JPH0713304A - Contrasty negative image forming method - Google Patents

Abstract

PURPOSE:To provide a highly sensitive contrasty negative image in which a gamma useful for a printing photolithographic process exceeds 10 and pepper is not caused. CONSTITUTION:An image forming method is constituted in such a way that one or more kinds of hetero atoms of phosphorus, nitrogen, oxygen, sulfur or selenium are contained, and under the existence of an organic compound whose reduction electric potential is lower than (-) 0.60 volt, development processing is carried out on a negative type halogenated silver photosensitive material by alkaline liquid developer containing aminophenol type developer and/or dehydroxy benzene developer.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an image forming method which is useful in a photolithography process for printing graphic arts and which is suitable for forming a negative tone image having high contrast. More specifically, a negative-type silver halide photographic light-sensitive material is treated with an aminophenol-based developer and / or a dihydroxybenzene-based developer in the presence of an organic compound having a reduction potential of -0.60 V which is less base to form a high contrast negative image. The present invention relates to a method of forming a high-contrast image by performing development processing with a photographic developer containing a developer.

[0002]

2. Description of the Related Art Since a sharp halftone image or a line image is required to be formed in a photolithography process for printing graphic arts, an image forming system having a high photographic characteristic with a gamma of 10 or more is required. Is.

Conventionally, for this purpose, a lithographic silver halide photographic light-sensitive material comprising a silver chlorobromide emulsion having a silver chloride content of more than 50 mol%, preferably 70 mol%, and containing a polyalkylene oxide compound. A method has been used in which the material is treated with a lith developer containing substantially only hydroquinone as a developing agent and having an extremely low concentration of free sulfite ions (usually 0.1 mol / liter or less). 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.

As another method for obtaining a high tone negative image, there is a method of selective development in which a tetrazolium salt compound is contained in a silver halide photographic light-sensitive material and development processing is carried out with a PQ developer. In this method, there are no special restrictions on the composition and grain size of the emulsion grains used, the presence or absence of chemical sensitization,
Although there is an advantage that the sensitivity can be controlled in a considerably wide range as needed, it is difficult to achieve high sensitivity because the selective suppression effect of a tetrazolium salt compound called selective development is utilized. There was a problem that the tetrazolium salt compound dissolved therein formed an insoluble matter.

Another method for obtaining a high contrast negative image is described in US Pat. Nos. 4,168,977 and 4,2.
No. 24,401, No. 4,241,164, No. 4,
269,929, 4,311,781, 4,650,746, and 4,927,734, and the like, and there are methods using a specific hydrazine derivative. 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 1
By processing with a developing solution of 1.0 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 the development by the nucleation development proceeds in addition to the usual development, higher sensitivity can be achieved as compared with the lith development system or the system using a tetrazolium salt. However, high contrast imaging systems using acylhydrazine derivatives have been found to have some drawbacks. That is, when an image forming system using a hydrazine derivative is used, a hard negative image can be obtained, and at the same time, a pepper (black spot) is generated, which 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.

[0006]

SUMMARY OF THE INVENTION Therefore, an object of the present invention is to form a negative image which is useful in a photolithography process for printing graphic arts and which is capable of high-sensitivity and high-contrast gradation without the occurrence of pepper. It is to provide a suitable image forming method.

[0007]

The above-mentioned problems of the present invention are as follows.
A negative type silver halide emulsion layer on a support in the presence of an organic compound containing one or more heteroatoms of phosphorus, nitrogen, oxygen, sulfur or selenium and having a reduction potential less than -0.60 V. And a silver halide photographic light-sensitive material having the above-mentioned are developed with an alkaline developing solution containing an aminophenol developing agent and / or a dihydroxybenzene developing agent.

The value of the reduction potential Ered used herein means the potential at which the organic compound is reduced by the injection of electrons at the cathode in the voltammetry. Reduction potential Er
The value of ed can be accurately measured by voltammetry. That is, in a acetonitrile containing tetra-n-butylammonium perchlorate 0.1M as a supporting electrolyte, 1 × 10 5 of dyes or pyridinium salt derivatives were prepared.
A voltammogram of ⁻³ M to 1 × 10 ⁻⁴ M was measured and determined as a half-wave potential obtained from this. Platinum was used as a working electrode and a saturated calomel electrode (SCE) was used as a reference electrode, and the measurement was performed at 25 ° C. More specifically, U.S. Pat. No. 3,501,307 and P. Delahay, New Instrumental Methods in Elec.
trochemistry) ((Interscience Publishers), 1954)
Etc.

Examples of the organic compound having a reduction potential less than -0.60 V are pyridinium salt derivatives represented by the general formula (NI) and quinolinium salts represented by the general formula (N-II). Derivatives and isoquinolinium salt derivatives represented by the general formula (N-III) (hereinafter, these pyridinium salt derivatives and the like are simply referred to as pyridinium salt derivatives), and dyes are particularly preferable.

[0010]

[Chemical 5]

In the formula, R ₁ is an amino group, an alkyl-substituted amino group (N-methylamino group, N, N-dimethylamino group, etc.), an aromatic group such as a phenyl group or a pyridyl group, or-.
Represents 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, a benzoyl group. And an acyl group such as an acetyl group, an alkoxycarbonyl group such as a methoxycarbonyl group and an ethoxycarbonyl group, a cyano group, an N-alkylamide group, an amide group or a group represented by the general formula (N-Ia).

[0012]

[Chemical 6]

General formula (N-I) and general formula (N-Ia)
Wherein R ₂ is a lower alkyl group ( ₂ -hydroxy group, such as a methyl group, an ethyl group, a propyl group, a butyl group), a hydroxyl group, an alkoxy group, or a phenyl group or a pyridyl group. Ethyl group, 3-hydroxypropyl group, 2-methoxyethyl group, 4-ethoxybutyl group, benzyl group, 2-phenylethyl group, 3- (4
-Pyridyl) propyl group) or amide group (-CO
NH ₂ , —CONHCH _{3 and the} like). n1 is 0, 1,
Represents 2 or 3. However, when a plurality of R ₂ 's are present, they may be different from each other. X ^- represents anion such as iodine ion, bromine ion, chlorine ion, p-toluenesulfonate ion, perchlorate ion and methylsulfate ion. However, X does not exist when the general formula (NI) has a betaine structure.

[0014]

[Chemical 7]

In the formula, R ₃ represents a substituted or unsubstituted lower alkyl group. As the substituent, a hydroxyl group, a methoxy group,
Lower alkoxy group such as ethoxy group, aromatic group such as phenyl group, acyl group such as acetyl group and benzoyl group,
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 ₃ 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. Examples thereof include a 2-phenylethyl group, a 3-acetylpropyl group, a 2-benzoylethyl group, a 2-methoxycarbonylethyl group, a 2-cyanoethyl group and a 2-carbamoylethyl group. R ₄ and R ₅ are each independently a halogen atom, a lower alkyl group (eg, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, pentyl group, etc.),
It represents a substituted lower alkyl group or lower alkoxy group (eg, methoxy group, ethoxy group, etc.). The substituent of the substituted lower alkyl group is preferably a hydroxyl group, a lower alkoxy group, or a substituted or unsubstituted aromatic group (eg, phenyl group, alkyl-substituted phenyl group). Specific examples of the substituted lower alkyl group include, for example, a hydroxymethyl group, a 2-hydroxyethyl group, a 3-hydroxypropyl group, a 2-methoxyethyl group, a 2-ethoxyethyl group, a benzyl group, a 2-phenylethyl group, a 2-tolylethyl group and the like. You can n2 and n3 each independently represent 0, 1 or 2. When there are a plurality of R ₄ and / or R ₅ , they may be different from each other. X ^- represents anion such as iodine ion, bromine ion, chlorine ion, p-toluenesulfonate ion, perchlorate ion and methylsulfate ion. However,
X does not exist when the general formula (N-II) has a betaine structure.

[0016]

[Chemical 8]

In the formula, R ₆ represents an alkyl group (methyl group, ethyl group, propyl group, butyl group, pentyl group, etc.) or a substituted alkyl group. Further, R ₆ and R ₈ may form a 6-membered ring or a 5-membered ring. R ₇ represents a hydrogen atom, a lower alkyl group (methyl group, ethyl group, propyl group, butyl group, pentyl group, etc.), a substituted alkyl group or an aryl group (phenyl group, alkyl-substituted phenyl group, etc.). Examples of the substituent of the substituted alkyl group in R ₆ and R ₇ include a hydroxyl group, an alkoxy group (methoxy group, ethoxy group, etc.), an aryl group (phenyl group, alkyl-substituted phenyl group, etc.) and the like. Specific examples of the substituted alkyl group include, for example, 2-hydroxyethyl group,
3-hydroxypropyl group, 2-methoxyethyl group, 2
Examples include -ethoxyethyl group, 3-methoxypropyl group, benzyl group and 2-phenylethyl group. R ₈ and R ₉ are each independently a lower alkyl group substituted with a hydrogen atom, a lower alkyl group (such as a methyl group, an ethyl group, a propyl group), a hydroxyl group, an alkoxy group or an aromatic group (2-hydroxyethyl group, 3-hydroxypropyl group, 2-methoxyethyl group, 3-ethoxypropyl group, benzyl group, 2-phenylethyl group), alkoxy group (methoxy group, ethoxy group, etc.) or amide group. Further, R ₈ and R ₉ may form an aromatic ring. R ₁₀ is a halogen atom (chlorine atom, bromine atom, etc.),
Optionally substituted lower alkyl group (methyl group, ethyl group, propyl group, 2-hydroxyethyl group, 3-hydroxypropyl group, 2-methoxyethyl group, benzyl group, etc.), alkoxy group (methoxy group, ethoxy group, etc.)
Alternatively, it represents an amino group which may be substituted with an alkyl group. n4 represents 0, 1 or 2. When a plurality of R ₁₀ 's are present, they may be different from each other. X ^- represents anion such as iodine ion, bromine ion, chlorine ion, p-toluenesulfonate ion, perchlorate ion and methylsulfate ion. However, when the general formula (N-III) has a betaine structure, X does not exist.

Typical examples of the pyridinium salt derivatives used in the present invention are shown below, but the present invention is not limited thereto.

[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]

[0031]

[Chemical 21]

[0032]

[Chemical formula 22]

[0033]

[Chemical formula 23]

[0034]

[Chemical formula 24]

[0035]

[Chemical 25]

[0036]

[Chemical formula 26]

[0037]

[Chemical 27]

[0038]

[Chemical 28]

[0039]

[Chemical 29]

[0040]

[Chemical 30]

[0041]

[Chemical 31]

These pyridinium salt derivatives are the corresponding pyridines, as described in "Large Organic Chemistry", Vol. 16 (III), pages 7 and 129 (1959, Asakura Shoten), edited by M. Otake. It can be synthesized by reacting a quinoline or isoquinoline derivative with an alkyl halide derivative. A specific synthesis method is described in A. Grob, E. Renk, Helv. Chem. Acta , 37 , 1672 (195).
4); RELyle, EFPerlowski, HJTroscianiec, GGL
yle, J. Org . Chem . , 20 , 1761 (195)
5); MR Lamborg, RMBurton, NO Kaplan, J. Am . Chem . Soc . , 79 , 6173 (1957); WC
Report by iusa, A. Buccelli, Gazzetta Chimia Italiana
88 , 393 (1958) and the like.

The dyes useful in the present invention are represented by the general formulas (D-I) and (D) where the reduction potential is less than -0.60 volt.
-II), (D-III) or (D-IV).

[0044]

[Chemical 32]

In the formula, m ₁ represents 0 or 1. Q ₁ and Q
₂ represents a non-metal atomic group necessary for forming a nitrogen-containing heterocycle. Examples of the nitrogen-containing heterocycle completed by Q ₁ and Q ₂ include a benzothiazole ring, a naphthothiazole ring, a benzocenazole ring, a benzoxazole ring, a quinoline ring and a thiazoline ring. Q ₁ and Q ₂
Substituents may be introduced into these nitrogen-containing heterocycles completed by, and the substituents include a lower alkyl group such as a methyl group and an ethyl group, a halogen atom, an alkoxy group such as a methoxy group, and the like. . R ₁₁ and R ₁₂ are lower alkyl groups such as methyl group, ethyl group and propyl group,
Used as a substituted alkyl group having a carboxyl group such as carboxymethyl group and β-carboxyethyl group, a substituted alkyl group having a sulfonyl group such as β-sulfoethyl group and γ-sulfopropyl group, an allyl group and other N substituents of ordinary cyanine dyes Represents a given substituent. R ₁₃ represents a hydrogen atom or a lower alkyl group such as a methyl group and an ethyl group. X ⁻ represents an anion usually used for forming a cyanine dye salt such as iodine ion, bromine ion, chlorine ion, perchlorate ion, p-toluenesulfonate ion, and methylsulfate ion. Alternatively, X is absent when the cyanine dye has a betaine structure.

[0046]

[Chemical 33]

In the formula, Y represents an oxygen atom or a sulfur atom. m ₂ represents 0 or 1. Q ₃ represents a group of non-metal atoms necessary for forming a nitrogen-containing heterocycle. A thiazole ring, a thiazoline ring, a pyrroline ring, a quinoline ring, a tetrazole ring and the like are useful as the nitrogen-containing heterocycle completed by Q ₃ . A substituent may be introduced into these nitrogen-containing rings completed by Q ₃ , and the substituent includes a lower alkyl group such as a methyl group and an ethyl group, a halogen atom, an alkoxy group such as a methoxy group, and the like. . R ₁₄ and R ₁₅ have a lower alkyl group such as a methyl group and an ethyl group, and a carboxyl group such as a carboxymethyl group and a β-carboxyethyl group (and the carboxyl group includes a quaternary ammonium salt such as a trimethylammonium salt). Substituted alkyl groups, hydroxymethyl groups, substituted alkyl groups having a hydroxyl group such as β-hydroxyethyl group, and allyl groups are included. R ₁₆ represents a hydrogen atom or a lower alkyl group such as a methyl group and an ethyl group.

[0048]

[Chemical 34]

In the formula, R ₁₇ represents a hydrogen atom or a lower alkyl group such as a methyl group, an ethyl group or a propyl group.
R ₁₈ , R ₁₉ , R ₂₀ , and R ₂₁ are each independently substituted with a hydrogen atom, a halogen atom, or a lower alkyl group such as a methyl group or an ethyl group, an amino group, or a lower alkyl group such as a methyl group or an ethyl group. Represents an amino group. R ₂₂
Represents a phenyl group which is unsubstituted or substituted with an amino group, a dialkylamino group, an organic carboxylic acid or the like. X ^- is iodine ion, bromine ion, chlorine ion, perchlorate ion,
Represents anions usually used for forming dye salts such as p-toluenesulfonate ion and methylsulfate ion.

[0050]

[Chemical 35]

In the formula, Q ₄ represents a nonmetallic atom group necessary for forming a nitrogen-containing heterocycle. Examples of the nitrogen-containing heterocycle completed by Q ₄ include a benzothiazole ring, a naphthothiazole ring, a benzocenazole ring, a benzoxazole ring, a quinoline ring and a thiazoline ring.
A substituent may be introduced into these nitrogen-containing heterocycles completed by Q ₄ , and examples of the substituent include a lower alkyl group such as a methyl group and an ethyl group, a halogen atom, an alkoxy group such as a methoxy group, and the like. included. R ₂₃ and R ₂₄
Each independently represents a hydrogen atom or a lower alkyl group such as a methyl group, an ethyl group or a propyl group. R ₂₅ and R ₂₆ are each independently a hydrogen atom, a lower alkyl group such as a methyl group or an ethyl group, or a lower alkyl group substituted with a halogen atom such as a β-chloroethyl group, or an unsubstituted or a methyl group or an ethyl group. Represents a phenyl group substituted with a lower alkyl group such as a group, a halogen atom, an alkoxy group such as a methoxy group, and the like. X
^Over represents iodine ion, a bromine ion, a chlorine ion, perchlorate ion, p over-toluenesulfonate ion, a normal anion used to form a dye salt, such as methylsulfate ion.

Typical examples of the dyes used in the present invention are shown below, but the present invention is not limited to these.

[0053]

[Chemical 36]

[0054]

[Chemical 37]

[0055]

[Chemical 38]

[0056]

[Chemical Formula 39]

[0057]

[Chemical 40]

[0058]

[Chemical 41]

[0059]

[Chemical 42]

[0060]

[Chemical 43]

[0061]

[Chemical 44]

[0062]

[Chemical formula 45]

[0063]

[Chemical formula 46]

[0064]

[Chemical 47]

[0065]

[Chemical 48]

[0066]

[Chemical 49]

[0067]

[Chemical 50]

These dyes are commercially available, for example, from The Cyanine Dy and Relayed Compounds by FH Hamer.
es and Related Compounds) 1964, Interscience Publishers, New York Publishing (Inters
cience Publishers, NY) page 55 et seq. and can be synthesized by the method described or a similar method.

The dye and / or pyridinium salt derivative used in the image forming method of the present invention may be present when the silver halide photographic light-sensitive material is developed.
Specific methods thereof include (1) a method of incorporating a dye and / or a pyridinium salt derivative into a silver halide photographic light-sensitive material, and (2) a method of adding a dye and / or a pyridinium salt derivative into a developing solution. , (3) a method of incorporating a dye and / or a pyridinium salt derivative into a silver halide photographic light-sensitive material and a developing solution. However, all of these methods can be adopted for the image forming method of the present invention. it can.

The dye and / or pyridinium salt derivative used in the present invention is a non-photosensitive material composed of at least one negative silver halide emulsion layer constituting the silver halide photographic light-sensitive material or other hydrophilic colloid layer. It may be contained in a functional layer such as a protective layer, an intermediate layer, an antihalation layer, a filter layer and the like.

To add the dye and / or pyridinium salt derivative 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 such as alcohols is used. , Ketones,
It may be dissolved in an ester or amide and added to the negative type silver halide emulsion or the non-photosensitive hydrophilic colloid solution used in the present invention.

The dye and / or pyridinium salt derivative 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 photographic light-sensitive material. 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 addition method, a solution of a dye and / or a pyridinium salt derivative is coated on a silver halide photographic light-sensitive material which has been dried after coating, and dried again to obtain a silver halide photographic light-sensitive material. There is also a “post-coating” method.

The amount of the dye and / or pyridinium salt derivative used in the present invention added to the silver halide photographic light-sensitive material is from ^10-6 mol to 1 mol per mol of silver halide.
A molar range is suitable, usually 10 ⁻³ mol to 0.1.
Molar is preferably used. Further, the dyes and / or pyridinium salt derivatives used in the present invention can be used alone or in combination.

The dye and / or pyridinium salt derivative used in the present invention can also be used by adding it to an alkaline developer. When used by adding to the alkaline developer, the amount used is 1 mg to 100 g, preferably 0.1 g to 10 g, per liter of the developer.

The dyes and / or pyridinium salt derivatives used in the present invention can be added directly to the developing solution, or water or an organic solvent miscible with water, such as alcohols. It may be dissolved in a ketone, an ester, an amide or the like and added to the developer used in the present invention.

The timing of adding the dye and / or pyridinium salt derivative used in the present invention to the developing solution is not particularly limited, and it may be added to the developing solution in advance and stored as a developing solution, or immediately before the development processing. Dyes used and /
Alternatively, pyridinium salt derivatives may be added for use in development processing.

Although the mechanism of action of the dye and the pyridinium salt derivative of the present invention is not sufficiently clear, the dye does not always need to be present at the time of exposure, so the dye is not involved in the ordinary spectral sensitizing action. It is presumed that the dye and the pyridinium salt derivative of the present invention act as a contrast enhancer for enhancing the sensitivity and gradation of the photographic light-sensitive material during development. In the image forming method using an alkaline developing solution containing an aminophenol type developing agent and / or a dihydroxybenzene type developing agent, the dye and the pyridinium salt derivative have been known to have a markedly high sensitivity and an ultrahigh contrast effect. This is a completely unexpected effect.

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 need to be chemically sensitized, but it is usually chemically sensitized. Sulfur sensitization, reduction sensitization, noble metal sensitization, selenium sensitization, tellurium sensitization and combinations thereof are used as the chemical sensitization method, and particularly preferable chemical sensitization for carrying out the present invention is the sulfur sensitization method. Alternatively, it is a method in which sulfur sensitization is combined with gold sensitization, which is one of the noble metal sensitizations.

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 may be spectrally sensitized with one kind or two or more kinds of sensitizing dyes in order to impart photosensitivity in a desired photosensitive wavelength range.
The sensitizing dye mentioned here is not particularly limited, and all the sensitizing dyes used in the art can be used.

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 type 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, if necessary, various photographic additives such as emulsion stabilizers (hydroxytetramethylindene such as 6-hydroxy-4-methyl-1,3,3a, 7-tetrazaindene) can be used. Zaindene compounds), extenders (such as saponins), gelatin plasticizers (such as acrylic ester copolymers), antistatic agents, coating aids, and photographic property improvement (for example, development acceleration and contrast enhancement).
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.

Next, the alkaline photographic developer used in the present invention will be described. The developer used in the present invention is characterized by being an alkaline developer containing an aminophenol-based developer and / or a dihydroxybenzene-based developer.

The aminophenol-based developer used in the developer of the present invention includes 4-aminophenol, 4-amino-3-methylphenol, 4- (N-methyl) aminophenol, 2,4-diaminophenol and N. -(4-
Hydroxyphenyl) glycine, N- (2'-hydroxyethyl) -2-aminophenol, 2-hydroxymethyl-4-aminophenol, 2-hydroxymethyl-
There are 4- (N-methyl) aminophenol and hydrochlorides and sulfates of these compounds, but N-methyl-4-aminophenol sulfate (methol) is particularly preferable.

Examples of the dihydroxybenzene type developer used in the developer of the present invention include hydroquinone, chlorohydroquinone, bromohydroquinone, isopropylhydroquinone, methylhydroquinone, 2,3-dichlorohydroquinone, 2,3-dibromohydroquinone,
2,5-Dimethylhydroquinone, potassium hydroquinone monosulfonate, sodium hydroquinone monosulfonate, catechol, pyrazol and the like can be used.

These aminophenol type developing agents and /
Alternatively, the amount of the dihydroxybenzene-based developer added is 0.5 to 100 g, preferably 10 per liter of the developer.
g to 50 g.

The developer of the present invention contains an alkaline agent in addition to the above-mentioned developing agent. The alkaline agent is added in order to set the pH of the developer to 9 or more, particularly preferably 10 or more. The alkaline agent used for pH adjustment is a usual water-soluble inorganic alkali metal salt such as sodium hydroxide,
Potassium hydroxide, lithium hydroxide, sodium carbonate, sodium bicarbonate, potassium bicarbonate, potassium carbonate, potassium triphosphate, etc. can be used.

The developer of the present invention preferably contains a preservative 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 addition amount of these sulfites is preferably 0.5 mol or less per liter of the developing solution.

In addition to the above components, the developer of the present invention contains a water-soluble acid (eg, acetic acid, boric acid), a pH buffering agent (eg, sodium triphosphate, sodium carbonate, potassium carbonate, metaborate) as necessary. Sodium phosphate, lithium borate, etc.), inorganic antifoggants (eg, sodium bromide,
Potassium bromide), an organic fog inhibitor (for example, 1-phenyl-5-mercaptotetrazole, 5-nitroindazole, etc.), an organic solvent (for example, ethylene glycol, diethylene glycol, methyl cellosolve, etc.),
Toning agents, surfactants, defoaming agents, water softeners and the like can be used within a range that does not impair the effects of the present invention.

Further, as described above, the developer of the present invention may be used by adding an organic compound having a reduction potential of less than -0.60 V.

The development processing temperature of the developer of the present invention is 18 degrees Celsius.
The range of degrees to 50 degrees is selected, more preferably the range of 20 to 40 degrees Celsius.

As the fixing solution 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 "SPSE HANDBOOK OF PHOTOGRAPHIC SCIENCE AN
D ENGINEERING) "W. Thomas, Jr. eds., John Wiley & Sons (1973), p. 528, etc. can be referred to. In addition to sulfates and thiocyanates, organic sulfur compounds known to be effective as fixing agents can be used, and acid agents (such as acetic acid and citric acid) and preservatives (such as preservatives) can be used as fixing aids. Sodium sulfite etc.), buffering agents (eg boric acid etc.) and hardening agents (eg potassium alum, alum, aluminum sulphate etc.) and the like can be used.

[0099]

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 1.5 × 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 soluble salts by a conventional method, 5 × 10 ⁻⁵ mol of sodium thiosulfate was added to 1 mol of silver halide and the mixture was chemically ripened at 50.0 ° C. for 100 minutes. This emulsion contains 80 g of gelatin per mol of silver halide. The emulsion thus prepared contains 6 mol / mol of silver halide.
× 10 ^-3 mol of 6-hydroxy-4-methyl-1,3,3
After adding 3a, 7-tetrazaindene, 1 on a polyethylene terephthalate base on which an undercoat layer was previously applied.
It was coated so that the amount of silver was 40 mg per 00 cm ² .
Onto these emulsion layers, a gelatin protective layer containing formalin and dimethylolurea as a hardening agent was applied and dried to obtain film sample No. 1.

The LB-200 filter was used as a sample of the film thus prepared, and a tungsten light source of 2666K was used to pass through a step wedge having a step of 0.15.
After exposure for 2 seconds, a developer 1 having the following composition and a dye whose reduction potential is less than -0.60 volt (Specific Example No. D-
18; Reduction potential-1.24 V) was used for the development treatment at 20 ° C for 7 minutes, and the development, termination, fixing, washing with water and drying were carried out.

Composition of Developer 1 Water 750 ml Metol 1.0 g Hydroquinone 9.0 g Potassium bromide 1.0 g Sodium carbonate 30.0 g Sodium sulfite 12.6 g Water was added to give 1 l pH (NaOH water). Adjusted by) 10.8

Composition of Developer 2 Water 750 ml Metol 1.0 g Hydroquinone 9.0 g Potassium bromide 1.0 g Sodium carbonate 30.0 g Sodium sulfite 12.6 g Dye (Specific example number; D-18) 572.5 mg water was added to 1 l pH (adjusted with NaOH water) 10.8

Table 1 shows the obtained photographic characteristics.

[0105]

[Table 1]

In Table 1, 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 film sample No. 1 of Experiment No. 2 is developed with the developer 2 at 20 ° C. for 7 minutes. The sensitivity at the time of development processing was expressed as 100. Gamma represents the average gradient between blackening densities of 0.5 and 3.0 excluding fog, and fog represents the density of the unexposed areas.

As is apparent from Table 1, the exposed film, which is an image forming method according to the present invention, has a reduction potential of −.
When development processing is performed with a developing solution containing an aminophenol-based developer and a dihydroxybenzene-based developer to which a dye that is less than 0.60 V is added, markedly high sensitivity and high contrast occur. However, in the comparative examples that do not satisfy the requirements of the present invention, such high sensitivity and high contrast do not occur. No pepper was generated in any of the samples.

Example 2 In a gelatin aqueous solution kept at 40 ° C., an aqueous silver nitrate solution and 2.0 × 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 at the same time over 60 minutes while maintaining pAg 7.2 to prepare a cubic monodisperse silver chlorobromide emulsion (AgCl 70 mol%) having an average particle size of 0.18 μm. After removing the soluble salts by a conventional method, 5 × 10 ⁻⁵ mol of sodium thiosulfate and 1 × 10 ⁻⁵ mol of chloroauric acid were added to 1 mol of silver halide, and the mixture was heated to 100 at 50.0 ° C.
Chemically aged for minutes. This emulsion contains 80 g of gelatin per mol of silver halide. Thus the emulsion prepared by the per mol of silver halide 12 × 10 ^-3 mol 6-hydroxy-4-methyl-1,3,3a, 7 over tetrazaindene, 1 × 10 ^-3 mol of potassium iodide and 60 ×
10 ^-3 moles of sodium hydroquinone sulfonate subdivided after addition, after the reduction potential of the present invention shown in Table 2 was added noble made compounds than -0.60 volts, respectively, in advance undercoat layer coating It was coated on the above polyethylene terephthalate base so that the amount of silver was 40 mg per 100 cm ² .

On these emulsion layers, a gelatin protective layer containing formalin and dimethylolurea as a hardening agent was applied and dried to obtain film sample numbers 2 to 6.

[0110]

[Table 2]

The film sample thus prepared was exposed in the same manner as in Example 1, and then developed with Developers 3, 4, and 5 having the following compositions for 5 minutes at 30 ° C., and stopped and fixed. Washed with water and dried.

Composition of Developer 3 Water 750 ml Metol 1.0 g Hydroquinone 9.0 g Potassium bromide 5.0 g Sodium carbonate 30.0 g Sodium sulfite 75.0 g Dye (Specific Example No. D-18) 572.5 mg 5-nitroindazole 32.0 mg Water was added to 1 l pH (adjusted with NaOH water) 12.4

Composition of Developer 4 Water 750 ml Metol 10.0 g Potassium bromide 1.0 g Sodium sulfite 75.0 g Sodium metaborate tetrahydrate 35.0 g 5-Nitroindazole 24.0 mg Water In addition, 1 l pH (adjusted with NaOH water) 12.3

Composition of Developer 5 Water 750 ml Hydroquinone 70.0 g Potassium bromide 5.0 g Sodium sulfite 10.0 g Sodium metaborate tetrahydrate 35.0 g Dipotassium phosphate 50.0 g 5-Nitroindazo -L 48.0 mg Dye (Specific example number; D-18) 572.5 g Water was added to 1 l pH (adjusted with NaOH water) 12.3

The photographic properties obtained are shown in Table 3.

[0116]

[Table 3]

In Table 3, 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 film sample No. 3 according to Experiment No. 4 is treated with the developer 3 at 30 ° C. for 5 minutes. The sensitivity at the time of development processing was expressed as 100. Gamma represents the average gradient between blackening densities of 0.5 and 3.0 excluding fog, and fog represents the density of the unexposed areas.

As is clear from Table 3, a film containing a compound having a reduction potential satisfying the requirements of the present invention and having a reduction potential of less than -0.60 volt was imagewise exposed, and then an aminophenol type developing agent and a dihydroxybenzene type developing agent were used. Containing 3 or 4, a developing solution 4 containing only an aminophenol-based developing agent as a developing agent, or a developing solution 5 containing only a dihydroxybenzene-based developing agent as a developing agent.
In case of development processing, the sensitivity is extremely high and gamma is 10
The contrast becomes higher than that. However, in the comparative examples that do not satisfy the requirements of the present invention, such high sensitivity and high contrast do not occur. Also, at this time, put a pepper
Did not occur.

Example 3 Film No. 2 prepared in Example 2 was coated with a 1% by weight methanol solution of the compound according to the present invention shown in Table 4 and dried to obtain film sample Nos. 7 to 10. It was At this time, the coating amount of the solution was measured to calculate the content per mol of silver.

[0120]

[Table 4]

The film sample thus prepared was exposed in the same manner as in Example 1 and then developed with the developer 4 of Example 2 at 30 ° C. for 5 minutes, stopped, fixed, washed with water and dried. did.

The photographic characteristics obtained are shown in Table 5.

[0123]

[Table 5]

In Table 5, the relative sensitivity is the relative value of the reciprocal of the exposure dose at which the density of the evaluation sample excluding fogging is 3.0, and the film sample No. 7 of Experiment No.
The sensitivity when developed at 30 ° C. for 5 minutes was 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 apparent from Table 5, a film containing a compound having a reduction potential of −0.60 V or less and satisfying the requirements of the present invention was imagewise exposed, and then an aminophenol type developing agent was contained as a developing agent. When the developing treatment is performed with the developing solution 4, a markedly high sensitivity and a high contrast with a gamma of more than 10 occur. At this time, no pepper was generated in any of the samples.

On the other hand, in the comparative examples which do not satisfy the requirements of the present invention, such high sensitivity and high contrast do not occur.

[0127]

INDUSTRIAL APPLICABILITY Negative-type silver halide photography in the presence of an organic compound containing one or more heteroatoms of phosphorus, nitrogen, oxygen, sulfur or selenium and having a reduction potential less than -0.60 V. By an image forming method of developing a light-sensitive material with an alkaline developer containing an aminophenol-based developer and / or a dihydroxybenzene-based developer,
It is possible to obtain a high-sensitivity negative tone image with high sensitivity without the occurrence of pepper, which has a gamma of more than 10 which is useful in the photolithography process for printing.

Claims (7)

[Claims] 1. A negative type on a support in the presence of an organic compound containing one or more heteroatoms of phosphorus, nitrogen, oxygen, sulfur or selenium and having a reduction potential less than -0.60 V. A method for forming a high contrast negative image, which comprises developing a silver halide photographic light-sensitive material having a silver halide emulsion layer with an alkaline developer containing an aminophenol-based developer and / or a dihydroxybenzene-based developer. 2. A negative silver halide emulsion layer or other hydrophilic colloid layer contains one or more heteroatoms of phosphorus, nitrogen, oxygen, sulfur or selenium, and has a reduction potential of −.
A negative type silver halide photographic light-sensitive material containing an organic compound that is less than 0.60 volt is developed with an alkaline developing solution containing an aminophenol-based developer and / or a dihydroxybenzene-based developer after imagewise exposure. The method for forming a high-contrast negative image according to claim 1, wherein 3. A negative type silver halide photographic light-sensitive material having a negative type silver halide emulsion layer is imagewise exposed to phosphorus, nitrogen,
An alkaline compound containing one or more heteroatoms of oxygen, sulfur or selenium and having an aminophenol type developing agent and / or dihydroxybenzene type developing agent as a developing agent and an organic compound having a reduction potential less than -0.60 V The method for forming a high-contrast negative image according to claim 1, wherein the development processing is performed with a developing solution. 4. An organic compound containing one or more heteroatoms of phosphorus, nitrogen, oxygen, sulfur or selenium and having a reduction potential less than -0.60 V is a dye. Item 2. A method for forming a high-contrast negative image according to Item 1. 5. An organic compound containing one or more heteroatoms of phosphorus, nitrogen, oxygen, sulfur or selenium and having a reduction potential less than -0.60 V is represented by the general formula (N-
The method for forming a high-contrast negative image according to claim 1, which is a pyridinium salt derivative represented by I). [Chemical 1] (In the formula, R ₁ represents an amino group, an alkyl-substituted amino group, an aromatic group or -AZ. A has 1 to 2 carbon atoms.
0 represents an alkylene group or —CH ₂ CH═CHCH ₂ —, Z is a hydrogen atom, an optionally substituted phenyl group,
It represents a hydroxyl group, an alkoxy group, an acyl group, an alkoxycarbonyl group, a cyano group, an N-alkylamide group, an amide group or a group represented by the general formula (N-Ia). [Chemical 2] In general formula (N-I) and general formula (N-Ia), R ₂ represents
It represents a lower alkyl group, a substituted lower alkyl group or an amide group. n1 represents 0, 1, 2 or 3. However, when a plurality of R ₂ 's are present, they may be different from each other. X ^- represents an anion. However, X does not exist when the general formula (NI) has a betaine structure. ) 6. An organic compound containing one or more heteroatoms of phosphorus, nitrogen, oxygen, sulfur or selenium, and having a reduction potential less than -0.60 V, is represented by the general formula (NI)
The method for forming a high-contrast negative image according to claim 1, which is a quinolinium salt derivative represented by I). [Chemical 3] (In the formula, R ₃ represents a substituted or unsubstituted lower alkyl group. R ₄ and R ₅ are each independently a halogen atom,
It represents a lower alkyl group, a substituted lower alkyl group or a lower alkoxy group. n2 and n3 each independently represent 0, 1 or 2. When there are a plurality of R ₄ and / or R ₅ , they may be different from each other. X ^over
Represents an anion. However, when the general formula (N-II) has a betaine structure, X does not exist. ) 7. An organic compound containing one or more heteroatoms of phosphorus, nitrogen, oxygen, sulfur or selenium and having a reduction potential less than -0.60 V is represented by the general formula (NI)
The method for forming a high-tone negative image according to claim 1, which is an isoquinolinium salt derivative represented by II). [Chemical 4] (In the formula, R ₆ represents an alkyl group or a substituted alkyl group. Further, R ₆ and R ₈ may form a 6-membered ring or a 5-membered ring. R ₇ is a hydrogen atom, a lower alkyl group or a substituted alkyl group. R ₈ and R ₉ each independently represent a hydrogen atom, a lower alkyl group, a substituted lower alkyl group, an alkoxy group or an amide group, and R ₈ and R ₉ are aromatic rings. R ₁₀ represents a halogen atom, an optionally substituted lower alkyl group, an alkoxy group or an amino group optionally substituted by an alkyl group, and n4 represents 0, 1 or 2. When a plurality of R ₁₀ 's are present, they may be different from each other, and X ^- represents an anion, provided that the general formula (N-II
X does not exist when I) has a betaine structure. )