EP0687952B1 - Colour photographic silver halide material - Google Patents

Description

The invention relates to a color photographic silver halide material with a novel coupler solvent.

Color photographic silver halide materials by the chromogenic process Color images usually contain at least one blue sensitive, silver halide emulsion layer containing at least one yellow coupler, at least one green-sensitive, containing at least one pupil coupler Silver halide emulsion layer and at least one red sensitive, silver halide emulsion layer containing at least one cyan coupler. The couplers are usually in fine droplets of a so-called coupler solvent dissolved or dispersed.

Suitable and common coupler solvents are e.g. tricresyl (TKP), dibutyl phthalate (DBP), but also fatty acid amides such as diethyl lauramide.

With these coupler solvents, the gradation is still not sufficiently steep and have not yet received sufficiently high maximum densities.

The object of the invention was therefore to provide new coupler solvents, with which improved maximum densities and steeper gradations are achieved but must not impair the stability of the dye.

It has now been found that this task can be accomplished with the following Can solve compounds of formula (I).

worin

R₁

Alkyl, Alkenyl, Cycloalkyl oder Cycloalkenyl,

R₂, R₃

Alkylen oder Alkenylen,

X

CO, NHCO oder SO₂,

n

0 oder 1 und

l, m

eine Zahl 1 bis 5 bedeuten.

The invention therefore relates to a color photographic silver halide material of the type mentioned at the outset, which is characterized in that at least one coupler is dissolved or dispersed in a compound of the formula (I),

wherein

R ₁

Alkyl, alkenyl, cycloalkyl or cycloalkenyl,

R ₂ , R ₃

Alkylene or alkenylene,

X

CO, NHCO or SO ₂ ,

n

0 or 1 and

l, m

represent a number 1 to 5.

NHCO groups for X are linked with their nitrogen atom to R ₁ .

Alkyl and alkenyl can be straight-chain or branched, unsubstituted or substituted his.

R ₁ is preferably linear or branched alkyl or alkenyl with 8 8 C atoms.

R ₂ and R ₃ are preferably identical and are preferably straight-chain or branched C ₂ -C ₈ alkylene.

l and m are preferably 1.

I-a:

I-b:

I-c:

I-d:

I-e:

I-f;

I-g:

I-h:

I-k;

I-l:

I-m:

I-n:

I-o:

I-p:

I-q:

I-r:

I-s:

I-t:

I-u:

I-w:

I-x:

I-y:

I-z:

Examples of coupler solvents according to the invention are.

Ia:

ib:

ic:

id:

Ie:

If;

Ig:

ih:

Ik;

Il:

In the:

In:

io:

ip:

iq:

Ir:

is:

It:

Iu:

iw:

ix:

iy:

Iz:

The couplers are usually used in an amount of 0.1 to 100 mmol / m ² . The coupler solvents according to the invention can be used in an amount of 0.05 to 3 g / g coupler. A mixture of several compounds according to the invention can also be used.

15 to 50% by weight of the total coupler solvent of at least one coupler are particularly preferably at least one coupler solvent according to the invention of formula (I). The coupler solvents according to the invention are in particular used for the purple couplers.

Teal couplers are usually phenol or α-naphthol type couplers.

Yellow couplers are usually couplers with an open chain ketomethylene grouping, in particular couplers of the α-acylacetamide type, for example Benzoylanilide couplers and α-pivaloylacetanilide couplers.

Pupur couplers are usually couplers of the 5-pyrazolone type Indazolons or the pyrazoloazole.

worin

R₄

H, Alkyl, Aralkyl oder Aryl;

R₅

H oder eine durch Kupplung freisetzbare Gruppe;

In a preferred embodiment, the recording material of the present invention contains, as magenta couplers, compounds of the formula (II)

wherein

R ₄

H, alkyl, aralkyl or aryl;

R ₅

H or a clutch releasable group;

Z _a , Z _b , Z _{c represent} an optionally substituted methine group, = N- or -NH-, where either the bond Z _a - Z _b or the bond Z _b - Z _{c is} a double bond and the other bond is a single bond.

Compounds of the formulas (II-A) to (II-G) below are particularly suitable:

In the general formulas (II-A) to (II-G), the radicals R ₄ , R ₆ , R ₇ and R _{8 represent} hydrogen, alkyl, aralkyl, aryl, alkoxy, aroxy, alkylthio, arylthio, amino, anilino, Acylamino, cyano, alkoxycarbonyl, carbamoyl, sulfamoyl, where these radicals can be further substituted.

Furthermore, R _{5 represents} hydrogen or a radical which can be split off on color coupling, such as a halogen atom or a preferably cyclic group attached to the coupling point via an oxygen atom, a sulfur atom or a nitrogen atom.

If the cleavable group is a cyclic group, can the connection to the coupling point of the coupler molecule either directly an atom that is part of a ring, e.g. a nitrogen atom, or indirectly be done via an intermediate link. Such split off Groups are known in large numbers, e.g. as escape groups of 2-equivalent purple couplers.

Examples of cleavable groups attached via oxygen correspond to the formula -OR ₉ , wherein R _{9 represents} an acyclic or cyclic organic radical, for example alkyl, aryl, a heterocyclic group or acyl, which is derived, for example, from an organic carbon or sulfonic acid. In particularly preferred cleavable groups of this type, R ₉ denotes an optionally substituted phenyl group.

Examples of cleavable groups linked via nitrogen are in DE-OS 2 536 191, 2 703 589, 2 813 522, 3 339 201.

These are often 5-membered heterocyclic rings, which a ring nitrogen atom connected to the coupling point of the purple coupler are. The heterocyclic rings often contain adjacent to that Activating binding to the coupler molecule mediating nitrogen atom Groups, e.g. Carbonyl or sulfonyl groups or double bonds.

If the cleavable group has a sulfur atom at the coupling point of the Coupler is bound, it can be the rest of a diffusible act carbocyclic or heterocyclic mercapto compound which the Can inhibit development of silver halide. Such inhibitor residues are often more than at the coupling point of couplers, also purple couplers bonded cleavable group, e.g. in US-A 3,227,554.

Particularly preferred couplers correspond to formulas II-D and II-E.

B-1

B-2

B-3

B-4

B-5

B-6

B-7

B-8

B-9

B-10

B-11

B-12

B-13

B-14

B-15

B-16

B-17

B-18

B-19

B-20

B-21

B-22

B-23

B-24

B-25

B-26

B-27

B-28

B-29

B-30

B-31

B-32

B-33

B-34

Examples of pyrazoloazole couplers of the formula II are:

B-1

B-2

B-3

B-4

B-5

B-6

B-7

B-8

B-9

B-10

B-11

B-12

B-13

B-14

B-15

B-16

B-17

B-18

B-19

B-20

B-21

B-22

B-23

B-24

B-25

B-26

B-27

B-28

B-29

B-30

B-31

B-32

B-33

B-34

worin

R₁

H, Alkyl, Aryl, Acyl;

R₂

-OR₁, -COOH, Alkyl, Aryl, Dialkylamino, Acylamino, Sulfonamido, Acyl, Sulfonyl;

R₃, R₄, R₅, R₆

H, Halogen oder einen Rest wie R₂ bedeuten oder

zwei benachbarte Reste -OR₁, R₂, R₃, R₄, R₅, R₆ zusammen einen 5- bis 8-gliedrigen Ring vervollständigen können.In a preferred embodiment of the invention, at least one light stabilizer of the formula (III) can be used together with the compounds according to the invention

wherein

R ₁

H, alkyl, aryl, acyl;

R ₂

-OR ₁ , -COOH, alkyl, aryl, dialkylamino, acylamino, sulfonamido, acyl, sulfonyl;

R ₃ , R ₄ , R ₅ , R ₆

Is H, halogen or a radical such as R ₂ or

two adjacent radicals -OR ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ together can complete a 5- to 8-membered ring.

An acyl group, also in the context of acylamino, is particularly important from a carbon, carbamate, carbonic or sulfonic acid.

The compounds of formula III are in particular in an amount of 0.05 up to 3 g / g coupler used.

worin

R₇

Alkyl, Acyl, Acylamino, Sulfonamido, Sulfonyl;

A

Einfachbindung, -CH(R₈)-, -O-, -S-, -SO₂-, -NR₉-,

X

-O-, -S-, -SO-, -SO₂-, -NAcyl-, -CO-;

R₈

H, Alkyl,

R₉

H, Alkyl, Acyl, Sulfonyl,

r

0, 1, 2, 3 oder 4;

s

0 oder 1;

t

0, 1, 2 oder 3;

u

0, 1, 2, 3, 4, 5 oder 6;

v

1 oder 2;

w

0, 1 oder 2 und

x

1, 2 oder 3 bedeuten.

In further preferred embodiments of the invention, the compound of the formula (III) corresponds in particular to one of the formulas (IIIa) to (IIIh).

wherein

R ₇

Alkyl, acyl, acylamino, sulfonamido, sulfonyl;

A

Single bond, -CH (R ₈ ) -, -O-, -S-, -SO ₂ -, -NR ₉ -,

X

-O-, -S-, -SO-, -SO ₂ -, -NAcyl-, -CO-;

R ₈

H, alkyl,

R ₉

H, alkyl, acyl, sulfonyl,

r

0, 1, 2, 3 or 4;

s

0 or 1;

t

0, 1, 2 or 3;

u

0, 1, 2, 3, 4, 5 or 6;

v

1 or 2;

w

0, 1 or 2 and

x

1, 2 or 3 mean.

Several radicals R ₇ or r, t, v, w, x can be the same or different. For the acyl group contained in the radical X (formula IIIe) and for a possible acyl group in the radicals R ₇ and R ₉ , the same applies to R ₁ to R ₆ .

C-1

C-2

C-3

C-4

C-5

C-6

C-7

C-8

C-9

C-10

C-11

C-12

C-13

C-14

C-15

C-16

C-17

C-18

C-19

C-20

C-21

C-22

C-23

C-24

C-25

C-26

C-27

C-28

C-29

C-30

C-31

C-32

C-33

C-34

C-35

C-36

mit n = 2,5Examples of compounds of the formula (III) are:

C-1

C-2

C-3

C-4

C-5

C-6

C-7

C-8

C-9

C-10

C-11

C-12

C-13

C-14

C-15

C-16

C-17

C-18

C-19

C-20

C-21

C-22

C-23

C-24

C-25

C-26

C-27

C-28

C-29

C-30

C-31

C-32

C-33

C-34

C-35

C-36

with n = 2.5

The color photographic recording material according to the invention contains at least a photosensitive silver halide emulsion layer, and preferably a sequence several such photosensitive silver halide emulsion layers and optionally further auxiliary layers, such as in particular protective layers and non-photosensitive arranged between the photosensitive layers Binder layers, according to the present invention at least one of the existing light-sensitive silver halide emulsion layers according to the invention Connection in combination with a color coupler, preferably a purple coupler.

Examples of color photographic materials are color negative films, color reversal films, Color positive films, color photographic paper, color reversal photographic paper, color sensitive materials for the color diffusion transfer process or the Silver dye bleach process.

Suitable supports for the production of color photographic materials are e.g. Movies and films of semi-synthetic and synthetic polymers, such as cellulose nitrate, Cellulose acetate, cellulose butyrate, polystyrene, polyvinyl chloride, polyethylene terephthalate and polycarbonate and with a baryta layer or α-olefin polymer layer (e.g. polyethylene) laminated paper. These carriers can be dyed and pigments, for example titanium dioxide. You can also go to For the purposes of shielding light, be colored black. The surface of the The carrier is generally subjected to a treatment to improve the adhesion of the to improve photographic emulsion layer, for example a corona discharge with subsequent application for a substrate layer.

Essential components of the photographic emulsion layers are binders, Silver halide grains and color couplers. The preferred binder is Gelatin used. However, this can be done in whole or in part by others synthetic, semisynthetic or naturally occurring polymers can be replaced.

The binders should have a sufficient amount of functional groups have so that sufficient by reaction with suitable curing agents resistant layers can be produced. Such functional groups are in particular amino groups, but also carboxyl groups, hydroxyl groups and active methyl groups.

The one found in the photographic material as a light-sensitive component Silver halide can be used as halide, chloride, bromide or iodide or mixtures of which included. For example, the halide content of at least one layer 0 to 15 mol% of iodide, 0 to 100 mol% of chloride and 0 to 100 mol% consist of bromide. In the case of color negative and color reversal films are usually silver bromide iodide emulsions, in the case of color negative and Color reversal paper typically has high silver chloride bromide emulsions Chloride content used up to pure silver chloride emulsions. It can be mainly compact crystals, which e.g. regular cubic or octahedral are or can have transitional forms. It can also be platy Crystals are present, their average ratio of diameter to thickness is preferably at least 5: 1, the diameter of a grain being defined as the diameter of a circle with a circle content corresponding to the projected Area of the grain. AgBrCl emulsions with at least 80 mol% AgCl, in particular at least 95 mol% AgCl used.

The silver halide grains can also have a multi-layered grain structure have, in the simplest case with an inner and an outer grain area (core / shell), the halide composition and / or other modifications, such as. Doping of the individual grain areas are different. The average grain size of the emulsions is preferably between 0.2 μm and 2.0 µm, the grain size distribution can be both homodisperse and heterodisperse. Homodisperse grain size distribution means that 95% of the grains do not exceed Deviate ± 30% from the average grain size. The emulsions can besides the silver halide also contain organic silver salts, e.g. silver benztriazolate or silver behenate.

There can be two or more types of silver halide emulsions that are separated are produced, used as a mixture.

The photographic emulsions can be prepared using various methods (e.g. P. Glafkides, Chimie et Physique Photographique, Paul Montel, Paris (1967), G.F. Duffin, Photographic Emulsion Chemistry, The Focal Press, London (1966), V.L. Zelikman et al, Making and Coating Photographic Emulsion, The Focal Press, London (1966) made from soluble silver salts and soluble halides become.

After completion of crystal formation or even to an earlier one At this point the soluble salts are removed from the emulsion, e.g. through pasta and washing, by flaking and washing, by ultrafiltration or by ion exchangers.

The silver halide emulsion generally undergoes chemical sensitization under defined conditions -pH, pAg, temperature, gelatin, silver halide- and sensitizer concentration - until the sensitivity and subjected to optimum veils. The procedure is e.g. at H. Frieser "The Basics of Photographic Processes with Silver Halides" Pages 675-734, Akademische Verlagsgesellschaft (1968).

The chemical sensitization with the addition of compounds of Sulfur, selenium, tellurium and / or compounds of the metals of subgroup VIII of the periodic table (e.g. gold, platinum, palladium, iridium) continue to occur can thiocyanate compounds, surface-active compounds, such as thioethers, heterocyclic nitrogen compounds (e.g. imidazoles, azaindenes) or also spectral sensitizers (described e.g. by F. Hamer "The Cyanine Dyes and Related Compounds ", 1964, or Ullmann's Encyclopedia of Chemical Engineering, 4th edition, vol. 18, p. 431 ff. And Research Disclosure 17643 (Dec. 1978), chapter III) are added. As an alternative or in addition, a reduction sensitization can with the addition of reducing agents (tin-II salts, amines, hydrazine derivatives, Aminoborane, silane, formamidine sulfinic acid) by hydrogen, by low pAg (e.g. less than 5) and / or high pH (e.g. above 8) become.

The photographic emulsions can be used to prevent the compounds Fog formation or to stabilize the photographic function during the Production, storage or photographic processing included.

Azaindenes are particularly suitable, preferably tetra- and penta-azaindenes, in particular those which are substituted by hydroxyl or amino groups. Such connections are for example from Birr, Z. Wiss. Phot. 47 (1952), pp. 2-58. Salts of metals such as mercury or cadmium, aromatic sulfonic or sulfinic acids such as benzenesulfinic acid, or nitrogen-containing heterocycles such as nitrobenzimidazole, nitroindazole, optionally substituted benzotriazoles or benzothiazolium salts can also be used as antifoggants. Heterocycles containing mercapto groups, for example mercaptobenzthiazoles, mercaptobenzimidazoles, mercaptotetrazoles, mercaptothiadiazoles, mercaptopyrimidines, are particularly suitable, these mercaptoazoles also being able to contain a water-solubilizing group, for example a carboxyl group or sulfo group. Other suitable compounds are published in Research Disclosure 17643 (Dec. 1978), Chapter VI.

The stabilizers can the silver halide emulsions before, during or after their maturation are added. Of course you can do the connections also other photographic layers associated with a halogen silver layer are to clog.

Mixtures of two or more of the compounds mentioned can also be used be used.

The photographic emulsion layers or other hydrophilic colloid layers of the light-sensitive material produced according to the invention can be surface-active Contains agents for various purposes, such as coating aids Prevention of electrical charging, to improve the sliding properties, to emulsify the dispersion, to prevent adhesion and to Improvement of the photographic characteristics (e.g. acceleration of development, high contrast, sensitization, etc.). In addition to natural surface-active Connections, e.g. Saponin, mainly find synthetic surfactants Compounds (surfactants) Use: non-ionic surfactants, e.g. alkylene oxide compounds, Glycerin compounds or glycidol compounds, cationic Surfactants, e.g. higher alkyl amines, quaternary ammonium salts, pyridine compounds and other heterocyclic compounds, sulfonium compounds or phosphonium compounds, anionic surfactants containing an acid group, e.g. Carboxylic acid, sulfonic acid, a phosphoric acid, sulfuric acid ester or phosphoric acid ester group, ampholytic surfactants, e.g. Amino acid and aminosulfonic acid compounds as well as sulfuric or phosphoric acid esters of an amino alcohol.

The photographic emulsions can be made using methine dyes or other dyes are spectrally sensitized. Particularly suitable dyes are cyanine dyes, merocyanine dyes and complex merocyanine dyes.

An overview of the polymethine dyes suitable as spectral sensitizers, their suitable combinations and super-sensitizing combinations contains Research Disclosure 17643 (Dec. 1978), Chapter IV.

1. als Rotsensibilisatoren
9-Ethylcarbocyanine mit Benzthiazol, Benzselenazol oder Naphthothiazol als basische Endgruppen, die in 5-und/oder 6-Stellung durch Halogen, Methyl, Methoxy, Carbalkoxy, Aryl substituiert sein können sowie 9-Ethyl-naphthoxathia-bzw. -selencarbocyanine und 9-Ethyl-naphthothiaoxa-bzw. -benzimidazocarbocyanine, vorausgesetzt, daß die Farbstoffe mindestens eine Sulfoalkylgruppe am heterocyclischen Stickstoff tragen.

2. als Grünsensibilisatoren
9-Ethylcarbocyanine mit Benzoxazol, Naphthoxazol oder einem Benzoxazol und einem Benzthiazol als basische Endgruppen sowie Benzimidazocarbocyanine, die ebenfalls weiter substituiert sein können und ebenfalls mindestens eine Sulfoalkylgruppe am heterocyclischen Stickstoff enthalten müssen.

3. als Blausensibilisatoren
symmetrische oder asymmetrische Benzimidazo-, Oxa-, Thia-oder Selenacyanine mit mindestens einer Sulfoalkylgruppe am heterocyclischen Stickstoff und gegebenenfalls weiteren Substituenten am aromatischen Kern, sowie Apomerocyanine mit einer Rhodaningruppe.

The following dyes, sorted by spectral region, are particularly suitable:

1. as red sensitizers
9-ethylcarbocyanines with benzthiazole, benzselenazole or naphthothiazole as basic end groups, which can be substituted in the 5- and / or 6-position by halogen, methyl, methoxy, carbalkoxy, aryl and 9-ethyl-naphthoxathia or. -selencarbocyanine and 9-ethyl-naphthothiaoxa or. -benzimidazocarbocyanine, provided that the dyes carry at least one sulfoalkyl group on the heterocyclic nitrogen.

2. as green sensitizers
9-ethyl carbocyanines with benzoxazole, naphthoxazole or a benzoxazole and a benzothiazole as basic end groups, and also benzimidazocarbocyanines, which may also be further substituted and must likewise contain at least one sulfoalkyl group on the heterocyclic nitrogen.

3. as blue sensitizers
symmetrical or asymmetrical benzimidazo, oxa, thia or selenacyanines with at least one sulfoalkyl group on the heterocyclic nitrogen and optionally further substituents on the aromatic nucleus, and apomerocyanines with a rhodanine group.

Sensitizers can be dispensed with if for a specific one Spectral range the intrinsic sensitivity of the silver halide is sufficient, for example the blue sensitivity of silver bromides.

The color couplers can be 4-equivalent couplers, but also Act 2-equivalent coupler. The latter are derived from the 4 equivalent couplers characterized in that they contain a substituent in the coupling site which at the clutch is split off. To the 2-equivalent couplers there are too count that are colorless, as well as those that have an intense intrinsic color, which disappears with the color coupling or through the color of the generated Image dye is replaced (mask coupler), and the white coupler, which in response with color developer oxidation products essentially colorless products result. The 2-equivalent couplers also include couplers that: contain a detachable residue in the coupling site, which reacts with Color developer oxidation products are set free and either directly or after the primary split off one or more more Groups have been split off (e.g. DE-A-27 03 145, DE-A-28 55 697, DE-A-31 05 026, DE-A-33 19 428), a certain desired photographic Effectiveness unfolds, e.g. as a development inhibitor or accelerator. Examples for such 2-equivalent couplers, the known DIR couplers are as well DAR and. FAR couplers.

DIR couplers, the development inhibitors of the azole type, e.g. Triazoles and benzotriazoles release, are in DE-A-24 14 006, 26 10 546, 26 59 417, 27 54 281, 28 42 063, 36 26 219, 36 30 564, 36 36 824, 36 44 416. Further Advantages for color rendering, i.e. Color separation and color purity, and for that Detail reproduction, i.e. Sharpness and graininess are too with such DIR couplers achieve, e.g. the development inhibitor not directly as a result of the coupling split off with an oxidized color developer, but only after one further follow-up reaction, which is achieved, for example, with a timing group. Examples of this are in DE-A-28 55 697, 32 99 671, 38 18 231, 35 18 797, in EP-A-0 157 146 and 0 204 175, in US-A-4 146 396 and 4 438 393 and in GB-A-2 072 363.

DIR couplers that release a development inhibitor that in the developer bath ineffective photographically ineffective products are, for example in DE-A-32 09 486 and in EP-A-0 167 168 and 0 219 713. With This measure will ensure trouble-free development and processing consistency reached.

When using DIR couplers, especially those that do a good job cleavable development inhibitor can be eliminated by suitable Measures for optical sensitization, improvements in color rendering, e.g. achieve a more differentiated color rendering, such as in EP-A-0 115 304, 0 167 173, GB-A-2 165 058, DE-A-37 00 419 and US-A-4,707,436.

The DIR couplers can be in a multi-layer photographic material various layers can be added, e.g. also insensitive to light or intermediate layers. However, they are preferably the photosensitive one Silver halide emulsion layers added, the characteristic properties the silver halide emulsion, e.g. their iodide content, the structure of the Silver halide grains or their grain size distribution have an influence on the achieved are photographic properties. The influence of the inhibitors released can, for example, by incorporating an inhibitor scavenger layer DE-A-24 31 223 can be limited. For reactivity or stability reasons it may be advantageous to use a DIR coupler that is in the respective Layer in which it is introduced, one of those to be generated in this layer Color deviates from the color of the coupling.

To increase sensitivity, contrast and maximum density can especially DAR or. FAR couplers are used which are a development accelerator or split off an fogger. Such connections are for example in DE-A-25 34 466, 32 09 110, 33 33 355, 34 10 616, 34 29 545, 34 41 823, in EP-A-0 089 834, 0 110 511, 0 118 087, 0 147 765 and in U.S.-A-4,618,572 and 4,656,123.

As an example for the use of BAR couplers (Bleach Accelerator Releasing Coupler) is referred to EP-A-193 389.

It may be advantageous to photograph the effect of a split off from a coupler effective group by modifying an intermolecular reaction according to this group after their release with another group DE-A-35 06 805 occurs.

Since the DIR, DAR or. FAR couplers mainly the effectiveness of the released in the clutch rest is desired and less on the color-forming properties of these couplers are also such DIR, DAR and. Suitable for FAR couplers, which are essentially colorless when coupling Products result (DE-A-15 47 640).

The cleavable residue can also be a ballast residue, so that in the reaction with Color developer oxidation products coupling products are obtained that are diffusible are or at least weak or limited mobility (US-A-4 420 556).

The material may also contain compounds other than couplers, which, for example, a development inhibitor, a development accelerator, a bleach accelerator, a developer, a silver halide solvent Can release fogging or an anti-fogging agent, for example So-called DIR hydroquinones and other compounds, such as those described in US-A-4 636 546, 4 345 024, 4 684 604 and in DE-A-31 45 640, 25 15 213, 24 47 079 and in EP-A-198 438 are described. Meet these connections the same function as the DIR, DAR or FAR couplers, except that they are none Form coupling products.

High molecular weight color couplers are described, for example, in DE-C-1 297 417, DE-A-24 07 569, DE-A-31 48 125, DE-A-32 17 200, DE-A-33 20 079, DE-A-33 24 932, DE-A-33 31 743, DE-A-33 40 376, EP-A-27 284, US-A-4 080 211. The high molecular color couplers are used in the Usually by polymerizing ethylenically unsaturated monomers Color couplers manufactured. But you can also by polyaddition or Polycondensation can be obtained.

Incorporation of the couplers or other compounds in silver halide emulsion layers can be done in such a way that first of the connection in question prepared a solution, a dispersion or an emulsion and then the Pouring solution for the layer in question is added. Choosing the right one Solvent or dispersant depends on the particular solubility of the compound from.

Methods for introducing compounds which are essentially insoluble in water by grinding processes are for example in DE-A-26 09 741 and DE-A-26 09 742.

Hydrophobic compounds can also be made using high-boiling Solvents, so-called oil formers, are introduced into the casting solution. Appropriate methods are described, for example, in US Pat. No. 2,322,027. US-A-2 801 170, US-A-2 801 171 and EP-A-O 043 037.

Instead of the high-boiling solvents, oligomers or polymers, so-called polymeric oil formers are used. Especially for the yellow dome Layer the compounds of the invention are used.

The compounds can also be in the form of loaded latices in the casting solution be introduced. Reference is made, for example, to DE-A-25 41 230, DE-A-25 41 274, DE-A-28 35 856, EP-A-O 014 921, EP-A-0 069 671, EP-A-0 130 115, US-A-4,291,113.

The diffusion-resistant storage of anionic water-soluble compounds (e.g. of dyes) can also be used with the help of cationic polymers, so-called Pickling polymers take place.

Suitable oil formers in addition to the compounds according to the invention are e.g. Alkyl phthalates, phosphonic acid esters, phosphoric acid esters, citric acid esters, Benzoic acid esters, amides, fatty acid esters, trimesic acid esters, alcohols, phenols, Aniline derivatives and hydrocarbons.

Each of the differently sensitized, light-sensitive layers can be made of consist of a single layer or two or more silver halide emulsion partial layers include (DE-C-1 121 470). Here are sensitive to red Silver halide emulsion layers are often closer to the substrate arranged as green sensitive silver halide emulsion layers and these again closer than blue-sensitive, with generally between green-sensitive layers and blue-sensitive layers are not photosensitive yellow filter layer.

With a suitably low intrinsic sensitivity of the green or red-sensitive Other layers can be used without the yellow filter layer Choose layer arrangements in which e.g. the blue sensitive, then the red-sensitive and finally the green-sensitive layers follow.

The usually between layers of different spectral sensitivity arranged non-light-sensitive intermediate layers can contain agents which an undesirable diffusion of developer oxidation products from a photosensitive to another photosensitive layer with different prevent spectral sensitization.

Suitable agents, also called scavengers or EOP-catchers, are described in Research Disclosure 17,643 (Dec. 1978), Chapter VII, 17,842 (Feb. 1979) and 18 716 (Nov. 1979), page 650 and in EP-A-0 069 070, 0 098 072, 0 124 877, 0 125 522.

If there are several sub-layers of the same spectral sensitization, then these with regard to their composition, especially what type and quantity the silver halide grains concern differentiate. In general, the Partial layer with higher sensitivity from the carrier can be arranged as the sublayer with less sensitivity. Sub-layers of the same spectral Sensitization can be adjacent to one another or through other layers, e.g. separated by layers of other spectral sensitization. For example, all highly sensitive and all low sensitive layers in one Layer package can be summarized (DE-A-19 58 709, DE-A-25 30 645, DE-A-26 22 922).

The photographic material can also contain UV light-absorbing compounds, whiteners, spacers, filter dyes, formalin scavengers, light stabilizers, antioxidants, D _min dyes, additives to improve dye, coupler and white stabilization and to reduce the color fog, plasticizers (latices), Contain biocides and others.

Certain layers of binder, especially those furthest from the carrier removed layer, but also occasionally intermediate layers, especially if the most distant layer during manufacture can represent photographically inert particles of inorganic or organic Contain nature, e.g. as a matting agent or as a spacer (DE-A-33 31 542, DE-A-34 24 893, Research Disclosure 17 643, (Dec. 1978), Chapter XVI).

The average particle diameter of the spacers is in particular Range from 0.2 to 10 µm. The spacers are water-insoluble and can be alkali-insoluble or alkali-soluble, the alkali-soluble in general alkaline developing bath can be removed from the photographic material. Examples of suitable polymers are polymethyl methacrylate, copolymers of Acrylic acid and methyl methacrylate and hydroxypropyl methyl cellulose hexahydrophthalate.

Additives to improve dye, coupler and whiteness stability and Reduction of the color fog (Research Disclosure 17 643 (Dec. 1978), chapter VII) can belong to the following chemical substance classes: hydroquinones, 6-hydroxychromanes, 5-hydroxycoumarans, spirochromanes, spiroindanes, p-alkoxyphenols, sterically hindered phenols, gallic acid derivatives, methylenedioxybenzenes, Aminophenols, sterically hindered amines, derivatives with esterified or etherified phenolic hydroxyl groups, metal complexes.

Compounds that have a hindered amine partial structure as well have a sterically hindered phenol partial structure in one molecule (US-A-4,268,593) are particularly effective in preventing impairment of yellow color images as a result of the development of heat, moisture and Light. About the impairment of purple color images, especially theirs Impairment as a result of exposure to light are to be prevented Spiroindane (JP-A-159 644/81) and chromane by hydroquinone diether or -monoethers are particularly effective (JP-A-89 835/80).

example 1

Schicht 1:

Substratschicht aus 200 mg Gelatine

Schicht 2:

Grünempfindliche Silberchloridbromidemulsionsschicht (99,5 mol-% Chlorid) aus 530 mg AgNO₃ mit 750 mg Gelatine

0,61 g Purpurkuppler B-23

0,61 g TKP

Schicht 3:

Schutzschicht aus 1 g Gelatine und 120 mg Härtungsmittel H1 der Formel

The following layers were applied to a layer support made of paper coated on both sides with polyethylene. The quantities given relate to 1 m ² .

Layer 1:

200 mg gelatin substrate layer

Layer 2:

Green-sensitive silver chloride bromide emulsion layer (99.5 mol% chloride) from 530 mg AgNO ₃ with 750 mg gelatin

0.61 g purple coupler B-23

0.61 g CPM

Layer 3:

Protective layer consisting of 1 g gelatin and 120 mg hardening agent H1 of the formula

In further samples, CPM was determined by the inventive methods shown in Table 1 Connections replaced.

a) Farbentwickler -45 s - 35°C Triethanolamin 9,0 g N,N-Diethylhydroxyamin 4,0 g Diethylenglykol 0,05 g 3-Methyl-4-amino-N-ethyl-N-methan-sulfonaminoethyl-anilin-sulfat 5,0 g Kaliumsulfit 0,2 g Triethylenglykol 0,05 g Kaliumcarbonat 22 g Kaliumhydroxid 0,4 g Ethylendiamintetraessigsäure-di-Na-Salz 2,2 g Kaliumchlorid 2,5 g 1,2-Dihydroxybenzol-3,4,6-trisulfonsäure-trinatriumsalz auffüllen mit Wasser auf 1.000 ml; pH 10,0 0,3 g

b) Bleichfixierbad - 45 s - 35°C Ammoniumthiosulfat 75 g/l Natriumhydrogensulfit 13,5 g/l Ammoniumacetat 2,0 g/l Ethylendiamintetraessigsäure (Eisen-Ammonium-Salz) 57 g/l Ammoniak 25 gew.-%ig 9,5 g/l Essigsäure auffüllen mit Wasser auf 1.000 ml; pH 5,5 9,0 g/l

c) Wässern - 2 min - 35°C

d) Trocknen Probe TKP (Gew.-%) Verbindung I Gew.-%) D_max 1 Vergleich 100 - - 2,21 2 Erfindung 80 I-a 20 2,31 3 Erfindung 60 I-a 40 2,38 4 Erfindung 60 I-d 40 2,36 5 Erfindung 60 I-o 40 2,43 6 Erfindung 60 I-p 40 2,35

The samples thus produced were exposed imagewise and processed in the customary manner in the processing baths listed below.

a) Color developer -45 s - 35 ° C triethanolamine 9.0 g N, N-diethylhydroxyamine 4.0 g diethylene glycol 0.05 g 3-methyl-4-amino-N-ethyl-N-methane-sulfonaminoethyl-aniline sulfate 5.0 g potassium 0.2 g triethylene 0.05 g potassium carbonate 22 g potassium hydroxide 0.4 g Ethylenediaminetetraacetic acid disodium salt 2.2 g potassium chloride 2.5 g 1,2-Dihydroxybenzene-3,4,6-trisulfonic acid trisodium salt make up to 1,000 ml with water; pH 10.0 0.3 g

b) bleach-fix bath - 45 s - 35 ° C ammonium 75 g / l sodium bisulfite 13.5 g / l ammonium acetate 2.0 g / l Ethylenediaminetetraacetic acid (iron ammonium salt) 57 g / l Ammonia 25% by weight 9.5 g / l Fill up acetic acid with water to 1,000 ml; pH 5.5 9.0 g / l

c) Soak - 2 min - 35 ° C

d) drying sample CPM (% by weight) Compound I Wt .-%) D _max 1 comparison 100 - - 2.21 2 invention 80 Ia 20 2.31 3 Invention 60 Ia 40 2.38 4 Invention 60 id 40 2.36 5 Invention 60 io 40 2.43 6 Invention 60 ip 40 2.35

As Table 1 shows, the coupler solvents according to the invention are used significant increase in maximum density achieved.

Example 2

A color photographic recording material suitable for a rapid processing process was produced by applying the following layers in the order given to a support made of paper coated on both sides with polyethylene. The quantities given relate to 1 m ² . The corresponding amounts of AgNO ₃ are given for the silver halide application.

Layer structure sample 1

Layer 1:

(Substrate layer)
0.2 g gelatin

Layer 2:

(blue sensitive layer)
blue-sensitive silver halide emulsion (99.5 mol% chloride,
0.5 mol% bromide, average grain diameter 0.8 µm)
0.45 g AgNO ₃ with
1.08 g gelatin
0.60 g yellow coupler Y-1
0.215 g white coupler W-1
0.30 g CPM

Layer 3:

(Protective layer)
1.1 g gelatin
0.03 g 2,5-dioctyl hydroquinone
0.03 g SC-1
0.06 g CPM

Layer 4:

(green sensitive layer)
green-sensitized silver halide emulsion (99.5 mol% chloride,
0.5 mol% bromide, average grain diameter 0.6 µm)
0.3 g of AgNO ₃ with
1.08 g gelatin
0.31 g purple coupler B-23
0.2 g image stabilizer C-20
0.1 g image stabilizer C-24
0.08 g 2,5-dioctyl hydroquinone
0.31 g DBP

Layer 5:

(UV protective layer)
1.15 g gelatin
0.4 g UV absorber UV-1
0.2 g UV absorber UV-2
0.022 g of 2,5-dioctyl hydroquinone
0.022 g SC-1
0.1g CPM
0.2 g diisononyl adipate

Layer 6:

(red sensitive layer)
red-sensitized silver halide emulsion (99.5 mol% chloride,
0.5 mol% bromide, average grain diameter 0.5 µm)
0.3 g of AgNO ₃ with
0.75 g gelatin
0.36 g of cyan coupler C-1
0.36 g CPM

Layer 7:

(UV protective layer)
0.35 g gelatin
0.1 g UV absorber UV-1
0.05 g UV absorber UV-2
0.2 g CPM

Layer 8:

(Protective layer)
0.9 g gelatin
0.3 g of H-1 curing agent

Y-1

SC-1

W-1

C-1

UV-1

UV-2

The samples thus produced were exposed and processed as in Example 1.

The processed samples were then covered with a UV protective film and irradiated in a xenon test device to determine the light fastness (15 · 10 ⁶ 1xh).

The UV protective film was produced as follows: a layer of 1.5 g of gelatin, 0.65 g of UV absorber UV-1, 0.07 g of dioctylhydroquinone and 0.36 g of CPM was placed on a transparent cellulose triacetate film provided with an adhesive layer applied. The amounts relate to 1 m ² .

The results are shown in Table 2.

As shown in Table 2, the compounds according to the invention as coupler solvents significantly increase the maximum density. Comparative sample 8 shows, compared to sample 7, no improvement in the maximum density and drastic deterioration in the light stability of the dye. In addition to increasing the maximum density, the compounds according to the invention also improve the light stability.

Claims (5)

1. Silver halide photographic colour material comprising at least one blue-sensitive silver halide emulsion layer containing at least one yellow-forming colour coupler, at least one green-sensitive silver halide emulsion layer containing at least one magenta-forming colour coupler, and at least one red-sensitive silver halide emulsion layer containing at least one cyan-forming colour coupler, at least one coupler being dissolved or dispersed in a coupler solvent, characterised in that the coupler solvent used is a compound corresponding to formula (I):

   

   wherein

   R₁ represents alkyl, alkenyl, cycloalkyl or cycloalkenyl,

   R₂, R₃ represent alkylene or alkenylene,

   X represents CO, NHCO or SO₂,

   n is 0 or 1 and

   l, m are numbers of 1 to 5.
2. The silver halide photographic colour material according to claim 1, wherein

   R₁ is linear alkyl or alkenyl having at least 8 carbon atoms;

   R₂ and R₃ represent linear or branched alkylene having 2 to 8 carbon atoms; and

   l and m are 1.
3. The silver halide photographic colour material according to claim 1, wherein said coupler dissolved or dispersed in said compound of formula I is a magenta-forming colour coupler corresponding to formula (II):

   

   wherein R₄ represents H, alkyl, aralkyl or aryl;

   R₅ represents H or a group releasable by coupling;

   Z_a, Z_b and Z_c represent a substituted or unsubstituted methine group, =N- or -NH-, either the bond Z_a - Z_b or the bond Z_b - Z_c being a double bond and the other bond being a single bond.
4. The silver halide photographic colour material according to claim 3, wherein said coupler corresponds to one of the formulae II-D or II-E:

   

   wherein

   R₄, R₆, and R₇ represent hydrogen, alkyl, aralkyl, aryl, alkoxy, aroxy, alkylthio, arylthio, amino, anilino, acylamino, cyano, alkoxycarbonyl; carbamoyl, sulphamoyl; said radicals optionally being further substituted; and

   R₅ represents hydrogen or a radical releasable upon colour coupling.
5. The silver halide photographic colour material according to claim 1, wherein further a light stabiliser corresponding to the formula III is used:

   

   wherein

   R₁ represents H, alkyl, aryl, acyl;

   R₂ represents -OR₁, -COOH, alkyl, aryl, dialkylamino, acylamino, sulphonamido, acyl, sulphonyl;

   R₃, R₄, R₅ and R₆ represent H, halogen or a radical with the same meaning as defined for R₂; or

   two adjacent radicals -OR₁, R₂, R₃, R₄, R₅ and R₆ together may complete a 5- to 8-membered ring.