JPH02262101A - Plastic lens having high refractive index - Google Patents

Abstract

PURPOSE:To prevent yellowing and to obtain a high refractive index by forming a coating film contg. a specified organosylicic compd. and a specified oil-soluble dye. CONSTITUTION:The surface of the substrate of a plastic lens based on polyurethane obtd. by polymerizing polyisocyanate and polythiol is coated with a compsn. contg. an organosylicic compd. represented by formula R<1>(R<3>)aSi(OR<2>)3-a or a hydrolyzate thereof and at least one kind of dye selected among anthraquinone violet type oil-soluble dyes and anthraquinone blue type oil-soluble dyes and the compsn. is hardened to form a coating film. In the formula, R<1> is an epoxy-contg. 4-14C org. group, R<2> is 1-4C alkyl or 1-4C acyl, R<3> is 1-6C alkyl and a is 0, 1 or 2. Yellowing is prevented and a high refractive index is obtd.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a high refractive index plastic lens used for various optical lenses such as eyeglass lenses and camera lenses.

[Prior Art] In recent years, demand for plastic lenses, for example as lenses for eyeglasses, has been increasing both domestically and internationally.

Plastic lenses that have been used in recent years include diethylene glycol bisallyl carbonate (hereinafter referred to as DAC).
Generally used is a DAC resin that is cast-polymerized. DAC resin has the advantages of being lighter than glass, less likely to break, and has excellent dyeability, and can meet the rich fashion needs of today's large frames combined with colored lenses. However, the refractive index (hereinafter abbreviated as nd) of DAC resin is only 1.500, which is lower than the ndl of glass eyeglass lenses, which is 523, so if the lens power is particularly strong, the lens must be made thicker. Not well liked by users.

On the other hand, the nd is 1.56 to 1.6 compared to the DAC resin lens.
Polyurethane lenses are known as plastic lenses that have a relatively high refractive index of 4.

As this polyurethane lens, for example, JP-A-60-1
No. 99016 proposes a polyurethane lens made of a copolymer of polyisocyanate and polythiol. This polyurethane lens is widely used in optical lenses such as spectacle lenses.

[Problems to be Solved by the Invention] However, the polyurethane lenses proposed in JP-A-60-199016 etc. are generally yellowish compared to DAC resin, and are more yellowish than conventional DAC resin eyeglass lenses. There was a problem in that the coloring was significant.

Therefore, an object of the present invention is to eliminate the above-described drawbacks of the prior art and to provide a polyurethane lens having a colorless transparency comparable to that of a DAC resin lens.

[Problem to be Solved by the Invention] As a result of intensive research to achieve the above-mentioned object, the present inventor has discovered that the surface of a plastic lens substrate containing polyurethane as a main component obtained by polymerizing polyisocyanate and polythiol. , discovered that a high refractive index plastic lens having a coating film obtained by applying and curing a composition containing the following components (A) and (B) has a colorless transparency comparable to that of a DAC resin lens,
The present invention has been completed.

(A) General formula R'(R3) S L (OR2) 3
-a (where R1 contains an epoxy group and has 4 to 14 carbon atoms)
R2 is an alkyl group having 1 to 4 carbon atoms or an acyl group having 1 to 4 carbon atoms, R3 is an alkyl group having 1 to 6 carbon atoms, a is 0 or an integer of 1 to 2) Organosilicon compound or its hydrolyzate.

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

As mentioned above, the present invention relates to a high refractive index plastic lens having a coating film on the surface of a plastic lens substrate containing polyurethane, and the present invention relates to a high refractive index plastic lens having a coating film formed on the surface of the plastic lens substrate. The lens substrate is obtained by casting polymerization of polyisocyanate and polythiol in a mold consisting of, for example, a lens mold and a resin gasket.

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, inphorone diisocyanate, xylylene diisocyanate, hydrogenated xylylene diisocyanate, hydrogenated diphenylmethane diisocyanate, lysine diisocyanate, triphenylmethane triisocyanate, Tris(isocyanate phenyl)thiophosphate, trans-cyclohexane 1,4-diisocyanate, p-phenylene diisocyanate, tetramethylene diisocyanate, 1. 6. 11-Undecane triisocyanate, 1,8-diisocyanate-4
-Isocyanate methyl octane, lysine ester triisocyanate, 1. 3. Polyisocyanate compounds such as 6-hexamethylene triisocyanate and bicyclohebutane triisocyanate, and allophanate-modified products, billet-modified products, isocyanurate-modified products, and adduct-modified products of these compounds with polyols or polythiols, etc. , may be used alone or as a mixture of two or more types as required. Other known isocyanate compounds may be used, but the incyanate compound serving as the main component must be bifunctional or higher. C in known aromatic isocyanate compounds
A halogen atom such as 1 or Br may be introduced. Particularly preferred isocyanate-1 compounds include 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, heptanedithiol, octanedithiol, cyclohexanedithiol, cyclohebutanedithiol, 2,5-dichlorobenzene-1°3-dithiol, pentaerythritol Examples include tetrakis 3-mercaptopropionate, pentaerythritol tetrakis 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. Since the plastic lens is also large, a plastic lens having sufficient performance to be used as a spectacle lens can be obtained.

(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. 0.01-
20 parts by weight, particularly preferably 0.02-5 parts by weight. The reason for this is that if the amount of phosphate ester used is less than 0.01 parts by weight, it is difficult to release the lens from the lens mold after polymerization, and if it exceeds 20 parts by weight, the lens may become cloudy. This is because foaming or gelation occurs during preparation.

In the present invention, the coating film formed on the surface of the plastic lens substrate containing polyurethane as a main component is obtained by applying a composition containing the following components (A) and (B) to the surface of the plastic lens substrate and curing it. .

(A) General formula R1 (R3) S L (OR2)
3-a (here, R1 contains an epoxy group and has 4 to 1 carbon atoms)
4 organic group, R2 is an alkyl group having 1 to 4 carbon atoms or an acyl group having 1 to 4 carbon atoms, R3 is an alkyl group having 1 to 6 carbon atoms, and a is 0 or an integer of 1 to 2). organosilicon compounds or their hydrolysates.

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

General formula R' (
R3) The organosilicon compound represented by S i (OR2) 3-a or its hydrolyzate includes γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropyl Dimethoxyethoxysilane, γ-glycidoxypropyltriacetoxysilane, β-(3,4-epoxycyclohexyl)ethyltriethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropyldimethylmonomethoxysilane etc. and their hydrolysates, but are not limited to these.

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

The amount of the oil-soluble dye used is preferably in the range of 5 to 1100 ppm, particularly preferably in the range of 20 to 50 ppm, based on the total weight of the composition containing the organosilicon compound and the oil-soluble dye. The reason for this is that if the amount of oil-soluble dye is less than 5 ppm, the lens will not be sufficiently transparent and colorless;
This is because if it exceeds 100 ppm, the lens will turn blue, which is not preferable.

Oil-soluble dyes other than the oil-soluble dye of component (B) described above, such as red oil-soluble dyes, yellow oil-soluble dyes, blue oil-soluble dyes made of phthalocyanine compounds, monoazo blue oil-soluble dyes, and It is not preferable to use phenylmethane blue oil-soluble dyes. The reason for this is that even if an oil-soluble dye other than component (B) is added to the coating composition and a coating film is formed, the coating film becomes colored during the curing reaction of the coating composition, making the polyurethane lens colorless and transparent. This is because it cannot be achieved. Further, it is not preferable to add dyes other than oil-soluble dyes, such as disperse dyes, cationic dyes, and acid dyes. This is because the above-mentioned dyes have problems such as poor solubility, not being uniformly dispersed, and coloring of the coating film during the curing reaction of the coating composition.

The coating composition used in the present invention includes A1, Ti, and Ti in order to reduce the occurrence of interference fringes due to the coating film.
, Zr5Sn, fine particle inorganic substances made of metal oxides such as Sb, fine particle inorganic substances made of metal oxides such as Si to improve scratch resistance, or inorganic substances provided on the coating film as necessary. In order to improve the adhesion with the antireflection film, an epoxy compound such as polyglycerol polyglycidyl ether, glycerol polyglycidyl ether, diglycerol polyglycidyl ether, etc. can be added. Further, ultraviolet absorbers, antioxidants, curing agents, etc. can also be used. Furthermore, the coating composition used in the present invention improves flowability during application,
7 Various surfactants may be added for the purpose of improving the smoothness of the coating film. As a coating method, commonly used methods such as a dipping method, a spin method, and a spray method can be applied, but the dipping method 1. A spin method is preferred.

[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.

Further, various physical properties of the polyurethane lenses obtained in the present examples and comparative examples were measured by the measurement methods shown below.

(1) Total light transmittance The light transmittance in the entire visible light range was investigated.

(2) Yellowness (YI value) Measured according to JIS-7103.

(3) Impact resistance A 16g steel ball was dropped from a height of 127cm onto the center of a lens with a center thickness of 2IT1m to check for damage.

(4) Appearance: The lenses were visually inspected under fluorescent light to see if they were colored.

[Example 1 Co. 1. Preparation of high refractive index polyurethane lens 100 parts by weight of m-xylylene diisocyanate, 142 parts by weight of pentaerythritol tetrakis 3-mercaptopropionate, 6 parts by weight of di-n-butyl phosphate, and 0° dibutyltin dilaurate. 25 parts by weight and 2- (2'
-Hydroxy-5'-t-octylphenyl)benzotriazole (0.5 parts by weight) was mixed and thoroughly stirred, followed by deaeration for 60 minutes under a vacuum of 1 mm/1 g.

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 is removed, the lens mold and lens are separated, and the center thickness is 2.
A high refractive index polyurethane lens with a diameter of 0 mm and a power of 0°00D was obtained.

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

2. Preparation of coating solution 54 parts by weight of O', 06N hydrochloric acid aqueous solution was added dropwise to 212 parts by weight of γ-glycidoxypropyltrimethoxysilane with stirring. After the dropwise addition was completed, the mixture was stirred for 24 hours to obtain a hydrolyzate. Then Bunacol E was added as an epoxy compound.
68 parts by weight of X-521 (manufactured by Nagase Kasei Co., Ltd., polyglycerol polyglycidyl ether), 34 parts by weight of titanium-1so-proboxyoctylene glycolate as a curing agent, and Orient Oil as an anthraquinone violet oil-soluble dye. Violet #
730 (manufactured by Orient Chemical Industry, CI Solvent)
A coating liquid was obtained by adding 20 ppm (corresponding to Violet 13) and aging for an additional 100 hours while stirring.

3. Formation of cured film 1. The high refractive index polyurethane lens produced by the method described in 2. above was thoroughly washed by immersing it in a 10% NaOH aqueous solution at 50° C. for 5 minutes. Using the coating liquid prepared by the method described above, the dip method (pulling speed 12c)
m/min) and heated at 120° C. for 1 hour to form a coating film, thereby obtaining a polyurethane lens with a coating film of this example.

As shown in Table 2, the evaluation results of the coated polyurethane lens of this example are that the impact resistance is good, the total light transmittance is 90%, and the YI value indicating yellowness is 0.8, which is DAC
The YI value of the resin lens was 0°8, and when visually observed under a fluorescent light, it was colorless and transparent.

[Example 2] Polyurethane having a coating film was prepared in the same manner as in Example 1 except that 4 opm of Orient Oil Violet #732 (manufactured by Orient Chemical Industry ■, equivalent to CI Solvent Violet 14) was used as the anthraquinone violet oil-soluble dye. I got the lens. The obtained polyurethane lens with a coating film had excellent physical properties similar to those of Example 1, as shown in Table 1.

[Example 3] As an anthraquinone blue oil-soluble dye, Diareson Blue P (manufactured by Mitsubishi Kasei ■, CI Solvent Blue 3) was used as an anthraquinone blue oil-soluble dye.
A polyurethane lens having a coating film was obtained in the same manner as in Example 1 except that 30 ppm (equivalent to 6) was used. As shown in Table 1, the obtained polyurethane lens with a coating film had excellent physical properties similar to those of Example 1.

[Example 4 As a coanthraquinone blue oil-soluble dye, Sumiplast Blue G (manufactured by Sumitomo Chemical Hina, CI Solvent Blue 1
A polyurethane lens having a coating film was obtained in the same manner as in Example 1 except that 10 ppm (equivalent to 1) was used. As shown in Table 1, the obtained polyurethane lens with a coating film had excellent physical properties similar to those of Example 1.

[Comparative Example 1] In place of 20 ppm of anthraquinone violet oil-soluble dye (Orient Oil Violet #730, manufactured by Orient Chemical Industries, Ltd.) in Example 1, Eisen Spiron Violet RH (manufactured by Hodogaya Chemical Company, Ltd.) was used as a monoazo violet oil-soluble dye. )301) A polyurethane lens with a coating film was obtained in the same manner as in Example 1 except that pm was used, but the YI value of the obtained polyurethane lens with a coating film was 1.6, and the color tone was light. It was brown.

[Comparative Example 2] A polyurethane lens having a coating film was obtained in the same manner as in Example 1 except that 40 ppm of Victoria Blue F4R (manufactured by BASF ■) was used as the triarylmethane blue oil-soluble dye. The polyurethane lens with a coating film τj has a YI value of 1.7,
Its color tone was dark brown.

[Comparative Example 3] As a phthalocyanine blue oil-soluble dye, 20 ppI of Eisen Spiron Blue GNH (manufactured by Odugaya Kagaku ■)
A polyurethane lens with a coating film was obtained in the same manner as in Example 1 except that No. 11 was used, but the obtained polyurethane lens with a coating film had a YI value of 1.5.
The color tone was astringent brown.

(The following is a blank space) [Effects of the Invention] As explained above, the present invention has the advantage of having a higher refractive index than diethylene glycol bisallyl carbonate (DAC) resin lenses, but is superior to DAC lens resins. By providing a coating film containing a specific organosilicon compound and a specific oil-soluble dye to a polyurethane lens, which has the disadvantage of being easily colored yellow, the disadvantage of yellowing was overcome, and a colorless and transparent polyurethane lens was obtained. This, combined with the above-mentioned advantage of having a high refractive index, makes it possible to expand the applications of polyurethane lenses.

Claims (1)

[Claims] (1) A coating film obtained by applying and curing a composition containing the following components (A) and (B) to the surface of a plastic lens substrate whose main component is polyurethane obtained by polymerizing polyisocyanate and polythiol. A high refractive index plastic lens characterized by having: (A) General formula R^1(R^3)_aSi(OR^2)_
3_-_a (where R^1 is an organic group having 4 to 14 carbon atoms including an epoxy group, R^2 is an alkyl group having 1 to 4 carbon atoms or an acyl group having 1 to 4 carbon atoms, and R^3 is Carbon number 1-6
(a represents an integer of 0 or 1 to 2) or a hydrolyzate thereof. (B) At least one selected from anthraquinone violet oil-soluble dyes and anthraquinone blue oil-soluble dyes
Seed dye.