JPH0336408B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Application Field] 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, and a phenolic resin or a phenolic compound. [Prior Art] The phenomenon in which a reversible color change occurs in a certain compound when the compound is irradiated with and removed by sunlight or light containing ultraviolet rays, such as light from a mercury lamp, is called photochromism. Those applied to lenses are generally known as photochromic lenses, and are widely used in sunglasses, prescription glasses, goggles, etc. [Problems to be solved by the invention] Conventionally, lenses having such a function have been limited to lenses made of inorganic glass containing minute silver halide particles, and these lenses have been widely used in recent years. Lenses made of resin, which are becoming increasingly popular, have not yet been put into practical use. The reason for this is that inorganic substances such as silver halide particles have low compatibility with resins, and therefore cannot be uniformly dispersed in sufficient amounts in resins, and it is thought that inorganic substances such as silver halide particles have high compatibility with resins. This is because there are few stable and useful organic photochromic compounds. For example, spiropyran compounds, the most common organic photochromic compounds, exhibit useful photochromism in organic solvents, but they do not exhibit useful photochromism in polymeric materials with relatively high second-order transition temperatures, which are widely used as optical materials. The rate of fading is extremely slow, and as a result, the resulting light control materials are subject to significant limitations in their use. 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, this spirooxazine compound was
As pointed out in Publication No. 48631, although changes in color and fading due to irradiation and removal of light occur well at low temperatures of around 10°C, the rate of fading is rapid at room temperature or higher temperatures. Therefore, it has the disadvantage that it is virtually uncolored. In general, photochromic lenses are designed to change color or change color when exposed to strong light from the sun, so that they suppress the transmission of that light. It goes without saying that spirooxazine compounds are required to have a sufficient coloring effect even when used in photochromic lenses, and in this sense, the use of spirooxazine compounds as photochromic substances for photochromic lenses is generally restricted. It's summery. The present invention aims to provide a photochromic lens made of resin that uses a spirooxazine compound as a photochromic substance and has sufficient coloring effect even in an environment slightly higher than room temperature. As a result of research, it was discovered that spirooxazine compounds unexpectedly exhibit excellent photochromism even in relatively high-temperature environments when they are contained in a hard medium in the presence of highly polar compounds. It has been discovered that, in particular, when it is included in the hard coat layer of a lens together with a phenolic resin or a phenolic compound, it exhibits a suitable function as a photochromic lens,
This has led to the completion of the present invention. [Means and effects for solving the problems] The photochromic lens of the present invention has a hard coat layer containing an organic photochromic compound represented by the following general formula () and a phenolic resin or a phenolic compound on a lens body made of resin. It is characterized by having on the surface. General formula () [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 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;
Alkyl group, (-CH ₂ )- _o COOH, (-CH ₂ )- _o CN,
(-CH ₂ )- _o Indicates COOR. However, R has 1 or more carbon atoms.
6 alkyl group, n represents an integer of 1-4. ] The photochromic lens of the present invention has a hard coat layer on the surface of the lens body made of resin, which is also called a plastic lens, and this hard hard coat layer contains a spirooxazine compound together with at least one of a phenolic resin and a phenolic compound. It is characterized by the fact that With this structure, the spirooxazine compound is contained in the hard hard coat layer together with the highly polar phenolic resin or phenolic compound, both at room temperature and in an environment slightly higher than room temperature, resulting in excellent photoresist properties. Chromism is exhibited and sufficient light control effect can be obtained.
The reason why the spirooxazine compound represented by the general formula () exhibits remarkable coloring even in a relatively high temperature environment is that in a hard hard coat layer containing a highly polar phenolic resin or phenolic compound, This is thought to be because the color-forming spirooxazine isomer that is ionically dissociated by light irradiation exists relatively stably, and therefore the color-forming state is maintained well. 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 (). Representative examples of such spirooxazine compounds include 1,3,3-trimethylspiro[indolino-
2,3'-naphtho[2,1-b](1,4)-oxazine], 1,3,3,5-tetramethylspiro[indolino-2,3'-naphtho[2,1-b]( 1,4)
-oxazine], 5-chloro-1,3,3-trimethylspiro[indolino-2,3'-naphtho[2,1-b]
(1,4)-oxazine], 5-methoxy-1,3,3-trimethylspiro[indolino-2,3'-naphtho[2,1-b]
(1,4)-oxazine], 1-isopropyl-3,3-dimethylspiro[indolino-2,3'-naphtho[2,1-b]
(1,4)-oxazine]. These spirooxazine compounds are produced by refluxing an equimolar solution of 1,3,3-trimethyl-2-methyleneindoline having various substituents and 2-nitroso-1-naphthol in ethanol or the like under a nitrogen gas atmosphere. It can be synthesized by reaction. In addition, indolinium iodide corresponding to the above methyleneindoline compound can be combined with a basic compound such as triethylamine and 2-nitroso-1
-It can also be synthesized by refluxing with naphthol. The spirooxazine compound as described above exhibits its effect significantly when it is contained together with a phenolic resin or a phenolic compound in a hard coat layer formed on the surface of a lens body. The hard coat layer in the present invention is usually formed by applying and drying a hard coat agent. As the hard coat agent for forming the hard coat layer, silicone hard coat agents, silica sol hard coat agents, organic hard coat agents, etc. are preferably used. In the present invention, the silicone hard coating agent may be any one that forms a multidimensional crosslinked structure by hydrolyzing organoalkoxysilane to form silanol and self-condensing to organopolysiloxane, as shown in the following formula. You can also use things. The hard coating agents used to improve surface hardness are mainly

【formula】

A polysiloxane core having trifunctional or higher functionality as shown in the formula is suitable, and such a material is also used in the present invention. In the above formula, R is -CH=
_CH2 ,

〔Example〕

Examples of the present invention will be described below, but the present invention is not limited thereto. Example 1 1 Synthesis of 1,3,3-trimethylspiro[indolino-2,3'-naphtho[2,1-b](1,4)-oxazine] Equimolar amounts of 1-nitroso-2-naphthol and 1,3,3-trimethyl-2-methyleneindoline was dissolved in ethanol and refluxed for 2 hours while blowing nitrogen. Next, after distilling off the reaction solvent ethanol, the residue was dissolved in acetone and cooled to give 1,3,3-trimethylspiro[indolino-2,3'-naphtho[2,1-b](1,
4)-Oxazine] was obtained. Purification was performed by recrystallization using acetone to obtain a pale yellow target product. 2 Preparation of hard coat liquid 40 parts by weight of phenyltrimethoxysilane, 7.6 parts by weight of methylphenyldimethoxysilane, 45.6 parts by weight of tetramethoxysilane, 100 parts by weight of isopropanol
Stir the weight part vigorously at room temperature and add the concentration.
35 parts by weight of a 0.05N aqueous hydrochloric acid solution 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 the coating liquid The spirooxazine compound synthesized in 1 above
1.7 parts by weight and 1.5 parts by weight of bisphenol A were dissolved in 100 parts by weight of the hard coat liquid obtained in step 2 to prepare a coating liquid. This coating liquid was applied to a lens body made of diethylene glycol bisallyl carbonate resin "CR-39" by a spray method, and heated to 50°C.
After preliminary drying for 1 hour in a hot air dryer, heat curing was performed at 80° C. overnight to obtain a photochromic lens of the present invention.
This photochromic lens was transparent with a slight bluish tinge. When this photochromic lens was irradiated with ultraviolet light from an ultraviolet inspection lamp "Model UVL-21" (manufactured by UVP INC.) at a temperature of 30°C, it instantly turned blue. The intensity of the coloration was approximately twice as strong as that of a comparison photochromic lens manufactured in the same manner using a coating liquid obtained in the same manner except that bisphenol A was removed. After that, when the UV irradiation was stopped,
The color fading was rapid and returned to almost its original state after 9 minutes at 30°C. Based on the above facts, it was confirmed that this photochromic lens exhibits excellent color development even at a temperature of 30° C., has a high fading rate, and has an excellent photochromic effect. Example 2 1 5-chloro-1,3,3-trimethylspiro[indolino-2,3'-naphtho[2,1-b]
Synthesis of (1,4)-oxazine] equimolar amount of 1-nitroso-2-naphthol, 5
-Chloro-1,2,3,3-tetramethylindole iodide and twice the amount of triethylamine were dissolved in ethanol and refluxed for 2 hours while blowing nitrogen. After distilling off the reaction solvent ethanol, the residue was dissolved in acetone and cooled to give 5-chloro-1,3,3-trimethylspiro[indolino-2,3'-naphtho[2,1-b]
(1,4)-oxazine] crude crystals were obtained. Purification was performed by recrystallization using acetone to obtain a light brown target product. 2 Preparation and coating of coating liquid Add the spirooxazine compound synthesized in 1 above to 100 parts by weight of the hard coat liquid obtained in 2 of Example 1.
1.7 parts by weight and 1.5 parts by weight of p-tertiarybutylphenol
parts by weight were dissolved to prepare a coating liquid. This coating liquid was applied to a lens body made of "CR-39" 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 a photochromic lens. This photochromic lens was transparent with a slight bluish tinge. When this photochromic lens was exposed to sunlight, it instantly turned blue. And the strength of the coloring is p-
It was much larger than a comparison photochromic lens manufactured in the same manner using a coating liquid obtained in the same manner except that tertiary butylphenol was removed. Immediately after that, it was moved to a dark place, and after 9 minutes at 30°C, it returned to its initial colorless state, indicating that it had an excellent dimming effect with a fast fading rate. Example 3 1.0 parts by weight of the spirooxazine compound 1,3,3-trimethylspiro[indolino-2,3'-naphtho[2,1-b](1,4)-oxazine] synthesized in Example 1 and tetra 1.0 parts by weight of Brombisphenol A and commercially available silicone coating primer "PH93" (manufactured by Toshiba Silicone Co., Ltd.)
A coating liquid was obtained by dissolving 30 parts by weight in 40 parts by weight of isopropanol, and this coating liquid was applied to a lens body made of "CR-39" by a spray method, and heated at 50°C.
After drying for 1 hour, a primer "PH93" diluted twice with isopropanol was further applied by spraying, and pre-dried again at 50°C for 1 hour. Next, a silicone coating agent "Tosguard 520" (manufactured by Toshiba Silicone Corporation) diluted with isopropanol to a concentration of 30% was applied using the dipping method, pre-dried at 50℃ for 1 hour, and then heated to 90℃ overnight. Heat curing was performed to obtain a photochromic lens of the present invention. This photochromic lens was colorless and transparent. When this photochromic lens was exposed to sunlight at a temperature of 30°C, it instantly turned dark blue. Immediately after that, it was moved to a dark place, and after 5 minutes at 30°C, it had almost returned to its initial colorless state. From the above facts, it was confirmed that this photochromic lens exhibits excellent color development even at a temperature of 30° C., has a high fading rate, and has an excellent photochromic effect. Example 4 1.5 parts by weight of the spirooxazine compound 1,3,3-trimethylspiro[indolino-2,3'-naphtho[2,1-b](1,4)-oxazine] synthesized in Example 1 and bis 1.0 parts by weight of phenol A was added to a commercially available phenolic resin solution "Pryophene TD-" in an amount such that the resin content was 100 parts by weight.
447" (manufactured by Dainippon Ink Chemical Co., Ltd.), and 100 parts by weight of a silica sol solution "LOSCAL-1432" (manufactured by Catalysts Kasei Kogyo Co., Ltd., SiO ₂ content 30%) was added thereto to obtain a coating liquid. This coating liquid is applied to "CR-39" using the dating method.
The photochromic lens was coated on a lens body made of material and dried at 80°C for 5 hours to obtain a photochromic lens of the present invention. This photochromic lens was transparent with a slightly yellow color. When this photochromic lens was exposed to sunlight at a temperature of 30°C, it instantly turned blue, making it useful as a photochromic lens. Immediately after that, it was moved to a dark place, and after 10 minutes at 30°C, it had almost returned to its initial colorless state. From the above facts, it was confirmed that this photochromic lens exhibits excellent color development even at a temperature of 30° C., has a high fading rate, and has an excellent photochromic effect. Example 5 2.0 parts by weight of the spirooxazine compound 1,3,3-trimethylspiro[indolino-2,3'-naphtho[2,1-b](1,4)-oxazine] synthesized in Example 1 and bis A coating liquid was obtained by dissolving 2.0 parts by weight of phenol A in 75 parts by weight of a commercially available epoxy resin solution "Eponics #1100 Clear" (manufactured by Dainippon Toyo Co., Ltd.). This coating liquid was applied to a lens body made of "CR-39" by a dipping method and dried at 60°C for 24 hours. Furthermore, on top of this, a silicone coating agent "Tosguard 520" (manufactured by Toshiba Silicone Corporation) is applied to a concentration using isopropanol.
Apply the solution diluted to 30% using the dipping method,
After preliminary drying at 50°C for 1 hour, heat curing was performed at 90°C for 2 hours to obtain a photochromic lens of the present invention. Those that are not coated with the above silicone coating agent also have a hard coat layer made of epoxy resin with a considerably high surface hardness, and a practical photochromic lens can be obtained. By doing so, it will have even more excellent surface hardness. The photochromic lens obtained as described above was colorless and transparent, and when exposed to sunlight at a temperature of 30°C, it turned dark blue after 3 seconds. Immediately after that, it was moved to a dark place, and the color fading was good, and after 5 minutes at 30°C, it had already returned to its original colorless state. From the above facts, it was confirmed that this photochromic lens exhibits excellent color development even in a relatively high temperature environment, has a high fading rate, and has an excellent photochromic effect.

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 () and a phenolic resin or a phenolic compound on the surface of a lens body made of resin. . General formula () [Wherein, 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 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;
Alkyl group, (-CH ₂ )- _o COOH, (-CH ₂ )- _o CN,
(-CH ₂ )- _o COOR. However, R has 1 carbon number
-6 alkyl group, n represents an integer of 1-4. 2. The photochromic lens according to claim 1, wherein the phenol compound is an alkyl-substituted phenol compound. 3. The photochromic lens according to claim 1, wherein the phenolic compound is bisphenol A or a derivative thereof. 4. The photochromic lens according to claim 1, wherein the hard coat layer is made of a polymer having a multidimensional crosslinked organosiloxane structure. 5. The photochromic lens according to claim 1, wherein the hard coat layer contains an organic hard coat agent.