JPS5957234A - Thermodevelopable photosensitive material - Google Patents

Abstract

PURPOSE:To prevent fog using a compd. small in toxicity by incorporating at least one kind of a specified compd. as a photosensitive material. CONSTITUTION:The specified compd. to be used as a photosensitive material is represented by formula I in which X is halogen; R<1>, R<2> are each optionally substd. acyl, oxycarbonyl, oxysulfonyl, sulfo, sulfamoyl, or the like, and each may be the same or different; X is halogen, and may be any of F, Cl, Br, and I, but Cl and Br is preferable, and especially Br has high fog preventing effect, said acyl group is exemplified by acetyl, propionyl, benzoyl, naphthoyl, nicotinoyl, or the like, and the benzoyl group is especially preferable, and said oxycarbonyl group is exemplified by methoxycarbonyl, ethoxycarbonyl, phenoxycarbonyl, or the like group.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a heat-developable photosensitive material! especially〃
) This relates to a heat-developable photosensitive material in which the occurrence of blurring is prevented.

The photographic method using silver halide has superior photographic properties such as MC#, gradation, and resolution compared to methods such as electrophotography and diazo method, so it has traditionally been the most widely used method.
However, in recent years, images can be obtained easily and quickly by using silver halide and changing the method of image forming of photosensitive materials from wet processing using a developer to dry processing using heating, etc. Various techniques have been researched and developed.

At present, the most successful photosensitive material in the field of photosensitive materials that can be fully formed using this dry processing method is U.S. Patent No. 3. isko, Rioti issue and the same number 3゜u! This is a heat-developable photosensitive material that utilizes a composition containing an organic silver salt, a catalytic small amount of a photocatalyst (for example, silver lokenide), and a reducing agent as essential components described in each specification of No. 7.076. Although this photosensitive material is stable in the current state, it is generally stable at a temperature of Ir00C or higher, preferably Iatoo 6 after imagewise exposure.
When heated above 0, the organic silver salt oxidizing agent and reducing agent in the photosensitive layer cause an oxidation-reduction reaction due to the catalytic action of the exposed photocatalyst that is present in the vicinity of the organic silver salt oxidizing agent and reducing agent. Generate and then A [
, J: The exposed portion of the photosensitive layer quickly turns black, creating a contrast contrast between it and the unexposed portion (background), forming an image.

However, conventional heat-developable photosensitive materials have the disadvantage that undesirable silver formation occurs in white background areas where there is no image, resulting in blurring and blurring.

Although it is almost impossible to completely prevent this force/buri,
As a means to reduce fog,
Publication No. 1/3 (US Patent No.!, JI R.

The method using the water scissors compound described in No. 203) is currently the most effective.

However, unfortunately, as is well known, mercury compounds are highly toxic, and for example, when heat-developed, mercury evaporates into the surrounding area, and when discarded after use, there is a risk of mercury leaking out, causing pollution. Considering the power of prevention, it cannot be used.

On the other hand, Unexamined Japanese Patent Publication No. 624I, JO-IXO
3 Koza issue, same! 6-70! No. 113, same, f6-193
3! It is stated in these publications that certain organic polyhalokene compounds are useful as antifogging agents for heat-developable photosensitive materials, but the antifogging effects of the organic polyhalokene compounds described in these publications are was extremely low compared to mercury compounds.

Therefore, an object of the present invention is to prevent fogging by using a less toxic compound and to provide a material with a high thermal development sensitivity.

Another object of the present invention is to provide a photosensitive material in which the white background fog density increases little after development.

An object of the present invention is to provide a heat-developable photosensitive material containing at least all of (a) an M silver salt, (b) a photocatalyst, (C) a reducing agent, and (d) a binder; This can be achieved by containing at least one of the compounds shown below.

The compound represented by the general formula (1) of the present invention is
It is far less toxic than the mercury compound described in Publication No. 1.3, and has a remarkable anti-fog effect compared to conventionally known organic polyhalogen compounds.

R''-CX 2-I is also 1 (11 In the above general formula (11), , oxysulfonyl group, aralkylsulfonyl group, arylsulfonyl group, aralkylsulfonyl group, carboxy group, sulfo group''!f or sulfuryl group? The halogen atom of OX may be F% α, Br or 1, but α and Br are preferable, and when it is Br, the antifogging effect is particularly strong.

Examples of acyl groups in R1 and R2 include acetyl, propionyl, benzoyl, naphthoyl, and nicotinoyl groups, with benzoyl being preferred.

Specific examples of the oxycarbonyl group for R1, B, and 2 include methanesulfonyl group, ethoxysulfonyl group, and phenoxycarbonyl group.

Specific examples of the oxysulfonyl group for R'' and R'' include a methoxysulfonyl group, an ethoxysulfonyl group, and a phenoxysulfonyl group.

Examples of the alkylsulfonyl group of RIR2 include methanesulfonyl group, n--methanesulfonyl group, and n-hexadecylsulfonyl group.

The arylsulfonyl group of R1, H, 2 and L7 include phenylsulfonyl group, naphthylsulfonyl group, etc.

Examples of the aralkylsulfonyl group for B 1 and B 2 include a norphenethylsulfonyl group.

above) t, 1. Even if each of the ryosyl group, oxycarbonyl group, oxysulfonyl group, alkylsulfonyl group, ryosulfonyl group, allanoyl sulfonyl group, and carbamoyl group represented by R2 has a substituent,
Examples of substituents include norogen atoms, hydroxyl groups, alkoxy groups, iri-ruogishi groups, oxycarbonyl groups,
Oxysulfonyl group, acyl group, carboxy group, ryosyloxy group, carbamoyl group, amino group, amido group, alkylsulfonyl group, mercabuto group, alkylthio group, sulfo group, sulfamoyl group, nitro group, cyano group Examples include groups.

Among the above R'' and R2, an acyl group, an alkylsulfonyl group, an aralkylsulfonyl group, and an aralkylsulfonyl group are preferred, and a substituted or unsubstituted benzoyl group and a phenylsulfonyl group are particularly preferred.

Specific compounds f represented by general formula (1) of the present invention are as follows:
11 is shown, but it is not limited to 1.

(11 His (penzoylundibromomethane (2) α
-benzenesulfonyl-α,α-cyfuromorosetophenone (3) his(l-chlorobenzoyl)dibromomethane (4) bis(benzenesulfonyl dichloromethane (5) α-benzenesulfonyl-α,α-cyfuromoacetone (6) ) α,α-dibromoα-methanesulfonyl-acetophenone (bis(l-7tylbenzene/Lhonyl)dibromomethane (8) α-pensoyl-α,α-dibromoacetate (9), α- Ding cetyl-α, α-dibromobenzophenone Oω α-pensoyl-α, α-phenyl dibromoacetate aυ α-benzenesulfonyl-α, α-methyl cyfuromoacetate 02 α, α-dibromobennylacetic acid 0.3)
α, α-Dichloroα-sulpoacetophenone α rubonilt α, α−
Ethyl dibromoacetate θ7) α-(gufluoropensene sulfonyl J-
α, α-ethyl diduromoacetate QgJ α-benzoyl-α, α-ethyl dichloroacetate α9-2-(benzenesulfonyldibromomethyl)-yo-phenyl-/, J, II-oxadiazole (a)
α-benzenesulfonyl-α, α-dibromo 2,11
1-dichloroacetophenone The preferred amount of the above-mentioned compound of the present invention (component (e)) varies depending on the type of compound, but is generally io'' mol to 1 mol per mol of silver, %.
10'' mole to sxt o mole, but is not limited thereto.

The above compound can be synthesized by halogenation of an active methylene compound represented by the general formula ⇠□-CH2-;El, 2 by a predetermined method.

An example of KA physical synthesis is shown below.

Synthesis Example/Bis(benzoyl)dibromomethane (1) Dibenzoylmethane// , 2 g (0.03 mol), anhydrous sodium acetate/l, 119 (0.2 mol) are dissolved in acetic acid ioomt, and ar' Bromine/6v (0.1 mol l'im) was added dropwise to C while heating and stirring. After completion, the reaction solution was allowed to cool, added to v00μ of water, and the resulting precipitate was filtered. After washing with water and drying. , and recrystallized from n-hexane to obtain the title compound ts, sy2 as white crystals.

m, p, ri 6-ta 7°C synthesis ftl -Z α
-benzenesulfonyl-α,α-dibromoacetophenone (2) Benzoylbenzenesulfonyl meta-y (T
Roger and Becks J-Pr, 5 (
2) r7, Kota II/3g<0.0f-F Neil)kF
As Family A, the title compound was synthesized in the same manner as in Example 1 and recrystallized with ethanol to obtain 17゜l2 of the title compound as white crystals.
Obtain 1ζ. (H, p, / /
6 − / / 7 ° (two combinations H, example 3
α to benzenesulfonyl-α, α-dibromoacetone (
5) Acetyl phenyl sulfonyl methane 9,79 synthesized from chloroacetone and sodium benzene sulfinate (
0,0 fmol)? As a raw material, it was prepared in the same manner as in Example 1, and recrystallized with n-hexane to obtain 7.4' fl of the title compound in light brown male crystals. m=p-!
0-jj'c synthesis example μ α-benzoyl-α, α-dibromoethyl acetate (8) Benzoylethoxycarbonylmethane l, cof (0
, Hawk and McEl as raw material for 1 mol 11
ain, J, Amer, Chem, Sac,
s41.

It was synthesized according to the method of No. 21 and further purified using a ShiiJ Kakeru column to obtain the title compound Col. 1 as a colorless oil.

71 (0.01.2 mol) was obtained.

Synthesis example j α-Benzenesulfonyl-α, α-methyl bromoacetate a0 Methyl bromoacetate/j, 39 (0.1 mol), sodium benzenesulfinate, -, water
A methanol solution of 1 so- of mol) was refluxed for 2 hours.

After completion, methanol was distilled off under reduced pressure, and the residue was washed with water, extracted with ethyl acetate, and dried over magnesium sulfate.

Ethyl acetate was distilled under reduced pressure and dried to give crude crystals of methoxycarbonylbenzenesulfonylmethane tP, try7f.
I got r.

Carbon tetrachloride was added to the crystals, and 3λf/(0.2 mole of bromine) was added dropwise while refluxing. Further, 3.r of potassium carbonate was added and the mixture was stirred for 5 hours. Carbon chloride was distilled off, and the residue was extracted with ethyl acetate, washed with water until neutral, and then dried over magnesium sulfate. Ethyl acetate was distilled off under reduced pressure to obtain lf″L,
The gel-like residue was filtered to remove oil and washed with ethanol to obtain white crystals.
, further recrystallized from methanol to obtain the title compound, 2
I got it on f1.

m+p, //j-//A °C Synthesis Example 6 α-benzoyl-α,α-dichloroacetic acid ethyl acetate form 8 Add ethyl benzoylacetate and 2f (0.7 mol) to carbon tetrachloride. Sulfuryl chloride λ under heating under reflux
79 (0.22 mol) was added dropwise to the mixture, and refluxing was continued for 3 hours. After cooling, the reaction solution was gradually added to 4,400 parts of ice water, and 2,000 parts of carbon tetrachloride was added! It was extracted with It and dried with calcium sulfate. The four carbon atoms are distilled off under reduced pressure to produce a yellow oily substance.
I got 27 fl. Separated by silica gel chromatography,
Purification yields the title compound t/, a colorless oil.
I got Jft.

The component used in the present invention (organic silver salt of horse chestnut) is colorless, white, or pale in normal state, but when exposed to light, the photocatalyst (described below)
It reacts with a reducing agent (described below) to form silver (image) when heated and rolled over io'cw in the presence of As such organic silver salts, there are known silver salts of organic compounds having an imino group, a mercapto group, a thione group, or a carboxyl group, and specific examples thereof include the following.

(1) Imino group? Examples of iron groups in organic compounds include silver salts of benzotrizoles, silver salts of phthalazinones, silver salts of benzoxazinediones, $12 of imidazoles, complex salts of tetraazaindenes, and pentazaindenes. Silver salt.

(2) Examples of silver salts of organic compounds having a mercapto group or 1,000-ion group include silver salts of normerkabutobenzoogizazoles, silver salts of mercaptooxadiazoles,
Silver salts of λ-mercaptobenzothiazoles, silver salts of normalcabutobenzimidazoles, silver salts of 3-mercapto-guphenyl/, 2゜μ-triesters, etc.

(3) Carboxyl group? Examples of silver salts of organic compounds include silver salts of aliphatic carboxylic acids, silver salts of aromatic carboxylic acids (e.g., iron benzoate, silver phthalate, silver phenylacetate, 4"n-octadecylogycidiphenylglucose, etc.). silver salts of carboxylic acids), etc.

For more detailed examples of these organic silver salts and examples of organic silver salts other than those described here, see, for example, U.S. Pat.
4t17,071, same No. 3. j≠2.372, 3.716, r, 30, 3.233. ! t07
No. 032 and British Patent No. 1. ko3
0, 1,172 each specification or JP-A-Sho! 0-931.
32, 0-Tata 71, J No/4A/λ Coco, and J3-362, and in the present invention, these known organic Silver salts can be appropriately selected and used as component (a). For example, silver halide or silver pigment as a photocatalyst! When a t-mediated complex is used, all those which are relatively stable to light are selected from among the above-mentioned known organic silver salts. As a preferable example, carbon number io to gO
In particular, silver salts of Nagatsuki aliphatic carboxylic acids of 1 to 33 are mentioned, specifically silver laurate, silver myristate, silver palmitate, stearic acid steel, silver chidic acid, Examples include silver behenate, silver liguxate, silver pentacosanoate, silver cerotate, silver heptacanoate, silver montanate, silver melisinate, and silver roughcellate.

For example, the synthesis of organic silver salts is described in U.S. Patent No. 3! j
No. 7.073, same No. J, 4 (jjr,, t4'lI No.
Same No. J, 700.41! lr No. 3.1.39
．． 0 geta issue, same number 3. ri60. No. 1 British Patent
, /73,426 specifications or Japanese Patent Application Publication No. 327,
-27. This can be accomplished by various known methods, such as those described in Japanese Patent Nos., J/-/, 220//, and J/4A122.In particular, U.S. Pat. , 700. Da! specification or Japanese Patent Application Laid-open No. 1973-
3.20/! The polymers described in U.S. Pat. Specification of J'7,377 or JP-A-Sho Geter
Preferably, the presence of the lf''L metal-containing compound described in Japanese Patent No. 13227 improves the particle morphology, particle size, and/or photographic properties of the organic silver salt. The preferred range is that the organic silver salt produced is 1
moles, for polymers (7,7 SF to about 10,009 g, especially from about 19 to about jOOg, and for metal-containing compounds, sometimes from 10 moles to 10 moles).

Among the organic silver salts prepared as described above, the major axis is about o, oi microns to about 10 microns, and the special Vc is about 0.
, /micron to about 5 microns are preferably used.

In the present invention, the organic @salt of component (a) is
Approximately 0. /9 to about GV, preferably about 0.2 f/ to about 2.57. Koj
L is a necessary and sufficient amount range to provide a suitable image density, and if it is used less than this range, the pixel density will be insufficient, and if it is used more than this range, the image density will not increase, and on the contrary, The cost will be high.

The components used in the present invention (b+ but, l!ll medium are:
By being irradiated with electromagnetic radiation, it changes into a substance that catalyzes the entire S (image) formation reaction between the organic # salt of component (a) and the reducing agent of component (Cl) under heating of 060 or higher.
or a photocatalyst that has the ability to release such a substance and functions as a t component that is felt in a photosensitive material that exhibits thermal phenomena and as a catalytic component for the above-mentioned steel (image) forming reaction. Inorganic photoconductive materials such as zinc oxide and titanium oxide: US Pat. /j co, ri θ1 No. 1 Specification of the heavy metal and diazosulfonic acid group or sulfinic acid described in the specification: and/or Japanese Patent Publication No. 1999 Jsllyr, Japanese Unexamined Patent Publication No. Sho Glogua 2r, or The scissors and dye sensitive complexes described in U.S. Pat. No. 3,233,307 and U.S. Patent No. 3. '13
7. Photosensitive silver salts such as photosensitive silver halides as described in No.
about o,001 mol to 10 mol, preferably about 0.0
It is used in a range of 1 mol to about 1 mol.

Among these photocatalysts, those most suitable for use in the present invention are photosensitive silver halides, such as silver chloride, silver bromide, silver iodide, silver chlorobromoiodide, silver chlorobromide, and silver chloride. Silver iodide, silver iodobromide or a mixture thereof.

The preferred grain size of the photosensitive silver halide is about 0.0/
Micron to about 2 microns, especially about 2 microns. .

The range is from 0.03 microns to about 7.0 microns (7.0 J microns).
The amount is from i mol to 0.7 mol, preferably from about 0.03 mol to about 0.005 mol.

The photosensitive silver halide can be prepared by any method known in the field of photography, such as the single jet method (7), e.g.
It can be prepared in advance as an emulsion such as an ammonia process emulsion, a thiocyanate or thioether aged emulsion, and then mixed with other components of the invention and incorporated into the composition used in the invention. In this case, in order to make sufficient contact between the organic silver salt and g-photosensitive silver halide, for example, as a protective polymer when preparing a photosensitive silver halide emulsion, U.S. Pat. J, 706, jt6
J' No. 3.7/3, 1rJJ No. 3, 74A
Means using polymers other than gelatin such as polyvinyl acetals described in British Patent Nos. 1.36 and 270, British Patent Nos. 1.36 and 270, and British Patent No. 13.
, a means for enzymatically decomposing gelatin in a photosensitive silver halide emulsion as described in the specification of IR6 or US Patent @4! , (776, applying various means such as omitting the use of a protective polymer by preparing photosensitive silver halide grains in the presence of a surfactant as described in the specification of JJ No. I can do it.

The 1flC photosensitive silver halide used in the present invention is also disclosed in British Patent No. 1. As described in Tei Gua, 'Ij Tei No. 12, an organic silver salt is produced by injecting a scissors ion solution into a mixed solution in which a halogenating agent and an organic steel lump-forming component are coexisting. can be generated almost simultaneously.

Still another method is to apply a photosensitive silver halide forming component to a solution or dispersion of an organic silver salt prepared in advance or to a sheet material containing the organic silver salt, so that some of the organic silver salt is exposed to light. It can also be converted into silver halide. The photosensitive silver halide thus formed is in effective contact with the organic silver salt and exhibits favorable effects. The above-mentioned photosensitive silver halide forming component is a compound that can react with an organic silver salt to produce Mc photosensitive silver halide, and what compounds fall under this category and are effective are as follows. It can be determined by a simple test. After mixing the organic silver salt with the compound to be tested and heating if necessary, the presence of diffraction peaks peculiar to silver halide is examined using X-ray diffraction. The photosensitive halogenated complex-forming components that were confirmed to be effective through such tests include inorganic halides, onium halides,
There are halogenated hydrocarbons, N-halokene compounds, and other halogen-containing compounds, and specific examples thereof include U.S. Pat. guj7.07AI
No. 1I, 003,7419, British Patent No. 1,1
79g, Ri No. 56, Ri No. 1. Geta t.

Specification No. 36 and JP-A No. 3-270 Noah, same!
3-. It is explained in detail in the 2jl120 specification publication, but an example is given below. show.

(1) Inorganic halide: For example, a halide represented by MXn (where M is H, N)]4 and a metal atom, X represents α+Br and
and /i for NH4, and its valence number when M is a metal atom. Metal atoms include lithium, sodium,
Gallium, cesium, magnesium, calcium, strontium, barium, zinc, cadmium, mercury, tin,
(includes antimony, chromium, manganese, iron, cobalt, nickel, rhodium, celium, etc.) Bromine water and halogen molecules are also effective.

(2) Onium halides: for example, trimethylphenylammonium bromide, cetylethyldimethylammonium bromide, trimethylbenzylammonium bromide, m4'R7 ammonium halides: primary phosphonium halides such as tetraethylphosphonium bromide : Tertiary sulfonium halides such as trimethylsulfonium iodide.

(3) Halogenated hydrocarbons: Examples include iodoporm, bromoform, carbon tetrabromide, and coprom-2-methylpropane.

(4) N-halokene compounds: For example, N-chlorosuccinimide, N-bromoacidimide, N-bromphthalimide, N-bromocetobumide, N-iodosuccinimide, N-bromophthalazone, N-bromooxazole °
+7non, N-talolophthalazone, N-bromoacetanilide, N,N-dibromobenzenesulfonamide, N
70 molar N-methylbenzenesulfonamide, l,3-
(5) Other halogen-containing compounds: Examples include triphenylmethyl chloride, triphenylmethyl bromide, copromacetic acid, copromethanol, and benzophenone dichloride.

These photosensitive silver halide forming components are used in chemically small amounts relative to the organic silver salt. Usually, the range is from about o,ooi mole to about 0.7 mole, preferably 1 mole per mole of organic silver salt.
The mechanism is set at about 0.03 mol to about 0.005 mol. The photosensitive silver halide forming components may be used in combination within the above range. A part of the organic silver salt is converted into photosensitive silver halide using the intervening halide forming components. Conditions such as reaction temperature, reaction time, and reaction pressure can be selected and set from a wide range depending on the purpose of production, but usually the reaction temperature is about -20°.
The reaction time is from about 0.1 seconds to about 72 hours, and the reaction pressure is preferably set at atmospheric pressure. It is preferable to carry out the polymerization in the presence of 1.0% of the polymer used in this case.
, oi to about ioo, preferably about 0. / to about 10 parts.

The photosensitive silver halide prepared by each of the above-mentioned methods can be chemically treated with, for example, a sulfur-containing compound, a gold compound, a platinum compound, a palladium compound, an iron compound, a tin compound, a chromium compound, or a combination thereof. Can be sensitized. This chemical sensitization procedure is described, for example, in U.S. Pat. No. 1.036. As2, British Patent No. t, sit,
Each specification of trso issue, JP-A-Sho specification-2241JO issue, same! /-78' Jl issue and the same 1t-rtt cog issue. In addition, US Pat. 10. An increase in g can be achieved by coexisting with a low molecular weight amide compound as described in the specification of GRACO.

The photocatalyst of component (b), especially #photohalogenated fM, can be optically sensitized by various known dyes.
Effective optical sensitizing dyes include, for example, cyanine, merocyanine, rhodacyanine, complex (ternary or mononuclear) cyanine or merocyanine, holopolar dianine, styryl, hexianine, 711-nol, hemioquinol or xanthene dyes. Ru. Among cyanine pigments, thiazoline nucleus, oxazoline nucleus,
It is preferable to have a bilorin nucleus, a pyridine nucleus, an ogizazole nucleus, a thiazole nucleus, a selenazole nucleus, an imitazole nucleus. In addition, as acidic nuclei, thiovidantoin nucleus, rotanine nucleus, oxazolidinedione nucleus, thiazolidinedione nucleus, Haruhitool eL chichozorinone nucleus, malonide II nucleus or pyrazolone nucleus? Among the above, cyanine and merocyanine dyes having an imino group or a carboxyl group are particularly effective. Specifically, the analogy is U.S. Patent No. 3.7.
6/, No. 272, No. J, 7/L? ,4I! No. 5, No. 3,177, No. 3, British Patent No. 1°G At, 2
0/No. 1. Specifications of Japanese Pat.
The pigment can be appropriately selected from among the known pigments described in the Publications No. 60-736 μλ, etc., and positioned near the photocatalyst according to the techniques of the above-mentioned known examples. These optical sensitizing dyes are used in an amount of about 10 mol to about 1 mol per mol of the photocatalyst as component (b).

The component (ci reducing agent) used in the present invention is
(When heated under a photocatalyst, it reacts with an organic silver salt to reduce n'ff, and in a heat-developable photosensitive material, a redox image-forming component is used together with an organic silver salt. A suitable reducing agent is determined based on the type and performance of the organic silver salt to be used. For example, it has a strong reducing power for organic silver salts that are difficult to reduce. The reducing agent in stock is suitable, and it is easy to reduce.
A reducing agent having a weak reducing power is suitable for silver salts.

Commonly known reducing agents used in heat-developable photosensitive materials include monophenols and those containing two or more phenol groups. polypheno-7+Ls, mononaphthols, bisnaphthol systems, polyhydroxybenzene systems with 2 or more hydroxyl groups, polyhydrophosinaphthalenes with two or more hydroxyl groups, ascorbic acid, 5
- Biran 17)'n M, pyrazoline-ones, pyrazolones 1 phenylene/dichloromethane droxylamines, hydroquinone monoethers, hydroxymines, hydrazides, midomeximes, There are N-hydroxyureas, and more specifically, for example, U.S. Patent Nos. 3,6/J, 6.33, U.S. Pat. , No. 3, 73/,
2J'2, same No. JI71r-2.2 Ko2, same No. J
, 10/, No. 321, same f, J, 7ri 11. Reference No. 1r, No. 3. rri J, No. 163, same No. 3. IF5.37
No. 6, No. J, No. 770.17111, No. 3.1/
3, No. 3,773,612, 4y, 3.
r3y, oqr number, same number 3.117371r, same number p
, ooy, osy issue, same issue.

02/, 2IJtO, UK patent y, t, prb, ip
or Belgian Patent No. 77/6,016 and JP-A-30-36/413, So-: 16/
/θ issue, jO-//b0.23, j0-Tata 71
ri issue, same 5o-ipoii: wo issue, same, f/-j/ri 3
3@, si-co No. 3721, si-co No. 32-411727 or Tokukosho! /-3, tlsi issue Specific details are given in each publication 1. There are reducing agents, and the component (Cl) of the present invention can be appropriately selected from such known reducing agents.The selection method is to actually produce a photothermographic material and evaluate its photographic properties. jJ) Is the reducing agent used better or worse? This method is considered to be the simplest.

Among the above t, tC reducing agents, when aliphatic silver carboxylate is used as the organic silver salt, preferable reducing agents include 2
Polyphenols in which more than one phenol group is linked by an alkylene group or sulfur, especially an alkyl group (e.g. methyl group, ethyl group, propyl group, t- Polyphenols (e.g. /, /-
bis(cohydroxy-3,j-dimethylphenyll-
3,3,J) Limethylhexane, /, /-bis(no-hydroxy-j-i-butyl-j-methylphenyl)methane, /,l-bis(7!-hydroxy-,3,jt-dit) -butylphenyl)methane 1.2.6-methylenebis(nohydroxy-J-t-butyl-!-methylphenyl)-+-methylphenol, 6. A'-benzylidene-bis(co-di-t-butylphenol), 6.6
'-benzylidene-bis (not--/chiluo-methylphenol), 6,6'-benzylidene-bis (J
, 4-dimethylphenol], /.

l-bis(2-hydroxy-3,5-dimethylphenyl)-2-methylpropane, /, /, j, j-tetrakis(nohydroxy-3,!-・7'methylphenyl)-
co, 4I-ethylpentane, λ9.2-bis(guhydroxy-J,J-dimethyl)propane, co, nobis(
Terhydroxy-3,! -di-t-butylphenyl]bronoξnato U.S. Patent No. 3. ! /r, No. 903, p. 01/.

No. 2V or British Patent No. t, ar6. i-gu issue'!
Mr. Sho and Akira Tokukai/-! /ri No. 33, same, TO-36
/No.10, 4!0-//602:1, same j2-zada7
Polyphenol compounds described in each publication (No. 27 or Japanese Patent Publication No. 727); U.S. Patent No. 3.6
7, n7' (bis-β-naphthols (eg.

λ'-dihydroxy/, //-binaphthyl, 6゜6'
-dibromo-λlλ'-dihydroxyl.

l'-binaphthyl, 6.6'-dinitro-λ, λ'-dihydroxyl 1. l'-binaphthyl, bis(nohydroxy-7-naphthyl)methane, Hiroshi.

G'-dimethoxyt, i'-dihydroxy-J co'-
(binaphthyl, etc.): U.S. Patent No. 3. Za0/.

Sulponamidophenols or sulfonamide naphthols NFII, t as described in specification No. 32/n
(tfe-benzenesulfonamide phenol, -benzenesulfonamide phenol, 2,6-cyclobenzenesulfonamide phenol, goubenzenesulfonamide naphthol, etc.).

The amount of reducing agent 11 used in the present invention varies depending on the type of organic silver salt, reducing agent, and other additives, but generally it is about Q, Oj mol to about 10 mol per mol of organic silver salt. moles, preferably about 0. / to about 3 mol is suitable. Also, within this range, one or more of the above-mentioned reducing agents may be used in combination.

It is desirable to use an additive called an activator toner (hereinafter referred to as a toning agent). Color toning agents are involved in the process of oxidation-reduction reaction between organic silver salts and reducing agents to produce images [--in particular, black, and a wide variety of compounds are already known as color toning agents. However, most of them are compounds having an imino group, a mercapto group, or a thione group. Among these, an appropriate color toning agent is selected depending on the type of organic silver salt and reducing agent used, and the color tone agent described in US Pat. /j Ko, Ri Oa No. 3, 14t Da, 7 Ri No. 7 or the same Da, (776,
7 thalazinones (e.g., phthalazinone, no-acetylphthalazinone, no-rubamoylphthalazinone, etc.) described in the specifications of No. J4I, U.S. Patent No. 3.11lb
, iJA specification n;I'(,2-pyrazoline-ones (e.g. 3-methyl-no-pyrazoline-!)
-ones, etc.) or quinazolinones (e.g., quinazolinone, goo-methylquinazolinone, etc.), pyrimidines (e.g., 6-methyl-, goo-dihydroxypyrimidines, etc.) described in U.S. Pat. , 2.j) riazines (e.g. 3-
methyluda, 6-cyhydroxy/, 2. j) riazine, etc.], phthalazinediones (e.g. phthalazine dione etc.) described in Japanese Patent Publication No. 6.3-36774/-, cyclic imides (e.g. U.S. Patent No. J, r4tl);
,,/Specification No. 36 or JP-A ShojJ-! The succisoimides, phthalimides, or urazoles described in U.S. Patent No. 3. Benzoxazinedione a specified in the specifications of JT, No. 660 or S, Trz, No. 267, benzothiadinediones described in JP-A-33-7B OJ0, US% Third
Examples include heterocyclic compounds having an imino group such as naphthalimides (described in Specification No. 1, No. 1, No. 1, No. 1, No. 1, No. 1, No. 1, No. 1, No. 1, No. 1, No. 1, No. 1, No. 1, No. 1, No. 2003-1). Two or more of these preparations may be used in combination, for example, % Kaisho! No. 3-1020 and 0 same j! -3-3
As described in the specifications of each publication of No. 3113, by using benzoxazinediones, benzoxazinediones, or phthalimides in combination with phthalazinones, the color tone derived from storage under high temperature and high humidity can be improved. Deterioration of effectiveness can be completely prevented.

'Also, U.S. Patent No. 3. Hiro 7, 61 and 3.
As described in each specification of No. 2-44.732, phthalic acid, naphthoic acid or phthalamic acid and imidazole acid or phthalazines can be used in combination as a color toning agent.

When using a color toning agent, the amount used is from about 0.0001 mol to about 2 mol per mol of organic silver group, particularly about
A range of mol to about 7 mol is preferred.

Additionally, mercaptotetrazoles (e.g., j-phthalptotetrazole, l-phenyl-j-mercaptotetrazole), U.S. Pat. J//.

4'71, the same m3.993.661-@lk [e] Precursors of mercaptotetrazoles (for example [/-
Fetel-j-(p-methylphenylsulfonylthio)
-tetrazoles, etc., j-1it-substituted-normerkabutoxadiazoles (e.g. j-methyl-2-mercaptooxadiazole, etc.), j-substituted 1-2-mercaptothiacyazoles (e.g. yo-methyl- λ-mercaptothiadiazole, etc.), j-substituted-3-norcut-
1,2, triazoles (e.g. lI, j-diphenyl-3-mercapto=l,co-triazole, etc.), disulfides (e.g. di(l-phenyl-S-
tetrazolyl]-disulfy F, etc.)? The color tone is further improved when 5/0 mol to 2 mol is used per mol of the organic silver salt.

In addition to each component of the heat-developable photosensitive material of the present invention, compounds known in the art that are effective in preventing discoloration of white portions of treated materials due to light may be used. For example, U.S. Patent No. 3. Stabilizer precursors such as azole thioethers and blocked azolethiones as described in US Pat. No. 3,70
0. Tetrazolyl compound or precursor thereof as described in Specification No. 1 of US Pat. No. 3,707
, J77, same No. s, rye, Ta 4tb, same W
E3, rijj, ri r2, same 1I, 10! l', 66
No. 6, Specifications 1] gIK-noted compounds, and other U.S. Patent Nos. " * ' J A,
bj There are fL1c sulfur alone or QJ sulfur-containing compounds mentioned in the specification of No. 0, and these may be used in combination.1. May be used together. For example, U.S. Patent No. 3゜j♂
The mercury compound described in No. 033, U.S. Patent No. 3
．． rij7. μri No. 3 Specification VL t'1. Tabe m-
・Rokeno compounds, benzenethiosulponic acids as discussed in JP-A-Shoj/-7a Cocoa Publication, JP-A-Shojj
In addition to cerium compounds such as those described in JP-A No. 5-2, No. 2-O, as well as cerium compounds as described in JP-A No. 5 O-IO TOI, % IBO J, No. 5 O-II 333, and JP-A No. 5 O-IO TOI
-/JF+J/ issue, 51-≠7 Hiroiri issue, same jt/-
4koj Kota, 6l-j13kota, 6l-j13kota, J/-674
t3! No. 5t-7op33r, rJ-320
1j, mukai 61-22gu 31, 5i-sgu hiro 2r, mukai jl-7s4tj3, 5i-ixaa3o,
same! No. 3-1020, j3-/rirJj, j3-
All of the thermal antifoggants described in Kozahiro 17 Specification Publication may be used alone or in combination.

17c, ordinary tetrazaintene stabilizers have a feeling of hot mass.
Although it is ineffective for phase materials, it suppresses the slight concentration increase caused by silver sulfide over a very long period of time when the photosensitive material contains sulfide (for example, when using sulfur-sensitized silver halide). For this purpose, e.g.
y of The Photographic Pr
"Ocess", +th Ed,, PP3ri 1-3
9ta, Macmillan Publishing
Co, Inc.

(Tetrasyndenes described in NEW YORK+ etc. can be used.

1. With the antifoggant of the present invention.
In addition to the mercapto compounds and thioether compounds mentioned in No. 3 and No. 3 of the same J6-Tata 3J3, disulfide phytos and polysulfides are used in combination.

It's okay.

Each of the components used in the present invention is composed of component (d) 4>9 as a binder (both dispersed in a type of colloid and 1
．． Ru. Suitable binders include hydrophobic polymer phase materials, but depending on the case, hydrophilic polymer materials may be used in combination or alone. The 1L polymeric material used as a binder has a transparent or translucent color when applied or cast, and has a white color or a light color layer or film.For example, Proteins such as gelatin, cellulose derivatives, polyaccharides such as Textran or natural polymers such as -7 Rabbit gum, and US Pat.
11 or Japanese Patent Publication No. 1973-126, No. 126, No. 126, No. 126, No. 126! /-/96 Koj issue or the same≠Tarzadag 4
! There are synthetic polymer materials that are extensively described in each publication No. 3, among which polyvinyl butyral, polyvinyl acetate, ethyl cellulose, vinylidene chloride-vinyl mide copolymer, polymethyl methacrylate, vinyl chloride-vinyl acetate copolymer, and cellulose. Particularly preferred are acetate, gelatin or polyvinyl alcohol.

If necessary, more than one of these polymeric materials may be used in combination. The polymer material is used in an amount sufficient to support the components dispersed therein, that is, within a range effective as a binder. The range can be appropriately determined by a person skilled in the art, but for example, in the case where at least one organic complex salt is to be supported in a completely dispersed manner, the weight ratio is about /θ to l to l to lθ to the organic silver group. About is used in the range from pair l to l pair g.

The composition containing each component of the present invention is a film in which the binder used has self-supporting properties. If it is to be given, each component according to the known casting method? Molded ζn beams as supporting films are usually conveniently coated on various supports selected from a wide range of materials in a single layer or divided into 11-1 or more layers to form a heat-developable photosensitive material. Wait until it's completed. Materials for this support include various polymeric materials, glass, wool cloth, cotton cloth, paper, metal (e.g. aluminum), etc. However, sheets or rolls that are used as information recording materials are flexible. Those that can be processed are preferred. Therefore, the support in the present invention may be a plastic film (for example, a cellulose acetate film, a polyester film, a polyethylene terephthalate film, a polyamide film, a polyimide film, a triacetate film, or a polycarbonate film) or paper (in addition to ordinary paper, For example, printing base paper such as photographic base paper, coated paper or art paper, baryta paper, resin coated paper, polysaccharide as described in Belgian Patent No. 71RG, No. 61! n
Particularly preferred are pigmented papers containing pigments such as titanium dioxide, and polyvinyl alcohol casized papers.

The heat-developable photosensitive material of the present invention may include various auxiliary layers, such as the vapor-deposited metal layer described in U.S. Pat. No. 3,7111,117, British Patent No. 1,107. ? Specification No. 7 and JP-A No. 5i-II3i3o or the same! /-/ Punk layer or JP-A-Sho described in the Kotako λθ Specification Publication! 0-/
In addition to the bank layer containing the f''L, 7'C magnetic material described in Tata Publication No. 31,0, an antistatic layer and the JP-A No. 3-4
A 1rLfc undercoat layer as described in Publication No. 772/ can be provided. , and U.S. Patent Nos. J, 9JJ, 30
No. 1, same No. J, l#6.

No. 526, same No. 3. ZajA, No. 5.27 or No. 3
, 193, 160, the provision of a single layer of overcoat polymer as described in the respective specifications of
7'cL7'c Is the effect on each layer improving the moisture resistance or ilr heat resistance of the layer? It is preferable because it brings about The thickness of the top coat polymer layer is suitably from about 1 micron to about 20 microns, and suitable polymers include those mentioned in the above-cited specifications as polymers for the top coat polymer layer agent.
Among them, polyvinyl chloride, polyvinyl acetate, vinyl-vinyl lactate cobo-11mer, polystyrene, methyl cellulose, ethyl cellulose, cellulose acetate fillate, vinyl chloride-vinyl chloride copolymer, sulfoxyesters, Cellulose acetate, vinylidene cyclization, polycarbonate, gelatin, polyhinyl alcohol and the like are preferred.

The film or layer containing each uninvented component or each auxiliary layer may contain additives known in the field of heat-developable photosensitive materials, such as plasticizers, capping agents, surfactants, sensitizers, brighteners, and light-absorbing agents. Contains substances, filter dyes, antihalation dyes, color couplers, hardeners, lubricants, development accelerators, stabilizers, etc., Volume 72 (J issue 1971)
A 9-2 J 2η 1107 pages Junpo, Unexamined Japanese Patent Publication 1986-
3. 361j, Mukai 30-/ri 6ko 3, Mukai 60-4
No. 76/R, No. J/-, No. 27, No. 23, or U.S. Pat. No. 3, No. 76, No. 31,
00/No. 3,667, Rijri No. 3.17/
, 1r7, same No. 3. rrs, ri 6/issue, same p.

2/, lso issue, same issue, 031. , 6jtO No. 3, 33/, Ko♂ No. 6, Ibid. No. 3.76≠, and No. 31r.

The method for preparing the heat-developable photosensitive material of the present invention is as follows. That is, the organic Shishio Purple prepared using one of the known methods is washed with water, alcohol, etc. as necessary, and then mixed with a photocatalyst to form a mixture in which the two are in close contact with each other. Alternatively, the photocatalyst may be produced simultaneously with the organic silver salt, and most preferably, a portion of the organic silver salt may be converted to silver halide by a silver halide-forming component. If a sensitizing dye is used, it is preferably added in the form of a solution to the mixture after the above mixing.

The mixture of organic silver salt and photocatalyst is desirably prepared as a polymer dispersion dispersed in a solution of a polymeric material which subsequently functions as a binder. This polymer can be added at any time, such as during the preparation of the organic silver salt, during the mixing of the photocatalyst, or during the preparation of the photocatalyst. This polymer matrix of Wm Sushi salt and photocatalyst may be formed into a film or coated in a layer on a support, and the other components of the present invention may be impregnated in a layer provided on the film or layer. However, preferably, other components used in the present invention, at least a reducing agent and the components of the present invention (d+'i) are further added to the polymer dispersion of the organic silver salt and photocatalyst to form a heat development-sensitive composition, It is cast to form a membrane by a known method or coated as a layer on a support.For coating, K can be applied by dipping, air knife, curtain coating, or hopper coating, or by various known coating methods. Furthermore, if desired, various auxiliary layers such as an undercoat layer and a topcoat layer may be applied prior to, simultaneously with, or after the application of the composition by similar application methods.

Any solvent may be used in the coating solution, but British Patent No. 1.
It is also possible to use all nonflammable solvents such as those described in Guco J./≠j.

If desired, the front or back side of the support, or the layer coated on the support, can be printed in a predetermined pattern, such as a train ticket, postcard or other document. It can be applied to

The heat-developable photosensitive material thus produced is cut into a size suitable for use, and then subjected to image exposure.

If necessary, preheat (10'C-/170'C1) before exposure.
may be given. Light sources suitable for image exposure include tungsten lamps, fluorescent lamps for copying which are mainly used for diazo-sensitive materials, mercury lamps, iodine lamps, xenon lamps, CRT light sources, laser light sources, and various other light sources. Fru.

The manuscript contains not only line images such as technical drawings, but also gradation? It is also possible to use a photographic image that you have, or use a camera to take pictures of people and landscapes. As a printing method, it may be printed by contact printing on top of the original, reflective printing, or enlarged printing.

The amount of exposure varies depending on the sensitivity of the sensitive material, but a high-sensitivity one requires about 1 lux seconds, and a low-sensitivity one requires about 103 lux seconds. η・〈imagewise exposed f'L7'c A sensitive material can be developed by simply being heated (approximately tθ0C or higher, preferably approximately 10° QC to approximately /jO”c). The heating time is 1
It can be arbitrarily adjusted such as seconds to 10 seconds. This is determined in relation to the heating temperature. Normally, /, about j seconds to about ≠ O seconds at 200C, about 2 seconds to about 20 seconds at 1306C, /1I00
Approximately c is about 10 seconds to about 10 seconds. There are various means for heating, for example, the sensitive material may be brought into contact with a simple heated plate, it may be brought into contact with a heated drum trap, or in some cases, the material may be passed through a heated space. good. Further, high frequency heating or laser beam heating may be applied.

The present invention will be described in more detail with reference to Examples below.O Example 1゜The above composition was dispersed with a homogenizer to prepare a polymer dispersion of silver salt.

This silver salt polymer dispersion was maintained at TO'C, and the following solution was added and heated for 0 minutes to convert part of the silver behenate to silver bromide.

The silver behenate-silver bromide polymer dispersion thus prepared was maintained at ≠ (76C) and the following compounds were added in the order listed.
The coating solution was prepared.

The coating solution thus prepared was coated onto photographic base paper at a silver content of 0.4Ay per m2, dried, and then coated with an overcoat layer of λ of cellulose diacetate.
Polymer amount of acetone solution is /ln2 o,
4! It was set so that y. The heat-developable photosensitive material thus prepared is referred to as A-/.6 As a comparative sample, a photothermographic material prepared in exactly the same manner as A-/ except that α-benzenesulfonyl-α and α-dibromoacetophenone (-2) were removed. The material is 13-/.

In order to prepare another comparison sample, α
- A sensitive material prepared in the same manner as B-1 except that 1% by weight methyl ethyl ketone solution of tribromoacetophenone (loo, 4) was added in place of the addition of Dunzensulfonyl-α,α-dibromoacetophenone (-2). . Further, a sensitive material prepared in exactly the same manner except that mercuric acetate/weight ratio methanol solution≠Oat was added was designated as B-J.

After exposing these samples to IO lux seconds through an optical wedge, a black image was obtained by heating for 10 seconds at a temperature of /,2 (70C).Next, the reflection density of these samples was measured, and fog was also detected. Q.

Sensitivity was calculated using the reciprocal of the exposure amount required to give a higher reflection density as a scale of sensitivity.Table 1 shows the measured values of relative sensitivity, heat fog, and maximum density when the sensitivity of 33-7 is set as 100. showed that.

From the measurement results shown in Table 1, sample A-
Compared to comparative samples B-/ and B-2, / had extremely high heat fog prevention properties, and the decrease in sensitivity and maximum concentration was slight. Also, 1. Comparison using mercury compounds. Sample B-
Even when compared with 3, it was found that there was almost no difference in performance. Further, when sample A-/ of the present invention was left on a Scherkasten for one hour, no increase in fogging occurred in the white background area. Furthermore, this sample was heated to 10'C, 704
Almost no increase in fogging on the white background was observed even when the sample was left in the dark for 3 days at RH.

Example 2 Example 1. α-benzenesulfonyl-α in the case of α-benzenesulfonyl-α.

A thermal mass f-image sensitive material was prepared in exactly the same manner as A-/, except that other compounds of the present invention were used in place of α-dibromoacetophenone (-2). (A-co-A-IO) The results of sensitometry performed on these samples in the same manner as in the examples are shown in Table 2.

The measurement results shown in Table 2 indicate that the present invention produced a photosensitive material with extremely low heat buildup.

Claims (1)

[Scope of Claims] A heat-developable photosensitive material comprising at least (a) an organic silver salt, (b) a photocatalyst, (c) a reducing agent, and (d) a binder, further comprising (e) the following general formula fil. A heat-developable photosensitive material characterized by containing at least seven types of compounds shown in the following. R-CX-R"fi+, and X represents a rogen atom; B1.B2 is an unsubstituted acyl group, an oxycarbonyl group, an oxysulfonyl group, an alkylsulfonyl group,
represents an arylsulfonyl group, an aralkylsulfonyl group, a carboxy group, a sulfo group or a sulfamoyl group,
几1 and R2 may be the same or different.