DE1950735A1 - Photographic imaging material - Google Patents

Description

Photographic imaging material

The invention relates to a photographic image recording material, consisting of a support and at least one light-sensitive, photobleachable dye.

It is known to be photosensitive for producing colored images photographic recording materials with bleachable Use dyes. When using these non-silver-containing photographic recording materials Images can be produced in that the dye or dyes of the recording material in relation to the irradiated Amount of light to be bleached. In this way, direct positive images can be obtained.

Multi-colored, direct-positive images can be produced from corresponding recording materials in that this contains several different colored fade-out dyes, in particular at least one blue-green, one purple-red and a yellow dye.

009817/1683

The disadvantage of the recording materials known to date is that the bleaching or discoloration of the dyes occurs through Exposure takes place relatively slowly, even when using sensitizers, so that the previously known Recording materials of this type have not achieved great industrial importance.

• The object of the invention was therefore to provide a photographic image recording material, consisting of a layer support and at least one light-sensitive, photobleachable dye, indicate from which colored pictures can be quickly produced.

The subject matter of the invention relates to a photographic image recording material consisting of a layer support and at least one light-sensitive, photobleachable dye, and is characterized in that the recording material as a photobleachable dye a dye with a heterocyclic ring with the group N-OR, wor-

t in R is an optionally substituted alkyl, acyl or

Aryl radical, contains one of the following formulas:

OR

^R l

OR

00-8 * 17 / VB 8 3

HI R ₄ '- © -) ^R 2 ⁵ ^ ^or

OR

- Κ » Α ² -

N-O-Rg N 0

R>

IV Q, N-O-Rg-N

where mean:

Z to complete an optionally substituted, 5- or 6-membered, heterocyclic Ring's required atoms;

R is an optionally substituted alkyl, aryl or acyl radical;

Ri is an optionally substituted methine or polymethine group with a terminal heterocyclic ring customary for cyanine dyes, an anilinovinyl radical or an optionally substituted styryl radical;

R ~ and R. each represent a hydrogen atom or optionally one substituted alkyl or aryl radical;

009817/1683

R _{5 is} an alkylene or alkyleneoxy radical having 1 to 8 carbon atoms in the alkylene chain or a radical of the formula -f-CH -) - R ₁ - ^ - 6 CH ₇ - O -, in which: s and t each denote numbers of 1 to 8, u ^e 0 or 1 and
R ^ _{0 is} an arylene radical;

Rg is an optionally substituted methine or polymethine group with a terminal heterocyclic ring customary for merocyanine dyes; a optionally substituted allylidene radical or an aldehyde radical;

Q ₂ and Qg the atoms required to complete a 5- or 6-membered heterocyclic ring and

T ^ an acid anion.

R ₁ Q is preferably an optionally substituted phenylene or naphthylene radical.

The photographic image recording material of the invention enables it to produce direct positive color images quickly. According to the invention for the production of the image recording material The dyes used have the advantage over the known, previously used, photobleachable dyes, that they can be faded faster. To bleach the dyes, the light sources customary for photobleaching processes can be used, z. B. Flash lamps and lamps with a lot of UV light can be used.

The usefulness of the dyes described is based on the fact that on exposure to light of a wavelength which is absorbed by them, the dyes are split up or fragmented into smaller fragments or components. The degradation or disintegration mechanism that occurs in the individual case depends somewhat on the structure of the compound used in the individual case. On the basis of observations, however, the degradation or destruction of the compounds by exposure to light takes place, for example, like ^ Ig ₁ J ₉₈ 1 7/1 6 83

CH = CH-CH = C

ην

CH ₃ O + I- +

further -> fragments

CH = CH-CH = C

C ₂ H ₅

H + CH ₂ O

There is thus a photobleaching through heterolytic splitting the nitrogen-oxygen bond to produce a Ions of the formula RO and a dye base, which in further Fragments or fragments can disintegrate.

The dyes used according to the invention for the production of the recording material become rapidly corresponding to the irradiated Amount of light destroyed.

The original color tone of the dyes appears when combined with a Acid treated so that the pH of the recording material is below 7. There is no further photo bending, when the dye is further exposed to energy.

009817/1683

_{If R 1} in the given structural formula II represents a methine or polymethine group with a terminal heterocyclic ring customary for cyanine dyes, this can be substituted or unsubstituted, for example by an alkyl or aryl radical, and z. B. have one of the following structural formulas:

-CH = CH-, -CH =, -C (CH ₃ ) =, -C (C ₆ H ₅ ) = or -CH = CH-CH =.

Heterocyclic rings customary for cyanine dyes, through which the methine or polymethine group can be terminated, are for example in the book by Mees and Jones "The Theory of the Photographic Process", MacMillan Verlag, 3rd edition, Pages 198 * 232.

00 * 817/1683

If R- has the meaning of an anilinovinyl radical, then has this preferably the formula:

-CH = CH-N

where Rj is a hydrogen atom or an alkyl has radicals with preferably 1 to 8 carbon atoms.

If R, has the meaning of an optionally substituted styryl radical, this preferably has the formula:

-CH = CH

wherein R2 is a hydrogen atom, an alkyl radical with preferably 1 to 8 carbon atoms, an aryl radical, preferably of the phenyl or naphthyl series, or an amino radical, inclusive a dialkyl audno residue, for example a dimethylamino residue, can be.

If R has the meaning of an optionally substituted Alkyl radical, this preferably has 1 to 8 carbon atoms and consists, for example, of a methyl, ethyl or Butyl radical, or for example from a Siifoalkylrest, z. B. of the formula /CH^SO.-, or an aralkyl radical, e.g. B. a Benzyl or pyridinato-oxyalkyl salt residue, e.g. B. of the formula - (C ^ Dj-O-Y, wherein Y is an optionally substituted pyridinium salt radical is.

If R has the meaning of an optionally substituted aryl remainder, then this preferably consists of one nc as well substituted phenyl or naphthyl radical »z, 3, a phenyl, Naphthyl or tolyl radical.

009117/1683

If R is an acyl radical, this preferably has the formula _Q

I!

-CR ₆

on, wherein R is an alkyl radical having 1 to 8 carbon atoms or is an aryl radical, preferably of the phenyl or naphthyl series, d. H. for example a methyl, ethyl, propyl, butyl, phenyl or naphthyl radical.

The S- or 6-membered, heterocyclic ring completed by Z can, in addition to the nitrogen atom already present in the ring optionally contain at least one further heteroatom, for example an oxygen, sulfur, selenium or Nitrogen atom. Z preferably represents those required to complete a pyridene - «^ βΗΗΙ or quinoline ring Atoms.

The methine group represented by R _g may be a methine group as defined in connection with R 1. Terminal heterocyclic rings customary for merocyanine dyes are described, for example, in the already mentioned book by Mees and Jones "The Theory of the Photographic Process".

If Rg has the meaning of an optionally substituted one Allylidenrestes, this can for example from a Dicyanoallylidenrest, an Alkylcai'boxyallylidenrest or a Alkylsulfonylallylidene radicals consist, the alkyl groups of these radicals preferably having 1 to 8 carbon atoms.

If R and R. are alkyl radicals, they preferably have 1 to 12 carbon atoms, in particular 1 to 4 carbon atoms. If R ₂ and Γ .. have the meaning of aryl radicals, these preferably consist of aryl radicals

009817/1683

ORlGiNAl INSPECTED

Phenyl or naphthyl series, d. H. For example, Rp and Rh can its methyl, ethyl, propyl, isopropyl, butyl, decyl or dodecyl radicals or phenyl, tolyl, naphthyl, methoxyphenyl, Chlorophenyl or nitrophenyl radicals.

Q ₂ and Qg preferably represent those 5- or 6-membered, heterocyclic rings which are typical of cyanine dyes and, in addition to the nitrogen atoms already present, can contain a further heteroatom, for example an oxygen, sulfur, selenium or nitrogen atom.

For example, X can be an acid anion, as in cyanine dyes occurs, for example a chloride, bromide, iodide, perchlorate, sulfamate, thiocyanate, p-toluenesulfonate, methyl sulfate or tetrafluoroborate anion.

R, - can be, for example, an ethyleneoxy, trimethyleneoxy, Tetramethyleneoxy, propylidenoxy, ethylenedioxy or phenylenebisethoxy radical.

According to a particular embodiment of the invention, the recording material contains a photobleachable dye Dye of one of the following formulas:

θ - '\ \ . * \ _θ N ^ f ^ CH — CH ^s 4 = ^ = CfL = L -) - τ-L «Cf-CH = CH ^) r NR, X

L-C "C" N-R

Χ ^θ

00S617 / 1683

j g-1 m

G Χ ^θ

RO-N = C-C'4 = LL = ^ = C - (- CH = CH- NR ₃

RO-ΐί - (- CH = CH-) = - C ^ = L-L = J = C C O or

^R 2
¹

RO-N-f-CH-CH-C-f-L-L

where mean:

R is an optionally substituted aryl, alkyl or acyl radical;

Rp is a hydrogen atom or an alkyl or aryl radical the meaning already given;

009817/1683

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

^to complete the 5- or 6-link

and Q ₇ ger, heterocyclic rings required

Atoms;
L is an optionally substituted methine group;

Rg and R ₇ each represent a cyano, ester or alkylsulfonyl radical;

D, E and J each represent a hydrogen atom or an alkyl or aryl radical;

Χ ^θ an acid anion;

G is an anilino or optionally substituted

. aryl radical;

g = 1 or 2;

m = 1, 2 or 3 and

η = 1, 2, 3 or 4.

In the structural formulas given, Q ₁ , Q ₂ , _{Q 1, Q 7} and Qn represent the atoms which are required to complete 5- or 6-membered heterocyclic rings, as are typical for cyanine dyes. The rings can consist of sensitizing or desensitizing rings and can have a second heteroatom, for example an oxygen, sulfur, selenium or nitrogen atom.

Qn »Qp * ^ V ^ 7 ^and ^ 9 ^can for example stand for the atoms that form one:

009617/1683

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-; Benzothiazoles 4-chlorobenzothiazole-; 4- or 5-nitrobenzothiazole-; 5-chlorobenzothiazole-; 6-chlorobenzothiazole-; 7-chlorobenzothiazole-; 4-methylbenzothiazole-; 5-methylbenzothiazole-; 6-methylbenzothiazole-; 6-nitrobenzothiazole-; 5-bromobenzothiazole-; 6-bromobenzothiazole-; 5-chloro-6-nitrobenzothiazole-; 4-phenylbenzothiazole-; 4-methoxybenzothiazole-; 5-methoxybenzothiazole-; 6-methoxybenzothiazole-; 5-iodobenzothiazole-; 6-iodobenzothiazole-; 4-ethoxybenzothiazole-; 5-ethoxybenzothiazole-; Tetrahydrobenzothiazole; 5,6-dimethoxybenzothiazole-; 5,6-dioxymethylene benzothiazole; 5-hydroxybenzothiazole-; 6-hydroxybenzothiazole-; a-naphthothiazole-; ß-naphthothiazole-; ß, ß-naphthothiazole-; 5-methoxy-ß, ß-naphthothiazole-; 5-ethoxyß-naphthothiazole-; 8-methoxy-a-naphthothiazole-; 7-methoxy-anaphthothiazole-; 4'-methoxythianaphtheno-7 ¹ , 6 ', 4,5-thiazole or a naphthothiazole ring substituted by a nitro radical;

an oxazole ring, e.g. B. a 4-methyloxazole; 4-nitro-oxazole-; 5-methyloxazole-; 4-phenyloxazole-; 4,5-diphenyloxazole-; 4-ethyloxazole-; 4,5-dimethoxazole-; 5-phenyloxazole-; Benzoxazole-; 5-chlorobenzoxazole-; 5-methylbenzoxazole-; 5-phenylbenzoxazole-; 5- or 6-nitrobenzoxazole-; S-chloro-o-nitrobenzoxazole-; 6-methylbenzoxazole-; 5,6-dimethylbenzoxazole-; 4,6-dimethylbenzoxazole-; 5-methoxybenzoxazole-, 5-ethoxybenzoxazole-; 5-chlorobenzoxazole-; 6-methoxybenzoxazole-; 5-hydroxybenzoxazole-; 6-hydroxybenzoxazole-; a-naphthoxazole-; ß-naphthoxazole or a naphthoxazole ring substituted by a nitro radical;

a selenazole ring, e.g. B. a 4-methylselenazole; 4-nitroselenazole-; 4-phenylselenazole-; Benzoselenazole-; 5-chlorobenzoselenazole-; 5-methoxybenzoselenazole-; 5-hydroxybenzoselenazole-;

00S817 / 1683

5- or 6-nitrobenzoselenazole-; S-chloro-δ-nitrobenzoselenazole-; Tetrahydrobenzoselenazole-; ot-naphthoselenazole-; ß-naphthoselenazole or a naphthoselenazole ring substituted by a nitro radical;

a thiazoline ring, e.g. B. a thiazoline; 4-methylthiazoline or 4-nitrothiazoline ring;

a pyridine ring, e.g. B. a 2-pyridine; S-methyl-2-pyridine-; 4-pyridine-; 3-methyl-4-pyridine or a pyridine ring substituted by a nitro radical;

a quinoline ring, ζ. B. a 2-quinoline; 3-methyl-2-quinoline-; 5-ethyl-2-quinoline-; 6-chloro-2-quinoline-; 6-nitro-2-quinoline-; 8-chloro ~ 2-quinoline-; 6-methoxy-2-quinoline-; 8-ethoxy-2-quinoline-; S-hydroxy-Z-quinoline-; 4-quinoline-; 6-methoxy-4-quinoline-; 6-nitro-4-quinoline-; 7-methyl-4-quino-lin-;
8-chloro-4-quinoline-; 1-isoquinoline-; 6-nitro-1-isoquinoline-;
3,4-dihydro-1-isoquinoline or 3-isoquinoline ring;

a 3,3-dialkylindolenin ring, preferably with a nitro
or cyano radical, e.g. B. a 3,3-dimethyl-5- or 6-nitroindolenine; 3,3-dimethyl-5 or 6-cyanoindolenine ring;

an imidazole ring, e.g. B. an imidazole; 1-alkylimidazole-;
1-alkyl-4-phenylimidazole-; 1-alkyl-4,5-dimethylimidazole-;
Benzimidazole-; 1-alkylbenzimidazole-; 1-alkyl-5-nitrobenzimidazole-; l-aryl-5, ^ - dichlorobenzimidazole-; 1-alkyl-α-naphthimidazole ring; or 1-aryl-β-naphthimidazole or 1-alkyl-5-methoxyu-naphthimiduzole ring.

an imidazo / 4,5-b-7-quinoxaline ring, e.g. B. a 1-alkylimidazo / "4,5-b_ / quinoxaline ring, z. B. a 1-ethylimidazo - / "4,5-b_7cliinoxalin ~; 6-chloro-l-ethylimidazo / ~ 4, 5-b_7-

0ÖS817 / 1883

quinoxaline-; l-Alkenylimidazo / ~ 4,5-b_7quinoxaline-, ζ. B. 1-Allyl imidazo / "4,5-b_7-quinoxaline-; 6-chloro-1-allylimidazo / ~ 4,5-b_7-quinoxaline-; 1-arylimidazo ^ ~ "4,5-b_7quinoxaline-, e.g. a 1-phenylimidazo / ~ 4,5-b_7quinoxaline- or 6-chloro-l-phenylimidazo- / 4,5-b-7-quinoxaline ring;

a 3,3-dialkyl ~ 3H-pyrrolo _j / "b_7pyridinring 2,3-,. for example a 3,3-dimethyl-3H-pyrrolo / ~ ~ 2,3-b_7pyridin or 3,3-diethyl-3H- pyrrolo ^ "2,3-b_7 pyridine ring;

a thiazolo / ~ 4,5-β-7quinoline ring;

If R ₆ and R _{7 have} the meaning of ester radicals, they can, for. B. order from methoxycarbonyl and ethoxycarbonyl residues. Have R ₆ and R ₇ the meaning of alkyl sulfonyl radicals, these can, for. B. consist of methyl sulfonyl and ethyl sulfonyl radicals. The lister or alkylsulfonyl radicals preferably contain 1 to 8 carbon atoms.

The heterocyclic ring completed by Q ₄ can, for example, have a nitrogen, sulfur, selenium or oxygen atom as a hetero atom or several of these atoms. For example, Q / can stand for the atoms that complete a:

2-pyrazolin-5-one ring, e.g. B. a 3-methyl-l-phenyl-2-pyrazolin-5-one, l-phenyl-pyrazolin-S-one or 1- (2-benzothiazolyl) -3-methyl-2-pyrazolin-5-one ring;

00 S117 / 16 8 3

an isoxazolone ring, e.g. B. a 3-phenyl-S- (4II) -isoxazolo: a- or 3- "ICtAyI-S- (4il) -isoxazolone ring;

an oxindole ring, e.g. B. a l-alkyl-2,3-dihydro-2-oxindole

a 2,4, o-Trikctohexahydropyrimidiiiring, z. B. a barbituric acid or 2-thiobarbituric acid ring with their 1-alkyl derivatives, e.g. B. 1-methyl, l-.Athy] -, 1-propyl or 1-IIeptyl derivatives, or 1,3-dialkyl derivatives, e.g. ! '. 1,3-diretliyl-, I, 3- [liäthyl-, 1,3-di ₁ -IrO ^ yI-, 1,3-diisopropyl-, 1,3-ni-cyclohexyl or 1,3-di (P-liiethoxyethyl ) derivatives, or 1, 3-diaryl derivatives, e.g. B. 1, 3-Piphcnyl-, 1, 3-Di (p-chloi-ophcnyl) - or 1,3-Di (p-ethoxycarbonylphynyl) derivatives, or 1-aryl derivatives, z. ", 1-phenyl-, 1-p-chlorophenyl-Of'er] -p -. ^ T'ioxycarbonylphenyl derivatives, or 1-alkyl-3-arylcierivatcn, z. B. 1-ethyl-3-phenyl- or ln-leptyl -3-phenyl derivatives;

a rhodanine ring, d. h, a 2-thio-2,4-thiazolidinedione ring, z. B. a rhodanine or 3-alkylr3iodanine ring, e.g. B. a 3-ethylrhodanine or 3-allylrhodanine p;, or a 3-carboxyalkylliodaaine ring, e.g. B. cin> -; n 3- (2-carboxyethyl) rhodanine- or 3- (4-carboxybutyl) rhodanine ring, or a 3-sulfoalkylrhoüanine ring, z. ". a 3- (2-sulfo'ithyl3 rhodanine, 3- (3-sulfopropy]) rhodanine or 3- (4-sulfobutyl) rhodanine ring, or a 3-arylrhodanine ring, e.g., a 3-phenylriodanine ring;

a 2 (311) -iniidazo / ~ 1, 2-a_ / pyridone ring;

eino.i 2-furanone ring, e.g. V>. a 3-cyano-4-phcn / l-2 (oi!) - furanone ring;

009817/1683

OHlQlHAL

a thiophene-S-on- ^ l-dioxyclring, ζ. ]>. a benzo / b _ / - thiophen-3 (2il) -one-l, 1-dioxy dring;

a 5, 7-D: ioxo-6, 7-dihydro ~ 5-tiiiazolo / ~ 3, 2-a_ / pyrine: idine ring, z. B. a 5,7-Dioxo-3-phenyl-6,7-dihydro-5-thiazolo / ~ 3,2-a-7 ~ pyrimidine ring;

a 2-thiio-2,4-oxazolidinedione ring, d. H. a 2-thio-2,4- (3II, 5Ii) -oxazoldione ring, z. B. a 3-Atnyl-2-thio-2,4-oxazolidiiidion-, 3- (2-sulfobutyl) -2-thio-2, 4 -oxazolidinedione- ', 3- (4-sulfobutyl) -2-1; hio-2,4-oxazolidinedione- or 3- (3-carboxypropyl) 2-thio-2,4-oxazolidinedione ring;

a thiianaphthenone ring, e.g. 13. a 2- (2II) thianaphthenone ring;

a 2-thio-2,5-thiazolidinedione ring, ie a 2-thio-2,5- [3II, 4II) -t3iiazoldione ring, e.g. B. a 3-methyl-2-thio-2,5-thia ζ ο 1 i < ¹ i η d 1 on ri: ig;

a 2 j4-thiazoliclintlionri] ig, e.g. ^T >. a 2,4-thiazolidinedione, 3-atliyl-2,4-t3iiazolidinedione, 3-P: -. onyl-2, 4-thiazolidinedione or 3-o: -xaplithyl-2,4-thiazolidinedione ring;

a thiazolidinone ring, e.g. B. a 4-thiazolidinone, 3-Xt] iyl-4-tliiazolidinon-, 3-Phe "hyl-4-thiazolidinone or 3-cx-naphthy1-4-thiazolidinone ring;

a 2-triazolin-4-one ring, e.g. ". a 2-Atliyln ⁱ ercapto-2-thiazolin-4-on-, 2-alkylp * acnyla: iiino-2-thiazo] i: il-on- or 2 ~ Diplicnylar.inö-2-thiazolia-4-onring_ ;

a 2-Ii-; ino-4-oxazol-idinonri: ig, el. h. a pseudohydantoinrin-;

009817/1683

BADORiGIMAt

a 2,4-iiiiidazolidinedione ring, d. H. an llydantoin ring, e.g. a 2,4-imiclazolidinedione, 3-ntlr / l-2,4-imidazolidinedione, 3-phenyl-2,4-iinidazolidinedione, 3-c ^ naphthyl-2,4-imidazolidinedione-, 1,3-diethyl-2,4-imidazolidinedione-, l-ethyl-3-phenyl-2, 4-imidazolidiridione-, l ~ Xthyl-2-a-napb.t] r / l-2,4-imidazolidinedione- or 1, 3-i) iplienyl-2,4-i! :: idazolidinedione ring;

ainone 2-thio-2,4-iuuoazolidinedione ring, d. 1). a 2-thiolydantoin ring, z. B. a 2-thio-2,4-imidazolidinedione, 3 -, "thyl-2-thio-2,4-inidazolidinedione, 3- (4-sulfobutyl) .- 2-thio-2,4-imidazolidinedione-, 3- (2-Carboxyethyl) -2-thio-2,4-imidazolidinedione-, 3-phenyl-2-thio-2,4-imidazolidinedione-, 3-criiäphthyl-2-thio-2,4-imidazolidinedione-, l, 3-diethyl-2-thio-2,4-imidazolidinedione, l-ethyl-3-phenyl-2-thio-2,4-imidazolidinedione-, l-Xthyl-3-a-naphthyl-2-thio-2,4-imidazolidinedione- or 1,3-Diphenyl ~ 2-thio-2,4-ircidazolidinedionrin £, or one

2-I; .. idazolin-5-one ring, e.g. B. a 2-propylmercapto-2-imidazolin-5-one ring.

Q2 provides ^T .; Ice for the atoms that complete an optionally substituted pyridine, flHHfe or quinoline ring.

D, E and J preferably represent v / cisc Arylre.otc.

Nuclei, ..ori "Q ,, Q-,» -Ir, Ί. <, '} Y and Qn £'<*? The ators, which are necessary to complete an imidazo ^ 4,5-b_ / quinoxaline ring or a thiazole, oxazole, selonazole, thiazoline, pyridine, chiriol Li, indole or Iinidazolriugcs are required, so-called deson- 'siMli.'iiorojice or descnsibilisiorond acting, "rage.

CÜS817 / 1S83

If R- has the meaning of an optionally substituted one Alkyl radical, this preferably has 1 to 12, in particular 1 to 4, carbon atoms. R, can thus for example consist of a methyl, ethyl, propyl, isopropyl, butyl, hexyl, cyclohexyl, decyl or dodecyl radical, or one Hydroxyalkyl radical, .ζ. B. a ß-hydroxyethyl or ω-hydroxybutyl radical, or an alkoxyalkyl radical, e.g. B. a ß-methoxyethyl or ω-butoxybutyl radical, or a carboxyalkyl radical, z. B. a ß-Carboxyäthyl- or ω-Carboxybutylrest, or one Alkoxy radical, e.g. B. a methoxy or ethoxy radical, or a sulfoalkyl radical, e.g. B. a ß-sulfoethyl or to-sulfobutyl radical, or a sulfatoalkyl radical, e.g. B. a ß-sulfatoethyl · 'or ω-sulfatobutyl radical, or an acyloxyalkyl radical, e.g. B. a ß-acetoxyethyl, γ-acetoxypropyl or ω-butyryloxybutyl radical, or an alkoxycarbonylalkyl radical ^ z. B. a ß-methoxycarbonylethyl or ω-ethoxycarbonylbutyl radical, or an aralkyl radical, z. B. a benzyl or phenethyl radical.

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

If R- has the meaning of an optionally substituted aryl radical, this preferably consists of an optionally substituted aryl radical of the phenyl or naphthyl series and consists, for example, of a phenyl, tolyl, naphthyl, Methoxyphenyl or chlorophenyl radical.

L can, for example, be one through an alkyl or aryl radical substituted methine group, for example a group of the following structural formulas:

-CII =, -C (CH ₃ ) =, -C (C ₆ H ₅ ) =.

L is preferably a methine group of the formula -C =, in which T is a hydrogen atom, an alkyl radical having 1 to T 4 carbon atoms or an aryl radical of the benzene series, Z ₀ B * is a phenyl radical. 009817/1683

If D, E and J are alkyl radicals, these preferably have 1 to 12, in particular 1 to 4, carbon atoms and consist, for example, of methyl, ethyl, propyl, isopropyl, butyl, decyl or dodecyl radicals.

If D, E and J have the meaning of aryl radicals, these preferably consist of aryl radicals of the phenyl or naphthyl series and consist, for example, of phenyl, tolyl, naphthyl, Methoxyphenyl, chlorophenyl or nitrophenyl radicals.

X can in turn, for example, be a perchlorate, tetrafluoroborate, Chloride, bromide, iodide, sulfamate, thiocyanate, p-toluenesulfonate or methyl sulfate anion.

If G has the meaning of an aryl radical, this preferably consists of an aryl radical of the phenyl or naphthyl series, for example a phenyl, naphthyl, dialkylaminophenyl, tolyl, chlorophenyl or nitrophenyl radical. Does G mean of an anilino radical, this preferably has the formula

wherein R _{3 is} a hydrogen atom or an alkyl or acyl radical having 1 to 8 carbon atoms.

_{The radical R 5} shown in structural formula IV can be, for example, an ethyleneoxy, trimethyleneoxy, tetramethyleneoxy, propylidenoxy, ethylenedioxy or phenylenebisethoxy radical.

If R has the meaning of an optionally substituted alkyl radical, so this can expediently have up to 12, preferably 1 to 8 and in particular 1 to 4 carbon atoms, d. H. R can be, for example, a methyl, ethyl, propyl, isopropyl, butyl, hexyl, cyclohexyl, decyl, dodecyl radical, or an alkaryl radical, such as a benzyl radical, or a sulfoalkyl radical, for example a ß-sulfoethyl, <X) sulfobutyl or co-sulfopropyl radical.

009817/1683

- 2 O - ο.

If R has the meaning of an acyl radical, this can be given by the formula: O

-C-R

are shown, where R is an optionally substituted alkyl radical of the meaning given or an aryl radical, preferably the phenyl or naphthyl series, d. H. for example a methyl, phenyl, naphthyl, propyl or benzyl radical can.

In the formulas Q ₂ preferably stands for the atoms which are necessary to complete a pyridine ^ βΗΒΙ or quinoline ring.

Furthermore, D, E and J preferably represent aryl radicals.

Advantageously, Q ₁ , Q 2, Q ₃ , Q ₇ and Q _g can also stand for the atoms which are required to complete an imidazo / ~ 4,5-b_ / quinoxaline ring or a thiazole, oxazole ring substituted by a nitro radical , Selenazole, thiazoline, pyridine, quinoline ^ MHP or imidazole ring are required. These rings are desensitizing rings.

Typical dyes which can be used according to the invention Connections are for example:

008817/1683

ORiOINAL INSPECTED

Tabel

1. 3-ethyl-1'-methoxyoxa-2'-pyridocarbocyanine perchlorate;

2. 1'-ethoxy-3-ethyloxa-2'-pyridocarbocyanine tetrafluoroborate;

3. 3'-ethyl-1-methoxy-2-pyridothiacyanine iodide;

4. l-ethoxy-S-ethyl ^ -pyridothiacyanine tetrafluoroborate;

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

6. 3 ¹ -ethyl-1-methoxy-2-pyridothiacarbocyanin iodide;

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

8. Anhydro-3'-ethyl-1- (3-sulfopropoxy) -2-pyridothiacarbocyanine hydroxide;

9. l-Benzyloxy-3 '-ethyl-2-pyridothiacarbocyanine perchlorate; ·

10. 3 ^t -ethyl-1-methoxy-2-pyridothiadicarbocyanine perchlorate;

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

12. 3'-ethyl-1-methoxy-4 ', 5'-benzo-2-pyridothiacarbocyanine perchlorate;

13. l-ethoxy-3 ¹ -ethyl-4 ¹ , 5'-benzo-2-pyridothiacarbocyanine tetrafluoroborate;

14. 1'-ethoxy-3-ethyloxa-2'-carbocyanine tetrafluoroborate;

15. 1'-ethoxy-3-athy.lth.ia-2 ¹ -cyanine tetraf luoroborate;

16. 1'-ethoxy-3-ethylthia-2'-carbocyanine tetrafluoroborate;

17. 1'-Ethoxy-3-ethylthia ^ '- dicarbocyanine tetrafluoroborate;

18. l-methoxy-3 ^l -methyl-2-pyridothiazolinocarbocyanine perchlorate;

19. 3'-ethyl-1-methoxy-4-pyridothiacyanine perchlorate;

20. 3'-ethyl-1-methoxy-4-pyridothiacarbocyanine perchlorate;

25. 1'-Ethoxy-3-ethy1-4,5-benzothia-2 ¹ -carbocyanine tetrafluoroborate;

26. 2-β-anilinovinyl-1-methoxypyridinium-p-toluenesulfonate;

27. l-ethyl-l ^l -methoxy-4,5-benzothia-4'-carbocyanine perchlorate;

009017/1683

44. 1,1'-ethylenedioxybispyridinium dibromide;

45. 1,1'-trimethylenedioxybispyridinium dibromide;

46. 1,1'-tetramethylenedioxybis (2-methylpyridinium) dibromide;

47. 1,1'-tetramethylenedioxybis (4-methylpyridinium) dibromide;

48. 1,1'-tetramethylenedioxybispyridinium dibromide;

49.1, T'-pentamethylenedioxybispyridinium dibromide;

52. 1-acetoxy-2- (4-dimethylaminostyryl) pyridinium perchlorate;

53. 1-benzoyloxy-2- (4-dimethylaminostyryl) pyridinium perchlorate;

003117/1883

54. 1,3-diethyl-5 - / "(l-methoxy-2 (lH) -pyridylidene) ethylidene-7-2-thiobarbituric acid;

55. 3-Ethyl-5- ₍ / "(l-methoxy-2 (1H) -pyridylidene) ethylidene-7-. Rhodanine;

56. 1,3-diethyl-5- ^ "(l-methoxy-2 (lH) -pyridylidene) ethylidGn_7-barbituric acid;

57. 2- (3,3-dicyanoallylidene) -l-methoxy-1,2-d5hydropyridine;

58. 2- / ~ (1-methoxy-2 (10-pyridylidene) ethylidene / benzo / "b-7-thiophene-3 (2H) -one-1,1-dioxide;

59. 3-Cyano-5 - ^ "(1-methoxy-2 (1H) -pyridylidene) ethylidene_7-4-phenyl-2 (5H) -furanone.

003817/1683

According to a further particularly advantageous embodiment of the invention, the recording material contains at least a dye with the following structural formulas:

η — χ

Q ₁ -.

-NO

OR

L -

R,

wherein R, R ₂ , R ^, R ^, R _7,. L, Q-,, Qj., X ₅ G, n, g and m have the meanings already given.

009117 / 1B83

Typical dyes in these formulas are dyes 1 - 13, 18, 2o and 5 2 to 59 of the table above.

According to one embodiment of the invention, there is the recording material from a support which is impregnated with one or more of the dyes used according to the invention or contains these absorbed.

According to a further advantageous embodiment of the invention, the recording material of the invention consists of a Layer support with at least one special layer that is at least Contains one of the bleachable dyes described. The dyes can thus' in the carrier or in the form a special layer, preferably in a layer with a film-forming binder, can be used.

To develop the recording material of the invention is no chemical development required. Since the invention usable dyes can have the most varied of hues, can be extracted from the recording materials produce multicolored images of the invention.

It has proven to be advantageous to disperse the dyes in a conventional film-forming binder and to disperse the resulting Dispersion in the form of a special layer on the

To apply layer support. Customary known binders can be used to produce such layers, such as they are known, for example, from US Pat. No. 3,039,873, column 13, or polymerized vinyl compounds that of U.S. Patents 3,142,568; 3,193,386; 3,062,674 and 3,220,844 of known type, including for example water-insoluble polymers of alkyl acrylates and

0Q9817 / 1S83

Alkyl methacrylates, acrylic acid, sulfoalkyl acrylates and sulfoalkyl methacrylates belong.

According to a particularly advantageous embodiment of the invention, the recording material consists of a layer support and a photosensitive gel layer applied thereto in which one or more of the compounds used in the present invention Dyes are dispersed. When using gelatin as a binder, the usual known methods can be used to harden the layer Gelatin hardeners can be used, for example formaldehyde, azlidine hardeners, hardeners, the j-oxypolysaccharides, such as, for example, consist of dioxane derivatives oxidized starch and oxidized vegetable gums, and the like.

The layers containing dyes can furthermore contain other conventional additives, for example lubricants, Stabilizers, plasticizers, buffer compounds and the like.

Since the photobleachable dyes which can be used according to the invention can have a wide variety of shades produce direct positive, multicolored reproductions from them. For example, it becomes a white substrate with a layer of a yellow dye, a layer of a magenta dye and a layer of one blue-green dye exposed imagewise with white light through a colored slide, in this way a direct positive color copy received.

However, the three dyes do not need separate or separate layers to be arranged on a support. Rather, it is also possible that the Dyes applied in one layer on a substrate

QQI817 / 1883

will wear. This also applies mutatis mutandis to dyes of other dyes or to other dye combinations.

The colored images are obtained by exposing the dyes to light of the wavelengths which they absorb to be bleached.

Since yellow dyes absorb blue light, the yellow dye will then be faded and colorless when placed on it Light of the blue part of the spectrum strikes. Corresponding applies to the other two layers or to the two other dyes, i.e. H. the purple dyes absorbs green light and is faded by green light and the blue-green dye absorbs red light and is bleached by red light according to the amount of light irradiated. This way it will be right-sided readable obtained color reproductions of the recorded color originals. The principle of the bleaching process becomes closer for example, in U.S. Patent 3,104,973.

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

example 1

A photographic recording material was produced by placing a solution of 50 mg of the dye Ur on a conventional cellulose acetate film support. 13 , dispersed in 50 g of a 20 # strength solution of poly (2-vinylpyridine) as a binder and 2 g of triethanolamine was applied.

After the layer had dried, the recording material was exposed to a positive line slide using a high-intensity electronic flash. It turned purple Excellent quality dye image obtained.

0Q8817 / 1683

Example 2

Another image-recording recording material was produced by being coated on a baryta-coated paper support a solution of 75 mg of the dye 26, dispersed was applied in 50 g of a gelatin emulsion and 3 g of pyridine. After the photosensitive layer has dried this was exposed through a positive line slide with a high pressure arc lamp. It turned out to be a positive picture excellent quality received.

Example 3

Further image recording materials were prepared using the process described in Example 1, using dyes 1, 3, 9, 15, 55, 56 and 59 in place of dye no. In all cases, positive images of excellent quality were obtained.

Example 4

A solution of 46.1 mg of Dye No. 12; H. a purple dye, 43.7 mg of dye # 10; i.e. H. of a cyan dye, and 39.8 mg of Dye No. 4 d, i. of a yellow dye, in 50 g of a 20% binder solution with poly (2-virrylpyridine) as a binder, 1.46 g of triethanolamine were added after mixing for 2 hours, what the. Mixture mixed again for 2 hours and then on a white-pigmented cellulose acetate support in a layer with a thickness of 0.005 em was applied. After the layer had dried, the recording material became exposed through a colored slide with a high intensity flash lamp. It became a colored one Positive excellent quality received.

Often M'17 / 1883

Manufacture of the dyes ^

1.) Preparation of compound no. 32 (method A)

A mixture of 10.9 g of 2-picoline-N-oxide and 27.9 g of methyl p-toluenesulfonate was heated on the steam bath with constant stirring until an exothermic reaction began. After completion of the supply of external heat, the temperature increased to a maximum of 12O ⁰ C etitfa. The mixture was then cooled, diluted with 200 ml of acetone and quenched. The deposited precipitate was filtered off * and washed with acetone * The yield of reaction product was 23.2 g, corresponding to 79 % of theory. The melting point of the compound! Ag at 113-4 ⁰ C.

2.) Preparation of compound no. 36 (method B)

10.9 g of 2-picoline N-oxide and 18.8 g of benzyl bromide were dissolved in 25 ml of acetone and the solution was refluxed for 10 minutes. After dilution with 150 ml of acetone, the solution was cooled. The deposited precipitate was filtered off and washed with acetone. The yield of reaction product was 19.0 g, corresponding to 68 % of theory. The melting point was 113 to 114 ^° C.

3.) Establishing compound no.26

5.90 g of compound no. 32 and 2.98 g of ethyl isoformanilide in 5 ml of dimethylformamide were heated on the steam bath for 1/2 hour. The mixture was then diluted with 50 ml of acetone and quenched. The resulting yellow precipitate was filtered off and washed with acetone. The yield was 3.3 g, corresponding to 41 % of theory. The melting point of the compound was 172 to 173 ^° C.

001117/1683

4.) Preparation of compound no-1 -I * -methoxyoxa-2 '-pyridocarbocyanine perchlorate

ClO,

2.22 g of 1-methoxy-2-methylpyridinium p-toluenesulfonate, 2.17 g
2-ß-Acetanilidovinyl-3-ethylbenzoxazolium iodide and 1.4 ml of triethylamine in 20 ml of ethanol were heated to reflux temperature for 2 minutes. A solution of 0.61 g of sodium perchlorate in hot methanol was then added. After cooling
the reaction product separated out. It was filtered off and washed with ethanol. The yield of reaction product was 1.50 g, corresponding to 77 % of theory. The melting point of the
Compound was 146 to 147 ^0C .

5.) Preparation of compound no. 3 S'-ethyl-l-methoxy - ^ - pyridothiacyaninj odid

CH ==

4.44 g of 1-methoxy-2-methylpyridinium p-toluenesulfonate, 4.00 g 3-ethyl-2-phenylthiobenzothiazolium iodide and 2.8 ml triethylamine

QG9817 / 1683

were refluxed in 20 ml of ethanol for 10 seconds. After quenching, the deposited precipitate was filtered off and washed with ethanol. The yield of reaction product was 1.55 g, corresponding to 38 % of theory. The melting point of the compound was 159 to 160 ⁰ C-

6.) Establishing compound no. 6

S'-ethyl-1-methoxy-Z-pyridothiacarbocyanine iodide

CIl = CH-CH =: Il Ί J °

2.22 g of 1-methoxy-2-methylpyridinium-p-toluenesulfonate, 2.25 g of 2-ß-acetanilidovinyl-3-ethylbenzothiazolium iodide and 1.4 ml of triethylarain were refluxed in 20 ml of ethanol for 2 minutes. The mixture was then quenched and the resulting precipitate was filtered off and washed with ethanol. The yield was 1.27 g, corresponding to 58 l of theory. The melting point of the compound was 115 ^° C.

7.) Establishing compound no. 10

3 ^l -ethyl-1-methoxy-2-pyridothiadicarbocyanine perchlorate

CH = CH-CH = CH-CH

ClO ₄

^C 2 ^H 5

001917/1683

3.54 g of l-methoxy-2-methylpyridinium-p-toluenesulfonate, 4.76 g of 2- (4-acetanilido-1,3-butadienyl) -3-ethylbenzothiazolium iodide and 1.8 ml of triethylamine were dissolved in 20 ml of dimethy lformairid Stirred for 2 minutes at room temperature. The mixture was then diluted with 400 ml of ether. The ethereal layer was then decanted off and the oily residue was dissolved in 50 ml of methanol. A solution of sodium perchlorate in methanol was then added to the resulting solution. The mixture was cooled, whereupon the deposited precipitate was filtered off and washed with methanol. The yield of reaction product was 0.95 g, corresponding to 22 % of theory.

8.) Production of compound no. 11

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

H ₃ C CH ₃

CH = CH-CH = '

COO '

0-N

2.22 g of 1-methoxy ~ 2-methylpyridinium p-toluenesulfonate, 2.23 g 2-ß-Acetanilidovinyl-l, 3,3-trimethyl-3H-indolium iodide and 1.4 ml of triethylamine were refluxed for 2 minutes in 20 ml of ethanol

0 01117/1883

temperature heated. The resulting solution was then cooled and a solution of 1.15 g of picric acid in ethanol was added. After cooling, the deposited precipitate was filtered off and washed with ethanol. The yield of reaction product was 1.12 g, corresponding to 40 % of theory.

9.) Establishing connection no. 12

3 ^f -ethyl-1-methoxy-4 ', 5'-benzo-2-pyridothiacarbocyanine perchlorate

OCIL

CII-CII-CH =,

'2 5

ClO,

2.22 g of l-methoxy-2-methylpyridinium-p-toluenesulfonate, 2.5.7 g of 2-ß-anilinovinyl-1-ethylnaphtho / "1,2-d_7thiazolium-p-toluenesulfonate and 1.4 ml of triethylamine in 25 ml Acetic anhydride was heated with stirring for 5 minutes to 40 ^° C. A small amount of undissolved compounds was filtered off, whereupon the filtrate was diluted with excess ether. The ethereal layer was then decanted off, whereupon the residue was dissolved in 25 ml of methanol a solution of 0.61 g of sodium perchlorate in methanol was added. After cooling, the deposited precipitate was filtered off and washed with methanol. The yield of reaction product was 1.48 g, corresponding to 65 % of theory.

QQM17 / 1683

135073 ^

10.) Establishing connection no, 21

1,1'-Dimethoxy-2 _s 2 ^f -diphenyl-3,3'-indolocarbocyanine perchlorate - ^ _ "

H ₃ CON

CH-CH-CH =

STILL.

• ClO

2.23 g of 1-methoxy-2-phenylindole were dissolved in 10 ml of hot acetic acid, whereupon 2.0 g of trimethoxypropene and 1.0 ml of 48% hydrobromic acid were added with stirring. The mixture was allowed to cool and then diluted with excess ether. The ethereal layer that formed was decanted off, and the viscous residue was then dissolved in 60 ml of methyl alcohol. Thereupon 1.5 ml of 60 ° perchloric acid were added, whereupon the mixture was chilled. The deposited precipitate was filtered off and washed with methanol, water and ether. After recrystallization from methanol and acidification with perchloric acid, 1.48 g of pure dye, corresponding to 52 % of theory, were obtained. The melting point of the dye was 228 to 23O ⁰ C.

11.) Establishing compound no. 22

1-methoxy-1'-methyl-2,2 ', 10-triphenyl-3,3'-indolocarbocyanine perchlorate.

00S817 / 1683

H ₃ CON

8NCH.

ClO,

1.26 g of 3-formyl-1-methoxy-2-phenylindole and 1.55 g of 1-methyl-2-methylenebenzyl-2-phenylindole were dissolved in 10 ml of hot acetic acid. Then 1.0 "ml of oily perchloric acid in 3 ml of acetic acid was added, whereupon the mixture was allowed to cool. After standing for 2 hours at room temperature, the solid precipitate was filtered off and washed with ethanol and ether. After recrystallization from acidified with perchloric acid Methanol, 1.92 g of pure dye, corresponding to 59 % of theory, were obtained
ranged from 258 to 259 ⁰ C.

12.) Production of compound no. 28

3'-ethyl-1-methoxy-6'-nitro-1-phenyl-S-indolothiacarbocyanine-p-toluenesulfonate

H ₃ CON

CH = CH

p-TS

009817/1683

- 3d -

1.26 g of 3-formyl-1-methoxy-2-phenylindole, 1.98 g of 3-ethyl-2-methyl-6-nitrobenzotjiiazolium-p-toluenesulfonate and 10 ml of acetic anhydride were heated to reflux temperature for 1 minute. After cooling, an excess of ether was slowly added. The deposited solid precipitate was filtered off and washed with ether. After recrystallization from methanol acidified with p-toluenesulfonic acid, 2.64 g of pure dye, corresponding to 84 % of theory, were obtained.

13.) Production of compound no. 30

"L, 3-diallyl ~ l ^{l-methoxy-2'-phenylimidazo} / ~ 4,5-b_7- · quinoxalines-3'-indolocarbocyaninperchlorat

CH ₂ CH = CH ₂

^C10 4

This dye was prepared according to the method described in the example, with the exception, however, that 2.18 g of 3-diallyl-2-methylimidazo / ~ 4,5-b-7-quinoxalinium-p-toluenesulfonate instead of 3-ethyl * -2-methyl -6-nitrobenzothiazolium p-toluenesulfonate were used. After recrystallization from a mixture of 65 ml of acetonitrile and 1 ml of 60 ^? ₀ % perchloric acid, 1.78 g of pure dye, corresponding to 60 % of theory, were obtained. The melting point of the dye was 229 to 231 ^° C.

009117/1683

14.) Establishing compound no. 38

l-methoxy-2-ph enylindole

3.0 g of sodium was dissolved in 200 ml of methanol. Then 20.9 g of l-IIydroxy-2-phenylindole, prepared as in Ber. 2_8 (1895), page 585, and Bert. 2-9 (1896), page 2063, and 25.6 g of methyl iodide were added, whereupon the mixture was heated to reflux temperature for 1 hour. The solution obtained was then quenched, whereupon the precipitate which had separated out was filtered off and washed with methanol. The yield of reaction product was 15.9 g, corresponding to 71 % of theory. The melting point of the compound was 51 to 52 ^° C.

15.) Establishing connection no. 40

1'-methoxy-1,3,3-trimethyl-5-nitro-2'-phenylindo-3'-indolocarbocyanine perchlorate

H ₃ CON

CH-- CH ■■

ClO,

. CH,

003 * 17/1683

1.26 g of S-formyl-1-methoxy - ^ - phenylindole, 1.30 g of 1,2,3,3-tetramethyl-5-nitro-3H-indolium-p-toluenesulfonate and 10 ml of acetic anhydride were 1 Heated to reflux temperature for a minute. After cooling, excess ether was added. The ethereal layer was decanted and the viscous residue was dissolved in 25 ml of methanol. Then 1.0 ml of 6.0 Hg perchloric acid in 5 ml of methanol was added. The mixture was then quenched and the resulting precipitate was filtered off and washed with methanol. After recrystallization from a mixture of methanol and acetonitrile, 1.20 g of pure dye, corresponding to 43 % of theory, were obtained. The melting point of the dye was 266 ^° C.

16.) Preparation of compound no. 41 1-MeUiOXy _- -I ¹ , 3 *, 3 ^l -trimethyl-2-phenyl-3-indolo-2 '- pyrrolo / 2,3-b_ / pyridocarbocyanine perchlorate

CH.

1.26 g of 3 "formyl-1-methoxy-2-phenylindole, 0.87 g of 1,3,3-trimethyl-2-methylene-2,3-dihydropyrrolo ^" 2,3-b-7-pyridine and vmrden 0.95 g of p-toluenesulfonic acid monohydrate and 10 ml of acetic anhydride Heated to reflux temperature for 1 minute. The mixture was then cooled and diluted with ether, whereupon the essential Layer was decanted. The residue was dissolved in 25 ml of methanol, whereupon 1.0 ml of perchloric acid in 5 ml

001117/168 3

Methanol were added. After cooling, the solid precipitate which had separated out was filtered off and washed with methanol. After a single recrystallization from acetonitrile, 1.78 g of pure dye, corresponding to 69 % of theory, were obtained. The melting point of the dye was 235 to 239 ^° C.

17.) Preparation of compound no. 50 3-formyl-1-methoxy-2-phenylindole

CIIO

5.2 ml of phospholyl chloride were slowly added to 15 ml of dimethylformamide with cooling so that the temperature did not rise above 20 ^° C. A solution of 11.15 g of 1-methoxy-2-phenylindole in 30 ml of dimethylformamide was then slowly added, the temperature being kept below 25 ^° C. The mixture was then heated 45 minutes at ⁰ C for 4Q, and then poured into 390 ml of ice water. Then 70 ml of a 5 N sodium hydroxide solution were added, whereupon a viscous mass separated out. The mixture was heated .to 65 ⁰ C, the lumps which had formed departed. The precipitate was filtered off and washed with water. The yield of reaction product was 11.95 g, corresponding to 96 % of theory. The MELTING was 116 to 117 ⁰ C, and did not change after recrystallization from ethanol.

QCS817 / 1683

Following the procedures described in Preparation Examples 1 to 17, Compounds 18-49 were prepared. From the The two following Tables III and IV show the individual manufacturing methods used and the yields achieved and the melting points of the compounds obtained.

Connect
manure
No. TABEXLE III 6th Solution
middle M. the end
prey
in % Mp. ⁰ C 237-41 Manuf
lungs bei
game no. 2 Intermediate method
binding. in
No example 5 Α M. 43 dec. 18th 4th 35 5 Λ EA 33 dec. 19th 5 35 6th Α Ä 18th 125-30 20th 7th 36 6th Ä M. 89 dec. 21 8th 35 4th IT 45 128-31 22nd 9 34 M. HS 45 125 23 13th
14th 36 9 EA
(without NaClO ₄ )
6 M. DF / EA ⁽²⁾ 81
38 dec.
143 24
25th 15th 35
37 5 EA 47 dec. 26th 16 37 6th EA 63 138-9 ■ 27 18th 37 . 9
(Reaction
temp. 80 °) EA 35 127-8 28 19th 32 5 EA 20th 186-7 29 20th 33 4th 58 128 30th 23 33 10 36 219-21 31 24 39 11th 55 205-9 32 25th 51 11th 40 dec. 33 29 37 12th 100 dec. 34 31 51 13th 58 220-1 35 42 51 15th
(without NaClO ₁ , 65 194-200 41 43 51 16 69 42 51

001117/1683

Manuf
lungs bei
game no. Connecting
manic
No. base TABLE IV Solution
Method medium the end
prey
O
O Mp. ⁰ C 36 33 4-picoline-N-
oxide Alkylation
middle Λ 97 153-4 37 34 2-? Icolin-N-
oxide Methyl p-toluene
sulfonate B acetone 95 202-3 O 38 35 2-? Icolin-N-
oxide 1,3-propane sultone B CHCl ₃ 80 53-7 % r
m 39 37 Chiiialdin-N-
O 2; yd Triethyloxonium
tetrafluoroborate B CH ₂ Cl ₂ 90 115-7 40 39 i-hydroxy-2-
phenylindole Triethyloxonium
tetrafluoroborate Example Ä
14th 100 oily 168 43 44 Pyridine-N-
oxide Ethyl iodide A. 81 170-1 <·> 44 45 Pyridine-N- '
oxide 1,2-dibromo
ethane A - ■ " 100 151-3 45 46 2-picoline-N-
oxide 1,3-dibromo
pr op at A. 88 153-4 46 47 4-picoline-N-
oxide 1,4-dibromo
butane B CH ₃ CN 39 109-11 47 48 Pyridine-N-
oxide 1,4-dibromo
butane A. 91 172 48 49 Pyridine-N-
oxide 1,4-dibromo
butane A. 88 115-7 49 51 l-ethoxy-2-
phenylindole 1,5-dibromo
pentane example
17th 98 95-6 _ "

(1) Reaction mixture diluted with acetone to precipitate of the dye

(2) Reaction ^{temperature 25 °} C., without addition of NaClO.

A = ethyl alcohol M = methyl alcohol EA = acetic anhydride ES = acetic acid DF = dimethylformamide

50.) Establishing compound no. 54

1,3-diethyl-5- / ~ (l-methoxy-2 (IH) -pyridylidene) ethyiiden_ / · 2-thiobarbituric acid

3.99 g of 2-ß-anilinovinyl-l-methoxypyridinium-p-toluenesulfonate, 2.00 g of 3-diethyl-2-thiobarbituric acid and 20 ml of acetic anhydride were stirred together, after which 5 ml of triethylamine were added. The mixture was then stirred for a few minutes until everything had dissolved. The solution was then seeded by adding a seed crystal obtained by diluting a small amount of the reaction mixture with excess ether. The mixture was then chilled for a few hours. The precipitated dye was filtered off and washed first with methanol and then with ether. The yield of pure dye was 1.48 g, corresponding to 44 % of theory. The melting point of the compound was 171 to 172 ^° C. dec.

009817/1683

Compounds 55 to 59 were prepared in the manner described in Preparation Example 50. The yields obtained and the melting points of the compounds result from of Table IV.

TABLE V

manufacturing
example no. Connective
No. yield
% Mp. ⁰ C 51 55 47 75.5 52 56 " 25th 154-5 53 57 73 dec. 54 58 79 169-70 55 59 88 1334

009817/1683

Claims (1)

PATENT CLAIMS (Iy photographic image recording material consisting of a support and at least one light-sensitive, photobleachable dye, characterized in that the recording material as a photobleachable dye a dye having a heterocyclic ring with the .t
Group N-OR ₃ in which R is an optionally substituted alkyl, t
Acyl or aryl radical, contains one of the following formulas: OR N ' OR III R ₁ , j- ₉ -, R ₂ X ^e or OR ? 2 / \ 9 9 ' IV Q ₅ - NOR, - NQ _Q 2 Χ ^θ 009817/168 where mean: Z to complete an optionally substituted, 5- or 6-membered, heterocyclic Ring's required atoms; R is an optionally substituted alkyl, aryl or acyl radical; R _{1 is} an optionally substituted methine or polymethine group with a terminal heterocyclic ring customary for cyanine dyes, an aniline ynyl radical or an optionally substituted styryl radical; R and R. each represent a hydrogen atom or optionally one substituted alkyl or aryl radical; R ^ is an alkylene or alkyleneoxy radical with 1 to 8 Carbon atoms in the alkylene chain or a residue of the formula -f CiI ₇ -) - R ₁ ^ - £ - CH ₉ 0, in which mean: s and t each denote numbers from 1 to 8; u »0 or 1 and R- _{Q is} an arylene radical; Rg is an optionally substituted methine or polymethine group with a terminal, customary for merocyanine dyes, heterocyclic ring, a optionally substituted allylidene radical or an aldehyde radical; Q ₂ and Qg the atoms required to complete a 5- or 6-membered heterocyclic ring and Xr is an acid anion. 009817/1683 2. Photographic image recording material according to claim characterized in that it contains a dye of one of the formulas given as photobleachable dye, wherein Z, Q ~ and Qq represent the atoms required to complete a pyridine, quinoline «ββΒΗΒββΑΓ Inges. 3. Photographic image recording material according to claims and 2, characterized in that the photobleachable dye is a dye of the formula II contains, in which R, a methine group with a terminal, 5- or 6-membered, customary for cyanine dyes, is heterocyclic ring with preferably at least one hetero nitrogen atom. ¹ I, photographic image recording material according to Claims 1 to 3, characterized in that it contains a dye of one of the following formulas as the photobleachable dye: N ^ = CH-CH C -ir L = L-) TL = (M- CH = CH- _ _Ί Ν— R ^ Χ ^β ι ^ "" X η "· χ g""X j · - C = t = L-L LCCNR ₃ Χ ^Θ OR E ^D Χ ^θ 0Q9617 / 1Ü83 TJ ^ \ ^ RO - NC - CfL - L4 - C - f - CH - CH -) - ^ jNR ₃ X RO-N - (- CH- = CH · ~} ~ "Γ [- C ^ f = L- L = ^ j = C c = O or R _n ", -. RO-N - (- CH = CH -> rC = 4 = LL4 = g-l m where mean: R is an optionally substituted aryl, Alkyl or acyl radical; R _{2 is} a hydrogen atom or an alkyl or Aryl radical- the meaning already given; R _{3 is} an optionally substituted alkyl, alkenyl, aryl or alkoxy radical; Q _{,, Q 2} , QZ, the atoms required to complete 5- or 6-membered Qh ■ and Q ₇ ger, heterocyclic rings; L is an optionally substituted methine group; 003Ι17 / Ί683 Rg and R ₇ each represent a cyano, ester or alkylsulfonyl radical; D, E and J each represent a hydrogen atom or an alkyl or aryl radical; Χ ^θ an acid anion; G is an anilino or optionally substituted aryl radical; "g = 1 or 2; m = 1,2 or 3 and η - = 1,2,3 or 4. 5. Photographic image recording material according to claim H, characterized in that it contains in the light-absorbing layer a compound of one of the formulas given in which Q ₂ and Qg bring about the completion of optionally substituted pyridine, quinoline «fltoft ^ P • represent required atoms. 6. Photographic image recording material according to claims 1 to 5 i, characterized in that it consists of a support which has absorbed one or more of the photobleachable dyes of the formulas given (or is impregnated with them). 7. Photographic image recording material according to Claims 1 to 5, characterized in that it consists of a layer support with at least one layer of at least one in a binder dispersed dye of the specified Formulas. 0 01117/1683 originally inspected 8. Photographic image recording material according to claims 1 to 7, characterized in that there is at least one photobleachable dye of one of the following formulas contains: ^R 2 C = O L - L wherein mean; an optionally substituted alkyl or Acyl radical; 008 * 1771683 ' L. an optionally substituted methine group; G is an anilino'vinyl or optionally substituted phenyl radical; m = 1 ", 2 or 3; X is an acid anion; Q, and Q ^ those for -completion of 5- or 6-membered, . atoms required for heterocyclic rings; R _{2 represents} a hydrogen atom or an optionally
substituted alkyl or aryl radical; Rg and Ry cyano residues; η = ^{1, 2, 3} or 1 I; R-, an optionally substituted alkyl,
Alkenyl, alkoxy or aryl radical and g = 1 or -2. - 9, photographic image recording material according to claim 7, characterized in that it contains gelatin as a binder in the light-sensitive layer, 10. Photographisehes image recording material according to claims 1 to 9 _t, characterized in that it as, .photo of bleachable dye ethyl-l-methoxy- ^ ¹ , 5 ^f ~ benzo-2-pyridothia- contains carbocyanine peroxide. 009117/1683 -Si Photographic image recording material according to claims 1 to 9, consisting of a support having one thereon applied layer of: a) a blue-green dye, b) a purple dye, c) a yellow dye as well d) a film-forming binder, characterized in that the dyes of the formula C ~ f-L — LH τ- L-C -t-CH-CH-) _S -1 ^H " ^R 5 correspond, in which R, Rp, R ,, Q-,, Q _n , L, X, g and η have the meanings already given. 12. Photographic image recording material according to claim 11, characterized in that it contains as blue-green dye: 3'-ethyl-1-methoxy-2-pyridothiadicarbocyanine perchlorate; as a purple dye: - 3'-ethyl-l-methoxy- ^ ', 5'-benzo-2-pyridothiacarbocyanine perchlorate and as a yellow dye: l-ethoxy-3 contains ^1- ethyl-2-pyridothiacyanine tetrafluoroborate. 001117/1683