DE2327731A1 - COLOR PHOTOGRAPHIC MATERIALS - Google Patents

Description

PATENTANWKLTE

DR. E. WIEGAND DIPL-ING, W. NiEMNN DR. M. KÖHLER DIPL-ING. C. GERNHARDT

MÖNCHEN HAMBURG Δ O Δ IIO \

TELEPHONE: 55547ί "8000 MD N CH EN 15, 30. Ι · ίε.1 1973

TELEGRAMS: KARPATENT · NUSSBAUMSTRASSE10

W. 41659/73 - TLo / tie

Fuji Photo FiIn Co., Ltd. . Minami Ashigara-shi, K'anagawa (Japan)

Color photographic materials

The invention is concerned with color photography and particularly relates to color photographic materials, those used to form Msgenta dye images with good heat and moisture resistance are suitable.

The color photographic materials of the present invention I'Iagenta dye images form and persist with excellent heat and moisture resistance made of e-inera! carrier with a photographic one on it Silver halide emulsion layer, vrelche a J-ureido - ^ - pyrazolone magenta coupler "together with a compound having an aldehyde group bonded to a carbon atom.

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It is known in the field of color photography that cyan, magenta and yellow dye images are formed by coupling the oxidation product of a primary aromatic Amine as a developing agent and from color-forming couplers. It is also known that various pyrazolone derivatives for the formation of magenta dye images can be used.

The magenta dye images are usually opposite Heat and moisture unstable and when exposed to 'heat or moisture or during are stored for a long period of time, the low-density parts of the magenta paraffin images show a tendency to eat. It is known that this Appearance due to what is seen in color photography Material remaining unreacted coupler occurs, so that the above inclination especially on the parts of the picture at low density is seen where a large amount of the unreacted coupler remains (see for example O.W. Vittum, Journal of the American Chemical Society, Vol. 72, 1553 (195O)).

Different methods to prevent fading of magenta dye images have already been proposed. For example, according to the method disclosed in US Pat. No. 5,140,177, a color photographic limaterial in an acidic treatment solution, which contains formalin, treated as the final treatment step of the color photographic material However, the procedure is unfavorable as formalin gives off a bad odor and continues to be harmful to the body is.

According to US Pat. No. 3,468,666, a

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by condensation of a J-acylaniino ^ -pyrasolons and bispyrazolone produced from an aldehyde as a magenta coupler used. However, this bispyx ^ azolone shows the defect that it does not have a sufficient coupling density the color development results. Furthermore, that is through this Color image formed by bispyrazolone is not very fast to heat and moisture.

The development of new machines for education of Hagenta dye images from gutex · Fastness to 'Warmth and moisture are therefore an urgent task.

An object of the invention therefore consists in color photography Materials that are suitable for forming true magenta images.

It has been found that the above objects of the invention can be achieved when a 5-ureido-5-pyrazolone and a compound having a s a carbon atom bound aldehyde group may be used. According to the invention, the silver halide photographic emulsion thus contains a magenta coupler of the 3-ureido-5-pyrazolone type and a compound having an aldehyde group bonded to the carbon atom.

According to one embodiment of the invention a fax "bphotographic material, which consists of a Support with a photographic silver halide emulsion layer coated thereon, which is at least a non-diffusible 3 ~ ureido-5-pyrazolone accordingly the general formula

-o ¹ -

E ₁ MHCBH-C -

¹ I! I!

ο N ^ ^ c = O (I)

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where IL · is an alkyl group or an aryl group and I ^ denote a phenyl group, and at least one compound with an aldehyde3.ru.ppe bonded to a carbon atom contains.

As used herein, the term "non-diffusible" means those used in color couplers in the field of color photography known statement that the coupler is practically in the colloid layers of the photographic material in the presence an aqueous, alkaline treatment solution practically does not move.

If 1L · . denotes an alkyl group, the alkyl group generally contains 1 to 32 carbon atoms, although this range is not limiting. Most preferably, if 1L is an alkyl group, it has 8 to 18 carbon atoms since an alkyl group with 8 or more carbon atoms acts as a ballast group, while alkyl groups with 19 or more carbon atoms are not preferred from the industrial point of view, that is, these compounds have an increased production cost, difficult manufacture, and the like.

If H-j is an aryl group, it orders from one Monoarylgx nippe, as discussed in the following paragraphs.

If Rp represents a substituted phenyl group, the preferred Gubstituenten halogen, cyano, nitro, alkyl with 1 to 18 carbon atoms, alkoxy with 1 to 18 carbon atoms, aryl, for example phenyl, ToIy1 and the like., Aryloxy, for example phenoxy and the like., Carbamoyl, sulfamoyl, sulfonamides) or acyl.

Specific examples of R2 include the following groups: phenyl, 2-chlorophenyl ₇ 4-chlorophenyl, 2,5-dichloro-phenyl, 2,6-dichlorophenyl, 2,4,6-trichloxphenyl, 2-bromophenyl, J ,, 5 -Dibromophenyl, 2-cyanophenyl, 3-I \ ^T itrophenyl,

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_ 5 -

4-methylphenyl, 2,6-I) imethylphenyl, 2,6-diethylphenyl, 4-butylphenyl, 2-trifluoromethylphenyl, 2-Ä "tho: xyphenyl, 4 ^ phenylphenyl, 4-phenoxyphenyl, N-methylbenzimidopheryl, In, IT-Diphenylcarbamoylphenyl, Ii, N-Dibutyl sulf amoylphenyl, Ή , Ef-Diphenyl sulf fanoylphenyl, N-Methylsulfonamldoph.eb.yl, 2-Methyl-5-nitrophenyl, 2-Chloro ~ 5-cyanphenyl, 5-Chlox- 2- methylphenyl, 2,6-dichloro-4-methylphenyl, 2,4-dichloro-6-methylphenyl, 2-chloro- ^z 1-, 6-dimethylphenyl, 2,6-dichloro-4-methoxyphenyl, 2,6- Dichloro-4-nitro-phenyl, 2,4,6-tri3-ethyl-3-nitrophenyl, 2,4,6-trimethyl-3-acetamidophenyl, 2,4,6-trimethyl-3- ^ a- (2, 4-di- tor t. '-Aaylphen oxy) -butylainido7-phenyl and similar groups.

Of the 3-ureido-5-pyrazolones according to general formula I ground the couplers of the formula wherein at least one o-position of the fhenyl group corresponding to " Plq with a halogen atom, an alkyl group with 1 to 5 carbon atoms or an alkoxyl group with 1 to 5 Carbon atoms is substituted, particularly preferred.

Specific examples of the groups IL of the general Formula I include alkyl groups such as methyl, ethyl, Propyl, isopropyl, butyl, isobutyl, tert-butyl, amyl, hexyl, cctyl, decyl, dodecyl, pentadecyl, Octadecyl, allyl, heptadecenyl and benzyl groups as well Aryl groups such as phenyl and tolyl groups.

Become phenyl groups with the following substituents as group IL in the general formula I preferred:

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(a) -NHCOS ₅

(b) -KHCO -f CH

(c)

(d) -SO ₂ NC _n ^ ^

^R 10

In the; The above formulas mean S ₇ , E ₁ -, Hp ₇ , H ₀ , R. ^ and ICp an alkyl group, E ^, E ^ and E ^ _Q a Uosser stofiatoa or an alkyl group and η an integer from 1 to 5 · General all alkyl groups for the H-, to E ^ _n radicals have a number of 1 to 18 carbon atoms and for practical purposes they are preferably unsubstituted.

It is preferred that at least one of the Eeste Ry, and Eo of the general formula I is a ballast group ·

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which makes the coupler non-diffusible. How on known in the art, ballast groups are hydrophobic Groups which usually have 8 to J2 carbon atoms contain.

Examples are in U.S. Patents 2,600,788, 2,865,751, 3,337 34-4 'and 3,418,129 and the Japanese Patent Publications 27563S64 and 19035/7O are viewed.

Specific examples of 3 ~ -urido-5-pyroz, olone couplers are given below:

Coupler ~ 1

t ert rC ^ H-, _χ

KHCOKIi-C - CH-2

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Γι Λ ·) 1 ' _-

rCcH, .-

NHCONH-C-CH

II I ² NC = O

Kupp 1 sr. "- 3

C ₁ CiH ₇₁ CO,
^{x ;? Jl} - ^ KCH ,, CH ₂ CONH

NHCONH-C-

Il

. w

-CH ₂
C = O

Cl

"Coupler - 4
tertrCr-i

- / V OCH ₂ COKH ~ i \
tert rCr-H- ,,

IiHCOIiH-C CH-,

II I ² NC = O

Cl "

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Coupler - 5

seer

MHCONH-C

M = ⁰

ei JL ei

Cl '

Suppler - 6

tert j

t ^

^ V-OCH ₂ COMH- / \

tertT NHCONH-C-CH

₂ _

N C = O \ /

Coupling -

-CH ₂ CH ₂ CONH

CONH-C CH-

OCH,

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Coupler - 8 tert _{-C 1} -H.

NHCOKH-O -— CH-

! r Lo

Coupler. * - 9

tert; C _c H

¹ Il

Coupler - 10 tertrC,

-O

tert r

NHCOfJH-C

I!

- CH.

Cl

CH-

OCH ₂ COKH

NECOFH-C CH.

ι C =;

Cl

OCH,

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Coupler - 11 tert? C _c H.

Kupp 1 es * _12 tertrC _c H,

Coupler- 13

—OCHCONH

tertZ

NHCONH-C CH-

-ii 1

N C = O \ /

Cl

OCH.

0CH ₂ COKH

rert: Cr NHCONH-C— CH,

Cl

CH,

OCH ₂ COKH (f \

NHCONH-C-CH

II

CH.

Π 9 B B 1/0 8 6

Coupler -

C. Ji ,, CONH

CONH-C-CH

Cl

Coupler. · - 3-5 tert JC ₅

Ituppler -. 16

OCHCONH

Y \

tert7C ^ H ₁₁

OCHCONH

NHCOKH-C

CH

CH,

NHCOKH-C CH

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Coupler - 17th

■ NHCONH-C-

«A

C = O

CH,

CH,

NHCOCH ₂ O

CH,

tert ^ CcH ₁₁

tert

Coupler- - 18 _x C ₁ HqNHCONH -

C—

CH,

NHCOCH

H,

-O - ζ \) -

tertTCcH ₁₁

tert7

Coupler - 19th

NKCONH - C -

Cl

Cl

Cl

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Coupler "20

NHCONH-C CH-

U C = O

Cl

Cl

Coupler «2I

CnH _1n OOC

ο I /

C ₀ H, "00C

NHCOiJH-C— CH-

• Ii i ²

Coupler - ZZ

Cl

CH-

tertJ

NHCOM-C - CH _D

I Ll \ /

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Coupler - 23

Coupler - 2k

MHCONH-C " II

Cl

CH ₀ I ²

Cl

(/ V-OCHCONH-Hf V-KIICOKH

Ir

OCH,

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The 3-ureido-5-pyraζolone couplers used according to the invention can be according to the procedures of U.S. Patent 3,558,319 and Japanese Patent Applications 100911/1970, IO67I6 / 197O and the like will.

In the silver halide emulsions according to the invention can use the 3-Ireidc-5-pyrazolone couplers listed above alone or as a combination of two or more couplers. Furthermore, the J-ureido-5-pyra ζ olon couplers together with other 2J equivalent or 4-equivalent couplers can be used. These couplers are sometimes referred to as colorless couplers, colored couplers, or DIIv couplers, and specific examples for this purpose-include those in US Patents 2,455,170 »

2 600 788, 2 9O8 573, 3 062 653, 3 14-8 062, 3 227 55 ^,

3 227 p54, 3 418 129, 3 5I6 831, 3 519 429 and 3 617 291 specified coupler.

The 3-ureido-5-pyrazolone couplers according to the invention, regardless of whether they are used individually or as a combination of two or more, are in terms of Ratios .not particularly limited as long as the objects of the invention are achieved. Generally speaking, however, they are used in amounts of from about 20 to about 100% by weight, preferably from 50 to 100% by weight of the total amount used Coupler used to form the magenta color.

These color couplers are incorporated into a hydrophilic colloid such as are typically used in photographic applications Materials used by any known method. For example, they can be in a hydrophilic Colloid using a high-boiling organic solvent such as dibutyl phthalate and tricresyl

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phosphate according to U.S. Patent 2,322,027 and / or a low-boiling organic solvent, such as ethyl acetate and tetrahydrofuran accordingly U.S. Patents 2,801,170, 2,801,171 and 2,946,360 be dispersed.

The aldehydes used in conjunction with the 3-ureido-5-pyrazolone couplers according to the invention include "Compounds having an alkyl group, an aryl group, or a heterocyclic group identical to the aldehyde group connected, d. H. there can be aliphatic ^ aldehydes, aromatic aldehydes or heterocyclic aldehydes are used according to the invention. The aliphatic aldehydes preferably contain 2 "to 20 carbon atoms, most" preferably 2 to 8 carbon atoms. Of the aromatic aldehydes are most strongly those with a formyl group. those on a phenyl or Naphthyl ring is bonded, preferably, albeit with halogen, nitro, hydroxy, C. - to Cg-alkyl, C ^ - to Cg-alkoxyallyl, Carboxy, SuIfο and the like. Substituted aryl groups are useful. . .

Among the aldehydes, benzaldehyde with or without the above substituents is preferred.

Specific examples of such compounds are acetaldehyde, propionaldehyde, butyraldehyde, isobutyraldehyde, Pivalaldehyde, heptaldehyde, lauric aldehyde, Stearaldehyde, succindialdehyde, crotonaldehyde, benzaldehyde, o-chlorobenzaldehyde, m-chlorobenzaldehyde, p-chlorobenzaldehyde, p-bromobenzaldehyde, p-nitrobenzaldehyde, p-hydi ^ oxybenzaldehyde, o-tolualdehyde, cinnamylaldehyde, α-naphthaldehyde and furfural and the like.

The aldehydes can be used alone or as a combination of two or more aldehydes. The additional

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amount of aldehydes is usually about 0.05 "° about 30 moles, especially about 0.1 moles "to about. 10 moles each Moles of the coupler.

It is preferred that the aldehyde be added to the hydrophilic Colloid is added when preparing the coupler dispersion by using the method outlined above Coupler or the couplers to the hydrophilic colloid together with the above high-boiling point organic Solvent and / or the low-boiling organic solvent are added. Alternatively, you can also to the silver halide emulsion in the preparation of the coating compositions together with the coupler dispersion, a hardening agent, a stabilizer, a wetting agent and the like be added.

The. The length of the coupler for magenta formation according to the invention is not limited insofar as the color photographic materials according to the invention perform the tasks set out above, d. H. a magenta dye image of good heat and moisture resistance result. However, since it is necessary for trading to supply an item for the A large number of consumers will provide pleasant results, the amount of coupler used for magenta color formation about 0.05 to about 0.5 mol per KoI silver halide, more preferably C.07-0.2 moles per mole Silver halide.

All known hydrophilic colloids "as used in the color photographic field, can be used as a hydrophilic colloid for the photographic silver halide emulsion layers according to the invention can be used. Preferred examples of such hydrophilic colloids are gelatin, albumin, gum arabic,

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Agar agar, cellulose derivatives such as alkyl esters of carboxymethyl cellulose , Hydroxyethyl cellulose, carboxymethyl hydroxyethyl cellulose and the like, as well as synthetic resins such as polyvinyl alcohol, polyvinyl pyrrolidone and the like. These hydrophilic colloids are also preferred as binders for the layers of the photographic materials except for the silver halide emulsion layers, for example as protective layers, filter layers, intermediate layers, Antilichbhofschichten, founders, Backside layers and the like. Used.

The hydrophilic used in various layers of the photographic materials according to the invention Colloids can be made effective by hardening agents such as 1,4-dioxane, Aziridines, isooxazoles, active halogens, active vinyl compounds and the like. Can be cured. Typical Examples of such hardening agents are disclosed in U.S. Patents 3,232,764, 3,288,775, 2,732,303, 3,635,718, 3 232,763, 2 732 316, 2 586 168, 3 103 437, 3 017 280,

2 983 611, 2 725 294, 2 725 295, 3 100 704, 3 091 537,

3,321,313 and 3,543,292 and British patents 874 723, 1 167 207 and 994 869 are given.

According to the invention, all silver halide emulsions, such as are commonly used in the field of photography, for example Silver bromide emulsions, silver iodobromide emulsions, Silver chloroiodobromide emulsions, silver chlorobromide emulsions and silver chloride emulsions. Also the so-called silver halide emulsions of the reverse Halide type, such as that disclosed in U.S. Patent 3,622,318 and British Patent 635 841 can be used «The preferred average grain size of the silver halide

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nides "is about 0.05" to about 1.5 microns. The weight ratio from silver halide to binder is most favorable in the range from about 0.2 to about 20 (syllable halide / binder), preferably about 0.3 to about 5 »in the layer. These values are not limiting, but rather ' provide the most superior elements.

The materials shown in the color photographs according to Silver halide emulsions used in the invention can be chemically modified by active gelatin or sulfur compounds sensitized according to the procedure of U.S. Patents 1,574-944, 1,62J,499, and 2,410,689 will. You can also use a noble metal salt such as a palladium or gold salt according to the US patents 2 448 060, 2 399 083 and 2 642 361 sensitized will. Furthermore, they can be separated by a reducing agent, for example a tin (II) salt speaking of U.S. Patent 2,487,850 or by a Polyalkylene derivative can be sensitized. You can also by a cyanine or a merocyanine dye corresponding to U.S. Patents 2,519,001, 2,666,761, 2,734,900, 2,739,964 and 3,481,742 spectral be sensitized.

The silver halide emulsions according to the invention can contain a stabilizer, such as mercury compounds, Mercoptotetrazole, thiazole, azaindene, and the like, plasticizers, such as glycerin, latex and the like, and wetting agents such as saponin, polyethylene glycol monolauryl ether and the like. Furthermore, the silver halide emulsions can contain antistatic agents, ultraviolet absorbers, fluorescent brightening agents, dyes and the like. Contain.

The 3-ureido-5-pyrazolone and the aldehyde

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"Silver halide emulsion containing a bond according to the invention is effective as a green-sensitive emulsion layer in ordinary multilayer color photographic Materials used. In this case, the order of the photosensitive emulsion layer may be from the support side of a red-sensitive emulsion layer, a green-sensitive emulsion layer and a blue-sensitive emulsion layer or can consist of a blue-sensitive emulsion layer, consist of a red-sensitive emulsion layer and a green-sensitive emulsion layer.

In addition to these light-sensitive emulsion layers, the color photographic materials according to FIG Invention of an antihalation layer, intermediate layers, Filter layers, protective layers and the like. Contain.

The supports of the photographic materials according to the invention, followed by the light-sensitive silver halide emulsion layers are preferably formed from cellulose ester films such as cellulose nitrate films, cellulose acetate films and the like, polyester films, such as polyethylene terephthalate films, polyvinyl chloride films, Polystyrene films, polycarbonate films, barite-coated papers, resin-coated papers and the like. This list is natural not limiting.

The color photographic materials according to the invention are exposed imagewise in the usual way and then after usual color photographic treatments developed. The main stages of development are color development, bleaching and fixing, and if necessary Vash levels that can be used between each level. After the fixation, this will be

3Q98S1 / Q869

color photographic material washed and dried, however it is convenient to place the color photographic material in a stabilizing bath. treat before drying.

As every specialist knows, the photograph! See lies Development temperatures typically between about 20 ° C or less and 60 ° C or higher. Temperatures of about JO ° C or higher are for high speed treatment processes suitable. The treatment times for treatment stage can vary widely, depending on the treatment temperature is dependent, but are usually a few seconds to a few minutes or more.

The usual color developers are aqueous alkaline Solutions containing a color developing agent. As the color developing agent, all known ones can be used primary aromatic amines as color-forming developing agents are used »Examples of such color developing agents are phenylenediamines; like N, N-diethyl-pphenylenediamine, IT, Ithylhydro ^ äthyl-p-phenylenediarüin, N-, Xthyl-IT-hydroxyethyl-2-methyl-p-x) henylenediamine, li-ethylß-N-methanesulfonamdoethyl-3-methyl-4-aminoaniline, IT, N-diethyl-2-methyl-p-phenylenediamine and the sulfates, hydrochlorides, sulfides, and the like, thereof, for which reference is made to C.E.K. Mees and T.H. Jases, The Theory of the Photographic Process, Pages 294-295 (The Macmillan Co., 1966) and U.S. patents 2 592 364 and 2 193 015 will be used. The color developers used for developing the color photographic materials according to the invention can furthermore common additives as used in the art contain, for example sulfites of alkali metals, carbonates, bisulfites, bromides, iodides ^ Benzyl alcohol and the like.

The bleaching solution can contain all known lead

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contain agents, such as ferricyanide, bichromate and the like. Also, the fixing solution can contain all known fixing agents, such as sodium thiosulfate, ivalium thioeyanate and the like, exhibit. Furthermore, the bleaching step and the fixing step can be carried out in one bath, and the like Blixbad is "given, for example, in U.S. Patent 3,582,322.

Typical bleaches are detailed in the Journal of the Society of Motion. Picture and Television Engineers 61, page 66? to? 01, and U.S. Patent 3,189-452, typical fixatives in Mason, Photographic Processing Chemistry, pp. 187-188, Focal Press (1966) and typical blix solutions in German patents 866 6O5 and 966 410, in British Journal of Photography, Pages 122 to 123 and 126 (1966) and in de :? U.S. Patent 3,5S2 3 ^ 2. In these references the generally applicable ratios are also listed.

The photographic materials according to the invention provide stable color images that do not fade if the color photographic material is exposed to heat or moisture exposed or stored for a long period of time. This advantage is due to the combination of 3 ~ ureido-5-pyrazoloii and the aldehyde without application from formalin, obtained, d. h., since the aldehydes according to the Invention limited to those with an aldehyde group attached to a carbon atom is formaldehyde ■ excluded from the scope of the present invention. This is completely surprising in view of the fact that if the above aldehyde is used together with a 3-kcylamino-5-pyrazolone, stability the color images cannot be improved.

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Furthermore, those used according to the invention have Aldehydes do not have a detrimental effect on photographic properties, for example hindering the Coupling of couplers and staining as in the case of the application of i'ormalin or compounds which Release ITormalin.

In addition, the aldehydes according to the invention have an effect of preventing the formation of fog upon magenta development. Continue to be Changes in the sensitivity of the highly sensitive emulsions prevented according to the invention during storage. This effect will continue in the above and below the oil halide emulsion layer The emulsion layers formed according to the invention are observed and is a completely surprising effect.

The following examples serve to further illustrate the invention.

example 1

To 100 g of a gelatine silver chlorobromide emulsion with a content of ^> 0 Mo 1% bromide and 0.05 mol of silver were a sensitizing dye with a sensitization maximum of about 54-5 ^ (150 mg per mole of silver halide) and 60 g a coupler dispersion, which had been prepared by dispersing the following masses using a comogenizer, added. The obtained silver halide emulsion was drawn up on a baryta-coated paper (drawn amount of silver 6 × 10 -4 mol / m). In this way, Samples A to D were produced.

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Coupler dispersion A BC D

Coupler 1 100 g 100 g 100 g

(specified below)

Coupler A (known) - - - 100 g

Dibutyl phthalate 100 g 100 g 100 g 100 g

Ethyl acetate 200 g 200 g 200 g 200 g

10% aqueous gelatin solution 1000 g 1000 g 1000 g 1000 g

Aqueous solution with

5 ^c / o sodium dodecylbenzene ■.

sulfonate 50 g 50 g 50 g 50 g

Acetaldehyde - 6g- -

Heptaldehyde - - 5 G ~

Known coupler A: condensation product from
1-Phenyl- 3- / 3 ~ (2-carboxymethyleic ο s-3-enami d) -b enzami do / -5-pyrazolone and acetaldehyde according to Ub patent specification 3,468,666.

Each of the samples prepared in this way was gradually (1000 lux, 1 sec.) Through a green filter with transmitted light from 500 to 600 rnu- and one Exposed to silver wedge and then treated in the following manner;

Treatment level temperature Time Parb development ■ 30 ⁰ G 4 min. Blix 30 ° C 2 min. Laundry 30 ⁰ G - 2 min. stabilization 3O ⁰ C 2 min.

The compositions of the treatment solutions used in the treatment stages are given below: .

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Color s wi c kl er
Sodium inetaborate
Sodium sulfite
Hydroxylamine (sulfate) potassium bromide

6-Elitrobenzimidazole (nitrate) sodium hydroxide
Benzyl alcohol
Dietary Glyco1

N-iLthyl-N-ß- (methaneulfonamidoethyl ) -p-phenylenediamine Uasser too

25th G 2 G 2 S. 0 , 5 s 0 , 02 g 4th S. 15th , 8 ml 20th ml 8th .e 1000 ml

Blix solution:

Iron salt of ethylenediamine

tetraessic acid 45 p Aranonium thiocyanate 10 c Hatriunis sulfite 10 g Ammonium thiosulfate (60 ^c / o) 1000 ml Tetr ^ sodium ethylenedianiine
tetracetate 5 s Water too 1000 ml. Statilizing bath: Tartaric acid 10 g Zinc sulfate 10 g. Natriuiametaborate 20 g - Water too 1000 ml.

After determining the reflection density of the kagenta dye images formed in this way, the treated samples were v; for 14 days at 60 ° C and 70 %> relative i ^! 'euchtir; ability to carry out a fading

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stored and then the ee flexion density of the color images determined again. The percentage of color remaining in the parts with image densities of 0.5 and 1.5 before the fade test according to the following equation calculated and are given in "La Table I:

Remaining dye (percentage) · = g- χ

A: Dye density after the fade test, fog density after the fade test »

B: Dye density before the fade test. Fog density before the fade test »

Table I.

Sample Maximum percentage of the remaining

Thick dye

Initial density Anfar.gsdichue "0.5 1.5.

A 2.5 -4-5- '60

B 2.5 85 90

c 2.5 87 90

D n, 7 55 65

Samples B and C, which contain the 3-ureido-5-pyrazolone Euppler and containing the aldehyde of the invention gave stable Magents dye images with little fading and this tendency was particularly pronounced on the low density parts. on the other hand Sample D containing the known coupler gave insufficient coupling density and gave unstable Dye images.

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.- 28 -

Example 2

A primer layer was formed on a cellulose acetate film backing with an antihalation layer containing carbon black on the opposite side, and then a coating composition containing a silver iodobromide emulsion containing 1.2 mol% of iodine and a coupler dispersion obtained by dispersing the Yellow coupler, a- (2-Hethylbenzoyl) -5-Zff- (2,4-di-tert-anylphenoxy) -8cetamido7-acetanili d had been prepared using dibutyl phthalate and ethyl acetate, attached to the base layer to form a "blue-sensitive layer A gelatin intermediate layer was formed on the blue-sensitive layer, and a coating composition containing a gelatin-silver chlorobronide emulsion containing 30 mol% of bromide and spectrally sensitized so that its maximum sensitization was about 685 µm was drawn up and a coupler dispersion, which by dispersing the cyan coupler 2-hydroxy-4-chloro-IT-hexadexyl-N- (2-cyanoaVfchyl) -2-naptht hamid was made using butyl phthalate and ethyl acetate, was coated on the Zv / i schen layer to form a red-sensitive layer. A gelatin intermediate layer was applied to the red-sensitive layer and then a coating composition containing 100 g of silver chlorobromide (content 0.06 mol of silver), which contained 35% silver and was spectrally sensitized such that its sensitization maximum was around 555 & Ά ? and 250 g of an Euppler dispersion, which had been prepared by dispersing the following components using a homogenizer, on the intermediate layer to form the green-sensitive one

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Layer raised. A protective gelatin layer was applied to the emulsion layer. Samples E through I were made this way. All systems consisted of gelatin systems.

Coupler dispersion E FG H I

Coupler 10 50 g 50 g 50 g. 50 g
(stated above)

Well-known Kuppfer B 50g 50 g 50 g 50 g 100 g Dibutyl phthalate 50 g 50 g 50 g 50 g 50 g Ethyl acetate 200 g 200 g 200 g 200 g 200 g 10% aqueous

Gelatin solution 1000 g 1000 g 1000 g 1000 g 1000 g aqueous solution

with 5 ° / ° sodium

dodecylbenzene

sulfonate. 100 g 100 g 100 g 100 g 100 g

Benzaldehyde - 5g

p-chlorobenzene

aldehyde - - 4g- 4- g

p-nitrobenzaldehyde - - 4g

Known coupler B: 1 ~ (2,4,6-trichlorophenyl) -5- / 5-ZÄ- ( 2,4-di-te rt.-amylphenoxy) -buty lami do7-benzami do 5-pyrazolone.

Each of the samples was exposed to light as in Example 1 and subjected to the following treatments.

309851/0869

temperature 2327731 Treatment level 2? ° C Time Pretreatment bath Il 10 sec. Laundry π 15 sec. Color development Il 5 min.,
20 sec. Laundry Si 15 sec. Blixung Il 4 min. Laundry II 2 Hin. Stabilization; 10 sec.

The compositions of those used in these stages Treatment solutions were the following:

Prepa ration ba d:

water

Sodium carbonate (monohydrate) Sodium sulfate (anhydrous) ■

Water too
Color developer: -

water
Sodium hexametaphosphate

Sodium sulfite anhydrous

2-amino-5-diethylaminotoluene hydrochloride

Sodium carbonate (monohydrate) potassium bromi d
Water too
Blix solution:

Sodium iron (III) ethylenediaminetetraacetic acid

Sodium carbonate (monohydrate) borax

Sodium thiosulfate

Water too

800 ml 10 B. 50 ε 1000 ml. 800 ml 2 G 4th S. 3 S. 2 , 5 s 2 , 0 g 1000 ml 34- S. 11 S. 45 S. 140 G 1000 ml.

309851/0869

Stabilizing bath:

Water 800 ml

Polyethylene glycol (molecular weight 400; , 40% aqueous solution 5 ml

V / ater of 1000 ml.

After determining the transmission density of the magenta dye images formed in this way, the treated samples were ^{stored for 30 days "at 50 ° C.} and 70% relative humidity, and then the transmission density of the dye images" was determined again. The percentages of dye remaining in the parts with image densities of 0.5 and 2, C before the fade test are given in Table II, all values being calculated as in Example 1

Table II

'robe ; Schiexer Percentage of dye remaining Initial density 2.0 density At the beginning s density 0.5 70 E. 0, Q8 50 90 F ' 0.07 85 91 F. 0.06 87 93 Ξ 0.06 88 70 I. 0.08 58

It can be seen from the above values that, according to the invention, stable magenta dyes, which hardly caused fading of the dye images, were obtained ^{in samples ϊ 1, G- and H, and that fog continued to occur in the case of magenta dyes.} Development under- ·

3098 51/0889

was pressed. On the other hand, in the case of comparative sample I, being a 3-acylanino-5-pyrazolone as a magenta coupler and the aldehyde were used according to the invention, the fading of the dye image is great. I.e. that the use of an aldehyde according to the invention only in combination with a J-ureido - ^ - pyrazolone was effective.

Example 3

On the surface of a paper, both surfaces of which were coated with a titanium dioxide-containing polyethylene, a "coating composition, which contained silver chlorobromide with a content of 85 Mo1% bromine, and a coupler dispersion, which by dispersing the yellow coupler, a- (4-methoxybenzyl ) -3- / cc ~ (2,4-di-tert-amylpheno ^ butylamido ^ -e-chloroacetanilide, prepared using dibutyl phthalate and ethyl acetate, was drawn up to form a blue-sensitive layer On the intermediate layer was a coating composition which contained 100 g of a silver chlorobromide emulsion with a content of 0.07% silver and a content of 30 mol% bromine, and 100 g of a coupler dispersion, which was obtained by dispersing a Sensibilizing dye with its sensitizing maximum of about 5 ^ 5 ^ ψ- and the components indicated below have been prepared by means of a homogenizer was, to a raised amount of silver

- 2 2

pulled up from 1 χ 10 mol / m.

3098S1 / Q869

Coupler dispersion JE. L M

Coupler 10 50 S. 50. S. 50 G 50 G Coupler - 11 5C. % .50 G 50 G 50 G Dibutyl phthalate 100 S. 100 G 100 G 100 G Ethyl acetate 150 G .150 G 150 G 150 G 10% aqueous Gelatin solution - 1000 ε. 1000 G 1000 G 1000 G Isopropyl aldehyde - VJI G - - m-chlorobenzaldehyde - - - 5 G - p-nitrobenzaldehyde - - - VJI G

A gelatin interlayer containing the Ultraviolet absorbent, 2- (2'-hydroxy-3'-methyl-5'-sec-butylphenyl) -benzotriazole, was drawn down on the emulsion layer and further on the intermediate layer a coating compound, which silver chlorobromide with a content of 40 mol% bromine, and a coupler dispersion, which by dispersing the Gyankouplers, ^ -, 6-dichloro-3-methyl-2-ZJä- (2,4-di-tert-amylphenoxy) -8cetamidg7-phenol, using dibutyl phthalate and ethyl acetate. In the end a protective gelatin layer was applied to the emulsion layer. In this way, samples J to M manufactured.

Immediately after the samples were prepared and after the samples had been stored for 3 days at 40 ° C. and 80 % relative humidity, the samples were tested with a wedge using a filter that allowed light from 500 to 600 mA to pass through and a filter that allowed light to pass through Wavelengths longer than 600 μm passed, exposed and then treated as in Example 1

309851/0869

possibility and the green sensitivity of the various Samples treated in this way were determined and the results became the change in sensitivity when stored under high temperature and high humidity determined. The results are shown in Table III, e.g. B. the vert "-0.30" indicates that the Sensitivity of the measured sample around 0.30 in logarithmic Units was elongated compared to the sensitivity of the fresh sample. Also the veil density and the results of the fade test carried out as in Example 1 are in the same table listed.

Change of
speed Table III Veil-
density - in the- ,
catching
density
1.0 sample Red sens Sensitive- 60
8 ^
90
95 opportunity Green feeling percentage
remaining -0.30
-0.15
-0.15
-0.15 opportunity 0.13
0.12
0.12
0.11 dye J
K
L.
M. -o,? o
-0.50
-0.50
-0.50 At first
density
0.5 45
80
85
90

From the above results, it can be seen that the stability of the magenta images according to the invention is improved and that furthermore the haze density of the Hagenta layer is lowered and the change in the Sensitivity of the green-sensitive layer itself as well as the sensitivity of the red-sensitive layer

309851/0869

according to the invention was reduced when the samples according to the invention under conditions of high temperature and high humidity.

See the excellent properties of color photography Materials according to the invention can thus be found in the above examples.

In the foregoing, the invention was "described on the basis of preferred embodiments" without them is limited to this.

3Q9851 / 0869

Claims (1)

Pat en t inspiring Ί \ l A color photographic material comprising a support having thereon photographic silver halide emulsion layer a 3-üreido-.5-pyrazolone magenta coupler and a compound having a bound to a carbon atom of the aldehyde group. . 2. color photographic material according to claim 1, characterized in that the magenta coupler consists of a compound corresponding to the formula R ,, NHCNH-C ¹ Il Il 0. N C = O R ₂ is wherein E ^, an alkyl group or an aryl group and Ro ^e i ^ne Hienylgruppe mean. 3 · color photographic material according to claim 2 _} characterized in that E. denotes an alkyl group with 1 to 32 carbon atoms or a monoaryl group and Rp denotes a phenyl group. 4 .. Color photographic material according to claim 3 » characterized in that E ^ is an alkyl group with Represents 8 to 18 carbon atoms, a phenyl group or a tolyl group. 5 color photographic material according to claim 2, 3 0 9851/0869 characterized in that Rp is one with one m halogen atom, an alkyl group having 1 to 5 carbon atoms or an alkoxyl group having 1 to 5 carbon atoms means substituted phenyl group. 6. A color photographic material according to claim 2 to 5i characterized in that at least one the Eeste E ^ or E2 represents a ballast group. 7. Farbphotographisch.es material according to claim 6, characterized in that the ballast group consists of a hydrophobic group with 8 to J2 carbon atoms consists. 8. Color photographic material according to claim 1 to 7i, characterized in that the amount of the coupler forming the magenta dye is about 0.05 to about 0.5 mol per mol of silver halide in the emulsion. 9 color photographic material according to claim 8, characterized in that the amount of the magenta dye forming coupler is from about 0.07 to about 0.2 moles per mole of silver halide in the emulsion. 10 .. Parbphotographic material according to claim 1 to 9 »characterized in that the ratio of Compound with the aldehyde group bonded to a carbon atom from 0.05 moles to about 30 moles per mole of the magenta coupler amounts to. 11. A carb photographic material according to claim 10, characterized in that the aldehyde group is attached to the carbon atom of an alkyl group, an aryl group or a heterocyclic group. 12. A color photographic material according to claim 11, characterized in that with the aldehyde group linked alkyl group 2 to 20 carbon atoms 3098B1 / 0889 23? 7731 contains and the aromatic group bonded via a carbon atom is a formyl-substituted phenyl or Is naphtliyl ring. , 13. A color photographic material according to claim 11, characterized in that the aryl group bonded via a carbon atom with a halogen atom, a Nitro-, hydroxy-, C. ~ to Cg-alkyl-, G.- to Cg-alkoxy-, Aryl, carboxy or sulfo group is substituted. 14. Farbpho togrsphisch.es material according to claim 11, characterized in that the aldehyde is derived from benzaldehyde consists. 15 i'arbphotographic material according to claim 14, characterized in that the benzaldehyde with a halogen atom, a nitro, hydroxy, C ^ - to Co-alkyl, C ^ to Cg alkoxy, aryl, carboxy or sulfo group is substituted. 16. A color photographic material according to claim 11, characterized in that the compound with the aldehyde group from acetaldehyde, propionaldehyde, butyraldehyde, Isobutyraldehyde, pivalylaldehyde, heptaldehyde, Lauric aldehyde, ßearic aldehyde, succindialdehyde, cro / tonaldehyde, Benzaldehyde, o-ChJ.benzsldehyd, n-chlorobenzaldehyde, p-chlorobenzaldehyde, p-bromobenzaldehyde, p-l-nitrobenzaldehyde, p-hydroxybenzaldehyde, o-tolualdehyde, cinnamaldehyde, a-naphthaldehyde or furfural. The color photographic material according to claim Ϊ to 16, characterized in that the average grain size of the silver halide present in the Emulsion etKa is 0.05 to about 1.5 microns. 18. Color photographic material according to. Claim. 17, characterized in that the weight ratio of Silver halide to binder-about 0.2 to about 20 (silver halide / binder) amounts to. 309851/0889 19 · Color photographic material according to claim 1 Ms 18, characterized in that E. from an alkyl " group "exists. . 20. A color photographic material according to claim 1 "to 18, characterized in that IL from an ary-1 group consists. 24 | · Color photographic material according to claim 1 "to 18, characterized in that IL consists of one of the following phenyl groups: Ca) -NHGOR ₃ (b) -NHGO4g (c) -MOOCH ₂ CD) (e) -COOH ₁₁ W. -OR ₁₂ E ₇ , ^E 8 ' ^E 9' ViOrin R ,, R ^, Rr ₇ , Rq, Rq, R ₁₁ and R _{12 are} an alkyl group and η is an integer from 1 to 5, 22. Color photographic material according to claim 21, characterized in that the radicals R _{1 to · R 12} contain 1 to 18 carbon atoms. 309851/0869