DE2214489A1 - Color photographic recording material - Google Patents

Description

22-89

Color photographic recording material

The invention relates to a color photographic recording material having at least one silver halide emulsion layer having one upon color photographic development a color coupler providing a cyan dye.

It is common knowledge to take color photographic images Use of color photographic recording materials and so-called. Color couplers, which with the oxidation products of coupling developer compounds consisting of primary aromatic amines. Noraalweise will be there the subtractive color formation process is applied, the coupling of the oxidized color developing agent with the couplers, dyes normally produced the complementary primary colors of cyan, magenta, or show yellow.

The couplers used to generate the dyes are typically either phenolic or naphtholic Compounds, pyrazolone compounds or benzoylacetamides.

The majority of the previously known color couplers are so-called. 4-equivalent color couplers, which are used to produce a Dye molecule through coupling reaction with the oxidized one Color developer the development of four exposed silver halide molecules require.

Furthermore, so-called 2-equivalent color couplers have become known which differ from the known 4-equivalent color couplers learn by deriving that the coupling position / the 4-equivalent color coupler are substituted by non-chromophoric coupling-off groups. This 2-equivalent color coupler are characterized in that they are used to develop a

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Dye molecule require the development of only two exposed silver halide molecules.

2-equivalent color couplers are, for example, from the USA patents 3,458,315 and 3,277,155 are known.

Although the 1-equivalent color coupler thus has advantages over have the 4-equivalent color couplers, the 2-equivalent color couplers could the 4-equivalent color couplers to not fully displaced today, namely because the production of color photographic recording materials suitable color couplers must have a number of specific characteristics.

It is essential for the suitability of color couplers that they are suitable for the production of thin photographic recording materials are suitable, are stable and stable photographic dyes with very special spectral absorption characteristics able to form. It is also important that the couplers work in a homogeneous manner in silver halide emulsions without affecting the viscosity of the emulsion, the adhesion of the emulsion to the support or the uniformity of the emulsion during the coating process, e.g. with the usual high-speed

influence.

coating process disadvantageous kKciitf & MftXk So it is, for example known on a film support including an antihalation layer and gelatin interlayers apply up to 8 or more coats. Reference is made, for example, to Kirk-Othmer, "Encyclopedia of Chemical Technology ", Volume 5, Pages 812 to 845. In view of the complicated coating process, couplers changes caused in the adhesion and coating properties of the photographic layers are not tolerated will.

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Ira remaining is the order of the arrangement containing the couplers Layers in such a recording material are also important, specifically with regard to the absorption properties of the dyes to be produced.

The color couplers can be incorporated into the photographic emulsions in various ways. A common one The method is to use color couplers which contain a water-solubilizing group. These color couplers can be in the form of a solution directly into a gelatin-silver halide emulsion be incorporated. According to another method, the couplers are high-boiling and / or low-boiling Dissolved organic coupler solvents and incorporated into the silver halide emulsions in the form of these solutions. Such methods are, for example, from US Patents 2,949,360, 2,304,939, 2,322,827, 2,801 and 2,801,171 known. It has proven to be particularly desirable to use such color couplers which are only low Require amounts or virtually no high boiling solvents because of the thickness (i.e. optical opacity and the resolving power) and the persistence of the h / er ~ The photographic recording material provided is directly influenced by the concentration of the solvent used will.

It has been shown that, with a few exceptions, this is not possible due to the molecular structure alone for a color coupler predict a desirable combination of coupler properties.

For the production of color photographic recording materials with at least one silver halide emulsion layer with one in color photographic development a blue-green

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Dye-supplying color couplers Suitable blue-green dye-supplying color couplers are, for example, from the U.S. Patents 2,474,273; 2,275,292; 2,895,826; 2,908,573; 3,148,062; 3,311,476; 3,227,551 and 3,227,554 are known.

The disadvantage of the known color couplers is that their heat and light stability not yet fully satisfied.

The object of the invention was therefore to provide color photographic recording materials having at least one silver halide emulsion layer having one upon color photographic development to indicate a cyan dye-producing color coupler that easily interacts with the oxidation products of developer compounds consisting of primary aromatic amines, in particular oxidized aryldiamines, for example Phenylenediamines couples while providing non-diffusing dyes of excellent stability and with desirable properties Light absorption spectrum supplies. The color couplers should also be very reactive and color photographic Provide images with a high resolution without causing undesired changes in the viscosity of the emulsions before or to lead after their application on a film support. Finally, the color couplers should be converted into conventional silver halide emulsions incorporate using minimal concentrations or virtually no coupler solvent permit. /

The invention was based on the finding that color couplers with the properties described are used to form blue-green dyes then obtained when one of the usual phenolic and naphtholic blue-green dyes yielding color couplers goes out and this in the 4-position by a heterocycloxy

/ ~ The object of the invention was also to find appropriate developer solutions indicate applicable couplers.

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group substituted.

The subject of the invention is thus a color photographic A recording material having at least one silver halide emulsion layer with a color photographic development a color coupler providing a blue-green dye of one of the formulas:

II.

X Y

III.

OH

0 R

Rr

or

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where mean:

R is a cyclic radical;

R, a hydrogen atom or an alkyl radical;

R ^ is a hydrogen atom or an optionally substituted one Aryloxy radical;

R _{5 is} a hydrogen atom or an alkyl radical;

R _{6 is} an alkyl, optionally substituted aryl or optionally substituted aryloxy radical; "

X is a hydrogen or halogen atom;

Y represents a hydrogen atom or an alkyl, alkoxy or alkylthio radical;

1λ the atoms required to complete a heterocyclic ring with 5 or 6 ring atoms;

η »0, 1, 2, 3, 4, 5, 6, 7 or 8; m »0 or 1

which is characterized in that the silver halide emulsion layer contains a color coupler of one of the specified formulas I to III, in which R is a radical of the formula:

ι \

1 I.

is where Z is the one to complete a heterocyclic Ring with 5 or 6 ring atoms represents the required atoms.

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The invention also provides a color developer solution containing one of Couplers I to III.

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If R _{3 is} an alkyl radical, this preferably consists of a short-chain alkyl radical having 1 to 8 carbon atoms, for example a methyl, isobutyl or octyl radical.

If R _{4 has} the meaning of an optionally substituted aryloxy radical, this preferably consists of an optionally substituted phenoxy or naphthoxy radical, for example a phenoxy radical substituted by an alkyl radical, the alkyl radical preferably having 1 to 15 carbon atoms and optionally being a branched-chain alkyl radical, in which case R. can be, for example, a phenoxy group substituted by two short-chain tertiary alkyl groups.

If Rr has the meaning of an alkyl radical, this exists preferably from a short-chain alkyl radical with 1 to carbon atoms.

If R _{6 is} an alkyl radical, this preferably has 1 to 20 carbon atoms. The alkyl radical can also consist of a cycloalkyl radical, in particular one with 4 to 6 carbon atoms, for example a cyclobutyl or cyclohexyl radical.

If R ^ has the meaning of an optionally substituted one Aryl radical, this can preferably consist of a radical from the phenyl or naphthyl series. In this case, R, for example, an alkylcarbonamidophenyl group, e.g., a phenoxyalkylcarbonamidophenyl group with a short chain Alkyl group or / a dialkylphenoxyalkylcarbonamidophenyl radical with short-chain alkyl groups or an alkoxyphenyl radical or a dialkoxyphenyl radical with alkyl groups with up to

/Consist of

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about 20 carbon atoms, furthermore a carboxyphenyl radical including a dicarboxyphenyl radical. Furthermore, the aryl radicals represented by R, - can have several different substituents, ie Rg can also consist of an alkoxy-alkylphenyl radical, for example. If R _{6 has} the meaning of an optionally substituted aryloxy radical, this preferably consists of an optionally substituted phenoxy radical, which can in particular be substituted by one or more alkyl radicals, ie R can, for example, be a phenoxy radical substituted by an alkyl radical, in which case the alkyl groups are preferred can have up to 20 carbon atoms and can consist of straight-chain or branched-chain alkyl radicals »be.

If X has the meaning of a halogen atom, this can be, for example consist of one chlorine atom.

If Y has the meaning of an alkyl radical, this can, for example, consist of an alkyl radical with 1 to 18 carbon atoms exist, for example a methyl, octyl or octadecyl radical. However, the alkyl radical preferably has 1 to 8 carbon atoms. If Y has the meaning of an alkoxy or alkylthio radical, thus the alkyl group of this radical preferably has 1 to 15 carbon atoms. Preferably is the alkyl group These radicals are short-chain, i.e. they have 1 to 8 carbon atoms and consist of a methyl, isopropyl or Octyl group.

η is preferably a number from 0 to 6, in particular from 2 to 4.

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The radical represented by R is preferably an unsaturated, unconjugated heterocyclic radical with at least a nitrogen, oxygen or sulfur heteroatom, preferably with 1 to 4 hetero nitrogen atoms. Of the heterocyclic ring represented by R can optionally be substituted or to other cyclic compounds or residues may have condensed.

R is preferably a tetrazolyl, benzoxazolyl, imidazolyl, benzimidazolyl, benzothiazolyl, furyl, pyrryl, thienyl, Benzofuranolyl, isoindolyl, pyranyl, benzopyranyl, oxazinyl, oxazolyl or thiazolyl radical.

The heterocyclic rings represented by R can, for example by halogen atoms, e.g. chlorine atoms, furthermore nitro or aryl radicals, in particular of the phenyl series, furthermore by alkyl radicals with in particular 1 to 20 carbon atoms, furthermore by alkylamido radicals, e.g. methyl or butylcarbonanido radicals, finally, alkylcarbonamidophenyl radicals, including phenoxyalkylcarbonamido radicals with short-chain ones Alkyl groups with in particular 1 to 8 carbon atoms, e.g. m-alkylphenoxyalkyl radicals, alkoxy radicals, alkylsulfonamido radicals, Alkylcarbamyl radicals, where the alkyl groups of these radicals can preferably have up to 20 carbon atoms, as well as amino groups may also be substituted.

Zj can, for example, be used to complete an oxazinyl or atoms having morpholino radicals.

In addition, all of the specified substituents, with the exception of the substituent R, can be those from the prior art have known meaning.

For the production of a color photographic recording material according to the invention suitable to provide a blue-green dye

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de color couplers are for example:

Coupler No. 1: 3-methylthio-4- (1'-phenyl-5-tetrazolyloxy)

phenol

OH

N N

I I

Coupler No. 2:

6-Acetamido-2-chloro-3-methyl-4- (1'-phenyl-5 tetrazoIyloxy) phenol OH

Cl

CH

NHCOCH.

N N

I I

Coupler No. 3:

o-Acetamido-Z-chloro-S-methyl- ^ benzoxazolyloxyphenol

OH JJ

NHCCH,

CH

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- rr-

Coupler No. 4:

6- [~ - (2 ', 4'-Di- (t) -amyl-phenoxy) -propylcarbonamido ^ -chloro-S-methyl ^ -benzoxazolyl-

oxyphenol
OH

Cl

CH

NHCfHO

^C 2 ^H 5

C ₅ H ,, - t

Coupler No. 5:

6- Iα- (2 ', 4'-Di-amyl-phenoxy) -propylcarbonamido 7-2-chloro-3-methyl-4- (1'phenyl-5'-tetrazoloxy) phenol OH

Coupler No. 6:

N - C, H.

D 5

1-Hydroxy-2- / N- (2 ', 4'-di- (t) -amylphenoxy) -butyl? -4- (1-phenyl-5'-tetrazoyloxy) -2-naphthamide OH

CONH (CH ₉ ) "0-" ^

N NC ₆ H ₅

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- tr -

Coupler No. 7:

i-Hydroxy-4- (benzoxazolyloxy) -N- / 4- (2 ', 4' -di (t) -amylphenoxyacetamido) -phenyl_7ethyl-2-naphthamide
OH

: ONH (CH ₂ ) ₂ - / V-NHCOCH ₂ OT Ί

Coupler No. 8: 1-Hydroxy-4- (2-benzimidazolyl) -N, N-dioctyl-2-

naphthamide

CON

^C 8 ^H 17 ^C 8 ^H 17

Coupler No. 9:

i-Hydroxy-4- (2-benzothiazolyloxy) -2 '- (tetra de cy1oxypheny1) -2-naphthamide

CONH

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Coupler No. 10:

1-Hydroxy-4- (2-furyloxy) -2 ~ _i / ~ N-octadecyl-N- (3 ·, 5 ^f -dicarboxyphenyl 7naphthamide

COOH

Coupler No. ti: 1-Hydroxy-4- (2-pyrrylyloxy) -N-octadecyl-2-

naphthamide

CONHC ₁₈ H ₃₇

Coupler No. 12:

1-Hydroxy-4- (5-dodecyl-2-thienyloxy) -2-nap thomorpholide

^CH

CON

CH

2 \

^C 12 ^H 25

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Coupler No. 15:

1-Hydroxy-4- (S-octadecyl-S-benzofuranyloxy) N-cyclohexyl-Z-naphthamide

OH

^C 18 ^H 37

Coupler No. 14

1-hydroxy-4- (2-isoindolyloxy) -N- (2-benzimidazoly5; buty1-2-naphthamide OH

CONH (CH ₂ ) ₄ -C

Coupler No. 15:

1-Hydroxy-4 ~ ^ 2 (H) -4-benzopyranyloxY7-N- (2-hexadecyloxy-5-methylphenyl) -2-nap! Thamide

OH

^OC 16 ^H 33

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Coupler No. 16:

1-Hydroxy-4- / ~ 3- £ uryloxy_7 ~ N "(2-decyloxy-4 · methoxy) phenyl-2-naphthamide

CONH

OCH

Coupler No. 17:

1-Hydroxy-2- ^ ~ N- (2-acetamidophenyl) -äthyl_7-4 - / "i- (3-ία- {3'-pentadecylphenoxy} -propyl} -carbonamido) phenyl _ / - 5-tetrazolyloxy-2-naphthamide

NHCOCH

Coupler No. 18: 1-Hydroxy-4- / ~ 2- (1,3-oxazinyl) oxy_7-N-

2,4-di-tertiary-amylphenoxy) butyl-2-naphthamide

0 N

Coupler No. 19;

1-Hydroxy-4- (2-oxazolyloxy) -N- (-2,4-di-tertiary-amylphenoxy) butyl) -2-naphthamide

OH

: OH (CH ₂ ) 40

Coupler No. 20: 1-Hydroxy-4- (2-imidazolyloxy-N / "- 4- (2 ·, 4» -

di - (t) -amylphenoxyacetamido) -phenyl_7 ~ ethyl-2-naphthamide

ONH (CH ₂ ) -Ä > NHCOCH ₂ OP}> - C ₅ H ₁₁ (n)

C ₅ H ₁ , (η)

N N-H

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Color couplers which provide further advantageous blue-green dyes for the production of a color photographic recording material according to the invention are:

21. 1-Hydroxy ~ N- / ~ β- (2 ^f -acetamido) phenethyl7-4-2 »- / ~ 3" - (2-carboxy) -3-eicosenylamido-7-phenyl-tetrazolyloxy-2-naphthamide; (mp = ■ 145 - 148 ⁰ C).

22. 1-Hydroxy-N - / "ß- (2 ^l -acetamido) phenethyl_7-4- {2 ¹ - /" 3 "- (2,4-di-n-amylphenoxy) acetamido_7phenyltetrazolyloxy>-2-naphthamide; ( M.p.-212 ^° C).

23. 1-Hydroxy-N- ^ "ß- (2'-acetamido) phenethyl_7-4- {2 ¹ - /" 3 "- (2,4-di-t.-amylphenoxy) acetamido ^ / phenyltetrazolyloxy} -2 -naphthamid; (mp = 180-182 ⁰ C).

24. 1-Hydroxy-N - / "ß- (2'-acetamido) phenäthyl_7-4- (2 · - /" 3 ^M -

(2-carboxy) eicosanido (7-phenyltetrazolyloxy) -2-naphthamide; (Mp = 130-140 ⁰ C).

25. 1-Hydroxy-N- / ~ 6- (2,4-di-t.-amylphenoxy) -butyl_7-4- / ~ 2 · - (5-aminobenzothiazolyloxy) _7-2-naphthamide; (mp = 195 - 198 ⁰ C).

26. 1-Hydroxy-N- ^ ~ 6- (2,4-di-t.-amylphenoxy) -butyl_7-4- / ~ 2 '- (5-nitrobenzothiazolyloxy) _7-2-naphthamide; (m.p. 145 - 147 ⁰ C).

27. 1-Hydroxy-N - / 'β- (2 ^l -acetamido) phenethyl 7-4- ^ "2 · - (3-hexadecylsulfonamido) phenyltetrazolyloxy-7-2-naphthamide; (m.p. - 190-192 ° C).

28. 1-Hydroxy-N- / ~ 6- (2,4-di-t-amylphenoxy) -butyl_7-4- ^ ~ 2 · - (3-aminophenyl) tetrazolyloxy_7-2-naphthamide; (Mp »120 -122 ⁰ C)

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is

29. 1-Hydroxy-N- / ~ ß- (2 ^f -acetamido) phenäthyl_7-4- {2 '- {3 "- ^" a- (2,4-di-t.-amylphenoxy) butyramido_7phenyl} tetrazolyloxy} -2-naphthamide; (Mp »173-176 ⁰ C).

30. 1 -hydroxy-N - ^ "ß-2 · acetamido) phenäthyl7-4- {2 '- {3" - ^ ~ ct- (2,4-di-n-amylphenoxy) butyramido_7phenyl} tetrazolyloxy} -2- naphthamide; (M.p. - 185-187 ° C).

Manufacture of the coupler

For the production of a color photographic recording material Color couplers which are suitable according to the invention and provide a cyan dye can be, for example Manufacture according to the following procedures:

As a particularly advantageous method for producing the Coupler has been found to be a process in which the following acid (A) under the conditions shown in the following reaction scheme with a heterocyclic Chlorine compounds, Cl- (Het.) Is reacted in dimethylformamide. The intermediate compound resulting from this conversion (B) is then reacted with phenol to form the intermediate compound (C), which in turn with heating to form the amine (D) the desired coupler is reacted.

(A) Y

(B) + HO

+ NaOH + Cl- (het.)

Dioxane

DMF

POCl.

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(C) + NH

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OH

ν _-

CONR ₁ R ₂

0 (het.)

Coupler

Y represents the completion of a polycycli see ring system required atoms, for example a naphthol or quinolinol ring.

The preparation of color coupler no. 2 can be illustrated, for example, by the following reaction scheme

CH-C, H_ Z ο 5

NHCOCH.

N-

.H-5

K ₉ CO

acetone

OCH ₂ C ₆ H ₅

NHCOCfl.

N NC ₆ H ₅

NHCOCH.

(Fp = 199 ⁰ C)

N == N

N-

= N

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By using the corresponding 4-benzoxazolyloxy, 3-methylthio or tetrazolyloxy analogues of the reactant indicated above and hydrogenating in tetrahydrofuran as solvent, couplers No. 3 (Fo = 22 7 ° C.) and No. 4 (mp = 194 ⁰ C) manufacture.

The preparation of the color coupler No. 6 can be represented by the following reaction scheme:

, N - N

+ 2NaOH + Cl-

"N N

^C 6 ^H 5

To a solution of 20.4 g (0.1 mol) of the acid (A) in 250 ml of dimethylformamide and 28 ml of 40% NaOH (0.2 mol) were added 18 g (0.1 mol) of 5-chloro-1 with stirring -Phenyltetrazole added. The mixture was stirred for 6 hours and then poured into 600 ml of cold water, whereupon it was acidified with concentrated HCl. The solid precipitate, ie the intermediate compound (B), was separated off and suspended in 600 ml of cold water, filtered off, washed again with cold water and recrystallized from acetonitrile. It decomposed at a temperature of 215 ⁰ C.

Intermediate compound (B) + HO

d Λ

O ₂ C ₆ H,

N = N

(C)

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A mixture of 22 g (0.063 moles) of intermediate compound (B), 150 ml of dioxane (dry),? g of phenol and 5 ml of POCl ₃ were heated to reflux temperature for 3 hours and then left to stand for 48 hours. After adding 10 ml of H ₂ O, a precipitate separated out, ie the intermediate compound (C) which was separated off, washed with water, air-dried and recrystallized from acetonitrile. (M.p. - 153-155 ° C).

Intermediate compound (C) + NH ₂ (CHp ₄ O- ^ VC ₅ H ₁₁ (t) (D)

C ₅ H ₁₁ U)

160

ONH (CH ₂ ) ₄ O- ^

NC ₆ H ₅

= Coupler no.6

A mixture of 11.88 g (0.028 moles) of intermediate (C) and 9.42 g (0.0308 moles) of the amine (D) was heated to 160 ⁰ C. The phenol developed in the process was separated off by distillation. The reaction mixture was cooled, dissolved in 250 ml of hot ethyl acetate and washed 2 with H-, 0. The organic phase was _{dried over MgSO 4} , evaporated to dryness, dissolved in hot ethanol, cooled and recrystallized. The solid reaction product, ie coupler no. 6, was separated off and washed with a little ethanol. The yield was 12.5 g, corresponding to 70.25% of theory. The melting point of the color coupler was 130 to 132 ° C.

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By reaction of the 5-Chlorotetrazols with 1,4-dihydroxy-2-naphthoic acid, and reacting the intermediate compound obtained with phenol and 2-Acetamidophenyläthylamin in the manner described can be of the color coupler No. 17 having a melting point of 183 - Prepare 185 ⁰ C.. This compound can also be prepared, for example, by reducing the corresponding i-nitrophenyl-4-chloro-tetrazolyl compound and reacting the amine obtained with an acid chloride.

The color couplers used for the production of a color photographic recording material according to the invention differ are particularly advantageous from structurally very similar color couplers, such as those from the USA patents 2,474,273, 2,275,292, 2,895,826, 2,908,573, 3,148,062, 3,311,476, 3,227,551, and 3,227,554 are known.

The color couplers used according to the invention are distinguished by a particular stability of the blue-green produced Dye images and furthermore by a precise, precise spectral absorption range of the dyes produced. Furthermore, the color photographic recording materials according to the invention are characterized in that the Degree of copying out or disintegration of unreacted color coupler residues in the photographic material in particular is low, especially in comparison to known 2-equivalent color couplers without the use of relatively high concentrations of development reaction inhibitors is required.

The color photographic recording materials according to the invention can moreover be those known for customary color photographic materials Recording materials usual structure

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St.

sit, This means that they can consist, for example, of a conventional substrate, an antihalation layer and one or more photosensitive silver halide emulsion layers, one providing a cyan dye Contains color coupler. The recording material can also have silver halide emulsion layers in the customary known manner with a magenta dye-forming color coupler and a yellow dye-forming color coupler. Finally, the recording material can have intermediate and / or outer layers in the usual way. For the production The usual known binders can be used for the individual layers can be used, in particular gelatin and gelatin derivatives, but also, for example, mixtures of gelatin and poly-N-vinyl lactane, gum arabic, also hydrophilic Copolymers of N-acrylamidoalkyl betaine (see USA patent 2,833,650), cellulose ethers and cellulose esters, also alkali-soluble polyvinyl phthalates (see USA patent 2 798 004), also water-soluble polymers with various. Degrees of solubility, e.g., polyvinyl alcohol, are more advantageous Way with a surface-active compound, polyvinylpyrrolidone, polyalkylene oxides, polyvinyl alcohols, and derivatives of the same, e.g. partial esters of polyvinyl alcohol, Ethers and acetals, for example hydrolyzed polyvinyl acetates, polyvinyl acetate aldehyde acetals, polyvinyl butyraldehyde acetals, also polyvinyl-sodium-o-sulfobenzaldehyde acetals, also polyvinyl disodium-2,4-disulfobenzaldehyde acetals and water-soluble copolymers and mixed polymers, for example of methyl vinyl ether and maleic anhydride, also from acrylic acid, methacrylic acid ethyl ester and maleic anhydride and finally Maleic anhydride, acrylic acid and vinyl acetate.

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The top layers can optionally contain further additives, e.g. buffer substances (for example an acidic or a basic compound). or ultraviolet light absorbing compounds, for example 2,2'-dihydroxy-4, 4'-dimethoxybenzophenone, 4,4'-diazidostilbene-2, 2'-disulfonic acid, Sodium salt and / or sodium (a-phenylhydrazone).

The couplers used in the present invention can be in one or more of the emulsion layers or interlayers of the color photographic recording material according to the invention, i.e. a color photographic recording material according to the invention can for example have a structure as it is from the USA patents 2,367,531, 2,474,293, 2 949 360, 2 304 939, 2 322 827, 2 801 170 and 2 801 171 is known. This means that they provide a blue-green dye Color couplers can optionally also be contained in one or more intermediate layers of the recording material can.

On the other hand, some of the dyes used according to the invention can optionally also be used subsequently in the form of diffusing ones Couplers are introduced into the color photographic recording material from a customary color developer solution.

The support of the color photographic recording material according to the invention can be made of one of the known for Color photographic recording materials consist of conventional layer supports, for example a layer support Cellulose acetate or a polyester, e.g. polyethylene terephthalate

lat /, i.e. a layer support, as it is, for example, in the etc.

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Duffin's book "Emulsion Chemistry", Chapter 3, pages 47 to 56 (1966). The support can also for example also consist of a paper layer support or a layer support of another fibrous form Material to which a hydrophobic surface film layer which is water-repellent can optionally be applied and does not absorb or adsorb water. As a substrate with hydrophobic surfaces, which are advantageous Can be used to produce a color photographic recording material according to the invention are those with a hydrophobic resin layer, which may optionally have been irradiated with electrons, in order to prevent the adhesion of the layer onto the substrate applied hydrophilic colloid layers to improve, as it is for example from the British patents 971 058 and 1060 526 and U.S. Patents 2,864,755 and 2,864,756 are suitable.

Such resin films or sheets can either be used as such, i.e. self-supporting or, as already stated, be applied to other substrates. Such supports are of particular advantage with hydrophobic surfaces which have been irradiated with electrons in such a way that the contact angle is below 45 ° (See, for example, US Pat. No. 3,220,842) or the one surface exposed to a corona discharge with a Chromium halide (see, for example, US Pat. No. 3,117,865) or which are paper backings with a hardened gelatin layer exposed to a corona discharge (see Belgian patent specification 671 661).

Optionally, the substrate different functionally effective may contain additives, for example, u ± m titanium dioxide, zinc oxide

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or silica particles, as is known, for example, from U.S. Patents 2,992,101 and 2,701,245 and finally, antistatic compounds, as described, for example, in US Pat. No. 3,253,922 will.

For the production of a color photographic recording material Emulsions used according to the invention can be chemically sensitized in a conventional manner. For example, the emulsions can or can be digested with naturally active gelatin Sulfur compounds are added, such as those in U.S. Patents 1,574,944, 1,623,499 and 2,410,689.

The emulsions may be of the precious metals are also provided with salt treated, for example with salts of ruthenium, rhodium, palladium, iridium and / or platinum, as is known for example from US Patents 1,148,060, 2,566,245 and 2,566,263.

The emulsions used for the production of a color photographic recording material according to the invention can furthermore be optically sensitized in the usual way, for example with cyanine and merocyanine dyes like es for example from US patents 1,846,301, 1,846,302,

1 942 854, 1 990 507, 2 112 140, 2 165 338, 2 493 747, 2 739 964,

2,493,748, 2,503,776, 2,519,001, 2,666,761, 2,734,900, 2,739 and British Patent 450,958.

The emulsions used for the production of a color photographic recording material according to the invention can be contain other compounds that increase sensitivity,

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e.g., quaternary ammonium compounds, e.g., that of the United States patents 2,271,623, 2,288,226 and 2,334,864, or polyethylene glycols such as that of U.S. Patent 2 708 162 known type.

Finally, the emulsions can also be chemically sensitized with gold salts, for example from the USA patent 2 399 803 is known or with GoldÜilzen as is known from U.S. Patents 2,597,856 and 2,597,915, for example. Suitable here Compounds are, for example, potassium chloroaurite, potassium aurithiocyanate, potassium chloroaurate, auritrichloride and 2-aurosulfobenzothiazole methochloride.

The customary known color developer compounds can be used for developing the color photographic recording materials according to the invention can be used, e.g. Ν, Ν-dialkyl-p-phenylenediamines. These developer compounds can optionally have a wide variety of electron-donating substituents, e.g. alkyl, alkoxy and / or alkylamino radicals or other groups in the ortho position to the primary amino group.

Typical color developer compounds suitable for developing the recording materials are, for example:

4-Amino-3-methyl-N-ethyl-N-ß- (methanesulfonamido) ethylaniline, Sesquisulfate hydrate,

4-amino-3-methyl-N-ethyl-N- hydroxyethylaniline sulfate, 4-amino-N-ethyl-N-ß-hydroxyethylaniline sulfate, 4-amino-3-methyl-N, N-diethylaniline hydrochloride and p-amino-NjN-diethylaniline hydrochloride.

209 B A 1/1068

221U89

The following examples are intended to illustrate the invention in more detail.

example 1

Color coupler No. 2 and the color coupler 6-acetamido-2,4-dichloro-3-methylphenol analogous to this color coupler following formula (color coupler no.2A):

NHCOCH

Cl

For comparison purposes, their reactivity with oxidized color developing agent was tested, the relative degree of deamination being determined as a function of the dye formation with oxidized color developing agent, as is known, for example, from the journal JACS Jl (1957) page 583 and JACS £ 2 (1960), page 19S8 is.

Five color coupling solutions were prepared that were 0.002 to 0.004 molar and had a pH of 11 using a phosphate buffer (u-0.75). The solutions were ^{mixed at 25 °} C. with K ₃ Fe (CN) ₆ and 4-amino-3-methyl-N-ß-sulfoethylaniline. The XMax density and the pH of the reaction mixture were then determined immediately. Taking into account the relative ionization of the couplers, a curve 1 / D versus J ₇ ^ was plotted, D being the color

209841/1068

221U89 30

is density and (C) the coupler concentration to give the slope of the curve and the Y-section values. The values determined in this way and the relationship between the rate of deamination and the pH of the reaction mixture (cf. Reference J.A.C.S. £ 2, (1960) page 1988) goes into the following formula:

Slope χ section

where K is the coupling constant and K ^ is the deamination rate constant, thereby determining the coupling rate or coupling activity in moles / second.

Table I. Coupling activity in liters / Mo! Seconds

1.1 χ 10 ³ 1.0 χ 10 ³

Coupler No. 2 2A example 2

Two test specimens from a total of 19 color photographic samples Recording materials with a gelatin silver bromide

Iodide emulsion layer with 75 mg of color coupler, 39 mg of di-n-butyl phthalate as a coupler solvent, 450 mg of gelatin and 136 mg of silver were in each case per 0.0929 m of support surface Usually exposed sensitometrically, developed in a color developer solution A of the composition specified below, fixed, washed, bleached, washed, fixed, washed and dried, proceeding in the usual known manner became.

209841/1068

The exposed and developed specimens were then subjected to the light fading and heat fading tests described below subject.

The heat fade test was performed as follows:

(a) The extent to which the image dyes fade under the influence of light was determined by taking the samples a 21-day exposure with simulated light from northern latitudes (SANS), whereupon the A decrease in dye densities was found in an area of the emulsion layer which had an original dye density of 1.2. This decrease in dye density, which is referred to as light fading is given in degrees of density units in the table below.

(b) The extent to which unreacted color coupler leads to undesirable discoloration under the influence of light was determined by exposing the test specimens in the manner described under (a), whereupon the resulting increase in density compared to blue light (420 μm ) of a D. "district of the test specimen was determined. This ^{increase, referred to as" copying 11} , is given in the table below in the form of the percentage increase in density.

The heat fade test was performed as follows:

(a) The extent to which the image dyes under the influence of heat and humidity ausblichen, was determined by placing samples one week were subjected to long exposure to a temperature of 60 ⁰ C at a relative humidity of 70%. The decrease in image dye density, as

209 8 A1 / 1068

22UA89

"• Heat fading" was designated as in the case of the light fading test as described under (a).

The degree of heat fading is given in the table below in terms of density units.

(b) The action of heat on unreacted color couplers was determined by testing the specimens as described under (a) Exposure to heat and moisture and that the increase in density, known as yellowing, determined by the method described in section (b) for the light fading test. The determined Values are given in the table below in the form of the percentage increase in density.

Two color developer solutions A and B were used to develop the test specimens. These color developer solutions had the following composition:

Color developing solution A

H ₂ O
Calgon

Well ₇ SO,

4-Amino-2-methyl-N, N-diethylaniline hydrochloride Na ₂ CO ₃ · H ₂ O 50% NaBr solution made up with H ₂ O to pH = 10.86.

800 ml 0.5 ε 2.0 G 2.0 G 20.0 ε 3.46 ml 1 liter.

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Color developing solution B

H ₂ O 800 ml

Benzyl alcohol Calgon

Na ₂ SO ₃

40% NaOH solution

4-Amino-3-methyl-N-ethyl-N-ß- (methylsulfonamido) -ethylaniline, Sesquisulfate hydrate

50 liter NaBr solution made up with water to pH value * 10.75.

4.0 ml 0.5 G 2.0 G 0.4 ml 5.0 G 1.72 ml 1 liter

For comparison purposes, together with those according to the invention The color couplers 4 to 6 and 17 used are structurally very similar to these color couplers used according to the invention Color couplers I to XV also tested.

Coupler

CONH (CH ₂ ) ₄ 0

R = H

R-O

NHCOCHO

209841/1068

Coupler

VI VII

2 2 Ί A A 8 9

- iar-

CF

NO

Cl

R «0

R »0

R = 0CJI ₀ 4 y

NH.

NO.

R = OCH

OH NHCOCH.

CONHCH ₂ CH ₂ -

NHCOCHO

C, H _C r , H

15 ^H 31

OH

CON

SO ₂ N

209841/1068

Coupler

22Ί4489

OH

CONH

^C 15 ^H 31

OCH,

OH

CONH

CONH (CH ₂ ) ₄ 0 ·

XIII R -

0-C

CH

C = O

₂ CIIC ₁

20 9 8 41/1068

22H489

XIV R = O = C C = O

XV R = O = C C = O

The sensitometric results obtained are shown in FIG compiled below in Table II. Mean:

LA = light fading (21 days of exposure) of the dye obtained from the color coupler;

WA = Wärmeausbleichen (1 week at 60 ⁰ C and relative humidity 70liger of the dye obtained from the color coupler;

AK = copying out (21 days of exposure) of the unreacted color coupler and

VG = yellowing (1 Wojfche exposure at 60 ⁰ C and relative humidity 70Uger) of the unreacted color coupler.

20984 1/1

Development Max 3 * e II WA 0.16 AK VG solution 3.00 T a b e 1 1 0.06 0.08 + 1% 5% Coupler A. 2.70 LA 0.08 0.00 0 8th% No. B. 3.25 Max 0.08 0.11 0.11 2% 3% 4th A. 3.08 656 0.05 0.13 written down 2% 3% B. 3.06 650 0.08 * 0.05 17% 7% 5 A. 2.80 662 0.07 0.02 16% 7% B. 3.17 656 0.05 0 15% 9% I. A. 3.04 700+ 0.06 0.03 15% 8th% B. 2.62 691 0.10 0.06 29% 17% II A. 2.30 700+ 0.07 0.04 32% 16% B. 2.39 695 0.26 0.28 21% 7% III A. 2.20 700+ 0.20 0.22 23% 7.5% B. 2.70 697 0.32 0.04 39% 14% IV A. 2.33 700+ 0.32 0.02 38% 15% B. 3.50 691 0.24 0.16 15% 9% V A. 2.50 700+ 0.20 0.10 Ί2.5% 7% B. 3.20 697 0.30 0.14 12.5% 7% VI A. 2.94 700 0.25 0.10 12.5% 7% B. 2.23 695 0.26 0 11% 9% VII A. 1.85 700 0.19 0.03 11% 9% B. 2.90 690 0.06 0.34 14% 49% VIII A. 1.48 678 0.06 0.10 13% 47% B. 3.24 660 0.20 0 12% 40% IX A. 2.68 700+ 0.12 0.06 15% 36% B. 1.60 700+ 0.04 0.08 11.5% 5% X A. 2.60 700+ 0.08 0.04 12% 10% B. 1.78 700+ 0.12 0.05 13.5% 28.5% XI A. 1.06 700 0.20 0.02 6% 22% B. 2.68 690 0.21 0.02 . 7% 6% XII A. 2.40 694 0.17 0.05 7% 6% B. 2.54 677 0.06 0.01 2% 5% 6th A. 2.03 700+ 0.04 0.02 2% 5% B. 695 0.05 written down 17th A. 1.34 657 0.06 0.12 2% 3% B. 1.26 652 0.02 2% 3.5% XIII A. 1.36 No values 0.04 1% 3.5% B. 1.34 696 0.08 2% 3.5% XIV A. 700+ B. 698 XV 700+ No values

209841/1068

22U489

- sr -

From the results obtained, it can be seen that the invention The color couplers used are surprisingly more stable than those used for comparison purposes Color couplers and that the photographic dyes obtained using the color couplers are excellent Have stability and provide a density level suitable for photographic purposes.

Example 3

There were four recording materials, each consisting of a layer support and a gelatin-silver bromide iodide emulsion layer in the manner described in Example 2, but without the addition of couplers and coupler solvents, manufactured.

(A) Two of the recording materials were then exposed sensitometrically in the customary known manner, developed, cured, color developed, fixed and bleached, as it is from the book by Glafkides "Photographic Chemistry", Volume 2, English Edition, pages 629 to 632. The color development took place at a pH of about 12.5, however with a color developing solution that consisted of:

Diethyl p-phenylenediamine HCl 3 g

Sodium sulfite 5 g

Sodium carbonate 50 g

Potassium thiocyanate 0.5 g made up with boiling distilled water

to 1000 ml

Coupler No. 1 2.5 g

Methanol 100 ml

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221U89

After bleaching, washing and drying, the blue-green dye images obtained were exposed to that in Example 2 subjected to the light fading test described. The results obtained are shown in Table III below.

(B) Two more film strips were exposed and developed as in Example 3 (A), but using a color developer solution, which contained color coupler no. 2 instead of color coupler no.

The fully developed specimens were tested as described in Example 3 (A).

The results compiled in the following table were obtained:

Table III SANS (LA) Test item 0.07
0.06
0.07
0.08 A.
B.

209841/1068

Claims (9)

HO PATENT CLAIMS 1. Color photographic recording material with at least one silver halide emulsion layer with one at the color photographic development a cyan dye-producing color coupler having one of the formulas: II. X or 209841/10 68 22U4 where mean: R is a cyclic radical; R _{3 represents} a hydrogen atom or an alkyl radical; R. a hydrogen atom or an optionally substituted aryloxy radical; R _{5 is} a hydrogen atom or an alkyl radical; R _{6 is} an alkyl, optionally substituted aryl or optionally substituted aryloxy radical; X is a hydrogen or halogen atom; Y represents a hydrogen atom or an alkyl, alkoxy or alkylthio radical; Z necessary to complete a heterocyclic ring atoms required with 5 or 6 ring arle members; η «0, 1, 2, 3, 4, 5, 6, 7 or 8; m = 0 or 1 characterized in that the silver halide emulsion layer contains a color coupler of one of the specified formulas I. to III, in which R is a radical of the formula: 209841/1 068 221U89 where Z is the necessary to complete a heterocyclic ring with 5 or 6 ring atoms Represents atoms. 2. Color photographic recording material according to claim 1, characterized in that the emulsion layer has a Contains color couplers of the specified formulas I to III, in which Z is used to complete a Thiazolyl, Tetrazolyl, Benzoxazolyl, Benzimidazolyl, Benzthiazolyl, Furyl, Pyrryl, Thienyl, Pyranyl, Benzofuranyl, Benzopyranyl, Isoindolyl, Benzopyranyl, Oxazinyl, Oxazolyl or Imidazolyl ring represents required atoms. 3. Color photographic recording material according to Claims 1 and 2, characterized in that the emulsion _{layer contains a color coupler of the formula I in which R 6 is} a phenyl or phenyloxy radical and η = 0,1,2,3,4,5 or 6. 209 84 1/1068 4. Color photographic recording material according to Claims 1 to 3, characterized in that the emulsion layer contains a color coupler of the formula I, in which: η = 0,1,2,3,4,5 or 6;
R _{3 is} a hydrogen atom; R _{6 is} a phenoxy group substituted by 2 short-chain alkyl groups or an alkyl-carbonamidophenyl group with a short-chain alkyl group and Z the atoms required to complete a tetrazolyl radical substituted by an aryl radical. 5. Color photographic recording material according to claim 4, characterized in that the emulsion layer has a color coupler of the formula I contains: η = 0, 1, 2, 3 or 4; R _{3 is} a hydrogen atom; Rg one through two short-chain tertiary alkyl radicals substituted phenoxy radical or an alkylcarbonamidophenyl radical with a short-chain alkyl group and Z the atoms required to complete a tetrazolyl radical which is substituted by one Phenoxy short chain alkyl carbonamido phenyl; Alkylcarbonamidophenyl-;
Alkene carbonamidophenyl-; 209841/10 68 Alkylsulfonamidophenyl or one Aminophenyl radical. 6. Color photographic recording material according to Claims 1 to 3, characterized in that the emulsion layer contains a color coupler of the formula I in which: η - 0,1,2,3 or 4; Rt is a hydrogen atom; R _{6 is} a phenoxy radical substituted by two tertiary short-chain alkyl radicals and Z the atoms required to complete a benzothiazolyl radical. 7. Color photographic recording material according to claims 1 and 2, characterized in that the emulsion layer contains a color coupler of the formula II, in which : X is a hydrogen or halogen atom; Y is a hydrogen atom or a short-chain alkyl or alkylthio radical; m »0 or 1; R ₃ . R ₄ and Rr each represents a hydrogen atom and Z the atoms required to complete a phenyl tetrazolyl or benzoxazolyl radical. 209841/1068 8. Color photographic recording material according to claims 1 to 7, characterized in that the emulsion layer contains one of the following color couplers: 6-acetamido-2-chloro-3-methyl-4- (1'-phenyl-5 ^f -tetrazolyloxy) phenol; 6 ~ 1 " - (2 ·, 4 ^f -di (t) -amylphenoxy) -propyl-carbonamido-2-chloro-3-methyl-4-benzoxazolyloxyphenol; 1-hydroxy- 2- ^ ~ N- (2 ', 4' -di (t) -amylphenoxy) -butyl7-4- (1-phenyl-5'-tetrazolyloxy) -2-naphthamide; 1-hydroxy-4- (benzoxazolyloxy) -N- / 4- (2 ', 4 ^f -di (t) -amylphenoxyacetamido) -phenyl-7ethyl-2-naphthamide; 1-hydroxy-4 - / "" 2 (H) -4-benzopyranyloxY7- N- (2-hexadecyloxy-5-methylphenyl) -2-naphthamide; 1-Hydroxy-2 - / "N- (2-acetamidophenyl) ethyl_7-4 - /" i- (3- {a- {3'-pentadecylphenoxy} -propyl} carbonamides) phenyl7-tetrazolyloxy-2-naphthamide or 1-Hydroxy-4 - / "2- (1,3-oxazinyloxy-7-N- (2,4-di-tertiary-amylphenoxy) butyl) -2-naphthamide. 9. Color developer solution for the development of a color photographic recording material with a a color coupler producing a blue-green image dye, characterized in that it is a color coupler Contains color coupler of one of the formulas I to III. 209841/1068