DE2326865A1 - HEAT DEVELOPMENT CAPABLE LIGHT SENSITIVE MATERIALS - Google Patents

Description

PATENTAKWKÜTE

DR. E. WIEGAND DiPL-ING, V /. HiEMANN DR. M. KÖHLER DIPL-iNG. C DIFFICULT

MÖNCHEN HAMBURG

TELEPHONE: 555476 8000 MONKS ^

TELEGRAMS: KARPATENT MATHILDENSTRASSE 12

232686

W. 41647/73 - Ko / üTe May 25, 1973

luji Photo Ulm Co., Ltd «Minami Ashigara - shi _; Kanagawa (Japwi)

Väimeentwic sound sensitive materials

The invention "relates to heat developable photosensitive Materials, which are often also called Varmeausentwicklungsmatei'ialien are referred to, these terms being interchangeable, and the invention relates in particular to such materials »which contain compounds that help prevent the occurrence of thermal fog upon heating (development) in the developed image, which is hereinafter referred to simply as "Sehleier" is called.

According to the invention, heat-developable Photosensitive materials indicated that have a support and contain a photosensitive layer applied to the carrier, which comprises the following components

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(a) an organic silver salt, Ob) a silver halide, which is preferably in situ by reaction with the organic Silver salt (a) is formed,

(c) a reducing agent and

(d) an IT halo-suecinimide.

The photosensitive material gives images of low fog, high density and high contrast «

Photographic Processes Using Silver Halides are widely used because the Process all electro-photographic processes or diazo type methods in terms of photographic Properties such as sensitivity, graduation and the like,

is superior.

However, the silver halide light-sensitive materials require various negotiations according to the picture-wise Exposure and development with a developer, such as stop treatment, fixation, water washing, 'stabilization and the like, so that the developed image will not be discolored or faded in the light and the undeveloped one Part hereinafter referred to as the "background" does not blacken -

Therefore, this type of photographic process requires rapid procedures a lot of work and time for the treatment and there are dangers for people due to the application of toxic chemicals in treatment and the inside of the treatment chamber, hands and clothing the workers are often stained or soiled.

Improvements to such methods using

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-2326885

von photograph! see silver ha 1 οgenid materials would be cheap, so that photograph! see materials in the dry state, that is, without a solution treatment, “could be treated and the“ treated images would be stable. Various attempts have also been made "to make such improvements. For example, the use of heat developable photosensitive materials is disclosed in Japanese Patent Publications 4921/68, 4924/68 ₅ , 26582/69, 18416/70, 12.00 /? 0 and 22185 / 70 un <I of British patent specification 1 205 500 proposed "These materials contain, as the main constituents of the photosensitive element, a silver salt of a long-chain aliphatic carboxylic acid, such as silver behenate, silver saccharin or silver benzotriazole and a catalytic amount of a silver halide"

In the usual heat developable photosensitive Materials that have previously been used and the masses of a silver salt of a fatty acid such as Silver behenate, a reducing agent and a catalytic agent Amount of a silver halide contained, x> iird After heating the exposed material, a silver image is formed which is due to an oxidation reaction between the fatty acid silver salt and the reducing agent due to the catalytic The action of the silver salt formed in the exposed part results, however, at the same time as the oxidation-reduction reaction pretty much continued even in the non-exposed parts, so that a non-distorted Veil adjusts in the image preserved «. The usual materials are thus due to the training of this Veil deficient.

A method of preventing this from developing

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The veil consists in the use of mercury ions. For example, in Japanese Patent Publication 11113/72, the preparation of heat developable photosensitive materials proposed that an organic silver salt, a reducing agent, or a catalytic amount of a photosensitive silver salt and, in addition to these components, contain a compound that supplies mercury ions »In these photographic materials, the occurrence of fog is reduced.

However, mercury compounds are known to be toxic. Therefore, there is at mercury compounds a serious risk and when .a consumed Überzugslö-SUDg ₅ contains such toxic mercury compounds, discharged into a river or the like ", the toxic compounds accumulate in the bodies of fish and shellfish, then that a serious There is danger to people who eat such mussels or fish. Furthermore, when the photographic materials are reused in the manufacture of regenerated papers or the like, the toxic mercury compounds are released, which also causes the problems discussed above.

It is an object of the invention to provide heat developable photosensitive materials that contain compounds that prevent fog from occurring in in the same way as the mercury compounds, which, however, have no toxicity like the mercury compounds the case is.

A further object of the invention consists in heat-developing photosensitive materials which a picture of decreased discoloration by light after the

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232686

Development of the same result.

Another object of the invention is heat developable photosensitive materials that form an image with reduced fog, high image density and result in high contrast =

Due to the invention, wänneentwicklungsfähige j photosensitive materials provide excellent photographic properties, ide indicated above, which consist of a support and a coated on the support the photosensitive tfehicht _t which layer contains the following components:

(a) an organic silver salt _s

(b) a silver halide, which is preferably in situ by reacting a halide with the organic silver salt '(a) to form the silver halide was formed *

(c) a reducing agent and

(d) a ΪΓ-halo succinimide

The organic silver salts ^ component (a) / * * die are used according to the invention, are colorless »They do not change their color, even if they are used for 1 week be left under normal light or at temperatures slightly lower than 80 ° G for JO minutes be heated. However, they will also use the reducing agents according to the invention / component (c) / in the presence of "exposed silver halide reduced =

Preferred organic silver salts are silver salts of organic compounds which have an imino group, Contain carboxyl group or mercapto group »

Examples of organic silver salts / "Component Ca) /? which are used according to the invention are silver salts of organic compounds with an imino group

or a mercapto group or silver salts of organic acids having 10 or more carbon atoms ₅ beispielsx-jeise silver benzotriazole, Silbersaccharin, silver phthalazinone, the silver salt of 3-mercapto-4-phenyl-1 _s 2 _{9 s} 4-triazole, the silver salt of 4-hydroxy ~ 6 -methyl ~ 1,3, yes, 7- ^ etrazainden _s ¹ OaS silver salt of 2- (S-ethylglycolamide) -benzothiazQl ₃ silver caprate, silver laurate _s silver myristate, silver palmitate, silver stearate silver behenate, silver phthalate, silver terephthalate, silver salmon Those organic compounds are preferred which contain more than 10 carbon atoms among the above organic compounds with an imino group or mercapto group »

The amount of component (a) present is only that which is necessary to produce a sufficient difference in density to provide good differentiation after the development of the light-sensitive element »The quantity can vary widely and if the above criteria are met, the exact amount used is not particular critical. However, since the visual acuity of consumers varies widely, are usually at least

about 1/600 mol / m of the carrier present and only rarely

In cases more than 1/10 mol / m ~ of the silver salt are used. In practically all circumstances, it is technically feasible to use 1/500 to about 1/40 mol / m ² of silver salt.

The component (b) used according to the invention consists either (1) of a compound which can react with the above silver salt (a) to form a silver halide or (2) of 'a silver halide '

Examples of the former compound (1) are inorganic compounds of the Pormal MXh _? where M is a hydrogen atom, an ammonium group or a metal, for example

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wise strontium, cadmium, zinc, tin, chromium, sodium, barium ₃ iron, cesium, lanthanum, copper, calcium, nickel, magnesium, potassium, aluminum, antimony, gold, cobalt, mercury, lead, beryllium, lithium, manganese, gallium , Indium, rhodium, ruthenium, palladium, indium, platinum, thallium, bismuth and the like, X is a halogen atom such as chlorine, bromine or iodine, and η is the number 1 if M is a hydrogen atom or an ammonium group, and n if M is a metal, the valence of the metal "mean.

■ Compound (1) also includes organic Halides, such as triphenylmethyl chloride, triphenylmethyl bromide, 2-brom-2-methylprop.an, 2-bromobutyric acid, 2-bromoethanol, Benzophenone dichloride, iodoform, bromoform, Tetrabromkohl ens to ff and the like ο

The formation of the silver halide can easily be obtained by examining the X-ray diffraction pattern Materials to be determined. If component (b) is a silver halide in the reaction with the organic Forms silver salt, it can be used xverden. Explanatory Examples of the silver halide (2) are silver chloride, silver bromide, silver iodobromide, silver iodobromochloride, silver bromochloride j silver iodide and; the like »

The photosensitive silver halides may consist of coarse and / or fine particles, and particularly, an emulsion of extremely fine particles is preferred. The emulsion containing the light-sensitive silver halide can be prepared by any conventional method known in the photographic art, for example by the single-nozzle or double-nozzle method, as a Lippmann emulsion, as an ammonia emulsion, as a thiocyanate or thioether-ripened emulsion, soifie emulsifiers described in IORM for example, in the US-patents 2 222 264- ₉ 3 320 069 and 3271157

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sions.

According to the invention, the silver halide should be Particle size from about 0.0001 micron to about 1 micron, more preferably from 0.001 micron to 0.1 micron.

The binder / silver halide ratio is not is particularly important, but is generally from about 4000/1 to about 1/10, more preferably from 400/1 to 1/1 (based on weight).

The silver halides used according to the invention can by means of chemical sensitizers, such as reducing agents, sulfur or selenium compounds or Gold, platinum or palladium compounds or mixtures thereof are sensitized. Some preferred methods of sensitization are disclosed, for example, in U.S. Patents 2,623,499, 2,399,083, 3,297,447, and 3,297,446 specified.

According to the invention, the photosensitive silver halide can be prepared separately as mentioned above be (pre-made silver halide) and a catalytic Set of the same as one. Component of the photosensitive layer of the photosensitive material is used will. However, more preferred is a halide with the organic silver salt, which is another component of the photosensitive compounds used in the present invention Layer is, in a catalytic amount, of the photosensitive silver halide forming component implemented so that the silver halide from part of the organic silver salt is formed (in situ silver halide).

The compounds listed above can be used individually or in the form of a mixture of two or more

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bindings are used. The amount of component (b) "added is preferably about 0.001 to about 0.5 moles per 1 mole of the organic silver salt. if the If the amount of it is far smaller than this range, the sensitivity of the layer will decrease. If on the other hand the amount is much larger, the component (b) will gradually blacken the non-image parts of the heated ones and developed photographic materials when the material is left to stand in the light and the contrast between the non-image parts and the image parts is deteriorated.

The inorganic or organic halide reacts practically stoichiometrically with the organic silver salt i - and consequently - the added amount of the inorganic Halide and the amount of silver halide present in the finished element being virtually equivalent to be viewed as.

The reaction proceeds easily, and in practice the organic or inorganic halide only becomes too added to the polymer dispersion of the organic silver salt when absorbed onto the carrier and the system contributes Aged room temperature for about 5 minutes.

The reaction conditions are not particularly critical and are generally between about 0 ° C. to about 80 ° C., preferably 20 to 60 ° C., and about 1 second to about 60 minutes, preferably 30 seconds to 30 minutes. . -

It can be sub-atmospheric pressure or sub-atmospheric pressure may be applied, however, by complicating the system in this way, little is gained and the reaction is generally carried out in a system open to the atmosphere.

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The reducing agent (c) used according to the invention reduces the organic silver salt with formation of a silver picture, if the photograph! see material is heated, in the presence of exposed silver halide as a catalyst.

Suitable reducing agents can be determined with regard to the combination with the organic silver salt and preferably consist of substituted phenols, substituted or unsubstituted bisphenols, substituted or unsubstituted bisnphthols, substituted or unsubstituted naphthols, dihydroxybenzenes or higher polyhydroxybenzenes ^ dihydro ^ ynaphthalenes or higher polyhydroxynaphthalenes or higher polyhydroxynaphthalenes , Hydroquinone monoethers, diethers, triethers and tetraethers, ascorbic acid or Derivaten.hiervon, J-Tjra zolidonen, pyrazolin-5-ones, reducing saccharides and the like.

Preferred substituted phenols, bisphenols, bisnaphthols and naphthols are those where the substituting Groups from alkyl groups (C ^ -Cg), alkoxy groups (C ^ -Co), phenyl groups, halogen atoms, amino groups, alkyl-substituted amino groups (C ^ -Cg), benzyl groups, Hydro2iyalkyl groups (G ^ -Cg), acetyl groups and nitro groups exist.

Most preferred of the hydroquinone ethers are the monoalkyl ethers (C 1 -C 6), the mono aralkyl ethers and the monoaryl ethers.

Most preferred of the ascorbic acid derivatives are the mono- or dicarboxylic acid esters of ascorbic acid.

Most preferred of the J-pyrazolidones substituted or unsubstituted 1-aryl-3-pyrazolidones, v / o the substituents are most preferably those given for the substituted phenols are.

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Of the pyrazolin-5-ones, those "before-, added, which are substituted with substituents, like them for the substituted phenols are given.

Specific examples of reducing agents are: the following: hydroquinone ^ methyl! Hydroquinone ^ chlorohydroquinone ,. Bromohydroquinone, phenylhydroquinone, hydroquinone laonosulfonate, tert.-octylhydroquinone, tert.-butylhydroquinone, 2,5- ^ i ^ ^e "fchy! Hydroquinone, 2,6-dimethylhydroquinone, methy! Hydroquinone, etho ^ hydroquinone, p-methoxyphenol, hydroquinoline , Pyrogallol, resorcinol, p-aminophenol, o-aminophenol, IY-methoxy-aminophenol, 2-methoxy-4-aminophenol, 2,4-diaminophenol, 2-ß- * hydroxyethyl ~ 4-aminophenol, p-tert-buty ! phenol, p-tert.-amylphenol, p-cresol, '2,6 ~ di-tert.-butyl-p-cresol, p-acetophenol, p-pheny! phenol, p-phenylphenol, 1,4-dimethoxyphenol, 3, M ~ xylenol, 2,4-xylenol, 2,6-dimetho2q7phenol, 1-amine-2-naphthol-6-sodium sulfonate, 1-haphthylamine-7-u.lfonic acid, 1-hydroxy-4-methoxynaphthalene , 1-Hydroxy-4-ethoxynaphthalene, 1,4-dihydroxynaphthalene, 1,3-dihydroxyiiaphthalene, 1-hydroxy-4-aminonaphthalene, 1,5-dihydroxynaphthalene, 1-hydroxy-2-phenyl - ^ - methoxynaphthalene, i-hydroxy -2-methyl-A-methoxynaphthalene, a-liaphthol, ß-naphthol, 1,1'-dihydroxy-2,2'-binaphthyl, 4,4'-dimethoxy-1, 1'-dihydroxy-2,2'-binaphthyl, 6,6'-dibromo-2.2 ^L -dihydroxy-1,1'-binaphthyl, 6,6'-dinitro-2,2'-dihydroxy-1,1 ^l -binaphthyl, bis (2-hydroxy-1-naphthyl) methane, bisphenol A, 1,1-bis (2-hydroxy ~ 3,5-dimethylphenyl) -3.5, 5- trimethylhexane, 2.4 , 4-trimethylbenzyl-bis- (2-hydroxy-3,5-dimethylphenyl) -methane, bis- (2-hydroxy-3-tert-butyl-5-methylpheny1) -methane, bis- (2- hydro3iy-5 (5'-di-tert-butylphenyl) -methane, 4,4'-methylenebis (3-methyl-5-tert-butylphenol), 4; 4'-methylene-bis- (2,6 ~ di-tert-buty! phenol), 2,2'-methylene-bis- (2-tert. »

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butyl-4-ethylphenol), 2,6-methylene-bis (2-hydroxy-3-tert.-butyl-5-methylphenyl) ~ 4-methylphenol, 3 ₅ 3'35i5'-tetra-tert. -butyl-4,4'-dihydroxybiphenyl,! -Ascorbic acid, 1-ascorbic acid monoester., 1-ascorbic acid diester, p-oxyphenylglycine, Ή , ET-diethyl-p-phenylenediamine, puroin, benzoin, dihydroxyacetone, G-lycerinaldehyde, methyldizonic acidetet , Propyl gallate, hydroxytetronic acid, N, N-III- (2-etho3Q ^! "Ethyl) -hydroxylamine, glucose, 1-phenyl-1-pyrazolidine, ^ methyl- ^ laydroxymethyl-i-phenyl-5-pyrazolidone, bis- (3 -meth. butyl-4 ~ hydroxyphenyl) dimethyl ether and similar compounds.

The reducing agents can be used singly or in combination of two or more. The reducing agents are selected in consideration of the combination thereof with the organic silver salt. For example, usually a silver salt of a higher one Fatty acids, such as silver behenate, are relatively difficult to reduce and therefore relatively strong reducing agents are suitable for this salt, for example bisphenols, such as 4,4 -'-methylenebis (3-methyl-5-tert-butylphenol) or similar materials, on the other hand, are relatively easily reducible for Silver salts, such as silver laurate, are relatively weakly reducing agents Suitable agents, for example substituted phenols, such as p ~ phenol "Kir extremely difficult to reduce Silver salts, such as silver benzotriazole, are extremely strong reducing agents, such as ascorbic acid and the like. used »

The amount of the reducing agent used according to the invention Agent varies depending on the silver salt and the reducing agent used «, The amount

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thereof may therefore not be determined absolutely ", but per 1 mole of the organic silver salt are generally between about 0 ₉ 1 to about 5 moles preferably =.

The component (d) is the most characteristic in the photosensitive materials according to the invention = illustrative examples thereof are N-bromosuccinimide _? N-iodosuecinimide, N-chlorosuccinimide and similar materials,

Me component (d) is most preferably applied as a solution, dissolved in a suitable solvent. The time of application can be before or after the preparation of the organic silver salt (a) or before or after the formation of the "silver halide (b) * In addition this layer may be immersed in a solution containing the component (d) _s after the layer comprising the components (a), (b) and (c) is coated on the support "or the component (d) can be applied to otherwise incorporated into a layer adjacent to the layer containing component (a) and / or component (b). The N-halosuccinimides can be represented by the following formula:

³ V ι

X ■ (X: Cl, Br ₅ J)

R "-

wherein the radicals R to R ^! "not necessarily have to be hydrogen atoms, but also substituted groups as radicals R to R" are in the scope of the invention ", the amount of component (d) is preferably about O ₅ OOI mol to about 5 mol! to 1 mole of component (s) »

! 865

According to the invention, the components Ca) ₁ Cb) ₅ (c) and (d) are dispersed in a binder and the dispersion obtained is applied to the carrier. On the other hand, some or all of these components can be applied to the carrier in the form of applied in separate layers «.

The binders used according to the invention are generally preferably hydrophobic, but can also be hydrophilic. The binders are preferably transparent or semi-transparent and consist, for example, of gelatin _? Gelatin derivatives or mixtures thereof with dispersed latex-type vinyl compounds, cellulose derivatives, and synthetic polymer substances such as polyvinyl compounds, acrylamide polymers, and the like. Specific examples of such binders include gelatin and gelatin derivatives such as phthalated gelatin, cellulose derivatives such as cellulose acetate, cellulose propionate and acetate Cellulose nitrate, polyvinyl compounds such as polyvinyl acetate, polyvinyl alcohol, polyvinyl butyral, polyvinyl chloride, polyvinyl acetate, polyvinylidene chloride and polyvinyl formal.

There are no significant restrictions on the binder, provided it is transparent or semi-transparent is, d. H. it can be colorless or white, and is Soluble in Vassex "· or organic solvents.

Specific examples of the binders also include cellulose acetate propionate, polymethyl methacrylate, polyvinyl pyrolidone, polystyrene, ethyl cellulose, chlorinated rubber, polyisobutylene, butadiene-styrene copolymers, ₉ vinyl chloride-yinylacetate copolymers, copolymers of vinyl acetate and vinyl chloride-maleic phthalulose, cellulose acetate and vinyl chloride-maleic phthalulose “As can be seen from the above list

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results, the copolymers can be freely selected as binders according to the invention and there are no special restrictions for this, although with a copolymer of vinyl acetate and maleic acid or of vinyl chloride and maleic acid, maleic acid is preferably less than 5% by weight of the total copolymer and in the case of the butadiene-styrene copolymers, the molar ratio of these components is favorably M- : 1 to 5 · 1.

The ratio of the amount of the binder to the organic silver salt is preferably about 4: 1 to about 1 s 4-, as Gextfichtteileee

As stated above, however, the elements need 5 according to the invention not all are present in one layer and two or three layers can be used »For example, component (c) or (d) be in a separate layer or two separate layers. In such embodiments with separate The binder used in the layers is the same as the binder used in the photosensitive layer, which contains all components (a) to (d). Generally, if component (c) or (d) in one separate layer or two separate layers, the layers being from about 1 micron to about 15 microns, preferably 3 to 10 microns and the components (c) or (d) are present in an amount of about 0.01 to about 10% by weight of the binder, preferably 0.1 to 5%, "

The carrier used according to the invention can consist of all known, customary pathogens. Illustrative examples of supports are cellulose nitrate film ₉ Celluloseesterfilaie, Polyvinylaceta1filme films, polystyrene films, PoIyä.thylenterephthalatfilme, Polycarbonatfi3-me, as well as films of other resin materials as well as glass, paper, metal and similar materials "

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Although not particularly limiting, good results are obtained if "the strength of the photosensitive Layer in the order of 1 micron to about 15 micron, more preferably 3 microns to 10 microns.

The heat developable photosensitive materials according to the invention can be antistatic

Layer or a conductive layer included. In addition, an antihalation substance (antihalation dye) are also incorporated into the photosensitive layers.

If desired, the photosensitive materials can according to the invention furthermore a matting agent, for example starch, titanium dioxide, zinc oxide, Silicic acid and the like. Contain. Furthermore, fluorescent whitening agents or brightening agents, for example of the stilbene type, triazine type, oxazole type or coumarine type, can be used can also be incorporated into the materials.

The heat-developable photosensitive layer according to the invention can be formed on the support in various ways Process, for example by the dip coating process, the air spread coating process or the Curtain coating process as well as according to the extrusion coating process using a funnel (see U.S. Patent 2,681,294). If desired two or more layers can be applied to the support at the same time.

Optical sensitizing dyes are preferably and advantageously used in the materials according to the invention used to impart further sensitivity to the photosensitive elements of photographic materials.

For example, the optical sensitizing dyes can be in the form of a solution or dispersion, dispersed

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gated or dissolved in an organic solvent, for optical sensitization can be added. Illustrative examples of such optical sensitizing dyes are, for example, cyanine type or merocyanine type dyes.

A final coating polymer layer can also be used if desired on the photosensitive layer to increase the transparency of the layer, to increase the density of the image formed and to improve the storability of the photosensitive materials. The thickness of the final overcoat polymer layer is preferably 1 to 20 microns.

The preferred polymers to form the final Coating polymer layers are, for example, polyvinyl chloride, polyvinyl acetate, copolymers of vinyl chloride and vinyl acetate, polyvinyl butyral, polystyrene, polymethyl methacrylate, Benzyl cellulose, ethyl cellulose, cellulose acetate butyrate, Cellulose acetate, polyvinylidene chloride, polyvinylpyrrolidone, cellulose propionate, polyvinyl formal, Cellulose acetate phthalate, polycarbonates cellulose acetate propionate and the like. Such coating polymers are described in detail in Japanese Patent Application 47-45,696 specified. The proportions of the monomers in the above copolymers can be varied freely.

The heat viable ones discussed above Photosensitive materials according to the invention can easily be prepared simply by heating the material after Exposure to a light source such as a xenon lamp, tungsten lamp, mercury vapor lamp or the like. Developed will.

The temperature for the heat treatment is favorably about 100 to about 160 ° C, more preferred

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110 to 140 ° C. By lengthening or shortening the Heating time can be higher or lower temperatures within the temperature range listed above to get voted. A stably developed image is generally formed in about 1 to 60 seconds.

All of the various heating devices can be used as heating devices Elements of the photographic materials according to the invention can be in contact with a simple hot plate or the like. Or can be brought into contact with a heating drum who can through a boiler room be guided, heated with high frequency induction heating or treated in a similar manner.

The heat developable photosensitive materials according to the invention give images with little Fog and high image density. Also fade or the obtained images hardly discolor under light after development. As a result, it is possible to take pictures of high sharpness for a long period of time using the photographic materials according to FIG Invention to obtain.

Generally in the materials according to the invention

component (a) in an amount of about 0.2 to 3 g,

2
preferably 0.4 g to 2 g per m of the support, calculated as silver used, these being approximate values, since the molar values given above change somewhat with regard to these values, in combination with components (b), (c) and (d) in the following amounts per mole of component (a): component (b) from 0.001 to 5 moles, component (c) from 0.1 mole to 5 moles and component (d) from 0.001 to 5 moles Mol. Working within these ranges gives excellent heat

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photosensitive materials susceptible to development.

The invention is explained in detail below with reference to the following examples. If nothing else indicated, all operations were carried out at atmospheric pressure.

example 1

3.4 g of behenic acid were dissolved in 100 ml of toluene at 60 ° 0 dissolved and the temperature of the solution obtained was kept at 60 ° C. 100 ml of an aqueous, dilute nitric acid solution (pH 2.0 at 25 ° C) are mixed with this while stirring. The resulting solution was kept at 60 G and, with continued stirring, 100 ml of another Solution to this added in the course of 10 minutes, wherein Prepare the additive solution by adding aqueous ammonia to about 80 ml of a solution containing. 1,? g silver nitrate with formation of the silver-ammonium complex salt (pH = 10.8) and addition of water to form 100 ml the aqueous solution had been prepared. This produced a dispersion containing fine crystals of silver behenate, manufactured. The dispersion prepared in this way was left to stand at room temperature for 20 minutes, so that the aqueous layer and the toluene layer separated.

Then the aqueous layer was removed and AOO ml of water was added to the remaining toluene layer to wash the same added by means of decanting. The decantation was repeated three times and then 400 ml of water was continued to remove the silver behenate after centrifugation added. As a result, 4 g of tubular or elongated crystals were obtained (long side about 1 micron, short side about

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0.05 microns) from silver behenate.

25 S of the obtained silver behenate became 20 ml an isopropyl alcohol solution with a content of 2 g Polyvinyl butyral (molecular weight about 1000) was added and placed on the ball mill at room temperature for 1 hour grind to form the polymer dispersion. To 20 ml of the obtained silver salt polymer dispersion were added the following listed components for the production of the heat generation s capable photosensitive mass added. Each component was added every 5 minutes and after all the additions were completed, the system was stirred for 5 minutes. The temperature was 50 ° C and the Pressure was atmospheric pressure. The mass obtained was on a polyethylene terephthalate film support for the preparation of a heat developable photosensitive material (A) plotted, the amount of silver in

the drawn-up mass was 1.5 g per 1 ι of the carrier.

Added components

Ammonium bromide (2.5% by weight, methanol solution) 1 ml of benzoxazolidene-rhodanine (0.025% by weight, Chloroform solution) x 1 ml

2,2'-methylenebis (6-tert-butyl-4-methyl-

phenol) (2.5% by weight, methyl cellosolve

solution) 3 ^m l

Phthalazinone (2.5% by weight, methylcellosolve

solution ') 1 ml

N-bromosuccinimide (5% by weight, methyl cellosolve solution) 1 ml

In addition to the above materials, two other heat-developable photosensitive Materials (B) and (ö ") in the same way for comparison

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produced, wherein the material (B) contained no antifoggant according to the invention and the material (C) as halogen component an equivalent amount (1 ml) Mercury bromide (5% by weight, Mathnoll solution) instead of the Ammonium bromide of material (A) contained but not Antifoggants according to the invention.

On the photosensitive layer of each of these photosensitive materials (A), (B) and (C), a Tetrahydrofuran solution with 15% by weight of a vinyl chloride-vinyl acetate copolymer (95% by weight vinyl chloride, 5% by weight Vinyl acetate, average degree of polymerisation approx. 400) applied to form the final coating layer, the thickness of the dried film being 10 microns.

The three photosensitive materials (A), (B) and (C) thus prepared were each attached to one Tungsten light source of 240,000 lux / sec. exposed and then to 120 ° C for 10 seconds for development heated. The photographic transmission density of the images obtained was measured in each case.

Furthermore, other specimens of materials (A), (B) and (C) were kept at 120 ° C. for 10 seconds without exposure heated and the transmission density in each specimen to observe the occurrence of a heat haze certainly. The basic point for determining the transmission density lay in the film base in this and the following examples. The results are summarized in the table below.

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Material (A) Material (B) Material (G)

Photographer! Look through 2.3 2.2 1.0 leakage density 0.15 0.4 0.13 Heat veil

The amount of light

coloration. (AD) +0.10 +0.34 +0.35

From the above values it is clear that the compounds according to the invention are signed Have an effect of preventing the occurrence of heat haze (comparison of materials A and B).

When comparing the material (A) according to the invention with the material (C) γ where a common mercury compound was used, material (A) proved to be the latter material in image transmission density and superior in contrast and the extent of the heat haze in material (A) was only slightly greater than in the material (G).

If the treated materials continue to have fluorescent light inside (about 300 lux) for 24 hours were exposed, the material (A) was superior to the materials (B) and (C) in that light discoloration of the background portion of the material (A) was lower than that of the other two materials.

In the table above and the tables below the increase will be with the extent of the light discoloration the transmission density due to exposure to fluorescent light in an interior space calculated in the following way:

AD = D _A - D _B

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where D. is the transmittance density after exposure to the fluorescent light in the interior and Dg is the transmittance density prior to suspension, d. H. immediately after the treatment, is »

It follows from this that the compounds according to the invention in contrast to the usual mercury compounds are non-toxic and are beneficial for use in photographic materials.

Example 2

The same procedure as in Example 1 was followed, but using an equivalent amount of N-iodosuccinimide was used in place of N-bromosuccinimide.

The results are summarized in the table below. The same effects as in Example 1 were obtained. ^;

Material (A) Material (B) Material (C)

Photographic by 2 , 2. 2 , 2 1 , 0 nonchalance 0 , 18 0 0 , 13 Heat veil

Extent of light discoloration (AD) +0.12 +0.34 +0.35

Example 3

The same procedure as in Example 1 was used, but using an equivalent amount of N-chlorosuccinimide was used instead of ΪΓ-bromosudcinimide. The results are summarized in the table below.

3 0 9 8 A 9/1 0 2

Material (A) Material (B) Material (C)

PhotograpM see through

leakage density 2.5 2.2 1.0 Heat veil 0.15 0.4 0.5 Extent of Lichtver coloring (Ad) . +0.10 +0.34 +0.5

There were the same effects as in Example 1 obtain.

Example 4

A solution of 11 g of lauric acid dissolved in 100 ml of butyl acetate was kept at 10 ° C., and 100 ml of a dilute aqueous nitric acid solution (pH 2.0 at 25 ° C.) was added thereto with stirring, and the system was mixed at 10 ° C. With continued stirring, 50 ml of an aqueous silver compound ammonium complex salt solution / Ag (NH ₃ ) ₂ ⁺ 0 ~ 2 (pH = 10.8) containing 8.5 g of silver nitrate (cooled to 0 ° C) added to this in the course of 1 minute to react the lauric acid with the silver ions.

Tubular crystals of silver laurate (long side about 1 micron, short side about 0.05 micron) were included obtain. After washing with water, the silver salt crystals were further washed with methanol and then 3.0 g of polyvinyl butyral (molecular weight about 1000) and 20 ml of isopropyl alcohol to 2.7 g of the obtained silver laurate admitted. The total amount was then measured using a ball mill to form a silver laurate polymer dispersion dispersed.

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To 20 ml of the silver salt polymer dispersion obtained the following ingredients were added to prepare a heat-developable photosensitive composition. At 50 ° C, the mass obtained was on a Polyethylene terephthalate film base for making the heat developable photosensitive material (A) applied, the amount of silver in the

P.
pulled mass 1.7 S per 1 m of the beam was:

Ammonium bromide (2.5% by weight,
Methanol solution) 1 ml -

Benzoxazoliden-rhodanine

(0.025% by weight, chloroform solution) 1 ml of p-phenylph.en.ol (70% by weight, methyl I-cellosolve solution) 3 ml

Phthalazinone (2.5% by weight, methyl cellosolyl solution) .1 ml

Tetrachlorophthalic anhydride

(0.6% by weight, methanol solution) 1 ml N-bromosuccinimide (wt.%, Me thy Ιο ellosolve solution) 1 ml

In addition to the above, two more were heat developable photosensitive materials (B) and (G) prepared in the same manner for comparison, wherein however, the material (B) does not have an antifoggant according to FIG Invention contained and the material (C) as a halide component an equivalent amount (1 ml) of mercury bromide (5% by weight, methanol solution) in place of the ammonium bromide of material (A) and no antifoggant according to the present invention.

On the photosensitive layer of each of these photosensitive Materials (A), (B) and (C) were a tetrahydrofuran solution suit 15 wt.% Of a vinyl chloride

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Vinyl acetate copolymers (95% by weight vinyl chloride, 5% by weight Vinyl acetate, average degree of polymerization 400) applied to form a final coating layer, the dried film thickness being 10 microns.

The three photosensitive materials (A), (B) and (G) thus prepared were each on a tungsten light source of 240,000 lux / sec « and then heated to 120 G for 10 seconds for development. The photographic transmission density the images obtained were measured in each case. There were also other specimens of the materials (A), (B) and (C) heated to 120 ° C for 10 seconds without exposure and the transmission density Measured on each specimen to determine the occurrence of heat haze. The results are in the following Table summarized.

Material (A) Material (B) Material (C) Photographic transparency

nonchalance 1.7 / \ Q
j _ Q 0 _$ 8 Heat veil 0.18 0 _s 45 0.15 Extent of LichtVer coloring CDD) +0.15 +0.42 +0.45

From the above values it can be seen that the material (A) according to the invention is superior to the material (C) is where the usual mercury is used because the obtained image has a high photographic transmittance density and high contrast, and that The extent of the heat curtain in material (A) is at most

309349/1024

is slightly larger than in material (C). If continue the treated materials to a! in-room fluorescent lamp was exposed, it was found that the material (A) is also superior to the other materials in this respect than the light discoloration in the background areas is far smaller than the material (C), which contains the mercury compound »

Example 5

The same procedure as in Example 4 was carried out, but using equivalent amounts, of N-iodosuccinimide were used in place of Itf-bromosuceinimide. There were obtained the following results.

Material (A) Material (B) Material (C)

Photographic transparency s density

Värmeschleier

Extent of light discoloration (4D)

The same effect as in Example 4 was clearly obtained.

Example 6

The same procedure as in Example 4 was followed, however, an equivalent amount of H-chlorosuccinimide was used instead of ΪΓ-bromosuecinimide. The results are given in the table below.

1.6 0.8 0.8 0.20 0.45 0.15 +0.17 +0.42 +0.45

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Material (A) Material (B) Material (C)

Photographic
Permeability
density 0.6 1.8 0.8 Heat veil 0.16 - 0.45 0.15 Extent of light
discoloration (4D) +0.16 +0.42 +0.45

The same effect as in Example 4- was clearly obtained.

Example 7

6 g of benzotriazole were dissolved in 100 ml of isoamylaeetat at 50 ° C and cooled to -15 ° G to adjust the temperature of the solution obtained. Under Kühren a further solution was added to the resulting solution, wherein the added solution prepared by dissolving 8.5 g of silver nitrate in 100 ml of aqueous, dilute Salpctersäurelösung (pH = _2? 0 at 25 ° G) and adjusting the temperature of the solution obtained 5 ° G was obtained. Thus, a dispersion containing fine crystals of silver benzotriazole was obtained.

The obtained dispersion was allowed to stand at room temperature for 20 minutes, followed by an aqueous layer and an isoamyl acetate layer separated. Then became removed the aqueous layer and then added 4-00 ml of water to the remaining isoamyl acetate layer to wash it added by decanting. The decantation was repeated three times and then 40Ό ml of methanol were continued added to remove the silver benzotriazole after centrifugation. 8 g of silver benzotriazole were thereby obtained

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obtain. The silver benzotriazole particles thereby obtained were almost spherical particles with particle sizes about 1 micron in diameter.

2.5 g of the obtained silver benzotriazole was added to 40 ml of an isopropyl alcohol solution containing of 4 g of polyvinyl butyral (molecular weight about 1000) added on the ball mill over 4 hours to form a silver salt polymer dispersion. To 40 ml of the silver salt polymer dispersion obtained, the following components to produce a heat developable photosensitive mass added. At 50 ° C, the resulting mass was on a polyethylene terephthalate film support applied to produce the heat-developable photosensitive material (A), the amount of silver drawn up is 1.2 g each

2
1 m of the beam.

Ammonium iodide (8.5% by weight ₅ % methanol solution) 1 ml

Solution with a content of · 2 g of ascorbic acid monopalmitate and 2g Ascorbic acid dipalmitate in 10 ml methyl cellosolve 10 ml

Benzoxazoliden-rhodanine &

(0.2% by weight, chloroform solution) 1 ml of N-ethyl-N-dodecy-urea

(2.5% by weight, methyl cellosolve

solution) 2 ml

N-bromosuccinimide (5 wt.%,
Methyl cellosolve solution) 2 ml

Besides the above, two more were heat developable photosensitive materials (B) and (C) prepared in the same manner for comparison, wherein however, the material (B) does not contain an antifoggant according to

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of the invention and the material (C) as a halide component 2 ml mercury bromide (5% by weight, methanol solution) instead of the ammonium iodide according to (A) and contained no antifoggant.

On the photosensitive layer of each of these photosensitive materials (A), (B) and (C), a Tetrahydrofuran solution with 15% by weight of a vinyl acetate-vinyl chloride copolymer (95% by weight vinyl chloride, 5% by weight Vinyl acetate) applied zur'Bildung the final coating layer, whereby the thickness of the dried Film was 8 microns. "

A small piece of each of these materials (A) ₃ (B) and (C) a ram Wolf light source of 120 000 lux / sec. Exposed and then heated to I3O ⁰ C for 30 seconds for development. The photographic transmittance density of the obtained image was determined in each EaIl. In addition, further specimens of materials (A) ₅ (B) and (C) were heated to 1 ^ 0 ° C x ^ for 30 seconds without exposure and the transmission density of each specimen was examined to determine the occurrence of heat haze = the results are in the the following table. ;

Material (A) Material (B) Material (C)

Photographer! See hey
Permeability
density ' 0 , 93 0 , 92 0 , 60 Wäniiesveil 0 0 , 3.8 0 , 12 Extent of light
discoloration (Ad) +0 , 07 +0 , 21 +0 , 23

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It is clear from the above that the material (A) according to the invention versus the material (C), where the usual mercury compound is used became superior in that the obtained image has a high photographic transmittance density and high contrast, while the extent of the

Occurrence of Värmeschleier in material (A) only slightly is larger than in the material (G). If the treated materials continue to an indoor fluorescent lamp were exposed, it was found that the material (A) compared to the other materials also in this respect is superior than the light discoloration of the background areas was far smaller than the material (C) containing the mercury compound.

Example 8

The same procedure as in example ^r ? was used, but using an equivalent amount of N-iodosuccinimide instead of U-bromosuccinimide. The following results were obtained «

Material (A) Material (B) Material (C) Photographic transparency

nonchalance 0.90 0 , 92 0.60 Heat veil 0.15 0 , 38 0.12 .Amount of light discoloration (4d) +0.08 • + 0 , 21 +0.25

It was clearly the same effect as in the example 7 received.

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Example 9

The same procedure as in Example 7 was followed However, an equivalent amount of N-chlorosuccinimide was used in place of N-bromosuccinimide. The following results were obtained.

Material (A) Material (B) Material (C)

Photographic by 0 , 94 0 , 92 0. 60 leakage density 0 , 13 0 , 38 O, 12th Heat veil

Extent of light discoloration (4D) +0.07 · +0.21 +0.23

In the foregoing, the invention has been described on the basis of preferred embodiments, without being subordinate to this is limited.

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Claims (1)

Claims 1. heat-developing photosensitive material, "consisting of. a support and a photosensitive layer applied to the support, thereby that the photosensitive layer contains the following components: (a) an organic silver salt, (b) at least one silver halide or one halide which interacts with the organic silver salt (a) can react to form a silver halide,. (c) a reducing agent and (d) an H-halosuccinimide. 2. Heat developable photosensitive material according to claim 1, characterized in that the halide as component (b) consists of a chloride, bromide or iodide. 3. Heat-developable photosensitive material according to claim 1 or 2 _S, characterized in that the organic silver salt (a) 'consists of a silver salt of an organic compound having an imino group or a mercapto group or a silver salt of an organic acid having 10 or more carbon atoms. · 4. Heat-developable photosensitive material according to claim 3 »characterized in that the silver salt of the organic compound of silver benzotriazole, silver saccharin," silver phthalazinone, silver-3-mercapto-4-phenyl-1,2,4-triazole, the silver salt of 4-hydroxy ..- 6-methyl-1 _S 3j3a »7-tetrazainden, the silver salt of 2- (S-ethylgiykolamino) -benzothiazole, silver caprate, 309849/1024 Silver laurate, silver myristate, silver palmitate, silver stearate or silver behenate. • 5 · Heat developable photosensitive material according to claim 1 to 4, characterized in that the compound (b) consists of an inorganic compound of the Formula MX ^ consists in which M is a hydrogen atom, ammonium group or a metal, Σ a halogen atom "and η the number 1, if M is a hydrogen atom or an ammonium group, and, if M is a "metal, η is the valence of the metal mean. 6. Heat developable photosensitive material according to claim 5 »characterized in that the material consists of strontrium, cadmium, zinc, tin, chromium, sodium, barium, iron, cesium, lanthanum, copper, calcium, nickel, magnesium, potassium ,, aluminum, antimony , GoId ₂ cobalt, mercury, lead _s beryllium, lithium, manganese, gallium, indium, rhodium, ruthenium, palladium _t indium, platinum, thallium or bismuth. 7. Heat developable photosensitive material according to claim 1 to 4, characterized in that the compound (b) consists of an organic halide. 8. Heat developable photosensitive material according to claim 7? characterized in that the organic halide from iriphenylmethyl chloride, triphenylmethyl bromide, 2-bromothy propane, 2-bromobutyric acid, 2-bromoethanol, Benzophenone dichloride, iodoform, bromoform or carbon tetrabromide. 9 · Heat developable photosensitive material according to claim 1 to 4, characterized in that the silver halide (b) of silver chloride, silver bromide, silver iodobromide, silver iodobromochloride, silver bromochloride or silver iodide. 309349/1024 10. Heat-developable photosensitive material according to claim 1 to 9, characterized in that the reducing agent (c) is composed of a substituted phenol, a substituted or unsubstituted bisphenol, a substituted or unsubstituted bisnaphthol, a substituted or unsubstituted naphthol, a dihydroxybenzene or higher polyhydroxybenzene, a dihydroxynaphthalene or higher polyhydroxynaphthalene, a hydroquinoniaonoether, an ascorbic acid or a derivative thereof, a '^ -' Sjxazolidon, a pyrazolin-5-one or a reducing saccharide. 13. Heat-developing photosensitive material according to claim 1 to 10, characterized in that the N-halosuceinimide from N-bromosucein'uaid, N-iodosuccinimide or N-chlorosuccinimide. 12. Heat-developable photosensitive material according to claim 1 to 11, characterized in that components (a) to (d) are dispersed in a binder are. 13. Väirme developable photosensitive material according to claim 12, characterized in that the binder is made of polyvinyl butyral, cellulose acetate butyrate, Cellulose acetate propionate, polymethyl methacrylate, polyvinylpyrrolidone, Polystyrene, ethyl cellulose, polyvinyl chloride, chlorinated rubber, polyisobutylene, butadiene-styrene copolymers, Vinyl chloride-vinyl acetate copolymers, copolymers of vinyl acetate and vinyl chloride-maleic acid, polyvinyl alcohol, Polyvinyl acetate, benzyl cellulose, cellu- · Loose acetate, cellulose propionate or cellulose acetate phthalate exist. • 309849/1024 14. Heat developable photosensitive material according to claim 1 "to 13» characterized in that that the carrier consists of a cellulose nitrate film, cellulose ester film, Polyvinyl acetal film, polystyrene film, Polyethylene terephthalate film, polycarbonate film, glass, paper or metal. 15. Heat developable photosensitive material according to claim 1 to 14, characterized in that that the amount of the component (b) is about 0.001 to about 0.5 mole per 1 mole of the organic silver salt (a). 16. Heat-developable photosensitive material according to claim 1 to 15 »characterized in that the amount of component (c) is about 0.1 to about 5 mol per 1 mol of the organic silver salt (a). 17 heat-developable photosensitive material according to claims 12 to 16, characterized in that that the ratio of binder to organic silver salt (a) is about 4: 1 to about 1: 4, based on weight, amounts to. 18. Heat developable photosensitive Material according to claim 1 to 17 »characterized in that the amount of component (d) is about 0.001 mol to is about 5 moles per 1 mole of component (a). 19 · Heat-developable photosensitive.es material according to claim 1 to 18, characterized in that a final polymer coating layer the photosensitive layer is applied. 20. Heat-developable photosensitive material according to claim 19? characterized by the fact that the final polymer coating layer as a polymer made of polyvinyl chloride, polyvinyl acetate, a copolymer Vinyl chloride and vinyl acetate, polyvinyl butyral, poly- 309849/1024 styrene, polymethyl methacrylate, benzyl cellulose, ethyl cellulose, Cellulose acetate butyrate, cellulose acetate, polyvinylidenes liloria, polyvinylpyrrolidone, cellulose propionate, Polyvinyl formal, cellulose acetate phthalate, polycarbonate or contains cellulose acetate propionate. '21. Heat-developable photosensitive material according to Claims 1 to 20, characterized in that, that the organic silver salt (a) in an amount of at least about 1/600 mol to about 1/10 mol per ι des Carrier, calculated as silver, is present. 22. Heat developable photosensitive Material according to claim 21, -daduTrch marked that the organic silver salt (a) in an amount of 1/300 mol up to about 1/40 mol per m of the support, calculated as silver, is present. 23. Heat-developable photosensitive Material according to claim 1 to 22, characterized in that the photosensitive layer has a thickness of about 1 micron to about 15 microns. 24. Heat developable photosensitive Material according to claim 10, characterized in that the substituted phenols ,, substituted bisphenols, substituted bisnaphthols or substituted naphthols having an alkyl group of 1 to 8 carbon atoms, one Alkoxy group of 1 to 8 carbon atoms, a phenyl group, a halogen atom, an amino group, an alkyl-substituted one Amino group in which the alkyl group has 1 to 8 carbon atoms, a benzyl group, a hydroxyalkyl group, wherein the alkyl moiety has 1 to 8 carbon atoms, or is substituted for an acetyl group or a nitro group are. 309849/1024 25- Heat developable photosensitive Material according to claim 1 to 24, characterized in that the amount of component (b) 0.001 to 0.5 mol, the amount of the component (c) 0.1 to 5 mol and the amount of component (d) is 0.001 to 5 moles, all based on 1 mole of component (a) " 3Q9849 / 1Q24