JPH02285341A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To enhance covering power, to reduce probability to be blackened by scratching, and to enable drying in a short time by incorporating a specified amount of gelatin phthalate to the total amount of gelatin and gelatin derivatives in a hydrophilic colloidal layer. CONSTITUTION:The gelatin phthalate substituted by 20 - 60% is contained in an amount of >=15wt.% of the total amount of gelatin and gelatin derivatives in the hydrophilic colloidal layer, and this is obtained by reacting phthalic anhydride or phthalic acid with gelatin but it is preferred to use phthalic anhydride, thus permitting the obtained film to be improved in physical properties, reduced in the probability of scratches and blackening due to pressures caused by handling, and dried at a sufficiently high speed, and high sensitivity to be obtained by processing in a short time.

Description

[Detailed Description of the Invention] (Industrial Application Field) The present invention relates to a silver halide photographic light-sensitive material, and in particular to a technology that has high covering power, is resistant to blackening due to scratches, and dries in a short time. In particular, the present invention relates to an X-ray film that has excellent suitability for ultra-rapid processing.

(Prior Art) In recent years, high-temperature, rapid processing has rapidly become popular in the development process of photographic light-sensitive materials, and the processing time of various light-sensitive materials in automatic processing has been greatly shortened.

In order to achieve high-temperature, rapid processing, we need a developer to achieve sufficient sensitivity in a short time, a photosensitive material with excellent developability that leaves no residual color even during short processing times, and a material that dries quickly after washing with water. Sensitive material is required. Many automatic processors have a built-in drying zone, and if the drying properties of the photosensitive material are poor, the automatic processor must have a higher drying capacity. I have no choice but to colander. Furthermore, as a result of generating a large amount of heat, there are also problems such as an increase in the temperature of the room in which the automatic processor is installed.

To prevent this from happening, efforts are made to make the drying speed of photosensitive materials as fast as possible.

The method used in the shell is to add a sufficient amount of hardening agent in advance during the photosensitive material coating process to reduce the amount of swelling of the emulsion layer and surface protective layer during the constant development and water washing process. This method reduces the water content in the photosensitive material before drying begins. In this method, the drying speed can be increased by using a large amount of hardening agent, but by strengthening the hardening agent, development may be delayed, resulting in low sensitivity, and even high aspect ratio tabular grains may be covered. It reduces the power, delays the fixing speed of undeveloped silver halide grains, worsens residual color,
This method has the disadvantage of causing various problems such as an increase in residual hypo in the photosensitive material after processing. - On the other hand, the water content in the photosensitive material before drying can be reduced by reducing the amount of hydrophilic substances coated on the photosensitive material, such as gelatin, synthetic polymers, hydrophilic low-molecular substances, etc. . The hydrophilic low-molecular substance is added to -m to prevent dry fog on silver halide grains during the coating process, and removing it will cause fog on the photosensitive material.On the other hand, it acts as a binder for silver halide grains. When gelatin and synthetic polymer substances used as silver halide particles are removed, the amount of binder relative to the silver halide grains decreases, and the silver/binder ratio increases.

Decreasing the amount of binder has the drawback of deteriorating graininess in terms of photographic performance, and especially with high aspect ratio tabular grains, sensitivity increases and decreases are more likely to occur due to scratches and bending when handling the photosensitive material before processing. Even if we try to improve drying properties, it is not possible to reduce the amount of binder due to these disadvantages.In this situation, we have achieved sufficient sensitivity in a short processing time, and have excellent fixing properties, water washability, and pressure resistance. There has been a demand for a technology that has excellent properties and can dry in a short time.

Furthermore, halogenated photographic materials have become increasingly sensitive in recent years. In high-sensitivity technology, it is essential to improve covering power (optical density per unit silver amount).
Methods such as those described in Japanese Patent Application Laid-open Nos. 61-116347 and 57-182132 are known. It is generally known that reducing the amount of gelatin, in other words, increasing the silver/gelatin ratio, improves the covering power.

However, il! When the gelatin/gelatin ratio is increased, scratches and blackening are more likely to occur due to rubbing between films, and problems of deterioration of film properties such as peeling are more likely to occur. Therefore, if the degree of hardness is increased in order to improve the physical properties of the film, the covering power decreases, making it impossible to achieve the desired improvement in covering power.

On the other hand, Japanese Patent Laid-Open No. 64-29834 discloses a technique for achieving both scratch resistance and covering power by incorporating water-soluble polyester into a sensitive material.

However, 1. this technology has not completely solved the problem.

On the other hand, JP-A No. 49-50919, No. 49-60213,
59-52239, 59-52240, 50-1
No. 5539 and No. 56-65133 disclose a technique for improving photographic performance by using a gelatin derivative in combination with gelatin or other water-soluble polymers. Among them, JP-A-59
-52239 and 59-52240 disclose methods utilizing phthalated gelatin. However, in this prior art, the method of applying phthalated gelatin was inappropriate, and therefore the effects of the present invention could not be fully exploited.

(Objective of the present invention) The object of the present invention is to solve the above-mentioned problems of the prior art, have good film properties, improve scratches and blackening caused by pressure during handling, and provide a sufficiently fast drying rate. However, it is an object of the present invention to provide a photographic light-sensitive material that maximizes the performance of silver halide grains, such as high sensitivity in a short processing time.

(Method of Achieving the Invention) The above object is to provide a silver halide photographic material having at least one layer containing a silver halide emulsion on at least one side of the support, in which gelatin and derivative gelatin in the hydrophilic colloid layer are used. This was achieved by containing 15% or more by weight of phthalated gelatin with a substitution rate of 20% or more and 60% or less with respect to the total amount of.

The phthalated gelatin of the present invention can be obtained by reacting phthalic anhydride or phthalic acids with gelatin, but it can be preferably used by reacting phthalic anhydride. Further, the gelatin used in the reaction may be acid-treated or alkali-treated, but alkali-treated gelatin is preferred.As a specific method, reference may be made to the method described in JP-A-56-65133.

The hydrophilic colloid layer of the present invention may also contain a water-soluble polyester.

Water-soluble polyester refers to polyester that is dissolved or dispersed in water, and examples of such water-soluble polyester include commercially available products such as FPY676 and MPS776a manufactured by Eastma Chemical Co., Ltd.
, WDj4jko, WTLjJ Hiro-1WNTPj/ri, W
MSJ/13, WD-8IZE, WNT, WMS, DF
B (both are trade names), etc. can be used. Especially WD-8IZE and WNT manufactured by Eastman Chemical Company.

WH8 is preferred.

Further, as water-soluble polyesters that can be used, U.S. Pat.
/6ri No., same No. DA, 3ri≠, Hiroda No., European Patent No. 1, No. 6-O, same No. 71. j! No. 3, Japanese Patent Publication No. 3 Hiroshi-4cJ
O/7 issue, Research Disclosure (Re5ear
ch Disclosure)/r92♂(/ri, r
- Water-soluble polyester gold described in the July issue).

Specifically, the following acids (one or more acids arbitrarily selected from acidic acid anhydrides or lower alkyl esters of acids) and the following glycols (under the reaction conditions for glycol or polyester or copolyester production) are used. A water-soluble polyester obtained by condensing one or more glycols arbitrarily selected from the group consisting of suitable substances that act as glycols and dissolving or dispersing the resulting polyester in water can be used.

In this case, the acids that can be used when synthesizing the water-soluble polyester include ester-forming aromatic carboxylic acids; terephthalic acid, inphthalic acid, phthalic acid,
j-dimethyltylphthalic acid, naphthalene dicarboxylic acids, biphenyldicarboxylic acid, benzopheno/tetracarboxylic acid, trimellidic acid, pyromellitic acid, trimesic acid, etc., and ester-forming aromatic nulphonic acids; sulfoterephthalic acid,! -Sulfoisophthalic acid, μm Sulfoisophthalic acid, Hiro-Sulfonaphthalene-1.

7-dicarboxylic acids, and saturated linear aliphatic dicarmenic acids having methylene groups μ to r; at least one organic acid selected from acids such as adipic acid, pimelic acid, sirinic acid, azelaic acid, and sepatanoic acid; There are ester-forming derivatives of such acids, ie anhydrides or lower alkyl esters (number of carbon atoms in the alkyl group IO or less).

Among these, especially trimellitic anhydride; Nurhotele 7
Tar acid, isophthalic acid, terephthalic acid or ester-forming derivatives thereof are preferred.

In addition, glycols that can be used when synthesizing water-soluble polyester include ethylene glycol,
, -1-prononediol, /, 3-propanediol,
/13-butanediol, /, Hiro-butanediol, /
,! -bentanediol, l,6-hex/diol,
/, r-octanediol, /, l-cyclohexanediol, neointyl glycol, diethylene glycol, dipropylene glycol, styrene oxide, phenyl glycidyl ether, and the like. Among these, diethylene glycol, ethylene glycol, /.

-Monopropanediol, diethylene glycol, neoantyl glycol and the like are preferred.

If necessary, as many as 1 or more heptahydric alcohols such as ethylene glycol monobutyl ether, tridecanol, butoxyethoxypropanol, benzyl alcohol, cyclohexanol, and hexadecanol, preferably benzyl alcohol or cyclohexanol, may be added to the polyester or copolyester. It is possible to modify the oxidation of the polyester or copolyester by adding enough royalties to the reaction mixture in which it is produced to react with the desired number of pendant carboxyl groups in the polyester or copolyester structure. be.

Control, if necessary, by adding one or more modifiers such as difunctional acids, carboxyglycols, polyfunctional alcohols, amines and amino alcohols to the reaction mixture in which the polyester or copolyester is produced. It can be modified by Suitable modifiers include isophthalic acid, tere-7-thaleric acid, 7-talic anhydride,
Formic acid, maleic anhydride, chlorendic anhydride, tetrachlorophthalic anhydride, succinic acid, dimethylolpropanoic acid, glycerin, ethanolamine, ethylenediamine and hexamethylenediamine, isophthalic acid, terephthalic acid, phthalic anhydride , chlorendic anhydride, maleic anhydride and ethanolamine are preferred.

The molecular weight of polyester or copolyester is joo
or jO,000.

In the present invention, the amount of water-soluble polyester added is preferably 1 to -oo4 based on the solid weight of gelatin, and j to
100 is particularly preferred. If the addition amount is small, the improvement of the film physical properties (scratch resistance) will be insufficient, and if it is more than 200%, the scratch resistance will not be improved any further, and in fact, the reduction in the covering finish will be greater. There are cases where this happens.

The water-soluble polyester may be added to any hydrophilic colloid layer on the side of the silver halide emulsion layer, but it is preferably added to the emulsion layer or a layer adjacent thereto.

Polyhydroxybenzenes can be preferably used in the hydrophilic colloid layer of the present invention for the purpose of improving pressure properties.

Representative examples of polyhydroxy-substituted benzene compounds that can be effectively used in the present invention are shown below.

H H Among these substituents, as X 100OH is particularly preferred.

1803K.

The compounds of the present invention are not limited to those described above.

Among these compounds, /, Hiro-dihydroxybe is preferred.

The polyhydroxy-substituted benzene compound is added to the silver halide emulsion layer or another hydrophilic colloid layer on the same side as the emulsion layer, but preferably to the silver halide emulsion layer.

The amount added is less than 41) 10-'' mol per mol of silver in the sensitive material, but especially! Less than × 10 moles, and / × 10 −
It is preferable that the amount is 10 mol.

As the emulsion of the present invention, conventionally known emulsions may be used depending on the purpose, but tabular grains are particularly effective.

The tabular silver halide emulsion is manufactured by Cugnac.
and Chateau, “Evolution of morphology of silver bromide crystals during physical ripening.”
"The Morphology of Silver Bromide Crystals Due to Physical Living)" Science/Industrial Photography, Volume 33, A, 2 (/RIO-), l:), / 2
/ -/ J j, Duffin, “
Photography Emulsion Chemistry (Ph
otographic emulsion Chemi
stry ) J 7 Ocal Pv, z (Focal
Press), New York, / 1966, p, aA
-p, 72, A, P, H, Trivcli
), W. F. Smith Photographic Journal
), Volume 10, Page 213 (/rihiro θ), etc., but JP-A-71-/Core, Tar/, JP-A-Shoj♂-//J
, Octopus 7, JP-A-Sho J-r-//3. It can be easily prepared by referring to the method described in U.S. Pat.

4. In an atmosphere with relatively low pB and r values of pBr/,j or less, form seed crystals in which tabular grains are present in an amount of aO% or more by weight, and add silver and halogen solutions while keeping the pBr value at the same level. can be obtained by growing seed crystals while simultaneously adding

During this grain growth process, it is desirable to add a silver and halogen solution to prevent the generation of new crystal nuclei.

The size of the tabular silver halide grains can be adjusted by controlling temperature adjustment, selection of the type and amount of solvent, silver salt used during grain growth, addition rate of halide, etc.

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

Details of the structure and manufacturability of the monodisperse hexagonal tabular grains referred to in the present invention can be found in the patent application Sho t/- Kotata/, t! However, briefly stated, the emulsion is a silver halide emulsion consisting of a dispersion medium and silver halide grains, and 70 or more of the total projected area of the silver halide grains has a minimum length. The ratio of the length of the side with the maximum length to the length of the side with the maximum length is λ
The grain size distribution of the hexagonal tabular silver halide grains is occupied by tabular silver halide grains having hexagonal hexagonal edges and parallel C planes as outer surfaces, and It has monodispersity of 20% or less (the value obtained by dividing the variation (standard deviation) in particle size by the circular diameter of the projected area by the average particle size). Although the crystal structure may be similar, it is preferable that the inside and outside have different compositions, and may have a layered structure. However, it is preferable that the particles contain reduction-sensitized silver nuclei.

The aspic ratio of the tabular grains is 3 or more and 30 or less, preferably! The above and below are below.

For the present invention, British Patent No. t3t, rμ/, US Patent No. 3. So-called halogen conversion type (conversion type) particles such as those described in ΔCoco, No. 3/r can be effectively used in %.

By converting the surface of the tabular silver halide grains of the present invention, silver halide emulsions with much higher sensitivity can be obtained.

As a method for halogen conversion, an aqueous halogen solution having a solubility product with silver that is smaller in solubility product than the halogen composition on the particle surface of the halogen conversion layer is usually added. For example, chloride fa′? For silver chlorobromide tabular grains, a potassium bromide and 10R potassium iodide aqueous solution is added, and for silver bromide and silver iodobromide tabular grains, a potassium iodide aqueous solution is added to cause conversion. The concentration of the aqueous solution to be added is preferably as low as 30
% or less, more preferably 10% or less. Furthermore, it is preferable to add the converted halogen solution at a rate of 1 mole per minute or less per mole of silver halide before halogen conversion. Further, a sensitizing dye may be present during halogen conversion, and silver halide fine particles of silver bromide, silver iodobromide, or silver iodide may be added instead of the aqueous halogen solution. The size of these fine particles is preferably 06-μm or less.
．． It is desirable that the thickness be 1 μm or less, particularly 0.01 μm or less. /・The amount of halogen conversion is 0 of silver halide before conversion.
．． 7 to 0.4 mo1%, particularly O67 to 0.4 mo1% is preferred.

The halogen conversion method of the present invention is not limited to any of the seven methods described above, but can be used in combination depending on the purpose. The silver halide composition of the narrow side of the grain before halogen conversion is preferably 7 mol % or less. In particular, it is preferably 0.3 mo1% or less.

When performing halogen conversion using the above method, a method in which a silver halide solvent is present is particularly effective.

Preferred solvents include thioether compounds, thiothia/acid salts, and da-substituted thioureas. Among them, thioether compounds and thiocyanates are particularly effective, and thiocyanates contain 7 moles of silver halide, o, jf-j
f. It is preferable to use 0.2 to 3 g of thioether.

In addition, in the present invention, Japanese Patent Application Laid-Open No. 61-230135 and Japanese Patent Application No. 6
A compound that releases an inhibitor during development, such as those described in Japanese Patent No. 1-169499, may be used in combination.

Cadmium salts, zinc salts, lead salts, thallium salts, iridium salts or their complex salts, rhodium salts or their complex salts, iron salts or iron complex salts, etc. coexist in the process of silver halide grain formation or physical ripening during silver halide production. You may let them.

In addition, during grain formation, so-called silver halide solvents such as thiocyanates, 1,000-onythyl compounds, thiazolidine nithiones, and tetrasubstituted thioureas may be present. Among them, thiocyanates, 4-substituted thioureas, and thioethers are used in the present invention. A preferred solvent.

As a method for chemically sensitizing the silver halide emulsion used in the present invention, known methods such as sulfur sensitization, selenium sensitization, reduction sensitization, and gold sensitization can be used. or used in combination.

Among them, especially patent applications No. 63-159888 and No. 63-2.
Application of reduction sensitization described in No. 58787 and Japanese Patent Application No. 1-15520 is preferred.

When chemically sensitizing the emulsion used in the present invention, it is desirable to have a sensitizing dye and/or a silver halide emulsion stabilizer present.

The term "silver halide emulsion stabilizer" refers to a silver halide adsorbent substance known as an antifoggant or a stabilizer.

Namely, azoles (e.g., benzothiazolium salts, benzimidazolium salts, imidazoles, benzimidazoles, nitroindazoles, triazoles, benzotriazoles, tetrazoles, triazines, etc.); mercapto compounds (e.g., mercaptothiazoles) , mercaptobenzothiazoles, mercaptoimidazoles, mercaptobenzimidazoles, mercaptobenzoxazoles, mercaptothiadiazoles, mercaptooxadiazoles, mercaptotetrazoles, mercaptotriazoles, mercaptopyrimidines, mercaptotriazines, etc.); for example, oxa Thioketo compounds such as drinthion; azaindenes (e.g. triazaindenes, tetraazaindenes (especially 4-hydroxy-substituted (1,3,3a,7) tetraazaindenes), pentaazaindenes, etc.)
known as antifoggants or stabilizers such as;
Many compounds can be mentioned as halogenated 11 adsorbents.

Furthermore, purines or nucleic acids, or
36213, JP-A No. 59-90844, and the like are also usable adsorbent substances.

Among them, azaindenes, purines, and nucleic acids are particularly preferred and can be used in the present invention. The amount of these compounds added is 0.5 to 5.0 mmol, preferably 0.5 to 3.0 mmol, per 111 moles of halogenide.

Specific examples of compounds effective in the present invention are shown below.

0H H 0■! -4! -10 NA NA [-6 NHCOCH3 ■-14 Jq ■ -17 Js C! HS In the present invention, preferable effects can be achieved by using the above-mentioned photographic performance stabilizer and sensitizing dye together during chemical sensitization.

As the sensitizing dye, cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopholarianine dyes, styryl dyes, hemicyanine dyes, oxonol dyes, hemioxonol dyes, etc. can be used.

Useful sensitizing dyes for use in the present invention include, for example, U.S. Pat.
, No. 522.052, No. 3,619,197, No. 3,
No. 713,828, No. 3,615゜643, No. 3,6
No. 15,632, No. 3.617.293, No. 3,62
No. 8,964, No. 3703.377, No. 3,666.
No. 480, No. 3.667.960, No. 3,679,4
No. 28, No. 3,672,897, No. 3,769.02
No. 6, No. 3,556,800, No. 3,615,613
No. 3,615,638, No. 3,615゜635, No. 3,705.809, No. 3.632.349,
No. 3,677.765, No. 3770.449, No. 3.770,440, No. 3.769.025, No. 3
, No. 745,014, No. 3,713,828, No. 3,
No. 567.458, No. 3,625,698, No. 2,5
No. 26,632, No. 2,503.776, Japanese Unexamined Patent Publication No. 1973
-76525, Belgian Patent No. 691,807, etc. The amount of sensitizing dye added is silver halide 1
600 to less than 1500 μ per mole, preferably 6
00■ or more and less than 1000■ is preferable.

Specific examples of sensitizing dyes useful in the present invention are shown below.

n-1 (Cut)s O3X (CHg)s SO1 03Na SO1 ■-16 02K SO! ■-18 SO, Na Or ■-10 (CHx)2 SO, Na (CE+ri3 Oi ■-15 heat SO= l-19 zFIS (C1h)s ON ■-20 tllS SOKOK Oi ■-23 n-24 ■-28 C! H5 C, Hs C surprise H% O3K ot (Cth) Ko Sui ■-25 ■-27 ■-31 ■-32 ■-33 Js L;, t+S ■-34 ■-35 C! lls ■-36 ■-40 ■-41 ■-42 4HI ■-37 O.J. ■-38 C! Hs ■-39 ■-43 O3K zHs C! Is ■-44 ■-45 1s tH5 ■-46 ■-47 C, Hs Among the above, cyanine dyes are particularly preferred.

/' / / 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. A specific example is US Pat. No. 11,010
No. 6/1, British Patent No. 6/1, oti No., etc.

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.

The combined use of sulfur sensitization using thiosulfate and gold sensitization can effectively exhibit the effects of the present invention.

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

As the tabular grains used in the present invention, Japanese Patent Application No. 6J-/4
The vertex development initiation type particles described in Liii2 are extremely useful.

The photographic emulsion used in the present invention has the following properties: to prevent turnip IJ '2 during the manufacturing process, storage or photographic processing of the light-sensitive material;
Alternatively, for the purpose of stabilizing photographic performance, it is possible to incorporate various compounds in addition to the silver halide adsorbing substance used in the chemical sensitization process of the present invention. Namely, azoles (e.g. benzothiazolium salts, nitroimidazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, nitroindazoles, be/citriazoles, aminotriazoles, etc.); mercapto compounds ( For example, mercaptotheazoles, mercaptoindithiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, mercaptotetrazoles, mercaptopyrimidines, mercaptopyrimidines, etc.1; thioketo compounds such as oxadorinthione; azaindenes (e.g. triazain ≠-Hydroxy-substituted (/, J, Ja, 7) tetraazaindenes), hantaazaindenes, etc.); henchiosulfonic acid, benzenesulfinic acid, benzenesulfonic acid amide A number of compounds known as antifoggants or stabilizers can be added, such as.

In particular, nitrone and its derivatives described in JP-A-4O-7A717 and JP-A-4O-r732-;
Mercapto compound described in OT3 publication, JP-A-77
The heterocyclic compound described in -/j≠737 and a complex salt of a heterocyclic compound and silver (for example, /-phenyl-!-mercaptotetrazole silver) can be preferably used.

The photographic emulsion layer or other hydrophilic colloid layer of the light-sensitive material prepared using the present invention may include coating aids, antistatic properties, nubularity improvement, emulsification dispersion, adhesion prevention, and photographic property improvement (e.g.
Various surfactants may be included for various purposes such as development acceleration, hardening, and sensitization.

For example, saponin (steroid type), alkylene oxide derivatives (e.g. polyethylene glycol, polyethylene glycol/polypropylene glycol condensate, polyethylene glycol alkyl Nonionic surfactants such as alkyl esters of sugars; alkyl null hepta-onates, alkyl benzene sulfonates, alkyl naphthalene nulfonates, alkyl sulfates, N-acyl-N-alkyl taurines, null phosuccinates anionic surfactants such as sulfoalkyl polyoxyethylene alkylphenyl ethers; amphoteric surfactants such as alkyl betaines and alkyl sulfobetaines; aliphatic or aromatic μ-class ammonium salts, pyridinium salts, Cationic surfactants such as imidazolium salts can be used.

Among these, saponin, dodecylbenzenesulfonic acid Na salt, gecoethylhexyl α-sulfosuccinate Na salt,
Sodium p-octylphenoxyethoxyethanesulfonate
salts, anions such as dodecyl sulfur 11NatJi, triimpropylnaphthalenesulfonic acid Na salt, N-methyl-oleoyltalarin Na salt, dodecyltrimethylammonium chloride, N-oleoyl-N', N',
cations such as N'-1 trimethylammoniodiaminopro/cumbromide, dodecylpyridium chloride,
N-dodecyl-N,N-dimethylcalcexybetaine,
Betaines such as N-oleyl-N,N-dimethylsulfobutyl itaine, poly(average degree of polymerization n=/0) oxyethylene cetyl ether, poly(n=λj) oxyethylene p-nonylphenol ether, bis(/-poly Nonions such as (n=/l) oxyethylene-oxy-λ1 μm di-terphenyl)ethane can be particularly preferably used.

Perfluorooctaneurphonic acid potassium is used as an antistatic agent.
[, N-propyl-N-perfluorooctanesulfonylglycine Na salt, N-'Robi-N-pN-fluorooctanesulfonylaminoethyloxypoly(n=J
) Oxyethylene butanesulfone 1llNa[, N-perfluorooctanesulfonyl-N', N', N'
- trimethylammoniodiaminopropane chloride,
N-perfluorodecanoylaminozolopyl-N/,N
/-Fluorine-containing surfactants such as dimethyl-N'-carboxybetaine, JP-A No. 2003-07-06/
-//u/4444, Tokugansho,! Nonionic surfactants, alkali metal nitrates, conductive tin oxide, zinc oxide, vanadium pentoxide, or doped with antimony, etc., as described in /-/JJ9r No. 6/-/40j6, etc. Oxides can be preferably used.

In the present invention, as a matting agent, U.S. Pat.
No. 1, No. 2707λ≠j, No. μ) Hiro-l, No. 4
A homopolymer of polymethyl methacrylate or a copolymer of methyl methacrylate and methacrylic acid as described in L3 Li No. 670, an organic compound such as starch, fine particles of an inorganic compound such as silica, tita 7 dioxide, sulfuric acid, barium strontium, etc. Can be used.

The particle size is i, o ~ IO μm, 1 in %! μm
It is preferable that

The surface layer of the photographic light-sensitive material of the present invention may contain silicone compounds as described in U.S. Pat. In addition to silica, paraffin wax, higher fatty acid esters, starch derivatives, etc. can be used.

Polyols such as trimethylolpropane, intanediol, butanediol, ethylene glycol, and glycerin can be used as plasticizers in the hydrophilic colloid layer of the photographic material of the present invention.

Gelatin is used as the binder for the emulsion layer, intermediate layer, and surface protective layer of the light-sensitive material of the present invention, but other binders having a hydrophilicity of 1° can also be used.

9 Rie is gelatin derivatives, graft polyphenyls of gelatin and other polymers, proteins such as casein; cellulose derivatives such as hydroxyether cellulone, carboxymethyl cellulose, cell P-nusulfate ester, etc., sodium alginate, dextran, Sugar derivatives such as starch derivatives; polyvinyl alcohol, polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide,
A wide variety of synthetic hydrophilic polymeric materials can be used, such as single or copolymers of 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 gelatin hydrolysates or enzymatically decomposed products may also be used.

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

For example, chromium salt (chromium alum), aldehyde If
(formaldehyde, glitaraldehyde, etc.), N
- Methylol compounds (such as dimethylol urea), dioxane derivatives (such as 2,3-dihydroxydioxane),
Active vinyl compound (1°3.5-)acryloyl-hexahydro-S-triazine, bis(vinylsulfonyl)methyl ether, N,N'-methylenebis-[β-
(vinylsulfonyl)propionamide], etc.), active halogen compounds <2.4-dichloro-6-hydroxy-
3-triazine, etc.), mucohalogen acids (mucochloric acid, etc.), isoxazoles, dialdehyde starch, 2
-Chloro-6-hydroxytriazinylated gelatin and the like can be used alone or in combination. Among them, JP-A No. 53-4122, No. 53-57257, No. 5
Preferred are the active vinyl compounds described in US Pat. No. 9-162546 and US Pat. No. 60-80846 and the active halides described in US Pat.

N-carpamoyl pyridinicum salts (e.g. (/-morpholinocarbonyl-3-pyri,)nio)methanesulfonate, etc.), haloamidinium salts (e.g. /-(/-
Also useful are chloro-l-pyridinomethylene) hyroricinium conaphthalene sulfonate.

Polymer hardeners can also be effectively used as hardeners in the present invention.

Examples of the polymeric hardener used in the present invention include dialdehyde starch, polyacrolein, U.S. Patent No. 3, JPt, 0
Polymers having aldehyde groups, such as the acrolein copolymers described in Kota, U.S. Pat. No. 3,623. r'yr
Polymers having epoxy groups described in U.S. Pat.
3tco, rJ7 issue, Research Disclosure magazine/
7333 (l 7F) etc. Polymers having active ester groups as described in JP-A No. 4-441,
Unexamined Japanese Patent Publication No. Shoj6-/Hiro-j Kohiro, U.S. Patent No. μ, /l, /
, Hiroshi 07, JP-A-Shoj Hiroshi-43033, Research Disclosure Magazine/&7jj (/271), etc., polymers having an active vinyl group or a group that is a precursor thereof, etc. A polymer having a group or a group serving as a precursor thereof is preferable,
Among these, polymers in which an active vinyl group or a group serving as a precursor thereof is bonded to the polymer main chain by a long sweeter, as described in JP-A-76-/≠-J-Hiro, are particularly preferred.

As the support, polyethylene terephthalate film or cellulose triacetate film is preferred.

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 it may be made of styrene-butadiene-based latex, vinylidene chloride-based latex, etc. An undercoat layer may be provided, and a gelatin layer may be further provided on top of the undercoat layer.

Further, an undercoat layer may be provided using an organic solvent containing a polyethylene swelling agent and gelatin. These undercoat layers can be subjected to surface narrowing treatment to further improve their adhesion to the hydrophilic colloid layer.

The silver halide photographic light-sensitive material of the present invention has a filter layer for the purpose of absorbing light in a specific wavelength range, that is, a filter layer that absorbs light in a specific wavelength range. The photographic emulsion layer or other layers may be colored with a dye for the purpose of controlling the color. In double-sided films, such as direct medical x-ray films, a cross-over layer may be provided below the emulsion layer. Examples of such dyes include oxonol dyes, azo dyes, azomethine dyes, anthraquino/dyes, odoridene dyes, styryl dyes, triarylmethane dyes, merocyanine dyes, and cyanine dyes having pyrazolone nuclei or barbylic acid nuclei. It will be done.

Representative dyes are shown below, but the present invention is not limited thereto.

! 0aNa CH2C) 12So3K CH2C) 12S (J3K S (J3 to 803 lo 8 (J3 to 3 (J3 to Mordanting is an effective technique. In this case, it is preferable to use a dye that irreversibly decolorizes during the constant development and washing process.

The layer in which the dye is mordant using a polymer having cationic sites may be in the emulsion layer, in the surface protective layer, or on the side opposite to the emulsion layer and the support, but is preferably between the emulsion layer and the support. Particularly for purposes of cross-over cutting of medical X-ray double-sided films, mordanting into the subbing layer is ideal.

Tokukaisho is the best method for fixing dyes! J-/! ! ,! The solid dispersion method described in No. 30 and Woe♂101fi77μ is also effective.

As a coating aid for the undercoat layer, a polyethylene oxide type nonionic surfactant can preferably be used in combination with the polymer having cateo/cy)f.

Anion conversion polymers are preferred as polymers that provide cation sites.

As the anion-modified polymer, various known quaternary ammonium salt (or phosphonium salt) polymers can be used.

Quaternary ammonium salt (or phosphonium salt) polymers are widely known as mordant polymers and antistatic polymers from the following publications.

Tokukai Akira! Tar/6 Otsu, Rihiro 01 US Patent 3. ri11,'
19j, Tokukai Showa 6! -/112339,% Kaisho 3-
/2t, 027, Tokukai Akira! Hiro-/! j.

rJJ, JP-A-Sho j3-JOJ2r, % Kai-Sho tg-2-2
Water-dispersed latex described in 74L; US Pat.
1! Hiro! ,! Hiromu, 3. /Hiroshi.

Polyvinylpyridinium salts described in U.S. Pat. Examples include the water-insoluble quaternary ammonium salt polymers described in RR and ORR.

further transferred from the desired layer to another layer or into the processing solution,
In order to avoid undesirable photographic effects, the ethylenically unsaturated group is at least λ or more (preferably λ~4c).
It is preferable to copolymerize the monomers and use the resulting crosslinked aqueous polymer latex.

Specific examples of compounds include the following.

/) Ko] x:y:z=4tj: Gu! : 10 x : y 2 2 = bow-ni, j; : bow-:
z: / .

In the present invention, there are no particular restrictions on the method of coating the emulsion layer, narrow surface protective layer, etc. on the support, but for example, US Pat. 01, P4j7
The multilayer simultaneous coating method described in No., No. 76/, No. 7F/, etc. can be preferably used.

The developer used in the present invention can contain known developing agents. As the developing agent, dihydroxybenzenes (e.g. hydroquinone), 3-pyrazolidones (e.g. /-phenyl-3-pyrazolidone), aminephenols (e.g. N-methyl-p-aminophenol, etc.) may be used alone or in combination. can.

The developing solution generally contains other known preservatives, alkaline agents, and
Contains H buffering agents, anti-fogging agents, etc., and further contains solubilizing agents, color toners, development accelerators (for example, ≠ grade salts, hydrazine, benzyl alcohol), surfactants, antifoaming agents,
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 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 developing method using an automatic developing machine in the present invention is described in US Pat. JZ No. 3J732/Hiro No. 36 Hiroshi 7 Hiroshi! It is preferable to use a roller conveyance type automatic developing machine as described in British Patent No. 7-67-O.

The developing temperature is ir'C-jo'C, especially 3o
'C-Hiroshi'C' is preferable, and the development time is preferably 1 second to 0 seconds, particularly t seconds to -3 seconds.

The total processing time from the start of development to the end of fixing, water washing, and drying is preferably 30 seconds to 200 seconds, particularly 0 seconds to 10 seconds.

There are no particular restrictions on the various additives, development methods, exposure methods, etc. of the photosensitive material of the present invention.
You can refer to the descriptions in the same volume III item /r4cJ/ (/7 years ago).

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

Example/ Preparation of emulsion Potassium bromide JP, potassium iodide 0. OJf.

Gelatin 3Q9, thioether HO(C)1 )S(CH2)2S(CH2)20H! Silver nitrate was added to the solution, which was kept at 73°C with JCC added, while stirring. , an aqueous solution of 33f, and potassium bromide! , Taku? , an aqueous solution containing 0.7jjt of potassium iodide using the double jet method! Added in seconds. Next is calico bromide! After adding f, an aqueous solution containing silver nitrate r and JJf was added over 26 minutes so that the flow rate at the end of addition was twice that at the start of addition. After this, λ! Tea ammonia solution - cc, jO attack N HN Os / O
After adding cc and physical aging for -O minutes, /N sulfuric acid -
The mixture was neutralized by adding 70% θCC. Next, silver nitrate/! 3
．． The aqueous solution of 3 Hiroshi 2 and the aqueous solution of potassium bromide at potential rl)A
gJ'.

tio using the controlled double jet method.
Added within minutes. The flow rate at this time is the flow rate at the end of addition.
The flow rate was accelerated to double that at the start of addition. After the addition was completed, 1 jcc of -N potassium thiocyanate solution was added,
Furthermore, 5Q cc of an aqueous potassium iodide solution of 1/2 was added over 30 seconds. After this, the temperature was lowered to 3z'c, soluble salts were removed by the sedimentation method, and then the humidity was raised to μ0°C to 30°C for gelatin. And 7 Enorou? was added, and pHA, 〇, pAgJ', /OK were adjusted with sodium chloride and potassium bromide.

After raising the temperature to 36°C, 600η of a sensitizing dye having the following structure and a stabilizer /jO■ were added.

Sodium thiosulfate in 10 minutes! Aquarium λ, Hiro ~, potassium thiocyanate/Hiro OW9, chloroauric acid λ, /~ were added to each emulsion, and after 10 minutes, the emulsions were rapidly cooled and solidified to form an emulsion. The resulting emulsion has a total projected area of all grains, and the average projected area diameter of all grains with an aspect ratio of 3 or more is /, Hiμ
m1 standard deviation/J%, average thickness was 0.117 μm, and aspect ratio was 7.1.

The following chemicals were added to the emulsion per mole of the northern limit of halogen to prepare a coating solution.

・Gelatin (lime treatment) Adjust the amount to be added to the amount listed in Table-1 Adjust the amount to be added to the type and bond listed in Table-1 ・Polyacrylamide, phthalated gelatin, polymer with an average molecular weight of 45,000 Latex (poly(ethyl acrylate/methacrylic acid) = 97/3) ・Hardening agent 1.2-bis(sulfonyl 25.0 g Table = 1 amount listed in acetamido)ethane SO3 ・2.6-bis(hydroxyamino) )-4-diethylamino-1,3゜5-triazine 80 ■ Sodium polyacrylate (average molecular weight 41,000) 4.0 g Potassium polystyrene sulfonate (average molecular weight 600,000) 1.0 g applied to the surface It was coated on both sides of a transparent PET support with a thickness of 175 um at the same time as the protective layer coating solution.

The amount of silver coated was 2.0 g/rrf per side.

The surface protective layer was prepared so that each component was coated in the following amounts, and designated as photographic materials 1 to 12 (Table 1).

mγ curvature ·gelatin ・4-hydroxy-6-meth Chill-1, 3, 3a.

7-chitrazaindene polyacrylamide (average molecular weight 450,000) - Sodium polyacrylate (average molecular weight 400,000) - Sodium salt of pt-octylphenoxydiglyceryl butyl sulfonate - poly(degree of polymerization 10) oxyethylene cetyl Ethyl poly(polymerization degree 10) oxyethylene-poly(polymerization skin 3) oxyglyceryl p-octylfeta-1,15g/bo 0.015g/bo 0,25 0,02 0,02 0.035 Tsukidiether 0 .01 meeting C@F+
tS(h to 0.003C
3H Ma CsF+tS01N-(-cHi←hd CH!→
45O3Na0.001 C,H?・ CsF 1tsOJ (C) ItCIbOten (C
HxCHCHtOh Ho, 003 ・Polymethyl methacrylate (average particle size 3.5 μm) 0.025 ・Poly(methyl methacrylate/methacrylate) (molar ratio 7:3, average particle size 2.5 μm) 0.020 Odor 11
Summer review I Photographic materials 1-1 with green light having a peak at 550 nm
After exposing 0 to 1/20 seconds, an automatic processor FPM9000 manufactured by Fuji Photo Film ■ was used. Developer RD7, fixer Fu
SP treatment at 35°C using jIF (Dry to Dry
45 seconds).

The sensitivity was calculated as the reciprocal of the exposure amount that gave a density of Fog+1.0, and the results are summarized in Table 1, with Photographic Material 1 set as 100.

1' Scratches 1' Photographic materials 1 to 12 were conditioned for 1 hour at 25°C and 25% RH, and under the same conditions, using a commercially available nylon scrubber, a load of 100g was applied to the area of 2
I rubbed at a speed of m. After performing the above-mentioned automatic processing in an unexposed state, the number of blackened scratches was counted.

Director Yingqiu Huangqiu■ In the above-mentioned automatic processor processing, after passing through the constant development and washing steps, the film was taken out just before it was squeezed and entered the drying zone, and the following measurements were made.

While blowing warm air onto the taken-out film using a commercially available dryer, the time required for the surface temperature to reach 30°C was measured using a surface thermometer. The developing temperature was 35°C, and the washing water temperature was 14°C.

The above results are summarized in Table-1.

From the results shown in Table 1, the superiority of the results to the objectives of the present invention can be clearly confirmed. Polyacrylamide, which was conventionally used to increase covering power, worsens scratches and drying properties, and scratches cannot be recovered even if the amount of hardener is increased.

The present invention has high sensitivity, scratches comparable to those of photographic materials, and has extremely excellent drying properties.

procedural amendment Calligraphy (spontaneous) & Target of correction Specification 6゜ Contents of correction We will submit a copy of the detailed statement (with no changes to the details).

Display of incidents 1995 Patent Application No. 1070/λ vinegar.

2. Name of the invention Silver halide photographic material 3゜ person who makes corrections Relationship with the incident

Claims (1)

[Claims] In a silver halide photographic light-sensitive material having at least one silver halide emulsion layer on a support, phthalation with a substitution ratio of 20% to 60% with respect to the total amount of gelatin and derivative gelatin in the hydrophilic colloid layer. A silver halide photographic material containing 15% or more by weight of gelatin.