CA1041116A - Color developer compositions containing improved yellow dye-forming coupler - Google Patents

Abstract

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 atoms; X is C1 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 or 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

` ` 1041~6 This il~vention rclates to diffusible yello~Y-dye-I forming coupler compounds ~xhibiting good solubility properties, unusually high color-forming efficiency and, in the dye form, unusually ~ood aging and absorption characteristics. Also, the present inve~tion relates to de~eloper compositions containing - such valuable ~iffusible yellow-dye-forming coupler materials.
i The coupler compounds of this invention are halo-; anilidophenoxycarboxy compounds having the structure I:

1 0 o ~i , R-C-C-C-NH- ~ X
~ X

- B
! : :
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 -COO~I, 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 of the structure I and one or more organic aromatic amino developing agents, which developer compositions are used in the form of aqueous solutions .;i ~ , . .
comprising water and having a pll of at 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 com-; pounds is well known. Color-forming coupler compounds have been . ~ . .
~; classified as "incorporated" and '!diffusible", based upon ~, the way sucl- compounds are ordinarily used. For example, "incorporate~" couplers have fairly large molecules ln 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 ` ~041~
lement. ~y comparision, "~iffusible" cou~lers are soluble in . alkaline solutions hhich a~so usually contain one or more organic . aromatic amino developing agents. Thus, when diffusible couplers are used, their capability of diffusing 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 diffusi.ble 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, 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 correspond-' ing dyes during the color developing process. . .... "' Diffus1b1e couplers that form yellow'dyes have, to date, exhib1ted more of a need in this respect than have other types : '' ... ' ~-~ 20~; of.color-forming couplers. ' ' ~' '' "' ~` ' '' Deiscription o the Invention :
It has now been discovered that a small group or class 'o~ pivalyl a-aryloxy anilide, yelIow-dye-forming coupler compounds . ;displays the valuable characteristics set out above.
The valuable properties of the couplers (and composi~
`tion9 containing them) of the present invention apparently result ' 'i from the~'unique combination of substituents on the basic keto-`~ .'.
methylene backbone structure of the coupler compounds encompassed by~F:o~mula I above,.' Thus, i~t was known heretofore,.as disclosed ~
O~:~`in~U~.~S~ Patent~s~3,265,506~now~Reissue No. 27,S48) and 3,408, 194, 'that v~r:`y ~ood~yellow dye`'stability and anti-stain properties -: result:when;coup'lers having ` :~::~ :.: '.

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loqi~

(a) an aryloxy "couplin~ oLf" group attached through the ether linXa~e 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.
It has 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 td) there is a carboxyl substituent (either a carboxylic ` ~cid or a photographically ina~tive salt or lower alkyl ester thereof) attached at either the "3" or "4" ;~
position on the aromatic ring of the "aryloxy" coupling-^ ~ff groupL
Preferred halogens, as in part "(c)" of the above dis-i ~r closure, are Ci 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 o the ~acetanilide portion of structure I, Regarding the photo-;1 graphically inactive cation designated "M" in structure I, above, it is preferred that M be selected from the group consisting of ~1, alkali metal and ammonium cations and tertiary amines. Of those couplers having the structure I, partlcularly preferred in th~ practice of the present invention is alpha-pivalyl-alpha-~-carboxyphenoxy)-2,~-dichloroacetanilide.
Hydrolytic Stability Test 30 ~ As it was stated above, one of the valuable properties of the materials of the present invention relates to ~heir su~rprlsingly hl~h resistance to hydrolysis under condltions , ~ : - -r ~, ~- , -- 1041~16 -which simulate cnd-usc con~itions; namely, in aqueous solution - at a buffered p~l of 1~.06 and at a temperature of 23.9 C. Under such conditions, with the coupler being dissolved in the aqueous buffered solution at a concentration of coupler about 6.6 x 10-5 molar, many couplers have been found to degrade ~hydrolyze) at varying rates of hydrolysis. The rates of hydrolysis are apparently unaffected b~ the presence or absence of color developing agent in the solution. By monitoring the rate of disappearance of the coupler from the buffered solution (by measuring the solution absorption at the optimum wavelength at ~hich the particular coupler anion absorbs), it was found that, generally, hydrolysis proceeded in a linear fashion, when the log of the absorption , was plotted vs. time. As a result, relative rates of hydrolysis t of couplers can be set out in terms of their respective "half- , lives" in this standard test. In terms of hours, practical acceptability for very high quality diffusible couplers is believed to require half-lines of at least about 1000 hours. The half-; lives of all of the coupler materials of the present invention are believed to substantially greater than 1000 hours in this test. tThis has been confirmed by tests on some of the coupler compounds oE structure I above.) In order to demonstrate the excellent hydrolytic stability that can result from coupler compounds having the structure I, a number of coupler materials were submitted to the . . . :,, "hydrolytic stability" test described above. Results from that test are set out in Table I.

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104~16 T~ble I ~ :
. ' HYDROLYTIC STABILITY D~TA ~ -.(Test at p~l = 12 and at T = 23.9C.) " , " ~ B5 ..
: . Structure II (C~13)3CC-C-C-N~ O ~ B3 ~ 4 :
,. - , B 2 : .
Coupler No. Z B2 B3 B4 B5 Half-life ~hrs.
.. 1 Cl -OCH3 H H H 0.026 .
:~ . , : . .

2 o ~ NO2 -OCH3 H H H 233 i . .
~ 3 O- ~ COOH -OCH3 H ~ H H 1132 ~" ~ ~ .
4 O - ~ :OCH3 H H H 1430 . ; COOH . .

`10 ~~ 5 ~Cl ~H -OCH3 H H 0.012 6 O- ~ NO2 : : H -OCH3 H H 8 7 ~ ~ Cl Cl H H H 0.082 8:: O~- ~ - COOII C1 H H H 2180 ;: :. 9 O - ~ -COOH Cl C1 H H ~2500 l0 ~acetoxy H H H H o.oi ;It is expected that the presence of another substituent (such ` :.
as~alkoxy, halogen or alkyl) on~the::.aromatic ring of the acet~
;`.anilld~e~portlon of the~couplers.~of~:this invention would not have ;~
..~ i.al-:appreclable;~ è~trimental~effect ùpon the hydrolytic stability ..... ~ 20 :~of the~resulting couplers;as compared to that of the couplers whlch~were~ lnvol~red in~.th~ls~test.~

~041:116 It is also note~ortlly that the coupler compounds of the present inve~tion ekhibit a very high degree of color-forming efficiency. In vie-i thereof, they can be used at some~hat lo-~er concentrations in photograpllic processes if desired, in ordcr to obtain yellol~ dye levels comparable to those presently obtainable by conventional methods using present commercial processes and coupler/color developer compositions Alternatively, colored photographic materials having greater yello~ dye density may be obtained via the practice of this . .
invention, particularly ~hen the invention is practiced commer-ciallyJusing aqueous solutions of coupler, color developer and alkaline materials in the usual manipulative manner.
The compositions of the present invention comprise one or more p-phenylenediamine type color developing agents.
Such agents are well known and need not be described in detail herein, since any phenylenediamine color developing agent can be . .
used. A preferred p-phenylenediamine-type color developing agent . .
` is 4-amino-N-ethyl-N-(2-methoxye~hyl)-m-toluidine, di-p-toluene-sulfonate salt. The coupler compounds of structure I can be ; 20 used successfully in combination with such color developing agents. The ratio of color developing agent to coupler in the compositions of this invention can vary widely, but will generally ` ~e within the (molar) range of from about 0.~ to 1 to about 10 to 1, respectively, and preferably within the (molar basis) range .,j .
j of from about 0.5 to 1 to about 3 to 1. The coupler/color developer compositions of this invention are preferably blends ~;~ of solid crystalline or powdered materials which blends can rea~ily be ~issol~ved in aqueous compositions in the preparation . ,~,.................................................................. : .
of color dfeveloper baths. Such baths, which contain yellow 30 ~ dye-orming coupler dissolved therein, can then be used in the conventional manner during the "yellow developer" step in a -~
multi-step process for manufacturing colored photographic articles.

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Use o~ the coupler compositions of this invention is demonstrated beloi. in the ~xample.
The couplers of this inve~tion can readily be manu-factured via ~.ell known techniques, as set out in U.S. 3,408,19~, for example, by simply using the appropriate raw materials.
In the following Example, all parts are by weight unless otherwise specified.
EXA~IPLE
A conventional photographic element comprising a transparent poly(ethyleneterephthalate) support coated with a gelatin/Lippman emulsion (coating 910 mg silver/m2) ~.as exposed conventionally to a step scale of increasingly intense light.
The exposed element was then subjected to the following developing procedure: (23.8C) Step ~ Time Accomplished 1 5 minutes Color Develop(l) .
- 2 S minutes Wash .i~ .
'~ 3 S minutes Fix(2) - 4~ 5 minutes l~ash ~; 20 5 5 minutes Bleach(3) 6 5 minutes Wash 7 5 minutes Fix(2) "~ , . . .
~; 810 minutes Wash ~ (i) Color Developer ;~ soluble coupler (5 x 10-3 moles)

3 N,N-dietl-yl-p-phenylenediamine HCl 3 0 g/l.
~; potasslum bromlde ~ 1.0 g/l.
sodium sulfite s 0.65 g/l.
~ potassium~triphosphate ~ 15.0 g/l.
pH adjusted to 12.0 at 23.8C.

.. . . .

~04~1~6 (2) Liquid li~ t ., sodium thiosulfate 220 g/l, , sodium sulfite 10.0 g/l.
sodium hydroxide 0.15 g/l.
(3) Bleach - sodium bromide 35,0 g/l.
- potasslum ferricyanide-10 H2O 200 g/l.
sodium hydroxide 0.1 g/l.
sodium tetraborate-5 H2O 1.0 g/l.
, Data resulting from subjecting the processed film strips to spectrophotometric absorption tests were recorded. In the following Tables II and III, "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 "four-equivalent" couplers, while those providing data , . for Table III wer,e "two-equivalent" couplers. Substituent groups appearing at the column headings in these Tables refer to the `, structural formula at the beginning of each table, ~ , .,. . ~.- ~: .

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- Ta~lc II
o o l6 S
- " " H ~
tC~l3)3c-c-cH2-c-N~ 4 : . 2 3 Coupler No. 2 3 4 5 6 Dmax - 11 F H F H H 1.93 12 Cl C1 H H H 2,42 - 13 C1 H Cl }I H 2.63 14 Cl H H Cl . H 2.73 lS H Cl Cl H H 2.02 16 C1 H H H Cl 0.32 17 ~ Cl ~,' Cl-~iOz H 1.98 :
18 Cl H Cl -NH2 H 1.80 19 . Cl H C1-NHSO2CH3 H 1.03 -: ~ 20 ~ Cl H Cl . H 2,15 : -Nllso2-~-cH3 21 Cl - H -NO2 C1 H 2.10 ~ :
;22 ~ C1 H H -NHSO2CH3 H 0.40 23 Cl H. H -CP3 H 2.60 ' ` ' ' ~' . , `
, . .

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.

109~116 - ~ -Y ~ U7 00 0 ~ ~ ''' '' ~' .. . - . ~

P. T c ~ 5 :
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lo,o ~ o, o o o o , .
o ~: U7 _1 X ~ ~ X
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Illustr~ti~c ~lanuf~cture of Coupler ~lateri~l St~p 1 .
- . o ~, o R~ -(C ~l3 ) 3C - C - C C - N~l ~}C 1 + (~1 ~ t 3N
Cl C02CH2C6H5 - ~I) (II) :
, O ~1 0 " ~ "
(CH3) 3C-C -C -C -NHJ~ O ~Cl ` :
O ~ : ,.': ' /~ Cl , co 2 C~1 2C 6H 5 ~ I I I ) - ~
- A solution of 76.9 g of the amide (I) and phenol (II) , , in 400,ml,of acetonitrile containing 30.1 g. triethylamine was ,, - heated at reflux for 2-1/2 hours. The solution was then evapora- ' , 10' ted in vacuum. The resulting solid material was dissolved in 500 ml chloroform, extracted 3 times with 100 ml water and then dried ovcr ~gSO4, filtered, and concentrated in vacuum. The resulting yellow syrup was dissolved in 200 ml methanbl and , crystallized at room temperature, The dried crystalline product had a melting point of 92-95C.
' Step'2 .
O ~1 0 -' Product from Step 1) H2lPd>C " ' " ~ Cl EtOAc ~ 3 3 III) ~ Cl I O I
(IV) ' ' COzH
, ,,. . ~ . .

.
~ : , , : : -104111~i ~ solution of ~1.4 g of the product from Step l, 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 recrystallized twice lth methanol containing charcoal (for color improvement) to yield a product (Compound IV) having a melting point of 185-187.5C.
The invention has been described in detail with : ... . .
particular reference to preferred embodiments thereof, but, it will be understood that variations and modificatîons can be : . .
effected within the spirit and scope of the invention.

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Claims (11)

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 yellow-dye-forming coupler material a compound having the structure:

wherein R is a branched alkyl group containing 3 to 6 carbon atoms; X is C1 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

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.

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

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

A coupler compound capable of reacting with oxidized aromatic amino color developer agent to form a yellow dye, said compound having the structure:

wherein R is a branched alkyl group containing 3 to 6 carbon atoms; X is C1 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.

6, A coupler compound havlng a structure as in claim 1, wherein X is C1, Y is H, and A is COOM.

7. .alpha.-4-carboxyphenoxy-.alpha.-pivalyl-2,4-dichloroacetanilide.

8. .alpha.-3-carboxyphenoxy-.alpha.-pivalyl-2,4-dichloroacetanilide

9. .alpha.-4-carboxyphenoxy-.alpha.-pivalyl-2,3-dichloroacetanilide,

10. .alpha.-3-carboxyphenoxy-.alpha.-pivalyl-2,4,5-trichloro-acentanilide.

11. .alpha.-4-carboxyphenoxy-.alpha.-pivalyl-2,5-dichloroacetanilide,