JPS59180551A - Heat-developable color photosensitive material and dye image forming method using it - Google Patents

Abstract

PURPOSE:To accelerate heat development by using a photosensitive material contg. photosensitive silver halide, a binder and a specified dye providing substance on a support. CONSTITUTION:A heat-developable color photosensitive material contg. flat platelike photosensitive silver halide, a binder and a dye providing substance which has power of reducing the silver halide and releases a hydrophilic diffusible dye by a reaction with the silver halide under heating on a support is used. The diameter of the particles of the silver halide is >=5 times the thickness. The dye providing substance used in this invention is represented by a general formula Ra-SO2-D, wherein Ra is a reducing moiety oxidizable with silver halide, and D is an image forming dye moiety having a hydrophilic group. For example, a compound represented by formula I or II is used as the dye providing substance. When the photosensitive material is heated to >=80 deg.C, the dye providing substance reduces the silver halide or the silver halide and an org. silver salt oxidizing agent using nuclei of a latent image as a catalyst to form silver, and the dye providing substance itself is oxidized to release the dye.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a new heat-developable color photosensitive material containing a dye-donating substance that reacts with photosensitive silver halide to release a hydrophilic dye upon heating in a substantially water-free state. It is.

The present invention further relates to a new method of forming dye images by heating in a substantially water-free state.

The present invention particularly relates to a new method for obtaining dye images by transferring dyes that have been released by heating to a dye fixing layer.

Photographic methods using silver halide have been used most widely since they have superior photographic properties such as sensitivity and gradation control compared to other photographic methods such as electrophotography and diazo photography. In recent years, a technology has been developed that allows images to be easily and quickly obtained by changing the image forming method for photosensitive materials using silver halide from the conventional wet processing using a developing solution to a dry processing using heating, etc. It has been.

The present applicant has proposed a new heat-developable color photosensitive material capable of obtaining a color image by dry processing, which comprises on a support a photosensitive silver halide, a binder, and a reducible material for the photosensitive silver halide. C Patent Application Akihito has applied for a patent for the invention of a heat-developable color photosensitive material having a dye-donating substance that reacts with the photosensitive silver halide by heating in a substantially water-free state to release a hydrophilic dye. -/,!
177ri r, 77-/jri 2tg). The present invention is intended to further improve this heat-developable color photosensitive material.

The object of the present invention is to provide a silver halide heat-developable color photosensitive material containing a dye-providing substance that reacts with silver halide to release a mobile hydrophilic dye when heated in a substantially water-free state; The object of the present invention is to provide a heat-developable color photosensitive material in which heat development proceeds rapidly in a method of forming a mobile hydrophilic dye in an imagewise manner by development, and a method of forming a dye image using the same.

The above-mentioned object of the present invention is to provide at least a support with a tabular photosensitive silver halide having a grain size of 5 times or more of the grain thickness, a binder, and the above-mentioned silver halide, which is reducible to the above-mentioned silver halide; A heat-developable color photosensitive material characterized by containing a dye-providing compound that reacts with silver halide to release a hydrophilic dye upon heating, and a heat-developable color photosensitive material as described below using this photosensitive material. , and further by a method of transferring a dye image.

The most important feature of the present invention is the use of tabular photosensitive silver halide whose grain size is at least 5 times the grain thickness.

The most unexpected effect of the present invention is that by using this tabular silver halide, it is possible to achieve a higher level of silver halide than by using silver halide with other crystal structures (for example, irregular, cubic, octahedral, etc.). The reaction in which the dye-donating substance reacts in a substantially water-free state to release a mobile dye becomes extremely fast.

In addition, in the present invention, the emulsion layer can be made thinner by using tabular silver halide, so the distance that the generated mobile hydrophilic dye moves to the dye fixed layer is shortened, which improves the transfer speed. The effect of significantly improving the sharpness of the transferred image is also obtained.

Since the present invention exhibits such various effects, it is particularly suitable for application to multilayer, multicolor photographic materials.

Next, the tabular silver halide grains used in the present invention will be described.

The tabular loge/silveride grains of the present invention preferably have a ratio of diameter/g of 5 or more, more preferably j
More than ioo, more preferably more than j! It is 0 or less (particularly preferably 7 or more and 20 or less).

The diameter of a silver halogenide grain herein refers to the diameter of a circle having an area equal to the projected area of the grain. In the present invention, the diameter of the tabular silver halide grains is preferably 0, /-10μ,
More preferably 0.3 to j, 0μ, particularly preferably 01
S-φ and θμ.

In general, tabular silver halide grains are tabular with two parallel faces, and therefore have a "thickness"
is expressed as the distance between two parallel planes constituting a tabular silver halogenide grain.

The compositions of tabular silver halogenide grains include silver chloride, silver chlorobromide, silver chloroiodide, silver bromide, silver iodobromide, silver chloroiodobromide, and silver iodide. . In the present invention, when an organic silver salt oxidizing agent described below is not used in combination, grains containing silver iodide crystals in part, that is, pure silver iodide when analyzed by X-ray diffraction of silver halide. Particularly preferred are those with a pattern of .

Next, a method for producing tabular silver halogenide grains will be described.

The tabular silver halogenide grains can be produced by appropriately combining methods known in the Todoroki industry.

For example, seed crystals containing 110% or more of tabular grains by weight are formed in an atmosphere with a relatively high pAg value of pf3r/, 3 or less, and silver and halogen solutions are simultaneously added while keeping the pBr value at the same level. Obtained by growing seed crystals.

During this grain growth process, it is desirable to add a silver and halogen solution to prevent the generation of new crystal nuclei.

The size of the tabular silver halide grains can be adjusted by controlling the temperature, selection of the type and amount of solvent, the silver salt used during grain growth, the addition rate of halide, etc.

When producing the tabular silver halide grains of the present invention, p, grain size,
Particle shape (diameter/thickness ratio, etc.), particle size distribution,
The growth rate of particles can be controlled. The amount of solvent used is to 3~/, 0 weight φ of the reaction solution, especially io ”
~10-1 vehicle volume ratio is preferable.

For example, as the amount of solvent used increases, the particle size distribution can be made monodisperse and the growth rate can be accelerated. On the other hand, there is also a tendency for the thickness of the particles to increase with the amount of solvent used.

Often used silver halide solvents include ammonia, thioethers and thioureas. Regarding thioethers, U.S. Pat. λ7/,/
No. 17, No. 3, No. 7, No. 3g7, No. 3. j7≠,
You can refer to No. t2Ir etc.

During the production of the tabular silver halide grains of the present invention, the addition rate, amount, and concentration of the silver salt solution (e.g., AgN03 aqueous solution) and halide solution (e.g., KBr aqueous solution), which are added to accelerate grain growth, are increased. A method is preferably used.

These methods are described, for example, in British Patent No. 1.33,
No. 2j, U.S. Patent No. 3. t7co, No. 200, No. J
, 430.7jt No. 7, same No. 1 Hiro, Ko Hiro 2, Hiro≠! Issue, Tokukai Show 3! -/ψ232nd issue, jj-/3112ψ,
Research Disclosure Magazine 3rd year/monthly issue
- You can refer to the descriptions on page S, etc.

The tabular silver halide grains of the present invention can be chemically sensitized if necessary.

As a chemical sensitization method, there is a so-called gold sensitization method using a gold compound (for example, US Pat. No. 2,4L≠r, ot.

U.S. Pat. 2.j1.t, No. 263) or a sulfur sensitization method using a sulfur-containing compound vOk (for example, U.S. Pat. No. 2.22
2.16≠), or reduction sensitization using tin salts, polyamines, etc. (for example, U.S. Pat. No. 2.'l17.gjO,
Same +2. It is possible to use a combination of two or more of these.

In the layer containing the tabular silver halide grains of the present invention,
It is preferable that the tabular grains are present in a weight ratio of ≠04 or more, particularly tOS or more, to all the silver halide grains in the layer.

The thickness of the layer containing tabular silver halide grains is from 0.3 to
It is preferable that r, oμ, load is O,S ~ 3.0μ.

The emulsion layer of the silver halide photographic light-sensitive material of the present invention may contain electrically conductive silver halide grains in addition to tabular silver halide grains. These are P, Glaf
kids-! jF Chimie etPhysi
que Photographique (Pau
Published by Montel / 1967), G, F, Duf
Photographic Emulsio by fin
n Chemistry (The Focal Pre
ss/re 1966), V, L, Zelikman et
Making and Coating Ph
otographic Emulsion(The
It can be prepared using the method described in Focal Press, /911f).

That is, any of the acidic method, neutral method, ammonia method, etc. may be used, and the method for reacting the soluble silver salt and soluble halogen salt may be any one-sided mixing method, simultaneous mixing method, or a combination thereof. .

It is also possible to use a method in which particles are formed in an excess of silver ions (so-called back-mixing method).

As one form of the simultaneous mixing method, a method in which the pNg in the liquid phase in which silver halide is produced can be kept constant, that is, a so-called Chondrald double jet method can also be used.

The silver halide may be any one such as silver bromide, silver iodobromide, silver iodochlorobromide, silver chlorobromide, and silver chloride.

In the process of silver halide grain formation or physical ripening,
Cadmium salt, zinc salt, lead salt, thallium salt, iridium salt or its complex salt, rhodium salt or its complex salt, iron salt -
! 7) Iron complex salts and the like may be present together. Further, if necessary, chemical sensitization can be carried out in the same manner as tabular silver halide grains.

In the image forming method of the present invention, a silver image and a movable dye can be simultaneously provided in the area corresponding to the silver image by simply heating at the same time as or after image exposure. That is, in the color image forming method of the present invention, image exposure is performed, and heat development is performed in a state substantially free of water, whereby the exposed photosensitive silver halide is used as a catalyst to form a photosensitive silver halide and a reducing dye-donating substance. A redox reaction occurs between the two, producing a silver image in the exposed area. In this step, the dye-donating substance is oxidized by silver halide to form an oxidant9, resulting in the release of a hydrophilic iiJ mobile dye, resulting in a silver image and a mobile dye in the exposed area. . At this time, the presence of a dye release aid accelerates the above reaction. A dye image is obtained by moving this mobile dye to, for example, a dye fixing layer.

The above is a case where a negative type emulsion is used, but when an autopositive emulsion is used, a silver image and a mobile dye are obtained in the unexposed areas, but it is the same as when using a negative type hole MIJ'e. It is.

The oxidation-reduction reaction between the photosensitive silver halide and the dye-donating substance of the present invention and the subsequent dye-releasing reaction are characterized in that they occur at high temperatures and in a dry state substantially free of water. . Here, high temperature refers to a temperature condition of tro 0c or higher, and a dry state that does not substantially contain water refers to a state in which the water in the air is in equilibrium but there is no water supplied from outside the system. . Such a state is “' The
theory of the photograp
hic process” HirothEd, (E
Dited by T. H. James.

Macmillan) 37tl member.

The fact that a sufficient reaction rate is exhibited even in a dry state containing substantially no water can be confirmed from the fact that the reaction rate of the sample vacuum-dried at f+L10-3 mmHg was not low.

Conventionally, the dye release reaction is thought to be caused by the attack of a so-called nucleophile, and is usually carried out in a liquid with a high pH of 10 or more. It is unexpected that the dye-providing substance of the present invention does not exhibit a high reaction rate in a dry state without containing water.Also, the dye-donating substance of the present invention can be used without the aid of a so-called auxiliary developer. Can perform redox reactions with silver. This is an unexpected result based on previous knowledge of wet development at temperatures around room temperature.

The above reaction sometimes proceeds well in the presence of an organic silver salt oxidizing agent and exhibits high image quality. Therefore, it can be said that it is a particularly preferable embodiment to coexist an organic silver salt oxidizing agent.

The organic silver salt oxidizing agent used in this particularly preferred embodiment includes (
aKIo 0c or higher, preferably io.

When heated to 6C or more, it reacts with a dye-donating substance or, if necessary, a reducing agent coexisting with the dye-donating substance, to form a silver image. By coexisting with an organic silver salt oxidizing agent, it is possible to obtain a photosensitive material exhibiting a highly concentrated color development.

Examples of such organic silver salt oxidizing agents include the following.

It is a silver salt of an organic compound having a carboxyl group, among which VC is a typical example of dtA of an aliphatic carboxylic acid.
and silver salts of aromatic carboxylic acids.

Examples of aliphatic carboxylic acids include silver salts of behe/ba, silver salts of stearic acid, silver salts of oleic acid, @ salts of lauric acid, silver salts of capric acid, silver salts of myristic acid, and olumitin. Silver salts of acids, silver salts of maleic acid, silver salts of fumaric acid, silver salts of tartaric acid, silver salts of furoic acid, silver salts of linoleic acid, silver salts of oleic acid, silver salts of adipic acid, silver salts of sepacic acid. salt,
These include silver salts of succinic acid, silver salts of butyric acid, silver salts of butyric acid, and silver salts of camphoric acid. Also effective are these silver salts substituted with a 7-rogen atom or a hydroxyl group.

Silver salts of aromatic carboxylic acids 2 and other carboxyl group-containing compounds include silver salts of benzoic acid, silver salts of 3゜j-dihydroxybenzoic acid, silver salts of 0-methylbenzoic acid, m
- silver salt of methylbenzoic acid, silver salt of p-methylbenzoic acid,
≠-dichlorobenzoic acid, JjA, silver salts of substituted benzoic acids such as silver salts of acetamidobenzoic acid, silver salts of p-phenylbenzoic acid, silver salts of erosion f acids, silver salts of tannic acid,
Silver salt of phthalic acid, silver salt of terephthalic acid, steel weight of salicylic acid, silver salt of phenylacetic acid, silver salt of pyromellitic acid, US Patent No. 3.7g! and silver salts such as 3-carboxymethyl-≠-methyl-≠-thiazoline-2-thione described in No. 30, and aliphatic compounds having a thioether group as described in U.S. Pat. No. 3,330°663 MB. Chew silver salts of carboxylic acids.

Other examples include silver salts of compounds having mercapto groups or thio/groups and derivatives thereof.

For example, 3-mercapto-l-phenyl-/, 2゜≠-
Silver salt of triazole, silver salt of 2-mercaptobenzimidazole, silver salt of λ-mercapdoter aminothiadiazole, silver salt of 2-mercaptobenzthiazole, 2-
(s-ethylglycolamide)benzthiazole silver salt, S-alkyl (alkyl group having 72 to 2 carbon atoms) thioglycolic acetic acid, etc. Silver salts of dithiocarboxylic acids, silver salts of thioamides, such as silver salts of thioglycolic acid and silver salts of dithioacetic acid, and silver salts of thioamides, as described in No. 1-2g2.
, silver salt of t-carboxyi-may-2-phenyl-≠-thioviridine, silver salt of mercaptotriazide, silver salt of 2-mercaptobenzoxazole, silver salt of mercaptooxadiazole, US patent≠ .

/23,27≠Silver salts described in Meikunsho, for example /.

3-7 minnow, which is a coumercaptotriazole derivative, and one benzylthio/2. ≠-Silver salt of triazole, U.S. Patent 3.30/, j-(
, 2carboxyethyl)-Hiro-methyl-≠-thiazoline-lambda thione.

In addition, there are complex salts of compounds having imino groups. For example, Tokko Showφ'/--30270, same≠5-/l'l/
Silver salts of benzotriazole and its derivatives as described in J Publication, such as be/zo) IJ thiazole silver salts, silver salts of alkyl-substituted be/citriazoles such as silver salts of methylbencitriazole, and silver j-chlorobenzotriazoles silver salts of rogen-substituted benzotriazoles, such as salts;
Silver salts of carbimidobenzotriazoles, such as silver salts of butylcarboimidobe/citriazole, U.S. Pat.
220゜709, 2. Examples include silver salts of l/--) riazole and /-1(-tetrazole, silver salts of carbazole, silver salts of saccharin, and silver salts of imidazole and imidazole derivatives).

-Also Research Disclosure Vol.1i7o.

Organometallic salts such as silver salts and copper stearate, which are described in A/7022 published in 2007, are also specific metal salt oxidizing agents that can be used in the present invention.

Two or more types of organic silver salt oxidizing agents can be used in combination.

Although the thermal development process during heating in the present invention is not fully understood, it can be considered as follows.

When a photosensitive material is irradiated with light, it becomes photosensitive) - A latent image is formed on the silver halide. Regarding this, T.

“The Theory of
thePhotographic process
” 3rdEdition ios page~/
It is described in Hiro, 1' Kai.

By heating the light-sensitive material, the reducing agent, in the case of the present invention, the dye-donating substance, converts silver halide or silver halide and an organic silver salt oxidizing agent using the a-image nucleus as a catalyst, It is produced throughout the thighs and itself is oxidized to release pigment. In this case, the coexistence of a nucleophilic reagent promotes the dye release reaction.

For information on how to make these silver halides and organic silver salt oxidizing agents and how to mix both, please refer to Research Disclosure/No.
i-≠ノ, 5'2, U.S. Patent 3.700. ≠str No., JP-A-Sho-tter/32.2'1, JP-A-Sho-i7.
It is described in issue 2ig.

In the present invention, the coating amount of photosensitive silver halide is suitably from 711 da to /0!/m'' in terms of silver.

Further, the coating amount of the Mayan silver salt oxidizing agent, which is used as necessary, is suitably less than /09/fn2 in terms of silver. Further, it is appropriate to use the amount in a range of 700 mol or less per 1 mol of silver halide, and more preferably in a range of 0.01 mol to SO mol.

The photosensitive silver halide, organic silver salt oxidizing agent of the present invention is prepared in the following binder. A dye-providing material is also dispersed in the binder described below.

The binders used in the present invention can be contained alone or in combination. This binder has
Hydrophilic materials can be used. Typical hydrophilic binders are hydrophilic colloids that are transparent or translucent, such as gelatin, gelatin derivatives, cellulose derivatives, and natural colloids such as starch and polysaccharides such as gum arabic. and synthetic polymeric materials such as water-soluble polyvinyl compounds such as polyvinylpyrrolidone, acrylamide polymers, and the like. Other synthetic polymeric compounds include dispersed vinyl compounds, which increase the dimensional stability of photographic materials, especially in the form of latexes.

The silver halide used in the present invention may be spectrally sensitized with methine dyes and others. The pigments used include cyanine pigments, merocyanine pigments, composite cyanine pigments, composite merocyanine pigments, holopolar cyanine pigments,
Included are hemicyanine dyes, styryl dyes and hemioxonol dyes. 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, oxazoline nucleus,
Thiazoline nucleus, virol 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 an aromatic hydrocarbon ring in these nuclei is fused, indolenine nucleus, benzindolenine nucleus, indole nucleus, benzoxadole nucleus, naphthoxazole nucleus, benzothiazole nucleus, naphthothiazole nucleus, benzoselenazole nucleus, benzimidazole nucleus,
Quinoline nuclei etc. can be applied.

These nuclei may be substituted on carbon atoms.For merocyanine dyes or complex merocyanine dyes, nuclei having a ketomethylene structure include pyrazolin-5-one nucleus, thiohydantoin nucleus, and 2-thioxazolidine-2,4-
5- to 6-membered heterocyclic nuclei such as a dione nucleus, a thiazolidine-2,4-dione nucleus, a rhodanine nucleus, and a thiobarbyl scattering are applicable.

Useful sensitizing dyes include, for example, German Patent No. 929.0
No. 80, U.S. Patent No. 2,231.658, U.S. Patent No. 2,493
, No. 748, No. 2.503.776, No. 2,519,
No. 001, No. 2,912゜329, No. 3,656,9
No. 59, No. 3.672.897, No. 3,694.21
'7, 4゜025.349, 4,046,57
No. 2, British Patent No. 1,242,588, Special Publication No. 1977-1
Examples include those described in No. 4030 and No. 52-24844.

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

A typical example is U.S. Patent No. 2,688,545, 2.9
No. 77.229, No. 3,397,060, No. 3,52
No. 2,052, No. 3.527.641, No. 3,617
, No. 293, No. 3,628°964, No. 3,666.
No. 480, No. 3,672.898, No. 3,679,4
No. 28, No. 3゜703.37'7, No. 3,769,3
No. 01, No. 3.814,609, No. 3,837,86
No. 2, No. 4,026,707, British Patent No. 1,344.
No. 281, No. 1,507,803, Special Publication No. 43-49
No. 36, No. 53-12,375, JP-A No. 52-110
, No. 618 and No. 52-109,925.

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,
Aminostyl compounds substituted with nitrogen-containing heterocyclic groups (for example, U.S. Pat. No. 2,933.390, U.S. Pat. No. 3,635,7)
21), 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, U.S. Patent No. 3,6
No. 15,641, No. 3,617,295, No. 3,63
The combinations described in No. 5,721 are particularly useful.

The support used in the present invention is one that can withstand the processing temperatures. Common supports include glass,
Not only paper, metal and their analogs are used;
Included are cellulose acetate film, cellulose ester film, polyvinyl acecool film, polystyrene film, polycarbonate film, polyethylene terecrate film, and films or resin materials related thereto. Polyesters described in US Pat. No. 3,634,089 and US Pat. No. 3,725,070 are preferably used.

The reducing dye-donating substance that releases the hydrophilic diffusible dye used in the present invention has the following general formula % (%) where Ra represents a reducing substrate that can be oxidized by silver halide, and D contains a dye part for image formation that has a hydrophilic group.

The reducing substrate in the dye-donating substance Ra 802 D (
Ra ) is the redox potential relative to a saturated calomel electrode in polarographic half-wave potential measurement using acetonitrile as a solvent and sodium perchlorate as a supporting electrolyte.
, JV or less is preferable. Preferred reducing substrates (Ra) have the following general formulas (I[) to (IX).

NH NH- NH- 几a aA NH- Here, Rλ, R, ", R,", and R'a are each a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group,
alkoxy group, aralkyl group, aralkyl group, acyl group, acylamino group, alkylsulfonylamino group, arylsulfonylamino group, arylokyneargyl group,
Alkoxyalkyl group, N-substituted carbamoyl group, N-
Represents a group selected from a substituted sulfamoyl group, a halogen atom, an argylthio group, and an arylthio group, and the D alkyl group and aryl group in these groups can further be an alkoxy group, a halogen atom, a hydroxyl group, an /ano group, an acyl group, It may be substituted with an acylamino group, substituted carbamoyl group, substituted sulfamoyl group, alkylsulfonylamine group, arylsulfonylamino group, substituted ureido group or carbo'alcoquine group.

Furthermore, the hydroxyl group and amino group in R and a may be protected with a protecting group that can be regenerated by the action of a nucleophilic reagent.

In a further preferred embodiment of the present invention, the reducing substrate R, a
is expressed by the following formula (X).

Ga Here, G represents a hydroxyl group or a group that provides a hydroxyl group through hydrolysis. Ra is intended to be an alkyl group or an aromatic group. Hail an integer between n and 3.

0 X represents an electron-donating substituent when n = /; when n = 2 or 3, it may be the same or different substituent; Alternatively, the third one is an electron-donating group or a halogen atom, and may form a condensed ring with X itself or a ring with ORa.

The total number of carbon atoms of both Ra and X is g or more.

Among those included in the formula ([) of the present invention, in a more preferred embodiment, the reducing substrate Ra is represented by the following formulas (Xa) and (Xb).

Here, Ga represents a hydroxyl group or a group that provides a hydroxyl group through hydrolysis. aa and Ra may be the same or different, and each may be an argyl group, or Ra and Ra may be linked to form a ring.

3 Ra represents a hydrogen atom or an alkyl group, and Ra represents an alkyl group or an aromatic group. X and X may be the same or different, and each represents a hydrogen atom, an alkyl group, an alkyloxy group, a halogen atom, an acylamino group, or an alkylthio group, and furthermore, Ra and You may.

Ga Here, Oa is a hydroxyl group or a group that provides a hydroxyl group upon hydrolysis, aa is an alkyl or aromatic group, X is a hydrogen atom, an alkyl group, an alkyloxy/group, a halogen atom, an acylamino group, or an alkylthio group, and X2 and R%O may be connected to form a ring.

Specific examples encompassed by (X), (Xa), and (Xb) are USp, orr, tt2g, %Kaisho! rl-
/, 2t gu! No., and same as left, <-/i! : / 3
Each is listed in No. 0.

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

(Tatashi, symbols Ga, X, Ra and n are expressed by the formula (X
) has the same meaning as oa, xlO, R%On. ) Among those included in (X[) of the present invention, in a more preferred embodiment, the reducing substrate (Ra) has the following formula (X[a) to
(Represented by X[c).

However, Ga is a hydroxyl group or a group that gives a hydroxyl group by hydrolysis; 1 Ra and Ra may be the same or different and each represents an alkyl group or an aromatic group; Ra and Ra combine to form a ring R2a5 represents a hydrogen atom, an alkyl group or an aromatic group; 4 Ba represents an alkyl group or an aromatic group; RJ2+
5 represents an alkyl group, an alkoxy group, an alkylthio group, an arylthio group, a norogen atom, or an acylamino group; p is 0, l or 2; Ra and Ra are combined to form a condensed ring; It's okay<;
Ra and 几a may be combined to form a condensed ring.
Ra, R, and a may be combined to form a condensed ring, and the total number of carbon atoms in Ra5RaX, \4Ra, and (Ra)p is greater than 7.

However, Ga is a hydroxyl group or a group that gives a hydroxyl group by hydrolysis; r (3a1 represents an alkyl group or an aromatic group; 2 Ra represents an alkyl group or an aromatic group; 3 Ra is an alkyl group, an alkoxy group, an alkylthio group , an arylthio group,) represents a rogen atom or an acylamino group; q is 0, / or λ; R3a2 and R3a3 may be combined to form a condensed ring<;Ra (!: Ra is a bond You can also form a fused ring by
; RV and Rt3 may be combined to form a condensed ring; and the total number of carbon atoms in RaXRa, (Ra ) q is 7
bigger.

Ga In the formula, Ga represents a hydroxyl group or a group that provides a hydroxyl group by hydrolysis; RV represents an alkyl group or an aromatic group; R4a2 represents an alkyl group, an alkoxy group, an alkylthio group, an arylthio group, /・rogen atom, or represents an acylamino group; r is 0. / or 2; No-, \, -', and the carbon atoms in the condensed ring that participate in the bonding to the phenol (or its precursor) mother nucleus; the atoms (---a-) are fused. A 37'-class carbon atom constituting one element of a ring, and even if some of the carbon atoms in the hydrocarbon ring (excluding the above-mentioned tertiary carbon atoms) are substituted with oxygen atoms. Alternatively, the hydrocarbons may have a substituent or may be further fused with an aromatic ring; they may form a ring. However, the specific examples included in Ra\ (Ra), and the above (XI), (X[a) to (X[b)] are as follows: - Described in Hiro 0113.

The essential part of formula (III) and formula (IV) is the .xilar(sulfonyl)amine phenol moiety.

A specific example is U'S3.22g, 3/2, US
41. , o7a , txri, US Publish
edPatent Application B
3! / , A2B, US'1. /31. Ri2ri,
IJi9#, 2! ;I.

Examples include reducing substrates disclosed in No. 120, which are also effective as reducing substrates (Ra) of the present invention.

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

Here, Ba1last represents a diffusion-resistant group.

Ga represents a hydroxyl group or a precursor of a hydroxyl group.

Ga represents a group that has an aromatic ring and forms a Natsutareno ring together with a benzene ring. n and m are/or -
Find the integers that are .

Specific examples included in the above (■) are US-ta, or3゜37
It is described in 2.

The reducing substrates of formulas (V), (■), (■), and (IX) are characterized by ξ containing a heterocycle; specific examples include US Hiromu, /91.23! , JP-A-Sho j3-≠g7s
OXU8≠, 273. g! ! These include those listed in . Specific examples of the reducing substrate represented by formula (Vl) are US≠, /Hirohi.

There is a description in g9-2.

The following properties are required for the reducing substrate Ra.

1. It is rapidly oxidized by silver halide and efficiently releases a diffusible dye for image formation through the action of a dye release aid.

2. The dye-donating substance must be difficult to diffuse in a hydrophilic or hydrophobic binder, and only the released dye needs to be diffusible. Therefore, the reducing substrate R has a large hydrophobic property. to have

3. It has excellent stability against heat and dye release aids, and does not release image-forming dyes until oxidized.

4. Easy synthesis.

Next, preferred specific examples of Ra that satisfy these conditions will be shown. In the examples, NH- represents a linkage with a dye moiety.

C4H9([) C5H□1([) C6H13 CH-C-CI(3 3H7 CH-C-CH3CH3 1 CH-C-CH3 CH3 oc engineering. H33 H 0C engineering. H33 0C16H33 0C□6H33 NH- NH- NH- Dyes that can be used as image-forming dyes include azo dyes, -dimethine dyes, a7traquinono dyes, naphthoquine dyes, styryl dyes, nitro dyes, quinolino L dyes, carbonyl dyes, and phthalocyanino dyes; representative examples include. is shown on the dye side.This dye can also be used in a temporarily shortened form, which allows multicoloring during development.

Erotic GR? 52 R, a 1 Ra C-C-C-NHRa H -zenta ■ 1 OR, 1 a 5.1 \ Ra OHONHRa 8-OH In the above formula, Ra to R, a each represent a hydrogen atom, an anokyl group, or a cyclo Alkyl group, aralkyl group, alkoxy group,
Aralkyl group, aryl group, acylamino group, afur group, cyan group, hydroxyl group, anokylsulfonylamine group, arylsulfonyl 7mino group, alkylsulfonyl group, hydroxyanokyl group, anoalkyl group, alkoxycarbonylalkyl group, alkoxyalkyl group group, aryleoxyalkyl group, nitro group, halokene, sulfamoyl group, N-substituted sulfamoyl group, car'-E i/+
4. Represents a substituent selected from N-ff substituted carbamoyl group, acyloxyalkyl group, ami7 group, substituted amine group, alkylthio group, arylthio group, and the alkyl group and The aryl group moiety further includes...a rogen atom, a hydroxyl group, a cyan group, an aryl group, an acylamino group, an alkoxy group, a carbamoyl group, and more! Substituted carbamoyl group, sulfamoyl group, w-substituted sulfamoyl group,
It may be substituted with a carboxyl group, an alkylsulfonylamine group, an arylsulfonylamino group or a ureido group.

Hydrophilic groups include hydroxyl group, carboxyl group, sulfo group,
Phosphoric acid group, imide group, hydroxamic acid group, quaternary anomonium group, carbamoyl group, substituted carbamoyl group, sulfamoyl group, substituted sulfamoyl group, sulfamoylamino group, substituted sulfamoylamino group, ureido group, substituted ureido group, Examples include an alkoxy group, a hydroxyalcoquino group, an alfkyl/alcoquine group, and the like.

In the present invention, those whose hydrophilicity is significantly increased by proton dissociation under basic conditions are particularly preferred, including phenolic hydroxyl groups, carboxyl groups, sulfo groups, phosphoric acid groups, imide groups, hydroxamic acid groups, ( (substituted) sulfamoyl group, (substituted) sulfamoylamino group, etc.

The characteristics required for image-forming dyes are: /) having a hue suitable for color reproduction; 2) having a large molecular extinction coefficient;
3) stability against light, heat, and dye release aids and other additives contained in the system; and t) ease of synthesis. Specific examples of preferable image-forming dyes that satisfy these conditions are shown below. Here H2N-8O2
represents the binding site with the radical substrate.

Ye 11 ow SO□NH2 02NH2 0H oso2NH2 CH3 02NH2 NHCOCH3 H Next, specific examples of preferred dye-providing substances will be shown.

C4H9([) (4) OC engineering. H33 C5H engineering, (1) C4H9(t) OH OH OH CH3C4■-■9(L) (12) OH (13) (]( (14) (15) (16) \ C4H9(L) C4H9(L) C4H9(L) (z2) (24) (25) OH 0C16H33 (28) OH OC engineer. H33 (30) OHC-n.

TCONO□H 2H5 Gate N=Npe=〉→0□ 02 α 5O2CH3 02NH [''7-cho<Hiradade OH [l °Work Ki 7゜0C16H33-n OC Engineering. H33-Ro 0C16H33n (36) OC16H33 (37) (38) (39) (40) 0H (44) OC16H33-〇(45) H (46) (47) QC,, I-133-n 0C16H33-n OC16H33n ( 53) H OC16H33 (55) (56) H (58) CH3-C-CH3 噸3H7 (61) o)l OC16H33 C(CH3)3 \ 16H33 (67) (68) (69) H OC06H33(n) ( 70) H H (71) H As the dye-donating substance of the present invention, in addition to the above specific examples, US≠, Oj+! ,≠,2g1 Tokukai Showa Otsu-/2
z≠2, same ta-/otsu/30, same st-/l/3/,
Same j7-Otsuya 01 same tough-410≠3, US3.921
．． 3/2, US! , 071. ．． 3.2, US
Published patent App
licationf33j/, Otsu73, USII, /3
Evening, riλri, USA, /7g1. ! 3rd evening, Tokukai Shoj3-
Hirotsu 730XUS,, 273.1! t, US+, /
≠ri.

gri2, USg, /≠λ1gri/, US≠, 2jJ,
Compounds described in /20 and the like are also effective.

Furthermore, US! ,0/3.633,US≠,/,5-
t, t09, IJS17. /! f, pt, US'A.

/ &J-, 7f7, US<z, /lzg, ba
3, US≠, /13,7j evening, (JS4.2 Hirotsu, ゛Hiro/Hiro, USIA, 26g, Otsu-1tXUS+, zφS
, Oλg1 JP-A-71072, J-A-, 2!
737, same jfj-/317'lll, same jjf-/3
1/1111, 32-10 Otsu 727, same j/-/l
Dye-donating substances that emit yellow dyes such as those described in Hiroki 3θ are also effective in the present invention. Also US3゜Tata≠
, ≠7 Otsu, US≠, 932.310. US31ri31.
/≠Hiroshi, US3, ri32,31/, US≠, 2tg
, t211-11S! ,, evening on 2, evening 0, Tokukai Sho 5
Otsu-73C#”7, 37.-710 Otsu 0, same jter/
3≠zata 01 jfj−≠0hiro Oλ, same 3! ;-36za0≠, same as left 3-237. λ and the same octopus-10t7.27
, Octopus J-33/Hiroshi λ, and SS-Ta 332 are also effective in the present invention. moda US3, ri2ri, 7ot0, US
≠, 0/3, Otsu 3 Yu, US 3.9a, 2,7g7, U
S≠,,273゜7(#Xus+ , /≠♂, Otsu4'j
, US≠, /13.7j Hiro, US Hiro, / Hiro7. r Hiro≠,
Hiroshi US.

/Otsuj, 23g, US≠, 21/11. ,≠/≠, US
≠, λotg, t2 evening, JP-A Showa s6-'yioti.

Same J-3-'l-7123, same left, 2-1#27, same!
Dye-donating substances that release cyan dyes such as those listed in No. 3-/1A3323 are also effective in the present invention.

Two or more types of dye-donating substances may be used in combination.

In this case, two or more of the same pigment may be used in combination, or two or more of the same pigments may be used in combination to produce black.

The total amount of dye-donating substances is 10m9/711/! ; It is suitable to use it in the range of g/@2, preferably in the range of 20 g/m2 to 109/m2.

Next, the method for synthesizing the dye-donating substance will be described.

Generally, the dye-donating substance of the present invention is obtained by condensing the amine group of the reducing substrate Ra with the chlorosulfonyl group of the image-forming dye part.

The amine group of the reducing substrate Ra can be introduced by reduction of nitro, nitroso, or azo groups or ring opening of be/dioxazole depending on the type of substrate, and can be used as a free base or as a salt of an inorganic acid. . On the other hand, the chlorosulfonyl group in the image-forming dye moiety can be derived from the sulfonate or sulfonate of the dye by a conventional method, ie, by the action of a chlorinating agent such as phosphorus chloride, phosphorus pentachloride, or thymenyl chloride.

The condensation reaction between the reducing substrate Ra and the image-forming dye moiety is as follows:
Generally, o- It can be carried out at a temperature of ro 0c, and the desired dye-donating substance can usually be obtained in an extremely high yield.

An example of its synthesis is shown below.

Synthesis example/: Synthesis of 6-hydroxy-2-methylbenzoxazole! , ≠-dihydroxyacetophenone 301g, hydroquinlamine hydrochloride 11 sodium acetate 321f
, engineering 3'nor 1000yn/, and water j 00
@l were mixed and heated to reflux for ≠ hours. The reaction solution was mixed with 10 parts of water.
1, count the number of crystals that have precipitated, and

37≠g of ≠-dihydroxy/acetophenone oxime were obtained.

This oxime 30f/ was dissolved in acetic acid II 00111, and while heating and stirring at /2θ0C, hydrogen chloride gas was blown into the solution for 2 hours. After cooling, the precipitated crystals were collected and washed with water to obtain 77 g of 6-hydroxy-,2-methylbenzoxazole.

Synthesis Example 2: Synthesis of 6-hexazosyloxy-λ-methylkunozoxazole Synthesis Example/To 6-hydroxy-λ-methyl synthesized in /suoxazole/lr, og, l-bromohexadecane 3
t, 7 g 1 potassium carbonate, :za, op, N, N-dimethylformamide/20 ffl was stirred at OoC for ≠, j hours. The solid was separated from the reaction solution and poured into methanol. Dividing the number of precipitated crystals, t-hexadecyloxy-2-methylbenzoxazole≠j
, get Offt.

Synthesis Example 3: Synthesis of 2-acetylamino-j-hexadecyloxyphenol O-hexade/luoki/-2-methylbenzoxazole obtained in Synthesis Example λ 1 liter/g, ethanol/300 ml,
33% hydrochloric acid/10.1. Mix water J-J-Oml, j
Stirred for ≠ hours from evening to 'c. After cooling, the precipitated crystals were collected, yielding 3 g of λ-acetylamino-j-hexadecyloxyphenol.

Synthesis example≠: 2-acetylamino-Hiroshi-E-butyl-!
-Synthesis of hexadecyloxyphenol No-acetylamino obtained in Synthesis Example 3 = j-hexadecyloxyphenol 3o, Og, 7no, Solist/Yu (registered trademark of Rohm and Haas, Inc., USA) 20.0
Mix 300 ml of toluene and add 10 to 300 ml of toluene.
While heating and stirring, isobuteno was blown into the mixture for 5 hours.

After removing the solid, the p solution was concentrated, and 3jOml of n-hexano was added to the residue to precipitate crystals. No acetylamino≠-t-f thyl-j-hexadecyloxyphenol, 23. I got jfl.

Synthesis Example J: 2-Amino-≠-[-butyl-j-hexade/ruoxyphenol synthesis λ-acetylamino-4-t-butyl- obtained in Synthesis Example Hiroshi
j-hexadecyloxyphenol 23゜0g, ethanol-#/, 20zl, 3,! ;% hydrochloric acid 76ml
The mixture was mixed and stirred and refluxed overnight. After the reaction solution was cooled, the precipitated crystals were collected to obtain λ-amino≠-L-butylterhexadecylox7phenol hydrochloride, 23.
2g was obtained.

Synthesis Example B: Synthesis of ≠-(-butyl-j--xadecyloxy-λ-(1-(2-methoxynoethoxy7)-3-nitrobenozenesulfonylamino)phenol λ-amino p- obtained in Synthesis Example J t-Butyl!-hexadecyloxyphenol hydrochloride≠,≠7 and 2-(
2-Methoxyethoxy)-ternitrobenzenesulfonylchloride.

After dissolving in 2 ql of N-dimethylacetamide and adding pyridine λ, jml, the mixture was stirred at 2 J-'(:') for 1 hour. When the reaction solution was poured into dilute hydrochloric acid, an oily substance was precipitated. When methanol 301H1 was added to the solution, it crystallized, and this was collected.

Yield q0. tg.

Synthesis Example 7: Synthesis of 2-C-6-amino-2-(n-methoxy/ethoxy)henzensulfonylamino]-hiro-[-butyl-j-hexadecyloxyphenol 10 fl of the compound obtained in Synthesis Example B above was Ethanol AOm
After adding about θ, j da of 10% palladium-carbon catalyst, hydrogen! ; J kg/tytr
and stirred at 600C for 6 hours. Next, the catalyst was removed from the furnace while it was hot, and when it was allowed to cool, crystals were precipitated, so it was removed.

Yield 7. jfffl.

Synthesis example ♂: 3-cyano-Hiro-[≠-(,2-methoxyethoxy)-j-sulfophenylazo]-/-phenyl-! - Synthesis of pyrazolone Sodium hydroxide r,oy and water 200? 5-amino-λ-(2-methoxyethoxy)benzenesulfonic acid≠7. Add 1/Lf and further add 1/3. An aqueous solution (!; Oml) of ♂g was added.

Separately, prepare a solution of concentrated hydrochloric acid AOtnl and water≠00ml,
The above-mentioned molten We was added dropwise to this at a temperature of 500 ml or less. then t'
The reaction was completed by stirring for 30 minutes at a temperature below C.

Separately, sodium hydroxide/Og, Og, water 200ml 1° Sodium acetate 33. A solution of Of and 200 ml of methanol was prepared, 37.0 da of 3-7 anor/-phenyl-j-pyrazolone was added, and the diazo solution prepared above was added dropwise at a concentration of 1,000 ml or less. After the completion of the dropwise addition, the mixture was stirred for 30 minutes at a temperature of 1,000 or less, and then for 1 hour at room temperature. The precipitated crystals were separated, washed with 200 g of acetone, and air-dried.

Yield j2+Of m, p+21! , 3-26j00 Synthesis Example: Synthesis of 3-cyano-hiro-[≠-(2-methoxyethoxy)-j-chlorosulfonylphenylaso]-/-phenyl-j-pyrazolone 3- obtained in the above synthesis example Cyano-≠-[[≠-methoxyethoxy-sulfophenyl 7]-/-phenylter pyrazolone, Of, add N,N-dimethylacetamide to a mixed solution of 2 soml of acetone and Oml of oxy/phosphorus chloride. It was added dropwise at a temperature of less than 10°C.

After the dropwise addition, the mixture was stirred for about 1 hour and gradually poured into ice water/O4O. After separating the precipitated crystals from house to house, acetonitrile 100. l
and air dried.

Yield≠t, 79 m, p, /J'/~/13°C Synthesis Example 10: Synthesis of dye synthesis property 10:1) Ethoxy)benzenesulfonylamino-+-t--7'thyl-5-hexadecyloxy/phenol t, 39 was dissolved in N,N-dimethylacetamide 3One, and 3-
Cyano-≠-[≠-(,2-methoxyethoxy)-terchlorosulfonylphenyl aso]-/-phenyl-j-
Pilaprong. Otsu 1 was added, and pyridine rml was further added. After stirring at room temperature for 7 hours, the reaction solution was poured into dilute hydrochloric acid, and the precipitated crystals were collected. Recrystallization from N,N-dimethylacetamide-methanol gave 7M.

m, p, II7~/ri10C Synthesis Example/l: Synthesis of Dye Donor Substance (2) λ-[Oamino-,!] obtained in Synthesis Example 7 -(2-methoxyethoxy)benzenesulfonylamino+-t-butyl-! -Dissolve 3 fl of hexadenyloxyphenol in 30 ml of N,N-dimethylacetamide, and dissolve 3-cyano-Hiro-
(j-chloro-2-methylsulfonylphenyl aso)-
i-Cti-chloroa sulfonylphenyl)-jelasoro/r,oy was added, and then pyridine jmt was added.

After stirring at room temperature for 7 hours, the reaction solution was poured into diluted salt.
The precipitated crystal eF was collected. Recrystallization from acetonitrile gave r, pg.

m, p, /≠≠～/≠ri0C Synthesis Example/2= Synthesis of dye-donating substance (10) O, J: Hi44-C3#lolosulfonyl-Hiro-(,2-methoxyethoxy)phenylazo)-
,2-(N,N-diethylsulfamoyl)-j-methylsulfonylamino-/-naphthol, jg is N,N
-Pyridino! dissolved in 201Bl of dimethylacetamide!
0.27 gJ was added. After stirring for 1 hour at 2j0C, the reaction solution was poured into dilute hydrochloric acid. The precipitated solid was collected and purified by glue column chromatography (eluted with a chloroform-ethyl acetate (2:/) mixed solvent).

Yield s,,zg.

Synthesis Example/3: Synthesis of dye-donating substance (17)! -Amino Hiroshi-1-Petyl router hexadecyloxyphenol hydrochloride i/,ty to N,N-dimethylacetamide 1
00g1 and added pyridine//, 2dl. To this, 5-(3-chlorosulfonylbenzenesulfonylamino)-,! '-(N-t--f tilsulfamoyl)
-/7-(2-Methylsulfonyl-≠-nitrophenylaso)-/-naphthol, 20 g was added. After stirring for 7 hours, the mixture was poured into 5,007 Bl of ice water, and the precipitate was recrystallized with inopropyl alcohol-acetonitrile (/:/) to obtain 0 g of Otsu.

Synthesis example/≠2 Synthesis of dye-donating substance (19)
-amino-no (nometogy/ethkin) benozenosulfonylamino] p-L-butyl-! -hexadecyl quinphenol 3/, jp, j-(3-chlorosulfonylbencephsulfonylamino)-≠-(2-#-rusulfonyl-≠-nitrophenylaso) -/-naphthol 3-.

7 g was dissolved in 100 ml of N,N-dimethylacetamide and pyridine-2/pl was added. After stirring for 0 minutes,
Methanol 2. fOql and 100πt of water were added. The precipitated resinous material solidified after a while, so it was classified as E.

This was recrystallized from a toluene-methanol-water (/Otsu:t:3) mixed system to 4L/...! I got 9.

Synthesis example/j Synthesis of compound≠O a), 2. Synthesis of terdihydroxy-≠-[-butylacetophenone [-butylhydroquinone g 3 f/'x vinegar e'l-
Boron trifluoride (BF3) was dissolved in 00 ml and heated to 10 to 70°C for about 3 hours.

After the reaction was completed, the mixture was poured into ice water and the precipitated viscous solid was collected. This solid was converted to −2N −N a 01 (100
It was dissolved in 1 Bl and the insoluble portion was removed. The P solution was made acidic with dilute hydrochloric acid, and the precipitated crystals were washed several times with water and then recrystallized from aqueous methanol.

Yield 2Bl (Otsuj%) b), 2. Synthesis of j-dihydroxy-t-L-butylacetopheno/, oxydim Keto 72/9 obtained in a) above was mixed with 70 ml of ethanol.
Hydroxylamine hydrochloride/21 was heated and dissolved with 2≠g of sodium acetate, and 70% of water was added with stirring. The solution dissolved in i was added and refluxed for about 1 hour. 30 minutes after completion of reaction
The mixture was poured into 0 ml of ice water, and the precipitated crystals were recrystallized from a P ladle/zen-hexane.

Yield: /7g (7th section) C) Otsu-1-butyl-j-hydroxy-! -Synthesis of Methylbenozoxazole"1;]) The oxime/11-g obtained in
Introduce dry hydrochloric acid residue while dissolving it in l and heating it, /
, and refluxed for 3 i hours. After the reaction was completed, the precipitated crystals were poured into 500 ml of ice water and washed with water.

Yield? 'J C70%) d) Synthesis of 7-1-dimethyl-5-hexade/luoquin-no-methylbe/zooxazole 9 g of benzoxazole obtained in c) above was dissolved in 30 ml of dimethylformamide.
1 and stirred with 1 and hexade/rubromide//g in anhydrous potassium carbonate at ~20°C for two hours.

After the reaction, remove the inorganic substances and add methanol/Ptj to Ptj.
When J-Oql was added and cooled on ice, crystals were precipitated. The title compound was obtained by separating this.

Yield g, y (tλ%) e) Synthesis of 2-amino-1-1-butyl-Hiro-hexadeneruoxyphenol hydrochloride 7.3 g of the penzoxazole compound obtained in step d) above was dissolved in ethanol J. Oml%
! The mixture was refluxed for 3 hours with 20 ml of hydrochloric acid. After the reaction was completed, the mixture was allowed to cool, and the precipitated crystals were washed with water and then with acetonate.

Yield Otsu, RiQ (Section 9, 2) f) Synthesis of Compound Example 4 LO (described) The hydrochloride ty obtained in "=description" and the sulfonyl chlorides g and gy of the dyes with the following structural formula are dimethylacetamide! ;
The mixture was dissolved in Oml, pyridine 4'me was added thereto, and the mixture was stirred at room temperature for 7 hours. After the reaction period R, the precipitated crystals were poured into dilute hydrochloric acid and washed with water.

After drying, it was purified by silica gel chromatography to obtain substantially/component of the title compound.2. ．． I got 2g.

Dye sulfonyl chloride: Synthesis example/z: Synthesis of dye-donating substance (42) In the above synthesis example tsd), 6-(-butyl-j-hydroquine-no-methyl)
O-hexadecylation was carried out using octyl-terhydroquine)-methylbenozoxazole. Next, a synthesis example/! A dye-donating substance (42) was obtained by the same treatment as e) and f).

The dye-donating substance of the present invention is disclosed in U.S. Patent No. 2,322.02.
It can be introduced into the layer of the photosensitive material by a known method such as the method described in No. 7. 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 (such as sibutyl fucray 1-1 cyoctyl fucrate), phosphoric acid esters (diphenyl phosphate, triphenyl bosphate, tricresyl phosphate, dioctyl butyl phosphate), and citric acid esters (such as 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 having a boiling point of about 30°C to 160°C, such as lower alkyl acetate-1- such as ethyl acetate, butyl acetate, ethyl propionate, secondary butyl alcohol, methyl isobutyl ketone, β-ethoxyethyl acetate, methyl cellosolve After dissolving in acetate, cyclohexanone, etc., hydrophilic colloid G is dispersed.

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 polymer G described in No. 3 can also be used. Also, when dispersing dye-donating substances into hydrophilic raw colloids, various surface activities can be used. J) can be used as a surfactant, and Hayabanjitachino can be used as a surfactant elsewhere in Banmako's specification.

G) Not more than 10 g per 1 g of the dye-donating substance used in the present invention.

Preferably it is 5g or less.

In the present invention, a reducing agent can be used as necessary. The reducing agent in this case is a so-called auxiliary developer,
It is oxidized by a silver halide and/or an organic silver salt oxidizing agent, and its oxidized product has the ability to oxidize the reducing substrate Ra in the dye-donating substance.

Useful auxiliary developers include alkyl-substituted hydroquinones such as hydroquinone, t-butylhyfluoroquinone, 2,5-dimethylhydroquinone, catechol, pyrogallols, halogen-substituted hydroquinones such as chlorohydroquinone and dichlorohydroquinone, and methoxyhydroquinone. alkoxy-substituted hydroquinones, such as
There are polyhydroxybenzene derivatives such as methylhydroxynaphthalene.

Furthermore, hydroxylamines such as methyl gallate, ascorbic acid, ascorbic acid derivatives 2p, N, N-di(2-ethyl)hydroxylamine, 1-phenyl-3-pyrazolidone, 4-nonal-4-hydroxymethyl Pyrazolidone reductones such as -1-phenyl-3-pyrazolidone.

Hydroxytetronic acids are useful.

Auxiliary developers can be used in a range of concentrations. A useful concentration range is from 0.0005 times molar to 20 times molar, and a particularly useful concentration range is from 0.001 times molar to 4 times molar relative to silver.

Various dye release aids can be used in the present invention. A dye-releasing agent is a photosensitive compound containing silver arsenic and/or organic silver hydrochloric acid, an arsenic agent, and a dye-donating substance. It can act nucleophilically on the dye-donating substance to promote the release of the dye, and the base precursor can be used as a base precursor.

In the present invention, it is advantageous to use these dye release aids to accelerate the reaction.

Examples of preferred bases include amines, including trialkylamines, hydroxylamines, aliphatic polyamines, N-alkyl substituted aromatic amines,
N-hydroxyalkyl-substituted aromatic amines and bis[
p-(dialkylaminoru) Also, US Pat.

Organic compounds containing amino acids, such as urea and aminocaproic acid, are described and useful in the JO Otsu, +≠Hiro issue. The base material releases basic components when heated. Examples of typical base precursors are described in British patent no. Preferred base precursors are:
Cal f. Examples of useful carbo/acids which are salts of /acids and organic bases include trichloroacetic acid and trifluoroacetic acid, and useful bases include guanidi/, piperidine, morpholine, p-toluidino, and supicoli/. U.S. Patent No. 3.

λ. 20, and guanidine trichloroacetic acid described in No. 4L& is particularly useful. Also, Japanese Patent Publication No. 30-1989. 2.2&λ
The aldone-amides described in the evening issue are preferably used because they decompose at high temperatures to produce bases.

These dye release aids can be used in a wide variety of ways. A useful range is 50% by weight or less, calculated as the total weight of the coated soft film of the photosensitive material, and more preferably 0.5% by weight or less. O
/weight percent to g.

Weight/Mecent range.

In the heat-developable color light-sensitive material of the present invention, it is advantageous to use a compound represented by the following general formula because development is accelerated and dye release is also promoted.

[General formula]

In the above formula, are A , A , A , A the same or 1?
2 3 or may be different, and each represents a hydrogen atom, an alkyl group, a substituted alkyl group, a cycloargyl group, an aralkyl group, an aryl group, a substituted aryl group, and a hated substituent among heterocyclic residues, and A1 and A2 or A3 and A4 may be connected to form a platform.

As a specific example, 1-12N 802NH2°H2N5
02N(CH3)2. H2N502N(C2H5)2゜H2N5O2NHCH3, H2N502N(c2H4o
H) 2°CH3NH303NHCH3.

” = 1 Compounds can be used in a wide range of ways.

A useful range is less than or equal to 20 g-cents, more preferably 0.7 g-cents, based on the weight of the coated buffy film.
from /, f weight percent.

In the present invention, it is advantageous to use a water-releasing compound because it accelerates the dye-releasing reaction.

A water-releasing compound is one that decomposes and releases water during thermal development.
It refers to hi-go-mono. These r-compounds are known in particular in transfer printing of textiles and are described in Japanese Patent Sho-g13g1.
NH4Fe(S04)2/2H20 described in the publication No.
etc. are useful.

Further, in the present invention, a compound can be used to stabilize the image at the same time as activating the development.

Among them, US Pat. No. 3.30/, t71, 2-
Hydroquine ethyl inthiuronium trichloro 7-t
Inothiuroniums represented by Tate, US Patent No. 3
, 6 Otsuri, 71g-(3,1,-dioxaoctane) bis(inothiuronium trifluoroacetate) described in No. 670, West German Patent No. 2
．． / Otsu 2, thiol described in publication in 7/4L issue "Kamidai Oki, U.S. Patent≠, 2-amino-1 thiazolium trichloroacetate described in 0/2..2tO, !-amino-S-bromoethyl-2-thiazolium. Thiazolium f compounds such as trichloroacetate, bis(2-amino-λ-
chiatulium) methylenebis(sulfonylacetate)
, U.S. Pat.
Preferable examples include those described in ll-ta No. 7, which have a normal carboxycarboxamide as the acidic moiety.
<Used.

In the present invention, a hot solvent can be contained.

The term "thermal solvent" here refers to a non-hydrolyzable organic material that is solid at ambient temperature but exhibits a mixed melting point with other components at or below the heat treatment temperature used. Useful thermal solvents include compounds that can serve as solvents for developing agents, and r-compounds, which are substances with high dielectric constants and are known to accelerate the physical development of silver salts.Useful thermal solvents include: U.S. Patent No. 3,341.7.t7.S-
No. Saimei's polyglycols, such as average molecular weight/! 00
~20,000 polyethylene glycols, derivatives such as oleate esters of polyethylene oxide, beeswax, monostearin, compounds with high dielectric constants with -8O2-1-C〇- groups, such as acetamide, sacunnimit, ethyl alcohol-1 -, urea, methylsulfonamide, ethylene-/y-phonate, U.S. Pat.
--yhydrothiophene-/,/-dioxide, Research Tissue Flower Magazine/Re7 wo/, February issue 26~
Preferably used as 2♂ are -diSaimein/, IO-decanediol, methyl anisate, biphenyl perate, and the like.

In the case of the present invention, the dye-donating substance is colored, and further,
Although it is not so necessary to incorporate anti-irradiation or anti-halation substances or dyes into light-sensitive materials, in order to further improve the sharpness, Japanese Patent Publication No. 4T, L'-3T Tano, U.S. Pat. No. 3.253, ri, No. 27, same, 2
．． 327,! It is possible to contain filter dyes and absorbent substances, which are described in specifications such as IG No. 3, Tata Otsu No. 1G No. 7, etc. -! Preferably, these dyes are thermally decolorizable dyes, such as those described in U.S. Pat.
0? No. 3. Dyes such as those described in Otsu/J, ≠ No. 3.2 are preferred.

The photosensitive material used in the present invention may optionally contain various additives known as heat-developable photosensitive materials and layers below the photosensitive layer, such as an antistatic layer, a conductive layer, a protective layer, an intermediate layer, an AH layer, and a peel-off layer. It can contain layers and the like.

The photographic emulsion layer or other hydrophilic colloid layer of the light-sensitive material of the present invention includes coating aids, antistatic properties, smoothness improvement, emulsification dispersion, adhesion prevention, and improvement of photographic properties (for example, development acceleration, high contrast, sensitization), etc. Various surfactants may be included for various purposes.

For example, Zaponi 7 (steroid type), alkylene oxide derivatives (such as polyethylene glycol, polyethylene crinol 7 polyyropylene glycol condensate, polyethylene glycol alkyl ethers or polyethylene glycol alkylaryl ether a, PoIJ
ethylene glycol esters, polyethylene glycol norbitane esters, polyalkylenoglycol alkylamine kasetake amides, polyethylene oxide adducts of 7-licon), glycidol derivatives (e.g. alkenylcono-phosphate polyglycerides, alkylphenol polyglycerides), glycerides), polyvalent acetate,.

Nonionic surfactants such as Cole's fatty acid esters and sugar alkyl esters; alkyl cal i7e salts, alkyl sulfonates, alkyl benozenosulfonate L, alkyl naphthalenosulfonates, alkyl sulfates, alkyl Phosphate esters, N-anru N-alkyltaurines, sulfosuccinates,
Anionols containing acidic groups such as carboxino groups, sulfo groups, phospho groups, sulfate ester groups, phosphate ester groups, etc. Surfactants; amphoteric surfactants such as amino acids, aminoalkyl sulfo/acids, aminoalkyl sulfates or phosphoric esters, alkyl betaias, amine oxides; alkylamine salts, aliphatic or aromatic surfactants;
Cationic surfactants can be used, such as heteroterminal ammonium salts, pyridinium, imidazolium, etc., and phosphonium or sulfonium salts containing aliphatic or heterocycles.

Among the above-mentioned surfactants, it is preferable to include a polyethylene glycol type nonionic surfactant having an ethylene oxide repeating unit in the molecule in the photosensitive material. Particularly preferred are those having 5 or more repeating units of ethylene oxide.

Nonionic surfactants that meet the above conditions are widely used outside the field, and their structures, properties, and synthesis methods are well known. Representative known documents include Surf
actanL Science Seriesvo
lume i, Nonionic Surfacja
nLs (Edited by Margin J.
Schick.

Marcel Dekker I mouth c. / ?
lr7), 3urface AcLive
ELhylene QxideAdducLs(S
choufeldL. PergamonPreSS by N.
Nonionic surfactants described in these documents that satisfy the above conditions are preferably used in the present invention.

These nonionic surfactants may be used alone or as a mixture of two or more.

The nonionic surfactant for polyethylene glycol is used in an amount equal to or less than the weight of the hydrophilic Pai/Goo, preferably 50% or less.

The light-sensitive material of the present invention can contain a cationic compound having a pyridinium salt. An example of a cationic compound with a pyridinium group is PSA Journal.
al, 5ecLion B 31 (/
213), USP u, A4J',
tc#, USP3. l.

71.2≠7, Special Public Akihiro-3007lLL, Special Public Akihiro≠
Hirota! 03 etc.

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.), activated hinyl compounds (1,3,5 -1-lyacryloyl-hexahydro-8-triazine, 1,3-vinylsulfonyl-2-propatol, etc.), active halogen compounds (2,4-dichloro-6-hydroxy-8-triazine, etc.), mucohalogen acids (mucochloric acid, mucophenoxychloric acid, etc.), etc. can be used alone or in combination.

Various additives include “Re5earch1)isclo”
Additives described in No./70.27 of the year /70.48797g such as accumulatives, sharpness improving dyes, AH dyes, sensitizing dyes, mantle agents,
Includes fluorescent brighteners, anti-fading agents, etc.

In the present invention, as well as the heat-developable photosensitive layer, coating solutions for the protective layer, intermediate layer, undercoat layer, pack layer, and other layers are prepared for each layer using the dipping method, air knife method, curtain coating method, or U.S. Patent 3. A light-sensitive material can be prepared by sequentially coating a support on a support using various coating methods such as the Hola/ξ-coating method described in the specification of tl/, 2rihiro, and the like and drying.

Furthermore, if desired, two or more layers can be applied simultaneously by the methods described in US Pat.

Various exposure means can be used in the present invention. The latent image is obtained by imagewise exposure to radiation, including visible light. In general, light sources used for normal color printing, such as tungsten lamps, mercury lamps, iodine lamps, etc., rogen lamps, xenon lamps, laser light sources, CR, T light sources, fluorescent tubes, light emitting diodes, etc. can be used as light sources. can.

The original drawing may be a line image such as a technical drawing, or a photographic image with gradation. It is also possible to photograph portraits of people and landscapes using a camera. The printing from the original drawing may be done by overlaying the original drawing by contact printing, reflection printing, or enlargement printing.

It is also possible to output images taken by a video camera or the like or image information sent from a television station directly to a CRT or FOT, and then form this image on a heat-developable material using a contact lens/Z for C1 printing. It is possible.

Furthermore, LEDs (light emitting diodes), which have recently seen great progress, are being used as exposure means or display means in various devices. It is difficult to make an LED that effectively produces backlight. In this case, to reproduce a color image, three types of LEDs are used that emit green, red, and infrared light, and the parts of the sensitive material that are exposed to these lights emit yellow mazenota and shea dyes, respectively. It should be designed like this.

That is, the green-sensitive part (layer) contains a yellow dye-donating substance, the red-sensitive part (layer) contains a maze/red dye-donating substance,
The infrared-sensitive portion (layer) may contain a cyan dye-donating substance. Other combinations are also possible as required.

In addition to the above-mentioned method of directly attaching or projecting the original image, so-called image processing involves reading the original image illuminated by a light source using a light-receiving element such as a phototube or CCD, storing it in the memory of a computer, etc., and processing this information as necessary. After applying, this image information is played back to CR,T,
There is also a method of using this as an image-like light source, or of directly causing the three types of LEDs to emit light based on the processed information.

In the present invention, the photosensitive material is obtained after exposure to light.

The developed latent image can be developed by heating the element at moderately elevated temperatures, such as, for example, from about 0.degree. C. to about 230.degree. C. for about 0.3 seconds to about 300 seconds.

As long as the temperature is within the above range, either high or low temperatures can be used by increasing or shortening the heating time. A temperature range of about /10°C to about /20°C is particularly useful.

The heating means may be a simple hot plate, an iron, a hot roller, a heating element using carbon or titanium white, or the like.

In the present invention, a specific method for forming a color image by heat development is to move a hydrophilic mobile dye. For this purpose, the light-sensitive material of the present invention has a light-sensitive layer (I) on a support, which contains at least silver halide, optionally an organic silver hydrochloride arsenic, a dye-donating substance which is also its reducing agent, and a binder. and (I) a hydrophilic and ambiguous dye fixing layer that can absorb all of the dye (
n).

The above-mentioned photosensitive layer CI) and dye fixing layer (II) may be formed on the same support, or may be formed on separate supports. The dye fixing layer (II) and the photosensitive layer (I) can also be separated. For example, after imagewise exposure, uniform heat development can be carried out, and then the dye fixing layer (II) or the photosensitive layer can be peeled off. In addition, the photosensitive layer It)
When a photosensitive material coated on a support and a fixing material coated on a support are formed separately, the photosensitive material is imagewise exposed and heated uniformly, and then the fixing material can be layered to transfer the mobile dye to the fixed layer (II).

There is also a method in which only the photosensitive material (1) is imagewise exposed, and then the dye fixing layer (n) is superimposed and uniformly heated.

The dye fixing layer (II) can contain, for example, a dye mordant for dye fixation. Various mordants can be used as the mordant, and polymer mordants are particularly useful. In addition to mordants, bases, base flexors, etc.
and a hot solvent. In particular, when the photosensitive layer (1) and the dye fixing layer (II) are formed on different supports, it is particularly useful to include a base or a base precursor in the fixing layer (n).

The polymer mordant used in the present invention is a polymer containing 7 secondary and tertiary amine groups, a polymer having a nitrogen-containing heterocyclic moiety, a polymer containing these quaternary cation groups, etc., and has a molecular weight of t, ooo to 20o. , ooo, especially 10,
000~so, ooo.

For example, a US patent! , ta ≠ g, st ≠ issue, same no.

IAI! 'A, No. 1A30, 3. /III, 0 Otsu/
Vinylpyrine/polymer and vinylpyridinium cationopolymer disclosed in U.S. Pat. Otsu 23-1 Otori ≠ No., Otsu 3.1 Ota, 0ri No. 6, Otsu t, /λg.

A polymer mordant capable of crosslinking with gelatin, etc., disclosed in No. 53g, British Patent No. 277, Kou No. 53, etc.;
US Patent 3. risg, No. 775, same, 2.7.2/,
No. 1732, No. 2,721, OA No. 3, Japanese Patent Publication No. 1732, Akihiro Aki-
//! ;22g issue, same ψ-/ψta j ivy issue, same 5'
ψ-/2t Aqueous sol-type mordant disclosed in US Patent No. 027, etc.; water-insoluble mordant disclosed in US Pat. A reactive mordant capable of forming a covalent bond with the dye disclosed in the specification, etc. (JP-A-KOKAI SHOTA!-/37333); furthermore, U.S. Patent No. 3,70, Otsuri No.
and j5, same 3. Otsu≠2. ≠g2 No.3, 'AI#
.

No. 706, No. 31, No. 3.27, /
≠ No. 7, same J, 27/, /Hirodo No., JP-A-Shota θ-7
No. 733, No. f3-30321, No. 2-73-
Ta 321, 33-/2! No. r, Ta 3-1021I
The mordant disclosed in the specification of No.

Other US patents, 2. , 1.73;, 3/, and the mordant described in 2°lfg 2,156.

Among these mordants, for example, those that crosslink with the matrix such as gelatin, water-insoluble mordants, and aqueous sol (or latex dispersion) type mordants can be preferably used.

Particularly preferred polymer mordants are shown below.

(1) A group having a j-class ammonium group and capable of covalently bonding to gelatin (e.g., aldehyde group, chloroalkanoyl group, chloroalkyl group, vinylsulfonyl group, pyridiniumpropionyl group, vinylsulfonyl group, alkylsulfonyl group, etc.) For example, a polymer having -ecH2-CH10--÷CH2-CH101c=oc=.

1 (2) A copolymer consisting of a repeating position of a monomer represented by the following general formula and a repeating unit of another ethylenically unsaturated monomer, a crosslinking agent (for example, hahisalkanesulfo-4-1-, hisyrenesulfonate), reaction product.

aryl group, or b At least R-J. λ are combined to form a hetero It may form a ring.

X: Anion (two sets of alkyl groups and aryl groups include substituted ones) (3) Polymer X represented by the following general formula: about 0, . 2
t to about j molar coefficient y: about 0 to about 7 θ molar coefficient Z: about 10 to about phtha molar coefficient A: monomer having at least λ ethylenically unsaturated bonds B: copolymerizable ethylenically unsaturated monomer Q: N , P ab Rb Rb : alkyl group, cyclic hydrocarbon 1\2\3 group, and at least two of alH and R% may be combined to form a ring. (These groups and rings may be substituted.) (4) Copolymer X consisting of (a), (b) and (C): hydrogen atom, alkyl group or...rogen atom (alkyl group may be substituted) ) (b) Acrylic acid ester (C) Acrylonitrile (5) Water-insoluble polymer having //3 or more repeating units represented by the following general formula b b b R□, R2, R3: each alkyl bb represents a group, and the total number of carbon atoms in R1-R3 is 12 or more. (The alkyl group may be substituted.) As the gelatin used in the mordant layer, various known gelatins may be used. For example, gelatin with different manufacturing methods such as lime-treated gelatin and acid-treated gelatin, or
It is also possible to use gelatin obtained by chemically modifying the obtained gelatin such as phthalation or sulbonylation. Moreover, if necessary, it can be used after being subjected to desalting treatment.

The mixing ratio of the polymer mordant and gelatin of the present invention and the coating amount of the polymer mordant can be easily determined by those skilled in the art depending on the amount of dye to be mordanted, the type and composition of the polymer mordant, and the image forming process to be used. You can, but
Mordant/gelatinization is 207. ! '0-40720 (
It is preferable to use the mordant in an amount of 065 to 117 m2 (weight ratio).

The dye fixing layer (II) may have a white reflective layer. For example, a layer of titano dioxide dispersed in gelatin can be provided over a mordant layer on a transparent support. The titano dioxide layer forms a white opaque layer, and by viewing the transferred color image from the transparent support side, a reflective color image can be obtained.

A typical fixative material used in the present invention is obtained by mixing a polymer containing an ammonium salt with gelatin and coating it on a transparent support.

For dye transfer from the photosensitive layer to the dye fixed layer.

Dye transfer aids can be used.

In a system in which the transfer aid is externally supplied, water or a basic aqueous solution containing caustic soda, caustic potash, or an inorganic alkali metal salt is used as the dye transfer aid. Also 1 methanol, N,N-dimethylborumamide, acetone,
A low boiling point solvent such as 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 by moistening the image-receiving layer with the transfer aid.If the transfer aid is incorporated into the light-sensitive 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 low temperatures and soluble at high temperatures is incorporated into the light-sensitive material or dye-fixing material. The hydrophilic thermal solvent may be incorporated into either the photosensitive material (1) or the dye-fixing material (2), or both (2). Further, the layer to be incorporated may be either the emulsion layer 2 intermediate layer or the protective layer 9 dye fixing layer, but examples of hydrophilic heat solvents preferably incorporated in the dye fixing layer 3 and/or its adjacent layer include ureas, pyridine, etc. Kind, Ami F neck, Surinamito cheeks, Imi 1
In order, there are alcohols, oximes, and other heterocycles.

The present invention will be explained in more detail with reference to Examples below.

Example 1 (1) Preparation of tabular silver halide grains In 1 liter of water, 30 g of gelatin, 10.3 f of potassium bromide, and 0.0 g of potassium bromide were added.
jwt Thithioether (HO(CH2)2S(CH2)2S(CH2)20H
) in a container containing 10 cc of aqueous solution and kept at 70 °C (p
Eguri.

i, pHA, j) with stirring, add the following solutions I and 7 to
After the addition for 5 seconds, solutions (1) and (2) were simultaneously added over 6j minutes by the double jet method. The pH'kA of the silver iodobromide emulsion thus prepared was adjusted, and the emulsion was precipitated to remove excess salt.

Thereafter, the pH was adjusted to 6.0 to obtain a silver iodobromide emulsion with a yield of 1 kg.

The silver halogenide grains thus obtained had an average diameter of 7.
The average diameter/thickness ratio of 43 μm was ii”, t.

The silver halide grains were chemically sensitized using chlorauric acid salt and sodium thiosulfate. Silver/gelatin weight ratio is/
, 30.

(2) Preparation of silver iodobromide (spherical grain) emulsion for comparison in the presence of ammonia by the double jet method.
Silver iodide was chemically sensitized with chlorauric acid salt and sodium thiosulfate to form spherical grains with an average grain size of 3 μm. The weight ratio of silver/gelatin is /,! ! Met.

(3) Preparation of zahedron particles for comparison In 1 liter of water, gelatin 30f, Kalita bromide, z% thioether (HO(CH2) 2S(CH2) 28(CH2
) 20H) Into a container (pAg, 0.pH 3,6) which had been maintained at 0C after adding aqueous solution jOcc, the following solutions I and ■ were simultaneously added for 1 minute while stirring, and then the solutions ■ and ■ were added for 30 minutes. It was added by double jet method.

The silver halide grains thus obtained had an average diameter of 1.3
They were 2 μm male-hedral particles. The silver halide grains were chemically sensitized using chlorauric acid salt and sodium thiosulfate. The silver gelatin ratio is /,! It was set as 10.

The amount of Ag per silver halide emulsion/illustration in (2) and (3) was adjusted to be equal to that in (1).

(4) Preparation of benzotriazole silver emulsion Gelatin, 2r
y and benzotriazole/3.21 are dissolved in J 000 of water. Keep this solution at uooc and stir. To this solution, add 2 ml of silver nitrate/7f dissolved in 100@l of water.
Add in minutes.

The pH of the benzotriazole silver emulsion is adjusted and allowed to settle to remove excess salt. Thereafter, the pH was adjusted to tt and o to obtain a benzotriazole silver emulsion with a yield of 100%.

(5) Preparation of gelatin dispersion of dye-donating substance Magenta dye-donating substance (42) was mixed with rg and 0.0 g of sodium succinate 2-ethylhexol ester sulfonate. Weigh the jfs treacle resin phosphate (TCP) sg,
Add 30 WIl of ethyl acetate and heat to dissolve at about t00C to form a homogeneous solution.

A 10% solution of this solution and lime-processed gelatin.

After stirring and mixing with f, use a homogenizer for 70 minutes.
Disperse at 0,00 ORPM.

(6) Preparation of photosensitive coating solution A-C The following components were sequentially mixed and photosensitive coating solution ti, h-c (7
) Preparation of protective layer coating solution A protective layer coating solution was prepared by sequentially mixing the following components.

(8) Preparation of photosensitive material The photosensitive coating solutions A, B, and C are coated on polyethylene terephthalate coated with an undercoat.
It was applied so that the area was 2 m2. At this time, an appropriate gelatin water bath solution was added to each coating solution so that the dry film thickness of each coating solution was the same. The above-mentioned protective layer coating solution was applied onto the coating layer of each photosensitive coating solution to a wet film thickness of 25 μm, and dried to produce photosensitive materials AXB and C.

(9) Preparation of dye-fixing material poly(methyl acrylate-no-N,'N,N-1-limethyl-N-vinylbenzylammonium chloride) (ratio of methyl acrylate and vinylbenzylammonium chloride is /:/) IOQ 200 @l of water and uniformly mixed with 100f of 10% lime-treated gelatin.

This mixed solution was uniformly applied to a wet film thickness of 0 μm on a paper support laminated with polyethylene in which titanium dioxide was dispersed. After drying, this sample is used as a dye fixing material with mordant I-.

The three color light-sensitive materials thus prepared were exposed to light at 2000 lux for 10 seconds using a tungsten straight ball through a step wedge. Thereafter, each of these photosensitive materials was divided into pieces, placed on a heat block heated to /3θ0C, and heated for io seconds, 20 seconds, 30 seconds, and ≠0 seconds, respectively.

Next, 301,111 liters of water was supplied to the membrane side of the dye-fixing material per 7 m 2 , and the heat-treated photosensitive materials were stacked on the fixing material so that their membrane surfaces were in contact with each other. za0'
After heating for 6 seconds on a C heat block, the color-fixing material was peeled off from the light-sensitive material and the maximum image density of the transferred dye was measured, and the results shown in the following table were obtained.

The photosensitive materials AXB and C are identical in other conditions such as film thickness except for the shape of the silver halide grains.

Therefore, in Table 1, the value of the maximum image formation shown by the oblique feeding of the photosensitive material using the tabular silver halide of the present invention is higher than that of other photosensitive materials when the tabular silver halide of the present invention is used. It is clear that the heat development progress (reaction speed between the silver halide and the dye-donating element) is significantly faster than that of silver halide.

Claims (2)

[Claims] (1) At least on the support, a tabular photosensitive silver halide having a grain size of 5 times or more the grain thickness, a binder, and a binder that is reducible to the silver halide, and heated with the silver halide. A heat-developable color photosensitive material characterized by containing a dye-providing compound that releases a hydrophilic dye upon reaction. (2) At least on the support, a tabular photosensitive silver halide with a grain size of 5 times or more the grain thickness, a binder, and a binder that is reducible to the silver halide and reacts with the silver halide by heating. A heat-developable color light-sensitive material containing a dye-providing substance that releases a hydrophilic dye is heated in a substantially water-free state at the same time as or after image exposure to a heat-developable color photosensitive material containing a dye-providing substance that releases a hydrophilic dye. A method of forming pigment into an image.