DE2326590B2 - COLOR PHOTOGRAPHIC RECORDING MATERIAL WITH AT LEAST ONE SILVER HALOGENIDE EMULSION LAYER CONTAINING A COLOR COUPLER - Google Patents

Description

R-CO-O- (CH ₂ J _n

in which:

(CH ₂ J _n -O-CO-R

R is a straight-chain or branched-chain alkyl radical having 3 to 15 carbon atoms and

π = 0, 1, 2, 3 or 4, with the proviso that the cyclohexyl ring is substituted in the 1,3- or 1,4-positions.

2. Color photographic recording material according to claim 1, characterized in that the Coupler solvents in the droplets comprised at least in part a liquid ester of one of the consists of the following formulas:

R'-CO-O- (CH ₂ ) XH> (CH ₂ ) "- 0-C0-R '

or

15th

20th

35

R ^ CO-O- (CH ₂ J _n , ΥηΛ

\ - /

(CH ₂ LO-CO-R "

R 'and R "
λ and / π

in each case an alkyl radical with 5 to 8 carbon atoms and
each O,! or 2.

in which mean:

3. A color photographic recording material according to claim 2, characterized in that the coupler solvent in the droplets consists at least in part of a liquid ester of one of the formulas given in which R 'and R "represent branched-chain alkyl radicals having 5 to 8 carbon atoms and η and m = 0 or 1

4. Color photographic recording material according to claims 1 to 3, characterized in that the coupler solvent in the droplets is at least partially
1,4-cyclohexyldimethylene bis (2-ethylhexanoate);
Quinitol di (2-ethylhexoate);
1,4-cyclohexy! diethylenebis (2-ethylhexanoate);

1,4-cyclohexyldiethylenebis (2-methylhexanoate);

or
1,4-cyclohexyldimethylene bis (2-methylhexanoate)

consists

5. Color photographic recording material according to claim 1, characterized in that the Droplets of at least one phenolic or Λ-naphtholic, a blue-green dye generating Coupler, a magenta dye forming 5-pyrazolone or 1-H-pyrazolo [3,2-c] -s-triazole coupler or a yellow dye-forming open chain ketomethylene coupler.

6. Color photographic recording material according to claim 5, characterized in that the Droplets of at least one yellow dye-forming acetoacetanilide or benzoylacetanilide coupler contain.

7. Color photographic recording material according to claim 6, characterized in that the Droplets contain at least one acetoacetanilide coupler, the non-oxo-carbon atom of which is the Aceto group is a tertiary carbon atom

The invention relates to a color photographic recording material in at least one color photographic Silver halide emulsion layer in finely divided droplets of at least one high-boiling point, contains at least one color coupler dissolved in water, which is practically immiscible with water.

It is generally known to use recording materials for the production of color photographic images, their light-sensitive layers non-diffusing or practically non-diffusing color couplers contain which with developer compounds consisting in particular of primary aromatic amines able to react to produce colored images.

The color photographic recording materials commonly used in practice exist usually composed of a support and several sensitized silver halide emulsion layers, wherein dispersed in each emulsion layer are droplets consisting of at least one complete or partially dissolved color coupler in a high-boiling water-insoluble coupler solvent or optionally also contain dispersed droplets, which consist of a polymeric or waxy Material in which a color coupler is included exist. For example, reference is made to the FR-PS 20 17 718 and 15 55 663 and US-PS 72 163.28 35 579 and 35 54 755. In the last two cited patents are described as coupler solvents phenol derivatives and alkanolamines.

When preparing dispersions of color couplers in silver halide emulsions, the procedure is followed Usually in such a way that you first of all the color coupler or color former in a high-boiling solvent dissolves, whereupon the coupler solution in an aqueous gelatin solution using a surface-active Compound is dispersed. The dispersion obtained can then be treated with a photosensitive

"Uberhalogenidemulsion, for example, gelatin-silver halide emulsion, are mixed, after which the extinction ^au f ^emen substrate are applied

The ratio of coupler to solvent is in

advantageous manner, as can be seen, for example, from the

US-PS 23 22 027 results in about ί to 2 or 1 to 3. In

Using some couplers can be a ratio

on coupler to coupler solvent from 1 to 1

Are sufficient. The actual solubility of most

Is coupler in known coupler solvents

However, it is considerably less than what can be seen from the

in the circumstances. In many cases

can in 10 parts of the coupler solvent no more

Is 1 part coupler to be dissolved. As a result, the

coupler solvents dispersed in the emulsions

usually very oversaturated

The relatively large amounts of inert coupler solvents required to dissolve the couplers are disadvantageous, in particular because, on the one hand, the solvent has no direct photographic function, but, on the other hand, impairs the stability of the emulsion layers

For the reasons outlined, there has been no lack of attempts to find ways which make it possible to reduce the amount of solvent to be used. For example, it has become known to Ib from US Pat. No. 29 49 360, 23 04 939, 23 22 827, 28 01 170, 28 01 171, 24 90 749, 35 54 755, 28 35 579 and 25 33 5 K ^{as coupler solvents} to use high-boiling so-called. Icristalloid coupler solvents alone or in combination with a wide variety of removable co-solvents.

Photographic emulsions made using such solvent systems are, for example, in the publication "Product Licensing Index", Volume 92, Publication 9232 of December 1971, Section XXII on page 110, lines 1 through 50.

The object of the invention is to find coupler solvents which can be used for the production of color photographic Recording materials are suitable which are suitable for the production of particularly stable color photographic Images, especially for the production of particularly heat-stable photographic images, are suitable.

The invention was based on the knowledge that extremely effective high-boiling solvents are liquid esters of dibasic cycloalkanols intended for photographic couplers.

The invention accordingly provides a color photographic recording material which is used in at least one silver halide color photographic emulsion layer in finely divided droplets of at least one high-boiling at least one solvent that is practically immiscible with water, contains at least one color coupler dissolved, which is characterized in that the solvent is in the droplets consists at least in part of a liquid ester of the following formula:

R is a straight-chain or branched-chain alkyl radical with 3 to 15 carbon atoms and

η = 0, 1, 2, 3 or 4, with the proviso that the cyclohexylnng is substituted in the 1,3 or 1,4 positions

Particularly useful liquid hydrophobic coupler solvents of the given formula (I) are esters of 1,4-dibasic cyclohexanol, of U-basic cyclohexanol and the corresponding U- and 1,4-hydroxy-ο alkylene derivatives of the following formulas:

R'-CO-O-iCH,)

r "-co-o- (ch ₂ lX η>(")

(CH ₂ LO-CO-R "

where R 'and R "are each straight-chain or branched-chain alkyl radicals having 5 to 8 carbon atoms and η and m are numbers from 0 to 4, preferably 0 to 2 and in particular 1 to 2.

The liquid esters containing cyclohexarine radicals used according to the invention are so-called permanent coupler solvents, ie solvents which permanently remain in the coupler solution droplets which are dispersed in the emulsion layers, in particular silver halide emulsion layers. They differ from so-called low-boiling auxiliary solvents, which consist of low-boiling organic solvents and which have a miscibility with water that does not exceed 6.5 parts per 100 parts of water and whose boiling point is around 76 to 205 ⁰ C and which are described, for example, in US Pat. No. 2,949,360.

The esters described can be used alone in the production of photographic recording materials Coupler solvents can be used, but also together with conventionally known cosolvents of the type described. This means that one in the preparation of coupler-containing silver halide emulsions the couplers in the esters alone or in solvent systems, which are at least in part the esters exist, can dissolve, whereupon the solutions are dispersed in the light-sensitive emulsions.

Permanent coupler solvents particularly suitable for the preparation of photographic materials according to the invention are listed in Tables I and II below. The substituents R ', R ", η and m listed in the tables on the one hand and R'", R ⁴ , π and η on the other hand result from the formula diagrams preceding Tables I and 1.

R-CO- O-

mean:

(D

(CIi ₂ ) "- O-CO-R

" ^s R '" - CO-O- (CH ₂ L- <H> (HD

"I.
(CH ₂ LO-CO-R "

Table I.

R "

Permanent coupler R- the same the same solvent CH ₃ (CH ₂ J ₃ CH- the same 1 CH ₃ (CH ₂ J ₄ QH ₅ CH ₃ (CH ₂ J ₁₀ 2 CH ₃ (CH ₂ J ₂ CH- - QH ₅ 3 CH ₃ (CH ₂ J ₂ CH- - QH ₅ - 4th - 5 6th 7th 8th 9 10 11th 12th 13th

0 -

0 -

4th - - 0 - 1 4th 0 - 0 - 0 1 - 4th 0

CH ₃ (CH ₂ J ₃ -

CH ₃ (CH ₂ J ₂ CH-

C ₂ H ₅

the same
the same
CH ₃ (CH ₂ J ₃ CH—

C ₂ H ₅

CH ₃ (CH ₂ J ₃ C H-

14 - I.

C ₂ H,

_ CH ₃ (CH ₂ J ₁₁

16 CH ₃ -CH- (CH ₂ J ₂

CH ₃

17 the same.

18 -

19 -

20 CH ₃ -C-

CH ₃

H 0 -

21 CH ₃ (CH ₂ J ₁₁ -C-

R- -CO -O- (CH ₂ ) "- \ H> - (ΓΗ.,) _Β -Ο - ^C ° ^R " _1V R '" -CO-OK IUI ,,, -'M ^(V

: h ₃ (CH ₂ ) "- 0 0 4th - CH ₃ -CH- (CH ₂ J ₂ - 0 CH ₃
the same - 4th 0

Table Il

Permanent coupler- R "
solvent

η m

CH ₃ (CH ₂ U-

23 the same the same 24 the same CH ₃ (CH ₂ U- 25th the same CH ₃ (CH ₂ U- 26th CH ₃ (CH ₂ ) ₂ CH- CH ₃ 27 28 29

CH ₃ (CH ₂ J ₃ CH-

C ₂ H ₅
the same
the same
the same
the same

the same

CH ₃ (CH ₂ ) ₆

CH ₃ (CH ₂ J ₆ -

1 - - 0 - 1 0 - 2 _ 1 - 1

The permanent coupler solvents which can be used in the present invention can be prepared according to processes produce, for example, from the US-PS

27 59 821 are known, i.e. for example by converting an equivalent quinitol (1,4-cyclohexanediol) with 4 equivalent 2-ethylhexaoic acid at 205 to 235 ° C in the presence of zinc dust under azeotropic Distilling off a mixture of water and 2-ethyl-hexoic acid. The desired reaction product can then be distilled off under reduced pressure. In the case of coupler solvent 5, for example collected the portion that boils at a pressure of 0.3 mm at 166 to 189 ° C and from a water-hot liquid

Another suitable synthesis method consists in the conversion of 1,4- or LS-cyclohexanedialkanol with an excess of an alkanoic acid having 6 to 13 carbon atoms in the presence of a platinum or Zinc catalyst. After the reaction, the reaction product obtained is distilled off under reduced pressure, neutralized with dilute sodium hydroxide solution, filtered and decanted, whereupon the neutralized Product is dried and subjected to molecular distillation.

The esters described can be used as coupler solvents for a wide variety of conventional known ones Use color couplers.

Typical color couplers which provide non-diffusing blue-green dyes and which can be found in the inventive The coupler solvents used are, for example, from US Pat. No. 23 73 293, 24 23 730 ,,

28 01171. 28 95 82f., 29 08 573, 30 46129, 3516 831, 3311476, 32 53 294, 34 58 315, 32 27 550, 34 76 563, 34 58 315,34 19 390 and 30 34 892 known

Typical non-diffusing, crimson dyestuffs producing color couplers, which are in the invention Let solvents used dissolve, for example from the following US-PS: 26 00 788, 28 01171, 29 83 608, 29 08 573, 32 52924, 3311476, 32 27 550, 3519 429, 34 32 521, 3419 391, 32 27 554, 34 08 194, 32 14 437, 31 52 896, 30 62 653 and 30 06 759 and the Belgian patent 7 24 427 known

Typical color couplers which provide non-diffusing yellow dyes and which can be found in the inventive Knppler solvents used can be solved, for example, from the following US-PS: 27 78 658, 28 75 057, 29 08 573, 32 27 550, 32 53 924, 32 27 155, 34 08 194, 34 47 928, 34 15 652, 33 84 657, 33 69 895, 32 65 506 and 32 27 554 known

The esters used according to the invention are also suitable, for example, for dissolving so-called. Liberation Coupler Development Inhibitors.

That is to say, with the aid of the solvents used according to the invention, such solvents can also be used, for example Disperse couplers in silver halide emulsions. Such development inhibitors set free Couplers are for example from US-PS 32 27 554 and 31 48 062 and 36 17 291 and DT-OS 18 00 420 known

For the production of the color photographic recording materials according to the invention, non-diffusing couplers are generally used in such amounts that there are 5 to 200 mg of coupler _{per emulsion layer on a substrate area of 0.0929 m 2.} In general, concentrations of 10 to 50 mg per 0.0929 m ^{2 have} proven fully satisfactory. If so-called development inhibitor liberating couplers are used in addition to 2- and / or 4-equivalent dye-forming couplers, it has been found that the development inhibitor liberating couplers are expediently in concentrations of about 5 to about 30 mol%, based on the amount

the 2- and / or 4-equivalent color couplers used are used

The recording materials according to the invention contain several in a particularly advantageous manner Silver halide emulsion layers.

The recording materials according to the invention are advantageously composed of:

(A) a layer support, for example the one from the publication "Product Licensing Index", Volume 92, Publication 9232 (December 1971), Section 10 of known type, e.g. B. a support from a Cellulose acetate, polystyrene, polyethylene, polypropylene, polyethylene terephthalate film and the like;

709519/238

(B) a red-sensitive, a green-sensitive and a blue-sensitive silver halide emulsion layer, as they are known, for example, from the publication "Product Licensing Index", volume 92, Publication 9232, December 1971, p. 107 (Sections I and III) and pages 108 and 109 (Section XV), the silver halide being the Silver halide emulsions e.g. B. of silver chloride, silver bromide, silver chloride bromide, silver bromide iodide, Silver chloride bromide iodide or silver chloride iodide, and it is understood that such Emulsions can contain the usual known additives, for example also so-called discoloration-preventing Compounds such as are known, for example, from US Pat. No. 2,865,752;

(C) one or more gelatin interlayers between the photosensitive emulsion layers and also a Carey Lea filter layer, such intermediate or separating layers optionally also removable additives to further improve the dye stability and the color separation can have and

(D) a conventional gelatin topcoat.

The following examples are intended to further illustrate the invention.

example 1

(A) First, a photosensitive gelatin-silver halide emulsion was made manufactured. To this end, first 20 g of 2- [a- (2,4-di-tert-amylphenoxy) acetamido] -4,6-dichloro-5-methylphenol were added (See. US-PS 24 23 730) in g of di-n-butyl phthalate in the presence of 30 ml Isopropyl acetate dissolved as an auxiliary solvent. The resulting solution was then poured into a solution of 181 j a 10% aqueous gelatin solution in the presence of an Aikylnaphthalinsulfonat sodium salt as above area active connection given. The mixture was then emulsified in a colloid mill quenched, washed with water and dried for the purpose of removing the auxiliary solvent. the The melted dispersion was then mixed with a photosensitive gelatin-silver chlorobromide emulsion

ίο sion mixed. In this way a test emulsion was obtained which was applied to a layer substrate in such a way that a layer substrate area of 0.0929 m ² accounted for:

136 mg silver, 450 mg gelatin and 78 mg coupler.

The coated recording material obtained is referred to as recording material A in the following was then exposed sensitometrically to a standard Tyf Eastman IB sensitometer, whereupon there; Record material developed in a conventional manner to produce a cyan dye record was celt. The blue-green dye image obtained with a neutral density of 1.5 was then said to be «heat stability at 77 ° C and a 40% relative Humidity tested. The duration of the test, i.e. H. dit time span in which the recording material dei Exposure to a temperature of 77 ° C lasted a week. The resulting loss of density results in from the following Table III.

(B) A further; Recording material, hereinafter referred to as record material B designates, as described under (A), with the exception, however, that al: permanent coupler solvent the solvent no. 5, namely quinitol di (2-ethylhexoate) instead of before Di-n-butyl phthalate was used. The loss of density of the developed cyan recording image is also shown in Table III below.

Table III Versuchsmaierial Coupler solvents

ratio of Coupler too solvent

Loss of density

A (comparison Di-n-butyl phthalate 1: l / 2 0.54 example B. Quinitol di- (2-ethylhexoate) (solution 1: l / 2 0.28 medium No. 5)

Example 2

According to the method described in Example 1, further recording materials were produced, using three different coupler solvents, namely di-n-butyl phthalate, tri-

nitol di (2-ethylhexoate) and 1,4-cyclohexyldimethylene bis- (2-ethylhexoate), the ratio of Kupple to solvent being varied and 1: 3.1: 2.1: 1 to 1: '/ 2 was. The results obtained are summarized in Table IV below

Table IV Test material coupler solvent

ratio of Coupler too solvent

Loss of density

C (comparison)
D (comparison)
E (comparison)

Di-n-butyl phthalate
the same
the same

1: 3 0.09 1: 2 0.18 1: 1 0.17

T 23 26 590 12th Vcrhillinis of IJii'hlcverlus π ' <iipplcr / H
. <iSllll | .'SllliUL'l VerMichsniaicrial KiipplcrWisimgsmitici : l / 2 0.21 0.02 F (comparison) Di-n-butyl phihalate 0.05 G Quinitol-di (2-ethylhcxoai) 0.10 H the same 0.15 1 the same 0.09 J the same 0.36 K. (comparison) Di-n-butyl phthalate 0.10 L (comparison) the same M. 1,4-cyclohexyldimethylene-bis- 0.02 (2-ethylhexoate) (solvent no.6) 0.09 N the same 0.14 O the same } P. the same 2 1 1/2 1/2 1 3 1 1/2

Example 3

(A) Another multilayer color photographic recording material was produced with the following structure: (the following concentration data relate to a layer support area of one Dm ² ):

(A) a cellulose acetate support;

(B) a blue sensitive silver bromide iodide emulsion layer with 1 mol% iodide with 6.6 mg Ag, 36 mg gelatin and 13.5 mg oc- {3- [a- (2,4-di-t-amylphenoxyj-butyramidojenzoyl ^ -methoxyacetani-Hd and 27 mg of di-n-butyl phthalate as a coupler solvent;

(C) an intermediate gelatin layer containing 6.2 mg gelatin;

(D) a red sensitive silver chlorobromide emulsion layer with 20 mol% bromide and 4.3 mg Ag, 31 mg gelatin and 12.1 mg 2 - («- Di-amylphenoxyn-butyrylamino) -4,6-dichloro-5-methylphenol and 24.2 mg of di-n-butyl phthalate as a coupler solvent;

(E) an intermediate gelatin layer containing 6.2 mg gelatin;

(F) a green-sensitive silver chloride bromide emulsion layer with 20 mol% bromide and 8.6 mg Ag, 24 mg gelatin and 19 mg 1- (2 ', 4', 6'-TnChIOrPhC-

nyl) -3- [3 "- (2"',4'"- di-tert-amyl-phenoxyacetamidoj-benzamidojo-pyrazolone and 38 mg of di-n-butyl phthalate as coupler solvent and

(G) a gelatin topcoat with 93 mg gelatin.

The recording material was exposed in a conventional Eastman IB sensitometer and then processed in the conventional manner. The stability of the blue-green dye in which the material! Was exposed to a temperature of 77 ° C with a relative humidity of 40% for a week. The density loss with respect to red light was determined for a neutral image with a density of 1.5.

(B) A second recording material was produced as described under (A), with the exception, however, that coupler solvent No. 6 was used in the D layer instead of di-n-butylnaphthalate as the coupler solvent.

The difference in density loss between recording materials A and B was practically the same the loss of density, which results from Table I of Example 1

Example 4 (comparative example)

Following the procedure described in Example 1 8 different color couplers, 2- [a- (2,4-di-tert-amylphenoxy) -butyramido] -4,6-dichloromethylphenol, which produce a blue-green dye containing SiI berhalide emulsions produced The produced Emulsions differ in the coupling solvents used for their production, which are used in are listed in the following table. As an auxiliary solution

jo agent, which was removed again when the emulsions were washed, 2- (2-butoxyethoxy) äthylacctat was used. The coupler dispersions initially prepared were mixed with glatine silver bromide emulsions. The silver halide emulsions containing the color coupler were applied to cellulose acetate layer support in such a way that a support area of 0.0929 m ² accounted for: 42 mg of Ag; 74 mg of color coupler and 350 mg of gelatin. The recording materials were exposed in a sensitometer type Ib Eastman and then developed in the usual way, the development was carried out by 2minütigcs development at 4O ⁰ C in a developer of the following composition:

Potassium sulfite 2.0 g Potassium carbonate 3.0 g Potassium bromide 1.25 g Potassium iodide 0.6 mg 4-Atnino-3-methyl-N, N-di & thylaniline, HCl salt 2.45 g Made up to 1 liter with water, pH-11

After development , the dilution materials were bleached in a leftover ferricyanide bleach bath and then fixed in a conventional sodium thiosulfate fixer

The developed Aufzeichmmgsmatcrialien were for the purpose of determining the Bcstindigkeit cyan dye tang 21 days at a relative humidity of 70%, "a temperature nd of 60 ⁰ C kept After the loss of density of an image district with a density of IJO before performing the StabilitStstcste was · to red light determined The data obtained «te4 contained in the following table:

13 ^w 14

Recording Coupler solvents ratio of Density loss material no. Kupp'er too solvent 1 1,4-cyclohexylenebis (2-ethylhexanoate) 1: l / 2 0.00 2 the same 1: 3 0.01 3 1,4-cyclohexylene-dimethylene 1: l / 2 0.00 bis (2-ethylhexanoate) 4th the same 1: 3 0.02 5 2,4-Di-n-amylphenol according to US Pat. No. 2,835,579 1: l / 2 0.47 6th the same 1: 3 0.84 7th Methylethanolamine butyramide according to 1: l / 2 0.11 U.S. Patent 3,554,755 8th the same 1: 3 0.13

Claims (1)

Patent claims: 1. Color photographic recording material in at least one color photographic Silver halide emulsion layer in finely divided droplets of at least one high-boiling point with Water contains practically immiscible solvent at least one color coupler dissolved, characterized in that the solvent in the droplets consists at least in part of a liquid ester of the following formula: