DE2727090A1 - COLOR PHOTOGRAPHIC DEVELOPMENT PROCESS - Google Patents

Description

PATENT LAWYERS

DR. E. WIEGAND DJ PL-1. »IG. V /. NiCMANN DR. M. KÖHLER DIPL-ING. C. GERNHARDT

MONKS "5" - HAMBURG TELEPHONE: 555476 8000 M ü N C H E N 2,

TELEGRAMS: KA R PATE, NT MATH I LD EN STRASSE

TELEX: 5 29 0 <S8 KARPD

W. 42903/77 - Ko / De June 15, 1977

Fuji Photo Film Co., Ltd. Minami Ashigara-Shi, Kanagawa (Japan)

Color photographic development process

The invention relates to a color photographic ,, development process, in particular, a color photographic development process using a color developer with improved Storage properties.

In the method for developing color photographic materials with a color developer according to the invention, which contains a primary aromatic amine as a color developing agent, a 3-pyrazolidone derivative and hydroxylamine or a derivative thereof, storage properties and stability of the color developer are improved if a compound in the color developer has a proportion corresponding to general formula

HO f C = C - ^ - A

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is incorporated, wherein A is a grouping -H or -NR ^ R ₂ , where R ^ and R _{2 is} a hydrogen atom or a group with fewer than 4 carbon atoms, and R ^ and R ₂ to form a 5-membered or 6 - membered ring can be united, and η is a positive number from 1 to 4-, and in which the remainder - £ C = C - ^ - can form a chain or a ring.

In color photographic developing systems for manufacture of color photographic images using color photography Silver halide materials are known to have the dye-forming couplers present in the color photographic material undergo imagewise coupling with the oxidized primary aromatic arain as a color developing agent in the color developing step with the formation of indoaniline, indophenol and azomethine dyes, whereby the color photographs Images are trained.

It is generally desired that the silver halide color photographic materials can be developed within a short period of time and therefore various attempts have been made so far for proposed a rapid color development process. In particular is a color developer additionally containing a black and white developing agent as a development accelerator as a super additive color developer known and as an example of such methods, it is known that a 3-pyrazolidone derivative has a very has strong development accelerating effect.

That achieved with the 3-pyrazolone derivatives in the color development For example, superadditivity is described in G.F. van Veelen, The Journal of Photographic Science, Volume 20, pp. 9A-106 (1972), German Patent 1,057,875 and the like.

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A 3-I ⁵ TTaZOlidonderivat containing color developer is, however, compared to a developer (PQ developer), the hydroquinone and containing 1-pyrazolidone 3-phenyl-and is commonly used for black and white development and a conventional color developer does not contain a 3-pyrazolidone derivative is very unstable, and consequently, when a color developer is used for industrial color photography development, it is beneficial to improve the storage properties of a color developer containing a 3-pyrazolidone derivative.

It is common in the photographic art to use a sulfite and a hydroxylamine salt as antioxidants in color developers, containing an aromatic primary amine as a color developing agent to prevent a decrease in the To incorporate developing property due to air oxidation. However, these antioxidants are for color developers, containing a 3-pyrazolidone derivative are not very effective. This means, they are decomposed via an intermediate that is green in color, which is a reaction intermediate with the 3-pyrazolidone derivative and the aromatic primary amine as a color developing agent due to air oxidation of the 3-pyrazolidone derivative itself and represents damage and air oxidation by alkaline hydrolysis, so that precipitates or sludge may be formed in the developer, making the use of the antioxidants listed above completely unsatisfactory as a preservative for the developer.

The use of a dihydroxyalkene and 2-anilinoethanol as an antioxidant instead of hydroxylamine is suggested in US Patents 3,615,503 and 3,823,017, however they are ineffective for a color developer containing a 3-pyrazolidone derivative. Also ascorbic acid and derivatives of these or dihydroxybenzenes are known as antioxidants for color developers and black-and-white developers, but

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they prevent the coloring of a color developer and are practically ineffective for color developers using a 3-pyrazolidone derivative and are also ineffective in preventing sludge and precipitate from forming in the color developer.

On the other hand, it is known that sucrose or sucrose as an antioxidant in a black and white developer containing a Contains N-alkyl-p-aminophenol as a developing agent but sucrose or sucrose is extremely ineffective in a color developer containing a 3-pyrazolidone derivative.

Therefore, it is a first object of the invention to provide a color photographic processing method using a color developer ^{containing a 3-1 3} yrazolidone derivative, which color developer has high storage properties and shows little change in photographic processing properties with the lapse of time.

A second object of the invention is a color photographic one A development method using a color developer containing a 3-fyrazolidone derivative, the Color developer is stable and no sludge or precipitate is formed in the developer if the developer is used during one is stored or used for a long period of time.

A third object of the invention is a color photographic one A development method using a color developer containing a 3-pyrazolidone derivative, none of which Green discoloration occurs due to air oxidation in the color developer.

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A fourth object of the invention is a color photographic one A development method using a color developer containing a 3-pyrazolidone derivative, none of which The coloring is prevented by an antioxidant in the color developer.

A fifth object of the invention is to provide a color developer with good stability that is suitable for photographic use Rapid development can be used.

It has now been found that the above objects of the invention using a compound which contains therein a proportion corresponding to the formula

HO - (- CC - ^ ₅ - A

contains, where A is a group -OH or -NR ^] ^ »where R ^ and R2 each represent a hydrogen atom or a group with fewer than 4 carbon atoms and R. and Rp can also be combined and form a 5-membered or 6- form a membered ring, and η denotes a positive integer from Λ to 4 and in which the moiety —f CC ■) - can form a chain or a ring, in a color developer which (1) a primary aromatic amine as a color developing agent, (2 ) contains a 3-pyrazolidone derivative and (3) hydroxylamine or a derivative thereof as an antioxidant can be achieved.

In the context of the description of the invention in detail, one of the particularly preferred compounds according to the invention among the compounds having a skeleton HO- £ CC ^ j-OH as part of the structure thereof is a hydroquinone, although it was previously known that if hydroquinone to is added to a color developer, the hydroquinone hinders the coloring and accelerates the oxidation of the color developing agent, in other words, hydroquinone

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acts as an oxidation accelerator rather than an antioxidant when used alone. Therefore it is completely unexpected that the storage properties of a 3-pyrazolidone derivative containing color developer is remarkable by using hydroxylamine or a derivative thereof, as follows referred to as a hydroxylamine compound, together with a suitable amount of a hydroquinone according to the invention to be improved remarkably.

Preferred examples of primary aromatic amines as color developing agents (component 1) of the color developer used according to the invention are the following p-phenylenediamine derivatives, for example Ν, Ν-diethyl-p-phenylenediamine hydrochloride, N, N-diethyl-p-phenylenediamine sulfate, 2-amino ~ 5 diethylaminotoluene hydrochloride, 2-amino-5- (N-ethyl-N-laurylamino) -toluene, 4- ^ N-ethyl-N- (β-hydroxyethyl) -aminq7-aniline sulfate, 2-methyl-4- ^ N-ethyl -N- (ß-hydroxyethyl) -amino7-aniline sulfate, NA * thyl-N- (ß-methanesulfoamidoethyl) -3-methyl-4-aminoaniline sesquisulfate monohydriate, as described in US Pat. No. 2,193,015, N- (2 -Amino-5-diethylaminophenylethyl) methanesulfonamide sulfate, as described in US Pat. No. 2,592,364, Ν, Ν-dimethyl-p-phenylenediamine hydrochloride and ^ -amino ^ -methyl-N-ethyl-N-methoxyethylaniline, A-amino 3-methyl-N-ethyl-N-ß-ethoxyethylaniline and 4-amino-3-methyl-N-ethyl-N-ß-butoxyethylaniline and salts thereof, for example the sulfates, hydrochlorides, sulfites, p-toluene sulfate fo- nate and the like, the like as described in US Patents 3,656,950 »3,698,525 and.

More preferred examples of primary aromatic amines as color developing agents are N, N-diethyl-p-phenylendiamine sulfate and 4- ^ TJ-ethyl-N- (β-hydroxyethyl) -amino7-aniline sulfate.

The suitable proportion of the color developing agent is usually about 0.1 to about 200 g, preferably 0.5 to 100 g, and more preferably 1 to 50 g, per liter of the color developer.

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The 3-I ^ rrazolidonderivate (component 2) of the invention The dye used are 3-pyrazolidone derivatives, their 1-position of the 3-pyrazolidone ring with an aryl group or a substituted aryl group, as for example in British Patents 5 ^ 2 502, W 928, 1,093,281, 1,182,198 and 1,242,112 and U.S. Patents 3,453,109, 3,261,885 and 3,740,221. In particular becomes a 3-pyrazolidone derivative with a phenyl group in the 1-position of the pyrazolidone ring preferred. Also from the point of view that the 3-pyrazolidone derivative itself has good water solubility has, forms little precipitate and dirt in the color developer, has good stability in the color developer and giving rise to far less deleterious influences, particularly fog, on the photographic properties of the formed If color images are obtained, 3-fyrazolidone derivatives with 1 or 2 Hydroxyalkyl groups in the 4-position of the 3-pyrazolidone ring, as described in British Patent 1,093,281 or US Patent 3,453,109 are particularly preferred.

Also those described in British Patent No. 542 502 " Compounds are particularly preferred examples of 3-pyrazolidone derivatives corresponding to British Patent 1,093,281 cited above, although the formation of haze takes place to a somewhat greater extent.

Suitable, usable 3-pyrazolidone derivatives are those of general formula

ν ^{2 5} c <- ^c

^R 2,

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wherein R ^ is an aryl group or a substituted aryl group and Rp, Rx, R ^., Sr and Rg are a hydrogen atom, an acyl group, represent an alkyl group, a substituted alkyl group, an aryl group or a substituted aryl group.

More preferably the radical R ^ in the 1-position is one Phenyl group or a substituted phenyl group, R £, Rc and Rg denote a Vasseretoffatom and R, and R ^ denote a hydrogen atom or an alkyl group, for example 1-phenyl-3-pyrazolidone, 4-methyl-1-phenyl-3-pyrazolidone and 4,4'-dimethyl-1-phenyl-3-pyrazolidone.

Most preferably at least one of the radicals R is and R ^ in the 4-position is a hydroxyalkyl group, for example 4-hydroxymethyl-4-methyl-1-phenyl-3-pyrazolidone and 4,4'-dihydroxymethyli-phenyl-3-pyrazolidone.

The appropriate amount of the 3-pyrazolidone derivative employed in accordance with the invention is also usually about 0.01 to about 50 g, preferably 0.05 to 10 g, and more preferably 0.1 up to 4g, per liter of the color developer.

There is no particular limitation on the hydroxyl compounds that can which can be used as component (3) according to the invention and examples of hydroxylamine compounds are hydroxylamine itself, N-monoalkylhydroxylamines, such as N-methylhydroxylamine hydrochloride, N, N-diethylhydroxylamines, aminoalkylhydroxylamines according to US Pat. No. 3,287,125, alkoxyhydroxylamines according to US Pat. No. 5,293,034, Ν, Ν-dialkylhydroxylamines and heterocyclic N-hydroxylamines such as N-hydroxylpiperidine. These can be used as such or as salts thereof, however, from the technical point of view, such as Cost, stability, water solubility, accessibility, applicability and the like, hydroxylamine sulfate, hydroxylamine hydro-

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Chloride, Ν, Ν-diethylhydroxylamine, Ν, Ν-diethylhydroxylamine oxalate and the like are preferred.

Particularly preferred hydroxylamine compounds are hydroxylamine and Ν, Ν-dialkylhydroxylamines, such as hydroxylamine sulfate and H, N-diethylhydroxyl amine.

The suitable proportion of the hydroxylamine compound used according to the invention is usually about 0.1 to about 100 g, preferably 0.5 to 50 g, and more preferably 1 to 20 g, each Liters of color developer.

Compounds with a skeleton HO— £ C = C "^ -OH as part of the structure thereof, which in the context of the invention as component (4) -1 are used, for example, in C.E.E. Mees & T.H. James, The Theory of the Photographic Process, pages 285-290 Macmillan Co., New York (1966) and J. Eggers, Zurich Conf., Chapter 3 (1961) described. Specific examples of such compounds are hydroquinone, dihydroxybenzene derivatives such as tert-butylhydroquinone, Chlorohydroquinone, phenylhydroquinone, pyrocatechol and the like, polyhydroxybenzene derivatives such as pyrogallol, reductones from Endiol type, such as L-ascorbic acid, triose reductone, reductic acid and the same. Of the compounds listed above, dihydroxybenzene derivatives and enediol type reductones are particularly useful. In particular, hydroquinone is most preferred because this material is widely used industrially. L-ascorbic acid is also preferred.

The compounds with the framework HO- £ C-C ^ jj-OH as part of the Structure of the same as used according to the invention who the nuts are added to such an extent that there is no staining. The suitable proportion of this compound is thus usually from about 0.01 to about 5.0 g preferably 0.05 to 2.0 g, more preferably 0.1 to 1.0 g, each Liter of color developer.

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The essential feature of the compound with the skeleton HO— £ CC 9 —OH as part of the structure thereof, as used in the context of the invention, is that the compound selectively prevents the occurrence of oxidative decomposition of the 3-pyrazolidone derivative and that furthermore the compound is extremely ineffective when it is together with a hydroxylamine derivative in a color developer not containing a 3-pyrazolidone derivative, as is readily shown by the results given in Example 1 below. It is therefore believed that the compound with the skeleton HO- £ CC ^ j-OH as part of the structure thereof has an effect of regenerating the 3-pyrazolidone derivative and consequently very effectively the occurrence of the oxidation of the 3-I ³ yrazolidone derivative in the initial stage when using a color developer containing this material. In other words, without being bound by this theory, it is believed that the compound having the skeleton HO- £ C = C ^ pOH as part of the structure thereof has very poor stability when used alone and is rapidly damaged however, since the compound is stabilized by the action of the hydroxylamine derivative used as an antioxidant together with the compound, so that the effect of 3-pyrazolidone as an antioxidant can be maintained for a long period of time in the presence of the above-mentioned compound. That is, it is believed that in the color developer containing the 3-pyrazolidone derivative used in the present invention, the 3-pyrazolidone derivative, which is the most unstable component of the components of the color developer, selectively by the compound having the skeleton HO- £ CC ^ -OE as Part of the structure of the same is stabilized, thus the compound with the skeleton HO— £ -CC ·) —OH and the primary aromatic amine as a color developing agent, which are contained in the color developer, are also stabilized by the hydroxylamine derivative and furthermore the hydroxylamine derivative to the

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Stabilization of the 3-pyrazolidone derivative through support the connection with the framework HO— £ C = C— ^ - OH contributes. the end The use of a hydroxylamine compound differs from that of ascorbic acid for the reasons discussed above or tetronic acid together with a primary aromatic amine as a color developing agent in a color developer for the purpose the prevention of sludge formation in the color developer, as described in US Pat. No. 2,923,627, clearly in the technical sense of the teaching of the present invention.

Examples of compounds with the skeleton HO- £ C = C ^ j ₁₂ as used according to the invention as component (4) -2 of the color developer composition are also described in detail in CEK Mees & TH James, supra, pages 290-293. Of these compounds, the compounds with the structure listed above HO- £ C = C - ^ _n -NR ₁ R ₂ , in which R ^ and R _{2 are} combined and form a 5-membered or 6-membered ring, for example a heterocyclic ring, and the hetero atom consists of nitrogen in which the number of nitrogen atoms is 4 or less, for example a pyrrolidino group, is preferred. Specific examples of such compounds are p-pyrrolidinophenol, p-morpholinophenol, p-piperidinophenol and p-pyridinophenol.

A greater amount of this type of compound can be used than that of the compound with the skeleton HO - C "C - ^ _n -OH. That is, the suitable amount of this compound as component (4) -2 is usually 0.01 to about 10 g, preferably 0.05 to 50 g, and more preferably 0.1 to 3.0 g, per liter of the color developer . It is also believed that the skeleton compound HO- £ C = _{C- ^ Jj-NR 1} Rg selectively inhibits ^the oxidative decomposition of the 3-pyrazolidone derivative in the same manner as when a skeleton compound is used

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HO-£ C "C - ^ - OH is as described above.

The one used according to the invention, containing the 3-pyrazolidone derivative A color developer can also be a sulfite, such as sodium sulfite, potassium sulfite, potassium hydrogen sulfite, sodium hydrogen sulfite and the like commonly used as antioxidants, as well as other known developing components in addition to the components listed above. The suitable amount of sulfite is about 1 to about 100 g / l, preferably 2 to 50 g / l, more preferably 5 to 30 g / l. Examples for other developer components are, for example, alkaline agents, buffers and the like, such as sodium hydroxide, potassium hydroxide, Sodium carbonate, potassium carbonate, sodium tertiary phosphate, potassium tertiary phosphate, potassium metaborate, borax and the like, and they can be used singly or as combinations. The color developer can also contain various salts, such as disodium hydrogen phosphate, dipotassium hydrogen phosphate, sodium hydrogen phosphate, Potassium dihydrogen phosphate, sodium hydrogen carbonate, Potassium hydrogen carbonate, boric acid, alkali nitrates, alkali sulfates and the like, for buffering the color developer, for Facilitate the manufacture of the color developer and increase it the ionic strength.

The color developer used in the present invention can also contain, if desired, a suitable development accelerating agent such as the various pyridinium compounds and other cationic compounds, cationic dyes, as Fhenosafranin, natural salts such as Thalliumnürat and potassium nitrate, polyethylene glycol and derivatives thereof corresponding to Japanese Patent publication 9504/69, and U.S. patents 2,533,990, 2,531,832, 2,950,970 and 2,577,127, nonionic compounds such as polythioethers , or-

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ganic solvents, organic amines, ethanolamine, ethylenediamine, Diethanolamine and the like corresponding to Japanese Patent Publication 9509/69 and Belgian Patent Publication 682 862 included. Further examples of development accelerators which can be used according to the invention, are in L.P.A. Mason, Photographic Processing Chemistry, pp 40-43 (1966), Focal Press London (1966). Further examples suitable development accelerators are benzyl alcohol and phenylethyl alcohol, as described in U.S. Patent 2,515 and pyridine, ammonia, hydrazine and amines as described in Journal of the Society of Photographic Science and Technology of Japan, Volume 14, Page? 4 (1952).

Further, the color developer used in the present invention can be used if desired contain any antifoggant; Alkali halides, such as potassium bromide, sodium bromide, potassium iodide and the like and organic antifoggants can be used as such antifoggants are used. Examples of organic antifoggants are nitrogen-containing heterocyclic ones Compounds such as benzotriazole, 6-nitrobenzimidazole, 3-nitroisoindazole, 5-methylbenzotriazole, 5-nitrobenzotriazole, 5-chlorobenzotriazole, Mercapto-substituted heterocyclic compounds such as 1-phenyl-5-mercaptotetrazole, 2-mercaptobenzimidazole, 2-mercaptobenzothiazole and the like, and also mercapto-substituted aromatic compounds such as thiosalicylic acid and the same. Particularly preferred development accelerators are nitrogen-containing heterocyclic compounds, In particular, mercapto-substituted nitrogen-containing heterocyclic ones Links. The appropriate proportion of the anti-fog ■ agent is about 1 mg to about 5 g »preferably 5 mg to 1 g per liter of the color developer.

Furthermore, polyphoephoric acid compounds, such as sodium hexanetaphosphate, Sodium tetrapolyphosphate, sodium tripolyphosphate, potassium hexametaphosphate, potassium tetrapolyphosphate, potassium tripolyphosphate

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phosphate and the like and aminopolycarboxylic acids, such as ethylenediaminetetraacetic acid, Nitrilotriacetic acid, cyclohexanediaminetetraacetic acid, iminodiacetic acid, N-hydroxymethylethylenediamine triacetic acid, Diethylenetriaminepentaacetic acid and the like as water softening agents in the present invention Color developer can be used. The amount of water softener depends on the hardness of the water used, however the suitable amount is usually within about 0.5 to about 1 g per liter of the color developer.

Furthermore, a calcium sequestering agent or magnesium sequestering agent can be used can also be used in the photographic developing solution. Examples are in detail in J. Willems, Belgische Chemische Industrie, Volume 21, page (1956) and ibid., Volume 23, page 1105 (1958).

The color developer used in the present invention may further contain stain inhibitors or sludge inhibitors, as described in U.S. Patents 3,161,513 and 3,161 and British Patents 1,030,442, 1,144,481 and 1,251,558, multilayer effects accelerators, as described in U.S. Patent 3,536,48? and the like are described, solvents such as diethylene glycol and color formers, such as couplers.

The pH of the color developer used in the invention is generally in the range of from 7 to about 14, preferably from about 8 to 13. The suitable temperature at which the invention may be used of the color developer according to is in the range of about 20 to about 7O ⁰ C, preferably 30 to 60 ⁰ C.

In the case of applying the method according to the invention to the Reverse color development can compete couplers, fogging agents and compensating developing agents further to that of the present invention used color developer can be added.

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Competitive couplers that can be used are citraζic acid, I-acid,
Η-acid and the like. Other examples of competitive couplers which can be used according to the invention are given in the US patent

2,742,832, Japanese Patent Publications 9504/69,
9506/69 and 9507/69 and U.S. Patents 3,520,690,

3,560,212 and 3,645,737.

The useful fogging agents include alkali borohydrides, aminoboranes, Ethylenediamine and the like. Further according to the invention useful examples of fogging agents are described in Japanese Patent Publication 38816/72.

The color photographic process according to the invention is applicable to color photographic systems employing color photographic materials containing color-forming couplers in the silver halide emulsion layers, such as those described in U.S. Patents 2,322,027, 2,376,679 and 2,801,171
and to color photographic systems employing color developers containing couplers such as those described in U.S. Patents 2,252,718, 2,590,970 and 2,592,243
are applicable.

However, the color photographic system is currently in use of couplers in the photographic emulsion are mainly practiced. In the color photographic system wherein the dye-forming couplers present in the color photographic light-sensitive materials generally become multilayered color photographic materials are used and in this case it is favorable that the couplers in each emulsion layer des multilayer color photographic material remain in each emulsion layer and not in other emulsion layers during the manufacture, storage and development of color photographic Diffuse materials.

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Furthermore, the color photographic method according to the invention is also applicable to the color photographic diffusion transfer system applicable as described in U.S. Patents 3,227,551 and 3,227,552. In this case, the couplers may or may not diffuse into other layers.

Furthermore, the color photographic process according to the invention is also applicable to color intensifying systems using hydrogen peroxide applicable, as in the German OLS 1 813 920,

1 950 102, 1 995 901, 1 961 029, 2 044 833, 2 044 993, 2 056 360,

2 056 359 and 2 120 091, or the color intensifier system using Co (III) complex salts as in U.S. Patents 3,826,652, 3,834,907, 3,738,138 and 3,765 described, applicable.

The process according to the invention can thus be applied to the development of all customary color photographic silver halide materials, such as negative color photographic films, color photographic papers, positive color photographic films, reversal color photographic films and the like can be used.

The basic development processes in the invention Methods for developing these common color photographic materials are as follows:

(1) color development -> bleaching - * washing -> Fixation -) Laundry - ^ Stabilization> Drying.

(2) color development -> blix treatment -> Laundry - ^ Stabilization - ^ Drying.

(3) color development -> stop fixing -? Blix treatment -> Laundry - ^ stabilization -> drying.

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In each of the processes (1) to (3), a pretreatment bath, a pre-hardening bath and the like before the color development step can be applied and the stabilizing step and also the washing step after the bleaching step can be omitted will.

On the other hand, the basic development processes in the method of the present invention are for color photographic development Reversal films typically include the following:

Black-and-white development -> stop treatment - ^ washing

Laying - ^ washing> Color development -> bleaching - ^

Laundry - ^ Fixation - ^ Laundry - ^ Stabilization - ^ Drying.

(5) Black and White Development -> Stop Treatment - ^ Wash - ^ Schi eierung - ^ washing - ^ color development - ^ blix treatment -; Laundry -> Stabilization - ^ Drying.

In each of the above methods (4) and (5), further a pre-treatment bath, a pre-hardening bath, a neutralization bath and the like can be used, or the stabilizing step may be used and also the washing step after the bleaching step can be omitted. Furthermore, the veil level can be renewed Exposure stage can be replaced and the fogging bath can also be used with the addition of a fogging agent, for example tert-butylaminoborane, Sodium borohydride, tin aminopolycarboxylic acid complex salts and the like to the color developer can be omitted

It can be clearly seen from the procedures outlined above (1) to (5), a blix bath can be used instead of a bleach bath and a fixer when a fixer is added to a bleach bath can be applied.

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Numerous compounds can be used as bleaching agents in the above listed development processes are used. Examples of suitable bleaching agents are polyvalent metal compounds, such as ferricyanides, dichromates, water-soluble cobalt (III) salts, water-soluble copper (II) salts, water-soluble ones Iron (III), cobalt (III) or copper (II) quinones and iron (III), cobalt (III) or copper (II) nitrosophenols, Metal complex salts of such polyvalent metal cations and organic acids, such as ethylenediaminetetraacetic acid, nitrilotriacetic acid, Iminodiacetic acid, N-hydroxyethylethylenediamine triacetic acid, Malonic acid, tartaric acid, malic acid, diglycolic acid and dithioglycolic acid, 2,6-dipicolinic acid copper complex salt, Peracids, such as alkyl peracids, persulfates, permanganates, hydrogen peroxide and the like, hydrochlorites, chlorine, bromine, bleach powder and the like. These bleaches can be used individually or can be used in the form of suitable combinations. The developing solutions used according to the invention can also various additives such as bleach accelerators disclosed in U.S. Patents 3,042,520 and 3,241,966 and Japanese Patent Publications 8506/70 and 8836/70 contain.

The methods (1) to (5) discussed above are useful in the color photographic development method according to FIG Invention, without the invention being restricted to these processes, and further processes can be used in the development process according to of the invention can be applied.

It is well known to form color images by exposing color photographic materials to radiation. Color radiographic materials used for this purpose have long been known and are generally described in (A) a system wherein general multi-layer color photographic materials are used as they are to form color images by exposure to the color

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photographic materials to an ordinary color photographic sheet Post-radiographic exposure treatment according to U.S. Patents 2,807,725; 2,931,904 and 3,114,833 can be employed, (B) a system in which coupler-containing photographic materials have an ordinary color development after exposure to form color images, as in U.S. Patents 2,994-610 and 3 121 232 and French patent 3 077 659 and (C) a system wherein coupler-containing photographic Materials after exposure in the steps of color developing fix washing to form dyes and silver-built images (the steps used not including a silver removal step) are developed, such as U.S. Patents 3,622,629, 3,627,530, 3,734,735, and 3 809 906, British Patent 1 122 085, German OLS 1 158 836 and Japanese patent application 37 539/72 described, divided.

Compared to black and white radiographic materials radiographic color materials have various advantageous points of view as they have a high resolution and a large The amount of information given by their excellent granularity provides a large amount of information for exposure of silver halide can be reduced and further the cost thereof is low.

Radiographic materials must be dated from radiographic very quickly Point of view to be developed and it is currently in the process of developing black and white radiographic materials It is customary for all stages of development, fixing, washing and drying to be completed within 2 minutes.

Therefore, radiographic color materials must of course can be developed rapidly as in the case of black and white radiographic materials, and in view of this requirement

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nis is system (C) listed above, which does not employ a silver removal step, out of those discussed above Systems (A), (B) and (C) are most suitable for practice. As in the light-sensitive developed according to the system (C) Materials dye images and silver images are present at the same time and each contribute to the image density and thus one high image density is obtained with a low content of silver halide in the case of employing the system (C), it becomes consequently, it is particularly preferred to use the system (C) for developing radiographic color materials and in the specification of the present invention, the system (C) is understood as a treatment method for radiographic color materials, unless otherwise stated.

In the case of developing radiographic color materials, the developing process according to the invention does not include a silver removal step in contrast to the development of general color photographic materials as described above, and usually includes the steps of color development, fixing, washing, drying as the basic steps. To the In practicing the method, it is preferred to use an automatic developing machine (1) of the roller conveyor type, (2) of the belt conveyor type or (3) chain conveyor type.

Since the inventive method using the 3-pyrazolidone derivative containing color developer can be carried out very quickly compared with an ordinary color developer can, the method of the invention is very advantageous for developing radiographic color materials, which are particularly require high speed of development.

In the color photographic materials including the above Treated radiographic materials to which the invention is applicable can all conventionally be used as supports

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materials used for general photographic materials. Examples of suitable ones in the Photographic materials to which the invention can be applied, supports used are cellulose nitrate films, cellulose acetate films, cellulose acetate butyrate films, cellulose acetate propionate films, polystyrene films, polyethylene terephthalate films, Eolycarbonate films, laminates made of these polymer films, papers and the like. These carriers can optionally be colored · Examples of dyes used to color such carrier films are in US Patents 2,571,319, 5 572 1J8, 3 488 195, 3 359 230, 3 413 257, 3 520 132 and 3 487 041.

Furthermore, a baryta-coated paper or a with a fl ^ olefin polymers coated or coated paper, in particular a polymer of a ^ G-olefin with 2 to 10 carbon atoms, such as polyethylene, polypropylene and the like, can also be used as a carrier. Synthetic resin films, the surface of which has been matted with other polymers to improve the adhesive property and to improve the printability, as described in Japanese Patent Publication 19O68 / 72, can also be used favorably as Supports for the color photographic materials to which the invention is applicable can be used.

Various types of hydrophilic colloids can be used in the dye photographic materials developed by the method of the present invention. Examples of suitable, as Hydrophilic colloids which can be used as binders for photographic emulsions and / or other photographic layers are, for example, gelatin, colloidal albumin, casein, carboxymethyl cellulose, hydroxyethyl cellulose, agar agar, sodium alginate, starch derivatives and synthetic hydrophilic colloids such as polyvinyl alcohol, poly-N-vinylpyrrolidone, poly-N-vinylpyrrolidone , Poly-

709852/0990

acrylamide and derivatives and partially decomposed products thereof. If desired, a compatible mixture of two or more such colloids are used. Of the colloids discussed above, gelatin is most commonly used and gelatin can be partially or completely replaced by synthetic polymers. Furthermore, gelatin derivatives, i. with reactive agents with one to react with amino groups, imino groups, hydroxyl groups or carboxy groups in the gelatin molecule gelatin or gelatin graft polymers modified as functional groups, which are formed by grafting a molecular chain of a further polymer produced thereon can also be used instead of gelatin.

The photographic ones which can be developed by the process according to the invention Silver halide emulsion layers or other layers of the color photographic materials can also be used synthetic polymers such as a latex made from a water-dispersible vinyl compound polymer, particularly a vinyl polymer latex to improve the dimensional stability of the photographic material, individually or as a mixture with others Polymers or a combination thereof with a hydrophilic water-permeable colloid. Various polymers, as described, for example, in U.S. Patents 2,376,005,

2 739 137, 2 853 4-57, 3 062 674-, 3 411 911, 3 488 708, 3 525 620,

3,635,715, 3,607,290, 3,645,740 and British patents 1 186 699 and 1 307 373 can refer to this Purpose to be used. Specific examples of advantageously usable polymers are copolymers and polymers, such as alkyl acrylates, alkyl methacrylates, acrylic acid, methacrylic acid, SuIfoalkylacrylate, SuIfoalkylmethacrylate, Glycidylacryl ate, Glycidyl methacrylates, hydroxyalkyl acrylates, hydroxyalkyl methacrylates, Alkoxyalkyl acrylates, alkoxymethacrylates, styrene, butadiene, Vinyl chloride, vinylidene chloride, maleic anhydride and itaconic anhydride. If such vinyl compounds of an emul-

709852/0990

«Ion polymerization can be subjected to a so-called emulsion polymerized latex of the graft type, which in the presence a hydrophilic protective colloid polymer was produced, may be used.

The photographic emulsion layers or other photographic layers can be hardened using conventional methods. Examples of suitable curing agents which can be used are aldehyde compounds such as formaldehyde, glutaraldehyde and the like, ketone compounds such as diacetyl, cyclopentadione and the like, reactive halogen-containing compounds such as 2-hydroxy-4,6-dichloro-1,3,5-triazine , Bis (2-chloroethyl urine) and the compounds corresponding to US patents 5 288 775 and 2 732 303 and British patents 974 723 and 1 167 207, reactive olefin-containing compounds such as divinyl sulfone, 5-acetyl-1, 3-diacryloylhexahydro-1,3ι5-triazine and the compounds according to US Patents 3,635,718, 3,232,763, 3 W 911, 3,542,486 and British Patent 994,869, N-methylol compounds such as N-hydroxymethylphthalimide or the compounds according to US Pat. No. 2,732,316 and 2,586,168, the isocyanates according to US Pat. No. 3,103,437, aziridine compounds according to US Pat. No. 3,017,280 and 2,983,611, acid derivatives according to US Patents 2,725,294 and 2,725,295, cerbodiimide compounds corresponding to US Patent 3,100,704, epoxy compounds corresponding to US Patent 3,091,537, isoxazole compounds corresponding to US Patents 3,321,313 and 3,543,292, halocarboxyaldehydes such as mucochloric acid and the like, dioxane derivatives such as dihydroxydioxane, dicblordioxane and the like, and inorganic hardening agents such as chrome alum * zirconium sulfate and the like. Precursors for such hardening agents can also be used in place of the hardening agents themselves. Examples of such levelers are alkali metal bisulfite-aldehyde addition products, methylol derivatives

709RS2 / 0990

of hydantoin, primary aliphatic nitro alcohols and the like.

The silver halide photographic emulsion of the color photographic Material is usually made by mixing an aqueous solution of a water-soluble silver salt, such as Example silver nitrate, and an aqueous solution of a water-soluble halide salt, for example potassium bromide, in the presence an aqueous solution of a water-soluble polymer such as gelatin. Suitable silver halides that can be used are silver chloride, silver bromide and mixed silver halides such as silver chlorobromide, silver iodobromide and silver chloroiodobromide. In the case of radiographic color materials, the use of silver iodobromide at a level of less than about 10 mole percent Silver iodide preferred. The grains of these silver halides can be prepared by known customary processes. A single nozzle process, a double nozzle method, a controlled double nozzle method and the like can advantageously be used Production of these silver halide grains can be used. Two or more different silver halide photographic emulsions can also be used be made separately and if desired be mixed. Various additives may be added to the silver halide photographic emulsions listed above to prevent a decrease in sensitivity and the formation of fog during manufacture, storage and Treatment of color photographic materials included. Additives that can be used for this purpose have long been 4-hydroxy-6-methyl-1,3 * 3a, 7-tetrazaindene, 3-methyl-benzothiazole, 1-phenyl-5-mercaptotetrazole as well as numerous heterocyclic compounds, mercury-containing compounds, mercapto compounds, metal salts and the like known. Specific examples of additives that can be used are given in U.S. Patents 1,758,576, 2 110 178, 2 131 038, 2 173 628, 2 697 040, 2 304 962, 2 324 123, 2 394 198, 2 444 605, 2 444 606, 2 444 607, 2 444 608, 2 566 245, 2 694 716, 2 697 099, 2 708 162, 2 728 663, 2 728 664, 2 728 665,

7098B2 / 0990

2,476,536, 2,824,001, 2,843,491, 2,886,437, 3,052

3 137 577, 3 220 839, 3 226 231, 3 220 839, 3 226 231, 3 236 652, 3 251 691, 3 252 799, 3 287 135, 3 326 681, 3,420,668, 3,619,198, 3,622,339 and 3,650,759 and British patents 893,428, 403 709, 1,173,609 and

1 200 188 listed.

The silver halide emulsions can continue to chemically under Be sensitized using normal procedures. Examples of chemical sensitizers that are used for chemical sensitization can be used are, for example, gold compounds such as chloroaurates, gold trichloride and the like, accordingly U.S. Patents 2,399,083, 2,540,085, 2,597 and 2,597,915, salts of precious metals such as platinum, palladium, Iridium, rhodium, ruthenium, and the like, corresponding to U.S. Patents 2,448,060, 2,540,086, 2,566,245, 2,566,263 and 2,598,079, sulfur compounds capable of reacting with silver salts to form silver sulfide, as in U.S. Patents 1 574 944, 2 410 689, 3 189 458 and 3 501 313 described, and reducing compounds such as stannous salts, amines, and the like, as described in U.S. Patents 2,487,850,

2 518 698, 2 521 925, 2 521 926, 2 694 637, 2 983 610 and

3,201,254.

Also quaternary ammonium salts, polyethylene glycols and the like can be incorporated into silver halide photographic emulsions as development accelerators.

If desired, the silver halide photographic emulsions can be used using cyanine dyes such as cyanine, merocyanine, carbocyanine dyes and the like, or one Combination of such dyes or, furthermore, a combination of such dyes with styryl dyes is spectrally sensitized or become eupersensitive. Such dye sensitization processes are well known and are for example

709852/0990

U.S. Patents 2,493,748, 2,519,001, 2,977,229, 3 480 434, 3 672 897, 3 703 377, 2 688 545, 2 912 329, 3,397,060, 3,615,635 and 3,628,964, British patents 1,195,302, 1,242,588 and 1,293,862, the German OLS 2,030,326 and 2,121,780, Japanese Patent Publications 4936/68, 14030/69 and 10773/68, U.S. Patents 3 511 664, 3 522 052, 3 527 641, 3 615 613, 3 615 632, 3,617,295, 3,635,721 and 3,694,217 and British patents 1 137 580 and 1 216 203. The dyes are used in a desired manner depending on the wavelengths, Sensitivities and the like to be sensitized and the purposes and applications of color photography Materials chosen.

For example, for radiographic ink materials become regular or orthochromatically sensitized emulsions are generally used and in the case of spectral sensitization of color radiographic materials for the wavelength range of about 480 to 600 m / rev, those in the Japanese are preferred Patent publications 14030/69, 33626/72 and 59828/73 listed sensitizing dyes are used.

The color photographic ones which can be developed by the process according to the invention Materials can plasticize the various polyols as, for example, in US patents 2 960 404, 3 042 524, 3 520 694, 3 656 956 and 3,640,721 are contained in the photographic layers.

The color photographic materials which can be developed by means of the process according to the invention can be conventional non-photosensitive ones photographic layers, such as protective layers, filter layers, intermediate layers, anti-inhalation layers, Primer coats, backing coats, anti-static coats, coats that counteract curl

709852/0990

and the like in addition to the photographic silver halide emulsion layers exhibit.

The color photographic materials to be developed by the process of the present invention may contain, in the non-light-sensitive photographic layers thereof, a whitening agent such as a stilbene, triazine, oxazole and coumarine compound, an ultraviolet light absorbing agent such as a benzotriazole, thiazolidine and Cinnamic acid ester compound, a light absorbing agent such as various dyes for photographic filters and dyes for reducing sensitivity to safety light, a lubricant or an anti-stick agent such as those in British Patents

1,320,564 and 1,320,565 and U.S. Patent 3,121,060 water-insoluble materials and the surfactant materials described in U.S. Patent 3,617,286. The color photographic materials may also be inorganic Compounds such as silver halide, silica, strontium barium sulfate and the like, each having an appropriate particle size or a polymer latex, such as a latex made of polymethyl methacrylate, included as matting agents.

The color photographic materials can also be antistatic Contain agents in the photographic layers, in particular in the antistatic layers formed as the topmost layers Layers. Examples of suitable antistatic agents are hydrophilic polymers such as those described in US patents 2 725 297, 2 972 535, 2 972 536, 2 972 537, 2 972 538, 3 033 679, 3 072 484, 3 262 807, 3 525 621, 3 615 531, 3 630 743, 3,653,906, 3,655,384 and 3,655,386 and British Patents 1,222,154 and 1,235,075 are hydrophobic Polymers such as those in US patents

2,973,263 and 2,976,148, biguanide compounds as described in U.S. Patents 2,584,362 and 2,591,590.

709857/0990

are written, anionic compounds of the sulfonic acid type, as described, for example, in U.S. Patents 2,639,234,

2,640,372, 3,201,251 and 3,457,076 are phosphoric acid esters and quaternary ammonium salts as described in U.S. Patents 3,317,344 and 3,514,291, cationic compounds such as those described in U.S. Patents 2,882,157, 2,982,651, 3,399,995, 3,549,369 and 3,564,045, nonionic compounds such as those described in U.S. Patent 3,625,695, amphoteric compounds, such as those described in US Pat. No. 3 73 ^ 268, complex compounds, as described, for example, in US Pat. No. 2,647,836, and organic salts, such as, for example in U.S. Patents 2,717,834 and 2,655,387 are.

The photographic silver halide emulsions of the photographic, materials to be developed according to the process of the invention may contain couplers, i.e. compounds the dyes in the reaction with oxidized color developing agents form.

Open chain diketomethylene compounds are commonly used as yellow couplers. Examples of suitable yellow couplers are for example in U.S. Patents 3,341,331, 2,875,057 and

3,551,155, German OLS 1,547,868, U.S. patents

3,265,506, 3,582,322 and 3,725,072, German OLS 2,162,899, U.S. Patents 3,369,895 and 3,408,194, and German OLS 2 057 941, 2 213 461, 2 219 917, 2 261 361 and 2 263 875 specified.

5-pyrazolone compounds are mainly used as magenta couplers is used, but indazolone compounds and cyanoacetyl compounds can also be used. Examples of suitable Magenta couplers are, for example, in US patents

709R52 / 0990

2,439,098, 2,600,788, 3,062,653 and 3,558,319, British U.S. Patent No. 956,261, U.S. Patent No. 3,582,322,

3,615,506, 3,519,429, 3,311,476, and 3,419,391, Japanese Patent applications 21454/73 and 56 050/73, the German patent specification 1,810,464, Japanese Patent Publication 2016/69, Japanese Patent Application 45971/73, and U.S. Patent Publication 2,983,608.

Phenol derivatives or naphthol derivatives are mainly used as cyan couplers. Examples of suitable cyan couplers are for example in U.S. Patents 2,369,929, 2,474,293,

2 698 794, 2 892 826, 3 311 476, 3 458 315, 3 560 212, 3 582 322,

3 591 383, 3 386 301, 2 434 272, 2 706 684, 3 034 892, 3 583 971, German OLS 2 163 811, Japanese patent publication 28 836/70 and Japanese patent application 33 238/73 described.

Furthermore, the color photographic materials can still be so-called Contain DIR couplers, i.e. couplers that do the development inhibitory compounds in the dye-releasing type or compounds which are development-inhibiting compounds in release the clutch. Examples of such couplers or compounds are given in U.S. Patents 3,148,062, 3,227,554, 3,253,924, 3,617,291, 3,622,328, 3,705,201, British Patent 1,201,110 and U.S. Patent 3,297,445, 3,379,529 and 3,639,417 are given.

The combination of two or more of the above-listed couplers can be formed into a single silver halide emulsion layer may be incorporated in order to obtain the properties required for the photographic materials, or the same kind of coupler can be in two or more different silver halide emulsion layers be incorporated.

709852/0990

On the other hand, with regard to radiographic materials, there is no special limitation on the absorption wavelength range of the color images, but the use of cyan dyes or blue dyes with a main absorption in the red wavelength range (about 600 to 700 m, \ x) or in the green wavelength range (about 550 to 600 nyu) des visible spectral range is particularly preferred. For this purpose, color couplers of the phenol type or OC-naphthol type, which are capable of forming quinone imine dyes with a maximum absorption in the spectral wavelength range of about 550 to 700 m / U, are preferably used as couplers. Examples of such couplers are shown in U.S. Patents 2,772,162, 3,222,176, 3,758,308, 3,737,318, 3,591,383 and 3,476,563, British Patents 1,111,110, 1,038,331, 727,693 and 7 ^ 7,628 and Japanese Patent Application 4480/72.

An oil solution dispersion system can be used to disperse the photographic color coupler or an aqueous solution dispersion system can be used.

As couplers for color radiographic materials, couplers having hydrophilic groups such as carboxy group, sulfo group and the like is preferred from the viewpoint of suitability for rapid development, and in this case, an aqueous one is preferred Solution dispersion system used to disperse these couplers.

In the oil solution dispersion system, an oleophilic Coupler is dissolved in a high-boiling organic solvent and the resulting solution becomes directly in the form of fine colloidal particles dispersed in a photographic silver halide emulsion or, alternatively, the resulting oil solution becomes the Coupler is dispersed in an aqueous medium, and the dispersion thus prepared becomes the silver halide emulsion

7098 S 2/0990

admitted.

The following methods can be used for the coupler aqueous solution dispersion system can be applied. A coupler with at least one ballast group, such as a long chain aliphatic Group such as an alkyl group or alkylene group having 5 to 20 carbon atoms and at least one salt-forming group Group, such as a carboxy group or sulfo group, becomes in the form of the alkali salt to provide a hydrophilic, water-soluble one making group therein and the coupler becomes a hydrophilic colloid mass as an aqueous solution of the Coupler added. That is, the coupler with the above structure is in a solution of an alkali hydroxide, such as an aqueous sodium hydroxide solution or an alcoholic one aqueous potassium hydroxide solution or dissolved in a mixture of water and an alcohol and the resulting solution is then added directly to a photographic silver halide emulsion or initially to a hydrophilic colloid mass such as added to an aqueous solution of a hydrophilic colloid or a molten gel containing a hydrophilic colloid and the mixture is added to the silver halide photographic emulsion.

Exposure for obtaining color photographic images can be carried out in the usual manner. That is, different known light sources, such as natural light (sunlight), tungsten lamps, fluorescent lamps, xenon arc lamps, Carbon arc lamps, xenon flash lamps, cathode ray tubes, moving spot lamps and the like can be used for exposure. A suitable exposure period is 1 / 1000th Second to 1 second, as it is used for exposure in a Kanera, or can be shorter than 1 / 1000th of a second for example 1/10 to 1/10 seconds in the case of application a xenon flash lamp or cathode ray tube light point

709852/0990

or can be longer than 1 second. Furthermore, if desired the spectral composition of the light used for exposure is controlled by using a color filter will. Laser light can also be used for exposure.

In the exposure of radiographic medical materials, an x-ray tube and a fluorescent intensifying grid are used generally used, and there is no particular limitation on the fluorescent one used Intensifying grid together with the radiographic color materials that expose the method according to the invention are, however, it is preferred to employ green emitting intensifying gratings as in the US patent 3,809,906 and Japanese Patent Applications 52,990/74 and 63,424/74.

Some of the effects and benefits obtainable from the present invention are as follows:

First of all, compared to the usual color developers which contain 3-pyrazolidone derivatives, those used according to the invention have Color developer very stable storage properties, show less damage in the development of the photographic Properties over time and does not form precipitates or sludge when the color developer is used during one be stored for a long period of time.

Further, according to the invention, the color developer which is a 3-pyrazolidone derivative does not turn green through air oxidation.

Third, the method of the invention using the color developer set forth herein can be carried out rapidly and the color developer has excellent stability

709852/0990

Since rapid development continues to be applicable within the scope of the invention the method according to the invention is particularly advantageous for the development of radiographic color materials.

Furthermore, the error of the usual, a 3-PyTaZOlidonderivat containing color developer that fog is formed during development, and the use of a 3-Pj tazolidone derivative with one or two hydroxyalkyl groups in the 4-position of the same is particularly favorable, since a color developer, which contains this type of 3-pyrazolidone derivative, less veil results.

The invention will now be described by way of the following examples using color radiographic materials as illustrative Examples of color photographic materials are illustrated, without the invention being limited to these examples. If unless otherwise indicated, all parts, percentages, ratios and the like are by weight.

example 1

In 50 ml of an aqueous solution with 1% by weight sodium hydroxide were

3 g of a coupler of the following structure were obtained at 40 ° C

HOOCCH ₂ Ch ₂ CONH

NHCOC ₁₃ H ₂₇

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Then 6 ml of an aqueous solution with 10 wt .-% citric acid and 2 ml of an aqueous solution of chrome alum to 57 g of a silver halide photographic emulsion containing the Content of 5.4 g silver chloroiodobromide (about 0.5 mol% silver iodide, Silver chloride content: trace) with an average grain size of about 0.6 to 1.5 / U and 7 g of gelatine were added and after adding the above-prepared coupler solution to the mixture, a spectral sensitizing dye became following structure

(CH ₂ ) ₃ SO ₃ Na

added to the resulting mixture in an amount of about 0.08 mg per 50 mg of silver.

Further, a coating aid was added to the mixture and then the pH of the mixture was adjusted to about 6.5 for formation of a silver halide photographic emulsion.

The silver halide emulsion then became one on both surfaces of a polyester film having a thickness of about 180 / U

p /

Total coverage of about 50 mg / 100 cm as silver for training of the photosensitive material.

The photosensitive material was passed through an SP-15 filter (Product of Fuji Photo Film Co., Ltd.) of light from a woI-

709852/0990

frame lamp exposed to an exposure amount of 1.6 CMS and then subjected to the following treatment:

Treatment levels: 35 ⁰ C 60 seconds Color development 35 ⁰ C 60 seconds Fixation 25 ⁰ C 60 seconds Laundry

The compositions of those used in the above development Treatment solutions were the following:

Color developer :

Ethylenediaminetetraacetic acid 2 g

Sodium sulfite (anhydrous) 10 g

Ν, Ν-diethyl p-phenylenediamine sulfate 6 g

Potassium carbonate 30 g

Potassium bromide 2 g

5-nitrobenzimidazole 30 mg

4-methyl-1-phenyl-3-pyrazolidone 0.8 g

Turkish red oil 5 mg

Additions (from the following tables
I to V visible)

Water to 11

Fixing solution :

Ammonium thiosulfate 60 g

Sodium sulfite (anhydrous) 5 g

Glacial acetic acid 1.5 ml

Boric acid 3 »8 g

Potassium alum 7 »5 g

Water to 11

(pH 4.6)

709852/0 9 90

After the preparation of the color developer, 500 ml of the color developer was put in a 1 liter beaker and _; After the color developer had been left to stand for 7 days at a temperature of 25 ^° C., the damage to the photographic properties and the formation of precipitates and sludge in the developer were checked. The results obtained are shown in Table I. The above procedure was also carried out using a comparative color developer which did not contain 4-methyl-1-phenyl-3-pyrazolidone; the results obtained are shown in Table II as a comparative example.

The value ΔΏ given in the tables below is the difference between the visual density (D ^) of the fresh color developer obtained during the development of the color photographic material at an exposure amount of 0.8 CMS and the visual density (D_) of the during 7 days at 25 ° C

el

stored color developers in the development of the color photographic material with the same amount of exposure (AD = D- - D). In the examples of the present invention, the value of D ~ was practically constant, while the value of ΔΏ became larger due to the low value of D _e in the color developer having poor storage properties. That is, in Tables I to V, the larger the value of AT) , the more deterioration of the color developer with the lapse of time, and the smaller the value of ΔD, the smaller the change in photographic properties with the lapse of time the time and the better the storage properties of the color developer.

The visual density is the density that was determined by means of a light corresponding to that for which the human Eye is sensitive.

709852/0990

Δ Fog is the difference between the fog values ( including the base density) obtained in the case of using the fresh color developer and in the case of using the stored color developer. The greater the value of APog, the greater the formation of the fog, ie the more pronounced the damage to the color developer.

Table I. additive Lot * additive Lot* AD Λ Fog Amount of never
derschlag and
mud Ver
search
No. without _ without _. 1.17 0.16 great 1 Ν, Ν-diethylhydroxyl
amine 5 ml N, N-diethylhydroxyl
amine 5 ml 0.39 0.05 small 2 Hydroquinone 0.2 g N, N-diethylhydroxyl
amine and
Hydroquinone 5 ml
0.2 g 1.20 0.15 great 3 Ν, Ν-diethylhydroxyl
amine and
Hydroquinone 5 ml
0.2 g 0.08 0.01 no 4th Table II ΔΏ AFo g Amount of never
derschlag and
mud Ver
search
No. 0.61 0.07 small 5 0.04 0 no 6th 0.06 0.01 no 7th

(*) Amount of additive added per liter of color developer

709852/0990

From the values in Table I it is clear that according to the Invention greatly improves the storage properties of the color developer containing the 3-pyrazolidone derivative (Experiment 4) and thus a color developer in which neither precipitate nor sludge occurred and which was very stable, was obtained.

It is also shown that the use of hydroquinone alone gives no effect, as can be seen from Experiment 3. How further can be seen from the values in Table II (experiments 5 and 6), provided the use of Ν, Ν-diethylhydroxylamine alone, which provides a good antioxidant effect for aromatic primary amines as color developing agents, none sufficient effects for a color developer using a 3-pyrazolidone derivative contained. That is, it became quite excellent antioxidant effect when using hydroquinone and Ν, Ν-diethylhydroxylamine together within the scope of the invention obtain.

Furthermore, a comparison of experiments 2 and 4 and experiments 6 and 7 shows that hydroquinone is selectively a strong one Shows antioxidant effect for a 3-pyrazolidone derivative and also from the fact that the use of hydroquinone alone has no effect, the Ν, Ν-diethylhydroxylamine one Contribution as an antioxidant for a primary aromatic amine as a color developing agent and hydroquinone at the same time brings. It is also assumed that the Ν, Ν-diethylhydroxylamine acts as an antioxidant for the 3-pyrazolidone derivatives, although the effect is not very high.

Example 2

In this example, the type of hydroxylamine derivative used according to the invention was changed; "". the results obtained are listed in Table III. In this example, after

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- 59 -

the same procedure as in Example 1 was followed, except that 1-phenyl-3-pyrazolidone was used in the color developer of Example 1 was used in place of 4-methyl-1-phenyl-3-pyrazolidone.

Table III

attempt

additive

Quantity * AD

Δ For

Amount of precipitation and mud

no

Hydroxylamine sulfate 5 g

Hydroquinone 0.2 g hydroxylamine sulfate 5 g

N-furanoethyl-N- (ethyl) - 5 g hydroxylamine

Hydroquinone 0.2 g

N-Furanoäthyl-N- (ethyl) - 5 g hydrochloride xylamin

N-pyridinoethyl-N- (methyl 5 g) hydroxylamine

Hydroquinone 0.2 g

N-pyridinoethyl-N- (methyl 5 g) hydroxylamine

N-methylhydroxylamine- 5 g hydrochloride

Hydroquinone 0.30 g

N-methylhydroxylamine- 5 g hydrochloride

3-methyl-N-hydroxy-5 g piperidine

Hydroquinone

3-Met hy1-N-hydrο xypiperidine

Bis- (ß-N-methylhydroxyaminoethyl) -su 1 fon

Hydroquinone
aminoethyl) sulfone

1.35 0.20 large

0.89 0.09 large

0.30 0.04 none

0.61 0.06 small

0.15 0.03 none

0.64 0.06 small

0.17 0.03 none

0.96 0.10 large

0.30 0.04 none

0.92 0.09 large

0.2 g

c 0.29 0.04 small

g 0.67 0.07 small

0.2 g

0.10 0.03 none

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- 40 -

Table III (continued)

21 Ν, Ν-diethylhydroxylamine

22 hydroquinone

N, N-diethy! Hydroxylamine

5 g 0.72 0.07 0.2 g 5 g

0.13 0.03

small none

Experiments 10, 12, 14, 16, 18 and 20 show those with the according to the invention Procedure obtained results.

The values in Table III show that the application a hydroxylamine derivative alone gives rise to in each case results in lower anti-oxidation effects and that the storage properties of the color developer when using hydroxylamine derivatives greatly improved along with hydroquinone.

Example 3

In this example, the type of connection with the structure HO- £ C = C - ^ - OH or HO- £ C = C 45 -NR ^ R _{2 was} changed in the process according to the invention; the results obtained are shown in Table IV. This example was carried out in the same manner as in Example 1.

Table IV

Ver
search
No. additive Lot * AD Δ Fog Amount of
Low
blow and
mud 23 no _ 1.24 0.17 great 24 p-pyrrolidinophenol 0.6 g 1.24 0.15 great 25th N, N-diethylhydroxyl 5 ml amine
1-pyrrolidinophenol 0.6 g 0.13 0.01 no 26th p-pyridinophenol 0.6 g 1.29 0.17 great

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Table IV (continued)

27 N, N-diethylhydroxylamine 5 ml 0.15 0.01 no p-fyridinophenol 0.6 6 28 L-ascorbic acid 0.4 g 1.29 0.17 great 29 N, N-diethyl hydroxyl amine 5 ml 0.20 0.02 no L-ascorbic acid 0.4 g 30th Heductic acid 0.5 g 1.02 0.13 great 31 N, N-diethylhydroxylamine 5 ml 0.13 0.01 no Reductic acid 0.5 g 32 t-butyl hydroquinone 0.2 g 1.27 0.16 great 33 N, N-diethylhydroxylamine 5 ml 0.19 0.02 no t-butyl hydroquinone 0.2 g 34 Pyrogallol 0.2 g 1.29 0.14 great 35 N, N-diethylhydroxylamine 5 ml 0.28 0.05 small Pyrogallol 0.2 g 36 Hydroquinone 0.2 g 1.25 0.15 great 37 Ν, Ν-diethylhydroxylamine 5 ml 0.12 0.01 no Hydroquinone 0.2 g

Experiments 25, 27, 29, 31, 33, 35 and 37 bring the results obtained by the method according to the invention.

From the values contained in Table IV it is shown that the use of a compound with a skeleton HO-f C = C - ^ - 0H or HO- (■ C = C 4 ^ -NB ₁ R ₂ alone shows no effect that however, the storage properties of the color developer can be greatly improved when such a compound is used together with Ν, Ν-diethylhydroxylamine.

Example 4

In this example, the types of 3-pyrazolidone derivatives and the aromatic primary amines as color developing agents

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changed; the results obtained are shown in Table V. That is, this example was following the same Procedure worked as in Example 1, except that Ν, Ν-diethylhydroxylamine and hydroquinone in amounts of 6.0 ml / liter and 0.2 g / liter, respectively, were used in the color developers, and that 3-pyrazolidone derivative used in Example 1 and the primary aromatic amines as color developing agents have been replaced by the compounds listed in Table V.

Tabel additive V e AD Δ Fog Amount of
Low
blow and
mud Ver
search
No. - G 1.21 0.17 great 38 3-pyrazolidone as in
example 1 lot G 0.10 0.01 no 39 1-phenyl-3-pyrazolidone 6th 0.17 0.03 no 40 4-Me thy 1 -4-hydro xym e thy I -
1-phenyl-3-pyrazolidone 0.8 E. 0.08 0.01 no 41 4,4'-dihydroxymethyl-I-
phenyl-3-pyrazolidone 0.8 G 0.05 O no 42 4,4'-dihydroxymethyl-1-
phenyl-3-pyrazolidone 0.8 0.11 0.02 no 43 4,4'-dihydroxymethyl-1-
phenyl-3-pyrazolidone 0.8 0.18 0.03 no 44 0.8 0.8

Note: In experiments 38 to 42, this was the same as in Example 1 specified color developing agent (6.0 g) used, in experiment 43 was ^ amino - ^ - methyl-N-ethyl-N-methoxyethylaniline-p-toluenesulfonate (5 »0 g) was used as the color developing agent and was used in Experiment 44 N-ethyl-N- (ß-methanesulfoamidoethyl) -3-methyl-4-aniinoaniline sesquisulfate monohydrate (6.0 g) was used as a color developing agent.

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In Table V, test 38 represents a comparative example and Runs 39 to 44 show the results obtained with the method of the invention.

From the values in Table V it is clear that in the case of the use of 3-pyrazolidone derivatives and primary aromatic Amines as color developing agents improve the storage properties of the color developers containing them through the use of the both types of antioxidants according to the invention can be greatly improved.

The invention has been described above on the basis of specific embodiments, without the invention being limited thereto.

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Claims (1)

2727OtO Claims A color photographic process for developing an exposed farbphotographisehen silver halide with a color developer, the vat, a primary aromatic amine color developing agent, a 3-Pyrazolidonderi- and contains thereof hydroxylamine or a derivative, characterized in that the color photographic silver halide material comprising such a color developer, the further additional Compound with a proportion according to the following general formula HO- £ C = C ^ ₅ -A contains, is developed, wherein A is a group -OH or -NR.Rg »where R ^ and Rg are each a hydrogen atom or represent a group with less than 4 carbon atoms and R ^. and R2 can also be combined and form a 5-membered or 6-membered ring, and η a positive an integer from 1 to 4-, where the group C = C -Jr- can form a chain or a ring. 2. Process for developing color photographic matter Lines according to claim 1, characterized in that the compound is a group corresponding to the formula HO- £ C = C wherein η is as defined above, and the amount of the compound in the color developer is from about 0.01 to about 5 * 0 g per liter of the color developer. 3 · Process for developing color photographic materials according to claim 2, characterized in that the amount of the compound is 0.05 to 2.0 g per liter of the color developer amounts to. 7098S2 / 0990
ORIGINAL INSPECTED H-. Process for developing color photographic materials according to Claim 1, characterized in that the compound contains a group corresponding to the formula HO- (· C = C - ^ - ^^, in which R,., R ₂ and η have the meanings given above, and the amount of the compound in the color developer is about 0.01 to 10 g per liter of the color developer. 5. A method for treating color photographic materials according to claim 4, characterized in that the amount of the compound is 0.05 to 5 »O g ie liter of the color developer. 6. A method for developing color photographic materials according to claim 1 to 5 »characterized in that as color photographic materials color radiographic materials be used. 7. A method for developing color photographic materials according to claim 1 to 6, characterized in that the primary aromatic amine used as the color _{developing agent is N 1} N-diethyl-p-phenylenediamine sulfate or 4 - ^ - ethyl-N-Cβ-hydroxyethyl) amino7aniline sulfate . 8. A method for developing color photographic materials according to claim 1 to 7%, characterized in that the 3-pyrazolidone derivative ^ -hydroxymethyl - ^ - methyl-i-phenyl-J-pyrazolidone, 4,4 · '-dihydroxymethyl-i-phenyl- 3-pyrazolidone or 4-methyl-1-phenyl-3-pyrazolidone can be used. 9- Process for developing color photographic materials according to claims 1 to 8, characterized in that hydroxylamine or, as a derivative thereof, N, N-diethy! hydroxylamine be used. 709 8 52/0990 10. Process for developing color photographic materials according to claims 1 to 7 »characterized in that the primary aromatic amine is used as the color developing agent Ν, Ν-diethyl p-phenylenediamine sulfate, as a 3-pyrazolidone derivative 4-methyl-1-phenyl-3-pyrazolidone, as a hyiroxylamine derivative Ν, Ν-diethylhydroxylamine and, as a compound with a group of the general formula HO— £ C = C - ^ r-A, hydroquinone is used. 11. A method for processing of color photographic materials according to claim 1 to 7i characterized in that as aromatic primary amine color developing agent Ν, Ν-diethyl-p-phenylenediamine, 3-i ³ 3 ^r razolidonderivat 4-methyl-4-hydroxymethyl-i -phenyl-3-pyrazolidone, as the hydroxylamine derivative N, N-diethy / hydroxylamine and as a compound with a group of the general formula HO— £ C = C—} —A hydroquinone is used. 12. A method for developing color photographic materials according to claim 1 to 7 »characterized in that the primary aromatic amine as the color developing agent N, N-diethyl-p-phenylenediamine sulfate, as a 3-pyrazolidone derivative 4 _t 4 ^l -dihydroxymethyl-1-phenyl-3 -pyrazolidone, as a hydroxylamine derivative Ν, Ν-diethylhydroxylamine and as a compound with a group of the general formula HO- £ · C = C - ^ - A hydroquinone is used. 13- color developer for developing color photographic materials " containing a primary aromatic amine as a color developing agent, a 3-I'yrazolidone derivative, a hydroxylamine derivative and a compound having a group corresponding to the formula HO- £ * C = C 709852/0990 wherein A is a group -OH or -NR.Rp, where R ^ and R ₂ each represent a hydrogen atom or a group with fewer than 4 carbon atoms and R. and Rp can also be combined and form a 5-membered or 6-membered ring can, and η is a positive number from 1 to 4-, in which the group —f C = C -) —— can form a chain or a ring. 709852/0990