JPS61281232A - Heat developable photosensitive element - Google Patents

Abstract

PURPOSE:To form a heat-developable photosensitive element small in desensitization in heat development and high in sensitivity by incorporating the sensitizing dye having a fundamental 5-membered hetero ring comprising a TeCN chain as ring constituent atoms in a photosensitive element. CONSTITUTION:The photosensitive element contains the sensitizing dye having at least one fundamental 5-membered hetero ring comprising a TeCN chain as ring constituent atoms. The 5-membered hetero ring of the sensitizing dye may have various structures in accordance with the number of unsaturated bonds (2, 1, 0) and the combination state of the N atom, and it is typified by a tellurazole ring, a tellurazoline ring, a tellurazolium ring, and tellurazolinium ring. The photosensitive element contains the sensitizing dye, especially preferably, in an amt. of 4X10<-5>-1X10<-3>mol per mol of silver halide.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a heat-developable photosensitive element, and more particularly to a highly sensitive heat-developable photosensitive element that exhibits little desensitization during heat development.

[Conventional technology]

The conventionally known photographic method using photosensitive silver halide is superior to other photographic methods in terms of photosensitivity, gradation, image preservation, etc., and is the most widely put into practical use. .

However, since this method uses wet processing for processing steps such as development, fixing, and water washing, processing is time-consuming and labor-intensive, and there are concerns that the processing chemicals may affect the human body, or the processing room and work area may be affected. There are many problems, such as concerns about contamination of people by the chemicals mentioned above, and consideration of pollution caused by waste liquid. Therefore, it has been desired to develop a photosensitive material that uses photosensitive silver halide and can be dry processed.

Many proposals have been made regarding the above-mentioned dry processing photographic method, and among them, heat-developable photosensitive materials in which the developing step can be performed by heat treatment are attracting attention as photosensitive materials that meet the above-mentioned requirements.

Regarding such heat-developable photosensitive materials, for example,
This is described in Japanese Patent No. 4921 and No. 43-4924, and discloses a photosensitive material comprising an organic silver salt, silver halide, and a reducing agent.

Attempts have been made to improve such heat-developable photosensitive materials and obtain color images by various methods.

For example, Research Disclosure No. 15108,
No. 15127, No. 16966, U.S. Patent No. 3.53
No. 1,286, No. 3,761.270 and No. 3
, 764, 328 and the like disclose heat-developable color photosensitive materials in which a color image is formed by a reaction between an oxidized product of an aromatic primary amine developing agent and a coupler.

These heat-developable photosensitive elements usually form images by being heat-developed after exposure or at the same time as exposure, but heat development is generally carried out at a high temperature of 80°C or higher.
The influence on silver halide is not small. One of the biggest effects is desensitization due to thermal development.

In other words, the sensitivity when an exposed heat-developable photosensitive element is developed at a temperature of 40°C or lower with a generally widely used wet photographic processing solution is the sensitivity when the exposed heat-developable photosensitive element is thermally developed at a temperature of 80°C or higher. was found to be lower. Furthermore, it has been revealed that in photosensitive elements containing sensitizing dyes, desensitization due to heat development is significant. This phenomenon is thought to be due to a part of the latent image formed on the exposed silver halide being thermally bleached during thermal development, but this is not clear.

Adding a sensitizing dye to silver halide gives silver halide high photosensitivity from visible light to infrared light, and is an essential material in photographic elements. Improvement of undesirable desensitization is strongly desired.

[Purpose of the invention]

Therefore, an object of the present invention is to reduce desensitization during thermal development.
An object of the present invention is to provide a highly sensitive heat-developable photosensitive element.

[Structure of the invention]

As a result of extensive studies, the present inventor has discovered that in a heat-developable photosensitive element having at least silver halide, a reducing agent, and a pygou on a support, the photosensitive element has a nitrogen atom and a tellurium atom sandwiched between carbon atoms as ring-constituting atoms. A sensitizing dye (hereinafter referred to as
The present inventors have discovered that the objects of the present invention can be achieved by a heat-developable photosensitive element characterized by containing a sensitizing dye of the present invention, and have thus arrived at the present invention.

The sensitizing dye of the present invention is a sensitizing dye having as at least one basic liquid a 5-membered polycyclic ring nucleus having a nitrogen atom and a tellurium atom as ring constituent atoms with a carbon atom in between, and Various structures can be taken depending on the presence or absence and the bonding state with the nitrogen atom, but representative examples include those having a tellurazole ring nucleus, a telluriazoline ring nucleus, a tellurium azolium ring nucleus, and a tellurium azolinium ring nucleus.

Among these, the following general formulas (1) to (It
/).

General formula CI) General formula (n) General formula c degree] General formula (ff) (Yp) In the formula, Rls and R8 are each a hydrogen atom or a monovalent group that may be substituted, and at least one are each an optionally substituted alkyl group or aryl group,
Preferably, each is a hydrogen atom or an optionally substituted alkyl group or aryl group, and at least one of them is an optionally substituted alkyl group or aryl group.

or a group of atoms that together complete a ring (preferably 5 to 6 members) fused to a ring containing tellurium and nitrogen, preferably an aromatic ring fused directly to the ring containing tellurium and nitrogen; A group of atoms completing an aromatic ring fused to a non-aromatic ring fused to a ring containing tellurium and nitrogen.

Rs and R each represent a hydrogen atom or an optionally substituted hydrocarbon moiety, R4 represents a hydrogen atom, an optionally substituted hydrocarbon moiety, or an amino group, and R6 represents an optionally substituted hydrocarbon moiety. R6 represents a hydrogen atom or a quaternized substituent, Y- represents a counter ion, and p represents O or a positive integer for matching ionic charges.

R5 and R7 may cooperate with R2 to complete a 5- to 6-membered fused heterocycle. R8 may cooperate with R4 or R6 to complete a fused heterocycle (preferably 5-6 membered).

R? may be combined with Ro to complete a fused heterocycle (preferably 5- to 6-membered).

Y-, which represents a counter ion, is a halogen atom (chlor,
Representative examples include anions such as bromine and iodine atoms) and sulfonic acids (methanesulfonic acid, trifluoromethanesulfonic acid, p-toluenesulfonic acid, etc.).

The ring completed by R and R1 is typically a 5- to 6-membered aromatic ring such as benzene, naphthalene, thiophene, benzothiophenefuran, benzofuran, and pyridine.

These rings may be substituted. Examples of substituents include hydroxy, hydroxyalkyl groups (e.g., hydroxyethyl, hydroxypropyl, etc.), alkyl groups (e.g., methyl, ethyl, isopropyl, t-butyl, etc.)
, alkoxy groups (e.g., methoxy, ethoxy, β-methoxyethoxy, γ-carboxypropyloxy, etc.), aryloxy (e.g., phenoxy, p-chlorophenoxy, etc.), aryl groups (e.g., p-)lyl,
phenyl, di-hydroxyphenyl, p-hydroxyphenyl, 2-hydroxynaphthyl, etc.), halogen atoms (e.g. chloro, fluoro, bromine, etc.), trifluoromethyl groups, amino groups (e.g. dimethylamino group, groups such as diethylamino group), cycloalkyl group (
For example, cyclohexyl group), sia group, carbamoyl group (
Examples include carbamoyl, N,N-dimethylcarbamoyl, N,N-diethylcarbamoyl, alkoxycarbonyl groups (eg, ethoxycarbonyl), and alkylthio groups (eg, methylthio).

Also, R2 and R5, R1 and R? , R1 and R3, R1 and R5
Examples of rings in which are bonded and fused with a tellurium-containing heterocycle include the following.

R1 is preferably an aryl group or an alkyl group, an alkenyl group, an alkynyl group, each of which may be substituted, R4 is preferably an aliphatic hydrocarbon which may be substituted, and R2 is preferably an unsubstituted R1 is preferably an optionally substituted aliphatic hydrocarbon.

The above description of general formulas (1) to (IV) is the same for each general formula described below.

The basic nucleus of the sensitizing dye according to the invention, for example a tellurium azolium ring, preferably forms part of the chromophore, so that it is in the form of a tellurium azolium ring in one resonance extreme and in the form of a tellurium azolylidene in the second resonance extreme. Translocates to the ring.

In a particularly preferred form, at least one of the sensitizing dyes of the invention is a polymethine dye containing a tellurium azolium ring. Such dyes include cyan, nin and merocyanine dyes. The dye can contain two nuclei linked through a methine linkage, which is most commonly present.

These dyes are sometimes referred to as simple cyanine or merocyanine to distinguish them from those containing three or more nuclei, called complex cyanine or merocyanine dyes. In addition to the above, these polymethine dyes used in the photographic elements of this invention can take the form of hemicyanine, styryl, neomycin, azacyanine, and allopolarcyanine dyes. Such dyes are direct analogs of conventional dyes in these classes, and the difference is at least in place of other divalent chalcogens! The presence of divalent tellurium atoms in the chalcogenazolium liquid.

General formula (U) can form a merocyanine dye represented by the following general formula (V) by Rs.

-8, EV) In the formula, FLI-FL* and R1 have the same meaning as in the general formula Cl0), and the same ones are exemplified.

Furthermore, R5 may be combined with H to complete a 5- to 6-membered fused heterocycle.

E represents an acidic nucleus, Lt and R each represent a methine bond which may be independently substituted, and n represents 0.1 or 2.

Examples of fused heterocycles formed by R5 and R5 include the following.

The acidic nucleus E represented by E in the general formula [V) and the following formulas can take the form of any ordinary merocyanine acidic nucleus. A typical example where the acidic nucleus is an acyclic group is shown below using a one-limit resonance structure.

a b c 7dIn the formula,
RlR, R and R each represent a -valent substituent, such as an alkyl group (e.g. methyl group, ethyl group, octyl group, dodecyl group, 5ea-octyl group, etc.), an aryl group (e.g. p-tolyl group, phenyl group, etc.) ), or a heterocyclic group (for example, a benzofuryl group).

A typical example where the acidic nucleus is a cyclic group is shown below using one limit resonance structure.

In the formula, R is a -valent substituent, such as an unsubstituted alkyl group (e.g., methyl group, ethyl group, etc.), substituted alkyl group (e.g., methoxyethyl group, hydroxyethyl group, carboxyethyl group, sulfoethyl group, carbamoylethyl group) etc),
Examples include aryl groups (eg, phenyl group) and cyclic groups (eg, pyridyl group, benzothiazolyl group, etc.). Further, a substituent such as a methyl group or a phenyl group can be placed on the ring. You can choose from etc.

Preferred compounds of general formula (V) are general formula [■'] [■
″].

General formula (VI) R1, R*, R8, n and E represent the same meanings as in the above general formula (V).

General formula [■'] R,, R1, R1, and E are synonymous with general formula (V), and R
(1) represents a hydrogen atom, an alkyl group, an alkoxy group, an aryloxy group, an aryl group, an aralkyl group, and a cyano group, or represents an atomic group that forms a 5- to 6-membered ring together with R1. Further, R"' and R" represent a hydrogen atom and an alkyl group, respectively.

General formula [■″] R1, R1, R1, and E are synonymous with general formula (V), and R
(4) is a hydrogen atom, alkyl (e.g., methyl, ethyl, etc.), alkoxy (e.g., methoxy, ethoxy, etc.), aryloxy (e.g., phenoxy group), aryl (e.g., phenyl group), aralkyl (e.g., benzyl group), group) and a cyano group.

R(4) and R1 may jointly form a 5- to 6-membered ring.

R(ll), R"' and CFRc") are hydrogen atoms, alkyl (e.g., methyl, ethyl, propyl, etc.), aralkyl (e.g., benzici, phenethyl, etc.), aryl (e.g., phenyl), petero ring (for example, groups such as chenyl and furyl), alkyloxy (for example, groups such as methoxy and ethoxy), aryloxy (for example, phenoxy group), cyano group, amino (for example, groups such as dimethylamino and anilino), Represents each group such as alkylthio (for example, methylthio group), arylthio (for example, phenylthio group), and an acidic nucleus. However, R(4), R"', R"
', R'' are not all hydrogen atoms. k is 0 or 1.

In a particularly preferred form, the compounds of the invention are cyanine dyes. These dyes can be symmetrical, so that they contain at least two identical tellurium azolium nuclei, or they can be asymmetrical, in which case the nuclei can each be a different tellurium azolium nucleus, or they can contain at least one tellurium azolium nucleus. tellurium azolium core and one or more conventional basic heterocyclic cyanine dye cores. The cores are linked via methine bonds, which can consist of a single methine group or a group of methine groups.

As mentioned above, the tellurium azolium ring can produce absorption shifts due to bathochromic effects, so fewer methine groups can be used to absorb longer wavelength electromagnetic radiation. However, methine linkages of up to 13 or more consecutive methine groups can be incorporated into the dye if desired.

The general formula (ill/) can form a cyanine dye represented by the general formula [■] by R6.

General formula [■] In the formula, Rt, Rt and R7 have the same meanings as in general formula (IV). R,, is preferably a quaternized substituent; R,
represents a quaternized substituent, and R1 jointly with Lt represents 5-
A G-membered fused heterocycle may also be completed.

L t, L y, L a, L 4 and ri each independently optionally substituted methine group, and n is 0.1 or 2.
, m is 0 or 1, Q is the atomic group that completes the nucleus of the basic azolinylidene or azinylidene heterocycle, Y-1
p has the same meaning as in general formula CIV).

Moreover, the substituents of and to L may be combined to form a ring. Examples of the fused heterocycle formed by R7 bonding with R1 or Ll include the following.

In the general formula [■] and each formula described below, R? and R1 is a substituted hydrocarbon having 1 to 6 carbon atoms (e.g. an alkyl or aryl group)
It is.

Representative substituents include sulfo, sulfato, carboxy, hydroxy, carbamoyl, cyano, succinimino, trimethylsilyl, alkoxy, and sulfo-substituted alkoxy.

Specifically, sulfomethyl, sulfoethyl, sulfopropyl, sulfobutyl, sulfophenyl, sulfatomethyl, sulfatoethyl, sulfatopropyl, sulfatobutyl, sulfatophenyl, carboxymethyl, carboxyethyl, carboxypropyl, carboxybutyl, carboxyphenyl. , hydroxyethyl, hydroxypropyl, carbamoylmethyl, carbamoylethyl,
Representative groups include carbamoylpropyl, carbamoylbutyl, carbamoylphenyl, cyanoethyl, cyanopropyl, iminoethyl succinate, iminopropyl succinate, trimethylsilylethyl, methoxyethyl, methoxypropyl, and sulfoethoxyethyl.

As is clear from the above formula, this cyanine dye is a type of quaternized tellurazolium salt of formula (IV), although the structure of the substitution R6 at the 2-position is complex.

The tellurium azolium nucleus has already been described above.

Although this nucleus could be characterized as a tellurium azolium nucleus or a tellurium azolinylidene nucleus, for convenience we will use the former designation, but for consistency we will refer to the remaining nuclei as aprinylidene or azinylidene nuclei.

In general, any aprinylidene or azinylidene nucleus satisfying formula (■) can be used in combination with the tellurium azolium nucleus. It is particularly envisaged that Q can be selected from: benzotelluriazolinylidene, naphthotellurium azolinylidene, 2- or 4-pyridylidene, imidazopyridylidene, 2- or 4-quinolinylidene, l - or 3- Intrilidene, penzoquinolinylidene, thiazoloquinolinylidene, imidazoquinolinylidene, 3H-intrilidene, IH or 3
H-Benzintrilidene, oxazolinylidene, oxazolidinylidene, penzoxazolinylidene, naphthooxazolinylidene, oxadiazolinylidene, thiazolidinylidene, phenanthrothiazolinylidene, acenaphthothiazolinylidene Liden, thiazolinylidene, penzothiazolinylidene, naphthothiazolinylidene, tetrahydropenzothiazolinylidene, dihydronaphthothiazolinylidene, thiadioxazolinylidene, selenium azolidinylidene, selenium azolinylidene, pen Zoselen azolinylidene, naphthoselen azolinylidene, selenium azolinylidene, birazolylidene, imidazolinylidene, imidazolidinylidene, penzimidazolinylidene, naphthiimidazolinylidene, diazolinylidene, tetrazolinylidene, and imidazoquinoxalini The core of Liden. This nucleus can be substituted in any conventional manner consistent with formula (■). R6 can, for example, be any conventional quaternized group and can be selected from any of the various forms of R7 described above.

In a preferred form, the cyanine dye of the present invention satisfying the general formula [■] is represented by the following general formula (IX).

General formula (IX) In the formula, RI%R, nSm, Y- and p represent the same meanings as in the above general formula [■]. R7 and R6 are independently optionally substituted alkyl and aryl groups, and Q
is a group of atoms that completes the basic apurinylidene or azinylidene nucleus, which may include a benzo or naphtho ring moiety.

In another preferred form, the cyanine dye of the present invention satisfying the general formula [■] is represented by the following general formulas (X) and (XI).

General formula (X) General formula (XI) In the formula, R, Rt, R? , R8, Q, Y-1m and p have the same meanings as in the general formula [■].

R'') to R(1 (1) are hydrogen atoms, alkyl (
(e.g., methyl, ethyl, dulopyl, etc.), aralkyl (e.g., benzici, phenethyl, etc.), aryl (e.g., phenyl), petero ring (e.g., chenyl, furyl, etc.), alkyloxy (e.g., methoxy, ethoxy, etc.), aryloxy (e.g., phenoxy group), cyano group, amino (e.g., dimethylamino, anilino, etc. groups), alkylthio (e.g., methylthio group)
, represents each group such as arylthio (for example, phenylthio group), and an acidic nucleus.

i′ represents O or l, n″ represents 1 or 2. However, n
' + When n-≦2, R">~R"0) and Rto
Not all of Rz are hydrogen atoms.

R111 and R11 are hydrogen atoms, alkyl (e.g., methyl, ethyl, etc.), alkoxy (e.g., methoxy, ethoxy, etc.), aryloxy (e.g., phenoxy), aryl (e.g., phenyl), aralkyl (e.g., benzyl), group) and a cyano group.

RIO and RII may jointly form a 5- to 6-membered ring. R1! represents a hydrogen atom or an alkyl group (for example, a methyl group), and R1 represents a hydrogen atom or an alkyl group (for example, a methyl group).

In another preferred form, the cyanine dye used in the photographic element of the present invention is represented by the following general formula (XI[], in addition to the general formula [■]).

General formula (XI[[) R1 and R3 are synonymous with general formula ([V), R7, R
8 is LI'=Ls, and Y-1Psmsn is synonymous with the general formula [■].

Examples of the ring that may be formed with R1, R1 or L+ include those described in general formula [■].

With the exception of the apriedene or azinylidene ring form completed by Q, the various components of formula (XI [[)
can be selected in the same way as described above. In the optimal form, Q of formula (XI[[) is pyrrolilidene,
selected from among the nuclei of intrilidene, carboazolilidene, benzintrilidene, virazolilidene, indacylylidene, and pyrrolopyridinylidene.

Again, common ring substituents consistent with formula (XI[I) are contemplated.

R1 and R1 optimally represent substituted alkyl and aryl substituents, respectively, as described above.

Specific examples of the sensitizing dye of the present invention are shown below, but the invention is not limited thereto.

No, R+ Rt Rs Rt
Rt Ran X0I OHHCHa
CHs OHHI CFaSOs2 0
CRs 0CRs CHa CHs 0C
Hs 0CHa2 CFsSOsNO, R+
Re Rt Rs Rt Ra G
n X'3 HHC11, CJsHHS 0
f04 CH, HCH, -csussosecs
CIN-C, H, 1-5CI! , HCHa-
CsH,SO,”HCQ Se 1-6 0C
H, OCH, CH, C, H, H [1011ONo,
8 IO No, 9 IO NO, IO full CQO,.

NO, 11 No, 12 No, 13 NO, 14 No, 15 NO, 16 No, 17 NO, 18 NO, 19 NO, 2O No, 21
4 soitit')! 10.22 No, 23 No, 24 No, 25 NO, 26 No, 27 No, 28 No, 29 No, 3O No, 31 No, 32 No, 33 No, 34 NO, 35 NO, 36 NO, 37 CH, C00C, H, C, L NO, 3B No, 39 O No, 4O NO, 41 NO, 42 No, 43 No, 44 No, 45 NO, 41+ (CHJ4SOsNa NO, 47 CJs NO, 48 CJs n=1 110 .49 NO, 50 CJs n=1 NO, 51 (CH,)ssO, K 1= lN0.52 NO, 53 NO, 54 NO, 55 NO, 56 CI.

NO, 57 NO, 58 rrenal- ! 10.59　　　　　　　　　　,,■.

No, 6O NO, 61 C113CF3SO3-””3 N0162 C.I.

110.63 NO, 64 (CL, 150sNa No, 65 NO, 66 No, 67 No, 68 No, 69 NO, 7O NO, 71 NO, 72 NO, 73 (CHz)2SO3- NO, 75 NO, 76 110, 77 C1Htsu NO, 78 No, 81 No, 82 110.83 CFJO3゜NO, 84 NO, 85 NO, 86 C*Tii, OH No, 87 NO, 88 NO, 89 CsuH5 No, 90 CH-CL Book The sensitizing dye of the invention can be obtained by referring to the following patents and documents.

British Patent No. 652.2.45, British Patent No. 654,690,
841,119, French Patent No. 757,767, US Patent No. 1,846,302, French Patent No. 28345.094
No. 2,369,646, No. 2,378.783, No. 2,385,815, No. 2.478.366,
2,610,121, 2,238.231, 2,213.995, 2,503.776, 2
, 734,900, JP-A-47-9678
No. 60-78445, Journal of the American Chemical Society, Vol. 67, 1875-18'89 (1945), F.M. Herma, Cyanine Soybean and Related. Comparan, '((Published by Inter Science Publishers, 1964) Pharmaceutical Journal, Vol. 668, 191-194 (First, specific synthesis examples are shown, but other compounds represented by the above general formula can also be synthesized by the following synthesis method. It can be synthesized according to the same method.

[Synthesis example! ]

4-(2-(5,6-sihydro2H,4H-tellazolo(5,4,3-f,D-quinoline-2-ylidene)ethylidene-5-oxo-2-thioxo-1,3-thiazolidine-1- Yyl acetic acid (Exemplary compound NO, 18) 2-acetanilide vinyl-5,6-sihydro 4H-
Tellazolo (5,4,3-f,j) quinolinium chloride 4.69 and 3-carboxymethylrhodanine 1.9
Dissolve g in absolute ethanol 50a+12, add 2g of triethylamine and heat under reflux for 15 minutes. The reaction solution is allowed to cool, and then sufficiently cooled in a water bath to crystallize, and the crystals are collected by filtration. The crude product is purified by repeated recrystallization from methanol.

Yield 1.49 Maximum absorption wavelength in methanol solution 55 Q nff1° [Synthesis Example 2] 3- (2-(3-(5,6-Sihydro28.4H-
Tellazolo(5,4,3-4,j)quinoline-2-ylidene)-1-propenyl)-1-naphtho(1゜2-α〕
Thiazolo] propanesulfonic acid inner salt (Exemplary compound NO, 24)
, 4, 3-7, j] 3.29 quinolinium chloride salt is suspended in 30 ml of acetic anhydride, 3.8 g of diphenylformamidine is added, and the mixture is heated under reflux for 10 minutes. After cooling, dilute with isopropyl ether and collect the precipitate by filtration.
Wash with ethyl acetate and dry. Yield 3.39,
2.39 of the crude product was dissolved in 20 ml of m-cresol, and 1.69 of 3-(2-methyl-1-naphtho[l,2-α]thiazolio)propanesulfonic acid inner salt and 2.09 of triethylamine were added. Heat and stir at 110°C for 20 minutes.

After cooling, dilute with isopropyl ether and discard the supernatant. Add acetone and stir to crystallize, collect the precipitate by filtration and wash with ethanol. The crude product is purified by repeated recrystallization from chloroform-methanol (1:1).

Yield In0.65y Melting point 300'C or higher Maximum absorption wavelength in methanol solution 607 nm [Synthesis Example 3] 2-(5-2-(3-methyl-4-phenyl-2(3H
) tellurazolidene) ethylidene) 4-oxo-2-thioxo-! , 3-thiazolidin-3yl)ethanesulfonic acid (exemplary compound NO, 2B) 2-acetamidovinyl-
2.99% of 3-methyl-4-7enyltellazolium trifluoromethanesulfonate and 1.29% of 3-β-sulfoethylrhodanine are dissolved in 30 mQ of absolute ethanol, 29% of triethylamine is added, and the mixture is heated under reflux for 15 minutes.

The reaction solution is allowed to cool, and then sufficiently cooled in a water bath to cause crystallization, and the precipitated crystals are collected by filtration. The crude product is purified by repeated recrystallization from methanol.

Yield 0.819 Maximum absorption wavelength in methanol solution 546 nm [Synthesis Example 4
] 2-(5-chloro-2-(3-(3-methyl-4-phenyl-2(3H)tellazoliden)-1-propenylidene)-3-penzooxazolio)ethanesulfonic acid inner salt (exemplary compound NO, 33) Dissolve 13.59 of 2-methyl-4-phenyltetrazole in 80% of dichloromethane to obtain 9.09% of methylnitrifluoromethanesulfonate.
Add, seal, and leave at room temperature for one week.

The precipitated crystals are collected by filtration and then suspended in acetic anhydride 120a+12.

Add 19.6 g of diphenylformamidine and heat under reflux for 10 minutes. After cooling, the mixture is diluted with isopropyl ether, and the precipitate is collected by filtration, washed with ethyl acetate, and dried.

Yield: 15.19 2.99 of the crude product was dissolved in 20 ml of m-cresol, and 1.49 2-(5-chloro-2-methyl-3-penzooxazolio)ethanesulfonic acid inner salt and 1 g of triethylamine were added. In addition, heat and stir at 110° C. for 15 minutes.

After cooling, dilute with isopropyl ether and discard the supernatant. Add acetone and stir to crystallize. The precipitate is collected by filtration and washed with ethanol.

It was purified by recrystallization from a mixed solvent of chloroform-methanol (1:2).

Yield 0.549 Maximum absorption wavelength in methanol solution 601 nm [Synthesis Example 5] Bis-3,8-3', 10-trimethylene tellacarbocyanine iodo salt (Exemplary compound NO, 43) 2.3-
4 g of trimethylene benzotellazolium iodo salt and orthoformic acid ethyl ester t, sg in 30 vans of pyridine.
added to.

Triethylamine was added and the mixture was heated under reflux for 15 minutes to allow crystallization to occur.

The precipitate was collected by filtration and washed with ethanol to obtain 1.09 of the crude product.

It was purified by repeated recrystallization from methanol.

Yield 0.69 Melting point 300°C or higher Maximum absorption wavelength in methanol 627 na+ [Synthesis Example 6] 5-(2-(3-ethyl-6-methyl-2(3H)penzothiazolidene)ethylidene-3-phenyl- 2-thiotelazolidine-2,4-dione (exemplary compound NO.
,48) 2-(2-acetanilidevinyl)-3-ethyl-6-
Methylbenzothiazolium iodo salt 4.59 and 3-phenyl-2-thiotelazolidine-2°4-dione 2 g
and dissolved in 30g ethanol + 12g.

Add triethylamine 29 and heat under reflux for 10 minutes, then cool. The precipitated crude product is collected by filtration and washed with ethanol. Recrystallize from methanol to obtain orange-red crystals.

Maximum absorption wavelength in methanol solution: 531 nm [Synthesis Example 7] 4-[5-hydroxy-3-methyl-4-(3-(4-
Oxo-3-phenyl-2-thioxotellazolidinylidene)-1-propenyl)pyrazolyl]benzenesulfonic acid potassium salt (exemplified compound N0153) 3-phenyl-2-thiotellazolidine-2゜4-dione 1 .09 and 2.19 of 4-(3-acetanilidearylidene)-3-methyl-1-(p-sulfophenyl)-5-pyrazolone are dissolved in 10 mg of dimethylformamide, and triethylamine 19 is added and stirred. After 4 hours, add 50 mQ of water to dilute and acidify with dilute hydrochloric acid.

The precipitate is collected by filtration and washed with methanol.

The crude product is purified by dissolving it in a methanol solution containing 1.2 equivalents of triethylamine and crystallizing it by adding 2 equivalents of potassium acetate.

Yield 1.39 [Synthesis Example 8] 2-(5-(2-(3-methyl-2(3H)cheno[2
,3-α]tellazoliden)ethylidene)-4-oxo-2-oxo-1,3-thiazolidin-3-yl)ethanesulfonic acid (exemplary compound NO, 56) 2-acetanilidevinyl-3-methyl-cheno[2 ,3-α]tellazolium trifluoromethanesulfonic acid 2.69 and 3
-β-sulfoethylrodani 21.2g and absolute ethanol 50a+1! Add 2 g of triethylamine and heat under reflux for 15 minutes.

The reaction solution is allowed to cool, and then sufficiently cooled in a water bath to cause crystallization, and the precipitated product is collected by filtration. The crude product is purified by repeated recrystallization from methanol.

Yield 0.859 Maximum absorption wavelength in methanol solution 562 nm [Synthesis Example 9
] 3.3'-Dimethyl-cheno[2,3-α]telluracarbocyanine trifluoromethanesulfonic acid (Exemplary Compound No. 61) 2-Methyl-cheno[2,3-α]tellazole 12.
59 was dissolved in dichloromethane 10t) a12 to form methyl trifluoromethanesulfonate 9. Add Og4, seal and leave at room temperature for one week.

The precipitated crystals are collected by filtration and then suspended in 120 ml of acetic anhydride.

Add 19.69 g of diphenylformamidine and heat to reflux for 10 minutes. After cooling, the mixture is diluted with isopropyl ether, and the precipitate is collected by filtration, washed with ethyl acetate, and dried.

Yield 14.89 2.69 of the crude product was dissolved in 20 ml of m-cresol and 2.09 of 2,3-dimethyl-cheno[2,3-α]tellazolium trifluoromethanesulfonate and 2.09 of triethylamine were added. Heat and stir at 110°C for 15 minutes.

After cooling, dilute with isopropyl ether and discard the supernatant. Add acetone and stir to crystallize. The precipitate is collected by filtration and washed with ethanol.

2.2.3. It was purified by recrystallization from a mixed solvent of 3-tetrafluoropropanol-methanol (1:3).

Yield 0.589 Maximum absorption wavelength in methanol solution 636 nm [Synthesis example [
0) 2-(5-(2-(5-fluoro-3-methyl-2(3
H)-benzotellazolidene)ethylidene)4-oxo-2-thioxo-1,3-thiazolidin-3-yl)ethanesulfonic acid (Exemplary compound 110.62)2-acetanilidevinyl-5-fluoro-3-methylbenzo 2.8 g of tellazolium trifluoromethanesulfonate and 0.959 g of 3-carboxymethylrhodanine are dissolved in 301112 absolute ethanol, 2 g of triethylamine is added, and the mixture is heated under reflux for 20 minutes.

The reaction solution is allowed to cool, and then sufficiently cooled in an ice-water bath to crystallize, and the precipitated crystals are collected by filtration. The crude product is purified by repeated recrystallization from methanol.

Yield 0.69 Maximum absorption wavelength in methanol solution 547 ng+ [Synthesis Example 11] Anhydro 3-(2-(3-(5-fluoro-3-methyl-2(3H)penzotellazolidene)-1-propenyl )-5-Methoxy-3-penzoselenazolio]propanesulfonic acid inner salt (Exemplary compound 110.69) 5-Fluoro-2-methylbenzotellazole 13.1
9 was dissolved in dichloromethane room 12 and methyl trifluoromethanesulfonate 9. Add Og, seal, and leave at room temperature for 2 weeks.

The precipitated crystals are collected by filtration and then suspended in 100 ml of acetic anhydride.

Add 9.69 g of diphenylformamidine L and heat to reflux for 10 minutes. After cooling, the mixture is diluted with isopropyl ether, and the precipitate is collected by filtration, washed with ethyl acetate, and dried.

Yield: 8.39 Dissolve 2.89 of the crude product in 20 mQ of m-cresol,
3-(5-Methoxy-2-methyl-3-penzoselenazolio)propanesulfonic acid inner salt t,7y and 2 g of triethylamine are added, and the mixture is heated and stirred at 110° C. for 15 minutes.

After cooling, dilute with isopropyl ether and discard the supernatant. Acetone is added and the mixture is stirred for crystallization, and the precipitate is collected by filtration and washed with ethanol.

Purification was performed by recrystallization from a mixed solvent of chloroform-methanol (1:2).

Yield: 0.519 Maximum absorption wavelength in methanol solution: 599 nm [Synthesis Example 12] 5'-Chloro-3,5,10-)rifthyl-3'-sulfopropyl tellulathiacarbocyanine inner salt (Exemplary compound NO, 72 ) 2.3.4.2 g of 5-trimethylbenzotellazolium-trifluoromethanesulfonate and 3-(5-chloro-2-(2methylthio-1-propenyl)-3benzothiazolio)propanesulfonic acid inner salt 3. Add 89 to 30 mQ of pyridine, add triethylamine 29, and make 4.
Stir at 0°C. The precipitated dye is collected by filtration and washed with methanol.

2.2.3.3-Recrystallize and purify the target product from a mixed solution of tetrafluoropropanol and methanol to 0.749
Obtained.

Maximum absorption wavelength in methanol solution 595 na + [Synthesis Example 13] 5-(4-(3-ethyl-5-methyl-2(3H)tellazoliden)-2-methyl-2-butenylidene)-4-
Oxo-2-thioxo-1,3-thiazolidin-3-yl acetic acid (Exemplary compound NO, 76) 2-(3-acetanilidomethylene-2-butenyl)-3-ethyl-5-methylbenzotellazolium iodo salt 5 .99 and 1.9 g of 3-carboxymethylrhodanine in ethanol 80II
Add to l12.

Add 3 g of triethylamine, heat under reflux for 30 minutes, cool with water, and precipitate as acetic acid.

The crude product is heated and dissolved in ethanol containing triethylamine, then cooled and acidified with acetic acid to crystallize it.

It was collected by filtration and washed with ethanol to obtain 1.29% of the desired product.

Maximum absorption wavelength in methanol solution: 608 nm Sensitizing color used in the present invention r\lXl per mole of silver halide
0-'' mol to 5xlO-' mol, preferably 1 x 10
-''mol to 2.5XLO-'mol, particularly preferably 4x
It is contained in a silver halide photographic emulsion in a proportion of to-' moles to txto-' moles.

The sensitizing dye used in the present invention can be added to the emulsion using methods known in the art. For example,
These sensitizing dyes can be directly dispersed in the emulsion or dissolved in a water-soluble solvent such as pyridine, methyl alcohol, ethyl alcohol, methyl cellosolve, acetone, or mixtures thereof, or diluted with water. The sensitizing dye can be dissolved in water or dissolved in water and added to the emulsion in the form of a solution.The sensitizing dye can be added to the emulsion at any time during the emulsion manufacturing process, but during chemical ripening or chemical ripening. The latter is preferable.

When forming a silver image in the heat-developable photosensitive element of the present invention, at least )-silver halide, the sensitizing dye of the present invention, a reducing agent, and a binder are provided on the support, and more preferably an organic silver salt. It also has

When forming a dye image in the heat-developable photosensitive element of the present invention, at least silver halide, the sensitizing dye of the present invention, a reducing agent, a dye-providing compound, and a binder are present on the support, or (2) At least a silver halide, a sensitizing dye of the invention, a reducing dye-providing compound, a binder, and each preferably also contains an organic silver salt.

Examples of the photosensitive silver halide include silver chloride, silver bromide, silver iodide, silver chlorobromide, silver chloroiodide, silver iodobromide, silver chloroiodobromide, and the like. The photosensitive silver halide can be prepared by any method in the photographic field, such as a single jet method or a double jet method, but the photosensitive silver halide prepared according to a conventional method for preparing a silver halide gelatin emulsion may be used. A light-sensitive silver halide emulsion containing .

The light-sensitive silver halide emulsion may be chemically sensitized by any method in the photographic art. Such sensitization methods include
Various methods include gold sensitization, sulfur sensitization, gold-sulfur sensitization, and reduction sensitization.

The silver halide in the above-mentioned photosensitive emulsion may be coarse grained or fine grained, but the preferred grain size is about 0,00 μm to about 1.5 μm, more preferably about 0 μm. 0.01 μm to approximately 0.5 μm.

The light-sensitive silver halide emulsion prepared as described above can most preferably be applied to a heat-developable light-sensitive element.

As another method for preparing photosensitive silver halide, a photosensitive silver salt-forming component may be allowed to coexist with the organic silver salt described below, and photosensitive silver halide may be formed in a portion of the organic silver salt. The photosensitive silver salt-forming component used in this preparation method is an inorganic halide, for example, a halide represented by M X n (where M represents an H atom, an N H4 group, or a metal atom, and X represents Represents CQlBr or I, n is Mh4H
1 for atoms, NH, and groups. When M is a metal atom, its valence is shown.

Metal atoms include lithium, sodium, potassium,
Rubidium, cesium, copper, gold, beryllium, magnesium, calcium, strontium, barium, zinc,
Cadmium, mercury, aluminum, indium, lanthanum, ruthenium, thallium, germanium, tin, lead, antimony, bismuth, chromium, molybdenum, tungsten, manganese, rhenium, iron, cobalt, nickel, rhodium, palladium, osmium, iridium, platinum,
Examples include cerium. ), halogen-containing gold@complexes (e.g., K zP tCQm , K *P tB rs
.

HAuCL , (NH4)tIrclL , (NHa)
sl rCQs.

(NHa)*RuCl2m, (NHa)aRucL
, (NH4)3RhCI2e, (NH4)aRh
Brs, etc.), onium halides (e.g., quaternary ammonium halides such as tetramethylammonium bromide, trimethylphenylammonium bromide, cetylethyldimethylammonium bromide, 3-methylthiazolium bromide, trimethylbenzylammonium bromide, quaternary phosphonium halides such as onium bromide, tertiary sulfonium halides such as benzylethylmethylsulfonium bromide, l-ethylthiazolium bromide, etc.), halogenated hydrocarbons (e.g. iodoform, bromoform, carbon tetrabromide, etc.) , 2-bromo-2-methylpropane, etc.), N-halogen compounds (N-chlorosuccinimide, N-bromosuccinimide, N-bromophthalimide, N-bromoacetamide, N-iodosuccinimide, N-bromophthalimide) Radinone, N-chlorophthalazinone, N-bromoacetanilide, N,N-dibromobenzenesulfonamide, N-bromo-N-methylbenzenesulfonamide, ■,3-dibromo4,4-dimethylhydantoin, etc.), and others Halogen-containing compounds (
Examples include triphenylmethyl chloride, triphenylmethyl bromide, 2-bromobutyric acid, 2-bromoethanol, etc.).

These photosensitive silver halides and photosensitive silver salt forming components can be used in combination in various methods, and the amounts used are as follows:
1+a'' per layer, preferably from 0.0019 to 509, more preferably from 0.19 to 109
It is.

The heat-developable photosensitive element can also have a multi-layer structure including layers sensitive to blue light, green light, and red light, that is, a heat-developable blue-sensitive layer, a heat-developable green-sensitive layer, and a heat-developable red-sensitive layer. . Further, the same color photosensitive layer can be divided into two or more layers (for example, a high-sensitivity layer and a low-sensitivity layer).

In the heat-developable photosensitive element, various organic silver salts can be used, if necessary, for the purpose of increasing sensitivity and improving developability.

Examples of organic silver salts used in heat-developable photosensitive elements include Japanese Patent Publications Nos. 43-4921, 44-26582, and 45-1.
No. 8416, No. 45-12700, No. 45-2218
No. 5, JP-A-49-52626, JP-A No. 52-31728
No. 52-137321, No. 52-141222, No. 53-36224, and No. 53-37610, as well as U.S. Patent No. 3,330°633,
3゜794.496, 4,105,451, 4.123,274, 4.168,980
Silver salts of aliphatic carboxylic acids such as silver laurate, silver myristate, etc.
Silver palmitate, silver stearate, silver arachidonate, silver behenate, silver α-(l-phenyltetrazolethio)acetate, etc., silver aromatic carboxylates, such as silver benzoate, silver phthalate, etc., Japanese Patent Publication No. 44-26582 No. 45-12
No. 700, No. 45-18416, No. 45-22185
No., JP-A-52-31728, JP-A No. 52-137321
No., JP-A-58-118638, JP-A No. 58-11863
Silver salts of imino groups as described in publications such as No. 9, such as silver benzotriazole, silver 5-nitrobenzotriazole, silver 5-chlorobenzotriazole, silver 5-methoxybenzotriazole, and silver 4-sulfobenzotriazole. silver, 4-hydroxybenzotriazole silver, 5-
Aminobenzotriazole silver, 5-carboxybenzotriazole silver, imidazole silver, benzimidazole silver, 6-nidropenzimidazole silver, pyrazole silver, urazole silver, 1,2,4-triazole silver, IH-tetrazole silver, 3-amino -5-benzylthio-1,2,
4-) Riazole silver, saccharin silver, phthalanonon silver,
Silver phthalimide, etc., 2-mercaptobenzoxazole silver, mercaptooxadiazole silver, 2-mercaptobenzothiazole silver, 2-mercaptobenzimidazole silver, 3-mercapto-4-phenyl-1゜2.
4-) Riazole silver, 4-hydroxy-6-methyl 1
．． 3.3a, 7-thitrazaindene silver and 5-methyl-7hydroxy-1.2.3.4.6-pentazaindene silver. Among the above organic silver salts, imino group silver salts are preferred, and silver salts of benzotriazole derivatives are particularly preferred, and silver salts of sulfobenzotriazole derivatives are particularly preferred.

The above-mentioned organic silver salts may be used alone or in combination of two or more, isolated ones may be dispersed in a binder by appropriate means, and silver salts may be used in a suitable binder. Salts may be prepared and used directly without isolation.

The amount of the organic silver salt used is preferably 0.01 to 500 mol, more preferably 0.01 to 100 mol, per 1 mol of photosensitive silver halide.

As the reducing agent used in the heat-developable photosensitive element, those commonly used in the field of heat-developable photosensitive elements can be used; for example, those disclosed in U.S. Pat.
270, 3.764, 328, and Research Disclosure No. 0012146, 3.764, 328,
15108, No. 15127 and JP-A-56-2
Examples include p-phenylenediamine-based and p-aminophenol-based developing agents, phosphoramidophenol-based and sulfonamidophenol-based developing agents, and hydrazone-based color developing agents described in Japanese Patent No. 7132 and the like.

Also, U.S. Patent No. 3.342,599, U.S. Patent No. 3.71
9.492, JP-A-53-135628, JP-A No. 54-
Color developing agent precursors described in No. 79035 and the like can also be advantageously used.

As a particularly preferable reducing agent, JP-A-56-146133
Examples include reducing agents represented by the following general formula (33) described in the specification of No.

Margin R18R1 below? In the formula, R1! and R1, is a hydrogen atom or has 1 to 30 carbon atoms (preferably 1 to 4) that may have a substituent
represents an alkyl group, and may be ring-closed with R1 and RI2 to form a heterocycle. R14, RtsRts and R17
is a hydrogen atom, a halogen atom, a hydroxy group, an amino group,
represents an alkoxy group, an acylamido group, a sulfonamide group, an alkylsulfonamide group, or an alkyl group having 1 to 30 carbon atoms (preferably 1 to 4) that may have a substituent, and R14 and R11 and Rte and R13 are Each may be ring-closed to form a heterocycle. M represents an alkali metal atom, an ammonium group, a nitrogen-containing organic base, or a compound containing a quaternary nitrogen atom.

The nitrogen-containing organic base in the above general formula (33) is an organic compound containing a nitrogen atom exhibiting basicity capable of forming a salt with an inorganic acid, and particularly important organic bases include amine compounds. Examples of chain amine compounds include primary amines, secondary amines, and tertiary amines, and examples of cyclic amine compounds include pyridine, quinoline, and piperidine, which are well-known as typical examples of heterocyclic organic bases. , imidazole and the like. In addition, hydroxylamine,
Compounds such as hydrazine and amidine are also useful as chain amines. In addition, as the salt of the nitrogen-containing organic base, inorganic acid salts of the organic base (eg, hydrochloride, sulfate, nitrate, etc.) as described above are preferably used.

On the other hand, examples of the compound containing quaternary nitrogen in the above general formula include salts or hydroxides of nitrogen compounds having a tetravalent covalent bond.

The reducing agent represented by the above general formula (33) can be obtained by known methods such as)
der Organisc-hen Chee+ie,
Band XI/2.64! )-703.

Other reducing agents as described below can also be used.

For example, phenols (e.g., p-phenylphenol, p-methoxyphenol, 2.6-tert-butyl-p-cresol, N-methyl-p-aminophenol, etc.), sulfonamide phenols [e.g., 4-
Benzenesulfonamidophenol, 2-benzenesulfonamidophenol, 2゜6-dichloro-4-benzenesulfonamidophenol, 2,6-dipromo-4-
(p-)luenesulfonamide) phenols, or polyhydroxybenzenes (e.g. hydroquinone,
tert-butylhydroquinone, 2,6-dimethylhydroquinone, chlorohydroquinone, carboxyhydroquinone, catechol, 3-carboxycatechol, etc.), naphthols (e.g. α-naphthol, β-naphthol, 4-aminonaphthol, 4-methoxynaphthol, etc.) ), hydroxybinaphthyls and methylene bisnaphthols [e.g. 1°1'-dihydroxy-2,2'
-binaphthyl, 6゜6-dipromo2,2'-dihydroxy-1,1'-binaphthyl, 6,6-sinitro2
．． 2'-dihydroxy-1,1'-binaphthyl, 4.
4'-dimethoxy-1,1'-dihydroxy-2,
2′-binaphthyl, bis(2-hydroxy-1-naphthyl)methane, etc.], methylenebisphenols [e.g. 1°1-bis(2-hydroxy-3,5-dimethylphenyl)-3,5,5-trimethylhexane , 1.1-bis(2-hydroxy-3-tert-butyl-5-methylphenyl)methane 1.1-bis(2-hydroxy-3
,5-di-tert-butylphenyl)methane, 2.6
-methylenebis(2-hydroxy-3-tert-butyl-5-methylphenyl)-4-methylphenol, α
-phenyl-α,α-bis(2-hydroxy-3,5-
di-tert-butylphenyl)methane, α-phenyl-α, α-bis(2-hydroxy-3-tert-butyl-5-methylphenyl)methane, 1,1-bis(2-
Hydroxy-3,5-dimethylphenyl)-2-methylpropane, 1,1,5,5-tetrakis(2-hyphenyl-3,5-dimethylphenyl)-2,4-ethylpentane, 2.2 -bis(4-hydroxy-3,5-tmethylphenyl)propane, 2.2-bis(4-hydroxy-3-methyl-5-t'ert-butylphenyl)propane, 2゜2-bis(4- Hydroxy 3,5-di-t
ert-butylphenyl)propane, etc.], ascorbic acids, 3-pyrazolidones, pyrazolones, hydrazones, and paraphenylenediamines.

These reducing agents can be used alone or in combination of two or more. The amount of reducing agent used depends on the type of photosensitive silver halide used, the type of organic acid silver salt, and the type of other additives, but it is usually 0 per mol of photosensitive silver halide. in the range of .01 to 1500 mol,
Preferably it is 0.1 to 200 mol.

Dye-providing substances that can be used in heat-developable photosensitive elements will be explained. The dye-donating substance may be one that participates in the reduction reaction of the photosensitive silver halide and/or organic silver salt used as necessary, and that can form or release a diffusible dye as a function of the reaction. , depending on its reaction form, a negative dye-donor that acts in a positive function (
(i.e., when using negative-working silver halide, it forms a negative dye image) and a positive-working dye-donor that acts on a negative function (i.e., when using negative-working silver halide, it forms a positive dye image). It can be classified as a type (forming a pigment image). Negative dye-donating substances are further classified as follows.

Each dye-providing substance will be further explained.

Examples of the extrinsic dye-releasing compound include the following general formula (1
Examples include compounds shown in 5).

General formula (15) % formula % In the formula, Car is a reducing substrate (so-called carrier) that is oxidized and releases a dye upon reduction of the photosensitive silver halide and/or the organic silver salt used as necessary. , Dy
e is a diffusible dye residue.

Specific examples of the above-mentioned reducing dye-releasing compounds include JP-A-57-179840, JP-A-57-116537, JP-A-5
No. 9-60434, No. 59-65839, No. 59-7
No. 1046, No. 59-87450, No. 59-8873
No. 0, No. 59-123837, No. 59-165054
No. 165055, each specification etc.
Examples include the following compounds.

OC,, H-(n) Other reducing dye-releasing compounds include, for example, the general formula (16
) are listed.

Man.

In the formula, A+-At each represents a hydrogen atom, a hydroxy group, or an amino group, and Dye represents Dy represented by the general formula (15).
It is synonymous with e. Specific examples of the above compounds are given in JP-A-59-1
No. 24,329.

As a coupled dye-releasing compound, general formula (17
) are listed.

General formula (17) % formula % In the formula, Cp is an organic group (so-called coupler residue) that can react with the oxidized form of the reducing agent to release a diffusible dye, and J is a divalent bond. The bond between CP+ and J is cleaved by reaction with the oxidant on the q element side. n represents O or 1, and Dye has the same meaning as defined in general formula (15). Further, Cpl is preferably substituted with various ballast groups in order to make the coupled dye-releasing compound non-diffusible, and the ballast group has 8 or more carbon atoms ( more preferably 12 or more organic groups, or hydrophilic groups such as sulfo groups or carboxy groups, or 8 or more (more preferably 12
It is a group having both carbon atoms (5 or more) and a hydrophilic group such as a sulfo group or a carboxy group. Another particularly preferred ballast group can include polymer chains.

Specific examples of the compound represented by the above general formula (17) include JP-A-57-186,744, JP-A-57-122,
No. 596, No. 57-160, 698, No. 59-174
, No. 834, No. 57-224, 883, No. 59-15
They are described in each publication of No. 9,159 and the specifications of Japanese Patent Application No. 104,901/1982, and include, for example, the following compounds.

CRs ■ S.O.

As the coupling dye-forming compound, general formula (18)
Examples include compounds represented by:

General formula (18) % formula %) In the formula, CPt is an organic group (coupling reaction) that can react with the oxidized product of the reducing agent to form a diffusible dye.
(so-called coupler residue), where X represents a divalent bonding group and Q represents a ballast group.

The coupler residue represented by Cp preferably has a molecular weight of 700 or less, more preferably 500 or less, in view of the diffusibility of the dye formed.

Further, the ballast group is preferably the same as the ballast group defined in general formula (17), and particularly has 8 or more (more preferably 12 or more) carbon atoms and a hydrophilic group such as a sulfo group or a carboxy group. Polymer chains are preferred, and polymer chains are more preferred. - As the coupling dye-forming compound having this polymer, a polymer having a repeating unit derived from a monomer represented by general formula (19) is preferable.

General formula (19) % formula %) In the formula, CptsX has the same meaning as defined in general formula (18), Y represents an alkylene group, arylene group, or aralkylene group, and Z represents a divalent organic group. and L represents an ethylenically unsaturated group or a group having an ethylenically unsaturated group.

Specific examples of coupling dye-forming compounds represented by general formulas (18) and (19) include JP-A-59-124.3
No. 39, No. 5G-181, 345, and patent applications filed in 1973.
No. 8-109,293, No. 59-179.657, No. 59-181.604, No. 59-182,506,
They are described in the specifications of No. 59-182.507, and include, for example, the following compounds.

■ CIJ3B polymer [phase]. u, cootly: 60% by weight @ CH3 [Phase] L ■ [Co.] CH3 In the above general formulas (17), (18) and (19), further regarding the coupler residue defined by CpI or CI)t Specifically, groups represented by the following general formula are preferred.

General formula (20) General formula (21) General formula (22) General formula (23) R・ General formula (24) General formula (25) General formula (
26) General formula (27) ..., '1 □ General formula (28) General formula (29) i
R? 0: In the formula, R2, R6, R7, and R6 are each a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, an aryl group, an acyl group, an alkyl group, an oxycarbonyl group, and an oxycarbonyl group. group, alkyl' L,,,). O =, tL
tl&, aIJ-,)Lp 7. k crab )V,,
M, 71. .

represents a moyl group, a sulfamoyl group, an acylation group, an oxy group, an amino group, an alkoxy group, an aryloxy group, a cyano group, a ureido group, an alkylthio group, an arylthio group, a carboxy group, a sulfo group, or a heterocyclic residue; Hydroxyl group, carboxy group, sulfo group, alkoxy group, cyano group, nitro group, 1. Substituted with alkyl group, aryl group - aryloxy group, acyloxy group, acyl group, sulfamoyl group, carbamoyl group, imide group, halogen atom, etc. It's been a long time since I've been in the middle of a long time since I've been in the middle of a long time.

These substituents are selected depending on the purpose of CP+ and CPt, and as described above, it is preferable that seven of the substituents in Cpt are ballast groups, and in Cps, in order to increase the diffusibility of the dye formed. The substituents are preferably selected so that the molecular weight is 700 or less, more preferably 500 or less.

As a positive dye-donating substance, for example, the following general formula (3
There are oxidative dye-releasing compounds represented by 0).

In the formula, Wl represents a collection of atoms necessary to form a quinone ring (which may have a substituent on this ring). ) or -5Ot-, r represents O or l, and Dye has the same meaning as defined in general formula (15). Specific examples of this compound are JP-A-59-166.954 and JP-A No. 59-1.
No. 54,445, etc., and include, for example, the following compounds.

IO3 [Co., Ltd.] CH3 Another positive dye-donating substance is represented by the following general formula (31)
There are compounds that lose their dye-releasing ability when oxidized, such as the compound represented by:

H In the formula, W represents a collection of atoms necessary to form a benzene ring (which may have a substituent on the ring), and R*S
B%Dye has the same meaning as defined in general formula (30). A specific example of this compound is JP-A-59-124,32
No. 9, No. 59-154.445, etc., and include, for example, the following compounds.

CHn Still another positive dye-donating substance is represented by the following general formula (
Examples include compounds represented by 32).

In the above formula, W, , R, and Dey have the same meaning as defined in general formula (31). Specific examples of this compound are described in JP-A No. 59-154.445, and include the following compounds.

[Phase] General formula (15), (16), (17), (30) described above
, (31) and (32), the residue of the diffusible dye represented by Dey will be described in further detail. Due to the diffusibility of the dye, the residue of the diffusible dye has a molecular weight of 800 or less,
More preferably, it is 600 or less, and azo dyes, azomethine dyes, anthraquinone dyes, naphthoquinone dyes, styryl dyes, nitro dyes, quinoline dyes,
Residues such as carbonyl dyes and phthalocyanine dyes were mentioned. These dye residues may be in a temporary short-waveform form that allows multiple colors during thermal development or transfer. Furthermore, for the purpose of increasing the light resistance of images, a preferable form of these dye residues is a dye residue that can be chelated, as described in, for example, Japanese Patent Application Laid-open Nos. 59-48765 and 59-124337.

These dye-providing substances may be used alone or in combination of two or more. The amount used is not limited and depends on the type of dye-providing substance, whether it is used alone or in combination, and whether the heat-developable photosensitive element is a single layer or a multilayer of two or more layers. For example, the usage amount is 1I11! It can be used in an amount of 0.0059 to 509 g, preferably 0.19 to 10 g.

The dye-providing substance may be incorporated into the thermal photosensitive element by any method, for example, by dissolving it in a low boiling point solvent (methanol, ethanol, ethyl acetate, etc.) or a high boiling point solvent (dibutyl phthalate, dioctyl phthalate, tricresyl phosphate, etc.). After that, it is subjected to long sonic dispersion or dissolved in an alkaline aqueous solution (e.g., 10% aqueous sodium hydroxide solution, etc.), followed by mineral acid (e.g., hydrochloric acid or nitric acid, etc.).
It can be used after being neutralized in a water bottle, or after being dispersed in a ball mill with an aqueous solution of an appropriate polymer (eg, gelatin, polyvinyl butyral, polyvinylpyrrolidone, etc.).

Binders used in heat-developable photosensitive elements include synthetic or natural polymeric substances such as polyvinyl butyral, polyvinyl acetate, ethyl cellulose, polymethyl methacrylate, cellulose acetate butyrate, polyvinyl alcohol, polyvinylpyrrolidone, gelatin, and phthalated gelatin. One or more can be used in combination.

In particular, it is preferable to use gelatin or a derivative thereof in combination with a hydrophilic polymer such as polyvinylpyrrolidone or polyvinyl alcohol, and more preferably
The following binder is described in No. 4249.

The binder includes gelatin and vinylpyrrolidone polymer. The vinyl pyrrolidone polymer may be polyvinyl bilidone, which is a homopolymer of vinyl pyrrolidone, or a copolymer of vinyl pyrrolidone with one or more other monomers copolymerizable (including kraft copolymers). ). These polymers can be used regardless of their degree of polymerization. Polyvinylpyrrolidone may be substituted polyvinylpyrrolidone,
Preferred polyvinylpyrrolidone has a molecular weight of 1, Goo~4
00. It belongs to Goo. Other monomers copolymerizable with vinylpyrrolidone include (meth)acrylic acid esters such as acrylic acid, methacrylic acid and alkyl esters thereof, vinyl alcohols, vinyl imidazoles, (meth)acrylamides, and vinyl carbinols. , vinyl alkyl ethers, and the like, but it is preferable that polyvinylpyrrolidone accounts for at least 20% (weight %, same hereinafter) of the composition ratio. Preferred examples of such copolymers have molecular weights of s, oo
o~400. It belongs to Goo.

The gelatin may be lime-treated or acid-treated, and may be ossein gelatin, big skin gelatin, hydrogelatin, or modified gelatin obtained by esterifying or phenylcarbamoylating these gelatins.

In the above binder, gelatin preferably accounts for 10 to 90% of the total binder amount, more preferably 20 to 60%, and vinylpyrrolidone accounts for 5 to 90%.
It is preferably 10 to 80%, more preferably 10 to 80%.

The binder may contain other polymeric substances,
Gelatin and molecules Wk 1,000-400,000 (
7) Mixtures of polyvinylpyrrolidone and one or more other polymeric substances, gelatin and moleculesill 5,00
A mixture of 0 to 400,000 vinyl pyrrolidone copolymer and one or more other polymeric substances is preferred. Other polymeric substances that can be used include polyvinyl alcohol, polyacrylamide, polymethacrylamide, polyvinyl butyral, polyethylene glycol, polyethylene glycol ester, or proteins such as cellulose derivatives, and polysaccharides such as starch and gum arabic. Examples include natural substances. These may be contained in an amount of 0 to 85%, preferably 0 to 70%.

The above-mentioned vinylpyrrolidone polymer may be a crosslinked polymer, but in this case, it is preferable to crosslink it after coating it on a support (including the case where the crosslinking reaction progresses by being left to stand).

The amount of binder used is usually 0 per 1m” per layer.
．． 059 to 509, preferably 0.19 to 1.0
It is 9. The binder is preferably used in an amount of 0.19 to 10 g, more preferably 0.25 to 49 g, per unit 19 of the dye-providing substance monomer.

Supports used in the thermal mass e and photosensitive elements include, for example, polyethylene films, polyimide films, cellulose acetate films, polycarbonate films, polyethylene terephthalate films, synthetic plastic films such as polyvinyl chloride, photographic base paper, printing paper, Examples include paper supports such as baryta paper, art paper, and resin-coated paper, and supports in which the above-mentioned synthetic plastic film is provided with a reflective layer.

In addition to the above-mentioned components, various additives may be added to the heat-developable photosensitive element as required. For example, as a development accelerator, U.S. Pat.
No. 1,285, No. 4,012゜260, No. 4.0
60420, 4.0880496, 4.2
No. 07,392, each specification, research disclosure! 10.15733, same No. l 5734, same +
10.15776, JP-A-56-130745, 5
Alkali release agents such as urea and guanidium trichloroacetate described in No. B-132332, etc., Japanese Patent Publication No. 1973
-12700, organic acids described in US Pat. No. 3,667,
-c o -, -s o t-, -s described in No. 959
Non-Aqueous Polar Solvent Compounds Having an o-Group, U.S. Patent No. 3,
Meltformer 1 described in US Pat. No. 438.776, polyalkylene glycols described in US Pat. In addition, as a color toning agent, for example, JP-A-46-4928, JP-A No. 46-6
No. 077, No. 49-5019, No. 49-5020,
No. 49-91215, No. 49-107727, No. 5
No. 0-2524, No. 50-67132, No. 60-67
No. 641, No. 50-114217, No. 52-3372
No. 2, No. 52-99813, No. 53-1020, No. 53-55115, No. 53-76020, No. 53-
No. 125014, No. 54-156523, No. 54-1
No. 56524, No. 54-156525, No. 54-15
Publications such as No. 6526, No. 55-4060, No. 55-4061, No. 55-32015, and West German Patent No. 2
, No. 140,406, No. 2,147,063, No. 2,
No. 220,618, U.S. Patent No. 3,080,254;
Same No. 3.847゜612, Same No. 3.782,941, Same No. 3,994.732, Same No. 4.123.282
Phthalazinone, phthalimide, pyrazolone, quinazolinone, N-hydroxynaphthalimide, benzoxazine, naphthoxazinedione, which are compounds described in the specifications of No. 4.20L, No. 582, etc., 2.3
-dihydro-phthalazinedione, 2,3-dihydro-1
, 3-oxazine-2,4-dione, oxypyridine,
Aminopyridine, hydroxyquinoline, aminoquinoline, isocarbostyryl, sulfonamide, 2H-1,3
- benzothiazine-2,4-(3H) dione, benzotriazine, mercaptotriazole, dimercaptotetrazapentalene, phthalic acid, naphthalic acid, phthalamic acid, etc., mixtures of one or more of these with imidazole compounds , a mixture of at least one acid or acid anhydride such as phthalic acid and naphthalic acid and a phthalazine compound, and combinations of phthalazine and maleic acid, itaconic acid, quinolinic acid, gentisic acid and the like. Also, JP-A No. 58-189628,
3-amino-5-mercapto-1,2,4-triazoles, 3-amino-5-mercapto-1,2,4-triazoles, 3-
Acylamino-5-mercapto-1,2°4-triazoles are also effective.

Furthermore, as anti-fogging agents, for example,
No. 7-11113, JP-A-49-90118, JP-A No. 49
-10724, 49-97613, 50-10
No. 1019, No. 49-130720, No. 50-123
No. 331, No. 51-47419, No. 51-57435
No. 5! No. -78227, No. 51-104338,
No. 53-19825, No. 53-20923, No. 51
-50725, 51-3223, 51-425
Publications such as No. 29, No. 51-81124, No. 54-51821, and No. 55-93149, as well as British Patent No. 1,455,271 and U.S. Patent No. 3,885.968.
No. 3,700.457, No. 4,137,07
No. 9, No. 4,138,265, West German Patent No. 2.61
7,907, etc., or oxidizing agents (e.g., N-halogenoacetamide, N-halogenosuccinimide, perchloric acid and its salts, inorganic peroxide substances, persulfates, etc.), or
Acids and their salts (e.g. sulfinic acid, lithium laurate, rosin, diterpenic acid, thiosulfonic acid, etc.),
or sulfur-containing compounds (e.g. mercapto compound-releasing compounds, thiouracil, disulfide, simple sulfur,
Examples include mercapto-1,2°4-triazole, thiazolinthione, polysulfide compounds, etc.), and other compounds such as oxazoline, 1,2°4-triazole, and phthalimide. Furthermore, thiol (preferably a thiophenol compound) compound described in JP-A-59-111836 is also effective as another antifoggant.

In addition, as other antifogging agents, Japanese Patent Application No. 59-565
Hydroquinone derivatives described in No. 06 (for example, G.E.
-octylhydroquinone, dodecanylhydroquinone, etc.) or hydroquinone derivatives described in Japanese Patent Application No. 59-66380, and benzotriazole derivatives (e.g., 4-sulfobenzotriazole, 5-carboxybenzotriazole, etc.) are preferably used in combination. can.

In addition, as a stabilizer, a printout preventive agent may also be used at the same time, especially after processing.
Halogenated hydrocarbons described in Publication No. 53-46020, specifically tetrabromobutane, tribromoethanol, 2-bromo-2-tolylacetamide, 2-bromo-2-tolylsulfonylacetamide, 2-tribromobutane, tribromoethanol, 2-bromo-2-tolylacetamide, 2-bromo-2-tolylsulfonylacetamide, Examples include bromomethylsulfonylbenzothiazole and 2,4-bis(tribromomethyl)-6-methyltriazine.

In particular, it is preferable to add various heat solvents to the heat-developable photosensitive element. The thermal solvent may be any substance that promotes thermal development and/or thermal transfer, and is preferably solid, semi-solid, or liquid at room temperature (preferably with a boiling point of 100°C or higher at normal pressure, more preferably 150°C or higher). ) which dissolves or melts in the binder by heating, preferably a urea derivative (e.g.
dimethylurea, diethylurea, phenylurea, etc.)
, amide derivatives (e.g., acetamide, benzamide, etc.), polyhydric alcohols (e.g., 1.5-bentanediol, 1.6-bentanediol, 152-cyclohexanediol, pentaerythritol, trimethylolethane, etc.), or polyethylene glycol Examples include: For a detailed example, see Japanese Patent Application No. 10424/1986.
9. These thermal solvents may be used alone or in combination of two or more.

Also, Japanese Patent Publication No. 4B-5393, Japanese Patent Publication No. 50-54329
Post-treatment may be performed using a sulfur-containing compound as described in No. 50-77034.

Furthermore, U.S. Patent No. 3,301,678;
No. 506,444, No. 3,824.103, No. 3
, 844,788, as well as U.S. Pat. No. 3.6.
No. 69,670, No. 4.012゜260, No. 4,
It may also contain activator stabilizer precursors and the like described in 060,420 and the like.

Also, sucrose, N H4F e(S O4) * ” 1
2 H! A water release agent such as 0 may be used, and furthermore,
Heat development may be carried out by supplying water as in JP-A-56-132332.

In addition to the above-mentioned components, the heat-developable photosensitive element may further contain various additives such as spectral sensitizing dyes, antihalation dyes, optical brighteners, hardeners, antistatic agents, plasticizers, spreading agents, etc. Coating aids etc. are added.

Heat-developable photosensitive elements basically include (
It is preferable that the composition contains 1) photosensitive silver halide, (2) a reducing agent, (3) a dye-providing substance, and (4) a binder, and further contains (5) an organic silver salt if necessary. However, these do not necessarily need to be contained in a single constituent layer,
For example, the photosensitive layer is divided into two layers, (1) (town), (
4) and (5) are contained in the photosensitive layer on one side, and the dye-providing substance (3) is contained in the layer on the other side adjacent to this photosensitive layer.
They may be contained separately in two or more constituent layers as long as they are in a state where they can react with each other.

Further, the photosensitive layer may be divided into two or more layers, such as a high-sensitivity layer and a low-sensitivity layer, and one or more other photosensitive layers having different color sensitivities may be provided. It may also have various photographic constituent layers such as an overcoat layer, an undercoat layer, a backing layer, and an intermediate layer.

As with the heat-developable photosensitive element, coating solutions for the protective layer, intermediate layer, undercoat layer, backing layer, and other photographic constituent layers are prepared respectively using the dipping method, air knife method, curtain coating method, or U.S. Pat. The light-sensitive material can be prepared by various coating methods such as the hopper coating method described in No. 681-294.

Furthermore, if desired, two or more layers can be applied simultaneously by the methods described in US Pat. No. 2,761,791 and British Patent No. 837,095.

The above-mentioned components used in the heat-developable photosensitive element are coated on a support, and the thickness of the coating after drying is l to t, o o o
The thickness is preferably .mu.m, more preferably 3 to 200 .mu.m.

The thermal development photosensitive element of the present invention is thermally transferred to an image-receiving element in a stacked relationship with the heat-developable photosensitive element of the present invention when it is thermally developed after imagewise exposure, or once it is reheated after completion of thermal development. It may also be a method of imparting an image to an image-receiving element, and this method is preferred in the case of a heat-developable color photosensitive element.

The above-mentioned image receiving element basically only needs to have the function of stopping the transfer of the imagewise distribution of the thermally transferred dye and fixing it.

For example, it may be a single layer of gelatin or other synthetic polymer, or it may be a layer of wood valve or other synthetic pulp fibers. Also, Research Disclosure Magazine No. 1516
Various mordants such as those shown in 2 may be used. Further, the image receiving element may include the image receiving element on a suitable support, and the support may also serve as the image receiving element. Furthermore, the image-receiving layer (element) may be formed on the same support as the support of the photosensitive element of the present invention.

Further, after the dye image is transferred to the image-receiving element, the image-receiving element may be peeled off, or it may be integrated with the photosensitive layer. Furthermore, an opaque layer (reflective layer) can be included if necessary. The opacifying layer can include various compounds that provide the necessary reflection, such as titanium dioxide and the like.

Effective image-receiving elements (which may have a separate support or may also serve as a support) include synthetic polymer films such as polyethylene terephthalate film, polycarbonate film, polyvinyl chloride film, and polyvinylidene chloride film. , ethyl cellulose film, etc., paper such as baryta paper, art paper, ipoly
Paper, plain paper, etc.

Particularly preferred image receiving elements have a single layer of synthetic polymer on a support, such as a baryta support with a polyvinyl chloride layer or a polycarbonate layer, a polyethylene terephthalate film support with a polychloride layer, etc. Some have a vinyl layer or a polycarbonate layer. Regarding these, please refer to the patent application No. 58-97.
No. 907 and No. 58-128600. Furthermore, polyvinyl chloride containing polyalkylene carbonate disclosed in JP-A No. 53-246,
Polyvinyl chloride containing silicone oil as disclosed in JP-A-51-88543 and JP-A-52-40557, as well as polyvinyl chloride with plasticizer retained by plasma treatment, are also useful as image-receiving layers.

The heat-developable photosensitive element is usually exposed to light at a temperature of 80% after imagewise exposure.
℃ to 200℃, preferably 120" to 170℃ for 1 second to 180 seconds, preferably 1.5 seconds to
Color development can be achieved by simply heating for 120 seconds. Further, if necessary, the film may be developed with a water-impermeable material in close contact with the film, or it may be preheated at a temperature in the range of 70° C. to 180° C. before exposure.

Various exposure means can be used for the heat-developable photosensitive element. For example, a tungsten lamp, a mercury lamp, a xenon lamp, a laser beam, a CRTl LED, etc. can be used as the light source.

As the heating means, all methods that can be used for ordinary photothermographic elements can be used, such as contact with a heated block or plate, a heated roller, or a heated drum. The Joule heat generated by electricity or a strong magnetic field can be suppressed by contacting the element, passing it through a high-temperature atmosphere, or using high-frequency heating, or by providing a conductive layer in the heat-developable photosensitive element or the heat-developable image-receiving element. You can also use There are no particular restrictions on the heating pattern, including methods of preheating and then reheating.
Although it is possible to perform heating at a high temperature for a short period of time, or at a low temperature for a long period of time, continuously raising the temperature once, lowering it, or repeating it, or even discontinuously, a simple pattern is preferable. Alternatively, a method in which exposure and heating proceed simultaneously may be used.

〔Example〕

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

Example-! 4-sulfobenzotriazole silver 5Q9 obtained by reacting 4-sulfobenzotriazole and silver nitrate in water, poly(N-vinylpyrrolidone) 209, and water 160
m(2) was dispersed in an alumina ball mill to prepare an organic silver salt dispersion.

Silver iodobromide (Ag Br:Ag I=97:3) having an average grain size of 0.125 μm and having a [111] plane was prepared as shown in the table below.
In the presence of the sensitizing dye shown in 1 and 4-hydroxy-6-methyl-1,3,3a,7-chitrazaindene, sulfur sensitization treatment was performed with sodium thiosulfate to obtain the following composition, and a photosensitive silver halide dispersion was prepared. A liquid was prepared.

However, the sensitizing dye is 4xio- per mole of silver halide.
'Mole added.

Silver halide (in terms of silver) 381g Gelatin 859/ 3530mf2 The following polymer dye-donor substance (1) 239 and the following hydroquinone compound 29 were dissolved in ethyl acetate 80a + I2, and Alkanol XC (manufactured by DuPont) 5% aqueous solution 50 -, phenylcarbamoyl gelatin (Rouslow, Type 1)
7819PC) l Aqueous gelatin solution containing 8.5 g 29
0 mQ and dispersed with an ultrasonic homogenizer to obtain a dye-providing substance dispersion.

Dye-donating substance (1) C.I.

Hydroquinone compound 0■ 15.5g of developer (1), 0.6g of the following development accelerator
, 10 g of poly(N-vinylpyrrolidone) and 1.25 g of the following fluorine-based surfactant were dissolved in water to make 100me,
A developer was obtained.

Developer (RIL) Development accelerator Surfactant NaO, S-5-Cl-C00CI (t(CFICFI)
)CI! -COOCR1(CF, CFri nH(+n, n
=2 or 3) Organic silver salt dispersion 20m+! , 4-sulfobenzotriazole lO% aqueous solution 6 mQ, dye-donor dispersion liquid 40 m
Qs photosensitive silver halide dispersion 15ml12. 3-methyl-1,3,5-pentanetriol as heat solvent 4.8
g, developer 10a + I2 were mixed, the pH was adjusted to 5.5 with 5% citric acid aqueous solution, and a hardener solution (tetra(vinylsulfonylmethyl)methane and taurine was mixed in l:1 (weight ratio)
and dissolved in a 1% aqueous solution of phenylcarbamoylated gelatin so that the content of tetra(vinylsulfonylmethyl)methane was 3% by weight. ) was added to a photographic transparent polyethylene terephthalate film with a thickness of 100 μm that had been undercoated.
A hydrophilic colloid layer made of a mixture of the phenylcarbamoyl gelatin and poly(N-vinylpyrrolidone) was provided thereon as a protective layer to prepare a heat-developable photosensitive element.

On the other hand, polyvinyl chloride (n=1
．． A heat-developable image-receiving element was prepared by applying a tetrahydrofuran solution of 100% (manufactured by Wako Pure Chemical Industries, Ltd.). Polyvinyl chloride is 12
9/m".

The photothermographic element was exposed to 1,600 C, M, and S through a step wedge, and was then placed in a heat developing machine (developer module 277.
After heat development at 160°C for 30 seconds at 3M Company,
When the photosensitive and receiver elements were separated, a magenta step wedge negative image was obtained on the surface of each receiver element.

On the other hand, the same exposed photosensitive element was developed at 20° C. for 3 minutes using a developer having the composition shown below, followed by stopping, fixing, washing with water, and drying to obtain a black and white image.

Table 1 shows the sensitivity of the black and white image and the sensitivity of the magenta transferred image obtained by heat development in relative values.

The sensitivity of the black image of the sample using comparative dye (A) was set to 100.
The sensitivity was determined using the fog +0.2 point.

Developer composition Metol 29 Anhydrous sodium sulfite 409 Hydroquinone
49 Sodium carbonate monohydrate
289 potassium bromide
Add 1g water to make tC.

Table 1 Comparative dye (A) Comparative dye (B) Comparative dye (C) As is clear from Table 1, the sensitizing dye of the present invention has the same desensitization effect as conventional sensitizing dyes due to heat development. is small and also has a large sensitizing effect on silver halide, making it possible to provide a highly sensitive heat-developable photosensitive element.

Example-2 Silver chlorobromide (AyC12:AyBr=5) was formed on the surface of silver iodobromide (A9Br:A9I = 93 nia) having an average grain size of 0.125 μm and having (111] planes as a core.
:95) to obtain tetradecahedral crystals with an average particle size of 0.17 μm, and the following sensitizing dye and 4-hydroxy-
A photosensitive silver halide dispersion was prepared by sulfur sensitization treatment with sodium thiosulfate in the presence of 6-methyl-1,3,3a,7-chitrazaindene to give the following composition.

However, the sensitizing dye is 1x10-4 per mole of silver halide.
Mol added.

Silver halide (in terms of silver) asi9 gelatin 859/3530m12 The following compound (1) 309 was dissolved in tricresyl phosphate and ethyl acetate, mixed with an aqueous gelatin solution containing a surfactant, dispersed with an ultrasonic homogenizer, and reduced. 500 mQ of an oil-in-water dispersion of the agent (reducing dye-providing compound) was prepared.

40 mQ of the photosensitive silver halide dispersion, 5. dispersion of reducing agent; OtaQ, further trimethylolethane 7
．． 5f, guanidine trichloroacetic acid 5.29, poly-4
- 40 ml of a 10% vinylpyrrolidone aqueous solution and a small amount of the same hardener solution as in Example 1 were added to prepare a coating solution.

The coating was applied to a photographic polyethylene terephthalate film that had been subjected to undercoating so that the silver content was 1.49/I11''.

On the other hand, as an image-receiving element, the following layers were sequentially coated on a transparent polyethylene terephthalate film having a thickness of 100 μm.

(1) Layer made of polyacrylic acid.

(2) A layer consisting of cellulose acetate.

(3) Styrene and N-benzyl-N, N-dimethyl-N
- a layer consisting of a 1=1 copolymer of (3-maleimidopropyl)ammonium chloride and gelatin.

For each sample obtained, a Ratten filter N0°29
and a step wedge to give an exposure of 4,000 CMS, and the developer module 277 gives an exposure of 150 CMS.
Heat development was performed at ℃ for 1 minute.

Thereafter, it was superimposed on the image receiving element soaked in water at 50°C.
After crimping 500 to 80097 cm for 30 seconds,
It was quickly peeled off to yield a yellow image on the receiving element.

On the other hand, the same liquid treatment as in Example 1 was performed to obtain a black and white image. The results are shown in Table 2 as in Example 1.

Table-2 Comparative dye (D) Cm's CtHs As is clear from Table-2, without containing organic silver salt,
Moreover, it can be seen that the sensitizing dye of the present invention is also excellent in a heat-developable photosensitive element containing a reducing dye-providing compound, with little desensitization caused by heat development.

Example 3 In Example 1, benzotriazole was used instead of 4-sulfobenzotriazole, the dye-providing compound dispersion was removed, and the following developer (2) was used instead of developer (1).
), and the same operations as in Example 1 were performed except for using the sensitizing dyes shown in Table 3 below to obtain a heat-developable photosensitive element.

H When the above heat-developable photosensitive element was exposed to light in the same manner as in Example 1 and thermally developed in the same manner, a silver image was obtained on the photosensitive element. Furthermore, liquid treatment was performed in the same manner as in Example 1, and the obtained results are shown in Table 3.

Table 3 Comparative Dye (E) As is clear from Table 3, the sensitizing dye of the present invention exhibits excellent desensitization due to heat development, even in heat-developable photosensitive elements that do not use a dye-providing compound. I understand that there is something.

Patent applicant Roku Konishi Photo Industry Co., Ltd. Agent Patent attorney Nobuaki Sakaguchi Procedural amendment (method) % formula % l Indication of the case 1985 Patent Application No. 123700 2 Name of the invention Heat-developable photosensitive element 3 Amendment Applicant name (127) Konishiroku Photo Industry Co., Ltd. 4 Agent 160 Address 5th floor, Building 2, 10-11 Nishi-Shinjuku 7-chome, Shinjuku-ku, Tokyo (0:1) :161-0055 (Main) FAX: 1
61-010:1 Name (7321) Patent Attorney Saka
Confidence Sho' (and 1 other person) 5 Date of amendment order August 27, 1985 6 Number of inventions increased by amendment 7 Specification subject to amendment (full text)

Claims (1)

[Claims] In a heat-developable photosensitive element having at least silver halide, a reducing agent, and a binder on a support, the photosensitive element includes at least a 5-membered heterocyclic nucleus having a nitrogen atom and a tellurium atom as ring atoms sandwiching a carbon atom. A heat-developable photosensitive element characterized by containing a sensitizing dye as one basic nucleus.