JPS6046502A - Plastic lens - Google Patents

Abstract

PURPOSE:To improve the resistance to wear, hot water and chemicals and dyeability by forming a hard coating film constituted by using specific raw materials on the surface of a plasitc lens. CONSTITUTION:A hard coating film consisting of 1 or >=2 kinds among the org. silicon compd. expressed by the formula (R<1> is 1-4C org. groups such as hydrocarbon group, vinyl group, methacryloxy group, epoxy group, etc., R<2> is 1- 4C hydrocarbon group, R<3> is 1-5C hydrocarbon group, alkoxyalkyl group or H atom, l is 0-1) as a compnent A, colloidal silica having 1-100mmu grain size as a component B, polyhydric alcohol or polybasic carboxylic acid or polybasic carboxylic anhydride as a component C and MgClO4 as a component D is formed on the surface of a plastic lens. The pot life as a coating is extended by adding MgClO4 which is the component D as a curing catalyst to the components A, B, C in the above-mentioned way. A coated fiml is formed by using such coating, by which the lens having good resistance to wear, hot water, chemicals and weather and dyeability is obtd.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides a lens made of synthetic resin that has a surface coated with 8-decoding M that has excellent abrasion resistance, hot water resistance, stainability, chemical resistance, and weather resistance. Regarding lenses.

Synthetic resin lenses are lighter than functional glass lenses.
Excellent impact resistance. It has various advantages such as good workability. However, on the other hand, it has a major drawback of being easily stained by marks, and furthermore, it has the drawback of being easily attacked by organic solvents.

As a method for improving these drawbacks, methods of coating the lens with various curable resins have been proposed, but at present none of them is fully satisfactory.

For example, hydrolysates of 3m-functional silanes such as methyltrialkoxysilane, tetramethylsilicates,
Examples of combinations of hydrolysates of tetrafunctional silanes such as tetraethyl silicate are known, but none have good properties in all aspects such as abrasion resistance, hot water resistance, and pot life.

Also, JP-A-51-42752. Endurance w352-1381
8, No. 53-15745 discloses the use of Lewis acids or their complexes, Brønsted acids, or metal salts of organic acids as curing catalysts for epoxy group-containing alkoxysilanes; It is not practical because it has a short life and takes a long time to harden.

On the other hand, Japanese Patent Publication No. 57-2755 discloses a mixture of one or more compounds selected from compounds containing both or one of a synthetic oxy group and a silanol and/or siloxane group, silica fine particles of 1 to 100 millimicrons, and aluminum. Coating compositions containing chelate compounds have been shown, but these cured coatings suffer from a decrease in hardness when immersed in hot water, and have the disadvantage of short lifespan of the coating solution in terms of uniform dyeability. have.

Furthermore, in synthetic resin lenses, especially eyeglass lenses, it is desirable that the coating film is easily dyed, and the pot life of the liquid with respect to stainability as well as abrasion resistance are important. JP-A-56-99265 discloses a hydrolyzate of an epoxy group-containing alkoxysilane, a vinyl A/group,
Hydrolyzate of alkoxysilane having methacryloxy group, amine 7 group, mercapto group or chlorine, particles M1-10
A coating composition containing colloidal silica of 0 millimicrons, one or more selected from organic titanium compounds, and ammonium perchlorate is disclosed, and JP-A-57-67665 discloses (A, ) Vinyl group, methacryloxy group, amide 7 group.

One type selected from organosilicon compounds having a mercapto group or chlorine, hydrolysates thereof, epoxy compounds 6, and polymers or copolymers obtained by polymerizing or copolymerizing monomers with vinyl/vinyl having at least one epoxy in the molecule. Or a coating composition containing two or more types of CB) colloidal silica with a particle size of 1 to 100 millimicrons, and Co) ammonium perchlorate.

However, these methods do not have excellent abrasion resistance and dyeability, and the dyeability itself changes from moment to moment depending on the pot life, so the inventors have found that they are of low practical use. As a result of repeated research in order to obtain a synthetic resin lens with excellent abrasion resistance, hot water resistance, stable stainability, #J chemical resistance, and weather resistance, the present invention was achieved.

That is, the present invention provides 1 or less (A) on the surface of a synthetic resin lens.
I (B), (0) and CD) (in the formula, R1 has 1 to 1 carbon atoms)
6 hydrocarbon group.

an organic group having a vinyl group, a methacryloxy group, or an epoxy group; B2 is a hydrocarbon group having 1 to 4 carbon atoms; R3 is a hydrocarbon group having 1 to 5 carbon atoms; an alkoxylalkyl group; or a hydrogen atom; t is 0 or 1. CB) Colloidal silica with a particle size of 1 to 100 millimicrons CO) Polyhydric alcohol or polycarboxylic acid or polycarboxylic acid anhydride (D) Perchlorine This is a synthetic resin lens with a hard coat film made from magnesium oxide as the main raw material.

Component (A) used in the present invention includes methyltrimethoxysilane, ethyltriethoxysilane, methyltriethoxysilane, phenyltrimethoxysilane, dimethyldimethoxysilane9. Phenylmethyldimethoxysilane, vinyltriethoxysilane, vinyl-tris(β-
methoxyethoxy)silane, vinyltriacetoxysilane yr-methacryloxypropyltrimethoxysilane.

r-glycidoxypropyltrimethoxysilane.

r-glycidoxypropylmethoxysilane e
/ (s * 4 epoxycyclohexyl) ethyltrimethoxysilane, etc. These may be used alone or in combination of two or more. Also, these can be hydrolyzed in the presence of an acid in an organic solvent such as alcohol. It is preferable to use it alone, either by hydrolyzing it alone and then mixing it with the colloidal silica of component CB), or by mixing it with component (B) and then hydrolyzing it.

Component CB) colloidal silica with a particle size of 1 to 100 millimeters is a colloidal solution in which high molecular weight inorganic silicic acid fine particles are dispersed in a water or alcohol-based dispersion medium.
Commercially available polyhydric alcohols as component (0) include (borine ethylene glycol, (poly)propylene glycol, neopentyl glycol, and catechol.

Examples include difunctional alcohols such as resorcinol and alkanediol, trifunctional alcohols such as glycerin and trimethylolpropane, and polyvinyl alcohol. Examples of polyhydric carboxylic acids include malonic acid, succinic acid, adipic acid, azelaic acid, maleic acid, 0-7 thalic acid, terephthalic acid, fumaric acid, itaconic acid, and oxaloacetic acid. Examples of the polycarboxylic anhydride include succinic anhydride, maleic anhydride, itaconic anhydride e 1 *2-dimethylmaleic anhydride,
Examples include 7-talic anhydride, hexahydro-7-I/acid anhydride, 7-tallic anhydride, and the like.

By using magnesium perchlorate (component CD) as a curing catalyst for one or more of component (A), component (B), and component (0), excellent hot water resistance, dyeability, and chemical resistance are achieved. It is possible to provide a coating M having good properties and weather resistance, and to have a coating material with an extremely long pot life.

Next, component CD) ammonium perchlorate will be explained.

Generally, the following types of curing catalysts are known, but each of them has the following drawbacks. In other words, amines such as looptylamine, triethylamine, guanidine, biguanide, amino acids such as glycine, etc., provide insufficient hardness of the coating film, and aluminum acetylacetonate, chromium acetylacetonate, titanyl acetylacetonate, cobalt etc. Metallic acetylacetonate such as acetylacetonate also has hardness <<, or even if it has a certain degree of hardness, it has poor water resistance, so it can be hardened by immersion in hot water. In addition, pot life is short in terms of uniform dyeability (same color and same density). In addition, sodium acetate, zinc heptathenate, cobalt naphthenate, dish lead octylate,
Metal salts of ta-acids such as tin octylate, perchloric acid, etc. have a short pot life, and ammonium perchlorate has variable dyeability, which changes depending on the life of the paint, so it is not practical. Not. Furthermore, hydrochloric acid, phosphoric acid,
Nitric acid, para-toluenesulfonic acid, etc. take a long time to make into one stool, and 8 n OZ4 e A Z OZ s *
Fe OLB , T i 014 , ZnO2,, S
With Lewis acids such as bOt6, the resulting coating film has extremely poor water resistance, and the hardness decreases when immersed in water at room temperature. Based on the above results, the present inventors have repeatedly investigated various curing catalysts, and have found that the potential We discovered that magnesium perchlorate, a type of chemical catalyst, has all the same properties. In other words, the practical bottear of the paint is more than one month when stored at room temperature, and the abrasion resistance of the resulting paint film is
It also has hot water resistance, chemical resistance, dyeability, and weather resistance.

The mixing amount of each component used in the present invention is preferably component (B) (solid content calculated as 810) 10
0 parts by weight, component (0) is 70 to 500 parts by weight, more preferably component (A) is 50 to 500 parts by weight, and component (A) is 70 to 500 parts by weight, based on the solid content calculated as component (A). is 70 to 300%.Furthermore, component CD) is preferably used within the range of 0.01 to 5.0% of the total residual solid content.

In addition, solvents such as alcohols, ketones, cellosolves, and carboxylic acids can be added alone or in combination.If necessary, small amounts of surfactants, antistatic agents, and ultraviolet absorbers can be added to coat the coating. It is also possible to improve the coating properties of the liquid and the performance of the coating film.

The present invention can be applied to various synthetic resins, and those with poor adhesion can be treated with a primer to obtain a high degree of adhesion.The present invention will be described in detail below based on Examples. The present invention is not limited to these.Example 1 (1) Preparation and application of paint 305 parts by weight of γ-glycidoxyprobyltrimethoxysilane, isopropanol-dispersed colloidal silica (Catalysts & Chemicals Co., Ltd. ) manufactured by '080AL-1432'', solid content concentration 30%) 155 parts by weight and isopropanol 406
While stirring the solution consisting of parts by weight, 84 parts by weight of 0.05N hydrochloric acid was gradually added dropwise to carry out hydrolysis. After the dropwise addition, the mixture was further stirred at room temperature for 2 hours, and then heated to 0°C.
It was aged for 24 hours. After aging, 47 parts by weight of 1,4-butanediol and 3 parts by weight of magnesium perchlorate were added at room temperature and stirred to make the mixture uniform. In addition, a flow control agent ("'I, -7001" manufactured by Nippon Unicar Co., Ltd.)
The paint was prepared by adding 0.6 parts by weight of A diethylene glycol bisallyl carbonate resin lens whose surface had been previously treated with a 4% sodium hydroxide aqueous solution, washed and dried was immersed in this solution, and the coating was applied by pulling it up at a rate of 20 crn per minute at 80°C for 1 hour and at 130°C for 1 hour. It was heated and cured for a period of time.

(2) Performance evaluation test abrasion resistance: 1cfl of #0000 steel wool (manufactured by Japan Steel Wool Co., Ltd.) was subjected to an Icy load,
The degree of adhesion when rubbed 10 times was evaluated on a scale of 10 to 10, with glass as A1 and acrylic resin as E'.

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 described above.

Stainability: BP1 G made in pure water at 95°C for 950 tons.
A staining solution was prepared by dissolving one bottle of RAY staining agent. I soaked the lens in this guy for 10 minutes and stained it with 510rLtrL.
The transmittance of monochromatic light was measured.

Chemical resistance was evaluated based on the appearance of the lens after being immersed in an 84% aqueous sodium hydroxide solution for 1 hour and the appearance after being immersed in 10% hydrochloric acid for 24 hours.

Weather resistance: Table 1 shows the evaluation results of the appearance of the coating film after 500 hours of ultraviolet irradiation using a xenon lamp fade meter.

Example-2 242 parts by weight of r-glycidoxyprobyltrimethoxysilane, methanol-dispersed colloidal silica (6 methanol silica sol manufactured by Nichijo Kagaku Kogyo Co., Ltd.), solid content concentration 60%
) and 408 parts by weight of isopropanol were gradually added dropwise to 66 parts by weight of 0.05N hydrochloric acid to effect hydrolysis. After the dropwise addition, the mixture was further stirred at room temperature for 2 hours, and then aged at 0°C for 24 hours. After aging, 4 parts of triethylene glycol fluoride and 3 parts by weight of magnesium perchlorate were added to the mixture at room temperature and stirred to make it homogeneous.

In addition, flow control agent L-7001 was added to a
, 5 parts by weight were added to prepare a paint. The lens treatment and coating methods are the same as in Example-1. Example-3 r-glycidoxypropylmethyl, jetoxysilane 2
20 parts by weight, water-dispersed colloidal silica (Nippon Kagaku Kogyo Co., Ltd.)
1 Snowtex O# manufactured by Co., Ltd., solid content concentration 20% N40
38 parts by weight of 0.05N hydrochloric acid was gradually added dropwise to a solution consisting of 0 parts by weight and 261 parts by weight of methyl cellosolve to effect hydrolysis. After the dropwise addition, the mixture was further stirred at room temperature for 2 hours, and then aged at 0°C for 24 hours. After aging, 79 parts by weight of diethylene glycol and 6 parts by weight of magnesium perchlorate were added at room temperature, and the mixture was stirred to be homogeneous. Further, 0.5 parts by weight of flow control agent L-700j was added to prepare a paint. The lens processing and coating methods were the same as in Example-1.

Example-4 β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane 163-couple moiety, water-dispersed colloidal silica (
Catalyst Chemical Industry Co., Ltd. ” 0ataloidBy H1
Solid content concentration y2o s > s 4 parts 0
, 43 parts by weight of 05 N hydrochloric acid was gradually added dropwise to carry out hydrolysis. After the dropwise addition, the mixture was further stirred at room temperature for 2 hours, and then
It was aged for 24 hours at ℃. After aging, 88 parts by weight of diethylene glycol and 3 parts by weight of magnesium perchlorate were added at room temperature, and the mixture was stirred to be homogeneous. In addition to this, flow control)
A paint was prepared by adding 0.3 parts by weight of 0-lue agent L-7Qol. The lens processing and coating methods were the same as in Example-1.

Example-5 "r-glycidoxypropylmethyl jetoxysilane"
4xitm, 2.85 M parts of methanol-dispersed colloidal silica (methanol silica sol), and 368 parts by weight of isopropanol were gradually added dropwise to 41 parts by weight of 0.05N hydrochloric acid to perform hydrolysis. After the dropwise addition, the mixture was further stirred at room temperature for 2 hours, and then aged at 0°C for 24 hours. After the preparation, 72 parts by weight of glycerin and 3 parts of magnesium perchlorate were added at room temperature, and the mixture was stirred to make it homogeneous. In addition, add 0.3% of the flow control agent L-7001.
The paint was adjusted by adding parts by weight. The lens processing and coating methods were the same as in implementation side-1.

Example-6 223 parts by weight of methyltrimethoxysilane, isopropanol-dispersed colloidal silica (080AL-1432) 3
106 parts by weight of 0.05N hydrochloric acid was gradually added dropwise to a solution consisting of 28 parts by weight and 212 parts by weight of isopropanol to effect hydrolysis. After the addition, the mixture was further stirred at room temperature for 2 hours, and then aged at 0°C for 24 hours. After aging, 150 parts by weight of glycerin and 3 parts by weight of magnesium perchlorate were added at room temperature and stirred to make the mixture uniform. Further, 0.3 parts by weight of flow control agent L-7001 was added to prepare a paint. The lens processing and coating methods were the same as in Example-1.

Example-7 227 parts by weight of γ-glycidoxyprobyltrimethoxysilane, 2 parts by weight of water-dispersed colloidal silica (Snowtex a)
62 parts by weight of 0.05N hydrochloric acid was gradually added dropwise to a solution consisting of 8 parts by weight of a and 330 parts by weight of methyl cellosolve,
Hydrolysis was performed. After the dropwise addition, the mixture was further stirred at room temperature for 2 hours, and then aged at 0°C for 24 hours. After ripening, 90 parts by weight of azelaic acid and three parts of magnesium perchlorate were added at room temperature and stirred to make it homogeneous. Further, 0.3 parts by weight of flow control agent L-7001 was added to prepare a paint. The method of lens treatment and coating is as shown in Example-1
is the same as

Example-8 β-(3,4-Eboxycyclohexylene ethyltrimethoxysilane 189 Luna moiety, water-dispersed colloidal silica (
50 parts by weight of 0.05N hydrochloric acid was gradually added dropwise to a solution consisting of Snowtex 0) 384 Jushabu and 279 parts by weight of ethyl cellosolve to effect hydrolysis. After the dropwise addition, the mixture was further stirred at room temperature for 2 hours, and then aged at 0°C for 24 hours. After ripening, 96 parts by weight of azelaic acid and 3 parts by weight of magnesium perchlorate were added at room temperature, and the mixture was stirred to be homogeneous.

Further, 0.5 parts by weight of flow control agent L-7001 was added to prepare a paint. The lens processing and coating methods were the same as in Example-1.

Example-9 γ-glycidoxypropylmethyl diethoxy 5:/
276 parts by weight hk, 134 parts by weight of methanol-dispersed colloidal silica (manufactured by Catalysts Kasei Kogyo Co., Ltd. "08OAL'-1132j', solid content 60%) and ethylnaloturu 1
48 parts by weight of 0.05N hydrochloric acid was gradually added dropwise to the solution consisting of 465 layers to effect hydrolysis. After the dropwise addition, the mixture was further stirred at room temperature for 2 hours, and then aged at 0°C for 24 hours.

After aging, 74 parts by weight of terephthalic acid and 3 parts by weight of magnesium perchlorate were added at room temperature, and the mixture was stirred to be homogeneous. A paint was prepared by adding 0.5 east fd part of flow control agent L-7001 to this mixture. The lens processing and coating methods were the same as in Example-1.

Example-10 Methyltrimethoxysilane 1'62i parts, meta/-#
Dispersed colloidal silica (methanol silica sol) 596
77 parts by weight of a05N amolic acid was gradually added dropwise to a solution consisting of 249 parts by weight and 249 parts by weight of methyl cellosolve to effect hydrolysis. After the dropwise addition, the mixture was further stirred at room temperature for 2 hours, and then aged at 0°C for 24 hours. After aging, 116 parts by weight of adipic acid and 3 parts by weight of magnesium perchlorate were added at room temperature.
Stir to make it homogeneous. Furthermore, 0.3 parts by weight of flow control agent L-7001 was added to the paint. A was set up. The lens processing and coating methods were the same as in Example-1.

Comparative example-1 r-glycidoxypropylmethyljethoxysilane 26
68 parts by weight of 0.05 N hydrochloric acid was added to 8 parts by weight with stirring, and after further stirring for 1 hour, the mixture was aged at room temperature for 24 hours. To this liquid, 630ii parts of colloidal silica (methanol silica sol), 17 parts by weight of aluminum acetylacetonate, and a flow control agent L-700 were added.
1wo0.4mff1iB and phenyl cellosolve 12
, 4 parts were added and stirred to prepare the paint. The lens processing and coating methods were the same as in Example-1.

Comparative example-2

Claims (1)

[Claims] The following (A) a (B) s(
1. A synthetic resin lens characterized by being coated with a node coated film made of 0.1 and CD) as main raw materials. (In the formula, R1 is an organic group having a hydrocarbon group having 1 to 6 carbon atoms, a vinyl group, a methacryloxy group, or an epoxy group R,
II is a hydrocarbon group having 1 to 4 carbon atoms R3 is a hydrocarbon group having 1 to 5 carbon atoms
hydrocarbon group. Alkoxyalkyl group or hydrogen atom, t is 0 or 1
CB) colloidal silica with a diameter of 1 to 100 millimicrons; (0) polyhydric alcohol or polycarboxylic acid or polycarboxylic acid anhydride; Magnesium chlorate