JPH04358146A - Photochromic photosensitive material and laminate - Google Patents

Abstract

PURPOSE:To improve a light resistance characteristic and to prevent the detefioration by long-term photoirradiation by incorporating a spirooxazine compd., nitroxy free radicals and a specific ratio of a UV absorbent and high- polymer material into the above material. CONSTITUTION:This material has a photochromic photosensitive layer 2 between at least two sheets of transparent substrates 1 and 4. This photochromic photosensitive material is constituted by incorporating the spirooxazine compd., the nitroxy free radicals, UV absorbent and the high-polymer material therein. In addition, the UV absorbent is incorporated therein in the amt. to shut off 30 to 90% of light of 350nm of incident light. The UV absorbent has absorption at <=400nm wavelength. Namely, the formation of undesirable compds. in the photochromic photosensitive compsn. essentially consisting of the spirooxadine compd. and the high-polymer material at the time of coloration and clecoloration reaction is prevented if the specific amt. of the UV absorbent is incorporated together with the nitroxy free radicals into this compsn.

Description

[Detailed description of the invention]

0001

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photochromic photosensitive material particularly excellent in light resistance and a photochromic laminate using the same.

0002

[Prior Art] Conventional photochromic photosensitive materials include, for example, those made by dispersing a spirooxazine-based photochromic compound in a polymer compound and forming a film, or those containing a photochromic compound on a substrate made of glass or a transparent polymer plate. A laminate in which a film of a polymer compound is attached or a transparent polymer film in which a photochromic compound is dispersed is sandwiched between substrates is known (Japanese Patent Laid-Open No. 60-205429). However, in conventional photochromic laminates containing such spirooxazine compounds, irreversible deterioration products are easily generated during coloring and decoloring, so there is a problem of deterioration due to long-term light irradiation. There was a point. In order to solve this problem, the present inventors first developed a triplet quencher (nitroxy free radical).
A photochromic photosensitive material with excellent light resistance has been proposed (Japanese Patent Laid-Open No. 1-74285), but there is a need for a material with even better light resistance.

0003

[Problems to be Solved by the Invention] The present invention has been made in view of the above-mentioned circumstances, and aims to further improve the light resistance of a photochromic photosensitive material containing nitroxy free radicals. This is the purpose.

0004

[Means for Solving the Problems] As a result of various studies in order to satisfy the above-mentioned requirements for photochromic photosensitive materials containing spirooxazine compounds, the present inventors have found that spirooxazine compounds and polymeric substances are the main components. In the photochromic photosensitive composition containing nitroxy free radicals and a specific amount of ultraviolet absorber, it is possible to prevent the formation of undesirable compounds during the coloring/decoloring reaction, thereby preventing long-term It was discovered that deterioration due to light irradiation can be prevented, and the present invention was completed.

That is, the gist of the present invention is that the ultraviolet absorber contains a spirooxazine compound, a nitroxy free radical, an ultraviolet absorber, and a polymeric substance, and that the ultraviolet absorber absorbs 30% of the 350 nm light of the incident light. The present invention relates to a photochromic photosensitive material containing an amount that blocks up to 90%, and a laminate using the same.

The present invention will be explained in detail below. Examples of spirooxazine compounds used in the photochromic photosensitive composition of the present invention include the following general formula (I):

[0007]

[Chemical formula 1]

(In the formula, R1, R2 and R3 are
each independently a substituted or unsubstituted alkyl group,
It represents a substituted or unsubstituted alkenyl group, cycloalkyl group or aryl group, and R2 and R3 may be bonded to each other and cyclized. Moreover, R1 is an alkylene group,
It may have another spirooxazine ring via an arylene group, forming a dimer compound as a whole. R4 represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. Rings X and Y each independently represent an optionally substituted hydrocarbon aromatic ring or heteroaromatic ring. Z represents an oxygen atom or a sulfur atom. ) can be mentioned.

In the compound represented by the above general formula (I), R1, R2 and R3 have a carbon number of 1
-28 Alkyl groups such as alkyl groups; alkoxyalkyl groups such as methoxyethyl group and ethoxyethyl group, alkoxyalkoxyalkyl groups such as methoxyethoxyethyl group and n-butoxyethoxyethyl group, methoxyethoxyethoxyethyl group, ethoxyethoxyethoxy Alkoxyalkoxyalkoxyalkyl groups such as ethyl groups, phenyloxyethyl groups, naphthyloxyethyl groups, aryloxyalkyl groups that may have substituents such as p-chlorophenyloxyethyl groups, benzyl groups, phenethyl groups, p- Arylalkyl groups which may have substituents such as chlorobenzyl group and p-nitrobenzyl group, cycloalkylalkyl groups such as cyclohexylmethyl group, cyclohexylethyl group, and cyclopentylmethyl group, allyloxyethyl group, 3-bromo Alkenyloxyalkyl groups that may have substituents such as allyloxyethyl groups, cyanoalkyl groups such as cyanoethyl groups and cyanomethyl groups, hydroxyalkyl groups such as hydroxyethyl groups and hydroxymethyl groups, tetrahydrofurfuryl groups, and tetrahydrofurfuryl groups. Substituted alkyl groups such as tetrahydrofuryl alkyl groups such as furylethyl groups; substituted or unsubstituted alkenyl groups such as allyl groups and 2-chloroallyl groups; cycloalkyl groups having 3 to 8 carbon atoms; or phenyl groups, p-
Substituted or unsubstituted aryl groups such as a methylphenyl group, a naphthyl group, and a m-methoxyphenyl group are mentioned, and R2 and R3 may be bonded to each other to form a cyclohexyl group, a cyclopentyl group, or the like. Furthermore, R1 can also be bonded to another spirooxazine ring via an alkylene group or an arylene group to form a dimeric compound as a whole. R4 represents a hydrogen atom; or an alkyl group having 1 to 5 carbon atoms such as a methyl group or an ethyl group.

In rings X and Y, examples of the hydrocarbon aromatic ring or heteroaromatic ring which may be substituted include a benzene ring, a naphthalene ring, a quinoline ring, and a phenanthrene ring. When having, as a substituent, a halogen atom such as a chlorine atom, a bromine atom, an iodine atom; an alkyl group having 1 to 6 carbon atoms; an alkoxy group;
Examples include alkoxycarbonyl group; alkoxysulfonyl groups such as methoxysulfonyl group and ethoxysulfonyl group; cyano group; amino group; dimethylamino group; nitro group.

The spirooxazine compounds used in the present invention are disclosed in, for example, Japanese Patent Publications Nos. 45-28892, 49-48631, 55-36284, 6
No. 0-112880, No. 61-186390, No. 61
-233079, 61-243087, 61-
No. 263982, No. 61-263983, No. 61-2
No. 68788, No. 63-14786, No. 63-115
No. 884, No. 63-115885, No. 63-3012
It can be easily synthesized by the method described in Publication No. 28, US Pat. No. 4,342,688, and the like.

In the present invention, among the compounds represented by the above general formula (I), the following general formula (II)

[Case 2]

(In the formula, R'1 is an alkyl group or alkoxyalkyl group having 1 to 20 carbon atoms, R'4 is a hydrogen atom or a methyl group, and X and Y are an optionally substituted hydrocarbon aromatic ring or hetero It is more preferable to use a spirooxazine compound represented by (representing an aromatic ring).

[0014] The nitroxy free radical, which is a triplet quencher, generally has the following formula:

It refers to a free radical having the structure shown below, and in the photochromic photosensitive material of the present invention, it is preferable to use a nitroxy free radical that is stable and can be isolated.

Specific examples of such nitroxy free radicals include those represented by the following general formula (III).

[C4]

(wherein R5 and R6 are each independently a substituted or unsubstituted aryl group, or
The carbon atom adjacent to the nitrogen atom represents a hydrocarbon group in which the third carbon atom or the fourth carbon atom is a carbon atom, and furthermore, R5 and R6 may be bonded to each other to form a ring, and the ring may be substituted. It may have a group. ) The synthesis of these nitroxy free radicals is described in "New Experimental Chemistry Course (edited by the Chemical Society of Japan, Maruzen Co., Ltd., Vol. 14, P. 1594-1598")
It can be carried out according to the method described in .

In addition, according to Bredt's rule, bicyclo-based nitroxy radicals are not oxidized to nitrone and stop at the nitroxy radical stage.

[Image Omitted] Other nitroxy free radicals include, for example,
Those listed in the above document, page 1597, Table 7.66 can be used.

Examples of nitroxyl free radicals particularly preferably used in the present invention include the following from the viewpoint of heat resistance and activity persistence.

[0019]

[C6]

As the ultraviolet absorber, for example, the following general formula (IV)

[C7]

Or general formula (V)

[Chemical formula 8]

Or general formula (VI)

[Chemical formula 9]

(In the formula, R7, R8, R9, R10
, R11, R12, R13, R14, R15, R16
, R17, R18, R19, R20, R21, R22,
R23, R24 and R25 each independently represent a hydrogen atom, a substituted or unsubstituted alkyl group, a cycloalkyl group or alkenyl group, a hydroxyl group, an alkoxy group, or a halogen group, and R26 is a substituted or unsubstituted alkyl group, Indicates an alkoxyalkyl group, n=0 or 1
shows. ) are listed.

Particularly preferred among the above ultraviolet absorbers are compounds that absorb at wavelengths of 400 nm or less, specific examples of which include the following.

[0025]

[Chemical formula 10]

[0026] Any polymeric substance may be used as long as it has good compatibility with the spirooxazine compound, nitroxy free radical and ultraviolet absorber, is optically transparent, and has excellent film-forming ability. For example, polymethyl methacrylate, polystyrene, polyvinyl acetate, polyvinyl butyral, cellulose acetate, polyvinyl chloride, polyvinylidene chloride, vinyl chloride.
Vinyl acetate copolymer, polypropylene, polyethylene,
polyacrylonitrile, urethane resin, epoxy resin,
Examples include phenoxy resin and polyester, among which polyvinyl butyral is preferred in terms of practicality and safety. Moreover, it may contain a plasticizer or be crosslinked, if necessary. Examples of plasticizers include phthalate-based plasticizers such as dibutyl phthalate and dioctyl phthalate, adipate-based plasticizers such as dioctyl adipate,
Examples include phosphate type plasticizers such as tricresyl phosphate, polyester type, polyether type, triethylene glycol di-2-ethyl butyrate type, etc. These plasticizers can be used alone or in combination. can.

The photochromic photosensitive material of the present invention is
Including a photochromic photosensitive layer formed on a film-like substrate, and further between at least two transparent substrates,
It is also possible to form a laminate by sandwiching the photochromic photosensitive layer described above. FIG. 1 shows a schematic cross-sectional view of an example of the photochromic laminate of the present invention, and in the figure, 1 is a transparent substrate, 2 is a photochromic photosensitive layer, 3 is a transparent intermediate film, and 4 is a transparent substrate. Examples of the transparent substrate include polyethylene terephthalate, cellulose acetate, polycarbonate, and glass. Further, when forming a photochromic laminate, it is preferable to provide a transparent interlayer film containing a thermoplastic polymer and a plasticizer as main components as a support. Examples of the thermoplastic polymer include polyacrylic ester, polystyrene, polyvinyl ester, halide, polyester, polyurethane, polyvinyl butyral, polyvinyl acetal, etc., and examples of the plasticizer include phosphates such as dibutyl phthalate and dioctyl phthalate, Examples include adipate types such as diorthyl adipate, phosphate types such as tricresyl phosphate, polyester types, polyether types, and triethylene glycol di-2-ethyl butyrate types. The thickness of the photochromic photosensitive layer is
Preferably 0.5 μm to 1 mm, more preferably 10
It is used in the range of ~500 μm.

The photochromic photosensitive material of the present invention, in which a UV absorber is used together with a nitroxy free radical in the photochromic photosensitive layer, can be prepared by, for example, adding these spirooxazine compounds, nitroxy free radicals, UV absorbers, and polymeric substances to a suitable solvent. It can be obtained by dissolving it in a suitable transparent support and coating this solution on a suitable transparent support using casting or a spinner. Furthermore, a laminate can be obtained by sandwiching this between the transparent substrates and using a conventional molding method such as vacuum pressure bonding.

In the present invention, the amount of the spirooxazine compound to be used is preferably 0.1 to the amount of the polymer compound.
It is set in the range of ~50% by weight, more preferably 0.3~20% by weight. If the amount of the spirooxazine compound is less than 0.1% by weight, sufficient optical density will not be obtained when the photochromic dye is colored, and if it exceeds 50% by weight, the optical density will remain constant and the cost will increase. So I don't like it. The amount of nitroxy free radicals used is preferably set in the range of 0.1 to 50% by weight, more preferably in the range of 0.3 to 20% by weight based on the polymeric substance. If the amount of nitroxy free radicals is less than 0.1% by weight, there is no effect, and even if the amount is more than 50% by weight, the effect remains constant and the cost increases, which is not preferable. Furthermore, the amount of the ultraviolet absorber, which is another additive component, needs to be such that it blocks 30 to 90 rays of 350 nm of the incident light. Such an amount is usually selected preferably in the range of 0.1 to 25% by weight based on the polymeric substance, but if the ultraviolet absorber is less than 0.1% by weight, it will not be effective, and if the amount is less than 10% by weight, If too much is added, it is not preferable because it will have a negative effect on the coloring properties of the photochromic dye. By using a specific amount of the ultraviolet absorber in the photochromic photosensitive material of the present invention, a certain amount of ultraviolet light of 400 nm or less of the incident light is absorbed, so deterioration of the spirooxazine compound itself can be prevented. Can be done.

[0030]

[Function] In addition to the photochromic compound, the photochromic photosensitive material of the present invention has nitroxy free radicals and an ultraviolet absorber added to improve light resistance, so that deterioration products are generated by light irradiation and turn red. Shows the effect of preventing the phenomenon. Therefore, the photochromic photosensitive material of the present invention can be used for light control materials such as light control glass for automobiles and building materials, optical filters, masking materials, light meters, and the like.

[0031]

EXAMPLES The present invention will be explained by the following Examples and Comparative Examples, but the present invention is not limited to these Examples in any way. In each of the Examples and Comparative Examples, a light resistance test was conducted using a xenon fade meter FAL-25A manufactured by Suga Test Instruments Co., Ltd.
This was done using X. Regarding the amount of degraded products produced, 520
The absorbance of light in the vicinity of nm was measured, and the light resistance was determined using the time when the difference in absorbance before and after the test reached 0.04 as the limit.

Example 1 and Comparative Example 1 [Preparation of photochromic laminate] Spirooxazine compound (A) represented by the following structural formula: 1% by weight,

00
33]

[Chemical formula 11]

Nitroxy free radical (2,2,5,5-tetramethylpiperidinyloxycarboxamide) represented by the following structural formula: 1% by weight,

[Chemical formula 12]

An ultraviolet absorber having the absorption spectrum shown in FIG. 2 and represented by the following structural formula (trade name Tinuvin-9)
00: Ciba Geigy): 0.25% by weight,

[Chem.13
]

Polyvinyl butyral containing plasticizer: 1
0% by weight. The above ingredients are mixed into a solvent (ethanol: toluene:
n-butanol = 50:45:5). The obtained solution was coated on a polyvinyl butyral interlayer film (manufactured by Monsanto Japan) by screen printing. After drying this coating film at 80° C. for 30 minutes under normal pressure, it was sandwiched between two glass plates and vacuum-pressed to produce a photochromic laminate (Example 1) having the layer structure shown in FIG. 1.

Next, a photochromic laminate (Comparative Example 1) was produced under the same conditions as in Example 1 except that the ultraviolet absorber was not used.

[Evaluation of Light Resistance] In order to evaluate the light resistance of the photochromic laminates of Example 1 and Comparative Example 1, an accelerated test was conducted using a xenon fade meter, and the amount of increase in the absorbance peak around 520 nm was measured. I looked into it. As a result, the usage limit for the photochromic laminate of Comparative Example 1 was 2000 hours, whereas the usage limit for the photochromic laminate of Example 1 was 3000 hours.

Examples 2 and 3 Photochromic laminates were produced in the same manner as in Example 1, except that spirooxazine compounds (B) and (C) having the following structural formulas were used. The light resistance of these photochromic laminates was evaluated in the same manner as in Example 1. The results are shown in Table 1 below together with the results of Example 1 and Comparative Example 1.

[0040]

[Chemical formula 14] However, in (B), the compound of R27=H, R28=CH3 and the compound of R27=CH3, R28=H are mixed in a ratio of 1:1.
It represents a mixture at a ratio of .

Comparative Examples 2 and 3 In Examples 2 and 3, photochromic laminates were prepared in the same manner as in Examples 2 and 3 except that no ultraviolet absorber was used, and the light resistance was evaluated. The results are shown in Table 1 together with Examples 2 and 3.

Examples 4 to 24 The spirooxazine compound of structural formula (B) in Example 2 was used as the photochromic compound, and the compounds shown in Table 1 below were used as the nitroxy free radicals and ultraviolet absorbers. A photochromic laminate was produced in the same manner as in Example 1, and the light resistance was evaluated in the same manner as in Example 1. The results are shown in Table 1.

[0043]

[Table 1]

[0044]

[0045]

[0046]

[0047]

[0048]

[0049]

[0050]

[0051]

Effects of the Invention Since the photochromic photosensitive material of the present invention is made by adding nitroxy free radicals and a specific amount of ultraviolet absorber, the light resistance is improved and the deterioration of the spirooxazine compound itself due to light irradiation is prevented. This makes it difficult for the phenomenon of generation and reddening to occur, and it is possible to prevent deterioration due to long-term light irradiation. Therefore, the photochromic photosensitive material of the present invention, in the form of a laminate or other form, can be used for light control materials such as light control glass for automobiles and building materials, optical filters, masking materials, light meters, etc. suitable.

[Brief explanation of the drawing]

FIG. 1 is a schematic cross-sectional view showing the layer structure of a photochromic laminate of the present invention.

FIG. 2 is a drawing showing the absorption spectrum of the ultraviolet absorber (Tinuvin-900: trade name manufactured by Ciba Geigy) used in the examples of the present invention.

[Explanation of symbols]

1...Transparent substrate 2...Photochromic photosensitive layer 3...Transparent interlayer film 4...Transparent substrate

Claims (3)

[Claims] Claim 1: A product comprising a spirooxazine compound, a nitroxy free radical, an ultraviolet absorber, and a polymeric substance, and the ultraviolet absorber absorbs three of the incident light.
A photochromic photosensitive material containing an amount that blocks 30 to 90% of 50 nm light. 2. The photochromic photosensitive material according to claim 1, wherein the ultraviolet absorber has absorption at a wavelength of 400 nm or less. 3. A photochromic laminate comprising a photochromic photosensitive layer made of the photochromic photosensitive material according to claim 1 between at least two transparent substrates.