JPS60214301A - Plastic lens - Google Patents

Abstract

PURPOSE:To obtain a high refractive index plastic lens having excellent wear resistance, hot water resistance, stable dyeability, chemical resistance, weatherability and adhesion to a cured coating layer by coating a primer compsn. on a base material then forming a cured silicon film layer thereon after curing. CONSTITUTION:The primer compsn. can be dissolved in an org. solvent in order to coat uniformly 0.1-50pts.wt. the diepoxy compd. obtd. by mixing 0.01-1pt.wt. an epoxy curing catalyst with 100pts.wt. a mixture composed of 1 or >=2 kinds among multifunctional epoxy compds. on the surface of a plastic base material. The primer compsn. is coated on the surface of the high refractive index plastic base material and is then dried at an optional temp. in a 30-200 deg.C, more preferably 100-150 deg.C range. The desired primer layer is formed by 1-60min heating. The cured thermosetting silicone film is formed on the high refractive index plastic base material on which the primer layer is formed. The thickness of the cured film layer is adjusted to 2-10mu.

Description

DETAILED DESCRIPTION OF THE INVENTION [Technical Field] The present invention relates to transparent plastic surfaces, particularly those having a refractive index of about 1.6.
The present invention relates to a glass lens in which a hardened coating layer having a total thickness of 2 to 10 microns, excellent in abrasion resistance, and further dyeable is formed on the surface of a plastic lens base material, using a climber.

[Prior art]

Glass material has come to be used as a lens material instead of conventional inorganic glass. Glass lenses are lighter and have higher impact resistance than inorganic glass lenses.
It has features such as good processability, and is especially safe, comfortable to wear,
It is often used in eyeglass lenses that emphasize fashionability.

However, compared to inorganic glass, plastic lenses
The drawback is that it is much more easily damaged.

Therefore, in order to provide a plastic lens with durability that does not cause any practical problems, it is necessary to provide a hardened coating layer on the surface of the plastic lens to improve its scratch resistance.

Additionally, plastic lenses have the disadvantage that they need to be thicker than inorganic glass lenses in terms of strength. In order to make lenses thinner, it is necessary to increase the refractive index of the plastic lens material, as is currently widely used in inorganic glass lenses, especially eyeglass lenses.

Conventionally, diethylene glycol bisallyl carbonate (trade name, 0R-59) has been widely used as a glass lens, but while this plastic has relatively excellent scratch resistance and processing performance, it is not suitable for 0R-39 lenses. Its refractive index is 1.50, so when using a strong eyeglass lens, the lens becomes thicker than an inorganic glass lens, which may result in total loss.

To eliminate this drawback of the 0'R-39 lens, it is better to use a plastic lens with a high refractive index comparable to inorganic glass. However, with the refractive plastics that are currently being used, it is difficult to obtain anything that is practically scratch resistant. Products with coatings have not been put into practical use.

In other words, in reality, high refractive index glass lenses have poor affinity for silicone famous thermosetting compositions, so their initial layer density is very poor, and under conditions such as particularly severe water resistance tests, they do not bond well with the base material. If the closeness with the coating is poor, a score of 1 is good.

Therefore, it is necessary to form a cured film layer by primer treatment on a high refractive index plastic substrate to be coated.

Regarding this, a method is disclosed in Japanese Patent Publication No. 57-45168, but if the high refractive index plastic described in the present invention is used as the base material, the initial adhesion may be slightly improved.
Under tests for hot water resistance, chemical resistance, weather resistance, etc., cracks and cracks occur between the base material and the coating, and cracks occur, making it practically impossible. Therefore, it is currently impossible to apply a silicone-based hardened coating layer to a high refractive index plastic lens.

〔the purpose〕

The present invention performs 1 limer treatment to apply a silicone-based hardened coating layer to a high refractive index plastic lens, and the purpose is to provide excellent abrasion resistance, hot water resistance, and stable stainability. One object of the present invention is to provide a high refractive index plastic lens having chemical resistance, weather resistance, adhesion to a cured film layer, etc.

〔overview〕 The plastic lens of the present invention is as follows.

High refractive index transparent plastic lens surface has ■ molecular weight of 200 to 1,0 with 1 to 3 hydroxyl groups in the molecule.
00 epoxy compound; 100 parts by weight.

■ Epoxy curing catalyst: 0.001 to 1 part.

After applying and curing a primer composition containing gold as a main component, a primer composition containing an organosilicon compound as a main component and having a film thickness of 2 to 10
A plastic lens made of a silicone-based hardened coating that can be dyed with μ.

Similarly, the refractive index plastic lens mentioned here consists of 20 to 80 parts by weight of a first monomer represented by the general formula [1] and a second monomer represented by the general formula [u]. By using a copolymer consisting of 20 to 80 quintillion parts, approximately 1.6 (1
, 55-i, 65) can be obtained. Compounds (13 and (11)) are shown below.

(In the formula, RI represents hydrogen or a methyl group; A copolymerizable monopolymer such as diethylene glycol bisallyl carbonate can also be added. Further, the polymerization is carried out by a casting method, and peroxides such as peracid ethers and peracid esters can be used as the initiator.

By the way, examples of the epoxy compound (2) include diglycidyl ethers such as glycerin, sorbitol, trimethylolpropane, and trimethylolmelamine. In addition, as examples other than Alcohols such as digrino and saeru ether are examples.

Furthermore, in the case of the present invention, as the epoxy curing catalyst (2),
Compounds mainly composed of perchlorates, such as zinc perchlorate, ammonium perchlorate, oxazine perchlorate,
Potassium perchlorate, silver perchlorate, mercuric perchlorate, ferric perchlorate, tetraethylammonium perchlorate, tetra-n-butylammonium perchlorate, tetra-n-furobyluan perchlorate Examples include mohnium, silver perchlorate, sodium perchlorate, lead perchlorate, nickel perchlorate, barium perchlorate, hydroxylamine perchlorate solution, magnesium perchlorate, and lithium perchlorate.

The primer composition used in the present invention is a mixture of one or more polyfunctional epoxy compounds mentioned in (1) above.
0 parts by weight, ■ epoxy curing catalyst i0.01-1
Jepoxy compound obtained by mixing parts by weight 0.1 to 5
0 parts by weight can also be dissolved in an organic solvent in order to uniformly and evenly coat the surface of the plastic substrate. Here, the organic solvent is not limited in type; for example, lower alcohols exemplified by methanol, ethanol, inglobanol, etc.; exemplified by methyl cellosolve, ethyl cellosolve, methyl cellosolve, P-dioxane, tetrahydrofuran, etc. Ethers:
Aqueous organic solvents such as acetone are preferred. It is also useful to add a nonionic, silane-based, or fluorine-based surfactant here as a flow control agent. Additionally, UV absorbers are added to increase the weather resistance of the plastic lens base material.
It is also possible to add an anti-static agent to the coating to prevent the adhesion of dirt, dust, etc. before applying the silicone-based cured film layer in the subsequent process.

When applying the primer composition used in the present invention, a known application method such as a spray method, a tipping method, or a subinczy method may be selected as appropriate.

After applying the primer composition used in the present invention to the surface of the above-mentioned high refractive index plastic substrate,
It may be dried at any temperature within the range of 100 to 150°C. A desired primer layer is formed by heating for 1 to 60 minutes.

As a thermosetting silicone-based cured film layer for a high refractive index plastic substrate on which a single layer of the primer of the present invention is formed on the surface of the substrate in this way, a coating composition liquid (formula R2 is a hydrocarbon group having 1 to 6 carbon atoms, a vinyl group, a methacryloxy group, or an organic group having an epoxy group. R1 is a hydrocarbon group having 1 to 4 carbon atoms. R4 is a hydrocarbon group having 1 to 5 carbon atoms, alkoxylalkyl. one or more organosilicon compounds represented by a group or a hydrogen atom, t represents 0 or 1; Colloidal silica with a particle size of 1 to 100 millimicrons ■ Multifunctional epoxy compound ■ Magnesium perchlorate Component (2) of the cured film layer includes methyltrimethoxysilane, ethyltriethoxysilane, methyltriethoxysilane, phenyltrimethoxysilane, dimethyldimethoxysilane, phenylmethyldimethoxysilane, vinyltriethoxysilane, and vinyltris(β-methoxysilane). Ethoxyfusilane, vinyltriacetoxysilane,
r-crisidoxyfurovirtrimethoxysilane, r-crisidoxyfurovirmethyldiethoxysilane, β-('
3.4 epoxycyclohexylphethyltrimethoxysilane and the like. These may be used alone or in combination of two or more. In addition, these can be used in organic solvents such as alcohol.
It is preferable to use it by hydrolyzing it in the presence of an acid, and it may be used alone after being hydrolyzed and then mixed with the colloidal silica of component (2), or after being mixed with component (2) and then hydrolyzed.

This is a commercially available colloidal solution prepared by dispersing inorganic silicic acid fine particles made of a polymer in an alcohol-based dispersion medium containing colloidal silica having a particle size of 1 to 100 millimeters (component (2)).

The polyfunctional epoxy compounds of component
Examples include diglycidyl ethers of difunctional alcohols such as alkylene glycol, hexanediol, bisphenol A1, bisphenol A1 butanediol, and diglycidyl ethers of trifunctional alcohols such as trimethylolpropane and glycerin.

A coating film with excellent hot water resistance, stainability, chemical resistance, and weather resistance by using one or more of component (2), component (2) and magnesium perchlorate (component) as a curing catalyst for component (2) and (2). By adding the curing catalyst of component (2), which is optimal for the above-mentioned components (2), (2), and (2), it is possible to obtain a coating material with an extremely long pot life, which is unprecedented.

The mixing amount of each component to obtain these cured film layers is preferably 50 to 600 parts by weight of component (◎) or component (calculated as S10□), more preferably component (■). S50~500 parts by weight, component (■) is 100~
It is 500 parts by weight. Furthermore, it is desirable to use component (1) within the range of 0.01 to 50% of the total residual solids.

In addition, solvents such as alcohols, ketones, cellosolves, carboxylic acids, etc. can be added alone or in combination, and if necessary, additives such as those added to the primer composition of the present invention can be used in small amounts. For example, non-ionic, silane-based, and dung-based surfactants improve the coating properties of the coating solution, and UV absorbers improve the adhesion of the cured film layer by improving the weather resistance of the fryer layer and plastic substrate.
The antistatic agent can further improve the performance of the coating film by preventing dirt, dust, etc. from adhering to the lens.

As for the coating method, similar to the primer treatment of the present invention, methods such as spraying, dipping, and spinner methods are used, and sufficient thermal saponification is achieved by reacting at a relatively low temperature of 90 to 100°C for 1 to 2 hours. It is possible.

The thickness of the cured film layer obtained in this way is 2 to 10
Adjust to μ. If the film thickness is less than 2μ, interference fringes will occur and the aesthetic appearance may be completely ruined, and if it is more than 10μ,
It takes a long time to harden. This required film thickness can be achieved by selecting coating conditions such as the type of bath agent added to the coating solution, and the spray time in the case of a spray method.

〔Example〕

EXAMPLES Hereinafter, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited by these Examples. Note that parts and percentages in the examples are based on Nt.

Example 1゜(1) Production of high refractive index plastic lens Styrene 5
0 parts, 2,2-bis(3,5-dibrome, 4-methacryloyloxyethoxyphenylnopropane 48.5 parts,
2.8 parts of diethylene glycol bisallyl carbonate, 1.5 parts of t-butyl baroxyneotecanate, 2-
(0.2 part of 2'-hydroxy-6'-methylphenylbenzotriazole is mixed and stirred. Next, the unbathable substances of this mixture are removed with a filter, and molded with soft polyvinyl chloride. It was injected into the space created by a gasket and two glass molds.Next, it was heated at 60℃ for 4 hours for 30 minutes.
℃ to 50℃ linearly for 10 hours, 50℃ to 70℃
After heating linearly for 2 hours at 70°C for 2 hours at 80°C, the gasket and glass mold were separated.

Further, the obtained lens was subjected to annealing for 2 hours at 110° C. to remove distortion inside the lens. The lens thus obtained had a refractive index of 1,595 and an Atsbe number of 52.
It was a good product as a high refractive index plastic lens for optical use. This lens is used as a base material lens for a high refractive index plastic lens used below.

(2) Adjustment of primer coating liquid and application curing Glycerin diglycidyl ether (Denacol F manufactured by Nagase Sangyo Co., Ltd.)
To a mixed solution of 86 parts by weight of , A few drops of a flow control agent (Nippon Unicar Koji Co., Ltd. #Y-7002IT) was added to this to prepare the coating solution. The high refractive index plastic lens described in (1) above was completely immersed in this solution, pulled up at a rate of 10 crn/min, applied, and heated at 100° C. for 1 hour to dry.

(6) Preparation of cured film liquid and coating curing 249 parts by weight of r-crisitoxyprobyltrimethoxysilane, colloidal silica (I methanol silica sol manufactured by Nichikagaku Kogyo ■)
, 0.05 normal (N) was added to a solution consisting of 126 parts by weight (solid content 30%) and 464 parts by weight of methyl cellosolve.
Gradually drip hydrochloric acid 68 Kominbu to hydrolyze! I did st.

After aging at 0℃ for 24 hours, glycerin diglycidyl ether (Nagao Sangyo #l Denacol KX31
3#) 86 parts by weight and magnesium perchlorate 7-layer iWI'
at room temperature and stirred to make it homogeneous.

Add this to a flow control agent (#Y- made by Nippon Unicar).
A coating liquid was prepared by adding several drops of 70021).

A high refractive index plastic lens 41 on which the primer was dried on a cloth in step (2) above was immersed in this liquid, and was applied by pulling up at a speed of 20 crn per minute at 80°C for 1 hour and at 150°C for 1 hour.
It was heated and cured for a period of time.

(4) Performance evaluation test Adhesion: Using a so-called cross-cut chief cutter, 11 parallel cuts are made with a knife at 111 am intervals to create 100 1- squares. Next, the adhesive tape (product name: Cellochie 1) was sharply kicked and rapidly peeled off in a 90° direction, and the results were displayed using the remaining squares as the numerator and the total squares as the denominator.

Abrasion resistance: 1d #○○○○ steel wool (manufactured by Nippon Steel Wool ■) is applied with an i Kf load and rubbed 10 times. Evaluated in stages.

Hot water resistance: After the lenses were immersed in boiling pure water for 1 hour, the abrasion resistance test was conducted in the same manner as above.

Stainability 2 96°C; 2 t of Suwa Seiko Kin's Vistabrax Diamond Coat staining agent and 5 ml of the same dyeing aid were dissolved in 1 t of pure water to complete the dyeing process.

The lens was immersed in this solution for 10 minutes and dyed, and 510n
The transmittance of monochromatic light of m was measured.

Wear resistance was evaluated based on the appearance of the lens after being immersed in a 4% sodium hydroxide water bath for 1 hour and the appearance after being immersed in 10X hydrochloric acid for 24 hours.

Weather resistance: Evaluated by the appearance of the coating film after 500 hours of ultraviolet irradiation using a xenon lamp fade meter.

The results of each evaluation are shown in Table-1.

In practice 2- As a primer coating liquid, glycerin diglycidyl ether (manufactured by Nagashio Sangyo ■) Denacol EX31! #J92 Juyaribe and 1,6-hexinediol diglycidyl ether (
A total of 678 parts by weight of Improper Tool was added at room temperature to a mixed solution of 92 parts by weight of I Evolai N15OO# (manufactured by Kyoeisha Yushi ■) and 5 parts by weight of magnesium perchlorate, and the mixture was stirred to be homogeneous. Add to this a flow control agent (Nippon Unicar Co., Ltd. #
The coating solution was adjusted by adding a few drops of Y-70021). The base lens and the coating method are the same as in Example 1.

Next, as a hardening coating liquid, methyltrimethoxysilane 1
0.8 parts by weight, imbronokenol-dispersed colloidal silica (manufactured by Catalysts & Chemical Industry ■ 08OAL-1432#, solid content 60%) 212 quintillion parts by weight, and isopropanol 4
52 parts by weight of 0.05 N hydrochloric acid was gradually added dropwise to a solution consisting of 39 parts by weight to effect hydrolysis. This solution is 0
After aging at ℃ for 24 hours, 1,6-hexanethiol dicrycidyl ether (Evolai manufactured by Kyoeisha Yushi ■) IS
186 parts by weight of OO'7 and 5 parts by weight of magnesium perchlorate were added at room temperature, and the mixture was stirred to be homogeneous. In addition, a flow control agent (#Y-7002 manufactured by Nippon Unicar Co., Ltd.)
The coating solution was adjusted by adding a few drops of #J. Lenses that have been treated with the primer mentioned above in this liquid? The coating and evaluation were carried out in the same manner as in Example 1.

Examples & As a primer coating liquid, 148 parts by weight of glycerin Jig 1 nosidyl ether (manufactured by Kyoeisha Yushi ■), 148 parts by weight of Evolite 80MFi, 16 parts by weight of Bisfetor A Jig 1 nosidyl ether (manufactured by Kyoeisha Yushi ■, Evolite 3002#), and perchloric acid. A total of 368 parts by weight of isobrophenol was added to a mixed solution containing 5M parts of magnesium at room temperature, and the mixture was stirred to be homogeneous.

A coating liquid was prepared by adding a few drops of Flow Control Qi+1 (manufactured by Bhon Unicar@//Y-7002//) to the coating solution. The base lens and the coating method are the same as in Example 1.

Next, as a hardening coating liquid, methyltrimethoxysilane 1
11 heavy weight part, methanol-dispersed colloidal silica (Catalyst Chemical Industry ■#0EIAL-11527, solid content concentration 30X
271 parts by weight and 695 parts by weight of isopropanol were gradually added dropwise to 56 parts by weight of 0.05N hydrochloric acid to effect hydrolysis. After aging this chemical solution at 0°C for 24 hours, the diglycidyl ether of bisphenol A (
30029164 parts by weight of Evolai (manufactured by Kyoeisha Yushi ■) and 5 parts by weight of magnesium perchlorate were added at room temperature, and the mixture was stirred to be homogeneous. Add a few drops of a flow control agent (J'Y-7002 made by Nippon Unicar) to this and mix the chemical solution with V@
I arranged it. The lenses subjected to the flamer treatment were immersed in this liquid, and the same coating and evaluation as in Example 1 were performed.

Comparative Example 1 As a primer coating liquid, 2.2-bis(4
'-Glycidyloxyphenyl] 2% solution of Furonokun dissolved in ethyl cellosolve (fluorinated surfactant IF)
C-400# (containing 0.05%) was used. As the base lens, (1) of Example 1 was used, which was immersed in the mixed solution, applied at a rate of 10 cm per minute, and dried by heating at 110° C. for 5 minutes.

The primer formation field was applied to the lens as described in Example 1 (5).
It was prepared under the same conditions as above, immersed in T coating solution, pulled up and applied at a speed of 20 crn/min, heated at 80°C for 1 hour, and at 130°C for 1 hour.
It was heated and cured for a period of time. The evaluation was performed in the same manner as in Example 1.

Comparative Example 2 As a fryer coating liquid similar to Comparative Example 1, a 10% bath of 2,2-bis(4'-cricidyloxyphenylphpropane), which is a disclosed climber mixture, in ethyl cellosolve was used. g (Fluorine surfactant〃FO-43
0.05%) was used. The base lens and coating method were the same as those in Comparative Example 1, but the drying was performed at 100°C.
Heating was performed for 0 minutes. Furthermore, a cured film j similar to that of Comparative Example 1
- After applying, is the evaluation carried out? It was carried out in the same manner as I11.

〔effect〕

As described above, the primer of the present invention described above is applied to the surface of the plastic base material having a high refractive index, and then heated and dried.Then, a thermosetting silicone paint is applied and heated to cure, thereby achieving wear resistance, Hot water resistance, stable dyeability,
It has now become possible to obtain a refractive index plastic lens that has excellent effects such as chemical resistance, weather resistance, and adhesion to the cured film layer. Furthermore, as an application field, the primer and silicone-based hardened film layer of the present invention can be used for special plastics such as polyethylene terephthalate, polystyrene, polycarbonate, As resin, and ABS resin, which cannot be treated with conventional hardened film layers. can.

that's all Applicant: Suwa Seikosha Co., Ltd. Representative Patent Attorney Mogami

Claims (1)

[Claims] (11^ refractive index transparent plastic lens surface, ■ molecular value 200 to 3 hydroxyl groups in the molecule
1.000 epoxy compound; 100 parts by weight. ■ Epoxy curing catalyst; 0.001 to 1 part by weight. After applying and curing a fryer composition containing as a product, a film containing an organosilicon compound as a main component and having a film thickness of 2 to 10 μm is formed.
A plastic lens made entirely of a dyeable silicone-based cured coating. (2) The plastic lens according to claim 1, wherein the epoxy compound is a glycidyl ester or a glycidyl ether. (6) Claim 2, wherein at least 50 parts by weight of the glycidyl compounds are diglycidyl compounds.
Plastic lenses as described in section. (4) The plastic lens 1 according to claim 1, wherein the epoxy curing catalyst is a perchlorate.(5) The plastic lens contains 20 to 80% by weight of the first monomer represented by the general formula (1). and 20 to 80 parts by weight of a second monomer represented by the general formula C11), as described in the scope 1 of Patent #f4'P. (In the formula, RI represents hydrogen or a methyl group, Xl represents a halogen excluding fluorine, and m and n represent an integer from D to 8). (6) The silicone-based cured coating layer is prepared by using a coating composition liquid consisting of the following (1), (2), (2) and (5).
Claim 1, wherein R2 is a carbon number of 1 to
O is an organic group having a hydrocarbon group, a vinyl group, a methacryloxy group, or an epoxy group; R8 is a hydrocarbon group having 1 to 4 carbon atoms; R4 is a hydrocarbon group having 1 to 5 carbon atoms, an alkoxylalkyl group, or a hydrogen atom; t is One or two organosilicon compounds represented by 0 (representing l'i'1)
More than a species. ■ Colloidal silica with a particle size of 1 to 100 millimicrons ■ Multifunctional epoxy compound ■ Magnesium perchlorate