JPS6330486A - Spirooxazine compound and sensitized material using said compound - Google Patents

Abstract

NEW MATERIAL:A compound shown by formula [n is 1-4; R<1> is alkyl; R<2> and R<3> are alkyl, alkoxyalkyl, cycloalkyl, aryl or R<2> and R<3> may be mutually bonded or subjected to ring formation; A is alkylene but is not -CH2CH2-; rings X and Y are (substituted) hydrocarbon aromatic ring or cyclic aromatic ring]. EXAMPLE:A compound shown by formula II. USE:A photochromic sensitized material having improved contrast, high coloring concentration and fastness. PREPARATION:For example, an indolenine derivative shown by formula III is alkylated with a p-toluenesulfonic ester shown by formula IV. Then the reaction product is reacted with a nirtoso-hydroxy derivative shown by formula V.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a novel spirooxazine compound and a photosensitive material using the compound.

Specifically, it relates to a novel compound with photochromic properties that can be used as a light control material such as light control glass for automobiles and building materials, an optical filter, a masking material, or a light meter, and a photosensitive material using the compound. .

[Conventional technology]

It is known that spirooxazine compounds have photochromic properties that cause them to develop or discolor when irradiated with light.
Various photochromic light-sensitive materials using this material have been proposed.

For example, a photochromic material containing a spironaphthoxazine compound as shown in the following formula is proposed in Tokuko Sho≠Yoichi 2♂♂ri No. 2.

Oh.

(In the formula, the bracket represents a hydrogen atom, a halogen atom, a cyan group, an alkyl group or an alkoxy group having carbon number/-r.) In addition, in Tokko Sho≠2-μm63/No. Photochromic light-sensitive materials have been proposed in which oxazine compounds are dispersed in polymeric substances.

(In the formula, ♂ is +OH, +n0OOH, +OF!, -jO
N or +OH, +n0OOR (R is an alkyl group with 1 carbon atoms): RC and ≠ are alkyl groups with 7 carbon atoms; R8 is a hydrogen atom, an alkyl group with 1 carbon atoms, a halogen atom, a nitro group, cyan group, alkoxycarbonyl group having 2 to 6 carbon atoms, or alkoxy group having carbon number/-1. ) Furthermore, in Japanese Patent Application Laid-Open No. 2003-120003, a folkchromic compound as shown in the following formula is proposed.

(In the formula, Rf and one of the moieties are) 10 gen or lower alkoxy, and the other is hydrogen, and Rh and R1 represent hydrogen, lower alkyl, lower alkoxy, or halogen. ) Mata, U B P 41. J! 241J', a photochromic compound as shown in the following formula is proposed.

(In the formula, one of Rj and Rk is halogen or lower alkoxy, the other is hydrogen, and R1 and Hm represent hydrogen, lower alkyl, lower alkoxy, or halogen. Hn
represents an alkyl group having 2 to 10 carbon atoms. ) Photochromic light-sensitive materials are usually used by forming a film in which a spironaphthoxazine compound is dissolved or dispersed in a polymer compound as described above.

[Problem that the invention seeks to solve]

However, in the case of conventional spirooxazine compounds, the color density and fastness of the colored state were not necessarily sufficient due to poor compatibility with polymer compounds.

Therefore, a robust photochromic light-sensitive material exhibiting good contrast and high color density cannot be obtained.

[Means for solving problems]

The present invention is based on the general formula [l] (A-0 in R1 (where n represents an integer of 7 to μ), R1 represents an alkyl group, and R'' and R'' represent an alkyl group, an alkoxyalkyl group, a cyclo represents an alkyl group, an aryl group, or R”
, R'' may be bonded to each other and cyclized. A represents an alkylene group, provided that it is not OH, OH, or -.

jJiX, Y represents an optionally substituted hydrocarbon aromatic ring or heterocyclic aromatic ring. ) and a photosensitive material provided with a photosensitive layer containing the compound.

The present invention will be explained in detail below.

The snokexazine compound of the present invention is represented by the above general formula [1].

In the formula, R1 is C1-2. H* represents an alkyl group such as an alkyl group of O1-2s: an alkoxyalkyl group such as a methoxyethyl group or an ethoxyethyl group; a cycloalkyl group such as a dichlorohexyl group or a cyclopentyl group: It represents a substituted or unsubstituted aryl group such as a phenyl group, p-methylphenyl group, naphthyl group, m-methoxyphenyl group, R' and R1 are connected to each other to form a cyclization group, and a cyclohexyl group, a cyclopentyl group,
A cyclohebutyl group or the like may be formed. R1%R3
In particular, lower alkyl groups such as ethyl group, ethyl group, propyl group, butyl group, phenyl group, or R2 and R
Preferably, 1 is a cyclized cyclohexyl group.

Examples of the alkylene group include the following.

〒H.

OH, O, H, RO, H, OH.

0H, 0Hs -OR, OH, OH, -, -OH! OH, ○H, OH!
-, -OH,0HOH! OR, -1QH.

Mouth H, OH.

Examples of the optionally substituted hydrocarbon aromatic ring or heterocyclic aromatic ring of @X%Y include benzene ring, naphthalene ring, quinoline ring, phenanthrene ring, etc. Substituents for these rings include chlorine atom, bromine Atom, halogen atom such as iodine atom: Alkyl group such as C, a alkyl group:
Alkoxy groups such as C8-6 alkoxy groups: Alkoxycarbonyl groups such as C12 alkoxycarbonyl groups: Alkoxysulfonyl groups such as methoxysulfonyl groups and ethoxysulfonyl groups: Alkylsulfonyl groups such as methylsulfonyl groups and ethylsulfonyl groups, etc. It will be done.

In the spirooxazine compound of the present invention, especially
is benzene, and ring Y is preferably a naphthalene ring, a quinoline ring, or a phenanthrene ring.

The compound of the present invention can be produced, for example, as follows. That is, the following general formula (wherein R1, R1
1 Ring X is the same as defined above. ) is represented by the following general formula [1] OH, -kuni=>-so! O(mu-o)nR1...,
,..., (P-) represented by (Otori) (in the formula, A, n, R'' are the same as the previous sound definitions), alkylated with a luenesulfonic acid ester, and then the following general formula (IY) O zo It can be produced by reacting with a nitro 2-hydroxy derivative represented by:

The alkylation reaction using p-toluenesulfonic acid ester is carried out without a solvent or in a nonpolar solvent such as an aromatic solvent such as chlorobenzene or dichlorobenzene at a temperature of up to -200°C.
The reaction temperature is . Preferably without solvent /, 30
It can be carried out smoothly at -110°C.

Next, the reaction with the nitro β-hydroxy derivative is carried out in the presence of a basic catalyst such as piperidine, piperazine, or morpholine, using an alcohol solvent such as methanol, ethanol, propatool, or butanol, a ketone solvent such as acetone, methyl ethyl ketone, dichloromethane, It is carried out in the presence of a polar or non-polar solvent such as a halogenated hydrocarbon solvent such as trichloroethane. The reaction temperature is 0~. 2
It is carried out in the range of OO°C. Preferably ethanol,
The reaction can be carried out smoothly in methyl ethyl ketone or acetone in the presence of a piperidine catalyst at 0°C to 10°C.

The compound of the present invention can also be produced by the following method, for example. That is, the following general formula [
v] (A-B)nR1 (wherein, R", R", R", m, n% fllX
is the same as the above definition. ) can be produced by reacting a compound represented by the following general formula CI with a nitro β-hydroxy derivative represented by 0 (wherein, ring Y is the same as defined above).

The reaction is usually carried out using methanol, ethanol, propatool,
The reaction is carried out in the presence of a polar or non-polar solvent such as an alcohol solvent such as butanol, a ketone solvent such as acetone or methyl ethyl ketone, or a halogenated hydrocarbon solvent such as dichloromethane or trichloroethyl ketone. The reaction temperature is carried out in the range of θ°C to 200°C, preferably 0°C to 0°C, so that the reaction can be carried out smoothly.

l) The compound of the present invention is a novel pigment and is a compound exhibiting photochromism. That is, this compound develops color when irradiated with ultraviolet rays, and then irradiated with visible light or heated at 70°C.
When heated above this level, it returns to its original state, and this change can be repeated.

The photosensitive material of the present invention has a photosensitive layer containing a novel compound and resin on a substrate, and can be obtained according to a known method.

The substrate applicable to 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, supports such as glass, plastic, paper, plate-shaped or foil-shaped metal, and composites thereof are used, and glass and plastic are preferable from various points of view. Examples of the plastic include acrylic resin, methacrylic resin, vinyl acetate resin, vinyl chloride resin, polyethylene resin, polypropylene resin, polycarbonate resin, and polysulfone resin.

Examples of the resin for dissolving or dispersing the compound of the present invention include polyester resin, polystyrene resin, polyvinyl butyral resin, polyvinyl chloride, polyvinyl chloride, polymethyl methacrylate, polyvinyl acetate, cellulose acetate, epoxy resin, phenol resin, etc. 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~!
o3, preferably! ~Ko. %.

Other additives other than the compound and resin of the present invention include transition metals + L/-[1: as a -heavycyclic oxygen quencher, compounds (for example, acetylacetate anatochelate, bisphenyldithiol, salicylaldehyde oxime, bisdithiol-α-diketone, etc.).

As a method for forming the film, 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 film is o,!
μ~i, o w, IEi! μ~100μ.

〔Example〕

Next, the present invention will be explained in more detail with reference to Examples.

Example/J! represented by the following structural formula: ,j,! -trimethylindolenine l
! A mixture of ri I and p-toluenesulfonic acid ester derivatives represented by the following structural formula t, o y was reacted at /10C for μ hours, and after cooling to room temperature, ethanol-00- was added, and further the following structural formula l-nitroso-λ-naphthol/7.3
77 and triethylamine/0. / Add li,
The reaction was carried out under reflux for 2 hours under a nitrogen atmosphere. After cooling, extract with chloroform, dry with sodium sulfate, evaporate the solvent,
Separation and purification by silica gel column chromatography (solvent: benzene) gave colorless crystals 2J, (71/C yield: 7%).

The obtained compound is represented by the following structural formula and has the physical property values shown below.

QH, OH! QHOOH.

CHa (physical property value) Melting point Tar ~ 100℃ Mass spectrum (measurement conditions near (1) eV, /!QC)
m/@4AOO(M”) 3ts (M”-CHa) J J 7 CM+-an, oHOOH,)CHa Absorption spectrum (solvent niacetonitrile) Ultraviolet region 3
4<rnm j / I nn m30(1)n Using the present compound gy, thermoplastic polyester resin 70I
(manufactured by Toyobo Co., Ltd., trade name: Vylon-200), a solution consisting of the solvent methyl ethyl ketone tool was applied using a polyester film (manufactured by Diafoil Co., Ltd., thickness: iooμ) using a bar coater/I63, and 7! "C1" was dried for 10 minutes. The obtained sample was colorless under normal conditions, but when irradiated with ultraviolet light, it developed a high-density blue color (λmax=joAnm).

Next, when it was irradiated with visible light or heated to 20°C or higher, it returned to its original colorless state. This change could be repeated.

In Example/Example/, p-toluenesulfonic acid ester 2A, O represented by the following structural formula
In place of j/, the following structural formula 'IFwasa iru p-) luenesulfonic acid ester λp,
A colorless crystal of a spirooxazine compound represented by the following structural formula % Formula % was prepared in the same manner as in Example 3 except that r g was used.
, y (embedding yield 6%) was obtained. The physical property values of this compound are as follows.

(Physical property values) Melting point: 1ao-iaa℃ Mass spectrum (measurement conditions 70θV, 1410℃) m
/e J t t (M”)J 7 / (M
”-OH,) 3 cores (M”-0HOOH,) 0H.

Absorption spectrum (solvent acetonitrile) ultraviolet 3
μ2 nm J/t nm J 00 nm When this compound was applied to a polyester film in the same manner as in Example 1, it turned dark blue (λmax=t06rm) f
It developed color. Next, it returned to its original colorless state by irradiating it with visible light or heating it above rO°C.

This change could be repeated.

Example 3 l-nitrosoconaphthol/7.3 represented by the following structural formula
Instead of 77, it is represented by the following structural formula! -Nitorone-6-hydroxyquinoline/
Using r, o i, and in the same manner as in Example 1, pale yellow crystals of a spirooxazine compound represented by the following structural formula % formula % were obtained. The physical properties of this compound are as follows.

(Physical property value) Mass spectrum (measurement conditions 70eV, /GO℃) m/8
ILtot (M") 3 (M"-04) Jkor (M"-OH, 0HOOH,) 0H.

When this compound was applied to a polyester film in the same manner as in Example, it developed a deep blue color (λmax=AλOnm) upon irradiation with ultraviolet rays. Next, when exposed to visible light or heated to 10°C or higher, it returned to its original colorless state. This change could be repeated.

Example ≠ 2 g of indolenine visiting conductor represented by the following structural formula % was dissolved in 1000 ml of methyl ethyl ketone, compound 3, tl represented by the following structural formula was added, and the mixture was reacted under reflux for 3 hours. . Cool to room temperature, distill off the solvent, separate and purify using silica gel column chromatography (solvent used: benzene) to obtain colorless crystals of a spirooxazine compound represented by the following structural formula.
, 31 (embedded yield rate J) was obtained.The physical property values of this compound are as follows.

(Physical property value) Mass spectrum (measurement conditions 70eV 1190℃) m/e
Hirox+(M”) J 67 (M”-OH!OH,001(,) Absorption spectrum (solvent Niacetonitrile) Ultraviolet region 3 μAn
m J / 7 nm OOnm This compound was used in the same manner as in Example/, except that polyvinylidene chloride resin (Denki Kagaku #1000"lI) was used instead of thermoplastic polyester resin iog in Example/. When a polyester film was applied, it turned dark blue (λmaw = JOAn) due to ultraviolet irradiation.
m)→This color developed. Next, when it was irradiated with visible light or heated to temperatures above 0.degree. C., it returned to its original colorless state.

This change could be repeated.

Example! l-nitrone-naphthol/7. J
A compound represented by the following structural formula in place of i, 22. The reaction was carried out in the same manner as in Example 1 using J i, and a colorless crystal of a spirooxazine compound represented by the following structural formula 0 was obtained.
Z, J, 9 (embedding yield!μ%) was obtained. The physical properties of this compound are as follows.

(Physical property values) Melting point 210λ~10℃ Mass spectrum (Measurement conditions 70eV%/1.0℃)
m/・≠yo0(M+) J77 (M”-0!It, 0HOOH,)0H.

Absorption spectrum (solvent niacetonitrile) ultraviolet
When this compound was applied to a polyester film in the same manner as in Example 1, it turned dark blue (
The color was developed at λmax = AoOnm). Next, when it was irradiated with visible light or heated to temperatures above 0.degree. C., it returned to its original pale blue state.

This change could be repeated.

Example 6 A compound represented by the following general formula (1) was synthesized by a method according to Example/-1. When coated on a polyester film and irradiated with ultraviolet rays, the color tones shown in Table 1 were obtained in winter.
Color developed to λmax.

Next, when exposed to visible light or heated to 70°C or higher, it returned to its original colorless state. This change could be repeated.

[Effect of rows and brightness] The uninvented compound has excellent compatibility with polymeric compounds because it has an ether bond-containing group ((A-0)RJ introduced into the molecule, and the coloring state And since the state of the colored state is immediately adjusted, it is possible to obtain a composition which is deep in color and has good stability over repeated coloring and decoloring.

Such compounds of the present invention are used as light control materials such as light control glass for automobiles and building materials, optical filters, masking materials, and materials for light meters.

production

Claims (4)

[Claims] (1) The following general formula [I] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (In the formula, n represents an integer from 1 to 4, R^1 represents an alkyl group, and R^2 and R^3 It represents an alkyl group, an alkoxyalkyl group, a cycloalkyl group, an aryl group, or R^2 and R^3 may be bonded to each other and may be cyclized. A represents an alkylene group, provided that -CH_2CH_2-
isn't it. Rings X and Y represent an optionally substituted hydrocarbon aromatic ring or heterocyclic aromatic ring. ) A spirooxazine compound represented by (2) The spirooxazine compound according to claim 1, wherein ring X is an optionally substituted benzene ring, and ring Y is an optionally substituted naphthalene ring, quinoline ring, or phenanthrene ring. (3) On the substrate, there are the following general formula [1] ▲ Numerical formula, chemical formula, table, etc. ▼ (In the formula, n represents an integer from 1 to 4, R^1 represents an alkyl group, R^2, R^3 represents an alkyl group, an alkoxyalkyl group, a cycloalkyl group, or an aryl group, or R^2 and R^3 may be bonded to each other and may be cyclized. A represents an alkylene group, provided that -CH_2CH_2 −
isn't it. Rings X and Y represent an optionally substituted hydrocarbon aromatic ring or heterocyclic aromatic ring. ) A photosensitive material comprising a photosensitive layer containing a spirooxazine compound represented by: (4) The spirooxazine compound contained in the photosensitive material according to claim 3 is a benzene ring which may be substituted with ring X, a naphthalene ring which may be substituted with ring Y, or a quinoline ring phenanthrene. Something that is a ring.