DE2237823A1 - PHOTOGRAPHIC RECORDING MATERIAL - Google Patents

Description

2737823

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

8 MONKS 22 l.9.T .... J. ^ kl · ... ! .? ..? ²

THIERSGHSTRASSE 8

PHONE; (0811) 293297 25/81

Reg. No. 123 395

Eastman Kodak Company, 343 State Street, Rochester, New York State, United States of America

Photographic recording material

309807/1220

The invention relates to a photographic recording material, consisting of a layer support and at least one on top applied, by alkaline treatment in a photosensitive Layer transferable, at least one organoazide-containing image-generating layer.

Photographic recording materials are known which can be used for the production of photographic images by a dry or practically dry route. Of particular importance are the two-component diazotype recording materials which contain a diazonium salt and a color coupler which is capable of reacting under alkaline conditions with the diazonium salt to form an azo dye. The structure of diazotype recording materials is known in detail, for example, from the book by Kosar, "Light-Sensitive Systems", published by John Wiley & Sons, Inc., New York (1965), in particular Chapter 6. If such recording materials are exposed in an imagewise manner, the light-sensitive diazonium salt is destroyed in an imagewise manner. Subsequent treatment with an alkaline developer, for example ammonia, initiates a dye-forming reaction in the unexposed areas between the diazonium salt and the color coupler, a positive reproduction of the original being obtained. However, recording materials of the diazotype type described have certain disadvantages, in particular because the background areas easily copy out during storage. This tendency zua printout can be minimized by the addition of acid, the premature clutch preventing inhibitors decrease, however, causes the addition of such compounds a Vanukedermg of 4 int "ftckl" ftgsg «« € mwi * digktit the Aufceichnungsnaterialien because the inhibitors before the coupling reaction newly " “ate sen will be centralized. In addition , the usual known development compounds, such as ammonia, are generally toxic, but miadestems are harmful or unpleasant to you * «··« sim4 · _; ,, ■,

BATH ORIGINAL

309807/1220

-Sr-

They are also of the diazotype type recording materials became known which contain diazosulfonates. J) hese Diazosulfonates form diazonium salts on exposure, which in The usual way can couple with color couplers. These known recording materials are negative-working Materials, since when they are used, color images are obtained corresponding to the exposed areas. Disadvantageous one thing about these recording materials is that in their use "Wet image stabilization is required in which the recording material is removed for the purpose of removal any sensitive components still present must be washed.

US Pat. No. 3,062,650 are also negative working photographic recording materials become known, for their production organic azides and so-called Dye precursor compounds can be used. Using Such recording materials are obtained directly on exposure to copy-out images. Also in the use of this Recording materials is disadvantageous in that they are used for the purpose of Removal of unreacted components must be washed in order to stabilize the background areas before copying out.

The object of the invention is to provide silver-free photosensitive photographic Indicate recording materials which, when used, can be used to obtain stable images without the Material must be washed for the purpose of stabilization and without the use of harmful or poisonous developers, connections is necessary. In particular, the manufacture should more stable photographic images solely through the action of light, possibly in combination with the action of Warmth, made possible | without the images for the purpose of Stabilization need to be washed. *

309807/1/20

-Jf-

The invention was based on the knowledge that the asked Object by using photographic recording materials having at least one light-sensitive layer with a Organoazide and a phosphonium salt, which form a phosphine-azide complex when exposed to light, can be dissolved.

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 alkaline treatment, contains at least one organoazide, image-generating layer, which is characterized in that is that, in addition to at least one organoazide, the image-generating layer contains an isolatable phosphonium salt of the formula:

P R

in which R is an organic radical and X is an anion and R 'is an alkyl radical which is in the ß-position by at least one Electron-withdrawing radical is substituted, contains, which can be converted by alkaline treatment into a triorganophosphine which forms a radiation-sensitive complex with the organoazide.

In the photographic recording material according to the invention a phosphonium salt is thus used, which when exposed to a forms a radiation-sensitive complex of a triorganophosphine and an organoazide. Isolable means that the phosphonium salt can graze in isolation.

30980 7/1220

According to a particularly advantageous embodiment of the invention the photographic recording material additionally contains a so-called dye former, i.e. for example one color couplers capable of forming an azo dye with the azide,

The invention enables the production of photographic images starting from the photographic recording materials described by simple exposure without the use of special developing compounds. All that is required is generation of a radiation-sensitive phosphine-azide complex, the background areas of the images obtained by exposure can if necessary before copying out by a simple heat fixation be stabilized. If necessary, such a heat stabilization with an intensification or strengthening of the obtained image can be combined.

The expression "photographic images." includes both visible as well as latent photographic images.

Before the recording materials according to the invention are exposed in an imagewise manner, it is only necessary to use the phosphonium salt to set free a corresponding phosphine, which forms the radiation-sensitive complex with the azide. The setting in freedom the phosphine from the phosphonium salt can be done in a simple manner by an alkaline pretreatment »for example by bringing the recording material into contact with a base.

If the recording material itself does not contain a color coupler, the recording material is advantageously then followed treated to the exposure with a color coupler solution *

A photographic recording material according to the invention can also advantageously be used for the production of positives Use thermophotographic images In this case

309807/122 0

L,

the recording material is first exposed to heat imagewise, whereupon a full exposure with one activating the complex Radiation connects, d. H. radiation that is sensitive to the phosphine-azide complex.

Heat fixation is not required per se, but can these can be used in an advantageous manner in order to achieve an image intensification.

Furthermore, for the production of the photographic recording materials According to the invention, hydrophilic polymeric azides can be used and also hydrophilic polymeric couplers, see above that lithographic printing plates can also be produced from the photographic recording materials.

Characteristic of the photographic recording materials according to the invention is thus the presence of an isolable phosphonium salt, i. H. a P-alkyl-P, P, P-triorgano-substituted Phosphonium salt, in which the alkyl radical is substituted by at least one electron withdrawing radical.

An electron-withdrawing radical is to be understood as meaning chemical radicals or groups that tend to attract electrons, for example from the neighboring atoms of a molecule. The expression electronegative can be used synonymously for the expression withdrawing electrons. Electron-withdrawing or electro-negative radicals are often used to reduce the lability of substituents, e.g. B. a hydrogen atom which is bonded to a carbon atom and which is adjacent to an electron withdrawing group in a molecule, to increase.

The term sensitive to radiation means the sensitivity to electromagnetic rays including X-rays, ultraviolet rays, visible light rays and the same.

309807/1220

The phosphine-azide complexes used in the present invention for imaging are radiation-sensitive chemical complexes »the exposure to activating rays forms reaction products, which can react with a color coupler to produce an image dye.

For the production of the photographic recording materials according to of the invention are all phosphonium salts that are used in treatment form a triorganophosphine with a base, which is able to form a radiation-sensitive complex with an organoazide.

The utility of a phosphonium salt for the production of a recording material according to the invention can easily be ascertained determine a simple test attempt »

This test consists in sharing the phosphonium salt with a commonly known organoazide, e.g. B. with p-morpholinophenyl azide and / or 4-azidobenzenesulfonamide, expediently in equivalents molar amounts or with a small excess of phosphonium salt and a ß-naphthol color coupler, for example Dissolve 2-naphthol, or 2,3-naphthalenediol, whereupon the obtained Solution applied to a conventional layer support and dried is, whereupon the dried layer is treated with a base and then exposed to activating radiation is exposed to the phosphine-azide complex and thus a photographic Generate image. In this way, visible., Or to a visible image can be intensified or amplified Images are obtained. Is the image obtained, if it is visible, in its hue and / or in its intensity of the different photographic image obtained when a corresponding recording material containing only the azide and the color coupler, d. H. without the phosphonium salt is tested in a corresponding manner, then the special phosphonium salt used can be used are considered to be suitable for the production of a recording material according to the invention.

309807/1220

Albeit dye formation immediately upon exposure a recording material can take place, but a subsequent heating may occasionally be necessary to initially to make the obtained latent image visible.

As particularly advantageous phosphonium salts for the production of a photographic recording material according to the invention those of the following structural formula were found:

R ¹ CH - CH - P - R ⁵

Herein mean:

R ¹ and R ²

individually a residue that withdraws electrons,

individually a hydrogen atom, an alkyl or aryl radical or an electron withdrawing radical,

together, the atoms that are required to complete a 2-oxocycloalkyl radical with 5 to 6 ring atoms,

R is a hydrogen atom or an alkyl or aryl

rest or a heterocyclic radical,

R, R 'and R, independently of one another, each represent an alkyl, alkoxy, aryl or amino radical, preferably of the formula -N- (R ⁷ ) ₂ , in which R ^{7 is} either an alkyl or aryl radical , and furthermore holds that R ^{6 can} additionally be a residue of the following structural formula:

309807/1220

R ⁴ ■ ι

CH, f CII, - * - PR ⁵ Χ ^θ

R ⁴

where η is a positive integer from 1 to 18 and R and R have the meanings already given own and

X is an anion.

1 2
The electron withdrawing radicals represented by R and R can consist, for example, of substituted carbonyl radicals, for example carboxyl radicals, acyl radicals, aroyl radicals, carbalkoxy radicals, for example carbomethoxy, carbethoxy or carbopropoxy radicals, or further aryloxycarbonyl radicals, for example phenoxycarbonyl or naphthoxycarbonyl radicals, carbonyl radicals or naphthoxycarbonyl radicals, for example phenoxycarbonyl or naphthoxycarbonyl radicals. B. Ally, carbonyl or styrylcarbonyl residues, or P ~ carbonylethyl-P, P, P-triorganophosphonium salt residues, as well as from cyano and nitrogen residues.

X represents a common one for phosphonium salts. Anion, for example a halide anion, e.g. B. a bromide, chloride or iodide anion, or a tetrafluoroborate, tetraphenylborate, perchlorate, Hexafluorophosphate, hexafluorotitanate, hexafluoroantimonate or Sulphate anion, for example a sulphate, hydrosulphate or short-chain alkylsulphonate anion, ζ. B. methyl sulfate or ethyl sulfate anion, or an aromatic sulfonate anion, for example a p-toluenesulfonate or benzenesulfonate anion, or an anion that derived from a carboxylic acid, for example a trifluoroacetate anion or also a cyanate, thiocyanate or Sulfamate anion.

309807/12 20

An "alkyl radical ¹ " here means an optionally substituted, straight-chain or branched-chain alkyl radical with preferably 1 to 8 carbon atoms in the aliphatic chain. The alkyl radicals can thus consist, for example, of methyl, ethyl, 2-chloroethyl, n-propyl -, 3-Phenylpropyl, isopropyl, η-butyl, tert-butyl, pontyl, fiexyl, heptyl, n-octyl or tert-octyl radicals. Under "Alkoxy radicals" ¹ are to be added understand that preferably have 1 to 8 carbon atoms in the alkyl group, which may correspond to the listed alkyl radicals. Short-chain alkyl and alkoxy radicals are to be understood as meaning those with 1 to 4 carbon atoms in the aliphatic chain.

The aryl radicals preferably consist of mono- or polycyclic aromatic carboxyclic radicals with 6 to 14 nuclear atoms, in particular radicals of the phenyl, naphthyl and anthryl series, e.g. B. from phenyl, tolyl, xylyl, methoxyphenyl, carbethoxyphenyl, p-dimethylaminophenyl, naphthyl, hydroxynaphthyl or anthryl radicals. Preferably the aryl radicals consist of optionally substituted phenyl radicals.

Heterocyclic radicals here are saturated and unsaturated monocyclic or condensed ring systems with at least to understand a heteroatom in the ring core, for example furyl radicals, e.g. B. 2-furyl radicals, also morpholino, piperidono-, Quinoline, piperidyl, pyridyl, thienyl, morpholinyl, thio-morpholino or thiomorpholinyl radicals.

If the phosphonium salts have substituted carbonyl radicals as electron-withdrawing radicals, then these advantageously correspond to the following structure furrnel:

¹¹ 8 CR ⁸

309807/1220

wherein R is either a hydrogen atom, an optionally substituted one Alkyl radical with 1 to 20 carbon atoms, an alkoxy radical having 1 to 10 carbon atoms, an alkenyl radical, d. H. an optionally substituted alkyl radical having 3 to 10 carbon atoms and one or more ethylenically unsaturated bonds in the aliphatic chain, e.g. an allyl, butadienyl or styryl radical, or an aryl radical, in particular the phenyl or naphthyl series, e.g. B. a phenyl or naphthyl radical, or an aryloxy radical, e.g. B. a phenoxy or naphthoxy radical, or a radical of the following formula:

αϊ - cn - ρ

R ² R ³ R ⁶

where R ² , R, R, R ^, R and X have the meaning already given, represents »

In addition to the phosphonium salts of the structural formula given, furthermore various other phosphonium salts are used which have an alkyl radical which is substituted by at least one electron withdrawing radical. The usability Such phosphonium salts can be determined in a simple manner by means of a test experiment. This test is particularly suitable to determine to what extent a specific electron the remainder is the release of the triorganophosphine promotes or favors when treated with a base. For this purpose, the phosphonium salt to be tested can first be dissolved in water or a mixture of water and an organic solvent. Suitable organic solvents, preferably can be used in only moderate concentrations, for example in concentrations of 1 to 51, based on the total volume of the solution, for example, alcohols * »After the solution of the to testing phosphonium salt is mm a weak base, for example Ammonia, sodium bicarbonate or pin organic amine added

3 0 9 8 0 7/1220 bad original

give. If a precipitate forms when the base is added or after the base has been added and the solution is heated gently at the same time, so this is an indication that the corresponding triorganophosphine has been set free and that the tested one is Phosphonium salt is suitable for the production of a recording material according to the invention. The setting in freedom should be part of this a pH of about 8 or above.

Triorganophosphine, for example, easily obtained from corresponding Let phosphonium salts set free are:

Triphenylphosphine

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

P, P-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 (diphenylamono) phosphine P-methyl-P, P-diphenylphosphine Tris (4-chlorophenyl) phosphine Tris (4-methoxyphenyl) phosphine Triethoxyphosphine 1,2-bis (diphenylphosphine) ethane 1,4-bis (di-n-butylphosphine) butane and 1,8-bis (di-4-chlorophenylphosphine) octane.

Phosphonium salts suitable for the production of photographic recording materials according to the invention can be prepared according to customary methods known processes. For example,

309807/1220

43

wise suitable phosphonium salts via a Michael addition reaction by making an Athens with an electron withdrawing group with dry hydrogen chloride gas and an Ρ, Ρ, Ρ-triorgano-substituted phosphine is converted into ether. The resulting solid chloride salt can be filtered are isolated, whereupon an anion exchange is optionally carried out in water or an alcohol in a conventional manner can be.

The reaction can be represented by the following reaction equation:

R ² R ⁴ R ² R ⁴

II θ
R ¹ -C = CH + PR ⁵ - ^ ^ R ^T -CH-CH-P ^e -R ⁵ Χ ^θ

R ³ R ⁶ R ³ R ⁶

wherein R, R, R, R, R, R and X have the meaning already given own.

This method has proven to be particularly advantageous when when the Athens substituted by an electron withdrawing group and the trisubstituted phosphine in warm alcohol and if an acid with the desired anion, for example fluoboric acid or perchloric acid, is added to the solution whereupon the precipitated reaction product can be separated off and dried.

The phosphonium salts used according to the invention can, however, also be prepared by other processes, for example by Implementation of a / trisubstituted phosphine with a 1-bromo-2-ethane, that in the 2-position by an electron withdrawing residue is substituted in ether. The preparation of suitable phosphonium salts in this way can be, for example, by reproduce the following reaction equation:

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-Wf-

R ^ CH-CH-Br + PR ⁵

R-CH-CH-R-

R ³ R ⁶

Br

Finally, the phosphonium salts can also be prepared by reacting a trisubstituted phosphonium!) Romide with an athen _t which is substituted by an electron withdrawing radical according to the following reaction equation:

R ⁵ -P ♦ HBr

-> R ⁵ -PH +

θ R * -C = CHR ³

R ^ CH-CH-PR ³

R ³ R ⁶ J

According to the method described, a wide variety of Prepare phosphonium salts which are suitable for the production of a recording material according to the invention. Particularly advantageous phosphonium salts for the production of photographic Recording materials according to the invention include, for example, the compounds listed below:

1. P- (2-cyanoethyl) -P, P, P-triphenylphosphonium bromide

2t P- (2-acetyl-1-phenylethyl) -Ρ, Ρ, Ρ-triphenylphosphonium tetrafluoroborate

3. P- (2-acetyl-1-phenylethyl) -P, P, P-triphenylphosphonium-

perchlorate

4. P- ^ 2,2-bis (ethoxycarbonyl) -1-phenylethyl7-P | P, P-triphenyL

phosphonium tetrafluoroborate

5. P- / 2,2-bis (ethoxycarbonyl) -l-phenylethyl7-P »P, P-triphenyl

phosphonium perchlorate

6. P- ₍ / 2-Benzoylethyl) -P, P, P-triphenylphosphonium perchlorate

3 (J ü Ü (J 7 / I 2 2 0

7th P- (2-benzoyl-1 -phenylätliyl) -P, P, P 'triphenylphosphoniumtetrafluorborat>

8. P- (2-Benzoyl-1-phenylethyl) -P, P _s P = triphenylphasphonium-

perchlorate

9. P- (2-Benzoyl-1-phenylethyl) »Ρ, Ρ, Ρ-triphenylphosphonium

tetraphenylborate

10. P- (3-oxobutyl) -P _II P _i P ° triphenylphosphonium chloride

11. P- (3-oxobutyl) -P _i P, P ° triphenylphosphonium tetra-luorborate

12. P- (3-oxobutyl) -P, P _r P-triphenylphosphonium perchlorate

13. P- (2-cyanoethyl) -PjPjP-triphenylphosphonium dietrafluoroborate

14. Ρ- ^ ϊ-methoxybenzoyl) -1 -phenylethyl7-P s> P, P-triphenyl-

phosphonium tetrafluoroborate

15. P- ^ 2-Benzoyl ~ 1- (4-methoxypli @] iyl) ethyl 7-P ₈ P _! > P ™ triphenyl

phosphonium tetrafluoroborate

16. P- (2-ethoxycarbonyl-1-phenylethyl) -P _i PpP-tripheayiphospho-

nium perchlorate

17. P- (2-ethoxycarbonylethyl) -P _B P "P ~ triphenylphosphonium-

tetrafluoroborate

18. P- (2-Benzoyl-1-phenylethyl) -P ₁ P ₈ , P ^ triphenylphosphonium-

tetrafluoroborate

19. P- (2-Benzoyl-1-phenylethyl) -P, P, P-tris (p-tolyl) -phospho-

nium tetrafluoroborate

20. P- (2,2-diacetyl-1-phenylethyl) -P, Pj, P-triphenylphosphonium-

tetrafluoroborate

21. P- / 2- (1-Hydroxy-2-naphthoyl) -1-phenylethyl7-P | _l PiP-triphenylphosphonium tetrafluoroborate

22. P- (2-Benzoyl-1-phenylethyl) -P, Ρ, Ρ-tris (4-methoxyphenyl) -

phosphonium tetrafluoroborate

23. P- (2-Benzoyl-1-phenylethyl) -Ρ, Ρ, Ρ-triphenylphosphoniuin-

hexafluorophosphate

24. P- (2-Benzoyl-1-phenylethyl) -P, P, P-triphenylphosphonium-

hexafluorotitanate

25. P- (2-Benzoyl-1-phenylethyl) -Ρ, Ρ, Ρ-triphenylphosphonium-

liejcafluorantimonat

26. "P- (2-Benzoyl-1-phenylethyl) -P, P-dimethyl-P-phenylp] iospho-

nium perchlorate

309807/1220

27. P-CS-Oxo-i-phenylbutylJ-PjP ^ -triphenylphosphoniuin-p-.

toluenesulfonate

28. P- (2-methyl-3-oxo-1-phenylbutyl) -P, P, P-tripheny! Phosphonium-

perchlorate

29. P- ^ T- (4-methoxycarbonylphenyl) -S-oxobuty ^ -PfPrP-tri-

phenylphosphonium tetrafluoroborate

30. P- / T- (4-methoxyphenyl) -3-oxobutyl7-P, P, P-triphenylphos-

phonium tetrafluoroborate

31. P- ^ S- (2-Oxocyclohexyl) benzyl7-P, P # P-triphenylphosphonium-

tetrafluoroborate

32. P- ^ a- (2-oxocyclopentyl) furfuryl7-P »P» P-triphenylphospho-

nium tetrafluoroborate

33. P- ^ a- (2-Oxocyclohexyl) -2-methylbenzyl7-P »P» P-triphenyl-

phosphonium tetrafluoroborate

34. P- (2-cyanoethyl) -P _t P, P-tris (3-methylphenyl) phosphonium-

perchlorate

35. P-CS-ÜxobutylJ-PjP-diphenyl-P-ynethylphosphoniurotetra-

iluoborat

36. P- (2,2-diacetyl-1-phenylethyl) -Ρ, Ρ, Ρ-tris (4-methylphenyl) -

phosplionium p-toluene sulfonate

37. P- / 2- (1-hydroxy-2-naphthoyl) -1 -phenylethy ^ -P ^ .P-tri-

methylphosphonium tetrafluoroborate

38. P- (2-Benzoyl-1-phenylethyl) -P, P-diphenyl-P-ethoxy-

phosphonium tetrafluoroborate

39. P- (2-Benzoyl-1-phenylethyl) -P ^ P-dimethyl-P-phanylphos-

phonium laxafluorophosphate

40. P- (2-Benzoyl-1-phenylethyl) -P-pentafluorophenyl-P, P-di-

phenylphosphonium perchlorate

41. P- (2-Benzoyl-1-phenylethyl) -P-butyl-P, P-dimethoxy-

phosphonium tetrafluoroborate

4 2. P- (3-0xo-1-pheny! Butyl) -Ρ, Ρ, Ρ-tiis (n-butyl) phosphonium p-tou1 sulfonate

4 3. Ρ-γΤ- (4-Μί l: lioxycarboiiylphcny]) -? - üxobutyl7-P »P» P-tris- (Hinieihy j amino) phosphoniunite elrai luorborate

4 4. P- / »f (2-0xoc) (lohexyl) benzyl 7 ~ P, P, P-trie (n-octyl) phos-

.'honiuiiifet rafluoi bornt:

3098G7 / 1220

45. P- ^ ~ ct- (2-Oxocyclopentyl) furfuryl J-I ^ Pil'-tri-s (diphenylamino) phosphanium tetrafluoroborate

46 »P- (2-cyanoethyl) -P, P, P-tris (4-chlorophenyl) phosphonium tetrafluoroborate

4 7. P- (3-0xobuty 1) -P, P, P-1 ris (4-methoxyphenyl) ρ hus-plioni unite met luorborat and

48. P- (2-Acetyl-1-phenylethyl) -P, P, P-triethoxyphosphonium tetrafluoroborate.

For the production of the photographic recording materials according to According to the invention, at least one phosphonium salt is mixed with at least one organoazide and the mixture is applied to a layer support applied, preferably using a suitable binding or dispersing agent. By treatment with a base supplies the phosphonium salt a triorganophosphine, which on chemically with the azide to form a radiation-sensitive Phosphine-azide complex converts »These complexes are formed while doing this under normal ambient conditions.

In addition to a wide variety of phosphonium salts, can be used for the production of the recording materials furthermore the most diverse use customary known organoazides, the suitability of a specific azide being determined in a simple manner can, according to the test described, which is suitable for this, the suitability of phosphonium salts on their usability ascertain. In this case, however, the azide to be tested is dissolved together with a phosphonium salt, known from the is that it is used to manufacture a recording material according to of the invention, for example a triphenylphosphine supplying phosphonium salt.

For the production of recording materials according to the invention fleojfinete Orginoazide, 4. h. organic azides are the various compounds sensitive to radiation that have so far been used for Ilorite Il mg. photographischür AuükopieiMiatcrialion dos Typ. ·; used

K η C

If

were, in which on exposure an az id with a! "arbstof fbi Idiiar due to the formation of a dye in the exposed areas is implemented. Suitable azides thus include, for example those from the liSA patents.> 062 650 and 3,282,693 known aryl azides, aminoary azides and iieterocycliselten azides. Further those azides which are known as photosensitizers for polymers are suitable. Such photosensitizers can be made from consist of the same azides as are used in the manufacture of print-out materials and as, for example, in the book by Kosar, "Light-Sensitive Systems", published by John Wiley & Sons, Inc., New York, (1965), in particular pages 330-336 including the footnotes, or they can be derived from these Azides consist of different azides.

Others for the production of photographic recording materials Organic azides suitable according to the invention are known, for example, from U.S. Patents 2,940,853, 3,061,435 and 3,143,417. When using heterocyclic azides, preference is given to using those in which the azido radical is in the heterocyclic Ring is not in the ortho position to the heterocyclic ring atom. Azides have also proven to be advantageous composed of polymeric azides such as those described in U.S. Patents 3,002,003 and 3,096,311.

Particularly beneficial organoacides include the following:

4-azidobenzenesulfonamide Ethyl 4-azidubenzoate Uhyi-2-azitlobenioate (Uyceryl 4-azidobenzoate 3-azidobenzocic acid

AsO (OiI)

4-AzidobenzoL rsonic acid 4-Azidobenzainid 4-AzidOfN-inetiiylacetanilid -l-azidobenzophynone 7 iV-A2idopheii] rl) -6-methylbenzothi.i- »1 ■ 'iJo-α, (!, a-trifluoromethylbeiiiol

BAD ORiQiNAL 1 \

AS

3-Azido-4-ciiloro-a, a, a-trifluoromethylbenzene 4-azidobenzonitrile

3-Hydroxyprppyl-4-azidobenzoate Phenyl-4-azidobenzoate.

2- (3-hydroxynaph, thyl) -4-azidobenzoate N-methyl-N-phenyl-4-azidobenzamide N- (2,6-dimethylphenyl) -4-azidobenzamide 4-azidobenzopiperidide N- (1-naphthyl) -4- azidobenzamide N- (Pentafluoropheny2) -4-azidobenzamide Phenyl-4-azidophenylsulfonate 2,4,6-TrichloTplienyi-4-azidophenylsulfonate H- (4-Azidophenylsulfonyl) phthalimide 4-Azidobenzophthalyl-N-phenyl-N-phenyl-phenyl-azide N- (4-Azidophenylsulionyl) -piperidine N- (2,6-Dimethylphen) J) -4 -azi dophenyls _f ul f on amide N- (4-Azidophenylsulionyl) swccinimide N- (6-Azido-2-naph thy 1sulfonyl) piperidine N-methyl-N-phenyl-2-azidonaphtljalin-G-sulfonamide phenyl-6-azidonaphthalene-2-sulfonate N- (6-azido-2-naplithyl sulfonyl) succinimide N- (6-azido-2- naphthylsulfonyl) phthalimide 1-azido-2,4,6-trichlorobenzene 2-azido-3-nitrobenzene 4-azidobenzoic acid

3-azidophthalic anhydride 4-azidocinnamic acid 3-azidobenzenesulfonamide

2-Azido-9-fluorenone - .., .. ·

1-azido-5-metho2: ynapht.halin _{; v}

2- (4-A7.idoj ⁱ henyl) -5-phenyl'oxazole ............

■ \ '-Azi ÜO-4 -chloiochalcon / - (4'-Λ:''' - '"i -henyl) for £ zoxazole

: BAD ORIGINAL

30S807 / 12? 0

2-phenyl-5- (4-azidoph * nyl) oxazole 2- (4-azidobenzylidene) -3,4-dihydro-2H-1-naphthone 4-azidochalcone

N- (4-azidobenzylidene) -4-chloroaniline 2- (4-azidophenyl) benximidazole 1-azido-2 ₍ 4-dichlorobenzene 2- (3-azidopheny1) -5-phenyloxazo1 4.4 ^t -diucido-3,3 ⁽ -diB «thoxybiphenyl 2-azidophenetol

4-azidophenetol

Trimethylene bis (4-azidobenzoate)

Bis (4-azidophenyl) disulfide 4-azido-3, S-iiethoxybent * nilide N-methyl-4-azidoacttanilide 4-azidophenyl sulfide 4-azido-3-nitroanisole N-CS-azidophenylsulfonyl-succinimide 4-azido-3,5-diBi # thoxyphenylmorpholine 3-azidoquinoline

2-azidocarbazole

2-azidobenzoic acid 4-azidophenoxyessi.giaure N-methyl-N-octadecyl-4-aiidoaniline t-Azido-4-bromonaphthalene

Bis (4-aiidophenyl) ether

4-azidoazobenzene

N- (4-Azidoph * nyl) -N-methylmorpholinium tetrafluoroborate

4'-azido-4-toluenesulfonanilide 4-azidobenzenesulfonate 1 -Axido-4-aethoxynaphthali.

4-azidostyryl-1- maphtkyl ketone 3- (4-azidophenyl) cuaar in 1,2,3,4,5,6-llexa- (4-azi4ob # nzoxy) hexane 4 _f 4 '-diazidodibenzalftone 1-azido-2,4, 6-tribroeob »a» ol

4-azidoacetanilide __

BATH ORIGINAL

309807/1220

2-azidodiphenyl ether

2,5-bis (4-azidophenyl) oxazole 2- (4-azidophenethyl) -5-phenyloxazole 2- (4-azidophenethyl) benzoxazole

4,4 · -Diazido-2,2'-stilbene-di (N> N-dibutylsulfonamide)

2,6-Bi (4-azidobenzal) -4-methylcyclohexanone poly (vinyl acetate-co-4-azidobenzoate) 1-azido-3-cyano-4-methoxybenzene 1-azido-3-cyano-4-morpholinobenzene N- (4 -Azido-2-cyanophenyl) piperidine N-Penty1-4-azido-2-cyanoaniline N _r 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-chloroaniline 4-azidodiphenylamine

4-azido-2-cyanodiphenylamine, 4-azido-2-cyano-4'-methoxydiphenylamine 4-Azido-2-cyano-4-dimethylaminodiphenylamine 1-Azido-2-methoxy-4-morpholinobenzene 1-Azido-3-methoxy-4-morpholinobinzole

N-methyl-4- (4-azidophenyl) -2,6-diphenylpyridinium perchlorate

N-methyl-4- (4-azidostyryl) -2, i-diphenylpyridinium perchlorate and

2 _t 5-bis (4-azidophenyl) oxadiazoJ.

The photographic recording materials according to the invention are not or only insignificantly sensitive to radiation before the phosphine is released. Their sensitivity corresponds to the sensitivity of the interwoven azide, so that the recording materials according to the invention are distinguished by an extremely high storage stability © x spontaneously "in situ" ,, used after which the generated complex for imaging can warden "

309807 / I 220 BATH

Geraäli an advantageous embodiment of the invention is the Image-forming layer using one made of a polymer existing binder generated. Suitable binders are the conventionally known film-forming binders, including Commonly known hydrophobic polymers, which are made using organic solvents for the production of film-forming Layers can be used and which are so permeable to bases, including gases and liquids, that they are do not hinder phosphine formation and image dye development. Typical binders suitable for producing the recording materials according to the invention are, for example Cellulosic polymers, e.g. B. ethyl cellulose, butyl cellulose, as well as cellulose esters, e.g. B. cellulose acetate, cellulose triacetate, Cellulose butyrate, cellulose acetate butyrate, and also vinyl polymers, e.g. B. polyvinyl acetate, polyvinylidene chloride, polyvinyl butyral, Copolymers of vinyl chloride and vinyl acetate, polystyrene, polymethyl methacrylate, homopolymers and copolymers of acrylamides ^ Copolymers of alkyl acrylates and acrylic acid and the like, for example:

Poly (N-isopropyl acrylamide)

Poly (diacetone acrylamide)

Copolymers of diacetone acrylamide and

N-isopropyl acrylamide

Copolymers of methacrylamide and N-isopropyl acrylamide Copolymer «of N-isopropyl acrylamide and

I-vinyl-2-pyrrolidone copolymers of methyl methacrylate and

Methacrylic acid and copolymers of butyl acrylate and acrylic acid.

Furthermore, such polymers as polyphenylene oxides, terpolymers of ethylene glycol, isophthalic acid and terephthalic acid, terpolymers from p-cyclohexanedicarboxylic acid, isophthalic acid and cyclohexyleubismethanol, Copolymers of p-Cyclohexanedicarbons: iure and 2,2,4,4-Tetram * thylcyclobutan-J, 3-dLol and also finally Condensation products of epichlorohydrin and IHsphenol-A.

3 0 9 8 0 7/1220 BAD ORIGINAL

Advantageously, the photographic recording materials according to the invention can additionally form a dye Contain couplers, for example in the image-forming layer or in a layer adjacent thereto, which presumably with a photolytic product of the phosphiii-azide complex are able to react to produce a dye in the exposed areas.

Such color couplers are advantageously used in molar concentrations which correspond to the concentrations of the phosphine-azide complex are equivalent are used or in a slight molar excess, for example a 5 to 10ligen molar excess, to ensure maximum dye formation.

However, the color couplers are not needed in the photographic material to be present according to the invention »Si® can rather, they can also be supplied later, for example by means of a solution.

For the production of a photographic recording material according to the invention or for the development of the same, a wide variety of customary known color couplers can be used, such as are used, for example, in the known two-component diazo-type recording materials and as described, for example, in the book by Kosar "Light-Sensitive Systems ", Published by John Wiley & Sons, New York (1965), particularly pages 220-240. Other color couplers, di © Mach of the invention or the development thereof using blank for the production of photographic Aufzeichniingsmaterialien ₈ are known for example from US Patent 3 S 73 052, in particular from column 6, line 17 to column 7, line 20, is known.

Typical color couplers that can be used according to the invention are, for example:

ORIGINAL

309807 / 122.0

2,3-naphthalenediol

2-hydroxy-3-naphthanilide

2-IIydroxy ^l-2 ~ methyl-3-naphthanilide, 2-hydroxy-2 ·, 4'-dimethoxy-5'-chloro-3-naphthanilide, 2-hydroxy-2 *, 4 'dimethoxy-3-naphthanilide, 2-hydroxy -2, 5'-dimethoxy-4'-chloro-3-naphthanilide 2-hydroxy-1'-naphthyl-3-naphthanilide 2-hydroxy-2'-naphthyl-3-naphthanilide 2-hydroxy-4 ^f -chloro- 3-naphthanilide, 2-hydroxy-3-naphthanilide

2-hydroxy-2 ', 5'-dimethoxy-3-naphthanilide, 2-hydroxy-2 ^l, 4 ^l -dimethyl-3-naphthanilide 1-hydroxy-2-naphthamide

N-methyl-1-hydroxy-2-naphthamide, N-butyl-1-hydroxy-2-naphthamide N-octadecyl-1-hydroxy-2-naphthamide N-phenyl-1-hydroxy-2-naphthamide, N-methyl-N-phenyl-1-hydroxy-2-naphthamide N- (2-tetradecyloxyphenyl) -1-hydroxy-2-naphthamide

Ν- / Ϊ- (2,4-di-tert-amylphenoxy) butyl7-1-hydroxy-2-naphthamide

1-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 (1-hydroxy-2-nmphthamidobenzene) 2-acetamido-5-methylphenol 2-acetamido-5-pentadecylphenol 2-butyramido-5-methylphenol

2- (2,4-di-tert-amylphenoxyacetamido) -5-methylphenol and

2-benzamido-5-methylphenol.

Further suitable couplers are those which have a reactive methylene or methine radical, such as those from der i; S.A-Pat.eni.schrift 3 062 650, in particular from column 4, line

309807/1220 ORIGINAL BATHROOM

le 8 to column 4, line 27, are known. The use of such Color couplers, e.g. B, of 3-methyl-1-phenyl-5-pyrazolone » has proven to be particularly advantageous when an organoazide is used which is substituted by an amino radical is, for example when an aminoarylazide is used. Particularly advantageous aminoarylazides are the 4-amino-i-azidobeBzoi and its derivatives.

The production of the image-forming layers is expediently carried out by using at least one phosphonium salt and at least one organoazide in a suitable © !! Solvent can be dissolved, whereby a wide variety of organic solvents can be used for the solution, for example methyl _{ethyl ketone, methylene chloride, acetone f} short-chain alkanol © ₈ dichloroethane, tetrahydrofuran, toluene and the like. individually or in combination with one another. "In the solution initially prepared," the ratio of phosphoniam salt to azide can be very different. Preferably, however, the phosphonium is used in a slight molar excess, for example a 5 to 10% molar excess, in order to ensure that all of the azide is complexed by the triorganophosphine which is set free from the phosphonium salt.

The support of a photographic recording material according to the invention can consist of one of the usual supports, such as are customary, for example, for known diazo-type recording materials. for example a cellulose ester, for example cellulose acetate, cellulose triacetate, cellulose acetate butyrate or a poly _a -olefin, in particular one made from an olefin with 2 to 10 carbon atoms, e.g. made from polyethylene, polypropylene or from polystyrene, and also polyesters, eg Polyäthylenierephthalat, or from a polycarbonate, but also from metals, eg. B. zinc and aluminum, as well as paper,

309θ07 / 122α

including one that has been coated with polyethylene or polypropylene.

The coating of the support takes place in an advantageous manner according to the customary known coating processes. For this purpose, the components of the image-generating layer are initially in one dissolved in a suitable solvent, d. H. with or without a binder. It has proven to be expedient to use coating solutions which contain about 5 to about 20% by weight, in particular about 8 to 15% by weight, contain solids. If the solution contains a binding agent, then it is advisable to use about 20 parts of binding agent for every 100 parts up to about 50 parts by weight of the image-forming components, especially about 25 to about 45 parts by weight per 100 parts by weight of binder. The substrate can be coated by dipping of the support into the coating solution, by spin coating, by painting or brushing, or by means of a Coating nissers or a coating funnel take place. The layers are expediently applied in a layer thickness of - measured wet - about 0.0025 to 0.005 cm, whereupon the applied layer is dried in the customary known manner will.

The activation of the photographic recording materials according to the invention for the purpose of producing a phosphine-azide complex A wide variety of bases can be used in the image-generating layer, in particular those used to initiate the Coupling reaction can be used in the diazo type recording materials. Suitable bases are, for example, ammonia, organic amines and other organic nitrogen-containing bases. Typical bases suitable for carrying out the activation are for example the bases described in the already cited book by Kosar and also the bases, for example, in U.S. Patent 3,578,452 and Canadian Patent 772,109.

309807/1220

Baeem or solutions thereof with a pH of at least 8 are preferably used, so that rapid activation takes place. The treatment can be ⁰ nungsraaterials done in a solution of Bas® or by steaming with vapors of the base and the like ₀ by immersing the Aufzeich "

After treatment of the recording material with the base, it is sensitive to radiation and can be exposed image-wise without further pretreatment easily through. Establish a step wedge spectrogram for the phosphine-azide complex in question. It has been shown that the complexes produced in the photographic recording materials according to the invention are sensitive to the action of ultraviolet rays and other actinic rays, so that the recording materials according to the invention are generally exposed with conventionally known mercury arc lamps. are köEii @ n _{0 is} the © in to ultraviolet rays rich in light emitting »As a result, can contribute to the exposure of the Aufseichnung'smaterialien .After oF INVENTION = dung the customary known Diazokopiergeräte and other © be used commercially available photocopying devices which have exposure chambers or exposure sections, the ultraviolet Emit radiation »

It should be noted that the radiation sensitivity of the phosphine-azide complexes is not to be equated with the sensitivity of aryl azides, for example those used in photographic applications Vesicular processes or used in other photographic systems will. Such aryl azides are known to have only one low photoreactivity, whereas the radiation-sensitive phosphine-azide complexes found in a photographic recording material be generated according to the invention, a relative have photographic sensitivity which is about 10 times greater than the sensitivity of no comparable

3 0 9 8 0 7/1 22 0

If

bound azides

If a photographic recording material according to the invention is exposed to activating rays after the sensitive phosphine-azide complex has been formed, an image is produced in the exposed areas if a color coupler is present in the recording material. Usually this is an easily visible or easily recognizable dye image, the optical density of which depends on the particular composition of the imaging layer. In certain cases, however, only a latent image can be generated which is not readily recognizable. In this case, however, this latent image can be made visible by heating the recording material.

It is believed that the dye-forming reaction is caused by the imagewise liberation of hydroxyl ions and ammonium hydroxide is initiated upon exposure of the phosphine-azide complex. It is also assumed that the image-wise Release of hydroxyl ions and ammonium hydroxide due to a reaction of a phosphine imine anion, which forms upon exposure, takes place with water which is present in the recording material is naturally present.

Following the imaging exposure, the recording material be heated in an advantageous manner, namely to a temperature which the material before the copying out Non-image areas stabilized.

It is assumed that the phosphine-azide complex rearranged to form a stable, practically colorless phosphinimine.

A low optical density image is obtained upon exposure or a latent image, the heat stabilization simultaneously causes an image intensification or an image intensification under Creation of an image easily recognizable by the eye.

309807/1220

The recording material is preferably heated to a temperature of at least approximately 60 ^° C. up to approximately 130 ^° C. for stabilization. It applies here that correspondingly shorter heating times are to be used at higher temperatures. The duration of the heat fixation can be very different. Si «depends on various factors, for example the temperature used. It has proven to be useful to heat the recording material for about 5 seconds to 2 minutes. The heating can take place in the usual b & annter manner, for example by bringing it into contact with a heated surface, by introducing it into a heated chamber and the like.

In those cases in which no color coupler is present in the recording material, exposure of the phosphine-azide complex is followed by treatment with one or more couplers of the type already described «Either spontaneously dense dye images or even intensification or Reinforcement in the manner already described.

In this case, the color couplers can be used in the form of a solution brought into contact with the recording material, for example by dipping the recording material into the solution containing the color coupler or by buffing or spraying the solution onto the recording material. After this Treatment, the recording material can be washed and / or dried, optionally drying with the Heat stabilization can be combined.

309807/1220

3P

The use of photographic recording materials according to the invention which has a phosphonium salt, a radiation-sensitive azide of that known from US Pat. No. 3,062,650, has also proven particularly advantageous Type, with an amino radical, e.g. B, a p-disubstituted aminophenyl azide, and a color coupler that reacts with the azide able to contain. The use of such photographic recording materials enables, inter alia, production two-color photographic images as follows:

The recording material is first imagewise imagewise Subjected to radiation sensitive to the azide. In this way a visible dye image is obtained in the exposed areas. The recording material is then activated by treatment with a base, z. B. by treatment with ammonia vapors, whereby the dem Phosphonium salt corresponding triorganophosphine is set free and a phosphine-azide complex is generated. Then will the recording material is exposed a second time imagewise to radiation that is sensitive to the complex be different from the azide. As a result, two different sources of radiation may be required for the imagewise exposures, although, in general, ultraviolet rays are suitable for both cases Exposure forms another picture in the exposed areas. This second dye image can in certain cases be intensified or strengthened in the manner already described. If a visible image is obtained as the second image, it advantageously has one of the first Exposure obtained image different hue. Thus, on the second exposure, it becomes an image with only low optical density or obtain a latent image, the recording material

309807/1220

If the concentration of the azide in the recording material is sufficient and the first exposure is not so intense that all of the azide in the exposed areas is photolized, then the azide present in these areas can contribute form a complex with the phosphine upon activation with a base, with the second exposure producing a second dye image in the areas ₀ which are common to both exposures «

The novel recording materials are suitable fro = excellently for making negative Bilders, d "> h _o ^ which correspond to the exposed areas of images"

However, the photographic Aufzeichnuiigsmaterialien make the invention can be developed on thermophotogffaphischem way under supply positive images ι · ι®τά®η _ΰ like _a tu BildeOt ^ said non-irradiated areas entsps'Qefeeno do it © m purpose eim photographic Aufzeichniisigsxiiaterisl macli ä @ t invention _D that was initially activated for the purpose of the formation of a phosphine-azide = KompIsssos an imagewise thermal exposure raites ¹ «throwing _β whereby the thermally exposed areas are stabilized before copying ornaments» This is followed by a full exposure, namely with a Radiation activating the complex for the purpose of producing a visible or intensifiable or intensifiable dye image «. In the case ₀ in which no color coupler is present in the recording material ₆ the image development includes a treatment with a coupler solution in the manner already described

According to a further advantageous embodiment of the invention, lithographic printing plates can be produced by using a hydrophilic polymeric AgId _0, for example of the type _P known from US Pat. No. 3,002,003, as the azide. In a corresponding manner, lithographic printing plates can be produced by using hydrophilic polymeric color couplers

BATH ORIGINAL 309807/1220

can be used, for example polymeric pyrazolones. Preferred number wise, the azide used together with a polymeric coupler consists of a bis-azide. After exposure and subsequent Development stages in the manner already described, the developed surface is moist from the water that is not exposed Districts is included. Bold printing ink can be applied to a surface to be printed from the exposed areas transfer.

In the following, the production of some according to the invention will begin usable phosphonium salts are described in more detail.

1) Production of phosphonium salts

A) Production of P- (2-cyanoethyl) -P, P, P-triphenylphosphoniura-

Lune mixture of 2, 6 g of triphenylphosphine and 5 ml of 3-Uromopropionitri] winds on a steam bath until solidification (several hours) heated. After isolation, the solid mass obtained was washed with diethyl ether and dried. The smoldering z]) imi 1 of the phosphonium salt was 212-215 ⁰ C.

H) Horst el ment of F- (2-acetyl-1-phenylethyl-P ^ jP-triphenyl phosphoniuiii f luo ) borate ,

Dry hydrogen chloride gas was passed into a solution of 2.6 g of triphenylphosphine and 1.5 g of benzalactone in 7 ml of diethyl ether until the deposition of a solid white mass had ceased. The solid chloride was then filtered off, dissolved in water and treated with iluoboric acid. Again a solid white mass separated out, which was filtered off and dried. Ms a total of 4.5 g of the Phosphoniumfluorborates having a melting point of 205-206 ⁰ C obtained.

BATH ORIGINAL

309U07 / U2

C) Production of P- (2-acetyl-1-phenylethyl) -P, P, P-triphenyl phosphonic jumper chlorate

1 ml of a 70% perchloric acid was added to a solution of 1.5 g of benzalactone and 2.6 g of triphenylphosphine in 25 ml of warm ethanol. An extensive white precipitate separated out, which was filtered off, washed with ethanol and then with diethyl ether and finally dried. The yield of phosphonium salt was 5 g. The melting point of the phosphonium salt was 214 ^° C.

II) The following examples are intended to illustrate the invention in more detail.

example 1

A solution of 3 g of P-sulfamoylphenyl azide and 2.6 g of 2,3-naphthalenediol in 25 ml of acetone was added to 210 ml of a 1 oily solution of cellulose acetate butyrate in 1,2-dichloroethane. Thereupon a solution of 0.00 t mol of phosphonium salt, namely P- (2-cyanoethyl) -P, P, P-triphenylphosphoniuabromide in 7 ml of acetone, was added to 7 ml of the batch described above, whereupon the mixture was applied to a polyethylene terephthalate support in one layer thickness from - measured wet - 0.015 cm was applied. The photographic recording material thus obtained according to the invention was then gassed with ammonia vapors, exposed in the exposure unit of a commercial Diazokopiervorrichtung with a Quecksilberbogenlarape through a silver negative and then heated for 1 minute at a temperature of 120 ⁰ C.

In this way a stably fixed copy was obtained with a clearly visible dye image corresponding to the exposed areas obtain.

The procedure was carried out using the phosphonium salts 2-JH repeated. Accordingly, favorable results were obtained.

309007 / t22tt

Example 2

Another 21 photographic recording materials became (A-U) prepared by the method described in Example 1, including the phosphonium salts given in Table I below were used"

Table I.

Phosphonium salt record · No. material

2 A

4 B

5 C

6 D

7 E.

8 F 10 G Π η 12 I.

14 y

15 K

18 L

19 M.

22 N.

23 0 25 P.

30 Q

27 R.

28 p

31 T

In some cases a mixture of acetone was used as the solvent and methanol used in a volume ratio of 95: 5. the

7/1220

Recording materials were then used to produce images by the method described in Example 1. The recording materials AP were exposed and heated after being stored for 9 days at 40 ^° C. and normal atmospheric humidity. In the case of the QT recording materials, exposure and heating took place after the recording materials had been incubated for 2 days at 40 ° C. and 100% relative humidity. In all cases, good visible photographic images were obtained »

For comparison purposes, another recording material was produced which contains cyclohexanon-3-yl-triphenylphosphonium chloride as the phosphonium salt. Using this recording material, a normal image was obtained when the material was developed immediately after its preparation and heated "3Cc in image, however, was obtained when the exposure and Lrhitzung after 2 days of storage was carried out at 40 ⁰ C and normal humidity.

Example 3

liine solution of 0.15 g of p-morpholine-ophenylazide, a color coupler, namely 0.2 g of 2,4-dich.loi-6- (2,4-dipentylphenoxyacetamido) -3 «methylphenol and 0.8 g of P- ( 2-Acetyl-1 »phenyl ätJiy.I) -P ₉ P, Pt ji p, \> my 1 - phosphonium tetrafluoroborate in 15 ml of acetone was prepared, the resulting solution was then added to 15 ml of a 101% cellulose acetate butyrate solution in dichloroethane, whereupon the mixture is applied by means of a coating knife to a polyalkylene terephthalate film support in a layer thickness of - wet - 0.015 cn; was applied.

I) as obtained photographic material was then initially in a commercially available diazo copier a transport speed of 1.52 m / minute under Bi of a blue dye image in the exposed areas

close σ «v was the recording s-jiiöteriaJ 10 seconds in. ; - ■

309807/1/20 ORIGINAL BATHROOM

"f /

placed at 5O ⁰ C with wet ammonia vapors in contact "to set the phosphine from the phosphonium salt in freedom. Finally, the material was exposed again, specifically in a commercially available ozalide copier at a transport speed of 4.57 m / minute, producing an orange-colored dye image in the areas that were now exposed.

The background areas were stabilized ^{by heating at 110 ° C. for 5 seconds.} In this way a pale pink background was obtained.

In further experiments to activate the recording material, d. H. to set the phosphine free, using aqueous solutions of organic bases from the phosphonium salt, as described in U.S. Patent 3,578,452. Equally favorable results were obtained in all cases.

Example 4

There have been a number of other photographic recording materials produced, exposed and fixed according to the method described in Example 1. This time, however, those in the Azides listed below in Table II and the couplers listed in Table III below were used. Furthermore were the 20 phosphonium salts listed in Example 2 for the experiments used. Irrespective of the phosphonium salt used in the individual case, dye images were obtained whose color was from the azide coupler combination used in the individual case (cf. Table IV) depended.

Table II (Azides)

I. m-sulfamoyl phenyl azide

II. J) -SuI fanioylphenyl azide

III. 0-i: sulfamoylnaphth-2-y] azide

IV. 4-l'.romonaphthylazide

VI. 4,4 »-Bis (azido) -3,3'-dimethoxybiphenyl

VII. 5-Azido isoquinoline

VIII. 4-morpholinophenyl azide

IX. 4-cyanophenyl azide

X »phenyl 4-azidobenzoate

Table III (coupler)

A. Quinaldinium iodide

B. 3- / f? - (o «Tolyl) carbaraoyl7-2-anthrol

C. 3- ^ ft- (4-methoxy-o-tolyl) carbamoyl7-2-naphthol

D. 2-Hydroxy-> 3- ^ iI- (4-methoxypheEyl) carbanioyl7-t 1H-

benzo ^ a7carbazole

E. 2,3-naphthalenediol

F. 2-Acetamido-5-methylphenol

G. Acetoacetanilide H. 8-Hydroxyquinoline J. 2,3-pyridinediol

K. 1-Hydroxy-2-naphthopiperidide

309807/1220

tab

lie IV (image color l

Coupler

A. Red Λ. J.
yellow P. pink orange C. orange pink D. purple purple O 03 E. orange orange GD
O F. orange yellow -J
"S. G yellow yellow 1220 H
J Red
Red yellow
yellow K Scarlet fever oranao

III

IV

red purple

crimson blue red purple

purple blue

red purple

orange red yellow yellow

crimson crimson crimson purple

_Azid_

V VI

red purple
blue green
purple green
blue blue

VII

VIII

crimson crimson
purple green
purple blue
blue green

purple blue brown

orange red-brown red
yellow orange yellow

purple brown purple

purple brownish purple
black

purple

yellow

orange

purple

purple

Il x

crimson purple purple red-brown purple rust-colored

yellow

orange

orange

weak
Red

orange
pink
yellow .
weak yellow
purple

weak
purple

orange

Red

orange

purple

orange

orange

yellow

orange

purpui

purple

Claims (1)

Pliotographic recording material ₉ consisting of a layer support and at least one applied thereto, which can be converted into a photosensitive layer by alkaline treatment, at least one organoazide-containing image-generating layer, characterized in that in the image-generating layer, in addition to at least one organoazide, there is an isolable phosphonium salt of the formula: R in which R stands for an organic radical "ad X stands for © in anion and R ^{1 is} an alkyl radical" which is substituted for an electron withdrawing radical in the ß-position dlwreh mimd © st @ Ei "contains _t that by alkaline treatment in one with the Organoazide a radiation-sensitive complex forming triorganophosphine is transferable. 2. Photographic recording material according to claim H _9, characterized in that it contains a phosphonium salt of the following formula = 1 in the layer generating the image: η 2 CH - CH - P ü: wui.i 1 7 2V where mean: ■ X is an anion; R ¹ individually is an electron withdrawing group; R ² individually represents an electron withdrawing radical or a hydrogen atom or an alkyl or aryl radical; r 'and R together to complete a 2-oxocycloalkyl radical required atoms; 2-oxocycloalkyl radical with 5 or 6 ring atoms R is a hydrogen atom or an alkyl or Aryl radical or a heterocyclic radical; R ⁴ , R ⁵ and R ⁶ each represent an alkyl, alkoxy, aryl or Amino radical, where it applies that R can additionally be a radical of the following formula: R * P · -R ⁵ Χ ^θ in which η is an integer from 1 to 18 A 5 θ and R, R and X are those already given Have meaning 3. A photographic recording material according to claim 2, characterized in that it contains a phosphonium salt of the formula given in which those represented by R * and R 2 Electron withdrawing radicals consist of cyano, substituted carbonyl or nitro radicals. 4. Photographic recording material according to claim 2, characterized in that it contains a phosphonium salt of the formula given in which at least one of the radicals R ⁴ , R ⁵ and R ^{6 is} an aryl radical. 5 «Photographic recording material according to claim 2, characterized in that it contains a phosphonium salt of the specified formula» in which the substituted carbonyl radical represented by the grids R 'and R corresponds to the following formula; 0, in which R ⁷ means «in hydrogen atom * -C-Ä ⁷ an alkyl, alkoxy, aryl, aryloxy or Alkenylreat ode? a rest of the Formula; Q Ä * - e - * CH -— CH - *. " h I,: ι * »fr where R ^a , '■% * $ ^ t ^ * R * uiid X * have the meaning given. # * Photographic recording material according to claim 2, This is characterized by the fact that it is a t- C 2 »Acetyl-I -pheny lÄthy 1J m? _t F ₁ ^ - (4-Methoxyphenyl) -3-exobutyi7-P »P» P-tripheny! Phosphonium-, P- / ä-C2-Oxocyclohexyi) ben * y _e 7-P »F» P-triph # nylphosphoniun-, Vein e-C2-yl phosphejiiunsal » • holds. r 42 - 7. Photographic recording material according to Claims 1 to 6, characterized in that it contains at least one dye-providing coupler. 8. Photographic recording material according to claims 1 to 7, characterized in that the phosphonium salt, the organoazide and any coupler present in the picture generating layer are present dispersed in a polymeric binder. 9. Photographic recording material according to claim 1, characterized in that it: in the image-forming layer contains an arylazide or heterocyclic azide as the organoazide. 10. Photographic recording material according to Claim 9, characterized in that it is in the Bi] Id generating layer as OTganoazid Sulfaaoylazid, p-Morpholinophenylazid or 4-Asl4obensol »ulfonamid contains. 11. A method for producing photographic images using a photographic recording material according to Claims 1 to 10, characterized in that the material is first subjected to an alkaline pretreatment, then exposed biligefecht, optionally treated with a color coupler and optionally also for purposes of the Stabilization of the non-image areas heated before copying. ■ ■. '■ ^{; i} » 11 «Procedures for making photographic images using a photograph! See recording material Claims 1 to 10, characterized in »that the measure material * a.o. is subjected to an alkaline pretreatment, then heated imagewise and finally fully exposed to activating radiation to produce an image in the exposed, unheated areas. BADORIGtNAL 309807/1220 ttStllt 13. Method of making photographic images using of a photographic recording material according to claims 1 to 10 having a layer containing: (a) a p-disubstituted aminophenyl azide, (b) a coupler reactive with the azide and (c) a phosphonium salt of the specified structure, characterized in that 1.) the material first imagewise with radiation activating the azide to produce a first image in the exposed areas exposed, the material 2.) subjected to an alkaline treatment, the material 3.) again imagewise with production of a second image exposed in the exposed areas and the material if necessary 4.) for stabilization additionally heated. 1 0 U 8 0 7/1 Γ 2nd Π