JP2000321734A - Color photographic copying machine material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To remove a defect of causing color shift of couplers to blue and cyan color tones to make it possible to use the merits of the couplers. SOLUTION: This color photographic copying machine material comprises at least one red sensitive silver halide emulsion layer containing at least one kind cyan coupler, at least one green sensitive silver halide emulsion layer containing at least one kind of magenta coupler, and at least one blue sensitive silver halide emulsion layer containing at least one kind of yellow coupler, and at least one of the red sed sensitive layers contains at least one kind of pyrazoloazole cyan coupler represented by the formula, and a 2-equivalent yellow coupler combines with at least red sensitive layer or a red sensitized silver halide emulsion combines with at least one blue sensitive silver halide emulsion layer. In the formula, each of R11 and R12 is, independently, an electron-withdrawing group; X11 is an H atom or a group releasable by reaction with the oxidation product of a developer; Y11 is a group necessary to complete an N-containing hetero ring, but R12 combines with the carbon atom; and (n) is 1 or 2.

Description

DETAILED DESCRIPTION OF THE INVENTION

The present invention relates to a color photographic copier material containing at least one pyrazoloazole as a cyan coupler.

In particular, color photographic copier materials are opaque image or display materials and generally comprise a positive image. They are therefore not recording materials like color photographic films.

[0003] Pyrazoloazoles are described, for example, in JP-A6
4-554 and cyan couplers known from EP 717 315, which give very bright cyan dyes with a relatively short wavelength absorption band and a very high absorbance, and consequently silver halide savings Enable. Furthermore, the cyan dyes of these couplers show very good stability on storage, excluding light.

A disadvantage of these couplers is that they cause a color change to blue and cyan tones.

It is an object of the present invention to eliminate the disadvantages and to make use of the advantages of these couplers.

Surprisingly, this time, at least one red-sensitive silver halide emulsion layer containing at least one cyan coupler, at least one green-sensitive silver halide emulsion layer containing at least one magenta coupler,
And at least one blue-sensitive silver halide emulsion layer containing at least one yellow coupler, wherein at least one red-sensitive layer contains at least one compound of formula (I)

[0007]

Embedded image

Wherein R ¹¹ and R ¹² independently represent an electron-withdrawing group, X ¹¹ represents H or a group capable of leaving by reaction with a developer oxidation product, and Y ¹¹ represents nitrogen - group for the completion of containing heterocyclic ring, provided that the groups represented by R ¹² is bonded to the carbon atom of the heterocycle, and the pyrazoloazole cyan couplers n is 1 or 2] A material of the type referred to at the outset wherein the 2-equivalent yellow coupler is associated with at least one red-sensitive layer or the red-sensitized silver halide emulsion is associated with at least one layer containing a yellow coupler. It has been found that this objective can be achieved if you do.

At least one 2-equivalent yellow coupler
When associated with two red-sensitive layers, the yellow coupler is preferably used in at least one red-sensitive layer.
In particular, the amount of yellow coupler in the red-sensitive layer is in the range from 1 to 10 mol% of the amount of cyan coupler of formula (I).

The 2-equivalent yellow coupler used in the red-sensitive layer preferably exhibits a coupling speed no greater than five times the coupling speed of the pyrazoloazole cyan coupler. Coupling speed is J. Phot. Sci. 3
6, (1988), page 14.

The 2-equivalent yellow coupler almost always couples significantly more rapidly than the cyan coupler. Cyan couplers constructed in accordance with the present invention exhibit a color shift from low to high densities, with low densities expected to shift strongly toward yellow or green.

Surprisingly, however, this does not happen.

Preferred 2-equivalent yellow couplers are acetanilides, especially pivaloylacetoanilides and malonanilides, the volatile groups of which are linked via O or N to the coupler molecule and which are ortho to the anilide component. Position is substituted by chlorine, alkoxy or aryloxy.

Very particularly preferred 2-equivalent yellow couplers have the formula (II):

[0015]

Embedded image

[Wherein, R_{twenty one}Preferably has 1 to 4 carbon atoms
Alkyl, especially methyl, R_{twenty two}Is preferably carbon
Represents an alkyl of 1 to 4, especially methyl, R_{twenty three}Is hydrogen
Atom or preferably alkyl having 1 to 4 carbon atoms, especially
Represents methyl, or R_{twenty two}And R_{twenty three}Are together
Indicates the remaining members of the chloropropyl group,_{twenty four}Is chlorine or
Indicates alkoxy, R_{twenty five}Is -NHCO-R₂₇, -SO_TwoN
HR₂₇, -NHSO_Two-R₂₇, -COOR ₂₇, Cl,
Represents Br or alkoxy, R₂₆Is hydrogen or chlorine source
Indicates a child, R₂₇Represents a substituent, especially a ballast group, and
Q is substituted imidazole, imidazolidinedio
, Oxazolidinedione or triazolidinedione
Indicates the remaining members of the ring, wherein the alkyl group is further substituted
May be used].

There are many possibilities for the co-incorporation into one of the cyan and yellow couplers according to the invention, these compounds being:-in a common emulsion in at least one coupler solvent, Or-optionally in two separate emulsions, each comprising at least one coupler solvent.

When the red-sensitive silver halide layer is associated with at least one blue-sensitive layer, the emulsion corresponds to 1 to 30%, preferably 3 to 15%, of the cyan density over the entire density range for red exposure. The amount of yellow density to be applied.

The term "associated" means that a red-sensitized silver halide emulsion is formed in this layer upon development because it is located in or adjacent to the blue-sensitive layer. It means that the developer oxidation product (DOP) simply couples with one coupler, the yellow coupler, in at least one blue-sensitive layer.

The red-sensitized silver halide emulsion is preferably located in the at least one blue-sensitive layer itself.

In this situation, the present invention employs both blue and red sensitized silver halide emulsions or mixes two separate blue and red sensitized silver halide emulsions together. Can be executed. Finally, the red-sensitized silver halide emulsion can be used in a separate layer with a yellow coupler.

The red-sensitized silver halide emulsion associated with the blue-sensitive layer is especially chosen such that it approximately corresponds to the red sensitivity of the layer containing the cyan coupler. This can be done with an amount of sensitizer, or it can be done, for example, by grain size.

Suitable blue sensitizers are of the formula (III)

[0024]

Embedded image

Wherein R _{31 to} R ₃₃ and R _{36 to} R ₃₈ are H, alkyl, alkoxy, halogen, 2-thienyl,
3-thienyl, 1-pyrrolyl, 2-pyrrolyl, phenyl, 1-indolyl, 2-furanyl, 3-furanyl or indicates carbazolyl, R ₃₄ and R ₃₅ alkyl, sulfoalkyl, carboxyalkyl, - (CH _{2) n} SO _{2
N-COR 39, - (CH} 2) n SO 2 N-SO 2 R 39, - (C
H ₂ ) _n CON-SO ₂ R ₃₉ or-(CH ₂ ) _n CON-CO
R ₃₉ represents X ₃₁ and X ₃₂ represent O, S, Se, NR ₃₀ , M represents a counter ion, n represents a number of 2 to 4, and R ₃₉ and R ₃₀ represent C ₁ -C Represents ₄ alkyl, or R ₃₁ and R ₃₂ or R ₃₂ and R ₃₃ , R ₃₆ and R ₃₇
Or R ₃₇ and R ₃₈ represent the remaining members of the fused benzene or naphthalene ring.

Preferred blue sensitizers are of the formula (IV)

[0027]

Embedded image

Wherein R ₄₁ and R ₄₃ represent hydrogen;
₄₂ is halogen, especially chlorine or fluorine, or 2-thienyl, 3-thienyl, 1-pyrrolyl, 2-furanyl, 1
-Represents indolyl or phenyl, or R ₄₁ and R ₄₂ together, or R ₄₂ and R ₄₃ together, represent the remaining members of the fused benzene or naphthalene ring, R ₄₄ represents hydrogen, R ₄₅ is halogen, especially chlorine or fluorine, phenyl, 2-thienyl, 3-thienyl,
1-pyrrolyl, 2-furanyl, 1-indolyl,
Or R ₄₄ and R ₄₅ represents a remaining membered fused benzene or naphthalene ring together, X ₄₁ represents S or O, M is a counterion, in particular shows a triethylammonium, and l and m are 2 4 is shown].

Suitable red sensitizers are of the formula (V)

[0030]

Embedded image

Wherein X ₅₁ , X ₅₂ , R ₅₁ -R ₅₈ and M
Has the same meaning as R ₃₁ -R ₃₉ , X ₃₁ , X ₃₂ and M in Formula III, R ₅₉ represents H, alkyl, halogen, dialkylamino or thio, and R ₅₀ and R ₆₀ represent H or Represents alkyl].

The red sensitizer is preferably of the formula (VI)

[0033]

Embedded image

Wherein R ₆₄ , R ₆₅ , X ₆₁ and M are of the formula II
R has the same meaning as R ₃₄ , R ₃₅ , X ₃₂ and M in I,
₆₁ , R ₆₂ , R ₆₃ , R ₆₆ , R ₆₇ and R ₆₈ independently of one another are H, CH ₃ , OCH ₃ , Cl, 1-pyrrolyl, 1-indolyl, 2-thienyl, 3-thienyl, 2-furanyl ,
Represents 3-furanyl, N-carbazolyl or phenyl, or R ₆₁ and R ₆₂ or R ₆₂ and R ₆₃ , and R ₆₆ and R ₆₇ or R ₆₇ and R _{68 taken} together as benzo, 1,2-naphth or Shows the remaining members of the 2,3-naphtho ring].

The term “alkyl” for the purposes of the present application
Is to be understood as meaning a linear or branched, straight-chain or cyclic, substituted or unsubstituted hydrocarbon radical. An alkyl group having 1 to 32 carbon atoms is preferred. Particularly suitable open chain alkyl groups are methyl, ethyl, n
-Propyl, n-butyl, n-octyl, n-dodecyl, n-hexadecyl and n-octadecyl groups, and particularly suitable branched alkyl groups are 2-hexyldecyl, 2-octyldodecyl and 2-ethylhexyl Groups. Cycloalkyl groups, especially 4-tert-butyl, cyclohexyl, and 2,6-di-tert-butyl 4-methylcyclohexyl, are preferred among the alkyl groups. The term "alkenyl", for the purposes of this application, refers to linear or branched, straight or cyclic, substituted or unsubstituted unsaturated hydrocarbon groups such as ethenyl, 2-propenyl, isopropenyl and It should be understood that it means an oleyl group. It is to be understood that the term "aryl" for the purposes of this application means an aromatic hydrocarbon group, preferably phenyl or naphthyl. These may be substituted or unsubstituted. The term "hetaryl" for the purposes of this application
Is to be understood as meaning an aromatic system containing at least one heteroatom. These can preferably be present as monocyclic or fused ring systems.
-Or a 6-membered ring system. They can comprise both substituted and unsubstituted ring systems.
N, S and O are particularly suitable heteroatoms. The ring system preferably contains 1 to 3 heteroatoms, which can be the same or different heteroatoms. In a fused ring system, a plurality of identical or different systems, for example, a hetaryl group and an arylene group, can be fused. Representative examples are pyridine, pyridazine, pyrimidine, pyrazine, oxazole, isoxazole, thiazole, 3,4-oxadiazole, 1,2,4-oxadiazole, imidazole, 1,2,3-triazole and 1,2,4 -Including tri-azoles, especially furan, pyrrole, thiophene and indole.

The term “alkoxy” for the purposes of the present application
Should be understood to mean a radical of the formula OR ', wherein R' represents an alkyl radical according to the definition given above.

The term “aryloxy” for the purposes of the present application is to be understood as meaning radicals of the OR ″ type, wherein R ″ represents an aryl group according to the definition given above. .

An acyl group for the purposes of this application is an aliphatic, olefinic or aromatic carboxylic acid, carbonic acid, carbamic acid, sulfonic acid, amidosulfonic acid, sulfinic acid, phosphoric acid, phosphonic acid or phosphorous acid group. It is possible.

Suitable substituents for the purposes of this application are aryl, alkyl, alkoxy, aryloxy, acyl, acyloxy, acylamino, hetaryl, alkynyl, hydroxy, cyano, carboxy and sulfo groups, and halogens, preferably fluorine, chlorine Or bromine.

Electron-withdrawing groups for the purposes of this application are carboxy, carbamoyl, acyloxy, oxycarbonyl, halogenated alkoxy, aryloxy, aryloxy, acyl, sulfonyl, all optionally substituted carboxy, carbamoyl, acyloxy, oxycarbonyl, Sulfinyl, sulfonyloxy, sulfonylmethyl, sulfamoyl, tetrazolyl, pyrrolyl, phosphonyl, alkyl halide, aryl halide, cyano, alkylsulfonylmethyl, arylsulfonylmethyl or nitro group, and halogen atom.

The cleavage group X ₁₁ is an N-heteroaromatic compound which is attached via a halogen, for example chlorine, N and is optionally substituted;
For example, pyrazoles, imidazoles, triazoles, or non-aromatic heterocycles such as hydantoins, oxazolidine-diones, aliphatic or aromatic mercaptans linked via S, such as mercaptopropionic acid, 2-acylamino Phenylmercaptans,
Or an aliphatic or aromatic hydroxy compound bonded via O, for example, ethylene glycol or p-
It can be ethyl salicylate.

The compounds of the formula (I) which are preferably used are those of the formula (IA)

[0043]

Embedded image

Wherein R ₁₃ and R ₁₄ independently of one another have the meaning of R ₁₁ or R ₁₂ , X ₁₂ has the meaning of X ₁₁ and Z ₁₂ represents H or a substituent. belongs to.

Some particularly preferred compounds of formula (I) or (IA) are listed in the table below.

[0046]

[Table 1]

[0047]

[Table 2]

[0048]

[Table 3]

[0049]

[Table 4]

Suitable yellow couplers of the formula (II) are:

[0051]

Embedded image

[0052]

Embedded image

Suitable compounds of the formula (IV) are the following, where l and m = 3 and which comprise triethanolammonium as counterion.

[0054] X ₃ R ₂₁ R ₂₂ R ₂₃ R ₂₄ R ₂₅ IV-1 SH 2-thienyl HHCl IV-2 SH 3-thienyl HHCl IV-3 SH 1-pyrrolyl HHCl IV-4 SH 2-furyl HHF IV-5 SH 1-Indolyl HHCl IV-6 SH benzo HCl IV-7 S H Cl H H Cl IV-8 SH 1,2-Naphtho HCl IV-9 OH 2,3-naphtho H phenyl X ₃ R ₂₁ R ₂₂ R ₂₃ R ₂₄ R ₂₅ IV-10 O 1,2-Naphtho H benzo IV-11 SH Cl H H phenyl IV-12 SH Benzo Benzo IV-13 O H benzo 1,2-naphtho IV-14 SH 2-thienyl H H 2-thienyl IV-15 SH 3-thienyl H H 3-thienyl IV-16 SH 1-pyrrolyl HH 1-pyrrolyl IV-17 SH 1-Indolyl HH1-Indolyl Suitable red sensitizers are:

[0055]

Embedded image

[0056]

Embedded image

[0057]

Embedded image

[0058]

Embedded image

[0059]

Embedded image

[0060]

Embedded image

Examples of color photographic copier materials include color photographic paper, paper, color reversal photographic paper and translucent display materials. For an overview, see Research Disclosure 37038 (1995), Res
earchDisclosure 38957 (1996) and Research Discl
osure 40145 (1997).

Photographic copier materials consist of a support having deposited thereon at least one photosensitive silver halide emulsion layer. Thin films and foils are particularly suitable as supports.
An overview of the support material and the auxiliary layers deposited before and after
Research Disclosure 37254, Part 1 (1995), page 28
5 and Research Disclosure 38957, Part XV (199
6), page 627.

The color photographic copier materials generally contain at least one red-sensitive, at least one green-sensitive and at least one blue-sensitive silver halide emulsion layer,
In some cases, an intermediate layer and a protective layer are also contained.

Depending on the type of photographic copier material, these layers may be arranged differently. Let me explain this for the most important products.

Color photographic papers and color photographic display materials are generally prepared on their supports in the following sequence by means of a blue-sensitive yellow-coupling silver halide emulsion layer,
A green-sensitive magenta-coupling silver halide emulsion layer and a red-sensitive cyan-coupling silver halide emulsion layer. No yellow filter layer is required.

Departures from the number and arrangement of the photosensitive layers may be made to achieve a determined result. For example, a color paper may comprise an intermediate layer which can be sensitized differently and thereby influence the tone.

The essential components of the photographic emulsion layer are a binder, silver halide grains and a color coupler.

Information on suitable binders is available from Research Di
sclosure 37254, Part 2 (1995), page 286, and Re
search Disclosure 38957, Part II.a (1996), page 59
It is shown in Figure 8.

Suitable silver halide emulsions, their preparation,
Information on spectral sensitization, including ripening, stabilization, and suitable spectral sensitizers is available from Research Disclosure 37254, Pa.
rt 3 (1995), page 286, Research Disclosure 37038, P
art XV (1995), page 89, and Research Disclosure
38957, Part VA (1996), page 603.

In addition, pentamethine cyanines are defined as basic end groups which are substituted by halogen or methyl or methoxy groups and can be cross-linked by 9,11-alkylene bonds, in particular by 9,11-neopenthylene bonds. It can be used as a red sensitizer for red-sensitive layers comprising naphthothiazole, naphthoxazole or benzthiazole. The methine chain may further comprise other substituents. Pentamethines having only one methyl group on their cyclohexene ring can also be used. Red sensitizers can be supersensitized and stabilized by the addition of heterocyclic mercapto compounds.

Furthermore, the red-sensitive layer can be spectrally sensitized between 390 and 590 nm, preferably at 500 nm, for better differentiation of the red hue.

The spectral sensitizers can be added to the photographic emulsion in dissolved form or in dispersion. Both solutions and dispersions can contain additives, such as wetting agents or buffers.

The spectral sensitizer or combination of spectral sensitizers can be added before, during or after the preparation of the emulsion.

Photocopier materials can contain up to 80 mol% AgB
Either a silver chloride-bromide emulsion comprising r or a silver chloride-bromide emulsion comprising more than 95 mol% AgCl.

Information on color couplers is available from Research
Disclosure 37254, Part 4 (1995), page 288, Research
Disclosure 37038, Part II (1995), page 80, and
Research Disclosure 38957, Part XB (1996), page
See 616. For copier materials, the maximum absorption of the dye formed from the coupler and from the oxidation product of the color developer preferably falls within the following ranges: yellow coupler 440-450 nm, magenta coupler 540-56.
0 nm, cyan coupler 640-670 nm.

The yellow couplers used in copier materials generally associated with the blue-sensitive layer are, with few exceptions, 2-equivalent couplers of the pivaloylacetanilide and cyclopropylcarbonylacetanilide type.

Magenta couplers used in copier materials are almost without exception anilinopyrazolones, pyrazolo [5,1-c] (1,2,4) triazoles or pyrazolo [1,5-b]. It is from a system comprising (1,2,4) triazoles.

Generally, a photosensitive interlayer disposed between layers of different spectral sensitivities provides for an undesirable diffusion of developer oxidation products from one photosensitive layer to another photosensitive layer having a different spectral sensitivity. It may contain a medium to prevent it.

Suitable compounds (white couplers, scavengers or DOP scavengers) are described in Research Disclo
sure 37254, Part 7 (1995), page 292, Research Disc
losure 37038, Part III (1995), page 84, and Res
earch Disclosure 38957, Part XD (1996), page 621
et seq.

The photographic material further comprises a compound absorbing ultraviolet rays, a lightening agent, a spacer, a filter dye, a formalin scavenger, a light stabilizer, an antioxidant, a D _Min dye, a plasticizer (latex), a bactericide, and a dye. -, Couplers and additives to improve white stability and reduce color cast, and may contain other substances. Suitable compounds are Research Disclosure 37254, Pa
rt 8 (1995), page 292, Research Disclosure 37038,
Part IV, V, VI, VII, X, XI and XIII (1995), page 84
et seq., and Research Disclosure 38957, Part V
I, VIII, IX, X (1996), pages 607, and 610 et seq.

The layers of the color photographic material are generally hardened, ie the binder used, preferably gelatin,
Is cross-linked by a suitable chemical method.

Suitable hardener materials are available from Research Disclosure
37254, Part 9 (1995), page 294, Research Disclosu
re 37038, Part XII (1995), page 86, and Researc
h Disclosure 38957, Part II.B (1996), page 599.

After image-by-image exposure, color photographic materials are processed in different ways depending on their properties. For details on the processes used and the chemicals required for them, see Research Disclosure 37254, Part
10 (1995), page 294, Research Disclosure 37038, P
art XVI to XXIII (1995), page 95 et seq., and Re
search Disclosure 38957, Part XVIII, XIX, XX (199
6), page 630 et seq., With material examples.

Light stabilizers suitable for use in the layer containing the pyrazoloazole cyan coupler of formula (I) are described in EP for co-use with pyrazoloazole cyan couplers.
544 316, EP 544 317 and EP 54
5 305.

Preferred light stabilizers are those of the formula (IX)

[0086]

Embedded image

Wherein R ₉₁ represents an alkyl, alkenyl or aryl group, R ₉₂ and R ₉₃ each independently represent a hydrogen atom or an alkyl or alkoxy group having up to 16 carbon atoms, and R ₉₄ represents a hydrogen atom or Represents an alkyl group, especially a methyl group, R ₉₅ represents a C ₁ -C ₃ alkylene group, and X ₉₁ represents an oxygen atom or a free electron pair, wherein the alkyl group may be further substituted. I do.

Formula

[0089]

Embedded image

Light stabilizers are preferred.

Other suitable light stabilizers are of formula (VIII)

[0092]

Embedded image

Wherein R ₈₁ represents H or alkyl, alkenyl, aryl or acyl; R ₈₂ represents H or alkyl, alkoxy, aryloxy, acylamino, alkylamino, arylamino, hydroxy or hetaryl, And R ₈₃ represents H or alkyl, alkenyl, aryl, acyl or chlorine, wherein a plurality of R ₈₂ and R ₈₃ groups can be the same or different.

Representative examples of the compounds of formulas (VIII) and (IX) are:

[0095]

Embedded image

[0096]

Embedded image

[0097]

Embedded image

Oil-forming agents which are particularly suitable for co-use with pyrazoloazole cyan couplers of the formula (I) for improving the absorption properties and the light stability of the corresponding dyes are of the formula (VI)
I)

[0099]

Embedded image

[Wherein, R ₇₁ represents alkyl, alkenyl, aryl, alkoxy, aryloxy, alkylamino, arylamino, acyl, acylamino, acyloxy, hetaryl, halogen, nitro or cyano, and R ₇₂ represents OH Or has the same meaning as R ₇₁ ,
n and m independently represent 0 or 1, o represents 0, 1, 2, 3, 4 or 5, provided that the total carbon number of the compound is at least 16.

Some examples of particularly preferred formula (VII) according to the present invention are given below.

[0102]

Embedded image

[0103]

Embedded image

The compounds of the formulas (I) and (II) according to the invention can be used in conventional amounts in photographic materials. The compound of formula (I) is preferably from 20 to 2000 mg / m ²
Of the photographic material, in particular in an amount of photographic material 50 to 500 mg / m ^2. The compounds of the formula (VII) are preferably used in a weight ratio in the range from 20: 1 to 1:10 with respect to the compound of the formula (I), and in particular in a weight ratio of 10: 1 to 1: 5, most preferably Are used in a weight ratio of 5: 1 to 1: 2.

The compounds of the formulas (I) and (VII) according to the invention are preferably used directly in or adjacent to a red-sensitized silver halide emulsion layer. . In particular, the compounds of the formulas (I) and (VII) are used in the same layer.

In one preferred embodiment, the at least one red-sensitive layer further comprises at least one N, N of formula (IX)
-Contains a di-substituted p-aminophenol ether.

[0107]

EXAMPLE 1 A color photographic recording material suitable for the rapid processing step was prepared by depositing the following layers in the order described on a film base comprising paper coated on both sides with polyethylene. . Quantitative data are given in each case for 1 m ² . The corresponding amounts of AgNO ₃ are given relative to the silver halide precipitation. Layer Structure 101 Layer 1: (substrate layer) 0.10 g gelatin Layer 2: (blue-sensitive layer) 0.4 g A spectrally sensitized with 0.6 mg compound IV-6
comprising a Gno _3, blue-sensitive silver halide emulsion (99.
5 mol% chloride, 0.5 mol% bromide, average particle diameter 0.75 μm) 1.25 g gelatin 0.50 g yellow coupler GB-1 0.30 g tricresyl phosphate (TCP) 0.10 mg stable Agent ST-1 Layer 3: (Intermediate layer) 0.10 g of gelatin 0.06 g of DOP scavenger SC-1 0.06 g of DOP scavenger SC-2 0.12 g of TCP Layer 4: (green sensitive layer) 0.12 mg 0.2 g spectrally sensitized with the compound GS-1
Comprising the AgNO _3, green-sensitive silver halide emulsion (99.5 mol% chloride, 0.5 mol% bromide, average grain diameter 0.45 [mu] m) magenta coupler gelatin 0.10g of 1.10g PP-1 0.10 g of magenta coupler PP-2 0.15 g of stabilizer ST-2 0.20 g of stabilizer ST-3 0.20 g of TCP 0.02 g of isotetradecanol Layer 5: (UV protective layer ) 1.05 g of gelatin 0.20 g of UV absorber UV-1 0.05 g of UV absorber UV-2 0.22 g of UV absorber UV-3 0.06 g of DOP scavenger SC-1 0.06 g of DOP Scavenger SC-2 0.25 g TCP layer 6: (red sensitive layer) Spectral sensitized with 0.54 mg compound V-1 and 0.5
0.28 g of A stabilized with 6 mg of stabilizer ST-4
A red-sensitive silver halide emulsion comprising gNO ₃ (99.
5 mol% chloride, 0.5 mol% bromide, average particle diameter 0.48 μm) 1.00 g gelatin 0.40 g cyan coupler BG-1 0.40 g TCP layer 7: (UV protective layer) 1 0.05 g gelatin 0.20 g UV absorber UV-1 0.05 g UV absorber UV-2 0.22 g UV absorber UV-3 0.15 g TCP layer 8: (protective layer) 0.90 g Gelatin 0.05 g Optical brightener W-1 0.07 g polyvinylpyrrolidone 1.20 ml silicone oil 2.50 mg spacer material comprising polymethyl methacrylate, average particle size 0.8 μm 0.30 g Instant curing agent H-1 layer structure 102 Layer structure 102 differs from layer structure 101 only in layer 6. Layer 6: (Red-sensitive layer) Spectral sensitized with 0.03 mg of compound V-1 and 0.4
0.20 g of Ag stabilized with mg of stabilizer ST-4
A red-sensitive silver halide emulsion comprising NO ₃ (99.5
Mol% chloride, 0.5 mol% bromide, average particle diameter 0.48 μm) 1.00 g gelatin 0.30 g cyan coupler I-9 0.40 g TCP layer structure 103 Layer structure 103 Only the structure 101 and the layer 2 differ. Layer 2: (Blue-Sensitive Layer) A blue-sensitive silver halide emulsion comprising 0.40 g of AgNO ₃ spectrally sensitized with 0.6 mg of compound IV-6 (9
9.5 mol% chloride, 0.5 mol% bromide, average particle diameter 0.75 μm); spectrally sensitized with 0.005 mg of compound V-1 and stabilized with 0.05 mg of ST-4. Red-sensitive silver halide emulsion (99.5 mol% chloride, 0.5 mol% bromide, average particle diameter 0.65 μm) comprising 0.02 g of AgNO ₃ 1.25 g of gelatin 0.50 g of yellow coupler GB-1 0.10 g of stabilizer ST-1 0.30 g of TCP layer structure 104 The layer structure 104 differs only in layer structure 102 and layer 2. Layer 2: (Blue-Sensitive Layer) A blue-sensitive silver halide emulsion comprising 0.40 g of AgNO ₃ spectrally sensitized with 0.6 mg of compound IV-6 (9
9.5 mol% chloride, 0.5 mol% bromide, average particle diameter 0.75 μm); spectrally sensitized with 0.01 mg of compound V-1 and stabilized with 0.1 mg of ST-4. 0.
Comprising the AgNO ₃ of 05G, a red-sensitive silver halide emulsion (99.5 mol% chloride, 0.5 mol% bromide,
Addition of an average particle diameter of 0.65 μm) 1.25 g of gelatin 0.50 g of yellow coupler GB-1 0.30 g of TCP 0.10 g of stabilizer ST-1 layer structure 105 layer structure 105 layer structure 105 And only in layer 4. Layer 4: (green sensitive layer) 0.2 g spectrally sensitized with 0.12 mg of compound GS-1
Comprising the AgNO _3, green-sensitive silver halide emulsion (99.5 mol% chloride, 0.5 mol% bromide, average grain diameter 0.45 [mu] m) magenta couplers of 1.10g of gelatin 0.15g PP-3 0.05 g stabilizer ST-2 0.10 g stabilizer ST-3 0.4 g TCP layer structure 106 Layer structure 106 differs only in layer structure 105 and layer 2. Layer 2: (Blue Sensitive Layer) 0.40 g spectrally sensitized with 0.6 mg of compound III-6
Comprising the AgNO ₃ of blue-sensitive silver halide emulsion (99.5 mol% chloride, 0.5 mol% bromide, average grain diameter 0.75 .mu.m); spectroscopy at 0.01mg of Compound V-1 A red-sensitive silver halide emulsion (99.5 mol% chloride, 0.5 mol% bromide, comprising 0.05 g AgNO ₃ sensitized and stabilized with 0.1 mg ST-4. 1.25 g of gelatin 0.50 g of yellow coupler GB-1 0.30 g of TCP 0.10 g of stabilizer ST-1 The following compounds were used in Example 1:

[0108]

Embedded image

[0109]

Embedded image

[0110]

Embedded image

[0111]

Embedded image

Processing: Negatives comprising Macbeth color chart exposure were transferred to samples using a conventional printer. Filtration during this step was chosen so that the gray area N5 of the Macbeth chart was reproduced on the copy as a dull gray with a density of 0.7. Processing was performed using the AP94 method (Agfa) as follows. Color areas # 18 (cyan), # 6 (bluish green), # 2 (light flesh color) and # 1 (dark flesh color) were subsequently measured on the copy (Gretag SPM).
100-II) and the difference between each {E} CieLab system color difference between original and print was recorded. a) Color developer-45 seconds -35 ° C Triethanolamine 9.0 g N, N-diethylhydroxylamine 2.0 g Bis (2-sulfoethyl) -hydroxylamine, disodium salt 2.0 g Diethylene glycol 0.05 g Sulfuric acid 3- Methyl-4-amino-N-ethyl-N-methane-sulfonamidoethyl-aniline 5.0 g Potassium sulfite 0.2 g Triethylene glycol 0.05 g Potassium carbonate 22 g Potassium hydroxide 0.4 g Ethylenediaminetetraacetic acid, di-Na salt 2.2 g Potassium chloride 2.5 g 1,2-Dihydroxybenzene-3,4,6-trisulfonic acid, trisodium salt 0.3 g Make up to 1000 ml with water, pH 10.0 b) Bleaching-curing agent-45 seconds- 35 ° C. ammonium thiosulfate 75g sodium bisulfite 13.5g ammonium acetate And 1000ml with .0g ethylenediaminetetraacetic acid (iron ammonium salt) 57 g 25% aqueous ammonia 9.5g vinegar, pH 5.5 c) washing -2 min -33 ° C. d) Drying

[0113]

[Table 5]

From the table it can be seen that the degradation of color reproduction for # 18 due to the use of the pyrazoloazole cyan coupler was significantly improved by the method according to the invention. There is also an improvement in the difference measured for # 6 and an improvement in that measured for flesh tone.

Example 2 Layer Structure 201 The layer structure 201 differs from the layer structure 101 only in the layer 6. Layer 6: (Red sensitive layer) Spectral sensitized with 0.04 mg of compound V-1 and 0.5
0.28 g of Ag stabilized with 0 g of stabilizer ST-4
A red-sensitive silver halide emulsion comprising NO ₃ (99.5
(Mol% chloride, 0.5 mol% bromide, average particle diameter 0.48 μm) 1.00 g gelatin 0.30 g cyan coupler I-9 0.04 g yellow coupler GB-2 0.40 g TCP layer Structure 202 The layer structure 202 differs from the layer structure 101 only in the layer 6. Layer 6: (Red sensitive layer) Spectral sensitized with 0.04 mg of compound V-1 and 0.5
0.28 g of Ag stabilized with 0 g of stabilizer ST-4
A red-sensitive silver halide emulsion comprising NO ₃ (99.5
Mol% chloride, 0.5 mol% bromide, average particle diameter 0.48 μm) 1.00 g gelatin 0.30 g cyan coupler I-9 0.01 g yellow coupler GB-2 0.40 g TCP In Example 2, the following compounds were used in addition to those used in Example 1:

[0116]

Embedded image

The sample was exposed and evaluated as described in Example 1.

[0118]

[Table 6]

From the table it can be seen that the degradation of color reproduction for # 18 and # 6 due to the use of pyrazoloazole cyan couplers was considerably improved by the method according to the invention. There is also an improvement in the skin tone range.

Example 3 Layer structures 101, 201 and 2 respectively with the only exception that 0.15 g / m ² of magenta coupler PP-3 was used in layer 4 instead of the coupler mixture.
02 and layer structures 301 and 302
And 303 were produced. Samples were exposed, processed and evaluated as described in Example 1. It has also been shown here that the addition of a yellow coupler can significantly improve the color reproduction for # 18 and # 6.

[0121]

[Table 7]

Example 4 The layer structures of Examples 1 and 2 shown in the table were exposed to red light and processed as described in Example 1. Place them at 85 ° C and 6
Stored at 0% relative humidity and measured the percentage decrease in maximum concentration.

[0123]

[Table 8]

It was shown that the stability of the cyan image in the dark was significantly improved by the addition of the pyrazoloazole cyan coupler, and that measures to improve color reproduction did not negatively affect the stability.

Example 5 Layered Structures 501/502 The layered structures 501 and 502 are each a layered structure 104
And 102 only in layer 6, to which in each case 0.02 g of compound IX-1 was added. Layer structure 503/504 layer structure 503 and 504, respectively layer structure 104
And 202 only in layer 6, where in each case 0.20 g of TCP was replaced with 0.20 g of compound VII-7
Was replaced by Each of the layer structures 505/506 has a layer structure 503.
And 504 only in layer 6, to which in each case 0.1 g of compound IX-1 was added.

The layer structures were exposed to red light behind a neutral wedge filter and processed as described in Example 1. 10x1 following them
0 ⁶ looks - is irradiated with light from the standardized xenon lamp daylight when, and initial cyan density D = 1.
The rate of reduction at a concentration of 0 was measured.

[0127]

[Table 9]

This example shows that the photostability of pyrazoloazole cyan dyes is, for example, LM-1 and / or the formula (VI
It can be shown that considerable improvement can be achieved by the use of suitable dye stabilizers such as the compounds of I).

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) G03C 7/36 G03C 7/36 7/392 7/392 A (72) Inventor Jürgen Jung Germany Day 51379 Reef Elkusen Miyuntsushjülase 12 (72) Inventor Guyenter Herring Deutsch Day-51 519 Odenthal Indeahild Schite 16 (72) Inventor Michael Mishueld Deutsch Day-42799 Reichlingen Shi Yunooks Heide 27 (72) Inventor Edgar Draber German Day-51519 Odenthal Si Utraserhof 78

Claims (10)

[Claims] 1. At least one red-sensitive silver halide emulsion layer containing at least one cyan coupler, at least one containing at least one magenta coupler.
At least one green-sensitive silver halide emulsion layer and at least one blue-sensitive silver halide emulsion layer containing at least one yellow coupler, wherein at least one red-sensitive layer contains at least one compound of the formula (I) ) Wherein R ¹¹ and R ¹² independently represent an electron-withdrawing group, X ¹¹ represents H or a group capable of leaving by reaction with an oxidation product of a developer, and Y ¹¹ represents a nitrogen-containing group. Represents a group for the completion of the heterocycle, provided that the group represented by R ¹² is attached to a carbon atom of the heterocycle and n represents 1 or 2]. A photographic copier material, wherein the 2-equivalent yellow coupler is associated with at least one red-sensitive layer, or the red-sensitized silver halide emulsion is associated with at least one blue-sensitive halide layer. Characteristic color photocopier material. 2. The method of claim 2, wherein the 2-equivalent yellow coupler has at least
Disposed in one red-sensitive layer and of formula (II)[Wherein, R_{twenty one}Represents alkyl, and R_{twenty two}Indicates alkyl
Then R_{twenty three}Represents a hydrogen atom or an alkyl;_{twenty two}
And R_{twenty three}Are together the remaining members of the cyclopropyl group
And R_{twenty four}Represents chlorine or alkoxy, and R_{twenty five}Is-
NHCO-R₂₇, -SO_TwoNH-R₂₇, -NHSO_Two-R
₂₇, -COOR ₂₇, Cl, Br or alkoxy
Then R₂₆Represents a hydrogen or chlorine atom;₂₇Is a substituent
And Q is a substituted imidazole, imidazoly
Zindione, oxazolidinedione or triazolidy
Indicates the remaining members of the dione ring, where the alkyl group is
Which may be replaced by
The color photographic copier material of claim 1. 3. The method according to claim 1, wherein the at least one blue-sensitive layer comprises
I): Wherein R ₃₁ -R ₃₃ and R ₃₆ -R ₃₈ are H, alkyl,
Alkoxy, halogen, 2-thienyl, 3-thienyl,
Represents 1-pyrrolyl, 2-pyrrolyl, phenyl, 1-indolyl, 2-furanyl, 3-furanyl or carbazolyl, wherein R ₃₄ and R ₃₅ are alkyl, sulfoalkyl, carboxyalkyl, — (CH ₂ ) _n SO ₂ N— COR ₃₉ ,-
_{(CH 2) n SO 2 N} -SO 2 R 39, - (CH 2) n CON-SO
₂ R ₃₉ or — (CH ₂ ) _n CON-COR ₃₉ , and X ₃₁
And X ₃₂ represents O, S, Se, NR ₃₀ , M represents a counter ion, n represents a number of 2 to 4, and R ₃₉ and R _39
30 represents a C ₁ -C ₄ alkyl, or blue R ₃₁ and R ₃₂ or R ₃₂ and R _33, R ₃₆ and R ₃₇ or R ₃₇ and R ₃₈ represent the remaining members of a fused benzene or naphthalene ring] 2. The composition according to claim 1, further comprising a sensitizer.
The color photographic copier material described in 1. 4. The red sensitizer in at least one blue-sensitive layer is of the formula (V) [In the formula, X ₅₁ and X ₅₂ represent O, S, Se or NR ₃₀ , and R _{51 to} R ₅₃ and R _{56 to} R ₅₈ represent H, alkyl, alkoxy, halogen, 2-thienyl, 3-thienyl, 1
Represents -pyrrolyl, 2-pyrrolyl, phenyl, 1-indolyl, 2-furanyl, 3-furanyl or carbazolyl, wherein R ₅₄ and R ₅₅ are alkyl, sulfoalkyl, carboxyalkyl,-(CH ₂ ) _n SO ₂ N-COR ₃₉ ,-
_{(CH 2) n SO 2 N} -SO 2 R 39, - (CH 2) n CON-SO
₂ R ₃₉ or - indicates _{(CH 2) n CON-COR} 39, R 59
Represents H, alkyl, halogen, dialkylamino or thio, M represents a counter ion, n represents a number from 2 to 4, and R ₅₀ and R ₆₀ represent H or C ₁ -C ₄ alkyl; ₃₀ and R ₃₉ represent C ₁ -C ₄ alkyl, and R ₅₁ and R ₅₂ or R ₅₂ and R ₅₃ , R ₅₆ and R ₅₇ or R ₅₇ and R ₅₈ represent the remaining members of the fused benzene or naphthalene ring 2. The color photographic copying machine material according to claim 1, wherein: 5. The compound of formula (I) in at least one blue-sensitive layer
V): Wherein R ₄₁ and R ₄₃ represent hydrogen and R ₄₂ is halogen, especially chlorine or fluorine, or 2-thienyl, 3-
Represents thienyl, 1-pyrrolyl, 2-furanyl, 1-indolyl or phenyl, or R ₄₁ and R ₄₂ together or R ₄₂ and R ₄₃ together form the remaining benzene or naphthalene ring Member, R ₄₄
Represents hydrogen, R ₄₅ represents halogen, especially chlorine or fluorine, phenyl, 2-thienyl, 3-thienyl, 1-pyrrolyl, 2-furanyl, 1-indolyl, or R _45
44 and R ₄₅ together represent the remaining members of the fused benzene or naphthalene ring; X ₄₁ represents S or O;
Represents a counter ion, in particular triethylammonium, and l and m represent a number of from 2 to 4]. 6. A red sensitizer in at least one blue-sensitive layer.
The agent has the formula (VI):[Wherein, R₆₄And R₆₅Is alkyl, sulfoalkyl,
Carboxyalkyl,-(CH_Two)_nSO_TwoN-COR₆₉,
− (CH_Two)_nSO_TwoN-SO_TwoR₆₉,-(CH_Two)_nCON-S
O_TwoR₆₉Or-(CH_Two)_nCON-COR₆₉And R
₆₁, R₆₂, R₆₃, R₆₆, R₆₇ And R₆₈Are independent of each other
H, CH_Three, OCH _Three, Cl, 1-pyrrolyl, 1-a
, 2-thienyl, 3-thienyl, 2-furani
, 3-furanyl, N-carbazolyl or phenyl
Or R₆₁And R₆₂ Or R₆₂ And R₆₃,
And R₆₆ And R₆₇ Or R₆₇ And R₆₈ Is together
Becomes a benzo, 1,2-naphtho or 2,3-naphtho ring
The remaining members of X₆₁Represents O or S, and M represents
Indicates on, and R₆₉Is C₁-C_FourRepresents alkyl)
2. A color photograph according to claim 1, wherein:
Copier materials. 7. The method according to claim 1, wherein the at least one red-sensitive layer has the formula (I)
X) [Wherein, R ₉₁ represents an alkyl, alkenyl or aryl group, R ₉₂ and R ₉₃ each independently represent a hydrogen atom or an alkyl or alkoxy group having up to 16 carbon atoms, and R ₉₄ represents a hydrogen atom or an alkyl group. And R ₉₅ is C
₁ -C ₃ represents an alkylene group, and X ₉₁ represents an oxygen atom or a free electron pair, containing N, N-substituted p- aminophenol ethers wherein the alkyl group may be further substituted] 2. A color photographic copier material according to claim 1, wherein: 8. The p-aminophenol ether has the formula: Wherein R ₉₁ represents C ₁ -C ₂₀ alkyl, R ₉₄ represents hydrogen or methyl, and R ₉₂ and R ₉₃ are defined in claim 7
Wherein the total number of carbon atoms in R ₉₁ , R ₉₂ and R ₉₃ is at least 8]. 9. The compound of formula (I) has the formula (I-
A): Wherein R ₁₃ and R ₁₄ are independently R ₁₁ or R
Has the meaning of _12, X ₁₂ have the meanings given X _11, and Z ₁₂
Represents H or a substituent.] The color photographic copying machine material according to claim 1, wherein 10. A compound of the formula (VIII) Wherein R ₈₁ represents H or alkyl, alkenyl, aryl or acyl, R ₈₂ represents H or alkyl, alkoxy, aryloxy, acylamino, alkylamino, arylamino, hydroxy or hetaryl, and R ₈₃ Represents H, or an alkyl, alkenyl, aryl, acyl or chlorine, wherein the plurality of R ₈₂ and R ₈₃ groups can be the same or different]. The described color photocopier material.