JPS59146001A - Spectacle lens - Google Patents

Abstract

PURPOSE:To improve water resistance and to provide substantial resistance to scratching after processing for preventing reflection by providing an inorg. reflection preventive layer via a hardened coating layer composed of a partially hydrolyzed substance and a multifunctional epoxy compd. on a specific plastic lens. CONSTITUTION:The coating layer formed by using total 100pts.wt. consisting of the partially hydrolyzed substance of a mixture composed of 42-67pts.wt. the compd. expressed by SiX4 (X is alkoxy of <=C4) and 13-44pts.wt. the compd. expressed by the formula (R; is an org. group having epoxy, gamma-methacyloxypropyl; R<2> is H, an org. group of 1-4C, Y is halogen except fluorine or alkoxy, l, m are such a number of >=0 at which l+m is 1, 2) and 14-32pts.wt. a multifunctional epoxy compd. as an essential component and curing thermally the same with 0.01-0.0pts.wt. ammonium perchlorate as a curing catalyst is applied on the surface of a lens formed of diethylene glycol bis-allylcarbonate and further a single or multilayered reflection preventive layer consisting of an inorg. material is provided thereon.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a plastic eyeglass lens that is resistant to scratches and has low surface reflection.

Plastic lenses are lighter than inorganic glass lenses; 1. They have excellent impact resistance; 4. They are resistant to pressure. ! It has various advantages such as good I. However, on the other hand, the biggest drawback is that it is easily scratched, and the biggest challenge is to achieve full scratch resistance.

In addition, there is a strong demand for eyeglass lenses, both plastic lenses and inorganic glass lenses, to have less surface reflection, and at present, most eyeglass lenses in Japan are treated with anti-reflection treatment.

In other words, plastic lenses are required to simultaneously improve scratch resistance and reduce surface reflection.

Conventionally, many methods have been studied to reduce #1 abrasion resistance of plastic lenses, and they can be roughly divided into:
It can be divided into two methods. One is b 1.02 +A
One method is to apply a hard coat of an inorganic material such as R, 2, O3, etc., and the other method is to apply a hard coat of an organic material such as acrylic or phosphor.

An inorganic hard coat (IL) is applied by applying an inorganic layer with a thickness of about 0.5 to 3.0 m by vacuum evaporation or the like. Since it is possible to apply multiple layers of various types of films with accurate film thickness, it is also possible to apply an anti-reflection layer at the same time.
This is the most commonly used method at present. but,
The inorganic 7-docoat has the disadvantage that if a film is formed thick enough to provide sufficient scratch resistance, the impact resistance will be extremely low.

On the other hand, the organic hard coat film does not deteriorate in impact resistance, warping force, or depth even when the film is thick, with a total thickness of 1 to 10 μm, and moreover, it is possible to add dyeability to the hard coat film. For this reason, it has received particular attention in recent years. Regarding the second condition, the anti-reflection effect, in the case of an organic coating film, it is impossible to accurately control the film thickness, and on top of that, it is impossible to accurately control the film thickness. It is safe to use a film thickness of at least 2μ772 or more, and since it is difficult to obtain an appropriate refractive index as an anti-reflection film, it is extremely difficult to have an anti-reflection effect with an organic coating alone. -C It's difficult. Therefore, in order to make a complete lens with high surface scratch resistance and anti-reflection effect, we believe that the easiest method is to provide an organic hard coat layer as the first layer, and then apply an inorganic anti-reflection layer on top of that. Rahal.

However, many organic hard coat films currently in use have major drawbacks. SofL is that even if the initial hardness is sufficient, the water resistance is weak, so the scratch resistance significantly decreases after immersion in hot water.

This is largely due to the composition and the curing catalyst. In JP-A-56-72 [+54, the main component is an epoxy group-containing organic 7 run]-decoat, when ammorum perchlorate, which is a latent catalyst, is used, the water resistance is the same as above, and It has been disclosed that the life of the node coating liquid is also extended.

However, the hard coat is not dyeable and cannot take advantage of the great advantages of resin lenses.

Furthermore, in the case of the node coating film, when all six inorganic anti-reflection layers were applied, the layering properties between the two were poor, resulting in a decrease in scratch resistance after anti-reflection treatment, or a decrease in film resistance in cross-cut tests.・Ging occurs. This phenomenon also occurs in the case of coats made of other compositions, and in some cases, after anti-reflection treatment, they become as easily scratched as 0R-39. ! JP-A-55-92844 contains the following A and B.
A coating composition consisting of C and C is shown.

A, a silicon compound represented by the general formula 5i (ORS4) and a silicon compound represented by the general formula H3C-81(OR2)3 (where R' and R2 are a hydrocarbon group having 1 to 5 carbon atoms, alkoxy"alkyno 1° group or (1 to 4 carbon atoms)
one or more selected from the following acyl groups)
2 No. 2 Hinei decomposition product 2 ZO ~ 80.0 parts by weight.

B, general formula (wherein R3 is an organic group containing at least one group selected from ethinovinyl, pro-megabutyl, amino, grindquine, methacryloquine, phenyl, and SH group; I(4 is Hydrogen, methyl, ethyl or vinyl
11% R' is a hydrocarbon group having 1 to 5 carbon atoms, alkoxyalkyl 1-! Or 2, 7 is U mag ζ is 1, x + y
≦2) 7) 1 or 2
Seed, above hydrolyzate 1 (], [J ~ 72, 5 heavy inspector.

C. 0.6=10.0 parts by weight of at least one selected from epoxy compounds, polyalkylene glycol fats and oils, dicarboxylic acid esters, and phosphoric acid esters.

The same is true in this case, if the amount of B or C component is increased within the above range IJE, the adhesion will be poor when the entire anti-reflection layer is applied, and the final lens state will have extremely low abrasion and swirl resistance. bad. On the other hand, if B and C are decreased and Ai is increased within the above range, a cracking sound will occur in the coating film, and the value as an eye-pleasing lens will be 1i! I lose f. Furthermore, in this case, the curing catalyst is not specified, and the water resistance of the coated film is poor in the case of solid seeds. In this way, even if a coating film has good scratch resistance, one that has both adhesion and water resistance when coated with an anti-reflection IF film'fr:mL7
It didn't exist before.

The present inventors focused on a method of leaving an inorganic anti-reflection layer on an organic hard coat film and conducted repeated research, and succeeded in developing an organic hard coat and an anti-reflection film with good adhesion between the two, and further, In order to improve the water resistance of hard coats, we conducted extensive research on various curing catalysts and discovered that ammonium perchlorate is the most effective curing catalyst for organic hard coat liquids, leading to the present invention. .

As stated above, the object of the present invention is to provide scratch resistance.

The object of the present invention is to provide a plastic eyelid lens with excellent water resistance and sufficient scratch resistance even after antireflection treatment.

That is, the present invention provides 67@Sei-116 from 42 parts by weight of a compound represented by the general formula (1) (wherein, X represents an alkoxy group having 4 or less carbon atoms) on the surface of 0R-59jl Renos. and,
General formula [■] 2m Rlt-8i-Y4-4- [■] (In the formula, R1 is an organic group having an evogiso group, O, γ-methacryloquine probyl group, R2Vi hydrogen or (carbon number 1 to 4 organic groups, Y is a halogen-sized alkoxy group excluding fluorine, °C and m are integers of 0 or more such that Q -1-m is 1 or 2) : parts by weight to 44 parts by weight of the partial hydrolyzate of the mixture and 14 parts by weight to 32 parts by weight of a polyfunctional eboxo compound as main components, and 0.011 parts by weight to 1.[1 parts by weight]. A coating layer thermally cured using ammonium perchlorate as a curing catalyst is applied, and a 14i layer made of an inorganic substance or (l
It is an ophthalmic lens with a multi-layered anti-reflective layer.

Compound 1 represented by the first general formula [1] used in the present invention
Examples include tetramethoxysilane, tetraethoxysilane, tetraisoproboquinane, tetran-propoquinesilane, and tetra-n-butquinsilane. If the amount of the compound represented by the general formula CD is less than 42 parts by weight, sufficient scratch resistance as a hard coat will not be obtained, and if it exceeds 67 parts by weight, cracks will occur during heat curing.

Examples of the compound represented by the general formula [111] include methyltrimethoxysilane, ethyltrimethoxysilane, propyltrimethoxysilane, butyltrimethoxysilane, methyltriethoxy/silane, ethyltriethoxysilane, propyltriethoxysilane, butyltrimethoxysilane, triethyldimethoxy, dimethyldimethoxy, dimethylshedquin, dimethyldimethoxy, 77, diethyldiethoxy, γ-glysopropyltrimethoxy,
γ-Grindkimp "J Pylmethyldimethoxy7rinran,
γ-Glysodox/Brovirtriethoxone, γ-Glysodox/Brovirtriethoxone, β-(5
, 4-Evoquinecyclohexyl) methyltrimethoxysilane, β-(3,4-Evoquinecyclohexyl)ethyltriethoxysilane, γ-methacrylicyltrimethoxy77ran, γ-methacrylicyltrimethoxy77ran, etc. can be given. In the general formula [■],
If the amount of the compound is less than 13 parts by weight, cracks are likely to occur, and if it exceeds 44 parts by weight, the adhesion with anti-reflection 1 to 1 will deteriorate.

Polyfunctional Evoquin compounds include diglyrindyl ethers of difunctional alcohols such as (poly)ethylene glycol, (poly)propylene glycol, neopentyl glycol, catechol, resolunol, and alkylene glycol; Examples include l-diglycidyl ether, F-light, trimedylolbroban, lr, and triglycidyl ether. If the polyfunctional Evoquin compound is less than 14 parts by volume, cracks will occur during heat curing, and if it exceeds 32 parts by volume, the anti-reflection layer will not have sufficient scratch resistance. The adhesion also decreases.

As shown below, by controlling the ratio of each component, the organic hard coat itself has unprecedented hardness, and at the same time, the adhesion with the anti-reflection layer has been dramatically improved. At the final reflection, a 1:1 layer was applied (I was able to obtain a high 11% purple color in the negative state).

As a result of various studies, ammonium perchlorate was found to be the most effective curing catalyst due to its balance between scratch resistance and water resistance. It should be noted that if ammonium perchlorate is less than 0.01% of Bartko-1's main constituent, sufficient hardness will be obtained; if it exceeds 1.0% gold, the lens will become seriously yellowed.

The anti-reflection layer is made up of 81 oz.

ZrO2,ARz03t'rio,,,Tags,Y
2O31Yb203 Metal oxide, FE i N
4 Shield metal nitride, metal fluoride such as 14gF2, (
There are metals such as JR, W, and Ta.

The lens obtained in this way (r,'↓ overcomes the susceptibility to scratches, which was the biggest drawback of glass lenses), and also has an anti-reflection IF, which is required as an eyeglass lens. Effect, 1i'1 aqueous gold fr % tL
7j lens.

In addition, the present invention (is not limited to C!R-39 lens VC, but also polycarbonate, polymethyl methacrylate,
Plastic V-coats such as polystyrene can also be used, and if the adhesion is poor, the same effect can be obtained by applying a brimer treatment to each case.

Hereinafter, based on Examples, the present invention will be explained in detail. <For the purpose of explanation, the present invention is limited to these people.
do not have.

Example-1 (1) Hard coat and anti-reflection treatment consisting of 55 parts by weight of tetramethoxysilane, 22 parts by weight of β-(3゜4-evoquinonecrohequinyl)ethyltrimethoxysilane and 80 parts by weight of isopropyl alcohol. 0 in the broth
．． 05N hydrochloric acid 57 car ii: Mis gold was added and hydrolyzed. A hard coat liquid was prepared by adding 26 parts of ethylene glycol diglycidyl ether and 0.1 part of ammonium perchlorate to this bath liquid. Immerse a washed and dried OR-39 lens in this solution with a 4-dose diluted sodium hydroxide water bath solution, pull it up at a rate of 20 minutes per minute (soaking), and apply it at 100°C. 1 hour, 160
It was cured by heating at ℃ for 1 hour. Is the film thickness of Myouki hard coat film 5.5μ? 7+, and the refractive index C was 1.5υ.

This lens was further coated with 5i02. Z
After anti-reflection treatment of 5 layers consisting of rO2. The film thickness of the anti-reflection layer was O.S.mu.m, 1/ns visible gap (:) and the transmittance was 9B, 5 inches or more.

(2) Performance evaluation test Scratch resistance was evaluated on a scale of 7 and 11, where #0000 sudir wool was loaded with 1 load and 10 cycles were applied, with glass as A and acrylic resin gold as E'. .

For surface 1 weatherability, we evaluated the changes in the film after 500 hours of irradiation using a xenon fade meter (12), and those with no change were evaluated as (1), those with cracks (1) (represented as 1) with cracks.

After anti-reflective treatment, the close contact 1 cow was subjected to a cross-cut test with
I'L stone' potato ○, the area around the wound is a little 1-peeling t1'-/\, clearly the length of the membrane, expressed by rumoba ×k.

Complete table of evaluation results for Examples 1 to 6 and Comparative Examples 1 to 5-1
Shown below.

Example 91-2 3,17 Men's 1 in which 1.6-Hegi AJ'7 Diol Digrin Jil Utel was used instead of Abe 1 Non-Glycono (Jigrin Jill Nidel) in Example-1
■I processing and other operations are the same as those in actual example-1. The film thickness of this organic hard boat film is 17j13.7
The refractive index was 15.1, and the visible light transmission rate after antireflection treatment was 98.5.

Example-6 Neopentyl glycol diglycidyl ether was used instead of ethylene glycol diglycidyl ether in Sister Example-1. Lens pretreatment and other operations were the same as in Example-1. The film thickness of this organic hard coat film is 3.4 μm, the refractive index is 17j: 1.50, the reflection resistance is 1F, υIJ, and the visible light 4 pass rate is 9a5.
It was more than 1.

Example-4 In place of β-(3,4-evoquinone clohequinyl)ethyltrimethine I-quinran in Actual Case-1, γ-gridquinpropyltrimethynesilane was used. Lens pretreatment and other operations were the same as in Example-1. The film depth of this 41 hard coat film was 36 μm, the refractive index (f) was 1.50, and the visible light transmittance was 98.5 cm.

Example 5 Pretreatment of 1,6-Hegyrindiol diglycidyl ether instead of ethylene glycol diglycidyl ether in Example 11-4 and other operations are the same as in Practical HH Example-4. . II'A thickness of this organic hard coat film is 137μ
The refractive index (m) was 1.50, and the visible light false index after antireflection coating was 9/35 or higher.

Example-6 Neopentyl glycol diglyndyl ether was used instead of ethylene glycol diglyndyl ether in Example 1, row-4. Lens Ail treatment H [and other operations ζ・Yo, real 6ih 19! Same as I'. The film thickness of this hard coat is 58μm,
The refractive index was 1.50, and the visible light transmittance after antireflection treatment was 9a5% or more.

Comparative Example-1 Tetramethoxynolan 69':j'j Total part and γ-Grindoki/Probiltrinotinran 19 heavy jt part Oyohi Isoprobil Ryukol 80 PM'. iiB
44 parts by weight of 0.05N hydrochloric acid was added to a solution consisting of 1,6-hexafushiol diglyzodyl ether 12 parts by weight and 0.07 parts of ammonium perchlorate.
A hard coat solution was prepared by adding parts by weight.

Although the lens pretreatment and other operations were the same as in Example 1, cracks appeared in the surface layer during heat curing, and the lens lost its value as an eyeglass lens.

Comparative Example-2 25 parts by weight of 0.05N hydrochloric acid was added to a solution consisting of 25 parts by weight of tetramethoxy 77ran and 58 parts by weight of γ-grid kiprobil trimethquin 7ran and 80 parts by weight of oyohi isobrobyl alcohol. 3 parts by weight of 1,6-hexafushiol diglycidyl ether and 18 parts by weight of ammonium perchlorate CL were added to prepare a hard coat solution. Lens pretreatment and other operations are
It is the same as Example-1. The thickness of the hard coat film (r4) was 5.7 pm, the refractive index was 1.5D, and the visible light transmittance after antireflection treatment was 9a5% or more.

Comparative Example-6 In Example-1, no curing catalyst was used. Pre-processing of the lens and operation of its music are the same as in Example-1. The thickness of this organic]-decoated film was 6.5 μm, the refractive index was 1.50, and the visible light transmittance after antireflection treatment was 9.5 mm or more.

Comparative Example-4 In place of ammonium perchlorate in Example-1, acetylacetone aluminum salt was used. Lens pretreatment and other operations were the same as in Example-1. This organic coating film had a thickness of 58 μm, a refractive index of 1.50, and a visible light transmittance of 9a5% or more after antireflection treatment.

Comparative Example-5 Instead of ammonium perchlorate in Example-1,
Friend using stannous chloride. Lens pretreatment and other operations were the same as in Example-1. The thickness of this organic hard coat film was 4.0)tm.

The refractive index was 1.50, and the visible light transmittance after antireflection treatment was 98.5% or more.

Table 1

Claims (1)

[Claims] On the surface of a lens made of diethylene glycol bisallyl carbonate (hereinafter referred to as 0R-39), Si 67 parts by weight from the i branch of a compound 42-;
General formula [■] R% R'l-S i -Y 47□ group] (However, in the formula, an organic group 'I with R'
f γ-methacryloki/propyl group R2 is hydrogen or f
? :, is an organic group having 1 to 4 carbon atoms, Y is a halogen excluding fluorine gold, or v; 1 alcogine group, f and hirn are 0 or more such that 2 to - Ill is 1 x l ζ &; l: 2 represents an integer. ) A partial hydrolyzate of a mixture of 1 part to 44 parts by weight of f'L compound 1 and polyfunctional Evogin compound 14
From heavy 3 parts, 52 weight Rei S sword, 10 (J weight part gold main component, o, oiη [weight part power, 1.0 heavy 16
A coating layer is thermally cured using ammonium perchlorate as a curing catalyst. Eyeglass lenses with all the features.