JPH02210344A - Photochromic photosensitive material - Google Patents

Abstract

PURPOSE:To prevent deterioration due to irradiation with light for a long time by incorporating a specified spiroxazine compd. and oxazolidine type nitroxy free radicals into a polymer. CONSTITUTION:A spiroxazine compd. represented by formula I and oxazolidine type nitroxy free radicals represented by formula II are incorporated into a polymer. In the formula I, each or R<1>-R<3> is optionally substd. alkyl, cycloalkyl or aryl, R<4> is H or 1-5C alkyl, each of X and Y is an optionally substd. arom. hydrocarbon or hetero ring and Z is O or S. In the formula II, each of R<5> and R<6> is optionally substd. alkyl, each of R<7> and R<8> is optionally substd. alkyl or aryl and A is optionally substd. alkylene. Weather resistance is considerably improved.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to a photochromic photosensitive material, and particularly to a photochromic photosensitive material having excellent weather resistance.

(Prior Art) Conventional photochromic photosensitive materials include, for example, films made by dispersing a spirooxazine-based photochromic compound in a polymer compound, such as a transparent polymer film in which a photochromic compound is dispersed, or glass or transparent materials. A film of the above-mentioned polymer compound containing a photochromic compound is adhered to a substrate made of a polymer plate, or a transparent polymer film containing a photochromic compound dispersed therein is sandwiched between the substrates to form a laminate. There is something. This laminate is described in detail in Japanese Patent Laid-Open No. 60-205429.

(Problem to be Solved by the Invention) However, in photochromic materials containing such conventional spirooxazine compounds, irreversible deterioration products are likely to be generated during the coloring/decoloring reaction, so it cannot be used for a long time. There was a problem that it deteriorated due to light irradiation.

(Means for Solving the Problems) The present invention relates to a photochromic photosensitive material containing a spirooxazine compound, and in particular, by adding an oxazolidine nitroxy free radical to a polymeric substance in addition to a spirooxazine photochromic compound. ,
This can prevent the formation of undesired compounds during the coloring/decoloring reaction.

That is, the present invention provides polymeric substances with the following general formula (in which R
1, R1 and R'3 represent a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a cycloalkyl group, or a substituted or unsubstituted aryl group,
RZ and R3 may be bonded to each other and may be cyclized. R4 represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. R1
Alternatively, it may have another spirooxazine ring via an alkylene group or an arylene group, forming a dimer compound as a whole. Rings X and Y represent an optionally substituted hydrocarbon aromatic ring or heteroaromatic ring. Z represents an oxygen atom or a sulfur atom. ) and an oxazolidine-based nitroxy free radical represented by the following Monka (II) (wherein RS and R6 each represent a substituted or unsubstituted alkyl group, R7 and R11
each represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group, and R? and Re
are bonded to each other and may represent an optionally substituted hydrocarbon ring. A represents an optionally substituted alkylene group. ). The present invention will be explained in detail below.

In the compound represented by the above formula (1), RIR2 and R3 are alkyl groups such as alkyl groups having 1 to 28 carbon atoms, alkoxyalkyl groups such as methoxyethyl group and ethoxyethyl group, methoxyethoxyethyl group, n-butoxyethoxy Substituted alkoxyalkoxyalkyl groups such as ethyl groups, alkoxyalkoxyalkoxyalkyl groups such as methoxyethoxyethoxyethyl groups, ethoxyethoxyethoxyethyl groups, phenyloxyethyl groups, naphthyloxyethyl groups, p-chlorophenyloxyethyl groups, etc. Moyoiori-ruoxyalkyl group, benzyl group, phenethyl group, p-chlorobenzyl group, p-
An optionally substituted arylalkyl group such as nitrobenzyl, a cycloalkylalkyl group such as a cyclohexylmethyl group, a cyclohexylethyl group, a cyclopentylmethyl group, an allyloxyethyl group, a 3-bromoallyloxyethyl group, etc. Substitution of alkenyloxyalkyl groups, cyanoalkyl groups such as cyanoethyl groups and cyanomethyl groups, hydroxyalkyl groups such as hydroxyethyl groups and hydroxymethyl groups, and tetrahydrofuryl alkyl groups such as tetrahydrofurfuryl groups and tetrahydrofurylethyl groups; Examples include unsubstituted alkyl groups, substituted or unsubstituted alkenyl groups such as allyl group and 2-chloroallyl group, substituted or unsubstituted alkenyl groups such as phenyl group, p-methylphenyl group, naphthyl group, m-methoxyphenyl group, etc. Examples include unsubstituted oryl groups, and cycloalkyl groups such as cyclohexyl and cyclopentyl groups, and even if R2 and R3 are linked to each other to form a cyclohexyl group, cyclopentyl group, cycloheptyl group, etc. good. Examples of R1 include compounds that are 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.

Examples of the optionally substituted hydrocarbon aromatic ring or heteroaromatic ring of rings X and Y include a benzene ring, a naphthalene ring, a quinoline ring, and a phenanthrene ring. Substituents for these rings include a chlorine atom, Halogen atoms such as bromine atoms and iodine atoms, alkyl groups having 1 to 6 carbon atoms, alkoxy groups, alkoxycarbonyl groups, methoxysulfonyl groups,
Examples include alkoxysulfonyl groups such as ethoxysulfonyl groups, cyano groups, amino groups, dimethylamino groups, and nitro groups.

In the present invention, among the spirooxazine compounds represented by the above formula (1), the following general formula (III) (wherein R
1 is an alkyl group or alkoxyalkyl group having 1 to 20 carbon atoms, R4 is a hydrogen atom or a methyl group, X and Y are an optionally substituted hydrocarbon aromatic ring or a heteroaromatic ring). Preferably, oxazine compounds are used.

Further, in the oxazolidine-based nitroxy free radical of -Momonena (I[), the substituted or unsubstituted alkyl group of R5, R6, R'l and R8 is preferably a lower alkyl group.

The aryl group of the substituted or unsubstituted aryl group of R7 and R8 is preferably a phenyl group.

Substituents for these alkyl groups and aryl groups include lower alkyl groups, carboxyl groups, lower alkoxy groups, and lower acyl groups.

Further, when R1 and Rs combine to form an optionally substituted hydrocarbon ring, this ring may represent a monocyclic ring, a condensed ring, a bridged hydrocarbon ring, or the like.

Substituents for this hydrocarbon ring include the above-mentioned hydroxyl group,
Another nitroxy radical group or one or more carbon atoms of the ring may form a carbonyl group. A represents an optionally substituted alkylene group.

Specific examples of A are -CH2-, -CHHz CH2CHz, CH, CHzCHzCHz
C,H.

etc.

Examples of the polymer substance include the spirooxazine compound,
Any material that has good compatibility with nitroxy free radicals, is optically transparent, and has excellent film-forming ability, such as polymethyl methacrylate, polystyrene, polyvinyl acetate, polyvinyl butyral, cellulose acetate, and Vinyl chloride, polyvinylidene chloride, vinyl chloride
Vinyl acetate copolymer, polypropylene, polyethylene,
polyacrylonitrile, urethane resin, epoxy resin,
Examples include, but are not limited to, phenoxy resin and polyester. Moreover, it may contain a plasticizer or be crosslinked, if necessary.

The photochromic photosensitive material of the present invention can be in the form of a film,
This includes those in which a photosensitive layer is formed on a substrate, and those in which a photochromic photosensitive layer is sandwiched between substrates to form a laminate. Examples of the substrate include polyethylene terephthalate, cellulose acetate, polycarbonate, glass, etc., and laminated as necessary. It may be something you have done.

The spirooxazine compound is 0.1 to 0.1 to the polymer substance.
It is used in an amount of 50% by weight, preferably 0.5-20% by weight. If the amount of the spirooxazine compound is less than 0.1% by weight, sufficient optical density cannot be obtained when the photochromic dye is colored, and if it exceeds 50% by weight, the optical density becomes constant and the cost increases, which is not preferable.

The thickness of the photochromic photosensitive layer is 0.5 to 11 μm, preferably 10 to 250 μm.

The photosensitive material of the present invention, in which the photochromic photosensitive layer contains an oxazolidine-based nitroxy free radical, can be prepared by, for example, dissolving a spirooxazine-based compound, a polymeric substance, and a nitroxy free radical in an appropriate solvent; This solution can be obtained by coating a suitable transparent support by casting or using a spinner. In this case, the nitroxy free radical is used in an amount of 0.1 to 50% by weight, preferably 0.5 to 20% by weight, based on the polymeric substance. There is no effect when the nitroxy free radical is less than 0.1% by weight, and 5
Even if the amount is more than 0, the effect will be constant and the cost will be high, which is not preferable.

(Function) The photochromic photosensitive material of the present invention has significantly improved weather resistance. This effect is thought to be due to the fact that the generation of irreversibly degraded products of spirooxazine molecules is prevented by the nitroxy free radicals contained in the photochromic photosensitive layer.

(Example) The invention will be illustrated by the following examples and comparative examples.

In each Example, the weather resistance was evaluated by the residual coloring performance using a xenon lamp, and expressed as the time until the coloring performance decreased to 50% or less of the initial coloring performance.

As a deterioration accelerating device, a xenon fade meter manufactured by Suga Test Instruments Co., Ltd. was used.

Side 1. Comparative Example 1 Spirooxazine compound (A) having the following structure:
0.1% by weight and 0.1% of the nitroxy free radical having the following structure.
1% by weight and 10% by weight of polyvinyl butyral containing a plasticizer were dissolved in a solvent (toluene:ethanol = 674).

The resulting solution was coated onto a glass substrate by casting. After this coating film was dried in a vacuum dryer at 70° C. under reduced pressure for 6 hours, a glass plate was further stacked on top of the photosensitive layer and vacuum-pressed to produce a laminate photosensitive material.

As Comparative Example 1, a photosensitive material of Comparative Example 1 was produced under the same conditions as in this example except that the nitroxy free radical was not used.

In order to evaluate the weather resistance properties of these samples, the initial coloring performance was measured using a xenon lamp, and then light irradiation was performed in a xenon fade meter to measure the change in coloring performance over time.

As a result, the photosensitive material of this example showed a coloring performance of 50% or more of the initial value even after 2000 hours of irradiation.
The photosensitive sample of the comparative example had an initial value of 50 within 400 hours.
% or less.

2-64. 2-3 Using the same method as in Example 1, subirooxazine compounds (B) and (C) having the following structures were used in combination with various nitroxy free radicals as shown in Table 1, and Examples 2-3 were prepared. Samples of the photosensitive materials of Example 64 and Comparative Examples 2 and 3 were prepared, and each sample was subjected to a weather resistance test. The results are shown in Table 1 together with the results of Example 1 and Comparative Example 1. In this example, the effects of three types of spirooxazine compounds were shown, but
Needless to say, we are not subject to these.

However, CB) is a compound with R9 = H, Rto = CH3 and a compound with Rq "CH3, R+.-H in a 1:1 ratio.
It represents a mixture at a ratio of .

(B) (C) (Effects of the Invention) As explained above, according to the present invention, the photochromic compound is composed of a spirooxazine-based photochromic compound of 2N) and an oxazolidine-based nitroxy free radical. Because it is a composition, the generation of irreversible deterioration products can be prevented to about 175 compared to conventional methods. The photochromic photosensitive material of the present invention has significantly improved weather resistance compared to conventional materials, so it can be used in electronic materials such as recording, memory materials, copying materials, laser photosensitive materials, printed photoreceptors, light control materials, etc. Used for display etc.

Furthermore, the red discoloration associated with deterioration in the laminate can also be prevented by containing the oxazolidine-based nitroxy free radical.

Applicant: Nissan Motor Co., Ltd. Mitsubishi Chemical Corporation

Claims (1)

[Scope of Claims] 1. Polymer substances have the following general formula [I] ▲mathematical formula, chemical formula, table, etc.▼…[I] (In the formula, R^1, R^2 and R^3 are , represents a substituted or unsubstituted alkyl group, a cycloalkyl group, or a substituted or unsubstituted aryl group, and R^2 and R^3 may be bonded to each other to form a cyclization.R^4 is a hydrogen atom or a number of carbon atoms. 1 to 5 alkyl groups.Also, R^1 may have another spirooxazine ring via an alkylene group or an arylene group to form a dimeric compound as a whole.Ring X , Y represents an optionally substituted hydrocarbon aromatic or heteroaromatic ring. Z represents an oxygen atom or a sulfur atom) and the following general formula [II] ▲ Numerical formula, chemical formula , tables, etc. ▼... [II] Oxazolidine-based nitroxy free radical represented by Each represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group, and R^7 and R^8 are bonded to each other and may represent an optionally substituted hydrocarbon ring.A is (represents an optionally substituted alkylene group).