JPH09227830A - Coating composition and synthetic resin lens with cured coating of said composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a cured coating which has a high refractive index, is colorless and transparent, and processes excellent various types of fastness by using a colloidal dispersion (A) of a composite fine particle comprising an oxide of Sn and an oxide of Zn, an organosilicon compd. (B), and other components. SOLUTION: The component (A) has a particle diameter of 1 to 300mμand the ratio of ZnO to SnO2 (by wt.) should be 0.1 to 10.0. The component (B) is a hydrolyzate and/or partial condensate of an organosilicon compd. represented by the formula R<1> R<2> a Si(OR<3> )3-a (R<1> represents a 1-6C hydrocarbon group, vinyl, methacryloxy, mercapto, amino or epoxy; R<2> represents a 1-4C hydrocarbon group; R<3> represents a 1-8C hydrocarbon group, an alkoyxyalkyl, or acyl; and a is 0 or 1) (e.g. methyltrimethoxysilane). The above two components are used as indispensable components, and other components are added for improving the properties of a coating fluid and imparting functions to the cured coating.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention has a refractive index of 1.54.
Provide a transparent coating on the surface of the synthetic resin lens that has the same refractive index as the base material and is excellent in various durability such as abrasion resistance, chemical resistance, warm water resistance, heat resistance, and weather resistance. And a synthetic resin lens having no interference fringes, which has a cured coating of the composition. Further, the present invention relates to a synthetic resin lens having an antireflection film made of an inorganic material provided on the 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, easy processability, fashionability, etc.
It has rapidly spread 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 lower than that of the glass lens, the myopic lens has a drawback that the outer peripheral portion is thicker than the glass lens. Therefore, in the field of synthetic resin spectacle lenses,
Technological developments aimed at reducing the thickness using high-refractive index resin materials are being actively conducted. As technical proposals for that purpose, JP-A-59-133211, JP-A-63-46213, JP-A-2-270859 and JP-A-7-25.
No. 2207 proposes a high refractive index resin material having a refractive index of 1.60 or higher.

On the other hand, the plastic spectacle lens has a drawback that it is easily scratched. Therefore, a method of providing a silicon type hard coat film on the surface of the plastic lens is generally used. However, when the same method is applied to a high-refractive index resin lens having a refractive index of 1.54 or more, interference fringes are generated due to the difference in the refractive index between the resin lens and the coating film, which causes poor appearance. As a technical proposal for solving this problem, a colloidal dispersion of silicon dioxide fine particles used in a silicon-based coating composition as disclosed in JP-B-61-54331 and JP-B-63-37142 has a high refractive index. Al, Ti, Zr, S having a ratio
A coating technique of replacing with a colloidal dispersion of n, Sb inorganic oxide fine particles is disclosed. Further, JP-A-1-301517 discloses a method for producing a composite sol of titanium dioxide and cerium dioxide, and JP-A-2-264902 discloses a composite inorganic oxide fine particle of Ti and Ce, and JP-A-3201. JP-A-68901 discloses a technique in which fine particles obtained by treating a composite inorganic oxide of Ti, Ce and Si with an organic silicon compound are used in a coating composition.

[0004]

However, among the coating techniques described above, 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 inorganic oxide fine particles of Sn and Sb is used as a coating composition for a high refractive index resin lens having a refractive index of 1.54 or more, the degree of interference fringes after coating and curing is higher than that of a silicon-based coating composition. Can be improved. However, when the inorganic oxide fine particles of Al and Sb are used, the refractive index of the coating film is limited, and therefore 1.6
It was impossible to completely suppress the interference fringes for the lens base material of 0 or more. 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, an organic silicon compound, an epoxy resin, etc. are generally mixed, so that the filling rate decreases and the refractive index of the coating film decreases. This is because the index becomes lower than that of 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 it was not possible to form a transparent coating film if the amount was sufficient to form the high refractive index coating film. 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 above-mentioned inorganic oxides, and thus the formed film has 1. There is an advantage that a high refractive index film having a refractive index of about 60 or more is provided and, at the same time, the range of selection of the refractive index of the film is widened. However, since TiO ₂ has extremely poor weather resistance, a coating formed of TiO ₂ causes decomposition of the organic component of the organosilicon compound in the coating, decomposition of the epoxy resin component, and further deterioration of the coating on the resin substrate surface. It happened and there was a problem in its durability.

Further, in the coating compositions using composite fine particles of titanium dioxide and cerium dioxide disclosed in JP-A-2-264902 and JP-A-3-68901,
Cerium dioxide was used as a composite for improving the weather resistance of titanium dioxide, but the obtained coating was still insufficient in terms of weather resistance. Furthermore, since cerium dioxide has a yellowish tint, the cured coatings obtained from these composite sols were more or less yellowish.

Therefore, the present invention is to solve these problems, and the object thereof is to obtain a refractive index of 1.5.
A coating composition capable of preventing the generation of interference fringes on a lens made of a synthetic resin having a high refractive index of 4 or more and obtaining sufficient weather resistance, colorless transparency, high surface hardness, durability and, if necessary, dyeability. Another object of the present invention is to provide a thin synthetic resin lens provided with a cured coating of the composition.

[0007]

In order to achieve the above object, the coating composition of the present invention and a synthetic resin lens having a cured coating of the composition will be described below in order.

The coating composition according to claim 1 contains the following components A and B as essential components, and is further selected from the following components C, D, E, F and G: 1
It is characterized by containing the above components as constituent components.

Component A. A colloidal dispersion of composite fine particles having a particle diameter of 1 to 300 mμ and composed of oxides of Sn and Zn.

B component. One or more hydrolyzates and / or partial condensates of organosilicon compounds represented by the general formula of R ¹ R ² _a Si (OR ³ ) _3-a .

(Wherein R ¹ is a) a hydrocarbon group having 1 to 6 carbon atoms, a) a vinyl group, or c) a methacryloxy group,
Represents an organic group having a mercapto group, an amino group or an epoxy group, R ² represents a hydrocarbon group having 1 to 4 carbon atoms, and R ³ represents a hydrocarbon group having 1 to 8 carbon atoms, an alkoxyalkyl group or an acyl group. And a represents 0 or 1. )
C component. One or more hydrolyzates and / or partial condensates of organosilicon compounds represented by the general formula Si (OR ⁴ ) ₄ .

(Here, R ⁴ represents a hydrocarbon group having 1 to 8 carbon atoms, an alkoxyalkyl group or an acyl group.) D component. Si, Al, Sn, Sb, Ta, Ce, La,
One or more colloidal dispersions of oxide fine particles selected from Fe, Zn, W, Zr and In and / or Si, A
l, Sn, Sb, Ta, Ce, La, Fe, Zn, W,
One or more colloidal dispersions of composite fine particles composed of two or more kinds of oxides selected from Zr, In and Ti (excluding composite fine particles composed of inorganic oxides of Sn and Zn).

E component. One or more selected from polyfunctional epoxy compounds, polyhydric alcohols, polycarboxylic acids or polycarboxylic anhydrides.

F component. One or more selected from hindered amine compounds.

G component. One or more selected from amines, amino acids, metal acetylacetonates, organic acid metal salts, perchloric acids and salts thereof, acids, and metal chlorides.

The component A is a composite fine particle composed of tin dioxide and zinc oxide, and has a particle diameter of 1 to 300 mμ.
Is a colloidal dispersion in water or an organic solvent. The refractive index of tin dioxide is around 1.9, which is an inorganic oxide having a high refractive index. However, a colloidal dispersion of fine particles of tin dioxide is unstable in dispersibility, and thus a transparent film cannot be obtained when used as a coating composition. On the other hand, zinc oxide is an inorganic oxide having a refractive index close to that of tin dioxide. By making composite particles of tin dioxide and zinc oxide, it is possible to improve the dispersion stability of the particles consisting of tin dioxide alone. The film obtained from the coating composition using the colloidal dispersion of the composite particles is colorless and transparent. You can get something. Moreover, since the composite fine particles have a high refractive index, it is possible to obtain a coating film having a high refractive index. In the composite of these two kinds of inorganic oxides, the composite ratio of tin dioxide and zinc oxide must be ZnO / SnO ₂ (weight ratio) of 0.1 or more. Further, when the amount of zinc oxide is too much, the obtained coating is colored, so that it is preferably used at 10.0 or less. The composite fine particle sol of tin dioxide and zinc oxide here means a sol in which composite fine particles of tin dioxide and zinc oxide are chemically bonded or a single particle of tin dioxide and zinc oxide physically bonded. It is a dispersed sol or a mixed sol of these. In particular, the composite form in which tin dioxide and zinc oxide described in claim 3 form a solid solution is preferable in terms of dispersion stability. The particle size of the composite fine particles is preferably about 1 to 300 mμ, and those having a too small particle size are difficult to prepare, and the cost is high and not practical. Therefore, those within the above range are preferable. As the dispersion medium for the composite fine particles, water, hydrocarbons, esters, ketones, alcohols, cellosolves, amines, organic carboxylic acids and the like can be used. Also, these dispersion media can be used as a mixture of two or more kinds. Further, in order to further enhance the dispersion stability when a coating liquid is used as described in claim 4, it is possible to use the composite fine particle surface treated with an organosilicon compound or an amine compound. Examples of the organic silicon compound used at this time include R ₃ SiX (R is an alkyl group, a phenyl group, a vinyl group, a methacryloxy group,
Organic group having mercapto group, amino group, epoxy group,
X is a monofunctional silane represented by 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 ,
For example, methylsilane, phenylsilane, etc., and Si
There are tetrafunctional silanes represented by X ₄ , such as tetraalkoxysilanes. In the treatment, the hydrolyzable group may be untreated or hydrolyzed. Further, after the treatment, a state in which the hydrolyzable group has reacted with the —OH group of the fine particles is preferable, but there is no problem in stability even when a part remains. Examples of the amine compound include ammonium or alkylamines such as ethylamine, triethylamine, isopropylamine and n-propylamine, aralkylamines such as benzylamine, alicyclic amines such as piperidine, and alkanolamines such as monoethanolamine and triethanolamine. There is. The addition amount of these organosilicon compound and amine compound must be within the range of about 0.001 to 15% with respect to the weight of the composite fine particles.

The proportion of the above-mentioned inorganic oxide fine particles in the cured coating is preferably 10% by weight to 90% by weight, and it is necessary to adjust the coating composition so as to fall within this range. If the amount is 10% by weight or less, the hardness of the obtained cured film is insufficient and the refractive index of the film is also low. On the other hand, when it is 90% by weight or more, the adhesion between the base material and the coating film is deteriorated, and cracks are generated in the coating film after curing, so that use within the above range is preferable.

The organosilicon compound represented by the general formula R ¹ R ² _a Si (OR ³ ) _3-a , which is the component B, includes methyltrimethoxysilane, ethyltriethoxysilane, methyltriethoxysilane and phenyltrisilane. Ethoxysilane, dimethyldimethoxysilane, phenylmethyldimethoxysilane,
Vinyltriethoxysilane, vinyltrimethoxysilane, vinyltris (β-methoxyethoxy) silane, γ
-Glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, β- (3.4-epoxycyclohexyl) Ethyltrimethoxysilane, γ-
Methacryloxypropyltrimethoxysilane, N-β
(Aminoethyl) γ-aminopropyltrimethoxysilane, N-β (aminoethyl) γ-aminopropylmethyldimethoxysilane, γ-aminopropyltriethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, γ-mercapto Examples include propyltrimethoxysilane and the like. These may be used alone or as a mixture of two or more. In addition, it is preferable that these are hydrolyzed in the absence of a solvent or in an organic solvent such as an alcohol in the presence of an acid. Further, it may be mixed with a colloidal dispersion of inorganic oxide fine particles after hydrolysis or may be mixed with a colloidal dispersion of inorganic oxides and then hydrolyzed. The proportion of the coating component derived from the hydrolyzate of the organosilicon compound as the component B in the cured coating is preferably 10% by weight to 90% by weight. This is not preferable when the amount is 10% by weight or less because the adhesive force between the base material and the coating decreases, and when the amount is 90% by weight or more, the adhesiveness of the antireflection film made of an inorganic substance decreases, so that the content is within this range. The preparation of the coating composition is preferred.

The coating composition according to claim 1 contains the above components A and B as essential components, and further contains the following components for the purpose of improving the performance of the coating liquid and imparting functionality to the coating film after curing. To add.

The organosilicon compound represented by the general formula Si (OR ⁴ ) ₄ , which is the C component, can easily adjust the refractive index of the formed film while maintaining the transparency of the film, and further apply the coating solution. It is used for the purpose of accelerating the curing speed of the subsequent coating. By using the component C, the refractive index of the coating after curing can be appropriately changed according to the refractive index of the base lens, and the adhesion of the antireflection film can be improved even if the content of the composite inorganic oxide decreases. It is possible to obtain. Further, by using the tetrafunctional silane compound represented by the component C as a coating composition, the curing speed at the time of forming a cured film is increased, and in particular, a base material such as a sulfur-containing urethane resin in which a dyeing agent is easily released from a textile lens. It is possible to suppress the amount of omission when forming the film on the first layer and to reduce the color tone change of the dyed lens before and after the film formation. 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 and the like. These may be used alone or as a mixture of two or more.
In addition, it is preferable that these are hydrolyzed in the absence of a solvent or in an organic solvent such as an alcohol in the presence of an acid.
The proportion of the coating component derived from the hydrolyzate of the tetrafunctional silane compound as the C component in the cured coating is preferably 0% by weight to 50% by weight. This is because if the amount is 50% by weight or more, cracks are likely to occur in the coating film after curing.

Si, Al, Sn, Sb, T which are D components
at least one of colloidal dispersions of oxide fine particles selected from a, Ce, La, Fe, Zn, W, Zr and In and / or Si, Al, Sn, Sb, Ta, Ce, La, F
A colloidal dispersion of composite fine particles composed of two or more kinds of oxides selected from e, Zn, W, Zr, In and Ti (excluding composite fine particles composed of oxides of Sn and Zn). One or more kinds are used for optimizing the refractive index, adhesion, dyeability, heat resistance, etc. of the obtained coating depending on the type of the base lens. These are specifically Si
_{O 2, Al 2 O 3,} SnO 2, Sb 2 O 5, Ta 2 O 5, CeO
₂ , La ₂ O ₃ , Fe ₂ O ₃ , ZnO, WO ₃ , ZrO ₂ , I
Fine particles of oxide such as n ₂ O ₃ are colloidally dispersed in water or an organic solvent. Alternatively, the composite fine particles composed of two or more kinds of these oxides are colloidally dispersed in water or an organic solvent. Both have a particle size of about 1
˜300 mμ is suitable, and the type of application and the amount used in the coating composition of the present invention are determined by the desired coating performance. Further, as described in claim 3, in order to enhance the dispersion stability in the coating liquid, it is possible to use a fine particle surface treated with an organosilicon compound or an amine compound by the same method as described above. .

At least one selected from the polyfunctional epoxy compounds, polyhydric alcohols, polyhydric carboxylic acids, and polyhydric carboxylic acid anhydrides, which are the E component, improves the dyeability of the coating film formed or has various durability. It is used for the purpose of improving.
Examples of polyfunctional epoxy compounds include diglycidyl ethers of difunctional alcohols such as (poly) ethylene glycol, (poly) propylene glycol, neopentyl glycol, catechol, resorcinol, and alkylene glycol, or triglycerides such as glycerin and trimethylolpropane. Examples thereof include di- or triglycidyl ethers of functional alcohols. As the polyhydric alcohol, (poly) ethylene glycol, (poly) propylene glycol, neopentyl glycol, catechol, resorcinol, alkylene glycol and other bifunctional alcohols, glycerin, trimethylolpropane and other trifunctional alcohols, 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. Examples of polycarboxylic anhydrides include succinic anhydride, maleic anhydride, itaconic anhydride,
Examples thereof include 1.2-dimethyl maleic anhydride, phthalic anhydride, hexahydrophthalic anhydride, and naphthalic anhydride. The proportion of the coating component derived from the E component in the cured coating is preferably 0% by weight to 40% by weight. This is because when the content is 40% by weight or more, the adhesion between the cured coating and the antireflection coating made of an inorganic material provided thereon deteriorates.

The hindered amine compound as the F component is used for the purpose of improving the dyeability of the coating film formed. For example, bis (2,2,6,6, -tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, 1- [2-
[3- (3,5-Di-t-butyl-4-hydroxyphenyl) propionyloxy] ethyl] -4- [3-
(3,5-di-t-butyl-4-hydroxyphenyl)
Propionyloxy] -2,2,6,6-tetramethylpiperidine, 8-benzyl-7,7,9,9-tetramethyl-3-octyl-1,3,8, -triazaspiro [4,5] Undecane-2,4-dione, 4-benzoyloxy-2,2,6,6, -tetramethylpiperidine, 8-acetyl-3-dodecyl-7,7,9,9-tetramethyl-1,3,8 -Triazaspiro [4.5] decane-2,4-dione, dimethyl succinate 1- (2-
(Hydroxyethyl) -4-hydroxy-2,2,6,6
-Tetramethylpiperidine polycondensate, poly [[6-
(1,1,3,3-tetramethylbutyl) amino-1,
3,5-triazine-2,4-diyl] [(2,2,2
6,6-Tetramethyl-4-piperidyl) imino] hexamethylene [(2,2,6,6, -tetramethyl-4-
Piperidyl) imino]], N, N′-bis (3-aminopropyl) ethylenediamine.2,4-bis [N-butyl-N- (1,2,2,6,6-pentamethyl-4piperidyl) amino] -6-chloro-1,3,5-triazine condensate, 2- (3,5-di-t-butyl-4-hydroxybenzyl) -2-n-butylmalonic acid bis (1,
2,2,6,6-pentamethyl-4-piperidyl) and the like. The upper limit of the amount used is preferably 3% by weight or less with respect to the solid content of the coating liquid, and above this range, the hardness, hot water resistance and the like of the cured film decrease, which is not desirable.

At least one selected from the G component amines, amino acids, metal acetylacetonates, organic acid metal salts, perchloric acids and salts thereof, acids, and metal chlorides accelerates curing of silanol or epoxy groups. It is a curing catalyst used for curing. The use of these curing catalysts makes it possible to accelerate the film formation reaction. Specific examples thereof include amines such as n-butylamine, triethylamine, guanidine and biguanide, amino acids such as glycine, metal acetyls such as aluminum acetylacetonate, chromium acetylacetonate, titanylacetylacetonate and cobalt acetylacetonate. Acetonates, 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, Acids such as hydrochloric acid, phosphoric acid, nitric acid, paratoluene sulfonic acid, SnCl ₂ , AlCl ₃ , FeCl ₃ , T
A metal chloride which is a Lewis acid such as iCl ₄ , ZnCl ₂ , and SbCl ₃ can be used. These G component curing catalysts can be used by adjusting the type and the amount used depending on the composition of the coating liquid and the like. The upper limit of the amount used is preferably 5% or less based on the solid content of the coating liquid, and if it is more than this, the hardness, hot water resistance and the like of the cured film decrease, which is not desirable.

The coating composition according to claim 2 is the above-mentioned component A, component B and component H described below.

[0026]

[Chemical 6]

(Wherein R ⁵ and R ⁶ are hydrocarbon groups having 1 to 6 carbon atoms, R ⁷ and R ⁸ are hydrocarbon groups having 1 to 8 carbons, alkoxyalkyl groups, and A is an organic group having a carbonate group or an epoxy group. Group, b and c represent 0 or 1), and for the purpose of improving the performance of the coating liquid and imparting functionality to the coating film after curing, the component C to G is added if necessary. is there.

The following are specific examples of the organic group having a carbonate group or epoxy group of A.

[0029]

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[0030]

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[0031]

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[0032]

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[0033]

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[0034]

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[0035]

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[0036]

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[0037]

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[0038]

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By using the H component, it is possible to reduce or improve bumps and pinholes in the coating film. Generally, the coating work on a plastic lens or the like is performed in a dustproof environment, but if the dustproofness is insufficient, the yield will be low. Therefore, the coating composition of the present invention is particularly effective in improving the yield in such an environment. When the H component is used, it is preferable to use it without a solvent or in an organic solvent such as alcohol after hydrolysis in the presence of an acid. The proportion of the coating component derived from the hydrolyzate of the organosilicon compound as the H component in the cured coating is preferably 3% by weight to 50% by weight. This is not preferable if the amount is 3% by weight or less because the yield improving effect is insufficient, and if the amount is 50% by weight or more, the scratch resistance is lowered, so that the coating composition is preferably prepared within this range.

Further, in order to adjust the solid content concentration of the coating composition of the present invention and adjust the liquid properties such as surface tension, viscosity and evaporation speed, a general organic solvent can be used. Specifically, solvents such as alcohols, ketones, cellosolves, and carboxylic acids are used alone or as a mixture.

The coating composition of the present invention may contain a small amount of a surfactant, an antistatic agent, an ultraviolet absorber, an antioxidant, a disperse dye, an oil-soluble dye,
It is also possible to add a fluorescent dye / pigment, a photochromic compound, etc. 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 substance or an organic substance in order to improve the adhesion between the substrate lens and the coating. It is effective to perform polishing treatment with fine particles, primer treatment, or plasma treatment.

As a coating and curing method, a coating film is formed by applying a coating solution by dipping, spinner, spraying or flow, and then heating and drying at a temperature of 40 to 200 ° C. for several hours. be able to. In particular, for a base material having a heat distortion temperature of less than 100 ° C., a spinner method that does not require fixing the lens base material with a jig is suitable. The thickness of the cured film is 0.5-30μ
When m is less than 0.5 μm, the scratch resistance of the resulting coating is insufficient, and when it exceeds 30 μm, cracks are likely to occur in the coating.

Another object of the present invention is to provide a thin synthetic resin lens having a cured coating of the coating composition as described in claim 5 and having excellent appearance and various durability. As a technical proposal for obtaining a lens made of a synthetic resin having a high refractive index, many published patent applications have been filed. The synthetic resin lens for thin eyeglasses which is an object of the present invention preferably has a lens substrate having a refractive index of 1.54 or more, and further has transparency, dyeability, heat resistance, water absorption, bending strength, resistance of the material. As a base lens capable of satisfying desired characteristics in terms of impact resistance, weather resistance, processability, etc., a sulfur-containing urethane type or (meth) acrylate type lens base material is suitable.

Furthermore, by providing a single-layer / multi-layer antireflection film made of an inorganic material on the cured film as described in claim 6, it is possible to reduce reflection and improve transmittance, and thus the spectacle lens. The function as can be further improved. Inorganic substances include SiO, SiO ₂ , Si ₃
N ₄ , TiO ₂ , ZrO ₂ , Al ₂ O ₃ , MgF ₂ , Ta ₂ O ₅
Etc., the antireflection film can be formed by a thin film forming method such as a vacuum vapor deposition method.

The base lens will be described in detail below.

The sulfur-containing urethane resin lens described in claim 7 has at least one polyisocyanate compound and the following formula 1

[0048]

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4-mercaptomethyl-3,6 represented by
-Dithio-1,8-octanedithiol, the following formula 2

[0050]

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Pentaerythritol tetra (3-mercaptopropionate) represented by:

[0052]

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It can be obtained by injecting a mixed solution of one or more thiol compounds selected from the tetrathiol compounds represented by the following into a mold consisting of a glass mold and a gasket and polymerizing by heating. As the polyisocyanate compound, tolylene diisocyanate, diphenylmethane diisocyanate, polymeric diphenylmethane diisocyanate, tolidine diisocyanate, naphthalene diisocyanate, hexamethylene diisocyanate,
Isophorone diisocyanate, xylylene diisocyanate, hydrogenated xylylene diisocyanate, hydrogenated diphenylmethane diisocyanate, tetramethyl xylylene diisocyanate, 2.5-bis (isocyanatomethyl) bicyclo [2.2.1] heptane, 2.6-bis (isocyanate methyl) 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, and two or more of them may be used alone or as necessary. You may use it as a mixture of the above.

The following compounds can be mentioned as specific examples of the tetrathiol compound represented by the formula 3.

[0055]

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The polyisocyanate compound and the thiol compound are used in a ratio of NCO / SH (functional group) molar ratio of usually 0.5 to 3.0, preferably 0.5 to 1.5. Further, an internal mold 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 By providing a cured coating comprising the coating composition of the present invention on the sulfur-containing urethane resin lens substrate thus obtained, the appearance is good and various durability is excellent,
Further, it is possible to provide a spectacle lens having a high refractive index / Abbe number and high impact strength.

The (meth) acrylate resin lens described in claim 8 is obtained by copolymerizing a (meth) acrylate monomer represented by the following general formula 4 with another polymerizable monomer.

[0058]

[Chemical 21]

(In the formula, R ¹³ represents a hydrogen atom or a methyl group, and R ¹⁴ represents a CH ₂ CH ₂ group or CH ₂ CH (OH) CH ₂
Represents a group, X represents a hydrogen atom or a halogen atom other than fluorine, and m + n represents an integer of 0 to 8. ) Specific examples of the (meth) acrylate-based monomer represented by the general formula 4 include 2,2-bis (3,5-dibromo-4- (meth) acryloyloxyethoxyphenyl) propane,
2,2-bis (4- (meth) acryloyloxyethoxyphenyl) propane, 2,2-bis [4- (β-hydroxy-γ- (meth) acryloyloxy) propoxyphenyl] propane and the like can be mentioned.

Other polymerizable monomers used at the same time include styrene, chlorostyrene, bromostyrene,
Aromatic monofunctional vinyl monomer such as α-methylstyrene, aromatic polyfunctional vinyl monomer such as divinylbenzene or its chlorine / bromine substituted derivative, methyl (meth) acrylate, ethyl (meth) acrylate, 2-
Monofunctional (meth) acrylate monomers such as hydroxyethyl (meth) acrylate, glycidyl methacrylate, benzyl methacrylate, phenoxy methacrylate, cyclohexyl methacrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di ( (Meth) acrylate, tetraethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, di (meth) acrylate of butanediol, various isocyanate compounds and hydroxyl group or mercapto group-containing (meth) ) Polyfunctional (meth) acrylic monomers such as urethane (meth) acrylate obtained from acrylate,
Furthermore, a thiol compound such as the thiol compound of Formula 1 or Formula 2 and pentaerythritol tetra (mercaptoacetate) can be used. It is also possible to use two or more of these monomers at the same time. Upon molding, a composition comprising 20 to 80% by weight of the (meth) acrylate-based monomer of the general formula 4 and 80 to 20% by weight of another polymerizable monomer is poured into a mold comprising a glass mold and a gasket, Thermal polymerization and / or photopolymerization is performed. At this time, general thermal polymerization initiators such as organic peroxides and azo compounds and / or general photopolymerization initiators such as acetophenone-based, benzoin-based, benzophenone-based, crosslinking agents, light stabilizers, and ultraviolet absorbers , Antioxidants, disperse dyes, oil-soluble dyes, colorants such as pigments, and the like can be added as appropriate. By providing the (meth) acrylate-based resin lens substrate thus obtained with a cured coating of the coating composition of the present invention, the appearance is good, the durability of various coatings is excellent, and the refractive index is high and the bending strength is excellent. It is possible to provide a spectacle lens having

The resin lens according to claim 9 is a copolymer obtained from a (meth) acrylate-based and / or vinyl-based monomer having a sulfur atom and an aromatic ring in its molecular structure and another polymerizable monomer. . Examples of the (meth) acrylate-based and / or vinyl-based monomers having a sulfur atom and an aromatic ring in the molecular structure include compounds represented by the following formulas 5 and 6 and the like.

[0062]

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[0063]

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(Wherein R ¹⁵ represents a hydrogen atom or a methyl group, and R ¹⁶ and R ¹⁷ each represent an alkylene group having 1 to 8 carbon atoms). Aromatic monofunctional vinyl monomer, aromatic polyfunctional vinyl monomer, monofunctional (meth) acrylate-based monomer, polyfunctional (meth) acrylate-based monomer,
One kind or two or more kinds such as a thiol compound can be used. In molding, a composition comprising 20 to 80% by weight of a (meth) acrylate-based and / or vinyl-based monomer having a sulfur atom and an aromatic ring in its molecular structure and 80 to 20% by weight of another polymerizable monomer is used. It is poured into a mold composed of a glass mold and a gasket, and thermal polymerization and / or photopolymerization is performed. At this time, general thermal polymerization initiators such as organic peroxides and azo compounds and / or general photopolymerization initiators such as acetophenone-based, benzoin-based, benzophenone-based, crosslinking agents, light stabilizers, and ultraviolet absorbers , Antioxidants, disperse dyes, oil-soluble dyes, colorants such as pigments, and the like can be added as appropriate. By providing a cured coating of the coating composition of the present invention on the resin lens substrate thus obtained, an eyeglass lens having a good appearance, excellent durability of various coatings, and a high refractive index and excellent heat resistance Can be provided.

[0065]

DESCRIPTION OF THE PREFERRED EMBODIMENTS 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 0.04 g of methylcellosolve dispersed tin dioxide zinc monoxide composite fine particle sol (SnO ₂ / ZnO = 65
/ 35 (weight ratio), solid content concentration 24.5% by weight, composite form SnO ₂ and ZnO solid solution constitutes individual fine particles) 103.39 g was added and sufficiently stirred, then left at 0 ° C. for 24 hours Then, aging was carried out 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 0.15 g, 2 After 0.09 g of-(5-methyl-2-hydroxyphenyl) benzotriazole was mixed and sufficiently stirred, deaeration was performed for 60 minutes under a vacuum of 5 mmHg. 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, and after cooling, the glass mold The gasket was removed to obtain a sulfur-containing urethane resin lens. 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 is immersed in a 5% by weight sodium hydroxide aqueous solution for 5 minutes, washed and dried, and then the coating solution prepared in (1) is applied. It was applied by spin coating. The spin coating was performed by applying the hard coat 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 film was 2.3 μm. In addition, using a commercially available dye for plastic lenses (Amber D for Seiko Plax),
A similar coating was applied to the fabric dyed for 3 minutes in a 0 ° C. dyeing bath. 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 calculated. ΔE _ab was 0.6, and no large color tone change was visually perceived. It was (4) Formation of Antireflection Film After exposing the lens having the cured film formed by the above method to the argon gas plasma with an output of 200 W in vacuum for 30 seconds, the lens side is changed to the atmosphere side by the vacuum evaporation method. Toward SiO ₂ , ZrO ₂ , SiO ₂ , ZrO ₂ , SiO
A 5-layer thin film of ₂ was formed. Optical film thickness of the formed anti-reflection film, in turn SiO ₂ is about lambda / 4, the total thickness of the next ZrO ₂ and SiO ₂ is about lambda / 4, the next ZrO ₂ is about lambda / 4, and the uppermost SiO ₂ is about λ / 4.
(Design wavelength λ is 510 nm) The synthetic resin lens obtained above was subjected to the following performance evaluation test, and the results are shown in Table 1. Appearance: The presence or absence of coloration of the undyed lens (white lens) was visually evaluated. Transmittance: The average transmittance of visible light of a lens (white lens) not dyed was measured with a spectrophotometer. Interference fringes: 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 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: 10000k due to ^# 0000 steel wool
The state of the coating film after 10 reciprocations at g / 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, the lens surface is cut with a knife to make 11 parallel line-shaped scratches at 1 mm intervals, and 100 squares are 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 presence or absence of coloration of the lens (white lens) which was not dyed was visually evaluated. ii) Transmittance: After the test, the average transmittance of visible light of the lens (white lens) not dyed was measured with a spectrophotometer. iii) 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 In the preparation of the coating composition of Example 1, methyl cellosolve dispersed tin dioxide zinc monoxide composite fine particle sol (SnO ₂ / ZnO = 65/35 (weight: Ratio), the solid content concentration is 24.5% by weight, and in the composite form, a solid solution of SnO ₂ and ZnO constitutes individual fine particles) 103.39 g of methylcellosolve-dispersed tin dioxide zinc monoxide composite fine particle sol
(SnO ₂ / ZnO = 55/45 (weight ratio), solid content concentration 24.5% by weight, composite form is the same as above) 103.3
A coating composition was prepared in the same manner as in Example 1 except that the amount was changed to 9 g. (2) Preparation of plastic lens substrate A tetrathiol compound (A component, represented by the following structural formula,
The mixing ratio of B component and C component is a molar ratio, A / B / C = 80
/ 10/10) 100 g,

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M-xylylene diisocyanate 103
g, dibutyltin dilaurate 0.02 g, an internal mold release agent 0.15 g, and 2- (5-methyl-2-hydroxyphenyl) benzotriazole 0.09 g are mixed and sufficiently stirred, and then the mixture is vacuumed at 5 mmHg for 60 minutes. Degassed.
Then, the mixture was poured into a mold composed of a glass mold and a gasket and kept at 40 ° C for 7 hours, and then from 40 ° C to 12
Polymerization was performed in a heating furnace in which the temperature was raised to 0 ° C. for 10 hours, and after cooling, the glass mold and the gasket were removed to obtain a sulfur-containing urethane resin lens. The obtained lens has a refractive index of 1.
66 and Abbe number 33. (3) Formation of Cured Coating Using the coating composition prepared by the above method, a cured coating was provided on the above-mentioned sulfur-containing urethane resin lens substrate by the same coating and curing as in Example 1. The film thickness of the obtained coating is
It was 2.3 μm. (4) Formation of Antireflection Film An antireflection film was applied to the lens having the cured film formed by the above method by the same method 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.

Example 3 In the preparation of the coating composition of Example 1, methyl cellosolve dispersed tin dioxide zinc monoxide composite fine particle sol (SnO ₂ / ZnO = 65 /
35 (weight ratio), solid content concentration 24.5% by weight, composite form is a solid solution of SnO ₂ and ZnO constitutes individual fine particles) 103.39 g of methyl cellosolve dispersed tin dioxide zinc monoxide composite fine particle sol (SnO ₂ / ZnO = 65/3
5 (weight ratio), solid content concentration 24.5% by weight, in the composite form, SnO ₂ and ZnO solid solution constitutes individual fine particles, and the surface of the composite fine particles is treated with methyltrimethoxysilane) 103.39 g A coating composition was prepared in the same manner as in Example 1 except that Using this coating composition, a cured coating was provided on the same sulfur-containing urethane resin lens substrate as polymerized in Example 1 by the same coating and curing as in Example 1. The film thickness of the obtained coating film is 2.2.
μm. Further, an antireflection film similar to that in Example 1 was applied on this film. 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. The coating compositions prepared in Examples 1 and 2 showed some particle precipitation when left standing for 2 weeks at room temperature, but the coating composition of Example 3 showed no particle precipitation under the same standing conditions. I couldn't see it.

Example 4 (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 added in order with 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 94.44 g of methylcellosolve-dispersed tin dioxide-zinc monoxide composite fine particle sol were added and sufficiently stirred, and then at 24 ° C. at 24 ° C.
The coating composition was obtained by allowing it to stand for a period of time for aging. (2) Preparation of plastic lens base material Pentaerythritol tetra (3-mercaptopropionate) 130 g, m-xylylene diisocyanate 100 g, dibutyltin dichloride 0.018 g, internal release agent 0.18 g, 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 a 5 wt% sodium hydroxide aqueous solution for 5 minutes, washed and dried, and then the coating solution prepared in (1) is used. A cured coating was provided 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 0.4, and no large color tone change was visually perceived. (4) Formation of Antireflection Film Example 1 was applied to the lens having the cured film formed by the above method.
An anti-reflection film was provided in the same manner as described 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.

Example 5 (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 sequentially added while stirring, and then, 18.02 g of 0.05N hydrochloric acid water was added and stirred for 30 minutes. Then, methanol dispersed tin dioxide zinc monoxide composite fine particle sol
(SnO ₂ / ZnO = 55/45 (weight ratio), solid content concentration is 30% by weight, and in the composite form, the surface of the SnO ₂ fine particles is Zn
60.05 g having a structure covered with O and further having a surface treated with dimethoxydiphenylsilane) and 5.67 g of glycerin diglycidyl ether (trade name “Denacol EX-313” manufactured by Nagase & Co., Ltd.), silicon-based interface Activator (Nippon Unicar Co., Ltd., trade name "L-700"
1 ″) 0.04 g, and 0.4713 g of magnesium perchlorate as a curing catalyst were added and dissolved in this order, and then 0 ° C.
The coating composition was obtained by allowing it to stand for 24 hours for aging. (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 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 Hardened Coating Using the methacrylic resin lens produced by the above method, using a plasma apparatus for surface treatment (manufactured by Vacuum Instrument Co., Ltd.), air flow rate 100 ml / min, output 50 W, vacuum degree 0.2 To
or for 30 seconds. After that, the coating liquid prepared in (1) was used to apply by a dipping method at a pulling rate of 15 cm / s. After application, 120
It was cured at 3 ° C for 3 hours to form a cured film. The film thickness of the obtained coating was 2.2 μm. When this lens was dyed using the same dyeing agent as in Example 1, the total light transmittance was 53%, indicating good dyeability. (4) Formation of Antireflection Film An antireflection film was provided on the dyed lens having the cured film formed by the above method by the same method 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.

Example 6 A coating composition prepared in the same manner as in Example 5 was added with bis (2,2,6,6, -tetramethyl-4-piperidyl) sebacate (trade name: Sanol) as a hindered amine compound. LS-77
0, Sankyo Co., Ltd. 0.1 g was added, and aging was performed in the same manner. Using this coating composition, the same methacrylic resin-based resin lens substrate as polymerized in Example 5 was subjected to the same pretreatment, coating and curing as in Example 5 to form a cured coating. The film thickness of the obtained coating was 2.3 μm.
When this lens was dyed with the same dye as in Example 1, the total light transmittance was 35%.
It showed better dyeability. Further, an antireflection film similar to that in Example 1 was applied on this film. 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 7) (1) Preparation of coating composition Methyl cellosolve 3 was placed in a flask equipped with a stirrer.
7.87 g and 34.01 g of γ-glycidoxypropyltrimethoxysilane were added in order with stirring, and then added to 0.
9.34 g of 05N hydrochloric acid water was added and stirred for 30 minutes. Subsequently, 0.04 g of the same silicon-based surfactant as used in Example 1, methanol-dispersed tin dioxide zinc monoxide composite fine particle sol (SnO ₂ / ZnO = 70/30 (weight ratio), solid concentration 24.5). % By weight, composite form is SnO ₂
Solid solution of ZnO and ZnO constitutes individual fine particles) 84.4
4 g, methanol-dispersed colloidal silica (solid content 3
After adding 0 wt%, 21.17 g of trade name: Oscar 1132, manufactured by Catalysts & Chemicals Industry Co., Ltd. in this order and stirring sufficiently, the mixture was left standing at 0 ° C. for 24 hours for aging to obtain a coating composition. (2) Preparation of plastic lens substrate 40 g of styrene and 60 g of p-bis (2-methacryloyloxyethylthio) xylylene represented by the following formula

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After 0.7 g of t-butylperoxy 2-ethylhexanoate and 0.2 g of 2- (5-methyl-2-hydroxyphenyl) benzotriazole were mixed and sufficiently stirred, a glass mold and a gasket were used. It was poured into a mold. Then, 8 hours at 50 ℃, 8 hours from 50 ℃
5 hours to 0 ℃, 4 hours from 80 ℃ to 120 ℃, 12
After heating at 0 ° C. for 2 hours, it was cooled and the glass mold and the gasket were removed to obtain a methacrylic resin lens. The obtained lens had a refractive index of 1.59 and an Abbe number of 35. (3) Formation of cured coating 5% by weight of the methacrylic resin lens produced by the above method
Immerse in a concentrated sodium hydroxide aqueous solution for 5 minutes and wash
After drying, the coating liquid prepared in (1) was used to apply the coating liquid by a dipping method at a pulling rate of 12 cm / s. After coating, the coating was heat-cured at 120 ° C. for 3 hours to form a cured coating. The film thickness of the obtained coating was 2.0 μm.
Met. (4) Formation of Antireflection Film Example 1 was applied to the lens having the cured film formed by the above method.
An anti-reflection film was provided in the same manner as described 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.

(Example 8) (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, and γ-glycidoxypropylmethyldiethoxysilane 27.58 g were sequentially added with stirring, and then 0.05N hydrochloric acid water 8.41 g was added. Stir for 30 minutes. Subsequently, the same methanol-dispersed tin dioxide zinc monoxide composite fine particle sol used in Example 7, 21.98 g of the same methanol-dispersed colloidal silica used in Example 7, and glycerin diglycidyl ether (Nagase Sangyo Co., Ltd.)
Made, trade name "Denacol EX-313") 5.67 g,
0.04 g of a silicon-based surfactant (manufactured by Nippon Unicar Co., Ltd., trade name "L-7001"), 0.4713 g of magnesium perchlorate as a curing catalyst, and bis (1,2,2,6,6) as a hindered amine compound. 6-pentamethyl-
4-piperidyl) sebacate (trade name: Sanol LS-
765 and Sankyo Co., Ltd. (0.05 g) were added and dissolved in this order, and 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 40 g, hydrogenated diphenylmethane diisocyanate 60 g, dibutyltin dilaurate 0.1 g,
0.1 g of an internal mold release agent and 0.09 g of 2- (5-methyl-2-hydroxyphenyl) benzotriazole are mixed,
After sufficiently stirring, deaeration was performed for 60 minutes under a vacuum of 5 mmHg. Then, it was poured into a mold composed of a glass mold and a gasket and kept at 40 ° C for 7 hours, and then 40 ° C.
Polymerization was performed in a heating furnace in which the temperature was raised from 10 to 120 ° C. over 10 hours, 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 1.60 and an Abbe number of 42. (3) Formation of cured coating The sulfur-containing urethane resin lens produced by the above method is immersed in a 5 wt% sodium hydroxide aqueous solution for 5 minutes, washed and dried, and then the coating liquid prepared in (1) is used. Application was performed by a dipping method under the condition of a pulling rate of 12 cm / s. After coating, the coating was heat-cured at 120 ° C. for 3 hours to form a cured coating. The film thickness of the obtained coating is 2.5μ.
m. When this lens was dyed using the same dyeing agent as in Example 1, the total light transmittance was 40%, indicating good dyeability. (4) Formation of Antireflection Film Example 1 was applied to the lens having the cured film formed by the above method.
An anti-reflection film was provided in the same manner as described 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.

(Example 9) (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, and γ-glycidoxypropylmethyldiethoxysilane 27.58 g were sequentially added with stirring, and then 0.05N hydrochloric acid water 8.41 g was added. Stir for 30 minutes. Subsequently, 50.05 g of the same methanol-dispersed tin dioxide-zinc oxide composite fine particle sol used in Example 7 and methanol-dispersed tin oxide-tungsten oxide composite fine particle sol (solid content concentration 30% by weight, triethylamine-treated product) 2
2.38 g and glycerin diglycidyl ether (manufactured by Nagase & Co., Ltd., trade name "Denacol EX-313")
5.67 g, silicon-based surfactant (manufactured by Nippon Unicar Co., Ltd., trade name "L-7001") 0.04 g, magnesium perchlorate 0.4713 g as a curing catalyst, and bis (1,2,2) as a hindered amine-based compound. 2, 6, 6
-Pentamethyl-4-piperidyl) sebacate (trade name: Sanol LS-765, manufactured by Sankyo Co., Ltd.) 0.05 g
Was added and dissolved in this order, and the mixture was allowed to stand at 0 ° C. for 24 hours for aging to obtain a coating composition. (2) Formation of Cured Coating The same sulfur-containing urethane resin lens substrate prepared in Example 2 was dipped in a 5 wt% sodium hydroxide aqueous solution for 5 minutes, washed and dried, and then, in (1). Using the adjusted coating liquid, coating was performed by a dipping method at a pulling rate of 15 cm / s. 3 at 120 ° C after coating
It was heat cured for a period of time to form a cured coating. The film thickness of the obtained coating was 2.6 μm. This lens is used in Example 1.
When dyeing was carried out using the same dyeing agent as in (1), the total light transmittance was 38%, and good dyeability was exhibited. (3) Formation of Antireflection Film Example 1 was applied to the lens having the cured film formed by the above method.
An anti-reflection film was provided in the same manner as described 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.

Example 10 (1) Preparation of coating composition Methyl cellosolve 9 was placed in a flask equipped with a stirrer.
2.94 g, γ-glycidoxypropyltrimethoxysilane 20.55 g, an organosilicon compound represented by the following structural formula,

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14.28 g was sequentially added with stirring, then 8.65 g of 0.05N hydrochloric acid water was added, and the mixture was stirred for 30 minutes. Subsequently, 63.98 g of the same methanol-dispersed tin dioxide and zinc monoxide composite fine particle sol used in Example 1 and 10.66 g of glycerin diglycidyl ether (manufactured by Nagase & Co., Ltd., trade name "Denacol EX-313"), silicon-based Surfactant (Nippon Unicar Co., Ltd., trade name "L-7"
001 ″) 0.04 g and 0.6765 g of magnesium perchlorate as a curing catalyst were added and dissolved in this order,
The coating composition was obtained by allowing it to stand at 0 ° C. for 24 hours for aging. (2) Formation of Hardened Coating The same sulfur-containing urethane resin lens substrate prepared in Example 1 was immersed in a 5 wt% aqueous sodium hydroxide solution for 5 minutes, washed and dried, and then, in (1). Using the adjusted coating liquid, coating was performed by a dipping method at a pulling rate of 15 cm / s. 3 at 120 ° C after coating
It was heat cured for a period of time to form a cured coating. In addition, the film thickness of the obtained film was 2.3 μm. This lens is used in Example 1.
When dyeing was carried out using the same dyeing agent as in (1), the total light transmittance was 42%, and good dyeability was exhibited. In addition, the appearance of the lens after the formation of the cured film was inspected, and it was found that the lens had less bumps and had a good appearance, as compared with the lens of the above-mentioned example prepared in the same manner without dust. (3) Formation of Antireflection Film Example 1 was applied to the lens having the cured film formed by the above method.
An anti-reflection film was provided in the same manner as described 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.

Comparative 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, 0.04 g of the same silicon-based surfactant as used in Example 1 was further added, and methyl cellosolve-dispersed titanium dioxide-cerium dioxide-
Silicon dioxide composite fine particle sol (TiO ₂ / CeO ₂ / Si
O ₂ = 68/17/15 (weight ratio), solid content concentration 20.
5% by weight, tetramethoxysilane-treated product) 103.39
After adding g and stirring sufficiently, the mixture was allowed to stand at 0 ° C. for 24 hours for aging to obtain a coating composition. (2) Formation of Hardened Coating The same sulfur-containing urethane resin lens prepared in Example 1 was immersed in a 5% by weight sodium hydroxide aqueous solution for 5 minutes, washed and dried, and then adjusted in (1). The coating liquid thus prepared was applied by spin coating. The coating conditions and curing conditions during spin coating were the same as in Example 1. The film thickness of the obtained film was 2.2 μm. A similar coating was provided on a material obtained by dyeing a fabric for 3 minutes in a dyeing bath at 90 ° C. using a commercially available dyeing agent for plastic lenses (Amber D for Seiko Plax). 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 calculated. ΔE _ab was 0.6, and no large color tone change was visually perceived. It was (3) Formation of Antireflection Film Example 1 was applied to the lens having the cured film formed by the above method.
An anti-reflection film was provided in the same manner as described 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.

(Comparative Example 2) 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 used in Example 1 was further added, and 96.83 g of a methanol sol of antimony pentoxide (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 a sulfur-containing urethane resin lens having a refractive index of 1.66 produced in Example 1
A cured coating was provided by the same coating and curing method as described in. 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 thus obtained 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 2.0, and a change in color tone was visually perceived.

(Comparative Example 3) 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 used in Example 1 and 64.54 g of methylcellosolve-dispersed titanium dioxide-cerium dioxide-silicon dioxide composite fine particle sol were added and sufficiently stirred, and then at 0 ° C. for 24 hours. The coating composition was obtained by allowing it to stand for aging. The coating composition was applied to the sulfur-containing urethane resin lens having a refractive index of 1.59 prepared in Example 4 by the same coating and curing method as in Example 1 to form a cured film. The film thickness of the obtained film was 2.3 μm. Further, an antireflection film was provided by the same method 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. 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 2.1, and a change in color tone was visually perceived.

[0085]

[Table 1]

[0086]

According to the invention of claim 1, a colloidal dispersion of composite fine particles composed of tin dioxide-zinc oxide and one or more components selected from organic silicon compounds and other components are coated. By using it as a material, it is possible to obtain a cured film having a high refractive index, being colorless and transparent, and excellent in various durability. Furthermore, by appropriately adjusting and using the constituent components of the coating composition according to the desired coating performance, it is possible to accelerate the coating formation speed during curing and impart dyeability to the cured coating.

Further, according to the second aspect of the present invention, since the bumps and pinholes in the coating film can be reduced or improved, the yield improving effect can be obtained.

According to the invention of claim 5, a cured film formed from the coating composition of any one of claims 1 to 4 is a synthetic resin lens substrate having a refractive index of 1.54 or more. By providing it in, it is possible to provide a lightweight and thin lens made of synthetic resin which is free from interference fringes and coloring of the cured film and has excellent durability.

According to the invention of claim 6, by laminating an antireflection film made of an inorganic material on the cured film of claim 5, the reflection on the surface is suppressed and the function as a spectacle lens is further improved. You can

Claims (9)

[Claims] 1. A coating comprising the following components A and B as essential components, and further containing at least one component selected from the following components C, D, E, F and G as constituent components. Composition. A component. A colloidal dispersion of composite fine particles having a particle diameter of 1 to 300 mμ and composed of oxides of Sn and Zn. B component. One or more hydrolyzates and / or partial condensates of organosilicon compounds represented by the general formula of R ¹ R ² _a Si (OR ³ ) _3-a . (Wherein R ¹ is a) a hydrocarbon group having 1 to 6 carbon atoms, a) a vinyl group, or c) an organic group having a methacryloxy group, a mercapto group, an amino group or an epoxy group, and R ² is a carbon group. R ³ represents a hydrocarbon group having 1 to 4 carbon atoms, R ³ represents a hydrocarbon group having 1 to 8 carbon atoms, an alkoxyalkyl group or an acyl group, and a represents 0 or 1. ) C component. One or more hydrolyzates and / or partial condensates of organosilicon compounds represented by the general formula Si (OR ⁴ ) ₄ . (Where R ⁴ has 1 to 8 carbon atoms
Represents a hydrocarbon group, an alkoxyalkyl group or an acyl group. ) D component. Si, Al, Sn, Sb, Ta, Ce, La,
One or more colloidal dispersions of oxide fine particles selected from Fe, Zn, W, Zr and In and / or Si, A
l, Sn, Sb, Ta, Ce, La, Fe, Zn, W,
One or more colloidal dispersions of composite fine particles composed of two or more kinds of oxides selected from Zr, In and Ti (excluding composite fine particles composed of oxides of Sn and Zn). E component. 1 selected from polyfunctional epoxy compound, polyhydric alcohol, polycarboxylic acid and polycarboxylic anhydride
More than seeds. F component. One or more selected from hindered amine compounds. G component. One or more selected from amines, amino acids, metal acetylacetonates, organic acid metal salts, perchloric acids and salts thereof, acids, and metal chlorides. 2. The coating composition according to claim 1, further comprising the following component H as an essential component. H component. The general formula is One or more types of hydrolyzates and / or partial condensates of organosilicon compounds represented by. (Here, R ⁵ and R ⁶ represent a hydrocarbon group having 1 to 6 carbon atoms, R ⁷ and R ⁸ represent a hydrocarbon group or an alkoxyalkyl group having 1 to 8 carbon atoms, and A has a carbonate group or an epoxy group. Represents an organic group, b and c
Represents 0 or 1. ) 3. The coating composition according to claim 1, wherein the composite fine particles of the component A are fine particles made of a solid solution of tin dioxide and zinc oxide. 4. The coating composition according to any one of claims 1 to 3, wherein the fine particle surfaces of the component A and / or the component D are treated with an organosilicon compound or an amine compound. Coating composition. 5. A cured film obtained by applying and curing the coating composition according to any one of claims 1 to 4,
A synthetic resin lens provided on a lens substrate having a refractive index of 1.54 or more. 6. A synthetic resin lens comprising the cured coating according to claim 5 and an antireflection coating made of an inorganic material laminated on the cured coating. 7. The synthetic resin lens according to claim 5 or 6, wherein the lens substrate is at least one selected from mercapto compounds represented by the following formulas 1, 2, and 3 and 1 of polyisocyanate. A synthetic resin lens, which is a sulfur-containing urethane resin obtained by reacting at least one kind. Embedded image Embedded image Embedded image 8. The synthetic resin lens according to claim 5, wherein the lens base material is a copolymer obtained from a monomer represented by the following general formula 4 and another polymerizable monomer. Resin lens. Embedded image (In the formula, R ¹³ represents a hydrogen atom or a methyl group, and R ¹⁴ represents C
X represents a H ₂ CH ₂ group or a CH ₂ CH (OH) CH ₂ group, and X
Represents a hydrogen atom or a halogen atom other than fluorine, and m +
n represents an integer of 0 to 8. ) 9. The synthetic resin lens according to claim 5, wherein the lens base material is a (meth) acrylate-based and / or vinyl-based monomer having a sulfur atom and an aromatic ring in a molecular structure, A synthetic resin lens, which is a copolymer obtained from another polymerizable monomer.