JPH06324422A - Silver halide photographic sensitive material and high-contrast negative image forming method by using the same - Google Patents

Abstract

PURPOSE:To obtain an ultrahigh-contrast image without causing pepper through a developing system not using harmful hydroquinone as a developing agent by incorporating a specified organic compound in an emulsion layer or another hydrophilic colloidal layer. CONSTITUTION:The emulsion layer or another hydrophilic colloidal layer contains the organic compound represented by formula I in which R1 is alkyl, alkenyl, alkynyl, amino, alkoxycarbonyl, aryl, or -A-Z; A is 1-20C alkylene or -CH2CH=CHCH2-; Z is H, aryl, hydroxy, alkoxy, acyl, alkylcarbonyl, cyano, N-akamido, amido, or a group represented by formula II; each of R2, R3, R5, and R6 is H, lower alkyl, or the like; and R4 is H or aryl.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide photographic light-sensitive material useful in a photolithography process for printing graphic arts and a method of forming a negative tone image having high contrast using the same.

[0002]

2. Description of the Related Art In the photolithography process for printing graphic arts, since it is required to form a sharp halftone dot image or a line image, image formation showing extremely hard photographic characteristics (especially gamma of 10 or more). System required.
Conventionally, for this purpose, the content of silver chloride is 50 mol%,
A lithographic silver halide photographic light-sensitive material comprising a silver chlorobromide emulsion preferably exceeding 70 mol% has an extremely low free sulfite ion concentration containing only hydroquinone as a developing agent (usually 0.1 mol / liter or less). The process of processing with a lith developer has been used. However, it has been difficult to achieve high sensitivity because a lithographic silver halide photographic emulsion must use a silver chlorobromide emulsion having a high silver chloride content.

Another method for obtaining a high-tone negative image is US Pat. Nos. 4,168,977 and 4,224.
No. 401, No. 4,241, 164, No. 4,26
9,929, 4,311,781, 4,6
There is a method using a specific hydrazine derivative disclosed in, for example, No. 50,746 and No. 4,927,734.
According to this method, a surface latent image type silver halide photographic light-sensitive material containing a specific hydrazine derivative (generally an acylphenylhydrazine derivative) as a nucleating agent is adjusted to pH 11.0.
To 12.3, a photographic characteristic of ultrahigh contrast and high sensitivity with a gamma of more than 10 can be obtained. In this method, since silver bromide or a silver chlorobromide emulsion having a high silver bromide content can be used, higher sensitivity can be achieved as compared with lithographic silver halide.

However, it has been found that the high contrast image forming system using an acylhydrazine derivative has some drawbacks. That is, when the above-mentioned image forming system is used, a hard negative image can be obtained, and at the same time, the occurrence of paper (black spots) is a serious problem in the photomechanical process. Pepper is a spot such as black sesame that occurs in the unexposed area, for example, the area that should be the non-developed area between the dots, and it significantly reduces the commercial value as a photomechanical material. Cause a breakdown. Therefore, great efforts have been made to develop a technique for suppressing peppers, but improvements in peppers often result in a decrease in sensitivity and gamma, and the development of an image forming system that achieves high-sensitivity contrast enhancement without the occurrence of peppers. Is strongly desired. The second drawback of the conventional high-contrast image forming system is that hydroquinone, which is a harmful and environmental pollutant, must be used in a large amount in order to keep the activity of the developer constant. Since the squirrel developing solution has a low concentration of sulfite ion, it is easily air-oxidized and the consumption of hydroquinone as a developing agent is remarkable. Further, although it is allowed to add a high concentration of sulfite to a developer of a high contrast image forming system using a hydrazine derivative, it is necessary to add a high pH (11.0).
Because of the above), it is susceptible to air oxidation and the consumption of hydroquinone is remarkable. Therefore, in order to maintain the development activity of these developers, a large amount of hydroquinone, which is a harmful and environmental pollutant, is used, or the amount of hydroquinone consumed by air oxidation is supplemented to increase the amount of hydroquinone in the developer. It is necessary to maintain a certain level or more, and it is desired to develop a high contrast image forming system using a developer that consumes less hydroquinone or does not use hydroquinone as a developing agent.

[0005]

SUMMARY OF THE INVENTION Therefore, the first object of the present invention is a development system which does not use harmful hydroquinone as a main developing agent, and a silver halide photographic light-sensitive material capable of obtaining a super-high contrast image without generation of pepper. To provide.

Further, a second object of the present invention is to provide an image forming method for forming a negative tone image having a high contrast by subjecting the above silver halide photographic light-sensitive material to imagewise exposure and development treatment with an alkaline developer containing reductones. Especially.

[0007]

The above-mentioned object of the present invention is to provide a silver halide photographic light-sensitive material having on a support at least one negative type silver halide emulsion layer and, if necessary, another hydrophilic colloid layer. In the above, a silver halide photographic light-sensitive material characterized by adding an organic compound represented by the general formula (I) to an emulsion layer or another hydrophilic colloid layer and a reductone after imagewise exposure to the photographic light-sensitive material. It was achieved by an image forming method in which development processing was performed with an alkaline developer containing the same.

[0008]

[Chemical 4]

In the formula, R ₁ represents a substituted or unsubstituted alkyl group, alkenyl group or alkynyl group, and as the substituent, a hydroxyl group, a lower alkoxy group such as a methoxy group or an ethoxy group, a phenyl group, a tolyl group or a pyridyl group. Aromatic groups such as, acetyl groups, acyl groups such as benzoyl groups,
An alkoxycarbonyl group such as a methoxycarbonyl group and an ethoxycarbonyl group, an amide group, a cyano group and the like are preferable. Specific examples of R ₁ include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, pentyl group, 2-hydroxyethyl group, 3-hydroxypropyl group, 2-methoxyethyl group, 3-ethoxypropyl group. 2-phenylethyl group, 3-acetylpropyl group, 2-benzoylethyl group, 2-methoxycarbonylethyl group, 2-cyanoethyl group, 2-carbamoylethyl group, butenyl group, propargyl group, benzyl group,
Examples thereof include a toluyl group and a phenethyl group.

Further, R ₁ is an amino group, an alkyl-substituted amino group (N-methylamino group, N, N-dimethylamino group, etc.), or an optionally substituted alkoxycarbonyl group (methoxycarbonyl group, ethoxycarbonyl group). , A propoxycarbonyl group, a butoxycarbonyl group,
Phenoxycarbonyl group, tolyloxycarbonyl group,
2-hydroxyethyloxycarbonyl group), an optionally substituted aromatic group such as a phenyl group or a pyridyl group. A halogen atom as a substituent of the aromatic group,
Lower alkoxy groups such as nitro group, hydroxyl group, methoxy group, ethoxy group, aromatic groups such as phenyl group, tolyl group, pyridyl group, acyl groups such as acetyl group, benzoyl group, methoxycarbonyl group, ethoxycarbonyl group, etc. Alkoxycarbonyl group, alkyl-substituted amide group,
A cyano group, an alkyl-substituted sulfonamide group, an alkyl-substituted carbamoyl group and the like are preferable.

Furthermore, R ₁ may be a molecular structure represented by -AZ. A represents an alkylene group having 1 to 20 carbon atoms or —CH ₂ CH═CHCH ₂ —, Z is a hydrogen atom, an optionally substituted phenyl group, a hydroxyl group, an alkoxy group such as a methoxy group or an ethoxy group, It represents an acyl group such as a benzoyl group or an acetyl group, an alkoxycarbonyl group such as a methoxycarbonyl group or an ethoxycarbonyl group, a cyano group, an N-alkylamide group, an amide group or a group represented by the general formula (A).

[0012]

[Chemical 5]

In the general formula (I) and the general formula (A), R ₂ ,
R ₃ , R ₅ and R ₆ are each independently a hydrogen atom, a halogen atom, a lower alkyl group (methyl group, ethyl group, propyl group, butyl group, etc.), a hydroxyl group, an alkoxy group (a methoxy group, an ethoxy group, a propoxy group, Butoxy group, etc.),
Alkoxycarbonyl group which may be substituted (methoxycarbonyl group, ethoxycarbonyl group, propoxycarbonyl group, butoxycarbonyl group, 2-hydroxyethyloxycarbonyl group, tolyloxycarbonyl group etc.), formyl group, optionally substituted a carbamoyl group (-CONH _2, -CONHCH _3, -CONHC
_{2 H 5, -CON (CH 3} ) 2, CON (C 2 H 5) _2, etc.)
Or an optionally substituted amino group (-NH _2, -NHS
O ₂ C ₅ H _11, such as -NHSO ₂ Ph), hydroxyl group, an alkoxy group, a lower alkyl group substituted with an aromatic group such as a phenyl group or a pyridyl group (2-hydroxyethyl group,
3-hydroxypropyl group, 2-methoxyethyl group, 4
-Ethoxybutyl group, benzyl group, 2-phenylethyl group, 3- (4-pyridyl) propyl group, etc., optionally substituted aromatic group (halogen atom as a substituent,
Lower alkyl group such as nitro group, hydroxyl group, methyl group and ethyl group, lower alkoxy group such as methoxy group and ethoxy group, aromatic group such as phenyl group, tolyl group and pyridyl group, acyl group such as acetyl group and benzoyl group , An alkoxycarbonyl group such as a methoxycarbonyl group and an ethoxycarbonyl group, an alkyl-substituted amide group, a cyano group,
It represents an alkyl-substituted sulfonamide group, an alkyl-substituted carbamoyl group or the like and an optionally substituted sulfonyl group (such as an alkylamino group, a dialkylamino group, a substituted phenylamino group or a di (substituted phenyl) amino group as a substituent). Also, between R ₂ and R ₃ and / or R
_A ring such as a 5-membered ring, a 6-membered ring or a 7-membered ring or an aromatic ring may be formed between ₅ and R ₆ .

In the general formulas (I) and (A), R ₄ is a hydrogen atom, a lower alkyl group (such as a methyl group, an ethyl group, a propyl group or a butyl group), a hydroxyl group, an alkoxy group, a phenyl group or a pyridyl group. Lower alkyl group substituted with an aromatic group such as hydroxymethyl group, 2-hydroxyethyl group, 3-hydroxypropyl group, 2-methoxyethyl group, 2-ethoxyethyl group, benzyl group, 2-phenylethyl group, 2-tolylethyl group, etc. An optionally substituted aromatic group (as a substituent, a halogen atom, a nitro group, a hydroxyl group, a methyl group, a lower alkyl group such as an ethyl group, a methoxy group, a lower alkoxy group such as an ethoxy group,
Aromatic groups such as phenyl group, tolyl group, pyridyl group, acyl groups such as acetyl group, benzoyl group, alkoxycarbonyl groups such as methoxycarbonyl group, ethoxycarbonyl group, alkyl substituted amide group, cyano group, alkyl substituted sulfonamide Group, alkyl-substituted carbamoyl group, etc., formyl group, optionally substituted alkoxycarbonyl group (methoxycarbonyl group, ethoxycarbonyl group, propoxycarbonyl group, butoxycarbonyl group, 2-hydroxyethyloxycarbonyl group, tolyloxycarbonyl group) Etc.), an optionally substituted amide group (—CONH ₂ , —CONHCH ₃ , —CONHC _{2
H 5, -CON (CH 3)} 2, CON (C 2 H 5) 2 , etc.) or an optionally substituted amino group (-NH _2, -NHSO ₂
C ₅ H _11, represents a -NHSO etc. ₂ Ph).

Typical examples of the organic compound represented by the general formula (I) used in the present invention are shown below, but the present invention is not limited thereto.

[0016]

[Chemical 6]

[0017]

[Chemical 7]

[0018]

[Chemical 8]

[0019]

[Chemical 9]

[0020]

[Chemical 10]

[0021]

[Chemical 11]

[0022]

[Chemical 12]

[0023]

[Chemical 13]

[0024]

[Chemical 14]

[0025]

[Chemical 15]

[0026]

[Chemical 16]

[0027]

[Chemical 17]

[0028]

[Chemical 18]

[0029]

[Chemical 19]

[0030]

[Chemical 20]

The organic compound represented by the general formula (I) used in the present invention can be easily synthesized by the reduction reaction of the corresponding pyridinium salt derivative. For example, D.
Mauserall, FH Westheimer, J. Am . Chem . Soc . , 1955 , 77 , 2
261: JWBunting, S.Sindhuatmaja, J.Org.Chem . , 1981 , 4
6 , 4219: H.Meyer, H.Tropsch, Monatsh. , 1914 , 35 , 207: J.
F. Munshi, MM Joullie, Tetrahedron , 1968 , 24 , 1923: S.Sh
inkai, H.Hamada, Y.Kusana, O.Manabe, J.Chem.Soc ., Perki
n Trans. , 2 , 1979 , 699. etc. can be referred to for the synthesis.

Regarding the pyridinium salt derivative as a starting material for the organic compound represented by the general formula (I), 16 (III), Vol.
As described on pages 129 and 129 (1959, Asakura Shoten), it can be synthesized by reacting the corresponding pyridine, quinoline or isoquinoline derivative with an alkyl halide derivative. The specific synthesis method is described in A. Grob, E.
Renk, Helv.Chim.Acta 37 , 1672 (1954); RELyle, E.
F.Perlowski, HJTroscianiec, GGLyle, J.Org.Che
m. , 20 , 1761 (1955); MRLamborg, RMBurton, NO
Kaplan, J. Am . Chem . Soc . , 79 , 6173 (1957); W. Ciusa, AB
uccelli, Gazzetta Chimia Italiana 88 , 393 (1958) and the like.

The organic compound represented by the general formula (I) used in the present invention is composed of at least one negative silver halide emulsion layer constituting the silver halide photographic light-sensitive material or other hydrophilic colloid layer. Non-photosensitive layer,
For example, it is used by being contained in a protective layer, an intermediate layer, an antihalation layer, a filter layer and the like.

The addition amount of the silver halide photographic light-sensitive material of the organic compound represented by the general formula (I) used in the present invention, per mol of silver halide 1 × 10 ^-6 moles appropriate equimolar range And usually 1 × 10 ⁻⁴ to 0.1 mol is preferably used. Further, the organic compounds represented by the general formula (I) used in the present invention can be used in combination of two or more kinds.

To add the organic compound represented by the general formula (I) used in the present invention to the negative type silver halide emulsion layer or the other non-photosensitive layer, water or an organic solvent miscible with water, For example, it may be dissolved in alcohols, ketones, esters, amides and the like and added to the negative silver halide emulsion or the non-photosensitive hydrophilic colloid solution used in the present invention. At this time, the organic compound represented by the general formula (I) is unstable in acid, and therefore it is preferable to add it to the emulsion layer or the hydrophilic colloid layer using an alkaline solution.

Another addition method is to disperse in a hydrophilic colloid solution by an oil / water emulsion type dispersion method. As the oil component used in the oil / water emulsion type dispersion method, the coupler-dissolving oil component used in the oil protect type light-sensitive material can be used. For example, tri-o-cresyl phosphate, trihexyl phosphate, dioctyl butyl phosphate, dibutyl phthalate,
Diethyllaurylamide, 2,4-diallylpheno-
And octyl benzoate.

To disperse the oil phase in which the organic compound represented by the general formula (I) is dissolved in the aqueous phase, a usual surfactant is used. For example, anionic surfactants containing acidic groups such as carboxylic acid, sulfonic acid, phosphoric acid, sulfuric acid ester and phosphoric acid ester groups, and nonionic, cationic and amphoteric surfactants are used.

As the hydrophilic colloid, those known as photographic binders such as gelatin are used. For example, gelatin derivatives, graft polymers of gelatin and other polymers, cellulose derivatives such as hydroxyethyl cellulose, carboxymethyl cellulose and cellulose sulfate, sodium alginate, starch derivatives, polyvinyl. Alcohol partial acetal, poly-N-
A wide variety of synthetic hydrophilic polymeric substances such as vinylpyrrolidone, polyacrylic acid, polymethacrylic acid polyacrylamide, polyvinyl imidazole, polyvinyl pyrazole, and other single or copolymers can be used. Alternatively, latex or the like may be added. As an example,
U.S. Pat.No. 3518088, Research Disclosure August 197
6, the compound described in No. 148-14850 can be mentioned.

The organic compound represented by the general formula (I) used in the present invention may be added to the silver halide photographic light-sensitive material at any time during the process for producing the silver halide photographic light-sensitive material. it can. For example, when it is added to a negative type silver halide emulsion, it can be added at any time from the start of chemical ripening to before coating, but it can be added at any time after the end of chemical ripening and immediately before coating. preferable. As another method of adding the organic compound represented by the general formula (I) to the silver halide photographic light-sensitive material, an organic compound represented by the general formula (I) is applied after coating and drying a silver halide photographic emulsion. There is also a “post-coating” method in which the alkaline solution of is coated on the film and dried.

Although the mechanism of action of the organic compound represented by the general formula (I) of the present invention is not sufficiently clear, the organic compound represented by the general formula (I) uses a reductone or a salt thereof as a main developing agent. It is presumed that a nucleation reaction is carried out during the development processing using the contained alkaline developer to act as a contrast enhancer for enhancing the sensitivity and gradation of the silver halide photographic light-sensitive material. In an image forming method using an alkaline developer containing a reductone as a main developing agent,
The markedly high sensitivity and ultrahigh contrast effect by the organic compound represented by the general formula (I) have not been known so far, and are completely unexpected effects.

Next, the silver halide photographic light-sensitive material of the present invention will be described. The silver halide photographic light-sensitive material used in the present invention has at least one emulsion layer composed of a negative type silver halide emulsion. There is no particular limitation on the halogen composition of the silver halide emulsion used, and any composition such as silver chloride, silver chlorobromide, silver iodobromide, silver iodobromochloride can be used. The content of silver iodide is 5 mol% or less, preferably 3 mol% or less.

The silver halide grains used in the present invention are
It is possible to have a relatively wide particle size distribution, but it is preferable to have a narrow particle size distribution, especially 9% of all particles.
A monodisperse emulsion in which the grain size accounting for 0% is within ± 40% of the average grain size is preferable.

The silver halide grains used in the present invention are
The average particle size is preferably 0.7 μm or less, particularly 0.4 μm
The following are preferred. Further, silver halide grains having a regular crystal form such as a cube and an octahedron are spherical,
It may have an irregular crystal shape such as a plate shape or a clam shape.

The silver halide grains used in the present invention can be prepared by any known method. That is, any of an acidic method, a neutral method, an ammonia method and the like may be used. As a reaction mode of the soluble silver salt and the soluble halogen salt, any one of a forward mixing method, a back mixing method, a simultaneous mixing method, a combination thereof and the like may be used. Good. As one of the simultaneous mixing methods, the silver ion concentration (pA
g) is kept constant, that is, the pAg controlled double jet method (CDJ method) is used to obtain monodispersed silver halide grains having a uniform crystal form and a substantially uniform grain size. . In the process of silver halide grain formation or physical ripening, a cadmium salt, an iridium salt or a rhodium salt may coexist in order to increase the contrast of the silver halide emulsion.

The binder contained in the silver halide photographic emulsion layer used in the present invention is 250 g per mol of silver halide.
It is preferable not to exceed. Gelatin is most preferable as the binder, but a hydrophilic colloid other than gelatin can be used. For example, albumin, casein,
Graft polymers of gelatin and other polymers, hydrophilic polymers such as polyvinyl alcohol and polyacrylamide can be used.

The silver halide emulsion used in the present invention does not have to be chemically sensitized, but it is usually chemically sensitized. Sulfur sensitization, reduction sensitization, noble metal sensitization, zelenium sensitization, tellurium sensitization and combinations thereof are used as the chemical sensitization method. Preferred chemical sensitization for the practice of the present invention is sulfur sensitization or This method combines sulfur sensitization and gold sensitization, which is one of the sensitizations of precious metals.

As the sulfur sensitizer, active gelatin, thiosulfate, thioureas, allylthiocarbamide and the like can be used. HAuCl ₄ , Au as gold sensitizer
(SCN) ₂ ^-salt , Au (S ₂ O ₃ ) ₂ ^{3 -salt and the} like can be used.

The silver halide emulsion used in the present invention is spectrally sensitized with one or two or more sensitizing dyes in order to impart photosensitivity in a desired light-sensitive wavelength region. As the sensitizing dye, a cyanine dye, a merocyanine dye, a styryl dye, a hemicyanine dye, a holopolar cyanine dye, an oxonol dye, and a hemioxonol dye can be used. Particularly useful dyes are cyanine dyes and merocyanine dyes. Any of the nuclei normally used for cyanine dyes as the basic heterocyclic nuclei of dyes can be applied. That is, a pyrroline nucleus, an oxazole nucleus, an oxazoline nucleus, a thiazole nucleus, a thiazoline nucleus, a pyrrole nucleus,
A selenazole nucleus, an imidazole nucleus, a tetrazole nucleus, a pyridine nucleus, an indole nucleus, a benzoxazole nucleus, a benzothiazole nucleus, a benzoselenazole nucleus, a benzimidazole nucleus, a quinoline nucleus and the like can be applied.

The silver halide photographic light-sensitive material according to the present invention comprises a support and at least one hydrophilic colloid layer containing a negative silver halide emulsion coated on the support. A protective colloid layer, for example, a protective layer, an intermediate layer, an anti-halation layer, a filter layer, or the like may be coated. These hydrophilic colloid layers may contain an inorganic or organic hardener. Hardeners include chromium salts (chromium alum, etc.), aldehydes (formaldehyde, glyoxal, etc.), N-methylol compounds (dimethylol urea, methylol dimethylhydantoin, etc.), active halogen compounds (2,4-dichloro-6-hydroxy-s-). Triazine, mucochloric acid, etc.),
Active vinyl compounds (1,3,5-triacryloyluluhexahydro-s-triazine and the like), epoxy and aziridine hardeners and the like can be used.

In the hydrophilic colloid layer used in the present invention, various photographic additives such as emulsion stabilizer (6
-Hydroxy-4-methyl-1,3,3a, 7-tetrazaindene and other hydroxytetrazaindene compounds), spreading agents (saponins, etc.), gelatin plasticizers (acrylic acid ester copolymers, etc.), antistatic, coating aids Agent and photographic property improvement (for example, development acceleration, high contrast)
Various surfactants (cationic,
Anionic, nonionic, amphoteric surfactants), antifoggants (hydroquinone, 5-methylbenzotriazole, 1-phenyl-5-mercaptotetrazole, etc.), matting agents, purposes for improving dimensional stability of photographic light-sensitive materials A water-insoluble or sparingly-soluble polymer latex (homo or copolymer of alkyl acrylate, alkyl methacrylate, acrylic acid, glycidyl acrylate, etc.) can be used within a range that does not impair the effects of the present invention.

The support that can be used in the silver halide photographic light-sensitive material is a polyolefin such as polyethylene, polypropylene or polystyrene, cellulose acetate, cellulose nitrate.
Cellulose ester film such as polyester, polyester film such as polyethylene terephthalate, paper, synthetic paper, or a composite thereof, for example, paper or film coated on both sides or one side with polyolefin,
Any known support such as a glass plate can be used.

After the image is exposed on the silver halide photographic light-sensitive material of the present invention, an alkaline developing solution containing a reductone or a salt thereof as a main developing agent is preferably used as a developing solution in order to obtain a good contrast image. .

The reductones used in the developer of the present invention are endiol type (Endiol), enaminol type (Enaminol), and enediamine type (Endiam).
ine), thiol enol type (Thiol-Eno)
l) and the enamine thiol type (Enamine-T
hiol) is generally known as a compound. Examples of these compounds are described in US Pat. No. 2,688,549, JP-A-62-237,443 and the like. Methods for synthesizing these reductones are well known, and are described in detail, for example, in "The Chemistry of Reductones" by Yuji Nomura and Hirohisa Omura (1969, Uchida Lao Tsukuba Shinsha).

Of these, reductones which are particularly preferred for use in the present invention are compounds represented by the following general formula (II).

[0055]

[Chemical 21]

Here, R ₇ is a hydrogen atom or a hydroxyl group, and l is an integer of 1 to 4.

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

[0058]

[Chemical formula 22]

[0059]

[Chemical formula 23]

The reductones used in the present invention can also be used in the form of alkali metal salts such as lithium salt, sodium salt and potassium salt. These reductones are used in an amount of 1 to 100 g, preferably 5 to 50 g per liter of developer.
g is preferably used.

The developing solution of the present invention contains dihydroxybenzenes (eg, hydroquinone, chlorohydroquinone, bromohydroquinone, isopropylhydroquinone, methylhydroquinone, 2,3-dichlorohydroquinone) as auxiliary developing agents in addition to reductones which are main developing agents. 2,3-dibromohydroquinone, 2,5-dimethylhydroquinone, potassium hydroquinone monosulfonate, sodium hydroquinone monosulfonate,
Catechol, pyrazol, etc.), 3-pyrazolidones (eg, 1-phenyl-3-pyrazolidone, 1-phenyl-4-methyl-3-pyrazolidone, 1-phenyl-
5-methyl-3-pyrazolidone, 1-phenyl-4-ethyl-3-pyrazolidone, 1-phenyl-4,4-dimethyl-3-pyrazolidone, 1-phenyl-4-methyl-
4-hydroxymethyl-3-pyrazolidone, 1-phenyl-4,4-dihydroxymethyl-3-pyrazolidone,
1,5-diphenyl-3-pyrazolidone, 1-p-tolyl-3-pyrazolidone, 1-phenyl-2-acetyl-
4,4-dimethyl-3-pyrazolidone, 1-p-hydroxyphenyl-4,4-dimethyl-3-pyrazolidone,
1- (2-benzothiazolyl) -3-pyrazolidone, 3
-Acetoxy-1-phenyl-3-pyrazolidone, etc.), 3-aminopyrazolines (eg, 1- (p-hydroxyphenyl) -3-aminopyrazoline, 1- (p
-Methylaminophenyl) -3-aminopyrazoline, 1
-(P-amino-m-methylphenyl) -3-aminopyrazoline and the like), phenylenediamines (for example, 4-
Amino-N, N-diethylaniline, 3-methyl-4-
Amino-N, N-diethylaniline, 4-amino-N-
Ethyl-N-β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N
-Β-methanesulfonamidoethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methoxyethylaniline, etc., and aminophenols (for example,
4-aminophenol, 4-amino-3-methylphenol, 4- (N-methyl) aminophenol, 2,4-
Diaminophenol, N- (4-hydroxyphenyl)
Glycine, N- (2'-hydroxyethyl) -2-aminophenol, 2-hydroxymethyl-4-aminophenol, 2-hydroxymethyl-4- (N-methyl) aminophenol, etc.) and hydrochlorides of these compounds And sulfates.

The amount of these auxiliary developing agents added is the amount of developer 1
It is 0.2 to 20 g, preferably 0.5 to 5 g per liter.

The developer used in the present invention preferably contains a preservative and an alkali in addition to the above essential components. Sulfite can be used as a preservative. Examples of sulfites include sodium sulfite, potassium sulfite, lithium sulfite, ammonium sulfite, sodium bisulfite, potassium bisulfite, and potassium metabisulfite. The amount of these sulfites added is 0.5 per liter of the developing solution.
It is preferably not more than mol.

The alkaline agent is added to set the pH of the developing solution to 9 or more. As the alkali agent used for setting the pH, use a usual water-soluble inorganic alkali metal salt such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, potassium carbonate, potassium bicarbonate, potassium triphosphate, etc. You can

In addition to the above-mentioned components, the developer used in the present invention contains, if necessary, a water-soluble acid (eg acetic acid, boric acid), a pH buffering agent (eg sodium triphosphate, sodium carbonate, potassium carbonate). , Sodium metaborate, 4
Lithium borate, etc.), inorganic fog inhibitors (eg sodium bromide, potassium bromide), organic fog inhibitors (eg 1-phenyl-5-mercaptotetrazole, 5
-Nitroindazole, etc.), organic solvents (eg, ethylene glycol, diethylene glycol, methyl cellosolve, etc.), toning agents, surfactants, defoamers, water softeners, etc. are used within a range that does not impair the effects of the present invention. be able to.

The developing treatment temperature of the developing solution used in the present invention is selected in the range of 18 to 50 degrees Celsius, and more preferably in the range of 20 to 40 degrees Celsius.

As the fixing agent used in the present invention, those having a generally used composition can be used. For example, “The Basics of Photographic Engineering: Silver Salt Photography” edited by the Photographic Society of Japan 3
Page 30 onwards (Corona Publishing Co., Ltd. in 1979), Akira Sasai "Chemistry of Photography" page 320 onwards (Photo Industry Publishing Co. Ltd., 1982)
And Thomas (W.THOMAS, Jr.), "SP-S-Handbook of Photographics"
Science and Engineering (SPSE HANDBOOK
OF PHOTOGRAPHIC SCIENCE AND ENGINEERRING ", JOHN WILEY & SONS (1973) page 528, etc. can be referred to. As the fixing agent base, thiosulfates, thiocyanates, and organic sulfur compounds known to be effective as a fixing agent can be used. Further, as fixing aids, acid agents (eg, acetic acid, citric acid, etc.), preservatives (eg, sodium sulfite, etc.), buffer agents (eg, boric acid, etc.) and hardeners (eg, potassium alum, alum, sulfuric acid). Aluminum, etc.) can be used.

[0068]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to the following examples as long as the gist thereof is not exceeded.

Example 1 In a gelatin aqueous solution kept at 40 ° C., an aqueous silver nitrate solution and 3.0 × 10 ⁻⁷ mol of rhodium hexachloride (I) were ^added per mol of silver.
II) Mixed aqueous solution of potassium bromide and sodium chloride containing sodium (molar ratio Br: Cl = 30: 70)
Was added simultaneously over 75 minutes while maintaining pAg 7.2 to prepare a cubic monodisperse silver chlorobromide emulsion (AgCl 70 mol%) having an average particle size of 0.28 μm. After removing the soluble salts by a conventional method, 5 × 10 ⁻⁵ mol of sodium thiosulfate per mol of silver halide, 1.
0 × 10 ⁻⁵ mol of chloroauric acid and 1.24 × 10 ⁻³ mol of potassium iodide were added, and the mixture was chemically aged at 52.2 ° C. for 100 minutes. 80 g per mol of silver halide in this emulsion
Contains gelatin. To the emulsion thus prepared, 12 × 10 ^-3 mol of 6-hydroxy-4-methyl-1,3,3a, 7-tetrazaindene was added per mol of silver halide, and polyethylene terephthalate was preliminarily coated with an undercoat layer. It was coated on the base so that the amount of silver was 40 mg per 100 cm ² . Onto these emulsion layers, a gelatin protective layer containing formalin and dimethylolurea as a hardening agent was applied and dried. Next, the same amount of a methanol solution containing 0.1% by weight of the organic compound represented by the general formula (I) shown in Table 1 was added to the aqueous solution adjusted to pH 7.7 with sodium bicarbonate. Then, an alkaline aqueous solution (concentration: 0.05% by weight) of the organic compound represented by the general formula (I) was prepared, applied to the above film and dried. When the coating amount was measured, the average content of the organic compound represented by the general formula (I) was 14 × 10 ⁻³ mol per mol of silver.

[0070]

[Table 1]

The film produced as described above was
Using a B-200 filter, a tungsten light source of 2666K exposed through a step wedge having a step of 0.15 for 5 seconds, and then developed with a developer 1 having the following composition at 35 ° C. for 30 seconds, stopped, fixed and washed with water. And dried.

Composition of Developer 1 Metol 7.5 g Sodium ascorbate 30.0 g (Sodium salt of reductone 1-1) Potassium bromide 1.0 g Sodium metaborate tetrahydrate 70.0 g 5-Nitroindazo -L-8.0 mg Water was added to the mixture, and the pH was adjusted to 1.0 l with 10% NaOH aqueous solution.

The photographic characteristics obtained are shown in Table 2.

[0074]

[Table 2]

In Table 2, the relative sensitivity is the relative value of the reciprocal of the exposure dose at which the density of the evaluation sample excluding fog is 3.0, and the sensitivity of Film No. 2 according to the present invention is expressed as 100. Gamma is black density 0.5 and 3.0 excluding fog
Fog represents the density of the non-exposed areas.

As is clear from Table 2, the image forming method of the present invention using the film containing the organic compound represented by the general formula (I) according to the present invention gives a highly sensitive and extremely high contrast image. In the case of the comparative example containing no organic compound represented by the general formula (I), such a high contrast image cannot be obtained.

Example 2 12 × 10 1 per mol of silver halide prepared in Example 1
^-3 mol of 6-hydroxy-4-methyl-1,3,3a,
To the emulsion to which 7-tetrazaindene was added, 3 × 10 ⁻³ mol of 5-methylbenzotriazole was added per mol of silver halide, and the pH of the emulsion was adjusted to 7.0. It was coated on the coated polyethylene terephthalate base so that the amount of silver was 40 mg per 100 cm ² .

Then, dimethylolurea as a hardener and the compounds of the present invention shown in Table 3 were added to these emulsion layers to adjust the pH to 7.0. It was coated on top and dried. Also, the over
The amount of the applied compound was measured to measure the amount of added compound per mol of silver halide.

[0079]

[Table 3]

Film samples obtained 1, 5, 6 and 7
In the same manner as in Example 1, the sample was exposed, developed, fixed, washed with water, and dried to obtain an evaluation sample. The results are shown in Table 4.

[0081]

[Table 4]

The photographic characteristics in Table 4 are the same as in Example 1, and the relative sensitivity is shown by setting the sensitivity of film No. 5 using the compound N-19 of the present invention to 100.

As is clear from Table 4, the film containing the organic compound represented by the general formula (I) of the present invention is imaged according to the image forming method of the present invention.
It can be seen that a high-sensitivity and high-contrast image can be obtained.

Example 3 In a gelatin aqueous solution kept at 60 ° C., an aqueous silver nitrate solution and 3.0 × 10 ⁻⁷ mol of rhodium hexabromide (II) were ^added per mol of silver.
I) An aqueous potassium bromide solution containing sodium was added to pAg7.
A cubic crystal monodisperse silver bromide emulsion having an average grain size of 0.22 μm was prepared by simultaneously adding over 60 minutes while keeping at 0. After removing soluble salts by a conventional method,
25 × 10 ⁻⁵ mol of sodium thiosulfate was added to 1 mol of silver halide, and the mixture was chemically ripened at 60 ° C. for 70 minutes. This emulsion contains 80 g of gelatin per mol of silver halide. The emulsion thus prepared contained 18 × 10 ^-3 mol of 6-hydroxy-4-methyl-per mol of silver halide.
After adjusting the pH to 7.4 by adding 1,3,3a, 7-tetrazaindene, the general formula (I) shown in Table 5 in advance.
On a polyethylene terephthalate base coated with an undercoating layer having a pH of 8.8 containing an organic compound represented by
The coating amount was 40 mg of silver per cm ² . By measuring the coating amount of the undercoat layer in advance, the amount of the added compound per mol of the coated silver amount was measured.

[0085]

[Table 5]

A gelatin protective layer containing formalin and dimethylolurea as a hardening agent was coated on this emulsion layer and dried to obtain a film sample.

Film samples obtained 1, 8, 9 and 1
0 is subjected to the same operations as in Example 1 by exposing, developing, fixing,
It was washed with water and dried to obtain an evaluation sample. The results are shown in Table 6.

[0088]

[Table 6]

The photographic characteristics in Table 6 are the same as in Example 1, and the relative sensitivity is shown with the sensitivity of film No. 8 using the compound N-19 of the present invention as 100.

As is clear from Table 6, a film containing the organic compound represented by formula (I) of the present invention is imaged according to the image forming method of the present invention.
It can be seen that a high-sensitivity and high-contrast image can be obtained.

Example 4 An oil prepared by dissolving the compounds shown in Table 7 in dioctyl butyl phosphate was added to a silver bromide emulsion obtained by the same procedure as in Example 3 and having the pH adjusted to 7.4. Disperse and 40 per 100 cm ² on polyethylene terephthalate base.
It was applied so that the amount of silver was mg.

[0092]

[Table 7]

Onto this emulsion layer, a gelatin protective layer containing formalin and dimethylolurea as a hardening agent was applied and dried to obtain a film sample.

The obtained film samples 11, 12, 13 and 14 were exposed in the same manner as in Example 1 and then exposed at 35 ° C. using Developer 1 and Developers 2 and 3 having the following compositions.
After development processing for 30 seconds, fixing, washing with water and drying were performed to obtain an evaluation sample.

Composition of Developer 2 Sodium ascorbate (sodium salt of reductone 1-1) 10.0 g Phenidone 1.2 g Sodium metaborate tetrahydrate 35.0 g Potassium bromide 1.0 g 5-Nitroindazo -L 10.0 mg Water was added and adjusted with 1.0 l 10% NaOH aqueous solution pH 10.8

Composition of Developer 3 Sodium ascorbate (sodium salt of reductone 1-1) 10.0 g 2-Methyl-4-N-ethyl-N-β-hydroxyethylaniline sulfate monohydrate 4.75 g Metabo Sodium acid tetrahydrate 35.0 g Potassium bromide 1.0 g 5-Nitroindazole 14.0 mg Water was added to 1.0 l After adjustment with 10% NaOH aqueous solution pH 12.0

The results are shown in Table 8.

[0098]

[Table 8]

The photographic characteristics in Table 8 are the same as those in Example 1, and the relative sensitivity is the sensitivity when the film No. 12 using the compound N-19 of the present invention is developed with Developer 1 at 35 ° C. for 30 seconds. Was shown as 100.

As is clear from Table 8, a film containing the organic compound represented by formula (I) of the present invention is imaged according to the image forming method of the present invention.
It can be seen that a high-sensitivity and high-contrast image with a gamma of more than 10 can be obtained.

[0101]

According to the present invention, it is possible to form a high tone negative image having a gamma of more than 10 which is useful in a photolithography process for printing.

Claims (8)

[Claims] 1. A negative type silver halide photographic light-sensitive material having at least one negative type silver halide emulsion layer on a support and, if necessary, another hydrophilic colloid layer, the emulsion layer or another hydrophilic layer. A silver halide photographic light-sensitive material, characterized in that the colloidal layer contains an organic compound represented by formula (I). [Chemical 1] (In the formula, R ₁ is an optionally substituted alkyl group, an optionally substituted alkenyl group, an optionally substituted alkynyl group, an optionally substituted amino group, an optionally substituted alkoxy group. carbonyl group, a substituted .A representing an aromatic group or -A-Z even though the Matawa alkylene group having 1 to 20 carbon atoms CH ₂ CH = C
Represents HCH ₂ —, Z is a hydrogen atom, an optionally substituted aromatic group, a hydroxyl group, an alkoxy group, an acyl group, an alkoxycarbonyl group, a cyano group, an N-alkylamide group,
It represents an amide group or a group represented by formula (A). [Chemical 2] In the general formula (I) and the general formula (A), R ₂ , R ₃ , R ₅ and R ₆ are each independently a hydrogen atom, a halogen atom, an optionally substituted lower alkyl group, a hydroxyl group, an alkoxy group or a substituted group. It represents an optionally substituted alkoxycarbonyl group, a formyl group, an optionally substituted carbamoyl group, an optionally substituted aromatic group, an optionally substituted amino group and an optionally substituted sulfonyl group. Further, a ring such as a 5-membered ring, a 6-membered ring or a 7-membered ring or an aromatic ring may be formed between R ₂ and R ₃ and / or between R ₅ and R ₆ . In formulas (I) and (A), R ₄ is a hydrogen atom, an optionally substituted lower alkyl group, an optionally substituted aromatic group, a formyl group, or an optionally substituted alkoxycarbonyl. Represents a group, an optionally substituted amide group and an optionally substituted amino group. ) 2. A method for forming a high contrast negative image, which comprises subjecting the silver halide photographic light-sensitive material according to claim 1 to image exposure and then developing it with an alkaline developer containing a reductone or a salt thereof. 3. The method for forming a high-tone negative image according to claim 2, wherein the reductone is a compound represented by the general formula (II) or a salt thereof. [Chemical 3] (In the formula, R ₇ represents a hydrogen atom or a hydroxyl group, and l represents an integer of 1 to 4.) 4. The method for forming a high contrast negative image according to claim 2, wherein the alkaline developing solution contains dihydroxybenzenes or salts thereof as an auxiliary developing agent. 5. The alkaline developing solution contains 3-pyrazolidones or a salt thereof as an auxiliary developing agent.
Alternatively, the method for forming a high-contrast negative image according to claim 3. 6. The method for forming a high contrast negative image according to claim 2, wherein the alkaline developing solution contains a 3-aminopyrazoline or a salt thereof as an auxiliary developing agent. 7. The method of forming a high contrast negative image according to claim 2, wherein the alkaline developer contains p-phenylenediamines or a salt thereof as an auxiliary developing agent. 8. The method for forming a high-contrast negative image according to claim 2, wherein the alkaline developer contains p-aminophenol or its salt as an auxiliary developing agent.