JPH03296594A - Photochromic material - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a novel photochromic material that develops color when exposed to ultraviolet light and has the function of decolorizing when left in a dark place or when irradiated with visible light.

The photochromic material of the present invention can be preferably used in a wide range of fields, such as textiles, toys, decorative materials such as makeup cosmetics, optical filters, display materials, masking materials, recording materials, image forming materials, and materials for photosensitive materials. can.

[Prior Art] Spiro-based photochromic compounds exhibit a wide variety of color tone changes, many of which have large molar absorption coefficients, and have been conventionally used in various fields.

Conventionally, such compounds having photochromic properties have generally been used in the form of being dispersed or dissolved in a polymer compound or the like. However, in this technology,
Although good color density can be obtained, the photochromic compound may bleed out from the polymer compound,
Furthermore, there is a problem that it is eluted by other solvents. In order to solve these problems and improve durability, Japanese Patent Application Laid-Open No. 63-250380 discloses a technique in which a substituent that can be polymerized or condensed is introduced into a photochromic compound and incorporated into a polymer compound through a covalent bond. , JP-A No. 63-25081, etc.

[Problems to be Solved by the Invention] However, the techniques disclosed in Japanese Patent Application Laid-Open No. 63-250380 are inferior in terms of light resistance and color density.

The present invention aims to solve the problems of the prior art, and aims to provide a photochromic material that has excellent durability in photochromic properties, light resistance, and color density.

[Means for Solving the Problems] The present invention has the following configuration to achieve the above object.

"A photochromic material comprising at least a polymer containing a spirooxazine compound as a polymerizable component and a photochromic compound." A spirooxazine compound (hereinafter referred to as a polymerizable spirooxazine compound) used as a polymerizable component in the present invention (referred to as "compound") refers to a compound represented by the following large quantity [I].

A type selected from a lysine ring, a tetrahydropyridine ring, a dihydropyridine ring, an indoline ring, a benzindoline ring, a tetrahydroquinoline ring, an acridine ring, a benzoxazoline ring, and a benzothiazoline ring, and α
The nitrogen atom in the ring is Y.

It is bonded to R2 or an organic group R. Here, R
is an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, and an aralkyl group having 6 to 20 carbon atoms.
represents a substituent selected from 19 aryl groups and cycloalkyl groups having 3 to 10 carbon atoms.

The β ring is a benzene ring, a naphthalene ring, an anthracene ring,
One type selected from a phenanthrene ring, a quinoline ring, a dibenzofuran ring, a dibenzothiophene ring, a carbazole ring, and a benzonaphthothiophene ring.

R1 is hydrogen, an amino group having θ to 20 carbon atoms, and 1 to 2 carbon atoms.
0 alkoxy group, aralkoxy group having 7 to 20 carbon atoms,
Aryloxy group having 6 to 14 carbon atoms, acyloxy group having 2 to 20 carbon atoms, alkyl group having 1 to 20 carbon atoms, 7 carbon atoms
represents a substituent selected from an aralkyl group having ~20 carbon atoms and an aryl group having 6 to 20 carbon atoms.

R2 represents a radically polymerizable functional group.

n is an integer of 1 or more.

Y represents an organic group having 1 to 20 carbon atoms.

m represents 0 or 1. However, when Y, R2 is bonded to the nitrogen atom in the α ring, m represents 1. ) In general formula (I), the α ring is selected from a pyrrolidine ring, a pyrrole ring, a piperidine ring, a tetrahydropyridine ring, a dihydropyridine ring, an indoline ring, a benzindoline ring, a tetrahydroquinoline ring, an acridine ring, a benzoxazoline ring and a benzothiazoline ring. It is a kind of

The nitrogen atom contained in this α ring exists bonded to Y□R2 or an organic group R, and is represented by.

Here, specific examples of the substituent R include a chain alkyl group having 1 to 20 carbon atoms such as a methyl group, ethyl group, and octadecyl group, and a chain alkyl group having 3 to 20 carbon atoms such as a tert-butyl group and a 2-methylpentyl group. Branched alkyl groups, cyclohexyl groups, norbornyl groups, adamantyl groups, etc. with 3 or more carbon atoms
10 cycloalkyl groups, alkenyl groups having 2 to 20 carbon atoms such as vinyl groups, allyl groups, hexenyl groups, 1,3-butadienyl groups, isopropenyl groups, benzyl groups, phenethyl groups, (2-naphthyl)methyl groups, etc. carbon number 7~
20 represents an aryl group having 6 to 19 carbon atoms, such as an aralkyl group, a phenyl group, or a 2-naphthyl group.

R may be substituted, and in such a case, specific examples of the substituent include a hydroxy group; an amino group such as an amino group and a dibenzylamino group; an alkoxy group such as a methoxy group, an ethoxy group, and a propoxy group; Acyloxy groups such as benzoyloxy; alkyl groups such as methyl, ethyl, trifluoromethyl, butyl; benzyl, 4-(
Aralkyl groups such as 2,3-epoxypropyl) phenethyl groups; Aryl groups such as phenyl groups; Halogen groups such as fluoro and chloro groups; Cyano groups; Carboxy groups; Nitro groups;
Acyl group such as acetyl group; ethoxycarbonyl group, 3.
Alkoxycarbonyl groups such as 4-epoxybutyloxycarbonyl group; Carbamoyl groups such as carbamoyl group and N-phenylcarbamoyl group; Carbamoyloxy groups such as (N-(acetoxy)propylcarbamoyl)oxy group; Sulfonic acids, metal salts thereof ( Examples include sulfonic acid groups such as sodium and lithium salts.

Y in R2, which is another substituent that can be bonded to the nitrogen atom of the α ring, is an organic group having 1 to 20 carbon atoms, specific examples of which include methylene group, propylene group, etc. alkylene group, CH3 -(-CH2CH2Ote], -←CH2CH-0-masu.

Examples include alkyleneoxy groups such as (a represents a natural number), arylene groups such as phenylene groups, and naphthylene groups. Here, the substituents/bonds represented by Y are present. Also, m must be 1. Furthermore, R2 is a radical polymerizable functional group, and specific examples thereof include acryloxy group, methacryloxy group, methacrylamide group, p-vinylbenzoyloxy group, m-vinylbenzyl group, (2-(meth)acryloxy group, (loxyalkyl)amino group, N-(2-(meth)acryloxy)alkylcarbamoyl group, (N-(3-(meth)acryloxy)alkylcarbamoyl)oxy group, and the like.

The above Y, R2 groups can be substituted on atoms other than the nitrogen atom in the α ring, on each atom in the β ring, and in R1, etc. In that case, even if m is 0, It may be 1. Further, n, which is the number of functional groups included in the general formula (I) of Y, .

There is no problem whether R2 is of the same type or different types.

On the other hand, β included in general formula (1) like the α ring
The ring is selected from a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a quinoline ring, a dibenzofuran ring, a dibenzothiophene ring, a carbazole ring, and a benzonaphthothiophene ring.

Various substituents can be introduced into the α ring and β ring,
By introducing a substituent, it is possible to control the speed of color development and fading, which is one of the photochromic properties, and further control the color tone of color development. Specific examples of substituents that can be introduced and are preferably applied include those having 1 to 20 carbon atoms;
alkyl groups having 7 to 20 carbon atoms, aryl groups having 6 to 19 carbon atoms, cycloalkyl groups having 3 to 10 carbon atoms including the 3' carbon in the α ring, hydroxy groups, amino group, organic substituted amino group having 1 to 20 carbon atoms, alkoxy group having 1 to 20 carbon atoms, 7 to 20 carbon atoms
20 aralkoxy group, aryloxy group having 6 to 19 carbon atoms, acyloxy group having 2 to 20 carbon atoms, halogen group, cyano group, carboxy group, nitro group, acyl group having 2 to 20 carbon atoms, acyl group having 2 to 20 carbon atoms Substituents selected from alkoxycarbonyl groups, carbamoyl groups, carbamoyloxy groups, and sulfonic acid groups can be mentioned.

Furthermore, those containing a heteroatom in the β ring are particularly effective as a means for shortening the wavelength of the coloring species or for including a plurality of absorption maximum wavelengths.

Among them, a carbazole ring containing a nitrogen atom and a dibenzofuran ring containing an oxygen atom are preferably used from the viewpoint that they are relatively easy to synthesize and exhibit the above-mentioned properties significantly.

The above-mentioned polymerizable spirooxazine compounds of the present invention are disclosed in JP-A-63-93788, JP-A-63-199279, JP-A-63-250380, etc., and naturally these are also disclosed in the present invention. This is a polymerizable spirooxazine compound that can be used in the invention.

These polymerizable spirooxazine 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 a mixed color, and further improve the apparent durability.

In the present invention, a polymer containing at least one polymerizable spirooxazine compound (hereinafter referred to as a photochromic polymer) is used as one of the polymerizable monomers. That is, the photochromic polymer may be formed by polymerizing only the polymerizable spirooxazine compound of the present invention, or may be a copolymer with other copolymerizable monomer components. When using a copolymer, the proportion of the polymerizable spirooxazine compound contained in the copolymer varies depending on the intended function of the copolymer, but it should be determined by considering sufficient color density and economic efficiency. In terms of quantity, it is preferably contained in a proportion of 0.2% by weight or more and 60% by weight or less in the copolymer. If this content is less than 0.2% by weight, it is difficult to obtain a sufficient concentration during color development. Moreover, if it exceeds 60% by weight, the price of the obtained cured product becomes high.

Together with the polymerizable spirooxazine compound of the present invention,
As the polymerizable monomer to form the copolymer, any monomer can be used as long as it is copolymerizable, but it is important that the degree of polymerization is controlled and monomer selection is easy. In particular, it is preferable to use a monomer having a radically polymerizable functional group because it can be introduced.

Examples of monomers having radically polymerizable functional groups include acrylic monomers, styrene monomers, diene monomers, vinyl monomers, and nitrile monomers. Acrylic monomers are preferred. The acrylic monomer is acrylate or methacrylate, and specific examples of acrylic monomers having an alkyl group or alkylene oxide group having 4 or more and 20 or less carbon atoms include n-butyl (meth)acrylate,
Isobutyl (meth)acrylate, 2-ethylhexyl (
meth)acrylate, isodecyl (meth)acrylate, n-lauryl (meth)acrylate, dodecyl (meth)acrylate, n-stearyl (meth)acrylate and methoxydiethylene glycol (meth)arylate, methoxytriethylene glycol (meth)acrylate, methoxytetraethylene Examples include glycol (meth)acrylate, methoxypolyethylene glycol (meth)acrylate such as methoxytripropylene glycol (meth)arylate, and the like.

In addition, for the purpose of further improving light resistance, chemical resistance, etc., (meth)acrylic monomers having a hindered amino group, (meth)acrylic monomers containing a carboxyl group, (meth)acrylic monomers containing an amino group, and (meth)acrylic monomers containing an amide group (
It is preferable to copolymerize a meth)acrylic monomer or the like.

Polymerization of such a polymerizable spirooxazine compound and a covalently bonded monomer can be achieved by methods such as addition reaction and vinyl polymerization, but from the viewpoint of ease of reaction and ease of controlling the amount added, etc. , radical polymerization, especially vinyl polymerization is preferred. In addition, various methods such as ionic polymerization, radical polymerization, and radiation polymerization can be applied to vinyl polymerization, but in particular, azo-based polymers such as azobisisobutyronitrile are used in order to prevent the decomposition of spirooxazine compounds. Radical polymerization using a radical initiator is preferably applied.

Furthermore, it is also useful to add various crosslinking agents, and examples of the crosslinking agents include epoxy resins, melamine resins, urea resins, and urethane compounds. 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 the photochromic material of the present invention, a photochromic compound (the photochromic compound here means a monomer having photochromic properties) is dispersed and dissolved in order to further improve the coloring density of the above photochromic polymer. Specific examples of such photochromic compounds include organic photochromic compounds such as spiropyran compounds, spirooxazine compounds, spiropyridoxazine compounds, azobenzene compounds, triarylmethane compounds, fulgide compounds, stilbene compounds, dithizone mercury complex compounds, viologen compounds, and halogen compounds. Silveride compounds, titanium-containing salt compounds, Ag2
Examples include inorganic photochromic compounds such as O-8i02 compounds.

Among such photochromic compounds, ion-cleavable photochromic compounds such as spirooxazine compounds, spiropyran compounds, and spiropyridoxazine compounds are particularly useful from the viewpoint of easy achievement of coloring density and excellent solubility.

The proportion of these photochromic compounds dispersed and dissolved in the photochromic polymer is determined depending on the use of the photochromic material, but it is 1% by weight or more,
It is preferably within the range of 15% by weight or less. If the content is less than 1% by weight, it is difficult to obtain sufficient color density, and if it exceeds 15% by weight, the photochromic compound tends to bleed out from the resulting photochromic material.

When the photochromic material of the present invention is used by coating various molded articles, sheets, fibers, etc., various organic solvents can be used as the solvent used in the coating composition, and specifically, various alcohols,
Ketones, ethers, esters, aromatic (halogenated) hydrocarbons, aliphatic (halogenated) hydrocarbons,
It is not particularly limited as long as it dissolves the matrix resin and other components, such as cellosolves, various formamides, and sulfoxides.

When applied as a coating composition, it is preferable to add various surfactants as surface smoothing agents.

It is also preferable to add various sensitizers, ultraviolet absorbers, etc. for the purpose of improving photochromic properties, for example, color density. Furthermore, adding an antioxidant, a doublet oxygen quencher, and an ultraviolet absorber is effective in extending the life of the spirooxazine compound and preventing color change.

The photochromic material obtained by the present invention preferably has a thickness of 0.5 μm to 50 μm or more from the viewpoint of color density and the like. Also, from the perspective of light resistance,
It is particularly preferable that it is 5.0 μm or more. In addition, the base materials to be coated include inorganic glass, fabric, wood, paper, metal,
Various materials such as plastic and ceramics can be used.

In addition, the shape of the substrate to be coated is film, sheet,
It is not particularly limited to molded products, etc.

[Examples] Hereinafter, the present invention will be explained in more detail with reference to Examples.
The present invention is not limited to these.

Example 1 (1) Preparation of photochromic polymer 40 parts by weight of octyl methacrylate (hereinafter, parts by weight are simply expressed as parts), 40 parts of n-butyl methacrylate,
10 parts of methyl methacrylate, 1 (3-methylbenzyl)
10 parts of -3,3-dimethyl-9'-methacryloxyindolinospironaphthoxazine was polymerized using an azobis-based initiator in a nitrogen atmosphere at a polymerization temperature of 70 to 80°C for a polymerization time of 7 hours using toluene as a solvent. , a photochromic polymer with a solid content of 50% was prepared.

(2) Preparation of photochromic material 5 parts of 1-(3-methylbenzyl)-3,3-dimethyl-indolinospironaphthoxazine are blended with 100 parts of the photochromic polymer of (1) above, and a butyl acetate solvent is added. A photochromic material with a solid content of 30% was prepared by diluting with

(3) Sample preparation and evaluation The photochromic material obtained in 2) above was
It was applied onto a glass plate by a flow coating method to produce a film with a thickness of about 20 μm. 2.5mW/ by chemical lamp
When irradiated with cnr ultraviolet rays, the coloring density at 23° C. was 50% in terms of total light transmittance, indicating a deep color and an excellent deep blue and transparent appearance.

Comparative Example 1 Performance was evaluated in the same manner as in Example 1, except that in Example 1, only the photochromic polymer was used without adding any photochromic compound, and a photochromic material with a solid content of 30% was diluted with a butyl acetate solvent. did.

As a result, the total light transmittance was 60%, the color density was low, and the color development was insufficient.

Comparative Example 2 The content of n-butyl methacrylate in the photochromic polymer was changed to 40 parts, and 1-(3-methylbenzyl)3,3-dimethyl-9'-methacryloxyindolinospironaphtho was added to Example 1. The content of oxazine is 0 parts,
Furthermore, 1-(3-methylbenzyl)-3,3 to be blended
A photochromic material was obtained in the same manner as in Example 1, except that the content of -dimethyl-indolinospironaphthoxazine was 15%, and its performance was evaluated in the same manner.

As a result, the total light transmittance was 40%, which was good in terms of color density, but there were problems such as bleed-out of the photochromic compound from the coating film and precipitation of the photochromic compound from the coating liquid.

[Effects of the Invention] The photochromic material of the present invention has excellent durability and color density in photochromic properties.

Claims (1)

[Claims] (1) A photochromic material comprising at least a polymer containing a spirooxazine compound as a polymerizable component and a photochromic compound.