US3929484A

US3929484A - Color developer compositions containing improved yellow dye-forming coupler

Info

Publication number: US3929484A
Application number: US492116A
Authority: US
Inventors: Robert E Ross
Original assignee: Eastman Kodak Co
Current assignee: Eastman Kodak Co
Priority date: 1974-03-08
Filing date: 1974-07-26
Publication date: 1975-12-30
Anticipated expiration: 1992-12-30
Also published as: FR2263537B1; CA1041116A; CH593500A5; FR2263537A1; JPS559697B2; IT1034108B; DE2510075A1; JPS50123342A; DE2510075B2

Abstract

Color developer compositions are described which contain, dissolved therein, both (a) an organic aromatic primary amino developing agent and (b) a yellow-dye-forming coupler having the structure:

WHEREIN R is a branched alkyl group containing 3 to 6 carbon 10 atoms; X is Cl or Br; Y is X, hydrogen or alkyl (1 to 8 carbon atoms); and A and B differ and are either H or -COOM, wherein M is a photographically inactive cation or a methyl or ethyl group. Use of such compositions results in more efficient coupler usage and color products having yellow dyes with improved aging characteristics. The invention encompasses such liquid developer compositions, blends of (a) and (b), and the yellow dye-forming couplers, per se.

Description

United States Patent [1 1 Ross [ Dec. 30, 1975 COLOR DEVELOPER COMPOSITIONS CONTAINING IMPROVED YELLOW DYE-FORMING COUPLER [75] Inventor: Robert E. Ross, Rochester, NY.

[73] Assignee:- Eastman Kodak Company,

Rochester, NY.

[22] Filed: July 26, 1974 [21] Appl. No.: 492,116

Related US. Application Data [63] Continuation-in-part of Ser. No. 449,800, March 8,

1974, abandoned.

Primary ExaminerJ. Travis Brown Attorney, Agent, or Firm .l. T. Lewis [57] ABSTRACT Color developer compositions are described which contain, dissolved therein, both (a) an organic aromatic primary amino developing agent and (b) a yellow-dye-forming coupler having the structure:

II I! H wherein R is a branched alkyl group containing 3 to 6 carbon 10 atoms; X is C1 or Br; Y is X, hydrogen or I alkyl (1 to 8 carbon atoms); and A and B differ and are either H or -COOM, wherein M is a photographically inactive cation or a methyl or ethyl group. Use of such compositions results in more efficient coupler usage and color products having yellow dyes with improved aging characteristics. The invention encompasses such liquid developer compositions, blends of (a) and (b), and the yellow dye-forming couplers, per

4 Claims, No Drawings erties, unusually high color-forming efficiency and, in

the dye form, unusually good aging and absorption characteristics, Also, the present invention relates to developer compositions containing such valuable diffusible yellow-dye-forming coupler materials.

The coupler compounds of this invention are haloanilidophenoxycarboxy compounds having the structure I:

wherein R is a branched alkyl group containing 3 to 6 carbon atoms: X is Cl or Br; Y is X, hydrogen or alkyl (1 to 8 carbon atoms); and A and B differ and are either H or -COOM, wherein M is a photographically inactive cation, a methyl group or an ethyl group. This invention also includes developer compositions containing one or more of the compounds ofthe structure I l and one or more organic aromatic amino developing agents, which developer compositions are used in the form of aqueous solutions comprising water and having a pH ofat least about 10.

The formation of colored photographic images in silver halide emulsion layers by coupling the oxidation products of aromatic amino developing agents with color-forming coupler compounds is well known. Color'forming coupler compounds have been classified as incorporated" and diffusible", based upon the way such compounds are ordinarily used. For example, incorporated" couplers have fairly large molecules in order to prevent the diffusion or substantial movement of such couplers within the particular hydrophilic colloid layer into which they were incorporated during the manufacture of the photographic element. By comparison, diffusible' couplers are soluble in alkaline solutions which also usually contain one or more organic aromatic amino developing agents. Thus, when diffusible couplers are used, their capability ofdiffusing into (and through) the emulsion layers of the photographic element being treated makes it possible for them to react (couple) with oxidized aromatic amino color developer(s) and thereby become effectively bound into the emulsion layer. In this situation. unreacted diffusible coupler can be readily removed from the photographic element via simply washing the element with water.

Although many very useful diffusible couplers have been manufactured and used commercially heretofore,

2 manufacturers of developer compositions are continually'striving to discover couplers having outstanding solubility, coupling efficiency and hydrolytic stability in developer compositions and excellent aging characteristics after they have been converted into the corresponding dyes during the color developing process.

Diffusible couplers that form yellow dyes have, to date, exhibited more of a need in this respect than have other types of color-forming couplers.

DESCRIPTION OF THE INVENTION It has now been discovered that a small group or class of pivalyl a-aryloxy anilide, yellow-dye-forming coupler compounds displays'the valuable characteristics set out above.

The valuable properties of the couplers (and compositions containing them) of the present invention apparently result from the unique combination of substituents on the basic ketomethylene backbone structure of the coupler compounds encompassed by Formula I above. Thus, it was known heretofore, as disclosed in U.S. Pat. Nos. 3,265,506 (now Reissue No. 27,848) and 3,408,194, that very good yellow dye stability and anti-stain properties result when couplers having a. an aryloxy coupling of group attached through the ether linkage directly to the active carbon atom of the coupler and b. a branched alkyl group (such as R in structure I above) attached to one of the activating carbonyl groups in an acetanilide coupler. Ithas now been discovered that a still better coupler can result when c. there are two halogen substituents on the aromatic ring of the anilide portion of structure I, provided that one of the halogens is attached at the 2 position on the aromatic ring and that the halogens are identical; and

(I. there is a carboxyl substituent (either a carboxylic acid or a photographically inactive salt or lower alkyl ester thereof) attached at either the 3 or 4 position on the aromatic ring of the aryloxy" coupling-off group. Preferred halogens, as in part (c) of the above disclosure, are Cl and Br. Of these, Cl is still further preferred. Similarly, it is preferred that a halogen be at both the 2 and 4 position on the aromatic ring of the acetanilide portion of structure I. Regarding the photographically inactive cation designated M in structure I, above, it is preferred that M be selected from the group consisting of H, alkali metal and ammonium cations and tertiary amines. Of those couplers having the structure I, particularly preferred in the practice of the present invention is alpha-pivalyl-alpha- (4-carboxyphenoxy)-2,4-dichloroacetanilide.

HY DROLYTIC STABILITY TEST As it was stated above, one of the valuable properties of the materials of the present invention relates to their surprisingly highresistance to hydrolysis under conditions which simulate end-use conditions; namely, in aqueoussolution at a buffered pH of 12.06 and at a temperature of 239C. Under such conditions, with the coupler being dissolved in the aqueous buffered solution at a concentration of coupler about 6.6 X 10' molar, many couplers have been found to degrade (hydrolyze) at varying rates of hydrolysis. The rates of hydrolysis are apparently unaffected by the presence or absence of color developing agent in the solution. By

monitoringithe rateii'of disapperance-yof the coupler from the buffered solution (by measuring the-solution absorption at the optimum wavelength at which the particular coupler. anion absorbs it. was found that. generally, hydrolysis proceeded in a linear fashion, whenthe logof; the absorptionwas plotted vs. time. As

a result,- relative-rates of hydrolysis ofcouple'rs can .be

set out in terms of their-respective half-lives in .this standard test. In terins of hours, praetical'acceptability for very high quality diffusible couplers is believed to require half-lives of atleast about l000hours. The half-livesof. all of the. coupler materials of the present invention-=are believed to "substantially greateruthan I000 hours in this test. (This haspbeenrconfirmed by tests on some of the coupler compounds of structure I ,1 +1

In order to demonstrate the' excellent 'hydrolytic-s'tability that can result from'coupler'compounds having the structure'l, a number-.of-coupler materialswere submitted to the hydrolytic stability test-described above. Results from that: test are set out in T able l..-

.Tablel HYDROLYTIC sIAel JTvpAr 331 r i zy f I used at sor'newhat' :lowerconcentrations. in photographic processes if' desired; in order to obtain yellow dye-levels comparable :to': those." presently obtainable by conventional: methods using present commercial processes: andcoupler/color developer compositions. Alternatively, colored photographic materials having greater yellow dye. density ,maybe obtained' via the practice of this, invention, particularly when the invention is .practiced'.commercially, using aqueous solutions of couplen-col'or. developerand alkaline materials in theusualamanipulative manner. v :The. compositionsof the-present invention comprise one or more p.-'phenylenedia mine type color developing agents. Such agents are well known an'dneed not be described in detail herein, since any phenylenediamine color developing-agent .can be'used. A preferred pphenylenediamine-type color developing agent is 4- amino-N-ethyl-N-(2-methoxyethyl)-m-toluidine, di-ptoluenesulfonate salt. The coupler compounds of structure I can be used successfully in combination with such color developing agents. The ratio of color develinthis test. I

It is expected that "the prcscnce of'ano' ther substituent" respectively; and preferably within the (molar basis)- It is also noteworthy that' the coupler compounds of the present invention exhibit a'vc'r'y high' degre'o'f color-forming efficiency. In view thereofj'they cambc op'ing"a'gent' tocoupler in the' compositions of this invention c'an varywidely, but will generally be within the ('rnolarliangeef fromabout 0:2 to l to about 10 to 1,

range of 'fror'nabout- 0.5" to l.to about 3 to l. The coupier/color developer compositions of this invention are preferably' b'lends of solid ,icr-ystalline or powdered materials whichb-lendscanreadily be dissolved in aqueous compositions in the preparation of color developer bziths: Such baths, which contain yellow dye-forming 2'5 coupler dissolved therein, can then be used in the conventional manner during the yellow developer step in a multi-step process for manufacturing colored pho- EXAMPLE A conventional photographic element comprising a Data resulting fromqsubjeeting the processed film strips to spectrophotometric absorption tests were recorded. In the following Tables II and Ill, Dmax values for several diffusable yellow-dye-forming couplers resulting from this type of test are shown. Couplers providing data for Table II were so-called fourequivalent-couplers, while those providing data for Table lIl were two-equivalent" couplers. Substituent groups appearing at the column headings in these Tables refer to the structural formula at the beginning of each table. 1

transparent poly(ethyleneterephthalate) support A coated with a gclatin/Lippman emulsion (coating 910 1 mg silver/m was exposed conventionally to a step scale of increasingly intense light. The exposed element Table was then subjected to the following developing procedure: (238C) 4 20 Step No. Time Accomplished (CH CC-CH l minutes Color Develop" I 3 2 5 minutes Wash 3 5 minutes Fix 25 4 5 minutes Wash 5 5 minutes Bleaeh o 5 minutes Wash 7 5 minutes Fix Coupler 2 i 4 5 6 8 l0 minutes Wash "'Color Developer H F H F H H :i f 30 12 Cl H H. soluble coupler (5 X moles) 1 Cl H Cl 7 H 1 3 N,N-diethyl-p-phenylenediamine HCl" 3.0 g/l. Cl H H Cl H 2 potassium bromide 1.0 g/l. 15 H Cl H H 1 2 sodium sulfite 0.65 g/l. [6 Cl H H Cl 2 potassium triphosphate 150 g/l 17 Cl H Cl H p9 pH adjusted to 120111 218C. H H L81) 35, 19 c1 H 01 1-1Hso.,cH, H 1.03 sodium thiosulfate Z20 gll. 20 Cl H C] H 2.15 sodium sulfile 10.0 g/l. i 1 NHso, Ph cH,, I sodium hydroxide 0.15 g/l. 21 Cl H N() Cl H Z.l0 ""Blcilflh 22 Cl H H N HSO- .CH;, H 0.40 sodium bromide 35.0 g/l. 23 Cl H H =1 H 260 potassium fcrrieyanide l0 H 0 200 g/l. sodium hydroxide 0.l g/lv 4 sodium tetraborate 5 H O l.0 g/l.

2 Table III Coupler No. 2 3 4 5 X Dmax 24 OCH H H H O-Ph-CO0H-(,p) 1.47 25' 'Cl H -H H OC0Ph L52 26 c1 H H H -o-- No 1.86

27 01 H H H -o-.- SO @OH 2.90

28 Cl H H H -O COOH 2.82

20 1-1 H H H -o@-cooH 2.21s

30 C1 01 H H O 0 H 3.28

31 Cl H Cl H o 3.30

Table Ill-continued o 0 ll H I H (CH3)3C-C-(IZ-CN 4 Coupler No. 2 3 4.5 X i Dmax 32 Cl H CI H -Q --COOH 3.26

33 Cl H H Cl -o -@cooH 3142 1 1 34 Cl H Cl Cl -@-cooH 3.8

35 Cl H CI CI -o-@ 3.32

cooH Illustrative Manufacture of Coupler Material O H O CO2CH2C6H5 A solution of 76.9 g of the amide (I) and phenol(ll) times with 100 ml water and then dried over M SO in 400 ml of acetonitrile containing 30.1 g. triethylam- 55 filtered, and concentrated in vacuum. The resulting ine was heated at reflux for 2 /2 hours. The solution was yellow syrup was dissolved in 200 ml methanol and then evaporated in vacuum. The resulting solid matecrystallized at room temperature. The dried crystalline rial was dissolved in 500 ml chloroform, extracted 3 product had a melting point of 92-95C.

Step 2 O H O H2/Pd 1| 1 u (Product from Step l)- (CH C-C-C-C-NH C1 EtOAc 3 3 1 C I I I) O CO l-l A solution of 51.4 g of the product from Step 1, above, in 300 ml ethyl acetate and 2.0 g of 10% palladium on carbon was shaken under 40 psi of hydrogen until hydrogen uptake ceased. Then the solution was warmed to completely dissolve the product. The resulting suspension was filtered to remove catalyst, and the filtrate was dried. The pale, pink solid material was recrystalized twice with methanol containing charcoal (for color improvement) to yield a product (Compound lV) having a melting point of l85l87.5C.

The invention has been described in detail with particular reference to preferred embodiments thereof, but, it will be understood that variations and modifications can be effected within the spirit and scope of the invention.

What is claimed is:

1. In a color developer composition comprising at least one organic aromatic primary amino developing agent and a yellow-dye-forming coupler material; the improvement which comprises using as said yellowdye-forming coupler material a compound having the structure:

wherein R is a branched alkyl group containing 3 to 6 carbon atoms; X is Cl or Br; Y is X, hydrogen or alkyl (l'to 8 carbon atoms); and A and B differ and are either H or COOM, wherein M is a photographically inactive cation or a methyl or ethyl group.

3. An improved developer composition as in claim 2, wherein said coupler material is a 2,4-dichloroacetanilide compound.

4. An improved developer composition as in claim 1, wherein said coupler material is a-4-carboxyphenoxy- B-pivalyl-2,4-dichloroacetanilide.

Claims

1. IN A COLOR DEVELOPER COMPOSITION COMPRISING AT LEAST ONE ORGANIC AROMATIC PRIMARY AMINO DEVELOPING AGENT AND A YELLOW-DYE-FORMING COUPLER MATERIAL; THE IMPROVEMENT WHICH COMPRISES USING AS SAID YELLOW-DYE-FORMING COUPLER MATERIAL A COMPOUND HAVING THE STRUCTURE:

2. An improved developer composition as in claim 1, wherein R is t-butyl, Y is hydrogen, and M is selected from the group consisting of hydrogen, alkali metal, ammonium and tertiary amino cations, and wherein said developing agent is a p-phenylenediamine-type color developing agent.

4. An improved developer composition as in claim 1, wherein said coupler material is Alpha -4-carboxyphenoxy- Beta -pivalyl-2,4-dichloroacetanilide.