JPS63115885A - Spiroxazine compound and photosensitive material utilizing said compound - Google Patents

Abstract

NEW MATERIAL:A compound expressed by formula I [X<1>, X<2>, Y<1> and Y<2> are (alkoxy)alkyl or aryl; X<1> and X<2> and Y<1> and Y<2> together may link to form a ring; Z is (substituted)alkylene or (substituted)arylene; R<1>-R<8> are H, halogen, alkyl, alkoxy(carbonyl), alkoxysulfonyl or alkylsulfonyl)]. EXAMPLE:A compound expressed by formula II. USE:A photochromic photosensitive material, having excellent heat resistance, high coloring density as well as improved fastness, capable of coloring by irradiation with ultraviolet rays and then returning to the original color by irradiation with visible rays or heating to >=80 deg.C. PREPARATION:2,3,3-Trimethylindolenine derivatives expressed by formulas II and IV are reacted with a dihalide expressed by the having A-Z-A (A is halogen) and the resultant products are then reacted with 5-nitroso-6- hydroxyquinoline derivatives expressed by formulas V and VI.

Description

Detailed Description of the Invention (Industrial Application Field) The present invention relates to a photosensitive material having a photosensitive layer on a substrate containing a novel caspirooxazine compound having photochromic properties and a resin in which the compound is dissolved or dispersed. It is.

(Prior Art) It has been known that spirooxazine compounds have photochromic properties in which they develop or discolor when irradiated with light, and various photochromic light-sensitive materials using the same have been proposed.

For example, a photochromic material containing a spironaphthoxazine compound as shown in the following formula is proposed in Japanese Patent Publication No. 9.2.

(In the formula, r represents a hydrogen atom, a halogen atom, a cyan group, an alkyl group with carbon number/~r, or an alkoxy group.) In addition, in Japanese Patent Publication No. 44163/, the following formula A photochromic light-sensitive material in which a spironaphthoxazine compound is dispersed in a polymeric substance has been proposed.

R(l Ha (wherein, R1 is +CtooOH, ÷CH Goose aN or +(:!Hs+QCOOR (R is an alkyl group with carbon number/~j); R''- and R4 are carbon number/~! Alkyl group; R'''wQ elemental atom, alkyl group having 7 to 5 carbon atoms, halogen atom, nitro group, cyano group, alkoxycarbonyl group having 2 to 6 carbon atoms, or alkoxy group having 7 to 5 carbon atoms In addition, a photochromic compound as shown in the following formula is proposed in Japanese Patent Application Laid-open No. Sho! J-Jt Cor.

(In the formula, one of ytf and Hg is a halogen atom or a lower alkoxy group, and the other is a hydrogen atom, and Rh and R1 represent a hydrogen atom, a lower alkyl group, a lower alkoxy group, or a halogen atom.) Also, l1lr 8 P 4', J
For 44J, (j/, a photochromic compound as shown in the following formula has been proposed.

(In the formula, one of R3 and xk is a halogen atom or a lower alkoxy group, the other is a hydrogen atom, and R1 and R1
represents a hydrogen atom, a lower alkyl group, a lower alkoxy group, or a halogen atom, and Rfi represents an alkyl group having from - to 10 carbon atoms. ) Maku, Tokukai Akira, gO-//, 2
Publication lr0 proposes a spiropyridobenzoxazine compound represented by the following formula and a photochromic light-sensitive material in which the compound is dispersed in a polymeric substance.

(In the formula, R'' is an alkyl group having a carbon number of 1 to 1, a phenyl group, a phenylalkyl group having a carbon number of 1 to 1, an allyl group, and a mono- or di-substituted phenyl group (substituted R' and R6 are each a
Alkyl group with carbon number l-j, phenyl group, carbon number/~!
selected from the group consisting of alkoxy groups, mono- or di-substituted phenyl groups, and benzyl groups, or combined with 4 to 2
form a cyclic ring selected from the group consisting of an alicyclic groove, a norbornyl ring, and an adamantyl ring, each containing a hydrogen atom and a carbon number/~ ! (selected from the group consisting of an alkyl group, a notyrogen atom, an alkoxy group having 7 to 5 carbon atoms, a nitro group, a cyano group, and an alkoxycarbonyl group having 1 to 1 carbon atoms) Usually, the photochromic light-sensitive material is A spirooxazine compound is dissolved or dispersed in a polymer compound and then formed into a film.

However, in the case of conventional spirooxazine compounds, the color density and fastness of the colored state were not necessarily sufficient, the melting point was low, and the heat resistance was poor. Therefore, there has been a problem in that it is not possible to obtain a photochromic light-sensitive material that is robust and has good heat resistance, exhibiting good contrast between color development and decolorization, and high color density.

(Problems to be Solved by the Invention) The present invention provides spironaphthoxazine which has good heat resistance, high coloring density, excellent fastness of the colored state, and good photochromic properties with good stability in repeated coloring and decoloring. The object of the present invention is to provide a photosensitive material comprising a compound and a photosensitive layer containing the compound.

(Rounding Means to Solve Problems) That is, the present invention is based on the general formula (1) (where xl, yl, and yl represent an alkyl group, an alkoxyalkyl group, a cycloalkyl group, and an aryl group; x8, Yl and Y snow may be bonded to each other and may be cyclized. 2 is an optionally substituted alkylene group or an optionally substituted arylene group, which may be via another group or atom. , R1, R1, H*
, R4, R11, R6, R? , Ra represents a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an alkoxycarbonyl group, an alkoxysulfonyl group, an alkylsulfonyl group.

In the spirooxazine compound represented by the general formula (1) of the present invention, xl, XI, Yl, Y2 are at to ts,
Preferably an alkyl group such as a C1-4 alkyl group; an alkoxyalkyl group such as a methoxyethyl group; a cycloalkyl group such as a cyclohexyl group or a cyclopentyl group; a phenyl group, a p-methyl 7enyl group, or a naphthyl g% m- Indicates an aryl group such as methoxyphenyl group, xl and x2, Y
l and Yl may each form a cycloalkyl group such as dicyclized, cyclohexyl group, cyclopentyl group, or cycloheptyl group. A butyl group, a phenyl group, a cyclized cyclohexyl group, and the like are preferred.

2 is 10H, -1÷OR,)2-1-(CHt)
3-1(-(!Hri4-1+CHt),-1":"
"t ) @ , +01h), -1-((H鵞)t-0(
OHz)z-0-(OHz)z-,-(! T1! u
Examples include CH2-1○l or an arylene group which may be substituted or substituted through an atom.

R1, R2, R*%R4, RI%R・, R7, 'Rs are hydrogen atoms; halogen atoms such as chlorine atom, bromine atom, methane atom; alkyl groups such as C1 ~, alkyl groups;
An alkoxy group such as an alkoxy group of C1~, or C
Examples include alkoxycarbonyl groups such as alkoxycarbonyl groups of 4 to 4, alkoxysulfonyl groups such as methoxysulfonyl group and ethoxysulfonyl group, and alkoxysulfonyl groups such as methylsulfonyl group and ethylsulfonyl group.

The compound of the present invention can be produced, for example, as follows. That is, the following general formula % formula % () (where xl, z!, yl, Y2, R1, R1, R',
R@ is the same as the above definition. ) 2,J,! -Trimethylindolenine derivative has the following general formula 〇V) A-Z-A... Parable... Fist... (I
V) (wherein A represents a halogen atom, and 2 represents the above-mentioned constant IA
Same as K. ) is reacted with a dihalide represented by the following general formulas (V) and (W) O (wherein R1%R4, R1 and Bl are the same as defined above)! -It can be produced by reacting a nitrone-t-hydroxyquinoline derivative.

The alkylation reaction using a dihalide is carried out at a reaction temperature of 20 to 200° C. in a nonpolar solvent such as hot fs or an aromatic solvent such as chlorobenzene or dichlorobenzene. Preferably 730~/! without solvent. It can be carried out smoothly at θ℃.

Next,! The reaction with hydroxyquinoline derivatives is carried out in the presence of a basic catalyst such as piperidine, piperazine or morpholine, in an alcoholic solvent such as methanol, ethanol, globanol or butanol, in a ketone solvent such as acetone or methyl ethyl ketone, or in dichloromethane. , in a polar or non-polar solvent such as a halogenated hydrocarbon solvent such as trichloroethane. The reaction temperature is carried out in the range of 0 to 200°C. Preferably, ethanol and methyl are used.The compound of the present invention can also be produced, for example, as follows. That is, the following general formula [■] Ko2... River [■] (In the formula, X!, z2.yl, Y!, Z, p, l, R
", RM, H@ are the same as the above definitions) and the following general formula (V), [■]?IO (wherein, R1, R4, R?, R") C The above definition K Same as 1
．． . ) can be produced by reacting with a j-nitroso-6-hydroxyquinoline derivative represented by K.

The reaction is usually carried out using methanol, ethanol, propatool,
The reaction is carried out at a temperature of 200° C., such as an alcohol solvent such as butanol, a ketone solvent such as acetone or methyl ethyl ketone, dichloromethane, or trichloroethane, and preferably a compound exhibiting 4cO romism. That is,
This compound develops a color when irradiated with ultraviolet rays, and then returns to its original colorless state when irradiated with visible light or heated to 10° C. or higher, and this change can be repeated.

A photosensitive material having a photosensitive layer on a substrate containing a resin in which the novel compound of the present invention is dissolved or dispersed can be obtained according to a known method.

Examples of the resin that dissolves or disperses the compound of the present invention include polyester resin, polystyrene resin, polyvinyl butyral resin, polyvinylidene chloride, polyvinyl chloride, polymethyl methacrylate, polyvinyl acetate, cellulose acetate, epoxy resin, and phenol resin. Examples of the solvent used include carbon tetrachloride, benzene, cyclohexane, methyl ethyl ketone, tetrachloroethane, toluene, ethanol, and ethyl cellosolve.

The ratio of the compound of the present invention to be used is 3~!
0%, preferably 5-20%.

Other additives other than the compound and resin of the present invention include transition metal chelate compounds (for example, acetylacetonate) as a heavy ring oxygen quencher for the purpose of stabilizing the photosensitive material and improving light resistance. -4.2 U, 8 = air oya, kawaraldehyde oxime, bisdithiol -α
- diketone, etc.) may be contained. Alternatively, an ultraviolet absorber or an antioxidant may be added.

As a method for forming the photosensitive layer, commonly used coating methods such as a doctor blade method, a casting method, a spinner method, and a dipping method are used.

The thickness of the photosensitive layer is O1Sμ~/, θLi, preferably 5~7
00μ.

The substrate in the present invention may be either transparent or opaque, but when substrates are provided on both sides of the photosensitive layer, at least one side must be transparent in order to be exposed to light. As the material of the substrate, glass, plastic, paper, plate-like or foil-like metal, and composites thereof can be used, but glass and plastic are preferable from various points of view. Examples of the plastic include acrylic resin, methacrylic resin, vinyl acetate resin, and vinyl chloride.

(Examples) Next, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited to the following Examples.

Example/1,J,J-)limethylindolenine/! represented by the following structural formula!
, rif and dibromobutane represented by the following structural formula % formula % / 0. r f mixture t
- / Reacted at 10°C for a period of time, cooled to room temperature, added ethanol λ001E/, and further represented by the following structural formula! -Nitroso-4-hydroxyquinoline/7. J f
and triethylamine 10. /l was added thereto, and the mixture was reacted under reflux for 2 hours under a nitrogen atmosphere. Spirooxazine, extracted with chloroform, dried with layers and crumbs, distilled off the solvent, separated and purified by column chromatography (solvent benzene), has a melting point of 2IO-co/4I-℃ and is represented by the following structural formula. Colorless crystals of the compound were obtained.

The physical property values (mass spectrum) are as follows.

(Measurement conditions: 70 eV s J j ('℃) m/
et/a(M”) 6/sr(base peak) Using this compound≠2, thermoplastic polyester resin 109 (Toyobo Ura Byron-2oo), solvent methyl ethyl ketone 100
A solution consisting of 9 was applied to a polyester film (manufactured by Diafoil Co., Ltd., thickness 100 μm) using bar coater A3, and dried at 7j° C. for 70 minutes. The obtained sample is colorless under normal conditions, but when irradiated with ultraviolet light it becomes a highly concentrated blue color (
λmaw = Go/Onm) K color and mourning. The absorption spectrum is shown in Figure-/.

Next, when exposed to visible light or heated to 10° C. or higher, it returned to its original colorless state. This change can be repeated repeatedly.

Example 2 Practical Example/Dibromobutane/0. ♂? The following compound was obtained in the same manner as in Example, except that dibromobutanta, ゛≠2 was used in place of .

CH3ca3 The physical property values (mass spectrum) are as follows.

(Measurement conditions: 70 evs J 00℃) m/e
t s &(M")6/(M"-/ri/j r (base peak) When this compound was applied to a polyester film in the same manner as in Example 1, it turned dark blue (λmax) by ultraviolet irradiation. = t
/Onm). Next, irradiate with visible light or
Alternatively, when heated above 29°C, it returned to its original colorless state. This change could be repeated.

Example 3 Compound 4cJt, Of represented by the following structural formula (% formula %) was dissolved in 1000 tdK of methyl ethyl ketone, and compound 3≠, g f represented by the following structural formula was added and reacted under reflux for 3 hours. The mixture was cooled to room temperature, the solvent was distilled off, and the mixture was separated and purified by column chromatography (using benzene as the solvent) to obtain a spironaphthoxazine compound represented by the following structural formula.

cHsO1’l= The physical property values (mass spectrum) are as follows.

(Measurement conditions near θev, 3xO℃) When applied, it developed a deep blue color (λmaX = Go/Onm) due to UV irradiation. Next, irradiate with visible light or
Or a hole that returns to its original colorless state when heated above 20℃.

This change could be repeated.

A spirooxazine compound represented by the general formula (1) and shown in Table 1 below was synthesized by a method similar to that described in Examples Hiroshi, C and JK. When the obtained compounds were applied onto a polyester film and irradiated with ultraviolet rays, each of the first
The color tone shown in the table is 9, and the color develops to λmax. Next, when exposed to visible light or heated to 20°C or higher, it returned to its original colorless state. I was able to do this trick over and over again.

(Effects of the Invention) The spirooxazine compound of the present invention has photochromic properties, has particularly good heat resistance, and has excellent color density and color fastness, so it is deep in color and stable in repeated color development and decolorization. In good condition.

A photosensitive material having on a substrate a photosensitive layer containing a resin in which a spirooxazine compound is dissolved or dispersed can be used as various light control materials, optical filters, masking materials, and light meters.

[Brief explanation of the drawing]

Figure / shows the absorption spectrum of an example of the spirooxazine compound of the present invention in a colored state upon irradiation with ultraviolet rays. The vertical axis shows absorbance and the horizontal axis shows wavelength. Patent applicant: Nissan Motor Co., Ltd. (7 others) Agent: Patent attorney - (1 other person) Figure 1 (Voluntary) Procedural amendment dated 79///1982 2 Name of the invention Spirooxazine Compound and photosensitive material using the compound 4 agents 〒100 (and 1 other names) 5 Subject of amendment 6 "Detailed Description of the Invention" column of the specification 6 Contents of amendment (1) I received the specification letter 1! Correct "film formation" in the row to "film formation". (2) In the third line from the bottom of the same page of the specification, "Svironal tooxazine compound" is corrected to "spirooxazinated/-compound." 13) "Pylon" in the second line from the bottom of 1000 of the specification is corrected to "Byron". (4) "Percoater Fu 3" on page 21, line 2 of the specification is corrected to "Percoater Fu 3". (5) Except for the structural formula on page 23 of the specification, "spironaphthookimedine compound" in the first row from the top is corrected to "spirooxazine compound." (6) Add "Table 1" to page J of the detailed letter. (The compound in Example/16v of Table 1 on page 33 of the specification is corrected as follows. (8) The compound in Example/1617 of Table 1 on page 33 of the specification is corrected as. Page 1 Table 1 Example Example A62 (Compound 4 is corrected as Table 1 Example A62 (4) is corrected as Takako17g62, respectively.αυ Details Bookcase page 6 Table 1 Examples/l6tl Add the following examples after 7. That's all.

Claims (4)

[Claims] (1) General formula [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼・・・・・・[I
] (In the formula, X^1, X^2, Y^1, and Y^2 represent an alkyl group, an alkoxyalkyl group, a cycloalkyl group, and an aryl group, and X^1 and X^2, Y^1 and Y ^2 may be bonded to each other and cyclized.Z represents an alkylene group that may be substituted or an arylene group that may be substituted via another group or atom, and R^ 1
, R^2, R^3, R^4, R^5, R^6, R^7,
R^8 represents a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an alkoxycarbonyl group, an alkoxysulfonyl group, or an alkylsulfonyl group. ) A spirooxazine compound represented by (2) X^1, X^2, Y^1 in general formula [I]
, Y^2 is a methyl group, the spirooxazine compound according to claim (1). (3) X^1, X^2, Y^1 in general formula [I]
The spirooxazine compound according to claim (1), wherein and Y^2 are bonded to each other to form a cyclohexane ring. (4) General formula [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼・・・・・・[I
] (In the formula, X^1, X^2, Y^1, and Y^2 represent an alkyl group, an alkoxyalkyl group, a cycloalkyl group, and an aryl group, and X^1 and X^2, Y^1 and Y ^2 may be bonded to each other and may be cyclized. Z may be connected to another group or atom, and represents an optionally substituted alkylene group or an optionally substituted arylene group. ,R
^1, R^2, R^3, R^4, R^5, R^6, R^
7. R^8 represents a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an alkoxycarbonyl group, an alkoxysulfonyl group, or an alkylsulfonyl group. ) A photosensitive material having, on a substrate, a photosensitive layer containing a resin in which a spirooxazine compound represented by the following formula is dissolved or dispersed.