DE817398C - Process for the preparation of colored photographic layers - Google Patents

Description

The invention relates to a method of making colored photographic materials Layers, in particular of filter and antihalation layers, using methine dye salts.

It is known to use basic azomethine compounds for the production of filter and antihalation layers to be used with an open chain. Such compounds can be obtained by condensation of substituted or unsubstituted aromatic or heterocyclic aldehydes with appropriately substituted anilines or amines and an organic acid, which is at least contains a group capable of salt formation.

It is known that organic layers are also used to produce such colored photographic layers Salts of analogous dyes used that have a

ι
contain intracyclic -C = N group.

It has now been found that the salts of a known group of methine dyes have the properties possess which are necessary to these salts according to the invention in the production of colored Use photographic layers, in particular filter as and antihalation layers, with success to be able to. These dyes correspond to the general formula I, in which:

R _{1 is} hydrogen, substituted or unsubstituted alkyl or R ₁ + R ₂ together form a heterocyclic nucleus, R ₂ , R ₃ , R ₄ , R _{5 are} hydrogen, alkyl, acyl, substituted

ated or unsubstituted aryl, substituted or unsubstituted aralkyl, where

■ ρ ι τ> * ί

r> ⁴ , r> ⁵ > each form a heterocyclic nucleus K ₂ τ K ₃ j

can,

L is a substituted or unsubstituted methine group,

MO, I, 2, 3, 4,

X is an organic or inorganic acid residue.

The dyes are produced by known processes.

If R ₁ + R ₂ together do not form a heterocyclic nucleus, the dyes are obtained by the action of 2 mol of a primary or secondary amine on ι mol of a compound which supplies the carbon atoms of the methine chain, such as orthoformate, orthoacetate, / S-oxyacroleindiacetal, N -Dinitrophenylpyridinium chloride,

ao Glutacondialdehyde, Chlorglutacondialdehyd, Furfurol, Furfuracrolein etc.

If R ₁ + R ₂ together form a heterocyclic nucleus, the dyes are obtained, for example, by the action of ι mol 2 ~ methyl

»5 cyclammonium salt to ι mole of the above Colorants or the semi-aldehydes derived therefrom.

In addition to the inorganic acid residues, such as. B. chlorine, bromine, iodine, organic acid residues can also with salt-forming carboxyl groups such as acetate, salicylate, phthalate, etc., or organic Acid residues with salt-forming sulfo groups, such as toluenesulfonate and benzenesulfonate, are chemically attached to the Nitrogen atoms be bound. In certain cases it is possible to obtain internal salts.

This salt formation essentially differs the process according to the invention from the known methods, the properly colored basic, by the action of ι Mol Use furfural compounds available on 2 moles of aminophenol or derivatives.

The dyes corresponding to general formula I have the significant advantage without any binder to give a varnish-like colored layer. You can go to cheap and are easy to manufacture, have a very high absorbency and behave Completely indifferent to the sensitive layers and the developer. In addition, they can very easy and irreversible decolorization without leaving annoying residues.

These dyes can be used to make filter and antihalation layers will; they are in the photographic support or in the layer, in a gelatin-containing medium, in one aqueous or alcoholic solution applicable.

Their solubility and their irreversible discoloration in the development baths can thereby be influenced advantageously that in the course of the dye synthesis amines or cyclammonium bases, which carry a carboxyl group or a sulfo group are introduced.

By lengthening or shortening the methine chain or by introducing suitable ones The absorption range can be shifted within wide limits for substituents in the chain. Such substituents are e.g. B. —Cl, —OH, O-acyl, etc.

example 1

2 mol of 4 · 4'-dimethylamino-4 "-aminotriphenylmethane are condensed in acetic acid Mileu with 1 mol of o-formic acid ethyl ester, then converted into a free base by adding an aqueous Na ₂ C Oj solution and finally with ι mol of methylenedisalicylic acid in an alcoholic medium The dye formed corresponds to the formula II and produces a red-violet filter and antihalation layer.

80 Example 2

2 moles / 3-naphthylamine are in alcoholic Environment converted into a dye according to formula III by means of 1 mol of benzoic acid and 1 mol of furfural. This dye gives a red-violet layer.

Example 3

2 moles of o-aminobenzoic acid and 1 mole of furfuracrolein are used together with 1 mole of salicylic acid condensed in an alcoholic medium. The resulting dye according to formula IV gives green layers.

Example 4

By condensation of 2 moles of N-methylaniline the dye is obtained with ι mole of furfural in the presence of 1 mole of alcoholic HBr according to formula V, which results in red-violet layers.

Acetylation gives the dye according to formula VI, which has a yellow-colored layer results.

Example 5

By condensation of 2 moles of aniline with / 9-chloroglutacondialdehyde in the presence of alcoholic HCl you get the dye according to formula VII, which gives a red layer.

Example 6

By condensation of 2 moles of N-methylaniline with ι moles of N-2 · 4-dinitrophenylpyridinium chloride The dye is obtained in an alcoholic environment and with subsequent action of H Cl according to formula VIII, which gives an orange-colored layer.

Example 7

By the action of 1 mol of aniline chlorohydrate on ι mol of furfural in the presence of 1 mol Acetanilide and in an alcoholic environment you get a dye according to formula IX, the one pink layer results.

Example 8

By heating 1.2 moles of glutacondianilide chlorohydrate with 1 mole of 2-methylbenzthiazolethyl

bromide in an alcoholic medium and with subsequent treatment in an aqueous KJ solution you get the dye according to formula X, which gives a blue-violet layer.

Example 9

By condensation of 2 mol of aniline with ι mol of furfuracrolein in the presence of 1 mol p-Toluenesulfonic acid gets in an alcoholic medium a dye according to formula XI, which has a very nice, intense blue layer on glass results.

Example 10

2 mol ι · 2 · 3 · 4-tetrahydro - /? - naphthoquinoline with 1 mole of furfural in an alcoholic medium and in the presence of 1 mole of methylenedisalicylic acid mixed. The formed dye of formula XII gives on the back of a photographic Materials a blue-violet antihalation layer.

Example 11

1.5 g of diisoamylamine and 0.5 g of furfural are ^{dissolved in 15 cm 3 of} alcohol at room temperature, and 1.4 g of methylenedisalicylic ^{acid in 14 cm 3 of} alcohol are added to this solution. The dye of formula XIII thus formed gives a yellow antihalation layer on the back of a photographic plate.

B e i s ρ i e 1 12

1.7 g of diphenylamine and 0.5 g of furfural are dissolved in 5 cm ^{3 of} alcohol and 1.4 g of methylenedisalicylic acid in 14 cm ^{3 of} alcohol are added to this solution. The dye of formula XIV thus formed produces a purple antihalation layer on the back of a photographic plate.

Claims (1)

Patent claims: NICR ₁ (-L = L) _{n -N} Process for the production of colored photographic layers, in particular filter and antihalation layers, characterized in that methine dyes are used accordingly the general formula used in which mean: R _{1 is} hydrogen, substituted or unsubstituted alkyl or R ₁ + R ₂ together form a heterocyclic nucleus, R ₂ , R ₃ , R ₄ , R _{5 are} hydrogen, alkyl, acyl, substituted or unsubstituted aryl, substituted or unsubstituted aralkyl, where YY I TD \ r> ² 1 r> ³ / form a heterocyclic nucleus ^K 4 + ^K 5 y can, L is a substituted or unsubstituted methine group,
η ο, ι, 2, 3, 4, X is an organic or inorganic acid residue. 1 sheet of drawings Q 1813 10:51