JPS6143747A - Silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To enhance sharpness and stability by forming a layer contg. a polymer coupler latex on a support and a nonphotosensitive layer contg. a compd. for forming a development inhibitor or the like in contact with said layer. CONSTITUTION:The layer contg. a polymer coupler latex is formed on the support and the nonphotosensitive layer contg. a DIR compd. capable of forming the development inhibitor or its precursor upon the coupling reaction with the oxidation product of a developing agent is formed in contact with said layer to obtain a silver halide color photographic sensitive material. The usable polymer couplers are polymers having repeating units each represented by the formula in which R is H, 1-4C alkyl, or Cl; X is -CONH- or the like; Y is -CONH- or the like; A is 1-10C alkylene or the like; and m, n are each 0 or 1.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a silver halide color photographic light-sensitive material, and particularly to a silver halide color photographic light-sensitive material with improved sharpness.

(Prior art) Over the past few years, with the spread of /J) format cameras, small-screen color negatives have often been enlarged to large-screen color prints, and even better sharpness has been required than ever before. It's becoming more and more K.

For this purpose, it is proposed to add so-called DII (compounds) which couple with the oxidized form of the color developing agent and release a development inhibitor or development inhibitor precursor, as described in U.S. Pat. Kaisho!λ−rλ
4Lλ≠, described in the same J Co./176 Co. 7, etc.

This is because the edge effect increases due to the development inhibiting action of the development inhibitor released from the DIR compound, thereby improving the sharpness.

In addition, it is a well-known technique in the art to reduce the total light scattering of an emulsion film by making the emulsion film thinner, thereby improving sharpness.

As a means of thinning the emulsion layer, the amount of gelatin applied,
There are reductions in the amount of coupler coated and the amount of high boiling point V solvent used to disperse the coupler, but both of them affect the coatability and pressure characteristics of the emulsion film.
Side effects such as deterioration of emulsion stability and decrease in color density are significant. The use of polymer coupler latex as a method for thinning emulsion films other than these is disclosed in JP-A-1
J Hiroshi 3, JP Sho J1-10731. Tokukai Sho Jr-442
It is described in Of-4c etc.

In this case, the layer can be made thinner without any side effects.

Here, when using a polymer coupler latex in a layer containing a DIR compound, a high boiling point organic solvent is required for dispersing the DIR compound. Therefore, when these two metals are emulsified and dispersed, a very large amount of a high boiling point organic solvent is required, resulting in an increase in film thickness. On the other hand, a method can be considered in which the DIFL compound and the polymer coupler latex are each individually emulsified and dispersed and then added separately, but in this case,
While these are dissolved as a coating solution in a mixed mold, the oil droplets in these two emulsified dispersions may coalesce, resulting in the precipitation of DIR compounds on the coated article and the photographic properties. In some cases, it may have an adverse effect on the person.

(Objective of the Invention) The object of the present invention is firstly to improve the above-mentioned drawbacks, and secondly to provide a color photosensitive material with high sharpness and excellent stability. 2. To provide a photosensitive material that does not cause precipitation of additives even if the amount is small.

(Structure of the Invention) The above object is to provide a layer containing a polymer coupler latex on a support and a development-inhibiting compound or a development-inhibiting precursor formed by a coupling reaction with an oxidation product of a developer. Compounds formed (hereinafter referred to as DI
This is achieved by a silver halide color light-sensitive material having a non-light-sensitive layer containing a compound (referred to as R compound).

That is, by incorporating the DIR compound into a non-photosensitive layer adjacent to this layer, rather than in the layer containing the polymeric 2-latex itself, thinning can be achieved extremely efficiently. By layering, a significant improvement in sharpness can be achieved without causing disadvantages such as precipitation of DIR compounds in coated materials and adverse effects on photographic properties.

In the present invention, it is particularly preferred that the polymer coupler latex is included in the silver halide emulsion layer.

Further, from the viewpoint of improving the sharpness due to the edge effect, it is particularly advantageous and preferable for the DIR compound to have a diffusive development inhibiting compound (hereinafter referred to as a diffusive DIFL compound).

The polymer coupler used in the present invention has the following general formula (C
1) At least one ethylene compound derived from the monomeric sciller represented by the formula [C] and having a repeating unit represented by the general formula [C] or having no ability to oxidatively couple with an aromatic-grade amine developer. Preferably, it is a copolymer with one or more non-chromogenic monomers containing groups. Here, more than two types of monomers 2- may be simultaneously polymerized.

General formula (Cl) C1-12=C+Y-)-JA-3-;
CII) In the formula R represents a hydrogen atom, a lower alkyl group having 1 carbon atoms, or chlorine, and X represents -CUNk-1-1-
Nf(CONf(-1-NHCOO-1-COO-1-
SO□-1-CO-1 or -〇-, Y represents 100NH-1 or -〇〇〇-, and human is carbon number/-10
unsubstituted or substituted alkylene groups, aralkylene groups,
Alternatively, it represents an unsubstituted or substituted arylene group, and the alkylene group may be linear or branched. (Examples of alkylene groups include methylene, methylmethylene, dimethylmethylene, dimethylene, trimethylene, tetramethylene, pentamethylene, hollow sameethylene, decylmethylene,
Aralkylene groups include, for example, benzylidene; arylene groups include, for example, phenylene, naphthylene, etc.) Q is a cyan color-forming coupler residue or a magenta color-forming coupler residue that can be coupled with an oxidized product of an aromatic-grade amine developer to form a dye. represents a group and a yellow color-forming coupler residue.

mXn represents 0t or l.

Examples of substituents for the alkylene group or phenylene group represented by A include aryl group (e.g. phenyl group), nitro group, water rRIS1, cyano group, sulfo group, alkoxy group (e.g. methoxy group), aryloxy group (e.g. phenoxy group). ), acyloxy groups (e.g. acetoxy groups), acylamino groups (e.g. acetylamino groups), sulfodiamide groups (e.g. methanesulfonamide groups), sulfamoyl groups (e.g. methylsulfamoyl groups), halogen atoms (e.g. fluorine, chlorine, bromine, etc.) ), carboxy group, carbamoyl group (e.g. methylcarbamoyl group)
, alkoxycarbonyl group (e.g. evamethoxycarbonyl group etc.), sulfonyl M (e.g. methylsulfonyl group)
can be mentioned. When there are two or more substituents, they may be the same or different.

Among the color coupler residues represented by Q, cyan color-forming coupler residues include the phenol type (CI[I) or naphthol type described in European Patent Publication Ioi No. 47].
CVD ones are preferred, where &, z1ti, respectively, European Patent Publication No. 10/.

It means the same thing as described in No. 421.

The magenta color-forming coupler residue is preferably of the pyrazolone or indashilon type, for example "5z a5□" (CM) described in European Patent Publication No. 101,621.
It is the same as that described in .

Yellow color-forming coupler residues include those of the acruacetanilide type, especially of the pivaloylacetanilide type (CV
l ), benzoylacetanilide type c c vn )
, [C■] is preferable.”It 4
'! In formula 13, L, 3, "54, .5,"56 and Z3 are the same as those described in European Patent Publication No. 101,411.

Next, non-color-forming ethylene-like monomers that do not couple with aromatic-grade amine developers and oxidation products include acrylic acid, α-chloroacrylic acid, α-deracrylic acid (such as methacrylic acid), and Esters or amides derived from these acrylic acids (e.g. acrylamide, n-butylacrylamide, t-butylacrylamide, diacetone acrylamide, methacrylamide, methyl acrylate, ethyl acrylate, 1
1-propyl acrylate, n-butyl acrylate,
t-butyl acrylate, 1so-butyl acrylate, coethylhexyl acrylate, n-octyl acrylate, lauryl acrylate, methyl methacrylate, ethyl methacrylate), n-7' methyl methacrylate and β-hydroxy methacrylate), methylene Dibisacrylamide, vinyl esters (e.g. vinyl acetate, vinyl propionate and vinyl laurate), acrylonitrile, methacrylonitrile, aromatic vinyl compounds [e.g. styrene and its rust derivatives, vinyltoluene, divinylbenzene, vinylacetophenone and sulfostyrene] , itaconic acid, citraconic acid, crotonic acid, vinylidene chloride, vinyl alkyl ether (e.g. vinyl ethyl ether), maleic acid, maleic anhydride, maleic ester, N-
Examples include vinyl-copyrrolidone, N-vinylpyridine, and co- and ≠-vinylpyridine. One or more of the non-color-forming ethylenically unsaturated monomers used here can also be used together. Examples include n-butyl acrylate and methyl acrylate, styrene and methacrylic acid, methacrylic acid and acrylamide, methyl acrylate and diacetone acrylamide, and the like.

The polymer coupler used in the present invention may be water-soluble or water-insoluble, but polymer coupler latex is particularly preferred.

Polymer coupler latex can be made by first taking out a hydrophilic polymer coupler made by polymerizing a monomer, and then redissolving it in an organic solvent and dispersing it in the form of latex. A solution of polymeric cassillary may be directly dispersed in the form of a latex.

Alternatively, a polymer coupler latex prepared by an emulsion polymerization method or a layered polymer coupler latex may be directly added to the gelatin silver halide emulsion.

U.S. Patent J, for water-soluble polymer Cassirer;
'／ j j, ! / No. 0, same J, here / , 1
No. 62, 3, 2? Polymer coupler latex can be prepared by the method described in U.S. Pat. , No. 120, a method of directly adding a polymer coupler latex prepared by an emulsion polymerization method to a gelatin silver halide emulsion is described in U.S. Pat.
o, co// issue, 3゜370, ri 62, 3,126
．． It can be made by the method described in Ko 3, J, 747, ≠lλ, British Patent/, 2≠7,6it.

These methods are also applicable to the formation of homopolymers and copolymers.

A description of polymerization and dispersion can be found in European Patent Publication 10/
, No. 62/.

The proportion of the coloring part in the polymer coupler is usually j-
10 weight is desirable, but 20 to 70 weight is particularly preferred in terms of color reproduction, color development and stability. In this case, the molecular weight (grams of polymer containing 7 moles of monomeric coupler) is about 2jO to .mu.000, but is not limited thereto.

Examples of monomeric couplers suitable for polymerization to produce polymeric cassillars in accordance with the present invention and their synthesis methods are found in various publications, such as Belgian Patent No. 11 Hiroshi, No. 4cP4C, Belgian Patent No.
No. 462,271, British Patent No. 247,103
No. 1. /30,111, same No. i, x4! 'y,
Try No. 1. JA5', 3j! No., U.S. Patent No. J, Jjt, Art No. J, 7A7,4A/Co,
4? Wishing you all the best! -/7/j444A, zA-41F7
No. 9, same j″6-10ri0!, same jt-1lAOA
& No. 7, same! Seen on the 7-λ Hiroiri issue.

Representative examples are as shown below, but are not limited thereto.

(C-/n (C-co) OH α (C-J) (C-Hiroshi) OH (C-j) α (C-B) (C-7) OH α (C-2) (C-10) α (C-/J) H α (C-/Ir) C) 12C) 12CN C) 12CF3 α (M-A) SO□CH3 (M-t) (M-/j) (JC)I3 (M-/ri) α (M-20) α (M-col) (M-Coco) α (M-ko3) ○ Pity to ℃ Humiliation Q hmm (M-Kori (M-5' C) i3 ■ α (M-27) C1-13 (M-kot) H3 (M-Kota) (M-Jo) α (M-J/) (M-32) H3 (M-Jj) QC)I.

CM-31IL) d3 (M-Jj) C1 (3 (M-j4) ~ QC) (3 (M-37) H3 (M-Jr) (Y-Co) COOC) (3 (Y-J) (Y -j) (Y-1) Cf(3 (Y-7) (Y-r) (Y-ta) (Y-70) (Y-//) NHCOC)i=cH2 Polymer coupler latex is coupler monomer It is preferable to add 0.001 mol to O0! mol, preferably 0.0/-0.0! mol, per 7 mol of silver.

As the DIR coupler used in the present invention, for example, US Pat. Ko27, j! ≠ No. 3゜617.4
No. 21, No. 3.43, No. 3 Hiroj, No. 3.7 oi
,'yrJ issue, 3.7?0. JI≠, West German Patent Application (OLS) No. 2,44/4゜oat, OLS No. 2. ≠
JlL, No. 301, No. 2゜lAj≠, No. J2, British Patent No. 3. ≠Yo San No., JP-A No. 7-/2233j, J, Z-4941 No., JP-A No. 7/-/l, /≠1
There are some listed in the issue.

f) Compounds other than IR couplers that release a development inhibitor upon development include, for example, US Pat. Ko P7
．． No. ≠ j-, same No. 3. J7, No. 522, West German Patent Application (OLS) No. u, 4C/7. Fl Hiro issue, Tokukai Shoj Co/jλ71 issue, same! There is one described in No. 3-2iit.

The diffusible DIR compound as used in the present invention means a compound that can form a highly diffusive development inhibiting substance during development, but in the present invention, the diffusivity is 0. (Measurement method and diffusivity D
IR compounds are described in European Patent IO/Aco 1.

DIR that can release the highly diffusible development inhibitor substance of )
Compounds are preferred, and among the DIR compounds, DIR and couplers are preferred. Such an IFI coupler is represented by the following general formula (1).

General formula (1) In the formula, A represents the oak 2-component, m represents/or
Y represents a group that binds to the coupling position of the cazole component and leaves by reaction with the oxidized product of the color developing agent, and represents a highly diffusible development inhibitor or a compound capable of releasing a development inhibitor.

In general formula (1), Y is the following general formula (Ila) ~ (
V).

General formula (Ha) General formula [■b] General formula [River] (Rue) n General formula (IV) 薯ρ General formula (V) Ru3 General formula [■! l), ([[b) and ([l[), al is an alkyl group, an alkoxy group, acylamino f,
, 7% 0 Ken atom, alkoxycarbonyl group, thiacylyrizo/amino group, aryloxycarbonyl group, acyloxy group, carbamoyl group, N-furkylcarbamoyl M, N*N-dialkylcarbamoyl group, nitro group, amino group, N-aryl group 7 carbamoyloxy groups, sulfamoyl & N-alkylcarbamoyloxy groups, 7 hydroxy groups, alkoxycarbonylamino groups, alkylthio groups, arylthio groups, aryl groups, heterocyclic groups, cyano groups, alkylsulfonyl groups or haaryloxycarbonylamino groups represents a group. General formula (Ila), (ff
In b) and (III), n represents l or
When is 1, R□ may be the same or different, and the total number of carbons contained in n a's is o-io.

In the general formula (fV), R2 represents an alkyl group, an aryl group or a heterocyclic group.

In general formula (V), R3 is a hydrogen atom, an alkyl group,
Represents an aryl group or a heterocyclic group, R4 is a hydrogen atom, an alkyl group, an aryl group, a halogen atom, an acylamino group, an alkoxycarbonylamino group, a dicarbonylamino group, an alkanesulfonamide group, a cyano group, or a heterocyclic group. cyclic group, alkylthio group or amine at
represent.

When R3 or R4 represents an alkyl group, it may be substituted or unsubstituted, linear or cyclic. The 1lfi substituent is a halogen atom, a nitro group,
Cyano group, aryl group, alkoxy group, aryloxy group, alkoxycarbonyl group, aryloxycarbonyl group, sulfamoyl group, carbamoyl group, hydroxy 7
group, alkanesulfonyl group, arylsulfonyl group, alkylthio group, or arylthio group.

When R1, R2, R3 or R14 represents an aryl group, the aryl group may be substituted. As a substituent,
Alkyl group, alkenyl group, alkoxy group, alkoxycarbonyl group, halogen atom, nitro group, amino group, sulfamoyl group, hydroxy group, carbamoyl group, aryloxycarbonylamino group, alkoxycarbonylamino group, acylamino group, cyano group or ureido group These are the basics.

When R, , R2, R3 or R4 represents a heterocyclic group, the heteroatom includes a nitrogen atom, an oxygen atom, and a sulfur atom! Represents a monocyclic or fused ring of a membered or t-membered ring, a pyridyl group, a quinolyl group, a heptadyl group, a benzothiazolyl group,
These selected from oxasilyl group, imidazolyl group, thiazolyl group, triazolyl group, benzotriazolyl group, imido group, oxazine group, etc. may be further substituted with the substituents listed for the above-mentioned aryl group.

In general formula (IV), the number of carbons contained in R2 is /
~/j.

In the general formula (V), the total number of carbons contained in R3 and 1 is 1 to 1.

In the general formula (1), Y can also be represented by the following general formula i).

General formula i) -TIME-INHIBIT In the formula, the TIME group is a group that is bonded to the coupling position of the coupler and can be cleaved by reaction with a color developing agent,
After cleavage from Kab2-, it is a group that can release the IN)IIBIT group in a moderately controlled manner.

The INHIBIT group is a development inhibitor.

In the above formula, the -TIME-INHIBIT group is preferably represented by the general formula (■) ~-- as described in European Patent Ioi, t2.
It has the general formula XI).

Among the above diffusible DIR compounds, general formulas [■a), (
Particularly preferred are those with withdrawal funds represented by Ilb) to (V).

The yellow image-forming coupler residue represented by A includes pino(roylacetanilide type, be/diylacetanilide type, malondiester type, 10-diamide type, dibenzoylmethane type, benzothiazolylacetamide type, malone ester monoamide type). type, benzothiazolylacetate type, benzoxacylylacetamide type, benzoxacylylacetate type, malone diester type, pen, zimidazolylacetamide type or benzimidazolylacetate type coupler residue, U.S. Pat. No. 3, t
≠/, coupler residues derived from heterocycle-substituted acetamides or heteroterm-substituted acetates contained in US Pat. No. 110, or U.S. Pat. ≠! , No. 17/, West German Patent (OLS) No. 1. ! 0
No. 3,092, coupler residues derived from acylacetamides described in JP-A No. 731 or Research Ken Disclosure/J737, or U.S. Patent No. ≠, O≠6. ! Examples include the heteroterminal coupler residues described in No. 7≠.

The magenta image-forming coupler residues represented by humans include the j-oxo-λ-pyrazoline nucleus, pyrro(/,
j-a) Coupler residues having a benzimidazole core or a cyanoacetophenone type coupler residue are preferred.

The cyan image-forming coupler residues expressed in humans are:
Coupler residues with a phenolic or alpha-naphthol core are preferred.

In the general formula (1), the general formula CIA), [■A], [■A], (■A) described in European Patent No. 10/621
, (MA), [■person], [■A], [■A), (IXA
) is preferred.

Specific examples of diffusible DIR couplers are shown below.

H C) 13CH3 J)-J D-see OC engineering, H2゜ ])−j N=N D-i.

(t)C, H1□ 1) -/ko I)-/J H2 -1s D-/A D-/7 α D-/1 I α Otsu m , “I! ])-21A l D-ko α D-, 2A -a 7 D-kot Nf(COCf-I,.

D-Kota α -JO D-J/ D-J KoD-JJ D-JJ1 -3s D -J t (t)C
,f(Yu.

(t) C, H1□ -Jro2 D-San〇D-4Li D-Taiko D-μJ -4L4c D-≠j -4A The amount of DIR compound and diffusible DIR compound added is o, oo
ooi~o,oo mol/m'' is preferred, more preferably o, oooo ko~0.00/mol/m
It is m.

The above diffusible DIR compound according to the present invention is disclosed in U.S. Patent No. 3,2 Core, jj≠, U.S. Pat.
Same 3rd. ri JJ, No. 100, same No. J.

yjr, yy3, same No. ≠, l hiro, tit no, same no, hiro, co JIA, 471, JP-A-11-1999/J43-1, same 17-! No. 4137, British Patent No.

It can be easily synthesized by the method described in 070.266, 07λ1363, Research Disclosure No. 212, December 1st, No. 21 λ, etc.

According to the present invention, the effect of the present invention itself is not affected whether I/silver halide is contained in the non-photosensitive layer or not at all. When photosensitive silver halide is contained, 10% or more of the total molar amount of compounds that can cause a coupling reaction with the oxidation product of the developing agent contained in the non-photosensitive layer, preferably 7096 or more, More preferably, by making the DIR compound account for 0% or more (100% is extremely advantageous), the development of the photosensitive layer/silver oxide in the layer is significantly suppressed, and the This is because it can be said to be non-photosensitive.

The thickness of the non-photosensitive layer is preferably 0.
3 to 3μ is more preferable.

In the present invention, diffusible DIR, compounds, and other cazolers described below can be introduced into silver halide emulsion layers or non-photosensitive layers using known methods, such as U.S. Pat.
The method described in this issue is used. For example, phthalic acid alkyl esters (dibutyl phthalate, dioctyl phthalate, etc.), phosphoric acid esters (diphenyl heptophosphate, triphenyl phosphate, tricresyl phosphate, dioctyl butyl phosphate), citric acid esters (e.g. acetyl tributyl citrate),
Benzoic acid esters (e.g. octyl benzoate), alkylamides (e.g. diethyl laurylamide), fatty acid esters (e.g. dibutoxyethyl succinate, diethyl azelate), trimesic acid esters a (e.g. trimene/tributyl acid), etc. Boiling point io'c or l! 00C organic solvents, such as lower alkyl acetates such as ethyl acetate, butyl acetate, ethyl zolopionate, co-butyl alcohol, methyl isobutyl keto/, β
- After being dissolved in ethoxyethyl acetate, methyl cellosolve acetate, etc., it is dispersed in a hydrophilic colloid.

The above-mentioned high boiling point organic solvent and low boiling point organic solvent may be used in combination.

Also, Tokko Akira! It is also possible to use the dispersion method using a polymer described in Japanese Patent Application Laid-Open No. 2003-120003.

When the cazoler has an acid group such as carboxylic acid or sulfonic acid, it is introduced into the hydrophilic colloid as an alkaline aqueous solution.

As the binder or protective colloid used in the emulsion layer or intermediate layer of the light-sensitive material of the present invention, it is advantageous to use gelatin, but other hydrophilic colloids can also be used.

For example, gelatin conductors, graft polymers of gelatin and other polymers, proteins such as albumin and casein; cellulose derivatives such as hydroquine ethyl cellulose, carboxymethyl cellulose, and cellulose sulfate esters; sugar derivatives such as sodium alginate and starch derivatives; polyvinyl Various synthetic hydrophilic polymeric substances such as single or copolymers of alcohol, N-IJ vinyl alcohol partial acetal, P-IJ N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, polyvinylpyrazole, etc. can be used.

Examples of gelatin include lime-processed gelatin, talc acid-processed gelatin, Bull, 8oc, 8ci, and Phot.

Enzyme-treated gelatin as described in Japan, JI6/1, PJO (/FAA) may be used, and gelatin hydrolysates and enzymatically decomposed products may also be used. Examples of conductors for gelatin include acid rides, acid anhydrides, incyanates, bromoacetic acids, alkanesultones, vinylsulfonamides, maleimide compounds, polyalkylene oxides, epoxy compounds, etc. Those obtained by reacting various compounds can be used.

Any of silver bromide, silver iodobromide, silver iodochlorobromide, silver chlorobromide and silver chloride may be used as silver halide in the photographic emulsion layer of the photographic light-sensitive material used in the present invention. Preferred silver halide is silver iodobromide containing less than or equal to is morte iodide faf:. Particularly preferred is silver iodobromide containing silver iodide ranging from λ morti to lλ morti.

The average grain size of silver norogenide grains in photographic emulsions (the grain diameter is used for spherical or approximately spherical grains, the grain size is taken as the principal grain size for cubic grains, and the average size is expressed as the projected area) is particularly important. Although it does not matter, it is preferably 3μ or less.

The particle size may be narrow or wide.

The silver halide grains in the photographic emulsion may have a regular crystalline structure such as a cube or a hexagonal, or may have a spherical or hexagonal shape.
It may have an irregular crystalline shape such as a plate shape, or it may have a composite shape of these crystalline shapes. It may also consist of a mixture of particles of various crystalline forms.

Further, an emulsion may be used in which ultratabular silver halide grains having a diameter of at least j times the grain thickness occupy at least jO- of the total projected area.

The silver halide grains may have a layered structure in which the interior and surface layers have different phases, a bonded structure, or a uniform phase. Further, the particles may be particles in which a latent image is mainly formed on the surface, or may be particles in which a latent image is mainly formed inside the particles.

The photographic emulsion used in the present invention is P, Glafkide.
Written by Chimie et Physique Photo
ographique (published by Paul Monte 1, 15F67), G, F.

Photographic Emuls by Duffin
ionChCmistry (The Focal
Press, 1ytt), V, L, Ze eyes k
Making and C by man et al.
oating Photographic Emulsi
on (The Focal Press, l
The axial strain can be applied using the method described in 6≠year). That is, any of the acidic method, neutral method, ammonia method, etc. may be used, and the method for reacting the soluble silver salt with the soluble halogen salt may be any one-sided mixing method, simultaneous mixing method, or a combination thereof. good.

A method in which particles are formed in an excess of silver ions (so-called back-mixing method) can also be used.

As one type of simultaneous mixing method, a method in which the pAg in the liquid phase in which silver halide is formed can be kept constant, that is, the so-called Chondrald double jet method can also be used.

According to this method, a silver halide emulsion having a regular crystal shape and a nearly uniform grain size can be obtained.

One or more silver halide emulsions formed separately may be used in combination.

In the process of silver halide grain formation or physical ripening, cadmium salts, zinc salts, lead salts, thallium salts, iridium salts or their complex salts, rhodium salts or their lead groups, iron salts or iron complex salts, etc. may be present in the coexistence. good.

After the emulsion is precipitated or physically ripened, soluble salts are usually removed. For this purpose, the long-known Tardel water washing method, which involves gelling gelatin, may be used. Inorganic salts such as sodium sulfate, anionic surfactants, anionic polymers (e.g. polystyrene sulfonic acid), or gelatin derivatives (e.g. aliphatic acylated gelatin, aromatic acylated gelatin, aromatic carbamoylated gelatin, etc.) A flocculation method may also be used.

Silver halide emulsions are usually chemically sensitized.
e Grundlagen der Photogr
aphischenProzesse mtt Sil
berhalogeniden” (Akademisc
he Verlagsgesellschaft.

15'4F) 47j to 7J4C The method described in the negative section can be used.

That is, sulfur sensitization using sulfur-containing compounds that can react with active gelatin and silver (e.g., thiosulfates, thioureas, mercapto compounds, rhodanines); reducing substances (e.g., stannous salts, amines, hydrazine conductors, formamidine sulfinic acid, silane compounds); noble metal compounds (e.g., total complex salts, Pt, I
The photographic emulsion used in the present invention may be used alone or in combination with a noble metal sensitization method using complex salts of metals of group I of the periodic table such as Pd, Pd, etc. Alternatively, various compounds vlJ' can be used to prevent fogging during photographic processing or to stabilize photographic performance.
e can be included. That is, azoles such as penzothiazolicum salts, nitroimidazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, aminotriazoles, etc. , azoles, benzotriazoles, nitrobenzotriazoles, mercaptonatozoles (especially l
-Phenyl-! Mercaptopyrimidines; Mercaptotriazines: Thioketo compounds such as oxadolinthion; Azaindenes OJ'ls For example, triazaindenes, tetraazaindenes (especially ,
3a, 7) Tetraazaindenes), pentaazaindenes; add many compounds known as antifoggants or stabilizers such as henzenethiosulfonic acid, benzenesulfinic acid, benzenesulfonic acid amide, etc. be able to.

The photographic emulsion layer or other hydrophilic colloid layer of the light-sensitive material prepared using the present invention may contain coating aids, i# antistatic properties, slip property improvement, emulsification dispersion, adhesion prevention, and photographic property improvement (e.g., development acceleration, Various surfactants may be included for various purposes such as high contrast, sensitization, etc.

For example, saponins (steroids), alkylene oxide cast conductors (e.g. polyethylene glycol, polyethylene glycol/polypropylene glycol condensates, polyethylene glycol alkyl ethers or polyethylene glycol alkyl aryl ethers, polyethylene glycol esters, polyethylene glycol sorbita/esters polyalkylene glycol alkylamines or amides, silicone polyethylene oxide adducts), glycidol derivatives (e.g. alkenyl succinic modified polyglycerides, alkylphenol polyglycerides), fatty acid esters of polyhydric alcohols, alkyl esters of sugars, etc. Nonionic surfactants; alkyl carboxylates, alkyl sulfonates, alkylbenzene sulfonates, alumina 7talene sulfonates, alumina sulfuric acid esters, alkyl phosphate esters E, N-acyl-N-alkyl Carboxylic 7iL such as taurine, sulfosuccinic esters, sulfoalkyl polyoxyethylene alkylphenyl ethers, polyoxyethylene alkyl phosphates, etc.
Anionic surfactants containing acidic groups such as sulfo groups, phospho groups, sulfate ester groups, phosphate ester groups; amino acids;
Ampholytic surfactants such as aminoalkyl sulfonic acids, aminoalkyl sulfates or phosphoric acid esters, alkyl betaines, and amine oxides; Alkylamine salts, aliphatic or aromatic primary ammonium salts M1 Complex compounds such as pyridinium and imidazolium Cationic surfactants such as cyclic am7nium salts and phosphonium or sulfonium salts containing aliphatic or heterocycles can be used.

The photographic emulsion layer of the photographic light-sensitive material of the present invention contains, for example, polyalkylene oxide or its derivatives such as ethers, esters, and amines, thioether compounds, thiomorpholines, quaternary Ammonium chloride, urethane rust conductor,
It may also contain urea derivatives, imidazole enzyme derivatives, 3-pyrazolidones, and the like.

The photographic light-sensitive material used in the present invention may contain a dispersion of a water-insoluble or sparingly soluble synthetic polymer in the photographic emulsion layer or other hydrophilic colloid layer for the purpose of improving dimensional stability. For example, alkyl (meth)acrylates, alkoxyalkyl (meth)acrylates, glycidyl (meth)acrylates, [methacrylamide, vinyl esters (e.g. vinyl acetate), acrylonitrile, olefins, styrene, etc. alone or in combination, or together with acrylic acid, methacrylate, etc. A polymer containing a combination of acid, α, β-unsaturated dicarbonate, hydroxyalkyl (meth)acrylate, sulfoalkyl (meth)acrylate, styrene sulfonic acid, etc. as a monomer component can be used.

For photographic processing of Id made of a photographic emulsion made using the present invention, any of the known methods and known processing solutions as described, for example, in Research Disclosure No. 174, pages 2r to 30, may be used. can be used. This photographic processing may be carried out depending on the purpose or dye a! Any photographic processing (color photographic processing) that forms the image may be used. The processing temperature is usually selected between /r'CJk and jOoC, but may be lower than /rC or higher than l-1t, so'C.

As a special form of development processing, a developing agent is added to the light-sensitive material.
For example, a method may be used in which the photosensitive material is included in the emulsion layer and developed by processing the photosensitive material in an alkaline aqueous solution. Research Disclosure 1 for hydrophobic developing agents
16 Octopus T1 US Patent Co., 7J Ri, I Ri No. 0,
British patent ti3゜koj3 or West German patent/, jhiro7.7
It can be included in the emulsion layer by various methods described in tJ issue and the like. Such development treatment may be combined with silver salt stabilization treatment with thioheptananate.

As the fixer, one having a commonly used composition can be used. As the fixing agent, in addition to thiosulfates and thiocyanates, organic sulfur compounds known to be effective as fixing agents can be used. The fixing solution may contain a water-soluble aluminum salt as a hardening agent.

When forming a dye image, conventional methods can be applied.

For example, negative/positive method (e.g. “Journal of
the 5ociety of motion
Picture and Te1evision Eng
ineers''&/volume (/9j 3rd year), 4A7-70
/ page) etc.

Color developers generally consist of an alkaline aqueous solution containing a color developing agent. The color developing agent is a known primary aromatic amine developer, such as a phenylene diamine developer (e.g. ≠-
Amino-N, N-diethylaniline, 3-methyl-Hiro-
Amino-N, N-diethylaniline, ≠-amino-N-
Ethyl-N-β-hydroxyethylaniline, 3-methyl-μmamino-N-ethyl-N-β-hydroxyethylaniline, 3-methyl-≠-amino-N-ethyl-N-β-methanesulfamide ethylaniline, ≠- amino-3-methyl-N-ethyl-N-β-methoxyethylaniline, etc.) can be used.

Besides this, pHotograph by F.A. Mason
icProcessing Chemistry (F
published by ocalPress, ixt), 22t-%-
24? , US Patent λ, /? J, 0/J issue, same, j octopus.

Jt No. 33, JP-A No. 4-4 Hiroki No. 33, etc. may be used.

Color developers may also contain development inhibitors or antifoggants such as p)tkWr agents such as alkali metal sulfites, carbonates, borates, and phosphorous radicals, bromides, iodides, and organic antifoggants. It can also contain agents such as If necessary, water softeners, preservatives such as hydroxylamine, organic solvents such as benzyl alcohol and diethylene glycol, polyethylene glycol, quaternary ammonium salts, and amines may be used. a Development accelerator, dye-forming coupler, competitive coupler, fogging agent such as sodium boron/S hydride, auxiliary developer such as l-phenyl-3-pyrazolidone, viscosity agent, polycardiic acid chelate It may also be included in agents, antioxidants, etc.

The photographic emulsion layer after color development is generally subjected to a whitening process.

The bleaching process may be performed simultaneously with the fixing process, or may be performed separately. As a bleaching agent, for example, iron (Ill.
), compounds of polyvalent metals such as cobalt (ill), chromium (Vt ), copper i), peracids, quinones, nitrone compounds, etc. are used.

For example, ferri heptaanide, dichromate, iron (Ill
) or organic complex salts of cobalt(III), such as ethylenediaminetetraacetic acid, nitrilotriacetic acid, l.

Complex salts of aminopolycarboxylic acids such as 3-diaminocopro/@nortetraacetic acid or organic acids such as citric acid, tartaric acid, and malic acid; persulfates, permangaffes, and nitronephenols can be used. Among these, potassium ferricyanide, ethylenediamine/iron tetraacetate (I
II) Sodium and ethylenediamine/ferric tetraacetate (Il
l) Ammonium is particularly useful. Ethylenediaminetetraacetic acid iron (In) complex salts are useful in both stand-alone bleach solutions and -bath bleach-fix solutions.

For bleaching or bleach-fixing solutions, see U.S. Pat. It
No., Special Publication No. 441-1117. In addition to the bleaching accelerator described in JP-A-13-4173, etc., and the thiol compound described in JP-A No. 13-4173, various additives can also be added.

The photographic emulsions used in the present invention may be spectrally sensitized with methine dyes and others. The lare dye VCd used,
7-anine dye, merocyanine dye, complex cyanine dye,
Included are complex merocyanine dyes, holopolar-7 anine dyes, hemicyanine dyes, styryl dyes and hemioxonol dyes. Particularly useful dyes are cyanine dyes,
It is a pigment belonging to merocyanine pigments and complex merocyanine pigments. Any of the nuclei commonly used for cyanine dyes can be used as basic heterocyclic nuclei for these dyes. Namely, pyrroline nucleus, oxysilin nucleus, thiazoline nucleus, pyrrole nucleus, oxazole nucleus, thiazole nucleus, selenazole nucleus, imidazole nucleus, tetrazole nucleus, pyridine nucleus, etc.; A nucleus in which an alicyclic hydrocarbon ring is fused to these nuclei. ; and a nucleus in which an aromatic hydrocarbon ring is fused to these nuclei, i.e., an indolenine nucleus, a benzindolenine nucleus,
Applicable are indole nucleus, penzoguisadol nucleus, naphthooxazole nucleus, benzothiazole nucleus, naphthothiazole nucleus, benzoselenazole nucleus, benzimidazole nucleus, quinoline nucleus, etc. These nuclei may be substituted on carbon atoms.

Merocyanine dyes or complex merocyanine dyes include a pyrazoline-yone nucleus, a thiohydantoin nucleus, a corchioxazolidine nucleus, a ≠-dione nucleus, a thiazolidine-λ, a ≠-dione nucleus, a rhodanine nucleus, and a thiobarbyl nucleus having a ketomethylene structure. A 3-4 membered heteroartic ring nucleus such as an acid nucleus can be applied.

These sensitizing dyes may be used alone or in combination, and combinations of sensitizing dyes are often used particularly for the purpose of supersensitization.

Along with the sensitizing dye, a color S that itself does not have a spectral sensitizing effect or a substance that does not substantially absorb all visible light,
The emulsion may contain a substance exhibiting supersensitization.

The invention is also applicable to multilayer, multicolor photographic materials having at least λ different spectral sensitivities on the support. A multilayer natural color photographic material usually has at least one each of a red-sensitive emulsion layer, a green-sensitive emulsion layer, and a blue-sensitive emulsion layer on a support.

The order of these layers can be arbitrarily selected as required. Usually, the red-sensitive emulsion layer contains a cyan-forming coupler, the green-sensitive emulsion layer contains a magenta-forming coupler, and the blue-sensitive emulsion layer contains a yellow-forming cazoler, but different combinations may be used depending on the case.

The photographic emulsion layer and non-light-sensitive layer of the photographic light-sensitive material prepared using the present invention contain dye-forming couplers, that is, aromatic primary amine developers (for example, phenylenediamine rust conductor, aminophenol etc.) in the color development process. A compound that can develop a color by oxidative coupling with a derivative (such as a derivative) may also be used.

For example, magenta couplers include j-pyrazolone couplers, pyrazolobenzimidazole couplers, pyrazolotriazole couplers, cyanoacetyl coumaron couplers, open-chain acylacetonitrile couplers, and yellow couplers include acylacetamide couplers (e.g., benzoylacetanilides, piparoyl cyan couplers include naphthol couplers and phenol couplers. These couplers are preferably non-diffusible, in which all hydrophobic groups called ballast groups are present in the molecule, or polymerized. The coupler may be either equivalent or bi-equivalent to the silver ion.

It may also be a colored coupler that has a color correction effect or a coupler that releases a development inhibitor during development (so-called DIR coupler).

Further, in the present application, the diffusive DIR compound can be used not only in the non-photosensitive layer according to the present invention, but also in other photosensitive layers and intermediate layers. The layers do not need to be colored in the same hue.

In addition to DIR couplers, the coupling reaction product is colorless and releases a development inhibitor.
It may also contain an R coupling compound.

In addition to DIII and the coupler, a compound that releases all of the development inhibitor/inhibitor during development may be included in the entire photosensitive material.

In order to satisfy the above-mentioned coupler coordinates and properties required for photosensitive materials, two or more types can be used together in the same layer, or the same compound can be added to different co-layers or more.
Of course it doesn't matter.

The photographic coloring agent used is the intermediate scale image gIf.
The maximum absorption band of a cyan dye formed from a cyan color former, which is conveniently selected to give t, is between about tOO and 7 Onm, and the maximum absorption band of a magenta dye formed from a magenta color former is about ! Preferably, the maximum absorption band of the yellow dye formed from the yellow color former is between about 000 and 4LrOnm.

In the photographic light-sensitive material of the present invention, there is no Al in the photographic emulsion layer or other hydrophilic colloid layer! Alternatively, it may contain an organic hardener. Examples include chromium salts (chromium alum, chromium acetate, etc.), aldehydes (formaldehyde, glyoxal, geltaraldehyde, etc.), N-methylol compounds (dimethylol urea, methylol dimethylhydantoin, etc.), dioxane derivatives (2,3-dihydroxydioxane, etc.) ), active vinyl compound (/,!,!-triacryloyl-hexahydro-S-triazine, /
,! -vinylsulfonyl-cozoropanol, etc.), active halogen compounds (co-dichloro-6-hydroxy-5-)riazine), mucohalogen acids a (mucochloric acid, mucophenoxychloric acid, etc.), etc. Can be used alone or in combination.

In the photosensitive material produced using the present invention, when the hydrophilic colloid layer contains dyes, ultraviolet absorbers, etc.
They may be mordanted, such as by cationic polymers.

The photosensitive material made using Kinai 8At- may contain a hydroquinone crocodile conductor, an amine phenol derivative, a gallic acid derivative, an ascorbic acid derivative, etc. as a color antifogging agent, and specific examples thereof include U.S. Patent λ, 31,0.
Kota O, Kota, JJt.

No. 327, 2. uOj, No. 72/J, 4C/1.
No. 413, λ, 471. J/≠ issue, same λ.

70/, /ri No. 7, same, 70'l, 71J, same,
721,1. ! No. r, 2.7J2. JOO issue, same 2.
7J! , No. 761, JP-A-Sho-to-yxyr No. 1, SO
-Ta λri t, 10-ta J91, 10-1
No. 10337, 1 Tsukasa 32-74! AJJj issue, special public Akira!
0-231/3% etc. K 1seet is sold out.

The photosensitive material produced using the present invention may contain an ultraviolet absorber in the hydrophilic colloid layer. For example, benzotriazole compounds substituted with aryl groups (e.g., those described in U.S. Pat. , 3j.

tri-tHzeta battle), benzophenone compound '1
12F (for example, the one described in JP-A-Kokai Akihiro 6--7r≠)
, cinnamate ester compounds (eg US Pat. No. 3,7o!
, ror No. 3,707,371),
Butageno compounds (e.g. U.S. Pat.

04cr, No. 2 Kota), or benzoxidol compounds (for example, those described in U.S. Pat. No. 3,700.1A).
(described in No. jj) can be used. moreover,
US Patent 3. ≠RiF, No. 74.2, Tokukai Sho! Hiro-+L!
Those described in No. rjJj can also be used. An ultraviolet absorbing coupler (for example, an α-naphthol cyan dye-forming coupler) or an ultraviolet absorbing polymer may be used. These ultraviolet absorbers may be mordanted in specific layers.

The photosensitive material produced using the present invention may contain a water-soluble dye in the hydrophilic colloid layer as a filter dye or for various purposes such as preventing irradiation. Moreover, 1llct:t, oxonol dye, hemioxonol dye, styryl dye, merocyanine dye,
Included are cyanine dyes and azo dyes. Among them, oxonol dyes; hemioxonol dyes and merocyanine dyes are useful.

In carrying out the present invention, the following known anti-fading agents may be used in combination, and the color image stabilizers used in the present invention may be used alone or in combination of one or more. Known anti-fading agents include hydroquino/conductor, gallic rat
Examples include s conductors, p-alkoxyphenols, p-oxyphenol derivatives, and bisphenols.

Specific examples of hydroquinone derivatives include US Patent-9360,
2PO issue, same 2. ≠It, No. 613, Same, 47! , J.
/μ issue, same co, 70/, /27 issue, same 2.70M, 7
No. 13, 2,721! , 1. ! No. 2, same, 731.
No. 300, same co, 7! j, 7t! No. 2,710. I
No. I1, same a, tit.

No. 021, British Patent/, 363. Wco No. 1, etc., and gallic acid derivatives are described in U.S. Pat. No. 3, ≠j7.
No. 072, No. 3.06 and No. 1.262, etc., and those of p-alkoxyphenols are described in U.S. Pat.
7J! , 71. ! The p-oxyphenol derivatives are described in U.S. Pat.
, 4AJ2゜300, same J, No. 173,010, same 3. ! 7≠, T-core No. 3.76μ, No. 337, JP-A No. 33633, No. 33633, same! 2-/4c71A3, same! 2-/j12 Coj, and that of bisphenols is described in U.S. Patent J, 700. Hiroj! There is a description in the issue.

Hereinafter, the present invention will be described in more detail with reference to Examples.
The present invention is not limited thereby.

Example 1 Photosensitive material consisting of each layer having the composition shown below on a cellulose acetate film support, sample 10/~IO
≠ was created.

(Sample 101) 1st layer: Antihalation layer Gelatin layer containing black colloidal silver Gelatin coating amount λ, / f / m 2 1st layer:
Intermediate layer λ, gelatin layer containing an emulsified dispersion of j-di-t-octylhydroquinone Serratia W1 fabric #/, t? / m”
3rd layer: blue-sensitive emulsion layer coating amount of silver 1,117 m2 color
Coupler D-33... O,015 mol per 1 mol of silver (J, /X10' mol/m2) Gelatin coating amount λ, o f / m
2 tricresyl phosphate o cloth t 1.1 cc/m” No. 1 Iil: Intermediate rf4 (gelatin layer) Gelatin coating amount o, At/m2 J layer: Resistance layer polymethyl methacrylate particles (diameter approx./ , jμ) (gelatin coating amount /, 097 m) In addition to the above composition, gelatin hardening agent H-7 and a surfactant were added to each layer.

The sample prepared as described above was designated as sample 101.

Compound JK-1 COOC,2)(25 (10 samples) used to prepare the samples) Coupler 1)-33 was not added to the third layer of sample 10/, and instead coupler D was added to the third layer of sample 10/. -33, the emulsified dispersion of tricresyl phosphate was applied with a coating amount of D-33 of 2
．． 'riA was added to give /xlO mol/m2. (
At this time, the gelatin coating amount of the third layer was 0.62/m2, the tricresyl phosphate coating amount #io, λcc/
It was set to tn 2. ) (Sample 10J) Instead of the coupler EX-/ in the third layer of Sample 10/, a polymer coupler latex AO (described later) was added so that the number of moles of its coloring unit portion was equal to the number of moles Ic of EX-/. . However, one hour of tricresyl phosphate
It was set as sample 101//2.

(Sample 10≠) In place of -7, polymer coupler latex AO'i was added to coupler E in the third layer of sample 10 so that the number of moles of its coloring unit portion was equal to EX-/. . However, i of tricresyl phosphate was set to //10 for 10 samples.

When the obtained samples ioi and iop were wedge exposed to sunlight and processed, almost the same sensitivity and IlI tone were obtained.

The development process used here was carried out at JIroC as shown in dC below.

t Color development ・・・・・・・・・ 3 minutes/j
Second bleaching... 6 minutes 30 minutes
Second J water wash... Old... 3 minutes/J seconds Hiroshi Fixation ......... Minute 30 seconds Water wash ...... ... Stable for 3 minutes/lj seconds 3 minutes/j seconds The composition of the treatment liquid used in each step is as follows.

Color developer sodium nitrotriacetate 1. Ofsodium sulfite μ,oysodium carbonate JO0Ofpotassium bromide
i, ay hydroxylamine sulfate ゛ ko, φ, 2gu (N-ethyl-N-β-hydroxy7ethylamino)-comethyl-aniline sulfate ta,! ? Add water /1 Bleach α Ammonium bromide /40. Of ammonia water (kotchi) Koj, 0goethylenediamine-tetraacetic acid sodium iron salt /30? glacial acetic acid
l pi tgl add water
/1 Fixer Sodium Tetrapolyphosphate K, Of Sodium Sulfite ≠, oy Ammonium Thiosulfate (70%) /7! , oz6 sodium bisulfite, add Jf water
ip stabilizer formalin r, OMI water was poured/1 The brightness of the yellow color image of these samples was judged by the conventional M'l'F method.

Table-/Ic/mm MTF values at frequencies of 920 lines per m are summarized.

As is evident from the table, a polymer coupler latex is used in the emulsion layer and a diffusive DI is used in the layer adjacent to this layer.
The sharpness of the sample to which R coupler was added (sample 1oIA) is significantly superior.

*Polymer coupler latex AO European Patent Publication No. 10/, J Co/No. is described, JP Patent Publication Shoj? - Layer (1 layer) made by the manufacturing method described in
It is a polymer Kabutsu latex with 4 stripes, and the monomer for the seed part is prepared with ethyl acrylate.
f, The monomers in the outer gold-coated part of the seed part are (Y-/) and λ-ethyl acrylate, the amount of which is 10f, and the monomer in the 6-polymer made with (70f). One unit of physical strength Zola is 17.3%.

Example 2 A multilayer color photosensitive material, sample 20/-20f7, having each layer having the composition shown below was prepared on a cellulose triacetate film support.

1st layer: antihalation layer black gelatin layer containing colloidal silver gelatin coating amount i, sy7'm2 7': intermediate layer co, j-t gelatin layer containing an emulsified dispersion of nioctylhydroquinone gelatin coating amount 1. Cota/m 3rd layer: 1st red-sensitive emulsion 1 @ silver coating t/, 7ri y/m2 Sensitizing dye I...... rxio per mole of silver
Molar sensitizing dye ■・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・． 0.003 moles per mole of silver Coupler EX-Hiroshi... o, ooot per mole of silver
Moltricresyl phosphate coating amount 0, J cc/m 2 Gelatin coating amount ko, J f/m
2nd μ layer: Coating amount of silver in red-sensitive emulsion layer 1. ≠27m2 Sensitized color, cable I・・・・・・・・・3×10 per mole of silver
Molar sensitizing dye / per mole of silver
, 2×l O mole coupler E -j...0.0 comol coupler for 1 mole of silver EX-J...o, ooit for 7 mole of silver
Moltricresyl phosphate coating amount O,cc cc/m” Gelatin coating amount/,/f/m2th j
Layer: Intermediate layer Same as second layer Layer: First green-sensitive emulsion layer Coating amount of silver 1. zf/m2 sensitizing dye■
・・・・・・・・・JXIO mol sensitizing dye for 1 mol of silver - 1x for 1 mol of silver
lOmolcassij-EX-A...0.0 per mole of silver! Molar coupler D-λ7...0I100/for 1 mole of silver
j mol (ko, /x10 '4 l/m") tricresyl phosphate m cloth t /, Jcc/m2 Gelatin coating i /, jf/m2 m71
R: Intermediate N4C gelatin W1) Ceratin coating no-ty/m2 1st layer: Fourth green-sensitive emulsion layer coating silver t, ≦1/m2 Sensitizing dye■
・・・・・・・・・・・・Co for 1 mole of silver, jX1
0 mo, le sensitizing dye ■・・・・・・・・・ o, rxio mole coupler EX-t for 7 moles of silver... 0.003 mole coupler EX-A for 7 moles of silver ...0.017 mole per mole of silver Coupler EX-7...0.003 mole of tricresyl phosphate per mole of silver m Cloth t OIlucc/ln2 Gelatin coating amount /, 417 m2 Second layer:
Yellow filter Single-layer gelatin aqueous solution containing yellow colloidal silver and co-j-t
- an emulsified dispersion of octylhydroquinone.

Gelatin coating amount 1,597m2 1st O layer: 1st blue-sensitive emulsion layer coating silver amount /, 197m2 Cazolar E
X-/...O, 25 mol coupler BK-Hiroo, oil mol tricresyl phosphate m cloth i/,! cc/m2 Gelatin coating amount i, 2y7m2 11th layer: 1st rough emulsion layer / , / 17m2 Coupler EX-/...o, ot mole tricresyl 7 osphate coating amount per 1 mole of silver 0.2 cc/m ” Gelatin coating amount /, 097 m2 1st layer: Protective layer polymethylmethanoacrylate particles (diameter approx. l).

! Apply a gelatin layer containing μ).

Gelatin coating amount /, Of/m2 In addition to the above composition, a gelatin hardening agent H-/ and a surfactant were added to each layer.

The sample prepared as described above was separated from the sample coi by 1°.

Compounds Used to Prepare Samples 111 Color I I: Anhydro r, r'-Cyclol 3.3 Nozi(r-sulfopropyl)
゛Ethylthiacarbocyanine human゛Roxide・
Pyridinium salt sensitizing dye ■: anhydroethyl-3,3/-di(r-sulfopropyl)-hiro, 4c/-! !
-Dibenzothiacarbocyanine hydroxide triethylamine salt sensitizing dye■:Anhydroterethyl-1,j/-dichloro-3,3'-di(r-sulfopropyl)oxacarbocyanine nato1nocum salt sensitizing dye ■: Anhydro j, A, j'14'-tetrachloro-7,/'-diethyl-3,37-di(β-CI-(r-sulfoprophoki7)ethoxy)ethylimidazolocarbocyanine hydroxide sodium salt EX- Lambda D-27 in the 7th layer, emulsified dispersion f of tricresyl phosphate, coating amount of D-27 is /X10
Sample λ0 except that it was added so that mol/m
It was produced in the same manner as 1.

(The amount of gelatin applied in the 7th layer at this time was 0,497 m2,
The amount of tricresyl phosphony cloth was 0°0λμ/m2. ) (Sample 03) Fourth layer turnip of sample 20/; 1) Instead of -EX-4, polymer coupler latex 8 (described later) was added so that the number of moles of its coloring unit portion was equal to EK-j. It was produced in the same manner as sample λ01 except for adding salt. However, the amount of tricresyl 7 osphate was 20//// of sample.

(Sample Co., Ltd.) Instead of the coupler EK-t in the 6th layer of Sample Co.,
Sample 20.2 was prepared in the same manner as Sample 20.2, except that Polymer Coupler Latex S was added so that the number of moles of its coloring unit portion was equal to that of BK-4. (At this time, tricresyl phosphate was removed from the sixth layer.) The obtained sample Ql-CoOIA was exposed to light for MTI, and then subjected to the same treatment as in Example 1. The sharpness of the magenta color image of the processed sample was determined by the MTF method.

The MTF values at 20 frequencies (F/mm/mm) are summarized in the table.

As is clear from Table 1, polymer coupler latex is used in the emulsion layer, and diffusive DI is used in the layer adjacent to this WIK.
The sharpness of the sample to which R coupler was added (sample ≠) is extremely excellent.

Polymer coupler latex S...European patent publication 10
1.411, as described in manufacturing method example 33, (
M-xt) and methyl acrylate aggregate (M-J
! Kashi 0, weight stI,, meb).

Patent applicant: Fuji Photo Film Co., Ltd. Showa! 2nd year 10
Mon/6th

Claims (1)

[Claims] A non-photosensitive material comprising a layer containing a polymer coupler latex on a support, and a compound adjacent thereto that is formed by a coupling reaction of a development-inhibiting compound or a development-inhibiting compound precursor with an oxidation product of a developer. A silver halide color photosensitive material having a color layer.