JPH02216138A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To reduce pressure fog due to contact friction between the surface of the photosensitive material and a backing face by adding a matting agent containing a prescribed amount or more of particles of a prescribed diameter or more to the backing layer. CONSTITUTION:This photosensitive material has one or more photosensitive layers composed of silver halide emulsion spectrally sensitized to >=600nm wavelengths and contains a hydrazine derivative, such as a compound of formula I, in this layer or another hydrophilic colloidal layer, and the backing layer contains the matting agent, such as SiO2, containing particles of >=5mum diameter in an amount of >=30 volume % of total particles. It is preferred to add a polyhydroxybenzene compound, such as a compound of formula II to this photosensitive layer or the other hydrophilic colloidal layer, and a sliding agent and/or a colloidal silica to the outermost layer of the photosensitive layers.

Description

Detailed Description of the Invention [Field of Industrial Application] The present invention relates to ultra-high contrast silver halide photographic light-sensitive materials spectrally sensitized to wavelengths longer than 600 nm. This relates to silver photographic materials.

[Prior art]

In the field of graph ink and arc, an image forming system that exhibits photographic characteristics of ultra-high contrast (especially gamma of 10 or more) is required in order to achieve good reproduction of continuous tone images using halftone images or reproduction of line images. It is.

Traditionally, a special developer called a Lith developer has been used for this purpose. Lith developer contains only hydroquinone as a developing agent, and uses sulfite as a preservative in the form of an adduct with formaldehyde to keep the concentration of free sulfite ions extremely low so as not to inhibit its infectious development properties. (0.1 mol/It or less). Therefore, the Lith developer has a serious drawback in that it is extremely susceptible to air oxidation and cannot be stored for more than 3 days.

As a method for obtaining high-contrast photographic properties using a stable developer, U.S. Pat.
, No. 168.977, No. 4.166.742, No. 4.311.781, No. 4,272,606, No. 4. 211. No. 857, same No. 4.243,739
There is a method using a hydrazine derivative described in No. 1, etc. According to this method, photographic properties with ultra-high contrast and high sensitivity can be obtained, and since it is permissible to add a high concentration of sulfite to the developer, the stability of the developer against air oxidation is better than that of the lithium developer. A dramatic improvement in comparison.

In recent years, single-scanner systems have been widely used in the printing plate-making field. There are various types of recording apparatuses that use image forming methods using a scanner, and the recording light sources of these scanner-only recording apparatuses include glow lamps, xenon lamps, tungsten lamps, LEDs, or He-N.
There are e-lasers, argon lasers, semiconductor lasers, etc.

The photosensitive materials used in these scanners are required to have various properties, but in particular, because they are exposed for a short exposure time of 10-3 to 10-' seconds, they have high sensitivity and high contrast even under such conditions. It is an essential condition. Especially in the field of facsimile, in order to emphasize promptness,
It is important to have excellent suitability for rapid processing, and in the future, it will be desirable to increase the number of lines and narrow down the light beam in order to achieve faster scanning and higher image quality.
There has been a strong desire to develop photosensitive materials with high sensitivity and high contrast.

On the other hand, in recent years, various devices equipped with an automatic conveyance mechanism, such as a device for automatically conveying, exposing, and developing photographic materials, have been developed, and these devices have also been applied to the above-mentioned scanner-type recording devices.

When transporting photographic materials using such an automatic transport system,
Failures often occur where the photosensitive material gets caught on the way, or when large sheet films are conveyed one by one from the sheet tray or stack zone, two sheets are fed at the same time (two-sheet feeding).

As a method for improving transportability, there has conventionally been a method of reducing the sliding friction of photosensitive materials. For example, US patent cylinder 3,0
42.522, U.S. Patent No. 3゜080.317, British Patent No. 1,466.304, British Patent No. 1,143
, No. 118.

However, when applied to automatic conveyance equipment equipped with various conveyance mechanisms as described above, it is no longer possible to ensure sufficient conveyance simply by providing such slipperiness. As described in Japanese Patent Application No. 61-188945, a method is known in which the transportability of a photosensitive material is improved by adding a large capping agent to the backing layer of a support. When a large-sized mantle agent is used, the photosensitive material has the disadvantage of causing pressure blur due to contact friction between the surface of the photosensitive material and the back surface during transportation.

As a means of improving density changes caused by pressure, there are methods in which polymers contain plasticizers such as emulsions, and methods in which silver halide/gelatinization is reduced in silver halide emulsion layers and sensitive materials. A method is known in which the pressure is relaxed before it reaches the particles.

British Patent No. 738.618 describes heterosegmental cyclic compounds.
No. 38,637 contains alkyl phthalate, No. 738,
No. 689 describes alkyl esters in U.S. Patent No. 2.96.
No. 0.404 contains polyhydric alcohol, No. 3.121. '
No. 060 discloses a method using carboxyalkylcellulose, JP-A-49-5017 discloses a method using paraffin and a carboxylic acid salt, and JP-B No. 5328086 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, development progress will be delayed and suitability for rapid processing will be impaired. has.

In addition, polyhydroxybenzene compounds have been introduced into silver halide photographic materials containing hydrazine derivatives for various purposes, such as U.S. Patent No. 4,332.108 and U.S. Pat.
．． No. 385,108, US Pat. No. 4,377.634, etc., and Japanese Patent Application Laid-Open No. 62-21143 describes a technique for preventing pressure sensitization.

However, even if these methods are used, they are not perfect, and are particularly insufficient in preventing the generation of capri due to abrasion due to contact friction with a backing layer using a large particle matting agent.

[Purpose of the invention]

An object of the present invention is to provide an ultra-high contrast silver halide photographic material that is spectrally sensitized to wavelengths longer than 600 nm and has excellent transportability and improved pressure blur due to friction with a backing layer. be.

[Structure of the invention]

An object of the present invention is to provide a silver halide photographic light-sensitive material having at least a -layer formed of a silver halide emulsion spectrally sensitized to wavelengths longer than 600 nm on a transparent support. Contains a hydrazine derivative in the hydrophilic colloid layer, and has a particle size of 5μ on the opposite side of the photosensitive layer.
This was achieved by a silver halide photographic light-sensitive material characterized by providing a backing layer containing a matting agent containing 30% by volume or more of grains of m or more.

The backing layer of the present invention will be explained in detail.

Matting agents are well known in the photographic art and can be defined as discrete solid particles of inorganic or organic material dispersible in a hydrophilic organic colloid binder. The matting agent may or may not be eluted during the development process.

Examples of inorganic matting agents include oxides (e.g. silicon dioxide, titanium oxide, magnesium oxide, aluminum oxide, etc.), alkaline earth metal salts (e.g. sulfates and carbonates, specifically barium sulfate, carbonate, etc.). calcium, magnesium sulfate, strontium sulfate, calcium carbonate, etc.)
, silver halide grains that do not form images (lately mature grains,
particles desensitized with rhodium salts, etc.), glass, etc.

In addition, West German patent no. 2,529.321, British patent no. , No. 662, No. 3.062.64.9, No. 3,257,206, No. 3.322.555, No. 3
, 353.958, 3,370.951, 3,
No. 411,907, No. 3,437,484, No. 3.5
No. 23022, No. 3,615,554, No. 3,635
．． No. 714, No. 3,769,020, No. 4°021.
Inorganic matting agents described in No. 245, No. 4,029,504, etc. can also be used.

Examples of organic capping agents include starch, cellulose esters (e.g., cellulose acetate propionate, etc.)
, cellulose ether (e.g. ethyl cellulose etc.),
Examples of synthetic resins include water-insoluble or fli8 synthetic polymers, such as alkyl acrylate, alkyl methacrylate, alkoxyalkyl acrylate, alkoxyalkyl methacrylate, glycidyl acrylate, glycidyl methacrylate, acrylamide methacrylamide. , vinyl esters (e.g. vinyl acetate), acrylonitrile, olefins (e.g. ethylene, etc.), styrene, benzoguanamine, formaldehyde condensates, etc. alone or in combination, or together with acrylic acid, methacrylic acid, α, β
-Unsaturated dicarboxylic acids, hydroxyalkyl acrylates, hydroxyalkyl methacrylates, sulfoalkyl acrylates, sulfoalkyl methacrylates,
Polymers containing combinations of styrene sulfonic acid and the like as monomer components can be used.

In addition, epoxy resin, nylon, polycarbonate, phenol resin, polyvinylcarbazole, polyvinylidene chloride, etc. can also be used.

In addition, British Patent No. 1,055,713, U.S. Patent No. 1,939,213, U.S. Pat.
．． No. 376.005, No. 2゜391.181, No. 2,
No. 701,245, No. 3.079,257, No. 3.2
No. 62.782, No. 3,443.946, No. 3,51
No. 6,832, No. 3,539,344, No. 3. 59
1. No. 379, No. 3,754,924, Japanese Unexamined Patent Publication No. 1973
Organic matting agents described in No. 106821, No. 57-14835, etc. can be used.

Also, U.S. Patent Nos. 4,142,894 and 3.76
It is also possible to use a mantle agent which can be dissolved by a development process as described in No. 7.448 and No. 2,992,101.

In particular, spherical water-dispersible vinyl polymers such as homopolymers of acrylic esters such as methylmequaacrylate, glycidyl acrylate, and daccidyl methacrylate, or copolymers of these acrylic esters with each other or with other vinyl monomers. Matting agents and benzoguanamine/formaldehyde condensation polymers (benzoguanamine resins, specifically those shown by the following formula, such as the product Meiko Poster, manufactured by Nippon Shokubai Chemical Co., Ltd.: Existing Chemical Substance 7-31, etc.)
, polyolefin (for example, trade name Flowbeads LE-1
080, CL-2080, HE-5023; Steel Chemical Department or trade name Chemivar ■100; manufactured by Mitsui Petrochemicals), polystyrene beads (manufactured by Moritex), nylon beads (manufactured by Moritex), As resin beads
(manufactured by Moritex), epoxy resin beads (manufactured by Moritex), polycarbonate resin (manufactured by Moritex), etc. are preferable.

Examples of alkali-soluble capping agents include alkali-soluble capping agents such as alkyl methacrylate/methacrylic acid copolymers described in JP-A-537231, JP-A-58-66937, and JP-A-60-8894, and JP-A-58-166341. It is also possible to use an alkali-soluble polymer having an anionic group as described in the above.

Also, JP-A-63-8736, JP-A-61-2301
The capping agent having a narrow particle size distribution as described in No. 41 can be advantageously used.

These mantle agents may be used in combination.

In the present invention, among the above-mentioned matting agents, particles having a particle size of 5 μm or more are used in a total of 30 vol. % or more, especially 35ν01
1%~90vo1. Use a matting agent containing %.

In addition, cloak agents whose maximum particle size does not exceed 20 μm, and those with a particle size of 10 μm or more are 10νo1. % or less is preferable.

The above matting agent is preferably used in an amount of 0.01 to Ig/d, particularly 0.1 to 0.5 g/rr+ per support IM.

The backing layer of the present invention also contains various additives, such as hardeners, thickeners, pH regulators, surfactants, charge regulators, conductive polymers (metal oxides), and antifoggants (developers). Accelerators, development inhibitors), dyes, etc. can be contained for the purpose of preventing halation, improving safelight safety, and improving front-back discrimination.

For example, pyrazolone oxonol dyes as described in U.S. Pat. No. 2,274,782, diarylazo dyes as described in U.S. Pat. No. 2,956,879, U.S. Pat.
No. 207, styryl dyes and zutadienyl dyes described in U.S. Patent No. 3.384.487, U.S. Pat.
Merocyanine dye as described in No. 3, U.S. Pat. No. 3.486
, No. 897, No. 3,652. ．． No. 284, No. 3, 7
18.472, the enamine hemyoxonol dyes described in U.S. Pat. No. 3,976.661 and British Patent No. 584.60.
No. 9, No. 1,177.429, Japanese Unexamined Patent Publication No. 48-851
No. 30, No. 49-99620, No. 49-114420
No. 2,533,472, U.S. Pat. No. 3,148
, No. 187, No. 3.177.078, No. 3.24
No. 7127, No. 3,540.887, No. 3゜57
The dyes described in No. 5.704 and No. 3,653,905 can be used.

Further, it is preferable to contain a slipping agent such as a silicone type, a higher fatty acid type, an alcohol type, an acid amide type, a metal soap, an ester type, an ether type, or a taurine type as described in JP-A-61-188945.

The banking layer may be composed of one layer or two or more layers, and the mantle agent may be added to any layer. The thickness of the backing layer is preferably 0.5 μ to 10 μ, and may be within this range. In this case, the effect of improving the conveyance property of the present invention is clearly recognized.

In the present invention, the sensitizing dyes that spectrally sensitize to wavelengths longer than 600 nm include cyanine dyes, merocyanine dyes, complex scyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, styryl dyes, hemicyanine dyes, oxonol dyes, and hemioxol dyes. Nol dyes and the like can be used.

Useful sensitizing dyes for use in the present invention include, for example, R[! 5E
ARCII 0ISCLO5URE Item 176
43 Section IV-A (December 1978 P, 23), 1teml 83 Section LX (August 1979 P, 437)
) or in the literature cited.

In particular, a sensitizing dye having a spectral sensitivity suitable for the spectral characteristics of various scanner light sources can be advantageously selected.

For example, for light sources for A) helium-neon lasers, Japanese Patent Application Laid-open Nos. 50-62425 and 5418726;
Regarding the trinuclear cyanine dyes shown in No. 59-102229, and B) LED light sources, they are described in Japanese Patent Publications No. 48-42172, No. 51-9609, No. 55-39818, and Japanese Patent Application Laid-open No. 62-284343. Thiacarbocyanin L
C) For semiconductor laser light sources, JP-A-59-191
Tricarbocyanines described in JP-A No. 032, JP-A No. 1-80841, and dicarbocyanines containing a 4-quinoline nucleus described in JP-A-59-192242 are advantageously selected. .

Representative compounds of those sensitizing dyes are shown below.

Specific compound of A) General formula (1) [In formula 2. and Z2 each represent a nonmetallic atomic group necessary to complete a 5- or 6-membered nitrogen-containing heterocyclic nucleus, R2 and R2 each represent an alkyl group, a substituted alkyl group, or an aryl group, Q, and Q2 together represent a group of nonmetallic atoms necessary to complete the 4-thiazolidinone, 5-thiazolidinone or 4-imidazolidinone nucleus, n
l and n2 each represent a methine group or a substituted methine group.

X represents an anion. ml represents O or 1,
When forming an inner salt, m and -Q are used. ] Specifically, the specific compound of e A-4 B) has the general formula (II).

RS1 represents a lower alkyl group. X represents an anion.

n2 and n4 represent 1 or 2.

m3 represents I or O, and when it is an inner salt, m! -0] Specifically, (L) eax [wherein Y and Y2 each form a heterocycle such as a hendithiazole ring, a benzoselenazole ring, a naphthodeazole ring, a naphthoselenazole ring, or a quinoline ring. These heterocycles represent a group of nonmetallic atoms necessary for
It may be substituted with an alkoxycarboxy group or a halogen atom.

R2 and R4 each represent an alkyl group having a lower alkyl group, a sulfo group, or a carboxyl group, re (CH*)ssOJ (CL) ssOx e C) zlls Ct II.

fJl,cOo)I C,H.

■ ■ II g +, ; & 115 119L;.

Shi4119 C.J.

Cz It s 2υ4 These sensitizing dyes may be used alone or in combination, and combinations of sensitizing dyes are often used particularly for the purpose of supersensitization.

Along with the sensitizing dye, it is a dye that itself does not have a spectral sensitizing effect or a substance that does not substantially absorb visible light,
A substance exhibiting supersensitization may also be included in the emulsion.

Useful sensitizing dyes, supersensitizing dye combinations, and supersensitizing substances are listed in Research Disclosure+-(R
esearch Disclosure) Volume 176 1
7643 (published in December 1978), page 23, item 3.

The hydrazine derivative used in the present invention has the general formula (
A compound represented by III) is preferably used.

General formula (III) R, -N-□N□G, ---R! A, At In the formula, R1 represents an aliphatic group or an aromatic group, R2 represents a hydrogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an amino group, a carbamoyl group, or an oxycarnebonyl group, and G .

represents a carbonyl group, a sulfonyl group, a sulfoxy group, a P-group, or an iminomethylene group; A1, R;

Both At's represent a hydrogen atom, one a hydrogen atom and the other a substituted or unsubstituted alkylsulfonyl group, a substituted or unsubstituted arylsulfonyl group, or a substituted or unsubstituted anru group.

In the general formula (III), the aliphatic group represented by R1 preferably has 1 to 30 carbon atoms, particularly a straight, branched or cyclic alkyl group having 1 to 20 carbon atoms.

The branched alkyl group may be cyclized to form a saturated heterocycle containing one or more heteroatoms, and the alkyl group may be an aryl group, an alkoxy group, or , sulfoxy group, sulfonamide group,
It may have a substituent such as a carbonamide group.

- In form (III), the aromatic group represented by R is a monocyclic or bicyclic aryl group or an unsaturated heterocyclic group. Here, the unsaturated heterocyclic group may be combined with a monocyclic or bicyclic aryl group to form a heteroaryl group.

For example, benzene ring, naphthalene ring, pyridine ring, pyrimidine ring, imidazole ring, pyrazole ring, quinoline ring,
Examples include isoquinoline ring, benzimidazole ring, thiazole ring, and benzothiazole ring, among which those containing a benzene ring are preferred.

Particularly preferred as R1 is an aryl group.

The aryl group or unsaturated heterocyclic group of R1 may be substituted, and typical substituents include a linear, branched or cyclic alkyl group (preferably one having 1 to 20 carbon atoms), an aralkyl group (preferably a monocyclic or bicyclic alkyl group having 1 to 3 carbon atoms), an alkoxy group (preferably a carbon number of 1 to 20), a substituted amino group (preferably an alkyl group having 1 to 20 carbon atoms) (amino group substituted with
), ureido group (preferably 1 to 30 carbon atoms)
) etc.

- The alkyl group represented by R2 in format (1) is preferably an alkyl group having 1 to 4 carbon atoms,
It may have a substituent such as a halogen atom, cyano group, carboxy group, sulfo group, alkoxy group, or phenyl group.

The aryl group represented by R is preferably a monocyclic or bicyclic aryl group, and includes, for example, a benzene ring. This aryl group may be substituted with, for example, a halogen atom, an alkyl group, a cyano group, a carboxy group, a sulfo group, or the like.

The alkoxy group is preferably an alkoxy group having 1 to 8 carbon atoms, and may be substituted with a halogen atom, an aryl group, or the like.

The aryloxy group is preferably monocyclic, and the substituent includes a halogen atom.

The amine group includes an unsubstituted amino group and a carbon number of 1 to 10.
Preferably, an alkylamino group or an arylamino group, which may be substituted with an alkyl group, a halogen atom, a cyano group, a nitro group, a carboxy group, etc., and a carbamoyl group is an unsubstituted carbamoyl group, and a carbon number of 1 to 10. An alkylcarbamoyl group or an arylcarbamoyl group is preferred, and may be substituted with an alkyl group, a halogen atom, a cyano group, a carboxy group, or the like.

The oxycarbonyl group is preferably an alkoxycarbonyl group having 1 to 10 carbon atoms or an alkyloxycarbonyl group, which may be substituted with an alkyl group, a halogen atom, a cyan group, a nitro group, or the like.

Among the groups represented by R1, when G is a carbonyl group, preferred are a hydrogen atom, an alkyl group (for example, a methyl group, a trifluoromethyl group, a 3-hydroxypropyl group, a 3-methanesulfonamidopropyl group, etc.). ), aralkyl group (for example, θ~hydroxybenzyl group, etc.)
, oryl group (e.g., phenyl group, 3,5-dichlorophenyl group, 0-methanesulfonamidophenyl group, 4
(methanesulfonylphenyl group, etc.), and a hydrogen atom is particularly preferred.

Furthermore, when G is a sulfonyl group, R2 is an alkyl group (e.g., methyl group, etc.), an aralkyl group (e.g., 0
-hydroxyphenylmethyl group), aryl group (e.g. phenyl group) or substituted amino group (e.g.
dimethylamino group, etc.) are preferred.

When G1 is a sulfoxy group, R2 is preferably a cyanobenzyl group or a methylthiobenzyl group, and when Gl is a -P group, R2 is a methoxy group, ethoxy group, butoxy group, phenoxy group, or phenyl group. A group is preferred, and a phenoxy group is particularly preferred.

When G is an N-substituted or unsubstituted iminomethylene group,
Preferred R2 is a methyl group, an ethyl group, or a substituted or unsubstituted phenyl group.

As the substituent for R2, in addition to the substituents listed for R1, for example, an acyl group, an aralkyl group, an alkyl or aryloxycarbonyl group, an alkenyl group, an alkynyl group, a nitro group, etc. can be applied.

G in general formula (Ill) is most preferably a carbonyl group.

Also, R2 splits the G1Rx part from the remaining molecules, -
It may be one that causes a cyclization reaction to produce a cyclic structure containing an atom of the G-R2 moiety, and specifically, one that can be represented by the general formula (al).

General formula (a) R, -2 In the formula, Zl nucleophilically attacks G.

It is a group that can split the Ry Z + moiety from the remaining molecules, and R8 is the one hydrogen atom removed from R2, and Zl makes a nucleophilic attack on GI, and a cyclic structure can be generated with GI, R3, and Zl. It is something.

More specifically, Zl easily undergoes a nucleophilic reaction with G when the hydrazine compound of general formula (III) generates the next reaction intermediate by oxidation etc. R, -N=N-G, ~R3- Z.

R, -N=A group that can split N from G, specifically 0HXSH or NHRa (R4 is a hydrogen atom, an alkyl group, an aryl group, -COR, or -S
o, R, and R3 represents a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, etc.), or a functional group that directly reacts with G1 such as COOH (where OH, SH, NHR.

-COOH is ON-R even if it is temporarily protected to generate these groups by hydrolysis with an alkali or the like.

Or, -0-R6-C-R, (R,, R7 represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, or a heterocyclic group), such as a hydroxide ion or a sulfite ion. It may be a functional group that can react with G1 by reacting with a nucleophile.

Furthermore, the ring formed by G, R3, and Z is preferably 5R or 6-membered. - Among those represented by format (a), - formats (b) and (
Examples include those represented by Cl.

(general formula) i, where RbI and R4 are a hydrogen atom, an alkyl group (preferably one having 1 to 12 carbon atoms), an alkenyl group (preferably one having 2 to 12 carbon atoms), an aryl group (preferably one having 6 to 12 carbon atoms); 12), and may be the same or different. B1. is an atom necessary to complete a 5-membered ring or a 6-membered ring that may have a substituent, and m and n are 0 or 1
and (n+-m) is 1 or 2.

Examples of the 5-membered or 6-membered ring formed in this reaction include a cyclohexene ring, a cycloheptene ring, a Hensen ring, a naphthalene ring, a pyridine ring, and a quinoline ring.

Zl has the same meaning as in general formula (a).

-Format (C) Rc -fN-)-T-(-CRc' Re!-)-T-Z
.

In the formula, Rc' and Rc'' represent a hydrogen atom, an alkyl group, an alkenyl group, an aryl group or a halogen atom, and may be the same or different.

Rc' represents a hydrogen atom, an alkyl group, an alkenyl group, or an aryl group.

p represents 0 or l, and q represents 1-4.

Rc', Rc" and Rc" may be bonded to each other to form a ring as long as the structure is such that Zl can make an intramolecular nucleophilic attack on Gl.

Rc' and Rc'' are preferably a hydrogen atom, a halogen atom, or an alkyl group, and Re3 is preferably an alkyl group or an aryl group.

q preferably represents 1 to 3; when q is 1, p represents 1 or 2; when q is 2, p represents 0 or 1; when q is 3, p represents 0 or 1; or CR when 3
c'Rc'' may be the same or different.

Zl has the same meaning as in general formula (a).

A+ and Ag are a hydrogen atom, an alkylsulfonyl group having 20 or less carbon atoms, and an alkylsulfonyl group (preferably a phenylsulfonyl group or a sum of Hammett's substituent constants -
Make it more than 0.5! an acyl group (preferably a benzoyl group, or a benzoyl group substituted so that the Hammett substituent constant ring is -0.5 or more), a linear or branched or cyclic unsubstituted and substituted aliphatic acyl groups (
Examples of the substituent include a halogen atom, an ether group, a sulfonamide group, a carbonamide group, a hydroxyl group, a carboxy group, and a sulfonic acid group. )) A 1. A2
The most preferred is a hydrogen atom.

R3 or R2 in the -i formula ([Il) may have a ballast group commonly used in immobile photographic additives such as couplers incorporated therein.

The ballast group is a group having 8 or more carbon atoms and is relatively inert to photography, such as an alkyl group, an alkokene group, a phenyl group, an alkylphenyl group, a phenoxy group,
You can choose from among alkylphenoxy groups, etc.

-R2 or R2 in the formula (I[ groups, mercaptoheterocyclic groups, triazole groups, etc., U.S. Pat. No. 4,385.108;
459,347, JP 59-195.233, JP 59-200231, JP 59-201,045, JP 59201.046, JP 51-201.047, 1
No. 159-201.048, No. 159-201.049,
JP-A-61-170,733, JP-A No. 61-270.74
Examples thereof include the groups described in No. 4, No. 62-948, Tokukai No. 61-67.508, No. 62-67.501, and No. 62-67.510.

Specific examples of the compound represented by general formula (III) are shown below. However, the present invention is not limited to the following compounds.

■ l) ■-2) ■ ■ ■ ■ Cl1ICIICI-1,5) 1 ■-5) ■-6) ■ ■ III-13) ■ ■ ■ ■ ■ 2+) ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ 2日) ■ \ , c, ++ l + ■ ■ ■ ■ ■ csH1l ■ ■ ■ し１１. tH1 ill-42) m-43> nl-n1- In addition to the above-mentioned hydrazine derivatives used in the present invention, RIESEARC)I DISCLO3U
RE Item 23516 (November 1983 issue, P
, 346) and the documents cited therein, as well as U.S. Pat.
No. 276.364, No. 4,278,748, No. 4,3
No. 85,108, No. 4.459 No. 347, No. 4.56
No. 0,638, No. 4,478,928, British Patent No. 2,
011.391B, JP 60-179734, JP 61-ITO 733, JP 61-270,744,
No. 62-948, EP No. 217,310, Special +llI
No. 61-175.234, No. 61-251.482, No. 61-268.249, No. 61-276 283
No. 62-67.508, No. 62-67529,
62-67.510, 62-58.513, 61-130.819, 62-143.469,
Those described in No. 62-166.117 can be used.

In the present invention, when the hydrazine derivative represented by the general formula (III) and the sensitizing dye are contained in a photographic light-sensitive material, they are preferably contained in the silver halide emulsion layer, but other non-photosensitive hydrophilic colloids are used. It may be included in layers (eg, protective layer, intermediate layer, filter layer, antihalation layer, etc.).

Specifically, when the compound used is water-soluble, it is prepared as an aqueous solution, and when it is poorly water-soluble, it is prepared as a solution of water-miscible organic solvents such as alcohols, esters, and ketones, and as a hydrophilic colloid solution. If it is added to the silver halide emulsion layer, it can be added to the silver halide emulsion layer from the start of chemical ripening.
It may be added at any time up to, but it is preferably added between after the chemical ripening and before coating. In particular, it is preferable to add it to a coating solution prepared for coating.

The content of the sensitizing dye of the present invention depends on the grain size of the silver halide emulsion, the halogen composition, the method and degree of chemical sensitization, the relationship between the layer containing the compound and the silver halide emulsion, the type of antifogging compound, etc. It is desirable to select the optimal amount accordingly, and testing methods for this selection are well known to those skilled in the art. Usually preferably from 10-7 mol to 1X10-" mole per 111 moles of halogenide, especially io-"
It is used in a range of 5×10 4 mol to 5×10 4 mol.

In the present invention, the hydrazine derivative represented by formula (III) -a is preferably contained in an amount of 1 x 10-' mol to 1 x 10-' mol per mol of silver halide, particularly 1 x 10-S to 4 x Preferably, the content is 10-'' moles.

Next, in the present invention, it is preferable to use a polyhydroxybenzene compound used for the purpose of improving pressure resistance without impairing sensitivity and improving storage stability. The polyhydroxybenzene compound is preferably a compound having one of the following structures.

X and Y are respectively -H, -OH, 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, -
COOH, -CH,CI-(, COOH.

-CH,,~CH! CHs, CI (CHt
)z, C(CHs), , -0CH,, -CH○, S
Os N a , S O * H.

etc. X and Y may be the same or different; particularly preferred representative examples of compounds are: D-(1) D-(2) D-(3) D-Go) D-(II) D-11δ OH D14) D-(5) D-(6) D-03) D-(lω D-Qω D~θ force D-(lit) D-(7) D-(8) D-(9) D-(19) D - (20) D - (21) il D = (22) 11+1 The polyhydroxybenzene compound may be added to the emulsion layer in the sensitive material or to a layer other than the emulsion layer. is effective in the range of 1O-5 to 1 mol per 1 mol, and particularly effective in the range of 104 mol to 1O-1 mol.
In the present invention, it is preferable to use a slip agent and/or colloidal silica in the outermost layer.

The colloidal silica used in the present invention has an average particle size of 7 μm.
m to 120 μm, the main component is silicon dioxide, and may contain alumina or sodium aluminate as a minor component. These colloidal silicas also contain sodium hydroxide, potassium hydroxide, lithium hydroxide as stabilizers. , an inorganic base such as ammonia, or an organic base such as tetramethylammonium ion.

Regarding these colloidal silicas, JP-A-53-11
2732, Special Publication No. 57-009051, Special Publication No. 57-0
No. 51,653.

A specific example of colloidal silica is Nichijo Kagaku (Japan,
Tokyo), Snowtex 20 (sho.

/Na, O≧57), Snowtex 30 (SiOz
/NagO≧50), Snowtex C (SiOz/N
azO≧100), Snowtex O (SiOz/Na
zO≧500), etc. Here, (SiO, /Na, O is the content weight ratio of silicon dioxide (Sing) and sodium hydroxide, and sodium hydroxide is N
The values are expressed in terms of azO, and all values are listed in the catalog.

The preferred amount of colloidal silica used in the present invention is 0.05 to 1.0, particularly preferably 0.2 to 0.5 in terms of dry weight ratio to gelatin used as a binder in the outermost layer. be.

The polymer latex used in the present invention is an aqueous dispersion of a water-insoluble polymer with an average particle size of 30 μm to 80 μm.
The preferred amount used is 0.01 to 1.0, particularly preferably 0.1 to 0.5, in terms of dry weight ratio to the gelatin used as a binder in the outermost layer.

Typical slip agents used in the present invention include, for example, U.S. Patent No. 3,042,522 and British Patent No. 955.
．． No. 061, U.S. Patent No. 3. o80.317, same 4,
No. 004,927, No. 4゜047.958, No. 3.7
189.567, British Patent No. 1.143.118, etc., and US Pat. No. 2.454.
No. 043, No. 2.732.305, No. 2.976.1
No. 48, No. 3,206,311, German Patent No. 1,28
Higher fatty acid-based, alcohol-based, acid amide lint removal agents described in No. 4.295, No. 1,284.294, etc., British Patent No. 1.263.722, U.S. Patent No. 3,933,51
Metal soap described in No. 6, etc., U.S. Patent No. 2,588,7
No. 65, No. 3.121060, British Patent No. 1,198
．． Ester-based and ether-based slip agents described in No. 387, etc.
U.S. Patent No. 3,502,473, U.S. Patent No. 3,042.22
There are taurine-based slip agents described in No. 2.

As the slip agent of the present invention, an alkylpolysiloxane represented by the following general formula (IV), -format (V) or -format (Vl) and liquid paraffin which is in a liquid state at room temperature are preferably used. More preferably, an alkylpolysiloxane having a polyoxyalkylene chain in the side chain represented by the general formula (IV) and an alkylpolysiloxane represented by the general formula (V) are used.

General formula (IV) l? '' In the formula, R is an aliphatic group (e.g., an alkyl group (preferably carbon j to 18), a substituted alkyl group (e.g., an aralkyl group, an alkoxyalkyl group, an aryloxyalkyl group, etc.)) or an aryl group (e.g., phenyl base, etc.)
represents. R' represents a hydrogen atom, an aliphatic group (e.g., an alkyl group (preferably one having 1 to 12 carbon atoms), a substituted alkyl group, etc.) or an aliphatic group (e.g., a phenyl group, etc.); R# represents an alkyl group; (e.g. methyl group, etc.) or alkoxyalkyl group (e.g. methoxymethyl group, etc.), A represents a divalent residue of an aliphatic hydrocarbon, n is O or an integer from 1 to 12, and p is 0 to 50. number of, q
is a number from 2 to 50 (preferably 2 to 30), and X is a number from 0 to 10
The number of 0, y is a number of 1 to 50, Z is a number of 0 to 100, and X+y+z is 5 to 250 (preferably 10 to 50)
is the number of

Specific examples of R include methyl, ethyl, propyl, pentyl, cyclopentyl, cyclohexyl, dimethylpentyl, heptyl, methylhexyl, octyl, dodecyl, octadecyl, phenylethyl, methylphenylethyl, phenylpropyl, cyclohexylpropyl, benzyloxy. Includes propyl, phenoxypropyl, ethyloxypropyl, butyloxyethyl, phenyl, etc.

The group represented by A is methylene, 1-one-trimethylene,
Examples of the alkyl group represented by Rr include 2-methyl-1-one-trimethylene, methyl, ethyl,
Examples include propyl, butyl, amyl, hexyl, heptyl, octyl, nonyl, decyl, and dodecyl groups.

General formula (V) General formula [V] is a cyclic siloxane having a siloxane unit represented by the following general formula (V-1) and a general formula (V
-2) includes a linear siloxane having the terminal group shown in .

General formula (V-1) CH.

i −0 General formula (■-2) CH.

R,=Si-0CHl In the formula, R represents an alkyl group having 5 to 2 carbon atoms, a cycloalkyl group, an alkoxyalkyl group, an arylalkyl group, an aryloxyalkyl group, or a glycidyloxyalkyl group.

R2 represents an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 5 to 20 carbon atoms, an alkoxyalkyl group, a 71noralkyl group, an aryloxyalkyl group, and a glycidyloxyalkyl group.

l represents O or a number greater than or equal to 1, m represents a number greater than or equal to 1, and E+m represents a number from 1 to 1000. Preferably E0m is 2 to 500.

Specific examples of R5 in the compound represented by formula (V) include pentyl, methylpentyl, cyclopentyl, cyclohexyl, dimethylpentyl, heptyl, methylhexyl, octyl, eicosyl, phenylethyl, methylphenylethyl, phenylfurohyl, cyclohexylpropyl, hensyloxypropyl, phenoxypropyl,
Examples include tolyloxypropyl, naphthylpropyl, ethyloxypropyl, butyloxyethyl, octadecyloxypropyl, glycidyloxypropyl, and glycidyloxybutyl.

General formula (Vl) In the formula, R1 is an alkyl group having 1 to 3 carbon atoms, and R4 is a carbon number 1
-3 alkyl group or an alkoxy group having 1 to 2 carbon atoms. m is an integer from O to 2000.

Next, representative examples of compounds represented by the general formula (rV) will be shown.

(■-I) (■-2) (OCHzC)It) sOH Hs X+Y+Z-30 X+Y+Z=50 (■-口) (■-E) (OCHzC)It) +. QC4Hqx 10y1zte4
0 X+Y+Z=100 (■~c) (to ■-) (OCHzcH) lo (OCII□CHi) +.

0C3H? CH.

x+'y'+z-a　5 General formula (V) Among the compounds represented by the (■ e) Representative compound examples are shown below.

(■ stomach) (■-) (■ mouth) (■-t) (■-c) (■ D) General formula (Vl) Among the compounds represented by the Representative compound examples are shown below.

(■-i) Specific compound examples of the anionic surfactant used in the present invention are shown below.

(■-Port) In the present invention, it is more preferable to use an anionic surfactant represented by the following format [■].

-Format [■] R' R-CON-(CHI), ISO3M In the formula, R represents a substituted or unsubstituted alkyl group, alkenyl group, or aryl group having 3 to 30 carbon atoms, and R' represents a hydrogen group, a carbon It represents a substituted or unsubstituted alkyl group, alkenyl group or aryl group of number 1 to 10, n represents a number of 2 to 6, and M represents a hydrogen atom or an inorganic or organic cation.

(■-I) (■-口) (■-C) (■-2) (■-E) (■-Go) (■-T) CJtCONHCToCHzSOJa CJ+*C0NHC)IzC! IzSOJaC+ql1
3ffCONHCHzCIIzSOJa1h Cdl+ 5cON-CtltCJIzSO3KCH.

C,,II,,C(14-CIlzCIIzSOJaC
ll.

C+:+l1ztCO-N-CIlzCIIzSOJa
C+JsiCO-N-CIL2CllzSOJa(■-
NU) CxHr C+sTo+C0-N-C)IzC)IzSOJ The coating amount of the slip agent is 0.005 to Ig/rrf, especially 0.005 to Ig/rrf.
01~O, 1g/r+? It is preferable that

In addition, when using an anionic surfactant of formula -119 (■), the amount is 0.001 to 0.5 g/bo, especially 0.01 to 0
It is preferable that it is 2 g/nf.

The silver halide used in the present invention may be, for example, any one of silver chloride, silver bromide, silver iodide, silver chlorobromide, silver chloroiodide, silver iodobromide, silver chloroiodobromide, and the like. In the present invention, among the above-mentioned silver halides, silver chloroiodobromide, silver chlorobromide, and silver iodobromide are preferred. More preferably, silver chlorobromide or silver chloroiodobromide containing 0 to 1 mol % of silver iodide is advantageously used.

The average grain size of the silver halide used in the present invention is preferably fine (for example, 0.7 μm or less), particularly 0.7 μm or less.
It is preferably 5μ or less. There is basically no restriction on the particle size distribution, but monodisperse is preferable. Monodisperse means that at least 95% of the particles are within ±40% of the average particle size in terms of weight or number of particles. It is composed of a group of particles that have

Silver halide grains in photographic emulsions may have regular (reg+ar) crystals such as cubic or octahedral, or irregular (irre) crystals such as spherical or plate-like.
It may have crystals such as tar) or a composite of these crystal forms.

The interior and surface layers of the silver halide grains may consist of a uniform phase or may consist of a simple phase.

Two or more silver halide emulsions formed separately may be used in combination.

Further, the silver halide emulsion layer may be a single layer or may be a multilayer (two layers, three layers, etc.). In the case of zero multilayers, different silver halide emulsions may be used. However, the same one may be used.

In the silver halide emulsion used in the present invention, cadmium salt, sulfite, lead salt, thallium salt, rhodium salt or its complex salt, iridium salt or its complex salt, etc. are allowed to coexist in the silver halide grain formation or physical ripening process. Good too.

Silver halides particularly suitable for use in the present invention are prepared in the presence of io-' to 1O-5 moles of iridium salt or complex salt thereof per mole of silver, and have a silver iodide content on the grain surface of The silver iodide content is higher than that of silver iodide. When an emulsion containing such silver haloiodide is used, photographic characteristics with higher sensitivity and higher gamma can be obtained.

In the above, it is desirable to add the iridium salt in the above amount before the completion of physical ripening in the silver halide emulsion manufacturing process, especially during grain formation.

The iridium salt used here is a water-soluble iridium salt or an iridium complex salt, such as iridium trichloride, iridium tetrachloride, potassium hexachloroiridate (In), potassium hexachloroiridate (rV),
Examples include ammonium hexachloroiridium ([[)].

Gelatin is advantageously used as a binder or protective colloid in photographic emulsions, 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: hydroxyethyl cellulose,
Cellulose derivatives such as carboxymethyl cellulose, cellulose sulfate esters, sodium alginate, starch derivatives, etc. ! ! Various synthetic hydrophilic polymers such as derivatives, single or copolymers of polyvinyl alcohol, polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, polyvinylpyrazole, etc. Substances can be used.

The silver halide emulsion used in the present invention does not need to be chemically sensitized, but may be chemically sensitized. Methods for chemical sensitization of silver halide emulsions include sulfur sensitization, reduction sensitization, and noble metal sensitization. Sensitization methods are known, and any of these methods may be used alone or in combination for chemical sensitization.

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

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 light-sensitive material of the present invention includes JP-A Nos. 60-140340 and 6]-1679 for the purpose of promoting high sensitivity and high contrast.
Compounds described in No. 39 can be added. These may be used alone or in combination of two or more.

The light-sensitive material of the present invention may contain various compounds for the purpose of preventing fogging during the manufacturing process, storage, or photographic processing of the light-sensitive material, or for stabilizing photographic performance. That is, azoles such as hendithiazolium salts, nitroindazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptohenzothiazoles, mercaptothiadiazoles, aminotriazoles, benzothiazoles, nitrobenzotriazoles. mercaptopyrimidines; mercaptotriazines; thioketo compounds such as oxazolinthione; azaindenes, such as triazaindenes, tetrazaindenes (especially 4-hydroxy-substituted (133a,7) tetrazaindenes) , pentaazaindenes, etc.; compounds known as antifoggants or stabilizers can be added, such as benzenethiosulfonic acid, benzenesulfinic acid, benzenesulfonic acid amide, etc. Among these, Preferred are penzotriazoles (eg, 5-methyl benzotriazole) and nitroindazoles (eg, 5-nitroindazole), and these compounds may also be included in the treatment liquid.

The photographic emulsions and non-photosensitive hydrophilic colloids of the present invention may contain inorganic or organic gelatin hardeners. For example, activated vinyl compounds (1゜3.!l+-)
Liacryloyl-hexahydro-3-triazine, bis(vinylsulfonyl)methyl ether, N,N'-methylenebis-(β-(vinylsulfonyl)propionamide), etc.), active halogen compounds (2,4-dichloro-
6-hydroxy-5-lyazine, etc.), mucohalogen acids (mucochloric acid, etc.), N-carbamoylpyridinium salts ((1-molpoly,carbonyl-3-pyridinio)methanesulfonate, etc.) haloamidinium salts [(
1-(1-chloro-1-pyridinomethylene)pyrrolidinium, 2-naphthalenesulfonate, etc.) can be used alone or in combination. Among them, JP-A-53-
41220, 53-57257, 59-16254
The active vinyl compounds described in No. 6, No. 60-80846 and the active halides described in U.S. Pat. No. 3,325,287 are preferred.

The photographic emulsion layer or other hydrophilic colloid layer of the light-sensitive material of the present invention may contain coating aids, antistatic agents, emulsification dispersion, adhesion prevention, and improvement of photographic properties (e.g., development acceleration, contrast enhancement, aggravation), etc. , and may contain various surfactants.

For example, saponins (steroids), alkylene oxide derivatives (e.g., polyethylene glycol, polyethylene glycol/polypropylene glycol condensates,
Polyethylene glycol alkyl ethers or polyethylene glycol alkylaryl ethers, polyethylene glycol esters, polyethylene glycol sorbitan esters, polyalkylene glycol alkyl amines or amides, silicone polyethylene oxide adducts M), glycidol derivatives (e.g. alkenyl succinic acid) Nonionic surfactants such as polyglycerides, alkylphenol polyglycerides), fatty acid esters of polyhydric alcohols, and alkyl esters of sugar; alkyl carboxylates, alkyl sulfonates, alkylbenzene sulfonates, alkylnaphthalene sulfonates , alkyl sulfate esters, alkyl phosphate esters, N-acyl-N-alkyl taurine's, sulfosuccinates, sulfoaltels, polyoxyethylene alkyl phosphates, etc., carboxy groups, sulfo groups, etc. , anionic surfactants containing acidic groups such as phospho groups, sulfate ester groups, and phosphate ester groups; Surfactants: Alkylamine salts, aliphatic or aromatic quaternary ammonium salts, heterocyclic quaternary salts such as pyridinium, imidazolium, etc.
Cationic surfactants such as ammonium salts and phosphonium or sulfonium salts containing aliphatic or heterocycles can be used.

The photographic light-sensitive material of the present invention may contain a capping agent such as silica, magnesium oxide, polymethyl methacrylate, etc. in the photographic emulsion layer and other hydrophilic colloid layers for the purpose of preventing adhesion.

The photosensitive material of the present invention includes, for the purpose of improving dimensional stability, etc.
Can include dispersions of water-soluble or IiO-based synthetic polymers. For example, alkyl (meth)acrylates,
Alkoxyalkyl (meth)acrylate, glycidyl (meth)acrylate, (meth)acrylamide, vinyl ester (e.g. vinyl acetate), acrylonitrile, olefin, styrene, etc. alone or in combination, or together with acrylic acid, methacrylic acid, αβ −
Polymers containing as monomer components a combination of unsaturated dicarboxylic acids, hydroxyalkyl (meth)acrylates, sulfoalkyl (meth)acrylates, styrene sulfonic acids, etc. can be used.

As the support for the photosensitive material of the present invention, cellulose triacetate, cellulose diacetate, nitrocellulose, polystyrene, polyethylene terephthalate, etc. can be used, but a polyethylene terephthalate film is most preferred.

These supports may be subjected to corona treatment by a known method, and may also be subjected to downstream processing by a known method if necessary.

Furthermore, a waterproof layer containing a polyvinylidene chloride polymer may be provided in order to improve so-called dimensional stability, in which the dimensions change with changes in temperature and humidity.

Development accelerators or nucleating and infectious development accelerators suitable for use in the present invention include JP-A-53-77616 and JP-A-53-77616;
4-37732, 53-137゜133, 60-1
In addition to the compounds disclosed in No. 40.340, No. 60-14959, etc., various compounds containing N or S atoms are effective.

It is preferable that the silver halide emulsion layer and other layers of the photographic light-sensitive material of the present invention contain a compound having an acid group. Examples of compounds having acid groups include organic acids such as salicylic acid, acetic acid, and ascorbic acid, and polymers or copolymers having acid groups such as acrylic acid, maleic acid, and phthalic acid as repeating units. Regarding these compounds, see JP-A-61-223834 and JP-A No. 61-223834.
No. 228437, No. 62-25745, No. 62-55
642 and Japanese Patent Application No. 61-62740 can be referred to. Among these compounds, particularly preferred are ascorbic acid as a low molecular compound, and acid monomers such as acrylic acid and crosslinkable monomers having two or more unsaturated groups such as divinylbenzene as high molecular compounds. A water-dispersible latex copolymer consisting of

In order to obtain ultra-high contrast and high sensitivity photographic properties using the silver halide photosensitive material of the present invention, it is necessary to use a conventional infectious developer or a highly alkaline developer with a pH close to 13 as described in U.S. Pat. No. 2,419,975. It is not necessary to use a stable developer, and a stable developer can be used.

That is, the silver halide photosensitive material of the present invention contains 0.15 mol/1 or more of sulfite ion as a preservative, and P
HI O, 5-12.3, especially pH/1.0-12.0
A sufficiently high contrast negative image can be obtained using this developer.

There are no particular restrictions on the developing agent used in the developer used in the present invention, but it preferably contains dihydroxybenzenes, and dihydroxybenzenes and 1-phenyl-3- A combination of pyrazolidones or a combination of dihydroxybenzenes and P-aminophenols may also be used.

The dihydroxybenzene developing agent used in the present invention includes hydroquinone, chlorohydroquinone, bromohydroquinone, isopropylhydroquinone, methylhydroquinone, 2,3-dichlorohydroquinone, 2,5-
Examples include dichlorohydroquinone, 2,3-dibromohydroquinone, 2,5 dimethylhydroquinone, and hydroquinone is particularly preferred.

As the developing agent for 1-phenyl-3-pyrazolidone or its derivative used in the present invention, 1-phenyl-3-virapritone, 1-phenyl-4,4-dimethyl-4-pyrazolidone, 1-phenyl-4-methyl-4 -Hydroxymethyl-3-virapritone, 1-phenyl-4,4-dihydroxymethyl-3-pyrazolidone, l-phenyl-5
-Methyl-3-virapriton, 1-P-aminophenyl 4,4-dimethyl-3-virapriton, l-Ptolyl-
Examples include 4,4-dimethyl-3-pyrazolidone.

Examples of the p-aminephenol developing agent used in the present invention include N-methyl-p-aminophenol, p-aminophenol, N-(β- and droxyethyl)-p-aminephenol, and N-(4-hydroxyphenyl)glycine. ,
There are 2-methyl-p-aminephenol, p-hensylaminophenol, etc., among which N-methyl-p-aminephenol is preferred.

The developing agent is preferably used in an amount of usually 0.05 mol/2 to 0.8 mol/2. In addition, when using a combination of dihydroxybenzenes and 1-phenyl-3-virapritones or p-amino-phenols, the former is 0.
05 mol/l to 0.5 mol/l, the latter 0.106 mol/l
It is preferable to use it in an amount equal to or less than R.

Preservatives for sulfite used in the present invention include sodium sulfite, potassium sulfite, lithium sulfite, ammonium sulfite, thorium bisulfite, potassium metabisulfite,
Examples include formaldehyde and sodium bisulfite. Sulfite is 0.4 mol/P or more, especially 0.5 mol/I! , or more are preferable. Further, the upper limit is preferably 2.5 mol/i.

Alkaline agents used for setting pH include pH adjusting agents and buffers such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, tribasic sodium phosphate, and tribasic potassium phosphate. The pH of the developer is 10.
It is set between 5 and 12.3.

Additives used in addition to the above ingredients include compounds such as boric acid and borax, development inhibitors such as sodium bromide, potassium bromide, and potassium iodide; ethylene glycol, diethylene glycol, triethylene glycol, dimethylformamide, and methyl cellosolve. , organic solvents such as hexylene glycol, ethanol, and methanol; antifoggants such as indazole compounds such as 1-phenyl to 5-mercaptotetrazole and 5-nitroindapool; and penttriazole compounds such as 5-methylbenztriazole; or It may also contain a black pepper inhibitor, and if necessary, a color toning agent, a surfactant, an antifoaming agent, a water softener, a hardening agent, and JP-A-56-10
It may also contain the amino compounds described in No. 6244.

In the developing solution of the present invention, JP-A-56-2 is used as a silver stain preventive agent.
Compounds described in No. 4,347 can be used. Special Ij1 1986-109 as a solubilizing agent added to the developer
．． Compounds described in No. 743 can also be used. Furthermore, as a pH buffering agent used in the developer, JP-A-6 (193)
Compounds described in No. 433 or Japanese Patent Application No. 1987-2870
Compounds described in No. 8 can be used.

As the fixing agent, those having commonly used compositions 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 water-soluble aluminum (eg, aluminum sulfate, light bread, etc.) as a hardening agent. Here, the amount of water-soluble aluminum salt is usually 0.4 to 2.0
g-Al/l. Furthermore, a trivalent iron compound can also be used as an oxidizing agent in the form of a complex with ethylenediaminetetraacetic acid.

The developing temperature is conventionally selected between 18°C and 50°C, but more preferably between 25°C and 43°C.

Example-1 Aqueous solutions of silver nitrate, potassium iodide, and potassium bromide were prepared in a gelatin water solution maintained at 50 °C overnight in the presence of 4 x 10-' mol of potassium iridium (III) hexachloride and ammonia per 1 mol of Ag. was added at the same time for 60 minutes and the PAg was maintained at 7.8 during that time, resulting in an average particle size of 0.28μ.
A cubic monodisperse emulsion having an average silver iodide content of 1 mol % was prepared. Further, this emulsion was washed with water in a conventional manner to remove soluble salts, and then 7' latin was added. Continuing, i
Emulsion A was prepared by adding a sensitized potassium aqueous solution of 0.11 mol % per 1 mol of ff to convert the grain surface.

To this emulsion A, compound examples B-1 and B-4 of formula [■] were added as sensitizing dyes at 4.0 x 10-' mol 1 mol Ag, respectively, and compound example IIT- of general formula (III) was added as a hydrazine derivative. 5 to 1.2X10-' mol 1 mol Ag,
5.0 x 10-' mol 1 mol Ag of I[1-19 was added sequentially, and further 8 mg/4-hydroxy-6-methyl-1,3,3,a,7-titrazaindene was added as a stabilizer.
if, polyethyl acrylate latex (particle size 0.0
5μ) 600mg/ITr, 5-methylbenztriazole 20mg/n, Vinylsulfonylacetamido)ethane 145■/
The gelatin was added sequentially and coated on a polyethylene terephthalate film having a thickness of 100 μm so that the amount of gelatin was 3.5 g/rrr and the gelatin was 2.0 g/%.

Furthermore, the following formulation = 1.2 was sequentially applied as a protective layer thereon.

Prescription-1 Gelatin 1.0 g/Bo L-
Ascorbic acid 30ag/ITf compound example D-(1) 190■/vinity acrylate latex (average particle size 0.05 u) 2401g
/rrtPolystyrene sulfonic acid sodium trilam salt 3■/rTf formulation-
2 Gelatin 0.6g/nt polymethyl methacrylate fine particles (average particle size 2.5μ) 60■/PO compound example ■- (gelatin dispersion) 10■/back dodecylbenzenesulfonic acid sodium salt 201IIg/BON-
Perfluorooctane sulfonyl-N-propylglycine bottaium salt 4■/rrf Colloidal silica (Snowtex C) 90■/po Next, on the other side, apply a back layer of Formulation 3, as shown in Table 1. A back protective layer of Formulation-4 with a different cape agent was applied.

Formulation-3 Gelatin 3g/A compound-1
60■/Bo compound-290aIg
/Bo compound-3 80+ng/Posohexyl α-sulfosacnate sodium salt 40mg/Pododecylbenzenesulfonic acid sodium salt 40mg/Bo1.3-
Divinylsulfonyl 2-propatol 120mg/Polyethyl acrylate Latenx (particle size 0.05 u) 300mg/
n? Formulation-4 Gelatin 0.8 g / posihexyl-α-sulfozacnate sodium salt 15 ■ / bododecylbenzenesulfonic acid sodium salt sodium acetate matting agent ■ - (gelatin dispersion) Compound-1 Compound-2 15 mg / Po40 ■/A (Table-1) 100■/Bore Samples 1 to 7 obtained in this way were heated to 50cu+X50C.
Cut to size Il, stack 100 sheets, 75
Vacuum-pack the sample in a polyethylene-coated paper bag under reduced pressure conditions of mHg, leave it for 24 hours, then open the bag. Immediately after that, use a bite plate to suck up the edge of the sample, and when transporting one sample, the second sample will be placed together. When I counted the number of times it was lifted, the results shown in Table I were obtained.

It can be seen that in Samples 3 and 4.67 of the present invention, the number of times the second sheet is lifted is drastically reduced.

The particle size of the mantle agent was measured by dispersing the mantle agent in saline using a Coulter Counter manufactured by Coulter Electronics with an aperture of 100 μm, and the particle size distribution was expressed in volume percentage.

Example-2 An aqueous solution of silver nitrate and sodium chloride containing 3X10-' mol of KxIrC1- and 3X10-' mol of (N11.)coRhCl b per 1 mol of silver and 1 mol of Sl were added to an aqueous gelatin solution kept at 48°C. By simultaneously adding a sodium bromide aqueous solution equivalent to 30 mol% per 30 minutes and keeping the potential at 70 mV during that time, the average particle size was reduced to 0.
．． A 28μ monodisperse silver chlorobromide emulsion was prepared. After conversion was carried out by adding 0.2 mol % of a 1% aqueous potassium iodide solution per mol of silver to this emulsion, desalting was carried out by the flocculation method. Hypo and chloroauric acid were added to this emulsion, and after chemical ripening at 60°C, 4-hydroxy-6-methyl-1,3,3 was added as a stabilizer.
a.

A 1% solution of 7-chitrazaindene was added in an amount of 30 m/mol.

1 kg of this emulsion contains 0% of the infrared sensitizing dye represented by C-6.
．． Sensitization in the infrared region was performed by adding 0.05% solution for 60 days.

This emulsion was treated with 4,4'-bis-(4,6-dinaphthoxypyrimidin-2-ylamino)-stilbendisulfonic acid disodium salt for supersensitization and stabilization.
Seventy degrees of a 5% methanol solution and ninety degrees of a 0.5% methanol solution of 2,5-dimethyl-3-allyl-benzothiazole iodo salt were added. Furthermore, as a hydrazine derivative, compound example 111-5 of -format (1) is used! , 3 X
10 bow mole 1 mole Ag, m-19 5.3XlO-' mole 1 mole Ag, hydroquinone 1100I1/rr? ,
Polyethyl acrylate latex was used as a plasticizer at a gelatin binder ratio of 25%, and 2-bis(vinylsulfonylacetamide) ethane was used as a hardening agent at 1601 ng/%.
, and coated onto a polyester support at a silver content of 3.7 g/rd. Gelatin was 2.5 g/I.

On top of this, gelatin 0.6g/rd, polymethyl methacrylate 60111g/I with a particle size of 3 to 4μ as a cloak agent, colloidal silica (Snowtex C) with a particle size of 10 to 20μμ 70M/I, compound example ■-to 100■ A protective layer upper layer containing dodecylbenzenesulfonate sodium salt as a coating aid and a fluorine-based surfactant of the following structural formula (2), gelatin 0.7 g/rd, polyethyl acrylate latex 2251I 1 g/rrf,
Dye of the above structural formula (■) 20 ■/rr, dye of (■) 10 ■/rr
A lower protective layer containing r and sodium dodecylbenzenesulfonate as a coating aid was simultaneously coated on a polyethylene terephthalate film having a thickness of 100 μm.

■ CaFt tsOJ-CHxCOOKCgoH? (CIl□Lsoz (C1h) 4SOJ Next, on the opposite side, a back layer having the following formulation was applied, and a back protective layer with different matting agents as shown in Table 2 was applied thereon.

(Back layer) Gelatin 3.0 g / Sodium bododecylbenzenesulfonate 80 ■ Dye a
80■b
30■C100111g 1.3-divinylsulfonyl 2-propatol 60■/niPolyvinyl-hensensulfonate potassium 30g/r4/\115c! (For CIl□>asOz (back protective layer) Gelatin matting agent sodium dodecylbenzenesulfonate 0.75 g/po (Table-2) 20 ■/po Fluorine surfactant (above compound ■) 2 ■/n (compound Example ■- (gelatin dispersion) 100 ■/rrl Samples 8 to 14 thus obtained were evaluated for transportability in the same manner as in Example 1. The results are shown in Table 2.

As is clear from Table 2, sample 10.11.13 of the present invention
．． It can be seen that No. 14 has clearly improved transportability.

Example-3 A polyhydroxybenzene compound was added to the protective IN layer of Formulation-1 of Sample-7 of Example-1, and a slip agent was added to the protective layer of Formulation-2.
Samples with colloidal silica added as shown in Table 3
The fog of the emulsion layer when the emulsion side and back side of the same sample are rubbed together under a certain load (
The evaluation of Owi transportability, which investigated the occurrence of smear fog (hereinafter referred to as "slick fog"), was carried out in the same manner as in Example-1. The results are shown in Table 3.

As is clear from Table 3, samples of the present invention had good transportability and no scouring occurred.

Display of incidents name of invention person who makes corrections Relationship with the incident Heisei/Year Patent Application No. 777/0 Silver halide photographic material

Claims (3)

[Claims] (1) A silver halide photographic material having at least one photosensitive layer made of a silver halide emulsion spectrally sensitized to wavelengths longer than 600 nm on a transparent support, the photosensitive layer or other hydrophilic colloid layer. A halogen compound containing a hydrazine derivative therein, and a backing layer containing a matting agent containing particles with a particle size of 5 μm or more and 30% by volume or more is provided on the opposite side of the support from the photosensitive layer. Silver chemical photographic material. (2) The silver halide photographic material according to claim 1, wherein each of the photosensitive layer or other hydrophilic colloid layer contains one or more polyhydroxybenzene compounds. (3) Claim 1, characterized in that the outermost layer of the photosensitive layer contains a slip agent and/or colloidal silica.
Silver halide photographic material described in Items 1 and 2