DE2431223A1 - COLOR PHOTOGRAPHIC MULTILAYER MATERIAL - Google Patents

Description

PR. E. WIEGAND DtH.-ING. W. NIcMA ^ N DR. M: KÖHLER DIPL-ING. C. GERNHARDT

MÖNCHEN HAMBURG

TELEPHONE: 55547 « TELEGRAMS! CARPATENT

8000 MUNICH 2, MATHILDENSTRASSE12

W 42 062/74 - Ko / Yes

June 28, 1974

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

Multilayer color photographic material

The invention relates to a multilayer color photographic material with improved color reproducibility, which color images with uniform quality in color development supplies. In particular, the invention relates to a multilayer color photographic material which is used in High temperature development is not developed unevenly,

According to the invention there is provided a multilayer color photographic material indicated which one carrier with at least

409882/1091

a photosensitive emulsion layer thereon which is an interlayer color correction coupler or a contains organic accelerators for the interlayer inter-image effect or the under-cut inter-image effect, a colloidal one A layer for adsorbing an organic development inhibitor, the colloid layer being silver halide grains which practically does not develop in color development on the photosensitive emulsion layer or between the photosensitive emulsion layer and includes the carrier. The provision of this colloid layer increases the color reproducibility of the color photographic material and the color photographic material can be used at a higher temperature without causing development trouble to be developed.

A multilayer color photographic material usually has on a support a blue-sensitive emulsion layer containing a yellow coupler mainly for blue Light (BL) sensitive, a green sensitive emulsion layer containing a magenta coupler and mainly is sensitive to green light (GL), a red-sensitive emulsion layer which contains a cyan coupler and mainly sensitive to red light (RL), intermediate layers (ML), filter layers (FL) used for adsorption of Ultraviolet light and visible light in a specific wavelength range are capable of forming an antihalation layer (AHL), a protective layer (PL) and other photosensitive emulsion layers containing various couplers and contain different spectral sensitivity distributions depending on the purposes.

Various attempts have been made to improve color reproducibility of multilayer color photographic materials.

409882/1091 *

■■ "■ - ■ 3 - -

2A31223

In the first attempt an organic compound, which increases the interlayer inter-image effect is applied. In one such attempt, it is known, for example, to use an organic heterocyclic compound with a Use an oxo group or a thioxo group. Such connections are for example in the German Offenlegungsschriften 2 043 943 and 2 043 944 indicated *

A second attempt will connect to a Mercapto group or a thioether bond is used. Examples such compounds are 2-mercaptobenzotriazole, ß-hydroxyethyl isothiouronium nitrate, 2,3-dimethylthiazolium salts, 1- (2-mercaptoethyl) -1,4,4-trimethylpiperidinium salts and 2-thioxobenzotriazole. These connections are in detail for example in US Pat. No. 3,536,487 and US Defensive Publications T 909 022 and T 909 023. give.

A third attempt uses a colored coupler.

A fourth attempt becomes an uncolored coupler used for interlayer color correction. Such uncolored couplers are disclosed in U.S. Patent 3,632,345 and U.S. patent applications Serial No. 467 539 dated May 6, 1974 and serial no. 454 525 of March 25, 1974.

On a fifth attempt, the halogen composition is in particular, the density distribution of the Si3b er iodide in the light-sensitive silver halide emulsion in each Emulsion layer of a multilayer color photographic material controlled as described in U.S. patent application serial no. 454 525 of March 25, 1974. The effect on that however, the fifth attempt is lower than the experiments listed above.

On a sixth attempt, a hydroquinone derivative is used used for interlayer color correction. This ver

409882/1091

Coils are disclosed in U.S. Patent Application Serial No. 461 087 dated April 15, 1974.

These attempts can effectively improve the color reproduction of multilayer color photographic materials however, on the other hand, it also gives rise to serious errors.

A first error exists with regard to the so-called interlayer inter-image effect or the under-cut inter-image effect, namely the effect that a development inhibitor is released at the beginning of development and diffuses into the adjacent layer to inhibit the development of the adjoining layer, that is, the released inhibitor diffused into a developer through the group of photosensitive emulsion layers for inhibiting development within an unnecessarily wide range, so as to result in the initiation of uneven development. The latter defect also lowers the quality of the developed color images. Therefore, in order to improve the effects so that the desired best color reproduction is obtained, the working range of the released development inhibitor must be limited to only the area between those photosensitive emulsion layers for which an interlayer interimage effect is obtained with each other. The first defect listed above occurs when the first, second, third, fourth and sixth attempts, particularly the fourth attempt, are used to improve the color reproduction of multilayer color photographic materials, and furthermore, this defect occurs to an even greater extent when rapidly Development for color photographic materials is applied at temperatures greater than about 3CPC . On the other hand, it is known that if the fifth experiment mentioned above is used, the interlayer inter-image effect occurs favorably even in the high temperature development.

409882/1091

The second flaw is that if the first, second, fourth and sixth attempts listed above can be used to improve the color reproduction of a multilayer color photographic material, the quality of the images obtained with a developer which has been used repeatedly, much inferior to that Quality of the images obtained with the fresh developer were is. On the other hand, if the fifth attempt is used, it is known that the inter-picture effect between the two is known remarkably occurs even in the case of using a developer which has been used repeatedly. Of the deleterious influence on the image quality due to the development inhibitor released in the developer, if color photographic Multi-layer materials with which the first, second, third, fourth and sixth attempt applied to be developed differs from the case of the development-des multilayer color photographic material to which the fifth attempt was applied. It is known that the Iodide ion practically entirely from undeveloped silver halide grains is captured by a replacement reaction and thus diffuses less into the developer.

One object of the invention is to improve the errors that occur if the above first, second, third, fourth and sixth attempts to improve the color reproduction of multilayer color photographic materials can be applied.

Another object of the invention is a color photographic one Multi-layer material which shows improved color reproducibility and which has the ability for treatment using high-temperature, high-speed treatment at temperatures higher than 3CPC without uneven development occurring.

409882/1091

These and other objects of the invention will become apparent from the following description.

The objects of the invention can be achieved by using in a multilayer color photographic material which a support having thereon at least one photosensitive emulsion layer which is an interlayer color correction coupler or contains an organic accelerator for the interlayer interimage effect, a colloid layer for adsorbing an organic development inhibitor, this colloid layer contains silver halide grains which are useful in color development do not become devolatilized, on the photographic emulsion layer or between the photographic emulsion layer and the carrier is formed.

The invention thus results in a multilayer color photographic material which has a support at least one photographic emulsion layer thereon, those an interlayer color correction coupler or an organic accelerator for the interlayer cht interpicture effect, and a colloid layer for Adsorption of an organic development inhibitor, this colloid layer containing silver halide grains, which practically not developed during color development, on the photosensitive emulsion layer or between the photosensitive emulsion layer and the support.

Figs. 1 to 3 show layered structures for embodiments of phot ographisehen materials according to the invention as described in Examples 1 to 3.

Figures 4 through 7 show graphical representations of the red filter density and the green filter density of embodiments of the photographic materials according to the invention and of photographic materials for comparison as described in the

409882/1091

Examples 1 and 2 are given.

According to a preferred embodiment of the invention has the multilayer color photographic material on one Carrier at least two light-sensitive emulsion layers, which result in images with practically different colors from each other in color development, and at least one of these photosensitive emulsion layers contains an interlayer color correction coupler or an organic one Accelerator for the interlayer interimage effect, as well as an organic colloid layer for adsorption an organic development inhibitor, which silver halide grains which are practically not developed upon color development on the light-sensitive emulsion layer or between the photosensitive emulsion layer and the wearer.

The interlayer color correction coupler used in the present invention is a coupler corresponding to FIG U.S. patent application serial no. 467 539 of May 6, 1974, i.e. a coupler which provides an interlayer interimage effect and consequently the function of "color correction" shows «Preferred interlayer color correction couplers are those described in US patent application SerM. 454 525 of March 25th 1974 listed couplers and include the so-called DIR couplers or development inhibitor-releasing couplers.

In particular, the couplers of the general formula (I) can be used as the interlayer color correction couplers according to the invention be used:

Cp-Z (I)

wherein Cp is a coupler residue which couples with the oxidation product of a primary aromatic amine as a developing agent, and Z is an organic group which is present in the Coupling reaction with the oxidation product of the primary

409882/1091

aromatic amine released as a developing agent, mean, this organic group after the release diffuses with inhibition of development.

The coupler residue indicated by Cp may be a 4-equivalent coupler commonly used for color photographic materials be. Examples of such couplers are 5-pyrazolone couplers, pyrazolobenzimidazole couplers, cyanaeetylcoumarone couplers, Indazolone couplers, acetylacetanilide couplers, pivaloylacetanilide couplers, acryloylacetamide couplers, naphthol couplers and phenolic couplers. Examples of such coupler residues are those listed in the following US patents the coupler:

Yellow: U.S. Patents 3,277,155, 3,415,652, 3,447,928, 3 408 194, 2 875 057, 3 265 506, 3 409 439, 3 551 155, 3,551,156, 3,582,322 and the like.

Magenta: U.S. Patents 2,000,788, 2,983,608, 3,006,759, 3,062,653, 3,214,437, 3,253,924, 3,311,476, 3,419,391, 3,419,808, 3,476,560, 3,582,322 and the like. Cyan: U.S. Patents 2,474,293, 2,698,794, 3,034,892, 3,214,437, 3,253,924, 3,311,476, 3,458,315, 3,582,322, 3,591,383, and the like.

Examples of groups corresponding to Z are heterocyclic Radicals which correspond to the 1-triazole ring to 1-diazole ring U.S. patent application serial no. 454 525 of March 25, 1974 form 2-benzotriazole radicals according to the US patent 3,617,291, aryl monothio groups and heterocyclic thio groups. Specific examples of heterocyclic rings "are tetrazole groups, Triazinyl groups, Triazoly groups, OxaζοIy groups, Imidazolyl groups, oxadiazolyl groups, thiadiazolyl groups, benzothiazolyl groups, pyrimidyl groups and pyridiny groups. These groups are described in detail, for example, in U.S. Patents 3,617,291, 3,622,328, 3,632,373, 3,620,745, 3,620,747 and 3,615,506 and British patents

403882/1091

1 201 110, 1 261 0611, 1 269 075 and .. 1 269 073. In particular, radicals corresponding to the general formulas (Ia), (Ib) and (Ic) can be used according to the invention

_N 'N -N N -N L

V / \ J

wherein V is a benzene aromatic ring or a heterocyclic ring aromatic ring with at least one nitrogen atom and L represents a methine group or a methine derivative group. The group indicated by V can be substituted with groups be like amino groups, acylamino groups, halogen atoms, Alkyl groups, nitro groups, alkoxy groups, alkylthio groups and aryl groups.

Examples of ZH are shown in U.S. Patents 3,185,570, 3,244,521, 3,499,761, 3,473,924, 3,575,699 and 3,554,757, British patents 919 061 and 1,031,262, French patents 1,346,227 and 1,594,983 and German Patent 1,294,188.

The expression "organic accelerators for the interlayer Inter-picture effect or under-cut inter-picture effect "such as As used herein, it refers to an organic compound that is selectively incorporated into a specific photosensitive emulsion layer is incorporated and the interlayer inter-picture effect or the under-cut inter-image effect on another adjacent photosensitive emulsion layer during development and these organic compounds are described in U.S. Patent 3,536,487, U.S. Defensive Publication

409882/1091

T 909 022 and T 909 023 and German Offenlegungsschriften 2,043,943 and 2,043,944.

For example, such organic accelerators are compounds corresponding to the following formula (II)

< ^{C = C} \

T /

R ₁ 0

wherein X is a sulfur atom, an oxygen atom, a selenium atom or a group = N-FU, in which R-, a hydrogen atom, a aliphatic group, e.g. an alkyl group such as methyl group, hydroxyethyl group, sulfopropyl group, carboxyethyl group, Methoxyethy! Group, chloroethyl group, benzy! Group or a Alkenyl group such as an allyl group and the like, an aryl group, for example an aryl group such as a phenyl group, hydroxyphenyl group, Methylphenyl group, methoxyphenyl group, chlorophenyl group and the like, or a heterocyclic group such as a pyridyl group and the like, R 1 and R p a hydrogen atom, an aliphatic group, for example an alkyl group such as a methyl group, hydroxyethyl group, Sulfopropyl group, carboxyethyl group, methoxyethyl group, Chlorethyl group, Benzy! Group and the like. Or an alkenyl group, for example, an allyl group and the like., Or a Aryl group, for example an aryl group such as phenyl group, hydroxyphenyl group, methylphenyl group, methoxyphenyl group, Chlorophenyl group and the like and Q a non-metal atom grouping to form a heterocyclic ring, as it is usually used as a nucleus for a cyanine dye, for example a 4-pyridyl, 2-quinolyl, Oxazolyl, benzoxazolyl, imidazolyl, benzimidazolyl,

409882/1091

Thiazolyl, Benzthiazoly! Group and the like. Mean, or the general formula (III)

-V

(HD

ι ■■■

R ₂

wherein Q and R _{2 have} the same meaning as Q and R ^ in the general formula (II).

Furthermore, mercapto compounds such as 1-phenyl-5-mercaptotetrazole, 2-methylthio-5-mercaptothiadiazole, 2-mercapto-5-sulfobenzothiazole, 1-methyl-2-mercapto-5-sulfobenzimidazole ■ and the like., Usable.

If the releasable group inhibiting development, i.e., Z in the general formula (I), in the interlayer color correction coupler is a mercapto radical, the mereapto group is strongly adsorbed on the light-sensitive silver halide, so that the interlayer color correcting effect is quite weak and the development inhibiting effect in the emulsion layer occurs strongly. On the other hand, if the releasable group inhibiting development is a residue corresponding to the general Is formulas (Ia), (Ib) or (Ic), the interlayer color correction effect occurs strong on. In this case, the valuable effect of the colloid layer appears to adsorb the organic Development inhibitor to a remarkable extent.

The organic accelerator for the interlayer inter-image effect, in particular the organic accelerators corresponding to the general formulas (II) and (III) shows a high interlayer interpicture effect or under-cut

409882/1091

Inter-image effect in rapid development at temperatures higher than 3CT ⁵ C, but on the other hand uneven development occurs. The uneven development is prevented by providing a colloid layer for adsorbing the organic development inhibitor according to the invention. The interlayer color correcting effect is also increased due to the use of the organic accelerator and the interlayer color correcting coupler. The colloid layer for adsorbing the organic development inhibitor prevents uneven development in this case. "Uneven development" is explained in detail in Example 1.

The colloid layer for adsorbing the organic development inhibitor, as used in the present invention is a colloid layer having the function of fixing the development inhibitor residue or the development inhibitor residue released from the interlayer color correction coupler upon development in developing the silver halide grains from the organic accelerator for the interlayer interimage effect released development inhibitor by adsorption, which on the silver halide grains in the light-sensitive Emulsion layer has been absorbed, thereby preventing the development inhibitor residue from being released into the developer will. The colloid layer also has the function of adsorbing the development once released in the developer. inhibitor residue, i.e. the function of removing the development inhibitor residue from a developer or the appropriate control of the diffusion of the development inhibitor residue in the developer in the event a development inhibitor residue is released into the developer. Therefore it is preferred that the colloid layer according to the invention is provided on or under the photosensitive emulsion layer group, i.e., between the photosensitive layer group and the support.

409882/1091

The colloid layer can contain grains of silver halide and so on an adsorbent, such as colloidal silica, aluminum hydroxide, colloidal metal such as colloidal silver, colloidal gold and the like. The appropriate amount of adsorbent is in the range of about 0.01 to 10 g / m, preferably 0.1 to 5 g / m. It is preferred that the silver halide grains fine grains are, making them a large one Adsorption capacity and adsorption capacity and further that the amount of iodide ions in the silver halide grains is low. It is particularly preferred that the silver halide grains superfine grains with a mean grain size less than about 0.2 microns, for example about 0.005 to 0.2 microns, preferably 0.01 to 0.1 microns. The appropriate amount of silver halide grains in the colloidal grains ranges from about 0.01 to 30 g / m 2, preferably 0.1 to 5 g / m .. In order to continue the strong adsorptive power in the To retain developer, it is preferred that the silver halide grains are not developed by the developer and do not dissolve in the developer. Therefore, silver halide grains, which have not been chemically aged or ripened or silver iodobromide grains with a content of less than 10 MoISK) silver oodid preferred. Silver chloride grains are used for not preferred this purpose.

One of the features of the invention resides in the position of the colloid layer to adsorb the organic development inhibitor. In one embodiment of the invention, the Colloid layer between the light-sensitive emulsion layer, those of the interlayer color correction coupler or the organic accelerator for interlayer interimage effect and the photosensitive emulsion layer for which the interlayer interimage is provided, appropriate. In this case the colloid layer lowers the the light-sensitive emulsion layer under the colloid

409882/1091

Layer released development inhibitor to control the working area of the development inhibitor in planar direction and to prevent uneven development from occurring.

In a second embodiment of the invention, the Colloid layer attached under the photosensitive emulsion layer, i.e. on the support side of the photosensitive Emulsion layer. In this case, the colloid layer lowers the development inhibitor released on the photosensitive emulsion layer and prevents the further diffusion of the development inhibitor and the propagation of the development inhibitor in a further planar direction, so that an uneven Development is prevented. It also catches due to the formation of the colloid layer on the back of the carrier the colloid layer incorporates the development inhibitor released into the developer, thereby preventing the developer from getting is contaminated by the development inhibitor.

Both in the first embodiment and in the second embodiment according to the invention, it is preferred that the silver halide grains employed in the colloid layer have an average grain size of less than about 0.2 microns and consist of silver iodobromide or silver iodide, which dissolve only with difficulty in the color developer.

The colloid layer of the invention is preferably used in

an amount of about 0.01 to 10 g, preferably 0.1 to 5 g

2
Silver wound up per m.

It has been found that when the work area is in a planar direction, the development-released development inhibitor is too wide, the so-called "uneven development", i.e. a Mackie line-like unusual Color unevenness occurs in a fine color area. This disadvantage can be caused by the arrangement of the paint layer of the invention can be improved.

409882/1091

According to the invention, not only can the "uneven Development "can be prevented, but also the unevenness of the development process as a result can be greatly increased can be improved, since the method of the invention, the release of the organic development inhibitor in the developer, which is a major factor in developer contamination represents, can be prevented *

Another feature of the invention is a high processing temperature. The term "high temperature development" used according to the invention means development at a temperature of more than about 30 ^° C., preferably about 30 ^° C. to about 40 ^° C. or 60 ^° C. or higher. It is known from Japanese Patent Specification 28 836/1970 and French Patent Specification 2132675 that the iodine ion released during development is very easily captured by silver chloride or SiI overbromide in the silver halide grains in the adjacent silver halide emulsion layer due to a displacement reaction, whereby the possibility of Release of the organic development inhibitor into the developer is decreased and the displacement reaction is accelerated at higher temperatures to prevent the release of the organic development inhibitor into the developer. On the other hand, the releasable group of monothiotype disclosed in U.S. Patent 3,227,554 causes chemical adsorption to the silver halide grains in an adjacent silver halide emulsion, which is commonly used to form a silicon bermercapto compound, and at higher temperatures, chemical adsorption tends to accelerate to reduce the release of frees usable group in the developer. However, the interlayer color correction couplers, particularly, have the couplers having the releasable groups represented by the general formulas (Ia), (Ib) and Ic) and the organic development accelerator

40988 2/1091

for the interlayer interimage effect, especially the compounds of the general formula (II) or (III) (in which, however, R _{2 is} substituted with a substituent), a weaker adsorption capacity for the silver halide used in the photographic silver halide emulsion layer than the above iodine ions and mercapto compounds. Thus, interlayer color correction couplers become easily diffusible and are quickly released in the developer when the temperature of the developer becomes high. In such a case, the effect of using the colloid layer for adsorbing organic development inhibitor according to the invention is remarkable.

The couplers used in the present invention can be 4th equivalent couplers or 2-equivalent couplers and in particular the couplers of the general formulas (IV), (V) or (VI) described below are suitable:

R ₃ -C-CH-Z ₁

N C = O (IV)

where PU is a primary, secondary or tertiary alkyl group, for example a methyl group, a propyl group, an n-butyl group, a tert-butyl group, a hexyl group, a 2-hydroxyethyl group, a 2-phenylethyl group, a pentadecyl group and the like, an alkoxy group such as a methoxy group, an ethoxy group, a benzyloxy group and the like, an aryloxy group such as a phenoxy group, an aryl group, e.g. a phenyl group, a 2,4-di-tert-phenyl group and the like., a heterocyclic ring residue, e.g. a quinoliny group, a piperidyl group, a benzofuranyl group

409882/1091

group, an oxazolyl group and the like, an amino group such as a methylamine) group, a diethylamino group, a phenylamino group, a tolylamino group, a 4- (3-sulfobenzamino) anilino group, a 2-chloro-5-acylaminoanilino group, an S-chlorine -S-alkoxycarbonylanilino group, a 2-trifluoro, methylphenyl group and the like, an acylamino group such as an alkylcarbonamido group such as an ethylcarbonamido group and the like, an arylcarbonamido group, a heterocyclic carbonamido group such as a benzothiazolylcarbonamido group and a sulfonamido group, a sulfonamido group The like. Or an ureido group, e.g. an alkylureido group, an arylureido group, a heterocyclic ureido group and the like., R ^ an aryl group, e.g. a naphthyl group, a phenyl group, a 2,4,6-trichlorophenyl group, a 2-chloro-4,6- dimethylphenyl group, a 2,6-dichloro-4-methoxyphenyl group, a 4-methylphenyl group, a 4-acylaminophenyl group, a 4-alkylamine phenyl group, a 4-trifluoromethylphenyl group, a 3,5-dibromophenyl group and the like, a heterocyclic group such as a benzofuranylbenzothiazolyl group, a quinolyl group and the like. Or a primary, secondary or tertiary alkyl group such as a methyl group, an ethyl group, a tert .-Butyl group, a Benzy! Group and the like. And Z ^ a hydrogen atom or a group releasable upon color development such as a thiocyano group, an acyloxy group, an aryloxy group, an alkoxy group, an alkoxycarbonylöxy group, an aryloxycarbonyloxy group, an amino group such as an alkylamino, arylamino, alkylsulfonamido, arylsulfonamido, arylamido group, cyclic imino, cyclic imido group and the like., an arylazo group and a heterocyclic azo group, for example according to US patents 3,419,391, 3,252,924, 3,311,476 and 3 227 550 and U.S. Patent Applications 461 204 and

409882/1091

471 639

R ₁ - - CO - CH - CO - NH - Rf-
⁵ «6 _(v)

^Z 2

where Rj- is a primary, secondary or tertiary alkyl group, for example a tert-butyl group, a 1,1-dimethylpropyl group, a 1,1-dimethyl-1-methoxyphenoxymethyl group and the like, or an aryl group, for example a phenyl group, an alkylphenyl group such as a 2-methylphenyl group, a 3-octadecylphenyl group and the like. and an alkoxyphenyl group such as a 2-methoxyphenyl group, a 4-methoxyphenyl group and the like, a halophenyl group, a 2-chloro-5-alkylcarbamidophenyl group , a 2-chloro-5- [α- (2,4-di-tert-aminophenoxy) -butyramido] -phenyl group, a 2-methoxy-5-alkylamidophenyl group, a 2-chloro-5-6ulfcnamidophenyl group and the like., Rg is a phenyl group, for example a 2-chlorophenyl group, a 2-halo-5-alkylamidophenyl group, a 2-chloro-5- [a- (2,4-di-tert.-amylphenoxy) acetamido] phenyl group, a 2- Chloro-5- (4-methylphenylsulfonamido) -phenyl group, a 2-methoxy-5- (2,4-di-tert-amylphenoxy) -acetamidophenyl group and the like and Zp a hydrogen atom or the like a group releasable on color development, such as a halogen atom (especially a fluorine atom), an acyloxy group, an aryloxy group, a heterocyclic aromatic carbonyloxy group, a sulfimido group, an alkylsulfoxy group, an arylsulfoxy group, a phthalimido group, a dioxazolidoylidynyl group, a dioxazolidoylidynyl group, a dioxazolidoylidynyl group, a dioxazolidoyldynyl group, a dioxazolidynyl group, an acyloxy group, an aryloxy group ! group, a Dioxymorpholinogruppe and the like., for example according to US patents 3,227,550, 3,253,924, 3,277,155, 3,265,506, 3, 408 and 3,415,652, French Patent 1,411,384, British patents 944,490 , 1040 710 and 1 118 028,

409882/1091

DT-OS 2 057 941, 2 163 812, 2 213 461 and 2 219 917 and of US patent application 469,923 »mean

OH

(VI)

(V)

where R ₁ ? a substituent used for cyan couplers such as a carbamyl group such as an alkylcarbamyl group, an arylcarbainyl group such as a phenylcarbamyl group and the like, a heterocyclic carbamyl group such as a benzylthiazolylcarbamyl group and the like, a sulfamyl group such as an alkylsulfamyl group, e.g. for example, a phenylsulfamyl group and the like, a heterocyclic sulfamyl group and the like, an alkoxycarbonyl group, an aryloxycarbonyl group and the like, R _{Q is} an alkyl group, an aryl group, a heterocyclic group, an amino group, an amido group, e.g. ., a sulfamido group, a sulfamyl group "or a garbamyl group, Rg, R ^ q and R>jj" die

409882/1091

each have the same meaning as Rg and additionally represents a halogen atom or an alkyl group, and Z- represents a hydrogen atom or one releasable upon color development Group such as a halogen atom, a thiocyano group, a cycloimido group such as a maleido group, a Succinimido group, 1,2-dicarboxyimido group and the like. mean an arylazo group or a heterocyclic azo group.

To make the coupler nondiffusible, a Group with a hydrophobic residue with about 8 to 32 carbon atoms introduced into the coupler molecule. One of those The rest is referred to as the "ballast group". The ballast group is attached to the coupler core directly or through an imino bond, an ether bond, a carbonamido bond, a sulfonamido bond, an ureido bond, an ester bond, an imido bond, a carbamoyl bond, a sulfamoyl bond, and like bound.

Examples of suitable ballast groups are given in the specific examples of the couplers given below of the invention described.

Examples of the ballast groups are specifically explained below:

(1) Alky! Groups and alkenyl groups such as

₂₂ ^ £ 1225 1633 i7 ^ 3

(2) Alkoxyalkyl groups such as - (CH ₂ UO-CCH ₂ ) ₇ CH ₃ and - (CH ₂ ), OCH ₂ -CH- (CH ₂ U-

C ₂ H ₅

as in Japanese Patent Publication No. 27 563/1964 described.

(3) alkylaryl groups such as

409882/1091

(4) alkylaryloxyalkyl groups such as

G ₂ H 5
CHO

C ₅ H ₁₁ Ct), -

C ₅ H ₁₁ Ct),

C ₅ H ₁₁ Ct)

C ₅ H ₁₁ Ct)

CH ₃
i
ι F. / ₅ H. 3iCn) -CH ₂ O- ^) --C ₅ Hn CH ₃ V = CH ₃ -C-CH 3 CH ₂ -C I ₁ ed Ct) > Ci

CJl

C ₂ H

C ₅ Hi ₁ Ct)

C ₅ HnCt)

(5) Acylamidoalkyl groups such as "for example

.COCi ₅ H ₃₁

-CH ₂ CH ₂ NC % -CH ₂ CH ₂ N C4H9

COCi ₃ H ₂₇ C ₃ H ₇

-CH ₂ CH ₂ NH COCH ₂ CH ₂ N:

-COC1 3H _{2 7} C ₃ H ₇

and

409882/1091

as described in U.S. Patents 3,337,344 and 3,418,129.

(6) alkoxyaryl groups and aryloxyaryl groups, as in for example

• V V

° -V \ ci2H ₂₅ (n) ₅

(7) Residues with a long-chain aliphatic alkyl or an alkenyl group together with a water-solubilizing carboxyl or sulfo group, such as, for example

-CH-CH = CH-C ₁₆ H ₃₃ : -. T -CH-C ₁₆ H ₃₃

i -T-

CH ₂ COOH and SO ₃ H

(8) Alkyl groups substituted with an ester group such as

-CH-C ₁₆ H ₃₃ (n) - '-CH ₂ -CH ₂ -COOC ₁₂ H ₂ 5 (n) COOC ₂ H ₅ ^Xm

(9) Alkyl groups substituted with an aryl group or a heterocyclic alkyl group such as

CH ₂ -CH ₂ -V ^ NHCOCH ₂ CH-C ₁₈ H ₃ SCn)

COOCH ₃

Ij and

-CH ₂ CH ₂ K ⁷ > -Μ

η ^^ CisHsvCn) O

A098 82nd/1091

(10) aryl groups substituted with an aryloxyalkoxycarbonyl group such as

C ₅ Hu (t)

Furthermore, examples of the invention materials used, although the invention is not limited to these examples.

Yellow coupler:

(1) cc- {3- [oc- (2,4-Di-tert -amylphenoxy) -butyramido] -benzoyl) -2-methoxyacetanilide

(2) α-Acetoxy-α-3- [γ- (2,4-di-tert-amylphenoxy) -butyramido] -benzoyl-1-methoxyacetanilide

(3.) N- (4-Anisoylacetamidobenzenesulfonyl) -N -benzyl-N-toiuidine

(4) α- (2,4-Dioxo-5,5-dimethyloxazolidinyl) -a-pivaloyl-2-chloro-5-Ca- (2,4-di-tert-amylphenoxy) butyramido}; -acetanilide

(5) a- (4-Carboxyphenoxy) -a-pivaloyl-2-chloro-5-ία- (2,4-di-tert-amylphenoxy) -butyramido ^ acetanilide

(6) a- {3- (i-Benzyl-2,4-dioxo) -hydantoin} -oc-pivaloyl ^ -chloro-S- {a- (2,4-di-tert-amylphenoxy) -butyramidoj acetanilide

(7) et- (4-methoxybenzoyl) -α- (3,5-dioxomorpholino) -5- € γ- (2,4-di-tert-amylphenoxy) butyramido} -2-chloroacetanilide

Magenta Coupler:

(8) 1- (2,4,6-Trichlorophenyl) -3- [3- (2,4-di-tert-amylphenoxyacetamido) benzamido] -5-pyrazolone

(9) 1- (2,4,6-Trichlorophenyl) -3- {3- [a- (2,4-di-tert-amylphenoxy) acetamido ] -benzamidol ^ -acetoxy ^ -pyrazolone

409882/1091

(10) 1- (2,4,6-Trichlorophenyl) ^ - tridecylamido ^ - (4-hydroxyphenyl) -azo-5-pyrazolone

(11) 1 - (2,4,6-Trichlorophenyl) -3 - [(2-chloro-5-tridecanoylamino) anilino] -5-pyrazolone

(12) 1- (2,4,6-Trichlorophenyl) -3- (2-chloro-5-tetradecyloxycarbonyl) -anilino-4- (1-naphthylazole) -5-pyrazolone

(13) 1- (2,4-Di-chloro-6-methoxyphenyl) -3 - [(2-chloro-5-tridecanoylamino) anilino] ^ - benzyloxycarbonyloxy-S-pyrazolone

(14) 1- (2,4,6-Trichlorophenyl) -3- [3 - ((2,4-di-tert-amylphenoxy) acetamido) benzamido] -4-piperidino-5-pyrazolone

(15) 1- (2,4,6-Trichlorophenyl) -3- [2-chloro-5- {a- (2,4-di-tert-amylphenoxy) -butyramido 3 anilino] -4-N-phthalimido-5-pyrazolone

(16) 1- (2,4,6-Trichlorophenyl) -3- (2-chloro-5-tetradecylaminoanilino-4- (3-methyl-4-hydroxyphenylazo) -5-pyrazolone

(17) 1-Hydroxy-N- [γ- (2,4-di-tert-amylphenoxypropyl) J-2-naphthamide

(18) 1-Hydroxy-4- [2- (2-hexyldecyloxycarbonyl) phenylazo] -2- [N- (1-naphthyl)] naphthamide

(19) 1-Hydroxy-4-chloro-N- [α- (2,4-di-tert-amylphenoxy) butyl] -2-naphthamide

(20) 5-methyl-4,6-dichloro-2- [α- (3-n -pentadecylphenoxy) butylaminophenol

(21) 1-Hydroxy-4- (2-ethyloxycarbonylphenylazo) -N- (2-ethylamyl) 2-naphthamide

Undyed Intermediate Color Correction Couplers:

(22) α-Benzoyl-α- (2-benzothiazolylthio) -4- [N- (γ-phenylpropyl) -N- (4-toly1) sulfamyl] -ac etanilide

(23) 1-14- [γ- (2,4-Di-tert -amylphenoxybutyramido) ^ phenyl] -3-piperidinyl-4- (1-phenyl-5-tetrazolylthio) -5-pyrazolone

(24) 1- (2,4,6-Trichlorophenyl) -3-f4- [α- (2,4-di-tert-amylphenoxy ) -butyramido] -anilinoj -4- (1-phenyl-5-tetrazolylthio) -5-pyrazolone

409882/1091

(25) ί- [4- a- (2/4-di-tert-amylphenoxy) -acetaraido phenyl] -3-.inethyl-4- (5- or 6-bromo-1-benzotriazole) -3-pyrazolon '

(26) 5-Methoxy-2- [α- (3-n -pentadecylphenoxy) butyrainido] -4- (1-phenyl-5-tetrazolylthio) phenol

(27) N- {α- (2,4-Di-tert-amy! Phenoxy) -acetyl ^ -w ~ (1-phenyl-5-tetrazolylthio) -m-aminoacetophenone

(28) a-pivaloyl-> a- (5- or 6-bromo-1-benzotriazolyl) -5- [a- (2,4-di-tert-amy! Phenoxy) -propionamido] -2-chloro- acetanilide

(29) a- (Methoxybenzoyl) -a- (5- or 6-nitro-1-benztriazolyl) -5- {a- (2,4-di-tert-.-Amy! Phenoxy) -butyramido} -2-chloro-acetanilide

(30) a- (4-Stearyloxybenzoyl) -a- (5- or 6-bromo-i-benzotriazolyl) 2-methoxyacetanilide

(31) 1-Hydroxy-4- (1-phenyltetrazolylthio) -N - {(2-chloro-5-hexad cyloxy) phenyl} · -2-naphthamide

(32) 1 -Benzyl ^ -Tr ^ -chlor-S-tetradecanamido) -anilino} -4- (5- or 6-methyl-1-benzotriazolyl) -5-pyrazolone

(33) 1- [4- {a- (2,4-Di-tert-amy! Phenoxy) -acetamido ^ phenyl] -3-ethoxy-4- (5- or 6-bromo-benzt2 (zolyl) -5-pyrazolone

Specific examples of the organic accelerator for the interlayer inter-picture effect are as follows reproduced, although the invention is not limited only to these examples.

(34) 5- (3-Ethyl-2-benzothiazolylidene) -3-bericylrhodanine (35 ") 5- [3-T-sulfopropyl) -2-benzoxazolylidene.] -3-cyclohexylrhodanine

(36) 5- (3-Methyl-2-benzoselenazolylidene) -3- (γ-sulfobutyl) rhodanine "

(37) 5- [3- (β-Hydroxyethyl) -β-naphthoxazolylidene] -1-phenyl-2-thiohydantoin

(38) 2-Thipxo-3-ethyl-benzothiazole

(39) 2-mercapto-5-methyl-benzothiazole

(40) 2-Thioxo-3-n-propyl-benzoxazole

09.8-8 2/1 09 1

(41) 1, S-Di-n-propyl-Z-thioxo-benzimidazole (42) N-methyl-2-thioxo-6-'chloro-quinoline

The couplers used according to the invention are generally classified into the so-called Fischer-type couplers having a water-soluble one Group such as a carboxyl group, a hydroxyl group and a sulfo group and hydrophobic Classified coupler.

The couplers used in the present invention can be added to a silver halide emulsion or a hydrophilic colloid using any conventional technique. For example, a method for dispersing the coupler as a mixture of the coupler and a high-boiling (above about 17 (K!) Organic solvent such as dibutyl phthalate, tricresyl phosphate, a fatty oil that is liquid at normal temperature, a wax, a higher fatty acid or their esters according to U.S. Patents 2,3o4,939 and 2,322,027; a method for dispersing the coupler as a mixture with a low-boiling organic solvent (below about 17CKl) or a water-soluble organic solvent and a method for dispersing the coupler as this mixture along with a high-boiling organic solvent such as described in U.S. Patents 2,801,170, 2,801,171 and 2,949,360 and a method of dispersing the coupler when the coupler itself has a sufficiently low melting point (e.g., lower than 75 ^° C) can be used alone or as a mixture thereof with others n couplers, for example a colored coupler or an uncolored coupler as described in DT-PS 1,143,707 can be used.

As the dispersing aid which can be used in this case, an anionic surfactant such as sodium alkylbenzenesulfonate, Sodium octyl sulfosuccinate, sodium

409882/1091

dodecyl sulfate, sodium alkyl naphthalene sulfonate, a coupler Fischer type and the like, an amphoteric surfactant such as N-tetradecyl-NjN-dipolyethylene-α-betaine and the like. and a nonionic surfactant such as sorbitan monolaurate and the like. Can be used.

The coupler is usually used in an amount of about 1/100 to 2 per mole of silver halide used. The interlayer color correction coupler can be used alone or as a mixture with other couplers and the amount thereof is usually from about 1 to about 50 mole percent, preferably 5 to 20 mol% of the total amount in the photosensitive Emulsion layer used couplers.

The organic accelerator for the interlayer inter-image effect can be added as a solution in a water-miscible organic solvent such as methanol, ethanol, pyridine, methyl cellosolve and the like, or in water. The amount is usually from about 10 to about 10 ^J moles per mole of silver halide.

The silver halide emulsion used according to the invention is a fine dispersion of silver chloride, silver bromide, Silver chlorobromide, silver iodobromide and silver chloroiodobromide in a hydrophilic polymer. As the hydrophilic polymer, those commonly used in the field of photography used to be used in an advantageous manner ^ including Gelatin, a gelatin derivative such as an acylated gelatin, a graft gelatin and the like., Albumin, gum arabic, agar, a cellulose derivative such as hydroxyethyl cellulose, carboxymethyl cellulose and the like, a synthetic resin such as polyvinyl alcohol, polyvinyl pyrrolidone, polyacrylamide and the like. The silver halide can have a uniform grain size or a broad grain size distribution. Also lies Size, of the silver halide in the range of about 0.1 to about

409882/1091

3 microns. The silver halide emulsion can be used for any purpose a single nozzle method, a double nozzle method, or a combination of these methods, for example matured using an ammonia method, a neutralization method, an acid method and the like will.

The silver halide emulsion used as the photosensitive emulsion layer in the invention can be chemically sensitized such as by a gold sensitization method according to U.S. Patents 2,399,083, 3,597,856 and 2,597,915, a reduction sensitization method U.S. Patents 2,487,850 and 2,521,925, a sulfur sensitization method as disclosed in U.S. Patents 1,623,499 and 2,410,689, a sensitization method using metal ions other than silver according to U.S. Patents 2,566,263, 2,566,245, and 2,566,263, or a combination of these methods.

The silver halide emulsion can also be prepared using a spectral sensitization method generally used in Manufacture of color photographic materials used to be sensitized. For this purpose can be more suitable Manner, a sensitizing dye such as a cyanine dye or merocyanine dye according to US patents 2 526 632, 2 5o3 776, 2 493 748, 3 384 486, 2 933 390 and 2 937 089 can be used. According to the invention The silver halide emulsion used can also contain a stabilizer, such as, for example, a 4-hydroxy-1,3,3a, 7-tetraazaindene derivative and the like, an antifoggant such as a mercapto compound and a benzotriazole derivative, a coating aid, a hardening agent, a wetting agent, a sensitizer such as an onium derivative, e.g. a quaternary ammonium salt according to U.S. Patents 2,271,623 and 2,288,226 and also a polyalkylene oxide derivative disclosed in U.S. Patents 2 708 162, 2 531 832, 2 533 990, 3 210 191 and 3 158 484

409882/1091

keep. The silver halide emulsion can also act as a radiation preventive Contain dye.

Furthermore, the color photographic material of the invention is spellbinding Layers contain, such as a filter layer, a stain-containing layer, a colored layer, containing a hydrophobic dye and the like.

The silver halide emulsions used in accordance with the invention can be drawn onto various supports, such as a cellulose acetate film, a polyethylene naphthalate film, a polyethylene film, a polypropylene film, a glass plate, a baryta-coated paper, a resin-coated one Paper or a synthetic paper.

The photographic material according to the invention is treated with a color developer which contains a color developing agent, a p-phenylenediamine derivative and a p-aminophenol derivative contains. Examples of preferred p-phenylenediamine derivatives are p-amino-N-ethyl-N-ß- (methanesulfonamidoethyl) -m-toluid tnsesquisulfate monohydrate, Diethylamino-p-phenylenediamine sesquisulfite, p-Amino-HjiM'-diethyl-m-toluidine hydrochloride, p-Amino -N-äthy 1-N-ß -hy dr oxy äthylanilin- s es qui sulfate monohydrate and the like

The color photographic materials of the invention can be developed using developers generally used for developing conventional color negative or positive color photographic materials, color photographic papers and instant color photographic materials. For example, the color development processes described in the following references can be used: British Patent 1 203 316, US Patent 3,695,883, US Patent Applications 234 163 and 240 287, H. Gordon, The British Journal of Photography, pp. 559 ff (1954 ); ibid., 'page 440 ff., (1955) and ibid'. _t page 2 ff. (1956); .S-. Horwith, The British Journal-of Photography. Page 212 ff. (1960); E. Gehret, The British Journal of Photography , p

409882/1091

122 ff. _F (1960) and ibid. , Page 396 ff. (1965); J. Meech, The British Journal of Photography. Page 182 ff. (1959) and DT-OS 2 238 051. ·

The following examples serve to illustrate the invention without restricting it. Unless otherwise stated is, all parts, percentages, ratios and the like are based on weight.

example 1

Sample A illustrated in Figure 1 of the drawings was by drawing up a first layer, a second layer, a third layer, a fourth layer and a fifth Layer on a transparent cellulose triacetate film manufactured as a carrier. The coating composition and the manufacturing methods of the layers were as follows:

First layer (blue-sensitive emulsion layer): A mixture of 1 kg of a silver iodobromide emulsion (0.52 mol of silver and 6 mol% of iodine) and 600 g of emulsion (I) obtained by dispersing a solution of 100 g of coupler (4) in a mixture of 100 ml of dibutyl phthalate and 200 ml of ethyl acetate in 1 kg of an aqueous gelatin solution using 4 g of sodium dodecylbenzenesulfonate was prepared

drawn onto the carrier in an amount of 0.6 g of silver per m.

Second layer (grain-sensitive emulsion layer): 1 kg of a silver iodobromide emulsion (0.6 mol of silver and 6 mol% of iodine) was under. Using 2 χ 10 mol of sensitizing dye I and 6 χ 10 mol of sensitizing dye-II, and then the silver halide emulsion was sensitized with 600 g of Emulsion (II) by dispersing a solution of 600 g of Coupler (8) and Coupler (25) in a mixture of 100 ml of tricresyl phosphate and 200 ml of ethyl acetate in 1 kg of an aqueous 10bigen gelatin solution using 4 g of sodium dodecylbenzenesulfonate

409882/1091

. - 31 -

had been prepared, mixed to produce a coating composition for the second layer. The coating compound was then on the first layer in an amount of 0.9 g of silver

2
each m raised.

Third layer (adsorptive colloid layer);

1 kg of a silver halide emulsion made of super fine silver iodobromide grains (0.5 mol of silver, 2 mol ^ iodine, medium Grain size 0.05 micron) was applied to the second layer to a thickness of 3 microns (in an amount of 2Jg silver per m) as a colloid layer for adsorbing an organic development inhibitor of the invention raised.

Fourth layer (red sensitive emulsion layer);

1 kg of a silver iodobromide emulsion (the same as the silver halide emulsion used to form the first layer) was made with 4. χ 10- mol sensitizing dye III and 1 χ ΙΟ "- * mole of sensitizing dye IV spectrally sensitized. The silver halide emulsion was prepared with 450 g of Emulsion III, which was prepared in the same manner as Emulsion II using 100 g of Coupler (17), mixed, and the coating thus formed was applied to the third layer applied as a coating of 1.7 g silver per m.

Fifth layer (protective layer);

An aqueous gelatin solution became the fourth layer raised as a protective layer.

Sodium polyvinylbenzenesulfonate was also used as a thickener and sodium dodecylbenzenesulfonate as a surface-active agent Agent and the sodium salt of Z-Hydroxy ^ jG-dichloro-S-triazine as a hardening agent for gelatin to any of the above-described coating compositions in addition to those described above Components added.

The materials used to make Sample A were as follows;

409882/1091

Sensitizing dye I: anhydro-9'-ethyl-5.5 ^l dichloro-3,3'-disulfopropyloxacarbocyanine sodium salt

Sensitizing dye II: anhydro-5,6,6 ¹ , β'-tetrachloro-1,1'-diethyl-3,3'-disulfopropoxyethoxyethylimidazole carbocyanine hydroxide sodium salt

Sensitizing dye III: anhydro-5,5'-dichloro-3,3 ' -disulfopropyl-9-ethyl-thiacarbocyanine hydroxide-pyridinium salt

Sensitizing Dye IV: anhydro-9-ethyl-3.3 ^l di- (3-sulfopropyl) -4,5,4 ', 5' -dibenzothiacarbocyanine hydroxide triethylamine salt

Each of the samples A and B prepared as described above was exposed through a green light source using a step wedge, uniformly exposed through a red light source and developed ^{at 38 ° C. using the following steps.}

1st color development 3 min 15 sec

2. Bleaching 6 min 30 sec

3. Wash 3 min 15 sec

4. Fixation 6 min 30 sec

5. Wash 3 min 15 sec

6. Stabilize 3 min 15 sec

The compositions of the treatment masses used in the above process steps were as follows: Dye developer:

Natriunnitrilotriac etat Sodium Sulphate Sodium Carbonate Potassium Bromide Hydroxylamine Sulphate

4- (N-ethyl-N-ß-hydroxyethylamino) -2-methylaniline sulfate

Water too

409882/1091

1.0 G 4.0 G 30.0 G 1.4 G 2.4 G 4.5 G 1 1

2431223 Bleach solution: Ammonium bromide 160.0 g Aqueous ammonia (28%) 25.0 ml Sodium iron (III) ethylenediamine tetraacetic acid 130 g Glacial acetic acid 14 ml water 1 1 Fixing solution: Sodium tetrapolyphosphate 2.0 g 'Sodium Sulphite 4.0 g Ammonium thiosulphate (70 oil) 175.0 ml Sodium bisulfite. 4.6 g Water too 1 1 Stabilizing solution: Formalin (40%) 8.0 ml Water too 1 1

The red filter density and the green filter density were measured for the samples thus treated. The results obtained are shown in Figures 4 and 5 of the drawings. In Fig. 4, curve 1 shows the red filter density of sample A of the invention, and curve 2 shows the green filter density of sample A, and in Fig. 5, curve 3 shows the red filter density of sample B and curve 4 shows the green filter density of sample B. Like As can be seen from these results, in Sample B, the green filter density increases as the exposure amount increases (curve 4) _; , and the red filter density decreases (curve 3) as the exposure amount is increased. On the other hand, in sample A according to the invention with the adsorptive colloid layer, the green filter density was practically the same as that of sample A, but no reduction in the red filter density (curve 1) was observed. These results show that in Sample B

4098 8 2/109 1

of coupler (25) in the second layer due to color development 5-Broinbenztriazol released into the fourth layer diffused to develop the fourth layer while in Sample A of the invention, the 5-bromobenzotriazole released from the coupler in the second layer trapped in the third layer (the adsorptive colloid layer), causing the diffusion of the development inhibitor in the fourth layer was practically prevented, and the objects of the invention were achieved by this third layer achieved.

Further, samples each of which were the same as Samples A and B prepared above were uniformly passed through a Red light source exposed under the same conditions as above, then a line exposure with a width of 500 microns and a length of 10 mm using a green light source and then using the above-described treatment compositions developed under the following conditions (a), (b) or (c).

(a) 15 min at 24 ^° C

(b) 7 min with 3CPC ■ *

(c) 4 min at

In Sample B, uneven purple to magenta development was seen around the blue dye images in the one below Conditions (a) and (b) developed streaks were observed, while no non-uniformity was observed for any of the conditions for Sample A Development was observed.

Example 2

(Proof of the effect of the adsorptive colloid layer)

Sample C illustrated in Fig. 2 was peeled off the following first layer and second layer

409882/1091

made a transparent cellulose triacetate film.

First layer (red sensitive emulsion layer):

The same as the fourth layer of Sample A or B. in example 1.

Second layer (adsorptive colloid layer);

1 kg of an emulsion of superfine silver iodobromide grains (0.6 mol of silver, 14 mol of iodine, average grain size 0.03 microns) became a thickness on the first layer of 3 microns (an amount of 2.3 g of silver per m).

Sample D was prepared in the same manner as described above except that the second layer is made up of an all gelatin layer of the same thickness as was above.

Each of Samples C and D was exposed using a step wedge and then the same developing procedures as in example 1 (development (1)). After exposure, the samples were also subjected to the same development processes of development (1) with the exception that 0.023 g of 5-bromobenzotriazole to 1 liter of the color developer for development (1) (development (2)) were added.

The red filter densities of sample C during development

(1) and development (2) are shown in Fig. 7 as curve (1) and curve ('2), respectively, and the red filter densities of the sample D in development (1) and development (2) are shown in Fig. As curve (1) and curve (2), respectively. How from these Results became apparent in the case of Sample C, which has the colloid layer for adsorbing an organic development inhibitor contained, practically no difference in density between Eu-winding (1) and development (2) obtained ^ as can be seen from Fig. 7, while in the case of the Sample D showed a significant decrease in density on development

(2) compared to development (1) it was observed how reproduced in FIG. 7. It is thus clear that in Sample D 5-bromobenzotriazole in the developer in the first layer

40 9 8 8 2/1 091

diffused and the development of the layer inhibited, while in sample C 5-bromobenzotriazole through the second layer was trapped, preventing the diffusion by development inhibitor in the first layer and thus the objects of the invention have been achieved. That is, it is clear that the sample with the colloid layer for adsorption of the organic development inhibitor (adsorptive colloid layer) according to the invention normally itself in a developer contaminated with a development inhibitor released from a coupler.

Example 5

A multilayer color photographic film, Sample E, as shown in Fig. 3, was prepared by drawing the following layers onto a cellulose triacetate film .

First layer (antihalation layer) ι

A gelatin layer containing black colloidal silver.

Second layer (intermediate layer);

A dispersion of 2,5-di-tert-octylhydroquinone containing gelatin layer.

Third layer (first red sensitive emulsion layer):

Silver iodobromide emulsion (8 Mo1% iodine), amount of silver 1.2 g / m ² . . . · ■ - ■ "■ /

Sensitizing dye I (as shown in Example 1) 6 10 " ⁵ mol per mol of silver

Sensitizing dye II (as in Example 1 reproduced) 1.5 x 10 ^-5 mol per mol of silver
Coupler (17) 0.09 moles per "mole of silver
Coupler (18) 0.02 mole de mole silver.

409882/1091

Fourth layer (second red-sensitive layer): silver iodobromide emulsion (8 mol% iodine) amount of silver 1.1 g / m sensitizing dye I 3 x t3 "" ⁵ mol per mol of silver sensitizing dye II 1.2 10 "- * mol per mol of silver coupler (30) 0.02 moles per mole of silver

Coupler (18) 0.06 moles per mole of silver

Coupler (17) 0.08 moles per mole of silver

Fifth Layer (Intermediate Layer): The same as the second layer

Sixth Layer (first green-sensitive emulsion layer) silver iodobromide emulsion (8% Mo1 iodine) silver amount 1.4 g / m ^ sensitizing dye III (as described in Example 1) .3 x 10 ^-5 mol per mol of silver

Sensitizing dye IV (as indicated in Example 1) 1 x to " ⁵ 'mole per mole of silver
Coupler (8) 0.05 moles per mole of silver. Coupler (30) 0.002 moles per mole of silver. Coupler (31) 0.001 moles per mole of silver

Seventh layer (second green-sensitive layer): silver iodobromide emulsion (6 moles of iodine) amount of silver 1.5 g / m sensitizing dye III 2.5 x 10 ~ ⁵ moles per mole of silver sensitizing dye IV 0.8 10 ~ ⁵ moles per mole of silver coupler (8th layer) ) 0.004 moles per mole of silver

Coupler (16) 0.02 moles per mole of silver

Coupler (31) "- 0.0003 moles per mole of silver

Eighth layer (yellow filter layer):

An aqueous gelatin layer containing yellow colloidal silver and a dispersion of 2,5-di-tert-octylhydroquinone was raised on the eighth layer.

Ninth layer (first blue-sensitive emulsion layer): silver iodobromide emulsion (6 mol # iodine) amount of silver 1 g / m of coupler (4) 0.25 mol per mol of silver

Coupler (30) 0.01 moles per mole of silver

409882/1091

Tenth layer (second blue-sensitive emulsion layer) silver iodobromide emulsion (6 mol / 96 iodine) amount of silver 1.1 g / m of coupler (4) 0.06 mol per mol of silver

Coupler (30) 0.002 moles per mole of silver

Eleventh layer (adsorptive colloid layer); The same as the second layer in Sample C of Example 2

Twelfth layer (protective layer);

A gelatin layer containing polymethyl methacrylate particles about 1.5 microns in diameter.

Each of the above-described layers also contained a hardening agent for gelatin, a surface active agent and a thickening agent in suitable amounts in addition to the ingredients listed above.

Sample F was also made in the same manner as for Sample E except that the eleventh layer was gelatin only and did not contain silver halide.

Each of Samples E and F thus prepared was cut into a film having a width of 35 mm _? and after uniform exposure to white light, the samples were subjected to development (1) as described in Example 2. In sample F, the red filter density, the green filter density and the blue filter density were reduced considerably with an increased exposure amount, while in sample E, which had the colloid layer for adsorbing the organic development inhibitor according to the invention, the reduction in density was much smaller, whereby the objects of the invention in have been achieved in a satisfactory manner.

Example 4

Sample G was made by adding a layer of silver bromide grains with an average grain size of 0.15 microns in

409882/1 091

an amount of 5 * 5 g silver per m on the back surface of the cellulose triacetate film base of Sample F prepared in Example 3 was formed. The sample turned to cut a film with a width of 35 mm and after uniform exposure to white light, the sample became subjected to development (1) as in Example-3. The received Results show that the coupling density decreased became, as the amount of the treated film increased, that however, the amount of reduction was much less than that of Sample F.

Example 5

Sample H was obtained by pulling up the adsorptive colloid layer, blue-sensitive emulsion layer, green-sensitive emulsion layer, red-sensitive emulsion layer and Protective layer using the same coating compositions that were used for the preparation of sample A in example 1, made on a cellulose triacetate film support. The sample was evenly exposed to a red light source and then line exposure using a green light source as in_Example 1 subjected. The sample was then developed using conditions (c) described in Example 1. The formation of uneven development in sample H was considerably lower than for sample B in Example 1.

Example 6

Using the procedure described in Example 2, samples of the same composition and configuration were obtained as Samples C and D in the same manner as described in Example 2 except that 1x10 "mole of the organic accelerator for the interlayer inter-

40988 2/109 1

bildeffekt (36) or (37) were added to 1 1 developer. The results show that in Sample C, which is the adsorptive colloid layer, the coupling density hardly decreased v / ar, while in sample D the coupling density decreased was and inhibited the progress of development.

The above facts show that even when using a developer containing an organic accelerator for the interlayer interimage effect was contaminated, a color photographic material having the adsorptive colloid layer or the colloidal layer for adsorbing the organic development inhibitor according to the invention without occurring Difficulties can be developed.

The invention can be applied to any color photographic materials which interlayer color correction couplers or organic accelerators for the interlayer interimage effects contain, and in particular the invention is suitable for color photographic materials, which require true color reproduction, such as color photographic negative films, color photographic films Reversal films, color photographic transparent positive films and color photographic papers. Furthermore, the invention can also be applied to color radiographic materials and color photographic microfilms in cases where uniformly developed quality is demanded and the developer to a considerable extent by organic development inhibitors or organic accelerators for the interlayer interimage effect is contaminated.

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

409882/109 1

Claims (14)

P a t e η t a η s ρ r ü c h e Π /. Multi-layer suitable for high temperature development color photographic material, characterized in that it has a carrier with at least one coated thereon a photosensitive emulsion layer which contains an interlayer color correction coupler or an organic Contains accelerators for the interlayer interimage effect, the multilayer color photographic Material a colloid layer for absorbing an organic development inhibitor on the photosensitive emulsion layer or between the photosensitive emulsion layer and the support, the colloid layer having silver halide grains which practically does not contain due to color development to be developed. 2. Multi-layer color photographic material according to claim 1, characterized by d a d u r c h, that the multilayer color photographic material applied to the support is a red-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer and a blue-sensitive silver halide emulsion layer, wherein at least one of the silver halide emulsion layers the interlayer color correction coupler or the organic accelerator for interlayer interimage effect and a layer of fine silver halide grains having a grain size of less than about 0.2 microns containing emulsion on which the interlayer color correction coupler or the organic accelerator for the intermediate 40988 2/109 1 emulsion layer containing interlayer interimage effect as a colloid layer for adsorbing the organic development inhibitor. 3. Multi-layer color photographic material according to claim 1 or 2, characterized in that the interlayer color correction coupler is a coupler represented by the general formula Cp-Z (I) is where Cp is a coupler radical associated with the oxidation product of a primary aromatic amine color developing agent couples ^ and Z is an organic radical consisting of the Couplers are released upon coupling with the oxidation product of a primary aromatic amine developing agent can and which has the function of diffusing into the silver halide emulsion layer and developing in the To inhibit silver halide emulsion layer mean. 4. Multi-layer color photographic material according to claim 3, characterized in that Z in the general formula (I) by the following general Formulas is reproduced: _/ Cla) y, N N-N N- -N wherein -V is a benzene aromatic ring or a heterocyclic aromatic ring with at least one '* 409882/1091 .Nitrogen atom and L is a methine group or a derivative of a Mean something group. 5. A multilayer color photographic material according to claim 2, characterized in that the Interlayer color correction coupler one of the general ones formula Cp-Z (I) wherein Cp is a coupler moiety _/ which couples with the oxidation product of a primary aromatic amine color developing agent / And Z an organic moiety which can be released from the coupler "upon coupling with the oxidation product of a primary aromatic amine developing agent and which has the function of adding into the silver halide emulsion layers diffuse and inhibit the development of the silver halide emulsion layer. 6. A multilayer color photographic material according to claim 5, characterized in that Z in , of the general formula (I) by the following general formulas is reproduced: -N N -N N V N S. (lc) - - -N 4th L. V I. f \ V wherein V is a benzene aromatic ring or a heterocyclic ring aromatic ring with at least one nitrogen 409 88 2/1091 atom and L represents a methine group or a derivative of a methine group. 7. Multi-layered farbphotographisch.es material according to claim 1, characterized in that the multilayer color photographic material is on the support coated a red-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer, a filter layer and a blue-sensitive silver halide emulsion layer, at least one of the silver halide emulsion layers the interlayer color correction coupler or the organic accelerator for interlayer interimage effect and the colloid layer for absorbing the organic development inhibitor is adjacent the filter layer is formed. 8. A multilayer color photographic material according to claim 1, characterized in that the colloid layer for absorbing the organic development inhibitor comprises a silver halide emulsion which fine silver jodobromide grains or fine silver bromide grains respectively a mean grain size of less than about 0.1 micron 2 ron in an amount of about 0.1 to 5 g per m contains. 9. Multi-layer color photographic material according to claim 1, characterized in that the organic accelerator for the interlayer interimage effect a compound of the general formula (II) [ C = C "C = S 4G9882 / 1091 wherein Z is a sulfur atom, an oxygen atom, a selenium atom or the grouping = N-R ^, in which fU is a hydrogen atom, a represents an aliphatic group, an aryl group or a heterocyclic group, R ,, and Rp each represent a hydrogen atom, a aliphatic group or an aryl group and Q is a non-metal atom group to form a heterocyclic ring; or the general formula t C = S R ₂ wherein Q and Rp have the same meaning as Q and R ^ in the general formula (II), _f and the interlayer color correction coupler has the following general formula Cp-Z (I) wherein Cp is a coupler moiety associated with the oxidation product of a primary aromatic color developing agent couples and Z is an organic radical that emerges from the coupler upon coupling with the oxidation product of a primary aromatic Amine developing agent can be released and which has the function of in the silver halide emulsion layers to diffuse and develop in the silver halide emulsion layer to inhibit mean. 10. Multi-layer color photographic material according to claim 1; as characterized in that the multilayer color photographic material attached to the support at least one anti-inhalation layer, a red-sensitive 409 88 2/1091 Borrowed silver halide emulsion layer, a green-sensitive Silver halide emulsion layer and a blue-sensitive silver halide emulsion layer wherein at least one of the silver halide emulsion layers comprises the interlayer color correction coupler or contains the organic accelerator for the interlayer interimage effect, and the colloid layer is arranged on the antihalation layer for adsorption of the organic development inhibitor. 11. Multi-layered farbphotographisch.es material according to claim ' I, characterized in that the colloid layer for adsorbing the organic development accelerator represents a protective layer for the multilayer color photographic material. 12. A multilayer color photographic material according to claim II, characterized in that the Colloid layer for adsorbing the organic development inhibitor as a protective layer, an emulsion of fine silver halide grains With an average grain size of less than about 0.1 micron and a polymer latex or colloidal silica, Comprises aluminum hydroxide or a colloidal metal. 13. Multi-layer color photographic material according to claim 1, characterized in that the Colloid layer for adsorbing the organic development inhibitor; a filter layer for multi-layer color photographic Material is. 14. Multi-layer 'color photographic material according to claim 1, characterized in that the multilayer color photographic material at least one light-sensitive emulsion layer containing fine silver halide grains with an average grain size of less than about 0.2 40 9882/1091 Microns, in addition to containing the interlayer color correction couplers or photosensitive ones containing the organic accelerator for interlayer inter-image effect Emulsion layer on or under the colloid layer has emulsion layer serving to adsorb the organic development inhibitor. 409-88 2/1091