JPS6210604A - Dimming lens - Google Patents

Abstract

PURPOSE:To provide an adequate dimming function by providing a hard cost layer contg. a specific org. photochromic compd. on the surface of a lens body consisting of a resin. CONSTITUTION:The hard cost layer contg. the org. photochromic compd. expressed by the formula is provided on the surface of the lens body consisting of the resin. The reason for the noticeable coloration which arises in the spirooxazune compd. expressed by the formula even in an environmental condition of a relatively high temp. lies in that the colorable spirooxazine isomer ionized by light irradiation relatively stably exists in the extremely hard and highly polar hard coat layer and that the colored state is consequently maintained. The content ratio of the spirooxazine compd. is generally made 0.01-80pts.wt., more preferably 0.02-50pts.wt. by 100pts.wt. resin for hard coat and the preferable thickness of the hard coat layer is 1-100mu. The dimming effect by light is thereby obtd. and the color tone satisfactory even at an ordinary temp. is generated.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a photochromic lens having a hard coat layer on its surface containing a spirooxazine compound, which is a photochromic substance.

[Prior art]

Photochromism is a phenomenon in which a reversible color change occurs in a certain compound when the compound is irradiated with light containing ultraviolet light such as sunlight or mercury lamp light, and the light is removed. The applied lens is a photochromic lens, which can be widely applied to sunglasses, prescription glasses, goggles, etc.

Conventionally, lenses with this kind of function have been limited to those made by inorganic glass containing minute silver halide particles, and lenses made of resin, which have become widely used in recent years, are still very few. It has not been put into practical use.

The reason for this is that inorganic substances such as silver halide particles have low compatibility with resins, so it is difficult to uniformly disperse them in sufficient quantities in resins, and organic substances, which are thought to have high compatibility with resins, cannot be uniformly dispersed in resins. This is because no photochromic compounds are known to be stable and useful.

For example, spiropyran compounds, the most common organic photochromic compounds, exhibit useful photochromism in organic solvents, but fade in polymeric materials with relatively high second-order transition temperatures that are widely used as optical materials. is extremely slow, and as a result, the resulting light control materials are subject to significant limitations in their applications.

On the other hand, Japanese Patent Publication No. 45-28892 discloses that spirooxazine compounds exhibit photochromic effects in general non-crosslinked polymers, regardless of their secondary transition temperature. However, as pointed out in Japanese Patent Publication No. 49-48631, this spirooxazine compound shows good changes in coloration and fading due to irradiation and removal of light at a low temperature of about 10°C.
It has the disadvantage that it fades at a high rate at high temperatures, so it is virtually uncolored. Photochromic lenses generally change color or change color when exposed to strong light from the sun.
Since the purpose is to suppress the transmission of that light, it is natural that it is required to have sufficient coloring effect even in an environment where the temperature is slightly higher than room temperature. It is generally believed that spirooxazine compounds are not practical as photochromic substances for photochromic lenses.

[Problem to be solved by the invention]

The present invention aims to provide a photochromic lens made of resin that uses a spirooxazine compound as a photochromic substance and has a sufficient coloring effect even in an environment slightly higher than room temperature. As a result of research conducted by , it was discovered that spirooxazine compounds unexpectedly exhibit excellent photochromism even at relatively high temperatures when contained in a highly polar and hard medium, and are particularly useful in the so-called hard coat layer of lenses. The present inventors have discovered that when it is contained, it has a suitable function as a photochromic lens, leading to the present invention.

[Means and actions for solving problems]

The photochromic lens of the present invention is characterized by having a hard coat layer containing an organic photochromic compound represented by the following general formula (I>) on the surface of the lens body made of resin.

General formula (I) [wherein R1 is a hydrogen atom, a halogen atom, a cyano group, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms, R2 is an alkyl group having 1 to 6 carbon atoms, - G
CI (thcOOH, -4CHz axis CN.

Indicates HCHz juice COOR, where R is carbon number 1-6
an alkyl group, n represents an integer of 1 to 4. ] The photochromic lens of the present invention is characterized in that it has a hard coat layer on the surface of the lens body made of resin, and the spirooxazine compound is contained in this hard hard coat layer. Excellent photochromism is exhibited and a sufficient light control effect can be obtained both at room temperature and in an environment slightly higher than room temperature. Like this -i
The reason why the spirooxazine compound represented by formula (I) shows remarkable coloration even in relatively high temperature environmental compounds is because
This is thought to be because in the hard coat layer, which is extremely hard and highly polar, color-forming spirooxazine isomers that are ionically dissociated by light irradiation exist relatively stably, and therefore the color-forming state is maintained.

Of course, since the hard coat layer protects the surface of the lens body made of resin, the photochromic lens of the present invention also has excellent scratch resistance.

The spirooxazine compound used in the present invention is represented by the above general formula (I).

Representative examples of such spirooxazine compounds include:
The following can be mentioned:

1.3.3-1-dimethylspiro[indolino-2,3
"-naphtho(2,1-b) (I,4)-oxazine]1.3.3.5-tetramethylspiro[indolino-
2,3''-naphtho(2,l-b) (I,4)~oxazine] 5-chloro-1,3,3-)dimethylspiro[indolino-2,3'-naphtho(2,1-b) (I, 4)
-oxazine] 5-methoxy-1,3,3-trimethylspiro [indolino-2,3'-naphtho(2,1-b) (C4)
-Oxazine] 1-isopropyl-3,3-dimethylspiro[indolino-2,3°-naphtho(2,1-b) (I,4)-
[Oxazine] These spirooxazine compounds are produced by mixing equimolar solutions of 1,3,3-1-dimethyl-2-methyleneindoline having various substituents and 2-nitroso-1-naphthol in ethanol, etc. under a nitrogen gas atmosphere. It can be synthesized by refluxing and reacting. In addition, indolinium iodide corresponding to the above methyleneindoline compound can be combined with a basic compound such as triethylamine and 2-nitroso-
It can also be synthesized by refluxing with 1-naphthol.

The spirooxazine compound as described above exhibits its effect by being contained in the hard coat layer formed on the surface of the lens body.For that purpose, the hard coat layer in the present invention is hard and has a molecular structure. It is desirable that the polarity is large. The hard coat layer is usually formed by applying and drying a hard coat agent.

In the present invention, the hard coat agent for forming the hard coat layer can be broadly classified into silicone hard coat agents, polyfunctional acrylic hard coat agents, melamine hard coat agents, urethane hard coat agents, alkyd hard coat agents, and silica sol. Hard coating agents and the like are preferably used.

In the present invention, the silicone hard coating agent includes:
As shown in the following formula, any organoalkoxysilane can be used as a hard coating agent to improve surface hardness, as long as it is hydrolyzed to form silanol and self-condensed to organopolysiloxane to form a multidimensional crosslinked structure. The materials used in this invention are mainly those having trifunctional or higher functional polysiloxane cores such as the following, and such materials are also used in the present invention. In the above formula, R is -CH=CHt, CHzCl
, organic functional groups such as C1hSH, -H, -CI
, -OR, etc., an aliphatic or aromatic hydrocarbon residue, and n is an integer of 2 or less. Moreover, Ro is an aliphatic or aromatic hydrocarbon residue,
Others.

Specifically preferred silicone hard coating agents include:
Methyltrimethoxysilane, tetramethoxysilane, phenyltrimethoxysilane, methacryloxytriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-aminoprobiltV ethoxysilane, vinyltrimethoxysilane, vinyltris(2-methoxyethoxy) ) silane, and others. Of course, the invention is not limited to these examples.

In the present invention, it is particularly preferable to use the above-mentioned silicone hard coating agent in combination with spirooxazine, but other hard coating agents include melamine represented by the following formula, which can obtain a layer with high strength by heating. , urethane and alkyd-based organic hard coating agents are used.

? CN -C11,0)1 CH,OR (In the formula, R represents a phenyl group or an alkyl group having 1 to 8 carbon atoms.) Also, a polyfunctional acrylic or methacrylic hard coat that can be cured with ultraviolet rays. A silica sol-based hard coating agent can also be used. Further, in the present invention, it is of course possible to use a combination of the various hard coating agents described above. That is, after forming an acrylic node coating agent as a lower layer to improve the adhesion between the lens body made of resin and the hard coating agent, a silicone hard coating layer is formed on top of it to form a multilayer hard coating layer. You may. In this case, the spirooxazine compound can be contained in either or both layers.

In the present invention, the content of the spirooxazine compound in the hard coat layer varies depending on the purpose of use of the photochromic lens obtained, but -S is 0.01 to 80 parts by weight per 1 part of hard coat resin. , more preferably 0.02 to 50 parts by weight. In addition to the spirooxazine compound, various dyes, ultraviolet absorbers, and aggravating agents may be used in the present invention in order to make the dimming effect more comfortable.

The material of the lens body made of resin in the present invention is not particularly limited. In other words, materials such as polymethyl methacrylate, diethylene glycol bisallyl carbonate resin (e.g. rCR-39), polycarbonate, and polystyrene, which have traditionally been used as materials for so-called plastic lenses, as well as high refractive index materials that have recently begun to be used rapidly. It is also possible to use nylon-based, polyacrolein-based, bromine-substituted aromatic methacrylate-based resins, and the like.

In order to manufacture the photochromic lens of the present invention, a solution of a hard coating agent diluted in a solvent containing a spirooxazine compound is coated on the surface of a lens body made of resin, and then The coating method is performed by drying, heat curing, ultraviolet irradiation, electron beam irradiation, etc., and the coating method can be applied as is. Specifically, the lens body is immersed in the coating liquid. A method of pouring a coating liquid onto the lens body and coating it uniformly with a spinner or the like, a method of spraying the coating liquid onto the lens body, etc. are carried out. The hard coat layer containing the spirooxazine compound may be formed on one side or both sides of the lens body. The thickness of the hard coat layer is 1-10
0μ is preferred.

The photochromic lens of the present invention produced as described above exhibits a photochromic effect by light, and produces a sufficient color tone even at room temperature of about 25°C, and has a practically sufficient speed of discoloration and fading. It's a big one.

The photochromic lens of the present invention can be used in sunglasses, prescription eyeglasses, various goggles, and the like.

〔Example〕

Examples of the present invention will be described below, but the present invention is not limited thereto.

Example 1 1) 1,3.3-)limethylspiro[indolino-
Synthesis of 2,3''-naphtho(2,1-b)(I,4)-oxazine] Equimolar amounts of 1-nitroso-2-naphthol and 1.3.3-)samethyl-2-methyleneindoline were dissolved in ethanol. Dissolved in acetone and subjected to centrifugal flow for 2 hours while blowing nitrogen.Next, after distilling off the reaction solvent ethanol, the residue was dissolved in acetone, cooled, and diluted with 1,3
．． Crude crystals of 3-trimethylspiro [indolino-2,3'-naphtho(2,ib) (I,4)-oxazine] were obtained. Purification was performed by recrystallization using acetone to obtain a light brown target product.

2) Preparation of hard coat liquid 40 parts by weight of phenyltrimethoxysilane, 45.6 parts by weight of methylphenyldimethoxysilane, 7.6 parts by weight of tetramethoxysilane, and 100 parts by weight of Impropatol were vigorously stirred at room temperature. 35 parts by weight of an aqueous hydrochloric acid solution having a concentration of 0.05N was added dropwise, and the mixture was further stirred for 2 hours. Thereafter, stirring was stopped and the mixture was aged at room temperature for one day to obtain a hard coat liquid.

3) Preparation and coating of coating liquid 1.7 parts by weight of the spirooxazine compound synthesized in 1) above was dissolved in 100 parts by weight of the hard coat liquid obtained in 2) to prepare a coating liquid. The coating liquid was applied to a lens body made of diethylene glycol bisallyl carbonate resin rCR-39J by a spray method, pre-dried for 1 hour in a hot air dryer at 50°C, and then heated and cured at 80°C overnight.
A photochromic lens of the present invention was obtained.

This photochromic lens is transparent with a slight bluish tinge, and is suitable for use with ultraviolet inspection lamps rModel UVL 21J (UV
P INC.

When irradiated with ultraviolet rays (manufactured by Sekisui Chemical Co., Ltd.), it instantly turned blue. When the irradiation with ultraviolet rays was then stopped, the color fading was rapid, and after 9 minutes at 30° C., it had almost returned to its original state. From the above facts, it was confirmed that this photochromic lens has a high fading rate and has an excellent photochromic effect.

Example 2 1) 5-chloro-1,3,3-)limethylspiro[indolino-2,3'-naphtho(2,1-b) (I,4)
-oxazine] Equimolar amounts of 1-nitroso-2-naphthol, 5-chloro-1,2,3,3-tetramethylindole iodide and twice the amount of triethylamine were dissolved in ethanol, and while blowing nitrogen, Reflux was carried out for 2 hours. After distilling off the reaction solvent ethanol, the residue was dissolved in acetone and cooled to give 5-chloro-1,3,3-)limethylsubiro[indolino-2,3°-naphthoC2,1-b].
Crude crystals of (I,4)-oxazine] were obtained. Purification was performed by recrystallization using acetone to obtain a light brown target product.

2) Preparation and coating of coating liquid 1.7 parts by weight of the spirooxazine compound synthesized in 1) above was dissolved in 100 parts by weight of the hard coat liquid obtained in 2) of Example 1 to prepare a coating liquid. This coating liquid was applied to a lens body made of rCR-39J by a spray method, pre-dried in a hot air dryer at 50°C for 1 hour, and then heated and cured at 80°C overnight. I got it.

This photochromic lens was transparent with a slight bluish tinge, and when exposed to sunlight, it instantly turned blue. Immediately after that, it was moved to a dark place, and after 9 minutes at 30°C, it returned to its initial colorless state, and it was recognized that it had an excellent dimming effect with a fast fading rate.

Example 3 Spirooxazine compound synthesized in Example 1 1.
3.3-) Limethylspiro [indolino-2゜3゛-
naphtho(2,1-b) (I,4)-oxadi731.
0 parts by weight of commercially available Brimer RP for silicone coating.
Dissolve the solution in 40 parts by weight of isopropanol along with 30 parts by weight of H93J (manufactured by Toshiba Silicone Co., Ltd.), apply the solution to a lens body made of "rCR-39" by a spray method, and dry at 50°C for 1 hour. After that, BRIMER r PH93J diluted twice with isopropanol was further applied by spraying on this, and dried again at 50° C. for 1 hour.

Next, a silicone coating agent "Tosugat 505" (manufactured by Toshiba Silicone Co., Ltd.) was applied by a dipping method, pre-dried at 50°C for 1 hour, and then heated and cured at 90°C overnight to obtain a photochromic lens of the present invention. Ta.

This photochromic lens is colorless and transparent, and when exposed to sunlight, it instantly turned dark blue. Immediately after that, it was moved to a dark place, and the color fading was rapid, and after 5 minutes at 30°C, it had already returned to its original colorless state, indicating that it has an excellent dimming effect with a fast fading rate. This was recognized.

Procedural amendment (voluntary) September 4, 1985 Michibu Uga, Commissioner of the Patent Office 1, Indication of case 149343 2, Name of invention Photochromic lens 3, Person making the amendment Case and Relationships Patent Applicant Address 1-9-11 Nihonbashihoridome-cho, Chuo-ku, Tokyo Name (I10) Kureha Chemical Industry Co., Ltd. 4, Agent Okano Building Column 6 of the detailed description of the invention in the specification, Amendment Contents (2) “Methyl...
・7.6 parts by weight,'' should be corrected as follows.

"7.6 parts by weight of methylphenyldimethoxysilane, 45.6 parts by weight of tetramethoxysilane," ■

Claims (1)

[Scope of Claims] 1) A photochromic lens comprising a hard coat layer containing an organic photochromic compound represented by the following general formula (I) on the surface of a lens body made of resin. General formula (I) ▲ Numerical formulas, chemical formulas, tables, etc. are available▼ [In the formula, R_1 is a hydrogen atom, a halogen atom, a cyano group, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms, and R_2 is Alkyl group having 1 to 6 carbon atoms, -
(CH_2)-_nCOOH, -(CH_2)-_nC
N, -(CH_2)-_nCOOR. However, R represents an alkyl group having 1 to 6 carbon atoms, and n represents an integer of 1 to 4. 2) The photochromic lens according to claim 1, wherein the hard coat layer is a polymer having a multidimensional crosslinked structure of organosiloxane.