DE1547813B - - Google Patents

Description

1 O4 / ö1 D

The invention relates to a photographic color development process, in the case of a paraphenylenediamine derivative, a halide silver emulsion which has a colored and a colorless purple coupler is developed. In this procedure, the one is colored Coupler is a pyrazolone which has an —N = N — R— group in position 4, in which R is an alkyl radical or is a heterocyclic radical. The colorless coupler is a pyrazolone which has a phenyl group in the 1-position wearing.

With the color negative positive technique using the subtractive process, it is well known distorted color reproduction due to undesired spectral absorption of the dyes. To compensate for this, the so-called masking is used. The use of a yellow-colored coupler is known for this, in which a pyrazolone derivative bears an —N = N - R - group in the 4-position (US Pat 2 455 170). When the halide silver emulsion layer containing such a coupler is made by means of of a paraphenylenediamine derivative is developed, the coupler produces an in the exposed areas Purple color as negative. The remaining coupler produces a positive yellow image in the unexposed areas.

When the exposed silver halide is treated with a paraphenylenediamine derivative for color development is, its oxidation product couples with said coupler in the 4-position, and at the same time the azo group is released. However, the application of the colored coupler is as follows Difficulties associated: the extinction coefficient of the colored coupler with the —N = N — R— group is too high, resulting in an excessive masking effect. It is therefore necessary to regulate the masking. For this purpose, the colored coupler is used according to US Pat. No. 2,428,054 mixed into the emulsion layer together with a colorless coupler. According to the USA patent 2,688,539, two emulsion layers of the same color sensitivity are used, one of which is the colored coupler and the other the colorless coupler.

When using a colored coupler in which the hydrogen atom of the active methylene group is substituted by an azo group, is formed during development using paraphenylenediamine derivatives a significant fogging effect. Although avoiding veils is very important so far no effective methods for preventing haze have become known. The fog formation at The presence of azo-substituted colored couplers occurs only when paraphenylenediamine derivatives are used as color developing agents can be used, but not if the same emulsion is mixed with a black and white developer, such as methol or hydroquinone. There is also considerable fogging, when developed in the presence of a diazonium compound by means of paraphenylenediamine derivatives. It can therefore be considered that fogging occurs in the presence of a colored coupler and development with paraphenylenediamine derivatives through diazonium compounds occurring as by-products is increased if the oxidation product of the developing agent in the unexposed areas couples with the colored coupler. This type of fogging can be prevented by the usual anti-fogging agents and stabilizers can hardly be prevented.

It is an object of the invention to prevent fogging during color development by means of paraphenylenediamine derivatives to prevent.

The invention relates to a photographic color development process in which with a paraphenylenediamine derivative a silver halide emulsion is developed, one colored and one colorless Contains magenta coupler, the colored coupler being a pyrazolone which is in the 4-position - N = N - R - carries a group in which R is an aryl radical or a heterocyclic radical, and the colorless coupler is a pyrazolone which is in the 1-position Phenyl group, characterized in that the phenyl group of the colorless coupler to be used is substituted with a sulfonic acid or carboxyl group.

According to the invention, a compound of the general formula I or an alkali or Ammonium salt of such compounds is used.

R ₁ CCN-R R2

(I)

In this formula, R ₁ denotes an alkyl group, a substituted alkyl group, an acylamino group, an N-arylamino group, an N-substituted arylamino group or a sulfoamide group, R ₂ denotes a phenyl group, a substituted phenyl group, a naphthyl group, a substituted naphthyl group or a heterocyclic group, X _1, X ₂ and X ₃ is a hydrogen atom, an alkyl group, a halogen atom, a substituted alkyl group, an acylamino group, an alkylcarbamoyl group, a substituted alkylcarbamoyl group, a sulfoamide group, an alkoxy group _(group, an aryloxy group, a sulfonic acid * or a carboxyl group.

A compound of the general formula II or an alkali or ammonium salt is used as the colorless coupler such compounds are used.

(Π)

In formula II, R ₁ , X ₁ and X _{2 have} the same meaning as in formula I; X ₄ is a sulfonic acid or carboxyl group or an alkali or ammonium salt of such groups.

1 54 / Ö13

According to the invention, by additionally adding a colorless coupler of the general formula III the masking can be regulated.

(III)

In formula III, R _{1 has} the same meaning as in formula I, X ₅ , X ₆ and X ₇ are hydrogen atoms, halogen atoms, alkyl groups, substituted alkyl groups, acylamino groups, alkylcarbamoyl groups, substituted alkylcarbamoyl groups, sulfoamide groups, alkoxy groups or aryloxy groups.

The main structural feature of a coupler of the formula II used to prevent fogging is that the 1-position of the pyrazolone nucleus is substituted by a phenyl group which has the water-solubilizing group X ₄ as a direct substituent. The coupling ability or speed of a colorless coupler of the formula II is very much higher than that of a coupler of the formula I or III compared to the oxidation product of the paraphenylenediamine derivative. So if couplers of the formulas I, II and III are present at the same time, the coupling takes place predominantly with the coupler of the formula II. Furthermore, if the coupling capacity of the colored coupler I compared to the oxidation product of the paraphenylenediamine is about the same as that of the coupler III you can adjust the masking to the desired extent.

Since the colorless coupler II mainly enters into the coupling reaction, it cannot mask regulate, or it only leads to partial masking! However, there is no fogging caused by the Coupler I.

If a small amount of colorless coupler II is added to colored coupler I and then an appropriately chosen amount of colorless coupler III is added, coupler II is first consumed during color development, and then coupling with couplers I and III takes place. If the amount of coupler II added is selected appropriately, taking into account the silver halide emulsion used and the developing conditions, then the formation of fog can be prevented without the masking being adversely affected. The useful amount of colorless coupler II added to prevent fogging is about 4 to 50 percent by weight, based on colored coupler I.
Examples of colored couplers of the formula I which can be used according to the invention are:

(M)

SO, H

(1-2)

H ^ C ₁₈ -CH - CONH - C

CH, -COOH

OCH,

(1-3)

H "C, o-CH-CONH-C

CHoCOOH

SO ₃ H

IQiD

(1-4) (1-5)

(1-6)

H "C ₁₇ -C CN = N-

N C-OH

SO ₃ H

H ₃ CC-

N C-OH

NHCOCH-C ₁₈ H ₃₅ CH ₂ -COOH

/ \ -C0NH-C
H ₃₃ C ₁₆ -CHCONH

OCH,

OCH,

N C-OH

SO ₃ H Cl-Τ Tl-Cl

Cl

(1-7)

(1-8)

H "C ₇ CO NH-C

U = U -N-
OH -C-CH ₃
N φ -N C-
Il
HO-C Λ Y

SO ₃ H

SO ₃ H

H ₃₅ C ₁₈ CHCONH CH ₂ COOH SO ₃ H

NH C C-N = N

H ,, C _1R -CH-CONH CH ₂ COOH

NH C C-N = N-C

Il Il

N C-OH

CH ₃

' ^nX n

\ NH CH ₃

H ₃₅ C ₁₈ - CH - CONH CH ₂ --COOH

^ -CONH-C-

Il

y \

H ,, C «- CH-CONH

CH ₉ -COOH

Cl

CONH-C-

Cl

C-N = N-C-OH

Cl

NHCOCH,

-C-N = N- ^

Il
C-OH

CH,

^S N "

Cl

Cl

N C-OH

1 / -SO ₃ H 0 S0, H

SO ₁ H

s C ₁₇ -C 9 " ¹ ^ ¹

N C-OH

SO ₁ H

OCH,

(1-14)

C ₅ H ₁₁

1 C ₂ H ₅ 547 8th 13th OCHCONH —C— -C-
Il N Il
c-

ίο

CN = N ^ / V- OCH ₃

Il \ = /

Cl

Cl

Cl

Examples of haze prevention according to the invention (Π-4) Couplers of the formula II to be used are:

(II-l)

C CH ₂

20 H ₃₅ C ₁₈ CHCONH CH ₇ COOH

CONH - C-CH ₂

N CO \ /

N CO
\ /

SO ₁ H

rlasV ^ iT (

N CO
\ /

COOH

30 (Π-5)

35

40 H ₃₅ C ₁₇ CONH-C-CH ₂

N CO N /

SO ₃ H

45 (Π-6) H ₃₅ C ₁₇ CONH

SO, H

■ 50

55 Il I

N CO

N /

COOH

(Π-3)

] ^ ^^ CONH C CH ₂

N CO
\ /

SO ₁ H

6o

H ₃₅ C ₁₇ CONH-C CH ₂

N CO \ /

SO ₁ H

(III-l)

NHCOCH-C ₁₈ H ₃₅ CH ₃ -COOH

(ΙΠ-2)

H ₃₃ C ₁₆ CHCONH-C -— CH ₂

SO ₃ H

(III-3)

H ^ C ₁₈ CHCONH

CONH - C

CH ₉ -COOH

Examples of according to the invention for masking (III-4) Colorless couplers of the formula III to be used for regulation are:

CONH - C CH ₂

H ₃₃ C ₁₆ -CH-CONH
SO ₃ H

OCH,

(III-5)

H ₃₅ C ₁₈ -CHCONH

CONH - C CH

I.
CH ₂ -COOH

30th

35

40

CONH - C CH

CH ₇ COOH

(III-7)

H ₁₁ C.

C, H,

O — CHCONH

5 ¹ St.

Examples follow to further illustrate the invention * The amounts are given in parts by weight. . .

example 1

A color sensitizer for green sensitivity was added to 100 parts of a silver bromide emulsion. Then, each 20 parts of a 5 ° / _o by weight alkaline aqueous solution of the colored couplers listed in Table 1 I and antifogging 3 parts of a 5% alkaline aqueous solution of the colorless coupler II were added. These emulsions were coated on film bases coated with a substrate layer. The films were treated for 10 and 15 minutes at 20 ⁰ C in a solution containing a developing agent N, N-Diäthylparaminoamilin. It was then bleached and fixed. Table 1 shows the results relating to the green light density of the color fog.

i O4 / ö1 D

Table 1

Dyed
Coupler I Colorless
Coupler II Color haze density at
Development time from 15 minutes 10 mins 0.88 1-6 without 0.44 0.21 1-6 II-l 0.15 0.14 .1-6 II-2 0.11 0.21 1-6 II-3 0.14 0.29 1-6 II-4 0.20 0.38 1-1 without 0.24 0.14 1-1 II-l 0.12 0.14 1-1 II-2 0.10 0.20 1-1 II-5 0.14 0.11 1-1 II-6 0.08 0.15 1-1 II-7 0.13 0.65 1-2 without 0.38 0.24 1-2 II-l 0.16 0.44 1-3 without 0.30 0.21 1-3 II-l 0.14 0.40 1-4 without 0.27 0.14 1-4 II-l 0.09 0.77 1-5 without 0.39 0.26 1-5 n-i 0.16 0.31 1-7 without 0.20 0.14 1-7 II-l 0.11 0.56 1-8 without 0.35 0.19 1-8 II-l 0.14 0.74 1-9 without 0.41 0.25 1-9 II-l 0.17 0.51 1-10 without 0.33 0.18 1-10 II-l 0.12 0.34 I-11 without 0.22 0.14 I-IJ II-l 0.10

given colored coupler 1.15 parts of a 5% strength alkaline aqueous solution of the colorless coupler III for masking regulation and 2 parts of one 5% alkaline aqueous solution of the colorless coupler II was added to prevent haze. With film supports coated with a substrate layer were coated on these emulsions. The color development took place as in Example 1. The results with regard to color fog density of the unexposed areas Table 3 shows.

Table 3 Example 2

5 g of the colored coupler 1-14 was dissolved in 10 g of dibutyl phthalate. The solution was the addition of a dispersing agent in 100 g of a / dispersed 10 ° _o aqueous solution of gelatin. With otherwise the same procedure as in Example 1, 23 parts of this dispersion were used in place of 20 parts of an alkaline aqueous solution of coupler I. The results are shown in Table 2

Table 2

Colorless Color haze density at 15 minutes Dyed Coupler II Development time from 0.43 Coupler I 0.16 without 10 mins 0.17 1-14 II-l 0.28 0.22 1-14 II-3 0.12 1-14 II-4 0.11 1-14 * 0.15

Dyed
Coupler I Colorless
Coupler II Colorless
"Coupler III Color haze density
Development time
10 mins 1-2
1-2
1-9
1-9
1-9
1-6
1-6 without .
II-l:
without
II-l
II-2
without
II-2 III-5
III-5.
III-2
III-2
III-2
III-3
III-3 0.34
0.15
0.48
0.27
0.16
0.28
0.14

Example 4

1.0 g of Coupler I and 2.0 g of Coupler III were dissolved in 10 g of dibutyl phthalate, and while adding one Dispersing agent dispersed in 100 g of 10% aqueous gelatin solution. When working according to In Example 3, 30 parts of this dispersion were used in place of the aqueous alkaline solutions of the couplers I and III used.

In a further experiment, the dispersion with the addition of 2 parts of a 5% alkaline aqueous solution of the coupler II used.

The color development took place as in Example 1. The fog density of the unexposed areas is shown Table 4.

Table 4 Example 3

A color sensitizer for green sensitivity was added to 100 parts of a silver bromide emulsion. Then in each case 10 parts of a 5% alkaline aqueous solution of the other in Table 3

Dyed
Coupler I Colorless
Coupler II . Colorless
Coupler III Color haze density
Development time
10 mins 1-14
1-14
1-14 without
II-l
II-2 III-7
III-7
III-7 0.28
0.12
0.09

The examples show that the addition of the colorless coupler II suppresses the formation of fog quite considerably.

Claims (5)

Patent claims: 1. A photographic color development process in which with a paraphenylenediamine derivative a silver halide emulsion is developed which contains a colored and a colorless purple coupler contains, the colored coupler being a pyrazolone which has an —N = N - R - group in the 4-position in which R is an aryl radical or a heterocyclic radical, and the colorless coupler is a pyrazolone which has a phenyl group in the 1-position, characterized in that that the phenyl group of the colorless coupler to be used with a sulfonic acid or carboxyl group is substituted. 2. A photographic color development process according to claim 1, characterized by the use of a colored coupler I of the general formula R ₁ -C CN = NR ₂ IO (I) 20th wherein R ₁ denotes an alkyl group, a substituted alkyl group, an acylamino group, an N-arylamino group, an N-substituted arylamino group or a sulfoamide group, R ₂ denotes a. Phenyl group, a substituted phenyl group, a naphthyl group, a substituted naphthyl group or a heterocyclic group, X ₁ , X ₂ and X ₃ a hydrogen atom, an alkyl group, a halogen atom, a substituted alkyl group, an acylamino group, an alkylcarbamoyl group, a substituted alkylcarbamoyl group, a sulfoamide group, a Alkoxy group, an aryloxy group, a sulfonic acid group or a carboxyl group or alkali or ammonium salts of the sulfonic acid or carboxyl group. 3. Photographic color development process according to claim 1 or 2, characterized by the Use of a colorless coupler II of the general formula (Π) wherein R ₁ , X ₁ and X _{2 have} the same meaning as in claim 2 and X _{4 is} a sulfonic acid or carboxyl group or an alkali or ammonium salt of such groups. 4. A photographic color development process according to claims 1 to 3, characterized in that that the colorless coupler II in amounts of about 4 to 50 percent by weight, based on the colored Coupler I is added. 5. Photographic color development process according to claim 1 to 4, characterized by additional use of a colorless coupler III of the general formula Ri-C-CH ₂ (III) wherein R _{1 has} the same meaning as in claim 2 and X _{5 , X 6 and X 7 are} hydrogen atoms, halogen atoms, alkyl groups, substituted alkyl groups, acylamino groups, alkylcarbamoyl groups, substituted alkylcarbamoyl groups, sulfoamide groups, alkoxy groups or aryloxy groups. 009 526/24