JPS62247351A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain a silver halide photographic sensitive material having such photographic characteristics as high sensitivity, high contrast and few black spots by incorporating an acid polymer and a quinone trapping agent into an emulsion layer or other hydrophilic colloidal layer. CONSTITUTION:An acid polymer and a quinone trapping agent and incorporated into an emulsion layer or other hydrophilic colloidal layer. The acid polymer used is preferably represented by formula I or II and the preferred amount of the acid polymer used is 0.2-3g/m<2>. The quinone trapping agent is a compound which reacts with quinone and makes the quinone lose its oxidizing action, that is, a compound used generally as a reducing agent or an antioxidant or a compound capable of nucleophilic addition to quinone. Catechol, hydroquinone or other dihydroxybenzene is preferably used as the quinone trapping agent.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention is used in the field of photolithography. This invention relates to a silver halide photographic material (particularly a negative disc) which can be rapidly formed using a highly stable processing solution to produce ultra-high contrast images.

(Prior Art) It is known that certain silver halides can be used to form extremely high contrast photographic images, and methods for forming such photographic images are used in the field of photolithography.

For example, silver chlorobromide (at least the silver chloride content is jO
Lith type silver halide photosensitive material 11 consisting of qIb or higher)
The effective concentration of sulfite ions is kept very low (usually O5
7 mol/i or less) A method for obtaining line or halftone images with high contrast and high blackening density, with image areas and non-image areas being clearly distinguished, by processing with a hydroquinone developer is mentioned. . However, with this method, the concentration of sulfite in the developer is low, making the development extremely unstable against air oxidation.Currently, various efforts and innovations have been made to keep the solution activity stable. Met.

For this reason, the above development method (lith development system)
There is a need for an image forming system that eliminates the instability of image formation caused by the process, develops with a processing solution that has good storage stability, and obtains ultra-high contrast photographic characteristics, and U.S. Pat.
Hiro 2, Dohiro, 76? , No. 277, Dohiro, 22/, ♂j
No. 7, Dohiro.

22 Hiro, Hiro O1 issue, Do Hiroe J tA3e 735' issue, Same≠, 272,401s issue, Same≠, 3//, 7r1 issue, 5,! A surface latent image type silver halide photographic light-sensitive material to which a certain acylhydrazine compound was added was prepared at pH/
/,0-/2.3, containing a sulfite preservative of 0,/j mol/L or more, and processing with a developer having good storage stability,
r is 10y! A system has been proposed for forming negative images with ultra-high contrast exceeding l-.

This new image forming system can also be used with silver iodobromide and silver chloroiodobromide, whereas conventional ultra-tone image formation could only use silver chlorobromide, which has a high silver chloride content. It has characteristics. This new image-forming system not only increases the sensitivity to high contrast, but also causes the undesirable phenomenon of black spots due to contagious development, which is a problem in the photolithography process.

A black spot is a black spot made of minute developed silver that occurs in an unexposed, non-image area.

Special request to improve black spots like this /7≠
Hiroko 0, Tokkun Sho 60-6≠19g, Tokkun Sho 1.0-64
It has been disclosed that the invention can be improved by introducing a water-soluble mercapto compound, an organic acid, an acid polymer, etc. However, even with these methods, due to fatigue of the developer over time, if the sulfite introduced as a preservative decreases significantly or the pH increases, problems occur frequently, and at the same time, the concentration (L) max) It had the disadvantage of a decrease in Therefore, great efforts have been made to prevent the occurrence of black spots, but efforts to improve black spots are often accompanied by a decrease in sensitivity and density (Dmax) or a decrease in image contrast. There was a strong desire for a system that could prevent black spots and maintain high sensitivity and high density.

(Problems to be Solved by the Invention) Therefore, the object of the present invention is to provide a silver halide photographic material which uses a stable developing solution and has photographic properties with extremely high sensitivity and high contrast, with γ exceeding IO, and with significantly less black spots. It is an object of the present invention to provide an image forming method using the present invention.

(Means for Solving the Problems) The above object of the present invention is to have at least one silver halide emulsion layer on a support and contain a hydrazine derivative in the emulsion layer or other hydrophilic colloid layer. A silver halide photographic light-sensitive material characterized in that the emulsion layer or other hydrophilic colloid layer contains an acid polymer and a quinone trap L, and a silver halide photographic light-sensitive material characterized in that the emulsion layer or other hydrophilic colloid layer contains an acid polymer and a quinone trap L. This could be achieved by an image forming method in which development is performed using a developer containing sulfite ions of /J mol/i or more and having a pH of 10.J-/2.3.

As the hydrazine derivative in the present invention, US Patent Hirohiro 7! Sulfinyl group described in r22g issue! Examples include hydrazine derivatives having the following formula (1) and compounds represented by the following general formula (1).

General formula (1) %formula% In the formula, R1 represents an aliphatic group or an aromatic group.

In general formula (1), the aliphatic group represented by 1 preferably has 7 to 30 carbon atoms, particularly carbon number/~
20 straight chain, branched or cyclic alkyl groups. The branched alkyl group herein may be cyclized to form a saturated heterocycle containing seven or more heteroatoms therein. In addition, this alkyl group is a ryoryl group,
It may have a substituent such as an alkoxy group, a sulfoxy group, a sulfonamide group, or a carbonamide group.

For example, t-buty/l/4% I'm-octyl group, t-
Examples include octyl group, cyclohexyl group, pyrrolidyl group, imidazolyl group, tetrahydrofuryl group, and morpholy7 group.

In the general formula (1), the aromatic group represented by 1 is a monocyclic or λ-ring aryl group or an unsaturated heterocyclic group. Here, the unsaturated heterocyclic group may be condensed with a monocyclic or λ-ring aryl group to form a heteroaryl group.

For example, benzene ring, naphthalene ring, pyridine ring, pyrimidine ring, imidazole ring, pyrrolidyl group, 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 aryol group.

The aryl group or aromatic group of R1 may have one substituent.

Typical substituents include straight-chain, branched or cyclic alkyl groups (preferably those with a carbon number of up to 20), aralkyl groups (preferably monocyclic or cocyclic groups with an alkyl moiety of up to 3 carbon atoms). monoton, alkoxy group (preferably carbon number/~20), substituted amino group (preferably carbon number/~20),
(amino group substituted with ~20 alkyl groups), acylamino group (preferably having 2 to 30 carbon atoms), sulfonamide group (preferably having carbon number/~30)
, ureido group (preferably one having carbon number/~3Q)
and so on.

R1 in the general formula (1) may have a ballast group commonly used in immobile photographic additives such as couplers incorporated therein. Ballast group has 1 or more carbon atoms
It is a relatively inert group with respect to photographic properties, and can be selected from, for example, an alkyl group, an alkoxy group, a phenyl group, an alkylphenyl group, a phenoxy group, an alkylphenoxy group, and the like.

R1 in the general formula (1) may have a group incorporated therein to enhance adsorption to the silver halide grain surface. Such adsorption groups include thiourea groups, heterocyclic thioamide groups, mercapto heterocyclic groups, triazole groups, etc.
Examples include the groups described in No. 313.10.

Synthesis methods for these compounds are described in JP-A No. 33-20-27,
No. 33-20222, No. j3-16732, No. 33
-20311 etc.

In the present invention, when a hydrazine derivative is contained in a photographic light-sensitive material, it is preferably contained in a silver halide emulsion layer, but other non-photosensitive hydrophilic colloid layers (e.g., a protective layer, an intermediate layer, a filter layer, It may be included in an 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 alcohols, esters, and organic solvents that are miscible with water, such as hydrophilic colloids. Just add it to the solution. When added to the silver halide emulsion layer, it may be added at any time from the start of chemical ripening to before coating, but it is preferably added between after the end of chemical ripening and before coating. In particular, it is recommended that the content of the hydrazine derivative of the present invention be added to the coating solution prepared for coating. It is desirable to select the optimum amount depending on the relationship between the layer containing the compound and the silver halide emulsion layer, the type of antifogging compound, etc., and testing methods for selection are well known to those skilled in the art. Usually, it is preferably used in a range of 10@-6 mol to 1.times.IQ@-1 mol, particularly lo@-5 to ≠xio@-2 mol, per mole of silver halide.

Specific examples of the compound represented by general formula (1) are shown below.

However, the present invention is not limited to the following compounds.

1-Hiroshi −j ]-/1A 1-/j CH3 CH2CH2CH2SH 1-7g 1-/ri (,:0CH3 1-2≠ 1-. 2j 1-, 2za In addition, as described in U.S. Patent No. ≠, Ko 7♂, Ri 2r and so on.

As the acid polymer in the present invention, a polymer having a repeating unit represented by the following general formula is preferably used, and is particularly preferably used in the form of a water-dispersible polymer latex.

云A→--云B辷--YOC→-x y zA: Repeating unit derived from ethylenically unsaturated monocarboxylic acid or monocarboxylic acid salt copolymerizable with ethylenically unsaturated monomer Unit) represents 1.

B: Represents a repeating unit derived from a polyfunctional crosslinking agent.

C: Ethylenically unsaturated mo/mer other than A and B X: λQ~
Examples of 100 molti y: ON 30 molti z: 0-30 molti A include the following.

H3 H3 -CH2-C- CO, -CH2-Cl- C02CH2CH20CCH2CH2CO2H gamaleic acid, phthalic acid, Examples of B include divinylbenzene, trivinylcyclohexane, trivinylbenzene, j, j.

J, is-tetrachloro-/, Hiro-divinylbenzene,
Esters of unsaturated acids and unsaturated alcohols such as vinyl crotonate, allyl methacrylate, allyl crotonate, esters of unsaturated acids and polyfunctional alcohols such as trimethylolpropane trimethacrylate, neopentyl glycol dimethacrylate, butanediol dimethacrylate , /, A-hexanediol-diacrylate, /,! - pentanediol diacrylate, intererythritol triacrylate, tetraethylene glycol diacrylate, triethylene glycol diacrylate, esters of unsaturated alcohols and polyfunctional acids such as diethyl phthalate, unsaturated polyethers such as pigeon IJ ethylene glycol-divinyl ether, or water-soluble bis-acrylamides such as methylene-bis-acrylamide, glyoxal-bis-acrylamide, N,N'-dihydroxyethylene-bis-acrylamide, N,N'-cystamine-bis-acrylamide, trialylamide; Riludiethylenetriamine, acrylic acid (or methacrylic acid) ester of polyether, polyethylene glycol
Examples include diacrylate (or dimethacrylate) and divinyl sulfone.

Particularly preferred component B is divinylbenzene and diethylene glycol dimethacrylate.

Examples of component C include alkyl ester acrylate, alkyl methacrylate, ethylene, propylene, styrene, acrylamide, methacrylamide, and the like.

Next, specific examples of preferred acid polymers are shown.

It-2) Cl-13■-6) ShitJ2-n L4Hg Shi02L-H2 to H20 (UH2LH2C02H WORK 壬crtcn2-+ ■-g) CH3 + CCHz + CH3 If i o ) CH3CH3 X:)':Z- +≠:ri:27(mol 5)It-/i) CH3 x:y:z-bo:is2j(mol 俤)n-/2) +CH-CH2→ 30 (mol%>x:y:z
-Ahiro: //: 2 J (mol 俤) The amount of these acid polymers used is 0.0 to ioy, especially 0.0 to ioy per 1 square meter.
It is preferable that it is 2-3p.

The silver halide emulsion layer is preferred as the place where these acid polymers are added, but other hydrophilic colloid layers may also be used.

In the present invention, the non-trapping agent is a compound that reacts with quinone to eliminate the oxidizing effect of quinone, and is a compound that is generally used as a reducing agent or antioxidant, or a compound that can undergo nucleophilic addition to quinone. be. Preferred among these are dihydroxybenzenes such as catechol and hydroquinone, -Nf (hydrazine or hydrazides having NH- bond 7), sulfites, organic sulfinic acids, N-substituted hydroxylamines, ascorbic acid and reductones, etc. /, 2-enediols (so-called reductones), and compounds that release these compounds during development processing.

Preferred among dihydroxybenzenes are compounds represented by the following general formula (1), where at least one of Gl and 02 represents a hydroxy group, and the other is a group having the same meaning as 81 to R4 below. selected from. R to R4 independently represent a hydrogen atom, a hydroxy group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted alkylthio group, a substituted or unsubstituted arylthio group, a halogen atom,
/, 2.tertiary amine group, substituted or unsubstituted carbonamide group, substituted or unsubstituted sulfonamide group, substituted or unsubstituted alkyl group, substituted or unsubstituted teriyaru group, substituted or an unsubstituted, j- or 6-membered heterocyclic group containing 7 hexa, 0, or S atoms, a formyl group, a keto group,
Examples include a nulphonic acid group, a carboxylic acid group, a substituted or unsubstituted alkylsulfonyl group, and a substituted or unsubstituted arylsulfonyl group.

Specific examples of these dihydroquibenzene derivatives include, for example, The MerCk Index 10 th
edition K In addition to many examples,
U.S. Pat. No. 2,72♂, No. 63, No. 3, 700.

Hiroshi No. 33, Hiroshi No. 3,227,332, Unexamined Akihiro Tar 10
No. 1, 32, No. 30-/Els, No. 1IL3r, No. t
b-iori34I! -≠ No. 37-. No. 22.237, No. 2021AlsJ, No. 37 of J♂-17, No. 2/2tA of Tokuko Show 30, No. of JA-IAOr/1
No. 77, British Patent No. 7j27≠6,
No. 1016201, West German Patent Publication 2. /≠7,7♂ issue, Chemical, MabStructs, Vol. J & 37,7h, JP-A-37-/7741, etc. Among these preferred dihydroxybenzenes, particularly preferred ones are unsubstituted and/or ≠! The sum of Hammett's sigma values of the two substituents other than hydroxyl groups is -7.2 to +/, 2.%, preferably -/, 0 to 10. It is within the range of

Specific examples of these dihydroxybenzenes are shown below, but the present invention is not limited thereto.

H 00H H H r O H OH OH Among organic sulfinic acids or salts thereof, preferred are compounds represented by the following general formula (IV).

General formula (1v) R, -802M (wherein M represents a water atom, an alkali metal atom, unsubstituted or/or ≠ ammonium of the electric film, R represents an alkyl group having 7 to 300 carbon atoms, a phenyl group, Oras 7
It represents a chill group and may have a substituent. ) Preferred M in formula (1) is a hydrogen atom or an alkali metal atom (Li, Na, K).

Cs), and preferred examples of the f substituent of the group represented by
Branched or cyclic alkyl group (preferably number of carbon atoms
20 to 20), aralkyl group (preferably monocyclic or λ ring, alkyl moiety has 7 to 3 carbon atoms), alkoxy group (preferably 7 to 20 carbon atoms), or 2-functionalized amine 7 group (preferably 7 to 20 carbon atoms)
an alkyl group, -r sol group, alkyl or arylsulfonyl i, and in the case of 1.2Wt substitution, the total number of carbon atoms in the substituents is 20 or less), / to 3 substitutions,
or an unsubstituted ureido group (preferably one with 1 to 2 carbon atoms), a substituted or unsubstituted ureido group (preferably one with 6 to λ carbon atoms and/or 2 rings), a substituted or unsubstituted ureido group (preferably one with 6 to λ carbon atoms), Substituted aryl groups (preferably 6 to 2 carbon atoms), It- or no-1tsO alkylthio groups (preferably 1 to 2 carbon atoms), substituted or unsubstituted alkylsulfoxy groups (preferably carbon atoms) a number of carbon atoms to λ), a substituted or unsubstituted monocyclic or -
ring), substituted or unsubstituted alkylsulfonyl group (
Preferably carbon atoms / to λ), substituted or unsubstituted ryylsulfonyl group (preferably 6 to 29 carbon atoms, monocyclic or bicyclic), ryyloxy group (preferably monocyclic or bicyclic)
Preferably one having 6 to λ carbon atoms, monocyclic or λ ring), carbamoyl group (preferably fL< has 7 to 2 carbon atoms), sulfamoyl group (preferably 7 to 2 carbon atoms)
or 2), a hydroxy group, a halogen atom (for example, F, α, Br, etc.), a sulfonic acid group, or a carboxylic acid group. Among these substituents, those which may have further substituents may have the following substituents; namely, alkyl groups (1 to 20 carbon atoms), aryl groups (6 to 20 carbon atoms) monocyclic or bicyclic θ),
Alcoquine group (1 or some carbon atoms), aryloxy group (6 to 20 carbon atoms), alkylthio group (1 to 20 carbon atoms), arylthio group (6 to 20 carbon atoms), alkylsulfonyl group (number of carbon atoms/to 20), ryyl sulfonyl group (number of carbon atoms 6 to 20), carbonyl esterimido group (number of carbon atoms 7 to 20), sulfonamido group (number of carbon atoms 0 to 20)
), carbamoyl group (number of carbon atoms / to 2o), sulfamoyl group (number of carbon atoms / to 2o), alkylsulfoxy group (number of carbon atoms / to 20), I)-rusulfoxy group (number of carbon atoms / to 20), 20), ester group (
C2-C2o), hydroxy group, -COOM
or -802M (M is a hydrogen atom or an alkali metal atom,
Replacement or no I! or halogen atoms (k゛, α, k3r, I). These groups may be linked to each other to form a ring. These groups may also form part of a homopolymer or copolymer chain.

Examples of organic sulfinic acids are shown below, but the scope of the present invention is not limited to these. .

Wagner, )i, D, Zook lISynthe
ticQrganic Chemistry, p
107～110゜John Wiley & 5ons
, Inc., New'1'ork, 1933, along with other compound examples.

Preferred among N1ftM hydroxylamines are:
This is a compound represented by the following general formula (V).

General formula (V) R-fC? N)(0-Q (in the formula, m represents O or 71, Q is a hydrogen atom, an acyl group having 7 to 20 carbon atoms, or a number of carbon atoms) to 20
7 represents a substituted or unsubstituted phenyl group; R is a carbon atom t
! / to 30 monosubstituted or unsubstituted alkyl groups or carbon atoms */ to 30 substituted or unsubstituted phenyl groups. ) Among the compounds represented by the general formula (V), m is preferably O or /1, and Q is a hydrogen atom. Preferred substituents for the alkyl group or 7-enyl group are as follows. That is, straight-chain, branched, or cyclic alkyl groups (preferably having 1 to 20 carbon atoms), aralkyl groups (preferably monocyclic or λ-ring, and the number of carbon atoms in the alkyl moiety is 7 to 3), alkoxy groups , (preferably 7 to 20 carbon atoms)
/ or 2-substituted amino group (preferably an alkyl group, acyl group, alkyl or halosulfonyl group having 1 to 20 carbon atoms; in the case of co-substitution, the total number of carbon atoms in the substituent is 20 or less), l to 3 substituted or unsubstituted ureido groups (preferably those having 1 to 2 carbon atoms), substituted or unsubstituted aryl groups (preferably those having 6 to λ carbon atoms), 7 or -rings), substituted or unsubstituted arylthio groups (preferably carbon atoms i [
substituted or unsubstituted alkylthio group (preferably 1 to 2 carbon atoms), substituted or unsubstituted alkylsulfoxy group (preferably 1 to 2 carbon atoms)
), a substituted or unsubstituted aryl sulfoxy group (preferably a monocyclic or λ ring with 6 to λ carbon atoms)
, a substituted or unsubstituted alkylsulfonyl group (preferably having 7 to 2 carbon atoms), a substituted or unsubstituted arylsulfonyl group (preferably having 6 to λ carbon atoms, monocyclic or bicyclic) ), Ryloxy group (preferably one having 6 to λ carbon atoms and a monocyclic or λ ring),
Carbamoyl group (preferably number of carbon atoms/to 2)
, sulfamoyl group (preferably 7 to 2 carbon atoms)
), hydroxyl group, halogen atom (e.g. Ni, α,
Br, ■), a sulfonic acid group, or a carboxylic acid group. Among these substituents, those that can have further substituents may have the following substituents; that is, alkyl groups (number of carbon atoms/to 2Q), aryl groups (number of carbon atoms 6 to 20), monocyclic or λ ring), alkoxy: 4 (number of carbon atoms 1 to λO), aryloxy group (number of carbon atoms 6 to 20), alkylthio group (number of carbon atoms 7 to 20), Number of carbon atoms: 6
to 20), alkylsulfonyl 1fI (number of carbon atoms/to 20), arylsulfonyl group (number of carbon atoms/to 20),
20 to 20), carbonamide group (number of carbon atoms/to 20), sulfonamide group (number of carbon atoms 0 to 20)
, carbamoyl group (7 to 20 carbon atoms), sulfamoyl group (7 to 20 carbon atoms), alkylsulfoxy group (7 to 20 carbon atoms), irisulfoxy, ! (carbon X number/to 20), ester group (carbon number 2 to 20), hydroxy group, -COOM or -8o2M (M represents a hydrogen atom or an alkali metal atom, substituted or unsubstituted ammonium), or It is a halogen atom (F, α, Br, engineering). Specific examples of these compounds include R, H, Wagner, H, D, Zook.
Author, 5ynthetir, Organi CC
hemistry.

Pills, p. 376, etc., together with the synthesis method.

Specific examples of these monosubstituted hydroxylamines are listed below, but the scope of the present invention is not limited thereto.

(V) −/C)13CH2CON)101(
2n-C15H31CONHOH j n Cl2H25NHOH 4L n-C17H34CONHOH Examples of hydrazine derivatives include Research Disclosure Magazine, λ
3310 (/RIZA3), US Patent No. ≠, ≠7g.

No. 22g, Japanese Patent Publication No. 1sO-/1AO33r, No. 60-/
7973 Hiro, same jter l ri jko 3/, same j9-/ri j2
33. Same! Tar 2010+LJ, Tar 20104A
6, Jy-201011-7, Jy-39-2010 Hirog
Examples include the compounds described in 2010 Ko2, etc., but among these, compared to the compound of general formula (1) used to obtain high-contrast photographic characteristics, compounds that have a weaker ability to provide high-contrast photographic characteristics Preferably, compounds are used. A particularly preferred compound is represented by the following general formula (VI).

General formula (V Substituted alkylsulfonyl group, substituted or unsubstituted arylsulfonyl group,
Substituted or unsubstituted alkylsulfinyl group, substituted or unsubstituted arylsulfinyl group, N-substituted or unsubstituted carbamoyl group, he-substituted or unsubstituted sulfamoyl group, alkoxycarbonyl group, aryloxyarbonyl group, N- Substituted or unsubstituted sulfinamoyl group, substituted or unsubstituted thioacyl group, he-substituted or unsubstituted carbamoyl group, or j-membered or 6-membered heterocyclic group yt
Representation: Both RO1 and 2 represent a hydrogen atom, or one is a hydrogen atom and the other is a substituted or unsubstituted arylsulfonyl group, or a substituted or unsubstituted acyl group.

) Among the compounds represented by the general formula (Vl), preferred are the compounds represented by the following general formula (■a).

General formula (Vla): Ar -NHNH-G-B (in the formula, Ar represents 1 phenyl group substituted so that the sum of Hammett's digma constants is equal to or less than O1j, G represents 1 sulfonyl group or carbonyl group, B is a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group!) Examples of substituents on the phenyl group represented by Ar in general formula (VIA) include the following substituents. .

That is, a straight chain, branched, or cyclic alkyl group (preferably a carbon atom number of / to 20), an aralkyl group (preferably a monocyclic or bicyclic ring, and the carbon atom number of the alkyl moiety is /
to 3), an alkoxy group (preferably having 7 to 20 carbon atoms)/or a disubstituted amino group (preferably an alkyl group, acyl group, alkyl or arylsulfonyl group having 7 to 20 carbon atoms), λ-substituted (in which case the total number of carbon atoms in the substituent is 20 or less), / to 31f substituted or unsubstituted ureido group (preferably one having 1 to 2 carbon atoms), substituted or unsubstituted ureido group (preferably one having 1 to 2 carbon atoms), Aryl group (preferably having 6 to 2 carbon atoms/or 2
substituted or unsubstituted arylthio group (preferably having 6 to 29 carbon atoms), substituted or unsubstituted alkylthio group (preferably having 7 to λ carbon atoms), substituted or unsubstituted alkylsulfoxy group (preferably a number of carbon atoms/to 25P), a substituted or unsubstituted arylsulfoxy group (preferably a monocyclic or bicyclic one having 6 to 2 carbon atoms), a substituted or unsubstituted alkylsulfonyl group ( (preferably carbon atoms / to λ), substituted or unsubstituted arylsulfonyl groups (preferably carbon atoms 6 to 2, monocyclic or bicyclic), aryloxy groups (preferably carbon atoms a6 to 2), (lambda), monocyclic or cocyclic), carbamoyl group (preferably carbon atoms/to 2), sulfamoyl group (preferably carbon atoms!!/ to lambda), hydroxy group, halogen atom (
For example, F, α, Br, I), a sulfonic acid group, or a carboxylic acid group. Among these substituents, those that may have further substituents may have the following substituents;
That is, alkyl groups (1 to 20 carbon atoms), aryl groups (monocyclic or bicyclic groups having 6 to 20 carbon atoms), alkoxy groups (1 to 20 carbon atoms), aryloxy groups (1 to 20 carbon atoms), aryl groups (1 to 20 carbon atoms), 6 to 2Q), alkylthio group (number of carbon atoms / to 20), arylthio group (number of carbon atoms / to 20), alkylsulfonyl group (number of carbon atoms / to 20), Ryorylsulfonyl group (number of carbon atoms / to 20) to 20), carbonamide group (number of carbon atoms/
20 to 20>, sulfonamide group (0 to 20 carbon atoms), carbamoyl group (carbon atoms/to 20),
Sulfamoyl group (7 to 20 carbon atoms), alkylsulfoxy group (1 to 20 carbon atoms), arylsulfoxy group (7 to 20 carbon atoms), ester group (2 to 20 carbon atoms), hydroxy group ,-COO
M or -8Q2M (M represents a hydrogen atom or an alkali metal atom, substituted or unsubstituted ammonium), or a halogen atom (F, ct.

Br, I). These groups may be linked to each other to form a ring.

A specific example of the compound represented by the general formula (Vl) is shown below, but the present invention is not limited thereto.

In addition to the above-mentioned hydrazine compounds, examples of hydrazine compounds that can be effectively used in the present invention include JP-A No. 2003-121013 and JP-A No. 2002-20023.

Same 3q-2oio≠j, same jter 2010 Hiro 6, +M3
F, 2010147, same! ! 9-20101AIr.

same! ? -20/4tA.

In addition to the above hydrazine derivatives, the following general formula (Vff)
Cyclic hydrazides represented by are also effective.

General formula (VIA): (wherein, Z represents j or an atomic group necessary to form a 6-membered heterocycle, X and Y are independently an oxygen atom, -he-R group (R is a hydrogen atom) , a substituted or unsubstituted alkyl group, a substituted or unsubstituted phenyl group), or a sulfur atom.) Specific examples of the compound represented by the general formula (■) are shown below, but they do not fall within the scope of the present invention. is not limited only to these.

H30-C16H33 Other than the above compounds, preferred quinone trapping agents include reductones.

The reductones used in the present invention are enediol type (
E former 1io1), thiol enol form (Thio
1-Eno l), enaminol type (Enamino
l), the enediamine type (Endiam 0) and the enamine-thiol type (Enamine-Th1ol) are generally known as compounds. It is described in detail in ``The Chemistry of Reductones'' (Rotsuru Uchida-Shinsha, 1942), co-authored by Danji Nomura and Hirohisa Omura.

Among these, particularly preferred reductones are 3-carbonyl-enediol type compounds represented by the following general formula.

H Here, R8 and R' are an alkyl group, a substituted alkyl group (as a substituent, a hydroxyl group, an alkoxy group, an aryl group, a carboxyl group, an amide group, an imino group), an allyl group, an aryl group, and a substituted aryl group. (Water as a substituent!!1!
group, alkoxy group, aryl group - carboxyl group, halogen atom, amino group), or a ring containing an oxygen atom - a nitrogen atom, a sulfur atom, or a carbon linkage between 几 and 几'
may be formed.

Alternatively, as a precursor for generating general formula (Vl)Y, an alkyl or aryl ether or ester of these may be used.

Another preferable reductone is the following general formula (■),
There are amylreductone and imildactone indicated by (■).

Here, 几 is the same as 几 in the general formula (■).

Next, a particularly preferred specific example of reductones used in the present invention will be given.

HOOC (■-≠) H) 1 (■-7) (I-10) ([-//)H ■ ([-/J) Bun (If(-/1) (ff-/6) (■- (monomethyl ether of /) (■- monoacetone derivative of /) (■-monomethyl ether of /) (X-ri H In the present invention, these quinone trapping agents! It is preferably contained in the silver emulsion layer, but it may be contained in other non-photosensitive hydrophilic colloid layers.

Specifically, it can be added in the same manner as in the case of the compound represented by general formula (1). The content of these quinone trapping agents is from 10 mol to 1 mol of silver halide.
A range of /x70 mol, particularly /Xl0-5 to jx10 mol is preferred.

The silver halide emulsion used in the present invention may have any composition such as silver chloride, silver chlorobromide, silver iodobromide, and silver iodochlorobromide.

The average grain size of the silver halide used in the present invention is preferably fine grains (for example, 0.7μ or less), and O0
jμ or less is preferable. There are basically no restrictions on the particle size distribution, but monodisperse distribution is preferable. Monodisperse herein means that at least 73% of the particles by weight or number of particles is composed of particles having a size within ±lAO% of the average particle size.

Silver halide grains in photographic emulsions may have regular crystals such as cubic or octahedral, or irregular crystals such as spherical or plate-like.
ular) crystals, or a composite form of these crystal forms.

The interior and surface layers of the silver halide grains may be composed of uniform phases or may be composed of different phases.

Separately formed silver halide emulsions of 2aI or higher may be mixed and 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 may coexist in the silver halide grain formation or physical ripening process. good.

In the present invention, the silver halide emulsion which is particularly suitable as a light-sensitive material for line drawing and halftone dot creation is
Preferably, silver halide is produced in the presence of 0-8 to 70-5 moles of iridium salt or a complex salt thereof, and 70 moles or more, especially 90 moles or more, of silver bromide. Also,
The content of silver iodide is less than 10 mol, especially 0.1 to 5 mol 4
Silver haloiodide is preferred, and the silver iodide content on the grain surface is higher than the average silver iodide content of the grains. An emulsion containing silver iodide! When used, photographic properties with higher a degree 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, particularly 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, potassium hexachloroiridate (ff),
Examples include ammonium hexachloroiridate (I).

As a binder or holding colloid for photographic emulsions, it is advantageous to use gelatin (such as lime-treated gelatin or acid-treated gelatin), but other hydrophilic colloids can also be used. For example, gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein; cellulose derivatives such as hydroxyethyl cellulose, carboxymethyl cellulose, and sulfurized cellulose esters; sugar salts such as sodium alginate and starch salt conductors; Conductors, various synthetic hydrophilic materials such as single or copolymers of polyvinyl alcohol, polyvinyl alcohol partial acetal, polyvinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, polyvinylpyrazole, etc. Polymeric materials can be used.

The silver halide emulsion used in the method of the present invention does not need to be chemically sensitized, but may be chemically sensitized. Sulfur sensitization, ring element sensitization, and noble metal sensitization are known as methods for chemical sensitization of silver halide emulsions, and any of these methods can be used alone or in combination to achieve chemical sensitization. It's okay.

Among the noble metal sensitization methods, the gold sensitization method is a typical one, and uses a gold compound, a total complex salt as the king. There is no problem in containing complex salts of noble metals other than pure metals, such as platinum, palladium, and rhodium. Specific examples include U.S. Patent No. 1,1,060 and British Patent O/I.

It is described in No. 067, 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.

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

The photosensitive materials used in the present invention! f! Tokukaisho for the purpose of increasing Ic degree! Sensitizing dyes (for example, cyanine dyes, merocyanine dyes, etc.) described in No. J-32030, Hiromu pages J to J3 can be added.

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, there is no spectral sensitizing effect or visible light 'P! : Substances that do not substantially absorb and exhibit strong coloration may be included in the emulsion.

Useful sensitizing dyes, combinations of dyes exhibiting superchromic enhancement Mc, and substances exhibiting superchromic enhancement If& are listed in Research Disclosure (
Volume 76/
It is described in Section 5 of page 23 (■) of 76 Ko 3 (issued in December 2007).

The photosensitive material of the present invention includes a photosensitive material manufacturing process.

Various compounds may be included for the purpose of preventing IJY during storage or photographic processing or for stabilizing photographic performance. That is, azoles such as pendithiazolium salts, nitroindazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptothiadiazoles, aminotriazoles, benzothiazoles, nitrobenzotriazoles, etc. Ryosols,
mercaptopyrimidines; mercaptotriazines: thioketo compounds, such as oxazolinthione; azaindenes, such as triazaisuane, tetraazaindenes (especially Hiro-hydroxy substituted (/,
3*3a, 7) tetragaindenes), pentaazaindenes, etc.; adding many compounds known as anti-capri agents or stabilizers such as benzenethiosulfonic acid, benzenesulfinic acid, benzenesulfinamide, etc. be able to. Among these, preferred are benzotriazoles (eg, j-methyl-benzotriazole) and nitroindazoles (eg, j-nitroindazole). Also, these compounds! It may be included in the processing liquid.

The photographic material of the present invention may contain an inorganic or organic hardener in the photographic emulsion layer or other hydrophilic colloid layer.

For example, chromium salts (chromium alum, chromium acetate, etc.)
, aldehydes, (formaldehyde, glyoxal, geltaraldehyde, etc.), hemethylol compounds (dimethylol urea, methylol dimethylhydantoin, etc.), dioxane conductors (2,3-dihydroxydioxane, etc.), activated vinyl compounds (/ , j , 3
- triacryloyl-hexahydro-S-triazine, /, 3-vinylsulfonyl-2-propatol, etc.)
, active halogen compounds (2,44-dichloro-6-hydroxy-3-triazine), mucohalogen acids (
mucochloric acid, mucophenoxychloric acid, etc.), etc. can be used alone or in combination. Among these hardeners, active vinyl compounds and active halogen compounds are particularly preferred.

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

Examples include saponins (steroids), alkylene oxide derivatives (e.g. polyethylene glycol, polyethylene glycol/polypropylene glycol condensates, polyethylene glycol alkyl ethers or polyethylene glycol alkylaryl ethers, !') ethylene glycol esters, polyethylene glycol sorbitan esters, polyalkylene glycol alkylamines or amides, silicone polyethylene oxide adducts), glycidol derivatives (e.g. alkynylsuccinic acid polyglycerides, alkylphenol polyglycerides), fatty acid esters of polyhydric alcohols, alkyl esters of sugars Nonionic surfactants such as alkyl carboxylates, alkyl sulfonates, alkylbensene sulfonates, alkylnaphthalene sulfonates, alkyl sulfates, alkyl phosphates, heacyl-alkyl taurines, Acidic groups such as carboxy groups, sulfo groups, phospho groups, sulfate ester groups, phosphate ester groups, etc. Anionic surfactants containing; amphoteric surfactants such as amino acids, aminoalkyl sulfonic acids, aminoalkyl sulfates or phosphates, alkyl betaines, and amine oxides; alkylamine salts, aliphatic or aromatic tertiary Cationic surfactants can be used, such as monomer salts, heterocyclic ψ-class ammonium salts such as pyridinium and imidazolium, and phosphonium or sulfonium salts containing aliphatic or heterocycles.

In particular, surfactants preferably used in the present invention are polyalkylene oxides having a molecular weight of 600 or more and described in Japanese Patent Publication No. 72. Further, as the antistatic agent, a fluorine-containing surfactant is preferable.

The photographic light-sensitive material of the present invention may contain a matting 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 light-sensitive material used in the present invention may contain a dispersion of a water-insoluble or sparingly soluble synthetic polymer for the purpose of improving dimensional stability. For example, a polymer containing alkyl (meth)acrylate or a combination of these and acrylic acid or methacrylic acid as a monomer component can be used.

There are no particular restrictions on the developing agent used in the developer used in the present invention, but it is preferable that it contains dihydroxybenzenes, dihydroxybenzenes and 7-phenyl, since it is easy to obtain good halftone quality. A combination of -3-pyrazolidones or a combination of dihydroxybenzenes and p-aminophenols may also be used.

Examples of dihydroxybenzene developing agents used in the present invention include hydroquinone, chlorohydroquinone, bromohydroquinone, isopropylhydroquinone, methylhydroquinone, 2,3-dichlorohydroquinone, 2. j-
Examples include dichlorohydroquinone, λ, 3-dibromohydroquinone, and 2,3-dimethylhydroquinone, with hydroquinone being particularly preferred.

The developing agent for /-phenyl-3-pyrazolidone or its derivative used in the present invention is /-phenyl-3-pyrazolidone, /-phenyl-Hiroshi, Hiro-dimethyl-3-pyrazolidone, /-phenyl-Hiroshi-methyl-≠ -Hydroxymethyl-3-bira/IJton, l-phenyl-Hiroshi, ≠-dihydroxymethyl-3-pyrazolidone, /-phenyl-
j-mef 3-hira 7"ri)"n, /-p-aminophenyl-hiro, hiro-dimethyl-3-pyrazolidone,
/-p-trilu≠, ≠-dimethyl-3-pyrazolidone, and the like.

Examples of the p-aminophenol developing agent used in the present invention include hemethyl-p-aminophenol, p-aminophenol, N-(β-hydroxyethyl)-p-aminophenol, N-(Hiro-hydroxyphenyl)glycine,
There are 2-methyl-p-aminophenol, p-benzylaminophenol, etc., among which he-methyl-p-aminephenol is preferred.

The amount of developing agent is usually 0.0jmol/12. -0. gmol/1
Preferably used with dragons. When a combination of dihydroxybenzenes and phenyl-3-birasolitons or p-amino-phenols is used, the amount of the former is 0.0 jmol/ANO.

j mol/i, the latter preferably used at 0.06 mol/L or less.

Preservatives for sulfite used in the present invention include sodium sulfite, potassium sulfite, lithium sulfite, ammonium sulfite, sodium bisulfite, potassium metabisulfite,
Examples include formaldehyde and sodium bisulfite. The sulfite is preferably O0≠Morph 2 or more, particularly preferably 0.3 mol/L or more. Further, the upper limit is preferably 2.3 mol/L.

Alkaline agents used to set pH include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, trisodium phosphate, and potassium triphosphate.
Contains H regulators and buffers. The pH of the developer is preferably //, O to /λ.

It is Q.

Additives used in addition to the above ingredients include compounds such as boric acid and borax, IJium bromide, potassium bromide,
Development inhibitors such as potassium iodide: ethylene glycol,
Organic solvents such as diethylene glycol, triethylene glycol, dimethylformamide, methyl cellosolve, hexylene glycol, ethanol, methanol etc.
Fogging prevention using mercapto compounds such as phenyl-3-mercaptotetrazole, 2-mercaptobenzimidazole-j-sulfonic acid sodium salt, indazole compounds such as j-nitroindazole, and benztriazole compounds such as j-methylbenztriazole. or a black pepper inhibitor: and, if necessary, a color toning agent, a surfactant, an antifoaming agent, a water softener, a film hardening agent, and JP-A-37-2012. -101p2≠An amino compound described in Hiroshi No., etc. may be included.

The light-sensitive material of the present invention is preferably processed with a fixing solution containing a gelatin hardening agent such as an aluminum compound (Examples) The present invention will be explained in detail with reference to Examples below.

Example l ≠ × 1 per mole of silver in an aqueous gelatin solution maintained at jOoC
In the presence of 0-7 mol of potassium iridium hexachloride and ammonia, a silver nitrate aqueous solution, potassium iodide, and a potassium bromide aqueous solution were simultaneously added over 60 minutes, and the pAg during that time was 7. A cubic monodisperse emulsion having an average grain size of 0.23 μm and an average silver iodide content/motv% was prepared by maintaining the grain size to be ♂.

As a sensitizing dye in these silver iodobromide emulsions! , J'-cyclotorethyl-3,3'-bira(3-sul7obropyl)oxacarbocyanine sodium salt, as a stabilizer Hiro-hydroxy-6-methyl-/,3,3a,7
- Citrazaindene, a dispersion of polyethyl acrylate, /, 3-divinylsulfonyl-2-propanol, and the compound 1-ta of the general formula (1) of the present invention in a proportion of jX7()-3 moles per mole of silver. In addition to the first
As shown in the table, after adding the acidic polymer latex (II)-10 of the general formula (U) and the compound of the general formula (1) or (■), it was coated on a polyethylene terephthalate film with a silver content of 3. 'AP/rrtK was applied.

Each sample was exposed and developed, and photographic properties were measured. The results are shown in Table 1. As is clear from Table 1, samples 6-ri and /2.13 of the present invention are different from comparative samples /-j and io,
Compared to ii, there is no significant difference under standard development conditions (photographic properties/), but under conditions where the pH is increased and sulfite ions are decreased, the decrease in Dmax is small and the black spots are good.

(Photographic properties 2) Photographic physical properties were measured using the FG-AAOF automatic developing machine (Fuji Photo Film Co., Ltd.) using a developer with the following formulation.
This is the result of processing at r°C 30'.

Photographic characteristics 2 are as follows: A developing solution with the following formulation is aged over time without replenishment for a week, and the pH is 0. Processing was carried out in the same manner as in Photographic Characteristics 1 with the OJ increased and the sulfite ion concentration reduced to the SOS of the new solution.

(Developer formulation) Hydroquinone, oyN, methyl P, aminophenol/2 sulfate, Q, 1 sodium hydroxide, 1.0 potassium hydroxide
3J,0Pj-sulfosalicylic acid
4L3.01 Boric acid
23.09 Potassium sulfite //
θ, oy ethylenediaminetetraacetic acid disodium salt /, Oy potassium bromide 6.0 lj methylbenz° triazole θ, 67 nψ butyl jetanolamino /s, OP with water added
/ 2 (pH-//, 6) Here, the relative sensitivity is jf"0 density g/,
The value of sample l is 100 with the relative value of the reciprocal of g sight that gives J.
And so.

Kurobot was graded J based on microscopic observation.
"j" represents the best quality and "l" represents the worst quality. "j"
Or, "≠" is practical, "3" is poor but barely practical, and "λ" or r/J is impractical. "≠" and "
Those in the middle of ``3'' were rated as ``3, jJ.''

(Example 2) Emulsions (A) and CB) were prepared as shown below.

[Emulsion A] Silver nitrate aqueous solution and potassium iodide and potassium bromide aqueous solutions were added simultaneously over 60 minutes in the presence of iridium hexachloride and ammonia in an amount of ≠ × 10 mol per 7 mol of silver to an aqueous gelatin solution kept at 30°C. pAg to 7. A cubic monodisperse emulsion having an average grain size of 0.3 .mu.m and an average silver iodide content of 1 mol was prepared by maintaining the emulsion at f, and was desalted by the 70 curing method.

[Emulsion B] Potassium iodide was prepared in the same manner as the emulsion; the amount of ammonia was adjusted to form grains, and after desalting, sulfur sensitization was performed using hypo, and the average grain diameter was 0°22μ, and the average silver iodide content was 0. A .1 molar cubic monodisperse sulfur sensitized emulsion was prepared.

j as a sensitizing dye in these silver iodobromide emulsions.

3'-cycloterethyl-3,3'-bis(3-sul7obropyl)oxacarbo/anine sodium salt, ≠-hydroxy-6-methyl/ as stabilizer, 3.
3a, 7-chitrazaindene, polyethyl agellylate dispersion, /, After adding 3-divinylsulfonyl-1-propanol, emulsions A, B, silver halide weight ratio /
: Mix in a ratio of 2 and then 3X10'
After adding 1 mol Ag of hydrazine derivative 1-37 and a latex of the acidic polymer U-10 of the present invention and a quinone trapping agent IV-/ as shown in Table 2, a silver amount of 3 mol was deposited on a polyethylene terephthalate film together with a protective layer. ．．
The photographic properties were evaluated in the same manner as in Example 2.

W. As is clear from Table 2, is the sample of the present invention? -/3 is
Compared to the comparative sample, the decrease in Dmax is small and the black porosity is good.

(Example 3) The same additives were added to the emulsion (A) used in Example 2,
A sample was prepared by adding the hydrazine derivative ()-3O of the present invention and the quinone trapping agent (IV)-j, (V)-/furthermore, the latex of (if)-7 as an acid polymer. These samples were subjected to W development and evaluation in the same manner as in Example 2.

With the combination of the present invention, good results were obtained with less decrease in Dmax and less occurrence of black spots.

Patent Applicant: Fuji Atsuma Film Co., Ltd. Procedural Amendment

Claims (1)

[Claims] In a silver halide photographic material having at least one silver halide emulsion layer on a support and containing a hydrazine derivative in the emulsion layer or other hydrophilic colloid layer, in the emulsion layer or other hydrophilic colloid layer. A silver halide photographic material comprising an acid polymer and a quinone trapping agent.