the general formula

[0023]

[Chemical 6]

It is obtained by injecting a mixed solution of pentaerythritol tetra (3-mercaptopropionate) thiol compound represented by the following into a mold consisting of a glass mold and a gasket and polymerizing by heating. Examples of the polyisocyanate compound include tolylene diisocyanate, diphenylmethane diisocyanate, polymeric diphenylmethane diisocyanate, tolidine diisocyanate, naphthalene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, hydrogenated xylylene diisocyanate, hydrogenated diphenylmethane diisocyanate, tetramethylxylylene diisocyanate. Isocyanate, 2.5-bis (isocyanatomethyl) bicyclo [2.2.1] heptane,
2.6-bis (isocyanatomethyl) bicyclo [2.
2.1] heptane, 3.8- bis (isocyanatomethyl) tricyclo [5.2.1,0 ^2,6] - decane, 3.
9-bis (isocyanatomethyl) tricyclo [5.
2.1.0 ^2,6 ] -decane, 4.8-bis (isocyanatomethyl) tricyclo [5.2.1.0 ^2,6 ] -decane, 4.9-bis (isocyanatomethyl) tricyclo [5. 2.1.0 ^2,6 ] -decane, polyisocyanate compounds such as dimer acid diisocyanate, and allophanate modified products, buret modified products, and isocyanurate modified products of these compounds are listed, and they may be used alone or, if necessary, in two types. You may use it as a mixture of the above. The polyisocyanate compound and the thiol compound are used at a ratio of NCO / SH (functional group) molar ratio of usually 0.5 to
It is within the range of 3.0, preferably 0.5 to 1.5. In addition, an internal release agent, a chain extender, a cross-linking agent, a light stabilizer, an ultraviolet absorber, an antioxidant, a colorant such as a disperse dye / oil soluble dye / pigment, a reaction catalyst, etc. should be appropriately added to the raw material You can also The sulfur-containing urethane resin thus obtained is a material suitable as a lens for spectacles, which has a feature that it has a high Abbe number despite its high refractive index. The (meth) acrylic resin lens according to claim 3 has the general formula

[0025]

[Chemical 7]

The (meth) acrylic monomer represented by

[0027]

[Chemical 8]

It is obtained by copolymerization of a styrene derivative monomer represented by As the (meth) acrylic monomer, 2,2-bis (3,5-dibromo-4- (meth) acryloyloxyethoxyphenyl) propane is preferable. Moreover, styrene, chlorostyrene, bromostyrene, etc. can be used as a styrene derivative monomer. In the copolymerization, a comonomer composed of 20 to 80% by weight of the (meth) acrylic monomer and 80 to 20% by weight of a styrene derivative monomer is injected into a mold composed of a glass mold and a gasket to carry out radical copolymerization. It is obtained by doing. At this time, a radical polymerization initiator such as an organic peroxide, a cross-linking agent, a light stabilizer, an ultraviolet absorber, an antioxidant, a coloring agent such as a dye or a pigment, and the like can be appropriately added. The (meth) acrylic resin thus obtained is a lens material for spectacles having the features of high refractive index and high strength.

A single-layer or multi-layer antireflection film comprising an inorganic material according to claim 4, after the coating composition of the present invention is applied to the synthetic resin lens substrate obtained by the above method and cured to form a cured film. By providing, it is possible to reduce reflection and improve transmittance, and it is possible to further improve the function as a spectacle lens. As an inorganic substance, Si
O, SiO ₂ , Si ₃ N ₄ , TiO ₂ , ZrO ₂ , Al
_The antireflection film can be formed using ₂ O ₃ , MgF ₂ , Ta ₂ O ₅ or the like by a thin film forming method such as a vacuum deposition method.

[0030]

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

Example 1 (1) Preparation of coating composition Ethyl cellosolve 4 was placed in a flask equipped with a stirrer.
1.15 g, γ-glycidoxypropyltrimethoxysilane 38.44 g, and tetramethoxysilane 4.13 g were sequentially added with stirring, and then 0.05N hydrochloric acid water was added 12.
90 g was added and stirred for 30 minutes. Subsequently, a silicon-based surfactant (manufactured by Nippon Unicar Co., Ltd., trade name "L-760"
4 ") and 0.04g further methyl cellosolve dispersed titanium dioxide one cerium dioxide - silicon composite fine particle sol dioxide _{(TiO 2 / CeO 2 / SiO} 2 = 68/17/15 ( weight ratio), solid content concentration of 20.5 wt% 103.39 g of tetramethoxysilane-treated product) and 0.016 g of Disperse Violet 1 as a bluing agent were added and sufficiently stirred, and then the mixture was allowed to stand at 0 ° C. for 24 hours for aging to obtain a coating composition.

(2) Preparation of plastic lens substrate 4-mercaptomethyl-3,6-dithio-1,8-octanedithiol 87 g, m-xylylene diisocyanate 94 g, dibutyltin dilaurate 0.02 g, internal release agent 15 g and 0.09 g of 2- (5-methyl-2-hydroxyphenyl) benzotriazole were mixed and sufficiently stirred, and then degassing was performed under a vacuum of 5 mmHg for 60 minutes. Then, the mixture is poured into a mold composed of a glass mold and a gasket, kept at 40 ° C. for 7 hours, and then polymerized in a heating furnace where the temperature is raised from 40 ° C. to 120 ° C. over 10 hours. After cooling, the glass mold is cooled. The gasket was removed to obtain a lens made of a sulfur-containing urethane resin. The obtained lens had a refractive index of 1.66 and an Abbe number of 33.

(3) Formation of cured film The sulfur-containing urethane resin lens produced by the above method was immersed in a 5 wt% sodium hydroxide aqueous solution for 5 minutes, washed and dried, and then adjusted in (1). The coating solution was applied by spin coating. Spin coating was performed by applying the hard coating solution during low rotation and then shaking off at a rotation speed of 2500 rpm and a rotation time of 1 second. After coating, the film was provisionally baked at 120 ° C. for 30 minutes, cooled, and then coated on the remaining surface under the same conditions and heated and cured at 120 ° C. for 3 hours to form a cured coating. The film thickness of the obtained coating was 2.3 μm. In addition, using a commercially available plastic lens dyeing agent (Amber D for Seiko Plax),
A similar coating was provided on the fabric that had been dyed in a dyeing bath at 0 ° C. for 3 minutes. The transmittance before and after the film formation was measured using a spectrophotometer (MCPD-1000, manufactured by Otsuka Electronics Co., Ltd.), and the color difference was obtained. ΔE _ab was 1.1, and no large color tone change was visually perceived. It was

(4) Formation of Antireflection Film The lens having the cured film formed by the method described above is exposed to argon gas plasma with an output of 200 W in vacuum for 30 seconds, and then vacuum evaporation is performed from the lens side. SiO ₂ , ZrO ₂ , SiO ₂ , ZrO ₂ , SiO toward the atmosphere side
_{A two-} layer, five-layer thin film was formed. The optical film thickness of the formed antireflection film is such that SiO ₂ is about λ / 4 and ZrO ₂
The total film thickness of SiO ₂ and SiO ₂ is about λ / 4, the next ZrO ₂ is about λ / 4, and the uppermost SiO ₂ is about λ / 4. The design wavelength λ is 510 nm. Perform the following performance evaluation test on the synthetic resin lens obtained above,
The results are shown in Table 1. Appearance: Regarding the presence or absence of the occurrence of interference fringes, the light of the fluorescent lamp was reflected on the lens surface in the state where the background was black, and the occurrence of a rainbow pattern due to the interference of light was visually observed. The judgment was performed as follows. ◯: No rainbow pattern is observed. Δ: A rainbow pattern is slightly observed. X: A rainbow pattern is clearly recognized. Scratch resistance: ^# 0000 steel wool with a load of 1
The state of the coating film after 10 reciprocations at kg / cm ² was observed. A: Almost no scratches. B: A little scratched. C: Many scratches. Adhesion: After immersing in warm water of 70 ° C for 2 hours, 11 parallel line-shaped scratches were made on the lens surface with a knife at 1 mm intervals vertically and horizontally, and 100 squares were made to adhere and peel cellophane tape. The number of squares remaining without peeling off the film was checked. Weather resistance: Using a xenon long life fade meter (manufactured by Suga Test Instruments Co., Ltd.), after exposure for 150 hours, the following evaluation was performed. i) Appearance: The coloring of the lens was visually observed. ii) Adhesion: The post-test lens was subjected to the same crosscut tape test as above on the exposed surface.

Example 2 (1) Preparation of coating composition Ethyl cellosolve 3 was placed in a flask equipped with a stirrer.
7.87 g, γ-glycidoxypropyltrimethoxysilane 34.01 g, tetraethoxysilane 21.90 g
Are sequentially added while stirring, and then 0.05N hydrochloric acid water 2
1.79 g was added and stirred for 30 minutes. Subsequently, 0.04 g of the same silicon-based surfactant as used in Example 1 and methyl cellosolve-dispersed titanium dioxide-cerium dioxide-silicon dioxide composite fine particle sol (TiO ₂ / CeO ₂ /
SiO ₂ = 68/16/16 (weight ratio), solid content concentration 2
0.5 wt%, methoxytrimethylsilane treated product) 8
4.44 g, and 0.016 g of the same bluing agent used in Example 1 were added and sufficiently stirred, and then allowed to stand at 0 ° C. for 24 hours for aging to obtain a coating composition.

(2) Preparation of plastic lens substrate 130 g of pentaerythritol tetra (3-mercaptopropionate), 100 g of m-xylylene diisocyanate, 0.018 g of dibutyltin dichloride, 0.18 g of internal mold release agent, 2- (2) '-Hydroxy-5'-
t-octylphenyl) benzotriazole 0.115
g was mixed and sufficiently stirred, and then degassing was performed for 60 minutes under a vacuum of 5 mmHg. Then, the mixture was poured into a mold composed of a glass mold and a gasket, polymerization was carried out in the same heating pattern as in Example 1, and after cooling, the glass mold and the gasket were removed to obtain a sulfur-containing urethane resin lens. The obtained lens had a refractive index of 1.59 and an Abbe number of 36.

(3) Formation of cured coating The sulfur-containing urethane resin lens produced by the above method is immersed in an aqueous solution of sodium hydroxide having a concentration of 5% by weight for 5 minutes, washed and dried, and then the coating prepared in (1). A liquid was used to form a cured film by the same coating and curing method as in Example 1. The film thickness of the obtained film was 2.5 μm. still,
When the color difference before and after applying the coating was determined for the material dyed in the same manner as in Example 1, ΔE _ab was 0.8, and no large color tone change was visually perceived.

(4) Formation of Antireflection Film Example 1 was applied to a lens having a cured film formed by the above method.
An antireflection film was provided in the same manner as in. The synthetic resin lens obtained above was subjected to the same performance evaluation test as in Example 1, and the results are shown in Table 1.

(Example 3) (1) Preparation of coating composition Methyl cellosolve 6 was placed in a flask equipped with a stirrer.
8.18 g, γ-glycidoxypropyltrimethoxysilane 13.12 g, γ-glycidoxypropylmethyldiethoxysilane 27.58 g, tetramethoxysilane 1
6.91 g was added in order with stirring, and then 18.02 g of 0.05N hydrochloric acid water was added and stirred for 30 minutes. Subsequently, methanol-dispersed titanium dioxide-cerium dioxide-silicon dioxide composite fine particle sol (TiO2 / CeO2 / SiO2)
= 64/16/20 (weight ratio), solid content concentration 30% by weight, dimethoxydiphenylsilane-treated product) 50.05 g
And glycerin diglycidyl ether (trade name “Denacol EX-313” manufactured by Nagase & Co., Ltd.) 5.6
7 g, silicon-based surfactant (manufactured by Nippon Unicar Co., Ltd.,
0.04 g of trade name "L-7001"), 0.4713 g of magnesium perchlorate as a curing catalyst, and 0.016 g of the same bluing agent used in Example 1 were added in this order.
After dissolving, the mixture was allowed to stand at 0 ° C. for 24 hours for aging to obtain a coating composition.

(2) Preparation of plastic lens substrate 50 g of styrene, 2.2-bis (3.5-dibromo-4)
-Methacryloyloxyethoxyphenyl) propane 4
8.5 g, diethylene glycol bisallyl carbonate 2.8 g, diisopropyl peroxydicarbonate 1.5 g, and 2- (5-methyl-2-hydroxyphenyl) benzotriazole 0.2 g were mixed and sufficiently stirred, and then glass type It was poured into a mold composed of a gasket. Then, at 30 ℃ for 4 hours, 30 ℃ to 50 ℃
After heating for 10 hours, 50 ° C. to 70 ° C. for 2 hours, 70 ° C. for 1 hour, and 80 ° C. for 2 hours, the glass mold and the gasket were removed by cooling to obtain a methacrylic resin lens. The obtained lens had a refractive index of 1.59 and an Abbe number of 32.

(3) Formation of cured film The methacrylic resin lens produced by the above method was subjected to an air flow rate of 100 ml / min, an output of 50 W and a vacuum degree of 0. 2To
or for 30 seconds. After that, the coating liquid prepared in (1) was used to perform coating by a depping method at a pulling rate of 15 cm / s. 120 ° C after application
And cured for 3 hours to form a cured coating. The film thickness of the obtained coating was 2.2 μm. This lens is used in Example 1
When dyeing was carried out using the same dye as the above, the total light transmittance was 53%, and good dyeability was exhibited.

(4) Formation of Antireflection Film An antireflection film was provided on the dyed lens having the cured film formed by the above method in the same manner as in Example 1. The synthetic resin lens obtained above was subjected to the same performance evaluation test as in Example 1, and the results are shown in Table 1.

Comparative Example 1 In a flask equipped with a stirrer, 54.63 g of ethyl cellosolve and 38.09 g of γ-glycidoxypropyltrimethoxysilane were sequentially added with stirring, and then 0.05N hydrochloric acid water 10 was added. 0.46 g was added and stirred for 30 minutes. Subsequently, 0.04 g of the same silicon-based surfactant as used in Example 1 was further added, and 96.83 g of antimony pentoxide methanol sol (manufactured by Nissan Chemical Industries, Ltd., solid content concentration 30% by weight) was added and sufficiently stirred. rear,
The coating composition was obtained by allowing it to stand at 0 ° C. for 24 hours for aging.

This coating composition was applied to the sulfur-containing urethane resin lens having a refractive index of 1.66 produced in Example 1 by the same coating and curing method as in Example 1 to form a cured film. The film thickness of the obtained film was 2.2 μm. Further, an antireflection film was provided by the same method as in the above-mentioned embodiment. The synthetic resin lens obtained as described above was subjected to the same performance evaluation test as in Example 1, and the results are shown in Table 1. When the color difference before and after applying the coating was determined for the fabric dyed in the same manner as in Example 1, ΔE _ab was 2.0 and a change in color tone was visually perceived.

[Comparative Example 2] In a flask equipped with a stirrer, 69.21 g of ethyl cellosolve and 51.98 g of γ-glycidoxypropyltrimethoxysilane were sequentially added with stirring, and then 0.05N hydrochloric acid water was added. 14.27 g was added and stirred for 30 minutes. Subsequently, 0.04 g of the same silicon-based surfactant as used in Example 1 and 64.54 g of methylcellosolve-dispersed titanium dioxide-cerium dioxide-silicon dioxide composite fine particle sol, the same bluing agent as used in Example 1 were used. After 016 g was added and sufficiently stirred, the mixture was allowed to stand at 0 ° C. for 24 hours for aging to obtain a coating composition. The coating composition was applied to the sulfur-containing urethane resin lens having a refractive index of 1.59 prepared in Example 2 by the same coating and curing method as in Example 1 to form a cured film. The film thickness of the obtained coating was 2.3 μm. Further, an antireflection film was provided in the same manner as in Example 1 above. The synthetic resin lens obtained above was subjected to the same performance evaluation test as in Example 1, and the results are shown in Table 1. In addition, when the color difference before and after applying the coating was determined for the material dyed in the same manner as in Example 1, ΔE _ab was 2.1, and a change in color tone was visually perceived.

Comparative Example 3 In a flask equipped with a stirrer, 43.40 g of ethyl cellosolve and 34.01 g of γ-glycidoxypropyltrimethoxysilane were sequentially added with stirring, and then 0.05N hydrochloric acid water was added. 9.34 g was added and stirred for 30 minutes. Subsequently, 0.04 g of the same silicon-based surfactant as used in Example 1, 84.44 g of methylcellosolve-dispersed titanium dioxide-cerium dioxide-silicon dioxide composite fine particle sol, isopropyl alcohol-dispersed colloidal silica (Catalyst Kasei Kogyo Co., Ltd.). (Trade name: "OSCAL-1432"), 0.016 g of the same bluing agent used in Example 1 was added, and after sufficiently stirring, the mixture was allowed to stand at 0 ° C for 24 hours for aging to obtain a coating composition. The coating composition was applied to the sulfur-containing urethane resin lens having a refractive index of 1.59 prepared in Example 2 by the same coating / curing method as in Example 1, and the coating became cloudy and did not become a lens. ..

[0047]

[Table 1]

[0048]

As described above, the synthetic resin lens of the present invention is a composite fine particle obtained by treating a composite fine particle composed of an inorganic oxide of titanium dioxide-cerium dioxide-silicon dioxide with an organic silicon compound. Sulfur-containing urethane resin or (meth) having a refractive index of about 1.60 or higher with a coating liquid using a colloidal dispersion
By providing an acrylic resin lens, it is possible to provide a thin eyeglass lens that suppresses the generation of interference fringes and has excellent durability. Further, the coating composition of the present invention can freely adjust the refractive index of the coating without lowering the durability by using a tetrafunctional silane compound, and the curing speed of the hard coating liquid is high, so that the sulfur-containing coating composition is vulcanized. It is possible to suppress the change in color tone after film formation as much as possible on a base material such as a urethane resin lens from which a dyeing agent easily comes off after dyeing a material.

Claims (4)

[Claims] 1. A synthetic resin lens having a cured coating obtained by applying and curing a coating composition containing the following components A, B and C as main components. A. A colloidal dispersion of composite fine particles having a particle diameter of 1 to 300 mμ, which is obtained by treating composite fine particles composed of an inorganic oxide of Ce, Ti and Si with an organic silicon compound. B. An organosilicon compound represented by the general formula R ¹ R ² _a Si (OR ³ ) _3-a , or a hydrolyzate thereof. C. An organosilicon compound represented by the general formula Si (OR ³ ) ₄ or a hydrolyzate thereof.
(Here, R ¹ is an organic group having a hydrocarbon group having 1 to 6 carbon atoms, a vinyl group, a methacryloxy group, a mercapto group, an amino group, or an epoxy group, and R ² is an organic group having 1 to 4 carbon atoms.
Hydrocarbon group of R ³ , R ³ is a hydrocarbon group having 1 to 8 carbon atoms,
The alkoxyalkyl group, the acyl group and a represent 0 or 1. ) 2. A lens substrate is a sulfur-containing urethane resin obtained by reacting at least one mercapto compound represented by the following general formula 1 or 2 with at least one polyisocyanate. The synthetic resin lens according to claim 1. [Chemical 1] [Chemical 2] 3. The synthetic resin lens according to claim 1, wherein the lens substrate is a copolymer obtained by radically polymerizing a comonomer having the following general formulas 3 and 4 as a main component. [Chemical 3] [Chemical 4] (In the formula, R ⁴ represents hydrogen or a methyl group, X ¹ and X ² represent hydrogen or halogen except fluorine, and m + n represents an integer of 0 to 8.) 4. A lens made of synthetic resin, wherein an antireflection film made of an inorganic material is laminated on the cured film according to claim 1.