JP3191194B2 - Silver halide photographic materials - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide photographic light-sensitive material, and more particularly to a silver halide photographic light-sensitive material which does not peel off when processed rapidly by an automatic processor and has good drying properties.

[0002]

2. Description of the Related Art In rapid processing of a silver halide photographic light-sensitive material by an automatic developing machine, improvement of the drying property of the light-sensitive material is an essential condition for shortening the time. For this reason, proposals have conventionally been made to reduce the amount of binder (mainly gelatin) in the hydrophilic colloid layer constituting the light-sensitive material and to reduce the drying load by reducing the swelling property of the film.

[0003] However, if the amount of gelatin is reduced until the drying property is accelerated, the pinhole-like shape will not be produced when the film is conveyed at high speed by an automatic processor.
(Dot-like) film peeling and fatal failure.

[0004] This phenomenon is called a pick-off failure and includes a conventionally known stalinite failure (stardust failure),
This is a failure different from pinholes caused by dust adhesion.

[0005]

In order to improve the pick-off failure when the photosensitive material is thinned and rapid processing is performed, the present inventors have attempted to add a conventionally known polymer latex. Sufficient results were not obtained.
Also, a method for increasing the melting time of a photosensitive material in an aqueous alkaline solution to improve pick-off failure
(Hardening) has been proposed, but this method has a problem that the residual color is deteriorated.

An object of the present invention is to provide a silver halide photographic material which is excellent in drying property, has no residual color property and has no pick-off failure in rapid processing by an automatic processor.

[0007]

SUMMARY OF THE INVENTION The object of the present invention is to polymerize at least one monomer having a solubility in water at 25 ° C. of not more than 0.025% by weight in at least one layer on a support. At least one polymer latex, and 0.2 to 100 fluorine-containing surfactants.
mg / m ^2, which was achieved by a silver halide photographic material. More preferably, the polymer contains at least one polymer latex obtained by polymerizing the monomer in an amount of 50% by weight or more, and contains a fluorine-containing surfactant in an amount of 0.2%.
It is achieved by a silver halide photographic light-sensitive material characterized in that it contains -100 mg / m ² .

The above-mentioned monomer is preferably an acrylate compound, particularly preferably when both an acrylate compound and a methacrylate compound are used. The particle size of the polymer latex of the present invention is preferably 300 nm or less.

The polymer latex of the present invention is preferably polymerized in the presence of a water-soluble polymer and / or a surfactant.

At least one of the monomers forming the polymer latex used in the present invention has a solubility in water at 25 ° C. of not more than 0.025% by weight, preferably not more than 0.015% by weight. Such ethylenic monomers include, for example, hexyl acrylate, 2
-Acrylates such as ethylhexyl acrylate, octyl acrylate, tert-octyl acrylate, nonyl acrylate, iso-nonyl acrylate, cyclohexyl acrylate, n-stearyl acrylate, lauryl acrylate, tridecyl acrylate, butyl methacrylate, iso-butyl methacrylate, tert -Butyl methacrylate, hexyl methacrylate, 2-ethylhexyl methacrylate, octyl methacrylate, iso-octyl methacrylate, tert-octyl methacrylate, nonyl methacrylate, iso-nonyl methacrylate, cyclohexyl methacrylate, n-stearyl methacrylate, lauryl Examples include methacrylates such as methacrylate and tridecyl methacrylate, and divinylbenzene.

The solubility of the monomer forming the polymer latex used in the present invention in water at 25 ° C. can be measured by the method described in Basic Experiment 1 of New Experimental Chemistry Course (Maruzen Chemical, 1975). . When measured by this method, the solubility of the monomer of the present invention in water at 25 ° C. is, for example, 0.01% by weight for 2-ethylhexyl acrylate, 0.00% by weight for 2-ethylhexyl methacrylate, and 0.00% by weight for cyclohexyl methacrylate. The comparative monomer was 0.03% by weight for styrene, 0.32% by weight for butyl acrylate, and 0.03% by weight for butyl methacrylate.

[0012] The polymer latex used in the present invention may be copolymerized with other monomer compounds other than the above monomer compounds.
For example, acrylic esters, methacrylic esters, vinyl esters, olefins, styrenes, crotonic esters, itaconic diesters, maleic diesters, fumaric diesters, acrylamides, allyl compounds, vinyl ethers, Examples thereof include monomer compounds selected from one or two or more selected from vinyl ketones, vinyl heterocyclic compounds, glycidyl esters, unsaturated nitriles, polyfunctional monomers, and various unsaturated acids.

More specifically, these monomeric compounds are exemplified by methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, and sec-butyl acrylate. , Tert-butyl acrylate, amyl acrylate,
Hexyl acrylate, 2-chloroethyl acrylate,
2-bromoethyl acrylate, 4-chlorobutyl acrylate, cyanoethyl acrylate, 2-acetoxyethyl acrylate, dimethylaminoethyl acrylate, methoxybenzyl acrylate, 2-chlorocyclohexyl acrylate, furfuryl acrylate, tetrahydrofurfuryl acrylate, phenyl acrylate, 2- Hydroxyethyl acrylate, 5-hydroxypentyl acrylate, 2,2-dimethyl-3-hydroxypropyl acrylate, 2-methoxyethyl acrylate, 3-methoxybutyl acrylate, 2-ethoxyethyl acrylate,
2-iso-propoxy acrylate, 2-butoxyethyl acrylate, 2- (2-methoxyethoxy) ethyl acrylate, 2- (2-butoxyethoxy) ethyl acrylate, ω-
Examples include methoxypolyethylene glycol acrylate (additional mole number n = 9), 1-bromo-2-methoxyethyl acrylate, 1,1-dichloro-2-ethoxyethyl acrylate, and the like.

Examples of the methacrylates include methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, amyl methacrylate, chlorobenzyl methacrylate, sulfopropyl methacrylate, N-ethyl-N-phenylaminoethyl methacrylate, (3-phenylpropyloxy) ethyl methacrylate, dimethylaminophenoxyethyl methacrylate, furfuryl methacrylate,
Tetrahydrofurfuryl methacrylate, phenyl methacrylate, cresyl methacrylate, naphthyl methacrylate, 2-hydroxyethyl methacrylate, 4-hydroxybutyl methacrylate, triethylene glycol monomethacrylate, dipropylene glycol monomethacrylate, 2-methoxyethyl methacrylate, 3-methoxybutyl methacrylate , 2-acetoxyethyl methacrylate, 2-acetoacetoxyethyl methacrylate,
2-ethoxyethyl methacrylate, 2-iso-propoxyethyl methacrylate, 2-butoxyethyl methacrylate, 2- (2-methoxyethoxy) ethyl methacrylate, 2-
(2-ethoxyethoxy) ethyl methacrylate, 2- (2-butoxyethoxy) ethyl methacrylate, ω-methoxy polyethylene glycol methacrylate (additional mole number n =
6), allyl methacrylate, dimethylaminoethyl methyl methacrylate chloride salt and the like.

Examples of vinyl esters include vinyl acetate, vinyl propionate, vinyl butyrate,
Examples thereof include vinyl isobutyrate, vinyl caproate, vinyl chloroacetate, vinyl methoxy acetate, vinyl phenyl acetate, vinyl benzoate, and vinyl salicylate.

Examples of olefins include dicyclopentadiene, ethylene, propylene, 1-butene, 1-pentene, vinyl chloride, vinylidene chloride, isoprene, chloroprene, butadiene, and 2,3-dimethylbutadiene. it can.

Examples of styrenes include styrene,
Examples include methylstyrene, dimethylstyrene, trimethylstyrene, ethylstyrene, isopropylstyrene, chloromethylstyrene, methoxystyrene, acetoxystyrene, chlorostyrene, dichlorostyrene, bromostyrene, trifluoromethylstyrene, and methyl vinyl benzoate.

Examples of crotonates include butyl crotonate and hexyl crotonate.

Examples of the diethyl itaconates include dimethyl itaconate, diethyl itaconate, and dibutyl itaconate.

The maleic acid diesters include, for example, diethyl maleate, dimethyl maleate, dibutyl maleate and the like.

As the fumaric acid diesters, for example,
Examples thereof include diethyl fumarate, dimethyl fumarate, and dibutyl fumarate.

Examples of acrylamides include acrylamide, methyl acrylamide, ethyl acrylamide, propyl acrylamide, butyl acrylamide, tert-
Butylacrylamide, cyclohexylacrylamide, benzylacrylamide, hydroxymethylacrylamide, methoxyethylacrylamide, dimethylaminoethylacrylamide, phenylacrylamide,
Dimethyl acrylamide, diethyl acrylamide, β
-Cyanoethylacrylamide, N- (2-acetoacetoxyethyl) acrylamide and the like; methacrylamides, for example, methacrylamide, methyl methacrylamide, ethyl methacrylamide, propyl methacrylamide, butyl methacrylamide, tert-butyl methacrylamide, cyclohexyl methacrylamide , Benzyl methacrylamide, hydroxymethyl methacrylamide, methoxyethyl methacrylamide, dimethylaminoethyl methacrylamide, phenyl methacrylamide, dimethyl methacrylamide, diethyl methacrylamide, β-cyanoethyl methacrylamide, N- (2-acetoacetoxyethyl) methacrylamide Allyl compounds such as allyl acetate, allyl caproate, allyl laurate, allyl benzoate and the like; Le, such as, for example,
Methyl vinyl ether, butyl vinyl ether, hexyl vinyl ether, methoxyethyl vinyl ether, dimethylaminoethyl vinyl ether, etc .; vinyl ketones, for example, methyl vinyl ketone, phenyl vinyl ketone, methoxyethyl vinyl ketone, etc .; vinyl heterocyclic compounds, for example, vinyl pyridine, N -Vinylimidazole, N-vinyloxazolidone, N-vinyltriazole,
N-vinylpyrrolidone and the like; glycidyl esters such as glycidyl acrylate and glycidyl methacrylate; unsaturated nitriles such as acrylonitrile and methacrylonitrile; and polyfunctional monomers such as divinylbenzene and methylenebisacrylamide;
Ethylene glycol dimethacrylate and the like.

Further, acrylic acid, methacrylic acid, itaconic acid, maleic acid, monoalkyl itaconate, for example,
Monomethyl itaconate, monoethyl itaconate, monobutyl itaconate, etc .; monoalkyl maleate such as monomethyl maleate, monoethyl maleate, monobutyl maleate, etc .; citraconic acid, styrene sulfonic acid, vinylbenzyl sulfonic acid, vinyl sulfonic acid, acryloyl Oxyalkylsulfonic acid, for example,
Acryloyloxymethylsulfonic acid, acryloyloxyethylsulfonic acid, acryloyloxypropylsulfonic acid and the like; methacryloyloxyalkylsulfonic acid such as methacryloyloxydimethylsulfonic acid, methacryloyloxyethylsulfonic acid and methacryloyloxypropylsulfonic acid; acrylamidoalkylsulfonic acid For example, 2-acrylamido-2-methylethanesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, 2-acrylamido-2-methylbutanesulfonic acid and the like; methacrylamidoalkylsulfonic acid, for example, 2-methacrylamido- 2-methylethanesulfonic acid, 2-methacrylamido-2-methylpropanesulfonic acid, 2-methacrylamido-2-methylbutanesulfonic acid, etc .; acryloyloxyalkyl phos Phosphates, for example, acryloyloxyethyl phosphate, 3-acryloyloxypropyl-2-phosphate, etc .; methacryloyloxyalkyl phosphates, for example, methacryloyloxyethyl phosphate, 3-methacryloyloxypropyl-2-phosphate, etc .; 3 having two hydrophilic groups -Naphthyl allyloxy-2-hydroxypropanesulfonate and the like. These acids may be salts of alkali metals (eg, Na, K, etc.) or ammonium ions. Still other monomer compounds, U.S. Pat.Nos. 3,459,790, 3,438,708, 3,554,987,
Crosslinkable monomers described in JP-A-4,215,195, JP-A-4,247,673 and JP-A-57-205735 can be used. Specific examples of such a crosslinkable monomer include N- (2-acetoacetoxyethyl) acrylamide, N- {2- (2-acetoacetoxyethoxy) ethyl} acrylamide and the like.

Of these monomer compounds, acrylic esters, methacrylic esters, vinyl esters, styrenes, and olefins are preferably used.

The surfactant used in the polymerization of the polymer latex of the present invention includes an anionic surfactant,
Any of a nonionic surfactant, a cationic surfactant, and an amphoteric surfactant can be used, but an anionic surfactant and / or a nonionic surfactant are preferable. As the anionic surfactant and the nonionic surfactant, various compounds known in the art can be used, and an anionic surfactant is particularly preferably used.

The water-soluble polymer used in the polymerization of the polymer latex of the present invention includes, for example, a synthetic polymer and a natural water-soluble polymer, and any of them can be preferably used in the present invention. Among them, synthetic water-soluble polymers include those having a nonionic group in the molecular structure, those having an anionic group, those having a cationic group, those having a nonionic group and an anionic group, those having a nonionic Examples include those having a group and a cationic group, those having an anionic group and a cationic group, and the like. Examples of the nonionic group include an ether group, an alkylene oxide group, a hydroxy group, an amide group, and an amino group. Examples of the anionic group include a carboxylic acid group or a salt thereof, a phosphoric acid group or a salt thereof, a sulfonic acid group or a salt thereof, and the like. Examples of the cationic group include a quaternary ammonium base and a tertiary amino group.

As the natural water-soluble polymer, those having a nonionic group in the molecular structure, those having an anionic group, those having a cationic group, those having a nonionic group and an anionic group, Examples include those having a nonionic group and a cationic group, those having an anionic group and a cationic group, and the like.

The water-soluble polymer used in the polymerization of the polymer latex of the present invention may be any one of a synthetic water-soluble polymer and a natural water-soluble polymer having an anionic group, a nonionic group and an anionic group. Those having the following can be preferably used.

In the present invention, the water-soluble polymer is 2
0.05 g or more should be dissolved in 100 g of water at 0 ° C., and preferably 0.1 g or more.

As the natural water-soluble polymer, a comprehensive technical data collection of water-soluble polymer water-dispersible resins (for example, those described in detail in the Business Development Center, but preferably lignin, starch, pullulan, cellulose, dextran) Dextrin, glycogen, alginic acid, gelatin, collagen, guar gum, gum arabic, laminaran, lichenin, nigran, etc. and derivatives of natural water-soluble polymers such as sulfonation, carboxylation, phosphorylation, sulfo Alkenylated, carboxyalkylated, alkylphosphorylated and salts thereof are preferably used, particularly preferably glucose, gelatin, dextran, cellulose and derivatives thereof.

The polymer latex used in the present invention can be easily produced by various methods. For example, there is a method of redispersing a polymer obtained by an emulsion polymerization method, a solution polymerization, a bulk polymerization, or the like.

In the emulsion polymerization method, water is used as a dispersion medium, and 10 to 50% by weight of a monomer based on water and 0.05 to 5% by weight of a polymerization initiator based on water, and 0.1 to 20% by weight of a monomer. Using a dispersant, about 3
It is obtained by polymerizing under stirring at 0 to 100 ° C, preferably 60 to 90 ° C for 3 to 8 hours. The concentration of the monomer, the amount of the initiator, the reaction temperature, the time and the like can be widely and easily changed.

Examples of the initiator include a water-soluble peroxide (eg, potassium persulfate, ammonium persulfate, etc.) and a water-soluble azo compound (eg, 2,2′-azobis- (2-amidinopropane)-
Hydrochloride, etc.).

Examples of the dispersant include anionic surfactants, nonionic surfactants, cationic surfactants, and amphoteric surfactants in addition to the water-soluble polymer. These may be used alone or in combination. In solution polymerization, which is preferably a combination of a water-soluble polymer and a nonionic or anionic activator, generally a mixture of monomers in a suitable solvent (eg, ethanol, methanol, water, etc.) at a suitable concentration (usually, An appropriate temperature (for example, benzoyl peroxide, azobisisobutyronitrile, ammonium persulfate, etc.) in the presence of a polymerization initiator (e.g., benzoyl peroxide, azobisisobutyronitrile, ammonium persulfate, etc.) at 40% by weight or less, preferably 10 to 25% by weight based on the solvent. The copolymerization reaction is carried out by heating to 40 to 120 ° C, preferably 50 to 100 ° C). Thereafter, the reaction mixture is poured into a medium that does not dissolve the formed copolymer, the product is allowed to settle, and then the unreacted mixture is separated and removed by drying.

Next, the copolymer is dissolved in a solvent that dissolves the copolymer but is not soluble in water (eg, ethyl acetate, butanol, etc.), and is vigorously dispersed in the presence of a dispersant (eg, a surfactant, a water-soluble polymer, etc.). Is distilled off to obtain a polymer latex.

The Tg (glass transition temperature) of the polymer forming the polymer latex used in the present invention is preferably 60 ° C. or lower, particularly preferably 40 ° C. or lower.

The Tg of many polymers of the ethylenic monomers used in the present invention can be found in Brand Polymer et al., Polymer Handbook, pages III-139 to III-179 (1966).
Year) (Wiley & Sons, Inc.)
The Tg (° K) of the copolymer is represented by the following formula.

[0038] Tg _{(copolymer) = v 1 Tg 1 + v} 2 Tg 2 + ... + vWTgW However Ueshiki in v _1, v ₂ ... vW represents the weight fraction of the monomer in the copolymer, Tg _1, Tg ₂ ... TgW represents the Tg (° K) of the homopolymer of each monomer in the copolymer.

Tg calculated according to the above equation is ± 5 ° C.
There is accuracy.

Regarding the method for synthesizing the polymer latex used in the present invention, US Pat. Nos. 2,852,386 and 2,853,457,
No. 3,411,911, No. 3,411,912, No. 4,197,127, Belgian Patent No. 688,882, No. 691,360, No. 712,823, JP-B No. 45-5331, JP-A No. 60-18540, No. 51-130217, No.
It is described in detail in 58-137831 and 55-50240.

The average particle size of the polymer latex used in the present invention is preferably 0.5 to 300 nm, and any average particle size is preferably 30 to 250 nm.

The particle size of the polymer latex used in the present invention is determined by the following formula: “chemistry of polymer latex” (Polymer Publishing Association,
1973), which can be measured by an electron micrograph, a soap titration method, a light scattering method, or a centrifugal sedimentation method. The light scattering method is preferably used. As an apparatus for the light scattering method, D
LS700 (manufactured by Otsuka Electronics Co., Ltd.) was used.

Although there is no particular limitation on the molecular weight, the total molecular weight is preferably 1,000 to 1,000,000, more preferably 2,000.
0 to 500,000.

The polymer latex used in the present invention can be contained in the photographic component layer as it is or after being dispersed in water. The content of the polymer latex is preferably 5 to 70% by weight based on the binder of the photographic constituent layer. The location of addition may be a photosensitive layer or a non-photosensitive layer.

The polymer latex used in the present invention includes a case where a functional polymer such as a polymer coupler or a polymer ultraviolet absorber is added in the form of a latex.

Next, an example of a method for producing a polymer latex will be described, but the present invention is not limited to the following example.

(Production Method of Polymer Latex) Production Example 1 (Synthesis of Lx-1) A 1,000 ml four-necked flask was equipped with a stirrer, a thermometer, a dropping funnel, a nitrogen inlet tube, and a reflux condenser, and nitrogen gas was supplied. While introducing and deoxidizing, 350 cc of distilled water was added and heated until the internal temperature reached 80 ° C. 4.5 g of Sf-1 was added as a dispersant, and 0.45 g of ammonium persulfate was further added as an initiator, and then 90 g of ethylhexyl acrylate was added dropwise using a dropping funnel over about 1 hour. After the reaction is continued for 5 hours after the completion of the dropwise addition, unreacted monomers are removed by steam distillation. Thereafter, the mixture is cooled and adjusted to pH 6 with aqueous ammonia to obtain a polymer latex. The particle size was 150 nm.

Production Example 2 (Synthesis of Lx-2) A 1,000 ml four-necked flask was equipped with a stirrer, thermometer, dropping funnel, nitrogen inlet tube and reflux condenser, and nitrogen gas was introduced to perform deoxygenation. 350 cc of distilled water was added, and the mixture was heated until the internal temperature reached 80 ° C. P-3 according to the present invention as a dispersant,
4.5 g of ammonium persulphate as initiator and 0.45 g of ethyl hexyl acrylate
90 g is dropped with a dropping funnel over about 1 hour. After the reaction is continued for 4 hours after the completion of the dropwise addition, unreacted monomers are removed by steam distillation. After cooling, pH 6 with ammonia water
To obtain a polymer latex. The particle size was 200 nm.

Production Example 3 (Synthesis of Lx-10) 200 ml of dioxane was placed in a 500 ml three-necked flask, and deoxygenation was carried out with nitrogen gas. Then isononyl acrylate
15 g and 35 g of cyclohexyl acrylate were added, and 1.2 g of dimethyl azobisisobutyrate was added as an initiator.
Continue the reaction at 0 ° C. for 6 hours. After the reaction is completed, 3 l of the reaction solution is added.
Of distilled water with vigorous stirring to give white crystals.

The white crystals were collected by filtration, dried, dissolved in 100 ml of ethyl acetate, and distilled water 5 added with 2 g of Sf-2.
Add to 00 ml with vigorous stirring, then remove the ethyl acetate to obtain a polymer latex. The particle size was 180 nm.

Production Example 4 (Synthesis of comparative latex L) 0.25 kg of KMDS (dextran sulfate sodium salt) and ammonium persulfate in 40 liters of water
A mixture of 4.51 kg of n-butyl acrylate, 5.49 kg of styrene and 0.1 kg of acrylic acid was added to the liquid containing 0.05 kg over 1 hour under a nitrogen atmosphere while stirring at a liquid temperature of 81 ° C., and then ammonium persulfate was added. After adding 0.005 kg and further stirring for 1.5 hours, the mixture was cooled and the pH was adjusted to 6 with aqueous ammonia.

The obtained latex solution was washed with Whotman GF.
The mixture was filtered with a / D filter, and finished to 50.5 kg with water to prepare a monodisperse latex (L) having an average particle size of 250 nm.

Specific examples of the polymer latex according to the present invention and the dispersant used in the synthesis thereof are shown below. The suffix of the monomer unit indicates the content percentage of each.

[0054]

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[0055]

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[0056]

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[0057]

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[0058]

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[0059]

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In the present invention, the amount of the polymer latex used is at least 10% by weight based on 100 gelatin.
It is 300% or less, preferably 30% or more and 200% or less. If the amount of the polymer latex is too small, the effect of the present invention is not sufficiently exhibited, and if the amount of the polymer latex is too large, sufficient film strength cannot be obtained. Further, the water-soluble polymer used in the present invention is a polymer latex 10
It is 0.5% or more and 30% or less, preferably 1% or more and 15% or less by weight with respect to 0.

The fluorinated surfactant according to the present invention will be described. The fluorine-containing surfactant preferably used in the present invention is a compound represented by the following general formula [I].

Formula (I) Rf- (A) _n -Y In the formula, Rf represents a partially or completely fluorinated substituted or unsubstituted alkyl or alkenyl group containing at least three fluorine atoms. , A represents a divalent linking group,
n is 0 or 1, Y is -COOM, -SO ₃ M -OSO ₃ M or
-(OCH ₂ CH ₂ ) _m represents OR. Here, M represents a hydrogen atom, an alkali metal atom, an alkaline earth metal atom or a quaternary ammonium group, m represents 6 to 20, and R represents an alkyl group or an acyl group.

The divalent linking group represented by A represents a divalent organic group, and preferably represents an alkylene, arylene, carbonyl, sulfo, imino group or the like. It may have a substituent.

Hereinafter, specific examples of the compound represented by the above general formula [I] will be shown.

[0065]

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These compounds are commercially available.

The amount of the compound represented by the above general formula [I] used in the present invention is 0.05 m / m ² on the side having the silver halide emulsion layer of the silver halide photographic light-sensitive material according to the present invention.
g to 100 mg, preferably 0.3 mg to 30 mg. In order to add the compound of the general formula [I] to the hydrophilic layer of the photosensitive material, it is preferable to add the compound by dissolving it in water or a hydrophilic solvent such as methanol, ethanol, glycols, or a single or mixed solvent such as acetone. .

As the photographic constituent layers of the silver halide photographic light-sensitive material according to the present invention, for example, an emulsion layer, an emulsion protective layer, an intermediate layer, a dye layer,
Examples include a filter layer and an antistatic layer. On the other hand, the side having no photosensitive silver halide emulsion layer includes, for example, an antihalation layer, the same protective layer, an antistatic layer, an intermediate layer, and other backing layers.

The fluorinated surfactant represented by the above general formula [I] according to the present invention is added to the above-mentioned hydrophilic colloid layer having the photosensitive silver halide emulsion layer.

Preferred hydrophilic colloid layers are photosensitive silver halide emulsion layers and protective layers. Particularly preferred hydrophilic colloid layers include a protective layer on the outermost surface of a photosensitive material.

The silver halide emulsion used in the silver halide photographic light-sensitive material of the present invention includes silver bromide, silver iodobromide,
Alternatively, it may be a silver iodochlorobromide emulsion containing a small amount of silver chloride.
The halogenated grains may be of any crystal type as long as they have the constitution of the present invention, for example, cubic, octahedral, 14
It may be a single crystal such as a face crystal or a polytwin particle having various shapes.

The emulsion used in the silver halide photographic light-sensitive material of the present invention can be produced by a known method. For example, Research Disclosure (RD) No. 17643 (December 1978), 22
~ 23, or the method described in (RD) No. 18716 (November 1979), page 648, described in "Emulsion Preparation and Types".

Emulsions used in the silver halide photographic light-sensitive material of the present invention are described, for example, in "The Theory of the
Photographic process ”4th edition, published by Macmillan (1977
The method described on pages 38-104, GFDuffin, “Photograph
ic Emulsion Chemistry ”, Focal Press (1966),
“Chimie et Physique Photographique” by P. Glafkides
Paul Montel (1967) or VLZelikman et al. “Makin
g And Coating Photographic Emulsion "by Focal Press (1964).

That is, mixing conditions such as a forward mixing method, a reverse mixing method, a double jet method, and a control double jet method under solution conditions such as an acidic method, an ammonia method, and a neutral method;
The particles can be produced using particle preparation conditions such as a conversion method and a core / shell method, and a combination thereof.

The emulsion used in the silver halide photographic light-sensitive material of the present invention is preferably a monodispersed emulsion in which silver iodide is localized inside the grains. The term “monodispersion” as used herein means that at least 95% of the particles in terms of the number or weight of the particles are within ± of the average particle diameter when the average particle diameter is measured by an ordinary method.
The silver halide grains are within 40%, preferably within ± 30%.

The grain size distribution of the silver halide may be either a monodisperse emulsion having a narrow distribution or a polydisperse emulsion having a wide distribution. The crystal structure of silver halide may have a different silver halide composition inside and outside,
For example, a core / shell type monodisperse emulsion having a clear two-layer structure in which a core portion of high silver iodide is covered with a shell layer of low silver iodide may be used.

The method for producing the above monodisperse emulsion is known.
J. Phot. Sci, 12.242-251, (1963), JP-A-48-36890,
Nos. 52-16364, 55-142329, 58-49938, British Patent 1,413,748, U.S. Pat. Nos. 3,574,628, and 3,655,394. The emulsion used in the silver halide photographic light-sensitive material of the present invention is obtained by, for example, using a seed crystal as a method for obtaining the above-mentioned monodispersed emulsion, and supplying and growing silver ions and halide ions using the seed crystal as a growth nucleus. May be used. The method for producing the above-mentioned core / shell type emulsion is known, for example, J. Phot. Sci, 24.198. (1976), U.S. Pat. Nos. 2,592,250, 3,505,068, 4,210,450 and 4,210,450.
No. 4,444,877 or JP-A-60-143331 can be referred to.

The emulsion used in the silver halide photographic light-sensitive material of the present invention may be tabular grains having an aspect ratio (ratio of grain diameter / grain thickness) of 3 or more. The advantages of such tabular grains are disclosed in, for example, British Patent No. 2,112,157, U.S. Pat.No. 4,414,310, and U.S. Pat.No. 4,434,226, as they can improve spectral sensitization efficiency and improve the graininess and sharpness of images. Emulsions can be prepared by the methods described in these publications.

The emulsions described above are either of a surface latent image type in which a latent image is formed on the grain surface, an internal latent image type in which a latent image is formed inside the grain, or a latent image type in which a latent image is formed on both the surface and inside. It may be an emulsion.

At the stage of physical ripening or grain preparation, these emulsions are prepared by using, for example, cadmium salt, lead salt, zinc salt, thallium salt, iridium salt or its complex salt, rhodium salt or its complex salt, iron salt or its complex salt and the like. You may.

The emulsion may be subjected to a Nudel washing method or a flocculation sedimentation method to remove soluble salts. Preferred examples of the washing method include aromatic hydrocarbons containing a sulfo group described in JP-B-35-16086. Examples thereof include a method using a system aldehyde resin, and a desalting method using G-3, G-8, etc., which are polymer flocculants described in JP-A-63-158644.

The emulsion used in the silver halide photographic light-sensitive material of the present invention can use various photographic additives before and after physical ripening or chemical ripening. As the compound used in such a step, for example, the aforementioned (RD) No. 1
7643, Nos. 18716 and 308119 (December 1989) can be used. The locations of these three (RD) are listed below.

Additive RD-17643 RD-18716 RD-308119 page classification page page classification chemical sensitizer 23 III 648 upper right 996 III sensitizing dye 23 IV 648-649 996-8 IV desensitizing dye 23 IV 998 B dye 25 ~ 26 VIII 649 ~ 650 1003 VIII Development accelerator 29 XXI 648 Upper right fog inhibitor / stabilizer 24 IV 649 Upper right 1006 ~ 7 VI Brightener 24 V 998 V Hardener 26 X 651 Left 1004 ~ 5 X Surfactant 26-27 XI 650 right 1005-6 XI plasticizer 27 XII 650 right 1006 XII sliding agent 27 XII matting agent 28 XVI 650 right 1008-9 XVI binder 26 XXII 1003-4 IX support 28 XVII 1009 XVII Halogenation of the present invention Examples of the support used for the silver photographic light-sensitive material include those described in the above (RD) .A suitable support is a plastic film or the like, and the surface of the support improves the adhesion of the coating layer. For this purpose, an undercoat layer may be provided, or corona discharge or ultraviolet irradiation may be applied.

The photographic processing of the light-sensitive material of the present invention can be carried out, for example, by the above-mentioned (RD) -17643, XX to XXI, pages 29 to 30, or 308, 119 to XX to XXI.
Treatment with a treatment solution as described in XXI, pp. 1011-1012 may be performed. This process may be a black and white photographic process for forming a silver image. Processing temperature is usually between 18 ° C and 50
Processed in the range of ° C.

As a developer in black-and-white photographic processing, dihydroxybenzenes (eg, hydroquinone), 3-pyrazolidones (eg, 1-phenyl-3-pyrazolidone), aminophenols (eg, N-methyl-P-aminophenol) Etc. can be used alone or in combination. In the developer, for example, known preservatives, alkali agents, pH buffering agents, antifoggants, hardeners, development accelerators, surfactants,
An antifoaming agent, a color tone agent, a water softener, a dissolution aid, a viscosity imparting agent, and the like may be used as necessary.

The fixing solution contains a fixing agent such as thiosulfate and thiocyanate, and may further contain a water-soluble aluminum salt such as aluminum sulfate or potassium alum as a hardening agent. In addition, it may contain a preservative, a pH adjuster, a water softener and the like.

[0087]

EXAMPLES The present invention will be described below in detail with reference to examples, but embodiments of the present invention are not limited thereto.

Example 1 (Preparation of red-sensitive emulsion A) AgBrI having an average particle size of 0.1 μm
(AgI content: 2 mol%) Using a seed emulsion, an aqueous solution of ammoniacal AgNO _{3 and an} aqueous solution of potassium bromide are added by a double jet method, and AgBrI having an average particle size of 0.25 μm (average AgI content of 0.1 mol%) is cubic. A crystal monodisperse emulsion was grown. The coefficient of variation (σ / r) was in the range of 0.15 to 0.20.

This emulsion was dissolved immediately before chemical ripening, and when the temperature became constant, the following dyes (1) and (2) were added. The dye amounts were each 90 mg / mol silver halide. Then, ammonium thiocyanate, chloroauric acid and hypo were added to perform chemical sensitization, and then 4-hydroxy-6
-Methyl-1,3,3a, 7-tetrazaindene was added.

[0090]

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(Backing layer) Backing lower layer coating solution Gelatin 400 g i-Amyl-n-decyl sulfosuccinate sodium 0.4 g Antihalation dye (1) 10 g Potassium polystyrene sulfonate (average molecular weight 150,000) 50 g Diethylene glycol 5.0 g Glyoxal 2.0 g Dye emulsified dispersion (the following content) 33g

[0092]

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Make up to 7 liters with water.

[Method for Preparing Dye Emulsion Dispersion] The following dyes
10Kg of tricresyl phosphate 28l and ethyl acetate 85l
At 55 ° C. This is called an oil-based solution. On the other hand, 270 l of a 9.3% gelatin aqueous solution containing 1.35 kg of an anionic surfactant (AS) was prepared. This is called an aqueous solution. Next, the oil-based solution and the aqueous-based solution were placed in a dispersion vessel, and dispersed while maintaining the liquid temperature at 40 ° C. Phenol and 1,1'-dimethylol-1-bromo-1 were added to the resulting dispersion.
-An appropriate amount of nitromethane was added and the mixture was made up to 240 kg with water.

[0095]

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Backing upper layer coating solution Gelatin 400 g i-Amyl-n-decylsulfosuccinate sodium salt 10 g Antihalation dye (1) 10 g Polymethyl methacrylate (average particle size 6 μm) 12 g SAM-1 3.0 g SAM-2 0.75 g Glyoxal 13.6g

[0097]

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Make up to 7 liters with water.

Red-Sensitive Silver Halide Emulsion Layer Coating Solution A red-sensitive silver halide emulsion coating solution was prepared by adding the following per mol of silver halide to Emulsion A described above.

Trimethylolpropane 10 g Nitrophenyl-triphenylphosphonium chloride 50 mg Ammonium 1,3-dihydroxybenzene-4-sulfonate 1 g 2-Mercaptobenzimidazole-5-sodium sodium sulfonate 10 mg 1,1-Dimethylol-1-bromo- 1-Nitromethane 10mg Latex of the present invention Amount shown in Table 1

[0101]

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Emulsion Surface Side Protective Layer The following addition amounts were shown per 1 m ² of film.

Lime-treated inert gelatin 0.9 g sodium i-amyl-n-decylsulfosuccinate 27 mg polymethyl methacrylate (average particle size 5 μm) 20 mg silicon dioxide particles (area average particle size 1.2 μm) 20 mg Ludox AM (colloidal silica [Dupont 5mg 2-4-dichloro-6-hydroxy-1,3,5-triazine sodium (2% aqueous solution) Topside 300 (manufactured by Permchem Asia Ltd.) 1 mg SAM-1 20 mg SAM-2 7.7 mg Fluorinated surfactant of the present invention Amount shown in Table 1 Application of sample Halogenated on both sides of 180 μm thick polyethylene terephthalate support A silver emulsion and an emulsion surface protective layer coating solution were applied.

On the other side, the lower layer and the upper layer described above were applied.

The amount of gelatin in the backing layer was 1.5 g in the lower layer.
/ m ² and the upper layer was 0.9 g / m ² at the same time by a slide hopper method. Samples were obtained by coating the emulsion layer and the protective layer so that the amounts of gelatin were as shown in Table 1.

The following evaluation was performed on the obtained film sample.

(Evaluation method of melting time) 1 cm × 2
A film sample cut into 1.5 cm N was kept at 60 ° C.
It was immersed in an aOH aqueous solution without stirring, and the time until the emulsion layer eluted was measured and defined as a melting time (MT) (minute).

(Evaluation Method of Remaining Color) An automatic developing machine SRX-1001 (Konica Corporation) was modified so that the film sample was left unexposed and the transport speed of the automatic developing machine was changed to dry to dry processing for 45 seconds. Was used for the treatment. (Developing temperature: 33 ° C., fixing temperature: 33 ° C.) The evaluation of the residual color was visually evaluated in five steps as follows.

A: no residual color B: slight residual color but good C: residual color but no problem in use D: residual color severely unusable E: level at which residual color does not endure severely (pick off Evaluation method) After giving uniform exposure to the entire surface so as to obtain a density of 3.0, use an automatic developing machine similar to that for the evaluation of residual color, and continuously process 10 samples of quarter size to reduce the degree of pick-off. evaluated. Pickoff is quarter size
The following standard was used as an average value for 10 sheets.

A: very good B: good C: poor D: very poor 470g Potassium sulfite (50% solution) 3000g Diethylenetriaminepentaacetic acid 45g Sodium bicarbonate 150g 5-Methylbenzenetriazole 2.0g 1-Phenyl-5-mercaptotetrazole 0.2g Hydroquinone 390g Add water to make 5000ml Part-B (for 15l finishing) Glacial acetic acid 220g triethylene glycol 200g 1-phenyl-3-pyrazolidone 27g 5-nitroindazole 0.45g n-acetyl-D, L-penicillamine 0.15g Part-C (for 15l finishing) glutaraldehyde 50g fixer prescription Part-A (For 19l finishing) Ammonium thiosulfate (70wt / vol%) 4000g Sodium sulfite 175g Sodium acetate / trihydrate 400g Sodium citrate 50 g gluconic acid 38 g boric acid 30 g glacial acetic acid 140 g Part-B (for 19 l finishing) Aneninium sulfate 65 g sulfuric acid (50 wt%) 105 g starter formulation (for 1 l finishing) (Use 2.0 ml per 1 l of developing solution. ) Glacial acetic acid 138g Potassium bromide 325g 5-Methylbenzotriazole 1.5g Make up to 1 liter with pure water.

The results obtained are shown in Table 1 below.

[0112]

[Table 1]

As is clear from the table, the sample of the present invention shows excellent residual color properties and no occurrence of pick-off failure, although the melting time is not different from the comparison.

Example 2 Preparation of Grains Monodisperse grains of silver iodobromide containing 2.0 mol% of silver iodide having an average grain diameter of 0.2 μm were used as nuclei, and silver iodobromide containing 30 mol% of silver iodide was adjusted to pH 9 .8, grown at pAg7.8, then pH8.2, pAg9.1
The average grain size is obtained by adding equimolar amounts of potassium bromide and silver nitrate to obtain silver iodobromide grains having an average silver iodide content of 2.2 mol%.
Monodisperse emulsion grains of 0.395 μm were prepared.

The emulsion was subjected to desalting of excess salts by a usual aggregation method. That is, while maintaining the temperature at 40 ° C., a formalin condensate of sodium naphthalene sulfonate and an aqueous solution of magnesium sulfate were added to cause aggregation. After removing the supernatant, further at 40 ° C
Was added, and an aqueous solution of magnesium sulfate was added again to cause aggregation, and the supernatant was removed.

The particle size dispersibility of the silver halide grains thus obtained was 0.15, indicating that they had good monodispersity.

Preparation, processing and evaluation of sample The silver halide grains thus obtained were added with pure water so that the volume per mole was 500 ml, and then the temperature was raised to 55 ° C. B and 200: 1 by weight in a total amount of 300 mg per mole of silver halide, and after 10 minutes, ammonium thiocyanate is added in an amount of 2.6 × 10 ⁻³ mole per mole of silver and an appropriate amount of chloride. Gold acid and hypo were added to initiate chemical ripening.

At this time, the pH was 6.15 and the silver potential was 50 mV.

Fifteen minutes before the completion of chemical ripening (70 minutes after the start of chemical ripening), 200 mg of potassium iodide was added per mole of silver, and five minutes later, 10% (wt / Vol) acetic acid was added. The value
The pH was lowered to 5.6 and the pH was maintained for 5 minutes, after which a 0.5% (wt / Vol) solution of potassium hydroxide was added to bring the pH to 6.15.
After that, 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene was added, and the chemical ripening was completed to obtain a photographic emulsion coating solution.

The pH after preparation of the photographic emulsion coating solution was 6.10.
The silver potential was 81 mV (35 ° C.).

Using this emulsion coating solution, a sample was prepared as follows. That is, the photographic emulsion layer has a gelatin content of 1.6 g.
so that / m ^2, amount of silver such that a 3.0 g / m ² in terms of silver value and a protective layer solution was prepared using additives infra, the protective layer is a quantity with gelatin It was applied so as to be 0.9 g / m ² .

The spectral sensitizing dyes are as follows.

Sensitizing dye (A) 5,5'-dichloro-9-ethyl-
3,3'-Di- (3-sulfopropyl) oxacarbocyanine sodium salt anhydride Sensitizing dye (B) 5,5'-di- (butoxycarbonyl) -1,
Anhydrous 1'-diethyl-3,3'-di- (4-sulfobutyl) benzimidazolocarbocyanine sodium salt Additives used in emulsion (photosensitive silver halide coating solution) are as follows. . The amount of addition is shown in an amount per mole of silver halide.

1,1-Dimethylol-1-bromo-1-nitromethane 70 mg t-butyl-catechol 400 mg polyvinylpyrrolidone (molecular weight 10,000) 1.0 g styrene-maleic anhydride copolymer 2.5 g trimethylolpropane 10 g diethylene glycol 5 g nitrophenyl- Triphenylphosphonium chloride 50mg Ammonium 1,3-hydroxybenzene-4-sulfonate 4g 2-Mercaptobenzimidazole-5-sodium sulfonate 1.5mg Latex of the present invention Amount shown in Table 2

[0125]

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The additives used in the protective layer solution are as follows. The amount of addition is shown as an amount per 1.0 liter of the coating solution.

[0127] In the emulsion coating solution, in addition to the above-mentioned additives, the following compound (1) was prepared from an oil consisting of the compound (2) according to the method described in Example 1 (3) of JP-A-61-285445. A solution dissolved in a hydrophilic colloid solution and added thereto was added in the following amount per mole of silver halide.

[0128]

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(2) 0.6 g of tricresyl phosphate The following solutions were prepared and used for the backing layer.

(Backing layer) (Backing lower layer solution) Per liter of coating solution Lime-treated gelatin 70 g Acid-treated gelatin 5 g Trimethylolpropane 1.5 g Backing dye A 1.0 g Backing dye B 1.0 g Glyoxal aqueous solution (40%) 8 mL (Backing upper solution) Lime-treated gelatin 70 g Acid-treated gelatin 5 g Trimethylolpropane 1.5 g Backing dye A 2.0 g Backing dye B 2.0 g KNO ₃ 0.5 g 2,4-Dichloro-6-hydroxy-1,3,5-triazine sodium per liter of coating solution 2% aqueous solution of salt 20 ml Polymethyl methacrylate particles having an area average particle size of 4.0 μm 1.1 g C ₁₁ H ₂₃ CONH (CH ₂ CH ₂ O) ₅ H 1.0 g SAM-1 1.0 g SAM-3 0.3 g di-ethylhexyl sulfosuccinate Sodium salt 0.4g

[0131]

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The backing lower layer liquid was 1.6 g in gelatin amount.
/ m ² and an upper layer solution of 0.9 g / m ² to obtain a sample. Coating is performed every minute with two slide hopper type coaters
At a speed of 80m, glycidyl methacrylate 50wt%,
Methyl acrylate 10wt%, butyl acrylate 40wt%
An aqueous dispersion of the copolymer obtained by diluting the copolymer consisting of the three types of monomers to a concentration of 10% by weight was simultaneously coated on a 175 μm polyethylene terephthalate film base provided as a subbing liquid. , Dried in 2 minutes 20 seconds,
A sample was obtained.

The obtained samples were evaluated in the same manner as in Example 1 and the results are shown in Table 2 below. According to the method of the present invention, a silver halide emulsion free from pick-off failure and having no residual color was obtained. It turns out that it can be obtained.

[0134]

[Table 2]

[0135]

According to the present invention, a silver halide photographic light-sensitive material free of film peeling (pick-off failure) and having no residual color upon rapid processing by an automatic processor can be obtained.

Claims (3)

(57) [Claims] At least one layer on a support contains at least one polymer latex having a monomer unit of at least one monomer having a solubility in water at 25 ° C. of not more than 0.025% by weight. A silver halide photographic material comprising 0.2 to 100 mg / m ^{2 of a} fluorine-containing surfactant. 2. A polymer latex having at least 50% by weight or more of at least one monomer having a solubility in water at 25 ° C. of 0.025% by weight or less as a monomer unit in at least one layer on the support. the silver halide photographic light-sensitive material characterized by containing at least one, and a fluorine-containing surfactant containing 0.2~100mg / m ^2. 3. The silver halide photographic material according to claim 1, wherein the fluorine-containing surfactant is a compound represented by the following general formula [I]. General formula [I] Rf- (A) _n -Y (wherein, Rf represents a partially fluorinated or perfluorinated substituted or unsubstituted alkyl or alkenyl group containing at least 3 fluorine atoms; represents a divalent linking group, n is 0 or 1, Y is -COOM, -SO ₃ M -OSO ₃ M or -. represents a (OCH ₂ CH _{2) m} oR wherein M is a hydrogen atom, Represents an alkali metal atom, an alkaline earth metal atom or a quaternary ammonium group, m is 6 to 20, and R represents an alkyl group or an acyl group.)