JPS60221751A - Silver halide color photosensitive material - Google Patents

Abstract

PURPOSE:To enhance sensitivity and sharpness by using an aromatic primary amine developing agent, and incorporating a compd. for releasing a fogging agent, a development promoter, or the precursors of them in accordance with an amt. of silver to be developed, and a polymer coupler latex. CONSTITUTION:When silver halide in a silver halide emulsion layer formed on a support is developed with an aromatic primary amine developing agent, an FR compd. for releasing a fogging agent, a development promoter, or their precursors, and a polymer coupler latex are incorporated in accordance with an amt. of silver to be developed. The FR compds. includes a coupler capable of coupling the oxidation product of the aromatic primary amine developing agent and releasing the FR compd., a coupler capable of coupling with said product and releasing a colored or colorless dye, and acting on said FR compds., a redox compd. capable of causing oxidation reduction reaction with said product and releasing the FR compds. resulting from decomposition reaction following the oxidation reaction, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a log/silver oxide photographic light-sensitive material that is highly sensitive and has excellent sharpness.

(Background Art) In recent years, silver halide photographic materials, especially photographic materials, have been developed to include ultra-high sensitivity materials such as l5O100O films, and photosensitive materials such as lIO size cameras and disk cameras. There is a growing demand for photosensitive materials with high image quality and high sharpness in small formats.

As a technology to improve sharpness, U.S. Patent 3 dyes the film with water-soluble dye to prevent irradiation, φO ri, ≠
No. 33, U.S. Pat. U.S. Patent No. J, I, 3, which similarly uses a substance that does not form a dye but releases a development inhibitor when coupled with an oxide of a herbal drug.
2.

The method described in No. 34A, No. 1 is known (
These are conventionally called DIR, compounds. ).

Furthermore, US patent≠, 24! -♂, Ri6-2, Tokukai Shoj
No. 7-14137 discloses a DIR compound that releases a highly diffusible development inhibitor, and JP-A-37-1! that releases a development inhibitor via a timing group. ≠No. 23 and the same J-/44j/
3! Discloses a method of improving sharpness using DIR compounds as described in the patent.

Although sharpness can be improved slightly by these methods, each method has the disadvantage of reducing sensitivity.

In addition, attempts have been made to improve sharpness by thinning the emulsion film and improving the MTF value in the high frequency range due to light scattering. As Tokko Sho≠Yoichi≠0/j! No., same≠t-2λ113, JP-A-57-TA-Hiro No.75-, same! It is disclosed in No. t-217≠j. It is true that the thickness of the emulsion film can be reduced by using these polymer cassillars, and the sharpness is significantly improved by making the layer thinner. However, it has become clear that polymer oak 2-latex has the drawbacks of poor coloring performance, lower density, and lower sensitivity than oil-protected type cazolers.

In order to prevent a decrease in sensitivity, increasing the amount of silver coated or the amount of cassoler coated not only increases the product cost, but also increases the film thickness and reduces the MTF value in the high spatial frequency region. Regarding the CMTF value, which results in a decrease in the sharpness of the emulsion layer as well as the sharpness of the underlying layer, see "The Theory of the Photo" by Mies.
graphicProcesses″, 3rd, E
dition, -r Cumilan Co., Ltd.).

(Object of the Invention) The first object of the present invention is to provide a silver halide color photographic material that has high sensitivity and improved sharpness. The second object is to provide a highly sensitive silver halide color photographic material that is silver-saving and has excellent sharpness. The third object is to provide a silver halide color photographic material that has excellent developability and sharpness.

(Structure of the Invention) An object of the present invention is to develop silver halide using an aromatic primary amine developing agent in a silver halide photographic material having at least one silver halide emulsion layer on a support. This was achieved using a silver halide color photographic light-sensitive material characterized by containing a compound that releases a fogging agent, a development accelerator, or a precursor thereof in response to the amount of developed silver, and a polymer cassillary latex.

The present invention will be specifically described below.

In the present invention, during development, a fogging agent or a development accelerator (hereinafter referred to as rFA compound) is added depending on the amount of developed silver.
Alternatively, a compound that releases a precursor thereof (hereinafter referred to as a "PR compound") may be added to any of the photographic layers.

PR compounds that can be used in the present invention include the following.

(1) Coupling with the oxidation product of the aromatic primary amine developing agent to release the PR compound 2-(11) Coupling with the oxidation product of the aromatic primary amine developing agent to release the PR compound Forming a colored or colorless dye, the diffusible dye undergoes a redox reaction with the oxidation product of the 2-(ii+) developing agent, which occurs subsequent to the oxidation reaction. A redox compound that releases an F8 compound through a decomposition reaction.

The above compounds (D, (i+) and qll) are represented by the following general formulas [l], [ko] and [3], respectively.

(1) cp-PR [Co) FR-cp-BALL (J) RED-PR In the above formula, the FR group is -(TIME)m-(L)n-F
Represents A. Here, the FA group represents a group having the ability to fog silver halide or a group having the ability to promote development, L represents a divalent linking group, and TIME represents a timing group.

It is particularly preferred if the FR group has a group capable of adsorbing silver halide. m and n each represent 0 or l. In addition, cp represents a cazolar residue capable of a coupling reaction with an oxidized form of an aromatic primary amine developing agent, BALL represents a diffusion-resistant group, and RED represents an oxidized form of an aromatic primary amine developing agent. Represents a compound residue that can be cross-oxidized.

Each of the general formulas (1), [C] and [3] will be explained below.

In the general formula [/], the F'B group is bonded to the coupling position of the coupler and is a group that leaves during the coupling reaction with the oxidized product of the aromatic primary amine developing agent.

Among these couplers, typical examples of yellow couplers are those disclosed in U.S. Pat.
210, same j, 26j, jO4, same, 22za, Hiro≠3, same 3.0≠t, i reference 1 same 3.4' ≠7
r 921/etc.

Among these yellow couplers, acylacetamide derivatives such as benzoylacetanilide and pivaloylacetanilide are preferred.

Therefore, as the yellow coupler residue (Cp), those represented by the following general formulas CI) and [■] are suitable.

几2 Old R □ Same, kuku represents the bonding position of the FR group (hereinafter the general formula (
Same up to IX).

Here, R□ represents the diffusion resistance of the total number of carbons from g to 3,
几2 is a hydrogen atom, a halogen atom of 1 or more, a lower alkyl group, a lower alkoxy group, or a total carbon number of 1 to 3
represents the diffusion-resistant group of 2.

When there are two or more R2's, they may be the same or different.

A typical example of a magenta coupler is a U.S. patent.

600.7tt, same, 362 Goita, same 2.3≠
No. 3,703, same J, J//, No. 012, same! ,/
J-2, ♂ri No. 4, same J,! /ri2≠Kota, same3,
It is described in OA, No. 2.437, Identical, Reor, No. Z73, etc. Among these magenta couplers, pyrazolones or pyrazoloazoles (pyrazolopyrazole, pyrazoloimidazole, pyrazolotriazole, pyrazolotetrazole, etc.) are preferred.

Therefore, the magenta coupler residue (Cp) is
In the following general formulas (In), (IV) and (V), 0 is also preferred.

Bud 2 2 Here, R1ti represents a diffusion-resistant group having a total carbon number of t to 3, and R2 represents one or more halogen atoms, lower alkyl group, lower alkoxy group, phenyl group, or substituted phenyl group. represent. Z represents a group of nonmetallic atoms necessary to form a J-membered azole ring containing 2 to 3 nitrogen atoms, and the azole ring may have a substituent (including a fused ring).

A typical example of a cyan coupler is the U.S. Patent Co.

77J, /4J issue, same J, rF! , No. 124, 3.0
02, 13/, No. 3, 03≠, T Taco, No. 2. $
70. λri No. 3, same co, 4c2B, 730, same λ, J
T7, No. 13/, and J, (Reference 7/, No. 23/s, etc.). Among these cyanogens, phenols or naphthols are preferred.

Therefore, as the cyankazolar residue (Cp), those represented by the following general formulas (Vl), [■], [■] and (IX) are suitable.

Here, R1 represents a diffusion-resistant group having a total carbon number of g to 32, and R2 represents a 7-rogen atom of 1 or more, a lower alkyl group, or a lower alkoxy group, but when R2 is 2 If further north, they may be the same or different.

The FA group is the most basic functional group that expresses the functions of PR compounds. This group includes reducing compounds (hydrazine, hydrazide, hydrazone,) 1-hydroquinone, catechol, p-aminophenol, p-phenylenediamine, l-phenyl-3-pyrazolone, enamine, aldehyde, polyamine, acetylene, aminoborane, tetrazolium salts, quaternary salts represented by ethylene bispyridinium salts, carbazic acid, etc.), or compounds that can form silver sulfide during development (such as thiourea, thioamide, dithiocarbamate, rhodanine, thiohydantoine, thiazolidinethione). , -C-N-, etc.).

TIME represents a timing group, which includes U.S. Pat. 14137
Those that utilize intramolecular substitution reactions, as described in No.
British Patent Co., 07 Co., JA JA No., Japanese Patent Application Publication No. 1983-
/j Hiroshi, 23≠ issue, JP-A-1987-/1toJs issue, JP-A-Sho jza-'? Examples include those that utilize electron transfer via a conjugated system within the molecule, as described in the LV J section.

The covalent linking group represented by L includes an alkylene group,
alkenylene group, phenylene group, naphthylene group, -0-
A group selected from the group consisting of 1-S-1-SO-1-SO2-1-N=N-, carbonamide group, thioamide group, sulfo/amide group, ureido group, thioureido group, heterocyclic group, etc. used.

The FR group consisting of the above FA group, TIME, and L is
It is particularly preferable to have a group capable of adsorbing silver halogenide (this group may be present in any part of FA, TIME, or L).

Groups that can be adsorbed to silver halide include dissociable water, a nitrogen-containing heterocyclic group having a hydrogen atom, a heterocyclic group having at least one nitrogen atom and another heteroatom in the ring,
Examples include a heterocyclic group having a mercapto group, a group derived from a compound, etc.

In the general formula [co], the Ff(, group is bonded to the non-coupling position of the cazole. The BALL group is
It is a group that is bonded to the coupling position of and leaves during the cassilling reaction with the oxidized product of the aromatic primary amine developing agent. Here, Cp and FR are represented by the general formula (/,
It has the same meaning as described in l.

The diffusion-resistant group represented by BALL has a size and shape that imparts non-diffusibility to the cazoler, and may be in the form of a polymer in which multiple leaving groups are linked, or an alkyl group that imparts non-diffusivity. It may have a group and/or an IJ & group. In the latter case, the total number of carbon atoms in the alkyl group and/or aryl group is preferably about t to 3.2. BALL has a group that binds to the coupling position of Cp, and a typical example is -o-1-8-1-N=N-1-O-C-1 be.

In the general formula [3], R and ED have a skeleton of hydroquinonone, catechol, 0-aminophenol, or p-aminephenol (including cases in which any of the above are fused rings), and represents a group that cross-oxidizes with the oxidized product of a class amine developing agent and undergoes alkaline hydrolysis to release an FR group. FR represents the same meaning as stated in general formula (1), but when PR is directly connected to the benzene ring of RED, -〇-1-S-1-N=N-1-〇 -C-1 is bonded to RED through any group, RED has an 0-aminephenol or p-aminophenol skeleton (including the case of a fused ring), and FR is a benzene ring of these. If not directly bonded to the amino group, FR is bonded to these amino groups via 1-8- (ie, forming a sulfonamide group).

Next, specific examples of F8 compounds represented by general formulas (1), [2], and [3] will be shown, but the invention is not limited thereto.

Example of a compound represented by the general formula (1) (I −/ ) (1-J ) (1-10) C 11 Example of a compound represented by the general formula (1-/) 0(CH2)15CH3 ( II-2) OCR2CH28CH(CL(2), C1(3(■-3
) 0(CH2)□1Cf(3 (■ -≠) (n-j) (II-A) NO□ (n-7) 0(CE■2)20C1□H25 Of the compound represented by the general formula [3] Example (III -/) (■-2) (1-3) OH OH (l[I-j) OH3 (Ill-6) (III-7) OH C)I2C)I2CHO (Ill-r) OH NHNHCCH3 ( ■-ta) (m-/0) Ni(N)1802C2)I8C8H□7-1 These compounds of the present invention were developed based on generally known compounds, as disclosed in JP-A-17-1101 Hiroj1. 17-/3♂t
3A, U.S. Patent 3. Coll≠, No. 377, 3. Ko! 3.
λ≠ issue, special application 1986-741! /! , special application 1976ir-
1116097, Japanese Patent Application No. 5R-J/μrot, etc.

The F8 compounds used in the present invention may be combined in combination.

The F8 compound of the present invention can be used in the silver halide emulsion layer of a silver halide color photographic light-sensitive material or its lll! Although it is contained in the i-contact layer, it is preferably contained in the silver halide emulsion layer.

In order to introduce the FR compound of the present invention and a cazole other than the polymer latex cazole into the silver halide emulsion layer, a known method such as the method described in US Pat. No. 322.027 can be used.

For example, phthalic acid alkyl esters (dibutyl phthalate, dioctyl phthalate, etc.), phosphoric acid esters (diphenyl phosphate, triphenyl phosphate, tricresyl phosphate, dioctyl butyl phosphate), citric acid esters (such as acetyl tributyl citrate), Benzoic acid esters (e.g. octyl benzoate), alkylamides (e.g. diethyl lauramide), fatty acid esters (e.g. dibutoxychechasuccinate, diethyl azelate), trimesic acid esters (e.g. tributyl trimesate), etc. Organic solvents having a boiling point of about 300 C to 30 C, such as lower alkyl acetates such as ethyl acetate and butyl acetate, ethyl zolopionate, butyl alcohol, methyl isobutyl ketone, β-ethoxyethene acetate, and methyl cellosolve acetate. It is then dispersed into hydrophilic colloids. The above-mentioned high boiling point organic solvent and low boiling point organic solvent may be used in combination.

Also, special public Shoj/-32rss, special public Shoj/-! Tata≠
The dispersion method using polymers described in No. 3 can also be used.

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

Further, the amount of the FR compound of the present invention added is from Bio to 10" mole, preferably from lo-8 to 1o-2, per mole of silver in the silver halide emulsion contained in the layer containing the PR compound or the layer adjacent thereto. It is a mole.

The polymer cassillor used in the present invention has the following general formula [≠
] is derived from the monomer strength Schiller represented by the general formula [
! ] or with one or more non-color-forming monomers containing at least one ethylene group that does not have the ability to oxidatively couple with aromatic-grade amine developers. Preferably, it is a polymer.

Here, two or more types of monomeric scillers may be simultaneously polymerized.

General formula [≠] cn2=c-CD) d-(E)e-G-cp General formula (j
) No←CH2-C) (D) d-(E) e-G-cp In the above formula, 几 represents a hydrogen atom, a lower ashky group having l-μ carbon atoms, or a chlorine atom, and G represents -CONH −
1-NHCONH-1 -NHCO□-1-co2-1-so2-1-CO-1
i fc bar 0-ヲ表wa L, D represents -CON)I- or -〇〇□-, and E has 7 to i carbon atoms.

represents a number of hydrocarbon groups.

d and e each independently represent Q or l.

Cp has the same meaning as cp in general formula (1) and [λ] of the PR compound, but G must be bonded to a non-coupling position of Cp.

Next, non-color-forming ethylene-like monomers that do not couple with the oxidation products of aromatic-grade amine developers include acrylic acid, α-chloroacrylic acid, α-alkyl acrylic acid, and derivatives of these acrylic acids. Examples include esters or amides, methylenebisacrylamide, vinyl esters, acrylonitrile, aromatic vinyl compounds, maleic acid derivatives, and vinylpyridines. ζ Two or more types of non-color-forming ethylenically unsaturated monomers used here can also be used at the same time.

The proportion of the coloring part in the polymer cassillor is usually 5.
~to weight % is desirable, and -0 to 70 weight % is particularly preferred from the viewpoints of color reproduction, color development, and stability. In this case, the molecular weight (grams of polymer containing 1 mole of monomeric schiller) is approximately 2jO to ti,,ooo, but is not limited thereto.

Next, a specific example of the monolithic oak 2- will be shown.

(C-/)OH (C-3)cH3 \ α (C-4t) (C-S) (C-O) (M-4) (Y-2) α (Y-j) (Y-6) Methods for synthesizing coupler polymers are broadly divided into 1) emulsion polymerization, +t) seed polymerization, and 111) solution polymerization.
i) a layered polymer coupler latex, and iii
) A lipophilic polymer Cassirer is obtained. The method for producing these polymers and the method for adding them to emulsions are disclosed in 1) US Pat. t-≠ko, 1 island number, +++ ) U.S. Patent J, 4A! / , is described in fco no.

The compositions of Polymer Casilar 2 Texts synthesized according to these patents are shown in Tables 3 to 3.

The polymeric coupler latex of the present invention has a silver content of 1,000%, based on the coupler monomer.

! Mol~O0! It is advisable to add mol, preferably 0.0/~0.10 mol.

Both the FR compound and the polymer coupler latex are added to the same silver halide emulsion layer.

Other dye-forming couplers may be used in the same or other photographic emulsion layers or non-light-sensitive layers of photographic materials made using the present invention in conjunction with the polymeric Cassillary described above. These include compounds having a structure in which the FA group shown in the above-mentioned general formula [1] is replaced with a hydrogen atom or a coupling-off group.

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).

In addition to DI couplers, there are also colorless DIRs in which the coupling reaction product is colorless and releases a development inhibitor.
It may also contain a coupling compound. In addition to the DI cazoler, the light-sensitive material may contain a compound that releases a development inhibitor during development.

The polymer coupler of the present invention and the above-mentioned couplers can be used in combination in the same layer in order to satisfy the characteristics required for photosensitive materials, or the same compound can be added in two or more different layers. , of course it doesn't matter.

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 halides are silver iodobromide containing silver iodide in the /jmomol range. Particularly preferred is silver iodobromide containing silver iodide in the λ molar range to/comomolar range.

The average grain size of the silver halide grains in the photographic emulsion (in the case of spherical or approximately spherical grains, the grain size is taken as the grain diameter; in the case of cubic grains, the principal grain size is taken as the grain size, and expressed as an average based on the projected area) is not particularly limited. 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 grain diameter of five times or more the grain thickness occupy SO% or more of the total projected area.

The silver halide grains may have different phases inside and on the surface. Further, the particles may be particles in which the latent image is mainly formed on the surface; or particles in which the latent image is mainly formed inside the particles.

The photographic emulsion used in the present invention is P, Glafkid
Chimie et Physique Pho by es
tographique (Paul Monte 1, 1947), G, F.

Photographic Emuls by Duffin
ionChemistry (The Focal P
ress, 1266), V, L, Zel i
Making and Coa by kman et al.
ting Photographic Emulsion
(Published by The Focal Press, li64
! It can be prepared using the method described in 2010). 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.

It is also possible to use a method in which particles are formed in an excess of silver ions (so-called back-mixing method).

As one form of the simultaneous mixing method, a method in which p-Ag in the liquid phase in which silver halide is produced can be kept constant, that is, a so-called controlled double jet method can also be used.

According to this method, the crystal shape is regular and the particle size is uniform.
A silver halide emulsion close to that obtained is obtained.

Two or more types of silver halide emulsions formed separately may be mixed and used.

In the process of silver halide grain formation or physical ripening, a cadmium salt, a zinc salt, a lead salt, a thallium salt, an iridium salt or a complex salt thereof, a rhodium salt or a complex salt thereof, an iron salt or an iron complex salt, etc. may be allowed to coexist.

Silver halide emulsions are usually chemically sensitized.

For chemical sensitization, see, for example, H. Frleser, ed.
Die Grundlagen der Photog
raphischenprozesse mit 8i
1berhalogeniden” (Akademis
che Verlagsgesellschaft.

/941)47! The method described in p. r-73 can be used.

That is, a sulfur sensitization method using a compound containing sulfur that can react with active gelatin or silver; a reduction sensitization method using a reducing substance; a noble metal sensitization method using a noble metal fly compound, etc. can be used alone or in combination. .

The photographic emulsion used in the present invention can contain various compounds for the purpose of preventing capri during the manufacturing process, storage, or photographic processing of the light-sensitive material, or for stabilizing photographic performance. Namely, azoles, mercaptotriazines, mercaptotriazines, azaindenes, benzenethiosulfonic acid, benzenesulfinic acid,
Many compounds known as antifoggants or stabilizers can be added, such as benzene theta phonamide and the like.

The photographic emulsion layer or other hydrophilic colloid layer of the light-sensitive material prepared using the present invention may contain coating aids, antistatic properties, smoothness improvement, emulsification dispersion, adhesion prevention, and photographic property improvement (e.g.
Various surfactants may be included for the purpose of accelerating development, increasing contrast, increasing g), etc.

For the purpose of increasing sensitivity, increasing contrast, or promoting development, the photographic emulsion layer of the photographic light-sensitive material of the present invention contains, for example, polyacykylene oxide or its derivatives such as ethers, esters, and amines, thioether compounds, thiomorpholines, and class ammonium salt compounds, urethane derivatives,
It may also contain urea derivatives, imidazole 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.

Photographic processing of layers comprising photographic emulsions made using the present invention includes, for example, Research Disclosure/76 No. i
Any of the known methods and known treatment liquids as described on pages t to 30 can be applied. The processing temperature is usually chosen between lr 0C and so 0c, but
The temperature may be lower than ttr 0c or above 100(:).

As the fixing solution, 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.

Color developers generally consist of an aqueous acyl solution containing a color developing agent. As the color developing agent, known general aromatic amine developers, such as phenylene diamines, can be used.

In addition, Photograph by F. A. Mason
icProcessing Chemistry (F
Pco 26-2 published by ocal Press, 1966)
．． Those described in US Pat. No. 22, U.S. Pat.

The color developer may also contain a pH buffer, a development inhibitor, an antifoggant, and the like.

Also, if necessary, water softeners, preservatives, organic solvents, development accelerators, dye-forming cazolers, competitive cazolers, fogging agents, auxiliary developers, viscosity imparting agents, polycarboxylic acid chelating agents, antioxidants. It may also contain agents.

After color development, the photographic emulsion layer is usually bleached.

The bleaching process may be performed simultaneously with the fixing process, or may be performed separately. Examples of bleaching agents include iron (■),
Compounds of polyvalent metals such as Kobayato (■), chromium (■), and copper (II), peracids, quinones, and nitroso compounds are used.

The photographic emulsions used in the present invention may be spectrally sensitized with methine dyes and others. The dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes and hemioxonol dyes.

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, it is a dye that itself does not have a spectral sensitizing effect or a substance that does not substantially absorb visible light,
A substance exhibiting supersensitization may also be included in the emulsion. The invention is also applicable to multilayer, multicolor photographic materials having at least two 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 cazoler, the green-sensitive emulsion layer contains a magenta-forming cazoler, and the blue-sensitive emulsion layer contains a yellow-forming cazoler, but different combinations may be used depending on the case.

In the photographic light-sensitive material of the present invention, inorganic or organic hardeners can be used alone or in combination in the photographic emulsion layer and other hydrophilic colloid layers.

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 light-sensitive material produced using the present invention may contain a hydroquinone derivative, an aminephenol derivative, a gallic acid derivative, an ascorbic acid derivative, etc. as a color antifoggant.

The photosensitive material produced using the present invention may contain an ultraviolet absorber in the hydrophilic colloid layer. 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.

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 two or more. Known anti-fading agents include hydroquinone derivatives, gallic acid derivatives, p-alkoxyphenols, p-oxyphenol derivatives and hibisphenols.

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

In the present invention, the gelatin may be either lime-treated or acid-treated. Details of the method for producing gelatin are described in The Fist of Macromolecular Chemistry of Gelatin, written by Arthur Vuis (Academic Press, published in 2010).

Example 1 In order to evaluate the effectiveness of the compound of the present invention, a multilayer color photosensitive material sample 1O7 having each layer having the composition shown below was prepared on a cellulose triacetate support.

The amount of emulsion coated was expressed as the amount of silver coated.

(Sample ioi) 1st layer: Antihalation layer Black colloidal silver 0.1197m2 Ultraviolet absorber U-to, /lf/m2 Same -20
, 17f//m2 gelatin layer λth layer: intermediate layer 2I! -di-t-pentadecylhydroquinone 0, / It / m
"Coupler cp-/ 0, / / 97m2 Gelatin layer containing silver iodobromide emulsion o, isy7m2 3rd layer: 7th red-sensitive emulsion layer Silver iodobromide emulsion 0.72f/m2 Sensitizing dye I...silver 7.0XIO moles per 1 mole of sensitizing dye■...Co per 7 to silver l, o'p<io mole Sensitizing dye■...Co, rxio mole per mole of silver Sensitive dye■...Co, O x 10 mole coupler for 1 mole of silver cp-az 0609317m2 coupler
cp-J O03/ 97m2 coupler Op-II
Gelatin layer containing 000109/m2 Second layer: Second red-sensitive emulsion layer Silver iodobromide emulsion 1.4 f/m2 Sensitizing dye I...1.2 x 10' mol sensitizing dye per 1 mol silver ■...for 1 mole of silver/, 1x10 mol sensitizing dye■...for 1 mole of silver, /'X,10' mol sensitizing dye■...for 1 mole of silver/ , jxlo mole coupler Cp-20,1017m” coupler 0p-J O,04/ 17m2 coupler
0p-u O,00! t/m” coupler Cp-j o
, o HiroAt/m2 Gelatin layer 5th layer: 3rd red-sensitive emulsion layer Silver iodobromide emulsion /, it/m2 Sensitizing dye Sensitizing dye s, 5xio moles per mole of silver Sensitizing dye■ ...per 1 mole of silver/, Axlo mole sensitizing dye■...co, coXIO mole per 1 mole of silversensitizing dye■...per 1 mole of silver/, tXlo mole coupler cp- J 01OjtOf/m2 coupler
Gelatin layer containing 0 p-to, Its 97 m2 Layer: Intermediate gelatin layer Seventh layer: First green-sensitive emulsion layer Silver iodobromide emulsion 0, j j ? / m2 sensitizing dye■...3 per mole of silver, rxio mole sensitizing dye■...3.0x10 mole per mole of daughter Sensitizing dye■...per 1 mole of silver /, 2XlO molar coupler Cp-bo, 2ta 2/m2 coupler 0p
-7o, ouot7m2 Cub 9- Cp-10,013
1/m2 Cazolar Cp-ta 0, Oj If
/ m 2nd layer: 1st green-sensitive emulsion layer Silver iodobromide emulsion /, jf/m2 Sensitizing dye λ, 7X10' mol per mol of sensitizing dye silver Sensitizing dye ■... Silver/- 11-/l/for ko, l
×10 molar sensitizing dye ■...1.1X/0 molar coupler Cp-601,2317m2 Cazolar cp-70,0/J f/m2 Cazolar Cp-10,00 f/m Kashi2-Cp
Gelatin layer containing -20,0//f/m" Second layer: Third green-sensitive emulsion layer Silver iodobromide emulsion /, 1117 m" Sensitizing dye ■...3.0X10 4 against silver haze Molar sensitizing dye ■...λ, ≠×lO for silver l haze Molar sensitizing dye ■...jx, io for silver 1 mole Molar coupler 〇p-100,07097m2 Casoler c
p-70,0/39/m" Gelatin layer containing tricresyl phosphate O0 Hiro O17m" I/O layer: Yellow filter layer Yellow colloidal silver 0.04Af/m2 λ,! - Gelatin layer containing 0.03197 m2 of D-t-pentadecyl hydroquino 7 Eleventh layer: First blue-sensitive emulsion layer Silver iodobromide emulsion 0. J Coy 7m 2 Casoler Op-// 0.77 97m2 Coupler
Gelatin layer containing cp-/2 0.030f//m2 tricresyl phosphate) 0.3+297m2 72nd layer: First blue-sensitive emulsion layer Silver iodobromide emulsion Q, ≠Of//m2 Casoler C
p-// 0.23 97m2 tricresyl phosphate) 0. /7 f/m2 Sensitizing dye ■... 13th layer of gelatin layer containing 10 moles of λ, JX per 7 moles of silver: Fine grain emulsion layer 1st gelatin layer containing silver iodobromide emulsion 0.2 jf/m2 ≠ Layer: 3rd blue-sensitive emulsion layer Silver iodobromide emulsion i, oot7m2 Cazolar CI) -// θ0.2x 17m2 Tricresyl phosphate o, ia 17m2 Sensitizing dye ■... per mole of silver +2.3×lO mole IS layer: 7th protective layer ultraviolet absorber [J-/'0. /Hiroshi 2/m2 Gelatin layer containing ultraviolet absorber U-20,2297m2 14th layer: 2nd protective layer Polymethyl methacrylate particles (diameter /, jμ) o, oz 17m silver iodobromide emulsion
In addition to the above composition, a gelatin hardening agent H-7 and a surfactant were applied to each layer of the gelatin layer containing the gelatin layer.

Compound U-/U-coCp-/Cp-co0CH2CH2So2C)(3CN(t)C5Hyu, Cp-μ CH2Cp-j p-x polymer Cp-10 Cp-/2H-/sensitizing dye■ (CH2)4503Na ■ CCH2)380aNa 2H5 ■ Here, the second layer couplers Cp-10 and Cp-7
was prepared and added as an emulsion as follows.

Coupler Cp-107, Off, 3f to Cp-7 with tricresyl phosphate≠oy and vinegar vt ethyl AOml
Bone gelatin 7% by weight aqueous solution 4009
and a mixture of 20g and 11 of a 10% aqueous solution of sodium lauryl sulfate, and emulsified for io minutes using a household mixer to obtain emulsion A.

(Sample 102.103) The FR compound (1-1) of the present invention was added to the φ-th layer of sample 10/.
Sample 102 and Sample 10J were prepared in the same manner as Sample 101 except that z vry / m 2 of each of Sample 102 and Sample 10J were added.

The PR compound was dissolved in tricresyl phosphate and ethyl acetate together with couplers CP-10 and Cp-7 to prepare emulsion B, and then emulsion B was prepared.
Added.

(Sample to≠) Sample 10/second layer coupler 0p-10 (0°071
Sample 104A was prepared in the same manner as Sample 10/, except that 0.0722/m 2 of the lipophilic polymer Cassilar (0) was added instead of 0.0722/m 2 /m'').

Lipophilic polymer Kashi 7-Co) 7.21 and Cp-7 7
．． 32 and trifleja phosphate! .

St. and 60 txl of ethyl acetate were heated and dissolved, then mixed with a mixture of a 7% by weight bone gelatin aqueous solution (coot) and a 10% sodium lauryl sulfate aqueous solution (j ml), and emulsified for 10 minutes with a household mixer to obtain emulsion C. Added.

(Sample 10!, /It) The same procedure as Sample io was carried out except that the PR compounds (■-4) and (1-f) of the present invention were added to the second layer of Sample 10 at j my / m 2, respectively. , Sample 10! and sample iot was prepared.

The PR compound was prepared by dissolving the lipophilic polymer Cassilar (0), the coupler CP-7, and the F compound in trifleja phosphate and ethyl acetate V to prepare an emulsion. After that, it was added.

Sample 10/-104 was imagewise exposed to white light and subjected to color development processing as described below.

The development process used here was carried out at 5r0c as described below.

t Color development・・・・・・・・・・・・3 minutes/
J seconds 2 Bleaching・・・・・・・・・・・・6 minutes 3
0 seconds 3, wash with water・・・・・・・・・3 minutes/
j second hiro fixing......... for 3 minutes
Wash for 0 seconds...Old/Dan...3 minutes is seconds,
Stability: 3 minutes/j seconds The composition of the treatment liquid used in each step is as follows.

Color developer Sodium nitrilotriacetate 1.02 Sodium sulfite or Sodium carbonate 30.09 Potassium bromide '°''7 Hydroxy or amine sulfate Ko, ≠2 ≠-(N-ethyl-N-β-hydroxyethyamino) -λ- Methyl-aniline sulfate Hiroshi!? Add water /l Bleach solution Ammonium bromide /1O1Of Aqueous ammonia (Jff%) 21.0MI Ethylenediamine-tetraacetic acid sodium iron salt /309 Glacial acetic acid Ha11 Add water /1 Fixer Sodium Tetrapolyphosphate 2.01 Sodium Sulfite Ammonium Thiosulfate (70 txl) tys,,0qt Sodium Bisulfite Hiroshi, ty Add water /1 Stabilizer Formalin t, 0txl Add water / 1. The relative sensitivity of the magenta image of these samples (sensitivity of the sample 1O/10O) and the MTF value of the cyan image at a frequency of Hiro θ lines per im were calculated.

The results are shown in the fourth column.

From Table 4, samples ioz and iot to which the present invention was applied
has higher sensitivity than sample 10/.
The sharpness expressed by sample 1 is excellent.
It is clear that the sensitivity is significantly higher compared to 04A.

Example 2 (Sample 201) The couplers Cp=// of the 11th layer, 1.2 layer, and 7th layer of Sample 10/ of Example 1 were added to the polymer Kab 2-latex (E) of the present invention, respectively. Equimolarly substituted polymer coupler latex (E) in each layer/3
f/m, 0. jilt/? "),) Sample 20/ was prepared in which both licresyl phosphate and gelatin for emulsification and dispersion were removed.

(Sample 202.203) The FB compound of the present invention (1-t
) and (1-4) at 7 wry/m, respectively.

Samples prepared by adding 3897 m'' were designated as samples 0 and 203, respectively.

Addition to the emulsion layer is polymer oak 2-latex (E)
A dimethylformamide solution of (I-4) or (1-4) was added dropwise to the aqueous solution under stirring to halogenate the polymer cassilla latex solution impregnated with (I-j) or Cl-4). This was done by mixing with silver emulsion.

These samples were subjected to imagewise exposure with white light, and Example 1
The same color development process was performed. The relative sensitivity of the yellow image (100 for sample IO7) and the MTF value of the magenta image at a frequency of pao per mm were measured. The results are shown in Table 5.

From Table 5, it can be seen that by using the FB compound and the polymer coupler in combination, a light-sensitive material with high sensitivity and excellent sharpness expressed by the MTF value can be obtained.

Patent Applicant Fuji Photo Film Co., Ltd. Procedural Amendment 1. Indication of the case: Showa-Year Patent Application No. 771nlI 2,
Title of the invention: Silver halide color photographic light-sensitive material 3, Relationship with the person making the amendment Patent applicant Address: 210-4 Nakanuma, Minamiashigara City, Kanagawa Prefecture Subject of amendment: "Detailed Description of the Invention" column 5 of the specification , the statement in the "Detailed Description of the Invention" column of the Description of Contents of the Amendment is amended as follows.

(1) Page 2, line 2 "Small formatted" "Suitable for photosensitive materials" and correct it.

(2) Page 5, line 12 rFR compound” rFA compound” and correct it.

(3) Page 5, line 15 rFR compound” rFA compound” and correct it.

(4) Page 5, lines 18-19 rFR compound” rFA compound” and correct it.

(5) Page 6, line 3 rCp-FRJ rCp-FBJ and correct it.

(6) Page 6, line 4 rFR-Cp-BALLj rFB-Cp-BALLJ and correct it.

(7) Page 6, line 5 rRED-FRJ rRED-FBJ and correct it.

(8) Page 6, line 6 rFB group” rFB group” and correct it.

(9) Page 7, line 3 rFB group” rFB group” and correct it.

Q Moan, page 8, line 3 rFB group” rFB group” and correct it.

(11) Page 14, lines 1-2, rFB group” rFB group” and correct it.

(12) Page 14, line 11 rFB group” rFB group” and correct it.

(13) Page 14, line 16 rFB group” rFB group” and correct it.

(14) Represents a group that releases the rFB group on page 15, lines 16-17. FR is "rFB"
Represents a group that releases a group. FB corrects "cyano image" to "magenta image".

(24) "Correct the MTFJ of the cyan image to the MTFJ of the magenta image" in the oldest upper column of Table 4 on page 70.

Procedural amendment January 7, 1985 Dear Commissioner of the Japan Patent Office 1, Indication of the case 1989-1999 Patent Application No. 7711!4I 2, Title of the invention Silver halide color photographic material 3,
Relationship with the case of the person making the amendment Patent applicant Location 210-4 Nakanuma, Minamiashigara City, Kanagawa Prefecture Subject of amendment Column 5 of “Detailed Description of the Invention” in the specification, “Detailed Description of the Invention” in the description of the contents of the amendment ” should be amended as follows.

(1) Change the structural formula on page 2j/line I to “R CH2=C-(D), 1-(E)e-(G)g-Cp
Correct with J.

(2) The structural formula on page 27, line 2 is [R ■ -(-CH2-C→- ■ (D) d (E) e (G) g-CpJ and correct it.

(3) After “-〇〇-1” on page 27, line 7, r-N
HCO+, -NH8O2-1-8ONH-1-OCO-
Insert 1-0CONH-1-NH+, -5-J.

(4) Page 27, line io "d and e" "d, e, and g" and correct it.

(5) Page 27 // line After "Wasu." rd, e, and g are never 0 at the same time. ” Insert.

Claims (1)

[Claims] A silver halide photographic light-sensitive material having at least one silver halide emulsion layer on a support, or containing a compound that releases a development accelerator or a precursor thereof, and a polymer cassillary latex. Silver halide color photographic material.