JPH0338310B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Applicability] The present invention relates to a composition having photochromic properties with excellent color development/decolorization properties, durability, heat resistance, and fatigue resistance. In particular, it relates to compositions with photochromic properties that have excellent tourist properties against sunlight and a high concentration when coloring, and are particularly useful for optical articles such as sunglasses and corrective lenses, and window glass for automobiles, homes, offices, etc. It is preferably used for purposes that require light regulation related to sunlight. [Prior Art] A large number of photochromic compounds are already known, including the most famous spiropyran compound (GHBrown,
“Photochromism, Wiley Interscience, New
York (1971)). Among these, spirooxazine compounds are known as compounds with excellent coloring speed, color erasing speed, and repeatability (Japanese Patent Publication No. 45-28892, Japanese Patent Publication No. 49-48631,
(Japanese Patent Application Laid-Open No. 55-36284). In addition, several attempts have already been made to prepare composites using these photochromic compounds. For example, JP-A-59-78271, JP-A-Sho.
No. 59-78282 describes a photochromic coating composition containing a spiropyran compound in a silane compound. [Problems to be Solved by the Invention] Spiropyran compounds have a problem in fatigue resistance during repeated use of light-emitting and decoloring. In addition, Kochi's spiro(indoline) oxazine compounds and spiro(indoline) pyridoxazine compounds both had excellent properties in terms of coloring and decoloring speeds, but they were found to have excellent properties when exposed to high temperatures in summer or weak sunlight in winter. The drawback was that the color density under light was not sufficient. [Means for Solving the Problems] The present invention relates to a composition having photochromic properties for solving the above problems. That is, the present invention consists of the following configuration. "Related to a composition having photochromic properties characterized by containing a spirooxazine compound represented by the following general formula (), a matrix resin, and a thioxanthone having a triplet energy of 40 to 68 kcal/mole or a substituent derivative thereof" be. (However, X is C- _R9 or nitrogen, and _R9 is selected from hydrogen, _{a C1} to _{C8 alkyl} group, an _alkoxy group, and a halogen. selected from the group consisting of C ₇ to C ₂₀ substituted or unsubstituted aralkyl groups; _{R 2} and R ₃ each represent hydrogen, C ₁ to C ₅ alkyl, phenyl,
Cyclic rings selected from the group consisting of mono- and di-substituted phenyls, benzyls, or cycloaliphatic rings containing 6 to 8 carbon atoms (including spiro carbon atoms), norbornyls, adamantyls in combination; selected from the ring. _R4 , _R5 , _R6 , _R7 and _R8
each of which is hydrogen, a C ₁ to C ₅ alkyl group, an alkoxy group, a halogen, a nitro group, a cyano group, a hydroxy group, a C ₁ to C ₅ halogenated alkyl group,
Selected from alkoxycarbonyl group and amino group. )" Here, the spirooxazine compound represented by the general formula (I) is a known spiro(indoline) compound.
Oxazine compounds, or spiro (indolines)
Pyridoxazine compounds can be used. (Japanese Patent Publication No. 45-28892, Japanese Patent Publication No. 55-36284,
JP-A-60-53586, JP-A-60-112880, JP-A-61-233079, DE P33456259). These photochromic compounds can be used not only alone, but also in combination of two or more to make the absorption wavelength of the coloring species broader, to create a mixed color, and to improve the apparent durability. Among these compounds, especially the triplet energy described below is 40 ~
68 kcal/mole, which can be significantly sensitive to the sensitizing effect of a so-called sensitizer, is C ₇ in R _1.
Spiro(indoline)naphthoxazines with ~ _C20 substituted or unsubstituted aralkyl groups are preferred. In particular, those having a substituted or unsubstituted benzyl group in R ₁ are preferably used from the viewpoint of light resistance, color development rate, color erasure rate, selectivity of color forming species, and the like. Here, the triplet energy is 40 to 68 kcal/mole
A thioxanthone or its substituent derivative has a triplet excitation energy level of 40 to
It refers to thioxanthone or its substituent derivatives that have a high level of 68 kcal/mole. Excitation of such compounds is generally achieved by ultraviolet light or light in the short-wavelength visible light region, but from the point of view of application to compositions with photochromic properties, it is moreover From the viewpoint of application to compositions that change into systems, compounds that are excited by light of 300 to 400 nm are preferred. Here, thioxanthone is a general term for compounds represented by the following general formula (A), and includes various substituent derivatives. However, R ₀ and R ₁₀ are halogen, C ₁ to C ₆ alkyl group, alkoxy group, alkoxycarbonyl group,
glycidoxy group, allyl ether group, cyano group,
It is a hydroxy group, etc., and K and l are 0, 1, 2 or 3. Furthermore, thioxanthone oxides represented by general formula (A) such as those represented by general formula (A') below are also included. Note that j in (A′) is 1
Or 2. A spirooxazine compound represented by the above general formula () and a triplet energy of 40 to
Thioxanthone or its substituent derivative, which has a concentration of 68 kcal/mole, is used in a state where it is dispersed in a suitable matrix resin.The matrix resin that can be used here is one in which each of the above-mentioned compounds is compatible with each other. There is no particular limitation as long as it is dispersible. In order to increase the rate of color development and fading, a resin having a low glass transition temperature is preferable, and in order to appropriately darken the color, a resin having a glass transition temperature higher than room temperature is preferably used.
Further, for the purpose of improving solvent resistance, chemical resistance, etc., it is preferable to use a crosslinked matrix resin. Specific examples of such matrix resins include polymers and copolymers of polyol (allyl carbonate) monomers, polymers and copolymers of (meth)acrylate, melamine resins, urethane resins, nylon resins, polycarbonates, polyethylene terephthalate, and styrene polymers. Examples include polymers and copolymers, celluloses, epoxy resins, vinyl acetate polymers and copolymers, polyvinyl alcohol, urea resins, polyvinyl chloride, polyvinyl butyral, and polyvinyl acetate. These resins can be used not only alone, but also as a mixture of two or more. The ratio of the amounts added of each component in the present invention should be optimized depending on the purpose, application, and required characteristics. The spirooxazine compound represented by the general formula () is 0.01% by weight based on 100 parts by weight.
~20% by weight, and the triplet energy is ~40
The sensitizer is 68 kcal/mole per mole of the spirooxazine compound represented by the general formula ().
The use of 0.01 mol to 20 mol is preferred. The composition of the present invention can be made into articles by various manufacturing methods shown below. For example, a spirooxazine compound represented by the general formula () and a sensitizer are dissolved in various monomers,
There is a method in which the matrix resin is then polymerized by an appropriate means such as the use of a radical initiator and contained as a matrix resin, or a method in which the matrix resin and other components are dissolved in an appropriate solvent and formed into a film by casting. . In particular, in the latter method, it is preferable to coat a suitable substrate such as an inorganic glass substrate, a plastic substrate, a film, paper, wood, metal article, ceramics, etc. from the viewpoint of a large degree of flexibility in the range of application. It can be done. Furthermore, by applying the solution to nails and drying it, it can be used for purposes such as manicure. On the other hand, in addition to the above-mentioned essential ingredients, light resistance, heat resistance,
In order to improve antioxidant properties and coating properties during application, especially the smoothness of the coating film, we add UV absorbers, antioxidants, singlet oxygen quenchers, surfactants, etc. It is also possible to improve practical performance. In addition, various organic solvents can be used as a solvent when applying the composition of the present invention to various substrates as a coating composition, and specifically, various alcohols, ketones, and ethers can be used. , esters, aromatic (halogenated) hydrocarbons, aliphatic (halogenated) hydrocarbons, cellosolves, various formamides, sulfoxy compounds, etc., which are particularly limited as long as they dissolve the matrix resin and other components. It's not a thing. In addition, coating methods include applying a coating composition consisting of a mixed solution of the matrix resin and other components by dipping or spin coating, or coating the substrate with the matrix resin in advance and then photochromic coating. Various methods can be applied, such as a method in which a compound and a sensitizer are incorporated into the matrix resin using a dyeing method or the like. For the purpose of further improving the practicality of the composition having photochromic properties in the present invention, it is also possible to provide a coating having hard coat properties on the article to improve the scratch resistance of the article. Preferred embodiments of the present invention include photochromic molded articles, such as sunglass lenses made of transparent plastic or colored transparent plastic, or corrective lenses, coated with the composition of the present invention. Furthermore, a composition in which the composition of the present invention is laminated in a sandwich-like manner using inorganic glass plates is also preferable from the viewpoint of light resistance, heat resistance, and the like. Examples are shown below to clarify the gist of the present invention, but the present invention is not limited to these Examples. Examples 1 to 10, Comparative Example 1 (1) Production of photochromic articles (a) Preparation of coating composition Copolymer consisting of methyl methacrylate/butyl methacrylate/butyl acrylate/hydroxyethyl methacrylate/acrylic acid (OH value: 10 ) and 300 g of a 50% by weight solution of toluene/butyl acetate (50/50 weight ratio) and 37.5 g of melamine resin (Yuban 22R, manufactured by Mitsui Toatsu Chemical Co., Ltd.) were further diluted to 25% by weight with methyl ethyl ketone, and silicone-based A surfactant was added, and 10.5 g of each of the photochromic compounds shown in Table 1 and the respective amounts (g) of a sensitizer were added to prepare a coating composition. (B) Coating and drying The coating composition obtained in (a) above was applied to a thickness of about 15 μm on a 1.0 mm thick glass plate by flow coating. The coated glass plate was heat-cured at 90°C for 10 hours. (2) Performance test The following tests were conducted. The results are shown in Table 1. (a) Photochromic performance Winter sunlight 0.6mW/cm ² (Oak Manufacturing Co., Ltd.
The difference in color density was measured when irradiated with an ORC ultraviolet luminometer (Model UV-302A, manufactured by Co., Ltd.), with no sensitizer added as a blank.

【table】

[Table] [Effects of the Invention] The composition obtained by the present invention has the following effects. 1. Has photochromic performance with excellent color developing and erasing properties. In particular, sufficiently high color density can be obtained even under high temperatures in summer and weak sunlight in winter. 2. Has photochromic performance with excellent repeatability and good durability. 3. It is possible to produce articles with photochromic properties that are excellent in heat resistance, water resistance, and chemical resistance.

Claims (1)

[Scope of Claims] 1. A photochromic device characterized by containing a spirooxazine compound represented by the following general formula (), a matrix resin, and a thioxanthone having a triplet energy of 40 to 68 kcal/mole or a substituent derivative thereof. A composition with. (However, X is C- _R9 or nitrogen, and _R9 is selected from hydrogen, a _C1 - _C8 alkyl group, an alkoxy group, and a halogen. _R1 is a _C1 - _C6 alkyl group or a _C7 ~ _C20 substituted or unsubstituted aralkyl group; _R2 and _R3 each represent hydrogen, _C1 to _C5 alkyl, phenyl, mono-
and a cycloaliphatic ring selected from the group consisting of di-substituted phenyl, benzyl, or in combination containing 6 to 8 carbon atoms (including spiro carbon atoms);
alicyclic ring, norbornyl, and adamantyl. _R4 , _R5 , _R6 , _R7
and R ₈ is hydrogen, a C ₁ to _{C 5} alkyl group, an alkoxy group, a halogen, a nitro group, a cyano group, a hydroxy group, a C ₁ to _{C 5} halogenated alkyl group, an alkoxycarbonyl group, or an amino group. To be elected. 2. The composition having photochromic properties according to claim 1, wherein the matrix resin is a plastic material. 3 The plastic material is a polymer or copolymer of polyol (allyl carbonate) monomer,
(meth)acrylate polymers and copolymers,
Melamine resin, urethane resin, nylon resin, polycarbonate, polyethylene terephthalate,
Styrene polymers and copolymers, celluloses,
Claim 2 characterized in that it is one or more selected from the group consisting of epoxy resins, vinyl acetate polymers and copolymers, polyvinyl alcohol, urea resins, polyvinyl chloride, polyvinyl butyral, and polyvinyl butyrate. A composition having photochromic properties as described in 1.