JPH0253049A - Thermodevelopable color photosensitive material - Google Patents

Abstract

PURPOSE:To obtain a positive type color picture having good color reproducibility and high optical density by incorporating a specified compd. as an electron transferring agent (ETA) in the subject material. CONSTITUTION:The compd. shown by formula I as ETA, is incorporated in the photosensitive material. In formula I, R1-R9 are each hydrogen atom or a group capable of substituting. The sum of the hydrophobic substituent group constant (log P) of the groups R1-R9 is <=2.5. The groups R1-R9 capable of substituting, are exemplified by hydroxyl, alkyl, alkoxy, alkylthio, aryl or aralkyl group, etc. Thus, the thermodevelopable color photosensitive material incorporated a pigment applying compd. to be reducible, has the improved color reproducibility, image density and (S/N) ratio.

Description

[Detailed Description of the Invention] <Industrial Q Application Field> The present invention is a book related to heat-developable color photosensitive materials,
In particular, the present invention relates to a heat-developable color photosensitive material with improved color reproduction and with which positive color images with high density can be obtained.

Background technology> Heat-developable photosensitive materials are well known, and for information about heat-developable photosensitive materials and their processes, see, for example, "Fundamentals of Photographic Engineering" Non-Silver Salt Photography Edition (published by Corona Publishing Co., Ltd.), page 4c. ~λj, U.S. Pat. No. 4, Azootat, etc.

Many methods have also been proposed for obtaining positive color images by heat development.

For example, US Patent No. O includes the so-called DR.
An oxidized compound of the R compound that does not have the ability to release a dye is made to coexist with a reducing agent, and the reducing agent is oxidized according to the exposure amount of silver halide by heat development, and the remaining unoxidized reducing agent is used to reduce the compound. Methods have been proposed to release diffusible dyes. In addition, European Patent Publication No. 2O71ft and Technical Report ♂7-6/Tata (Kokai Technical Report Vol. 1λ--Issue) disclose a heat developable positive using a new compound that releases a diffusible dye using a similar mechanism. An image forming method is described.

In the positive image forming method using the above-mentioned reducible dye-donating compound, an electron donor and an electron transfer agent are usually used together as the reducing agent.

Here, the electron transfer agent (hereinafter referred to as ETA) refers to a compound that is oxidized by silver halide and whose oxidized form has the ability to cross-oxidize an electron donor. Conventionally, such compounds include alkyl-substituted hydroquinones such as no-hydroquinone, t-butylno-hydroquinone, and J,j-dimethylhydroquinone, catechols, pyrogallols, and halogen-substituted compounds such as chlorohydroquinone and dichlorohydroquinone. -Idoquinones, alkoxy-substituted hydroquinones such as methoxynohydroquinone, and polyhydroxybenzene derivatives such as methylhydroxynaphthalene. Furthermore, methyl gallate, ascorbic acid, ascorbin? [I[class, N.

Q hydroxylamines such as N'-di(-monoethoxyethyl)hydroxylamine, pyrazolidones such as /-phenyl-5-Q zolidone, Hiro-methyl-Hiro-hydroxyylfk-/-phenyl-3-pyrazolidone, p- Amine phenols such as amine phenol, p-methylamine phenol, p-dimethylaminophenol, p-pyridinoaminophenol, ≠-dimethylamino-, O-dimethoxyphenol, N-methyl-p-7 22-diamine , N, N, N', N'-tetramethyl-p-
Many compounds are known, such as phenylene diamines, phenylene diamines such as Hiro-ethylamine mono- and 6-simethoxyaniline, reductones such as pyrodinohexose reductone and pyrodinohexose reductone, and hydroxytetronic acids. ing.

<Problems to be Solved by the Invention> However, in the heat-developable photosensitive material using the above-mentioned reducible dye-donating compound and an electron donor, the electron transfer agent has low diffusivity in a polar solvent (in water). When a low value is used, the image stain is high and R, G
In the following case, exposure is performed through a color separation filter ', B,
It has been found that there is a problem that staining is high in layers that should not originally develop color, and cloudiness of the color image occurs.

An object of the present invention is to improve the color reproducibility, image density, and S/N of a heat-developable color photosensitive material using a reducible dye-providing compound.

Means for Solving the Problems> An object of the present invention is to provide on a support at least a photosensitive silver halide, a binder, a non-diffusible dye-donating compound that releases a diffusible dye when reduced, and an electron-donating compound. In a heat-developable color photosensitive material having an electron transfer agent, the electron transfer agent (hereinafter sometimes referred to as ETA) has the following general formula (
This was achieved by a heat-developable color photosensitive material characterized by using the compound represented by 1).

General Formula (I) In the formula, R1 to R0 are hydrogen atoms or substitutable groups. However, the sum of the hydrophobic substituent constants 1oftP of R1 to R0 is less than or equal to j.

Examples of substitutable groups for R1 to 'EL include hydroxy groups, alkyl groups (e.g. methyl, ethyl, propyl, isopropyl, hydroxymethyl, hydroxyethyl),
Alkoxy groups (e.g. methoxy, ethoxy, butoxy)
, alkylthio groups (e.g. methylthio, ethylthio),
Examples thereof include aryl groups (eg, phenyl, tolyl, 3-methoxyphenyl, 3-acetylaminobuenyl≠-methanesulfonylaminophenyl), aralkyl groups (eg, benzyl), and the like.

R5-Rin. Substitutable groups include alkyl groups (e.g. methyl, ethyl, propyl, hydroxyethyl), alkoxy groups (e.g. methoxy, ethoxy), alkoxycarbonyl groups (e.g. methoxycarbonyl, ethoxycarbonyl), acylamide groups (e.g. acetamide, propionylamino), sulfonylamino groups (e.g. methanesulfonylamine), carboxyl groups, non-logon atoms (C
(I, Br, etc.), amine groups, hydroxy groups, etc.

In the present invention, these groups are combined to provide a hydrophobic substituent constant of 1.
o? The sum of P is ko! A compound represented by the following general formula (1) is used.

In the present invention, the hydrophobic substituent constant (5oPP) is n-
Octatool/It is the logarithmic value of the water partition coefficient, but the constant values of various substituents and the calculation method for their sum are described in Chemistry Area Special Issue/No. 2λ "Structure-Activity Relationships of Drugs" (Nankodo), page 7~
/□1o described in page J and defined in the present invention
The value of fP was also determined using this method.

The values of 1ofP of proxy substituents are shown below.

几□〜几、ni -C, H3 +o,ry -CH2(JH -/, 10 OH -/, J da R5-R0: 0CH3 One α CH3 -C(J2H -C(J2CH3 Br -NHCUCH3 -NH8O2CH3 -(J.H. NH2 In the present invention, lO of □~R9 yo and below, especially -i, o to 10-1 ~Select R0.

-〇, 0 +0.7/ +o, rt -0,32 -0,0/ +o, rt -〇, ri7 1/, /r -0,67 1/, JJ The sum of fP values is -0 O It has been found that compounds of general formula (1) are particularly useful for achieving the objects of the present invention.

When using the compound of general formula (1) as ETA, ET
The A precursor can also be used in a form in which the active site is blocked with a protecting group.

The ETA precursor referred to here does not have a developing effect during storage of the photosensitive material before use, but it is capable of developing ETA for the first time through the action of an appropriate activator (e.g., base, nucleophile, etc.) or heating. It is a compound that can be released.

This E 'I' A precursor has the reactive functional group of ETA blocked with a blocking group.Next, it does not have the function as ETA before development, but it can be treated under alkaline conditions or heated. Since the blocking group is further cleaved, it can function as an ETA.

Furthermore, as another type of ETA precursor,
As described in No. 2PIj7/, in order to prevent the loss of ETA during storage over time, an ETA precursor that gradually decomposes during storage and has the ability to supplement ETA was prepared for the ETA of the present invention and used together with ETA. It's okay.

As the above ETA precursor, for example, /-phenyl-3
- and 3-acyl derivatives of pyrazolidinone, -mono-aminoalkyl or hydroxylalkyl derivatives, hydroquinone, metal salts such as catechol (lead, cadmium, calcium, palladium), halogenated acyl derivatives of hydroquinone, In addition to oxazine and bisoxazine derivatives, lactone-type ETA# precursors, hydroquinone precursors having a 4-ammonium group, cyclohex--en-/, and 4L-dione-type compounds, compounds that release ETA by electron transfer reactions, Examples include compounds that release ETA through an intramolecular nucleophilic substitution reaction, ETA precursors blocked with phthalide groups, and ETA precursors blocked with indomethyl groups.

The above-mentioned ETA precursor is a known compound, for example, JP-A-Shoyoter/71r≠rr, JP-A No. 71r≠rr, JP-A No. ? -/r co ILt≠2, same j turf! Precursors of 7-phenyl-3-pyrazolidinones are described in No. -G.O.

The amount of ETA used in the present invention has a wide range, but especially 0.00/~ for silver halide! It is preferably mol, more preferably 0.0/-/molar.

Specific examples of the compound represented by the general formula [I] are shown below.

The compound of the present invention can generally be easily obtained by (1) condensation of hydrazine and acrylic acid ester or (n) condensation of hydrazine and r-hydroxycarboxylic acid.

In the present invention, a reducible dye-donating compound is combined with an electron transfer agent and an electron donor, a binder, and a silver halide emulsion to form a 7-unit photosensitive layer. The reducible dye-providing compound may be added to the same layer as the silver rognide emulsion, or may be added separately to adjacent layers. In the latter case, it is preferable from the viewpoint of sensitivity that the layer containing the reducible dye-providing compound is located below the silver halide emulsion layer.

In this case, the electron transfer agent and electron donor can be added to either the silver halide emulsion layer or the reducible dye-donating compound layer, but at least the electron transfer agent is present in the silver halide emulsion layer. preferable.

In the present invention, at least two sets of such photosensitive layers are used.

Normally, after full color reproduction, three sets of photosensitive layers with mutually different color sensitivities are provided. For example, there are three combinations of a blue-sensitive layer, a green-sensitive layer, and a red-sensitive layer, and a three-set combination of a green-sensitive layer, a red-sensitive layer, and an infrared-sensitive layer. Each color-sensitive layer can be arranged in various orders known for conventional color-sensitive materials.

Moreover, each of these color-sensitive layers may be divided into one or more layers as necessary.

Next, the reducible dye-providing compound used in the present invention will be explained.

The reducible dye-providing compound used in the present invention is preferably a compound represented by the following general formula (C-I).

PWR-(Time)t-Dye General formula (C-I) In the formula, PWR is reduced to -(Ttme)
A group that releases t Dye is true.

From TirneFiPWR-(Time)t-()ye
represents a group that releases f)ye through a subsequent reaction after being released as f).

t represents an integer of 0 or 9/.

Dye represents the dye and 1fc represents its precursor.

First, I will explain KPWRK in detail.

PWR 戊U.S. Patent≠, /3ri, No.3t, or U.S. Patent≠, /35P, No.37, Dokei, talI, 177
No., Tokukai Akira! Tar/IjtJ33, same 7-417≠
J3, which corresponds to the part containing an electron-accepting center and an intramolecular nucleophilic tIt substitution reaction center in a compound that releases a photographic reagent by an intramolecular nucleophilic substitution reaction after being reduced as follows. Also, U.S. Patent Law, 2
No. 32,707, JP-A-ShojP-10/A≠No., Research Disclosure (/rit4t)■, 24102!
As disclosed in Japanese Patent Application Laid-open No. Shoj/-112!7, an electron-accepting quinonoid center in a compound that eliminates a photographic reagent through an electron transfer reaction within the molecule after being reduced, and the combination thereof with a photographic reagent. It may correspond to a part containing bonding carbon atoms. Also, Unexamined Japanese Patent Publication No. 130, U.S. Patent ≠, J4tj, 19
Aryl group substituted with an electron-withdrawing group in a compound whose single bond is cleaved to release a photographic reagent after reduction as disclosed in No. 3, Dokei, No. 6/RI, No. LRQ, and the combination thereof with a photographic reagent. It may correspond to a moiety containing a connecting atom (sulfur atom, carbon atom, or nitrogen atom). Also, as disclosed in U.S. Pat. It may also be a US patent≠
This corresponds to the geminal dinitro moiety in the dinitro compound that beta-desorbs the photographic reagent after electron acceptance and the carbon atom-containing moiety that connects it to the photographic reagent described in No. 410. It's okay.

In addition, compounds having 5o2-X (X represents any of rI!, sulfur, or nitrogen) and an electron-withdrawing group in one molecule as described in the patent application Sho AJ-10tl#j, 4.2
-7041ri! There is a po-x bond (
(X has the same meaning as above) and an electron-withdrawing group, patent application No. 7.2-104? ? c-x in one molecule written in No. 7
Examples include compounds having a 'bond (X' is synonymous with X or represents -5O2-) and an electron-withdrawing group. J-J/9. It is described in Riri issue, 4J-32077/fc! Compounds that cleave the single bond and release Dye after reduction due to the π bond conjugated with the child-accepting group can also be used.

In order to more fully achieve the object of the present invention, the general formula (C
Among the compounds represented by -I), those represented by the general formula (Cut) are preferred.

General formula (CHI) (T i me+, Dy e is R101, R10
2) Binds with at least one of the EAGs.

The portion corresponding to PW in the general formula (CIO) will be explained.

X represents a group (-NCR''3)-) containing an oxygen atom (-0-), a sulfur atom (-8-), or a nitrogen atom.

PLlol, R102 and 几103 represent a group other than a hydrogen atom or a simple bond.

Groups other than hydrogen atoms represented by 几, R% and R include alkyl groups, aralkyl groups, alkenyl groups, alkynyl groups, aryl groups, heterocyclic groups, sulfonyl groups, carbamoyl groups, sulfamoyl groups, etc. may have a substituent.

Preferred examples of R101 and R103 include substituted or unsubstituted alkyl groups, alkenyl groups, alkynyl groups, aryl groups, heterocyclic groups, acyl groups, and sulfonyl groups. B1
The number of carbon atoms in 01 and R103 is preferably / to 1/-O.

R102 is preferably a substituted or unsubstituted acyl group or sulfonyl group. Examples include the acyl group and sulfonyl group mentioned for R101 and B103. The number of carbon atoms is preferably l-HiroO.

B 101, R102 and R103 may be combined with each other to form a hill or ring.

As X, enzymes are particularly preferred.

EAG will be described later.

Furthermore, in order to achieve the object of the present invention, the general formula (CII
) Among the compounds represented by the formula (Cull), those represented by the general formula (Cull) are preferred.

General formula (C1n) General formula (A) In general formula (A), (bonds to at least one of Time+Dye ViREAG).

X has the same meaning as above.

R104 represents an atomic group that is bonded to the x and g1 atoms to form a monocyclic or condensed heterocycle of five or more members including the nitrogen atom.

EAG has a group that accepts or takes electrons from a reducing substance and is bonded to a nitrogen atom. EAG is preferably a group represented by the following general formula (A).

V represents an atomic group forming a 3- to 3-member aromatic group together with Z Z , and n represents an integer from 3 to t.

v3;-25-1v, , 7.37.4-1■5
;-z -z -z -v6:-z3-z.

z 5-z , -1v7. -z3-z, -z5-z6-
z7-V8i-Z3-Z, -Z5-Z.

-27-28-.

-(J--8-1 or 180□-'f, fi, S
Each of ub represents a simple bond (pi bond), a hydrogen atom, or a substituent described below. Subs may be the same or different,
They may also be bonded to each other to form a saturated or unsaturated carbocyclic or heterocyclic ring.

In general formula (A), the sum of the Hammett substituent constant sigma/R of the substituents is +0.10 or more, more preferably +0
．． 70 or more, most preferably 10.

Select Sub so that it is 25 or more.

EAG is preferably a ring group or a heterocyclic group substituted with at least one electron-withdrawing group. Substituents bonded to the aryl group or heterocyclic group of EAG can be used to control the physical properties of the entire chemical compound. Examples of physical properties of the entire compound include ease of accepting electrons, water solubility, oil solubility, diffusibility, sublimation, melting point, dispersibility in binders such as gelatin, and resistance to nucleophilic groups. It can be used to adjust reactivity, reactivity toward electrophilic groups, etc.

A specific example of EAG is described in European Patent Publication No. 07/07/AJ, pages 1-7.

Time may lead to the cleavage of nitrogen-oxygen, nitrogen-nitrogen S, or nitrogen-sulfur bonds, and D via subsequent reactions.
Represents a group that releases ye.

Various groups represented by T im e are known, for example, in JP-A-Kokai Shobu/-/Gua2gu≠Pages (5)-(6);
/-λ34j ≠ Issue (8) Page-64, Patent Application 1976/-t
Examples include the groups described on page 1621 (36) (Hirogu).

Dyes include azo dyes, azomethine dyes, anthraquinone dyes, naphthoquinone dyes, styryl groups, nitro dyes, quinoline dyes, carnyl dyes, and phthalocyanine dyes. It should be noted that these dyes can also be used in the form of temporarily shortened wavelengths that are capable of producing multiple colors.

Specifically, EP7j, 44PjA issue, Tokukai Sho! Tar 7
Dye disclosed in No. 610jμ can be used.

The compound represented by the above general formula (Cn) (CI[I) must itself be immobile in the photographic layer,
Therefore, the number of carbons in EAG, R, R R1°4 and Hx position (EAG position in %)!
It is desirable to have the above ballast group.

Specific examples of the reducible dye-providing compound used in the present invention are listed below, but the present invention is not limited thereto. Dye-providing compounds described in ♂7-4/Tata et al. can also be used.

(the law of nature (JCH8 (4’) (the law of nature (l/) (/Ko) NH8O2C1(.

(ri) R: -11 These compounds can each be synthesized by the methods described in the patent specifications cited above.

The amount of the dye-donating compound to be used depends on the extinction coefficient of the dye, but is 0.0j-j mmol/m, preferably 0.7 to 5.
It is in the range of 3 mmol/m2.

The dye-donating substances can be used alone or in combination. In addition, in order to obtain images of black or different hues, silver halide may be added to each cyan, magenta, and yellow dye-providing substance by at least /ya as described in JP-A No. 1257/1257. It is also possible to use a mixture of one or more dye-providing substances that release mobile dyes having different hues, such as by mixing and containing them in a layer or an adjacent layer.

Electron donors are used in the present invention, and details of these compounds are described in European Patent Publication No. 074ttA-, Publication Branch No. 17-4/Tata, and the like. A particularly preferable electron donor (or its precursor) is the following general formula (
C) or CD).

General Formula [D] In the formula, A and AlO2 each represent a hydrogen atom or a protecting group for a phenolic hydroxyl group that can be deprotected with a nucleophile.

Here, the nucleophilic reagents include anionic reagents such as (JHe, ROe (R; alkyl group, aryl group, etc.), hydroxamic acid anions 803'θ, and/or primary amines, dorazine, hydroxylamine, etc.). Examples include compounds with lone pairs of electrons, such as alcohols, thiols, and the like.

Preferred examples of A101 and AlO2 include a hydrogen atom, an acyl group, an alkylsulfonyl group, an arylsulfonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a dialkylphosphoryl group, a dialkylphosphoryl group, or JP-A-Sho! Tatar No. 7037, Tatar 20
It may be a protecting group disclosed in No. 1OJ, and
is 101% 102 If possible, R201, R2°2, 203 and 204 may be bonded to each other to form a ring. MafcA
1o□ and A102fi may be the same or different.

, 几 , R and R204 are each a hydrogen atom, an alkyl group, an aryl group, an alkylthio group, an arylthio group, a sulfonyl group, a sulfo group, a halogen atom, a cyano group, a carbamoyl group, a sulfamoyl group, an amide group,
Imide group, carboxyl group, sulfonamide group, etc.
FEwasu. These groups may have a substituent if possible.

However, the total carbon number of R201 to R204 is t or more. Further, in the general formula (C), R201 and R203 and/or R203 and R204, and/or FiR203 and R204 may combine with each other to form a saturated or unsaturated ring.

In the general formula [C) 1fc, among the electron donors represented by [D], those in which at least two of 几201 to 几204 are substituents other than hydrogen atoms are preferable. Particularly preferred compounds are those in which at least one of R201 and 202, and at least one of R2O3 and 204 are f substituents other than hydrogen atoms.

A plurality of electron donors may be used in combination, or an electron donor and its precursor may be used in combination. Further, the electron donor may be the same compound as the reducing substance of the present invention. Specific examples of the electron donor will be listed, but the invention is not limited to these compounds.

(ED-J) (ED-J) (ED-a) (ED-j) (ED-/) (ED-bu) (ED-10) H (ED-7) (ED-//) (ED- 4) (ED-/J) (ED-/μ) Among the above, 124A-dialkyl-substituted idokuquinones are preferred. This alkyl group includes those further substituted.

The amount of the electron donor (or its precursor) to be used has a wide range, but is preferably 0.5% (F) per 7 moles of the positive dye-donating substance.
07 mole ~ 0 mole, especially 001 mole ~! The preferred range is on the molar scale. Also, 0.001 mol to 1 mol of silver halide IIC! Moles - preferably from 0.01 mols
1. ! It is a mole.

In order to introduce the reducing substances, dye-donating substances, electron donors, electron transfer agents or their precursors and other hydrophobic additives of the present invention into the hydrophilic colloid layer, high-boiling organic solvents such as alkyl phthalates can be used. Esters (dibutyl phthalate, dioctyl 7-thale N!F), phosphate esters (
diphenyl 7 phosphate, triphenyl phosphate, tricyclohexyl phosphate, tricresyl phosphate, dioctyl butyl 7 phosphate),
Citric acid esters (e.g. acetyl tributyl citrate), benzoic acid esters (e.g. octyl benzoate), alkylamides (e.g. diethyl laurylamide), fatty acid esters (e.g. dibutoxyethyl succinate),
Dioctyl azelate), trimesate esters (e.g. tributyl trimesate)%
Carboxylic acids described in No. 00, JP-A-Shojterr3-no! Hirogo, same jP-/7rlA! / issue, same 1? -/711/-j
- No., same! Tar/No. 711713, same! Tar/714
c! Number 4, same! Tar / 714 inches! Same issue! ? -/7
1μ! U.S. Patent No. 13 using the compounds described in No. 7 and the like.

Using the method described in No. 027, or boiling point 3o'
Organic solvents of C to "c", such as lower alkyl acetates such as ethyl acetate and butyl acetate, ethyl propionate, secondary butyl alcohol, methyl in butyl ketone,
It is dissolved in β-ethoxyethyl acetate, methyl cellosolve acetate, cyclohexanone, etc., and then dispersed in a hydrophilic colloid. The above-mentioned high boiling point organic solvent and low boiling point organic solvent may be mixed and used. Furthermore, after dispersion, the low boiling point organic solvent can be removed by ultrafiltration or the like as required. The amount of high boiling point organic solvent is IO? Below, preferably! is below. Also, j for the diffusion-resistant reducing agent /f? Below, preferably one? It is as follows. Furthermore, it is appropriate that the amount of the high boiling point organic solvent / to the binder /2 be below, preferably below o, zt, more preferably below 0.3r. Mata Tokkoaki! /-32113, Tokukai Sho! /-! The polymer dispersion method described in Tata ≠ No. 3 can also be used. It can be directly dispersed in the local agent, or it can be dissolved in water or alcohol and then dispersed in gelatin or in an emulsion.

In the case of a compound that is substantially insoluble in water, it can be dispersed and contained in the form of fine particles in the binder in addition to the method described above. (For example, JP-A No. 74c130, No. 13-
102733, Japanese Patent Application No. 102733, Japanese Patent Application No. 102733, etc.) When dispersing a hydrophobic substance in a hydrophilic colloid, various surfactants can be used. For example, JP-A-1989-
The following surfactants are listed in pages (37) to (3r) of the /j7tJ issue and can be used.

The heat-processable photosensitive material of the present invention basically has a photosensitive silver halide, a binder, an electron donor, an electron transfer agent, and a reducible dye-donating compound on a support. Depending on the situation, an organic metal salt oxidizing agent or the like may be included. These components are often added to the same layer, but if they are in a reactable state, they can be divided and added to separate layers. For example, if a colored dye-providing compound is present in the lower layer of the silver halide emulsion, a decrease in sensitivity can be prevented. It is preferable that the reducing agent be incorporated into the photothermographic material, but it may also be supplied from the outside, for example by diffusing it from a dye fixing material, which will be described later.

In order to obtain a wide range of colors in the chromaticity diagram using the three primary colors yellow, magenta, and cyan, K uses a combination of at least three silver halide emulsion layers each sensitive to a different spectral region.

For example, there are combinations of three layers including a blue-sensitive layer, a green-sensitive layer, and a red-sensitive layer, and a combination of a green-sensitive layer, a red-sensitive layer, and an infrared-sensitive layer. Each photosensitive layer can be arranged in any order known for conventional color photosensitive materials.

Further, each of these photosensitive layers may be divided into co-layers or more as necessary.

The heat-developable photosensitive material can be provided with various auxiliary layers such as a protective layer, an undercoat layer, an intermediate layer, a yellow filter layer, an antihalation layer, and a back layer.

Silver halides that can be used in the present invention include silver chloride, silver bromide,
Any of silver iodobromide, silver chlorobromide, silver chloroiodide, and silver chloroiodobromide may be used.

The silver halide emulsion used in the present invention is a surface latent image type emulsion. A surface latent image type emulsion is an emulsion in which latent images are mainly formed on different surfaces of grains, and is also called a negative type emulsion. The definition of surface latent image emulsion is written by Tokkosho! It is described in the r-tahiro io publication.

The silver halide emulsion of the present invention may be a so-called core-shell emulsion in which the grain interior and the grain type layer have different phases. The silver halide emulsion may be monodisperse or polydisperse, or a mixture of monodisperse emulsions may be used. Particle size is O87
~λμ, %KO, -2~/, jμ is preferred. The crystal habit of the silver halide grains may be cubic, hedahedral, heptahedral, tabular with a high aspect ratio, or any other form.

Specifically, U.S. Patent Nos. Year),! #Kaisho 6---! Any of the silver halide emulsions described in No. Jljz etc. can be used.

Although the silver halide emulsion may be used unripe, it is usually used after being chemically sensitized. Emulsions for conventional light-sensitive materials can be manufactured using the well-known sulfur sensitization method, reduction sensitization method, noble metal sensitization method, etc.
The following can be used in combination. These chemical sensitizations can also be carried out in the presence of a nitrogen-containing heterocyclic compound (Japanese Unexamined Patent Publication No. 10-120013-λj3/j).

The coating amount of the photosensitive silver halide used in the present invention is in the range of 19 to 1017 m2 in terms of silver.

In the present invention, an organic metal salt can also be used as an oxidizing agent together with photosensitive silver halide.

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

Organic compounds that can be used to form the above-mentioned organic silver salt oxidizing agents include U.S. Patent No. V, JOO.

Otoko≦No.! Ko~! There are benzotriazoles, fatty acids, and other compounds described in column 3, etc. Also, Japanese Patent Application Publication No. 1973-/
Silver salts of carboxylic acids having an alkynyl group such as silver phenylpropiolate described in /J2JJ-, and JP-A-61
-Acetylene silver described in Kohiro O Hiromu is also useful. These or more types of organic silver salts may be used in combination.

The above-mentioned organic silver salts are as follows: per 7 mol of photosensitive silver halide,
O1θ/ to 10 mol, preferably /'iO.

A combination of 0/1 to 1 mole can be used. The total coating amount of photosensitive silver halide and organic silver salt is 5otny in terms of silver.
A suitable distance is between 1017m and 1017m.

Various antifoggants or photographic stabilizers can be used in the present invention. For example, 几D/7t
l/-3 (1971)! 4 (~u) are listed on page o Azoles and azaindenes, JP-A-Sho! Tar/t1
Nitrogen-containing carboxylic acids and phosphoric acids described in No. 4t4-, or JP-A-Sho! Turf/1Mercapto compounds and metal salts thereof described in JJJ, JP-A Shobu-47rij7
Acetylene compounds described in , etc. are used.

The silver halide used in the present invention may be spectrally sensitized with methine dyes and others. The pigments used include cyanine pigments, merocyanine pigments, composite cyanine pigments, composite merocyanine pigments, holopolar cyanine pigments,
Included are hemicyanine dyes, styryl dyes and hemioxonol dyes.

Specifically, US Pat. No., R
D/702? (1971) /J~/3 pages and the like.

These sensitizing dyes may be used alone or in combination, and combinations of sensitizing dyes are often used particularly for the purpose of one-strong color sensitization.

Along with the sensitizing dye, the emulsion may contain a dye that does not itself have a spectral sensitizing effect or a compound that does not substantially absorb visible light and exhibits supersensitization (for example, as described in US Pat. , 411゜t≠No. 7, those described in Japanese Patent Application Sho t/-Kota Kota≠, etc.).

These sensitizing dyes may be added to the emulsion at or before chemical ripening, and may be added to the emulsion at the time of chemical ripening or before or after chemical ripening.
It may be carried out before or after nucleation of silver halide grains according to No. 71, Vol. JJj, No. 444. The amount added is generally about lo-8 to 10 moles per mole of silver halide.

A hydrophilic binder is preferably used for the constituent layers of the photosensitive material or dye fixing material. An example of this is Tokukai Sho tco 2!3/! Examples include those described on pages (cobu) to (-l) of the issue.

Specifically, transparent or translucent hydrophilic binders are preferred, and include natural compounds such as proteins such as gelatin, gelatin spindles, cellulose derivatives, starch, polysaccharides such as gum arabic, textolan, pullulan, etc.
Examples include polyvinyl alcohol, polyvinylpyrrolidone, acrylamide polymer, and other synthetic polymer compounds. In addition, the super absorbent polymer described in JP-A No. 6260, etc., namely -〇〇〇M Manenha-8 (J3M
Homopolymers of vinyl monomers having (M is a hydrogen atom and an alkali metal) or co-S combinations of these vinyl monomers with each other or with other vinyl monomers (e.g. sodium methacrylate, ammonium methacrylate, Sumitomo Chemical Sea Bream Sumikagel) L −jH) is also used. These binders can also be used in combination of one or more types.

When employing a system that performs thermal development by supplying a small amount of water, the use of the above-mentioned super absorbent polymer makes it possible to quickly absorb water. In addition, when a highly water-absorbing polymer is used in the dye-fixing layer or its retainer, it is possible to prevent the dye from being re-transferred from the dye-fixing material to other materials after transfer.

In the present invention, the amount of binder applied is preferably less than or equal to 7 m2, particularly IO? It is appropriate to set the value to 71 or less.

The constituent layer (including the back layer) of the photosensitive material or dye-fixing material K is made of various polymers for the purpose of improving film properties such as dimensional stabilization, prevention of curling, prevention of adhesion, prevention of film cracking, and prevention of pressure sensitivity. It can contain latex. in particular,! ! ! f Kaisho tλ--≠yo-! ? It is possible to use any of the polymer latexes described in the same No., Otsuko/3bu6hiro, No.7J-/100bu3, etc. In particular, if a polymer latex with a low glass transition point (≠00C or less) is used in the mordant layer, cracking of the mordant layer can be prevented, and if a polymer latex with a high glass transition point is used in the back layer, curling can be prevented. Effects can be obtained.

In the present invention, a compound that activates development and stabilizes images can be used in the light-sensitive material. For specific compounds that are preferably used, please refer to the US Pat.
o, t, 2 as the number of the issue! /~! - is described in the column.

In systems that form images by diffusion transfer of dyes, dye fixing materials are used together with photosensitive materials. The dye fixing material may be coated separately on a support separate from the light-sensitive material, or may be coated on the same support as the light-sensitive material. The relationship between the light-sensitive material and the dye-fixing material, the relationship with the support, and the relationship with the white reflective layer is described in U.S. Patent No. μ.

zoo, t, 2 as issue number! The relationship described in column 7 is also applicable to the present application.

The dye fixing material preferably used in the present invention has at least one layer containing a mordant and a binder. As the mordant, those known in the photographic field can be used, and specific examples thereof include U.S. Pat.
Column 79 ('% mordant described in Kaisho ti-itλjA No. (3-) to (Reference/) pages, JP-A-Sho 2-ri ≠ Hiro O ≠ 3,
Same 12-. 2! Examples include those described in the No. 03. Maku, U.S. Patent No. 4tAJ, 072
Dye-receiving polymeric compounds such as those described in the above may be used.

The dye fixing material may be provided with auxiliary layers such as a protective layer, a release layer, and an anti-curl layer, if necessary.

In particular, it is useful to provide a protective layer.

A high boiling point organic solvent can be used in the constituent layers of the light-sensitive material and the dye-fixing material as a plasticizer, a slippery agent, or a peelability improver between the light-sensitive material and the dye-fixing material. Specifically, Tokukai Sho Otko 2!3/! No. 2, page (-j), 1-2 Buddhas! There are some listed in No. 3.

Furthermore, for the above purpose, various silicone oils (all silicone oils from dimethyl silicone oil to modified silicone oil in which various organic groups are introduced into dimethylsiloxane) can be used. As an example, various modified silicone oils described in "Modified Silicone Oil" Technical Bulletin 1Pj-/rBK published by Shin-Etsu Silicone ■, particularly carboxy-modified silicone (trade name: X-Ikko 3710), are effective.

In addition, the Japanese Patent Publication No. 1983-aizyzi, the Japanese Patent Application No. 1986-1-co Jt.
The silicone oil described in No. 17 is also effective.

Antifading agents may be used in the photosensitive materials and dye fixing materials. Examples of anti-fading agents include antioxidants, ultraviolet absorbers, and metal complexes.

Examples of antioxidants include chroman compounds, coumaran compounds, phenol compounds (for example, hindered phenols), hydroquinone derivatives, hindered amine derivatives, and spiroindane compounds. [Compounds described in Japanese Patent Application Publication No. 2003-110001-1/-/J9t441t are also effective.

Benzotriazole compounds (
U.S. Patent No. J, jJJ, No. 72, etc.), Hiro-theacylidone compounds (U.S. Patent No. 3,3ja, tri, etc.)
, benzophenone compounds (JP-A No. 4TT-Kore≠ etc.), other JP-A No. 4A-Hiro IjJJ, JJ-
/Jjbu 4/L/ issue, same 4/-1t! There are compounds listed in Item B, etc.

Further, the ultraviolet absorbing polymer described in JP-A No. 6-atoiz-1 is also effective.

Examples of metal complexes include U.S. Pat. , JP-A-Sho tJ-/74t74
(/issue, same a/-rrszt issue (core) to (-ta) pages,
There are compounds described in Japanese Patent Application Sho.

An example of a useful anti-fade agent is JP-A-Sho t2-λ/! Ko7ko (
/Jj) to (/77) pages.

The anti-fading agent for preventing fading of the dye transferred to the dye-fixing material may be included in the dye-fixing material in advance, or may be supplied to the dye-fixing material from outside the photosensitive material. .

The above antioxidants, ultraviolet absorbers, and metal complexes may be used in combination.

A fluorescent whitening agent may be used in the light-sensitive material or the dye-fixing material. It is preferable that the fluorescent whitening agent is incorporated into the dye-fixing material or supplied from outside the light-sensitive material. As an example, K.

Edited by Veenkataraman [The Chemis]
tryof 5ynthetic DyesJ
Compounds described in Vol. More specifically, examples include stilbene compounds, coumarin compounds, biphenylene/'-based compounds, benzoxacylyl compounds, naphthalimide compounds, pyrazoline compounds, and carbostyryl compounds.

Fluorescent brighteners can be used in combination with antifade agents.

Hardeners used in the constituent layers of photosensitive materials and dye-fixing materials include U.S. Patent No. μ, No. 671,73, column 4, JP-A-Sho! Tar//ltj! No. 2, 24t! Kootsu/No.,
Hardeners described in J/-/r94 No. 2 and the like can be mentioned. More specifically, aldehyde hardeners (formaldehyde, etc.), aziridine hardeners, epoxy hardeners, etc.), vinylsulfone hardeners (N, N'-ethylenebis(vinylsulfonylacetamide)) ethane, etc.), N-methylol hardeners (dimethylol urea, etc.), or polymer hardeners (JP-A-6λ-254t1j
Compounds described in No. 7 etc.) can be mentioned.

Various surfactants can be used in constituent layers of photosensitive materials and dye fixing materials for purposes such as coating aids, improving peelability, improving slipperiness, preventing static electricity, and promoting development. Specific examples of surfactants are disclosed in JP-A No. 4,2-/73≠t3, JP-A No.
13≠j7, etc.

The constituent layers of photosensitive materials and dye-fixing materials include improved slipperiness,
An organic fluoro compound may be included for the purpose of preventing static electricity and improving peelability. A typical example of an organic fluoro compound is Tokko Sho! 7-ta OjJ No. r~/column 7, JP-A-Sho t/-
, 20Plf4 No., tco/111co No.2, etc., or oily fluorine compounds such as fluorine oil, or solid fluorine compound resins such as tetrafluoroethylene resin, etc. Examples include hydrophobic fluorine compounds.

A matting agent can be used in the photosensitive material and the dye fixing material. As a matting agent, silicon dioxide, polyolefin or polymethacrylate may be used.
In addition to the compounds described on page A (-ta), benzoguanamine resin beads, polycarbonate resin beads, A8 resin beads, etc. are also available in Japanese Patent Application No. Sho JJ-/100bu≠, No. 4J-/1
00t! There are compounds described in this issue.

In addition, the constituent layers of the light-sensitive material and the dye-fixing material may contain a thermal solvent, an antifoaming agent, an antibacterial agent, colloidal silica, and the like. Specific examples of these additives are given in Japanese Unexamined Patent Application Publication No. 1973/1989.
It is described in No. 1123rt, pages (-6) to (3).

In the present invention, an image formation accelerator can be used in the light-sensitive material and/or the dye-fixing material. Image forming promoters include promoting redox reactions between silver salt oxidizing agents and reducing agents, promoting reactions such as production of dyes from dye-donating substances, decomposition of dyes, and release of diffusible dyes, and photosensitive materials. It has functions such as promoting the movement of dye from the layer to the dye fixed layer, and from a physicochemical perspective, it has the following functions: base, base precursor, nucleophilic compound, high boiling point organic solvent (oil), thermal solvent, and surface activity. Silver ions are classified as compounds that interact with silver ions. However, these substance groups generally have multiple functions and usually have some of the above-mentioned promoting effects. For details on these please refer to US Patent ≠, A7F
, is written in the 73rd whistle 3r-ao column.

Examples of base precursors include salts of organic acids and bases that are decarboxylated by heat, compounds that release amines by intramolecular nucleophilic substitution reaction, Rossen rearrangement, or Beckmann rearrangement. Specific examples thereof are described in U.S. Pat.

In a system in which thermal development and dye transfer are performed simultaneously in the presence of a small amount of water, it is preferable to include a base and/or a base precursor in the dye fixing material in order to improve the storage stability of the photosensitive material.

In addition to the above, combinations of a poorly soluble metal compound and a compound (referred to as a complex-forming compound) that can react to form a complex with a metal ion constituting the hardly soluble metal compound described in European Patent Publication No. 10,660, JP-A-6/-27j4tj
Compounds that generate bases by electrolysis as described in No. 1 can also be used as base precursors. The former method is particularly effective. It is advantageous to add the poorly soluble metal compound and the complex-forming compound to the light-sensitive material and the dye-fixing material separately.

Various development stoppers can be used in the light-sensitive material and/or dye-fixing material of the present invention in order to always obtain a constant image despite fluctuations in processing temperature and processing time during development.

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

Specifically, an acid precursor that releases acid upon heating;
Examples thereof include electrophilic compounds that undergo a substitution reaction with coexisting bases when heated, nitrogen-containing heterocyclic compounds, mercapto compounds, and precursors thereof.

For more details, see JP-A-12-23-3/j issue (3/)~
It is described on page (3-).

As a support for the light-sensitive material or dye-fixing material of the present invention, one that can withstand several degrees of processing is used. Common examples include paper and synthetic polymers (films). Specifically, polyethylene terephthalate, polycarbonate, polyvinyl chloride, polystyrene, polypropylene,
Polyimide, cellulose a (for example, triacetylcellulose) or films containing pigments such as titanium oxide, film-based synthetic paper made from polypropylene, synthetic resin valves such as polyethylene, and natural pulp. Mixed paper, Yankee paper, baryta paper, coated paper (particularly cast coated paper), metal, cloth, glass, etc. are used.

These can be used alone, or can be used as a support laminated on one or both sides with a synthetic polymer such as polyethylene.

In addition to this, there are also
/) can be used.

A hydrophilic binder, alumina sol, a semiconductive metal oxide such as tin oxide, carbon black or other antistatic agent may be applied to the surface of these supports.

Methods of exposing and recording images on photosensitive materials include, for example, directly photographing landscapes and people using a camera, exposing through reversal film or negative film using a printer or enlarger, and using a copying machine. A method in which the original image is scanned and exposed through a slit using an exposure device, etc. A method in which image information is transmitted via an electric signal to a light emitting diode, various lasers, etc. for exposure; There are methods of outputting the image to an image display device such as a spray or plasma display and exposing it directly or through an optical system.

As light sources for recording images on photosensitive materials, as mentioned above, natural light, tungsten lamps, light emitting diodes, laser light sources, CRT light sources, etc. are used, as described in US Patent No. G, J00. It is possible to use the light source described in the A section of the Buichi Delta No. 1 whistle.

Further, image exposure can also be performed using a wavelength conversion element that combines a nonlinear optical material and a coherent light source such as a laser beam. Here, nonlinear optical materials are materials that can exhibit nonlinearity between the polarization and electric field that appear when a strong optical electric field such as a laser beam is applied, and include lithium niobate, potassium dihydrogen phosphate (KDP) ), lithium iodate, inorganic compounds such as B a B 204, urea derivatives, nitroaniline derivatives, such as 3-
Methyl-Hiro-nito a pyridine-N-oxide (P(JM
) and the compounds described in JP-A-Shoj/-jJ44J- and JP-A-1-2IO-Ko-3- are preferably used.

As the form of the wavelength conversion element, single crystal optical waveguide type, fiber type, etc. are known, and both are useful.

In addition, the above-mentioned image information can be obtained from an image signal obtained from a video camera, an electronic still camera, etc., a television signal substituted for the Nippon Television Signal Standard (NTSC), or an original image obtained by dividing it into a large number of pixels using a scanner. image signal, CG,
Image signals created using a computer such as CAD can be used.

The photosensitive material and/or the dye-fixing material may have a conductive heating layer as a heating means for heat development or diffusion transfer of the dye.

In this case, the transparent or opaque heating element is
/-/'IJJ-≠Those described in the specification of No. j can be used. Note that these conductive layers also function as a band prevention layer.

The heating temperature in the heat development process ranges from approximately 10°C to approximately -10°C.
It can be developed at approximately
c is useful. The dye diffusion transfer step may be performed simultaneously with the heat development, or may be performed after the heat development step is completed. In the latter case, the heating temperature in the transfer process can be in the range from the temperature in the heat development process to room temperature;
It is more preferable that the temperature be 0 or more and up to about 100C lower than the temperature in the heat development step.

Dye migration can also be caused by heat alone, but a solvent may be used to promote dye migration.

Also, Tokukai Akira! Turcono Ir Hiro≠3, same A/-aJr
A small amount of solvent (especially water), as detailed in the ozt issue etc.
Also useful is a method in which development and transfer are performed simultaneously or sequentially by heating in the presence of. In this method, the heating temperature is preferably at least to'C and at most the boiling point of the solvent; for example, when the solvent is water, it is preferably at least Viro'C and at most 1000C.

Examples of solvents used to accelerate development and/or transfer the diffusible dye to the dye fixing layer include water as a primary aqueous solution containing an inorganic alkali metal salt or an organic base (such as a basic aqueous solution containing an inorganic alkali metal salt or an organic base). For example, those described in the section of image formation accelerators can be used. Furthermore, a low boiling point solvent or a mixed solution of a low boiling point solvent and water or a basic aqueous solution can also be used. Further, a surfactant, an anti-capri agent, a complex-forming compound with a sparingly soluble metal salt, etc. may be included in the solvent.

These solvents can be used in a method of applying them to dye fixing materials, photosensitive materials, or both.

The amount used may be as small as less than the weight of the solvent corresponding to the maximum swelling volume of the entire coating (particularly less than the weight of the solvent corresponding to the maximum swelling volume of the entire coating minus the weight of the entire coating).

As a method of applying a solvent to the photosensitive layer or the dye fixing layer, for example, JP-A-Sho≦/-/! There is a method described on page 7j4t4. Further, the solvent can be incorporated in advance into the photosensitive material, the dye fixing material, or both, such as by encapsulating the solvent in microcapsules.

Furthermore, in order to promote dye transfer, a method may be adopted in which a hydrophilic thermal solvent that is solid at room temperature and dissolves at high temperature is incorporated into the t-photosensitive material or the dye fixing material. The hydrophilic thermal solvent may be incorporated into either the photosensitive material or the dye fixing material.
It may be built into both. The layer that contains it is also an emulsion layer,
Any of the intermediate layer, protective layer, and dye fixing layer may be used, but it is preferable that the dye fixing layer and/or the dye fixing layer be built into an adjacent layer.

Examples of hydrophilic heat solvents include ureas, pyridines, amides, sulfonamides, imides, alnyls, oximes, and other heterocycles.

Further, in order to promote dye transfer, a high boiling point organic solvent may be included in the light-sensitive material and/or the dye fixing material.

Heating methods in the development and/or transfer process include contact with a heated block or plate, contact with a hot plate, hot presser, heat roller-halogen lamp heater, infrared and far-infrared lamp heater, etc. , passing through a high-temperature atmosphere, etc.

The pressure conditions and method of applying pressure when overlapping the photosensitive material and the dye-fixing material and bringing them into close contact are described in JP-A-67-7μ72.
The method described on page ≠μ issue (-7) can be applied.

Processing of the Photographic Elements of the Invention Any of a variety of KFi thermal development equipment can be used. For example, Tokukai Akira! Turf J Kohiro No. 7, same jP-/77j! No. 7, same jter/No. 11313,
Same 40-/1r9j1 issue, Jitsukai Shoul Ko! The apparatus described in Hari et al. is preferably used.

〔Example〕

Hereinafter, the present invention will be specifically explained with reference to Examples.

<Example 1> A method for preparing emulsion (I) for the first layer will be described.

A well-stirred gelatin aqueous solution (gelatin λOf5 potassium bromide l?, and OH (CH2) in 100 m of water)
28 (0M2) 20Ho and tf were added and kept warm at zo 0c, and the following solutions (1), (n) and (III) were simultaneously added at equal flow rates over 30 minutes. In this way, a monodisperse cubic emulsion adsorbed with a dye having an average grain size of 0.1-μ was prepared.

After washing with water and desalting, lime-treated ossein gelatin-01 was added to adjust the pHtl-6, II, pAgtr, and JVC%, and then kept warm at OoC, and sodium thiosulfate 7μ and chloroauric acid 0.07% aqueous solution Add d2 ≠-Hydroxy-t-methyl-/, J, Ja, 7-chitrazaindene and Hiroshi! Carefully perform chemical sensitization for a minute. The yield of emulsion is tJf
It was t.

Dye (a) Dye (b) Triethylthiourea/, 6tlli and μm hydroxy-4-methyl-/, J, 3a, 7-titrazaindene 100 ~, and the ripening time was 13 minutes. Also, the yield of this emulsion is 63? Met.

(Drug A) Next, the emulsion (n) for the third layer will be described.

A well-stirred aqueous solution (gelatin in water 7301)
〇■, potassium bromide 0.30? , sodium chloride t? and the following drugs kO, 07! The following solutions (I) and (n) were simultaneously added at equal flow rates over 10 minutes. (1) After the addition of the solution, a methanol solution (III) of the following sensitizing dye was added.

In this way, a monodisperse cubic emulsion adsorbed with a dye having an average grain size O0≠5μ was prepared.

After washing with water and desalting, gelatin and 2Of were added, and the pH was adjusted to t and μ.
, pAg to 7. After adjusting to r, Ao.

Chemical sensitization was performed with OoC. The chemicals used at this time were (sensitizing dye C), lium, chloroauric acid, and goohydroxy-4-methyl-/,
Next, optimally chemically sensitized by adding J, Ja, 7-chitrazaindene. In this way, a monodisperse hedral silver iodobromide emulsion (/J-) 600f with an average grain size of o and to .mu.m was obtained.

Next, a method for preparing emulsion (III) for the j-th layer will be described.

Gelatin 3θi% potassium bromide 311 and HU (C
H2)2S(CH2)28(OH2)2(J)10,!
? The following solutions (1) and (II) were added simultaneously over 40 minutes. Thereafter, the following solutions (1) and (ry') were added simultaneously over 30 minutes. After washing with water and desalting, right ash treated ossein gelatin - 〇? Add and adjust the pH to 66Js pAg! Next, we will discuss how to make a gelatin dispersion of a dye-donating substance. Yellow dye donor *(1) -〇? , electron donor (ED-2) i3. t
y, tricyclohexyl phosphate-t10?1f
PJk, add ethyl acetate J7tttl, and heat at about 30°C.
The mixture was heated and dissolved to form a homogeneous solution. This solution and a 70% solution of lime-treated gelatin/10? , water 6jtte and sodium dodecylbenzenesulfonate/, 7? After stirring and mixing, use a homogenizer for 10 minutes at 1100 OO
Dispersed with rp. This dispersion is called a yellow dye-providing substance dispersion.

Dispersions of magenta and cyan dye-providing substances are similar to dispersions of yellow dye-providing substances.
/l).

With these, color photosensitive material 1 with multilayer structure shown in Table
I made 0/.

Water-soluble polymer (1) cage polymer( 1)” Surfactant (1)” Aerosol CIT Surfactant (-)” Surfactant (3)” Antifoggant (1) Screen C (JC5H, 1 Anti-capri agent (λ)” Surfactant (4A)” Hardener ( 1)” / 2-bis( vinyl sulfonylacetate toamide) ethane High boiling point organic solvent ( nourishment to Licyclohexyl phosphate Electron transfer agent ( 1) to ! Total sum of 02P = +3 /7) Next, we will discuss how to make the dye fixing material.

A dye fixing material R-i was prepared by coating on a paper support laminated with polyethylene according to the composition shown in the following table.

Table - Composition of dye fixing material Surfactant 2 Aerosol OT Surfactant 3 Surfactant 4 Surfactant 5 Silicone oil 1 Polymer ax 5 Vinyl alcohol sodium acrylate copolymer (7J
-/JJ- molar ratio) Polymer "7" Dextran (molecular weight 70,000) Mordant "6 802 and high boiling point organic solvent 18 Rheofuosta! (Manufactured by Ajinomoto ■) Hardener “9 /\ (C)12)4÷(J-CH2-C)i-C)12)
2 Mantle agent "10 benzoguanamine resin (average particle size l!μ)" Next, the electron transfer agent (1) used in photosensitive material 10/
ETAX-J, X-//, X-JJ, X-jA of the present invention
Photosensitive materials IO- to IO-106 having exactly the same compositions were prepared, except that the same moles were changed.

B and G, in which a tungsten bulb is used in the above-mentioned multilayered color photosensitive material, and the density changes continuously.

Exposure was carried out at 1000 lux for 7770 seconds through dark and gray color separation filters.

While the exposed photosensitive material was being fed at a linear velocity of -omm 7'sec, water of /jrd/m was supplied to the emulsion surface using a wire bar, and then immediately superimposed so that the image-receiving material and the film surface were in contact with each other.

The temperature of the water-absorbed membrane was adjusted to rz 0c using a heat roller, and /! Heated for seconds. Next, when it was peeled off from the image-receiving material, clear colors of blue, green, red, and gray were evenly obtained on the damaged material, corresponding to the B, G%R, and gray color separation filters.

Furthermore, when a color photosensitive material 10/~ioz < is exposed using a spectrograph through a wedge whose density changes continuously in the direction perpendicular to the wavelength, and then the same process is performed, the wavelength is Correspondingly, blue, green, and red colors are sure to give you a ctorogram.

The results of measuring the densities of cyan and magenta in the blue light area, cyan and yellow in the green light area, and magenta and yellow in the red light area, as well as the cyan, magenta, and gray parts of the gray areas during exposure and development using a color separation filter. Yellow maximum density (Dmax), minimum! 1 degree (Dmin) is shown in Figure 3.

In [True 3], when comparing the photosensitive materials ioi to 10j, there is no noticeable difference in Dmin for gray exposure. When comparing the density of magenta), ioz, ioa, 1o4t, i
The values increase in the order of oz and ioi, which is due to the ET used.
A's 1ofIP value is followed. #OPP value is 10 in %
! At 10/, which greatly exceeds , the magenta # degree is O, aO
It can be seen that the color reproducibility is deteriorated.

<Example 2> Using the same emulsion, dye-donating substance, electron donor, and electron transfer agent as in color photosensitive material 10/ of Example/, a multilayer color photosensitive material 20/ having the configuration shown in the table was prepared. . [Omotehiro] Unless otherwise specified, the same additives as those used in the photosensitive material ioi were used.

Please note that the organic silver salt emulsion was prepared as follows.

Gelatin-O? and acetylaminophenylprobiolic acid! ,the law of nature? 0. /% sodium hydroxide water fg solution 1
000J and ethanol co00ydVCFJ. The solution was kept at ≠00C and stirred. In this solution, silver nitrate≠,
A solution of jf dissolved in water-00m! Added in minutes. Excess salt was then removed by sedimentation. Then the pH was adjusted to t,
・Yield 300 according to 3? An organic silver salt dispersion was obtained.

Further, an antifoggant precursor (1) having the following structure was added in 0.2 times the molar amount to the dye-donating substance, and both the dye-donating substance and the ME electron donor were dispersed in oil using the method of Example 1.

Electron transfer agent (-)” CH3 Antifoggant precursor (1)” C (JNHCl, H33(b) Hot solvent (1)” Benzene sulfonamide Base precursor (1)” μm chlorphenylsulfonylacetate quanidine Next, how to make the dye fixing material (R-a) will be described.

Poly(methyl acrylate: ff-N,N,N-trimethyl-N-vinylbenzylammonium chloride) (
The ratio of methyl acrylate and vinylbenzylammonium chloride is /:/) Dissolve 10f in water of 00g,
Next, mix uniformly with 100 ml of 10% lime-treated gelatin. A hardening agent was added to this mixture, titanium dioxide was dispersed, and the mixture was uniformly coated to a wet film thickness of Poμm on a paper support laminated with polyethylene. After drying this sample, it is used as a dye fixing material (R-x) having a mordant layer.

Next, the electron transfer agent (, 2) of the photosensitive material -O/ was added to ETAX-J, X-bu, X-73, and X-23 of the present invention, respectively.
A photosensitive material with exactly the same composition as -〇/ except that equimolar amounts were replaced with -〇-~40! were created respectively.

In the same manner as in Example 1, the photosensitive material was exposed using a color separation filter and a spectral wedge, and then heated uniformly for 30 seconds on a heat block heated to O0C.

Film side tic/m of dye fixing material (R-J) J per m
After supplying Om of water, the heat-treated photosensitive materials were stacked on the fixing material so that the film surfaces were in contact with each other.

The line speed/comm is applied to the laminator heated to ro 0c.
After passing through the material at a speed of m/sec, both materials were peeled off to form a skin.

As in Example/, the Dmax/Dm of each color of the gray part of the nine-sensitive material exposed to light using a color separation filter
For photosensitive materials that have been spectral exposed to the in value,
B, G, each color density of 8 parts [I! ].

Similar to Example/, ETAO used in this Example as well.
It can be seen that color turbidity decreases according to the lofP value.

Patent applicant: Fuji Photo Film Co., Ltd.
2tt7tla

Claims (1)

[Scope of Claims] A heat-developable color having on a support at least a photosensitive silver halide, a binder, a non-diffusible dye-donating compound that releases a diffusible dye when reduced, an electron donor, and an electron transfer agent. A heat-developable color photosensitive material comprising a compound represented by the following general formula [I] as the electron transfer agent. General formula [I] ▲There are numerical formulas, chemical formulas, tables, etc.▼ In the formula, R_1 to R_9 represent a hydrogen atom or a substitutable group. However, the hydrophobic substituent constant log of R_1 to R_9
The sum of P is 2.5 or less.