US3876429A

US3876429A - Basic mordants containing n-(3-dialkylamino-2-hydroxypropyl) succinimide

Info

Publication number: US3876429A
Application number: US335409A
Authority: US
Inventors: Ernst-Joachim Poppe; Gunther Bach
Original assignee: Filmfabrik Wolfen VEB
Current assignee: Filmfabrik Wolfen VEB
Priority date: 1973-02-23
Filing date: 1973-02-23
Publication date: 1975-04-08
Anticipated expiration: 1992-04-08

Abstract

Wherein m and n are integral numbers from 20 to 100 and m/(m+n) =0.3 to 0.5, R.sub.1 is a hydrogen atom or an alkyl group of up to 8 C atoms and R.sub.2 is an alkyl of up to 8 C atoms or an aryl group of 6 C atoms or R.sub.1 and R.sub.2 together with the N atom to which they are bonded constitute a N-containing heterocyclic ring having up to 5 C atoms in the ring, R.sub.3 is a hydrogen atom, an aryl of 6 C atoms or carboxyl group, and R.sub.4 is a hydrogen atom or an alkyl group of up to 4 C atoms.

Polymeric basic mordants, particularly useful for acidsubstituted dyes in photographic elements, of the formula

Description

United States Patent [1 1 Poppe et al.

[ Apr. 8, 1975 [73] Assignee: Veb Filmfabrik Wolfen-Fotochemisches Kombinat, Wolfen, Germany [22] Filed: Feb. 23, 1973 [21] App1.No.:335,409

3,639.357 2/1972 Cohen 96/84 A Primary E.\'uminer-J. Travis Brown Attorney, Agent, or Firm-Nolte and Nolte [57] ABSTRACT Polymeric basic mordants, particularly useful for acidsubstituted dyes in photographic elements, of the formula wherein m and n are integral numbers from 20 to 100 and m/(m+n)=0.3 to 0.5, R, is a hydrogen atom or an alkyl group of up to 8 C atoms and R is an alkyl of up to 8 C atoms or an aryl group of 6 C atoms or R and R together with the N atom to which they are bonded constitute a N-containing heterocyclic ring having up to 5 C atoms in the ring, R is a hydrogen atom, an aryl of 6 C atoms or carboxyl group. and R is a hydrogen atom or an alkyl group of up to 4 C atoms.

5 Claims, No Drawings BASIC MORDANTS CONTAINING N-(3-DIALKYLAMINO-Z-HYDROXYPROPYL) SUCCINIMIDE This invention relates to the mordanting of compounds which contain one or more acid groups and the use of the mordanted compounds in photography.

It is known that easily soluble acid compounds, such as dyes, for example, which contain at least one basic group in the molecule, can be so fixed, i.e., mordanted, in certain layers of a photographic multilayer unit that their diffusion into neighboring regions of the material can be practically prevented. When certain mordants are used, it is also possible to split these dye-mordant adducts of the layers in the baths into their components by varying the pH-value of the layers in the baths during the photographic development so that the dyes can be washed out from the photographic unit. A photo graphic unit is, of course, a support carrying at least one layer of a photographic composition.

Basic mordants for this purpose have already been repeatedly described. Thus, for example, copolymers which contain a N-(3-dialkylamino-propyl)-maleic imide unit are disclosed for color transfer processes (see US. Pat. Nos. 3,184,309; 3,488,706 and 3,048,487). These compounds have the disadvantage that in high dosages they can have a precipitating effect on silver halide, which leads to considerable difficulties and losses in the production of photographic materials.

A principal object of the invention is the qualitative improvement of the photographic properties, for example, of the color reproduction, of silver halide materials.

Other objects and advantages of the invention will be apparent from the following description.

The invention is directed to the problem of incorporating acid-substituted compounds, for example, dyes, in a diffusion-resistant manner in certain layers with the use of mordants and to cancel the mordanting during the development process.

It has been found according to the invention that a particularly good mordanting effect is achieved if at least one silver halide emulsion layer or auxiliary layer of the photographic unit contains an acid-substituted compound mordanted by a basic polymer containing at least 30% N-(3-dialkylamino-Z-hydroxy-propyl- )succinimide units, the polymer corresponding to the general formula wherein m and n are integral numbers from to 100 and m/(m+n)=0.3 to 0.5, R, is a hydrogen atom or an alkyl group of up to 8 C atoms and R is an alkyl of up to 8 C atoms or an aryl group of 6 C atoms or R and R together with the N atom to which they are bonded constitute a N-containing heterocyclic ring having up to 5 C atoms in the ring, R. is a hydrogen atom, an aryl of 6 C atoms or carboxyl group, and R is a hydrogen atom or an alkyl group of up to 4 C atoms.

Particularly suitable as the N-containin g heterocyclic rings are piperidine and morpholine.

The basic mordants according to the invention can be used for mordanting compounds which are capable of forming salts with the molecule of the mordant by substitution with several acid] groups, such as -COOH or SO H groups, of the compound. lf equivalent amounts of mordant and dye are used, the extinction drops, i.e., the color density decreases, due to the salt formation, but it can be increased again to the original value of the unmordanted dye-containing layer by using excess mordant. But even with a great excess of mordants according to the invention, the remaining coloring of the gelatin layers after the photographic development is not greater than with unmordanted dye. The diffusion of the dye through the mordant, however, is almost completely prevented.

The compounds according to the invention exhibit, along with the same mordanting properties as the mordants of the prior art, a great gelatin compatibility, which is due to the additional hydroxyl group in the molecule. Another advantage is the easy production of the necessary 2-dialkylamino-Z-hydroxy-propylamines. The effectiveness of the mordants accordant to the invention varies with different dye classes. While oxonol dyes of formula 1 N\N/ O HO N N l where R is a hydrogen atom or an aryl group containing up to 18 C atoms which may be substituted, e.g., by carboxyor sulfogroups; R is a hydrogen atom or an alkyl group containing up to 5 C atoms or aryl group containing up to 6 C atoms; n is O, l or 2; R is a hydrogen atom or an alkyl group of up to 3 C atoms, aralkyl group of up to 7 C atoms or aryl group of up to 10 C atoms, can be mordanted in a diffusion-resistant manner with only an equivalent amount of mordants according to the invention, a greater excess of mordants according to the invention is required for certain azodyes, e.g., tartrazine (formula II), p-dialkylaminobenzal compounds, e.g., the dye of formula III, and merocyanines, such as dyes of formula IV, in order to be able to achieve sufficient diffusion resistance in gelatm.

III

But dyes such as Green PL (see Dr. Gustav Schultz, Dye Tables, Berlin 1923, Weidmannsche Buchhandlung. No. 4, p. 4) as well as bisazo dyes (as described in D.D.R. Patent No. 54,882) can also be mordanted diffusion resistant with good results with the mordants according to the invention.

The following examples will demonstrate the use of the mordants on the basis of their effect on dyes. But

acid-substituted compounds which are not dyes can also be mordanted diffusion-resistant, such as the anthraquinone desensitizers disclosed in D.D.R. Pat. No. 1 1,035.

The dyes and mordants can be added to a silver halide emulsion layer or to a special auxiliary layer of silver halide-free gelatin. lf dye developers are used together with the mordants. this may have a negative effect on the mordanting action; it is therefore necessary to make a suitable selection of developer, for example, by using so-called protected developers.

EXAMPLE 1 A. Production of the copolymer of styrene and maleic-N-(3-diethylamino-Z-oxypropyl-)imide. 3-diethylamino-2-hydroxy-propylamine is obtained by reacting concentrated NH solution with 3- diethylamino-l,2-epoxy-propane, the latter being obtained by reaction of epichlorohydrin with dimethylamine, in a very good yield. To a solution of 19 g. (0.13 mole) of the 3-diethylamino-2-oxypropylamine in 200 ml. dimethyl formamide is added dropwise with stirring and heating in a steam bath 18.7 g. of a styrene-maleic anhydride (1:1 mole ratio) copolymer in 200 ml. dimethyl formamide. and subsequently 100 ml. dimethyl formamide is distilled off. The mixture is cooled to room temperature and introduced slowly with vigorous B. In a similar manner, basic polymers of the following structures were produced:

HO-CH-CH a. R R; (CH- b. R R CH CH OCH -CH by reactmg a. 3-piperdino-Z-hydroxypropylamine b. 3-morpholino-Z-hydroxypropylamine with the aforementioned 1:1 copolymer of styrene and maleic anhydride. The compounds dissolved in undiluted acetic acid. C. Production of quaternized derivatives of compounds of Example 1(A) by reaction with alkylating agents. 8.2 g. of the product of Example 1(A) is dissolved in 100 ml. acetone and mixed with 4.5 g. dimethyl sulfate. The solution is heated to a boil for minutes with refluxing and the quaternary salt formed precipitates. After cooling, the product is drained and washed thoroughly with acetone. Yield 12 g. The product dissolves easily in water.

EXAMPLE 2 Respective ml. quantities ofa 6% gelatin solution are stained with 100 mg. of an exonol dye of the formula and mixed with or not mixed with a solution of 200 mg. of the mordant of Example 1(A) in 1% acetic acid, as well as being mixed with 1 ml. of a 4% wetting agent solution. The colored gelatins obtained are poured on a cellulose acetate base and dried. In order to test the diffusion, colorless gelatin layers, pre-swollen in water, are rolled on the dried test pieces and left there for a short time (10 minutes). After separating the two layers and drying, the stained receiving layers are now measured by means of a spectrophotometer. The layer of each of the two test pieces has also been measured 3 ,8 7 6,429 5 6 with a spectrophotometer prior to the application The layers have the following spectral densities in the thereonto of the colorless gelatin layer. The staining of absorption s'pectrumz' the receiving layers represents a measure of the diffu- Test mbrdam density of density of measumd at sion of the dye from the test piece into the receiving ulntlrxposed re ceivin Amax layer. Both original layers prior to application there- 5 gfg ayer onto of the colorless gelatm have a spectral density of D 0.60. The receiving layer which was applied to the A l 051 550 nm unmordanted layer has a density of D 0.57 due to the 3 300 mg. v 49 (106 diffusion of the dye, whereas the receiving layer which 3 l 640 nm. was applied to the mordanted layer has a density of D 2 200 mg 032 0.05 =0.08. c1 0.20 0.13

700 nm. 2 100 m 0.22 0.06 EXAMPLE 3 g 4 0,30 With the same test procedure as in Example 2, 100 2 250 mg 033 (H0 435 mg. each of the following dyes are used: E 1 0.45 0.21 4

85 nm. 3 2 150 mg. 0.39 0.06 l Fl 0.40 0.27 i6 -v 'w" a; n r-::' 11)C:3 on 0.. 7v F1 W3 3 300 m 0.41 0.08

IKN O HO 53/1: D EXAMPLE 4 k Example 3(A) is repeated but with the following go g 2 mordanting basic polymers instead of the mordanting L 3 3 basic polymer of Example 1(A):

A; CH CH CH-CH B)Cn u-'- 2 A m n o f 0 m; g. 41- l ch \1. b l 'l'i Q :-;o-

O 1 R I I H 0H CH N R 7 2 so :1 1

3 test mordant mordant amoumt density density R1 R2 at morof unexof redant mg. posed ceiving 55C layer layer C Green PL 4 A no mordant 0.51 0.45 4 B --CH- ,CH2CH2-CH- 200 0.53 0.05 D. Tartrazlne (see Dr. G. Schultz, Dye Tables, Berlm, 0 c

l9l4, Weidmannsche Buchhandlung, No. 23, p. '-f' 250 050 013 14 2 C11 3 .i) C1-i While the invention has been described with particul J 3 lar reference to preferred embodiments thereof, it will =0 be understood that variations and modifications can be effected within the spirit and scope of the invention as described hereinabove and as defined in the a ended PP cla1ms.

What is claimed is: $0... 1'. l. A photographic element comprising a support and having a layer which contams an acld-substituted compound mordanted by a basic polymer, the basic polymer containing 30% to 50% N-(3-dialkylamino-2- mula hydroxy-propyl) succinimide units and having the forwherein m and n are integral numbers from 20 to and m/(m+n)=0.3 to 0.5, R is a hydrogen atom or an alkyl group of up to 8 C atoms and R is an alkyl of up to 8 C atoms or an aryl group of 6 C atoms or R and R together with the N atom to which they are bonded constitute a piperidino or morpholino ring having up to 5 C atoms in the group, R is a hydrogen atom. an aryl of 6 C atoms or carboxyl group and R is a hydrogen atom or an alkyl group of up to 4 C atoms.

2. A photographic element according to claim 1, in which the acid-substituted compound is a dye.

halide-free.

Claims

1. A PHOTOGRAPHIC ELEMENT COMPRISING A SUPPORT AND HAVING A LAYER WHICH CONTAINS AN ACID-SUBSTITUTED COMPOUND MORDANTED BY A BASIC POLYMER, THE BASIC POLYMER CONTAINING 30% TO 50% N-(3-DIALKYLAMINO-2-HYDROXY-PROPYL) SUCCINIMIDE UNITS AND HAVING THE FORMULA