JPH02230103A - High refractive index plastic lens - Google Patents

Abstract

PURPOSE:To obtain a lens which has good scratching resistance and adhesive strength, does not generate interference fringes and is thin and light by forming a cured film consisting of a coating compsn. contg. specific components on a polyurethane lens. CONSTITUTION:The cured film consisting of the coating compsn. contg. the components A, B, C, D is formed on the surface of the plastic lens substrate essentially consisting of the polyurethane. The component A is the org. silicon compd. expressed by general formula R<1>Si(OR<2>)3 (where R<1> denotes 4 to 14C org. group contg. an epoxy group; R<2> denotes 1 to 4C alkyl group or 1 to 4C alkyl carbonyloxy group) or the hydrolyzate the thereof. The component B is an antimony pentaoxide sol of 5 to 50nm dispersed colloidally in an org. solvent. The component C is one or more kinds of epoxy compds. expressed by general formulas I, II. The component D is titanium-iso-propoxyocctylene glycolate.

Description

Detailed Description of the Invention [Industrial Application Field] The present invention relates to a high refractive index plastic lens, and more specifically, to a polyurethane lens substrate having a high refractive index, a hardened resin having a small refractive index difference with the polyurethane lens substrate is used. The present invention relates to a high refractive index plastic lens on which a film is applied, and more preferably an inorganic antireflection film is applied thereon.

[Prior Art and Rankings] In recent years, plastics have come to be used as eyeglass lens materials instead of inorganic glass. Plastic lenses have many advantages over inorganic glasses, such as being lighter and having better impact resistance than conventional glass lenses, and being easier to dye.

However, diethylene glycol bisallyl carbonate (hereinafter abbreviated as CR-39), which is mainly used in plastic lenses, has a refractive index of 1.50, which is lower than that of inorganic glass, and the edge thickness becomes large, especially in negative lenses. There is a demand for thinner plastic lenses.

Various proposals have been made in response to the demand for thinner plastic lenses. For example, JP-A-60-21730
No. 1 proposes a copolymer of a polyisocyanate, a polyol, and a vinyl compound having an aromatic ring. Furthermore, JP-A-59-164501 proposes a copolymer of a halogen-containing aromatic vinyl compound.

However, although these copolymers can provide a refractive index of 1.60 or more, the Atsube's number is approximately 30, which poses a problem when applied to eyeglass lenses.

As an alternative to the above-mentioned copolymers which have a high refractive index but cannot be applied to eyeglass lenses,
No. 199016 proposes a polyurethane lens made of a copolymer of polyisocyanate and polythiol. This polyu? For tan lenses, n■ is 1.56~
It is as high as 1.64 and has a specific gravity of 1622~]. 44, it is particularly suitable as a thin and light eyeglass lens. Additionally, this polyurethane lens inherently has excellent impact resistance and stainability.

However, like other plastic lenses, this polyurethane lens also has poor scratch resistance, and in order to improve this scratch resistance, for example, Japanese Patent Publication No. 56 = 18
A cured film was formed by applying a coating composition containing a hydrolyzate of an organosilicon compound and colloidal silicate as main components, as disclosed in Japanese Patent Publication No. 62-4 and Japanese Patent Publication No. 60-39291, to a polyurethane lens. In this case, the scratch resistance is greatly improved and a product that can withstand use is obtained, but since the refractive index of the cured film is lower than that of a polyurethane lens, interference fringes are observed and it is not practically preferred.

A cured film of melamine-based resin having a refractive index close to that of the lens substrate is formed on the surface of a synthetic resin lens with a relatively high refractive index, such as a polymer such as diallyl phthalate, diallyl isophthalate, diallyl rendate, etc. A method for obtaining an antireflection high refractive index lens by forming an antireflection film made of an inorganic substance on top (Japanese Patent Publication No. 61-4812)
In this method, a solvent and a crosslinking catalyst are added to hexamethoxymethylolmelamine and a resin containing OH groups, Coo}I groups, NH2 groups, epoxy groups, etc. that undergo a crosslinking reaction with the melamine compound. A cured melamine resin film is obtained by applying the mixed solution onto the synthetic resin lens substrate and curing it by heating.

However, in the case of resins that are cured by addition condensation, such as melamine-based resins, the heat curing processing temperature must be quite high for one meter, and substrates with good heat resistance such as metal and glass have considerable hardness. Although a certain film can be obtained, there is a drawback that a long curing time is required because there is a limit to the processing temperature in the case of a substrate with poor heat resistance such as plastic. In addition, because the processing temperature is low, even if the curing time is prolonged, the hardness is not as strong as that applied to metal or glass. It is clear that similar drawbacks arise.

Furthermore, Japanese Patent Application Laid-open No. 56-99236 describes metals, alloys,
A colloidal dispersion selected from metal salts and a colloidal dispersion of the formula T-jsi
Disclosed is a cured film obtained from a coating composition comprising a partial condensate of an organo-gayelite compound having <OH)3 and a cured contact of the partial condensate of the organosilicon compound. Its relatively high refractive index satisfies one of the requirements for a cured film for high refractive index plastic lenses, but the stability of the coating composition is limited because sodium acetate, choline acetate, etc. are used as curing catalysts. However, there were practical problems such as the transparency of the cured film after coating.

Furthermore, Japanese Patent Publication No. 61-54331 discloses a composition comprising a colloidally dispersed antimony pentoxide sol, an epoxy group-containing organosilicon compound, and one or more epoxy resin curing agents selected from various metal complex compounds and metal alkoxides. A cured film obtained from a coating composition is disclosed, and the cured film also satisfies one of the conditions as a cured film for a high refractive index plastic lens in that its refractive index is relatively high. If the amount of antimony pentoxide sol added is increased in order to increase the refractive index, the cured film becomes cloudy and tends to crack, making it undesirable for use as an eyeglass lens. In Manako's prior art, an aluminum compound such as aluminum acetylacetonate is used as an epoxy resin curing agent, but a coating composition containing such an epoxy resin curing agent is applied to a polyurethane lens substrate and cured. In this case, there is a problem in the adhesion between the obtained cured film and the substrate.

Therefore, it is an object of the present invention to solve the above-mentioned drawbacks of the prior art, and to not only satisfy basic properties such as hardness, transparency, and adhesion with a polyurethane lens substrate, but also to improve refraction with a high refractive index polyurethane lens substrate. The object of the present invention is to provide a new polyurethane lens having a cured film that does not generate undesirable interference fringes because the index difference is small.

Means for Solving Problem 1] As a result of intensive studies to achieve the above object, the present inventors have found that
A coating composition containing the following components (A), (B), (C) and (D) is applied to the surface of a plastic lens mainly composed of polyurethane obtained by polymerizing polyisocyanate and polythiol, and cured. The resulting cured film not only satisfies basic properties such as hardness, transparency, and adhesion to the polyurethane lens substrate, but also
We discovered that because the difference in refractive index with high refractive index polyurethane lenses is small, there is no generation of undesirable interference fringes, etc.
Let's complete this invention.

(A) An organosilicon compound or its Hydrolyzate.

(8) Particle size 5 colloidally dispersed in organic solvent
- 50 nm antimony pentoxide sol.

(C) One or more epoxy compounds represented by the following general formula.

Q (Here, n is 2 or 3.) Represents U H, C H 3 or -CH2 CH3. ] (D) Titanium-iso-proboxyoctylene glycolate.

In the present invention, the high refractive index plastic lens substrate on which the cured film is formed is obtained by cast polymerization of a mixed solution of polyisocyanate and polythiol in a mold consisting of a lens mold and a resin gas get. .

There are no particular limitations on the polyisocyanate used as a monomer for manufacturing polyurethane lenses, but
Tolylene diisocyanate, diphenylmethane diisocyanate, polymeric diphenylmethane diisocyanate, naphthylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, hydrogenated xylylene diisocyanate, hydrogenated diphenylmethane diisocyanate, lysine diisocyanate, triphenylmethane triisocyanate , tris(incyanate phenyl) thiophosphate, trans-cyclohexane 1,4-diisocyanate, p-phenylene diisocyanate, tetramethylene diisocyanate, 1,6.11-undecane triisocyanate, 1,8-diisocyanate-4-
Polyisocyanate compounds such as isocyanate methyl octane, lysine ester triisocyanate, 1,3,6-hexamethylene triisocyanate, and cyclohebutane triisocyanate, and allophanate modified products, biuret modified products, incyanurate modified products of these compounds, Examples include adduct modified products with polyols or boritiol, which may be used alone or in combination with two or more as necessary.
It may also be a mixture of more than one species. Other known isocyanate compounds may be used, but the isocyanate compound serving as the main component must be bifunctional or higher. C1 or Br in known aromatic isocyanate compounds
Particularly preferable incyanate compounds include non-yellowing type isocyanate compounds represented by xylylene diisocyanate, isophorone diisocyanate, and hexamethylene diisocyanate.

Further, the polythiol used in the reaction with polyisocyanate for producing a polyurethane lens is not particularly limited, and any known polythiol can be used. For example, ethanedithiol, propanedithiol, propanetrithiol, butanedithiol, pentanedithiol, hexanedithiol, hebutanedithiol, octanedithiol, cyclohexanedithiol, cyclohebutanedithiol, 2,5-dichlorobenzene-1,3-dithiol, Examples include pentaerythritol tetrakis 3-mercabutobrobionate, pentaerythritol detrakis thioglycolate, and pentaerythritol derivatives are particularly preferred.

During cast polymerization of polyisocyanate and polythiol, by adding a phosphoric acid ester represented by the following general formula as a mold release agent to the monomer mixture, it has an excellent optical surface, a high refractive index, and a low Atsube number. A plastic lens with sufficient performance to be used as a large eyeglass lens can also be obtained.

O (R-0)2 -P-OH (Here, R is an alkyl group having 8 or less carbon atoms.) The amount of phosphoric acid ester used is based on 100 parts by weight of the total amount of polyisocyanate and polythiol used. te 0.01-
The amount is 1 part by weight, particularly preferably 0.02-5 parts by weight. If the amount of phosphoric acid ester used is less than 0.01 part by weight, it will be difficult to form a paper mold between the lens mold and the lens after polymerization, and if it exceeds 20 parts by weight, the lens may become cloudy or the formulation may become difficult. Foaming or gelation occurs during the process.

In the present invention, the cured film formed on the polyurethane lens substrate is as follows (A), (B), (C) and (
It is obtained by applying and curing a coating composition containing component 0) on a polyurethane lens substrate.

(A) General formula R Si (OR > 3 (where R
1 represents an organic group containing an epoxy group having 4 to 14 carbon atoms, and R2 represents an alkyl group having 1 to 4 carbon atoms. ) or its hydrolyzate.

(B) Particle size 5 colloidally dispersed in an organic solvent
- 50 nm antimony pentoxide sol.

(C) One or more epoxy compounds represented by the following general formula.

(Here, n is 2 or 3.) [Here, X represents -CH20R3 or -OR3 (R3 represents H or C }-1, CH3 or 1082 CH3.] (D) Titanium - iso - Proboxyoctylene glycolate.

The general formula RSi(O
Examples of the organosilicon compound or its hydrolyzate represented by R2) include γ-glycidoxy pyrutrimethoxysilane, γ-glycidoxy pyrutriethoxysilane,
γ-glycidoxybrobyltrimethoxyethoxysilane, γ-glycidoxyprobyltriacetoxysilane, β
-(3,4-epoxyhexyl)ethyltriethoxysilane and the like and hydrolysates thereof.

Further, the antimony pentoxide sol used as component (B) in the present invention is a colloidal solution in which antimony pentoxide fine particles having a particle size of 5 to 501 m are dispersed in an organic solvent, and is produced by a well-known method.

There are two types of ammothine pentoxide sol: water-dispersed ones and organic solvent-dispersed ones, but when a water-dispersed antimony pentoxide sol is used, the stability of the coating liquid is poor, and there are also problems with the transparency of the cured film. Yes, it is not practical. Furthermore, coating compositions for plastic lenses are often diluted with a space-saving solvent before application, and in such cases, colloid stability deteriorates if the composition is water-dispersed. Therefore, the antimony pentoxide sol used in the present invention is limited to one dispersed in an organic solvent. Examples of organic solvents used as dispersion media include alcohols such as methanol, ethanol, and isoprobanol, methyl cellosolve, ethyl cellosolve,
Examples include cellosolves such as butyl cellosolve.

Antimony pentoxide having a particle size of 5 to 50 nm is preferably used. If the particle size is less than 50 nm, the stability of the liquid will deteriorate, and if the particle size exceeds 50 nm, there will be problems with the transparency of the cured film, which is not preferable.

The amount of antimony pentoxide sol used is preferably such that the ratio of solid content jl of antimony pentoxide/amount used of the organosilicon compound or its hydrolyzate is from ]/2 to 4/1. If the ratio is less than 1/2, the refractive index of the cured film will be low and interference fringes will become a problem. Moreover, if the ratio is 4/1 or more, problems arise in the adhesion between the cured film and the substrate and the adhesion between the cured film and the inorganic antireflection film provided as necessary, as will be described later.

The epoxy compound used as component (C) in the present invention is represented by the following general formula.

0.? , Yya is 11, C H 3 or 1C}{■
C }-] represents 3. ] This epoxy compound is used to improve the compatibility between the organosilicon compound or its hydrolyzate and the antimony pentoxide sol, and to improve the adhesion to the substrate and anti-reflection coating provided as necessary. The amount used is preferably 5 to 100 parts by weight based on the total of 1100 parts by weight of components (A) and (8). If the amount is less than 1 part by weight, there will be a problem with the transparency of the cured film, and if it exceeds 100 parts by weight, the refractive index of the cured crotch will be low and interference fringes will become a problem, and the hardness of the cured film will also decrease. I don't understand.

Titanium-is used as (li) component in the present invention
o-Proboxyoctylene glycolate is used to increase the adhesion between the lens substrate and the cured film, and between the cured film and the antireflection film.The amount of titanium-iso-proboxyoctylene glycolate used is (8). Total JI of component and (8) component
5-60 parts by weight based on parts by weight of IOO is preferably used. If the amount used is less than 5 parts by weight, problems will arise in the adhesion between the cured film and the antireflection film, and if it exceeds 60 parts by weight, problems will arise in the transparency of the cured film.

The coating composition used in the present invention may contain various surfactants for the purpose of improving flowability during coating and improving the smoothness of the cured film. Further, ultraviolet absorbers, antioxidants, etc. can also be used as long as they do not affect the physical properties of the cured film.

It can be used by diluting it with a suitable melt according to the application method. As the coating means, commonly used methods such as dipping, spinning, and spraying can be used, but dipping and spinning are particularly preferred from the viewpoint of surface accuracy.

Further, in the polyurethane lens with a cured film of the present invention, it is preferable to form an antireflection film made of an inorganic substance on the cured crotch. Such an anti-reflection film includes a film in which a high refractive index film and a low refractive index film are alternately laminated, and the material for the high refractive index film is particularly preferably zirconium oxide, aluminum oxide, titanium oxide, etc. , cerium oxide,
Indium oxide, neodymium oxide and tantalum oxide can also be used. Silicon oxide is particularly preferred as a material for the low refractive index film, and magnesium fluoride can also be used.

The order of stirring the nuclear layer may be high, low, ... high, low, or low, high, ... low.
A preferable effect can be obtained if the number of layers is 3 to 20.

[Examples] The present invention will be explained in detail below with reference to Examples, but the present invention is not limited to these Examples. It should be noted that all parts in the examples are based on weight.

[Example 1] (Preparation of high refractive index polyurethane lens) 100 parts by weight of m-xylylene diisocyanate, 42 parts by weight of pentaerythritol tetrakis 3-merkabutopionate, 6 parts by weight of di-n-butyl phosphate, and 0 parts by weight of dibutyltin dilaurate. .25 weight 1 part and 2-(
0.5 weight and 1 part of 2'-hydroxy-5'-t-octylphenylpenzotriazole was mixed and thoroughly stirred, followed by deaeration for 60 minutes under a vacuum of 1 mmflg.

Next, the mixed solution was poured into a mold consisting of a glass lens mold and a resin gasket, and heated from 25°C to 12°C.
The temperature was raised continuously to 0°C over 20 hours, then 120°C.
Polymerization was carried out by holding at ℃ for 2 hours. After polymerization, the gasket was removed and the lens mold and lens were separated to obtain a high refractive index polyurethane lens.

The obtained lens had good optical properties of nd=1.592 and vd=36.

<<Preparation of Coating Solution>> 54 parts by weight of a 0.06N hydrochloric acid aqueous solution was added dropwise to 212 parts by weight of γ-glycidoxib-pyrutrimethoxysilane while stirring. After the completion of the dropwise addition T, stirring was carried out for 24 hours to obtain a hydrolyzate. Then, antimony pentoxide sol (methanol dispersion sol, average particle size 10 nm, solid content 30%) was added to 42
4 parts by weight, Denacol EX-52 as an epoxy compound
1 (manufactured by Nagase Kasei Co., Ltd., polyglycerol boriglycidyl ether) and 1 part of 68 weight, and further titanium-I.
So-Bl7 boxyoctylene glycolate 34 times 1
A coating liquid was obtained by adding 100% of the mixture and aging the mixture for another 100 hours while stirring.

(Formation of cured film) The high refractive index polyurethane lens produced by the above method was
After thorough cleaning by immersion in a 10% NaOH aqueous solution at 0°C for 5 minutes, the coating solution prepared by the above method was used by the dipping method (pulling speed 12 cm/min).
Coat with 120'C and heat for 1 hour to obtain a cured film.

(Formation of antireflection film) An antireflection film was formed on the cured crotch formed by the above method by vacuum evaporation. In other words, the degree of vacuum is 3×10'mm
llg, Si023/2 people at substrate temperature 85℃, Zr02
]/16λ, Si02 1/10λ, Zr0 2 1
/2λ and Si021/4λ were deposited in this order to obtain an antireflection high refractive index polyurethane lens with a double-sided reflectance of 2%.

This lens was evaluated according to the evaluation method below.

(1) Scratch Resistance Test The lens surface was rubbed with still wool #OO00 and scratch resistance was visually judged. Use the following criteria for judgment.

A... There will be almost no scratches even if you rub it hard B... You will get a lot of scratches if you rub it hard C... You will get the same scratches as the lens board (Please note that the one between A and B is A', (2) The presence or absence of interference fringes was determined visually under a fluorescent lamp. The criteria for judgment are as follows.

A: Interference fringes are hardly visible B: A little visible C: Quite visible (The one between A and B is indicated as A', and the one between B and C is indicated as B') (3) Adhesion 100 cross-cuts were made at 1 mm intervals, cellophane tape was strongly applied and rapidly peeled off, and the presence or absence of peeling of the anti-reflection film and the cured film was examined.

(4) Appearance Visually check the transparency of the film and the presence of uneven coating.

(5) From a height of 27α to the center of a lens with a center thickness of 2 mm for impact resistance.
Drop a 6g steel ball and check for damage. As shown in Table 2, the evaluation results of the polyurethane lens with the cured film and antireflection film of this example are as follows: A' in scratch resistance and interference fringes;
Adhesion, appearance and impact resistance were good, and overall excellent results were obtained.

[Example 2-10] A polyurethane lens with a cured film and an antireflection film was manufactured in the same manner as in Example 1 except that a coating liquid having the composition shown in Table 1 was used, and evaluated in the same manner as in Example 1. . As shown in Table 2, the evaluation results were equivalent to or better than those of Example 1.

"Comparative Example 1-2" A polyurethane lens with a cured film and an antireflection film was manufactured in the same manner as in Example 1 except that a coating liquid having the composition shown in Table 3 was used, and evaluated in the same manner as in Example 1. As shown in Table 4, the evaluation results show that Comparative Example 1, which does not use titanium-iso-propoxyoctylene glycolate (component (0)), has poor adhesion, and epoxy compound +!!JJ
Comparative Example 2 in which component (C) was not used also had poor adhesion.

(The following is a blank space) [Effects of the Invention] The high refractive index plastic lens of the present invention, which has a cured film and preferably further has an antireflection film on the cured film, has high scratch resistance and has good adhesion between the cured film and the substrate. has good properties,
Furthermore, it does not have the disadvantage of interference fringes caused by a cured film and has excellent impact resistance, and when used as an eyeglass lens, it is thin, light, and highly safe and comfortable to wear.

Claims (1)

[Claims] 1. The following (A), (B), (C) and (
A high refractive index plastic lens characterized by having a cured film obtained by applying and curing a coating composition containing component D). (A) General formula R^1Si(OR^2)_3 (Here, R^1 represents an organic group containing an epoxy group having 4 to 14 carbon atoms, and R^2 represents an alkyl group having 1 to 4 carbon atoms.) An organosilicon compound represented by or a hydrolyzate thereof. (B) Particle size 5-50 colloidally dispersed in organic solvent
nm antimony pentoxide sol. (C) One or more epoxy compounds represented by the following general formula. (1) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (Here, n is 2 or 3.) (2) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [Here, X is -CH_2OR^3 or -OR ^3 (R^3 represents H or ▲numerical formula, chemical formula, table, etc.▼), and R^4 represents H, -CH_3 or -CH_2-CH_3. ] (D) Titanium-iso-propoxyoctylene glycolate. 2. The high refractive index plastic lens according to claim 1, further comprising an antireflection film made of an inorganic substance on the cured film.