JPH01188849A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To improve the effect of promoting development of the title material by incorporating at least one kind of a polyhydroxybenzene compd. or a polymer having a specified repeating unit and/or a dextran in the emulsion layer and/or the another hydrophilic colloid layer of the sensitive material. CONSTITUTION:At least one kind of the polyhydroxy benzene compd. and the polymer having the repeating unit shown by formula I and/or the dextran are incorporated in the emulsion layer and/or the another hydrophilic colloid layer of the sensitive material. In formula I, R<1> is hydrogen atom or alkyl group, R<2> and R<3> are each hydrogen atom or aryl group, L is (m+1) valent bonding group, (n) is 0 or 1, (m) is 1 or 2. Thus, the excellent development processing and pressure resisting property of the sensitive material are obtd.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to a silver halide photographic light-sensitive material, and particularly to a silver halide photographic light-sensitive material having excellent development progress and pressure resistance. .

(Prior art) In general, promoting the progress of development in silver halide photographic materials (hereinafter simply referred to as "sensitized materials") shortens the time it takes to obtain the desired image, which is a major factor in handling the materials. It is an advantage.

As a material that accelerates the progress of development, dextran is disclosed in U.S. Pat.
1st prize for polyacrylamide was U.S. Patent No. 3,271,15.
8, 3,514.289, etc.

However, in a light-sensitive material whose development is simply accelerated with dextran, the sensitivity changes greatly due to pressure, which is unfavorable in terms of image quality.

Pressure is applied to photosensitive materials during transportation and cutting during the manufacturing process. Furthermore, in handling, it is unavoidable that pressure is applied either manually or mechanically during exposure and development.

When pressure is applied to the sensitive material in this manner, pressure is applied to the halide grains using gelatin, which is a binder for the silver halide grains, or a polymeric substance as a medium.

When pressure is applied to silver halide grains, blackening or desensitization that does not correspond to the amount of exposure may occur. For example, K, B, M
ather, J, Opt, Soc, Am,, 3 8
, 1 0 5 4 (I948) and P. Fae
lens, J, Phot, Sci, 2. 105(
I954) and others. As a means of improving density changes caused by pressure, methods include methods of incorporating plasticizers such as polymers and emulsions, methods of reducing silver halide emulsion layers and silver halide/gelatinization in sensitive materials, etc. A method is known in which the pressure is relieved before it reaches the particles.

British Patent No. 738,618 describes a heterocyclic compound in British Patent No. 738,618.
No. 38,637 contains alkyl phthalate, No. 738,
No. 639 includes alkyl esters, and U.S. Pat.
No. 0.404 contains polyhydric alcohol, No. 3, 12.1,
No. 060 discloses a method using carboxyalkylcellulose, JP-A No. 49-5017 discloses a method using paraffin and a carbonate salt, and JP-B No. 53-28086 discloses a method using an alkyl acrylate and an organic acid.

However, the method of adding a plasticizer reduces the mechanical strength of the emulsion layer, so there is a limit to the amount of plasticizer that can be used.If the silver halide/gelatin ratio is increased, the development progress will be delayed, and development using polyacrylamide or dextran, etc. This reduces the promoting effect.

As described above, in light-sensitive materials using compounds such as polyacrylamide and textolan, which have a development accelerating effect, image deterioration due to pressure is large and they have not been fully utilized.

(Object of the Invention) An object of the present invention is to provide a light-sensitive silver halide photographic material having excellent development progress and excellent pressure resistance.

(Disclosure of the Invention) As a result of extensive research, the present inventor has discovered that in a photographic light-sensitive material having at least one light-sensitive silver halide layer on a support, the emulsion layer and/or other hydrophilic colloid layer contains contains at least one type of polyhydroxybenzene compound, and contains a polymer containing a repeating unit represented by the general formula (r) and/or dextran in the emulsion layer and/or other hydrophilic colloid layer. The above objectives could be achieved by using the characteristic silver halide photographic material.

General formula (I) % formula %) (In the formula, R1 is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, Rx and Rx are each a hydrogen atom, a substituted or unsubstituted alkyl group having 10 or less carbon atoms, They represent an aryl group or an aralkyl group, and may be the same or different.

Further, R2 and R3 may be bonded to each other to form a nitrogen-containing heterocycle together with the nitrogen atom, and L is an m+1-valent linking group. n is 0 or l, and m is 1 or 2. ) Techniques for adding polyhydroxybenzene compounds to sensitive materials are disclosed in JP-A-54-40629, JP-A-56-1936, JP-A-62-21143, and JP-A-62-26913.
It is disclosed in No. 7, etc.

In particular, in JP-A No. 62-21143, 5x per mole of silver
It has been shown that the presence of polyhydroxyhenzene at concentrations below 20 molar may reduce the sensitivity increase due to pressure. With negative development system,
This is a special system that uses monodisperse cubic grains of silver iodobromide.

In the present invention, silver halide grain shapes are not only cubic, but also octahedral, tabular (aspect ratio of 5 or more), twin slab-like (
(aspect ratio of 5 or less), the presence of polyhydroxybenzene when the development progress is improved by dextran and/or a polymer having repeating units represented by the general formula (I) in rounded amorphous particles. This improves sensitivity changes due to pressure on the photosensitive material.

(Specific structure of the invention) A specific configuration of the present invention will be explained in detail.

The polyhydroxybenzene compound of the present invention preferably has one of the following structures.

OH X and Y are respectively -H1-OH and halogen atom -OM
(M is an alkali metal ion), -alkyl group, phenyl group, amino group, carbonyl group, sulfone group, sulfonated phenyl group, sulfonated alkyl group, sulfonated amino group, sulfonated carbonyl group, carboxyphenyl group,
Carboxyalkyl group, carboxyamino group, hydroxyphenyl group, hydroxyalkyl group, alkyl ether group, alkylphenyl group, alkylthioether group,
or a phenylthioether group.

More preferably, -Hl-0H1-C1, Br,
C0OH, CHzCHzCOOH.

CHs, CHzCHi, CH(CHsh-C
(CH3)3, -0CH3, CHO, -3OsNa.

It may be.

Particularly preferable representative compound examples are A-(I) A=(2)
A −+31H A −(41A −(51A −(61A−(7)
A-(81A-(910I(OI( A-01A-Qll A-OnA-αIA
-(I41A -09 A -(II A -+171
A -CI+1 Substituents x, y of the present invention
and compounds are not limited to those listed above.

The polyhydroxybenzene compound of the present invention may be added to the emulsion layer of the sensitive material, or may be added to a layer other than the emulsion layer. Further, it may be added in one or more layers or in a plurality of layers.

The amount added is 3 g or less per log of the sum of the weight of gelatin in the sensitive material and the weight of the polymer and/or dextran containing repeating units represented by general formula (I), but
The amount added is preferably 0 to 1 g, especially 100 to 700 g.
■ is preferred.

In the general formula (I), R1 is a hydrogen atom or an alkyl T:1'! f- is preferably a hydrogen atom or a methyl group.

12.113 each represents a hydrogen atom, a substituted or unsubstituted alkyl group having io or less carbon atoms, a γ-aryl group, or an aralkyl &'t- group, which may be the same or different;
, Substituents include hydroxyl group, lower alkoxy group, halogen atom, amide group, cyano group, sulfonic acid group, carboxylic acid group, etc.
iHydrogen atom, methyl! &, ethyl group and phenyl group are preferred, and among these, hydrogen atom is most preferred.

L represents a covalent linking group, as an example of a group having 7 to 1 carbon atoms.
Examples include covalent groups obtained by combining zero alkylene groups, arylene groups, or a combination thereof with ether bonds, ester bonds, amide bonds, etc.

n represents 0 residue*ij/, and O is preferable.

m represents 1 or 0, and 0 is preferred.

- Of the ethylenically unsaturated seven-pointers constituting the repeating wind position represented by the pitch type (ri), specific examples of preferred metalwork are listed below: j -/ C) T2=CI-i 0NH2 ■-- CH2= CH C0NHCH3 -J CH2=CH C0NHC2H5 1-≠ cH2=cH Goose C0N) IC) 120H (-, < ■=7 CI (3 ■ CH2=C C0N) T2 -r C) (= ■ CH2= C Healing C0NI- TCH3 -P Ha CH3 CH2=C CONI-IC)T20C)T3 1-//C0NI-i-C-CHzSOsNa l-l3 1-/Col3 No.i-/J l3 T-/μ CH2=CH CON (CHs )2 1-/A j-/ 7 cH2=cH C0NI-IC(C)I3)2! -7! l3 CH2=C CON HCH2CH20H l-/lil3 ■ ■--〇0NH2 The repeating unit represented by the general formula (I) has two or more types of monomer bending positions in order to exhibit multi@-ability as a heavy structure. It may be included.

The polymeric structure of the present invention has a monomer represented by the general formula (I) as a polymer constituent unit, and has a polymer structure of 70 mol or more, preferably 10 mol or more, more preferably 0 mol or more, and has the following formula (II). It's a party.

In the formula, X represents a molar percentage, and preferably 70 to ioo.

The formula contains copolymerizable ethylenically unsaturated monomers]
F represents the combined monomer potential.

Examples of ethylenically unsaturated monomers in the preferred heavy bodies of the present invention include ethylene, propylene, l-7'tene, isobutyne, styrene, chloromethylstyrene, hydroxymethylstyrene, sodium vinylbenzenesulfonate,
Sodium vinylbenzyl sulfonate, N, N, N-)rifthyl-N-vinylbenzylammonium chloride, N
, N-dimethyl-N-benzyl-N-vinylbenzylammonium chloride, α-methylstyrene, vinyltoluene, μm vinylpyridine, covinylpyridine, benzylvinylpyridinium chloride, N-vinylacetamide, N-vinylpyrrolidone.

non-vinyl-comethylimidazole, monoethylenically unsaturated esters of aliphatic acids (e.g. vinyl acetate, allyl acetate), ethylenically unsaturated mono- or dicarboxylic acids and their salts (e.g. acrylic acid, methacrylic acid, itaconic acid) , maleic acid, sodium acrylate, potassium acrylate, sodium methacrylate), maleic anhydride e12, esters of ethylenically unsaturated monocarboxylic or dicarboxylic acids (e.g. n-butyl acrylate, n-hexyl acrylate, hydroxyethyl Acrylate, cyanethyl acrylate, N.

N-diethylamine ethyl acrylate, methyl methacrylate, n-butyl methacrylate, benzyl methacrylate, hydroxyethyl methacrylate, chloroethyl methacrylate, methoxyethyl methacrylate%
N,N-diethylaminoethyl methacrylate, N,N
, N-) riethyl-N-methacryloyloxyethylammonium, -) luenesulfonate, N,N-diethyl-N-methyl-N-methacryloyloxyethylammonium p-toluenesulfo+-), dimethyl itacon, monobenzyl maleate In addition to Esther), etc.
Special υ: 1 Akira! t-/J/9J7, JP-A-Sho r7-/04
'P27, JP-A-1996-1444, and other gelatin-reactive seven-spots are disclosed. In addition, the subunit of the present invention may contain two or more types of monomer units as one unit in order to exhibit a multifunctional function. Things can be mentioned. (The number of degree of gravity indicates the molar percentage.) Compound Example 1 [3-(+) Compound Example ・[3-(2) CI-13 0NHz Chemical Compound Example B-(SuH3 1 Hishimono gAI B-(4-) CONITCIT3co2p1 1hi compound example B-(5) H3 1hi compound example (3-(also) H3 ・ Chemical compound example B-(7) Chemical compound example B -(%) H3 Chemical compound example 8-('1) Compound full 6-(+o) Chemical compound example (3(+1) H3 C0NI(2C0N)iQ(2N1・TCOCH20T
2 SOzz C compound example 8-(I2) The weight average molecular weight (Mw) of the monomer having repeating units is preferably 7,000 to 100, more preferably 7,000 to 70,000, and more preferably 7,000 to 70,000. The amount of the polymer added can be selected arbitrarily, but the optimum amount for increasing the covering power varies depending on the type of photographic emulsion. However, it is generally 500 .mu./m or more, preferably 1 g/po or more and 5 g/rrr or less.

In the present invention, the dextran added to the photographic emulsion layer is
Dextran-producing bacteria such as Leuconostoc and Mesenteroides, or native dextran obtained by acting on sucrose solution with dextran sucrase isolated from the culture solution of these bacteria, are reduced in molecular weight by partial decomposition polymerization using acids, alkalis, and enzymes. This is what I did. The weight average molecular weight of desquitran used in the present invention is to, oo.

from 300,000, preferably from 15,000 to
o, ooo, more preferably 20.000 to 70.0
It is 00.

The polymer and/or dextran having repeating units represented by the general formula (I) used in the present invention may be used in an amount of 5 to 50% by weight, especially 30 to 4% by weight, based on the total binder in the photographic emulsion.
It is preferable to add it in an amount of 0% by weight.

The polymer used in the present invention may be contained in any photographic emulsion layer, but it is preferably contained in all photographic emulsion layers.

More preferably, the polymer density in the photographic emulsion layer adjacent to the support (weight of the polymer used in the present invention/weight of the binder in the layer to which the polymer is added) is lower than the polymer density in the other photographic emulsion layers. Smaller is better.

Even better results can be obtained if the non-photosensitive gelatin layer adjacent to the photographic emulsion layer also contains the polymer of the present invention.

When the polymer of the present invention is added to each layer of a photographic material, it is preferred that the binder ratio of the polymer/added layer is not significantly different from that of the adjacent layer.

In particular, the polymer density in the photographic emulsion layer adjacent to the support is lower than the polymer density in other photographic emulsion layers, and is not more than 30% by weight of the binder in the photographic emulsion layer adjacent to the support. is preferred.

The polymers of the invention may be added to the outermost layer of non-photosensitive gelatin, in which case the outermost layer preferably has a lower polymer density than any other layer of the photographic material.

The polymer may be added to the emulsion at any time, but it is suitable to add it after the second ripening and before coating.

Although the polymer may be added as a powder, it is convenient to use it as a 5-20% aqueous solution.

As the silver halide in the photosensitive silver halide emulsion used in the present invention, silver chloride, silver chlorobromide, silver bromide, silver iodobromide, and silver chloroiodobromide can be used, but iodine is preferably used. Silver bromide is used. Here, the Venus of silver iodide is preferably in the range of 30 mol% or less, particularly 15 mol% or less, and the distribution of iodine in the silver iodobromide grains may be uniform, and
The average particle size, which may be different between the inside and the surface, is preferably 0.4 μm or more. Especially 0.5-2
It is preferable that it is 0 μm. The particle size distribution may be narrow or wide.

The silver halide grains in the emulsion may have regular crystal shapes such as cubic, octahedral, tetradecahedral, rhombic dodecahedral, or irregular crystal shapes such as spherical, plate-like, potato-like, etc. It may consist of a mixture of particles of various crystal forms, which may have irregular crystal forms or composite forms of these crystal forms. Further, the particles may be tabular grains having a particle diameter of 5 times or more the particle thickness.

Further, among tabular silver halide grains, monodisperse hexagonal tabular grains are particularly useful grains.

The details of the structure and manufacturing method of the monodisperse hexagonal tabular grains referred to in the present invention are as described in Japanese Patent Application No. 61-299155, but briefly stated, the emulsion consists of a silver halide grain consisting of a dispersion medium and silver halide grains. An emulsion in which 70% or more of the total projected area of the silver halide grains has a ratio of the length of the side having the maximum length to the length of the side having the minimum length of 2 or less. It is square and is occupied by tabular silver halide having two parallel surfaces as outer surfaces,
Further, the coefficient of variation of the grain size distribution of the hexagonal tabular silver halide grains [the value obtained by dividing the variation (standard deviation) of the grain size expressed by the circular diameter of its projected area by the average grain size] is 20% or less. It has the paternity of subdivision 11. Although the crystal structure may be --like, it is preferable that the inside and outside have different halogen compositions, and may have a layered structure.Also, it is preferable that the grains contain reduction-sensitized silver nuclei. preferable.

The silver halide grains can be produced through nucleation-Ostwald ripening and grain growth,
The details are as described in Japanese Patent Application No. 61-299155.

Further, the silver halide grains used in the present invention may be used by forming a core/shell type reduced-layer emulsion using the hexagonal tabular grains as a core. In this case, regarding the chemical sensitization method of the core, the method of attaching the shell, and the development with a developer containing a silver halide solvent, Japanese Patent Application Laid-Open No. 59-1335
No. 42, British Patent No. 145,816.

The thickness of the shell in this case is preferably 1 to 100 lattices, preferably 5 to 50 lattices.

The hexagonal tabular grains used in the present invention may have dislocation lines inside. Whether or not there are dislocation lines and the number thereof can be determined by observing with a low-temperature (liquid He temperature) transmission electron microscope. It can be determined by

Hexagonal tabular grains containing dislocation lines are formed by adding iodide salt during the crystal growth period of the hexagonal tabular grains or using the hexagonal tabular grains as seed crystals and adding iodide salt during a certain period of the crystal growth period when the crystals are further grown. can do. In this case, a period of time ranges from an instantaneous period (approximately 1/2 second) to the entire crystal growth period. It is formed when the difference in the legal content of silver iodobromide is 5 mol% or more.

In the present invention, the light-sensitive silver halide emulsion may be a mixture of two or more types of silver halide emulsions, and the emulsions to be mixed may differ in grain size, halogen composition, sensitivity, etc. Substantially non-light sensitive emulsion (
(The surface or interior may or may not be covered) may be mixed and used, or may be separated into separate layers (for details, see US Pat. No. 2,996,382, No. 3. 3
97.987 etc.) 0 For example, a spherical or potato-shaped photosensitive emulsion and a photosensitive silver halide emulsion consisting of tabular grains with a grain size of 5 times or more than the grain thickness are placed in the same layer or It may be used in different layers as described in Publication No. 58-127921. When used in different layers, the photosensitive silver halide emulsion consisting of tabular grains may be on the side closer to the support, or vice versa. May be on the far side.

The photographic emulsion used in the present invention is P, Glafkide.
Chemie et Ph1sique l by s
'photographique (Paul Ma
nte1, 1967), G, F, Duffi
Written by n Photographic1! mulsion
Chemistry (the Focal P
ress, 1966), V, L, Zel
Makin5 and Cod by iksan at al
ing Photographic Emulsi
on (The Focal Press, 1
964) Japanese Patent Publication No. 58-127921 and 5B-1
It can be prepared using the method described in Japanese Patent No. 13926 and the like. That is, any of the acidic method, neutral method, ammonia method, etc. may be used, and the method for reacting the soluble root salt with the soluble halogen salt may be a one-sided mixing method, a simultaneous mixing method, or a combination thereof. .

A method in which silver halide grains are formed in an excess of silver ions (so-called back mixing method) can also be used. As one type of simultaneous mixing method, a method in which PAg in the liquid phase in which silver halide is produced can be kept constant, that is, a so-called Chondrald double jet method can also be used. According to this method, a silver halide emulsion consisting of silver halide grains having a regular crystal shape and a nearly uniform grain size can be easily changed.

Even if the crystal structure of silver halide grains is similar to the inside, there are also grains with a layered structure with different inside and outside, British Patent No. 635.841, U.S. Patent No. 3,622,3
It may be of the so-called conversion type as described in No. 18, or silver halides of different compositions may be joined by epitaxial joining, and for example, silver halide, silver oxide, silver halide, etc. It may be bonded with a compound other than the silver compound or with a compound other than the silver compound. Cadmium salts, zinc salts, lead salts, thallium salts are , an iridium salt or a complex salt thereof, a rhodium salt or a complex salt thereof, an iron salt or an iron complex salt, etc. may be present together.

In addition, during particle formation, a so-called halogenated solvent such as ammonia, thioether compound, thiazolidine-2-thione, tetrasubstituted thiourea, rhodanpotash, rhodanammonium, or amine compound may be present to control particle growth.

The silver halide emulsion used in the present invention may or may not be chemically sensitized. As a chemical sensitization method, known methods such as sulfur sensitization method, reduction enhancement method, and noble metal enhancement method can be used, and these may be used alone or in combination.

Among the noble metal sensitization methods, the gold sensitization method is a typical method and uses a gold compound, mainly a total complex salt. There is no problem in containing complex salts of noble metals other than pure metals, such as platinum, palladium, and iridium.

As the sulfur sensitizer, in addition to the sulfur compounds contained in gelatin, various sulfur compounds such as thiosulfates, thioureas, thiazoles, rhodanines, etc. can be used.

As the reduction sensitizer, stannous salts, amines, formamidine sulfinic acid, silane compounds, etc. can be used.

The photographic emulsion used in the present invention can contain various compounds for the purpose of preventing fog during the manufacturing process, storage, or photographic processing of the light-sensitive material, or for stabilizing photographic performance. namely, azoles (e.g. benzothiazolium salts, nitroimidazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, nitroindazoles, benzotriazoles, aminotriazoles, etc.) - mercapto compounds (e.g. mercapto thiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, mercaptotetrazoles (especially I-phenyl-5-mercaptotetrazole), mercaptopyrimidines, mercaptotriazines, etc.): for example, thioketo such as oxadorinthione Compounds; Azaindenes (e.g. triazaindene, tetraazaindene M (especially 4-hydroxy substituted (I, 3, 3a, 7) tetraazaindene), pentaazaindene, etc.); benzenethiosulfonic acid, benzenesulfine Many compounds known as antifoggants or stabilizers can be added, such as acids, benzenesulfonamides, etc.

Specifically, RESEARCII DISCLO5IIR
E Item 17643■ (December 1978 issue P
, 24-P, 25) or in the literature cited therein.

In particular, nitrone and its derivatives described in JP-A-60-76743 and JP-A-60-87322, JP-A-60-8
Mercapto compound described in Publication No. 0839, JP-A-57
The heterocyclic compound described in Japanese Patent No. 164735, and the complex salt of the heterocyclic compound and silver (for example, 1-phenyl-5-mercaptotetrazole!) can be preferably used.

The photosensitive silver halide emulsion of the present invention may be spectrally sensitized to relatively long wavelength blue light, green light, red light or infrared light using a sensitizing dye. Dyes such as complex cyanine dyes, complex merocyanine dyes, holopholar dianine dyes, styryl dyes, hemicyanine dyes, oxonol dyes, and hemioxonol dyes can be used.

Useful sensitizing dyes for use in the present invention include, for example, RESEA
RCHDISCLO3URE Ite+ll 7643
■-A section (December 1978 P, 23), same 1te
ml Section 831X (August I979 P, 437) or in the literature cited.

The sensitizing dye can be used at any stage of the photographic emulsion manufacturing process, or at any stage after manufacturing until immediately before coating. Examples of the former include a silver halide grain formation process, a physical ripening process, and a chemical ripening process.

The photographic emulsion layer or other hydrophilic colloid layer of the light-sensitive material produced using the present invention includes coating aids, antistatic 1F, 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 oxidation, sensitization, etc.

For example, saponins (steroids), alkylene oxide derivatives (e.g. polyethylene glycol, polyethylene glycol/polypropylene glycol condensates, polyethylene glycol alkyl ethers or polyethylene glycol alkyl aryl ethers, polyethylene glycol esters, polyethylene glycol alkyl ethers, polyalkylene glycol Nonionic interfaces such as glycol alkylamines or amides, polyethylene oxide adducts of silicone), glycidol derivatives (e.g. alkenylsuccinic acid polyglycerides, alkylphenol polyglycerides), fatty acid esters of polyhydric alcohols, alkyl esters of sugars, etc. Activator: Alkyl carboxylate, alkyl sulfonate, alkylbenzene sulfonate, alkylnaphthalene sulfonate, alkyl sulfate, alkyl phosphate L, N-acyl-N-alkyl taurine, sulfosuccinate, sulfonate Anionic surfactants containing acidic groups such as carboxy groups, sulfo groups, phospho groups, sulfate ester groups, phosphate ester groups, such as alkyl polyoxyethylene alkyl phenyl ethers and polyoxyethylene alkyl phosphate esters; Ampholytic surfactants such as amino acids, aminoalkyl sulfonic acids, aminoalkyl sulfates or phosphates, alkyl betaines, amine oxides; alkylamine salts, aliphatic or aromatic quaternary ammonium salts In, pyridinium, imidazo Cationic surfactants such as heterocyclic quaternary ammonium salts such as lithium, and phosphonium or sulfonium salts containing aliphatic or heterocycles can be used. These are written by Ryohei Oda et al. [Surfactants and their Applications J (Maki Shoten, 196/I), Hiroshi Horiguchi, "New Surfactants" (Sankyo Publishing ■, 1975) or "Matsuku Cations De Tergent Ande. "Marji Finers" (Matsufucation Divisions, MC Publishing Cumber 1-1985)
(rMccuLcheon's Deterrents
& Eaulsifiers” (McCutcheon
Divisions, MC Publishing
Co, I985) ), JP-A-60-7674
No. 1, Patent Application No. 61-13398, No. 61-16056
No. 61-32462, etc.

As antistatic agents, in particular, JP-A-59-74554,
No. 60-80849, Japanese Patent Application No. 60-249021,
Fluorine-containing surfactant or polymer described in JP-A-61-32462, JP-A-60-76742, JP-A-60-80
No. 846, No. 60-80848, No. 60-80839
No. 60-76741, No. 58-. No. 208743, Japanese Patent Application No. 61-13398, No. 61-16056,
No. 61-32462, etc. Nonionic surfactant or JP-A-57-20454
Conductive polymers or latexes (nonionic, anionic, cationic, amphoteric) described in Japanese Patent Application No. 61-32462 may be preferably used. Examples of inorganic antistatic agents include ammonium, alkali metal, and alkaline earth metal halogen salts, nitrates, persalt salts, sulfates, acetates, phosphates, and thiocyanates.
Composite oxides prepared by doping conductive tin oxide, zinc oxide, or these metal oxides with antimony or the like, as described in Japanese Patent No. 7-118242, can be preferably used.

In the present invention, as a matting agent, a homobomer of polymethyl methacrylate or a polymer of methyl methacrylate and methacrylic acid, an organic compound such as starch, or fine particles of an inorganic compound such as silica, titanium dioxide, sulfuric acid, strontium, or barium can be used. can. The particle size is preferably 1.0 to 10 μm, particularly 2 to 5 μm.

The surface layer of the photographic light-sensitive material of the present invention contains silicone compounds described in U.S. Pat. No. 3,489.576 and U.S. Pat. In addition, paraffin wax, higher fatty acid esters, starch derivatives, etc. can be used.

Polyols such as trimethylolpropane, bentanediol, butanediol, ethylene glycol, and glycerin can be used as plasticizers in the hydrophilic colloid layer of the photographic material of the present invention. Furthermore, the hydrophilic colloid layer of the photographic material of the present invention preferably contains a polymer latex for the purpose of improving pressure resistance. Polymers include homopolymers of alkyl esters of acrylic acid or copolymers with acrylic acid, styrene-
Butadiene copolymers, polymers or copolymers consisting of monomers having active methylene groups can be preferably used.

The photographic emulsions and non-photosensitive hydrophilic colloids of the present invention may contain inorganic or organic hardeners.

For example, chromium salts (chromium alum), aldehydes (
formaldehyde, glitaraldehyde, etc.), N-
Methylol compounds (such as dimethylol urea), dioxane derivatives, active vinyl compounds (I,3,5-)lyacryloyl-hexahydro-S-triazine, bis(vinylsulfonyl) methyl ether, N,N'-methylenebis-[β- (vinylsulfonyl)propionamide], active halogen compounds (such as 2,4-dichloro-6-hydroxy-5-1-riazine), mucohalogen acids, etc. can be used alone or in combination. Among them, JP-A No. 53-41220, No. 53-57257, No. 5
Preferred are the active vinyl compounds described in US Pat. No. 9-162,546 and US Pat.

When the photosensitive material of the present invention is used as an X-ray solvent, the hydrophilic colloid layer is preferably hardened with such a hardening agent so that the swelling ratio in water is 200% or less, particularly 150% or less. .

As the binder or protective colloid that can be used in the emulsion layer or intermediate layer of the light-sensitive material of the present invention, it is advantageous to use gelatin, but other hydrophilic colloids can also be used.

For example, gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein; cellulose derivatives such as hydroxyethyl cellulose, carboxymethyl cellulose, and cellulose sulfates; sodium alginate; polyvinyl alcohol, polyvinyl alcohol partial acetal, and A wide variety of synthetic hydrophilic polymeric materials can be used, such as single or copolymers of -N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyvinylimidazole, polyvinylpyrazole, and the like.

As the gelatin, in addition to lime-treated gelatin, acid-treated gelatin or enzyme-treated gelatin may be used, and hydrolysates of gelatin may also be used.

In addition to the light-sensitive silver halide emulsion layer, the silver halide photographic material of the present invention may have non-light-sensitive layers such as a surface protective layer, an intermediate layer, and an antihalation layer.

There may be two or more silver halide emulsion layers, and the sensitivity, gradation, etc. of the two or more silver halide emulsion layers may be different.
Further, one or more silver halide emulsion layers or non-photosensitive layers may be provided on both sides of the support.

-A cellulose triacetate film is preferred as the support for the acetic material, and may be colored or uncolored for antihalation purposes.

As the support for X-ray photography, polyethylene terephthalate film or cellulose triacetate film is preferred;
In particular, it is preferably colored blue.

In order to improve the adhesion with the hydrophilic colloid layer, the surface of the support is preferably subjected to corona discharge treatment, claw discharge treatment, or ultraviolet irradiation treatment, or styrene-butadiene-based latex, vinylidene chloride-based latex, etc. An undercoat layer may also be provided consisting of,
A gelatin layer may be further provided on top of the gelatin layer. Further, an undercoat layer may be provided using an organic solvent containing a polyethylene swelling agent and gelatin. These undercoat layers can be surface-treated to further improve their adhesion to the hydrophilic colloid layer.

For photographic processing of the light-sensitive material of the present invention, for example, Research Disclosure (RESEARCHD[5CLO5U
Any of the known methods and known treatment liquids as described in RE) No. 176, pages 28-30 (RD-17643) can be applied. Depending on the purpose, this photographic processing may be either photographic processing that forms a recorded image (black and white photographic processing) or photographic processing that forms a dye image (color photographic processing), and the processing temperature is usually I8. °C
to 50°C, but temperatures below 18°C or above 50″C may also be used.

For example, developers used in black-and-white photographic processing can include known developing agents.

As developing agents, dihydroxybenzenes (e.g. hydroquinone), 3-pyrazolidones (e.g. l-
phenyl-3-pyrazolidone), aminophenols (
For example, N-methyl-p-aminophenol), etc.
Can be used alone or in combination. The photographic processing of the light-sensitive material of the present invention can also be carried out using a developer containing imidazoles as a silver halide solvent as described in JP-A-57-78535. Also, JP-A-58-3
It can be processed with a developer containing a silver halide solvent and an additive such as indazole or triazole as described in No. 7643. The developing solution generally contains other known preservatives, alkaline agents, pH buffers, antifoggants, etc., and, if necessary, a solubilizing agent, a color toning agent, a development accelerator,
Surfactants, antifoaming agents, water softeners, hardening agents (eg, glutaraldehyde), viscosity-imparting agents, and the like may also be included.

As the constant @ solution, one having a commonly used composition can be used. As the fixing agent, in addition to thiosulfates and thiocyanates, organic sulfur compounds known to be effective as fixing agents can be used.

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

The present invention will be explained in more detail with reference to Examples below.

Example 1 In a container containing 25 g of potassium bromide, 9 cc of 2N potassium thiocyanate, and 24 g of gelatin in Ir1 water, a silver nitrate aqueous solution and odor were added using the usual ammonia method. An aqueous solution of potassium chloride was added using a double jet method to obtain an average particle size of 1.OI.
A thick plate-like silver bromide emulsion with a relatively amorphous shape of Im was prepared, and chemically sensitized using sodium periosulfate and chloroauric acid to obtain a photosensitive silver bromide emulsion with ρAg of 8.6 and pH of 6.4. Emulsion (A) was obtained. A photosensitive silver iodobromide emulsion with an immersion content of 6 mol % and an average grain size of 0.6 μm is obtained by making 9 g of potassium iodide exist in the initial solution, and performing grain formation and chemical sensitization in the same manner as in emulsion (A). (B) and the presence of 15 g of potassium iodide in the initial solution, with a solubility content of 10 mol % and an average particle size of 1
．． A 0μ photosensitive silver iodobromide emulsion (C) was obtained.

To a container containing potassium bromide and 25g gelatin in 11g of water, add silver nitrate aqueous solution and potassium bromide and potassium iodide aqueous solution by double jet method while maintaining PAg at 8.7. A regular octahedral silver iodobromide emulsion with an average grain size of 0.8 μm was prepared, and chemically sensitized using sodium thiosulfate and chloroauric acid to obtain an emulsion with a nominal content of 3 mol% at PAg 8.6 and pH 6.4. A regular octahedral photosensitive silver iodobromide emulsion (D) was obtained.

To a container containing 5 g of potassium bromide and 30 g of gelatin in water 11, a 5% silver nitrate aqueous solution and a mixed aqueous solution of potassium bromide and potassium iodide were added while maintaining the PAg at 9.5, and then the whole 5% of silver nitrate was added by a single jet method, and the remaining 90% of silver nitrate aqueous solution and a mixed aqueous solution of potassium bromide and potassium iodide were added by a double jet method while maintaining PAg at 8.1. Projected area diameter 1.3 μm, standard deviation 15%, aspect ratio 6.
A tabular silver bromide emulsion of No. 5 was prepared and chemically sensitized using sodium thiosulfate and chloroauric acid to give a pAg of 8.6.
A photosensitive silver iodobromide emulsion with a pH of 6.4 and an immersion density of 6 mol% (
E) was obtained.

8 bowl aspect 12.0 request Halonon's ■ In a container containing 5 g of potassium bromide and 30 g of gelatin, add 5% of the total silver nitrate aqueous solution and bromide while keeping the PAg at 9.5. A potassium aqueous solution was added in a double jet, followed by a single jet addition of 5% of the total silver nitrate, and then the remaining 85% was added while maintaining the pAg at 9.0.
A silver nitrate aqueous solution and a mixed aqueous solution of potassium bromide and potassium iodide were added to prepare a flat plate having a immersion degree of 110 mol %.

Furthermore, the remaining 5% of silver nitrate, potassium bromide, and a highly concentrated potassium iodide aqueous solution were added while maintaining the PAg at 7.5, and the average projected area diameter was 2.2 μm, the standard deviation was 22%, and the aspect ratio was 12.0. A tabular silver iodobromide emulsion with a content of 12 M% was prepared and chemically sensitized using sodium thiosulfate and chloroauric acid to obtain a photosensitive emulsion (F) with p, Ag 8.6, and pH 6.4. Ta.

Samples 1 to 28 were prepared by simultaneously applying the following formulation onto a triacetyl cellulose support that had been subbed in advance from the support layer side.

(Emulsion layer) Amount of coated silver: 3.5 g/Amount of pogelatin: 1.5 g/Ag 1 g Dextran (1.1 million molecules) Hydroquinone listed in Table 1
4-Hydroxy-6methyl-1.3.3a, ? -Tetrazaindene 10■/^gigPolyethylene oxide 8■/Ag1gPolybotacium p
-Vinylbenzene sulfonate 20/881g The addition of sensitizing dyes is listed in Table-1. For the dura mater, the coated sample is held at 25°.
After being stored at C65%RH for 7 days and immersed in distillation at 25°C for 3 minutes, the film thickness was 11! (7) 200±1
It was adjusted to 0% with bis-(vinylsulfonylacetamido)ethane.

(Surface protection N) Gelatin amount 0.8g/M polybotacium ρ-vinylbenzenesulfonate l rng / n
Polymethyl methacrylate fine particles (average size 3μ) Sensitome 1- Coated samples 4 to 28 were stored at 25° C. and 65% RH for 7 days. 20° with developer A exposed for 1/100 seconds using a filter with a wavelength distribution equivalent to sunlight.
C, it was developed for 17 minutes, fixed with fixer A, washed with water, and dried. The series of steps of development, fixing, washing, and drying are collectively referred to as processing hereinafter, and sensitometry was performed on the sample after processing. The progress of development was evaluated by measuring the amount of developed silver in the maximum density area and by the development rate with respect to coating development.

After negative exposure, the coated sample was kept at 25°C and 50% temperature and humidity for 2 hours. A load of 50 g was applied to a 0.1φ sapphire needle, and the needle was slid over the coated sample at a rate of 60 cm/sin to apply pressure to the sample. The emulsion surface of any of the coated samples prepared in the Examples was not destroyed.

After the treatment, the change in density at the scratched area was measured using a microdensitometer with an aperture of 50 μm in the sensitometric fogged area and the areas where the density was fogged +Q and 0, and the scratch resistance was evaluated.

Developer A l-phenyl-3-pyrazolidone 0.5g Hydroquinone 20.0g Ethylenediaminetetraacetic acid disodium dihydrate 2.0g Potassium sulfite 60.0g Boric acid
4.0g potassium carbonate 20
．． 0g sodium bromide 5.0g diethylene glycol Add water to 10g or less to make 1ffi, and adjust pH to 10.0 with sodium hydroxide.

Fixer A Ammonium 1000sulfate 200g Anhydrous sodium sulfite 15g Glacial acetic acid
15.4ad boric acid
7.5g potassium alum 15
g Add water to make In.

From Table 1, it can be seen that the damage resistance deterioration effect of dextran is greatly improved by hydroquinone, and the desired developability is not impaired.

Ura blind charcoal I Coating samples 29 to 38 were prepared with the following layer configurations.

First layer gelatin O, 6g/po 3.6■ from the support
/M Polybotacium p-vinylbenzenesulfonate 9+g/po second layer gelatin 1.0g/n (I75■
/M I CQzCH*SOJ CHzCHtS
OJ26■/Po16■/IHCI 0. 11mg/n
f 3rd layer gelatin 0.4g/rd Voribotacium p-vinylbenzene sulfonate 5/4th layer Emulsion B: 8 layers
1.36g/rrf gelatin
2.0g/rrf 4-hydroxy-6-methyl 1.3.3a,7-chitrazaindene 30mg/ is polyethylene oxide 7■/nr polybotacium p-vinylbenzenesulfonate 50■/Po 5th layer SIN using Emulsion C
4.2g/bogelatin amount
5.5g/bodextran (molecular weight 130,000) 1.8g
/nf4-hydroxy-6-methyl 1.3.3a,7-chitrazaindene 41■/Ipolyethylene oxide 23■/PoCH,OH H1OH Polypotassium p-vinylbenzenesulfonate 88■/rrf Top layer gelatin 0. 8g/rrf Polybotacium p-vinylbenzene sulfonate 6■/I C*F+t
SOt N CHt COO to CJt
The amount of 1.8/ihydroquinone (methanol solvent) added and the layers to which it was added are shown in Table 2.

For the dura mater, the coated sample was stored for 7 days at a temperature and humidity of 25 °C and 65% Rh, and then immersed in distilled water at 25 °C for 3 minutes so that the film thickness was 300% ± 10 of the dry film thickness. Prepared by bis-(vinylsulfonylacetamido)ethane.

For emulsions (B) and (C), dye-1 was added to 230I1 before after-ripening.
g/Ag mole was added.

The treatment and scratch resistance were evaluated in the same manner as in Example-1. The results are shown in Table-2.

As can be seen from Table 2, the scratch resistance is improved as the amount of hydroquinone added increases, but as the amount exceeds 100 μm, the improvement effect with respect to the amount added becomes smaller. Furthermore, it can be seen that hydroquinone is effective no matter what layer it is added to on the support.

Ability 1 Toni 1 Coating sample 39-56 was prepared using emulsion F with the same layer structure as in Example-1. However, instead of dextran, +CIl□-CIl→-C0N11□ was used, and in addition to hydroquinone, polyhydroxyhensen listed in Table 3 was used. Emulsion F is prepared in advance.
230mg of dye=1 1 mol Ag and 12■ of dye-3
After addition of 1 mol Ag, ripening occurred.

Dye-3: After storing the coated sample at a temperature and humidity of 65% Rh for 7 days, the film thickness after immersion in distilled water at 25°C for 3 minutes was 300% ± 10 of the dry film thickness. It was adjusted with bis-(vinylsulfonylacetamido)ethane so that

The coated samples were processed with developer A and fixer A.

Evaluation of scratch resistance was performed in the same manner as in Example-1.

The results are shown in Table-3.

As is clear from Table 3, various polyhydroxydihenzenes have improved scratch resistance without impairing TFI.

soil for 1 ko Coating samples 60 to 63 were prepared with the following layer configurations.

1st layer Emulsion B and Emulsion E are mixed in a ratio of 1:1 silver to produce 1 layer
2.
5g/rri gelatin 3.0g
/rr14-hydroxy-6-methyl-1,3,3a,7-chitrazaindene 30■/Polyethylene oxide 10mg/rrfPolybotacium p-vinylhenzenesulfonate 50mg/ni Second layer Using emulsion F, silver amount 3.5g /rrlgelatin amount 3.8g/bodextran (
molecules 1.1 million) 1.8 g/rrf4-hydroxy-6-
Methyl-1,3,3a,7-chitrazaindene 35■/polyethylene oxide 15mg/nf polypotassium p
-Vinylbenzenesulfonate 65■/poCHaOH CH,CH2-C-CH,OH300■/poCH,OH Top layer gelatin 0.8g/po13■/Bobolibotacium p-vinylbenzenesulfonate 6■/pon C1
51131COOC+6H3+ n 50
■/Poresorcin layer Gelatin 0.8 g/Iresorcin 150 ■/rrf The position of the resorcin layer is shown in Table 4.

Emulsions B, E, and F had dyes-4 to 7 added before after-ripening.

After storing the coated sample at a temperature and humidity of 25°C and 65% Rh for 7 days, the dura film was immersed in distilled water at 25°C for 3 minutes so that the film thickness was 300% ± 10 of the dry film thickness. Prepared by bis-(vinylsulfoacetamido)ethane.

The treatment and scratch resistance were evaluated in the same manner as in Example-1.

The results are shown in Table 4.

Dye-4 SOs. 5Osl1 250■1 mol Ag Dye-5 70a+g1 mol Ag Dye-6 CJs CJs I " 1 (C11□) 5sOs.CCHt) 5s (hH70
■1 mol Ag dye-7 C,1lisOs' CJiSOsNa10■1
Mol Ag Table 4 As is clear from Table 4, no matter which layer the resorcinol layer is placed between, the scratch resistance is improved without impairing river migration.

Patent IQf 1 person Fuji Photo Film Co., Ltd. procedural amendment

Claims (1)

[Scope of Claims] A silver halide photographic light-sensitive material having at least one light-sensitive silver halide emulsion layer on a support, in which the emulsion layer and/or other hydrophilic colloid layer contains at least one Contains a polyhydroxybenzene compound,
A silver halide photographic light-sensitive material characterized by containing a polymer containing a repeating unit represented by the following general formula (I) and/or dextran. General formula (I) ▲Mathematical formulas, chemical formulas, tables, etc. 10
represents a substituted or unsubstituted alkyl group, aryl group or aralkyl group, which may be the same or different. Furthermore, R^2 and R^3 may be bonded to each other to form a nitrogen-containing heterocycle together with a nitrogen atom. L is an m+1-valent linking group. n is 0 or 1, and m is 1 or 2. )