JPH08292526A - Method for forming ultrahigh contrast negative image, and silver halide photosensitive material and developing solution using the same - Google Patents

Abstract

PURPOSE: To obtain a good ultrahigh-contrast image to be used for a printing plate exceeding a contrast of 15 and small in occurrence of pepper and fog. CONSTITUTION: In this image forming method, the silver halide photographic sensitive material imagewise exposed in advance is subjected to development processing in the presence of a 1,2,5-thiadiazole derivative and/or a 2,1,3- benzothiadiazole derivative with an alkaline developing solution containing a reductone derivative as a main developing agent, and this invention also includes this photosensitive material and this developing solution both using the method. At that time, this 1,2,5-thiadiazole derivative and/or this 2,1,3- benzodithiadiazole derivative may be added into the photosensitive material or into the alkaline developing solution or into both of them.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a novel and useful super-high contrast image forming method. More specifically, the present invention relates to a method of forming a hard negative image, which is particularly useful in a photolithography process for printing of graphic arts, 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 of graphic arts, since it is required to form a sharp halftone dot image or a line image, an image forming system showing a photographic characteristic with high contrast (gamma of 10 or more) is required. is there.

Conventionally, a special developer called a lith developer has been used for this purpose. The lith developer contains only hydroquinone as a developing agent, and the concentration of free sulfite ion as a preservative is extremely low (usually 0.1 mol / liter or less) so as not to impair the infectious developability thereof.
Therefore, the lith developer has a drawback that it is easily oxidized by air and its activity becomes extremely unstable.

Another image forming system for obtaining high contrast photographic characteristics is US Pat. No. 4,168,977.
No. 4,224,401, No. 4,241,16
No. 4, No. 4,243,734, No. 4,269,9
No. 29, No. 4,272,614, No. 4,311,
No. 781, No. 4,323, 643, No. 4,38
No. 5,108, No. 4,650,746, No. 4,6
86,167, 4,927,734, 4,
No. 988,604, No. 4,994,365, No. 5,0
41,355, European Patent No. 253,665,
No. 322, 553, No. 333, 435, No. 3
45,025, No. 356,898, and JP-A Nos. 56-106244 and 61-267759.
61-230145, 62-270953, 62-178246, 62-180361, 6
2-275247, 63-223744, 63
-234244, 63-234245, 63-
234246, 63-253357, 63-2
65239, JP-A-2-77057, and JP-A-2-220.
042, 2-221953, 4-438, 4-5652, 4-5653, 4-6548.
No. 4, No. 6551, No. 4-9037, No. 4-15
No. 642, No. 4-16938, No. 4-19645,
4-19646, 4-19647, 4-19
No. 732, No. 4-21841, No. 4-29130,
No. 4-34430, No. 4-34545, No. 4-51
No. 142, No. 4-51143, No. 4-56842,
No. 4-56843, No. 4-56846, No. 4-56
No. 949, No. 4-60545, No. 4-62544,
4-67140, 4-67141, 4-70
No. 647, No. 4-76530, No. 4-76531,
No. 4-76532, No. 4-76533, No. 4-76
No. 534, No. 4-77732, No. 4-80741,
4-80748, 4-81841, 4-84
No. 134, No. 4-96053, No. 4-98239,
No. 4-98240, No. 4-106542, No. 4-1
14145, 4-114150, 4-1193.
No. 49, No. 4-122926, No. 4-133051.
No. 4, No. 4-136838, No. 4-13693839, No. 4-136840, No. 4-136841, and No. 4-1.
36843, 4-1161948, 4-1634.
No. 46, No. 4-163543, No. 4-166835,
4-174424, 4-178644, 4-
186343, 4-190227, 4-194
No. 923, No. 4-194928, No. 4-212144.
No. 4, No. 4-212950, No. 4-212952, No. 4-216544, No. 4-218039, No. 4-2.
No. 25346, No. 4-225347, No. 4-2253.
No. 48, No. 4-225349, No. 4-229859.
No. 4, No. 4-245243, No. 4-250444, No. 4-253051, No. 4-2589591, No. 4-2.
64440, 4-264545, 4-2659.
No. 70, No. 4-265971, No. 4-267248.
No. 4, No. 4-273241, No. 4-275541, No. 4-278939, No. 4-280245, No. 4-2.
No. 83743, No. 4-285951, No. 4-2913
No. 37, No. 4-298736, No. 4-311946
No. 4-316038, No. 4-316042, No. 4-317054, No. 4-321023, No. 4-3.
No. 30432, No. 4-331951, No. 4-3387
No. 45, No. 4-365032, No. 5-10675,
5-11384, 5-34853, 5-34
No. 854, No. 5-45761, No. 5-45762,
5-45763, 5-45764, 5-45
No. 765, No. 5-45767, No. 5-611139,
5-61140, 5-61141, 5-61
No. 142, No. 5-61143, No. 5-61144,
5-61145, 5-61146, 5-61
No. 159, No. 5-66526, No. 5-88288,
5-88290, 5-93977, 5-93
No. 990, No. 5-100371, No. 5-107667.
No. 5, No. 5-119422, No. 5-119426, No. 5-127285, No. 5-127286, and No. 5-1.
27287, 5-134337, 5-1343.
No. 38, No. 5-134339, No. 5-134357.
No. 5, No. 5-142688, No. 5-142689, No. 5-150392, No. 5-158179, and No. 5-1.
No. 65134, No. 5-173281, No. 5-1970.
No. 57, No. 5-197091, No. 5-204075.
No. 5, No. 5-204076, No. 5-216151, No. 5-216181, No. 5-216182, and No. 5-2.
No. 24330, No. 5-232616, No. 5-2412
No. 64, No. 5-249624, No. 5-257223.
No. 5, No. 5-257239, No. 5-257240, No. 5-265148, No. 5-265149, and No. 5-2.
There are methods using hydrazine compounds described in the specifications such as 73681 and 5-273709.

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 treated with an alkaline developer to obtain a high gamma of more than 10. High contrast photographic characteristics can be obtained. The stability of solution activity against aerial oxidation is also improved over lith developers because it is permissible to add high concentrations of sulfite to the developers used in this new imaging system. However, there is a problem in that a large amount of hydroquinone, which is harmful and becomes an environmental pollutant, must be used in order to keep the photographic activity of the developer constant.

As described above, the conventionally used developers use a large amount of hydroquinone, which is a harmful and environmental pollutant in order to maintain the development activity of these developers, or hydroquinone by air oxidation. It is necessary to maintain the amount of hydroquinone in the developer above a certain level by replenishing the amount of hydroquinone consumed, and to develop a high contrast image forming system using a developer that consumes less hydroquinone or does not use hydroquinone as a developing agent. It is rare.

Developers that can be used in the photolithography process for printing of graphic arts and do not use hydroquinone as a main developing agent include reductones, aminophenols and the like according to JP-A-4-32838 and JP-A-4-128742. A developer containing four components of a quaternary ammonium salt compound and a specific indazole compound, a developer using an ascorbic acid-based main developing agent at pH 12.0 or higher according to JP-A-5-88306 and JP-A-5-210220, JP-A-5-273710, 5-5
3231 and 5-273708 containing a specific quaternary salt compound in a silver halide photographic light-sensitive material,
A developing method using a developing solution containing ascorbic acid as a developing agent, US Pat. Nos. 5,264,323 and 5,2,5.
No. 36,816, a developer containing a hydrazine compound in a silver halide photographic light-sensitive material and using an ascorbic acid-based developing agent, U.S. Pat. No. 5,284,733, and silver halide photographic according to JP-A-5-142687. A developer containing a quaternary ammonium salt polymer in a light-sensitive material and a reductone compound, and JP-A-6-436.
No. 026, US Pat. No. 5,372,911, and a developer containing an organic compound having a negative reduction potential in the silver halide photographic light-sensitive material and containing an aminophenol developing agent and a reductone. To be However, these developers also have problems such as unstable photographic performance due to high pH, and high fog in the case of development processing with an automatic developing machine, which is still a problem in practical use.

On the other hand, as an example in which a thiadiazole compound is used by adding it to a photographic developing solution, JP-A-57-268 discloses a method for preventing silver sludge in the developing solution.
48, 58-169147 or 62-5695
No. 9, or JP-A-4-333046.

Further, it has been added to the processing solution for color / silver halide photographic light-sensitive material, and has a form for the purpose of development processing latitude and stabilization of color balance.
No. 2-178262 or Japanese Patent Publication No. 5-38942 or Japanese Patent Publication No. 5-74809.

Further, JP-A-53-61334 used in the form of a developing agent is mentioned, and it is already known, but in any case, the thiadiazole compound used is used. Is a 1,3,4-thiadiazole compound, which has been treated up to the present, 1,2,5
-It is not possible to find an example in which a thiadiazole compound is used by adding it to a developing solution.

Further, examples in which a 1,2,5-thiadiazole compound and / or a 2,1,3-benzothiadiazole compound are added to a silver halide photographic light-sensitive material are used in German Publication No. 2, No. 031,314 discloses an example in which a 2,1,3-benzothiadiazole compound having a nitro group on a benzene ring is used as an antifoggant. In this case, gamma is at most 3 and ，
2,5-thiadiazole compounds and / or 2,
1,3-benzothiadiazole compounds have a gamma of 1
It has not been known at all that the contrast becomes higher than 0.

As described above, the photographic effect that the 1,2,5-thiadiazole compounds and / or the 2,1,3-benzothiadiazole compounds cause remarkable development acceleration and high contrast is not known so far. It was unknown at all.

[0013]

Therefore, the first object of the present invention is to provide a stable developing solution which does not use hydroquinone, which is harmful and causes environmental pollution, as a main developing agent, and which has a high gamma of more than 10 and has a good contrast. It is an object of the present invention to provide a negative image forming method capable of obtaining an excellent image. A second object of the present invention is to provide a negative working silver halide photographic material used in the above-mentioned image forming method. A third object of the present invention is to provide an alkaline developing solution containing a stable reductone as a main developing agent, which is used in the above-mentioned image forming method.

[0014]

The above object of the present invention is to provide a negative-working silver halide photographic light-sensitive material having a negative-working silver halide emulsion layer on a support and, if necessary, another hydrophilic colloid layer. Is imagewise exposed, and then developed with an alkaline developer containing reductones in the presence of a 1,2,5-thiadiazole compound and / or a 2,1,3-benzothiadiazole compound. It could be achieved by the method of forming a high tone negative image.

Although the mechanism of action of the 1,2,5-thiadiazole compounds and the 2,1,3-benzothiadiazole compounds according to the present invention is not sufficiently clear, an alkaline developing solution containing a reductone compound as a main developing agent. When it is present during the development processing of a silver halide photographic light-sensitive material, it acts as a contrast enhancer that enhances the sensitivity and gradation of the silver halide photographic light-sensitive material by performing an imagewise nucleation reaction. Presumed. In an image forming method using an alkaline developing solution containing a reductone compound as a main developing agent, such 1,2,5-
The remarkably high sensitivity and ultrahigh contrast effect of the thiadiazole compounds and the 2,1,3-benzothiadiazole compounds have not been known so far, and are completely unexpected effects.

In the presence of the 1,2,5-thiadiazole compound and / or the 2,1,3-benzothiadiazole compound according to the present invention, the development treatment with an alkaline developer is carried out in advance as 1,2,5. -After a solution containing a thiadiazole compound and / or a 2,1,3-benzothiadiazole compound is applied to a negative silver halide photographic light-sensitive material and dried, or after the negative-type silver halide photographic light-sensitive material is imagewise exposed. A method of applying the solution and drying it, or using a pre-bath of the solution before the development treatment is also possible, and these aspects are also within the scope of the present invention.

However, in general, the following (1),
The main aspects of (2) and (3) can be mentioned.

(1) After image-exposing a negative type silver halide photographic light-sensitive material, it is developed with an alkaline developer containing a 1,2,5-thiadiazole compound and / or a 2,1,3-benzothiadiazole compound and a reductone. To process.

(2) An alkaline developing solution containing reductones after image exposure of a negative working silver halide photographic material containing a 1,2,5-thiadiazole compound and / or a 2,1,3-benzothiadiazole compound. To develop.

(3) After the imagewise exposure of a negative-working silver halide photographic light-sensitive material containing a 1,2,5-thiadiazole compound and / or a 2,1,3-benzothiadiazole compound, 1,2,5- Development is performed with an alkaline developer containing a thiadiazole compound and / or a 2,1,3-benzothiadiazole compound and a reductone.

The third mode can be considered as an example of the first mode in which the specific compound is contained in the negative-working silver halide photographic light-sensitive material. Therefore, the main modes (1) and (1) of the present invention will be described below. (2) will be described.

The present invention basically has the following general formula (I), (II), (III) or (IV) as an essential component.
A 1,2,5-thiadiazole compound and / or a 2,1,3-benzothiadiazole compound represented by

[0023]

[Chemical 6]

(However, R in the formula₁ And R₂ Are the same
Hydrogen atom, halogen atom
Child, hydroxyl group, formyl group, substituted or not
A good alkyl group, optionally substituted or unsubstituted
Kenyl group, alkynyl, which may or may not be substituted
A group, an alkoxy group which may or may not be substituted,
Alkoxycarbonyl which may or may not be substituted
A group, a carbonyl group which may or may not be substituted,
A carbamoyl group, which may or may not be substituted,
Mercapto group, which may or may not be substituted,
May or may not be an amino group and may be substituted
Sulfonyl group that may or may not be substituted
Alicyclic compound groups, which may or may not be substituted
An aromatic group, which may or may not be substituted,
Represents a prime ring group, and R ₁ And R₂ Between
Form a 5-membered, 6-membered or 7-membered ring, or an aromatic ring
It may be composed of these rings and
Nitrogen atom, sulfur atom, oxygen atom, etc. in the aromatic ring
It may contain a hetero atom. )

[0025]

[Chemical 7]

(However, R ₃ , R ₄ , R ₅ and R ₆ in the formula may be the same or different, and may be a hydrogen atom, a halogen atom, a hydroxyl group, a formyl group, or not substituted. Optionally alkyl group, optionally substituted or not alkenyl group, optionally substituted or not alkynyl group, optionally substituted or unsubstituted alkoxy group, optionally substituted or not Good alkoxycarbonyl group, optionally substituted or not, carbonyl group, optionally substituted or not carbamoyl group, cyano group, optionally substituted or not mercapto group, optionally substituted A thiocarbamoyl group which may or may not be present, an amino group which may or may not be substituted, and a sulfonyl group which may or may not be substituted,
A hydrazino group which may or may not be substituted, an alicyclic compound group which may or may not be substituted, an aromatic group which may or may not be substituted, or may or may not be substituted. Represents a heterocyclic group, and R
Between each of the substituents ₃ , R ₄ , R ₅ and R _{6 is} 5
A ring such as a member ring, a 6-membered ring or a 7-membered ring, or an aromatic ring may be formed, and in this case, a nitrogen atom, a sulfur atom or an oxygen atom is contained in these rings or the aromatic ring. And the like may contain a hetero atom. )

[0027]

Embedded image

(In the formula, R ₇ , R ₈ , R ₉ , R ₁₀ , R ₁₁ and R ₁₂ may be the same or different and are each a hydrogen atom, a halogen atom, a hydroxyl group, a formyl group or a substituted group. Optionally substituted or unsubstituted alkyl group, optionally substituted or not alkenyl group, optionally substituted or not alkynyl group, optionally substituted or unsubstituted alkoxy group, optionally substituted Alkoxycarbonyl group, which may or may not be substituted, carbonyl group, which may or may not be substituted, carbamoyl group, which may or may not be substituted, cyano group, mercapto group, which may or may not be substituted, substituted A thiocarbamoyl group which may or may not be substituted, an amino group which may or may not be substituted, and a sulfonyl group which may or may not be substituted,
A hydrazine group which may or may not be substituted, an alicyclic compound group which may or may not be substituted, an aromatic group which may or may not be substituted, or may or may not be substituted. Represents a heterocyclic group, and R
_A ring such as a 5-membered ring, a 6-membered ring or a 7-membered ring between the respective substituents represented by ₇ , R ₈ and R ₉ and / or between the respective substituents represented by R ₁₀ , R ₁₁ and R ₁₂ ; An aromatic ring may be formed, and at this time, a hetero atom such as a nitrogen atom, a sulfur atom or an oxygen atom may be contained in these rings or the aromatic ring. L ₁ is a divalent linking group, and L ₁ may be further substituted with another substituent. )

[0029]

[Chemical 9]

(In the formula, R ₁₃ , R ₁₄ , R ₁₅ , R ₁₆ , R ₁₇ and R ₁₈ are the same as R ₇ , R ₈ and R in the general formula (III).
_The same substituents as ₉ , R ₁₀ , R ₁₁ and R ₁₂ are represented. R ₁₉ and R ₂₀ are the same or different from each other, a hydrogen atom, an alkyl group which may or may not be substituted, an alkenyl group which may or may not be substituted, and an alkyl group which may be substituted. Alkynyl group which may or may not be substituted, aryl group which may or may not be substituted, polyalkyleneoxy group which may or may not be substituted, acyl group which may or may not be substituted, and which may be substituted It represents a sulfonyl group which may be omitted. L ₂ is a divalent linking group, and L ₂ may be further substituted with another substituent. The present invention is characterized in that at least one or more kinds of) are present to form an image.

The 1,2,5-thiadiazole compounds and 2,1,3-benzothiadiazole compounds used in the present invention will be described in more detail.

The substituents represented by R ₁ and R ₂ of the compound represented by the general formula (I) used in the present invention are independently hydrogen atom, halogen atom (for example, fluorine atom, chlorine atom, bromine atom, iodine). Atom, etc.), hydroxyl group, carboxyl group and its salt, sulfoxyl group and its salt, alkyl group which may be substituted or not (preferably alkyl group having 1 to 10 carbon atoms, for example, methyl, ethyl,
Propyl, isopropyl, butyl, tert-butyl,
Hexyl, octyl, decyl, etc.), an alkenyl group which may or may not be substituted (preferably an alkenyl group having 2 to 10 carbon atoms, such as vinyl, allyl, butenyl, octenyl, 1-butyl-4-hexenyl),

An alkynyl group which may be substituted or not (preferably an alkynyl group having 2 to 10 carbon atoms, for example, propargyl, hexynyl, octynyl, etc.), an alkoxy group which may be substituted or not (preferably carbon) An alkoxy group of the numbers 1 to 10, such as methoxy,
Ethoxy, isopropoxy, butoxy, decyloxy,
Allyloxy, phenoxy, etc.), an alkoxycarbonyl group which may or may not be substituted (preferably an alkoxycarbonyl group having 2 to 10 carbon atoms, for example, methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, nonyloxycarbonyl, phenoxycarbonyl, 2- Hydroxyethyloxycarbonyl etc.),

Acyl group which may or may not be substituted
(Preferably an acyl group having 1 to 10 carbon atoms, for example,
Mill, acetyl, propionyl, benzoyl, cyanoca
Lubonyl, etc.), with or without substitution
A vamoyl group (eg, -CONH ₂ , -CONHCH₃ ,
-CONHC₂H_Five, -CON (CH₃)₂, -CONHC
₆H₁₃ , -CONHPh {where Ph is a phenyl group
, But so on}), replaced
Mercapto groups that may or may not be present (eg hydro
Thio, methylthio, ethylthio, butylthio, octyl
Thio, phenylthio, etc.), with or without substitution
Also an amino group (for example, -NH₂ , -NHCH₃ , -N
(CH₃)₂, -N (CH₃ ) Ph, -NHCOCH₃ ,
-NHSO ₂C_FiveH₁₁, -NHSO₂Ph, etc.),

A sulfonyl group which may or may not be substituted (eg, —SO ₂ CH ₃ , —SO ₂ CH ₂ CH ₂ CH
_{3, -SO 2 NH 2, -SO} 2 NHCH 3, -SO 2 N (C
_{H 3) 2, -SO 2 NHC} 6 H 13, etc. -SO ₂ NHPh), an optionally substituted alicyclic compound group or without also (preferably alicyclic compound group having 3 to 10 carbon atoms, e.g. Cyclopentyl, cyclohexyl, cycloheptyl,
Cyclohexenyl, menthyl, etc.),

Aromatic groups which may or may not be substituted (eg phenyl, naphthyl, pyridyl, thienyl etc.), heterocyclic groups which may be optionally substituted (eg tetrahydrofuryl, pyrrolidyl, piperidyl, morpholyl, (Such as indrill).

A ring such as a 5-membered ring, a 6-membered ring or a 7-membered ring or an aromatic ring may be formed between R ₁ and R ₂ (for example, a benzene ring). At this time, a hetero atom such as a nitrogen atom, an oxygen atom or a sulfur atom may be contained in these rings or an aromatic ring (for example, a morpholine ring, a pyridine ring, a thiadiazole ring, a quinoline ring, an isoquinoline ring, a pyrazine ring, a pyrimidine ring). Such).

The substituent which may be substituted in R ₁ and R ₂ is a halogen atom, a hydroxyl group, a carboxylic acid group or a salt thereof, a sulfonic acid group or a salt thereof, a cyano group, a nitro group, or not substituted. Optionally a lower alkyl group (preferably a lower alkyl group having 1 to 5 carbon atoms, the substituent thereof is a halogen atom, a hydroxyl group, a carboxylic acid group or a salt thereof, a sulfonic acid group or a salt thereof,
Lower alkoxy group, aromatic group, etc., lower alkoxy group which may or may not be substituted (preferably having 1 carbon atom)
5 to a lower alkoxy group, and the substituent thereof is a halogen atom, a hydroxyl group, a carboxylic acid group or a salt thereof, a sulfonic acid group or a salt thereof, a lower alkoxy group, an aromatic group, etc.), which may or may not be substituted. And an alkylthio group (preferably a lower alkylthio group having 1 to 5 carbon atoms, the substituent thereof is a halogen atom, a hydroxyl group, a carboxylic acid group or a salt thereof, a sulfonic acid group or a salt thereof, a lower alkoxy group, an aromatic group Etc.), an aromatic group which may or may not be substituted (as a substituent, a halogen atom,
Hydroxyl group, nitro group, carboxylic acid group or salt thereof, sulfonic acid group or salt thereof, cyano group, lower alkyl group, lower alkoxy group, aromatic group, acyl group, alkoxycarbonyl group, alkyl-substituted carbamoyl group, alkyl-substituted sulfonamide Group, an acyl-substituted amino group, etc.), an optionally substituted alkoxycarbonyl group (eg, methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, nonyloxycarbonyl, phenoxycarbonyl, 2-hydroxyethyloxycarbonyl, etc.), substituted A carbamoyl group which may or may not be substituted (a lower alkyl group or an aromatic group as a substituent), a sulfonyl group which may or may not be substituted (a lower alkylamino group as a substituent), or a substituted group Ami that may or may not be Group (examples of the substituent lower alkyl group, a hydroxyalkyl group, an acyl group, an alkyl sulfonyl group), and the like.

Next, the 2,1,3-benzothiadiazole compound represented by the general formula (II) used in the present invention will be explained.

In the general formula (II), R ₃ , R ₄ and R ₅
And the substituents represented by R ₆ are each independently a hydrogen atom, a halogen atom (eg, fluorine atom, chlorine atom, bromine atom, iodine atom), hydroxyl group, cyano group, carboxyl group and salts thereof, sulfoxyl group and salts thereof. An alkyl group which may or may not be substituted (preferably an alkyl group having 1 to 10 carbon atoms, for example, methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, hexyl, octyl, decyl, etc.), substituted Alkenyl group which may or may not be present (preferably having 2 carbon atoms)
To 10 alkenyl groups, such as vinyl, allyl, butenyl, octenyl, 1-butyl-4-hexenyl, etc.),

Alkynyl groups which may or may not be substituted (preferably alkynyl groups having 2 to 10 carbon atoms, such as propargyl, hexynyl, octynyl, etc.), and alkoxy groups, which may or may not be substituted (preferably carbon). An alkoxy group of the numbers 1 to 10, such as methoxy,
Ethoxy, isopropoxy, butoxy, decyloxy,
Allyloxy, phenoxy, etc.), an alkoxycarbonyl group which may or may not be substituted (preferably an alkoxycarbonyl group having 2 to 10 carbon atoms, for example, methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, nonyloxycarbonyl, phenoxycarbonyl, 2- Hydroxyethyloxycarbonyl etc.),

Acyl group which may or may not be substituted
(Preferably an acyl group having 1 to 10 carbon atoms, for example,
Mill, acetyl, propionyl, benzoyl, cyanoca
Lubonyl, etc.), with or without substitution
A vamoyl group (eg, -CONH ₂ , -CONHCH₃ ,
-CONHC₂H_Five, -CON (CH₃)₂, -CONHC
₆H₁₃ , -CONHPh, etc.), optionally substituted
Optional mercapto groups (eg hydrothio, methylthio)
O, ethylthio, butylthio, octylthio, phenyl
Thio, etc.), thiocal, which may or may not be substituted
A vamoyl group (eg, -CSNH₂ , -CSNHCH₃ ,
-CSNHC₂H_Five, -CSN (CH₃)₂, -CSNHC
₆H₁₃ , -CSNHPh, etc.), may be substituted
An optionally substituted amino group (preferably in the following general formula (VI)
An amino group represented,

[0043]

[Chemical 10]

In the general formula (VI), R ₂₁ , R
_The substituents represented by ₂₂ may be the same as or different from each other, a hydrogen atom or an alkyl group (preferably having 1 carbon atom).
To 10 alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, hexyl, nonyl, decyl, cyclopropyl, cyclohexyl, etc., alkenyl groups (preferably alkenyl groups having 2 to 10 carbon atoms such as vinyl). , Allyl, butenyl, octenyl, 1-butyl-4-hexenyl, cyclohexenyl, etc.}, an alkynyl group (preferably having 2 to 10 carbon atoms).
Alkynyl groups such as propargyl, hexynyl, octynyl, etc.}, aromatic groups {preferably having 6 to 1 carbon atoms
0 aryl group such as phenyl, tolyl, naphthyl, etc.}, polyalkyleneoxy group (preferably polyalkyleneoxy group having 3 to 15 repeating units such as polyethylene oxide, polypropylene oxide etc.), amino group (eg -NH ₂ , -NHCH _3, -N (C
_{H 3) 2, -N (CH} 3) Ph, -NHCOCH 3, -N
HSO ₂ C ₅ H ₁₁ , —NHSO ₂ Ph, etc.), an acyl group (preferably an acyl group having 1 to 10 carbon atoms, such as formyl, acetyl, propionyl, octanoyl, acryloyl, benzoyl, etc.), a sulfonyl group (eg, methanesulfonyl, Ethanesulfonyl, butanesulfonyl,
Nonanesulfonyl, benzenesulfonyl, toluenesulfonyl, etc.},

It also represents an imino group (for example, methylimino, dimethylimino, pentylimino, tolylimino, pyridylimino, etc.) which forms a double bond with the carbon atom of the substituent of the amino group, and the substituents of the amino group are bonded to each other. A 3- to 10-membered nitrogen-containing heterocycle (eg, aziridine ring, piperidine ring, morpholine ring, piperazine ring, etc.) may be formed, and these amino group substituents R ₂₁ ,
R ₂₂ may be further substituted with another substituent, and examples of the substituent which may be further substituted include a halogen atom (for example, a chlorine atom, a bromine atom, an iodine atom, etc.), a hydroxyl group,
Carboxylic acid group or salt thereof, sulfonic acid group or salt thereof, alkyl group, alkenyl group, alkynyl group, aromatic group, acyl group, alkoxycarbonyl group, amino group, heterocyclic group, nitrogen atom, sulfur atom and phosphorus atom Examples thereof include onium bases containing at least one of them (for example, pyridinium, carbamoylpyridinium, quinolinium, triphenylphosphonium, isothiourenium, etc.). ),

A sulfonyl group which may or may not be substituted (eg, —SO ₂ CH ₃ , —SO ₂ CH ₂ CH ₂ CH
_{3, -SO 2 NH 2, -SO} 2 NHCH 3, -SO 2 N (C
_{H 3) 2, -SO 2 NHC} 6 H 13, etc. -SO ₂ NHPh), an optionally substituted alicyclic compound group or without also (preferably alicyclic compound group having 3 to 10 carbon atoms, e.g. Cyclopentyl, cyclohexyl, cycloheptyl,
Cyclohexenyl, menthyl, etc.),

Aromatic groups which may or may not be substituted (eg phenyl, naphthyl, pyridyl, thienyl etc.), heterocyclic groups which may or may not be substituted (eg tetrahydrofuryl, pyrrolidyl, piperidyl, morpholyl, (Such as indrill).

A ring such as a 5-membered ring, a 6-membered ring or a 7-membered ring or an aromatic ring may be formed with R ₃ , R ₄ , R ₅ and R ₆ (for example, a benzene ring). At this time, a hetero atom such as a nitrogen atom, an oxygen atom or a sulfur atom may be contained in these rings or an aromatic ring (for example, a morpholine ring, a pyridine ring, a thiadiazole ring, a quinoline ring, an isoquinoline ring, a pyrazine ring, a pyrimidine ring). Such).

Here, the substituent which may be substituted in R ₃ , R ₄ , R ₅ and R ₆ is a halogen atom,
Hydroxyl group, carboxylic acid group or salt thereof, sulfonic acid group or salt thereof, cyano group, nitro group, lower alkyl group which may be substituted or not (preferably having 1 to 5 carbon atoms)
A lower alkyl group of which a substituent is a halogen atom, a hydroxyl group, a carboxylic acid group or a salt thereof, a sulfonic acid group or a salt thereof, a lower alkoxy group, an aromatic group, etc.),
A lower alkoxy group which may or may not be substituted (preferably a lower alkoxy group having 1 to 5 carbon atoms, and the substituent thereof is a halogen atom, a hydroxyl group, a carboxylic acid group or a salt thereof, a sulfonic acid group or a salt thereof. , A lower alkoxy group, an aromatic group, etc., and an alkylthio group which may or may not be substituted (preferably a lower alkylthio group having 1 to 5 carbon atoms, and the substituent may be a halogen atom, a hydroxyl group or a carboxylic acid group. Or a salt thereof, a sulfonic acid group or a salt thereof, a lower alkoxy group, an aromatic group or the like), an aromatic group which may be substituted or not (a substituent is a halogen atom, a hydroxyl group, a nitro group, a carboxylic acid group or A salt thereof, a sulfonic acid group or a salt thereof, a cyano group, a lower alkyl group, a lower alkoxy group, an aromatic group, an acyl group,
An alkoxycarbonyl group, an alkyl-substituted carbamoyl group, an alkyl-substituted sulfonamide group, an acyl-substituted amino group, etc.), an optionally substituted alkoxycarbonyl group (eg, methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, nonyloxycarbonyl, phenoxy) Carbonyl, 2-hydroxyethyloxycarbonyl, etc.), a carbamoyl group which may or may not be substituted (a lower alkyl group, an aromatic group or the like as a substituent), a sulfonyl group which may or may not be substituted (substituted) As a group, a lower alkylamino group etc.),
Examples thereof include amino groups which may or may not be substituted (such as a lower alkyl group, a hydroxyalkyl group, an acyl group and an alkylsulfonyl group).

It is represented by the general formula (III) used in the present invention.
R of the compound₇ , R₈ , R₉ , R_Ten, R₁₁And R₁₂so
The substituent represented is R in the above general formula (II).
₃ , R _Four , R_Five And R₆ Represents the same substituent as.

The divalent linking group represented by L ₁ in the general formula (III) is not particularly limited, but a typical example thereof is an alkylene group which may be substituted or not (preferably having a carbon number). 1 to 10 alkylene groups such as methylene, ethylene, butylene, octylene, etc.), alkenylene groups which may or may not be substituted (preferably C 3-10 alkenylene groups such as propenylene, hexenylene etc.), substituted Alkynylene group which may or may not be present (preferably having 3 to 10 carbon atoms)
Alkynylene group of, for example, propynylene, octynylene and the like), and an arylene group which may be substituted or not (preferably an arylene group having 6 to 10 carbon atoms, such as phenylene and naphthylene).

The substituent which may be substituted in L ₁ is a hydroxyl group, a halogen atom (eg chlorine, bromine, iodine etc.), an alkyl group (preferably an alkyl group having 1 to 10 carbon atoms, eg methyl, ethyl, isopropyl). , T
ert-butyl, hexyl, nonyl, cyclohexyl, etc.), carboxylic acids or salts thereof, sulfonic acids or salts thereof, and the like.

The substituents represented by R ₁₃ , R ₁₄ , R ₁₅ , R ₁₆ , R ₁₇ and R ₁₈ of the compound represented by the general formula (IV) used in the present invention have the above-mentioned general formula (II). R ₃ in
The same substituents as R ₄ , R ₅ and R ₆ are represented.

The substituents represented by R ₁₉ and R ₂₀ in the general formula (IV) are hydrogen atoms which may be the same or different, alkyl groups which may be substituted or not (preferably carbon atoms). Alkyl groups of the numbers 1 to 10, such as methyl, ethyl, propyl, isopropyl, butyl, te
rt-butyl, hexyl, nonyl, decyl, cyclopropyl, cyclohexyl, etc., an alkenyl group which may be substituted or not (preferably an alkenyl group having 2 to 10 carbon atoms, for example, vinyl, allyl, butenyl, octenyl, 1 -Butyl-4-hexenyl, cyclohexenyl, etc.), an alkynyl group which may or may not be substituted (preferably an alkynyl group having 1 to 10 carbon atoms, for example, propargyl, hexynyl, octynyl, etc.), which may or may not be substituted. Optionally substituted aromatic group (preferably an aromatic group having 6 to 10 carbon atoms such as phenyl, tolyl, naphthyl, etc.), an optionally substituted acyl group (preferably an acyl group having 1 to 10 carbon atoms) , For example formyl, acetyl, propionyl, octanoyl, acryloyl, benzo Le etc.), substituted or may not be good sulfonyl group (e.g. methanesulfonyl, ethanesulfonyl, butanesulfonyl, nonanesulfonyl,
Benzenesulfonyl, toluenesulfonyl, etc.).

L in the general formula (IV)₂ Two represented by
There are no particular restrictions on the valency linking group, but typical
And optionally substituted alkylene group (preferred
More preferably, it is an alkylene group having 1 to 10 carbon atoms, such as methyl.
Ren, ethylene, butylene, octylene, etc.), substituted
Alkenylene group which may or may not be present (preferably
Alkenylene groups having 3 to 10 carbon atoms, eg propenylene
, Hexenylene, etc.), with or without substitution
A good alkynylene group (preferably one having 3 to 10 carbon atoms)
A rukinylene group such as propynylene or octynylene
Etc.), arylene groups which may or may not be substituted
(Preferably an arylene group having 6 to 10 carbon atoms, for example,
Phenylene, naphthylene, etc.), may be substituted
Optional xylylene group, whether substituted or not
A good polyalkyleneoxy group (preferably a repeating unit
Is 2 to 14 polyalkyleneoxy groups, for example:
(CH₂CH₂O)_Ten-CH₂CH₂−, − {CH (C
H₃) CH₂O}₇-CH (CH₃) CH ₂ -Etc.), General
A group represented by the formula (VII) may be mentioned.

[0056]

[Chemical 11]

(In the formula, the divalent linking group represented by L ₃ is the same as the divalent linking group represented by L ₁ in the general formula (III). A ₁ and A ₂ are independent of each other. Represents a carbonyl group, an aminocarbonyl group or a sulfonyl group, m, n
Are 0 or 1 respectively, and m + n is 1 or 2. )

The substituent which may be substituted in L ₂ is the same as the substituent which may be substituted in L ₁ in the general formula (III).

Next, 1, 2, represented by the general formula (I), the general formula (II), the general formula (III) and the general formula (IV)
Specific examples of the 5-thiadiazole compounds and the 2,1,3-benzothiadiazole compounds are shown below, but the present invention is not limited thereto.

[0060]

[Chemical 12]

[0061]

[Chemical 13]

[0062]

Embedded image

[0063]

[Chemical 15]

[0064]

Embedded image

[0065]

[Chemical 17]

[0066]

Embedded image

[0067]

[Chemical 19]

[0068]

Embedded image

[0069]

[Chemical 21]

[0070]

[Chemical formula 22]

[0071]

[Chemical formula 23]

[0072]

[Chemical formula 24]

[0073]

[Chemical 25]

[0074]

[Chemical formula 26]

[0075]

[Chemical 27]

[0076]

[Chemical 28]

[0077]

[Chemical 29]

[0078]

Embedded image

[0079]

[Chemical 31]

[0080]

Embedded image

[0081]

[Chemical 33]

[0082]

Embedded image

The 1,2,5-thiadiazole compounds and 2,1,3-benzothiadiazole compounds used in the present invention can be purchased by using commercially available reagents or industrial chemicals. Furthermore, it can also be synthesized, prepared and used according to known literatures as described below.

That is, as the literature describing such a synthesis method, US Pat. Nos. 2,983,730, 3,066,147, 3,279,909 and 3,440,246 are cited. , 3,501,285, 3,577,427, 4,544,400 or 4,555,521; or Russian Patent No. 1
37, 118, 145, 243, 168, 70
No. 6, No. 168,707, No. 169,941, No. 1
72,334, 176,588, 431,16
No. 6, No. 515, 748, No. 545, 643, No. 5
95,317, 932,801 or 1,0
87,521 specification,

Alternatively, German Published Patent No. 1,925,9
No. 89, No. 2,322,880, No. 2,404,85
No. 8 or No. 3,012,837; Old East German Patent No. 134,184; British Patent No. 2,12
2,492; Dutch Patent 6,716,629; Swiss Patent 579,565 or 5.
99,207; Austrian Patent No. 505.
664; or Belgi-Patent No. 629,55.
No. 1 or No. 892,084 specification,

V. G. Pesin et al., "Zh. Obs
hch. Khim. , 27, 1570 (1957),
Ibid 32,181 (1962), ibid 33,1746 or -1752 (1963), ibid 34,1258, -12
63, -1267, -1272, -1986, -247.
5, -3753, -3757 or -3763 (19
64) etc.,

V. G. Pesin et al., "Khim. G.
etherotsikl. Soedin. , Acad. N
auk Latv. , 1965, 354, and 196.
6,382, 1967,97, -289, -666 or -1048, 1968,249, 1969,
613 or −619 or 1973, 926, etc.,

Or V.I. G. Pesin et al., "Lat
vijas PSR ZinatnuAkad. Ve
tis. Khim. Ser. , 1965, 223
Or -233, etc., and further, V. G. P
Esin et al., "Izv. Vyssh. Ucheb.
n. Zaved. , Khim. Khim. Tekhn
ol. , 20, 180 (1977), etc.,

V. G. Pesin et al., "Zh. Or.
g. Khim. , 22, 421 (1986) or K.S. S. Pharma et al., "Indian J. C."
hem. Sect. B ", 14B, 1001 (197)
6), ibid. 15B, 968 (1977). , 16B, 8
92 (1978), ibid. 17B, 13 (1979), ibid. 1
8B, 556 (1979), 20B, 744 (198)
1), 21B, 65 (1982), 25B, 271
Or, -315 (1986), etc.,

K. S. “Synth,” et al.
, 1983, 581 or I.S. A. Bel
En'kaya et al., "Khim.-Farm.Z.
h. , 12, 66 (1978), the same 13, 33 (19)
79) or 18, 467 (1984), or I.I. A. Belen'kaya et al., "Fiziol.
Akt. Veshchestva ", 18, 79 (19)
86) etc.,

W. T. Smith, Jr. Et al., “J.
Org. Chem. , 27,676 (1962);
R. S. Muravniket et al., "Tr. Leni.
ngr. Khim. -Farmatsevt, Ins
t. , 1962, 176 or -184; or J. B. Wright's "J. Org. Che
m. , 29, 1905 (1964), etc.,

P. Hope et al., “J. Chem. So.
c. C, Org. , 1966, 1283; M. W
einstock et al., "Tetrahedron L
ett. , 1966, 2163, L.I. M. Weins
Tock et al., "J. Org. Chem.", 32, 2.
823 (1967); From Beecken,
"Chem. Ber.", 100, 2164 (196).
7) etc.,

D. D. Monte et al., "Bolll. S.
ci. Fac. Chim. Ind. Bologna ",
25, 3 (1967); J. van Daalen
Et al., "Rec. Trav. Chim., Pays-B".
as ", 86, 1159 (1967); Vince
nzo et al., "Gazz. Chim. Ital.", 9
7, 1614 (1967); or B. Vincentz
o, et al., "Corsi. Semin. Chim.", 1
968, 85 etc.,

J. D. Bower et al., “J. Am. C.
hem. Soc. , 91, 6891 (1969); or K.I. Pilgram et al., “J. Heterocy.
cl. Chem. , 7,629 (1970); or D.I. E. FIG. Bulitz et al., “J. Heteroc.
ycl. Chem. , 9, 539 (1972), etc.,

F. S. Mikhailitsyn et al.
"Khim. Deterotsikl. Soedi
n. , 1973, 319; or K.I. Pilgram
Et al., "J. Heterocycl. Chem.", 1
1,777 or -835 (1974), etc.,

Furthermore, A. P. Komin et al.
“J. Heterocycl. Chem.”, 12, 8
29 (1975), K. Pilgram
Et al., "J. Agric. Food Chem.", 2
3, 392 (1975); or F.I. S. Mikha
ilitsyn et al., "Khim. Geterotsi.
kl. Soedin. , 1976, 61 etc.,

Alternatively, G. I. Eremeeva et al.
"Khim. Geterotsikl. Soedi
n. , 1976, 340; or B.I. Danilec
Et al., "J. Heterocycl. Chem.", 1
5,537 (1978), etc.

T. Uno et al., “Chem.Phar.
m. Bull. , 26, 3896 (1978);
D. Warren et al., "J. Heterocycl.
Chem. , 16, 1617 (1979); Behforouz et al., "Tetrahedro
n Lett. , 1979, 4493, etc.,

M. A. Kaldrikyan et al., “S
int. Geterotsikl. Soedin. ],
12, 7 (1981) and the like, P. S. Rao
Et al., "Indian J. Chem., Sect.
B ", 20B, 111 (1981); Th
Omas et al., "Heterocycles", 20,
1043 (1983), etc.

Furthermore, the E. A. Bezzubets
, "Khim.-Farm.Zh.", 19,134.
8 (1985), R. Neidlein
Et al., "Chem. Ber.", 120, 1593 (1
987), etc., according to various methods as described and disclosed in these documents,
Alternatively, for reference, 1,2,5-thiadiazole compounds and 2,1,3 used in the present invention
-A benzothiadiazole compound can be synthesized and prepared.

A specific method for synthesizing a representative compound of the compounds represented by formula (II), formula (III) and formula (IV) used in the present invention will be described.

Specific Example Compound II-51 can be synthesized according to the following synthetic scheme (1).

[0103]

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1.51 g (10 mmol) of 4-amino-2,1,3-benzothiadiazole ( 1 ), 1.48 g (10 mmol) of phthalic anhydride ( 2 ) and 85 ml of anhydrous acetonitrile were mixed and stirred at room temperature. The reaction was carried out for 1 day. The crystals precipitated during the reaction were separated by filtration, washed with 15 ml of acetonitrile, and dried at room temperature to obtain 1.95 g of compound II-51 (yield 65.2%). The structure of compound II-51 is NM
Confirmed by R, IR and MS.

Specific Example Compound III-3 can be synthesized according to the following synthetic scheme (2).

[0106]

Embedded image

4-Amino-7-chloro-2,1,3-benzothiadiazole ( 3 ) 1.86 g (10 mmo)
l), 0.67 g (5 mm) of terephthalaldehyde ( 4 )
ol) and 30 ml of absolute ethanol are mixed, and the external temperature is 1
The reflux reaction was carried out at 00 ° C. for 8 hours. After cooling to room temperature, the crystals precipitated during the reaction were separated by filtration, the crystals were spray washed with 10 ml of ethanol, and dried at room temperature to obtain 1.36 g of compound III-3 (yield 57.9%).
Obtained. The structure of compound III-3 was confirmed by NMR, IR, and MS.

Specific Example Compound IV-4 can be synthesized according to the following synthetic scheme (3).

[0109]

Embedded image

Polyethylene glycol (PEG # 20
0, average molecular weight 200) ( 5 ) 2.00 g (10 mmo
1), 2.72 g (27 mmol) of triethylamine and 10 ml of tetrahydrofuran are mixed, and the internal temperature is cooled to 0 ° C. A solution of 4.77 g (25 mmol) of p-toluenesulfonyl chloride ( 6 ) in 10 ml of tetrahydrofuran was added dropwise thereto at an internal temperature of 5 ° C or lower. After that, the reaction was carried out by stirring at an internal temperature of 5 ° C or lower for 1 day. After completion of the reaction, water 3
After adding 5 ml, the mixture was extracted with 30 ml of dichloromethane. The dichloromethane layer was washed with 10% hydrochloric acid and water, dried over magnesium sulfate, and then dried up to obtain 3.87 g (yield 76.1%) of compound ( 7 ). 2.54 g (5 mmol) of compound ( 7 ), 1.5 of compound ( 1 )
1 g (10 mmol), sodium carbonate 1.06 g (1
0 mmol) and 40 ml of acetonitrile are mixed,
The reaction was carried out for 10 hours while stirring at an external temperature of 90 ° C. After cooling to room temperature, remove the residue by filtration and dry up,
The residue was dissolved in dichloromethane, washed with water and concentrated. The concentrate was separated and purified by silica gel column chromatography (eluent: methanol / ethyl acetate) to obtain 0.94 g (yield 41.0%) of compound IV-4. The structure of compound IV-4 was confirmed by NMR, IR, and MS.

[0111]

BEST MODE FOR CARRYING OUT THE INVENTION Modes (1) and (2) which are preferable modes for forming a super-high contrast image according to the present invention.
Will be described.

In the aspect (1) of the present invention, an alkaline developer containing reductones containing a 1,2,5-thiadiazole compound and / or a 2,1,3-benzothiadiazole compound as an essential component is used. An image forming method for obtaining a super-high contrast image by developing a negative type silver halide photographic light-sensitive material that has been imagewise exposed in advance.

In the preferred embodiment (1) of the present invention, the 1,2,5-thiadiazole compound and / or the 2,1,3-benzothiadiazole compound, which are the essential components of the present invention, are the reductone compounds. Used by being contained in an alkaline developing solution as a main developing agent.

1,2,5-thiadiazo- used in the present invention
The content of the ruthenium compound and / or the 2,1,3-benzothiadiazole compound in the developer is appropriately in the range of 0.1 mg to 20 g per liter of the developer, and usually 10 mg to 5 g is preferably used. To be Further, the 1,2,5-thiadiazole compounds and / or 2,1,3-benzothiadiazole compounds used in the present invention can be used in combination of one or more.

1,2,5-thiadiazo- used in the present invention
In order to add the compound and / or 2,1,3-benzothiadiazole compound to the developer, it may be added directly to the developer, or water or an organic solvent miscible with water,
For example, it may be dissolved in alcohols, ketones, esters, amides and the like and added to the developer of the present invention.

Next, the alkaline developer containing the reductone as the main developing agent used in the aspect (1) of the present invention will be described.

The reductones used as the main developing agent in the alkaline developer used in the aspect (1) of the present invention include:
Endiol type (Endiol), Enaminol type (E
naminol), endiamine type (Endiamin
e), thiol enol type (Thiol-Enol) and enamine thiol type (Enamine-Thio)
l) is generally known as a compound. Examples of these compounds are described in U.S. Pat. No. 2,688,549 and JP-A-62.
-237443 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 (V).

[0119]

[Chemical 38]

(In the formula, Z is a hydrogen atom or a hydroxyl group, and d is an integer of 0 to 3.)

Next, specific examples of the reductones used in the present invention will be given, but the present invention is not limited to these specific examples.

[0122]

[Chemical Formula 39]

[0123]

[Chemical 40]

[0124]

Embedded image

The reductones used as the main developing agent in the alkaline developer used in the aspect (1) of the present invention can be used in the form of alkali metal salts such as lithium salt, sodium salt and potassium salt. The amount of these reductones added is 1 g to 200 g per liter of the developer, especially 1
It is preferably used in the range of 0 g to 100 g.

In the alkaline developer containing reductone as a main developing agent used in the aspect (1) of the present invention, dihydroxybenzenes (for example, hydroquinone, chlorohydroquinone, bromohydroquinone, and Isopropyl hydroquinone, methyl hydroquinone, 2,3-dichlorohydroquinone,
2,3-Dibromohydroquinone, 2,5-dimethylhydroquinone, potassium hydroquinone monosulfonate, sodium hydroquinone monosulfonate, catechol, pyrazole, etc.), 3-pyrazolidones (for example, 1
-Phenyl-3-pyrazolidone, 1-phenyl-4-methyl-3-pyrazolidone, 1-phenyl-5-methyl-
3-pyrazolidone, 1-phenyl-4-ethyl-3-pyrazolidone, 1-phenyl-4,4-dimethyl-3-pyrazolidone, 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone, 1-phenyl -4,4-
Dihydroxymethyl-3-pyrazolidone, 1,5-diphenyl-3-pyrazolidone, 1-p-tolyl-3-pyrazolidone, 1-phenyl-2-acetyl-4,4-dimethyl-3-pyrazolidone, 1-p-hydroxy Phenyl-4,4-dimethyl-3-pyrazolidone, 1- (2-benzothiazolyl) -3-pyrazolidone, 3-acetoxy-1-phenyl-3-pyrazolidone, etc., 3-aminopyrazolines (for example, 1- (p -Hydroxyphenyl)-
3-aminopyrazoline, 1- (p-methylaminophenyl) -3-aminopyrazoline, 1- (p-amino-m-
Methylphenyl) -3-aminopyrazoline and the like), phenylenediamines (for example, 4-amino-N, N-diethylaniline, 3-methyl-4-amino-N, N-diethylaniline, 4-amino-N-ethyl). -N-β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-β-hydroxyethylaniline, 3-methyl-
4-amino-N-ethyl-N-β-methanesulfonamidoethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methoxyethylaniline and the like) and aminophenols (for example, p-aminophenol, 3-methyl-p-aminophenol, N-methyl-p-aminophenol, 2,4-diaminophenol, N- (4-hydroxyphenyl) glycine, N- (β-hydroxyethyl) -2-aminophenol, 2 -Hydroxymethyl-p-aminophenol, 2-hydroxymethyl-N-
Methyl-p-aminophenol etc.) and the like, and hydrochlorides and sulfates of these compounds can be added and used.
Two or more kinds of these auxiliary developers may be mixed and used.

The amount of these auxiliary developers added is the same as that of the developer 1.
0.2 to 20 g per liter, preferably 0. 5g
To 10 g.

The antifoggant used in the alkaline developer used in the aspect (1) of the present invention is as follows: Akira Sasai, "The Chemistry of Photography", p. 168, Photo Industry Publishing Co., Ltd., 1982, The Photographic Society of Japan. Basics, Silver Salt Photography ”326
Page, Corona, 1979, T.S. H. JAMES "TH
E THEORY OF THE PHOTOGR
APHIC PROCESS "4TH Ed. , Pag
e 396, Macmillan Pub. Co. , I
nc. Inorganic fog inhibitors described in 1979 (for example, sodium bromide, potassium bromide, potassium iodide, etc.) and organic fog inhibitors (for example, 1-phenyl-5-mercaptotetrazole, 5-nitroindazole, 6- Any known development inhibitor such as nitroindazole, benzotriazole, benzimidazole, 2-mercaptobenzimidazole, 5-methylbenzotriazole) can be used as the antifoggant of the present invention.

To add the antifoggant used in the alkaline developer of the present invention to the developer, the antifoggant may be added directly to the developer, or water or an organic solvent miscible with water, for example, It may be dissolved in alcohols, ketones, esters, amides and the like and added to the alkaline developer of the present invention. The amount of the antifoggant used in the present invention added to the developer is from 1 mg to 10 per liter of the developer.
It is up to g, preferably 0.1 to 5 g.

The borate compound used in the alkaline developer used in the aspect (1) of the present invention is orthoboric acid, boric trioxide, potassium tetraborate, sodium tetraborate, ammonium metaborate, potassium metaborate, metaborate. At least one selected from sodium acid, borax, and hydrates of these compounds is used. To add the borate compound used in the alkaline developer of the present invention to the developer, the borate compound may be added directly to the developer, or may be dissolved in water in advance and then added to the developer. May be. The amount of the borate compound used in the alkaline developing solution of the present invention added to the developing solution is 1 g to 250 g, preferably 15 g to 100 g per liter of the developing solution.
g.

1, 2, used in the aspect (1) of the present invention
5-thiadiazole compounds and / or 2,1,3
The alkaline developer containing a benzothiadiazole compound and a reductone as a main developing agent preferably contains a preservative in addition to the above essential components. Sulfite can be used as a preservative. Examples of sulfites include sodium sulfite, potassium sulfite, lithium sulfite, ammonium sulfite, sodium bisulfite, potassium bisulfite, and potassium metabisulfite. The addition amount of these sulfites is preferably 0.5 mol or less per liter of the developing solution.

The alkaline agent used in the alkaline developer used in the aspect (1) of the present invention includes a usual water-soluble inorganic alkali metal salt (eg, lithium hydroxide, sodium hydroxide, potassium hydroxide, sodium carbonate, bicarbonate). Sodium, potassium carbonate, potassium bicarbonate, potassium triphosphate, etc.) and organic amine compounds (eg, butylamine, diethylamine, triethylamine, ethanolamine, dimethylethanolamine, triethanolamine, ethylenediamine, pyridine, etc.) can be used.

The alkaline developer used in the aspect (1) of the present invention contains at least one of an amine compound, a hydrazine compound and a quaternary onium salt compound for the purpose of increasing sensitivity, increasing contrast or promoting development. You can As a specific example, JP-A-53-77616
No. 53-137133, No. 54-37732,
60-14959, 60-140340, JP-A-2-8833, 2-170155, 4-43.
No. 8, No. 4-5652, No. 4-5653, No. 4-6
No. 548, No. 4-114150, No. 4-212144.
No. 4-122926, No. 5-93977, U.S. Pat. No. 4,975,354, European Patent Publication 518,
Amine compounds described in 352A1 and the like, JP-A-4-51143, JP-A-5-127286 and JP-A-5-13
No. 4337, No. 5-134357, No. 5-19705.
7, amine compounds, hydrazine compounds, quaternary onium salt compounds, and the like, which are described in No. 7, No. 5-232616, and the like.

The alkaline developer used in the aspect (1) of the present invention contains, in addition to the above-mentioned components, a water-soluble acid (eg acetic acid, boric acid etc.) and a pH buffering agent (eg tertiary phosphoric acid) as necessary. Sodium, sodium carbonate, potassium carbonate, sodium metaborate, lithium tetraborate, etc.), organic solvents (eg ethylene glycol, diethylene glycol, methyl cellosolve, etc.), toning agents, surfactants, defoaming agents, water softeners, etc. It can be used within a range in which the effects of the present invention are not impaired.

The present invention is not limited to the following examples, but at least 1 is preferable as an example of the preferable alkaline developer of the aspect (1) for forming a super-high contrast image according to the present invention.
One or more 1,2,5-thiadiazole compounds and /
Alternatively, an alkaline developer composed of a 2,1,3-benzothiadiazole compound, a main developing agent represented by the general formula (V), an aminophenol compound as an auxiliary developing agent, an antifoggant, a borate compound and an alkaline agent. A liquid can be mentioned.

Next, the silver halide photographic light-sensitive material used in the preferred embodiment (1) of the present invention will be described. The silver halide photographic light-sensitive material used in the aspect (1) of the present invention has at least one emulsion layer composed of a 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 micron (μm) or less, and particularly preferably 0.4 μm or less. The silver halide grains may have a regular crystal form such as a cube or an octahedron, or may have an irregular crystal form such as a sphere, a plate or a clam.

The silver halide crystal used in the present invention is
The inside and the surface layer may be formed of uniform layers or different layers.

The silver halide grains used in the present invention are
It can be prepared using any known method. That is, any of an acidic method, a neutral method, an ammonia method and the like may be used, and as a reaction mode of a soluble silver salt and a soluble halogen salt, any one of a forward mixing method, a back mixing method, a simultaneous mixing method, a combination thereof and the like is used. May be. As one of the simultaneous mixing methods, a method of keeping the silver ion concentration (pAg) in the liquid phase where silver halide is produced constant, that is, a pAg controlled double jet method (CDJ method) is used. When used, monodispersed silver halide grains having a uniform crystal form and a substantially uniform grain size can be obtained. Further, grains can be formed by using a silver halide solvent such as ammonia, thioether, or tetra-substituted thiourea.

The control double jet method and the grain forming method using a silver halide solvent make it easy to form a silver halide emulsion having a regular crystal form and a narrow grain size distribution. It is an effective means to make.

The silver halide emulsion used in the present invention includes a cadmium salt, an iridium salt, a rhodium salt, a rhenium salt or a ruthenium salt in order to increase the contrast of the silver halide emulsion in the process of silver halide grain formation or physical ripening. And these complex salts and the like may coexist.

Emulsions usually remove soluble salts after the formation of precipitates or after physical ripening.
The noodle washing method performed by gelatinizing gelatin may be used, and inorganic salts composed of polyvalent anions (eg sodium sulfate, magnesium sulfate, etc.), anionic surfactants, anionic polymers (eg polystyrene sulfonic acid, β -Naphthalenesulfonic acid formalin condensate, aromatic sulfonic acid formalin condensate, etc.) or a gelatin derivative (eg, aliphatic acylated gelatin, aromatic acylated gelatin, aromatic carbamoylated gelatin, etc.) for precipitation (flocculation) ) May be used.

The silver halide emulsion used in the present invention is
It may or may not be chemically sensitized. As the chemical sensitization method, known methods such as a sulfur sensitization method, a reduction sensitization method, a noble metal sensitization method, a selenium sensitization method and a tellurium sensitization method can be used, and they can be used alone or in combination. To be

As the sulfur sensitizer, various sulfur compounds such as thiosulfates, thioureas, thiazoles, rhodanins and the like can be used in addition to the sulfur compounds contained in gelatin. Specific examples are US Pat. No. 1,574,
No. 944, No. 2,278,947, No. 2,41
0,689, 2,728,668, 3,5
No. 01,313 and No. 3,656,955.

As the reduction sensitizers, stannous salts, amines, formamidinesulfinic acid, silane compounds and the like can be used. Specific examples thereof include US Pat.
No. 487,850, No. 2,518,698, No. 2,983,609, No. 2,983,610, No. 2,694,637 and the like.

Among the noble metal sensitization methods, the gold sensitization method is a typical one and uses a gold compound, mainly a gold complex salt. A noble metal other than gold, for example, a complex salt of platinum, palladium, iridium or the like may be contained. Specific examples are U.S. Pat. No. 2,448,060 and British Patent 618,061.
No. etc.

In the selenium sensitization method, an inorganic selenium compound or an organic selenium compound can be used as a selenium sensitizer, and specific examples thereof are US Pat. No. 1,574,94.
No. 4, No. 1,602,592, No. 1,623,4
No. 99, No. 3,297,446, No. 3,297,
No. 447, No. 3,320,069, No. 3,40
No. 8,196, No. 3,408,197, No. 3,4
42,653, 3,420,670, 3,
591, 385, Japanese Patent Publication No. 52-34491, 52
-34492, 53-295, and 57-2209.
No. 0, JP-A-59-180536 and JP-A-59-1853.
30, No. 59-181337, No. 59-18733.
No. 8, No. 59-192241, No. 60-150046.
No. 60-151637 and No. 61-246738.
And JP-A-5-11385.

Regarding the tellurium sensitizing method and tellurium sensitizer, US Pat. Nos. 1,623,499 and 3,32 are cited.
No. 0,069, No. 3,772,031, No. 3,5
No. 31,289, No. 3,655,394, British Patent No. 235,211, No. 1,121,496, No. 1,295,462, Canadian Patent No. 800,958.
No. 5,11,386, No. 5-11387, No. 5-11388, No. 5-11390, No. 5-113.
No. 92, No. 5-11393, No. 5-19395, No. 5-45768, No. 5-45769, No. 5-457.
No. 72 and the like.

The silver halide emulsion used in the present invention is
It may be spectrally sensitized with a sensitizing dye in order to impart photosensitivity to a desired photosensitive wavelength range. The dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, oxonol dyes, styryl dyes and hemioxonol dyes. Particularly useful dyes are those belonging to the cyanine dyes, merocyanine dyes and complex merocyanine dyes. Any of the nuclei normally used for cyanine dyes as the basic heterocyclic nuclei of dyes can be applied. That is, pyrroline nucleus, oxazole nucleus, oxazoline nucleus, thiazole nucleus, thiazoline nucleus, pyrrole nucleus, selenazole nucleus, imidazole nucleus, tetrazole nucleus, pyridine nucleus, indole nucleus, benzoxazole nucleus, benzothiazole nucleus, benzoselenazole nucleus, benzimidazole nucleus. A nucleus, a quinoline nucleus, etc. can be applied.

These sensitizing dyes may be used alone, or may be used in combination for the purpose of providing spectral sensitivity according to the purpose or for the purpose of supersensitization. Supersensitization can also be performed by adding a dye that does not have a spectral sensitizing effect itself or a substance that does not substantially absorb visible light together with the sensitizing dye. Here, the sensitizing dye may be added at any stage of coating the silver halide emulsion.
For example, it is added during the formation of silver halide crystals, during physical ripening, during chemical ripening, and in the emulsion coating solution prepared for coating. The preferred amount of the sensitizing dye used in the present invention is 1 × 10 ⁻⁶ mol to 1 × per mol of silver.
It is in the range of 10 ^-1 mol, particularly preferably in the range of 5 × 10 ^-5 mol to 1 × 10 ^-2 mol.

The binder contained in the silver halide emulsion layer used in the present invention is 250 per mol of silver halide.
It is preferable not to exceed g. 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, etc. can be used.

The silver halide emulsion used in the present invention may contain various compounds for the purpose of preventing fog during the manufacturing process of the light-sensitive material, storage or photographic processing, or stabilizing photographic performance. it can. That is, an emulsion stabilizer (eg 6-hydroxy-4-methyl-1,
Hydroxytetrazaindene compounds such as 3,3a, 7-tetrazaindene), antifoggants (for example, azoles, mercaptotriazines, thiocarbonyl compounds such as oxazolinethione, azaindenes, benzenethiosulfonic acid, benzenesulfinine) Acid, benzene sulfonic acid amide, etc.), various surfactants (eg, cationic, anionic, nonionic, amphoteric surfactants, etc.), spreading agents (saponin, etc.), gelatin plasticizers (copolymers of acrylic acid ester) Etc.), photographic characteristic improving agents (for example, amine compounds, hydrazine compounds, quaternary onium salt compounds, polyalkylene oxides, etc.) and the like.

The silver halide photographic light-sensitive material used in the present invention is formed by coating at least one hydrophilic colloid layer containing a silver halide emulsion on a support, but other non-photosensitive hydrophilic Colloidal layers, such as protective layers, intermediate layers,
An antihalation layer, a filter layer, etc. may be provided by coating.

The photographic emulsion layer or other hydrophilic colloid layer of the silver halide photographic light-sensitive material used in the present invention 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 and the like), active vinyl compounds (1,3,5-triacryloyl-hexahydro-s-triazine and the like), epoxy compounds, aziridine compounds and pyridinium salt hardeners can be used.

In the photographic emulsion layer or other hydrophilic colloid layer of the silver halide photographic light-sensitive material used in the present invention, various photographic additives, antistatic agents, coating aids, slip improvers, matting agents, photographs For the purpose of improving the dimensional stability of the light-sensitive material, a water-insoluble or sparingly soluble polymer latex (a homo- or copolymer of alkyl acrylate, alkyl methacrylate, acrylic acid, glycidyl acrylate, etc.) is used within a range not impairing the effect of the present invention. Can be used in.

Mode (1) of forming a super-high contrast image of the present invention
In the above, since the 1,2,5-thiadiazole compound and / or the 2,1,3-benzothiadiazole compound according to the present invention are contained in the developing solution, halogen for the purpose of forming a high contrast image It is not necessary to contain a specific substance for forming a high contrast image in the silver halide photographic light-sensitive material. However, even if a compound which is generally known to be added to a silver halide photographic light-sensitive material to obtain a high contrast image is contained in the silver halide photographic light-sensitive material to which the developer of the present invention is applied, it can be used. Good. When a silver halide photographic light-sensitive material containing a compound having such a contrast-increasing action is developed with the developer of the present invention, the developer of the present invention has an action of promoting a contrast-increasing reaction. Is recognized.

As the specific substance for forming the above-mentioned high contrast image, a specific hydrazine derivative (generally an acylphenylhydrazine derivative), a quaternary ammonium salt polymer, or a quaternary ammonium salt polymer described in the section "Prior Art" of the present specification or Examples thereof include organic compounds having a negative reduction potential.

Of course, according to the present invention,
2,5-thiadiazole compounds and / or 2,
By containing a 1,3-benzothiadiazole compound in a silver halide photographic light-sensitive material and performing development processing with the alkaline developer according to the present invention, a good and high contrast image can be obtained.

Further, in the photographic emulsion layer or other hydrophilic colloid layer of the silver halide photographic light-sensitive material to which the developing solution of the present invention is applied, amine compounds, hydrazine compounds and quaternary onium compounds are used as nucleation promoting compounds. At least one of the salt compounds may be contained. Specific examples thereof include JP-A Nos. 53-77616 and 53-13713.
No. 3, No. 54-37732, No. 60-14959,
No. 60-140340, JP-A No. 2-8833, and No. 4
-438, 4-5652, 4-5653, 4-6548, 4-114150, 4-212.
No. 144, No. 4-122926, etc., amine compounds described as development accelerators or accelerators for nucleating and infectious development, JP-A-2-170155, 5-93977,
Amine compounds as "inclusion boosters" described in U.S. Pat. No. 4,975,354 and the like, JP-A-2-
No. 327402, pages 117 to 118, JP-A-4-
No. 51143, No. 5-127286, No. 5-1343.
No. 37, No. 5-134357, No. 5- 197057.
Nos. 5,232,616 and the like, and examples thereof include amine compounds, hydrazine compounds, and quaternary onium salt compounds used for improving photographic performance such as light-sensitive materials with less black spots and light-sensitive materials with less fog. You can

The above-mentioned hardening compound, nucleating agent compound and nucleation promoting compound are all suitable water-soluble solvents such as alcohols (methanol, ethanol, propanol, fluorinated alcohol), ketones (acetone, methyl ethyl ketone). ), Dimethylformamide, dimethylsulfoxide, methylcellosolve, etc., and added to the silver halide photographic light-sensitive material. Further, by a well-known emulsification dispersion method, dibutyl phthalate, tricresyl phosphate, oil such as glyceryl triacetate or diethyl phthalate, and an auxiliary solvent such as ethyl acetate or cyclohexanone are dissolved and mechanically emulsified and dispersed. It is also possible to create and use things. Alternatively, the powder of the additive substance may be dispersed in water by a ball mill, a colloid mill, or ultrasonic waves according to a method known as a solid dispersion method.

The support of the silver halide photographic light-sensitive material used in the present invention includes cellulose triacetate, cellulose diacetate, nitrocellulose, polystyrene,
Known supports such as polyethylene terephthalate, paper, synthetic paper, or a composite thereof (for example, paper or film coated with polyolefin on both sides or one side), a glass plate, or the like can be used. A polyethylene terephthalate film is particularly preferably used. These supports may be subjected to corona treatment by a known method, and if necessary, may be subjected to undercoating treatment by a known method. Further, a waterproof layer containing a polyvinylidene chloride-based polymer may be provided in order to improve so-called dimensional stability, which changes in dimension due to changes in temperature and humidity.

Next, the step of developing the imagewise exposed silver halide photographic light-sensitive material with the alkaline developer of the present invention in the aspect (1) of the present invention will be described.

The silver halide photographic light-sensitive material used in the present invention is prepared by a method suitable for the purpose of use of the light-sensitive material, for example, natural light, incandescent light, laser light, electronic light using a device such as a camera, a light irradiation device, or an imagesetter. Image exposure is performed using a light source such as a line. Then, 1, 2, 5- of the present invention
Development processing is carried out with an alkaline developer containing a thiadiazole compound and / or a 2,1,3-benzothiadiazole compound and containing reductones as a main developing agent. The development processing temperature is selected in the range of 18 to 50 degrees Celsius, and more preferably in the range of 20 to 40 degrees Celsius. The processing time varies depending on the development temperature and processing conditions, but is preferably 15 seconds from 10 seconds to 10 minutes.
It is from 5 seconds to 5 seconds.

The developed silver halide photographic light-sensitive material of the present invention may be optionally treated with an acidic solution so that the development does not proceed further. It is not always used when automatically conveyed and directly fixed as in the case of using an automatic development processor. As the acidic stop solution, a dilute acetic acid solution, a solution of isomeric potassium bisulfite, or an acidic solution of chrome alum can be used, and sodium sulfate that suppresses swelling of the gelatin film can also be added. Processing condition in the stop bath is 10 degrees Celsius
It is selected from a range of several seconds to several minutes at a temperature of 50 to 50 degrees.

As the fixing solution used in the present invention, those having a generally used formulation can be used. For example,
The Photographic Society of Japan, "Basics of Photographic Engineering, Silver Salt Photography," 330
Page after (1979 Corona Publishing Co.), Akira Sasai, "The Chemistry of Photography" from page 320 onwards (1982 Kogaku Kogyo Publishing Co., Ltd.) and "SPSE Handbook of Photographic Science and Engineering" (SPSE HANDBOOK OF PHOTOG)
RAPHIC SCIENCE AND ENGINE
ERING) "Thomas (W. THOMAS, Jr.)
Edited by John Willy and Sons (JOHN WI
Reference can be made to, for example, page 528 published by LEY & SONS (1973). As the fixer main agent, in addition to thiosulfates and thiocyanates, organic sulfur compounds known to be effective as fixers can be used. Further, as fixing aids, acid agents (eg, acetic acid, citric acid, etc.), preservatives (eg, sodium sulfite, etc.), buffering agents (eg, boric acid, etc.) and hardening agents (eg, potassium alum, alum, sulfuric acid). Aluminum or the like) can be used. The fixing treatment temperature is selected in the range of 18 to 50 degrees Celsius, and more preferably in the range of 20 to 40 degrees Celsius. The processing time varies depending on the fixing temperature and the processing conditions, but is preferably from 10 seconds to 10 minutes, preferably from 15 seconds to 5 minutes.

The rinsing water used in the present invention contains antifungal agents (for example, compounds described in "Chemistry of Antibacterial and Antifungal" by Horiguchi), rinsing accelerators (for example, sulfites), chelating agents, surface active agents. An agent (for example, anionic, nonionic, cationic, amphoteric, etc.) may be contained. Washing with water is carried out in order to almost completely remove the silver salt dissolved by fixing and the dye in the film, and is preferably carried out at about 20 ° C. to 50 ° C. for 10 seconds to 5 minutes.

Drying in the super-high contrast image forming step according to aspect (1) of the present invention is preferably carried out in the range of room temperature to 80 ° C., and the drying time is appropriately changed depending on the drying conditions, but is usually about 5 seconds to half a day. .

The above developing-fixing-washing-drying process steps are conveniently carried out by using a roller-conveying type automatic developing processor capable of continuously performing the steps, and a method generally used in the art as an effective means. Is. Regarding the automatic processor, U.S. Pat. Nos. 3,025,779 and 3,5
45,971 and the like.

[Aspect (2) of the Present Invention] Next, a 1,2,5-thiadiazole compound and / or a 2,1,3-benzothiadiazole compound, which is the aspect (2) of the present invention, was contained. A method for forming a high-contrast image in which a negative type silver halide photographic light-sensitive material is imagewise exposed and then developed with an alkaline developer containing reductones will be described.

In the aspect (2) of the present invention, 1, 2 represented by the general formula (I), the general formula (II), the general formula (III) and the general formula (IV) which are essential components according to the present invention. , 5
-Thiadiazole compounds and / or 2,1,3-
At least one benzothiadiazole compound is contained in the negative-type silver halide photographic light-sensitive material, and the 1,2,5-thiadiazole compound and / or 2,1,3-benzo contained in the photographic light-sensitive material is contained. The amount of the thiadiazole compound is preferably 1 × 10 ⁻⁷ mol to 1 × 10 ⁻¹ mol per mol of silver halide contained in the photographic light-sensitive material. Especially from 5 × 10 ^-4 mol to 3 × 10
It is preferably in the range of ^-2 mol.

The method for producing a silver halide photographic light-sensitive material containing a 1,2,5-thiadiazole compound and / or a 2,1,3-benzothiadiazole compound according to the present invention is described in the above mode (1). The silver halide photographic light-sensitive material described above can be manufactured by exactly the same method. That is, crystal preparation, various chemical sensitizations, dye sensitizations, various additives (emulsion stabilizer, antifoggant, hardener, extender, polymer latex, various surfactants, nucleating agents, nucleating accelerators, (A contrast-increasing agent, etc.) and the like, except that the 1,2,5-thiadiazole compound and / or the 2,1,3-benzothiadiazole compound according to the present invention are added to the silver halide photographic light-sensitive material. Can be manufactured.

The method for adding the 1,2,5-thiadiazole compound and / or the 2,1,3-benzothiadiazole compound according to the present invention to a silver halide photographic light-sensitive material is direct silver halide photographic light-sensitive material. It may be added to the hydrophilic colloid layer in the material, or a suitable water-miscible organic solvent such as alcohols (for example, methanol, ethanol, propanol, fluorinated alcohol, etc.), ketones (for example, acetone, methyl ethyl ketone, etc.), It can be added by dissolving it in dimethylformamide, dimethylsulfoxide, methylcellosolve and the like. Further, by well-known emulsion dispersion method, dibutyl phthalate, tricresyl phosphate, oil such as glyceryl triacetate or diethyl phthalate,
It is also possible to dissolve by using an auxiliary solvent such as ethyl acetate or cyclohexanone and mechanically prepare an emulsion dispersion for addition. Alternatively, 1,2,5-thiadiazole compounds and / or
Alternatively, the powder of the 2,1,3-benzothiadiazole compound may be dispersed in water and added by a ball mill, a colloid mill, or ultrasonic waves.

To incorporate the 1,2,5-thiadiazole compound and / or the 2,1,3-benzothiadiazole compound according to the present invention into the silver halide photographic light-sensitive material of the present invention, hydrophilicity in the light-sensitive material is required. It is preferably contained in the hydrophilic colloid layer, particularly preferably in the silver halide emulsion layer and / or the hydrophilic colloid layer adjacent to the silver halide emulsion layer.

When the 1,2,5-thiadiazole compound and / or the 2,1,3-benzothiadiazole compound according to the present invention are added to the silver halide photographic light-sensitive material, the silver halide photographic light-sensitive material is produced. Any time during the process can be selected. For example, when it is added to a silver halide emulsion, it can be added at any time from the start of chemical ripening to before coating, but it is preferably added at any time from the end of chemical ripening to just before coating. .

A silver halide emulsion layer and / or a hydrophilic colloid layer containing a 1,2,5-thiadiazole compound and / or a 2,1,3-benzothiadiazole compound according to the present invention are coated on various supports. Then, by drying, the silver halide photographic light-sensitive material used in the aspect (2) according to the present invention can be prepared.

1, 2, 5- in the aspect (2) of the present invention
The reductone compound is used as a developing agent in the developer used in the development processing after the image exposure of the silver halide photographic light-sensitive material containing the thiadiazole compound and / or the 2,1,3-benzothiadiazole compound. An alkaline developer is used.

The alkaline developer containing the reductone compound used as the developing agent in the aspect (2) of the present invention is the 1,2,5-thiadiazole compound of the present invention and / or 2 described in the aspect (1). From an alkaline developer containing 1,3,3-benzothiadiazole compounds
2,5-thiadiazole compounds and / or 2,
A developer excluding the 1,3-benzothiadiazole compound is used. As a matter of course, it is possible to use the developer of aspect (1) as the developer of aspect (2).

That is, the alkaline developer containing a reductone compound as a developing agent used in the aspect (2) of the present invention contains various reductone compounds such as an enediol type reductone compound as a main developing agent and an aminophenol compound. You can use various auxiliary developers such as
Furthermore, various antifoggants, borate compounds, preservatives, alkali agents, amine compounds, hydrazine compounds, quaternary onium salt compounds, and other additives (acids, pH buffers, organic solvents, color tones, surfactants, decolorizers, decolorizers). A foaming agent, a water softener, etc.) such as the same developer as that in the mode (1) can be used. Also, the amounts of these additives used are exactly the same as those in the developing solution of the aspect (1).

Preferred examples of the alkaline developing solution containing a reductone compound as a developing agent used in the aspect (2) of the present invention include at least a main developing agent represented by the general formula (V) and aminophenol as an auxiliary developing agent. Compound,
An alkaline developer composed of an antifoggant, a borate compound and an alkaline agent can be mentioned.

In the aspect (2) of the present invention, the silver halide photographic light-sensitive material containing the 1,2,5-thiadiazole compound and / or the 2,1,3-benzothiadiazole compound of the present invention is processed. The processing step for obtaining a super-high contrast negative image can be performed under exactly the same steps and conditions as in the mode (1).

That is, after the image exposure of the silver halide photographic light-sensitive material of the present invention, the steps of developing-fixing-washing-drying can be carried out under the same processing chemicals and conditions as in the mode (1). Further, it is convenient to use a roller-conveying type automatic development processor capable of continuously performing these processing steps, and it is a method generally used in the art as an effective means.

[0183]

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 Commercially available films FA and S
FA (above Fuji Photo Film Co., Ltd.), UFZ and CG
P (above Eastman Kodak) LB-200
Using a filter, a tungsten light source of 2666K was used to expose for 5 seconds through a step wedge having a step of 0.15, and then a developer 1 (comparative example) and a developer 2 (present invention).
Development process at 35 ° C for 120 seconds, and then stop.
Fixing, washing with water and drying.

Composition of Developer 1 (Comparative Example) N-methylparaaminophenol.1 / 2-sulfate 7.5 g Ascorbic acid (reductone compound R-1) 30.0 g Potassium bromide 1.0 g Potassium metaborate・ 4/3 water salt 54.0 g Water was added to prepare 1.0 liter of 5% sulfuric acid aqueous solution to obtain pH 9.2.

Composition of Developer 2 (Invention) p-Aminophenol 7.0 g Ascorbic Acid (Reductone Compound R-1) 30.0 g Potassium Bromide 1.0 g Sodium Metaborate Tetrahydrate 70.0 g 2,1,3-benzothiadiazole 0.5 g (Specific Example Compound II-1) 5-nitroindazole 8.0 mg Water was added to 1.0 liter 5% sulfuric acid aqueous solution to prepare pH 9.2

The results of the obtained photographic characteristics are shown in Table 1.

[0188]

[Table 1]

The relative sensitivity in Table 1 is the relative value of the reciprocal of the exposure amount at which the density of 3.0 excluding fogging is obtained, and each film is subjected to development treatment with Developer 1 (Comparative Example) at 35 ° C. for 120 seconds. The sensitivity is shown as 100. Gamma represents the average gradient between blackened densities of 0.5 and 3.0 excluding fog, and fog represents the density of unexposed areas. With respect to the pepper, the unexposed portion of the film was observed with a magnifying glass of 50 times and evaluated in 5 grades. A represents the best quality (no substantial occurrence of pepper), and E represents the worst quality. A,
B is suitable for practical use, C is somehow acceptable but practically acceptable, and D and E are not practical.

As is clear from Table 1, 2,1,3-benzothiadiazole according to the present invention (specific compound; I
It can be seen that when developed using the developer 2 containing I-1), any commercially available film shows a marked increase in sensitivity and high contrast. However, the developer 1 of the comparative example
Does not show such an increase in sensitivity or an increase in contrast. No pepper was found in any of the films. As described above, by using the developing solution 2 according to the present invention, it is found that a good high contrast image with less pepper and fog can be obtained from various commercially available films.

Example 2 Commercially available film LS5500
(Fuji Photo Film Co., Ltd.), SAI and ESY (Eastman Kodak Company) sensitometer MA
Using RK-VII (manufactured by EG & G), a step wedge having a step of 0.15 was brought into close contact and exposed for 1 × 10 ⁻⁵ seconds, and then a developer 1 (comparative example) described in Example 1 and a developer 3 (having the following composition) ( 120) at 35 ° C. with the developer of the present invention)
It was developed for seconds, stopped, fixed, washed with water and dried.

Composition of Developer 3 (Invention) N-Methylparaaminophenol.1 / 2 Sulfate 7.5 g Ascorbic Acid (Reductone Compound R-1) 30.0 g Potassium Bromide 1.0 g Sodium Metaborate Tetrahydrate 70.0 g 4-amino-2,1,3-benzothiadiazole 0.5 g (Specific Example Compound II-6) 5-nitroindazole 30.0 mg Water was added to 1.0 liter 5% Prepared with sulfuric acid aqueous solution, pH 9.3

Table 2 shows the results of the photographic characteristics obtained.

[0194]

[Table 2]

The relative sensitivity in Table 2 is the reciprocal value of the reciprocal of the exposure amount to obtain a density of 3.0 excluding fogging, and the sensitivity when each film was developed with Developer 1 at 35 ° C. for 120 seconds was 100. It is shown. Gamma is the average slope between blackening density 0.5 and 3.0 excluding fog,
Fog indicates the density of the non-exposed area. With respect to the pepper, the unexposed portion of the film was observed with a magnifying glass of 50 times and evaluated in 5 grades. A represents the best quality (no substantial occurrence of pepper), and E represents the worst quality. A and B are suitable for practical use, and C is somehow acceptable but practically acceptable.
D and E are not practical.

As is clear from Table 2, 4 according to the present invention
When a developing treatment using a developing solution 3 containing -amino-2,1,3-benzothiadiazole (specific example compound; II-6) is performed, a significant increase in sensitivity and gamma are observed in any commercially available film. It can be seen that a super-high contrast of over 15 is exhibited. However, the developer 1 of the comparative example does not show such increase in sensitivity or increase in contrast. No pepper was found in any of the films. As described above, it can be seen that when the developer 3 according to the present invention is used, a good high-contrast image with less generation of pepper and fog can be obtained by using various commercially available films for laser exposure.

[Example 3] Gelatin aqueous solution kept at 40 ° C
Aqueous silver nitrate solution and 1.5 x 10 per mol of silver^-7
Bromide containing moles of sodium rhodium (III) hexachloride
Mixed aqueous solution of potassium and sodium chloride (molar ratio
Br: Cl = 30: 70) while keeping pAg 7.2
Average particle size by adding over 75 minutes at the same time
0.18 μm cubic monodisperse silver chlorobromide emulsion (AgCl
 70 mol%) was prepared. Soluble salts are prepared by the usual method.
2.5 × 10 per mol of silver halide after removal^-FiveMo
Sodium thiosulfate and 1.6 x 10^-FiveMol salt
Hydrauric acid trihydrate (HAuCl _Four ・ 3H₂ O) and add 5
Chemically aged for 100 minutes at 0.0 ° C. This emulsion has a halo
It contains 80 g of gelatin per mol of silver genide. like this
To the emulsion prepared in accordance with 1 mol of silver halide
1 × 10^-3Molar potassium iodide and 1.2 x 10^-2
Mol of 6-hydroxy-4-methyl-1,3,3a, 7
-Tetrazaindene was added. Divide this emulsion into 3
Split,

(1) No addition,

(2) The following compound 1 was added in an amount of ³ × 10 ^-3 mol per mol of silver halide,

(3) The following compound 2 was added in an amount of ³ × 10 ^-3 mol per mol of silver halide, and 100 c on each polyethylene terephthalate (PET) base.
The coating amount was 40 mg of silver per m ² . This emulsion layer was protected by a gelatin protective layer containing formalin and dimethylolurea as a hardening agent, and film number 1 (no additive), film number 2 (compound 1 added) and film number 3 (compound 2 added), respectively. And

[0201]

Embedded image

[0202]

[Chemical 43]

The film sample produced as described above was exposed for 5 seconds using a LB-200 filter with a tungsten light source of 2666K through a step wedge having a step of 0.15, and then the developer 1 of Example 1 (comparative) was compared. Example) and the developer 4 (invention), at 35 ° C.,
It was developed for 60 seconds, stopped, fixed, washed with water and dried.

Composition of Developer 4 (Invention) N-Methylparaaminophenol.1 / 2 Sulfate 7.5 g Ascorbic Acid (Reductone Compound R-1) 30.0 g Potassium Bromide 1.0 g Potassium Metaborate 4/3 hydrate 54.0 g 2,1,3-benzothiadiazole 0.5 g (Specific Example Compound; II-1) 1.0 liter prepared by adding 5% sulfuric acid aqueous solution to pH 9.2

Table 3 shows the results of the obtained photographic characteristics.

[0206]

[Table 3]

The relative sensitivity in Table 3 is the relative value of the reciprocal of the exposure amount at which a density of 3.0 excluding fogging is obtained, and the film No. 1 is subjected to development treatment at 35 ° C. for 60 seconds at a developing solution 4 (invention). The sensitivity is shown as 100. Gamma represents the average gradient between blackened densities of 0.5 and 3.0 excluding fog, and fog represents the density of unexposed areas. With respect to the pepper, the unexposed portion of the film was observed with a magnifying glass of 50 times and evaluated in 5 grades. A represents the best quality (no substantial occurrence of pepper), and E represents the worst quality. A and B are suitable for practical use, C is somehow acceptable but practically acceptable, and D and E are not practical.

As is clear from Table 3, 2,1,3-benzothiadiazole (specific example compound; I
In the case of the development processing using the developing solution 4 containing I-1), a remarkable increase in sensitivity and a gamma of 15 can be obtained even if the film does not contain a special compound that causes a high contrast like the film No. 1. The above ultra-high contrast is shown. Further, in the film containing a hydrazine type nucleating agent like the film number 3, since the pH of the comparative developer 1 is low, the hydrazine type nucleating agent does not increase the sensitivity and increase the contrast.
It can be seen that the addition of 2,1,3-benzothiadiazole according to the present invention to the developer causes a marked increase in sensitivity and super-high contrast. Furthermore, in the film such as the film No. 2 to which a quinolinium salt type nucleating agent is added, by further adding 2,1,3-benzothiadiazole to the developing solution, the sensitivity can be further increased and the contrast can be increased. I understand. No pepper was found in any of the films. As described above, it is understood that the developer 4 according to the present invention can provide a good high contrast image with less pepper and fog.

Example 4 In a gelatin aqueous solution kept at 60 ° C., an aqueous silver nitrate solution and 3.0 × 10 ⁻⁷ per mol of silver were ^prepared.
Aqueous potassium bromide solution containing 1 mol of sodium rhodium (III) hexabromide at 60 pAg at the same time.
Average particle size 0.22μ
m cubic monodisperse silver bromide emulsion was prepared. After removing the soluble salts by a conventional method, 2.5 × 10 ^-5 mol of sodium thiosulfate was added to 1 mol of silver halide,
Chemically aged at 70 ° C. for 70 minutes. This emulsion contains 80 g of gelatin per mol of silver halide. To the emulsion thus prepared, 1.2 × 10 ^-2 mol of 6-hydroxy-4-methyl-1,3,3a, 7- was added per mol of silver halide.
After adding tetrazaindene, subdivide into three,

(1) No additives,

(2) Compound 1 was added in an amount of ³ × 10 ^-3 mol per mol of silver halide,

(3) Compound 2 was added in an amount of ³ × 10 ^-3 mol per mol of silver halide, and each was coated on a polyethylene terephthalate (PET) base so that the amount of silver was 40 mg per 100 cm ² . This emulsion layer was protected by a gelatin protective layer containing formalin and dimethylolurea as a hardening agent, and film number 4 (no additive) and film number 5 (compound 1 added), respectively.
And film number 6 (compound 2 added).

Film Nos. 4 to 6 thus produced were exposed for 5 seconds using a LB-200 filter with a tungsten light source of 2666K through a step wedge having a step of 0.15, and then the developer 1 described in Example 1 was used.
(Comparative example) and a developer 5 (invention) having the following composition were developed at 35 ° C. for 120 seconds, stopped, fixed,
Washed with water and dried.

Composition of Developer 5 (Invention) N-Methylparaaminophenol 1/2 Sulfate 7.5 g Ascorbic Acid (Reductone Compound R-1) 30.0 g Potassium Bromide 1.0 g Potassium Metaborate 4/3 hydrate 54.0 g 4-amino-2,1,3-benzothiadiazole 0.5 g (Specific Example compound; II-6) 5-nitroindazole 24.0 mg Water was added 1.0 Liter pH 10.3

Table 4 shows the results of the obtained photographic characteristics.

[0216]

[Table 4]

The relative sensitivity in Table 4 is the relative value of the reciprocal of the exposure amount at which the density of 3.0 excluding fogging is obtained, and the film No. 4 is developed with the developing solution 5 (invention) at 35 ° C. for 120 seconds. The sensitivity is shown as 100. Gamma represents the average gradient between blackened densities of 0.5 and 3.0 excluding fog, and fog represents the density of unexposed areas. With respect to the pepper, the unexposed portion of the film was observed with a magnifying glass of 50 times and evaluated in 5 grades. A represents the best quality (no substantial occurrence of pepper), and E represents the worst quality. A and B are suitable for practical use, C is somehow acceptable but practically acceptable, and D and E are not practical.

As is clear from Table 4, 4 according to the present invention
When a developing treatment was carried out using a developing solution 5 containing -amino-2,1,3-benzothiadiazole (specific example compound; II-6), a marked increase in sensitivity and a gamma of 15 were obtained in any film. It can be seen that it shows a super-high contrast over. No pepper was found in any of the films. As described above, it is understood that the developer 5 according to the present invention can provide a good high contrast image with less pepper and fog.

Example 5 The sample of film No. 1 produced in Example 3 was used for 2 with an LB-200 filter.
After exposure for 5 seconds through a step wedge having a step of 0.15 with a tungsten light source of 666K, a specific example compound of the 2,1,3-benzothiadiazole compound according to the present invention is added to the developing solution 6 and the developing solution 6 having the following composition. The developed solution was developed at 35 ° C for 40 seconds, stopped, fixed,
Washed with water and dried.

Composition of Developer 6 N-Methylparaaminophenol.1 / 2 Sulfate 7.5 g Ascorbic Acid (Reductone Compound R-1) 30.0 g Potassium Bromide 1.0 g Potassium Metaborate.4 / 3 Water salt 54.0 g Water was added to 1.0 liter pH 9.8

Table 5 shows the results of the photographic characteristics obtained.

[0222]

[Table 5]

The relative sensitivity in Table 5 is the relative value of the reciprocal of the exposure amount at which the density of 3.0 excluding fogging is obtained, and the experimental number 1
The sensitivity is 100 when the film is developed with the developer 6 at 35 ° C. for 40 seconds. Gamma is the average slope between blackening density 0.5 and 3.0 excluding fog,
Fog indicates the density of the non-exposed area. With respect to the pepper, the unexposed portion of the film was observed with a magnifying glass of 50 times and evaluated in 5 grades. A represents the best quality (no substantial occurrence of pepper), and E represents the worst quality. A and B are suitable for practical use, and C is somehow acceptable but practically acceptable.
D and E are not practical.

As is clear from Table 5, when the development processing is carried out using the developer containing the specific compound of the 2,1,3-benzothiadiazole compound according to the present invention,
It can be seen that even a film containing no specific contrast enhancing compound in the film exhibits a marked increase in sensitivity and a contrast enhancement of gamma exceeding 14. No pepper was found in any of the films. As described above, it is understood that the developer 6 containing the specific compound of the 2,1,3-benzothiadiazole compound according to the present invention can provide a good high contrast image with less generation of pepper and fog.

Example 6 Six silver halide emulsions prepared in exactly the same manner as in Example 3 until 6-hydroxy-4-methyl-1,3,3a, 7-tetrazaindene was added. After adding each of the specific compounds according to the present invention and the comparative compound shown in Table 6 to the polyethylene terephthalate (PET) base previously coated with the subbing layer, the amount of silver was 40 mg per 100 cm ^2. Was applied to. This emulsion layer was protected by a gelatin protective layer containing formalin and dimethylolurea as a hardening agent to prepare films of sample numbers 7 to 12.

[0226]

[Table 6]

[0227]

[Chemical 44]

The film sample prepared as described above was exposed for 5 seconds using a LB-200 filter with a tungsten light source of 2666K through a step wedge having a step of 0.15, and then a developing solution 7 and a developing solution having the following formulations were used. 8 using each, development treatment at 35 ℃, 60 seconds,
Stopped, fixed, washed with water and dried.

Formulation of Developer 7 N-Methylparaaminophenol 1/2 Sulfate 7.5 g Sodium Ascorbate 30.0 g Potassium Bromide 1.0 g Sodium Metaborate Tetrahydrate 70.0 g Water In addition, the pH was adjusted to 9.8 by preparing 1.0 liter of 5% sulfuric acid aqueous solution.

Formulation of Developer 8 1-Phenyl-3-pyrazolidone 7.1 g Sodium ascorbate 30.0 g Potassium bromide 1.0 g Sodium metaborate tetrahydrate 70.0 g Water was added 1. PH 9.8 prepared with 0 liter 5% sulfuric acid aqueous solution

The results of the photographic characteristics obtained (1 in Table 7)
And (2 in Table 7).

[0232]

[Table 7]

[0233]

[Table 8]

The relative sensitivities in (1 in Table 7) and (2 in Table 7) are relative values of the reciprocal of the exposure amount at which a density of 3.0 excluding fog is obtained, and the film No. 9 is 35 with the developer 7.
The sensitivity when developed at 60 ° C. for 60 seconds is shown as 100. Gamma is a blackening density of 0.5 excluding fog
Fog indicates the density of the non-exposed area, with an average slope between 3.0 and 3.0. With respect to the pepper, the unexposed portion of the film was observed with a magnifying glass of 50 times and evaluated in 5 grades. A represents the best quality (no substantial occurrence of pepper), and E represents the worst quality. A and B are suitable for practical use, C is somehow acceptable but practically acceptable, and D and E are not practical.

In the case of Film No. 7 containing no 2,1,3-benzothiadiazole compound according to the present invention and Film No. 8 containing the comparative compound,
Hardening does not occur with either developer. In particular, in the case of film No. 8 to which the comparative compound was added, it was found that the relative sensitivity was remarkably lowered.

However, in the case of Film No. 9, Film No. 10, Film No. 11 and Film No. 12, which are films to which the 2,1,3-benzothiadiazole compound according to the present invention is added, Developer 7 and Developer 8 No matter which developer is used for development, both gamma and sensitivity are high.
A good image can be obtained. No pepper was found in any of the films. As described above, by developing the silver halide photographic light-sensitive material to which the specific example compound of the 2,1,3-benzothiadiazole compound according to the present invention is added with an alkaline developing solution containing a reductone compound as a developing agent, It can be seen that a good high contrast image with less occurrence of pepper and fog can be obtained.

Example 7 Samples of film No. 7, film No. 9, film No. 10, film No. 11 and film No. 12 produced in Example 6 were L
Use a B-200 filter and a tungsten light source of 2666K to pass through a step wedge with a step of 0.15.
After exposure for 2 seconds, the developer 4 described in Example 3 (invention)
At 35 ° C. for 60 seconds, development, stopping, fixing, washing with water and drying. The results of the obtained photographic properties are shown in (Table 1-1) and (Table 8-2).

[0238]

[Table 9]

[0239]

[Table 10]

The relative sensitivities in (1 in Table 8) and (2 in Table 8) are relative values of the reciprocal of the exposure amount at which a density of 3.0 excluding fogging is obtained, and the film of Experiment No. The sensitivity when developed at 35 ° C. for 60 seconds is shown as 100. Gamma represents the average gradient between blackened densities of 0.5 and 3.0 excluding fog, and fog represents the density of unexposed areas. With respect to the pepper, the unexposed portion of the film was observed with a magnifying glass of 50 times and evaluated in 5 grades. A represents the best quality (no substantial occurrence of pepper), and E represents the worst quality. A and B are suitable for practical use, C is somehow acceptable but practically acceptable, and D and E are not practical.

As is clear from (1 in Table 8) and (2 in Table 8), the developer 4 containing the 2,1,3-benzothiadiazole (specific compound; II-1) according to the present invention was added. In the case of the development processing using No. 7, even in the film No. 7 containing no specific contrast-increasing compound in the film, a gamma exceeding 20 is shown. further,
Film No. 9, Film No. 10, Film No. 11 and Film No. 12 in which the specific compound of the 2,1,3-benzothiadiazole compound according to the present invention was added to the film were replaced with 2,1,3-benzo according to the present invention. It can be seen that when the development processing is performed using the developing solution 4 to which thiadiazole (specific example compound; II-1) is added, the sensitivity is further increased. No pepper was found in any of the films.

As described above, 2,1,3-according to the present invention
Specific examples of benzothiadiazole compounds A silver halide photographic light-sensitive material to which a compound is added is prepared according to the present invention.
It can be seen that by performing development processing with a developing solution containing a specific compound of a 3-benzothiadiazole compound, a high-sensitivity, good high-contrast image with less generation of pepper and fog can be obtained.

[0243]

The effects of the present invention are 1,2,5-thiadiazo-
Of a silver halide photographic light-sensitive material which has been imagewise exposed in the presence of a ruthenium compound and / or a 2,1,3-benzothiadiazole compound, by a developing method using an alkaline developing solution in which a reductone is a main developing agent. However, a good image could be obtained with a contrast exceeding 15 and a super-high contrast with less occurrence of pepper and fog. At this time, the 1,2,5-thiadiazole compound and / or the 2,1,3-benzothiadiazole compound according to the present invention may be contained in a silver halide photographic light-sensitive material, or an alkaline developer. It may be contained in both the silver halide photographic light-sensitive material and the alkaline developer.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification number Internal reference number FI Technical display location G03C 5/305 G03C 5/305 (72) Inventor Yasuhiko Kojima 339-1 Minota, Konosu City, Saitama Horie Heights 203 (72) Inventor Yasuro Shigemitsu 1-555, Horinouchi Town, Omiya City, Saitama Prefecture Grand City N-616

Claims (13)

[Claims] 1. At least one layer of negative-working silver halide on a support in the presence of at least one or more 1,2,5-thiadiazole compounds and / or 2,1,3-benzothiadiazole compounds. A super-high-contrast negative characterized in that a negative-working silver halide photographic light-sensitive material having an emulsion layer and, if necessary, another hydrophilic colloid layer is imagewise exposed and then developed with an alkaline developer containing reductones. Image formation method. 2. The 1,2,5-thiadiazole compound according to claim 1 has the following general formula (I): (However, R ₁ and R ₂ in the formula, which may be the same or different, are a hydrogen atom, a halogen atom, a hydroxyl group,
A carboxylic acid group and a salt thereof, a sulfonic acid group and a salt thereof, an alkyl group which may or may not be substituted, an alkenyl group which may or may not be substituted, an alkynyl group which may or may not be substituted, An alkoxy group which may or may not be substituted, an alkoxycarbonyl group which may or may not be substituted, an acyl group which may or may not be substituted, a carbamoyl group which may or may not be substituted, A mercapto group that may or may not be substituted, an amino group that may or may not be substituted, and a sulfonyl group that may or may not be substituted,
Represents an alicyclic compound group which may or may not be substituted, an aromatic group which may or may not be substituted, or a heterocyclic group which may or may not be substituted, and R ₁ and A ring such as a 5-membered ring, a 6-membered ring or a 7-membered ring or an aromatic ring may be formed with R ₂ .
At this time, a hetero atom such as a nitrogen atom, a sulfur atom or an oxygen atom may be contained in these rings or the aromatic ring. The method for forming a super-high contrast negative image according to claim 1, which is a 1,2,5-thiadiazole compound represented by the formula (1). 3. The 2,1,3-benzothiadiazole compound according to claim 1 has the following general formula (II): (However, R ₃ , R ₄ , R ₅ and R ₆ in the formula, which may be the same or different, are a hydrogen atom, a halogen atom, a hydroxyl group, a cyano group, a carboxylic acid group and a salt thereof, or a sulfonic acid. Groups and salts thereof, alkyl groups which may or may not be substituted, alkenyl groups which may or may not be substituted, alkynyl groups which may or may not be substituted, and which may or may not be substituted. Alkoxy group, alkoxycarbonyl group which may be substituted or not, acyl group which may be substituted or not, carbamoyl group which may be substituted or not, mercapto which may be substituted or not Group, thiocarbamoyl group which may or may not be substituted, amino group which may or may not be substituted, sulfonyl group which may or may not be substituted, Represents an alicyclic compound group which may be substituted or not, an aromatic group which may be substituted or not, or a heterocyclic group which may be substituted or not, and R ₃ , R ₄ , R ₅ and R ₆ may form a ring such as a 5-membered ring, a 6-membered ring or a 7-membered ring, or an aromatic ring between the respective substituents. , And these rings and aromatic rings may contain a hetero atom such as a nitrogen atom, a sulfur atom or an oxygen atom.). A method for forming a super-high contrast negative image according to claim 1. 4. The 2,1,3-benzothiadiazole compound according to claim 1 has the following general formula (III): (In the formula, R ₇ , R ₈ , R ₉ , R ₁₀ , R ₁₁ and R ₁₂ may be the same or different and are a hydrogen atom, a halogen atom, a hydroxyl group, a cyano group, a carboxylic acid group and salt,
Sulfonic acid groups and salts thereof, alkyl groups which may or may not be substituted, alkenyl groups which may or may not be substituted, alkynyl groups which may or may not be substituted, and which may or may not be substituted. Good alkoxy group,
An alkoxycarbonyl group which may or may not be substituted, an acyl group which may or may not be substituted, a carbamoyl group which may or may not be substituted, a mercapto group which may or may not be substituted, a substituent A thiocarbamoyl group which may or may not be substituted, an amino group which may or may not be substituted, a sulfonyl group which may or may not be substituted, and an alicyclic compound group which may or may not be substituted. Represents an aromatic group which may or may not be substituted, or a heterocyclic group which may or may not be substituted, and between each substituent R ₇ , R ₈ and R ₉ and And / or a ring such as a 5-membered ring, a 6-membered ring or a 7-membered ring or an aromatic ring may be formed between the respective substituents of R ₁₀ , R ₁₁ and R ₁₂ , and at this time, To these rings In the aromatic ring, a nitrogen atom, it is assumed that may contain heteroatoms such as sulfur or oxygen atom. L ₁ is a divalent linking group, and L ₁ may be further substituted with another substituent. ) 2,1,
The method for forming an ultrahigh contrast negative image according to claim 1, which is a 3-benzothiadiazole compound. 5. The 2,1,3-benzothia according to claim 1.
The diazole compound has the following general formula (IV):(In the formula, R₁₃, R₁₄, R_Fifteen, R₁₆, R₁₇And R₁₈Is
R in the general formula (III)₇ , R₈ , R₉ , R_Ten, R
₁₁And R₁₂Represents the same substituent as. R₁₉And R ₂₀Is
Hydrogen atoms which may be the same or different from each other,
An alkyl group, which may or may not be substituted, is substituted
Alkenyl group, which may or may not be substituted,
Alkynyl group, which may or may not be substituted, whether or not substituted
Optionally an aryl group, which may or may not be substituted
A polyalkyleneoxy group, whether substituted or not
A good acyl group, a sulfo that may or may not be substituted
Represents a nyl group. L₂ Is a divalent linking group, L₂ Isara
May be substituted with another substituent. ) 2,1,
The compound according to claim 1, which is a 3-benzothiadiazole compound.
A method for forming a super-high contrast negative image as described above. 6. A 1,2,5-thiadiazole compound and / or a 2,1,3-benzothiadiazole compound represented by formula (I), (II), (III) or (IV) is at least The method for forming a super-high contrast negative image according to claim 1, wherein one or more kinds are present in the negative type silver halide photographic light-sensitive material. 7. A 1,2,5-thiadiazole compound and / or a 2,1,3-benzothiadiazole compound represented by formula (I), (II), (III) or (IV) is at least The method for forming an ultrahigh contrast negative image according to claim 1, wherein one or more kinds are present in the alkaline developer. 8. The method for forming a super-high contrast image according to claim 1, wherein the reductone according to claim 1 is a compound represented by the following general formula (V) or a salt thereof. Embedded image (In the formula, Z represents a hydrogen atom or a hydroxyl group, and d represents an integer of 0 to 3.) 9. An alkaline developer containing the reductone according to claim 1 as an auxiliary developer, dihydroxybenzenes, 3-pyrazolidones, 3-aminopyrazolines, phenylenediamines and aminophenols. A method for forming a super-high contrast image, comprising at least one compound selected from the group consisting of: 10. General formulas (I), (II) and (III)
And at least one or more selected from (IV) 1,
2,5-thiadiazole compounds and / or 2,
A negative-working silver halide photographic light-sensitive material comprising a negative-working silver halide emulsion layer and / or another hydrophilic colloid layer containing a 1,3-benzothiadiazole compound. 11. At least one or more 1,2,5-thiadiazole compounds selected from the general formulas (I), (II), (III) and (IV) as essential components and / or An alkaline photographic developing solution for a silver halide photographic light-sensitive material, which contains a 2,1,3-benzothiadiazole compound and a reductone compound. 12. The formula (I) as an essential component,
At least one or more 1,2,5-thiadiazole compounds and / or 2,1,3-benzothiadiazole compounds selected from the group consisting of (II), (III) and (IV), reductone compounds and An alkaline photographic developer containing an auxiliary developer, as a reductone compound, an enediol-type reductone compound, an enaminol-type reductone compound, an enediamine-type reductone compound,
At least one or more reductone compound selected from the group consisting of thiol enol type reductone compound and enamine thiol type reductone compound, and further, as an auxiliary developing agent, dihydroxybenzenes, 3-pyrazolidones, 3-aminopyrazolines, The alkaline photographic developing solution for a silver halide photographic light-sensitive material according to claim 11, which contains at least one compound selected from the group consisting of phenylenediamines and aminophenols. 13. The formula (I) as an essential component,
At least one or more 1,2,5-thiadiazole compounds and / or 2,1,3-benzothiadiazole compounds selected from (II), (III) and (IV) and represented by the general formula (V) Alkaline photographic material for silver halide photographic light-sensitive material, characterized in that it contains an endiol-type reductone compound as well as an aminophenol compound, an antifoggant and a borate compound as auxiliary developers. Developer.