DE2548880A1 - COLOR INVERSION DEVELOPMENT - Google Patents

Description

The invention relates to a color reversal development process. In particular, the invention relates to a photographic one Color reversal process for the delivery of color photographic images with improved multi-layer effect, grain and sharpness.

According to the invention, in a color reversal development process including a black and white development and a color development, the sharpness, grain and the multilayer effect of the formed color photographic Images improved remarkably when the color photographic Black and Veiss development silver halide reversal materials in the presence of a DIR connection, d. H. a compound of non-coupler Tfp that leads to release of a development hemp is capable of developing "

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You will be subjected to the color photographic materials in an aqueous solution of a fogging agent and then the color photographic materials of color development be subjected.

The color reversal development method for multilayer color silver salt photographic materials is, for example in C.E. Mees, The Theory of the Photographic Frocess ", 2nd edition, Paragraph 25ν 1954-, described. As such a development method two systems are generally known; namely, a reversal development process, wherein the color development with couplers in the photographic emulsion layers color photographic materials is carried out and a reversal development process, whereby the color development with Couplers is carried out in the developer. In both systems, the treatment is built up from the following procedural stages.

An exposed color photographic material undergoes a first development using a black and white developer subjected, whereby the silver salt is reduced in the exposed areas to form a negative image will. Then the ptdtographic material undergoes color development subjected, whereby the unexposed silver halide, which is not reduced in the first development is developed to form developed silver and at the same time the oxidized color developing agent is used Implementation with the couplers is brought to form a positive color image. Then the silver is in a Removed the silver removal step and a sharp color image remains on the support of the color photographic Materials. The silver removal step can be a bleaching step to convert the developed silver to a water soluble one or water-insoluble silver salt by oxidizing the same and a fixing step for dissolving the water-soluble one

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Silver salt or to convert the water-insoluble silver salt into a water-soluble silver complex salt with subsequent dissolution of the water-soluble silver complex salt or can alternatively consist of a blix stage, in which the bleaching stage and the fixing stage in one Stage is effected.

In all cases are the first development (or black and white development), the color development and the Silver removal does the basic steps of reverse color development, however the process can continue if desired Auxiliary level, such as B. a stop stage, a hardening stage, a stabilizing step and the like., Included.

Reverse development of the type in which color development is carried out with couplers in the developer includes a cyan development, a yellow development and a magenta development, and each color developer contains the corresponding one Matchmaker in it. On the other hand, in the reverse development of the other type, the color photographic material contains the couplers in the photographic emulsion layers.

One of the most important aspects of the latter type of color reversal development is efficiency the second development (color development), and for this purpose chemical fogging becomes common applied after the first development of the color photographic material instead of a light haze. To the chemical To carry out veils, ethylenediamine, n-butylamine, Alkali salts of borohydride, amine borane and the like. Alone or added as a mixture thereof to the second developer or color developer as a fogging agent.

On the other hand, a method has been applied in the last time, wherein a Entwicklungshenmstoff from the developed layer containing it is released in the course of development and the development of the adjacent p> c-t '.: ~ ^::: z

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phical emulsion layer is inhibited, so the multi-layer effect or the development of the layer containing the development inhibitor or the development inhibitor therefor "adjacent layer is inhibited so that fine grains are obtained. A compound that releases a development inhibitor in the development reaction is called "Development inhibitor releasing compound" or "DIR compound" and such compounds may be composed of a coupler, a developing agent or a material which releases an inhibitory compound on development.

Since such DIR compounds are used in color photographic Negative materials are used, it might be seen as obvious, DIR compounds in color reversal development to use to achieve an improved multi-layer effect and a grain refinement, however. the practical application of this method poses considerable problems. That is, the effect of the first development The DIR coupler used also influences the following Levels and inhibits sufficient color development. This phenomenon is also found in dye developers who have a Fogging agents as listed above contain observed. Therefore it is difficult with the usual procedures DIR materials along with color negative materials color photographic reversal systems for industrial or technical use. Even when the DIR couplers are used in reversal color photographic materials, they can only be used in an area which does not strongly inhibit the color development and consequently their effect is low.

If there is a remarkable effect of the DIR compounds in the color negative development in the reverse color development could be achieved, the quality of the color images would ^ ar-

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edged to be improved.

The Application of DIR Couplers to Development Processes for color photographic reversal materials also brings problems with the grain and the sharpness of the color images, d. H. if the color development is inhibited, it was found that the grain of the color images formed is coarsened so that the sharpness thereof is reduced. The reason for this effect is not complete understandable, however, it is believed that if a development inhibitor is strongly adsorbed around the silver salt grains, the number of development initiation points is less and the colors formed are around the development initiation parts concentrate, whereby an enlargement of the densely distributed dye spots with coarsening adjusts the graininess and reduction of the sharpness of the color images. From this point of view, the application is damaging the DIE compound in reversal color photographic developments actually the picture quality.

It is therefore an object of the invention to provide a reversal color photographic process using effective DIR compounds can be used without any detrimental effect on color development, d. H. a task The invention consists in a new color photographic reversal development process which does not only increase the multi-layer effect of the DIR connections used can be carried out, but also without any Coarsening of the grain of the color images or a reduction in the sharpness of the images, which was previously considered special for the usual reversal color development was considered when a Development inhibiting effect was achieved.

A specific object of the invention is a reversal color development process by which is remarkable

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the multi-layer effect of color photographic reversal materials the kind which couplers contain in the photographic emulsion layers of the photographic materials, Can be improved and the color photographic Deliver images with improved grain and sharpness.

The above objects of the invention are achieved by the method according to the invention, namely a color photographic process Inverse development process with inclusion a first development and a color development, wherein a reversal color photographic material of the first development in the presence of a non-coupler type compound, capable of releasing an anti-development material that is developed in this way photographic material with an aqueous solution of a reducing compound capable of chemical fogging of the silver halide of the photographic material is treated and then the photographic material is subjected to color development.

In practicing the color reversal development process according to the invention, the reversal color photographic materials sufficiently exhibit the multilayer effect and continue to be color photographic images Preserved with improved grain and sharpness. As can also be seen from the following examples, if the DIE. connection s in the usual reverse color process are used, the grain and sharpness of color photographic images are reduced. Even if just one Fog bath in the usual color development reversal process is applied, there is little improvement in grain and Sharpness of the color images achieved. However, by combining the above two methods, i. H. the application the DIR compounds and the veil bath, unexpectedly get a better result, d. H. the ungürisi ^ r «

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Influence of the DIR connections on the reversal color development can be removed in the veil bath, so that the DIR compounds have excellent effects for improving the grain and provide sharpness of color photographic images as in the case of color photographic negative development.

In the process according to the invention, the DIR compounds can be added to the first developer (black-and-white developer) may be incorporated into one or more silver halide emulsion layers of the color photographic Materials are incorporated. The DIR connections set an anti-development connection in development free and have the property that the compounds do not form any color when the color is developed. (In this point of view the DIR connections differ from a DIR coupler). These DIR connections are in the U.S. Patents 3,297,445, 3,364,022, 3,379,529, and 3,639,417, Japanese Patent Applications 41,870/1973, 73 445/1973, 103 542/1973, 110 703/1973, 143 291/1973, 25 482/1974 and 39 662/1974. The DIR compounds specified in these patents or patent applications can be used according to the invention.

According to the invention, all customary winding agents can be used under all the usual black and white developments

conditions can be used.

Particularly preferred DIR compounds for use

in the method according to the invention are hydroquinone compounds. There are basically two types of hydroquinone compounds for these DIR connections. ■ One type of hydroquinone compound is a compound that is direct releases a diffusible mercapto development inhibitor upon development of the silver halide grains, or one diffusible mercapto development inhibitor in the reaction with the oxidation product from the ZL-.t ·:, j.:l-:ng of the silver halide formed colors twicklunssni ire .. and the other type is the hydroquinone compounds

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a compound which similarly releases an iodine ion.

The DIR connections, which mercapto development implants in the manner described above, include compounds of the general formula

(D

wherein R ^ and Sp are a hydrogen atom or a group which can be split off in an alkaline solution to form a hydroquinone, for example an acetyl group, chloroacetyl group, dichloroacetyl group, monofluoroacetyl group, difluoroacetyl group, trifluoroacetyl group, pyridyl group, alkoxyaliyl group, alkoxybenzoyl group, alkyanoxbenzoyl group, and ditrobenzoyl group. , A ^, A ^ and A, each a hydrogen atom, a group, polythey make the compound diffusible, soluble and water-soluble and which increases the activity of the hydroquinone, (ie the development activity of the hydroquinone is increased by the substituent when the OIR compound from the compound of formula (I):), for example an alkyl group having 1 to 20 carbon atoms, an alkoxy group, an aryloxy group, a hydroxyl group, an aryl group such as a phenyl group, tolyl group, xylyl group and the like, an aralkyl group, a halogen atom , for example chlorine atom, bromine atom, iodine atom, fluorine atom, and the like, a heterocyclic group, the carbon region being ^ "i? heterocyclic monocyclic atoms, preferably 3 to 11 Zchl zz a ζ c_f ~ atoms, for example a tetrazolyl group, thiasoyl group and the like, or a radical SY, in which Y is an alkyl

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group with 1 to 18 carbon atoms, for example a 2-ethylhexyl group, an n-dodecyl group, a hexadecyl group, an n-octadecyl group, a hydroxycarbynyl group, an ethoxy carbonylmethyl group, a 2-hydroxyethyl group and the like, or represents an aryl group such as phenyl group and the like, or a group S-Z, where Z is a heterocyclic radical, being the carbon atom range of the heterocyclic ring is preferred

in sebundeiia, ^ usTJand Comprises 3 to 11 carbon atoms, the type Tatiscn photographic is inert if the group S-Z is bonded to the compound of the formula (I), such as, in particular, the tetrazolyl group, for example 1-phenyltetrazolyl group and like., a triazolyl group, for example 4-phenyl-1,2,4- triazol-5-yl group, 3-n-pentyl-4-phenyl-1,2,4-triazol-5-yl group and the like, a thiazolyl group, for example 2-methyltido-1, 3J ^ tMaZoI-5-yl group, 2-amino-1,3 »4- thiazol-5-yl group and the like., an oxadiazoIyIgruppe, for example 2-phenyl-1,3,4-oxadiazol-5-yl group and the like, a tetraazaindenyl group, for example 6-methyl-1,3i3st-i7 ~ tetraazainden-4-yl group, 6-n-Uonyl-1,3 »3a» 7-tetraazainden-4-yl group and the like, an oxazolyl group such as benzoxazol-2-yl group and the like, or a thiazolyl group such as benzothiazol-2-yl group and the like., wherein in particular · A, - preferably consists of an -S-Z radical.

In the above formula, it is preferred that A ^, k ^ or A, have a ballast group, and further, it is particularly preferred that R ^ and R2 consist of hydrogen atoms and A ^, A2 and A, consist of hydrogen atoms or an alkyl group.

In order to make the DIR compounds and couplers indicated below resistant to diffusion, a hydrophctc-r radical 0 is ar v a ballast group having 8 to 32 carbon atoms, as they are commonly referred to in the art; ^e::;:.

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incorporated into the molecule of the DIR compound and the coupler, The ballast group can be attached to the framework structure of the DIR compound or the coupler directly or via an imino bond, an ether bond, a carbonamide bond, a sulfonainide bond, an ureide bond, an ester bond, an imide bond, a carbamoyl bond or a sulfamoyi bond.

Specific examples of ballast groups within the scope of the invention are the following:

(I) Alkyl groups and alkenyl groups: For example -CH ₂ -CH (C ₂ Hc) ₂ * - ^c i2 ^H 25 ⁱ ~ ^C 16 ^H 33

" ^C 17 ^H 33 *

(II) alkoxyalkyl groups:

For example - (CH ₂ ) ^ - O- (CH ₂ ), -, CH, and - (CH ₂ ) ₅ OCH ₂ -GH- (CH ₂ ) q-CH ₅ corresponding to the Japanese C ₂ H ₅

Patent Publication 27 563/1964.

(III) alkylaryl groups: For example

4 ^H 9 ^(t)

* - ■ - v ^ -C _Q H, Q, and. - "

(IV) alkylaryloxyalkyl groups: For example

G ₅ H ₁₁ (I),

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- li -

CH,

Cl

-CH ₂ O

CH ₅ -C-CH

'V ₅ H ₁₁ Ct)

CH ₂ -C ₄ H ₉ (t)

(V) acylamidoalkyl groups, for example

^{> C} 4 ^H 9

-CH ₀ CH ₀ NH-COCH ₀ Ch ₀ N

-CE

COC ₁₃ H

/ COC-,

and

C ₅ H ₇

ι Tr

₅ H ₇

corresponding to U.S. Patents 5,337 3 ^^ and 3,418,129.

(VI) alkoxy ary groups and ary loxy ary groups, for example

[n) and - ^ 0-0-O) -C ₁₂ H ₂₅ (η).

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(VII) radicals with a long-chain aliphatic alkyl or alkenyl group and a water-solubilizing carboxyl or sulfo group, for example -CH-CH-CH-Ci ₆ H ₃ 3 and -CH-Ci ₆ H ₃₃ .

I I

■ CH ₂ COOH SO ₃ H

(VIII) Alkyl group substituted with an ester group, for example

-CH-Ci ₆ H ₃₃ Cn) and -CH ₂ -CH ₂ -COOC ₁₂ H ₂₅ Cn).

COOC ₂ H ₅

(IX) Alkyl groups substituted with an aryl group or a heterocyclic group: for example

-CH ₂ -CH ₂ - / '^ -NHCOdUCH ₂ CH-CIeH ₃₅ Cn) and λζζ / Ι

COOCH a

CVT ΓΊ.Τ '/ * * ^Λ ~

-Ln? Lsz 2 - \ / - '

(X) Aryl groups substituted with an aryloxyalkoxycarbonyl group:

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for example

C ₅ H ₁₁ Ct) CH- '

- // ^ -CCOCH ₂ CO - //
CH

Specific examples of compounds of the general Formula I are given below: Compound 1:

2-n-Dodecylthio-5- (1'-phenyltetrazoi-5 ^f -yl-thio) -hydroquinone. Connection 2:

2-n-octadecylthio-5- (1'-phenyl-tetrazol-5'-yl-thio) -hydroquinone.
Connection 3:

2-n-Hexadecylthio-5- (1'-phenyl-tetrazol-5'-yl-thio) -hydroquinone.
Compound 4:

2- {2 ', 5'-Dihydroxy-6 · - (1 ⁿ -phenyltetrazol-5 ^ll -yl ~ thio) -4' - (1 "', T", 3 "', 3"'tetramethylbutyl) j- phenylthiobenzoic acid. Compound 5 '· 2- {2', 5'-Dihydroxy-6 '- (1 "-phenyltetrazol-5" -yl-thio) -3' - (1 ⁿⁱ , 1 ^l "_> 3 ^Mt , 3" ^! - tetramethylbutyi)} - phenylthiobenzoic acid. Connection 6:

2- (i ^l -Phenyltetrazol-5 ^t -yl-thio) -3-phenylthio-6- (1 ", 1", 3 ⁿ , 3 "-tetramethylbutyl) -hydroquinone. Compound?:

2- (1 ^l -phenyltetrazol-5 ^l -yl-thio) -3-phenylthio-5- (1 ", 1", 3 ", 3" -tetramethylbutyl) hydroquinone.

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Connection 8:

2,5-dihydroxy-5- £ i '-phenyltetrazol-5' -yl-thio) -4 ~ (1 ", 1 ⁿ , 3", 3 "-

tetramethylbutyl) ^ - phenylthioacetic acid.

Compound 9 J

2- {2 ¹ , 5 ¹ -dihydroxy-3 '-n-hexadecylthio-6' - (1 "-phenyltetrazole-

5 "-yl-thio) 3-pnenylthiobenzoic acid.

Connection 10:

2-n-hexadecylthio-5- (1 '-phenyl tetrazol-5' -yl-thio) -6-phenyl-

hydroquinone.

Connection 11:

^ - (1 ^l -Phenyltetrazol-5 ^t -yl-thio) -5-hydroxy-7- (1 ", 1'S3", 3 "-

tetramethylbutyl) benzoxathiol-2-one.

Connection 12:

2-f2 ·, 5'-dihydroxy-6 '- (1 "-phenyltetrazole-5" -yl-thio) -3' - (1 ^HI , 1 " ¹ ^" •, ^ "- tetrametnylbutyl ^ -phenylthiobenzoic acid-

methyl ester.

Compound 13 y

2-f 2 ^1, 5 '-dihydroxy-6 * - (1 "-phenyltetrazol-5" -yl-thio) -4' (1 ^nl, 1 "',3"' ϊ3 "'tetramethylbutyl) | -phenylthiobenzoesäure -

methyl ester.

Connection 14:

2- (2 *, 5 ¹ -dihydroxy-3 ^l -n-pentadecylthio-6 '- (1 ^tl -phenyltetrazole-

5 ⁿ -yl-thio) J-phenylthiobenzoic acid methyl ester.

Connection 15:

2-n-octyloxycarbonylmethylthio-6-phenyl-3- (i'-phenyltetrazole ~

5'-yl-thio) -hydroehinone.

Connection 16:

2-p-Nitroph.enyltb.io-3- (1 '-phenyl tetrazol-5' -yl-thio) -6- (1 " , 1 ", 3", 3 "-tetramethylbutyl) hydroquinone.

Connection 17:

2- (2'-Methylthio-1 ^f , 3 ^f , 4'-thiadiazol-5 '~ yl-tliio) -6- (r', 1 "-

3 "* 3 ^w " - "tetra (ethylbutyl) hydroquinone.

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Connection 18: '■

3- (2'-Methylthio-1 ¹ , 3 ', 4 ^l -thiadiazol-5 ^f -7l-tliio) -6- (1 ^tt , 1 "-" 3 ", 3" -tetramethylbutyl) -hydroquinone, compound 19 :

a ^ bis - ^ - metnylthio-i ¹ , 3 ', 4 -'-thiadiazol-5-yl-thio) -6- (1 ", 1", 3 ", 3 ^M -tetramethylbutyl) -hydroquinone. Compound 20:

2- (3'-pentyl-4 ^<l -phenyl-1, 2 ', 4 -'- triazol-5-yl-thio) -5- (1 "" 1 ^{M "1} 3 * 3" tetramethylbutyl ) hydroquinone. Connection 21:

2- ^(6-methyl-l 1 ^l, 3 ', 3a ^1, 7 ^l -tetraazaindene-4'-yl-thio) -6 - (T ^l, 1 - -tetrametliylbutyl "3 j 3 ^n") -hydrocninon . Connection 22:

2,3-bis- (6 ^l -methyl-1 ^l , 3 ', 3a ¹ , 7 ^l- tetraazainden-4'-yl-thio) -1- (1 "» 1 "ί 3"»3" -tetramethylbutyl ) -hydrocbanon. Compound 23 - '2-n-Hexadecyltllio-5- (2 x methylthio-1 ^1, 3', 4 ^t thiadiazol-5-ylthio)-hydro quinone. Connection 24:

2-f2 ', 5 ^f -Dihydroxy-6' - (2 "-IEe ^ yItMo-I", 3 ", 4 -" - thiadiazol-5 ^H -yl-thio) -3 '- (1 ^Ml , 1 " ·, 3 "', 3"' -tetramethylbutyl) j - phenylthiobenzoic acid. Compound 25:

2- (2'-AmInO-I ¹ , 3 * _i 4 ^l -thiadiazol-5 ^l -yl-thio) -5- (1 ", 1 ^M , 3 ⁿ , 3" -tetramethylbutyl) hydroquinone. Connection 26:

2- £ 2 ', 5'-I>ihydroxy-6' - (2 "-amino-1", 3 ", 4" -thiadiazol-5 ^It -ylthio) -5- (i ^lfl , 1 "', 3 ^"1, 3" - tetramethylbutyl) J-phenylthiobenzoic acid.

Connection 27:

2- (2'-Amino-1 ', 3', 4 ^f -thiadiazol-5'-yl-thio) -3-n-dcdecyltliic-6- (1 ", 1", 3 ", 3" -tetramethylbutyl) -hydroquinone.

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Connection 28:

2- (6 ^f ~ tert-Butyl-1,3,3a, 7-tetraa2ainden-4-yl-tliio) -6- (i ^{! L} -1 " , 3" , 3 "-tetramethylbutyl) -hydrocMnone. Compound 29:

2- (6'-U-NOiIyI-I ¹ , 3 ', 3a ¹ , 7'-tetraazainden - ^ - ¹ -yl-thio) -6- (1 ", 1", 3 ", 3" -tetramethylbutyl) -hydroquinone. Connection 30:

2- (4'-phenyl-1 \ 2 \ ^4'-triazol-I -yl 5-thio) -2-0 '>, 1 ^ll, 3, 3 "-tetrametliylbutyl) ^n-hydro cMnon. Compound 3Ί = 2 - (2'-Phenyl-1 ^f , 3 ', 4 ¹ -oxadiazol-5 ^l -yl-tkLo) -5 - (' ^ll , ^/ » ^II , 3 ^II , 3" -tetramethylbutyl) -hydroquinone, compound 32 :

2- (1'-Phenyltetrazol-5'-yl-thio) -5-n-octyloxycarbonylmethylthiohydroquinone. Compound 33 ^ 2-tert-Dodecylthio-5- (1 '-phenyltetrazol-5' -yl-thio) -hydroquinone.

Compound 3 ^ '· 2- (Benzoxazol-2'-yl-thio) -5-n-octadecylhydroquinone «Compound 35:

2- (2'-methylphenylthio) -6-n-octadecylthio-3- (1'-phenyltetrazole-5 " -yl-thio) -hydroquinone. Connection 36:

2-n-octyloxycarbonylmethylth ± o-3- (i '-phenyltetrazol-5' -ylthio ) -6-p-to lylhydro quinone. Connection 3 ?:

2-Ethoxycarbonylmethylthio-6-n-hexadecylthio-3- (1'-phenyltetrazole-5 '-yl-thio) hydroquinone. Connection 38:

2-phenylthio-3- (i'-phenyltetrazol-5'-yl-thio) -5-n-dodecylthiohydroquinone.

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Connection 39:

2-methyl-5- (1-phenyl-5-te trazolyl thio) -hydroquinone.

Connection 40:

(1-Phenyl-5-1etrazoIyIthio) -trimethylhydroquinone.

The compounds of general formula I can be prepared by the process of US Pat. No. 3,379,529 be, d. H. by addition reaction of the mercapto compounds with benzoquinones.

The compounds which release an iodine ion include compounds corresponding to the general formula

I 0

^. II

I 0

where R ^, and Rp ^ ie the same meaning as in the general Formula I own and R,? R ^, Hr and Rg each one Hydrogen atom, an iodine atom, an alkyl group with 1 to 20 carbon atoms, a hydroxyl group, an amino group or an aryl group, for example phenyl group, tolyl group, Xylyl group and the like, mean and at least one the radicals R ,, R ^, R, - and Rg is an iodine atom and at least one of the remaining groups R ^ to Rg has a different substituent represents as a hydrogen atom.

In the above formula, it is particularly preferred if R ^ and Rg are hydrogen atoms, Rg is an iodine atom and R ,, R ^

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and Rc are substituents other than iodine atoms.

Specific examples of compounds of general formula II are given in US Pat. No. 3,297,445. Some of these are given below: Connection 41:

2- Jo d- 5-p ent ade cylhy dr ο chinon. Compound 42: 2,6-diiodohydroquinone. Connection 43:

6- iodo-2,3 »5- trimethylhydro quinone. Connection 44:

2-iodo-3-i & ethyl-6-isopylhydro quinone Connection 45:

2-iodo-3,5-diiaethyl-6-dodecylhydroquinone. Compound 46: 1 _t 4-bis (chloroacetyloxy) -2,6-digodbenzene.

When the DIR compound is in a photographic emulsion is incorporated, the amount of the compound is usually from about 1/4 to about 1/2 hol, preferably from 1/10 to 1/100 mole, per mole of coupler in the emulsion. if the DIR-Yerbindüng is incorporated into the first developer, the compound can be used within a wide range of concentrations, but is usually that Amount thereof from about 1/3000 to about 1/10 mole per mole of the Developing agent in the developer. In this case, since a veil bath is used in the context of the invention, the DIR compound can be used in high concentration and therefore the i) IR compound is most preferred in the developer within a range of 1/200 to 1/20 mole per mole of developer.

In the case of the method according to the invention, it is advantageous that the DIR compounds in the photographic emulsion layers of the color photographic materials are included. the

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Objects of the invention can, however, also be sufficient Way can be achieved when the DIR connections in the first developer (black and white developer) incorporated will. Furthermore, as may be the case, color photographic Materials containing one or more DIR compounds in the photographic emulsion layers, in the first developer containing one or more DIR compounds.

The fog bath used according to the invention is customary and can contain the various known fogging agents. Typical examples of fogging agents are alkali salts of borohydride, for example the sodium salt, potassium salt, lithium salt and the like, compounds of the formula YBIU, in which Y is ammonia or an amine, for example an alkylamine, such as methylamine, dimethylamine, triethylamine, ethylamine, ethanolamine, diethylamine, Triethylamine, diethanolamine, propylamine, dipropylamine, butylamine, sec-butylamine, tert-butylamine and amylamine, a polyamine such as ethylenediamine, diethylenetriamine and the like, an aromatic amine such as aniline and the like, an aromatic amine such as pyridine and the like Lutidine or a phosphine, such as methylphosphine and ethyl phosphine _f or hydrazine, denotes compounds of the formula

/ B-H "B-N H

wherein Rr ₇ , Rg and Rq are a hydrogen atom, a halogen atom such as a chlorine atom, a bromine atom, an iodine atom, a fluorine atom, and the like, an alkyl group such as a methyl group, an ethyl group. Propyl group and the like, or an alkoxy group such as methoxy group, ethoxy group, propoxy group and the like,

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of the formula ( ^L _{+ n} ) _x C ^B _Y ^H _z ) "" ^nX i where L is an n-valent cation, where η is an integer greater than 1, χ an integer greater than 1, y an integer greater than 2 and z ζ represent an integer greater than 4, it being particularly preferred that η 1-31 are x 1 or 2, y 2 to and 6 to 14; Tin (II) complex salts "of amino carboxylic acids, for example nitrilotriacetic acid, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic, Äthylenglykolbis- (aminoäthyläther) tetraacetic acid, diaminopropanol, N-Hydroxyäthyläthylendiamintetraessigsäure, Äthyliminodipropionsäure and cyclohexanediaminetetraacetic acid, hydrazine compounds, for example, phenylhydrazine and naphthylhydrazine, tin (II) chelate of organic Phosphorus compounds corresponding to the formula R ^ QlT (CH ₂ PO, M ₂ ) 2 or R ^ R ^ CCPO ^ M ^^ where M is a hydrogen atom, an alkali atom such as a sodium atom, potassium atom, lithium atom, an ammonium group or pyridinium group, R ^ q an alkyl group having 1 to 4 carbon atoms such as methyl group, ethyl group, propyl group and n-butyl group, an aryl group such as phenyl group, o-tolyl group, m- tolyl group, p-tolyl group, o-carboxyphenyl group and p-carboxyphenyl group or an aralkyl group, like a benzyl group, and R _x . ^ a hydrogen f atom, an alkyl group having 1 to 4 carbon atoms, such as a methyl group, ethyl group, propyl group and n-butyl group, or a group of the formula P0, M ₂ , in which M is as defined above.

Specific examples of fogging agents which can be used according to the invention are the following:
Sodium borohydride,
Potassium borohydride,

Diethylacineborane, _ ..

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Triethylamine borane, trimethylamine borane, tert-butylamine borane, Pyridine borane,

2,6-lutidine borane, Ethylenediamine diborane Hydrazinediborane dimethylphosphine borane, Dimethylstibine borane, borazine,

N ₁ N 'IT' trimethylborazine, N, N ^1, N ⁿ - Trimethoxyborazin, T-etramethylammonium οctahydrotriborat, Ditetramethylammonium-hexahydrodiborat, Ditetramethylammonium-tetradecahydrodecaborat, Trimethyloctadecylammonium-oetahydrotribοrat, pyridinium octahydrotriborat, tetramethylphosphonium oetahydrotriborat, trimethylsulfonium octahydrotriborate, disodium hexahydrodiborate disodium tetradecahydrodecaborate, tin (II) ethylenediamine tetraacetate disodium salt, tin (II) nitrilotriacetate sodium salt, tin N-hydroxyethylenediamine triacetate, tin imino di acetate

Chelate of tin (II) and ethylenediamine-υ, ΙΓ, Ν ¹ , N'-tetramethylene phosphonic acid,

Chelate of tin (II) and nitrilo-IT ^^ - trimethylene phosphonic acid,

Chelate of tin (II) and 1,2-cyclohexanediamine-2T ₁ 2T, H ^I , N ¹ -tetramethylene phosphonic acid,

Chelate of tin (II) and propylamino-iT ^ N-dimethylene phosphonic acid, -

609825/0850

Chelate of tin (II) and 4- (pyrrolidino) -butylamine-li, N-bis- (methyl enpho sphonic acid,

Chelate of tin (II) and I ^ -diaminopropanol-N,] !!, ^ ', IT'-tetramethylene phosphonic acid,

Chelate of tin (II) and 1,3-propanediamine-N, N, N ·, N'-tetramethylenepho sphonic acid

Chelate of tin (II) and o-acetamidobenzylamino-ΪΤ, ΙΙ-dimethylenepho sphonic acid,

Chelate of tin (II) and 2-pyridylamino-N, N ¹ -dimethylene phosphonic acid.

Chelate of tin (II) and o-toluidine-N ^ N-dimethylene phosphonic acid,

Chelate of tin (II) and 1-hydroxyethylidene-i, 1-dipho sphonic acid,

Chelate of tin (II) and ethylidene-1,1,1-triphosphonic acid,

Chelate of tin (II) and 1-hydroxypropylidene-1,1-diphosphonic acid,

Ethylenediamine borane and

Hydrazine diborane.

Examples of fogging agents are given in U.S. patents 2,984,567, 3,246,987 and 3,554,748.

The veil bath used according to the invention is a alkaline aqueous solution (pH 7 to 14) of one or more fogging agents. The pH of the veil bath becomes by adding one or more alkaline agents such as sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, Potassium carbonate, sodium tert-phosphate, potassium tert-phosphate, Sodium metaborate, potassium metaborate, borax or ammonium hydroxide.

The veil bath can also contain a water softener, such as an aminopolycarboxylic acid or a polyphosphate and layer swelling inhibitors such as Glauber's salt. If so desired can be an acid, an alkali or a salt

60 9 8 25/0850

-23- 25A8S80

can be added to the veil bath to give the bath buffer capacity.

The concentration of the fogging agent in the fogging bath depends on the halide composition of the silver halide and the amount of silver in the silver halide emulsion layers of the color photographic materials to be treated from, but the proportion of the fogging agent usually is not less than about 10 mg per liter of the veil bath. The concentration of the fogging agent, for example the boron compound, is usually 10 to 1000 mg, preferably 20 to 300 mg, per liter of Schleierbsn:

Regarding the halide compositions, a color photographic material produced using. Silver halides were produced with a relatively large proportion of iodine, generally sufficient results, however, even if the concentration of the fogging agent in the fogging bath is high, too large one decreases Excess of the concentration of the fogging agent increases the color density. Concerning the amount of silver, the concentration can of the fogging agent of the fog bath can be reduced when the proportion of silver is lower.

The fogging agents are of course used at the optimum concentrations according to the properties of the color photographic materials to be treated in each case. If, for example, a color photographic Standard silver iodide material; d. H. a color photographic reversal material, which is 3.5 grams calculated as silver, of silver iodobromide with a content of 5 mol% silver iodide in the Silver halide emulsion layers per m of the color photographic material contains, in a borohydride containing Schleierbad is treated, the optimal concentration of sodium borohydride is 60 mg / l.

The pH value of the veil bath can be chosen within a wide range. When a skier ac Ξί, ζ · Ζ. ·: ~

609825/0850

Content of a boron compound is used, it is preferred that the bath is set to an alkalinity higher than pH 7, since a lower pH value of the veil bath leads to decomposition of the fogging agent. It is particularly preferred that the pH of the veil bath is higher than 9 am most preferably about 11 to 13

The color photographic reversal method according to the invention can be used according to the usual ones in the art Color reversal procedures can be carried out except that an independent fog bath is used; H. according to the pictorial Exposure is desired for the color photographic material if there is any pre-treatment, such as pre-hardening and aldehyde neutralization and then subjected to the first development (black and white development) to develop the exposed Parts subject. The color photographic material is then placed in the fog bath to transfer the remaining silver halide treated in the viable state. Then the color photographic material becomes a Subjected to color development and then to a bleaching stage and Fixing stage or a blix stage to remove the silver from it. If desired, various auxiliary baths, such as image stabilization baths, hardening baths, stop baths, neutralization baths, washing baths and rinsing baths between the respective Stages and after such stages are connected.

For the color development an alkaline aqueous Solution with a pH greater than 8, preferably 9 to .12, containing a primary aromatic amine as a color developing agent contains, used. It is known that color developers can contain benzyl alcohol. The color developing agent is a compound that a colored product produces in the reaction of its oxidation product with a color coupler forms. Examples of preferred color developing agents are

60 9 8 25/0850

p-ßenylenediamines, such as ζ. B. 4-Amino-N, N-diethylaniline, 4-Amino ^ -ethoxy-N ^ -diethylaniline, 4 — Amino-3,5-dimethyl-N, N-diethylaniline, 4 — Amino-3-methyl-N-ethyl-N- (ß-hydroxyethyl) aniline, 4-Amino ^ -methyl-N ^ -diethylaniline, 4-Amina ^ -methyl-N-ethyl-N-Cß-methylsulf onamidoethyl) -aniline, 4-amino-3- (ßmethylsulfonamidoethyl) -N, N-diethylaniline, 4-Amino-N-ethyl-N- (ß-hydroxyethyl) - <- aniline, 4-Amino-N, N-diethylaniline, and ^ Amino-N-ethyl-N - ^ - sulfobutylaniline. Mixtures of these amines or their salts, for example hydrochlorides, sulfates, sulfites and the like, can also be used.

Furthermore, those disclosed in U.S. Patents 2,193,015 and 2,592,364 and Japanese Patent Laid-Open The compounds described in patent application 64.933/1973 can be used as color developing agents in the context of the invention.

The black-and-white developers used according to the invention and color developers can furthermore contain conventional additives such as salts, e.g. B. sodium sulfate and the like., PH adjusting agents such as sodium hydroxide, sodium carbonate, sodium phosphate and the like., Buffers such as acetic acid, carbonic acid, boric acid and salts of such acids and development accelerators, e.g. B. the different Pyridinium compounds as described in US Patents 2,648,604 and 3,671 24-7, cationic compounds, Potassium nitrate, sodium nitrate, the polyethylene glycol condensates and derivatives thereof as disclosed in U.S. Patents 2,533,990, 2,577,127 and 2,950,970, non-ionic compounds such as those in British Patents 1,020,033 and 1,020,032 polythioethers, the polymeric compounds described in U.S. Patent 3,068,097 with sulfate ester groups, organic amines such as pyridine, ethanolamine and the like, benzyl alcohol and hydrazines.

The color developers may further contain an antifoggant such as an alkali bromide, an alkali iodide, the

609825/0850

254B880

Nitrobenzimidazoles according to US patents

2,496,940 and 2,656,271, mercaptobenzimidazoles, 5-methylbenzotriazole, i-phenyl-5-mercaptotetrazole, the compounds for rapid development, as in the US patents

3,113,864, 3,342,596, 3,295,976, 3,615,522, 3,295,976 and 3,597,199, the thiosulfonyl compounds described in British Patent 972 211, the phenazine described in Japanese Patent Publication 41 675/1971 N-oxides and the antifoggants listed in Kagaku Shashin Binran (Handbook of Scientific Photography), Volume 2, pages 6-47., which in the US patents 3,161,513 and 3,161,514 and British Patent Specifications 1 030 442, 1 144 481 and 1,251,558 stain or sludge inhibitors containing multilayer effect accelerators as described in U.S. Patent 3,536 and preservatives such as sulfite, acid sulfite and hydroxylamine hydrochloride.

In the process according to the invention, the color photographic Materials are pretreated in the usual way prior to initial development. As such a pretreatment a pre-hardening is usually used. The pre-hardening bath contains an aldehyde, with the effect of hardening by reaction with the gelatin in the photographic emulsion layers, for example the aliphatic aldehydes according to US Pat. No. 3,232,761, e.g. B. formaldehyde, Glyoxal, succinaldehyde, glutaraldehyde, pyruvic aldehyde and the like, as well as the aromatic aldehydes as described in U.S. Patents 3,565,632 and 3,677,760.

The pretreatment bath can still contain the usual additives, such as B. inorganic salts such as sodium sulfate and the like., pH control agents or buffering agents such as borax, boric acid, Acetic acid, sodium acetate, sodium hydroxide, sulfuric acid and the like, and antifoggants for the developers ·?;,

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like alkali halides, ζ. Β. Potassium bromide.

In general, the use of the pre-hardening bath is included A neutralization bath is also used to prevent the aldehydes used in the pre-hardening stage be introduced into the subsequent development stage. The neutralization bath contains an aldehyde remover, such as hydroxylamine and L-ascorbic acid, optionally together with an inorganic salt, a pH control agent and a buffer.

Those listed above in terms of treatment levels Additives, as well as the amounts of these additives, are well known for color photographic processes.

After the color development is finished, the color photographic Material usually bleached and fixed. The bleaching step and the fixing step can be carried out in one bath called a blix bath. The bleaching, fixing and blix baths according to the invention are customary and there is no limit to their composition.

As the bleaching agent, there are numerous compounds which can be used, but these include the following in particular Materials commonly used: complex salts of organic acids and polyvalent cations, such as ferricyanates, dichromates, water-soluble iron (III) salts, water-soluble cobalt (III) salts, water-soluble copper (II) salts, water-soluble quinones, nitrosophenol, iron (III), cobalt (III) and copper (II), Aminopolycarboxylic acids, such as ethylenediaminetetraacetic acid, nitrilotriacetic acid, iminodiacetic acid, N-hydroxyethylethylenediamine triacetic acid and the like, metal complex salts of acids such as malonic acid, tartaric acid, malic acid, diglycolic acid, and dithioglycolic acid, 2,6-dipicolinic acid copper complex salts, Peracids or peracid salts, such as alkyl peracids, persulfates, Permanganates and hydrogen peroxide, hypochlorites, chlorine,

60982 5/08 50

Bromine and bleach powder. These materials can be used individually or can be used as a combination.

All customary fixing solutions can be used for the fixing stage be used according to the invention, for example a fixing solution with a content usually from 50 to 200 g / liter ammonium thiosulphate, sodium thiosulphate or potash umthio sulfate. The fixing solution can also contain a stabilizer, like a sulfite and a metabisulfate, a hardening agent, such as potassium alum and the like, a pH buffering agent such as an acetate or a borate. The pH of the fixing solution is not limited, and acidic or basic fixing solutions can be used.

Bleaches, fixatives, and blix baths are detailed in U.S. Patents 3,22? 552 and 3,582,322.

The image stabilizing baths which can be used according to the invention can according to the US patents 2,515,121, 2,518,686 and 3,140,177.

In the method described above according to the Invention can each treatment step at temperatures below 20 C or, if desired, at temperatures higher than 20 ° C or higher than about 30 ° C and on most preferably the treatment can be carried out at temperatures from about 32 to 60 ° C. The ones to run this The temperatures required for the stages do not always have to be the same in every stage, but can be different.

The silver halide photographic emulsions used in the present invention are common and they are made by dispersing silver chloride, silver bromide, silver chlorobromide, Silver iodobromide »silver chloroiodobromide and the like, in aqueous Solutions of natural or synthetic materials from

609825/0850

high molecular weight such as gelatin, gelatin derivatives, for example Gelatin phthalate, gelatin malonate and the like, colloidal albumin and cellulose derivatives.

The silver halide emulsions can be chemically sensitized in a conventional manner. The chemical sensitizers used for this purpose are, for example, gold compounds, such as chloroaurates and gold trichloride in accordance with US Patent 2,399,831, 2 ^ O 085, 2597856 and 2540085, salts of platinum, palladium, iridium, rhodium and ruthenium in accordance with the U.S. Patents 2,448,060, 2,540,086, 2,566,245, 2,566,263, and 2,598,079, sulfur compounds capable of forming silver sulfide upon reaction with silver salts, such as in U.S. Patents 1,574,944, 2,410,689 , 3,189,458 and 3,501,313, stannous salts and other reducing materials such as in U.S. Patents 2,487,850, 2,518,698, 2,521,925, 2,521,926, 2,694,637, 2,893,610 and 3,201,254.

Various compounds can be used in the photographic Silver halide emulsions to prevent sensitivity and fog reduction during manufacture, Storage or processing of the color photographic materials to be incorporated. Examples of such additives are 4-hydroxy-6-methyl-1,3,3a, 7-tetraazaindene, 3-methylbenzothiazole, 1-phenyl-5-mercaptotetrazole and various others heterocyclic compounds, mercury compounds, mercapto compounds, and metal salts as used in the art are known for these purposes.

Specific examples of such additives are in E. Mees, The Theory of the Photographic Process, 3rd Edition, 1966 and in US 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, 2 444 603, 2 566 245, 2 694 716, 2 697 099, 2 708 162, 2 728 663, 2 728 664, 2 72? 665, 2,476,536, 2,824,001, 2,843 Vr ;, 2 886 437, 3 0 = 2 5-4, 3 137 577, 3 220 839, 3 226 231,

609825 / .0 850

25488

3 236 652, 3 226 231, 3 236 652, 3 251 691, 3 252 799, 3,287,135, 3,326,681, 3,420,668, 3,622,339, and British Patents 893,428, 403,789, 1,173,609 and

1 200 188 stated.

The photographic emulsion layers can be used in conventional Way to be hardened. Examples of hardening agents v) which can be used for this purpose are aldehyde compounds such as Formaldehyde, glutaraldehyde, and the like. Ketone compounds such as Diacetyl, cyclopentadione and the like, bis (2-chloroethylurea), 2-hydroxy-4,6-dichloro-1,3,5-triazine, reactive halogen containing compounds disclosed in U.S. Patents 3,288,775 and 2,732,303 and British Patents 974 723 and 1 167 207, divinyl sulfone, 5-acetyl-1,3-diacroylhexahydro-1,3,5-triazine, the reactive olefin containing compounds according to U.S. Patents 3,635,718 and 3,232,763 and British patent specification 994,869, ΙΓ-hydroxymethylphthalimide, which is described in US patents

2,732,316 and 2,586,168 listed N-methylol compounds, the isocyanates according to US Pat. No. 3,103,437, the azxridine compounds according to US Patents

3,017,280 and 2,983,611, the acid derivatives corresponding to U.S. Patents 2,725,924 and 2,725,295, the carbodiimide compounds according to US Pat. No. 3,100,704, the epoxy compounds according to US Pat 3,321,313> the isooxazole compounds according to US patents 3,321,313 and 3,543,292, halocarboxyaldehydes such as mucochloric acid and the like, dioxane derivatives such as Dihydroxydioxane, dichlorodioxane and the like; and chrome alum and zirconium sulfate as inorganic hardening agents.

Furthermore, precursors thereof, such as addition products of an alkali bisulfite and an aldehyde, a methylol derivative can be used of hydantoin and a primary aliphatic nitro alcohol can be used.

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The silver halide photographic emulsions used in the present invention may use spectral sensitization or supersensitization if desired of cyanine dyes, such as. B. cyanine, merocyanine, carbocyanine dyes and the like., Individually or as a combination thereof or further to a combination of such dyes and a styryl dye and the like., Are subjected. Such Dye sensitization methods are well known and are disclosed in 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 1 293 302, 1 242 588, and

1 293 862, the German Offenlegungsschriften 2 030 326 and

2,121,780, Japanese Patent Publications 4936/1968, 14 030/1969 and 10 773/1968, 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 can according to the end use of the photographic materials and wavelength ranges and desired ones Sensitivities are chosen.

The color photographic used according to the invention Reversal materials can be used in the silver halide emulsion. containing layers of magenta couplers, cyan couplers and yellow couplers, as known in the art.

For example, 5-pyrazolone compounds, indazolone compounds or cyanoacetyl compounds with active methylene groups can be used as a magenta coupler. Examples of magenta couplers which can be used according to the invention are given in the US patents 2 600 788, 2 983 608, 3 006 759, 3 062 653, 3,214,437, 3,253,924, 3,311,476, 3,337,344, 3,419,391, 3,419,808, 3,476,560 and 3,582,322, British Patent

60982 5/085 0

font 1 142 553 »of Japanese Patent Publication 20 636/1970 and 26 133/1972. Preferred magenta couplers within the scope of the invention are compounds corresponding to the general formula

(III)

where IL · «is a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group or a substituted or unsubstituted heterocyclic group, Ε,., An alkyl group, a carbamyl group, an amino group or an amido group and X a coupling, non-releasable group, for example a hydrogen atom, or a coupling releasable group, for example a thiocyano group, an acyloxy group, an aryloxy group, an alkoxy group or a halogen atom.

Specific examples of preferred magenta couplers are the following:

1-p-sec-amylphenyl-3-n-amyl-5 - pyΓazolon, 2-cyanoacetyl-5- (p-sec-amylbenzoylamino) -coumarone,

2-cyanoacetylcoumarone-5- (N-n-amyl-p-tert-amylsulfoanilide),

2-cyanoacetylcoumarone-5-sulfone-N-n-butylanilide, 1_.p_Laurylphenyl-3-methyl-5-pyrazolone, 1-p-Naphthyl-3-amyl-5-pyrazolon, 1 ~ p-liitrophenyl-3-E-s.myl-5-pyrazolon,

60 9 8 25/0850

i-phenyl- ^ acetylamino- ^ pyrazolon, 1-Phenyl-3-Il-v aleryiIamino-5-pyΓazolon, 1-phenyl-3-chloroacetylamino-5 ~ pyrazolone, 1-phenyl-3- (ft-aminobenzoyl) -amino-5-pyi'azolon, i-p-Phenoxyphenyl-3- (p-tert -amyloxybenzoyl) -amino-5-

pyrazolone,

1- (2 ', 4', 6'-trichlorophenyl) -3-benzamido-5-pyrazolone, 1- (2, 4'-dichloroplienyl) -3 ~ Z3 ⁿ (2 ^l ", 4 ^IM -di tert-amylphene

oxyacetamido) -benzamidq7-5-py-razolon,

1- (2 ', 4 ^ Mmethyl-6i-chlorophenyl) -3- / 3 ^M - (2 ^m , 4 ⁿ -di-tert.-

amylphenoxyacetamido) -benzamid7-5-pyrazolone,

Λ- ( 2 ^f , V, 6 ^ rriehlorphenyl) -3- (4 ^ nitroanilino) -4-stearoyl-

oxy-5-pyrazolone,

Λ- (2W1 6 ^ trichlorophenyl) -3- f3-Z- (2 ^ Ai-tert.-amyl-

plienoxy) -acetamidq7-benzamidoJ-4-acetoxy-5-pyrazolone _i

1- (2 ', 4' '", 6 ♦ -Trichlorphenyl) -3-pentadecyl-4-thiocyan-5-pyrzolone, 1- (2 ', 4', ei-Trichlorplienyl) - 3-Z3- (2 ", 4 ^ di-t ert. -Amylphenoxy-

acetamido) -benzamido7-4-thiocyan-5-pyrazolone,

1- (2 ^/ , 4 ', 6 ⁱ -Triciilo2? Pb.enyl) -3-peiitadecyl-4-sulfo-5-pyrazolone, 1- (2' _t 4 ^/ _i 6-tricloroplienyl) -3-peiitadecyl-4 -c] ilor-5-pyrazoIon _e phenolic compounds or naphtholic compounds are used as

Cyan coupler used according to the invention. According to the invention usable cyan couplers are in the US patents

2,474,293, 2,698,794, 3,034,892, 3,214,437, 3,253,924,

311,476, 3,458,315, 3,582,322, and 3,591,383 and the Japanese Patent Publications 11304/1967 and 32461/1969.

The phenolic cyan couplers and naphtholic cyan couplers preferably used in the context of the invention are represented by the general formulas (IV) and (V):

609825/0850

wherein

Rl 6

(V)

17th

Hydrogen atom,

Alkyl

group, an aryl group, a heterocyclic group, an amino group such as an amine group, alkylamino group, arylamino group, heterocyclic amino group and the like , sulfonamido heterocyclic group and the like, a sulfamoyl group such as an alkylsulfamoyl group, arylsulfamoyl group, a heterocyclic sulfamoyl group and the like, a carbamoyl group such as an alkylcarbamoyl group, arylcarbamoyl group, heterocyclic carbamoyl group and the like, a cyano group, a halo atom and the like, a chlorine group, for example. an alkoxy group or an aryloxy group, where Rvj ^, R / | c »R ^ g and R ^ r _{7 can} advantageously be substituted with a ballast group, as explained earlier, and X is a coupling non-releasable group, such as a hydrogen atom, or a k repelling releasable group, such as a chlorine atom,

6 0 9 8 2 5/0850

Bromine atom, iodine atom, thiocyanate group, acyloxy group, for example Alkoyloxy group, aroyloxy group, heterocycloyloxy group and the like., or a cyclic imide group such as maleimide group, succinimide group, 1,2-dicarboxyimide group, 2-dicarboxyimide group, phthalimide group and the like., mean.

In the above description regarding compounds of general formulas (I) to (III), all of the alkyl moieties preferably have 1 to 20 carbon atoms
unless otherwise noted, and the preferred aryl groups include the following examples:

(X: Cl, CONH)

-ΓΛ-ΤΧ

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It can be seen from this that the aryl groups can consist of monoaryl groups or polyaryl groups.

Specific examples of those which can be used according to the invention Cyan couplers are the following:

5- (p-Amylphenoxybenzenesulfοamino) ~ 1-naphthol, 5- (N-Benzyl-N-naphthedinsulfοamino) -1-naphthol, 5- (N-Benzyl-N-n-valerylamino) -1-naphthol, 5-caproylamino-1-naphthol,

2-chloro-5- (p-nitrobenzoyl-ß-o-hydroxyethylamino) -1-naphthol,

2-chloro-5-palmitylamino-1-naphthol, 2,2'-dihydroxy-5,5'-dibromostilbene, ^ Diphenylethersulfonamido-i-naphthol, 1-hydroxy-2- (N-sec-amylphenyl) -naphthamide,

Monochloro-5- (Ν-γ-phenylpropyl-N-p-sec.-amylbenzoylamino) -1-naphthol,

2-acetylamino-5-methylphenol, 2-benzoylamino-3 _? 5-dimethylphenol,

1-Hydroxy-2- / a- $ ia - ^, 4 _T di-tert-amylphenoxy-n-butyl? - naphthamide,

2- (4 "-tert.-amyl-3'-phenoxybenzoylamino) -phenol.

Open chain diketomethylene compounds are becoming common used as a yellow coupler. Examples of yellow couplers which can be used according to the invention are given in the US patents 3 341 331, 2 778 658, 2 908 573, 3 227 550, 3 253 924, 3 384 657, 2 875 057 and 3 551 155, the German Offenlegungsschrift 1,547,868, U.S. Patents 3,285,506, 3 582 322 and 3 725 072, the German Offenlegungsschrift

2,162,899, U.S. Patents 3,369,895, 3,408,194,

3 227 155, 3 447 928 and 3 415 652 and the German Offenlegungsschriften 2,057,941, 2,213,461, 2,219,917, 2,261,361 and 2,263,875.

6 0 9825/0850

_ 37 - 254888Q

The preferred yellow couplers which can be used according to the invention are compounds according to the general formula

VI

wherein R ^ q is an unsubstituted or substituted alkyl group, an unsubstituted or substituted aromatic group or an unsubstituted or substituted heterocyclic group, X is a coupling non-releasable group such as a hydrogen atom _/ or a coupling releasable group and W is a cyano group or a carbamoyl group.

Specific examples of preferred ones according to the invention Yellow couplers used are the following:

a- / 3- ^ öc-2 _t 4-di-tert-amylphenoxy) -butyramido7-benzoyl] -2-methoxyacetanilide,

α— f3-Za-2,4-di-tert-amylphenoxy) -acetamido7-b enzoylj2-chloroacetanilide,

2, -0ωοΓ-3'- t- (2,4-di-tert-amylphenoxy) -butyramido7-benzoylacetanilide,

α- £ 3- ^ α- (2,4-di-tert-amylphenoxy) -acetamide <a7-benzoyl ^ - benzoylacetanilide,

a-Pivaloyl-2,5-dichloro-4-Z & ¹ - (n-octadecyl) -N · -methylsulfamyl7-acetanilide,

2- (^ - "- tert-Amyl-3 '-phenoxybenzoyl) -phenol,

a-Pivaloyl-2-chloro-5-Z- (2 ', 4'-di-tert-amylphenoxy) -butyramidoZ-acetanilide,

α- {3-z-m-pentadecylphenoxy) butyramido7-benzoyi \ -2- chloroacetanilide

6 09825/0850

α- (2 ', 4'-Dimetho3cybenzoyl) -2-chloro-5- (2 ^l -hexyldecyloxycarbonyl) -acetanilide,

oc-Pivaloyl-a - / ^ (4-benzoyloxyphenylsulfonyl) -phenoxyy-2-chloro-5-ZY- (2,4-di-tert.-amylp] ieiioxy) -butyramido7-acetanilide,

a-o-Metlioxybenzoyl-a-chloro-4- / ä- (2,4- di-tert-amylphenoxy) -n-butylamido7-acetanilide,

OC-Fluoro-pivaloyl-5-Zy-2,4-di-tert-amylphenoxy) -batyramido7-2-c3iloracetanilid _i

a-Aceto3q7-a-ί3-Ζγ- (2,4-di-1-tert-amylplienoxy) -butyr ~ amido7-benzoyl ^ -2-methoxyacetaIlilid,

a-pivaloyl-a-stearoyloxy-4-sulfaniylacetanilide,

chloracetanilide,

α- £ 3-Z- (2,4-di-tert-amylphenoxy) -butyramido7-benzoylj 2-methoxyacetanilide,

α-Benzoyl-α-thiocyanacetanilide.

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CH

H ^ C-C-COCKCOITH - // V

NHCO (CH ₂ ) * ⁰ -

^cH

. CH

H ₅ CC-COCHCONH

HHOOCHO

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CH,

H ₅ CC COCHCOKH.

^CH; A.

oc co

H ₃ CC- -NH

CHx

SHCOCHO-

OCH,

i-;

/ VS-COCHCOKH - // ^)

COOC

_1Zf

NHCOCiIO-

0 9 8 2 5/08 6 D

OC I

H, C-C- ^ i

Cl

/ -Ν

COCHCOUH - // V!

I / ¹ K

NHCOCHO-

co

• NH

CH,

H ₃ CC COCHCOITH

CH,

OC

V ₅ H ₁₁ Ct)

CH _z -C-COCEC0NII-ι

CH,

NHC0 (CH ₂ ) ₃ 0 - // ^ M C ₅

Cl

CCOH

609825/0850

CH,

Ch ₃ -C-COCHCONH CH

^ ■ z

.C0 (CH _2), Q

' ^C 5 ^H ll ^(t)

COCH-

CH,

.O-C-COCHCOIiH CH-

/ K

O = C C = O

609825/0850

OCH

HCOCKO-

.COOC ₁₂ H ₂₅ Cn)

COOH

09825/0850

-COCHCOKH-

O = C C = O

HN

C-CH

CH

COCHCOIIH- '

) -C C = O

NHC0QHO -

60982b / 0850

Γ ⁵

HCQCEO-

COCHCOIiH

O = C C = O

OCH ₃

// W Λρττ -j -jv

NHCOCHO-

O = C C = O

609828/0850

OCH,

-OH,

NHCOCHO-

M-COCHCONHhV V)

NHCOCHO

O = C-CH ₃

-C ₅ H ₁₁ Ct)

609825/0 8 50

CH,

I ³ / ^s

ch, -c-cochco: ih-c

⁵ I.

CH

= C C = O

KHCOC-

V ^ -IIHCOCH ₂ CH ₂ N,

COC, K ^ (η)

Cl

■ /

O = C

C = O

CH ₂ -CH ₂

OCH,

OCH

-IiHCOCKCO-O I AS -COCHCOrTII

/ V

O = C C = O O = C C = O

609825/0850

_ 48. -

(n) H ₂₃ c _{i; L} co: ni,

Cl

COOCH-

CH-

OCH,

COCHCOlTH-;

, N

O = C 'C = O

/ V

O = C C = O

OCH

-COCHCOIiK-

60982 b / 08 5

COOH

ch, -c-coceco: t & ³ I.

CH,

COOH

O = C C = O

CH ₃ -C-COCKCONh

CH

NHCOCHO-

Cl

HC IiH

Ct)

CHp
HC NH

CHx-C-COCHCCITH-

CH.

C ₂ H ₅

NHCOCHO- <

C ₅ H ₁₁ Ct)

25/08. ^ 0

HCOCHO

CH-

COCHCOXH-

Cl -

CH,

CH ^ -C-COCHCOim-! I.

Cl

O. AL · O

: cocho

Supreme Court ₃

-COCECOIIH-.0

CK.

-COOCH-

609825/085

CIL

^ P

HCOCH-O-

CH ^ -C-COCHCONH-V V

CH, -C-COCHC0! TH ι

CH,

.COOCH-COOC _n

609825/0850

HCOCHO-

K-CH,

609826/0 8.-510

25A8S80

Cl

CH ₅ -C-COCHCOIrH-CH ₃

VY

^A 2 \ r ^Cn 3

H ₅ CO

-Cl

J / vS-COCHCOiiH - // \

C ₅ H ₁₁ Ct)

TiHCOCKO-

Ct)

609825/0850

Cl

, -C-COCKC

CH ₃ -C-COCKCOHh

CH.

O 21 O

VV

■ NHCHO JJ N) -C ^ H ₁ -, (t)

VV '5 "1Γ

CH

- COCHCONJ

ON _x

CH,

C H- η)

60982 5/08 5

Further examples of the invention are used according to GeIb- coupler of the following, wherein X is a coupling-off or "releasable on coupling group:

(CH,) ₃ CCOCHCO2iH

Cl /

(CH,), CCOCHCOITH - //

Cl

NHCOCCH-

60 9 8 25/0850

Cl

/ VS-COCHCOITH - // \ S S = / i N = /

"NHi

? ₅ ^Η ιι

nhcocho

- ^ μ -C ₅ H ₁₁ C t)

₅ H ₁₁

CH

-COCH

X

Cl

HC0I7H - // NX

609825/085 0

OCH,

COCHCONH-

COOCH-COOC ₁₂ H ₂₅ (η)

CH ₃

609825/08 5 0

Furthermore, the following coupling-off groups or groups which can be released during coupling can be used in the groups according to the invention used yellow couplers:

CO

H ₂ C-. -O

OC

H-C

■ GEL

CO
0

OC '

H ₃ CC

CH

-K-CH,

CO CO

OC CO

OC CO

H _x CC

-N- (CH ₂ ) ₂ 0E

60982S / 0850

OC CO

H _x CC-

CH,

OC '^ CO

H ₃ CC

C ₂ H ₅

OC CO

-N-CH ₂ -CH = CH ₂

CH,

609825/0850

25488

oc

H ^ C-C

0 (

H-C

^C0

OC ^ H ₉ Cn)

H-C

CO

NH

■ Ν-

H-C 0

CO

-! III

OC

CnJi ₇ C ₃ -

CO

-ίΤΗ

60 9 8 25/0850

CO

N-

OC ₂ H ₅

oc "co

/ X

OC CO

OC

H ₃ CC

CH, CO N (CH ₂ ), OH

'N-

CO

- ITCOCH OC.

co

• K (CH ₂ J ₃ OCOCH ₃

609825/0850

co

E ^ C-C

οσ cc

H ^ C-C -

CH,

OC ■ CO

H-C -1-ΪΗ

ocr co

H ₃ CC

■ H (CH ₂ ) ₃ -f!

CH,

oc co

-N (CH ₂ ) ^ - N

60 9 825/0850

The couplers listed above can be prepared by the methods described in U.S. Patents 3,277,155, 3 408 194 and 3 447 028, the German Offenlegungsschrift 2,057,941, U.S. Patents 2,350,138, 2,359,332,

2 407 210, 2 875 057, 3 265 506, 3 341 331, 3 409 439,

3,551,155, 3,551,156, 3,649,279 and British patents 1,261,156 and 1,296,411 will. The couplers can also be dispersed by the methods set forth in U.S. Patent 2,801,171 will.

Surface-active agents can be added to the invention silver halide photographic emulsions used can be added individually or as mixtures thereof. They are usually used as coating auxiliaries but sometimes also for other purposes, such as emulsification, Dispersion, sensitization, photographic improvement Properties, static prevention and adhesion prevention are used.

Examples of such surfactants are nonionic surfactants such as surfactants Alkylene oxide type agents, glycerin type surfactants and glycidol type surfactants, cationic surfactants such as higher alkyls quaternary ammonium salts, pyridines and other heterocyclic compounds, phosphonium compounds and sulfonium compounds, anionic surfactants having a carboxylic acid, sulfonic acid, phosphoric acid, phosphoric acid ester group or sulfuric acid ester group and amphoteric surfactants such as amino acids, aminosulfonic acids and sulfuric acid esters or phosphoric acid esters of amino alcohols.

Numerous such surfactants are described in U.S. Patents 2,271,623, 2,240,472, 2,288,222,6,

609825/0850

2 739 891, 3 068 101, 3 158-484, 3 201 253, 3 210 191,

3,294,540, 3,415,649, 3,441,413, 3,442,654, 3,475,174

and 3 545 974, the German Offenlegungsschrift 1 942 665, British patents 1,077,317 and 1,198,450, Ryohei Oda et al., Synthesis of Surface Active Agents and Applications thereof, 1964 Maki Shoten, A.W. Perry, Surface Active Agents, Interscience Publication Incorporated, 1958 and J.P. Sisley and P.J. Wood, Encyclopedia of Surface Active Agents, Volume 2, Chemical Publishing Co., 1964.

The photographic emulsion layers of the photographic Materials can be entrapped on a carrier by any of various conventional coating techniques dip coating, air knife coating, curtain coating, extrusion coating using a funnel according to US Pat. No. 2,681,394 and the like. If so desired For example, two or more emulsion layers can be coated simultaneously by methods such as those described in US patents 2,761,791, 3,508,947, 2,941,898 and 3,526,528 are described.

The photographic emulsions can be used on any common carriers that do not suffer any significant dimensional changes during treatment, such as glass plates, Metal plates, ceramic plates or flexible supports. Typical examples of flexible supports are cellulose nitrate films, Cellulose acetate films, cellulose acetate butyrate films, cellulose acetate propionate films, polyethylene terephthalate films, Polystyrene films, polycarbonate films, laminates from these films, thin glass films and papers. Furthermore, barite-coated papers, coated with α-olefin polymers Papers, especially a polymer made of one

609825/08 5 0

α-olefin with 2 to 10 carbon atoms, such as polyethylene, Polypropylene and ethylene-butene copolymers, and plastic films with matt surfaces to improve adhesion to other polymers and printability, as in Japanese Patent Publication 19 068/1972 / can be used with good results.

Transparent or opaque! Markers can be used according to the end use purpose of color photographic materials applied will. Furthermore, colorless supports and those colored with dyes or pigments can be used as transparent supports Carriers are used. Colored transparent supports are commonly used for X-ray photographic films and are described in Journal of S.M.P.T.E., Volume 67, page 295 (1958).

The opaque supports can be inherently opaque supports such as papers, or can consist of opaque films, by incorporating dyes or pigments such as titanium oxide into transparent films or by treatment the surfaces of a transparent film according to, for example, the Japanese Patent Publication 19 068/1972 described method be produced opaque films and papers or plastic films with a complete shielding property by adding carbon black or dyes. If liability is between insufficient for the support and the photographic emulsion layer is, a layer with high adhesion for both elements can be formed on the support as a primer layer will. To improve the adhesion of the carrier, the surface of the carrier can also be subjected to a pretreatment, such as corona discharge, Be subjected to ultraviolet radiation or flame treatment.

The method according to the invention can be used for various color photographic silver halide reversal siateria] .ieii,

609825/0850

such as color photographic reversal papers, color photographic reversal films, color photographic reversal films for slides, color, reversal photographic films and color reversal photographic films can be used for television.

One of the features of the method according to the invention lies in the aspect of using a veil bath separate from the color developing baths without incorporating a fogging agent in the color developing bath and that the first development (black and white development) carried out in the presence of one or more DIR compounds, eliminating the harmful effects of the Avoided DIR connection in color reversal development can be, as described above.

The achievable by the method according to the invention The advantages are as follows:

1. Sufficient color density is obtained even when a DIR connection is used. If the When the first development is performed in a reverse color process in the presence of the DIR compound, the undeveloped Silver halide grains are influenced by the development inhibitor and make the progress of color development difficult, resulting in a decrease in color density. On the other hand shows the invention Process the DIR connection its effect and

a sufficient color density is nevertheless obtained.

2. Color photographic images with sufficient sharpness are obtained. While the DIR connection is the sharpness the color images improved during negative color development, in reverse development, the silver halide grains become strong due to the development inhibitor (due to the presence of the DIR connection in the first developer), which are subject to color development, and are in a sol-

609825/0850

chen condition that the sharpness of the formed color images usually weak. On the other hand, by using the veil bath according to the invention, this error can be avoided and color images with excellent sharpness are obtained.

3. Color photographic images with sufficient grain will get. That is, by using the veil bath according to the invention, the grain size of the color images formed are improved, as in the above case.

4-. The stability of the color developer is improved. That is, the color developer for reversal color processing is originally unstable, which is an error the quality control of color developer manufacturing. On the other hand, by using the veil bath improves the stability or the life of the color developer, which is a secondary effect according to the invention represents. The method according to the invention thus has the advantage that the life of the color developer is extended and the color development can be carried out stably. On the other hand, with a usual Color reversal system, in which the fogging agent is incorporated into the color developer, the color developer is quickly damaged, so that it becomes difficult to maintain the stable quality of the color developer.

The invention is explained below with the aid of a few exemplary embodiments explained without the invention being limited thereto.

example 1

The color photographic materials A and B were in made in the following way.

609825/0850

/ 7 ίΧ el ι ff OtL-J ί ι c (- _L

A color photographic material (sample A)

was made by drawing on a cellulose triacetate film base an emulsified mixture of a red-sensitive silver iodobromide emulsion (containing 7 mol% silver jo ~ did) and as a cyan coupler i-hydroxy-4- chloro-2-n-dodecylnaphthamide, an emulsified mixture of a green-sensitive silver iodobromide emulsion ( Content 6 mol% silver iodide) and as a magenta coupler 1- (2 ', 4-', 6'-trichlorophenyl) -3- ^ 3 «« _ (2 ^lll , 4 "'- di-tert-amylphenoxyacetamido) -benzamido7- 5-pyrazolone and an emulsified mixture of a blue-sensitive silver iodobromide emulsion (content 6 mol% silver iodide) and, as a yellow coupler, a-pivaloyl-2-chloro-5- / y- (2,4-di-tert-amylphenoxy) -butyramido-7-acetanilide manufactured.

Another color photographic material (Sample B) was made in the same manner as in the case of preparation of Sample A except that 2,5-dimethyl-3- (1-phenyl ^ 5-tetrazolylthio) -hydroquinone into the emulsified mixture of the green-sensitive silver iodobromide emulsion as THE connection was incorporated.

In preparing the above color photographic materials, each coupler was prepared using Dibutyl phthalate or tricresyl phosphate as a coupler solvent and sodium dodecylbenzenesulfonate and sorbitan monolaurate emulsified as an emulsifier. l Sodium 1- (p-nonylphenoxytrioxyethylene) butane-4-sulfonate and the lauric acid ester of sucrose were used as coating aids used for the photographic emulsions.

In the above photographic material and that of the following examples, the following ratios were used:
AgX / gelatin (weight = 2.0)

Coupler / gelatin (weight: blue-sensitive layer J., 6

green-sensitive layer O ₁ ; -red-sensitive layer 1

609825/0850

The thickness of each emulsion layer bt-t-rug is 5 microns each The solvent for the cyan and magenta couplers existed from dibutyl phthalate and the solvent for the yellow coupler consisted of tricresyl phosphate. The coupler / The solvent was: blue-sensitive layer 200 g / ccm; green sensitive layer 80 g / ccm; red sensitive layer 180 g / cc. ,

The thickness of each auxiliary layer, e.g. filter layer, Protective layer, intermediate layer was about 1 μ. Each of Samples A and B had a filter sheet yellow colloidal silver between the green-sensitive Silver halide emulsion layer and the blue-sensitive silver halide emulsion layer, an intermediate layer Gelatin with di-tert-amylhydroquinone dispersed therein to prevent diffusion of the oxidized developing agent from one layer to another layer, thereby Color fog or color staining is reduced between the green-sensitive silver halide emulsion layer and the red-sensitive silver halide emulsion layer and one composed mainly of gelatin on the blue-sensitive silver halide emulsion layer Protective layer.

Furthermore, for each sample, the coverage was the red-sensitive Silver halide emulsion layer 1.5 g Ag / m, that of the green-sensitive silver halide emulsion

layer 1.5 g Ag / m and that of the blue-sensitive Silver halide emulsion layer 1.5 g Ag / m. The silver/ Coupler ratio in each layer was 8.0 in terms of MoI ratio in the red-sensitive silver halide emulsion layer, 9 * 5 in the green-sensitive silver halide emulsion layer and 8.0 in the blue-sensitive silver halide emulsion layer.

Sample A is a common reversal color photographic material, while Sample B is a color photographic material Represents reversal material according to the invention.

The following treatments were carried out using each of the thus prepared samples.

Each of the photographic films thus prepared was exposed to light (tungsten lamp, Farbtenperatur 3200 ⁰ K, shutter speed 1/100 second, as in the examples ιeisenden unless andereres indicated)

6 098 25/0850

and then subjected to the following treatments I, II and III.
Treatment stages I.

First development (black and white

Development) 30 C 5 minutes

Stop treatment "1 minute

Wash "2 minutes

Color development "7 minutes

Stop treatment "2 minutes

Hardening "2 minutes

Wash "2 minutes

Bleaching "4 minutes

Wash ^M 2 minutes

Fixation "4 minutes

Wash "2 minutes

Drying "2 minutes

The compositions of the treatment solutions used in the above treatment were as follows:

Black and white developer

Sodium sulfite 60.0 S. 1-phenyl ~ 3-pyrazolidone 0.3 G Hydroquinone 5.0 G Sodium carbonate (monohydrate) 41.0 G Potassium bromide 2.0 6th Potassium iodide (1%, aqueous
Solution) 1.0 ml Potassium thiocyanate (aqueous,
1n solution) 10.0 ml Sodium hydroxide (10%, aq
ge solution) 2.0 ml Water too 1.0 liter

60982 5/08 5 0

Stop solution:

Sodium acetate 30 g ml Glacial acetic acid 8 ml G Water too ml Color developer: L. G Benzyl alcohol 1 liter G Sodium hydroxide G Diethylene glycol 5.0 G Sodium hexametapho sphat 0.5 Sodium sulfate 3.0 G Potassium bromide 2.0 ml 4-amino-3-methyl-N-ethyl-ß-
hydroxyethylaniline-sesquis. ^ sulphate-
monohydrate 2.0 G Citrazinic acid 2.0 liter Metaboric acid 5.0 Ethylenediamine (70%, aqueous 0.4 G Nabox 0.5 G Water too 0.4- ml Hardening bath: 77.0 Sodium hexametaph.o sphat 1.0 G Borax pentahydrate G Formalin (37 %) 1.0 Z Bleach solution 20.0 G Sodium ferric ethylenediamine
tetraacetic acid dihydrate 10.0 liter Potassium bromide Disodium ethylenediamine tetra-
acetate 30.0 Boric acid 50.0 Water too 5.0 Fixing solution 3.0 Sodium thio sulfate 1.0 Sodium salfit 150 g 15 g

609825/0850

Borax ζ 12 g

Glacial acetic acid 15 ml

Potassium alum 20 g

1 liter of water.

Treatment II

As in Treatment I, except that 0.1 g / liter of sodium borohydride was added to the color developer. Treatment III

As in Treatment I, but with the completion of the first wash, the photographic material in one Was treated at 30 ° C for 2 minutes and then subjected to color development. The composition of the veil bath used was the following:

Composition of the veil bath

Sodium hydroxide 2.0 g

Sodium borohydride 0.1 g

1.0 liter of water

The photographic properties of the color images obtained are shown in the following table.

60982S / 0850

Attempt-
No. Photographic
phical
material Treat
lung R. Dm
G B. Sharpness
20 l / mm 30 l / mm Grit
(Distance (cm)) annotation ■ Λ 1 A. I. 2.9 2.9 3.0 40 20th 150 Comparative
example 2 A. II 3.1 3.1 3.2 45 25th 150 ti CD 3 A. III 3.1 3.1 3.2 45 25th 150 Il O 4th B. I. 2.0 1.9 1.8 25th 10 220 Il OO 5 B. 11 2.6 2.8 2.8 35 20th 180 ti 25/0850 6th B. III 3.1 3.1 3.2 50 30th 130 Inventive
according to
example

OO CO CO

Footnotes:

1) Dm, R, G and B: When determining the permeability density of each sample strip, the density of the unexposed part, i.e. H. the density of the part with the maximum Density ^ denoted as Dm, E, G and B mean in the table the values for Dm, measured with red light, green light and blue light.

2) The sharpness was determined in the following manner: If the square wave frequency response of the density determination designated as 100 by green light at a frequency of O l / mm the response values are at 20 1 / mm and

30 1 / mm given as relative values.

3) The grain size was determined in the following way: The sample was subjected to color reversal development after uniform exposure to gray light on a canvas with 10x magnification projected by means of a projector and the observer gradually turned away from the screen. the Grain was indicated by the distance from the screen where the projected pattern of the grains no longer aligns with the could be observed with the naked eye. Thus, the lower the value, the finer the grain.

As is clear from the results of Experiments 1, 2 and 3, in the case where the DIR compound was not used, sufficient color density was obtained when the fogging agent was in the developer or a fogging bath containing the fogging agent was separately applied and the sharpness and grain of the color photographic images became normal. Furthermore, in test 1 _t where the fogging agent (sodium borohydride) was not present, the color density of the color images was reduced and the sharpness was considerably reduced.

6 09825/0850

It should be noted that in Experiment 1 where there was no sodium borohydride was present, but the ethylene diamine in the color developer used has a weak fogging effect. If ethylenediamine was not present, the color density was reduced more.

On the other hand, if the one containing the DIR connection When the sample was subjected to Treatment I, the color density of the formed color images was insufficient and the Sharpness of the same was insufficient and the grain was coarser. When the foggant to the developer (like shown in Treatment II) was added, the above errors were significantly improved, but was the degree of improvement worse than the results of experiments 1 and 2, which are common procedures, d. H. had the presence of the DIR connection a detrimental effect on the color density, sharpness and grain of the color images formed. Therefore it emerges clearly from the results of Experiment 5 * that the DIR connections are unsuitable for the usual reverse color development. If on the other hand, color photographic materials, the DIR compounds contained, in the fog bath or in the presence of the fogging agent according to the inventive method treated as shown in Experiment 6, both sharpness and grain of the color images formed were improved remarkably improved. The effects according to the invention are thus achieved through the simultaneous application of the features Firstly, the development is carried out in the presence of the DIR compound and, secondly, a fog bath before the color development was used, achieved; the effects according to the invention cannot be achieved using the Levels (1) or (2) can be achieved individually. The individual application of steps (1) or (2) does not result in the above The effect of the invention can still be expected from this. -

609825/0850

2548080

Furthermore, there was a sharpness in color images Due to the multi-layer effect, the sharpness of the color images in experiment 6 is far superior to that in the experiments 1 and 2, demonstrating that the multilayer effect was effectively obtained by using the DIE compound. Both On the other hand, in Experiments 4 and 5, the color density was insufficient and, as a result, the sharpness of the color images became lower despite the use of the DIH connection. Also at In experiment 3, the sharpness of the color images was better than in experiment 2, which proves that the multi-layer effect was not without the presence of the DIS compound, even when a fog bath was used.

The invention has been described above on the basis of preferred embodiments without being limited to this.

60982b / 08b0

Claims (11)

Claims _A reversal color development process for silver halide reversal color photographic materials including a first development and a color development, characterized in that the first development is carried out in the presence of a non-coupler compound capable of releasing a development inhibitor and the photographic materials with an aqueous solution of a fogging agent capable of chemically fogging the silver halide of the photographic materials, and then subjecting the photographic materials to color development. 2. color reversal development method according to claim 1, characterized in that the the A non-coupler type development inhibitor releasing compound in the photographic emulsion layer of the color photographic Material is present. 3. color reversal development method according to claim 1, characterized in that the the The non-coupler-type development inhibitor releasing compound consists of a development inhibitor which releases a hydroquinone compound. 4. color reversal development method according to claim 1 to 3, characterized in that the aqueous solution of the fogging agent is an alkaline one 609825/08 5 aqueous solution of an alkali salt of a borohydride, a
A compound corresponding to the formula YBEU, in which Y is ammonia
or is an amine, a compound of the formula ■ HR ₈ ■ ι ι B - Ii R ₇ -K '^ BH \ b - ir I! where R ~, R _Q and Rg are a hydrogen atom, a halogen atom,
denote an alkyl group or an alkoxy group, a polyborohydride corresponding to the formula (^ ₊ Jj) _x (ByH ₂ ) "" ¹¹³ S in which
L is an n-valent cation, where η is an integer greater than 1, χ is an integer greater than 1, y is an integer
A number greater than 2 and ζ means an integer greater than 4 ', a tin (II) complex salt of an aminocarboxylic acid, a tin (II) chelate compound of an organic phosphorus compound or a hydrazine compound is used. 5. color reversal development process according to claim 4, characterized in that η is the value 1 to 3, χ the value 1 or 2, y the value 2 to 20 and ζ den Have a value of 6 to 14. 6 _β color reversal development method. according to claim 4, characterized in that Y consists of a methylamine, dimethylamine, triethylamine, ethylamine, ethanolamine, diethylamine, triethylamine, diethanolamine, propylamine, dipropylamine, butylamine, sec * -butylamine, tert-butylamine or ainylamine group consists " 60 982 5/08 50 7. color reversal development method according to claim 4, characterized in that Y is selected from Group consists of ethylenediamine and diethylenetriamine. 8. color reversal development process according to claim 1 to 7, characterized in that the development inhibitor releasing compound is of the non-coupler type in the first developer. 9. color reversal development process according to claim 1 to 8, characterized in that a compound selected from the group consisting of sodium borohydride, potassium borohydride, diethylamine borane, triethylamine borane, trimethylamine borane, tert.-butylamine borane, pyridine borane, 2,6-lutidine borane, ethylenediamine borane, hydrazine borane, dimethylphosphine is used as fogging agent Dimethylstibinboran, borazine, N, N ^1, N "-Trimethylborazin, N, N ^1, N" -Trimethoxyborazin, Tetramethylammoniumoctahydrotriborat, Ditetramethylammoniumhexahydrodiborat, di-tetramethylammoniumtetradecahydrodecaborat, Trimethyloctadecylammoniumoctahydrotriborat, Pyridiniumoctahydrotriborat, Tetramethylphosphoniumoctahydrotriborat, Trimethylsu3fbniumoctahydrotriborat, Dinatriumhexahydroborat, Dinatriumtetradecahydrodecaborat, tin (II) - Ethylenediamine tetraacetate disodium salt, 2inn (II) nitrilotriacetate sodium salt, tin N-hydroxyethylenediamine triacetate, tin iminodiacetate, chelate compounds of tin (II) and ethylenediamine Ν, Ν, Ν », N'-tetramethylene phosphonic acid , Chelate compounds of tin (II) and nitrilo-N, N, N-trimethylene phosphonic acid, chelate compounds of tin (II) and 1,2-cyclohexanediamine-N, N, N ^t , N'-tetramethy lenpho sphonsäur e, chelate compounds of tin (II) and propylamino-N, N-dimethylene phosphonic acid, chelate compounds of tin (II) and 4- (pyrrolidino) butylamine-N, N-bis (mexhylenphosphonic acid), chelate compounds of tin (II) and 1 , 3-Dianincprcpanol-M »N, N ', N' -tetramethylene phosphine-; varz , 60982b / 08bO Chelate compounds of tin (II) and 1,3-propanediamine-N, N, N ¹ , N ^t -tetramethylene phosphonic acid, chelate compounds of tin (II) and o-acetamidobenzylamino-1 ^ N-dimethylene phosphonic acid, chelate compounds of tin (II ) and 2-pyridylamino-N, N'-dimethylene phosphonic acid, chelate compounds of tin (II) and o-toluidine- ^ N-dimethylene phosphonic acid, chelate compounds of tin (II) and 1-hydroxyethylidene-1,1-diphosphonic acid, chelate compounds of Tin (II) and ethylidene-1,1,1-triphosphonic acid, chelate compounds of tin (II) and 1-hydroxypropylidene-1,1-diphosphonic acid, ethylenediaminoborane and hydrazine borane is used. 10. color reversal development method according to claim 1 to 9, characterized in that the for Release of a development inhibitor capable of non-Kupplef in the first developer in an amount of about 1/300 to about 1/10 mole per mole of the coupler in the color photographic Silver halide reversal materials. 11. color reversal development method according to claim 1 to 9, characterized in that the for Release of a development inhibitor suitable non-coupler compound in the photographic emulsion of the reversal silver halide color photographic material in an amount from about 1/400 to about 1/2 mole per mole of coupler in the photographic emulsion. 609825/0850