JPS61209443A - Formation of image - Google Patents

Abstract

PURPOSE:To obtain a dye image having high maximum density in a short time by heating a photosensitive material in the presence of a specified compound in a state in which the material does not contain water after or during imagewise exposure to form imagewise a mobile dye. CONSTITUTION:A photosensitive material having photosensitive silver halide, a binder, a substance acting as a reducing agent on the photosensitive silver halide during heating and a dye providing substance releasing a hydrophilic dye by a reaction with the oxidized product of the reducing agent on the support is heated in the presence of a compound represented by the formula in a state in which the material does not contain water after or during imagewise exposure to form imagewise a mobile dye. In the formula, R<1> is preferably a univalent 1-40C satd. hydrocarbon group such as methyl, and each of R<2> and R<3> is preferably H or a 1-40C satd. hydrocarbon group such as methyl.

Description

BACKGROUND OF THE INVENTION TECHNICAL FIELD The present invention relates to a method of forming a dye image by heating in a substantially water-free state, and particularly relates to a method of forming a dye image by heating in a substantially water-free state, and in particular a method of forming a dye image by heating a dye released by heating into a dye fixing layer. The present invention relates to a method of moving a dye image to form a dye image.

Prior art and its problems Photography using silver halide has traditionally been the most widely used method because it has superior photographic properties such as sensitivity and gradation control compared to other photographic methods such as electrophotography and diazo photography. It has been used in

In recent years, a technology has been developed that allows images to be easily and quickly obtained by changing the image forming method for photosensitive materials using silver halide from the conventional wet processing using a developing solution to a dry processing using heating, etc. It has been.

Many methods have been proposed for obtaining color images using a dry method.

A method for forming a color image by combining an oxidized developer with a coupler is described in U.S. Pat. ,761,
No. 270, p-amino/phenolic reducing agents are described in Belgian Patent No. 802,519 and in Research Disclosure, September 1975, p. 31-32, sulfonamide phenolic reducing agents are also described in U.S. Pat.
, 021.240 proposes a combination of a sulfonamidophenolic reducing agent and a 4-equivalent coupler.

In addition, a method of introducing a nitrogen-containing heterocyclic group into a dye, forming a silver salt, and releasing the dye by heat development is described in Research Disclosure Magazine, May 1978 issue, pages 54-58 RD.
-16966.

Further, regarding the method of forming a positive color image by thermal silver dye bleaching method, for example, see Research Disclosure Magazine, April 1976 issue, pages 30-32 (RD-144
33), December 1976 issue of the same magazine, pages 14-15 (R
D-15227) and U.S. Pat. No. 4,235,957, useful dyes and bleaching methods are described.

Further, methods for forming color images using leuco dyes are described, for example, in US Pat. No. 3,985,565 and US Pat. No. 4,022,617.

The above-mentioned methods generally require a relatively long time for development, and the resulting images have the drawbacks of high fog and low density.

In order to improve these drawbacks, Japanese Patent Application Laid-Open No. 58-79247
No. 6, No. 2003-11-109, discloses a heat-developable photosensitive material using a dye-donating substance that releases a hydrophilic dye by reacting with the oxidation product of a reducing agent. With this type of dye-donating substance,
Although the development progresses quickly, the resulting image has high fog.
It is still unsatisfactory as it cannot solve the drawback of low maximum concentration.

■Object of the Invention The object of the present invention is to provide a dye which accelerates the formation rate of a dye image when a dye image is formed by heating in a substantially water-free state, and which has a sufficiently high maximum density by heating for a short time. An object of the present invention is to provide an image forming method that allows an image to be obtained.

■Disclosure of invention Such objects are achieved by the invention described below.

That is, 1, the present invention includes at least a photosensitive silver halide, a binder, a substance that acts as a reducing agent for the photosensitive silver halide when heated, and a hydrophilic dye released by reacting with an oxidized form of this reducing agent. A photosensitive material having a dye-providing substance is heated in a substantially water-free state after or simultaneously with imagewise exposure in the presence of a compound represented by the following general formula (A) to make it movable. This is an image forming method characterized by forming a liquid dye into an image.

In the general formula (L general formula (A), R1 is a hydrogen atom or n
represents a substituted or unsubstituted aliphatic hydrocarbon group.

R2 and R3 each represent a hydrogen atom or a substituted or unsubstituted aliphatic hydrocarbon group or aromatic hydrocarbon group, and R2 and R3 may be the same or different.

R1 and R2 and R2 and R3 may be linked to each other to form a heterocycle.

n represents 1 or 2) ■Specific structure of the invention Hereinafter, a specific configuration of the present invention will be explained in detail.

In the image forming method of the present invention, the photosensitive material is prepared in a substantially water-free state after or simultaneously with the imagewise exposure! When a dye that can be heated and moved in an island is formed into an image, the following general formula (
A compound represented by A) is present.

General formula E In general formula (A), R1 is a hydrogen atom or n
represents a substituted or unsubstituted aliphatic hydrocarbon group with a valence of 1 to 2, preferably a saturated hydrocarbon group with a valence of 1 to 60 carbon atoms (more preferably 1 to 40), a saturated hydrocarbon group with a valence of 1 to z and a carbon number An unsaturated hydrocarbon group of number 1 to 60 (more preferably 1 to 20), or monovalent to divalent and carbon number 1 to 6
0 (more preferably 1 to 40) cyclic hydrocarbon groups. These groups further include an alkoxy group, an acyloxy group, a carbalkoxy group, a carboxyl group, a hydroxyl group, an epoxy group, or a halogen atom (preferably chlorine, bromine or fluorine).

A more preferable example of R1 is monovalent and has 1 to 4 carbon atoms.
0 saturated hydrocarbon group, such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, 5e
c-butyl group, inbutyl group, t-butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group,
Decyl group, undecyl group, dodecyl group, tridecyl group,
Pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, etc., and are generally represented by CH- (
k is an integer from 1 to 40 (2+1 number).

Another preferred example of R1 is divalent and carbon/prime number 1 to 4.
0 saturated hydrocarbon group with the general formula -CkH2,-(k
is an integer from 1 to 40), for example, -CH2-1
(-CH2+2, (-CH2+4, (-CH2+r
, (-CH2+s, etc.).

Another preferred embodiment of )11 is a monovalent unsaturated hydrocarbon group having 1 to 40 carbon atoms. It is preferably represented by -1 in the general formula CkH2, where k is 1 to 40
integer) 1 for example.

Examples include Ca Ht7CH=CH(CH2)7-.

Another more preferable embodiment of R1 is that it is divalent and has 1 carbon number.
~40 unsaturated hydrocarbon groups.

This is preferably represented by -3 in the general formula +CH+ k 2 (k is an integer from 1 to 40), for example -CH=C
Examples include H-CH2=C- CH2-.

Another more preferable embodiment of R1 is a monovalent cyclic hydrocarbon having 1 to 40 carbon atoms, preferably having the general formula C
-4 to kH2 (k is an integer from 1 to 40, 3,5
or 7). Examples include cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclododecyl group, cyclohexenyl group, adamantyl group, and the like.

Another preferred embodiment of R1 is a divalent cyclic hydrocarbon having 1 to 40 carbon atoms, preferably represented by the general formula +c
, R2 is represented by -j+ (where k is an integer from 1 to 40, and j represents 2, 4 or 6). For example, etc.

Above 1 (the saturated hydrocarbon group given as an example of 1 has 1 carbon number)
-40 (preferably 1-20) alkoxy groups (e.g. methoxy, ethoxy).

butoxy group, hexadenoxy group, etc.) primary prime number 1 to 4
0 (preferably 1 to 20) acyloxy groups (for example, fatty acid ester groups having 1 to 20 carbon atoms, aromatic carboxylic acid ester groups having 1 to 20 carbon atoms, etc.), carboalkoxy groups having 2 to 40 carbon atoms, carboxyl groups , hydroxyl group, epoxy group, chlorine atom or fluorine atom are also mentioned as preferred examples of R1.

R2 and R3 each represent a hydrogen atom or a substituted or unsubstituted aliphatic hydrocarbon group or aromatic hydrocarbon group, preferably a hydrogen atom or a saturated hydrocarbon having 1 to 60 carbon atoms (more preferably 1 to 40 carbon atoms). group, carbon number 1~
60 (more preferably 1 to 20) unsaturated hydrocarbon group, cyclic hydrocarbon group having 1 to 60 carbon atoms (more preferably 1 to 40), or 6 to 60 (preferably 6 to 40) aromatic hydrocarbon group These groups further represent alkoxy groups.

Acyloxy group, carbalkoxy group, carboxyl group, hydroxyl group, epoxy group, or halogen atom (
(preferably chlorine, bromine or fluorine).

More preferred examples of R2 or R3 are a hydrogen atom or a saturated hydrocarbon group having 1 to 40 carbon atoms, such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, 5ec-butyl group, isobutyl group, t -butyl group, pentyl group, hexyl group, heptyl group, octyl group,
Nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, pentadecyl group, hexade 1+, -44+
E-k f-+-+ 廿 上hh 1-11 あんしん- exists, and is generally represented by CH- (k is an integer from 1 to 40, k2 + 1 number).

Another more preferable embodiment of R2 or R3 is that R2 or R3 has 1 carbon number.
~40 unsaturated hydrocarbon groups. This is preferably represented by -1- in the general formula CkH2 (k is an integer from 1 to 40) 1, for example, C8H17CH=CH(CH2)a -
etc.

Another more preferable embodiment of R2 or R3 is that R2 or R3 has 1 carbon number.
-40 cyclic hydrocarbon, preferably with the general formula 〇kH
2 to -1 (k is an integer from 1 to 40, and the sentence represents 3.5 or 7). Examples include cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclododecyl group, cyclohexenyl group, adamantyl group, and the like.

The saturated hydrocarbon group listed as an example of R2 or R3 has an alkoxy group having 1 to 40 carbon atoms (preferably 1 to 20 carbon atoms, such as a methoxy group, ethoxy group, butoxy group, hexadenoxy group, etc.), or a carbon number 1 to 40 (preferably 1 to 20). 40 (preferably 1-20
), 7-syloxy group (for example, fatty acid ester group having 1 to 20 carbon atoms, aromatic carboxylic acid ester group having 1 to 20 carbon atoms, etc.), carbalkoxy group having 2 to 40 carbon atoms, carboxyl group, hydroxyl group, epoxy group , those substituted with a chlorine atom or a fluorine atom are also cited as preferred examples of R2 or R3.

Further, 7112 and R3 may be the same or different.

Furthermore, R1 and R2 and R2 and R3 may be connected to each other to form a heterocycle, and a preferable example is a nitrogen-containing heterocycle, and among these, a 5- or 6-membered ring is preferable. The heterocycle can contain 1 to 2 nitrogen atoms or oxygen atoms in addition to carbon atoms.

Examples of the compounds of the present invention are shown below, but the compounds of the present invention are not limited thereto.

(1) C7HIS CON (CH3)2(2)
C7HIS CON (C2R5) 2(3)
Co R23CON (CH3)2(4) C1
1H2I CON (C2Hs)2(5)
C3HI7 CH=CH(CH2)7CON(OH3
)2(6) C3HI70H=ICH(CII2)
+t C0NH2top (28) C11HzI CON+C2H4CIL
)2(29)CIl H2I C0N(-C2H40
CH3)2 The compound of general formula (A) above can generally be easily synthesized by reacting a corresponding carboxylic acid ester with an amine, reacting a carboxylic acid chloride with an amine, or reacting a carboxylic acid anhydride with an amine. be done. S and R for these synthetic reactions.

Sandler (S, R, 5andler), W, Caro (W
, Karo) 11. ”Organic Fun
ctionalGroup I) reparatio
ns)”.

Academic Press
(1968), pages 269-300, and the references cited therein are useful references. Also written by V, Migrdicbian.

“Organic Sensibility Volume 1 (OrganicS
Reinhold Publishing Corp.
(1957), pages 367-394 and references thereof, H, Bertsch, H, Reinheckel, G, Qi/
Co-authored by Mkey (G, Czichocki), Hetzte, Seihen.

Anstrichmittel (Fette, 5eif
en.

Anstricb+5ittel) 6 once, 81
7-24 (1966), 11: Mie Zeitung (C
Hew.

Zent, ) 37-2494 (1967), T
, H, Applewhite
e) J, S, Binde
r), Journal of the American Oil Chemistry Society, Volume 44 (J, Ara, Oil Chew
, Sac, ±4), 423-424 (1967) and Yamate, Irobe, "Fatty Acid Chemistry" (Revised and Expanded Edition), Saiwai Shobo (1974), pages 81-95, are also helpful.

As a synthesis example, the synthesis of N-butyl-12-hydroxystearic acid amide is shown below.

(Synthesis Example) 12-, 50 g of methyl droxystearate, 300 ml of methanol, and 20 ml of a 28% methanol solution of sodium methoxide were mixed, and then 50 mJL of n-butylamine was added. This mixture was heated to reflux for 6.5 hours.

After cooling the reaction solution, it was poured into dilute hydrochloric acid, and the precipitated crystals were collected. Yield 47g, mp 100-102°C.

The compounds exemplified above can also be synthesized in the same manner, as well as in the above-mentioned literature and Oil and Fat Chemistry Handbook (revised 2nd edition) Maruzen (1971).
) 142 pages Table 2・116, Table 2・l l 7,
R,B, Wagner (R,B.

Wagner), H, D, Zouk (H, D, Z
ook) Co-author.

“Synthetic Organifuku Chemistry (5ynth
etic Organic Chemigtr7)”,
Published by John Willey (1953),
It can also be synthesized by the method of the literature cited on pages 578-583.

The compounds of the present invention can be dispersed singly or in combination of two or more in an aqueous solution of a hydrophilic colloid using a dispersion aid. This method of dispersion is described, for example, in U.S. Pat. No. 2,304.

No. 939, No. 2.322,027, No. 2.801
, No. 170, No. 2.801.171, No. 2.94
9.360 etc.

At this time, the compounds of the present invention include, for example, phthalic acid alkyl esters (dibutyl phthalate, dioctyl phthalate, etc.), phosphoric acid esters (diphenyl phosphate,
triphenyl phosphate, tricresyl phosphate, dioctyl butyl phosphate), citric acid esters (e.g. acetyl tributyl citrate), benzoic acid esters (e.g. octyl benzoate), fatty acid esters (e.g. dibutoxyethyl succinate, dioctyl It can also be used in combination with a high boiling point organic solvent such as (acetate).

Typically, the compounds of the present invention are dispersed in an aqueous solution of hydrophilic colloids together with a dye-donating substance and a low-boiling organic solvent with a boiling point of 30°C to 160°C using a dispersion aid.
It is also possible to simultaneously disperse other photographic additives, if desired.

As a low boiling point organic solvent with a boiling point of 30°C to 160°C,
For example, lower alkyl acetates such as ethyl acetate and butyl acetate, ethyl propionate, secondary butyl alcohol, methyl isobutyl ketone, and β-ethoxyethyl acetate.

Methyl cellosolve acetate and cyclohexanone are used.

In addition, dispersion aids include anionic surfactants (for example, sodium alkylbenzene sulfonate, sodium dioctyl sulfosuccinate, sodium dodecyl sulfate, sodium alkylnaphthalene sulfonate, Fischer type couplers, etc.), amphoteric surfactants, etc. Agent (
For example, N-tetradecyl-N,N-dipolyethylene-α
- betaine) and nonionic surfactants (such as sorbitan monolaurate) are used. Furthermore,
As dispersion aids, surfactants described elsewhere in this specification can be used as well.

A dispersion consisting of Taiyi Ming's dispersion as described above for dye provision may be added to either an emulsion layer such as a silver halide emulsion layer, an intermediate layer, or the same in a heat-developable photosensitive material. I can do it. Furthermore, a dispersion of the compound of the present invention that does not contain a dye-donating substance can be used in a hydrophilic colloid layer (for example, a surface protective layer, an intermediate layer, etc.) or an emulsion layer (for example, a silver halide emulsion layer, etc.) of a photothermographic material. .

Further, it can be used in a layer containing a mordant and other layers of a fixing material to be described later. Here, when introducing the compound of the present invention into the layer of the photosensitive material, US Pat.
．． Known methods such as the method of No. 322.027 No. 322.027 may be used.

The compound of the present invention is generally used in an amount of 0.01 to 20 times, more preferably o, oi to 5 times, by weight relative to one dye-providing substance.

In addition, when the compound of the present invention is contained in a layer that does not contain a dye-providing substance, the compound of the present invention may contain 0.001 to 5
Preferably, g/m2 is used.

The dye image of the present invention includes multicolor and monochrome dye images, and the monochrome image in this case includes a monochrome image obtained by mixing two or more types of dyes.

In the image forming method of the present invention, a silver image and a mobile dye can be simultaneously provided in the area corresponding to the silver image by simply heating the image after exposure. In the present invention, the image forming reaction proceeds particularly well in the presence of an organic silver salt oxidizing agent, resulting in high image density. Therefore, the coexistence of an organic silver salt oxidizing agent is a particularly preferred embodiment. The silver halide that can be used in the present invention may be silver chloride, silver bromide #I5 iodide, or silver chlorobromide, silver chloroiodide, silver iodobromide, or silver chloroiodobromide. The halogen composition may be uniform, or it may have a multiple structure with different compositions on the surface and inside (Japanese Patent Application Laid-open No. 154232/1983, 58-
No. 108533, No. 59-48755, No. 59-52
No. 237, US Pat. No. 4,433,048 and European Patent No. 100,984);
5 Bm or less, the diameter is at least 0.6 Bm, and the average aspect ratio is 5 or more (U.S. Pat. No. 4,414.3).
No. 10, OLS No. 4.435.499 and OLS No. 3,241°646AI, etc.), or monodispersed emulsions with nearly uniform particle size distribution (JP-A-57-1
No. 78235, No. 58-100846, No. 58-14
829, International Publication No. 83102338A1, European Patent No. 64,412A3 and European Patent No. 83°377A1, etc.) may also be used in the present invention. Two or more types of silver halides with different crystal habit, halogen composition, pattern size, grain size distribution, etc. may be used in combination. One gradation can be adjusted by mixing two or more types of monodispersed emulsions with different grain sizes. You can also.

The average grain size of the silver halide used in the present invention is preferably from 0.0011 Lm to 104 m, more preferably from 0.0014 m to 5 gm.

These silver halide emulsions may be prepared by any of the acid method, neutral method, or ammonium method, and the reaction method of the soluble silver salt and soluble halide salt may be one-sided mixing method, simultaneous mixing method, or any of these methods. A back-mixing method in which particles are formed in an excess of silver ions, or a Chondral double-jet method in which pAg is kept constant can also be employed. Furthermore, in order to accelerate grain growth, the concentration, amount, or rate of addition of silver salts and halogen salts may be increased (Japanese Patent Application Laid-open No. 55-142329
No. 55-158124, U.S. Patent No. 3, 650
.

No. 757, etc.).

Epitaxial junction type silver halide grains can also be used (JP-A-56-16124, U.S. Patent No. 4
, No. 094, 684).

Although the silver halide emulsion may be used unripe, it is usually used after being chemically sensitized. Known sulfur sensitization method and reduction sensitizer for emulsions for conventional light-sensitive materials.
It can be used as follows. These chemical sensitizations can also be carried out in the presence of nitrogen-containing heterocyclic compounds (JP-A-58-126526, JP-A-58-21).
No. 5644).

The silver halide emulsion used in the present invention may be a surface latent image type where a latent image is mainly formed on the grain surface or an internal latent image type where a latent image is formed inside one grain. Direct inversion emulsions combining emulsions and nucleating agents can also be used.

The coating amount of the photosensitive silver halide used in the present invention is in the range of 1 mg to 10 g/m 2 in terms of silver.

In the present invention, as mentioned above, it is desirable to use an organic metal salt relatively stable to light, especially an organic silver salt, as an oxidizing agent together with the photosensitive silver halide. and the organic silver salt need to be in contact or at a close distance. When an organic silver salt is used in combination in this way, the temperature of the heat-developable photosensitive material is 80°C or above.
Preferably, when heated to a temperature of 100° C. or higher, the organic silver salt oxidizing agent is also considered to participate in redox using the latent image of silver halide as a catalyst.

Examples of organic compounds that can be used to form the organic silver salt oxidizing agent include aliphatic or aromatic carboxylic acids, thiocarbonyl group-containing compounds having a mercapto group or α-hydrogen, and imino group-containing compounds. Can be mentioned.

For details of these, please refer to Japanese Patent Application No. 59-213978.
No. 30-34.

The silver halide used in the present invention may be spectrally sensitized with methine dyes and others.

Regarding these pigments and their details, please refer to the patent application filed in 1983.
-213978, pages 34 to 38.

In the present invention, a substance that acts as a reducing agent for photosensitive silver halide upon heating is included. Such substances include those generally known as reducing agents, as well as dye-donating substances having reducing properties. Also included are reducing agent precursors that do not themselves have reducing properties but develop reducing properties through the action of nucleophiles and heat during the development process.

Examples of reducing agents used in the present invention include inorganic reducing agents such as sodium sulfite and sodium bisulfite, benzenesulfinic acids, hydroxylamines, hydrazines, hydrazides, borane-amine complexes, hydroquinones, and aminophenols. , catechols, p-phenylenediamines, 3-pyrazolidinones, hydroxytetrones, ascorbic acid, 4-amino-5-pyrazolones, and the like.

T. H. Jayaes, “
The theory of the photographic process
photographic process)”
The reducing agents described in 4th Edition (4th Ed), pages 291-334 can also be used.

Also, JP-A-56-138736, JP-A No. 57-4024
Reducing agent precursors such as those described in US Pat. No. 5, US Pat. No. 4,330,617 can also be used. US Patent No. 3
．． Combinations of various developers can also be used, such as those disclosed in US Patent No. 039,869.

In the present invention, the amount of reducing agent added is 0 per mole of silver.
．． 01 to 20 mol, particularly preferably 0.1 to 10 mol.

The light-sensitive material of the present invention contains a dye-donating substance that reacts with the oxidized form of the reducing agent mentioned above to release a hydrophilic dye.

The dye-donating substance that releases a hydrophilic dye used in the present invention is represented by the following general formula 〇-LD.

Here, C represents a substrate that binds to an oxidant produced by the reaction between a reducing agent and an organic silver salt oxidizing agent, D represents an image-forming dye moiety, and L represents a linking group between C and D. , the C-L bond is cleaved by the reaction between the oxidized form of the reducing agent and C.

The substrate C that can bind to the oxidant produced by the reaction between the reducing agent and the organic silver salt oxidizing agent is an active methylene, active methine, phenol, or naphthol residue, and preferable substrates are represented by the following general formulas (I) to ( ■).

R1, R2, R3, and R4 are each a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an alkoxy group,
Aryloxy group, aralkyl group, acyl group, acylamino group, alkoxyalkyl group, aryloxyalkyl group, N-substituted rubamoyl group, alkylamino group, arylamine group, halogen atom, acyloxy group, acyloxyalkyl group, cyano group These substituents further include a hydroxyl group, a cyano group, a nitro group, an N-substituted sulfamoyl group, a carbamoyl group, an N-substituted rubamoyl group, an acylamide group, an alkylsulfonylamino group. , an arylsulfonylamino group, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an aralkyl group, or an acyl group.

Substrate C must have the function of releasing a hydrophilic dye by combining with the oxidized form of the reducing agent, and must also have a ballast group to prevent the dye-donating substance itself from diffusing into the dye-receiving image-receiving layer. The /<last group is preferably a hydrophobic group such as an alkyl group, an alkoxyalkyl group, or an aryloxyalkyl group, and these ballast groups preferably have a total number of carbon atoms of 6 or more, and the total number of carbon atoms in the substrate C is preferably 6 or more. The number of carbon atoms is preferably 12 or more.

The linking group connects the substrate C and the dye moiety through a covalent bond, and at the same time functions as a leaving group in the reaction between the oxidized product of the reducing agent and the substrate C.

The linking group is preferably a divalent residue selected from the following general formula.

-NHCONH- n=IJ N;j where R and R' represent a hydrogen atom, a methyl group, or an ethyl group, and the benzene ring further represents a hydroxyl group, a sulfamoyl group, or a methyl group.

It may be substituted with an ethyl group, an alkoxy group, a hydroxyalkyl group, a hydroxyalkoxy group, an alkoxyalkoxy group, or a halogen atom.

Among these linking groups, those having a total carbon number of 12 or less and those having high hydrophilicity give good results.

Dyes that can be used as image-forming dyes include azo dyes, azomethine dyes, and anthraquinone dyes.

naphthoquinone dyes, indigoid dyes, carbonium ion dyes, styryl dyes, quinoline dyes, nitro dyes,
There are phthalocyanine dyes, etc., a typical example of which is represented by the general formula on pages 25 to 34 of European Patent Publication No. 79,056, and specific examples thereof are those described on pages 36 to 42 of this publication. .

Further, specific examples of the compound represented by CLD are described, for example, on pages 43 to 51 of European Patent Publication No. 79,056.

The dye-donating substance used in the present invention is described in US Pat.
They can be incorporated into the layers of the photosensitive material by known methods such as the method described in No. 322,027. In that case, the above-mentioned high boiling point organic solvents and low boiling point organic solvents can be used.

Also, Japanese Patent Publication No. 51-39853, Japanese Patent Publication No. 51-5994
The dispersion method using polymers described in No. 3 can be used. In addition, various surfactants can be used when dispersing the dye-donating substance in the hydrophilic colloid, and these surfactants include those listed as surfactants elsewhere in this specification. You can use it.

In the present invention, an image formation accelerator can be used in the light-sensitive material. Image formation accelerators include accelerating redox reactions between silver salt oxidizing agents and reducing agents, accelerating reactions such as generation of dyes from dye-donating substances, decomposition of dyes, and release of mobile dyes, and photosensitive material layers. It has functions such as promoting the movement of dye from the dye fixing layer to the dye fixing layer, and from a physicochemical function, it interacts with bases or base precursors, nucleophilic compounds, oils, hot solvents, surfactants, silver or silver ions. It is classified as a compound with . However, these substance groups generally have multiple functions and usually have some of the above-mentioned promoting effects.

For details of these, see Japanese Patent Application No. 59-213978 6.
It is described on pages 7-71.

In the present invention, various development stoppers can be used in the photosensitive material in order to always obtain a constant image despite fluctuations in processing temperature and processing time during thermal development.

The development stopper referred to here is a compound that neutralizes the base immediately after proper development or reacts with the base to lower the base concentration in the film and stop development, or a compound that inhibits development by interacting with silver and silver salts. It is a compound that

For specific examples, see Japanese Patent Application No. 59-213978, 72-7.
It is described in the literature shown on page 3.

Further, in the present invention, a compound that activates the development and stabilizes the image can be used in the photosensitive material.

For specific compounds that are preferably used, see Japanese Patent Application No. 1983.
-213978, pages 73-74.

In the present invention, the photosensitive material may contain an image toning agent if necessary. Specific examples of effective toning agents are described in Japanese Patent Application No. 59-213978, pages 74-75.

The binders used in the photosensitive material of the present invention may be contained alone or in combination. A hydrophilic binder can be used for this binder. Hydrophilic binders are typically transparent or translucent, such as gelatin, gelatin derivatives,
Other synthetic polymeric substances include natural substances such as proteins such as cellulose derivatives, polysaccharides such as starch and gum arabic, and synthetic polymeric substances such as water-soluble polyvinyl compounds such as polyvinylpyrrolidone and acrylamide polymers. There are dispersed vinyl compounds, especially in latex form, which increase the dimensional stability of photographic materials.

In the present invention, the binder is applied in an amount of 20 g or less per m2, preferably 10 g or less, more preferably 7 g or less.

The ratio of the high boiling point organic solvent dispersed in the binder together with a hydrophobic compound such as a dye-donating substance and the binder is 1'cc or less of solvent per 1g of binder, preferably 0.
．． A suitable amount is 5 cc or less, more preferably 0.3 cc or less.

The photographic light-sensitive materials and dye-fixing materials of the present invention may contain inorganic or organic hardeners in the photographic emulsion layer and other binder layers, such as chromium salts (chromium alum,
chromium acetate, etc.), aldehydes (formaldehyde, glyoxal, geltaraldehyde, etc.), N-methylol compounds (dimethylol urea, methylol dimethylhydantoin, etc.), dioxane derivatives (2,3-dihydroxydioxane, etc.), activated vinyl compounds (1, 3,5-
triacryloyl-hexahydro-8-triazine, 1
．． 3-vinylsulfonyl-2-propatol, 1,2-
bis(vinylsulfonylacetamido)ethane, etc.), active halogen compounds (2,4-dichloro-6-hydroxy-s-triazine, etc.), mucohalogen acids, (mucochloric acid, mucophenoxychloroic acid, etc.), etc., singly or in combination. It can be used as

The support used in the light-sensitive material and dye-fixing material used in the present invention is one that can withstand processing temperatures. As a general support,
Glass, paper, metal and their analogs are used, as well as cellulose acetate films, cellulose ester films, polyvinyl acetal films, polystyrene films, polycarbonate films, polyethylene terephthalate films and related films or resin materials. Paper supports laminated with polymers such as polyethylene can also be used. U.S. Pat. No. 3,634.

The polyesters described in No. 089 and No. 3,725,070 are preferably used.

When using a dye-donating substance that releases an image-wise mobile dye in the present invention, a dye transfer aid can be used to transfer the dye from the photosensitive layer to the dye fixing layer. Regarding, Japanese Patent Application No. 59-213978 78
It is described on pages ~79.

When the light-sensitive material used in the present invention contains a colored dye-donating substance, it is not necessary to further contain an irradiation-preventing substance, an anti-irradiation substance, or various dyes. Although not necessary, filter dyes, absorbent substances, etc. described in the literature exemplified on page 80 of Japanese Patent Application No. 59-213978 can be included.

The photosensitive material used in the present invention may optionally contain various additives known as heat-developable photosensitive materials and layers 1 below the photosensitive layer, such as an antistatic layer.

It can contain a conductive layer, a protective layer, an intermediate layer, an AH layer, a release layer, and the like. Examples of various additives include additives described in Research Disclosure Magazine Vol. 1.170. June 1978, No. 17029, such as plasticizers, sharpness improving dyes, AH dyes, sensitizing dyes, and matting agents. ,
Additives include surfactants, optical brighteners, and anti-fading agents.

The photographic elements of this invention optionally are photosensitive elements that form or release dyes upon thermal development.

It consists of a dye fixing element that fixes the dye.

In particular, in systems that form images by diffusion transfer of dyes, a photosensitive element and a dye fixing element are essential, and in one typical form, the photosensitive element and dye fixing element are separately coated on two supports. It is broadly divided into two types: a form in which it is coated on the same support and a form in which it is coated on the same support.

There are two types of forms in which the photosensitive element and the color/prime fixing element are formed on separate supports: one is a peelable type and the other is a peelable type. In the case of the former peel-off type, after image exposure or heat development, the coated surface of the photosensitive element and the coated surface of the dye-fixing element are overlapped, and the photosensitive element is immediately peeled off from the dye-fixing element after the transfer image is formed. Depending on whether the final image is of a reflection type or a transmission type, the support of the dye fixing element can be selected as an opaque support or a transparent support.

In addition, a white reflective layer may be coated if necessary. In the latter type, which does not require peeling, a white reflective layer is interposed between the photosensitive layer in the photosensitive element and the dye fixing layer in the dye fixing element. This white reflective layer may be coated on either the photosensitive element or the dye-fixing element.The support of the dye-fixing element must be a transparent support.

A typical configuration in which the photosensitive element and the dye-fixing element are coated on the same support is a configuration in which there is no need to peel off the photosensitive element from the image-receiving element after the transfer image is formed. In this case, a photosensitive layer, a dye fixing layer and a white reflective layer are laminated on a transparent or opaque support. Preferred embodiments include, for example, transparent or opaque support/photosensitive layer/white reflective layer/dye fixing layer/transparent support/dye fixing layer/white reflective a/photosensitive layer.

Another typical form in which a photosensitive element and a dye fixing element are coated on the same support is disclosed in JP-A-56-67840, for example.
．． Canadian Patent No. 674,082, U.S. Patent No. 3,73
As described in No. 0,718, there is a form in which part or all of the photosensitive element is peeled off from the dye fixing element, and a peeling layer is coated at an appropriate position.

The photosensitive element or dye fixing element may be in the form of a heating developer or a conductive heating layer as a heating means for diffusion transfer of the dye.

In order to obtain a wide range of colors in the chromaticity diagram using the three primary colors yellow, magenta and cyan, the light-sensitive element used in the present invention comprises at least three layers of silver halide, each sensitive to a different spectral region. It is necessary to have an emulsion layer.

Typical combinations of at least three light-sensitive silver halide emulsion layers sensitive to different spectral regions include a combination of a blue-sensitive emulsion layer, a green-sensitive emulsion layer and a red-sensitive emulsion layer, a green-sensitive emulsion layer, and a red-sensitive emulsion layer. A combination of a sensitive emulsion layer and an infrared sensitive emulsion layer, a combination of a blue sensitive emulsion layer, a green sensitive emulsion layer and an infrared sensitive emulsion layer, a blue sensitive emulsion layer, a red sensitive emulsion layer and an infrared sensitive emulsion. There are combinations of layers, etc.

In addition, the infrared light-sensitive emulsion layer is 7001111 or more,
In particular, it refers to an emulsion layer that is sensitive to light of 740 nm or more.

The light-sensitive material used in the present invention may have two or more emulsion layers sensitive to the same spectral region, depending on the sensitivity of the emulsion, if necessary.

Each of the above emulsion layers and/or the non-photosensitive hydrophilic colloid layer adjacent to each emulsion layer contains a dye-donating substance that releases or forms a yellow hydrophilic dye, and a dye-donating substance that releases or forms a magenta hydrophilic dye. It is necessary to contain at least one of a dye-donating substance and a dye-donating substance that releases or forms a cyan hydrophilic dye. In other words, each emulsion layer and/or the non-photosensitive hydrophilic colloid layer adjacent to each emulsion layer must contain dye-donating substances that release or form hydrophilic dyes of different hues. If desired, two or more dye-providing substances of the same hue may be mixed and used. In particular, if the dye-providing substance is colored from the beginning, the dye-providing substance may be used separately from this emulsion layer. It is advantageous to include it in the layer. In addition to the above-mentioned layers, the photosensitive material used in the present invention may be provided with auxiliary layers such as a protective layer, an intermediate layer, an antistatic layer, an anti-curl layer, a release layer, and a matting agent layer, if necessary.

In particular, the protective layer (PC) usually contains an organic or inorganic matting agent to prevent adhesion. In addition, this protective layer may contain a mordant, a UV absorber, etc.
Each of the protective layer and the intermediate layer may be composed of two or more layers.

The intermediate layer may also contain a reducing agent for preventing color mixture, a UV absorber, and a white pigment such as TiO2.The white pigment may be added not only to the intermediate layer but also to the emulsion layer for the purpose of increasing sensitivity. You can.

In order to impart each of the above-mentioned color sensitivities to a silver halide emulsion, each silver halide emulsion may be dye-sensitized using a known sensitizing dye to obtain the desired spectral sensitivity.

The dye-fixing element used in the present invention has at least one layer containing a mordant, and when one dye-fixing layer is located on the surface, if necessary, further retains 14yI! can be provided.

Furthermore, a water absorption layer or a layer containing a dye transfer aid can be provided in order to sufficiently contain a dye transfer aid or to control the dye transfer aid if necessary. These layers may be adjacent to the dye fixing layer or may be applied via an intermediate layer.

The dye fixing layer used in the present invention may be composed of two or more layers using mordants having different mordant powers, if necessary.

In addition to the above-mentioned layers, the dye fixing element used in the present invention can be provided with auxiliary layers such as a release layer, a matting agent layer, and an anti-curl layer, if necessary.

One or more of the above layers may include a base and/or base precursor to promote dye migration, a hydrophilic thermal solvent, an anti-fade agent to prevent color mixing of the dyes, a UV absorber, a dimensional stability agent, etc. Dispersed vinyl compound for increasing
A fluorescent whitening agent or the like may be included.

The binder in the above layer is preferably hydrophilic, and transparent or translucent hydrophilic colloids are typical. For example, gelatin, gelatin conductors, polyvinyl alcohol, proteins such as cellulose derivatives, starch, natural substances such as polysaccharides such as gum arabic, dextrin, pullulan,
Synthetic polymeric substances such as polyvinyl alcohol, polyvinylpyrrolidone, water-soluble polyvinyl compounds such as acrylamide polymers, etc. are used. Especially gelatin,
Polyvinyl alcohol is effective.

In addition to the above, dye fixing elements include a reflective layer and a neutralizing layer containing white pigments such as titanium liquefaction, depending on the purpose.

It may also have a neutralization timing layer or the like.

These layers may be coated not only in the dye-fixing element but also in the light-sensitive element, such as the reflective layer described above.

The configuration of the neutralization layer and the neutralization timing layer is 1, for example, U.S. Pat. No. 2,983,606, U.S. Pat.
It is described in Canadian Patent No. 3,362,821, Canadian Patent No. 3,415,644, Canadian Patent No. 928.559, etc.

Furthermore, it is advantageous for the dye fixing element of the present invention to contain a transfer aid as described below. The transfer aid may be included in the dye fixing layer, or may be included in a separate layer.

In the present invention, the transparent or opaque heat generating element when electrical heating is employed as the developing means can be made using conventionally known techniques as a resistance heating element.

As a resistance heating element, there are two methods: one uses a thin film of an inorganic material that exhibits semiconductivity, and the other uses a thin film of an organic material in which conductive fine particles are dispersed. These include silicon, molybdenum silicide, lanthanum chromate, barium titanate ceramics used as PTC thermistors, soot oxide, zinc oxide, etc., and transparent or opaque thin films can be made by known methods.The latter method uses fine metal particles. conductive particles such as carbon black, graphite, rubber, and synthetic polymers.

By dispersing it in gelatin, it is possible to create a resistor with temperature characteristics of a given ψ. These resistors may be in direct contact with the photosensitive element or may be separated by a support, intermediate layer, or the like.

An example of the positional relationship between the heat generating element and the photosensitive element is shown below.

Heat generating element/support/photosensitive element support 7 Heat generating element/photosensitive element support/heat generating element/intermediate layer/photosensitive element support/photosensitive element/heat generating element support/photosensitive element/intermediate layer/heat generating element Image in the present invention As the image-receiving layer, there is a dye fixing layer used in heat-developable color light-sensitive materials, and any mordant can be selected from commonly used mordants, but polymer mordants are particularly preferred.Here, what is a polymer mordant? .

These include polymers containing a tertiary amino group, polymers having a nitrogen-containing heterocyclic moiety, and polymers containing these quaternary cation groups.

Regarding this specific example, please refer to Japanese Patent Application No. 59-213978.
It is described in the literature exemplified on pages 1 to 91.

In the present invention, as well as the heat-developable photosensitive layer, coating solutions for the protective layer, intermediate layer, undercoat layer, backing layer, and other layers are prepared for each layer using the dipping method, air knife method, curtain coating method, or U.S. A light-sensitive material can be prepared by sequentially coating onto a support by one of various coating methods, such as the hopper coating method described in Japanese Patent No. 3,681,294, and drying.

Furthermore, if desired, two or more layers can be applied simultaneously by the methods described in US Pat. No. 2,761.791 B and British Patent No. 837.095.

As a light source for image exposure for recording an image on a heat-developable photosensitive material, radiation including visible light can be used. In general, light sources used for normal color printing include tungsten lamps, mercury lamps, iodine lamps, xenon lamps, laser light sources, CRT light sources, fluorescent tubes, and light-emitting diodes (LEDs).
Various light sources such as can be used.

The heating temperature in the heat development step can be developed at about 0°C to about 250°C, but about 10°C to about 180°C is particularly useful, and within this range, 140°C or higher is preferable, especially 1
The heating temperature in the transfer step, which is preferably 50° C. or higher, can be transferred in the range from the temperature in the heat development step to room temperature, and is particularly preferably about 10° C. lower than the temperature in the heat development step. As a heating means in the development and/or transfer process, a simple hot plate, iron, hot roller, heating element using carbon, titanium white, etc. can be used.

A dye transfer aid (for example, water) is added between the photosensitive layer of a heat-developable photosensitive material and the dye fixing layer of a dye fixing material to promote image transfer. Alternatively, a dye transfer aid may be applied to both, and then the two may be superimposed.

Examples of methods for applying the dye transfer aid to the photosensitive layer or the dye fixing layer include the roller coating method or wire bar coating method as described in Japanese Patent Application Laid-open No. 58-55907, and the method described in Japanese Patent Application No. 58-55908. A method of applying water to a dye-fixing material using a water-absorbing member as described above, and a method of applying water between a heat-developable photosensitive material and a dye-fixing material as described in Japanese Patent Application No. 58-55906. Method for applying dye transfer aid by forming, Japanese Patent Application No. 58-5591
As described in No. 0, a method of applying a dye transfer aid by forming a bead between a water-repellent roller and a dye fixing layer, and other methods include a dipping method, an extrusion method, and applying by ejecting it as a jet from pores. Various methods can be used, such as a method of applying the material by crushing the bod, and a method of applying the material by crushing the bod.

The dye transfer aid may be measured in advance and given in an amount within the range as described in Japanese Patent Application No. 58-37902, or
The amount can be adjusted and used by applying sufficient amount and then squeezing it out by applying pressure with a roller or the like or drying it by applying heat.

For example, there is a method in which a dye transfer aid is applied to a dye fixing material using the above method, the excess dye transfer aid is squeezed out by passing between pressurized rollers, and then the material is overlapped with a heat-developable photosensitive material.

The heating means in the transfer process includes heating by passing between hot plates or heating by contacting with the hot plates (for example, Japanese Patent Application Laid-Open No. 50-62635).
No. 1), heating by rotating and contacting a heated drum or heated roller (for example, Japanese Patent Publication No. 43-10791), heating by passing through hot air (for example, Japanese Patent Publication No. 53-3273)
No. 7), heating by passing through an inert liquid kept at a constant temperature, heating by passing it along a heat source using a roller, belt, or guide member (for example, Japanese Patent Publication No. 44-2546), etc. can be used. . In addition, graphite, carbon black,
Layers of electrically conductive material, such as metal, may be applied and the electrical current may be passed through the electrically conductive layers to heat them directly.

The heating temperature applied in the transfer step can be in the range from the temperature in the heat development step to room temperature, but in particular 6
The temperature is preferably 0° C. or more and 10° C. or more lower than the temperature in the heat development step.

The pressure when overlapping the heat-developable photosensitive material and the dye-fixing material and bringing them into close contact varies depending on the embodiment and the materials used.
0.1-100 kg/c2 Preferably 1-50 Kg
/c+s2 is appropriate (for example, Japanese Patent Application No. 58-556
91).

Methods for applying pressure to the photothermographic material and the dye-fixing material include a method of passing the material between a pair of rollers, a method of pressing using a plate with good smoothness, and the like.

Various methods can be used. Furthermore, the roller and plate used to apply pressure can be heated within a range from room temperature to the temperature used in the thermal development process.

■Specific effects of the invention According to the invention, a light-sensitive material is heated in a substantially water-free state after or simultaneously with imagewise exposure in the presence of the compound represented by the general formula (A). Since the movable dye is formed in the form of an image, the rate of formation of the dye image is accelerated.

Moreover, an image forming method is obtained which provides a dye image having a sufficiently high maximum density by heating for a short time.

(2) Specific Examples of the Invention Hereinafter, specific examples of the present invention will be shown, and the effects of the present invention will be explained in further detail.

Example 1 A method for preparing a benzotriazole silver emulsion containing photosensitive silver bromide will be described.

6.5g of benzotriazole and 10g of gelatin in 1 part of water
Dissolved in 0100O. This dissolution was maintained at 50°C and stirred. Next, a solution prepared by dissolving 8.5 g of silver nitrate in 100 mJ1 of water was added to the above solution over a period of 2 minutes.

Next, a solution of 1.2 g of potassium bromide dissolved in 50 mft of water was added over 2 minutes. The prepared emulsion was precipitated by PHW conditioning to remove excess salt. Then the pH of the emulsion was adjusted to 6.
．． Adjusted to 0.

Yield was 200g.

Next, we will describe how to make a gelatin dispersion of a dye-donating substance.

Weigh out 10 g of the following dye-donating substance (A), 0.5 g of sodium succinate-2-ethyl-hexyl ester sulfonate as a surfactant, and 4 g of the compound (1) of the present invention, and pour it into a cycle for 20 m. ! L was added and dissolved by heating to about 60°C to form a homogeneous solution. After stirring and mixing this solution and 100 g of a 10% solution of lime-treated gelatin, the mixture was heated to and oo for 10 minutes using a homogenizer.

Dispersed at RPM. This dispersion liquid is called a dispersion of a dye-providing substance.

Dye-donating substance (A) Next, a method for preparing a photosensitive coating will be described.

(&) Benzotriazole silver emulsion containing photosensitive silver bromide
10g (b) Dispersion of dye-donating substance 3.5g (C) Guanidine trichloroacetic acid $22
A solution of 0 mg dissolved in 2 m water (d) 2,6-dichloro-4-7 minophyl 200
(a) to (d) were mixed with a solution of 1.0 mg dissolved in 2 m of methanol, heated and dissolved, and then applied to a wet film thickness of 601 Lm on a polyethylene terephthalate film with a thickness of 180 m. This coated product is designated as sample A.

Moreover, the compound of the present invention (1
) Sample B was prepared in the same manner as Sample A except that Comparative Compound (1) below was used instead of Comparative Compound (1).

Comparative compound (1) (ζΣO)rP=0 After drying these coated samples, using a tungsten light bulb,
Imagewise exposure was made for 10 seconds at 2000 lux. #1
e Heated uniformly for 30 seconds on a heat block heated to 150°C.

Next, a method for forming an image-receiving material having an image-receiving layer will be described.

-1-1 mef711I++-1-1 no', +----
-%JkV! 10 g of -trimethyl-N-vinylbenzylammonium chloride (ratio of methyl acrylate and vinylbenzylammonium chloride is 1:1) was dissolved in 200 mff1 of water and uniformly mixed with 100 g of 105 lime-treated gelatin. This mixed solution was uniformly applied onto a polyethylene terephthalate film to a wet film thickness of 204 m. After drying, this sample was used as an image receiving material.

After the image-receiving material was immersed in water, the photosensitive material heated as described above was superimposed on it so that the film surfaces were in contact with each other. 30 seconds later,
When the image-receiving material was peeled off from the photosensitive material, a negative magenta color image was obtained on the image-receiving material. The density of this negative image with respect to green light is measured using a Macbeth transmission densitometer (TD-504).
).

The results are shown in Table 1.

Table 1 Table 1 shows that when the compound of the present invention is used, development is accelerated and a sufficient maximum density can be obtained.

Example 2 The compound of the present invention (1
) Example 1 except that the compounds shown in Table 2 were used instead of
Perform exactly the same operation.

Samples C-H were prepared.

Using these samples C-H, the same processing as in Example 1 was performed to obtain a negative magenta color image on an image-receiving material, and the density with respect to green light as in Example 1 was measured.

The results are shown in Table 2.

Table 2 It can be seen from Table 2 that in all cases, the use of the compound of the present invention facilitates development and provides a sufficient maximum density.

From the above, the effects of the present invention are clear.

1riy.

Official Proceedings NetH (spontaneous) 1. Indication of the case Patent Application No. 20698 of 1985 2. Name of the invention Image forming method 3. Person making the amendment Relationship with the case Patent applicant address Nakanuma, Minamiashigara City, Kanagawa Prefecture 210 Address Name (520) Fuji Photo Film Co., Ltd. 4, Agent
101 Telephone: 864-4498 Address: 3-2-2-6 Iwamoto-cho, Chiyoda-ku, Tokyo Contents of amendment (1) "Color mixture" on page 54, line 6 of the specification is corrected to "fading."

(2) “Gelatin derivatives,” on page 54, lines 12-14,
Polyvinyl alcohol, cellulose 1. "Proteins such as gelatin derivatives, cellulose derivatives, etc." will be corrected to "proteins such as gelatin derivatives, cellulose derivatives, etc."

(3) On page 58, lines 16 to 18, "about 180°C is useful and preferable." is corrected to "about 180°C is useful."

Claims (1)

[Scope of Claims] At least a photosensitive silver halide, a binder, a substance that acts as a reducing agent for the photosensitive silver halide when heated, and a hydrophilic dye that reacts with the oxidized form of this reducing agent are formed on a support. A photosensitive material having a dye-providing substance to be released is heated in a substantially water-free state after or simultaneously with imagewise exposure in the presence of a compound represented by the following general formula (A), and the material is movable. 1. An image forming method characterized by forming a pigment in the form of an image. General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (A) (In the above general formula (A), R^1 represents a hydrogen atom or an n-valent substituted or unsubstituted aliphatic hydrocarbon group. R^2 and R^3 each represent a hydrogen atom or a substituted or unsubstituted aliphatic hydrocarbon group or aromatic hydrocarbon group, and R^2 and R^3 may be the same or different. R^1 and R^ 2 and R^2 and R^3 may each be connected to form a heterocycle. n represents 1 or 2.)