DE2508344A1 - HEAT DEVELOPMENT LIGHT SENSITIVE MATERIAL - Google Patents

Description

PATENT ADVOCATES A. GRÜNECKER

DIPL.-INQ.

H. KINKELDEY

DR.-INQ.

^. . W. STOCKMAIR

2 5 0 0 3 * n / a DR.-INQ. AeE (CAl-TEOH)

K. SCHUMANN

DR. RER. NAT. · DIPL.-PHYS.

P. H. JAKOB

DIPL.-INQ.

G. BEZOLD

DR. RER. NAT. · DIPL.-CHEM.

MUNICH

E. K. WEIL

DR. RER. OEC. INTO THE.

LINDAU

8 MUNICH 22

MAXIMILIANSTRASSE 43

P 8940

February 26, 1975

Fuji Photo Film Co., Ltd.

Ho. 210, Nakanuma, Minami Ashigara-Shi, Kanagavia, Japan

Heat developable photosensitive material

The invention relates to a heat developable photosensitive Material (hereinafter referred to as "heat developable photosensitive material"); it concerns in particular a thermally developable material that is suitable for the production of high-contrast images and thus for reproduction after the reflection printing process is suitable.

The photographic carried out using silver halide Process is the most widely used photographic process as it is the electrophotographic process or the photographic diazo process in terms of photographic properties such as sensitivity and

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TELEPHONE (089) 22 28 62 TELEX O5-29 38O TELEGRAMS MONAP

Gradation, is superior. A silver halide light-sensitive material used in this process is imagewise exposed, developed with a developer, and further subjected to several steps of treatment such as stopping, fixing, washing with water and stabilizing in order to prevent the developed image from being discolored or faded and in order to prevent the undeveloped area (hereinafter referred to as the "background") from blackening. The photographic process carried out using silver halides therefore has the disadvantage that a lot of time and work are required for its development or treatment, that the handling of the chemicals is harmful to the human body and that the treatment rooms and the hands of the operating personnel are dirty or . become discolored. It has long been eager to improve the photographic process using silver halides so that development can be carried out in a dry state without the use of solutions and the developed image can be stabilized. Many suggestions have been made in this regard. One suggestion is to heat developable photosensitive materials to use _t as much if in the US Patent 3,152,904 th, 3 4-57075, J 635 719 3 64-5739, 3756829, 3589903 ₁ 3 802 888, 3 764 329 »3 672 904-, 3 846 136, 3 839 04-1, 3 708 304, 3 761 279, 3 751 249, 3 770 THId 3 773 512, in Canadian Patent 811 677 and in Japanese Patent Applications (OPI) ITr, 4728/1971 and 8972O / I973. In these methods, a photosensitive member composed of a silver salt of a long-chain aliphatic carboxylic acid such as silver behenate, silver saccharin or silver benzotriazole as a main component and a catalytic one is used. There is an amount of silver halide. However, these heat-developable photosensitive materials cannot produce high-contrast images of satisfactory quality, and these materials are unsatisfactory when high-contrast sensitive

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Material is required, such as one of a positive Original made using the reflection printing process and one using this negative Positive produced as an original. The reflective printing process is described by J. Kosar in "Light-Sensitive Systems", pp 290-291, John Wiley & Sons, Inc., New York (1955).

A sensitive silver halide material that is produced by a wet process using an analogue reflection printing process has to be developed is, for example, that of Fuji Photo PiIm Co., Ltd. produced quick copy Paper. This material does provide a picture with an: excellent Quality, however, since it must be wet developed, problems arise with the use of chemical solutions Therefore, for a long time there has been a search for sensitive materials that can be developed or developed using a dry process. can be treated.

The aim of the present invention is to provide a heat developable (heat developable), sensitive, high contrast Specify material, in particular one that, when the reflection printing process is used, produces images with a good Quality delivers.

The invention relates to a heat developable photosensitive Material which is characterized by a carrier and at least one layer applied to it, the contains

a) an organic silver salt,

b) a catalytic amount of a photosensitive silver halide or a compound which reacts with the organic silver salt to form a photosensitive silver halide can react (hereinafter referred to as "a photosensitive silver halide forming component") and

c) a reducing agent,

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wherein at least a portion of the catalytic amount of the photosensitive Silver halide has been produced by the reaction of a. Compound made with the organic silver salt can react to form a photosensitive silver halide in the presence of a rhodium salt selected is from the group of a halo rhodium complex of the general formula

^M 'h ^CRh k ^X "l ^(OH) m ³ - ^pH 2 ^O

where- mean:

M 'a monovalent cation,

X "is a halogen atom,

h is an integer from 2 to 5,

k is the integer 1 or 2,

1 is an integer from 5 to 11,

in. the integer O or 2 and

ρ is an integer from 0 to 12

and rhodium nitrate.

The fiction, contemporary heat developable photosensitive Media is suitable for printing that requires high contrast. Other objectives, features and benefits of the Invention emerge from the following description

The organic silver salts that can be used according to the invention as component a) are those that are comparatively stable to light, are colorless, white or faintly colored and when heated to a temperature above about 80 ° C., preferably above 100 ° C., in the presence of exposed silver halide deliver SiIb er (images) by reaction with a reducing agent. Su suitable examples of organic silver salts

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include the silver salts of organic compounds with an imino, mercapto, thio, hydroxyl or carboxyl group. Suitable specific examples of these compounds are as follows:

1.) Silver salts of compounds with an imino group: the silver salt of benzotriazole, the silver salt of Nitrobenzotriazole, the silver salt of an alkyl substituted en benzotriazole (e.g. the silver salt of methylbenzotriazole and the like), the silver salt of a halogen-substituted benzotriazole (e.g. the silver salt of Bromobenzotriazole, the silver salt of chlorobenzotriazole and the like), the silver salt of a carbide-substituted one Benzotriazole (e.g.

'Ν

or

and the like

The silver salt of a substituted benzimidazole (e.g. the silver salt of 5-chlorobenzimidazole, the silver salt of

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5-nitrobenzimidazole and the like) »the silver salt of carbazole, the silver salt of saccharine, the silver salt of phthalazinone, the silver salt of a substituted phthalazinone, the silver salt of a phthalimide, the silver salt of pyrrolidone, the silver salt of tetrazole, the silver salt of imidazole and the like .;

2.) Silver salts of compounds with a mercapto or thione group:

the silver salt of 3-Mercapto-4 ™ phenyl - 1,2,4-triazole, the silver salt of 2-mercaptobenzimidazole, the silver salt of 2-mercapto-5-aminothiadiazole, the silver salt of 1-phenyl-5-diercaptotetrazole, the Silver salt of 2-mercaptobenzothiazole, the silver salt of 2- (S-ethylthioglycolamido) benzothiazole disclosed in Japanese Patent Application (OPI) ITr. 2822/1973 described silver thioglycolates (e.g. the silver S-alkyl (C ₁₂ ~ C ₂₂ ) thioglycolate and the like), SiI-

Berdithiocarboxylates (e.g. silver dithioacetate and the like), the silver salt of thioamide, the silver salt of thiopyridine (e.g. the silver salt of 5-carbethoxy-1-methyl-2-phenyl-4-thiopyridine and the like), the silver salt of dithiodihydroxybenzene, the silver salt of mercaptotriazine, the Silver salt of 2-mercaptobenzoxazole, the silver salt of mercaptooxadiazole, and the like;

3.) Silver salts of compounds with a carboxy group: i) Silver salts of aliphatic carboxylic acids: silver caprate, silver laurate, silver myristate, silver palmitate, silver stearate, silver behenate, silver maleate, silver fumarate. , Silver tartrate, silver furoate, silver linoleate, silver oleate, silver hydroxystearate, silver adipate, silver sebacate, silver succinate, silver acetate, silver butyrate, silver camphorate and the like,

, ii) Silver salts of aromatic carboxylic acids and others: Silver benzoate, substituted silver benzoate (e.g. silver 3,5-dihydroxybenzoate, Silver-o-methylbenzoate, silver-m-

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methylbenzoate, silver p-methylbenzoate, silver 2,4-dichlorobenzoate, Silver acetamidobenzoate, sirber p-phenylbenzoate and the like), silver gallate, silver tannate, silver phthalate, Silver terephthalate, silver salicylate, silver phenyl acetate, silver pyromellitate, the silver salt of 4 * -n-octadecyloxydiphenyl-4-carboxylic acid, the silver salt of a thionecarboxylic acid, as in U.S. Patent 3,785,830. described the silver salt of an aliphatic carboxylic acid with a thioether group, as in the US patent 3,330,663 and the like;

4.) other silver salts: the silver salt of 4 ~ hydroxy-6-methyl-1,3,3a, 7 ~ tetrazaindene, the silver salt of 5-methyl-7-hydroxy-1,2,3 »4,6-pentazaindene, the silver salt of Tetrainden, as in British Patent 1,230,642 described, the silver salt of S-2-aminophenylthiosulfuric acid, as described in U.S. Patent 3,54-9,379,

the silver salt of a metal containing amino alcohol, as in Japanese Patent Application (OPI) No. 6586/71 described, the silver salt of an organic acid metal chelate, as described in Belgian patent 768 411, and the like

The preparation of these organic silver salts is generally used carried out in such a way that a solution of a a silver salt-forming organic compound dissolved in a suitable solvent and an aqueous solution of one Silver salt, such as silver nitrate or a silver complex salt, mixed together. Suitable methods include, for example a method for producing silver benzotriazole by mixing a methanol solution of benzotriazole and a aqueous solution of silver nitrate with reaction of the benzotriazole with the silver nitrate and a method as described in Japanese Patent Publication 30270/1969, which consists in dissolving a solution of silver nitrate

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in a solvent A, the silver nitrate and nitric acid can dissolve, but silver benzotriazole can only dissolve weakly, e.g. water, dimethylformamide or dimethyl sulfoxide with a solution of benzotriazole, dissolved in a solvent B, which can dissolve benzotriazole, but which is silver benzotriazole and silver nitrate cannot dissolve or only weakly and has a solubility of about 1 to about 30% by weight in solvent A, based on the total weight of the solvent (solvent A + solvent B), such as phosphoric acid ester, Phthalic acid esters and dibasic fatty acid esters of alcohols and phenols or higher fatty acid esters of glycerol, such as tri— cresyl phosphate, dimethoxyethyl phthalate, di-n-butyl phthalate, Diethyl sebacate, monooctyldibutylpho sphat, tributylpho sphat, Castor oil and linseed oil, mixes and thereby converts the silver nitrate with the benzotriazole. Other organic silver salts can generally often be prepared by analogous processes will.

A suitable process for the production of organic silver salts, e.g. silver salts of organic carboxylic acids, such as silver laurate, silver caprate, silver myristate, silver palmitate, Silver stearate, silver behenate, silver adipate and silver sebacate consists of the fact that an aqueous solution of a water-soluble Carboxylic acid salt, such as an alkali metal salt, wde the sodium, potassium or Lithium or ammonium salt thereof, with an aqueous silver nitrate solution, mixes.

In addition, a silver salt of an organic carboxylic acid can be prepared by a method in which a solution of an organic carboxylic acid dissolved in a solvent which can dissolve the organic carboxylic acid but poorly dissolves the organic carboxylic acid silver salt and silver nitrate and is only slightly soluble in water such as organophosphate as tricresyl phosphate Tributy • and Monooctyldibutylphosphat, phthalates such as Biäthylsr;., Sibutylphthalat, dimethyl _r Dioctylph!

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and dimethoxyethyl phthalate, carboxylic acid esters such as amyl acetate, . Isopropyl acetate, isoamyl acetate, ethyl acetate, 2-a'thylbutylaeeta ' Butyl acetate, propyl acetate, dioctyl sebacate, diethyl succinic acid Ethyl formate, propyl formate, butyl formate, amyl formate, ethyl valerate, Diethyl tartrate, methyl butyrate, ethyl butyrate, butyl butyrate and isoamyl butyrate, glycerol esters of higher fatty acids, such as castor oil, aromatic hydrocarbons such as benzo, toluene and xylene, aliphatic hydrocarbons such as n-hexane and cyclohexane and the like, if necessary, emulsified with water or an alkaline aqueous solution such as one aqueous solution of sodium hydroxide, an aqueous solution of potassium hydroxide or an aqueous solution of ammonia, with an aqueous solution of silver nitrate or a silver complex salt, preferably an alkali-soluble silver complex salt with a higher dissociation constant than the silver salt of the organic acid, such as a silver amine complex salt, a silver methylamine complex salt or a silver ethylamine complex salt mixes, or a process in which an emulsion of an aqueous solution of a salt of an organic carboxylic acid, e.g. of the sodium, potassium or ammonium salt thereof in the above-mentioned solvent, which is only weakly in Is water soluble, mixed with an aqueous solution of a silver salt such as silver nitrate or a silver complex salt. These processes can also be used for the production of other organic Silver salts are applied.

These processes for the production of organic silver salts are, for example, in U.S. Patent 3,458,544 in U.S. Patent No. 3,458,544 Japanese Patent Publication No. 30 270/1969, in German Laid-Open Applications 2,322,096, 2,401,159 and 2,402,906, in French Patent 2,147,286 and Japanese Patent Publication No. 49436/1969.

üie component b) used according to the invention, the catalytic Amount of the photosensitive silver halide, according to a

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Process are produced in which the production of the. organic silver salt described above in the presence of a photosensitive silver halide-forming component, which is explained in more detail below, is carried out. This procedure is for example in the German Offenlegungsschrift 2,428,125. Under application this process, modified according to the invention by production of component b) in the presence of a rhodium salt, a high-contrast, heat-developable, photosensitive material can be produced.

It is ensured that a photosensitive silver halide-forming component is present during the preparation of the organic silver salt (component a)) by adding the photosensitive silver halide-forming component to a solution of an organic carboxylic acid or a salt thereof to form a solution, a Emulsion or dispersion. (For the sake of simplicity, the invention is described below with reference to the preparation of a silver salt of an organic carboxylic acid, but it goes without saying that this description also applies to the preparation of other organic silver salts.) Alternatively, the photosensitive silver halide-forming component can be provided is present by mixing a solution of an organic carboxylic acid or a salt thereof and a solution of a silver salt such as silver nitrate or a silver complex salt with a solution, dispersion or emulsion of the photosensitive silver halide forming component. The object of the present invention can be achieved, that it is ensured that a rhodium salt in one of the solutions and emulsions described above, is present or _f that a solution, dispersion or emulsion is added a rhodium salt previously prepared in this method. Any order of addition can be used as long as the rhodium salt is present during silver halide formation. Preferably

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one ensures that the rhodium salt during the addition of the the silver halide forming component or before the addition the same is present, but the rhodium salt can also be added after the addition of the component forming the silver salt will. In the latter case, the effect of the rhodium salt is somewhat reduced. The time indicated above for adding the Rhodium salt is also applicable to the following cases.

Another, more preferred method of making a The catalytic amount of a photosensitive silver halide is that of a photosensitive silver halide forming component reacts with a previously prepared organic silver salt and thus part of the organic Silver salt converted into a catalytic amount of silver halide, as described in US Pat. No. 3,457,075 and US Pat Japanese Patent Application No. 126,658/1973.

In this method, the object of the present invention can be achieved by ensuring that in a Dispersion of the organic silver salt, a rhodium salt is present, or that it is ensured that in a solution or Dispersion of the component forming the silver halide, a rhodium salt is present, or that a solution or dispersion a rhodium salt is added before or after the addition of the component forming the silver salt.

In the case of the first-mentioned s and the last-mentioned modifications, an increase in the sensitivity and an improvement in the other properties can be achieved by, after the addition of the rhodium salt and / or the component forming a silver halide, at a high temperature, for example at about 3 ° to about 80 ⁰ C, a sufficient time can be about 20 minutes to about 3 hours, mature example.

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Another method of making a catalytic The amount of the photosensitive silver halide is to prepare a silver halide and this halide in advance mixed with an organic silver salt as disclosed in Japanese Patent Applications ITr. 82 852/1975 and 82 851/1973, in British Patents 1,362,970 and 1,354-186; in French patent 2,078,586 and in US patents 3 152 904, 3 706 564-, 3 706 565 and 3 713 833 is described. In this method, the object of the present invention can be achieved by for it ensures that a rhodium salt is present together with the component forming a silver halide, that one ensures that that a rhodium salt is present when the organic silver salt and the silver halide are mixed together, or that after mixing the organic silver salt with the silver halide, a rhodium salt is added. In the latter case it is the effect of the rhodium salt is somewhat reduced.

As a silver halide forming component, any of the compounds can be used which are capable of reacting with an organic silver salt to form a silver halide. To determine which silver halide-forming component is more effective, a routine experiment can be used, which is easy to carry out · That is, the component forming a silver halide is reacted with an organic silver salt and then the X-ray diffraction peak properties of the formed silver halide are examined.

Examples of suitable components which form a silver halide are inorganic halides of the general formula

where M is a hydrogen atom, an ammonium group or a metal atom, E.g. one of lithium, sodium, potassium, rubidium, cesium, copper, gold, beryllium, magnesium, calcium,

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Strontium, barium, zinc, cadmium, mercury, aluminum, gallium, indium, thallium, germanium, tin, lead, antimony, Bismuth, chromium, molybdenum, tungsten, manganese, rhenium, ruthenium, palladium, osmium, rhodium, iridium or platinum, X Cl, Br or J and η the number 1, if M is a hydrogen atom or a Ammonium group, or the valence of the metal when M is a metal atom.

Other examples of components forming a silver halide are halogen-containing metal complexes such as K ₂ PtCl ₆ , KpPtBr ₆ , HAuCl ₄ , (NH ₄ ) ₂ IrCl ₆ , (NH ^) ₅ IrCl ₅ , (NH ^) ₂ RuCl ₆ and (NH ^) ₃ RuCl ₆ . Further examples of components forming a silver halide are N-halogen compounds with a -COHX 'group, in which X ¹ denotes Cl, Br or J, such as N-haloacetaniides, N-halophthalazinones and N-halosuccinimides

wherein R is a nitrogen-containing 5- or 6-membered heterocyclic ring forming atomic group and X ^{1 is} Cl, Br or J

Further examples of components forming a silver halide are onium halides such as cetylethyldimethylammonium bromide and Trimethylbenzylammonium bromide. Preferred examples of a Components forming silver halide are halogenated hydrocarbons, such as iodoform, bromoform and 2-bromo-2-methylpropane and carbon tetrabromide. In addition, as a silver halide-forming component, halogen-containing compounds such as Triphenylmethyl chloride, triphenylmethyl bromide, 2-bromobutyric acid, 2-bromoethanol and benzophenone dichloride can be used.

The above-described, a photosensitive silver halide

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Genid-forming components can be used individually or in combination. The amount of components used is generally about 0.001 to about 0.5 »preferably 0.01 to 0.2 moles per mole of the organic silver salt component (a). If less than about 0.001 moles is used, -will decreases sensitivity, while if more than about 0.5 moles are used, there is an increase in light discoloration and there is a decrease in the contrast between the image area and the background. The term used here "Light discoloration" means a gradual discoloration of the non-image area (the background) when a heat developed Material is stored under normal room light.

The above as examples of one forming a silver halide Component specified rhodium halides, such as rhodium chloride and rhodium bromide, have no effect according to the invention as the rhodium salt when used in combination with the silver halide forming component and they fall therefore not under the term "rhodium salt" used here. On the other hand, the halo rhodium complexes are those given below Formula under this definition

^ J ₅₁₁₁₁ ] .pH ₂ O where:

M ^{1 is} a monovalent cation, preferably an alkali metal ion, e.g. a lithium, sodium or potassium ion, or an onium ion, such as a pyridinium, dimethylammonium, tetramethylammonium or tetraethylammonium ion or an ammonium ion (where a quaternary ammonium ion, e.g. tetramethylammonium , Tetraethylammonium ion and the like, is particularly preferred),

X "is a halogen atom, e.g. chlorine, bromine or iodine, preferably chlorine or bromine, both of which can be present at the same time

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h is an integer from preferably 2 to 5,

k is an integer, preferably the number 1 or 2,

1 is an integer from preferably 5 to 11,

m is an integer, preferably the number O or 2, and

ρ is an integer from preferably 0 to

Typical examples of halo rhodium complex salts of the general formula given above are the following ":

Na ₂ (RhCl ₅ (OH) ₂ ), Rb ₂ (RhCl ₅ (OHX ₂ ), Cs ₂ (RhCl ₅ (OH) ₂ ), LIx (KhClg) · 12Η ₂ 0, Na, (RhCl ₆ ) -12H ₂ O,

6H ₂ O,

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10H ₂ O,

, (RhC lg) '

. (NH,), (KhCIg) -12H ₂ O

H ₂ O,

(CH ₃ NH ₃ ) ^ (RhCl ₇ ),

(JCH ₃ CH ₂ ) _{i +} NJ ₃ (Rh ₂ Cl ₉ ), K ₃ (RhBr.),

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(^ NH) ₃ (Rh ₂ Br ₉ ),

), (Rh ₂ Br ₉ ),

! and the like.

Rhodium nitrate can also be used. These halo rhodium complex salts and rhodium nitrate can be used singly or in combination of two or more thereof will.

The amount of such a rhodium salt used is generally about 0.0001 to about 0.5 »preferably 0.001 to 0.1 mol per mol of the silver halide forming component. The most suitable silver halide forming components used in combination with such. Rhodium salt can be used, are N-halogen compounds with a -CONX'-G group, in which X ^{1 is} Cl, Br or I, but other compounds can of course also be used.

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As component c) according to the invention, ie as a reducing agent, any compound can be used which is capable of reducing an organic silver salt (component a)) to form a silver image when it is heated in the presence of exposed silver halide as a catalyst . A suitable reducing agent is selected depending on the particular organic silver salt with which the reducing agent is combined, but in general substituted phenols, substituted or unsubstituted bisphenols, substituted or unsubstituted mono- or bisnaphthols, di- or polyhydroxybenzenes, di- or polyhydroxynaphthalenes , Hydroquinone monoather, ascorbic acid or derivatives thereof, 3-pyrazolidones, pyrazolin-5-ones, reducing S _accnar i ^ _e , p-phenylenediamine or its derivatives, aminoreductones, kojic acid and hinokithiol can be used.

These reducing agents are described in U.S. Patents 3,152,904, 3,457,075, 3,531,286, 3,589,903, 3,756,829, 3 679 4-26, 3 667 958, 3 672 904-, 3 751 24-9, 3 770 44-8, 3,773,512 and 3,819,382 in Japanese Patent Application No. 27242/1973, in German Offenlegungsschrift 2 4-34- 4-15, in Belgian patent 786 086 and Canadian patent 811 677.

Suitable examples of reducing agents are the following:

1.) Substituted phenols:

p-aminophenol, o-aminophenol, N-methyl-p-aminophenol, 2-methoxy-4— aminophenol, 2,4 ~ diaminophenol, 2-ß-hydroxyethyl-4- aminophenol, p-t-buty! phenol, p-t-aminophenol, p-cresol, p-acetophenol, 2,6-di-t-butyl-p-cresol, p-phenylpheno1, p-ethy! phenol, p-sec-butylphenol, o-phenylphenol, 1,4-dimethoxyphenol, p-acetoacetyl-4-methylphenol, 2,3-dimethylphenol, 3,4-xylenol, 2,4-xylenol, 2,6-dimethoxy-2,4-, 5-trimethylphenol.

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2,4-di-t-butylphenol, phenol, 3,5-di-t-butyl-4 ~ hydroxybenzyldimethylamine, Chlorothymol, α-phenyl-o-cresol, p-hony! Phenol, p-octylphenol and the like.

2.) Substituted or unsubstituted bisphenols: bisphenol. A, 1,1-bis (2-hydroxy-3,5-dimethylphenyl) -3,5,5-trimethylhexane, 2, 4 ·, 4 ~ trimethylpentyl bis (2-hydroxy-3 »5-dimethylphenyl) methane, bis (2-hydroxy-3-t-butyl-5-methylphenyl) methane, bis (2-hydroxy-3? 5-di-butylphenyl) methane, 4, ^ -'-methylene bis (3-methyl-5 -t- "butylpheriol), 4-, 4'-methylene" bis (2,6-di-t-butylphenol), 2,2'-methylene-bis (2-t-butyl-4-ethylphenol), 2,6 -Methylene-bis- (2-hydroxy-3-t-butyl-5-methylphenyl) -4-methylphenol, 3 ■> 3 '? 5 j 5 '-tetra-t-butyl-4, 4' -dihydroxybiphenyl, 1,1-bis- (4-hydroxyphenyl) -cyclohexane, chloro-2-hydroxyphenyl) methane ^ 2,2-bis- (3, 5 phenyl) propane, 2,2-bis- (4-hydroxyphenyl) -propane, 2,2-bis- (3,5-dimethyl-4-hydroxyphenyl) propane, 2,2-bis- (3-methyl-4 ~ hydroxyphenyl) propane, bis (3-methyl-4-hydroxy-5-t-butylphenyl) sulfide, α, α '- (3 »5- ^D it-butyl-4-hydroxyphenyl) dimethyl ether, 3Sr, N ^I - Di (^ ~ hydroxyphenyl) urea, diethylstilbestrol, hexostrol and the like.

3.) Substituted or unsubstituted mono- or bisnaphthols and di- or polyhydroxynaphthalenes:

Sodium - amino-2-naptehol ~ 6-sulfonate, 1-naphthylamine-7-sulfonic acid, 1-hydroxy-4-methoxynaphthalene, 1-hydroxy-4-athoxynaphthalene, 1,4-dihydroxynaphthalene, 1,3-dihydroxynaphthalene, i -Hydroxy-4-aminonaphthalene, 1,5-dihydroxynaphthalene, Ί-hydroxy-2-phenyl-4-methoxynaphthalene, 1 -hydroxy ^ -methyl - *! - methoxynaphthalene, ß-naphthol, a-faphtho1, 1,1 * - Dihydroxy-2,2'-binaphthyl, 4,4'-diinethoxy-1,1'-dihydroxy-2,2'-binaphthyl 6,6'-dibromo-2,2 ^f -dihydroxy-1,1'-binaphthyl, ^, e'-Dinitro ^^ ¹ -dihydroxy-1,1'-binaphthyl, bis (2-hydroxy-1-naphthyl) methane and the like.

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4-.) Di- or polyhydroxybenzenes and hydroxyquinone monoethers: hydroquinone, methylhydroquinone, chlorohydroquinone, bromohydroquinone, phenylhydroquinone, hydroquinone monosulfonate, t-octylhydroquinone, t-butylhydroquinone, 2,5-dimethylhydroquinone, methylhydroquinone, methylhydroquinone , Catechol, pyrogallol, resorcinol, i-chloro-2,4-dihydroxybenzene, 3 ₅ 5-di-t-butyl-2,4-dihydroxybenzoic acid, 2,4-dib.hydroxybenzoic acid, 2,4-dihydroxyphenyl sulfide, p- Methoxypheno1 - _f p-lthoxypheno1, hydroquinone monobenzyl ether, 2-t-butyl-4-methoxyphenol, 2,5-di-t-butyl-4-methoxyphenol, hydroquinone mono-n-propyl ether, hydroquinone mono-n-hexyl ether, methyl gallate , Propyl gallate and the like.

5.) Ascorbic acid or derivatives thereof and other reducing agents which can be decomposed by light:

1-aseorbic acid, isoascorbic acid, ascorbic acid monoester, such as ascorbic acid monolaurate, monomyristate, monopalmitate, -möiiostearat and -monobehenate, ascorbic acid diester, such as Ascorbic acid dilaurate, dimyristate, dipalmitate and distearate, Furoin, benzoin, dihydroxyacetone, glyceraldehyde, tetrahydroxyquinone rhodizonate and the like

6.) 3-I ⁾ 3rcazolidone and Pyrazolone:

i-phenyl-3-pyrazolidone, 4-methyl-4-hydroxymethyl-1-phenyl-3-pyrazolidone, 1- (2-quinolyl) -3-methyl-5-P7TazolQn and the like.

'?.) Reducing saccharides and others:

Glucose, lactose, p-oxyphenylglycine, hydroxytetronic acid , Ή, H-di- (2-ethoxyethyl) hydroxylamine, Ή , H-dialkyl-p-phenylenediamine, 5 _t 7-dib.ydroxy-4-methylcoumarin _s kojic acid and hinokithiol.

These reducing agents can be used individually or in a summer

"oination of two or more can be used, 3is. A suitable reducing agent is seen in dependence on the cirgsa

509835 /

Silver salt (component a)) with which it is combined, selected. For example, a silver salt of a fatty acid such as silver behenate is relatively difficult to use reduce so that a relatively strong reducing agent such as hydroquinone is suitable. In contrast, a is proportionate weak reducing agent, such as bisphenol A, suitable for a silver salt, such as silver caprate, which is relatively easy to reduce. That is, the reducing agent can be easily selected depending on the organic silver salt used.

The amount of the reducing agent used varies depending on the kinds of the organic silver salt, reducing agent and other additives such as color toner used, and cannot be clearly specified, but a suitable amount is generally about 0.1 to about 5> preferably 0 , 2 to 2 moles per mole of the organic silver salt (component a). Color toners (coloring agents) are used as an important additive in combination with these reducing agents. The color toner is expediently added when a black color toner image is desired. The most commonly used color toners are phthalazinone and its derivatives. Other known effective colored toners are phthalimides, oxazinediones, pyrazolin-5-ones, oxazolinones and mercapto compounds as disclosed in Japanese Patent Application Nos. 41,969/1972, 41,967/1972 and 50,427/1973, in Japanese Patent Publication No. 60 77 / ^ 971 and in the German Offenlegungsschriften 2 140 406 and 2 141 063 are described.

The components (a), (b) and (c) used according to the invention -vsrden preferably dispersed in a binder (d) and applied to a carrier. In this case 'all components (a), (b) and (c) dissolved or dispersed and then applied as a layer to a support or the components (a / 5 (b- and (c) are dissolved separately in binders or

509835/0936

dispersed and applied in the form of different layers .

Suitable binders that can be used include any materials commonly used in the art. Ordinary hydrophobic binders are useful, but hydrophilic binders can of course also be used. These binders are transparent or semi-transparent natural materials such as gelatin and gelatin derivatives, mixtures of these materials with vinyl polymers of the latex type, cellulose derivatives and synthetic polymers. Suitable examples of such binders are gelatin, phthalated gelatin, polyvinyl butyral, polyacrylamide, cellulose acetate acrylate acetate, Polyvinylpyrrolidone, polystyrene, ethyl cellulose, polyvinyl chloride, chlorinated rubbers, polyisobutyler _H butadiene / styrene mixed polymers, vinyl chloride / vinyl acetate mixed polymers, vinyl acetate / vinyl chloride / maleic acid copolymers, cellulose acetate, cellulose diacetate and cellulose diacetate, cellulose diacetate and cellulose diacetate, cellulose diacetate, cellulose diacetate, cellulose diacetate, cellulose diacetate, cellulose acetate, polyisobutyl acetate and styrene . These binders can be used singly or in combination of two or more.

The binders are preferably used in a weight ratio of 10: 1 to 1:10, preferably 4: 1 to 1: 4, to component (a), the organic silver. If component (a) or (c) is a material with a high molecular weight which also has the ability to act as a binder, the use of such a binder can be omitted. The amount of silver applied to a support in Έότκ of a layer is. generally about 0.2 to about 0 ·, preferably G.3 to 2 S per tsl ~. Carrier. If less than about 0.2 g are used. ,, ka ^ i none = sufficient image density achieved wex-cl ^ -ii, while άε.ητ .. _: white,: .. fiiever used than about 3 g, the Eos ^ en increase irad

50983 5/0938

no additional photographic benefits are obtained.

If desired, the heat developed according to the invention can be used photosensitive material matting agents, such as starch, titanium dioxide, zinc oxide, silicon dioxide and kaolin and / or Fluorescent brighteners such as stilbenes, triazines, oxazoles and coumarins can be incorporated.

According to the invention, the heat-developable photosensitive Layer using various coating processes, for example an immersion process, an air knife coating process, a curtain coating process and an extrusion coating process using a hopper as described in U.S. Patent 2,681,294, be applied. If necessary, two or more layers can also be applied at the same time.

In order to further increase the sensitivity of the heat developable photosensitive material according to the invention, it is possible to use Advantage of some optically sensitizing dyes that are. suitable for silver halide emulsions. For example, a sensitizing dye in the form be added to a solution or dispersion in an organic solvent. Examples of suitable optical sensitizers are cyanines, merocyanines, ehodacyanines, styryl dyes and acidic dyes such as erythrosin, eosin and fluorescein. Me amount of such a dye used is

—6 '* —2

generally from about 10 to about 10 moles per mole of component (a), that is, the organic silver salt. Suitable sensitizing dyes are disclosed in U.S. Patents 3,152,904, 3,719 4-95 and 3,761,279, in Belgian Patent 788,695, in German OffenlegungsSchriften 2,328,868, 2,363,586, 2,405,713, 2,401,982 and 2 4-04-591, in Japanese Patent Application Nos. 50903/1973 and 97 05O / I973 and Lz of Japanese Patent Publication Wr. 4-728 / 1971.

509835/0936

In addition, in the heat developable photosensitive Layer, if necessary, also additives to prevent the heat haze. (one when heating a non-exposed Area formed undesirable veil), such as mercury salts and N-shark iron compounds. These additives are disclosed in U.S. Patent 3,589,903, US Pat German Offenlegungsschriften 2 326 865, 2 4-02 161 and 2,364,630 and Japanese Patent Application No. 4-3,935/1973 described. Acids, e.g. higher fatty acids and benzenesulfonic acid, can also be contained as stabilizers, as in the Japanese Patent Applications Nos. 37,965/1973 and 106 724/1973. Benzotriazole and ._ its derivatives and i-phenyl-5-mercaptotetrazole are added.

If desired, a polymer top layer can be applied to the photosensitive layer in order to improve the transparency of the heat developable photosensitive layer, to increase the image density and to retain the original storage properties (i.e. the retention of the photographic properties that it originally had, even after storage ) to improve. The thickness of such a coating layer is preferably from about 1 to about 20 microns. Examples of suitable polymers for the film coating layer are polyvinyl chloride, polyvinyl acetate, yinyl chloride / vinyl acetate copolymers, polyvinyl butyral, polystyrene, polymethyl methacrylate, polyurethane rubber, xylene resin, benzyl cellulose, a "thyl cellulose, cellulose acetate, polyvinyl acetate, cellulose acetate, polyvinyl acetate, cellulose acetate, polyvinyl acetate, cellulose acetate, polyvinyl acetate, cellulose acetate, yinyl chloride / vinyl acetate copolymers / vinyl acetate mixed polymers, yinyl chloride / vinyl acetate copolymers, cellulose acetate, polyvinyl acetate, cellulose acetate, polyvinyl acetate, cellulose acetate, polyvinyl acetate, cellulose acetate , Polyviny! Formal, cellulose acetate phthalate, polycarbonate and cellulose acetate propionate.

If a material such as kaolin or Silicon dioxide, may be the thermally developable light-sensitive material with a ballpoint pen or with a pencil after making the picture "b-ssöliriebsn

503835/0336

will. An ultraviolet absorber, e.g. a diaminostilbene sulfonic acid derivative, an imidazole derivative, a coumarin derivative and the like, or a higher fatty acid, e.g. "an aliphatic carboxylic acid with at least 10 carbon atoms, such as behenic acid, stearic acid, palmitic acid, aluric acid and the like., are incorporated. In addition, a phenol coupler can be used in combination with a p-phenylenediamine as a reducing agent or a color coupler having an active methylene group can be used to form a color image, as in FIG U.S. Patent 3,531,286.

The heat developable photosensitive material described above is applied with a light source such as a xenon lamp, a tungsten lamp, a mercury lamp or a

-7

Copying fluorescent _lamp} example, from about 10 'to about 100, preferably from 10 "long exposed image-wise to 10 seconds and then developed in a simple manner by heating. A suitable Erhitzungsteiaperatur is generally from about 80 to about 180, preferably at 110 to 15O ⁰ C. Of course, A higher temperature or lower temperature can also be used if the heating time is suitably decreased or lengthened, and a suitable development time is generally about 1 to about 60 seconds.

The heating and development of the photosensitive body of the present invention Material can be made using various methods, for example by making the photosensitive Material with a "simple heated plate or with contacting a heated drum or by passing the material through a heated room or by use in high frequency heating or a laser beam.

From the foregoing description, it is understood that:> The heat developable photosensitive of the present invention Material around a heat developable photosensitive material

509835/0936

acts that can provide a high-contrast image and " suitable for reflection printing «,

The invention is illustrated in more detail by the following examples, without, however, being restricted thereto. All of the examples given therein Parts, percentages, ratios and the like relate to weight unless otherwise specified.

example 1

3,4 g of behenic acid was dissolved at 60 ⁰ C in 100 ml of toluene and the temperature was maintained at 60 ⁰ G. While stirring with a stirrer, the solution was mixed with 100 ml of a dilute aqueous nitric acid solution having a pH of 2.0 (of 25 ° C.). To the mixed solution thus obtained, which was kept at 60 ^° G, while stirring with a stirrer, was added a solution obtained by adding a concentrated aqueous ammonia solution to about 80 ml of an aqueous solution containing 1.7 g of silver nitrate to form a silver ammonium complex salt, and then adding water to make up the total volume to 100 ml of the prepared aqueous solution and 50 ml of an aqueous solution of 0.047 g ammonium bromide, 0.001 g ammonium;} ο did and 0.0025 S ammonium rhodium (III) hexachloride added to form silver behenate and silver iodobromide. After the reaction product had been allowed to stand at room temperature for 20 minutes, separation into an aqueous phase and a toluene phase occurred. after the aqueous phase was removed, 400 ml of fresh water was added to the toluene phase and the product was washed by decantation. Then 400 ml of methanol was added and the mixture was subjected to centrifugal separation to obtain a mixture of silver behenate and silver iodobromide. In this way 4 g of spindle-shaped crystals with a length of about 0.9 microns and a width of about 0.03 microns were obtained *

509835/0936

2.5 S of the resulting mixture of silver behenate and Silver iodobromide was added to 25 grams of a 2 gram polyvinyl butyral containing isopropanol solution was added and the mixture was ground for one hour in a ball mill to form a polymer dispersion of the silver salt.

To 25 g of the resulting polymer dispersion of the silver salt the following components were added to prepare a heat developable photosensitive Coating composition and then the composition in the form of a layer on an art paper support according to a Amount of silver of 0.5 g P ^ o m carrier applied, with a thermally developable photosensitive material (A) became. For comparison, another heat developable photosensitive material (B) was prepared in a similar manner using a mixture of silver behenate and silver iodobromide analogous to above, but without adding the rhodium salt.

Mercury (II) acetate (heat curtain inhibitor)
(1% methanol solution) 1 ml

Dye*

(0.025% 2-methoxyethanol solution) 1 ml

Phthalazinone (color toner)

(2.5% 2-methoxyethanol solution) 5 ml

2,2'-methylene-bis (6-t-buty 1-4-methyl-

phenol) (reducing agent)

(25% 2-methoxyethanol solution) 5

Tetrabromophthalic acid (anhydrous)

(0.5% methanol solution) 2 ml

Behenic acid

(3% 2-methoxyethanol solution) 5

lT> CH-CH _r . η

509835/0936

These two light-sensitive materials (A) and (B) were exposed through an optical step wedge and ^{heated to 120 °} C. for 20 seconds and developed. When the difference in the logarithm of the exposure amount giving an image density above fog of + 0.6 and the exposure amount giving an image density above fog of + 0.1 for both photosensitive materials was compared with each other, the difference was 0 , 33 for the photosensitive material (A) and 0.95 for the photosensitive material (B). From this result, it can be seen that the light-sensitive material (A) in which a rhodium salt was used had a high contrast. In the case of the photosensitive material - (A), when a negative image of the positive original was formed by reflection copying using the photosensitive material (A) or (B), and when a positive image was again formed from this negative image as the original by transmission copying. -a high contrast sharp positive. Image reproduced, while in the case of the light-sensitive material (B) only a low-contrast, dark positive image was reproduced.

Example 2

6 g of benzotriazole were dissolved at 50 ⁰ G in 100 ml of isoamyl acetate and the solution was cooled to -15 C. A solution was added to the solution while stirring with a stirrer, which was prepared by dissolving 8.5 g of silver nitrate in 100 ml of a dilute aqueous nitric acid solution having a pH of 2.0 (of 25 ° C.) and adjusting the temperature to 0 ⁰ C had been produced, a dispersion containing fine crystals of silver benzotriazole being obtained in this way. When this dispersion for 20 minutes at room temperature (ie, about 20 to 30 ⁰ C) was allowed to stand, entered a separation into an aqueous phase and an Isoamylacatatphase

5 O S 8 3 D i

/ Γ-

on. After the aqueous phase had been removed, were another 400 ml of water was added to the isoamyl acetate phase and the product was washed by decantation. Then were '400 ml of methanol were added and the dispersion was subjected to centrifugal separation subjected, with 8 g of silver benzotriazole having a particle size of about 1 micron in diameter. 2.5 g of the silver benzotriazole obtained in this way were added to 40 ml of a methyl ethyl ketone solution containing 4 g of ethyl cellulose added and the mixture was ground for 1 hour in a ball mill to produce a polymer dispersion of the silver salt. To 45 g of the silver salt polymer dispersion The following components were added to prepare a heat developable photosensitive Coating compound and the coating compound was then in the form of a layer on a paper support, the surface of which was coated with clay and styrene / butadiene rubber,

ρ applied corresponding to an amount of silver of 1 g per m support, whereby a heat developable photosensitive material (A) was obtained. For comparison, it was also made in an analogous manner a heat developable photosensitive material (B) was prepared, but this time without adding the rhodium salt.

Methyl ethyl ketone 20 ml

Cadmium iodide (forming a silver halide Component) (8.5% methanol solution) 1.5 ml Ammonium rhodium (III) hexachloride

(Ehodium salt) (0.1% aqueous solution) 3 ml ascorbic acid monopalmitate / ascorbic acid

dipalmitate mixture (reducing agent)

(2 g each in 10 ml 2-methoxyethanol) 10 ml N-ethyl-IT ¹ -dodecylurea (development accelerator) (2.5% 2-methoxyethanol solution) 2 ml

Dye*

(0.015% 2-methoxyethanol solution) 2 ml

509835/0936

K - N
| i

NJ = CH-CH = - Ι

Both of the light-sensitive materials (A) and (B) were treated in a similar manner to Example 1. Development was carried out by heating at 130 ° for 10 seconds. The difference in the logarithms of the amount of exposure was _? similar to example 1, the following values:

difference

light-sensitive material (A) 0.61

(B)

From this result it is evident that the photosensitive Material (A) has a higher contrast.

Example 5

1j9g of sodium hydroxide was dissolved in 100 ml of water and added to 25 ° 0 with a solution of 12 g of lauric acid, dissolved in 1OO ml ! Dcluol, mixed xmd emulsified. An aqueous solution was used for this purpose of 8.5 S silver nitrate, dissolved in 50 ml of water, was added. There was a separation into an aqueous vase and a bilber lanrat containing ioluo! phase on "laughing at the removal of the aqueous phase was the * 3k »luolpl ± ase in 200 ml Methanoi dispsr gated and the dispersion was subjected to a Zsn.trifuge separation thrown, with 12 g of spindle-shaped silver laurel-all one-length of about 3 microns.

6 g of the resulting silver laurate and 12 g

509835/0936

were dispersed in 70 ε isopropyl alcohol using a mixer to produce a polymer dispersion of the silver salt. This polymer dispersion of the silver salt was kept at 50 ⁰ G, stirred with a stirrer, mixed with 0.003 g Ammoniumrhodium (III) hexachloride, stirred for 20 minutes, allowed to stand, with 0.15 S N-bromosuccinimide (which is a silver halide-forming component) mixed , Stirred for 90 minutes and left to stand. The components indicated below were added to the dispersion, which was adjusted to 30 ° C. and stirred, one after the other at intervals of. 5 minutes each was added to prepare a heat-developable photosensitive coating material, and the coating material was applied in the form of a layer on an art paper accordingly

an amount of silver of 0.4 g per m applied, with a heat developable light-sensitive material (A) was obtained.

Dye*

(0.015% 2-methoxyethano! Solution) 10 ml

Phthalazinone (color toner)

(3% methanol solution) 50 ml

2,2-bis (3,5-dimethyl-4-hydroxyphenyl) propane

(20% acetone solution) 300 ml

Stearic acid

(3% 2-methoxyethano! Solution) 15 ml

CH COOH

For comparison, another heat developable photosensitive was prepared in a similar manner, but without adding the rhodium salt.

509835/0936

made of liohes material (B).

Both light-sensitive materials (A) and (B) were also treated with a 1% acetone solution of cellulose diacetate, containing 1.5% silica coated to form an overcoat layer.

Both pretreated light-sensitive materials were exposed through a step wedge similarly as in Example 1 stepwise and heated to 120 ⁰ G then for 10 seconds and developed. Similar to Example 1, a logarithmic difference of the exposure amounts was obtained.

difference

Photosensitive material (A) 0.45

"(B) 1.02

As can be seen from this result, the light-sensitive material (A) had a high contrast.

When a positive image was reproduced similarly to Example 1, the photosensitive material (A) gave a lot sharper positive image.

Example 4

8.6 g of capric acid were dissolved in 100 ml of butyl acetate, at Maintained 5 C, stirred with a stirrer, with 50 ml of a 0.4 % aqueous hydrobromic acid solution mixed and emulsified. 50 ml of an aqueous solution of a silver nitrate were added to the emulsion obtained in this way over a period of 30 seconds ammonium complex salt, which contained 8.5 g of silver nitrate (cooled to 50), added to the capric acid and the hydrogen bromide to be implemented simultaneously with silver ions. The SiI-bercaprat and the silver bromide were formed at the same time.

509835/0936

The aqueous phase was removed and the "butyl acetate phase containing both silver salts" was dispersed in 120 g of a 15% isopropanol solution of polyvinyl butyral to produce a polymer dispersion of the silver salt. The following components were added to this polymer dispersion of the silver salt to produce a heat-developable solution photosensitive Beschichtungsm _a sse and the coating composition was in the form of a layer on a coated paper in accordance with a silver amount of

2
1.0 g per m 2 of support to obtain a heat developable photosensitive material (A).

Mercury (II) acetate (heat curtain inhibitor)

(1% methanol solution) 10 ml

Ehodium bromide

(4% methanol dispersion) 4- ml

Tetrachlorotetrabromofluorescein (dye) (0.025% methanol solution). 70ml

Phthalazinone (color toner)

(2.5% 2-methoxyethanol solution) 25 ml

Bisphenol A (reducing agent)

(70% 2-methoxyethanol solution) 70 ml

For comparison, another heat developable photosensitive material (B) was prepared in a similar manner but without adding the rhodium salt. These light-sensitive materials were exposed through an optical wedge and long for 5 seconds heating at 14-0 ⁰ C, similarly as in Example 1, developed. The logarithmic difference of the exposure amounts was obtained in a manner similar to that in Example 1.

difference

Heat developable photosensitive

Material (A) 1.20

Heat developable photosensitive

Material (B) 1.08

509835/0936

As can be seen from this result, the photosensitive exhibited Material (A) exhibited a lower contrast, i.e. the rhodium bromide was ineffective.

Example |?

3,4 g of behenic acid was dissolved in 100 ml of benzene at 60 ° G and kept at 60 ⁰ C · While stirring with a stirrer were 100 ml of a dilute aqueous nitric acid solution having a pH value of 2.0 (25 ⁰ C) containing 7 mg of shodium nitrate was added. The resulting mixed solution was kept at 60 ° C, stirred with a stirrer, and mixed with an aqueous solution obtained by adding aqueous ammonia to about 80 ml of an aqueous solution containing 1.7 g of silver nitrate to form a silver ammonium complex salt and then adding Water was made up to a total volume of 100 ml, whereby fine rhodium-containing silver behenate crystals were obtained. When the resulting dispersion was allowed to stand at room temperature for 20 minutes, separation into an aqueous phase and a toluene phase occurred. After removing the aqueous phase, 400 ml of fresh water were again added to the toluene phase and the product was washed by decantation. Then 400 ml of methanol was added and the mixture was subjected to centrifugal separation to give 4 g of spindle-shaped silver behenate crystals about 1 micron in length and about 0.05 micron in width.

2.5 S of the silver behenate thus obtained became 20 ml of a 2 g of isopropyl alcohol solution containing polyvinyl butyral were added and the mixture was then ball milled for 1 hour to prepare a polymer dispersion of the Silver salt. The components indicated below were added to 20 ml of this polymer dispersion of the silver salt for producing a heat developable photosensitive

50983 5/0936

Coating compound and the coating compound was developed in the form of a layer on a photographic original paper

p applied corresponding to an amount of silver of 0.6 g per m of carrier being a heat developable photosensitive material (A) was obtained.

Ammonium bromide (a component forming silver halide]) (2.5% methanol solution)

Dye*

(0.025% 2-methoxyethanol solution)

2,2'-methylene-bis (6-t-but νΙ-Λ-methylphenol) (Reducing agent) (20% acetone solution)

Phthalazinon (color toner) (2.5% 2-methoxyethanol solution)

anhydrous tetrabromophthalic acid

(Stabilizer)

(0.6% methanol solution)

1 ml 1 ml

3 ml 3 ml

1 ml

-S

H ₂ CH = CH ₂

For comparison, a heat developable photosensitive was obtained in a similar manner but without adding the rhodium nitrate Material (B) was prepared and also was prepared in a similar manner, but using an equimolar amount of Rhodium bromide instead of rhodium nitrate and without using ammonium bromide ^ in heat-developable photosensitive Material C made. The logarithmic difference of the. Exposure amount was obtained in a similar manner to Example 1.

509835/0936

difference , 96 O , 50 O 1

.- 36 -

The development was carried out by heating to 120 ^° C. for 10 seconds.

Heat developable photosensitive material '(A)

Heat developable photosensitive Material (B)

Heat developable photosensitive material (G)

From the above result, it can be seen that the heat developable light-sensitive material (A) in which the rhodium salt was used had a higher contrast and that the rhodium halides were not effective in accordance with the invention.

Example 6

0.8 g of cetylethyldimethylammonium bromide and 0.05 g of potassium rhodium (III) hexachloride were dissolved in 100 ml of water to form a solution, which was mixed with 100 ml of toluene and emulsified. A solution of 0.4-25 g of silver nitrate in 10 ml of water was added to this emulsion to prepare Silver bromide containing rhodium. This silver bromide was in an emulsified state. A solution of 12 g of lauric acid in 100 ml of toluene and a solution of 1.9 g of sodium hydroxide in 100 ml of water were mixed with one another, emulsified and admitted. Then a solution of 8.5 g of silver nitrate in 50 ml of water was added to produce silver laurate. A mixture of rhodium-containing silver bromide in contact with silver laurate was obtained. The one made in this way Mixture was separated by centrifugal separation and then using a mixer in 200 g of a 30 g Ethanol solution containing polyvinyl butyral dispersed for the production of a silver salt polymer dispersion. To this Silver salt polymer dispersion, the following specified

509835/0936

"added components to produce a thermally developable photosensitive coating material, which is then applied to a photographic original paper according to a

ρ
Silver amount of 0.5 g per m carrier was applied.

Dye*

(0.025% methanol solution) '' 10 ml phthalazinone (color toner)

(3% methanol solution) 35 ml

2,2-bis (3-methyl-4-hydroxyphenyl) propane

(Reducing agent)

(20% acetone solution) 70 ml

Victoria Blue B (whitener)

(0.015% methanol solution) 2 ml

Then a 10% tetrahydro was used for a solution of a vinyl chloride / vinyl acetate mixed polymer, which contained 1.5% kaolin, applied underneath to produce a top layer Form a film thickness of 2 microns (heat developable photosensitive material (A)). For comparison, a other heat developable photosensitive material (B) was prepared in a similar manner but without using the Rhodium salt. Similar to Example 1, development was carried out by heating at 130 ° C for 3 seconds and the logarithmic difference of the exposure amounts was obtained.

509835/0936

difference

Heat developable photosensitive

Material (A) * 0.48

Heat developable photosensitive

Material (B) 1.20

As can be seen from this result, this was demonstrated by the bhodium salt thermally developable photosensitive material (A) containing a higher contrast.

The invention has been described above with reference to specific Embodiments explained in more detail, but it is for it goes without saying to the person skilled in the art that it is by no means restricted thereto, but that it is modified in many ways and can be modified without departing from the scope of the present invention.

Claims;

50S835 / 0936

Claims (9)

Claims Heat developable photosensitive material, characterized by a support and at least one applied thereon Layer that contains a) an organic silver salt, b) a catalytic amount of a photosensitive silver halide or a compound which reacts with the organic silver salt (a) to form a photosensitive silver halide can react, and c) a ^ reducing agent, wherein at least a portion of the catalytic amount of the photosensitive Silver halide has been made by the reaction of a compound with the organic silver salt can react to form a photosensitive silver halide in the presence of a rhodium salt selected is from the group of a halo rhodium complex of the general formula where mean: M 'a monovalent cation, X "is a halogen atom, h is an integer from 2 to 5 ₅ k is the integer 1 or 2 j 1 is an integer from 5 ^ is 11, m is the integer O or 2 and ρ is an integer from 0 to 12, and rhodium nitrate. 2. Material according to claim 1, characterized in that it is a silver salt of an organic compound as the organic silver salt 50983ΰ / 0936 bond with an imino, mercapto, thione, hydroxyl or Contains carboxyl group. 3. Material according to claim 1 and / or 2, characterized in that it is a silver salt as an organic silver salt Contains fatty acid. 4-, material according to at least one of claims 1 to 3 »characterized in that the halo-rhodium complex is the compound _-, _, '■ ), K ₂ (EhCl ₅ (OH) ₂ D, (NH ^) ₂ (EhCl ₅ (OH) ₂ ) »■, Eb ₂ (EhCl ₅ (OH) ₂ ), Cs ₂ (EhCl ₅ (OH) ₂ ) -, Li ₅ OEhCl ₆ ) Na ₃ (EhClg) 12H ₂ O, Li ₃ (EhClg) 6H ₂ O, Ka ₃ (EhClg) 10H ₂ O, Na, (EhClg) 6H ₂ O, Na ₃ ( EhClg) -2H ₂ O, Na ₃ (EhClg), K ₃ (EhClg) -H ₂ O, (HH.) ₃ C'j3hCl ₆ ) _{.12H 2} O, (NH ^) ₃ (EhClg) -H ₂ O , (JCH ₃ ) ^ H ₂ J ₃ (EhCIg), (CH ₃ NH ₃ ) ^ (EhCl ₇ ), (I ₂ ^ NH ₃ J ₂ (EhCl ₇ ), ((CH ₃ ) ^ ₃ (Eh ₂ Eq ₉ ), ((CH ₃ CH ₂ ) ₄ N) ₃ (Eh ₂ Cl ₉ ), K ₂ (EhBr ₃ ), (NHJ ₂ (BhBr ₅ ) ZEb ₂ (EhBr ₅ ), Na ₃ (EhBr ₆ ) Na ₃ (EhBr ₆ ) -H ₂ O, Na ₃ (EhBr ₆ ), (^ NH) (RhBr ₆ ), IC ₂ H ₄ NH ₃ ) _£ (EhBr ₇ ), (C ₃ H ₆ NH ₃ I ₂ ( BhBr ₇ ), (^ JiH) ₄ (EhBr ₇ ) -6H ₂ O, K ₃ (Eh ₂ Br ₉ ), (NH ^) ₃ (Eh ₂ Br ₉ ), (CH ₅ NH ₃ X ₅ (Rh ₂ Br ₉ ), (^ QiH) ₃ (Eh ₂ Br ₉ ) - ) ₃ (Bh ₂ Br ₉ ) hande It. 5. Material according to at least one of claims 1 to 4-, characterized in that it. as a compound capable of reacting with the organic silver salt (a) contains a inorganic halide of the general formula MX _n 509835/0936 where mean: M is a hydrogen atom, an ammonium group or a metal atom, X is a chlorine atom, a bromine atom or an iodine atom and η the number 1, if M is a hydrogen atom or an ammonium group is, or the valence of the metal atom, if M is a metal atom, a halogen-containing metal complex, an IT-halogen compound having a -CONX 'group, wherein X ^{f is} a chlorine atom, a bromine atom or an iodine atom, an onium halide, a halogenated hydrocarbon from the group iodoform, bromoform, 2-bromo-2-methy Propane and carbon tetrabromide or a halogen-containing compound from the group consisting of triphenylmethyl chloride, triphenylmethyl bromide, 2-bromobutyric acid, 2-bromoethanol and benzophenone dichloride. 6. Material according to claim 5> characterized in that it as a compound capable of reacting with the organic silver salt (a), an N-halogen compound having a -COHX 'group, wherein X ^{I has} the meanings given in claim 5 contains. 7. Material according to at least one of claims Λ to 6, characterized in that the rhodium salt is present in an amount of about 0.0001 to about 0.5 mol per mol of the compound which can react with the organic silver salt (a) . 8. Material according to at least one of claims 1 to 7 »characterized in that it is a substituted reducing agent Phenol, a substituted or unsubstituted bisphenol, a substituted or unsubstituted naphthol, a substituted or unsubstituted bisnaphthol ^ a dioder Polyhydroxynaphthylene, a di- or polyhydroxybenzene, a hydroquinone monoether, ascorbic acid or a derivative thereof, 509835/0936 a photodegradable reducing agent, a 3-don, a]? yrazolon, a reducing saccharide, p-oxyphenylglycine, Hydroxytetronic acid, N, ET-di- (2-ethoxyethyl) hydroxylamine, a Ν, Π-dialkyl-p-phenylenediamine, 5 j 7-dihydroxy-4-methylcoumarin, Contains kojic acid or hinokithiol. 9. Material according to at least one of claims 1 to 8, characterized in that at least one layer contains a binder (d). 509835/0936