JPS61193143A - Heat developing photosensitive material - Google Patents

Abstract

PURPOSE:To obtain the titled material having a high sensitivity and a rapid developing rate and a raised max. concn. of an image, and an improved storage property by incorporating to the titled material, a sensitive silver halide emulsion prepared in the presence of a sensitizing coloring matter from the silver halide contg. 60-100mol% silver bromide and either <=6mol% silver iodide or not contg. silver iodide and also contg. a residual amount of silver chloride, when the residual amount of the silver halide component presents. CONSTITUTION:The titled material is selected from the groups comprising silver bromide,silver iodide bromide, silver chloride iodide bromide and silver chloride bromide, and comprises 60-100mol%, preferably 70-100mol% silver bromide, 0-6mol%, preferably 0-4mol% silver iodide and 0-30mol% silver chloride. The titled material comprises the sensitive silver halide emulsion formed from said silver halide particles in the presence of the sensitizing coloring matter. As the result that the silver halide particles are formed in the presence of the sensitizing coloring matter, the sensitizing coloring matter is adsorbed to the silver halide particles in a stable state, and may enable to change the sensitivity in an inherent sensitive range of the silver halide and to maintain the sensitivity in a range outside of said inherent sensitive range.

Description

Detailed Description of the Invention (1) Background of the Invention Technical Field The present invention relates to a heat-developable photosensitive material. For more details,
The present invention relates to a heat-developable photosensitive material using silver halide.

Prior art and its problems Photography using silver halide has been traditionally used because it has superior photographic properties such as sensitivity and gradation control compared to other photographic methods, such as electrophotography and diazo photography. It has been the most widely used.

In recent years, a technology has been developed that allows images to be easily and quickly obtained by changing the image forming method for photosensitive materials using silver halide from the conventional wet processing using a developing solution to a dry processing using heating, etc. has been developed.

Heat-developable photosensitive materials are well known in this technical field, and the heat-developable photosensitive materials and their processes are described in 1, for example, "Photographic T.
Fundamentals of Science J (Published by Corona Publishing, 1979), 553~
p. 555, p. 40 of Eizo Information J (published in April 1978), Nebletts Handbook of Photography and Reprogramming 74 (NeblettsHa
nd-book of Photography
and Reprography) Part 7
Volume 77 Nostrand Reinhold Company (Van No5trand Re1nhold C
US Pat. No. 3,152.904, US Pat. No. 3,301°678, US Pat.
,075, British Patent No. 1,131.108, British Patent No. 1
, No. 167.777, and Research Disclosure magazine, June 1978 issue, pp. 9-15 (RD-1702
9).

Many methods have already been proposed for obtaining color images. For a method of forming a color image by the combination of an oxidized developer and a coupler, U.S. Pat. U.S. Pat. No. 3,761,270 describes p-7 minofenol reducing agent 1j<, Hergie Patent No. 80
No. 2,519 and Research Disclosure Magazine 1
September 975, pp. 31-32, sulfonamidophenol reducing agents are also described in U.S. Patent No. 4,021,2.
No. 40 proposes a combination of a sulfonamidophenol reducing agent and a 4-equivalent coupler.

Further, regarding the method of forming a positive color image by photosensitive silver dye bleaching method, for example, Research Disk Jar Magazine, April 1976 issue, pages 30 to 32 (RD-14433
), December 1976 issue of the same magazine, pages 14-15 (RD-1
5227) and U.S. Pat. No. 4,235,957, useful dyes and bleaching methods are described.

Furthermore, an image forming method based on thermal development using a compound that has a dye moiety in advance and can release a mobile dye in response to or inversely to the reduction reaction of silver halide to silver at high temperatures has been developed in Europe. Patent publication number 76.492, same number 79.0
No. 56, JP-A-58-28928, JP-A No. 58-260
It is disclosed in No. 08.

These image forming methods have the advantage that images can be obtained more easily and quickly than conventional wet processing methods. However, in order to obtain sharper images more quickly, it is necessary to accelerate the thermal development process and improve the maximum density.

Further, as a light source for recording an image on a heat-developable photosensitive material, various light sources can be used as described below. However, in recent years, high-speed recording methods using high-intensity light sources such as laser light sources, CRT light sources, and light-emitting diodes have been developed (for example, Japanese Patent Application Laid-Open No. 57-151733 filed by the present applicant, or Japanese Patent Application No. 57-226555). (described in issue).

Therefore, when using the L recording method, it is necessary for the photothermographic material to have high sensitivity and rapid heat developability under high illuminance and short exposure. As an emulsion, the present applicant previously used 70 to 10
If the emulsion contains 0 mol% silver bromide and 4 mol% or less silver iodide, or no silver iodide, and the remaining content is present, an emulsion of silver halide grains containing silver chloride is proposed. (Recorded in Japanese Patent Application No. 59-253745)
.

However, when a light-sensitive material containing the above-mentioned emulsion is sensitized with a sensitizing dye, it has poor storage stability and a particularly significant decrease in sensitivity. This is especially true when an organic silver salt is present or when a dye-donating substance containing a dye is present in the molecule, and improvements in this respect are desired.

II. OBJECTS OF THE INVENTION An object of the present invention is to provide a fully developed photosensitive material that has high sensitivity and rapid development under high-intensity short-time exposure, has a high maximum image density, and has excellent storage stability. It is in.

■Disclosure of invention Such objects are achieved by the invention described below.

That is, 1 the present invention contains 60 to 100 mol% silver bromide and 6 mol% or less of silver iodide, or does not contain this, and if the remaining content is present, further silver chloride. This is a heat-developable photosensitive material characterized by having a photosensitive silver halide emulsion in which silver halide grains containing the following are formed in the presence of a sensitizing dye.

■Specific structure of the invention Hereinafter, a specific configuration of the present invention will be explained in detail.

The heat-developable photosensitive material of the present invention contains 60 to 100 mol% (preferably 70 to 100 mol%) of silver bromide, 0 to 6 mol% (
silver iodide (preferably 0 to 4 mol%), and silver bromide, silver iodobromide, containing 0 to 30 mol% silver chloride as a component thereof;
It has a photosensitive silver halide emulsion containing silver chloroiodobromide and silver chlorobromide, and these silver halide grains are formed in the presence of a sensitizing dye.

As a result of forming silver halide grains in the presence of a sensitizing dye as described above, the sensitizing dye is adsorbed to the silver halide grains in a stable state, changing the sensitivity in the inherent sensitivity range of silver halide, This can be done by providing sensitivity outside the natural sensitivity range.

The reason why the composition of the silver halide grains is set as above is that if the silver bromide content is less than 60 mol%, the high-light sensitivity decreases, and even if the silver iodide content exceeds 6 mol%, the chloride 3 silver
This is because even if it exceeds 0 mol %, the high-light sensitivity decreases.

Methine dyes are usually used as sensitizing dyes, and these include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes, and hemioxonol dyes. A particularly useful dye is cyanine dye.

It is a pigment belonging to merocyanine pigments and complex merocyanine pigments. Any of the nuclei commonly used for cyanine dyes can be applied to these dyes as basic heterocyclic nuclei. Namely, pyrroline nucleus, oxazoline nucleus, thiazoline nucleus, pyrrole nucleus, oxazole nucleus, thiazole nucleus, selenazole nucleus, imidazole nucleus, tetrazole nucleus, pyridine nucleus, etc.; nuclei in which an alicyclic hydrocarbon ring is fused to these nuclei: and these A nucleus in which an aromatic hydrocarbon ring is fused to the nucleus, sokuchi, indolenine nucleus, benzindolenine nucleus.

Indole nucleus, benzoxadol nucleus, naphthoxazole nucleus, benzothiazole nucleus, naphthothiazole nucleus, benzoselenazole nucleus, benzimidazole nucleus, quinoline nucleus, etc. are applicable. These nuclei may be substituted on carbon atoms.

Merocyanine dyes or composite merocyanine dyes include a pyrazolin-5-one nucleus and a thiohydantoin nucleus as a nucleus having a ketomethylene structure.

5- to 6-membered heterocyclic nuclei such as 2-thioxazolidine-2,4-dione nucleus, thiazolidine-2,4-dione nucleus, rhodanine nucleus, and thiobarbic acid nucleus can be applied.

Specific examples of sensitizing dyes useful in the present invention include the following general formulas (A) to (H), (J) to (U), (W), and (Y).
Examples include pigments represented by

General formula (A) In the formula, z and z2 are heterocyclic nuclei commonly used in cyanine dyes, particularly thiazole nucleus, thiazoline nucleus, benzothiazole nucleus, naphthothiazole nucleus, oxazole nucleus, oxazoline nucleus, benzoxazole nucleus, and naphthoxazole nucleus. , tetrazole nucleus, pyridine nucleus, quinoline nucleus, imidazoline nucleus imidazole nucleus, benzimidazole nucleus, naphthoimidazole nucleus, selenazoline U selenazole nucleus, benzoselenazole nucleus.

These nuclei represent the atomic groups necessary to complete the naphthoselenazole nucleus or indolenine nucleus, etc. These nuclei include lower alkyl groups such as methyl groups, halogen atoms, phenyl groups,
Hydroxyl group, C1-C4 flukoxy group, carboxyl group, alkoxylcarbonyl group, alkylsulfamoyl group, alkylcarbamoyl group, acetyl group, ace) + cy group, cyano group, trichloromethyl group, trifluoromethyl group, It may be substituted with a nitro group or the like.

Ll or L2 represents a methine group, a substituted methine group,
The substituted methine group is a methyl group.

Examples include ethyl, a lower argyl group of [F, a phenyl group, a substituted phenyl group, a methoxy group, a methine group substituted with ethoxy &''4.

R1 and R2 are an alkyl group having 1 to 5 carbon atoms; a substituted alkyl group having a carboxyl group; γ-sulfopropyl group, δ
-Sulfobutyl group, 2-(3-sulfopropoxy)ethyl group, 2-(2-(3-sulfopropoxy)ethoxy)
A substituted alkyl group having a sulfo group such as an ethyl group or a 2-hydroxy sulfopropyl group; e mi represents an allyl group or other substituted alkyl group commonly used as the N-substituent of cyanine dyes. 1.2 or 3.

xl- represents an acid anion group usually used in cyanine dyes such as iodide ion, bromide ion, p-)luenesulfonate ion, perchlorate ion, etc. n represents 1 or 2, and when a betaine structure is adopted, n is l.

In the formula, Z3 is the general formula usually used for cyanine dyes (
Represents a heterocyclic nucleus as shown in A). Z4 represents an atomic group necessary to form a ketoheteronucleus usually used in merocyanine dyes. For example, rhodanine,
These are the cores of thiohydantoin, oxindole, 2-thioxazolinedione, 1,3-indanedione, and the like. L3 and L4 have the same meaning as L1 and L2, and R3 has the same meaning as R1 or R2.

m2 represents 1, 2.3 or 4.

- In the formula, Z5 is a 4-quinoline nucleus, a 2-quinoline nucleus, a benzthiazole nucleus, a benzoxazole nucleus, a naphthothiazole nucleus, a naphthoselenazole nucleus, a naphthoxazole nucleus,
Represents the atomic group necessary to complete the benzoselenazole nucleus and indolenium nucleus. pt represents 0 or 1.

R4 represents the same meaning as R1 or R2, L5 and L6 represent the same meaning as L3 or L4, R3 represents 0 or 2, L7 and L3 represent the same meaning as Ll or L2,
and ), at least one of which is a =N-R5 group.

Wl represents 1 or 2.

General formula (D) P2 W2 formula, Z7
is Z5, Za is Za, R6 is R1 or R2 and p
2 represents the same meaning as pl, Y3 and Y4 are Yl and Y2
w2 has the same meaning as Wl.

In the formula, R7 and R8 are R1, Z9 and Zll) are Z5,
P3. P4 is PI, L9~L131, Ll, and X
2 represents xl and R2 represents nl and assimilation &. Y
5 and Y6 have the same meaning as Yl. p5, R
4 represents 0 or 1.

W3 has the same meaning as Wl.

General formula (F) In the formula, Z II and 212 are unsubstituted, or in particular, a lower alkyl group such as a butyl group, a halogen atom-phenyl group,
Hydroxyl group, aflecoxy group having 1 to 4 carbon atoms, carboxylluponyl group, alkylsulfamoyl group, alkylcarbamoyl group, acetyl group, cyano J. (.

Trichloromethyl group, trifluoromethyl group.

Represents an atomic group necessary to complete a benzene ring converted by a nido CI group, etc., or an atomic group safe to form a naphthalene ring. R9 and RIn have the same meaning as R1, Y7 and Y8 are oxygen atoms, sulfur atoms, selenium atoms, RI+ = C (Ro and R+2 are methyl or ethyl groups), =N-R
I3(l(+3 is an alkyl group 1, usually cyanine-colored N-
Substituted alkyl group or allyl (al
lyl) group) or -CH=CH-,
Y9 represents an atomic group necessary to form a 5- or 6-membered heterocycle.

・General formula (G) (X3-) 213, z141tZn, RI4, R+s
ltR+, Y+o, and Y+1 have the same meaning as Y7. Y 17 represents an atomic group necessary to form a 5- or 6-membered carbon ring. x3 represents the same meaning as xl, and R3 represents the same meaning as nl.

-・General formula (H) General formula (J) A+ (-LAG = Ll?U-Lte = A2X
4. R4 represents the same meaning as Xl, nl.

P6 is 0 or 1. m5, m6 is 1 or 2°L1
4-L IR represents the same meaning as Ll, 215 represents the same meaning as Zl, Pl5 has the same meaning as Pl in general formula (C).

Here, as A1.

N(J2 Also, as A2.

0' can be mentioned as preferred.

RlG and R18 represent a hydrogen atom, an alkyl group, a substituted alkyl group, or an aryl group; R17 represents a halogen atom, a nitro group, a lower alkyl group, an alkoxy group, an alkoxycarbonyl group, an alkylsulfonyl group, or an arylsulfonyl group.

RlG, R20, R2'l are hydrogen atoms, halogen atoms,
Represents an alkyl group, cycloalkyl group, aryl group, pyridine group, carboxy group, alkoxycarbonyl group,
Q is rhodanine, 2-thioxazolidinedione, 2
-Represents the atomic group necessary to complete a 5- to 6-membered heterocyclic nucleus such as thiohydantoin and barbituric acid.

General formula (K) R22 is R1, Z IG is 2. and Lt9. L20 represents the same meaning as beam, R7 is O or l, R8
represents 1.2 or 3.

G, , G2 may be the same or different, have the same meaning as R1, and jointly represent a cyclic secondary amine (eg, pyrrolidone, 3-pyrroline, piverizinene, piperazine, morpoline, 1.2, 3. 4-tetrahydroquinoline, decahydroquinoline, 3-7zabicyclo (3,2.

2] Representing the necessary atomic group to form nonane, indoline, azetine, and hexahydroazepine), x5
represents the same meaning as xl, and R5 represents the same meaning as 1%.

General formula (L) zI7 is Z4, t2. , L22. t23 is Lt 1!
:.

G3. G4 has the same meaning as G1, R9 is 0.1
．． Represents 2 or 3.

Particularly useful dyes for imparting infrared sensitivity are dyes represented by the following general formulas (M) to (U), (W), and (Y).

General formula (M) , propyl group, butyl group, pentyl group (heptyl group, etc.), substituted alkyl group (substituents such as carboxy group, sulfo group, cyano group, halogen atom (e.g. fluorine atom, chlorine atom, bromine atom, etc.), hydroxy group , alkoxycarbonyl group (having 8 or less carbon atoms, e.g. carbonyl group, ethoxycarbonyl group, 7yloxycarbonyl group, etc.), alkoxy group (having 7 or less carbon atoms, e.g. methoxy group, ethoxy group, propoxy group) , butoxy group, .＼acyloxy group, etc.), aryloxy group (e.g. phenoxy group, P-1yloxy group, etc.)
Acyloxy groups (3 or less carbon atoms, e.g., acetyloxy, propionyloxy, etc.), acyl groups (8 or less carbon atoms, e.g., acetyl, (, propionyl, benzoyl, mesyl, etc.), cal/hemoyl groups ( (e.g., carbamoyl group, N,N-dimethylcarbamoyl group, morpholinocarbamoyl group, piperidinocarbamoyl group, etc.), sulfamoyl group (e.g., sulfamoyl group, N,N-dimethylsulfamoyl group, morpholinosulfonyl group, etc.), aryl group (e.g. phenyl group,
p-hydroxyphenyl group, p-carboxyphenyl group.

P-sulfophenyl group, α-naphthyl group, etc.) or the like) (having a carbon atom number of 6 or less. However, two or more of these substituents may be substituted with an alkyl group in combination.

).

In general formula (M), Y and Y are # elementary atoms,
Sulfur atom, selenium atom, /R = C (R and R are methyl or ethyl groups), =
N-R (R is a substituted or substituted alkyl group having 5 or less carbon atoms (substituents include hydroxyl group, halogen atom, carpoxyl group, sulfo group, alkoxy group, etc.) or allyl group] or 10H= CH=
represents.

In the general formula (M), Z and Z represent an atomic group necessary to form a benzene ring or a naphthyl boron substituted or substituted; substituents include lower alkyl groups such as methyl groups, halogen atoms, phenyl groups, hydroxyl group.

Examples include alkoxy groups having 1 to 4 carbon atoms, carboxyl groups, alkoxycarbonyl groups, alkylsulfamoyl groups, alkylcarbamoyl groups, acyl groups, cyano groups, trifluoromethyl groups, and nitro groups.

Desire and Z containing Ylol, or ring containing Y and 2
Examples of nitrogen-containing heterocycles made with 102 include thiazole nuclear systems [e.g., benzothiazole, 4-chlorobenzothiazole, 5-chlorobenzothiazole, 6-chlorobenzothiazole, 7-chlorobenzothiazole, 4-methylbenzothiazole, 5 -methylbenzothiazole,
6-methylbenzothiazole, 5-bromobenzothiazole, 6-bromobenzothiazole, 5-iodobenzothiazole, 5-7enylbenzothiazole, 5-methoxybenzothiazole, 6-methoxybenzothiazole, 5-ethoxybenzothiazole, 5 -Carboxybenzothiazole, 5-ethoxycarbonylbenzothiazole, 5-2-benzothiazole, 5-fluorobenzothiazole, 5-trifluoromethylbenzothiazole, 5,6-dimethylbenzothiazole, 5-methyl- 6-methoxybenzothiazole, 5-hydroxy-
6-methylbenzothiazole, tetrahydrobenzothiazole, 4-2-phenylbenzothiazole, naphtho(2,
1-d) Thiazole, naph)(1,2-d) Thiazole, natu[2°3-d]thiazole, 5-methoxynaphtho[1,2-d)thiazole, 7-medoxynaf)(2
,1-d)thiazole,8-methoxynaphtho(2,1-
d) Thiazole, 5-methoxynat(2,3-d)thiazole, etc.], selenazole grafting [e.g., benzoselenazole, 5-chlorobenzoselenazole core, 5-methoxyhenzoselenazole, 5-methylbenzoselenazole, 5-Hydroxybenzoselenazole.

(2,1-d) selenazole, naphtho (1,2
-d) selenazole, etc.], oxazole nuclear systems [e.g. benzoxazole, 5-chlorobenzoxazole,
5-methylbenzoxazole, 5-bromobenzoxazole, 5-fluorobenzoxazole, 5-phenylbenzoxazole, 5-methoxybenzoxazole, 5-trifluoromethylbenzoxazole, 5
-Hydroxybenzoxazole, 5-carboxybenzoxazole, 6-methylbenzoxazole, 6-
Chlorbenzoxazole, 6-methoxybenzoxazole, 6-hydroxybenzoxazole, 5.6-
Dimethylbenzoxazole.

4.6-dimethylbenzoxazole, 5-ethoxybenzoxazole, naph)(2,1-d]oxazole, naphtho(1,2-d)oxazole, naph)(2,3
-d) oxazole etc.], quinoline nucleus [e.g. 2-quinoline.

3-Methyl-2-quinoline, 5-ethyl-2-quinoline, 6-methyl-2-quinoline, 8-fluoro-2-quinoline, 6-medoxy-2-quinoline, 6-hydroxy-
2-quinoline, 8-chloro-2-quinoline, 8-fluoro-4-quinoline, etc.), 3.3-dialkylindolenine core (for example, 3.3-dimethylindolenine, 3.
3-';'Ethylindolenine, 3,3-dimethyl-5
-cyanoindolenine, 3.3-dimethyl-5-methoxyindolenine, 3.3-dimethyl-5-methylindolenine, 3.3-dimethyl-5-chlorindolenine, etc.), imidazole nuclei (e.g. 1- Methylbenzimidazole, 1-ethylbenzimidazole, l-methyl-5-chlorobenzimidazole.

1-Ethyl-5-chlorobenzimidazole.

l-Methyl-5,6-dichlorobenzimidazole, 1
-ethyl-5,6-dichlorobenzimidazole, l-
Ethyl-5-methoxybenzimidazole, l-methyl-5-cyanobenzimidazole, l-ethyl-5-cyanobenzimidazole, l-methyl-5-fluorobenzimidazole, l-ethyl-5-fluorobenzimidazole, l- Phenyl-5,6-dichlorobenzimidazole, 1-allyl-5,6-dichlorobenzimidazole, ■-allyl-5-chlorobenzimidazole, 1-7enylbenzimidazole, 1-phenyl-5
-Chlorbenzimidazole, l-methyl-5-trifluoromethylbenzimidazole.

l-ethyl-5-trifluoromethylbenzimidazole, l-ethylnat(1,2-d)imidazole, etc.).

In the general formula CM), Y simply represents an atomic group necessary to form a 5- or 6-membered carbon ring, or a methine chain when no ring is formed.

In general formula (M), m101 represents 1 or 2, X represents an acid residue.

m102 represents O or l, and is 0 when one dye has a betaine structure.

L and L represent a methine group or a substituted methine group. The substituted methine group is a lower alkyl group or a lower alkoxy group having 1 to 5 carbon atoms.

Aryl group (this aryl group may be substituted with a halogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a sulfo group, a carboxy group, etc.), an aralkyl group (such as a benzyl group) ), etc. are substituted with methine groups.

General formula (N) In the formula, Y and Y have the same meaning as Y , and R and R have the same meaning as R 108107101. 2. 2 has the same meaning as Z.

X has the same meaning as X.

m has the same meaning as m.

(Here, the same meaning means the same meaning as the definition of general formula (M).) -〇巳! -X Koichino - In the formula, Z represents an atomic group necessary to complete the 4-quinoline nucleus and the 2-quinoline nucleus.

Z has the same meaning as Z.

Plol represents 0 or 1.

m104 represents 2 or 3.

Y has the same meaning as Y.

R and R have the same meaning as R.

X has the same meaning as X, m105 has the same meaning as m.

L and L have the same meaning as L.

(Here, the same meaning means the same meaning as the definition of general formula (M).) Harm N In the formula, 2. 2 has the same meaning as Z.

R and R have the same meaning as R.

Y has the same meaning as Y, 0B X has the same meaning as X.

+04 101 m10B has the same meaning as m, Y, Y has the same meaning as Y.

(Here, the same meaning means the same meaning as the definition of general formula (M).) R and R are an alkyl group having 1 to 4 carbon atoms or a phenyl group, or R and R are connected to each other to form a group with 5 or 6 carbon atoms. Represents a group of atoms necessary to form a membered heterocycle.

薯　　　N During the ceremony, Z has the same meaning as Z.

Y has the same meaning as Y.

Y1□1 is oxygen atom, sulfur atom, selenium atom, =N-R
(R represents the same meaning as R 118118105).

R has the same meaning as R.

R is R 1□5. In addition to the group having the same meaning as 1, it represents a phenyl group, a pyridyl group, a substituted phenyl group, a substituted pyridyl group,
! Examples of the i substituent include a sulfone group, a carboxy group, a cyano group, a halogen atom (for example, a chlorine atom, a bromine atom, a fluorine atom, etc.), a C1-C4f)7At'P group, a C1-
Examples include a C4(7) alkoxy group, dialkylamino group, acyl group, and alkoxycarbonyl group.

Yllo has the same meaning as Y.

m107 has the same meaning as m, L and L have the same meaning as L.

(Here, the same meaning means the same meaning as the definition of general formula (M).) In the formula, Z , Y , Y , Y , R114゜RL10
8 107 115 105 and L and m are of the general formula (Q
) has the same meaning as that in ).

,! /].

8",, >,,W-" =,= In the formula 2. 2 has the same meaning as Z, and Ill
112 101 Y, Y has the same meaning as Y.

112 114 1ot R and R have the same meaning as R.

R7+19 101 R has the same meaning as R, Yl, 3 has the same meaning as Y.

X has the same meaning as X, has the same meaning as m.

m10B +02 (Here, the same meaning means that it is the same definition as the general formula (M), and has the α meaning.) General formula (T) In the formula.

2. 2 has the same meaning as Z.

113 114 10+y,y
has the same meaning as Y.

115 1111i 201R,R
has the same meaning as R.

X has the same meaning as X, m has the same meaning as m.

(Herein, the same meaning means the same meaning as the definition of general formula CM).) R has the same meaning as R118 of general formula (S).

General formula (U) (x107-) Town.

During the ceremony.

Y1□7 has the same meaning as Y, Y has the same meaning as Y, 10B +01 Z has the same meaning as Z, +15 105 Z has the same meaning as Z.

11B +01 R, R have the same meaning as R, +23 124 101q has the general formula (
It has the same meaning as pl in C), or has the same meaning as , and m has the same meaning as m + 10 102.

(In the above, the same meaning means the same meaning as the definition of general formula (M).) R has the same meaning as R in general formula (S).

General formula (W) In the formula, 2. 2 has the same meaning as Z 117 118 101 ・Y1□
9, Y has the same meaning as Y +20 101, and R128, R has the same meaning as R 127□o1.

X is X It has the same meaning as +08 1°1.

m1□1 has the same meaning as m102.

L has the same meaning as L 107 101. (In the above, the same meaning means that it has the same meaning as the definition of general formula (M).) R128 has the same meaning as R in general formula (S).

General formula (Y) In the formula, 2. 2 has the same meaning as Z, Y,
Y has the same meaning as Y, +21 122
101 R, R has the same meaning as R.

L, L, L, L, L
l, 2゜+08 109 110 111L
, L has the same meaning as L, and X has the same meaning as
has the same meaning as m, and has the same meaning as m.

mth 2!02 (Here, the same meaning means the same meaning as the definition of general formula (M)) In the present invention, the sensitizing dye is
, 756, or in a reaction system between a soluble silver salt (e.g., IR nitrate) and a halide (e.g., potassium bromide), or as described in U.S. Pat. No. 4,225,666. Accordingly, it may be present in the above reaction system after nucleation of silver halide grains and before the completion of the silver halide grain formation step, or simultaneously with the formation of silver halide grains, that is, the silver salt and halide may be present in the above reaction system. A sensitizing dye may be present in the reaction solution at the same time as mixing, and this method is superior in storage stability and gradation under high temperature conditions of the photographic material containing the emulsion prepared in this way. It is particularly preferable in this respect.

In any of the above addition methods, the total amount of one dye may be added at once, or may be added in several parts. Pigments may be added in the form of a mixture.

In addition, even if one type of pigment is used alone, or two types of pigments are used together (even if added mixed or added separately,
Alternatively, they may be added one by one at different times. In the latter case, a supersensitizer may be included.

The dye can be added either on the liquid surface or in the liquid, and any conventional stirring method can be used.

Sensitizing dyes can be added after being dissolved in water-compatible organic solvents such as methanol, ethanol, propyl, fluorinated alcohol methylcellosolve, dimethylformamide, acetone, or water (which may be alkaline or acidic). Alternatively, two or more of the substances described in E may be used in combination, or they may be added in the form of a dispersion in a water/gelatin dispersion system or in the form of a freeze-dried powder, or they may be further dispersed using a surfactant. The powder may be added in the form of a solution.

The appropriate amount of the sensitizing dye used is 0.001 g to 20 g per 100 g of silver used in emulsion production, preferably 0.001 g to 20 g.
01g to 2g.

The concentration of the sensitizing dye in the reaction solution in the silver halide grain forming reaction process is suitably 1% by weight or less, preferably 4% or less.

Chemistry of /'10 Silver Genide Emulsion Prepared by the Present Invention'IA
The same or different sensitizing dyes or supersensitizers may be additionally added during the formation process or during other processes before emulsion coating.

Examples of supersensitizers include aminostyryl compounds substituted with nitrogen-containing heterocyclic groups (for example, U.S. Pat. No. 2.93
No. 3,390, No. 3,635,721), aromatic organic acid formaldehyde condensates (such as those described in U.S. Pat. No. 3,743,510), cadmium salts, azaindene compounds, etc. May include;
U.S. Patent No. 3,615,613, U.S. Patent No. 3,615,
No. 641, No. 3,617,295, No. 3,635
, 721 are particularly useful.

Silver chlorobromide, silver bromide, silver chloroiodobromide, and silver iodobromide used in the present invention as silver halides in the photosensitive silver halide emulsion have a uniform /10 gene composition within the grains. Often, it may have a multiple structure with different compositions on the surface and inside (JP-A-57-154232, JP-A No. 5B-108533,
No. 59-48755, No. 59-52237.

US Patent No. 4,433,048 and European Patent No. 100
．． No. 984), and the thickness of the particles is 0.5 pm or less,
The diameter is at least 0.61 Lm and the average aspect ratio is 5.
The above tabular grains (U.S. Pat. No. 4,414,310, U.S. Pat. No. 4,435.499, OLS No. 3.241.646A+, etc.) or monodispersed emulsions with a nearly uniform grain size distribution ( @ open/close number 57-178235,
No. 58-100846, No. 58-14829 1 International Publication No. 83102338A, European Patent No. 64,412
A3 and No. 83.377A, etc.).

Two or more types of silver halides with different crystal habit, halogen composition, grain size, grain size distribution, etc. may be used in combination.
The gradation can also be adjusted by mixing two or more monodispersed emulsions with different grain sizes.

The grain size of silver halide in the present invention is such that the average grain size is O.
, OOIBm to 10 gm is preferable, and 0.00
1 JLm to 5 gm is more preferred.

These silver halide emulsions may be prepared by any of the acidic method, neutral method, or ammonia method, and the reaction method of the soluble silver salt and soluble halide salt is the one-sided mixing method,
Either the simultaneous mixing method or a combination of these methods may be used.
back-mixing method in which particles are formed under silver ion excess, or p
The Chondral double jet method, which keeps Ag constant, can also be used. Furthermore, in order to accelerate grain growth, the concentration, addition rate, or addition rate of silver salts and halogen salts to be added may be increased (Japanese Patent Application Laid-open Nos. 142329-1982, 158-158124, and U.S. Pat. ,650,75
No. 7, etc.).

Epitaxial junction type silver halide grains can also be used (4!f open w456-16124, U.S. Pat. No. 4.0).
No. 94,684).

In the step of forming silver halide grains used in the present invention, ammonia is used as a silver halide solvent, and Japanese Patent Publication No. 47-1
Organic thioether derivatives described in No. 1386 or ¥4
Contains described in No. 53-144319! &Yellow compounds etc. can be used.

In the process of particle formation or physical ripening.

Cadmium salt, zinc salt, lead salt, thallium salt, etc. may be coexisting.

Furthermore, for the purpose of improving high illumination failure and low illumination failure, water-soluble iridium salts such as iridium chloride (Dl, IV) and ammonium hexachloroiridate, or water-soluble rhodium salts such as rhodium chloride can be used.

The soluble salts may be removed from the silver halide emulsion after precipitation or physical ripening, and thus the Nudel water washing method or the precipitation method can be applied.

Although the silver halide emulsion may be used unripe, it is usually used after being chemically sensitized. For emulsions for conventional light-sensitive materials, well-known II&S sensitization methods, binary sensitization methods, blue metal sensitization methods, etc. can be used alone or in combination. These chemical sensitizations can also be carried out in the presence of nitrogen-containing heterocyclic compounds (JP-A-58-126526, JP-A-58-2156).
No. 44).

The silver halide emulsion used in the present invention may be a surface latent image type in which a latent image is mainly formed on the grain surface or an internal latent image type in which a latent image is formed inside one grain. Direct inversion emulsions combining emulsions and nucleating agents can also be used. Internal latent image emulsions suitable for this purpose are disclosed in U.S. Pat. No. 2,592,250, U.S. Pat.
It is described in No. 41 etc. A preferred nucleating agent for combination in the present invention is U.S. Pat. No. 3,227,552.

No. 4,245,037.

No. 4,255,511.

No. 4,266.013.

No. 4,276.364 and It is described in 0L32,635,316, etc.

As a method for forming the silver halide grains used in the present invention, a known single jet method or double jet method can be used.・Double jet method can also be used. In addition, a combination of these methods may be used.In any of the above-mentioned silver halide emulsion forming methods, either the known single-stage addition method or multi-stage addition method may be used, and the addition rate may be a constant rate. , or a stepwise or continuous rate change (this could be, for example, a soluble silver salt and/or
Alternatively, there is a method of changing the addition flow rate of these solutions while keeping the concentration of the halide constant, or a method of keeping Vi, the soluble silver salt in the additive solution and/or the addition rate constant,
(can be achieved by changing the concentration of halide, or by a combination of these)
Further, the reaction solution may be stirred by any known stirring method, and the temperature and pH of the reaction solution during silver halide grain formation may be set in any manner.

The coating amount of photosensitive silver halide of the present invention is calculated as silver equivalent I B
to 10g/go.

Gelatin is advantageously used as a protective colloid and as a binder for other hydrophilic colloid layers used in the preparation of the emulsions of the invention, but other hydrophilic colloids can also be used.

For example, gelatin derivatives, graft polymers of gelatin and other polymers, pale substances such as albumin and casein; hydrodiethylcellulose.

Cellulose derivatives such as carboxymethylcellulose and cellulose sulfate esters, sugar derivatives such as sodium alginate and starch derivatives: vorivinyl alcohol, polyvinyl alcohol partial acetal, poly-N rubinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, A wide variety of synthetic hydrophilic polymeric materials can be used, such as single or copolymers of polyvinylimidazole, polyvinylpyrazole, and the like.

Gelatin includes lime-processed gelatin, acid-processed gelatin, Bull, Soc, and Sci.

Photo, Japan, No, l 6,
Enzyme-treated gelatin as described in P.30 (1966) may be used, and gelatin hydrolysates and enzymatically decomposed products may also be used.

In the present invention, an organic silver salt relatively stable to light can be used in combination with the photosensitive silver halide as an oxidizing agent. In this case, it is necessary that the photosensitive silver halide and the organic silver salt be in contact with each other or at a close distance.

When an organic silver salt is used in combination in this way, when the heat-developable photosensitive material is heated to a temperature of 80°C or higher, preferably 100°C or higher, the organic m-oxidizing agent also undergoes redox using the latent image of silver halide as a catalyst. It is thought that it is involved in

Examples of organic compounds that can be used to form the organic silver salt oxidizing agent described above include aliphatic or aromatic carboxylic acids, compounds containing a mercapto group or a thiocarbonyl group having an α-hydrogen, and compounds containing an imi7 group. Examples include.

Silver salts of aliphatic carboxylic acids include behenic acid, stearic acid, oleic acid, and lauric acid.

Capric acid, myristic acid, palmitic acid, maleic acid, fumaric acid, tartaric acid, furoic acid.

linoleic, linuric, adipic, sebacic, succinic, acetic, acetic, or camphoric acid.

A typical example is a silver salt derived from . Silver salts derived from these fatty acids substituted with halogen atoms or hydroxyl groups, or aliphatic carboxylic acids having thioether groups can also be used.

Silver salts of aromatic carboxylic acids and other carboxyl group-containing compounds include benzoic acid, 35-dihydroxybenzoic acid, o-, m- or p-methylbenzoic acid, 2.
4-dichlorobenzoic acid, acetamidobenzoic acid, p-phenylbenzoic acid, 9. Aromaic acid, gallic acid, tannic acid, phthalic acid, terephthalic acid, salicylic acid, phenylacetic acid, pyromellitic acid or 3-carboxymethyl-4-methyl-4-
Representative examples include silver salts derived from thiazoline-2-thione and the like.

As a silver salt of a compound having a mercapto or thiocarbonyl group, 3-mercapto-4-7enyl 1.2
．． 4-triazole, 2-mercaptobenzimidazole, 2-mercapto-5-aminethiadiazole, 2-
Mercaptobenzthiazole, S-furkylthioglycolic acid (alkyl group with 12 carbon atoms), dithiocarboxylic acids such as dithioacetic acid, thioamides such as thiostearamide, 5-carboxy-1-methyl-2-phenyl- 4-thiopyrin, mercaptotriazine, 2
-Mercaptohenzoxazole, mercaptooxadiazole or 3-amino-5-benzylthio-1,2
, 4-triazole, etc. U.S. Pat. No. 4,123,274
Examples include silver salts derived from mercapto compounds described in the above.

As a silver salt of a compound having an imino group.

Benzotriazole or its derivatives described in Japanese Patent Publication No. 44-30270 or JiIQ45-18416 1 For example, benzotriazole, alkyl-substituted penzotriazoles such as methylbenzotrianol, halogen-substituted benzotriazoles such as 5-chlorobenzotriazole, butyl carbo Carboimidobenzotriazoles such as imidobenzotrizole, nitrobenzotriazoles described in JP-A-58-118639, sulfobenzotriazole, carboxybenzotriazole or a salt thereof, or hydroxybenzotriazole as described in JP-A-58-118838 Such,
1.2.4-1 described in U.S. Patent No. 4.220.709
Representative examples include silver salts derived from lyazole, lH-tetrazole, carbazole, saccharin, imidazole, and derivatives thereof.

Also, Research Disclosure Magazine No. 170, 1702
Silver salts of carboxylic acids having alkyl groups, such as the silver salts described in No. 9 (June 1978) and 2-enylpropiolic acid described in Japanese Patent Application No. 58-221535, can also be used in the present invention.

The above organic silver salts are 0 per mole of photosensitive silver halide.
．． 01 to 10 mol, preferably 0,0 to 1 mol can be used in combination. The total coating amount of photosensitive silver halide and organic silver salt is 50-g to 1 Og/m
” is appropriate.

It is desirable that the photothermographic material of the present invention contains an alkali or an alkali precursor.

The alkali precursor referred to in the present invention is one that releases a base component upon heating, and the released salt) & component may be an inorganic base or an organic base.

Examples of preferred alkalis include alkali metal or alkaline earth metal hydroxides, secondary
or tertiary phosphate, borate, carbonate, quinolinate, metaborate; ammonium hydroxide: hydroxide of quaternary alkyl ammonium; hydroxide of other metals, etc. Examples of alkalis include aliphatic amines (trialkylamines, hydroxylamines, aliphatic polyamines), aromatic amines (N-alkyl-substituted aromatic amines, N-hydroxylalkyl-substituted aromatic amines, and bis(p -(dialkylamino)phenylcomethanes), heterocyclic amines, amidines, cyclic amidines, guanidines, cyclic guanidines, and U.S. Pat. , diaminobutane dihydrochloride, U.S. Pat. No. 3,506,444 describes organic compounds containing amino acids such as urea, 6-7 minocaproic acid, and are useful.
Those having a Ka value of 8 or more are particularly useful.

Examples of alkali precursors include salts of organic acids and alkalis that decompose by decarboxylation upon heating, compounds that decompose through Rossen rearrangement, Beckmann rearrangement, etc. and release amines, and other substances that cause some kind of reaction upon heating and release alkali. used.

Preferred alkali precursors include the aforementioned organic alkali precursors.

For example, trichloroacetic acid, trifluoroacetic acid, propiolic acid, cyanoacetic acid, sulfonylacetic acid.

Salts with thermally decomposable organic acids such as acetoacetic acid, U.S. Pat.
．． Examples include salts with 2-carboxycarboxamide described in No. 088.496.

Preferred specific examples of alkali precursors include the following as examples of compounds whose acid moieties are thought to decarboxylate and release alkali.

Examples of trichloroacetic acid s derivatives include guanidine trichloroacetic acid, piperidine trichloroacetic acid, morpholine trichloroacetic acid, p-)luidine trichloroacetic acid, 2-picoline trichloroacetic acid, and the like.

Other British Patent No. 998,945, U.S. Patent No. 3,2
Use the alkali precursor described in No. 20,846, JP-A No. 50-22625, etc. 1G is possible.

Other than trichloroacetic acid, U.S. Patent No. 4,0
Examples include 2-carboxycarboxamide derivatives described in US Pat. No. 88,496, α-sulfonyl acetate derivatives described in U.S. Pat. . As the alkali component, in addition to organic alkalis, salts using alkali metals and alkaline earth metals are also effective and are described in Japanese Patent Application No. 58-69597.

Precursors other than L include -0-, hydroxamic carbamates disclosed in Japanese Patent Application No. 43860/1986 using cene rearrangement, and Japanese Patent Application No. 3161/1983 which produces nitriles.
Fludoxime lupamates described in No. 4 are effective.

In addition, amine imides described in Research Disclosure magazine May 1977 issue No. 15776, JP-A-50-22
Aldonamides described in Japanese Patent No. 625 are preferably used because they decompose at high temperatures to produce bases.

A wide variety of alkalis or alkali precursors can be used in the present invention.

A useful range is 50% by weight or less, more preferably from 0.01% to 40% by weight of the coated dry film of the photosensitive material.

In the present invention, a compound (dye-donating substance) that generates or releases a mobile dye, that is, a diffusible dye, in response to or inversely to this reaction when photosensitive silver halide is reduced to silver by heating. Contains.

This type of compound can be represented by the following general formula (LI).

(Dye-X)n-Y (LI) Dye represents a dye group or a dye precursor group; Correspondingly (Dye-X)n
-Creating a difference in the diffusivity of the compound represented by Y,
Alternatively, Dye is released and the released Dye and (Dye
-X) represents a group that has the property of causing a difference in diffusivity between n and Y, where n represents 1 or 2, and when n is 2, the two Dye-Xs may be the same or different. You can leave it there.

Specific examples of the dye-donating substance represented by the general formula (LI) include 1. For example, a dye developer in which a hydroquinone developer and a dye component are linked is disclosed in US Pat. No. 3,134,764.
No. 3, No. 362.819, No. 3,597,20
No. 0, No. 3,544,545, No. 3,482.9
It is described in No. 72, etc. In addition, a substance that releases a diffusible dye by an intramolecular nucleophilic substitution reaction was disclosed in JP-A-51-
63,618 etc.

A substance that releases a diffusible dye through an intramolecular rewinding reaction of the isoxacilone ring was disclosed in JP-A-49-111,628.
It is stated in the number etc. In all of these methods, the diffusible dye is released or diffused in areas where development has not occurred, and the dye is neither released nor diffused in areas where development has occurred. Also, in these methods, development and dye release or diffusion occur in parallel.

It is very difficult to obtain an image with a high S/N ratio. Therefore, in order to improve this drawback, a dye-releasing compound is made into an oxidized form without seismically isolated release ability and coexisted with a reducing agent or its precursor, and after development, it is reduced by the remaining unoxidized reducing agent. A method has also been devised in which a diffusible dye is released using a method of releasing a diffusible dye.

JP-A-53-110,827, JP-A No. 54-130.92
No. 7, No. 56-164, 342, No. 53-35, 53
It is stated in No. 3.

On the other hand, as a substance that releases a diffusible dye in the area where development occurs, a substance that releases a diffusible dye through the reaction between a coupler having a diffusible dye as a leaving group and an oxidized form of a developer is disclosed in British Patent No. 1. .330,524, Special Publication 1973-39.
No. 165, U.S. Pat. No. 3,443,940, etc., and U.S. Pat. No. 3, U.S. Pat. .227,550 etc.

In addition, in systems using these color developers, image contamination due to oxidative decomposition products of the developer becomes a serious problem.
In order to improve this problem, color patch-releasing compounds that do not require a developer and have reducing properties themselves have also been devised.

Representative examples are described in the following documents.

U.S. Patent No. 3,928,312 U.S. Patent No. 4.
No. 053.312, U.S. Patent No. 4.055.428;
U.S. Patent No. 4,336,322, JP 59-658
No. 39, JP-A-59-69839, JP-A-53-38
No. 19, JP-A-51-104,343, U.S. Patent No. 3
No. 725.062, Research Disclosure No. 17465, U.S. Patent No. 3,725.062, U.S. Patent No. 3,728,113, U.S. Patent No. 3,443,
No. 939, JP-A-59-116,537, etc.

Any of the various dye-providing substances described above can be used in the present invention.

The dye-donating substance that can serve as a reducing agent for releasing a mobile dye used in the present invention is preferably represented by the following general formula (Lll
): R-S O2-D (L II ).

In the above formula (L II), [1 is cleaved correspondingly or inversely to the photosensitive silver halide having a latent image, releasing a dye, and combining the released dye and a dye-donating substance. Represents a reducing substrate that has the property of causing a difference in mobility between.

D is a mobile image-forming dye (including its precursor)
may also include a linking group connecting the 'pure' dye moiety and the S02 group.

Reducing substrate (IR
) has a redox potential of 1.2 V with respect to a saturated calomel electrode in Voterograph half-wave potential measurement using acetonitrile as a solvent and sodium perchlorate as a supporting electrolyte.
The following are preferred: Preferred general examples of reducing substrates represented by elbows include:
JP-A No. 59-84236.

General formulas (II) to (X) described on pages 17 to 37
, (Xa), (X b), CXI).

(X[a), ()Cb), (X[c), and 0QI)
Various groups represented by can be mentioned.

Preferred specific examples of (1) are described on pages 30 to 37 of JP-A-59-84236.

Further, the dye moiety represented by D includes an azo dye, an azomethine dye, and an anthraquinone dye.

It is derived from naphthoquinone dyes, styryl dyes, nitro dyes, quinoline dyes, carbonyl dyes, phthalocyanine dyes, etc., and this dye part may be temporarily shortened in wavelength, and is released from a dye-donating compound. For specific examples of the dye portion, see the above-mentioned JP-A-59-
Examples include those described on pages 37 to 59 of Publication No. 84236.

Specific examples of the dye-donating substance that can be used in the present invention include the compounds described on pages 60 to 91 of the aforementioned JP-A-59-84236. Compounds (1) to (3), (10) to (1) described
3).

(16)-(19), (28)-(30).

(33), (35), (38)-(40).

(42) to (64) are preferred.

The dye-donating substance can be used in a certain concentration range. A generally useful concentration range is from o,oi moles of two dye-donating material to about 4 moles of dye-donating material per mole of silver halide.

Particularly useful concentrations in the present invention are about 0.03 mole to 1 mole of halogenation.

In the present invention, the dye-donating substance is U.S. Pat.
They can be introduced into the layers of the photosensitive material by known methods such as the method described in No. 2,027. In that case, high 8 point organic solvents and low boiling point organic solvents as described on pages 63 to 64 of Japanese Patent Application No. 59-213978 can be used.

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

In the present invention, it is desirable to include a reducing substance in the light-sensitive material. Examples of the reducing substance include those generally known as reducing agents, as well as dye-donating substances having the above-mentioned one-dimensionality.

Also included are reducing agent precursors that do not themselves have reducing properties but develop reducing properties through the action of nucleophiles and heat during the development process.

'' For specific examples of reducing agents and reducing agent precursors and documents describing them, see Japanese Patent Application No. 59-213978 65-
It is described on page 66.

In the present invention, an image formation accelerator can be used in the light-sensitive material. Image formation accelerators include those that promote redox reactions between silver salt oxidizing agents and reducing agents, promote reactions such as generation of dyes from dye-donating substances, decomposition of dyes, and release of mobile dyes, and photosensitive materials. It has functions such as promoting the movement of dye from the layer to the dye fixing layer, and from a physicochemical function, it has the above-mentioned alkali (base) or alkali precursor (base precursor), nucleophilic compound, oil, hot solvent, It is classified as a surfactant, a compound that interacts with silver or silver ions, etc. However, these substance groups generally have multiple functions and usually have some of the promoting effects listed in F.

For details of these, see Japanese Patent Application No. 59-213978 6.
It is described on pages 7-71.

In the present invention, various development stoppers can be used in the photosensitive material in order to always obtain a constant image despite fluctuations in processing temperature and processing time during thermal development.

The development stopper mentioned here is a compound that neutralizes the base or reacts with the base to reduce the base concentration in the film and stop development, or a compound that interacts with silver and silver salts to stop development. It is a compound that suppresses

Specifically, it is described in Japanese Patent Application No. 59-213978, pages 72-73.

Further, in the present invention, a compound that activates development and simultaneously stabilizes the image can be used in the photosensitive material.

Regarding the compounds preferably used among them, the patent application
No. 9-213978, pages 73-74.

In the present invention, the photosensitive material may contain an image toning agent if necessary.

For effective specific examples, see Japanese Patent Application No. 59-21397.
No. 8, pages 74-75.

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

In the present invention, the binder is applied in an amount of 20 g or less per trn'', preferably 10 g or less, more preferably 7 g or less.

The ratio of the high boiling point organic solvent dispersed in the binder together with a hydrophobic compound such as a dye-donating substance and the binder is as follows:
Less than lee of solvent per 1g of binder, preferably 0
．． A suitable amount is 5 cc or less, more preferably 0.3 cc or less.

The material of the present invention may contain an inorganic or organic hardener in the photographic emulsion layer or other binder layer. For example, there is one described in Japanese Patent Application No. 59-213978, pages 76-77.

The support used in the light-sensitive material and dye-fixing material used in the present invention is one that can withstand processing temperatures. As a general support,
Glass, paper, metal and their analogs are used, as well as cellulose acetate films, cellulose ester films, polyvinyl acetal films, polystyrene films, polycarbonate films, polyethylene terephthalate films and related films or resin materials. Paper supports laminated with polymers such as polyethylene can also be used. U.S. Pat. No. 3,634.

The polyesters described in No. 089 and No. 3.725.070 are preferably used.

In the present invention, when a dye-donating substance that releases an image-wise mobile dye is used, a dye transfer aid can be used to transfer one dye from the photosensitive layer to the dye fixing layer.

Regarding this specific example, please refer to Japanese Patent Application No. 59-213978 7.
It is described on pages 8-79. When the light-sensitive material of the present invention contains a colored dye-donating substance, it may further include an anti-irradiation substance or an anti-halation substance.
Alternatively, although it is not so necessary to incorporate various dyes into the light-sensitive material, in order to improve the sharpness of one image, Filter dyes, absorbent substances, etc. can be included.

In the present invention, the photosensitive material may contain various additives known as heat-developable photosensitive materials and layers below the photosensitive layer, such as an antistatic IF layer, a main layer, a protective layer, an intermediate layer, and an AH layer, as necessary.
It can contain layers, release layers, etc. For various additives, see Research Disclosure Magazine Vol.
．． 170. Additives described in Sun, June 1978, No. 17029, such as plasticizers, sharpening dyes, A
Additives include H dyes, sensitizing dyes, capping agents, surfactants, optical brighteners, and anti-fading agents.

The photographic material of the present invention is preferably a light-sensitive material that forms or releases a dye by heat development.

If necessary, a dye fixing material for fixing the dye is included.
In particular, in systems that form images by diffusion transfer of dyes, a light-sensitive material and a dye-fixing material are essential, and in a typical form, the light-sensitive material and the dye-fixing material are separately coated on two supports. It is broadly divided into two types: one in which it is coated on the same support, and the other in which it is coated on the same support.

Regarding the form and layer structure of the dye-fixing material and the manufacturing method and processing method (including the developing method) of the photographic material, please refer to the patent application filed in 1973.
The method described in No. 9-213978, pages 81 to 96 can be applied.

■Specific effects of the invention According to the present invention, it contains 60 to 100 mol% of silver bromide, and contains 6 mol% or less of silver iodide, or does not contain silver iodide,
Moreover, when the remaining content is present, it contains a photosensitive silver halide emulsion in which silver halide grains containing silver chloride are formed in the presence of a sensitizing dye. It has high sensitivity in exposure, rapid development progress, and high maximum image density.

A photothermographic material having excellent F storage stability can be obtained.

In terms of storage stability, it is particularly effective in preventing a decrease in sensitivity due to storage of photosensitive materials.

(2) Specific Examples of the Invention Hereinafter, specific examples of the present invention will be shown to explain the effects of the present invention in further detail.

Example 1 The method of making the silver halide emulsion used here will be described.

(1-a) Emulsions 1 to 6 Well-stirred gelatin aqueous solution (water 1000100O
20g of gelatin and 2g of sodium base are dissolved and kept at 75°C) containing potassium bromide and sodium chloride (potassium iodide may be added as necessary) (combined) 0.59 mol) aqueous solution 600
1300 ml of an aqueous solution containing m and 0.59 mol of silver nitrate
were added at the same time in equal flow over 60 minutes. At that time, 10 minutes after the start of silver halide grain formation, the dye I O,16
A solution prepared by dissolving 100 g of methanol in 400 cc of methanol was added over 40 minutes during particle formation. 40g gelatin after washing with water and increasing
and 200 m of water to adjust the pH, and sodium thiosulfate and 4-hydroxy-6-methyl-1,3,3a,7
- Optimal chemical sensitization was carried out using chitrazaindene. The yield of emulsion is 700 g.

Dye Process Emulsions 1 to 6 thus obtained are summarized in Table 1.

(1-b) Emulsions 7 to 12 A well-stirred gelatin aqueous solution (in 600 mu of water,
20g gelatin, 0.5g KBr and HO(CH
2) 2S (CH2)25(CH2)20HO,25
11 potassium bromide in a ge-dissolved sample (kept at 7°C)
160 mi of an aqueous solution (liquid I) containing 4.2 g of potassium iodide and 0.2 g of potassium iodide, and an aqueous solution (■
160 ml of liquid) was added at an equal flow rate over 20 minutes.
After leaving it as it is for 10 minutes, 450ml of an aqueous solution (M solution) containing potassium bromide and potassium iodide! 450 ml of an aqueous solution (■ solution) containing L and 0.47 mol of silver nitrate was
PAg was kept constant and added using a controlled double jet method over a period of minutes.

At the same time as the solutions (1) and (2) were added, a dye solution in which 0.16 g of the dye (2) was dissolved in 400 cc of methanol was added over 30 minutes.

After washing with water and desalting, 40g of gelatin and 200m of wood! ; Adjust pH by adding L, sodium thiosulfate and 4-hydroxy-6-methyl-1,3,3a.

Optimal chemical sensitization was performed using 7-chitrazaindene. The yield of emulsion is 700 g.

Dye II Emulsions 7 to 12 thus obtained are summarized in Table H.

Table II Halogen composition (%) Emulsion Br I Shape
Average grain size (extension) Emulsion 7 (invention) 9916 hexahedron
0.5 connection 8 (invention) 9736 hexahedron 0.5
End 9 (present invention) 95 5 tetradecahedron
0.5 le 10 (invention) 99 1
Tedecahedron 0.5 pot 11 (comparison) 9
3 7 Tedecahedron 0.5 body 12 (comparison) 9098 hedron 0.5 JL We will describe how to make a benzotriazole silver emulsion.

28 g of gelatin and 13.2 g of benzotriazole were dissolved in 3000 mM of water. This solution was kept at 40°C and stirred. A solution prepared by dissolving 17 g of silver nitrate in 100 mM of water was added to this solution over 2 minutes.

The pH of the benzotriazole silver emulsion was adjusted and allowed to settle to remove excess salt. Thereafter, the pH was adjusted to 6.30, and a yield of 400 g of benzotriazole silver emulsion was obtained.

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

Weigh out 5 g of yellow dye-donating substance (A), 0.5 g of sodium succinate-1-dithylhexyl ester sulfonate as a surfactant, and 10 g of triiso-nonyl phosphate, and add 30 mfL of ethyl acetate. about 6
The mixture was heated and dissolved at 0°C to form a uniform solution. This solution and 100 g of a 10% solution of lime-treated gelatin were stirred and mixed, and then dispersed using a homogenizer for 10 minutes at OOORPM. This dispersion is called a yellow dye-providing substance dispersion.

Dye-donating substance (A) Next, a method for preparing a photosensitive coating will be described.

a) Benzotriazole silver emulsion 10gb) Silver halide emulsion 1 (same preparation method for emulsions 2 to 12) 15gC) Dispersion of dye-providing substance 25gd) 5% aqueous solution of the following compound
5mMCs H+q+O(cH2c)120)a He
) 10% methanol solution of benzenesulfonamide
5m f) 10% aqueous solution of 4-methylsulfonylphenylsulfonylacetate guanidine
Mix a) to f) of 15 mQ or more, add a thickener (e.g., polystyrene-p-sodium sulfonate) and water, and mix 10 mQ or more.
It was set to 0 mJl. This liquid was applied to a wet film thickness of 50 gm on a polyethylene terephthalate film having a thickness of 180 Bm.

Next, the following protective layer coating composition was prepared.

g) 10% gelatin 400 gh) 4
- 710% aqueous solution of guanidine methylsulfonylphenylsulfonylacetate 240 mA) 4% aqueous solution of hardener with the following structural formula:
so gCH2=CH-502CH2C0NH-
(CH2)2 NHCOCH2502CH=CH2 g) to i) were mixed, a thickener and water were added, and LOOOm
I went to see it.

This was coated with the above photosensitive coating material and further thickened to a thickness of 30 mm.
It was applied with gm. Silver halogen emulsion 1 to 1 used
Samples A-L (Table ■)
It is called.

These samples A-L were measured using an EG&G sensitometer Mark-■
Imagewise exposure was carried out for 10-4 seconds using a 500-600 nmcy) c:,z pass filter. After that, each was placed on a heat block heated to 150℃ for 20 minutes.
The film was uniformly heated and developed for 2 seconds, 30 seconds, and 40 seconds.

Also, a tungsten light bulb was used for comparison.

The film was imagewise exposed at 500 lux for 1 second through the above band-pass filter, and developed by heating at 150° C. for 30 seconds.

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

Poly(acrylic acid methyl-co-N,N,N-trimethyl-N-vinylbenzylammonium chloride) (ratio of acrylic methyl and vinylbenzylammonium chloride is 1:1) Dissolve 10g in 200ml of water,
5. Mixed uniformly with 100 g of 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 dry blasting, this sample was used as a dye fixing material having a mordant layer.

Next, after supplying 20 ml of water per 1 m2 to the membrane side of the dye-fixing material, the heat-treated coated samples A-L were stacked on the fixing material so that their membrane surfaces were in contact with each other.

After heating on a heat block at 80°C for 6 seconds, the dye fixing material was peeled off from the photosensitive material.

A yellow color image was obtained on the fixed material. The density of this was measured using a Macbeth reflection type densitometer (RD519). Sensitivity was also determined from this.

These results are shown in Table m.

From Table 1, it can be seen that the emulsion of the present invention has excellent performance in that it has high sensitivity and accelerates the thermal development process in high-intensity, short-time exposure.

Example 2 The method of making the silver halide emulsion used here will be described.

(2-a) Emulsions 13 to 17 A well-stirred gelatin aqueous solution (gelatin 20g, KBrl, 2g and HO(CH2)2 in 600mu of water)
Controlled double jet method: 620mM of an aqueous solution containing 0.59 mol of silver nitrate and 620mJ1 of an aqueous solution containing potassium bromide and potassium iodide were dissolved in S (CH2)25(CH2)20H0.45g and kept at 50°C). The pAg was maintained at 8.9 and added over 50 minutes. At that time, at the same time as the addition of the halogen solution and silver nitrate solution, 360 mjL of methanol solution containing 0.14 g of dye m was added.
was added and then the entire coagulation was added over a period of 25 minutes.

After washing with water and desalting, add 40 g of gelatin and 200 ml of water.
Adjust H, add sodium 100sulfate, chloroauric acid and 4-hydroxy? Optimal chemical sensitization was performed using -6-methyl-1°3.3a and 7-chitrazaindene.
The yield of emulsion is 700 g.

Dye (1) Emulsions 13 to 17 thus obtained are summarized in Table (2).

Table ■ Halogen composition (%) Emulsion Br I Shape Average grain size (pot) Emulsion 13 (invention) 99
1 Tedecahedron 0, 551L14 (invention) 97 3 Tedecahedron 0.5
p15 (present invention) 95 5 Tedecahedron 0.5 well 16 (comparison) 93
7 Tedecahedron 0.5 p17 (comparison)
91 9 Tedecahedron 0.45 pot (2
-b) Silver halide emulsions 18 to 22 Emulsions 1 to 22 of Example 1
Emulsion 13 was used instead of the methanol solution of dye I used in 6.
~ Using the dye ■ used in 17, dye II [0.14 g
Emulsions 1 to 6 were prepared in exactly the same manner as Emulsions 1 to 6, except that a 380 mM methanol solution containing .

Emulsions 18 to 22 thus obtained are summarized in Table V.

Table V Halogen composition (%) Emulsion Br 0 sentences Shape
Emulsions 13 to 22 were used instead of emulsions 1 to 12 in Example 1, and the following magenta dye was used in place of the yellow dye-providing substance (A) in the dispersion of a dye-providing substance. A photosensitive coating was prepared in the same manner as in Example 1 except that the donor substance (B) was used. Samples M-V were selected according to the emulsions used as shown in Table (2).

The same process as in Example 1 was performed except that these samples M-V were exposed through a 600-700 nm bandpass filter.

Sensitivity was determined.

The results are shown in Table ■.

Dye-donor substance (B) Table 1 shows that the emulsion of the present invention has excellent performance in terms of high sensitivity in high-intensity, short-time exposure.

Example 3 The method of making the silver halide emulsion used here will be described.

(3-a) Emulsions 23 to 27 A well-stirred gelatin aqueous solution (20 g of gelatin and 1.5 g of sodium chloride dissolved in 100,100 O of water and kept at 75°C) was added with potassium bromide and sodium chloride ( Potassium iodide may be added as necessary) (total 0.59 mol) aqueous solution 600ml
An aqueous solution of silver nitrate (059 mol of silver nitrate dissolved in 600 m of water) was added at the same time in equal flow over 70 minutes. At this time, the dye IVO is added at the same time as silver halide grain formation.
, 12 g dissolved in 300 cc of methanol was added over 40 minutes. After washing with water and desalting, gelatin 40g and water 2
00 mJ1 was added to adjust the pH, and optimal chemical sensitization was performed using triethylthiourea and a nucleic acid dispersion. The yield of emulsion is 700 g.

Dye (2) Emulsions 23 to 27 thus obtained are summarized in Table (2).

(3-b) Silver halide emulsions 28-33 Potassium bromide and a well-stirred aqueous gelatin solution (20 g of gelatin and 3 g of sodium chloride dissolved in 1000 ml of water and kept at 60°C) were added. Contains sodium chloride (potassium iodide may be added if necessary)
600 ml of an aqueous solution (total of 0.59 mol) and 600 ml of an aqueous solution containing 0.59 mol of silver nitrate were simultaneously added at equal flow rates over 60 minutes. At that time, 50 minutes after the start of silver halide grain formation, a solution prepared by dissolving 015 g of dye V 2 O in Methyl Celsorop 300CC was added over 10 minutes.

After washing with water and desalting, add 40g of gelatin and 200ml of water.
The pH was adjusted, and optimal chemical sensitization was performed using triethylthiourea and a nucleic acid decomposition product. The yield of emulsion is
It is 700g.

Emulsions 28 to 33 thus obtained are summarized in Table 2.

The above emulsions 23 to 3 were used instead of emulsions 1 to 12 in Example 1.
A photosensitive coating was prepared in the same manner as in Example 1 except that the following cyan dye-providing substance (C) was used in place of the yellow dye-providing substance (A) in the dye-providing substance dispersion. was prepared. As shown in Table (2), the samples were given as $4W-Z and a-g depending on the emulsion used.

The sensitivities were determined by performing the same process as in Example 1 except that these samples were exposed through a sharp cut filter that transmits wavelengths of 740 nm and above.

The results are shown in Table ■.

Dye-donating substance (C) From Table 1, it can be seen that the emulsion of the present invention has high sensitivity in high-intensity, short-time exposure.

Example 4 How to make silver halide emulsions 34 to 36 will be described.

A well-stirred gelatin aqueous solution (containing 20 g of gelatin and 3 g of sodium chloride in 10,100 O of water at 75°C)
Mix 600 m of an aqueous solution containing sodium chloride and potassium bromide (kept warm at
0.59 mol of silver nitrate dissolved in 0 mM) was simultaneously added at an equal flow rate over 60 minutes. In this way, a monodisperse kepipedic silver chlorobromide emulsion (80 mol % of bromine) with an average grain size of 0.401 L was prepared.

After washing with water and desalting, add 40g of gelatin and 200ml of water.
After adjusting H, 5 mg of sodium thiosulfate and 20 mg of 4-hydroxy-6-methyl-1,3°3a,7-titrazaindene were added to perform chemical sensitization at 60°C. The yield of emulsion is 700 g.

First, a multilayer 4R color photosensitive material as shown in Table Had made.

In exactly the same manner, multilayer photosensitive materials i to q were prepared by changing the emulsion used in the photosensitive emulsion layer as shown in Table X [
).

However, when Emulsion 34 is used in the fifth layer, dye (Example 1), when used in the third layer, dye (Example 2), and when used in the first layer, dye (Example 3) is used. When preparing the coating solution, the coating noise was 1 mol/m2 of IO, 8
X was added at a concentration of 10-7 mol/m2, 10-a mol/m2.

Note that emulsions other than emulsion 34 were prepared in the same manner as in Examples 1-3. Further, the dye-donating substance was prepared in the same manner as in Examples 1-3.

G
, R, IR 3 color separation filter (G is 500~600n
m, R are 600-700 nm bandpass filters,
The IR was exposed to -4 seconds through a filter that transmits wavelengths below 740 nm. For comparison, a tungsten bulb was used and exposed through the above films at 500 lux for 1 second.

Thereafter, it was heated uniformly for 20 seconds on a heat block heated to 150°C.

Next, 20 rnl/m2 of water was supplied to the film surface side of the dye fixing material, and the heat-treated photosensitive coatings were combined with the fixing material so that the film surfaces were in contact with each other.
After heating for 6 seconds in a heat block at 80°C, remove the dye fixing material 1 from the photosensitive material 1 and place it on the fixing material.
Yellow, magenta, and cyan color images were obtained corresponding to the G and RlIR three-color separation filters, respectively. The density of each color was measured using a Macbeth reflection densitometer (RD 519) to determine the sensitivity.

The results are shown in Table X.

From Table X, it can be seen that the emulsion of the present invention has high sensitivity in high-intensity, short-time exposure even when applied to a color light-sensitive material having a multilayer structure.

Example 5 Multilayer color photosensitive materials h, j, 1. m,
n was stored at 40° C. and 70% RH or at 50° C. in a dry state for 4 days. Thereafter, the same treatment as in Example 4 was performed, and the density was measured to determine the sensitivity. These values were compared with the sensitivity of the light-sensitive material before storage under the conditions described above, and variations in sensitivity were investigated for each.

The results are shown in the table name.

It can be seen from the table that the emulsion of the present invention exhibits no decrease in sensitivity upon storage and has excellent storage stability.

From the above, the effects of the present invention are clear.

・With Tsubo.

Claims (1)

[Claims] Silver halide grains containing 60 to 100 mol% of silver bromide and 6 mol% or less of silver iodide, or containing no silver iodide, and further containing silver chloride if the remaining content is present. 1. A heat-developable photosensitive material comprising a photosensitive silver halide emulsion formed in the presence of a sensitizing dye.