JP2003315501A - Plastic lens - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a plastic lens having improved adhesiveness with a coating film and maintaining the effect without increasing the production cost. <P>SOLUTION: The plastic lens contains silica fine particles in a thiourethane resin lens obtained by cast polymerization of a polyisocyanate compound and a polythiol compound. <P>COPYRIGHT: (C)2004,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a plastic lens having excellent transparency and adhesion.

[0002]

2. Description of the Related Art In order to improve the adhesion between a plastic lens and a coating film applied to the surface of the plastic lens, improvement measures have been taken such as providing a primer layer between them. In addition, a method of modifying the surface of the plastic lens by using various treatments has also been studied, for example, plasma treatment,
Surface modification treatments such as caustic treatment, acid treatment, ozone treatment, ultraviolet treatment, electron beam treatment, surfactant treatment and polishing treatment can be mentioned. However, the method of applying a primer increases the number of steps for applying and curing the primer, which leads to an increase in manufacturing cost. In addition, surface modification methods such as caustic treatment may be costly due to the introduction of equipment,
In addition, there are aspects where it is very difficult to establish technology, such as the sustainability of its effects.

[0003]

SUMMARY OF THE INVENTION Therefore, an object of the present invention is to provide a plastic lens having a long-lasting effect and a significantly improved adhesion of a coating film without increasing the manufacturing cost.

[0004]

Means for Solving the Problems The present invention can achieve the above object by containing fine silica particles when a thiourethane resin lens is produced by cast polymerization of a polyisocyanate compound and a polythiol compound. It was completed after obtaining the knowledge of. That is, the plastic lens of the present invention is characterized by containing silica fine particles in a thiourethane resin lens obtained by cast polymerization of a polyisocyanate compound and a polythiol compound.

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, silica fine particles can be mixed with one or both of a polyisocyanate compound and a polythiol compound, which are monomer components, and then cast polymerized. At this time, the mixing ratio of the silica fine particles to the total weight of the plastic lens is 1 × 1.
It is preferably 0 ^{−4 to} 0.1% by weight. When the mixing ratio of silica fine particles is less than 1 × 10 ⁻⁴ wt%,
The effect of improving the adhesiveness cannot be obtained, and when it is more than 0.1% by weight, the silica fine particles agglomerate inside the plastic lens and it becomes difficult to uniformly disperse them, and unevenness easily occurs.

The particle size of the silica fine particles is 5 to 10
It is preferably 0 nm. If the particle size is out of this range, for example, less than 5 nm, the effect of improving adhesion may not be sufficiently obtained, and if it exceeds 100 nm,
The transparency of the lens deteriorates.

The surface of the silica fine particles may be modified, but the modification method must be one that does not impair the adhesion between the plastic lens and the coating film on the surface thereof. Further, the form of the silica fine particles used in the present invention may be a single fine powder, or may be a state of being dispersed in a solvent such as water or an organic solvent, for example, a liquid such as a sol or an emulsion. In the case of these liquids, the silica fine particles may be surface-treated in order to enhance the affinity with the monomer components such as the polyisocyanate compound and the polythiol compound. The method of surface treatment is not particularly limited, and various methods can be applied, and examples thereof include coating with a transition metal and irradiation with radiation such as ultraviolet rays and electron beams.

The polyisocyanate compound used in the present invention is not particularly limited, and aliphatic, alicyclic or aromatic polyisocyanate can be used. For example, tolylene diisocyanate, 4,
4'-diphenylmethane diisocyanate, hexamethylene diisocyanate, octamethylene diisocyanate, naphthalene diisocyanate, isophorone diisocyanate, m-xylylene diisocyanate, p-xylylene diisocyanate, methylcyclohexane diisocyanate, 1,3-bis (isocyanatomethyl) cyclohexane, 1, 3,6-hexamethylene triisocyanate, tetrachloro-m-xylylene diisocyanate, tetrachloro-p-xylylene diisocyanate and the like can be mentioned. Further, as the polythiol compound,
Di (2-mercaptoethyl) ether, 1,2-ethanedithiol, 1,4-butanedithiol, ethylene glycol dithioglycolate, trimethylolethane trimercaptopropionate, trimethylolethane dimercaptopropionate, trimethylolpropane Dimercaptoacetate, trimethylolpropane trimercaptoacetate, trimethylolpropane dimercaptopropionate, trimethylolpropane trimercaptopropionate, trimethylolpropane dimercaptobutyrate, trimethylolpropane trimercaptobutyrate, pentaerythritol tetra (3 -Mercaptopropionate), 4-mercaptomethyl-3,
6-dithia-1,8-octanedithiol and the like can be mentioned.

The polyisocyanate compound and the polythiol compound are preferably mixed so that the molar ratio of -NCO / -SH (functional group) is 0.5 to 1.5, preferably 1.0. Outside this range, the desired performance cannot be obtained in terms of workability and refractive index.

A polymerization initiator is added to polymerize the polyisocyanate compound and the polythiol compound. As the polymerization initiator, organic peroxides, organic tin compounds, amine compounds and the like are used. In addition to the above components, the monomer mixture may also contain various additives, if necessary.
For example, an ultraviolet absorber, an antioxidant, an internal release agent, etc. can be added within a range that does not impair the object of the present invention. When manufacturing the plastic lens of the present invention,
The above-mentioned monomer components, silica fine particles, and other various components may be mixed, cast, and heat-polymerized.

A hard coat layer is provided on the plastic lens for the purpose of increasing the surface hardness. This hard coat layer is obtained by applying a coating liquid containing various components to a lens and curing the coating liquid. The lens of the present invention made of the silica fine particle-containing thiourethane resin produced as described above exhibits excellent adhesion to various hard coat layers.

As the coating liquid, a liquid mainly containing a colloidal dispersion of metal oxide fine particles and an organic silicon compound is generally used. The colloidal dispersion of metal oxide fine particles contained in the coating liquid is a fine particle of one or more metal oxides selected from silicon, tin, tungsten, iron, zirconium, titanium, etc. having a particle diameter of 1 to 300 nm. Alternatively, it is dispersed in an organic solvent in a colloidal form. The organosilicon compound contained in the coating liquid is preferably a hydrolyzable compound, and examples thereof include methyltrimethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, methyltriethoxysilane, phenyltriethoxysilane, and dimethyldimethoxy. Silanes, alkoxysilanes such as phenylmethyldimethoxysilane, vinyltriethoxysilane, vinyltrimethoxysilane, vinyltris (β-methoxyethoxy) silane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane. ,
γ-glycidoxypropylmethyldimethoxysilane, γ
-Glycidoxypropylmethyldiethoxysilane, β-
(3,4-Epoxycyclohexyl) ethyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-β (aminoethyl) γ-aminopropylmethyldimethoxy Examples thereof include silane coupling agents such as silane, γ-aminopropyltriethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, and γ-mercaptopropyltrimethoxysilane. These may be used alone or in combination of two or more. Further, it is preferable to hydrolyze these organosilicon compounds with an acid before use.

A curing catalyst may be added to the hydrolyzate of the organosilicon compound contained in the coating liquid for the purpose of promoting the curing thereof. Examples of the curing catalyst include amines, metal chelates, organic acid metal salts, perchloric acids, metal chlorides and the like. Specifically, amines such as guanidine, triethylamine and aniline, chromium (III), cobalt (III) and iron (II) coordinated with acetylacetone.
Metal acetylacetonates such as I), zirconium (IV), indium (III), sodium acetate, zinc naphthenate, cobalt naphthenate, zinc octylate, organic acid metal salts such as tin octylate, perchloric acid, perchlorine Ammonium chloride, perchloric acid such as magnesium perchlorate, tin chloride,
Examples thereof include metal chlorides such as aluminum chloride, iron chloride, titanium chloride and zinc chloride. The addition amount of the curing catalyst is preferably 0.1 to 10.0% by weight with respect to the organosilicon compound, considering the solubility in the solvent and the effect as the curing catalyst, and is 0.5 to 3%. More preferably, it is in the range of 0.0% by weight.

The coating liquid may further contain a leveling agent, an ultraviolet absorber, an antioxidant, a dye, a pigment, a filler, a stabilizer, a surfactant, an antistatic agent, a nonflammable agent, etc., depending on the use conditions. Addition can improve the coating properties of the coating liquid, the properties of the coating, the workability of the coating processing, and the like. As a component contained in the coating liquid, various solvents such as alcohol, ketone and cellosolve can be used alone or in combination for the purpose of obtaining stability of the coating liquid itself and further obtaining uniformity of the coating film. The coating liquid is applied and cured by a uniform method such as a flow method, a spray method, a spin method, a dip method, and the like.
It can be performed by heating and drying at a temperature of 70 to 150 ° C. for 1 to 4 hours. The thickness of the hard coat layer is 1
It is preferably 10 μm. When the film thickness of the hard coat layer is less than 1 μm, the scratch resistance is insufficient and 10
If it exceeds μm, heat resistance tends to be a problem.

On the hard coat layer formed by the above method
Anti-reflection film is formed by forming a single layer or multiple layers of inorganic compounds
be able to. This film forming method is, for example, vacuum vapor deposition.
Deposition method, sputtering method, ion plating method, etc.
To be Further, as specific examples of the inorganic compound used,
SiO, ZnO, TiO₂, CeO₂, Sb₂O₃, Sn
O₂, ZrO₂, Al₂O₃, MgF₂, SiO₂, Li
F, 3NaF / AlF₃ , AlF₃, Na₃AlF₃,
Ta₂O_FiveAnd so on.

[0016]

The present invention will be described in more detail based on the following examples, but the invention is not intended to be limited thereto.

Example 1 (1) Production of thiourethane resin lens Silica fine particles (primary particle diameter 12 nm) 6 × were placed in a reaction vessel.
10 ^-4 g, m-xylylene diisocyanate 62.4 g
Was added to uniformly disperse the silica fine particles in m-xylylene diisocyanate. Then, in the same container, 57.6 g of 4-mercaptomethyl-3,6-dithia-1,8-octanedithiol, dibutyltin dilaurate 0.02
g, internal release agent (manufactured by DuPont, trade name "Zelec U"
N ") 0.12 g and 2- (2'-hydroxy-5'-methylphenyl) benzotriazole 0.06 g were sequentially added and mixed, and after stirring, deaeration was performed under vacuum for 1 hour. Then, the mixture was poured into a mold composed of a glass mold and a gasket and kept at 55 ° C for 7 hours, and then from 55 ° C to 10
The temperature was raised to 5 ° C over 5 hours and then from 105 ° C to 12
The temperature is raised to 0 ° C. in 0.5 hours. Subsequently, polymerization was carried out at 120 ° C. for 2 hours, followed by cooling to remove the glass mold and the gasket to obtain a thiourethane resin lens containing silica fine particles. (2) Adjustment of coating liquid In a flask equipped with a stirrer, 105 g of γ-glycidoxypropyltrimethoxysilane was added, 36 g of 0.01N hydrochloric acid was added, hydrolysis was performed, and the resulting hydrolyzate was stirred overnight. Prepared. Methanol-dispersed zirconium oxide-titanium dioxide-silicon dioxide composite fine particle sol (manufactured by Catalysts & Chemicals Co., Ltd., trade name "Optlake 113
0Z ", solid content concentration 30% by weight) 450 g, aluminum acetylacetonate 1.5 g as a curing catalyst, methanol 70 g and a silicone-based surfactant 0.02 g are sequentially added, and after stirring for 20 hours, the stirring is stopped, and 20 ± Four
The coating liquid was obtained by allowing the mixture to stand for 20 hours at a temperature of ℃ for aging and filtering. (3) Preparation of Hard Coat Layer The thiourethane resin lens prepared by the method of (1) above was washed and then applied by the dipping method using the coating liquid prepared in (2) above. The pulling speed at this time is 2
It was 00 mm / min. After coating, pre-cure by heating at 95 ° C. for 15 minutes and main curing by heating at 115 ° C. for 3 hours to form a hard coat layer on the lens. (4) Fabrication of antireflection film SiO ₂ and Ti are formed on the hard coat layer obtained in the above (3) from the lens side toward the atmosphere side by vacuum vapor deposition.
A thin film of 5 layers of O ₂ , SiO ₂ , TiO ₂ , and SiO ₂ is SiO ₂ —TiO ₂ —SiO ₂ and has a thickness of λ / 4, TiO ₂
At λ / 2 and SiO ₂ at λ / 4 (where λ = 530n
It was formed with the optical film thickness of m), and the antireflection film was produced.

(5) Test and Performance Evaluation The lens obtained by the above operation was tested by the following method, and the results are shown in Table 1. Adhesion After immersing in hot water of 90 ° C for 1 hour, put 11 parallel lines vertically and horizontally with a cutter knife on the lens at 1 mm intervals.
00 squares were made, cellophane adhesive tape (manufactured by Nichiban Co., Ltd.) was adhered and adhered, rapidly peeled off, and the number of squares left without peeling was counted. The state of the coating film after 10 reciprocations under a load of 500 g was observed with the naked eye using steel wool with scratch resistance # 0000, and the judgment was made according to the following criteria. A: Not scratched B: Less than 50% of the scratched surface is scratched C: 50% or more of the scratched surface is scratched using a weather resistant xenon weather meter (manufactured by Suga Test Instruments Co., Ltd.)
After exposure for 300 hours, the state of the coating film was observed with the naked eye and judged according to the following criteria. A: No change in the coating film B: The coating film is rough C: The coating film is dissolved Put the lens in an oven with heat resistance of 80 ° C., take out after 10 minutes, and illuminate it with a slide projector. Judgment was made on the basis of. Good: No abnormality in the coating film Poor: The coating film has cracks

Example 2 In the production of a thiourethane resin lens, silica fine particles were mixed with 4-mercaptomethyl-3,6-dithia-1,8-.
The procedure was carried out under the same conditions as in Example 1 without changing the mixing amount, the treatment method, etc., except that the process was carried out by dispersing in octanedithiol and mixing the other components with the solution. Table 1 shows the evaluation results.
Shown in.

Example 3 In the production of a thiourethane resin lens, silica fine particles are dispersed in a mixture of m-xylylene diisocyanate and 4-mercaptomethyl-3,6-dithia-1,8-octanedithiol. Except for the mixed amount,
The same conditions as in Example 1 were applied without changing the treatment method. The evaluation results are shown in Table 1.

Example 4 The procedure was carried out under the same conditions as in Example 1 except that the mixing amount of silica fine particles was 1.2 × 10 ⁻³ g and the operating procedure, treatment method, etc. were not changed. The evaluation results are shown in Table 1. Example 5 The same conditions as in Example 1 were carried out without changing the mixing amount, the operating procedure, the treatment method, etc., except that silica fine particles having a primary particle diameter of 7 nm were used. The evaluation results are shown in Table 1.

Comparative Example 1 The same conditions as in Example 1 were carried out without changing the mixing amount, the operating procedure, the treatment method, etc., except that the silica fine particles were not mixed. The evaluation results are shown in Table 1. Comparative Example 2 The thiourethane resin lens containing no silica fine particles obtained in Comparative Example 1 was immersed in a 10% by weight aqueous solution of caustic soda for 5 minutes, washed and dried, and then coating was performed except for coating. The procedure was carried out under the same conditions as in Example 1 without changing the procedure and treatment method. The evaluation results are shown in Table 1.

[0023]

[Table 1]

[0024]

According to the present invention, it is possible to provide a plastic lens in which the effect is sustained and the adhesion of the coating film is remarkably improved without increasing the manufacturing cost.

   ─────────────────────────────────────────────────── ─── Continued front page    F term (reference) 2K009 AA15 BB11 CC09 CC21 DD02                 4J002 CK021 CK051 DJ016 FD016                       GP01                 4J034 BA02 CA32 CB03 CB07 CC01                       CD06 CD08 HA01 HC03 HC12                       HC22 HC64 JA01 MA04 QD03                       RA13

Claims (6)

[Claims] 1. A plastic lens characterized by containing fine silica particles in a thiourethane resin lens obtained by cast polymerization of a polyisocyanate compound and a polythiol compound. 2. The mixing ratio of silica fine particles is 1 × 10 ⁻⁴ .
The plastic lens according to claim 1, which is 0.1% by weight. 3. The silica fine particles have a particle size of 5 to 100 nm.
The plastic lens according to claim 1, wherein 4. The plastic lens according to claim 1, wherein the silica fine particles are powder. 5. The plastic lens according to claim 1, wherein the polyisocyanate compound is m-xylylene diisocyanate. 6. The plastic lens according to claim 1, wherein the polythiol compound is 4-mercaptomethyl-3,6-dithia-1,8-octanedithiol.