JPH07248572A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain a silver halide photosensitive material in which no roller mark and no processing unevenness are generated and which has good drying property and autofeeder conveyance characteristic by providing the photosensitive material with a backing layer that contains gelation in a specified content and also a polymer latex. CONSTITUTION:This photosensitive material has at least one photosensitive silver halide emulsion layer and a protective layer on at least one side of a substrate and a backing layer on the other side. At this time, the emulsion layer contains a fluorine containing surfactant and saponin and the backing layer contains <=1g/m<2> gelation and also at least one kind of polymer latex. Further, the ratio of the amount of the fluorine containing surfactant contained in the silver halide photographic emulsion to that of the saponin added thereto is preferably 1:2 to 3:1 by weight. Thus, the photosensitive material excellent in rapid-processability conveyable characteristics in the autofeeder conveyance and improved in characteristics with respect to the generation of roller marks, drying and generation of processing unevenness can be obtained.

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 emulsion which is excellent in rapid processing performance and transportability in an auto feeder and has improved roller mark, drying property and processing unevenness.

[0002]

2. Description of the Related Art In recent years, rapid processing properties as well as high sensitivity and high image quality have been strongly desired for silver halide photographic light-sensitive materials. At the same time, there is a strong demand to reduce the amount of processing waste liquid in order to eliminate pollution. However, rapid processing of the light-sensitive material and reduction of the processing solution tend to cause uneven development.

On the other hand, a silver halide photographic light-sensitive material has a property of being easily charged with static electricity under a low humidity, and when it is discharged, a fog called "static mark" is generated, which causes a fatal obstacle to an image. That is.

There have been many proposals as an antistatic method in the photographic industry, for example, various surfactants used in other fields, or JP-A-48-207.
The charge sequence regulator described in JP-A No. 85 and JP-A-57-104931 to which conductivity is imparted are disclosed.

Further, the roller mark is a cause of pressure desensitization because mechanical stress is applied in the steps of carrying and processing the silver halide photographic light-sensitive material. One of the methods of eliminating these is to reduce the force transmitted to the silver halide grains when external pressure is applied to the emulsion film, and the binder component of the emulsion, namely gelatin, hydrophilic polymer, or water-soluble latex is Although many methods can be used, the large amount of gelatin, hydrophilic polymer, or water-soluble latex tends to cause uneven treatment, which slows the drying speed and does not meet the purpose of rapid processing.

The present inventor has investigated various activators including known polyalkylene oxide compounds as antistatic agents. As a result, although antistatic performance is obtained, roller marks frequently appear in rapid processing. It turned out to have drawbacks.

There has been a demand for a silver halide photographic light-sensitive material which does not cause roller mark development unevenness even when it is rapidly processed with low replenishment, has excellent sensitivity and gradation, and also has antistatic properties.

[0008]

SUMMARY OF THE INVENTION Therefore, an object of the present invention is to provide a silver halide photographic light-sensitive material which is excellent in transportability in rapid processing or autofeeder transportation and has improved roller marks, drying properties and processing unevenness. That is.

[0009]

The objects of the present invention have been achieved by the following.

A silver halide photographic light-sensitive material having at least one light-sensitive halogen emulsion layer and a protective layer on at least one side of a support, and a backing layer on the opposite side, in the emulsion layer of the light-sensitive material. Contains fluorine-containing surfactant and saponin, and the backing layer gelatin is 1 g /
m ² or less, and silver halide photographic material, characterized in that it contains at least one polymer latex, the, the ratio of the added amount of the fluorine-containing surfactant and a saponin containing silver halide photographic emulsion , 1: 2 by weight
It was achieved by the silver halide photographic light-sensitive material described in the item 1 to 3: 1.

The present invention will be described in detail below.

On the side having a photosensitive silver halide emulsion layer as a photographic constituent layer 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 thereof include a filter layer and an antistatic layer. On the other hand, on the side not having the photosensitive silver halide emulsion layer, for example, an antihalation layer, the same protective layer, an antistatic layer, an intermediate layer, and other backing layers can be mentioned.

In order to bring out the effect of the present invention most remarkably, it is preferable to add the following fluorine surfactant and saponin according to the present invention to the emulsion layer. Examples of the fluorine-containing surfactant used in the present invention include, for example, JP-A-4-3626.
Exemplary Compound 1-6, 1-10, 2-1-2-
6,3-1 to 3-4,4-1 to 4-6, Japanese Patent Application No. 4-150841
Compounds FA-1, FA-2, FA-4 to F
A-10, FA-12 to FA-16, FA-18 to FA-29, F
A-31 ~ FA-49, FK-2 ~ FK-6, FK-8 ~ F
K-11 and FK-13 to FK-20 can be used.

Specific examples of these compounds are shown below, but the invention is not limited thereto.

[0015]

[Chemical 1]

[0016]

[Chemical 2]

The fluorine-based anionic activator or the fluorine-based cationic activator according to the present invention is described in, for example, US Pat.
No. 751, No. 2,567,011, No. 2,732,398, No. 2,764,602
No., No. 2,806,866, No. 2,809,998, No. 2,915,376,
2,915,528, 2,934,450, 2,937,098, 2,9
57,031, 3,472,894, 3,555,089, 2,918,50
1, British Patent 1,143,927, 1,130,322, Japanese Patent Publication No. 45-
37304, JP-A-47-9613, 50-121243, 50-1177
05, 49-134614, 50-117727, 52-41182,
51-132392, each specification, British Chemical Society Journal (J. Chem. Soc.)
1950, 2789, 1957, 2574, and 2640, American Chemical Society Journal (J. Amer. Chem. Soc.) Vol. 79, 2549, Oil Chemistry (J. Japan O
il Chemists Soc.) 12: 653, American Society of Organic Chemistry (J.Or)
g. Chem.) 30: 3524 (1965) and the like.

Some of these fluorine-based activators are trade names of Megafacs F from Dainippon Ink and Chemicals, Inc.
The name of Fluorad FC from And Manufacturing Company, and Monflor (Mo) from Imperial Chemical Industry
nflor), the product name Zonyls from E. I. DuPont Nemeras & Company, and the product name Licowet VPF from Farbeberke Hoechst.

The total amount of the fluorinated cationic surfactant and the fluorinated anionic surfactant used in the present invention is preferably 0.1 to 1000 mg per 1 m ² of the photographic light-sensitive material, preferably
The amount is preferably 0.5 to 300 mg, more preferably 1.0 to 100 mg. When used in combination, two or more kinds may be used in combination. Other fluorine-based nonionic activators, fluorine-based betaine activators, and hydrocarbon-based activators may be used in combination.

The addition ratio of the fluorine-based anionic activator and the fluorine-based cationic activator of the present invention is 1:10 to 10: in molar ratio.
1 is preferable, and 3: 7 to 7: 3 is more preferable.

The saponin according to the present invention is used in the emulsion layer in the hydrophilic colloid layer of the silver halide photographic light-sensitive material constituting layer of the present invention.

The saponin used in the present invention is a steroidal or triterpene type glycoside distributed in the plant kingdom,
It is a known compound which has been known as a coating aid or a wetting agent for a long time in the photographic industry. Regarding the type of saponin used in the present invention, it can be used without particular limitation, preferably Quillaja saponin extracted from Quillaja bark, Mukurojisaponin extracted from the skin of disease-free (mukuroji), and the like, these are It can be easily obtained as a commercial product.

Both the above-mentioned fluorine-containing surfactant and saponin are materials known in the photographic industry.
However, there is no disclosure of using both in an emulsion layer. According to the study of the present inventor, it was unexpected that the above-described object of the present invention could be achieved by the combination of these two specific amounts. That is, the objective effect of the present invention is achieved when the weight ratio of the above-mentioned fluorine-containing surfactant and saponin is 1: 2 to 3: 1, more preferably 1: 2 to 2: 1. Plays well. It has been found that if the ratio is out of this range, the effect of preventing development unevenness and static marks is poor and the photographic performance is not excellent.

The amount used in the silver halide photographic light-sensitive material in the present invention is not uniform depending on the type, form or coating conditions of the light-sensitive material, but usually the above ratio per 1 m ^{2 of} silver halide photographic light-sensitive material. Therefore, the total amount may be 5 mg to 200 mg, preferably 10 mg to 100 mg. To add to the emulsion layer in the light-sensitive material constituent layer, dissolve in water or an organic solvent such as methanol, ethanol, acetone, or a mixed solution of water and these organic solvents, and then terminate the chemical sensitization or spectral sensitization. ,
When the maximum sensitivity is reached, a stabilizer is added for stabilization, and then other emulsion layer additives are added and then added.

Gelatin is preferably used as the hydrophilic colloid used in the light-sensitive material of the present invention, but other hydrophilic colloids can also be used. For example, gelatin derivatives, graft polymers of gelatin and other polymers, albumin, protein such as casein hydroxyethyl cellulose, carboxymethyl cellulose, cellulose derivatives such as cellulose sulfates, sodium alginate, dextran, starch derivatives and other sugar derivatives, polyvinyl alcohol Polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, polyvinylpyrazole and the like can be used various synthetic hydrophilic polymer substances such as homopolymers or copolymers. it can. Especially average molecular weight of 5,000 with gelatin
It is preferable to use 10,000 dextran or polyacrylamide together. Examples of these are, for example, JP-A-1-307738.
No. 2, No. 2-62532, No. 2-24748, No. 2-44445, No. 1-660
31, JP-A 64-65540, 63-101841, 63-153538
It is disclosed in the official gazette such as No.

Examples of gelatin include lime-processed gelatin, acid-processed gelatin, enzyme-processed gelatin as described in Bull. Soc. Sci. Phot. Japan, No. 1630 (1966), as well as gelatin derivatives (eg Halides, acid anhydrides, isocyanates, bromoacetic acid, alkane sultones, vinyl sulfonamides, maleinimide compounds, polyalkylene oxides, those obtained by reacting various compounds such as epoxy compounds) Included.

In the silver halide photographic light-sensitive material of the present invention, the above hydrophilic colloid gel is used as a protective layer for the silver halide light-sensitive emulsion layer at the position farthest from the support. Examples of these colloids include gelatin, colloidal alumbumin, polysaccharides, cellulose derivatives, synthetic resins such as polyvinyl compounds containing polyvinyl alcohol derivatives, acrylamide polymers, and the like.
Mention may be made of hydrophilic colloids commonly used in the field of photography. Gelatin is preferred as these colloids.

In the present invention, the coating amount of gelatin as the hydrophilic colloid layer of the protective layer of the silver halide emulsion is 1.0 g.
/ M ² or less. If it is 1.0 g / m ² or more, scratching property and pressure desensitization are improved, but poor fixing and dryness are deteriorated. The preferable gelatin coating amount is 1.0 to 0.5 g / m ² .

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 0.25% by weight, preferably not more than 0.015% by weight. Examples of such ethylenic monomers include hexyl acrylate, 2-ethylhexyl acrylate, octyl acrylate, tert-octyl acrylate, nonyl acrylate, iso-nonyl acrylate, cyclohexyl acrylate, n-stearyl acrylate, lauryl acrylate, tridecyl acrylate, etc. Acrylic acid esters, butyl methacrylate, iso-butyl methacrylate, tert-butyl methacrylate, hexyl metallate, 2-ethylhexyl metallate, octyl metallate, iso-octyl methacrylate, tert-octyl metallate, nonyl metallate, iso- Methacrylic acid ester such as nonyl metalylate, cyclohexyl metalylate, n-stearyl metalylate, lauryl methacrylate, tridecyl methacrylate S etc. and divinyl benzene.

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 New Experiment Chemistry Course Basic Operation 1 (Maruzen Kagaku, 1975). . The solubility of the monomer of the present invention in water at 25 ° C. measured by this method is, for example,
2-ethylhexyl acrylate is 0.01% by weight, 2-ethylhexyl methacrylate is 0.00% by weight, and cyclohexyl methacrylate is 0.00% by weight. The comparative monomer was 0.03 wt% for styrene, 0.32 wt% for butyl acrylate and 0.03 wt% for butyl methacrylate.

The polymer latex used in the present invention may be copolymerized with another monomer compound other than the above-mentioned monomer compounds, and as the copolymerizable ethylenic monomer compound,
For example, acrylic acid esters, methacrylic acid esters, vinyl esters, olefins, styrenes, crotonic acid esters, itaconic acid diesters, maleic acid diesters, fumaric acid diesters, acrylamides, allyl compounds, vinyl ethers, Examples thereof include vinyl ketones, vinyl heterocyclic compounds, glycidyl esters, unsaturated nitriles, polyfunctional monomers and monomer compounds selected from a combination of two or more kinds selected from various unsaturated acids.

More concretely showing these monomer compounds, acrylic acid esters include methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, 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-
Methoxy polyethylene glycol acrylate (additional mol number n = 9), 1-bromo-2-methoxyethyl acrylate, 1,1-dichloro-2-ethoxyethyl acrylate and the like can be mentioned.

Examples of methacrylic acid esters are methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, amyl methacrylate, chlorobenzyl methacrylate, sulfopropyl methacrylate, N-ethyl-N-phenylaminoethyl methacrylate, 2- (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-methoxypolyethylene glycol methacrylate (additional mol number n =
6), allyl methacrylate, dimethylaminoethyl methyl methacrylate salt of methacrylic acid and the like.

Examples of vinyl esters include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl isobutyrate, vinyl caproate, vinyl chloroacetate, vinyl methoxyacetate, vinyl phenyl acetate, vinyl benzoate, vinyl salicylate. And so on.

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 thereof include methylstyrene, dimethylstyrene, trimethylstyrene, ethylstyrene, isopropylstyrene, chloromethylstyrene, methoxystyrene, acetoxystyrene, chlorostyrene, dichlorostyrene, bromstyrene, trifluoromethylstyrene, and vinylbenzoic acid methyl ester.

Examples of crotonic acid esters include butyl crotonic acid and hexyl crotonic acid.

Examples of diethyl itaconates include dimethyl itaconate, diethyl itaconate, dibutyl itaconate and the like. Examples of maleic acid diesters include diethyl maleate, dimethyl maleate, dibutyl maleate and the like. Examples of the fumarate diesters include diethyl fumarate, dimethyl fumarate, dibutyl fumarate and the like.

Examples of acrylamides include acrylamide, methyl acrylamide, ethyl acrylamide, propyl acrylamide, butyl acrylamide and tert-acrylamide.
Butylacrylamide, cyclohexylacrylamide, benzylacrylamide, hydroxymethylacrylamide, methoxyethylacrylamide, dimethylaminoethylacrylamide, phenylacrylamide,
Dimethyl acrylamide, diethyl acrylamide, β
-Cyanoethylacrylamide, N- (2-acetoacetoxyethyl) acrylamide, etc.

Methacrylamides, for example, methacrylamide, methylmethacrylamide, ethylmethacrylamide, propylmethacrylamide, butylmethacrylamide, tert-butylmethacrylamide, cyclohexylmethacrylamide, benzylmethacrylamide, hydroxymethylmethacrylamide, methoxyethylmethacrylamide. Amide, dimethylaminoethyl methacrylamide, phenyl methacrylamide, dimethyl methacrylamide,
Diethylmethacrylamide, β-cyanoethylmethacrylamide, N- (2-acetoacetoxyethyl) methacrylamide, etc.

Allyl compounds such as allyl acetate, allyl caproate, allyl laurate, allyl benzoate and the like.

Vinyl ethers such as methyl vinyl ether, butyl vinyl ether, hexyl vinyl ether, methoxyethyl vinyl ether and dimethylaminoethyl vinyl ether.

Vinyl ketones such as methyl vinyl ketone, phenyl vinyl ketone and methoxyethyl vinyl ketone.

Vinyl heterocyclic compounds such as vinyl pyridine, N-vinyl imidazole, N-vinyl oxazolidone, N-vinyl triazole and N-vinyl pyrrolidone.

Glycidyl esters such as glycidyl acrylate and glycidyl methacrylate.

Unsaturated nitriles such as acrylonitrile, methacrylonitrile and the like; polyfunctional monomers such as divinylbenzene, methylenebisacrylamide,
Ethylene glycol dimethacrylate etc.

Further, acrylic acid, methacrylic acid, itaconic acid, maleic acid, monoalkyl itaconate, for example,
Monomethyl itaconate, monoethyl itaconate, monobutyl itaconate, etc.

Monoalkyl maleates such as monomethyl maleate, monoethyl maleate and monobutyl maleate.

Citraconic acid, styrene sulfonic acid, vinylbenzyl sulfonic acid, vinyl sulfonic acid, acryloyloxyalkyl sulfonic acid, such as acryloyloxymethyl sulfonic acid, acryloyloxyethyl sulfonic acid, acryloyloxypropyl sulfonic acid.

Methacryloyloxyalkyl sulfonic acids such as methacryloyloxydimethyl sulfonic acid, methacryloyloxyethyl sulfonic acid, methacryloyloxypropyl sulfonic acid and the like.

Acrylamidoalkylsulfonic acid, for example, 2-acrylamido-2-methylethanesulfonic acid, 2-
Acrylamido-2-methylpropanesulfonic acid, 2-acrylamido-2-methylbutanesulfonic acid, etc.

Methacrylamide amidoalkyl sulfonic acid, for example, 2-methacrylamido-2-methylethanesulfonic acid, 2-methacrylamido-2-methylpropanesulfonic acid, 2-methacrylamido-2-methylbutanesulfonic acid and the like.

Acryloyloxyalkyl phosphates such as acryloyloxyethyl phosphate,
3-acryloyloxypropyl-2-phosphate etc.

Methacryloyloxyalkyl phosphates such as methacryloyloxyethyl phosphate, 3-methacryloyloxypropyl-2-phosphate and the like.

Examples thereof include naphthyl 3-allyloxy-2-hydroxypropanesulfonate having two hydrophilic groups.
These acids may be salts of alkali metals (eg Na, K, etc.) or ammonium ions. Still other monomer compounds include U.S. Patents 3,459,790 and 3,4.
38,708, 3,554,987, 4,215,195, 4,247,67
The crosslinkable monomers described in JP-A-57-205735 and JP-A-57-205735 can be used. Specific examples of such a crosslinkable monomer include N- (2-acetoacetoxyethyl) acrylamide and N- {2- (2-acetoacetoxyethoxy) ethyl} acrylamide.

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

As the surfactant used in the polymerization of the polymer latex of the present invention, an anionic surfactant,
Although any of nonionic surfactants, cationic surfactants and amphoteric surfactants can be used, anionic surfactants and / or nonionic surfactants are preferred. As the anionic surfactant and the nonionic surfactant, various compounds known in the art can be used, but the anionic surfactant is particularly preferably used.

Examples of the water-soluble polymer used in the polymerization of the polymer latex of the present invention include synthetic polymers and natural water-soluble polymers, both of which are preferably used in the present invention. Among them, the synthetic water-soluble polymer, for example, 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, nonionic Examples thereof 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, for example, one having a nonionic group, one having an anionic group, one having a cationic group, one having a nonionic group and an anionic group in the molecular structure, Examples thereof include those having a nonionic group and a cationic group, those having an anionic group and a cationic group, and the like.

As the water-soluble polymer used in the polymerization of the polymer latex of the present invention, a synthetic water-soluble polymer, a natural water-soluble polymer having an anionic group, and a nonionic group and an anionic group are used. Those having a group can be preferably used.

In the present invention, the water-soluble polymer is 20
It may be dissolved in 0.05 g or more with respect to 100 g of water at 0 ° C., preferably 0.1 g or more.

As the natural water-soluble polymer, water-soluble polymer water-dispersed resin comprehensive technical data collection (Management Development Center)
, But preferably includes lignin, starch, pullulan, cellulose, dextran, dextrin, glycogen, alginic acid, gelatin, collagen, guar gum, gum arabic, laminaran, lichenin, nigran, etc. and derivatives thereof. is there. As the natural water-soluble polymer derivative, sulfonated, carboxylated, phosphorylated, sulfoalkylenated, carboxyalkylenated, alkylphosphorylated and salts thereof are preferably used. Particularly preferred are 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 are an emulsion polymerization method, a solution polymerization method, a method of redispersing a polymer obtained by bulk polymerization, and the like.

In the emulsion polymerization method, water is used as a dispersion medium, and 10 to 50% by weight of a monomer, 0.05 to 5% by weight of a polymerization initiator and 0.1 to 20% by weight of a monomer are used. About 3 with dispersant
It can be obtained by polymerizing with 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, etc. can be changed widely and easily.

As the initiator, water-soluble peroxides (eg potassium persulfate, ammonium persulfate, etc.), water-soluble azo compounds (eg 2,2′-azobis- (2-amidinopropane)-) are used.
Hydrochloride etc.) and the like.

Examples of the dispersant include water-soluble polymers, anionic surfactants, nonionic surfactants, cationic surfactants and amphoteric surfactants, which may be used alone or in combination. , Preferably a combination of a water-soluble polymer and a nonionic or anionic activator. In solution polymerization, a mixture of monomers at a suitable concentration in a suitable solvent (eg, ethanol, methanol, water, etc.) (generally, A mixture of 40% by weight or less, preferably 10 to 25% by weight with respect to the solvent) in the presence of a polymerization initiator (eg, benzoyl peroxide, azobisisobutyronitrile, ammonium persulfate, etc.) at an appropriate temperature (eg, The copolymerization reaction is carried out by heating to 40 to 120 ° C, preferably 50 to 100 ° C. After that, the reaction mixture is poured into a medium in which the produced copolymer is not dissolved, 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 which dissolves but does not dissolve in water (eg, ethyl acetate, butanol, etc.), and is vigorously dispersed in the presence of a dispersant (eg, surfactant, water-soluble polymer, etc.), and then the solvent is added. Is distilled off to obtain a polymer latex.

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

The Tg's of many polymers of ethylenic monomers used in the present invention are determined by Brand Wrap et al., "Polymer Handbook", pages III-139 to III-179 (1966).
Year) (Wiley and Sons Edition),
The Tg (° K) of the copolymer is represented by the following formula.

Tg (copolymer) = v ₁ Tg ₁ + v ₂ Tg ₂ + ... + vw Tgw where v ₁ , v ₂ ... Vw represent the weight fraction of the monomers in the copolymer, Tg ₁ , Tg ₂ ... Tgw represent the Tg (° K) of the homopolymer of each monomer in the copolymer.

The Tg calculated according to the above equation has an accuracy of ± 5 ° C.

Regarding the method for synthesizing the polymer latex used in the present invention, US Pat. Nos. 2,852,386 and 2,853,457,
3,411,911, 3,411,912, 4,197,127, Belgian Patents 688,882, 691,360, 712,823, JP-B-45-5331, JP-A-60-18540, 51-130217, and 51-130217.
58-137831, 55-50240 and so on.

The average particle size of the polymer latex used in the present invention is 0.5 to 300 nm, preferably 100 to 250 nm.

The particle size of the polymer latex used in the present invention is determined by electron micrograph method, soap titration method, light scattering method, centrifugal sedimentation method described in "Chemistry of Polymer Latex" (Kobunshi Kogakukai, 1973). Although it can be measured by the method, the light scattering method is preferably used. DLS700 (manufactured by Otsuka Electronics Co., Ltd.) was used as a device for the light scattering method.

The molecular weight is not specified, but the total molecular weight is preferably 1,000 to 1,000,000, more preferably 2,000.
It is 0 to 500,000.

The polymer latex used in the present invention can be contained in the photographic constituent layer as it is or after being dispersed in water.

The content of the polymer latex is 50 to 1000 mg, preferably 200 to ⁵ per 1 m ² of the backing layer.
It is 00 mg.

The polymer latex used in the present invention includes the case where a functional polymer such as a polymer dye or a polymer ultraviolet absorber is added in the form of 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 provided with a stirrer, a thermometer, a dropping funnel, a nitrogen introducing 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, 0.45 g of ammonium persulfate was added as an initiator, and then 90 g of ethylhexyl acrylate was added dropwise with a dropping funnel over about 1 hour. After the completion of the dropping, the reaction is continued for 5 hours as it is, and then unreacted monomers are removed by steam distillation. Then, it 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, a thermometer, a dropping funnel, a nitrogen introducing tube, and a reflux condenser, while introducing nitrogen gas to perform deoxidation. Distilled water (350 cc) was added and heated until the internal temperature reached 80 ° C. P-3 according to the present invention as a dispersant,
4.5 g of ammonium persulfate was added as an initiator, and then 0.45 g of ammonium persulfate was added, followed by ethylhexyl acrylate.
90 g is added dropwise with a dropping funnel over about 1 hour. After the completion of dropping, the reaction is continued for 4 hours as it is, and then unreacted monomers are removed by steam distillation. Then cool and pH 6 with ammonia water.
To obtain polymer latex. The particle size was 200 nm.

Production Example 3 (Synthesis of Lx-10) A 500 ml three-necked flask was charged with 200 ml of dioxane and introduced with nitrogen gas to perform deoxidation. After that, 15 g of isononyl acrylate and 35 g of cyclohexyl acrylate were added, and 1.2 g of dimethyl azobisisobutyrate as an initiator.
Is added and the reaction is continued at 60 ° C. for 6 hours. After completion of the reaction, the reaction solution is added to 3 l of distilled water with vigorous stirring to obtain white crystals.

The white crystals were collected by filtration, dried and dissolved in 100 ml of ethyl acetate.
It was added to 00 ml with vigorous stirring, and then ethyl acetate was removed to obtain a polymer latex. The particle size was 180 nm.

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

The latex solution thus obtained was used as GF / manufactured by Whotman.
Filtered with D filter, finished with water to 50.5kg, average particle size 2
A 50 nm monodisperse latex (Lx) was prepared.

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

[0087]

[Chemical 3]

[0088]

[Chemical 4]

[0089]

[Chemical 5]

[0090]

[Chemical 6]

[0091]

[Chemical 7]

[0092]

[Chemical 8]

The silver halide emulsion layer according to the present invention is an emulsion layer containing silver iodobromide having an average silver iodide content of 3 mol% or less, or silver halide grains composed of silver chloroiodobromide. It is preferable.

The silver halide emulsion of the silver halide photographic light-sensitive material of the present invention may be silver bromide, silver chloroiodobromide, or silver iodochlorobromide emulsion milk containing a small amount of silver chloride. The silver halide grain may be of any crystal type as long as it has the constitution of the present invention, for example, a single crystal such as a cube, octahedron or tetrahedron, and has various shapes. It may be polytwinned grains.

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
Can be prepared by the method described in "Emulsion Preparation and Types" on page 23 or the method described in (RD) No. 18716 (November 1979), page 648.

The emulsion used in the silver halide photographic light-sensitive material of the present invention is described, for example, in "The Theory of the" by TH James.
Photographic process ”4th edition, published by Macmillan (1977
Year) Method described on pages 38-104, GF Duffin, “Photograph
ic Emulsion Chemistry ”, published by Focal Press (1966),
“Chimie et Physique Photographique” by P. Glafkides
Published by Paul Montel (1967) or VL Zelikman et al. “Makin
g And Coating Photographic Emulsion "can be prepared by the method described in Focal Press (1964).

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

A preferred embodiment of the emulsion used in the silver halide photographic light-sensitive material of the present invention is a monodisperse emulsion in which silver iodide is localized inside the grains. The monodisperse referred to here, when measuring the average particle diameter by a conventional method,
At least 95% by number or weight of grains are silver halide grains having an average grain size within ± 40%, preferably within ± 30%.

The grain size distribution of 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 be composed of different silver halide compositions inside and outside,
For example, a core / shell type monodisperse emulsion in which a core portion of high silver chloride is coated with a shell layer of low silver chloride to have a clear two-layer structure may be used.

The method for producing the above-mentioned monodisperse emulsion is known and, for example,
J. Phot. Sci, 12.242 to 251, (1963), JP-A-48-36890,
52-16364, 55-142329, 58-49938, British Patent 1,413,748, US Patents 3,574,628, 3,655,394 and the like.

For the emulsion used in the silver halide photographic light-sensitive material of the present invention, for example, a seed crystal is used as a method for obtaining the above monodisperse emulsion, and the seed crystal is used as a growth nucleus to supply silver ions and halide ions. A grown emulsion may be used.

A method for producing the above core / shell type emulsion is well known, for example, J. Phot. Sci, 24.198. (1976), US Pat.
The methods described in 250, 3,505,068, 4,210,450, 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 has an aspect ratio (ratio of grain diameter / grain thickness).
May be 3 or more tabular grains. As an advantage of such tabular grains, improvement of spectral sensitization efficiency and graininess of an image, and improvement of sharpness can be obtained, for example, British Patent 2,112,157, U.S. Patents 4,414,310, 4,434, 4,434,
No. 226, etc., and the emulsion can be prepared by the methods described in these publications.

The above-mentioned emulsion may be either a surface latent image type which forms a latent image on the grain surface, an internal latent image type which forms a latent image inside the grain, or a type which forms a latent image both on the surface and inside. It may be an emulsion.

These emulsions are subjected to physical ripening or grain preparation at the stage of, for example, cadmium salt, lead salt, zinc salt, thallium salt, iridium salt, or complex salt thereof, rhodium salt, or complex salt thereof, iron salt or complex salt thereof. May be used.

In order to remove soluble salts, the emulsion may be subjected to the Nudel water washing method, the flocculation sedimentation method, or the like. Preferred water washing methods include, for example, aromatic hydrocarbons containing a sulfo group described in JP-B-35-16086. Examples include a method using a system aldehyde resin, and a desalting method using a polymer flocculant described in JP-A-2-7037 and exemplified G-3 and G-8.

The emulsion used in the silver halide photographic light-sensitive material of the present invention can use various photographic additives in the steps before and after physical ripening or chemical ripening. Examples of the compound used in such a step include (RD) No. 1 described above.
Various compounds described in 7643, (RD) No. 18716 and (RD) No. 308119 (December 1989) can be used. The types and locations of the compounds described in these three (RD) Research Disclosures 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 A Desensitizing dye 23 IV 998 IV 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 Whitening agent 24 V 998 V Hardener 26 X 651 Left 1004-5 X Interface Activator 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 Examples of the support used for the silver halide photographic light-sensitive material include those described in the above RD,
A suitable support is a polyethylene terephthalate film or the like, and the surface of the support may be provided with an undercoat layer to improve the adhesiveness of the coating layer, or may be subjected to corona discharge or ultraviolet irradiation.

The photographic processing of the light-sensitive material of the present invention is carried out, for example, in RD-17643, XX to XXI, pages 29 to 30 or 308119, XX to X.
Treatment with a treatment liquid may be performed as described in XI, pp. 1011-1010.

The treatment temperature is usually in the range of 18 ° C to 50 ° C.

As the treating agent, dihydroxybenzenes (eg hydroquinone), 3-pyrazolidones (eg
1-phenyl-3-eurazolidone), ammonophenols (eg N-methyl-P-aminophenol) and the like can be used alone or in combination.

A known developer such as a preservative,
If necessary, an alkali agent, a pH buffering agent, an antifoggant, a hardener, a development accelerator, a surfactant, a defoaming agent, a toning agent, a water softener, a solubilizing agent, a viscosity imparting agent, etc. may be used. Good.

A fixing agent such as thiosulfate or thiocyanate is used in the fixing solution, and a water-soluble aluminum salt such as aluminum sulfate or potassium alum may be further contained as a hardening agent.

In addition, a preservative, a pH adjusting agent, a water softener and the like may be contained.

[0115]

EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited to the following examples.

Example 1 Preparation of Seed Emulsion 1 While controlling at 60 ° C., pAg = 8 and pH = 2.0, a single silver iodobromide containing 2 mol% silver iodide having an average grain size of 0.1 μm was obtained by the double jet method. A dispersed cubic crystal emulsion (A) was obtained. The number of twins in this emulsion was 1% or less from the electron micrograph. This emulsion (A) was used as a seed crystal and grown as follows.

That is, the seed crystal (A) was dispersed in 8.5 l of a solution containing a protected gelatin kept at 40 ° C. and, if necessary, ammonia water, and the pH was adjusted with acetic acid. Using this solution as a mother liquor, an aqueous 3.1 N ammonia silver nitrate solution and an aqueous solution of potassium bromide and potassium iodide were added by the double jet method.

That is, pAg was controlled to 7.3 and pH was controlled to 9.7 to form a layer having a silver iodide content of 35 mol%. Next, the pH is 9.0-8.
It was continuously changed to 0, pAg was kept at 9.0, and 3.2N ammoniacal silver nitrate aqueous solution and potassium bromide aqueous solution were added by the double jet method to grow. Then, a potassium bromide solution was added through a nozzle for 8 minutes, pAg was dropped to 11.0, and mixing was completed 3 minutes after the addition of the potassium bromide was completed.

This emulsion is a monodisperse emulsion having an average grain size of 0.3 μm and rounded vertices, and the average silver iodide content of the entire grain is
It was 1.5 mol%.

Next, desmol N aqueous solution manufactured by Kao Atlas Co. and magnesium sulfate solution were used for desalting, and then gelatin solution was added for redispersion.

After desalting, the emulsion was heated to 55 ° C., and ammonium thiocyanate, chloroauric acid and sodium thiosulfate were added for chemical sensitization to give 40 mg of the following spectral sensitizing dye (a):
Spectral sensitization was performed by adding 30 mg of (b) and 10 mg of (c).

[0122]

[Chemical 9]

When the maximum sensitivity was reached, 4-hydroxy-6
-Methyl-1,3,3a, 7-tetrazaindene to silver halide 1
It was stabilized by adding 1.2 g per mol.

The emulsion thus obtained was described in JP-A-2-301744, p. 95, 16
Additives as shown on lines 20 to 96, line 20.

1 g of gelatin was used as a protective layer for the emulsion layer.
The following was added to make a coating solution.

[0126]

[Chemical 10]

Further, the following was added per gelatin as a protective layer for the emulsion layer to prepare a coating solution.

70 mg of colloidal silica having an average particle size of 0.013 μm,
i-Amyl-n-decyl-sodium sulfosuccinate 7mg, 40%
Glyoxal aqueous solution 1.5 ml, 35% formalin aqueous solution,
The following antiseptics, the fluorine-containing surfactant according to the present invention, and saponin were added as shown in Table 1 to prepare a protective layer coating liquid.

[0129]

[Chemical 11]

Next, 400 mg of gelatin as a backing layer liquid,
The amount of the polymer latex of the present invention shown in Table 1, 2 g of polymethylmethacrylate, 6 g of sodium dodecylbenzenesulfonate, 20 g of the following antihalation dye, and a backing layer liquid consisting of gliol were prepared, and glycidyl methacrylate 50 wt% methyl acrylate 10 wt% , A butyl methacrylate 40 wt% copolymer consisting of three monomers was diluted to a concentration of 10 wt%, and an aqueous copolymer dispersion was obtained. A backed and backed support was prepared by coating with a protective solution consisting of gelatin, a matting agent, sodium dodecylbenzenesulfonate and glyoxal.

[0131]

[Chemical 12]

The coating amount was that shown in Table 1 for the amount of gelatin on each of the backing layer and the protective layer.

On one side of the backed support thus obtained, the emulsion layer coating solution and the protective layer coating solution were simultaneously coated in two layers by a slide hopper to obtain a sample.

The coating amount was such that the silver amount per 1 m ² was 3 g, the amount with gelatin was 3 g in the emulsion layer, and 1.2 g in the protective layer.

The obtained sample film is processed with an automatic processor SRX-50.
3. Develop with treatment liquid SR-DF (both manufactured by Konica Corporation)
The fixing, washing with water, and drying were performed in a mode that completed in 45 seconds, and the following evaluations were performed.

[Treatment Process] Process Treatment temperature (° C) Treatment time (sec) Replenishment amount Insertion-1.2 Development + crossover 35 14.6 33cc / cross cut Fixing / crossover 33 8.2 63cc / crosscut Water wash + crossover 18 7.2 3.5 liters / Min Squeeze 40 5.7 Dry 45 8.1 Total −45.0 <Evaluation of roller mark> The sample was cut into 127 × 305 mm and exposed to three levels so that the density after development was 1.0, 0.6 and 0.4 After processing two kinds of exposed samples with the above-mentioned automatic developing machine, the generation of spotted marks on the film was evaluated in the following 5 stages.

Evaluation Criteria 5: No occurrence 4: Slight occurrence 3: Occurrence, but practically possible 2: Many occurrences, practical impossibility 1: Significant occurrence < Evaluation of dryness> A large-angle (356 x 356 mm) size sample film that has been exposed so that the density after development is about 1.0 is processed continuously, and five evaluation samples are continuously processed with a processing solution. The sample film after drying was evaluated with a tentacle.

A: It is completely dried (dry state) B: There is a slightly moist part (substantially at the usage level) C: It is moist and sticks when the films are piled up D: Wet <Auto Whether or not two sheets are conveyed by the feeder> 1 set 1 using the film auto feeder KDA-500 (manufactured by Konica Corporation)
The number of times two sheets are conveyed when five sets of 500 sheets are conveyed with 00 sheets is shown.

<Evaluation of processing unevenness> Four cuts (254 × 305 m
m) The sample film, which was entirely exposed to a density of 0.5 after the processing, was processed in the same manner as described above, and visually evaluated by transmitted light on a photographic observation table. The following 5 grades were used for the evaluation.

5: No unevenness was generated at all 4: Slight unevenness was generated 3: There was unevenness, but there was no practical problem. A1: The unevenness is remarkably generated. The evaluation results are shown in Tables 1 and 2.

[0141]

[Table 1]

[0142]

[Table 2]

[0143]

From Table 1, a photographic light-sensitive material having a fluorine-containing surfactant and a silver halide emulsion having saponin was treated with a roller mark and a treatment with a backing layer containing a polymer latex with a gelatin content of 1 g / m ^2. A silver halide photographic light-sensitive material having no unevenness, good drying property and good auto-heater property was obtained.

Claims (2)

[Claims] 1. A silver halide photographic light-sensitive material having at least one light-sensitive halogen emulsion layer and a protective layer on at least one side of a support, and a backing layer on the opposite side, wherein an emulsion layer of the light-sensitive material is provided. Contains fluorine-containing surfactant and saponin, and the backing layer contains 1 g / m ² of gelatin.
A silver halide photographic light-sensitive material comprising the following and containing at least one polymer latex. 2. A silver halide photographic emulsion containing the fluorinated surfactant and saponin in a weight ratio of 1: 2 to 3: 1. Silver halide photographic light-sensitive material.