JPS60103347A - Synthetic resin photochromic lens - Google Patents

Abstract

PURPOSE:To obtain a titled lens which is highly resistant to wear, heat, etc. by forming an org. hard coat contg. an org. compd. having photochromic performance on the surface of a plastic lens consisting of a specific copolymer resin and having a high refractive index. CONSTITUTION:(A) A monomer expressed by the formula I (R<1>, R2 are -OCH2CH2-, etc.; R<3> is O, etc.; X is halogen except fluorine; (a), (b) are 1-4; (m), (n) are 0-4) and (B) the monomer expressed by the formula II are copolymerized. The coating compsn. consisting of colloidal silica having 1-100mmu grain size, the hydrolyzate or partial condensation product of the silicon compd. expressed by the formula III (R<4> is an org. group; R<5>, R<6> are hydrocarbon, etc.; (a), (b) are 0, 1, 2), a polyfunctional epoxy compd. and a monomer of >=1 kind among the formula IV, the formula V and the formula VI (R<7>, R<8>, X are chlorine, etc.; R<9>- R<14> are aryl) is coated on the surface of a high refractive index resin lens consisting of the resulting copolymer resin, by which the titled lens is obtd.

Description

Detailed Description of the Invention [Technical Field] The present invention provides a synthetic resin high refractive index lens that is easy to manufacture and has vague optical properties, and has a photochromic function on the surface, and also has surface hardness and durability. The present invention relates to a synthetic resin photochromic lens characterized by being provided with a film having excellent surface properties such as abrasion resistance, heat resistance, hydrothermal resistance, chemical resistance, and stainability.

[Prior art]

Synthetic resin lenses, especially diethylene glycol bis(allyl carbonate) resin lenses, are safer (impact resistance), easier to process, more fashionable (resistant to staining), and have anti-reflection technology compared to inorganic glass lenses. , No.
With the development of the 4-branch technique E, it has become rapidly popular in recent years. The plasticization of the 11-lens λ lens has the potential to be used as a higher-grade lens, 1) a thin plus-F-7') lens made of a high refractive index resin material, 2) a photochromic [94 ``It goes without saying that plastic lenses that have both of these characteristics are desirable.

1) Conventional technology for high refractive index resin materials The refractive index of diethylene glycol bis(allyl carbonate) polymer is 1.50, and several technical proposals have been made to overcome this drawback. There is. For example, JP-A-5/L
In JP-A-41965, a copolymer of diethylene glycol bis(allyl carbonate) and ``22 dimethyl 10 note, and in JP-A-54-77/1986, a copolymer of diethylene glycol bis(allyl carbonate) and 4-iodostyrene. JP-A-58-15513 discloses a copolymer of diallyl terephthalate or diallyl isophthalate and methyl methacrylate prepolymer as a lens material.The problem in manufacturing lenses using these copolymers is that they are completely reactive. Different allyl group and (
The method is to react the meth)acrylic group or (gupinyl group).In other words, the acrylic or vinyl group, which has a fast reaction rate, polymerizes first, and the acrylic group, which has a slow reaction rate, not only does not polymerize later, but also the allyl compound. It is extracted as an unreacted product without being completely polymerized, or it is polymerized first (
Since meth)acrylic compounds or vinyl compounds are monofunctional monomers, they are 100% polymerized and completely incorporated into the polymer chain.'1. t1. It is impossible to extract the monomer, and it is partially extracted as a monomer and is thermally unstable. Furthermore, these techniques are unsatisfactory because the refractive index is not sufficiently high.

Furthermore, in JP-A-55-13747, for example, a lens material made of a copolymer of bisphenol A dimethacrylate and phenyl methacrylate or benzyl methacrylate has been proposed.
The reaction between acrylic groups and vinyl groups is very difficult to control during lens manufacturing; in other words, the reaction is too fast, so even if the casting process is carried out in an atmosphere,
Even if you do it underwater, it's fli! In addition, vinyl groups and (meth)acrylic groups are extremely sensitive on the reaction surface, making them highly susceptible to external influences. The disadvantage is that it is easily susceptible to polymerization and it is very difficult to control conditions other than polymerization conditions. Furthermore, since the second monomer is a monofunctional monomer, it also has the disadvantages of poor thermal stability and organic solvent resistance due to unreacted monomers, as in the previous example. 57-54901. JP-A-58-1
In 8602, we proposed a copolymer of a styrene monomer, a di(meth)acrylate with a nuclear halogen-substituted aromatic ring, and an allyl compound or a trifunctional di(methacrylate) as a total lens material.Using these technologies, we have developed an excellent synthetic resin material. Although it is possible to obtain lenses with high refractive index, they still have the disadvantage of making the process extremely complicated in terms of the difficulty in controlling the polymerization reaction and the completion of the polymerization reaction. However, even though the lens is dyed using diethylene glycol bis(allyl carbonate), it has another drawback in that it is much more complex than lenses made of diethylene glycol bis(allyl carbonate).

2) Conventional technology for lenses with photochromic function 2'7 Synthetic resin lenses with otochromic function have functional aspects (light attenuation rate 1 coloring speed, fading speed, durability of dimming performance), coloring due to light absorption In terms of performance, they are insignificantly inferior to inorganic glass photochromic lenses.Also, technologically speaking, research is underway to fully improve the abrasion resistance and durability of plastic lenses, as well as research into materials that exhibit all photochromic functions. Although a number of separate proposals have been made, no research has been conducted that comprehensively considers both, and a photochromic lens with excellent wear resistance and durability has not yet been established.

Typical examples of techniques for improving the abrasion resistance etc. of plastic materials are JP-A-50'10674 + JP-A-RO5.
1-42752. JP-A-56-99263゜VSF-3
No. 986997, etc.

On the other hand, the technology related to photochromic materials (lenses) is d'ke Kosho A3-12716. Tokuko Sho 45-2889
3. ! Special public service 116-1106. Japanese Patent Publication No. 48-8917
9. Japanese Patent Publication No. 51-45541. Japanese Patent Publication No. 54-11085
4, Japanese Patent Publication No. 55-121412, Special Publication No. 57-4924
4. % Publication No. 57-55747゜ Japanese Patent Publication No. 57-13614
Many of them have been disclosed in the 5th class. In order to impart photochromic properties 11H to synthetic resin materials using these techniques, molecules or particles exhibiting photochromic properties consisting of organic or inorganic substances are added to the synthetic resin, or they are bonded to polymer chains. However, resin and photochromic materials are limited to pendant polymer method, heat transfer method, V-immersion lamination method, etc. It's still there.

Furthermore, the method of adding a photochromic substance to the resin is not preferable in terms of the appearance of the lens. When using a casting method like this, it is generally used rL, /, :)
Peroxides such as diimpropyl peroxydicarbonate deactivate most photochromic molecules.

In this way, the current manufacturing process and f! ! A high refractive index lens made of synthetic resin that has both the characteristics of a round shape, photochromic performance, surface hardness, and abrasion resistance.

[Purpose] The purpose of the present invention is to solve all of the above-mentioned problems comprehensively.
It was done for the purpose of deciding on a child.

In order to obtain a synthetic resin high refractive index lens, we use a compound that has a relatively slow reaction rate, is easy to control the reaction, and is less affected by various factors, making it very easy to control the copolymerization process using only allyl monomers. It is to use sound. (By making all monomers bifunctional, it is possible to minimize unreacted monomers that cannot be incorporated into the polymer chain and improve incorporation properties such as heat resistance and solvent resistance.) ,Fourth, for another purpose, ηi, ff whose general formula is represented by [l]
By introducing a carbonate group into the t-body, Wit′
11! Another major objective is to improve adhesion to hearts (particularly silicone hard coats) and inorganic substances. Since the abrasion resistance of the resin according to the present invention is almost equivalent to that of polymethyl methacrylate or polycarbonate, a coating such as an organic hard coat or an inorganic hard coat or an anti-reflection coat is required on the lens surface. Baking soda is a key point in improving sex.

Adds photochromic function, and also has surface hardness, abrasion resistance, surface heat resistance, hot water resistance, and ltI mulberry quality.

In order to provide surface characteristics such as dyeability, the present invention uses an organic hard coat and an organic compound having a photochromic function dispersed in the hard coat. Existence of the present invention 4. The hard coat layer has the property of forming a strong and dense layer on the surface of the high refractive index lens made of the synthetic resin 11 described above. This hard coat layer has surface hardness, abrasion resistance, heat resistance, and hot water resistance.

Contains surface properties such as mulberry resistance and stainability. Here, surface hardness and stainability are contradictory performances, and this tL is the E component of the patent P blue water range depending on the purpose. In other words, it can be freely adjusted using a polyfunctional epoxy compound. Furthermore, the organic hard coat of the present invention is largely dependent on the functional stability of the photochromic compound.

Compound u, (m) exhibiting photochromic performance.

These are benzobyrillosvirane and dithizone mercury compounds represented by the structural formulas [IV] and [v], and these compounds have excellent light reduction rate 2, coloring speed, fading speed, and durability of dimming performance. In terms of performance, especially in the hard coat, durability is significantly improved.

〔overview〕

That is, the present invention provides a coating composition containing the following O, D, BE, F, G'i as main components, the surface of a high refractive index lens made of a synthetic resin copolymerized with a comonomer having By2 as a main component. This article is about a photochromic lens made of synthetic resin, which is coated and cured.

A, one or more types of sokuryutai whose general formula is CI) (in the formula, L'l', R is t -0-011, C!H, -, -
0-OH, OH, -.

X represents a halogen 7 excluding fluorine, a and b each independently represent an integer of 1 to 4, and m+l; I-1'L each independently represents an integer of 0 to 4. ) B. One or more types of 1 yen # world body represented by the general formula [11]
1 1 C[l] () Colloidal silica D whose grains are 1 to 100 mμ, a hydrolyzate or partial condensate of one or more silicon compounds whose general formula is represented by [■].

(In the formula R4 (a vinyl, amino, imino, epoxy.

An organic group containing at least one group selected from (meth)acryloxy, phenyl, alkylthiol, and thiol group, R5 is hydrogen, a hydrocarbon group (C, ~c,) and a halogenated hydrocarbon group (at~06), R 'U hydrocarbon group (01
~ C), alkoxyalkyl group (at~c, ) and acyl group (C2~C4), a is 0,1*U2. b[0,
1 or 2 and a+bs; 2)■, polyfunctional epoxy compound Fo, the general formula is (m:], C■], one or more monomers represented by CVD, [■) R''-N= N-C=N-NHR・2 [v] R11-N=N-C=N-NHR” 1 11 cloud [■j ([N) &1 In the formula R?
tr.

Hydrogen, fluorine, 11 (mine and bromine BR is hydrogen, fluorine.

At least one or more substituted compounds selected from chlorine, bromine, nitro group and methoxy group, [VE, (Vl:]
is a dithizone compound, where R9 to R''n are the same or different aryl groups, and X is fluorine, chlorine, or bromine.

It is a phenyl group or a naphthyl group, some or all of which have the following substituents. Fluorine.

Salt, central, iodine, hydrocarbon group (C□~C4), halogenated argyl (C+~C6), alkoxyalkyl group (C1~C^), carboxyl JLi (0,~C6)
and carpoquin alkylnol! (n+-Cs)+
Sulfonyl group, cyano group.

Catalyst for forming halogenated alkylsulfonyl group (C1 to C6) and acyl group ((!, -0.)1o,1IIIlj The present invention will be described in detail below.

First, a high refractive index lens made of synthetic wood 11 will be described.

Since most of the monomers whose general formula is represented by (1) are solid at room temperature, it is necessary to decompose the II'IB component as the B component and the trifunctional diallyl compound as the third component. The composition ratio of A and B is the refractive index of the resin lens to be obtained, the brightness, and the N color.

Impact resistance, adhesion to axial heart coat, flame retardant.

It is better to decide from the viewpoint of balance with durability.

Monomer A can exhibit the highest refractive index.

As the halogen for nuclear substitution represented by the general formula [1], chlorine, bromine, and iodine, excluding fluorine, are used, but bromine is preferable in view of the balance between refractive index amplifier and durability. The content of component A depends on the solubility in component B, or the mixture of B DL and a functional diallyl compound as a third component, but it is important that it is a high refractive index resin, that it improves the adhesion to the organic coating, Considering the improvement of flame retardancy, 25 to 95% is preferable.

Typical examples of component A include 2.2-bis(4-allylox7carponyloxy-3.s-dichlorophenyl)furopane, 2.2-bis(4-allyloxycarbonyloxy-3,5-dibromo) phenyl)propane, 7,2-bisC4-(2-'rallyloxycarbonyloxyethoxy-3,5-dichlorophenyl]propane, 2,2-bisC4-(2-allyloxycarbonyloxyethoxy)-3,5 -dibromophenylg L7 van, 2,2-bis(4'-(2-allyloxycarbonyloxyethoxy)-2,3,5゜6-titrabromophenyljpropane, 2,2-bis[4-
(2-allyloxycarbonyloxypropoxy)-1
, 5-dibromophenyl 1-propane, 2,2-bisCA
-(3-allyloki7carbonyloxybrobogyshi)
-3,5-dibromophenyl 1propane, 2,2-bis[:4-(3-(2-allyloxycarbonyloxyethoxy)ethoxy)-3,5-dibromobuenyl]probane, 2,2-bis(/1 -(3-allyloxycarbonyloxy-(2-hydroxy)-propoxy)-3
, s-dibromophenyl 1-propane, bis(4-allyloxycarbonyloxy-3,5-dibromophenyl)
sulfide, bisCd-C2-allyloxycarbonyloxyethoxy)-5,5-dibromophenyl]sulfide, bisC4-(2-allyloxycarbonyloxyethoxy)-3,5-dichlorophenyl]sulfide.

Bis[4-(2-allyloxycarbonyloxyethoxy)-s,5-dibromophenyl]sulfone, bis[4
-(2-allyloxycarbonyloxyethoxy)-3
,5-cyflomophenyl]ether, bisCA-(2-
Examples include allyloxy7carponyloxyethoxy)-3,5-dibromophenylcomethane.

In addition, as component B, there are diallyl orthophthalate r diallyl isophthalate, sial terephthalate, and -
Although it is possible to form a lens by polymerizing only the 6B component, which can be used as a ridge or in a mixture of two or more types,
The cause is not clear, but the polymer turns yellow and forms a dense layer with the organic coating film.

The impact resistance is also poor and the lens material (which cannot be formed, the B component has no effect on the material). In addition to the OT ability, the refractive error of the A component is also lowered.
Because the B component is a diallyl compound, reaction control is relatively simple, and because it is trifunctional, there are few unreacted monomers that do not bind to the polymer.

The content of component B should be at an appropriate concentration of s ~ 75]; if it is too large, it may cause coloring, poor adhesion to the organic coating, and poor impact resistance. It is fully possible to add a third component, a diazine compound, to the components to improve the characteristics 9 functions as a lens.

For example, diethylene glycol bisallyl carbonate is added as a third component to improve impact resistance and light resistance.

It is possible to increase the overall refractive index by adding monomers such as l-4fr: naphthalene dicarboxylic acid diallyl ester, and by adding tartrate diallyl ester to improve the adhesion of the organic hard coat film. It is also possible to improve the adhesion with the organic or organic coating film, and various other properties can be added by adding sial esters of dicarboxylic acids.

The synthetic resin lens according to the present invention has a high refractive index, easy control of lens fabrication, and good adhesion with the organic coating because all monomers can have a crosslinked structure.
Bath resistant agent 1<IE, has good heat resistance, durability in daily life, cutting workability, dimensional stability, is flame retardant due to component A, and is an excellent small lens with high refraction.

The high refractive index lens according to the present invention is obtained by template polymerization of comonomers containing A and B'i as main components in the presence of a radical polymerization initiator. The radical association initiator is not particularly limited and known ones can be used, but hydroxides such as t-butyl hydroperoxide, di-t-
dialkyl peroxides such as butyl peroxide, diacyl peroxides such as benzoyl peroxide, naha oxydicarbonates such as diisopropyl peroxydicarbonate; peroxy esters 9 ketones such as -t,t-butyl peroxypivalate There are peroxides such as peroxide and peroxyketal, and azo compounds such as azobis(imbutyronitrile). Monomer group.I+Z,
Although it cannot be definitively specified as it varies depending on the case, etc., 01
~5. It is preferable to use 11' Tlij beam base ((4). It is also possible to initiate polymerization with light energy such as ultraviolet rays and γ rays, or radiation. The lens is obtained by a known casting method, i'L;':), that is, two glass molds designed to give the lens power, two glass molds, and two glass molds. Thick hair: Can be obtained by a combination of elastomer gaskets designed to obtain ?nil by injecting the monomer containing a radical association initiator and heat curing, etc.).

Conditions such as heat curing temperature vary depending on the blending ratio of monomers and the type and concentration of the polymerization initiator used, but in general, heating starts from a temperature of about 60°C and finishes at a temperature of about 80 to 130°C. It is desirable to do so.

It is also desirable to polymerize gradually over a long period of time at low temperatures.

It is also possible to prepolymerize the entire monomer mixture in the presence of a polymerization initiator and increase the viscosity of the mixture before injection. This preliminary mold@ can not only reduce the volumetric shrinkage of the monomer but also prevent liquid leakage from the cavity.

Incidentally, when carrying out the casting process, an ultraviolet absorber is added to the monomer mixture in order to impart various properties to the lens or to improve the process. Additives such as antioxidants, antistatic agents, various stabilizers, p4i # type agents, etc. can all be used as required.Next, each component of the coating composition of the present invention will be described.

Colloidal silica with a particle size of 1 to 100 mp is a polymeric acid anhydride silica completely dispersed in a dispersion medium such as water, alcohol, or cellosolve.
It is manufactured by a well-known method and is not commercially available.
), those with a thickness of 5 to 40 mμ are particularly useful in carrying out the present invention, and the C component has the necessary 14 wear resistance,
It is an important component for the machinability and stability of photochromic materials.

A silicon compound, represented by the general formula Cu1l) of DIN, is an essential component for the adhesion between the liquid film and the high refractive index resin containing A and B as main components, and is also removable.

” Effective in improving abrasion resistance and stainability. Specific examples include vinyltrimethoxysilane, vinyltriethoxysilane, and vinylacetoxysilane.

γ-Aminopropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropyldimethoxysilane, β-(3゜4-epoxycyclohexyl) Ethyltrimethoxysilane, γ-(3,a-epoxycyclohexyl)ethyltriethoxysilane, γ-
Metac IJ Oxypropyltrimethoxysilane, γ-
Methacryloxybrobylmethyldimethoxysilane, γ-
Mercaptogropyltrimethoxysilane, phenyltriacetoxysilane, γ-chloropropyltrimethoxy 7
Ran, β-cyanoethyltriethoxysilane, tetramethoxysilane, tetraethoxysilane, tetraglopoxysilane, tetrabutoxysilane, methyltrimethoxysilane, methyltriethoxysilane, methyl refoxysilane.

Methyltributoxycrane, ethyltrimethoxysilane, ethyltriethoxysilane, dimethyldimethoxysilane, dimethyljethoxysilane, phenylmethyljethoxysilane, etc. Hydrolysis of these silicon compounds is carried out by a well-known method, for example, in a mixed solvent such as water and alcohol in the presence of an acid. When the compound of component D is used without being hydrolyzed, abrasion resistance and adhesion to the lens surface are insufficient. Furthermore, when two or more types of silicon compounds are hydrolyzed and used, better results are often obtained by mixing them and simultaneously hydrolyzing them than by hydrolyzing them separately and then mixing them. Further, although hydroxyl groups generated by hydrolysis are present in a partially condensed form, this does not affect the effects of the present invention.

Kg of polyfunctional epoxy compound is an essential component for dyeability - coating compositions 0 and D.

Depending on the ratio of E, dyeability and abrasion resistance are greatly affected.
do. In particular, when the ratio of the B component is large, the dyeability increases and the abrasion resistance deteriorates, and on the other hand, when the proportion of the EX component is small, the dyeability deteriorates and the abrasion resistance increases.
This ratio needs to be selected depending on the application. Specific examples of component E include (poly)ethylene glycol, (poly)
Ingredients include diglycidyl ethers of difunctional alcohols such as propylene glycol, neohentyl glycol, catechol, resorcinol, and alkylene glycol, and di- and triglycidyl ethers of trifunctional alcohols such as glycerin and trimethylolpropane. In addition to the dyeability, there are also town problems.

It is also effective in chemical resistance.

Next, compounds with excellent photochromic functions (light attenuation rate, coloring speed, fading speed 11, durability of dimming performance, coloring property due to light absorption) will be described.

Specific examples of the benzopyrillospiran compound represented by the ttlt formula [IV] of component F include ld, 1,5.3-)dimethylindolino-6'-nitropenzobilinospirane, and 1,3.3-trimethylindo. rhino-5-chloro-6
Hoonitrobenzohirirospiran.

1.3.5-trimethylindolino-6'-nitro-8
'-Methoxybenzopyrillospirane, 1,3゜3-trimethylindolino-7'-nitrobenzobyrillospirane, 1,3.5-)rifthylindolino-8-bromobenzobilillospirane, 1,5゜3-) IJ methyl-
6'-nitro8'-fluorobenzopyrrillospiran,
1. s,s-trimethylindolino-6'-furomo8
'-Nitrobenzobyrillospiran, 1,3.3-)rifthylindolino-5'-nitro8'-methoxybenzobilillospiran.

1.3.3-) Benzobilillospiranes such as dimethylindolino-8'-methoxybenzobilillosbilane, and the like.

Examples of dithizone mercury compounds represented by structural formulas (V) and [■] for 7 g include bisdithizone mercury halide, bis(dinaphthylthiocarbazone) mercury halide, and monodithizone mercury halide.

Examples include alkyl compounds and aryl compounds, monodinaphthylthiocarbazone mercury; halides, alkyl compounds and aryl compounds, and halogens include fluorine, chlorine, bromine and iodine. In addition, some or all of the hydrogen atoms in the phenyl group or naphthyl group can be replaced with fluorine, chlorine, bromine, or iodine.

A hydrocarbon group having 1 to 6 carbon atoms, a halogenated alkyl group, an alkoxyalkyl group, a carboxyalkyl Jk, an acyl group, and a sulfonyl group.

It may be substituted with one or more substituents selected from cyan groups.

Further, in the present invention, a desired color can be obtained by combining two or more of the above-mentioned compounds. For example, to obtain a dark brown color, 1,3,3-trimethylindolino-8-bromo-6'-bromobenzpyrylospirane, 1
, 3.3-trimethylindolino-71-nitropensohyryrospirane.

1.3.3-) riftylindolino-5'-nitro8
'-Methoxybenzobiliros biranes can be obtained in a weight ratio of 3:1:2.

In the present invention, a photochromic substance [■].

[V), [:V) n, it is generally said that the dimming performance deteriorates with repeated use, but the bird coat component [c]
and CD), a significant improvement was obtained.

It is effective to use an epoxy curing catalyst as the curing catalyst for component G. Specific examples include alkali metal salts of carboxylic acids such as sodium acetate, and amine carboxylates such as ethanolamine.

Quaternary ammonium carboxylates such as tetramethylammonium acetate and condensation catalysts such as hydrethylamine, glycine, pyridine, alkali hydroxides, tin chloride [■), [lV], aluminum chloride and boron trifluoride. It is effective to use Lewis acids or Brønsted acids, aluminum chelate compounds, other metal chelate compounds, perchlorine oxides such as ammonium perchlorate and magnesium perchlorate, and epoxy curing catalysts such as those mentioned above.

Furthermore, compounds such as metal chelate compounds and perchloric acid compounds have the function of suppressing the condensation of silanol groups at room temperature, in addition to their role as 'l'K curing catalysts.
It is particularly useful for compositions with a short life of 11 da.

By uniformly applying the Bζ coating film obtained in this way to the lens surface, it is possible to solve problems such as the light attenuation rate (S degree gradient) due to differences in lens thickness. In addition, if you want to obtain a density gradient at the bottom of the lens fL, (l) (such as a half-tinted lens), one node of coating 11ψ is used. This can be easily obtained by completely changing the refractive index of the lens due to the difference in the thickness of the film.
Since it is 30μ or less, there is no problem.

It is possible to add various types of fusing, surfactants, thixotropic abrasions, ultraviolet absorbers, antioxidants, and various polymers to improve the coating process and impart the necessary properties as a paint. Alcohols, ketones, esters as solvents or diluents.

Cellosolve, halogenated hydrocarbons, carboxylic acids.

Six types of solvents such as aromatic compounds can be used, and it is also possible to use one or more of these as a mixed mortar.

The method of applying the photochromic coating composition to the high refractive index lens made of synthetic resin 11 of the present invention includes a dipping method, a spray method, a spin coating method, a flow coating method, and other known methods.

The synthetic resin high refractive index lens coated in this manner becomes a cured film by heating and drying.

This is determined by various conditions such as heating temperature and heating time, as well as the composition of the resin, but usually the maximum temperature during curing is 60 to 150℃.
Applicable in 5 degrees Celsius.

The thickness of the resulting cured film is preferably 1 to 30 ti. If it is less than 1 μm, it is impossible to obtain satisfactory wear resistance, and in order to maintain the required properties, the amount of photochromic material must be limited. On the contrary, even if the thickness is set to 30 μm or more, no effect can be expected from increasing the film thickness, and the incidence of cracks will increase.

In order to improve the adhesion between the high refractive index lens made of synthetic resin and the coating composition, each 41-hour primer is treated with activated gas, RTY, alkali, and other chemical treatments to pre-caulk the lens surface. [Examples] The present invention will be explained in detail based on Examples below, but the present invention is not limited to these Examples. do not have.

In addition, I would like to use the method shown below for the evaluation method of Co1-II:
-223 (manufactured by Hasegawa Picault) was used, the maximum absorption wavelength in the visible range shifted by at least 50 nm in one test, and the average extinction rate decreased by more than 20% than the previous average extinction rate. The one that shone was named Sora.

2. Abrasion resistance +oooo Steel wool was used to apply a load of 1 kq to a 1 m wide strip, and the surface was abraded 10 times back and forth, and the degree of scratching was divided into the following grades and evaluated.

A: Hardly any scratches B: Some scratches - C: Significant scratches 6. Adhesion of the coating film In the so-called cross-cut tape test, a knife is used to cut the coating film surface vertically and horizontally at 1-space intervals. Insert parallel lines, cross-cut 100 squares, peel off the Seronon adhesive tape on top of it, and remove the 49 squares that will not be peeled off among the 100 squares. Displayed with money.

4. Heat resistance: Visually inspected the condition of the coated film after storage in a hot air drying oven at 90°C for 5 hours. 5. Side hydrothermal property: Shape of coated film after immersed in hot water at 80°C for 3 hours. was visually inspected.

6. Chemical resistance ethanol, acetone K. The state of the coated film was examined after immersion for 2.4 hours. l Ability to dye with disperse dye Tetrasil Black B (Chino (manufactured by Geigy) 2V).
5℃ warm water 1! and immerse in this solution for 5 minutes (/l
L, the average loss C rate of the TiJ viewing zone is shown.

8th page 11 city I attack Based on FDA standards, steel balls were dropped and the entire box was cleaned.

That is, the steel ball was allowed to fall naturally to the center of the lens from a height of about 16.4'i and 1127ffl, and the lens was cracked. This test was repeated three times, and those with no foreign appearance were considered good. In addition, the center thickness of the lens used in this test was between 2 and 3.

9. Deafness was observed visually after being exposed to a copper xenon lamp for 500 hours on a Zanshine weather meter.
Examined.

10 After completing the durability test method (9), the lens was tested using test methods (1) to
The test (8) was conducted and the results were used as the results of the durability test.

Example 1 (1) Production of synthetic tree 1 compound high refractive index lens 2.2-bis(4-(2-allyloxylponyloxyethoxo))
-3,5-dibromophenyl]propane 50 parts by weight, diallyl orthophthalate 50 parts by weight, 2-(2'-hydroxy-5'-methylphenyl)benzotriazole 0
, 1 part of Ht were mixed and stirred, and then 2# of diisopropyl peroxydicarbonate and 1 part of Ht as a polymerization initiator were added and mixed well. After filtering the insoluble matter of this mixture, -
It was injected into a space made of a glass mold set to give a power of 6,00D and a casket made of ethylene-vinyl acetate copolymer designed to have a center thickness of 2.0Og. Polymerization was carried out in an atmospheric furnace at 40°C for 4 hours at 60°C.
The temperature was raised to 90° C. for 18 hours, and the mixture was heated at 90° C. for 2 hours. Thereafter, the gas foot and glass mold were separated from the lens. When the entire mold of a -6,00D lens was polymerized using this method at 65nrsφ, the incidence of scratching between the glass mold and the lens was less than 1%. Next, post-curing was performed at 100° C. for 3 hours to remove distortion inside the lens.

The optical surface condition of the completed lens is very good.
The Jiff refractive index was 1.585.

(2) Preparation and application of coating liquid γ-glycidoxypropyltrimethoxysilane 37@Kibu, ethanol-dispersed colloidal silica (Catalysts & Chemicals Co., Ltd.
fL) Rep "u130AL-1252" Solid content square 1 yen 30
%) 112 parts by weight, 2-methylpropertool 40 Fl
To a solution consisting of fl.
A flow control agent (Nippon Unicar Co., Ltd.
夷""L-'7001") was added as 0, and Q 311;

Furthermore, as a light modulating component, 1,3.3-) rifthyl indolino-8-promo 6'-bromobenzpyrylosbilane 1.8 heavy cavalry, 1,3.3-) rifthyl indolino-
5'-nitro-8'-methoxybenzovirillospiran'
, 2 f1 cm, 1.3, 5) 0.6 parts by weight of Limethylindolino-7'-nitropenzopyrylosbilane was added and stirred at room temperature for 1 hour to obtain a coating solution. The lens obtained above was pulled up using the immersion method at a rate of 15 tm.
/ wdx (liquid temperature: 10°C) and cured by heating in a hot air dryer at 70°C for 1 hour and then at 90°C for 2 hours. The thickness of the obtained film was 2.3 μm, which was similar to that of a lens. The test results are shown in Table 1.

Example 2 (1) Manufacture of synthetic IIW'M high refractive index lens Same as Example 1-fl) (2) Preparation and application of coating liquid 86 parts by weight of γ-glycidoxyprobyltrimethoxysilane, isopropyl alcohol Dispersed colloidal silica (catalyst and chemical industry piosOAL-1432” solid content concentration) 25
A solution of 6 parts by weight of normal butanol and 520 parts of normal butanol was stirred at room temperature.
It dripped in time. After further stirring for 1 hour, glycerin diglycidyl ether (6Denacol EX31 manufactured by Nagashio Sangyo ■)
70 parts by weight of L-7604 (Nippon Unicar @ Hibiscus) was added as a flow control agent, and 70 parts by weight of α3'' was added to this solution, and stirring was continued for 3 minutes.
,3,3-trimethylindolino-8-furomo6'-
Fromopenzohirirosubi 575. a weight f41S +
1+ 3, 3-trimethylindolino-5'-nitro8'-methoxybenzopyrylospirane 3.6 wt 2f'11ζ, 1,3. ! I-) Limethylindolino 7
1.8 parts by weight of '-nitrobenzobyrillospiran was added and stirred at room temperature for 1 hour. To this solution was added 1.5 parts by weight of magnesium perchlorate as a curing catalyst, and the mixture was stirred for 30 minutes to form a cold liquid. This coating liquid was applied to the lens obtained in Example 1-(1) using the immersion method at a pulling rate of 10 crn/f (liquid temperature 10°C).
1 hour in a hot air dryer at 70℃, and 110℃ for 4 hours.
It was dried for 2 hours. The thickness of +13 was 4μ. The test results of the obtained lens are shown in Table 1. Example 2- Same as +21 Example 1-(1)
A hardened coating was provided on the lens obtained in . Table 1 shows the test results of the obtained lenses.

Example 4 (1) Production of synthetic tree 1 Old pear high refractive index lens 2. 2-bis(4-(2-allyloxycarbonyloxyethoxy))
50 parts by weight of -3,5-dibromophenyl]propane, 42 parts by weight of diallyl 7-talate, 8 parts by weight of diethylene glycol bisallyl carbonate, 2-hydroxy-
Mix and stir 4-methoxybenzophenone in 02 parts,
A lens was produced by mixing 1.5 parts by weight of di-n-propyl peroxydicarbonate as a polymerization initiator and polymerizing in the same manner as in Example 1-(1). The refractive index of the obtained lens was It was 1.57.9.

(2) Preparation and application of coating liquid γ-glycidoxypropylmethyldimethoxysilane L5
9343 parts, isopropyl alcohol-dispersed colloidal silica (“08CAL-1432” manufactured by Catalysts Kasei Kogyo ■) 2
In a solution consisting of 57 parts by weight and 444 parts by weight of dioxane,
28 parts by weight of 0.05N hydrochloric acid was added at once, and the mixture was stirred at room temperature for 3 hours. To this solution, 250 parts by weight of glycerin triglycidyl ether ("EX-314" manufactured by Nagashio Sangyo Co., Ltd.) and 0.2 parts by weight of L-7602 (Nippon Unicar Pear Co., Ltd.) as an rx agent. r - Add and stir for 1 hour r
Bis(dimephthylcarbazone) mercury 10 degrees PA: f? as a continued dimming component. Ii, ammonium perchlorate was added as a curing catalyst at room temperature, and the mixture was stirred for 1 hour to form a coating solution. This coating solution was applied to the above lens by a dipping method at a pulling rate of 20 cnI/MjR (liquid temperature 5°C), and cured by heating in a hot air dryer at 90°C for 3 hours. The thickness of the obtained film was 8 μηt. The test results of the obtained lenses are shown in Table 1V.Example 5 The light control components of Example A-+21 were 1, 3. ! 1-Trimethylindolino 6'-nitrobenzobilirosvirane 671r Yebe, 1,3,3-trimethylindolino-5'
- The lens obtained in Example A-m was provided with a cured coating in the same manner as in Example 4-(2), except that the lens was changed to a 9-fold triple-layered part on Nitro 8'-methoxybenzovirilos. Table 1 shows the test results for the lenses.

Example 6 Production of high J1d refractive index lens made of synthetic resin 11 bis(a-(2-allyloxycarbonyloxy-15,5
-50 parts by weight of dibromophenyl]sulfone, 50 parts by weight of diallyl inphthalate, 0.2 parts by weight of 2-hydroxy-4-octo, xybenzophenone were mixed and stirred, and di-2-ethylhexyl chloride was added as a polymerization initiator. Mixing 3.5 parts by weight of oxydicarbonate, Example 1
-(A lens was produced by polymerization in the same manner as in 11. The refractive index of the obtained lens was 1.592.

(2) Coating liquid preparation and application γ-glycidoxypropylethyljethoxysilane 10
8 parts by weight, 70 parts by weight of tetramethquine, methyl alcohol-dispersed colloidal silica (manufactured by Catalysts & Chemicals Corporation)
70 parts by weight of 0.05N hydrochloric acid was gradually added dropwise over 1 hour to a solution consisting of 184 parts by weight of 80AL1132'') and 426 parts by weight of thrt-butanol while maintaining the temperature at 10 to 20 tons.

Stirring was continued for an additional hour. After the stirring was completed, the liquid temperature was kept at 5° C. and the mixture was allowed to stand overnight. After aging, globylene glycol diglycidyl ether (manufactured by Nagashio Sangyo @Dena:
140 parts by weight of bis[di(2,2,2-)refluoro)orthotolylthiocarbazone mercury as a light control component, L-7602'i02 as a flow control agent. The coating solution was prepared by sequentially adding 1100ml of water and stirring at room temperature for 2 hours. This coating solution was applied to the above lens using the immersion method at a pulling rate of I D cm /
The coating was applied at a liquid temperature of 10°C) and heat-cured at 60°C for 1 hour and at 80°C for 2 hours.

The thickness of one piece obtained was 5 μm. The test results of the obtained lenses are shown in Figure 1.

Example 7 Example 6-1.3.3-) Reime-1 of the dimming component of f2+
Example 6-(21
A cured film was provided on the lens obtained in Example 6-(II) in the same manner as in Example 6-(II).The test results of the obtained lens are shown in Table 1.

Example 8 A hardened film of Example 4=f21 was provided on the lens of Example 1-(11). The test results of the obtained lens are shown in Table 1.

Example 9 The cured coating of Example 6-(2) was provided on the lens of Example 1-+11. The test results of the obtained lens are shown in Table 1.

Example 10 The lens of Example a-(1) was provided with a hardened coating of Actual Artillery Example 2-+21. The test results of the obtained refined lenses are shown in Table 1.

Example 11 Table 1 shows the test results of the lens obtained by applying the curing liquid M of Example 6-121 to the lens of Example 4-(1).

Example 12 Example 6-(The cured coating of Example 2-121 was provided on the lens of Il. The test results of the obtained lens are shown in Table 1.

Example 13 Table 1 shows the test results of the lens obtained by applying the hardened coating of Example 4-+21 to the lens of Example 6-(1).
Indicated.

Table 1-1 Lens test results (before weather resistance test) JP-A-Sho GO
-103347 (12) Table 1-2 Lens test results (after weather resistance test) [Effects] According to the present invention, a high refractive index lens made of synthetic resin that is both easy to manufacture and has excellent optical properties is produced. By providing surface characteristics such as photochromic function (light attenuation rate, coloring speed, fading speed, durability of dimming performance, coloring property due to light absorption), surface hardness, abrasion resistance, hot water resistance, and stainability, eyeglass lenses can be improved. 1) High refractive index lens,
2) A photochromic lens that combines both functions.
Applicant: Suwa Seikosha Co., Ltd. 1

Claims (1)

[Claims] A comonomer mainly composed of A and B of H1 below is copolymerized, and the surface of the synthesized poly(i, l II', i) high refractive index lens is formed by the following 0, ]), 1e. , F, G?
A soft chromic lens made of synthetic wood, characterized in that it is coated and cured with a coating composition containing it as a main component. A, general formula is [1] and 74. One or more quantifiers (formula + 1 + b', R2F yaw (l-OH, 0H
2-, -0-OH,OH,01(,-. Represents, (Represents an integer of ~4.) B, Colloidal silica D whose general formula is represented by [11] and has one or more monomers 1 C1 particle size of 1 to 100 mm, μ;
A hydrous product or partial condensate of one or more silicon compounds represented by the general formula [111] (in the formula R
4q vinyl, amine, imino, epoxy. An organic group containing at least one selected from (meth)acryloxy, phenyl, alkylthiol, and thiol group, R5 is hydrogen, a hydrocarbon group (C, ~C6) and a halogenated hydrocarbon group (C+~06), R' U hydrocarbon group (at
~Ca) r alkoxyalkyl group (c, ~06) and acyl group (0+ ~O*) + a? ': 10, 1 or 2.1) is 0.1 or 2, and a+b≦2)
Polyfunctional epoxy compound F, general formula "(:IV), CVII, [:V
l'] One or more immediate fuzzy bodies represented by
is hydrogen, fluorine, salt and bromine, and RI'l is hydrogen, fluorine. At least one or more substituted compounds selected from chlorine, bromine, nitro group and methoxy group, [v] and [■] are dithizone mercury compounds, and in the formula, R9 to R+4 are the same or different aryl groups, or fluorine, chlorine, bromine . Fluorine, which is iodine and the same or different aryl group, and the aryl group is a phenyl group or a naphthyl group, some or all of which have the following substituents. Chlorine - bromine, iodine, hydrocarbon group (C+ "'-Ca
) +norogenated alkyl (C8-C6), alkoxyalkyl group (at~(:a), carboxyl group (
at~Cs) and carboxyalkyl groups (C8~Ca
) +Sulfonyl group, cyano group, halogenated alkylsulfonyl group<C+~C6)acylzo~(C,~C6)) G, curing catalyst