JPS6227739A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain a silver halide photographic sensitive material good in color developing ability, superior in color reproductivity and also in dye storage stability by incorporating a color nondeveloping compound. CONSTITUTION:The photosensitive material contains the color nondeveloping compound represented by the formula shown on the right in which each of R<1> and R<2> H or alkyl, but not simultaneously H; R<3> is halogen or an electron attractive group except -COR<4> and -SOR<5>; R<4> is alkyl, aryl, or heterocyclic, alkoxy, aryloxy, heterocyclic oxy, or amino; and R<5> is alkyl, aryl, or heterocyclic. This compound having an anionizing group has a function improving a phenomenon of hindering diffusion of a developing solution and quinonediimine, etc., into an oil occurring in the case of an oil-protected type. At least one silver halide emulsion layer is formed on a support in such a photographic sensitive material, and as a coupler, yellow, magenta, and cyan couplers can be used, and the high-boiling oil agent to be used is an organic solvent not reacting with the oxidation product of a color developing agent and having a boiling point of >=150 deg.C, such as phenol derivatives and alkyl phthalates.

Description

DETAILED DESCRIPTION OF THE INVENTION [Technical Field] The present invention relates to a photographic light-sensitive material, particularly a silver halide color photographic light-sensitive material, and more particularly to a silver halide color photographic light-sensitive material I having excellent color development properties.

[Prior art]

It is well known that in silver halide photographic materials, dyes are formed by the reaction between coupler anions and quinone diimines.

The currently mainstream method of incorporating couplers into emulsions is the so-called oil pull protection method. Therefore, the coupler is converted into a 7-ion by the penetration of the developer into the oil. Similarly, penetration of quinone diimine and the like into oil causes a Cambrinobu reaction and produces a colored pigment. Typical oils used in the method of incorporating oil 7'W are phosphoric acid esters, phthalic acid esters, and the like.

These oils serve as a site for the above-mentioned reaction, and at the same time, they also serve as a place for preserving the produced pigments.

The preservation of the produced dye is generally better when oil is present than when it is not, and the spectral absorption (color reproducibility) of the dye is also better. On the other hand, regarding oil as a reaction site, the reaction rate (dye production rate) is generally slower than, for example, Fischer dispersion type.

What is clear here is that the oil protection type oil is a factor that inhibits the coloring reaction.

As a solution to this problem, attempts have been made to introduce an anionizable group into the coupler molecule.

For failure to do so, JP-A-58-42045, JP-A-58-59
-174836, 59-177553, 59-
No. 177554, No. 59-177555, No. 59-1
No. 77556, No. 59-177557, No. 59-17
Examples include publications such as No. 8459 and No. 59-214854.

Although improvements in color development have been achieved through these techniques, some of them have problems such as low solubility in oil, making them unsuitable for oil pull protection type dispersion, or causing precipitation in emulsions. ing.

In addition, some birch products have the problem of impairing the storage stability of the produced pigment, which is a feature of the oil-protected type described above, and causing color staining.

Additionally, some introduce anionizing groups, which significantly increases the cost of the coupler. This means that the synthesis method is generally more complicated than for conventionally used couplers, and the synthesis route is longer. (
In other words, when an anionizing group is introduced, a protecting group and the like are often required, and a deprotection step is also required. ) [Object of the Invention] The first object of the present invention is to provide a silver halide photographic light-sensitive material having good color development properties.

The second object is to provide a silver halide photographic material with excellent color reproducibility (spectral absorption) and excellent dye storage stability.

The third object is to provide an inexpensive silver halide photographic material.

[Structure of the invention and its effects]

That is, the present invention relates to a silver halide photographic material characterized by containing a non-color-forming compound represented by the following general formula [I].

General formula [■] 11.1 tj In the formula, YL! O and 几2 represent a hydrogen atom or an alkyl group, and ILL and 几2 cannot be hydrogen atoms at the same time.

R3 represents a halogen atom or an electron-withdrawing group.

However, -COIL4 and -So几5 are excluded. Here, R4 represents a fulgyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, a peterocyclic group, or an amide group, and R5 represents an alkyl group, an aryl group, or a heterocyclic group.

The alkyl groups represented by R1 and R2 preferably have 1 to 32 carbon atoms and may be linear or branched. In addition, substituents (aryl, diano, ), pge〉' atoms, heterocycles, 7-rings, carboxy, carbamoyl, alphkydicarbonyl, aryloquinecarbonyl, hydroxy,
(alkoxy, oryloxy, acyl, luoquine, nitro, amine, sulfonyl, sulfamoyl, etc.). Specifically, methyl group, ethyl group, inpropyl group, [-butyl group, t-7mil group, dodecyl group, 1-hexynrunonyl group, 2-chloro-t-butyl group, trif1
Examples include olomethyl group and 1-methoxyinpropyl group.

The halogen atom represented by 1 and R3 is a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom, preferably a fluorine atom or a chlorine atom.

Examples of the electron-absorbing group represented by 几3 include s-lephonyl groups (e.g., methylsulfonyl groups, furkylsulfonyl groups such as dobnorsulfonyl groups, benzenesulfonyl groups, p-)aryl groups such as p-)ruenesulfonyl groups, etc. sulfonyl group, etc.), halogen-substituted alkyl group (e.g., trifluoromethyl group, trifluoromethyl group, perfluoro ai-propyl group, perfluoro-nj thyl group, etc.)
, a phosphonyl group (e.g., a butyloctylphosphonyl group, a phenylphosphonyl group such as an ophthenylphosphonyl group, an aryloxyphosphonyl group such as a phenoxyphosphonyl group, a four-ring arylphosphonyl group such as a phenylphosphonyl group) '4), sulfamoyl group (e.g. N
-purpylsulfamoyl group, N.

N-diethylsulfamoyl group, N-(2-pentadenoloxy/ethyl)sulfamoyl group, N-1,000-N-
dodecylsulfamoyl group, N-phenylsulfamoyl group, etc.), acyloxy group (e.g., 7 cetyloxy group, α-chloroacenaloxy group, benzoyloxy group, etc.), cyano group, di10 group, sulfo group, carboxyl Examples include groups. Among these, a cyano group, a nitro group, and a sulfonyl group are preferred.

According to the present invention, it has been found that the above-mentioned deterioration of color development can be effectively prevented by using the compound represented by the above general formula [I]. That is, oil prochik 1. W
The compound of general formula [I] having a 7-ionized group has the function of improving the phenomenon in which the penetration of the developer into the oil and the penetration of quinone diimine etc. are inhibited in the case of the above. It is thought that the fact that it also has the effect of relatively lowering the PKa of the coupler in the oil and promotes the formation of the coupler into 7-ions is one of the reasons for the above effect.

The photographic light-sensitive material according to the present invention has at least one
A silver halide emulsion layer is provided, and the coupler can be a yellow p-coupler, a magenta coupler, or a cyan coupler.

Representative specific examples of the non-chromogenic compound represented by the general formula [1] of the present invention will be described below, but the present invention is not limited to these compounds.

Shi5101A C3l-
111ftl(Cl12) s Cll3 H2O-C-CH3 (Cl-12) s C1-13 H3C-C-CH3 I CH3 CH3 Salary) C) 13 1 person CH3 802-C2Hs ゛<,, L as a yellow dye-forming coupler Known acylacetanilide couplers can be preferably used.

Among these, benzoylacetanilide and pivaloylacetanilide compounds are advantageous. Specific examples of yellow couplers that can be used are given in British Patent 1. ．． 077.874, JP 45-40757, JP 47-1031, JP 47-26133, JP 4B-94432, JP 5
0-87G50, 51-3631, 52-11
No. 5219, No. 54-99433, No. 54-1333
No. 29, No. 56-30127, U.S. Patent No. 2,875,
No. 057, No. 3,253,924, No. 3,265゜5
No. 06, No. 3,408,194, No. 3,551,15
No. 5, No. 3,551゜156, No. 3,684.841
No. 3,725,072, No. 3, 730.

No. 722, No. 3,891,445, No. 3,900,4
No. 83, No. 3,929゜484, No. 3, 933,
No. 500, No. 3,973,968, No. 3,990°8
No. 96, No. 4,012,259, No. 4,022,62
No. 0, No. 4,029゜508, No. 4,057,432
No. 4,106,942, No. 41133゜958, No. 4,269,936, No. 4,286,053,
4,304°845, 4,314,023, 4,336.327, 4,356.

No. 258, No. 4.38Q, No. 155, No. 4,401,7
This is described in No. 52, etc.

As the magenta dye-forming coupler, known 5-pyrazolone couplers, pyrazolobenzimidazole couplers, pyrazolotriazole couplers, and closed acylacetonitrile couplers can be preferably used.

A specific example of a magenta coupler that can be advantageously used is disclosed in the patent application filed in 1973.
No. 8-164882, No. 5B-167326, No. 58
-206:1121, 5B -214863, 58-217339, 59-24653, Special Publication No. 40-6031, 40-6035, 45-40
No. 757, No. 47-27411, No. 49-37854
No., JP-A No. 50-13041, 5l-2f3541
No. 51-37646, No. 51-105820,
No. 52-42121, No. 53-123129, No. 5
No. 3-125835, No. 53-129035, No. 54
-48540, 56-29236, 56-75
No. 648, No. 57-17950, No. 57-35858
No. 57-148251, No. 59-99437,
Fu' National Patent No. 1,252,418, US Patent No. 2,600
, No. 788, No. 3゜005.712, No. 3,062,
No. 853, No. 3,127,269, No. 3゜214.4
No. 37, No. 3,253,924, No. 3,311,47
No. 6, No. 3゜419.391, No. 3,519,429
No. 3,558,319, No. 3582.322, No. 3,615,506, No. 3,658,544,
3゜705.896, 3,725,067, 3,758,309, 3゜823.156, 3
, No. 834,908, No. 3,891,445, No. 3907.571, No. 3,926,631, No. 3,9
No. 28,044, No. 3935.015, No. 3,96
No. 0,571, No. 4,078,533, No. 4゜133
．． No. 686, No. 4,237,217, No. 4,241,
No. 168, No. 4゜2134.723, No. 4,301,
It is described in No. 235, No. 4,310,623, etc.

As the cyan dye-forming coupler, known cabtol couplers and phenol couplers can be preferably used. Specific examples of cyan couplers that can be advantageously used include British Patent No. 1,038,331, British Patent No. 1゜543.040, Japanese Patent Publication No. 36894/1982, and Japanese Patent Application Laid-open No. 59838/1989.
No. 50-137137, No. 51-146828, No. 53-105226, No. 54 115230,
No. 56-29235, No. 513-104333, No. 56-126833, No. 57-133850, No. 5
No. 7-155538, No. 57-204545, No. 58
- No. 118643, No. 59-31953, No. 5G -
No. 31954, No. 59-59656, No. 59-124
No. 341, No. 59-16095-6, U.S. Patent No. 2, 3
(No. 39,929, No. 2,423,730, No. 2,4
34゜272, 2,474.293, 2,69
No. 8,794, No. 2,772゜162, No. 2,801
, No. 171, No. 2,895,826, No. 3, 253
.

No. 924, No. 3,311,476, No. 3,458,3
No. 15, No. 3,476゜563, No. 3,591,38
No. 3, No. 3,737,816, No. 3,758°308
No. 3,767.411, No. 3,790.384, No. 3,880゜661, No. 3,926,684,
4,004,929, 4,009゜035, 4,012,258, 4,052,212, 4
, 124°396, 4,134,766, 4,
No. 138,258, No. 4*146゜396, No. 4,1
No. 49,886, No. 4,178,183, No. 4,20
5゜990, 4,254,212, 4,204
, No. 722, No. 4,288゜532, No. 4.29 (3
, No. 199, 4,296. Zoo No. 4,299゜914, No. 4,333,999, No. 4,334,0
No. 11, No. 4,386° No. 155, No. 4,401.75
No. 2, No. 4,427,767, etc.

As a colored coupler, for example, British patent 937.6
No. 21, No. 1,035,959, No. 1,255,11
No. 1, JP-A-48-22028, JP-A No. 52-42121
No., Special Publication No. 38-22335, No. 44-2016,
No. 44-15754, U.S. Patent No. 2,449,966, U.S. Patent No. 2,521,908, U.S. Patent No. 2,543,691,
No. 2,801,171, No. 2,983,608, No. 3,005,712, No. 3,034,892, No. 3
, No. 061,432, No. 3,419,391, No. 3,
No. 476.560, No. 3,476.563, No. 3,4
No. 81,741, No. 3,519,429, No. 3,58
No. 3,971, No. 3,622.328, No. 3,684
, No. 514, No. 4, 004, No. 929, No. 4,07
No. 0,191, No. 4,138,258, No. 4,138
, No. 264, No. 4,163,670, No. 4,292,
400, No. 4,369,248, etc. can be used.

As a DIR coupler, for example, British patent 953°45
No. 4, U.S. Patent No. 3,227,554, U.S. Patent No. 3,615,
No. 506, No. 3,617,291, No. 3,701.7
No. 83, No. 3,933,500, No. 4y095y98
No. 4, No. 4,149,888, No. 4,286,054
No. 4t35L521, JP-A-52-90932, JP-A-56-118029, JP-A-57-151944, etc., and U.S. Pat. No. 4,248,962,
No. 4,409.323, JP-A-57-1542:11
No. 4, No. 58-162949, No. 58-205150
No. 59-195643, No. 59-206834, No. 59-206836, No. 59-210440,
The timing DIR coupler described in Japanese Patent No. 60-7429 and the like can be preferably used.

As a DIR compound, for example, U.S. Patent No. 3,632゜3
No. 45, No. 3,928,041, No. 3,938,99
No. 6, No. 3,958°993, No. 3,981,959
No. 4,046,574, No. 4,052゜213, No. 4,171,223, No. 4,186,012,
JP-A-52-6543U, JP-A No. 52-130327,
Compounds described in No. 57=128335 and the like can be preferably used.

As colorless couplers, U.S. Patent No. 2,998,314 and British Patent No.
, 284, 649 and West German Patent 1,1 [38,7
A so-called Weiss coupler described in No. 69 can be used.

Furthermore, cyan couplers, magenta couplers, and yellow couplers preferably used in the present invention will be described. Specific couplers that are particularly preferably used include the following general formula (
11) (III) (IV) (V) [■] [■] [■)
[IK ) (X) (XI) (XI[) or (
Xllll).

General formula [■] General formula (1) General formula (IV) I General formula [V] General formula [■] General formula [■] General formula [■] N -N -N General formula (IK) N-N- Nl+ General formula (X) General formula [Kari] N -N -811 General formula [■] General formula [X In] In the general formulas ([1), (Ill) and [■], R7 is a halogen atom , alkyl group, acylami/group,
Or represents an alkoxy group.

R8 represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic residue.

R9 represents an alkyl group, an aryl group, a heterocyclic residue, an alkylami 7 group, or an arylami 7 group.

Mi represents an integer of 1 to 4, W represents an integer of 0 to 3, and n represents an integer of O to 5. When two or more R7s exist in the same molecule, each R7 may be the same or different.

In the general formulas (V) to [■], R10 represents an alkyl group, an aryl group, a heterocyclic residue, an acylamino group, a ureido group, or an anilino group.

R" represents a phenyl group which may be substituted with a halogen atom, an alkyl group, an alkoxy group, or a cyano group.

R's represents a halogen atom, an alkyl group, an alkoxy group, an acylamino group, a carbamoyl group, or a sulf-7 moyl group.

p represents an integer of 0 to 4.

When two or more R'2's exist in the same molecule, each R'2 may be the same or different.

R'3 represents an alkyl group, a 7-aryl group, or a heterocyclic residue.

R'4 represents an alkyl group, an aryl group, or an alkylthio group.

R'' represents an alkyl group or an aryl group.

In the general formula (XI), R'' represents an alkyl group, an aryl group, an alkylamino group, or an arylamino group.

R'7 represents a hydrogen atom, a halogen atom, or an alkoxy group.

R+a represents a hydrogen atom, an acylamide group, an alkyl group, an arylsulfonamide group, a sulf7moyl group, a carbamoyl group, an alkoxy group, or a denyl atom.

X represents a hydrogen atom or a detachable group.

The compound of general formula (1), including commercially available compounds, can be easily synthesized by conventionally known methods.

Examples of high-boiling point oils include phenol derivatives that do not react with the oxidized form of the developing agent, phthalic acid alkyl esters, phosphoric esters, citric acid distylates, anbenzoic acid esters, alkylamides, fatty acid esters, trimesic acid esters, etc. An organic solvent having a temperature of 150°C or higher is used.

High boiling point organic solvents that can be used in the present invention include:
U.S. Patent Nos. 2,322,027 and 2,533,51
No. 4, No. 2,835,579, No. 3,287,134
No. 2, No. 353,262, No. 2,852,383, No. 3,554,755, No. 3. (No. 376,137, No. 3,676.142, No. 3,700,454,
No. 3,748,141, No. 3,779,705, No. 3,837.863, British Patent No. 958°441, No. 1,222,753, OL S 2,538,889
, JP-A No. 47-1031, JP-A No. 49-90523, JP-A No. 50-238: "1, JP-A No. 51-20037, JP-A No. 51
-27921, 51-27922, 51-20
No. 035, No. 51-213036, No. 50-6263
No. 2, No. 53-1520, No. 53-1521, No. 5
No. 3-15127, No. 54-119921, No. 54-
No. 119922, No. 55 25057, No. 55-36
No. 869, No. 56-19049, No. 56-81836
No. 48-29060, etc.

When couplers are added to silver halide emulsions, usually
It is added in an amount of about 0.01 to 2 mol, preferably 0.03 to 0.5 mol, per mol of silver halide.

Furthermore, the more the compound of the present invention is added to the coupler, the greater the effect of the present invention will be.
, preferably in a range of 0.25 to 3 g.

The silver halide photographic light-sensitive material of the present invention can be, for example, color negative or positive film, color photographic paper, etc., but in particular, when using color photographic paper that is directly provided to The effects of the invented method are effectively exhibited.

The silver halide photographic material of the present invention, including this color photographic paper, may be for monochrome use or for multicolor use. In the case of multicolor silver halide photographic light-sensitive materials, in order to perform subtractive color reproduction, a silver halide emulsion layer containing magenta, yellow, and cyan couplers as photographic couplers and a non-light-sensitive silver halide emulsion layer are usually used. Calendar is applied to the support as appropriate V/l! ! Although it has an addendum stacked in order,
The number of layers and the V-type may be changed as appropriate depending on the thickness, performance, and purpose of use.

The silver halide emulsion used in the silver halide photographic light-sensitive material of the present invention includes conventional halides such as silver bromide, silver iodobromide, silver iodochloride, silver chlorobromide, and silver chloride. Any grains used in silver emulsions can be used.6 The silver halide grains used in the silver halide emulsion of the present invention may be those obtained by any of the acid method, neutral method, and ammonia method. . The particles may be grown all at once, or may be grown after seed particles are created. The method of creating and growing the seed particles may be the same or different.

Silver halide emulsions can be prepared by mixing halide ions and silver ions at the same time, or by mixing one in the presence of the other. ions and silver ions in a mixing pot
Growth may be performed by sequentially and simultaneously adding H and pAg while controlling them. Conversion methods may be used to change the silver halide composition of the grains after growth.

By using a silver halide solvent as necessary during production of the silver halide of the present invention, the grain size, grain shape, grain size distribution, and grain growth rate of silver halide grains can be controlled.

The silver halide grains used in the silver halide emulsion of the present invention are formed during the process of grain formation and/or grain growth. complex salts, iron salts or complex salts,
Metal ions can be added to the inside of the particles and/or included on the particle surfaces, and by placing them in an appropriate reducing atmosphere, reduction sensitizing nuclei can be provided inside the particles and/or on the particle surfaces. .

In the silver halide emulsion of the present invention, unnecessary soluble salts may be removed after the growth of silver halide grains is completed, or even salts may be contained therein. When removing the salts,
It can be done based on the method described in Research Disclosure No. 17843.

The silver halide grains used in the silver halide emulsion of the present invention may consist of uniform layers inside and on the surface, or may consist of different layers.

The silver halide grains used in the silver halide emulsion of the present invention may be grains in which a latent image is mainly formed on the surface, or grains in which a latent image is mainly formed inside the grains. - The silver halide grains used in the silver halide emulsion of the present invention may have a regular crystal shape or may have an irregular crystal shape such as a spherical shape or a plate shape. In these particles, the [100] plane and the (11
1) Any surface ratio can be used.

Further, the particles may have a composite form of these crystal forms, or particles of various crystal forms may be mixed.

The silver halide emulsion of the present invention may be a mixture of two or more silver halide emulsions that have been separately formed.

The silver halide emulsion of the present invention is chemically sensitized by a conventional method. That is, compounds containing sulfur that can react with silver ions,
A sulfur sensitization method using activated gelatin, a selenium sensitization method using a selenium compound, a reduction sensitization method using a reducing substance, a metal sensitization method using gold or other noble metal compounds, etc. can be used alone or in combination. .

The silver halide emulsion of the present invention can be optically sensitized to a desired wavelength range using a dye known as a sensitizing dye in the photographic industry. The sensitizing dyes may be used alone or in combination of two or more. Along with the sensitizing dye, a super sensitizer, which is a dye that does not itself have a spectral sensitizing effect, or a compound that does not substantially absorb visible light, and which enhances the sensitizing effect of the sensitizing dye, is added to the preservative. It may be included.

The silver halide emulsion of the present invention can be used to prevent fogging during production of light-sensitive materials, during storage, or during photographic processing, and/or
Or during chemical ripening for the purpose of maintaining stable photographic performance,
and/or at the end of the chemical ripening, and/or after the end of the chemical ripening and before coating the silver lodenide emulsion, compounds known in the photographic industry as antifoggants or stabilizers can be added. .

It is advantageous to use gelatin as the pineapple (or protective colloid) in the silver halide emulsion of the present invention.
In addition, hydrophilic colloids such as gelatin derivatives, graft polymers of gelatin and other polymers, proteins, sugar derivatives, cellulose derivatives, and synthetic hydrophilic polymer substances such as single or copolymers can also be used.

The photographic emulsion layer and other hydrophilic colloid layers of the light-sensitive material using the silver halide emulsion of the present invention can be formed by using a hardening agent alone or in combination to crosslink the baingu (or protective colloid) molecules and increase the film strength. It is hardened. It is desirable to add the hardening agent in an amount that can harden the photosensitive material to such an extent that it is not necessary to add the hardening agent to the processing solution, but it is also possible to add the hardening agent to the processing solution.

A plasticizer is added for the purpose of increasing the flexibility of the silver herodenide emulsion layer 1/or other hydrophilic colloid layer of a photosensitive material using the I12 silver dende emulsion of the present invention.

A dispersion of a water-insoluble or sparingly soluble synthetic polymer (
latex).

During the emulsion layer stage of the color photographic light-sensitive material of the present invention (between the same color-sensitive layers and/or between different color-sensitive layers), the oxidized form of the developing agent or the electron transfer agent may migrate, causing color turbidity or sharpness. A color antifoggant may be used to prevent deterioration in properties and noticeable graininess.

The antifoggant may be used in the emulsion layer itself, or in the intermediate on layer provided between the V# emulsion layers.

In the color light-sensitive material using the silver halide emulsion layer of the present invention, an image stabilizer can be used to prevent deterioration of the dye image.

Ultraviolet absorbers are added to hydrophilic colloid layers such as the protective layer and intermediate layer of the photosensitive material of the present invention to prevent fogging due to discharge caused by charging of the photosensitive material due to friction, etc., and to prevent image deterioration due to UV light. May contain.

A color photosensitive material using the silver halide emulsion of the present invention can be provided with an auxiliary layer such as a filter layer, an antihalation layer I, and/or an anti-ilanoation layer M.

These dye and/or emulsion layers may contain dyes which are leached from the color photosensitive oil or bleached during main processing.

The silver halide emulsion layer of a silver halide photosensitive material using the silver halide emulsion of the present invention, and/or the hydrophilic colloid layer thereof, reduces the gloss of the photosensitive material and increases the addability.
A matting agent can be added to prevent photosensitive materials from sticking to each other.

A lubricant can be added to reduce the sliding friction of the light-sensitive material using the silver halide emulsion of the present invention.

An antistatic agent for the purpose of preventing static electricity can be added to a light-sensitive material using the silver halide emulsion of the present invention.

Antistatic agents are sometimes used in the antistatic layer on the side of the support on which no emulsion is laminated, or in the emulsion layer on the side where emulsion layer 8 is layered on the emulsion layer 1/or support. It may also be used in other protective colloid layers.

The photographic emulsion waste-containing V/or other hydrophilic colloid layer of the light-sensitive material using the silver halide emulsion of the present invention may include improved coatability,
Antistatic, improved slipperiness, emulsification and dispersion, prevention of adhesion, and V(
Various surfactants are used for the purpose of improving photographic properties (such as accelerating development, increasing contrast, sensitization, etc.).

The photographic emulsion layer of a light-sensitive material using the halozonated silver emulsion of the present invention is composed of a baryta layer or a flexible reflective support such as paper laminated with an α-olefin polymer, synthetic paper, cellulose acetate, nitric acid, etc. cellulose, polystyrene,
It can be applied to films made of synthetic or synthetic polymers such as polyvinyl chloride, polycarbonate, polyamide, etc., as well as rigid bodies such as lath, metal, and ceramics.

The silver halide photosensitive material of the present invention is prepared by subjecting the surface of the support to corona discharge, ultraviolet irradiation, flame treatment, etc. as necessary.
1 or 2 or more for improving adhesion, antistatic properties, dimensional stability, abrasion resistance, hardness, antihalation properties, friction properties, and/or other properties directly or on the surface of the support. It may be applied through a subbing layer.

When coating a photographic light-sensitive material containing the silver halide emulsion of the present invention, a thickener may be used to improve coating properties. Particularly useful coating methods are extrusion coating and curtain coating, which allow two or more layers to be applied simultaneously.

The light-sensitive material of the present invention can be exposed using electromagnetic waves in a spectral region to which the emulsion layer of the light-sensitive material of the present invention is sensitive. Light sources include natural light (sunlight), tungsten electric lamp, fluorescent lamp, mercury lamp, xenon arc lamp, carbon arc lamp, xenon flash lamp, cathode 5 tube flying spot, laser light, light emitting diode, and electron beam. Any known light source can be used, such as light emitted from a phosphor caused by RJ by X-rays, γ-rays, a-rays, etc.

Exposure times include not only exposure times of 1 millisecond to 1 second commonly used with cameras, but also exposure times shorter than 1 microsecond, such as exposure times of 100 microseconds to 1 microsecond using a negative ray tube or xenon flash lamp.
Microsecond exposures can be used, or longer exposures of 1 second or more are possible. The exposure may be carried out continuously or intermittently.

Images can be formed using the silver halide photosensitive material of the present invention by color development as known in the art.

The aromatic primary amine color developing agents used in the color developing solution of the present invention include known ones that are widely used in various color photographic processes. These developers include aminophenol and 11-phenylenenoamine derivatives. These compounds are generally used in the form of a salt, such as a hydrochloride or a sulfate, since they are more stable than the isolated state. Additionally, these compounds generally have a color developer IQ of about 0. IF1 to a concentration of about 1 to about 1 g, preferably about I+ for color developer IQ? ~About 1.
Use at a concentration of 5g.

Examples of aminophenol-based developers include 〇-Ami/
7 er/-er, 11-7 min 7 er/-er, 5-7 er/-2
-oxytoluene, 2-ami/-3-oxytoluene,
Includes 2-oxy-3-7/-1°4-methylbenzene. - Particularly useful m1-class cubic ami/based color developers are N,N'-dialkyl-1]-phenylenenoamine compounds, in which the alkyl group and phenyl group may be substituted with any substituent. good. Among them, examples of particularly useful compounds include N,N'-diethyl-p-phenylenediamine hydrochloride, N-methyl-p-722-diamine hydrochloride, N,N'-tumethyl-1)7! Nylennoamine hydrochloride, 2-7mi/-5-(N-ethyl-N-dodecylami7)-toluene, N-ethyl-N-β-methanesulfonamidoethyl-3-methyl-4-ami/aniline sulfate, N-ethyl-N-β-hydroxyethylamine/
Aniline, 4-amino-3-methyl-N, N'-diethylaniline, 4-ami/-N-(2-methoxyethyl)
-N-ethyl-3-methylaniline-p-toluenesulfonate and the like.

The color developing solution used in the processing of the photographic light-sensitive material of the present invention includes, in addition to the above-mentioned primary aromatic amine color developing agent, various components that are usually added to color developing solutions.
For example, alkaline agents such as sodium hydroxide, sodium carbonate, and potassium carbonate, alkali metal sulfites, alkali metal bisulfites, alkali metal thiocyanates, alkali metal herodides, benzyl alcohol, and water softeners.
It is also possible to contain a thickening agent and a thickening agent.

The 1) ■■ value of this color developing solution is usually 7 or more, most generally about 10 to about 13.

After color development processing, J! I! However, if the processing solution having the fixing ability is a fixing solution, or before bleaching is performed. In addition, the bleaching treatment and the fixing treatment may be carried out with -.ni.As the bleaching agent used in the bleaching process, an acidic gold If & complex salt is used, +iJ
The metal complex salt has the effect of oxidizing raw metal silver during development and converting it into silver halide, while at the same time coloring the uncolored areas of the color former, and its composition is amide/polycarboxylic acid or oxalic acid, Metal ions such as iron, cobalt, and copper are coordinated with organic acids such as citric acid. The most preferred IT T'S acids used to form such metal complexes of organic acids include polycarboxylic acids or ami-7 polycarboxylic acids. These polycarboxylic acids or aminopolycarboxylic acids are alkali metal salts,
It may be an ammonium salt or a water-soluble amine salt.

A typical example of these weapons is a large one.

[1] Ethylenenoamine thitraacetic acid [2] Nitrirotriacetic acid [3] A
Mi / Shi' Acetic Acid [4] Ethylenediaminetetraacetic acid monosodium salt [5] Ethylenenoaminetitraacetic acid tetra(trimethylammonium salt) [6] Ethylenenoaminetitraacetic acid tetranatritum salt (7) di) Lilotriacetic acid sodium salt The bleaching solution or bleach-fixing solution used contains the above-mentioned gold S# complex salt of an organic acid as a bleaching agent, and may also contain various additives. As additives, it is particularly desirable to include rehalogenating agents, metal salts, and hexagonal agents such as alkali halides or ammonium halides, such as potassium bromide, sodium bromide, sodium chloride, and ammonium bromide. . It is also known that borates, oxalates, acetates, carbonates, phosphates, etc. 1) 1) Buffer removers, alkylamines, polyethylene oxy-VM, etc. can be added to ordinary bleaching solutions or) white paper fixing solutions. It is possible to add as appropriate.

Furthermore, the fixer and bleach-fixer contain ammonium sulfite,
Potassium sulfite, ammonium bisulfite, potassium bisulfite, thorium bisulfite, ammonium metabisulfite, potassium metabisulfite, metabisulfite) l) Sulfites such as rum, boric acid, borax, sodium hydroxide, potassium hydroxide , sodium carbonate, potassium carbonate, sodium bisulfite, sodium bicarbonate, potassium bicarbonate, ri
t: I) H buffer consisting of acid, sodium acetate, famous salts such as ammonium hydroxide, etc., alone or in combination
or more.

Bleach fixing IIl! When carrying out the process η11 of the present invention while replenishing the bleach-fixing replenisher (bath), the bleach-fixing solution (bath) contains 1,000 oz. Acid salts, thiocyanates, sulfites, etc. may be contained, or the bleach-fixing replenisher may contain these salts and be replenished into the processing bath.

In the present invention, in order to increase the activity of the bleach-fix solution, air or oxygen may be blown into the bleach-fix bath and the bleach-fix replenisher storage tank, if desired, or a suitable oxide, For example, hydrogen peroxide, bromate, persulfate, etc. may be added as appropriate.

〔Example〕

Hereinafter, the present invention will be described in detail with reference to Examples, but the mode of carrying out the present invention is not limited thereto.

Example 1 A coupler as shown below was taken in an amount of 0.1 mol per mol of silver, and a compound of the general formula CI) of the present invention or 2,4-di[-amylphenol as a comparison was added as a high-boiling oil agent. Ethyl acetate was added in an amount of 1 times the weight of the coupler and then 3 times the weight of the coupler, and the mixture was heated to 60° C. to completely dissolve. This solution was mixed with a 5% aqueous gelatin solution 1200j+4' containing 120 units of a 5% aqueous solution of Flukanol B (manufactured by Flukylnaphthalene Sulfonate Tubon), and emulsified and dispersed using an ultrasonic dispersion machine to obtain an emulsion. Ta. Thereafter, this dispersion was mixed into a green-sensitive silver iodobromide emulsion (containing 6 mol% silver iodide).
4 kg, hardener was added, coated on a subbed transparent polyester base and dried, 12 types of samples (A6
x-A, D, C-, vg4-A, B,
C) was created (coated silver [20 shoulder g/ioo cn)
.

The sample thus obtained was subjected to wedge exposure according to a conventional method, and then subjected to the following development treatment. The results are shown in Table 1 below.

[Processing process] (38°C) Processing time Color development
Bleach for 3 minutes and 15 seconds Wash with water for 1 minute and 30 seconds Set for 3 minutes and 15 seconds
Arrive 6 minutes 30 seconds Wednesday
Washing 3 minutes 15 seconds stabilization bath
The composition of the treatment liquid used in the 1 minute 30 second treatment step was as follows.

[Color developer composition]

4-amino-3-methyl-N-ethyl-N-(β-hydroxyethyl)-7 dillone sulfate 4.751 anhydrous sodium sulfite 4.25 g hydroxylamine I/2 R salt 2.0 ji anhydrous Potassium carbonate 37.5, p
To sodium bromide 1.3, add 2.5 g of tolyltriacetic acid trisodium salt (monohydrate), potassium hydroxide 1.0, 9 water to make 11, and use potassium hydroxide to pH 10.0.
1c adjustment through.

[Bleach solution composition]

Ethylenediaminetetraacetate iron ammonium salt
1
00.0. 9Ethylenedi7minetetraacetic acid diammonium salt
10.0.9 Ammonium Bromide
150.0g glacial acetic acid
Add 10.0m/l/water and bind pl-I using ammonia water 6. Adjust to o.

[Fixer composition]

Ammonium thiosulfate (50% aqueous solution) 16.2m
t Add 12.4g of anhydrous sodium sulfite water II! Close and adjust pH to 6.5 using acetic acid.

[Stabilizing liquid composition]

Formalin (37% aqueous solution) s, o
ml Funida Sox (manufactured by Konishiroku Photo Industry Co., Ltd.) 7.5
Add ml water to make Ij'.

Sensitivity in Table 1 is the reciprocal of the exposure that gives a density of Capri density + 0.1, and is the relative sensitivity when each sample (a) is taken as 100. Coupler (1) Coupler (2) d7? Coupler (3) CI! Example 2 By sequentially coating the following layers on polyethylene resin coated paper containing anacuse-type titanium oxide...
A silver p-genide color photographic material was prepared (sample/16
5 and 6).

The amounts added below are per +00 cl.

(1) 20 g of gelatin, 5 mg of silver as a blue-sensitive silver chlorobromide emulsion, B mg of Y-coupler powder and 0.1 M9 of 2,5-di-t- as a high-boiling oil.
A layer containing 5 g of a compound of the general formula CD in which octylhydroquinone is dissolved or, for comparison, 2,4-not-t-amylphenol.

(2112 ■ gelatin, 0.5 ■ 2.5-di-t-
Intermediate layer containing 2 mg digtylphthalate in which octylhydrquinone was dissolved.

(312,311 fl of gelatin, 4 N green-sensitive silver chlorobromide emulsion as the silver amount, 5 μm of M-coupler powder and 0.2 mg of 2,5-di-t-octylhydroquinone as a high-boiling oil agent were dissolved. Compounds of general formula CI),
Or a layer containing 2,4-di-t-7milphenol 5119 for comparison.

+41 Intermediate layer containing the same composition as f21.

+5+ 16 mfl gelatin, 4 m as silver
g red-sensitive silver chlorobromide emulsion, and 3. (JTR9's C-
0.1 mg of 2. as coupler x and high boiling point oil.
A compound of the general formula CD in which 5-di-1-octyl-idroginone was dissolved, or 2,4-di-t-
A layer containing 20IIIg of amylphenol.

(6) Gelatin protective layer containing 'JIg gelatin.

(+l) A coating aid is added to each layer of (6), and further (
A gelatin crosslinking agent was added to layers 4) and (6).

Y-coupler, 1'-e M-coupler *C-coupler 10 l Samples were light simulated exposed according to the sensitometric method and then processed at a temperature of 33°C according to the following sequence.

Processing steps: Color development: 3 minutes and 30 seconds Bleach-fixing: 1 minute and 30 seconds: Washing with water: 3 minutes As the color developer and bleach-fix solution, processing solutions having the following formulations were used.

Color developing solution prescription rN-Ethyl-N-β-methanesulfone 7mide Bleach-fixing solution prescription Table 2 Sensitivity is shown as relative sensitivity when the sensitivity of the corresponding layer of sample 46 is taken as 100.

Claims (1)

[Scope of Claims] A silver halide photographic material characterized by containing a non-color-forming compound represented by the following general formula [I]. General formula [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, R^1 and R^2 represent a hydrogen atom or an alkyl group, and R^1 and R^2 cannot be hydrogen atoms at the same time. . R^3 represents a halogen atom or an electron-withdrawing group. However, -COR^4 and -SOR^5 are excluded. Here, R^4 represents an alkyl group, an aryl group, a heterocyclic residue, an alkoxy group, an aryloxy group, a heterocyclic oxy group, or an amino group, and R^5 represents an alkyl group, an aryl group, or a heterocyclic residue. ]