JPS62260148A - Silver halide photographic sensitive material improved in antistaticness and antitackiness - Google Patents

Abstract

PURPOSE:To obtain a silver halide photographic sensitive material superior in antistaticness and antitackiness and prevented from occurrence of sludge and deterioration of sensitivity by incorporating an organic fluorocompound in at least one of hydrophilic colloidal layers and hardening this layer with a polymer hardener. CONSTITUTION:The silver halide photographic sensitive material has on a support at least one of the hydrophilic colloidal layers containing the organic fluorocompound, preferably such as fluorinated surfactants and fluoropolymers, and having been hardened with the polymer hardener having at least 2 hardening groups for reacting with hydrophilic colloids like gelatin or the like in the same molecule and a molecular weight of >=3,000. Said fluorinated surfactant is represented by the formula: Rf-(A)m-X in which Rf is alkyl, alkenyl, or aryl each having at least 3 F atoms; A is a divalent bonding group; X is a hydrophilic group; and m is 0 or 1.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a silver halide photographic material, and more particularly to a silver halide photographic material with improved antistatic properties and adhesion resistance.

[Background of the Invention] Generally, the outermost layer of a silver halide photographic light-sensitive material uses a hydrophilic colloid, typified by gelatin, as a binder. Therefore, the adhesiveness or tackiness of the surface of silver halide photographic materials increases under high temperature and high humidity atmospheres.
When it comes into contact with other objects, it easily adheres to it.

This adhesion phenomenon occurs during the production of silver halide photographic materials.
During storage, during shadowing, etc., problems often occur between silver halide photographic materials or between silver halide photographic materials and other objects that come into contact with them, often resulting in serious failures. In particular, silver halide color photographic materials contain a large number of additives such as color couplers in their photographic layers, so adhesion has been a major problem.

In order to solve this problem, the outermost layer contains fine particles of silicon dioxide, magnesium oxide, titanium dioxide, calcium carbonate, etc., and organic substances such as polymethyl methacrylate, cellulose acetate propionate, and fluororesin. A method has been proposed for increasing the roughness of the surface of a silver oxide photographic light-sensitive material to make it so-called matte and to reduce its adhesion. Particularly in silver halide color photographic materials, it is necessary to use a large number of matting agents for the above-mentioned reasons. However, since the addition of a large amount of matting agent adversely affects photographic image quality, particularly sharpness, there are limits to the use of matting agents.

Incidentally, since silver halide photographic materials generally have an electrically insulating support, accumulation of electrostatic charges is a serious problem in addition to adhesion. This accumulated electrostatic charge causes many problems, but the most important one is that the photosensitive emulsion layer becomes sensitized by discharging the accumulated electrostatic charge before processing, and when the photographic film is processed. This is the formation of dot-like spots or dendritic or feather-like density spots on the skin.

This is what is called a static mark, and it significantly reduces the commercial value of the photographic film, and in some cases completely destroys it. This phenomenon becomes apparent only after development, and is one of the most troublesome problems. In addition, these accumulated electrostatic charges may cause secondary failures such as dust adhesion to the film surface or inability to apply uniformly.

The best way to eliminate these static electricity hazards is to increase the electrical conductivity of the material so that the static charge can be quickly dissipated before the stored charge is discharged.

Therefore, methods have been considered to improve the conductivity of supports and various coated surface layers of silver halide photographic materials, and attempts have been made to use various hygroscopic substances, water-soluble inorganic salts, surfactants, polymers, etc. I've been exposed to it. Examples of these include, for example, U.S. Patent No. 2,982,651;
No. 28.456, No. 3.457.076, No. 3.45
4.625, JP-A-55-7762, JP-A No. 56. -4
No. 3636, US Pat. No. 56-114944, etc., for example, US Pat.
No. 57, No. 3.062.785, No. 3.938.99
No. 9, JP-A-56-78834, JP-A No. 57-2045
No. 40, No. 57-179837, No. 58-8224
There are polymers described in No. 2 and others.

However, it is extremely difficult to prevent static electricity on a hydrophilic colloid layer, and known antistatic means may not reduce the surface resistance sufficiently at low humidity, or may cause adhesion failure of silver halide photographic materials at high temperature and high humidity. There are often cases. Moreover, if the necessary amount of antistatic agent (for example, the fluorine-based surfactant described in Japanese Patent Publication No. 56-44411) is included in the hydrophilic colloid layer to obtain a sufficient antistatic effect, the film It may adversely affect physical properties or leak into the developing solution, causing sludge.

The present inventors have discovered that the outflow of an organic fluoro compound such as a fluorosurfactant into a developing solution can be suppressed by increasing the hardness of the organic fluoro compound-containing layer.

However, when the hardness of the organic fluoro compound-containing layer is increased by the conventional method, the silver halide emulsion layer is also hardened, making it impossible to obtain sufficient sensitivity.

[Object of the Invention] An object of the present invention is to provide a silver halide photographic material which has excellent antistatic properties and adhesion resistance, and which does not generate sludge or reduce sensitivity.

[Structure of the Invention] The above object of the present invention is to provide a silver halide photographic material having at least one hydrophilic colloid layer on a support, wherein at least one of the hydrophilic colloid layers contains an organic fluoro compound; This was achieved using a silver halide photographic material hardened with a polymer hardener.

[Specific Structure of the Invention] The organic fluoro compound used in the present invention will be explained.

Examples of organic fluoro compounds in the present invention include British Patent Nos. 1□293.189, 1, 259.398,
U.S. Patent No. 3,589,906, 3.666, 47
No. 8, No. 3,754°924, No. 3.775.236
No. 3.850.640, JP-A-54-48520
No. 56-114944, No. 50-16123
No. 6, No. 51-151127, No. 50-59025
No. 50-113221, No. 50-99525, Japanese Patent Publication No. 48-43130, Japanese Patent Publication No. 57-6577, Japanese Patent Application No. 57-133566, Japanese Patent Application No. 57-80773, Japanese Patent Publication No. 53-84712, No. 57-64228, Iron Easy Product Research and Development (1&E CP product R
esearch and [) development)
Yu (3”) (1962, 9), Oil Chemistry 2 (12>
(1963) p653, etc., or JP-A-15822-1989.
No. 2, No. 52-129520, No. 49-23828, British Patent No. 1, 352.975, No. 1,497,
No. 256, U.S. Patent No. 4,087.394,
No. 016,125, 3,240,604 amount, 3,
No. 679,411, No. 3,340,216, No. 3,6
No. 32,534, JP-A-48-30940, JP-A No. 52-
Fluorine-containing polymers described in No. 129520, US Pat. No. 3.753.716, etc. are preferably used.

The organic fluoro compound particularly preferably used in the present invention is a fluorine-containing surfactant, and is represented by the following general formula.

Rf-(A), , 7X In the formula, Rf is an alkyl group having at least three fluorine atoms (including those having substituents).

For example, dodecafluorohexyl group, heptadecafluorooctyl group, etc.), alkenyl M (including those with substituents; for example, heptafluorobutylene group, tetradeca)lolooctyl group, etc.), or aryl groups (including those with substituents) For example, it represents a trifluorophenyl group, a pentafluorophenyl group, etc.). A represents a divalent linking group, X represents a hydrophilic group, or - represents O or 1.

The divalent linking group represented by A includes, for example, an alkylene group (including one having a substituent).

Specifically, ethylene groups, trimethylene groups, etc.), arylene groups (including those with substituents, specifically phenylene groups, etc.), alkylarylene groups (including those with substituents, etc.), (butylphenylene group, etc.)
, arylalkylene group (including those having substituents, specifically ≦ phenylethylene group, etc.), -802-1-N- (R represents a hydrogen atom or an alkyl group), -C-O- 1-
O-C-1-C-1-〇-tera is used, and a divalent linking group formed by arbitrarily combining these groups may be used.

X is a hydrophilic group, preferably, for example +8-0SR
+ (Here, 8 represents an alkylene group including one having a substituent, for example, -CH2-CH2-1-CH2-
CH2-CH2-, etc. are mentioned. n represents the average degree of polymerization of the polyoxyalkylene group, and is an integer of 1 to 50. Further, R1 represents a hydrogen atom, an alkyl group including those having a substituent, or an aryl group including those having a substituent. ), for example, [wherein R4 represents an alkylene group having 1 to 5 carbon atoms (e.g., methylene group, ethylene group, propylene group, butylene group), and R2 and R3 each represent an alkylene group having 1 to 5 carbon atoms.
It represents an alkyl group including those having 8 substituents (for example, methyl group, ethyl group, benzyl group, etc.) or an aryl group including those having substituents (for example, phenyl group, tolyl group, etc.). ] A hydrophilic betaine group represented by, for example, R'3 has the same meaning as R2 and R3, respectively, R5 has the same meaning as R2, and Ye represents an anion (e.g., hydroxy group, halogen group, sulfate group, carbon'W1 group, perchloric acid group, organic carboxylic acid group, organic sulfonic acid group, organic sulfuric acid group, etc.). ] A hydrophilic cationic group represented by, for example -8
03M-0303M1-C00M, -○-P(OM)2
, 1-0-P-O (wherein M is inorganic or organic -A-R
f represents a cation, preferably a hydrogen atom, an alkali metal, an alkaline earth base, ammonium, or a carbon atom number of 1 to 3
alkylamines, etc. Examples include hydrophilic anionic groups represented by A and R "are the same as defined above." Among the hydrophilic groups represented by X, particularly preferred are woodphilic anionic groups and hydrophilic betaine groups. .

Another preferred organic fluoro compound of the present invention is a fluorine-containing polymer.

In the fluorine-containing polymer used in the present invention, one monomer unit having a fluorine atom has the following general formula [I] 1.
Those derived from vinyl monomers represented by [II] or [I[[ ], and those obtained by reacting a polymer of maleic anhydride with a fluorinated alcohol are preferred.

Note that the fluorine-containing polymer may have one monomer unit derived from another monomer that can be copolymerized with a monomer having a fluorine atom, as long as the effects of the present invention are not impaired.

Below is a blank general formula [I] I CH2=(l coo-4XRf3 General formula [II] C/-1,=C!-Rf2 In the formula, R1 and R2 are each substituted with a hydrogen atom or a fluorine atom Rf2 represents a straight chain, branched or cyclic alkyl group substituted with a fluorine atom, and this alkyl group preferably has 1 carbon atom.
~10, and may have a substituent other than the fluorine atom, and examples of these replacement groups include a hydroxy group, a halogen atom (for example, a chlorine atom, a bromine atom, etc.).

Further, the alkyl group represented by Rt2 may have a linking group such as an oxo group, thio group, or carbonyl group interposed between the carbon chains.

In the formula, R3 is a hydrogen atom, a chlorine atom, or a carbon number of 1 to
3 represents an alkyl group, R4 represents a monovalent substituent, and when q is 2 or more, R4 may combine with each other to form a ring. In the formula, Rf3 represents an alkyl group having 1 to 30 carbon atoms, an arylalkyl group, an aryl group, or an alkylaryl group in which at least one hydrogen atom is substituted with a fluorine atom, and X represents the general formula →R-v- L-or-
Represents a divalent linking group represented by L-(-R\-, where R represents an alkylene group, arylene group, or aralkylene group having 1 to 10 carbon atoms, and -L-1,1-〇-1
-S-1-NH-1-CO-1-OCO-1-C〇-〇-1-8C○-1-CONH-1-NHCO-1-8O
2-1-NRs SO2 (here R5 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms), -8O2NH
-1-8O-1-0PO2-, [is 0 or 1
It is. q is an integer from 0 to 4, p is an integer from 0 to 4, S is 1
It is an integer of ~5.

Next, among the fluorinated monomers represented by the general formula [I], [II] or [I[[], typical specific examples of those preferably used in the present invention are shown below.
41.

Margin field-1 CH2-OH C00CJ (CPz) n)I n = 2~9
Integer M-2 Hi CH Engineering and Agriculture C ■ C00CI (, (CF,) nHn = 2 to 9 atM
-3 CI(.

CH, phantom C C00C)1. (:1110((:II,)nF 1
1-2~8 ql River-4 River-5 M-a CH2-Cl1 C00C%CI, 4CFz) nF n ” 2~
8's number A-7 HI-C1 C00CH1CHCHL (CPz)nFOHn=2~8
Integer CH Yo -C - C YuHs M-10 M3 Gate -12 C) 1 Knee C) 1-0-C1l□-(CF2)-^H Integer from 2 to 8 CIh5COCHz (Ch) I. H NHCO (CF), H Tsuyoshi-17G) 13 CI(,jlHcO(CF Yu%H Ch CHzNHCO(CF2) 1oH Cl YuNHCF:LCF20H CHzOCO(CF,) I 6) 1 SO□C+!ICH2(CF Yu%H )&H FM-3? Local FM-phrase c Q OCFI z (CFz )yv F
n: 2 to 9 Monomers copolymerizable with the fluorine-containing monomer include acrylic acid esters such as butyl acrylate and cyclohexyl acrylate, methacrylic acids such as methyl methacrylate, ethyl methacrylate, cyclohexyl methacrylate, and sulfopropyl methacrylate. esters, vinyl esters such as vinyl acetate and vinyl propionate, vinyl ethers such as methyl vinyl ether and butyl vinyl ether, vinyl ketones such as methyl vinyl ketone and ethyl vinyl ketone, styrene,
Examples include styrenes such as methylstyrene and chloromethylstyrene, acrylonitrile, vinyl chloride, vinylidene chloride, butadiene, and isoprene.

Specific examples of typical organic fluoro compounds of the present invention are shown below.

Margin below C,F,,C0OH H(CF,)8CH2COCH,NH.

CgF+tSO,K F 4 C5HtC,F,? S.O.
,N-CH2C00K H(CF2)acOOcHtcH,CB,So,NaC
,F,5CON-CH,CH,5OxNaH(CF,)
, CH200C-CH3 I(CFz)acH200c CH30,NaC,F
,,So,NCH,COONa C2H.

p: average 3 C,H.

C, F, 7SO2N (-CH2CH20÷--(-C)
I,-) iso3Nap: average 4C,H.

C, F, 7SO, N+CH2CH, O→-÷CH, sy
sO5Nap: Average 7C+oFt+CHzCHzO+CH2CH2O±-C
) I 2 U TS Os Na ap: Average 6 Na p : Average 5 F lb C3H7 C3F17SO2N-CH2CH205O3Nan5:
10 old=12 F”? C3Ht CgF+7SOzN+CH2CPh0+,, Hns:1
1 F-21cH! C5F17S02N+cHz CH2O+85OiNa
CaFq+CH2CH2O+3SO3NaC7F15
CH2CH2CH20+7-+CHz+4SO3KF
-2'7 C3H7C3F1y 5l)
2 N+CHz CHz O+6 CH2COONaN
a CH2CHtOH CH3 p: Average 4 CRF17CH2CH200CCH5OxNaF 4
2cH.

x:y=80:20 (molar ratio, same below) CHs SOqθ” ” ” =o″′°6°x:
y: z=50:20:3Qx: y=2.1:
97.9 x:y=35:65 CH2NHC(J(CF2911 x: y=3.7: 96.3 (water shift latex) x:y:z=50:20:30 0 CH2÷CFz÷, HO÷CH2CH20),.

C5x: y=40: 60 F-52CR, CH3 x: y==70: 30 0H x:y=50:50 F”4 C(JOHx: y
=50:50 The amount of the organic fluoro compound according to the present invention added to the hydrophilic colloid layer is preferably 0.1 mg to 2 g per 1f, and 0.
．． Particularly preferred are 5n+g to 800111111.

The organic fluoro compound is contained in a hydrophilic colloid layer, and examples of the hydrophilic colloid layer include a silver halide emulsion layer, an intermediate layer, and a protective layer.

In the present invention, the organic fluoro compound is particularly preferably contained in the outermost layer of the silver halide photographic material. The outermost layer includes a surface protective layer, a back layer, etc., and a surface protective RJ layer is particularly preferred, but when the back layer is composed of a hydrophilic colloid layer, a back layer is also preferred.

To add an organic fluoro compound to the hydrophilic colloid layer, the fluorine-based surfactant is added directly to the hydrophilic colloid liquid, and the fluorine-based polymer is dissolved in an appropriate solvent and then added to the hydrophilic colloid liquid. Just add it.

In the present invention, an organic fluoro compound may be overcoated on the surface protective layer by the method described in Japanese Patent Publication No. 57-8456. In this case, the fluorine-based surfactant in particular penetrates into the surface protective layer during drying after coating, and the effects of the present invention can be obtained.

In the silver halide photographic light-sensitive material according to the present invention, at least one hydrophilic colloid layer on the support contains the above-mentioned organic fluoro compound and is hardened with a polymer hardener described below.

The polymeric hardener of the present invention has at least two hardening groups in the same molecule for reacting with hydrophilic colloids such as gelatin.
It means a compound having a molecular weight (number average molecule fi) of 3,000 or more.

Examples of hardening groups for reacting with hydrophilic colloids such as gelatin include aldehyde groups, epoxy groups, active halide groups (such as dichlorotriazine), active vinyl groups, and active ester groups. In addition, it is sufficient that there are at least two of these groups in the same molecule of the polymer hardening agent,
Preferably it is 10 to 5000 pieces. In addition, the molecular weight may be 3.000 or more, but 3.000 to 50
About 10,000 yen is preferably used.

Generally, a hydrophilic polymer having a hardening group for reacting with a hydrophilic colloid such as gelatin is preferably used, but even if it is not hydrophilic, it can be emulsified and dispersed in a hydrophilic colloid (e.g. gelatin). It can also be used by dissolving (dissolving and dispersing in an organic solvent if necessary).

Examples of the polymeric hardener used in the present invention include dialdehyde starch, polyacrolein, and U.S. Pat.
Polymers having aldehyde groups such as the acrolein copolymers described in US Pat. No. 6.029, US Pat. No. 3.623.8
Polymers having epoxy groups described in No. 78, polymers having dichlorotriazine groups described in U.S. Patent No. 3,362,827, Research Disclosure Magazine 17333 (1978), etc., JP-A-56-66
Polymers having active ester groups as described in No. 841, JP-A-56-142524, U.S. Pat. No. 4,1
61,407, JP-A No. 54-65033, Research Disclosure Magazine 16725 (1978), etc., polymers having active vinyl groups or groups that become precursors thereof, etc. Polymers having a group or a group serving as a precursor thereof are preferred, and in particular, a long spacer as described in JP-A-56-142524 allows an active vinyl group or a group serving as a precursor thereof to be attached to the polymer main chain. Particularly preferred are such polymers that are conjugated.

Specific examples of the polymer hardener of the present invention are shown below.

Below margin (J-Z-Q ■-Z
^-= In addition, the polymeric hardener of the present invention, like the polymer described above, contains at least two hardening groups per molecule from the beginning to react with hydrophilic colloids such as gelatin. It is possible to use any polymer having the above properties, but it is best to use a hydrophilic colloid hardening agent such as gelatin and a polymer that reacts with the hardening agent to give a polymer having at least two hardening groups in the same molecule. In this way, a polymeric hardener can be created in the applied hydrophilic colloid layer, thereby coupling the objects of the present invention.

Thus, as hardeners for gelatin used to make polymer hardeners in hydrophilic colloid layers, low molecular hardeners, such as T.H.
The Theory of the Photographic Process (The Theory of the Photographic Process) by
the Photoaraphic Process)
J, 4th edition, pages 77 to 84 are used, and among them, low molecular weight hardeners having a vinyl sulfone group or a triazine ring are preferred, especially those described in JP-A-53-41221. The hardeners described in No. 60-225143 are preferred.

Specific examples of gelatin hardeners that provide polymeric hardeners according to the present invention are shown below.

Below margin (CH2=CHSO2CH2CONHCH), -(CH
2=CH3O2CH, CONHCH,), CH2CH,
=CH3O, CH, CHCH, 5o2CH=CH.

Goods CH, =CH-3O, -CH=CH.

CH2=CH-8o, CH, OCH, -8o□-CH=
CH.

CH,=CH8O,CH,CH2Cl,So,CH=C
H.

0)(C(CHt)3CHO Formalin COCH=CH2 Cage I-IfT /MYTCI/'t/'+
0 1”LT Ql”1 ρLJ=rTJ-
(CHt =CHS Oz CH2nowτC((CH,=
CH8O, CI (2?z clause・H2NCH, CH, SO,
In addition, the polymer used to make the polymeric hardener in the hydrophilic colloid layer contains at least nucleophilic groups in the same molecule that react with the gelatin hardener. It is necessary to have two or more, for example, British Patent No. 2,011,912
Polymer having a primary amine group described in JP-A-56-
Polymers with sulfinic acid groups as described in US Pat. No. 4,207,109, polymers with phenolic hydroxyl groups as described in US Pat. No. 4,215,195 Examples include polymers having methylene groups.

Specific examples of polymers that provide polymer hardeners of the present invention are shown below.

Margin below So, K Q -3Q -4Q -5 NH (CH,), NH, NH.

CH.

Polymer V! used in the present invention below! The synthesis method of the membrane agent is shown.

Synthesis Example 1 Poly-N- [3- (vinylsulfonyl)
BuO bioyl 1aminomethylacrylamidecoacrylamide-2-methylpropanesulfonic acid sodium (H
Synthesis of P-3) (a) Synthesis of N-[3-(chloroethylsulfonyl)propioyl 1-aminomethylacrylamide Into a 2ffi reaction vessel, add 1,400 g of distilled water and add 1,400 g of distilled water. iIi
t1g! 224g sodium, 224g sodium bicarbonate
201;l of chloroethanesulfonyl chloride was added thereto, dissolved with stirring, cooled to 5° C., and 260 g of chloroethanesulfonyl chloride was added dropwise over about 1 hour and 30 minutes. After finishing dropping, 49% sulfur 1160
Add Q, filter the precipitated crystals, and add 40
Washed with 0.1112 g of distilled water. Add this filtrate and washing solution to 32 reaction vessels, add 246 g of methylenebisacrylamide to 480,112 parts of distilled water and 1,480 ml of distilled water.
A solution of No. 2 in ethanol was added dropwise at 5° C. over about 30 minutes.

After the reaction sample was left in the refrigerator for 5 days to complete the reaction, the precipitated crystals were collected by filtration and cooled.
After washing with distilled water, it was recrystallized from a 50% ethanol aqueous solution at 2000 iR to obtain 210 g of white powder. The yield was 49%, and the melting point of this compound was above 192°C (decomposition).

(b)) (Synthesis of P-3 2 Into the reaction solution of Q OvQ, add 5.6
Add 5 g of sodium acrylamide-2-methylpropanesulfonate 9.16 (1,8011) in a 50% ethanol aqueous solution, stir to dissolve, and dissolve while passing nitrogen gas.
The temperature was raised to 0°C, and 0.1 g of 2.2'-azogose (2,4
-dimethylvaleronitrile) was added, and after another 30 minutes, the same amount of the same was added, and heating and stirring were continued for 1 hour. Thereafter, the room was cooled to 10°C, and a mixture of 2.5 g of triethylamine and 80112 ethanol was added, stirring was continued for 1 hour, and the reaction sample was mixed with 1!2. In addition to acetone,
The resulting precipitate was collected by filtration and dried under vacuum to obtain 12.4a, a white polymer. The yield was 85%, the nominal viscosity [η] of the polymer was 0.227, and the vinyl sulfone content was 0.
95×10 −3 m/g polymer.

Synthesis Example 2 Synthesis of poly-N-[2-(vinylsulfonyl)acetylcoaminomethylacrylamide-coacrylamide (HP-7) (a) Synthesis of N-[2-(chloroethylsulfonyl)acetyl]aminomethylacrylamide 1t To the reaction solution, add 720 iffi of methanol and 80.8 g of N-methylolacrylamide, add 40 v1 of concentrated hydrochloric acid at room temperature while stirring, continue stirring for 16 hours, add 0.4 g of hydroquinone monomethyl ether, and evaporate methanol with an evaporator. Distilled away. To the remaining 62.4 g of oil, add 1001; l of chloroethanesulfonylacetamide.
, hydroquinone monomethyl ether 0.32 (1, p
-Toluenesulfonic acid 0, 22 (+) was added and heated to 150°C to distill off the generated CH308. The reaction was completed in about 15 minutes, and the remaining crystals were recrystallized from a 250 iN 50% ethanol aqueous solution. A white powder of 61o was obtained.

The yield was 42%.

(b) Synthesis of HP-7 300 (haj2 reaction vessel, monomer 5 of (a)
3.7 (1, acrylamide 163.3 (1, , 4-dimethylvaleronitrile) and heated for 4 hours, cooled to room temperature and diluted with triethylamine 2.
0.2 () was added, stirred for 2 hours, and the precipitate was collected by filtration and dried under vacuum to obtain 194.3 g of a white polymer. The yield was 92.7%, and the content of the nylsulfone in this polymer was 0.50 x 10-3 equivalents jft/(l polymer).

A method for synthesizing a polymer that provides a polymeric hardener is shown below.

Synthesis Example 3 Synthesis of Potassium Polyvinylbenzenesulfinate-Co-Sodium Acrylamide-2-Methylpropanesulfonate <Q-1) In a reaction vessel of 1, 45 mL of sodium acrylamide-2-methylpropanesulfonate was added.
．． 8 (1, potassium vinylhenzenesulfinate 20.
6Q, 180 d of ethanol, and distilled water were added, and heated to 75°C while stirring to obtain [2,2'-azobis-(
Add 0.821 l of 2-amine)butane dihydrochloride, heat for 4 hours, let cool to room temperature, add 72aQ of ethanol and 278iN of distilled water, filter, and obtain a colorless, transparent and viscous solution. I got some liquid. of this polymer solution at 25°C.
The viscosity is 3.25 centivoise (CD), the solids concentration is 10.3% by weight, and the sulfinic acid content is 6.2×
It was 10 to 6 equivalents/g.

Other polymeric hardeners can also be easily synthesized based on the above-mentioned synthesis examples or the methods described in the above-mentioned patent specifications. Some polymer hardeners are also commercially available.

The amount of the polymer hardener of the present invention to be used can be arbitrarily selected depending on the purpose. Usually, the functional group that reacts with hydrophilic colloid such as gelatin corresponds to a range of 0.5 x 10-3 equivalent to 5 x 10-2 equivalent per 100 Q of hydrophilic colloid such as gelatin in the layer to be added. Polymeric hardeners are used. Particularly preferred is 0.5X 10-3
The range is from 1 to 2×10 −2 equivalents.

Furthermore, the polymer hardener of the present invention may be used alone as a hardener, or
No. 1221, No. 60-225143, U.S. Patent No. 3,
No. 325,281, No. 3.945.853, Japanese Unexamined Patent Publication No. 1973
No. 9-31944, No. 55-736, No. 55-987
No. 41, No. 55-46745, No. 54-13093
It may be used in combination with other low-molecular hardeners or polymer hardeners such as those described in No. 0. In the present invention, it is preferable to use them together. 1ZJl agents that can be used in combination include 2-
Compounds having a reactive halogen atom such as hydroxy-4,6-dichloro-1,3,5-t-riazine, compounds having a reactive olefin such as divinylsulfone,
There are isocyanates, aziridine compounds, epoxy compounds, mucochloric acid, chrome light bread, and aldehydes.
Specifically, the compounds shown in H-1 to H-21 above can be mentioned.

The following margins The silver halide emulsion used in the silver halide photographic light-sensitive material of the present invention contains silver bromide 1. Any of those commonly used in silver halide emulsions can be used, such as silver iodobromide, silver iodochloride, silver chlorobromide, silver chloroiodobromide, and silver chloride, but especially silver bromide, silver iodobromide, and silver chloride can be used. Silver bromide and silver chloroiodobromide are preferred.

The silver halide grains used in the silver halide emulsion may be 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.

In the silver halide emulsion, halide ions and silver ions may be mixed simultaneously, or one may be mixed in a liquid in which the other is present. Further, while taking into consideration the critical growth rate of silver halide crystals, halide ions and silver ions may be generated by sequentially and simultaneously adding the DHlDAO in the mixing pot while controlling it. By this method, silver halide grains having a regular crystal shape and a nearly uniform grain size can be obtained. Conversion methods may be used at any step in the formation of Agx to change the halogen composition of the particles.

Known silver halide solvents such as ammonia, thioether, thiourea, etc. can be present during the growth of silver halide grains.

During the process of grain formation and/or growth, silver halide grains are produced using cadmium salts, zinc salts, lead salts, thallium salts, iridium salts (including complex salts), rhodium salts (including complex salts), and iron salts ( (including complex salts) to add metal ions to the inside of the particles and/or
Alternatively, these metal elements can be contained on the particle surface, and reduction sensitizing nuclei can be provided inside the particle and/or on the particle surface by placing the particle in an appropriate reducing atmosphere.

The silver halide emulsion may be free of unnecessary wettable salts after the growth of silver halide grains is completed, or may be left containing them. When removing the salts, Research Disclosure (Research [) 1
sclosure (hereinafter abbreviated as RD) No. 17643■
It can be carried out based on the method described in Section.

The silver halide grains may have a uniform silver halide composition distribution within the grain, or may be core/shell grains in which the silver halide composition differs between the inside of the grain and the surface layer.

The silver halide grains may be such that the latent image is mainly formed on the surface, or may be such that the latent image is mainly formed inside the grain.

The silver halide grains may have a regular crystal shape such as a cube, octahedron, or dodecahedron, or may have an irregular crystal shape such as a spherical shape or a plate shape. In these particles, any ratio of the (100) plane to the (111) plane 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 size of silver halide grains is 0.05 to 30μ,
Preferably, those having a diameter of 0.1 to 20μ can be used.

Silver halide emulsions having any grain size distribution may be used. An emulsion with a wide grain size distribution (referred to as a polydisperse emulsion) may be used, or an emulsion with a narrow grain size distribution (referred to as a monodisperse emulsion). When divided by the average grain size, the value is 0.20 or less.The grain size is the diameter in the case of spherical silver halide, and the projection of the grain in the case of grains with shapes other than spherical. This indicates the diameter when the image is converted into a circular image with the same area.) may be used alone or in combination. Further, a mixture of a polydisperse emulsion and a monodisperse emulsion may be used.

The silver halide emulsion may be a mixture of two or more separately formed silver halide emulsions.

Silver halide emulsions can be chemically sensitized by conventional methods. That is, sulfur sensitization method, selenium sensitization method, reduction sensitization method,
A noble metal sensitization method using gold or other noble metal compounds can be used alone or in combination.

Silver halide emulsions can be optically sensitized to a desired wavelength range using dyes known in the photographic industry as sensitizing dyes. The sensitizing dyes may be used alone or in combination of two or more. Along with the sensitizing dye, the emulsion contains a dye that itself does not have a spectral sensitizing effect, or a supersensitizer, which is a compound that does not substantially absorb visible light and enhances the sensitizing effect of the sensitizing dye. Good too.

Sensitizing dyes include cyanine dyes, merocyanine dyes,
Complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, steryl dyes and hemioxanol dyes are used.

Particularly useful dyes include cyanine dyes, merocyanine dyes,
and a complex merocyanine pigment.

Silver halide emulsions are used during the manufacturing process of photosensitive materials, during storage,
Alternatively, for the purpose of preventing fog during photographic processing or maintaining stable photographic performance, photographic Compounds known in the art as antifoggants or stabilizers can be added.

It is advantageous to use gelatin as a binder (or protective colloid) for silver halide emulsions, but gelatin derivatives, graft polymers of gelatin and other polymers, other proteins, sugar derivatives, cellulose derivatives, single Alternatively, hydrophilic colloids such as synthetic hydrophilic polymeric substances such as copolymers can also be used.

A plasticizer can be added to the silver halide emulsion layer and/or other hydrophilic colloid layer of the light-sensitive material for the purpose of increasing flexibility. Preferred plasticizers are the compounds described in RD 17643, section X-A.

The photographic emulsion layer and other hydrophilic colloid layers of the light-sensitive material may contain a dispersion (latex) of a water-insoluble or sparingly soluble synthetic polymer for the purpose of improving dimensional stability.

For example, alkyl (meth)acrylate, alkoxyalkyl (meth)acrylate, glycidyl (meth)acrylate, (meth)acrylamide, vinyl ester (e.g. vinyl acetate), acrylonitrile, olefin, styrene, etc. alone or in combination, or these and acrylic acid, A polymer containing a combination of methacrylic acid, α, β-unsaturated dicarboxylic acid, human O-oxyalkyl (meth)acrylate, sulfoalkyl (meth)acrylate, styrene sulfonic acid, etc. as a monomer component can be used.

The emulsion layer of the photosensitive material contains a dye-forming agent that forms a dye through a coupling reaction with an oxidized form of an aromatic primary amine developer (for example, p-phenylenediamine derivatives, aminophenol derivatives, etc.) during color development processing. A coupler is used. The dye-forming couplers are typically selected for each emulsion layer such that a dye is formed that absorbs light in the light-sensitive spectrum of the emulsion layer, with a yellow dye-forming coupler for the blue-sensitive emulsion layer and a dye for the green-sensitive emulsion layer. A magenta dye-forming coupler is used in the sensitive emulsion layer and a cyan dye-forming coupler is used in the red-sensitive emulsion layer. However, depending on the purpose, silver halide color 9 can be used in different ways than the above combinations.
A page-sensitive material may also be produced.

These dye-forming couplers preferably have a group called a ballast group in the molecule, which makes the coupler non-diffusive and has 8 or more carbon atoms. In addition, even if these dye-forming couplers are 4-equivalent, in which 4 silver ions need to be reduced in order to form one molecule of dye, only 2 silver ions need to be reduced. Either equivalence is acceptable. Dye-forming couplers include colored couplers that have a color correction effect and, by coupling with oxidized forms of developing agents, can be used as development inhibitors, development accelerators, bleaching accelerators, developers, silver halide solvents, and toning agents. Compounds that release photographically useful fragments such as hardeners, fogging agents, antifoggants, chemical sensitizers, spectral sensitizers, and desensitizers are included. Among these, couplers that release a development inhibitor during development and improve image sharpness and image graininess are called DIR couplers. In place of the DIR coupler, a DIR compound which undergoes a coupling reaction with the oxidized form of the developing agent to produce a colorless compound and at the same time releases a development inhibitor may be used.

The DIR couplers and DIR compounds used include those with an inhibitor directly attached to the coupling position and those with an inhibitor attached to the coupling position.
It is bonded to the coupling position via a valent group, and the inhibitor is bonded in such a way that the inhibitor is released by an intramolecular nucleophilic reaction within the group separated by the coupling reaction, an intramolecular electron transfer reaction, etc. timing DIR couplers, and timing DrR compounds). Also, depending on the purpose, inhibitors that can be dispersed after release and those that are not so dispersible can be used alone or in combination. A colorless coupler (also referred to as an a-coupler) which undergoes a coupling reaction with an oxidized product of an aromatic primary amine developer but does not form a dye can also be used in combination with a dye-forming coupler.

As the yellow dye-forming coupler, known acylacetanilide couplers can be preferably used.

Among these, benzoylacetanilide and pivaloylacetanilide compounds are advantageous. Specific examples of yellow coloring couplers that can be used include, for example, U.S. Patent No. 2,87
No. 5,057, No. 3.265,506, No. 3.4
No. 08.194, No. 3,551,155, No. 3.
No. 582.322, No. 3,725,072, No. 582.322, No. 3,725,072, No.
No. 3,891,445, West German Patent No. 1,547,86
No. 8, West German Application No. 2,219,917, No. 2,26
No. 1,361, No. 2,414゜006, British Patent No. 1
, 425,020, JP 51-10783, JP 47-26133, JP 48-73147, JP 50
-6341, 50-87650, 5o-12
No. 3342, No. 50-130442, No. 51-21
No. 827, No. 51-102636, No. 52-824
No. 24, No. 52-115219, No. 58-95346
This is what is written in the number etc.

As the magenta dye-forming coupler, known 5-pyrazolone couplers, pyrazolobenzimidazole couplers, pyrazolotriazole couplers, open-chain acylacetonitrile couplers, indacylon couplers, and the like can be used.

Specific examples of magenta color-forming couplers that can be used include, for example, U.S. Pat.
No. 3.062.653, No. 3,127,26
No. 9, No. 3,311.476, No. 3.419.3
No. 91, No. 3.519.429, No. 3,558,
No. 319, No. 3.582.322, No. 3,615
．． No. 506, No. 3.834.908, No. 3.89
1.445, West German Patent No. 1.810.464, West German Patent Application (OLS) 2, 408.665, OLS 2,41
No. 7,945, No. 2,418,959, No. 2.42
4.467, Japanese Patent Publication No. 1973-6031, Japanese Patent Application Publication No. 1973-
No. 74027, No. 49-74028, No. 49-12
No. 9538, No. 50-60233, No. 50-159
No. 336, No. 51-20826, No. 51-26541
Examples include those described in Japanese Patent Application No. 52-42121, No. 52-58922, No. 53-55122, and Japanese Patent Application No. 55-110943.

Phenol or naphthol couplers are commonly used as cyan dye-forming couplers. Specific examples of cyan color-forming couplers that can be used include, for example, U.S. Patent No. 2.42.
3.730, 2.474.293, 2.8
No. 01,171, No. 2,895,826, No. 3.
No. 476, 563, No. 3.737, 326, No. 3
, No. 758,308, No. 3.893.044 MeiI
JP-A-47-37425, JP-A No. 50-10135, JP-A No. 50-25228, JP-A No. 50-112038,
Couplers described in JP-A-50-117422, JP-A-50-130441, etc., and couplers described in JP-A-58-98731 are preferred.

Dye-forming couplers, colored couplers, DIR couplers, DIR that do not need to be adsorbed on the silver halide crystal surface
compounds, image stabilizers, color antifoggants, ultraviolet absorbers,
Among fluorescent brighteners, hydrophobic compounds can be prepared using various methods such as solid dispersion method, latex dispersion method, and oil-in-water emulsion dispersion method. It can be selected as appropriate. Various methods for dispersing hydrophobic additives such as couplers can be applied to the oil-in-water emulsion dispersion method. Usually, a high boiling point organic solvent with a boiling point of about 150°C or higher is mixed with a low boiling point and/or water-soluble additive as necessary. Dissolve using an organic solvent and emulsify using a surfactant in a hydrophilic binder such as an aqueous gelatin solution using a dispersion means such as a stirrer, homogenizer, colloid mill, flow jet mixer, or ultrasonic device. After being dispersed, it may be added to the target aqueous colloid solution. A step of removing the low boiling point organic solvent may be included simultaneously with the dispersion or dispersion.

Examples of high-boiling point solvents include organic compounds with a boiling point of 150°C or higher, such as phenol derivatives, phthalate alkyl esters, phosphate esters, citric acid esters, benzoic acid esters, alkylamides, fatty acid esters, and trimesic acid esters, which do not react with the oxidized form of the developing agent. A solvent is used.

Low boiling or water-soluble organic solvents can be used in conjunction with or in place of high boiling solvents. Examples of the low-boiling-point, substantially water-insoluble dicarboxylic solvent include ethyl acetate, propyl acetate, butyl acetate, butanol, chloroform, carbon tetrachloride, nitromethane, nitroethane, and benzene.

When dye-forming couplers, DIR couplers, colored couplers, DIR compounds, image stabilizers, color antifoggants, ultraviolet absorbers, optical brighteners, etc. have acid groups such as carboxylic acid or sulfonic acid, they can be used as an alkaline aqueous solution. They can also be incorporated into hydrophilic colloids.

Anionic surfactants and nonionic surfactants are used as dispersion aids when dissolving a hydrophobic compound in a low boiling point solvent alone or in combination with a high boiling point solvent and dispersing it in water mechanically or using ultrasonic waves. , cationic surfactants and amphoteric surfactants can be used.

The oxidized form of the developing agent or the electron transfer agent may migrate between the emulsion layers of the light-sensitive material (between the same color-sensitive layers and/or between different color-sensitive layers), causing color turbidity or deterioration of sharpness. A color antifoggant can be used to prevent graininess from becoming noticeable.

The color antifoggant may be contained in the emulsion layer itself, or
An interlayer may be provided between adjacent emulsion layers and contained in the interlayer.

An image stabilizer can be used in the photosensitive material to prevent deterioration of the dye image. Compounds that can be preferably used are those described in RD No. 17643, Section 2 J.

Hydrophilic colloid layers such as protective layers and intermediate layers of photosensitive materials contain ultraviolet absorbers to prevent fogging due to discharge caused by charging of photosensitive materials with GM, etc., and to prevent deterioration of images due to ultraviolet rays. good.

In order to prevent deterioration of magenta dye-forming couplers and the like due to formalin during storage of the light-sensitive material, a formalin scavenger can be used in the light-sensitive material.

When containing dyes, ultraviolet absorbers, etc. in the hydrophilic colloid layer of a photosensitive material, they may be mordanted with a mordant such as a cationic polymer.

Compounds that change the developability, such as development accelerators and development retarders, and bleaching accelerators can be added to the silver halide emulsion layer and/or other hydrophilic colloid layers of the light-sensitive material. Compounds that can be preferably used as development accelerators include RD 1
The compound is a compound described in Section XXI B to D of No. 7643, and the development retardant is a compound described in Section XXI E of No. 17643. A black and white developing agent and/or its precursor may be used to accelerate development or for other purposes.

The emulsion layer of a photographic light-sensitive material is made of polyalkylene oxide or its derivatives such as ethers, esters, and amines, thioether compounds, thiomorpholines, ammonium compounds, urethane derivatives, etc. for the purpose of increasing sensitivity, increasing contrast, or promoting development. It may also contain urea derivatives, imidazole derivatives, and the like.

A fluorescent whitening agent can be used in the photosensitive material for the purpose of emphasizing the whiteness of the white background and making the coloration of the white background less noticeable. Compounds which can preferably be used as optical brighteners are described in section 1 of RD 17643.

The photosensitive material can be provided with auxiliary layers such as a filter layer, an antihalation layer, an antiirradiation layer, and the like. These layers and/or the emulsion layer may contain dyes that are washed out or bleached from the light-sensitive material during the development process. Such dyes include oxonol dyes, hemioxonol dyes, styryl dyes, merocyanine dyes, cyanine dyes, azo dyes, and the like.

In the silver halide emulsion layer and/or other hydrophilic colloid layer of the light-sensitive material, reduction of gloss of the light-sensitive material, improvement of writeability,
A matting agent can be added for the purpose of preventing photosensitive materials from sticking to each other. Any matting agent can be used, but examples include silicon dioxide, titanium dioxide, magnesium dioxide, aluminum dioxide, barium sulfate, calcium carbonate, polymers of acrylic acid and methacrylic acid and their esters, polyvinyl resin, polycarbonate, and styrene. and copolymers thereof. The particle size of the matting agent is preferably 0.05μ to 10μ. The amount added is preferably 1 to 300 mg/lt.

A lubricant can be added to the photosensitive material to reduce sliding friction.

An antistatic agent can be added to the photosensitive material for the purpose of preventing static electricity. The antistatic agent may be used in the antistatic layer on the side of the support on which the emulsion is not laminated, and the protective colloid layer other than the emulsion layer on the side on which the emulsion layer is laminated with respect to the emulsion layer and/or the support. May be used for. Preferably used antistatic agents are the compounds described in RDl No. 7643 X■.

The photographic emulsion layer and/or other hydrophilic colloid layer of the light-sensitive material may be coated with coating properties, antistatic properties, slipperiness properties, emulsification dispersion,
Various surfactants can be used for the purpose of preventing adhesion and improving photographic properties (development acceleration, film hardening, sensitization, etc.).

The support used in the photosensitive material of the present invention includes α-olefin polymers (e.g. polyethylene, polypropylene,
flexible reflective supports such as synthetic abrasives, semi-synthetic or synthetic polymers such as cellulose acetate, cellulose nitrate, polystyrene, polyvinyl chloride, polyethylene terephthalate, polycarbonate, polyamide, etc. These include films made of , flexible supports made of these films with reflective layers, glass, metals, ceramics, etc.

After subjecting the surface of the support to corona discharge, ultraviolet irradiation, flame treatment, etc. as necessary, the photosensitive material can be used directly or to improve the adhesion, antistatic properties, dimensional stability, abrasion resistance, hardness, etc. of the support surface.
It may be applied through one or more subbing layers to improve antihalation properties, frictional properties, and/or other properties.

When coating the photosensitive material, a thickener may be used to improve coating properties. Also, for things like hardeners, which have quick reactivity and will cause gelation if added to the coating solution before coating, it is best to mix them using a static mixer or the like just before coating. preferable.

As a coating method, extrusion coating and curtain coating, which allow two or more types of layers to be applied at the same time, are particularly useful, but packet coating may also be used depending on the purpose. Further, the coating speed can be arbitrarily selected.

Examples of surfactants include, but are not limited to, natural surfactants such as saponin, nonionic surfactants such as alkylene oxide, glycerin, and glycidol, higher alkylamines, quaternary ammonium salts, pyridine, and others. Cationic surfactants such as heterocyclic phosphoniums or sulfoniums, anionic surfactants containing acidic groups such as carboxylic acids, sulfonic acids, phosphoric acids, sulfuric esters, phosphoric esters, amino IS! Amphoteric surfactants such as Type 2, aminosulfonic acids, sulfuric acid or phosphoric acid esters of amino alcohols may be added.

To obtain a dye image using the photosensitive material of the present invention, after exposure,
Perform color photo processing. Color processing includes a color development process, a bleaching process, a fixing process, a water washing process, and, if necessary, a stabilizing process, but instead of the process using a bleach solution and the process using a fixer. In addition, a bleach-fixing process can be performed using a one-bath bleach-fixing solution, or a monobath processing process using a one-bath developing, bleach-fixing solution that allows color development, bleaching, and fixing to be performed in one bath. You can also do

In combination with these treatment steps, a neutralization step, a stop-fixing treatment step, a post-hardening treatment step, etc. may be performed in combination with these treatment steps. In these treatments, instead of the color development process, an activator process may be performed in which a color developing agent or its precursor is contained in the material and the development process is performed using an activator solution, or an activator process may be performed in the monobath process. Processing can be applied. Among these processes, typical processes are shown below. (These treatments are carried out as the final step, which is either a water washing process, a water washing process, or a stabilization process.) Color development process - Bleach process Constant fixation process - Color development process - Bleach-fixing process Processes: Pre-hardening process - Color development process - Stop fixing process - Washing process - Bleaching process Constant fixation process - Washing process - Post-hardening process - Color development process - Washing process - Supplementary information Color development process - Stop process - Bleach process Constant monitoring process/Activator process - Bleach-fixing process/Activator process - Bleaching process Constant fixation process/Monobath process Processing temperature is usually 10°C. It is selected in the range of ~65℃,
The temperature may exceed 65°C. Preferably from 25°C
Processed at 45°C.

A color developing solution generally consists of an alkaline aqueous solution containing a color developing agent. The color developing agent is an aromatic primary amine color developing agent, and includes amine phenol derivatives and p-phenylenediamine derivatives. These color developing agents can be used as salts of organic acids and inorganic acids; for example, hydrochloric acid, sulfate, p-toluenesulfonate, sulfite, oxalate, benzenesulfonate, etc. can be used. can.

These compounds are generally about 0.0% in color developer 12.
Concentration of 1 to 30q, more preferably color developer 111
It is used at a concentration of about 1 to 15 (+).If less than 0.1 g is added, sufficient color density cannot be obtained.

Examples of the above amine phenol developer include 0-aminophenol, p-7 minophenol, 5-amino-phenol,
Included are 2-oxy-toluene, 2-amino-3-oxy-toluene, 2-oxy-3-amino-1,4-dimethyl-benzene, and the like.

Particularly useful primary aromatic amine color developers are N, N'
-Dialkyl-p-phenylenediamine type compound, and the alkyl group and phenyl group may be substituted or unsubstituted. Among them, particularly useful examples include N-N'-dimethyl-p-phenylenediamine hydrochloride, N-methyl-p-phenylenediamine hydrochloride, N,N'-dimethyl-p-phenylenediamine hydrochloride, 2- Amino-5-(N-ethyl-N-dodecylamino)-toluene, N-ethyl-N-β-methanesulfonamidoethyl-3-methyl-4-aminoaniline sulfate, N-ethyl-N-β-hydroxy Ethylaminoaniline, 4-amino-3-methyl-N, N'-diethylaniline, 4-amino-N-(2-methoxyethyl)-N-ethyl-3-methylaniline-〇-toluenesulfonate, etc. Can be done.

Further, the above color developing agents may be used alone or in combination of two or more. Furthermore, the above color developing agents may be incorporated into color photographic materials.

In this case, it is also possible to treat the silver halide color photographic light-sensitive material with an alkaline solution (activator solution) instead of a color developing solution, and the bleach-fixing process is carried out immediately after the alkaline solution treatment.

The color developing solution used in the present invention may contain alkaline agents commonly used in developing solutions, such as sodium hydroxide, potassium hydroxide, ammonium hydroxide, sodium carbonate, potassium carbonate, sodium sulfate, sodium metaborate, or borax. In addition, various additives such as benzyl alcohol, alkali metal halides such as potassium bromide or potassium chloride, development regulators such as citradinic acid, preservatives such as hydroxylamine or sulfite M salts, etc. May contain. Furthermore, various antifoaming agents and surfactants, as well as organic solvents such as methanol, dimethylformamide or dimethyl sulfoxide, etc. can be appropriately contained.

The pH of the color developing solution used in the present invention is usually 7 or more,
Preferably it is about 9-13.

In addition, the color developing solution used in the present invention may contain antioxidants such as diethylhydroxyamine, tetronic acid, tetronimide, 2-anilinoethanol, dihydroxyacetone, aromatic secondary alcohol, hydroxamic acid, pentose, or hexose, pyrogallol-1,
3-dimethyl ether etc. may be contained.

Various chelating agents can be used in combination as metal ion sequestering agents in the color developing solution used in the present invention. For example, as the chelating agent, amine polycarboxylic acids such as ethylenediaminetetraacetic acid and diethylenetriaminopentaacetic acid,
-organic phosphonic acids such as hydroxyethylidene-1,1'-diphosphonic acid, aminopolyphosphonic acids such as aminotri(methylenephosphonic acid) or ethylenediaminetetraphosphoric acid, oxycarboxylic acids such as citric acid or gluconic acid, 2-phosphonobutane-1 , phosphonocarboxylic acids such as 2,4-tricarboxylic acid, polyphosphoric acids such as tripolyphosphoric acid or hexametaphosphoric acid, and polyhydroxy compounds.

The bleaching process may be performed simultaneously with the fixing process as described above, or may be performed separately.

As a bleaching agent, a metal complex salt of *M is used, for example, a polycarboxylic acid, an aminopolycarboxylic acid, or an R acid such as oxalic acid or citric acid coordinated with a metal ion such as iron, cobalt, or copper. used. Among the above organic acids, the most preferred R acid includes polycarboxylic acids and aminopolycarboxylic acids. Specific examples of these include ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, and ethylenediamine-N=(β-oxyethyl)-
N,N',N'-triacetic acid, propylenediaminetetraacetic acid, nitrilotriacetic acid, cyclohexanediaminetetraacetic acid, iminodiacetic acid, dihydroxyethylglycincitric acid (or tartaric acid), ethyl etherdiaminetetraacetic acid, glycol etherdiaminetetraacetic acid, Examples include ethylenediaminetetrapropionic acid and phenylenediaminetetraacetic acid.

These polycarboxylic acids may be alkali metal salts, ammonium salts or water-soluble amine salts. These bleaches are 5-450 Q/l, more preferably 20
~250Q/(l) is used.

In addition to the above bleaching agent, the bleaching solution may contain a sulfite as a preservative, if necessary. Alternatively, it may be a bleaching solution containing an ethylenediaminetetraacetate iron (III) complex salt bleaching agent and a large amount of a halide such as ammonium bromide added thereto. As the halides, in addition to ammonium bromide, hydrochloric acid, hydrobromic acid, lithium bromide, sodium bromide, potassium bromide, sodium iodide, potassium iodide, ammonium iodide, etc. can also be used. can.

The bleaching solution used in the present invention includes JP-A No. 46-280, JP-B No. 45-8506, JP-B No. 46-556, Belgian Patent No. 770,910, JP-A No. 45-8836,
Various bleach accelerators described in JP-A-53-9854, JP-A-54-71634 and JP-A-49-42349 can be added.

The pH of the bleaching solution used is 2.0 or higher, but generally it is 4.
．． It is used between 0 and 9.5, preferably between 4.5 and 80, and most preferably between 5.0 and 7.0.

A fixer having a commonly used composition can be used. As a fixing agent, a compound that reacts with silver halide to form a water-soluble complex salt, such as a thiosulfate such as potassium thiosulfate, sodium thiosulfate, or ammonium thiosulfate, or potassium thiocyanate, which is used in ordinary fixing processing, may be used. Typical examples thereof include thiocyanates such as sodium thiocyanate and ammonium thiocyanate, thiourea, and thioether. These fixatives are 5
It is used in an amount of 972 gzl or more, but is generally used in an amount of 70 to 250 gzl. Incidentally, a part of the fixing agent can be contained in the bleaching tank, or conversely, a part of the bleaching agent can also be contained in the fixing tank.

In addition, the bleaching solution and/or fixing solution includes Ta acid, borax, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, acetic acid, sodium acetate, ammonium hydroxide, etc. with various pH values. )il
! Fi agents may be contained alone or in combination of two or more. In addition, various optical brighteners, antifoaming agents, or surfactants can be contained.

Also, hydroxylamine, drazine, aldehyde compound heavy nitrogen! Preservatives such as i7N acid adducts, organic chelating agents such as aminopolycarboxylic acids, stabilizers such as nitro alcohols and nitrates, hardeners such as water-soluble aluminum salts, methanol, dimethylsulfamide, dimethylsulfoxide, etc. An organic solvent or the like can be appropriately contained.

The I)H of the fixer is used at 3.0 or more, generally from 4.5 to 10, preferably from 5 to 9.5, and most preferably from 6 to 9.

Examples of the bleaching agent used in the bleach-fixing solution include the gold i-complex salts of organic acids described in the above bleaching process, and preferred compounds and concentrations in the processing solution are also the same as in the above bleaching process.

The bleach-fixing solution contains a silver halide fixing agent in addition to the above bleaching agent, and if necessary, a sulfite salt as a preservative. In addition, a bleach-fix solution consisting of an ethylenediaminetetraacetate iron (I [ Bleach-fix solutions containing a large amount of halides such as halides, and special bleach-fix solutions containing a combination of ethylenediaminetetraacetate iron (m ) complex salt bleach and large amounts of halides such as ammonium bromide. can also be used. In addition to ammonium bromide, the halides include hydrochloric acid, hydrobromic acid,
Lithium bromide, sodium bromide, potassium bromide, sodium iodide, potassium iodide, ammonium iodide, and the like can also be used.

Examples of the silver halide fixing agent that can be included in the bleach-fixing solution include the fixing agents described in the above fixing process. The concentration of the fixing agent, the pH buffer that can be contained in the bleach-fixing solution, and the additives thereof are the same as in the fixing process described above.

The bleach-fix solution is used at a pH of 4.0 or higher, but is generally used at a pH of 5.0 to 9.5, preferably 6.0 to 8.
5, most preferably 6.5 to 8.5.

[Effects of the Invention] According to the silver halide photographic light-sensitive material of the present invention, the leaching of specific fluorocompounds into the processing solution is eliminated, and the generation of sludge is suppressed, so that the use of large amounts of organic fluorocompounds is avoided. The antistatic properties and adhesion resistance have been significantly improved.

In addition, there is no disadvantage that the silver halide emulsion layer is also hardened more than necessary as the organic fluoro compound-containing layer is hardened, unlike the conventional method, so there is no reduction in sensitivity.

[Examples] Specific examples of the present invention will be described below, but the embodiments of the present invention are not limited thereto.

In the following examples, the amount added in the silver halide photographic light-sensitive material is per 112 unless otherwise specified.

In addition, silver halide and colloidal silver are shown in terms of silver.

Actual Droplet Example 1 Multilayer color photographic material sample 1 was prepared by sequentially forming layers having the compositions shown below on a triacetyl cellulose film support from the support side.

Sample-1 1st layer; antihalation layer Gelatin layer containing black colloidal silver.

Gelatin 2.2i11/i’ Second Tang: Middle class 2.5-di-t-octyl hydroxide A gelatin layer containing an emulsified dispersion of non-alcoholic acid.

Gelatin 1.2(]/i2 3rd layer; low sensitivity red-sensitive silver halide emulsion layer average grain size (r
) 0.30 um, Aa containing 16 mol% Ag
Monodisperse emulsion consisting of Brl (emulsion technique)...trowel application 1! 1.8! ]
/ *2 Sensitizing dye■... 6x1o-'55 moles for 1 mole of silver Sensitizer■... 1.0x10-5 moles cyan coupler (C-1>... for 1 mole of silver) Colored cyan coupler (CG-1): 0.003 mol per mol of silver DIR compound (D-1): 0.0015 mol per mol of silver Mol DIR compound (D-2)... 0.002 mol gelatin 1.4 g/v' for 1 mol silver 4th layer: Highly sensitive red-sensitive silver halide emulsion layer average grain size (r
) 0.5 μm, , II containing 7.0 mol%
Monodisperse emulsion consisting of g8rl (emulsion ■)...trowel application f
l 1.3 (1/12 sensitizing dye ■... 3 x 10-5 mol sensitizing dye ■... 1.0 x 10-5 mol cyan coupler (C-1 >>0.02 mol colored cyan coupler (CC-1>...11-E/
L, 1. Jl SITO, 0015-E/L.

DIR compound (D-2)... 0001 mol per 1 mol of silver Gelatin 1.0 (1/n2 5th layer; middle layer Gelatin layer, same as M2 layer.

Gelatin 1.013/1' 6th layer; Low sensitivity green sensitive silver halide emulsion layer Emulsion - ■...
・Coated silver @ 1.5o /12 sensitizing dye ■... 2.5 x 10-5 mol sensitizing dye ■... per 1 mol of silver
- 1.2 x 10-5 mole magenta coupler (M-1) per mole of silver... 0.050 mole per mole of silver Colored magenta coupler (CMl)... 0.05 mole per mole of silver. 009 mol [) JR compound (D-1)... 10 mol of O,0O per 1 mol of tM DIR compound (D-3)... 0.0030 mol gelatin per 1 mol of silver. OQ/n' 7th layer: High-sensitivity green-sensitive silver halide emulsion layer Emulsion - ■...
・Coating silver 11.4 (1/+' sensitizing dye ■... 1.5 x 10-5 mol sensitizing dye ■ for 1 mol of silver ・
... 1.0x10-5 mole magenta coupler (M-1) for 1 mole of silver...0.02 for 1 mole of silver
0 mol colored magenta coupler (CM-1)...0.002 mol DIR compound per 1 mol silver (D-3>... 0.0010 mol gelatin 1.8Q per mol silver) /1' 8th layer; yellow filter layer: a gelatin layer containing yellow colloidal silver and an emulsified dispersion of 2,5-di[-octylhydroquinone.

Gelatin L5g/12 9th layer: Low sensitivity blue-sensitive silver halide emulsion layer Average grain size 0.
48 ttm, l+Brl containing 6 mol% AgI
Monodispersed emulsion (emulsion ■) consisting of...silver-shaped cloth It O,9! ]/
v2 sensitizing dye V... 1.3 x 10-5 mol yellow coupler (Y-1>...0.29 per mol silver)
Morgelatin 1.9 (1/n2 10th layer; high sensitivity blue-sensitive emulsion layer average grain size 0.8 μm, containing 15 mol% AgI)
Monodisperse emulsion consisting of Brl Emulsion ■)...Silver type cloth m O, 50/i'
Sensitizing dye ■... 1.0 x 10-5 mol per mol of silver Yellow coupler (Y-1)... 0.08 mol per mol of silver DIR compound (D-2)... Silver 0.0015 mol gelatin per 1 mol 1.6 Q /f 11th layer; 1st protective layer silver iodobromide (A! 1111 mol % average particle size 0.01 μm)
Silver type cloth ffi O, 50/v' ultraviolet absorber UV-1,
Gelatin layer containing UV-2.

Gelatin 1.2 g/i' 12th layer; second protective layer polymethyl methacrylate particles (diameter 165 μm) copolymer particles of ethyl methacrylate: methyl methacrylate: methacrylic acid (average particle size 2.5 μm) organic fluoro compound of the present invention (Table-1) Polymer hardener of the present invention (Table-1) Low-molecular hardener (H-7) 2.5X 10-3 equivalent/100 (+gelatin formalin scavenger (H3-1) gelatin layer containing.

Gelatin 1.2 (1/f) Samples 2 to 1 in which the organic fluoro compound and polymer hardener in the 12th m1f of Sample 1 were changed as shown in Table 1.
3 was produced.

The compounds contained in each layer of Sample 1 are as follows.

Sensitizing dye ■: Anhydro 5,5'-dichloro-〇-edy-3,3'-di(3-sulfopropyl)thiacarbocyanine human oxide Sensitizing dye ■: Anhydro 9-ethyl-3,3'-di (
3-sulfopropyl)-4,5,4',5'-dibenzothiacarbocyanine hydroxide sensitizing dye■; anhydro5,5'-diphenyl-9-ethyl-3,3'-di(3-sulfopropyl) Rubocyanine hydroxide sensitizing dye ■: Anhydro-9-ethyl-3.3'-di(
anhydro 3,3'-di(3-sulfopropyl)-4,5-benzo-5'- Margin CH below methoxythiacyanine.

M-1 I I CJ? V-1 JV-2 C,H.

[Adhesion resistance] For each sample, cut two pieces into 5 cm square pieces and heat them at 23°C and 80% R so that they do not touch each other.
After being stored in an atmosphere of H for one day, two protective layers of the same sample were brought into contact with each other, and a load of 800 g was applied.
The sample was stored in an atmosphere of 40° C. and 80% RH, and then the sample was peeled off and the area of the adhesive portion was measured to measure the adhesiveness.

The evaluation criteria are as follows.

Rank Area of adhesive part A 0-20% 8 21-40% 0 41-60% D 61% or more The results are shown in Table-1.

[Sludge Generation] Each sample was cut into 30.5 cm x 17.1 cm squares, and 50 sheets were continuously developed in the following development process to check whether sludge was generated.

[Sensitivity] In addition, each sample was wedge-exposed with white light and then subjected to the following development process, and the sensitivity was compared. Sensitivity is fog +0
．． Comparative sample 1 is the reciprocal of the exposure mother required to obtain a density of 5
The relative sensitivity is shown with the sensitivity of 1 being 100. Display the results -
Shown in 1.

[Antistatic property 1 The antistatic property of each sample was examined using the following method.

After conditioning the unexposed sample at 25°C and 25% RH for 2 hours, the emulsion side of the sample was rubbed with a neoprene rubber wax in a dark room under the same air conditioning conditions, and then developed with the following processing solution.
After bleaching, fixing, washing and stabilization, the degree of static mark occurrence was examined.

The evaluation of the degree of static mark occurrence is A: No static marks are observed. B: Some static marks are observed. C: A considerable amount of static marks are observed. D: No static marks are observed. It was divided into four stages, which were almost universally recognized. The results are shown in Table-1.

Processing process (38℃) Color development 3 minutes 15 seconds Bleaching 6 minutes 30 seconds Water washing 3 minutes 15 seconds
Arrive: Wash for 6 minutes and 30 seconds
Stabilized for 3 minutes and 15 seconds
Drying for 1 minute and 30 seconds The composition of the treatment liquid used in each treatment step is as follows.

[Color developer] 4-amino-3-methyl-N-ethyl-N-(β-hydroxyethyl)-aniline sulfate 4.751J anhydrous sodium sulfite 4.25 (1 hydroxylamine 1/2 sulfur 150 salt 20g anhydrous potassium carbonate 375g sodium bromide
1.3g nitrilotriacetic acid trisodium salt (monohydrate) 2.51J potassium hydroxide 1.09 Add water to make 12.

[Bleach solution] Ethylenediaminetetraacetic acid iron ammonium salt ioo, o g Ethylenediaminetetraacetic acid M2 Ammonium salt 10.0g Ammonium bromide iso, o g Wood vinegar M
Add 10.01N water to make the solution 12, and adjust the pH to 6.0 using ammonia water.

[Fixer] Ammonium thiosulfate 175.0 (1 Anhydrous sodium sulfite 8.5 g Sodium metasulfite 2.3 g Water was added to 12
and adjust the pH to 6.0 using acetic acid.

[Stabilizer] Formalin (37% aqueous solution) 1.5 year old Konidax (manufactured by Konishiroku Photo Industry Co., Ltd.) Add 7.5 d of water to make 12.

From the results in Table 1, it is clear that although it contains organic fluoro compounds,
Sample 11, which did not use a polymeric hardener, generated sludge due to leaching of the organic fluoro compound, and also had insufficient adhesion resistance and antistatic properties. Sample 12, in which the amount of organic fluoro compound added was reduced, did not generate sludge, but had poor adhesion resistance and antistatic properties. In addition, in sample 13 in which the amount of low-molecular hardening agent was increased, the degree of hardening of the organic fluoro compound-containing layer was increased, and no sludge was generated.
Adhesion resistance and antistatic properties are also good, but the degree of hardness of the silver halide emulsion layer is too high, resulting in a significant decrease in sensitivity.

On the other hand, Samples 1 to 10 of the present invention have good adhesion resistance and antistatic properties, and do not generate sludge or reduce sensitivity.

Example 2 Example 1 was carried out by using H-6 instead of the low-molecular hardening agent H-7 used in the sample in Example 1, and using Q-2 as the polymer to provide the high-molecular hardening agent. A similar sample was prepared and evaluated in the same manner as in Example 1.

The results are shown in Table-2.

The results shown in Table 2 show that the effects of the present invention can be obtained even when using a polymer hardener formed from a polymer that provides a polymer hardener and a low molecular hardener. That is, Samples 14 to 18 of the present invention have good adhesion resistance and antistatic properties, and do not generate sludge.

Margin Example 3 Each layer having the composition shown below was sequentially formed on both sides of a subbed polyethylene terephthalate support from the support side to obtain an X-ray photosensitive material sample. Additives other than silver halide are shown in amounts per mole of silver halide unless otherwise specified.

1st layer Crossover cut layer Dye (I) 3n+a/f gelatin layer Gelatin 0.20/l' 2nd layer Emulsion layer Average grain size 1.2μ, AgB containing 1.5 mol% Ag1
Emulsion-coated silver m consisting of r1...4 CJ/f4-hydroxy-6-methyl-1゜3.3a, 7-chitrazaindene...1.2g Diethylene glycol...ii, og paranitrophenyltriphenylphos Phytochloride 0.2g Gelatin 2.5+11 /f 3rd layer Protective layer Sodium diethylhexyl succinate sulfonate ...0.015Q /12 Glyoxal ...0.02Ω/f Mucochloric acid
...0.015 (1/12 Particles of polymethyl methacrylate (average particle size 3 to 4 μ) -50 mQ/v' Gelatin 0.9 (1/f Organic fluoro compound of the present invention 600111 (1/ i") of the present invention Polymer hardener i, ax i o 'dougo / 100g gelatin dye (I
) The obtained sample was evaluated in the same manner as in Example 1.

However, the treatment steps were as shown below.

The results are shown in Table-3.

[Processing process] Current (i! 30℃ 45
Second fixation 25℃ 35 seconds water
Wash and dry at 15℃ for 35 seconds
45℃ 20 seconds [Developer] Phenidone o, agmetol 5Q hydroquinone
1g anhydrous sodium sulfite
sog hydrated sodium carbonate
54 (15-nitroimidazole 1
00n+g potassium bromide 2.5
g Add water to make 1000d and make pl-110,20.

[Fixer] (Part A) Ammonium thiosulfate 170g Sodium sulfite 15g
6.5Q glacial acetic acid
12iR Sodium citrate (dihydrate) 2.5 (J Add water to make 275 d.

(Part B) Aluminum sulfate 15 q98%
Add 2.5g of 5A acid water and add 4
Finish to 01g.

When using Part A: 2751f, Bar i-B:
Add water to 40 g to make 12.

From the results shown in Margin Table 3 below, even when the present invention is applied to X-ray photosensitive materials, Samples 21 to 28 according to the present invention have good adhesion resistance and antistatic properties, and moreover, they do not generate sludge. I know it won't happen.

Patent applicant Konishiroku Photo Industry Co., Ltd. Representative Patent Attorney Totoo Ichinose procedure:? Ittz book (spontaneous) November 26, 1986

Claims (2)

[Claims] (1) In a silver halide photographic material having at least one hydrophilic colloid layer on a support, at least one of the hydrophilic colloid layers contains an organic fluoro compound and is hardened with a polymer hardener. A silver halide photographic material characterized by: (2) The hydrophilic colloid layer containing an organic fluoro compound and hardened with a polymer hardening agent is a non-photosensitive layer located farthest from the support. A silver halide photographic material according to scope (1).