JPS59182449A - Thermodevelopable photosensitive material - Google Patents

Abstract

PURPOSE:To obtain a thermodevelopable photosensitive material capable of releasing a developing adjuvant at controlled speed at the time of thermodevelopment by incorporating a specified developing adjuvant precursor in the thermodevelopable photosensitive material. CONSTITUTION:A thermodevelopable photosensitive material contains a dye donor and a developing adjuvant precursor represented by the general formula shown here in which A is a group cleavable by alkali hydrolysis; R is aryl; and R<1>-R<4> are each H, alkyl, or aryl, and optionally same or different as and from each other.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel photosensitive material with excellent developability and storage stability. More specifically, the present invention relates to a photosensitive material containing a dye-donating substance that reacts with photosensitive silver halide to release a hydrophilic dye when heated in a substantially water-free state, and in particular, This invention relates to a novel silver halide photosensitive material with excellent performance and storage stability before use.

Photography using silver halide has traditionally been the most widely used method because it has superior photographic properties such as sensitivity and gradation control compared to other photographic methods, such as Shigeko photography and diazo photography. Ta. In recent years, a technology has been developed that allows images to be formed easily and quickly on photosensitive materials using silver halide by changing from the conventional wet processing using a developing solution to a dry processing using heating, etc. It's here.

Heat-developable photosensitive materials are well known in the art;
553 of Fundamentals of Photographic Engineering (published by Koshi1susha in 1979)
100-555 pages, published in April 1978 Eisenjo Yato 140T
5, N e b I e t t S Hand
-h o o k o r P h o t o
g r a p h ya n (l Rep r
o g r a p h y 7 L h [E
d.

(Van No5trand RI: Ii, nho
32T (-33
U.S. Pat. No. 3.152.4, published on page 1.
) No. 04, No. 3.3 (li, No. 678, No. 3.392,
No. 020, No. 3. No. 457.075, UK Patent No. 1
131゜No. 108, No. 1,167.777 and Research Disc Jul-Jar Magazine June 1978 No. 9
Pages 1-15 (RD-17029).

Many methods have already been proposed for dry-processing color images.Yoneko 1 Riroko No. 3 describes a method for forming color images by combining an oxidized developer and a coupler. , 531.286, a p-phenylenediamine compound and a phenolic polymer-active mediton coupler are used, and in U.S. Pat. - Go Disclosure Magazine, September 1975, September 31-32, describes the reduction of sulfonamide phenols in US Pat. No. 4.
No. 021,240 supra, S) II Inton Amidov J.
Combinations of a nol-based reducing agent and seven 4-equivalent couplers have been proposed.

However, in such a method, exposure after thermal development j!
Since the reduced silver image and the color image are simultaneously produced in 1 minute, the color image becomes cloudy. To solve this problem, there is a method of removing the silver image using liquid processing, or transferring only the dye to a sheet with a black layer, for example, a sheet with a 1-mil color. Reaction 1: Transferring only the dye by distinguishing between the colorant and the dye 1; 1: It has the disadvantage that it is not easy.

In addition, a nitrogen-containing heterocyclic group is introduced into the dye to form a silver salt,
4! Method for releasing dyes by development, Research Disclosure Magazine 1978, "5J", p. 54~
Page 5B (RD-16966) A note has been written.

In this way, (1) f! i, '+'tl' of the dye at 3 min: I[ can be suppressed by 1
．． Since it is T1 ff, it is impossible to obtain a bright image, and this is not a common method.

Regarding the method of forming a positive color image by thermal silver dye bleaching method, see, for example, Research Disk rI-Gear Magazine, April 1976, pp. 30-32 (1 copy)-144.
33), same t, and December 1976 issue 14-15J' (
(RD-15227), U.S. Patent No. 4.235.95
No. 7 and other publications describe useful dyes and bleaching methods.

However, this method requires extra steps such as stacking and heating activating agent sheets to accelerate the bleaching of the dye and 44 r'i. 1ff1 gradually due to M Felt vision etc. in which colored images coexist
Because it was originally bleached, it had a long-term (inability to survive) deficiency.

Regarding the method of forming a color image using a single color dye, for example, U.S. Pat. No. 3,985,565 and U.S. Pat. It is described in the appendix of fi 1.7. However, with this method, dyes of 1:2 and 2 can be stably transferred.■4. (
It is difficult to incorporate it into food, and it has the disadvantage of becoming discolored during storage.

The Ministry of the Invention and others have already provided a new photosensitive material that can overcome the drawbacks of the conventional methods.

This is a photosensitive silver halide, an inder and a photosensitive 1j!: unlike silver halide, it is ionic, and contains substantially water after or at the same time as the exposure. When heated in a non-free state, a mobile hydrophilic dye is released in an imagewise manner (fr)71), and this mobile hydrophilic dye G1 is transferred to the dye fixed layer mainly in the presence of a solvent. It was something that could be moved.

Although the photographic material 1 was excellent in that high-quality images could be obtained by an extremely simple method, there was still room for improvement in terms of storage stability and developability before use.

However, it is generally not easy to improve the developing performance and storage performance before use while maintaining the sensitivity of the photosensitive dye.

Therefore, the first object of the present invention is to provide a photosensitive material for thermal development that can produce a high-density dye image by applying F1 to (v) for a short time after exposure or at the same time as exposure. , 4
The purpose is to provide t'l.

A second object of the present invention is to provide a photosensitive material for heat development that can reduce the fog of a high W4 dye image caused by heat development after exposure or simultaneously with exposure. It is in.

The third object of the present invention is to
At the speed rolled? The purpose is to provide a spiritual amulet for thermal phenomena that can release RLI co-developer.

Furthermore, a fourth object of the present invention is to provide a .mu.-light material for heat development that has excellent storage stability before heat treatment.

Such features of the present invention provide at least (D
Photosensitive silver halide, ■Baingu, and ■Photosensitive 11°
6) A color imparting substance that is reducible to silver halide and reacts with photosensitive 1+ silver halide to release a hydrophilic dye when added, and 6) is represented by the following general formula. A heat-developable photosensitive material characterized by having an auxiliary developing agent precursor (where Δ represents a group that can be cleaved by alkaline hydrolysis;
R does not represent an aryl group. R1, R2, R3 and R4 represent a hydrogen atom, an alkyl group or an aryl group, and may be the same or different.

In the photosensitive material according to the present invention, the exposed photosensitive halogenated material is used as a catalyst by heating in a substantially water-free state after imagewise exposure or at the same time as imagewise exposure. Because an oxidation-reduction reaction occurs between the dye-donating substance and the reducing dye-donating substance, in addition to the silver image in the exposed area, there is also a silver image separated from the dye-donating substance that has been oxidized by silver halide and turned into an oxidant. The mobile hydrophilic dye image is also removed at the same time. However, in many cases, unreacted dye-donating substances coexist when surface development is performed, resulting in the presence of a mobile ? Distinguish from IL aqueous dye image. NitogataFF1 (and not lit. In this case, 117)
) The hydrophilic dye can be transferred to the dye fixing layer under an atmosphere to which it has affinity, thereby obtaining a dye image with excellent image quality and storage stability. be able to. In this case, is it a hydrophilic dye?
The atmosphere that makes the ll III property 1'1 supplies the solvent-J
In addition, it can be easily realized by using a hydrophilic heat absorbing agent.
However, it is also possible to realize a sieve that has an affinity for hydrophilic dyes without supplying a special medium from the outside.

This principle is qualitatively the same whether a negative-tone emulsion or an auto-positive emulsion is used as the emulsion for the light-sensitive main dye. , Color reproducibility was determined in the same manner as when using a negative emulsion, except that of the 3Y image and mobile dye image obtained in the unexposed area, the Z part of the dye image was moved to the color fixation waste. You can get a good pigment side (elephant).

Photosensitivity in the present invention can be caused by heating in a state substantially free of F6 medium, as well as the redox reaction between TA and the dye-donating substance and the subsequent dye-releasing reaction. Here, heating means heating at 80°C to 250°C, and H3, which does not substantially contain water, means that the reaction system is in a normal state with moisture in the air, and the reaction does not occur. This means that no water is specifically supplied to trigger or promote the reaction.
yo f t h ep h o t Ogr
ap h I c p r o c e s s ”
4thud, (F, d it edby T,
Il, , JEl m e n ,
M a r, m i I I a
n ) W self is listed in 3 7 4 1'j.

In the present invention, the dye-donating substance is +51 +1"!
Since each 'l' can increase the emitted dye by +5, various colors can be expressed by i'Tf.

Therefore, by selecting the combination -υ, it is possible to obtain multiple colors. A dye image includes not only a monochrome image but also a multicolor image, and a medium color image also includes a monochrome image formed by a mixture of two color layers.

Conventional dye release reactions are thought to be caused by attack by so-called nucleophiles, and given that they are generally carried out in an aqueous solution with a pH of 10 or higher, the dyes used in the present invention can be used in the present invention. It is extremely unusual for a photosensitive material to exhibit a high reaction rate only by heating in a state substantially free of water.

Furthermore, according to the conventional knowledge obtained from the wet development of Tsuneko T (; ``It is also extremely unusual that a redox reaction can occur with silver saponide (Japanese Patent Application No. 56-157..79B).

The second reaction proceeds particularly well in the presence of an organic silver salt oxidizing agent, and high image density can be obtained.

Therefore, it is a particularly preferred embodiment to coexist an organic silver salt oxidizing agent.

The reducing dye-donating substance has the following general formula (%) (%) where Ra represents a reducing substrate that can be oxidized by silver halide, and D represents an image-forming dye moiety having a hydrophilic group. Hail.

The reducing substrate (R
In a), in polarographic half-wave potential measurement using acetonitrile as a solvent and sodium perchlorate as a supporting electrolyte, the redox potential with respect to a saturated calomel electrode was 1. It is preferable that it is less than or equal to C. A preferred reducing substrate (R
a) are the following general formulas (II) to (IX).

II H- H- E3. a Alkyl group, cycloalkyl group, aryol group, alkoxy group, aryloxy group, aralkyl group, acyl group, acylamino group, alkylsulfonylamine group, arylsulfonylamino group, arylokynealkyl group, alkoxyalkyl group, Represents a group selected from an N-substituted carbamoyl group, an N-substituted sulfamoyl group, a halogen atom, an alkylthio group, and an arylthio group, and the alkyl group and aryl group in these groups can further be an alkoxy group, a halogen atom, or a hydroxyl group. , a cyan group, an acyl group, an acylamino group, a substituted carbamoyl group, a substituted sulfamoyl group, an alkylsulfonylamino group, an arylsulfonylamino group, a substituted ureido group, or a carboxy group.

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

In a preferred embodiment of the present invention, the reducing substrate na is represented by the following formula (X).

Here, 0 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 between / and 3.

When O The second or third one is an electron donating group or...a rogen atom,
X may form a fused ring by itself or may form a ring with ORa.

The combined total carbon number of both Ita and X is g or more.

Among those included in formula (X) 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. T%a and Ra may be the same or different, and each may be an alkyl group, or Ra and Ra may be linked to form a ring.

3 Ra represents a hydrogen atom or an alkyl group, and FLa represents an alkyl group or an aromatic group. and 2 may be formed by forming a ring.

Oa Here, Ga is a hydroxyl group or a group that can generate a hydroxyl group by hydrolysis, Ra is an alkyl or aromatic 78 group,
ld represents a hydrogen atom, an alkyl group, an alkylthio group, a halogen atom, an acylamino group or an alkylthio group,
2 and R%O may be linked to form a ring.

Specific examples included in (X), (Xa), and (Xb) are IJS41-, 0! ;! , 11. ．． 2g,
! Samurai Kaisho jg-/, 2Al12, and 5t-it
Each is described in issue i3゜.

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

(However, the symbols Ga, X, Ra and mouth are expressed by the formula (
It has the same meaning as Ga, X, and R3n in X). ) Among those included in (XI) of the present invention, in a more preferred embodiment, the reducing substrate (Ra) has the following formulas (Xla) to (
It is represented by X[c).

i' 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; May form a ring; R%5 is a hydrogen atom,
Alkyl group represents an aromatic group; 4 Ra represents an alkyl group or an aromatic group; a %5
represents an alkyl group, an alkokene group, an alkylthio group, an arylthio group, a norogen atom, or an anolamino group; p is O1/or λ; R, a and Ra combine to form a condensed ring; Even if you stay
;Ra and 几a may be combined to form a condensed ring<
; Ra and Ra may be combined to form a condensed ring, and Ra XRa XI(' a\4 The total number of carbon atoms in Ra and (Ra)p is greater than 7.

However, Ga is a hydroxyl group or a group that gives a hydroxyl group by hydrolysis; 1 Ra represents an alkyl group or an aromatic group; R3a2 represents an alkyl group or an aromatic group; q represents θ, l or y; Ra and Ra may be combined to form a condensed ring.
and Ra may be combined to form a condensed ring < + Ra
,! :" may be combined with a to form a condensed ring; and the total number of carbon atoms of Ra, Ra, and (Ra ) q is greater than 7.

Ga In the formula, Ga represents a hydroxyl group or a group that provides a hydroxyl group by hydrolysis; R411 represents an alkyl group or an aromatic group; R4a
2 represents an alkyl group, an alkoxy group, an alkylthio group, an arylthio group, a norogen atom, or an aburamino group; "represents 0./or co; , -1.5 \, -', and The carbonized -\, atom in the condensed ring that participates in bonding to the phenol (or its precursor) mother nucleus (----a-> is a 37'-class carbon atom constituting one element of the condensed ring, Further, some of the carbon atoms in the hydrocarbon ring (excluding the tertiary carbon atoms mentioned above) may be substituted with oxygen atoms, or the hydrocarbons may have substituents. , or further aromatic rings may be fused; a ring may be formed.However, Ra, (Ra)r and the above (XI), '(Xla) to (X[b)] Specific examples are Tokkun Sho Kl, -/Otsu/3/, same j7-Otsuj
O1 same! 17-110173.

The essential parts of formula (In) and formula (IV) are para-
(sulfonyl)amine phenol moiety.

Specific examples include US3.72g, 3/, 2, U
S! , 071. ,J-,! 7. US Publications
hedPaLe, nt Application
B 3j/, 673, USg, /3 evening, ri2ri, (
JSll, 2 evenings.

Reducing substrates disclosed in No. 1, No. 2006-2012 are also effective as the reducing substrate (Ra) of the present invention.

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

Here, Ba1last contains a diffusion-resistant group.

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

Ga forms an aromatic ring and forms 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 definition are US-<t, os3゜3/
It is described in 2.

Reducing substrates of formulas (V), (■), (Vllll) and (IX) are characterized by containing a heterocycle, and specific examples include USIl, 19g, 23; j3
-≠t, 73o, US+, 27J, Zajj. A specific example of the reducing substrate represented by formula (Vl) is [JS+,/μri.

It is described in 192.

Things can be mentioned.

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 is diffusible in a hydrophilic or hydrophobic binder, and only the released dye needs to be diffusible. Therefore, the reducing substrate R has large hydrophobicity. thing.

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

4. Easy synthesis.

Next, a preferred specific example of f%a that satisfies these conditions will be shown. In the examples, NH- represents a linkage with a dye moiety.

04[I9(Sc 5H1□([) C3[1□ H OC16H33 H 0H OC161I33 0C16H33 N1)- N1(- H- I-1- Dyes that can be used as image-forming dyes include azo dyes, azomethine dyes, and anotraquinone. There are dyes such as naphthoquinone dyes, styryl dyes, nitro dyes, chi/IJ dyes, carbonyl dyes, and phthalonani7 dyes, and representative examples are shown on the dye side.These dyes can have multiple colors during development processing. However, it can also be used in a temporarily shortened form.

Yellow+L%" It wise a R"alCCCNHRa II II 11 N0 01-( Magenta 1 Ra 1 Ra \ Ha Ra - Ra TLa O0 3 OH In the above formula, Ra-Ra is a hydrogen atom, an alkyl group, Cycloalkyl group, aralkyl group, alkokene group, aryloxy group, aryl group, anruamino group, acyl group, cyano group, hydroxyl group, arylsulfonylamino group,
Arylsulfonylamino group, alkylsulfonyl group,
Hydroquinoalkyl group, cyanoalkyl group, alkoxycarbonylalkyl group, -r-rukoxyalkyl group, arylokynealkyl group, nitro group, halogen, sulfamoyl group, N-substituted sulfamoyl group, carbamoyl group, N-substituted carbamoyl &, 7'/ /L = represents a substituent selected from an okyne alkyl group, an amine group, a substituted amine group, an alkylthio group, and an aryl group, and among these substituents, the alkyl group and the aryl group further include a halogeno atom. , hydroxyl group, /ano group, acyl group,
Anruamino group, alkokino group, carbamoyl group, substituted carbamoyl group, sulfamoyl group, R-substituted sulfamoyl group, carboxyl group, alkylsulfonylamino group,
It may be substituted with 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 -r-no,
monouno group, carbamoyl group, substituted carbamoyl group,
Examples include a sulfamoyl group, a substituted sulfamoyl group, a sulfamoylamine group, a substituted sulfamoylamine group, a ureido group, a substituted ureido group, an alkoke group, a hydroxyalkoxy group, and an alkoxy/alkoxy/group.

In the present invention, tS whose hydrophilicity is significantly increased by proton dissociation under basic conditions is particularly preferred. group, (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 other additives such as a dye release aid contained in the system; and 3) ease of synthesis. Specific examples of preferred image-forming dyes satisfying these conditions are shown below. Here H2N-8O2
represents a binding site with a reducing substrate.

yellow 80　N1( 22 \ 5O2NII2 11 MagenLa C113 SO2NII2 80 Ni1 2 NlIC0Ctl 3 Of-1 H H CI(3 yan 1 8(1,NH□ Next, specific examples of preferable dye-donating substances will be shown.

(3) C41-19(L) OC161133 C51111(t) C4H9(0 14 04[190) (11) HC4119(L) (+ :+) (14) 1T (16) \C4119(E) \C4119( L) C4119 (1) C4119 (E) S (J2 (, H3 (22) (24) (25) 11 Rishi 16" 33 (28) H OC16H33 QC engineering. 1133 QC161133n QC, 6) 133-n: 3s ) QC16IT33-n 36) OC161133 (17) (38) (: horse C113 (40) (El 6H330CI (3 (43) OC! 6TI 3311 (visit) QC161133-1 (45) Oll ge] R1137-++ (46) CI]3C113 0C16II33-I] 0C161133-11 0(ko+611:+3-I+ 011 (54) 11 0C16■l33 (56) Of( (57) Qll (58) CII 3-C-CH3 3II7 (6” 011 0C16II33 (63) QH \ C16II33 (67) (69) OH OC161133 (11) (70) OH OH 1-1 In addition to the specific examples of -1=, as the dye-donating substance of the present invention, USIl, , Oss, 1121.% Kaishoj&
-/, 2! Nige! , same evening &-/l/30, same tg -7
Otsu/3/, same t7-tjO, same j7-g0tI3, US
j,? 21.3/2, US! ,07t,! 2ri,
US Published patent A
applicationB3j/, t73, USj, /3
! , Takota, USj, /ri1.23j, JP-A-Shoji3-
11t73o, CJSg,, 273. grr, USq
, /4/ri.

192, USj, lg2. Zari/, USj1. ! jJ'
, /20 etc. are also effective.

Furthermore, USj, 0/3, 1, 33, US4', /s
6, 4o ri, USj, /≠F, 4hiro/, USj.

its, Riza7, US4', /gug, t≠3, tJ S
g, /lr3. ysr, USj, 2p&, google,
(JStl, 2tl, t2j, US4', λas
, oλr1 Japanese Patent Publication No. 3 & -7/072, same j6-2
j737, same! r-/3171111, 33-/31
11'lli, same j, 2. -10 Otsu 7λ7, same 5/-1
Dye-donating substances that release dyes, such as those described in /ψri3O, are also effective in the present invention. Also 1, IsJ
.

Rijhiro, Guat,, US≠, 51I3), 3ro, (-
183, Ri3/,/Hiroshi II, US3, Ri3.2,3
17, USj, cotg, t211, USj, 236.3
07, Tokukai Shoj & -730t 7, Tokukai J'Otsu-71
0601 same evening t-/3≠zajO, same js-≠olI-o
, z, same! j-31,101/-, 33-. 23/,
2g, same jλ-10t7.27, same! J'-33/Hiroshi!
Dye-donating substances that emit magenta dyes, such as those listed in , J-J 33.2, and the like, are also effective in the present invention. Also US3.922,760, USj, 0/3,1°33,
USJ M2.91r7, USIl, 273°70g
, USII , /III , 1,172, US! ,/f
3, '7t/iZ, US<z, /≠7. j≠≠,
USj.

/6r, r3r, USp, zttt,, pip, US
Hiroshi, 26g, &lt, Tokukai Sho t&-7/θ611 same j3
-≠7gko3, same evening λ-rza27, same evening j3-/≠332
Dye-donating substances that release N'an dyes such as those listed in No. 3 are also effective in the present invention.

The dye-donating substance may be used in a total amount of 1.2% or more.

In this case, it is also possible to use one or more of the same pigment in combination, or to use two or more in combination to produce black.

The total amount of dye-donating substances is 10 mg/m2 g
/m2 is suitable and preferably used within the range of 2
Advantageously, a range of 0 mg/m2 to 10 I/m2 is used.

Generally, the dye-donating substance of the present invention is a reducing substrate 11. It is obtained by condensing the amino group of a with the chlorosulfonyl group of the image-forming dye.

Depending on the type of substrate, the amine group of the reducing substrate Ra can be introduced by reduction of nitro, nitroso, or azo groups or ring opening of petzoxazole, and can be used as a free base or as a salt of an inorganic acid. can. 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 chloride/sulfur chloride, phosphorus pentachloride, or thymenyl chloride.

A condensation reaction between the reducing substrate Ra and the image-forming dye moiety,
Generally dimethylformamide, dimethylacetamide,
It can be carried out at o-so'c temperature in an aprotic polar solvent such as dimethyl sulfokide, N-methyl birolide, acetonitrile, etc., in the presence of an organic base such as pyridino, picolino, rutin, triethylamine, diisopropylethylamino, etc. Usually, the desired dye-donating substance can be obtained in extremely good yield.

An example of its synthesis is shown below.

Synthesis Example/: Synthesis of Otsu-hydroquine-nomethylbe/zooxazole, 30t of 2,4'-dihydroxyacetophenone! /.

Hydroxylamine hydrochloride/Otogua 1 Sodium acetate 3
21f, ethanol 10007. and jθOml of water were mixed and heated under reflux for an hour. The reaction solution was poured into 101 ml of water, and the precipitated crystals were taken out and C1! .

31≠g of ti-dihydroxy/acetophenol/mu was obtained.

This Oxytum 30f/ was dissolved in 11.0OTjfK of acetic acid, and while stirring and heating at 1.20'C, hydrogen chloride gas was blown into the solution for 1 hour. After cooling, the precipitated crystals were collected and washed with water to give t-hydrogyno! - Methylbenzoxazole/7% k.

Synthesis example, 2=6-Hegiyadenluo, ¥, l;/-,!
-Synthesis of medylkunozoxazole Synthesis example/t-hydroxy/-2-meglubenzoxazole ig, oy, i-promo\xadeca/3
t, ri g1 potassium carbonate 211.0! .

N,N-dimethylformamide/2θat was stirred at OoC for hours. Separate the solids from the reaction solution, l!
I-/Vi was poured into 300 methanol. The precipitated crystals are collected by E 1~, and -\kizadecyl ox/-! −
Published by Methylbenoz Cazole≠, g, o Q Obtained F'r-8 Synthesis Example 3: Synthesis of 2-acetylamino-j-hexadecyloxy/phenol! t-heki-length desolucine-2-methylbenzogyazole obtained from ///g, ethanol/300g1,
1ioy of 33% hydrochloric acid (, 5'oH) were mixed and stirred at SS-zO°C for ψ hours. After cooling, the precipitated crystals were collected and treated with 2-acetylamino-5-hegizade/luoquin. Phenol t/3 g o fv.

Synthesis Example 1/, :, 2-acedelamino-≠-(-butyl-butylene-hexane/phenol synthesis obtained in Synthesis Example 3!-acetylamino/-4-hexyl->note/
Luoquinphenol 30. OI/, '7'' 7 bar list/j (registered trademark of Rohm Amidos Co., Ltd., USA) 2
0. Ofl and 300@l of toluene were mixed, and while stirring and heating at 0 to 0°C, Ino7'-7-no was blown into the mixture for 5 hours. The solid was removed by σ), then □M(vL was concentrated, the residue was converted to n-,
+ Crystals precipitated. Number of houses: 1-Ahiti-1
23.5 g of (.-amino-ψ-[-butyl-j-hexadecyl oxy/phenol) was obtained.

Synthesis Example 5: Synthesis of 2-amino-ψ-1-butyl-5-hexadeneluoquinophenol Noacetylamino-ψ-1-butyl- obtained in Synthesis Example ψ
j-Hexadecyl oxy/phenol, 23゜0g, ethanol/, 2θ shoulder t135% hydrochloric acid 6t scraps were mixed, 5
Stir and reflux for hours. After cooling the reaction solution, the precipitated crystals were separated to obtain λ-amino-ψ-1-duty-hexadecyloxy/phenol hydrochloride, 230.29.

Synthesis Example t; Synthesis of v-1-butyl-j-hexadenluoquine-2-(,2-(λ-methoxy/ethquin)-s-2)・robenzenesulfonylamino]phenol Obtained in Synthesis Example 2! -amino≠-E-butyl-j-heki'leech/luoquinphenol hydrochloride, ≠7 and λ
3.7 g of -(2-methkinethoxy/)-j-2]-lovenozenosulfonyl chloride was dissolved in NlN-dimethylacetamide/211, and after adding viriditsuno and ri mt, the mixture was heated at 2t'C for 1 hour. The reaction solution was poured into dilute hydrochloric acid, and an oily substance was precipitated. When 30 parts of methanol was added to this oily substance, it crystallized, and this was collected.

Yield ke, j da.

Synthesis Example 7: Synthesis of 2-amino-λ-(,2-methoxynoethquin)henzensulfonylamino]-t-butyl-terhekizaryloxy/phenol - Compound obtained in Synthesis Example t/θ7 ethanol AOm
Dissolved in t, 10 modulus ξ radiuno, - carbon catalyst about o, s
After adding y, hydrogen is added to J-,t kg/cm
and stirred at to 0C for 2 hours. Next, the catalyst was heated and allowed to cool, crystals precipitated, so P was removed.

Yield 7. jt! .

Synthesis Example G: Synthesis of 3-cyano-hiro-(ll-(1-methoxyethquin)-j-sulfophenylazo]-/-phenyl-terpyrazolone In a solution of sodium hydroxide g, oy and water, 20θml) -Amino-!-(2-methoxy/ethoxy/)benzenesulfonic acid geta, g, and then nitric acid/3.
An aqueous solution (, t o yt ) of ♂g was added.

Separately, a solution of 60 g of concentrated hydrochloric acid and water≠00 M1 was prepared, and the above solution was added dropwise to this at 50 C or lower. Thereafter, the reaction was completed by stirring for 30 minutes at a temperature below 00:00.

Separately, sodium hydroxide/Og, Og, 200 ml of water, sodium acetate 33. A mixed solution of θ and methanol-θθ was prepared, 3-anor/-phenyl=5-pyrazolo/37.0 g was added, and the diada solution prepared in -F was added dropwise at 70 °C or below. . Drops 3 at 100C or higher after the end
After stirring for 0 minutes and then stirring at room temperature for 7 hours, the precipitated crystals were collected, washed with 200 qi of -r setone, and air-dried.

Yield 3.2.0 (l m, po, 2t3~21.3
'C Synthesis Example: Synthesis of 3-/anogu[gu(]-memethoxyethoxy-j~chlorosulfonylphenylaazo-/-phenyl-j-pyrazolone) 3-cyano-hiro obtained in the above synthesis example -[(coumetquinethoxy-j-sulbophenylazo]-l-phenyl-
j-pyrazolone J/, Of, acetone, 2sOynl and oxychloride. N,N-dimethylacetamide was added dropwise to the mixed solution of tnl at 90 ml f:jO0C or less. After the dropwise addition, the mixture was stirred for about an hour and gradually poured into ice water. The precipitated crystals were placed on the E side edge and acetonitrile 10
It was washed with 0πl and air dried.

Yield: 416.7 F m, p, /I/ ~ /13°C Synthesis Example IO = Synthesis of dye-donating substance (1) λ-dij-amino-,2-(,2-methoxy) obtained in Synthesis Example 7 ethoxy)benzenesulfonylamino-ψ-t-phthyl-j-hexadenluoquinphenol A, 3 ywon, N
- 3-77''No≠-[≠-(2-Methoquinetoquine)-j-chlorosulfonylphenylazo]-/-phenyl-5-e' Lazolone q, B, dissolved in 30 ml of dimethylacetamide and obtained according to the synthesis example. 1 g of pyridine was added, followed by 1 ml of pyridine. After stirring at room temperature for 7 hours, the reaction solution was poured into dilute hydrochloric acid, and the precipitated crystals were counted. N, N-
Recrystallized from dimethylacetamide-methanol and obtained 7
I got M.

m, p, 1 g~/ri QC Synthesis Example 1/: Synthesis of dye-donating substance (2) λ-(teramino-2-(2-methquinethoxy) obtained in Synthesis Example 7)
Benzenesulfonylamino~≠-t-y'decylj-hexadecyloxyphenol 6.31 was dissolved in 30 ml of N,N-dimethylacetamide, and 3-/ano-gu(
j-Chloronomethylsulfonylphenyl 7)-/
-(≠-chlorosulfonylphenyl) -s -hirasoro/j, OQ was added, and then pyridi7j ql was added.

After stirring at room temperature for 7 hours, the reaction solution was poured into dilute hydrochloric acid, and the precipitated crystals were collected. After recrystallizing with acetonitrile, Guda was obtained.

m,p,/4LII~/Itta 0C synthesis example/2
2. Synthesis of dye-donating substance (lO) λ-amino+-1
-Butyl-j-hekitatecyloki/phenol hydrochloride≠
, <B and ψ-C3-chlorosulfonyl≠-(2-
methoxyethoxy)phenylazo)-,2-(N,N-
Diethylsulfamoyl)-j-methylsulfonylamino-/-naphthol <, tfiN, N-dimethylacetamide was dissolved in λOml and pyridine ψ-2d was added.

After stirring at 2J0C for 7 hours, the reaction solution was poured into dilute hydrochloric acid. The precipitated solid was collected and subjected to gel column chromatography (chloroform-ethyl acetate (?:
/) was purified by elution with a mixed solvent).

Total income J, 2 da.

Synthesis Example/3: Synthesis of dye-giving substance (17)! -Amino-ψ-1-butyl-j-hexadedyloki/phenol hydrochloride ii, ty is N, N-dimethylacetamide t
00ml and added pyridine/λyet. To this, j-(3-chlorosulfonylbenzenesulfonylamino)-,2-(N-[-butylsulfamoyl)-
≠-(,2-methylsulfonyl-dito-phenylazo)-/-1-phthol λOg was added. After stirring for 1 hour, it was poured into ice water j0011, and the precipitate was recrystallized from isopropyl alcohol-acetonitrile (/:/).6. Zaf
I got it.

Synthesis example/! : Synthesis of dye-donating substance (19) λ-[
j-amino-2-(2-methogyneethoxy/)benzenesulfonylamino]-≠-1-butyl-j-hexadecyloxyphenol 3/,! ;7, yo-(3” p o
oAz $; #i, i, o/l/d: nil7mi/)-4-(,2-methylsulfonyl-12-to-phenylazo)-/-naphthol3-.

1 g was dissolved in N,N-dimethylacetamide loOwtl and Viridi71/Hl was added. After tO separation and market stirring,
Methanol-2j OrlLl x 100 ml of water was added. The precipitated resinous material solidified after a while, so it was mixed several times. Add this tolue/-methanol-water (/Otsu: ψ:
3) F-crystal from the mixed system 'l/,! ;'l got it.

Synthesis Example 7.5' Synthesis of compound≠O a) 2. Synthesis of t-butylacetophenone 13 g of 1-butylhydroquinone was dissolved in acetic acid.

Boron trifluoride (BF3) was introduced into the solution for about 3 hours while dissolving it in water and heating it to 0°C.

After the completion of the reaction, pour the precipitated viscous solid into ice water in step 14.
I took it. This solid was dissolved in 2N-N;'l01 (600 shoulder t) and the undissolved part was made into F7!f. The r solution was made acidic with dilute hydrochloric acid, and the precipitated crystals were washed with P and then dissolved in water-containing methanol. It crystallized.

Convergence Ogg<ts%) 1)) 2. Synthesis of t-dihydroxy/-butylacetopheno/, og/mu:, 27 g of the ketone obtained in step a) was dissolved in 7 ethanol of ethanol.
0m1. Heat and dissolve with sodium acetate iti-g, and add hydroquinone hydrochloride y''mi//,!9 while stirring.
A solution prepared by dissolving 7θ in water was added and refluxed for about 7 hours. Crystals '5c are precipitated in ice water of reaction path I''r & 300m for tL.
F was taken and crystallized from benzene-hekilyne.

Collection 1i:/7. &(7&%) c) Synthesis of 4-t-butyl-j-hydroquine-2-methylbenzene ogizazole Oquine/≠9 obtained in b) above was dissolved in 700 ml of acetic acid, and while heating, dry hydrochloric acid gas was added. and refluxed for 5 hours. After reaction path i', the mixture was poured into 500 ml of ice water and the precipitated crystals were washed with water.

Total 9f/ (70th section) d) J-1-Butyl-j-heki-lyso/ru] No!
-Synthesis of methylbenozoxazole
ml and stirred with anhydrous potassium carbonate gg and hexade/rubromide//g at gθ ~ 00C for 6 hours/ζ0 After completion of the reaction, the inorganic matter was removed, and methanol tsOml was added to P solution and cooled on ice. Then, crystals precipitated. By counting this, the title compound was obtained.

Yield g, I! (1,,2%) C) Synthesis of 2-amine-5-1-butyl-1%-\Gyride/Phenol hydrochloride f-4e d)
Te4'Jfc Penzoxanol compound 7゜3g
Ethanol 30#It, concentrated hydrochloric acid! . The mixture was refluxed with me for 3 hours. After the reaction was completed, the mixture was allowed to cool, and the precipitated crystals were washed with 6 portions of water and then washed with A7 water.

Yield fi, t, riy (2,2%) f) Synthesis of compound example 0 The hydrochloride obtained in e) above! and the sulfonyl chloride g, ig of the dye with the structural formula F, and the dimer-f-acetamide jθ
The mixture was dissolved in water and stirred for 1 hour in a chamber pot with viridis/≠gold. After the reaction is complete, pour the precipitated crystals into dilute hydrochloric acid and collect them with E.
It was taken out and washed with water.

After drying, the residue was purified by glue gel chromatography to obtain 20.2 g of the title compound containing substantially all of the components.

Dye sulfonyl chloride: Synthesis example/l: Synthesis of dye-donating substance (42) In the above synthesis example/jd), 6-1 was used instead of 1,4-1-butyl-j~hydroxy/-2-methylbenzocazole. −
O-hexadecylation was performed using octyl-terhydroquine-λ~methylbenzoxazole. Next, a dye-donating substance (42) was obtained by the same treatment as in Synthesis Examples/je) and f).

The colored bone material of the present invention is manufactured by US NL No. 2,322.
It can be introduced into the layer of the photosensitive material f1 by a known method such as the method described in No. 27q. In that case, the following high boiling point organic solvents and low boiling point Nu/8 mediums can be used.

For example, phthalic acid alkyl ester (dibdelphthalate)
-, thioctylphthale-1, etc.), phosphoric acid ester (
Cyphenylphosphe-1
, 1 lycyl phosphate, dimexyl butyl phosph 7-1'), cydi/acid esters (e.g. acetyl triphtyl citrate), benzoic acid esters (octyl benzoate), -j'siluramides (e.g. diethyl laurylamide) , fat NJi acid ester l! n (e.g. dibutoxyethylsac,/nate, dioctyl azelate) = 1 High boiling point organic solvent such as rimesic acid esters (e.g. tributyl trimesate), or a boiling point of about 30"C to 1
60° (organic solvents such as ethyl acetate, lower alkyl acetate of butyl acetate, 10-pionic acid, secondary butyl alcohol, methyl isobutyl alcohol,
β-engineered ethyl acetate 1. After being dissolved in methyl cellosolve acetate, cyclohexanone, etc., it is dispersed in a hydrophilic colloid. The above-mentioned high boiling point organic solvent and low boiling point organic solvent may be used in combination.

Also, Special Publication No. 51-3 'l 853, Japanese Patent Publication No. 51-59
The polymer dispersion method described in No. 943 can also be used. In addition, various surfactants can be used when dispersing a dye-donating substance in a hydrophilic colloid, and these surfactants include surfactant 11t agent and U7 elsewhere in this specification. You can use the items listed below.

The amount of the high boiling point organic solvent used in the present invention is 10 g or less, preferably 5 g per 1 g of the dye-donating substance used.
J) Below.

In the present invention, "ζ" can be an auxiliary developer, if necessary.

The auxiliary developer used in the present invention is oxidized by a silver halide and/or an organic Iy salt oxidizing agent, and the oxidized product thereof is
It has the ability to provide a dye and oxidize the reducing substrate Ra in the chemical substance.

As a useful medicinal agent, and as a general one, high]'1 todone, L-butylno\hydroquinone, 2゜5
-Alkyl-substituted compounds such as dimethylhydroquinone 1
``Clanones, catecholes, pyrogallols, halogen-substituted high-1-electroquinones such as ri-1-co-1-cohydroquinone and cycloba-iF-quinone, alkaline compounds such as methoxyno, id[]+non, etc. There are polyhydroxyhembin derivatives such as 1-xy-substituted \-(l; tl quinones, methyl-substituted 1'ro'ton-nocarene, etc.).
Ascorhinic acid, asnilupic acid derivatives, N,
Hydroxylamines such as N'-C(2-di-toxyethyl)hydroxylamine, pyrazolidones such as ■-phenyl-3-pyrazolidone, 4-methyl-4-hydroxymethyl 1-phenyl-3-pyrazolidone, and reductones. and hydroxytetronic acids.

The auxiliary developing agent precursor used in the present invention: 1. Since it substantially exhibits the function of the above-mentioned auxiliary developing agent, the auxiliary developing agent precursor of the present invention is used to remove the auxiliary developing agent precursor. The above-mentioned auxiliary developer may be used in combination with the photosensitive material 'M'.
There is no need to wet the V contained in the photosensitive material:
It is possible to improve the storage performance before use while maintaining the performance of P1.

That is, the auxiliary developer precursor used in the present invention is defined as "τ" which has no developing effect but which is present during storage of the photosensitive material before use.
It is only through the action of an appropriate activator (e.g. base, nucleophile, etc.) or heating that it can be assisted! A compound that can release a drug.

In particular, the auxiliary developing agent precursor used in the present invention has no function as an auxiliary developing agent before heating because the reactive functional group of the auxiliary developing agent is blocked with a blocking group. Since the blocking group is thereby cleaved, the co-developing agent can be released at a reasonable rate.

The auxiliary developer precursor used in the present invention has the following general formula (1).
It can be expressed as

In the formula, R represents a group that can be cleaved by alkali hydrolysis, and R does not cross an aryl group. R1, R2, R3 and R4 represent a hydrogen atom, an alkyl group or an aryl group, and these may be the same or different.

In General 24], examples of the hydrolyzable group represented by A include R5-c-1R5-0-C-1111: 0 0 6 N-, C, -- /11 R7 (1, etc. However, 7 and R5 represent an aliphatic group having 1 to 22 carbon atoms, an aromatic group having 6 to 10 carbon atoms, or a heterocyclic group, and R6 and R7 represent a hydrogen atom, an aliphatic group having 1 to 22 carbon atoms, a carbon Represents an aromatic group or a heterocyclic group of 6 to 1 o,
R5 and R+= may be the same or different. R5,
The aliphatic groups represented by R6 and R7 may be substituted or unsubstituted, chain-like or buried.

Preferred substituents for the aliphatic group are an alkoxy group, an aryloxy group, an acylamino group, a carbamoyl group, a halogen atom, a sulfonamide group, a sulfamoyl group, a carboxy group, an alkanoyloxy group, a benzoyloxy group, a cyano group, a hydroxyl group, and an ureido group. , carbonyl group, aryl group, alkylsulfonyl group, alkoxycarbonyl group,
Examples include an alkylureido group, an imidazolyl group, a furyl group, a nitro group, a phthalamide group, a thiazolyl group, an alkanesulfonamide group, an alkanesulfamoyl group, an arylcarbonyl group, an imide group, and an alkoxycarbonylamino group.

R5, R6 and R7 are each aromatic groups (especially phenyl groups)
, the aromatic group may be substituted. Hepta-aromatic groups such as phenyl group include halogen atom, nitro group, hydroxyl group, cyano group, carboxy group, carbon F [, 32 or less Al 4
-ru group, alkenyl group, alkenyl group, a! Recoxycarbonyl group, rlucanoyloxy group, alkoxycarbonyl-7mino group, aliphatic amide group, alkylsulfamoyl group, alkylsulfonamide group, arylureido group, alkylsulfonyl group, alkylrf? The alkyl group may be substituted with a succinimide group, etc., and in this case, the alkyl group may have an aromatic group such as phenylene interposed in the chain. The phenyl group may also be substituted with an aryloxy group, an aryloxycarbonyl group, an arylcarbamoyl group, an arylamido group, an arylsulfamoyl group, an arylsulfonamido group, an arylureido group, etc., and these substituents may be substituted. The - group moiety may be further substituted with an alkyl group having from 1 to 22 carbon atoms.

When R''8), R6 and R7 do not represent a heterocyclic group, each heterocyclic group is bonded to the linking group to which the auxiliary developer is bonded via one of the carbon atoms forming the ring. Examples of heterocycles include thiophene, furan, pyran, pyrrole,
Examples C include pyrazole, pyridine, pyrazine, pyrimidine, pyridazine, indolizine, imitazole, deazole, oxazole, triazine, thiadiazine, and oxazine. These may further have a substituent on ring -L.

Examples of the aryl group represented by R in general formula (1) include phenyl group, naphthyl group, tolyl group, and xylyl group. These groups may be substituted. For example, halogen atoms (chlorine atoms, bromine atoms, etc.), amino groups, alkoxy groups, aryloxy groups, hydroxyl groups, aryl groups, carbonamide groups, sulfonamide groups, alkanoyloxy groups, benzoyloxy groups, ureido groups, carbamate groups, It may also be an aryl group substituted with a carbamoyloxy group, carbonate group, carboxy group, alkyl group (methyl group, ethyl group, propyl group, etc.).

The alkyl group represented by RI, R2, R3, and R4 in general formula (1) is an alkyl group having 1 to 1 o carbon atoms (for example, methyl group, ethyl group, propyl group, butyl group, etc.),
These alkyl groups may be substituted with hydroxyl groups, amino groups, and the like. Further, as the aryl group, a phenyl group, a naphthyl group, a lyl group, a lyl group, etc. can be used. These aryl groups include halogen atoms (Shiosuya Ryo, bromine atoms, etc.), altol groups (methyl, ethyl, prot', +1/ groups, etc.), hydroxyl groups, alkoxy groups (methoxy In the present invention, R7, R2, and R4 are hydrogen atoms, -? Lukyl group,
Preferably, the carbon number is 1 to 10, and the aryl group is more preferable.

WaT? B: Examples of the auxiliary developer precursor used in the present invention are shown below.The auxiliary developer precursors of the present invention can generally be synthesized according to the reaction formula shown below.

1st stage H-Z + CH20-4100H2-Z 2nd stage In the formula, A and Z represent the same meanings as the groups already defined, and L represents a halogen atom or a hydroxyl group. In the second stage reaction, when L represents a hydroxyl group, a membrane water tank mixture is used, such as carposi-imide, and when L represents a halogen atom, a base is used as a deoxidizing agent. It may be used or it may not be used.

Next, a typical synthesis example of the precursor compound of the present invention will be shown.

Synthesis example (1) Synthesis step of exemplified compound (1) ■, 4,
15 of 4-dimethyl-1-phenyl-3-pyrazolidone
2 g was dissolved in 600 ml of acetic acid. To this solution, 97 g of an aqueous solution containing 37% formaldehyde was added dropwise at room temperature with stirring. After stirring for 2 hours, the solvent was distilled off under reduced pressure. To the residue was added 1 liter (100 m/liter), and water was distilled off azeotropically under reduced pressure together with 1 liter of ene.

900ml of hexane and 7° of ethyl acetate to the residue]mj!
After heating and melting, the crystals were cooled to room temperature, and the shattered crystals were collected by filtration, and 1120 g of 4.4 dimethyl-2-hyF
Roxymethyl-1-phenyl-3-pyrazolidone was obtained.

Stage■.

Obtained 4,4-dimethyl-2-hydroxomedyl-1
- 66 g of phenyl-3-pyrazolidone and 39 g of 4-chlorobenzoic acid were added to a solution of N,N-dimethylformamide at room temperature with stirring, and 48 g of N-ethyl-N'-(3-dimethylaminopropyl)carbodiimide hydrochloride was added. Added gradually. After reacting for 4 hours at room temperature, the reaction mixture was poured into water and extracted with ethyl acetate Ip. After washing the organic phase with water,
Sulfuric anhydride L IJ J. After commenting, the solvent was distilled off under reduced pressure. The residue was recrystallized from hexane and ethyl acetate to obtain 55 gt'7 of the desired product (1). The melting point was 88-89°C.

Synthesis Example (2) Synthesis of Exemplary Compound (2) Synthesis Example (1)
) 6.6 g of 4,4-dimethyl-2-hydroxymethyl-1-phr-3-pyrazolidone obtained in step (2) and 4-
Chloro-3-methanesulfonamide 1'benzoin Fl#7.
2 g was dissolved in 20 m6 of N,N-dimethylformamide. 2.6 g of N,N'-diisopropylcarbodiimide was added dropwise to this solution. Incubate the reaction at room temperature for 1 hour.
The precipitated Vn(t(N,N'-diisopropylurea) was separated by filtration, and the filtrate was poured into water. Ethyl acetate 20
The a-phase was separated and washed with water. After ethyl acetate was distilled off under reduced pressure, the residue was recrystallized from a mixed solvent of ethyl i1' acid and hexane to yield 6.7 gf'J', = of the target compound (2). The melting point was 138-140°C.

Synthesis Example (3) Synthesis of Exemplary Compound (3) Synthesis Example (1)
22 g of 4,4"-2-methyl-2-hydroxymethyl-1-phenyl-3midobenzoic acid obtained in Step ① was combined with dimethylsulfoxy 1'2Q m j! and N,N-dimethyl. It was dissolved in a mixed solvent consisting of formamide.

0.3 g of 4-dimethylaminopyridine was added, and 13 g of N,No-diisopropylcarbodiimide was added dropwise at room temperature. After stirring for 4 hours, add 500mj of ethyl acetate! was added and washed with water. After filtering off the crystals deposited in the oil phase, the filtrate was concentrated under reduced pressure. The residue was recrystallized from ethyl acetate to obtain 29 g of the target compound. The melting point was 153-154''C.

Synthesis Example (4) Synthesis of Exemplary Compound (4) Synthesis Example (1)
In step (1), 13.2 g of 4,4'-dimethyl-2-hydroxymethyl-3-pitizolidone and 9.2 g of 2-chlorophenyl isoisoaner were dissolved in 40 ml of dimethyl sulfoxide. After reacting at room temperature for 3 hours, 100rr+/ of ethyl acetate was added and washed with water.

The oil phase was separated and concentrated. The residue was recrystallized from a mixed solvent of ethyl acetate and hexane to obtain 8 g of the desired product (4). The melting point was 119-120°C.

Synthesis Example (5) Synthesis of Exemplary Compound (7) Synthesis Example (1)
4,4°-dimethyl-2-human r obtained in step ■,
3 g of 3-pyrazolidone and 1 ethyl acetate
Suspended in O+ne. One phenoxy compound was added dropwise at 10"C.Additionally, 7L of viridi, 1m1
The mixture was stirred at 10°C for 3 hours at this temperature. After being transferred to a branch funnel, it was washed with water. Urawa was mixed with anhydrous sodium sulfate for 1 minute, and then the solvent was distilled off under reduced pressure. The residue was mixed with 2 liters of hexane and ethyl acetate, and chromatographed using a JFla solution using a power ram packed with 250 g of silica gel.
Concentrate the product-containing fractions to obtain the desired compound in 3
．． I got 5g. The melting point was 98-101°C.

The auxiliary developer precursor used in the present invention can be used within a certain concentration range. Useful concentration range is 0.0 for silver
A particularly useful concentration range is from 0.005 times molar to 20 times molar, and from 0.001 times molar to 4 times molar.

To introduce the auxiliary developer precursor into the hydrophilic colloid layer,
High-boiling organic solvents such as socuric acid alkyl esters (dibutyl phthalate, dioctyl phthalate, etc.), phosphoric acid esters (diphenyl phosphate, triphenyl fumesnoe-1,1 licresyl phosphate, dioctyl butyl tumesphate), citric acid Acid esters (e.g. acetyl tributyl citrate), benzoate esters (e.g. octyl benzoate), alkylamides (e.g. diethyl laurylamide'), fatty acid esters (e.g. dibutoxyethyl succinate, dioctyl azelate)
, using the method described in U.S. Pat. After dissolving in lower alkyl acetate, ethyl propionate, secondary butyl alcohol, methyl isobutyl ketone, β-ethoxyethyl acetate, methyl cellosolve acetate, cyclohexanone, etc., it is dissolved in a hydrophilic colloid. .The above high 61 point twist is mixed with a solvent (!l':
It may also be used in combination with Wit point +i, 'j beach medium.

Also, Special Publication No. 51-39853, Japanese Patent Publication No. 51-59943
It is also possible to use the dispersion method using polymers described in No. It can be directly dispersed in the emulsion, or it can be dissolved in water or alcohol and then dispersed in geladine or in the emulsion.

The auxiliary developer niJ precursor of the present invention can be used in combination of two or more types, and each emulsion JW (i'? sensitive layer, green sensitive layer,
It can be added to all emulsion layers (red-sensitive layer), it can be added to all emulsion layers, and it can also be added to layers adjacent to the emulsion (antihalation layer, undercoat layer, intermediate layer, protective layer, etc.). I can do it.

? 11i 11. When should IJ developer be added? Although it may be carried out at any time during the 1λ manufacturing process, it is generally preferable to do so immediately before coating.

The reaction mechanism by which the S7 drug precursor releases the auxiliary developer (Iik) expressed as A1-force x, r, CI used in the present invention is not necessarily clear, but for example, when the auxiliary developer is The reaction released by a base can be considered to be expressed by the following reaction formula.

When the compound of general formula (1) is expressed as A-OCH2-B below, 2 □□----- 110H2C-B CH2O+ HB3 In the above reaction formula, kl, k2 and ni3 are the reactions of the respective reactions. Represents the rate constant.

In the second stage equilibrium reaction, it is generally known that the rate of methylol formation (k3) is greater than the rate of decomposition of methylol (k2) (e.g. Bul ),
Soc, Chint, Franr:e,
.

138 (1955) provides a detailed report on the production and decomposition reaction of methylolhenzamide).

Furthermore, in the second step of flat t9j reaction, the methylol component 11
The A' reaction is a first-order reaction, whereas the reaction for producing a methylol compound is a second-order reaction. In the second-order reaction, the product production rate does not depend on the concentration of shellfish material, but in the second-order reaction, the product production rate depends on the raw material concentration.

In a secondary reaction, the reaction rate at a certain time is higher at a high concentration than at a low concentration.

Therefore, in the second stage equilibrium reaction, a certain k 2
When 3 is given to and, changing the concentration conditions will change the ratio of concentration Q (to
well known.

The precursor compounds of the present invention are usually used in films with high r'1
4i, +! It is dissolved in ti, :;I, and dispersed in seratin, etc.

1. (L) When the raw film is stored, the precursor compound exists at a high concentration in the oil droplets, and even if it decomposes into the ゛ζi; In the reaction, the Qllll of the methylol compound is kept high, and it is thought that the release of B-, which is a useful group for photography, is extremely low. Excellent stability during storage, desensitization,
The experimental fact that no adverse effects such as fogging were observed is believed to be based on the reasons explained above.

On the other hand, during heating, a basic component generated by thermal decomposition is generated, and as a result, the precursor compound is hydrolyzed (first step reaction), and then a decomposition reaction of the methylol compound occurs, and a sufficient amount of photographically useful material is generated. It will be understood that a group is released.

When the precursor compound of the present invention is incorporated into the film,
It exhibits sufficient photographic properties when heated, and the raw film J.
It is believed that the experimental fact that the stability during storage is good is based on the reasons stated above.

The rate at which the auxiliary developer is released naturally varies depending on the nature of the atomic group represented by A in general formula (1). Therefore used in the present invention? 11i co-developing agent precursors are a group of compounds that allow the release rate of co-developing agent upon heating to be adjusted to the required rate.

Silver halides used in the present invention include silver chloride, silver bromide, silver chloroiodide, silver bromide, silver iodobromide, chloroiodobromide, and iodide tM'! There is +;

In the present invention, when using tin halide alone without using an organic silver salt oxidizing agent, it is preferable to use silver halide containing silver iodide crystals in a part of the grains. A 1-gen IB tri like .1: is indicated by its x19 diffraction pattern and U7 pattern of pure silver iodide.

'T; - For the true sensitization process, silver halide containing two or more types of hydrogen atoms is used. In the L agent, silver halide fi:'r T- is complete≦
So'J IJj products are made. For example, iodobromide t9tL
In 7i'IJ, when the X-ray diffraction is measured, patterns of silver iodide crystals and silver bromide crystals appear. .

In the present invention, particularly preferred silver halide contains silver iodide crystals in the grains. And e is chloriodide tl, where the X-ray pattern of silver iodide crystal appears! , silver iodobromide, chloroiodobromide-based IC9 can be obtained by first making silver bromide grains by adding a silver nitrate solution to a potassium bromide solution, and then adding potassium iodide. .

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

The grain size of the silver halide used in the present invention has an average grain size of 0.001 μm to 10.0 μm. ljm, preferably from 0.001 μm to 5 pm.

The silver halide used in the present invention may be used as it is, but it may also be compounded with chemical sensitizers such as compounds such as sulfur, selenium, tellurium, etc., compounds such as gold, platinum, palladium, rhodium and iridium, and halogenated silver halide. Chemical sensitization may also be achieved by the use of reducing agents such as tin or combinations thereof. For more information,
“Th eTheory of the Ph.
oto-graphlc, Process”4th edition,
T.

1 (pages 149-169 of the 5th edition of James II).

In a particularly preferred embodiment of the present invention, silver halide is used in combination with a silver salt oxidizing agent, but the silver halide used in this case includes pure silver iodide crystals when silver halide is used alone. It is not necessary to have these characteristics, and all silver halides known in the art can be used.

The organic silver salt oxidizing agent used in the present invention is produced at a temperature of 80°C or higher, preferably at 100°C or higher in the presence of photosensitive silver halide.
When heated above ℃, reacts with the image-forming substance or a reducing agent coexisting with the image-forming substance if necessary,
It forms a silver image.

By coexisting with an organic silver salt oxidizing agent, it is possible to obtain a photosensitive material that develops color with higher density.

Examples of such organic silver salt oxidizing agents include silver salts of organic compounds having a carboxyl group, and typical examples include silver salts of aliphatic carboxylic acids and silver salts of aromatic carboxylic acids. There is.

Examples of aliphatic carboxylic acids include silver salts of behenic acid, silver salts of stearic acid, silver salts of oleic acid, tin salts of lauric acid, silver salts of capric acid, silver salts of myristic acid, and silver salts of palmitic acid. , silver salt of maleic acid, silver salt of fumaric acid, silver salt of tartaric acid, silver salt of furoic acid, silver salt of linoleic acid, silver salt of oleic acid, silver salt of adipic acid, silver salt of sebacic acid, succinic acid. ta salt, acetic acid 2y salt, butyric acid silver salt, (Q brain 1
There are silver salts of ψ, etc., and those substituted with cogen or hydroxyl groups of these silver salts are also effective.

Examples of silver salts of aromatic carboxylic acids and other carboxyl group-containing compounds include silver salts of ￥benkokan, 3゜5-dipidroxyben, silver salts of shikojo'-(1 to methylbenzoic acid,
■ + Silver salt of 1-medylbenzoic acid, silver salt of p-medylbenzoic acid, silver salt of 2,4-dichlorobenzoic acid, acetamide (
Silver salts of substituted benzoic acid such as benzoic acid, silver salt of p-phenylbenzoic acid, silver salt of gallic acid, silver salt of tannic acid, silver salt of phthalic acid, Silver salt, silver salt of salicylic acid, silver salt of phenylacetic acid, silver salt of pit:I mellitic acid, 3-carboxymethyl-4-methyl-4-thiazoline- described in U.S. Pat. No. 3.785.53oi4 Silver salts such as 2-thione, U.S. Pat. No. 3,330°663
There are silver salts of aliphatic carboxylic acids having a thioether group as described in the specification of the above patent.

In addition, there are silver salts of compounds having a mercapto group or a thione group and derivatives thereof.

For example, 3-mercapto-4-phenyl-1゜2.4-
Silver salt of triazole, silver salt of 2-mercaptobenzimidazole, silver salt of 2-mercapto-5-aminothiadiazole, silver salt of 2-mercaptobenzthiazole, 2-
Silver salts of thioglycolic acid described in JP-A-48-28221, such as silver salt of (s-ethylglycolamide) benzthiazole, S-alkyl (alkyl group having 12 to 22 carbon atoms) thioglycolic acid, dithio Silver salts of dithiocarboxylic acids such as silver salts of acetic acid, silver salts of thioamides, silver salts of 5-carboxy-1-methyl-2-phenyl-4-thiopyridine, silver salts of mercapto[lyazine, 2-mercaptobenzthiazole silver salts of mercaptooxadiazole, silver salts described in U.S. Pat. No. 4,123,274, e.g.゜4-
Silver salts of thione compounds such as silver salts of triazoles and silver salts of 3-(2-carboxyethyl)-4-methyl-4-thiazoline-2-thione described in U.S. Pat. No. 3,301.678. .

In addition, there are silver salts of compounds having imino groups. For example, Tokuko Sho 44. Silver salts of benzo-1-lyazole and its derivatives as described in No. 30270 and No. 45-18416, such as silver salts of benzotriazole, silver salts of alkyl-substituted benzotriazole such as silver salt of methylhensitriazole, and 5-chlorobenzo Silver salts of halogen-substituted henctriazoles, such as silver salts of triazoles, silver salts of carboimidobenzotriazoles, such as silver salts of butylcarboimidobenzotriazoles, U.S. Pat. No. 4,220.70
1.2.4-) lyazole and 1-H- described in Specification No. 9
Examples include silver salts of tetrazole, silver salts of carbazole, silver salts of saccharin, and silver salts of imidazole and imidazole derivatives.

In addition, in the present invention, Research Disclosure -V
Organometallic salts such as silver salts and copper stearate described in No. 117029, June 1978 can also be used in the same manner as the various silver salts mentioned above. Two or more types of organic silver salt oxidizing agents can be used in combination.

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

When a photosensitive material is irradiated with light, a latent image is formed on the photosensitive silver halide. Regarding this, °C is T, H, J a
“The Theory of the
PhotographicProcess"3rd
Edition, pages 105 to 148.

Furthermore, by heating the photosensitive material, the dye-donating substance of the present invention acts as a reducing agent, and the latent image nuclei act as a catalyst.
The silver halide and/or organic silver salt oxidizing agent is reduced to form silver, which is itself oxidized. This oxidized dye-donating substance is cleaved to release the dye. In this case, the coexistence of a nucleophilic reagent promotes the dye release reaction. When an organic silver salt oxidizing agent is used in combination, the silver halide and the organic silver salt oxidizing agent must be present at a substantially effective distance in order to promptly initiate the reaction. It is desirable that the silver halide and the organic silver salt oxidizing agent exist in the same layer.

Development by heating differs from so-called wet development in that the reaction requires time because the diffusion of reactive molecular species is restricted. However, if too much time is spent on heating for development, the thermal reaction in the unexposed areas cannot be ignored and so-called fog occurs, which is undesirable.

In the present invention, a hot solvent can be used as one means for improving such disadvantages. Here, "thermal solvent" is a solid at ambient temperature,
A non-hydrolyzable organic material that exhibits a mixed melting point with other components at or below the heat treatment temperature used, and increases the development speed when heat-developed in the presence of a hot solvent. , it is possible to improve the image quality. As such a thermal solvent used in the present invention, a compound that can serve as a solvent for a developer, a compound that is a substance with a high dielectric constant and is known to accelerate the physical development of a silver salt, and the like are useful. Useful thermal solvents include U.S. Pat.
, 347,675, such as polyethylene glycol with an average molecular weight of 1,500 to 20,000, derivatives of polyethylene oxide such as oleate ester, beeswax, monostearin, -3O2-1-CO
- compounds with a high dielectric constant, such as acetamide,
Succinimide, ethyl carbamate, urea, methyl sulfonamide, ethylene carbonate, U.S. Patent No. 3
, 667.959, lactone of 4-hydroxybutanoic acid, methylsulfinylmethane, tetrahydrothiophene-1,1-dioxide, Research.
Disclosure magazine December 1976 issue pages 26-28
1,10-decanediol, methyl anisate, described on page
Biphenyl schelate and the like are preferably used.

Although the role of the thermal solvent in the present invention is not necessarily clear, it is understood that its main role is to promote the diffusion of reactive molecular species during development.

The photosensitive silver halide, organic silver salt oxidizing agent of the present invention is prepared in the following binder. Also dispersed in the binder is a color-imparting substance.

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

The silver halide used in the present invention may be spectrally sensitized by medium pigments or the like. The pigments used include cyanine pigments, merocyanine pigments, composite cyanine pigments, composite merocyanine pigments, boropolar cyanine pigments,
Included are hemicyanine dyes, styryl dyes and hemioxonol dyes. Particularly useful dyes are cyanine dyes,
It is a pigment belonging to merocyanine pigments and complex merocyanine pigments. Any of the nuclei commonly used for cyanine dyes can be used as the basic heterocyclic nucleus for these dyes. Namely, pyrroline nucleus, oki-purine nucleus, thiazoline nucleus, virol nucleus, oxazole nucleus, thiazole nucleus, selenazole nucleus, imidazole nucleus, tetrazole nucleus, pyridine nucleus, etc.; these nuclei are fused with an alicyclic hydrocarbon ring. : and nuclei in which aromatic hydrocarbon rings are fused to these nuclei, i.e., indolenine nucleus, benzindolenine nucleus, indole nucleus, benzoxadole nucleus, naphthoxazole nucleus, hendithiazole nucleus, naphthothiazole nucleus, henzoselenazole. Nuclei, benzimidazole nuclei, quinoline nuclei, etc. are applicable. These nuclei may be substituted on carbon atoms.

Examples of nuclei having a ketomethylene structure in merocyanine dyes or complex merocyanine dyes include birapurin-5-one nucleus, thiohydantoin nucleus, 2-thioxazolidine-2,
A 5- to 6-membered heterocyclic nucleus such as a 4-dione nucleus, a thiazolidine-2,4-dione nucleus, a rhodanine nucleus, a thiobarbic acid nucleus, etc. can be applied.

Examples of useful sensitizing dyes include German Patent No. 929.
No. 080, U.S. Patent No. 2,231,658, U.S. Patent No. 2,
No. 493,748, No. 2.503.776, No. 2
, No. 519,001, No. 2.912,329, No. 3,656,959, No. 3.672.897, No. 3,694°217, No. 4,025,349 ,
4゜04G, 572, British Patent No. 1,242.5
No. 88, Special Publication No. 44-14030, No. 52 2484
Examples include those described in No. 4.

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

Representative examples are U.S. Patent Nos. 2,688,545 and 2.
．． 977.229, 3,397.060, 3,522,052, 3,527.641, 3.617,293, 3,628,964,
Same 3rd. 666, 480, same No. 3,672,89
No. 8, No. 3,679.428, No. 3,703,3
No. 77, No. 3,769,301, No. 3,814.
No. 609, No. 3,837,862, No. 4,026
No. 707, British Patent No. 1,344,281;
．． No. 507.803, Special Publication No. 43-4936, No. 53
-12375, JP-A-52-110618, JP-A No. 52
-109925.

Along with the sensitizing dye, the emulsion may contain a dye that itself does not have a spectral sensitizing effect or a substance that does not substantially absorb visible light and exhibits supersensitization. For example, aminosujiru compounds substituted with nitrogen-containing heterocyclic groups (e.g., 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. 3,615.6], No. 3, U.S. Patent No. 3
, 615,641, 3,617° 295, and 3,635,721 are particularly useful.

In the present invention, various dye release aids are used in various ways,
For example, it can be used by being included in any layer of a photosensitive material or any layer of a dye fixing material. A dye release aid is a photosensitive silver halide and/or
Or promotes the redox reaction between the organic silver salt oxidizing agent and the dye-donating substance, or acts nucleophilically on the dye-donating substance oxidized in the subsequent dye release reaction to promote dye release. Bases or base precursors are used. In the present invention, it is particularly advantageous to use these dye-releasing aids in order to accelerate the reaction, but when these dye-releasing aids are included in the light-sensitive material,
It is necessary to particularly select a material that does not impair the storage stability of the photosensitive material. Examples of preferable bases that can be used in photosensitive materials include amines, including trialkylamines, hydroxylamines, aliphatic polyamines, N-alkyl substituted aromatic amines, N-b
J: oxyalkyl-substituted aromatic amines, and bis[p
-(dialkylamino)phenylcomethanes can be mentioned. Also, in U.S. Patent No. 2゜410.644,
Betaine tetramethylammonium iodide, diaminobutane dihydrochloride, is disclosed in U.S. Patent No. 3.506.4.
No. 44 describes organic compounds containing amino acids such as urea and 6-aminocaproic acid, which are useful. The base precursor releases a basic component when heated. Examples of typical base precursors are described in British Patent No. 998.949. Preferred base precursors are salts of carboxylic acids and organic bases; useful carboxylic acids include trichloroacetic acid, trifluoroacetic acid; useful bases include guanidine, piperidine, morpholine, p-toluidine, 2-
There are picoline etc. Guanidine trichloroacetic acid, described in US Pat. No. 3,220,846, is particularly useful.

Aldonamides described in JP-A No. 50-22625 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 of the coating buffing film of the photosensitive material, preferably o, oiM amount% to 4%.
o% by weight.

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

[General formula]

A2 A4 In the above formula, AI, A2, A3, and A4 may be the same or different, and each represents a hydrogen atom, an alkyl group, a substituted alkyl group, a cycloalkyl group, an aralkyl group, an aryl group, a substituted aryl group, and a heterocyclic residue. It represents a substituent selected from among the groups, and Al and A2 or A3 and A4 may be linked to form a ring.

As a specific example, H2N502NH2, 82NS02N
(CH3)2, H2N502N (C2H5)2, H
2N5O2NHCH3, H2N502N (C2H40
H) 2, Cl5NH3O7NHC! (3, etc.)

The above compounds can be used in a wide range of applications.

A useful range is 20ffi amount % or less based on the weight of the coated soft film of the photosensitive material, more preferably 0.1 to 1
It is 5% by weight.

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 a compound that decomposes and releases water during thermal development. These compounds are particularly known for transfer printing of fibers, and NH,:Fc (504)2.12H20 described in JP-A-50-88386 is useful.

The support for the photosensitive material used in the present invention is one that can withstand processing temperatures. Common supports include glass, paper, metal and their analogs, as well as cellulose acetate film, cellulose ester film, polyvinyl acetal film, polystyrene film, polycarbonate film, polyethylene terephthalate film and related materials. Includes film or resin materials. U.S. Patent No. 3,634.
The polyesters described in No. 089 and No. 3,725.070 are preferably used. Particularly preferably, a polyethylene terephthalate film is used.

The coating solution used in the present invention can be prepared by mixing separately formed silver halide and organometallic salt oxidizing agent before use, but it is also possible to prepare the coating solution by mixing the two separately. Mixing in a ball mill for hours is also effective. Also effective is a method in which a halogen-containing compound is added to the prepared organic silver salt oxidizing agent to form halogen silver with the silver in the organic silver salt oxidizing agent.

For information on how to make these silver halides and organic silver salt oxidizing agents, how to mix them, etc., see Research Disclosure No. 17029, JP-A-50-32928, and JP-A-50-32928.
No. 1-42529, U.S. Patent No. 3,700,458;
It is described in JP-A-49-13224, JP-A-50-17216, etc.

In the present invention, the coating amount of the photosensitive silver halide and organic silver salt oxidizing agent is 50 mg to 10 g/lOg in total in terms of silver.
m2 is appropriate.

8. The photographic emulsion or other hydrophilic colloid of the light-sensitive material of the present invention may contain coating aids, antistatic properties, improving shearing properties, emulsification dispersion, preventing adhesion, and improving true characteristics (e.g., accelerating development, increasing contrast, Various surfactants may be included for various purposes such as sensitization).

For example, saponin (Steshi 1 + S system), )' alkylene oxide derivatives (e.g., polyethylene glycol, polystyrene glycol J-/S/polypropylene glycol condensate, polyethylene glycol alkyl ethers or polyethylene glycol alkyl aryl ethers,
polyethylene glycol x esters, polyethylene glycol alkyl ethers, polyalkylene glycol alkyl amines or amides, silicone polyethylene oxide adducts), glycidol derivatives (e.g. alkenylsuccinic acid polyglycerides, alkylphenol polyglycerides), fatty acids of polyhydric alcohols Nonionic surfactants such as esters and sugar alkyl esters;
Alkylcarphonates, alkylsulfonates, alkylhenzenesulfonates, alkylnaphthalenesulfonates, alkyl sulfates, alkyl phosphates, N-acyl-N-alkyltaurines, sulfosuccinates, Anionic surfactants containing acidic groups such as carboxy groups, sulfo groups, phospho groups, sulfate ester groups, phosphate ester groups, such as sulfoalkyl polyoxyethylene alkylphenyl ethers, polyoxyethylene alkyl phosphate esters; Amino rM! , kind,
Aminoalkyl sulfone! Amphoteric surfactants such as S, aminoalkyl sulfates or phosphoric esters, alkyl betaines, and amine oxides; amphoteric surfactants such as alkylamine salts, aliphatic or aromatic quaternary ammonium salts, and heterocyclic surfactants such as pyridinium and imidazolium. Cationic surfactants such as quaternary ammonium salts and phosphonium or sulfonium salts containing aliphatic or heterocycles can be used.

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 S.
U r f a c t a n tScience
5eries Volume, Non1onic
5urfactants (Edited by
Martin J.

5hick, Marcel Dekker Inc, 1
967), 5surfaceActiveEthy
lene Oxide Adducts (Schou
feldt, N. Pergamon Press
1969), and the 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 polyethylene glycol type moiety/ionic surfactant is equal to or less than the weight of the hydrophilic binder, preferably 50%.
Used below.

The photosensitive 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, 5ection B36 (1953), US
P2,648,604, USP3,671,247, Japanese Patent Publication No. 4.4-30074, Japanese Patent Publication No. 44-9503, etc.

In the light-sensitive material used in the present invention, a compound that activates development and simultaneously stabilizes the image can be used. Among them, 2-hydroxyethylisothiuronium, trichloroacetate, described in U.S. Pat. No. 3,301°678,
Isothiuroniums represented by 1-, U.S. Patent No. 3,
Hisisothiuronium compounds such as 1,8-(3,6-thioxaoctane)bis(isothiuronium trifluoroacetate) described in No. 669,670, West German Patent No. 2゜1
62.714, thiazolium compounds such as 2-amino-2-thiazolium trichloroacetate and 2-amino-5-bromoethyl-2-thiazolium trichloroacetate described in U.S. Pat. No. 4,012,260. Compounds, U.S. Patent No. 4,060,420
His(2-amino-2-thiazolium)methylenebis(sulfonylacetate), 2-amino-2-thiazolium phenylsulfonylacetate, etc. described in No.
Compounds having α-sulfonylacetate as an acidic moiety, compounds having 2-carboxycarboxamide as an acidic moiety described in US Pat. No. 4,088,496, and the like are preferably used.

In the case of the present invention, since the dye-providing substance is colored, it is not so necessary to further contain an anti-irradiation substance, an anti-halation substance, or various dyes in the light-sensitive material. In order to improve the sharpness of
No. 3.921, No. 2.527,583, No. 2.9
It is possible to contain filter dyes, absorbent substances, etc. described in various specifications such as No. 56,879.

Further, these dyes are preferably thermally decolorizable, such as those described in U.S. Pat. Nos. 3,769,019 and 3,145.
．． No. 009, No. 3. 615. Dyes such as those described in No. 432 are preferred.

The photosensitive material used in the present invention may 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 A
It can contain an H layer, a release layer, etc. For various additives, see Research Disclosure Magazine Vol. 1.17.
0. Additives described in No. 17029 of June 1978, such as plasticizers, sharpness improving dyes, A H
Dyes, sensitizing dyes, capping agents, surfactants, fluorescent brighteners,
There are additives such as anti-fading agents.

In the present invention, similar to the heat-developable photosensitive layer, coating solutions are prepared for the dye fixing layer, protective layer, intermediate layer, undercoat layer, hack layer, and other layers using the dipping method, air knife method, curtain method, etc. A light-sensitive material can be prepared by sequentially coating onto a support by a seed coating method such as a coating method or a hopper coating method described in US Pat. No. 3,681,294 and drying each time.

Further, if necessary, see US Pat. No. 2,7bL 791 and British Patent No. 837. It is also possible to apply 21 or more layers simultaneously by the method described in 095-';

In the present invention, the latent image obtained after the exposure of the photosensitive material-2 is approximately 0.95°C at a moderately elevated temperature of, for example, approximately 80°C to approximately 250°C. Development can be accomplished by generally heating the element for 5 seconds to about 300 seconds. As long as the temperature is within the above range, it can be used at either high or low temperatures by increasing or shortening the heating time. A temperature range of about 110°C to about 160'C for the intestine is useful.

The heating means includes a hot plate 1.TF. 1 icon,
Other methods such as heat rollers, heating elements using carbon, titanium white, etc., or similar methods can be used.

In the present invention, a specific method for forming a color image from an Atagawa image is to move a hydrophilic mobile dye. For this purpose, the photosensitive material of the present invention has a photosensitive layer (1) containing at least silver halide, an organic silver salt oxidizing agent and a dye-donating substance which is also a reducing agent thereof, and a binder on a support. ) and (1) a dye immobilizer 1m (II) that can accept the hydrophilic and mobile dye formed by ffl.

The above-mentioned photosensitive layer (1) and dye fixing M (II) may be formed on the same support, or may be formed on separate supports. The dye fixing layer (■) and the photosensitive layer (2) can also be peeled off.

For example, imagewise exposure can be followed by uniform heat development, after which the dye-fixed N (n) or photosensitive layer can be peeled off. or,
When a photosensitive material in which the photosensitive layer (1) is coated on a support and a fixing material in which the fixing layer (II) is coated on the support are formed separately, the photosensitive material is imagewise exposed to uniform light. After heating,
The mobile dye can be transferred to the fixed H(If) by overlaying the fixed material.

There is also a method in which only the photosensitive material (1) is imagewise exposed, and then the dye-fixed 'FM (II) is superimposed and uniformly heated.

The dye-fixing Tm (II) can include a dye-fixing paste, such as a dye mordant. A variety of mordants can be used as the mordant, with polymeric mordants being particularly useful. In addition to mordants, j-groups, base precursors, etc.
It may also contain a hot solvent. In particular, when the photosensitive layer (1) and the dye fixing layer are formed on different supports, it is particularly useful to include a base or a base precursor in the fixation J'5 (II). .

The polymer mordants used in the present invention include polymers containing secondary and tertiary amine groups, polymers with nitrogen-containing hydrogenated ring moieties, and polymers containing these quaternary cation groups, and have a molecular weight of s, ooo to 20o, ooo, especially 10,0
00 to 30,000.

For example, US Patent 2. j Hiro, 1+≠ issue, same 2゜l/, ni≠, '1-30 issue, same 3. /Hirog, 0 Otsu/issue, same 3.7
31. Vinyl pyridine polymers and vinyl vinyl pyridine polymers disclosed in U.S. Pat. z Tsuta, Otsu 7≠ issue, same 3. g
, 3-ta, 0riwo issue, Dohiro, 1.2g.

Polymer mordant crosslinkable with gelatin, etc. disclosed in No. 33g, British Patent/Cocoa, Specification of Aj3, etc.; US Patent No. 3,7j, No. 99, Ibid. , 7! / , Zayu No. 1, same! , 79g, Otsu No. 3, Tokukai Sho J4-/15
22g No. 311--/≠jj2 No. 2, same Ta≠-/2
Otsu No. 027 Akira +1. Aqueous sol-type mordant disclosed in Book IlI et al.; US Pat. No. 3. 7g, water-insoluble mordant disclosed in Ogg specification, U.S. Patent≠, /Ogg,
Ri7 Otoyumi ('Samurai Kaisho 3-Hiroshi-/No. 37333) Ming) 11
Fortress of disclosure in Book H etc. (・Reactive mordant capable of covalent bonding with 1, U.S. Patent 3,709.Otsu 70 bow,
g1gss on 3.7th, same 3. Otohiro λ, 11-bow, 1
r-ij 3, ≠ and.

No. 706, 3, 3-57. Ott issue, 39. ! 7/
,/Gua issue, 3.27/, 111g issue, Ho 1 Kaisho 5
0-7/33-2, same ta 3-303.2g, same t,
2-15332g issue, j3-/) 3- issue, 3-3-
Mention may be made of the mordants i≦ which are disclosed in No. 10.21A.

Other US Patents 2. t73-, 3/1 issue, ]T” 1.2
The mordant described in ゜ggs/Yuotsu No. Meiho 1 Summer can also be mentioned.

Among these mordants, for example, those that crosslink with 7-trinox such as gelatin, water-soluble mordants, and aqueous sol (or latex dispersion) type mordants can be preferably used.

Particularly preferred polymer mordants are shown in F below.

(1)11. has an ammonium group and a group capable of covalently bonding with gelatin (e.g., aldehyde group, chloroalkanoyl group, chloroalkyl group, vinylsulfonyl group, pyridiniumzolopionyl group, vinylsulfonyl group, alkylsulfocchino group, etc.) Polymer, for example, C=Oc20; 1 (2) %'j of a monomer represented by the following general formula; a copolymer consisting of a repeating unit and a repeating unit of another ethylenically unsaturated monomer, and crosslinking 1'! 'i ('l'l
Reaction product with 'J

Aryl group, sweet C;t b R, 1, ~ ding (at least 5 ) Or do you have a demonstrative occupation? [I It is good to form a ring.

X: Aniso (the above alkyl group, aryl group (including substituted ones)) (3) Polymer X represented by the following general formula: about 0.25
~about j mol% y: about O to about 90 moles Head 2: about 70 to about 7 moles A: monomer having at least two ethylenically unsaturated bonds B: copolymerizable ethylenically unsaturated bond -Q: N, P b ■t1, ■(2, to I: alkyl group, cyclic hydrocarbon group,
At least two of the following compounds 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 halogen atom (alkyl group may be substituted) ) (b) Acrylic acid ester (C) Acrylic nitrile (5) Water-insoluble polymer 1 having //3 or more repeating units represented by the following general formula (bXe bb □, R2, 几,: Each represents an alkyl group, and ■(~The sum of the carbon classes of R3 is /2 or more.)
Alkyl groups may be substituted. ) X: Ceratin used in the anionic mordant layer may be any of various known ceratins. For example, lime-processed gelatin, acid-processed gelatin, seratin with different manufacturing methods, or
Seratin obtained by chemically modifying the obtained gelatin such as phthalation or sulfonylation can also be used. Further, if necessary, it can be used after being subjected to a desalination treatment.

Mixing ratio of polymer mordant and gelatin of the present invention and
The amount of J-mer mordant to be applied depends on the amount of dye to be mordant, the type and composition of the polymer mordant, and the image forming process to be used, and can be easily determined by those skilled in the art. 20/10-40/, 20(@
end pressure), mordant application interval is 0. It is suitable for use in evening f//R2.

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

The dye fixing layer (n) may have a white reflective layer. For example, a titanium dioxide layer dispersed in gelatin can be provided on a mordant layer on a transparent support. The 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 dye transfer aid can be used to transfer the dye from the photosensitive layer to the dye fixing layer. As the dye transfer aid, water or a basic aqueous solution containing caustic soda, caustic potash, or an inorganic alkali metal salt is used. Further, a low boiling point solvent such as methanol, N,N-dimethylformamide, a7tone, 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 is
The image-receiving layer may be moistened with a solvent, or crystal water or microcapsules may be incorporated into the material.

As the dye transfer aid, a hydrophilic heat solvent can also be used in addition to the above-mentioned solution system.

In the present invention, a "hydrophilic thermal solvent" is a compound that is in a solid state at product temperature but becomes a liquid state when heated,
(Inorganic/Organic) Value>1 and solubility in water at this temperature is defined as a compound of 1 or more. Here, inorganic and organic are concepts for predicting the properties of compounds, and the details can be found, for example, in the field of chemistry, Earthworks, p. 719 (
1957).

Since the hydrophilic thermal solvent has the role of assisting the movement of the hydrophilic dye, it is considered that it is preferably a compound that can act as a solvent for the hydrophilic dye.

In general, preferred solvents for dissolving organic compounds are those whose (inorganic/organic) value is
It is known empirically that the value is close to the inorganic/organic) value. On the other hand, the (inorganic/organic) value of the dye-donating substances used in the present invention is around 1, and the (inorganic/organic) value of the hydrophilic dyes released from these dye-donating substances is approximately 1.
The value is larger than the (inorganic/organic) value of the dye-donating substance, preferably 1.5 or more, particularly preferably 2 or more. The hydrophilic thermal solvent used in the present invention is preferably one that moves only the hydrophilic dye and does not move the dye-providing substance, so its (inorganic/organic) value is (natural/organic)
Must be greater than the value. That is, as a hydrophilic thermal solvent, it is an essential condition that the (inorganic/organic) value is 1 or more, preferably 2 or more.

On the other hand, from the viewpoint of molecular size, it is considered preferable that molecules that can move by themselves without inhibiting the movement exist around the moving dye. Therefore, the molecular weight of the hydrophilic heat solvent is preferably small, about 200 or less, and more preferably about 100 or less.

Heating for dye transfer is from 60°C to 250°C from the viewpoint of storage stability and workability of the photosensitive material, so in the present invention, it functions as a hydrophilic thermal solvent within this temperature range. I can choose things appropriately. It goes without saying that hydrophilic thermal solvents must be able to quickly aid the movement of dyes when heated, but if we also consider the heat resistance of photosensitive materials, we need to consider the melting point required for hydrophilic thermal solvents. is 40°C to 250°C, preferably 40°C to 200°C, more preferably 40°C to 150°C.

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

The hydrophilic thermal solvent used in the present invention only needs to be able to substantially assist the movement of the hydrophilic dye generated by heat development to the dye fixing layer. First, it can be contained in a photosensitive material such as a photosensitive layer, it can be contained in both a dye fixing layer and a photosensitive layer, or it can be included in a photosensitive material or in an independent dye fixing material having a dye fixing layer. It is also possible to provide a separate stone containing a hot solvent. From the viewpoint of increasing the transfer efficiency of the dye to the dye fixing layer, it is preferable that the hydrophilic thermal solvent is contained in the dye fixing layer and/or the layer adjacent thereto.

The hydrophilic thermal solvent is dissolved in water and dispersed in the binder, but it can also be used by dissolving it in alcohols such as methanol, ethanol, etc.

The hydrophilic thermal solvent used in the present invention has a coating amount of 5 to 500% by weight, preferably 20 to 200% by weight, particularly preferably 30 to 150% by weight of the total coating amount of the photosensitive material and/or dye fixing material. It can be used.

When the dye fixing layer is located on the surface, a protective layer can be further provided if necessary. As such a protective layer, one generally used as a protective layer for photosensitive materials can be used as is, but if the dye fixing layer is provided on the dye fixing material separately from the photosensitive material, In order not to inhibit the movement of the hydrophilic dye, it is preferable to impart hydrophilicity to the protective layer as well.

The photographic light-sensitive material and dye fixing material of the present invention may contain an inorganic or organic hardener in the binder layer of the photographic emulsion 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.) , active vinyl compound (1,3,5-triacryloyl-hexahydro-5-)riazine, 1.3
-vinylsulfonyl-2-propatol, etc.), active halogen compounds (2,4-dichloro-6-hydroxy-5-
) riazine, etc.), mucohalogen acids (mucochloric acid, mucophenoxychloroic acid, etc.), etc. can be used alone or in combination.

Further, as the heating means for moving the dye, various means similar to the heating means used in heat development as described above can be employed.

In the present invention, various exposure means can be used. The latent image is obtained by imagewise exposure to radiation, including visible light. Generally, light sources used for A-color printing include tungsten lamps, mercury lamps, halogen lamps such as iodine lamps, xenon lamps, laser light sources,
Also, a CRT light source, a fluorescent tube, a light emitting diode, etc. can be used as a light source.

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, by reflection printing, or by enlarging printing.

In addition, images taken with a video camera, etc., and image information sent from a television station are sent directly to a CRT or FOT,
It is also possible to form this image on a heat-developable photosensitive material either in close contact with it or through a lens, and then print it.

Furthermore, LEDs (light emitting diodes), which have recently seen significant progress, are being used as exposure means or display means in various devices. It is difficult to make an LED that effectively emits blue light, so in order to reproduce color images using LEDs, three types of LEDs that emit green, red, and infrared light are used. The portions of the photosensitive material that are sensitive to these lights may be designed to emit yellow, magenta, and cyan dyes, respectively.

That is, the green-sensitive part (Ff) contains a yellow dye-donating substance, the red-sensitive part (layer) contains a magenta 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, it is also possible to read the original image illuminated by a light source with a light receiving element such as a phototube or CCD, and store this information in the memory of a computer etc. as necessary. After performing so-called image processing, this image information is reproduced on a CRT and used as an image-like light source, or there is a method of directly causing three types of LEDs to emit light based on the processed information. be.

When the heat-developable photosensitive material of the present invention is used, the developing time can be shortened, and the density of the dye image is high and there is no fog. Since the photosensitive material of the present invention has extremely improved storage stability before thermal development, it is possible to eliminate variations in image reproducibility, making it an extremely easy-to-use photosensitive material.

The image forming method using the photosensitive material of the present invention having such characteristics can meet not only the field of photography but also the recent demand for converting so-called soft images to hard images. Since the formed dye image is fixed on the dye fixing layer, the color reproducibility is good (and the image has good storage stability, so it can be easily used even when long-term storage is required. In this respect, the present invention surpasses conventional photographic technology, and the present invention has great significance.

The present invention will be explained in more detail below with reference to Examples, but the present invention is not limited thereto.

Example 1: 40 g of gelatin and 26 g of KBr were dissolved in 3000 ml of water. This solution was kept at 50°C and stirred.

Next, add 34g of silver nitrate to 200mj of water! 10% of the liquid dissolved in
It was added to the above solution in between. Then potassium iodide 3
．． A solution of 3 g dissolved in 100 m6 of water was added over 2 minutes.

The pH of the silver iodobromide emulsion thus prepared was adjusted, the emulsion was precipitated, and after removing excess salt, pf-1 was adjusted to 6.0 to obtain a silver iodobromide emulsion with a yield of 400 g.

Next, how to make a U-latin dispersion of a dye-donating substance will be described.

Dispersion containing the auxiliary developer precursor of the present invention (A) 5 g of magenta dye-donating substance (10), 0.02 g of the auxiliary developer precursor (1) of the present invention, 2-ethyl-1 succinate・Weighed 0.5 g of sodium xyl ester sulfonate, 15 g of leak resyl fumesoate (TCP), and added ethyl acetate 3 Q m I! was added and melted by heating to about 60°C to form a uniform /8/&. After stirring and mixing this solution and 100 g of a 10% solution of lime-treated gelatin, the mixture was mixed with a homogenizer for 10 minutes. Dispersed using OOORPM. This dispersion liquid is called a dispersion (A) of a dye-providing substance (1o).

Dispersion containing no auxiliary developer precursor (B) In the preparation of the dispersion of (A), the auxiliary developer precursor (1) of the present invention
A dispersion (B) was prepared in exactly the same manner except for the following.

Next, how to make photosensitive coatings A* and B* will be described.

Photosensitive coating A* (a) 25 g of the above silver iodobromide emulsion (b)
? i! i Dye-donating substance containing co-developer precursor (1) (
10) Dispersion (A) 33 g (C) 5% aqueous solution of a compound with the following structure 5 mAl1 \
/0(d) 10% ethanol solution of guanidine trichloroacetic acid
12ml.

<e> 10% aqueous solution of dimethylsulfamide
4m7! <r>Water
After mixing and melting (Cr) to (S) with a value of 8 mβ or more, it was coated on polyethylene terephthalate film-F to a wet film thickness of 30 μm and dried. Furthermore, the following composition was applied to this L as a protective layer.

(a) Gelatin 10% water 1 volume overnight 35g (
b) 10% ethanol solution of 11 guanidine acetic acid 5 mβ(c)coba')Ua-1
-, :- 1% aqueous solution of nityl-hexole ester nulphonic acid sorta 4mβ (go-) Fu',',,

5 6 m E was mixed, the solution was applied to a wet film thickness of 25 pm, and then dried to give a photosensitive/! Fabric A* was produced.

In the method of preparing photosensitive coating material A*, a dye-providing substance (10) containing no auxiliary developer precursor is used instead of the dispersion (A) of a dye-providing substance (10) containing an auxiliary developer precursor.
A photosensitive coating B* was prepared in exactly the same manner except that the dispersion (B) was used.

Next, this coated sample was heated to 2000 using a tungsten light bulb.
Imagewise exposure was made for 10 seconds at lux. Thereafter, it was heated uniformly for 15 seconds on a heat block heated to 130°C.

Next, a method for forming a dye fixing material containing a dye fixing agent will be described.

Poly(methyl acrylate-N,N,N-)trimethyl-
N-vinylbenzylammonium chloride) (ratio of methyl acrylate and vinylbenzylammonium chloride is 1:1) 10g to 200mj! dissolved in water, 1
It was uniformly mixed with 100 g of 0% lime-treated gelatin. This mixed solution was uniformly applied to a wet film thickness of 90 μm on a paper support laminated with polyethylene in which titanium dioxide was dispersed.

After soaking this dye-fixing material in water, heat each of the above-mentioned heated photosensitive materials A* and B* on the film surface for 6 seconds, then peel off each photosensitive material and place magenta on the dye-fixing material. A color image was obtained. The reflection density of this negative image was measured using a Macbeth densitometer (RD-519) and the following results were obtained.

Sample size Maximum concentration Minimum concentration A* (invention) 2.07 0.17B* (comparison) 1.300
．． From the results in 1., it was demonstrated that the photosensitive material of the present invention using an auxiliary developer precursor can obtain high image density in a short thermal development time.

Example 2゜Dispersion of the dye-providing substance (10) was carried out in exactly the same manner as in Example 1, except that the following compound was used instead of the auxiliary developer precursor (8) used in Example 1. Things (C), (
D), (E), (F), and (G) were prepared. Next, (C
) to (G) in Example 1. Photosensitive coatings (C*, D*, E*, F*, G*) were prepared in the same manner as above.

The same treatment as in Example 1 was carried out using these photosensitive coatings. The results obtained are shown below.

Dye-donating substance Auxiliary development Maximum concentration Minimum concentration dispersion Drug precursor dispersion (B) None 1.300.16 (comparison) Dispersion (C) (5) 2.05 0.1?
(Present invention) Dispersion (D) (6) 2.00 0.16
(This invention) Dispersion (E) (8) 2.03 0.16
(This invention) Dispersion (F) (10) 1.95 0.1
5 (present invention) Dispersion (G) (12) 1.80 0.1
5 (Invention) The above results demonstrate that high image density can be achieved in a short heating time when the photothermographic material of the invention containing an auxiliary developer precursor is used. .

Example 3 The following dye-donating substances were used in place of the dye-donating substance (10) used in Example 1, and the same procedures as in Example 1 were carried out to produce ? A dispersion of a dye-providing substance containing the di co-developing agent precursor (1) and a dispersion of a dye-providing substance not containing the co-developing agent II1 precursor were prepared.

Dye-donating substance (4,2) 5 g Dispersion (1
() Dye-donating substance (68) 7.5g Dispersion (1)
Dye-donating substance (21) 5g Dispersion (J) Example 1. A sample was prepared in exactly the same manner as in Example 1, and the results were shown below.

Margin dye-providing substance Auxiliary developer Maximum Minimum dispersion Precursor (1) Concentration Concentration dispersion (I])
Yes (invention) 2.11 0.16 Magenta (comparison without) 1.33 0.12 Dispersion (1) Yes (invention > 2.05 0.
15 yellow (compared without) 1.28
0.11 Dispersion (J) Yes (invention) 2.10
0.16 cyan (compared without) 1.4
0 0.13 These results demonstrate that the photothermographic material of the present invention provides high density in a short heating time.

Example 4゜ Next, an example using an organic silver salt oxidizing agent will be shown.

Preparation of hensitriazole silver emulsion: 28 g of gelatin and 13.2 g of hensitriazole are mixed with 3 parts of water.
000 mj2, and this solution was kept at 40°C and stirred. A solution prepared by dissolving 17 g of silver nitrate in 100 mβ of water was added to this solution over 2 minutes.

The pH of this benzotriazole silver emulsion was adjusted, and after sedimentation and removal of excess salt, p] was adjusted to 6.0 to obtain a hensitriazole silver emulsion with a yield of 400 g.

The following photosensitive coatings were prepared using this hensitriazole silver emulsion.

(a) Silver benzotriazole emulsion 10 g (b) Silver iodobromide emulsion 20 g (C) Dispersion of dye-donating substance (10) containing auxiliary developer precursor (1) (
A) 33g (d) 5% aqueous solution of a compound with the following structure 5ml 1 (e) 10% ethanolic solution of guanidine trichloroacetic acid 12.5mff (f) 10% aqueous solution of dimethylsulfamide 4ml (g) Water 7. After mixing and melting 5m#, 30μm on polyethylene terephthalate film.
It was applied to a wet film thickness of , and then dried.

The protective layer was applied in the same manner as in Coating A*. This is referred to as photosensitive coating A**.

In the method of preparing a photosensitive coating A**, a dispersion (A) of a dye-donating substance (1o) containing an auxiliary developer precursor (1)
A photosensitive coating material B** was prepared in exactly the same manner except that a dispersion (B) of a dye-providing substance (1o) containing no auxiliary developer precursor was used instead.

Using this photosensitive coating, the same treatment as in Example 1 was carried out, and the results obtained are shown below.

Below are the margin sample numbers, maximum density, minimum density A**
2.08 0.19 (invention) Blk 1.32 0.17 (comparison) These results demonstrate that the photothermographic material of the invention is effective in producing a high maximum density in a short processing time. Ta.

Example 5 Immediately after coating, the photosensitive materials A*, B* of Example 1 and the photosensitive materials C*, D*, E, F*, G* of Example 2 were placed in a constant temperature container at 50°C. After storage for 2 days, n
Light, heating, and transfer were performed, and the reflection density against green light was measured.

The results obtained are shown below.

It has been demonstrated that the heat-developable photosensitive material contained in the photothermographic material suppresses the increase in minimum density during storage and improves stability over time.

Example 6 In the production of photosensitive coatings*, instead of the dispersion of the dye-providing substance (10) containing the auxiliary developer precursor (1), a dye containing 1 g of the following auxiliary developer 1) O,O was used. A photosensitive coating H* was prepared in exactly the same manner except that dispersion 1) of donor substance (10) was used. Photosensitive timber of Example 1-I
A*, B* and above 1 (* after coating i and fj at 50℃
After storage for 2 days in a thermostatic container, exposure, heating, and transfer were carried out in the same manner as in Example 1, and the fouling density against green light was measured. The results obtained are shown below.

Auxiliary developer (h) 113 to CH3 From the above results, in the sample containing the developing agent precursor according to the present invention, the sensitivity increases immediately after application, and even after the photosensitive material is aged, there is no increase in Dmin. In fact, it has been shown that the sensitivity increases.

Example 7 This example is a case in which a dye fixing material suitable for completely dry image formation is used.

As photosensitive materials, photosensitive coatings A* and B* of Example 1 were used. Next, a method for forming a dye fixing material containing a dye fixing agent will be described.

Poly(methyl acrylate-N,N,N-trimethyl-
N-vinylhensylammonium chloride) (The ratio of methyl acrylate and vinylhensylammonium chloride is 1:1) Dissolve 10g in 200mg of water,
It was uniformly mixed with 100 g of 0% lime-treated gelatin. This mixed solution was uniformly applied onto a polyethylene terephthalate film having a thickness of 120 μm in which titanium dioxide was dispersed so as to have a wet IQ thickness of 90 g.

The following (a) to (f) were mixed on the surface of the dye fixing agent, and a dissolving solution (referred to as A/&) was uniformly applied to a wet film thickness of 60 μm.

(a) Urea 2g (b) N-
--Methylurea 2゜(C) Water
10m1 (d) 1 of polyvinyl alcohol (degree of porosity 98%)
0 weight ice water 8 liquids 12 g (e) Compound with the following structure], OOmgHO (f) 5% aqueous solution of sodium dodecylhenzenesulfonate 0.5 me After drying, this coated sample was used as a dye fixing material.

The above photosensitive material was imagewise exposed for 10 seconds at 2000 lux using a tungsten bulb. Thereafter, it was heated for 15 seconds on a heat block heated to 130°C. This heated photosensitive material and the above-mentioned dye-fixing material were placed one on top of the other so that the film surfaces were in close contact with each other, and placed on a heat block at 140°C for 2 hours.
After heating for 0 seconds, the dye-fixing material was peeled off from the light-sensitive material, and a negative magenta color image was obtained on the dye-fixing material.

The reflection density of this negative image was measured using a Maches densitometer (RD-519).
) and obtained the following results.

Photosensitive material Maximum density Minimum density A* (invention) 2.0B 0.20B* (comparison)
1.25 0.18 These results demonstrate that the heat-developable photosensitive material of the present invention can provide good results as in Example 1 even in the completely dry image forming process.

Claims (1)

[Scope of Claims] On the support, at least (1) a photosensitive silver halide, (2) a binder, and (1) a photosensitive silver halide which is butyric to the photosensitive silver halide and which is photosensitive to the photosensitive silver halide and which is then heated, is added. A dye-donating substance that releases a hydrophilic dye by reacting with silver;
A photothermographic material characterized by having an auxiliary developer precursor represented by the following general formula. In the formula, heji [represents a group that can be cleaved by alkaline hydrolysis, R4; j does not represent an aryl group. R1, R2, R3 and R
4 represents a hydrogen atom, an alkyl group, or an aryl group, and each may be the same or different.