JP2604254B2 - Color photosensitive material - Google Patents

Description

Description: FIELD OF THE INVENTION The present invention relates to a color light-sensitive material, and more particularly to obtaining a positive color image having a high maximum image density, low stain, and excellent color reproducibility. The present invention relates to a color light-sensitive material capable of forming a color image.

(Background Art) Many methods have been proposed for obtaining a positive color image.

For example, U.S. Pat.No.4,559,290 discloses a so-called DRR compound in the form of an oxidized form having no dye releasing ability in the presence of a reducing agent or a precursor thereof, and oxidizing the reducing agent in accordance with the exposure amount of silver halide by development, A method has been proposed in which a diffusible dye is released by reduction with a reducing agent remaining without being oxidized. In addition, European Patent Publication No. 220746, Published Technical Report 87
-6199 (Vol. 12, No. 22) discloses a compound capable of releasing a diffusible dye by a similar mechanism by reductive cleavage of an NX bond (X represents an oxygen atom, a nitrogen atom or a sulfur atom). A color light-sensitive material using a compound that releases a sex dye is described.

However, the above color light-sensitive material which gives a positive color image has not reached the level of a commercially available color print material, particularly in the stain on the white background of the image.

In the positive photosensitive material, in order to improve the stain on the white background, it is necessary to increase the consumption rate of the reducing agent by silver development in the exposed portion as much as possible. To do this,
A method of increasing the amount of an electron transfer agent, and a method disclosed in
No. 1, 62-182738, JP-A-1-456552, etc., and a method using a development accelerator releasing type redox compound can be considered. However, the former method causes a problem that the color reproducibility is remarkably deteriorated because the concentration of the electron transfer agent in the initial stage of development is increased. Also, in the latter method, not only the exposed portion, but also fog development of the unexposed portion is promoted,
It was found that there was a problem that D _max was greatly reduced.

<Problems to be Solved by the Invention> An object of the present invention is to improve the discrimination and color reproducibility of a color photographic material using a reducible dye-providing compound.

<Means for Solving the Problems> An object of the present invention is to provide at least a photosensitive silver halide, a binder, a non-diffusible dye-donating compound which emits a diffusible dye upon reduction, and an electron donor. The present invention has been attained by a color light-sensitive material having an electron transfer agent, wherein the color light-sensitive material further comprises at least one compound represented by the following general formula [I] or [II].

General formula [I] XL _{1 t} Dev General formula [II] XL _{2 v} YL _{3 w} Dev In the general formula [I], X represents an oxidation-reduction nucleus, and is oxidized during the development process. It is a group that makes it possible to emit L _{1 t} Dev.

L ₁ represents a group that cleaves Dev after cleavage from X.

In the formula (II), X represents a redox nucleus, and represents a group that is oxidized during development to cleave L _{2 v} YL _{3 w} Dev, and L ₂ is YL after cleavage from X. Y represents a group that cleaves _{3 w} Dev, Y represents a group that cleaves L _{3 w} Dev by being oxidized after cleavage, and L ₃ represents a group that cleaves Dev after cleavage from Y.

t, v, and w each represent 0 or 1. Dev is
It represents a group that functions as an electron transfer agent after being released from L _{1 t} Dev or L _{3 w} Dev.

Hereinafter, the compounds of the general formulas [I] and [II] will be described in detail.

The group represented by X in the general formulas (II) and (II) undergoes an oxidation-reduction reaction with the exposed silver halide or the electron transfer agent radical, and subsequently undergoes alkali hydrolysis to give L _{1 t} Dev, or Represents a group that releases L _{2 v} YL _{3 w} Dev. Examples of such groups are described in
Examples thereof include groups such as hydroquinone derivatives, aminophenol derivatives, naphthalene diol derivatives, aminonaphthol derivatives, and hydrazine derivatives as described in 1-145652.

Among these groups, preferred specific examples are shown in the following formulas [Va] to [Vf] and [VIa] to [VIc].

Where * is L _{1 t} Dev or L _{2 v} YL _{3 w} De
Represents the position to join with v.

In the above formula, R ₁₁ is a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, a cyano group, an alkoxycarbonyl group, a carbamoyl group, a sulfamoyl group, a carboxyl group, Sulfo group, sulfonyl group, acyl group, carbonamide group, sulfonamide group,
Represents a hydroxy group, an acyloxy group or a heterocyclic group, and when there are two or more R _{11 s} , they may be different from each other;
It may form a 7-membered non-benzene hydrocarbon ring or a 5- to 7-membered hetero ring. R ₁₂ represents an alkyl group, an aryl group, an acyl group, a carbamoyl group, a sulfonyl group or a sulfamoyl group. T ₁ represents a hydrogen atom or a group capable of being hydrolyzed and removed under alkaline conditions. In the molecule
It may be different from each other if the T ₁ there are two. Representative examples of T ₁ include a hydrogen atom, an acyl group, a sulfonyl group, an alkoxycarbonyl group, a carbamoyl group, an oxalyl group, and the like.

[VIa] R ₂₁ NHNH-R ₂₂ - * In the formula, R ₂₁ is a substituted or unsubstituted alkyl group (preferably having 20 or less carbon atoms. For example, methyl, ethyl, propyl, i-propyl, butyl, i-butyl, t-butyl,
Hexyl, t-amyl, octyl, t-octyl, decyl, dodecyl, hexadecyl, octadecyl, alkoxymethyl, halogenomethyl group, etc., aryl group (preferably having 20 or less carbon atoms, for example, phenyl, tolyl, xylyl, halogenophenyl, alkoxy) Phenyl, cumyl,
Anisyl, mesityl, naphthyl group), or a Hajime Tamaki (number 20 or less carbon atoms preferably, for example represents pyridyl, quinolyl, isoquinolyl, methylpyridyl, furyl, thiophenyl, etc. group), R ₂₂ is -SO -., - SO ₂ -, R ₂₃ represents a mere bond or R ₂₇ , R ₂₄ represents R
A group with the same meaning as ₂₁ , Represents a group or a hydrogen atom, a group or a hydrogen atom of the same meaning as R ₅ and R _21, R ₂₆ represents a nitro group, a cyano group, a carboxyl group, a sulfo group, or -R ₂₂ -R ₂₃ -R _21,
R ₂₇ represents an oxygen atom, a sulfur atom or an NR ₂₁ group.

The functions of the groups represented by the general formulas [VIa], [VIb] and [VIc] are considered as follows. These groups react with an oxidized developing agent to oxidize -NHNH- to -N = N-. -N = N- is electron withdrawing compared to -NHNH-. As a result of a group represented by the general formula [VIa] reaction of nucleophilic species occurs against R _22. As a result, the group bonded to the * mark is cleaved. When -N = N- is generated in the groups represented by the general formulas [VIb] and [VIc], the hydrogen atom at the β-position of the bond indicated by * is activated, and the acidity is increased.
As a result, β-elimination occurs, and the group bonded to the * mark is cleaved.

Each of the groups represented by L _{1 to} L ₃ represents a divalent linking group and may have a timing control function.

Each of t, v, and w represents 0 or 1, and when 0, it represents that they are bonded without via the linking groups L _{1 to} L ₃ .

When the divalent linking group represented by L _{1 to} L ₃ has a timing control function, L _{1 to} L ₃ release a bonded leaving group through one or more steps of reaction. Represents a group.

As the divalent linking group represented by L _{1 to} L ₃ , for example, a leaving group (in the intramolecular ring closure reaction of a p-nitrophenoxy derivative described in U.S. Pat. No. 4,248,962 (Japanese Patent Application Laid-Open No. 54-145,135)). Those which release A); those which release A by an intramolecular ring closure reaction after ring cleavage described in U.S. Pat. Nos. 4,310,612 (JP-A-55-53,330) and 4,358,525;
U.S. Pat.Nos. 4,330,617, 4,446,216, and 4,483,919
Which release PUG with the formation of an acid anhydride by an intramolecular ring-closure reaction of a carboxyl group of a succinic acid monoester or an analog thereof described in JP-A-59-121,328;
U.S. Pat. Nos. 4,409,323 and 4,421,845, Research Disclosure No. 21,228 (December 1981), U.S. Pat. No. 4,416,977 (JP-A-57-135,944), JP-A-58-20
Nos. 9,736, 58-209,738, etc., which produce quinomonomethane or an analog thereof by electron transfer via a double bond conjugated with an aryloxy group or a heterocyclic oxy group to release A; US Patent No. 4,420,554 (JP-A-57-136,640), JP-A-57-135,945, and JP-A-57-188,035
Which release A from the γ-position of enamine by electron transfer of a portion having an enamine structure of a nitrogen-containing heterocyclic ring described in JP-A-57-598, JP-A-58-98,728 and JP-A-58-209,737;
U.S. Patent No. 4,1437, No. 4,837, which releases A by an intramolecular ring closure reaction of an oxy group generated by electron transfer to a carbonyl group conjugated to a nitrogen atom of a nitrogen-containing heterocyclic ring described in US Pat.
No. 6,396 (JP-A-52-90932), JP-A-59-93,442, JP-A-59-75475, etc., which release A with formation of aldehydes; JP-A-51-146,828 No. 57-179,842
Having the structure of -O-COOCR _a R _b -A, accompanied by decarboxylation and subsequent formation of aldehydes. What releases A; JP-A-60-7,4
No. 29, which releases A with generation of isocyanate; U.S. Pat. No. 4,438,193, etc., which releases A by a coupling reaction with an oxidized form of a color developing agent. .

The group represented by Y in the general formula [II] is XL _{2 v}
It represents a group that is further cleaved to be a redox group, and is preferably a group represented by the following general formula [VII].

(VII)

* -P- (E = F) _n -QB wherein P and Q each independently represent an oxygen atom or a substituted or unsubstituted imino group, and at least one of n E and F is (L ₃ ) represents a methine group having _w- Dev as a substituent, other E and F represent a substituted or unsubstituted methine group or a nitrogen atom, and n represents an integer of 1 to 3 (n E, n F represents the same or different ones), and B represents a hydrogen atom or a group which can be removed by an alkali. Where P, E,
The case where any two substituents of F, Q and B are linked to form a divalent group to form a cyclic structure is also included. For example
(E = F) This is the case where _n forms a benzene ring, a pyridine ring or the like.

When P and Q represent a substituted or unsubstituted imino group, it is preferably a sulfonyl group or an imino group substituted with an acyl group.

 At this time, P and Q are represented as follows.

General formula (N-1) General formula (N-2) Here, the * mark indicates the position that bonds to B, and the ** mark indicates-
(E = F) represents the position where one of the free bonds of _n- is bonded to one.

In the formula, a group represented by G is a linear or branched, chain or cyclic, saturated or unsaturated, substituted or unsubstituted aliphatic group having 1 to 32, preferably 1 to 22 carbon atoms (eg, methyl,
Ethyl, benzyl, phenoxybutyl, isopropyl), a substituted or unsubstituted aromatic group having 6 to 10 carbon atoms (eg, phenyl, 4-methylphenyl, 1-naphthyl, 4-dodecyloxyphenyl, etc.), or A 4- to 7-membered heterocyclic group selected from a nitrogen atom, a sulfur atom or an oxygen atom as a hetero atom (for example, a 2-pyridyl group, a 1-phenyl-4-imidazolyl group, a 2-furyl group, a benzothienyl group, etc.) Is a preferred example.

In the general formula [VII], P and Q are preferably each independently an oxygen atom or a group represented by the general formula (N-1).

When B represents a group which can be removed by an alkali (hereinafter, referred to as a precursor group), preferably, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group,
Hydrolyzable groups such as carbamoyl group, imidoyl group, oxazolyl group, sulfonyl group, U.S. Pat.
No. 029, a precursor group of the type utilizing the reverse Michael reaction, U.S. Pat.No. 4,310,612, a precursor group of the type utilizing an anion generated after the ring cleavage reaction as an intramolecular nucleophilic group, U.S. Pat. No. 3,932,480
No. 3,993,661, a precursor group in which an anion is electron-transferred through a conjugated system and thereby causes a cleavage reaction, and a cleavage reaction is caused by electron transfer of an anion reacted after ring opening described in U.S. Pat.No.4,335,200. Precursor groups or U.S. Pat.
No. 10,618, a precursor group utilizing an imidomethyl group.

In the general formula [VII], it is preferred that p represents an oxygen atom and B represents a hydrogen atom.

In the general formula [VII], more preferably, E and F are substituted or unsubstituted methine groups except when E and F are methine groups having-(L ₂ ) _w -Dev as a substituent. It is time.

Particularly preferred groups represented by the general formula [VII] are those represented by the following general formulas [VIII] or [IX].

In the formula, * represents a position bonding to X- (L ₁ ) _v ;
The asterisk indicates the position where (L ₂ ) _w -Dev is bonded.

R ₃₁ represents a substituent, and q represents an integer of 0, 1 to 3. When q is 2 or more, two or more R _{31 's} may be the same or different, and when two R _{31' s} are substituents on adjacent carbons, they each become a divalent group to link to form a ring structure. The case where it expresses is also included. In that case, it becomes a benzene condensed ring, for example, naphthalenes, benzonorbornenes, chromans, indoles, benzothiophenes,
Ring structures such as quinolines, benzofurans, 2,3-dihydrobenzofurans, indanes, and indenes, which may further have one or more substituents. Examples of preferred substituents when these fused rings have a substituent, and R when R ₃₁ does not form a fused ring
Preferred examples of ₃₁ are as follows.

That is, an alkoxy group (eg, methoxy group, ethoxy group, etc.), an acylamino group (eg, acetamido group,
Benzamide group), sulfonamide group (eg, methanesulfonamide group, benzenesulfonamide group, etc.), alkylthio group (eg, methylthio group, ethylthio group, etc.), carbamoyl group (eg, N-propylcarbamoyl group, Nt-butylcarbamoyl) Group, Ni-
A propylcarbamoyl group), an alkoxycarbonyl group (eg, a methoxycarbonyl group, a propoxycarbonyl group, etc.), an aliphatic group (eg, a methyl group, a t-butyl group, etc.), a halogen atom (eg, a fluoro group, a chloro group, etc.), A sulfamoyl group (eg, N-propylsulfamoyl group, sulfamoyl group, etc.), an acyl group (eg, acetyl group, benzoyl group, etc.), a hydroxyl group,
Examples thereof include a carboxyl group and a heterocyclic thio group (for example, a 1-phenyltetrazolyl-5-thio group, a 1-ethyltetrazolyl-5-thio group, and the like). A typical example of the case where two R ₃₁ are linked to form a cyclic structure is (* And ** have the same meaning as described in formula [IX]).

When the group represented by -Dev is bonded in the state of general formula (I) or (II), the active site is blocked and the compound does not show developing activity, but when released, develops silver halide. Represents an electron transfer agent residue having the ability to Although the electron transfer agent used in the present invention will be described later, as the electron transfer agent used for the group represented by -Dev, as described in claim (2), the following general formula [III] or [ The 1-phenyl-3-pyrazolidone derivative represented by IV] is preferred.

In the formula, each of R _{1 to} R ₄ is a hydrogen atom or a substituted or unsubstituted alkyl group (preferably having 20 or less carbon atoms. For example, methyl, ethyl, propyl, butyl, t-butyl,
Hydroxymethyl, hydroxyethyl, acetoxymethyl, chloromethyl, cyanoethyl, etc.), aryl group (preferably having 20 or less carbon atoms, for example, phenyl, tolyl,
Xylyl, methoxyphenyl, chlorophenyl, carboxyphenyl, cyanophenyl, cumyl, pseudocumyl, aminophenyl, bromophenyl, naphthyl, etc., and a heterocyclic group (preferably having 20 or less carbon atoms, such as pyridyl, furyl, quinolyl, thiophenyl, methylpyridyl, etc.) ).

R represents a substituted or unsubstituted aryl group (preferably having 20 or less carbon atoms; for example, phenyl, tolyl, xylyl, methoxyphenyl, chlorophenyl, carboxyphenyl,
And cyanophenyl, cumyl, pseudocumyl, aminophenyl, bromophenyl, naphthyl, etc., and a heterocyclic group (preferably having 20 or less carbon atoms, for example, pyridyl, furyl, quinolyl, thiophenyl, methylpyridyl, etc.). Hereinafter, specific examples of the compound represented by the general formula [I] or [II] are shown, but a Drex part in the general formulas [I] and [II], that is, XL _{1 t} in the general formula [I]
Part, and XL _{2 v} YL _{3 w} part in [II], and the release active substance part, ie, -De in [I] and [II].
The example is described in v section. The combination between the two is free.

It is assumed that the above bond is formed at a site represented by “*” in the following formula.

<Redox part> <Release main drug department> In the present invention, when the compound represented by the general formula (I) or (II) is added to the photosensitive material, the addition amount has a wide range, preferably 0.001 to 10 mol of the total amount of the reducing agent,
Particularly preferably, it is 0.01 to 1 mol.

In addition, any of a photosensitive layer, an intermediate layer, and a protective layer can be selected as a layer to be added.

 Examples of preferred compounds in the present invention are shown below.

A ₂ B ₅ A ₁₉ B ₁₁ A ₄₆ B ₅₇ A ₉ B ₇₄ A ₂ B ₃₁ A ₁₉ B ₁₈ A ₄₆ B ₆₂ A ₉ B ₆₁ A ₂ B ₂₄ A ₁₉ B ₁₉ A ₄₆ B ₆₄ A ₉ B ₆₈ A ₆ B ₂₁ A ₄₃ B ₅₁ A ₆₁ B ₆₆ A ₉ B ₇₁ A ₆ B ₂₀ A ₄₃ B ₅₄ A ₆₁ B ₆₉ A ₄₀ B ₇ A ₁₀ B ₂₂ A ₄₃ B ₆₁ A ₆₁ B ₅ A ₄₀ B ₃₀ A ₁₀ B ₆ A ₄₃ B ₇₁ A ₆₁ B ₁₃ A ₄₀ B ₁₃ A ₁₀ B ₈ A ₄₃ B ₆₂ A ₆₅ B ₅₅ A ₅₄ B ₆₂ A ₁₉ B ₆ A ₄₆ B ₆₅ A ₆₅ B ₅₆ A ₅₄ B ₆₄ A ₅₄ B ₇₈ A ₇₃ B ₁₅ A ₇₃ B ₁₉ A ₈₀ B ₁₇ A ₈₀ B _{27 In the} present invention, the compound represented by the general formula [I] or [II] can be synthesized using the method described below.

19.7 g of phenidone (Ia) and 17 ml of triethylamine
Was mixed with 200 ml of tetrahydrofuran, and 20.1 g of p-nitrophenyl chloroformate was added. After the mixture was stirred at room temperature for 1 hour, the mixture was poured into water and the precipitated crystals were separated by filtration. The obtained crystals were recrystallized from acetonitrile to obtain 25 g of (Ib).

20 g of (Ib) obtained above and 37 g of (Ic) synthesized by the method described in JP-A-61-236549 were mixed with 200 ml of acetonitrile, 4.5 ml of pyridine was added, and the mixture was heated under reflux for 3 hours. After cooling to room temperature, water was added to the reaction mixture, extracted with ethyl acetate, washed with water, and the solvent was distilled off under reduced pressure. The residue was purified by silica gel column chromatography, and recrystallized from hexane / ethyl acetate to give the desired compound (A ₁₉ B
₆ ) 21 g were obtained as pale yellow crystals.

20 g of phenidone (II-a) was added to 100 ml of acetic acid,
The mixture was dispersed in 0 ml, and 20 g of a 37% formaldehyde solution was added dropwise while stirring at 50 to 55 ° C. After heating and stirring at 50 ° C. for 4 hours, 100 ml of water was added to the reaction mixture, and the precipitated crystals were separated by filtration and dried to obtain 15 g of (II-b).

(II-b) 15 g of p-nitrophenyl chloroformate and 11.3 g of p-nitrophenyl chloroformate were dissolved in 100 ml of tetrahydrofuran.
5.4 ml were added and the mixture was stirred at room temperature for 3 hours.

Next, 25 g of hydrazine hydrochloride (II-d) and 5.4 ml of pyridine were added to the reaction mixture, and the mixture was heated under reflux for 2 hours. To the solution cooled to room temperature was added 10% aqueous hydrochloric acid, extracted with ethyl acetate, washed with water and concentrated under reduced pressure. The residue was purified by silica gel column chromatography and recrystallized from acetonitrile to obtain 8 g of the desired compound (A ₄₃ B ₇₁ ) as colorless crystals.

In the present invention, a reducible dye-donating compound is combined with a binder and a silver halide emulsion together with an electron transfer agent and an electron donor to form a single photosensitive layer. The reducible dye-providing compound may be added to the same layer as the silver halide emulsion, or may be added separately to an adjacent layer. In the latter case, the layer of the reducible dye-donating compound is preferably located below the silver halide emulsion layer from the viewpoint of sensitivity. In this case, the electron transfer agent and the electron donor can be added to any of the silver halide emulsion layer and the reducible dye-donating compound layer.

In the present invention, at least two such photosensitive layers are used. Usually, in order to reproduce full color, three sets of photosensitive layers having different color sensitivity are provided. For example, blue layer, green layer,
There are three combinations of red-sensitive layers, three combinations of green-sensitive layers, red-sensitive layers, and infrared-sensitive layers. Each color-sensitive layer can have various arrangement orders known for a conventional color light-sensitive material. In addition, each of these color-sensitive layers may be used as needed.
It may be divided into layers or more.

Next, the reducible dye-providing compound of the present invention will be described.

The reducible dye-providing compound in the present invention is a compound which reacts with a reducing agent (electron donor) remaining without undergoing oxidation accompanying the development of silver halide to release a diffusible dye.

Examples thereof are U.S. Pat.
No. 9,379, JP-A-59-185333, compounds capable of releasing a diffusible dye by a nucleophilic substitution reaction in a molecule after reduction described in U.S. Pat.
No., JP-A-59-101649, JP-A-61-88257, RD24025 (1984
Compounds which release a diffusible dye by an electron transfer reaction in the molecule after being reduced as described in
008,588A, JP-A-56-142530, U.S. Pat.No. 4,343,893
No. 4,619,884, etc., compounds that release a diffusible dye by cleavage of a single bond after reduction, and nitro, which releases a diffusible dye after electron acceptance described in U.S. Pat.No. 4,450,223, etc. Compound, U.S. Pat.No. 4,609,610
And the like, which release a diffusible dye after electron acceptance as described in the above publication.

Also, as more preferred, EP 220,746A
No. 2, Published Technical Report 87-6199, U.S. Pat. No. 4,783,396, JP-A-63-201653, JP-A-63-201654, etc., in which NX bond (X is oxygen, sulfur or nitrogen) in one molecule. compounds representative of the atoms) and having an electron withdrawing group, SO ₂ -X (X in U.S. Pat in one molecule described in No. 4,840,887 are compounds having the same meaning as defined above) and an electron attractive group, JP 63 A compound having a PO-X bond (X is as defined above) and an electron-withdrawing group in one molecule described in JP-A-271344, and a C-X 'in one molecule described in JP-A-63-271341. Bond (X 'is the same as X or -S
O _2- ) and a compound having an electron-withdrawing group. Further, compounds described in JP-A Nos. 1-161237 and 1-161342, in which a single bond is cleaved after reduction by a π bond conjugated to an electron-accepting group to release a diffusible dye, can also be used.

Among them, a compound having an NX bond and an electron-withdrawing group in one molecule is particularly preferable. A specific example is European Patent No. 22
0,746A2 or compounds (1) to (3), (7) to (10), (12), (13) described in US Pat. No. 4,783,396.
(15), (23)-(26), (31), (32), (35),
(36), (40), (41), (44), (53)-(59),
(64), (70), Compounds (11) to (2) of Published Technical Report 87-6199
3) and so on.

Specific examples are listed below, but the present invention is not limited to these.

Each of these compounds can be synthesized by the methods described in the patent specifications cited above.

The amount of the dye-providing compound used depends on the extinction coefficient of the dye, but is in the range of 0.05 to 5 mmol / m ² , preferably 0.1 to 3 mmol / m ² . The dye-providing substances can be used alone or in combination of two or more. Further, in order to obtain an image of black or a different hue, as described in JP-A-60-162251, for example, at least one of cyan, magenta and yellow dye-providing substances in a layer containing silver halide or Two or more dye-donating substances that release a mobile dye having a different hue, such as a mixture contained in an adjacent layer, can also be used.

In the present invention, an electron donor and an electron transfer agent (ETA) are used.
220746A2 and published technical report 87-6199.
Particularly preferred electron donors are described in JP-A-64-13546 (page 42).
(48) page and JP-A-1-120553 (5) to (9)
P. U.S. Pat. No. 4,783,396, column 73 to column 82, etc., which are nondiffusible hydroquinone derivatives and catechol derivatives.

Specific examples of the electron donor are listed, but the present invention is not limited to these compounds.

A plurality of compounds can be used in combination as the electron donor, and the amount of the electron donor has a wide range, but is preferably 0.01 mol to 50 mol, more preferably 0.1 mol to 5 mol, per 1 mol of the positive dye-donating substance. Is a preferable range. Also, 0.001 mol to 5 mol, preferably 0.01 mol to 1 mol of silver halide.
Mol to 1.5 mol.

As the ETA used in combination with these electron donors, any compound can be used as long as it is a compound that is oxidized by silver halide and the oxidized form has the ability to cross-oxidize the electron donor. Are preferred.

A particularly preferred ETA is U.S. Pat.No. 4,783,396 at column 81, column 38.
1-phenyl-3-pyrazolidinone derivatives described in -49 lines and the like.

Specific examples of the ETA are listed, but the present invention is not limited thereto.

In the present invention, an ETA precursor can also be used.

The ETA precursor used in the present invention does not have a developing action during storage of the light-sensitive material before use, but the ETA is first activated by a suitable activator (eg, chlorine, nucleophile, etc.) or action such as heating. It is a compound that can be released.

In particular, the ETA precursor used in the present invention does not have a function as ETA before development because the reactive functional group of ETA is blocked by a blocking group, but it is obtained under alkaline conditions or when heated. The blocking group can be cleaved to function as ETA.

As the ETA precursor used in the present invention, for example, 1-
2 and 3-acyl derivatives of phenyl-3-pyrazolidinone, 2-aminoalkyl or hydroxylalkyl derivatives, metal salts such as hydroquinone and catechol (lead, cadmium, calcium, barium, etc.), acyl halide derivatives of hydroquinone, oxazines of hydroquinone And bisoxazine derivatives, lactone-type ETA precursors, 4
Hydroquinone precursors having a quaternary ammonium group, cyclohex-2-ene-1,4-dione type compounds, compounds that release ETA by an electron transfer reaction, compounds that release ETA by an intramolecular nucleophilic substitution reaction, phthalides Examples include an ETA precursor blocked with a group, an ETA precursor blocked with an indomethyl group, and the like.

The ETA precursor used in the present invention is a known compound, for example, U.S. Patent Nos. 767,704, 3,241,967, 3,246,988, 3,295,978, 3,462,266,
No. 3,586,506, No. 3,615,439, No. 3,650,749
No. 4,209,580, No. 4,330,617, No. 4,310,61
No. 2, UK Patent Nos. 1,023,701, 1,231,830,
No. 1,258,924, No. 1,346,920, JP-A-57-40245,
58-1139, 58-1140, 59-178458, 59-182449
And JP-A-59-182450 can be used.

In particular, JP-A-59-178458, JP-A-59-182449, JP-A-59-18245
Preferred are precursors of 1-phenyl-3-pyrazolidinones described in No. 0 and the like.

ETA and an ETA precursor can be used in combination. The electron donor, ETA or their precursors can be used in combination of two or more kinds, respectively, and the emulsion layer (blue-sensitive layer,
Green-sensitive layer, red-sensitive layer, infrared-sensitive layer, ultraviolet-sensitive layer, etc.), only some of the emulsion layers, or a layer adjacent to the emulsion (an antihalation layer, an undercoat layer). , An intermediate layer, a protective layer, etc.), or further, to all the layers. The electron donor and ETA can be added to the same layer or to different layers. In addition, these reducing agents can be added to the same layer as the dye-donating substance or to another layer, but the diffusion-resistant electron donor is preferably present in the same layer as the dye-donating substance. preferable. The preferred amount of the electron donor, ETA or a precursor thereof is 0.01 to 50 mol, preferably 0.1 to 5 mol, and 1 mol of silver halide per mol of the dye-providing substance.
It is 0.001-5 mol, preferably 0.01-1.5 mol.

Also, ETA accounts for 60 mol% or less, preferably
0 mol% or less. When ETA is dissolved in water and supplied, the concentration of ETA is preferably 10 ^-4 mol / l to 1 mol / l.

The reducing substance of the present invention, a dye-donating substance, an electron donor,
In order to introduce an electron transfer agent or a precursor thereof and other hydrophobic additives into the hydrophilic colloid layer, a high-boiling organic solvent such as an alkyl phthalate (eg, dibutyl phthalate or dioctyl phthalate) or a phosphate (eg, diphenyl phosphate) is used. Fate, triphenyl phosphate, tricyclohexyl phosphate, tricresyl phosphate, dioctyl butyl phosphate), citrate (eg, tributyl acetyl citrate), benzoate (eg, octyl benzoate), alkylamide (eg, diethyl) Lauryl amide), fatty acid esters (eg, dibutoxyethyl succinate, dioctyl azelate), trimesic acid ester (eg, tributyl trimesate) Japanese Patent Application No. 61-231
No. 500 carboxylic acids, Japanese Patent Application Nos. 59-83154, 59-17
8451, 59-178452, 59-178453, 59-178454
No. 59-178455, using the method described in U.S. Pat.No. 2,322,027 using the compounds described in the same 59-178457,
Or an organic solvent having a boiling point of about 30 ° C. to 160 ° C., for example, ethyl acetate, lower alkyl acetate such as butyl acetate, ethyl propionate, secondary butyl alcohol, methyl isobutyl ketone, β-ethoxyethyl acetate, methyl cellosolve acetate, cyclohexanone, etc. After dissolving,
Dispersed in hydrophilic colloid. The above-mentioned high-boiling organic solvent and low-boiling organic solvent may be mixed and used. Further, after the dispersion, if necessary, the low-boiling organic solvent may be removed by ultrafiltration or the like before use. The amount of the high boiling organic solvent is 10 g or less, preferably 5 g per 1 g of the dye-providing substance used.
g or less. Further, the amount is 5 g or less, preferably 2 g or less per 1 g of the diffusion-resistant reducing agent. Further, the amount of the high-boiling organic solvent is 1 g or less, preferably 0.5 g or less, more preferably 0.3 g or less per 1 g of the binder. In addition, Tokiko Sho 51-39853
And a dispersion method using a polymer described in JP-A-51-59943 can also be used. In addition, it can be directly dispersed in an emulsion, or can be dissolved in water or alcohols and then dispersed in gelatin or an emulsion.

In the case of a compound which is substantially insoluble in water, it can be dispersed and contained as fine particles in a binder in addition to the above method. (For example, methods described in JP-A-59-174830, JP-A-53-102733, Japanese Patent Application No. 62-106882, etc.) When a hydrophobic substance is dispersed in a hydrophilic colloid, various surfactants are used. be able to. For example, JP-A-59-1
The surfactants listed on pages (37) to (38) of 57636 can be used.

The photothermographic 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, and further, if necessary. And an organic metal salt oxidizing agent. These components are often added to the same layer, but may be added separately to another layer if they can react. For example, if a coloring dye-providing compound is present in the lower layer of the silver halide emulsion, the sensitivity can be prevented from lowering. The reducing agent is preferably incorporated in the photothermographic material, but may be supplied from the outside by, for example, a method of diffusing from a dye fixing material described later.

In order to obtain a wide range of colors in the chromaticity diagram using the three primary colors of yellow, magenta and cyan, at least three silver halide emulsion layers sensitive to different spectral regions are used in combination. For example, blue layer, green layer,
There are a combination of three red-sensitive layers, a combination of green-sensitive layers, red-sensitive layers, and infrared-sensitive layers. Each photosensitive layer can adopt various arrangement orders known for ordinary type color photosensitive materials. Each of these photosensitive layers may be divided into two or more layers as necessary.

The photothermographic 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.

The silver halide that can be used in the present invention may be any of silver chloride, silver bromide, silver iodobromide, silver chlorobromide, silver chloroiodide, and silver chloroiodobromide.

The silver halide emulsion used in the present invention may be a surface latent image type emulsion or an internal latent image type emulsion. The internal latent image type emulsion is used as a direct reversal emulsion in combination with a nucleating agent or light fogging. A so-called core-shell emulsion in which the inside of the grain and the surface layer of the grain have different phases may be used. The silver halide emulsion may be monodispersed or polydispersed, or a mixture of monodispersed emulsions may be used. Particle size is 0.1 ~
2μ, especially 0.2-1.5μ, is preferred. The crystal habit of the silver halide grains may be any of cubic, octahedral, tetrahedral, high aspect ratio tabular, and the like.

Specifically, U.S. Patent No.
Any of the silver halide emulsions described in No. 28,021, Research Disclosure Magazine (hereinafter abbreviated as RD) 17029 (1978), and JP-A No. 62-253159 can be used.

The silver halide emulsion may be used as it is after unripe, but usually it is used after chemical sensitization. A known sulfur sensitization method, reduction sensitization method, noble metal sensitization method, or the like can be used alone or in combination for an emulsion for a normal photosensitive material. These chemical sensitizations can also be carried out in the presence of a nitrogen-containing heterocyclic compound (JP-A-62-253159).

It is appropriate to use 50 mg to 10 g / m ² .

In the present invention, various antifoggants or photographic stabilizers can be used. An example is RD17643
(1978) Azoles and azaindenes described on pages 24 to 25, carboxylic acids and phosphoric acids containing nitrogen described in JP-A-59-168442, or mercapto compounds and metals thereof described in JP-A-59-111636 Salts and acetylene compounds described in JP-A-62-87957 are used.

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

Specifically, U.S. Pat.No.4,617,257, JP-A-59-1805
No. 50, No. 60-140335, RD17029 (1978), pp. 12-13, and the like.

These sensitizing dyes may be used alone, or a combination thereof may be used.
Often used for supersensitization.

Along with the sensitizing dye, a dye which does not itself have a spectral sensitizing effect or a compound which does not substantially absorb visible light and exhibits supersensitization may be contained in the emulsion (for example, US Pat. No. 3,615,641). And those described in JP-A-63-23145).

These sensitizing dyes may be added to the emulsion at or before or after chemical ripening.
According to JP-A Nos. 6 and 4,225,666, it may be before or after the nucleation of silver halide grains. The addition amount is generally about 10 ^-8 to 10 ^-2 mol per mol of silver halide.

As the binder for the constituent layers of the photosensitive material and the dye fixing material, hydrophilic binders are preferably used. Examples thereof include those described on pages (26) to (28) of JP-A-62-253159. Specifically, transparent or translucent hydrophilic binders are preferred, for example, gelatin, proteins or cellulose derivatives such as gelatin derivatives, starch, gum arabic, dextran, natural compounds such as polysaccharides such as pullulan, polyvinyl alcohol, Examples include polyvinylpyrrolidone, acrylamide polymers, and other synthetic polymer compounds. Furthermore, superabsorbent polymers described in JP-A-62-245260, i.e. -COOM or -SO ₃ M (M
Is a homopolymer of a vinyl monomer having a hydrogen atom or an alkali metal) or a copolymer of the vinyl monomers or other vinyl monomers (for example, sodium methacrylate, ammonium methacrylate, Sumikagel L-manufactured by Sumitomo Chemical Co., Ltd.) 5H) is also used. These binders can be used in combination of two or more kinds.

When a system for performing thermal development by supplying a small amount of water is used, it is possible to quickly absorb water by using the above superabsorbent polymer. When the superabsorbent polymer is used for the dye-fixing layer and its protective layer, it is possible to prevent the dye from being re-transferred from the dye-fixing material to another after transfer.

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

Various polymers are included in the constituent layers (including the back layer) of the photosensitive material or the dye fixing material for the purpose of improving film physical properties such as dimensional stabilization, curling prevention, adhesion prevention, film crack prevention, and pressure sensation. Latex can be included. Specifically, JP-A-62-245258, JP-A-62-136648, and JP-A-62-1
Any of the polymer latexes described in No. 10066 can be used. In particular, when a polymer latex having a low glass transition point (40 ° C. or less) is used for the mordant layer, cracking of the mordant layer can be prevented, and when a polymer latex having a high glass transition point is used for the back layer, the curl prevention effect is reduced. can get.

In the present invention, a reducing agent known in the field of photothermographic materials can be used in combination. These reducing agents may be used to prevent color mixing and stain.

Examples of reducing agents used in the present invention include U.S. Pat.
Columns 49-50 of 4,500,626, 30-31 of 4,483,914
Column, No. 4,330,617, No. 4,590,152, JP-A-60-140
No. 335, pages (17)-(18), No. 57-40245, No. 56-1387
No. 36, No. 59-178458, No. 59-53831, No. 59-182449,
No. 59-182450, No. 60-119555, No. 60-128436 to No. 6
0-128439, 60198540, 60-181742, 61-
259253, 62-244044, 62-131253 to 62-131
Up to 256, there are reducing agents and reducing agent precursors described on pages 78 to 96 of EP 220,746 A2.

In the present invention, a compound capable of activating development and simultaneously stabilizing an image can be used in the light-sensitive material. Specific compounds preferably used are described in U.S. Pat.
No. 626, columns 51-52.

In a system for forming an image by diffusion transfer of a dye, a dye fixing material is used together with a photosensitive material. The dye-fixing material may be in the form of being separately coated on a support separate from the photosensitive material, or may be in the form of being coated on the same support as the photosensitive material. As for 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, the relationships described in column 57 of US Pat. No. 4,500,626 can be applied to the present invention.

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 are described in U.S. Pat.
No. 88256, pages (32) to (41), mordants described in
Nos. 244043 and 62-244036. Further, a dye-receiving polymer compound as described in US Pat. No. 4,463,079 may be used.

The dye-fixing material may be provided with an auxiliary layer such as a protective layer, a release layer, and an anti-curl layer, if necessary. It is particularly useful to provide a protective layer.

The constituent layers of the photosensitive material and the dye fixing material include a plasticizer,
A high boiling organic solvent can be used as a slipping agent or an agent for improving the releasability of the photosensitive material and the dye fixing material. Specific examples include those described in JP-A-62-253159, page (25) and JP-A-62-245253.

Further, for the above purpose, various silicone oils (all silicone oils from dimethyl silicone oil to modified silicone oil obtained by introducing various organic groups into dimethyl siloxane) can be used. Examples thereof include various modified silicone oils described in Technical Data P6-18B issued by Shin-Etsu Silicone Co., Ltd., especially carboxy-modified silicone (trade name: X-22-371).
0) is effective.

Also, silicone oils described in JP-A-62-215953 and JP-A-63-46449 are effective.

An anti-fading agent may be used in the light-sensitive material and the dye-fixing material. Anti-fading agents include, for example, antioxidants, ultraviolet absorbers, or certain metal complexes.

Examples of the antioxidant include chroman compounds, coumaran compounds, phenol compounds (eg, hindered phenols), hydroquinone derivatives, hindered amine derivatives, and spiroindane compounds. The compounds described in JP-A-61-159644 are also effective.

Examples of ultraviolet absorbers include benzotriazole-based compounds (such as US Pat. No. 3,533,794), 4-thiazolidone-based compounds (such as US Pat. No. 3,352681), benzophenone-based compounds (such as JP-A-46-2784), and others. JP 54-48
Nos. 535, 62-136641, 61-88256 and the like. Further, ultraviolet absorbing polymers described in JP-A-62-260152 are also effective.

As metal complexes, U.S. Pat.Nos. 4,241,155 and 4,2
Nos. 45,018, columns 3-36, 4,254,195, columns 3-8, JP-A-62-174741, JP-A-61-88256, pp. 27- (29), 6
There are compounds described in 3-199248, Japanese Patent Application Nos. 62-234103 and 62-230595.

Examples of useful anti-fading agents are described in JP-A-62-215272 (125)
(137).

An anti-fading agent for preventing fading of the dye transferred to the dye-fixing material may be contained in the dye-fixing material in advance, or may be supplied to the dye-fixing material from outside such as a photosensitive material. .

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

A fluorescent whitening agent may be used for the light-sensitive material and the dye-fixing material. In particular, it is preferable to incorporate a fluorescent whitening agent into the dye-fixing material or to supply it from outside such as a photosensitive material. For example, K. Veenkataraman ed., "The Chemistry of Synt
hetic Dyes ", Vol. V, Chapter 8, and JP-A-61-143752. More specifically, a stilbene compound, a coumarin compound, a biphenyl compound, a benzoxazolyl compound, a naphthalimide compound, a pyrazoline compound, a carbostyril compound, and the like can be given.

The optical brightener can be used in combination with a fading inhibitor.

Examples of the hardening agent used in the constituent layers of the light-sensitive material and the dye fixing material include U.S. Pat.No. 4,678,739, column 41, and JP-A-59-116655.
And hardening agents described in JP-A Nos. 62-245261 and 61-18942. More specifically, aldehyde hardeners (such as formaldehyde), aziridine hardeners, epoxy hardeners Vinyl sulfone hardeners (such as N, N'-ethylene-bis (vinylsulfonylacetamide) ethane), N-methylol hardeners (such as dimethylol urea), or polymer hardeners (Japanese Patent Laid-Open No. Sho 62) -234157).

Various surfactants can be used in the constituent layers of the light-sensitive material and the dye-fixing material for the purpose of coating aid, improving releasability, improving slipperiness, preventing static charge, and accelerating development. Specific examples of the surfactant are described in JP-A Nos. 62-173463 and 62-183457.

The constituent layers of the light-sensitive material and the dye-fixing material may contain an organic fluoro compound for the purpose of improving slipperiness, preventing static charge, and improving releasability. Representative examples of organic fluoro compounds include JP-B-57-9053, columns 8 to 17, JP-A-61-20944.
No. 62-135826 and hydrophobic surfactants such as fluorine-based surfactants described in No. 62-135826, or a solid fluorine compound resin such as an oily fluorine compound such as fluorine oil or a tetrafluoroethylene resin. Can be

A matting agent can be used for the photosensitive material and the dye fixing material. Examples of the matting agent include compounds described on page 29 of JP-A-61-88256, such as silicon dioxide, polyolefin and polymethacrylate, and benzoguanamine resin beads, polycarbonate resin beads, and AS resin beads. Nos. 62-110065 and 62-110065.

In addition, the constituent layers of the photosensitive material and the dye fixing material include:
A heat solvent, an antifoaming agent, an antibacterial and antibacterial agent, colloidal silica, and the like may be included. Specific examples of these additives are described in Japanese Patent Application No. 61-8 / 1986.
No. 8256, pages (26) to (32).

In the present invention, an image formation accelerator can be used for the light-sensitive material and / or the dye-fixing material. Examples of the image formation accelerator include the promotion of a redox reaction between a silver salt oxidizing agent and a reducing agent, the promotion of a reaction such as the generation of a dye from a dye-providing substance or the decomposition or release of a diffusible dye, and the use of a photosensitive material layer. From the physicochemical function to bases or base precursors, nucleophilic compounds, high-boiling organic solvents (oils), thermal solvents, surfactants, silver Or, it is classified into a compound having an interaction with silver ions. However, these substance groups generally have a composite function and usually have some of the above-mentioned promoting effects. See U.S. Pat.
No. 9, No. 38-40.

Examples of the base precursor include salts of an organic acid and a base which are decarboxylated by heat, compounds which release amines by an intramolecular nucleophilic substitution reaction, Rossen rearrangement or Beckmann rearrangement, and the like. Specific examples thereof are disclosed in U.S. Pat.
No. 65038.

In a system in which thermal development and transfer of a dye 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 from the viewpoint of improving the storage stability of the photosensitive material.

In addition to the above, EP 210,660, U.S. Pat.
No. 40,445, a combination of a hardly soluble metal compound and a compound capable of forming a complex with a metal ion constituting the hardly soluble metal compound (referred to as a complex forming compound);
A compound that generates a base by electrolysis described in 61-232451 can also be used as a base precursor. In particular, the former method is effective. The sparingly soluble metal compound and the complex forming compound are advantageously added separately to the light-sensitive material and the dye-fixing material.

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

The term "development terminator" as used herein means that after appropriate development, the base is quickly neutralized or reacts with the base to reduce the base concentration in the film, and interact with a compound that stops development or silver and silver salts to suppress development. Compound. Specific examples include an acid precursor that releases an acid when heated, an electrophilic compound that causes a substitution reaction with a coexisting base when heated, or a nitrogen-containing heterocyclic compound, a mercapto compound, and a precursor thereof. More specifically, JP-A-62-253159 (31) to (32)
Page.

As a support for the light-sensitive material and the dye-fixing material of the present invention,
Those that can withstand the processing temperature are used. Generally, paper and synthetic polymers (films) are used. Specifically, polyethylene terephthalate, polycarbonate, polyvinyl chloride, polystyrene, polypropylene, polyimide, celluloses (for example, triacetyl cellulose) or a film containing pigment such as titanium oxide in these films, and polypropylene. For example, mixed paper, Yankee paper, baryta paper, coated paper (especially cast-coated paper), metal, cloth, glass, etc. are used.

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

In addition, the supports described in JP-A-62-253159, pages (29) to (31) can be used.

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

Methods of exposing and recording images on photosensitive materials include, for example, a method of directly photographing landscapes and people using a camera, a method of exposing through a reversal film or a negative film using a printer or a enlarger, and a method of copier. Scanning and exposing the original image through slits using an exposure device, etc., exposing the image information by emitting light from a light emitting diode or various lasers via electrical signals, CRT, liquid crystal display, electroluminescence display And a method of outputting the image to an image display device such as a plasma display and exposing the image directly or via an optical system.

As a light source for recording an image on a photosensitive material, as described above, natural light, a tungsten lamp, a light emitting diode, a laser light source, a U.S. Pat.
The light sources described in the column can be used.

Also, image exposure can be performed using a wavelength conversion element in which a non-linear optical material and a coherent light source such as laser light are combined. Here, a nonlinear optical material is a material that can exhibit nonlinearity between polarization and electric field that appears when a strong optical electric field such as laser light is applied, such as lithium niobate and potassium dihydrogen phosphate (KDP ), Inorganic compounds represented by lithium iodate, BaB ₂ O _{4 and the} like, urea derivatives, nitroaniline derivatives such as nitropyridine-N-oxide such as 3-methyl-4-nitropyridine-N-oxide (POM). Oxide derivatives, JP-A-61-53462, 62
The compounds described in -210432 are preferably used. As a form of the wavelength conversion element, a single crystal optical waveguide type, a fiber type and the like are known, and any of them is useful.

The image information includes an image signal obtained from a video camera, an electronic still camera, a television signal represented by the Nippon Television Signal Standard (NTSC), and an image obtained by dividing an original image into a number of pixels such as a scanner. Signals, image signals created using a computer represented by CG and CAD can be used.

The photosensitive material and / or the dye-fixing material may have a form having a conductive heating element layer as a heating means for heat development or diffusion transfer of the dye. In this case, as the transparent or opaque heating element, those described in JP-A-61-145544 can be used. Note that these conductive layers also function as antistatic layers.

The heating temperature in the thermal development step can be developed at about 50 ° C. to about 250 ° C., and particularly about 80 ° C. to about 180 ° 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. In the latter case, the heating temperature in the transfer step is such that the transfer can be performed in the range from the temperature in the heat development step to room temperature, but it is particularly preferable that the heating temperature is 50 ° C. or higher and about 10 ° C. lower than the temperature in the heat development step.

Dye transfer is caused only by heat, but a solvent may be used to promote dye transfer.

Further, as described in detail in JP-A-59-218443, JP-A-61-238056, etc., a method in which development and transfer are carried out simultaneously or continuously by heating in the presence of a small amount of a solvent (particularly water) is also available. Useful. In this method, the heating temperature is preferably 50 ° C. or higher and the boiling point of the solvent or lower.
100 ° C or less is desirable.

Examples of the solvent used for promoting development and / or transferring the diffusible dye to the dye-fixing layer include water or a basic aqueous solution containing an inorganic alkali metal salt or an organic base (these bases include Those described in the section of the formation accelerator are used. In addition, a low-boiling solvent or a mixed solution of a low-boiling solvent and water or a basic aqueous solution can also be used. Further, a surfactant, an antifoggant, a sparingly soluble metal salt and a complex-forming compound may be contained in the solvent.

These solvents can be used in a method for imparting to the dye fixing material, the photosensitive material, or both. The amount used may be as small as not more than the weight of the solvent corresponding to the maximum swelling volume of the entire coating film (especially not more than the weight of the solvent corresponding to the maximum swelling volume of the entire coating film minus the weight of the entire coating film).

As a method for applying a solvent to the photosensitive layer or the dye fixing layer, there is, for example, a method described in JP-A-61-147244, page (26). Further, the solvent may be contained in the photosensitive material or the dye-fixing material or both in advance, for example, by enclosing the solvent in microcapsules.

In order to promote dye transfer, a method in which a hydrophilic thermal solvent which is solid at normal temperature and dissolves at high temperature is incorporated in the photosensitive material or the dye fixing material can be adopted. The hydrophilic thermal solvent may be incorporated in any of the photosensitive material and the dye fixing material,
It may be built in both. Also, the layer to be incorporated is an emulsion layer,
Any of an intermediate layer, a protective layer, and a dye-fixing layer may be used, but it is preferable to be incorporated in the dye-fixing layer and / or a layer adjacent thereto.

Examples of hydrophilic thermal solvents include ureas, pyridines, amides, sulfonamides, imides, alkenyls,
There are oximes and other heterocycles.

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

As a heating method in the development and / or transfer step, it is contacted with a heated block or plate, or in contact with a hot plate, hot presser, heat roller, halogen lamp heater, infrared and far infrared lamp heater, For example, passing through a high temperature atmosphere.

The method described in JP-A-61-147244, page 27, can be applied as a pressure condition and a method of applying pressure when the photosensitive material and the dye-fixing material are overlapped and brought into close contact with each other.

Any of a variety of thermal development equipment can be used to process the photographic elements of the present invention. For example, JP-A-59-75247, JP-A-59-1
Nos. 77547, 59-181353, 60-18951, 62-259
An apparatus described in No. 44 or the like is preferably used.

The color light-sensitive material of the present invention can also be applied to a color diffusion transfer photographic method in which processing is performed using a developer at around normal temperature. At this time, a peeling (beer apartment) type or an integrated type as described in JP-B-46-16356 and JP-B-48-33697, JP-A-50-13040 and British Patent 1,330,524, A structure of a film unit that does not need to be peeled as described in JP-A-57-119345 can be employed. The use of a polymeric acid layer protected by a neutralization timing layer in any of the above formats is advantageous for widening the processing temperature latitude. Further, the developer is used in the form of a viscous developer having a high viscosity, and may be supplied to the photosensitive material by putting it in a breakable container, combining with the photosensitive material, and breaking the container after exposure.

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

A well-stirred aqueous gelatin solution (20 g of gelatin, 3 g of potassium bromide, 0.03 g of the following compound, and HO in 800 cc of water)
(CH ₂ ) ₂ S (CH ₂ ) ₂ S (CH ₂ ) ₂ OH (0.25 g was added and kept at 50 ° C.), the following solution (1) and solution (2) were added simultaneously over 30 minutes. Thereafter, the following solution (3) and solution (4) were simultaneously added over 20 minutes. After the addition of (3) solution,
From 5 minutes, the following dye solution was added over 18 minutes.

After washing with water and desalting, 20 g of lime-treated ossein gelatin was added to adjust the pH to 6.2 and the pAg to 8.5, and then sodium thiosulfate and 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene were added. And chloroauric acid was added for optimal chemical sensitization. Thus, 600 g of a monodispersed cubic silver chlorobromide emulsion having an average grain size of 0.40 μm was obtained.

The method for preparing the third layer emulsion (II) will be described.

The following solution (I) and (II) were added to a well-stirred aqueous gelatin solution (a solution obtained by adding 20 g of gelatin, 0.30 g of potassium bromide, 6 g of sodium chloride and 0.015 g of the following chemical A to 730 ml of water and keeping the temperature at 60.0 ° C.) The liquid was added simultaneously at an equal flow rate over 60 minutes. After the addition of the solution (I), a methanol solution (III) of the following sensitizing dye was added. Thus, a monodispersed cubic emulsion adsorbing a dye having an average particle size of 0.45 μm was prepared.

After washing with water and desalting, add 20 g of gelatin, pH 6.4 and pAg.
After adjusting to 7.8, chemical sensitization was performed at 60.0 ° C. The chemicals used at this time were triethylthiourea 1.6 mg and 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene 100 m
In g, the aging time was 55 minutes. The yield of this emulsion was 635 g.

The method for preparing the first layer emulsion (III) will be described.

The following solution (I) and solution (II) were added to a well-stirred gelatin aqueous solution (a solution of 20 g of gelatin, 0.3 g of potassium bromide, 6 g of sodium chloride, and 30 mg of the following chemical A added in 800 ml of water and kept at 50 ° C). Was added simultaneously at an equal flow rate over 30 minutes. Thereafter, the following solution (III) and solution (IV) are simultaneously
Added over 0 minutes. Also, 3 minutes after the start of the addition of the liquids (III) and (IV), the following dye solutions were added over 20 minutes.

After washing and desalting, 20 g of lime-treated ossein gelatin was added to adjust the pH to 6.2 and the pAg to 7.7, and then sodium thiosulfate and 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene were added. Then, chloroauric acid was added and the mixture was optimally sensitized at 60 ° C. Thus, a monodispersed cubic silver chlorobromide emulsion having an average grain size of 0.38 μ was obtained. The yield was 635 g.

Dye solution The following dye (a) 67mg and dye (b) 133mg were added to methanol 1
Dissolved in 00ml.

A method for preparing a dispersion of zinc hydroxide will be described.

12.5 g of zinc hydroxide having an average particle size of 0.2 μm, 1 g of carboxymethylcellulose as a dispersant, and 0.1 g of sodium polyacrylate are added to 100 cc of a 4% aqueous gelatin solution, and crushed for 30 minutes using glass beads having an average particle size of 0.75 mm in a mill. did. The glass beads were separated to obtain a dispersion of zinc hydroxide.

 Next, a method for preparing a dispersion of activated carbon will be described.

2.5 g of activated carbon powder (reagent, special grade) manufactured by Wako Pure Chemical Co., Ltd., 1 g of Demol N manufactured by Kao Soap Co., Ltd. and 0.25 g of polyethylene glycol nonyl phenyl ether as a dispersant are added to 100 cc of a 5% aqueous gelatin solution, and the average particle size is milled. Grinding was performed for 120 minutes using 0.75 mm glass beads. The glass beads were separated to obtain a dispersion of activated carbon having an average particle size of 0.5 μm.

10 g of the following electron transfer agent, 0.5 g of polyethylene glycol nonylphenyl ether as a dispersant, and 0.5 g of the following anionic surfactant are added to a 5% aqueous gelatin solution, and the mixture is milled using glass beads having an average particle size of 0.75 mm for 60 minutes. Crushed. The glass beads were separated to obtain a dispersion of an electron transfer agent having an average particle diameter of 0.3 μm.

Next, a method for preparing a gelatin dispersion of the dye-providing compound will be described.

Yellow, magenta, and cyan dye-donating compounds were added to 50 cc of ethyl acetate according to the following formulation, and added to the mixture.
The solution was dissolved by heating to a uniform temperature. This solution, 100 g of a 10% aqueous solution of lime-processed gelatin, 0.6 g of sodium dodecylbenzenesulfonate and 50 cc of water were stirred and mixed, and then dispersed with a homogenizer for 10 minutes at 10,000 rpm. This dispersion is called a gelatin dispersion of the dye-providing compound.

Next, a method for preparing a gelatin dispersion of the electron donor for the intermediate layer will be described.

The following electron donor 23.6 g and the above high boiling solvent 8.5 g
Was added to 30 cc of ethyl acetate to obtain a uniform solution. This solution, 100 g of a 10% aqueous solution of lime-processed gelatin, 0.25 g of sodium bisulfite, 0.3 g of sodium dodecylbenzenesulfonate and 30 cc of water are mixed with stirring, and then mixed with a homogenizer for 10 minutes.
Dispersed at 10,000 rpm. This dispersion is referred to as a gelatin dispersion of the electron donor.

Using the above materials, a heat-developable color light-sensitive material 101 having a multilayer structure shown in Table 1 below was prepared.

Note 1) Surfactant Note 2) Surfactant Note 3) Water-soluble polymer Note 4) Antifoggant Note 5) Surfactant Note 6) Surfactant * 7) Hardener 1,2-bis (vinylsulfonylacetamide) ethane * 8) Antifoggant Note 9) Polyvinyl alcohol (molecular weight: 2000) Next, the method of making the dye fixing material will be described. A dye-fixing material R-1 having the composition shown in the following table was prepared.

Note 1) Silicone oil Note 2) Surfactant Note 3) Surfactant Note 4) Surfactant Note 5) Optical brightener 2,5 bis (5-tert-butylbenzoxazol (2)) thiophene Note 6) Surfactant Note 7) Water-soluble polymer Sumikagel L5-H (Sumitomo Chemical Co., Ltd.) Note 8) Water-soluble polymer dextran (molecular weight 70,000) Note 9) Staining agent Note 10) High boiling point solvent Note 11) Hardener Note 12) Matting agent: Benzoguanamine resin (average particle size: 15μ). To photosensitive material 101, the amount of electron transfer agent was changed as shown in Table 3 and the compound of the present invention and the comparative compound were added. Photosensitive materials 102 to 11 of exactly the same composition
5 were created respectively.

In addition, when adding the said compound, it used by the method of co-emulsifying in the emulsion of each addition layer.

Using a tungsten electrode for the multi-layered color light-sensitive material 101 to 115, the density is continuously changed B, G, R and 1/10 at 5000 lux through a color separation filter of gray
Exposure for seconds.

While feeding the exposed photosensitive material at a linear speed of 20 mm / sec, water of 15 ml / m ² was supplied to the emulsion surface with a wire bar, and immediately thereafter, the image receiving material was superimposed on the film surface so as to be in contact with the film surface.

The film was heated for 15 seconds using a heat roller whose temperature was adjusted so that the temperature of the water-absorbed film became 85 ° C. Next, when peeled off from the image receiving material, clear images of blue, green, red, and gray corresponding to the B, G, R, and gray color separation filters were uniformly obtained on the image receiving material.

Similarly, the color photographic materials 101 to 115 were exposed using a spectrograph through a wedge whose density continuously changes in the direction perpendicular to the wavelength.

(Spectral exposure) When the exposed photosensitive material is heated and developed in the same manner as described above, a blue,
Green and red spectrumgrams were obtained.

The results of measuring the maximum density (D _max ) and minimum density (D _min ) of each color of cyan, magenta, and yellow in the gray-exposed area of the color separation filter, and the cyan, magenta, and yellow densities of the green spectrumgram in spectral exposure. Are shown in [Table 4].

Example 2 Using the same emulsion and dye-donating substance as the color light-sensitive material of Example 1, a multi-layered color light-sensitive material 20 shown in Table 5 was used.
Made one.

Note 1) Latex of polymer polyethylene acrylate Note 2) Hardener Triacryloyl perhydrotriazine Note 3) Electron donor Note 4) Polymer Note 5) Electron donor Next, how to make a cover sheet will be described.

 A cover sheet having the configuration shown in Table 6 was prepared.

Note 1) Polymer Note 2) Polymer Cellulose acetate Note 3) Polymer Further, a treatment liquid having the following composition was prepared.

Potassium hydroxide 48 g 4-hydroxymethyl-4-methyl-p-tolyl-3-
Pyrazolidinone 10g 5-Methylbenzotriazole 1.5g Sodium sulfite 1.5g Potassium bromide 1g Benzyl alcohol 1.5ml Carboxymethylcellulose 6.1g Carbon black 150g Water Amount to make the total amount 1 The photosensitive material 201 is exposed as shown in Table 7 Photosensitive materials 202 to 210 having exactly the same composition except that an electron transfer agent was added to the fourth layer of the material or that the compound of the present invention was added were prepared.

The color photosensitive material 201-210 was subjected to wedge exposure and spectral exposure in the same manner as in Example 1, then superposed on the cover sheet, and using a pair of rollers, the processing solution was uniformly spread between the two with a thickness of 80 μm. Expanded.

One hour after this treatment, the result of sensitometry in the same manner as in Example 1 is shown in Table 8.

Claims (2)

(57) [Claims] 1. A color light-sensitive material comprising at least a light-sensitive silver halide, a binder, a non-diffusible dye-donating compound which is reduced to release a diffusible dye, an electron donor and an electron transfer agent on a support. And a color photographic material further comprising at least one compound represented by the following general formula [I] or [II]. General formula [I] XL _{1 t} Dev General formula [II] XL _{2 v} YL _{3 w} Dev In the general formula [I], X represents an oxidation-reduction nucleus, and is oxidized during the development process. It is a group that makes it possible to emit L _{1 t} Dev. L ₁ represents a group that cleaves Dev after cleavage from X. In the formula (II), X represents a redox nucleus, and represents a group that is oxidized during development to cleave L _{2 v} YL _{3 w} Dev, and L ₂ is YL after cleavage from X. Y represents a group that cleaves _{3 w} Dev, Y represents a group that cleaves L _{3 w} Dev by being oxidized after cleavage, and L ₃ represents a group that cleaves Dev after cleavage from Y. t, v, and w each represent 0 or 1. Dev is L
_It represents a group that functions as an electron transfer agent after being released from _{1 t} DeV or L _{3 w} Dev. 2. The color light-sensitive material according to claim 1, wherein
The group represented by -Dev in the general formula [I] is represented by the following general formula [I
A color light-sensitive material having a structure represented by the formula [II] or [IV]. General formula (III) (IV) In the formula, R _{1 to} R ₄ each represent a hydrogen atom, or a substituted or unsubstituted alkyl group, aryl group, or heterocyclic group. R represents a substituted or unsubstituted aryl group or heterocyclic group.