JPS5957233A - Thermodevelopable photosensitive material - Google Patents

Abstract

PURPOSE:To provide a photosensitive material prevented from fog, especially increase of fog on the white background after development by using a compd. small in toxicity. CONSTITUTION:A thermodevelopable photosensitive material containing at least (a) an org. silver salt, (b) a photocatalyst, (c) a reducing agent, and (d) a binder further contains at least one of compds. represented by general formula I in which X is halogen, any or F, Cl, Br, and I may be used, but Cl and Br are preferable, especially Br is suitable; Z is S, O, or N-R<1>; R<1> is optionally substd. 1-18C alkyl or such 6-22C phenyl, naphthyl, or such 2-18C acyl; when Z is S or O, a fog preventing effect is raised; R is a substituent on the benzene ring; (n) is 0 or an integer of 1-4; when (n) is 1-4, R is halogen, OH, COOH, sulfo, nitro, cyano, or the like, and when (n) is 2, 3, or 4, the substituents may be the same or different.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a heat-developable light-sensitive material, and particularly to a heat-retainable heat-developable light-sensitive material in which the occurrence of fogging is prevented.

Silver halide? The photographic method used has superior photographic properties in terms of g, gradation, and resolution compared to methods such as electrophotography and diazo photography, so it has traditionally been the most widely used method. In recent years, various techniques have been developed that can easily and quickly obtain images by changing the image forming process of photosensitive materials using silver a-genide from wet processing using a developer to dry processing using heating, etc. has been researched and developed.

Currently, photographic images are created using this dry processing method.

The most successful π material in the field of photosensitive materials that can be achieved is U.S. Patent No. 3. IIλ, riθμ and 3゜177.0
This is a π heat-developable photosensitive material that utilizes all of the compositions described in each specification of No. 75, including an organic silver salt, a small amount of a catalytic photocatalyst (for example), a halogenation agent, a silver fluoride, and a reducing agent as all essential components. This light-sensitive material is stable at a temperature of 100° C., but after image exposure, it is usually heated to a temperature of 10° C. or higher, preferably 10° C.
When heated above θ0C, the organic silver salt oxidizing agent and reducing agent in the photosensitive layer undergo an oxidation-reduction reaction under the catalytic action of the exposed multiplication catalyst present in the vicinity, thereby producing silver. The exposed areas of the photosensitive layer quickly turn black and create a contrast with the unexposed areas (background) to form 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 the formation of fog.

It is almost impossible to completely prevent this fog, but as a means to reduce it,
Publication No. 13 (US % J, 319).

The method using mercury compounds described in No. 703 has been the most effective so far.

Unfortunately, however, mercury compounds are known to be highly toxic, and when heat is developed, mercury evaporates in the vicinity, and when discarded after use, mercury leaks out. It is so thick that it cannot be used from a pollution prevention perspective.

On the other hand, Unexamined Japanese Patent Publication Showjθ-/liri 6 cog No. 1 KamojfO-i2
No. 03.2r, JA-70 Yo41-3, J6-Tata No. 335, etc. describe that certain organic polylogen compounds are useful as antifoggants for heat-developable photosensitive materials. However, the antifogging effect of the organic poly(I)/-rogen compounds described in these publications is extremely low compared to that of mercury compounds.

Therefore, the purpose of the present invention is to use less toxic compounds to prevent fogging. An object of the present invention is to provide a heat-developable photosensitive material that prevents the occurrence of heat development.

Another object of the present invention is to provide an advantage in which the increase in fog 9e of a white background after development is small.

The object of the present invention is to provide a heat-transferable 1J2 photosensitive material containing at least (a) an organic silver salt, (b) a photocatalyst, (C) a reducing agent, and (d) a binder, and further comprising the following general formula (, I). This is achieved by containing at least seven of the compounds shown.

The compound represented by the general formula (1) of the present invention is
////The mercury compound described in Publication No. J is far less toxic and has a remarkable effect of preventing erectile dysfunction, which is a conventionally known organic polyhalogen compound stabilizer.

In the general formula (1), X is represented on a halogen atom and may be any of F%0, B'', and ■, but α and Br are preferable, and Br is particularly preferable.

Z represents a sulfur atom, an oxygen atom or N-R11. R
1 is substituted or unsubstituted C2-C18 alkyl group, substituted or 7c is unsubstituted C6-C22 phenol group, naphthyl group, and substituted trap is unsubstituted C2-C18 acyl group. represent. In particular, when Z is a sulfur atom or an oxygen atom, the effect of preventing η vibration is strong.

(R) nl″t represents the substitution fund on the benzene nucleus, n is O
M71- represents an integer from 1 to Hiro. When n is 1 to 1), examples include a halogen atom, a human myxyl group, a carboxy group, a sulfo group, a nitro group, a cyan group, or a substituted or unsubstituted alkyl group, an alkyl group, an alkoxy group, an aryl group. Oxy group, argyloxycarbonyl group,
Examples include aryloxycarbonyl group, alkyloxysulfonyl group, aryloxysulfonyl group, acyl group, acyloxy group, carbamoyl group, amine group, amide group, alkylsulfonyl group, arylsulfonyl group, mercapto group, and sulfamoyl group. When n=2 to μ, the above substituents may be the same or different. In particular, when one electron-withdrawing group is substituted, a favorable antifogging effect can be obtained.

Specific examples of the compound of the present invention represented by general formula (I) are shown below, but are not limited thereto.

(1) Coated tripromomethylbenzothiazole (2
)! -Chloronote tribromomethylbenzothiazole (3)j, A-dichloroa-,2-1 bromomethylbenzothiazole (4) A-dichloro-2-)! J Dichlorotylbenzothiazole (5) Yo, 6-dimethyl-u-)! j dibromotylbenzothiazole +6)! -Methoxycarbonyl-no-trifluoromethylbenzothiazole (7) 6-medoxy-no-tribromomethylbenzothiazole (8) j-phenyl-no-trichloromethylbenzothiazole (9) j-acetyl-,2-MJ dibromotylbenzothiazole OI λ-Trifluoro a-methylbenzoxazole 0
1), 2-) Ribromomethylbenzoxazole Us-
p-6-methyl-2-tribromomethylbenzoxazole (t3i -t-octyl-no-tribromomethylbenzoxazole (1414-phenoxy-no-tribromomethylbenzoxazole α51/-methyl-co-tribromomethylpenzimidazole QQ j I & 9chloro-7-ethyluno)
IJ Furomomethylbenzimidazole α7)/-Methyl-II,j, 6,7-titrachloro-tribromomethylbenzimidazole Ql19/-(-2-methoxyethyl), 2-toIJ Bromomethylbenzimidazole a! 16-chloro-hiro-nidro/-(μm sulfoptylene-1-trichloromethylbenzimidazole t2Bi-pensoyl-j, A-cyclolose-tribromomethylbenzimidazole Preferred usage amount of the above compound of the present invention (component (e)) Although it varies depending on the type of compound, it is generally 10 mol per 1 mol of silver, especially 10-3 mol to zxio
The range is in moles, but is not limited thereto.

The above-mentioned compounds can be prepared using known general synthesis methods for benzothiazoles, benzoxazoles and benzimidazoles, such as Belsteln B, Vol. 27, page 2.
/, pageJ (Synthesis of 2-methyl, J-7 dynylbenzothiazole) s page%λθlr1.9/,
/17 (Synthesis of methyl, -mono-phenylpenzoxazoles), pagel 1j-2, /60 (Synthesis of /-methyl, no-methylbenzimidazole); Large Organic Chemistry, Volume I ■ Written by Masaki Ota, li 57 Year, Breakfast Bookstore, p.
lψ6 (benzothiazole), p, lIs<benzoxazole), p.

, 2JJ' (benzimidazole) I The c
hemIstryof Heterocyclic c
compounds, ”lm1dazoleand i
ts Derivatives, Part I, /
”?j3.

Interscience Publlshers I
nc,, New York.

p, 2g-7 (benzimidazole), etc., using trihaloacetic acid or trihaloacetyl halide (■1) and (nJ
It is easily synthesized by the condensation reaction of (Scheme (1)
)) (However, x, z, (general) n have the same meaning as general formula (I)) In addition, the compound where X=Br in general formula (I) is represented by general formula (IV
)'['It can also be easily synthesized by direct bromination of the non-methyl form shown. (x Scheme (2)) Specific synthesis examples are shown below.

Synthesis Example 1> λ-Tribromomethylbenzothiazole (1) λ-aminethiophenol/-2. I? (0.10 mol), Viridi 71.7? In addition to 700 ml of (0,//mok)-f tetrahydromifuran, tribromoacetyl chloride 369 (o, tQ mol) was added dropwise to a water-cooled bottom stopper.

After completion of the dropwise addition, the mixture was heated and stirred for 30 minutes at room temperature and then for 7 hours.

Reaction liquid! 00ml of ice water, and the resulting precipitate was filtered, dried, and then recrystallized from n-1 xane L5 to obtain the title compound (1). m, p, 7F-10'C Synthesis Example 2>a-) Lipcumomethylbenzothiazole (
Separate synthesis method of 1) No-methylpenzothia y-hia,yy(o.

While refluxing an acetic acid solution of sodium acetate u/f (0, j mol), drop odor (0# mol) into the trap. After completion, reflux for /#, and release. After cooling 2
00- was added to ice water.

After settling, Rt-filtering, washing with water, drying and trapping,
Recrystallization from n-hexane gave the title compound (1) as pale brown crystals.
)/J, 4(If obtained. m, p, 7 F-
101'C Synthesis Example a), r,4-dichloro-λ-tribromomethylbenzothiazole (JJ' t-dichloro-λ-methylbenzothiazole co/,If (Q,/%) with lc charge T, T, By the same procedure as in the synthesis example, the title compound of light brown crystals was obtained.
Obtained. m, p, 103-10 synthesis example 4>J-)
Lipromomethylbenzoxazole (//) No-methylbenzoxazole J, 3f (Q.

The same procedure as in Synthesis Example 1 was carried out using 1 mol) t as a raw material, and the product was purified using a silica gel column, trapped, and recrystallized from methanol to obtain the title compound t, sy2 as pale brown crystals. m,p,retar/QC Synthesis Example 5> l-Methyl-coatlip amomethylbenzimidazole (/j) N-methylnonitroaniline/! ,,2f(Q-/
%le), R-based iron-14'? ,Ammonium chloride.

, water, water, and impropanol were added to a 75-liter vessel, and the mixture was heated and stirred at about 75 degrees centigrade for 3°. The reaction solution was filtered, and the F solution was distilled off under reduced pressure to obtain a crude product of LJ, N-methylphenylenediamine. This was dissolved in 100% of tetrahydro7ran, pyridine r, yy (o, ii mol) was added, and 36 fl (0,1 mol) of tribromoacetylbromide was added dropwise under water cooling. After the dropwise addition was completed, the mixture was heated and stirred on a steam bath for 1 hour at room temperature and then for about 2 hours. Reaction liquid? In addition to about 5OO- of ice water,
After filtering the precipitated crystals, the title compound <1s
) io, 6y2 gain 1ζ. m, p, 101'~/
/λOC The organic silver salt of component (a) used in the present invention is:
Normally, it is colorless, white, or light-colored, but in the presence of an exposed photocatalyst (described later), it sometimes reacts with a reducing agent (described later) when heated to a temperature of 1 RO 0 C or more, and the silver (image) is mainly composed of gold. It functions as an image-forming component in a heat-developable photosensitive material. Such organic silver salts include imino groups and mercapto groups.

Silver salts of organic compounds having a thione group or a carboxyl group are known, and specific examples thereof include the following.

(1) Examples of silver salts of organic compounds containing imino groups include silver salts of benzotriazoles, silver salts of phthalazinones, silver salts of benzoxazinediones, silver salts of imidazoles, and tetraazaindenes. silver salts of pentaazaindenes, etc.

(2) Examples of silver salts of organic compounds having a mercapto group or thione group include silver salts of λ-mercaptobenzoxazoles, silver salts of mercaptooxadiazoles, silver salts of nor-mercaptobenzothiazoles, and Silver salt of mercaptobenzimidazole, 3-mercapto-Hiro-phenyl 1. λ.

Silver salts of μ-triazoles.

(3) Examples of silver salts of organic compounds having a carboxyl group include silver salts of aliphatic carboxylic acids, silver salts of aromatic carboxylic acids (for example, silver benzoate, silver phthalate, silver phenylacetate, g'-n -Octadecyloxydiphenyl-Hiroshi-
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, US Patent No. 3.
Ko 17.073, same No. 3. j Geta, No. 372, No. 3
, 711j, No. 130, No. 3, No. 33,107, No. 3, No. 33,107, No. 33,107, No. 33, 107, No. 032, and British % revision No. 1,230.6.
Hiroko issue specifications or JP-A-Sho-ta No. 313, same! 0
−? R71? No. 1+2-/g/, No. 2J+2, and No. 53-34.2.2f, and in the present invention, appropriately selected from these known organic silver salts. It can be used as component C (a). For example, when silver halide or a silver dye photosensitive complex is used as a photocatalyst, a relatively stable one is selected from among the above-mentioned known organic silver salts. Preferred examples thereof include @ salts of long-chain aliphatic carboxylic acids having 10 to 4 AO% carbon atoms, especially lIr to 33 carbon atoms, and specifically, silver laurate, silver myristate, silver nomyrmitate, silver stearate, and alaxin. Examples of gold include silver l#, silver behenate, silver lignocerate, silver bontacosanoate, silver cerotate, silver heptacosane M, silver montanate, silver melisin, and silver lafuselate.

The synthesis of such organic silver salts is described, for example, in U.S. Pat. Approximately No. 1,81, 1i4 No. 3
．． yoo, USR No. 3, Ire? , 0
Kou No. 2, Kou No. 3. rito, yor, British Patent No. 1, /
7! , Gu No. 6 each 8Aa book or JP-A-Sho μter j26.2
No. 6, same! I-1, 2, 20// issue, same! J-/41-
This can be achieved by various known methods described in various publications. In particular, during the formation of organic silver salts, rice IS%#'l'
Jll, 7 o o, az No. 1 specification or JP-A-Sho! Trap polymers described in 3-3-01j, U.S. Pat. Preferably, a metal compound is present because it can improve the particle morphology, particle size, and/or quaternity of the organic silver salt. The preferable range of the usage amount of these coexisting components is from about 0, iy to about 10,001 in the case of polymers, especially from about /f to about 5ooy, and 10,000 in the case of metal-containing compounds, per 1 mole of the organic silver salt produced. moles to lQ moles.

Among the organic silver salts prepared as described above, those having a particle size of about 0.01 micron to about 2 micron, particularly about 0.1 micron to about 5 micron in major diameter are preferably used.

In the present invention, the organic silver salt of component (a) is
Approximately 0.0 in terms of silver amount per L2. It is used in the range of /f to about≠11, preferably about O, 1 to about JV. This is a necessary and sufficient amount range to give an appropriate image density; if you use less than this range, the pixel density will be insufficient, and even if you use more than this range, the image density will not increase. However, the cost will increase.

Component (b), the photocatalyst used in the present invention, is produced by ``by being irradiated with electromagnetic radiation, the organic silver salt of component (a) and the reducing agent of component (C) are combined under a force of ro0c or higher and under heat. It has the ability to convert into a substance that catalyzes the silver (1#) formation reaction or to release such a substance, and is used as a photosensitive component and a catalyst component for the silver (image) formation reaction in heat-developable photosensitive materials. Such photocatalysts include inorganic photoconductive materials such as oxidized!11!lead and titanium oxide; Salts with diazosulfonic acid or sulfinic acid; and/or described in Japanese Patent Publication No. 4Ay-Kojhiro R, JP-A No. 6-47λr, or U.S. Patent No. 3.33,107 Photosensitive compleras of silver and dyes and U.S. Patent No. 3.Hiroshi!7.071
There are photosensitive silver salts such as photosensitive silver halides described in the specification, and usually 1 mole of organic iron salt is about o, oo
The amount used is from t mol to io mol, preferably from about o,oi 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, silver chloroiodide, silver iodobromide, or a mixture thereof.

The preferred grain size of the photosensitive silver halide is about 0.0/
microns to about 2 microns, particularly about 0.03 microns to about 0.3 microns. The range of the amount used is approximately 0.00 mole to 0.00 mole per 1 mole of organic silver salt.
7 moles, preferably about 0.03 moles to about O0! It is a mole.

The photosensitive silver halide can be prepared by any method known in the field of photography, such as a single jet method or a double jet method, such as Lippmann emulsion, ammonia method emulsion,
It can be prepared in advance as an emulsion, such as a thiocyanate or thioether aged emulsion, and then mixed with the other components of the invention and incorporated into the composition for use in the invention. In this case, in order to bring the organic silver salt into sufficient contact with the photosensitive silver halide, for example, as a protective polymer when preparing a photosensitive silver halide emulsion, US Pat.
No. 44, No. 3,706.66! No. 3.7/3,
No. 133, No. 3, 7, /su No. 3, British Patent No. 1,
No. 36 and No. 270, there are methods in which polymers other than gelatin such as polyvinyl acetals are used all around, and British Percentage No. 1°3!4! :, Gelatin of photosensitive silver halide emulsion as described in /za No. 6 Specification? Means for enzymatic degradation or U.S. Pat. No. 4', 074.1
As described in the specification of No. 37, various means such as a means of completely omitting the use of a protective polymer by uncoupling photosensitive silver halide grains in the presence of a surfactant? Can be applied.

Photosensitive silver halide trap used in the present invention British Patent No. 1. As described in Hirohiro 7.4Ajt specification, a halogenating agent and an organic silver salt forming component? By injecting a silver ion solution into the coexisting mixed solution, the silver ion solution can be produced almost simultaneously with the production of the organic silver salt.

Still another method is to use a solution or dispersion of a trapping organic silver salt prepared in advance or a solution or dispersion of the organic silver salt. It is also possible to convert a portion of the organic silver salt into photosensitive silver halide by acting on the sheet material containing the photosensitive silver halide forming component. 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 photosensitive silver halide.Which compounds fall under this category and are effective can be determined by the following simple steps. It can be determined by testing. That is, after mixing the organic silver salt and the compound to be tested and heating if necessary, X-ray diffraction reveals a diffraction peak specific to silver halide. Photosensitive silver halide forming components that have been confirmed to be effective through such tests include inorganic halides, onium halides, halogenated hydrocarbons, halogen compounds, and other halogen-containing compounds. For specific examples, see U.S. Patent No. 00? , No. 032, Same No.! , 1lj7.07.
No. 44,003,741, British Special No. 'f No. 1. ≠2g, ri No. 56, same No. 1. Geta r.

P16 specifications and JP-A-Shoj3-Core No. 027, same!
13- and 2j'l Ko No. 0 are detailed in the respective publications, and an example thereof is shown below.

(1) Inorganic halides: for example, expressed as MXn
halides (where M represents H, NH4 and metal atoms, X represents Q!, Br and I, n represents M when H
When M is a metal atom, it represents its valence. Metal atoms include lithium, sodium,
Potassium, cesium, magnesium, calcium, strontium, barium, zinc, cadmium, mercury, tin,
These include antimony, chromium, manganese, iron, cobalt, nickel, rhodium, and cerium). Additionally, bromine water and other chlorine molecules are also effective.

(2) Onium halides: For example, trimethylphenylammonium bromide, cetylethyldimethylammonium 7"a mite, trimethylpensylammonium bromide, ggi ammonium halide: tetraethylphosphonium bromide g<z
Class 7 osphonium halides; tertiary sulfonyramno1lides such as trimethylsulfonium iodide; and the like.

(3) Halogenated hydrocarbons: Examples include iodoform, bromoform, carbon tetrabromide, copromunomethylpropane, and the like.

(4) N-halogen compounds: For example, N-chlorosuccinimide, N-bromosuccinimide, N-bromphthalimide, N-bromoacetamide, N-iodosuccinimide, N-promphthalazone, N-bromooxacillinone , hechlorophthalazone, N-bromoacetanilide, N,N-dibromobenzenesulfonami)', N
-bromo-N-lf rubenzenesulfonamide, l, 3
-Dibromog, 4+! -dimethylhydantoin, N-
Bromourazole, etc.

(5) Other halogen-containing compounds: Examples include triphenylmethyl chloride, triphenylmethyl bromide, λ-bromoacetic acid, J-bromoethanol, 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 organic silver salt 1
The amount is set at about o, ooi moles to about 0.7 moles, preferably about 0.03 moles to about 0.1 moles. More than one type of photosensitive silver halide forming component may be used in combination within the above range. Some organic silver salts using photosensitive silver halide forming components? The reaction temperature, reaction time, reaction pressure, etc. in the step of converting into photosensitive silver halide can be selected and set as appropriate from a wide range according to the purpose of production, but usually the reaction temperature It is preferable that the reaction time is about -00C to about 706C1, the reaction time is about 001 seconds to about 7λ hours, and the reaction pressure is set to atmospheric pressure. Further, this reaction is preferably carried out in the presence of a polymer used as a binder, which will be described later. The amount of polymer used in this case is about 0.0 to about 1 part i*x part of the organic silver salt.
00 parts by weight, preferably about 0.00 parts by weight. / to about 70 parts by weight.

Photosensitive silver halides prepared by the various methods described above include, for example, sulfur-containing compounds, gold compounds, platinum compounds,
Chemical sensitization can be performed with palladium compounds, silver compounds, tin compounds, chromium compounds or combinations thereof. This chemical sensitization procedure is described, for example, in the US wit
No. 1, 036, 6! Q, British Patent No. i, s/r, rj
No. o each specification, patent application specification/-j2! jO issue, same! /-7
No. 131, the same ZL-RII specification publication. In addition, in an embodiment in which a part of the organic silver salt is converted into a photosensitive silver halide forming component, the U.S. Percentage No. 3. This can be achieved by coexisting with a low molecular weight amide compound as described in the specifications of the IRO and TIT♂ co-issues.

The photocatalyst of component Φ), in particular the photosensitive silver halide, can be optically sensitized by a variety of known dyes. Effective optical sensitizing dyes include, for example, cyanine, merocyanine, rotacyanine, complex (tri-nuclear or homocyanine) cyanine or merocyanine, holopolar cyanine,
Examples include styryl, hemicyanine, oxonol, hemioxonol, and xanthine dyes. Among the cyanine pigments, those having basic nuclei such as thiazoline nucleus, oxazoline nucleus, viroline nucleus, pyridine nucleus, oxazole nucleus, thiazole nucleus, selenazole nucleus, and imidazole nucleus are preferred, and among the merocyanine pigments, those having basic nuclei such as thiazoline nucleus, oxazoline nucleus, viroline nucleus, pyridine nucleus, oxazole nucleus, thiazole nucleus, and imidazole nucleus are preferable. It is preferable to have a thiovidantoin nucleus, a rotanine nucleus, an oxazolidinedione nucleus, a thiazolidinedione nucleus, a halchturic acid nucleus, a thiazolinone nucleus, a malonitrile nucleus, or a pyrazolone nucleus as an acidic nucleus together with the above basic nucleus. Among the above, cyanine and merocyanine dyes having an imino group or a carboxyl group are particularly effective. Specifically, for example, U.S. Patent No. 3.76/, 279
No. 3,77? , Hiroshi No. 3, same No. 3. Za77, Rihiro No. 3, British % edition No. 1゜Hiro66, λoi No. 1. Gu6ri, No. 717, same No. 1. (Appropriately selected from among the known pigments described in the specifications of No. 7J7, JP-A No. 27-27-2012, and publications of No. 5-O-IST Kou-24L, etc.),
It can be placed near the photocatalyst according to the above-mentioned known method. These optical sensitizing dyes are used in an amount of about io mol to about 1 mol per mol of the photocatalyst of component (b).

The reducing agent used in the present invention as component (C) reacts with the organic silver salt when heated to 70C or higher under the exposed photocatalyst and reduces it. It functions as an oxidation-reduction image-forming composition together with organic silver salts in photosensitive materials for development.A suitable reducing agent is determined based on the type of organic silver salt used and overall performance criteria.For example, it is difficult to reduce. A reducing agent with strong reducing power is suitable for organic silver salts, and a reducing agent with weak reducing power is suitable for organic silver salts that are easily reduced.

Generally known as a reducing agent used in heat-developable photosensitive materials.
These include monophenols, polyphenols with λ or more phenol groups, mononaphthols,
Bisnaphthols, - or more hydroxyl groups? polyhuman mixybenzenes having λ or more aqueous dispersion groups, ascorbic acids, 3-pyrazolidones, pyrazolin-j-ones, bidizolines, 7-ethylenediamines, hydroxylamines, Hydroquinone monoethers, hydrooxamic acids, hydrazides, amidoximes, N-hydroxyurines, etc., and more specifically, for example, U.S. Patent No. J, t/Jr.
No. 133, No. 3.67, No. 2, No. J, 47.
2. ri Oμ, 3.7si, srJ, 3.7
♂λ, Rihiro No. 3, 10/, 32/, No. 3,
72μ, Hirot 1, same 'jK J, J'ri 3,
f l, No. 3, same No. J, 1r17.376, same No. 3,
770. Biri T No. 3, RI No. 312, No. 3
, 773. j/, No. 2, 4a3. s'3y, oar issue,
Ibid No. 3, 117.

! No. 71, No. 71, No. 00, No. 71, No. 71, No. 71, No. 71, No. 71, No.

o, y, i, Ko4AO, British Patent No. i, 4Art, i
i1 or Belgian Patent No. 7ff4.016, each specification and JP-A-Sho! 0-J6/μ3, same ro-JAI1
No. 0, same! 0=//lOko3, SO-Tata71ri, sametoi4Aoii, y, samej / -j /2
No. 33, same! No. l-23721, same! No. 11727 or Tokko Akira! There are specific examples of trap reducing agents listed in each publication, and the component (C) of the present invention can be appropriately selected from such known reducing agents. As for the selection method, it is considered to be the simplest method to examine the superiority or inferiority of the reducing agent used by actually producing a photothermographic material and evaluating its three essential properties.

Among the trap reducing agents described above, when using aliphatic silver carboxylate as the organic silver salt, preferable reducing agents include polyphenols in which λ or more phenol groups are linked behind an alkylene group or sulfur. , in particular, an alkyl group (such as a methyl group, ethyl group, propyl group,
t-butyl group, cyclohexyl group, etc.] or acyl group (
Polyphenols (e.g. /, /-bis(
λ-Hydroxy3. J-dimethylphenyl) -3#
j # j-) +) methylhexane, /Il-bis(,2-hydroxy-J-t-butyl-j-methylphenyltumethane, l*/-bis(euhydroxy-3,j
-di-t-butylphenyl)methane, j,J-methylenebis(,2-hydroxy-J -t -7'thyl-yo-
Methylphenyl-a-merphenol, 4,
l, '-Hensiritenubis(,21 goosey t-
butylphenol], Otsu, 6'-benzylidene-bis(
4-1-butyl-'l-methylphenol), 6,6'
-Benzylidene-bis(-2, Hiro-dimethylphenol), l.

l-bis(nohydroxy-3.j-dimethylphenyl)-nimethylpro/(n, /, /, J,!r-tetrakis(nohydroxy-3.j-dimethylphenyl)-
2+≠-Ethylpentane, 2-bis(Hiro-hydroxy-J,j-dimethyl)furonon, -92-bis(4
! -Hydroxy-31j-di-t-butylphenylphpropane, etc., in US Pat. jIP, No. 103, @u
, 02/.

, No. 24# or British Patent No. 1. μtrt, iVg specifications and specifications Sho pi-zty No. 33, same! 0-46
/No. 10, No. 3; 0-//No. 6023, No. 7
A7t polyphenol compound described in No. 27 or Japanese Patent Publication Shoj/-3jt727 Kerr 3jt);
71. Bis-β-naphthols (e.g.

Co'-dihydroxy-1.11-binaphthyl%41t'
-dibromo-2,2/-dihydroxy-l.

l'-binaphthyl, 616'-dinitro-λ, λ'-dihydroxy/, /l-binaphthyl, bis(2-hydroxy-1-naphthyl)methane, ψ.

μ'-dimethoxy/,/'-dihydroxyco.

-'-binaphthyl, etc.; US% Permit No. 3,10/.

Sulponamidophenol or sulfonamidonaphthol as described in Specification No. 3 Co. No. 1 (fLt is <
Examples include z-benzenesulfonamidophenol, -benzenesulfonamidophenol, 4,6-dichloro-benzenesulfonamidophenol, and l-benzenesulfonamidophenol.

The amount of reducing agent used in the present invention varies depending on the type of organic silver salt, reducing agent, and other additives, but is generally about 0.0 j mol to about 10 mol per 1 mol of organic silver salt. ,
Preferably, about 0.1 to about 3 moles are suitable. Further, within this range of amounts, two or more of the above-mentioned reducing agents may be used in combination.

It is desirable to use additives called toning agents, toning agents, or activator toners (hereinafter referred to as toning agents) together with the above-mentioned components. Color toning agents participate in the redox silver (image) formation reaction process between organic silver salts and reducing agents, resulting in images? It has the function of making dark colors, especially black. A wide variety of compounds are already known as color toning agents, but most of them are compounds having an imino group, a mercapto group, or a thione group. From these, all suitable color toning agents are selected according to the type of organic silver salt and reducing agent to be used, and those that provide a preferable color tone effect in the present invention are those described in US Patent No. 3. /12, RiO4A No. 3
．． Phthalazinones (e.g., phthalazinone, λ-acetyl phthalazinone, norylbamoyl phthalazinone, etc.) described in the specifications of No. 1μμ, No. 727 or No. 07T, jJ≠, U.S. Patent No. 3. n7r-λ-pyrazolin-j-ones (e.g., 3-methyl-novirazolin-!-one) or quinazolinones (e.g., quinazolinone, Hiro-methylquinazolinone, etc.) described in the specification of Hirot, Ist, US Pat. Chapter V.

030.5'J17, n7c pyrimidines (e.g., 6-methyl-Hiro, Hiro-dihydroxypyrimidines, etc.) or/, J,, J-triazines (e.g., 3-Methyl-Hiro, 6-dihydroxypyrimidines, etc.) -/, co, j-triazine, etc.), phthalazinediones (e.g., phthalazinedione, etc.) described in Japanese Patent Publication No. 3-36771, /-, cyclic imides (e.g., U.S. Patent No. s, r
The succinimides, phthalimides, or urazoles described in Hirot./36 specification or Japanese Patent Application Laid-open No. 1983-Sziis, U.S. Pat. No. 3,111,660 or U.S. Pat. Benzoxazinediones described in each specification of No. 11jt, No. 967, benzothiazinediones described in Japanese Patent Application Laid-open No. Shoj J-760-0, U.S. Patent Nos. 3 and 7.
jλ, naphthalimides described in Tar No. 1 specification]
Examples include heterocyclic compounds having an imino group such as.

These color toning agents can also be used in combination of two or more, for example, JP-A No. 70-70 and JP-A No. 13-jjl//! As stated in each publication, the use of all benzoxazinediones, benzothiazinediones, or phthalimides in combination with phthalazinones can cause deterioration of the color tone effect due to storage under high temperature and high humidity. It can be prevented.

In addition, US special #'F No. s, R Ko 7, 61 and the same Fj
, Tatapi, No. 7jλ As stated in each specification 7
Tallic acid, naphthoic acid, or phthalamic acid and imidazoles or phthalazines can also be used in combination as a color toning agent.

When a color toning agent is used, the amount used is about 0,0001 mol to about 2 mol per mol of organic silver salt, particularly about
A range of oz moles to about 1 mole is preferred.

Additionally, mercaptotetrazoles (eg!-mercaptotetrazole, l-phenyl-j-mercaptotetrazole, US%#'F No. 3.J//).

μ74C No. 3. Tata 3. It is written in the tti issue etc.
Precursors of L7'c mercaptotetrazoles (e.g. td
/ -7xnyl-5 (p-methylphenylsulfonylthione-tetrazole, etc., j-substituted 11-mercaptooxadiazoles (e.g. j-methyl-no-mercaptooxadiazole, etc.), j-substituted-2 -Mercaptothiadiazoles (e.g., j-methyl-normerkabutothiadiazole, etc.), !-Substituted-3-mercaptol, λ, Hiro-triazoles (e.g., 4.j-diphenyl-3-mercazoto/, λ, Hiro-triazole) ) and disulfides (for example, di(/-phenyl-y-tetrazolyl)-disulfide) are used per mole of the organic silver salt to further improve the color tone.

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 the white portion of each processed material due to light may be used. For example, stabilizer precursors such as the azole thioethers and blocked azolethiones described in U.S. Pat. No. 3,139.0≠1, U.S. Pat.
0, Tetrazolyl compounds or precursors thereof as described in Hiroyo No. 7, U.S. Pat. No. 3,70
No. 7.377, same jl'jJ, 1r741', ri1/-
No. A, No. 3.9. fj, 5'J', No. 2, No. 'A',
101. Air! No.
! There are compounds such as L7ζ sulfur alone or sulfur-containing compounds described in the specification of No. 0, and these may be used in combination.

Mano ξ, a known thermal antifoggant along with component (e) of the present invention? It also works well when used together. For example, the nyc mercury compounds described in U.S. Pat. No. 3,203; rij7. Described in the specification of Kou No. 23, 9N-no.
σgen compounds, benzenethiosulfonic acids as described in JP-A-Shoj/-71r227, JP-A-Sho! λ
−λμ! In addition to cerium compounds such as those described in Japanese Patent Application Laid-open No. 10101 and No. 5o-
iibo Kohiro issue, same jO-/23jJ/ issue, same so-/
J Hiro 4A Ko No. 1, JL-447μl No. 1, Same! /
-tA Koj Kota issue, same! /-4/3.23 issue, same! r
/-374'3 evening issue, 5i-io hiro 33r, same j3
-320Ij, zi-, zi4A3i, zi/-
No. 64AIIJt, No. 6l-7jμ33, No. s/
-/ko24A30, 53-10.20, j3-
/91ko S issue, same j3-kol! All of the heat capri inhibitors described in μ77 Specification Publication may be used alone or in combination.

Generally, tetrazaindene-based stabilizers are ineffective for heat-developable light-sensitive materials, but they can be used when the light-sensitive material contains silver sulfide (for example, sulfur sensitized fL9) or when silver halogenide is used. etc.) It has been recognized that silver sulfide has the effect of suppressing the slight increase in concentration caused by silver sulfide over a very long period of time.
of The PhotograpbicPro
cess”, Hiroth nd,, PPJYI~3 Tata.

Macmillan Publishing (:
'o, Inc.

(NhiW YO 几K) etc.'nπ tetraazaindene can be used.

In addition, together with the antifoggant of the present invention, JP-A-Sho! 6-70j
In addition to the mercapto compounds and thioether compounds described in Reference No. 3 and J6-Dita 3j No. 3, disulfides and polysulfides may be used in combination.

Each component used in the present invention is dispersed in at least one layer of colloid as component (d).

Suitable binders include hydrophobic polymeric materials, but depending on the case, hydrophilic polymeric materials can be used in combination or alone. The polymeric material used as the binder is preferably one that provides a transparent or transparent and colorless, white or light-colored layer or film when coated or cast. For example, natural polymeric materials such as proteins such as gelatin, cellulose derivatives, polysaccharides such as dextran, or gum arabic, and US Pat.
t (No. 10&', No. j/-JP/46, No. 1-/Y
12! Among them, polyvinyl butyral, polyvinyl acetate, ethyl cellulose, vinylidene chloride-vinyl chloride copolymer, polymethyl methacrylate, and vinyl chloride. - vinyl acetate copolymer,
Cellulose acetate butyrate, gelatin or polyvinyl alcohol are particularly preferably used.

If necessary, two or more of these polymeric materials may be used in combination. The amount of such polymeric material to be used is within the range of an amount sufficient to support the trapping component dispersed therein, that is, an amount effective as a binder. The range can be appropriately determined by those skilled in the art; for example, at least organic silver clay? When supported in a dispersed manner, the weight ratio to the organic silver salt is about io:l to 1:10, particularly about 1:1 to 1:10.

Is the composition containing each component of the present invention a film in which the binder used has self-supporting properties? If the material is to be provided, it may be formed into a film capable of carrying each component according to known casting methods, but it is generally preferable to form the film in one layer or layers on a variety of supports selected from a wide range of materials. The heat-developable photosensitive material is divided and coated into 1. A child is born. Materials for this support include various polymeric materials, glass, wool cloth, cotton cloth, paper, gold FA (e.g. aluminum), etc.; Those that can be processed are preferred. Therefore, the support in the present invention may be a plastic film (for example, cellulose acetate film, polyester film, polyethylene terephthalate film, polyamide film, polyimide film, triacetate film, or polycarbonate film) or paper (in addition to general paper, for example, for photographic use). Base paper, printing base paper such as coated paper or art paper, baryta paper, resin coated paper, paper sized with polysaccharide etc. as described in Belgian Patent No. 7 rμ, A15, titanium dioxide, etc. (7) Pigment paper containing pigment V, paper sized with polyvinyl alcohol) is particularly preferred.

The heat-developable photosensitive material of the present invention includes auxiliary layers for each layer, such as the trap-deposited gold plate layer described in U.S. Pat. No. 1,607, P. JP-A-Shosi-Hiroshi 3/30 or same j/-/
2 Octopus λθ The back layer described in the specification publication or JP-A-Sho!
In addition to the back layer containing the AM material described in Tata No. 0-/340, an antistatic layer and an undercoat layer described in JP-A-1'77-1 can be provided. . Also, U.S. Patent No. j, P33.108', U.S. Patent No. 3,116゜jJA, U.S. Patent No.
j, z No. 7 i1. <1driJ 3rd. lli3,160
It is preferable to provide a single layer of overcoat cypolymer as described in Specification No. 8 of the present invention because it has the effect of increasing the transparency of each layer provided on the support and improving the moisture resistance or heat resistance of the layer. The thickness of the top coat 9 polymer layer is suitably about 1 micron to about 20 microns, and suitable polymers include those mentioned in the above-mentioned specifications as polymers for the top coat polymer layer. Among them, polyvinyl chloride, polyvinyl acetate, vinyl chloride-vinegarff
Preferable examples include vinyl copolymer, polystyrene, methyl cellulose, ethyl cellulose, cellulose acetate butyrate, vinyl chloride-vinylidene chloride copolymer, carboxy ester, cellulose diacetate, vinylidene chloride, polycarbonate, ceratin, and polyvinyl alcohol.

The film or layer containing each component of the present invention or each auxiliary layer may include a glass filler known in the field of photothermographic materials, such as a plasticizer, a matting agent, a surfactant, a sensitizer, and a whitening agent. , light-absorbing substances, filter dyes, anti-nolation dyes, color couplers, hardeners, dNffi agents, development accelerators, stabilizers, etc., Vol. 22 (December 1971 issue) ) A 23λ 107th negative and later, JP-A-Shojf3-
No. 3361j, to-//2623, jO-j7
61? No. J/-λ7 Octopus 3 Specification Publication or U.S. Permit No. 3767, OIY No. rai, oo1,
No. 3,667.931, No. 3. r”yi, rt7
No. 3. its, ri No. 6j, same No. a.

Coll., Jso No. 44,036,650, No. 3
, 13/, No. 216, No. 3.76, and No. 3λr.

The method for preparing the heat-developable photosensitive material of the present invention is as follows. In other words, one of the known methods? The organic silver chloride prepared using L7m is washed with water, alcohol, etc. if necessary, and then mixed with a photocatalyst so that the two come into close contact to form a mixture. Photocatalyst as an alternative method? It may be produced at the same time as the organic silver salt, and the most preferred method is to form part of the organic silver salt.・
・There is also a method of converting silver halogenide into silver halogenide. When 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 preferably prepared as a polymer dispersion dispersed in a solution of a polymeric material that 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. The polymer dispersion of this organic silver salt and photocatalyst may be formed into a gold film or coated in a layer on a support, and the other components of the present invention may be contained in the layer provided on the film or layer. Preferably, other components used in the present invention, at least a reducing agent and component (d) of the present invention are further added to the polymer dispersion of the organic silver salt and photocatalyst to prepare a heat-developable photosensitive composition, and the composition is prepared by a known method. Cast into a membrane or coated as a layer on a support. For coating, various known coating methods such as a dipping method, an air knife method, a coating method, a hopper coating method, etc. can be applied. Further, if desired, any solvent may be used in the coating solution as well as all the various auxiliary layers such as the 9 undercoat layers and the top coat, prior to, simultaneously with, or after the coating of the composition, as described in British Patent No. 1.
It is also possible to use non-flammable solvents such as those described in Hiro J. Co./$4'.

If desired, the front or back side of the support, or a layer coated on the support, can be printed to provide a predetermined pattern for use on vehicle tickets, postcards or other documents. It can be applied.

The heat-developable photosensitive material thus produced is cut into a size suitable for convenient use, and then exposed to light.

Must! Preheat 16mm before light (rO'C-14Ao oC)
Even if you give it, it's wrong. Companion light sources suitable for image 9J exposure include tungsten lamps, multiple-reuse fluorescent lamps such as those used mainly for exposing diazo-sensitive materials, mercury lamps, iodine lamps, xenon lamps, CRT light sources, laser light sources, and other lightning sources. Can be mentioned.

The manuscript may include not only line drawings IM such as technical drawings, but also gradation-containing 7C true images, and it is also possible to take pictures of people and landscapes with a camera. As for the printing method, contact printing may be used to overlap the original, reflection printing may be used, or enlargement printing may be used.

The amount of exposure varies depending on the sensitivity of the photosensitive material, but a high-sensitivity one requires about 1 lux seconds, and a low-sensitivity one requires about ios lux seconds. The photosensitive material image-exposed in this way is heated (approximately ro
0c or more, preferably about i.

o'C to about /s00c).

The heating time is arbitrarily adjusted, such as from 1 second to 60 seconds. This is determined in relation to the heating temperature. Generally, it is about j seconds to about ao seconds at tsooc, about λ seconds to about -0 seconds at 130oC, /
4 (about 1 second to about 10 seconds at θ0C is appropriate. There are various heating methods. For example, the sensitive material may be brought into contact with a simple heated plate, or the sensitive material may be brought into contact with a heated drum. In some cases, it may be heated and passed through the space. Also, high frequency heating or Reitz'-beam heating may be applied.

The present invention will be explained in more detail by showing examples below. Example l.

The above composition? Prepare a polymer dispersion of silver salt by dispersing it with a homogenizer and trap it.

This silver salt polymer dispersion was maintained at 2so 0C, and the following solution was added and heated for 90 minutes. It was converted to silver bromide.

The thus prepared polymer dispersion of π-behene silver-silver bromide was maintained at 2ao'C, and the following compound was added to kmc-based j@ to prepare a coating solution.

The trap coating solution prepared in this manner was coated on photographic base paper so that the silver amount was 1 TrL2, 1 TrL2, and 2 ζ, and after drying, 2
% by weight of acetone solution with a polymer amount of 0.0% per m2. μ
It was set up to be 2. The heat-developable photosensitive material prepared in this way is called A-/.

As a comparative sample, sensitive material 2B-t was prepared in exactly the same manner as A-/ except that coatipromomethylbenzothiazole (1) was removed.

In order to prepare further comparative samples, J
A π-sensitive material iB-λ was prepared in exactly the same manner except that a 1% by weight methyl ethyl ketone solution of tribromoacetophenone ioomt2 was added instead of adding tribromomethylbenzothiazole (1). A material 7'c, W& material 2B-3 was prepared in exactly the same manner except that 1% by weight of mercuric acetate was added to a methanol solution Omtf.

These samples were passed through an optical wedge at 103 lux seconds.
After L7t, a black image was obtained by heating at a temperature of 120c'C'''ClO for seconds.Next, the reflection @FK' was measured for these samples, and the fog υ was also ζ (necessary), which gave a reflection density as high as Oll. The reciprocal of the exposure amount?Sensitivity is calculated as a measure of sensitivity.Table 1 shows the sensitivity of B-s as ioo and the measured values of relative sensitivity, fever, and maximum density during trapping.

From the measurement results shown in Table 1, sample A-
Compared with comparative samples B-t and B-2, / has a very large heat buildup prevention property, and the decrease in sensitivity and maximum concentration is slight, and π comparative sample B using a mercury compound. −
Even when compared with J, it turns out that there is almost no difference in the performance of tl. Further, when the sample A-/ of the present invention was left on a sheet metal sheet for 1 hour, no increase in the fogging of the white background area occurred and the roof tile. Furthermore, this sample tzs
o 0c, yo%YLll for 3 days IIf )! iK
Even if I left it alone, no increase in the strength of the white background was observed.

Example 2 A heat-developable photosensitive material was prepared in exactly the same manner as Sample A-/, except that the compounds shown in Table 2 were used in place of coatipromomethylpenzothiazole (1) in Example 1. Created.

Let the respective samples be iA-co-A-ta.

Table 3 shows the results of sensitometry carried out on the sample of Kohori et al. in the same manner as in Example 1.

Table 3 The measurement results shown in Table 3 show that the present invention produced a sensitive phase with extremely low thermal strength.

Claims (1)

[Scope of Claims] A photothermographic material comprising at least (a) an organic silver salt, (b) a photocatalyst, (C) a reducing agent, and (d) a binder, further comprising (e) a general formula (1). ) A heat-developable photosensitive material containing at least one compound represented by the following. However, Xl-1 represents 7 nitrogen atoms, 2 represents a sulfur atom, an oxygen atom, or :N-4L"f-, R1 represents an alkyl group, and 4 traps for an aryl group represent an acyl group.
l, ) n represents a substituent on the benzene nucleus, and O represents an integer of nflO or l-hiro.