DE4001784C2 - Color photographic silver halide material - Google Patents

Description

The invention relates to a color photographic silver halide material with a carrier, at least one red-sensitive, containing at least one cyan coupler Silver halide emulsion layer, at least a green-sensitive, at least one purple coupler containing silver halide emulsion layer, at least a blue-sensitive, at least one yellow coupler containing silver halide emulsion layer and two non-photosensitive layers A and B, all photosensitive layers and layers A and B are attached to the same side of the carrier that Layer A is farther from the support than any photosensitive Layers and layer B further from Carrier is removed as layer A.

Silver halide color photographic materials of the above are mentioned with two outer layers already known from EP-A 2 57 515, the layer A gelatin, a thickener and an instant hardener  and layer B gelatin, a thickener polymer having reactive groups, a lubricant and a spacer (matting agent) that can be alkali-soluble or alkali-insoluble, contains.

In the previously known material, layers A and B in a separate operation on the material that all other layers including UV absorption layer and contained the last intermediate layer applied, be applied, otherwise serious Set disadvantages. Since it is with known technology it is readily possible to use at least four layers Help from cascade or curtain casters at the same time pouring, the application uses only two layers in one Pouring the given possibilities are not optimal from, resulting in an additional pouring process over the depending on the material and the casting device determined optimal number of casting processes leads. It was also found that that described in EP 2 57 515 Procedures often had to be interrupted to the pouring device clean of deposits.

The object of the invention was therefore the composition to change layers A and B so that they are common with other photosensitive and photosensitive Layers can be poured without the previous mentioned adverse effects or other disadvantages observed become. Another job was to use UV absorbers and micro emulsion in one of the layers A or B  to integrate, so that an additional UV absorber layer can be dispensed with.

These tasks are solved in that
layer A

• (a) a UV absorber,
• (b) optionally a finely divided, not photosensitive silver halide emulsion,
• (c) a hydrophilic binder, in particular gelatin,
• (d) a plasticizer and
• (e) a thickener and

layer B

• (a) an alkali-insoluble spacer,
• (b) a polymer containing reactive groups,
• (c) a lubricant,
• (d) a thickener,
• (e) an instant hardener,
• (f) an alkali-soluble spacer and
• (g) optionally a finely divided, non-photosensitive Contain silver halide emulsion,

where at least one of layers A or B is the finely divided, non-photosensitive silver halide emulsion contains.  

In a preferred embodiment, between the last photosensitive layer and layer A no further layer arranged.

In other preferred embodiments Layer A contains at least one correction dye Layer B a hydrophilic binder, in particular gelatin, and contains layer B a finely divided quartz dispersion.

Alkaline soluble spacers, in particular an average particle diameter of 0.5 to 8 µm, preferably 1 to 6 µm with a particle size distribution of ± 2 µm, z. B. graft polymers based on methacrylic acid and methyl methacrylate on styrene maleic acid half ester copolymers as Graft base and in particular cellulose derivatives that are described by the general formula below to let:

(R₁) _m - (R₂) _n - (R₃) _p - A

in which
A a cellulose residue,
R₁ is a hydroxyalkyl radical with 2 to 4 carbon atoms,
R₂ is an alkyl radical with 1 to 3 carbon atoms,
R₃ is the monoacyl radical of a benzenedicarboxylic acid or such an acid in partially or fully hydrogenated form,
m 0.2-1,
n 0.8-2.0 and
p mean 0.5-1.5
and the sum m + n + p is at most 3.

Examples of the above-mentioned dicarboxylic acid monoesters are esters of phthalic acid, tetrahydrophthalic acid or hexahydrophthalic acid. In the cellulose derivatives of the invention, these dicarboxylic acid monoesters are about one of their carboxyl groups with mixed ethers of cellulose, e.g. B. hydroxyethyl methyl cellulose, hydroxypropyl methyl cellulose, Hydroxyethyl ethyl cellulose or hydroxypropyl ethyl cellulose, esterified. The content of the cellulose derivatives of dicarboxylic acid monoesters is said to correspond to The hydrophobic effect of the cellulose ethers is adjusted be that the desired in alkaline solution Solubility is achieved.

The alkali-soluble spacers come in a lot from 10 to 500 mg / m², preferably 50 to 200 mg / m² of material applied.  

Particularly suitable cellulose derivatives have e.g. B. following composition:

Connection A:
17.4% by weight methoxy groups
7.2% by weight hydroxypropoxy groups
35.0 wt% hexahydrophthaloyl groups.

Compound B:
18.0% by weight methoxy groups
9.0 wt% hydroxypropoxy groups
35.0% by weight of phthaloyl groups.

The polymers containing reactive groups have a Molecular weight Mn of at least 10,000 and in particular from 100,000 to 2,000,000, whereby for cross-linked polymers that are used as latices, Molecular weights up to 10¹² result.

They consist of at least 0.2 mol% and in particular to 0.5 to 40 mol% of monomers of the formula

wherein
R₄, R₅ and R₆ are the same or different and are hydrogen, alkyl, in particular with 1 to 4 carbon atoms, halogen, in particular Cl,
L is a chemical bond or a common link,
X represents a reactive group.

A reactive group is a group the containing with -NH₂-, -COOH or -OH groups Substances in an addition or condensation reaction can react so that a chemical linkage with the appropriate substance. Especially these are reactive groups with Gelatin can react in the specified manner.

These polymers have an average particle diameter from 0.05 to 0.20 µm and are particularly in an amount of 30 to 250 mg / m² of material used.

Preferred reactive groups are

with R₇, R₈ = alkyl, aryl, aralkyl.

In a preferred embodiment, the Monomers of the compounds containing reactive groups of the formula

wherein X, R₄, R₅ and R₆ have the meaning given above,
L₁ -COO-, -CONH- or phenylene and
L₂ is a simple bond, alkylene, alkenylene, -SO₂- alkylene or alkylene-NHCO-alkylene.

As further monomers of the polymers with reactive groups come z. B. ethyl methacrylate, methyl methacrylate, isobornyl methacrylate, Phenyl methacrylate, cyclohexyl chloroacrylate, Methyl chloroacrylate, 4-tert-butylstyrene, 2,5- Dimethylstyrene, styrene, vinyl toluene, acrylonitrile, methacrylonitrile into consideration.

Examples of suitable high molecular compounds where the monomer content is given in% by weight:

As a binder in layers A and B as well gelatin preferably used in other layers. However, this can be partly due to other synthetic, semisynthetic or naturally occurring polymers be replaced. Synthetic gelatin substitutes Examples include polyvinyl alcohol, poly-N-vinyl pyrrolidone, Polyacrylamides, polyacrylic acid and their derivatives, especially their copolymers. Naturally Occurring gelatin substitutes are, for example other proteins such as albumin or casein, cellulose, Sugar, starch or alginates. Semi-synthetic gelatin substitutes are usually modified natural products, Cellulose derivatives such as hydroxyalkyl cellulose, Carboxymethyl cellulose and phthalyl cellulose as well as gelatin derivatives, which by reaction with alkylation  or acylating agents or by grafting on polymerizable monomers have been obtained Examples of this.

The binders should have a sufficient amount of functional groups so that by implementation sufficiently resistant with suitable hardening agents Layers can be created. Such functional Groups are especially amino groups, but also Carboxyl groups, hydroxyl groups and active methylene groups.

The gelatin which is preferably used can be acidic or alkaline digestion. It can also oxidized gelatin can be used. The production such gelatin is described, for example, in The Science and Technology of Gelatine, edited by A.G. Ward and A. Courts, Academic Press 1977, page 295 ff. The gelatin used should be as possible low level of photographically active impurities contain (inert gelatine), gelatine with high viscosity and low swelling are special advantageous.

Layer A preferably contains 100 to 300 mg / m², in layer B if this layer is hydrophilic Binder contains up to 10 to 300 mg / m² of hydrophilic Binder used.

As a lubricant z. B. polyethylene waxes and Polysiloxanes such as dimethylpolysiloxane with a molecular weight Mn from 2000 to 5000.  

These compounds are used in an amount of 5 to 60 mg / m² Material used.

High-molecular compounds are suitable as thickeners, which are used in small quantities in an aqueous System for a large increase in viscosity. they must be photographically inert and should not be used with the reactive polymer-bearing polymer with the Immediate curing agents described below react.

The thickeners are preferred in layer A. in an amount of 10 to 100 mg / m² and in layer B preferably in an amount of 10 to 50 mg / m² material used.

Suitable thickeners are e.g. B. polystyrene sulfonic acid and copolymers of acrylamide and N-sulfo-t-butyl acrylamide.

Alkali-insoluble spacers can be more inorganic or be organic in nature and have average particle diameters from 0.5 to 10 µm, especially 1 to 8 µm. The alkali-insoluble spacers are preferred in an amount of 5 to 30 mg / m² material used.

Suitable examples of alkali-insoluble spacers are silicon oxide, magnesium dioxide, titanium dioxide, calcium carbonate and polymethyl methacrylate.  

Immediate hardeners are understood to mean connections that crosslink suitable binders so that immediately after Watering or at the latest after 24 hours, preferably after 8 hours, the hardening is so far completed that none further change due to the crosslinking reaction the sensitometry and the swelling of the layer structure occurs. The difference between Wet film thickness and dry film thickness in the aqueous Processing of the film understood (Photogr. Sci. Eng. 8 [1964], 275; Photogr. Sci. Closely. 16 [1972], 449).

These hardening agents that react very quickly with gelatin is it z. B. carbamoylpyridinium salts, which presumably with free carboxyl groups of proteinaceous binder are able to react, so that the latter with free amino groups under training of peptide bonds and crosslinking of the binder can react. Because of this quick effect the instant hardeners mentioned contain gelatin-containing casting solutions are generally only added shortly before the watering, otherwise, due to premature reaction, the casting properties especially the viscosity of the casting solutions would be changed quickly and disadvantageously. In general becomes the immediate hardener of the top layer (protective layer) added. It gets into the by diffusion other layers to be hardened containing gelatin and crosslinked in it the gelatin so quickly that already after drying is almost complete and those for the physical and photographic properties characteristic parameters their final Have reached values.  

Suitable examples of instant hardeners are compounds of the following general formulas:

wherein
R₁ denotes alkyl, aryl or aralkyl,
R₂ has the same meaning as R₁ or means alkylene, arylene, aralkylene or alkaralkylene, the second bond having a group of the formula

is linked, or
R₁ and R₂ together mean the atoms required to complete an optionally substituted heterocyclic ring, for example a piperidine, piperazine or morpholine ring, the ring being e.g. B. may be substituted by C₁-C₃-alkyl or halogen,
R₃ for hydrogen, alkyl, aryl, alkoxy, -NR₄-COR₅, - (CH₂) _m -NR₈R₉, - (CH₂) _n -CONR₁₃R₁₄ or

or a bridge link or a direct bond to a polymer chain, wherein
R₄, R₆, R₇, R₉, R₁₄, R₁₅, R₁₇, R₁₈, and R₁₉ are hydrogen or C₁-C₄-alkyl,
R₅ is hydrogen, C₁-C₄-alkyl or NR₆R₇,
R₈ -COR₁₀
R₁₀ NR₁₁R₁₂
R₁₁ C₁-C₄ alkyl or aryl, especially phenyl,
R₁₂ is hydrogen, C₁-C₄ alkyl or aryl, especially phenyl,
R₁₃ is hydrogen, C₁-C₄ alkyl or aryl, especially phenyl,
R₁₆ is hydrogen, C₁-C₄-alkyl, COR₁₈ or CONHR₁₉,
m is a number 1 to 3,
n is a number 0 to 3,
p is a number 2 to 3 and
Y is O or NR₁₇ or
R₁₃ and R₁₄ together represent the atoms required to complete an optionally substituted heterocyclic ring, for example a piperidine, piperazine or morpholine ring, the ring z. B. can be substituted by C₁-C₃-alkyl or halogen,
Z is the carbon atoms and necessary for the completion of a 5- or 6-membered aromatic heterocyclic ring, optionally with a fused benzene ring
X⊖ is an anion which is omitted if an anionic group is already linked to the rest of the molecule;

wherein
R₁, R₂, R₃ and X⊖ have the meaning given for formula (a);

wherein
R₂₀, R₂₁, R₂₂, R₂₃, C₁-C₂₀-alkyl, C₆-C₂₀-aralkyl, C₅-C₂₀-aryl, each unsubstituted or by halogen, sulfo, C₁-C₂₀-alkoxy, N, N-di-C₁-C₄- alkyl-substituted carbamoyl and, in the case of aralkyl and aryl, substituted by C₁-C₂₀-alkyl,
R₂₄ mean a group cleavable by a nucleophilic agent and
X⊖ has the meaning given for formula (a), where
2 or 4 of the substituents R₂₀, R₂₁, R₂₂ and R₂₃ together with a nitrogen atom or the group

optionally including other heteroatoms like O or N also one or two saturated, 5-7-membered rings united could be;

R₂₅-N = C = N-R₂₆ (d)

wherein
R₂₅ is C₁-C₁₀-alkyl, C₅-C₈-cycloalkyl, C₃-C₁₀-alkoxyalkyl or C₇-C₁₅-aralkyl,
R₂₆ has the meaning of R₂₅ or for a radical of the formula

stands, where
R₂₇ C₂-C₄ alkylene and
R₂₈, R₂₉ and R₃₀ are C₁-C₆-alkyl, where one of the radicals R₂₈, R₂₉ and R₃₀ can be substituted by a carbamoyl group or a sulfo group and two of the radicals R₂₈, R₂₉ and R₃₀ together with the nitrogen atom to form an optionally substituted heterocyclic ring, For example, a pyrrolidine, piperazine or morpholine ring can be linked, the ring z. B. can be substituted by C₁-C₃-alkyl or halogen, and
X⊖ has the meaning given for formula (a);

wherein
X⊖ has the meaning given for formula (a),
R₂₄ has the meaning given for formula (c),
R₃₁ C₁-C₁₀-alkyl, C₆-C₁₅-aryl or C₇-C₁₅-aralkyl, in each case unsubstituted or substituted by carbamoyl, sulfamoyl or sulfo,
R₃₂ and R₃₃ represent hydrogen, halogen, acylamino, nitro, carbamoyl, ureido, alkoxy, alkyl, alkenyl, aryl or aralkyl or together the remaining members of a ring condensed with the pyridinium ring, in particular a benzo ring,
in which
R₂₄ and R₃₁ can be linked when R₂₄ is a sulfonyloxy group;

wherein
R₁, R₂ and X⊖ have the meaning given for formula (a) and
R₃₄ is C₁-C₁₀ alkyl, C₆-C₁₄ aryl or C₇-C₁₅ aralkyl;

wherein
R₁, R₂ and X⊖ have the meaning given for formula (a),
R₃₅ is hydrogen, alkyl, aralkyl, aryl, alkenyl, R₃₈O-, R₃₉R₄₀N, R₄₁R₄₂C = N- or R₃₈S-,
R₃₆ and R₃₇ alkyl, aralkyl, aryl, alkenyl,

or together with the nitrogen atom the remaining members of a heterocyclic Ringes or the grouping

R₃₈, R₃₉, R₄₀, R₄₁, R₄₂, R₄₃, R₄₄ and R₄₅ alkyl, Aralkyl, alkenyl, R₄₁ and R₄₂ in addition Hydrogen, R₃₉ and R₄₀ or R₄₁ and R₄₂ furthermore the remaining links of a 5- or 6-membered, saturated carbocyclic or heterocyclic ring;

wherein
R₄₆ is hydrogen, alkyl or aryl,
R₄₇ acyl, carbalkoxy, carbamoyl or aryloxycarbonyl,
R₄₈ is hydrogen or R₄₇,
R₄₉ and R₅₀ are alkyl, aryl, aralkyl or together with the nitrogen atom the remaining members of an optionally substituted heterocyclic ring, for example a piperidine, piperazine or morpholine ring, the ring being z. B. can be substituted by C₁-C₃-alkyl or halogen, and
X⊖ has the meaning given for formula (a);

wherein
R₅₁ is an optionally substituted heteroaromatic ring which contains at least q ring C atoms and at least one ring O, ring S or ring N atom, and
q is an integer 2.

The heteroaromatic ring represented by R₅₁ is for example a triazole, thiadiazole, oxadiazole, Pyridine, pyrrole, quinoxaline, thiophene, furan, Pyrimidine or triazine ring. He can at least besides the two vinylsulfonyl groups, optionally further Substituents and optionally fused benzene rings contain, which in turn also substituted could be. Examples of heteroaromatic Rings (R₅₁) are listed below:

wherein
r is a number from 0 to 3 and
R₅₂ is C₁-C₄-alkyl, C₁-C₄-alkoxy or phenyl.

Finally, in are suitable as immediate hardening agents Japanese laid-open documents 38 540/75, 93 470/77, 43 353/81 and 1 13 929/83 and in the US-PS 33 21 313 described compounds.

Unless otherwise defined, alkyl is particular optionally by halogen, hydroxy, sulfo, C₁-C₂₀- Alkoxy substituted C₁-C₂₀ alkyl.  

Unless otherwise defined, aryl is special optionally by halogen, sulfo, C₁-C₂₀ alkoxy or C₁-C₂₀ alkyl substituted C₆-C₁₄ aryl. Aralkyl, provided not otherwise defined, especially by halogen, C₁-C₂₀ alkoxy, sulfo or C₁-C₂₀ alkyl substituted C₇-C₂₀ aralkyl. Alkoxy, unless otherwise defined, is in particular C₁-C₂₀ alkoxy.

X⊖ is preferably a halide ion such as Cl⊖, Br⊖ or BF₄⊖, NO₃⊖, (SO₄²⊖) _1/2 , ClO₄⊖, CH₃OSO₃⊖, PF₆⊖, CF₃SO₃⊖.

Alkenyl is especially C₂-C₂₀ alkenyl. Is alkylene in particular C₂-C₂₀ alkylene; Arylene, especially phenylene, Aralkylene, especially benzylene and alkaralkylene especially xylylene.

Suitable ring systems containing N, which can stand for Z, are shown above. Prefers is the pyridine ring.

R₃₆ and R₃₇ form together with the nitrogen atom that they are bound, especially one by 2 in o- and o'-position bonded oxo groups pyrrolidine or Piperidine ring that condenses benzo, cyclohexeno or [2.2.1] bicyclohexeno can be.

Acyl is especially C₁-C₁₀ alkylcarbonyl or benzoyl; Carbalkoxy is especially C₁-C₁₀ alkoxycarbonyl; Carbamoyl is especially mono- or di-C₁-C₄ alkylaminocarbonyl; Carbaroxy is especially phenoxycarbonyl.  

Groups R₂₄ which can be split off by nucleophilic agents are for example halogen atoms, C₁-C₁₅ alkylsulfonyloxy groups, C₇-C₁₅ aralkylsulfonyloxy groups, C₆-C₁₅ arylsulfonyloxy groups and 1-pyridinyl residues.

Suitable examples of instant hardeners are in EP-A 2 57 515 listed. Compounds of are preferred general formula (a). The immediate hardeners in particular in an amount of 500 to 1000 mg / m² material used.

Suitable UV absorbers are, for example, in US-A 32 53 921, DE-C 20 36 719 and EP-A 57 160. Preferred UV absorbers correspond to the formula

wherein
R is hydrogen, halogen or alkyl,
R₁ is hydrogen or alkyl and
R₂ is alkyl.

The UV absorbers are used in particular in an amount of 300 to 800 mg / m² used.  

The fine-particle, non-light-sensitive silver halide emulsion (Mikratemulsion) consists of grains with an average particle diameter <0.1 µm.

The halide composition of the micrate emulsion can fluctuate within wide limits. Silver halide emulsions are preferred with 0 to 100 mol% of silver chloride, 0 to 100 mol% silver bromide and 0 to 15 mol% silver iodide.

The Mikratemulsion is in layer A and / or B in one Amount used that the material 0.2 to 0.6 mg Ag / m² contains.

Acrylate polymers are particularly suitable as plasticizers Consider, preferably as an acrylate polymer latex be used.

The polymer consists mainly of polymerized Monomers of the formula

CH₂ = CH-COO-R

where R is an alkyl radical having 1 to 8 carbon atoms. Examples for R are ethyl, propyl, butyl, 2-ethylhexyl.

The acrylic polymer used may be one Homopolymer or a copolymer that one lower proportion of one or more with alkyl acrylate has copolymerizable monomers (comonomers),  act for which, for example, acrylamide, acrylic acid, acrylic monomers containing sulfonic acid groups, e.g. B. ω-acrylamido ω-methylpropanesulfonic acid (AMPS), hydroxyalkyl acrylate, Glycidyl acrylate, alkoxyalkyl acrylate in question come.

The composition must be chosen so that the Copolymerization is always a water-insoluble polymer received as latex.

Graft polymers of are also used as polymer latex Polyalkyl acrylate on suitable polymeric graft bases, e.g. B. on polyurethanes (described for example in US-A 37 91 857), or on gelatin or on Suitable for polyvinyl pyrrolidone.

Alkyl acrylate copolymers with a small proportion of a copolymerized copolymerizable Wetting agent (EP-A 00 10 335) suitable.

The glass transition temperature T _g is decisive for the suitability as a softening acrylate polymer latex.

The glass transition temperature is determined using differential thermal analysis determined (G. W. Miller, Applied Polymer Symposia No. 10 [1969], pp. 35-72). Emollient Are polymers in the sense of the present invention especially those with a glass transition temperature below -10 ° C.  

To estimate the T _g values of copolymers, the equation from Gordon-Taylor, J. Appl. Chem. 2, 492 (1952) can be used. It enables in form

(T _g - T _A ) W _A + K (T _g - T _B ) W _B = 0

the calculation of the glass transition temperature T _{g of} a particular copolymer if the glass transition temperatures of the corresponding homopolymers T _A and T _B and the proportions by weight W _A and W _{B of} the comonomers in question in the copolymer are known. In this way, a suitable selection of monomers which are suitable for the construction of the acrylate polymer latex according to the invention can thus be made. The T _g values of conventional homopolymers are tabulated in the "Polymer Handbook" by Brandrup et al., Interscience Publishers, Wiley & Sons, New York, 1966.

Plasticizers in layer A are in particular 0.1 to 1 g / m² used.

Examples of polymers according to the invention are given below:
P-1 polyethylene acrylate
P-2 polybutyl acrylate

Other plasticizers are known from DE-OS 27 45 287, DE-OS 15 22 387, DE-OS 14 72 746, US 47 14 671 and Research Disclosure 308 119, p. 1006, chap. XII, Dec. 1989.

Wetting agent A:

Wetting agent B:

Water-soluble ones are generally usable as correction dyes Dyes. The dyes preferably contain one or more carboxyl or sulfo groups or their water-soluble salts such as Na, K or ammonium salts. The dyes can be of all kinds Classes of dyes such as merocyamines, oxonols, styryl dyes, Azo dyes belong to anthraquinone dyes. Examples of suitable dyes are the following:

Other useful dyes are in Research Disclosure 17 643 (1978) Section VIII. At Correction dyes are especially 5 in layer A. up to 500 mg / m² used.

In particular come as finely divided quartz dispersions those with an average particle diameter (number average) from 0.7 to 1.2 µm and a proportion of particles <4 µm of <0.2% by volume. Preferably included the quartz dispersions have an anticoagulant additive and are received as follows:

The freshly prepared aqueous quartz particle dispersion with 30-50 wt .-% quartz particles with each 0.1-1% by weight of the anticoagulant additive added, 5 min  stirred and left at room temperature for 2-8 weeks (Sedimentation).

After 2 weeks and 2 months, the stirrability becomes with a laboratory stirrer with a rotational speed of 300 rpm after 10 minutes.

The dispersion must then be completely redispersed.

Quartz particle dispersion with anticoagulant:

• QD 1) Sodium polystyrene sulfonic acid Molecular weight Mn: 20,000
• QD 2) Copolymer of acrylamide and acrylamido-2-methylpropanesulfonic acid Molecular weight Mn: 500,000
• QD 3) block copolymer from 10 parts of polyvinyl alcohol and 2 parts of acrylic acid (as Na salt) Mn: 100,000
• QD 4) Copolymer of vinylpyrrolidone and styrene sulfonic acid 84: 16% by weight as sodium salt Mn: 20,000
• QD 5) Sodium polyacrylic acid Mn: 80,000
• QD 6) Polyvinylpyrrolidone K 90 Mn: 50,000
• QD 7) polyvinyl alcohol Mn: 40,000
• QD 8) gelatin
• QD 9) Phthaloyl gelatin with 5% by weight of phthaloyl groups
• QD 10) carboxymethylsulfoethyl cellulose, 2% by weight carboxy groups; 4% by weight sulfoethyl groups; Mn: 20,000
• QD 11) sulfoethyl cellulose, 4.5% by weight sulfoethyl groups; Mn: 40,000
• QD 12) cellulose sulfate, 2% by weight sulfate groups; Mn: 40,000
• QD 13) polydextran, Mn: 100,000

The finely divided quartz dispersion in layer B in particular 50 to 500 mg / m² used.

Layer A preferably has a dry layer thickness of 0.3 to 1 µm, layer B a dry layer thickness of 0.2 up to 1 µm.  

In a preferred embodiment, the casting solutions adjusted to produce layers A and B that the casting solution for layer A 4.5% by volume hydrophilic binder and the casting solution for layer B contains 1.5% by volume of hydrophilic binder.

Examples of color photographic materials are color negative films, Color reversal films, color positive films, color photography Paper and color reversal photographic Paper. The invention relates in particular to Color negative and color reversal films.

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

The color photographic materials usually contain at least one red sensitive, green sensitive and blue sensitive silver halide emulsion layer and optionally intermediate layers and Protective layers.  

Essential components of the photographic emulsion layers are binders, silver halide grains and Color coupler.

That as a light-sensitive component in the photographic Silver halide present as material Halide chloride, bromide or iodide or mixtures of which included. For example, the halide content at least one layer of 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 usually silver bromide iodide emulsions, in the case of color negative and color reversal paper usually high silver chloride bromide emulsions Chloride content used up to pure silver chloride emulsions. It can be mostly compact crystals act the z. B. are regular cubic or octahedral or can have transitional forms. Preferably however, platelet-shaped crystals can also be present, their average ratio of diameter to Thickness is preferably at least 5: 1, the diameter a grain is defined as the diameter of a Circle with a circle content corresponding to the projected Area of the grain. The layers can also have tabular silver halide crystals, where the ratio of diameter to thickness is significantly larger than 5: 1, e.g. B. 12: 1 to 30: 1.  

The silver halide grains can also be multi-layered Have grain structure, in the simplest case with an inner and an outer grain area (core / shell), the halide composition and / or other modifications, such as B. endowments of the individual Grain areas are different. The middle The grain size of the emulsions is preferably between 0.2 µm and 2.0 µm, the grain size distribution can be both be homo- and heterodisperse. Homodisperse grain size distribution means 95% of the grains are not deviate more than ± 30% from the average grain size.

In addition to the silver halide, the emulsions can also contain organic silver salts, e.g. B. silver benzotriazolate or silver behenate.

Two or more types of silver halide emulsions, which are made separately, as a mixture be used.

The photographic emulsions can be different 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) soluble silver salts and soluble halides become.

The silver halide emulsions are made in the usual way matured, spectrally sensitized and stabilized.  

According to color photographic recording materials The present invention is preferably multilayer materials that have multiple silver halide emulsion layers or emulsion layer units with have different spectral sensitivity. When Emulsion layer units are laminates from 2 or more silver halide emulsion layers of the same Spectral sensitivity understood. Layers of the same Spectral sensitivity does not necessarily have to be arranged adjacent to each other, but can also through other layers, especially by layers of different spectral sensitivity from each other be separated. The binder in these layers is usually a proteinaceous binder with free carboxyl groups and free amino groups, preferred Gelatin. The layer binder can, however, besides the proteinaceous binder not up to 50% by weight proteinaceous binders such as polyvinyl alcohol, N- Vinyl pyrrolidone, polyacrylic acid and their derivatives, especially copolymers, or cellulose derivatives contain.

Everyone is in color photographic recording materials of said photosensitive silver halide emulsion layers or emulsion layer units at least a coloring compound, usually a Color couplers, associated with color developer oxidation products forming a non-diffusing or diffusible in terms of time or location Dye is able to react. Are expedient the color couplers are non-diffusing and light sensitive  Shift yourself or in close proximity housed for this. The two or more sub-layers a color coupler associated with an emulsion layer unit don't necessarily need to be identical his. They should only be used for color development result in the same color, usually a color that is complementary to the color of the light against which the photosensitive silver halide emulsion layers are sensitive.

The red sensitive silver halide emulsion layers is therefore at least one non-diffusing color coupler to generate the blue-green partial color image assigned, usually a coupler from phenol or α-naphthol type. Particularly noteworthy are, for example Teal couplers as described in US-A 24 74 293, US-A 23 67 531, US-A 28 95 826, US-A 37 72 002, EP-A 00 28 099, EP-A 01 12 514.

The green sensitive silver halide emulsion layers is usually at least one non-diffusing Color coupler for the generation of the purple partial color image assigned, usually color coupler of the type 5-pyrazolone or indazolone can be used. Also further as purple couplers are cyanoacetyl compounds, Oxazolone and Pyrazoloazole in question. Especially For example, purple couplers such as these are to be emphasized are described in US-A 26 00 788, US-A 43 83 027, DE-A 15 47 803, DE-A 18 10 464, DE-A 24 08 665, DE-A 32 26 163.  

The blue sensitive silver halide emulsion layers after all, there is usually at least one non-diffusing Color coupler for generating the yellow partial color image assigned, usually a color coupler with an open chain ketomethylene grouping. Especially yellow couplers such as they are described in US-A 34 08 194, US-A 39 33 501, DE-A 23 29 587, DE-A 24 56 976.

Color couplers of these types are known in large numbers and described in a variety of patents. Exemplary be further here on the publications "Color coupler" by W. Pelz, "News from the research laboratories the Agfa, Leverkusen / Munich ", volume III (1961), p. 111, and by K. Venkataraman in "The Chemistry of Synthetic Dyes ", Vol. 4., 341 to 387, Academic Press (1971).

The color couplers can be 4-equivalent couplers, but also act as 2-equivalent couplers. Latter are known to derive from the 4-equivalent couplers that they have a substituent in the coupling site included, which is split off at the clutch. The 2-equivalent couplers include both those that are practically colorless, as well as those that have an intense color of their own, that of the color coupling disappears or by the color of the generated Image dye is replaced (mask coupler). To the 2- In principle, equivalent couplers are also the known ones White couplers to be expected, but with reaction Color developer oxidation products essentially colorless Products result. To the 2 equivalent couplers are  furthermore to count such couplers in the coupling point contain a cleavable residue, the reaction with color developer oxidation products in freedom is set, either directly or after the primary split off one or more others 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 develops certain desired photographic effectiveness, e.g. B. as a development inhibitor or accelerator. Examples of such 2-equivalent couplers are known DIR couplers as well as DAR or FAR couplers.

Suitable DIR couplers are described, for example in GB-A 9 53 454, DE-A 18 00 420, DE-A 20 15 867, DE-A 24 14 006, DE-A 28 42 063, DE-A 34 27 235.

Suitable DAR or FAR couplers are described, for example in DE-A 32 09 110, EP-A 00 89 834, EP-A 01 17 511, EP-A 01 18 087.

As with the DIR, DAR or FAR couplers mainly the effectiveness of the released at the clutch The rest is desirable and it is less on the color-forming Properties of these couplers are well received DIR, DAR or FAR couplers suitable for the Coupling essentially colorless products result like described for example in DE-A 15 47 640.

The detachable residue can also be a ballast residue, see above that in the reaction with color developer oxidation products  Coupling products e.g. B. dyes can be obtained can, which are diffusible or at least one have weak or restricted mobility like described for example in US-A 44 20 556.

High molecular weight color couplers are described, for example in DE-C 12 97 417, 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 00 27 284, US-A 40 80 211. The high molecular color couplers are used in the Usually by polymerizing ethylenically unsaturated monomeric color couplers. But you can too obtained by polyaddition or polycondensation become.

In addition to the components mentioned, the Layers contain other additives, for example Antioxidants, dye stabilizers and Means for influencing the mechanical and electrostatic Properties. To the adverse impact from UV light to the color photographic according to the invention Color images produced recording material to reduce or avoid, too hardening layers UV light absorbing compounds contain.

Example 1

A color photographic recording material for the Color negative development was created by a transparent base made of cellulose triacetate the following layers in the order given were applied. The quantities refer to each on 1 m². For the silver halide application the corresponding amounts of AgNO₃ indicated. All silver halide emulsions were per 100 g of AgNO₃ with 0.5 g 4-Hydroxy-6-methyl-1,3,3a, 7-tetrazainden stabilized.

There are layers 1 to 4, layers 5 to 8 and layers 9 through 12 together with a quintuple cascade caster applied.

Layer 1 (antihalo layer)
Black colloidal silver sol with 0.5 g Ag, 0.2 g octylhydroquinone and 1.5 g gelatin, 0.4 g polyethyl acrylate (plasticizer P-1)
Layer 2 (1st red-sensitized layer)
red-sensitized silver bromide iodide emulsion from 3.5 g AgNO₃, with 1.7 g gelatin and 0.7 g coupler mixture C1 emulsified with 0.7 g tricresyl phosphate (TKP). 0.15 P-1
Layer 3 (2nd red-sensitized layer)
red-sensitized silver bromide iodide emulsion from 2.0 g AgNO₃, with 2.0 g gelatin and 0.2 g coupler mixture C1 emulsified with 0.2 g CPM, 0.2 g P-1
Layer 4 (intermediate layer)
0.7 g gelatin and 0.09 g 2,5-diisooctylhydroquinone
Layer 5 (1st green-sensitized layer)
green-sensitized silver bromide iodide emulsion from 2.2 g AgNO₃, with 1.7 g gelatin and 0.5 g coupler M1 emulsified with 0.5 g CPM, 0.2 g P-1
Layer 6 (2nd green-sensitized layer)
green-sensitized silver bromide iodide emulsion from 1.5 g AgNO₃, with 1.7 g gelatin and 0.2 g coupler M1 emulsified with 0.2 g CPM, 0.08 g P-1
Layer 7 (intermediate layer)
0.5 g gelatin and 0.06 g 2,5-diisooctyl hydroquinone, 0.09 g P-1
Layer 8 (yellow filter layer)
yellow colloidal silver sol with 0.1 g Ag, 0.35 g gelatin and 0.2 g P-1

Material 1 (according to the invention; layers 9-12 applied together)

Layer 9 (1st blue sensitive layer)
Silver bromide iodide emulsion from 0.8 g AgNO₃, with 2.5 g gelatin and 1.2 g coupler Y1 emulsified with 0.55 g CPM and 0.2 g P-1
Layer 10 (2nd blue sensitive layer)
Silver bromide iodide emulsion from 0.6 g AgNO₃, with 0.5 g gelatin and 0.06 g coupler Y1 emulsified with 0.03 g CPM and 0.05 g P-1
Layer 11
1.4 g gelatin
0.5 g micrate emulsion
0.5 g UV-1
0.5 g P-1
0.01 g of cyan dye K8
0.02 g purple dye K5
0.02 g yellow dye K4
0.04 g of compound I-1
Layer 12
0.2 g gelatin
0.02 g of compound II
0.2 g alkali-soluble spacers made of hydroxypropyl methyl cellulose hexahydrophthalate
0.03 g of dimethylpolysiloxane as a dispersion in gelatin, particle diameter 0.1 μm, Mn: 3500
0.05 g of compound I-1
0.8 g instant hardener H

Material 2 (according to the invention)

Apply layers 9-12 together.
Layers 9, 10 and 12 as for material 1.
Layer 11 as for material 1 with the following changes:
0.02 g bluish green K8
0.05 g purple dye K5
0.05 g yellow dye K4
0.1 g of compound I-1

Material 3 (according to the invention)

Layers 9-12 applied together.
Layers 9, 10 and 12 as for material 1.
Layer 11 as for material 1 with the following changes:
0.1 g purple dye K5
0.1 g yellow dye K4

Material 4 (according to the invention)

Layers 9-12 applied together.
Layers 9, 10 as for material 1.
Layers 11 as for material 1 but without a micrate emulsion.
Layer 12
0.4 g gelatin
0.02 g of compound II
0.5 g micrate emulsion
0.2 g alkaline spacers
0.1 g of compound HM1
0.03 g dimethylpolysiloxane
0.03 g of compound I-1
0.8 g instant hardener H

Material 5 (according to the invention)

Layers 9-12 applied together.
Layers 9, 10 and 11 as for material 1.
Layer 12
0.26 g gelatin
0.05 g alkali-soluble spacers
0.20 g SiO₂ fine quartz crystals QD8 average diameter 1.0 µm
0.30 g of compound I-1
0.35 g dimethylpolysiloxane
0.1 g of compound HM1
0.8 g instant hardener H

Material 6 (not according to the invention)

Layers 9 + 10 as for material 1.
Layers 9 to 12 applied together, dried and layer 13 applied in a separate operation.
Layer 11
0.7 g gelatin
0.5 g UV-1
0.25 g P-1
Layer 12
0.7 g gelatin
0.5 g micrate emulsion
0.25 g P-1
Layer 13
0.2 g gelatin
0.02 g of cyan dye K8
0.05 g purple dye K5
0.05 g yellow dye K4
0.05 g spacer polymethyl metharylate with an average particle diameter of 2.0 µm
0.8 g instant hardener H

Material 7 (not according to the invention)

Layers 9-12 as for material 6.
Layers 9 to 12 applied together, dried and layer 13 applied in a separate operation.
Layer 13
0.2 g gelatin
0.02 g of cyan dye K8
0.05 g purple dye K5
0.05 g yellow dye K4
0.4 g SiO₂ dispersion average particle diameter 0.1 µm
0.35 g dimethylpolysiloxane dispersion as for material 1
0.05 g spacer as material 6
0.8 g instant hardener H

Material 8 (not according to the invention)

Layers 9-11 as for material 3.
Layers 9 to 13 applied together.
Layer 12
0.27 g gelatin
0.27 g alkaline spacers
0.07 g of compound HM1
0.25 g dimethylpolysiloxane
0.02 g polystyrene sulfonic acid
Layer 13
0.02 g gelatin
0.02 g of compound II
0.07 g of compound HM1
0.01 g of dimethylpolysiloxane
0.03 g of compound I-1
0.8 g instant hardener H

Material 9 (not according to the invention)

Structure like material 8.
Layer 13 but with the following changes:
0.12 g gelatin
0.1 g alkali-soluble spacers

Table 1

Table 2

The following connections were used

95 mol% methyl methacrylate and 5 mol% ethylene glycol dimethacrylate, Mn: 1011.

II copolymer of 98 wt .-% methyl methacrylate and 2 wt .-% methacrylate in the form of beads with a diameter of 3 microns.
C1 mixture of 5% by weight of cyan coupler of the formula

and 95% by weight cyan couplers of the formula

M1 purple coupler of the formula

Y1 yellow coupler of the formula

Instant hardener H

After drying, the cast image was assessed visually. Wet scratch resistance, parallel breaking strength, Dry scrapability, rewinding torque and the friction values in tropical climates and retouchability (pencil acceptance) measured. The casting quality is 1 best, 5 the worst grade. With retouchability is given the pencil hardness that is still assumed becomes.

Wet scratch resistance: The material to be tested is located with the layer side up on a horizontal Sample holder, in a with 10 ° DH water at 38 ° C filled tub. The sample to be measured is completely covered with water. After a swelling period of 5 Minutes, a firmly locked steel ball (⌀ 3.2 mm) guided over the surface of the test object and with increasing weight.  

As a measure of the wet scratch resistance of the material that force (N) specified at which after sample drying the first layer injuries on the test section is recognizable by means of the human eye. Average from 9 measuring sections each.

The parallel breaking strength was determined by the parameters Breaking diameter [mm] and breaking strength [N] characterized. Here was a 35 mm wide strip of the concerned Material that perforates along a cross line was formed into a loop and this between two parallel, steadily approaching each other Cheeks pressed together. Fracture diameter is the distance The two jaws and breaking strength is the force with which the two jaws act on the loop, namely the moment the loop runs along the perforation line breaks. The method is described in Research Disclosure 25,302 (5/85).

The coefficient of friction (coefficient of friction = tensile force / normal force × 100) is a measure of static friction when the material with the Coating side under the influence of a tensile force over a surface made of V2A steel (V2A / S) or over the Back of the same material (R / S) to slide begins.

The rewinding torque [mN · cm] during forward and backward transport was determined as follows.  

The ready-made films were in the cartridge adjusted to the test climate (35 ° C, 90% RH) without a 7d socket, then in an Orthomat cassette from the company Leitz inserted and every second by one 35mm film transported. Immediately after completion the film was transported within 7 seconds rewound. Of the above values, the respective contributions for the friction of the cassette mechanism subtracted. As a measure of advance transport the maximum occurring torque and the mean X out of 36 transport operations specified. For return transportation the torque from the beginning of the transport (A) and the maximum torque occurring at the end of the Transportes (E) specified.

The dry scrapability is with a device of Heidon measured according to TIS standard 6178. Stylus sapphires Radius 0.050 mm, angle 90 °. The sapphire tip was passed over the dry layer and with increasing Weight loaded. The samples were taken before measurement 24 hours at 23 ° C, 50% rel. Conditioned moisture. The scratch resistance is determined by the force (mN) given at which the tip is microscopic visible damage to the layer. Average of 20 scratch marks each.

Claims (6)

1. Color photographic silver halide material with a support, 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, at least one blue-sensitive silver halide emulsion layer containing at least one yellow coupler and two non-photosensitive layers A and B, all photosensitive layers and layers A and B are applied to the same side of the support, layer A is further away from the support than all light-sensitive layers and layer B is further away from the support than layer A, characterized in that
layer A

• (a) a UV absorber,
• (b) optionally a finely divided, non-light-sensitive silver halide emulsion,
• (c) a hydrophilic binder, in particular gelatin,
• (d) a plasticizer and
• (e) a thickener and

layer B

• (a) an alkali-insoluble spacer,
• (b) a polymer containing reactive groups,
• (c) a lubricant,
• (d) a thickener,
• (e) an instant hardener,
• (f) an alkali-soluble spacer and
• (g) optionally contain a finely divided, non-light-sensitive silver halide emulsion, at least one of layers A or B containing the finely divided, non-light-sensitive silver halide emulsion.

2. Color photographic silver halide material after Claim 1, characterized in that between the last photosensitive layer and layer A no further layer is arranged. 3. Color photographic silver halide material after Claim 1, characterized in that layer A contains at least one correction dye. 4. Color photographic silver halide material after Claim 1, characterized in that layer B a hydrophilic binder, especially gelatin contains. 5. Color photographic silver halide material according to claim 1, characterized in that layer B contains a fine-particle quartz dispersion.