JPH0766174B2 - Color-sensitive material - Google Patents

Description

The present invention relates to a novel cyanazo dye image-forming compound and a color light-sensitive material containing the same.

(Prior Art) Color diffusion transfer photography using an azo dye image-forming compound that provides an azo dye having a diffusivity different from the image-forming compound itself as a result of development under basic conditions has long been well known. ing.

For example, as an image-forming compound that releases a cyan dye, US 3,942,987, US 4,013,635, US 4,273,708 can be used.
No., US. 4,268,625.

However, it has been clarified that all of the compounds shown in these prior art documents have a nitro group at the para position of the azo group, and this has the secondary point of being reduced and discolored during development processing. . Further, generally, an azo dye having a nitro group has a photo-reducing property, so that the light fastness of an image is not good.

Furthermore, when these image-forming compounds are contained in the same layer as the photosensitive silver halide emulsion, a phenomenon of suppressing the development of silver halide may be observed, and the cause is probably due to the nitro group. It is estimated.

JP-A-53-66227 describes a cyanazo dye image-forming compound having a trifluoromethanesulfonyl group at the para position of the azo group. However, in addition to the synthetic and pollution problems that the compound contains fluorine, further improvement is desired in terms of sharpness of hue and diffusibility of released dye. British Patent 1,490,248 and JP-A-55-40402
JP-A No. 1989-242 discloses a magenta azo dye image-forming compound using a diazo component having a plurality of alkylsulfonyl groups, and these all have an unsubstituted or electron-withdrawing group at the 2-position of naphthol. Both of them have too short a hue and cannot be used as a cyan dye image forming compound.

That is, a nitro group at the para position of the azo group, or
Nothing was known other than cyan dye image-forming compounds with a trifluoromethanesulfonyl group.

Recently, a novel cyanazo image forming compound obtained by azo coupling of a diazo component having no nitro group or trifluoromethanesulfonyl group with 2-acylamino-1-naphthols has been disclosed in JP-A-60-93434. Kaisho 60
-87134, 60-257579. The image-forming compounds described in these documents are useful as cyan dyes as compared with conventional compounds, but they have a light hue and poor color reproducibility. In addition, since the hue is light, an image forming compound has to be additionally used in order to obtain a good gray balance.

(Object of the Invention) The first object of the present invention is to provide an image forming compound which gives a beautiful dye having a hue of cyan. The second object is to provide a compound which forms an image having excellent light fastness. Third, to provide an image-forming compound that does not inhibit the development of silver halide. Fourth, to provide a stable image-forming compound during storage and during development processing.
Fifth, it is to provide a color light-sensitive material having excellent light fastness and forming a cyan image having an excellent hue.

(Means for Solving Problems) As a result of various studies, the present inventors have made a color having at least one photosensitive silver salt layer containing an image forming compound represented by the following general formula (I) on a support. The light-sensitive material effectively achieves the above-mentioned objects, overcomes the drawbacks of the prior art,
It has been found to give fully satisfactory photographic performance.

(Dye-X) qY (I) Dye represents a cyan dye group or a dye precursor group represented by the following formula (II), X represents a simple bond or a linking group, and Y represents a photosensitive image having a latent image. Dye is released in response to or against the reversible silver salt.
ye-X) qY represents a group having the property of causing a difference in diffusivity from the compound represented by Dy,
e and X are bonded by A or E in the formula (II).

q is 1 or 2, and when q is 2, Dye-X may be the same or different.

A is a mere bond, a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic residue, or (A ² and A ³ are the same as those represented by A.
Further, A ² and A ³ may combine with each other to form a heterocycle. ) Is represented.

R ¹ represents a hydrogen atom, an alkyl group, or a substituted alkyl group.

B is a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic residue, a substituted or unsubstituted amino group, a substituted or unsubstituted alkyl or aryl It represents an oxy group, a substituted or unsubstituted alkyl or alurthio group, an acylamino group, a sulfonylamino group, a hydroxyl group, a carboxyl group, or a substituted or unsubstituted carbamoyl group.

E is a bond, a hydrogen atom, an alkyl group, a substituted alkyl group, a halogen atom, -OR ⁴ , (R ⁴ and R ⁵ each represent a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, and R ⁴
And R ⁵ may form a 5- or 6-membered ring. ).

G represents a hydroxyl group or a salt thereof, and a group selected from the following (T) to (V).

However, R ²¹ and R ²² may be the same or different and each is a substituted or unsubstituted alkyl group, cycloalkyl group, alkenyl group, aralkyl group, aryl group, heterocyclic residue, alkyloxy group. Represents an aryloxy group, an alkylthio group, an arylthio group and an amino group. R ²¹ and R ²² may combine with each other to form a 5- or 6-membered ring.

When the substituents of A, B and E are further substituted, preferred examples of the substituents that are allowed are an alkyl group, an aryl group, a —OR ² group, a —SR ² group, a —SO ₂ R ² group, There are disubstituted amino groups, acylamino groups, sulfonylamino groups, halogen atoms, cyano groups, sulfo groups, carboxyl groups, and alkyloxycarbonyl groups, where R ² and R ³ are each a hydrogen atom, an alkyl group, or an aryl group. Represents a group selected.

The dye portion of the image-forming compound (I) of the present invention (in the general formula (I
I)) has a structural feature that it has a cyano group at the 4-position and 5-position of the azo group (3-position and 4-position when both ortho-positions of the azo group are both hydrogen atoms), and the 2-position. It does not have an electron-withdrawing group such as a sulfonyl group or a cyano group. As a result, the hue was significantly lengthened.

Generally, in the azo dye, the resonance position of the azo group (the 2-position of the azo group,
It is known that introduction of an electron-withdrawing group at the 4th and 6th positions makes the hue longer.

However, in the compound of the present invention, an electron-withdrawing group (cyano group)
Is substituted at the 4-position and 5-position (or 3-position and 4-position) of the azo group, the electron-withdrawing group at the resonance position (2-position, 4-position and 6-position) of the azo group. It has been found that the hue is longer than that in the case where two or more positions are substituted, and the hue becomes longer as the electron donating property of the substituent at the 2-position of the azo group increases.

This result is a new finding that is not disclosed or suggested in the above-mentioned publicly known materials, and is an unexpected fact.

Furthermore, JP-A-60-9343, Japanese Patent Application Nos. 60-87134 and 60-2575.
It was also found that the light fastness was as good as the cyanazo dye disclosed in No. 79.

The image forming compound represented by formula (I) of the present invention is described in detail below.

The linking group represented by X is a -NR ⁶ -group (R ⁶ represents a hydrogen atom, an alkyl group or a substituted alkyl group), -SO _2-
Group, -CO- group, alkylene group, substituted alkylene group, phenylene group, substituted phenylene group, naphthylene group, substituted naphthylene group, -O- group, -SO- group and groups formed by combining two or more of these . Preferred among linking groups _{^{-NR 6 -SO 2 -, - NR}} 6 -CO- or _{^{R 7 - (L) k -}} (R 8) l - is a group represented by, R ⁷ and R ⁸ are each alkylene group, substituted alkylene group, a phenylene group, substituted phenylene group, a naphthylene group, a substituted naphthylene group, L is -O -, - CO -, - SO -, - SO 2 -, - SO 2 NH -, - NHSO
_{2 -, - CONH -, -} NHCO- represent, k represents 0 or 1, l represents 1 when k = 1, represents 1 or 0 when k = 0.

Also -NR ⁶ -SO ₂ - or -NR ⁶ -CO- and _{^{-R 7 - (L) k -}} (R 8) l -
A combination of and is also preferable.

Preferred examples of R ⁶ include a hydrogen atom, a lower alkyl group having 1 to 4 carbon atoms, and a substituted alkyl group having 1 to 4 carbon atoms (the substituent includes a halogen atom, a hydroxyl group, an alkoxy group, a cyano group and the like). In particular, hydrogen atom is excellent. Preferable examples of R ⁷ and R ⁸ include an alkylene group having 1 to 6 carbon atoms and a substituted alkylene group having 1 to 8 carbon atoms (as a substituent, an alkyl group, an alkoxy group, a hydroxyl group, a halogen atom, a cyano group and the like can be mentioned. ), A phenylene group (including ortho, meta, and para), a substituted phenylene group having 6 to 10 carbon atoms (as a substituent, an alkyl group, an alkoxy group, a substituted alkoxy group, a halogen atom, a substituted alkyl group, a hydroxyl group, a carboxyl group) , Sulfamoyl group, substituted sulfamoyl group, alkylsulfonylamino group, sulfamide group, substituted sulfamide group, disubstituted amino group, etc.), naphthylene group, substituted naphthylene group having 10 to 14 carbon atoms (substituted phenylene as a substituent) Group substituents can be mentioned).

The alkyl group represented by A is preferably a linear or branched alkyl group having 1 to 8 carbon atoms, specifically, methyl group, ethyl group, n-propyl group, t-butyl group, n-butyl group, 2 -Ethylhexyl group, 2,2-dimethylpropyl group, se
Examples thereof include c-butyl group. The cycloalkyl group is preferably a 5- to 6-membered cycloalkyl group having 5 to 8 carbon atoms, and specific examples thereof include a cyclopentyl group and a cyclohexyl group.

As a preferable substituent of the substituted alkyl group or the substituted cycloalkyl group, a halogen atom (preferably Cl, Br
Etc.), an —OR ² group [R ² has the same meaning as described above. For example, an alkyl group having 1 to 8 carbon atoms (eg, methyl group, ethyl group, methoxyethyl group, ethoxymethyl group, trichloromethyl group, cyanomethyl group, methanesulfonylaminomethyl group, sulfamoylmethyl group, etc.), carbon number 6 ~Ten
An aryl group (for example, a phenyl group, a tolyl group, a methoxyphenyl group, a chlorophenyl group, a cyanophenyl group, a methanesulfonylaminophenyl group, etc.)], a cyano group, (Preferably R ² is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 10 carbon atoms, and R ³ is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or 6 to 10 carbon atoms.
Aryl group), -SO ₂ R ² group (preferably an alkyl group having 1 to 8 carbon atoms or an aryl group having 6 to 10 carbon atoms as R ² ), a carboxy group, a sulfo group, an acylamino group (preferably having 2 carbon atoms). ~ 8), a sulfonylamino group (preferably having a carbon number of 1 to 8) and the like.

The aryl group represented by A is preferably an aryl group having 6 to 10 carbon atoms, and specific examples thereof include a phenyl group and a naphthyl group. The preferred substituent of the substituted aryl group is substituted or unsubstituted, preferably having 1 to 1 carbon atoms.
8 alkyl group; -OR ² group (preferably R ² is an alkyl group having 1 to 8 carbon atoms in total, or a substituted alkyl group (preferably as a substituent, an alkoxy group having 1 to 5 carbon atoms, a halogen atom (Cl , Br etc.) cyano group, etc.); halogen atom;
Acylamino group (preferably having 2 to 8 carbon atoms); Sulfonylamino group (preferably having 1 to 8 carbon atoms); Cyano group;
₂ R ² group (preferably C 1-8 alkyl group as R ² ); hydroxyl group; (R ² and / or R ³ is preferably a hydrogen atom or an alkyl group having 1 to 8 carbon atoms); (R ² and / or R ³ is preferably a group selected from a hydrogen atom and an alkyl group having 1 to 8 carbon atoms); a carboxy group; a sulfo group; an alkyloxycarbonyl group (preferably having 1 to 8 carbon atoms) A disubstituted amino group having 2 to 8 carbon atoms and the like.

The heterocyclic residue represented by A is preferably a 5- or 6-membered heterocyclic ring containing oxygen, nitrogen or sulfur as a hetero atom, and examples thereof include a pyridyl group, a furyl group, a thienyl group, a pyrrole group and an indolyl group. Is mentioned. Further, this heterocyclic residue may have a substituent shown as an example of the substituent of the above-mentioned substituted aryl group.

Represented by A A ² and / or A ³ is preferably a hydrogen atom, an alkyl group having 1 to 8 carbon atoms or an aryl group having 6 to 10 carbon atoms, and particularly preferably, both A ² and A ³ are alkyl groups. Is the case. The ring formed by connecting A ² and A ³ is preferably a 6-membered ring.

Specific examples thereof include a diethylamino group, an anilino group, a piperidino group, and a morpholino group.

When E is bonded to X, particularly preferable substituents among the substituents represented by A are ethyl group, isopropyl group, t-butyl group, cyclohexyl group, 3-heptyl group, methoxyethyl group, phenyl group. Group, p-methylsulfonylphenyl group, p-methylsulfonylaminophenyl group, p-sulfamoylphenyl group, and the like.

Preferred examples of R ¹ include a hydrogen atom, a lower alkyl group having 1 to 4 carbon atoms, and a substituted alkyl group having 1 to 4 carbon atoms (such as a substituent include a halogen atom, a hydroxyl group, an alkoxy group and a cyano group). The hydrogen atom is particularly preferable.

The halogen atom represented by B is preferably F or C.
l, Br and the like.

The alkyl group represented by B is preferably a lower alkyl group having 1 to 4 carbon atoms (for example, a methyl group, an ethyl group, an isopropyl group, etc.), a substituted lower alkyl group {as a substituent, preferably a halogen atom (preferably Is Cl, Br
Etc.), an —OR ² group (preferably R ² is an alkyl group having 1 to 6 carbon atoms), a cyano group, an —SO ₂ R ² group (preferably R ² is an alkyl group having 1 to 6 carbon atoms, an acylamino group ( Preferably 2 to 6 carbon atoms, a sulfonylamino group having 1 to 6 carbon atoms, (R ² and / or R ³ is preferably a hydrogen atom,
An alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 10 carbon atoms), (As R ² and / or R ³ , preferably hydrogen, an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 10 carbon atoms)
And the like}.

The aryl group represented by B is preferably a phenyl group or a naphthyl group, which may be substituted. The substituent is preferably an unsubstituted or substituted alkyl group having 1 to 6 carbon atoms (the substituent includes the same as those described above for the substituted lower alkyl group),
OR ² group {R ² is preferably an unsubstituted or substituted alkyl group having 1 to 6 carbon atoms, and the substituent of the substituted alkyl group is preferably an alkoxy group having 1 to 4 carbon atoms, a halogen atom (Cl , Br, etc.), a cyano group, a —SO ₂ R ² group (R ² is an alkyl group having 1 to 4 carbon atoms), a disubstituted amino group having 2 to 6 carbon atoms, and the like. }, A halogen atom (preferably,
Cl, Br, etc., an acylamino group (preferably having a carbon number of 2 to 2)
4), a sulfonylamino group (preferably having a carbon number of 1 to
4), a cyano group, -SO ₂ R ² (R ² is preferably an alkyl group having 1 to 4 carbon atoms), (R ² and / or R ³ is preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms), (R ² and / or R ³ are preferably hydrogen atom and carbon number 1
~ 4 alkyl group), preferably a 2-substituted amino group substituted by each alkyl group having 1 to 4 carbon atoms, a carboxy group, a sulfo group, an alkyloxycarbonyl group (preferably having 1 to 4 carbon atoms) and the like. .

The heterocyclic residue represented by B is preferably a 5- or 6-membered heterocyclic ring containing oxygen, nitrogen or sulfur as a hetero atom, and examples thereof include a pyridyl group, a furyl group, a thienyl group, a pyrrole group and an indolyl group. Groups and the like. Further, this heterocyclic residue may have a substituent shown as an example of the substituent of the above-mentioned substituted aryl group.

The alkyl or aryloxy group represented by B and the alkyl or arylthio group are preferably represented by the following (P) and (Q).

—OR ¹³ (P) —SR ¹⁴ (Q) Preferable examples of R ¹³ and R ¹⁴ are the same as the examples of the substituted or unsubstituted alkyl group and the substituted or unsubstituted aryl group, which are also mentioned above in the section B. The following are listed.

The substituted or unsubstituted amino group represented by B is R ¹⁵ and / or R ¹⁶ is preferably a hydrogen atom, an unsubstituted alkyl group having 1 to 4 carbon atoms or a substituted alkyl group thereof, an unsubstituted aryl group having 6 to 10 carbon atoms or a substituted aryl thereof. R ¹⁵ and R ¹⁶ may be connected to each other to form a ring. Examples of preferred substituents of the substituted alkyl group include a halogen atom (Cl, Br, etc.), a cyano group, an alkoxy group having 1 to 4 carbon atoms, and the like.
Preferred substituents of the substituted aryl group include a halogen atom (Cl, Br, etc.), a cyano group, an alkoxy group having 1 to 4 carbon atoms, and a —SO ₂ R ⁴ group (wherein R ⁴ is alkyl having 1 to 4 carbon atoms). Group), a disubstituted amino group having a total of 2 to 6 carbon atoms, and the like. Preferred examples of the substituted or unsubstituted amino group include a methylamino group, a diethylamino group, an anilino group, a monofolino group and the like.

The substituted or unsubstituted carbamoyl group represented by B is R ¹⁷ and / or R ¹⁸ is preferably selected from a hydrogen atom, an alkyl group having 1 to 6 carbon atoms and an aryl group having 6 to 10 carbon atoms, and specific examples thereof include an ethylcarbamoyl group and dimethylcarbamoyl group. Group and anilinocarbonyl group.

The acylamino group represented by B preferably has 2 to 10 carbon atoms, and examples thereof include an acetylamino group, a propionylamino group, an isobutyrylamino group and a benzoylamino group. The acyloxy group represented by B preferably has 2 to 6 carbon atoms, and examples thereof include an acetyloxy group and a propionyloxy group. Examples of the sulfonylamino group represented by B include those having an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 10 carbon atoms, and examples thereof include a methanesulfonylamino group, an ethanesulfonylamino group and benzene. There are sulfonylamino groups and the like.

Among the substituents represented by B above, particularly preferred are
A hydrogen atom, a halogen atom (F, Cl, Br, etc.), a methylthio group, a methoxyethoxy group, an acetylamino group and the like.

The alkyl group represented by E preferably has 1 to 8 carbon atoms, and examples thereof include a methyl group, an ethyl group and an isopropyl group. Preferred substituents of the substituted alkyl group include a halogen atom (Cl, Br, etc.), a cyano group,
An alkoxy group having 1 to 5 carbon atoms, a sulfonylamino group, an acylamino group, a carbamoyl group, a sulfamoyl group,-
Examples include SO ₂ R ² groups (R ² is an alkyl group having 1 to 8 carbon atoms), disubstituted amino groups having 2 to 6 carbon atoms, and the like.

The halogen atom represented by E is preferably C
l, Br and the like.

Preferred substituents for R ⁴ of —OR ⁴ represented by E are unsubstituted or substituted alkyl groups having 1 to 8 carbon atoms and 6 to 10 carbon atoms.
Examples of the unsubstituted or substituted aryl group include, and the substituent of the substituted alkyl group is preferably the same as those mentioned above as the substituent in the section of the substituted alkyl group. The substituent of the substituted aryl group is preferably an alkyl group having 1 to 8 carbon atoms, a halogen atom (Cl, Br, etc.), a cyano group, a substituted or unsubstituted alkoxy group having 1 to 5 carbon atoms, A sulfonylamino group, an acylamino group, a substituted or unsubstituted carbamoyl group, a substituted or unsubstituted sulfamoyl group, -SO ₂ R ² group (R ² is a C1-8 alkyl group), a C2-6 A disubstituted amino group etc. are mentioned.

Represented by E R ⁴ and / or R ⁵ is preferably a hydrogen atom, an unsubstituted alkyl group having 1 to 8 carbon atoms or a substituted alkyl group thereof, an unsubstituted aryl group having 6 to 10 carbon atoms or a substituted aryl group thereof, As the substituent of the substituted alkyl group, preferably, the same substituents as those mentioned above as the substituent in the section of the substituted alkyl group can be mentioned. Further, as the substituent of the substituted aryl group, preferably -OR ⁴
The same substituents as those mentioned above in the section of the substituted aryl group can be mentioned.

Represented by E R ⁴ and / or R ⁵ is preferably a hydrogen atom, an unsubstituted alkyl group having 1 to 8 carbon atoms or a substituted alkyl group thereof, an unsubstituted aryl group having 6 to 10 carbon atoms or a substituted aryl group thereof, Examples of preferable substituents of the substituted alkyl group include the same substituents as those mentioned above in the paragraph of the substituted alkyl group. Preferred examples of the substituent of the substituted aryl group include the same substituents as those mentioned above in the paragraph of the substituted aryl group of —OR ⁴ . Similarly, R ⁴ and / or R ⁵ is preferably a hydrogen atom,
An unsubstituted alkyl group having 1 to 8 carbon atoms or a substituted alkyl group thereof, an unsubstituted aryl group having 6 to 10 carbon atoms or a substituted aryl group thereof, and a preferable substituent of the substituted alkyl group is a substituted alkyl group previously. The same substituents as those mentioned in the section (1) can be mentioned, and the preferable substituents of the substituted aryl group include the same substituents as those mentioned above in the section of the substituted aryl group. Similarly, R ⁴ and / or R ⁵ is preferably a hydrogen atom,
An unsubstituted alkyl group having 1 to 8 carbon atoms or a substituted alkyl group thereof, an unsubstituted aryl group having 6 to 10 carbon atoms or a substituted aryl group thereof, wherein the substituent of the substituted alkyl group is
Preferred examples thereof include the same groups as those mentioned above as the substituent in the substituted alkyl group, and the substituent of the substituted aryl group is preferably the above-mentioned substituted aryl group in -OR ⁴ The same as those listed as the group can be mentioned.

When A is bonded to X, -NHCOCH ₃ group is particularly preferable as a substituent among the substituents represented by E above.
-NHSO ₂ CH ₃ group, -NHCOC ₃ H ₇ group, -NHSO ₂ C ₂ H ₅ group, Etc.

G is a hydroxyl group or a salt thereof, such as an alcar metal salt (eg,
For example-O Li , -O K Etc.) and photographically inactive
Ammonium salts (eg -O NH_Four , -O N (C
_TwoH₅)_Four Etc.) and from the following (T) to (V)
Represents a selected group.

The alkyl group represented by R ²¹ and R ²² is preferably a linear or branched alkyl group having 1 to 18 carbon atoms, specifically, methyl group, ethyl group, n-propyl group, n-butyl group,
n-hexyl group, n-heptyl group, 2-ethylhexyl group, n-
Examples thereof include a decyl group and an n-dodecyl group. The cycloalkyl group is a monocyclic or polycyclic 5-5 carbon atom.
To 6-membered cycloalkyl groups are preferred, and specifically,
Examples include cyclopentyl group and cyclohexyl group. As the substituent of the substituted alkyl group or the cycloalkyl group,
Halogen atom, alkoxy group (preferably having 1 to 1 carbon atoms)
8), an aryloxy group (preferably having 6 to 18 carbon atoms),
Cyano group, alkylthio group (preferably having 1 to 1 carbon atoms)
8), arylthio groups (preferably 6 to 18), unsubstituted or preferably disubstituted carbamoyl groups having 2 to 18 carbon atoms, alkylsulfonyl groups (preferably 1 to 1 carbon atoms).
8), an arylsulfonyl group (preferably having 6 to 1 carbon atoms)
8), preferably a disubstituted amino group substituted by an alkyl group having 1 to 18 carbon atoms or an aryl group having 6 to 18 carbon atoms, a carboxy group, a sulfo group, preferably an acylamino group having 1 to 18 carbon atoms, and a sulfonyl group An amino group etc. are mentioned.

Examples of the alkenyl group include vinyl group, allyl group, crotyl group, styryl group and the like.

Examples of the aralkyl group include a benzyl group and a β-phenethyl group.

The aralkyl group may have the substituent shown as an example of the substituent of the substituted alkyl group.

The aryl group is preferably an aryl group having 6 to 18 carbon atoms, and specific examples thereof include a phenyl group, a naphthyl group and an anthryl group. Substituents permissible for these include a substituted or unsubstituted alkyl group (preferably having 1 to 18 carbon atoms), a substituted or unsubstituted alkoxy group (preferably having 1 to 18 carbon atoms), a substituted or unsubstituted aryl group. A group (preferably having 6 to 18 carbon atoms), a halogen atom, an acylamino group (preferably having 1 to 18 carbon atoms), a sulfonylamino group,
Cyano group, nitro group, alkylthio group (preferably having 1 to 18 carbon atoms), arylthio group (preferably having 6 to 1 carbon atoms)
8), an alkylsulfonyl group (preferably having 1 to 1 carbon atoms)
8), an arylsulfonyl group (preferably having 6 to 1 carbon atoms)
8), a carbamoyl group, a substituted (mono-substituted or di-substituted carbon number is preferably 2 to 18) carbamoyl group, a sulfamoyl group, a substituted (mono-substituted or di-substituted carbon number is preferably 1-18) Sulfamoyl group, preferably a disubstituted amino group substituted with an alkyl group having 1 to 18 carbon atoms or an aryl group having 6 to 18 carbon atoms, a carboxy group,
Examples thereof include a sulfo group, an alkyloxycarbonyl group (preferably an alkyl moiety having 1 to 18 carbon atoms), an aryloxycarbonyl group (preferably an aryl moiety having 6 to 18 carbon atoms), and the like.

The heterocyclic residue is preferably a 5- or 6-membered heterocycle containing oxygen, nitrogen, or sulfur as a hetero atom, and examples thereof include a pyridyl group, a furyl group, a thienyl group, a pyrrole group,
Examples include indolyl groups. Further, this heterocyclic residue may have a substituent shown as an example of the substituent of the above-mentioned substituted aryl group.

Preferred examples of the substituted or unsubstituted alkyl group, aryloxy group, alkylthio group or arylthio group are represented by the following (W) and (Z).

—OR ²³ (W) —SR ²⁴ (Z) Preferable examples of R ²³ and R ²⁴ include a substituted or unsubstituted alkyl group and a substituted or unsubstituted aryl group mentioned above in the section of R ²¹ and R ²² . The same as the example is given.

Preferable examples of the substituted amino group include those substituted with an alkyl group having 1 to 18 carbon atoms and an aryl group having 6 to 18 carbon atoms.

The more preferred compound of the present invention is the case where R ¹ is a hydrogen atom and G is a hydroxyl group in the general formula (II). More preferably, it is represented by the following general formula (IA) or (IB).

Where M is -SO ₂ -or The expressed, X ² is _{^{-R 7 - (L) k -}} (R) 8 l - (R 7, L, K, R
⁸ and l represent the same as described above). i and j each represent 0 or 1. A, B and Y have the same meanings as those in formulas (I) and (II).

Next, Y will be described in detail, but the present invention is not limited to this.

Y is first selected such that the compounds of the invention are non-diffusible imaging compounds which, as a result of development processing, oxidize and self-cleave to give a diffusible dye.

An example of Y useful for this type of compound is an N-substituted sulfamoyl group. Examples of Y include groups represented by the following formula (YI).

In the formula, β represents a nonmetallic atom group necessary for forming a benzene ring, and a carbon ring or a heterocycle is condensed with this benzene ring to form, for example, a naphthalene ring, a quinoline ring, 5,6,7,8-
You may form a tetrahydronaphthalene ring, a chroman ring, etc.

α represents a group represented by -OG ¹¹ or -NHG ¹² . Here, G ¹¹ represents a hydrogen atom or a group which is hydrolyzed to form a hydroxyl group, and G ¹² represents a hydrogen atom, an alkyl group having 1 to 22 carbon atoms, or a group capable of hydrolyzing —NHG ¹² . Ball represents a ballast base. b is 0, 1 or 2.

Specific examples of Y of this kind are disclosed in JP-A-48-33826 and JP-A-48-33826.
No. 53-50736.

As another example of Y suitable for this type of compound, the following formula (YI
Examples thereof include groups represented by I).

In the formula, Ball, α, and b have the same meaning as in formula (YI), and β ′
Represents an atomic group necessary to form a carbon ring, for example, a benzene ring, and a carbon ring or a heterocycle is further condensed with the benzene ring to form a naphthalene ring, a quinoline ring, or a 5,6,7,8-tetrahydronaphthalene ring. , A chroman ring and the like may be formed.

Specific examples of Y of this kind are disclosed in JP-A-51-113624 and JP-A-56-113624.
12642, 56-16130, 56-16131, 57-4043,
57-650 and U.S. Pat. No. 4,053,312.

Still another example of Y suitable for this type of compound is a group represented by the following formula (YIII).

In the formula, Ball, α, and b have the same meanings as in formula (YI) and β ″
Represents an atomic group necessary for forming a heterocycle such as a pyrazole ring and a pyridine ring, and a carbocycle or a heterocycle may be bonded to this heterocycle. Specific examples of Y of this kind are described in JP-A-51-104343.

Further, as Y which is effective for this type of compound, there is one represented by the formula (YIV).

In the formula, γ is preferably a hydrogen atom or an alkyl group having a substituent or an unsubstituted group, an aryl group or a heterocyclic group, or -CO-G ²¹ ; G ²¹ is -OG ²² ,
-SG ²² or The stands, (G ²² represents hydrogen, an alkyl group, a cycloalkyl group or an aryl group, G ²³ represents the same group as the G ²² group, or G ²³ is electrically from aliphatic or aromatic carboxylic or sulfonic acid Represents an acyl group represented by
²⁴ represents hydrogen or an unsubstituted or substituted alkyl group); δ represents a residue necessary to complete a fused benzene ring.

Specific examples of Y of this kind are disclosed in JP-A-51-104343 and JP-A-53-104343.
46730, JP-A-54-130122 and JP-A-57-85055.

Further suitable as Y for this type of compound of the invention is the formula (Y
Examples thereof include groups represented by V).

In the formula, Ball has the same meaning as in formula (YI), ε is an oxygen atom or = NG ³² group (G ³² represents a hydroxyl group or an amino group which may have a substituent), Examples of the compound H ₂ N-G ³² include hydroxylamines, hydrazines, semicarbazides, thiosemicarbazides and the like, and β in the formula is a 5-membered, 6-membered or 7-membered saturated or unsaturated ring. It is a group of atoms necessary for forming a non-aromatic hydrocarbon ring.

G ³¹ represents a hydrogen atom or a halogen atom such as fluorine, chlorine or bromine. As a specific example of this kind of Y, Japanese Patent Laid-Open No. 53918/1983
No. 54-48534.

Other examples of Y of the compound of the present invention of this type include, for example, JP-B-48-32129, JP-A-48-39165, JP-A-49-64436,
Examples thereof include those described in US Pat. No. 3,443,934 and the like.

Further, Y in the present invention includes a group represented by the formula (YVI).

In the formula, A ⁴¹ represents an atomic group necessary for forming an aromatic ring, Ball is an organic immobilizing group present on the aromatic ring, and Balls may be the same or different and m is an integer of 1 or 2. is there.

X is a divalent organic group having 1 to 8 atoms, and the nucleophilic group (Nu) and the electrophilic center (carbon atom of *) generated by oxidation form a 5 to 12-membered ring. Nu represents a nucleophilic group. n is an integer of 1 or 2. α has the same meaning as in the case of the above formula (YI). A specific example of Y of this type is disclosed in JP-A-57-207.
There is a description in No. 35.

Further, as another type of compound of the present invention, a diffusible dye is released by self-ring closure in the presence of a base.
There are non-diffusible imaging compounds which, when reacted with oxidized developer, cause substantially no dye release.

Examples of Y effective in this type of the compound of the present invention include those shown in formula (YVII).

In the formula, α ′ is an oxidizable nucleophilic group such as a hydroxyl group, a primary or secondary amino group, a hydroxyamino group, a sulfonamide group or a precursor thereof,
α ″ is a dialkylamino group or any of the groups defined in α ′, G ⁵¹ is an alkylene group having 1 to 3 carbon atoms, a represents 0 or 1, and G ⁵² represents 1 carbon atom. A substituted or unsubstituted alkyl group containing up to 40,
Or a substituted or unsubstituted aryl group containing 6 to 40 carbon atoms, G ⁵³ is an electrophilic group such as —CO—, —CS—, G ⁵⁴ is an oxygen atom, a sulfur atom, a selenium atom, It is a nitrogen atom or the like, and when it is a nitrogen atom, it may be substituted with a hydrogen atom, an alkyl group or a substituted alkyl group containing 1 to 10 carbon atoms, or an aromatic residue containing 6 to 20 carbon atoms.

G ⁵⁵ , G ⁵⁶ , and G ⁵⁷ are each a hydrogen atom, a halogen atom,
A carbonyl group, a sulfamyl group, a sulfonamide group, an alkyloxy group having 1 to 40 carbon atoms or the same meaning as G ^52, and G ⁵⁵ and G ⁵⁶ together may form a 5- to 7-membered ring. .

Also, G ⁵⁶ May be However, at least one of G ⁵² , G ⁵⁵ , G ⁵⁶ and G ⁵⁷ represents a ballast group. Specific examples of Y of this kind are described in JP-A-51-63618.

Further suitable as Y for this type of compounds of the invention is the formula (YV
III) and (YIX).

Nu ⁶¹ and Nu ^{62, which} may be the same or different, represent a nucleophilic group or its precursor, Z ⁶¹ is R ⁶⁴ and
R ⁶⁵ represents a divalent atomic group which is electronegative with respect to the substituted carbon atom, and each of R ⁶¹ , R ⁶² and R ⁶³ is hydrogen, halogen, an alkyl group, an alkoxy group or an acylamino group, or R ⁶¹ And R ⁶² form a fused ring with the rest of the molecule when they are in adjacent positions on the ring, or R ⁶² and R
⁶³ forms a condensed ring with the rest of the molecule, and each of R ⁶⁴ and R ⁶⁵ may be the same or different, hydrogen, a hydrocarbon group,
Or represents a substituted hydrocarbon group, the substituents R ⁶¹ , R ⁶² ,
A ballast group (Ball) of sufficient size is present in at least one of R ⁶³ , R ⁶⁴ or R ⁶⁵ to render the compound immobile. A specific example of Y of this kind is disclosed in JP-A-53-69033.
No. 54-130927.

Further suitable Y for this type of compound of the invention is a group of formula (YX).

Where Ball and β ′ are the same as those in equation (YII), and G
⁷¹ represents an alkyl group (including a substituted alkyl group). Specific examples of Y of this type are described in JP-A-49-111628 and JP-A-52-4819.

Another type of compound of the compounds of the present invention includes non-diffusible imaging compounds that do not themselves release a dye, but do release a dye when reacted with a reducing agent. In this case, it is preferable to use a compound that mediates the redox reaction (so-called electron donor) in combination.

Examples of Y effective for the compound of the present invention of this type include a group represented by the formula (YXI).

Where Ball and β ′ are the same as those in equation (YII), and G
⁷¹ is an alkyl group (including a substituted alkyl group). Specific examples of Y of this type are described in JP-A Nos. 53-35533 and 53-1.
It is described in No. 1082.

Further suitable as Y for this type of compound of the invention is (YXI
There is a group represented by I).

(However, α ′ _ox and α ″ _ox are groups that give α ′ or α ″ respectively by reduction, and α ′, α ″, G ⁵¹ , G
⁵² , G ⁵³ , G ⁵⁴ , G ⁵⁵ , G ⁵⁶ , G ⁵⁷ and a have the same meanings as in formula (YVII). ) Specific examples of Y are described in JP-A-53-110827, US4356249 and US4358525.

Suitable Y for this type of compound of the present invention further includes those represented by formulas (YXIIIA) and YXIIIB).

(However, (Nu ox) ¹ and (Nu ox) ² may be the same or different and each represents an oxidized nucleophilic group, and other symbols have the same meanings as in formulas (YVIII) and (YIX). The specific examples of Y of this type are described in JP-A-54-13092.
7 and 56-164342.

Further suitable Y for this type of compound is the group represented by (YXIV).

In the formula, EAG represents a group that receives an electron from a reducing substance. N and O represent a nitrogen atom and an oxygen atom, respectively, and this single bond is cleaved after EAG receives an electron.

D ¹ and D ² each represent a mere bond or a substituent other than a hydrogen atom. When D ¹ or D ² is bound to Time _t , D ¹ or D ² may be a mere bond. D ¹ and D ² may combine with each other to form a ring.

Time represents a group that releases the dye through a subsequent reaction using the cleavage of the nitrogen-oxygen single bond in the formula as a scratch.

t represents an integer of 0 or 1.

Further, in the formula, the solid line indicates the connection, and the broken line indicates that at least one of them is connected.

A specific example of Y is described in Japanese Patent Application No. 60-244873.

The patent specifications listed in YXI, YXII, YXIIIA, YXIIIB, and YXIV describe electron donors used in combination.

Yet another type of compound of the invention is LDA
Compounds (Linked Donor Acceptor Compounds) are listed. This compound is a non-diffusible image-forming compound that causes a donor-acceptor reaction in the presence of a base to release a diffusible dye, but does not substantially cause dye release when reacted with an oxidized product of a developing agent.

Examples of Y effective for this type of the compound of the present invention include those represented by the formula (YXV). A specific example of this Y is described in Japanese Patent Application No. 58-60289.

In the formula, n, x, y, z are 1 or 2, m is an integer of 1 or more, Don is an electron donor or a group containing a precursor moiety thereof, L ₁ is Nup and -L _2- It is an organic group that connects El-Q and Don, Nup represents a precursor of a nucleophilic group, El is an electrophilic center, Q is a divalent group, Ba
ll represents a ballast group. L ₂ represents a linking group. M ¹ represents an arbitrary substituent.

Still another compound represented by formula (I) or (II) is an oxidized product of a general reducing agent used in a photographic system, which decomposes under basic conditions in the unexposed area to release a dye. It is a non-diffusible compound that is cross-oxidized by and does not substantially cause dye release. Examples of Y effective for this type of compound include those represented by the formula (YXVI). A specific example of this Y is Japanese Patent Application No. 61-89809.
No.

In the formula, D ³ and D ⁴ represent a hydrogen atom or a substituted or unsubstituted alkyl group, cycloalkyl group, alkenyl group, alkynyl group, aralkyl group, aryl group, or heterocyclic residue; D ₅ represents a substituted or unsubstituted group. Substituted alkyl group, cycloalkyl group, alkenyl group, alkynyl group, aralkyl group, aryl group, heterocyclic residue, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group,
Represents a sulfonyl group or a sulfamoyl group; D ⁶ and D ⁷ represent a hydrogen atom or a substituted or unsubstituted acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group; W ¹ represents an oxygen atom, a sulfur atom or an imino group ; (Ti
me) represents a timing group; t represents 0 or 1.

The ballast group in the general formulas (YI) to (YXIII) and (YXV) is an organic ballast group capable of making the compound of the present invention non-diffusible, and this is a hydrophobic group having 8 to 32 carbon atoms. It is preferably a group containing. Such an organic ballast group may be directly or linked to the compound of the present invention (for example, imino bond, ether bond, thioether bond, carbonamide bond, sulfonamide bond, ureido bond,
(Ester bond, carbamoyl bond, sulfamoyl bond, etc., alone or in combination).

Some specific examples of the ballast group will be described below. For example,
Alkyl group (eg, dodecyl group, octadecyl group, etc.), alkenyl group (eg, dodecenyl group, octadecenyl group, etc.), alkoxyalkyl group {eg, Japanese Patent Publication No. 39
-27563, such as 3- (octyloxy)
Propyl group, 3- (2-ethylundecyloxy) propyl group, etc., alkylaryl group {eg, 4-nonylphenyl group, 2,4-di-tert-butylphenyl group, etc.}, alkylaryloxyalkyl group { For example, 2,4-di-tert
-Pentylphenoxymethyl group, α- (2,4-di-tert-pentylphenoxy) propyl group, 1- (3-pentadecylphenoxy) ethyl group, etc.}, acylamidoalkyl group {eg US Pat. No. 3,337,344 and A group as described in 3,418,129, 2- (N-butylhexadecane amide)
Ethyl group, etc., alkoxyaryl and aryloxyaryl groups {eg, 4- (n-octadecyloxy) phenyl group, 4- (4-n-dodecylphenyloxy) phenyl group, etc., long alkyl or alkenyl chains A residue having an aliphatic group and a water-solubilizing group such as a carboxyl or sulfo group (eg, 1-carboxymethyl-2-nonanedecenyl group, 1-sulfoheptadecyl group, etc.), an alkyl group substituted with an ester group { For example, a 1-ethoxycarbonylheptadecyl group, a 2- (n-dodecyloxycarbonyl) ethyl group, etc.}, an alkyl group substituted with an aryl group or a heterocyclic group {eg, 2- [4- (3-methoxycarbonylun Eicosanamido) phenyl] ethyl group, 2- [4- (2-n-
Octadecylsuccinimide) phenyl] ethyl group,
Etc., and an aryl group substituted with an aryloxyalkoxycarbonyl group {eg, 4- [2- (2,4-di-tert
-Pentylphenyloxy) -2-methylpropyloxycarbonyl] phenyl group, etc.} and the like.

Among the above-mentioned organic ballast groups, particularly preferable ones are those bonded to a linking group represented by the following general formulas (B ₁ ) to (B ₄ ).

-CONH-R ⁸¹ -OR ⁸³ (B2) -OR ⁸⁴ (B3) -CONHR ⁸³ (B4) wherein R ⁸¹ is an alkylene group having 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms, For example, it represents a propylene group or a butylene group, R ⁸² represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms, such as a tert-amyl group, and n is an integer of 1 to 5 ( It preferably represents 1 or 2). R ⁸³ has 4 to 30 carbon atoms, preferably 1
It represents an alkyl group of 0 to 20, for example, dodecyl group, tetradecyl group, hexadecyl group and the like. R ⁸⁴ is an alkyl group having 8 to 30 carbon atoms, preferably 10 to 20 carbon atoms (eg, hexadecyl group, octadecyl group, etc.) or a substituted alkyl group having 8 or more carbon atoms (the alkyl residue has 1 or more carbon atoms. Is, for example, a carbamoyl group, etc.).

Next, specific examples of the compound of the present invention represented by the general formula (I) will be shown, but the invention is not limited thereto. In the formula, Ph represents a phenyl group.

The specific synthesis example is shown below.

Synthesis Example Synthesis of Compound (1) The compound (1) was synthesized by the following route.

Synthesis of Intermediate (a) 5- (3-Sulfophenylsulfonylamino) -1-naphtho-
A mixture of 209 g of potassium salt, 136 g of zinc chloride, 500 ml of ethanol and 100 ml of water is heated to 50 ° C with stirring, and a solution of 39 g of sodium nitrite in 100 ml of water is heated at 50 to 60 ° C.
It was dripped at. After heating at 60 ° C. for 3 hours, the mixture was allowed to cool to room temperature, the reddish brown crystals were filtered, washed with ethanol and dried.

Synthesis of Intermediate (b) A mixture of 11.6 g of the reddish brown crystals, 19 g of sodium hydrosulfite, 200 ml of water and 200 ml of acetonitrile was heated and stirred at 60 ° C. for 30 minutes under a nitrogen atmosphere. After cooling to 20 ° C, 3.3 g of propionyl chloride was added at 15-20 ° C. After stirring for 30 minutes, the mixture was heated at 60 ° C. for another 30 minutes. After adding 3.3 g of sodium hydrogen carbonate, 500 ml of saturated saline was added, and the mixture was stirred at 10 ° C. for 2 hours. The light brown crystals were filtered, washed with saturated brine and dried. Yield 7.5g.

Synthesis of Intermediate (c) First, the intermediate (c-4) was synthesized according to the above synthetic route.

Synthesis of intermediate (c-1) phthalimide 400g, concentrated sulfuric acid 2.8l, 94% nitric acid 474ml to Org
The intermediate (c-1) was synthesized and crystallized by the method described in anic Synthesis coll.vol.II p 459, and the target product was filtered and washed with water.

The crystals obtained here were not dried and used in the next step.

Synthesis of intermediate (c-2) While stirring a suspension of the intermediate (c-1) and acetonitrile 1 synthesized above, concentrated ammonia water 1
Was added and the reaction was allowed to proceed for 2 hours.

The precipitated crystals were filtered, washed with water and thoroughly dried. Yield: 341
g, yield: 60% (from phthalimide).

Synthesis of Intermediate (c-3) A suspension of N, N-dimethylformamide 1 containing 340 g of the intermediate (c-2) was stirred at 10 ° C. or lower, and 475 ml of phosphorus oxychloride was added dropwise thereto. . After the completion of dropping, the mixture was stirred at 10 ° C or lower for 1 hour and at room temperature for 3 hours. 6 l of this reaction liquid
It was poured into with stirring. After stirring at 10 ° C or lower for 1 hour, the precipitated crystals were filtered, washed with water and dried. Yield: 264g,
Yield: 94%.

Synthesis of intermediate (c-4) Reduced iron 300g, isopropanol 1, ammonium chloride
A suspension of 10 g and 200 ml of water was heated to reflux with stirring. To this, 260 g of the intermediate (c-3) was added in portions and reacted for 1 hour after the addition was completed. This was filtered through Celite while hot and washed with isopropyl alcohol 1. 6 l of this filtrate
Pour into water at 60 ℃ with stirring and stir for 30 minutes, then at 10 ℃
It was cooled to below and stirred for another hour. The precipitated crystals were filtered and washed with water. After thoroughly drying the crystals, ethyl acetate
Recrystallized from 500 ml. Yield: 113 g, yield: 53%.

Synthesis of Intermediate (d) First, the intermediate (c-4) to the intermediate (c) are prepared by the following method.
= 3,4-Dicyanoaniline diazonium salt was synthesized.
21.3 ml of concentrated sulfuric acid was stirred under ice cooling with sodium nitrite.
3.2 g was added. Next, the mixture was reacted at 70 ° C. for 30 minutes and then cooled on ice. To this, add 30 ml of acetic acid and 13 ml of propionic acid to the internal temperature.
It was added while keeping the temperature below 10 ° C. Next, the intermediate (c-4)
Gradually add 5.5g so that the internal temperature does not exceed 5 ℃.
The reaction was carried out for 3 hours below. To this, 1 g of sulfamic acid was added to decompose excess nitrous acid.

20.8 g of the intermediate (b), 142 ml of methyl cellosolve, 14 of water
The solution consisting of 2 ml was ice-cooled and stirred. The above diazo solution was gradually added to this so that the internal temperature was kept at 5 ° C or lower. After reacting at 5 ℃ or less for 1 hour, add to saturated saline solution 1 and 40 ～ 50 ℃
Heated for 1 hour. The precipitated crystals were filtered and washed with saturated saline. After sufficiently dried, it was used in the next step. Yield: 25.3g.

Synthesis of Intermediate (e) 25 g of Intermediate (d), 12 ml of N, N-dimethylacetamide
25 ml of phosphorus oxychloride was added dropwise to a suspension containing and 125 ml of acetonitrile while stirring. After reacting at 60 ° C. for 3 hours, the mixture was cooled to room temperature with water. 1000 ml of ice water
It was poured into and stirred at 10 ° C or lower for 1 hour. The precipitated crystals were filtered, washed with water and air dried. Yield: 16g.

Synthesis of Compound (1) 2-Amino-4-hexadecyloxy-5-t-octylphenol p-toluenesulfonate 22.4 g, N, N-dimethylacetamide 112 ml and α-picoline 13.8 ml are suspended in nitrogen. Keep at 5 ° C or lower while stirring under air flow. To this, 20 g of the intermediate (e) was added little by little. 2 more at 70 ° C for 1 hour
Stirring was continued for hours. To this, 160 ml of acetone and 146 ml of methanol were added, and 100 ml of water was added dropwise at 50 to 60 ° C. After 1 hour, water-cooling to room temperature resulted in precipitation of an oily substance.

Crystallization continued for a further 2 hours with stirring. The crystals were filtered and thoroughly washed with 200 ml of methanol. 30 ml of these crystals, 150 ml of ethanol, 50 ml of chloroform
It was dissolved by heating in the mixed solvent of, and filtered naturally with a paper filter. After cooling the filtrate to room temperature, 30 ml of acetic acid was added with stirring. After 3 hours, the precipitated crystals were filtered and acetonitrile 10
After washing with 0 ml, the crystals were recrystallized again from a mixed solvent of ethanol 400 ml, acetonitrile 100 ml, and n-hexane 500 ml.

Yield: 15g, Yield: 45%, Melting point: 216-7 ° C, Synthesis example-2 Synthesis of compound (50) Synthesis was carried out by the following route.

Synthesis of Intermediate (c-5) To a suspension of 28 g of the intermediate (c-4) and 300 ml of acetic acid, 10 ml of bromine was added dropwise at 10 ° C or lower while stirring. After reacting for 1 hour at the same temperature, 300 ml of water was added to the reaction mixture,
The precipitated crystals were filtered and washed with water. The crystals were thoroughly dried and then recrystallized from 100 ml of ethyl acetate.

Yield: 11 g, yield: 50%.

Synthesis of Intermediate () First, the intermediate (c-5) to the intermediate (f) are prepared by the following method.
= 2-Bromo-4,5-dicyanoaniline diazonium salt was synthesized. While stirring 60 ml of concentrated sulfuric acid under ice cooling, 9 g of sodium nitrite was added. Next, after reacting at 70 ° C for 30 minutes,
Chilled with ice. To this, 84 ml of acetic acid and 36 ml of propionic acid,
It was added while keeping the internal temperature below 10 ° C. Next, 24.2 g of the intermediate (c-5) was gradually added so that the internal temperature did not rise above 5 ° C., and the mixture was reacted at 5 ° C. or below for 3 hours. To this, 1 g of sulfamic acid was added to decompose excess nitrous acid.

45 g of the intermediate (b), 410 ml of methyl cellosolve, 410 m of water
The solution consisting of 1 was ice-cooled and stirred. The above diazo solution was gradually added to this so that the internal temperature was kept at 5 ° C or lower. After reacting for 1 hour at 5 ° C or below, add 3 liters of saturated saline to 1 at 40-50 ° C.
Heated for hours. The precipitated crystals were filtered and washed with saturated saline. After sufficiently dried, it was used in the next step. Yield: 100
g.

Synthesis of intermediate (p) 100 g of intermediate (o), 40 ml of N, N-dimethylacetamide
While stirring the suspension containing 500 ml of acetonitrile and 100 ml of acetonitrile, 100 ml of phosphorus oxychloride was added dropwise thereto. After reacting at 60 ° C. for 3 hours, the mixture was cooled to room temperature with water. The reaction solution was poured into 2 l of ice water and stirred at 10 ° C or lower for 1 hour. The precipitated crystals were filtered, washed with water and air dried. Yield: 28g.

Synthesis of compound (50) Synthesis of intermediate (h): Synthesis of 4-chloro-3-nitro-N-methyl-N-octadecylbenzenesulfonamide 100 g 4-chloro-3-nitrobenzenesulfonyl chloride in 300 ml chloroform Dissolved and cooled to 0 ° C. A chloroform solution of 84.3 g of methyl octadecylamine was added dropwise thereto. Then, add 39.5 g of triethylamine at 0 ° C to 1
The solution was added dropwise while keeping it at 0 ° C. After reacting for 1 hour after the completion of dropping, chloroform was distilled off, 500 ml of methanol was added and dissolved by heating, and crystals were precipitated by allowing to cool. The crystals were collected by vacuum filtration and dried. Yield: 109g, Yield: 71.2%, Melting point: 86-8
7 ° C.

Synthesis of Intermediate (i): Synthesis of 5-t-butyl-2- (4-N-methyl-N-octadecylsulfamoyl-2-nitrophenyl) -3-isoxazolone 4-chloro-3-nitro- 600 g of N-methyl-N-octadecylbenzenesulfonamide, 202 g of 5-t-butyl-3-hydroxyisoxazole (see Japanese Patent Application No. 60-244,873, page 75), 200 g of potassium carbonate and 1.8 l of dimethyl sulfoxide were mixed,
The reaction was carried out at 65 ° C for 6 hours. Then, the reaction solution was poured into ice water, and the precipitated crystals were filtered under reduced pressure, washed with water and then dried.
Yield: 709 g, yield: 98.0%, melting point: 68-69 ° C.

Synthesis of intermediate (j): Synthesis of 5-t-butyl-4-chloromethyl-2- (4-N-methyl-N-octadecylsulfamoyl-2-nitrophenyl) -3-isoxazolone 650 g of intermediate (i) (isoxazolone)
200 g of zinc chloride, 200 g of paraformaldehyde and 3 l of acetic acid were mixed, and the mixture was heated under reflux for 10 hours while sparging with hydrogen chloride gas. After cooling, the reaction solution was poured into water and the precipitated crystals were taken and recrystallized from acetonitrile: methanol = 1: 4. Yield: 579 g, yield: 82.4%, melting point: 55-56 ° C.

Synthesis of intermediate (k): 5-t-butyl-4- (4-acetylaminophenoxymethyl)
-2- (4-N-methyl-N-octadecylsulfamoyl-2-
Synthesis of (nitrophenyl) -3-isoxazolone 134 g of intermediate (j) (chloromethylisoxazolone) synthesized above, 34 g of potassium carbonate, 2 g of sodium iodide, 4
-32 g of acetylaminophenol and 800 ml of acetone were mixed and heated under reflux for 7 hours with vigorous stirring. After completion of the reaction, the reaction mixture was cooled and filtered under reduced pressure to remove inorganic substances, the solvent was distilled off under reduced pressure, and methanol was added to the residue to obtain crystals. Yield: 1
27.1 g, yield: 80.8%.

Synthesis of intermediate (l): 5-t-butyl-4- (4-aminophenoxymethyl) -2- (4-
Synthesis of N-methyl-N-octadecylsulfamoyl-2-nitrophenyl) -3-isoxazolone 500 g of the intermediate (k) (acetylaminophenoxymethylisoxazolone) synthesized above was added to 2 l of ethanol, 6N hydrochloric acid 1 was added and the mixture was heated under reflux for 8 hours. After cooling, it was neutralized with sodium hydrogen carbonate and extracted with ethyl acetate. The organic layer is concentrated and methanol: acetonitrile = 10: 1
More crystallized.

Yield: 445 g, yield 94.2%, melting point: 71-72 ° C.

Synthesis of Compound (50) 21 g of the intermediate (l) (amino compound) synthesized above was dissolved in 120 ml of dimethylacetamide, and 2.8 g of Py was added. Then, 20 g of the intermediate (p) was added. After reacting at room temperature for 2 hours, methanol was gradually added to precipitate crystals. Next, the same operation was repeated to crystallize from dimethylacetamide-methanol.

Yield: 28.0 g, yield: 69.7%, melting point: 108-112 ° C.

The amount of the dye image-forming compound used in the present invention can be varied within a wide range, but it is usually used in the range of 0.01 to 4 mol per mol of silver.

The above-mentioned image-forming compounds and hydrophobic additives such as image-forming accelerators described below can be incorporated into the layers of the light-sensitive element by known methods such as the method described in US Pat. No. 2,322,027. In this case, JP-A-59-83154 and 59-59
-178451, 59-178452, 59-178453, 59-1784
No. 54, No. 59-178455, No. 59-178457, and the like, a high-boiling organic solvent such as those described in, can be used in combination with a low-boiling organic solvent having a boiling point of 50 ° C. to 160 ° C., if necessary. .

The amount of high boiling organic solvent used is 1 g of the dye image-forming compound used.
On the other hand, it is 10 g or less, preferably 5 g or less.

Further, a dispersion method using a polymer described in JP-B-51-39853 and JP-A-51-59943 can also be used.

In the case of a compound which is substantially insoluble in water, fine particles can be dispersed and contained in a binder in addition to the above method.

When dispersing the hydrophobic substance in the hydrophilic colloid, various surfactants can be used. For example, JP-A-59-157
The surfactants listed on pages (37) to (38) of No. 636 can be used.

The dye image-forming compound of the present invention can be used in a light-sensitive element for a color diffusion transfer method which is developed with a processing solution at around room temperature, or can be used in a photothermographic element which is developed by heating. .

The silver halide that can be used in the above photosensitive element is silver chloride,
It may be any of silver bromide, silver chlorobromide, silver chloroiodide and silver chloroiodobromide.

Specifically, US Pat. No. 4,500,626, column 50, Research Disclosure, June 1978, pages 9 to 10 (RD17
029), Japanese Patent Application No. 59-228551, No. 60-225176, and No. 60-2282.
Any of the silver halide emulsions described in No. 67 etc. can be used.

The silver halide emulsion used in the present invention may be either a surface latent image type in which a latent image is mainly formed on the grain surface or an internal latent image type in which a latent image is formed inside the grain. It may be a so-called core-shell emulsion in which the inside of the grain and the surface layer of the grain have different phases. Further, in the present invention, a direct reversal emulsion in which an internal latent image type emulsion is combined with a nucleating agent and / or an optical fogging can be used.

The silver halide emulsion may be used as it is without ripening, but it is usually chemically sensitized before use. Well-known sulfur sensitizing methods, reduction sensitizing methods, noble metal sensitizing methods and the like can be used alone or in combination for the emulsions for conventional type light-sensitive materials. These chemical sensitizations can be carried out in the presence of a nitrogen-containing heterocyclic compound (JP-A Nos. 58-126526 and 58-215644).

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.

The silver halide used in the present invention may be spectrally sensitized with methine dyes and the like. The dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes and hemioxonol dyes.

Specifically, JP-A-59-180550 and JP-A-60-140335, Research Disclosure June 1978, pages 12 to 13 (RD
17029) and the like, and the heat-decolorizing sensitizing dyes described in JP-A-60-111239 and Japanese Patent Application No. 60-172967.

The light-sensitive material of the present invention can be used in combination with the compound of formula (I) in combination with a yellow or magenta image forming compound having a substrate Y having the same properties, or a known cyan dye image forming compound.

Examples of the dye image-forming compound that can be used in the present invention include couplers capable of reacting with a developing agent. The system utilizing this coupler is one in which an oxidized product of a developing agent generated by a redox reaction between a silver salt and a developing agent reacts with the coupler to form a dye, and it is described in many documents. The coupler may be a 4-equivalent coupler or a 2-equivalent coupler. Further, a 2-equivalent coupler having a diffusion resistant group as a leaving group and forming a diffusible dye by reaction with an oxidized product of a developing agent is also preferable. Specific examples of developing agents and couplers are described in "The Theory of the James" by James.
Photographic Process "4th Edition (THJames
"The Theory of the Photographic Process") 291-33
Page 4, and pages 354 to 361, JP-A-58-123533, 58-149.
046, 58-149047, 59-111148, 59-124399
No., 59-174835, 59-231539, 59-231540,
60-2950, 60-2951, 60-14242, 60-23474
No. 60-66249 and the like.

Further, a dye silver compound in which an organic silver salt and a dye are bound can also be mentioned as an example of the dye image forming compound. Specific examples of the dye silver compound are described in Research Disclosure, May 1978, pages 54 to 58 (RD-16966).

In addition, an azo dye used in the heat developable silver dye bleaching method can also be mentioned as an example of the dye image forming compound. Specific examples of azo dyes and bleaching methods are described in US Pat. No. 4,235,957, Research Disclosure, April 1976, 30-32.
Page (RD-14433) etc. In addition, US patent
The leuco dyes described in 3,985,565 and 4,022,617 can also be mentioned as examples of the dye-donor substance.

Further, as another example of the dye image forming compound, a compound having a function of releasing or diffusing the diffusible dye in an image form can be mentioned.

This type of compound can be represented by the following general formula [LI].

(Dye'-X ') _n -Y' [LI] Dye 'is represented by the general formula (II) or represents a known dye group, a temporarily shortened dye group or a dye precursor group, X'represents a simple bond or a linking group,
Y'corresponds to or corresponds to a photosensitive silver salt having an imagewise latent image, and causes a difference in diffusivity of the compound represented by (Dye'-X ') _n -Y', or Dye ' And (dye′-X ′) _n —Y ′ are released, and n is 1 or 2, and n is 1 or 2. Is 2, the two Dye'-X 'may be the same or different. Also, D
In the general formula (II), ye ′ and X ′ do not necessarily have to be bonded by A or E.

Specific examples of the dye-donating substance represented by the general formula [LI] include, for example, dye developers in which a hydroquinone-based developer and a dye component are linked to each other are disclosed in U.S. Patent Nos. 3,134,764 and 3,3.
62,819, 3,597,200, 3,544,545, 3,
No. 482,972, etc. Further, a substance which releases a diffusible dye by an intramolecular nucleophilic substitution reaction is disclosed in JP-A-51-6.
JP-A-49-11 discloses a substance that releases a diffusible dye by an intramolecular rewinding reaction of an isoxazolone ring in 3,618.
It is described in No. 1,628. In all of these methods, the diffusible dye is released or diffused in a portion where development has not occurred, and the dye is neither released nor diffused where development has occurred.

As another method, a dye-releasing compound is made into an oxidant type having no dye-releasing ability to coexist with a reducing agent or its precursor, and after development, the reducing agent remaining unoxidized is reduced to form a diffusible dye. A method of releasing the compound has been devised, and specific examples of the dye image-forming compound used therein are disclosed in
53-110,827, 54-130,927, 56-164,342, 53
-35,533.

On the other hand, as a substance that releases a diffusible dye at a portion where development has occurred, a substance that releases a diffusible dye by a reaction between a coupler having a diffusible dye as a leaving group and an oxidant of a developer is British Patent 1,330,524. No. 4, Japanese Patent Publication No. 48-39,165 and British Patent No. 3,443,940.

Further, in the system using these color developing agents, the contamination of the image due to the oxidative decomposition product of the developing agents poses a serious problem, so for the purpose of improving this problem, the developing agent is not necessary and it has a reducing property itself. Dye-releasing compounds have also been devised. A typical example thereof is, for example, U.S. Patent No. 3,928,312,
No. 4,053,312, No. 4,055,428, No. 4,336,322
No. 59-65839, No. 59-69839, No. 53-3819,
51-104,343, Research Disclosure 1746
5, U.S. Pat.Nos. 3,725,062, 3,728,113, and
3,443,939, JP-A-58-116537, JP-A-57-179840, US Pat. No. 4,500,626 and the like.

When the color light-sensitive material of the present invention is applied to a system for forming an image by diffusion transfer of a dye, a light-sensitive element and an image-receiving element or a dye fixing element are indispensable. It is roughly classified into a form coated separately on two supports and a form coated on the same support.

The relationship between the photosensitive element and the dye fixing element, the relationship with the support,
The relationship with the white reflective layer is 58 to 5 in Japanese Patent Application No. 59-268926.
The relationships described on page 9 and column 57 of US Pat. No. 4,500,626 can be applied to the present application.

A typical form of a film unit in which a light-sensitive element and an image-receiving element or a dye fixing element are provided on the same support is:
The image receiving element and the photosensitive element are laminated on one transparent support, and it is not necessary to peel the photosensitive element from the image receiving element after the completion of the transfer image. More specifically, the image-receiving element comprises at least one mordant layer, and in a preferred embodiment of the light-sensitive element, a combination of a blue-sensitive emulsion layer, a green-sensitive emulsion layer and a red-sensitive emulsion layer, or a green-sensitive emulsion layer. ,
A combination of a red-sensitive emulsion layer and an infrared-sensitive emulsion layer, or a combination of a blue-sensitive emulsion layer, a red-sensitive emulsion layer and an infrared-sensitive emulsion layer, and a yellow dye image-forming compound, magenta in each emulsion layer. A dye image-forming compound and a cyan dye image-forming compound are respectively combined to constitute (here, "an infrared light-sensitive emulsion layer is an emulsion layer having sensitivity to light of 700 nm or more, particularly 740 nm or more. Each of these photosensitive emulsion layers may be divided into two or more layers if necessary.
A white reflective layer containing a solid pigment such as titanium oxide is provided between the mordant layer and the photosensitive layer or the layer containing the dye image forming compound so that the transferred image can be viewed through the transparent support. A light-shielding layer may be further provided between the white reflective layer and the photosensitive layer so that the development process can be completed in a bright place. If desired, a peeling layer may be provided at an appropriate position so that all or part of the light-sensitive element can be peeled off from the image-receiving element (for example, such an embodiment is disclosed in JP-A-56-67840).
And Canadian Patent 674,082).

Further, in another form in which peeling is not required, the above-mentioned photosensitive element is coated on one transparent support, a white reflective layer is coated thereon, and an image receiving layer is further laminated thereon. A mode in which an image receiving element, a white reflective layer, a peeling layer and a photosensitive element are laminated on the same support, and a mode in which the photosensitive element is intentionally peeled from the image receiving element is described in US Pat. No. 3,730,718. On the other hand, there are roughly two representative forms in which a light-sensitive element and an image-receiving element are separately coated on two supports, one is a peeling type and the other is a peeling-free type. In more detail, in a preferable embodiment of the peelable film unit, the support has a light-reflective layer on the back surface thereof and at least one image-receiving layer is coated on the surface thereof. The photosensitive element is coated on a support having a light-shielding layer, and the photosensitive layer coating surface and the mordant layer coating surface do not face each other before the end of exposure, but the photosensitive layer coating surface after the end of exposure (for example, during development processing). Is devised so that it will turn over and overlap with the coated surface of the image receiving layer. After the transfer image is completed on the mordant layer, the light-sensitive element is rapidly separated from the image-receiving element.

In a preferred embodiment of the peel-free type film unit, at least one mordant layer is coated on a transparent support, and a photosensitive element is coated on a support having a transparent or light-shielding layer. The photosensitive layer coated surface and the mordant layer coated surface face each other and are superposed.

Any of the above-mentioned forms can be applied to both the color diffusion transfer system and the heat development system. In the former case, however, a pressure-rupturable container (processing element) containing an alkaline processing liquid is further combined. May be. Among others, in a peel-free type film unit in which an image receiving element and a photosensitive element are laminated on one support, the processing element is preferably arranged between the photosensitive element and a cover sheet overlaid thereon. Further, in the form in which the light-sensitive element and the image-receiving element are separately coated on the two supports, it is preferable that the processing element is disposed between the light-sensitive element and the image-receiving element at the latest during the development processing. The processing element preferably contains a light-shielding agent (such as carbon black or a dye whose color changes with pH) and / or a white pigment (such as titanium oxide) depending on the form of the film unit. Further, in the color diffusion transfer type film unit, it is preferable that a neutralization timing mechanism comprising a combination of a neutralization layer and a neutralization timing layer is incorporated in the cover sheet, the image receiving element, or the photosensitive element.

A polymer mordant is preferable as the mordant used in the image receiving element and the dye fixing element described later. Here, the polymer mordant is a polymer having a tertiary amino group, a polymer having a nitrogen-containing heterocyclic portion, a polymer having a quaternary cation group thereof, or the like.

Specific examples thereof are described in Japanese Patent Application No. 59-268926, pages 98 to 100, and U.S. Pat. No. 4,500,626, columns 57 to 60.

When the present invention is applied to a photothermographic material, an organic metal salt may be used as an oxidizing agent together with silver halide. In this case, the photosensitive silver halide and the organic metal salt need to be in contact with each other or in a close distance.

Among such organic metal salts, organic silver salts are particularly preferably used.

The organic compounds that can be used to form the above organic silver salt oxidizing agent include compounds described in Japanese Patent Application No. 59-228551, pages 37 to 39, U.S. Pat. There is. Further, silver salts of carboxylic acids having an alkynyl group such as silver phenylpropiolate described in Japanese Patent Application No. 60-113235, and silver acetylene described in Japanese Patent Application No. 60-90089 are also useful. Two or more kinds of organic silver salts may be used in combination.

The above organic silver salts are the following per mol of photosensitive silver halide:
0.01 to 10 mol, preferably 0.01 to 1 mol can be used in combination. The total coating amount of the photosensitive silver halide and the organic silver salt is preferably 50 mg to 10 g / m ² in terms of silver.

Hydrophobic additives such as the dye image-forming compounds and image-forming accelerators described below can be incorporated into the layers of the light-sensitive element by known methods such as those described in US Pat. No. 2,322,027. In this case, JP-A-59-83154,
59-178451, 59-178452, 59-178453, 59-
No. 178454, No. 59-178455, No. 59-178457, etc., a high boiling point organic solvent, if necessary, boiling point 50 ℃ ~ 160
It can be used in combination with an organic solvent having a low boiling point of ° C.

The amount of high boiling organic solvent used is 1 g of the dye image-forming compound used.
On the other hand, it is 10 g or less, preferably 5 g or less.

Further, a dispersion method using a polymer described in JP-B-51-39853 and JP-A-51-59943 can also be used.

In the case of a compound which is substantially insoluble in water, fine particles can be dispersed and contained in a binder in addition to the above method.

When dispersing the hydrophobic substance in the hydrophilic colloid, various surfactants can be used. For example, JP-A-59-157
The surfactants listed on pages (37) to (38) of No. 636 can be used.

In the present invention, it is desirable that the light-sensitive element contains a reducing substance. Examples of the reducing substance include those generally known as a reducing agent, and the dye image-forming compound having the above-described reducing property. Further, a reducing agent precursor which does not have reducing property itself but exhibits reducing property by the action of a nucleophile or heat during the development process is also included.

Examples of reducing agents used in the present invention include US Pat.
0,626, columns 49-50, 4,483,914, columns 30-31, JP-A-60-140335, pages (17)-(18), JP-A-60-1284.
The reducing agents described in No. 38, No. 60-128436, No. 60-128439, No. 60-128437, etc. can be used. In addition, JP-A-56-138,7
The reducing agent precursors described in US Pat. No. 36, 57-40,245, US Pat. No. 4,330,617 and the like can also be used.

Combinations of various reducing agents such as those disclosed in US Pat. No. 3,039,869 can also be used.

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

In the present invention, a compound capable of activating development and stabilizing an image at the same time can be used in the light-sensitive element. For specific compounds that are preferably used, see US Pat.
No. 6 columns 51-52.

Various antifoggants or photographic stabilizers can be used in the present invention. For example, research
Disclosure, December 1978, pages 24 to 25, azoles and azaindenes, nitrogen-containing carboxylic acids and phosphoric acids described in JP-A-59-168442, or mercapto described in JP-A-59-111636. Compounds and metal salts thereof, acetylene compounds described in Japanese Patent Application No. 60-228267 and the like are used.

In the present invention, the light-sensitive element may contain an image toning agent, if necessary. Specific examples of effective toning agents include the compounds described in Japanese Patent Application No. 59-268926, pages 92 to 93.

In order to obtain a wide range of colors in the chromaticity diagram by using the three primary colors of yellow, magenta and cyan, it is necessary to use a light-sensitive element having at least three silver halide emulsion layers having light-sensitivity in different spectral regions. Good. For example, the blue layer,
A combination of three layers of green-sensitive layer and red-sensitive layer, green-sensitive layer, red-sensitive layer,
There are combinations of infrared photosensitive layers. Each of these photosensitive layers may be divided into two or more layers if necessary.

The photosensitive element used in the present invention is, if necessary, various additives known for heat-developable photosensitive elements and layers other than the photosensitive layer, such as a protective layer, an intermediate layer, an antistatic layer, an antihalation layer and a dye. It may have a release layer, a matte layer or the like for facilitating release from the fixing element. Examples of various additives include plasticizers, matting agents, sharpness improving dyes, antihalation dyes described in Research Disclosure, June 1978, pages 9 to 15 and Japanese Patent Application No. 59-209563. There are additives such as surfactants, optical brighteners, anti-slip agents, antioxidants and anti-fading agents.

In particular, the protective layer usually contains an organic or inorganic matting agent to prevent adhesion. Further, this protective layer may contain a mordant and an ultraviolet absorber. The protective layer and the intermediate layer may each be composed of two or more layers.

Further, the intermediate layer may contain a reducing agent for preventing discoloration or color mixture, an ultraviolet absorber, or a white pigment such as titanium dioxide. The white pigment may be added to the emulsion layer as well as the intermediate layer for the purpose of improving the sensitivity.

If necessary, the dye fixing element can be provided with auxiliary layers such as a protective layer, a peeling layer and an anti-curl layer. In particular, it is useful to provide a protective layer. One or more of the above layers may include hydrophilic thermal solvents, plasticizers, anti-fading agents, UV absorbers, slip agents, matting agents, antioxidants, dispersed vinyl to increase dimensional stability. A compound, a surfactant, an optical brightener, etc. may be included. Further, particularly in a system in which heat development and transfer of a dye are simultaneously performed in the presence of a small amount of water, it is preferable that the dye-fixing element contains a base and / or a base precursor described later in order to enhance the storage stability of the photosensitive element. . Specific examples of these additives are shown in Japanese Patent Application No. 59-20956.
No. 3, pp. 101-120.

In the present invention, an image formation accelerator can be used in the light-sensitive element and / or the dye fixing element. The image formation accelerator includes a redox reaction between a silver salt oxidizing agent and a reducing agent, a reaction such as generation of a dye from a dye-donor substance, decomposition of the dye or release of a diffusible dye, and a light-sensitive material layer. Has a function of accelerating the transfer of the dye from the dye to the dye fixing layer, and from the physicochemical function, a base or a base precursor, a nucleophilic compound, a high boiling organic solvent (oil), a thermal solvent, a surfactant, silver Alternatively, they are classified into compounds that interact with silver ions. However, these substance groups generally have a composite function, and usually have some of the above-mentioned accelerating effects together. Details thereof are described in Japanese Patent Application No. 59-213978, pp. 67-71.

In addition to this, there are various methods for generating a base, and any compound used in the method is useful as a base precursor. For example, a method of generating a base by mixing a sparingly soluble metal compound described in Japanese Patent Application No. 60-169585 and a compound capable of complex-forming reaction with a metal ion constituting the sparingly soluble metal compound (referred to as a complex-forming compound). Alternatively, there is a method of generating a base by electrolysis described in Japanese Patent Application No. 60-74702.

The former method is particularly effective. Examples of the sparingly soluble metal compound include carbonates, hydroxides, oxides and the like of zinc, aluminum, calcium, barium and the like. Regarding complex-forming compounds, for example, co-authored by A.E. Martell and A.M.
"Critical Stability Constants (Critic
al Stability Constants ”, Volumes 4 and 5, Plenum Press. Specifically, aminocarboxylic acids, iminodiacetic acids, pyridylcarboxylic acids, aminophosphoric acids, carboxylic acids (mono,
Di, tri, tetracarboxylic acids and compounds with substituents such as phosphono, hydroxy, oxo, ester, amide, alkoxy, mercapto, alkylthio, phosphino), hydroxamic acids, polyacrylates, polyphosphoric acids, etc. and alkali metals, guanidine And salts with amidines, quaternary ammonium salts and the like.

The sparingly soluble metal compound and the complex-forming compound are advantageously added separately to the light-sensitive element and the dye-fixing element.

In the light-sensitive element and / or the dye-fixing element of the present invention, various development terminators can be used for the purpose of always obtaining a constant image against variations in processing temperature and processing time during development.

The term "development inhibitor" as used herein refers to a compound that immediately neutralizes or reacts with a base to reduce the concentration of the base in the film to stop the development after proper development, or to inhibit development by interacting with silver and a silver salt. Compound. Specific examples thereof include acid precursors that release an acid upon heating, electrophilic compounds that undergo a substitution reaction with a coexisting base upon heating, or nitrogen-containing heterocyclic compounds, mercapto compounds and precursors thereof (for example, Japanese Patent Application No. 58-216928, 59-48305, 59-85
Compounds described in No. 834 or No. 59-85836).

Further, a compound which releases a mercapto compound by heating is also useful, for example, Japanese Patent Application Nos. 59-190173 and 59-268926,
59-246468, 60-26038, 60-22602, 60-26
039, 60-24665, 60-29892, 59-176350,
There are compounds described in.

A hydrophilic binder may be used as the binder of the photosensitive element and / or the dye fixing element of the present invention. As the hydrophilic binder, a transparent translucent hydrophilic binder is typical, for example, gelatin, proteins such as gelatin derivatives, cellulose derivatives, starch, natural substances such as polysaccharides such as arabic gum, and polyvinylpyrrolidone,
Includes synthetic polymeric materials such as water soluble polyvinyl compounds such as acrylamide polymers. It is also possible to use a dispersed vinyl compound which is used in the form of a latex and which increases the dimensional stability of the photographic material. These binders can be used alone or in combination.

In the present invention, the binder is applied in an amount of 20 g or less per 1 m ² , preferably 10 g or less, more preferably 7 g or less.

The ratio of the high-boiling organic solvent and the binder dispersed together with the hydrophobic compound such as the dye-providing substance in the binder is 1 cc or less of the solvent per 1 g of the binder, preferably 0.5 cc or less, and more preferably 0.3 cc or less. is there.

The constituent layers (photographic emulsion layer, dye fixing layer, etc.) of the light-sensitive element and / or dye fixing element of the present invention may contain an inorganic or organic hardener.

Specific examples of the hardener include those described in Japanese Patent Application No. 59-268926, pages 94 to 95 and JP-A-59-157636, page (38), which may be used alone or in combination. Can be used.

In order to promote dye transfer, a hydrophilic thermal solvent which is solid at room temperature and dissolves at high temperature may be incorporated in the photosensitive element or the dye fixing element. The hydrophilic thermal solvent may be incorporated in either the photosensitive element or the dye fixing element, or may be incorporated in both. The built-in layer may be any of an emulsion layer, an intermediate layer, a protective layer, and a dye fixing layer.
Alternatively, it is preferably incorporated in the adjacent layer. Examples of hydrophilic thermal solvents include ureas, pyridines, amides, sulfonamides, imides, alcohols, oximes and other heterocycles. Further, a high-boiling point organic solvent may be contained in the light-sensitive element and / or the dye-fixing element in order to promote dye transfer.

The support used in the light-sensitive element and / or the dye-fixing element of the present invention can withstand the processing temperature.
As a general support, not only glass, paper, polymer film, metal and its analogues are used,
The support described on pages 95 to 96 of Japanese Patent Application No. 59-268926 can be used.

The light-sensitive element and / or the dye-fixing element may have a form having a conductive heating element layer as a heating means for heat development or diffusion transfer of a dye.

In this case, the transparent or opaque heating element can be manufactured by using a conventionally known technique as a resistance heating element. As the resistance heating element, there are a method of using a thin film of a semiconductive inorganic material and a method of using an organic thin film in which conductive fine particles are dispersed in a binder. As materials that can be used in these methods, those described in Japanese Patent Application No. 59-151815 can be used.

In the present invention, as the coating method of the photothermographic layer, protective layer, intermediate layer, undercoat layer, back layer, dye fixing layer and other layers, the methods described in US Pat. No. 4,500,626, columns 55 to 56 can be applied.

Radiation that also contains visible light can be used as a light source for image exposure for recording an image on the photosensitive element. Generally, light sources used for ordinary color printing, such as halogen lamps such as tungsten lamps, mercury lamps, iodine lamps, xenon lamps, laser light sources, CRT light sources,
The light source such as a light emitting diode (LED) described in Japanese Patent Application No. 59-268926, page 100 and US Pat. No. 4,500,626, column 56 can be used.

In the image forming method having a heating step to which the present invention is applied, for example, the steps of heat development and dye transfer may be independent or may be simultaneous. Further, it may be continuous in the sense that the scratch transfer is performed for the development in one step.

For example, (1) after imagewise exposing the photosensitive element and heating,
There are a method of stacking dye-fixing elements and heating as required to transfer the movable dye to the dye-fixing element, and a method of (2) image-exposing the photosensitive element and stacking and heating the dye-fixing elements.
The above methods (1) and (2) can be carried out in the substantially absence of water, or can be carried out in the presence of a trace amount of water.

The heating temperature in the heat development step is about 50 ° C. to about 250 ° C., and development is possible, but about 80 ° C. to about 180 ° C. is particularly useful. When heating in the presence of a small amount of water, the upper limit of the heating temperature is the boiling point or lower. When the transfer step is carried out after the completion of the heat development step, the heating temperature in the transfer step can be transferred in the range from the temperature in the heat development step to room temperature, but especially at 50 ° C or higher, about 10 ° C higher than the temperature in the heat development step. Up to a lower temperature is more preferable.

In the present invention, the preferred image forming method is heating in the presence of a trace amount of water and a base and / or a base precursor after or at the same time as the image exposure, and at the same time as the development, the diffusion generated in the portion corresponding to or inversely corresponding to the silver image. The sex dye is transferred to the dye fixing layer. According to this method
The generation or release reaction of the diffusible dye proceeds extremely quickly,
The migration of the diffusible dye to the dye-fixing layer also progresses rapidly, so that a high-density color image can be obtained in a short time.

The amount of water used in this embodiment is at least 0.1 times the weight of the total coating film of the light-sensitive element and the dye-fixing element, preferably 0.1.
It may be as small as or more than twice the weight of the solvent corresponding to the maximum swelling volume of the entire coated film (particularly less than or equal to the weight of the solvent corresponding to the maximum swelling volume of the entire coated film minus the weight of the entire coated film).

The state of the film during swelling is unstable, and local bleeding may occur depending on the conditions.To avoid this, the water content corresponding to the maximum swelling volume of the total coating film thickness of the light-sensitive element and the dye-fixing element should be avoided. Or less is preferable. Specifically, the total area of the photosensitive element and the dye fixing element is 1 g to 50 per 1 square meter.
The range of g, particularly 2 g to 35 g, and further 3 g to 25 g is preferable.

The base and / or base precursor used in this embodiment can be incorporated in both the light-sensitive element and the dye-fixing element. It can also be dissolved in water and supplied.

In the above aspect, the image-forming reaction system, as a base precursor, a water-insoluble basic metal compound and a metal ion constituting the hardly-soluble metal compound and a compound capable of a complex formation reaction in water as a medium, It is preferred to raise the pH of the system by the reaction of these two compounds on heating.
Here, the image reaction system means a region where an image forming reaction occurs. Specific examples include layers belonging to both the light-sensitive element and the dye-fixing element. When there are two or more layers, any of them may be used.

The sparingly soluble metal compound and the complex-forming compound must be added to at least another layer in order to prevent them from reacting before the development processing. For example, in a so-called monosheet material in which a light-sensitive element and a dye-fixing element are provided on the same support, it is preferable that the additive layers of the both are separate layers and that one or more layers are interposed therebetween. In addition, a more preferable form is
The sparingly soluble metal compound and the complex-forming compound are contained in layers provided on separate supports. For example, it is preferable that the poorly soluble metal compound is contained in the light-sensitive element and the complex-forming compound is contained in the dye-fixing element having a support different from that of the light-sensitive element. The complex-forming compound may be dissolved in water to be coexistent and supplied. The sparingly soluble metal compound is disclosed in JP-A-56-174830
No. 53-1027433 and the like, and it is desirable to include it as a fine particle dispersion prepared by the method described in JP-A No. 53-1027433. The average particle size thereof is preferably 50 microns or less, particularly preferably 5 microns or less. The sparingly soluble metal compound may be added to any layer of the photosensitive element such as the photosensitive layer, the intermediate layer and the protective layer, or may be added by dividing it into two or more layers.

The amount of the sparingly soluble metal compound or complex-forming compound to be added to the layer on the support depends on the compound species, the particle size of the sparingly soluble metal compound, the complex formation reaction rate, etc. It is suitable to use it in an amount of 50% by weight or less, more preferably 0.01% by weight to 40% by weight. When the complex-forming compound is dissolved in water and supplied, 0.005 mol to 5 mol, particularly 0.05 mol to 2 mol per liter.
Is preferred. Furthermore, in the present invention, the content of the complex-forming compound in the reaction system is preferably 1/100 to 100 times, and particularly preferably 1/10 to 20 times the molar ratio of the content of the sparingly soluble metal compound.

As a method of applying water to the photosensitive layer or the dye fixing layer,
For example, there is a method described in Japanese Patent Application No. 59-268926, page 101, line 9 to page 102, line 4.

As a heating means in the developing and / or transferring process, a heating plate, an iron, a heating roller, or the like is disclosed in Japanese Patent Application No. 59-26892.
No. 6, page 102, line 14 to page 103, line 11 is available. Further, a layer of a conductive material such as graphite, carbon black or metal may be superposed on the photosensitive element and / or the dye fixing element, and a current may be passed through the conductive layer to directly heat the conductive layer. .

Japanese Patent Application No. 59-268926, No. 1 of Japanese Patent Application No. 59-268926 describes the pressure conditions and the method of applying pressure when the light-sensitive element and the dye fixing element are superposed and closely contacted
The method described on pages 03 to 104 can be applied.

Any of a variety of thermal development apparatus can be used in processing the photographic elements of this invention. For example, JP-A-59-75247 and 59-177.
No. 547, No. 59-181353, No. 60-18951, No. 60-11673
The devices described in No. 4 etc. are preferably used.

Experimental Example The maximum absorption wavelength (λ _max ) of the cyan dye of the present invention and a known cyan dye was investigated. Note that (λ _max ) is a value when mordanted with a quaternary ammonium salt polymer *. Also,
The synthesis was carried out by the usual azo coupling method.

* Poly (methyl acrylate-co-N, N, N-trimethyl-N-vinylbenzylammonium chloride), but the ratio of methylacrylate to vinylbenzylammonium chloride is 1: 1.

From the above results, it can be seen that the dye of the present invention has a maximum absorption in long waves as compared with known dyes.

Example 1 A method for producing a benzotriazole silver emulsion will be described.

28 g of gelatin and 13.2 g of benzotriazole were dissolved in 3000 ml of water. The solution was stirred at 40 ° C. A solution prepared by dissolving 17 g of silver nitrate in 100 ml of water was added to this solution over 2 minutes.

The pH of this benzotriazole silver emulsion was adjusted and allowed to settle to remove excess salt. Then, the pH was adjusted to 6.30 to obtain a benzotriazole silver emulsion with a yield of 400 g.

Next, a method for preparing a silver halide emulsion will be described.

Well-stirred gelatin aqueous solution (1,000 ml of water containing 20 g of gelatin and 3 g of sodium chloride and kept at 75 ° C)
Aqueous solution containing sodium chloride and potassium bromide
600 ml and an aqueous solution of silver nitrate (600 ml of water in which 0.59 mol of silver nitrate were dissolved) were simultaneously added at an equal flow rate for 40 minutes. In this way, a monodisperse cubic silver chlorobromide emulsion (bromine 80 mol%) having an average grain size of 0.35 μ was prepared.

After washing with water and desalting, sodium thiosulfate 5 mg and 4-hydroxy-6
-Methyl-1,3,3a, 7-tetrazaindene 20mg added to 60
Chemical sensitization was performed at ° C. The yield of emulsion was 600 g.

Next, a method for preparing a gelatin dispersion of a cyan dye image forming compound will be described.

5 g of cyan dye image forming compound (A) and 5 g of triisononyl phosphate were weighed, 20 ml of tyl acetate was added, and the temperature was adjusted to about 70 ° C.
It was dissolved by heating into a uniform solution. This solution, 100 g of a 10% solution of coal-treated gelatin, and 60 ml of a 2.5% aqueous solution of sodium dodecylbenzenesulfonate as a surfactant were mixed with stirring, and then a homogenizer was operated for 10 minutes at 10,000 RPM.
Dispersed in. This dispersion is referred to as a cyan dye image-forming compound dispersion.

Next, the method for preparing the photosensitive coating material will be described.

a) Silver benzotriazole emulsion 10 g b) Photosensitive silver chlorobromide emulsion 15 g c) Dispersion of cyan dye image-forming compound 25 g d) 5% 5% aqueous solution of the following compound e) 10m methanol solution of benzenesulfonamide 5m
lf) p-Chlorophenylsulfonyl guanidine acetate 7%
15 ml or more of the liquid (50% ethanol aqueous solution) were mixed, and a thickener and water were added to make 100 ml. This solution was applied on a polyethylene terephthalate film having a thickness of 180 μm to a wet film thickness of 50 μm.

Next, the following protective layer coating composition was prepared.

Protective layer coating composition h) 10% gelatin 400g i) p-chlorophenylsulfonyl guanidine acetate 7%
Liquid (50% ethanol aqueous solution) 240 ml j) Hardener (4%) of the following structural formula 50 ml CH ₂ = CHSO ₂ CH ₂ CONH (CH ₂ ) ₂ NHCOCH ₂ SO ₂ CH = CH ₂ are mixed to increase viscosity. The agent and water were added to make 1000 ml. This coating composition is applied with the above-mentioned photosensitive coating material, and the thickness is further increased.
It was coated at 30 μm.

The photosensitive material 101 is prepared in this manner.

Same as the light-sensitive material 101 except that (B) or the compound (5), (19) or (37) of the present invention was used as the cyan dye image forming compound in the light-sensitive material 101 instead of the comparative compound (A). Then, photosensitive materials 102 to 105 were prepared.

After drying these photosensitive materials, use a tungsten bulb to
Imagewise exposed for 1 second with looks. Then, it was uniformly heated for 20 seconds on a heat block heated to 150 ° C.

Next, how to make the dye fixing material will be described.

45g on a paper support prepared by dissolving 63g of gelatin and 130g of a mordant having the following composition in 1300ml of water and laminating with polyethylene.
It was applied so as to have a wet film thickness of m and then dried.

Further, a solution prepared by dissolving 35 g of gelatin and 1.05 g of 1,2-bis (vinylsulfonylacetamidoethane) in 800 ml of water was coated and dried to a wet film thickness of 17 μm to prepare a dye fixing material.

After supplying 15 ml of water per 1 m ² to the film surface side of the dye fixing material, the above light-sensitive materials which had been subjected to the heat treatment were superposed on the fixing material so that the film surfaces were in contact with each other.

After heating for 6 seconds on a heat block at 80 ° C., the dye fixing material was peeled off from the light-sensitive material, and a cyan image was obtained on the fixing material.

The density was measured using a Macbeth reflection densitometer (RD 519).

The results are shown in Table 1.

Also, the maximum absorption wavelength (λ _max ) and the dye fixing material after the treatment were irradiated with xenon light of 80,000 lux for 2 weeks, and the concentration was 1.
Table 1 also shows the results of examining the change in concentration at 0.

It has been found that the cyan dye image-forming compound of the present invention gives an image having high density and low fog and high fastness to light.

The compounds of the present invention include (1), (9), (1
0), (11), (12), (27), (8), (31), (7
Similar results can be obtained by using (4), (70) and (36).

Example 2 A color photosensitive material 201 having a multilayer structure as shown in Table 2 was prepared. The yellow, magenta, and cyan dye image-forming compounds were each added as a dispersion by the method described in Example 1.

A light-sensitive material 202 having exactly the same composition and structure except that the cyan dye image forming compound used in the light-sensitive material 201 was replaced by the compound (2) of the present invention was prepared.

Cyan Dye Image Forming Compound: Comparative Compound (A) of Example 1 The dye fixing material used was that shown in Table 3.

A tungsten light bulb was used as the multi-layered color light-sensitive material, and exposure was performed at 2000 lux for 1 second through B, G, and R three-color separation filters whose densities were continuously changed.

Water of 15 ml / m ² was supplied to the emulsion surface of the exposed light-sensitive material with a wire bar, and then the dye fixing material was superposed so that the film surface was in contact.

Using a heat roller whose temperature was adjusted so that the temperature of the absorbed film was 90 ° C., it was heated for 25 seconds. Next, when the dye fixing material was peeled off, clear images of yellow, magenta and cyan were obtained on the fixing material corresponding to the three color separation filters of B, G and R.

Further, the light-sensitive material was stored under the conditions of 40 ° C. and 80% relative humidity for one week and then processed in the same manner.

Table 4 shows the measurement results of the maximum density (D _max ) and the minimum density (D _min ) of cyan.

Further, the results of a fading test using xenon light in the same manner as in Example 1 are shown.

From Table 4, it was found that the cyan dye image-forming compound of the present invention has good storage stability in a light-sensitive material and also has excellent image stability to light.

Example 3 A light-sensitive material 301 was prepared by sequentially coating the following layers (I) to (VII) on a transparent polyethylene terephthalate support.

(I) a) copoly [styrene-N-vinylbenzyl-N, N,
N-trihexyl ammonium chloride (4.0g / m ² ) b) Dye image receiving layer containing gelatin (4.0g / m ² ) (II) a) Titanium dioxide (22g / m ² ) b) Gelatin (2.2g / m ²⁾ (III) a) Carbon black (2.7 g / m ² ) b) Opaque layer containing gelatin (2.7 g / m ² ) (IV) a) Cyan dye image-forming compound (0.33)
Cyan dye-donor layer (V) a) Red-sensitivity containing 1.1 g / m ² ) including gelatin dispersion (mmol / m ² ) and compound C (0.4 mmol / m ² ) b) Gelatin (including gelatin of a) above) Silver iodobromide emulsion (0.5 gAg / m ² ) b) Red-sensitive layer containing gelatin (1.1 g / m ² including gelatin of the above a) (VI) a) 2,5-di (t-pentadecyl) Hydroquinone (0.82 gAg / m ² ) b) Vinyl acetate (0.8 g / m ² ) c) Intermediate layer containing gelatin (0.4 g / m ² ) (VII) a) Magenta dye image-forming compound shown below (0.3 mmol g) / m ² ) and a gelatin dispersion of compound C (0.4 mmol / m ² ) b) A magenta dye-donor layer containing gelatin (1.1 g / m ² including gelatin of the above a) (VIII) a) Green-sensitive iodine Silver bromide emulsion (0.5 mmolg Ag / m
² ) b) Intermediate layer which is the same as the green-sensitive layer (IX) (VI) including (g) gelatin (1.1 g / m ² ) including gelatin of the above (a) (X) a) The following yellow dye image compound (0.5 mmol) g / m ² ) and gelatin dispersion of compound C (0.6 mmol / m ² ) b) 1.1 g / m ² ) including gelatin (including gelatin of a) above) Yellow dye-donor layer (XI) a) Blue sensitivity Silver iodobromide emulsion (0.5 g / m ² ) b) Blue-sensitive layer containing gelatin (1.1 g / m ² including gelatin of the above a) (XII) a) Polyethylene acrylate latex (0.9 g / m ²⁾ ) B) Tinuvin (0.5 g / m ² ) c) Hardener triacryloyl perhydrotriazine (0.
026g / m ² ) d) Protective layer containing gelatin (1.3g / m ² ). A light-sensitive material 302 having exactly the same composition and structure except that the cyan dye image forming compound used in the light-sensitive material 301 was replaced with the compound of the present invention and the compound (50) was prepared.

Next, the lower layer was sequentially coated on a transparent polyethylene terephthalate film to prepare a cover sheet.

(I) a) polyacrylic acid (17 g / m ² ) b) N-hydroxysuccinimide benzene sulfonate gelatin (0.06 g / m ² ) c) acid neutralization layer containing ethylene glycol (0.5 g / m ² ). (II) a) Timing layer coated with cellulose acetate (degree of saccharification 54%) to a thickness of 2 μm (III) Timing layer coated with copolymerized latex of vinylidene chloride and acrylic acid to a thickness of 4 μm A treatment liquid was prepared.

Potassium hydroxide 48g 4-Hydroxymethyl-4-methyl-1-p-tolyl-3-pyrazolidinone 10g 5-Methylbenzotriazole 2.5g Sodium sulfite 1.5g Potassium bromide 1g Benzyl alcohol 1.5ml Carboxymethylcellulose 6.1g Carbon black 150g Water The total amount was set to 1. After exposing the light-sensitive material through a color separation wedge, the cover sheets were superposed and the processing liquid was uniformly spread with a thickness of 80 μm between them by using a pair of juxtaposed rollers.

After 1 hour, the density of the cyan image area was measured.

In addition, it is exposed to a fluorescent lamp (17,000 lux) for 2 weeks for concentration.
The image stability at 1.0 was investigated. The results obtained are shown in Table 5.

It has been found that the cyan dye image-forming compound of the present invention gives a good positive image and a dye image having excellent stability to light.

Further, the compounds of the present invention include (42), (49), (53)
Similar results are obtained with.

(Effects of the Invention) The cyan dye image-forming compound contained in the color light-sensitive material of the present invention can be synthesized relatively easily, and further, the hue of the cyan color image formed from the compound can be effectively made to have a long wavelength to improve light fastness. It is possible to give an excellent and beautiful color image, and further, it is possible to favorably preserve the color light-sensitive material.

Claims (1)

[Claims] 1. A color light-sensitive material having at least one light-sensitive silver salt layer containing an image-forming compound represented by the following general formula (I) on a support. (Dye-X) q-Y (I) Dye represents a cyan dye group or dye precursor group represented by the following formula (II), X represents a simple bond or a linking group, and Y represents a latent image in an image. Dye is released corresponding to or opposite to the photosensitive silver salt, and the released dye and (D
ye-X) qY represents a group having the property of causing a difference in diffusivity from the compound represented by Dy,
e and X are bonded by A or E in the formula (II). q is 1 or 2, and when q is 2, Dye-X may be the same or different. A is a bond, a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic residue, or (A ² and A ³ are the same as those represented by A.
Further, A ² and A ³ may combine with each other to form a heterocycle. ) Is represented. R ¹ represents a hydrogen atom, an alkyl group, or a substituted alkyl group. B is a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic residue, a substituted or unsubstituted amino group, a substituted or unsubstituted alkyl or aryl It represents an oxy group, a substituted or unsubstituted alkyl or arylthio group, an acylamino group, a sulfonylamino group, a hydroxyl group, a carboxyl group, or a substituted or unsubstituted carbamoyl group. E is a bond, a hydrogen atom, an alkyl group, a substituted alkyl group, a halogen atom, -OR ⁴ , (R ⁴ and R ⁵ each represent a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, and R ⁴
And R ⁵ may form a 5- or 6-membered ring. ). G represents a hydroxyl group or a salt thereof, and a group selected from the following (T) to (V). However, R ²¹ and R ²² may be the same or different and each is a substituted or unsubstituted alkyl group, cycloalkyl group, alkenyl group, aralkyl group, aryl group, heterocyclic residue, alkyloxy group. Represents an aryloxy group, an alkylthio group, an arylthio group and an amino group. R ²¹ and R ²² may combine with each other to form a 5- or 6-membered ring.