JPH0643602A - Ultrahigh contrast negative image forming method and silver halide light-sensitive material and developer used therefor - Google Patents

Abstract

PURPOSE:To form a negative image ultrahigh on contrast and exceeding a specified value and small in occurrence of pepper by processing a silver halide photographic sensitive material with a developing solution not containing hydroquinone as a developing agent. CONSTITUTION:The silver halide photographic sensitive material having at least one negative type silver halide emulsion layer on a support is imagewise exposed, and processed with the developing solution containing an aminophenol type developing agent and reductones in the presence of an organic compound, baser than -0.60volt, thus permitting a negative image being extremely high in contrast and exceeding a gamma value of 10, and small in occurrence of pepper to be obtained. The organic compound to be used is, preferably, a heterocyclic compound having O, N, S, Se, or P atom as ring-forming atoms, especially, a dye, a pyridinium salt or its derivatives, and isoquinolinium salt or its derivatives.

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 suitable for forming a very hard negative image useful in a photolithography process for printing graphic arts. More specifically, a silver halide photographic light-sensitive material is exposed to an image of an organic compound having a negative reduction potential capable of forming a super-high contrast negative image, and then contains at least an aminophenol-based developing agent and a reductone. The present invention relates to a method of forming an ultrahigh contrast image by developing with a photographic developer, and a silver halide photographic light-sensitive material and a photographic developer used therefor.

[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.

[0004]

However, it has been found that the high contrast image forming system using the above-mentioned 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 a large amount of expensive and environmental pollutant hydroquinone must be used 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, it is allowed to add a high concentration of sulfite to a developer of a high contrast image forming system using a hydrazine derivative, but since it has a high pH (11 to 12.3), it is easily oxidized by air and consumes hydroquinone. Is remarkable. Therefore, in order to maintain the development activity of these developers, a large amount of expensive and environmental pollutant hydroquinone is used, or the amount of hydroquinone consumed by air oxidation is replenished 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.

Therefore, a first object of the present invention is to process a silver halide photographic light-sensitive material with a developer which does not use hydroquinone as a developing agent to obtain a negative image having a very high gamma of more than 10 and less generation of pepper. It is to provide a method of forming.

A second object is to provide a silver halide photographic light-sensitive material which can be effectively used in the above image forming method.

A third object is to provide a photographic developer which is effectively used in the above-mentioned image forming method and which does not use hydroquinone as a developing agent and which is stable at low pH.

[0009]

The object of the present invention is to reduce the reduction potential of a silver halide photographic light-sensitive material having at least one negative-working silver halide emulsion layer on a support to a negative reduction potential. Was achieved by developing with a developer containing an aminophenol developing agent and reductones in the presence of an organic compound less than -0.60 volts, more preferably less than -0.80 volts. .

The organic compound having a negative reduction potential that can be used in the present invention is preferably a heterocyclic compound having nitrogen, oxygen, sulfur, selenium or phosphorus in addition to carbon as a ring-constituting atom, a dye, or the following general compound. Formula (N-
I) a pyridinium salt or a derivative thereof, a quinolinium salt or a derivative thereof represented by the general formula (N-II) and an isoquinolinium salt or a derivative thereof represented by a general formula (N-III) (hereinafter, these pyridinium Salts or derivatives thereof and the like, hereinafter simply referred to as pyridinium salt derivatives) and the like are particularly preferable.

[0011]

[Chemical 1]

(In the formula, R ₁ represents an alkyl group, an amino group, an alkyl-substituted amino group, an aromatic group such as a phenyl group or a pyridyl group, or -AZ. A is an alkylene having 1 to 20 carbon atoms. A group or —CH ₂ CH═CHCH ₂ —, Z is a hydrogen atom, an optionally substituted phenyl group, a hydroxyl group, an alkoxy group, an acyl group, an alkoxycarbonyl group, a cyano group, an N-alkylamide group, an amide group. Alternatively, it represents a group represented by Chemical formula 2.

[0013]

[Chemical 2]

In the general formula (NI) and Chemical Formula 2, R ₂ represents a lower alkyl group, a hydroxyl group, an alkoxy group, a lower alkyl group substituted with an aromatic group such as a phenyl group or a pyridyl 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 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. )

[0015]

[Chemical 3]

(In the formula, R ₃ represents a substituted or unsubstituted lower alkyl group. R ₄ and R ₅ each independently represent a halogen atom, a lower alkyl group, a substituted lower alkyl group or a lower alkoxy group. If n2 and n3 where .R ₄ and / or R ₅ each independently represent 0, 1 or 2 there are a plurality, which may .X ^over those respective different iodine ion, a bromine ion, a chlorine ion, p- Toluene sulfonate ion, perchlorate ion,
Represents an anion such as methylsulfate. However, when the general formula (N-II) has a betaine structure, X does not exist. )

[0017]

[Chemical 4]

(In the formula, R ₆ represents an alkyl group or a substituted alkyl group. Further, R ₆ and R ₈ are a 6-membered ring or 5
You may form a member ring. R ₇ represents a hydrogen atom, a lower alkyl group, a substituted alkyl group or an aryl group. R ₈ and R ₉ each independently represent a hydrogen atom, a lower alkyl group, a hydroxyl group, an alkoxy group, a lower alkyl group substituted with an aromatic group, an alkoxy group or an amide group. Further, R ₈ and R ₉ may form an aromatic ring. 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. n4 represents 0, 1 or 2. When a plurality of R ₁₀ 's are present, they may be different from each other. X
^{Chromatography} represents an iodine ion, a bromine ion, a chlorine ion, p- toluenesulfonate ion, perchlorate ion, an anion such as methylsulfate ion. However, the general formula (N-II
X does not exist when I) has a betaine structure. )

The value of the reduction potential Ered used herein means the potential at which the dye or the pyridinium salt derivative is reduced by the electron injection at the cathode in the voltammetry. The value of the reduction potential Ered can be accurately measured by voltammetry. That is, a dye or pyridinium salt derivative 1 × 10 ⁻³ M to 1 × 10 ⁻⁴ M voltammogram was measured in acetonitrile containing 0.1 M tetra-n-butylammonium perchlorate as a supporting electrolyte. It was determined as the half-wave potential obtained from the above. 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 Electrochemistry (New).
Instrumental Methods in E
Electrochemistry ((Interscience Publishers) (Interscience
Publishers), 1954) and the like.

The silver halide photographic light-sensitive material useful in the image forming method of the present invention has at least one negative type silver halide emulsion layer on a support, and the emulsion layer or at least one other hydrophilic layer. Dissociates one or more organic compounds with a negative reduction potential, or one or more organic compounds with a negative reduction potential and one or more polyalkylene oxides or their derivatives, or one or more organic compounds with a negative reduction potential into the hydrophilic colloid layer. The index pKa is 1
A negative type silver halide photographic light-sensitive material containing at least one inorganic or organic compound and at least one compound can be mentioned.

The photographic developer useful in the image forming method of the present invention includes (1) a photographic developer containing an aminophenol type developing agent and (2) a reductone, or (1) aminophenol. A quaternary ammonium salt compound represented by the general formula (C-I), or a general formula (C-II) or a general formula (C-III), containing a system developing agent and (2) reductone. Achieved by a photographic developer containing an amine or a cyclic imine represented by the general formula (C-IV).

[0022]

[Chemical 5]

(Wherein R ₁₁ , R ₁₂ , R ₁₃ and R ₁₄ are the same or different from each other, and are unsubstituted or substituted with a halogen atom, a hydroxy group, an alkoxy group, an acyloxy group,
1 to 2 carbon atoms substituted with carbamoyl group, trialkylammonium group or lower alkyl group
And 0 represents an alkyl group, an alkenyl group, a cycloalkyl group, an aralkyl group and an aryl group. X ^- represents an anion. )

[0024]

[Chemical 6]

(In the formula, R ₁₅ , R ₁₆ and R ₁₇ are each independently a hydrogen atom, an optionally substituted alkyl group having 1 to 10 carbon atoms, or an optionally substituted 3 to 10 carbon atom). Represents an optionally substituted cycloalkyl group, an optionally substituted aralkyl group having 7 to 10 carbon atoms, or an optionally substituted aryl group having 6 to 10 carbon atoms, and R ₁₅ , R ₁₆ and R ₁₇ A ring may be formed between any two selected from R ₁₅ , R ₁₆ and R ₁₇
Are not hydrogen atoms at the same time. )

[0026]

[Chemical 7]

(Wherein R ₁₈ , R ₁₉ , R ₂₀ and R ₂₁ are each independently a hydrogen atom, an optionally substituted alkyl group having 1 to 8 carbon atoms or an optionally substituted carbon atom). 3 to 8 represents a cycloalkyl group, R ₁₈ , R
_A ring may be formed between any two selected from ₁₉ , R ₂₀ and R ₂₁ . B is an alkylene group having 2 to 8 carbon _{atoms, - (E-CH 2 CH} 2 -) f - or - (E-CH ₂ C
H ₂ CH ₂ −) _g −. However, E represents an oxygen atom, a sulfur atom or -NH-, and f and g represent an integer of 1 to 4. )

[0028]

[Chemical 8]

(In the formula, Q ₁ represents a group of non-metal atoms necessary for forming an aromatic nitrogen-containing heterocycle, and the aromatic nitrogen-containing heterocycle completed by Q ₁ may be substituted or not. Good pyridine ring, quinoline ring, isoquinoline ring, acridine ring, pyridazine ring, pyrimidine ring, pyrazine ring,
It represents a cinnoline ring, a quinazoline ring, a quinoxaline ring, a phthalazine ring and a phenazine ring. )

Further, the reductone used in the alkaline developer used in the present invention is characterized by being a compound represented by the general formula (I) or a salt thereof.

[0031]

[Chemical 9]

(In the formula, R ₂₂ represents a hydrogen atom or a hydroxyl group, and l represents an integer of 1 to 4.) As the dye used in the present invention, symmetrical and asymmetrical cyanine dyes and merocyanine dyes are useful. Is.
Particularly useful dyes for use in the present invention have the following general formula (D-I), which has a negative reduction potential, preferably a reduction potential less than -0.60 volt, more preferably a reduction potential less than -0.80 volt. ), (D-II), (D-III) or (D-IV).

[0033]

[Chemical 10]

In the formula, m ₁ represents 0 or 1. Q ₂ and Q
₃ represents a group of non-metal atoms necessary for forming a nitrogen-containing heterocycle. Examples of the nitrogen-containing heterocycle completed by Q ₂ and Q ₃ include a benzothiazole ring, a naphthothiazole ring, a benzocenazole ring, a benzoxazole ring, a quinoline ring and a thiazoline ring. Q ₂ and Q ₃
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 ₂₃ and R ₂₄ are lower alkyl groups such as methyl group, ethyl group, 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 sulfo 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 ₂₅ 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.

[0035]

[Chemical 11]

In the formula, Y represents an oxygen atom or a sulfur atom. m ₂ represents 0 or 1. Q ₄ represents a non-metal atom group 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 ₄ . Substituents may be introduced into these nitrogen-containing rings completed by Q ₄ , 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 ₂₆ and R ₂₇ 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 ₂₈ represents a hydrogen atom or a lower alkyl group such as a methyl group and an ethyl group.

[0037]

[Chemical 12]

In the formula, R ₂₉ represents a hydrogen atom or a lower alkyl group such as a methyl group, an ethyl group or a propyl group.
R ₃₀ , R ₃₁ , R ₃₂ , and R ₃₃ 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 ₃₄
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.

[0039]

[Chemical 13]

In the formula, Q ₅ represents a non-metal atom group necessary for forming a nitrogen-containing heterocycle. Examples of the nitrogen-containing heterocycle completed by Q ₅ 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 ₅ , 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 ₃₅ and R ₃₆
Each independently represents a hydrogen atom or a lower alkyl group such as a methyl group, an ethyl group or a propyl group. R ₃₇ and R ₃₈ 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.

[0042]

[Chemical 14]

[0043]

[Chemical 15]

[0044]

[Chemical 16]

[0045]

[Chemical 17]

[0046]

[Chemical 18]

[0047]

[Chemical 19]

[0048]

[Chemical 20]

[0049]

[Chemical 21]

[0050]

[Chemical formula 22]

[0051]

[Chemical formula 23]

[0052]

[Chemical formula 24]

[0053]

[Chemical 25]

[0054]

[Chemical formula 26]

[0055]

[Chemical 27]

[0056]

[Chemical 28]

These dyes are commercially available from, for example, F.H. Hamer, "The Cyanine Soybean and Relayed Compounds (TheC).
yanine Dyes and Related C
1964, Interscience
Published by The New York Publishing Company (Intersci)
ence Publishers, N.M. Y. ) See page 55 et seq. And can be easily synthesized by the method described or a similar method.

Pyridinium salt derivatives useful in the present invention are compounds represented by the following general formula (N-I), (N-II) or (N-III).

[0059]

[Chemical 29]

In the formula, R ₁ represents an alkyl group, an amino group, an alkyl-substituted amino group (N-methylamino group, N, N-dimethylamino group or the like), an aromatic group such as a phenyl group or a pyridyl group, or -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,
Hydroxyl group, alkoxy group such as methoxy group and 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 Chemical formula 30.

[0061]

[Chemical 30]

In the general formula (N-I) and Chemical formula 30, R ₂ is an aromatic such as a lower alkyl group (methyl group, ethyl group, propyl group, butyl group, etc.), a hydroxyl group, an alkoxy group, a phenyl group or a pyridyl group. A lower alkyl group substituted with a group (2-hydroxyethyl group, 3-hydroxypropyl group, 2-methoxyethyl group, 4-ethoxybutyl group, benzyl group, 2-phenylethyl group, 3- (4-pyridyl) propyl group, etc.) or an amide group (-CONH ₂ ,
-CONHCH ₃ etc.). 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 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.

[0063]

[Chemical 31]

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, etc.). 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 are each independently 0, 1 or 2
Represents 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, when the general formula (N-II) has a betaine structure, X does not exist.

[0066]

[Chemical 32]

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.

[0069]

[Chemical 33]

[0070]

[Chemical 34]

[0071]

[Chemical 35]

[0072]

[Chemical 36]

[0073]

[Chemical 37]

[0074]

[Chemical 38]

[0075]

[Chemical Formula 39]

[0076]

[Chemical 40]

[0077]

[Chemical 41]

[0078]

[Chemical 42]

[0079]

[Chemical 43]

[0080]

[Chemical 44]

[0081]

[Chemical formula 45]

[0082]

[Chemical formula 46]

[0083]

[Chemical 47]

[0084]

[Chemical 48]

[0085]

[Chemical 49]

[0086]

[Chemical 50]

[0087]

[Chemical 51]

These pyridinium salt derivatives are the corresponding pyridines, as described in "Large Organic Chemistry", Vol. 16 (III), pages 7 and 129 (1959, Asakura Shoten) supervised by M. Otake. It can be synthesized by reacting a quinoline or isoquinoline derivative with an alkyl halide derivative. The specific synthesis method is. A. Grob,
E. Report by Renk, Helv. Chim. Acta
37 , 1672 (1954); E. Lyle,
E. F. Perlowski, H .; J. Trosia
niec, G.M. G. Lyle, J. J. Org. C
hem. 20 , 1761 (1955); R. Lam
Borg, R .; M. Burton, N.M. O. Kapla
n. Am. Chem. Soc. 79 , 61
73 (1957); Ciusa, A .; Buccel
Li's report, GazzettaChimia Ita
Liana 88 , 393 (1958) and the like.

The dyes and pyridinium salt derivatives used in the present invention are at least one negative-working silver halide emulsion layer constituting a silver halide photographic light-sensitive material or a non-light-sensitive layer consisting of other hydrophilic colloid layers. For example, it may be contained in a protective layer, an intermediate layer, an antihalation layer, a filter layer, or the like.

[0090] The addition amount of the silver halide photographic light-sensitive material of the dyes and pyridinium salts derivatives used in the present invention, the range of 10 ^-2 mol per mol of silver halide 10 ^-6 mol are suitable, dyes When it is alone, 10 ^-3 to 10 ^-1 mol is preferable, and when it is a pyridinium salt derivative alone, 10 ^-4 to 10 ^-2 mol is preferable, and polyalkylene oxide and its derivative (hereinafter simply referred to as polyalkylene oxide derivative). Is present, ^10-5 mol to ^10-3 mol is particularly preferred. Further, the dyes and pyridinium salt derivatives used in the present invention can be used alone or in combination.

To add the dyes and pyridinium salt derivatives used in the present invention to a negative type silver halide emulsion layer or other non-photosensitive layer, water or an organic solvent miscible with water such as alcohols and ketones is added. It may be added to the negative type silver halide emulsion or the non-photosensitive hydrophilic colloidal solution used in the present invention after being dissolved in the compounds, esters, amides and the like.

The dye and the 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. further,
The silver halide photographic light-sensitive material may be added after exposure.

The dye and the pyridinium salt derivative may be contained in the developer, and the content thereof is preferably 10 ^-6 mol / liter to 10 ^-1 mol / liter in the developer.

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, and therefore the dye is not involved in the usual 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 an image forming method using an alkaline developer containing an aminophenol-based developing agent and a reductone, the dye and the pyridinium salt derivative have not been known to have a markedly high sensitivity and a super-high contrast action, and they are completely unexpected. It is a non-effect.

When a very high contrast negative image is formed by the image forming method of the present invention, a further excellent superhigh contrast negative image can be obtained by developing in the presence of a polyalkylene oxide derivative.

Examples of the polyalkylene oxide derivative used in the present invention include polyalkylenes such as polyethylene oxide and polypropylene oxide, polyalkylene oxides such as polyethylene oxide and polypropylene oxide, and water, aliphatic alcohols, phenols and glycols. Fatty acids, addition polymerization products of one compound selected from the group of organic amines, condensates of polyalkylene oxide and one compound selected from the above compound group, or various alkylene oxides (eg ethylene Block copolymers of oxide and propylene oxide). The polyalkylene oxide derivative used in the present invention has a number average molecular weight of 500 to 20,000, particularly preferably 1,000 to 10,000.

Next, some specific examples of the polyalkylene oxide derivative used in the present invention are shown.

[0098]

[Chemical 52]

[0099]

[Chemical 53]

[0100]

[Chemical 54]

The polyalkylene oxide derivative used in the present invention may be contained in either the photographic light-sensitive material or the developer. However, it is more preferable to incorporate it in the photographic light-sensitive material.

In order to incorporate the polyalkylene oxide derivative into the photographic light-sensitive material, the compound may be added to the negative-working silver halide emulsion, or other non-light-sensitive layer comprising a hydrophilic colloid layer, for example, , A protective layer, an intermediate layer, an anti-halation layer, a filter layer and the like. It is preferably added to the negative type silver halide emulsion used in the present invention. To add the polyalkylene oxide derivative used in the present invention to a photographic light-sensitive material, it is dissolved in water or an organic solvent miscible with water, for example, alcohols, ketones, esters, amides, etc. It may be added to the negative type silver halide emulsion used or a non-photosensitive hydrophilic colloid solution.

The amount of the polyalkylene oxide derivative used in the present invention added to the photographic light-sensitive material is appropriately in the range of 0.1 to 10 g per mol of silver halide.
A range from g to 5 g is particularly preferred. Further, the timing of adding these compounds can be selected at any time during the process of producing the photographic light-sensitive material. For example, when it is added to the silver halide emulsion layer, it is preferably added at an arbitrary time after the second ripening and before the coating.

The polyalkylene oxide derivative used in the present invention is effective even if it is contained in the developer of the present invention. In this case, 0.1 to 15 g may be added per liter of the developing solution. .

By incorporating an inorganic or organic compound having a dissociation index pKa of 11 or less in the silver halide photographic light-sensitive material used in the image forming method of the present invention, it is possible to achieve a quicker development processing time and a wide development processing time. A super-high contrast image can be formed.

Inorganic compounds having a dissociation index pKa11 or less used in the present invention are described in, for example, "Chemical Handbook Basic Edition" edited by The Chemical Society of Japan, Maruzen Co., Ltd. (1975), page 8.178 and "Langez Handbook". Of Chemistry "(Lange's Handbook of
Chemitry, "John Dane" (Jo
hn A. Dean) 13th revised edition, "McGraw-Hill Book Com"
Inorganic compounds having a pKa value of 11 or less from the table of "acid dissociation index pKa of inorganic compound in water" in Tables 5-7, pp. 5-14 to 5-17. Can be used as a reference.

The dissociation index pKa used in the present invention is 11
The following inorganic compounds, nitric acid, sulfuric acid, sulfurous acid, bisulfite, phosphoric acid, phosphorous acid, hypophosphoric acid, metaphosphoric acid, hypophosphorous acid, amidophosphoric acid, carbonic acid, bicarbonate, hydrochloric acid, hydrobromic acid, hydroiodic acid, Examples thereof include acids such as orthoboric acid, metaboric acid, aluminic acid, amidosulfate, hydrazinosulfate, and sulfamic acid, and alkali metal salts, alkaline earth metal salts, aluminum salts, ammonium salts, and hydrazinium salts of these acids. Also, among the above acids, nitric acid,
In the case of a strong acid having a negative dissociation index pKa such as sulfuric acid, hydrochloric acid or hydrobromic acid, it is preferably used as a salt such as an aluminum salt, an ammonium salt or a hydrazinium salt.

Next, as specific examples of the acidic inorganic compound preferably used in the present invention, amidosulfuric acid, ammonium amidosulfate, amidophosphoric acid, ammonium sulfite, potassium sulfite, potassium hydrogen sulfite, sodium sulfite, sodium hydrogen sulfite, sodium aluminate, Magnesium aluminate, aluminum chloride, ammonium chloride,
Primary hydrazine chloride, secondary hydrazine chloride, magnesium ammonium chloride, orthoboric acid, orthophosphoric acid, potassium tetraborate, aluminum bromide, ammonium bromide,
Ammonium nitrate, aluminum nitrate, hydrazine mononitrate, hydrazine dinitrate, hypophosphoric acid, sodium hypophosphate, disodium dihydrogen phosphate, sulfonylimide, ammonium carbonate, ammonium hydrogen carbonate, potassium hydrogen carbonate, sodium hydrogen carbonate, magnesium hydrogen carbonate Potassium, lithium hydrogen carbonate, ammonium tetrachloroaluminate, sodium tripolyphosphate, sodium trimetaphosphate, potassium disulfite, sodium disulfite, pyrophosphoric acid, potassium pyrophosphate, sodium pyrophosphate, disodium dihydrogen pyrophosphate, magnesium pyrophosphate, Sodium peroxoborate, hydrazinosulfate, sodium sulfamate, phosphonic acid, potassium phosphonate, metaboric acid, ammonium metaborate, potassium metaborate, sodium metaborate System, metaphosphoric acid, potassium metaphosphate, sodium metaphosphate, aluminum iodide, aluminum sulfate, ammonium sulfate, ammonium aluminum sulfate, potassium aluminum sulfate, ammonium hydrogen sulfate, potassium hydrogen sulfate, sodium hydrogen sulfate, hydrazine monosulfate, hydrazine dihydroxide. , Magnesium ammonium sulfate, aluminum phosphate, ammonium phosphate, potassium phosphate, sodium phosphate, sodium ammonium phosphate, diammonium hydrogen phosphate, dipotassium hydrogen phosphate, disodium hydrogen phosphate, ammonium dihydrogen phosphate, potassium dihydrogen phosphate, dihydrogen phosphate Examples thereof include sodium and magnesium ammonium phosphate, but the present invention is not limited to these specific examples.

Dissociation index pK preferably used in the present invention
Organic compounds having a of 11 or less are organic carboxylic acids, amino acids, organic sulfonic acids, organic sulfinic acids, organic sulfonamides, organic phosphoric acids, organic phosphonic acids, organic phosphinic acids, organic compounds having a phenolic hydroxyl group, α- Diketones, β-diketones, active methylene compounds having a pKa of 11 or less, protic acids such as organic boric acid and organic boronic acid, and their ammonium salts, hydrazinium salts,
In addition to aluminum salts, alkali metal salts or alkaline earth metal salts, primary, secondary and tertiary amines, amides, organic hydrazines or heterocyclic compounds having a dissociation index pKa of 11 or less, and these compounds It is a salt of a strong acid or a weak acid.

The dissociation index pKa used in the present invention is 11
The following organic compounds are described, for example, in “Chemical Handbook Basic Edition” edited by The Chemical Society of Japan, Maruzen Co., Ltd. (1975), pp. 994 to 998, and Table 8.179 and “Langer's Handbook of Chemistry” (Lange's Han).
13th revised edition of John A. Dean, "Book of Chemistry", "John Dane"
"McGraw-Hill" (McGraw-Hill)
Book Company (1985), 5-18
PKa from the table of "acid dissociation index pKa of organic compound in water" in Table 5-8 on pages 5 to 60
An organic compound having a value of 11 or less can be selected and used.

Next, specific examples of the organic compounds preferably used in the present invention having a dissociation index pKa of 11 or less will be given.
The present invention is not limited to these specific examples. As preferred specific examples, for example, isovaleric acid, isobutyric acid, octanoic acid, cyclohexanecarboxylic acid, lactic acid, acetic acid, ammonium acetate, aluminum acetate, hydrazinium acetate, sodium acetate, potassium acetate, lithium acetate, cerium acetate, magnesium acetate, acetic acid. Calcium, strontium acetate, barium acetate, butyric acid, crotonic acid, azelaic acid, citric acid, succinic acid, oxalic acid, tartaric acid,
Fumaric acid, malonic acid, malic acid, lauric acid, myristic acid, palmitic acid, stearic acid, anisic acid, benzoic acid, p-aminobenzoic acid, naphthoic acid, terephthalic acid,
Pyromellitic acid, asparagine, aspartic acid, 4-
Aminobutyric acid, alanine, arginine, isoleucine, glycine, glutamic acid, cysteine, serine, valine,
Histidine, methionine, leucine, sodium benzenesulfonate, sodium p-toluenesulfonate, sodium lauryl sulfate, 5-sulfosalicylic acid, sodium laurylsulfoacetate, sodium 1-naphthalenesulfonate, sodium 2-naphthalenesulfonate, 1-
Sodium naphthol-4-sulfonate, sodium n-dodecylbenzenesulfonate, sodium 2,4-dimethylbenzenesulfonate, 4-aminonaphthalene-1
-Sodium sulfonate, disodium 1,5-naphthalenedisulfonate, sodium di-2-ethylhexyl sulfosuccinate, sodium benzenesulfinate, benzenesulfonamide, p-toluenesulfonamide,
Benzoic acid-2-phosphoric acid, adenosine-2'-phosphoric acid, phenol-3-phosphoric acid, galactose-1-phosphoric acid, sodium lauryl phosphate, benzenephosphonic acid, 2-aminoethylphosphonic acid, 2-bromo-p. -Tolylphosphonic acid, 2-
Methoxyphenylphosphonic acid, sodium phenylphosphinate, t-butylphosphinic acid, o-cresol,
m-cresol, p-cresol, 4-amino-m-cresol, 2,4-dinitrophenol, o-bromophenol, p-phenolsulfonic acid, p-acetylphenol , Ascorbic acid, reductin, ethyl 3-oxobutanoate, acetylacetone, ethyl malonate, N
-Methylacetoacetamide, 1-phenyl-3-methyl-5-pyrazolone, 3-hydroxyphenylboric acid,
3-aminophenylboronic acid, β-phenylethylboronic acid, aniline, aniline hydrochloride, aniline acetate, aniline sulfate, o-chloroaniline, anilinesulfonic acid, 1-naphthylamine, o-phenylenediamine, 2
-Aminoethanol hydrochloride, 2- (2-aminoethyl)
Pyridine hydrochloride, 3-aminoquinoline hydrochloride, 1,2-
Butanediamine hydrochloride, dietanolamine hydrochloride, diphenylamine, N-ethylaniline hydrochloride, N-methylethylamine hydrochloride, di (2-methoxyethyl) amine hydrochloride, triethanolamine hydrochloride, triallylamine hydrochloride, N , N-dimethyl-o-toluidine hydrochloride, N-methylmorpholine hydrochloride, acetamide hydrochloride, nicotinamide hydrochloride, isonicotinamide hydrochloride, phthalamide hydrochloride, hydrazine-N, N-diacetic acid, hydrazine-N, N'-diacetic acid, 4,4'-dipyridyl, methyl isonicotinate, 8-quinolinol hydrochloride, quinoline hydrochloride, methyl picolinate, 2,4-dimethylpyridine hydrochloride, 2,6-dimethylpyridine hydrochloride Mention may be made of salts, piperazine hydrochloride, adenine, guanine and cytosine.

The compound having a dissociation index pKa of 11 or less used in the present invention is used by being contained in at least one hydrophilic colloid layer constituting the silver halide photographic light-sensitive material, preferably a negative type silver halide emulsion layer. It is contained in a non-photosensitive hydrophilic colloid layer which is applied adjacent to the above, for example, a protective layer, an intermediate layer, an antihalation layer or a filter layer.

To add a compound having a dissociation index pKa of 11 or less used in the present invention to a negative-type silver halide emulsion layer or other non-photosensitive layer, water or an organic solvent miscible with water, such as alcohol. It may be added to the hydrophilic colloidal solution of the negative type silver halide emulsion layer or the non-photosensitive layer used in the present invention after being dissolved in a vinyl group, a ketone group, an ester group, an amide group and the like.

The amount of the compound having a dissociation index pKa of 11 or less used in the present invention added to the hydrophilic colloid layer is appropriately in the range of 10 ⁻⁵ to 5 mol, and particularly preferably 5 mol per mol of silver halide. It is in the range of × 10 ^-3 mol to 1 mol.

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 and combinations thereof are used as the chemical sensitization method, and particularly preferred chemical sensitization for the practice of the present invention is sulfur sensitization method or sulfur sensitization,
This is a method that combines gold sensitization, which is one of the noble metal sensitizations.

As the sulfur sensitizer, active gelatin, thiosulfates, 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 to a desired photosensitive wavelength range.

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, 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 at least an aminophenol-based developing agent and reductones. In order to obtain a high-contrast image more rapidly and stably, the following general formulas (C-I) and (C-II) are used as the third component.
It is preferable to contain one or more compounds represented by (C-III) or (C-IV).

[0126]

[Chemical 55]

In the formula, R ₁₁ , R ₁₂ , R ₁₃ and R ₁₄ are the same or different from each other and are unsubstituted or substituted with a halogen atom, a hydroxy group, an alkoxy group, an acyloxy group, a carbamoyl group, a trialkylammonium group or a lower group. Number of carbon atoms substituted with alkyl groups is 1 to 20
Represents an alkyl group, an alkenyl group, a cycloalkyl group, an aralkyl group and an aryl group. X ^- represents an anion.

[0128]

[Chemical 56]

In the formula, R ₁₅ , R ₁₆ and R ₁₇ are each independently a hydrogen atom, an optionally substituted alkyl group having 1 to 10 carbon atoms, or an optionally substituted 3 carbon atom.
To a cycloalkyl group having 10 to 10 carbon atoms, an optionally substituted aralkyl group having 7 to 10 carbon atoms, or an optionally substituted aryl group having 6 to 10 carbon atoms,
A ring may be formed between any two members selected from R ₁₅ , R ₁₆ and R ₁₇ . However, R ₁₅ , R ₁₆ and R ₁₇ are not hydrogen atoms at the same time.

[0130]

[Chemical 57]

In the formula, R ₁₈ , R ₁₉ , R ₂₀ and R ₂₁ are each independently a hydrogen atom, an optionally substituted alkyl group having 1 to 8 carbon atoms, or an optionally substituted 3 carbon atom. To a cycloalkyl group represented by R ₁₈ ,
A ring may be formed between any two selected from R ₁₉ , R ₂₀ and R ₂₁ . B is an alkylene group having 2 to 8 carbon _{atoms, - (E-CH 2 CH} 2 -) f - or - (E-CH ₂
CH ₂ CH ₂ −) _g −. However, E represents an oxygen atom, a sulfur atom or -NH-, and f and g represent an integer of 1 to 4.

[0132]

[Chemical 58]

In the formula, Q ₁ represents a non-metal atom group necessary for forming an aromatic nitrogen-containing heterocycle, and the aromatic nitrogen-containing heterocycle completed by Q ₁ may be substituted. It represents a pyridine ring, a quinoline ring, an isoquinoline ring, an acridine ring, a pyridazine ring, a pyrimidine ring, a pyrazine ring, a cinnoline ring, a quinazoline ring, a quinoxaline ring, a phthalazine ring and a phenazine ring.

The quaternary ammonium salt compound represented by formula (CI) used in the present invention will be described in detail.

As the alkyl group having 1 to 20 carbon atoms represented by R ₁₁ , R ₁₂ , R ₁₃ and R _{14 of the} general formula (CI), an alkyl group having 1 to 14 carbon atoms is particularly preferable,
For example, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, n-hexyl group, n-octyl group,
Examples thereof include n-decyl group, n-dodecyl group, and n-tetradecyl group. Further, these alkyl groups may be substituted, and the substituent is preferably a halogen atom, a hydroxy group, an alkoxy group, an acyloxy group, a carbamoyl group or a trialkylammonium group. Specific examples of the substituted alkyl group include, for example, 2
-Bromoethyl group, hydroxyethyl group, 3-hydroxypropyl group, methoxyethoxymethyl group, 2-acetoxyethyl group, 2-n-propionyloxyethyl group, 2-carbamoylethyl group, 6-trimethylammoniumhexyl group, and 10 -Trimethylammonium-n-decyl group etc. can be mentioned. R ₁₁ , R
_The alkenyl group represented by ₁₂ , R ₁₃ and R ₁₄ is particularly preferably an alkenyl group having 2 to 8 carbon atoms, for example,
Examples thereof include a vinyl group, an allyl group, a 2-butenyl group, a 3-hexenyl group and a 4-octenyl group.
The cycloalkyl group represented by R ₁₁ , R ₁₂ , R ₁₃ and R ₁₄ is preferably a cyclopentyl group or a cyclohexyl group. These cycloalkyl groups may be substituted, and as a substituent, a lower alkyl group (methyl group, ethyl group, etc.), a hydroxy group and a hydroxyalkyl group (hydroxymethyl group, 2-hydroxyethyl group, etc.)
Is preferred. Specific examples of the substituted cycloalkyl group include:
For example, 2-hydroxycyclopentyl group, 3-hydroxycyclohexyl group, 4-hydroxycyclohexyl group, 3- (2'-hydroxyethyl) cyclopentyl group, 3- (2'-hydroxyethyl) cyclohexyl group, 2-methylcyclopentyl group, etc. Can be mentioned.

The unsubstituted or optionally substituted aralkyl group represented by R ₁₁ , R ₁₂ , R ₁₃ and R ₁₄ is benzyl group, p-methoxybenzyl group, p-methylbenzyl group, p-hydroxymethylbenzyl group. And m-hydroxymethylbenzyl group are preferred. R ₁₁ , R ₁₂ , R
_The unsubstituted or optionally substituted aryl group represented by ₁₃ and R ₁₄ is phenyl group, p-tolyl group and p
-Hydroxymethylphenyl group and the like are preferable. X ⁻ represents an anion such as iodine ion, bromine ion, chlorine ion, perchlorate ion, p-toluenesulfonate ion, and methylsulfate ion.

Next, typical examples of the quaternary ammonium salt compound preferably used in the developer of the present invention will be listed, but the present invention is not limited to these examples. A-1 Tetramethylammonium bromide A-2 Tetraethylammonium chloride A-3 Ethyltrimethylammonium iodide A-4 Methyltriethylammonium chloride A-5 Ethyltri-n-propylammonium iodide A-6 Tetra-n-propylammonium bromide A -7 Tetra-n-butylammonium bromide A-8 Tetra-n-amylammonium bromide A-9 n-hexyltrimethylammonium bromide A-10 n-octyltrimethylammonium bromide

A-11 n-dodecyltrimethylammonium chloride A-12 n-dodecyltrimethylammonium bromide A-13 n-dodecyl-n-butyldimethylammonium bromide A-14 n-tetradecyltrimethylammonium bromide A-15 bromocholine bromide A-16 Choline bromide A-17 2-Hydroxyethyltriethylammonium iodide A-18 2-Methoxyethoxymethyltriethylammonium chloride A-19 Acetylcholine bromide A-20 n-Butyrylcholine bromide

A-21 Carbamylcholine chloride A-22 Hexamethonium bromide A-23 Decamethonium iodide A-24 Trimethylvinylammonium bromide A-25 Diallyldimethylammonium chloride A-26 2-Butenyltrimethylammonium bromide A- 27 3-Hexenyltrimethylammonium chloride A-28 4-octenyltrimethylammonium bromide A-29 Cyclopentyltrimethylammonium bromide A-30 Cyclohexyltrimethylammonium bromide

A-31 2-hydroxycyclopentyltrimethylammonium bromide A-32 3-hydroxycyclohexyltrimethylammonium bromite A-33 4-hydroxycyclohexyltrimethylammonium bromite A-34 3- (2'-hydroxyethyl) cyclopentyltrimethylammonium Bromide A-35 3- (2'-hydroxyethyl) cyclohexyltrimethylammonium bromide A-36 2-Methylcyclopentyltrimethylammonium bromide A-37 Trimethylbenzylammonium chloride A-38 Trimethylbenzylammonium bromide A-39 Triethylbenzylammonium bromide A- 40 trimethyl-p-methoxybenzyl ammonium bromide

A-41 Trimethyl-p-methylbenzylammonium bromide A-42 Trimethyl-p-hydroxymethylbenzylammonium chloride A-43 Trimethyl-m-hydroxymethylbenzylammonium chloride A-44 Phenyltriethylammonium iodide A-45 Trimethyl Trilylammonium bromide A-46 Triethyl-p-hydroxymethylphenylammonium bromide

Next, the general formula (C-I) used in the present invention is used.
I) or the amine represented by the general formula (C-III) or the cyclic imine represented by the general formula (C-IV) will be described in detail.

R ₁₅ , R ₁₆ and R in the general formula (C-II)
The alkyl group having 1 to 10 carbon atoms represented by ₁₇ is particularly preferably an alkyl group having 1 to 6 carbon atoms, for example, methyl group, ethyl group, propyl group, isopropyl group, n
-Butyl group, n-hexyl group and the like can be mentioned. Further, these alkyl groups may be substituted, and the substituent is preferably a hydroxy group, a hydroxyalkoxy group, a hydroalkylthio group or a carboxyl group. Specific examples of the substituted alkyl group include, for example, 2-hydroxyethyl group, 3-hydroxypropyl group,
2,3-dihydroxypropyl group, 2- (2'-hydroxyethoxy) ethyl group, 2- (2'-hydroxythioethyl) ethyl group, carboxymethyl group, 2-carboxyethyl group, 5-carboxypentyl group, etc. Can be mentioned. The cycloalkyl group having 3 to 10 carbon atoms represented by R ₁₅ , R ₁₆ and R ₁₇ is preferably a cyclopentyl group or a cyclohexyl group. These cycloalkyl groups may be substituted, and as a substituent, a lower alkyl group (methyl group, ethyl group, etc.), a hydroxy group, a hydroxyalkyl group (hydroxymethyl group, 2-
Hydroxyethyl groups) and carboxyl groups are preferred. Specific examples of the substituted cycloalkyl group include, for example, 2-hydroxycyclopentyl group, 3-hydroxycyclohexyl group, 4-hydroxycyclohexyl group,
3- (2'-hydroxyethyl) cyclopentyl group, 3
-(2'-hydroxyethyl) cyclohexyl group, 2-
Examples thereof include a methylcyclopentyl group and a 4-carboxycyclohexyl group.

The optionally substituted aralkyl group having 7 to 10 carbon atoms represented by R ₁₅ , R ₁₆ and R ₁₇ is benzyl group, p-methoxybenzyl group, p-methylbenzyl group, p-hydroxymethylbenzyl group. Groups, m-hydroxymethylbenzyl group, p-carboxybenzyl group and the like are preferable. The optionally substituted aryl group having 6 to 10 carbon atoms represented by R ₁₅ , R ₁₆ and R ₁₇ is a phenyl group, a p-tolyl group, a p-hydroxymethylphenyl group and an o- or p-carboxy group. A phenyl group and the like are preferable. The ring formed between any two members selected from R ₁₅ , R _{16 and} R ₁₇ is preferably a saturated 5-membered ring, 6-membered ring or 7-membered ring, such as a pyrrolidine ring, a piperidine ring or morpholine. And a ring and a hexamethyleneimine ring.

R ₁₈ , R ₁₉ , and R _{20 of the} general formula (C-III)
The alkyl group having 1 to 8 carbon atoms represented by R ₂₁ is preferably methyl group, ethyl group, propyl group, isopropyl group, n-butyl group and n-hexyl group. These alkyl groups may be substituted, and the substituent is preferably a hydroxy group, a hydroxyalkoxy group, a hydroxyalkylthio group or the like. Specific examples of the substituted alkyl group include, for example, 2-hydroxyethyl group, 3-hydroxypropyl group, 2,3-dihydroxypropyl group, 2- (2'-hydroxyethoxy) ethyl group, 2-
(2'-hydroxythioethyl) ethyl group etc. can be mentioned. The cycloalkyl group having 3 to 8 carbon atoms represented by R ₁₈ , R ₁₉ , R ₂₀ and R ₂₁ is preferably a cyclopentyl group or a cyclohexyl group. These cycloalkyl groups may be substituted, and examples of the substituent include a lower alkyl group (methyl group, ethyl group, etc.), a hydroxy group, a hydroxyalkyl group (hydroxymethyl group,
2-hydroxyethyl group) is preferred. Specific examples of the substituted cycloalkyl group include, for example, 2-hydroxycyclopentyl group, 3-hydroxycyclohexyl group,
4-hydroxycyclohexyl group, 2-hydroxymethylcyclopentyl group, 3-hydroxymethylcyclohexyl group, 2-methylcyclopentyl group and the like can be mentioned. The alkylene group having 2 to 8 carbon atoms represented by B is preferably an ethylene group, a trimethylene group, a tetramethylene group, a pentamethylene group or a hexamethylene group. The ring formed between any two members selected from R ₁₈ , R ₁₉ , R ₂₀ and R ₂₁ is preferably a saturated 5-membered ring or 6-membered ring such as a pyrrolidine ring, a piperidine ring or a morpholine ring. And a piperazine ring.

Q _{1 in the} general formula (C-IV) represents a nonmetal atom group necessary for forming an aromatic nitrogen-containing heterocycle, and Q ₁
The aromatic nitrogen-containing heterocycle completed by pyridine ring, quinoline ring, isoquinoline ring, acridine ring,
Examples include a pyridazine ring, a pyrimidine ring, a pyrazine ring, a cinnoline ring, a quinazoline ring, a quinoxaline ring, a phthalazine ring and a phenazine ring. A substituent may be introduced into these aromatic nitrogen-containing heterocycles, and examples of the substituent include a lower alkyl group such as a methyl group, an ethyl group, a propyl group, and a butyl group, a halogen atom, an alkoxy group, a hydroxyl group. , Carbamoyl group, acetyl group and amino group.

Typical specific examples of the above compounds which are preferably used in the developer of the present invention are shown below, but the present invention is not limited to these specific examples. A-47 methylamine A-48 ethylamine A-49 propylamine A-50 isopropylamine A-51 n-butylamine A-52 isobutylamine A-53 n-amylamine A-54 isoamylamine A-55 n-hexylamine A- 56 2-heptylamine A-57 dimethylamine A-58 diethylamine A-59 dipropylamine A-60 diisopropylamine

A-61 Di-n-butylamine A-62 Trimethylamine A-63 Triethylamine A-64 Cyclopentylamine A-65 2-Methylcyclopentylamine A-66 Cyclohexylamine A-67 N-Methylcyclopentylamine A-68 N-methyl Cyclohexylamine A-69 benzylamine A-70 p-methylbenzylamine A-71 p-methoxybenzylamine A-72 N-methylbenzylamine A-73 N-methyl p-methylbenzylamine A-74 N-methyl p- Methoxybenzylamine A-75 Aniline A-76 o-Toluidine A-77 m-Toluidine A-78 p-Toluidine A-79 o-Aminobenzyl Alcohol A-80 p-Aminobenzyl Alcohol

A-81 Methylaniline A-82 Pyrrolidine A-83 Piperidine A-84 Hexamethyleneimine A-85 Ethanolamine A-86 3-Amino-1-propanol A-87 2-Amino-1-propano A-88 4-amino-1-butanol A-89 2-amino-1-butanol A-90 5-amino-1-pentanol A-91 6-amino-1-hexanol A-92 2-hydroxycyclopentylamine A-93 3-hydroxycyclohexylamine A-94 4-hydroxycyclohexylamine A-95 3- (2'-hydroxyethyl) cyclopentylamine A-96 3- (2'-hydroxyethyl) Cyclohexylamine A-97 p-hydroxymethylbenzylamine A-98 m-hydroxyme Le benzylamine A-99 p-hydroxy-methylaniline A-100 2- (ethylamino) ethanol - Le

A-101 2-anilinoethanol A-102 N-benzylaminoethanol A-103 N- (p-methoxybenzyl) aminoethanol A-104 2-dimethylaminoethanol A-105 2- Diethylaminoethanol A-106 3-Dimethylamino-1-propanol A-107 1-Dimethylamino-2-propanol A-108 3-Diethylamino-1-propanol A-109 3-Dimethylamino- 1,2-Propanedol A-110 3-Diethylamino-1,2-propanediol A-111 3-Piperidino-1,2-propanediol A-112 3-Pyrrolidino-1,2-propane Diol A-113 4-Dimethylamino-1-butanol A-114 Morpholine A-115 1-Piperidino Tanol A-116 Diethanolamine A-117 N-Ethyldiethanolamine A-118 2,2 '-(n-Butylimino) diethanol A-119 N-Phenyldiethanolamine A-120 N-benzyldi Ethanolamine

A-121 N-phenethyldiethanolamine A-122 Triethanolamine A-123 Triisopropanolamino A-124 2- (N, N-diethylaminoethoxy) ethanol A-125 2- ( N, N-diethylamino-2'-
Ethylthio) ethanol A-126 Glycine A-127 β-alanine A-128 Serine A-129 2-Aminobutyric acid A-130 6-Amino-n-caproic acid A-131 1-Aminocyclohexanecarboxylic acid A-132 3-Aminocyclohexanecarboxylic acid A-133 p-carboxybenzylamine A-134 o-aminobenzoic acid A-135 p-aminobenzoic acid A-136 ethylenediamine A-137 N-ethylethylenediamine A-138 N, N'-dimethyl. Ethylenediamine A-139 N, N'-diethylethylenediamine A-140 N, N-dimethylethylenediamine

A-141 N, N, N ', N'-tetramethylethylenediamine A-142 1,3-diaminopropane A-143 N, N-dimethyl-1,3-diaminopropane A-144 N, N, N ', N'-tetramethyl-
1,3-diaminopropane A-145 1,4-diaminobutane A-146 N, N, N ', N'-tetramethyl-1,
4-diaminobutane A-147 1,5-diaminopentane A-148 2,2-dimethyl-1,5-diaminopentane A-149 N, N-dimethyl neopentanediamine A-150 1,6-diaminohexane A- 151 N, N'-dimethyl-1,6-diaminohexane A-152 1,7-diaminopentane A-153 1,8-diaminooctane A-154 2- (2'-aminoethylamino) ethanol A- 155 2-[(2'-aminoethylamino) ethylamino] ethanol A-156 3,3'-diaminodipropylamine A-157 piperazine A-158 N-methylpiperazine A-159 N, N'-dimethyl Piperazine A-160 1- (2'-aminoethyl) piperazine

A-161 Hexamethylenetetramine A-162 1,4-diazabicyclo [2,2,2]
Octane A-163 Polyethyleneimine A-164 Pyridine A-165 2-Acetylpyridine A-166 3-Aminopyridine A-167 3-Bromopyridine A-168 4-Ethylpyridine A-169 3-n-Butylpyridine A-170 2-picoline A-171 nicotinic acid amide A-172 2-methoxypyridine A-173 5-aminoquinoline A-174 5,6,7,8-tetrahydroisoquinoline A-175 3-methylpyridazine A-176 2-aminopyrimidine A-177 Pyrimidine A-178 Pyrazine A-179 2-Methylpyrazine A-180 Cinnoline

A-181 quinazoline A-182 quinoxaline A-183 phthalazine A-184 phenazine A-185 9-aminoacridine A-186 H ₂ N (CH ₂ CH ₂ NH) ₂ H A-187 H ₂ N (CH _{2 CH 2 NH) 3 H A-} 188 H 2 N (CH 2 CH 2 NH) 4 H A-189 H 2 N (CH 2 CH 2 CH 2 NH) 2 H A-190 H 2 N (CH 2 CH 2 CH ₂ NH) ₃ H A-191 H ₂ N (CH ₂ CH ₂ CH ₂ NH) ₄ H A-192 (CH ₃ ) ₂ NCH ₂ CH ₂ OCH ₂ CH ₂ N
_{(CH 3) 2 A-193} (CH 3) 2 N- (CH 2 CH 2 O) 2 CH 2
_{CH 2 N (CH 3) 2} A-194 (CH 3) 2 N- (CH 2 CH 2 O) 3 CH 2
_{CH 2 N (CH 3) 2} A-195 (CH 3) 2 N- (CH 2 CH 2 O) 4 CH 2
_{CH 2 N (CH 3) 2} A-196 (CH 3) 2 NCH 2 CH 2 SCH 2 CH 2 N
_{(CH 3) 2 A-197} (CH 3) 2 N- (CH 2 CH 2 S) 2 CH 2
_{CH 2 N (CH 3) 2} A-198 (CH 3) 2 N- (CH 2 CH 2 S) 3 CH 2
_{CH 2 N (CH 3) 2} A-199 (CH 3) 2 N- (CH 2 CH 2 S) 4 CH 2
CH ₂ N (CH ₃ ) ₂

[0155]

[Chemical 59]

[0156]

[Chemical 60]

[0157]

[Chemical formula 61]

General formula (C-I) used in the present invention,
The compounds represented by (C-II), (C-III) and (C-IV) are all known compounds and can be purchased and used as reagents or industrial chemicals.

General formula (C-I) used in the present invention,
The amount of the compounds represented by (C-II), (C-III) and (C-IV) added to the developer is 0.01 g to 100 g, preferably 0.1 g to 50 g per liter of the developer. Is. The compounds used in the present invention may be used alone or in combination.

General formula (C-I) used in the present invention,
To add the compounds represented by (C-II), (C-III) and (C-IV) to the developer, water or an organic solvent miscible with water, such as methanol, ethanol,
It may be added after being dissolved in triethylene glycol, diethylene glycol or the like. These compounds can be directly added to the developer of the present invention.

The reductones used in the developer of the present invention are endiol type (Endiol), enaminol type (Enaminol), 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 (I).

[0163]

[Chemical formula 62]

R ₂₂ 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.

[0166]

[Chemical formula 63]

[0167]

[Chemical 64]

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 preferably used in an amount of 1 to 100 g per liter of the developing solution.

An aminophenol type developing agent is used in the developer of the present invention. As aminophenol-based developing agents, 4-aminophenol, 4-amino-3-methylphenol, 4- (N-methyl) aminophenol, 2,
4-diaminophenol, N- (4-hydroxyphenyl) glycine, N- (2'-hydroxyethyl) -2-
There are aminophenol, 2-hydroxymethyl-4-aminophenol, 2-hydroxymethyl-4- (N-methyl) aminophenol and hydrochlorides and sulfates of these compounds, but especially N-methyl-4-aminophenol. Sulfate (methol) is preferred. The amount of these developing agents added is 0.5 to 10 g per liter of the developing solution.

The developer of 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 addition amount of these sulfites is preferably 0.5 mol or less per liter of the developing solution.

The alkaline agent is added in order to set the pH of the developing solution to 9 or more, particularly preferably 10 to 11. As the alkali agent used for setting the pH, a usual water-soluble inorganic alkali metal salt such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate or potassium triphosphate can be used.

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, metaboric acid) 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.

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 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 "SP-Handbook of Photographic Science and Engineering (SPSEHANDBOOK OF PHOT
OGRAPHIC SCIENCE ANDENGIN
EERING) "Thomas (W. THOMAS, J
r. ), John Willie and Sons (JOHN
Published by WILEY & SONS (1973) 52
Reference can be made to page 8 and the like. 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.

[0175]

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 the addition of 3a, 7-tetrazaindene, the emulsion was divided into two and no sensitizing dye (Specific Example No .; D-18: reduction potential; -1.24 V) was added (film sample No. 1) or The sensitizing dye was used in an amount of 8,0 per mol of silver halide.
After adding 00 × 10 ^-6 mol (film sample No. 2), it was coated on a polyethylene terephthalate base on which an undercoat layer had been coated in advance 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 to obtain film sample numbers 1 and 2, respectively.

Using the LB-200 filter as a sample of the film produced as described above, the film was exposed for 5 seconds through a step wedge having a step of 0.15 with a tungsten light source of 2666K, and then developers 1 and 2 having the following compositions were used. Processed at 3 and 4, stopped, fixed, washed with water and dried.

Composition of Developer 1 Metol 2.5 g Sodium ascorbate 10.0 g (Sodium salt of reductone 1-1) Potassium bromide 1.0 g Sodium metaborate tetrahydrate 35.0 g Water was added. 1.0 l pH 10.8

Composition of Developer 2 Water 750 ml Methyl 1.0 g Anhydrous sodium sulfite 75.0 g Hydroquinone 9.0 g Sodium carbonate monohydrate 30.0 g Potassium bromide 5.0 g Add water Total volume 1000 ml pH 10.3

Composition of Developer 3 Water 500 ml Anhydrous sodium sulfite 35.0 g Paraformaldehyde 9.0 g Sodium hydrogen sulfite 2.5 g Boric acid 8.0 g Hydroquinone 25.0 g Potassium bromide 2.0 g Water Total volume 1000 ml pH 10.2

Composition of Developer 4 Hydroquinone 35.0 g Methol 0.8 g Sodium hydroxide 9.0 g Potassium triphosphate 74.0 g Potassium sulfite 90.0 g Ethylenediaminetetraacetic acid disodium salt 1.0 g potassium bromide 4.0 g 5-methylbenzotriazol 0.5 g 3-diethylamino-1,2-propane 20.0 g diol water was added to 1000 ml pH 11.6

The photographic characteristics obtained are shown in Table 1.

[0183]

[Table 1]

In Table 1, the relative sensitivity is the relative value of the reciprocal of the exposure amount at which the density of the evaluation sample excluding fog is 3.0, and the film sample No. 1 of Experiment No. 1 is developed with the developer 1 at 20 ° 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 apparent from Table 1, when a film containing a large amount of a dye having a negative reduction potential satisfying the requirements of the present invention was developed with a developer containing an aminophenol type developing agent and reductones. Results in extremely high sensitivity and high contrast. However, Akira Sasai, "Latest Photographic Prescriptive Handbook", Photo Industry Publishing Co., Ltd., 1983, Developer 2 (Kodak D-11 formulation; high contrast MQ developer) and Developer 3
(Fuji Film FD-185 formulation; squirrel-type developer) or Developer 4 (developer developer formulation for super-high contrast development using hydrazine-based compound)
Even if a large amount of a dye having a negative reduction potential is contained in the film, the contrast does not increase and the sensitivity does not significantly increase. The phenomenon of high sensitivity and high contrast due to a dye having a negative reduction potential has not been known so far.
This is a completely new fact.

Example 2 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 the 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 52.2 ° C. for 120 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
3a, 7-Tetrazaindene was added and then subdivided, and the dyes shown in Table 2 or pyridinium salt derivatives or the polyalkylene oxide derivatives shown in Table 3 and the dyes or pyridinium salt derivatives were added to each. , 100 on polyethylene terephthalate (PET) base
The coating amount was 40 mg of silver per cm ² .

[0187]

[Table 2]

[0188]

[Table 3]

Onto the above emulsion layers, a gelatin protective layer containing formalin and dimethylolurea as a hardening agent was applied and dried to obtain film sample numbers 3 to 28, respectively. These samples were exposed to a tungsten light source of 2666K through a step wedge having a step of 0.15 for 5 seconds in the same manner as in Example 1 and then exposed to 20 ° C. with the developer 1 described in Example 1. Development for 5 minutes, stopped, fixed, washed with water and dried. The obtained photographic characteristics are shown in Tables 4 and 5.

[0190]

[Table 4]

[0191]

[Table 5]

In Tables 4 and 5, the relative sensitivity is the relative value of the reciprocal of the exposure amount that gives a density of 3.0 excluding fogging,
The sensitivity of the film sample No. 3 in which nothing was added and developed with the developer 1 at 20 ° C. for 5 minutes was expressed as 100. Gamma represents the average slope of the blackened density excluding fog between 0.5 and 3.0, and fog represents the density of the unexposed area. Pepper observes the unexposed area of the film with a magnifying glass of 50 times,
Graded A, A represents the best quality (substantially no pepper) and E represents the worst quality.
A and B are suitable for practical use, C is somehow low but is within the practical allowable range, and D and E are not practical.

As is clear from Tables 4 and 5, the dyes of the present invention having a negative reduction potential, pyridinium salt derivatives,
By developing a film containing a dye and a polyalkylene oxide derivative or a pyridinium salt derivative and a polyalkylene oxide derivative with a developer containing an aminophenol-based developing agent and a reductone, the compound of the present invention is contained in the film. It can be seen that, as compared with Sample Nos. 3 and 18 which do not contain, the sensitivity and the contrast are remarkably increased. No pepper was generated in the film of the present invention.

Example 3 The film of sample No. 3 produced in Example 2 was exposed in the same manner as in Example 2, and then 1 × 10 ^{−3 of} the compound shown in Table 6 was used.
Calculated amount of M ethanol solution is 8 per mol of silver halide.
Sample No. 29 was applied by coating so that the amount becomes × 10 ^-3 mol and dried.
37 were produced. Also, a film of Sample No. 3 pre-exposed by the same operation was halogenated with a calculated amount of an ethanol solution containing a dye 3 × 10 ⁻⁴ M and polyalkylene oxide (Specific Example No. P-8) 2 g / liter. Silver 1
Samples 38 to 39 were prepared by coating so that 0.3 mmol of dye and 2 g of polyalkylene oxide per mol were coated and dried. Further, the pyridinium salt derivative 8 × 10
^-4 M and polyalkylene oxide (Specific Example No. P-8)
An ethanol solution containing 2 g / liter was applied in a calculated amount so that 0.8 mmol of a pyridinium salt derivative and 2 g of a polyalkylene oxide per mol of silver halide were coated and dried to obtain sample numbers 40 and 41. did.

[0195]

[Table 6]

The film samples shown in Table 6 were treated with the developer 1 at 20 times.
Development was carried out at 5 ° C for 5 minutes, then stopped, fixed, washed with water and dried. The photographic characteristics obtained are shown in Table 7.

[0197]

[Table 7]

In Table 7, the relative sensitivity is the relative value of the reciprocal of the exposure dose at which a density of 3.0 excluding fogging is obtained, and the sample of Sample No. 29, in which nothing is added, was developed with Developer 1 at 20 ° C. for 5 minutes. The sensitivity 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. For the pepper, the unexposed area of the film was observed with a magnifying glass of 50 times and evaluated in 5 grades, with A being the best quality (substantially no pepper was generated).
, And E represents the worst quality. A and B are suitable for practical use, C is somehow low quality but within the practical allowable range,
D and E are not practical.

As is apparent from Table 7, a film, which has a negative reduction potential, of the present invention, a dye, a pyridinium salt derivative, a dye and a polyalkylene oxide derivative or a pyridinium salt derivative and a polyalkylene oxide derivative, is applied to a pre-exposed film. After drying, when developed with a developing solution containing an aminophenol-based developing agent and a reductone, remarkable high sensitivity and high contrast occur as compared with Sample No. 29 in which the compound of the present invention is not contained in the film. You can see that As described above, it is understood that the compound having a negative reduction potential does not necessarily have to be present at the time of exposure, and may be present at the time of development processing, in order to achieve high sensitivity and high contrast by the image forming method of the present invention. No pepper was generated in the film of the present invention.

Example 4 The film of Sample No. 3 produced in Example 2 was exposed in the same manner as in Example 2, and then the developer 1 and the compound of Table 8 were added to the developer 1 to give a pH of 10.8. The developing solutions 5 to 9 adjusted to 1. were used for development at 20 ° C. for 5 minutes, and the development was stopped, fixed, washed with water and dried.

[0201]

[Table 8]

Photographic properties were evaluated in the same manner as in Example 2, and the results obtained are shown in Table 9.

[0203]

[Table 9]

In Table 9, the relative sensitivity is shown with the sensitivity in Developer 1 (Comparative Example) as 100, and other photographic characteristics are the same as in Example 2.

As is apparent from Table 9, even if the compound according to the present invention having a negative reduction potential is added to the developing solution, an image with high sensitivity and high contrast can be obtained. On the other hand, when there is no compound having a negative reduction potential (Experiment No. 9), such high sensitivity and high contrast cannot be obtained.

Example 5 A chemically ripened emulsion obtained in the same manner as in Example 1 was added with 6 × 10 ^-3 mol of 6-hydroxy-4-methyl-1,3,3a per mol of silver halide. , 7-Tetrazaindene and 0.3 mmol of the dye D-18 according to the invention.
(Reduction potential; -1.24 V) was added, and then 4 per 100 cm ² on a polyethylene terephthalate base.
The amount of silver applied was 0 mg. The emulsion layer was protected by a gelatin protective layer containing formalin and dimethylolurea as a hardener. The film samples thus produced were exposed in the same manner as in Example 2 and developers 1 and 10 each having a composition shown in Table 10 and adjusted to pH 10.8.
Development was carried out at 30 to 3 ° C. for 3 minutes at 15 to 15, stopped, fixed, washed with water and dried.

[0207]

[Table 10]

Table 11 shows the obtained photographic characteristics.

[0209]

[Table 11]

The relative sensitivity in Table 11 is shown by setting the sensitivity in Experiment No. 15 (invention) as 100. The other photographic characteristics are the same as those in the second embodiment.

As is apparent from Table 11, when the development treatment is carried out in the presence of polyalkylene oxide according to the image forming method of the present invention, a high-sensitivity and good-contrast image can be obtained.

Example 6 A chemically ripened emulsion obtained in the same manner as in Example 1 was added with 6 × 10 ⁻³ mol of 6-hydroxy-4-methyl-1,3,3a, per mol of silver halide. After adding 7-tetrazaindene, the mixture was subdivided, and the polyalkylene oxide derivative shown in Table 12 was added to each of them, and 40 mg per 100 cm ² was added onto a polyethylene terephthalate base.
It was applied so that the amount of silver would be.

[0213]

[Table 12]

This emulsion layer was protected by a gelatin protective layer containing formalin and dimethylolurea as a hardener. The film sample thus produced was exposed in the same manner as in Example 2, and as shown in Table 13, the developer 1 of Example 1 and the dye having a negative reduction potential (D-9; Reduction potential-1.29 volts) or pyridinium salt derivative (N-63; reduction potential-1.08 volts)
Was developed for 3 minutes at 30.degree. C., and stopped, fixed, washed with water and dried.

[0215]

[Table 13]

Table 14 shows the obtained photographic properties.

[0217]

[Table 14]

In Table 14, the relative sensitivity is shown with 100 being the sensitivity when the sample No. 42 was developed with the developing solution 1 of Experiment No. 21 (comparative example). Other photographic characteristics are the same as in Example 2.

As is apparent from Table 14, even when the polyalkylene oxide is present in the film and the compound having a negative reduction potential of the present invention is present in the developing solution, high sensitivity and high contrast may occur. I understand. On the other hand, in the case of the comparative example which does not satisfy the requirements of the present invention, only a soft image is obtained.

Example 7 A chemically ripened emulsion obtained in the same manner as in Example 2 was added with 8 × 10 ^-3 mol of 6-hydroxy-4-methyl-1,3,3a, per mol of silver halide. After adding 7-tetrazaindene and 8 × 10 ⁻³ mol of a pyridinium salt derivative (Specific Example No. N-4; reduction potential −1.08 V), 100 parts of polyethylene terephthalate base were added.
The coating amount was 40 mg of silver per cm ² . The emulsion layer was protected by a gelatin protective layer containing formalin and dimethylolurea as a hardener. The film sample thus produced was exposed in the same manner as in Example 2 to give a developer 18 having the following composition and this developer 18
The general formulas C-I, C-II, C-III shown in Table 15 in
Alternatively, the developer 19 to 30 containing the compound of C-IV is added.
Was used for development at 30 ° C.

Composition of Developer 18 Methyl 2.5 g Sodium ascorbate 10.0 g (Sodium salt of reductone I-1) Potassium bromide 1.0 g Sodium metaborate tetrahydrate 70.0 g 5 -Methylbenzotriazole 4.5 mg Water was added to 1.0 l pH 10.8

[0222]

[Table 15]

After the development, the evaluation sample was obtained by stopping, fixing, washing with water and drying, and the photographic characteristics were measured.

Table 16 shows the photographic properties obtained. Table 16
The development time in (1) is the development time required from the start of development until the blackened density excluding fogging reaches 3.0, in units of 15 seconds. The relative sensitivity, fog, gamma, and pepper were the values when the blackened density excluding fog in the evaluation sample was 3.0. The relative sensitivity is the relative value of the reciprocal of the exposure amount at which a density of 3.0 is obtained excluding fog, and the sensitivity when developed for 3 minutes with a developer of Developer No. 18 which does not contain the compound of the present invention is expressed as 100. . Other photographic characteristics are the same as in Example 2.

[0225]

[Table 16]

As is clear from Table 16, high sensitivity and high contrast can be obtained with all the developing solutions, but the general formulas CI and CI are used.
Developers 19 to 30 containing I, C-III or C-IV formed a super-high contrast negative image having a density of 3.0 with a shorter development time than Developer 18 containing no compound of the present invention. I understand that Further, no pepper was generated in any case.

Example 8 A chemically ripened emulsion obtained in the same manner as in Example 2 was added to 8 × 10 ⁻³ mol of 6-hydroxy-4-methyl-1,3,3a, 7-tetrazaine per mol of silver halide. Den and 8 × 10 ⁻³ mol of a pyridinium salt derivative (Specific Example No. N-4; reduction potential −1.08 V) were added respectively, and then the amount of silver was 40 mg per 100 cm ² on the polyethylene terephthalate base. Was applied to. Onto this emulsion layer were coated various gelatin protective layers containing compounds according to the present invention having a dissociation index pKa shown in Table 17 of 11 or less and formalin and dimethylolurea as hardeners. The coating amount of the protective layer was measured by weighing before and after the coating of the protective layer, and the compound addition amount per 1 mol of the coated silver amount was calculated.

[0228]

[Table 17]

The LB-200 filter was used as a sample of the film produced as described above, and it was exposed for 5 seconds through a step wedge having a step of 0.15 with a tungsten light source of 2666K, and then used as an aminophenol type developing agent. -Example 7 containing ascorbic acid (reductone specific example number; 1-1) as a diol and a reductone
Developing solution 18 was used to stop, fix, wash with water and dry. The development processing conditions were 30 ° C., the development time was changed from 30 seconds to 5 minutes, and development was performed, and the change in photographic characteristics due to the change in development time was measured.

The photographic characteristics obtained are shown in Tables 18 and 19. In Table 18 and Table 19, the photographic performance is shown by the developing time required for each sample to obtain the maximum density of 3.0 in units of 15 seconds, and represents the photographic performance at that time. Further, the value at a developing time of 6 minutes is also shown.

In Tables 18 and 19, 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 sample of film sample No. 56 is 30 ° C.
The sensitivity at the time of development processing for 1 minute and 45 seconds was expressed as 100. Gamma represents the average slope between the blackened densities of 0.5 and 3.0 excluding fog, fog represents the density of the unexposed area, and Dmax represents the maximum density of the film excluding fog.

[0232]

[Table 18]

[0233]

[Table 19]

As is clear from Tables 18 and 19, the compounds having a negative reduction potential and the dissociation index pKa according to the present invention are shown.
Film No. 47 containing a compound of 11 or less
When Nos. 58 to 58 are developed with the developer 18, a super high contrast image with a gamma of 15 or more can be obtained in a quicker development time, and a stable and good super high contrast image can be obtained in a wider development processing time. To be As described above, it is understood that by using a film containing a compound having a negative reduction potential and a compound having a dissociation index pKa of 11 or less, image formation can be performed under more preferable practical development processing conditions.

Example 9 A chemically ripened emulsion obtained in the same manner as in Example 2 was added with 8 × 10 ^-3 mol of 6-hydroxy-4-methyl-1,3,3a, 7-tetrazaine per mol of silver halide. Den and 8 × 10 ⁻³ mol of the pyridinium salt derivative (Specific Example No. N-22; reduction potential −1.15 V) were added respectively, and the amount of silver was 40 mg per 100 cm ² on the polyethylene terephthalate base. Applied. 8 mol / mol of silver halide is formed on this emulsion layer.
3 mmol of 5-sulfosalicylic acid (pKa value; 2.
5, 12.0 (in water at 25 ° C.) and a gelatin protective layer containing formalin and dimethylolurea as a hardening agent. The coating amount of the protective layer was measured by measuring before and after the coating of the protective layer, and the amount of 5-sulfosalicylic acid to be added per mol of coated silver was calculated.

The LB-200 filter was used for the film sample manufactured as described above, and a tungsten light source of 2666K was used to pass through a step wedge with a step of 0.15.
After exposure for 2 seconds, the compound of Table 20 was added to the developer 18 of Example 7 containing methyl as an aminophenol-based developing agent and ascorbic acid (reductone specific example number: 1-1) as reductones. Liquid 32 to 3
Processed at 6, stopped, fixed, washed with water and dried. The development processing conditions were 30 ° C., the development time was changed from 30 seconds to 5 minutes, and development was performed, and the change in photographic characteristics due to the change in development time was measured.

[0237]

[Table 20]

The photographic characteristics obtained are shown in Table 21. Table 21
In the photographic performance, the development time required for each sample to obtain the maximum density of 3.0 is shown in units of 15 seconds, and represents the photographic performance at that time. The value at the development time of 5 minutes is also shown.

In Table 21, 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 when the film sample is developed with the developer 32 at 30 ° C. for 5 minutes. 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.

[0240]

[Table 21]

As is clear from Table 21, the silver halide light-sensitive material of the present invention containing a compound having a negative reduction potential and a compound having a dissociation index pKa of 11 or less was used as an aminophenol developing agent of the present invention, a reductone. According to the image forming method of the present invention, which is developed with the developer containing the amino compound and the amino compound, it is possible to form a favorable ultrahigh contrast negative image more rapidly and stably at 30 ° C. for 1 to 5 minutes. I understand.

Example 10 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 12 × 10 ⁻³ mol of 6-hydroxy-4-methyl-1,3,3a, 7-tetrazaindene and 8 × 10 ⁻³ mol per mol of silver halide.
After adding moles of the quinolinium salt compound (Specific Example No. N-28; reduction potential -0.80 V), 40 m / 100 cm ² was added onto a polyethylene terephthalate base.
It was applied so that the amount of silver was g. On this emulsion layer, a gelatin protective layer containing a compound according to the present invention having a dissociation index pKa shown in Table 22 of 11 or less and additionally containing formalin and dimethylolurea as a hardening agent was coated. To 65. The coating amount of the additive compound was measured by the same method as in Example 8.

[0243]

[Table 22]

Film samples 59 to 65 in Table 22 were exposed to light by operating in the same manner as in Example 2 and using Developers 18 and 29 of Example 7 and Developers 31 to 35 of Example 9 at 30 ° C. It was developed for 30 seconds to 5 minutes, stopped, fixed, washed with water and dried.

Table 23 shows the photographic properties obtained.

[0246]

[Table 23]

The photographic characteristics in Table 23 are the same as in Example 9, and the development time required from the start of development until the blackening density excluding fog reached 3.0 was expressed in units of 15 seconds. , The value when the development time is 5 minutes. The relative sensitivity is the relative value of the reciprocal of the exposure amount at which a density of 3.0 is obtained excluding fogging, and is the sensitivity when the sample of film No. 59 of the present invention of Experiment No. 39 is developed with the developer 29 at 30 ° C. for 2 minutes. Expressed as 100.

As is apparent from Table 23, according to the image forming method of the present invention, even in the case of silver bromide emulsion, high sensitivity and high contrast occur as in Experiment No. 36, and a good image can be obtained. . Then, in Experiment No. 37 in which an amino compound was added to the developer and Experiment No. 38 in which a compound having a dissociation index pKa of 11 or less was added to the film, a high-contrast image was formed more quickly and stably over a wide development processing time. can do. Furthermore, a film containing a compound having a negative reduction potential and a compound having a dissociation index pKa of 11 or less is exposed to light after development with a developing solution containing an aminophenol-based developing agent, a reductone compound and an amino compound in the developing solution. In Experiment Nos. 39 to 43 which were subjected to the development processing, it can be seen that the development processing can be performed more efficiently and a high contrast image can be stably formed.

Example 11 Film Sample Nos. 52 and 55 made in Example 8,
And the film sample Nos. 62 and 64 produced in Example 10 were imagewise exposed in the same manner as in Example 2 and then developed with a developer 36 having the following composition at 38 ° C. for 20, 30 and 40 seconds, and stopped. , Fixing, washing with water and drying.

Composition of Developer 36 Methyl 7.5 g Sodium ascorbate 30.0 g (Sodium salt of reductone specific example 1-1) Potassium bromide 1.0 g Sodium metaborate tetrahydrate 70.0 g 5-nitroindazol 4.5 mg pyrazine (amino compound specific example A-132) 1.0 g Water was added to 1.0 l pH 10.8

The obtained photographic performances are shown in Table 24.

[0252]

[Table 24]

In Table 24, the relative sensitivity is the relative value of the reciprocal of the exposure amount at which a density of 3.0 excluding fogging is obtained, and the sensitivity of the film No. 52 sample according to the present invention when developed at 38 ° C. for 30 seconds is 100. Expressed as Fog and gamma are the same as in Example 2. max represents the maximum density of the film excluding fog.

As is apparent from Table 24, according to the image forming method of the present invention, a stable and excellent super-high contrast negative image can be obtained in a practical development processing time of 38 seconds at a development time of 20 seconds to 40 seconds. You can see that you can get it.

[0255]

According to the present invention, by processing with a developer which does not use hydroquinone as a developing agent, it is possible to form a negative image having a gamma of more than 10 and having extremely high contrast and less generation of pepper.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (31) Priority claim number Japanese Patent Application No. 3-310755 (32) Priority date Hei 3 (1991) November 26 (33) Priority claiming country Japan (JP) (31) Priority Claim number Japanese patent application No. 4-23738 (32) Priority date No. 4 (1992) February 10 (33) Country of priority claim Japan (JP) (31) No. of priority claim Japanese patent application No. 4-30658 (32) Priority Hihei 4 (1992) February 18 (33) Priority claiming country Japan (JP) (31) Priority claim number Japanese Patent Application No. 4-133615 (32) Priority Sun Hei 4 (1992) May 26 (33) ) Priority claiming country Japan (JP) (31) Priority claiming number Japanese Patent Application No. 4-138639 (32) Priority date Hei 4 (1992) May 29 (33) Priority claiming country Japan (JP) (72) Inventor Kiyo Suematsu 4-8-17 Narimasu, Itabashi-ku, Tokyo

Claims (51)

[Claims] 1. A negative-type silver halide photographic light-sensitive material having a negative-type silver halide emulsion layer on a support and, if necessary, another hydrophilic colloid layer is exposed to an image, and then the reduction potential is negative. A method for forming a super-high contrast negative image, which comprises performing development processing with a developer containing an aminoferic developing agent and a reductone in the presence of an organic compound. 2. The method for forming an ultrahigh contrast negative image according to claim 1, wherein an organic compound having a negative reduction potential is present in the negative type silver halide emulsion layer or another hydrophilic colloid layer. 3. The method for forming an ultrahigh contrast negative image according to claim 1, wherein an organic compound having a negative reduction potential is present in the developer. 4. The method for forming a super-high contrast negative image according to claim 1, 2 or 3, wherein the reduction potential of the organic compound is less than -0.60 volt. 5. The method for forming an ultrahigh contrast negative image according to claim 1, wherein the polyalkylene oxide or its derivative is present in the negative type silver halide emulsion layer or other hydrophilic colloid layer. 6. The method for forming an ultrahigh contrast negative image according to claim 1, wherein polyalkylene oxide or a derivative thereof is present in the developer. 7. The ultrahigh contrast negative image according to claim 1, wherein the silver halide photographic light-sensitive material has an inorganic or organic compound having a dissociation index pKa of 11 or less in a negative-type silver halide emulsion layer or another hydrophilic colloid layer. Forming method. 8. The method for forming a super-high contrast negative image according to claim 1, wherein the developing solution contains an amine. 9. The method for forming a super-high contrast negative image according to claim 1, wherein the developer contains a cyclic imine. 10. The method for forming a super-high contrast negative image according to claim 1, wherein the developing solution contains a quaternary ammonium salt compound. 11. The method for forming a superhigh contrast negative image according to claim 1, 2 or 3, wherein the organic compound having a negative reduction potential is a heterocyclic compound. 12. The reduction potential of the heterocyclic compound is −0.6.
The method for forming an ultrahigh contrast negative image according to claim 11, which is less base than 0 volt. 13. The heterocyclic compound is a dye.
1. The method for forming a super-high contrast negative image described in 1. 14. The method for forming an ultrahigh contrast negative image according to claim 13, wherein the reduction potential of the dye is less than −0.60 V. 15. The method for forming an ultrahigh contrast negative image according to claim 11, wherein the heterocyclic compound is a pyridinium salt or a derivative thereof. 16. The method for forming an ultrahigh contrast negative image according to claim 15, wherein the reduction potential of the pyridinium salt or its derivative is less than −0.60 V. 17. The method for forming an ultrahigh contrast negative image according to claim 11, wherein the heterocyclic compound is a quinolinium salt or a derivative thereof. 18. The method for forming an ultrahigh contrast negative image according to claim 17, wherein the reduction potential of the quinolinium salt or its derivative is less than -0.60 V. 19. The method for forming an ultrahigh contrast negative image according to claim 11, wherein the heterocyclic compound is an isoquinolinium salt or a derivative thereof. 20. The reduction potential of the isoquinolinium salt or its derivative is less than -0.60 V.
A method for forming a super-high contrast negative image as described above. 21. A negative type silver halide photographic light-sensitive material having a negative type silver halide emulsion layer on a support and, if necessary, another hydrophilic colloid layer, the emulsion layer or another hydrophilic colloid. A negative-type silver halide photographic light-sensitive material comprising an organic compound having a negative reduction potential and a polyalkylene oxide or a derivative thereof in the same or different layers. 22. The negative type silver halide photographic light-sensitive material according to claim 21, wherein the organic compound having a negative reduction potential is a dye. 23. The negative working silver halide photographic light-sensitive material according to claim 22, wherein the reduction potential of the dye is less than -0.60. 24. The negative working silver halide photographic material according to claim 21, wherein the organic compound having a negative reduction potential is a pyridinium salt or a derivative thereof. 25. The negative type silver halide photographic light-sensitive material according to claim 24, wherein the reduction potential of the pyridinium salt or its derivative is less than −0.60. 26. The negative silver halide photographic light-sensitive material according to claim 21, wherein the organic compound having a negative reduction potential is a quinolinium salt or a derivative thereof. 27. The negative silver halide photographic light-sensitive material according to claim 26, wherein the reduction potential of the quinolinium salt or its derivative is less than -0.60. 28. The negative-working silver halide photographic material according to claim 21, wherein the organic compound having a negative reduction potential is an isoquinolinium salt or a derivative thereof. 29. The negative silver halide photographic light-sensitive material according to claim 28, wherein the reduction potential of the isoquinolinium salt or its derivative is less than −0.60. 30. A negative type silver halide photographic light-sensitive material having a negative type silver halide emulsion layer on a support and, if necessary, another hydrophilic colloid layer, the emulsion layer or another hydrophilic colloid. A negative-type silver halide photographic light-sensitive material, characterized in that the same or different layers contain an organic compound having a negative reduction potential and an inorganic or organic compound having a dissociation index pKa of 11 or less. 31. The negative working silver halide photographic material according to claim 30, wherein the organic compound having a negative reduction potential is a dye. 32. The negative working silver halide photographic light-sensitive material according to claim 31, wherein the reduction potential of the dye is less than −0.60. 33. The negative working silver halide photographic material according to claim 30, wherein the organic compound having a negative reduction potential is a pyridinium salt or a derivative thereof. 34. The negative type silver halide photographic light-sensitive material according to claim 33, wherein the reduction potential of the pyridinium salt or its derivative is less than −0.60. 35. The negative silver halide photographic light-sensitive material according to claim 30, wherein the organic compound having a negative reduction potential is a quinolinium salt or a derivative thereof. 36. The negative working silver halide photographic material according to claim 35, wherein the reduction potential of the quinolinium salt or its derivative is less than -0.60. 37. The negative silver halide photographic light-sensitive material according to claim 30, wherein the organic compound having a negative reduction potential is an isoquinolinium salt or a derivative thereof. 38. The negative silver halide photographic light-sensitive material according to claim 37, wherein the reduction potential of the isoquinolinium salt or its derivative is less than -0.60. 39. A developer for a negative type silver halide photographic light-sensitive material, comprising: (1) an aminophenol-based developing agent,
A developer for a negative-type silver halide photographic light-sensitive material, comprising (2) a reductone and (3) an organic compound having a negative reduction potential. 40. The developer for negative working silver halide photographic light-sensitive materials according to claim 39, wherein the organic compound having a negative reduction potential is a dye. 41. The developer for a negative working silver halide photographic light-sensitive material according to claim 40, wherein the reduction potential of the dye is less than -0.60. 42. The developer for a negative silver halide photographic light-sensitive material according to claim 39, wherein the organic compound having a negative reduction potential is a pyridinium salt or a derivative thereof. 43. The developer for a negative silver halide photographic light-sensitive material according to claim 42, wherein the reduction potential of the pyridinium salt or its derivative is less than -0.60. 44. The negative-working silver halide photographic material developer according to claim 39, wherein the organic compound having a negative reduction potential is a quinolinium salt or a derivative thereof. 45. The negative-type silver halide photographic material developer according to claim 44, wherein the reduction potential of the quinolinium salt or its derivative is less than -0.60. 46. The negative-working silver halide photographic material developer according to claim 39, wherein the organic compound having a negative reduction potential is an isoquinolinium salt or a derivative thereof. 47. The negative-working silver halide photographic material developer according to claim 46, wherein the reduction potential of the isoquinolinium salt or its derivative is less than -0.60. 48. A developer for a negative type silver halide photographic light-sensitive material, comprising: (1) an aminophenol-based developing agent,
(2) Reductones and (3) polyalkylene oxide or its derivative are contained, The negative-type silver halide photographic light-sensitive material developing agent characterized by the above-mentioned. 49. A developer for a negative type silver halide photographic light-sensitive material, comprising: (1) an aminophenol-based developing agent,
A developer for a negative-type silver halide photographic light-sensitive material, which contains (2) a reductone and (3) an amine. 50. A negative-type silver halide photographic light-sensitive material developer, comprising: (1) an aminophenol-based developing agent,
(2) Reductones and (3) cyclic imine are contained, The negative type developer for silver halide photographic light-sensitive materials characterized by the above-mentioned. 51. A negative-type silver halide photographic light-sensitive material developer, comprising: (1) an aminophenol-based developing agent,
(2) Reductones (3) A developer for a silver halide photographic light-sensitive material, comprising a quaternary ammonium salt compound.