JPS60211454A - Heat developable color photosensitive material - Google Patents

Abstract

PURPOSE:To obtain a color image with high sensitivity by forming on a support a heat-developable color photosensitive layer contg. photosensitive silver halide, a heat decomposable org. silver salt, a binder, and a reducing dye-doner capable of being oxidized on being heated and releasing a mobile dye imagewise. CONSTITUTION:A coating soln. is composed of photosensitive silver halide, a heat decomposable org. silver salt, a binder, and a reducing dye-doner capable of being oxidized on being heated and realsing a mobile dye, and a heat developable color photosensitive material is obtained by coating a support, such as glass, paper, metal, cellulose acetate film, or polyethylene terephtalate, with said coating soln. As said heat decomposable org. silver salt, silver carboxylates capable of being decarboxylated at 80-250 deg.C, preferably, 100-200 deg.C, are useful. The heat developable photosensitive material thus obtained can be used effectively for forming both of positive and negative images.

Description

DETAILED DESCRIPTION OF THE INVENTION (Technical Field of the Invention) The present invention relates to a heat-developable color photosensitive material containing a thermally decomposable organic silver salt.

(Background of the Invention) European Patent Publication Box 74,1122 describes silver halide, an organic silver salt, and a reducible dye that reacts with silver dihalide upon heating to form an image-like hydrophilic mobile dye. A heat-developable color photosensitive material containing a releasing dye-providing substance is described.

Various organic silver salts can be used in this heat-developable color photosensitive material. Representative examples of organic silver salts include silver salts of aliphatic carboxylic acids and silver salts of aromatic carboxylic acids.

Also, U.S. Patent No. 3,330. Examples include silver salts of aliphatic carboxylic acids having a thioether group, which are described in ttJ specification.

However, these carboxylic acid silver salts have the disadvantage that after reaction with a reducing agent, the acid is released, the pH in the film is lowered, and subsequent development is inhibited.

Organic silver salts other than carboxylic acids include silver salts of compounds having mercapto or thione groups and derivatives thereof.

Others: Special public show 4A4A-3oλ70. Same group J-1/1
There are silver salts of compounds having an imino group, such as silver salts of benzotriazole and derivatives thereof described in Publication No. 4AI and G.

However, these silver salts have the disadvantage that after reaction with reducing agents they release compounds which inhibit or even fog the development. It may also inhibit the action of spectral sensitizing dyes, resulting in high sensitivity.

(Purpose of the invention) The present invention ameliorates these drawbacks.

An object of the present invention is to provide a photosensitive material capable of producing high-density color images in a short period of time.

A first object of the present invention is to provide a photosensitive material capable of producing color images with high density and low fog.

A third object of the present invention is to provide an organic silver salt for heat-developable photosensitive materials that does not exhibit any side effects after heat development.

(Disclosure of the Invention) The object of the present invention is to provide at least a photosensitive silver halide, a thermally decomposable organic silver salt, a binder and a reducible material on a support, which is oxidized upon heating to imagewise release a mobile dye. This can be achieved using a heat-developable color photosensitive material containing a dye-providing substance.

Preferred among the above thermally decomposable organic silver salts are to
0cmλj00c, more preferable is ioo 'c
It is a carboxylic acid silver salt that is decarboxylated at -2oo'c.

Among the carboxylic acid silver salts that are decarboxylated at the above-mentioned temperature, preferred ones are those represented by the following general formula.

[General formula (1)] (R+C02)m)・mAg In the above formula, m represents an integer of /-4.

R is a substituted alkyl group having an electron-withdrawing group at the α position, a substituted aryl group having an electron-donating group at the ortho and/or para position, an alkynyl group, a substituted alkynyl group, an acyl group,
Alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, substituted carbamoyl group or residue (j or 6-membered ring, l(', :(//
represents a group selected from a hydrogen atom, an alkyl group, a substituted alkyl group, an aryl group, and a substituted aryl). To give a preferable example of R, the substituted alkyl group having an electron-withdrawing group at the α-position is CC/! a-1CBr3
-1CF (J2-5CF2C/-1NCCH, -1CH
3SO2C) T2-1j- 00 4- and /''!Substituted aryl groups having an electron donating group at the ξ position include: Examples of the aryloxycarbonyl group include CF 3 CH20C-, and examples of the aryloxycarbonyl group include OO-ter and the like.

In the above general formula, R is most preferably an alkynyl group or a substituted alkynyl group, which is represented by the following general formula.

[General formula (2)] RO(C=C-(02)m-mAg In the above formula, RO is a hydrogen atom, an alkyl group, a substituted alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, an aryl group, a substituted aryl group) group, heterocyclic residue, substituted heterocyclic residue, aralkyl group, substituted aralkyl group, acyl group, alkoxycarbonyl group, carbamoyl group, substituted carbamoyl group, -CO2M (M is an alkali metal), -co
2B represents a nonavalent residue selected from 2B, or a covalent residue selected from an alkylene group, an arylene group, and a heterocyclic covalent residue (which may further have a substituent).

B is a conjugate acid of an organic base or a quaternary ammonium group. Typical organic bases include guanidines, cyclic guanidines, amidines, and cyclic amidines.

Examples of axes include a hydrogen atom, a 1-alkyl group with a carbon number of /,j, a substituted alkyl group with a carbon number of /-7, a cycloalkyl group with a carbon number of j-t, and a carbon number of 2~! alkenyl group, carbon number λ
~ Alkynyl group, phenyl group, substituted phenyl group, naphthyl group, substituted naphthyl group, anthryl group, pyridyl group, substituted pyridyl group, chenyl group, substituted chenyl group, thiazolyl group, benzoxacylyl group, benzothiazolyl group, number of carbon atoms Aralkyl group having 7 to 10 carbon atoms, acyl group having λ to 1 carbon atoms, alkoxycarbonyl group having 2 to 1 carbon atoms, carbamoyl group, substituted carbamoyl group having λ to 2 carbon atoms, -C
O2N ms -CO2K.

-Co 2 Cs, -Co 2 ・B (B is the above-mentioned base component), /, J-phenylene group, /, 4C-phenylene group, /, j-naphthylene group 1.2, j-chenylene group , ri, io-antrylene group, etc. R
O preferably has a suitable electron-withdrawing property L<, alkenyl group, alkynyl group, phenyl group, substituted phenyl group,
Naphthyl group, substituted naphthyl group, anthryl group, pyridyl group, substituted pyridyl group, chenyl group, substituted chenyl group, benzoxacylyl group, benzothiazolyl group, acyl group,
Alkoxycarbonyl group, carbamoyl group, substituted carbamoyl group, -CO2M, -(?02- B, )x=v
Preferably used are a nyl group, a naphthylene group, a chenylene group, an anthrylene group, and the like.

Next, specific examples of preferable thermally decomposable organic silver salts used in the present invention will be shown, but the present invention is not limited thereto.

(1) Hc=c-co2・AI (2) CH3−(,=C−C02・A, 9 −l μ − −7!− 1/J− l 7− −/r− CH3 1/!/−翰21- 1λ O- -2co- C5-QC-[:=[-CO2・A, !901 o2cmc=c-co2・λAg 23- -2μ- (To) N-0) T 2 j- -OH -0H 6 2 t- The thermally decomposable organic silver salt of the present invention is produced by synthesizing a decarboxylating carboxylic acid by the method shown below, and using this acid as a silver ion donor (
For example, it can be prepared by mixing with silver nitrate).

Regarding the synthesis of decarboxylated carboxylic acids, the synthesis method differs depending on the type, but in any case, it can be synthesized by a known general method. To give a typical example, R
When is a substituted alkyl group having an electron-withdrawing group at the α-position, reaction of α-haloacetic acid with a nuclear reagent such as a sulfinate or cyanide, or reaction of an active methyl or active methylene compound with a carbonate ester in the presence of a base. Reactions such as: carboxylation by Kolbe-Schmidt reaction when R is a substituted aryl group having an electron-donating group, and addition of bromine to an acrylic acid derivative followed by dehydrogenation when IR is an alkynyl group. Regarding these reactions, please refer to the New Experimental Chemistry Course 7μ(n)ter 2l-1042 (/ri77, Maruzen):
OrganicFunc-onal Group P
reparationsblrit-co A J' (/
9 AI%Academic Press) has a detailed description. In addition, for relatively simple compounds such as trinoacetic acid, phenylacetic acid derivatives, and α-ketocarboxylic acids, commercially available products may be used.

An example of synthesis of a thermally decomposable organic silver salt will be described below.

Synthesis of O organic silver salt (3) Cinnamic acid λ, t9 was dissolved under heating in rOml of acetic acid, and then bromine 329 was added dropwise. After stirring for IS minutes at 0C, the mixture was allowed to cool, 1 ounce of water was gradually added, and the white crystals formed were washed several times with water and dried. Yield jtg. Potassium hydroxide jty was dissolved in 200 ynl of methanol, and then the above crystals were added little by little into the solution. Meta-2-sol was distilled off while heating and stirring on a hot water bath. The residue was dissolved in 2 ooml of water and neutralized with dilute sulfuric acid while cooling with water. The liberated pale yellow oil quickly solidified. The solidified crystals were recrystallized from water several times to obtain 22 g of phenylpropiolic acid.

Melting point/Jt-/j7 °C The above acid was converted into a silver salt according to a conventional method.

Synthesis of 0 organic silver salts (4!19) 260.2g of thioglycolic acid and toluene iz.

Add 33 fl of potassium hydroxide to the mixture and heat and stir.

The produced water was distilled off together with toluene, and when no more water was distilled off, 100 d of dimethylacetamide was added, and then p-bromodiphenylsulfone J'2.4A,! i+
was added little by little. After stirring at /jθ-/400C for 3 hours, the mixture was allowed to cool and the reaction solution was poured into cold dilute hydrochloric acid. Extract the liberated oil with ethyl acetate, wash the extract with water, dry it, and
Ethyl acetate was concentrated under reduced pressure, and the precipitated crystals were washed several times with toluene. Yield 1000 ml of the above crystalline aog, sodium tungstate co-30-hydrate salt 0 #9 and acetic acid/20 ml mixture.
Heat to 50-40°C and add hydrogen peroxide solution for 30 minutes.
Friend dripping with. After the dropwise addition, the mixture was stirred at 7!0C for 30 minutes, allowed to cool, and the reaction solution was poured into cold water.

The precipitated white crystals were washed several times with water and dried to obtain (p-phenylsulfonylphenyl)-sulfonylacetic acid≠ig. Melting point: 15,144-19 g'C (decomposition) The above acid was converted to silver salt (2) according to a conventional method.

Synthesis of O organic silver salt(s) t, 2/, tI finely divided into tooml dry ether
of diphenylmethylphosphine oxide was added thereto, and while stirring vigorously, a 0.1 mol equivalent of butyllithium hexane solution was added little by little. The reaction mixture was heated under reflux for 3 hours, then cooled to 200 C and added portionwise into a mixture of finely crushed 1009 dry ice and 3 ooytdl of ether.

After stirring for 70 minutes, the ether was distilled off, diluted hydrochloric acid was added to the residue, and the mixture was extracted with ethyl acetate. Ethyl acetate extract! Extraction was repeated with aqueous sodium bicarbonate solution, the extract was made acidic with dilute hydrochloric acid, and the precipitated white crystals were washed several times with water and dried to obtain 16° of carboxymethyl diphenylphosphine oxide. Melting point 7≠J-/4Z4'C Next, this free acid was converted into a silver salt according to a conventional method to obtain an organic silver salt 63).

The thermally decomposable organic silver salt may be prepared in the same system, that is, in combination with other components of the photothermographic material, or outside the same system, that is, prepared separately from other components of the photothermographic material. You may. However, in consideration of ease of control during preparation and ease of storage, it would be preferable to prepare it separately from the other components of the photothermographic material.

A salt of a decarboxylated carboxylic acid with silver can also be obtained by simply mixing a source of silver ions, such as silver nitrate, and a decarboxylated carboxylic acid in a hydrophilic solvent such as water and/or methanol. In this case, they may be mixed in the presence of a hydrophilic binder such as gelatin. Purification of the resulting product or dispersion can be carried out according to techniques known in the art.

Two or more kinds of organic silver salts of the present invention can be used. It can also be used in combination with known organic silver salts. The organic silver salt of the present invention can be used in the same layer as the photosensitive silver norogenide or in an adjacent layer.

The organic silver salt of the present invention can be used in a wide concentration range. Coating amount is 101n9 to 109/1 in terms of silver.
n2 is appropriate. It is also photosensitive and resistant to silver halide.
, oi ~ 200 mils 200 mols. Further, the shape and particle size of the organic silver salt of the present invention can be arbitrarily selected, but an average particle size of 10 μm or less is preferable.

The dye-donating substance that releases a mobile dye used in the present invention is a compound described as a maple element-donating substance in European Patent Publication No. 7J, No. 4' Octopus, and has the following general formula (I) Ra-8
It is represented by 02-D.

Here, Ra represents a reducing group, and D represents an image-forming dye having a hydrophilic group.

The above-mentioned substances are oxidized to imagewise release a mobile dye corresponding to or inversely corresponding to the latent image distributed imagewise in the silver halogenide.

The reducing substrate (Ra
) has a redox potential of 10.2 with respect to a saturated calomel electrode in polarographic half-wave potential measurement using acetonitrile as a solvent and sodium perchlorate as a supporting electrolyte.
V or less is preferable. A preferred reducing substrate (R
a) is the following general formula (%) N) T- -Jj- where R1, R2, R3, R4 are each a hydrogen atom, aaa alkyl group, cycloalkyl group, aryl group, alkoxy group, aryloxy group, Aralkyl group, acyl group, acylamino group, alkylsulfonylamino group, arylsulfonylamino group, aryloxyalkyl group, alkoxyalkyl group, N-substituted carbamoyl group, N-substituted sulfamoyl group, halogen atom, alkylthio group, arylthio group The alkyl group and aryl group in these groups further include an alkoxy group, a halogen atom, a hydroxyl group, a cyano group, an acyl group, an acylamino group, a substituted carbamoyl group, a substituted sulfamoyl group, and an alkylsulfonylamino group. , an arylsulfonylamino group, a substituted ureido group, or a carbalkoxy group.

The hydroxyl group and amino group in 9-Ra may be protected with a protecting group that can be regenerated by the action of a nuclear reagent.

In a more preferred embodiment of the present invention, the reducing group 37- The quality Ra is expressed by the following formula (X).

Here, G represents a hydroxyl group or a group that provides a hydroxyl group through hydrolysis. Ra represents an alkyl group or an aromatic group. n is an integer from 1 to 3.

When n==/, X1° represents an electron-donating substituent, and when n=λ or 3, it may be the same or different substituent, and when one of them is an electron-donating group, it represents an electron-donating substituent. or the third one is an electron donating group or a halogen atom J,
, XIO may form a condensed ring by itself or may form a ring with ORa.

The total number of carbon atoms in both RIO and XIO is equal to or greater than r.

Specific examples included in (X) are USg, oss.

3.
Each is described in No. t/30.

In another more preferred embodiment of the present invention, the reducing substrate (Ra) is represented by the following formula (XI).

(However, the symbols Ga, X10.R": and n have the same meanings as Ga, Ra) is expressed by the following formula (■).

Here, Ba1last contains a diffusion-resistant group.

Ga represents a hydroxyl group or a hydroxyl group precursor.

G1 represents an aromatic ring or a group that forms a naphthalene ring together with a benzene ring. n and m are/or λ
Hail an integer that turned out to be.

Specific examples included in the above (■) are US-μ, θ33.3
It is described in 12.

Formulas (V), (VIF), (■) and (IX)
The reducing substrate of is characterized by containing a heterocycle, and specific examples include USμ, /91r,, 23! , JP-A-13-114730% US 44.273.113. A specific example of the reducing substrate represented by formula (VI) is '[JS4A,/μri.

There is a description in Zatako.

Dyes that can be used as image-forming dyes include azo dyes, azomethine dyes, anthraquinone dyes, naphthoquinone dyes, styryl dyes, nitro dyes, quinoline dyes, carbonyl dyes, and phthalocyanine dyes. It should be noted that these dyes can also be used in a temporarily short-wave form that can be multicolored during development.

The dye-donating substance used in the present invention is European Patent Publication 7t
, No. 1792.

Specific examples of imaging materials for use in the present invention are described in the patents cited above. Since it is not possible to list all the preferred compounds here, some of them will be shown as examples. For example, examples of the dye-donating substance represented by the formula (I) include those described below.

(1) 14/-H-! 2-shi4Ho(tlH0H-4L, t-(1υH-μt-0)TQ4)0)T The compounds described above are examples and are not limited thereto.

In the present invention, the dye-donating substance is U.S. Pat.
It can be introduced into the layer of the photosensitive material by a known method such as the method described in , No. 027.

In that case, the following high boiling point organic solvents and low boiling point organic solvents can be used.

For example, phthalic acid alkyl esters (dibutyl tucrate, dioctyl phthalate, etc.), phosphoric acid esters (
diphenyl phosphate, triphenyl phosphate,
tricresyl phosphate, dioctyl butyl phosphate), citric acid esters (eg acetyl tributyl citrate).

High boiling point organic solvents such as benzoic acid esters (octyl benzoate), alkylamides (e.g. diethyl laurylamide), fatty acid esters (e.g. dibutoxyethyl succinate, dioctyl azelate), trimesic acid esters (e.g. tributyl trimesate) , or an organic solvent 2 with a boiling point of about 30°C to 160°C, such as lower alkyl acetate such as ethyl acetate, butyl acetate, ethyl propionate, secondary butyl alcohol, methyl isobutyl ketone, β-ethoxyethyl acetate, methyl cellosolve acetate, cyclohexanone, etc. After being dissolved in a hydrophilic colloid, it is dispersed in a hydrophilic colloid.

The above-mentioned high boiling point organic solvent and low boiling point organic solvent may be mixed and used.

Also, Japanese Patent Publication No. 51-39853, Japanese Patent Publication No. 51-5994
The dispersion method using a polymer described in No. 3 can also be used. In addition, a variety of surfactants may be used in dispersing the dye-donating substance in the hydrophilic colloid, including those listed as surfactants elsewhere in this specification. can be used.

The amount of the high boiling point organic solvent used in the present invention is 10 g or less per 1 g of the dye-providing substance used.

Preferably it is 5g or less.

In the present invention, a reducing dye-donating substance is used, but
This can be done by using a so-called auxiliary developer if necessary.

In this case, the auxiliary developer is oxidized by the halogen compound, and its oxidized product has the ability to oxidize the reducing substrate in the dye-donating substance.

Useful auxiliary developers include alkyl-substituted hydroquinones such as hydroquinone, t-butylhydroquinone, 2,5-dimethylhydroquinone, catechol, pyrogallols, halogen-substituted hydroquinones such as chlorohydroquinone and dichlorohydroquinone, and alkyl-substituted hydroquinones such as methoxyhydroquinone. There are substituted hydroquinones and polyhydroxyhensen derivatives such as methylhydroxynaphthalene. Furthermore, methyl gallate, ascorbic acid, ascorbic M derivative 4 IL N,N''-G(2
Hydroxylamines such as -ethoxyethyl) hydroxylamine, 1-phenyl-3-pyrazolidone, 4-
Useful are pyrazolins such as methyl-4-hydroxymethyl-1-phenyl-3-pyrazolidone, reductones, and hydroxytetronic acids.

Auxiliary developers can be used in a range of concentrations. A particularly useful concentration range is 0.0005 times molar to 20 times molar relative to silver.

It is 0.001 times mole to 4 times mole.

Silver halides used in the present invention include silver chloride, silver chlorobromide, silver chloroiodide, silver bromide, silver iodobromide, silver chloroiodobromide, and silver iodide.

Such silver halide can also be obtained, for example, by adding a silver nitrate solution to a potassium bromide solution to first form silver bromide grains, and then adding potassium iodide.

Two or more types of silver halide having different sizes and/or silver halide compositions may be used in combination.

The average grain size of the silver halide grains used in the present invention is preferably from 0.001 μm to 10 μm, more preferably from 0.001 μm to 5 μm.

The silver halide used in the present invention may be used as it is, but it may also be compounded with compounds such as sulfur, selenium, tellurium, etc., chemical sensitizers such as compounds such as gold, platinum, palladium, rhodium and iridium, tin halide, etc. Chemical sensitization may be achieved by the use of reducing agents such as or combinations thereof. In detail.

“The theory of the Ph.

tographic Process'' 4th edition, T, H,
James, Chapter 5, pages 149-169.

In the present invention, the coating amount of photosensitive silver halide is suitably 1 mg to 10 g/% in terms of silver.

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

Further, in the present invention, it is possible to use a compound that activates the development and stabilizes the image at the same time.

Among them, isothiuroniums represented by 2-hydroxyethylisothiuronium trichloroacetate described in U.S. Patent No. 3,301,678, U.S. Patent No. 3,6
Bis(isothiuroniums) such as 1,8-(3,6-thioxaoctane)bis(isothiuronium trichloroacetate) described in West German Patent No. 69,670, West German Patent No. 2.
162. Thiol compounds described in US Pat. No. 714, 2-amino-2-thiazolium trichloroacetate, 2-amino-5-
Thiazolium compounds such as bromoethyl-2-thiazolium trichloroacetate, U.S. Pat. No. 4,060
Compounds having 2-carboxycarboxamide as an acidic moiety, such as bis(2-amino-2-thiazolium)methylenebis(sulfonylacetate) and 2-amino-2-thiazoliumphenylsulfonylacetate described in , No. 420. is preferably used.

Furthermore, the azole thioether and prosocdoazolinion compounds described in Belgian Patent No. 768,071,
4-Aryl- as described in U.S. Pat. No. 3,893,859
1-Carbamyl-2-tetrazoline-5-thousandone compound, and other U.S. Patent Nos. 3,839,041 and 3,84
Compounds described in No. 4,788 and No. 3,877.940 are also preferably used.

In the present invention, an image toning agent may be contained if necessary. Effective toning agents are 1,2°4-triazole, IH-tetrazole, thiouracil and 1,3.4
- Compounds such as thiadiazole. Examples of preferred toning include 5-amino-1,3,4-thiadiazole-2-thiol, 3-mercapto-1,2,4-)riazole, bis(dimethylcarbamyl)disulfy]
Examples include 6-methylthiouracil and 1-phenyl-2-tetrathion-5-thion. Particularly effective toning agents are compounds capable of forming black images.

The concentration of the toning agent contained varies depending on the type of photothermographic material, processing conditions, desired image, and other factors, but generally it is about 0.00 per mole of silver in the photosensitive material.
It is 1 to 0.1 mole.

Two different dye release aids can be used in the present invention. The dye release aid is a compound exhibiting basicity and capable of activating development, or a compound having so-called nucleophilicity, and a base or a base precursor is used.

The dye-releasing aid can be used in either a light-sensitive material or a dye-fixing material. It is especially advantageous to use a base precursor when it is included in a light-sensitive material. What is the base precursor here?

A base component is released by heating, and the base component released may be an inorganic base or an organic base.

Examples of preferred bases include inorganic bases such as alkali metal or alkaline earth metal hydroxides, secondary or tertiary phosphates, borates, carbonates, quinolates, mekborate; anguinium water; Oxides; hydroxides of quaternary alkylammonium; hydroxides of other metals, etc., and organic bases include aliphatic amines (trialkylamines, hydroxylamines, aliphatic polyamines), aromatic Group amine RCN-alkyl substituted aromatic amine [
, N-hydroxylalkyl-substituted aromatic amines and bis(p-(dialkylamino)phenylcomethanes)
, heterocyclic amines, amidines, cyclic amidines, guanidines, and cyclic guanidines. U.S. Pat. , No. 506,444, organic compounds containing amino acids such as urea and 6-aminocaproic acid are described and useful. In the present invention, those having a pKaO value of 8 or more are particularly useful.

Examples of base precursors include salts of ta-acids and bases that decompose by decarboxylation upon heating, compounds that decompose through Rossen rearrangement, Beckmann rearrangement, etc. and release amines, and those that cause some kind of reaction upon heating to release bases. is used.

Preferred base precursors include the aforementioned organic base precursors. For example, salts with thermally decomposable organic acids such as trichloroacetic acid, ) lifluoroacetic acid, propiolic acid, cyanoacetic acid, sulfonylacetic acid, acetic acid, and salts with 2-carboxycarboxamides as described in U.S. Pat. No. 4,088,496. Examples include.

Preferred specific examples of base precursors are not shown. Examples of compounds whose acid moieties are thought to decarboxylate and release bases include the following:

Examples of trichloroacetic acid derivatives include guanidine trichloroacetic acid, piperidine trichloroacetic acid, 9 morpholine trichloroacetic acid, p-toluidine trichloroacetic acid, 2 picoline trichloroacetic acid 1, and the like.

Other British Patent No. 998,945, U.S. Patent No. 3,2
Base precursors described in No. 20,846, JP-A-50-22,625, etc. can be used.

Other than trichloroacetic acid, U.S. Patent No. 4,0
88,496, the 2-carboxycarboxamito derivatives described in U.S. Pat.
Sulfonia acetate derivatives, patent application No. 58-55,700
Examples include salts of propiolic acid derivatives and bases described in No. In addition to organic bases, salts containing alkali metals and alkaline earth metals are also effective as base components;
8-69,597.

Precursors other than those mentioned above include hydroxamic carbamates described in Japanese Patent Application No. 3,860/1986 that utilize Rossen rearrangement, and Japanese Patent Application No. 31/6/1983 that generates nitriles.
The aldoxime carbamates described in No. 14 are effective.

In addition, the amine imide cheek JP 50-22 published in Research Disclosure magazine, May 1977 issue No. 15776,
Aldonamides described in 625-9 are preferably used because they decompose at high temperatures to produce bases.

These bases or base precursors can be used in a wide variety of ways. A useful range is 50% by weight or less of the coating conversion of the photosensitive material, more preferably,
It ranges from 0.01% to 40% by weight.

Of course, the above bases or base precursors can be used not only for promoting dye release, but also for other purposes such as adjusting the pT-I value.

The above-mentioned components constituting the heat-developable photosensitive material of the present invention can be placed at any appropriate position. For example, one or more of the components can be disposed in one or more layers of the light-sensitive material, if desired. In some cases, it may be desirable to include certain amounts (proportions) of reducing agents, image stabilizers, and/or other additives, such as those described above, in the protective layer. In this case, it is possible to reduce the movement of additives between layers of the photothermographic material.

It can also be advantageous.

The heat-developable photosensitive material according to the present invention is effective for forming negative-type images or positive-type images. Here, forming a negative or positive image will depend primarily on the selection of a particular photosensitive silver halide. For example, internal image halogens as described in U.S. Pat. silver oxide emulsion, and U.S. Patent No.
A variety of exposure means can be used in the present invention, in which mixtures of surface-imaged silver halide emulsions and internal-imaged silver halide emulsions such as those described in US Pat. The latent image is obtained by imagewise exposure to radiation, including visible light. In general, 1 Light sources used for ordinary color printing, such as tungsten lamps, mercury lamps, halogen lamps such as iodine lamps, xenon lamps, laser beams, and CRT light sources, fluorescent tubes 1
A light emitting diode or the like can be used as a light source.

In the present invention, development is carried out by applying heat to the photosensitive material, but the heating means may be a simple hot plate, iron, hot roller, heating element using carbon, titanium white, etc., or a heat generating element thereof. The silver halide used in the invention may be spectrally sensitized with methine dyes and others. Usually spectrally sensitized to green or red sensitivity,
It may be desirable to have sensitivity in the infrared region. The dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes and hemioxonol dyes. Particularly useful dyes are those belonging to the cyanine dyes, merocyanine dyes, and complex merocyanine dyes. Any of the nuclei commonly used for cyanine dyes can be used as the basic heterocyclic nucleus for these dyes. That is, pyrroline nucleus, oxazinone nucleus, thiazoline nucleus, pyrrole nucleus, oxazole nucleus, thiazole nucleus, selenazole nucleus, imidazole nucleus, tetrazole nucleus, pyridine nucleus, etc.; a nucleus in which an alicyclic hydrocarbon ring is fused to these nuclei; and these A nucleus in which an aromatic hydrocarbon ring is fused to the nucleus, that is, an indolenine nucleus,
Benzia 1' ray Zn nucleus, ind'-ol nucleus, pensuoxatol nucleus, nano l-oxazole nucleus, benzothiazole nucleus, nano 1~thiazole nucleus, henzoselenazole nucleus, benzimidazole nucleus, quinoline nucleus, etc. can be used. . These nuclei may be substituted on carbon atoms.

Merocyanine dyes or composite merocyanine dyes include a pyrazolin-5-one nucleus, a thiohydantoin nucleus, and a 2=thioxazolidine-2 nucleus having a ketomethylene structure.
, 1-dione nucleus, thiazolidine-2,4-dione nucleus, rhodanine nucleus, thiobalhituric acid nucleus, and the like can be applied.

These sensitizing dyes may be used alone or in combination, and combinations of sensitizing dyes are often used particularly for the purpose of supersensitization.

Along with the sensitizing dye, it is a dye that itself does not have a spectral sensitizing effect or a substance that does not substantially absorb visible light,
A substance exhibiting supersensitization may also be included in the emulsion. for example,
Aminostyryl compounds substituted with nitrogen-containing heterocyclic groups (for example, U.S. Pat. No. 2,933.390, U.S. Pat. No. 3,635,
721), aromatic organic acid formaldehyde condensates (such as those described in US Pat. No. 3,743,510), cadmium salts, azaindene compounds, and the like. U.S. Patent No. 3,615,613;
No. 615,641, 3. 617. No. 295, same 3
, 635.721 are particularly useful.

The support used in the light-sensitive material and the dye-fixing material used in some cases in the present invention is one that can withstand processing temperatures. Common supports used include glass, paper, metal and their analogs, as well as cellulose acetate film, cellulose ester film.

Included are polyvinyl acecool film, polystyrene film, polycarbonate film, polyethylene terephthalate film, and films or resin materials related thereto. Paper supports laminated with polymers such as polyethylene can also be used. U.S. Patent No. 3,634.089, U.S. Patent No. 3,725,070
The polyesters described in the above are preferably used.

The photographic light-sensitive material and dye-fixing material of the present invention may contain an inorganic or organic hardener in the photographic emulsion layer or other binder layer. For example, chromium salts (chromium alum, chromium acetate, etc.), aldehydes (formaldehyde, glyoxal, geltaraldehyde, etc.), N-methylol compounds (dimethylol urea, methylol dimethylhydantoin, etc.), dioxane derivatives (2,3-dihydroxydioxane, etc.) etc.), activated vinyl compounds (1,
3,5-triacryloyl-hexahydro-3-triazine, 1,3-vinylsulfonyl-2-propatol, etc.), active halogen compounds (2,4-dichloro-6-hydroxy-5-)riazine, etc.), muco Halogen acids (
mucochloric acid, mucophenoxychloric acid, etc.), etc. can be used alone or in combination.

A dye transfer aid can be used to transfer the dye from the photosensitive layer to the dye fixed layer.

For dye transfer aids, water, caustic soda, or caustic potash can be used as a dye transfer aid in a method in which the transfer aid is supplied externally.

A basic aqueous solution containing an inorganic alkali metal salt is used. Further, a low boiling point solvent such as methanol, N,N-dimethylformamide, acetone, diisobutyl ketone, or a mixed solution of these low boiling point solvents and water or a basic aqueous solution is used.

The dye transfer aid may be used in such a way that the image-receiving layer is wetted with the transfer aid.

If the transfer aid is incorporated into the photosensitive material or dye fixing material, there is no need to supply the transfer aid from the outside.

The above transfer aid may be incorporated into the material in the form of crystal water or microcapsules, or may be incorporated as a precursor that releases the solvent at high temperatures. More preferably, a hydrophilic thermal solvent that is solid at room temperature and melts at high temperature is incorporated into the light-sensitive material or dye-fixing material. The hydrophilic thermal solvent may be incorporated into any of the three dye-fixing materials of the photosensitive material, or may be incorporated into both. Further, the layer to be incorporated may be an emulsion layer, an intermediate layer, a protective layer or a dye fixing layer, but it is preferably incorporated in the dye fixing layer and/or its adjacent layer.

Examples of hydrophilic thermal solvents include ureas, pyridines, amides, sulfonamides, imides, alcohols, oximes, and other heterocycles. The method of transferring these image dyes to a dye-fixing material (so-called diffusion transfer) and visualizing them is described in the above-cited patent or Japanese Patent Application No. -4
It is described in No. 2.092, No. 58-55,172, etc.

After exposure, the photosensitive material of the present invention can be heated to about 80 DEG to about 250 DEG C. to form a movable dye in the form of an image.

To visualize this image cage, for example, a mobile dye is moved to a dye fixing layer and fixed. Next, the color image can be viewed by peeling off this fixing layer or by providing an opaque layer between the dye-donating substance-containing layer and the dye fixing layer and viewing from the opposite side.

The dye fixing layer preferably contains a dye mordant, for example, a dye mordant for fixing the dye.

The support having the photosensitive layer and the support having the dye fixing layer may be the same or may be provided separately. When provided separately, the material having the dye fixing layer is called a dye fixing material.

Other compounds that can be used in the light-sensitive material in the present invention 1 For example, sulfamide derivatives, cationic compounds having a pyridinium group, surfactants having a polyethylene oxide chain, antihalation and irradiation dyes, and hardening agents.

Regarding mordants etc., European Patent No. 76.492 and European Patent No. 66.
No. 282, West German Patent No. 3,315,485, Patent Application No. 1983
28928 and No. 58-26008 can be used. Also, as for methods such as exposure, the methods cited in the above-mentioned patents can be used.

61) Example L This article describes how to make a silver iodobromide emulsion.

Dissolve gelatin pop and KBrλag in 3ooowrtK of water. This solution! Keep at O0C and stir.

Next, a solution of 3 ag of silver nitrate dissolved in xooml of water is added to the above solution over a period of 10 minutes.

Thereafter, a solution of 3.3 g of KI dissolved in 100 g of water was added over 2 minutes.

The silver iodobromide emulsion thus produced is pHtl-adjusted, precipitated, and excess salt is removed.

Thereafter, the pH was adjusted to t and o to obtain a silver iodobromide emulsion with a yield of uoog.

Next, we will discuss how to prepare a thermally decomposable organic silver salt (41 emulsion).

Gelatin λtg and i, 4A-phenylene-bispropiolic acid//g are dissolved in 3000 rd of water. The solution is kept at UO°C and stirred. Silver nitrate/
A solution of 7 g dissolved in 1001 tL of water is added over 2 minutes. The pH of this mixture is adjusted and allowed to settle to remove excess salt. Then the pH was adjusted to 4. o to 70 to obtain a thermally decomposable organic silver salt (4G emulsion) with a yield of aoog.

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

jg of magenta dye-donating substance (2), cono-lyric acid -
λ-Ethylhexyl ester sulfonic acid sodium 0.1
Weigh out jg of 9% trichlorethylene phosphate (TCP), add 30 ml of ethyl acetate, and dissolve by heating to about 0°C to form a homogeneous solution. This solution and 10 g of gelatin solution are stirred and mixed, and then dispersed using a homogenizer for io minutes at lθ and OOORPM.

This dispersion is called a dispersion of the dye-providing substance (2).

Next, how to make photosensitive materials A, B, and C will be described.

Photosensitive material A (a) The above silver iodobromide emulsion λzg (b) Dispersion of dye-providing substance (2) 33g (c)
of a compound with the following structure! Aqueous solution 10ml (d) Dimethylsulfamide 10 (4 μm methanol solution e) Guanidine trichloroacetic acid (/ / jrrt
Ethanol solution according to lo) After mixing and dissolving the above (a) to (e), it was coated on a polyethylene terephthalate film to a wet film thickness of 30B7B and dried. Furthermore, the following composition was applied as a protective layer to a wet film thickness of λjttyl and dried.

(a) Gelatin iodine aqueous solution 319 (Lead succinate-λ-ethylhexyl μmlm sodium ester sulfonate aqueous solution C1) Water tulul Photosensitive material B (a) Pyrolyzable organic silver salt emulsion 109 (b) Iodobromide Silver emulsion 20g (c) Dispersion of dye-providing substance (2) 33fl (e
) Dimethyl sulfamide 1014 ethanol solution (f) Guanidine trichloroacetic acid (/ltagO ethanol solution) After mixing and dissolving the above (a) to (f), apply a wet film thickness of 30B1rL on a polyethylene terephthalate film. Apply and dry. Further, a protective layer having the same composition as the photosensitive material A was applied thereon to a wet film thickness of BTrL and dried.

Next, we will discuss how to make the dye fixing material.

Poly(methyl acrylate-N,N,N-)samethyl-N-vinylbenzylammonium chloride) (ratio of methyl acrylate and vinylbenzylammonium chloride is /:l) Dissolve 10g in 200ml of water,
0 (4) was mixed uniformly with 100 g of lime-treated gelatin. This mixture was uniformly applied to a wet film thickness of 2OB711 on a paper support laminated with polyethylene in which titanium dioxide was dispersed. After drying, this sample was fixed with dyes. It was used as a material.

-73= The above photosensitive materials A, B, and C were imagewise exposed for 10 seconds at 1,000 lux using a tungsten bulb.

Next, it was heated uniformly for 2 c seconds on a heat block heated to /u00c.

After soaking the film surface of the dye fixing material in water, the above photosensitive material A,
B and C were overlapped with the fixing material so that the film surfaces were in contact with each other, and heated uniformly for 4 seconds on a heat block heated to ro 0c. When the dye fixing material was peeled off from the photosensitive material, a negative magenta color image was obtained on the fixing material.

Photosensitive material C Photosensitive material C was prepared in exactly the same manner as photosensitive material B except that 10 g of the benzotriazole silver emulsion prepared as follows was used instead of the thermally decomposable organic silver salt (4G emulsion) used in photosensitive material B. It was created.

Preparation of benzotriazole silver emulsion: Dissolve gelatin-2tg and benzotriazole/3.2y in JOOml of water. The solution is kept at ≠00C and stirred. A solution prepared by dissolving 17I silver nitrate in 100% water is added to this solution over a period of 2 minutes.

74t- Adjust p)T of this benzotriazole silver emulsion, settle and remove excess salt. Then the pH was adjusted to t.

0 to obtain a benzotriazole silver emulsion with a yield of uoog.

The density of this negative image was measured using a Maquis reflection densitometer (RD-412).
), the following results were obtained.

Sample shop Maximum concentration Minimum concentration A (comparison) 1. μJ O, 13 B (present invention) 2. /4A O, COOC (comparison) 7.7≦00lf The above results show that the thermally decomposable organic silver salt 4 of the present invention provides a high maximum concentration and a low minimum concentration.

Example 2 In place of the thermally decomposable organic silver salt emulsion used in Example 1, a thermally decomposable organic silver salt (4[) prepared as follows was used.

10 volumes of methanol and! 1 consisting of water with a capacity of O
Phenyl-/,44-dipropiolic acid s, sg was dissolved in 00ml of solvent. Separately, silver nitrate r.

A solution prepared by dissolving 100 g of 100 g of water was mixed and stirred into 1.4 L of phenylene-bispropiolic acid solution. pHt
, after adjusting to o, filter the formed yellowish white precipitate, /,
! - Phenylene to silver bispropiolate (4Q was obtained.

A coating material having the following composition was coated on a polyethylene terephthalate support to a wet film thickness of 30 BrrL and dried.

(a) Pyrolyzable organic silver salt (4(i 0 , 4 g(b
) Silver iodobromide emulsion (described in Example 1 -20g) (c) Dispersion of dye-providing substance (2) 33g (described in Example 1) (d) TL aqueous solution of a compound having the following structure 10rrtl
(e) Dimethylsulfamide (10% μvil ethanol solution) (f) Guanidine trichloroacetic acid (/ / l, vt
l! (g) Gelatin (3,j aqueous solution) iog Further, the protective layer described in Example 1 was coated thereon to a wet film thickness of -21 Bm and dried to prepare a photosensitive material.

When processed in the same manner as in Example 1, a negative magenta image with a maximum density of 2°07 and a minimum density of 0.22 was obtained on the fixed material. This shows that a useful thermally decomposable organic silver salt can be obtained simply by mixing a thermally decomposable organic acid solution and a silver nitrate solution.

Example 1 Table 1 shows the maximum and minimum densities of images obtained by performing exactly the same operations as in Example 2, except that the following thermally decomposable organic silver salt prepared in the same manner as in Example 2 was used. show.

It can be seen that the thermally decomposable organic silver salt of the present invention has high concentration and low fog.

Example A dispersion of the dye-donating substance was prepared in the same manner as in Example 1 using the following dye-providing substance in the dye-donating substance (2) of Table Example 1.

Dye-donating substance (8) 1g Dispersion (I) (417,
j g Dispersion (II) a'a jg Dispersion (In) Samples were prepared in exactly the same manner as in Example 1, and treated in the same manner. The results obtained are shown below.

The above results show that the thermally decomposable organic silver salt of the present invention is useful for any dye-donating substance.

Examples & How to make a thermally decomposable organic silver salt (4G emulsion) containing photosensitive silver bromide will be described.

/, μm) Dissolve 22-bisprobiolic acid tg and gelatin 109 in water 1000. This solution is po
Keep stirring at 0c.

Next, a solution prepared by dissolving r,jg of silver nitrate in 10 - of water is added to the above solution over a period of 2 minutes.

Next, a solution of 2 g of potassium bromide dissolved in 10 ml of water is added over 2 minutes.

The prepared emulsion is subjected to pH adjustment and sedimentation to remove excess salt. Then p)T of the emulsion was adjusted to 4. Adjusted to o. Yield was 200g.

Next, how to make the photosensitive material (C) will be described.

(a) A thermally decomposable silver salt containing photosensitive silver bromide (
41 Emulsion (b) Dispersion of dye-providing substance (2) (33g-
4/- male side 1) 33g (d) Dimethylsulfamide (10% 44ml ethanol solution) (e) Guanidine trichloroacetic acid (10% ethanol solution) 11ml Mix and dissolve above (a) to (e) After this, it was applied onto a polyethylene terephthalate film in a wet film thickness of 30 g and dried. Furthermore, a protective layer having the composition described in Example 1 was applied thereon to a wet thickness of 2jBm and dried.

A completely similar coating solution was prepared, except that 21 g of the photosensitive silver bromide emulsion shown below was used instead of the above-mentioned photosensitive silver bromide-containing thermally decomposable organic silver salt (41 emulsion), applied, dried, and exposed to light. Material (D) was prepared.

Preparation of silver bromide emulsion Gelatin iog and KBr7. -2. water lit / 00
Dissolves in 0d. This solution is kept at ≠o0c and stirred.

Next, a solution prepared by dissolving silver nitrate and Ig in water was added to the above solution over a period of 2 minutes. The prepared emulsion p)
Excess salt is removed by sedimentation using a TFJI filter.

Thereafter, the pH of the emulsion was adjusted to t and o. The yield is cooog
Met.

When the photosensitive materials (C) and (D) were processed in the same manner as in Example 1, the following magenta color images were obtained.

Sample shop Maximum concentration Minimum concentration (C) (invention) /, 13 0. /It(D) (comparison) 0. /r O6/2 It can be seen that the thermally decomposable organic silver salt of the present invention is effective even when prepared in the same system as the photosensitive silver halide.

Patent applicant: Fuji Photo Film Co., Ltd. r3 -

Claims (1)

[Claims] A heat developable material having on a support at least a photosensitive silver halide, a thermally decomposable organic silver salt, a binder, and a dye-providing substance that is reducible and releases a mobile dye in the form of an image when oxidized when heated. Color photosensitive material.