JPS6197601A - Plastic lens high in refractive index - Google Patents

Abstract

PURPOSE:To enhance abrasion resistance, etc., by forming a specified primer layer, a silicone type coat layer contg. perchloric acid or perchlorate as a hardening catalyst, and a reflection inhibiting layer made of an inorg. dielectric material in this order on the surface of a lens high in refractive index, made of a specified copolymer. CONSTITUTION:The primer layer A1 composed essentially of a copolymer of a (meth)acrylate type monomer and an aromatic vinyl type monomer, such as styrene type monomer, is formed on the surfaces of the plastic lens L1 high in refractive index made of the copolymer composed essentially of monomer units each represented by the formula I or II in which R<1> is H or CH3, X<1>, X<2> are each halogen except F, and m+n is 0-8. On this layer L<1>, the silicone type hardened film layer B1 contg. perchloric acid or perchlorate as the harden ing catalyst and epoxy groups, and the reflection inhibiting layer C1 made of an inorg. dielectric material, such as SiO2 or TiO2, are formed. The layer C1 is such as a laminate of ZrO2 thin film 11, Al2O3 thin film 12, ZrO2 thin film 13, and SiO2 thin film 14, thus permitting the obtained lens high in refrac tive index to be prevented from flickering due to the reflection from the surface and to be enhanced in resistances to scratch, heat, water, oil, etc.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention has low surface reflection and excellent scratch resistance, heat resistance, water resistance, oil resistance, weather resistance, durability, etc., and film adhesion. This invention relates to high refractive index plastic lenses. Furthermore, the present invention relates to a high refractive index plastic lens having a hard coat layer which can be cured by hot water and which has a further improved coating life.

[Conventional technology]

Synthetic resins have the properties of being easy to process, lightweight, difficult to break, and safe, and transparent materials are rapidly becoming popular in the field of optical materials, especially eyeglass lenses. This movement has increased the demand for high-quality lenses, that is, thin plastic lenses made of high refractive index resin, and as a material for this, Japanese Patent Application Laid-Open No. 57-2E1117
No. 57-549Q1, No. 57-66401, No. 57102601, No. 57-104101, No. 57
No.-104901, No. 5B-18602.

No. 58-72101, No. 58-72102, No. 58
No. 72105 discloses a resin comprising a copolymer of a styrene monomer, a di(meth)acrylate having a halogen-substituted aromatic ring, and an allyl compound or Ninomiya di(meth)acrylate. Rainbow has improved abrasion resistance for the high refractive index plastic lenses mentioned above,
Examples in which an antireflection layer made of a generally known inorganic dielectric material is provided as a surface antireflection layer are disclosed in JP-A-57-66401 and JP-A-57-66402.
No. 57-101801, No. 58-18604,
Various solutions have been proposed in No. 1 Tsukasa 58-55501, each of which achieves a given function.

[Problem that the invention seeks to solve]

However, although the above-mentioned technology has produced an unprecedented thermosetting high-refractive index plastic lens, this material has poor abrasion resistance and refraction, similar to ordinary plastics. Since the ratio is as high as about 1.6, when used as a lens material, the transmittance is greatly reduced due to the reflection of light generated at the interface between the lens and the outside world. Furthermore, only films made of inorganic dielectric materials have improved scratch resistance, reduced surface antireflection, and have sufficient adhesive strength for practical use.
There is room for several improvements in order to improve the viability and obtain the toughness characteristic of organic hardened layers.

Therefore, in order to solve this problem, we proposed a method of applying a single layer of primer between the fabric material and the cured coating layer in order to improve the layering properties between the fabric material and the cured coating layer.
-72092 The present invention proposes a silicone-based hard coating liquid that can be cured at low temperatures, has a long coating life, and is easy to reduce costs in production management.

That is, the present invention is intended to solve the above-mentioned problems, and its purpose is to apply a primer assembly to the high refractive index plastic surface shown in the present invention, which improves the surface condition and generates strong adhesion. After coating and curing the paraboloid, a silicone-based hardening coating containing a curing catalyst, which is a compound of perchloric acid or perchlorate, is applied, which has a long coating life and easy production control, and can be cured at a low temperature of about 100°C. By forming a layer of gold and then applying an anti-reflection layer made of an inorganic dielectric material to the surface layer, the surface reflection is one in seven (and scratch resistant).

The objective is to provide a high refractive index plastic lens that has excellent heat resistance, water and oil resistance, weather resistance, durability, etc., and film adhesion.

[Ninth way to solve the problem]

The high refractive index plastic lens described in this invention has the general formula (
Acrylic resin/methacrylic compound and aromatic vinyl are applied to the surface of a high refractive index plastic lens base material made of a copolymer mainly composed of polymerizable monomers represented by 1) and (It). A resin film containing a compound as a product is coated as a primer layer, followed by a silicone-based hardening film layer containing a hardening catalyst that is a compound of perchloric acid or perchlorate, and then an inorganic dielectric material is applied to the surface layer. This is a high refractive index plastic lens characterized by having an anti-reflection layer consisting of I-.

・・・・・・・・・〔! ] (In the formula, R1 represents hydrogen or a methyl group,
x2. represents a halogen excluding fluorine, and m+n represents an integer from 0 to 8).

In addition, the silicone-based curing liquid ill containing a curing catalyst which is a compound of perchloric acid or perchlorate refers to one consisting of ■ and ◎ below.

■ Colloidal 7 with a particle size of 1 to 100 millimeters
Rika.

(However, in the formula, R4 is an organic group containing epoxy, R'l
d hydrogen * methyl, ethyl, propyl, vinyl group R6 is a hydrocarbon group of carbon Fi 1 to 4, an alkoshidialkyl group,
or 1 or 2 of the organosilicon compounds represented by (representing a silyl group having 1 to 4 carbon atoms, where a is 2 or 2)
A curing catalyst that is a compound of perchloric acid or a perchlorate.

Here, the high refractive index plastic described in the present invention can be obtained, for example, by implementing the method disclosed in JP-A-58-72101. Also (1), C11)
In addition, copolymerizable monomers such as various ultraviolet absorbers, fluorescent abrasives, diethylene glycol bisallyl carbonate, alkylene glycol di(meth)acrylate, esters of organic acids and allyl alcohol, and allyl ether compounds can be added. You can also do it.

Examples of acrylic and methacrylic monomers used in the primer resin used in the present invention include acrylic acid and methacrylic acid, methanol, ethanol, 1-
Examples include esters with lower alcohols such as propatool and n-butanol, and esters of aromatic compounds having alcoholic hydroxyl groups such as benzyl alcohol. Further, remaining components such as aromatic vinyl compounds, styrene, chlorostyrene, bromostyrene, etc. can be mentioned. As components other than these, tree) i15! 5. Glycidyl methacrylate, glycidyl acrylate, aminoethyl acrylate, dimethylaminoethyl acrylate/IJFray, in an amount within 5 percent by weight of 5.
4-epo-synchronohexylethyl methacrylate V-)ttetrahydromifurfuryl acrylate, 2-hydro-dipropyl acrylate, 3-phenylene dipropyl acrylate, ethyl calhitol acrylate, 2- and droxyethyl acrylate, 2-hydroxy 7 Glopylacrylate, 2-acrylate is ethylsuccine! jl, 2-acrylic acid ethyl phthalic acid, or their methacrylates, ethylene glycol, diethylene glycol, polyethylene glycol, glycerin, trimethylolpropane, neopentyl glycol, 1,6-hex/diol, octylene glycol, etc. Di- or triacrylates or methacrylates of poly-11TFl alcohols, and acrylic or methacrylic acid, or also vinyl compounds such as vinyl acetate, vinyl chloride, and the like can be included.

The composition of this acrylic and/or methacrylic resin and aromatic vinyl resin is determined by the combination of compounds, but it contains at least 20% by weight of methyl methacrylate and at least 10% by weight of styrene. Preferably, it is a copolymer. In addition, even if these monomers are radically copolymerized in an organic solvent, a copolymer can be obtained, but in order to generate strong adhesion, nonionic or anionic interfaces are used in water. It is preferable to carry out radical polymerization in a dispersion using an activator to form an aqueous emulsion. In addition, the number average molecular weight at this time is 100,000 or more, and the particle size is 10 to 500 mμ.
It is necessary that

That is, in solution polymerization, a copolymer with a molecular weight of 10,000 or less can be obtained, but the layering properties of these are not as good as that of optical components, and the water resistance and weather resistance of the latest products are inferior. Also, engineering! If the particle size of the fusion particles is 500 mμ or more, 1.
Lima becomes even more cloudy. The resin emulsion obtained in this way can be further treated with methanol, ethanol,
Alcohols such as 1-propatol and n-butanol, methylcarpitol, and ethylcarpitol.

It is used after being diluted with carpitols such as butyl carpitol, cellosolves such as mer≠luceronolp, ethyl cellosolve, and butyl cellosolve, and water-soluble organic solvents such as dioxane, tetrahydrofuran, and acetone. Furthermore, methyl isobutyl ketone.

Methyl ethyl ketone, methyl acetate, ethyl acetate.

Butyl acetate, dimethylformamide, propylene glycerin;
It is useful to add solvents with various evaporation rates and viscosities, such as monomethyl ether, toluene, xylene, etc., and modify them to suit the coating operation. In addition, if necessary, we can improve the final product by adding silicone-based or fluorine-based surfactants to improve coating properties, ultraviolet absorbers, dyes, and gray-colored foliage materials. It is also possible to give a given function to The preferred thickness of this layer is α1-21.

The method for applying this single layer of primer can be arbitrarily selected from among the derubbing method, spin cord method, flow coating method, and spray method. Subsequently, a uniform resin layer can be formed by drying and curing for 2 to 60 minutes at a temperature of 50° C. to 130° C. with or without air drying.

Regarding the anti-reflection coating consisting of a silicone-based hardened film layer and an inorganic dielectric substance to be coated on the surface layer of the single layer of primer obtained in this manner, we have previously proposed the anti-reflection coating layer in Japanese Patent Application No. 158769 (1982). , 5B-155451
However, the present invention can be violated in a similar manner. That is, when weaving a cured film mainly consisting of the components (■), (■), and (◎), the components (■), (■), and (◎) are as described below.

Component (1) is a mixture of 7L fine particles with a particle size of 1 to 100 μm, more preferably 7L fine particles with a particle size of 5 to 40 μm, dispersed in a solvent. Examples of the dispersion medium include alcohols such as methanol, ethanol, 1-gropanol, and n-butanol, methyl cellosolve, and ethyl cellosolve.

Seronlubes such as butylseronlube, carpitols such as methylcarpitol, methylcarpitol, butylcarpitol, or water can be removed. This component is indispensable for increasing the rigidity, moisture resistance, and durability of the cured film, as well as for obtaining affinity or adhesion with the antireflection film applied thereon. (In fact, as the amount of the ■ component in the cured film increases, the strength and hardness of the inorganic material deposited on it increases!) From this fact, this ■ component improves the density and hardness of the deposited material. It is thought that this amount is also effective in reducing the amount of 75% to 55% by weight of the components of the cured film at the heating stage.
:D Preferably, 75 weight percent to 50 weight percent is used. If the amount of this component (■) used is 75% by weight or more, hard ft [[[[cracks] will occur, and
If it is less than 5% by weight, adhesion to the antireflection film 1 will be insufficient, which is not preferable. Furthermore, the concentration of component (1) in the dispersion medium of 20 to 55 weight percent is stable and convenient for use.

Next, the compound containing 7 epoxy groups as an organic chain, which constitutes the @ component, has an organic residue of (-CI(1)-0
(However, %p and q are 1 to 6, and r is 1 to 2.

) is a silicon compound having the group t-. Specific examples of such compounds include dipropyltrimethoxysilane in r-glyside, r-grindquinpropyltriethoxysilane, r-glycidoxypropyl(methyl)trimethoxysilane, β÷5°4-epoxysilane, Hair Sil)
Examples include ethyltriethoxy 7ran. In addition, this alkoxy group is partially or completely hydrolyzed and partially dehydrated when used, so hydrolyzable groups such as alkoxy-7 alkyl, acyl, hydrogen chloride,
Acetoxy groups and the like are also essentially equivalent.

Although this compound may be used directly, it is usually used in water or in a solvent such as alcohol, ceasorp, or ketone.
It can be used by hydrolyzing mineral acids or organic acids as catalysts.

At this time, this component (2) is essential for increasing the durability and flexibility of the cured film such as silicone resin (from 25% by weight to 65% by weight). It can be used, but it is determined by the amount of ingredients used.

If (2) is less than 25% by weight, cracks will occur in the cured film, and if it is more than 65% by weight, the adhesion to the antireflection film will be poor.

Next, examples of the curing catalyst which is a compound of perchloric acid or perchlorate in (2) include zinc perchlorate, ammonium perchlorate, and oxazine perchlorate.

Potassium perchlorate, silver perchlorate, mercuric perchlorate, ferric perchlorate, tetraethylammonium perchlorate, tetra-n-butylammonium perchlorate, tetra-n-propylammonium perchlorate, Examples include perchlorate steel, sodium perchlorate + Jumium perchlorate, lead perchlorate, nickel perchlorate, barium perchlorate, hydroquinolamine perchlorate solution, magnesium perchlorate, lithium perchlorate, and the like.

The amount of ■ used is α mouth 0 for the total amount of both ingredients ■ and ■.
From 1% to 1% by weight, preferably from 10% to 15% by weight. If the amount of ◎ used is more than 1% by weight, cracks will occur in the cured film even during the desired low-temperature curing treatment, and if it is less than (Loot precious bar + - cent), sufficient hardness will not be obtained even with the desired low-temperature curing treatment. Moreover, the life of the coating liquid cannot be maintained, which is not preferable.

It is useful to use these spread products after diluting them with the various solvents mentioned above. In addition, this includes ultraviolet absorbers,
It is possible to add dyes, photochromic dyes, skin color pigments, etc., and the following can be added as necessary. Examples of the stabilizer include coordination compounds such as acetyl-natton, acetoacetate, acetic acid, and the like. Examples of the drying, leveling and anti-noise agents include various ionic surfactants, anionic surfactants, silicone surfactants, and fluorine surfactants. Also in history are metal coordination compounds, acid halides, and alkoxides.

It is also possible to improve the water resistance and refractive index characteristics of the cured film by adding fine oxide powder or the like. Examples of these are aluminum, delconium, and cobalt.

Vanadium titanium, mental chromium, manganese.

Magnesium 7ium, nickel acid chloride and acid bromide.

Examples include alcolade polymers, acetylacetone, chelate compounds of acetoacetate, chelate compounds such as lactic acid, oxalic acid, and tartaric acid, esters of organic acids, and fine powders and colloidal sols of oxides.

In addition, these include glycidyl compounds of polyhydric alcohols,
Glycidyl ester of polycarboxylic acid.

Examples include methods of increasing the hardness of the cured film by adding glycidyl ether of bisphenol A, various vegetable amine compounds, or alkali metal salts of organic acids. However, these are the main ingredients of the composition. ■
,■It should be used to the extent that it does not impair the properties obtained from the work◎.

The basic characteristics aimed at by the present invention are those that are manifested by ■) Work ◎, which has already been described in the present invention.

The ink method can be selected from the various methods described for coating with the primer composition. This curing reaction progresses on heating and can easily form a cured film, but in particular, the uninvented silicone-based hard coat liquid is suitable for temperatures ranging from 80°C to 11QC%! L (ij: ?
By curing in low-temperature hot air at 0°C to 100°C for 50 to 180 minutes, it is possible to obtain the same hardness and other properties as conventional high-temperature heating type silicone hard coats (80°C to 150°C). It is possible. This is particularly suitable when the high refractive index plastic lens of the present invention, which is susceptible to thermal deformation etc. at high temperatures of 110° C. or higher, is used as a base material. Furthermore, treatment with infrared rays is also effective as preliminary curing. The lens obtained in this way may be proceeded to the next step as it is. In addition, cleaning or chemical treatment with acids, alkalis, solvents such as alcohol and Freon, ozone gas, etc., or surface activation using physicochemical means such as activated gases such as plasma, electron beam irradiation, and ultraviolet irradiation. is also effective.

The present invention can be achieved by forming an antireflection thin film made of an inorganic dielectric material on the surface layer thus obtained.

That is, vacuum distillation method, ion sputtering method, S
10. S10. , Si3N4. TiO2゜T i O,
, ZrO,, Al, 03, MgFl, Ta20
By laminating single or multilayer thin films made of a dielectric material such as a, a layer is formed to suppress reflection at the interface between the atmosphere and the lens.

Moreover, the optical film thickness is λ/4 (λ=450 to 650 nm)
single layer, or λ/4 - λ/2 - λ/4 or λ/4
-λ/4 - λ/4 three-layer multilayer structure with different refractive index 1@
It is useful to have a coat, or even a multilayer coat to suppress internal reflection. The refractive index at this time is determined by a material close to a physically calculated value, but for example, in the case of a single layer, a material having a refractive index equal to the square root of the refractive index of the base material is most preferable.

The lenses obtained in this way have excellent scratch resistance, heat resistance, water and oil resistance, adhesion and durability, and because they suppress surface reflection, they are prone to flickering (increased transparency. Thin and light. A highly practical high-refractive-index plastic lens can be obtained.This treatment can also be applied to plastics other than those mentioned above.
That is, the primer of the present invention can be used for special glass materials such as polycarbonate, As resin, ABS resin, polystyrene, polyethylene terephthalate, acrylic resin, etc., which cannot be treated with a conventional hardening layer and are unsuitable for high-temperature hardening treatment. and silicone-based cured membrane 1@ can be utilized.

[Effect]

With the above structure of the present invention, between the surface of the high refractive index plastic lens base material and the silicone-based cured coating layer containing a curing catalyst which is a compound of perchlorine #i or perchlorate,
Apply a single layer of primer made of acrylic or methacrylic compound and aromatic vinyl compound to act as an eyebrow layer (g!adhesive) and buffer 1- (impact resistance). I found out.

Furthermore, it has been discovered that the silicone-based hard coat composition, after curing, can be firmly attached to the upper antireflection layer made of an inorganic dielectric material.

Historically, we have discovered that by using a latent catalyst in the silicone hard coat composition, sufficient hardness can be obtained even during low temperature curing treatment.

In other words, the present invention is believed to be based on the effect of excellent bamboo dust properties and hardness between each layer from the base material to the anti-reflection layer, and in addition to this, the present invention has been achieved that fully satisfies various durability. It was done.

〔Example〕

Hereinafter, the present invention will be explained in detail based on Examples, but the present invention is not limited to these.

In addition, parts in the examples represent parts by weight.

Example 1 (1) High refractive index plastic lens made of H styrene 50
part, 2,2-bis(5,5-dibrom,4-methacryloylox7ethoxyphenyl)propane a EL S
Part r diethylene glycol bisallyl carbonate za
parts, t-butyl peroxoneodecanate 1.5 parts, 2 parts
2 parts of -(2/-hydrooxy7-5'-methylphenyl)benzotriazole α are mixed and stirred. Insoluble matter in this mixed solution was removed using a filter, and solution A was injected into a space formed by a gasket made of soft polyvinyl chloride and two glass molds. Next, at 60℃ for 4 hours, 5
Linearly from 0℃ to 50℃ for 10 hours, from 50℃ to 70℃
2 Uf darkness linearly to °C, 1 hour at 70 °C, 2 Uf at 80 °C
After heating for a period of time, the gasket and glass mold were separated. Furthermore, the obtained lens was annealed at 110° C. for 2 hours to remove distortion inside the lens. The lens thus obtained had a refractive index of 1.595 and an Abbe a of 52, making it suitable as a high refractive index plastic lens for optical use. This lens is used as a base lens for a high refractive index plastic lens used below.

(2) Preparation of primer coating solution and coating hardening In a 5J SUS autoclave equipped with a stirrer, add distilled water a.
o ag, emulsifier (manufactured by NOF ■).

The mixture was kept at 30-55° C. and stirred at 40-60 revolutions per minute to dissolve the contents. Lay down, K, S, 0. 4
part was dissolved. Next, 500 parts of methyl methacrylate, which had been distilled to remove the polymerization inhibitor, was mixed with 500 parts of styrene treated in the same manner, and 5 parts of n-dodenlumerkabutane was dissolved in the autoclave. After replacing the atmosphere in the container with a sufficient amount of nitrogen, stirring was started at 500 revolutions per minute.

The speed was then reduced to 50 revolutions per minute, the internal temperature was heated to 80°C, and the reaction was carried out for about 6 hours and 1 hour.

After the reaction was completed, a solution prepared by dissolving 5 parts of sodium dimethyldithiocarbamate in 100 parts of distilled water was injected as a stop solution to stop the reaction.

The emulsion solution thus obtained had a solid content concentration of 27% and a particle size of 500 mμ or less. Further, the molecular weight of this polymer approximated by the viscosity method was about 100,000.

Next, add 50 parts of this emulsion solution. Stir (
p, 60 parts of methanol was added, followed by 50 parts of methyl ethyl ketone, dimethyl formamide 109.7 recon type surfactant (manufactured by Nippon Unicar Aji, trade name "Y-700").
Add 0.005 parts of 2") to make a primer solution.

This primer solution was thoroughly filtered through a membrane filter with pores of 1 μm, and then applied to the crystal phase lens obtained in (1) by a dipping method. Incidentally, by setting the pulling rate at this time to 10 c1n per minute, a film having a thickness of 0.5 μm after curing can be obtained.

The coated lenses were cured and baked in a hot air drying oven at 100°C for 1 hour to obtain a lens with a good appearance. In a flask equipped with a hardening stirrer, ingropanol-dispersed colloidal silica (Catalysts & Chemicals Industry ■m″O) was added under a nitrogen atmosphere.
8C! Add 550 parts of AL-1452 (solid content concentration 50%), 220 parts of isopropanol, and 108 parts of γ-grid Φdipropyltrimethoxysilane with stirring, and add (52 parts of 105N hydrochloric acid for 50 minutes). Next, 111 parts of the silicone surfactant mentioned above was added to obtain a coating.This solution was heated at -20°C for 2
The mixture was left to ripen for 4 hours, and then 025 parts of magnesium perchlorate was added with stirring, and the dissolved o, t-
The mixture was left to stand at 20° C. for 24 hours to mature, and a coating solution was obtained.

Subsequently, the coating solution was applied to the lens obtained in step (2) using a dipping method. The pulling speed at this time was 20 m/min. This lens is dried in a hot air drying oven.
It was heated and cured by keeping it at 100°C for 2 hours. The cured layer thus obtained is hard, transparent, and has good adhesion. The thickness of this cured layer, including that of the previous primer layer, was 2-6 .mu.m.

(4) Formation of anti-reflection layer The lens obtained in step (3) was exposed to Ar gas plasma at an output of 200 W for 50 seconds in a vacuum, and then vacuum evaporated to form the structure shown in Figure 1. It has an anti-reflection layer. That is, from the lens side to the atmosphere side, zro, ,
41-thin films of A1103, ZrO2, and Sion are formed, and their thicknesses are, in order, Zr01 and A1! O.

The measured hood thickness is λ. 741st order ZrO, is λ. /4. Top lm17) SiO, is λ. /4. In addition, λ. is 510 parts m.

The lens obtained using this method has low surface reflection and excellent scratch resistance. This reflection characteristic is shown in FIG.

(5) Test and evaluation results The characteristics of the obtained lenses were evaluated by the method described below. The results are shown in Table 1.

(a) Abrasion resistance: A load of 1 kg was applied to the fl OQ Q O, c teal f)-, and the surface was rubbed 10 times back and forth, and the degree of scratches was visually evaluated by dividing into small grades.

A: All (W!, not included) in the range of 'l mX 5 sub.

B: 1 to 10 scratches within the above range.

C: 10 to 100 seagulls are found within the above range.

Ll: There is countless hot water on the surface, but a smooth surface remains.

FX=There is no smooth surface left because the hexagram is attached to the surface.

(1)) Water resistance and chemical resistance: The surface condition was examined by immersing it in water, alcohol, and kerosene for 48 hours.

(c) Acid resistance, detergent resistance: 1lINjfi acid work 1
% Mamaremo/(manufactured by Lion Oil IIIa) aqueous solution for 12 hours, and the surface condition was examined.

((1) Weather resistance: Using a xenon long life fade meter (manufactured by Suga Test Instruments), the surface condition was examined after exposure for 400 hours.

<13)) Adhesiveness: The adhesion between the cured layer and the lens or between the antireflection film and the cured film was determined by the cross-cut tape test method in accordance with J-Tech SL+-0202.

That is, using a knife, incisions are made on the lens surface at intervals of 111w to form t-10 1- squares. Next, after strongly pressing cellophane laminated tape (Nitto Chemical Co., Ltd. 1 Cellotape) on top of it, and peeling it off by pulling it in a 90° direction from the surface, use the remaining squares of the coating film as an indicator of layer quality. And so.

(f) Durability: Considering that durability is essentially the persistence of adhesion, we conducted the above-mentioned cross-cut tape test and evaluated the products tested in a) to d).

(g) Heat resistance (cold/hot cycle resistance): Lens 1701
:: It was stored in warm air for 1 hour and its appearance was examined. Another -5℃
A cycle of 15 minutes and 15 minutes at 60° C. was repeated 5 times, and the appearance and cross-cut tape test were conducted, and those with no peeling of the coating film were designated as fish.

(h) Impact resistance: A steel ball drop test was conducted based on the FlIA standard. That is, a steel ball of approximately 16.42 mm was allowed to fall naturally toward the center of the lens from a height of 127 m, and the lens was checked for cracks. This test was repeated three times, and those with no abnormal appearance were considered good. The center thickness of all lenses used in this test was 2fi.

Example 2 (1) Manufacturing example 1 of high refractive index plastic lens
In, diethylene glycol bisallyl carbonate, 'S? The process did not use 2-(2'-hydroxy-31-methylphenyl)hencytriazole, and t-
A good high refractive index lens was obtained in the same manner as in Example 1 except that 1.5 parts of t-butyl peroxy 7 biparate was used in place of butyl peroxy 7 neodecanate.

(2) Preparation of primer coating solution, coating and curing Commercially available acrylic-styrene water-based emulsion/F450 (Showa Kobunshi ■ product).

(solid content concentration 45%). That is, 20 parts of pure water and 20 parts of methanol were added to the aqueous emulsion under strong stirring for 20 sKh, and then 7 parts of ao of 1-ethyl cellosolve were added.
Add 10 parts of 0 pyrene glycol methyl ether and mix. Subsequently, para-1-butylphenylsali/late 2-
5 parts and a stabilizer for polymers (manufactured by Sankyo ■, trade name 6 Sanol LS-770'') (5 parts of L), and further 2 parts of ultraviolet absorber 2-(2'-hydroxy-3'-methylphenyl)benzotriazole α After adding and sufficiently dissolving, -
Then, apply a primer coat.

This blood was applied and cured on the lens obtained in this example in the same manner as in Example 1.

(3) Preparation of silicone resin coating solution Coating and curing To 100 parts of the coating solution obtained in (3) of Example 1, 20 parts of acetylacetone and tetraoctylene glycol titanate (Nippon Soda ■, trade name "TNi-") were added. 55″
) 20 parts of 10fR$*ft57t*cytin polymer (field product name "TBT-10") were added to make a homogeneous solution. This material was coated and hardened on the previously obtained lens in the same manner as in Example 1, and the thickness of the cured film obtained in this manner, including the primer, was 55 microns. Furthermore, the lens was good, with no interference between the lens base material and the hard coat.

(4) Formation of antireflection layer The obtained lens was treated with 200 W oxygen plasma for 50 seconds, and then an antireflection layer having the structure shown in FIG. 30 was provided by vacuum evaporation.

That is, from the lens side toward the atmosphere side, 810. .

A five-layer thin film of Zr01, 5iOt, Zr0t, and 5i02 was formed, and the thickness was determined in order from the lens side as El i
O,, ZrO3 and S10. The measured thickness is λ. /4.
The long ZrO is λo/4. 5102 of the top li is λ. /
It is 4. In addition, λ.

is the same as the one explained earlier.

FIG. 4 shows the surface reflection characteristics of the lens obtained in this manner.

(5) Test and evaluation results The lenses obtained in this manner were evaluated in the same manner as in Example 1. The results are shown in Table 1.

! 11! Example 5 In preparing the +11 primer solution of Example 2, as a commercially available acrylic-styrene aqueous emulsion?
The same procedure as in the example was carried out, except that Cevian 4719 (Daicel Chemical Industries, type product, solid content concentration 50%) was used in the -450 glue, and no salt or para-t-butylphenylsali 7late was added. A primer solution was obtained.

A high refractive index plastic lens of the present invention was obtained fc in the same manner as in Example 1 except that this solution was used as a primer solution.

The evaluation results of this lens are shown in Table 1.

Comparative Example 1 A lens was obtained in the same manner as in Example 1 except that the primer film described in (1) was not applied. The evaluation results are shown in Table 1.

Comparative Example 2 In the same manner as in Example 1, except that a commercially available polycarbonate primer (Shin-Etsu Chemical ■, product name 1 Primer PC'') was used for the primer solution described in (1), A lens was obtained. The evaluation results are shown in Table 1.

〔Effect of the invention〕

As described above, the effects of the present invention are as follows: abrasion resistance, heat resistance, water resistance, oil resistance, weather resistance, durability, etc.
It is possible to manufacture high refractive index plastic lenses with excellent film adhesion, and it is also possible to add an anti-reflection layer.
BS The object of the present invention is to provide an excellent high refractive index plastic lens that is thin and has a practically indispensable surface scratch resistance and prevents flickering due to surface reflection. In the first history, the lifespan of the coating liquid was further improved, leading to cost reductions in production management.In addition, it was engineered to have a silicone-based hardened coating layer that can be cured at low temperatures, improving surface accuracy and lens power through thermal deformation. The object of the present invention is to provide an excellent high refractive index plastic lens that does not have an adverse effect on the objects. Particularly in the field of eyeglass lenses, the above-mentioned characteristics are highly desired, and the effects obtained by the present invention are significant.

In other words, although it goes without saying that lenses are weak, even strong optic lenses are thin, light, and resistant to cracking. It has become possible to create eyeglass lenses for even more applications.
This has the great effect of increasing demand.

This property can also be used to create cameras, telescopes, and light beam concentrators.

It is expected to have a wide range of applications, including can plates for measuring instruments, transmission glasses, watch glasses, and optical lenses in general.

[Brief explanation of drawings]

FIG. 1 shows the olfactory structure of the lens in Examples 1 and 5 □□□. Ll is the base lens, AI is the primer m, B
l is a hardened layer, Ql is an antireflection layer, and thin film layer 11 is Z.
r01, layer 12 is A12o, , J is Zr
01, layer 14 is S10. It is. FIG. 2 is a diagram showing the spectral reflection characteristics of the lens of Example 1, where the horizontal axis shows the wavelength of light and the vertical axis shows the light reflectance of one surface. FIG. 5 is a diagram showing the film structure of a lens in Example 2. B5 is a base lens, A5 is a single layer of primer, B5 is a hardened layer, C5 is an antireflection layer, the thin film layer 51 is S i O,
, layer 52 is ZrO2, 7@ss is 5102, layer 54 is ZrO2
rO,, the layer 55 is Sin, the 41st threshold is a diagram showing the spectral reflection characteristics of the lens of Example 2), the horizontal axis is the wavelength of light, and the vertical axis is the light reflectance of one surface. shows. that's all

Claims (10)

[Claims] (1) Acrylic and/or methacrylic compounds and aroma A resin film made of a group-based vinyl compound as a product is applied as a primer layer, followed by a silicone-based hardening film layer containing a hardening catalyst that is a compound of perchloric acid or perchlorate, and then an inorganic dielectric film is applied on the surface layer. A high refractive index plastic lens characterized by having an anti-reflection layer made of a substance. ▲There are mathematical formulas, chemical formulas, tables, etc.▼・・・・・・・・・
[I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼・・・・・・・・・
[II] (In the formula, R_1 represents hydrogen or a methyl group, X^1,
X^2 is a halogen excluding fluorine, m+n is an integer from 0 to 8). (2) The high refractive index plastic lens according to claim 1, wherein the primer layer is a primer whose main component is a copolymer of acrylic and/or methacrylic compound and styrene. (3) The primer layer is mainly composed of a copolymer of acrylic acid or methacrylic acid ester and styrene)
3. A high refractive index plastic lens according to claim 2, which is obtained by applying an aqueous ionic or anionic emulsion and curing it with heat. (4) In addition to the main components of the emulsion, one or more polymerizable monomers having a residue selected from a hydroxyl group, a carboxyl group, an amino group, an imino group, an amide group, an acetyl group, and an epoxy group are added as a nonvolatile component. 4. The high refractive index plastic lens according to claim 3, wherein the high refractive index plastic lens contains less than 5% by weight. (5) The silicone-based cured coating layer has the following main components:
The high refractive index plastic lens according to claim 4, which is the following (A), (B) and (C). (A) Colloidal silica with a particle size of 1 to 100 millimicrons. (B) General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (However, in the formula, R^4 is an organic group R^5 containing an epoxy group.
is hydrogen, methyl, ethyl, propyl, vinyl group, R^
6 represents a hydrocarbon group having 1 to 4 carbon atoms, an alkoxyalkyl group, or an acyl group having 1 to 4 carbon atoms, and a is 0 to 2. compound and/or its hydrolyzate and partial condensate. (C) A curing catalyst that is a compound of perchloric acid or perchlorate. (6) The silicone-based hardened coating layers (A) and (B) are calculated as SiO_2, ▲Mathematical formula, chemical formula, table, etc.▼, and (A) is 75% by weight to 35% by weight, ( B) is 25 weight percent to 65 weight percent, and (C) is 0.001
6. A high refractive index plastic lens according to claim 5, wherein the high refractive index plastic lens is from 1 weight percent to 1 weight percent. (7) The high refractive index plastic lens according to claim 5, wherein the epoxy group of component B of the silicone-based cured coating layer is a glycidyl group or an epoxycyclohexyl group. (8) The antireflection layer made of the inorganic dielectric material is made of SiO
, SiO_2, Si_3N_4, TiO_2, ZrO_
2. The high refractive index plastic lens according to claim 1, which is made of a single-layer or multi-layer thin film made of one or a combination of two or more selected from the group consisting of Al_2O_3 and FgF_2. (9) A patent claim in which the lens base material is a copolymer consisting of 20 to 80 parts by weight of the monomer represented by [I] and 20 to 80 parts by weight of the monomer represented by [II]. A high refractive index plastic lens according to item 1. (10) In addition to [I] and [II] of the lens base material, as a third monomer, a diallyl compound, a diallyl carbonate compound, a di(meth)acrylate compound, and other polymerizable monomers are added in an amount of 0 to 20% by weight of the entire resin. A high refractive index plastic lens according to claim 9, including in the range of %.