JPS6315245A - Heat developable photosensitive material - Google Patents

Abstract

PURPOSE:To improve sensitivity and to decrease the fluctuation of the sensitivity and fogging with age by providing a silver halide emulsion layer contg. >=1 kinds of octahedron having (111) faces, fourteen-faced body and planar silver halide particles, sensitizing dye and benzotriazoles to a titled material. CONSTITUTION:The silver halide emulsion layer contg. >=1 kinds of the octahedron having (111) faces, fourteen-faced body and planar silver halide particles, sensitizing dye and benzotriazoles is provided to the material. Sulfonamide phenols and sulfonamide naphthols are preferably used in combination in order to additionally decrease the deteriorated sensitivity and increased fogging during preservation. Silver is usable as an image forming material and a compd. which forms or releases a mobile dye in response or reverse response to the reaction when the silver ions are reduced to silver in a high-temp. state, i.e., a dye donative material may be incorporated into the material as well.

Description

[Detailed description of the invention] ■ Background of the invention Technical field The present invention relates to a highly sensitive photothermographic material.

Prior Art and Its Problems Heat-developable photosensitive materials using silver halide are well known in this technical field, and many proposals have been made regarding methods for obtaining color images by heat development. U.S. Patent No. 3,531,286, U.S. Patent No. 3,761,270,
No. 4゜021.240, Belgian Patent No. 802.5
No. 19, Research Disclosure Magazine, September 1975, pages 31 and 32, etc., describe a method of forming a color image by combining an oxidized form of a developer with a coupler, and various developers used therein.

In addition, a method of introducing a nitrogen-containing heterocyclic group into a dye, forming a silver salt, and releasing the dye by heat development is described in Research Disclosure magazine, May 1978 issue, pages 54-58 (RD-
16966).

Further, regarding the method of forming a positive color image by a thermal silver dye bleaching method, for example, see Research Disclosure magazine, April 197s issue, pages 30-32 (RD-14433).
), December 1976 issue, pages 14-15 (RD-15
227) and U.S. Pat. No. 4,235,957, useful methods for bleaching dyes are described.

In addition, a new color image forming method using heat development was developed in Japanese Patent Application Laid-Open No. 57-
No. 179840, No. 57-186774, No. 57-1
98458, No. 57-207250, No. 58-58
No. 543, No. 58-79247, No. 58-11653
No. 7, No. 58-149046, [Tsukasa 59-48764
No. 59-65839, No. 59-71046, No. 59-87450, No. 59-88730, etc.

When these are exposed to photosensitive silver halide and/or S-containing silver salts or silver by thermal development, they generate or release mobile dyes in response to or inversely to this reaction. This is a method in which the dye is transferred to a dye-fixing element.

It is preferable that the silver halide emulsion used in the stiff heat-developable photosensitive material has high sensitivity.

Chemical sensitization and spectral sensitization are known as useful methods for increasing the sensitivity of silver halide photographic emulsions.

Spectral sensitization is the process of incorporating a sensitizing dye into a silver halide photographic emulsion to extend the sensitivity of the silver halide emulsion from the short wavelength range of visible light to the long wavelength range of visible light. 7'j: A technique for increasing the sensitivity of true emulsions. Cyanine dyes, merocyanine dyes, etc. are used as sensitizing dyes, and many sensitizing dyes and methods of applying them are now known. In particular, by using two or more types of sensitizing dyes in combination, or by using a compound with a sensitizing dye in combination with a compound that itself has no or very poor spectral sensitization, it is possible to A method of obtaining a greater sensitizing effect than sensitization is known, and is called supersensitization.

Among these, a supersensitization method using a combination of two or more types of sensitizing dyes is often used.

However, the superchromic sensitization method using a combination of sensitizing dyes changes the spectral sensitization wavelength range, and therefore it is often difficult to obtain preferable spectral characteristics of the photographic emulsion.

Therefore, a supersensitization technique using a compound that does not have a spectral sensitizing effect by itself is required.

In particular, unlike cubic silver halide emulsions having (100) faces, octahedral or 14 tetrahedral silver halide emulsions having (111) planes generally have superior properties such as low fog; It was disadvantageous in terms of sensitivity because it was not susceptible to spectral sensitization by sensitive dyes. In addition, tabular silver halide emulsions having the same (111) plane have a higher surface area to volume ratio than cubic, octahedral, and tetradecahedral emulsions, so they have high sensitivity when spectrally sensitized. the dyes used for spectral sensitization are limited;
Even when spectrally sensitized, the sensitivity expected from the ratio of surface area to volume cannot be achieved.

Further, in heat-developable photosensitive materials, silver salts of benzotriazoles have been known as organic silver salt oxidizing agents, but the supersensitizing effect of this compound is hardly observed.

Furthermore, JP-A-60-194449 discloses a technique for reducing fog by using a benzotriazole compound that forms a hydrophilic group. The benzotriazole compound having t: did not exhibit any supersensitizing effect.

Under these circumstances, a supersensitization technique for silver halide emulsions having (111) planes is required.

11 Objects of the Invention The present invention's ``first objective is to provide a heat-developable photosensitive material that has high sensitivity, exhibits little change in sensitivity over time and small fog, improves the change in sensitivity due to pressure, and exhibits little change in photographic properties during storage of the processed surface. The purpose is to provide materials.

■Disclosure of the Invention These objectives are achieved by the present invention described below.

That is, the present invention provides eight objects having (111) planes, one
This is a heat-developable light-sensitive material characterized by comprising 47 silver halide emulsion layers containing one or more types of silver halide grains in the form of blood cells and tabular shapes, a sensitizing dye, and a benzotriazole.

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

The heat-developable light-sensitive material of the present invention comprises silver halide grains in the form of 8 itself and/or tetradecahedron and/or '+-plates having (111) planes which are supersensitized with hensitriazoles and sensitizing dyes. A silver halide emulsion layer containing

The sensitizing dye used in the present invention is usually a methine dye, but it also includes cyanine dyes, merocyanide dyes, complex cyanine dyes, complex merocyanine dyes, and holopolar dyes.
Contains cyanine dyes, hemicyanine dyes, styryl dyes and hemioxonol dyes. Particularly useful dyes are those belonging to cyanine dyes, merocyanine dyes, and complex merocyanine dyes.

Any of the nuclei commonly used for cyanine pigments can be used as a basic heterocyclic nucleus for the Kowara pigments. That is, viroline nucleus, oxazoline nucleus, thiazoline nucleus,
Pyrrole nucleus, oxazole nucleus, thiazole nucleus, selenazole nucleus, imidazole nucleus, tetrazole nucleus, pyridine nucleus, etc.: A nucleus in which an alicyclic hydrocarbon ring is fused to a stiff nucleus; and an aromatic hydrocarbon ring is fused to these nuclei. Nuclei such as indolenine nucleus, benzindolenine nucleus, indole nucleus, benzoxadole nucleus, naphthoxazole nucleus, benzothiazole nucleus, naphthothiazole nucleus, benzoselenazole nucleus, henzimidazole nucleus, quinoline nucleus, etc. can be applied. . These nuclei may be substituted on carbon atoms.

Merocyanine dyes or composite merocyanine dyes include a pyrazolin-5-one nucleus, a thiohydantoin nucleus, and a 2-thioxazolidine-2 nucleus having a ketomethylene structure.
9,4-dione nucleus, thiazolidine-2,4-dione nucleus,
A 5- to 6-membered heterocyclic nucleus such as a rhodanine nucleus or a thiobarbic acid nucleus can be applied.

Specific examples of sensitizing dyes useful in the present invention include the following general formulas (A) to ()(), (J) to (U), (W), (Y
) can be mentioned.

Ichikoi ((A) (X+ -) In the formula, z, z2 are heterocyclic nuclei commonly used in cyanine dyes, especially thiazole nucleus, thiazoline nucleus, benzothiazole nucleus, naphthothiazole nucleus, oxazole nucleus, oxazoline nucleus, benzoxazole Nucleus, naphthoxazole nucleus, tetrazole nucleus, pyridine nucleus, quinoline nucleus, imidacilline nucleus, imidazole nucleus, benzimidazole nucleus, naphthoimidazole nucleus 1. Selenazoline nucleus, selenazole nucleus, benzoselenazole nucleus, naphthoselenazole nucleus or indolenine nucleus, etc. Represents the atomic group necessary to complete.These nuclei are lower alkyl groups such as methyl groups,
Halogen atom, phenyl group, hydroxyl group, carbon number 1
~4 even if substituted with an alkoxy group, carboxyl group, alkoxylcarbonyl group, alkylsulfamoyl group, alkylcarbamoyl group, acetyl group, acetoxy group, cyano group, trichloromethyl group, trifluoromethyl group, nitro group, etc. good.

L1 or L2 represents a methine group or a substituted methine group.
Examples of the substituted methine group include lower alkyl groups such as methyl group and ethyl group, phenyl group, substituted phenyl group, methoxy group,
Examples include methine groups substituted with ethoxy groups and the like.

R1 and R2 are alkyl having 1 to 5 carbon atoms, 2! : Substituted alkyl group having a carboxyl group; γ-sulfopropyl group, δ-sulfobutyl group, 2-(3-sulfopropoxy)
Allyl
) group and other substituted alkyl groups commonly used as N-substituents of cyanine dyes. ml represents 1, 2 or 3.

xl- represents an acid anion group commonly used in cyanine dyes, such as iodide ion, bromide ion, p-toluenesulfonate ion, and perchlorate ion. n represents 1 or 2, and n is 1 when it has a betaine structure.

General formula (B) In the formula, Z3 is the general formula (A
) represents a heterocyclic nucleus as shown. Z4 represents an atomic group necessary to form a ketohetero nucleus commonly used in merocyanine dyes. For example, the core is rhodanine, thiohydantoin, oxindole, 2-thioxazolidinedione, 1,3-indanedione, etc.
L3 and L4 have the same meaning as L1 and L2, and R3 has the same meaning as R 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 original r group necessary to complete the benzoselenazole nucleus and indolenine nucleus. pl represents 0 or l.

R4 has the same meaning as R1 or R2, and R5 and R6 have the same meaning as R3 or R4. m3 represents 0 or 2. R7 and R3, or the same as R2, represent zero meaning. Z6, like Z4, represents α sense. Yl and Yl
is an oxygen atom, sulfur JW 7', selenium base T or =N-
R5 (R5 is a group with 8 carbon atoms such as methyl, ethyl, or propyl group)
(Represents the following alkyl group, allyl group)
and at least one of them is =N-R5 group.

wl represents 1 or 2.

General formula (D) In the formula, Z7 is Z5, Z8 is Z6, R6 is R, or R2 and R2 are P! Same as , it represents zero meaning. Y3 and Y4 have the same meaning as Yl and Yl. W2 has the same meaning as Wl.

Acupuncture, where R7 and R8 are R1, Z9 and 210 are z5, and R
3. R4 has the same meaning as p+, L9 to L++, x2 has the same meaning as Xl, and R2 has the same meaning as nl. Y5 and Y6 have the same meaning as Yl. 151m4 is 0 or 1
represents.

W3 has the same seven color meanings as Wl.

General Formula (F) In the formula, Z 11 and 212 represent an atomic group necessary to complete an unsubstituted or substituted benzene ring or an atomic group necessary to form a naphthalene ring.

R9 and RIn represent the same meaning as R1. Y7 and Y8 are oxygen atom, sulfur atom, selenium atom, l2 (all, R17 is methyl group or ethyl group), -N
RI3 (RI3 is an alkyl group, usually N of cyanine dye
- Substituted alkyl group or allyl (a
llyl), J, i) or -CH=CH-
represents. Y9 represents an atomic group necessary to form a 5- or 6-membered heterocycle.

General formula (G) Zlff, 2111 is Z I+, R14 and R15 are R
, y+o, and yo have the same meaning as Y7. Y 1
7 represents an atomic group necessary to form a 5- or 6-membered carbon ring. X3 is the same as Xl, l3 is the same as nl, and represents the α sense.

General formula (H) General formula (J) X4. R4 represents the same 5-position meaning as Xl and nl.

R6 is O or 1. m5, rn6 is 1 or 2, L
14 to L18 represent the same meaning as Ll. Z Is
represents the same meaning as Zl. R6 is P in general formula (C),
It has the same meaning as

Here, as AI, ■ I8 1 day to Also, as A2, RI8 can be cited as preferable.

RIG, R11+ are hydrogen atoms f, alkyl 1□L, ;ζ?
Represents argyl J, (, aryl'1). R1,
・Bahalogen atom, nitro J, 4, lower alkyl J9 [
, alnigoxy group, alkoxysulfonyl J, ni, alkylsulfonyl R+9, R20, and R2+ represent a hydrogen atom f-, a halogen atom, an alkyl group, a cycloalkyl group, an aryl group, a pyridine group, a carboxy group, and an alkoxycarbonyl group. Q is rhodanine, 2-thioxazolidinedione, 2-thiohydantoin, barbituric acid, etc.
Represents the raw fXT required to complete the ~6fl heterocyclic nucleus.

-Dispersion formula (K) R 22 is R1, Z IG is Zl, Ll9,L'
Xo represents the same meaning as Ll. P7 is 0 or 1,
pδ represents 1, 2 or 3.

G,, G2 may be the same or different, and R. and jointly cyclic secondary amines (e.g. pyrrolidone, 3-viroline, piperidine, piperazine,
represents the necessary atomic group to form morpholine).

X5 represents X, and R5 represents the same meaning as nl, meaning 0.

General formula (L) 〇Z 17 is Z4 and L21. L22. L=is 1,1
, G3 and G4 have the same meaning as G. p9 represents 0.1.2 or 3.

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

Here, R and R may be the same or different, and each represents an alkyl group (preferably having 8 or less carbon atoms).

In general formula (M), Y and Y are oxygen +01
102 atoms, sulfur atoms, selenium atoms, \.

! 04 (R and R are a methyl group or an ethyl group), =NR (R is an unsubstituted or substituted alkyl group or allyl group having 5 or less carbon atoms), or -CH=CH-.

In general formula (M), 2. 2 represents an atomic group necessary to form a device-changed or substituted benzene ring or naphthyl ring.

A ring containing Y and Z, or +01 containing Y
101
As a nitrogen-containing heterocycle made of a 102 ring and Z! 02 For example, thiazole nuclear systems (e.g. benzothiazole, 4-
Chlorbenzothiazole, 4-methylbenzothiazole, 5-phenylbenzothiazole, 5-methoxybenzothiazole, 5-carboxybenzothiazole, 5-ethoxycarbonylbenzothiazole, tetrahydroben-thiazole, naphtho(2,1-d)thiazole, 5-
Methoxynaphtho(1,2-d)thiazole, selenazole thread grafting (e.g. benzoselenazole, 5-chlorobenzoselenazole core, 5-methoxybenzoselenazole, 5
-methylbenzoselenazole, 5-hydroxybenzoselenazole, naphtho(2,1-d) selenazole, naphtho(1,2-d) selenazole, etc.], oxazole nuclear systems [e.g. benzoxazole, 5-chlorobenzoxazole, 5 -methylbenzoxazole, 5-phenylhendioxazole, 5-methoxybenzoxazole, 5-hydroxybenzoxazole, 5-carboxybenzoxazole, naphtho(1,2-d)oxazole, etc.], quinoline nuclei [e.g. 2-quinoline, 3 -Methyl-2-quinoline, 8-fluoro-2-quinoline, 6
- medoxy-2-quinoline, 6-hydroxy-2-quinoline, etc.), 3.3-dialkylindolenine core (e.g. 3,3-dimethylindolenine, 3.3-dimethyl-5-cyanoindolenine, 3.3 -dimethyl-5-methoxyindolenine, etc.), imidazole core (e.g.,
l-Ethylhenshiimidazole, l-methyl-5-chlorobenzimidazole, 1-methyl-5-cyanohenshiimidazole, 1-phenyl-5゜6-dichlorobenzimidazole, 1-methyl-5-trifluoromethylhenshiimidazole , 1-ethylnaphtho(1,2-d)imidazole, etc.).

In the general formula (M), Y simply represents an atomic group necessary to form a 5- or 6-membered carbon ring, or a methine chain when a ring is not formed.

In general formula (M), m101 represents 1 or 2, ×101 represents an acid residue.

” +02 represents O or 1, and is 0 when a dye or hetain is used.

L and L are methine groups or substituted methine 101
1 unit represents 2 units.

One rib ((N) +uz m +03 In the formula, Y and Y have the same meaning as Y, +03
104 101R, R has the same meaning as R, +06 107 +012 . 2
has the same meaning as Z, +03 10
4 101X has the same meaning as X, and +02 101 ``103 has the same meaning as m.

(Here, the meaning 0 means the same meaning as the definition of general formula (M).) 1 ^ 11 ■ 3 Lo = II [) In the formula, Zlo5 is 4-quinoline nucleus, 2-quinoline nucleus represents the atomic group necessary to complete the .

Z1 has the same Q meaning as Z.

10o 101 P101 does not represent 0 or 1.

"104 represents 2 or 3.

Y has the same meaning as Y, +05 101 R, R has the same meaning as R, +08 109 101 , L , L
is the same as L, it has an urgent meaning.

10:l 104 1ot (Here, the same meaning means that it has the same meaning as the definition of the general formula (M).) In the formula ``108.Z has the same meaning as Z, +09
101 R, R have the same meaning as R, +10 11+ 101 Y1o8 has the same meaning as Y and has the same meaning, X has the same meaning as X, 104 +01 ''+06 has the same meaning as m, Y , Y has the same meaning as Y.

+06 107 101 (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 +12 113 or a phenyl group or R and R are connected +12 113 represents the atomic group necessary to form a 5- or 6-membered heterocycle.

ε− difference ! one 7.0 ＝　＝ ＞　　0 \, II −〇 ■ = ■ During the ceremony, Z has the same meaning as Z, +10 101 Y has the same meaning as Y.

+09 +(11 ” II+ is oxygen atom, sulfur atom, selenium atom, =N-
Represents R (R is the same as R, meaning 0).

R has the same meaning as R and has a zero meaning.

+14 101 R- represents a group having the same meaning as R, as well as a phenyl Ib+ 101 group, a dolysyl group, a substituted phenyl group, and a substituted dolysyl group.

``110 has the same meaning as Y, ”+07 has the same meaning as m, +01 L, L has the same meaning as L, meaning 0.

+05 106 101 (Here, the same meaning means the same meaning as the definition of the general formula (M).) = Three ε Shodobon N In the formula, Z , Y , Y , Y , R11G
+09 110 11+ 1+4゜RL
and L and m are +15 105
106 107 Same meaning as in general formula (Q).

,/l.

Acupuncture ゛N-In the set, 2. 2 has the same meaning as Z, and Ill
112 101 Y and Y have the same meanings as Y , and R and R have the same meanings as R.

+17 119 101 R has the same meaning as R, ”+13 has the same meaning as Y, X has the same meaning as X, +05 101 mIQ8 has the same meaning as m.

+02 (Here, the same meaning means the same meaning as the definition of general formula (M).) General formula (T) In the formula, 2. 2 has the same meaning as Z, and! 1:]
114 101 Y, Y has the same meaning as Y, N5
116 10+ R, R has the same meaning as R, +21 122 101 X has the same meaning as X, m109 has the same meaning as m, and has the α meaning.

(In the above, the same meaning means the same meaning as the definition of general formula (FA).) R has the same meaning as R in general formula (S) +20 118
Ru.

△ 孭、'(ri・= 性性 -In the set, Y117 has the same meaning as Y, Y has the same meaning as Y, +18 101 2 has the same meaning as Z, +15 105 2 has the same meaning as Z. +16 101 R, R have the same meaning as R, 123 124 +01 q has the same meaning as 21 in general formula (C), and X
It has the same meaning as 107 +01 ``I+.'' has the same meaning as m.

(In the above, the same meaning means the same meaning as the definition of general formula (M).) R, □5 has the same Q definition as R in general formula (S), and is 1B.

In the formula, 2. 2 is Q A, same as Z, and 117
118 10i Y , Y has the same meaning as Y , +19 1
20 101 R, R have the same meaning as R, +26 127 101 X has the same meaning as X, +08 101 m111 has the same meaning as m, and +02 L has the same meaning as L.

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

, de; N=\　　　　　　　 4th - Low IH, E Sharp ~81' During the ceremony.

2. 2 cohabits with Z: righteousness, +19
120 101 Y1□1, Y is the same as Y and has zero meaning.

+22 101 R, R have the same meaning as R, +29 130 101 L, L, L, L, L+08
109 110 Ill 112'L
, L has the same meaning as L, +13 1
14 101 X has the same meaning as X, and +09 101''+12 has the same meaning as m.

(Here, the same meaning means the same meaning as the definition of general formula (M)) Specific examples of sensitizing dyes suitable for use in the present invention include:
JP-A-59-180550, pages (14) to (2)
3) I can list what is written on the page.
Representative examples thereof are shown below, but the present invention is not limited thereto.

In the present invention, - Even if a divine sensitizing dye is used alone, or two or more types of sensitizing dyes are used in combination (even if they are added in a mixture or added separately, Alternatively, it is possible to shift the timing of addition and add one type of zuma (≦addition).

The sensitizing dye can be added either at the liquid level L≦addition or in the liquid, and any conventional stirring method can be used.

Sensitizing dyes include methanol, ethanol, propatool,
Organic solvents that are compatible with water, such as fluorinated alcohols, methyl cellosolve, dimethylformamide, and acetone, and water (
Dissolve it in an alkali (or an acid FF) so that U≦tj
ll L/teb may be used, and more than 21,000 of the above may be used together. In addition, f
It may be added in S form or in the form of freeze-dried powder.

The powder may be dispersed using an activator and added to the solution.

The sensitizing dye can be added at any time during emulsion production. For example, it may be added before or during the formation of silver halide grains, it may be added at the starting surface of chemical sensitization, or during chemical sensitization, or it may be added after the completion of chemical sensitization.
It may be added up to ii.

The amount of sensitizing dye used is 1 - halogenated 3 used in emulsion production.
I (10-8 to 10-1 mol per mol or appropriate, preferably 10-7 to 10-2 mol).

The hensitriazoles used in the present invention will be explained.

In the present invention, it is necessary to use Hen-f triazole 〒r1 which does not have wood-loving properties J and C.
, L is hydroxy”, shi, carboxyl, sulfo J,
5. Ruhamoil 1.し(CON R2) , ,',
Le T) A% rle J, L(-So, N) (,) 0 taste-・j-ru.

Unreleased 1! 7II is present in 11.'1 is a human trick in general formula (I).

General formula (I) p.

In the above general formula (I), R,, R2゜R3 and R
4 is a hydrogen atom, a substituted or unsubstituted alkyl group, an aralkyl group, an alkenyl group, an alkoxy group, or an aryl group, -NRR', -COOR'', -CO
NRR'.

-N HS 02 R, SO2N RR', or -CN; R and R' each represent a hydrogen atom, a substituted or unsubstituted alkyl group, an aryl group,
or an aralkyl group, and R'' represents a substituted or unsubstituted alkyl group, aryl group, or aralkyl group).

The alkyl group represented by R, R2, R, and R4 includes a substituted or unsubstituted alkyl group having 1 to 18 carbon atoms, such as a methyl group, an ethyl group, a butyl group, an isobutyl group, a hexyl group, an octyl group, F-decyl group, 2-methoxybutyl group, etc.: As the aralkyl group, substituted or unsubstituted aralkyl group having 7 to 20 carbon atoms, such as hensyl group, β-phenethyl group, α-methylhensyl group, etc.: As the alkenyl group, carbon 3! Hlvy of i2-12
p) or unsubstituted alkenyl groups, such as propenyl group, impropenyl group, styryl group, etc.: As the alkoxy group, substituted or unsubstituted alkoxy groups having 1 to 18 carbon atoms, such as methoxy group, ethoxy group, methoxyethoxy Group ring: Examples of the aryl group include substituted or unsubstituted aryl having 6 to 14 carbon atoms, (for example, phenyl group, tolyl group, etc.).

Furthermore, as the alkyl group represented by R and R',
Placement 4 with 1 to 12 carbon atoms! a b L < is an unsubstituted alkyl group, such as a methyl group, a butyl group, an isobutyl group,
Todecylno J: As the left neararyl group, the number of carbon atoms is 6 to 1
4 substituted or unsubstituted aryl groups, such as phenyl group, tolyl group, etc.; Examples of the aralkyl group include substituted or unsubstituted aralkyl groups having 7 to 14 carbon atoms, such as benzyl group, β-phenethyl group, etc. .

The alkyl group represented by R'' has 1 to 12 carbon atoms.
Substituted or unsubstituted alkyl groups, such as methyl group, butyl group, dodecyl group, etc.; Examples of aryl groups include substituted or unsubstituted aryl groups having 6 to 14 carbon atoms, such as phenyl group, tolyl group, naphthyl group, etc. Examples of the aralkyl group include substituted or unsubstituted aralkyl groups having 7 to 14 carbon atoms, such as benzyl group, β-phenethyl group, α-methylbenzyl group, etc.

In the above, "substituted or unsubstituted" substituents are:
Groups other than hydrophilic groups, such as halogen groups, alkoxy groups, aryloxy groups, alkyl groups, aryl groups, ester groups, alkylsulfonyl groups, arylsulfonyl groups, alkylsulfonylamino groups, arylsulfonylamino groups, alkylcarbonylamino group, arylcarbonylamino group, etc.

Specific examples of the benzotriazoles of the present invention are listed below.

J-I I-2H ■ -12 ■ -13 The amount of hensitriazoles added in the present invention is 10 to 10-6 mol per mol of silver halide, preferably lo-
The amount is preferably 2 to 10-5 mol. The amount added corresponds to 10' to 10 to 1 mol, preferably 103 to 1 mol, per mol of sensitizing dye.

The benzotriazoles used in the present invention can be directly dispersed in an emulsion, or can be dissolved in an appropriate solvent (for example, methyl alcohol, ethyl alcohol, methyl cellosolve, water, etc.) or a mixed solvent thereof to form an emulsion. It can also be added. In addition, it can be added to the emulsion in the form of a solution or a dispersion in a colloid according to the method for adding sensitizing dyes. Also, Japanese Patent Application Publication No. 50-80
It can also be dispersed and added into the emulsion by the method described in Japanese Patent No. 119. The benzotriazole may be added to the amount of the sensitizing dye, may be added at the same time, or may be added after the sensitizing dye is added before coating.

In the present invention, in addition to the supersensitization using benzotriazoles described above, various known supersensitization techniques can be used in combination. For example, aminostyryl compounds substituted with nitrogen-containing heterologous groups (e.g., U.S. Pat. No. 2,933,390
No. 3,635,721), formaldehyde condensates of aromatic organic acids (e.g., U.S. Pat.
, 743,510), cadmium salts, azaindene compounds, etc. may also be used. Also, U.S. Patent No. 3,615,613, U.S. Patent No. 3,615,641,
Combinations described in Japanese Patent No. 3,617.295 and Japanese Patent No. 3,635,721 can also be used.

The silver halide emulsion used in the present invention contains at least one of octahedral, tetradecahedral, and tabular silver halide grains having (111) planes.

That is, the morphology of silver halide grains suitable for use in the present invention is 8 which is substantially formed by (111) planes.
These are hedral grains, tetradecahedral grains formed from (111) planes and (100) planes, or tabular grains mainly formed from (111) planes.

The ratio of (111) planes to (100) planes on the surface of the tetradecahedral silver halide grains used in the present invention is not limited to a specific one, but the larger the ratio of (111) planes, the more effective the present invention is. The sensitization effect of the method is greater.

Further, the tabular grains used in the present invention have a thickness of 1 grain or 0.
, 5- or less, the diameter is at least 0.6, and the average aspect ratio is 5 or more.
No. 8525, No. 58-111935, No. 5B-111
No. 936, No. 58-111937, No. 58-1139
No. 34, No. 58-113928, No. 58-11393
No. 0, No. 58-113926, U.S. Patent No. 4,414
, No. 310, No. 4,435.499, 0LS3.2
It is described in No. 41,646, etc.

In the present invention, 50% by weight or more of the total silver halide in the silver halide emulsion layer to be supersensitized with a sensitizing dye and a benzotriazole has octahedral, tetradecahedral and Preferably, the silver halide grains are/or tabular silver halide grains. Particularly preferred is 70% by weight or more.

Silver halides that can be used in the present invention include silver chloride, silver bromide,
Alternatively, silver chlorobromide, silver chloroiodide, or silver chloroiodobromide may be used.

Epitaxial junction type silver halide grains can be used (JP-A-56-16124, U.S. Patent No. 4
, No. 094, 684).

In the present invention, a monodisperse emulsion with a nearly uniform particle size distribution (
JP 57-178235, JP 58-100846, JP 58-14829, International Publication No. 83102338A
1, European Patent No. 64.412A3 and European Patent No. 83.3
77A1 etc.) and polydisperse emulsions may also be used.

Particle shape, halogen composition, particle size, particle size!
Two or more types of silver halides having different values such as 5 may be used in combination. The gradation can also be adjusted by mixing two or more types of monodispersed emulsions with different grain sizes.

The silver halide that can be used in the present invention may have a uniform halogen composition within the grain, or may have a multiple structure (so-called core/shell emulsion) in which the composition differs between the surface and the inside (Japanese Patent Application Laid-open No. No. 57-154232, No. 58-10853
No. 3, No. 59-48755, No. 59-52237,
US Patent No. 4,433,048 and European Patent No. 10
No. 0,984).

When preparing a core/shell emulsion, the core particles may be formed first and then the shell portion may be formed as is, or the emulsion used for the core particles may be washed with water for desalting and then the shell portion may be formed. It's okay. A method of forming a shell after forming a core particle is disclosed in Japanese Patent Application No. 1983.
-248469 and Japanese Patent Application No. 60-56569.

The photographic emulsion used in the present invention is B. Grafkide (P,
GIafkides), Chimie eL Physique (Chimie eL Physique
PhoLographique (Paul Montel Corporation, 1967)], Photographic Emulsion Chemistry (1'Photographic Emulsion C) by G.F. Duffin
heI! l1stry) (The Focal Breath T
he Focal Press) Shama, 1966],
V. L. Zelikman et al.
net et, al), Making Ant Coating Photographic Emulsion El:/ (Ma
King and CoatingPhoto）Hra
phicEmulsion (The Focal Press, Inc., 1964).

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

It is also possible to use a method in which particles are formed in an excess of silver ions (so-called back-mixing method). As a type of simultaneous mixing method, p in the liquid phase in which silver halide is produced is
It is also possible to use a method in which Ag is kept constant, the so-called condorold double-shot method.

Furthermore, in order to accelerate grain growth, the concentration, addition -1 or addition rate of silver salts and halogen salts may be increased (JP-A-55-142329, JP-A No. 55-15).
8124, U.S. Pat. No. 3,650,757, etc.).

During or after grain formation, the surface of the silver halide grains may be substituted with halogen to form poorly soluble silver halide grains.

In the step of forming silver halide grains used in the present invention, ammonia and
Organic thioether derivatives described in No. 11386 or sulfur-containing compounds described in JP-A-53-144319 can be used.

In the process of particle formation or physical ripening, cadmium salt, zinc salt, lead salt, thallium salt, etc. may be present.

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

The soluble salts of the 1L agent are usually removed after the formation of a precipitate or after the physical formation, but as a first step for this purpose, the long-known zudel water washing method in which seratin is gelatinized may be used; Inorganic salts consisting of polyvalent anions, such as sodium sulfate, anionic surfactants, anionic polymers (e.g. polystyrene sulfonic acid), or gelatin conductors (e.g. aliphatic acylated seratin, hexaaromatic acylated seratin, aromatic carbamoyl A sedimentation method (flocculation) using chloride celadin may also be used. The step of removing soluble salts may be omitted.

The silver halide emulsion used in the present invention may have a surface Ni image where the latent image is mainly formed on the grain surface, or an internal latent image formed inside the grain. internal d
) It is also possible to use a direct reversal emulsion which is a combination of an image-forming emulsion and a nucleating agent. Internal τI) image reduction suitable for this purpose is disclosed in U.S. Pat. No. 2,592,250;
．． No. 276, JP 58-3534 and JP 57
-136641 etc. Preferred nucleating agents for combination in the present invention are U.S. Pat.
No. 27,552, No. 4,245,037, No. 4,
255゜511, same No. 4,266.031, same No. 4
．． No. 276.364 and OLS No. 2,635.316
It is stated in the number etc.

The photographic emulsion used in the present invention is preferably chemically sensitized. For chemical sensitization, for example Die Grundlag
en der Photography Pro
zcsse mij Si! berhalogenid
en) (Akademische Veriagsgesellschaft)
sellschafl), 1968] 675-7
The sulfur sensitization method, five-element sensitization method, selenium sensitization method, 57 metal sensitization method, etc. described on page 34 can be used alone or in combination.

For example, in sulfur sensitization, sulfur sensitizers, that is, compounds containing sulfur 16 obtained by reacting with active gelatin or silver, include thiosulfate, allylthiocarbamide, thiourea, allyl isothiacyanate, cystine, P-)luenethiosulfonate, rhodan, mercapto compounds, etc. are used. Others, U.S. Patent No. 1,74.9
No. 44, No. 2,410,689, No. 2.278,
947, 2q2.72a, s68, 3,65
6,955 etc. can also be used.

Addition of sulfur as a sensitizer 5. Snoring varies over a considerable range under various conditions, and is preferably about 10-7 to 10-2 mole per mole of silver.

In gold sensitization, the oxidation number of gold is + as a gold sensitizer.
It may be monovalent or +trivalent, and specifically, chlorauric acid salt, potassium chloroaurate, auric trichloride,
Potassium auric thiocyanate, potassium iodooleate, tetracyano auric acid, etc. are used.

The amount of these gold sensitizers added can vary over a considerable range under different conditions, but is usually 10 to 1 mole of silver.
It is preferably about -9 to 10-t mol.

In the present invention, selenium sensitization can also be used, and selenium sensitizers include aliphatic isoselenocyanates such as allyl isoselenocyanate, selenoureas, selenoketones, selenamides, selenocarboxylic acids and esters. selenophosphates, diethylselenide, diethylselenide, and other selenides can be used. Specific examples thereof are described in U.S. Pat.
No. 74,944, No. 1.602,592, No. 1,
No. 623,499.

The amount of selenium sensitizer added can be selected from a wide range, but is usually preferably from 10<-7> to 10<-2> mol per 1 mol of silver.

In addition to the above-mentioned sulfur sensitization, gold sensitization, and selenium sensitization, reducing substances (such as stannous salts, amines, and drazine derivatives,
Reduction sensitization using formamidine sulfinic acid, silane compounds): Noble metal compounds (e.g., gold complex salts, pt
A noble metal sensitization method using complex salts of metals of group 1 of the periodic table such as , Ir, and Pd can also be used in combination.

Regarding the reduction sensitization method, see U.S. Patent Nos. 2,983.609, 2,419,974, and 4,054,458
No. 2,399, U.S. Pat. No. 2,399, et al.
No. 083, No. 2.448,060, British Patent No. 61
It is described in each specification such as No. 8,061.

Furthermore, typical combinations of sensitizers include gold/sulfur sensitization and gold/selenium sensitization, but other combinations are also possible. In gold/sulfur sensitization, the ratio of the two sensitizers used varies depending on the aging conditions, etc., but usually about 1 to 1000 moles of the sulfur sensitizer are used per 1 mole of the gold sensitizer.

In gold/selenium sensitization, it is usually preferable to use about 1 to 1000 moles of selenium sensitizer per 1 mole of gold sensitizer.

In gold/sulfur sensitization or gold/selenium sensitization, the gold sensitizer may be added at the same time as the sulfur sensitizer or selenium sensitizer, or during or after sulfur or selenium sensitization.

Particularly preferred chemical sensitizations for use in the present invention are sulfur sensitization or gold-sulfur sensitization.

In the present invention, these chemical sensitizers are treated by conventional methods.
Added to silver halide photographic emulsions. That is, a water-soluble compound is added as an aqueous solution, and an organic solvent-soluble compound is added as a solution in an organic solvent that is easily miscible with water, such as methanol or ethanol.

In addition, there are no particular restrictions on the conditions such as pH, I)Ag, and temperature during chemical sensitization, but the pH value is preferably 4 to 9, particularly 5 to 8, and the Ag value is preferably 5 to 11, particularly 7. ~10
It is preferable to keep it at In addition, the temperature is 40 to 9
0°C, especially 45-75°C is preferred.

In the present invention, JP-A-58-126526, JP-A-58-126526,
As described in No. 8-215644, a nitrogen-containing heterocyclic compound may be present during chemical sensitization.

Examples of the heterocycle of the nitrogen-containing heterocyclic compound used in the present invention include the following. Pyrazole ring, pyrimidine ring, triazole ring, thiadiazole ring, tetrazole ring, pyridazine ring, triazine ring, triazolotriazole ring, diazaindene ring, triazaindene ring, tetrazaindene ring, pentazaindene ring, benzimidazole ring, indazole ring , benzothiazole ring, etc. Further, the heterocycle may have various substituents. For example, hydroxyl group,
Alkyl group, amino group, alkylthio group, halogen atom, cyano group, substituted alkyl group, substituted amino group (hydroxyamino group, alkylamino group, dialkylamine group,
arylamino group, etc.). Among these, hydroxyl group is preferred.

As the nitrogen-containing heterocyclic compound, those having an azaindene ring are preferable, and among them, hydroxytriazaindene,
Hydroxytetraazaindene, hydroxypentaazaindene and the like are preferred. A typical example is 4-
Hydroxy-6-methyl-1,3,3a,7-chitrazaindene: 7-hydroxy-1,2,3,4°6-bentaazaindene: 2,4-dihydroxy-6-methyl-
1,3a,7-doriazaindene:4-hydroxy-5
, 6-cyclobentiru 1.3.3a, 7-chitrazaindene and the like.

The amount of the nitrogen-containing heterocyclic compound used during chemical sensitization can be varied over a wide range depending on the size of the silver halide grains, halogen composition, and chemical sensitization conditions, but is usually 1 to 1 per mole of i halide. IXfO'+ng, preferably 1 to 1X103B is used.

Further, in order to further reduce the decrease in sensitivity and increase in fog during storage of the silver halide emulsion of the present invention, it is preferable to use sulfonamide phenols and sulfonamide naphthols in combination. Here, sulfonamidophenols or sulfonamide naphthols more specifically mean a compound represented by the following general formula (a).

General formula (a) all However, -NHSO2R1 is bonded to the carbon atom located at the 2nd or 4th position with respect to the carbon atom to which the 10H group is bonded. In the formula, R1 represents a substituted or unsubstituted alkyl group, cycloalkyl group, aralkyl group, aryl group, amino group, or heterocyclic group. Ba1l represents a ballast group. Y represents a carbon atom necessary to complete a benzene nucleus or a naphthalene nucleus.

Examples of the above preferred R1 include a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, such as a methyl group, an ethyl group, a dodecyl group; a substituted or unsubstituted cycloalkyl group having 5 to 30 carbon atoms, e.g. Cyclohexyl group ring:
a substituted or unsubstituted aralkyl group having 7 to 30 carbon atoms,
For example, benzyl group, β-phenethyl group, etc.: carbon number 6-3
0 substituted or unsubstituted aryl groups, such as phenyl group, naphthyl group, tolyl group, xylyl group Ring: 0 to 0 carbon atoms
30 substituted or unsubstituted amino groups, such as amino group, methylamine group, isopropylamino group, cyclohexylamino group, phenylamino group, benzylamino group,
N,N-dimethylamino group, N-methyl-N-ethylamino group, N,N-diisopropylamino group, N,N-dicyclohexylamino group, N,N-diphenylamino group, N.

N-dibenzylamino group: Substituted or unsubstituted heterocyclic group, such as pyridyl group, furyl group, chenyl group, etc.

In addition, to explain in detail the substituents of the above-mentioned alkyl groups, aryl groups, etc., the substituents include, for example, halogen atoms (chlorine atoms, bromine atoms, etc.), amino groups, alkoxy groups, aryloxy groups, hydroxyl groups, aryl groups, carboxyl groups, etc. Amide group, alkanoyloxy group, benzoyloxy group, ureido group, carbamate group, carbamoyloxy group, carbonate group, carboxy group, alkyl group (methyl group, ethyl group, propyl group, etc.), acylamino group, sulfamoyl group, ester group, Examples include an alkylsulfonyl group, an alkylsulfonylamino group, and an arylsulfonylamino group.

Ba1l represents an organic ballast group that can make the compound represented by general formula (a) non-diffusible. However, when R1 is a non-diffusible group, Ba1l may be omitted.

The nature of the ballast is not critical as long as the ballast imparts diffusion resistance to the compound. Typical ballast groups are straight or branched alkyl groups attached directly or indirectly to the compound, and directly or indirectly attached to the benzene nucleus. It includes benzene-based and naphthalene-based aromatic groups.

Effective ballast groups generally have at least 8 carbon atoms, for example substituted or unsubstituted alkyl groups having 8 to 30 carbon atoms, amide groups having 8 to 30 carbon atoms, Keto group having 8 to 30 carbon atoms, 8 carbon atoms
Examples include an alkoxy group having ~22 carbon atoms, an alkylthio group having 8 to 30 carbon atoms, and the like. Also,
Examples of indirect bonding include bonding via a carbamoyl group or sulfamoyl group (the nitrogen atom contained in these groups is bonded to the ballast group) as shown below.

Sodium-CN-Bal1 -S 02 N-Ba 11 Here, R2 is a hydrogen atom, an alkyl group having 1 to 7 carbon atoms (
For example, methyl group, ethyl group, etc.), cycloalkyl group (eg, cyclohexyl group, etc.), or aryl group (eg, phenyl group, etc.) are preferable.

Y represents a group of carbon atoms necessary to complete the benzene nucleus or naphthalene nucleus.

In addition, when Y represents the atomic group necessary to complete the naphthalene nucleus, Ba11 and R1 can be bonded to any of the ring systems thus formed.

The compounds represented by general formula (a) include those having substituents.

Examples of substituents include halogen atoms, substituted or unsubstituted alkyl groups, cycloalkyl groups, aralkyl groups, aryl groups, heterocyclic groups, alkoxy groups, aryloxy groups, acyl groups, alkyloxycarbonyl groups, and aryloxycarbonyl groups. group, carbamoyl group, sulfamoyl group, alkylsulfonyl group, arylsulfonyl group, acylamino group, alkylthio group, arylthio group, etc. Two or more of these substituents may be present. Also, bicyclo(2,2,1)hept-2- attached to each other to form a ring (for example, a Hensen ring completed by Y)
ene, cyclohexane, etc.).

Examples of conjugates of the compound represented by the general formula (a) are shown below, but the compounds of the present invention are not limited thereto.

Compounds such as I''11koshi n3 may be used alone or in combination of two or more.

The amount added is 0.0005 to 20 times mole relative to silver, and a particularly useful range of addition amount is o, ooi to 4 times mole.

In the present invention, an organic metal salt can also be used as an oxidizing agent together with photosensitive silver halide. In this case, the photosensitive silver halide and the organic metal salt need to be in contact or at a close distance.

Among such organic metal salts, organic silver salts are particularly preferably used.

Examples of organic compounds that can be used to form the above-mentioned organic silver salt oxidizing agent include Japanese Patent Application No. 59-228551, page 37-
Page 39, U.S. Pat. No. 4,500.626, No. 52FIa~
There is a compound described in Column 53, etc.+7). Also, special request in Showa 6
Also useful are silver salts of carboxylic acids having an alkynyl group, such as silver phenylpropiolate described in Japanese Patent Application No. 113235, and acetylene silver described in Japanese Patent Application No. 60-90089.

Two or more types of organic silver salts may be used in combination.

The above-mentioned organic silver salts contain, per mol of photosensitive silver halide,
0.01 to 10 mol, preferably 0.01 to 1
Moles can be used together. The total coating amount of photosensitive silver halide and i silver salt is 5 OnH to 1 in terms of silver.
0g/rn' is the current power.

In the present invention, silver can be used as the image forming material. It may also contain a compound that generates or releases a mobile dye in response to or inversely to this reaction when silver ions are reduced to silver under high temperature conditions, that is, a dye-donating substance. can.

Examples of the dye-donating substances used in the present invention include:
Compounds that form pigments by oxidative coupling reactions (
couplers). This coupler is 4
It may be an equivalent coupler or a 2-equivalent coupler. Also,
Two-equivalent couplers that have a diffusion-resistant group as a leaving group and form a diffusible dye by oxidative coupling reaction are also preferred. Specific examples of developers and couplers can be found in "The Theory of the Photographic Process" by James, 4th edition (T.H.).

James The Theory of the
PhotographicProcess”) 291~
334 pages and 354-361 pages, JP-A-58-12
No. 3533, No. 58-149046, No. 58-149
No. 047, No. 59-111148, No. 59-1243
No. 99, No. 59-174835, No. 59-23153
No. 9, No. 59-231540, No. 60-2950,
No. 60-2951, No. 60-14242, No. 60-
It is described in detail in No. 23474, No. 60-66249, etc.

Another example of the dye-donating substance is a compound that has the function of releasing or diffusing a diffusible dye in an imagewise manner. This type of compound can be represented by the following general formula (LI).

(Dye-X)n-Y (LI)Dy
e represents a dye group, a temporarily shortened dye group, or a dye precursor group; to cause a difference in the diffusivity of the compound represented by (Dye-X)n-Y, or to release Dye and increase the diffusivity between the released Dye and (Dye-X)n-Y. represents a group having the property of causing a difference in , n represents 1 or 2, and when n is 2, two
-X may be the same or different.

As a specific example of the dye-donating substance represented by the general formula (LI), 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. 3,362.819, 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 through an intramolecular nucleophilic substitution reaction is disclosed in U.S. Patent No. 3,
No. 980,479, etc., and JP-A-49-111.628, etc., disclose substances that release diffusible dyes through an intramolecular rewinding reaction of the inoxacilone ring.

Another example is to make the dye-releasing compound into an oxidized form without dye-releasing ability and coexist with a reducing agent or its precursor, and after development, the reducing agent that remains unoxidized allows light to pass through and become diffusive. A method for releasing a dye has also been devised, and a specific example of a dye-donating substance used in this method is disclosed in Japanese Patent Application Laid-Open No. 53
-110,827, 54-130,927, 5
It is described in No. 6-164,342 and No. 53-35.533. Japanese Patent Application No. 60-244,873 describes a compound that releases a diffusible dye when the N-0 bond is cleaved by a remaining reducing agent as a dye-donating substance that releases a diffusible dye using a similar mechanism. It's been done.

Furthermore, as described in JP-A-59-185333, a donor-acceptor reaction occurs in the presence of a base and releases a diffusible dye, but when it reacts with an oxidized form of a reducing agent, dye release does not substantially occur. Non-diffusible compounds (LDA compounds) can also be used.

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.

On the other hand, as a substance that releases a diffusible dye at the part where the phenomenon occurs, there is a coupler that has a diffusible dye as a leaving group and that releases a diffusible dye by reaction with an oxidized form of a reducing agent (DDR coupler). However, British Patent No. 1,330,52
No. 4, Special Publication No. 1986-39.165, British Patent No. 3゜4
No. 43.940, etc., and is preferably used in the present invention.

In addition, in methods using these reducing agents, image contamination due to oxidative decomposition products of the reducing agent becomes a serious problem. Dye-releasing compounds (DRR compounds) have also been devised and are particularly advantageously used in the present invention. Representative examples include U.S. Pat.
JP-A No. 4,336,322, JP-A No. 59-65839, JP-A No. 59-69839, JP-A No. 53-3819, JP-A No. 51
-104,343, Research Disclosure Magazine No. 17465, U.S. Patent No. 3,725,062, U.S. Patent No. 3,728,113, U.S. Patent No. 3,443,939, JP 58-116,537 , No. 57-179840,
It is a dye-donating substance described in US Pat. No. 4,500,626 and the like. Specific examples of this type of dye-donating substance include the compounds described in columns 22pJJ to 44 of the aforementioned U.S. Pat. No. 4,500,626, among which the compounds described in the aforementioned U.S. patent (1)～
(3), (10) to (13), (16) to (19)
), (28) to (30), (33) to (35), (38
) to (40) and (42) to (64) are preferred. Compounds described on pages 80 to 87 of Japanese Patent Application No. 59-246468 are also useful. In addition, as dye-donating substances other than those mentioned above, dye silver compounds in which a dye is combined with an R-containing silver salt (Research Disclosure magazine, May 1978 issue, pages 54-58, etc.), heat-developable silver dye bleaching method Azo dyes used in (U.S. Patent No. 4,235,957, Research Disclosure, April 1976 issue, 30-
32, etc.), leuco dye (U.S. Pat. No. 3,985°56)
No. 5, No. 4,022,617, etc.) can also be used.

The dye-providing compounds described above and hydrophobic additives such as the image-forming accelerators described below are described in U.S. Pat.
It can be introduced into the layer of the photosensitive material by a known method such as the method described in No. 7. In this case, JP-A-59
No. -83154, No. 59-178451, No. 59-1
No. 78452, No. 59-178453, No. 59-17
No. 8454, No. 59-178455, No. 59-178
A high boiling point organic solvent such as that described in No. 457 may be used in combination with a low boiling point organic solvent having a boiling point of 50° C. to 160° C., if necessary.

The amount of the high-boiling organic solvent is 10 g or less, preferably 5 g or less per 1 g of the dye-providing substance 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 the case of a compound that is substantially insoluble in water, it can be dispersed and contained in the binder in the form of fine particles other than the feeding method.

Various surfactants can be used when dispersing hydrophobic substances into hydrophilic colloids.

For example, Nos. (37) to (3) of JP-A No. 59-157636.
The surfactants listed on page 8) can be used.

In the present invention, it is desirable to include a reducing substance in the light-sensitive material. Reducing substances include those generally known as reducing agents, as well as the aforementioned dye-donating substances having reducing properties.

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.

Examples of reducing agents used in the present invention include U.S. Pat.
, No. 500,626, columns 49-50, same No. 4,483
, No. 914, columns 30-31, JP-A-60-14033
No. 5, pages (■7) to (18), JP-A-1284-1984
No. 38, No. 60-128436, No. 60-12843
Reducing agents described in No. 9, No. 60-128437, etc. can be used. Also, JP-A-56-138゜736, JP-A-56-138゜736,
Reducing agent precursors such as those described in US Pat. No. 7-40,245 and US Pat. No. 4,330,617 can also be used.

Combinations of various reducing agents can also be used, such as those disclosed in US Pat. No. 3,039,869.

In the present invention, the amount of reducing agent added is 0 per mole of silver.
．． 01 to 20 mol, particularly preferably 0.1 to 10 mol.

In the present invention, a compound that activates development and stabilizes images can be used in the light-sensitive material. For specific compounds preferably used, see U.S. Patent Nos. 4 and 5.
No. 00.626, columns 51-52.

Various antifoggants or photographic stabilizers can be used in the present invention. Examples include Research Disclosure magazine, December 1978 issue 24-2.
Azoles and azaindenes described on page 5, JP-A-59
Nitrogen-containing carboxylic acids and phosphoric acids described in Japanese Patent Application No. 168442, or mercapto compounds and metal salts thereof described in JP-A-59-111636, Japanese Patent Application No. 60-22
Acetylene compounds described in No. 8267 are used.

In the present invention, the photosensitive material may contain an image toning agent if necessary. Specific examples of effective toning agents include compounds described in Japanese Patent Application No. 59-268926, pages 92-93.

In order to obtain a wide range of colors in the chromaticity diagram using the three primary colors yellow, magenta, and cyan, it is necessary to use a light-sensitive element having at least three silver halide emulsion layers each sensitive to a different spectral region. good. For example, there are combinations of three layers such as a blue-sensitive layer, a green-sensitive layer, and a red-sensitive layer, and a combination of a green-sensitive layer, a red-sensitive layer, and an infrared-sensitive layer. Each of these photosensitive layers may be divided into two or more layers, if necessary.

The photosensitive material used in the present invention may optionally contain various additives known for use in heat-developable photosensitive materials and layers other than the photosensitive layer, such as a J layer, an intermediate layer, an antistatic layer, an antihalation layer, and a dye. It can have a release layer, a matte layer, etc. to facilitate peeling off from the fixing element. Various additives are listed in Research Disclosure Magazine, 1978, 6.
Plasticizers, matting agents, dyes for improving sharpness, which are described in pages 9 to 15 of the Japanese issue, Japanese Patent Application No. 59-209563, etc.
Additives include antihalation dyes, surfactants, optical brighteners, antislip agents, antioxidants, and antifading agents. In particular, the protective layer usually contains an organic or inorganic matting agent to prevent adhesion. Further, this protective layer may contain a mordant and an ultraviolet absorber. protective layer,
Each intermediate layer may be composed of two or more layers.

Further, the intermediate layer may contain a reducing agent to prevent color fading and color mixing, an ultraviolet absorber, and a white pigment such as titanium dioxide. A white pigment may be added not only to the intermediate layer but also to the emulsion layer for the purpose of improving sensitivity.

The photographic material of the present invention is composed of a light-sensitive material that forms or releases a dye by heat development and, if necessary, a dye-fixing material that fixes the dye.

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 dye-fixing material are separately coated on two supports. It is broadly divided into two types: a form in which it is coated on the same support and a form in which it is coated on the same support. The relationship between the light-sensitive material and the dye-fixing material, the relationship with the support, and the relationship with the white reflective layer are described in Japanese Patent Application No. 59-268926, pages 58-59, and U.S. Pat. No. 4,500,626, No. 579. The relationships described in can also be applied to the present application.

The dye fixing material preferably used in the present invention is as follows.

It has at least one layer containing a mordant and a binder.

As the mordant, those known in the photographic field can be used.
Specific examples thereof include those described in Japanese Patent Application No. 59-209563. The dye fixing material may be provided with auxiliary layers such as a protective layer, a peeling layer, and an anti-curl layer, if necessary. In particular, it is useful to provide a protective layer. One or more of the above layers may include hydrophilic heat solvents, plasticizers, anti-fade agents, UV absorbers, slip agents, matting agents, antioxidants, and dispersed vinyl to increase dimensional stability. Compounds, surfactants, optical brighteners, etc. may also be included. Further, particularly in a system in which thermal development and dye transfer are carried out simultaneously in the presence of a small amount of water, it is preferable to include a base and/or a base precursor as described below in the dye fixing material in order to improve the storage stability of the photosensitive material.
Specific examples of the stiff additives are described on pages 101 to 120 of Japanese Patent Application No. 59-209563.

In the present invention, an image formation accelerator can be used in the light-sensitive material and/or the dye-fixing material. Image formation promoters include promoting redox reactions between silver salt oxidizing agents and reducing agents;
It has functions such as promoting reactions such as generation of dye from dye-donating substance, decomposition of dye, and release of diffusible dye, and promotion of movement of dye from the light-sensitive material layer to the dye fixing layer. The functions include bases or base precursors, nucleophilic compounds, high-boiling organic solvents (oils), thermal solvents,
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 above-mentioned promoting effects. For details of these, please refer to the patent application in 1983.
No. 213978, No. 67-71.

There are various other methods of generating bases, and the compounds used in these methods are all useful as base precursors. For example, a method of generating a base by mixing a sparingly soluble metal compound and a compound (referred to as a complex-forming compound) that undergoes a complex-forming reaction with the metal ions constituting the sparingly soluble metal compound, as described in Japanese Patent Application No. 169585/1985. There is also a method of generating a base by electrolysis as described in Japanese Patent Application No. 74702/1983.

The face-to-face method is particularly effective. Examples of poorly soluble metal compounds include carbonates, hydroxides, and oxides of zinc, aluminum, calcium, barium, and the like. Also,
Regarding complex-forming compounds, see e.g.
RJ, Sa+1Lh) co-author, “Critical Stability Constant”
illity (:instants) J, Volumes 4 and 5, BlennumPress
is detailed in. Specifically, aminocarboxylic acids,
Imidinoacetic acids, pyridylcarboxylic acids, aminophosphoric acids, carboxylic acids (mono, di, tri, and tetracarboxylic acids and compounds with further substituents such as phosphono, hydroxy, oxo, ester, amide, alkoxy, mercapto, alkylthio, and phosphino) , hydroxamic acids, polyacrylates, polyphosphoric acids, etc., and salts of alkali metals, guanidines, amidines, or quaternary ammonium.

It is advantageous to add the poorly soluble metal compound and the complex-forming compound to the light-sensitive material and the dye-fixing material separately.

Various development stoppers can be used in the light-sensitive material and/or dye-fixing material of the present invention in order to always obtain a constant image despite fluctuations in processing temperature and processing time during development.

The development stopper referred to here is a compound that neutralizes the base immediately after proper development or reacts with the base to lower the base concentration in the film and stop development, or a compound that inhibits development by interacting with silver and silver salts. It is a compound that Specifically, examples include acid precursors that release acids when heated, electrophilic compounds that undergo a substitution reaction with coexisting bases when heated, nitrogen-containing heterocyclic compounds, mercapto compounds, and their precursors (for example, Application No. 58-216928, No. 59-4
No. 8305, No. 59-85834 or No. 59-85
Compounds described in No. 836, etc. ) Compounds that release mercapto compounds upon heating are also useful; for example, Japanese Patent Application No. 190173/1982
-268926, 59-246468, 60-
No. 26038, No. 60-22602, No. 60-260
There are compounds described in No. 39, No. 60-24665, No. 60-29892, and No. 59-176350.

A hydrophilic binder can be used for the photosensitive material and/or dye fixing material of the present invention. Typical hydrophilic binders are transparent or translucent hydrophilic binders, such as protein binders such as gelatin and gelatin derivatives, natural substances such as cellulose derivatives, polysaccharides such as starch and gum arabic, and polyvinylpyrrolidone. , synthetic polymeric materials such as water-soluble polyvinyl compounds such as acrylamide polymers. Dispersed vinyl compounds, which are used in latex form and increase the dimensional stability of the photographic material, can also be used. These binders can be used alone or in combination.

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

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 less than 1 cc of solvent per 1 g of binder, preferably 0.
．． A suitable amount is 5 cc or less, more preferably 0.3 cc or less.

The constituent layers (photographic emulsion layer, dye fixing layer, etc.) of the light-sensitive material and/or dye fixing material of the present invention may contain an inorganic or organic hardening agent.

Specific examples of hardening agents can be found in Japanese Patent Application No. 59-268926, pages 94 to 95, and Japanese Patent Application Laid-open No. 59-157636 (
Examples include those described on page 38), and these can be used alone or in combination.

Furthermore, in order to promote dye transfer, a wood-philic thermal solvent that is solid at low temperatures and soluble at high temperatures may be incorporated into the light-sensitive material or dye-fixing material.

The hydrophilic heat solvent may be incorporated into either the photosensitive material or the dye fixing material, or may be incorporated into both. Further, the layer to be incorporated may be an emulsion layer, an intermediate layer, a protective layer, or a dye fixing layer, but it is preferably incorporated in the dye fixing layer and/or a layer adjacent thereto. Examples of wood-philic thermal solvents include ureas, pyridines, amides, sulfonamides, imides, alnyls, oximes, and other heterocycles. Further, in order to promote dye transfer, a high boiling point printing press solvent may be included in the light-sensitive material and/or the dye fixing material.

The support used in the light-sensitive material and/or dye-fixing material of the present invention is one that can withstand processing temperatures. As general supports, glass, paper, polymer films, metals and their analogs are used, as well as Japanese Patent Application No. 59-268926, pages 95-96.
The supports listed on the page can be used.

The photosensitive material and/or the dye-fixing material may have a conductive heating layer as a heating means for heat development or diffusion transfer of the dye.

The transparent or opaque heating element in this case can be made using conventionally known techniques for producing resistive heating elements.
As a resistance heating element, there are two methods: a method using a thin film of an inorganic material exhibiting semiconductivity, and a method using a thin film of an organic material in which conductive fine particles are dispersed in a binder. Materials that can be used in the Kowara method include those described in Japanese Patent Application No. 151,815/1983.

In the present invention, the method for coating the heat-developable photosensitive layer, protective layer, intermediate layer, undercoat layer, back layer, dye fixing layer, and other layers is the method described in columns TfJ55-56 of U.S. Patent No. 4,500,626. is applicable.

As a light source for image exposure for recording an image on a photosensitive material, radiation including visible light can be used. In general, light sources used for normal color printing, such as tungsten lamps, water 211 iQ, halogen lamps such as iodine lamps, xenon lamps, laser light sources,
CRT light source, light emitting diode (LED), etc., patent application filed in 1982
-268926, page 100 and U.S. Patent No. 4.500.
The light source described in column 56 of No. 626 can be used.

In the present invention, the thermal development and dye transfer steps may be performed independently or simultaneously.
Further, = may be continuous in the sense that development is followed by transfer in one step.

For example, (1) After exposing the photosensitive material imagewise and heating it,
There are two methods: (1) a method in which dye-fixing materials are stacked and heated if necessary to transfer the mobile dye to the dye-fixing material; and (2) a method in which a light-sensitive material is imagewise exposed, and the dye-fixing materials are stacked and heated.

The methods (+) and (2) above can be carried out in the substantial absence of water or in the presence of a trace amount of water.

The heating temperature in the heat development step can be developed at about 0°C to about 250°C, and particularly useful is about 0°C to about 180°C. When heating in the presence of a trace amount of water, the heating temperature limit is below the boiling point. When the transfer process is performed after the heat development process, the heating temperature in the transfer process can be in the range from the temperature in the heat development process to room temperature, but in particular, it is 50°C or higher, which is about 10°C lower than the temperature in the heat development process. More preferably up to temperature.

A preferred image forming method in the present invention involves heating in the presence of a trace amount of water and a base and/or a base precursor after or simultaneously with image exposure, and at the same time as development, diffusion is generated in a portion corresponding to or inversely corresponding to a silver image. The coloring matter is transferred to the dye fixing layer. According to this method, the production or release reaction of the diffusible dye proceeds extremely quickly, and the movement of the diffusible dye to the dye fixing layer also proceeds rapidly, so that a high-density color image can be obtained in a short time.

The amount of water used in this embodiment is at least 0.1 times, preferably 0.1 times, the total 215 h mold break of the photosensitive material and dye fixing material, which corresponds to the maximum swelling volume of this total coating. Below the weight of the solvent (especially the maximum swelling volume of the entire coated film 1)
The weight of the total coating film is subtracted from the weight of the solvent corresponding to h
A small amount (1 or less) is sufficient.

The state of the film when it swells is unstable, and depending on the conditions, it may cause local bleeding.To avoid this, use water equivalent to the volume at maximum swelling of the total coating film thickness of the photosensitive material and dye fixing material. It is preferable that the amount is less than or equal to . Specifically, 1g per square meter of the total area of photosensitive material and dye fixing material.
A range of 50 g to 35 g, particularly 2 g to 35 g and even 3 g to 25 g is preferred.

The base and/or base precursor used in this embodiment can be incorporated into both the light-sensitive material and the dye-fixing material.
It can also be supplied dissolved in water.

In the above embodiment, the image forming reaction system contains, as a base precursor, a basic metal compound that is sparingly soluble in water, and a compound that undergoes a complex formation reaction with a metal ion constituting the sparingly soluble metal compound using water as a medium; Preferably, the pH of the system is raised by reaction of these two compounds upon heating.

Here, the image reaction system means a region where an image forming reaction occurs. Specifically, layers belonging to both photosensitive materials and dye fixing materials can be mentioned. If two or more layers are present, any of the layers may be used.

The poorly soluble metal compound and the complex forming compound need to be added at least in separate layers in order to prevent them from reacting before the development process. For example, in a so-called mono-sheet material in which a light-sensitive material and a dye-fixing material are provided on the same support, it is preferable that the two additive layers are separate layers, with one or more layers interposed between them. A more preferred embodiment is one in which the poorly soluble metal compound and the complex-forming compound are contained in layers provided on separate supports. for example,
It is preferable that the poorly soluble metal compound is contained in a light-sensitive material and the complex-forming compound is contained in a dye-fixing material having a support separate from the light-sensitive material. The complex-forming compound may be supplied after being dissolved in water to be coexisting. Hardly soluble metal compounds are disclosed in Japanese Patent Application Publication No. 5
6-174830, 53-102733, etc., and the average particle size thereof is 50 microns or less.
Particularly preferred is 5 microns or less. The sparingly soluble metal compound may be added to any layer of the photosensitive material, such as the photosensitive layer, intermediate layer, or protective layer, or may be added after being divided into two or more layers.

The amount of a poorly soluble metal compound or complex-forming compound to be added to the layer on the support depends on the type of compound, the particle size of the poorly soluble metal compound, the rate of complex formation reaction, etc. It is appropriate to use it in an amount of 50 weight percent or less, and more preferably a range of 0.01 weight percent to 40 weight percent. In addition, when the complex-forming compound is dissolved in water and supplied, 0,005mol to 5n+ol per liter,
In particular, a concentration of 0.05 mol to 211IO1 is preferred. Furthermore, in the present invention, the content of the complex-forming compound in the reaction system is set at a molar ratio of 1/1 to the content of the poorly soluble metal compound.
It is preferably 100 times to 100 times, particularly 1/10 times to 20 times.

The method for adding water to the photosensitive layer or dye fixing layer is as follows:
For example, page 101, line 9 of Japanese Patent Application No. 59-268926.
There is a method described on page 102, line 4.

As a heating means in the development and/or transfer process, a hot plate, an iron, a hot roller, etc.
There is a means described in No. 8926, page 102, line 14 to page 103, line 11. Alternatively, a layer of a conductive material such as graphite, carbon black, or metal may be applied to the photosensitive material and/or the dye-fixing material, and the conductive layer may be heated directly by passing an electric current through the layer. .

The pressure conditions and method of applying pressure when overlapping the photosensitive material and the dye-fixing material and bringing them into close contact are disclosed in Japanese Patent Application No. 59-2689.
The method described in No. 26, pages 103 to 104 can be applied.

Any of a variety of thermal development equipment can be used to process the photographic materials of this invention. For example, JP-A No. 59-75247,
Apparatuses described in Japanese Patent No. 59-177547, No. 59-181353, No. 60-18951, Japanese Utility Model Application No. 116734-1980, etc. are preferably used.

■Specific effects of the invention According to the present invention, silver halide grains containing octahedral, tetradecahedral and/or tabular silver halide grains having (111) faces are supersensitized with hensitriazoles and a sensitizing dye. Since it contains a silver halide emulsion, a highly sensitive photothermographic material can be obtained.

Further, sensitivity fluctuations and fog over time are small, and sensitivity enhancement due to pressure is improved.

Furthermore, since color sensitization is stably performed, there are small fluctuations in photographic properties such as sensitivity and fog due to fluctuations in temperature and humidity during exposure of the light-sensitive material.

Furthermore, during the production of light-sensitive materials, there is little change in photographic properties in the solution state until the silver halide emulsion is coated.

(2) Specific Examples of the Invention Hereinafter, specific examples of the present invention will be shown and the present invention will be explained in more detail.

Example 1 This article describes how to make a silver halide emulsion.

Gelatin aqueous solution (20 g of gelatin and 110 (Glh) 2S (C11□) 2S (C11
2) Double solution of 1 mol/2 potassium bromide aqueous solution and silver nitrate aqueous solution (silver nitrate 0.59 mol dissolved in 600 ml of water) The pAg was maintained at 8, 0°, 8.6, and 9.2, respectively, and added over 60 minutes using a jet method. Washing desalination? 140 g gelatin and water 200111
was added to adjust the pl+ to 6 and 5:A, and the optimum chemical sensitization was carried out using sodium thiosulfate to obtain emulsions 1 to 3 having the following artificial characteristics corresponding to each pAg. . Yield is 700g.

Table work 1 Cube 0.45μ 92 14
Facepiece 0.45μ 1゜3 Octahedron
0.4 μ 12 *Here, the coefficient of variation is the value obtained by dividing the standard deviation S of the particle size distribution by the average particle size 7, multiplied by 100.

Particles were prepared in exactly the same manner as Emulsion 3, 0.8 g of Exemplary Compound (+) was added during chemical sensitization, and optimal chemical sensitization was performed using sodium thiosulfate.

1.5 (octahedral emulsion in which a nitrogen-containing heterocyclic compound was present during chemical sensitization) A well-stirred gelatin aqueous solution (20 g of gelatin in 1000 nu of water, 4 ml of sodium chloride)
150ml of an aqueous solution containing 9.5g of potassium bromide and 1.5g of sodium chloride and 150ml of an aqueous solution containing 17g of silver nitrate were added simultaneously at equal flow rates over 6 minutes. did. Next, 400 ml of an aqueous solution containing 60 g of potassium bromide and 400 ml of an aqueous solution containing 83 g of silver nitrate were mixed at the same time while maintaining PAg at 9.0.
Added over 0 minutes. Washing desalination? Add 140 g of gelatin and 200 g of water, pl! 6.5, adjusted to pAg 8.4, optimally chemically sensitized using triethylthiourea and 4-hydroxy-6-methyl-1,3,3a,7-titrazaindene, and with an average particle size of 0.4μ. An octahedral emulsion 5; 700H was obtained.

A well-stirred gelatin aqueous solution (15 g of gelatin, 6 g of potassium bromide)
An aqueous solution containing 8 g of potassium bromide in a solution containing 8 g of potassium bromide.

100 mN and an aqueous solution containing 10 g of silver nitrate were added simultaneously over 5 minutes. Thereafter, the temperature of the solution was raised to 75°C, and 5001N of an aqueous solution containing 65g of potassium bromide and 1.5g of potassium iodide and 500Il of an aqueous solution containing 90g of silver nitrate were added.
1) was added simultaneously over 40 minutes while maintaining the Ag at 9.2.

After washing with water and desalting, 40 g of seratin and 200 mIQ of water were added to adjust the pH to 6.5 and pAg to 8.5, and optimal chemical sensitization was performed using chloroauric acid and sodium thiosulfate. In this way, 700 g of tabular silver iodobromide emulsion 6 having an average grain size of 1.2 μm and an iodine content of 2.5% in the shell portion and an aspect ratio of 8 was obtained.

A well-stirred gelatin aqueous solution (dissolve 7 g of gelatin and 4 g of potassium bromide in 1,000 ml of water and keep warm at 25°C) 60 cc of an aqueous solution containing 8 g of potassium bromide and 60 cc of an aqueous solution containing 10 g of silver nitrate
c was added at the same time over a period of 1 minute. Then gelatin 30
The temperature of the aqueous solution was raised to 65°C, and 200 cc of an aqueous solution containing 24 g of potassium bromide and 200 cc of an aqueous solution containing 30 g of silver nitrate were simultaneously added over 20 minutes while maintaining l) Ag at 8.5. In addition, sodium chloride 2
5 g of potassium bromide and 300 cc of an aqueous solution containing 40 g of silver nitrate were simultaneously added over 20 minutes. After washing with water and salting for 1 time, add 40g of gelatin and 2 parts of water.
00 was added and the pH was adjusted to 6.0. Adjust ρ^g to 7.3,
Triethylthiourea and 4-hydroxy-6-methyl-1
,3,3a,7-chitrazaindene was used for optimal chemical sensitization, with an average particle size of 1.3μ and an aspect ratio of 6.
700 g of tabular silver chlorobromide emulsion 7 of No. 5 was obtained.

This article describes how to make benzotriazole silver emulsion.

28 g of gelatin and 13.2 g of hensitriazole were dissolved in 300 ml of water. This solution was kept at 40° C. and stirred, and a solution of 17 g of silver nitrate dissolved in 100 ml of water was added over 4 minutes. After that, desalinate and adjust the pH to 7.
8 to obtain 400 g of benzotriazole silver emulsion.

This article describes how to make a dispersion of organic silver salt.

20 g of gelatin and 5.9 g of 4-acetylaminophenylpropiolic acid were mixed with 10 g of 0.1% sodium hydroxide aqueous solution.
00- and ethanol 200-. Add this liquid to 4
The mixture was kept at 0° C. and stirred, and a solution of 4.5 g of silver nitrate dissolved in 200 ml of water was added over 5 minutes. The pH of the dispersion was adjusted and excess salt was removed by settling. After this, adjust the pH to 6.
．． 3 to obtain a dispersion of organic silver salt in a yield of 300 g.

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

Weighed 5 g of cyan dye-donating substance (8), 0.5 g of sodium succinate 2-ethyl-hexyl ester sulfonate as a surfactant, and 10 g of triisononyl phosphate, Ethyl acetate 30111 was added and dissolved by heating to about 60°C to form a homogeneous solution.
After stirring and mixing this solution and 100 g of a 10% solution of lime-treated gelatin, the mixture was heated to 1100 g for 10 minutes using a homogenizer.
Dispersion was carried out at 00 rpm. This dispersion is called a dispersion of a cyan dye-providing substance.

(A) (a) Next, the above components were mixed in the order listed, and the exposure +J1. I made a coating liquid.

a)1. rselfhensitriazole SRa cut 10gb
)-G silver halide emulsions 1 to 4 15g C) O, oos% methanol solution of sensitizing dye (8) 5ccd) Dispersion of the above cyan dye-providing substance 25g C) 5% aqueous solution of the following compound 5111C*
H1900 ((:ilx Cll2O-)8H'') 20% aqueous dispersion of zinc hydroxide 6 gg) Dispersion of the above-mentioned R silver salt 15 g Also, at the same time as the above C) was added, hensitriazoles were added as shown in Table 1. was added.

To this mixture were added an 8I agent (polystyrene-p-sodium sulfonate) and water to make it 100 mN. This solution was applied to a polyethylene terephthalate film having a thickness of 180 mm to a wet film thickness of 50 mm.

Furthermore, the following composition is added as a protective layer on top of this: a) gelatin (
10% aqueous solution) 30g) 1,2-bis(vinylsulfonylacetamido)ethane 2% aqueous fi
5 if c) water 701
ml was applied to a wet film thickness of 30 mm and dried to prepare a photosensitive material (Table ■).

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

Dissolve 10g of poly(methyl acrylate-N,N,N-trimethyl-N-vinylbenzylammonium chloride) (the ratio of methyl acrylate and vinylbenzylammonium chloride is 1:1) in 175-water to give a 10%
It was uniformly mixed with 100 g of lime-treated gelatin. Add 2,4-dichloro-6-hydroxy-1,3,5 to this mixture.
-25 iJl of a 4% aqueous solution of 1-riazine was added and coated uniformly to a wet film thickness of 90 mm on a paper support laminated with polyethylene in which titanium dioxide was dispersed.

Furthermore, add 10 g of guanidine pyriconate and 18 m of water.
1.20 g of 10% gelatin, 1% aqueous solution of sodium succinate-2-ethyl-hexyl ester sulfonate 4.8-
A mixed and dissolved solution is applied to a wet film thickness of 30 mm, and after drying, it is used as a dye fixing material having a mordant layer.

Fuji photographic film is added to the photosensitive material made as above.
It was constructed using a 5C-74 filter manufactured by Kogyo Corporation. Imagewise exposure was made for 1 second at 500 lux through an infrared photoresolving filter.

101 ffi/ba of water was supplied to the emulsion side of the exposed light-sensitive material using a wire bar, and the material was then pressed together so that only one surface was in contact with the -F dye fixing material.

When the dye-fixing material heated for 20 seconds was removed from the light-sensitive material using a heat roller whose temperature was adjusted so that the temperature of the water-absorbed film was 90 to 95 DEG C., a bright cyan image was obtained. The obtained cyan image was measured using a Maches reflection densitometer (RD-519), and the results shown in Table 2 were obtained.

Table ■ 2 1 Cube (8) I-1 (3X1
0-') +0.25 0.143 1
Standing 7j' body (8) I 1 (9X10-3
) +0.32 0.1:]]4214T# (8
) −0,050,155214i? 1li(,
Jin (8) I-1 (3X10'-3)
,0.68 0.1:]6214m
(8) I-1 (9X10-3) +0.750.12
738 Miyabi (8) -o,eo O,12838N
B (8) I-1 (3xlO-3) +1.230.
10938 Miyabi (8) I-1 (9xlO-3) +1.
:150.081038 Miyabi (8) l-2 (6xlO-
') +1.300.091138 secret(8) l-8(
6xlO-3) +1.200.091458iYu
(8) -0-700,111558Uftn
(8) I-1 (6xlO-3) +1.080.07
166 Flat plate (8) -0,100,1
5176 flat plate (8) I-2 (6X10-3) ++
, so 0.09187 flat plate (8)
-0,150,14197 flat plate (8) l-2 (6
X10-3) +1.45 0.10*Relative sensitivity Relative value of the reciprocal of dew grain necessary to give fog +0.3,
The sensitivity of Emulsion 1 to which no benzitriazo7m was added was set to 0.

As is clear from Table 2, in the case of cubic silver halide emulsions, only a slight increase in sensitivity is observed even when benzotriazoles are used in combination, whereas in the case of octahedral and 14
In the case of hedral and tabular silver halide emulsions, an extremely large increase in sensitivity (supersensitization effect) was obtained by the combined use of benzotriazoles. Furthermore, benzotriazoles without a hydrophilic group exhibit a superior supersensitizing effect compared to benzotriazoles having a hydrophilic group such as a sulfo group.

In addition, the above-mentioned sensitizing dye (8) can be used as sensitizing dye (2), (3).
, (4) was used (however, minus blue sensitivity was examined for each), and the remarkable supersensitizing effect of the present invention was observed for these sensitizing dyes as well.

On the other hand, in order to control the degree of sensitivity to pressure, photosensitive materials 4 and 5 were bent at 180° along a 6 mm diameter iron rod under conditions of 25°C and 40% relative humidity. , exposure and heat development were carried out in the same manner as above. the result,
In the photosensitive material 5 of the present invention, no change was observed in the folded area, but in the comparison photosensitive material 4, an increase in density was observed in the folded area, indicating that sensitization was also caused by pressure. Ta.

Furthermore, it was confirmed that the photosensitive material 5 of the present invention shows less change in sensitivity and fog values due to fluctuations in temperature and humidity during exposure than the comparative photosensitive material 4. Furthermore, after preparing the coating solution of Photosensitive Material 5 of the present invention, it was stored at room temperature for 5 hours and then coated, and the photographic performance of the photosensitive material made was almost the same as that of the photosensitive material that was coated immediately after preparing the coating solution. When the coating solution of Comparative Photosensitive Material 4 was stored in the same manner, a significant decrease in sensitivity was observed.

Example 2 This article describes how to make a silver halide emulsion.

1 Eyebrow 1 A well-stirred gelatin aqueous solution (20 g of gelatin and 110 (11:1 h) 2S (C1h) 2S (C1h) 2 in 1000 ml of water)
Aqueous solution 600111 containing 70 g of potassium bromide and 2 g of potassium iodide and 600 aqueous solution containing 100 g of silver nitrate (dissolved and kept at 50 ° C.)
- was simultaneously added over 50 minutes while maintaining the pAg at 9.2. Thereafter, 60 ml of a 0.2% methanol solution of sensitizing dye (5) was added. Next, wash with water, desalinate, add 40g of gelatin and 200ml of water to pH 6.5, pAg 8.5.
The emulsion was adjusted to 700 g, and was optimally chemically sensitized using sodium thiosulfate to obtain 700 g of a red-sensitive octahedral silver iodobromide emulsion 8 with an average size of 0.4 μm.

An aqueous solution 6 containing 65 g of potassium bromide and 4 g of sodium chloride in a gelatin aqueous solution (20 g of gelatin, 4 g of sodium chloride, and 0.015 g dissolved in 1000 mit of water and kept at 65°C), which is stirred well.
600 mf of an aqueous solution containing 00 Ii and 100 g of silver nitrate
f1 was added simultaneously over 60 minutes. 0.1% methanol solution of sensitizing dye (4) 10 at the same time as adding silver nitrate
The addition started at 0 cc and continued for 50 minutes. After washing with water and desalting, add 40g of gelatin and 200ml of water to pl+6
．． 5. The pAg was adjusted to 8.0 and chemically sensitized optimally with triethylthiourea to obtain 9 nia 00 g of an octahedral green-sensitive silver chlorobromide emulsion with an average size of 0.5 μm. These emulsions 8
, 9 was used to prepare a photosensitive material (Table ■) in the same manner as in Example 1.

This photosensitive material was exposed to 500 lux for 1 second using a tungsten bulb through a minus blue filter. The results obtained by processing in the same manner as in Example 1 are shown in Table m.

Table ■ Photosensitivity General 11 Crystal Habit Sensitization Hensitriazoles Relative* Fog material Dye (added quantum mol/mole Ag) Sensitivity 20 8 Octahedron (5) 0 (u quasi) 0.1821 8 8 uip1
(5) I-1 (6X10-3 +0
．． 75 f), +422 9 octahedron (4
) 0 shout quasi) 0.162398 Miyabi (4) I-1
(6xlO-3) +0.55 0.11*Relative sensitivity The value of photosensitive material 20 or 22 was set to 0 as a relative value of the reciprocal of the exposure amount necessary to give a density of fog +0.3.

The supersensitizing effect of the present invention was also clearly observed in emulsions such as Emulsions 8 and 9, which were prepared by adding a sensitizing dye during the formation of silver halide grains.

Example 3 The photosensitive material prepared in Example 1 (Table ■) was heated at 50°C - 20%
The sample was left for 4 days under conditions of RH535 DEG C.-80% RH, and then treated in the same manner as in Example 2, and changes in sensitivity and fog before and after the forced test were examined.

The results are shown in Table ■.

Further, in the photosensitive material 8 of Example 1, the compound (1
A photosensitive material 8' was prepared in the same manner except that the following comparative compound was used in an equimolar amount in place of 7).

+141 Table ■ 1-0.35 +0.05-0.20 +0.133-
0.15 +0.03 -0.09 +0.
127-0.30 +0.04-0.35 +0.09
8-0.03 +0.01-0.02 +0.0210
-0.02 +0.01~0.01 +0.0112-
0.45 +0.08-0.25 +0.1313-0
．． 01 +0.01 +0.02014-0.34
+0.06 ~0.25 +0.1215-0
．． 02 +0.01 +0.01 +0.
0117-0.03 +0.02 +0.01 +0.
0219-0. o2 +0.01-0.01 +0.0
38'-0,10+0.10-0.08 +0.14 From Table 1 above, the photosensitive material of the present invention has less sensitivity fluctuations and fog over time before exposure than a photosensitive material that does not contain benzotriazoles. It can be seen that the increase is extremely small. Furthermore, by using the sulfonamidophenols or sulfonamide naphthols of the present invention,
Photosensitive material 8' using other reducing antifoggants
It can be seen that a significantly superior effect of improving storage stability can be obtained.

Example 4 The preparation of a dispersion of a yellow dye-providing substance will be described.

4 g of the following yellow dye-providing substance (B), (C) I
g, compound (17) of general formula (a) used in Example 10
．． A dispersion of a yellow dye-providing substance was prepared in exactly the same manner as in Example 1, except that 1 g of compound (b) and 0.15 g of compound (b) were used.

We will describe how to make a dispersion of a magenta dye-donating substance.

5 g of the following magenta dye-donating substance (D), Example 1
0.15 g of compound (17) of general formula (a) used in
A dispersion of a magenta dye-providing substance was prepared in exactly the same manner as in the preparation of a dispersion of a cyan dye-providing substance, except that 0.1 g of compound (b) was used.

(B) (C) (D) Using these materials, a color photosensitive material 40 having a multilayer structure as shown in Table V was prepared. Further, in the color photosensitive material 40, compound I-1 was added to the first layer, third layer, and fifth layer at a concentration of 5 mg/rn', 2 mg/rn', and 2 mg/rn', respectively. A color photosensitive material 41 having a multilayer structure was produced in the same manner except for coating.

Each of the photosensitive materials 40 and 41 was passed through a three-color separation filter of G, R, and IR using a high-intensity sensitometer Mark manufactured by EG&G.
After a 10-4 second exposure with Vn, the sample was processed as in Example 1 using the same dye fixing material used in Example 1. Further, the above-mentioned photosensitive materials 40 and 41 were subjected to strongly controlled aging under the same conditions as in Example 3, and then subjected to light exposure and heat development treatment in the same manner as above.

As a result, when the photosensitive material 41 is used, the photosensitive material 40
Higher sensitivity and development acceleration effects were observed in all hues of yellow, magenta, and cyan, and there was less decrease in sensitivity and increase in fog during storage.

Applicant Fuji Photo Film Co., Ltd. Agent Patent Attorney Minoru Watanabe K167. Oyo E Jl" IW -1 し゛"・-°1

Claims (3)

[Claims] (1) It is characterized by having a silver halide emulsion layer containing one or more of octahedral, tetradecahedral, and tabular silver halide grains having (111) planes, a sensitizing dye, and a benzotriazole. Heat-developable photosensitive material. (2) The photothermographic material according to claim 1, further comprising a dye-donating substance. (3) The photothermographic material according to claim 1 or 2, further comprising at least one of sulfonamide phenols and sulfonamide naphthols.