JPH11287901A - Colored plastic lens - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a lens for glasses having both of durability and fashionability by applying a coating film essentially comprising a dye and polyvinylacetal on a plastic lens base body. SOLUTION: This lens consists of a plastic lens base body and a coating film essentially comprising a dye and polyvinylacetal formed on the plastic lens base body. The plastic lens body is prepared by polymn. of a monomer mixture containing polymethylmethacrylate and its copolymer and acrylonitrile- styrene copolymer. As for the dye dispersed in the primer layer, an azo dye, nitro and nitroso dye or photochromic dye is used. The compounding amt. of the dye is preferably about 0.1 to 10 g based on 40 g of the resin. The primer layer essentially consists of polyvinylacetal and for example, a compd. having 0 to 20 carbon atoms in the alkyl group of the acetal part is used.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a colored plastic lens having excellent durability.

[0002]

2. Description of the Related Art In recent years, plastic lens substrates have been widely used as optical lenses, especially as spectacle lenses, because they have characteristics such as being easy to mold, being light and hard to break, and being easily colored by dyeing. Is being used. Particularly recently, there has been an increasing demand for highly durable spectacle lenses that can be used in various environments. Further, there is an increasing demand for a plastic lens which has not only durability but also fashionability.

[0003] The merit that the plastic lens substrate can be easily dyed and colored is a major reason that it is preferred as a spectacle lens in terms of fashionability and light shielding properties. At present, it is said that more than 70% of spectacle plastic lenses are dyed and put on the market. For these reasons, it has become necessary to uniformly and stably color highly durable plastic lenses with various colors.

[0004] A conventional method for dyeing a plastic lens is as follows.
A dyeing solution in which a disperse dye is dispersed in water together with a surfactant is prepared, heated, and heated, and a dip dyeing method (dip dyeing method) in which a plastic lens substrate is immersed therein has been mainly used.
As an alternative to the immersion dyeing method, for example, Japanese Patent Publication No. 35-1384 proposes a method of sublimating an organic pigment to color a plastic lens substrate.

Japanese Unexamined Patent Publications Nos. 56-153321, 56-159376 and 1-277814 disclose a method of dyeing a plastic lens substrate by sublimating a sublimable dye. ing. In addition, Japanese Unexamined Patent Publication No.
JP-A-6-153321 and JP-A-56-159376 describe gas-phase dyeing methods using solid dyes.

As described above, the plastic lens substrate has merits in terms of dyeability and workability, but the plastic lens substrate has a problem of abrasion resistance that it is easily scratched due to insufficient surface hardness. Also, there is a problem that surface reflection which causes flickering of an image or an object easily occurs. Conventionally, in order to improve the scratch resistance of a plastic lens substrate, a hard coat film mainly composed of a silicon-based material has been provided on the surface of the lens substrate for the purpose of increasing the surface hardness. Further, in order to improve surface reflection, an inorganic material is deposited on the surface of the glass substrate to provide an antireflection film.

However, when such a silicon-based hard coat film or an inorganic anti-reflection film is provided, there is a problem that the impact resistance of the plastic lens substrate is reduced.
Therefore, in order to improve the impact resistance of the plastic lens substrate, it has been proposed to perform a surface modification by providing a primer layer between the lens substrate and the hard coat film. As the primer composition for forming the primer layer, for example, a method using an epoxy resin (JP-A-60-214301) or a method using a primer composition comprising an acrylic polyol and a polyfunctional organic isocyanate compound (JP-A- 61-114203) and the like have been proposed.

[0008]

DISCLOSURE OF THE INVENTION The present inventors have investigated the problems of the conventional dyeing method and the method of imparting durability in order to easily and efficiently obtain a plastic lens having both fashionability and durability. Was. First, observation was performed on a lens substrate that was dyed by using the above-described conventional immersion method for dyeing a plastic lens substrate. As a result, the color tone may be greatly changed depending on each dyed lens, and it is difficult to obtain a large amount of a uniform and stable dyed plastic lens.

In addition, there is a problem that the color density of the lens substrate dyed by the vapor phase dyeing method using the solid dyeable dye is not uniform. Further, the lens substrate dyed by the method of dyeing in a vacuum atmosphere has a problem that optical performance is deteriorated. In addition, there is a problem that an operation of reducing the atmosphere to a vacuum is required, and equipment cost is required.

Further, a method of coloring with a pigment in a vacuum atmosphere described in Japanese Patent Publication No. 35-1384 is
In addition to the problem of equipment cost, the lens manufactured by this method has a problem that satisfactory optical performance cannot be obtained. When the type of the base material changes, the dyeing method must be changed accordingly.

As described above, each conventional dyeing method has various problems. Next, to examine the durability of the dyed lens, a primer layer is formed on the plastic lens substrate dyed by the immersion method to improve the impact resistance, and a silicon-based material is further formed on the primer layer by the dipping method. An attempt was made to apply a hard coat film as a component. As a result, when the hard liquid (a liquid substance serving as a raw material for forming a hard coat film) is colored, or when another lens substrate is immersed using the colored hard liquid, another lens substrate is obtained. Is also colored. In addition, the color tone may be different after dyeing and after forming the hard coat layer. In addition to the above-mentioned problems, plastic lenses dyed by the immersion method or the gas phase dyeing method are exposed to ultraviolet rays in the strong sunlight in summer or snowy mountains in winter, discolored when used for a long time, or lose color. May occur, and it is necessary to further improve light resistance and weather resistance.

[0012]

Means for Solving the Problems The present inventors have studied the above problems. It has been found that the problems of the immersion dyeing method are caused by the disperse dye concentration in the dyeing solution, the amount of the dyeing assistant, the temperature of the dyeing solution, and the dyeability of the plastic lens substrate. Gas phase dyeing method using solid dyeing dye,
This was due to the difficulty in adjusting the staining concentration.

The problem with the method of dyeing in a vacuum atmosphere is that
It was found that the processing temperature was 150 to 200 ° C., and the temperature of the plastic lens substrate was also high, so that the substrate was eroded, and as a result, the optical performance of the plastic lens substrate deteriorated. In the dyed plastic lens substrate, the dye is present on the lens substrate surface in the form of molecules.
Therefore, immerse the dyed lens substrate in the hard liquid,
Thereafter, it was found that the above-mentioned problem in the case of forming a hard coat film on the lens substrate was caused by the fact that the dye was dissolved in the hard liquid.

The present invention solves these problems and proposes a spectacle lens having both durability and fashionability. Therefore, the present invention firstly provides a "colored plastic lens comprising a plastic lens substrate and a coating film mainly composed of a dye and polyvinyl acetal formed on the plastic lens substrate (claim Item 1) ”is provided. Secondly, there is provided "a plastic lens according to claim 1, wherein a coating film mainly composed of a material different from the coating film is formed on the coating film." Third, the plastic lens according to claim 1 or 2, wherein the polyvinyl acetal is a reaction product using at least one of the following three compounds as a crosslinking agent.

A) Organometallic alkoxide compounds or alkoxide diketonate compounds b) Hydrolyzable organosilane compounds c) Dialdehyde compounds or dialdehyde acetal compounds (Claim 3). Fourth, “the plastic lens according to any one of claims 1 to 3, wherein the thickness of the coating film is about 0.1 to 5 μm (claim 4)”.
I will provide a.

[0016]

DETAILED DESCRIPTION OF THE INVENTION The plastic lens substrate used in the present invention is, for example, polymethyl methacrylate and its copolymer, acrylonitrile-styrene copolymer,
Polycarbonate, cellulose acetate, polyvinyl chloride, polyethylene terephthalate, epoxy resin, unsaturated polyester resin, polyurethane resin, CR-39
Or a polymer mixture obtained by polymerizing a monomer mixture containing one or more polyisocyanates and one or more polyols and / or one or more polythiols.

The dyes dispersed in the primer layer of the present invention include azo, nitro and nitroso, polymethine, aza- [18] -conjugated macrocyclic, di- or triarylcarbonium, sulfide, carbonyl Conventionally known general materials such as a system can be used. It is also possible to use a conventionally known general photochromic dye.

The amount of the dye in the primer layer is
It is preferable that about 0.1 to 10 g of the dye is contained with respect to 0 g. The primer layer used in the present invention is mainly composed of polyvinyl acetal having high dye-adsorbing property and high impact resistance. As a specific example of the material containing polyvinyl acetal as a main component, an alkyl group in the acetal portion having 0 to 20 carbon atoms can be used, and preferably 0 to 10 carbon atoms. Particularly preferred is polyvinyl butyral in which the alkyl group has 3 carbon atoms.

The degree of acetalization may be from 10 to 90%, preferably polyvinyl acetal having an acetalization degree of from 20 to 80%. Acetalization degree is 10
%, The impact strength is insufficiently improved, and the polyvinyl acetal having a degree of acetalization of more than 90% is difficult to synthesize, and even if synthesized, a decrease in adhesion to a plastic substrate is expected. Therefore, it is not preferable.

The degree of polymerization of the polyvinyl acetal is preferably 5,000 or less, more preferably 1 or less.
00 to 3,000. If the degree of polymerization is too high, it will be difficult to dissolve in a solvent. In addition, it becomes difficult to synthesize a polyvinyl acetal having an optimal acetalization degree. Conversely, if the degree of polymerization is lower than 100, the improvement in impact resistance becomes insufficient.

The amount of polyvinyl acetal added to the primer composition is 1 to 30% by weight, preferably 2 to 30% by weight.
20% by weight. The amount of polyvinyl acetal added is 3
If the amount is more than 0% by weight, the viscosity of the primer composition becomes too high, and it becomes difficult to apply the primer composition to a plastic lens substrate. Further, since the thickness of the primer layer becomes too large, uniformity of the coated surface is lost. Conversely, if the amount of polyvinyl acetal is less than 1% by weight, the thickness of the primer layer becomes too thin, and the improvement in impact resistance becomes insufficient.

In the case of a hydrolyzable organosilane compound, a hydrolyzable group in the organosilane compound is hydrolyzed to generate a silanol group, which is dehydrated and condensed with a hydroxyl group in polyvinyl acetal by the action of a catalyst and heat. Crosslinking takes place between or within molecules. The molecule participating in the crosslinking is a hydrolyzate of an organosilane compound or a condensate thereof. The organosilane compound may be added as it is, or a compound that has been hydrolyzed in advance may be added. Further, one kind of organosilane compound may be used alone, or two or more kinds of organosilane compounds may be used in combination.

Examples of the organosilane compound include halosilane compounds in which the hydrolyzable group is a halogen atom, carboxysilane compounds in which the hydrolyzable group is a carboxy group, ketoxime silane compounds in which the hydrolyzable group is a ketoxime group, or Alkoxysilane compounds in which the decomposing group is an alkoxy group can be used, but alkoxysilane compounds are preferred. Specific compounds include dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, phenylmethyldimethoxysilane, phenylmethyldiethoxysilane, γ-chloropropylmethyldimethoxysilane, γ-chloropropylmethyldisilane Ethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, γ-methacryloxypropylmethyldiethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropylmethyldiethoxysilane, γ-aminopropylmethyldimethoxysilane, γ
-Aminopropylmethyldiethoxysilane, methylvinyldimethoxysilane, methylvinyldiethoxysilane,
γ-glycidoxypropylmethyldimethoxysilane, γ
-Glycidoxypropylmethyldiethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, methyltributoxysilane, methyltris (2-methoxyethoxy) silane, ethyltrimethoxysilane, ethyltriethoxysilane,
Ethyltripropoxysilane, ethyltributoxysilane, ethyltris (2-methoxyethoxy) silane, propyltrimethoxysilane, propyltriethoxysilane, butyltrimethoxysilane, butyltriethoxysilane, hexyltrimethoxysilane, hexyltriethoxysilane, vinyl Trimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy)
Silane, phenyltrimethoxysilane, phenyltriethoxysilane, γ-chloropropyltrimethoxysilane, γ-chloropropyltriethoxysilane, 3,3
3-trifluoropropyltrimethoxysilane, 3,
3,3-trifluoropropyltriethoxysilane, γ
-Methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane,
Chloromethyltrimethoxysilane, chloromethyltriethoxysilane, N-β-aminoethyl) -γ-aminopropyltrimethoxysilane, N-β-aminoethyl)-
γ-aminopropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, (3,4-epoxycyclohexylmethyl) trimethoxysilane, (3,4-epoxycyclohexylmethyl) Triethoxysilane, β-
(3,4-epoxycyclohexylethyl) trimethoxysilane, β- (3,4-epoxycyclohexylethyl) triethoxysilane, tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane, 1,1-bis ( Trimethoxysilyl) ethane, 1,1-bis (triethoxysilyl) ethane,
1,2-bis (trimethoxysilyl) ethane, 1,2-
Bis (triethoxysilyl) ethane, 1,3-bis (trimethoxysilyl) propane, 1,3-bis (triethoxysilyl) propane, 2,2-bis (trimethoxysilyl) propane, 2,2-bis ( Triethoxysilyl)
And propane. The addition amount of the organosilane compound in the primer composition is 0.01 to 30% by weight, preferably 0.1 to 20% by weight.

As the crosslinking agent, an organometallic alkoxide compound can be used. Specifically, an alkoxide or an alkoxide diketonate having a metal such as aluminum, silica, tin, tungsten, cerium, zirconium, or titanium can be used. it can. Particularly, those represented by the following general formula (I) are preferable. General formula (I)

[0025]

Embedded image

This compound, even when used alone,
A mixture of a plurality of types of compounds may be used. The organometallic alkoxide compound easily reacts with the organosilane compound or a hydrolytic condensate thereof, and the reaction product reacts with a hydroxyl group in polyvinyl acetal, which is a main component of the coating film, by the action of a catalyst and heat. The organometallic alkoxide compound has a function as a catalyst for promoting a dehydration condensation reaction between a silanol group in the organosilane compound generated by hydrolysis and a hydroxyl group in the polyvinyl acetal, and as a cross-linking agent that hydrolyzes together with the organosilane compound. It seems to have an effect.

Specific examples of the compound represented by the general formula (I) include the following. Aluminum trimethoxide, aluminum triethoxide, aluminum tripropoxide, aluminum trib and oxide,
Titanium tetramethoxide, titanium tetraethoxide, titanium tetrapropoxide, titanium tetrabutoxide, aluminum dipropoxide acetylacetonate, aluminum dipropoxide ethyl acetoacetate, aluminum dibutoxide acetylacetonate, aluminum dibutoxide ethyl acetoacetate, titanium Dimethoxide bis (acetylacetonate), titanium diethoxide bis (acetylacetonate), titanium dibutoxide bis (acetylacetonate), titanium dipropoxide bis (acetylacetonate), titanium dibutoxide bis (ethylacetonate) And the like. Of these, titanium alkoxide is particularly preferred.

The preferred amount of the organometallic alkoxide compound in the primer composition is 0.01 to 10% by weight. A more preferable addition amount is 0.1 to
3% by weight, but 50% by mole of the organosilane compound
The following is preferred. This is because the addition amount of the organometallic alkoxide compound is 50 mol% of the addition amount of the organosilane compound.
This is because the impact resistance is reduced when the ratio exceeds the above range.

A dialdehyde compound or an acetal compound of dialdehyde can also be used as a crosslinking agent.
When a dialdehyde compound is used, the aldehyde group reacts with a hydroxyl group in the polyvinyl acetal by the action of a catalyst or forms an acetal bond by an acetal exchange reaction with an alkyl acetal group.
When a dialdehyde compound is used, since two aldehyde groups are present in the molecule, cross-linking between or within the molecules of the polyvinyl acetal becomes possible. When an acetal compound of a dialdehyde is used, it is considered that the cross-linking reaction mechanism is exactly the same as that of the dialdehyde, since it is in equilibrium with the corresponding dialdehyde in the presence of water and an acidic catalyst. The dialdehyde compound or the acetal compound of dialdehyde may be used alone, or two or more dialdehyde compounds may be used in combination. Specific dialdehyde compounds include glyoxal, glutaraldehyde, hexanedial, 2-hydroxyhexanedial, malonaldehyde tetramethylacetal, malonaldehyde tetraethylacetal, glutaraldehyde tetramethylacetal, glutaraldehyde tetraethylacetal, and the like. . The amount of the dialdehyde compound or the acetal compound of the dialdehyde in the primer composition is 0.01 to 30% by weight, preferably 50% by mole or less of the organosilane compound. This is because the addition amount of the dialdehyde compound or the acetal compound of the dialdehyde is 50 mol% of the addition amount of the organosilane compound.
If the ratio exceeds the above, impact resistance is reduced.

Fine inorganic oxide particles can be added to the primer layer. Thereby, the refractive index of the primer layer can be adjusted. Examples of the inorganic oxide that can be added include aluminum oxide, titanium oxide, zirconium oxide, iron oxide, antimony oxide, beryllium oxide, zinc oxide, tin oxide, cerium oxide, silicon oxide, and tungsten oxide. These inorganic oxides can be used alone, in the form of a compound or a composite comprising a plurality of inorganic oxides, or in the form of a solid solution or a mixture of solid solutions.

As these inorganic fine particles, commercially available fine particles dispersed in water or an organic solvent can be used. The average particle diameter of the inorganic oxide fine particles, the composite of these inorganic oxide fine particles, or the solid solution or the mixture of the solid solutions is about 1 to 300 nm, preferably 1 to 50 nm.
It is. If the average particle diameter exceeds 300 nm, the film becomes cloudy due to light scattering, resulting in a cloudy lens. In addition, when the diameter is smaller than 1 nm, the production becomes difficult.

The amount of the inorganic oxide fine particles added to the composition for forming the primer layer is 0.1 to 3 as a solid component concentration.
About 0% by weight is preferable. In addition to the setting of the addition amount, the refractive index is controlled by adjusting the type or the mixing ratio of the inorganic oxide such that the refractive index of the primer layer matches or is extremely close to the refractive index of the substrate. . For example, when a high refractive index substrate having a refractive index of 1.60 or more is used, titanium oxide, zirconium oxide, iron oxide, antimony oxide, tin oxide, cerium oxide, silicon oxide, and the like are used with respect to 1 part by weight of polyvinyl acetal. It is preferable to add 1 to 5 parts by weight of inorganic oxide fine particles having a high refractive index such as tungsten oxide as a simple substance, a mixture thereof, a composite or a solid solution or a mixture thereof. When a plastic lens substrate having a low refractive index of about 1.5 is used, it is preferable to add silicon dioxide fine particles having a relatively low refractive index.

The composite in the present invention is, for example, a state in which a certain oxide fine particle and a certain oxide fine particle adhere to each other, and the adhered portion is considered to be chemically bonded. It refers to a state in which inorganic oxide fine particles and certain oxide fine particles are mixed, and atoms to be present at a specific position of the crystal are replaced with atoms of the other inorganic oxide.

Examples of the curing catalyst include dehydration condensation between a silanol group formed by hydrolysis of a hydrolyzable organosilane compound and a hydroxyl group in polyvinyl acetal, and a dialdehyde compound or an acetal compound of dialdehyde and a hydroxyl group in polyvinyl acetal. There is no particular limitation as long as it accelerates the acetalization reaction with. Specifically, inorganic acids such as hydrochloric acid, nitric acid, sulfuric acid, and phosphoric acid, formic acid, acetic acid, benzoic acid, phthalic acid, methanesulfonic acid, benzenesulfonic acid, and alkylbenzenesulfonic acid having 1 to 18 carbon atoms in the alkyl group. And organic tin compounds such as dibutyltin dilaurate, dibutyltin dioctate and dibutyltin diacetate.
Among them, particularly preferred are inorganic acids such as hydrochloric acid and nitric acid, organic acids such as methanesulfonic acid, benzenesulfonic acid and p-toluenesulfonic acid, and organic tin compounds. These may be used alone or as a mixture of two or more kinds of catalysts. The addition amount of the curing catalyst in the primer composition is 0.002 to 10% by weight, preferably 0.005 to 2% by weight. If the amount of the catalyst exceeds 10% by weight, there is a problem that the film becomes hard and the impact resistance is reduced. On the other hand, if the content is less than 0.002% by weight, there is a problem that the alcohol resistance is lowered and the appearance of a hard coat film to be subsequently applied becomes poor.

As the organic solvent in the primer composition,
In hydrocarbons, halogenated hydrocarbons, alcohols, ketones, esters, ethers and other known solvents,
Those which dissolve polyvinyl acetal well can be used. Particularly preferred are methanol, ethanol, propanol, butanol, hexanol, acetone, methyl ethyl ketone, methyl isobutyl ketone, and diethyl ketone, but these may be used alone or in combination of two or more organic solvents. Good.

Various leveling agents for improving coating properties, ultraviolet absorbers and antioxidants for improving weather resistance, and other known additives for improving the performance and function of the film can be used in combination. The thickness of the primer layer is preferably from 0.01 to 30 μm, particularly preferably from 0.1 to 5 μm, from the viewpoint of improving impact resistance. 0.01
If the thickness is less than 30 μm, the impact resistance is insufficient.
If it is larger, the surface accuracy when applied to the lens substrate is reduced.

The method of applying the primer coating is not particularly limited as long as it is a known method such as a spin coating method or a dipping method. Further, it is preferable that the lens base material is subjected to a pretreatment such as an alkali treatment, a plasma treatment, and an ultraviolet treatment as necessary. To form a primer layer, after applying a primer coating to the lens,
Preferably, heating is performed at 70 to 110 ° C for 1 to 60 minutes. By this heat treatment, the hydrolyzed organosilane compound in the composition of the applied primer layer,
The dialdehyde compound or the acetal compound of the dialdehyde and the hydroxyl group contained in the polyvinyl acetal are dehydrated and condensed to crosslink the polyvinyl acetal molecule, and the water generated by the condensation reaction and the organic material previously contained in the primer composition The solvent and water evaporate. In this way, a three-dimensionally cross-linked polyvinyl acetal primer film is formed on the surface of the plastic lens substrate.

On the primer layer containing the above dye,
It is preferable to form a hard coat film in order to improve the scratch resistance of the plastic lens substrate. Particularly, an organosilicon compound represented by the following general formula (I) or a hydrolyzate thereof is preferable. General formula (II): R ¹ aR ² bSi (OR ³ ) _{4- (a + b)} (where R ¹ is a functional group or an organic group having 4 to 14 carbon atoms having an unsaturated double bond) And R ² has 1 carbon atom
6 to 6 hydrocarbon groups or halogenated hydrocarbon groups;
³ is an alkyl group having 1 to 4 carbon atoms, an alkoxyalkyl group or an acyl group, and a and b are each 0 or 1
And a + b is 1 or 2. Of the compounds of the general formula (II), those in which R ¹ has an epoxy group as a functional group are preferred because of their excellent abrasion resistance. For example, the following compounds are used. (1) General formula (III):

[0039]

Embedded image

[0040] (wherein, R ⁴ is an alkyl group or an alkoxyalkyl group or an acyl group having 1 to 4 carbon atoms, R ⁵
Is a hydrocarbon group having 1 to 6 carbon atoms or a halogenated hydrocarbon group, R ⁶ is a hydrogen or methyl group, m is 2 or 3, p
Is 1 to 6, and q is 0 to 2. ). (2) General formula (IV):

[0041]

Embedded image

(Where R ⁷ is an alkyl group or an alkoxyalkyl group or an acyl group having 1 to 4 carbon atoms, R ⁸ is a hydrocarbon group or a halogenated hydrocarbon group having 1 to 4 carbon atoms,
1 is 2 or 3, and r is 1-4. ). Since all of the compounds represented by the above general formula have an epoxy group, they are also called epoxysilane.

Specific examples of epoxysilane include, for example, γ-glycidoxypropyltrimethoxysilane, γ
-Glycidoxypropyltriethoxysilane, γ-glycidoxypropyltrimethoxyethoxysilane, γ-glycidoxypropyltriacetoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane , Β- (3,4-
Epoxycyclohexyl) ethyltriethoxysilane and the like.

Further, among the compounds of the general formula (I), R ¹
Examples of compounds other than those having an epoxy group as a functional group (including those having a = 0) include, for example, the following. Methyltrimethoxysilane, methyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriacetoxysilane, vinyltrimethoxyethoxysilane, γ-methacryloxypropyltrimethoxysilane, aminomethyltrimethoxysilane,
3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, γ-chloropropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, 3,3,3-trifluoro Various trialkoxysilanes such as propyltrimethoxysilane, trisiloxysilane or trialkoxyalkoxysilane compounds.

Exemplary compounds of the above general formula (II)
Is an OR that binds to any Si atom ^Three There are three groups
(A + b = 1) This is an example of trifunctionality, but OR^Three There are two groups
(A + b = 2)
Can be used. As an example of a bifunctional equivalent compound
Dimethyldimethoxysilane, diphenyldimethoxy
Sisilane, methylphenyldimethoxysilane, methylbi
Nildimethoxysilane, dimethyldiethoxysilane, etc.
There is.

The compound of the general formula (II) may be used alone or in combination of two or more according to the purpose. In particular, when a bifunctional compound is used, 3
It is preferable to use together with a functional compound. When trifunctional compounds are used in combination, 2> a + b> 1 on average.
Furthermore, it is also possible to use a tetrafunctional equivalent compound of a + b = 0 in combination. Examples of tetrafunctional equivalent compounds include methyl silicate, ethyl silicate, isopropyl silicate, n-propyl silicate, n-butyl silicate, t-butyl silicate, sec-butyl silicate and the like. As described above, by using a combination of trifunctional and tetrafunctional compounds, it is possible to impart appropriate hardness to the film.

The compound of the formula (II) may be used as it is, but is preferably used as a hydrolyzate for the purpose of increasing the reaction rate and lowering the curing temperature. 2-4
When two or more compounds having the same functional number are used in combination, or two or more compounds having different functional numbers are used in combination, they may be used after hydrolysis or may be used before hydrolysis. And co-hydrolysis. The alcohol HOR ³ is released by the hydrolysis, and the compound represented by the general formula (I
The compound of I) is the corresponding silanol:

[0048]

Embedded image become. Silanol rapidly undergoes dehydration condensation to become an oligomer. Therefore, for this reaction to proceed sufficiently,
After the hydrolysis, it may be left (cured) for 1 to 24 hours.
When these compositions are used, a sol may be added to increase the hardness. Further, in order to improve the flowability at the time of coating, to improve the smoothness of the cured film, for example,
Various solvents such as water, lower alcohols, acetone, ethers, ketones and esters can be used.

As the above-mentioned inorganic oxide fine particles, those which can be added to the above-mentioned primer layer can be used.
For example, a modified sol in which tin oxide fine particles are preferably used as nuclei and the surface of which is covered with a composite sol of tin oxide and tungsten oxide is preferable. This modified sol is a colloid having a double structure in which colloidal particles of tin oxide (sol) are completely or incompletely surrounded by colloidal particles of a tin oxide-tungsten oxide complex (sol). "Particles" are colloidally dispersed in a dispersion medium. The particle size of the colloidal particles of tin oxide serving as a core is generally 4 to 50 nm.
It is. The particle size of the surrounding colloidal particles of the composite is generally between 2 and 7 nm. Tin oxide particles serving as nuclei are positively charged. Therefore, when this is directly mixed with the component represented by the general formula (II), the general formula (II)
Are aggregated (gelled) because they have a negative charge due to -SiO ^- H ⁺ . In contrast, the composite particles are negatively charged. Therefore, this is represented by the general formula (I
No aggregation when mixed with I).

The tin oxide-tungsten oxide composite sol is generally produced by adding an aqueous solution of sodium stannate under vigorous stirring at room temperature to an aqueous solution of tungstic acid produced by ion exchange of an aqueous solution of sodium tungstate. . The weight ratio of WO ₃ / SnO ₂ composite sol is generally 0.5 to 100. When the coating composition of the present invention is prepared to form a coating film even if it is smaller than 0.5 or larger than 100, only a coating film having inferior performance can be obtained.

The modified sol is an aqueous sol of tin oxide, "S"
nO against ₂ 100 parts by weight in terms of "it is produced by adding an aqueous sol of the complex" WO ₃ and 2 to 100 parts by weight in total weight in terms of SnO ₂ "at room temperature, under vigorous stirring. Also in this case, when the coating composition of the present invention is prepared to form a coating film even if the amount is less than 2 parts by weight or more than 100 parts by weight, only a coating film having poor performance can be obtained.

The particle diameter of the double-structured colloidal particles of the modified sol is generally 4.5 to 60 nm. When the aqueous sol of the composite is mixed with the aqueous sol of tin oxide, it is presumed that the tin oxide particles and the composite particles are chemically bonded. Therefore, the produced modified sol is presumed to exist stably. More particularly, titanium oxide,
When antimony oxide, tungsten oxide, cerium oxide, zirconium oxide, or tin oxide is used, the refractive index of the composition can be increased. The present invention can exert particularly excellent effects when such a high refractive index component is used. These sols may be in the form of a solid solution in which a plurality of oxides are mixed to form a crystal structure different from these oxides.

As a dispersion medium, water, alcohol and other organic solvents are used. It is preferable to add an organic amine and other stabilizers to the sol. The particle size of the sol is 1
Those having a thickness of from 200 to 200 nm, particularly from 5 to 100 nm, are preferred.
If it is smaller than 1 nm, it is difficult to manufacture, the stability of the sol itself is poor, and the effect is small. Also 200
If it is larger than nm, the stability of the coating composition, the transparency and the smoothness of the coating film will be reduced.

In addition to the above components, if necessary, for example, for the purpose of improving the adhesion to the substrate (molded product) to be coated, or for the purpose of improving the stability of the coating composition. Alternatively, various additives may be used in combination. Examples of additives include pH adjusters, viscosity adjusters, leveling agents,
Matting agents, stabilizers, ultraviolet absorbers, antioxidants and the like.

Various surfactants can be used in combination with the coating composition for the purpose of improving the flow at the time of application, improving the smoothness of the coating film and reducing the friction coefficient of the coating film surface, In particular, a block or graft copolymer of dimethylsiloxane and alkylene oxide,
Further, a fluorine-based surfactant is effective. As the coating method, a usual coating method such as brush coating, dipping, roll coating, spray coating, and flow coating can be used.
At this time, the application conditions are determined mainly by the properties of the primer composition forming the primer layer.

To accelerate the reaction and cure at low temperature,
The following curing catalysts can be used. (1) Amines: monoethanolamine, diethanolamine, isopropanolamine, ethylenediamine,
Isopropylamine, diisopropylamine, morpholine, triethanolamine, diaminopropane, aminoethylethanolamine, dicyandiamide, triethylenediamine, 2-ethyl-4-methylimidazole.

(2) Various metal complex compounds: General formula: AlX _n Y _3-n (where X is OL (L is a lower alkyl group), and Y is general formula M ¹ COCH ₂ COM ² (M ¹ , M ² is a lower alkyl group) and a ligand derived from M ¹ COCH ₂ COOM ² , and n is 0, 1 or 2).

Particularly useful chelate compounds include aluminum acetylacetonate, aluminum bisethylacetoacetate monoacetylacetonate, and aluminum-di-n from the viewpoints of solubility, stability, and catalyst curing.
-Butoxide-monoethylacetoacetate, aluminum-di-iso-propoxide-monomethylacetoacetate and the like.

In addition, chromium acetylacetonate, titanyl acetylacetonate, cobalt acetylacetonate, iron acetylacetonate, manganese acetylacetonate, nickel acetylacetonate, EDT
A, and also a complex compound of Al, Fe, Zn, Zr, and Ti. (3) Metal alkoxides: aluminum triethoxide, aluminum tri-n-propoxide, aluminum tri-n-butoxide, tetraethoxytitanium, tetra-n-butoxytitanium, tetra-i-propoxytitanium.

(4) Organic metal salts: sodium acetate, zinc naphthenate, cobalt naphthenate, zinc octylate, tin octylate. (5) Perchlorates: magnesium perchlorate and ammonium perchlorate. (6) Organic acids or anhydrides: malonic acid, succinic acid, tartaric acid, adipic acid, azelaic acid, maleic acid, o-phthalic acid, terephthalic acid, fumaric acid, itaconic acid, oxaloacetic acid, succinic anhydride, maleic anhydride Acids, itaconic anhydride, 1,2-dimethylmaleic anhydride, phthalic anhydride, hexahydrophthalic anhydride, naphthalic anhydride.

(7) Lewis acid: ferric chloride, aluminum chloride. (8) Metal halide: stannous chloride, stannic chloride,
Tin bromide, zinc chloride, zinc bromide, titanium tetrachloride, titanium bromide, thallium bromide, germanium chloride, hafnium chloride, lead chloride, lead bromide.

The above catalysts may be used alone or in combination of two or more. In the colored plastic lens of the present invention formed as described above, the thickness of the pigment-dispersed resin coating film is several μm with respect to the thickness of the lens substrate of several mm, and the coating film (for example, a hard coat film) The film thickness is 2μ
m. Pigment-dispersed resin coating film and coating film
It may be provided on any surface of the lens. For example, it may be formed on one surface of the lens, for example, one surface on the eyepiece side, or may be formed on both surfaces.

The hard coat film can be formed by a CVD method in addition to the above-described one.
Examples of the material include compounds containing Si and / or Ti, and specific examples thereof include tetramethoxysilane, dimethoxysilane, methylmethoxysilane, tetramethoxysilane, tetramethoxytitanium, tetra-n-butoxytitanium, and tetradiethylaminotitanium. It is. The thickness of the hard coat film formed by the CVD method is greater than 0.4 μm and 5 μm.
It has a film thickness smaller than m. By forming a hard coat film by CVD, it becomes possible to form a hard coat film regardless of the lens substrate surface shape. In addition, since the method does not depend on the immersion dyeing method, a hard coat film can be formed on a large number of lenses at a time, and the production of a dyeable lens having durability can be facilitated.

Further, the colored plastic lens of the present invention can further form an antireflection film or a water-repellent film made of an inorganic oxide, if necessary. As the material for forming the water-repellent film, a silazane compound containing a fluoroalkyl group is preferable. As the amino group in the silazane compound, one having 1 to 3 functional groups can be used. Further, those having an alkoxy group as the substitution base material can also be used. By providing the water-repellent film, a stained lens that can withstand use in various environments can be obtained.

In the colored plastic lens of the present invention, a pigment-dispersed resin coating film is formed on the lens surface and is not impregnated into the substrate as in the prior art. Uniform and stable coloring is possible. Further, there is no occurrence of color loss due to long-term use. Further, when a hard coat film is formed as a coating film on the pigment-dispersed resin layer, the dye does not dissolve into the hard coat solution even when immersed in a hard coat solution such as a silicon resin.

Hereinafter, embodiments of the present invention will be described.

[0067]

EXAMPLES (1-1) Preparation of Primer Composition In a reaction vessel equipped with a rotor, 4.3 parts by weight of methyltrimethoxysilane and 40 parts by weight of ethanol were charged, and 0.001N hydrochloric acid was added to 0.5 part by weight. Add parts by weight and stir for 1 hour to effect hydrolysis. A solution of 2.7 parts by weight of titanium tetra n-butoxide as a crosslinking agent in 20 parts by weight of n-butanol was added to the hydrolyzate, and the mixture was stirred for 30 minutes to obtain a hydrolyzed condensate of organoalkoxysilane / organotitanate. Was.

In another reaction vessel equipped with a rotor, a polyvinyl butyral resin (Eslec BM) manufactured by Sekisui Chemical Co., Ltd.
-2, butyralization degree 68%, polymerization degree 800), 20 parts by weight of n-butanol 420 parts by weight, ethanol 330
In 100 parts by weight of water, 4.2 parts by weight of tetramethoxysilane as a crosslinking agent, and 50 parts by weight of ethyl cellosolve. The solution of the above-mentioned organoalkoxysilane / organotitanate hydrolyzed condensate is added to the obtained solution of polyvinyl butyral with stirring.

Next, a solution prepared by dissolving 175 parts by weight of methanol fine particles (HIS-30M, manufactured by Nissan Chemical Industries, Ltd.) dispersed in fine particles of tin oxide / tungsten oxide and 2 parts by weight of dibutyltin dilaurate as a curing catalyst in 20 parts by weight of ethanol. Then, a solution prepared by dissolving a fluorine-based surfactant (Fluorard FC430, manufactured by Sumitomo 3M Ltd.) in 10 parts by weight of ethanol and 50 parts by weight of pure water as a leveling agent are sequentially added, and the mixture is kept in a homogeneous state for 24 hours. Stir. Disperse thread 225 is added to this mixture for 1
g, 56 g of Disperse Blue and 1 g of Dusperse Yellow 33 were added and dissolved. Thereafter, the mixture was sufficiently stirred and then filtered through a 3 μm membrane filter. After completion of the stirring, the mixture was filtered through a 3 μm mesh filter to prepare a dye-containing primer composition.

(1-2) The coating and curing degree of the dye-containing primer composition is -4.00 diopter and the center thickness is 1.0 mm.
A plastic lens for R-39 glasses is used. This was immersed in a 10% NaOH aqueous solution at 60 ° C. for 5 minutes as a pretreatment, washed with warm water and dried. A dipping method (pulling speed 100 cm /
min), apply the primer composition prepared in (1-1), and apply the applied plastic lens at 100 ° C. for 15 minutes.
The primer was cured by heat treatment for minutes.

(1-3) Preparation of Silicon Hardcoat Solution In a reaction vessel equipped with a rotor, 180 parts by weight of γ-glycidoxypropyltrimethoxysilane were charged, and the mixture was vigorously stirred using a magnetic stirrer. , 0.01
40 parts by weight of a normal hydrochloric acid aqueous solution was added at a time, and hydrolysis was continued for 1 hour to obtain a partially condensed hydrolyzate.

To the above hydrolyzate, 630 parts by weight of methanol fine particles (HIS-30M, manufactured by Nissan Chemical Co., Ltd.) dispersed with fine particles of tin oxide and tungsten oxide were added, and 4 parts by weight of aluminum ethylenediaminetetraacetate as a curing catalyst. Then, 0.45 parts by weight of a silicon surfactant (SH30PA, manufactured by Toray Dow Corning Co., Ltd.) was added as a leveling agent, and the mixture was sufficiently stirred and mixed, followed by filtration with a 3 μm membrane filter to prepare a hard coat liquid.

(1-4) Coating and curing of the silicon-based hard coat liquid The silicon-based hard coat liquid obtained in (1-3) is applied to both sides of the plastic lens having the primer layer obtained in (1-2). Dipping method (pulling speed 100c
m / min). Apply coated lens at 100 ℃
For 4 hours to cure the hard coat layer.

(1-5) Formation of antireflection film An antireflection film composed of five layers of silicon dioxide / zirconium oxide on both surfaces of the plastic lens having the primer layer and the hard coat layer obtained in (1-4). Was formed by a vacuum evaporation method. (1-6) Performance Evaluation of Plastic Lens Having Composite Film FIG. 1 shows that a primer layer containing a dye was formed on a plastic lens made of CR-39 manufactured in this example, and a hard coat was formed thereon. A spectral transmittance curve 1 of a stained lens having a layer formed thereon and having an antireflection film thereon and a spectral transmittance curve 2 of a plastic lens made of a urethane base material are shown.

The luminous transmittance of each of the colored plastic lenses was 59%, and uniform and highly transparent lenses were obtained. Even when a silicone resin cured film is applied, neither the color tone nor the luminous transmittance changes, and the color difference between the above two lenses is
0.11. Comparative Example A disperse dye KPRD RED306 (manufactured by Mitsui Toatsu Chemicals, Inc.) was dispersed in water together with a surfactant to prepare a dyeing solution. This was heated, and the same plastic lens molded product as in Example 1 was immersed therein for about 10 minutes.

As a result, it was colored to have a luminous transmittance of 56%. The lens thus dyed was immersed in the same polyvinyl acetal resin-based primer vehicle as used in Example 1, heated and cured, and then immersed in a silicone resin solution. Was observed. In FIG. 2, after coloring with a dye, the spectral transmittance curve 3 before the formation of the polyvinyl acetal resin layer, the spectral transmittance curve 4 before the formation of the silicone resin layer after the formation of the polyvinyl acetal resin layer, and the spectral transmittance after the formation of the silicone resin layer. The rate curve 5 is shown.

As can be seen from the figure, immersion in the silicone resin liquid resulted in a luminous transmittance of 66%, a color difference before and after the formation of the silicone resin layer of 19.24, and severe color loss.

[0078]

The coloring of the plastic lens of the present invention is as follows.
Since the dyed lens is manufactured by including a dye in the coating film and applying it on the base material, a colored lens that is transparent and uniform in color regardless of the material of the base material and has no color variation can be obtained. . It can be colored under almost the same conditions regardless of the base material,
Since there is no need for a production line relating to different coloring for each substrate, it is possible to color substrates composed of different materials on a common production line. Therefore, the manufacturing cost can be reduced.

Further, when the hard coat layer is formed on the coating film, the dye does not seep into the hard coating solution even if the substrate on which the coating film is formed is immersed in the hard coating solution.
No change in color tone after hard coat formation due to color loss. Further, the hard coat liquid is not colored by the dye. Therefore, the replacement of the hard coat liquid is reduced. In addition, a hard-coating film having improved scratch resistance and excellent durability can be efficiently produced with good reproducibility.

Further, since the coating film has polyvinyl acetal, a colored plastic lens having excellent weather resistance and light resistance, and particularly having impact resistance can be obtained.
Therefore, it has become possible to use a colored lens having excellent fashionability in various use environments.

[Brief description of the drawings]

FIG. 1 is a graph showing a spectral transmittance curve of a colored plastic lens manufactured according to Example 1.

FIG. 2 is a graph showing a spectral transmittance curve of a colored plastic lens manufactured according to a comparative example.

[Explanation of symbols]

1 ... Spectral transmittance curve of lens before forming silicone resin cured film 2 ... Spectral transmittance curve of lens after forming silicone resin cured film 3 ... Formation of polyvinyl acetal resin layer after coloring with dye Spectral transmittance curve of lens before 4 ... Spectral transmittance curve of lens after forming polyvinyl acetal resin layer and before forming silicon resin layer 5 ... Spectral transmittance curve of lens after forming silicone resin cured film

Claims (4)

[Claims] 1. A colored plastic lens comprising: a plastic lens substrate; and a coating film formed on the plastic lens substrate and containing a dye and polyvinyl acetal as main components. 2. The plastic lens according to claim 1, wherein a coating film mainly composed of a material different from the coating film is formed on the coating film. 3. The plastic lens according to claim 1, wherein the polyvinyl acetal is a reaction product using at least one of the following three compounds as a crosslinking agent. A) Organometallic alkoxide compounds or alkoxide diketonate compounds b) Hydrolyzable organosilane compounds c) Dialdehyde compounds or acetal compounds of dialdehydes 4. The plastic lens according to claim 1, wherein said coating has a thickness of about 0.1 to 5 μm.