DE1643988C3 - Use of a masking cyan coupler for producing masked color images in color photographic silver halide emulsions - Google Patents

Description

The invention relates to the use of a masking cyan coupler for producing masked color images in silver halide color photographic emulsions.

Almost all of the cyan couplers used as color formers for color photography are l-naphthol-2-carboxy acid derivatives or aminophenol derivatives, and when using these couplers in photographic emulsions will have a long chain alkyl group or a dialkylphenoxy group in the Molecule of the coupler to impart diffusion resistance to the coupler introduced to the coupler to prevent it from diffusing out of a layer into which it had been incorporated.

U.S. Patent Nos. 2,449,966 and 2,455,169 describe couplers having an auto-masking effect for correcting errors or deficiencies in color formation in color photographic materials.

In US Pat. No. 2,521,908, 1-hydroxy-2-naphthamide compounds for colored couplers are the general formula

O X

in which X is hydrogen or an alkyl group, Y is a mononuclear aryl group or an aralkyl group and R _{1 is} a mononuclear aryl group. US Pat. No. 2,70,6684 describes colored 1-hydroxy-2-naphthaniIid coupler compounds having the formula given above, in which X is hydrogen, Y is a mononuclear aryl group which is in an o-position to the amide group with halogen, alkoxy or a mononuclear Aryloxy radical is substituted, and Ri represent a mononuclear aryl radical.

In US Pat. No. 3,034,892, 1-hydroxy-2-naphthamide compounds are w of the general formulas .is described:

-NH- (CH ₂ J _x O ₁ -R,

OH

wherein χ represents O or a positive number from 1 to 4, yO or 1, R2 represents a phenyl group, an alkyl group having 6 to 15 carbon atoms, an alkyl-substituted phenyl group or an alkyl-substituted phenoxyphenyl group and R3 represents an alkyl group having 1 to 4 carbon atoms.

In order for these couplers to have a sufficient self-masking effect, it is necessary that the

The ratio of green absorption to blue absorption is large and that in the course of color development, the coupler rapidly reacts with the oxidation product of a p-phenylenediamine type color developer to form a positive cyan image.

There is a Magentafarh coupler for this purpose with a large coupling activity is required. Although an orange or orange-red colored cyan coupler can be easily obtained, however, is the production of a magenta colored cyan coupler difficult.

The invention is based on the object of magenta-colored To provide cyan couplers for use in silver halide color photographic emulsions which the production of masked color images and in particular a correction of color errors or - allow deficiency in the cyan color image obtained in the development. According to the invention The masking cyan couplers used are said to have a large bathochromic shift.

This object is achieved according to the invention through the use of a masking Cyan coupler according to the preceding claim.

The masking cyan couplers used according to the invention are new compounds, in which a naphthalene ring in the -position via an amino group to a naphthol nucleus in the 2-position is bonded, with at least one alkoxycarbonyl group in an arylazo radical group present in the 4-position is introduced

A known coupler of the general formula given above, but in which R is a mononuclear Represents aryl group, has an absorption maximum in a much longer wavelength region. The matchmaker according to the invention of the general formula given above, in which, however, R is an unsubstituted one or is naphthyl group substituted in the 4-position with an amino group, but has an absorption maximum in the region of even longer wavelengths, where the molecular extinction coefficient of the coupler according to the invention at the absorption maximum higher than that of the known one Coupler is. This effect is with the coupler according to the invention in which R is attached to the amide group is bound in the "position, especially noteworthy and surprising in view of the fact that in a coupler in which R is attached to the amide group is bound in the ^ position, the achievable effect is almost the same as that obtained with a coupler of the above formula, in which R represents a mononuclear aryl group. Thus, the coupler compounds according to the invention are resistant to diffusion and have a high coupling activity and can be used in combination with uncolored cyan couplers can be used in photographic silver halide emulsions, these compounds in view of are completely surprising because of their small chemical differences.

In addition, the coupling activity of the coupler according to the invention is unexpectedly higher than that of the known coupler in which R represents a mononuclear aryl group These properties of the coupler are desirable for effective auto-masking when correcting secondary clients

As couplers which can be used according to the invention are those shown by the following Suitable formulas: In the formulas below, "s" denotes secondary.

Oll

CONH

> - CC) OCH,

OH

r-CONH

N- <

(OOCH ₂ CHC ₄ H,

OH

CONH

N-?

COOCH ₂ CHC ₈ H ₁₇ QH ₁₃

OH

COOCH ₂ CHC ₄ He C ₂ H ₅

oil

CONII

I,

11., C ₄ IfCII, COOC

C ₂ IU

(00 (11, CHCJl.,

C ₂ II,

OH

CONH

(', H ₁₁ (S)

J -x

> NIKOCH ₇ O

C ₅ H ₁₁ (S)

Il

J,

((X) C ₂ H ₅

OH

C ₅ H ₁₁ (S)

NHCOCH ₂ O

C ₅ H ₁ , (S)

Il

f VC-OOCH ₂ CHC ₄ H,

For comparison purposes, the structural formulas of the known comparative couplers shown in FIGS The following examples were used for comparison with the coupler according to the invention:

OH

QH _n (S)

CONH

NHCOCH ₂ O- <^ C ₅ H ₁₁ (S)

COOC ₂ H ₅

on

ίο

OCH,

(M ( Ii i ⁽ ' ^{() N} "

C ₂ H ₅ CONIICH ₂ CHc ₄ H.,

COOC ₁ H,

Table I below shows the wavelengths at the absorption maximum of positive images from photographic light-sensitive color films which were produced using the couplers according to the invention or the comparative couplers . The known control couplers (a) and (b) were each dissolved in: <> tricresyl phosphate, and the spectral absorption curves of these solutions are shown in FIG. 1 of the drawing. As can be seen therefrom, the coupler according to the invention is excellent in color tone as compared with those of known couplers.

Some examples of the preparation of the couplers according to the invention are detailed below explained:

IG

1.1- Hydroxy-4- (O- (2-ethylhexyloxycarbonyl) -

phenylazo) -2- (N- (1-naphthyl)) - naphthamide

(Formula II)

(1 -a) Production of 1 - hydroxy-2- (N- (I -naphthyl)) - naphthamide ^λΛ

A mixture of 53 g of 1-hydroxynaphthoic acid and phenyl ester and 29 g of Λ-naphthylamine became one Heated to 160 ° C for 1 hour. The solid product thus obtained was dissolved in acetone with heating and cooled to separate crystals, which are recovered by filtration and washed with acetone became. 39 g of the abovementioned compound with a melting point of 160 to 161 ° C. were obtained obtain. The yield of the product was 62%.

(1-b) Manufacture of 2-ethylhexyl-O-aminobenzoate

Ethyl-o-aminobenzoate was mixed with 2-ethylhexanol in an amount which l ^ fold was the theoretical amount, and the mixture was heated to 160 ⁰ C with stirring, after the addition of butyl titanate as a catalyst for carrying out the Esteraustauschreaktion wherein the ethanol formed was removed by distillation. Then, after removing excess 2-ethylhexanol by distillation under reduced pressure, the oily desired material was obtained.

(1-c) Manufacture of

1-Hydroxy-4- (0- (2-ethylhexyloxycarbonyl) phenylazo) -2- (N- (1-naphthyl)) naphthamide

In 100 ml of methanol, 15 g of the 2-ethylhexyl-O-aminobenzoate prepared in step (1-b) above dissolved the solution was cooled to a temperature below 5 ° C. and diazotized with stirring Addition of 16 ml of concentrated hydrochloric acid and 30 ml of water and also 5 g of sodium nitrite, dissolved in 10 ml Water, subject. In addition, 15 g of the I -hydroxy-2- (N- (1-naphthyl)) naphthamide obtained above in step (1 -a) were dissolved in 400 μl of pyridine, and in the solution became the solution of the diazonium salt * prepared above dropwise at a Temperature below 5 ° C while stirring :, wherein crystals were formed which were collected by filtration and removed from acetone after washing with water were recrystallized, 19 g (yield 69%) of the desired material with a melting point of 139 to 141 ° C and a nitrogen analysis value of 7.11% (calculated 733%) was obtained.

2.1 - Hydroxy-4- (O- (2-hexyldecyloxycarbonyl) -phenylazo) -2- (N- (1-naphthyl)) - naphthamide

(Formula III)

The same procedure as described above in step (1-b) in the example above was carried out in Using 2-hexyldecyl alcohol instead of 2-Ethylhexanol repeated an oily 2-hexyldecyl-O-aminobenzoate was obtained. Then the the same procedure as in step (1-c) of the example described above, using 2-hexylbenzl-O-aminobenzoate instead of 2-ethylhexyl-O-aminobenzoate, repeated for the desired material to be obtained with a yield of 63%. The melting point of the product was 111 to 113 ° C, and the nitrogen analysis value was 6.08% ('• ■ «calculated 6.14%).

3.1 -hydroxy-4- (O-ethyloxycarbonylphenylazo) -

2- (N- (1 - (4- (2,4-di-sec.-amylphenoxyacetamido)) -

naphthyl)) - naphthamide (Formula VI)

(3-a) Preparation of 1-Hydroxy-2- (N-I - (4-nitro) -naphthyi) -riaphthamide

A mixture of 38 g of 4-nitro-l-naphthylamine and 53 g of 1-hydroxynaphtholic acid phenyl ester was added to 500 ml of xylene was added and the resulting solution was refluxed for 3 hours. The solution was then cooled by ice, and the crystals so deposited were collected by filtration 40 g of the desired material (yield 55%) with a melting point of 240 to 242 ° C. (decomposition) obtain.

_fo (3-b) Preparation of l-hydroxy-2- (N- (l- (4-amino) -naphthyl)) -naphthamide

In 30OmI of dimethylformamide, there was added 30 g of the nitro compound obtained in Step (3-a) above dissolved and the system was a catalytic Peduktion using Raney nickel as Subjected the catalyst in a 1 liter autoclave. After removing the catalyst by filtration the filtrate was concentrated and cooled thereby

Crystals precipitate, which were collected by filtration and washed with methanol. 16 g (58% Yield) of the desired material with a melting point of 222 to 225 ° C.

(3-c) Production of 1-Hydroxy

2- (N- (l- (4- (2,4-di-sec.-amylphenoxyacetamido)) -

naphthyl)) - naphthamide

To 200 ml of acetonitrile was added 15 g of the amine obtained in Step (3-d) above, and the system was refluxed. Then, a solution of 15 g of 2,4-di-sec-amylphenoxyacetyl chloride in 50 ml of acetonitrile was added dropwise to the system. After further adding 10 g of triethylamine, the system was refluxed for 1 hour. After about 2 ml of acetonitrile had been removed by distillation, the reaction mixture was poured into 1 l of ice water to separate crystals, the vJürCii! 'Titration ξΰ5αίΓιΠϊ € ιι UHu ϊΰϊΐ ΑίιιαΠΟι Ufiikriäiäin , 18 g of the desired material (yield 65 · λ>) with a melting point of 178 to 180 ° C were obtained.

(3-d) Preparation of l-hydroxy-4-

(O-ethyloxycarbonyl-phenylazo) -

2- (N- (l- (4- (2,4-di-sec.-amylphenoxyacetamido)) -

naphthyl)) - naphthamide

A mixture of 50 ml of water and 10 ml of concentrated hydrochloric acid was cooled to 5 ° C. and 4 g of O aminobenzoate were added to the mixture with stirring. Then the system was subjected to diazotization by adding dropwise 2 g of sodium nitrite in 5 ml of water. In addition, 12 g of the l-hydroxy-2- (N- (l- (4- (2,4-di-sec.-amylphenoxyacetamido)) naphthyl)) naphthamide were dissolved in 300 ml of pyridine with subsequent ice cooling. The solution of the diazonium salt prepared above was added dropwise to the pyridine solution with stirring at a temperature below 5 ° C. A red resulting crystal precipitate was collected by filtration, washed with water and recrystallized from ethyl acetate, whereby 119 g (70% yield) of the desired material with a melting point of 198 to 199 ⁰ C and a nitrogen analysis value of 7.03% (calculated 7, 20%) were obtained.

The invention is explained in more detail below with the aid of examples:

example 1

In 10 parts of tricresyl phosphate, 1.5 parts of the colored Cyankupplets were added according to the invention under stirring at about 80 "C, and the solution was mixed with 100 parts of a 10% gelatin solution that had been heated to 60 ⁰ C and after addition of 2 parts of an aqueous 10% solution of sodium alkylbenzenesulfonate, the system for 5 minutes at about 60 ⁰ C by means of a rotary or rotary mixer was stirred by a high speed to disperse the solution, followed by lminütige interruption followed. by 5 times repeating this procedure, a dispersion of the colored coupler was obtained.

On the other hand, the same procedure as described above was carried out using 2.9 Parts of the cyanine coupler of the following structure

formula repeated to make a dispersion of the cyan coupler obtain:

OM

CONII Γ ,,, ΙΙ ,,

In 100 parts of a gelatin-iodobromomide emulsion containing a red-sensitive dye, 10 Portions of each of the emulsions prepared above are introduced at 35 ° C with stirring, and after Further addition of a hardening agent and a wetting agent, the resulting emulsion was reduced to one Film applied and dried to obtain a photographic, red-sensitive color film.

The photographic light-

1.111 ^ 111IUiIl ₁ IiV ■ uPi / ιιιΓμ "A'tiTciC mil rOlCrn L ^ iClIl VjürCll exposed an optical wedge and developed in the usual way in a developer of the composition given below:

Color developer:

N, N-diethyl-p-aminoaniline sulfate sodium sulfite

Sodium carbonate (monohydrate) hydroxylamine hydrochloride

Potassium bromide

water

(pH = 10.8 ± 0.1)

2.0 _fe 2.0 g 50.0 g 1.5 g 1.0 g remainder to 1 liter

.! s Subsequently, the thus developed photographic Film bleached and fixed, using a bleaching solution and a fixing solution with the following, respectively specified compositions was used to remove undeveloped silver halide and that by the Development to remove reduced silver formed.

Bleach solution:

Potassium ferricyanide
Potassium bromide
water

(pH = 6.9 ± 0.3)
Fixing solution:

Sodium thiosulfate (Hypo)
Sodium sulfite
Acetic acid (28 ° C)
Boric acid
Potassium alum
water

100g 20g remainder to 1 liter

200 g 20 g 4.5 g 7.5 g 20 g remainder to 1 liter

(pH = 4.5 ± 0.2)

Thus, a positive magenta image by the colored coupler remaining in the film and a negative cyan image formed by coupling were obtained. In Fig. 2 of the drawing are the measurement results of the density values of the images obtained by using the coupler (1) according to the invention, namely the relationships of the green fitter density (Da) and the blue filter density (De) of the positive magenta image to the

Red filter density (DrJ shown. From FIG. 2 it can be seen that a good masking effect was achieved when the colored cyan coupler according to the invention was used. The table below lists the wavelengths at maximum absorption of the positive magenta image in each case.

Tabel

Colored coupler used

Colored coupler used

Wavelength of the maximum absorption (πιμ) Formula (II)
Formula (III)
Formula (IV)
Formula (V)
Formula (VI)
Formula (VII)

Wavelength of maximum absorption (ιτιμ)

520 520 524 520 520 521

Formula (a) control
Formula (b) control
Formula 1)

514 516 519 The results show that when using de; colored cyan coupler according to the invention, a positive image with a deeper color than in the case of using the control coupler (a) or (b) was obtained.

Hicr / u 2 sheets ZcicIiiiuiiüiMi

Claims (2)

Patent claims: 1. Use of a masking cyan coupler of the general structural formula OH CONHR in the R an unsubstituted or in the 4-position with an amino lip substituted naphthalene residue attached to the amide group in the α-position is bonded, and X is a phenyl radical with at least one alkoxycarbonyl group, for the production of masked color images in color photographic see silver baJogenide emulsions. 2. Use of a masking cyan coupler according to claim 1, characterized in that the Cyan coupler corresponds to one of the following formulas: OH .1 ° C ₂ H ₅ COOCH ₂ CHC ₄ H ₉ (Π) 40 45 : OOCH, CHC ₈ H, QH ₁₃ N- ^ V- COOCH ₂ CHC ₄ H ₉ C, H, OH CONH H ₉ C ₄ HCH ₂ COOC-L ) C ₂ H ₅ / V COOCH ₂ OHC ₄ H ₉ C ₂ H ₅ CONH COOC ₂ H ₅ C ₅ H ₁₁ (S) NHCOCH ₂ O C ₅ H ₁₁ (S) OH QH ₁₁ (S) NHCOCH ₂ O - <f "VC ₅ H ₁₁ (S) (VII) COOCH ₂ OHC ₊ H ₉ C ₁ H ₅