DE2237848A1 - PHOTOGRAPHIC RECORDING MATERIAL AND METHOD FOR CREATING PHOTOGRAPHIC IMAGES - Google Patents

Description

PATENT LAWYERS

DR.-ING. WOLFF, H. BARTELS, ⁸ ÜSK "" ~: ~ "7"

DR-BRANDES ₁ DR-INCHELd TELEPHONE: (0811) 293297 W * »

Dipl.-Phys. Wolff

Registration number. 123 393

EASTMAN KODAK COMPANY, 343 State Street, Rochester, New York State, United States of America

Photographic recording material and method for producing photographic images.

309807/1222

The invention relates to a photographic recording material consisting of a layer support and at least one applied thereon, which can be converted into a photosensitive layer by chemical treatment, an organoazide-containing, image-generating layer and a method for production photographic images using such a photographic material.

It is well known that photographic images can be used by dry or practically dry development can produce such recording materials which contain in a photosensitive layer a diazonium salt and a coupler compound which react with one another under alkaline conditions to form an azo dye. The structure and use of such photographic recording materials known as diazotype materials is described, for example, in the book by Kosar, Light-Sensitive Systems, John Wiley & Sons, Inc., New York, USA (1965), described in detail in Chapter 6 in particular. The usability of such recording materials is based on the fact that the photosensitive diazonium salts present are destroyed when they are exposed in an imagewise manner, and that a subsequent exposure Treatment with an alkaline developer, e.g. ammonia, causes a dye-forming reaction in the unexposed areas to produce a positive reproduction of the Original causes.

A disadvantage of the known photographic recording materials of the diazotype type, however, is that the background density of the materials increases when the same is stored. These Although the tendency can be reduced by the simultaneous use of an acidic inhibitor which prevents premature coupling, the use of such an inhibitor has in turn the disadvantage that this increases the speed of development of the

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terials delayed because the inhibitor must be neutralized before a coupling reaction can take place. In addition, that common known developing agents such as ammonia have toxic and / or harmful side effects.

It is also known, cf. B. the already quoted Buch von Kosar, pages 269-270, for the production of photographic images, photographic recording materials of the diazotype type to use, which contain diazosulfonates which, when exposed to light, form diazonium salts which couple in a normal manner can. These recording materials are so-called negative-working materials, since these are image fibers are generated in the exposed areas. The disadvantage of these recording materials is that they follow the Image formation can be stabilized by a wet treatment to remove any photosensitive components still present have to.

Finally, it is also known, for example from the USA patent 3,062,650 to use negative-working photographic recording materials for the production of images which based on the use of an organic azide and a dye former. These recording materials provide the image-appropriate exposure direct copy images. Even when using these materials, however, it is necessary after to remove the unreacted components by a washing process in order to prepare the background areas to stabilize the copying.

The object of the invention is to provide a silver-free photographic recording material which is suitable for producing stable images of excellent quality without the need for production the images require washing after image formation for the purpose of stabilization and that for development no toxic and / or harmful developer compounds are required.

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The invention was based on the knowledge that one to such photographic recording materials by using a Organoazides and a compound which delivers a triorganophosphine and from which a triorganophosphine can be set free by chemical treatment. It was found, that, by using such recording materials, stable images can be produced by the action of light and heat without it being necessary to wash them for the purpose of stabilization. The method of the invention enables hence the production of stable images on thermal photographic devices Ways.

The invention thus provides a photographic recording material consisting of a layer support and at least an applied thereon, which can be converted into a photosensitive layer by chemical treatment, an organoazide-containing, image-generating layer, which is characterized in that is that it contains a layer as an image-forming layer

(a) a complex of a transition metal and a triorganophosphine of the formula:

(Z) ₂ MX ₂

where mean:

Z a triorganophosphine, M is a cobalt or nickel cation and X is a monovalent anion,

(b) an organoazide and, if appropriate, also (c) a coupler which provides a dye with the organoazide and / or (d) has a binder for (a) and (b) and optionally (c),

The complexes of the given formula (Z) ₂ MX ₂ can be used

describe by the following structural formula:

• X ^s .

i ¹ Hi! 7/1 ? ? ?

The utility of the photographic recording materials according to the invention is thus based on the fact that they have at least one complex of a transition metal and a triorganophosphine contain, i.e. a so-called triorganophosphine-former, which releases a phosphine through e.g. alkaline treatment, e.g. a Triarylphosphine, which is one with the further azide present radiation-sensitive complex. The invention according to used Transition metal complexes are particularly advantageous because they contain 2 moles of triorganophosphine per mole of metal complex deliver. The radiation-sensitive complex is replicated set free the phosphine spontaneously in situ. Advantageously, recording materials are used which additionally a dye-forming agent such as a dye-forming coupler.

The use of transition metal complexes also allows the absorption of the image dye at longer wavelengths move towards, presumably due to an action between the dye molecule and the transition metal.

chemical, e.g.
The material activated by alkaline pretreatment provides photographic images directly by exposure to activating rays. It is not necessary to supply further developer compounds. The background areas of the images produced can be stabilized before being copied out by means of an easy-to-perform heat setting. Such a heat fixation can furthermore also be used to intensify or amplify the image generated. The term photographic image here includes a visible as well as a latent photographic image.

If a photographic recording material is used which does not contain a color coupler, this color coupler can be used according to the Exposure of the recording material are supplied by means of a coupler solution.

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If necessary, positive images can be produced in an advantageous manner using a recording material according to the invention be produced by thermophotographic means, namely that the material is first exposed to heat imagewise which is followed by activating radiation, i.e. radiation that is sensitive to the phosphine-azide complex, is fully exposed. Heat fixation is not required. However, the material can be used for image intensification or Image intensification can be heated if so desired. Finally, using photographic recording materials according to the invention, lithographic printing surfaces can be produced in that hydrophilic polymeric azides and / or hydrophilic polymeric couplers can be used.

The invention thus further provides a process for producing photographic images using a Photographic recording material according to the invention, which is characterized in that the material is first a subjected to chemical, in particular alkaline, pretreatment, then exposed appropriately to the image, treated with a color coupler and optionally heated for the purpose of stabilization.

The invention also relates to a process for producing photographic images using a recording material according to the invention, which is characterized in that that the material is first subjected to a chemical, in particular alkaline, pretreatment and then heated imagewise and finally fully exposed to activating radiation to form an image in the unheated areas.

The complexes of transition metal and triorganophosphine used to produce the recording materials according to the invention are stable at non-basic pH values.

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■ * ■? ■

Under an activating radiation or radiation that to which phosphine-azide complexes are sensitive are electromagnetic rays, including X-rays, to understand ultraviolet rays and the rays of visible light.

The phosphine azide complexes that can form from the transition metal complexes are chemical ones Complexes which, when exposed to activating radiation, yield compounds which react with color couplers to produce Image dye elf react.

For the production of the photographic recording materials According to the invention, a wide variety of triorganophosphines, i.e. phosphines with 3 organic substituents, can be used. In general, all the triorganophosphines can be used, which together with an organoazide make a radiation-sensitive one Form complex. The fact whether a trioganophosphine is suitable for forming a complex with an organoazide can be determined determined by a simple experiment. This experiment can be carried out as follows:

A triorganophosphine is used together with an organoazide, such as are usually used in the production of photographic recording materials of the diazotype type, e.g., with p-morpholinophenyl azide and / or 4-azidobenzenesulfonamide, normally in equivalent molar proportions or in a small excess of phosphine and a ß-naphthol color coupler, e.g., 2-naphthol or 2,3-naphthalene diol to produce a Dissolved solution, which is then applied to a layer support and dried. The layer is then activated with Exposing radiation, i.e. rays to which the complex is sensitive, to produce a photographic image, that is visible or by amplification into a visible image

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can be transferred. If the image is, if it is visible, the hue and / or intensity of the photographic one Different image which is formed when a corresponding recording material with only the azide and the coupler, i. without the phosphine produced and exposed in the same way, then that is to carry out the experiment used triorganophosphine to produce a record materials according to the invention suitable. Although dye formation can take place directly during exposure, it may be necessary to heat the recording material. in order to convert the latent or practically latent image initially obtained into a visible image, i.e. into a visible one Reinforce image.

Triorganophosphines have proven to be particularly advantageous for the production of a recording material according to the invention those of the structural formula given below have been found;

R ² R ¹ -PR ³

where mean:

1 2 3
R, R and R each independently represent an alkyl radical,

preferably a short-chain alkyl radical or an alkoxy radical, preferably a short-chain one Alkoxy radical or an aryl radical, preferably of the phenyl series, in particular a phenyl radical or an amino radical of the following formula:

-N- (R ⁴ ) ₂

in which R. is an alkyl or aryl radical and it also applies that R can be of the following formula:

it also applies that R is also a radical

f! ^f: -

ι 7/1 '? >

-CH ₂

where η is a positive number from 1 to 18 and

1 2
R and R have the meaning already given.

The alkyl radicals of the substituents can consist of optionally substituted straight-chain or branched-chain alkyl radicals, which preferably have 1 to 8 carbon atoms in the aliphatic chain. Typical representatives of such alkyl radicals, for which R, R, R and R can stand are, for example, methyl, ethyl, 2-chloroethyl, n-propyl, isopropyl, η-butyl, tert-butyl, Pentyl, hexyl, heptyl, n-octyl and tert-octyl radicals. If the substituents R, R ² , R ³ and R represent alkoxy radicals, then these too preferably have 1 to 8 carbon atoms. Short-chain alkyl radicals and short-chain alkoxy radicals are to be understood as meaning those with 1 to 4 carbon atoms in the aliphatic chain.

If the substituents R ¹ , R, R and R are aryl radicals, these aryl radicals preferably have 6 to 14 atoms in the ring, ie the aryl radicals can consist of mono- and polycyclic, carbocyclic aromatic radicals, for example the phenyl, naphthyl and anthryl series, for example from phenyl, 4-chlorophenyl, 3-methylphenyl, naphthyl and anthryl radicals, but preferably from phenyl radicals.

Particularly advantageous triorganophosphines for producing a recording material according to the invention are, for example:

Triphenylphosphine, tris- (3-methylphenyl) phosphine, P, P-diphenyl-P-methylphosphine, Tris- (4-methylphenyl) phosphine, trimethylphosphine,

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Ρ, Ρ-diphenyl-P-ethoxyphosphine, Ρ, Ρ-dimethyl-P-phenylphosphine, P-pentafluorophenyl-P.P-diphenylphosphine, Butyldimethoxyphosphine, tris (n-butyl) phosphine, tris (dimethylamino) phosphine, Tris (n-octyl) phosphine,

Tris (diphenylamino) phosphine, PrMethyl-P, P-diphenylphosphine, Tris (4-chlorophenyl) phosphine, Tris (4-methoxyphenyl) phosphine, Triethoxyphosphine,

1,2-bis (diphenylphosphino) ethane, 1,4-bis (di-n-butylphosphino) butane and 1,8-bis (di-4-chlorophenyl) octane.

In the general structural formula for the complexes of a transition metal and a triorganophosphine, X stands for a wide variety of customary acid anions, for example halide anions, e.g. chloride, bromide and iodide anions, and also for example cyanide, thiocyanate and cyanate azide anions.

For the production of a photographic recording material Complexes of a transition metal and a triorganophosphine required according to the invention can be produced in a simple manner by adding a warm solution of a transition metal salt with a corresponding anion to a boiling saturated one Solution of a triorganophosphine is added. The complex is formed immediately and either separates out on cooling or can be isolated after evaporation of the solvent will. A wide variety of solvents can be used to prepare the complexes, preferably weakly coordinating solvents such as, for example, ethanol, 1-butanol, vinegar, i.e. weakly ionic solvents which are soluble in water subject to weak dissociation

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acid and the like. For example, ketones can also be used as solvents, although it should be noted that that the reaction products can be soluble in ketones, so that a concentration of the solution is necessary to the To be able to isolate the reaction product.

A wide variety of organoazides are also used to produce a photographic recording material according to the invention suitable. The availability of a special azide leaves determine themselves according to the test method described, this time using a phosphine to carry out the test known for its usefulness, for example triphenylphosphine.

Organoazides suitable for the production of a recording material according to the invention, i.e. organic azides can be obtained from the There are various radiation-sensitive compounds that have hitherto been used for the production of photographic print-out materials uses fibers, for the production of which an azide and a color former, that with the azide on exposure to activating radiation with the formation of a dye in the exposed areas, required are. For example, arylazides, aminoarylazides can be used to produce a recording material according to the invention and heterocyclic azides of the type disclosed in U.S. Patents 3,062,650 and 3,282,693 can be used. Further azides, which are suitable as photosensitizers for polymers, are suitable. Such photosensitizers can from the same. Azides exist or differ from the azides that are suitable for making copy-out materials, such as they are, for example, from Kosar, "Light-Sensitive Systems", published by John Wiley & Sons, Inc., New York (1965), in particular pages 330 to 336, including footnotes. Further, for Production of recording materials according to the invention suitable organic azides are, for example, from the

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U.S. Patents 2,940,853, 3,061,435 and 3,143,417 are known. In the case of heterocyclic azides, those in which the azido group is not in the ortho position to a heterocyclic atom in the heterocyclic ring are particularly suitable. Other advantageous azides, including polymeric azides, which are suitable for the preparation of the recording materials according to the invention, are described, for example, in US Patents 3,002,003 and 3,096,311.

Particularly advantageous organoazides for the production of a recording material according to the invention are, for example:

4-azidobenzenesulfonamide,

Ethyl 4-azidobenzoate,

Ethyl 2-azidobenzoate, glyceryl 4-azidobenzoate, 3-azidobenzoic acid, 4-azidobenzolarsonic acid, 4-azidobenzamide, 4-azido-N-methylacetanilide, 4-azidobenzophenone, 2- (4-azidophenyl) -6-methylbenzothiazole 3-azido -α, α, α-trifluoromethylbenzene, 3-azido-4-chiοro-α, α, α-trifluoromethylbenzene, 4-azidobenzonitrile, 3-hydroxypropyl-4-azidobenzoate,

Phenyl 4-azidobenzoate,

2- (3-hydroxynaphthyl) 4-azidobenzoate,

N-methyl-N-phenyl-4-azidobenzamide, N- (2,6-dimethylphenyl) -4-azidobenzamide,

4-azidobenzopiperidide,

N- (1-naphthyl) -4-azidobenzamide,

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-Vf-

N- (Penta £ luorophenyl) -4-azidobenzamide, phenyl-4-azidophenylsulfonate, 2,4,6-trichlorophenyl-4-azidophenylsulfonate, N- (4-azidophenylsulfonyl) phthalimide, 4-azidobenzophthalimide, N-phenyl-N-methyl-4-azidophenylsulfonamide, N- (4-Azidophenylsulfonyl) -pipe # idin, N- (2,6-dimethylphenyl) -4-azi dophenyIs ulfonami d, N- (4-azidophenylsul £ onyl) succinimide, N-methyl-N-phenyl-Z-azidonaphthalene-6-sulfonaraid, Phenyl-o-azidonaphthalene-2-sulfonate, N- (6-Azido-2-naphthylsulfonyl) succinimide, N- (6-Azido-2-naphthylsulfonyl) phthalimide, 1-azido-2,4,6-trichlorobenzene, 2-azido-3-nitrobenzene,

4-azidobenzoic acid,

3-acidophthalic anhydride »4-azidocinnamic acid,

3-azidobenzenesulfonamide, 2-azido-9-luorenone,

1-azi do-5-methoxynaphthaiin, 2- (4-azidophenyl) -5-phenyloxazole, 4'-azido-4-chlorochalcon _t 2- (4-azidophenyl) benzoxazole, 1-azidonaphthalene,

2-phenyl-5- (4-azidophenyl) oxazole, 2- (4-azidobenzylidene) -3,4-dihydro-2H-1-naphthone, 4-azidochicon,

N- (4-azidobenzylidene) -4-chloroaniline, 2- (4-azidophenyl) benzimidazole, 1-azido-2,4-dichlorobenzene, 2- (3-azidophenyl) -5-phenyloxazole, 4,4'-Di azido-3,3 · -dimethoxybipheny1, N- (6-Azido-2-naphthylsulfonyl) piperidide,

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2-azidophenetol,

4-azidophenetol,

Trimethylene bis (4-azidobenzoate), bis (4-azidophenyl) disulfide, 4-azido-3,5-diethoxybenzanilide, 4-azidophenyl sulfide, 4-azido-3-nitroanisole,

N- (3-Azidopheny! .Sulfonyl) succinimide

4-azido-3,5-dimethoxyphenylmorpholine, 3-azidoquinoline,

2-azidocarbazole,

2-azidobenzoic acid, 4-azidophenoxyacetic acid, N-methyl-N-octadecyl-4-azidoaniline, 1-azido-4-bromonaphthalene, bis (4-azidophenyl) ether, 4-azidoazobenzene,

N- (4-azidophenyl) -N-methylmorpholinium tetrafluoroborate, 4'-azido-4-toluenesulfonanilide, 4-azidobenzenesulfonic acid, 1-azido-4-methoxynaphthalene, 4-azidostyry1-1-naphthyl ketone, 3- (4-azidophenyl) coumarin, 1,2,3,4,5,6-hexa (4-azidobenzoxy) hexane, 4,4'-diazidodibenzalacetone, 1-azido-2,476-tribromobenzene, 4-azidoacetanilide,

2-azidodiphenyl ether, 2,5-bis (4-azidophenyl) oxazole, 2- (4-azidophenethyl) -5-phenyloxazole, 2- (4-azidophenethyl) benzoxazole, 4,4 ^l -diazido-2,2'-stilbene-di- (N, N-dibutylsulfonamide), 2,6-di (4-azidobenzal) -4-methy! Cyclohexanone,

Poly (vinyl acetate-co-4-azidobenzoate), N-methyl-4-azidoacetanilide,

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-H-

1-azido-3-cyano-4-methoxybenzene, i-Azido-S-cyano ^ -morpholinobenzene, N- (4-azido-2-cyanophenyl) piperidine, N-butyl-4-azido-2-cyanoaniline, N, N-diethyl-4-azido-2-cyanoaniline, N, N-dibutyl-4-azido ^ 2-cyanoaniline, N-hydroxyethyl-4-azido-2-cyanoaniline, N, N-diethyl-4-azido-2-chloroaniliji, 4-azidodiphenylamine,

4-azido-2-cyanodiρhenylaInin, 4-azido-2-cyano-4'-methoxydiphenylamine, 4-azido-2-cyano-4 ^l -dimethylaminodiphenylamine, 1-azido-2-methoxy-4-morpholinobenzene, 1-azido 3-methoxy-4-morpholinobenzene,

N-methyl-4- (4-azidophend) -2,6-diphenylpyridinium perchlorate, N-methyl-4- (4-azidostyryl) -2,6-diphenylpyridium perchlorate and

2,5-bis (4-azidophenyl) oxadiazole.

The image-forming layers of a photographic recording material according to the invention can advantageously be produced using a binder consisting of a polymer. For this purpose, the customary known binders, in particular film-forming binders, can be used, including customary known film-forming, practically hydrophobic polymers, which can be used for the production of coating compounds using solvents of low polarity and which have sufficient permeability to bases, Sxxkx and gases as well Have liquid and thus neither release the phosphine from the phosphine formers nor delay the development of the dye image.

3093 f; 7/1 ???

22378Λ8

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AIs particularly advantageous binder, for example, polymers have been found based on cellulose, such as ethyl cellulose, butyl cellulose, as well as Celluloseester, for example, cellulose acetate, cellulose triacetate, cellulose butyrate and cellulose acetate butyrate, further, however, vinyl polymers, for example polyvinyl chloride, polyvinylidene chloride, polyvinyl butyral, copolymers of vinyl chloride and vinyl acetate, Polystyrenes, poly methacrylates, homopolymers and copolymers of acrylamides, copolymers of alkyl acrylates and acrylic acid, for example:

Poly-n-isopropyl acrylamide,

Polydiacetone acrylamide,

Copolymers of acrylamide and N-isopropyl acrylamide,

Copolymers of diacetone acrylamide and N-isopropyl acrylamide,

Copolymers of methacrylamide and N-isopropyl acrylamide, 2,3-naphthalenediol,

2-hydroxy-3-naphthanilide, 2-hydroxy-2'-methyl-3-naphthanilide,

Copolymers of N-isopropyl acrylamide and 1-vinyl-2-pyrrolidone,

Copolymers of methyl methacrylate and methacrylic acid, Copolymers of butyl acrylate and acrylic acid

as well as other polymers such as polyphenylene oxides, terpolymers of ethylene glycol, isophthalic acid and terephthalic acid., Terpolymers of p-cyclohexanedicarboxylic acid, isophthalic acid and Cyclohexylenebismethanol, copolymers of p-cyclohexanedicarboxylic acid and 2,2,4,4-tetramethylcyclobutan-i, 3-diol and other polymers, such as the condensation products of epichlorohydrin and bisphenol-A.

To produce a recording material according to the invention and to carry out a method according to the invention, a wide variety of conventional dye-forming couplers can also be used, which - what is assumed - react with a photolytic product of the phosphine-azide complex to produce a dye in the exposed areas .

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To produce the recording materials, the couplers are advantageously used in molar concentrations, which are equivalent or practically equivalent to the concentrations of the phosphine-azide complexes or in a slight excess, for example a 5 to 1 oily molar excess to achieve a to ensure maximum dye generation.

For the production of a photographic recording material according to the invention and for carrying out the process of In the invention, the customary known couplers can be used, the use of which in the known diazotype materials is known is. For example, the couplers described in the book by Kosar "Light-Sensitive Systems", Verlag John Wiley & Sons, New York, USA (1965), in particular on pages 220 to 240. Other particularly advantageous Couplers for making a recording material according to the invention and for carrying out the process of the invention for example in US Pat. No. 3,573,052, in particular in column 6, line 17 to column 7, line 20. The color couplers listed below are therefore suitable, for example:

2,3-naphthalenediol,

2-Hydroxy-3-napthanilid, 2-Hy droxy- 2 '-meth) i- 3-naphthanilid, 2-Hydroxy-2', 4 ^f -dimethoxy-5 "-chloro-3-naphthanilid, 2-Hydroxy- 2 ', 5 ^f -dimethoxy-4'-chloro-3-naphthanilide, 2-hydroxy-1'-naphthyl-3-naphthanilide, 2-hydroxy-2'-naphthyl-3-naphthanilide, 2-hydroxy-4'- chloro-3-naphthanilide, 2-hydroxy-3-naphthanilide, 2-hydroxy-2, S'-dimethoxy-3-naphthanilide, 2-hydroxy-2 ', 4'-dimethyl-3-naphthanilide,

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1-hydroxy-2-naphthamide, N-Methy1-1-hydroxy-2-naphthamide, N-butyl-1-hydroxy-2-naphthamide, N-octadecyl-1-hydroxy-2-naphthamide, N-phenyl-1-hydroxy-2-naphthamide, N-methy1-N-pheny1-1-hydroxy-2-naphthamide, N- (2-tetiradecyloxyphenyl) -! - hydroxy-2-naphthamide,

N- / ~ 4- (2,4-di-tert-amylphenoxy) butyl_7-1-hydroxy-2-naphthamide,

i-Hydroxy-2-naphthopiperidide, N- (3,5-dicarboxyphenyl) -N-ethyl-1-hydroxy-2-naphthamide, N, N-dibenzy1-1-hydroxy-2-naphthamide, N- (2-chlorophenyl ) -1-hydroxy-2-naphthamide, N- (4-methoxyphenyl) -1-hydroxy-2-naphthamide, 1-hydroxy-2-naphthopipericide, 1,3-bis- (i-hydroxy-2-naphthamidobenzene), 2- Acetamido-5-methylpheno1, 2-acetamido-5-pentadecylphenol, 2-butyramido-5-methylphenol, 2- (2,4-di-tert-amylphenoxy acetamido) -5-methylpheno1 and 2- Ben ζami do-5-me thylphe no1.

Further suitable couplers are, for example, those which have a reactive methylene or methine group as they e.g. in U.S. Patent 3,062,650, particularly in column 4, line 8 to column 4, line 27. Such Color couplers, e.g., 3-methyl-1-phenyl-5-pyrazolone, are particularly advantageous when using organoazides which contain an amino radical i.e. if, for example, aminoarylazides are used at the same time. As particularly advantageous aminoarylazides 4-Amino-1-azidobenzene compounds and derivatives have been found.

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Coating compositions suitable for the production of photographic recording materials according to the invention can be obtained in a simple manner Way be prepared, for example, that at least one complex of a transition metal and a triorganophosphine of the formula given and at least one organoazide in a solvent be solved. A wide variety of organic solvents or solvent mixtures can be used for the solution be, for example methyl ethyl ketone, methylene chloride, acetone, short-chain alkanols, dichloroethane, tetrahydrofuran, toluene and the like., individually or in combination with one another. In The ratio of phosphine to azide in the solution can be very different. Preferably, however, the phosphine is at a low level molar excess, e.g., a 5 to 10 molar excess used to ensure that all of the azide is complexed. Without complete conversion of the azide in a complex background stabilization can be impaired will.

A solution prepared in this way can then be more advantageous Way to be applied to a layer support after the addition of a binder. The usual known Substrate materials are used, for example film substrates made of cellulose esters, for example cellulose acetate, Cellulose triacetate, cellulose acetate butyrate and the like, furthermore from poly-olefins, in particular from o-olefins with 2 to 10 Carbon atoms, for example from polyethylene, polypropylene and polystyrene or from polyesters, for example from polyethylene terephthalate or, made of polycarbonates, but also on layers made of zinc and aluminum as well as paper, as well as with polyethylene or polypropylene coated papers. This means that the coating compounds are applied to all common substrates, those suitable for the production of photographic diazotype materials are.

3 0 9 ^ U 7 / .1,2 2; 2.

30th

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The recording materials according to the invention are thus advantageously produced by customary coating processes using solvents, since these processes enable rapid, advantageous and continuous production of the recording materials. To produce the coating solutions, the components forming the image-forming layer are therefore first dissolved in a suitable solvent or solvent mixture, optionally with a polymeric binder. As it has proved expedient here to use coating solutions having a solids content of about 5 to 20 parts by I ₁ preferably 8 to 15 weight-I. In such solutions, if a polymeric binder is used, the image-forming components are typically present in amounts of from about 20 to about 50 parts by weight per 100 parts by weight of polymeric binder, preferably in concentrations of from about 25 to about 45 parts by weight to 100 parts by weight of binder. Of course, other relationships are also possible, but those specified have proven to be particularly advantageous. The coating can be done by dipping, by whirl coating, by spreading, by applying by means of a coating knife, by coating by means of a coating funnel or the like, whereby the layers are preferably applied in a thickness of about 0.0025 to about 0.0025 cm, measured wet * The coated material can then be dried in the usual known manner.

The recording materials produced in this way can then activated by chemical treatment / with a base, whereby a triorganophosphine is set free, which is able to form a phosphine-azide complex. To activate the customary known bases are used, which in the case of the customary diazotype reproduction materials for bringing about the Coupling reaction, e.g. ammonia,

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containing organic amines and other organic nitrogen Bases. Typical bases »those for activation and thus for implementation of the method of the invention can be used, for example in the already cited book by Kosar and also in U.S. Patent 3,578,452 and Canadian Patent Specification 772 109 indicated.

In addition to bases of the type listed, for example Lewis bases, including water, are used for activation »i.e. to release phosphines from the phosphine complexes.

The activation can take place, for example, in that the recording material is immersed in a solution of the activating agent, in particular the bases, or by action of fumes from the base.

It is important that the radiation sensitivity of the invention used phosphine * -Azidkdmpl $ x @ not with the known Sensitivity of arylazides, as in the photographic one Vesicular processes or other photographic processes are used, is to be equated. Such connections show a relatively low photoreactivity, whereas the radiation-sensitive complexes used according to the invention have a relatively high photographic sensitivity, the about 10 χ as * large as that of the comparable non-complex bound azides.

When a sensitive phosphine-azide complex of the type described is exposed to activating radiation in the presence of a color coupler, an image is produced in the exposed areas. Normally, this image of a readily identifiable or clearly visible dye image _s can vary its optical density, depending on its composition. In certain

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Cases, latent images can be created »which are not without further or not at all recognizable. In the latter In this case, these latent images can be enhanced in the manner already described.

It is believed that the dye-forming reaction goes through the imagewise release of hydroxyl ions and ammonium hydroxide is brought about by exposure of the phosphine-azide complex. Furthermore, it is believed that the release of hydroxyl ' ions and ammonium hydroxide by the reaction of a phosphine imine anion, which is formed upon exposure, with water. which is present in the layer of the recording material or the recording material.

The selection of the radiation source used to expose the recording material depends on the spectral properties of the phosphine-azide complex used in the individual case. The selection of suitable radiation or light sources can be easy by recording a step wedge spectrogram of the phosphine-azide complex used in individual cases. In general, however, the spectral sensitivity range of the complexes closes the range of ultraviolet rays and other actinic rays, so that the recording materials can be exposed, for example, with conventional mercury vapor or mercury arc lamps which produce light rich in ultraviolet rays emit, or with appropriate light sources. This means that for the exposure of the photographic recording materials according to the invention, the usual known diazotype copiers and other commercially available photocopiers are used can be used for exposure radiation source »that emit ultraviolet light.

After the image-appropriate exposure, the inventive Recording materials are heated for the purpose of stabilizing the photographic images produced, to a Tempe-

30980 7/1222

temperature which stabilizes the non-image areas against being copied out * Hs is assumed that a rearrangement when heated of the phosphine-azide complex takes place with the formation of a stable, practically colorless phosphinimine «

In those cases in which only an image of low optical density or a latent image is obtained with the imagewise exposure on the other hand, the heat stabilization causes an image intensification to produce a good and by the eye easily visible image.

Suitably, the recording materials for the reasons given to temperatures of at least about 6O ⁰ C, heated up to about 13O ⁰ C, "The applied in individual cases Erhitzuagsdauer depends on the height d @ r heating temperature from" such that shorter at higher temperatures fixation times were used This means that the recording materials can advantageously be heated for about 5 seconds to 2 minutes. The heating can take place, for example, by bringing them into contact with a hot surface, by inserting them into a hot chamber or the like.

In those cases in which the recording material itself does not have a color coupler, the exposure of the recording material « a treatment with one or more of the color couplers, for example by means of a color coupler solution. Through the treatment A high density dye image or an intensifiable image forms spontaneously. In an advantageous manner can thus for example, the exposed recording material can be brought into contact with a dye copper solution, which is for example can be done by dipping the recording material in the color coupler solution or by buffing or spraying the dye solution. Nash of the treatment with the color coupler solution

30980 7/1 ???

2737848

the recording material can be washed and / or dried where drying can optionally be combined with heat stabilization.

The method of the invention also enables, for example, the production of multicolored, for example two-colored Images obtained by converting a recording material with (a) a complex of a transition metal and a triorganophosphine of the formula given and (b) a radiation-sensitive organoazide of the type known from US Pat. No. 3,062,650 with an amino radical, for example a p-disubstituted Aminophenyl azide and a coupler that works with the Azide is able to react, goes out.

In this case, the recording material is first exposed imagewise to radiation that activates the azide, i. E. radiation that the azide is sensitive to.

This creates a visible dye image. The recording material is then subjected to chemical treatment, e.g. through contact with a base, e.g. ammonia vapors, activated, the triorganophosphine complex being the corresponding

- 24 -

309 mfm *

Triorganophosphine sets free, whereby a phosphine-azide complex forms. The recording material is then exposed imagewise for the second time to radiation which is sensitive to the phosphine-azide complex. Since the complex is chemically different from the azide, it can have a spectral absorption range different from the azide. As a result, a different light source may be required for each of the imagewise exposures, although generally a light source emitting ultraviolet rays can be used for both exposures. The second exposure creates an image in the exposed areas. If necessary, the second dye image produced in the second exposure can be intensified in the manner already described. The second image ₁ , if it is visible, preferably has a different color than the image produced during the first exposure. The image generation can be followed by heat stabilization, which can optionally be combined with an image intensification or image intensification of the second dye image, provided the latter has a low optical density.

Is the concentration of azide sufficient and the first exposure not so intense that all of the azide is in the exposed Districts is photolyzed, so can still existing azide in the district when activated with a base with the Phosphine form a complex with the second exposure to a second dye in the areas that each of the Exposures is common.

The invention thus also relates to a method for producing photographic images using a photographic recording material of the invention having a Layer containing:

309807/1222

(a) a p-aminophenyl azide,

(b) a coupler reactive with the azide and

(c) a triorganophosphine complex of the formula given, which is characterized in that 1. the material first image-wise with radiation that activates the azide exposed to produce a first image in the exposed areas, 2. subjecting the material to a chemical, in particular alkaline, treatment, the material 3. exposed again image-wise to produce a second image in the exposed reference areas and, if necessary, 4. additionally heated the material for stabilization.

The recording materials according to the invention are suitable for Production of negative images, i.e. images that correspond to the irradiated areas. The recording materials according to of the invention can, however, also be processed by thermophotographic means to produce positive images i.e. images whose image areas correspond to the non-irradiated areas. For example, it is possible to use a Photographic recording material according to the invention * which has been activated for the purpose of producing a phosphine-azide complex is to first heat imagewise, i.e. subject to an imagewise 'thermal exposure, whereby the exposed Districts are stabilized before aiskopieren. The recording material is then exposed to radiation which activates the complex fully exposed, whereby a visible or at least intensifiable dye image is obtained. In the cases in yours the recording material has no color coupler, the image development includes a treatment with a coupler solution in the manner described.

309807/1222

According to a further advantageous embodiment of the invention, the recording materials can be used for the production of lithographic Printing plates are used, by use of hydrophilic polymeric azides, for example those as described in US Pat. No. 3,002,003 and those therein References cited in the patent are known. Recording materials with surfaces suitable for lithographic purposes can also be passed through, for example Use of hydrophilic polymeric color couplers, for example polymeric pyrazolones, »Preferably be used with the polymeric color couplers bis-azides. After the recording materials are exposed in the manner described and have been developed, the developed surfaces can be treated with water from the unexposed areas is recorded. Of the exposed districts ^ which represent the printing surfaces, then bold printing inks can be transferred to other surfaces.

In the following, the first thing to do is to prepare for production of recording materials according to the invention usable complexes of a transition metal and a triorganophosphine to be described in more detail »

By addition of about 40 ⁰ C warm solution of cobalt carbonate, nickel carbonates nickel bromide, cobalt bromide or Nickelrhodanid to boiling saturated solutions of the complexes were prepared phosphines listed in Table I below. After the addition of the metal salt solutions to the phosphine solutions, the corresponding complexes were formed, which either by cooling

the solution / "uiid / or by concentration of the solutions for the purpose of precipitation were isolated.

In the following table are the formulas of the complexes prepared, the solvents used to prepare the complexes, the color shades and the melting points of the complexes are given.

3 0 9 8 0 7/1722

Formula of the complex TABLE I. hue Mp. ⁰ C Co (0 ₃ P) ₂ Cl ₂ Solvent blue Co (0 ₃ P) ₂ Cl ₂ acetone blue 246-250 °
247-251 ° (d) Co (0 ₃ P) ₂ Br ₂ Ethanol blue green 235-242 °
234-239 ° Co _Z - (nC ₈ H ₁₇ ) ₃ P.7 ₂ Cl ₂ acetone blue oil co
O Co / "(P-CH ₃ OC ₆ H ₄ ) ₃ P_7 ₂ Br ₂ Acetone / ethyl acetate /
benzene light green 195-198 ° cr>
GO Cf \ / ~ 1 * · »* fU Γ U ^ D 7" D · »*
\ * W / IP Wil T ** £ * · j | J - * / *) D I Λ Ethanol green 255-260 °
254-257 ° Co ^ "(Hi-CH ₃ C ₆ H ₄ ) ₃ P.7 ₂ C1 ₂ Ethanol Light Blue
light green 208-210 °
203-206 °
206-208 ° -ο
NJ
O Co ^ "(P-CH ₃ C ₆ H ₄ ) ₃ P_7 ₂ C1 ₂ Ethanol
Ethanol blue 208-212 ° Co / "(P-CH ₃ C ₆ H ₄ ) ₃ P_ / ₂ C1 ₂ Ethanol blue 213-218 ° Co (0 ₂ PC ₂ H ₅ ) ₂ Cl ₂ Ethanol blue 175-179 ° Co (0 ₂ PCH ₃ ) ₂ Cl ₂ Ethanol blue 175-179 ° CO (0 ₂ PC ₂ H _s ) ₂ Br ₂ Ethanol light green 198-203 °
186-196 \ (d) Ethanol

OO -C-OO

Continuation from Table I.

CD OO O

Ni (0 ₃ P) ₂ (SCN) ₂ Mf Cn-C ₄ H ₉ ) 3 Pj

(P-CH ₃ OC ₆ H ₄ ) ₃ p_7 ₂ ci ₂

Cm-CH ₃ C ₆ H ₄ ) ₃ PJ ₂ Cl ₂

mf CP-CH ₃ C ₆ H ₄ ) ₃ P_7 ₂ ci ₂

Ni (0 ₂ PC ₂ H _s ) ₂ Cl ₂ NiC0 ₂ PCH ₃ ) ₂ Cl ₂

1-butanol ethanol

Ethanol ethanol

Ethanol Ethanol Ethanol Ethanol

Ethanol

the symbol 0 stands for the phenyl radical,

Red Red

Red Green

dark red red-green red-green bright red

Orange red

228-229
217-218

43-46

48-49
148-150 ° 191-193 ° 168-171 ° 180-185 ° (d) 205-211 ° 225-235 ° (d) 145-150 ° 146-151 ° 147 -151 °

¹ U?

2737848 30

The following examples are intended to illustrate the invention in more detail. Bra game 1

First, a coating composition was made by mixing the the components listed below are manufactured:

0.2 g of Z "Co (C ₆ H ₅ ) ₃ P_7ci ₂ ;

0.1 g of p-azidobenzenesulfonamide and

0.1 g of 2,3-naphthalenediol, dissolved in 15 ml of 1,2 dichloroethane.

The blue solution obtained was then mixed with 15 ml of a 10% cellulose acetate butyrate solution in 1,2-chloroethane, whereupon the mixture was applied with a coating knife in a layer thickness of 0.015 cm, wet, and applied to a polyethylene terephthalate support. After the applied layer had dried, the recording material obtained was activated by bringing it into contact with moist ammonia vapors for 5 seconds. The recording material was then exposed imagewise in a conventional diazotype copier using a light source consisting of several fluorescent tubes. The background effects were ^{stabilized by heating at 110 °} C. for seconds.

This example thus shows that the phosphine metal coraplex precursor compound becomes one with the azide by exposure to ammonia provides photosensitive complex, so that the photosensitive material obtained can be exposed in an imagewise manner.

309807/1222

- 30 Example 2
A solution from:

0.05 g of i-azido-4- (2-benzimidazolyl) benzene; 0.20 g of Mf (C ₆ H ₅ ) ₃ P.7 ₂ C1 ₂ and 0.05 g of 4-methoxynaphthol

was poured onto a filter paper and dried.

The recording material obtained in this way was then activated by exposing it to moist ammonia vapors for 5 seconds was brought into contact. Thereupon the recording material Exposed for 10 seconds in contact with a silver negative by means of an infrared lamp. Thereupon the recording material with ultraviolet light, also generating @ in @ s dye image irradiated in the thermally not exposed areas.

Example 3

First a solution was made from:

0.15 g p-morpholinophenyl azide;

0.2 g of 2,4-dichloro-6- (2,4-dipentylphenoxyacetamide) -3-meth | oil phenol as a coupler and

0.8 g of Co On-CH ₃ C ₆ H ₄ ) ₃ P2Cl ₂ in 15 ml of acetone.

The solution then became 15 ml of a 1 (Higen solution of cellulose acetate butyrate added in dichloroethane, whereupon the mixture obtained by means of a coating knife on a polyethylene

3 0 ⁽ i H (I 7/1 ???

-N-

terephthalate film base in a layer thickness of 0.015 cm measured when wet. The recording material obtained was then first exposed in a diazotype copier using a conventional mercury arc lamp, producing a dye image in the exposed areas. The recording material was then brought into contact with moist ammonia vapors at 50 ^° C. for 10 seconds, as a result of which phosphine was set free from the phosphine transition metal complex. The recording material was then exposed again in the diazotype copier, but only 1/3 the time of the first exposure, whereby a dye image different from the initially obtained color image was obtained in the newly exposed areas. The background areas were then stabilized by heating for 5 seconds at 11O ⁰ C.

Corresponding results, as described in Examples 2 to 3, were obtained when equivalent concentrations of other azides and other transition metal complexes were used.

3 0 ¹ Y 8 0 7/17 ??

Claims (8)

PATENT CLAIM Ε Ι. Photographic recording material consisting of a Layer support and at least one applied to it, which can be converted into a light-sensitive layer by chemical treatment, an organoazide-containing, image-forming layer, characterized in that it is an image-forming layer Layer a layer containing (a) a complex of a transition metal and a triorganophosphine of the formula: (Z) ₂ MX ₂ where mean: Z a triorganophosphine, M is a cobalt or nickel cation and X is a monovalent anion, (b) an organoazide and, if appropriate, also (c) a coupler which provides a dye with the organoazide and / or (d) has a binder for (a) and (b) and optionally (c). 2. Photographic recording material according to claim 1, characterized characterized in that it contains a complex of the formula given in which Z is a triorganophosphine group of the following Formula is: R ² R ¹ - P - R ³ 1 2 \ in which R, R and R ° each mean: an alkyl, alkoxy, Aryl or amino radical of the following formula: 309 807/122? R ⁴ - N in which R in each case represents an alkyl or aryl radical, and where R can furthermore be a radical of the following formula: , R ¹ • - CH- f CH -) - P - R 2 ^v 2 η 1 2
in which R and R have the meaning already given and η is a number from 1 to 18. 3. Photographic recording material according to Claims 1 and 2, characterized in that it contains a complex of the formula given, in which 2 is a Triphenylphosphine, tri- (n-octyl) phosphine, Tri- (p-methoxyphenyl) phosphine, tri- (p-tolyl) phosphine, Tri- (m-tolyl) phosphine, diphenylethylphosphine, diphenylmethylphosphine, tri-n-butylphosphine or Dimethylphenylphosphine group 4. Photographic recording material according to Claims 1 to 3, characterized in that it contains a complex of the formula given in which M is cobalt or nickel and X is a halide or thiocyanate anion. 309807/1222 54 - 5. Photographic recording material according to Claims 1 to 4, characterized in that it is one of the following complexes
contains: co / "(C ₆ H ₅ ) ₃ P_7 ₂ ci ₂ Co /" (C ₆ H ₅ ) ₃ P.7 ₂ Br ₂ Co / "(C ₆ H ₅ ) 2PC ₂ H ₅ Co / "(C ₆ H ₅ ) ₂ C ₂ H ₅ .7 ₂ Br _{2 6} H ₅ ) ₂ C ₂ H ₅ .7 ₂ H ₅ (CH ₃ ) ₂ P_7 ₂ C1 ₂ co / "(HC ₈ H ₁₇ ) ₃ p_7 ₂ ci ₂ . Co / "(P-CH ₃ OC ₆ H ₄ ) ₃ P.7 ₂ Br ₂ Co /" (P-CH ₃ C ₆ H ₄ ) ₃ P_7 ₂ Br ₂ co / "(Hi-CH ₃ C ₆ H ₄ ) ₃ p_7 ₂ ci ₂ Co / - (m-CH ₃ C ₆ H ₄ ) ₃ P_7 ₂ Br ₂ co / "(P-CH ₃ C ₆ H ₄ ) ₃ p_7 ₂ ci ₂ Ni / - (nC ₄ H ₉ ) ₃ P_7 ₂ Cl ₂ Ni / "On-CH ₃ C ₆ H ₄ ) ₃ P_7 ₂ Br ₂ Ni / - (p-CII ₃ OC ₆ H ₄ ) ₃ P_7 ₂ Cl ₂ Ni /" (In-CH ₃ C ₆ H ₄ ) ₃ P_7 ₂ C1 ₂ or 6. Method of making photographic images using of a photographic recording material according to claims 1 to 5, characterized in that the material is first subjected to a chemical pretreatment, then image 3 0 4 8 0-7 / 1 ΊΊΊ , fairly exposed, treated with a color coupler and, if necessary still heated for stabilization. 7. A method for producing photographic images using a photographic recording material according to claims 1 to 5, characterized in that the material is first subjected to a chemical pretreatment, then heated imagewise and finally with spontaneous generation of an image in the unheated areas with activating
Radiation fully exposed. 8. Method of making photographic images using of a photographic recording material according to Claims 1 to 5 having a layer containing: (a) a p-aminophenyl azide, (b) a coupler reactive with the azide and (c) a triorganophosphine complex of the formula given, characterized in that 1.) the material first imagewise exposed to the azide activating radiation to produce a first image in the exposed areas which Material 2.) is subjected to a chemical treatment, the material 3.) again image-wise to generate a second one The image is exposed in the exposed areas and, if necessary, 4.) the material is additionally heated for stabilization. 3098Π7 / 1 ???