JPH01267640A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To improve graininess of a silver halide photographic sensitive material without reducing its sensitivity by incorporating at least one kind of liquid paraffin into an outermost layer, and regulating an amt. of a matting agent to be contained in the outer-most layer to <=15mg/m<2>. CONSTITUTION:At least one kind of liquid paraffin is incorporated into the outermost layer of the silver halide photographic sensitive material, and content of the matting agent in one of the outermost layer is regulated to <=15mg/m<2>. The kind of the liquid paraffin is not restricted particularly by a mol.wt. etc., and any kind of liquid paraffin may be useful so far as it reduces a coefft. of static friction and a degree of adhesion when it is present on the surface of a body as compared to that when it is absent. Preferred amt. of the matting agent to be used is <=50mg/m<2> when a mean particle size of the matting agent is <=2mum, and an improving effect for graininess is obtd. when it is <=30mg/m<2>, particularly, <=15mg/m<2> in the case of >=2mum particle size. Thus, graininess and sharpness of the silver halide photographic sensitive material are improved without reducing its sensitivity.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a silver halide photographic light-sensitive material (hereinafter referred to as "sensitive material"), and particularly to i! It is between sensitive materials with improved i-quality and adhesion resistance.

(Prior art) In recent years, photographic materials have been developed with high sensitivity, excellent graininess,
There are increasingly high demands for photographic performance such as high sharpness and low fog density.

In particular, technology that increases sensitivity without deteriorating grain quality and sharpness, or technology that improves graininess and sharpness without reducing sensitivity, is one of the areas we have focused most of our efforts on. . For example, if high sensitivity is achieved by increasing the silver halide grain size, the graininess deteriorates, and conversely, if the size is made small in an attempt to improve the graininess, the sensitivity decreases. Furthermore, various well-known stabilizers are well known for their graininess improving effects, but all of them cause some kind of decrease in sensitivity.

On the other hand, in the maintenance WN of silver halide banknotes, a matting agent is used in -S for purposes such as transportability, adhesion resistance, and prevention of scratches. For example, colloidal silica, barium strontium sulfate, polymethyl methacrylate, methyl methacrylate-methacrylic acid copolymer, patent application 1986-5
Matting agents made of methyl methacrylate-styrene sulfonic acid copolymer described in No. 0684 and particles containing fluorine groups described in JP-A-61-230136 are well known. A capping agent having a functional group capable of reacting with gelatin described in No. 62-1, 175485 is also preferably used.

However, these matting agents worsen graininess and
There are many inconveniences such as peeling off during transportation, staining the transported parts, and precipitation in the coating liquid state, so it is desirable to use as little as possible, but it has good slip properties, adhesion resistance, and scratch prevention. This could not be achieved due to the necessity of

(Object of the Invention) Therefore, an object of the present invention is to provide a photosensitive material with improved graininess without deteriorating transportability, adhesion resistance, and scratch resistance, and without reducing sensitivity. .

(Means for Solving the Invention) These objects of the present invention are to provide a light-sensitive material having at least one light-sensitive silver halide emulsion layer on a support, the outermost layer containing at least one type of liquid paraffin; And the content of mat material contained in one outermost layer is 15■/r
This was achieved by keeping it below rf. In addition, when the average particle size of pine) W is less than 2 pm, the content of pine + There are no particular limitations, and any substance that, when present on the surface of an object, can reduce the static friction coefficient and degree of adhesion of the surface compared to when it is not present may be used. When using liquid paraffin in the present invention, it is important to It is necessary to contain it in the outermost layer, and the amount used is 5 to 300 sq./p, preferably 10 to 100 sq./p, particularly preferably 20/60 sq./p.

The liquid paraffin of the present invention may be added by any method, but usually it is added directly to the coating solution for the outermost layer, or if it is insoluble in water, it is dissolved in an organic solvent beforehand, or it is added in advance. It may be prepared as a dispersion in an aqueous dispersion or a hydrophilic colloid liquid and added to the coating solution for the outermost layer, or when used as a dispersion, various surface active agents may be used as dispersants to form fine particles. It is preferable to use it as a dispersion.
Preferably used dispersants include dodecylbenzenesulfonic acid, p-nonylphenoxybutanesulfonic acid, α
Examples include sodium salts such as -sulfosuccinic acid dioctyl ester and N-methyloleoyl taurine.

In addition, as organic solvents, alsyls (e.g. methanol, ethanol, propatool, etc.), esters (e.g. methyl, ethyl, butyl esters of acetate, methyl, ethyl, propyl esters of formic acid, etc.), amides (dimethylformamide, dimethylacetamide, etc.). When dispersing liquid paraffin, it is better to use a hydrophilic colloid, and gelatin is particularly effectively used.

As for the dispersion method, for the hydrophilic colloid layer, an ultrasonic homogenizer or a pulp homogenizer is used in the presence of a suitable dispersant, preferably 0.05 to 10
It is sufficient to disperse the particles to have a particle size of μm.

Matting agents used in the present invention include colloidal silica, barium strontium sulfate, polymethyl methacrylate, methyl methacrylate-methacrylic acid copolymer, and
Examples include a methyl methacrylate-styrene sulfonic acid copolymer described in Japanese Patent Application Laid-open No. 50684, and a matting agent made of particles containing fluorine groups described in JP-A-61-230136. Furthermore, a matting agent having a functional group capable of reacting with gelatin described in Japanese Patent Application No. 175485/1985 is also preferably used.

The average particle size of these particles is preferably 10 μm or less, particularly preferably 6 μm.

These matting agents are usually preferably present in the outermost layer, but may be present in the same layer as the liquid paraffin-containing layer.
Further, in the case of a sensitive material having a bank surface, the layers may not be the same.

When the average size of the matting agent is 2 .mu.m or less, the amount used is preferably 50 .mu./d or less, and particularly when it is 30 .mu./d or less, there is a remarkable effect of improving graininess.

In addition, if the average size is 2μm or more, 30μm or more
/m2 or less, and particularly when it is 15/m2 or less, there is a remarkable effect of improving graininess.

Next, other constituent elements of the photosensitive material in the present invention will be described below.

In the photographic emulsion layer or other hydrophilic colloid layer of the photosensitive material made using the present invention, the binder that normally constitutes the photosensitive material is generally used.

For example, gelatin that participates in crosslinking with an average molecular weight of 70,000 to 100,000 (can be treated with lime or acid), and US Pat.
High-molecular-weight polyacrylamide, polyvinyl alcohol, polyvinylpyrrolidone, dextran, and derivatives thereof, etc. disclosed in US Pat. No. 14,289 can be preferably used. Polymers other than gelatin may be added separately from the organic substance (water-soluble polymer) of the present invention for the purpose of increasing the covering power of silver halide, or may be added to the water-soluble polymer used for the purpose of the present invention. has a wide molecular weight distribution,
The high molecular weight components may remain, or the components may be composed of components from which the low molecular weight components have not been completely eluted.

The amount of residual binder is preferably 1/3 to 3 times the amount of coated silver, particularly preferably 1/2 to 2 times. Of the binders in the sensitive material before development processing, gelatin is It is preferably 50% by weight or more and 90% by weight or less, more preferably 65% by weight or more and 80% by weight or less.

The amount of remaining binder is 1.5 to 6 g on one side.
/rd, preferably 2 to 4 g/rrr.

The residual binder is generally ensured by curing it with various crosslinking agents.

Although various crosslinking agents can be used, curing agents generally known in the art can be used. In particular, gelatin is used as a residual binder, and 2. gelatin is used as a hardening agent.
4-dichloro-6-hydroxy-1,3,5-) riazine or a compound having an active vinyl group, a hero-substituted formamidinium salt, or a carbamoylammonium salt can be preferably used.

Examples of compounds having an active vinyl group include JP-A-53-41221, JP-A-53-57257, JP-A-51-126124, JP-A-49-13563,
JP 51-44164, JP 52-21059, JP 3490911, JP 3539644, JP 362486, JP 50-35807, JP 5
Listed below are compounds described in Japanese Patent Publication No. 4-30022, Japanese Patent Publication No. 53-66960, Japanese Patent Publication No. 52-46495, Japanese Patent Publication No. 47-8736, U.S. Pat. be able to.

Examples of compounds having a halo-substituted formamidinium group include JP-A No. 60-225148 and JP-A No. 61-Sho.
Examples include metal compounds described in No. 240236.

As a compound having a carbamoylammonium group,
For example, JP-A-56-12853, JP-A-58-32
The compounds described in No. 699 can be mentioned.

Furthermore, as the gelatin hardening agent used in the present invention, a polymer hardening agent can be effectively used, and in particular,
The polymeric hardener described in No.-61742 provides favorable effects.

In the present invention, the film is hardened with these hardening agents, but it is hardened in water (at 21°C) as described in U.S. Pat. No. 4,414,304.
, 3 minutes) is preferably 300% or less, especially 2
00% or less is preferable.

The photosensitive silver halide emulsion used in the present invention includes:
Silver chloride, silver chlorobromide, silver bromide, silver iodobromide, and silver chloroiodobromide can be used, but from the viewpoint of high sensitivity, silver bromide or silver iodobromide is preferable, especially when the iodine content is low. Omo1%~3
．． 5 mo1% is preferred.

Among silver iodobromide, grains having a structure having a high iodide phase inside are particularly preferred.

Also, Japanese Patent Application Publication No. 61-230135 and Japanese Patent Application No. 61-169
Compounds that release inhibitors during development, such as those described in 499, may also be used.

The amount of coated silver in the photosensitive material of the present invention is 1.0 to 15.0 g/n (especially 1.5 to 6.0 g/n) per side of the support.
It is preferable that

The sphere-equivalent average particle size of the same volume as the particles is preferably 0.3 μm or more, particularly preferably 0.3 to 2.0 μm. The particle size distribution may be narrow (or wide).

The silver halide grains in the emulsion may have a regular crystal shape such as a cube or an octahedron, or may have an irregular crystal shape such as a spherical shape, a plate shape, a potato shape, etc.
The particles may have irregular crystal forms, or may have a composite form of these crystal forms, or may consist of a mixture of particles of various crystal forms.

Tabular grains are grains that can be particularly effectively used as silver halide grains applicable to the present invention.

The tabular silver halide grains can be produced by appropriately combining methods known in the art.

The tabular silver halide emulsion is disclosed in JP-A-58-127.92.
1, 58-113,927, 58-113.928
This can be easily adjusted by referring to the method described in U.S. Pat. No. 4,439,520.

Among these, the tabular grain emulsion preferably used in the present invention is US Pat.
According to the definition, the average aspect ratio is preferably 3 or more, particularly 4 to 8.

Details of the structure and manufacturing method of tabular grains can be found in Japanese Patent Application No. 1986-29.
9155.

Further, the silver halide grains used in the present invention form a core/shell type shallow latent emulsion with the tabular grain as a core,
You may use that.

Further, the silver halide grains used in the present invention may be grains in which the tabular grains are used as host grains and guest grains having various halogen compositions are epitaxially grown.

The tabular grains used in the present invention may have dislocation lines inside.

The photographic emulsion used in the present invention can contain various compounds for the purpose of preventing fogging or stabilizing photographic performance during the manufacturing process, storage, or photographic processing of the sensitive material. That is, azoles such as benzothiazolium salts, nitroindazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, aminotriazoles. , benzotriazoles, nitrobenzotriazoles, mercaptotetrazoles (especially 1-phenyl-5
mercaptopyrimidines; mercaptotriazines; thioketo compounds such as oxazolinthione; azaindenes, such as triazaindenes, tetraazaindenes (especially 4-hydroxy substituted (1,3,3a, 7 ) tetrazaindenes), pentaazaindenes, etc.; many compounds known as antifoggants or stabilizers can be added, such as benzenethiosulfonic acid, benzenesulfinic acid, benzenesulfonic acid amide, etc. For example, those described in U.S. Pat. No. 3,954,474, U.S. Pat.

The silver halide grains used in the present invention may be spectrally sensitized with an enhancing dye.

The dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes and hemioxonol dyes. Particularly useful dyes are those belonging to the cyanine dyes, merocyanine dyes, and complex merocyanine dyes. Any of the nuclei commonly used for cyanine dyes can be used as the basic heterocyclic nucleus for these dyes. Namely, viroline, oxazoline, thiazoline, pyrrole, oxazole, thiazole, selenadur, imidasol, tetrazole, pyridine, etc.; nuclei in which an alicyclic hydrocarbon ring is fused to these nuclei; and A nucleus in which an aromatic hydrocarbon ring is fused to the nucleus, that is, an indolenine nucleus,
Applicable examples include benz-indole/nin nucleus, indole nucleus, benzoxadol nucleus, naphthoxazole nucleus, hendithiazole nucleus, naphthothiazole nucleus, benzoselenazole nucleus, benzimidazole nucleus, and quinoline nucleus.

These nuclei may be substituted on carbon atoms.

70 Shiichi? Nin dyes or complex merocyanine dyes contain a virazolin-5-one nucleus, a thiohydantoin nucleus, and a 2-thioxazolidine nucleus as a nucleus having a ketomethylene structure.
2,4-dione nucleus, thiazolinone-2,4-dione nucleus,
A 5- to 6-membered heteroartic ring nucleus such as a rhodanine nucleus or a thiobarbir scattering nucleus can be applied.

Specifically, Research Disclosure Volume 176R
D-17643 (December 1978 issue) No. 23, and those described in U.S. Pat. No. 4,425,425 and U.S. Pat.

These sensitizing dyes may be used alone or in combination, and combinations of sensitizing dyes are often used particularly for the purpose of supersensitization.

Along with the sensitizing dye, it is a dye that itself does not have a spectral sensitizing effect or a substance that does not substantially absorb visible light,
The emulsion may contain a substance exhibiting supersensitization, such as an aminostilbene compound substituted with a nitrogen-containing heterocyclic group (for example, U.S. Pat. Nos. 2,933,390 and 3,63).
5,721), aromatic organic acid formaldehyde condensates (such as those described in U.S. Pat. No. 3,743.510), cadmium salts, azaindene compounds, etc., U.S. Pat. No. 613, No. 3,615,641, No. 3,617.295, No. 3
, 635.721 is particularly useful.

The timing of adding the sensitizing dye used in the present invention to the emulsion is as follows:
Preferably, the process is carried out before the emulsion is coated on a suitable support, but it may also be carried out in a chemical ripening step or in a silver halide grain formation step.

The emulsion layer of the photosensitive material of the present invention may contain a plasticizer such as a polymer or an emulsion for improving pressure characteristics.

For example, British Patent No. 738.618 describes heterocyclic compounds, British Patent No. 738,637 describes alkyl phthalates, British Patent No. 738,639 describes alkyl esters, and U.S. Patent No. 2,960.404 describes polyvalent cyclic compounds. Alcohol, 3.1
No. 21,060 contains carboxyalkyl cellulose,
Japanese Patent Publication No. 53-28086 discloses a method using an alkyl acrylate and an organic acid.

The hydrophilic colloid layer of the photosensitive material of the present invention can contain polymer latexes well known in the art, such as homopolymers or copolymers of alkyl acrylate and copolymers of vinylidene chloride. The polymer latex may be stabilized in advance with a nonionic surfactant as described in JP-A-61-230136.

The support used in the present invention can also be provided with an antihalation layer. For this purpose, carbon blanks or various dyes such as oxonol dyes, azo dyes, aryltin dyes, styryl dyes, anthraquinone dyes, merocyanine dyes and tri(or di)allylmethane dyes may be used. Cationic polymers or latexes may then be used to prevent the dye from diffusing out of the antihalation layer.

In addition, in order to improve the color tone of developed silver,
Magenta dyes such as those described in US Pat. No. 5,445 may also be used.

The photographic emulsion layer or other hydrophilic colloid layer of the photosensitive material of the present invention may contain coating aids, antistatic properties, smoothness improvement, emulsification dispersion, adhesion prevention, and improvement of photographic properties (e.g., development acceleration, high contrast,
Various surfactants may be included for various purposes such as sensitization.

For example, saponins (steroids), alkylene oxide derivatives (e.g. polyethylene glycol, polyethylene glycol/polybrobylene glycol condensates, polyethylene glycol alkyl ethers or polyethylene glycol alkylaryl ethers, polyethylene glycol esters, polyethylene glycol sorbitan esters, Nonionic surfactants such as alkylene glyco, -alkylamines or amides, silicone polyethylene oxide adducts), fatty acid esters of polyhydric alcohols, alkyl esters of sugar; alkyl carboxylates, alkyl sulfonic acids salts, alkylbenzene sulfonates, alkylnaphthalene sulfonates, alkyl sulfates, alkyl phosphates, N-acyl-N-alkyl taurines,
Acidic groups such as carboxy groups, sulfo groups, phospho groups, sulfate ester groups, phosphate ester groups, etc. Containing anionic surfactants; amphoteric surfactants such as amino acids, aminoalkyl sulfonic acids, aminoalkyl sulfates or phosphates, alkyl betaines, and amine oxides: alkylamine salts, aliphatic or aromatic quaternary ammonium Cationic surfactants such as salts, heterocyclic quaternary ammonium salts such as pyridinium, imidazolium, and phosphonium or sulfonium salts containing aliphatic or heterocycles can be used.

These include Ryohei Oda et al.'s ``Surfactants and Their Applications'' (Maki Shoten, 1964), Hiroshi Horiguchi's ``New Surfactants'' (Sanko Publishing ■, 1975), and ``Matsutakations Detergent and Emulsion''. Fires” (
Mc Cation Divijins, MC Publishing Calvany 1985) (rMc Cut
Cheons Detergents & Esuls
ifiersJ(Me Cutcheon Divis
ions, MC Publishing Co, 19
85)), JP-A-60-76741, vF Gan-Sho 61-
No. 13398, No. 61-16056, No. 61-324
No. 62, etc.

As the antistatic agent, in particular, fluorine-containing surfactants or polymers described in Japanese Patent Application Nos. 60-249021 and 61-32462, and JP-A-60-76742 and 60-8.
No. 0846, No. 60-80848, No. 60-8083
9, No. 60-76741, No. 58-208743, Japanese Patent Application No. 61-13398, No. 61-1605.6, No. 61-32426, etc.; Also, Japanese Patent Publication No. 57-20454
Conductive polymer or latex (nonionic, anionic,
cationic, amphoteric) can be preferably used. Inorganic antistatic agents include ammonium, alkali metal, alkaline earth metal halogen salts, nitrates, perchlorates, g-acids,
Acetate, phosphate, thiocyanate, etc. are preferred, and conductive tin oxide, zinc oxide, or composite oxides prepared by doping these metal oxides with antimony, etc., as described in JP-A-57-118242, etc. are preferred. Can be used. Furthermore, various charge transfer complexes, π-conjugated polymers and their doped products, organic metal compounds, and eyebrow compounds can also be used as antistatic agents, such as TCNQ/TTF, polyacetylene, and polypyrrole. These are described in Morita et al., Kagaku to Kogyo 59(3), 103-111 (1985), Saitama et al. (4), 146-152 (1985).

The photosensitive material of the present invention may also include an intermediate layer, a filter layer, an antihalation layer, etc., if necessary.

In the photosensitive material of the present invention, the photographic emulsion layer and other layers are coated on a flexible support such as a plastic film that is commonly used in photosensitive materials. Useful flexible supports include films made of semi-synthetic or synthetic polymers such as cellulose nitrate, cellulose acetate, cellulose nitrate butyrate, polystyrene, polyvinyl chloride, polyethylene terephthalate, polycarbonate, and the like. The support may be colored using dyes or pigments.

In the present invention, there are no particular limitations on the method for coating the surface protective layer of the emulsion layer 9 on the support, but for example, U.S. Pat.
The multilayer starting coating method described in JP-A No. 2,761,791 and the like can be preferably used.

In the present invention, a polymer that provides cation sites may be contained in the fixing solution, and a dye may be further added to the so-called! O14 mordant polymers may also be used.

The developer used in the present invention can contain a conventionally known developing agent. As the developing agent, dihydroxybenzenes (for example, hydroquinone), 3-pyrazolidones (for example, l-phenyl-3-pyrazolidone), aminophenols (for example, N-methyl-p-aminophenol, etc.) are used individually or in combination. be able to.

In addition to a, the developing solution contains a known preservative, an alkaline agent, and p.
Contains HI buffer agent, anti-fogging agent, etc., and further contains dissolving aid, color toning agent, development accelerator (e.g., quaternary salt, hydrazine, benzyl alcohol), surfactant, antifoaming agent, etc.
water softeners, hardeners (e.g. glutaraldehyde),
It may also contain a viscosity-imparting agent.

As the fixer, one having a commonly used composition can be used. As the fixing agent, in addition to periosulfate and thiocyanate, it is possible to use sulfur compounds known to be effective as fixing agents.

The fixing solution may contain a water-soluble aluminum salt as a hardening agent.

The developing method using an automatic developing machine in the present invention includes a roller conveyance type automatic processing method described in U.S. Pat. No. 3,025,779, U.S. Pat. It is preferable to use a developing machine.

The development temperature is 18°C to 50°C, especially 25°C to 45°C.
It is preferable that the development time is 10 seconds to 15 seconds.
It is preferably 0 seconds, particularly 30 seconds to 120 seconds.

In the present invention, silver halide grains containing tabular grains are used, and the swelling in water (21°C, 3 minutes) is 25°C.
It is particularly preferable that it is 0% or less.

There are no particular limitations on the various additives, development methods, exposure methods, etc. of the photosensitive material of the present invention, and there are no particular limitations on the various additives, development methods, exposure methods, etc.
(August 1999) can be referred to.

(Example) Next, the present invention will be specifically explained.

Example 1 (1-1) Preparation of emulsion coating solution Iodobromide 1! (silver iodide 2.6 mol%) forming potato-shaped grains (average grain size 0.6 μm), after desalting,
Inert gelatin was added and chemically sensitized with chlorauric acid salts and sodium periosulfate. After chemical sensitization, the antifoggant 4-hydroxy-6-methyl-1,3,3a,7-titrazaindene was added to obtain sensitizing dye (1) with the following structural formula.
Halogenated! ! Ortho sensitization was carried out by adding 200 μm per mole of particles.

C, H.

I CtHs (CHg) tSO! -Additionally, p-octylphenoxyethoxyethoxyethoxyethanesulfonic acid sodium salt as a coating aid, polybotacium p-styrene sulfonate as a thickener, and trimethylolpropane were added to prepare an emulsion coating solution. il at this time
/ gelatin weight ratio was 1.35.

(1-2) Preparation of coating solution for emulsion side protective layer The following gelatin solution was prepared as a coating solution for surface protection layer.

0 gelatin 1.2 g/n (0
Sodium polyacrylate (molecular weight: 400,000") 0.020 Potassium polystyrene sulfonate (molecule: 1.6 million) 0.0150 Polymethyl methacrylate (matting agent) Op-t- listed in Table 1
Sodium salt of octylphenoxydicryceryl butyl sulfonate 0.020 Poly(degree of polymerization 10) oxyethylene cetyl ether 0.035o1.2-bis(vinylsulfonylacetamido)ethane 0°150 Fluorine-containing compound CsF+, 5OsK O, 003C
3ft.

o CsF + qsOtN” (CllgCHloh
(CIlx)-tsOJao, 001 0 liquid paraffin Listed in Table 1 (1-3
) Preparation of photographic film The above-mentioned emulsion coating solution and a solution prepared by adding liquid paraffin and capping agent polymethyl methacrylate to the surface-preservation flIN solution in the proportions shown in Table 1 were applied to an undercoated polyethylene terephthalate support. Photographic materials (1-1) to (+-9) were prepared by coating and drying.

At this time, the amount of coated silver was 5g/rd, and the amount of silver was maintained! ! The amount of gelatin applied in the layer was 1.2 g/d.

(1-4) Measurement of granularity After irradiating the above raw sample with green light, tank development was performed at 30°C for 2 minutes using Fuji Photo Film's special developer "Hyrendol" until the density became 0.5. Samples for granularity measurement were prepared by adjusting the exposure amount.

This sample was exposed to white light with a luminous flux (aperture) of 48 μmφ.
Microdensity was measured using a beam of light, and the square root of the mean square of the density variation values (R, M, S) was used as an evaluation of granularity. The values are shown in Table 1. A larger value indicates poor granularity.

(1-5) Evaluation of adhesion resistance Samples (1-1) to (1-8) were moistened at 25°C, 70% RH for 2 hours, and sealed with the emulsion protective layers in contact with each other under a load of 50 g/ci. and keep warm at 50°C for 3 days.

A sample was taken out, the adhesive surface was peeled off, the ratio of the adhesive area to the total area 1 was measured, and the evaluation was graded A to D as shown below.

A... Adhesive area ratio is 0 to 5% (Good) B...
... l 5-25%C... #2
5-50% D... #50% or more The A-D ranks evaluated in this manner are shown in Table 1.

As is clear from Table 1, (T-5) to (1-
9) had good granularity and excellent adhesion resistance. Comparative sample for this! -1 and 1-4 have poor granularity due to the large amount of matte coating, and comparative samples 1-2 and I
Samples - and 3 had good granularity but poor adhesion resistance, and there was no difference in photographic properties among the samples.

Example 2 Photographic material t4 ( I[-1) to (IT-11) were created and evaluated.

From Table 2, (II-4) to (II-6), (■
-8) to (II-11) had good granularity and excellent adhesion resistance. Comparative sample [-1,! -3 had poor granularity (and comparative samples 1-2 and -7 had poor adhesion resistance. No difference was observed in photographic properties.

Example 3 (3-1) Preparation of emulsion coating solution D-F In 1 liter of water, 5 g of potassium bromide, 0.05 g of potassium iodide, 30 g of gelatin, 1 thioether HO (CHz) gs (CL) ms (CHg) to H
% aqueous solution was added and kept at 75°C, an aqueous solution of 8.33 g of silver sulfate and an aqueous solution containing 5.94 g of potassium bromide and 0.726 g of potassium iodide were added while stirring. It was added in 45 seconds by jet method. After adding 2.5 g of potassium bromide to Vt, 18.33 g of nitric acid
An aqueous solution containing A g was added over 7 minutes and 30 seconds, and further A g
500 - of an aqueous solution of 5150 g of N O and 80 (CHz) zs (CHz) is (CHz) zOHo of thioether
, and a 20% aqueous solution of KBr containing 5 g were added for 15 minutes by a double jet method at PBrl of 6 to form tabular grains (average diameter 0.7 μm, average thickness 0).
．． 12 μm).

After desalting, inert gelatin was added to this, and 2 sensitizing dyes (■) having the following structural formula were added per mole of silver halide grains.
00■ was added to perform dye sensitization, followed by chemical sensitization with chlorauric acid salt and sodium thiosulfate.

(■) t (CHz) xSO3-(CL) zsOsNa After chemical sensitization, antifoggant 4-hydroxy-6-methyl-
1, 3, 3a,? - Tetrazaindene was added, p-octylphenoxyethoxyethoxyethoxyethanesulfonic acid sodium salt as a coating aid, polybotacium p-styrene sulfonate as a thickener, and trimethylolpropane were further added to prepare an emulsion coating solution.

(3-2) Preparation of Coating Solution for Milk 7FIJ Side Protective Layer The following gelatin solution was prepared as a coating solution for surface protective layer.

0 gelatin 0.12g/r+?
0 Sodium polyacrylate (molecular weight 600,000) 0.05 g / Potassium polystyrene sulfonate (molecular weight 600,000) 0.03 #0 Textran (molecular weight 37,000”) 0.4 g/rrl
O polyacrylamide (only 0.8 million molecules) 0.4 〃sHt a CsF+qSOJ+CHtCH*f))i(CL
h = SOJa0.002 # Φ o C@F+, 5ONH(CHth 5N(CHz)s
・Ieo,ooos #CI.

Φ1 o C*F+qCONH(cnz)-ff? 1-C
HxCQOe shell CHz 0.0005 ” H 0,003N In addition to the above compound, liquid paraffin and polymethyl methacrylate (average particle size 3.4 μm) were added as a mantle agent.
was added to the coating amount shown in Table 3.

(3-3) Preparation of photographic film Liquid paraffin and matting agent were added to the above-mentioned emulsion coating solution to the surface protective layer solution in the proportions shown in Table 2. A photographic material (II
I-1) to (I[[-5) were created. At this time, the amount of coated silver was 2 g/n, and the amount of gelatin coated for the protective layer was 1.2 g/n.
(And so.

The method for measuring granularity and the evaluation of adhesion resistance were the same as in Example 1.

Table 3 shows that (III-3) to (III-5) of the present invention have excellent particle size.

Example 4 (4-1) Adjustment of emulsion coating solution Same as Example 3 (4-2) Adjustment of surface protective layer coating solution Remove liquid paraffin and agent polymethyl methacrylate The table of Example 1 except that it is as shown in Table 4. Same as coating liquid for surface protection layer.

(4-3) Adjustment of coating liquid required for banks. Gelatiny 2.4g/Sodium polyacrylate (molecular weight 600,000") 0.05g/f
frO potassium polystyrene sulfonate (molecular weight 600,000) 0.03# O dextran (molecular weight 37,000) 0.4 g/ldO polyacrylamide (molecular weight 08,000) 0.4 sC,
H.

6 c, F, ff5o! 11 (CLCL0ko(CL
Fas03Na0.002 # Φ o CsF+tSONH)CHz(5N(CHx)i
・I"o, ooos # L Φ1 o CJ+*C0NH(CHxh s N-CHtC
OOe sleep H2 0,0005- 0,02# C) 13 ΦI o C++HzsCONII (CHz + s N-C
HtCOOell3 0.003 # o CwF+ vcoo(CHzCHxOh-1i(C
HxCHC)IiO't-J嘗H 0,003g/Ward dol, 2-bis(vinylsulfonylacetamide) Ethane 0.15 〃0 Matting agent polymethyl methacrylate (average particle size 3.4 μm) 50■/M35■ /
I40■/rd O Liquid paraffin Listed in Table 4 (4-4
) Preparation of photographic film The above emulsion coating solution and surface protective layer coating solution are coated on a polyethylene terephthalate support coated with an undercoat and dried. Furthermore, the above-mentioned back layer coating solution was applied to the side opposite to the support and dried to obtain a photographic material (IV-1) as shown in Table 4.
) to (TV-4>) were prepared. At this time, the coating!Ji amount was 2 .mu./d.

/ As is clear from Table 4, it can be seen that even when liquid paraffin is present on the bank layer side, the adhesive resistance and granularity are excellent. (Sample 2-4).

Example 5 (5-1) Preparation of emulsion coating solution Same as Example 3 (5-2) Preparation of surface protective layer coating solution Matting agent polymethyl methacrylate (average particle size 3.4 μm) was applied to the cloth at 50 w/rd”! The same as Example 3 except that liquid paraffin was added in the proportion shown in Table 5.

(5-3) Adjustment of coating liquid required for banks removing liquid paraffin; Cloak agent polymethyl metal rylate By adding in the proportions shown in Table 5. For the outside, install the bank in the same way as in Example 4. A coating solution was prepared.

(5-4) Making photographic film Shown in Table 5 using the same method as Example 4 Create sensitive materials (V-1) to (V-4) did.

/ From Table 5, it can be seen that the present inventions (V-2) to (V-4) are excellent in granularity and adhesion resistance in this example as well.

Claims (2)

[Claims] (1) A silver halide photographic light-sensitive material having at least one light-sensitive silver halide emulsion layer on a support, the outermost layer of the silver halide photographic light-sensitive material containing at least one type of liquid paraffin, and A silver halide photographic material characterized in that the content of a matting agent contained in one outermost layer is 15 mg/m^2 or less. (2) A silver halide photographic material having at least one light-sensitive silver halide emulsion layer on a support, the outermost layer of the silver halide photographic material containing at least one type of liquid paraffin, and The average particle size of the matting agent contained in one outermost layer is less than 2 μm, and the content is 30 μm.
A silver halide photographic material characterized by having a silver halide content of mg/m^2 or less.