JPH0529671B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Field of Application] The present invention relates to an article having photochromic properties that is excellent in color developing and fading properties, durability, heat resistance, and fatigue resistance. [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, and are disclosed in Japanese Patent Publications No. 45-28892, Japanese Patent Publication No. 49-48631, and Japanese Unexamined Patent Publication No. 1983-1989. −36284, spiro (indoline)
Oxazine compounds, or spiro (indolines)
A technique has been disclosed in which a pyridoxazine compound is contained in polymethyl methacrylate, cellulose, vinyl chloride, or the like. In addition, several attempts have already been made to create composites using these photochromic compounds. For example, JP-A-59-78271, JP-A-59-78271,
Japanese Patent No. 78272 describes a photochromic coating composition containing a spiropyran compound in a silane compound. Further, an example of simply dispersing and mixing a hindered amine as a light stabilizer in a matrix is shown in JP-A-61-241383. [Problems to be Solved by the Invention] However, the spiropyran compound has a problem in fatigue resistance during repeated use of light-emitting and decoloring. Furthermore, the spirooxazine compound technology disclosed in Japanese Patent Publication No. 45-28892 has problems in light resistance, fatigue resistance, heat resistance, hot water resistance, and the like. In addition, techniques such as Japanese Patent Application Laid-open No. 59-78271,
It had problems such as poor light resistance, poor fatigue resistance, and slow decoloring speed. Furthermore, the technique disclosed in JP-A-61-241383 had a problem of poor heat resistance, water resistance, and solvent resistance. The present invention aims to eliminate the drawbacks of the prior art, and aims to provide an article having photochromic properties that is excellent in fatigue resistance, color development speed, color erasure speed, and hot water resistance in repeated actions. . [Means for Solving the Problems] The present invention has the following configuration to achieve the above object. "An article having photochromic properties characterized by containing at least the following components A and B. Component A: a photochromic compound represented by the general formula () (However, X is C-R ₉ or nitrogen, and R ₉
is hydrogen, _C1 - _C8 alkyl group, alkoxy group,
Selected from halogen. R ₁ is selected from the group consisting of a C ₁ to C ₆ alkyl group and a C ₇ to _{C 20} substituted or unsubstituted aralkyl group. R ₂ and R ₃ are each selected from the group consisting of hydrogen, a C ₁ to _{C 5} alkyl group, a phenyl group, a mono- or di-substituted phenyl group, and a benzyl group, or are combined to form 6 to 8 It is selected from a cyclic ring selected from alicyclic rings containing carbon atoms (including spiro carbon atoms), norbornyl groups, and adamantyl groups.
R ₄ , R ₅ , R ₆ , R ₇ and R ₈ each represent hydrogen, a C ₁ to C ₅ alkyl group, an alkoxy group, a halogen, a nitro group, a cyano group, a hydroxy group,
It is selected from a (meth)acryloxy group, a _C1 - _C5 halogenated alkyl group, an alkoxycarbonyl group, and an amino group. ) Component B: having a substituent selected from an amide group, an aminoalkyl group and a hindered amino group,
A polymer containing 0.2% to 50% by weight of at least one selected from acrylic and methacrylic monomers as a copolymerization component. Here, the spirooxazine compound represented by the general formula () can be a known spiro(indoline)oxazine compound or a spiro(indoline)pyridoxazine compound. (JP-A-45-28892, JP-A-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 broaden the absorption wavelength of the coloring species, create mixed colors, and further improve the apparent durability. Among the photochromic compounds represented by the above general formula (), R ₁ is particularly a lower alkyl group, a substituted or unsubstituted benzyl group, and R ₄ ,
As R ₅ , R ₆ , R ₇ , and R ₈ , compounds containing hydrogen, a lower alkyl group, a lower alkoxy group, or a halogen are particularly preferably used from the viewpoint of color density, fatigue resistance, and the like. These photochromic compounds are preferably present in a molecularly dispersed state in a matrix polymer consisting of component B described below from the viewpoint of color development and color erasing speed. Molecular dispersion here means that photochromic compounds do not associate or crystallize themselves, but each molecule exists independently in the matrix. The photochromic compound represented by the general formula () contained in the matrix polymer is
0.2% to 20% by weight is preferred. As a method for incorporating a photochromic compound into the B component, for example, a method of dissolving both the B component and the photochromic compound in a solvent system, and then removing the solvent, and furthermore, a method of incorporating the photochromic compound into the monomer forming the B component, is possible. Examples include a method in which a photochromic compound is dissolved and then polymerized using an appropriate polymerization initiator, for example, an azo compound such as azobisisobutyronitrile. The above-mentioned solvent is preferably one that can dissolve the photochromic compound as component A and also dissolve component B, but even if one of the components cannot be dissolved,
It is also possible to use mixed systems with soluble solvents. Examples of such solvents include various alcohols, ketones, ethers, esters, aromatic (halogenated) hydrocarbons, and aliphatic (halogenated)
Examples include hydrocarbons, cellosolves, various formamides, and sulfoxides. In addition, if the photochromic compound which is component A has a polymerizable functional group such as a (meth)acryloxy group, it can be simply converted into B as described above.
In addition to the method of adding it to the component, it is also possible to integrate it with the B component by copolymerizing it during the production of the B component. This is an effective means, especially in applications where solvent resistance is important. Component B in the present invention is a polymer containing 0.2% to 50% by weight of an acrylic and/or methacrylic monomer having a substituent selected from an amide group, an aminoalkyl group, and a hindered amino group. Here, what is an amide group?

It is a functional group represented by the formula: where Y and Z are hydrogen or an alkyl group having 1 to 4 carbon atoms. Further, Y and Z may be the same type or different types. On the other hand, what is an aminoalkyl group?

It is a functional group represented by the formula: L and M are hydrogen and an alkyl group having 1 to 4 carbon atoms. Furthermore, L and M may be of the same type or different types. These acrylic and methacrylic monomers having an amide group and an aminoalkyl group are generally obtained by a dehydration condensation reaction between acrylic acid or methacrylic acid and a corresponding amine or aminoalkyl alcohol, respectively. Further, the hindered amino group in the present invention is a functional group represented by the following general formula (). (In the formula, R ₁₀ , R ₁₁ , R ₁₃ and R ₁₄ are lower alkyl groups, and R ₁₂ is selected from lower alkyl groups and hydrogen.) Acrylic or methacrylic monomers having such hindered amino groups are referred to as hydroxy hindered amines. It is prepared by esterification with various (meth)acrylic acids or reaction with (meth)acrylic acid chloride. The (meth)acrylic monomer having at least one substituent selected from the above amide groups, aminoalkyl groups, and hindered amino groups must be contained in the polymer as component B in an amount of 0.2 to 50% by weight. It is. i.e. 0.2
If the content is less than 50% by weight, the effect of its inclusion will not be recognized, and if it exceeds 50% by weight, there will be problems such as yellow coloration, brittleness, and even inability to obtain a uniform polymer. It goes without saying that not only one type of monomer having these amide groups, aminoalkyl groups, or hindered amino groups as a substituent, but also two or more types thereof can be used in combination. Specific examples of monomers having at least one substituent selected from amide groups, aminoalkyl groups, and hindered amino groups include (meth)acrylamide, N-n-butoxymethyl (meth)acrylamide, N,N-dimethyl ( meth)acrylamide, N,N-diethyl(meth)
Acrylamide, N,N-di-n-butoxy(meth)acrylamide, N-methoxymethyl(meth)acrylamide, N,N-dimethoxy(meth)acrylamide, N,N-diethoxy(meth)acrylamide, N,N-di -n-propoxy (meth)acrylamide, dimethylaminomethyl (meth)acrylate, dimethylaminoethyl (meth)acrylate, dimethylaminopropyl (meth)acrylate, dimethylaminobutyl (meth)acrylate, (meth)acrylic acid diethylaminomethyl, diethylaminoethyl (meth)acrylate, diethylaminopropyl (meth)acrylate,
Diethylaminobutyl (meth)acrylate, dipropylaminomethyl (meth)acrylate, (meth)
Dipropylaminoethyl acrylate, dipropylaminopropyl (meth)acrylate, dipropylaminobutyl (meth)acrylate, -N,N-methylbutylaminoethyl (meth)acrylate,
2,2,6,6-tetramethyl-4-piperidinyl acrylate, 2,2,6,6-tetramethyl-4-piperidinyl methacrylate, 1,2,
Examples include monomers such as 2,6,6-pentamethyl-4-piperidinyl acrylate and 1,2,2,6,6-pentamethyl-4-piperidinyl methacrylate. It is also possible to add various crosslinking agents to component B in the present invention for the purpose of crosslinking and curing the polymer. Examples of crosslinking agents that can be added include melamine resins, urea resins, and epoxy resins. Furthermore, for the purpose of accelerating the crosslinking reaction, various accelerators such as acids, bases, various metal salts, metal chelate compounds, epoxy curing agents, etc. can be used in combination. In addition, although they do not participate in crosslinking, it is preferable to add various surfactants as surface smoothing agents for the practical use of the matrix, for example, when it is applied as a coating composition. In addition, various sensitizers and ultraviolet absorbers are preferably added for the purpose of improving photochromic properties, such as color density. When using the present invention for optical applications such as sunglass lenses and corrective lenses, the glass transition temperature of the polymer serving as component B should be 10°C or higher in order to satisfy color development and fading properties at room temperature. preferable. In order to satisfy the color development density especially in summer, it is more preferable that the temperature is 40°C or higher. The article obtained by the present invention can be used in various forms, such as a film, a coating film, or a molded product, depending on the purpose of use, but from a cost standpoint, it is preferable to apply it as a coating film to various base materials. desirable. When used as a coating film, 0.5μ
m to 50 μm is preferable. Moreover, various materials such as inorganic glass, fabric, wood, paper, metal, plastic, and ceramic can be used as the base material to be coated. Further, the shape of the base material is not particularly limited, such as a film, a sheet, a molded product, etc. Application methods include methods used in the conventional coating industry, such as dip coating, spin coating, flow coating, roll coating, curtain flow coating, bar coating, and brush coating, as well as screen printing methods. It is. 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, in order to further increase light resistance, heat resistance, antioxidant properties,
Furthermore, it is also possible to further improve practical performance by adding antioxidants, singlet oxygen quenchers, surfactants, etc. to improve the coating properties during application, especially the smoothness of the coating film. It is. In addition, various organic solvents can be used as a solvent when applying the article of the present invention to various substrates as a coating composition, and specifically, various alcohols, ketones, ethers, Those that dissolve matrix resin and other components, such as esters, aromatic (halogenated) hydrocarbons, aliphatic (halogenated) hydrocarbons, cellosolves, various formamides, and sulfoxides, are particularly limited. isn't it. In order to further improve the practicality of the article 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 in which the article of the present invention is coated on sunglass lenses or corrective lenses made of transparent plastic or colored transparent plastic. Furthermore, it is also preferable to laminate the article of the present invention in a sandwich-like structure using inorganic glass plates or the like from the viewpoint of light resistance, heat resistance, and the like. The article of the present invention is preferably used for optical articles such as sunglasses and corrective lenses, and window glass for automobiles, homes, offices, etc., and for purposes that require light adjustment particularly related to sunlight. . [Examples] 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 4, Comparative Examples 1 to 4 (1) Production of photochromic articles (a) Preparation of coating composition 50% by weight solution of the copolymer shown in Table 1 300
g and melamine resin (Mitsui Toatsu Chemical Co., Ltd. product, Yuban 22R) 37.5 g, further added methyl ethyl ketone to dilute to 25% by weight, added a silicone surfactant, and further added 1-
Benzyl-3,3-dimethylspiro[indolino-2,3'-[3H]naphtho[2,1-b]
A photochromic compound consisting of (1,4)-oxazine] was added to prepare a coating composition. As a comparative example, a coating composition was prepared using a polymer shown in Table 1 that was not copolymerized with an amide group-containing monomer or an aminoalkyl group-containing monomer. (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 solar radiation 0.58 mW/cm ² (Oak Manufacturing Co., Ltd.
The color density was measured when irradiated with an ORC ultraviolet illuminometer model UV-302A manufactured by Co., Ltd., and expressed as total light transmittance. (b) Light resistance test After 20 hours of light irradiation using a fade meter, a color development test was performed using a chemical lamp. Note that the determination is as shown below. A: No difference was observed before and after the fade meter test. B: There is a slight difference between before and after the test, but there is almost no difference. C: Although there is a difference between before and after the test, it has practical coloring properties. D: Color development is observed after the test, but an extreme decrease in density is observed. E: Almost no color developed. Incidentally, the intermediate values are indicated by A to B, etc.

【table】

[Table] Examples 5 to 7, Comparative Example 5 (1) Preparation of photochromic articles (a) Preparation of coating composition 300% solution of 50% by weight copolymer shown in Table 2
g and melamine resin (Mitsui Toatsu Chemical Co., Ltd. product, Yuban 22R) 37.5 g, further added methyl ethyl ketone to dilute to 25% by weight, added a silicone surfactant, and further added 1-
Benzyl-3,3-dimethylspiro[indolino-2,3'-[3H]naphtho[2,1-b]
A photochromic compound consisting of (1,4)-oxazine] was added to prepare a coating composition. In addition, as Comparative Example 5, it was produced in the same manner as Example 1 except that 5.0% by weight of bis(2,2,6,6-tetramethyl-4-piperidinyl) sebatate was used as the hindered amine. (b) Coating and drying The same procedure as in Example 1 was carried out. (2) Performance test The following tests were conducted. The results are shown in Table 1. (a) Photochromic performance Summer solar radiation 2.8 mW/cm ² (Oak Manufacturing Co., Ltd.
The color density was measured when irradiated with an ORC ultraviolet illuminometer model UV-302A manufactured by Co., Ltd., and expressed as total light transmittance. (b) Light resistance test It was conducted in the same manner as in Example 1. (c) Hot water test The appearance was examined after immersion in hot water set at 65°C for 16 hours.

[Table] Example 8 1-Benzyl-3,3-dimethylspiro[indolino-2,3'-[3H]naphtho[2,1-b]
The same procedure as in Example 1 was carried out using the same composition, except that a compound represented by the following formula () was used instead of the photochromic compound consisting of (1,4)-oxazine]. The evaluation results are shown in Table 3. Comparative Example 6 1-Benzyl-3,3-dimethylspiro[indolino-2,3'-[3H]naphtho[2,1-b]
The same operation was carried out using the same composition as in Comparative Example 1, except that a compound represented by the formula () was used instead of the photochromic compound consisting of (1,4)-oxazine]. The evaluation results are shown in Table 3. Example 9 1-benzyl-3,3-dimethylspiro[indolino-2,3'-[3H]naphtho[2,1-b]
The same operation was carried out using the same composition as in Example 2, except that a compound represented by the formula () was used instead of the photochromic compound consisting of (1,4)-oxazine]. The evaluation results are shown in Table 3. Comparative Example 7 1-Benzyl-3,3-dimethylspiro[indolino-2,3'-[3H]naphtho[2,1-b]
The same operation was carried out using the same composition as in Comparative Example 2, except that a compound represented by the formula () was used instead of the photochromic compound consisting of (1,4)-oxazine]. The evaluation results are shown in Table 3. Example 10 1-benzyl-3,3-dimethylspiro[indolino-2,3'-[3H]naphtho[2,1-b]
The same procedure as in Example 1 was carried out using the same composition, except that a compound represented by the following formula () was used instead of the photochromic compound consisting of (1,4)-oxazine]. The evaluation results are shown in Table 3. Comparative Example 8 1-Benzyl-3,3-dimethylspiro[indolino-2,3'-[3H]naphtho[2,1-b]
The same operation was carried out using the same composition as in Comparative Example 1, except that a compound represented by the formula () was used instead of the photochromic compound consisting of (1,4)-oxazine]. The evaluation results are shown in Table 3. Example 11 1-Benzyl-3,3-dimethylspiro[indolino-2,3'-[3H]naphtho[2,1-b]
The same operation was carried out using the same composition as in Example 2, except that a compound represented by the formula () was used instead of the photochromic compound consisting of (1,4)-oxazine]. The evaluation results are shown in Table 3. Comparative Example 9 1-Benzyl-3,3-dimethylspiro[indolino-2,3'-[3H]naphtho[2,1-b]
The same operation was carried out using the same composition as in Comparative Example 2, except that a compound represented by the formula () was used instead of the photochromic compound consisting of (1,4)-oxazine]. The evaluation results are shown in Table 3. Example 12 1-benzyl-3,3-dimethylspiro[indolino-2,3'-[3H]naphtho[2,1-b]
The same procedure as in Example 1 was carried out using the same composition, except that a compound represented by the following formula () was used instead of the photochromic compound consisting of (1,4)-oxazine]. The evaluation results are shown in Table 3. Comparative Example 10 1-Benzyl-3,3-dimethylspiro[indolino-2,3'-[3H]naphtho[2,1-b]
The same operation was carried out using the same composition as in Comparative Example 1, except that a compound represented by the formula () was used instead of the photochromic compound consisting of (1,4)-oxazine]. The evaluation results are shown in Table 3. Example 13 1-Benzyl-3,3-dimethylspiro[indolino-2,3'-[3H]naphtho[2,1-b]
The same procedure as in Example 1 was carried out using the same composition, except that a compound represented by the following formula () was used instead of the photochromic compound consisting of (1,4)-oxazine]. The evaluation results are shown in Table 3. Comparative Example 11 1-Benzyl-3,3-dimethylspiro[indolino-2,3'-[3H]naphtho[2,1-b]
The same operation was carried out using the same composition as in Comparative Example 1, except that a compound represented by the formula () was used instead of the photochromic compound consisting of (1,4)-oxazine]. The evaluation results are shown in Table 3.

[Table] [Effects of the Invention] The article having photochromic properties obtained by the present invention has the following effects. (1) Stability against light-induced degradation is significantly improved. (2) Excellent color development. (3) Durability, hot water resistance, and heat resistance can be easily improved by adding various crosslinking agents, antioxidants, surfactants, etc.

Claims (1)

[Scope of Claims] 1. An article having photochromic properties characterized by containing at least the following components A and B. Component A: Photochromic compound represented by general formula () (However, X is C-R ₉ or nitrogen, and R ₉
is hydrogen, _C1 - _C8 alkyl group, alkoxy group,
Selected from halogen. R ₁ is selected from the group consisting of a C ₁ to C ₆ alkyl group and a C ₇ to _{C 20} substituted or unsubstituted aralkyl group. R ₂ and R ₃ are each selected from the group consisting of hydrogen, a C ₁ to _{C 5} alkyl group, a phenyl group, a mono- or di-substituted phenyl group, and a benzyl group, or are combined to form 6 to 8 It is selected from a cyclic ring selected from alicyclic rings containing carbon atoms (including spiro carbon atoms), norbornyl groups, and adamantyl groups.
R ₄ , R ₅ , R ₆ , R ₇ and R ₈ each represent hydrogen, a C ₁ to C ₅ alkyl group, an alkoxy group, a halogen, a nitro group, a cyano group, a hydroxy group,
It is selected from a (meth)acryloxy group, a _C1 - _C5 halogenated alkyl group, an alkoxycarbonyl group, and an amino group. ) Component B: having a substituent selected from an amide group, an aminoalkyl group and a hindered amino group,
A polymer containing 0.2% to 50% by weight of at least one selected from acrylic and methacrylic monomers as a copolymerization component.