JPS60213901A - Synthetic resin lens - Google Patents

Abstract

PURPOSE:To improve the resistance to scratching, heat and impact, the dyeability and the antireflecting effect by providing a hard coat layer having a specific difference in refractive index from a base material of a synthetic resin lens having a specific refractive index on the surface of said base material and providing further antireflecting layers. CONSTITUTION:The hard coat layer 23 consisting of a synthetic resin having the refractive index of which the difference in refractive index from the base material 24 of the synthetic resin lens having 1.48-1.55 refractive index is within + or -0.04 and having 1-20mum film thickness is provided on the surface of said base material and further the antireflecting layers 21, 22 consisting of single or multiple layers of synthetic resin films having about 70-200nm film thickness are provided thereon. 1 Or >=2 layers among the layers forming the layer 23 and/or the layers 21, 22 consist essentially of I -IV, i.e., I ) the org. Si compd. expressed by the formula, II) colloidal silica having about 1-100mum grain size, III) >=1-2 kinds among polyhydric alcohol, polyhydric carboxylic acid and multifunctional epoxy compd., IV) oxides of Al, Ti, Zr, Sb, etc.

Description

[Detailed Description of the Invention] [Technical Field] The present invention relates to a synthetic resin lens that has excellent scratch resistance, heat resistance, M impact resistance, and dyeability, and prevents reflection. [Prior Art] Synthetic resins are superior to glass in terms of impact resistance, resistance to deterioration, dyeability, ease of processing, etc., so they are used in eyeglass lenses that emphasize safety and fashion, camera lenses that aim to be lightweight, etc. widely used. However, synthetic resin has the disadvantage that it is more easily scratched than glass, and this is a major impediment to the widespread use of synthetic resin lenses.

In order to eliminate this drawback, a dual force method has been used in the past. One method is to apply a hard coat layer of silicone resin, acrylic resin, melamine resin, epoxy resin, etc. to the surface of a synthetic resin lens using a dipping method, spinner method, flow method, or spray method, and then heat-cure or apply ultraviolet light. A film is formed by curing.

This method has the advantage that the coating has excellent durability such as heat resistance, water resistance, scratch resistance, and adhesion, can be dyed, and does not reduce the impact resistance of the lens. The drawback was that it had no preventive effect.

Another method is to form a corrugated film of an inorganic material such as silicon oxide or aluminum oxide on the surface of a synthetic resin lens using a method such as a vacuum evaporation method. This method is currently being put into practical use for eyeglass lenses in combination with an antireflection film. The film structure is as shown in Fig. 1. First, a hard coat layer made of silicon oxide, aluminum oxide, etc. is provided on a synthetic resin lens base material, and then silicon oxide is coated on top of that.

Zirconium oxide, zirconium acid, ibuterbium oxide, ibutorium oxide, aluminum oxide.

The anti-reflection layer is formed by alternating several layers of materials with a -1 higher refractive index and materials with a lower refractive index among materials such as tantalum pentoxide, chromium oxide, and magnesium fluoride. . This method has the advantage of combining nodal coating and anti-reflection, but the coating has poor durability and impact resistance, and lenses coated with this coating cannot be dyed from above. There are drawbacks.

Various studies have been conducted to overcome these deficiencies.

For example, a method of providing a synthetic resin film as a hard coat layer and forming an inorganic material thereon by vacuum deposition is considered, and some methods have already been commercialized. In this case, since the node coat layer is made of synthetic resin, the inorganic film can be made thinner, and as a result, durability such as heat resistance and scratch resistance can be improved, but this is not sufficient for practical use. There is also the idea that a thin synthetic resin film can achieve an anti-reflection effect. For example, % opening/closing 58-46501
In the case of lenses and base materials having a film structure such as that disclosed in 2003, a synthetic resin coating having a refractive index different from that of the lens base material is provided directly on the surface of the lens base material. This has disadvantages in that reflection at the interface of the lower layer increases, the antireflection effect is impaired, and stable interference colors cannot be obtained.

However, since the hard coat layer is thin, the scratch resistance may be poor in some cases.

〔the purpose〕

An object of the present invention is to solve the above-mentioned tr problems. The purpose of the present invention is to:

It is an object of the present invention to provide a synthetic resin lens that has excellent scratch resistance, old heat resistance, impact resistance, and dyeability, and also has an antireflection effect.

〔overview〕

That is, according to the present invention, (1) A film having a refractive index difference of 0.04 or less with respect to the base material, and a film thickness on the surface of a synthetic resin lens base material A having a refractive index of 1.48 to 1.55. ffff an eight-decoat layer made of synthetic resin coating B with a thickness of 1 to 20 μm, and an antireflection layer made of a single layer or multilayer synthetic resin coating OK with a thickness of 70 to 200 μm on the surface of the coating. Synthetic resin lens with f% characteristic.

(2) One layer or 1-t2 of the layers constituting the synthetic resin coating B and/or the g+1 synthetic resin coating C
A lens made of synthetic wood according to claim 1, characterized in that each of the layers contains the following (a), (b), and (c) as main components.

(b) The general formula is F1′.

R'a -Si (OR3), -a-b (in the formula RIH a hydrocarbon having 1 to 6 carbon atoms, a vinyl group, an amine group, an imino group, an epoxy group, a (meth)acryloxy group, a phenyl group, and a mercapto group) [R2 is hydrogen or a (halogenated) hydrocarbon group having 1 to 6 carbon atoms, R3 is a hydrocarbon group having 1 to 5 carbon atoms, an alkoxyalkyl group, or fc n carbon number 1
The γ-syl group of 4, a and b are 0.1 or 2, and one or more organic silicon compounds represented by α+b≦2).

(b) Colloidal silica with a particle size of 1 to 100 millimeters.

(c) One or more than 29 compounds selected from polyhydric alcohols, polyhydric carboxylic acids, and polyfunctional epoxy compounds.

(b) Magnesium perchlorate (3) @ The synthetic resin according to claim 2, wherein the component (b) is an oxide of a metal element such as aluminum, titanium, luconium, or antimony. made lens.

It is related to.

Next, each coating that constitutes the synthetic resin lens in the present invention will be explained.

The basic membrane preparation of the present invention is shown in Figure 2.
A synthetic resin hard coat layer 2 is formed on the synthetic resin lens 24.
5, and a single-layer or multi-layer antireflection layer 2 made of synthetic resin.
1 to 22 are provided.

Synthetic resin lens base materials include acrylic resins and ethylene glycol vinyl allyl carbonate resins, which are widely used in eyeglass lenses, as well as polyester resins.
Preferred are alkyd resins, epoxy resins, vinyl chloride resins, polyethylene resins, and the like.

The synthetic resin coating B must be sufficiently effective as a hard coat layer. The purpose of the hard coat layer is to improve the scratch resistance of the lens surface and also serve as a dyeing layer to improve dyeability with commercially available disperse dyes. Therefore, the synthetic resin coating B, which is a hard coat layer, should have a refractive index that has a refractive index difference within ±0.04 from the lens base material. It is necessary to use a synthetic resin that has a certain property, and the film thickness must be 1 to 20 μm, which is sufficient to improve scratch resistance and dyeability. If the difference in refractive index with the base material is 1004 or more, reflection will be high at the interface, which will adversely affect the antireflection effect, which is one of the characteristics of the present invention, and the thickness of the hard coat layer will be uniform. If not,
Since the interference color changes slightly, this is a fatal defect in the appearance of the lens.Furthermore, the film thickness varies by about 1 to 20 μm, and more preferably by about 2 to 10 μm. When the film thickness is less than 1 μm, the abrasion resistance is poor and it is insufficient as a hard coat layer. 20 μ sound compared to hK? If it exceeds the temperature, the thermal properties of surface 1 tend to deteriorate and cracks may appear. In the case of no hard coat in the present invention, since the difference in refractive index with the base material is within ±004, there is no need to strictly control the film thickness. no problem.

The component (a) used in the synthetic resin primary BK is methyltrimethydisilane.

Ethyltriethoxysilane, phenyltrimethoxysilane, dimethyldimethoxysilane, phenylmethyldimethoxysilane, vinyltriethoxysilane, vinyl-tris(β-methoxyfudiethoxysilane, vinyltriacetoxysilane, γ-glycidoxypyltrimethoxysilane) .

r-methacryloxypropyltrimethoxysilane, r-
Glycidoxypropyl(methyl)jethoxysilane, 3
-(3,4epoxycyclohexyl)ethyl-IJmethothodisilane and the like. These may be used alone or in combination of two or more. In addition, it is preferable to use these by hydrolyzing them in an organic solvent such as alcohol in the presence of an acid. b), and component e (can be mixed with either of them).

Ingredient (b) is colloidal silica with a particle size of 1 to 100 millimeters, and oxides of metal elements such as aluminum, titanium, zirconium, and gamma nitimony, water, and water.
cT/i is a colloidal solution in which high molecular weight metal oxide fine particles are dispersed in an alcohol-based dispersion medium. The types of metal oxides can be selected and mixed depending on the refractive index of the lens base material.

The polyhydric alcohol of component e includes difunctional alcohols such as (poly)ethylene glycol, (poly)propylene glycol, neopentyl glycol, catechol, resorcinol, and alkanediol, or glycerin, trimethylol fluoropane, etc. Examples include trifunctional alcohols. Additionally, polyvinyl alcohol and the like can also be included.

Examples of polyhydric carboxylic acids include malonic acid, cono-phosphoric acid, γ-dipic acid, azelaic acid, maleic acid, 0-phthalic acid, terephthalic acid, fumaric acid, itaconic acid, and oxaloacetic acid. , and may also include cono-phosphoric anhydride, maleic anhydride, itaconic anhydride, 1,2-dimethylmaleic anhydride, phthalic anhydride, hexahydrophthalic anhydride, naphthalic anhydride, and the like.

Examples of polyfunctional epoxy compounds include polyglycidyl ethers obtained from epichlorohydrin and bisphenol A, catechol, (poly)ethylene glycol, neopentyl glycol, glycerin, trimethylol fibrin, and pentaerythritol. Also included are epoxynopola, glycidyl methacrylate, and the like.

By using one or more of component (a), component (b), and magnesium perchlorate (in addition to component G) as a curing catalyst, excellent hot water resistance, dyeability, It is possible to obtain a coating film having chemical resistance and weather resistance, and a paint having a long pot life. Generally, aluminum acetylacetonate, ammonium perchlorate, and octylic acid are known as curing catalysts, but these have drawbacks such as hot water resistance, uniform dyeability, and liquid pot life. There is no other product other than magnesium perchlorate that satisfies all properties.

Like the resin used for the node coat layer, the synthetic resin coating C that constitutes the antireflection layer must have excellent wiring polarity and dyeability. In addition, in order to obtain a good anti-reflection effect, layers with a high refractive index and layers with a low refractive index are alternately layered, so synthetic resin coatings are required! llIO is not limited to a single layer, and may be multilayered. Further, in the case of a multilayer structure, a difference in refractive index of 0.05 or more is required between a layer with a high refractive index and a layer with a low refractive index. Therefore, high refractive index scraps include synthetic resins with a refractive index of 1.53 or higher, such as polystyrene, polycarbonate, aromatic rings other than polystyrene, heterocycles, alicyclic cyclic groups, or halogens other than 79 elements. Various polymer compositions, thermosetting resins using melamine resins, phenolic resins, epoxy resins, etc. as curing agents, and each f+'i that facilitates radical curing by introducing double bonds into the above compounds. Modified resins are preferred. Furthermore, the refractive index of the silicone resin can be increased by using it in combination with an organometallic compound, a metal coordination compound, or the like. In addition, 1 synthetic resin Ml! The resin used in IIB may also be used. In this case, each component must be adjusted to increase the refractive index. in particular,
Add alumina sol to the metal oxide colloid solution of component (b),
Alternatively, there are methods such as using titanium sol or the like, or using a polyfunctional epoxy compound as component (c). As a layer with a low refractive index, a synthetic resin 1 having a refractive index of less than 1.51, such as an acrylic resin or a vinyl resin.

Fluororesins, polyester resins containing aluminum, cellulose resins, silicone resins, and the like are preferred. There is also a method in which various synthetic resins are substituted with fluorine. In addition to this, the resin used for the first synthetic resin coating B may also be used. In this case, it is necessary to adjust each component in order to lower the refractive index. Specifically, silica sol is used as component (b). There are methods such as increasing the ratio of component (I:I) among each component. The mixing ratio of each component as indicated in claims 2 and 3 of the present invention is preferably Component (b) (solid content calculated as SiOz) 10
(converted to solid content calculated by weight) is 50-800 parts by weight, the total of component (c) is 50-600 parts by weight, and component (3) is 0.001-5.0 weight percent of the total residual solids. Use within the range. More preferably, component (a) is 100 to 500 parts by weight and component (c) is 100 to 500 parts by weight.
It is 500 parts by weight. Each of the above ingredients includes alcohol,
Solvents such as ketones, cellosolves, and carboxylic acids can be used alone or in combination. If necessary, small amounts of surfactants, antistatic agents, and ultraviolet absorbers can be added to improve the coating properties of the coating liquid. , the performance of the coating can also be improved.

〔Example〕

Hereinafter, the present invention will be explained in more detail with reference to Examples.

Example 1 (1) Synthetic resin lens base diethylene glycol bisallyl carbonate resin (c
R-39) The lens is immersed in an IJium aqueous solution for 3 minutes, then washed and dried.

The refractive index of this lens was u1.50.

(2) Hard coat layer 30 parts by weight of r-glycidoxypropyltrimethoxysilane, methanol-dispersed colloidal silica (manufactured by Catalyst Chemical Industry Co., Ltd., solid content m degree 30% 115.0 parts by weight, ethylene glycol glycidyl ether 10.2 parts by weight) and 36.6 parts by weight of ethyl cellosolve, 82 parts by weight of 005 normal hydrochloric acid was gradually added dropwise to complete hydrolysis.

Then, 0.1 part by weight of magnesium perchlorate was added and mixed by stirring.

0.1 part by weight of a silicone surfactant was added to this to prepare a paint.

A synthetic resin lens base material was immersed in the solution prepared as described above, pulled up at a speed of 20 minutes, and coated uniformly. The coated lenses were heated and dried in a hot air dryer at 80° C. for 30 minutes, and then heated in a hot air dryer at 120° C. for 1 hour. The refractive index of the obtained film was 1.50=film thickness of 4 μm.

(6) Antireflection layer (σ,) The aforementioned methanol colloidal silica 6-fold IJ parts, tetrabutoxy titanium 6 parts by weight, methanol 91 parts by weight, and silicone surfactant 01 parts by weight were added and stirred to form a paint. .

(b) r-glycidoxypropyltrimethoxysilane 1
．． 5-fold claw part, methanol-dispersed colloidal silica 5 mentioned above
．． 12 parts by weight of 0.05N hydrochloric acid were gradually added dropwise to a solution consisting of 2 N# parts, 2.0 parts by weight of ethylene glycol, and 90 parts by weight of methanol to perform hydrolysis. Thereafter, all 0.02 parts by weight of magnesium perchlorate was added and stirred to mix. Add silicone surfactant 0.08
A paint was prepared by adding parts by weight.

Add NO to the solution (α) prepared as above by (2).
- Immerse the synthetic resin lens on which the decoat layer has been formed, and
It was pulled up at a speed of 1/min to uniformly coat the solution. After the coated lenses were heated and dried with hot air at 80°C for 20 minutes,
It was dried by heating with hot air at 120° C. for 1 hour. The resulting broken membrane had a refractive index of 1.59 and a thickness of 84 nm. Next, a solution (bI′v:I
II was established. The coating and curing method is as follows: Solution (a)
I did it the same way as when I did it. The refractive index of the obtained film was 1.
48, the film thickness was 90 nm.

The average reflectance in the visible light range of the synthetic IL-1 resin lens thus obtained was 2.0 cm on one side, indicating a good antireflection effect.

Example 2 (1) Synthetic i1gI lens material K1-1', (1) of Example 1 was used.

(2) For the hard coat layer, (2) of Example 1 was used.

(3) Anti-reflection film (c) 2.0 parts by weight of r-glycidoxypropyltrimethoxysilane, 11.5 parts by weight of water-dispersed alumina sol (manufactured by Nissan Chemical Industries, solid content: 10%), 1.2 parts by weight of azelaic acid. 0.1 part of 0.3N hydrochloric acid was gradually added dropwise to a solution consisting of 1 part of 0.3 N hydrochloric acid and 75.5 parts of methanol to effect hydrolysis. Then, magnesium perchlorate 0.0
2 parts by weight were added and stirred to make it homogeneous.

A coating material was prepared by adding 0.087'i acid part of a silicone surfactant to this.

A synthetic 491 resin lens, which had been formed up to the hard coat layer in Example 1 (2), was coated with the solution (b). The coating and curing methods were the same as those for solution (a). The refractive index of the obtained film was 1.5
8. The film thickness was 85 nm. Next, a coating with a rough solution (b>K) was provided in the above-mentioned coating.

The average reflection in the visible light range of the synthetic resin lens thus obtained was 2.1% on one side, and a good antireflection effect was obtained.

Example 3 (1) Synthetic resin lens base material obtained by mixing 30 parts by weight of diethylene glycol bisallyl carbonate, benzyl methacrylate) 103 (bone part, 91 parts by weight of diallyl isophthalate 60M, and 3 parts by weight of diisopropyl peroxydicarbonate) A lens obtained by heating and polymerizing the solution is surface-treated in the same manner as in Example 1 (1).The refractive index of this lens is d1.
It was 55.

(2) Octopus coat layer r-f A solution consisting of 30 parts by weight of lysidoxyglobil trimethoxysilane, 15.0 parts by weight of methanol-dispersed titanium sol, 10.2 parts by weight of glycerin diglycidyl ether, and 6.6 parts of ethyl cellosolve S. 8.2 parts by weight of 0.005 scale hydrochloric acid was gradually added dropwise to carry out hydrolysis. Thereafter, 01 parts by weight of magnesium perchlorate was added and mixed by stirring. Add 0.0% silicone surfactant to this.
1 part by weight was added to prepare a paint.

A synthetic resin lens base material was immersed in the solution prepared as described above and pulled up at a rate of 20 crrL/min to uniformly coat the solution. The coated lenses are dried in a hot air dryer at 80"C for 30"
After drying by heating for a minute, it was dried by heating in a hot air dryer at 120''C for 1 hour.The refractive index was 1.591M and the thickness was 4 μm.

(3) The antireflection layer includes (3) to (6) of Example 1.
'lr was used. The average reflectance of the synthetic resin lens thus obtained in the visible light range was 1 on one side, indicating a good antireflection effect.

Example 4 (1) For the synthetic resin lens base material, (1) of Example 3 was used.

(2) Hard coat layer Ku, (2) of Example 1 was used.

(3) The antireflection layer contains (3) f! of Example 2. r was used.

Comparative example 1 1 (')! [14 "V 7 y: a #""0'
"j" D (1) 1 layer m was used.

(2) For the hard coat layer, (2) of Example 1 was used.

(3) This is an antireflection layer in which five antireflection layers Sio, zio, are alternately provided by a vacuum deposition method, and when viewed from the hard coat layer side, B
ib, ,2i0. , B10217) 3 M (D total light 1 [thickness is approximately λ/4, the next Zip2 is λ/4. The top layer 5i02 is composed of λ/4 in the order of λ/4. Obtained in this way The surface reflection of a synthetic resin lens is 0.9
%Met.

The transmittance, scratch resistance, heat resistance, and impact resistance of Examples 1 to 4 above were evaluated, and the results are shown in Table 1. The test method in Table 1 is as follows.

(1) Transmittance: Using a spectrophotometer, the transmittance in the visible range was averaged.

(2) Scratch resistance: The state of the coating was observed after it was peeled 100 times back and forth under a load of 200 g using #0000 Steel Cool.

A: Almost no scratches B: Slight scratches C: Many scratches (3) Heat resistance: Temperature that does not change in appearance even after being left in a hot air constant temperature bath for 1 hour.

(4) Impact resistance: A steel ball drop test was conducted according to FDA standards, and those that passed were marked ○, and those that failed were marked x.

Table 1 Transmittance Scratch resistance Heat resistance Impact resistance 0R-5992, 2% 0. 1306G O Example I
A 130°C○ 2 A 130°C 0 3 A 130°C○ 4 8 130°C ○ Comparative Example 1 98 B 80°C × [Effect] As described above, according to the present invention, the refractive index is 148 to 155 Because the surface of the synthetic resin lens is provided with a synthetic resin hard coat layer and an anti-reflection layer,
It is possible to obtain a synthetic resin lens having excellent scratch resistance, adhesion, weather resistance, heat resistance, impact resistance, stainability, optical properties, etc., and having practically sufficient performance.

In addition to the above-mentioned effects, the synthetic resin lens according to the present invention can relatively easily obtain properties such as antistatic properties, antifogging properties, etc. by selecting and combining the components that make up the film. Therefore, it has the potential to be used in a wide range of applications.

At the same time, by varying the combination of synthetic 4% IIW used in the hard coat layer and antireflection layer in the present invention, the range of desired performance can be expanded, and the resulting effects can be further enhanced. Not as much as stated.

[Brief explanation of drawings]

FIG. 1 shows a synthetic resin lens with a conventional antireflection film structure, which has performance equivalent to that shown in Comparative Example 1. 15-piece synthetic resin lens base material 14-piece synthetic resin hard coat film 13 pieces 5io2. The film has a film configuration of zio2.5io2, the total film thickness is λ/4, and the film is formed by a vacuum evaporation method. 12 is zzo, II! , and 11 are SZ:02 films each having a film thickness of λ/4. FIG. 2 shows a synthetic resin lens having a film structure according to the present invention, and corresponds to Example 1. The hard coat film 22 made of synthetic resin is a synthetic resin film 21 with a refractive index of 1.60 and a synthetic resin film with a refractive index of 148. FIG. 3 is an example of the application of the synthetic resin lens made by @Construction in the present invention, and corresponds to Example 4. The hard coat 55.51 made of 35 synthetic resin lens base materials and 34 synthetic resins has a synthetic resin coating with a refractive index of 1.48 and 32 synthetic resin coatings with a refractive index of 1.57. FIG. 4, FIG. 5, and FIG. 6 show the surface reflectance in the non-visible state of synthetic resin lenses having the film configurations shown in FIGS. 1, 2, and 3, respectively. Applicant Suwa Seikosha Co., Ltd. Attorney + Attorney

Claims (1)

[Claims] (1) The surface of the synthetic #4 resin lens base material with a refractive index of 1.48 to 1.55 has a refractive index difference of 10% with respect to the base material.
A hard coat layer made of synthetic 4thI fat coating BK having a refractive index of 0.04 or less and a thickness of 1 to 20 μm is provided on the surface of the coating, and further, each layer has a thickness of 70 to 20 μm,
A synthetic resin lens characterized in that it is provided with an antireflection layer made of a single layer or multilayer synthetic resin coating 0 of tn. (2) Among the layers constituting the synthetic resin coating B and/' or the synthetic resin coating C, one layer 2 JP
The synthetic resin lens according to claim 1, characterized in that the following (a), (b), and (c) are the main components. (a) If the general formula is 2b Rh -Bi (OR")4-a-p (in the formula, E/t is a hydrocarbon having 1 to 6 carbon atoms, a vinyl group, an amino group, an imino group, an epoxy group, a (meth) ) an organic group containing at least one selected from γcryloxy group, phenyl group, and mercapto group, dihydrogen, or a (halogenated) hydrocarbon group having 1 to 6 carbon atoms; R3 is a hydrocarbon having 1 to 5 carbon atoms; group, alkoxydialkyl group, or acyl group having 1 to 4 carbon atoms, α and buo, 1°f
fc n 2, one type or 1-12 or more types of organic silicon compounds represented by α+b≦2). (b) Colloidal silica with a particle size of 1 to 100 millimicrons (c) One or more of the compound groups selected from polyhydric alcohols, polyhydric carboxylic acids, and polyfunctional epoxy compounds. B) Magnesium perchlorate (5) The first two components (B) are characterized in that they are oxides of metal elements such as aluminum, titanium A, zirconium, and antimony. q! f Synthetic wood-made resin according to claim 2.