DE2635541A1 - THERMALLY DEVELOPMENT LIGHT SENSITIVE MATERIAL - Google Patents

Description

FATENTANWE-.TE

DR. E. WIEGAND DIPL-ING. W. NIEMANN DR. M. KÖHLER DIPL.-ING. C. GERNHARDT

MÖNCHEN HAMBURG 2635541

TELEPHONE: 55547 «8000 M ö N C H E N 2,

TELEGRAMS: KARPATENT MATH I LDENSTRAS3E 12

TELEX: 5 29 008 KARP D. | j

V. 42623/76 - Ko / Ne August 6, 1976

Fuji Photo Film Co. Ltd., Minami Ashigara-ßhi, Kanagawa (Japan)

Thermally developable photosensitive

material

The invention is concerned with a thermally developable photosensitive material, and in particular relates to a thermally developable. photosensitive material Material that has improved properties due to the Addition of a trivalent and / or tetravalent cerium compound owns.

According to the invention, a thermally developable photosensitive material is specified which comprises (a) an organic silver salt, (b) a photocatalyst and (c) a reducing agent in a support or in one or more layers on a support, which additionally comprises (d) has at least one cerium compound from three-valent and / or tetravalent cerium compounds in the carrier and / or in one or more of the above layers ,

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The improvement of various properties, such as long shelf life, high degree of whiteness, lower thermal fog, high sensitivity and the like are obtained.

Thermally developable photosensitive materials using a hatred of being essential Ingredients contains an organic silver salt, a small amount of silver halide and a reducing agent, are in U.S. Patents 3,152,904 and 3,457,075 specified. In these light-sensitive systems, the silver halides remain in the light-sensitive material the development and color change after exposure, d. H. they are not stabilized against light. Nevertheless these systems give satisfactory results like the other system, with the remaining silver halide receives a stabilizing treatment against light. The reason is that there is only a small amount of silver halide is used and a large proportion of the silver component in the form of white or pale yellow organic Silver salts, which are stable to light, are present, so that they hardly blacken during exposure. Even if a discoloration results from the decomposition of the remaining silver halide caused by the exposure, such a slight discoloration can hardly be perceived by the eye. In the case of the photosensitive ones described above Systems, the images are formed according to the following mechanism: The oxidizing agent (organic Silver salts) and that incorporated into the photosensitive layer reducing agents undergo a redox reaction in the presence of a catalytic amount of exposed silver halide one when the system is heated to 80 ° C, preferably up to 100 ° C after the completion of the imagewise exposure will, although the system is at ordinary temperature

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is inert, so that the release of silver occurs, which causes a rapid blackening of the exposed areas of the photosensitive layer, so that a contrast in relation to the non-exposed areas (background) will.

Also include the thermally developable photosensitive Materials of this kind those that act as a photocatalyst are a photosensitive complex made up of silver and a dye is contained in place of the above silver halide as in Japanese Patent Applications 4728/71 and 23221/75 and Japanese Patent publication 254-98 / 74- indicated, as well as those which as organic silver salts are a highly sensitive organic Contains silver salt and a low-sensitive organic silver salt in combination and is therefore free from May be silver halide as disclosed in Japanese Patent Application 8522/75. Thus, such are thermal developable photosensitive materials means the materials to which the method of the invention is applicable.

The addition of mercury compounds to thermally developable photosensitive materials improves the green storage life as reported in U.S. Patent 3,589,903. Mercury compounds are however therefore undesirable because they are generally highly toxic. Therefore, there is an important task in finding Compounds of low toxicity that can replace mercury compounds.

It is therefore an object of the invention to provide a thermally developable photosensitive material Improved green storage life (gree.i shelf life).

Another object of the invention is a thermally developable photosensitive material ait improved whiteness.

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Another object of the invention is a thermally developable photosensitive material, wherein increased thermal fog (corresponding to the fog formed in the background during thermal development), which is due to storage before development is suppressed.

Another object of the invention is a thermally developable photosensitive material which after image formation after prolonged storage, an image with a hue equal to that of one Provides an image obtained immediately after the light-sensitive material was prepared.

Another object of the invention is a thermally developable photosensitive material, wherein the coloring of the background of the image obtained after exposure (hereinafter referred to as being caused by light Color change) is reduced.

Another object of the invention is a thermally developable photosensitive material showing high sensitivity. ·,

Further objects of the invention will become apparent from the following description.

The above objects are achieved with a heat developable photosensitive material which contains one or more trivalent and / or one or more tetravalent cerium compounds.

A preferred embodiment of the present invention provides a thermally developable photosensitive material which (a) an organic silver salt, (b) a photocatalyst : and (c) a reducing agent in a support and / or in one or more layers on the support and further (d) at least one cerium compound from trivalent and tetravalent cerium compounds in the carrier

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and / or in one or more layers thereon, both trivalent and tetravalent cerium compounds can be used if desired.

The component (d), which is the most characteristic component according to the invention, includes one or more trivalent and / or one or more tetravalent cerium compounds. Tetravalent cerium compounds improve remarkably the green storage life. On the other hand, trivalent cerium compounds remarkably improve whiteness.

Preferred examples of trivalent or tetravalent cerium compounds include compounds according to FIG following general formulas (I) and (II):

(I) (II)

wherein Ce is a trivalent or tetravalent cerium atom, X is Anion or a group capable of being converted into an anion, specific examples of which are a nitrate ion Hydroxide ion, an oxygen ion, a titanate ion, an acetate ion, an acetylacetonate, a carbonate ion, a halogen ion, for example chlorine, bromine or iodine atoms, long chain aliphatic carboxyl groups, most preferably with 10 to 30 carbon atoms, for example laurate, palmitate, Stearate and behenate groups, a perchloration. a Phosphate ion and the like, with particularly preferred examples being titrations, halogen ions and long chain aliphatic Groups are where M is a cation or a group capable of being converted into a cation, with specific examples for this a hydrogen ion, an alkali ion, for example

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Lithium, sodium, potassium, cesium and rubidium atoms, onium groups, for example ammonium groups, phosphonium groups, arsonium groups, stibonium groups, sulfonium groups, selenonium groups, stannonium groups, iodonium groups, IUN groups being preferred, where RH, an alkyl group with 1 to 22 carbon atoms , an aryl group containing 6 to 22 carbon atoms, ζ. B. an NH ^ group, a tetramethylammonium group, represent 1, m, η, ρ and q are the necessary integers to make the compound neutral, for example 1 has the value Λ and m has the value 4 if Ce represents a tetravalent cerium atom, η is 2, ρ is 1 and q is 6 if Ce is a tetravalent cerium atom, M is a monovalent cation and X is a monovalent anion and 1 is 2 and m is 3 if Ce represents a trivalent cerium atom and X a divalent anion, and χ and y «each represent an integer including zero, most preferably 0 to 16, which cannot necessarily be defined as it is dependent on the conditions of manufacture and storage, where however, χ and y are generally such that a high degree of deliquescence is obtained, numerous technical hydrates of this type being represented by the designation 'xHpO. In the context of the invention, a mixture of compounds with varying degrees of water of crystallization can be used if desired.

Specific examples of trivalent and tetravalent compounds are given below: Ce (OH) ,, Ce (OH) ₄ , CeO ₂ , Ce ₅ O ₅ , LigCeOg, Na ₂ CeO ₅ , KCeO ₂ , K ₂ CeO ₅ , CeN, Ce ( NOj) ₃ , Ce (NO ₅ ) ^ eH ₂ O, Ce (NO ₅ ^ '51I ₂ O, Ce (NO ₅ ), ■ · 4H ₂ O, Ce (NO ₅ ) ₄ · 5H ₂ O, CeOH (NO ₅ ) j'xHgO *, (x = 0 and / or 3), KCe (NO ₅ ) ^ - HgO, K ₂ Ce (NO ₅ ) _c , K ₃ Ce (NOj) ₆ , RbCe (NO ₅ ) ^ H ₂ O, Rb ₂ Ce (NO ₅ ) _r. 4H ₂ O, Rb ₂ Ce (NO * ₅ ) ₆ , CsCe (NOj) ₅ -HgO.

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₃ ) ₆ , NH ₄ -HCe (NO ₃ ) ^ - H ₂ O, (NH ₄ ) ₃ ^ (χ = 0 and / or 4-), Ce (CH ₃ COO) ₃ ^ HpO, (CH ^ OCHCOCHj) ₃ Ce, (NH ^) ₂ Ce (SO ^) ₆ -XHpO (χ = 0.2 and / or 8), Ce ₂ (CO ₃ ) ₃ .8HpO, CeCl ₃ * 7H ₂ O, Ce ₂ (SO ^ ) ₃ * 8H ₂ O, Ce (SO ₄ ) ^ xH ₂ O (x = O ₁ 2, 4-7 5, 8, 9 and / or 12) CeBr ₇ , Ce (TiO ₇ ) _p , CeI ₃ «9H ₂ O, Ce (C10 ₄ ) ₃ · 6H ₂ O, CePO ₄ , Ce (C ₁₂ H ₂₅ COO) ₃ , Ce (C ₂ pH ₄₅ C00) ₃ , Ce (C ₁₈ H ₃₇ CDO) ₃ and the like.

Furthermore, cerium complex salts, which are organic as ligands Containing molecules can also be used. Nitrogen-containing organic compounds are used as ligands for the complex salts Compounds and dibasic acids are preferred. In particular, nitrogen-containing heterocyclic compounds are used and dibasic acids which have two carboxylic acid groups have bonded via 0 to 4 carbon atoms, preferably d. H. Bonds between the CO components. Specific examples of such ligands are 2,2'-bipyridyl, 1.10 « Phenanthroline, phthalocyanine, pyridine, quinoline, 8-hydroxyquinoline, Urotropin, diphenic acid, naphthalic acid, phthalic acid, Oxalic acid and the like. Mentioned.

Specific examples of cerium complex salts include Ce (DIp) ₂ (NO ₃ ) * xH ₂ 0 (where Dip is 2,2 ^! -Bipyridyl) (x = 0 to 16), Ce (DXp) ₂ Br ₃ , Ce (Phen) ₂ (NO ₃ ) ^ (where phen is phenanthroline), (Ce (PhCn) ₂ (SCN) ₃ , Ce (Phtha) 3r (where Phtha is phthalocyanine), Ce (UrO) ₂ (SCN) ₃ "8H ₂ O ( where Uro is urotropine), NaWfCe (DP) ^ / (where DP is diphenic acid, Ka / Ce (L ^r e.piith.) ₂ / (where ITaphth is naphthoic acid), NH ₄ / Ce (0X) _p 7-xH ₂ 0 (where OX is oxalic acid (x = 0 to 16) and similar compounds.

Component (d) can be used in any photographic layer of the thermally decomposable licitvensible material be incorporated, and it doesn't matter how and. when component (d) is added.

The amount of component (d) to be added cannot

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can be given as a general rule, as it depends on what types of connections are used for each of the additional components. As a conductance, however, it can be stated that the addition of about 5 × 10 moles to about 1 × 10 moles of component (d) per mole of organic silver salt (a) produces beneficial effects. A more preferred concentration range for component (d) is in the range of about 10 "to about 10 moles per mole of the organic silver salt (a).

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In the case of the organic silver salt component used in accordance with the invention (a) it is a colorless or faintly colored silver salt which is comparative to light is stable and reacts with a reducing agent to form a silver image when raised to a temperature heated at not less than about 80, preferably not less than 100 ° C in the presence of exposed silver halide will. Such organic silver salts include silver salts of organic compounds with an imino group, a mercapto group, a thione group or a carboxy group. Specific examples of this are the following:

1.) Silver salts of organic compounds with an imino group:

The silver salt of Benzotriazoi, the silver salt of ITitrobenzotriazole, the silver salt of an alkyl substituted benzotriazole (e.g. methylbenzotriazole and the like), the silver salt of a halogen-substituted benzotriazois (e.g. the silver salt of bromobenzotriazole, the silver salt of chlorobenzotriazole and the like.), the silver salt of a carboimide-substituted Benzotriazois,

CH, (CH ₂ ) COIiH

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The silver salt of benzimidazole, the silver salt of a substituted one Benzimidazole (e.g. the silver salt of 5-chlorobenzimidazole, the silver salt of 5-nitrobenzimidazole and the like), the silver salt of carbazole, the silver salt of saccharin, the silver salt of phthalazinone, the silver salt of a substituted Phthalazinons, silver salts of phthalimides, that Silver salt of pyrrolidone, the silver salt of tetrazole, the silver salt of imidazole, N- (benzoic acid-sulfonic acid- (2) imide) -silver, N- (4-nitrobenzoic acid sulfonic acid (2) imide) silver, F- (5-nitrobenzoic acid-sulfonic acid- (2) -imide) -silver and others N- (benzoic acid-sulfonic acid- (2) -imide) -silver salts and the like.

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

Silver S-alkyl thioglycolates in which the alkyl substituent Has 12 to 22 carbon atoms as in Japanese Patent application (OPI) No. 28 221/73 describes silver salts of 2-alkylthio-5- (carboxylate methylthio) -1.3> 4 ~ thiodiazoles, preferably those in which the alkyl group has 12 to 22 carbon atoms, or silver salts of 3- (carboxylate methylthio) -1,2,4-triazoles, silver salts of Thione compounds as in U.S. Patent 3,785,830 (where the thione compounds can be represented by the general formula

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R .C = S

Z-COOH

wherein R is the for the completion of a 5-membered heterocyclic ring, such as. B. a thiazoline, imidazoline, Pyrazoline ring and the like, required atomic group and Z is an alkylene group with 1 to 10 carbon atoms), Silver S-2-aminophenyl thiosulfate, as in U.S. Patent 3 54-9 379 described, 2-mercaptobenzoxazole silver, Mercaptoxadiazole silver, 2-mercaptobenzothiazole silver, 2- (S-ethylthioglycolamide) benzothiazole silver, 2-mercaptobenzimidazole silver, 3- ^ e ^ capto-4-phenyl-1,2,4-triazole silver, Silver salts of mercaptotriazines, silver salts of 2-mercapto-5-aminothiadiazoles, silver salts of 1-ph.enyl-.5-mercaptotetrazoles, Silver salts of dithiocarbonates, such as e.g. B. the silver salt of dithioacetate, thioamide silver, silver salts of thiopyridines, such as 5-carbethoxy-1-IIIethyl-2-phenyl-4-thiopyridinesilber, Dithiodihydroxybenzolsilber, silver diet hyl dithio car barn ate and the like.

3 «) Organic silver salts containing a carboxyl group

a) Silver salts of aliphatic carboxylic acids: Silbercapart, Silver laurate, silver myristate, silver palmitate, silver stearate, Silver behenate, silver maleate, silver fumarate, silver tartrate, Silver furoinate, silver linolate, silver oleate, silver hydroxystearate, Silver adipate, silver sebacate, silver succinate, silver acetate, silver butyrate, silver campforate, silver undecylenate, Silver lignocerate, silver arachidonate, silver erucinate, silver oxalate, Silver 10,12,14 octadecatrienoate, silver salts of aliphatic carboxylic acids containing a thioether group,

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as described, for example, in US Pat. No. 3,330,663, silver propionate, silver valerate, silver caproate, Silver caprylate, silver t-butyl hydroperoxide, silver malonate, Silver glutarate, silver pimelate, silver azelainate, Silver chloroacetate, silver trichloroacetate, silver fluoroacetate, silver iodoacetate, silver sarcosinate, silver aniline acetate, Silver almond, silver hippurate, silver naphthalene acetate, Silver creatinate, silver lactate, silver α- or β-mercaptopropionate, silver levulinate, silver salts of amino acids, such as L-alanine, γ-amino lactic acid, -aminocaproic acid,! -Aspartic acid, L-glutamic acid, L-leucine and the like, silver tricarballylate, Silver nitrilotriacetate, silver citrate, silver ethylenediamine tetraacetate, Silver acrylate, silver methacrylate, silver crotonate, Silver sorbinate, silver itaconate and the like.

b) Silver salts of aromatic carboxylic acids: silver benzoate, Silver 3,5-dihydroxybenzoate, silver o-methylbenzoate, silver m-methylbenzoate, Silver p-methylbenzoate, silver 2,4-dichlorobenzoate, Silver acetamidobenzoate, silver p-phenylbenzoate, 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, Silver m-nitrobenzoate, silver o-amine benzoate, silver furoinate, Silver p-hexoxybenzoate, silver octadecoxybenzoate, silver cinnainate, Silver p-methoxycinnamate, silver furoate, silver p-nitrophenyl acetate, Silver nicotinate, silver isonicotinate, silver picolinate, Silver pyridine-2,3-dicarbonate and the like.

4.) Silver sulfonates

Silicon ether sulfonate, silver 1-propanesulfonate, silver 1-butanesulfonate, silver 1-pentanesulfonate, silver allylsulfonate, silver benzoil sulfonate, silver 1-n-butylnaphthalene-4-sulfonate, silver naphthalene-1,5-disulfonate, silver α- or -ß-naphthalene sulfonate, silver p-toluene sulfonate, silver toluene 3 » ^/ i- disulfonate,

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Silver diphenylamine sulfonate, silver 2-naphthiiol-3i6-disulfonate, Silver anthraquinone ß-sulfonate, silver-2-amino-8-naphthol-6-sulfonate, Silver p-styrene sulfonate and the like.

5 ») silver sulfinates

Silver p-toluene sulfinate, silver p-acetoaminobenzene sulfinate, Silver benzene sulfinate and the like.

6.) Organic silver phosphates

Silver phenyl phosphate, silver p-nitrophenyl phosphate, silver ßglycerophosphate, Silver 1-naphthyl phosphate, silver adenosine 5'-3-phosphate and the like

7.) Silver salts of macromolecular compounds

Silver polyacrylate, silver polyvinyl hydrogen phthalate, silver polystyrene sulfonate and the like.

8. ) Other silver salts

The silver salt of 4-hydroxy-6-methyl-1,3 ₅ 3ai7 ~ tetrazaindene, the silver salt of 5-methyl-7-hydroxy-1,2,3,4-, 6-pentazaindene, silver salts of tetrazaindenes, as in the British Patent 1 230 642, metal-containing amino alcohols as described in British Patent 1 3 ^ 6 595, organic acid chelates of silver as described in US Patent 3 79 ^ 4-96, silver 5-nitrosalicylaldoxime, silver 5-chlorosalicylyldoxini, the silver salt of barbituric acid, silver picrate, silver rosinate, silver indophenol, the silver complex of cyclopentadiene, the silver complex of pyridine, the silver complex of cyclopentapolyene, the silver complex of N-vinylcarbazole, silver-o-sulfobenzimide and the like.

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• Λ

In addition, together with the above-mentioned silver salts, oxidizing agents such as titanium oxide, zinc oxide, gold salts of Carboxylic acids such as gold laurate, gold stearate, gold behenate and the like can be used if desired.

Among the organic silver salts mentioned above, comparatively light-resistant organic silver salts are suitable, when silver halides or photosensitive complexes of silver and dyes, as in the French patent 2 089 208, as light catalysts (photocatalysts) be used. Silver salts of aliphatic carboxylic acids having 10 to 35 carbon atoms are particularly preferred.

These organic silver salts can be produced by various methods. The simplest procedure is there in that one makes organic silver salts by mixing a solution which is an organic silver salt by dissolving one forming agent or a salt thereof in a water-miscible solvent (such as alcohol or acetone) or water has been made with an aqueous solution of a water-soluble silver salt (such as silver nitrate), as described in U.S. Patent 3,457,075. Besides that it is also possible to use a colloidal dispersion of an ammonium or alkali metal salt of an organic silver salt forming Mixing agent with an aqueous solution of a water-soluble silver salt (such as silver nitrate), as in the British U.S. Patent 1,34-7,350.

Using a similar method, it is also possible to use an aqueous Solution of a silver complex salt (such as a silver amine complex salt) or one by dissolving such a silver complex salt in a water-miscible solvent prepared solution instead of the aqueous solution of a

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water-soluble silver salt, such as silver nitrate, to use.

Another "method is described in US Pat. No. 3,558,544-4 the mixing of an oil-soluble solution that is practically insoluble in water (such as the benzene solution) with an organic Contains carboxylic acid dissolved therein with an aqueous solution of a silver complex salt to produce a silver salt an organic carboxylic acid. Preferably, the water for making an emulsion is the oil-soluble Solution added before mixing with the aqueous solution of the silver complex salt is carried out. A A similar procedure can also be applied to other organic silver salts.

In Japanese Patent Publication No. 30 270/69, a A similar process is described, which, however, results in organic silver salts which are more resistant to heat and light consists that one ei ne solution of an alkali-free silver compound, such as. B. an aqueous solution of silver nitrate instead of a silver complex salt is used. In this method, the silver salt of benzotriazole can be obtained in high yield will.

In addition, Japanese Patent Application No. 9362/73 a process for the production of organic silver salts is described. This method is preferred because it is heat developable light-sensitive material in which an organic silver salt prepared by this method is used suffers less from a veil of warmth. This is the process used to produce organic silver salts by mixing an emulsion of an aqueous solution of an alkali metal salt or an arumonium salt of a water soluble one organic silver salt forming agent and an oil (such as benzene, toluene, cyclohexane, pentane, hexane, an Carboxylic acid esters, such as. B. an acetate or phosphate,

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Castor oil and the like.) With a silver salt (silver nitrate and Like.) or a silver complex salt, preferably in the form of an aqueous solution. Alternatively, organic Silver salts are made by mixing an aqueous alkali solution with an oil-soluble solution (e.g. a toluene solution) an organic silver salt forming agent and emulsifying the same and then mixing the obtained Emulsion with a readily soluble silver salt, such as silver nitrate, or a silver complex salt, such as. B. a Silver amine complex salt, preferably in the form of an aqueous solution. As oils are used for making the above Oily solutions generally use the following: (1) Phosphates: tricresyl phosphate, tributyl phosphate, monooctyl dibutyl phosphate and the like; (2) Phthalic acid ester: diethyl phthalate, dibutyl phthalate, dimethyl phthalate, dioctyl phthalate, dimethoxyethyl phthalate and the like; (3) Carboxylic acid ester: acetic acid ester, such as amyl acetate, isopropyl acetate, isoamyl acetate, ethyl acetate, 2-ethylbutyl acetate, butyl acetate, propyl acetate and the like, sebacic acid ester, such as dibutyl sebacate, diethyl sebacate and the like., Succinic acid esters, such as diethyl succinate and the like, formic acid esters, such as ethyl formate, propyl formate, butyl formate, Amyl formate and the like, valeric acid esters such as ethyl valerate and the like, tartaric acid esters such as diethyl tartrate and the like, butyric acid esters, such as methyl butyrate, ethyl butyrate, butyl butyr; at, Isoamylbutyryte and the like, adipic acid ester and the like; (4-) oils such as castor oil, cottonseed oil, learning seed oil, tsubaki oil and the like; (5) aromatic hydrocarbons such as benzene, toluene, xylene and the like; (6) aliphatic hydrocarbons, such as pentane, hexane, heptane and the like; and (7) cyclic hydrocarbons such as cyclohexane and the like.

The silver complex salts are preferably allrail-soluble Uses silver complex salts with a dissocitation constant higher than that of organic silver salts,

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like ζ. B. a silver amine complex salt, a silver methylamine complex salt, a Silberäthylaminkomplexealζ and the like.

As a solvent for silver salts, such as silver nitrate, polar solvents such as dimethyl sulfoxide, Dimethylformamide, acetonitrile and the like can be used.

According to the information in Japanese patent application ITr. 7 619/73 it is also possible during the production of the organic silver salts apply ultrasonic waves. In particular, it facilitates the use of ultrasonic waves when emulsifying water and oil, emulsifying. It is also possible during the production of the organic silver salts to add a surface-active agent in order to regulate (adjust) the grain size of the organic silver salts. Besides that organic silver salts can be prepared in the presence of a polymer. According to a special procedure it is known, a non-aqueous solution of an organic carboxylic acid with a non-aqueous solution of a heavy metal salt, such as B. a trifluoroacetate or tetrafluoroborate to mix in the presence of a polymer for the preparation a heavy metal salt, such as. B. a silver salt, a organic carboxylic acid, as in U.S. Patent 3,700 4-58 described. Also in U.S. Patent No. 3,74814-3 is a method of making an emulsion using a similar non-aqueous solution.

As in Japanese Patent Application Nos. 4-9 4-36 / 72 and 43 867/72 as well as in the German Offenlegungsschrift 2 322 096 described, the shape and size of the granules of the organic Silver salts and their photographic properties, such as B. the heat haze, the light resistance, the sensitivity and the like., Are changed by the presence a metal salt, such as. B. a mercury or lead compound, or a metal complex during manufacture of organic silver salts. As metals have turned out to be

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Cobalt, manganese, nickel and iron proved effective alongside the mercury and lead mentioned above. These metalliferous Compounds can be used in such a way that there is a mixed solution or a dispersion of a solution of a a silver salt-forming organic compound and the metal-containing compound Combination with an aqueous solution of a readily soluble silver salt, such as silver nitrate, or a silver complex salt, such as B. a silver amine complex salt, mixed together. In addition, three components, namely a solution or dispersion of the metal-containing compound, an aqueous solution of a silver salt or a silver complex salt and a solution or dispersion of an organic compound forming a silver salt, mixed with each other will. It is also preferred to mix a solution or dispersion of a compound which forms a silver salt with a mixed solution or dispersion of the silver salt or silver complex salt and the metal-containing compound. The salary of the metal-containing compound is preferably from about 10 "to about 10 moles per mole of the organic silver salt and

-5 -2

about 10 to about 10 moles per mole of silver halide. The organic silver salt grains thus produced have a length of from about 10 to about 0.01, preferably from about 5 to about 0.1 λΐ.

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The photosensitive silver halide used as component (b) in the present invention may be silver chloride, silver bromide, silver iodide, silver chlorobromide iodide, silver chlorobromide, silver chloride iodide, silver bromide iodide, or a mixture thereof. The amount used is within the range of from about 0.001 to about 0.5, preferably from about 0.01 to about 0.3 moles per mole of the organic silver salt. The photosensitive silver halide may be coarse-grained or fine-grained, but the latter is preferred. A preferred grain size (length) of the silver halide is within the range from about 1 to about 0.001, preferably from about 0.5 to about 0.01 yes.

The photosensitive silver halide itself can be according to conventional Process as they are known in photography, for example according to a single beam process, according to a Double jet method and the like., Can be produced. It can for example a Lippmann emulsion, an ammoniacal one Emulsion, an emulsion matured with thiocyanate or thioether and the like. Can be used. According to the invention, silver halide emulsions s are used that are not washed or that with water, an alcohol or the like. To remove the soluble Salts have been washed. The light-sensitive silver halide produced in this way is treated with an oxidation-reduction composition, which contains an organic silver salt component (a) and a reducing agent as component (c), mixed, as described in U.S. Patent 3,152,904.

It is clear, however, that a "preprocessed" prepared according to the process described in US Pat. Silver halide because of insufficient contact between the silver halide and the organic silver salt often does not have sufficient photosensitivity, as indicated in US Pat. No. 3,457,075. Therefore,

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different methods to achieve sufficient contact has been developed between the silver halide and the organic silver salt. One of these procedures exists in that you have a coating solution that is used to manufacture used in a photosensitive layer, adding a surface active agent; suitable examples are in Japanese Patent Application Nos. 82 852/73 and 82 851/73. Another method is to that the prepared silver halide is mixed with the organic silver salt in a polymer; Examples are in U.S. Patents 3,705,565, 3,713,833, 3,706,564 and 3,761,273 in British Patent 1,354-186 in US Pat French patent 2 078 586 and in Belgian U.S. Patent 774-436 and the like. Another suitable one Process is described, for example, in British Patent 1,354-186 and the like, in which a silver halide emulsion mixed with an enzyme and then mixed the resulting emulsion with an organic silver salt will.

The silver halide used in the present invention can be used if desired can be produced substantially simultaneously in addition to the production of the organic silver salt, as described in US Pat German Offenlegungsschrift 2,428,125 is given. A specific example is the following: a solution of a silver salt, such as silver nitrate or a silver complex salt, is with a solution or dispersion of the above, an organic silver salt forming compound or a Salt thereof which is a photosensitive silver halide forming component (which will be described in detail below) contains, mixed or a solution of a photosensitive silver halide forming agent is mixed at the same time when wiping a solution or dispersion of an organic silver salt forming compound or a salt thereof with a solution of a silver salt such as silver nitrate and

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a silver complex salt, a photosensitive silver halide being formed simultaneously with the organic silver salt will. It is also possible to use a photosensitive silver halide forming component (which will be detailed below is described) with a previously prepared organic silver salt solution or dispersion or to implement this a sheet material containing an organic silver salt to react to form a photosensitive Silver halide in part of the organic silver salt. In US Pat. No. 5,457,075 it is stated that so produced silver halide is in effective contact with the organic silver salt and gives good results.

On the other hand, a component that can form a photosensitive silver halide is a compound which is able to form a silver halide by acting on the organic silver salt. It can go through A simple test, performed as indicated below, can determine which compounds are effective are: the silver halide forming component becomes, if desired reacted with the organic silver salt and after heating it is examined by X-ray diffraction analysis, to determine whether the diffraction maximum required for a Silver halide is characteristic, present or not. When the diffraction maximum is present, the compound can be used will. Specific examples of components that can form a photosensitive silver halide are connections specified below:

1.) Inorganic halides: halides which can be represented, for example, by the formula MX (in which M is H, NH ^ or a metal atom, X is Cl, Br or J and η is the number 1 if MH or BE is ₁ , or in then, when M is a metal atom, η means the valence of the metal, examples of the metal atom including: lithium, sodium, potassium, rubidium, cesium, copper, gold, beryllium, magnesium,

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Calcium, strontium, barium, zinc, cadmium, mercury, aluminum, gallium, indium, lanthanum, ruthenium, thallium, Germanium, tin, lead, antimony, vismuth, chromium, molybdenum, tungsten, manganese, rhenium, iron, cobalt, nickel, Rhodium, palladium, osmium, iridium, platinum and the like).

2.) Halogen-containing metal complexes: such as. B. K ₂ PtBr ₆ , HAuCl ₄ , (NH ₄ ^ IrCl ₆ , (NH ₄ ^ IrCl ₆ , (NH ₄ ) ^ (NH ₄ ) ₃ RuCl ₆ , (NH ₄ ) ₃ RbCl ₆ , (NH ₄ ^ RhBr ₆ and the like,

3) Onium halides: quaternary ammonium halides (e.g. Trimethylphenylammonium bromide, cetylethyldimethylammonium bromide, trimethylbenzylammonium bromide and the like.), Quaternary Phosphonium halides (such as tetraethylphosphonium bromide and the like), tertiary sulfonium halides (such as trimethyl sulfonium;) ο did and the like) and the like; they can do one Coating dispersion immediately before application in Be added in the form of a layer (e.g. a coating dispersion for the production of a light-sensitive layer, a protective layer, an adhesive layer (intermediate layer) or a backing layer) to lower the sensitivity and, in some cases, the background density, as in U.S. Patent 3,679,422. Can also be used to manufacture of a heat developable photosensitive and electrosensitive material as in Japanese Patent Publication (OPI) No. 84 443/74, an electrically conductive polymer with a high molecular weight of the Onium salt halide series can be used;

4.) Halogenated hydrocarbons: iodoform, bromoform, carbon tetrabromide, 2-bromo-2-methylpropane and the like;

5.) N-halogen compounds: such as e.g. B. Connections through the following general formulas can be represented:

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Λ0. Ri

x (ι)

and N-halides which contain a -SO ^ NX group (III), where for the formula III X is Cl or Br, while for the formulas I and II X is Cl, Br or J, Z which are necessary to form a 5- to 7-6li ^e third ring, which may be further condensed with another ring, required atomic group, A is a carbonyl group with R ^ and R ~ each represent a hydrogen atom, an alkyl group, an aryl group or an alkoxy group, as in the Japanese patent application No. 126 658/73 indicated. Suitable specific examples include N-chlorosuccinimide, IT-bromosuccinimide, U-bromophthalimide, N-Bromacetoamid, U-iodosuccinimide, N-Bromphthalazon, R-Bromoxazolinon, N-Chlorphthalazon, N-Bromacetoanilid, F, IT Dibrombenzolsulfonamid, bromine Ή- -N-methylbenzenesulfonamide, 1,3-dibromo-4,4-dimethylhydantoin, the potassium salt of dibromoisocyanuric acid, (trichloroisocyanuric acid and the like, as in Japanese patent applications Kr. 126 658/73, 19 760/74, 81 353/74. and the like; B-halogen compounds of unsubstituted or substituted benzotriazoles, of which the latter can be substituted, for example, by an alkyl group, preferably by an alkyl group having 1 to 5 carbon atoms, a nitro group, a halogen atom, an imide group and an amino group, as well as ^ - Halogen Compounds of Benzimidazole ^

6.) other halogen-containing compounds: triphenylmethyl chloride, Triphenylmethylbromide, 2-bromobutyric acid, 2-bromoethanol, Dichlorobenzophenone and the like.

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As stated above, according to the invention component (d) employed effectively to the thermally developable photosensitive material at any point in time be added.

However, particularly good results are obtained in the case where component (d) is used before or during manufacture component (a) is added to the organic silver salt or salts. The following methods are preferred Applied in the preparation of the organic silver salts: (1) Mixing a solution or dispersion which was prepared by adding component (d) to a solution of a silver salt-forming organic compound, with an aqueous solution of a water-soluble silver salt, such as silver nitrate, or with an aqueous solution of a silver complex salt such as a silver-amine complex salt; (2) simultaneous mixing of the three types of solutions resulting from a solution or a dispersion of the component (d), an aqueous solution of a silver salt or a silver complex salt and a solution or dispersion of a Silver salt-forming organic compound consist; (3) Mixing a solution or dispersion of a silver salt forming organic compound with a mixed solution or a dispersion, which by adding component (d) · to a solution of a silver salt or a silver complex · salt was produced.

Furthermore, there is a relatively preferred method, v / obei the component (d) after the preparation of the component (a) is added and further where the component (d) is added before or during the preparation of the component (b) will. This process includes the following processes: Preparation of a photosensitive silver halide under Use of a reactant solution to prepare the photosensitive silver halide, wherein the component

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(d) previously incorporated, according to one of the procedures corresponding to US Pat. No. 3,761,273 to German OLS 2,435,391, U.S. Patents 3,706,565 and 3,713,833 and British Patents 1,362,970 and 1,35,186, or adding component (d) to the reaction system for the preparation of the photosensitive silver halide according to those described above Procedure in the course of implementation. In the case that both the component (a) and the light-sensitive silver halide are formed almost simultaneously, as stated in the German OLS 2 428 125, component (d) in one of the reaction solutions prepared for the simultaneous production of the components described above or incorporated during the formation of the organic silver salt and silver halide. In the case of the Conversion of a certain part of the component (a), which was previously prepared, into the corresponding photosensitive Silver halide by the action of the photosensitive silver halide forming component on the For component (a), it is preferred to add component (d) to the reaction solution in the course of or before this conversion reaction. It is not always necessary in addition to add the component (d) to the reaction solution, if a trivalent or tetravalent cerium compound as photosensitive silver halide forming component is used.

In all of the processes outlined above, it is preferred to use component (d) in the form of a solution but it is also possible to add the component (d) in the form of a by dispersing it in an appropriate one Add solvent prepared dispersion. The addition temperature for the component (d) has no serious one Influence on the results of the present invention.

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It is added as a conductance at a temperature range from about 0 ° C to about 80 ° C, preferably from 10 ° C to 60 ° C.

Regardless of the mechanism of the improvements that can be achieved by adding component (d) according to the invention the following results are particularly surprising in light of current knowledge, namely improvement the green storage life, whiteness and sensitivity of the thermally developable photosensitive Material based on component (d) according to the invention.

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When using pre-prepared silver halides or when using the mixing method in which an organic silver salt with a reactance forming a silver halide is mixed, improvements in photographic properties, such as e.g. B. in relation to the increase the sensitivity and the reduction of the heat veil, can be achieved by adding the silver halide-forming agent, if desired in the presence of a Sulfur-containing compound (such as, for example, a thiösulfatε and the like), a metal (such as gold, chromium, tin, lithium, palladium and the like), a reducing agent, or a combination of these compounds, aging (storage) for a suitable period of time (for example 20 minutes to 48 Hours) at room temperature or elevated temperature (30 to 80 ° C).

Similar improvements in photographic properties can be obtained by using a precipitation process applies, which is widely used in this field for the preparation of gelatin silver halide emulsions in which the silver halide is allowed to form in the presence of a binder, the resulting silver salt is precipitated by means of a centrifugal separator and then redispersed in the remainder of the binder. If the renewed Dispersion is carried out, to improve the photographic properties advantageously nitric acid, an iron (III) cyanide, thiocyanates, thiosulfates, benzotriazole, tetrazaindenes, mercapto compounds, thione compounds, iodides, Heavy metal salts, such as B. a rhodium salt and the like., Added will.

These silver halide forming agents can be used alone or in combination. Your used The amount is within the range of from about 0.001 to about 0.5, preferably from about 0.01 to about 0.3 moles per mole

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of the organic silver salt. If the amount is below the lower limit, a small amount is often obtained Sensitivity, while when the amount is above the upper limit, the discoloration upon exposure of light often increases (an undesirable discoloration in the background areas that occurs when a developed photosensitive material is stored under room lighting).

Instead of a silver halide, if desired, other light catalysts (photocatalysts) can be used, as explained in more detail below. As a light catalyst For example, photosensitive complexes composed of silver and dyes can be used, such as in Japanese Patent Publication Mr. 25 4-98 / 74 and in Japanese Patent Applications (OPI) 4-728 / 71 and 28 221/73 described, the combined use of a highly photosensitive organic silver salt and one is also effective organic silver salt with a low sensitivity, as described in Japanese Patent Application (OPI) No. 8522/75. Metal salts of diazosulfonate can also be used and sulfonic acid salts can be used as a light catalyst. Furthermore, photoconductive materials such as zinc oxide, Titanium oxide and the like can be used. However, silver halide is that for making a highly sensitive thermally developable one photosensitive material the most suitable light catalyst.

Silver halide prepared in situ or in advance can be chemically sensitized using a chemical sensitizer s, such as B. a compound of sulfur, selenium, tellurium, gold, PJatin, palladium and the like., A reducing agent, such as B. silver, a tin halide and the like., Or a combination of these. Such methods are described, for example, in U.S. Patents 1,623,499, 2,399,083, and 3,29744-7

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described.

The photosensitive silver halide emulsions used in the present invention preferably an anti-fogging stabilizer, such as a triazolium salt, an azaindene, a mercury salt, Urazole, sulfocatechol, an oxime, nitrone, nitroindazole or the like, added to stabilize them against fogging. Such information is for example in the U.S. Patents 2,728,663, 2,839 4-05, 2,566,263, 2,597,915, British Patent 623,448, and the like.

Some optical sensitizing dyes used for gelatin-silver halide emulsions are effective also show a sensitizing effect to the heat developable photosensitive Material of the invention. Examples of effective optical sensitizing dyes are cyanines, merocyanines, complex (3- or 4-nuclear) cyanines, holopolar cyanines, Styryls, hemicyanines, oxonols, hemioxonols and the like Cyanine dyes are those that have a basic nucleus (Ring), such as B. a triazoline, oxazoline, pyrroline, pyridine, oxazole, thiazole, selenazole, imidazole core "(ring) and the like are preferred. These nuclei (rings) can be replaced by an alkyl group, an alkylene group, a hydroxyalkyl group, a sulfoalkyl group, a carboxyalkyl group, a Aminoalkyl group or an enamine group which condensed one Carbon ring or a heterocyclic ring can be substituted. Regarding their chemical structure Symmetrical and asymmetrical dyes can be used will. There can also be used those having an alkyl group, a phenyl group, an enamine group or a hetero substituent on their methine chain or polymethine chain Cyanine dyes are particularly effective at sensitizing with a carboxy group. Merocyanine dyes can in addition to the basic nuclei (rings) given above

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another acidic core (ring), such as B. a thiohydantoin, rhodanine, oxazolidinedione, thiazolidinedione, Barbituric acid, thiazolinone, malonitrile, pyrazolone core (ring) and the like. Contain. These acidic kernels (rings) can be further substituted by an alkyl group, an alkylene group, a phenyl group, a carboxyalkyl group, a suIfoalkyl group, a hydroxyalkyl group, an alkoxyalkyl group, an alkylamino group or a heterocyclic ring. Merocyanine dyes are particularly effective with an imino group or a carboxy group.

If desired, these dyes can be used in various combinations thereof. In addition, in combination with it, supersensitizing additives that do not absorb visible light, such as. Ascorbic acid derivatives, azaindenes, cadmium salts, organic sulfonic acids and the like, as described, for example, in US Pat. Nos. 2,933,390, 2,937,089 and the like, can be used. Examples of particularly effective sensitizing dyes for the heat-developable photosensitive materials according to the invention are merocyanine dyes with a rhodanine, thiohydantoin or 2-thio-2,4-oxazolidinedione core (ring), as described in US Pat. No. 3,761,279, e.g. 3-p-Carboxyphenyl-5-Zß-ethyl-2- (3-benzoxazolylidene) ethylidene-7rhodanine, 5-Z (3-ß-carboxyethyl-2- (3-thiazolinylidene) -ethylidene7-3-ethylrhodanine, 3-carboxymethyl- 5-Z (3-niethylthiazolinylidene) -a-ethylethylideo7rhodanine, 1-carboxymethyl-5-Z ^ 3-ethyl-2- (3H) benzoxazolinylidene) ethylidene7-3-phenyl-2-thiohydantoin, 5- / C3-ethyl-2 -benzoxazolylidene) -1-methylethylidene / -3- / l3-pyrrolin-1-yl) -propyl7rhoäanin, 3-ethyl-5- ^ 3-ethyl-2 (3H) -benzothiazolylidene) isopropylidene / -2-thio- 2,4-oxazolidinedione, 3-carboxymethyl-5-Zl3- ^im ethyl-2 (3H) -thiazo-iinylidene) isopropylidene7rhodanine, 3-ethyl-5-2X3-methyl-2-thiazolinylidene) ethylidene7rhodanine, 3-ethyl-5- (1-methyl-2 (iH) -pyridylidene) -rhodanine, 3-ethyl-5- (3,4-dimethyl-2 ( 3H) thiazo-

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lylidene) rhodanine, 1-carboxynietliyl-5- (3-ethyl-2-benzoxazolyni lidene) -3-phenyl-2-thiohydantoin-, 1-! thyl-Z3-ethyl-2 (3K) -benzoxazolidiene) ethylidene / - 3-n-butyl-2-thiohydantoin, 1-methyl-3-allyl-5-Z2- (3-ethylbenzoxazolidene- (2) -ethylideii7-2-thiohydantoin, 1-carboxyiaethyl-3 (K-methylbenzothiazolylindyl) -4 -thia-2-thiohydantoin, 5-ß. 3-ethyl-2 (3H) naphthoZ2, 17 oxazolylidene) ethylidene / -3-n-heptyl-2-thiohydantoin, 3-ethyl-5-ZC3-ethyl-2 (3H ) naphtho ^, 1_7oxazolyliden) äthyliden7 1-phenyl-2-thiohydantoin, 3-Ällyl-5-Z3-ethyl- (2-naphthoxazolylidene) ethylidene7 ^r -1-phenyl-2-thiohydantoin, 5 ~ Zl3 - ri-thylthiazolidine- 2-iridine) ethylidene 7-3-allyl-2-thioxazolidine-2,4-dione, 3-ethyl-5-ZC3 ~ ^a iethyl-2 (3H) benzothiazolidene) ethylidene / -2-thio-2,4-oxazolidinedione, and also merocyanine dyes of the general formulas

y CH - CH

CH ₂ CHgCOOH

C ₂ H ₅

CH-COOH

CH ₂ -CH _? -C00H

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(j? CH- CH =

CH,

C ₂ H ₂

iS

CHgCOOH

CHgCOOH

S,

fa CH,

CH

j S

CH,

CH ₂ COONH ₄

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C ₂ H ₅

= CH - CH = f N

/ CH,

COOH

- CH =] N-CH ₀ COOH

CH ₂ -CH = CH ₂ O \
^ CH J> -NH ^
- CH = C "> = S > j NH ^ N U I. U
O C ₂ H ₅

N '

r ^vx o

CH

CH ₂ COOH

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It should be noted, however, that the invention does not apply to the preferred examples given above Merocyanine dyes which can be used according to the invention are limited is.

Specific examples of cyanine dyes used in the present invention are given below. In this regard, too, it should be pointed out that the invention is by no means limited to the specific examples of dyes that can be used below:

COOH

0OH

CH ₂ CH ₂ COOH

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^ 6 3 5 5 4 1

In addition, trinuclear merocyanine dyes, like them in U.S. Patent 3,719-495 are polycyclic aromatic dyes as described in Belgian patent 788 695, sensitizing dye e mainly for silver iodide as described in Japanese Patent Publication (OPI) Kr. 17 719 / 74- are styrylquinoline dyes, as described in the Japanese Patent Publication (OPI) ITr. 84-637 / 74- are described, rhodacyanine dyes, as they are in the German Offenlegungsschrift 2,405,713 are acidic dyes (e.g. 2 ', 7'-dichlorofluorescein dye) as described in German Offenlegungsschrift 2,401,982, 2 404 591 and Japanese Patent Application Nos. 50 903/73 and 81 550/73 Merocyanine dyes as described in Japanese Patent applications Fr. 9565/74, 10 815/74 and 63 732/74 are described, and the like. Can be used. Specific examples of effective merocyanine dyes having a pyrazolone core (-Hing) are the following:

= CH - CH =

N H

'COOH

COOH

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CH-

CH ^ ^ CH ₃

i | > CH - CH

• Ν '0OH

-N

CIL

.COOH

> CH - CH =

N-

-N

CH ₂ CR

H ₃ C

■ ^

COOH

> CH - CH

CH-.

SOOH

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—4 · These dyes are used in an amount of about 10 to about 1 mole per mole of the component (b), the silver halide or the silver salt-forming component. In addition, when silver halide is not used, sensitizing dyes such as those in Japanese Patent Applications (OPI) Nos. 28 221/73 and 91 214/74 are to be used. In such a case, it is more effective to use the heat developable photosensitive To heat materials prior to imagewise exposure (up to a temperature of about 70 to about 120 ° C, preferably for a period of about 1 to about 30 seconds).

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The component (c) used according to the invention, the reducing agent, is one that the organic silver salt (the component (a)) can reduce when in the presence is heated by exposed silver halide. Among these reducing agents, the one used is selected in Depending on the type and properties of the organic silver salt used. Specific examples of usable Reducing agents are the following:

(1) Substituted phenols: aminophenols such as 2,4-diaminophenol, Methylaminophenol, p-aminophenol, D-aminophenol, 2-methoxy-4-aminophenol, 2-ß-hydroxyethyl-4-aminophenol, 4- Amino-2,6-dibromophenol, 4 — amino-2-methylphenol sulfate, 4— Amino-3-methylphenol sulfate, 4-amino-2,6-diiodophenol, 4-amino-2,6-dichlorophenol hydrochloride, N-methyl-p-aminophenol sulfate, 4-benzylideneaminophenol, 4-isopropylideneaminophenol, 2,4-diamino-6-methylphenol, 4-acylaminophenol, which is an acyl group with 2 to 18 carbon atoms contains N- (4— hydroxyphenyl) -aminoacetic acid, 4 — hydroxyphenylcarbamic acid ethyl ester, 6-dimethylamino-3-hydroxytoluene, N- (4-hydroxyphenyl) -N'-alkylurea, which contains an alkyl group with 1 to 18 carbon atoms, N- (4-hydroxy-3,5-di-t-butylphenyl) -N'-octadecylurea, N- (4-hydroxy-3,5-dichlorophenyl) -N'-octadecylurea, 3-chloro-4-hydroxydiphenylamine, 4- (4-hydroxybenzylideneamino) -2-methylphenol, 4- (4-hydroxybenzylideneamino) -3-methylphenol, 4- (3-Hydroxybenzylideneamino) phenol, α, α'-bis- (4-hydroxyphenyl amino) -p-xylene, 4-benzylideneamino-2-methylphenol, 4 ~ (2-hydroxybenzylideneamino) phenol, α, α'-bis (4-hydroxy-3-methylphenylimino) -p-xylene, 2-acylaminophenol, which is an acyl group contains 1 to 18 carbon atoms, N- (2-hydroxyphenyl) -N'-alkylurea, which contains an alkyl group with 1 to 18 carbon atoms, 6-aminophenolsulfonic acid (3) amide, 6-aminophenolsulfonic acid- (3) -dimethylamide, 2-aminophenolsulfonic acid- (4 -) - amide, 2-Benzylideneamino phenol, 4— (4— Hydroxybenzylideneamino) phenol, α, α'-bis- (2-hydroxyphenyl-

7 09825/0861

263S5A1

amino) -ρ-xylene, 3- (2-hydroxyphenylhydrazono) -2-oxo-oxolane, 3- (4-hydroxyphenylhydrazono) -2-oxo-oxolane, 4-hydroxyanilinomethanesulfonic acid, 4-hydroxy-3-methylanilinomethanesulfonic acid, and the like; alkyl-substituted phenols such as pt-butylphenol, pt-amylphenol, p-cresol, 2,6-di-t-butyl-pcresol, p-ethylphenol, p-sec-butylphenol, 2,3-dimethylphenol, 3,4-xylenol , 2,4-xylenol, 2,4-di-t-butylphenol, 2,4,5-trimethylphenol, p-nonylphenol, p-octylphenol, 2,4,6-tri-t-butylphenol, 2,6-di-t -butyl-4-octylphenol, 2,6-di-t-butyl-4-ethylphenol, 2,4,6-tri-t-amylphenol, 2,6-di-t-butylphenol, 2-isopropyl-p-cresol , 3-methyl-3- (3-ynethyl-4-hydroxyphenyl) pentane, 2,6-di-t-butyl-4-nonylphenol, 2,4-di-t-butyl-6-nonylphenol, and the like; aryl-substituted phenols such as p-phenylphenol, o-phenylphenol, oc-phenyl-o-cresol and the like; other phenols, such as p-acetophenol, p-acetoacetylphenol, 1,4-dimethoxybenzene, 2,6-dimethoxyphenol, chlorothymol, 3 ₅ 5-di-t-butyl-4-hydroxybenzyldimethylamine, 2,6-di-cyclohexyl-pcresol, 2,6-di-t-butyl-4-methoxymethylphenol, 4-methoxyphenol, 2-methyl-4-methylniercaptophenol, 2, G-dicyclopentyl-p-cresol, 2-t-butyl-δ-cyclopentyl-p-cresol, 2-t-butyl-6-cyclohexyl-pcresol, 2,5-dicyclopentyl-p-cresol, 2,5-dicyclohexyl-p-eresol, 2-cyclopentyl-4-t-butylphenol, 3,5-di-t- butyl-4-hydiOxybenzophenon, 3? 5-di-t-butyl-4-hydroxy cinnamic acid, 3i5-di-t-butyl-4-hydroxybenzaldehyde, 3 ₅ 5-di-t-butyl-4-hydroxyzim.tsäureäthylester and sulfonamide as described in U.S. Patent 3,801,321; Polyvinyl (2-hydroxy-3-methoxybenzal); Hydroxyindanes as described in German Offenlegungsschrift 2,319,080, hydroxycuniarones and hydroxycumarans as described in US Pat. No. 3,819,382, and novolak resin reaction products made from formaldehyde and phenol derivatives (such as 4- methoxyphenol , m-cresol, o- or pt-butylphenol, 2,6-di-tbutylphenol and mixtures thereof).

(2) Substituted or unsubstituted bis, tris and

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Tetrakisphenols: o-bisphenols (such as ζ. B 1,1-bis- (2-hydroxy-3,5-dimethylphenyl) -3,5,5-trimethylhexane, bis- (2-hydroxy-3-1-butyl-5 -ttiethylphenyl) methane, bis- (2-hydroxy-3,5-di-t-butylphenyl) methane, bis- (2-hydroxy-3-t-butyl-5-atb.ylpb.enyl) methane, 2.6 -Methylen-bis- (2-hydroxy-3-tbutyl-5-methylphenyl) -4-metb.ylpb.enol, 1,1-bis- (5-chloro-2-hydroxyphenyl) methane, 2 , 2'-methylene-bis- / 4-methyl-6- (i-methylcyclohexyl) pheno] L7i 1 »1-bis (2-hydroxy-3,5-dimetbylphenyl) -2-aietb.ylpropane, 1.1 , 5,5-tetrakis- (2-b.ydroxy-3,5-dimeth.ylph.enyl) -2,4, ethylpentane, 3,3 ', 5,5'-tetramethyl-6,6'-dihydroxytripb. enylmethane, 1,1-rbis- (2-hydroxy-3,5-di-t-butylphenyl) pentane, 1,1-bis- (2-hydroxy-3,5-di-t-butylpbeny.l) ethane, 1,1-bis- (2-hydroxy-3,5-di-t-butylphenyl) -propane, 1,1-bis- (2-hydroxy-3,5-di-t-butylphenyl) -butane and 1,1 -bis- (2-hydroxy-3,5-di-t-amylpb.enyl) -ätban); 1,1-bis- (2-Hydroxy-3-cyclohexyl-5-t-butylph.enyl) metal, 1,1-bis- (2-hydroxy-3-cyclopentyl-5-t-butylpnenyl) -2.2 dimethylethane, bis (2-hydroxy-3-cyclopentyl-5-methyl-6-cyclopentylphenyl) sulfide, 1,1-bis (2-hydroxy-3-cyclopentyl-5-t-butylphenyl) butane , 1,1-bis- (2-hydroxy-3-cyclopentyl-5-t-butylphenyl) methane, 1,1-bis- (2-hydroxy-3,5-di-cyclopentyl-6-meth. ylpb.enyl) methane, 1,1-bis- (2-hydroxy-3,6-di-cyclopentyl-5-nietb.ylphenyl) methane, bis- (2-hydroxy-3-cyclopentyl-5-t- butylph.enyl) sulfide, bis- (2-hydroxy-3-cyclohexyl-5-t-butylphenyl) sulfide, 1,1-bis- (2-hydroxy-3-t-butylphenyl) methane, p-cresol acetaldehyde or formaldehyde Hovolak resins, bis (2-hydroxy-3-t-butyl-5-methylphenyl) sulfide, 1,1-bis (2-hydroxy-3,5-dimethylphenyl) methane, 1,1-bis ( 2-hydroxy-3,5-di-t-butylphenyl) -2-methylpropane, 1,2-bis- (2-hydroxy-3-t-butyldibenzofuryl) ethane and 3,3 ', 5,' - tetra-t -butyl-6,6'-dihydroxytriphenylmethane); p-bisphenols (such as ζ. Β. bisphenol A, 4,4'- ^l -I1ethylene-bis- (3-niethyl-5-t-butylphenol), 4,4'-methylene-bis- (2,6-di- t-butylphenol), 3,3 ', 5,5'-tetra-t-butyl-4,4'-dihydroxybiphenyl, 4,4'-dihydroxybiphenyl, 1,1-bis (4-hydroxyphenyl) cyclohexane, 2 , 2-bis- (3,5-dibromo-4-hydroxyphenyl) -propane, 2,2-bis- (3,5-dichloro-4-hydroxyphenyl) -propane, 2,2-bis- (3,5- £ imethyl-4-hydroxy-

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phenyl) propane, 2,2-bis- (3-methyl-4-hydroxyphenyl) propane, bis- (3-methyl-4-hydroxy-5-t-butylphenyl) sulfide, 2,2-bis- (4- Hydroxy-3,5-di-t-butylphenylthio) propane, 4,4'-butylidene-bis- (6-t-butyl-3-methylphenol), 4,4 '-' thio-bis- (6-t -butyl-3-methylphenol), 4,4'-thio-bis- (6-t-butyl-2-methylphenol), 4,4'-butylidene-bis (6-methylphenol), 4,4'-benzylidene -bis- (2-t-butylphenol), 4,4'-ethylidene-bis- (6-t-butyl-o-cresol), 4,4'-ethylidene-bis- (2-t-amylphenol), 4 , 4 -'- (p-chlorobenzylidene) -di (2,6-xylenol), 4,4'-ethylidene-bis- (2-cyclohexylphenol), 4,4'-pentylidene-di (o-cresol) , 4,4 '- (p-Brotabenzylidene) -di-phenol, 4,4'-Propylidene-bis- (2-phenylphenol), 4,4'-Ethylidene-di- (2,6-xylenol), 4, 4'-heptylidene-di- (o-cresol), 4,4'-ethylidene-bis- (2,6-di-t-butylphenol), 4,4 '- (2-butenylidene) -di (2, 6-xylenol), 4,4 '- (p-methylbenzylidene) -di (ocresol), 2,2-bis- (3-methyl-4-hydroxy-5-t-butylphenyl) propane, α, α'- (4-Hydroxy-3,5-di-t-butylphenyl) dimethyl ether, 4,4'-dihydroxy-3? 3 ' t ^ -, ' -tetra-t-butylbiphenyl-, 4,4'-dihydrox3i - 3,3'-dimethylbiphenyl, 2,2-bis- (3-methyl-4-hydroxy-5-t-butylphenyl ) -propane, 2,2-bis- (4-hydroxy-3,5-di-t-butylphenyl) propane, 2,2-bis- (4-hydroxy-3,5-diethylphenyl) propane, 2,2- bis- (4-hydroxy-3-niethyl-5-t-aniylphenyl) propane, 2,2-bis- (4-hydroxy-3 ₅ 5-di-t-amylphenyl) propane); Polyphenols, such as ζ. Β. 2,4,6-tris- (3,5-di-t-butyl-4-hydroxybenzyl) phenol, N, II'-di- (4-hydroxyphenyl) urea, tetrakis-methylene- (3 ■> 5-di-t-butyl-4-hydroxy-hydrocinnamate Q.7-diethane and the like, diethylstilbestrol, hexostrol, bis- (3i5-di-t-butyl-4-hydroxybenzyl) ether, 2,6-bis- (2'-hydroxy-3 '-t-butyl-5'-methylbenzyl) -4-methylphenol and the like;

(3) substituted or unsubstituted mono- or bisnaphthols and D: '.- or polyhydroxynaphthalenes: bis-ß-naphthols (e.g. 2,2 * -dihydroxy-1, Λ ' -binaphthyl, 6,6'-dibromo- 2,2'-dihydroxy-1,1'-binaphthyl, 6,6'-dinitro-2,2'-dihydroxy-1,1'-dinaphthyl, bis (2-hydroxy-1-naphthyl) tethane, 4, 4'-dimethoxy-1,1'-dihydroxy-2,2'-binaphthyl and the like),

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-fs-

Naphthols (v / ie e.g. a-naphthol, ß-naphthol, 1 ~ hydroxy-4 ~ aminonaphthalene, 1,5-dihydroxynaphthalene, 1,3-dihydroxynaphthalene, i-Hydroxy ^ -phenyl - ^ - niethoxynaphthalin, 1-Hydroxy-2 ~ methyl-4-methoxynaphthalene, 1-hydroxy-4-methoxynaphthalene, 1,4-dihydroxynaphthalene, methylhydroxynaphthalene, 1-amino-2-naphthol-6-sodium sulfonate, i-kaphthylamine-7-sulfonic acid and the like), 2,3-dihydroxynaphthalene, 1-hydroxy-2-carboxynaphthalene, i-hydroxy-4-methoxydihydronaphthalene, 2-hydroxy-3-carboxynaphthalene, 1-hydroxy-4-ethoxynaphthalene, i-hydroxy-4-propoxynaphthalene, i-hydroxy-4-isopropoxynaphthalene, i-Hydroxy-5-methoxynaphthalene, morpholino- (1-hydroxy-4-methoxynaphthyl- (2) ) methane, sulfonateid naphthols, as described in U.S. Patent 3,801,321 are, 2-hydroxy-3-aminonaphthalene and 1-hydroxy-5-acylaminonaphthalene, containing an acyl group having 1 to 18 carbon atoms and the like;

(4) Di- or polyhydroxybenzenes and hydroxymonoethers: Hydroquinone, alkyl-substituted hydroquinones (preferably those with an alkyl group with 1 to 5 carbon atoms, such as methyl hydroquinone, t-butyl hydroquinone, 2,5-biniethyl hydroquinone, 2,6-dimethyl hydroquinone, t-octyl hydroquinone and the like), halogen-substituted hydroquinones (such as, for example, chlorohydroquinone, dichlorohydroquinone, bromohydroquinone and the like), alkoxy-substituted hydroquinones (preferably those with an alkoxy group having 1 to 3 carbon atoms, such as methoxyhydroquinone, ethoxyhydroquinone and the like), other substituted hydroquinones (such as, for example, hydroquinones) Phenylhydroquinone and the like), hydroquinone monosulfate, 2,5-dihydroxyalkylhydroquinone (in which alkyl radicals with 1 to 18 carbon atoms are preferred), 2-ethoxycarbonylhydroquinone, acetylhydroquinone, 2-cyclohexylhydroquinone, (2,5-dihydroxyphenyl) -5- (i-phenyltetrazolyl-tetrazolyl) ) sulfide, (6-methyl-2,5-dihydroxyphenyl) -5- (phenyltetrazolyl) sulfide, (2,5-dihydroxyphenyl) -2 - (benzothiazolyl) sulfide, 2-dodecyl-5- (6-carboxy-

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ρ entyl hydroquinone, 2-dodecyl-5- (9-carboxynonylhydroquinone, 2-tetradecyl-5- (5-carboxypentyl hydroquinone, 2-tetradecyl-5- (9-carboxynonylhydroquinone and the like); hydroquinone monoethers (such as p-methoxyphenyl - Or p-ethoxyphenol-hydroquinone monobenzyl ether, 2-t-butyl-4-πlethoxypllenol- or 2,5-di-t-butyl-4-methoxyphenol-hydroquinone-mono-n-propyl ether, -hydroquinone-mono-n-hexyl ether; and others, such as pyrocatechol, 4-phenylpyrocatechol, 3- (dihexylaminomethyl) -5-phen; catechol, 3- (di-n-hexylaminomethyl) -5-phenylpyrocatechol, 3-cyclohexylpyrobrenzcatechol, 4-4- cyclohexylpyrocatechol, (a-Iiethylbenzyl) pyrobrenzcatechin, Dicyclohexylpyrobrenzcatechin, 5- (N, I7-Dihexylaminometh3rl) -4-phenylbrenzcatechin, 4-Lauroylbrenzcatechin, t-butyl catechol, pyrogallol, Azeloylpyrogallol, Behenoylpyrogallol, 4-Stearoylpyrogallol, di-t-butylpyrogallol, Butyrylpyrogallol, 4 -Azeloylbipyrogallol, phloroglucinol, resorcinol, 4,6-di-t-butylresorcinol, 4-alkylresorcinol, which has an alkyl group mi t contains 1 to 18 carbon atoms, ^/ 1-chloro-2,4-dihydroxybenzene, 3 »5-di-t-butyl-2,6-dihydroxybenzoic acid, 2,4-dihydroxybenzoic acid, 2,4-dihydroxyphenyl sulfide, 2,3 -Dihydroxybenzoesäure, 3 »^ dihydroxybenzoic acid, 2,5-dihydroxybenzoic acid, o-aminobenzoic acid, m-aminobenzoic acid, p-aminobenzoic acid, protocatechualdehyde Äthylprotocatechuat, Cetylprotocatechuat, 4- (3 *» 4'-dihydroxyphenylazo) benzoic acid, 3 ^{'ζ ί-} Dihydroxyphene ^^ lessetic acid, 1-acetyl-2,3,4-trihydroxybenzene, 2,2'-methylenebis (3,4,5-trihydroxyphenyl) benzoic acid, gallic acid, ilethyl gallate, propyl gallate, butyl gallate, itodium gallate, ammonium gallate, dodecyl gallate, Ethyl gallate, isopropyl gallate, gallic acid anilide, 3i ^/ * - »5-trihydroxyacetophenone and the like;

(5) ascorbic acid and derivatives thereof: a-ascorbic acid, isoascorbic acid, Ascorbic acid monoesters (such as ilonolaurate, monomyristate, monopalmitate, monostearate, monobehenate, Monobenzoate, 6-palmitate-5-β-carboxypropionate and the like of ascorbic acid), diesters of ascorbic acid (such as

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the dilaurate, dimyristate, dipalmitate, distearate and the like of ascorbic acid). The ascorbic acids described in US Pat. No. 3,337 3 ^ -2 can also be used will.

(6) 3-pyra-zolidones, pyrazolines and pyrazolones: 1-phenyl-3-pyrazolidone, A-methyl - ^ - hydroxymethyl-i-phenyl ^ -pyrazolidone, those described in British Patent 930,572, 1- (2-quinolyl) -3-methyl-5-pyrazolone and the same;

(7) reducing sugars: glucose, lactose and the like;

(8) Phenylenediamines: e.g. B. o-phenylenediamine, p-phenylenediamine, IN, N'-dimethyl-p-phenylenediamine, N, N'-diethyl-p-phenylenediamine, N-phenyl-N'-isopropyl-p-phenylenediamine, ΪΤ, Ν ¹ -dibenzylidene- p-phenylenediamine, Ν, Ν-diethyl-N'-sulfomethyl-pphenylenediamine, li-benzylidene-N ', N'-diethyl-p-phenylenediamine, Ν, Ν-dimethyl-IT'-sulfomethyl-p-phenylenediamine, 3- Methoxy-4-sulfomethylamino-N, N-diethylaniline, Ν, Ν'-disulfomethyl-pphenylenediamine, N- (2-hydroxybenzylidene) -N ', N'-diethyl-pphenylenediamine, N- (3-hydroxybenzylidene) -N', N'-diethyl-pphenylenediamine, IT- (4-hydroxybenzylidene) -N ', N'-diethyl-pphenylenediamine, IT, N-diethyl-3-πlethyl-p-phenylenediamine, ΪΤ, Ν-diethyl-p-phenyleneaaintrifluoroacetate, hydroxyethylparamine and the like which can provide color images when used in conjunction with phenolic or active methylene color couplers as disclosed in U.S. Patents 3,531,286 and 3,764-328, and also disclosed in U.S. Patent 3,761,270 described methods can produce color images;

(9) Hydroxyamines: e.g. B. Hydroxyamines, as in Tier US patent 3,667,958 and Japanese Patent Application (OPI) No. 28 221/73 and the like;

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(10) Reductone: ζ. B. Aminohexosereductone, Anhydroaminohexosereductone and anhydrodihydroaminohexose reductones as described in U.S. Patent 3,679 4-26 Aminoreductones as in Belgian patent 786 086 described, and the like;

(11) hydroxamic acids: e.g. B. hydroxamic acids, as in US patents 3 751 252 and 3 751 255, and like;

(12) hydrazides: e.g. B. hydroxy-substituted fatty acid arylhydrazides, as described in U.S. Patent 3,782,949 and the like;

(13) Others: e.g. B. indane-1,3-dione, each of which at least Contains 1 hydrogen atom in the 2-position, such as in U.S. Patent 3,773,512 substituted amidoximes as described in U.S. Patent 3,794-488 Hydropyridines, as in the German Offenlegungsschrift 2 3Ο8 766 described, organic hydrazone compounds, such as described in US Pat. No. 3,615,533, hydrazines as described in US Pat. No. 3,667,958, amino-9,10-dihydrοacridine, 1,4-dihydropyridines as in the US patent 3 839 048 described, acetoacetonitrile, homogentisic acid and homogentisoamides, hydroxytetronic acids and Hydroxytetronimide, kojic acid, hinikitiol, p-oxyphenylglycine, 4,4'-diaminodiphenyl, 4,4'-dimethylaminodiphenyl, 4,4 ', 4 "-diethylaminotriphenylmethane, Spiroindane and 4-methylesculetin,

Among the above-mentioned reducing agents, phenols having an alkyl group, e.g. B. a methyl, ethyl, propyl, isopropyl or butyl group, or have an acyl group in at least one position adjacent to the position with is a hydroxyl substituent in an aromatic nucleus, such as B. those containing a 2,6-di-t-butylphenol group

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Mono-, bis-, tris- or tetrakisphenols, the property that their color changes only slightly when exposed to light because they are resistant to light. The combined Use of these phenolic reducing agents and of silver salts of fatty acids is particularly advantageous Effect from, for example, in the German Offenlegungsschrift 2,321,328 and in Japanese Patent Application Nos. 81 625/73, 22 135 / 74-, 55 114/74 »89 603/74, 105 290/74 and 126 366/74 is described.

In addition, as in the TJS patent 3 827 889 stated, reducing agents that can be deactivated by exposure, such as photolytic reducing agents, good for the use according to the invention because a reducing agent of this type is deactivated or decomposed by light when a photographic material containing such a reducing agent becomes lighter after development at Room lighting is preserved, causing an interruption of the reduction and therefore to an interruption of the Color change leads. Specific examples of photolytic reducing agents are ascorbic acid and derivatives thereof, Furoin, benzoin, dihydroxyacetone, glyceraldehyde, rhodisone tetrahydroxyquinone, 4-methoxy-1-naphthol and the like. As indicated in U.S. Patents 3,827,889 and 3,756,829, For example, a direct positive image can be produced by using such a photolytic reducing agent the preparation of heat developable photosensitive materials and imagewise exposure of them to the reducing agent to decompose. You can also, if desired in addition, compounds which can accelerate the photolysis of the reducing agent can be used. the most preferred reducing agents are 2,4-dialkyl substituted o-bisphenols, 2,6-dialkyl-substituted p-bisphenols and mixtures thereof. Particularly preferred reducing agents according to the invention are those indicated below

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general formulas

HO—

12 5 6

wherein R, R, R and R each represent an alkyl group having 1 to 5 Carbon atoms, a cyclopentyl group or a cyclo-

T 1\ '"7 f5

hexyl group and R- ⁵ , R, R 'and R each represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an aryl group (e.g., a phenyl group, an ITaphthyl group and the like), a substituted aryl group (e.g., a carboxyphenyl group , a halogen-substituted phenyl group, an alkoxy-substituted phenyl group, a nitro-substituted phenyl group and the like, as described in German Offenlegungsschrift 2,321,328) or an aralkyl group (e.g. a benzyl group, a β-phenylethyl group and the like).

The appropriate reducing agents are selected depending on the kind (s) of the (s) used organic silver salt (silver salts) '' component (a)). So For example, a stronger reducing agent is suitable for silver salts, which are comparatively difficult to reduce are, such as B. the silver salt of benzotriazole, silver

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belienat and the like, while weaker reducing agents are suitable for silver salts which are comparatively easy to reduce, such as silver caprate, silver laurate and the like. Examples of reducing agents for the silver salt of benzotriazole are i-phenyl-3-pyrazolidone, ascorbic acid, Ascorbic acid monocarboxylic acid ester, naphthols (e.g. 4-methoxy-1-naphthol and the like) and the like - examples of reducing agents for silver behenate are many compounds, such as B. o-bisphenols of the bis (hydroxyphenyl) methane series, Hydroquinone and the like. Examples of reducing agents for silver caprate and silver laurate are substituted Tetrakisphenols, o-bisphenols of the bis (hydroxyphenyl) alkane series, p-bisphenols (e.g. a bisphenol Α derivative), p-phenylphenols, and the same. Suitable reducing agent / organic silver salt combinations can after a simple Test can easily be determined. For this purpose, for example, a sample of the reducing agent with a das organic silver salt-containing coating solution is mixed and the mixed coating solution is molded into a layer applied to the carrier. The heat developable photosensitive sample thus obtained is then exposed to light and heated; the test at this stage allows the person skilled in the art to determine the optimal combinations.

The amount of reducing agent used in the present invention varies depending on the kind of organic silver salt or reducing agent and other additives, however, generally a suitable amount is within the range of about 0.05 to about 10, preferably from about 0.1 to about 3 moles per mole of the organic silver salt.

The various reducing agents described above can be in the form of combinations of two or more of them Connections are used. Specific examples of the

709825/0861

263SS41

Use of two reducing agents in combination with each other is disclosed in Japanese Patent Application No. 27,242/73 and in U.S. Patents 3,667,958 and 3,751,249. A particularly effective combination of reducing agents is e.g. B. the combination of at least one carboxylic acid ester, which is derived from a phenol with a bulky o-substituent or an o- or p-bisphenol, wherein the carboxylic acid ester of the above ester between a carboxylic acid, that of a phenol with a bulky o-substituents is derived, and a mono- or polyhydroxy alcohol or a phenol or the ester between one of a polyhydroxyphenol with a bulky o-substituent or from a phenol with a bulky o-substituent derived alcohol and a mono- or polycarboxylic acid is. With this combination it is possible to reduce the heat haze and increase the degree of whiteness and to achieve stabilization against light after development. In addition, the combined use of two mono- or polyphenol reducing agents with alkyl groups in the two substitution positions that of the hydroxy-substituted Position of the aromatic nucleus are adjacent, preventing discoloration upon exposure to Light. It has also been shown that the development through the combined use of a compound of tin, Iron, cobalt or nickel such as a metal salt of a long chain fatty acid such as iron stearate, lead behenate and the like (such compounds represent auxiliary reducing agents dar), and the reducing agent can be accelerated. The amounts of these auxiliary reducing agents vary widely in Dependence on the reducing power of the main reducing agent and the auxiliary reducing agent and the reducibility the oxidizing agent (the organic silicon salt), however, they are generally used in an amount of 10 to

mm ^

about 1, preferably from 10 to 0.8 moles per mole of the main reducing agent used.

70982 5/0861

A coloring agent can be used together with these reducing agents. The coloring agent is preferably used to produce images in a dark shade, especially a black shade. That Tinting agent is most effective when it is in a concentration ranging from about 0.0001 moles to about 2 moles, preferably about 0.0005 mole to about 1 mole per mole of the organic silver salt is used. The choice of the effective tinting agent depends on the organic silver salt and the reducing agent used. The on Most commonly used coloring agents include heterocyclic ones organic compounds that form a unit-C-N-

M I

0 R

where R is a hydrogen atom, a hydroxyl group, metal ions such as Na ⁺ , Li ⁺ , Ag ⁺ or K ⁺ , acyl groups having 2 to 10 carbon atoms such as an acetyl group, propionyl group and the like, for example phthalazinones, oxazinediones, cyclic imides , Quinazolinones, N-hydroxyphthalimides, urazoles, 2-pyrazolin-5-ones and the like. Specific examples of coloring agents of this kind are phthalazinone, 2-acetylphthalazinone, 2-phthalylphthalazinone, N-methylphthalazinone, 2-pivaloylphthalazinone, 2-carbamoylphthalazinone, 2-carbamoylphthalazinone, 2-carbamoylphthalazinone - (3,4-Dimethoxybenzoyl) phthalazinone, 2-lauroylphthalazinone, 2-benzoylphthalazinone, 2- (p-methoxybenzoyl) phthalazinone, 2-ethoxyformylphthalazinone, phthalazinone derivatives according to Japanese patent application 116022/73 and US Patent Specification 3,844,797, phthalazinone salts, such as phthalazinone silver, quinazolinediones and benzoxazinediones or naphthooxazinediones corresponding to Japanese patent applications 91215/74 and 25-4 / 75 »cyclic imides, such as subst ituted phthalimides according to German OLS 2,140,406 and 2,141,063, quinazolines according to US Pat. No. 3,846,136, pyrazolin-5-ones, N-hydroxy

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naphthalimides according to US Pat. No. 3 782 94-1, mercapto compounds according to US Pat. No. 3,832,186 and Japanese Patent Application 5020 / 74-, phthalazinediones according to Japanese Patent Application 1164-71 / 731, uracile according to Japanese Patent Application 18378 / 74-, Barbitale, saccharin, 5-nitrosaccharin, phthalic anhydride, 2-iIercaptobenzoxazol, 2-hydroxybenzothiazole, 2-amino-6-methylbenzothiazole, 2-amino-4 ~ (4-biphenr / lyl) thiazole, imidazole, 2-hydroxybenzimidazole, N ₅ K'-ethylene thiourea and 1-acetyl-2-thiohydantoin.

The combined use of an imidazole and phthalic acid or naphthoic acid or phthalamic acid can also be used Give images with a black tone as disclosed in U.S. Patent No. 3,84-7,612. Another preferred example consists in the combined use of phthalazinone and 2-acylphthalazinone. Simultaneous use of Two or more kinds of the above-listed coloring agents can produce various favorable photographic results provide. The coloring agents can be in the support, in a backing layer, in one present on the support Primer layer or can be incorporated into the subsequently applied layer. Good results can be achieved in all cases can be obtained.

Various methods can be used to further prevent the formation of thermal fog in the thermal developable photosensitive materials according to the invention can be used. For this purpose, N-halogen compounds, such as N-halosuccinimides, N-haloacetamides, N-halogenoxazolinones, N-halogenobenzotriazoles, N-halogenobenzimid'isoles, Ν, Ν'-dichloro-I, 2-ethylene bisbenzsmide and the like, such as in Japanese Patent Applications 10724- / 74-, 97S13 / 74 · and 90113/74 and 94- 84-7 / 74- are given. In another method for

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A wide variety of acidic compounds and salts thereof can be used for the prevention of thermal fog, as disclosed in Japanese Patent Applications 125016/7 ⁷ J-, 130720/74 and 89720/73, U.S. Patent 3,645,739, and Japanese Patent Applications 106724/73 , 121631/74, 29463/74, 13I827 / 74, 128767/74, 187/75 and 299/75. Specific examples of such acids include lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, succinic acid, maleic acid, tetrahalophthalic acid or anhydrides thereof, arylsulfonic acids such as benzenesulfonic acid and p-toluenesulfonic acid, arylsulfinic acids such as benzenesulfinic acid and p-urosulfinic acids with one of these Oxidation value greater than 120, for example gum resin, wood resin, hydrogenated rosin, and the like, salicylic acid, alkyl-substituted benzoic acids such as p-hydroxybenzoic acid, 2,6-dihydroxybenzoic acid, tetrabromobenzoic acid, p-acetamidobenzoic acid, p-tert-butylbenzoic acid and the like, Isophthalic acid, trimellitic acid, pyromellitic acid, diphenic acid, 5 ¹ > 5 ^f -ethylene bis-salicylic acid, capric acid, arachidic acid, lignoceric acid, cerotic acid, linoleic acid, linoleic acid, adipic acid, sebacic acid, dimethylstearic acid, dimethyl behenic acid, phinnamic acid, z-. B. abietic acid, pimaric acid, iso-d-pimaric acid, neoabietic acid, levoabietic acid and the like., Alkali salts or esters of benzenethiosulphonic acids and combinations thereof. Examples of suitable combinations include a combination of a sulfinic acid and a polyhalophthalic acid, the combination of a sulfinic acid and a natural resin, the combination of a sulfinic acid and a diterpenic acid and the combination of a thiosulfonic acid and an imidazole.

Lithium salts of higher fatty acids, such as lithium myristate, Lithium stearate, lithium behenate, lithium palmitate, lithium

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Laurate and the like can be used as thermal fog stabilizers. As further examples of compounds that can effectively prevent the occurrence of thermal haze, include benzotriazole and derivatives thereof, phenylmercaptotetrazoles, Thiouracils according to Japanese patent application 72992/74, for example 2-thiouracils according to the following formula

wherein R is a hydrogen atom, a hydroxyl group, a Alkoxy group, a halogen atom, a lower unsubstituted or substituted alkyl group, a benzyl group, an aryl group, an amino group, a nitro group or a nitroso

2
group and R denotes a hydrogen atom, a hydroxyl group, a halogen atom, an amino group, an acetamide group, an unsubstituted or substituted alkyl group with 1 to 22 carbon atoms, a phenyl group or a substituted aryl group, peroxides and persulfates according to Japanese patent application 54-53 / 74- 1 Disulfides according to Japanese patent application 115781/74, palladium-containing compounds according to Japanese patent application 125037/74, such as a palladium-acetylacetone complex salt and the like.

Particularly preferred antifoggants used together with component (d) according to the invention are Thiosulfonic acid. Diterpenic acids, long chain aliphatic ^ Carboxylic acids, benzotriazoles and sulfinic acids.

It is preferred to use a compound capable of preventing color change by light in the treated light

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sensitive material to the thermally developable photosensitive Adding materials, the term "color change due to light" denoting the appearance that unexposed areas of the treated photosensitive material gradually color themselves when they are in a light color Space to be left. Specific examples of effective compounds for this purpose include precursors of stabilizing agents Agents such as azole thioethers and blocked azole thiones, as disclosed in U.S. Patent 3,839,041, are tetrazolylthio compounds according to US Pat. No. 3,700-4,557 and light-sensitive shark-containing organic Oxidizing agent according to US Pat. No. 3,707,377 · Further, sulfur is useful for preventing color change favorable by light.

It is possible to further stabilize the treated photosensitive material against light and heat. Examples of methods effective for such stabilization are stabilization of the sensitive one being treated Materials by applying a solution containing a mercapto compound according to the US patent 3,617,289, forming a layer that one Stabilizer contains on or in the light-sensitive material according to Japanese Patent Application 102337/73 * stabilization with aldehyde compounds, stabilization or fixation using a thiocyanate, thiosulfate or of triphenylphosphine and the treatment of the treated photosensitive material with benzotriazoles Phenylmercaptotetrazole, trichloromelamine, or potassium iodide a solvent such as trichlene, ethanol, acetone, isopropanol or the like. Mentioned.

The addition of acids or certain N-halogen compounds to the thermally developable photosensitive materials allows the photosensitive material

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to stabilize to light before the application of heat and to preheat before imagewise exposure can be used to make them photosensitive, as in U.S. Patents 3,764,329, 3,802,888S, and 3,816 and Japanese Patent Applications 89720/73, 10039/74 and 91214 / 74- indicated. Furthermore, sensitivity and Contrast can be changed by heating before imagewise exposure, such as in Japanese Patent application 43630/73 executed.

The thermally developable photosensitive materials according to the invention can be antistatic Layer or a conductive layer if desired. Halides, water-soluble salts such as nitrates, ionic Polymers according to U.S. Patents 2,861 and 3,206,312 or insoluble inorganic salts according to US Pat. No. 3,428,451 can additionally be incorporated into these layers. Furthermore, a thin metal layer produced by vapor deposition can also be present.

In the thermally developable photosensitive material used in practicing the invention can be antihalatxon substances or antihalation dyes can be incorporated if desired. Through warmth decolorizable dyes are preferably used as antihalation agents. Examples of such dyes are in U.S. Patents 3,769,019 and 3,745,009 and Japanese Patent Publication 43321/74 and are preferably used in the context of the invention. Further, the thermally developable photosensitive materials like the invention may include filter dyes and light absorbing agents Contain substances such as in U.S. Patents 3,253,921, 2,527,583, 2,956,879 and 2,274,782. The thermally developable light

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.41.

sensitive materials according to the invention can if desired Matting agents, such as calcium carbonate, Starch, titanium dioxide, zinc oxide, silica, dextrin, barium sulfate, aluminum oxide, kaolin, clay, diatomaceous earth and the like. contain.

Fluorescent, knowledge-increasing agents such as stilbenes, triazone, oxazoles, coumarin and the like., Accordingly for example the German patents 972 067 and

1 150 274, French patent specification 1 530 244 and U.S. Patents 2,933,390 and 3,406,070 can also be used in accordance with the invention. These Fluorescent whitening agents are used as aqueous solutions or dispersions.

The thermally developable photosensitive materials according to the invention can furthermore be plasticizers and lubricants. Examples of preferred plasticizers or lubricants are glycerin, Diols, polyhydric alcohols, for example corresponding to d U.S. Pat. No. 2,960,404, fatty acids and esters thereof corresponding to, for example, U.S. Patents

2,588,765 and 3,121,060 and silicone resins, for example, correspondingly British Patent 955 061 mentioned. Also surfactants such as saponin and Alkylarylsulfonates according to, for example, the US patent 2,600,831, anphoteric compounds accordingly for example U.S. Patent 3,133,816 and glycidol-alkylphenol adducts and surfactants the alkoxyphenol series corresponding, for example, to British patent 1 022 878 can be converted into the thermally developable light-sensitive materials according to the invention are incorporated.

Certain layers of the thermally developable photosensitive Elements, such as a photosensitive

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Layer that has received a hardening treatment can cured using various organic and inorganic hardeners in the practice of the invention will. The hardeners can be used either individually or in combination. Preferred examples for Hardeners include aldehydes, blocked aldehydes, ketones, carboxylic acids and carbonate derivatives, sulfonate esters, sulfonyl halides, Vinyl sulfonyl ester, active halogen compounds, epoxy compounds, Aziridines, active olefins, isocyanates, carbodiimides, polymeric hardeners such as dialdehyde starches, and the like.

Various additives can also be added to increase the image density. For example, connections are the groups -CO-, -SO- or -SOp- contain, as for example in U.S. Patent 3,667,959; and non-aqueous organic polar solvents such as Tetrahydrothiophene-iii-dioxide, 4-hydroxybutanone lactone and Methylsulfinylmethane suitable for this purpose. Except for this For example, the acetates of zinc, cadmium and copper, as described in US Pat. No. 3,708,504, are effective.

Furthermore, compounds which change to alkaline compounds when heated are like those containing water of crystallization Compounds according to U.S. Patents 3,635,719 and 3,531,285, guanidinium salts, acid salts of amines and Metal oxides or hydroxides are effective to accelerate the development. For the purpose of increasing the development speed Moisture releasing agents can be added if desired. Moisture releasing Agents not only include the above-described compounds that contain water of crystallization and metal hydroxides, but also ureas, caprolactam, p-ü-nitroethanol, ß-cyanoethanol, Glycol, polyethylene glycol, glycerine, sorbitol and mono- or oligosaccharides.

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.64.

In addition to the additives described above, the combination of a polyalkylene glycol and a mercaptotetrazole can also be used can be used to improve sensitivity, contrast and image density. Furthermore, leuco dye compounds, as stated in Japanese Patent Application 110287/73, to further improve the green storage life can be used.

It is also possible to change the white color by blueing due to the addition of blue dyes, such as Victoria blue, to increase, so that there is an improvement in the residual color formed by the dyes.

In the thermally developable photosensitive materials according to the invention, a primer layer can be used between the support and the heat developable ones drawn on the support be formed light-sensitive layers.

Polymeric acids, which have a behenic acid unit, a palmitic acid unit, a lauric acid unit, a rosin unit, a diterpenic acid unit, a polyacrylic acid unit, a maleic acid unit or an acrylic acid unit contain, benzotriazoles, mercaptoazoles, metal salts of Fatty acids such as lithium laurate, lithium behenate and the like, can be used in the primer layer to improve photographic properties such as color change by light and thermal Veil to be incorporated. Furthermore, it is possible to prevent the emulsion from penetrating into the carrier and increase the resolution by adding matting agents such as clay, kaolin, starch, barium sulfate, aluminum oxide, silica, Titanium dioxide, zinc oxide and the like, incorporated in the primer layer will. A conductive metal layer formed by an electrolytic process can also be used as a primer layer be used.

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Furthermore, a polymer layer is preferably formed on the back of a paper support in order to improve moisture resistance to increase, to protect the wearer from puckering, to facilitate the markings and to facilitate transport of coloring agents or subliming compounds from the emulsion layers or the like. To prevent. The polymers usable for the backing layer include Gelatin, polyvinyl alcohol, polyvinyl pyrrolidone, cellulose acetate butyrate, Acrylate copolymers, polyamide resins ,. Coumarone indene resins, cellulose diacetate, ethyl cellulose, the above for the primer layer and described polymers the binders listed below for the emulsions. This backside polymer layer can additionally do the above Contain the described coloring agents and reducing agents, dyes and other additives. Furthermore you can thermally developable light-sensitive materials that a back layer containing a heat transportable Own dye, can be used as a thermal transfer material. For such thermal transfer Materials are described in U.S. Patent 3 76? 394 and Japanese patent application 103639 / 74-.

A final polymeric coating can be used if desired can be formed on the photosensitive layer to reduce the transparency of the thermally developable photosensitive Increase layer, increase image density, and improve green storage life, as in the 3 tables Patent applications 6917/74 and 128726/74 97050/73, Belgian patent 798 367 and US patents 3 856 526 and 3 d56 527 is given. A final polymer layer, which is applied in a thickness in the range of about 1 micron to about 20 microns is for the

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26355A1

Best to use. Suitable polymers for the polymer layer include polyvinyl chloride, polyvinyl acetate, "vinyl chloride-vinyl acetate copolymers, Polystyrene, polymethyl methacrylate, methyl cellulose, ethyl cellulose, cellulose acetate butyrate, Cellulose acetate, polyvinylidene chloride, cellulose propionate, cellulose acetate phthalate, polycarbonate, ceilulose acetate propionate, Polyvinylpyrrolidone, polyvinyltoluene, nitrocellulose, styrene-isobutylene copolymers, gelatin, Polymer latex, for example 2-acetoacetoxyethyl methacrylate and carboxy polyester.

It is possible to apply stamping ink, tin top seal ink, ballpoint pen ink or a pencil to the polymeric final coating by incorporating therein a carrier such as titanium dioxide, kaolin, zinc oxide, silica, aluminum oxide, polysaccharin such as starch and the like. Further, the polymeric coating completion antihalation, filter dyes, ultraviolet Strahlabsorbierinittel, acid stabilizers, such as higher fatty acids and color toning agents may be included such as _{phthalazinone}. t}

Each compound used in the context of the invention is preferably dispersed in at least one colloid, that can be used as a binder. Most of the useful binders are generally hydrophobic, however hydrophilic binders can also be used. These binders are clear or translucent and include, for example Gelatin, proteins such as gelatin derivatives, cellulose derivatives, polysaccharides such as dextran, natural Substances such as gum arabic, latex-like vinyl compounds of the kind that reduce the dimensional stability of the materials increase, and synthetic polymers as described below. Suitable synthetic polymers are in

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U.S. Patents 3,142,586, 3,193,586, 3,062,674, 3,220,844, 3,287,289 and 3,411,911 are listed. Effective polymers include water-insoluble polymers that act as a monomer unit Alkyl acrylate, alkyl methacrylate, acrylic acid, Sulfoalkyl acrylates, sulfoalkyl methacrylates or the like., contain, and polymers, the repeating sulfobetain units as stated in Canadian Patent 774-054. Additional suitable macromolecular Compounds and resins for use as binders include polyvinyl butyral, polyacrylamide, cellulose acetate butyrate, Cellulose acetate propionate, polymethyl methacrylate, Polyvinyl pyrrolidone. Polystyrene, ethyl cellulose, polyvinyl chloride, chlorinated rubber, polyisobutylene, butadiene-styrene copolymers, vinyl chloride-vinyl acetate copolymers, Vinyl chloride-vinyl acetate-maleic acid terpolymers, Polyvinyl alcohol, polyvinyl acetate, benzyl cellulose, Cellulose acetate, cellulose propionate, cellulose acetate phthalate, Polyvinyl formal, polyvinyl pyridine, polyvinylidene chloride, Methyl vinyl ether-maleic anhydride copolymers, polyvinyl acryl amide, cellulose nitrate, ■ 'butyl cellulose, carboxymethyl cellulose, Hydroxyethyl cellulose, nitrocellulose, polyethylene, polyethylene glycol, polyethylene oxide, polyacrylates, Polysulfoalkyl acrylates, polysulfoalkyl methacrylates, Polyamides, terpene resins, alginic acid and derivatives thereof, onium halide series conductive polymers and phenolic resins. Of these polymers, particularly preferred polymers are polyvinyl butyral, polyvinyl acetate, ethyl cellulose, polymethyl methacrylate, Cellulose acetate butyrate, gelatin and polyvinyl alcohol. These polymers can also be used if desired can be used in combination. The preferred weight ratio the amount of the binder to that of component (a), the organic silver salts, is in Range from about 10: 1 to about 1:10, particularly preferably about 4: 1 to 1: 4.

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A lithographic plate can also be made using special binders as in Japanese patent application 4659/72 and U.S. Patent 3,679 4-14- indicated, getting produced. A lithographic plate can also be made by making advantageous use of the special layer structure according to the US patent 3 811 886 is made.

This is also made possible in U.S. Patent 3,767 and Japanese Patent Application No. 103639 / 74- in its application to the present photosensitive System - its use as a thermal transfer sheet.

Layers, each in the thermally developable Photosensitive materials used components according to the invention contain, and the other layers can be mounted on any carrier selected from a wide variety of materials. These carriers can have any shape. However, sheet, sheet, roll, and ribbon shapes are generally known as flexible carriers are referred to, advantageous in handling as information recording material.

The materials useful as supports include plastic sheets, sheets, glass, wool, cotton cloth, paper and Metals such as aluminum. As plastic films, cellulose acetate films, polyester films, for example polyethylene terephthalate films, Polyamide films, polyimide films, triacetate films, polycarbonate films, oriented polyethylene terephthalate films, Cellulose nitrate films, cellulose ester films, polyvinyl acetal films, polystyrene films, polyethylene terephthalate films, which are colored by titanium dioxide or the like, dye-containing ones which can be decolorized by heat Foils, polyester foils with a hydrophilic surface,

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by. Dispersion of silica or the like. And a partially hydrolyzed vinyl chloride-vinyl acetate copolymer and polyethylene terephthalate films on which a gelatin primer layer is formed is to be applied. Examples of paper supports include not only the commonly used paper, but also photographic base paper, reproduction paper such as coated paper and art paper, baryta paper, resin-coated paper Paper, waterproof paper, paper having sizing treatment using a polysaccharide or the like. received, as indicated in Belgian patent 784, partially acetylated paper, pigmented paper containing titanium dioxide or the like. With a oc-01efinpolymerem, for example polyethylene, polypropylene, Ethylene-butene copolymers and the like, coated paper, Paper that has previously been treated with polyvinyl alcohol or a metallic thin film, Foils or papers which: are equipped with conductivity due to a carbon treatment ^ Paper with a Gelatin undercoating, glassine paper, Kent paper, paper coated with a map coating, paper with one made from clay, insolubilized casein, or carbox7 / methylcellulose fabricated surface, paper that has received a calendering treatment, paper that is made with acidic polymers is impregnated or coated with it and the like.

In addition to the above, aluminum plates, that are equipped with a polyacrylamide as an undercoat, aluminum plates that are treated with a hydrophilic Obtained silicate and used substrates containing a conductive metal layer as a primer layer will.

If desired, patterns can be engraved on both the top layer and the back layer of the wearer

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will. This type of engraving is required to make a postcard or a time card.

The various types of layers described above are generally applied to any of the above Carrier formed, but some components can also be incorporated into the carrier itself. Incorporation Some components in a carrier, such as plastic sheeting, glass or metal foils, is of course with numerous Difficulty accompanies in order to achieve that the components effectively exert their desired effect. However The incorporation of some components in a paper carrier allows the components to have their effect in the same way Show the extent to which they are incorporated into a layer formed on the carrier.

Antifoggants, tinting agents and antihalation agents are examples of materials that can be incorporated into the carrier. Within the scope of the invention can an organic silver salt, a photocatalyst and optionally a sensitizing dye into the same Layer can be incorporated if desired, d. H. these Layer is called a light-sensitive layer.

Other ingredients according to the invention, for example reducing agent, tinting agent, antifoggant and ultraviolet absorbent and the like can be used into the above photosensitive layer or further layers on the support, such as a primer layer or protective layer can be incorporated if desired.

In the context of the invention it is most preferred to use an organic silver salt, a photocatalyst a reducing agent, a tinting agent, an antifoggant and a binder are incorporated in a layer on the support.

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The photosensitive composition is applied to the support at a coverage in the range from about 0.2 g to about 5% preferably about 0.3 g to about 2 g, indicated as silver content both from organic silver salt and silver halide, pulled up per m of the carrier. When the coating amount is less than the above lower limit, it becomes the maximum Density of the image obtained is too low, while a tendency to saturate the maximum density of the image in the Range is more than the upper limit. As a result, an excessive amount of the coating increases against the above upper limit only covers the cost of the product.

A manufacturing method of thermally developable photosensitive materials which can be used in the invention is roughly explained below. The agent forming the organic silver salt is caused to react with an agent generating silver ions, for example silver nitrate, by one of the various methods described above, so that the production of the organic silver salt results. It is preferred to add component (d) in the course of the production process of the organic silver salt or beforehand. The production process is usually carried out at atmospheric pressure and a suitable temperature in the range from -50 ° C to + 80 ° C, in particular from about 20 ° C to about 60 ° C. The organic silver salt is contacted with water _i an alcohol or the like., And then washed in a binder for emulsion formation by means of a colloid mill, a mixer, a ball mill or DGL ₁ dispersed. The dispersion is usually carried out at ordinary temperature (15 to 25 ° C). Then, a silver halide forming agent is added to the thereby obtained polymer dispersion of the silver salt for conversion

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of a certain part of the organic silver salt in the corresponding silver halide was added. The reaction temperature is approximately in the range from room temperature to 80 ° C and the appropriate reaction time can desirably range from about 1 minute to about 48 hours to get voted. As stated above, a previously prepared silver halide can be added to the above Dispersion can be added or the organic silver salt and the silver halide can be used at the same time are formed. It is preferred to use the component (d) in the course of the manufacturing process of the silver salt or to be added beforehand. Various additives such as sensitizing dyes, reducing agents, coloring agents and the like. Are then added, preferably in the form of a solution in the order of the listing. Also the component (d) can be added at this point. Usually the components alternate with stirring at a temperature in the range from room temperature to 50 ° C at suitable time intervals (usually 5 to 20 minutes) added. The coating solution thus prepared is applied to a suitable support without drying raised. Around the final overcoat polymer layer, primer layer, back layer or other To obtain layers, the respective coating solutions are prepared in a similar manner to the above and by immersion, air knife opening, curtain covering or funnel-coated. Two or more layers can be used at the same time as desired Process according to US Pat. No. 2,761,791 and US Pat British Patent 837 095 are drawn up.

If desired, printing can be carried out on the surface or the rear side of the support or on the support Attached layer can be executed to a season ticket or a similar ticket, a postcard or other

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To train labels.

The heat developable produced in this way photosensitive material will be used if necessary cut to the appropriate size and then exposed imagewise. The resulting material can, if desired, be allowed to dry up to 80 ° C to 140 ° C prior to imagewise exposure be preheated. Light sources suitable for imagewise exposure include Volfrani lamps, fluorescent lamps for copying, which are mainly used for the exposure of light-sensitive diazo materials, Mercury lamps, xenon lamps, CRT light sources, lasers and the like. As the original, not only a line image such as a drawing but also a photographic one can be used Graduated images, portraits, and scene images captured with the camera can be used.

The rendering methods applicable to the present invention include contact printing, where the original is placed tightly on the sensitive material, the reflection pressure and the enlargement pressure. The exposure amount depends on the sensitivity of the received sensitive material. An exposure amount of around 10 lux-seconds is a guide value for highly sensitive people Materials required during an exposure

approximately 10 lux-seconds is required for low sensitivity materials.

The sensitive materials imagewise exposed in this way can only be developed by heating (up to about 80 ° C. to about 180 ° C., preferably to about 100 ° C. to about 150 ° C.). Diss heating time for the development is controlled ± ^r c ranges from 1 to 60 seconds in a suitable manner. It depends on the heating temperature. Typically, heating from about 5 to 4-0 seconds at 120 ° C, about 2 to about 20 seconds at ⁰ C I30

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• V-

and heating at 140 ° C. for about 1 to about 10 seconds is required.

A great variety of measures can be taken for heating of the sensitive material. For example, the sensitive material can come into contact with a simply heated plate or brought with a heating drum. Depending on the circumstances, the sensitive material may be be guided through a heated room. It can also be performed using high frequency waves or laser beams be heated. The odor generated upon heating can be removed by using a deodorant equipped treatment machine to be masked. Perfumes can be used in the delicate material to mask the odor generated from the sensitive material upon heating are incorporated, as in Japanese Patent Application 82518 / 74- specified.

The thermally developable photosensitive materials produced within the scope of the invention have im generally have the character of slight damage when they are in contact with moisture. Therefore it is favorable that the finished sensitive materials are shipped as a package together with a desiccant as disclosed in Japanese Patent Application No. 2523/75.

According to a preferred embodiment of the invention become thermally developable photosensitive materials of excellent green storage life, which has a high degree of whiteness and high sensitivity own, receive.

The following examples serve to further illustrate the invention.

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M-

example 1

1.9 g of sodium hydroxide was dissolved in 100 ml of water. This aqueous solution was with a dissolving of 12 g.Lauric acid in 100 ml of toluene obtained solution under Mixed to form an emulsion at 25 ° C. An aqueous solution with 8.5 g of silver nitrate dissolved in 50 ml of water and an aqueous solution of 0.3 g of (NH ^) ^ Ce (NO ^), -, dissolved in 25 ml of water, became an emulsion at 21 ° C at the same time added. The rate of addition of both solutions was regulated in the same way. At the end of the dropwise addition of the aqueous solution of the silver nitrate, the emulsion separated into an aqueous phase and a toluene phase, which Contained silver laurate. After the aqueous phase had been removed, the precipitates (containing cerium ions Silver laurate) separated from the toluene phase by centrifugation.

The precipitate was dispersed in a polymer solution, which by adding 2315 g of polyvinyl butyral (Polymerization number 1000) to 160 ml of isopropanol had been prepared by means of a homogenizer, so that a polymer dispersion of the silver salt containing about 1/20 mol of silver laurate was prepared. A 80 g portion of the polymer dispersion of the silver salt was kept at 50 ° C and 16 cm * of a solution with 1.1 wt.% N-Bromoacetamide in acetone was added with stirring and the reaction system was allowed to stand for 60 minutes while heating was continued to be at 50 ° C keep.

After the dispersion obtained was quenched at 30 ° C., the following components were in the The order in which they are listed is added to the resulting dispersion every 5 minutes while stirring is continued became.

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M.

Components

(a) Sensitizing dye (merocyanine dye of the following formula)

CH2COOK

(Solution with 0.025% by weight in 2-methoxyethanol) 10 ml of other merocyanine dyes, other cyanine dyes and acidic dyes can be used in place of this dye in the same manner.

(b) Antifoggants

Sodium thiobenzenesulfonate 24 ml

(Solution with 0.02 wt.% In

Methanol)

(c) Antifoggants

Rosin (Oxidation Number 162, Staybelite Rosin, product of Hercules Powder, Inc.) (Solution with 10% by weight in ethanol) 8 ml

(d) Antifoggants
Benzotriazole

(Solution with 0.15 wt.% In
Methanol) 12 ml

(e) Coloring Agents
Phthaiazon

(Solution with 3% by weight in methanol) 32 ml

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M.

(f) Reducing Agent

{Solution with 24 wt.% In acetone)

40 ml

The coating dispersion prepared in this way

was applied to an art paper to give a cover of 0.4 g

ρ
Silver wound up per m. A thermally developable photosensitive material A was thereby obtained.

For comparison purposes, a thermally developable photosensitive material B was prepared in the same manner as the sensitive material A except that the addition of (NH ^) 2Ce (BO ₇ ,) ^ was omitted.

The heat developable photosensitive materials A and B thus prepared were each made exposed to tungsten light through a wedge (3 x 10 ^ lux. Seconds) and then heating at 14-0 C for δ seconds developed. They were then subjected to sensitometry. Identical samples of the thermally developable photosensitive Materials A and B were 7 days at 35 ° C allowed to stand in an atmosphere containing humidity having a relative humidity of 80%, and then like above subject to the sensitometric. The results are summarized in Table I.

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[Sensitivity Table I. Sensitive
Material B • s veil
(^ Dmax Sensitive
Material A 100 f Sensitivity * 103 0.18
1.41 Fresh <Schieier
Q Dmax
Y 0.17
1.45 120 * 107 0.80
1.33 To
7 days
at 35 °
and 80 { 0.20
1.35

The reciprocal of the amount of exposure required to obtain a fog density + 0.1, and relative value obtained when the sensitivity of the sensitive material B is set to 100.

It follows from the values in Table I that the sensitive material A according to the invention is a has excellent green storage life.

Example 2

A thermally developable photosensitive material C was prepared in the same manner as the sensitive material A in Example 1 except that 0.2 g of Ce (SO ^) _{2 was added} instead of (NH ^) ₂ Ce (NO,) -. Development and sensitometry were carried out under the same conditions as in Example 1. The results are shown in Table II.

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. ¹ H.

Table II

Delicate material

ί sensitivity veil Dmax

After 7

Days

at 35 ⁰ C

and 80% U> max

(Sensitivity • {Veil

95 0.18

1.35

99

0.25

1.30

B.
(Comparison)

100 0.18

120

0.80

1.33

It follows from the values in Table ± 1 that the sensitive material C according to the invention is a had excellent green storage life.

Example 3

The thermally developable photosensitive material D was made in the same manner as the sensitive material A of Example 1, except that 24 mg CeBr ^ * 5HpO were added instead of (NH ^,) pCe (NO -,) g. The sensitive material B (comparison) and the sensitive material D were each developed and the sensitometry subjected under the same conditions as in Example 1.

The developed materials B and D were each connected to a fluorescent lamp (10,000 lux, 10 hours) via the entire surface exposed. Then, the increase in background density (non-image area) was examined. Regarding the extent of the whiteness after the total exposure the sensitive material D turned out to be much better than the sensitive material B.

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Vi III 2635541 Tabel D. Delicate material 330 B (comparison) Sensitivity* 0.14 100 veil 1.13 0.18 Dmax 0.05 Δ D ** 0.15

Relative value obtained when the sensitivity of sensitive material B is set to 100.

Value obtained by subtracting the fog value obtained shortly after the end of the heat generation of that after total exposure to a fluorescent lamp obtained haze value.

It can be seen from the values in Table III that the sensitive material D greatly improved one Shows sensitivity and better behavior of color change by light.

Example 4-

The thermally developable photosensitive material E was prepared in the same manner as the sensitive material A of Example 1, except that 20 mg of Ce (NO,) ^ * 6HpO instead of (NH ^) _p Ce _{(NO,) f} - were added . The sensitive material B (comparison) and the sensitive material E were compared according to the treatment according to Example 3 and under the same conditions as in Example 3.

With regard to the degree of whiteness after the overall exposure the sensitive material E was far better. The results of the experiments are summarized in Table IV.

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Tabel Delicate material IV B (comparison) sensitivity
veil
Dmax
Ad E. 100
0.18
1.41
0.15 280
0.15
1.15
0.07

It can be seen from the values in Table IV that the sensitive material E in terms of sensitivity and color change by light is superior.

Example 5

The thermally developable photosensitive material F was prepared in the same manner as the sensitive material A of Example 1, except that 12 g of stearic acid instead of lauric acid, 20 ml of a ¹ solution in acetone containing 20% by weight of the reducing agent of the following formula

(CH..KC _Λ. Η J. ^ C (CH-J ^

instead of the reducing agent (f) of the following formula

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c (ck ₃ ) ₃

were added, and a stencil paper for a pressure-sensitive Sheets with polyvinyl alcohol applied as an undercoat was used in place of the art paper used.

For comparison, a thermally developable photosensitive material G was prepared in the same manner as the sensitive material F except that (NH ₂ J ^ Ce (NO,.), - was not added.

Each of the sensitive materials F and G was developed and sensitometric under the same conditions as in Example 1 subjected. The results are summarized in Table V.

Table V
Delicate material FG

Fresh *

To

Sensitivity of the veil "Dmax

^ Sensitivity 7 days Jl _s ,,. at 35 ° d ^{bcnie: Ler}

and 80% U) max

103 100 0.17 0.20 1.30 1.25 100 95 0.23 0.75 1.27 1.20

It can be seen from the fourths of Table V that the sensitive material F according to the invention is excellent Had green storage life.

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Example 6

The thermally developable photosensitive material H was made in the same way as sensitive material B, but one by dissolution solution prepared from 10 mg CeBr, -5HpO in 10 ml methanol was added prior to the addition of N-bromoacetamide.

The sensitive material B (comparison) and the sensitive material H were exposed as in Example 3, developed and tested. The results are given in Table VI.

Table VI

Delicate material

Veil sensitivity Dmax Ad

H B (comparison) 230 100 0.15 0.18 1.20 1.4-1 0.08 0.15

With regard to the degree of certainty according to the total exposure, the sensitive material H was far better

Example 7

The thermally developable photosensitive material I was prepared in the same manner as the sensitive material H in Example 6 _{except that 10 mg of Ce (CH 5} COCHCOCH ^) _{5 was added} instead of CeBr, 5H ₂ O.

The results obtained after treatment and testing as in Example 3 are summarized in Table VII.

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Af

Table VII

Delicate material

Sensitivity veil

Dmax

I. B (comparison) 195 100 0.17 0.18 1.25 1.41 0.08 0.15

It is found that the sensitive material I with regard to the degree of whiteness after the overall exposure is far better.

Example 8

The thermally developable photosensitive material J was prepared in the same manner as the sensitive material B of Example 1, except that a solution of 0.1 g of (NH ^) ₂ Ce (NO,) _& in 15 ml of methanol was added before the addition of the coloring agent (e) (phthalazone) was added.

The results obtained after treatment and testing as in Example 1 are summarized in Table VIII.

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Table VIII

Delicate material

(Sensitivity fresh - \ veil (-Dmax

After 7 (sensitivity days at

35 C and

80 % (Dmax

B (comparison)

98 100 0.18 0.18 1.35 1.41 103 120 0.45 0.80 1.30 1.33

From the above values, it can be seen that the haze due to storage under the conditions high temperature and high humidity can be prevented when using ammonium cerium nitrate,

Further, it can be seen from Tables I and VIII that the fogging preventive effect was advantageous when Ammonium cerium nitrate was used in the formation of the silver laurate.

The invention has been described above on the basis of preferred embodiments without being limited thereto is.

709825/0861

Claims (9)

Claims 1. A heat developable photosensitive material containing (a) an organic silver salt, (b) a photocatalyst and (c) a reducing agent in a carrier or in at least one on a carrier: formed layer, wherein the carrier or at least one layer of these layers further (d) at least a trivalent and / or tetravalent cerium compound as Contains cerium compound. 2. Photosensitive material according to claim 1, characterized in that the trivalent or tetravalent Cerium compounds by the following general formulas (I) are reproduced, wherein Ce is a trivalent or tetravalent cerium atom, X an anion or a group suitable for conversion into an anion, 1, m, η, ρ and q the necessary integers to make the connection neutral, χ and y an integer from 0 to 16, and M each mean a cation or a group which can be converted into a cation. 5. Material according to claim 2, characterized in that that the anion or the group capable of being converted into an anion, consisting of nitrate ions, oxygen ions, titanate ions, Acetate ions, acetylacetonate ions, carbon ions, halogen ions, long-chain aliphatic carboxylic acid groups, perchlorate ions or phosphorus ions. 709825/0861 4. Material according to claim. 2 or 3 * marked that M is a hydrogen ion, an alkali ion or means an oniua group. 5. Material according to claim 2 to 4, characterized in that the trivalent or tetravalent cerium compounds consist of one or more of the following compounds: Ce (OH) ₅ . Ce (OH) ₄ , CeO ₂ , Ge ₅ O ₅ , Li ₃ Ce-O ₆ , Na ₂ CeO ,,, KCeO ₂ , K ₂ CeO ₅ , CeK, Ce (IiO ₇ J ₅ , Ce (NO ,.) ^ 6H ₀ O. Ce (EO ₅ ), '5H ₂ O, Ce (NO ₅ ) ₇ * / + H ₂ O. Ce (NO ₅ ) ^ _{-5K 2} O, "CeOH (NO ₇ ) ₅ · xH ₂ 0, (x = 0 and / or 3), KCe (NO ₅ ) ^ H ₂ O, K ₂ Ce (NO ₅ ) _s / K ₂ Ce (NO ₃₅ ) ₆ , RbCe (NO ^) ₄ -H ₀ O , Rb ₂ Ce (NO _7. ^ -4-H ₉ O, Ub ₀ Ce (IiO,.),:, CsCe (NO ^) ₅ -H ₂ O, (NH ^) ₂ Ce (KO ₅ ) ₆ 7 NH ₄ IICe (NO ₅ J ₅ -H ₂ O7 (NH ₄ ) ₂ Ce (N0) ₅ · χΗ ₂ 0 (χ = 0 and / or 4), Ce (CH ₅ COO) _x -H ₉ O, (CH ₅ COCHCOCh ₅ ), Ce, (KH ₄ ) ₂ Ce (S0 ₄ ) ₆ -xH ₂ 0, (x = 0.2 and / ccier 6) Ce ₂ (CO ₅ ) _7. 8H ₂ O, CeCl ₅ * 7H ₂ O, Ce ₂ (SO ^),. 8H _? 0, Ce (SO ₄ ) ₂ "xH _p 0 (x = 0, 2, 4, 5, 8, 9 and / or 12), CeBr ₅ , Ce ( TiO ₅ ) ₂ , CeJ ₅ -9H ₂ O, Ce (C10 ₄ ) .. 6H _p 0, CePO ₄ , Ce (C ₁₂ H ₂₅ COO) ^, Ce (C ₂₂ H _4n OOO) ₅ and Ce (C ^ gH ₅₇ COO) ₅ , where χ has a value from 0 to 10 ". 6. Material according to spoke 1 to 4, characterized in that that the trivalent or tetravalent cerium compound consists of a cerium complex. 7. Material according to claim 6, characterized in that the cerium complex salt consists of one of the following salts: Ce (Dip) ₂ (N0 ^) ^ «xH _o 0 (where Dip is 2, _f ? '- bipyridyl) (x = 0 to 16), Ce (DIp) ₂ Br ₅ , Ce (Fhen) ~ (ITQ ^) ₅ (where phen is phenanthroline), Ce (Pheu) ₂ (SCN) ₂ , Ce (Phtha) Bx- (where Phtha is phthalocyanine ), Ce (UrO) ₂ (SCH) ₅ -SH ₂ O (v / orin uro is urotropine), Ha ₇ ^ Ce (DP), 7 (v.-orin DP is diphenic acid), Ka / Ce (naphth) p7 (where kaphthi-iaphthoic acid) and NH ₄ ZCe (OX) ₂ Z-XHpO, (where OX is oxalic acid (x = ■ 0 to 16). is; 709825/0861 8. Material according to claim 1 to 7 * thereby marked -1 -5 records that about 5 x 10 moles to about 1 χ 10 moles of component (d) per mole of the organic silver salt (a) is present. 9. Material according to claim 1 to 8, characterized —Λ —4 · records that about 10 to about 10 moles of the component (d) are present per mole of the organic silver salt (a). 70982 5/0861