DE2120958A1 - Light and heat sensitive recording material - Google Patents

Description

PATENT LAWYERS DR.-ING. WOLFF, H. BARTELS, DR. BRANDES, DR.-ING. HERO

MDNCHEN22 ... 5..Np.V .. 197O THIERSCHSTRASSE 8 TELEPHONE: (Mil) 2932W

HA-o

Registration number. 122 712

Eastman Kodak Company, 34-3 State Street, Hochester, New York State, United States of America

Light and heat sensitive recording material

1098U / 168S

The invention relates to a light- and heat-sensitive recording material with at least one layer applied to a layer support with a fetch on one for production an oxidation-reduction image, consisting of a silver salt oxidizing agent and a reducing agent Combination, a binder and at least one activator-toner agent.

It is known that the latent produced during the exposure of a photographic recording material containing silver halide Image using a silver halide developing agent by the so-called dry exposure method from developing heat. A photographic recording material that can be developed by this known process can to be suitable for producing a fully developed stable image to be, contain a silver halide developing agent and other substances of various types. By the Heating the exposed photographic recording material the latent image is developed and stabilized. A known method of the specified type is described, for example, in U.S. patent specification 3 301 678.

Other methods and recording materials suitable for carrying out the so-called dry development taking place under the action of heat are, for example, in US Patents 3 ^ 52 904, 1 441 619, 3 392 020 and 2 910 377 as well as in the Belgian patent 705 872.

Many of the known light and heat sensitive photographic Recording materials consist of a layer support , on which are arranged (a) a combination capable of generating an oxidation-reduction image, e.g. A combination of an oxidizing agent, for example silver behenate, and a reducing agent, is particularly advantageous A phenolic reducing agent, (b) a so-called catalyst

109848/1685

sator for the formation of an oxidation-reduction image capable combination, e.g. a photographic silver halide, (c) a binder such as polyvinyl butyral; and (d) a toner. Are recording materials of the specified type suitable for carrying out the dry development brought about by heating and are, inter alia, in the references given described. However, it is disadvantageous that the specified recording materials are often not used results in the desired black image tone or developed image, as also shown in the examples given below will.

In heat-sensitive recording materials, i.e. in recording materials, in which an image can be developed by image-wise heating, are known to be the most varied so-called toner is used. A typical such known toner for heat sensitive recording materials is e.g., phthalazinone, such as described in U.S. Patent Nos. 5,080,254 and 3,107,174.

However, the use of phthalazinones and other known toners often leads to adverse results, e.g. poorly developed image and an insufficiently black image tone. Are no or known toners of certain types light- and heat-sensitive recording materials When the exposed recording materials are heated, surprisingly none are visible Images developed.

The object of the invention is to provide a light-sensitive and heat-sensitive recording material that is used during exposure and the dry development brought about by heating a high-quality image with an advantageous, in particular improved, image black image tone.

Ί09846 / 1685

The invention is based on the surprising finding that the stated object can be achieved in a particularly advantageous manner can be solved in that the light and heat sensitive Precisely defined recording materials, so-called Aktivatoi'-Tonermittel Type.

The invention relates to a light and heat sensitive Recording material with at least one on a layer support applied layer with a G content at one for production an oxidation-reduction image, consisting of a silver salt oxidizing agent and a reducing agent Combination, a binder, and at least one activator-toner agent, which is characterized in that the Activator toner off

a) a 2-pyrazolin-5-one,

b) a cyclic imide of the general formula

^N - ^Z

Il

where mean:

R ~ die to complete a heterocyclic ring required atoms and

Z is a hydroxy radical or a hydrogen, silver, mercury, Potassium, sodium, lithium or gold atom, or

c) a quinazolinone
consists.

109846/1685

Recording materials have proven to be "particularly advantageous Proven according to the invention, which also enabled a catalyst for the generation of an oxidation-Keduktionsbildes Combination, particularly advantageously a photographic silver halide, contain.

In the light- and heat-sensitive recording materials according to the invention, 2-pyrazolin-5-ones, cyclic imides and / or quinazolinones of the most varied types are present. The degree of blackness of the image tone and other properties of the with the aid of a certain compound of the specified classes of compounds in a light- and heat-sensitive recording material achievable images can be determined with the help of a test, which is carried out as follows:

A dispersion, referred to below as dispersion A, is produced by mixing ^{the following components with one another for several hours at about 20 °} C. and atmospheric pressure in the Hegel using a ball mill:

Dispersion A:

Polyvinyl butyral 1.25 g

Behenic acid 3 »50 g

Silver behenate 3 »90 g

Sodium bromide 0.20 g

Acetone-toluene mixture 50.00 ml (1: 1 parts by volume)

A coating compound is then produced by mixing the dispersion obtained and the following components with one another :

Dispersion A 3.76 ml

Acetone with a content of 5% w / v 3.76 ml 2,2'-M * ethylene-bis (4-methyl-6-tert-butylphenol)

Acetone with a content of 0.013 fe / V 0.70 ml

Benzoxazolylidine-thiohydantoin-Sensibiliaitrungaferbetoff

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Acetone containing 10.0% w / v 1.20 ml of tetrahydrothiophene-1,1-dioxide

Acetone-toluene mixture 2.58 ml

(1: 1 parts by volume)

volatile, organic solvent 1.88 ml preferably / with an exnem content of 2. Ο5έ w / v Activator toner agent

The coating compound obtained is then applied to one off made of polyethylene coated paper applied in such a way that the layer thickness of the layer obtained is about 0.05 mm. To dry the formed Layer becomes the recording material obtained at about 20 to 40 ° C and atmospheric pressure for so long until the layer is practically solid.

The dried recording material is exposed imagewise to tungsten light for 5 seconds, after which the exposed recording material is developed by heating by placing it with the side opposite the layer side on a metal plate heated ^{to 100 ° C. for 5 to 60 seconds.}

Compounds suitable according to the invention as activator-toner agents cause in the specified way the generation of a visible image, its maximum density and image tone at least corresponds to that of a comparative sample image obtained using quinazolinone as an activator-toner agent was obtained.

The image tone and image density are assessed using a rating scale ranging from 0 to 10, with the grade 0 is assigned if a very poor image or no image was generated j and the grade 10 is assigned for "excellent", when produces a fully developed, high quality image

1Q98A67168S

became. Activator-toner agents which can be used in a particularly advantageous manner receive grades from 7 "to 10 according to the specified rating scale. For example, using the specified '. Tests as well as the specified rating scale according to the invention usable activator-toner agents succinimide and phthalimide Assessment grades of at least 7 and 3-phenyl-2-pyrazolin-5-one as well as 3-I'lethyl-2-pyrazolin-5-one evaluation grades of at least 8 to be assigned. The specified compounds are therefore preferred activator / toner agents. Will the specified Test done without using an activator-toner agent so is very weak or at all no developed image detectable.

In the light- and heat-sensitive recording material after A wide variety of activator-toner agents of the 2-pyrazolin-5-one type can be present in the invention. With these 2-pyrazolin-5-one compounds are those that have been found to be suitable in the specified test. Typical suitable such Active gate toner agents are, for example, 2-pyrazolin-5-one cLer general formula II

N W

wherein R ^ is a hydrogen atom, a lower alkyl ^r ait eg 1 to 4 carbon atoms, for example a methyl, ethyl, propyl or butyl, or an aryl group having preferably 6 to 12 carbon atoms such as a phenyl, tolyl or XyIyIrest means.

10 9846 / 168S

Typical suitable activator-toner agents of the 2-pyrazolin-5-one type are e.g.

3-methyl-2-pyrazolin-5-one,
3-ethyl-2-pyrazolin-5-one and 3-phenyl-2-pyrazolin-5-one.

The use of J-phenyl-2-pyrazolin-5-one has proven to be particularly advantageous and / or 3-methyl-2-pyrazolin-5-one proved.

In the light- and heat-sensitive recording material According to the invention, cyclic imides of various types can be present as activator / toner agents. With these cyclic Imides are those that have been found to be suitable in the specified test. According to the invention as an activator-toner agent suitable cyclic imides are those of the general formula I.

It

R ₂ 'FZ

where mean:

the ^{atoms required to} complete a heterocyclic ring, in particular an atom grouping of the i _f γ

Formula -NN ^- - in which R "'represents an aryl radical having preferably 6 to 12 carbon atoms, for example a phenyl, tolyl or xylyl radical, and in particular an atomic grouping of the formulas

109846/1685

R "

or

G H

in which R ¹ and R ″ alone are hydrogen atoms, or together those to complete a carbocyclic ring, for example one of the formula

represent required atoms, such a carbocyclic Ring through substituents that enhance the toner properties of the cyclic imide not adversely affect, can be substituted, for example by an alkyl radical with preferably 1 to 4 carbon atoms, or a hydroxyl or amino radical; and

Z is a hydroxyl radical or a hydrogen or metal atom, for example a silver, mercury, potassium, sodium, lithium or gold atom.

Typical such cyclic activator-toner agents useful Imides are e.g .:

N-hydroxysuccinimide, Succinimide,

ίϊ-hydroxyphthalimide, Phthalimide,

dös potassium salt of phthalimide, 4-cyclohexane-i, 2-dicarboximide, Glutarimide,

2,4-thiazolidinedione, the mercury of phthalimide,

1 09846/1688

the gold salt of phthalimide and the lithium salt of phthalimide, as well as further

Urazoles of the general formula III

R-

HN

= 0

wherein H, a hydrogen atom or an aryl radical with preferably 6 to 12 carbon atoms, for example a phenyl, tolyl or xylyl radical.

Typical suitable urazoles of this type are, for example, 1-phenyl urazole and i-phenyl-2-methylurazole.

Surprisingly, the specified urazoles are used as activator-toner agents less effective than the specified 2-pyrazolin-5-one activator toner agents and succinimide and phthalimide.

In the light and heat sensitive recording material after According to the invention, so-called quinazolinones can also be present as activator-toner agents. Surprisingly, however, it turned out that quinazolinones are less active than the specified 2-pyrazolin-5-ones or succinimide or phthalimide.

Quinazolinones which can be used according to the invention as activator-toner agents are compounds of the general formula IV

O
109846/1685

wherein R ^, a hydrogen atom, an alkyl radical with preferably 1 to 5 carbon atoms, "for example a methyl, ethyl, propyl, butyl or pentyl radical, or an aryl radical preferably having 6 to 12 carbon atoms, for example a phenyl, tolyl or xylyl radical.

The heat-developable photosensitive and heat-sensitive recording materials of the invention may be a developed one Provide image in "physical development, as described, for example, in U.S. Patent No. 3,457,075 will. Other suitable recording materials are described in U.S. Patents 3,4-29,706 and 3,152,904, for example. The recording materials described in the cited references generally consist of one Layer carrier that is provided with a light-stable organic silver salt oxidizing agent, an organic reducing agent and a photographic silver salt, in particular a silver halide, and are thus photographic and heat-sensitive recording materials. The light- and heat-sensitive recording materials are exposed to light to produce a visible image and then heated to moderately elevated temperatures, for example to temperatures of about 80 to 250 ° C, which is within a few seconds causes the image to develop.

Light- and heat-sensitive recording materials according to the invention have proven to be particularly advantageous, which, applied to a layer substrate, have the following components:

(a) one capable of generating an oxidation-reduction image Combination consisting of (I) silver behenate and (II) a phenolic reducing agent,

(b) photographic silver halide,

(c) polyvinyl butyral and

109846/1685

(d) an activator-toner agent consisting of succinimide and / or phthalimide.

Optionally, the light- and heat-sensitive recording materials can according to the invention additionally a strongly dielectric polar solvent, e.g. tetrahydrothiophene-1,1-dioxide, contain. Solvents of the specified type result in a denser black image.

In the light- and heat-sensitive recording materials According to the invention, the activator-toner agents can be present in a wide variety of concentrations. Usually lie they are present in concentrations such that about 1 to 3 moles of activator-toner agent per mole of photographic silver halide omitted. The optimal concentration depends on various Factors, e.g. the type of activator-toner used, the type of image desired, the type of components present in the recording material and those used Developing temperature.

The light- and heat-sensitive recording materials According to the invention, as already mentioned, a silver salt can be used as the oxidizing agent. With the silver salt used should it be one that is lightfast and does not turn dark when exposed to light to avoid detrimental destruction of the developed image. As a particularly advantageous compound class of silver salts such organic acids have been found, especially the water-insoluble silver salts of long-chain fatty acids, that are resistant to light. Typical suitable such silver salts are, for example, silver behenate, silver stearate, Silver oleate, silver laurate, cilber hydroxystearate, silver caprate, Silver myristate and silver palmitate. Silver benzoate, silver phthalazinone, Silver benzotriazole, silver saccharin, silver - ^ -'- ji-octade-

109846/1685

cycloxydiphenyl-4-carboxylic acid, silver aminobenzoate, silver acetamido "benzoate, Silver furoate, silver camphorate, silver p-phenylbenzoate, Silver phenyl acetate, silver salicylate, silver butyrate, silver terephthalate, silver phthalate, silver acetate and acid silver phthalate.

Suitable oxidizing agents are also those in which it are not silver salts, e.g. zinc oxide, gold stearate, mercury behenate and gold (III) behenate.

Combinations of the specified oxidizing agents can also be used.

In the light- and heat-sensitive recording materials According to the invention, organic reducing agents of the most varied types can also be present in combination with the specified oxidizing agents are capable of producing viable images. These reducing agents act they are usually silver halide developing agents. Typical suitable silver halide developing agents or organic reducing agents are e.g. polyhydroxybenzenes, e.g. hydroquinone developer compounds, e.g. hydroquinone, alkyl-substituted hydroquinones, for example tert-butyl hydroquinone, Methylhydroquinone, 2,5-Mmethylhydroquinone and 2,6-dimethylhydroquinone; Catechins and pyrogallol; halogen-substituted Hydroquinones such as chlorohydroquinone and dichlorohydroquinone; alkoxy substituted hydroquinones, e.g., methoxy hydroquinone and ethoxyhydroquinone; Methylhydroxy naphthaline also phenymiamine developer compounds; Methyl gallate; Aminophenol developing agents such as 2,4-diaminophenols and methylaminophenols; Ascorbic acid developer compounds, e.g. ascorbic acid, ascorbic acid ketals and ascorbic acid derivatives, e.g., those of the type described in U.S. Patent 3,337,34-2; also hydroxylamine developer compounds,

109846/1685

e.g. N, N-Di (2-ethoxyethyl) hydroxylaminej 3-pyrazolidone developer compounds, e.g. 1-phenyl-3-pyrazolidone and 4-methyl-4-hydroxymethyl-1-phenyl-3-pyrazolidone, for example those of the type described in British Patent Specification 930 572; further Hydroxytetronic acid and hydroxytetronimide developer compounds. Combinations of the specified ones can also be used Reducing agent.

The light- and heat-sensitive recording materials According to the invention, as already mentioned, preferably contain photographic salts, in particular photographic salts Silver salts. Typical suitable photographic silver salts are, for example, silver chloride, silver bromide, silver bromoiodide, silver chlorobromoiodide and mixtures thereof. The present Silver halides can be coarse-grained or fine-grained, the use of very fine-grained emulsions as has proven particularly beneficial.

For the production of the recording materials according to the invention Usable emulsions containing the specified photographic silver halides can be of a wide variety customary known processes. So it can be, for example, emulsions that after irradiation or Double jet precipitation process established; are e.g. Lippmann emulsions, ammoniacal emulsions or emulsions ripened with thiocyanates or thioethers, as described, for example, in U.S. Patents 2,222,264-3 320 069 and 3 271 157. With the silfeer halide emulsions it can also be those which have the latent image predominantly on the surface of the silver halide grains form, or to form emulsions of the so-called internal grain type, which form the latent image predominantly in the interior of the silver halide grains, such as those in U.S. Patent 2 592 250, 3 206 313, 3 367 778 and 3 44? 927. Mixtures of emulsions of the surface and inner grain type can also be used, such as those in the USA patent

109846/1685

script 2 996 382 ". Can also be used negative emulsions or direct positive silver halide emulsions, such as these e.g. in U.S. Patents 2 184-013, 2 541 4-72, 3 36? 778, 2 563 785, 2 4-56 953 and 2 861 885, as well as in British patent specification? 23 019 and the French patent 1,520,871. The silver halide emulsion used can also be a hegular grain emulsion, such as that used e.g. in "Journal of Photographic Science", Vol. 12, No. 5 »Sept./ Oct. 1964, pages 24-2 to 251.

For the production of the light- and heat-sensitive recording materials Silver halide emulsions used in the invention can also be unwashed or removed soluble salts. The washing to remove the soluble salts can be carried out in such a way that the emulsion is gelled by cooling and then leached, or by the so-called coagulation washing method.

For the production of the recording materials according to the invention Usable silver halide emulsions can be sensitized with the help of chemical sensitizers, e.g. with the help of reducing agents, silver, selenium or tellurium compounds, gold, platinum or palladium compounds, or with the help of combinations of such sensitizers. Typical suitable such sensitization procedures will be e.g. in U.S. Patents 1 623 4-99, 2 399 083, 5 297 44-7 and 3 297 446.

For the production of the recording materials according to the invention Silver halide emulsions which can be used can also be protected from fogging during storage be stabilized against loss of sensitivity. Typical suitable antifoggants and stabilizers that can be used alone or in combination with one another

09846/1685

- Ib -

Bind, are e.g. thiazolium salts, azaindenes, mercury salts, e.g., those of the type described in U.S. Patent 2,728,663, urazoles, sulfocatechols, oximes, e.g. of the type described in British patent specification 62 $ 448, nitrone, ITitroindazole, polyvalent metal salts, e.g. Such as those of the type described in U.S. Patent 2,839,405 and platinum, palladium and gold salts such as those that described in U.S. Patents 2,566,263 and 2,597,915 " Type.

In the light and heat sensitive recording materials according to the invention, the most varied of customary known colloids can be present. With such colloids that as a binder in various layers of the recording material B. can be present, it is usually a question of hydrophobic substances, but hydrophilic substances can also be used. These binding agents can be "transparent" or form translucent layers and from both naturally occurring and synthetically produced Connections exist. Typical substances suitable as binders are e.g. naturally occurring proteins, for example gelatin, gelatin derivatives, cellulose derivatives and polysaccharides, for example dextran and gum arabic, and synthetic produced polymers, e.g. water-soluble polyvinyl compounds, such as polyvinylpyrrolidone and Acrylamide polymers have also proven to be suitable synthetic polymers of other types, e.g. dispersed vinyl compounds, e.g. those in latex form, in particular those that affect the dimensional stability of the recording materials raise. Typical suitable synthetic polymers of this type are described, for example, in U.S. Patents 3,142,586, 3,193,386, 3,062,674, 3,220,844, 3,287,289, and 3,411,911.

Such polymers which can be used are, for example, water-insoluble polymers of alkyl acrylates and methacrylates, acrylic acid

109846/1685

re, sulfoalkyl acrylates or methacrylates, and those which have groups suitable for the formation of cross-links that facilitate curing and solidification, as well as those with recurring sulfobetaine units of the type described in Canadian patent 77 ¹ I-054- ".

Polyvinyl butyral, cellulose acetate butyrate, polymethyl methacrylate, polyvinylpyrrolidone, ethyl cellulose, polystyrene, polyvinyl chloride, chlorinated rubbers, polyisobutylene, polyisobutylene, mixed-vinyl butadiene-vinyl acetate, vinyl chloride-vinyl chloride copolymers, vinyl chloride-vinyl chloride, have proven particularly advantageous as high molecular weight substances and resins and maleic acid, polyvinyl alcohol and high molecular weight ethylene oxide polymers, for example ethylene oxide polymers with an average molecular weight of about Λ, 000 to 3,000,000 or even higher.

The light- and heat-sensitive recording materials According to the invention, the most varied of customary known layer supports can be used. Typical suitable substrates are e.g. foils made of cellulose nitrate, cellulose esters, polyvinyl acetals, Polystyrene, polyethylene terephthalate, polycarbonates and resinous substances of the corresponding type, as well as Laminates made of glass, paper and metals. Flexible layer supports are used in the Hegel, in particular layer supports made of paper, which is optionally partially acetylated or provided with a layer of barite and / or a ^ -olefin polymer are, in a particularly advantageous manner with a polymer layer of an ok-olefin having 2 to 10 carbon atoms, for. B. made of polyethylene, polypropylene or ethylene-butene copolymers,

109846/1685

In the light and heat sensitive recording materials curable layers present according to the invention can be coated with a wide variety of customary known organic or inorganic hardeners. Typical suitable curing agents used alone or in combination which can be used with each other are e.g. aldehydes and blocked aldehydes, ketones, carboxyl and carboxylic acid derivatives, Sulfonate esters, sulfonyl halides and vinyl sulfonyl ethers, active halogen compounds, epoxy compounds, aziridines, active olefins, isocyanates, carbodiimides, curing agents with mixed functional groups and polymeric curing agents, e.g., oxidized polysaccharides, e.g., dialdehyde starch and oxyguargum.

The light- and heat-sensitive recording materials according to the invention can be conventionally known antistatic or have electrically conductive layers. Soluble salts such as chlorides can be present in such layers or nitrates, furthermore it can be layers of vapor-deposited metals or of ionic polymers, such as those described in U.S. Patents 2,861,056 and 3,206 3 ^ 2, or they may be layers act from insoluble inorganic salts, such as these z. As described in U.S. Patent 3 4-28 4 ^ 1. The recording materials according to the invention can also Atrial protective layers and the substances that build them up, e.g. dyes suitable as antihalation agents.

The layers present in the light- and heat-sensitive recording materials according to the invention may further contain conventionally known plasticizers and lubricants. Typical suitable such plasticizers and lubricants are, for example polyalcohols, e.g., glycerin and diols as described, for example _e in US Patent 2,960,404 ·

10 3 846/1685

are as described in example ₁ of British Patent Specification 955 061 also fatty acids or fatty acid ester, as described in the US Patents 2,588,765 and 3,121,060, for example, silicone resins and Z.

The ones in the light and. thermosensitive recording materials Layers according to the invention may further contain conventionally known surface-active agents. Typical suitable such surfactants are e.g. saponin, anionic compounds e.g. they are described, for example, in US Pat. No. 2,600,831, and amphoteric compounds such as those described, for example, in US Pat 3 133 816 as well as addition compounds from glycidol and an alkylphenol, as they are, for. As described in British Patent 1,022,878.

If necessary, in the light and heat sensitive Recording materials according to the invention are conventional and known Matting agents are present, e.g. starch, titanium dioxide, zinc oxide, silicon dioxide and spherical polymer solid particles, as described, for example, in U.S. Patents 2,992,101 and 2,701,245.

The light and heat sensitive recording materials according to the invention may further contain conventionally known brightening agents, for example stilbenes, triazines, oxazoles and coumarin brightening agents. It is also possible to use water-soluble brightening agents, such as those in the German patent specification 972 067 and U.S. Patent 2,933,390, as well as dispersions of lightening agents, such as those described in, for example the German patent specification 1 150 274, in the USA patent specification 3 406 070 and in the French patent specification 1 530 244 should be trimmed. '

109846/1686

Those present in the recording materials according to the invention Layers, including those sensitive to light and xväriae Layers can also contain light-absorbing substances and filter dyes, for example those in the United States patents 3,253,921, 2,274,782, 2,527,583, and 2,956,879 Type. Optionally, such dyes can be stained, for example in the manner described in the United States patent 3,282,699.

Those present in the recording materials according to the invention light- and heat-sensitive layers can be applied to the support by a wide variety of customary known processes applied, e.g. with the help of so-called immersion coating, Air knife coating, drop curtain coating or using extrusion coating carried out by hoppers, such as this is noted, for example, in U.S. Patent 2,681,294. Optionally, two or more layers can be used at the same time can be applied, for example according to those described in US Pat. No. 2,761,791 and British Pat. No. 857,095 Procedure.

The photographic silver halide can optionally be formed in situ in the light- and heat-sensitive recording materials according to the invention, for example by the process described in US Pat. No. 3,457,075. For example, a dilute solution of a hydrohalic acid, e.g. B. dilute hydrochloric acid, on the surface a: "On a layer support, a thin layer containing an organic silver salt, eg silver behenate, is applied and then, if necessary, the solvent is removed. In this way, the entire surface of the layer containing the organic silver salt silver halide formed in situ,

Dnr photograpiiir.chc oil berli ^ lcv-riii.'l k-uiu J ¹ Uf? den air- Ox; ydnt i-iri'-iiiLtto L \ ^r (M ^> v <-t - »- ⁾ (.: 1; rn or; ¹ ; · =: · i. <·. (· 'umi ^ i! .no pnnl / .en,. "..! 3. Si] -: .ι ·, ι. n.'ib pif r> · '!. ι'! ':' · leMi'i-it; , ■ '(M> 1 S Ui, wiv; \ l < ^: ii, iii'VOi ¹ die

BATH ORIGINAL iU9846 / 168S

Coating of the substrate takes place. This procedure too is described in referenced U.S. Patent 3,457,075 ". For example, a hydrohalic acid, e.g. Hydrochloric acid or hydrobromic acid, in a suitable reaction medium be mixed with an organic silver salt. A suspension can be used to form the silver halide the organic silver salt with a halide salt which has a higher solubility than the organic silver salt, be moved. The reaction medium is water and other solutions that do not affect the specified reaction, proved suitable.

The recording materials according to the invention can also to expand the range of sensitization spectral sensitizing dyes be incorporated. For example, an additional spectral sensitization can be brought about by that the silver halide present with a sensitizing dye in the form of a solution in an organic solvent or treated in the form of a dispersion as described, for example, in British Patent 1,154,781. To the The sensitizing dyes can achieve optimal results incorporated into the emulsions either at the end of the process or at an earlier stage during emulsion preparation will.

Typical sensitizing dyes suitable for the spectral sensitization of silver halide are described, for example, in the United States patents 2,526,632, 2,503,776, 2,493,748 and 3,394,486 described. Typical suitable spectral sensitizers are, for example, cyanines, merocyanines, complex trinuclear or tetranuclear Merocyanines, complex trinuclear or tetranuclear cyanines, holopolar cyanines, styryls, hemicyanines, e.g. enamine hemicyanines, Oxonols and hemioxonols.

The dyes belonging to the cyanine class can contain a wide variety of basic cores, e.g.

109846/1686

Thiazolines, oxazolines, pyrrolines, pyridines, oxazoles, thiazoles, Selenazoles and imidazoles. These nuclei can be substituted pure, e.g. by alkyl, alkylene, hydroxyalkyl, sulfoalkyl, carboxyalkyl, Aminoalkyl or enamine radicals, and they can also be fused onto carbocyclic or heterocyclic ring systems, which can be either unsubstituted or substituted by halogen atoms, phenyl, alkyl, haloalkyl, cyano or alkoxy radicals. With the specified dyes it can are symmetrical or asymmetrical dyes whose methine or polymethine chain is replaced by alkyl, phenyl, enamine or heterocyclic radicals can be substituted.

The specified merocyanine dyes can have the specified basic nuclei as well as a wide variety of acidic nuclei, for example thiohydantoins, rhodanines, oxazolidendiones, thiazolidendiones, barbituric acids, thiazolinones and malonitrile. These acidic nuclei may be substituted by alkyl, alkylene, phenyl, carboxyalkyl, sulfoalkyl, hydroxyalkyl, alkoxyalkyl or ₅ alkylamino or heterocyclic nuclei.

If appropriate, combinations of the specified dyes can also be used. Furthermore, supersensitive additives that do not absorb visible light may be present, e.g. B. ascorbic acid derivatives, azaindenes, cadmium salts and organic sulfonic acids, such as S ₀ B * in the US patents

2,933,390 and 2,937,089.

The indicated sensitizing dyes and additives of other types can be added in the form of aqueous solutions or solutions in suitable organic solvents. These compounds can be added according to the most varied of customary "known processes," aB according to the US Patents 2,912 3 ^ 3, 3 342 605 ₁ 2 9% 28?

3 425 835 described procedure »

19SS4I / 1SIS

The dyes indicated can be present in the display materials according to the invention in the most varied of concentrations. The optimum concentrations are determined by a wide variety of factors, for example the desired range of spectral sensitivity, the type of components present in the recording material, the type of image desired and the development and processing conditions used. In general, the appropriate sensitizing dyes are in the light- and heat-sensitive recording material according to the invention in a concentration of about 0.5 to 10 mg / m ^ support area (0.05 to 1 mg / sq.ft.) , suitably in a concentration of about 1 mg / m support surface (O, ¹ mg / so.ft '.) before.

In the light and heat sensitive recording materials According to the invention, other activator-toners than those specified can also be used in combination with the specified components are present. In the Hegel the use of organic toning agents with a heterocyclic Hing, which contains at least two heteroatoms, of which at least one is a nitrogen atom, has been found to be expedient, as described, for example, in U.S. Patent 3,080,254 will. Typical toner media of the specified T; fps are e.g., phthalazinone, phthalic anhydride, 2-acetylphthalazinone and 2-phthalyl-phthRlazinone. Other such toning agents are described, for example, in U.S. Patent 3,444-6,648.

la the light- and heat-sensitive recording materials iKCi of the invention is particularly advantageous - i. "ter V / eise ols -toduktio-isruittel a bis-naphthol of the fol ^ ca-lon general ι · οL'Kif-l verv.'encTn ·: r

H) 9 8 A 6/1 fc

BAD OfUGJNAL

where mean:

E ₁ - and R ^ hydrogen atoms, alkoxy radicals with, for example, 1 to 5 carbon atoms, for example ilethoxy, xthoxy or propoxy radicals, alkyl radicals with 1 to 3 carbon atoms, for example methyl, ethyl. Or propyl radicals, nitro radicals, amino radicals or azonium radicals of the formula -HsN, and

η = 0 or 1.

Typical suitable such bis-naphthol reducing agents are for example:

6,6'-dibromo-2,2'-dihydroxy-1,1'-binaphthol, 6,6'-dinitro-2, 2 * -dihydroxy-1,1'-binaphthol, bis-2-h.ydroxynaphth. yl-1-methane and 2,2'-dihydroxy-1,1'-binaphthol.

As already mentioned, it is assumed that the borrowed and heat-sensitive recording material according to the invention present photographic silver halide those for image formation leading reaction that takes place when the combination of silver salt oxidizing agent and reducing agent is heated, catalyzed. The concentration of photographic silver halide present may vary depending on the type of image desired, the silver salt oxidizing agent used and the reducing agent used, the exposure time and intensity, the type of components present in the recording material and the like can be very different. Usually is the photographic silver halide in the light and heat sensitive Recording material according to the invention in a concentration of about 0.01 to 10 mol%, based on Silver salt oxidizing agent.

The concentration of reducing agent can also vary greatly be. The optimal concentration depends on various factors, such as the type of in the recording material

109846/1685

present silver salt oxidizing agent, reducing agent and the other components, as well as the type of the desired image. As a rule, the use of stoichiometric amounts of reducing agent and silver salt oxidizing agent has proven to be expedient. The reducing agent and the silver salt oxidizing agent are therefore generally present in a molar ratio of about 1: 1. As a rule, the concentration of reducing agent and oxidizing agent is approximately 55 "to ^{1,100 mg / m 2 of} support surface (5 Ms 100 mg / sq.ft.).

For the production of the recording materials according to the invention Certain coating compositions are made by mixing the specified components with the help of suitable, customary known mixing devices can be produced. The photographic Silver halide is preferably prepared in situ by admixing a halide ion donating compound with the indicated silver salt oxidizing agents, as described, for example, in the cited U.S. Patent No. 3,457,075.

The latent image produced in the light- and heat-sensitive recording material according to the invention on exposure to actinic radiation can be developed by simply heating the recording material. Heating is continued until the desired visible image is developed. The heating temperatures may be very different and are from about 70 to 25O ⁰ C, usually about 80 to 150 ⁰ O. By increasing or decreasing the heating time, higher or lower temperatures are also applicable within the specified range. A fully developed and stable image is usually obtained within about 1 to 60 seconds, for example within about 1 to 30 seconds.

Development usually takes place under normal pressure and humidity conditions. If necessary, there are also pressures and moisture levels outside of normal atmospheric

109846/1685

Area applicable, but has become the use of normal atmospheric Conditions proved particularly beneficial.

The light- and heat-sensitive recording material according to the invention can optionally be constructed in such a way that the specified catalyst, ie the photographic silver halide, is arranged in one layer and the other components are arranged in other layers of the recording material. Thus, for example, consist recording material of the invention comprising a layer support, on which a photographic W silver halide-containing layer, and means disposed adjacent to the latter, the group capable of generating an oxidation-reduction image combination and layer containing the specified activator-toning agents are applied.

The heating can take place in a wide variety of customary known ways. For example, the exposed recording material be brought into contact with a simple heated plate, e.g. iron plate.

The light and heat sensitive recording materials according to the invention, in addition to the specified yet, other known principles for such purposes supply commonly used *, as described in British Patent 1,161,777 and US Patent No. 3,152 904- eg, contain.

The following examples are intended to explain the invention in more detail.

example 1

A dispersion corresponding to the indicated dispersion A was used by mixing the specified components in a ball mill for 16 hours. Using ar The resulting dispersion A was then a coating measure? »

109846/1685

made by mixing the following components together became:

Dispersion A 3.76 ml

Acetone with a content of 5% w / v 3 »76 ml 2,2 * -methylene-bisC ^ -methyl-ö-tertiary-butylphenol)

Acetone containing 0.01% w / v 0.70 ml benzoxazolylidine thiohydantoin sensitizing dye

Acetone containing 10.0% w / v 1.20 ml Tetrahydrothiophene-1 "1-dioxide

Methanol containing 2.0% w / v 1.88 ml of 3-phenyl-2-pyrazolin-5-one

Acetone-toluene mixture 2.38 ml

(1: 1 parts by volume)

The resulting coating mass was "at about 20 ° G on a Layer support, which consisted of paper coated with polyethylene, applied in such a way that a layer with a layer thickness of about 0.05 mm measured in the moist state was obtained. The obtained layer was then allowed to dry under atmospheric conditions.

The light- and heat-sensitive recording material obtained was then exposed sensitometrically to the light of a tungsten lamp for 5 seconds. The exposed recording material was taken for 30 seconds with a heated to a temperature of 10O ⁰ C metal plate in contact. A fully developed image with a neutral black image tone was obtained. Using the rating scale given for image tone and density, which ranges from 0 for very poor or no image at all to 10 for an excellent developed image was assigned to the image received a review score of eighth

109846/1685

For comparison purposes, it was done in the manner indicated, however with the exception that 3 "hienyl-2- pyraaolin-5-one is omitted a comparative sample was prepared, exposed and developed. This comparison sample had to be rated with O, since no image was developed "

Example 2

The procedure described in Example 1 was repeated with the exception that instead of 3-phenyl-2-pyrazolin-5-one 3-methyl-2-pyrai2olin-5-one used as activator-toner agent became. During development, the recording material obtained gave an image to which evaluation grade 8 could be assigned was »

Example 3

The procedure described in Example 1 was repeated with the exception that instead of 3-phenyl-2-pyrazolin-5-one succinimide was used as an activator-toner agent. The recording material obtained gave in the development an image that was rated at 7.

Example M-

The procedure described in Example 1 was repeated with the exception that phthalimide was used as the activator-toner agent in place of 3-rienyl-2-pyrazolin-5-one. The recording material obtained gave an image on development which was to be evaluated with the Fote 7.

109846/1685

Example 5

The procedure described in Example 1 was repeated with the exception that ^{quinazolinone was used as the activator-toner agent instead of 5-I>} henyl-2-pyrazolin-5-one. During development, the recording material obtained gave an image which was to be given a grade of 4.

Example 6

A dispersion designated as dispersion B was obtained by mixing the following components in one for 18 hours Ball mill manufactured:

109846/1685

Dispersion B:

Silver behenate 23.3 g

Behenic acid 26.0 g

Polyvinyl butyral 1.25 g

Sodium bromide 1.31 g

Acetone-toluene mixture 500.0 ml (1: 1 parts by volume)

Using the dispersion B obtained a coating composition ψ by intimately mixing the following com- ponents prepared:

Dispersion B

4-, 4'-isopropylidenediphenol (5% by weight in acetone)

Phthalimide

(1 wt -.% In acetone)

Sensitizing dye I * (0.01 wt. 70 in acetone)

* 3-ethyl-5- (3-ethyl-2 (3H) -benzothiazylideneisopropylidene) -2-thio-2,4- (3 _s 5) -oxazole dione

The coating compound obtained was applied to a substrate made of paper provided with a resin layer in the form of a layer with a layer thickness of 0.1 mm measured in the wet state. The layer obtained was allowed to dry under atmospheric conditions. The light- and heat-sensitive recording material obtained was exposed sensitometrically to a contact copying device for 0.5 seconds using a step wedge. The exposed record was brought into contact with a hot Metsllfeloek ύοϊι _{ot ^ a for about `` seconds or so}

2.0 ml 2.0 ml 2.0 ml 0.5 ml

A visible line image with 8 visible developed steps was obtained. The image obtained was gray-black Image tone.

Example 7

Using the indicated dispersion B, a coating was made prepared by intimately mixing the following components:.

Dispersion B of the 225 nu in Example 9. written 2 composition

2 _> 2'-methylenebis (4-ethyl-6-t-butyl ~ 58 ml phenol) (5% by weight in acetone)

Succinimide 45 ml

(1 wt .- # in acetone)

Sensitizing dye I of the type given in 3 »8 ml of Example 9
(0.01% by weight in acetone)

Acetone-toluene mixture 68 ml

(1: 1 parts by volume)

The Beschichtufigsmasse obtained was coated on a coated out with a resin! Paper existing substrate in the form of a layer with a measured in the moist state layer thickness of O ₁ ^"1 mm. The layer obtained was under atmospheric conditions allowed to dry. The light obtained and thermosensitive recording material was exposed in a contact copying apparatus for 0.5 seconds using a step wedge tungsten light sensitometry. The exposed recording material was brought about seconds with a hot metal block of about 135 ⁰ O in Eontakt.

109846/1885

It became a visible line image with 10 visible levels obtain. The image obtained had a brown-gray image tone and a brown-yellow image background.

Example 8

Using the indicated dispersion B, a coating composition produced by intimately mixing the following components:

Dispersion B of the 225 ml in Example 9 written composition

2,2'-methylene-bis ~ (4-methyl ~ 6-t- 58 ml butyl-phenol)

(5% by weight in acetone)

Succinimide 4-5 ml

(1% by weight in acetone)

Sensitizing dye I of the 5? Yps given in 5.8 ml of Example 9
(0.01% by weight in acetone)

Aeeton-iöluolitffiisch 68 ial

(1ί1 full parts)

The coating composition obtained was applied to a substrate made of paper provided with a resin layer in the form of a layer with a layer thickness of 0.1 mm, measured in the moist state. The layer obtained from Me was allowed to dry under atmospheric conditions. The resulting photosensitive and heat-sensitive recording material was exposed sensitometrically in a coitact copier for 0.5 seconds using a stepping device. * The exposed recording material was cracked for about 10 seconds with a hot metal block of about 135 ° G.

109846/1685

A visible line image with 10 visible levels was obtained. The image tone of the image obtained was dark brown and the background of the picture is brown and yellow.

Example 9

Using the indicated dispersion B, a coating race was made produced by intimately mixing the following components:

Dispersion B of the 2.0 ml in Example 9

described composition

2,2'-thiobis (4-methyl-6-t-butyl-phenol) 2.0 ml (5% by weight in acetone)

Phthalimide 2.0 ml

(1% by weight in acetone)

Sensitizing dye II * 0.5 ml

(0.01 wt .- # in methanol)

* 3-Carboxymethyl-5- / 0-methyl-2 (3) -thiazolinylidene) -isopropylidene-7rhodanine

The obtained dope was coated on a support made of resin-coated paper in iPorm of one layer with one measured in the wet state Layer thickness of 0.1 mm applied. The resulting layer was allowed to dry under atmospheric conditions. That obtained light- and heat-sensitive recording material was sensitometric on a contact copier for 0.5 seconds using a step wedge exposed. The exposed recording material was about Seconds with a hot metal block at about 135 ° C in Brought in contact.

109846/1685

A visible line image with 9 visible levels was obtained. The image obtained had a green-brown image tone and the image background was gray-green.

Example 10

Using the indicated dispersion B, a coating was made smasse by intimately mixing the following components manufactured:

Dispersion B of the 2.0 ml in Example 9

described composition

4,4'-dihydroxy-3,3'-dimethyl-biphenyl 2.0 ml (5 wt .- ^ 6 in acetone)

Succinimide 2.0 ml

(1% by weight in acetone)

Sensitizing dye I of the 0.5 ml Tj ⁷ PS given in Example 9 (0.01% by weight in acetone)

The coating composition obtained was made of one with one Resin-coated paper existing base applied in the form of a layer with a layer thickness of 0.1 mm measured in the moist state. The layer obtained was allowed to dry under atmospheric conditions. The light- and heat-sensitive recording material obtained was sensitometric in a contact copier for 0.5 seconds using a step wedge tungsten light exposed »The exposed recording material was about Seconds with a hot metal block at about 135 ° G in Brought in contact. An advantageous visible line image was obtained.

109346/1685

Example 11

The procedure described in Example 10 was repeated, with the exception that instead of 4-, 4- ¹ -dihydroxy ~ 3 ₎ 3 ^l -di- «methylbiphenyl ^ -, V-dihydroxybiphenyl was used. Accordingly, favorable results have been obtained.

Example 12

The procedure described in Example 1 was repeated with the exception that etrahydrothiophene-1,1-dioxide was omitted became. Exposure and development were carried out according to the method described in Example 1. It became a picture obtained with a neutral (black) image tone, the density of which was slightly lower than that in Example 1 obtained image.

Example 15

This example shows the production of a thermograph Recording material without the use of photographic Silver halide.

There was prepared a labeled Dispersion C Dispersion by mixing the following components were 16 "hours mixed together in a ball mill at about 20 ⁰ G and atmospheric pressure:

Dispersion C

Polyvinyl butyral 1.25 g

Behenic acid 3 »50 g

silver behenate 3.90 g

Acetone-toluene mixture 50.0 ml (1: 1 parts by volume)

109846/1685

-36- 212095b

Using the obtained dispersion C, a coating material was made made by mixing the following components:

Dispersion C 4.0 ml

e-t- 5.8 ml

butylphenol)

(5% by weight in acetone)

5-phenyl-2-pyrazolin-5-one 1.9 ml

(2% by weight in methanol)

The coating composition obtained was applied to a substrate made of paper provided with a polyethylene layer in the form of a layer with a layer thickness of about 0.05 mm. The layer obtained was dried by allowing the coated substrate to ^{lie at about 40 °} C. and atmospheric pressure until the layer was practically completely solidified. The recording material obtained was heated by applying the opposite side to the layer side to a metal plate heated to 160 ° C. for 20 seconds. The image obtained had a warm black image tone and a maximum density of 1.58.

Example 14 (comparative example)

The procedure described in Example 15 was repeated, with the exception that instead of 1.9 ml of methanol containing 5-kienyl-2-pyrazolin-5-one in one concentration of 2 wt .-% this time 1.9 ml.1 acetone were used. The image obtained had a warm black image tone as well a density of 0.79 on

Example 15

The procedure described in Example 15 was repeated except that the recording material was 15 seconds

109 8 46/11585

was heated at 140 ^{0 C long.} The image obtained had a warm black tone and a density of 1.05.

Example 16 (liability example)

The process described in Example 14 was repeated with the exception that the recording material was ^{heated at 140 °} C. for 15 seconds. The image obtained had a warm black tone and a density of 0.23.

Example 17 (comparative example)

The procedure described in Example 1 was repeated with the exception that instead of J-rienyl ^ -pyrazoline - ^ - on used as activator-toner agent N-methyl-phthalazinone became. Exposure and development were carried out according to the method described in Example 1. It didn't become a visible one Image received.

109846/1685

Claims (11)

- 58 - Claims ! SXSS SS ZS - w SS - SS SC SSSS SC SS SS SS SS S Χΐ SS SU SS SS SSSSSS SX SX SS Light- and heat-sensitive recording material with at least one applied to a layer support Layer containing one for producing an oxidation-reduction image capable of consisting of a silver salt oxidizing agent and a reducing agent Combination, a binder, and also at least one activator-toner agent, characterized in that at least one of the activator / toner agents present a) a 2-pyrazolin-5-one, b) a cyclic imide of the general formula It N - Z It where mean: R ₂ the atoms required to complete a heterocyclic ring and Z is a hydroxy radical or a hydrogen, silver, mercury, potassium, sodium, lithium or gold atom, or c) a quinazolinone
consists. 09846/1685 2. Light- and heat-sensitive recording material according to claim ^Λ _%, characterized in that the activator-toner agent consists of a 2-pyrazolin-5-one of the general formula • N wherein R ^ is a hydrogen atom, an alkyl radical with 1 to 4 carbon atoms or an aryl radical with 6 to 12 carbon atoms means consists. 3. Light- and heat-sensitive recording material after Claims Ί and 2, characterized in that the activator-toner agent consists of 3-rienyl-2-pyrazolin-5-one or 3-methyl-2-pyrazolin-5-one consists. 4. Light- and heat-sensitive recording material after Claim 1, characterized in that the activator-To nermittel consists of succinimide or phthalimide. 5. Light and heat sensitive recording material after Claim ^, characterized in that the activator To nermittel from a quinazolinone of the general formula wherein R ^ is a hydrogen atom, an alkyl radical with 1 to 5 carbon atoms or an aryl radical with 6 to 12 carbon atoms means exists. 109846 / 16R5 2120358 _ 40 - 6. Light- and heat-sensitive recording material according to Claims 1 to 5 »characterized in that it additionally contains photographic silver halide. 7. Light- and heat-sensitive recording material according to claims 1 to 6, characterized in that it (a) a combination of silver behenate and a phenolic reducing agent capable of generating an oscillation-reduction image, (b) pliot; © graphic silver halide, (c ) Contains polyvinyl butyral and (ά) an activator-toner agent consisting of succinimide, phthalimide, ^ -Fhenj 2-pyrazolin-5 ~ one or 3-hetnyl-2-pyrazolin-5 - one. 8. Light- and heat-sensitive recording material according to Claims 1 to 7? characterized in that it is additionally contains a highly dielectric polar solvent. 9. Light- and heat-sensitive »s recording material according to claim 8, characterized in that the strongly dielectric polar solvent consists of ü ^ rrsJiyarotiiiophen-i ₅ 1-di-03cyd. 10. Light and heat sensitive on drawing material according to claims 6 to S _5, characterized in that it contains about 1 to 3 moles of activator-toner agent per mole of photographic silver halide. 11. Light and heat sensitive recording material after Claims 1 to 5, characterized in that it is free of silver halide and 0.1 per mole of oxidizing agent Contains up to 3 moles of activator-toner. 109846 / 16P5