JPS62123457A - Transfer type heatdevelopable photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain the titled material capable of reducing the stain of an image by incorporating a specific sensitizing coloring matter which disappears a color by heating to the titled material. CONSTITUTION:The sensitizing coloring matter which disappears the color by heating and is shown by formulas I-IV is incorporated to the photographic sensitive material. In the formulas, Z<1>-Z<3> are each an atomic (group) necessary to forming a coloring matter nucleus, R<1> is a sulfo (sulfonate), a sulfato or a cyano group, etc., R<2> is H or 1-4 C and alkyl group, R<3>, R<5> and R<8> are each a atomic group necessary to forming a coloring matter, R<4> is H, or 1-10 C an acyl group, R<6> and R<7> are each a carboxyl (salt), a sulfo (salt) or 1-10 C an acyl group, R<9> is a carboxyl or a sulfo group, etc., R<10> is a carboxyl (salt), or a sulfo (salt) group, X<-> is an anionic ion, (l)=0 or 1, (m)=1 or 2, (n)=0, 1 or 2, Q is an atomic group necessary to form a heterocyclic ring. Said sensitizing coloring matter may be added to the titled material, thereby reducing the stain of the image, when effecting a chemical sensitization.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a heat-developable photosensitive material in which a dye image is formed by transferring a dye formed or released by heat development, and in particular, it relates to a photothermographic material that reduces staining. The present invention relates to a transfer type heat-developable photographic material improved as described above.

[Conventional technology]

Problems with the technology of obtaining dye images through wet processing using conventionally known photosensitive silver halides and dye-forming couplers, such as the large amount of time and effort required for processing, and concerns about the effects of processing chemicals on the human body. , as a technology aimed at solving problems such as the risk of contamination of processing rooms and workers with processing chemicals, and the need to consider pollution caused by processing waste liquid, using photosensitive silver halide, reducing agents,
A photosensitive material in which a dye-providing substance and a binder capable of forming or releasing a diffusible dye by heat development are formed on a support, and the dye formed or released by heat development is transferred to an image-receiving layer to obtain a dye image. Japanese Patent Publication No. 57-186744
No. 5g-123533, No. 58-149046, No. 5111-149047, etc.

However, this type of photosensitive material has a common drawback in that the resulting images have large stains. Therefore, it is considered that the development of a technology to reduce this stain is for a purpose.

[Purpose of the invention]

An object of the present invention is to improve the drawback of the above-mentioned types of photosensitive materials, which have large stains.

[Structure of the invention]

An object of the present invention is to provide a transfer type heat-developable photographic light-sensitive material having at least a layer containing photosensitive silver halide on a support, characterized in that the photographic light-sensitive material contains a sensitizing dye whose color disappears by heat. This is achieved by a transfer type heat-developable photosensitive material.

The present invention will be explained in detail below.

The present invention is based on the fact that the inventors of the present invention and others have discovered that a considerable portion of stain is derived from sensitizing dyes for spectral sensitization of silver halide while conducting research on stain reduction. be.

In the case of normal photosensitive materials that use a liquid-integrated processing solution, there is a fixing process, during which most of the sensitizing dye is eluted, so staining due to the sensitizing dye is unlikely to be a problem, or in the case of transfer methods. Since there is no such elution in Al11, it is assumed that the sensitizing dye released from the silver halide due to an increase in temperature tends to contaminate the image-receiving element.

The sensitizing dye whose color disappears due to heat used in the present invention is a sensitizing dye whose color substantially disappears when it is incorporated into a heat-developable light-sensitive material and thermally developed.

The feeling of color disappearing due to the heat used in the present invention is f! ! , the following general formula (1) or IV) as a basic and preferable case
Examples include compounds represented by:

In the formula, Zl is R which completes the basic anine dye nucleus. Atoms or atomic groups necessary for (e.g. -6-, -N-).

R' and R'' each represent a hydrogen atom or an optionally substituted alkyl group having 1 to 6 carbon atoms.
may be substituted with a sulfo group, a salt thereof, a fulfato group, a diosulfato group, a cyano group, an arylsulfonyl group (e.g. phenylsulfonyl), an acyl 2,t', (e.g. acetylbenzoyl), or an argyl group. represents a sulfinocarnomoyl alkyl group, R
2 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms (for example, methyl, ethyl, propyl, tert-butyl, etc.), R8 represents an atomic group necessary to complete the cyanine dye, and X represents an anion. and Q represents 0 or 1. In the general formula [II], Z2 has the same meaning as zl in the general formula CI), and R4 is a hydrogen atom or an acyl group having 1 to 10 carbon atoms (for example, acetyl, propionyl, Butyryl, benzoyl (k), I (5 represents an atomic group necessary to complete the cyanine dye, Xo represents an anion, Q is 0), and represents 1.

General formula (m) H2 R'-C-R' H (XM In the formula, Z3 has the same meaning as Zl in general formula (1), and R' and R7 each represent a carboxyl group or sulfo Is or a salt thereof (e.g. R8
represents the atomic group necessary to complete the cyanine dye,
xG represents an anion, and Q represents 0 or l.

General formula CCV) In the formula, R9 is a carboxyl group, a sulfo group, or a salt thereof (for example, an alkali metal salt, an ammonium salt, etc.)
(e.g., methyl, ethyl, propyl, sulfopropyl, carboxybutyl, etc.), and R10 represents an alkenyl group (e.g., allyl, isopropenyl, etc.), and R10 is a carboxyl group or a sulfo group. These salts (e.g. alkali metal salts, ammonium 1),
+n+Snarke 9L $1. - 硼 stands for 1 or 2, Q
represents an atomic group necessary to complete a heterocycle containing a nitrogen atom together with the carbonyl activity in the formula. The heterocycle represented by Q is preferably a 5- or 6-membered heterocycle having an atom selected from oxygen, sulfur, and nitrogen as a heteroatom, such as a thiohydantoin ring, an imidazolinone-2-thione ring, or a rhodanine ring. ring, thioxasilinonedione ring, pyrazolin-3-one ring, pyrimidine-2-dione-4,6
-Dione rings and the like.

General formulas (1) to ClTl], each of ~N>1 in the formula? − to N>R” and to, I>1□゛)
l 1 1(
R11, rtl- and R13 represent atomic groups necessary to complete the Tanyan noanine dye. ).

The anion represented by Examples include those used for salt.

Typical examples of sensitizing dyes whose color disappears due to heat, which are advantageously used in the present invention, are listed below, but the present invention is not limited thereto.

(D-1) (D-6) (D-7) (D-8) (D-9) (D-10) (D-11) (D-12) CD-14) (D-15) (D-16) Coooxf (D-24) CaO3 cod shi112-shi11 = 1. , Ilt (D-32) (D-33) (D-34) (D-35) (1)-36) (D-:(7) C112COOI1 (D-39) to [2 to υ01l (D-40) Item 2 e O=C-N-5o2C113 (D-44) (ill, C2+15 C11l, C,l+.

(D-46) r (D-47) l　　　e　　　　　　　＋ CI+20S03C, I+5 (D-51) (D-52) (D-, 53) l( (D-54) I] (D’　””)Cdl.

(D-56) (D-59) (D-60)
C, 11° turtle CI+1. C2+1゜These compounds can be synthesized by any known method, and the compounds shown in the general formulas CI) to Cl) are
-111239, or the compound of general formula [■], U.S. Patent No. 2,493.748, U.S. Pat.
．． No. 876, No. 2,497.878, No. 2,519.
O old number, 3゜625.698, 3.384.48
No. 6, No. 3,625,698, No. 3゜567.458
You can synthesize it by referring to the numbers etc.

These enhancing dyes can be introduced into the light-sensitive material by various methods well known in the art.

The most common method is to dissolve the sensitizing dye in a solvent such as water, methanol, or trimethylpolamide, and add silver halide during chemical sensitization.

There is no particular restriction on the timing of addition, but since the timing will affect the sensitivity, gradation, storage stability, etc. of the photographic material obtained, care should be taken to find the optimal conditions through experiments when designing the photographic material. There is a need to.

It can also be added at times other than chemical sensitization, such as when preparing a coating solution.

There is no particular restriction on addition 1, and it is sufficient to add 1 that provides the desired performance, but I range or appropriate. More preferably, it is lX 10-' mol to I X 10-' mol.

Examples of the photosensitive silver halide used in the present invention include silver chloride, silver bromide, silver iodide, silver chlorobromide, silver chloroiodide, silver iodobromide, and silver chloroiodobromide. The photosensitive silver halide can be prepared by any method used in the photographic field, such as the single-jet method or the double-jet method. Photosensitive silver halide emulsions prepared according to the method of preparation give favorable results.

The light-sensitive silver halide emulsion may be chemically sensitized by any method known in the photographic art. Such sensitization methods include
Various methods include gold sensitization, sulfur sensitization, gold-sulfur sensitization, and reduction sensitization.

The silver halide in the above photosensitive emulsion may have coarse or fine grains, but the preferred grain size is about 0.001 μm to about 1.5 μm, more preferably about 0.001 μm to about 1.5 μm. 01 μm to about 05 μm.

The photosensitive silver halide emulsion prepared as described above can be most preferably applied to the heat-developable photosensitive layer which is a constituent layer of the photosensitive material of the present invention.

In the present invention, as another method for preparing photosensitive silver halide, a photosensitive silver salt-forming component can be made to coexist with an organic silver salt described below, and a photosensitive silver halide can be formed in a part of the organic silver salt. . The photosensitive silver salt-forming component used in this preparation method is an inorganic halide, for example, a halide represented by M X n (where M is an I-(atom, N
+-14 group or metal jH;
Represents C12, 13r or ■, n: yoM or f-1
In the case of atoms, NIl, and W, I and M are metal atoms, respectively. Metal atoms include lithium, sodium, potassium, rubidium, cenium, copper, gold, helium, machinenium, carnoium, strontium, barium, zinc, cadmium, mercury, aluminum, indium, mercury, ruthenium, thallium, kermanium, and river. , lead, antimony, hismuth, chromium, molybdenum, tungsten, manganese, rhenium, iron, cobalt, nickel, ronium, palladium, osmium, iridium, platinum, cerium, etc. ), halogen-containing metal complexes (eg, KzPtCI2a).

K2Pt, Bre, 1lAu CL, (NL)t
1rc(!ll, (NL)+Ir CQg.

(Nl14)z Ru C(!o, (Nl14)iRL
I C(!a, (NIl4)3Rh Cl2e.

(Nl14), RhBre, etc.), onium halide, (
For example, tetramethylammonium halides such as tetramethylammonium bromide, trimethylphenylammonium bromide, cetylethyldimethylammonium bromide, 3-methyldeazolium bromide, trimedelbenzylammonium bromide, 11-treated phosphatides such as tetraethylphosphonium bromide 3-treated sulfonium halides such as phonium halide, pennoethylmethylsulfonium bromide, 1-ethylthiazolium bromide, etc.), halogenated hydrocarbons (
For example, iodoform, bromoform, carbon tetrabromide, 2
-bromo-2-methylpropane, etc.), N-halogen compounds (N-chlorosuccinimide, N-bromosuccinimide, N-bromophthalimide, N-bromoacetamide, N-iodosuccinimide, N-bromophthalanononone) , N-chlorophthalazinone, N-bromoacetanilide, N,N-dibromobenzenesulfonamide, N-
Bromo-N-methylbenzenesulponamide, 1,3-
dibromo-4,4-dimethylhydantoin, etc.), other halogen-containing compounds (such as triphenylmethyl chloride,
triphenylmethyl bromide, 2-bromobutyric acid, 2-bromoethanol, etc.).

These photosensitive silver halides and photosensitive silver salt forming components can be used in combination in various methods, and the amount used is 0.002 mol to 1 mol per unit of the dye-providing substance or dye-providing substance monomer. The amount is preferably 10 moles, more preferably 0.2 to 2.0 moles.

When the present invention is applied to a heat-developable color photosensitive material, it is sufficient that the material has at least one layer containing the sensitizing dye of the present invention, and each layer is sensitive to blue light, green light, and red light; That is, a heat-developable blue-sensitive layer, a heat-developable green-sensitive layer, and a heat-developable red-sensitive layer can be used to form a multilayer structure. Furthermore, the photosensitive layer of the same color is divided into two or more layers (for example, a high-sensitivity layer and a low-sensitivity layer).1. It is possible to set up

In the above cases, each of the blue-sensitive silver halide emulsion, green-sensitive silver halide emulsion, and red-sensitive silver halide emulsion is added with the spectral sensitizing dye of the present invention to the silver halide emulsion. You can get it by doing this. The light-sensitive material of the present invention can contain the sensitizing dye of the present invention in combination with other known sensitizing dyes.

Typical spectral sensitizing dyes that can be used in combination with the present invention include, for example, nanine, melonanine, complex, (trinuclear or mononuclear) noanine, holobolanine, styryl, heminanine, oxonol, etc. It will be done. Among the cyanine dyes, those having a basic nucleus such as deazoline, oxazoline, viroline, pyridine, oxazole, thiazole, selenazole, and imidazole are more preferred. In such a nucleus, an alkyl group,
It may contain an alkylene group, a hydroxyalkyl group, a sulfoalkyl group, a carboxyalkyl group, an aminoalkyl group or an enamine group to form a fused carbocyclic or heterocyclic ring. Further, it may be symmetrical or asymmetrical, and the methine chain or polymethine chain may have an alkyl group, a phenyl group, an enamine group, or a heterocyclic substituent.

In addition to the above-mentioned basic nucleus, the melonanine dye may have an acidic nucleus such as a thiohydantoin nucleus, a rhodanine nucleus, an oxazoturic acid solution, a deazolinthion nucleus, a malononitrile nucleus, or a pyrazolone nucleus. These acidic nuclei further include alkyl groups, alkylene groups, phenyl groups, carboxyargyl groups, sulfoalkyl groups, hydroquinalkyl groups,
Alcoquine may be substituted with an alkyl group, an alkylamine group or a heterocyclic nucleus. If necessary, these dyes may be used in combination. Furthermore, ascorbic acid derivatives, azaindene cadmium salts, organic sulfonic acids, etc.
For example, U.S. Patent Nos. 2,933,390 and 2,93
A supersensitizing additive that does not absorb visible light, such as those described in the specification of No. 7,089, can be used in combination.

The amount of these dyes added is 1 x 10-' mol-[mol] per mol of silver halide or silver halide-forming component. More preferably, IX 10-' mol to LX 10
−'Mole.

In the heat-developable photosensitive material of the present invention, various a-type silver salts can be used, if necessary, for the purpose of increasing sensitivity and improving developability.

The thermal development photosensitive material of the present invention (used together with the 4 ingredients) (as a crude salt, Japanese Patent Publication No. 434921, Japanese Patent Publication No. 44-26582)
No. 4518416, No. 45-12700, No. 4
No. 5-22185, JP-A No. 49-52626, No. 52
-31728, 52-137321, 52-1
No. 41222, No. 53-36224 and No. 53-3
No. 7610-4 and U.S. Patent No. 3.330,6
No. 33, No. 3,794,496, No. 4,105,
No. 451, No. 4,123,274, No. 4,168
Silver salts of aliphatic carboxylic acids such as silver laurate, silver myristate, silver palmitate, silver stearate, silver aragidonate, silver behenate, α -(1-phenyltetrazolethio)silver acetate, etc., aromatic silver carbhonates, such as silver aromatate, silver phthalate, etc., Japanese Patent Publication No. 44-26582, No. 4
No. 5-12700, No. 45-18416, No. 45-2
No. 2185, JP-A-52-31728 and JP-A-52-31728
Publication No. 137321 No. 6 and patent application No. 1065/1986
Silver salts of imino groups, such as benzotriazole silver, as described in the specifications of No. 57-1066, etc.
5-Nitrohencitriazole silver, 5-chlorobenzotriazole silver, 5-methoxybenzotriazole silver, 4
-Sulfobenzotriazole silver, 5-aminobenzotriazole silver, 5-calhoki/hensitriazole silver, 5
-Methylbenzotriazole silver, 4-(N-denorsulfamoyl)hensitriazole silver, 4-(N,N~noethylsulfamoyl)hensitriazole silver, imidazole silver, benzimidazole silver, 6-nidropenzimidazole Silver, pyrazole silver, 1.2.4-triazole silver, IH-tetrazole silver, 3-amino-5-pennorthio-1,2,4-triazole silver, saccharin silver, phthalazinone silver, phthalimide silver, and other 2 -Silver mercaptohenzoxazole, silver mercaptooxanoazole, silver 2-mercaptobenzothiazole, silver 2-mercaptobenzimidazole, silver 3-mercapto-4-phenyl-l, silver 2,4-triazole, 4-hydroquine-6-methyl -1,3,3a,7-titrazaine silver and 5-methyl-7-hydroxy-1,2,3.

Examples include 4.6-pentazaindene silver.

Among the above-mentioned alFi salts, silver salts of imino groups are preferred, and silver salts of benzotriazole derivatives are particularly preferred, and silver salts of sulfobenzotriazole derivatives are particularly preferred. The organic silver salts used in the present invention may be used alone or in combination of two or more, and they may be isolated and used by dispersing them in a binder by an appropriate means, or they may be used in a suitable manner. The silver salt may be prepared in a binder and used as is without isolation.

The amount of silver salt used is 1
The amount per mole is preferably 0.1 to 5 mol, more preferably 0.3 mol to 3 mol.

As the reducing agent used in the heat-developable photosensitive material of the present invention, those commonly used in the field of thermal color photosensitive materials can be used, such as U.S. Pat. No. 3.764, 328 by Akira Tani q+n, also RD No. 12146, No.
, 15108, same No.

! 5127 and JP-A-56-27H2, p-phenylenenoamine type and p-aminophenol type developing agents, fukesphoramide phenol type 15 and sulponamide phenol type developing agents, and manonihydrazone type coloring agents. Examples include the main drug. Also, U.S. Patent No. 3
, No. 342,599, No. 3,719.492, JP-A-53-135628, JP-A-54-79035, etc., such as the color developing agent breaker, etc. can be used for fl+.

As a particularly preferable reducing agent, JP-A-56-146133
1) Reducing agents represented by the following general formula (V) described and relied upon in the specification may be mentioned.

General formula (V) [] In the formula, RI' and R15 are hydrogen atoms, or have a carbon atom number of 1 to 30 (preferably 1), which may have a substituent.
-4) represents an alkyl group, and RI4 and RI5 may be ring-closed to form a heterocycle. RI8. R”.

RII' and R" each have a hydrogen atom, a halogen atom, a hydroquine group, an amino group, an alkoxyn group, an anolamide group, a sulfonamide group, an alkylsulfonamide group, or a carbon atom number I to 30 (preferably) that may have a substituent. is 1~
4) represents an alkyl group, and rtlB and 1114 and RIB and R'5 may each be ring-closed to form a heterocycle. M represents a compound containing an alkali gold@4 atom, an ammonium group, a nitrogen-containing base, or a quaternary nitrogen atom.

In the above general formula [■], the nitrogen-containing organic salt is a compound containing a basic nitrogen atom that can form a salt with an inorganic acid, and particularly important organic bases include amine compounds. It will be done. Examples of chain amine compounds include primary amines, secondary amines, and tertiary amines, and examples of cyclic amine compounds include typical heterocyclic organic bases such as pyridine and quinoline. , piperinone, imidazole and the like. In addition, compounds such as hydroquinylamine, hydranone, and amidine are also useful as chain amines. Salts of nitrogen-containing organic bases include the above-mentioned inorganic acid salts of a-organic bases (e.g. hydrochlorides, sulfates,
nitrates, etc.) are preferably used.

On the other hand, as the l″f compounds containing quaternary nitrogen in the above general formula, -nitrogen compounds 4,'7 having a monovalent covalent bond
Examples include salts or hydroxides of No. 4.

Next, preferred specific examples of the reducing agent represented by the general formula [] are shown below.

(R-2) (fl　-3') ([1-5i　) Shito 1 (R-5) OCII.

(R-6) (R-7) (R-8) (R-9) Shi■ri (r(-10) ullfu (R-11) ull co (R-12) (R-13) (R-14) N.H.

(R-15) (R-16) ('R-17) (R-18) (R-1,9) (R-20) (n-21) (fl -22) l'X C, l11 ( IN-23) The reducing agent represented by the above general formula [■] can be used by a phase separation method,
For example l-1ouben Weyl, Mcthode
ndcrOrganischen Chemie,
It can be synthesized according to the method described on page 03 of B andX [/2.645].

Other reducing agents as described below may also be used.

For example, phenols (e.g., p-phenylphenol, p-methquinphenol, 2.6-tert-butyl-p-cresol, N-methyl-p-aminophenol, etc.), sulfonamide phenols (e.g., 4-benzene) Sulfonamidophenol, 2henzenesulfonamidophenol, 2゜6-fuchloro-4-benzenesulfonamidophenol, 2,6-dipromo 4-(p
- toluenesulfonamide) phenol, etc.], Manoni is a polyhydroquinohenzene (e.g. hydroquinone, t
ert -butylhydroquinone, 2,6-dimethylhydroquinone, chlorohydroquinone, carboxyhydroquinone, catechol, 3-carboxycatechol, etc.), naphthols (e.g. α-naphthol, β-naphthol, 4-aminonaphthol, 4-methoquinonaphthol, etc.) ), hydroxybinaphthyls and methylene bisnaphthols [e.g. 1,1'-dihydroquino, 2,2'-
Binaphthyl, 6,6'-nobromo2,2'-nohydroquine-1,1'-binaphthyl, 6,6-dinitro-
2,2'-dihydroquine-1,1'-binaphthyl, 4.
4'-diphthoquino-1,1'-dihydroquino 2.2'
-Binaphthyl, bis(2-hydroxy-1-naphthyl)
methane, etc.], methylene hisphenols [e.g. 1.1
-His(2-hydroquine-3,5-dimethylphenyl)
-3,5,5-trimedelhexane, 1,1-his(2
-hydroquine-3-tert-butyl-5-methylphenyl)methane, 1,1-his(2-hydroquino-3,5
-not-tert-butylphenyl)methane, 2,6-methylenebis(2-hydroquine-3-tert-butyl-
5-methylphenyl)-4-methylphenol, α-phenyl-α, α-his(2-hydroquino-3,5-not-tert-butylphenyl)methane, α-phenyl-α
, α-bis(2-4doroquino-3-tcrt-butyl-
5-Medylphenyl)methane, 1,1-his(2-hydroquine-3,5-dimethylphenyl)-2-methylpropane, 1,1,5,5-tetrakis(2-hydroxy-
3,5-dimethylphenyl)-2,4-ethylpentane, 2,2-bis(4-hydroxy/-3,5-dimethylphenyl)propane, 2,2-bis(4-hydroxy-3
-methyl-5-tert-butylphenyl)propane,
2,2-bis(・1-hydroxy-3,5-diter
t-butylphenyl)propane, etc.], ascorbic acids, 3-pyrazolidones, ascorbic acids, 3-pyrazolidones, pyrazolones, hydrazones, and paraphenylenediamines.

These reducing agents can be used alone or in combination of two or more. The amount of the reducing agent to be used depends on the type of photosensitive silver halide used, the type of broiler acid silver salt rj, and the types of other additives, but it is usually equal to 1 mole of color T and donor monomer. The amount is in the range of 0.05 to 10 mol, preferably 0.1 to 5 mol.

Examples of the binder used in the heat-developable photosensitive material of the present invention include synthetic or natural binders such as polyhinyl butyral, polyvinyl acetate, ethyl cellulose, polymethyl methacrylate, cellulose acetate butyrate, polyvinyl alcohol, polyvinylpyrrolidone, gelatin, and phthalated gelatin. One or more of these polymeric substances can be used in combination. In particular, it is preferable to use gelatin or a derivative thereof in combination with a hydrophilic polymer such as polyvinylpyrrolidone or polyvinyl alcohol, and more preferably the following binder described in Japanese Patent Application No. 104249/1982.

This binder includes gelatin and vinylpyrrolidone polymer. The vinylpyrrolidone polymer may be polyvinylpyrrolidone, which is a homopolymer of vinylpyrrolidone, or a copolymer of vinylpyrrolidone with one or more other monomers that can be copolymerized (including kraft copolymers). ). These polymers can be used regardless of their degree of polymerization. Polyvinylpyrrolidone may be substituted polyvinylpyrrolidone,
Preferred polyvinylpyrrolidone has a molecular weight of 11.000 to 4
00,000 Rano. Vinylpyrrolitono and J (other polymerizable monomers include acrylic acid, methacrylic acid and its (meth)acrylic acid esters such as alkylnisdales, vinyl alcohols, vinylimidazoles, (meth)acrylamides, and Examples include vinyl monomers such as carbinols and vinyl alkyl ethers, but it is preferable that at least 20% (by weight) of the composition is polyvinylpyrrolidone. Preferred examples of such copolymers are Its molecular weight is 5,00
0 to 400.000.

The gelatin may be treated with lime or treated with teric acid, and may be ossein gelatin, bickskin gelatin, hydrogelatin, or modified gelatin obtained by esterifying or phenylcarbamoylating these gelatins.

In the binder, gelatin preferably accounts for 10 to 90%, more preferably 20 to 60%, and the polymer of the present invention preferably accounts for 5 to 90%, more preferably 10 to 80%. .

The binder may contain other polymeric substances,
Gelatin and a mixture of polyvinylpyrrolidone with a molecular weight of 1,000 to 400,000 and one or more other polymeric substances, gelatin and a molecular weight ffl of 5,000 to 400
A mixture of a vinylpyrrolidone copolymer of 0.0000°C and one or more other polymeric substances is preferred. Other polymeric substances that can be used include polyvinyl alcohol, polyacrylamide, polymethacrylamide, polyvinyl butyral, polyethylene glycol, polyethylene glycol ester, proteins such as cellulose derivatives, and polysaccharides such as starch and gum arabic. Natural substances such as These range from 0 to 85%, preferably from 0 to 85%.
It may be contained in an amount of 70%.

Note that the vinyl pyrrolidone polymer may be a crosslinked polymer, but in this case, it is preferable to crosslink it after coating it on a support (including the case where the crosslinking reaction progresses by leaving it naturally).

The amount of binder used is usually 0.0 per support In'.
05g to 100g, preferably 001g to 40g
It is. Further, the binder is preferably used in an amount of 0.1 to 10 g, more preferably 0.25 to 4 g, per 1 g of one unit of the dye-donating substance monomer.

The support used in the heat-developable photosensitive material of the present invention includes:
For example, polyethylene film, cellulose acetate film, polyethylene terephthalate film, synthetic brass ink film such as polyvinyl chloride, paper supports such as 1F2, photographic cardboard, printing paper, baryta paper and resin coated paper, etc.) can be used.

In particular, it is preferable that each ←t thermal solvent is added to the thermal phenomenon and photosensitive (original) material of the present invention.The thermal solvent of the present invention may be any substance that promotes thermal development and/or thermal transfer, and is preferably is a substance that is solid, semi-solid, or liquid at room temperature and dissolves or becomes a solvent in bangu by heating for 1 inch, and is preferably a urea derivative (for example, dimethylurea, jedilurea, phenylurea, etc.) or an amide derivative. , (e.g. acetamide, benzamide, etc.),
Examples include polyhydric alcohols (eg, 1.5-bentanediol, 1.6-bentanediol, 1.2-chlorohexaneol, pentaerythritol, trimethylrolethane, etc.), and polyethylene glycols. A detailed example is described in Japanese Patent Application No. 5L104249. These thermal solvents may be used alone or in combination of two or more.

In addition to the above-mentioned components, type additives may be added to the photothermographic material of the present invention, if necessary.

For example, as a development accelerator, U.S. Pat.
No. 40, No. 3,531.285, No. 4,012,
No. 260, No. 4゜060.420, No. 4,088
, 496 No. 4,207.392 Specifications, RD
No. 15733, No. 15734, No. 15734.

15776, special u (1985-130745, same 56
Alkali release agents such as urea and guanidium trichloroacetate described in No. 132332, etc.,
Organic acids described in US Pat. No. 12,700, US Pat. No. 3,667.9
Non-aqueous polar solvent compounds having -CO-, -so, -, -so- groups described in US Patent No. 3,438.
Meltfumer A-mer described in '776, U.S. Patent No. 3.66
6.477, and polyalkylene glycols described in JP-A-51-19525. In addition, as a color toning agent, for example, JP-A Nos. 46-4928, 46-6077, 49-5019, 49-5020, 49-
No. 91215, No. 49-107727, No. 5L252
No. 4, No. 50-67132, No. 50-67641,
No. 50-114217, No. 52-33722, No. 5
No. 2-99813, No. 53-1020, No. 53-55
No. 115, No. 53-76020, No. 53-12501
No. 4, No. 54-156523, No. 54-156524
No. 54-156525, No. 54-156526, No. 55-4060, No. 55-4061, No. 55-
Publications such as No. 32015 and West German Patent No. 2.14Q,
No. 406, No. 2,147,063, No. 2.220.
618, U.S. Pat. No. 3,080, 25413, U.S. Pat. No. 3,847.612, U.S. Pat. 2. Phthalazinone, phthalimide, pyrazolone, quinazolinone, N-hydroquinaphthalimide, penzogisazine, naphthoxazinedione, 2. 3-dihydro-1,3-
Oxazine-2,4-dione, oxazoline, aminopyrinone, hydroquinequinoline, aminoquinoline, isocarbostyryl, sulfonamide, 2H-1,3-benzothiazine-2°4-(3H)dione, hensitriazine, mercaptotriazole, di Examples include mercabutotetrazapentalene, phthalic acid, naphthalic acid, phthalamic acid, etc., mixtures of one or more of these with imidazole compounds, and at least one of acids or acid anhydrides such as phthalic acid, naphthalic acid, etc. Examples include mixtures of phthalazine and phthalazine compounds, and combinations of phthalazine and maleic acid, itaconic acid, quinolinic acid, gentinonic acid, and the like.

Also, JP-A-58-189628, JP-A No. 58-1934
3-amino-5-mercapto-1゜2.4-triazoles, 3-anruamino-5, described in Publication No. 60
-Mercapto-1,2,4-triazoles are effective.

Furthermore, as an antifoggant, for example,
No. 7-1111.3, JP-A-49-90118, No. 4
9-10724 tatami-darkness 4q-! 171'i+1 trace-between 5
n-InlolQ tatami-same, IQ-130720, same 5
No. 0-123331, No. 51-47419, No. 51-
No. 57435, No. 51-78227, No. 51-104
No. 338, No. 53-19825, No. 53-20923
No. 51-50725, No. 51-3223, No. 5
No. 1-42529, No. 51-81124, No. 54-5
Publications such as No. 182-1 and No. 55-93149, as well as British Patent No. 1,455,271 and U.S. Patent No. 3.8.
No. 85.968, No. 3,700,457, No. 4.
137,079, German Patent No. 4.138.265, West German Patent No. 2.617,907, or oxidizing agents (for example, N
- halogenacetamides, N-halogenosuccinimides, perchloric acid and its salts, inorganic peroxides, persulfates, etc.), or acids and their salts (such as sulfinic acids,
lithium laurate, rosin, diterpene acid, thiosulfonic acid, etc.), or sulfur-containing compounds (e.g., mercapto compound-releasing compounds, thiouracil, disulfide, simple sulfur, mercapto-!, 2,4-triazole, thiazolinthione, polysulfide compounds, etc.) ), and other compounds such as oxazoline, I, 2,4-triazole, and phthalimide. Furthermore, thiol (preferably a thiophenol compound) compound described in JP-A-59-111636 is also effective as another antifoggant. In addition, as an anti-fogging agent,
-56506 (e.g., di-ocdylhydroquinone, dodecanylhydroquinone, etc.) and hydroquinone derivatives and benzotriazole derivatives (e.g., 4-sulfobenzotriazole, 5-sulfobenzotriazole, etc.) described in Japanese Patent Application Nos. 59-66380. It can be preferably used in combination with carboquine (benzotriazole, etc.).

In addition, as a stabilizer, a printout preventive agent may also be used at the same time, especially after processing.
Halogenated hydrocarbons described in Publication No. 53-46020, specifically tetrabromobutane, tribromoethanol, 2-bromo-2-tolylacetamide, 2-bromo-2-tolylsulfonylacetamide, 2-tribromobutane, tribromoethanol, 2-bromo-2-tolylacetamide, 2-bromo-2-tolylsulfonylacetamide, Examples include bromomethylsulfonylbenzothiazole and 2,4-bis(tribromomethyl)-6-methyltrianone.

Antifoggants include hydroquinone derivatives (for example, di-t-octylhydroquinone, dodecanylhydroquinone, etc.) described in Japanese Patent Application No. 59-56506, hydroquinone transparent conductors described in Japanese Patent Application No. 59-66380, and benzene. It can be preferably used in combination with a triazole derivative (for example, 4-sulfobenzotriazole, 5-carboxybenzotriazole, etc.).

Also, Japanese Patent Publication No. 46-5393, Japanese Patent Publication No. 50-54329
A post-treatment may be carried out using a sulfur-containing compound as described in No. 50-77034.

Additionally, U.S. Patent No. 3.301. ．． No. 678, No. 3
, 506゜444, 3,824.103, and 3.844,788, as well as the isothiuronium stabilizer precursor described in U.S. Pat.
No. 669.670, No. 4,012.260, No. 4
．． It may contain the actylvator stabilizer precursor described in 060,420 and the like.

Also, Shi51! I5NH4Fe(SO4)t-1
A water release agent such as 21120 may also be used;
Heat development may be carried out by supplying water as in JP-A-56-132332.

In addition to the above-mentioned components, the heat-developable photosensitive material of the present invention may optionally contain various spectral sensitizing agents, antihalation dyes, optical brighteners, hardeners, antistatic agents, plasticizers, and spreading agents. Additives, coating aids, etc. are added.

The heat-developable photosensitive material of the present invention basically has (1
) A photosensitive silver halide, (2) a reducing agent, (3) a dye-providing substance, (4) a binder, and, if necessary, preferably (5) an organic silver salt. However, these do not necessarily need to be contained in a single photographic constituent layer; for example, the photosensitive layer may be divided into two layers, (1) and (2).
), (4), and (5) are contained in a photosensitive layer on one side, and a dye-providing substance (2) is contained in a layer on the other side adjacent to this photosensitive layer, so that they can react with each other. It may be contained separately in two or more photographic constituent layers as long as it is in a suitable state.

Furthermore, the photosensitive layer may be divided into two or more layers, such as a high-sensitivity layer and a low-sensitivity layer, and various photographic constituent layers such as an overcoat layer, an undercoat layer, a backing layer, an intermediate layer, or a single filter layer may be provided. may have.

The heat-developable photosensitive layer, protective layer, intermediate layer, undercoat layer, back layer, and other photographic constituent layers of the photosensitive material of the present invention can be prepared by a dipping method, an air knife method, a curtain coating method or the method disclosed in U.S. Pat. No. 3,681.
．． It can be produced by various coating methods such as the Hozobar coating method described in No. 294.

2 Additionally, if desired, two or more layers can be applied simultaneously by the methods described in US Pat. No. 2,761,791 and British Patent No. 837,095.

The above-mentioned components used in the photographic constituent layer of the thermal phenomenon light-sensitive material of the present invention are coated on a support, and the coating thickness after drying is preferably 1 to 1.000 μm, more preferably 3 to 1.000 μm.
It is 20 μm.

After the heat-developable photosensitive material of the present invention is imagewise exposed as it is,
Usually 80°C to 200°C, preferably 102°C to 170°C
With a temperature range of ℃! seconds to 180 seconds, preferably 1.
Color development can be achieved by simply heating for 5 seconds to 120 seconds.

Further, if necessary, the water-impermeable material may be tightly packed to develop the film, or the exposed surface may be preheated at a temperature in the range of 70°C to 180°C.

In the present invention, the temperature and time of the thermal phenomenon are also limited by the white nature of the sensitizing dye compared to known photothermographic materials. However, the sensitizing dye of the present invention disappears in 2 to 30 seconds at 120 DEG C. to 170 DEG C., so there is virtually no problem.

Various exposure means can be used for the photothermographic material according to the present invention. The latent image is obtained by imagewise exposure to radiation, including visible light. Generally, light sources used in ordinary color printing, such as tungsten lamps, mercury lamps, xenon lamps, laser beams, CRT beams, etc., can be used as the light source.

The heating means can be any method applicable to ordinary photothermographic materials, such as contacting with a heated block or plate, contacting with a heated roller or drum, or passing through a high temperature atmosphere. Alternatively, high-frequency heating may be used, and furthermore, in the photosensitive material of the present invention, a conductive layer may be provided in the image-receiving layer (element) for thermal transfer, and Joule heat generated by energization or a strong magnetic field may be utilized. You can also do it. The heating pattern is not particularly limited;
Child in advance! After A (preheating), apply the heating and filtering method again and heat at a high temperature for a short time or at a low temperature for a long time.
Continuous rising, falling, repeated heating, and even discontinuous heating are possible, but a simple pattern is preferable.

Alternatively, a method in which exposure and heating proceed simultaneously may be used.

In the present invention, as the image-receiving layer that receives the diffusible dye imagewise formed by image exposure and thermal processing of the photographic constituent layer, a material commonly used in this field can be used, such as paper. , cloth, plastic, etc. can be used, but preferably a support provided with an image-receiving layer containing a mordant or a compound that reduces dye-receiving ability is used.

As a particularly preferable image receiving layer, Japanese Patent Application No. 58-97907
Layer made of polyvinyl chloride and patent application No. 1983-
128600, which is made of polycarbonate and a plasticizer.

The image-receiving layer may be provided on the same support as the photographic constituent layer, in which case it may have a structure that can be peeled off from the photographic constituent layer after the dye has been transferred, or it may be provided on a separate support. Well, there are no particular restrictions on its formation, and any technique can be used.

As a support for image-receiving material, transparent support, opaque 1111
Any flexible support may be used, such as polyethylene terephthalate, polycarbonate, polystyrene, polyvinyl chloride, polyethylene, polypropylene film, and titanium oxide, sulfuric acid, etc. RC, which is made by laminating a thermoreversible resin containing a pigment on a support containing pigments such as barium, carbonate, talc, etc., or on baryta paper or other paper.
Examples include 14 supports in which an electron beam curable resin composition containing a pigment is coated and cured on paper or paper, and supports in which a coated layer containing a monovalent pigment is provided on these supports. It will be done. In particular, a support that has a pigment-containing electron beam curable resin directly or a pigment coating layer on paper, and an electron beam curable resin composition coated and cured on the pigment coating layer, can itself contain 6 resins. Since the layer can be used as an image-receiving layer, it can be used as is as an image-receiving paper.

Next, preferred embodiments will be presented for the purpose of better understanding of the present invention. Therefore, the present invention is not limited thereby.

<Embodiment-1> A photosensitive element including a photosensitive layer and an image receiving layer including an image receiving layer are supplied as separate sheets, and after being exposed to light on the photosensitive element, they are laminated with the image receiving element during a thermal phenomenon.

The element was coated with blue-sensitive silver 10-genide, yellow, and blue-sensitive silver on a subbed polyethylene terephthalate film support.
- a layer in which a chromogenic dye-providing substance, a silver salt reducing agent and a binder are combined, green-sensitive)\a layer in which silver halogenide, a magenta chromogenic dye-providing substance, an organic silver salt reducing agent and a binder are combined; and red photosensitive silver halide, /
It has a combination of anchromic dye-providing layers, a silver salt, a reducing agent and a binder, with an intermediate layer disposed between each layer and a protective layer disposed on the top layer.

At least one of the photosensitive silver halides is spectrally sensitized using the sensitizing dye of the present invention as a main component.

In particular, the sensitizing dye of the present invention is preferably applied to spectral sensitization of green-sensitive silver halide.

The sensitizing dye of the present invention may be added before, during, or after chemical sensitization, or at the time of preparing the coating solution. The addition method is water,
It is preferable to add it by dissolving it in an alcohol such as methanol or ethanol, or a solvent such as acetone or N,N-dimethylformamide. Appropriate addition amounts are as described above.

The image-receiving element is a paper support or a plastic support into which a white pigment such as titanium dioxide is incorporated, on which an image-receiving layer mainly composed of a polymer and, if necessary, a protective layer are provided. The polymers mentioned above can be used, but polyvinyl chloride and polycarbonate are particularly preferably used. After exposing the photosensitive area, it is laminated with an image receiving paper and processed through a thermal processing device such as a heat roller or a heat press.

The phenomenon temperature is 120°C to 170°C, and the phenomenon time is 1.5 seconds to 120 seconds. After the phenomenon is completed, the photosensitive element and the image receiving element are peeled off to obtain an image on the image receiving element.

<Embodiment-2> It has the same configuration as Embodiment-1, but the support of the image-receiving element is a transparent plastic deck, and a transparent color image (image) is obtained by exposure and thermal development.

<Embodiment 3> The same components as in Embodiment 1 are used, but the photosensitive element and the image receiving element are combined in advance into a unit, and the photosensitive element is exposed from the back side and then directly exposed to the heat roller,
It is developed using a heat developing device such as a heat press, and then both sorts are separated.

The rain sounds may be brought into close contact from the beginning, or may be arranged with a thin gap formed by a spacer member, and may be brought into close contact by applying a slight pressure during thermal development. The latter is preferable in terms of stability during storage.

<Embodiment-4> Directly on the image receiving element similar to embodiment-1, embodiment =
A one-sheet type heat-developable photosensitive material provided with each layer similar to the photosensitive element No. 1. After exposure and heat development, the exposed area is peeled off using adhesive tape or the like.

When processing is carried out in roll form, the photosensitive area can be peeled off continuously, so it is not necessarily necessary to use adhesive tape or the like.

<Embodiment-5> The photosensitive r? described in Embodiment-1 A thermochromic monochromatic photosensitive material that is made into a photosensitive element by coating only one layer of the above on a support and providing a protective layer. This includes the case where it is combined with a black color-forming dye-providing substance to form a black-and-white light-sensitive material.

〔Example〕

Hereinafter, the present invention will be explained in more detail with reference to Examples.
The present invention is not limited thereby.

[Example-I]

A coating solution based on the following formulation was applied onto a primed transparent polyethylene terephthalate film with a thickness of 100 μm to a film thickness of 87 μm.
A photosensitive area of a transfer type heat-developable color photosensitive material was prepared by applying the coating to a thickness of .mu.m. However, the silver bromide emulsion was spectral sensitized using the sensitizing dye of the present invention and a comparative sensitizing dye other than the present invention.

Sample No.,
I~No, 14.

Coating, heavy liquid formulation ゛Silver bromide emulsion (chemically sensitized) 11.8m
QLIO%a base agent aqueous solution 1.08
m (adjusted to pi-(5,5 with citric acid, 10 with water
00m12.

The third solution was prepared as follows.

Sulfobenztriazole silver dispersion "Sulfobenztriazole silver sodium salt 123.4
g 10% polyvinylpyrrolidone in 746gL water iooom (! Disperse this in a ball mill for 2 days to obtain a sulfobenztriazole silver dispersion.

Silver Bromide Emulsion - A silver bromide emulsion for comparison was prepared by the following method. 5
In Q0C, JP-A-57-92523, JP-A-57-92523
Using the mixer shown in Publication No.-92524, 20 g of ossein geladine, 10100 O of distilled water, and A solution containing ammonia, 500 mf2 of an aqueous solution containing 1.1 mol of potassium bromide, and 1 mol of silver nitrate were added. Aqueous solution C containing ammonia at 500 mC was simultaneously added while keeping the pAg constant.

The shape and size of the emulsion grains to be prepared are determined by pHlpAg and B.
Adjustment was made by controlling the addition rates of liquid and liquid C.

A silver bromide emulsion was prepared in this manner.

The obtained silver halide grains were monodisperse (coefficient of variation of grain size distribution 8%) and octahedral grains with an average grain size of 0.3 μm. This emulsion was washed with water and desalted. Emulsion yield is 800m
It was 12.

Prepared above 1. The silver halide emulsion was converted into 4-hydroquino-
6-Methyl-1,3,3a, sensitized with sodium thiosulfate in the presence of fuchtrazaindene, and further sensitized dyes according to the present invention shown in Table 1 and sensitizing dyes for comparison below. (D-64) was spectrally sensitized.

(D-64) Chemical sensitizer silver halide emulsion composition "Silver halide (in terms of silver) 381
gL gelatin 85g/35
The amount of 30mf2 sensitizing dye added is 8X 10 per mole of silver.
−'Mole.

Color-pigment-donating substance dispersion A/mouth pigment-providing substance (see below) 62.
5gL ethyl acetate 2008B
"10% geladine aqueous solution 315ml121
Sodium sulfonate 125m! After mixing and stirring 2 L water (348 m) and B solutions, solutions A and B were dispersed for 90 minutes using an ultrasonic homogenizer.

After that, remove the ethyl acetate and wash all the insects with water for 1000 m.
It was evening.

dye-donating substance (ill・ reducing agent Separately, an image receiving section was manufactured as follows.

Coat a coating liquid with the following recipe on photographic baryta paper to a film thickness of 100.
It was coated in micrometers and dried with hot air at 100°C for 3 minutes.

Coating solution formulation [polyhynylidene chloride 1009L in tetrahydrofuran 1000ml] Next, coat the above photosensitive area in 3.
After cutting to a size of 5cm x 14cm, performing wedge exposure, aligning with an image receiving part cut to the same size, 15
The film was developed at 0°C for 1 minute, and then both films were peeled off.

In addition, the same sample was spectral exposed and subjected to the same treatment to examine the state of spectral sensitization.

Table 1 shows the types of sensitizing dyes and experimental results.

Further, the stain is the value of the magenta reflection density in the fogged area.

1≧＼ or less, white □!゛,/Table-] had less staining after heat development than the comparative sensitizing dye (D-64).

Example 2 The photosensitive section prepared in Example 1 was combined with an image receiving section prepared as described below, and the same processing as in Example 1 was performed.

30 g/m2 of the following mixture was coated on one side of photographic base paper weighing 160 g/m' and then exposed to 11 M energy beams.
It was cured using a rad electron beam. The composition of the mixture is as follows.

-Shin Nakamura Chemical Co., Ltd. NK Ester EPM800 25 parts by weight Titanium dioxide (rutile type, average particle size 0.2 μm) 4at
A hardened layer was also provided on the back side of the T-paper using the same procedure.

The photographic base paper having the cured layer thus obtained was used as an image-receiving material.

The effects are shown in Table-2.

The following discussion) 0. ! 1. / Table 2 Table 2 shows that substantially the same results as in Example 1 can be obtained even when the electron beam cured resin layer is used as the image receiving layer.

〔Effect of the invention〕

According to the present invention, staining of an image obtained by a transfer type heat-developable photosensitive material in which a dye image is formed by transferring a dye formed or released by a thermal phenomenon is improved.

Note that the addition of sensitizing dyes 1 generally has a large effect on the sensitivity of light-sensitive materials, and in order to design light-sensitive materials with sufficient sensitivity, increasing the amount of sensitizing dyes added results in increased staining. However, this drawback is improved by the present invention.

Applicant: Roku Konishi Photo Industry Co., Ltd. Procedural Amendment November 21, 1985 1, Licensed Office Official 1985 Patent i! 1 No. 263565 2. Name of the invention: Transfer-type heat-developable photographic material 3, II jl: Person who does ■Relationship with the matter Patent applicant address: 1-26-2 Nishi-Shinjuku, Shinjuku-ku, Tokyo 191 Tokyo, Japan Konishiroku Photo Industry Co., Ltd., 1 Sakuracho, Kuchino City (Tel: 0425-83-152)
1) Patent Section 4...? 0 positive instruction date 5,! III Positive Month Unspecified; 1: No. 1 - Detailed Description of the Invention" column.

6. Contents of amendment The detailed description of the invention is amended as follows.

(1) Correct the official '-' on page 9, line 1 of ξJ1+2 as follows.

Claims (2)

[Claims] (1) A transfer type heat-developable color photographic light-sensitive material having a layer containing at least a photosensitive silver halide on a support, characterized in that the photographic light-sensitive material contains a sensitizing dye whose color disappears due to heat. A transfer-type heat-developable photosensitive material. (2) The transfer type heat-developable photographic material according to claim 1, wherein the sensitizing dye is a compound represented by the following general formulas [1] to [IV]. General formula [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, Z^1 represents an atom or atomic group necessary to complete the basic cyanine dye nucleus, and R^1 is a sulfo group or its salt , represents a sulfinocarbamoyl alkyl group which may be substituted with a sulfato group, a thiosulfato group, a cyano group, an arylsulfonyl group, an acyl group, or an alkyl group, and R^2 is a hydrogen atom or a carbon atom number of 1 to 4
represents an alkyl group, R^3 represents an atomic group necessary to complete the cyanine dye, X^■ represents an anion, and l
represents 0 or 1. ] General formula [II] ▲ Contains mathematical formulas, chemical formulas, tables, etc. It represents an acyl group of numbers 1 to 10, R^5 represents an atomic group necessary to complete the cyanine dye, X^■ represents an anion, and l represents 0 or 1. ] General formula [III] ▲ Contains mathematical formulas, chemical formulas, tables, etc. ▼ [In the formula, Z^3 represents an atom or atomic group necessary to complete the basic cyanine dye nucleus, and R^6 and R^7 a carboxyl group or a sulfo group, or a salt thereof, respectively;
Alternatively, it represents an acyl group having 1 to 10 carbon atoms, R^8 represents an atomic group necessary to complete the cyanine dye, X^■ represents an anion, and l represents 0 or 1. ] General formula [IV] ▲ Numerical formulas, chemical formulas, tables, etc. R_1_0 represents a carboxyl group or a sulfo group, or a salt thereof, n represents 0, 1 or 2, m represents 1 or 2, and Q together with the carbonyl group in the formula completes a heterocycle containing a nitrogen atom. Represents the required atomic group. ]