Search Images Maps Play YouTube News Gmail Drive More »
Sign in
Screen reader users: click this link for accessible mode. Accessible mode has the same essential features but works better with your reader.

Patents

  1. Advanced Patent Search
Publication numberUS3892572 A
Publication typeGrant
Publication dateJul 1, 1975
Filing dateJul 1, 1974
Priority dateJun 29, 1973
Also published asCA1026613A, CA1026613A1, DE2431223A1
Publication numberUS 3892572 A, US 3892572A, US-A-3892572, US3892572 A, US3892572A
InventorsHirose Takeshi, Shiba Keisuke
Original AssigneeFuji Photo Film Co Ltd
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
Multilayer color photographic material
US 3892572 A
Abstract
A multilayer color photographic material comprising a support having thereon at least a photosensitive emulsion layer containing an interlayer color correction coupler or an organic accelerator for the interlayer interimage effect or the under-cut interimage effect, a colloid layer for adsorbing an organic development inhibitor, the colloid layer containing silver halide grains which are substantially not developed by color development, on the photosensitive emulsion layer or between the photosensitive emulsion layer and the support. By the positioning of such a colloid layer, the color reproducibility of the color photographic material is improved and also the color photographic material can be developed at a higher temperature without causing development difficulties.
Images(1)
Previous page
Next page
Claims  available in
Description  (OCR text may contain errors)

United States Patent [1 1 Shiba et a].

[ MULTILAYER COLOR PHOTOGRAPHIC MATERIAL [75] Inventors: Keisuke Shiba; Takeshi Hirose, both of Minami-Ashigara, Japan [73] Assignee: Fuji Photo Film Co., Ltd.,

Minami-Ashigara,.lapan 22 Filed: July 1, 1974 211 App]. No.: 484,742

[30] Foreign Application Priority Data July 1,1975

Primary ExaminerNorman G. Torchin Assistant Examiner-Alfonso T. Suro Pico Attorney, Agent, or F [rm-Sughrue, Rothwell, Mion,

Zinn & Macpeak [5 7 I ABSTRACT A multilayer color photographic material comprising a support having thereon at least a photosensitive emulsion layer containing an interlayer color correction coupler or an organic accelerator for the interlayer interimage effect or the under-cut interimage effect, a colloid layer for adsorbing an organic development inhibitor, the colloid layer containing silver halide grains which are substantially not developed by color development, 0n the photosensitive emulsion layer or between the photosensitive emulsion layer and the support. By the positioning of such a colloid layer, the color reproducibility of the color photographic material is improved and also the color photographic material can be developed at a higher temperature without causing development difficulties.

14 Claims, 7 Drawing Figures LAYER I2 LAYER# ll LAYER I0 LAYER# 9 LAYER# 8 LAYER# 7 LAYER#6 LAYER# 5 LAYER #4 LAYER# 3 YER 2 LAYER# SUPPORT LAYER MULTILAYER COLOR PHOTOGRAPHIC MATERIAL BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a multilayer color photographic material showing improved color reproducibilty and providing color images having uniform quality by color development. In particular, the invention relates to a multilayer color photographic material which is not developed unevenly in high temperature development.

2. Description of the Prior Art A multilayer color photographic material usually has on a support a blue-sensitive emulsion layer which contains a yellow coupler and is mainly sensitive to blue light (BL), a green-sensitive emulsion layer which contains a magenta coupler and is mainly sensitive to green light (GL), a red-sensitive emulsion layer which contains a cyan coupler and is mainly sensitive to red light (RL), intermediate layers (ML), a filter layer (FL) capable of absorbing ultraviolet light and visible light in a specific wavelength region, an antihalation layer (AHL), a protective layer (PL), and other photosensitive emulsion layers containing various couplers and having various spectral sensitivity distributions depending on the purposes.

Various attempts have been made for improving the color reproducibility of multilayer color photographic materials.

In a first attempt, an organic compund which can increase the interlayer interimage effect is applied. For instance, in such an attempt it is well known to use an organic heterocyclic compound having an oxo group or a thioxo group. Such compounds are described in, for instance, the specifications of German Ofienlegungsshriften (OLS) 2,043,943 and 2,043,944.

In a second attempt, a compound having a mercapto group or a thioether bond is used. Examples of such a compound are 2-mercaptobenzotriazole, B-hydroxyethyl isothiouronium nitrate, 2,3-dimethylthiazolium salt, l-(2-mercaptoethyl)-l,4,4-trimethyl piperidinium salt, and 2-thioxobenzotriazole. These compounds are also described in detail in the specification of, for instance, U.S. Pat. No. 3,536,487 and the specifications of U.S. Defensive Publications T909,022 and T909,023.

In a third attempt, a colored coupler is used.

In a fourth attempt, an uncolored coupler for interlayer color correction is used. Such uncolored couplers are described in U.S. Pat. No. 3,632,345 and U.S. patent application Ser. No. 467,539, filed May 6, 1974 and Ser. No. 454,525, filed Mar. 25, 1974.

In a fifth attempt, the halogen composition, in particular, the density distribution of silver iodide in a photosensitive silver halide emulsion in each emulsion layer of a multi-layer color photographic material is controlled as described in U.S. patent application Ser. No. 454,525, filed Mar. 25, 1974. The effect with the fifth attempt is, however, less than those of the above mentioned attempts.

In a sixth attempt, a hydroquinone derivative for interlayer color correction is used. These compounds are described in U.S. patent application Ser. No. 461,087, filed Apr. 15, 1974.

These attempts can improve effectively the color reproduction of multilayer color photographic materials but, on the other hand, give rise to serious defects. A first defect is with respect to the so-called interlayer interimage effect or the under-cut interimage effect, namely the effect that a development inhibitor is released from the start of the development and diffuses in the adjacent layer to inhibit the development of the adjacent layer occurs, in that the released inhibitor diffuses in a developer through the group of photosensitive emulsion layers to inhibit the development in an unnecessarily wide range, results in inducing uneven development. The latter defect also reduces the quality of the developed color images. Therefore, in order to provide improved effects so that the desired best color reproduction is obtained, the working range of the released development inhibitor must be restricted to only the range between those photosensitive emulsion layers for which an interlayer interimage effect with each other is obtained. The first defect as mentioned above tends to occur when the aforesaid first, second, third, fourth, and sixth attempts, in particular, the fourth attempt of improving thecolor reproduction of multilayer color photographic materials is applied and further this defect occurs to an even greater extent when rapid development is applied to color photographic materials at temperatures higher than about 30C. On the other hand, it is known that when the fifth attempt mentioned above is applied, the interlayer interimage effect occurs advantageously even in high temperature development.

Also, the second defect is that when the aboveindicated first, second, fourth and sixth attempts for improving the color reproduction of a multilayer color photographic material are applied, the quality of the images obtained with a developer which has been used repeatedly is greatly inferior to the quality of the images obtained with a fresh developer. On the other hand, it is known that when the fifth attempt is applied, the interlayer interimage effect occurs remarkably even in the case of using a developer which has been used repeatedly. The harmful influences on the image quality due to the development inhibitor released in a developer when the multilayer color photographic materials to which these first, second, third, fourth, and sixth attempts are applied are developed differs from the case of developing the multilayer color photo graphic materials to which the fifth attempt is applied. It is known that an iodine ion is caught almost totally by undeveloped silver halide grains by a replacement reaction and thus diffuses less in a developer.

SUMMARY OF THE INVENTION An object of this invention is to improve the defects resulting when the aforesaid first, second, third, fourth, and sixth attempts of improving the color reproduction of multilayer color photographic materials are applied.

Another object of this invention is to provide a multilayer color photographic material which shows improved color reproducibility and which has the ability to be processed using high-temperature high-speed processing at temperatures higher than 30C without uneven development resulting.

These and other objects of this invention will become apparent from the descriptions of this invention given hereinafter.

3 4 The objects of this invention can be attained by form- I particular, the couplers represented by the general in in a multilayer color photographic material comformula (I) can be used as the interlayer color correcprising a support having thereon at least one photosenti Couplers i this invention;

sitive emulsion layer containing an interlayer color correction coupler or an organic accelerator for the inter- 5 P' (0 layer g effect; a layer for Pdsorblhg ah wherein Cp represents a coupler residue which couples h f g wp lhhlbltohi thls 9011919 layer with the oxidation product of a primary aromatic amine taming silver halide grams which are substantially not developing agent and Z represents an Organic group develqped at color development, on the Ph h which can be released in the coupling reaction with the emulsion layer or between said photographic emulsion oxidation product of a primary aromatic amine deve] layer and the PPP oping agent, this organic group diffusing after release Therefore, th1s invention provides a multilayer color to inhibit the development Photographlc material compnsfng a sLfpport having The coupler residue represented by Cp can be a four h h l one vhotographlqemulslon layer equivalent coupler conventionally used for color photaming an interlayer color correction coupler or an ortographie materials Examples of Such couplers are a ganic accelerator for the interlayer interimage effect 5 pyraZo1One Coupler, a pyrazolobenzimidazole and f n f layef for afisorbmg an F f pler, a cyanoacetylcumarone coupler, an indazolone i thls collold comammg sllver coupler, an acylacetanilide coupler, a pivaloylacetanigrams much are substanuany not,c leveloped by lide coupler, an acroylacetamide coupler, a naphthol color development, on the photosensitive emulsion coupler and a phenol coupler Examples of such cow layer or between the photosensltwe emulslon layer and pler residues are residues of the couplers disclosed in the Support the following U.S. Patents.

IE DESCRIPTION THE DRAWINGS Yellow: U.S. Pat. Nos. 3,277,155; 3,415,652; 3,447,928; 3,408,194; 2,875,057; 3,265,506;

FIGS. 1 to show layer structures for embodiments 3,409,439; 3,551,155; 3,551,156; 3,582,322; cm of photographic materials ofth1s1nvent1on described 1n Magenta: US Pat Nos 2,600,788; 2,983,608; Examples 1 YeSPeCtWFIY- 3,006,759; 3,062,653; 3,214,437; 3,253,924;

FIGS. 4 to 7 show graphlcal presentations of the red- 3 311 476; 3 419 3 419 3 476 filter density and green-filter density of embodiments etc of photographic materials of this invention and of phop 2 474 2 698 tographic materials for comparison as described in Ex- 3,034,892; 3,214,437; 3253 924; amles 1 and respectlvely' 3,458,315; 3,582,322; 3,591,383; etc.

DETAILED DESCRIPTION OF THE INVENTION Examples of groups represented by Z are heterocyclic residues forming the l-triazole ring to l-diazole According to apreferred embodiment of this invenring as shown in U.S. patent application Ser. No. tion, the multilayer color photographic material has on 454,525, filed Mar. 25, 1974; the Z-benzotriazole resia support at least two photosensitive emulsion layers dues 8S Shown in U.S. Pat. N0. 3,617,291; arylwhich provide images having substantially different monothio groups; and heterocyclic thio groups. Specolors from each other on color development and at' 40 cific examples of heterocyclic rings are a tetrazole least one of these photosensitive emulsion layers congroup, a triazinyl group, a triazolyl group, an oxazolyl tains an interlayer color correction coupler or an orgroup, an imidazolyl group, an oxadiazolyl group, a ganic accelerator for the interlayer interimage effect, thiadizolyl group, a benzothiazolyl group, a pyrimidyl and further an organic colloid layer for adsorbing an group, and a pyridinyl group. These groups are deorganic development inhibitor and containing silver scribed, more in detail, in, for instance, U.S. Pat. Nos. halide grains which are substantially not developed by 3,617,291; 3,622,328; 3,632,373; 3,620,745; color development on the photosensitive emulsion 3,620,747 and 3,615,506 and the specifications of Britlayer or between the photosensitive emulsion layer and iSh Pat. NOS. 1,201,110; 1,261,061; 1,269,075; and

the support. 1,269,073. In particular, the residues represented by The interlayer color correction coupler used in this general formulas (1a) (lb) and (10) are useful in this ininvention is a coupler as described in U.S. patent applivention:

\ 1160, I, I I V I l I v 1 V I I cation Ser. No. 467,539, filed May 6, 1974, that is to wherein V represents a benzenic aromatic ring or a say, a coupler which provides an interlayer interimage heterocyclic aromatic ring having at least one nitrogen effect and has, as the result thereof, the function of atom and L represents a methine group or a methine color correction. Preferable interlayer color correcderivative group. The group represented by V can be tion couplers are the couplers described in U.S. patent substituted with a group such as an amino group, an acapplication Ser. No. 454,525, filed Mar. 25, 1974 and ylamino group, a halogen atom, an alkyl group, a nitro include the so-called DIR coupler or development ingroup, an alkoxy group, an alkylthio group, and an aryl hibitor-releasing couplers. group.

Also, examples of 2H are described in U.S. Pat. Nos. 3,185,570, 3,244,521; 3,499,761; 3,473,924; 3,575,699; and 3,554,757; the specifications of British Pat. Nos. 919,061 and 1,031,262; French Pat. Nos. 1,346,227 and 1,594,983 and German Pat. No. 1,294,188.

The term organic accelerator for the interlayer interimage or under-cut interimage effect as used in this invention designates an organic compound which is incorporated selectively in a specific photosensitive emulsion layer and increases the interlayer interimage effect or the under-cut interimage effect on other adjacent photosensitive emulsion layer at development and these organic compounds are described in US. Pat. No. 3,536,487; U.S. Defensive publication T909,022 and T909,023 and German Offenlegungsschriften (OLS) 2,043,943 and 2,043,944.

For instance, these organic acclerators are compounds represented by general formula (II);

R R2 (II .1

wherein X represents a sulfur atom, an oxygen atom, a selenium atom, or an =NR:, group, wherein R represents a hydrogen atom, an aliphatic group (e.g., alkyl such as methyl, hydroxyethyl, sulfopropyl, carboxyethyl, methoxyethyl, chloroethyl, benzyl, etc., or alkenyl such as allyl, etc.), an aryl group (e.g., aryl such as phenyl, hydroxyphenyl, methylphenyl, methoxyphenyl, chlorophenyl, etc.), or a heterocyclic group (e.g., pyridyl, etc.); R and R each represents a hydrogen atom, an aliphatic group (e.g., alkyl such as methyl, hydroxyethyl, sulfopropyl, carboxyethyl, methoxyethyl, chloro ethyl, benzyl, etc., or alkenyl such as allyl, etc.), or an aryl group (e.g., aryl such as phenyl, hydroxyphenyl, methylphenyl, methoxyphenyl, chlorophenyl, etc); and Q represents a non-metallic atomic group for forming a heterocyclic ring usually used as a nucleus ofa cyanine dye (e.g., 4-pyridyl, 2-quinolyl, oxazolyl, benzox azolyl, imidazolyl, benzimidazolyl, thiazolyl, benzothiazolyl, etc); or the general formula (III);

(III) wherein Q and R have the same meaning as Q and R in general formula (ll).

Further, a mercapto compound such as l-phenyl-S- mercaptotetrazole, 2 methylthio-5- mercaptothiadiazole, 2-mercapto-5- sulfobenzothiazole, l-methyl-2-mercapto-5- sulfobenzimidazole, etc., are useful.

When the development inhibiting releasable group (i.e., Z in general formula (I) in the interlayer color correction coupler is a mercapto residue, chemically the mercapto group adsorbs strongly on a photosensitive silver halide and thus the interlayer color correction effect is rather weak and the development inhibition effect in the emulsion layer occurs strongly. On the other hand, when the development inhibiting releasable group is the residue represented by general formulas (Ia), (lb) or (lc), the interlayer color correction effect appears strongly. In this case, the useful effect of the colloid layer for adsorbing the organic development inhibitor appears to a remarkable extent.

The organic accelerator for the interlayer interimage effect, in particular, the organic accelerators represented by general formulas (ll) and (Ill) show a high interlayer interimage effect or under-cut interimage effect in rapid development at temperatures higher than 30C but, on the other hand, uneven development occurs. Uneven development is prevented by the positioning of a colloid layer for adsorbing the organic development inhibitor according to the present invention. Also, the interlayer color correction effect is increased due to the use of the organic accelerator and the interlayer color correction coupler. The colloid layer for adsorbing the organic development inhibitor prevents uneven development from occurring in this case. Uneven development will be explained in detail in Example 1 stated. below.

The colloid layer for adsorbing the organic development inihibitor used in this invention is a colloid layer having the function of fixing by adsorption the development inhibitor residue released from an interlayer color correction coupler at development or the development inhibitor residue released by the development of silver halide grains from the organic accelerator for the interlayer interimage effect which has been adsorbed on the silver halide grains in a photosensitive emulsion layer, whereby the development inhibitor residue is prevented from being released in a developer. The colloid layer has also the function of adsorbing the development inhibitor residue once released in a developer, if any, namely the function of removing the development inhibitor residue from a development or appropriately controlling the diffusion of the development inhibitor residue in a developer when the development inhibitor residue is released in the developer. Therefore, it is preferable that the colloid layer of this invention be disposed on or under the photosensitive emulsion layer group, i.e., between the photosensitive layer group and the support.

The colloid layer can contain silver halide grains and further an adsorbent, such as colloidal silica, aluminum hydroxide, a colloidal metal such as colloidal silver, colloidal gold, etc. A suitable amount of the adsorbent ranges from about 0.01 to 10 g/m preferably 0.1 to 5 g/m It is preferable that the silver halide grains be fine grains so that they have a large adsorption ability and adsorption capacity and further that the amount of iodide ions in the silver halide grains be small. In particular, it is preferable that the silver halide grains be super fine grains having a mean grain size less than about 0.2 microns, e.g., about 0.005 to 0.2 microns, preferably 0.01 to 0.1 microns. A suitable amount of the silver halide grains in the colloid grains ranges from about 0.01 to 30 g/m preferably 0.1 to 5 g/m Furthermore, in order to retain the strong adsorption power in a developer, it is preferable that the silver halide grains not be developed by the developer and not be dissolved in the developer. Therefore, silver halide grains which have not been chemically matured or ripened or are silver iodobromide grains containing less than 10 mol percent silver iodide are preferred. Silver chloride grains are not preferred for this purpose.

One of the features of this invention is the position of the colloid layer for adsorbing the organic development inhibitor. In one embodiment of this invention the colloid layer is positioned between the photosensitive emulsion layer containing the interlayer color correction coupler or the organic accelerator for the interlayer interimage efffect and the photosensitive emulsion layer to which the interlayer interimage is provided. In this case the colloid layer captures the development inhibitor released from the photosensitive emulsion layer under the colloid layer to control the working realm of the development inhibitor in a planar direction and to prevent uneven development from occurring.

In a second embodiment of this invention the colloid layer is disposed under the photosensitive emulsion layer, that is to say, at the support side of the photosensitive emulsion layer. In this case the colloid layer captures the development inihibitor released from thephotosensitive emulsion layer to control the development inhibitor from diffusing further and the action of the development inhibitor from spreading in a planar direction further, whereby the uneven development is prevented. Also, by forming the colloid layer at the back side of a support, the colloid layer captures the development inhibitor released in a developer, whereby the developer is prevented from being contaminated by the development inhibitor.

In any of the first embodiment and the second embodiment of this invention, it is preferable that the silver halide grains used in the colloid layer have a mean grain size of less than about 0.2 microns and are silver iodobromide or silver iodide which dissolves in the color developer with difficulty.

The colloid layer of this invention is preferably coated at a coverage of about 0.01 to 10 g, preferably 0.1 to 5 g silver per square meter.

It has been found that if the working realm in a planar direction of the development inhibitor released by development is too broad, the so-called uneven development, that is to say, a Mackie line-like unusual unevenness in color, occurs in a fine color image. This defeet can be improved by the disposition of the colloid layer of this invention.

According to the present invention not only is uneven development prevented but also the uniformity of the development processing can be remarkably improved as the result thereof because by the present invention the release of the organic development inhibitor in the developer, which is a decisive factor in developer contamination, can be prevented.

Another feature of this invention is in a hightemperature development. High-temperature development as used in this invention means development at a temperature higher than about 30C, preferably from about 30 to about 40 or 60C or higher. It is known as shown in Japanese Pat. No. 28836/1970 and French Pat. No. 2,132,675 that the iodine ion released at development is very easily captured by silver chloride or silver bromide in the silver halide grains in the adjacent silver halide emulsion layer due to a replacement reaction reducing the possibility of the release of the organic development inhibitor in the developer, and the replacement reaction is accelerated at higher temperatures to prevent the release of the organic development inhibitor in the developer. On the other hand, the monothio type releasable group as shown in US. Pat. No. 3,227,554 causes chemical adsorption on the silver halide grains in an adjacent silver halide emulsion usually used to form a silver-mercapto compound and at higher temperatures the chemical adsorption tends to be accelerated decreasing the release of the releasable group in the developer. However, interlayer color correction couplers, in particular, the couplers having the releasable groups represented by general formulas (Ia), (lb) and (Ic) and the organic development accelerator for the interlayer interimage effect, in particular, the compounds represented by general formula (II) or (III) (in which, however, R has been substituted with a substituent) have weaker adsorptive ability to the silver halide used in a photographic silver halide emulsion layer than the aforesaid iodine ions and mercapto compounds. Thus, interlayer color correction couplers become readily diffusible and are readily released in the developer when the temperature of the development becomes higher. In such a case, the effect of the employment of the colloid layer for adsorbing organic development inhibitor according to this invention is remarkable.

The couplers used in this invention can be fourequivalent couplers or two-equivalent couplers and in particular, the couplers represented by general formulas (IV), (V) or (VI) described below are useful;

a, c cu 2,

II I N c o l Rt, (I

wherein R represents a primary, secondary or tertiary alkyl group (e.g., a methyl group, a propyl group, a nbutyl group, a tert-butyl group, a hexyl group, a 2- hydroxyethyl group, a 2-phenylethyl group, a pentadecyl group, etc.), an alkoxy group (e.g., a methoxy group, an ethoxy group, a benzyloxy group, etc.), an aryloxy group (e.g., a phenoxy group), an aryl group (e.g., a phenyl group, a 2,4-di-tert-phenyl group, etc.), a heterocyclic ring residue (e.g., a quinolinyl group, a piperidyl group, a benzofuranyl group, an oxazolyl group, etc.), an amino group (e.g., a methylamino group, a diethylamino group, a phenylamino group, a tolylamino group, a 4-(3-sulfobenzamino)anilino group, a 2 -chloro-5-acylaminoanilino group, a 2- chloro-5-alkoxycarbonyanilino group, a 2-trifluoromethylphenyl group, etc.), an acylamino group (e.g., an alkylcarbonamido group such as an ethylcarbonamido group, etc., an arylcarbonamido group, a heterocyclic carbonamido group such as a benzothiazolylcarbonamido group, a sulfonamido group, a heterocyclic sulfonamido group, etc.), or a ureido group (e.g., an alkylureido group, an arylureido group, a heterocyclic ureido group, etc.); R represents 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- alkylaminophenyl group, a 4-trifluoromethylphenyl group, a 3,5-dibromophenyl group, etc.), a heterocyclic group (e.g., a benzofuranylbenzothiazolyl group, a quinolyl group, etc), or a primary, secondary or tertiary alkyl group (e.g., a methyl group, an ethyl group, a tbutyl group, a benzyl group, etc.); and Z represents a hydrogen atom or a group which can be released at color development, such as a thiocyano group, an acyloxy group, an aryloxy group, an alkoxy group, an

alkoxycarbonyloxy group, an aryloxycarbonyloxy group, an amino group such as alkylamino, arylamino, alkylsulfonamido, arylsulfonamido, arylamido, cyclic imino, cyclic imido, etc., an arylazo group, and a heterocyclic azo group as described in, for instance, US. Pat. Nos. 3,419,391; 3,252,924; 3,311,476 and 3,227,550 and US. Pat. applications Ser. No. 461,204, filed Apr. 15, 1974 and Ser. No. 471,639, filed May 20, 1974;

R co cu co NH R,

wherein R represents a primary, secondary, or tertiary alkyl group (e.g., a tert-butyl group, a 1,1- dimethylpropyl group, a 1,1-dimethyl-1-methoxyphenoxymethyl group, etc.), or an aryl group (e.g., a phenyl group, an alkylphenyl group such as a 2- methylphenyl group, a 3-octadecylphenyl group, etc., and alkoxyphenyl group such as a 2-methoxypheny1 group, a 4-methoxyphenyl group, etc., a halophenyl group, a 2-chloro-5-alkylcarbamidophenyl group, a 2- chloro-S-[a-(2,4-di-tert-aminophenoxy)butyramido]- phenyl group, a 2-methoxy'5-alkylamidophenyl group, a 2-ch1oro-5-sulfoamidophenyl group, etc.); R represents a phenyl group (tag, a 2-chlorophenyl group, 2- halo-5-alkylamidophenyl group, a 2-chloro-5-[a-(2,4- di-tert-amylphenoxy)acetamido]phenyl group, a 2- chloro-S-(4-methylphenylsulfonamido)phenyl group, a 2-methoxy-5-(2,4-di-tertamylphenoxy)acetamidophenyl group, etc.); and Z represents a hydrogen atom or a group which can be released at color development, such as a halogen atom (in particular 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 dioxoimidazolidinyl group, a dioxooxazolidinyl group, a dioxythiazolidinyl group, a dioxymorpholino group, etc., as described in, for instance, US. Pat. Nos. 3,227,550; 3,253,924; 3,277,155; 3,265,506; 3,408,194; and 3,415,652; French Pat. No. 1,411,384; British Pat. Nos. 944,490; 1,040,710; and 1,118,028; German Offenlegungsschriften (OLS) 2,057,941; 2,163,812; 2,213,461; and 2,219,917; and US. Pat. application Ser. No. 469,923, filed May 14, 1974;

whereinR represents a substituent used for cyan couplers, such as a carbamyl group (e.g., an alkylcarbamyl group, an arylcarbamyl group such as a phenylcarbamyl group, etc., a heterocyclic carbamyl group such as a benzythiazolylcarbamyl group, etc.), a sulfamyl group (e.g., an alkylsulfamyl group, an arylsulfamyl group such as a phenylsulfamyl group, etc., a heterocyclic sulfamyl group, etc.), an alkoxycarbonyl group, an aryloxycarbonyl group, etc.; R represents an alkyl group, an aryl group, a heterocyclic group, an amino group, an amido group (e.g., an alkylcarbamido group, an arylcarbamido group, etc.), a sulfamido group, a sulfamyl group, or a carbamyl group; R,,, R,,,, and R each has the same meaning as R and in addition represents a halogen atom or an alkyl group and Z represents a hydrogen atom or a group which can be released at color development, such as a halogen atom, a thiocyano group, a cycloimido group (e.g., v a maleido group, a succinimido group, a 1,2-dicarboxyimido group, etc.), an arylazo group, or a heterocyclic azo group.

In order to render the coupler non-diffusible, a group having a hydrophobic residue having about 8 to 32 carbon atoms is introduced in the coupler molecule. Such a residue is called ballast group. The ballast group is bonded to the coupler nucleus directly or through an imino bond, an ether bond, a carbonamido bond, a sulfonamido bond, a ureido bond, an ester bond, an imido bond, a carbamoyl bond, a sulfamoyl bond, etc.

Examples of suitable ballast groups are described in the specific examples of the couplers of this invention given hereinafter in this specification.

Examples of the ballast group are illustrated specifically below:

1. Alkyl groups and alkenyl groups such as CH OH as described in the specification of Japanese patent 7 publication No. 27,563/1964.

(3) Alkylaryl groups such as Z3 (VI) cm; (t)

@CQHJQ and CQHBUD) and 1) Alkylaryloxyalkyl groups such as CZHS -CHO C H (t), -(cH2)3 CH l -co CH O 0 H I CH C1 SH; 1 (1'1) CH3C-CH3 CHO C H (t) C5H11(t) (5) Acylamidoalkyl groups such as COCl 5H3 1 /COC1 -CH2CH2N CH2CH2N Cql'ig C3H7 COC13H27 -CH CHzNH coca cnzu C H as described in US. Pat. Nos. 3,337,344 and 3,418,129.

6. Alkoxyaryl groups and aryloxyaryl groups such as CH COOH 1-1 8. Alkyl groups substituted with an ester group such and CH CH -COOC 2H25(n) 'f 1 SE3 3 COOC H 9. Alkyl groups substituted with an aryl group or a heterocyclic group such as COOCH 3 a zv , and

O H C -cH2cH2 N H C1eI'la7(n.)

l0. Aryl groups substituted with an aryloxyalkoxycarbonyl group such as ca, @coocn iw CSHHM) Then, examples of the materials used in this invention are illustrated below although the invention is not to be construed as being limited to these examples only.

YELLOW COUPLERS 5. a-(4-Carboxyphenoxy)-a-pivaloyl-2-chloro-5{a- (2,4-di-tertamylphenoxy)butyramidolacetanilide 6. a-{3-(1-Benzyl-2,4-dioxo)hydantoinl-a-pivaloyl- 2-chloro-5-{oz-(2,4-di-tert-amylphenoxy)- butyramido}acetanilide 7. a-(4-Methoxybenzoyl)-a-(3,5-dioxomorpholin0)- 5-{'y-(2,4-di-tert-amvlphenoxy)butyramidol-Z- chloroacetanilide MAGENTA COUPLERS 8. 1-(2,4,6-Trichlorophenyl)-3-[3-(2,4-di-tertamylphenoxyacetamido)benzamido]-5-pyrazolone 9. 1-(2,4,6-Trichlorophenyl)-3{3[a-(2,4-di-tertamylphenoxy)-acetamido]benzamidol-4-acetoxy- S-pyrazolone 10. l-( 2,4,6-Trichlorophenyl)-3tridecylamido-4-(4- hydroxyphenyl)-azo-5-pyrazolone 1 1. 1-(2,4,6-Trichlorophenyl)-3-[(2-chloro-5- tridecanoylamino)-anilin]-5-pyrazolone 12. 1(2,4,6-Trichlorophenyl)-3-(2-chloro-5- tetradecyloxycarbonyl )anilino-4-( 1-naphthylazo)- S-pyrazolone 13. 1-(2,4-Di-ch1oro-6-methoxyphenyl)-3-[(2- chloro-S-tridecanoylamino)anilinol-4- benzyloxycarbonyloxy-S-pyrazolone 14. l-( 2,4,6-Trichlorophenyl )-3-[ 3-{ 2,4-di-tertamylphenoxy)-acetamido}benzamido]-4- piperidino-S-pyrazolone 15. l-( 2,4,6-Trichlorophenyl)-3-[ 2-chloro-5- {a- (2,4-di-tertamylphenoxy )butyramido} anilino]-4- N-phthalimido-S-pyrazolone 16. 1-( 2,4,6-Trichlorophenyl)-3-( 2-chloro-5 tetradecylaminoani1ino-4-( 3-methyl-4-hydroxyphenylazo)--pyrazolone l7. 1-Hydroxy-N-[ y-( 2,4-di-tertamylphenoxypropyl)]-2-naphthamide 18. l-l-lydroxy-4-[ 2- (2hexyldecyloxycarbonyl )phenylazo]-2-[N-( l naphthyl)]naphthamide 9. l-Hydroxy-4-chloro-N-[ a-( 2,4-di-tertamylphenxoy)butyl]-2-naphthamide 20. 5-Methyl-4,6-dichloro-2-[a-(3-n-pentadecylphenoxy)butylaminoJ-phenol 21 l-Hydroxy-4-( 2-ethyloxycarbonylphenylazo)-N- (2-ethylamyl )-2-naphthamide INTERLAYER COLOR CORRECTION UNCOLORED COUPLERS 22. a-Benzoyl-a(2-benzothiazolythio)-4-[N-(yphenylpropyl)-N-(4-tolyl)sulfamyl]acetanilide 23. l-l4-[y-(2,4-Di-tertamylphenoxybutyramido)phenyl]-3-piperidinyl-4- 1-phenyl-5-tetrazolylthio)-5-pyraz0lone 24. l-(2,4,6-Trichlorophenyl)-3-{4-[a-(2,4-di-tertamylphenoxy)-butyramido]anilinol-4-( l-phenyl- S-tetrazolylthio)-5-pyrazolone 25. l-[4-{a-(2,4-Di-tertamylphenoxy)acetamido}phenyl]-3-methyl-4-(5- or 6-bromol -benztriazole) 3-pyrazolone 26. 5-Methoxy-2-[ a-( 3-npentadecylphenoxy)butyramido]-4-( l-phenyl-S- tetrazolylthio)phenol 27. N-{a-(2,4-Di-tert-amylphenoxy)acetyl}-w-( 1- phenyl-S-tetrazolylthio)-m-aminoacetophenone 28. a-Pivaloyl-oz-(S- or 6-bromo-l-benztriazolyl)-5- [oz-(2,4-ditert-amylphenoxy)propionamido]-2- chloro-acetanilide 29. a-(4-Meth0xybenzoyl)-a-(5- benztriazolyl )-5-{ y-( 2,4-ditertamylphenoxy)butyramido}-2-chloro-acetanilide 30. a-(4-Stearyloxybenzoyl)-a-(5- or 6-br0mo-lbenztriazolyl)-2-methoxyacetanilide 3 l 1-Hydroxy-4-( 1-phenyltetrazolylthio)-N{ (2- chloro-S-hexadecyloxy)-phenyll-2-naphthamide 32. 1-Benzyl-3-{2-chloro-5-tetradecanamid0)anilino} -4-(5- or 6-methyl-l-benztriazolyl)-5-pyrazolone 33. 1-[4-{a-(2,4-Di-tertamylphenoxy)acetamido} phenyl]-3-ethoxy-4-( 5 or 6-bromo-benztriazolyl)-5-pyrazolone Specific examples of the organic accelerator for the interlayer interimage effect are shown below although the invention is not to be construed as being limited to these examples only.

34. 5-(3-Ethyl-2-benzothiaz0lylidene)-3-benzylrhodanine 35. 5-[3-(y-Sulfopropyl)-2-benzoxazolylidene]-3- cyclohexylrhodanine 36. 5-(3-Methyl-2-benzoselenazolylidene)-3-(-ysulfobutyl)-rhodanine 37. 5-[ 3-( B-Hydroxyethyl )-B-naphthoxazolylidene 1-phenyl-2-thiohydantoin 38. 2-Thioxo-3 ethyl-benzothiaz0le 39. 2-Mercapto-5-methyl-benzothiazole 40. 2-Thioxo-3-n-propyl-benzoxazo1e 41. l ,3-Di-n-propyl-2-thioxo-benzimidazole 42. N-Methyl-2-thioxo-6-chloro-quinoline The couplers used in this invention are generally classified into the so-called Fischer type couplers having a water-soluble group such as a carboxyl group, a hydroxyl group, and a sulfo group and hydrophobic couplers.

The coupler used in this invention can be added to a silver halide emulsion or a hydrophilic colloid using any conventional technique. For instance, a method of dispersing the coupler as a mixture of the coupler and a higher boiling (above about 170C) organic solvent such as dibutyl phthalate, tricresyl phosphate, a fatty oil which is a liquid at normal temperature, a wax, a higher fatty acid or an ester thereof as described in, for instance, the specifications of U.S. Pat. Nos. 2,304,939 and 2,322,027; and method of dispersing the coupler as a mixture thereof with a low boiling organic solvent (below about 170C) or a water-soluble organic solvent and a method of dispersing the coupler as this mixture together further with a high boiling organic solvent as described in, for instance, U.S. Pat. Nos. 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 C), alone or as a mixture thereof with other couplers to be used together, for instance, a colored coupler or an uncolored coupler as described in, for instance, German Pat. No. 1,143,707, can be used.

As a dispersion aid used in such case, an anionic surface active agent (e.g., sodium alkylbenzene sulfonate, sodium octylsulfosuccinate, sodium dodecylsulfate, sodium alkylnaphthalene sulfonate, a Fischer type coupler, etc.), an amphoteric surface active agent (e.g., N- tetradecyl-N,N-dipolyethylene-a-betaine, etc), and a or 6-nitro- 1 5 nonionic surface active agent (e.g., sorbitan monolaurate, etc.) can be used.

The coupler is usually used in an amount of from about 1/10 to 2 per mol of the silver halide. The interlayer color correction coupler can be used alone or as a mixture with other couplers and the amount thereof is usually about 1 to about 50 mol percent, preferably 5 to 20 mol percent to the total amount of the couplers used in a photosensitive emulsion layer.

The organic accelerator for the interlayer interimage effect can be added as a solution in a water-miscible organic solvent such as methanol, ethanol, pyridine, methyl cellosolve, etc., or in water. The amount thereof is usually from about to about 10' mols per mol of silver halide.

The silver halide emulsion used in this invention is a fine dispersion of silver chloride, silver bromide, silver chlorobromide, silver iodobromide, and silver chloroiodo-bromide in a hydrophilic polymer. As the hydrophilic polymer those conventionally used in the photographic art can be advantageously employed including gelatin, a gelatin derivative such as an acylated gelatin, a graft gelatin, etc., albumin, gum arabic. agar agar, a cellulose derivative such as hydroxyethyl cellulose, carboxymethyl cellulose, etc., a synthetic resin such as polyvinyl alcohol, polyvinyl pyrrolidone, polyacrylamide, etc. The silver halide can have a uniform grain size or a broad grain size distribution. Also, the size of the silver halide ranges from about 0.1 microns to about 3 microns. The silver halide emulsion can be prepared using a single jet method, a double jet method, or a combination of these methods or can be matured using,for instance, an ammonia method, a neutralization method, an acid method, etc.

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

The silver halide emulsion can also be sensitized using a spectral sensitization method which is generally employed in producing color photographic materials. For such purpose a sensitizing dye, such as a cyanine dye or a merocyanine dye, as described in U.S. Pat. Nos. 2,526,632; 2,503,776; 2,493,748; 3,384,486; 2,933,390 and 2,937,089 can be suitably used. The silver halide emulsion used in this invention can further contain a stabilizer such as a 4-hydroxy-l,3,3a,7- tetraazaindene derivative, etc., 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 derivatives, for instance, a quanternary ammonium salt as described in U.S. Pat. Nos. 2,271,623 and 2,288,226 and also a polyalkylene oxide derivative as described in US. Pat. Nos. 2,708,162; 2,531,832; 2,533,990; 3,210,191; and 3,158,484. The silver halide emulsion layer further can contain an irradiation preventing dye.

Furthermore, the color photographic material of this invention can contain layers such as a filter layer, a mordant dye-containing layer, a colored layer containing a hydrophobic dye, etc.

The silver halide emulsions used in this invention can be coated on various supports such as, for instance, a cellulose acetate film, a polyethylene terephthalate film, a polyethylene film, a polypropylene film, a glass plate, a baryta-coated paper, a resin-coated paper, or a synthetic paper.

The photographic material of this invention is processed with a color developer containing, as a color developing agent, a p-phenylenediamine derivative and a p-aminophenol derivative. Examples of preferred pphenylenediamine derivatives are p-amino-N-ethyl-N- ,B-(methanesulfoamidoethyl)-m-toluidine sesquisulfate monohydrate, diethylamino-p-phenylenediamine sesquisulfite, p-amino-N,N-diethyl-m-toluidine hydrochloride, p-amino-N-ethyl-N-B-hydroxyethylaniline sesquisulfate monohydrate, and the like.

The color photographic materials of this invention can be developed using developers generally used for developing conventional color photographic negative materials, cine color photographic negative or positive materials, color photographic papers, and instant color photographic materials. For instance, the color development processes as described in the specification of British Pat. No. 1,203,316; in U.S. Pat. No. 3,695,883; U.S. Pat. application Ser. No. 234,163, filed Mar. 13, 1972 and Ser. No. 240,287, filed Mar. 31, 1972; H. Gordon, The British Journal of Photography, page 559 eq seq., Nov. 15, 1954; ibid., page 440 et seq., Sept. 9, 1955; and ibid., page 2 et seq., Jan. 6, 1956; S. Horwitz, The British Journal of Photography, page 212 et seq., Apr. 22, 1960; E. Gehret, The British Journal of Photography, page 122 et seq., Mar. 4, 1960 and ibid., page 396 et seq., May 7, 1965; .l. Meech, The British Journal ofPhotography, page 182 et seq., Apr. 3, 1959; and the specification of German Offenlegungsschrift (OLS) 2,238,051, can be used.

The invention is illustrated in greater detail by reference to the following examples which are given for the purpose of understanding the embodiments of this invention and the objects of this invention but are not to be construed limiting the invention. Unless otherwise indicated, all parts, percents, ratios and the like are by weight.

EXAMPLE 1 Sample A as illustrated in FIG. 1 of the accompanying drawings was prepared by coating a first layer, a second layer, a third layer, a fourth layer, and a fifth layer on a transparent cellulose triacetate film as a support. The coating compositions and the preparation 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 silver and 6 mol percent iodine) and 600 g of Emulsion 1 prepared by dispersing a solution of 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 10 percent gelatin solution using 4 g of sodium dodecylbenzenesulfonate was coated on the support at a coverage of 0.6 g silver per square meter.

SECOND LAYER (GREEN-SENSITIVE EMULSION LAYER) 1 kg of a silver iodobromide emulsion (0.6 mol silver and 6 mol percent iodine) was spectrally sensitized using 2X10 mol of Sensitizing Dye l and 6X10 mol of Sensitizing Dye 11 and then the silver halide emulsion was mixed with 600 g of Emulsion 11 prepared by dispersing a solution of 60 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 gelatin solution using 4 g of sodium dodecylbenzenesulfonate to provide the coating composition for the second layer. The coating compossition was then coated on the first layer at a coverage of 0.9 g silver per square meter.

THIRD LAYER (ADSORPTIVE COLLOID LAYER) 1 kg of a silver halide emulsion of super-fine silver iodobromide grains (0.5 mol silver, 2 mol percent iodine, and a mean grain size of 0.05 microns) was coated on the second layer at a thickness of 3 microns (at a coverage of 2.1 g silver per square meter) as the colloid layer for adsorbing an organic development inhibitor of this invention.

FOURTH LAYER (RED-SENSITIVE EMULSION LAYER) 1 kg of a silver iodobromide emulsion (the same as the silver halide emulsion used for forming the first layer) was spectrally sensitized with 4X10 mol of Sensitizing Dye III and 1X10 mol of Sensitizing Dye IV. The silver halide emulsion was mixed with 450 g of Emulsion Ill prepared in the same manner as preparing Emulsion II using 100 g of Coupler (l7) and the coating composition thus formed was coated on the third layer at a coverage of 1.7 g silver per square meter.

FIFTH LAYER (PROTECTIVE LAYER) An aqueous gelatin solution was coated on the fourth layer as the protective layer.

Also, sodium polyvinylbenzenesulfonate as a thick-' ener, sodium dodecylbenzenesulfonate as a surface active agent, and 2-hydroxy-4,6-dichloro-S-triazine sodium salt as a hardening agent for gelatin were added to each of the above-described coating compositions in addition to the above described components.

The materials used for making Sample A were as fol-.

1. Color Development 3 min. sec. 2. Bleach 6 min. 30 sec. 3. Wash 3 min. 15 sec. 4. Fix 6 min. 30 sec. 5. Wash 3 min. l5 sec. 6. Stabilization 3 min. l5 sec.

The formulations of the processing compositions used in the above processing steps were as follows:

Color Developer:

Sodium Nitrilotriacetate l Sodium Sulfite 4 Sodium Carbonate 30. Potassium Bromide l Hydroxylamine Sulfate 2 4-(N-Ethyl-N-B-hydroxyethylamino)- 4 2-methylaniline Sulfate Water to make I Bleach Solution:

Ammonium Bromide Aqueous Ammonia (28%) Sodium Ferric Ethylenediamine Tetraacetic Acid Glacial Acetic Acid Water to make 1 1 Fix Solution:

Sodium Tetrapolyphosphate Sodium Sulfite Ammonium Thiosulfate Sodium Bisulfite Water to make Stabilization Solution:

Formalin (40%) Water to make I I The red filter density and the green filter density were measured for the samples thus processed. The results obtained were shown in FIG. 4 and FIG. 5 of the accompanying drawings. In FIG. 4 curve 1 shows the red filter density of Sample A of this 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. As shown in these results, in Sample B the green filter density increased as the exposure amount increased(curved 4) and the red filter density decreased (curve 3) as the exposure amount increased. On the other hand, in Sample A of this invention having the adsorptive colloid layer, the green filter density was almost the same as that of Sample A but no reduction in red filter density (curve 1) was observed. These results show that in Sample B 5-bromobenztriazole released from Coupler (25) in the second layer due to color development diffused into the fourth layer to inhibit the development of the fourth layer, while in Sample A of this invention S-bromobenztriazole released from the coupler in the second layer was captured in the third layer (the adsorptive colloid layer), whereby the diffusion of the development inhibitor into the fourth layer was substantially prevented and the objects of this invention were achieved by the third layer.

Furthermore, samples each the same as Samples A and B prepared above, were uniformly exposed to a red light source under teh same conditions as above, subjected to, then, a line exposure of a width of 500 microns and a length of 10 millimeters using a green light osurce, and then developed using the above-described processing compositions under the following conditions (a), (b), or (c).

a. for 15 minutes at 24C b. for 7 minutes at 30C c. for 4 minutes at 38C In Sample B purple to magenta uneven development was observed around the blue dye images in the strips developed under the conditions (a) and (b), while no uneven development was observed for any of the conditions for Sample A.

EXAMPLE 2 (Demonstration of the effect of the adsorptive colloid layer) Sample C as illustrated in FIG. 2 of the accompanying drawings was prepared by coating the following first layer and second layer on a transparent cellulose triacetate film.

FIRST LAYER (RED-SENSITIVE EMULSION LAYER) The same as the fourth layer of Sample A or B in Example l.

SECOND LAYER (ADSORPTIVE COLLOID LAYER) 1 kg of an emulsion of super fine silver iodobromide grains (0.6 mol silver, 14 mol percent iodine, and a mean grain size of 0.03 microns) was coated on the first layer at a thickness of 3 microns (at a coverage of 2.3 g silver per square meter).

Sample D was prepared in the same manner as described above except that the second layer was a layer of gelatin only having the same thickness as above.

Each of Samples C and D was exposed using a step wedge and then subjected to the same development procedures as in Example 1 (Development (1)). Alternatively, the samples were, after exposure, subjected to the same development procedures of Development (1) except that 0.023 g of S-bromobenztriazole was added to 1 liter of the color developer for Development (1) (Development (2)).

The red filter densities of Sample C in Development (1) and in Development (2) are shown in FIG. 7 as curve (1) and curve (2), respecxtively, and the red filter densities of Sample D in Development (1) and in Development (2) are shown in FIG. 6 as curve l) and curve (2), respectively. As clear from these results, in the case of Sample C having the colloid layer for absorbing an organic development inhibitor, substantially no difference in density between Development (1) and Development (2) was obtained as shown in FIG. 7,

while in the case of Sample D a great reduction in density was observed in Development (2) as compared with Development l) as shown in FIG. 6. Thus, it can be understood that in Sample D S-bromobenztriazole in the developer diffused into the first layer and inhibited the development of the layer, while in Sample C 5-bromobenztriazole was captured by the second layer, whereby the diffusion of the development inhibitor in the first layer was prevented and thus the objects of this invention were attained. In other words, it can be understood that the sample having the colloid layer for' EXAMPLE 3 A multilayer color photographic film, Sample E, as

illustrated in FIG. 3 was prepared by coating the following layers on a cellulose triacetate film.

First Layer (Antihalation layer) A gelatin layer containing black colloidal silver.

Second Layer (Intermediate layer) A gelatin layer containing a dispersion of 2,5-di-toctylhydroquinone.

Third Layer (First red-sensitive emulsion layer):

Silver iodobromide emulsion (8 mol% iodine) silver coverage of 1.2 g/m Sensitizing Dye l (as shown in Example 1) 6 X 10 mol per mol of silver Sensitizing Dye II (as shown in Example 1) Coupler l7) Coupler 18) 1.5 X 10 mol per mol of silver 0.09 mol per mol of silver 0.02 mol per mol of silver Fourth Layer (Second red-sensitive layer):

Silver iodobromide emulsion (8 mol% iodine) Sensitizing Dye I Sensitizing Dye 11 silver coverage of 1.1 g/m 3 X 10' mol per mol of silver 1.2 X 10' mol per mol of silver Coupler (30) 0.02 mol per mol of silver Coupler (18) 0.06 mol per mol of silver Coupler 17) 0.08 mol per mol of silver Fifth Layer (lnterrnediate layer):

The same as the second layer.

Sixth Layer (First green-sensitive emulsion layer):

Silver iodobromide emulsion (8 mol% iodine) silver coverage of 1.4 g/m ,Sensitizing Dye III (as shown In Example 1) 3 X 10 mol per mol of silver Third Layer (First red-sensitive emulsion layer):

Sensitizing Dye IV (as shown in Example 1) l X 10 mol per mol of silver Coupler (8) 0.05 mol r mol of silver Coupler (30) 0.002 mo per mol of silver Coupler (31 0.001 mol per mol of silver Seventh Layer (Second green-sensitive layer):

Silver iodobromide emulsion (6 mol iodine) gilver coverage of 1.5 m

Eighth Layer (Yellow filter layer) An aqueous gelatin layer containing yellow colloidal silver and a dispersion of 2,5-di-t-octylhydroquinone was coated as the eighth layer.

Ninth Layer (First bluesensitive emulsion layer):

Silver iodobromide emulsion (6 mol% iodine) Coupler (4) Coupler (30) silver coverage of 1 g/m 0.25 mol per mol of silver 00] mol per mol of silver Tenth Layer (Second blue-sensitive emulsion layer):

Silver iodobromide emulsion (6 mol% iodine) Coupler (4) Coupler (30) silver coverage of 1.1 g/m 0.06 mol per mol of silver 0.002 mol per mol of silver Eleventh Layer (Adsorptive colloid layer) The same as the second layer of Sample C in Example 2.

Twelfth Layer (Protective layer) A gelatin layer containing particles of polymethyl methacrylate (diameter about 1.5 microns).

Each layer described above contained further a hardening agent for gelatin, a surface active agent, and a thickener in suitable amounts in addition to the aforesaid components.

Sample F was also prepared in the same manner as described for Sample E except that the eleventh layer was only a gelatin layer containing no silver halide.

Each of Samples E and F thus prepared was cut into a film of a width of 35 mm and after subjecting to uniform white light exposure, was subjected to Development (1) as described in Example 2. In Sample F the red filter density, the green filter density, and blue filter density were reduced greatly as the exposure amount increased, while in Sample E having the colloid layer for adsorbing the organic development inhibitor according to this invention, the density reduction was much less, attaining sufficiently the objects of this invention.

EXAMPLE 4 Sample G was prepared by forming a layer of silver bromide grains having mean grain size of 0.15 microns at a coverage of 5.5 g silver per square meter on the back surface of the cellulose triacetate film support of Sample F prepared in Example 3. The sample was cut into a film of a width of 35 mm and after being uniformly exposed to white light, was subjected to Development (1) as in Example 3. The results obtained show that the coupling density was reduced as the amount of the film processed increased but the reduction extent was much less than the case of Sample F.

EXAMPLE 5 Sample H was prepared by coating the adsorptive colloid layer, blue-sensitive emulsion layer, greensensitive emulsion layer, red-sensitive emulsion layer, and protective layer using the same coating compositions as used for preparing Sample A in Example 1 on a cellulose triacetate film support. The sample was exposed uniformly to a red light source and then subjected to line exposure using a green light source as in Example 1. The sample was, then, developed using condition (0) as described in Example 1. The formation of uneven development in Smple H was markedly less than for Sample B in Example 1.

EXAMPLE 6 Using the procedure as described in Example 2 samples having the same composition and configuration as Samples C and D were developed in the same manner as described in Example 2 except that l l()" mol of the organic accelerator for the interlayer interimage effect (36) or (37) was added to 1 liter of the developer. The results show that in Sample C having the adsorptive colloid layer the coupling density was hardly reduced, while in Sample D the coupling density was reduced inhibiting the progress of development.

The above fact shows that even in the case of using a developer contaminated with an organic accelerator for the interlayer interimage effect, a color photographic material having the adsorptive colloid layer or the colloid layer for adsorbing the organic development inhibitor according to this invention can be developed without any difficulties occurring.

The present invention can be applied to all color photographic materials containing interlayer color correction couplers or organic accelerators for the interlayer interimage effects and, in particular, the invention is useful for color photographic materials which require faithful color reproducibility, such as color photographic negative films, color photographic reversal films, color photographic transparent positive films, and color photographic papers. Furthermore, the invention can be also applied to radiographic color materials and color photographic micro films in those cases where uniform developed quality is required and the developer is contaminated to a great extent by organic development inhibitors or organic accelerators for the interlayer interimage effect.

While the invention has been described in detail and with reference to specific embodiments thereof, it will be apparent to one skilled in the art that various changes and modifications can be made therein without departing from the spirit and scope thereof.

What is claimed is:

l. A multilayer color photographic material suitable for high temperature development comprising a support having coated thereon at least one photosensitive emulsion layer containing an interlayer color correction coupler or an organic accelerator for the interlayer interimage effect, the multilayer color photographic material having a colloid layer for adsorbing an organic development inhibitor on the photosensitive emulsion layer or between the photosensitive emulsion layer and the support, said colloid layer containing silver halide grains which are substantially not developed by color development.

2. The multilayer color photographic material as set forth in claim 1, in which said multilayer color photographic materials has coated on the support a redsensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer, and a blue-sensitive silver halide emulsion layer, at least one of said silver halide emulsion layer containing the interlayer color correction coupler or the organic accelerator for the interlayer interimage effect and a layer of an emulsion containing fine silver halide grains having grain sizes of less than about 0.2 microns on said emulsion layer containing the interlayer color correction coupler or the organic accelerator for the interlayer interimage effect as the colloid layer for adsorbing the organic development inhibitor.

3. The multilayer color photographic material as set forth in claim 1, in which said interlayer color correction coupler is a coupler represented by general formula (l) wherein Cp represents a coupler residue which couples with the oxidation product of a primary aromatic amino color developing agent; and Z represents an organic residue which can be released from the coupler on coupling with the oxidation product of a primary aromatic amino developing agent and which has the function of diffusing into the silver halide emulsion layer and inhibiting the development in the silver halide emulsion layer.

4. The multilayer color photographic material as set forth in claim 3, in which Z in general formula (I) is represented by following general formulas la), lb) or 23 24 represented by general formula (ll) or -N L Q X I C C C S V I I1] //C- N (1o; R 0 R2 (11) wherein V represents a benzenic aromatic ring or a hetwherein Z represents a sulfur atom, an oxygen atom, a erocyclic aromatic ring containing at least one nitrogen selenium atom or an =NR group, wherein R repreatom and L represents a methine group or a derivative sents a hydrogen atom, an aliphatic group, an aryl of a methine group. group, or a heterocyclic group; R and R each repre- 5. The multilayer color photographic material as set sents a y g atom, an aliphatic g p, r an ary forth in claim 2, in which said interlayer color correc- 5 group, and Q represents a non-metal atomic group for tion coupler is a coupler represented by the gen l f rforming a heterocyclic ring; or the general formula (III) mula (l) Q CpZ I wherein Cp represents a coupler residue which couples N with the oxidation product of a primary aromatic l amino color developing agent; and Z represents an or- R2 (III) ganic residue which can be released from the coupler wherein Q and R have the same meaning as Q and R, on coupling with the oxidation product of a primary arin general formula (II), and the interlayer color correcomatic amino developing agent and which has the function coupler represented by general formula (1) tion of diffusing into the silver halide emulsion layers p Z and inhibiting the development in the silver halide emulsion layer. I wherein Cp represents a coupler residue which couples 6. The multilayer color photographic material as set with the oxidation product of a primary aromatic forth in claim 5, in which Z of general formula (I) is amino color developing agent; and Z represents an orrepresented by following general formulas (la), (lb) or ganic residue which can be released from the coupler (lc) on coupling with the oxidation product of a primary arv l v I wherein V represents a benzenic aromatic ring or a het omatic amino developing agent and which has the funcerocyclic aromatic ring containing at least one nitrogen tion of diffusing into the silver halide emulsion layers atom and L represents a methine group or a derivative and inhibiting the development in the silver halide of a methine group. emulsion layer.

7. The multilayer color photographic material as set T multilayer 9 photogralhic material as Set forth in claim 1, in which said multilayer color photoforth i r which 581d ilayer color photographic material has Coated on the support a graphic material has coated on the support at least an sensitive silver halide emulsion layer, a green-sensitive annhalauon layer sllver hahde emulslo" silver halide emulsion layer, a filter layer, and a bluelayer a greenfsenshwe sllvfar hahde emulsion layer and sensitive silver halide emulsion layer, at least one of a b1ue'SePS1t We sllvefr hahde Fmulsloh layer" least said silver halide emulsion layers containing the inter- F of Sand sllver hahdefimulsloh layers cohtalmhg the layer color correction coupler or the organic acceleralnterkyer Color CPUCCUOH Q P F the Organ: tor for the interlayer interimage effect and said colloid celerator for the mterlayer mtenmage effect and 531d layer for adsorbing the organic development inhibitor colloid layer for ad sorbing the organic defelopmem bein formed adjacent said filter lawn hibitor being positioned on said antihalatlon layer.

g r 1 l. The multilayer color photographic material as set The multilayer Color photograph: material as Set forth in claim 1, in which said colloid layer for adsorbm clalm m whlch layer adsorb ing the organic development accelerator is a protective mg theiorgamc (levelopmfarlt "lhlbltqr compnses a layer for said multilayer color photographic material. ver halide emulsion containing fine silver lodobromlde 12. The multilayer color photographic material as Set 9 fine blomlde gramsFach havmg a mean forth in claim 11, in which said colloid layer for adsorbgram 5126 of less that} about mlcrons at a coverage ing the organic development inhibitor as the protective of about to 5 g Sllvler per Square meter layer comprises an emulsion of fine silver halide grains 9. The multilayer color photographic material as set having a mean grain size of less than about 0.1 microns forth in claim 1, in which said organic accelerator for and a polymer latex or colloidal silica, aluminum hythe interlayer interimage effect comprises a compound droxide, or a colloidal metal.

ing a mean grain size of less than about 0.2 microns in addition to said photosensitive emulsion layer containing the interlayer color correction coupler or the organic accelerator for the interlayer interimage effect on' or under the layer emulsion layer to function as the colloid layer for adsorbing the organic development inhibitor.

Patent Citations
Cited PatentFiling datePublication dateApplicantTitle
US3728121 *Aug 19, 1970Apr 17, 1973Agfa Gevaert AgMultilayer color photographic material
US3790384 *Oct 26, 1971Feb 5, 1974Fuji Photo Film Co LtdLight-sensitive color photographic elements with improved image quality
Referenced by
Citing PatentFiling datePublication dateApplicantTitle
US4153460 *Feb 7, 1978May 8, 1979Konishiroku Photo Industry Co., LtdLight-sensitive silver halide color photographic material
US4413054 *Mar 30, 1982Nov 1, 1983Fuji Photo Film Co., Ltd.Silver halide color photosensitive materials
US4456682 *Sep 21, 1982Jun 26, 1984Fuji Photo Film Co., Ltd.Silver halide color photographic material
US4614707 *Feb 19, 1985Sep 30, 1986Fuji Photo Film Co., Ltd.Color reversal photographic light-sensitive materials
US4652515 *Aug 5, 1985Mar 24, 1987Fuji Photo Film Co., Ltd.Silver halide color photographic materials having improved development characteristics
US4770980 *Jun 15, 1987Sep 13, 1988Agfa-Gevaert AgMultilayer color photographic recording material wherein a red secondary sensitivity is produced in the blue and green layers
US5646297 *Aug 1, 1996Jul 8, 1997Imation Corp.Process for preparation of 2-equivalent 4-arylthio-5-pyrazolone magenta couplers
US6045985 *Nov 23, 1998Apr 4, 2000Tulalip Consultoria Comercial Sociedade Unipessoal S.A.Light-sensitive silver halide photographic elements containing yellow filter dyes
EP1980908A1Apr 11, 2008Oct 15, 2008FUJIFILM CorporationSilver halide photographic material and image forming method using the same
Classifications
U.S. Classification430/504, 430/543, 430/361
International ClassificationG03C7/00, G03C7/32, G03C7/30, G03C7/18
Cooperative ClassificationG03C7/3029, G03C7/3225
European ClassificationG03C7/32C, G03C7/30M