DE2046018A1 - Photographic recording material - Google Patents

Description

The invention relates to a photographic recording material, consisting of a layer support and (a) at least one colorless or practically colorless organic layer applied to it Compound A, which can be oxidized to a colored compound, and (b) at least one organic compound applied thereto Compound B, which upon exposure to light forms at least one of compound A into a colored compound oxidizing compound disintegrates.

It is known e.g. B. from Phot. May be. Eng., £ »Pages 98 bis (1961) and U.S. Patent 3,042,515 for division of images by photographic means to use photographic recording materials with leuco compounds, which by means of certain polyhalogen compounds that act as oxidizing agents are converted into the corresponding leuco dyes can. For example, it is possible to use recording materials to produce images by photographic means which contain a mixture of diphenylmethane and carbon tetrabromide. Will be such a recording material If exposed to ultraviolet radiation right to lie, this is what causes it

109816/1854

2Q46018

this, that the carbon tetrabromide decomposes. The educated Decomposition products oxidize the diphenylmethane to the corresponding blue dye.

The disadvantage of this known process is that it acts as a photo-oxidizing agent Halogen-containing hydrocarbons used are generally not panchromatic sensitive, but rather only in relation to the ultraviolet range and the areas of the spectrum that are close to this range of the spectrum Sensitive to the spectrum. Another disadvantage of these halogen-containing hydrocarbons is that they result can only produce recording materials of a relatively short life, since the halogen-containing compounds are either highly volatile and / or thermally unstable. Finally, it is also disadvantageous that they differ during image fixing not easy to remove.

The object of the invention is therefore to provide a photographic recording material, consisting of a layer support and (a) at least one colorless or practical applied to it colorless organic compound A which can be oxidized to a colored compound, and (b) at least one applied thereon organic compound B, which upon exposure to light leads to the formation of at least one compound A to a colored compound oxidizing compound disintegrates, indicating the disadvantages of the previously known recording materials does not have this type, d. H. to indicate a photographic recording material of the type described, which is not only sensitive to the ultraviolet region and the near ultraviolet regions of the spectrum and which is also stable.

10981 6/1854

The object of the invention is based on a photographic Recording material consisting of a layer support and (a) at least one colorless or practically applied thereto colorless organic compound A which can be oxidized to a colored compound, and (b) at least one thereon applied organic compound Ii, which on exposure to light with the formation of at least one compound A to a colored compound oxidizing compound disintegrates, from una is characterized in that it is an organic compound L is a heterocyclic compound with an acyloxy or alkoxy substituted ring nitrogen atom of one of the following Formulas contains:

on

OK

-2 \

-N '

OR

or

10901G / 1854

'Φ

; ■! ■

H,

where mean:

■ 1!
t

2 a

those to complete an optionally substituted 5- or 6-membered heterocyclic Ring's required atoms j

an optionally substituted alkyl or acyl radical;

an optionally substituted methine or Polymethine group with a terminal heterocyclic ring customary for cyanine dyes, an anllinovinyl, an optionally substituted styryl, alkyl, aryl or aldehyde radical, an acyl radical or a hydrogen atom;

in each case a hydrogen atom or an optionally substituted alkyl or aryl radical;

an alkylene or alkyleneoxy radical with 1 to ο carbon atoms in the alkylene chain;

an optionally substituted methine or polymethine group with a terminal, for

109816/1854

Merocyanine dyes customary, heterocyclic ring or an optionally substituted one Allylidene residue;

Q2 and Qg the tsar completion of a 5- or 6-

membered, heterocyclic ring required atoms and

0
X is an acid anion.

Becomes a photographic material according to the invention exposed to actinic radiation, e.g. visible, infrared or ultraviolet Light or X-rays as well as electron beams, the compound B, i.e. the photo-oxidizing agent, breaks down with generation of at least one oxidizing compound. This oxidizing compound then oxidizes the colorless organic compound A, which can also be called a color generator, transforming it into a colored compound is convicted. The color produced in the individual case depends on the oxidizable compound A used in the individual case, i.e. the so-called color generator.

The organic compounds B used for the production of the photographic recording material according to the invention, i. the photo-oxidizing agents used, have such properties that it is easy to remove the exposed and developed Record material from discoloration of the background areas to protect «This can be achieved by the recording material is treated with an acidic or basic solution of a pH value, in which the photo-oxidizing agent is disturbed.

The invention creates recording materials, compared to known, comparable recording materials

10981 6/1854

have the advantage that they are photo-oxidizing compounds which are sensitive to various forms of actinic radiation and not just to the ultraviolet region or the regions of the spectrum near the ultraviolet region. Furthermore, they are used for production The photo-oxidizing agents used in the recording material according to the invention are less volatile than those used for production of the known recording materials used halogenated Hydrocarbons. As a result, the recording materials according to the invention also have a very large one IMPROVED LIFE. Another advantage of the inventive photographic recording materials are that they can be easily removed by treatment with either an acid or base, depending on the photo-oxidizing agent used in the individual case.

The recording materials according to the invention can be used in an extremely versatile manner. They can, for example in the context of simple copying process used in which a substrate, such as paper, who soaked 1st, frame of the original is exposed with an organic compound A and an organic compound B, which is to be imaged or copied. Another area of application is the production of cracks in metalworking. Finally , the recording materials according to the invention are suitable for the production of M ^

* Xx micrographs.

The drawing materials of the Er are particularly suitable

hlldern

invention for the production of MikroxSuuuMB, since they have an excellent resolving power «A high resolving power can be achieved because the active particles of the recording material !! have a very small molecular size,

109816/185 *

i.e. for example from 1 to 35 Å * in the case of the so-called Color generator molecules »i.e. those forming the compound A. Molecules compared to about 500 Å * of very fine-grained ones Silver halide particles.

A wide variety of colorless materials are suitable for producing a photographic recording material according to the invention or practically colorless organic compounds A, which can be oxidized to a colored compound. Suitable ^ are all colorless or practically colorless organic compounds, which through an oxidation turn into a colored one Let the connection be transferred and that under normal conditions in which the recording material is stored are stable to oxidation. The oxidation process can consist of a simple oxidation process. the Oxidation reaction can possibly also be of a more complex nature, i.e. the reaction can possibly take place over several Steps run off. It is also possible that several molecules of the photo-oxidizing agent and of the color generator can be attached to the Reaction to be involved.

If appropriate, mixtures of the most varied of organic materials can also be used Compounds A, i.e. the various color generators, can be used.

The organic compounds of type B required for the production of a photographic recording material according to the invention, that upon exposure to light with the formation of at least one compound which oxidizes compound A to a colored compound disintegrate, i.e. to produce a recording material Photooxidizing agents suitable according to the invention

1OSC; . / 1354

given structural formulas I to IV, which extend up to the action actinic radiation, d. H. visible, ultraviolet or infrared light or X-rays or electron beams, behave inertly, have different peak sensitivities, depending on their special structure. As a result it is possible during the production of the recording material Compounds B used to be selected according to the light source or radiation source used later.

According to a particularly advantageous embodiment of the invention If the recording material contains, as photosensitive compound B, a compound of the following formulas:

C - (- L = L

CH ^β CH

- - ° -2 V ^R 2

H ■

OR

CH-CIi

VIUiO - N -ir CH «CH

or

109816/1854

VIII.

^ 2

^x . _ ^> IXs-

K yS 6

RO - N - f - CH * CH -} r ^S C ψ ^{L -} L ^ - "" * C

g-1 m p.

where mean:

K is an optionally substituted alkyl

or acyl radical;

Rp is a hydrogen atom or optionally one substituted alkyl or aryl radical;

R, an optionally substituted alkyl, alkenyl, aryl or alkoxy radical;

Q ₁ , Q ₂ and

Q ₂ J the atoms required to complete 5- or 6-membered heterocyclic rings;

L is an optionally substituted methine group;

Rg and R "each represent a cyano, ester or alkylsulfonyl radical;

Χ ^θ an acid anion;

G is an anilino or optionally substituted one

Aryl radical; or an anilinovinyl residue;

g = 1 or 2;

m = 1,2 or 3 and

η ü 1, 2, 3 or ^.

109816/1884

- ίο -

Has in the given formula II R. 'the meaning of a optionally substituted methine or polymethine group with a terminal heterocyclic which is customary for cyanine dyes Ring, this can be methine or polymethine roup pen with their usual heterocyclic rings for cyanine dyes have a constitution such as those from the book by Mees and James "The Theory of the Photographic Process ", MacMillan Verlag, 3rd edition, pages 198-232.

For example, the methine and polymethine groups can have the following structural formulas:

-CH =, -C (CH) =, -C (C ₆ H ₅ ) =, -CH = CH and -CH = CH-CH =.

If R has the meaning of an optionally substituted one Alkyl radical, this preferably has 1 to 8 carbon atoms.

If R _{1 has} the meaning of an optionally substituted aryl radical, this preferably consists of an optionally substituted aryl radical of the phenyl or naphthyl series, ie R ₁ can for example consist of a phenyl, naphthyl or tolyl radical.

If R _{1 has} the meaning of an acyl radical, this can be given by the following formula:

CR _g

are reproduced, where R ~ has the meaning of a hydrogen atom or an alkyl radical with preferably 1 to 8 carbon atoms.

109816/1854

- li -

If R _{1 has} the meaning of an anilinovinyl residue, this can be represented by the following structural formula:

CH - CH - N

wherein R, the meaning of a hydrogen atom or an acyl or alkyl radicals each having preferably 1 to 8 carbon atoms.

If R _{1 has} the meaning of an optionally substituted styryl radical, this can, for example, have the following structural formula:

CH

wherein R "represents a hydrogen atom, an alkyl group Aryl radical or an optionally substituted amino radical, e.g. B. a dialkylamino, e.g. B. a dimethylamino radical, owns. If R_ has the meaning of an alkyl radical, this preferably has 1 to 8 carbon atoms on. If R_ has the meaning of an aryl radical, this preferably consists of an aryl radical of the phenyl or Waphthyl series.

In the structural formula I given, Ro can, for example, be a such, optionally substituted methine or polymethine group with a terminal, customary for merocyanine dyes be heterocyclic ring, such as those from

109816/1854

the already quoted book by Mees and James are known.

If R ^ has the meaning of an optionally substituted one Allylidenrestes, this can for example consist of a cyanoallylidene, alkylcarboxyallylidene or an alkylsulfonylallylidene radical.

In the formulas I to III R has the meaning of optionally substituted alkyl radical, this preferably has 1 to 8 carbon atoms and consists, for example, of a methyl, propyl, ethyl or butyl radical or a sulfoalkyl radical, z. B. of the formula - (CHp) ^ SO -.- or an aralkyl radical, z. B. a benzyl or pyridinato-oxyalkylsalzrest, z. B. the Formula - (CHp), - O-Y, in which Y is an optionally substituted pyridinium salt radical.

In the given formulas I bJs III R has the meaning an optionally substituted arrest, this can be expressed, for example, by the formula n

Play -C-Rn,

wherein R ^ is an alkyl radical preferably having 1 to 8 carbon atoms or an aryl radical, preferably of the phenyl or Iaphthyl series, is. This means that R ^. for example can be a Methyl, ethyl, propyl, butyl, phenyl or naphthyl radical.

The heterocyclic ring completed by Z can, in addition to the ring nitrogen atom already present, at least one more have another common hetero atom, for example an oxygen, sulfur, selenium or nitrogen atom.

In detail, Z can, for example, stand for the atoms which are necessary for a complete understanding, if applicable substituted thiazole, oxazole, selenazole, thiazoline,

109816/1854

Pyridine, quinoline, 3,3-dialkylindolenine, imidazole, imidazo / ~ 4,5-b-7quinoxaline, 3,3-dialkyl-3H-pyrrolo / ~ 2,3-b-7-pyridine or a thiazolo / ~ 4,5-b-7-quinoline ring.

X can be a common acid anion, for example a chloride, bromide, iodide, perchlorate, sulfamate, thiocyanate, p-toluenesulfonate, Methyl sulfate or tetrafluoroborate anion,

Q ₂ and Qg can, for example, represent the atoms which are able to form one of the heterocyclic rings specified in connection with Z.

The radical R, - shown in structural formula IV can, for example be an alkyleneoxy or arylenealkoxy radical, e.g. an ethyleneoxy, trimethyleneoxy, tetramethyleneoxy, propylidenoxy, Ethylene, trimethylene, tetramethylene, propylidene or phenylene ethoxy radical.

Particularly advantageous photosensitive compounds have been found to be those of the formulas I and II in which Z is the for Completion of an optionally substituted pyridine or quinoline ring represents the required atoms.

In the specified photosensitive compounds of the formulas IV to VIII

Continued on page 15

109016/1854

Q ₁ , Q ₂ , Q ₄ and Q _{g represent} the non-metallic atoms necessary to complete a ring of 5 to 6 atoms in the heterocyclic ring. These rings can be sensitizing or desensitizing rings and, in addition to the nitrogen atom already present, optionally also have at least one second heteroatom, for example an oxygen, sulfur, selenium or nitrogen atom. The rings represented by Q ₁ , Q, 0, and Q ₉ are those that are common for cyanine dyes.

For example, Q ₁ , Q ₂ and Qq can represent the atoms that form one:

Thiazole ring, ζ. B. a thiazole, 4-methylthiazole, 3-ethylthiazole, 4-phenylthiazole, 5-methylthiazole, 5-phenylthiazole, 4,5-dimethylthiazole, 4,5-diphenylthiazole, 4- (2-thienyl) thiazole, Benzothiazole, 4-chlorobenzothiazole, 4- or 5-nitrobenzothiazole, 5-chlorobenzothiazole, 6-chlorobenzothiazole, 7-chlorobenzothiazole, 4-methylbenzothiazole, 5-methylbenzo

1098 16/1854

thiazole, 6-methylbenzothiazole, 6-nitrobenzothiazole, 5-bromobenzothiazole, 6-bromobenzothiazole, 5-chloro-6-nitrobenzothiazole, ji-phenylbenzothiazole, 4-ilethoxybenzothiazole, 5-methoxybenzothiazole, 6-methoxybenzothiazole -, 5-iodobenzothiazole, 6-joüobenzothiazole, 4-ethoxybenzothiazole, 5-sthoxybenzothiazole, tetrahydrobenzothiazole, 5,6-dimethoxybenzothiazole, 5,6-methylenedioxybenzothiazole, 5xy-hydroxybenzothiazole, -NaphtThothiazole-, ß-llaphthothiazole-, ß _t ß-naphthothiazole-, 5-methoxy-ß, ß-naphthothiazole-, 5-ethoxy-ßnaphthothiazole-, 8-methoxy-a-naphthothiazole-, 7-methoxy- "

naphthothiazole, 4 ^f -Methoxythianaphtheno-7 ^f , o ^^. S-thiazole or a waphthothiazole ring substituted by a nitro radical;

Oxazole ring, e.g. D. a 4-methyloxazole, 4-nitro-oxazole, 5-ethyloxazole, 4-phenyloxazole, 4,5-diphenyloxazole, 4-iithyloxazole, ⁱ l, 5-dimethoxazole, 5-phenyloxaaole, Benzoxazole, S-chlorobenzoxazole, 5-methylbenzoxazole, 5-phenylbenzoxazole, 5- or 6-nitrobenzoxazole, S-chloro-δ-nitrobenzoxazole, 6-methylbenzoxazole, 5,6-diinethylbenzoxazole, 4,6 -Diiaethylbenzoxazole-, 5-methoxybenzoxazole-, 5-hydroxybenzoxazole-, 6-methoxybenzoxazole-, 5-thoxybenzoxazole-, S-chlorobenzoxazole-, 6- g

Hydroxybenzoxazole, a-naphthoxazole, ß-liaphthoxazole or a naphthoxazole ring substituted by a nitro radical;

Selenazole ring, ζ. B. a 4-methylselenazole, ^ l-nitroselenazole, 4-phenylselenazole, benzoselenazole 5-chlorobenzoselenazole, 5-methoxybenzoselenazole, 5-hydroxybenzoselenazole, 5- or 6-nitrobenzoselenazole, S-chloro-o-nitrobenzoselenazole, Tetrahydrobenzoselenazole, a-naphthose azole, ß-waphthoselenazole or a naphthoselenazole ring substituted by a nitro radical;

109816/1854

Thiazoline ring, ζ. B. a thiazoline, ^ -Methylthiazolin- or 4-nitrothiazoline ringj

Pyridine ring, a. B. a 2-pyridine, 5-methyl-2-pyridine, 4-pyridine, 3-methyl- ⁱ l-pyridine or a pyridine ring substituted by a nitro radical;

Quinoline ring, e.g. ß. a 2-chlnoline, 3-i4ethyl-2-quinoline, S-ethyl ^ -quinoline-, 6-chloro-2-quinoline-, 6-hitro-2-quinoline-, 6-chloro-2-quinoline-, ö-methoxy-S-quinoline-, 8-ethoxy-2-quinoline 8-hydroxy-2-cliinolin-, ^ l-quinoline-, ö-IIethoxy- ^ - quinoline-, 6-Nitfo-il-quinoline-, 7-methyl-i-quinoline-, B-chloro-iJ-quinoline-, 1-isoquinoline, 6-nitro-l-isoquinoline, 3,4-dihydro-l-isoquinoline or 3-isoquinoline ring;

3,3-Dialkylindoleninring, preferably with a nitro or Cyano residue, e.g. B. a 3 »3-dimethyl-5- or 6-LJitroiridolenin-, 3,3-dimethyl-5- or 6-cyanoindolenine ring;

Imidazole ring, e.g. i :. an imiuazole, 1-alkyllmidazole, l-alkyl-Ί-phenylimidazole, l-alkyl- ^ jS-cürnethylimidazol-, benzimidazole-, 1-alkylbenzimidazole, l-alkyl-5-nitrobenzimidazole, l-aryl-5,6-dichlorobenzimidazole, 1-alkyl-ct-naphthimidazole ring; or 1-aryl-ß-naphthimidazole or 1-alkyl-5-methoxy-a-naphthimldazole ring;

Irnidazo / "" 4, S-bZquinoxaline ring, e.g. B. a 1-alkylimidazo / ~ k , 5-t) 7-quinoxaline ring, e.g. B. a l-Ethyllmidazo / ~ 4,5-b7-quinoxaline-, 6-chloro-l-ethylimidazo / "" ^, 3- ^ 7ChInOXaIIn-, 1-Alkenylimiaazo / "^, 5- ^ 7ChInOXaHn-, z. B. l-Allyliinidazo / ~ 4,5-b7 quinoxaline-, o-chloro-l-allylimidazo / "^, ^ - b7quinoxaline-, 1-arylimidazo /" ¹ !, Sb / quinoxaline-, e.g. a 1 -Phenylimidazol "h , 5-b7-quinoxaline or 6-chloro-1-phenylimidazo / ~ ^, 5-b7-cninoxaline ring;

8AD ORfQiNAL

j ^ ii-m-) ij »H 109016/1854

3,3-dialkyl-3H-pyrrolo / ~ 2,3-b7pyridine ring, e.g. a 3,3-diaiethyl-3H-pyrrolo / ~ 2,3-o7pyrlclin- or 3, 3-I ⁾ l ^ thyl- 3 "-pyrrolo / ~ 2,3-b7pyridinrin3j

'i'hla2olo / "* 4 _> 5-b7chiriolinrlrii _{i <}

If R- has the meaning of an optionally substituted alkyl radical, this preferably has 1 to 12, in particular 1 to H, carbon atoms. R ~ can thus beispielswei- g se consist of a iiethyl-, A'thyl-, propyl, isopropyl, butyl, hexyl, cyclohexyl, Pecyl- or dodecyl radical, or a hydroxyalkyl radical, z. B. a ß-hydroxyethyl or ω-hydroxybutyl radical, or an alkoxyalkyl radical, z. B. a ßilethoxyäthyl- or ω-butoxybutyl, or a carboxyalkyl, z. B. a ß-Carboxyäthyl- or ω-Carboxybutylrest, or eini alkoxy, z. B. a methoxy or iithoxy radical, or a sulfoalkyl radical, e.g. B. a Ü-sulfoäthyl- or ω-sulfobutyl radical, or a sulfatoalkyl radical, z. B. a ß-3ulfatoäthyl- or ω-sulfatobutyl, or an acyloxyalkyl, z. B. a ß-Acetoxyäthyl-, γ-acetoxypropyl tyryloxybutylrest or "_SS _U, or an alkoxycarbonylalkyl group, z. Beta. A ß-i-ietnoxycarbonyläthyl- or ω-A'thoxycarbonylbutylrest, or an aralkyl group i, z. B. a Denzyl or phenethyl radical.

If R, has the meaning of an alkenyl radical, this exists for example from an allyl, 1-propenyl or 2-butenyl radical.

If R has the meaning of an optionally substituted one Aryl radical, this is preferably ordered from an optionally substituted aryl radical of the phenyl or ilaphthyl series and consists, for example, of a phenyl, tolyl, haphthyl, Ethoxyphenyl or chlorophenyl radical.

8AD

109816/1854

The through Q ₁ . A completed heterocyclic ring can, for example, have a nitrogen, sulfur, selenium or oxygen atom as a hetero atom, or several of these atoms. In detail, Qj. for example stand for the atoms that complete a:

2-pyrazolin-5-one ring; z. B. a 3-methyl-l-phenyl-2-pyrazolin-5-one, l-phenyl-2-pyrazolin-5-one or l- (2-benzothiazolyl) -3-methyl-2-pyrazolin-5-one ringj

Isoxazolone ring, e.g. B. a 3-phenyl-5 - (^ H) -isoxazolon- or 3-Me thy 1-5- ⁽¹ JH) -isoxazolonring;

Oxindole ring, e.g. B. a 1-alkyl-2,3-dihydro-2-oxindole ring;

2,4,6-triketohexahydropyrimidine ring, e.g. B. an earbituric or 2- ^r i'hiobarbitursäurering with their 1-alkyl derivatives, z. B. 1-methyl, 1-ethyl, 1-propyl or 1-heptyl derivatives, or 1,3-dialkyl derivatives, e.g. B. 1,3-dimethyl, 1,3-diethyl, 1,3-dipropyl, 1,3-diisopropyl, 1,3-dicyclohexyl or 1,3-di (ίά-methoxy'ithyl) derivatives, or 1,3-diaryl derivatives, e.g. B. 1,3-diphenyl, 1,3-Dl (p-chloroplienyl) or 1,3-di (p-athoxycarbonylphenyl) derivatives, or 1-aryl derivatives, e.g. δ. 1-phenyl, 1-p-chlorophenyl or 1-p-iithoxycarbonylphenyl derivatives, or 1-alkyl-3-aryl derivatives, e.g. B. l-ethyl-3-phenyl or 1-n-heptyl-3-phenyl derivatives;

Rhodanine ring, e.g. For example, a 2-Thio-2, ¹ l-thiazolldindionring, z. B. a rhodanine or 3-alkylrhodanine ring, e.g. B. a 3-A'thylrhodanin- or 3-Allylrhodanlnring, or a 3-Carboxyalkylrhodaninring, z. B. a 3- (2-carboxyethyl) rhodanine or 3- (4-carboxybutyl) rhodanine ring, or a 3-oulfoalkylrhodanine ring, e.g. B. a 3- (2-3ulfoethyl) rhodanine, 3- (3-sulfopropyl) rhodanine or 3- (4-oulfobutyl) rhodanine ring, or a 3-arylrhodanine ring, e.g. B. a 3-phenylrhodanine ring;

109816/1854 θαο

/ S

2 ( 5Ii) -TuA Üa2o / ~ 1, 2-a7pyridonrine _f ^r ;.;

2-furanonrinc, ζ. "Ss. A 3-cyano-4-phenyl-2 (5H) furanone ring;

s, ζ. 3. a 3enzo / ~ b7thiophene

3 (2ίΙ) -ori-1,1-dioxydrinc;

5,7 ^ DIcXo-G, 7-dihyäro-5-tliiazolo / ~ 3,2-a7pyrir.iidinrin _t r, ζ. Β. a 5,7-dioxo-3-piienyl-6,7-dihydro-5-thiazolo / 3,2-a7i-yri-

2-thio-2, ⁱ 4-oxazolidinedine ring, o. H. a 2- 'oxazoldionrin ^, e.g. B. a 3-] ethyl-2-thio-2, ⁱ J-oxazolidinedione, 3- (2-3ulfoiltüyl) -2-thio-2,4-oxazolidinedione, 3- (4-sulfobutyl) -2-lhic -2,4-oxazolidinedione or 3- (3-carbxyprox) yl) -2-thio-2,4-oxazolidinedione ring;

^r i'hiariaphfhenonrin _{i , z. B. a 2- (2Ii) -thianaphthenonriii {i;

2-thio-2,5-thiazoliaindionrine ^, d. H. a 2-ΤΜο-2,5- (3Κ, 4Η) -tiiiazoldionrin. ^, z. B. a 3-ethyl-2-thio-2,5-thiazolidinedionriiie;

2,4-ΪΙιχ3ζο1ίΰίηα1οηΓΐηβ, ζ. 3. a 2,4-thiazolidinedione, 3-ethyl-2, i ^ -thiazolidinedione-, 3-phenyl-2,4-thiazolidinedione 3-α-naphthyl-2,4-thiazolidinedione [beta];

Thiazolidinone ring, e.g. B. a 4-thiazolidinone, 3-A thiazolidinone, 3-phenyl-A-thiazolidinone or 3-α-haphthyl-4-thiazolidinone ring;

2-thiazolin-4-one ring, e.g. B. a 2-; ithylmercapto-2-thiazolinif-one, 2-Alkylρhenylaraino-2-tiliazolin-4-one or 2-Diphenyla.üino-2-tniazolin-4-oner Jiif; j

1 0 9 0 ι υ / 1 Ö 5 4 ßÄD

2-imino- ¹ l-oxazolidinone _ring> ie a pseudohydantoin ring;

2,4-iinidazolidinedione ring, ie a hydantoin ring, ·. ζ. Β. a 2,4-Ιΐη1ά3ζοϋα1ηα1οη-, 3-ethyl-2, ⁱ J-imidazolidinedione-, 3-phenyl-2, ^ - imidazolidinedione-, 3-a-naphthy1-2,4-imidazolldinedione-, 1,3-diethyl- 2,4-iraidazolidinedione-, l-Ä "ethyl-3-phenyl-2,4-irnidazolldinedione-, 1-ethy 1-2-a-naphthy 1-2,4 -iraidazoli dindione- or 1,3-diphenyl -2, ⁱ l-imidazolidinedione ring;

2-thio-2, ⁱ J-imidazolidinedione ring, ie a 2-thiohydantoin ring, e.g. B. a 2- ■ thio-2,4-imidazolidirldione, 3-ethyl-2-thio-2,4-imidazolidinedione, 3- (4-sulfobutyl) -2-thio-2,4-imidazolidinedione, 3 - (2-Carboxyethyl) -2-thio-2, ⁱ l-imidazolidinedione-, 3-phenyl-2-thio-2,4-imidazolidinedione-, 3-a-naphthyl-2-thio-2,4-imldazolidinedione- , 1,3-diethyl-2-thio-2,4-imidazolidinedione ~, l-ethyl-3-phenyl-2-thio-2,4-imidazolidinedione-, l-) ithyl-3-cinaphthyl-2-thio- 2,4-imidazolidinedione or 1,3-diphenyl-2-thio-2,4-imldazolidinedione ring, or one

2-imidazolin-5-one ring, e.g. D. a 2-propylmercapto-2-imidazolin-5-one ring.

Qp preferably stands for the atoms which one may have Completed substituted pyridine or quinoline ring.

If R ^ and R_ have the meaning of Esterresben, so can she z. B. consist of methoxycarbonyl and ethoxycarbonyl radicals. Have Kg and R "the meaning of alkylsulfonyl radicals, so these z. B. aua methylsulfonyl and ethyl sulf onyl residues exist. Preferably contain the Esterbzw. Alkylsulfonyl radicals 1 to δ carbon atoms.

L may be for example an odor by an alkyl aryl rest substituiei'te iietliinirruppe, wherein α \ Λ el üvreise a (lrui ^ pe

109816/1854 SADOFMGtNAt

of the following structural formulas:

-CH =, -C (CII ₃ ) =, -C (C ₆ Il ₅ ) =

Preferably L is a methine group of the formula -C =, wherein T is a hydrogen atom, an alkyl radical with T 1 to 4 carbon atoms or an aryl radical of üenzollinie, z. B. is a phenyl radical.

If R "uid Rj. Have the meaning of alkyl resoans, they preferably have 1 to 12 carbon atoms, in particular 1 to 4 carbon atoms. If R _? And Rj. Have the meaning of aryl radicals, these preferably consist of aryl radicals of the phenyl groups. or iJaphthyl series, ie h_ and R _1. can be, for example, ethyl, ethyl, propyl, isopropyl, butyl, decyl or dodecyl radicals or phenyl, tolyl, ilaphthyl, ilethoxypxienyl, chlorophemyl or mitrophenyl radicals.

Χ ^θ can, for example, be a perchlorate, tetrafluoroborate, chloride, bromide, iodici, sulfamate, thiocyanate, p-toluenesulfonate anion.

if G has the meaning of an aryl radical, then this is palpable preferably from an aryl radical of the phenyl or naphthyl series, for example a phenyl, naphthyl, dialkylaminophenyl, Tolyl, chloropxienyl or ilitrophenyl radical. Does G have the meaning of an anilino residue, this z. ß. from an anilinovinyl residue.

If R has the meaning of an optionally substituted one Alkyl radical, 00 this can expediently up to 12, preferably 1 to B and in particular 1 to 4 carbon atoms, α. H. R can, for example, be a llethyl, ethyl, propyl, Isopropyl, butyl, hexyl, cyclohexyl, decyl, dodecyl radical or an alkaryl radical, such as, for example, a denzyl radical, or a üulfoalkylreat, for example a ß-iJulfoäthyl-, ω-Gulfo-

109816/1854

BATHROOM ÖR1GI8ÄL

butyl or ω-sulfopropyl radical.

If R has the meaning of an acyl radical, this can be through the formula

are reproduced, v / obei R an optionally substituted Alkyl radical of the meaning given or an aryl radical, preferably the phenyl or methyl series, d. H. for example a Methyl, phenyl, uapnthyl, propyl or uenzyl radical can be.

Typical advantageous compounds suitable for the production of a photographic recording material according to the invention B, d. H. Photooxidants are:

1. 3-ethyl-l'-methoxyoxa-2'-pyridocarbocyanine perchlorate,

2. l'-A "thoxy-3-ethyloxa-2 '-pyridocarbocyanine tetrafluoroborate,

3. 3 ^l -A'thyl-1-methoxy-2-pyridothiacyanine iodide,

k. l-ethoxy-3 ^l -ethyl-2-pyridothiacyanine tetrafluoroborate,

5. l-benzyloxy-3'-ethyl-2-pyridothiacyanine iodide,

6. 3 ^l -ethyl-l-methoxy-2-pyridothiacarbocyanin iodide,

7. l-ethoxy-3'-ethyl-2-pyridothiacarbocyanine tetrafluoroborate,

8. Anhydro-3 ^f -ethyl-1- (3-3ulfopropoxy) -2-pyridothiacarbocyanine hydroxide,

9. l-Benzyloxy-3'-ethyl-2-pyridothiacarbocyanine perchlorate,

10. 3'-ethyl ~ 1-methoxy-2-pyridothiacarbo gyanine perchlorate,

11. 1'-methoxy-1,3,3-trimethylindo-2'-pyridocarbocyanine picrate,

12. 3 ^l -ethyl-1-ynethoxy-4 ', 5' -benzo-2-pyridothiacarbocyanine perchlorate,

13. l-ethoxy-3 ^l -ethyl-4 ', 5'-benzo-2-pyrldothiacarbocyanine tetrafluoroborate,

10 9 8 16/1854 ^ßAD

14. 1 '- / ithoxy-3-ethyloxa-2' -carbocyanine tetrafluoroborate,

15. 1 ^t -i \ thoxy-3-ethylthia-2'-cyanine tetrafluoroborate,

16. 1 '-Ab.oxy-3-ätliylthIa ~ 2' -carbocyariintetrafluoroborat,

17. 1 ¹ -ethoxy-3-ethylthia-2 ^l -dicarbocyanine tetrafluoroborate,

18. l-Iiethoxy-3 ^f -methyl-2-pyriuothiazolinocarbocyanine perchlorate,

19 · 3'-ethyl-l-methoxy - ^ - pyridothiacyanine perchlorate, 20 »3 ^f - ^ tnyl-l-methoxy - ^ - i; yridothiacarbocyanine perchlorate,

21. 1 ^t -ethoxy-3-ätliyl- ⁱ }, 5-benzothia-2 '-carbocyanine tetrafluoroborate, f

22. 2-ß-Anilinovinyl-1-methoxypyridinium-p-'toluQlsulforiat,

23 · 1-Athy 1-1'-methoxy-4,5-t) ensothia-4'-carbocyanine perchlorate,

24. l-i-iethoxy-2-diethylpyridinium-p-toluenesulfonate, 25 l-i'Iethoxy-4-methylpyridiniuin-p-toluene sulfonate, 2G. Anhydro-2-methyl-1- (3-sulfopropoxy) pyridinium hydroxide,

27. l-Ethoxy-2-methZylpyrddiniumtetran.uoroborat, 2cl. l-ben2yloxy-2-methylpyridinium broinide, 29 ♦ l-Ätyioxy-2-methylehinoliniumtetraf luoroborat,

30. 1,1'-λ ', / lendioxybisp.yridiniumdibroinid,

^{31.1 r} - ⁱ i ^I rix: iethylenedioxybispyridiniundibromide,

32.1,1'-TetraKethylendioxybis (2-methy lpyridinium) dibroraia, 33 · 1,1 '-TetramethylenedioxybisC ^ -methyliyridiniunOdibromld,

34. 1,1'-tetramethylenedioxyblspyridinium dibromide, I.

35 1> 1'-fentamethylene oxybispyridinium aibromide,

36. l-acetoxy-2- ( ⁱ l-dimethylaininostyryl) pyridinium porchlorate, 37 · l-benzoyloxy-2- ( ² l-diinethylaminootyryDpyridinium perchlorate,

36. 1,3-diethyl-5- / ~ (l-methoxy-2 (III) -pyridylidene) ethyliaen7-2-thiobarbituric acid,

39. 3- ^ thyl-5- / ~ (l-iaethoxy-2 (lII) -pyridylidene) ethylidene-rhodanln, 'IC. l, 3-Dietl-5 - / "(l-Kiethoxy-2 (lH) -pyridylidene) ethylidene-7-barbituric acid,

^ l. 2- (3,3-Dcyancall: ylidene) -l-methoxy-1,2-dihydropyridi 1, 42. 2- / ~ (l-.ethüxy-2 (lH) -pyridylidGn) -atJiyliden7benzo / "b7-

thio] ⁱ Jien-3 (2n) -one-l, l-fiioxid,
4 3. 3-Cyaiio-5- / ~ (l-Kiethoxy-2 (lIi) -i>yridylidene);: thyliden7-4-plieny 1-2 ( ^r ja) -furanone,

- «^^ 9 8.0 / 186 4

44. I \ l-ethoxy-2-picolinium iodide,

4 [j. i, ^r -] ithoxy-2-picoliniumhexafluoropho3phat and

46. N-methoxy-2-anilinovinylpyridinium para-toluenesulfonate.

According to a further particularly advantageous embodiment of the invention, the recording material contains as compound A:

1. a leuco dye,

2. an IJ-acyl derivative of a leuco dye,

3. a triaryl methane, its single remaining methane bond by a benzylthio, 2-phenylhydrazino, Alkoxycarbonyl or disulfide radical is substituted, or

4. an organic amine.

The following are intended to produce a photographic recording material compounds A particularly suitable according to the invention are described in more detail.

I. Leuco dyes

The suitable leuco dyes are the reduced form of a dye. As a rule, they have 1 or 2 hydrogen atoms the removal of which, together with one or two electrons, leads to the generation of a dye. Since the Leuco form of a dye is colorless or practically colorless or at least has a different hue than the dye or the hue of the leuco dye has a lower intensity than the actual dye, they are suitable excellent for creating color images.

So that the leuco dyes can be oxidized, it is necessary they in intimate mixture with a compound B,

10 9 8 16/1854

8AD ORIGINAL

d. H. a photo-oxidizing agent to use. The impact actinic radiation then leads to the removal of 1 or removable hydrogen atoms, depending on the structure of the. Leuco- · form of the chosen dye, producing a colored image with a non-irradiated and therefore unchanged background.

Typical dyes used in their leuco form for manufacture of a recording material of the invention can be used are: "

a) Aminotriary! methane »ζ. B .:

Bis {4-amino-2-butylphenyl) (p-dimethylaminophenyl) methane, Bis (4-amino-2-chlorophenyl) (p-aminophenyl) methane, Bis (4-amino-3-chlorophenyl) (o-chlorophenyl) methane, bis (4-amino-3-chlorophenyl) phenylmethane, Bis (4-amino-3,5-diethy! Phenyl) (ο-chloropheny1) methane, Bis (4-amino-3,5-diethylpheny1) (ο-ethoxyphenyl) methane, Bis (4-amino-3,5-diethylphenyl) (p-methoxyphenyl) methane, Bis (4 -amino-3 »5 -diäthy lpheny l) pheny line than,

Bis (4-amino-3-ethylphenyl) (o-chlorophenyl) methane, λ

Bi3 (p-aminophenyl) (5-amino-m-tolyl) methane, bis (p-aminophenyl) (o-chlorophenyl) methane, BisCp-aminophenylJCp-chlorophenyl-methane, bis (p-aminophenyl) (2,4-dichlorophenyl methane, bis (p-aminophenyl) (2,5-dichlorophenyl) methane, 'bis (p-aminophenyl) (2,6-dichlorophenyl) methane, bis (p-aminophenyl) phenyl methane,
Bis (4-amino-o-tolyl) (p-chlorophenyl) methane, bis (4-amino-o-tolyl) (2,4-dichlorophenyl) methane, bis (p-anilinophenyl) (4-amino-m-tolyl ) methane, bis (4-benzylamino-2-cyanophenyl) (p-ciminophenyl) methane,

10 9 8 I 6/18 5 A

Bi3 (p-benzylethylaminophenyl) (p-chlorophenyUmethane, Bi-s (p-benzylethylaminophenyl) (ρ-diethylaminophenyl) methane, Bis (p-benzylethylaminophenyl) (ρ-diethylamlnophenyl) methane, Bis (4 ~ benzylethylamino-o-tolyl) (p-methoxyphenyl) methane, BisCp-benzyläthylaminopheriyDphenylmethari, BisC ^ -benzyläthylaiaino-o-tolyl) (o-chloropheiiyl) methane, • bis (4-benzylethylamino ~ o-tolyl) (p-diethylaminophenyDmethane, ßisCJ-benzyläthylamlno-o-tolyl) (4-diethylamirio-o-tolyl) methane,

Bis (4-benzylcithylamino-o-tolyl) (p-diniethylaminopiienyl) methane, Bis / ~ 2-chloro-4- (2-diethylaminoethyl) ethylaminophenyl7 (ochlorophenyDmethane,

Bis / ~ p-bis (2-cyanoethyl) amiriophenyl7phenylmethane, Bis / ~ p- (2-cyanoethyl) äthylamino-o-tolyl7 (p-dinö; hylamlnü-

phenyl) methane,
Bis / ~ p- (2-cyanoethyl) methylaminophenyl7 (p-diethylamino-

phenyl) methane,
Bis (p-dibutylaminophenyl) / ~ p- (2-cyanoethyl) methylarainophenyl7methane,

Bis (p-dibutylaminophenyl) (p-diethylaminophenyl) methane, bis ( ⁱ l-diethylamino-2-butoxyphenyl) (ρ-diethylaminophenyl) methane,

Bis ( ⁱ l-diethylamino-2-fluorophenyl) -o-tolylmethane, bis (p-diethylaminophenyl) (p-aminophenyl) methari, bis (p-diethylaminophenyl) (^ - anilino-l-naphthyljraethane, bis (p-diethylaminophenyl) (m-butoxyphenyl) methane, bis (p-dicithylaminophenyl) (o-chloropheriyl) methane, bis (p-diethylaminophenyl) (p-cyanophenyl) methane, bis (p-diethylaminophenyl) (2, ⁱ } -dlchlorophenyl) methane, bis (p-diethylaminophenyl) (A-diethylamino-l-naphthyl) methane, bis (p-diethylaminophenyl) (p-dimethylaminophenyl) raethane, Bi3 (p-diethylaminophenyl) (A-ethylamino-l-naphthyl) methane, bis (p- diethylaminophenyl) -2-naphthylmethane, bis (ρ-diethylaminophenyl) (p-ditlOphenyl) raethane,

1098 16/1854

Bis {p-diethy _; laiflinophenyl) ~ 2-pyridylraethane _J bis (p ~ dläthylamina-m-tolyl) (p-diethylaminophenyl) methane ₁ bisC ^ -diethylamino-o-tolyl) (o-chlorophenyl) methane, bis ( ¹ I-UXi; thylamino-o -tolyl) (p-diethylaminophenyl) methane, bisi ^ -dläthylaiaino-o-tolyl) (p ~ diphenylaminophenyl) methane, bis (4-dläthylamino-o-tolyl) phenylmethane, bis ( ⁱ l-dimethylamino-2-bromophenyl) phenyl than, bis (p-dimethylaminophenyl) (^ ~ anilino-l-naphthyl) methane, bis (p-dimethylaniinophenyl) (p-butylamlnophenyl) methane, bis (p-dimethylaminophenyl) (p-sec.-butylethylaminophenyl) - "methane,

Bis (p-dimethylaminophenyl) (p-chlorophenyl) methane, Bis (p-dimethylaminophenyl) (p-diethylaminoi> henyl) metal, Bis (p-diiriethylaiainophenyl) (4-dimethylamino-1-naphthyl) methane,

Bis (p-dimethylaminophenyl) (6-dimethylamino-m-tolyl) methane, bis (p-dimethylamino-o-tolyl) methane, bis (p -iimethylaminophenyl) (4-ethylamino-1-naphthydmethane, Bis (p-di -., Ethylaminophenyl) (p-hexyloxyphenyl) methane, bis (p-dimethylaruinophenyl) (p-methoxyphenyl) methane, bis (p-dlmethylaminophenyl) (5-methyl-2-pyridyl) methane, bis (p -dimethylaniinophenyl) -2-quinolylmethane, g

Bis (p-dimethylaminoiihenyl) -o-to Iy line than, Bis (p-dimethylaminophenyl) (1,3,3-trimethyl-2-indolinylidenemethyl) methane,

BisCii-dimethylamino-Oi-tolyl) (p-aminophenyl) methane, Bis (4-dimethylamino-o-tolyl) (ο-bromophenyl) methane, Bis (4-dimethylamino-o-tolyl) (o-cyanophenyl) methane, BisCii-dimethylamino-o-tolyl) (o-fluorophenyl) methane, BisC ^ -diinethylainino-o-tolyD-l-naphthylmethane, Bis (4-dimethylamino-o-tolyl) phenylmethane, Bis (p-ethylaminophenyl) (o-chlorophenyl) methane, bisC ^ -äthylamino-m-tolyl) (o-methoxyphenyl) methane,

98 16/1854 ew> <* W »» t.

It

Bis (4-ethylamino-m-tolyl) (ρ-methojcyphenyl-methane, bis (4-ethylamino-m-tolyl) (p-dimethylaminophenyl-methane, bis (4-ethylamino-m-tolyl) (p-hydroxyphenyl) methane, ... Bis / ~ 4-ethyl (2-hydroxyethyl) amino-m-tolyl7 (p-diethylaminophenyl) methane,

Bis / "p- (2-hydroxyethyl) aminophenyl7 (o-chlorophenyl) methane, bis /" p-bis (2-hydroxyethyl) aininophenyl7 ( ¹ l-diethylamino-otolyl) methane,

Bis / ~ p- (2-methoxyethyl) aminophenyl7phenylmethane, bis (p-methylaminophenyl) (o-hydroxyphenyl) methane, bis (p-propylaminophenyl) (m-bromophenyl) raethane, Tr is (^) -amino -ο -to IyI ) methane, tris (4-anilino-o-tolyl) methane, tris (p-benzylaminophenyl) methane, trisif ~ 4-bis (2-c, yanoethyl) amino-o-tolyl7niethan _> ■ Tris / "p- (2 -cyanoäthyl) äthylaminophenyl7methan, ^r rris (p-dibutylaminophenyl) methane, tris (p-di-t-butylaminophenyl) methane, tris (p-dimethylaminophenyl) methane, tris (iJ-üiäthylamino - ^ - chlorophenyl) methane, tris (p -diäthylaininöpheny l) methane, tris (^ l-diethylamino-o-tolyl) methane, tris (p-dihexylamino-o-tolyl) methane, tris (4-dimethylamino-o-tolyl) methane, tris (p-hexylaminophenyl) methane, Tris / "p-bis (2-hydroxyethyl) aminophenyl7methane, tris (p-methylaminophenyl) methane and TrisCp-dioctadecylaminophenylmethane.

b) amlnoxanthenes , e.g. B.

3-amino-6-dimethylamino-2-methyl-9- (o-chlorophenyl) xanthene, 3-amino-6-dimethylamino-2-methyl-9-phenylxanthene, 3-amino-6-dimethylamino-2-methylxanthene,

10 9 8 16/1854 βΑΟ

3,6-bis (aiäthylamino) -9- (o-chlorophenyl) xanthene, 3,6-bis (diethylamino) -9-hexylxanthene, 3,6-bis (diethylamino) -9- (o-methoxycarbonylphenyl) xanthene, 3,6-bis (diethylamino) -9-methylxanthene, 3,6-bis (diethylamino) -9-phenylxanthene, 3,6-Bi s (diethylamino) -9-o-tolylxanthene, 3,6-3is (dimethylamino) -9- (o-chlorophenyl) xanthene, 3,6-bis (dimethylamino) -9-ethylxanthene, 3,6-3is (dimethylamino) -9- (o-methoxycarbony! Phenyl) xanthene

and
3,6-bis (dimethylamino) -9-methylxanthene.

c) aminothioxanthenes , e.g. B.

3,6-bis (diethylamino) -9- (o-ethoxycarbony! Phenyl) thio-

xanthene,
3,6-bis (dimethylamine) -9- (o-methoxycarbonylphenyl) thioxanthene,

3,6-bis (dimethylamino) thioxanthene and 3> 6-dianilino-9- (o-ethoxycarbonylphenyl) thioxanthene.

d) Amlno-g.ilO-dihydroacridine »z. B.

3,6-bis (benzylamino) -9, 10-dihydro-9-methylacridine, 3,6-bis (diethylamino) -9-hexyl-9,10-dihydroacridine, 3,6-bis (diethylamino) -9, 10 -dihydro-9-methylacridine, 3,6-bis (diethylamino) -9> 10-dihydro-9-phenylacridine, 3,6-diamino-9-hexyl-9,: LO-dihydroacridine, 3,6-diamino-9 , 10-dihydro-9-methylacridine, 3,6-diamino-9,10-dihydro-9-phenylacridine, 3,6-bis (dimethylamino) -9 ~ hexyl-9-10-dihydroacridine and 3,6-bis ( dimethylamino) -9 » 10-dihydro-9-methylacridine.

10 9 8 16/1854

e) Aminophenoxazine _s ζ. Β.

3,7-bis (diethylamino) phenoxazine and 9-dimethylamino-benzo / α-7-phenoxazine.

f) aminophenothiazines _t z. B.
3,7-bis (benzylamino) phenothiazine.

g) Aminodih.ydrophenazines , e.g. B.

3,7-bis (benzylethylamino) -5,10-üihydro-5-phenylphenazine, 3,7-bis (diethylamino) -5-hexyl-5,10-dihydrophenazine, 3,7-bis (dihexylamino) -5,10-dihydrophenazine, 3,7-bis (dimethylamino) -5- (P-chloropheny1) -5,10-dihydrophenazine,

3,7-diamino-5- (o-chloropheny1) -5,10-dihydrophenazine, 3,7-diamino-5,10-dihydrophenazine, 3,7-diamino-5,10-dihydro-5-methylphenazine, 3,7-diaraino-5-hexy1-5,10-dihydrophenazine, 3,7-bis (dimethylamino) -5 »10-dihydrophenazine, 3,7-bis (dimethylamine) -5 »10-dihydro-5-phenylphenazine and 3,7-bis (dimethylamino) -5,10-dihydro-5-methylphenazine.

h) aminodipheny! methane,. Β.

1,4-bis / ~ bis-p- (diethylaminophenyl) methyl7piperazine, Bis (p-dicithylaminophenyl) anilinomethane, Bis (p-diethylaminophenyl) -l-benzotriazolylmetlian, Bis (p-diethylaminophenyl) -2-benzotriazolylmethane, bis (p-diclthylaminophenyl) (p-chloroanilino) methane, Bis (p-diethylaminophenyl) (2,4-dichloroanilino) methane, Bis (p-diethylaminophenyl) (methylamino) methane, bis (p-diethylaminophenyl) (οetadecylamino) methane, Bis (p-dimethylaminophenyl) aminomethane,

109816/1854

BisCp-QiniethylaminophenyDanilinoraethan, 1,1-bis (diine t hy laminophenyl) ethane, l, l-üis (dimethylarniiiophenyl) heptane and ijis (4-methylamino-ra-tolyl) auinoethane;

i) Leucoindamirie _a z. B.

-4'-dimethylarninodrpheny larain and ρ - ( i- -Dirne thylaminoanilino) phenol.

j) Aminohydrocinnamic acid (cyanoethane, leucomethine) , z.i3.

-a, 3-dic5 ^r anohyärocinnaminsÄLure, methyl ester, 4-anilino-a, 3-aicyanOhydrocinnamic acid, ilethylester, ^ - (p-CliloroanilinoJ-ajß-dicyanohydrocinnaniinsäure, lietliylester,

a-Cj-ano-il-dimethylaminohydrocinnamide, a-Cyano-ü-dimethylaininohydrocinnamic acid, I-lethylester, ex, g-Dicyano-iJ-diethylaiiiinohydrocinnamic acid, methyl ester, α, β-dicyano-4-dimethylaminohydrocinnaraamid, «, Ii-Dicyano - ^ - diinethylarainohydrocinnamic acid, methyl ester, α, 3-dicyano-4-dimethylaminohydrocinnamic acid,

ajS-Dicyano - ^ - dimethylaininohydrocinnainic acid, hexyl ester, "

α, β-dicyano-4-äthylarainohydrocinnamic acid, methyl ester, α, 3-dicyano-4-hexylaminohydrocinnamic acid, methyl ester, ajß-dicyano-Jj-methylaminocinnamic acid, methyl ester, p- (2,2-dicyanoethyl) -H, IJ-dimethylaniline, 4-methoxy- k '- (1,2,2-tricyanoethyl) azobenzene, ^! - (l ^^ - tricyanoäthyDazobenzol and p- (1,2,2-tricyanoethyl) -Ν, Ν-dimethylaniline.

k) hydrazines _t e.g. B.

l- (p-Diethylaminophenyl) -2- (2-pyridyl) hydrazine, l- (p-Dimethyla ^ inophenyl) -2- (2-pyridyl) hydrazine,

109816/1854

2046Q18 - ιή -

l- (3-methyl-2-benzothiazolyl) -2- (4-hydroxy-l-naphthyl) hydrazine,

1- (2-naphthyl) -2-phenylhydrazine,
lp-nitrophenyl-2-phenylhydrazine and l- (1,3 »3-trimethyl-2-indolinyl) -2- (3-N-phenylcarbamoyl-4-hydroxy-1-naphthyl) hydrazine.

*) Amlno-2 _{i >} .3 "dihydroanthrac.hlnone _> ζ. Β.

\ _t k -dianilino-2,3-dihydroanthraquinone and 1,1-bis (ethylamino) -2,3-dihydroanthraquinone.

χ) Phenäthy.! aniline _s ζ. Β *

N- (2-cyanoethyl) -p-phenethylaniline, Ν, Ν-diethyl-p-phenylethylaniline and N, N-dimethyl-p - / "2- (l-naphthyl) ethyl7aniline.

II. Acyl derivatives of Le.ucofarb are open

Acyl derivatives of leuco dyes are particularly suitable, which have a basic NH group and which form amides by acylation. Such compounds include for example the dihydrophenazines, phenothiazines and phenoxazines. Typical such connections are:

10 9 8 16/1854

- 2 sts -

10-acetyl-3,7-bis (dimethylamino) phenothiazine, 10- (p-chlorobenzoyi) -3,7-bis (diethylamino) phenothiazine, 5,10-dihydro-10- (p-nitrobenzoyl) -5-pheny1-3,7-bis-

(phenylethylamino) phenazine and 10- (p-benzoyl) -3,7-bis (naphthylmethylamino) phenoxazine.

III. Substituted triarylmethane compounds in which the simple remaining methane bond is substituted, for example by a benzylthio, 2-phenylhydrazino, alkoxycarbonyl, disulfide or organic amine residue. Mention may be made at * ä play as:

Tris-Cp-dimethylaminophenyl) benzylthiomethane, 1-tris (p-diethylaminophenyl) methyl-2-phenylhydrazine, Tris (4-diethylamino-o-tolyl) ethoxycarbony! Methane, Bis (4-dipropylamino-o-tolyl) (o-fluorophenyl) butoxy-

carbonylmethane and
Bis / "tris (4-diethylamino-o-tolyl) methyl_7disulfide.

IV. Organic amines

For the production of a recording material according to the invention suitable organic amines, the colored compound I supply fertilizers are, for example, those from the USA patents 3,042,515 and 3,042,517 known amines, for example:

4,4 * -ethylene dianiline,
Diphenylamine,
N, N-dimethylaniline,
4,4'-methylenedianiline,
Triphenylamine and
N-vinyl carbazole.

109S iü / 18S4

The photographic recording materials according to the invention can be prepared by customary known methods. This means that, as a rule, initially by mixing at least one compound A with at least one compound B a dispersion or solution is prepared, preferably using a customary binder and preferably using a solvent, whereupon the coating composition obtained is applied to a support in the usual way is applied. On the other hand, however, it is also possible to use a solution of at least one compound Λ and at least a compound B to be used for impregnation of a conventional layer support or from a mixture of compound A, compound B and a binder form a self-supporting recording material without a special support to manufacture.

The usual known binders can be used as binders for the production of a recording material according to the invention used for the manufacture of photographic recording materials are customary and by which the mixture of compound A and compound B, i. H. the hate from the color generator and photo-oxidizing agents, adhered to a substrate. The binder can also be used as Thickeners are used to thicken the solution.

Typical binders for the production of a photographic recording material according to the invention are:

Styrene-butadiene copolymers, silicone resins, styrene-alkyd resins, Silicone alkyd resins, soy alkyd resins, polyvinyl chloride, Polyvinylidene chloride, vinylidene chloride-acrylonitrile copolymers, Polyvinyl acetate, vinyl acetate-vinyl chloride copolymers, Polyvinyl acetate, e.g. B. polyvinyl butyral, polyacrylic and polymethacrylic esters, e.g. B. polymethyl methacrylate,

10 9 8 16/1854

- 58 - '

Riy-ri-butyl methacrylate, poly (isobutylene methacrylate) »polystyrene, nitrated polystyrene, polymethylstyrene, isobutylene polymers, polyester, z. B. poly (ethylene alkaryloxyalkylene terephthalate), phenol-formaldehyde resins, ketone resins, polyamides, polycarbonates, polythiocarbonates, poly (ethylene glycol-eo-bis-hydroxyethoxyphenylpropane terephthalate), copolymers of vinyl haloarylates and vinyl acetate, e.g. B. poly (vinyl-m-bromoben.zoate-co-vinylaeetat), ethyl cellulose, polyvinyl alcohol, cellulose acetate, cellulose nitrate, chlorinated gums, gelatin and the like. Ä

Methods for making such resins are known. They are described in a large number of patents. The preparation of suitable styrene-alkyd resins is described, for example, in U.S. Patents 2,361,019 and 2,258 known. In addition, a large number of such binders are commercially available. Finally, can be used as a binder also such substances as paraffin, mineral waxes and the like., be used.

As already stated, the compounds A and B can be applied to a suitable support by applying a special Layer or by impregnating the substrate ^ are applied. For the production of a recording material According to the invention suitable layer supports can be made from the most varied Papers exist, for example papers as light as tissue paper to cardboard paper. Ais Finally, films made of plastic polymeric materials can also be used for the support, e.g. B. from regenerated Cellulose, cellulose acetate, cellulose nitrate, and also polyesters, e.g. B. from glycol and terephthalic acid, vinyl polyning and vinyl copolymers, polyolefins, e.g. B. Polyethylene ^ Polyvinyl acetate, polyine thy l methacrylate, polystyrene and polyvinyl chloride. If necessary, textile fabrics and knitted fabrics can also be used as a layer carrier, and layered

1 Q 9 8 1 6/1 8 b 4

■■ '■ " ' - · BADORtGlNAL

supports made of glass, wood and metal. Dec further can go to Production of an opaque as well as transparent recording material Base used v / ground. Layer supports or substrates, polygons containing the compounds Λ and B in dissolved form, d. H. for example those supports which have been impregnated with compounds A and B, or which contain the compounds Have Λ and B in the form of a special layer on the back, d. H. that of the one used for exposure The side facing away from the radiation must be transparent, namely xxxxtxxxx opposite xjraxxxxxxxxjcxxxftWKXXXxaKXXgxxKXXXJix XXKXKKIf XXXXftXKXXgXgXKSXXX the radiation used by the Light source is emitted.

Suitable solvents for producing a recording material according to the invention, with the aid of which the compounds A and B can be applied to a layer support, must of course be compared to the compounds A and B. be inert. Typical suitable solvents used for the preparation of recording materials according to the invention can be, for example:

Formamide, Ν, Ν-dimethylformamide, Ν, Ν-dimethylacetamld, hexanimide, Styramide, alcohols e.g. B. methanol, ethanol, 1-propanol, 2-propanol and butanol, glycols, e.g. B. ethylene glycol and polyethylene glycol, Ketones e.g. E.g. acetone and 2-butanone, esters, e.g. ethyl acetate and ethyl benzoate, ethers, e.g. B. tetrahydrofuran and dioxane; chlorinated aliphatic hydrocarbons, e.g. B. methylene chloride and ethylene chloride, aromatic hydrocarbons, z. B. benzene and toluene, as well as other common solvents such. B. dimethyl sulfoxide, o-dichlorobenzene, Dlcyanocyclobutane, l-methyl-2-oxahexamethyleneimine and mixtures this solvent.

8AD ORIGINAL

109816 / 18bA

Different ratios of compound A to compound ß can be used to produce the drawing materials. It has proven expedient to use the two compounds in molar ratios of about 10: 1 to 1:10, preferably 2: 1 to 1: 2. If a binder is used to produce the recording materials, it has proven advantageous to use this in concentrations of about 0.5 to 10 parts by weight per part by weight of compound A and compound B. However, a photosensitive layer of a recording material according to the invention can very generally like when using a binder to 1 Gev! .-% composed of Compound A and Compound B. The two compounds A and B are preferably present in the photosensitive layer in a concentration of 2 to 60 % by weight.

If a layer of compound A, compound B and a binding agent is applied to a layer substrate, it has proved to be useful, these shoes in a layer thickness, Measured wet, to apply from 0.0025 to 0.025 cm, preferably 0.005 to about 0.015 cm.

// In contrast, the recording materials are grounded by Im- f made impregnation of a layer carrier, it has proven to be useful to apply about Apply 0.01 mg to about 5.0 mg of Compound A and Compound B to a 6.45 cm support area.

The application and impregnation of the substrate can be carried out in take place in the usual way, for example by spraying, Spreading the sizing compound or impregnation solution or by application by means of rollers or by means of a dip coating device by (overflowing. over the surface of the substrate and the like. After applying the light-sensitive

109816/1854 BAD

Fincllicheri connections can be coated or impregnated Dry the materials in the usual way at room temperature or in a vacuum or at elevated temperatures.

The recording materials obtained can then be processed according to customary Methods are exposed in an image-appropriate manner. The exposure k-ann using the usual contact copying process, by lens projection, by reflex exposure, by bireflex exposure and the like.

The exposed recording materials can then fixed v / earth to residual connection B, d. H. still available Photooxidant, to be destroyed, v / as by treatment can be done with an alkaline solution or acidic solution, depending on the structure of the compound B used, Finally, reducing agents can also be used to fix the photo-oxidizing agent, which is not present in the Exposed districts exist to be destroyed.

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

example 1

First, a coating composition was made from the following specified components produced on a layer support in a Schichbfcärke, measured wet, of 0.0076 cm was applied:

0.1 ε color former (compound A)

0.25 g photo-oxidizing agent (compound B)

2.0 g polyvinyl acetate (binder)

18.0 grams of methylene chloride

8AD ORIGtNAl. 109816/1854

- W-

There have been several different recording materials using different color formers (compounds Λ) and different Photooxidant (compounds B) produced. The compounds Λ and verb in dun-ι used in the Linzelfalle iien B are compiled in Table I below. In The table also shows the image colors which were obtained by oxidation of the color formers.

Uach applying the colorless coating compositions, the coated layers were dried for 30 minutes at 4O ⁰ C. They were then exposed for 30 seconds through a lialbton positive using an Illitrophot lamp.

Tabel

Color former (compound A)

Tris (p-dimethylaminophenyl) methane

Il Il It Il Il Il 11 It It

Photo-oxidizing agents

(Connection B) _t Image color

Connection no.44 blue

It It 24 It Il I! 25th Il Il It 29 Il Il ti 1 It Il ti 12th Il It It 18th ti It It 20th ti ti It 28 Il without colorless

Λ Q = OB 1 6/1 8 B k

BATH

Example 2

The procedure described in Example 1 was repeated, with the exception, however, that this time a mercury lamp (film type 086) was used as the light source. Similar results were obtained. The lamp is a commercially available high-pressure mercury lamp that emits light that is rich in UV radiation.

Example 3

Further recording materials were produced using a coating composition from the im the following specified components. The coating mass was measured in a layer thickness of 0.0076 cm, wet, applied to a paper support.

0.02 g color former (compound A) 0.04 g II-Kthoxy-2-picolinium hexafluorophosphate

as a photo-oxidizing agent (compound B) 2.0 g of polyvinyl butyral as a binder 18.0 grams of methylene chloride

The colorless recording materials produced using various color formers (compounds A) were then exposed in the usual way with a mercury arc lamp in accordance with the image. Using various compounds A The results obtained are shown in Table II below.

Table II Color former image color

Tris (p-dimethylaminophenyl) methane blue

Tris (p-hydroxyphenyl) methane red

p- (2,2-Dicyanoethyl) -N, H-dimethylaniline yellow

n- (1,2,2-tricyanoethyl) -N, M-dimethylaniline orange ■

1 0 9 8 1 ö / 1 8 b 4

8AD ORIGINAL

• Μ

Table II (continued)

p-phenylenediamine. . Mrs

Tris ^ l-diethylainino-o-tolyljmethantrlhydrochlorld blue

example > \

The procedure described in Example 3 was repeated with the exception, however, that the photo-oxidizing agent (compound B) this time N-methoxy-2-anilinovinylpyridinium-para-toluene sulf fonat was used. Similar results were obtained. Became the I! - 'iethoxy-2-anilinovinylpyridinium paratoluenesulfonate omitted, the exposed recording material remained colorless even after exposure.

1098,1,6 / 1854

Claims (1)

Claims lly photographic recording material, consisting of a layer support and (a) at least one colorless or practically colorless organic compound Λ applied to it, "which is oxidizable to a colored compound, and (b) at least one organic compound B applied to it, which when exposed to light decomposes with the formation of at least one compound which oxidizes compound A to a colored compound, characterized in that it contains as organic compound B a heterocyclic compound with a ring nitrogen atom substituted by an acyloxy or alkoxy group of one of the following formulas: \ 7 ^R t OR
(II.) ν φ / OR (III.) R ₁₁ f- —τ R ₀ Χ ^θ or OR
109816/1854 SAD ORIGINAL O - R U 5 < R ₁ where mean: 2 Χ ^θ those to complete an optionally substituted 5- or 6-membered, heterocyclic ring required atoms; an optionally substituted alkyl or acyl radical; an optionally substituted methine or polymethine group with a terminal, for cyanine dyes usual, heterocyclic ring, an anilinovinyl, an optionally substituted styryl, alkyl, aryl or aldehyde radical, an acyl radical or an Itfassstoffatom; in each case a hydrogen atom or an optionally substituted alkyl or aryl radical; 1090 ί ο / 1 8b 4 Η _Γ an alkylene or alkyleneoxy radical with 1 to 8 carbon atoms in the alkylene chain; Ro is an optionally substituted methine or polymethine group with a terminal heterocyclic group customary for merocyanine dyes Ring or an optionally substituted allylidene radical; Q ₂ and Qq to complete a 5- or 6-membered, heterocyclic ring required Atoms and Χ ^{θ is} an acid anion. Photographic recording material according to Claim 1, characterized in that it is used as a light-sensitive compound D contains a compound of the formulas I or II, in which Z is the optional to complete a Substituted pyridine or quinoline ring represents required atoms. Photographic recording material according to Claim 1, characterized in that it is used as a light-sensitive compound B contains a compound of the following formulas: R _p ^ 2 "^ N - if CH-CH C - (L
OR 109816/1854 20A6018 M »4» CH-CH C - (- L »L-j G X R _{2 m} - Q ₂ - * ^ ^ Q ₁ , AT / KO-N - {- CHsCH C ^ L - L ^ "* C C * 0 or ti ^ -U.p-. RO -N-f-CH * CH-) --C- ^ L-L C g-1 in s. ^R 7 viorln mean: R is an optionally substituted alkyl or acyl radical; R ^ is a hydrogen atom or a given if substituted alkyl or aryl group; R-, an optionally substituted alkyl, Alkenyl, aryl or alkoxy radical; Q ₁ , Q ₂ and Q ₁ J are the atoms required to complete 5- or 6-membered heterocyclic rings; L is an optionally substituted methine group j 109 816/1854 R-. and Ii ₇ each represents a cyano, ester or alkylsulfonyl radical; Χ ^θ .an acid anion; G an anilino or optionally substi tuated aryl radical; or an anilino-vinyl radical; g = 1 or 2; m = 1, 2 or 3 and η = 1,2, 3 or 4. 4. Photographic recording material according to claims to 3i characterized in that it is the connection A and B contained on the support in a 5Jcnot, dispersed in a binder, arranged. 5. Photographic recording material according to Claims to 3 »characterized in that it is used as compound A contains: 1) a leuco dye, 2) an N-acyl derivative of a leuco dye, 3) a triarylmethane, its individual remnants Methane bond through a benzylthio, 2-phenylhydrazino, alkoxycarbonyl or disulfidreat is substituted, or ¹ O is an organic amine. 6. Photographic recording material according to claim k _t 109816/1854 uaaurch in that the layer disposed on the support layer are each 0.1 to 10 wt -% Compound Λ and compound contains ß.. 7. Photographic recording material according to claims 1 to 6, characterized in that it is used as connection A Tris (p-dimethylaminophenyl) methane and as compound B -a ii-alkoxy-2-picolinium salt or a lJ-alkoxy-2-anilino contains vinylpyridirium salt. 8AD