US3652286A

US3652286A - Color photographic silver halide multi-layer material containing cyan-forming couplers

Info

Publication number: US3652286A
Application number: US22998A
Authority: US
Inventors: Hans-Heinrich Credner; Hans Glockner; Fritz Nittel
Original assignee: Agfa Gevaert AG
Current assignee: Agfa Gevaert AG
Priority date: 1969-03-28
Filing date: 1970-03-26
Publication date: 1972-03-28
Anticipated expiration: 1989-03-28
Also published as: FR2040126A5; DE1915948A1; BE747782A; DE1915948C3; GB1240804A; DE1915948B2

Abstract

WHEREIN R1 is H, or a short chain alkyl; R2 is H, Cl, or a straight or branched chain alkyl; R3 is a straight or branched chain alkyl and WHEREIN THE CHAIN CARBON ATOMS OF R2 and R3 total to at least eight carbon atoms; N IS 0,1 OR 2.

Color photographic material having a color coupler of the general formula

Description

United States Patent (,redner et al.

[ 51 Mar. 28, 1972 Glockner, Pullach; Fritz Nittel, Koln- Stammheim, all of Germany 731 Assignee: Agta-Gevaert Aktiengesellschait, Lei/erkusen, Germany [22] Filed: Mar. 26, 1970 21 Appl. No.: 22,998

[30] Foreign Application Priority Data Mar. 28, 1969 Germany ..P l9 15 948.9

521 U.S. Cl ..96/1 00 [51] Int. (I .....G03c 1/40 [58] Field of Search ..96/100, 55 a [56] References Cited UNITED STATES PATENTS 2,698,794 l/l955 Godowsky ..96/100 2,908,573 10/1959 Bush et al. ..96/100 Primary Examiner-J. Travis Brown Attorney-Connolly and Hutz [57] ABSTRACT Color photographic material having a color coupler of the general formula B1 Cl NH-COaH-(CHEh-O wherein R is H, or a short chain alkyl; R is H, Cl, or a straightor branched chain alkyl; R is a straight or branched chain alkyl and wherein the chain carbon atoms of R and R alfi w a rsisb a l n a m is 0 1 or 1 Claims, No Drawings COLOR PHOTOGRAPHIC SILVER I'IALIDE MULTI- LAYER MATERIAL CONTAINING CYAN-FORMING COUPLERS BACKGROUND OF THE INVENTION The invention relates to new diffusion-proof blue-green components for the preparation of color photographic materials in accordance with the principle of the chromogeneous developing.

The dyestuffs developed by color developing must have certain optical properties. A blue-green dyestuff should ideally absorb entirely red'light and allow the green as well as the blue light to penetrate as much as possible. A color coupler should give the highest possible color density. Next to the optical properties there are special requirements placed on the hydrolysis stability and the fastness of the dyestuffs. In addition, for the applicability of a color component, important is a good dispersability; also a high developing speed and with respect to the resulting dyestuff the most homogeneously dispersed color granules possible.

As the color coupler for blue-green, very well suited are the derivatives of aminophenol, and here in particular the conden sation products of 2-amino-4,6-dichloro-5-methyl-phenol with certain phenoxy carbonic acids (see for example U.S. Pat. No. 2,908,573). However, these components have the disadvantage that they are strongly inclined to crystallize. The reason for this is due to their chemical composition and the fact that the usual representatives of this class have a very high melting point. The recrystallization of these color components makes itself disagreeably noticeable in its employment both during the standing of the dispersion as well as after pouring in the finished layer. It may be utilized, therefore, only with the aid of a high-boiling solvent, a so-called oil forming agent. However, it is known that the use of such olefins works out disadvantageously on the properties of the photographic material. This is described, for example, in the U.S. Pat. No. 2,801,171.

The object of the invention is to find novel blue-green developers which have good properties of the named aminophenols but are less inclined to recrystallization, so that they may be employed without oil forming agents.

SUMMARY OF THE INVENTION It has now been found that diffusion-proof blue-green couplers of the general formula I B1 G1 (In i are particularly well suited for the structure of a color photographic multilayer material.

In this formula R H or a short alkyl chain up to three carbon atoms; R H, chlorine or a straight or branched alkyl chain; R a straight or branched alkyl chain; the total chain length of R and R amounting up to at least eight carbon atoms; n 0, l or 2.

DETAILED DESCRIPTION OF THE INVENTION Couplers of the invention are for example the following compounds:

The melting points of the novel couplers are relatively low,

' usually under C. For example, the coupler of Formula II! has a melting point which is by ca. 15 C. lower than that of the corresponding unchlorinated couplers according to the U.S. Pat. No. 2,908,573.

The new couplers are easily dispersed in water or gelatin solutions. For this purpose, the coupler is dissolved, for example, in a known manner in a low boiling solvent, immiscible with water, e.g., acetic ester or methylene chloride, and is then dispersed with the aid of a wetting agent in water or in gelatin solution. This method is particularly suitable for the novel couplers since their solubility is preferable in the low boiling solvents. The use of anoil forming agent is unnecessary in most instances. The dispersions are stable for several days and even in storage of the finished materials there is generally no recrystallization observed. Due to this property, the novel .coupler is clearly superior to the known comparable compounds.

Also in other important properties is the novel coupler excellent: good reactivity with all customary color developing substances and good optical properties of the formed dyestuffs. The obtainable color densities are particularly high which is equally traced back to the high degree of dispersion of the components.

The novel components may be employed both in the negative as well as in the reverse process. They are equally suitable for film as well as for paper materials.

The synthesis takes place in a known manner by condensation of the aminophenol with the chlorophenoxy carbonic acids.

The preparation and properties of the novel components are explained by the following example: 2-(2-a-Methyltridecyl-4'-chloro-phenoxyacetylamino)-4,6- dichloro-S-methyl-phenol:

First Step: 2-a-Methyltridecyl-4-chlorophenol 675 g. pchlorophenol are melted in the reaction retort. In the course of 45 minutes, 10 g. BF3 are introduced while stirring. 295 g. Tetradecene-(lare added by drops, the temperature being maintained at 55-60 C., and stirred for 1 hour, 250 ml. benzene are added and the reaction mixture is three times washed with 5 percent ammonia and then with water. Benzene is distilled off and the excess p-chlorophenol is completely driven off. The residue is distilled in high vacuum. Principal fraction (0.02 mm.) C. Yield: 290-300 g.

Second Step: Z-a-Methyltridecyl-4-chlorophenoxy acetic acid. 650 g. 2-a-methyltridecyl-4-chlorophenol and 490 g. chloroacetic acid ethyl ester are heated over a steam bath, then are added by drops within one hour 440 ml. of 30 percent sodium methylate solution and subsequently boiled 1 hour under reflux. Thereupon, at boiling temperature, a mixture of 550 ml. 30 percent soda lye and 550 ml. methanol is added by drops for 10-15 minutes and again restirred for 20 minutes. The reaction mixture is poured out on 4 l. water and 0.6 1. concentrated hydrochloric acid and agitated a number of times with methylene chloride. The united extracts are washed with water, dried, stirred with charcoal, drawn off over theorite and concentrated. There remains a syrup-like liquid. Yield: 750 g. I

Third Step: 2-a-Methyltridecyl-4-chlorophenoxyacetyl chloride. 750 g. of Carbonic acid according to step 2 and 380 ml. thionyl chloride are heated together for 3 hours in an oil bath at 100 C. Then the excess thionyl chloride is distilled ofi' and the remaining crude acid chloride is immediately reprocessed. Yield: 800 g.

Fourth Step: 2-(2'-a Methyltridecyl-4-chlorophenoxyacetylamino)-4,6-dichloro-5-methyl-phenol. 6 l. Acetone, 516 g. quinoline and 457 g. 2-amino-4,6-dimethyl-5- methylphenol chlorohydrate are stirred for 15 minutes at room temperature, 800 g. acid chloride are added and heated for 3 hours under reflux. The reaction mixture is stirred into 12 l. water and 250 ml. concentrated hydrochloric acid, a brown oil being precipitated which is deposited. The supematant aqueous solution is carefully siphoned off, the oil dissolved in 2 l. benzine (boiling' point 50"75 C.), filtered ofi from the added solid product, dried, and purified with charcoal. At 20 C., the component crystallizes as a whitesub v stance. Yield: 650 g. Melting point 52-54 C.

Use of These Couplers Of this color component, 3 g. are dissolved cold in l ml. acetic ester and dispersed with 50ml. of a percent gelatin solution, which contains 4 ml. sodium dodecyl benzene sulfonate percent). The dispersion is added to a photoll] Cl' 01- NH-CO-CH-(CHzh-OQ R H3 C 1 a wherein R H or a short alkyl chain up to three carbon atoms;

R H, chlorine or a straight or branched alkyl chain;

R a straight or branched alkyl chain; the total chain length of R and R amounting to at least eight carbon atoms; n= 0, l or 2.

* l I I