JPS62278542A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain a sensitive material ensuring smoothly proceeding development by adding a prescribed amount of iodine to the emulsion of a silver halide emulsion layer on a support, incorporating a specified surfactant into at least one layer on the support and regulating the swelling ratio of all of layers as a multilayered film to a prescribed value. CONSTITUTION:At least one photosensitive silver halide emulsion layer is formed on a support with an emulsion contg. silver halide having >=8mol% iodine content. A polyoxyethylene surfactant is incorporated into at least one layer on the support and the swelling ratio of all of layers as a multilayered film is regulated to >=200%. The expansion coefft. is controlled according to the amount of a hardening agent. The photographic emulsion used may be any of silver iodide, silver iodobromide, silver chloroiodobromide and silver chloroiodide emulsions but a silver iodobromide emulsion is preferable. The emulsion is preferably used after chemical sensitization.

Description

Detailed Description of the Invention 3. Detailed Description of the Invention (Field of Industrial Application) The present invention relates to a silver halide photographic light-sensitive material, particularly a silver halide photographic material having excellent development progress and excellent graininess. Related to silver photographic materials.

(Prior Art) Generally, the image 3j of a silver halide photographic light-sensitive material is determined by sharpness and graininess. In particular, graininess is an important item because it has a strong appeal to observers. Techniques for improving this graininess include reducing the grain size, using AgBrI as the silver halide, and in particular increasing the iodine content (C).

However, reducing the particle size directly leads to lowering the sensitivity, which is difficult to achieve in practice.

On the other hand, when the iodine content is increased, the graininess improves without significantly lowering the sensitivity, but only a sensitive material with poor gradation (low gamma) can be produced. In particular, when the iodine content exceeds tmolti, this tendency becomes extremely pronounced and becomes a serious problem. This tendency was particularly serious for development with a black and white developer having a low pH.

(Objective of the Invention) The object of the present invention is to provide a photosensitive material with good development progress (high gamma) with respect to a silver halide photographic material containing a photosensitive silver halide layer with an iodine content exceeding g mol. It is about providing.

(Disclosure of the Invention) The present inventor has provided at least one photosensitive silver halide emulsion layer on a support, and the emulsion contains silver halide having an iodine content of r molar percent or more. To produce a silver halide photographic light-sensitive material, which further contains a polyoxyethylene surfactant in at least one layer on a support, and has a swelling ratio of the entire film of 200% or more. It was found that the problem could be improved by

In the present invention, a polyoxyethylene surfactant is added only when the silver halide emulsion has an iodine content of more than 200% to form a film with a swelling rate of 200% or more and reduce graininess.
It was possible to improve the developability without any damage.

For films with a swelling ratio of less than 200%, the effect of the present invention is very small, probably due to the diffusion of development fatigue products during development.

(2) Merely adding a polyoxyethylene surfactant to a silver halogenide emulsion having a content of r mol or more results in poor graininess despite the improvement in developability. Conversely, even if the swelling ratio is increased by changing the hardness without adding a polyoxyethylene surfactant to a silver halide emulsion with an iodine content of r mol or more, the graininess remains even though the developability is improved. Sexuality becomes worse.

In the present invention, the swelling ratio is defined as the total thickness (D1) of the entire hydrophilic colloid layer when dry and the thickness (D2) of the total hydrophilic colloid layer after being immersed in distilled water at 200C for 5 minutes (D2 Dl ). /
It can be obtained from DIX/00.

Here, Do means 2j0C4! It refers to the film thickness after being left for SJ days.

As a method of controlling the swelling ratio, there is a method of adjusting the amount of a so-called curing agent. The layer to which a curing agent is added may be a photosensitive silver halide layer, a non-photosensitive silver halide layer, or a layer containing no silver halide.

The curing agent may be, for example, a polymeric curing agent with diffusion resistance as described in JP-A-4-2-2/2006, or a low-molecular curing agent as shown below.

Examples of low molecular curing agents include C.E.Mies (C,
E., Mees) and T.H.G.A.M., <
(T.H. James), The Theory of the
Photographic Process (The Theory)
of the PhotographicPro
cess) 3rd edition (151% 4 years), US Patent No. 3.3
/A, No. 09j, No. 3123λ, No. 76≠, No. 3.21
r1.77j, 2,732.303, J, l,
! ! , 7/♂ Judo 3I23λ, 7th layer No. 3, Doko, 73ko, No. 37, Doko, j? Otsu.

No. 141, same! , No. 103, 1737, 3. O/7.
No. 2tO, No. λ, No. 13, 61/No., same.

7, Kota≠, same, 7λj, 2 Tata, 3.1
00,70 Hiro issue, 3,0ri/, 337, 3.3λ
/ , 3/A, 3.5ψ3.2 octopus, 3,
/2! , Hirohiro issue, British patent Tata μ.

Suitable curing agents are those described in No. 169, No. 169, No. 47,207, and the like. Typical examples include mucochloric acid, mucobromic acid, mucophenoxychloric acid, mucophenoxybromic acid, formaldehyde, dimethylol urea,
Trimethylolmelamine, glyoxal, monomethylglyoxal, co, 3-dihydroxy-/, 44-dioxane, 2°3-dihydroxy-! −Methyl−/, ≠
- Aldehyde compounds such as dioxane, succinic aldehyde, u,j-dimethoxytetrahydro7rane, daltaraldehyde; divinylsulfone, methylenebis-maleimide,! -acetyl/, 3-diacryloyl-hexahydro-5-triazine,/.

J, j-) lyacryloyl-hexahydro-3-triazine, /, 3. j-) Rivinylsulfonyl-hexahydro-3-1 riazine, bis(vinylsulfonylethyl)
Active vinyl compounds such as ether, /, 3-bis(vinylsulfonyl)-1-propanol, /13-bis(vinylsulfonylacetylamido)pro/silane; -1-dichloro-6-hydroxy-S- Triazid sodium salt, 2.4! -dichloro-6-medoxys-) riazine, co, hiro-nechloro-6-(≠-sulfoanilino) -s-triazine sodium salt, λ,≠-dichloroA-(2-sulfoethylamino)-5-triazine , N, N'-bis(2-chloroethylcarbamyl)pi is an active halogen compound such as butane;
, 3-epoxypropyl) methylpropylammonium p-toluenesulfonate, /, ≠-bis(x t
, J f-epoxypropyloxy)butane, /,
3. J-triglycidyl isocyanurate, 1,3-diglycidyl-! -Epoxy compounds such as (r-acetoxy-β-oxypropyl)isocyanurate;2. ≠
.

O-triethyleneimino-S-triazine, /.

Ethylene/imine compounds such as 6-hexamethylene-N, N'-bisethylene urea, bis-β-ethyleneiminoethyl thioether; /, λ-di(methanesulfonoxy)ethane, /l≠-di(methanesulfone) metal sulfonic acid ester compounds such as oxy)butane, 1Ij-di(methanesulfoneoxy)pentane; dicyclohexylcarbodiimide, /-cyclohexyl-J-(
3-trimethylaminopropyl)carbodiimide・1)
-) Carbodiimide compounds such as luenesulfonate, l-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride; λ,! -dimethylisoxazole perchlorate, λ-ethyl! -phenylisoxazole-3'-sulfone-1', j, t' -(
) and rough enylene) isoxazole compounds such as bisisoxazole; and inorganic compounds such as chromium acetate and chromium acetate.

Particularly preferred among these compounds are compounds having a vinyl sulfone group and active halogen compounds.

The silver halide grains in the photographic emulsion used in the photographic light-sensitive material of the present invention may have regular crystal bodies such as cubic, octahedral, rhombohedral, and rhombohedral. Also, irregular shapes such as spherical, plate-like, etc.
It may have a crystalline form (egular) or a composite form of these crystalline forms. In addition, Research Disclosure (Research Disclosure)
ure) As stated in Volume 22r, No. 0 to SR pages (/9♂January 3) is kuto ratio! The above tabular grains may be used.

Further, the particles may have an epitaxial structure, or may have a multilayer structure in which the inside and the surface of the particle are composed of different ffl structures (for example, halogen group &).

Ninth, the particle size distribution may be broad or narrow. The latter is known as a so-called monodisperse emulsion, and has a dispersion coefficient of 20 (16 or less, preferably 11% or less. (Here, the dispersion coefficient is the standard deviation divided by the average grain size). Photographic emulsion Q by N et al. Written by Glafkides, Chimie et al.
PhyaiquePhotographique) (
Published by Paul Monte1, 1267) G.F. Dauphin, (G, F, D
uffin) Photographic Emulsion
Chemistry (Photographic Emul)
sion Chemistry) (The Focal Chemistry)
Published by The Focal Press,
/ri 1966), Hui El Zelikman (V, L, Ze
Making and Coating Photographic Emulsion (Maki)
ng and coating photography
icEmulsion) (The Focal Press (T
It can be prepared using the method described in HeFocal Press (published by Lit≠), etc. In other words, any method such as acidic method, neutral method, ammonia method, etc. may be used, and methods for reacting soluble silver salt and soluble halogen salt include one-sided mixing method, simultaneous mixing method, and combinations thereof. You may also use a zucchini.

These photographic emulsions may be any combination of silver iodide, silver iodobromide, silver chloroiodobromide, and silver chloroiodide.

Silver iodobromide is preferred. Further, silver iodide gold it is more than t mole, preferably g, 5 to 30 mole, more preferably g,! ~/! It's morchi. Here r
If it is less than molten, the granularity will not improve much, and there will be almost no effect of the polyoxyethylene surfactant and the film having a swelling rate of 200% or more.

Cadmium salts, zinc salts, lead salts, thallium salts, iridium salts, or complex salts thereof, rhodium salts or complex salts thereof, iron salts, or complex salts thereof may be allowed to coexist in the stage of silver halide grain formation or physical ripening. good.

Gelatin is used as a binder for the emulsion layer and other layers.
Proteins such as casein; carboxymethylcellulose,
Cellulose compounds such as hydroxyethylcellulose;
Sugar derivatives such as agar, dextran sodium alginate, and starch derivatives; synthetic hydrophilic colloids such as polyvinyl alcohol, poly-N-vinylpyrrolidone, polyacrylic acid copolymers, polyacrylamide, and derivatives of these and partially hydrated Decomposition products etc. can also be used.

Gelatin referred to herein refers to so-called lime-processed gelatin, acid-processed gelatin and enzyme-processed gelatin.

Further, the photographic light-sensitive material of the present invention has a photographic groove bottom layer which is manufactured by U.S. Patent No. 3. μ//, ri No. 77, same 3. ≠//.

72, Tokko Sho≠Yo-Yo No. 337, etc. may be included.

The emulsion used in the photosensitive silver halide emulsion layer of the present invention is preferably chemically sensitized.

For the sake of chemical sensitization, the aforementioned Glafkides or Zeli
Kman) et al. or H. Freezer (H,
Die Grundlagen de
rPhotographischen Prozes
se mitSilberhaloge'n1den)
Akademische Fellerags Gezersha 7) (A
kademischeVerlagsgesellsc
haft), (/di+r) can be used.

In other words, sulfur sensitization using a compound containing sulfur that can react with silver ions or activated gelatin, reduction sensitization using a reducing substance, and prize metal sensitization using gold or other noble metal compounds may be used alone or in combination. Can be used. As the sulfur sensitizer, thiosulfates, thioureas, thiazoles, rhodanines, and other compounds can be used, and specific examples thereof include U.S. Pat.
s, uio, 1sty issue, 2,271.9'l-7 issue 1
, Z, 74r, No. 44r, j, No. 614.911. Reduction sensitizers include stannous salts, amines, hydrazine derivatives, formamidine sulfinic acid,
Silane compounds and the like can be used, and specific examples thereof include US Pat. No. 2≠17. I! O, Ko, 4c/Ri, Ri7
Hirogo, 2. ! /I, tri No. 2, 2.913.1s09, 2,913. /s10, Ko, tri≠, No. 637.

For noble metal sensitization, in addition to total complex salts, complex salts of metals in group I of the periodic table, such as platinum, iridium, and /e-radium, can be used.
No. 2, +<cr, oto No., British Patent All, 0
It is written g-gn in the 6/ issue etc.

The photosensitive material of the present invention may contain various compounds as stabilizers. That is, azoles such as benzothiazolium salts, nitroindazoles, triazoles, benzotriazoles, benzimidazoles (
Heterocyclic mercapto compounds such as mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, mercaptotetrazoles (particularly nitro-mercapto compounds) (especially nitro-mercapto compounds); ), mercaptopyridines; the above-mentioned heterocyclic mercapto compounds bearing a water-soluble group such as a carboxyl group or a sulfone group; thioketo compounds, such as oxazolinthione; azaindenes, such as tetraazai/denes; (
Many compounds known as stabilizers can be added, such as, in particular, hydroxy-substituted (/, J, Ja, 7) tetraazaindenes); benzenethiosulfonic acids; benzenesulfinic acid; and the like.

The photographic emulsion layer or other constituent layers of the light-sensitive material of the present invention include coating aids, antistatic properties, smoothness improvement, emulsification dispersion, adhesion prevention, and photographic property improvement (such as fc development acceleration, high contrast, and sensitization). Surfactants may be included for various purposes such as.

For example, saponins (steroids), alkylene oxide derivatives (e.g. polyethylene glyco-h, rl'?
+) Ethylene glycol/polypropylene glycol condensates, polyethylene glycol alkyl ethers or polyethylene glycol alkyl aryl ethers, polyethylene glycol esters, polyethylene glycol alkyl ethers, polyalkylene glycol alkyl amides or amides, polyethylene oxide adducts of silicone ), nonionic surfactants such as glycidol derivatives (such as alkenyl succinic polyglycerides and alkylphenol polyglycerides), fatty acid esters of polyhydric alcohols, and alkyl esters of sugars; alkyl carboxylates, alkyl sulfonic acids salts, alkylbenzene sulfonates, alkylnaphthalene sulfonates, alkyl sulfates, alkyl phosphates, N-acyl-N-alkyl taurates, sulfosuccinates, sulfoalkyl polyoxyethylene alkylphenyl ethers, poly Anionic surfactants containing acidic groups such as carboxy groups, sulfo groups, phospho groups, sulfate ester groups, phosphoric ester groups such as oxyethylene alkyl phosphates; amino acids, aminoalkyl sulfonic acids, aminoalkyl sulfates, etc. fc is phosphoric acid ester, alkyl betaine,
Ampholytic surfactants such as amine oxides; alkyl amine salts, aliphatic or aromatic v-class ammonium salts, heterocyclic quaternary ammonium salts such as pyridinium and imidazolium, and phosphonium or aliphatic or heterocyclic-containing phosphonium salts. Cationic surfactants such as sulfonium salts can be used.

The polyoxyethylene surfactant used in the present invention preferably has at least 2 or more oxyethylene groups, more preferably λ to 100 oxyethylene groups.

As the polyoxyethylene surfactant, surfactants represented by the following general formulas (1-/], [I-2] and [■-3] are particularly preferred.

General formula CI /] RIA + CH2CH2O almost R2 General formula (1-j) In the formula, R1 is a limescale atom or a substituted or unsubstituted alkyl group having 7 to 30 carbon atoms, an alkenyl group or an aryl group, and for humans it is 10- group, -8- group, -COO--8O2N R1
represents an s group (here, R14 represents a hydrogen atom or a substituted or unsubstituted alkyl group).

R2 has the same meaning as R1 or R1-A- described above.

R3, R4, R8, RIO% R12 and R14 are hydrogen atoms, substituted or unsubstituted alkyl groups, aryl groups,
It represents an alkoxy group, a halogen atom, an acyl group, an amide group, a sulfonamide group, a carbamoyl group or a sulfamoyl group. In the formula, R7, R9, R11 and R13 represent a substituted or unsubstituted alkyl group, aryl group, alkoxy group, halogen group, acyl group, amide group, sulfonamide group, carbamoyl group or sulfamoyl group.

R5 and R6 represent a hydrogen atom, a substituted or unsubstituted alkyl group, or an aryl group, and fc represents a heteroaromatic ring.

R5 and R6, R7 and R8, R9 and RIO% R11 and R
12, R13, and R14 may be connected to each other to form substituted or unsubstituted EJl. nl, R2, R3 and n
It is the average degree of polymerization of 4u ethylene oxide and is a number from 2 to 100.

Also, m is the average degree of polymerization, and! ~ is the number of O.

In the general formulas 1-/), [l-λ] and CI-J), R1 is preferably a hydrogen atom or an alkyl group, alkenyl group, or alkylaryl group having a carbon number of μ to co≠,
Particularly preferred are hydrogen atom, butyl group, hexyl group, dodecyl group, isostearyl group, oleyl group, t-butylphenyl group, 2゜hiro-di-t-butylphenyl group, 21≠
-C represents monohantylphenyl group, p-dodecylphenyl group, m-pentadecaffenyl group, t-octylphenyl group, co-, dinonylphenyl group, octylnaphthyl group, and the like.

R3% R4% R7XR8% R9, R10% ul
l\R12, R13 and R44 are preferably methyl, ethyl, i-propyl, t-7'thyl, t-amyl, t-
hexyl, t-octyl, nonyl, tesyl, dodecyl,
Carbon number of trichloromethyl, tribromomethyl, / -7, X-nyl:thyl, λ-phenyl-2-propyl, etc. / ~
20 substituted or unsubstituted alkyl groups, phenyl groups, p-
Substituted or unsubstituted aryl group such as chlorophenyl group, -
0R16 (herein, R16 represents a substituted or unsubstituted alkyl group or aryl group having a carbon number of 0 to 0; the same applies hereinafter), a substituted or unsubstituted alkoxy group, a chlorine atom, a bromine atom, etc. a halogen atom, an acyl group represented by -COR16, -NR17COR (where R17t
ri represents a hydrogen atom or an alkyl group having 7 to 20 carbon atoms. The same applies hereinafter) n amide group, -NR175o2
R16 is a sulfamoyl group, and R3, R4, R8・RIO・R12 and R14
may be a hydrogen atom. Of these, R7, R9,
R11 and R43n are preferably an alkyl group or a halogen atom, particularly preferably a bulky t-butyl group,
These are tertiary alkyl groups such as t-amyl group and t-octyl group. R8, RIO1R12 and R44 are particularly preferably hydrogen atoms. That is, a compound of general formula 111-J) synthesized from λ, Hiro-disubstituted phenol is particularly preferred.

R5 and R6 are preferably a hydrogen atom, methyl group, ethyl group, n-propyl group, i-propyl group, n-heptyl group, /-ethylamyl group, n-undecyl group, trichloromethyl group, tribromomethyl group, etc. substituted or unsubstituted alkyl group, α-furyl group, phenyl group, naphthyl group, p-chlorophenyl i, p-methoxyphenyl group, m
- Substituted or unsubstituted aryl group such as nitrophenyl group.

'! fc-Jt5 and R6, R7 and R8, R9 and RIQ
.

R11 and R12 and R13 and R14 may be linked together to form a substituted or unsubstituted ring, such as a cyclohexyl ring. Among these, R5 and R6 are particularly preferably a hydrogen atom, an alkyl group having carbon number/~r, a phenyl group, or a furyl group. nl, R2, R3 and R4 are particularly preferably numbers from t to 30. R3 and R4 may be the same or different.

Next, specific examples of the polyoxyethylene compound of the present invention will be shown.

Compound example C11H23cOO+cH2cH20) rHC15H3
1COO+CH2CH2O+TrHC17H33C00
+C1(2CH20-)TTCT,,I3■-≠ C1sH3so+cH2cH20廿H -j C12H2sO+cHzcH20+T'fHI-BC16H330+CH2CH2O+TrH(-r C22H450+CH2CH2O+-2THI-? 1-/j l-/6 H3 C13H27CON+CH2CHzO)rrH■-72 C12H25S+CH2CH2o juice, H -20 CH2CH20+CF(2CH20+TrH1-u ≠ ■-2 yo C4H9 ■-26 !-27 1-2♂ ■-λri1-Jko■-33 n 1 +n 2=J O, m=/ 0!-3≠ -3j -JG HO+CH2CH2O+T?rH 1-J ♂ 1-,?riI-Hiroshi0 ni5H11-t C3H11-t■-Hiroshi/ C3H11-t !-≠2 ■-Hiroshi≠ !-Hiroshi! ■-Hiroshi6 The amount of the polyoxyethylene surfactant of the present invention used varies depending on the type, form, coating method, etc. of the photographic material used, but in general, the amount used is 1.0 per mole of Ag in the photographic material. ■The above is sufficient, especially toIR9
The above is preferable.

The polyoxyethylene surfactant of the present invention is preferably added to the photosensitive emulsion layer of the photographic light-sensitive material, but it may be added to other non-photosensitive layers.

These polyoxyethylene surfactants are used in layers of photographic light-sensitive materials (ζ). These compounds are added as they are or added to a coating solution in order to form a layer. fc is dissolved in a M solvent such as methanol, ethanol, acetone, or a mixed solvent of water and the above-mentioned shoulder wall solvent, and then added, and the coating solution is applied and dried, or it is sprayed, coated, or coated on the surface of the support. All you have to do is immerse it in a solution and dry it.

When added to the emulsion layer, it may be added to the emulsion during the emulsion manufacturing process (such as a chemical ripening process) or after the process is completed.

The photographic emulsions of this invention are spectrally sensitized with methine dyes and others. Dyes that may be used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, steryl 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. That is, pyrroline nucleus, oxanoline nucleus, thiazoline nucleus, pyrrole nucleus, oxazole nucleus, thiazole nucleus, selenazole nucleus, imidazole nucleus, tetrazole nucleus, pyridine nucleus, etc.;
An alicyclic hydrocarbon ring is fused to these nuclei to form a friendly nucleus; and an aromatic hydrocarbon ring is fused to these nuclei to form a friendly nucleus; namely, an indolenine nucleus, a benzindolenine nucleus, an indole nucleus, and a benzoxazole nucleus. Cough, naphthoxazole nucleus, benzothiazole nucleus, naphthothiazole nucleus, he/zoselenazole nucleus, benzimidazole nucleus, quinoline nucleus, etc. are applicable. These nuclei may be substituted on carbon atoms.

Merocyanine pigments are complex merocyanine pigments that contain pyrazoline as a core with a ketomethylene structure. -one nucleus, thiohydantoin nucleus, l-thioxazolidine-co, Hiro-dione nucleus, thiazolidine-2,≠-dione nucleus, rhodanine nucleus, thiobarbic acid nucleus, etc.! -Member heterosegmental rings can be applied.

The amount of the sensitizing dye used in the present invention is 70/x70 6~ per mole of silver! It is preferable that the amount is ×10 3 moles.

The photographic emulsion of the present invention may contain a color image-forming coupler, that is, a compound (hereinafter abbreviated as coupler) that reacts with the oxidation product of an aromatic amine (usually a primary amine) developing agent to form a dye. It is desirable that the coupler be a non-diffusible coupler that has a hydrophobic group called a pallast group in its molecule. The coupler may be either leg-equivalent or di-equivalent to the silver ion. It may also contain a colored coupler that has a color correction effect or a coupler that releases a development inhibitor during development (so-called DIR coupler). The coupler may be such that the product of the coupling reaction is colorless.

As the yellow coloring coupler, a known open-chain ketomethylene coupler can be used. Among these, benzoylacetanilide-based and piparoylacetanilide-based compounds are advantageous.

As the magenta coupler, pyrazolone compounds, indacylon compounds, cyanoacetyl compounds, etc. can be used, and pyrazolone compounds are particularly advantageous.

As the cyan coupler, phenolic compounds, naphthol compounds, etc. can be used.

The protective layer of the silver halide photographic light-sensitive material of the present invention is a layer consisting of a hydrophilic colloid, and the hydrophilic colloids used include those mentioned above.

Further, the protective layer may be a single layer or a layer.

A matting agent and/or a smoothing agent may be added to the emulsion layer or the preservation layer of the silver halide photographic X-sensitive material of the present invention, preferably to the preservation layer. Examples of matting agents include polymethyl methacrylate with a suitable particle size (particle size of 0.3 to 10 μm, preferably fc of at least twice the floating bed of the protective layer, especially at least 10 times larger). Organic compounds such as water-dispersible vinyl polymers, etc., or inorganic compounds such as silver halide, barium strontium sulfate, etc. are preferably used. Smoothing agents are useful in preventing contact failure similar to matting agents, and are also effective in improving *i% properties, which are related to camera compatibility during filming or projection of movie films.Specific examples include: Waxes such as liquid paraffin, esters of higher fatty acids, polyfluorinated hydrocarbons or derivatives thereof, polyalkylpolysiloxanes, polyalline polysiloxanes, polyalkylarylpolysiloxanes, or alkylene oxide addition derivatives such as Preferably, such as /recones are used.

The silver halide photographic material of the present invention may also be provided with an intermediate layer, a filter layer, etc., if necessary.

Specific examples of the silver halide photographic material of the present invention include X-ray photosensitive materials, Lithium photosensitive materials, black and white photosensitive materials, color negative photosensitive materials, color reversal photosensitive materials, and color photographic paper.

Preferably, it is a negative photosensitive material.

Various other additives may be used in the photographic material of the present invention, if necessary. Examples include development accelerators, fluorescent whitening agents, color antifoggants, and ultraviolet absorbers. Specifically, research disclosure (RES)
EARCHDISCLO8URE) / 7g issue 2t~
A7t described on page 30 (RD-/7t4t3, /P7J') can be used.

Any known method can be used for photographic processing of the light-sensitive material produced by applying the present invention.

A known treatment liquid can be used. The processing temperature is usually chosen between 7r0C and so0c, but lr
Temperatures lower than 0C "1fclrlro Temperatures above 0C may be used. Depending on the purpose, it can be applied to either a development process that forms a silver image (black and white photographic process) or a color photographic process that consists of a development process that forms a dye image. can.

For details, see Research Disclosure Vol. 17/7A Hiro J, pages 1r to λ, Vol. 117 A/17.
Development processing can be carried out by the method described in the left column and right column of page 631 of 1.

The photosensitive material of the present invention exhibits particularly remarkable effects when a black and white developer preferably having a low IPU is used.

The black and white developer contains known developing agents such as dihydroxybenzenes (e.g. hydroquinone), 3-pyrazolidones (e.g. /-phenyl-3-pyrazolidone), and aminephenols (e.g. N-methyl-p-aminephenol). They can be used alone or in combination. Maf
The effect is remarkable when the pH is between 7.j and 2.2.

(Example) The present invention will be illustrated below with reference to Examples, but the present invention is not limited thereto.

(Example 1) (1) Preparation of photosensitive silver halide emulsion Potassium bromide, potassium iodide, and silver nitrate were added to an aqueous gelatin solution with vigorous stirring. (AgI=≠Morti) was prepared. Thereafter, it was washed with water by a conventional precipitation method, and then chemically sensitized by a gold/sulfur sensitization method using chloroauric acid and thiosulfuric acid (IJ) to obtain a photosensitive iodobromide emulsion At-. Silver halide emulsion B was prepared in the same manner as silver halide emulsion A except that the amount of potassium iodide and the temperature of preparation were adjusted to have the structure shown in Table 1.

(2) Preparation of coated sample Each layer of the following formulation was sequentially provided on a triacetyl cellulose support from the support side to prepare a sample of ~2μ. For details, the groove bottom is marked on the first garment.

(Emulsion layer-1) Binder: Gelatin ♂, j? /m2 Coated silver amount: r, J t/71
2m Fabric aid: )” Decylbenzenesulfonic acid sodium salt 0.1m9/1rL2 poly p-
Potassium styrene sulfonate salt No. 7 to 2 (surface protective layer) Binder: Gelatin 0.7? /rrL2
Coating aid: N-oleoyl-N-methyltauric acid sodium salt 0.2m9/rrL2 Matting agent: Polymethyl methacrylate fine particles (average particle size 3μ) 0. /31n9/m2 (3) Sensitometry After applying these samples at a temperature and humidity of 2j0cbr%RH7
Stored for days. Pass each sample through an optical wedge
After exposure for 7710 seconds with Lux's tungsten light,
Then, it was developed with the following developer for 7 minutes at 00C. The fog density was 0.0 for the fixed, washed, and dried sample. / Exposure at a point with high optical density! (βogEo, 1)
and the exposure amount at a point where o, r optical density is higher than fog density <
Gamma was determined using logEo, g). The formula for determining gamma is the following formula 9.

l o g EO, g l o g Eo, t(4)
Measurement of Graininess Graininess was evaluated by rms graininess measured at an aperture diameter of atμ (however, at optical densities o and r). rm
Regarding graininess, T. H. James (T, H.
, James) editor The Theory of the Photographic Process
the Photographic Processes
s) (/def7, Macmilfan
) Company) 6/T1, page 420.

(5) Swelling rate The total thickness (D1) of the total hydrophilic colloid layer upon drying and to
Measure the film thickness (D2) of 'c' after immersing it in distilled water for 5 minutes, and calculate the ratio by (D2-DI)/D1x10O.

Developer solution methol λ and sodium sulfite 100? hydroquinone
! V Borax / (7E (
2029 Add water /l fixer ammonium thiosulfate -〇0. Of Sodium Sulfite (Anhydrous) 20. Ofboric acid
r,ot ethylenediaminetetraacetic acid disodium 0. / to aluminum sulfate /! , Of sulfuric acid (/rN)
J, Of glacial acetic acid
Add 2 cups of water
/, 0l (pH adjusted to φ, ko) Samples in the table above≠~6.10~/2 compared to samples /6~/
It can be seen that the graininess is greatly improved when I, here~λ≠. However, at that time, the gamma also decreases as the temperature increases, and if left as is, the product will have no commercial value. However, at this time, when a polyoxyethylene surfactant was added and at the same time a membrane with a swelling rate of 200% or more was obtained (Sample 13,
/6~/r and sample/≠, l! It is clear that the gamma can be increased without significantly impairing the graininess.

(Example 2) The following experiment was conducted using silver halide emulsions B and C described in Example 1.

Preparation of a coating sample, sensitometry, measurement of granularity, and measurement of swelling ratio were carried out in accordance with Example 1.

[Brief explanation of drawings]

Figure 1 shows all the results plotted for the samples in Table 1. The horizontal axis represents graininess, and the vertical axis represents gamma. Comparative samples of Example 1 are indicated by white circles, and samples of the present invention are indicated by black circles. Figure 2 plots the results for the samples in Table 2. The horizontal axis represents graininess, and the vertical axis represents gamma. The comparative sample of Example 2 is represented by a white circle, and the sample of the present invention is represented by a black circle.

Claims (1)

[Scope of Claims] A silver halide emulsion having at least one photosensitive silver halide emulsion layer on a support, the emulsion of the emulsion layer containing 8 mol% or more of iodine, A silver halide photographic light-sensitive material characterized in that a polyoxyethylene surfactant is contained in at least one layer on a support, and the swelling ratio of the total film thickness is 200% or more. Swelling rate: Total thickness of the total hydrophilic colloid layer when dry (D_1
) and immersed in distilled water at 20°C for 5 minutes, the film thickness (D_2) of this is measured and determined by (D_2-D_1)/D_1×100%.