JPH08314053A - Silver halide photographic material - Google Patents

Abstract

(57) [Summary] [Purpose] To provide a light-sensitive material with high contrast and sufficient maximum density that can be handled in a bright room for a long time with little silver halide elution into the developer and little silver stain. provide. (1) At least one photosensitive layer having silver halide grains is provided on a support, and a hydrazine derivative and a hydrazine derivative are provided on a hydrophilic colloid layer on the same surface of the support as the photosensitive layer or support. Alkyl (aryl) polyether sulfonic acid as a surfactant and a minimum film formation temperature of 0 ° C
A silver halide photographic light-sensitive material comprising the following water-dispersible fine particle polymer. (2) At least one photosensitive layer having silver halide grains containing 90 mol% of silver chloride and containing 5 × 10 ⁻⁷ to 2 × 10 ⁻⁴ mol of a water-soluble rhodium salt per mol of silver halide. The silver halide photographic light-sensitive material as described in (1), which has.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide photographic light-sensitive material, and more particularly to a light-sensitive material for an ultra-bright light room mainly used in the printing and plate-making industry.

[0002]

2. Description of the Related Art In recent years, in the field of printing, due to the complexity of printed materials and the development of scanners, there has been a demand for improving the efficiency of the returning work process. Therefore, a photographic film with a low sensitivity of about 10 ^-4 to 10 ^-5 has been developed compared to the conventionally used return film, and the return film can be handled in a bright room (under a white fluorescent lamp excluding ultraviolet rays). It is practically used as a film, that is, a light-sensitive material for a bright room. The performance required for such a light-sensitive material for a bright room is that it can be handled for a long time in a light room and has high sensitivity to a printer light source. It has a sufficient maximum density with moderate or higher hardness.

Special developers called lith developers have been used in the art to provide high contrast and sufficient maximum density. The squirrel developer contains only hydroquinone as a developing agent, and a sulfite salt as a preservative is used in the form of an adduct with formaldehyde so as not to impair the infectious developability, and the concentration of free sulfite ion is extremely low. .
Therefore, the lith developer has a serious drawback that it is extremely susceptible to air oxidation and cannot be stored for more than 3 days. On the other hand, in order to obtain a sufficient maximum density with high contrast using a developing solution more stable than this, U.S. Pat.
No. 1, No. 4,168,977, No. 4,166,742
Issue 4,311,781, Issue 4,272,606
No. 4,221,857, and No. 4,243,739. According to this method, since a high concentration of sulfite can be added to the developer, the stability of the developer against air oxidation is dramatically improved as compared with the lith development.

However, it is applied as a light-sensitive emulsion for a bright room or a hydrophilic colloid layer containing a general surfactant and containing a large amount of a water-soluble rhodium salt for the purpose of extremely reducing the sensitivity. When this hydrazine compound is used for the coating liquid, the hydrazine compound does not uniformly disperse and aggregates when the coating liquid is left in a liquid state,
There is a problem that a sufficient maximum concentration cannot be obtained, and in order to make up for such a drawback, a method using an alkyl (aryl) polyethersulfonic acid as a surfactant as described in JP-A-5-61142. There is.

On the other hand, in the printing plate making industry, in the plate collecting process, a work of so-called sticking is often used in which several light-sensitive materials subjected to exposure and development are stuck together,
In many cases, the tape is attached directly to the emulsion side as well as the back side. In addition, there are cases where the tape once attached to the emulsion surface is peeled off, such as when using the pasted object again, when changing only a part of the pasted object, when making corrections due to a pasting error, etc. At this time, if the adhesiveness between the photographic constituent layer on the emulsion side and the support is poor, there is a problem that the photographic constituent layer is peeled off at the same time as the tape when the tape is peeled off, and the image disappears. Even when an alkyl (aryl) polyethersulfonic acid is used as a surfactant for the purpose of suppressing aggregation of the hydrazine compound in the material, there is a problem with this adhesiveness.

Polymer latex has often been added for the purpose of improving their adhesion.
The present inventors have used a common polymer latex commonly used by those skilled in the art for improving the adhesion of a photographic constituent layer on a support to a photosensitive layer or a support on the same surface as the photosensitive layer. It was confirmed that when used in a hydrophilic colloid layer, hard photographic characteristics due to the hydrazine derivative cannot be obtained.

Furthermore, it enables long-term handling in a bright room,
In other words, in order to minimize the sensitivity to white fluorescent lamps excluding ultraviolet light and to have a high contrast and a sufficient maximum density, increase the proportion of silver chloride in the silver halide emulsion (or make it 100% silver chloride). Using a water-soluble rhodium salt is a technique often used by those skilled in the art. However, this method also has a problem that the handling safety in a bright room is deteriorated by using the hydrazine derivative and the polymer latex in combination.

[0008]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a bright room photographic light-sensitive material having a high contrast, a sufficient maximum density and excellent adhesion of photographic constituent layers on a support. is there.

[0009]

The objects of the present invention have been achieved by the following paragraphs. (1) At least one photosensitive layer having silver halide grains is provided on a support, and a hydrazine derivative and the following compound are added to a hydrophilic colloid layer on the same surface of the support as the photosensitive layer or the support. A silver halide photographic light-sensitive material comprising a compound represented by 3 and a water-dispersible fine particle polymer having a minimum film formation temperature of 0 ° C. or less.

[0010]

Embedded image [In chemical formula 3, n is a natural number from 1 to 10. M represents a hydrogen atom or an alkali metal. X represents a C5 to C15 alkyl group or a substituent represented by Chemical formula 4. In Chemical Formula 4, X1 represents a C5 to C15 alkyl group, and X2 represents a C1 to C3 alkyl group, a hydrogen atom, or a halogen atom. ]

[0011]

[Chemical 4]

(2) A photosensitive layer having silver halide grains containing 90 mol% of silver chloride and containing 5 × 10 ⁻⁷ to 2 × 10 ⁻⁴ mol of a water-soluble rhodium salt per mol of silver halide. The silver halide photographic light-sensitive material as described in (1) above, which has at least one layer.

The present invention will be described in more detail below. As the water-dispersible fine particle polymer used in the present invention, a so-called synthetic polymer latex, a wide range of polymer latexes having a minimum film formation temperature of 0 ° C. or lower can be used. The minimum film-forming temperature of the synthetic polymer latex can be measured by the temperature gradient plate method as described in "Chemistry of Polymer Latex" (1970) by Soichi Muroi (p. 260).

The water-dispersible fine particle polymer used in the present invention, a so-called synthetic polymer latex, is preferably a latex composed of ethylenically unsaturated monomers, so-called vinyl polymer particles, and particularly preferably a copolymer of vinyl monomers. . It is possible to synthesize the polymer latex having the lowest film-forming temperature used in the present invention by selecting the constituent components and the constituent ratio.

Suitable vinyl monomers include acrylic acid esters (methyl acrylate, ethyl acrylate,
Propyl acrylate, butyl acrylate, t-butyl acrylate, amyl acrylate, hexyl acrylate, octyl acrylate, etc.), α-substituted acrylates (methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, 2-ethylhexyl hexyl methacrylate, etc.),
Acrylamide (butylacrylamide, hexylacrylamide, etc.), vinyl ester (vinyl acetate, etc.), vinyl halide (vinyl chloride, etc.), vinylidene halide (vinylidene chloride, etc.), vinyl ether (vinyl methyl ether, vinyl octyl ether, etc.), styrene,
Examples thereof include ethylene, butadiene and acrylonitrile. Particularly preferred are alkyl acrylate and alkyl methacrylate. Alkyl acrylate or alkyl methacrylate copolymers containing vinyl monomers having acrylic acid, methacrylic acid, itaconic acid, or sulfonic acid groups, preferably in a proportion of up to 30 mol%, are particularly useful. Specific examples of these are disclosed in JP-B-46-22506, JP-A-56-56227 and JP-A-51.
Reference can be made to the specification such as -59942. The synthetic polymer latices disclosed in the above patent specifications can be used particularly advantageously. For example, preferred synthetic polymer latices include (butyl acrylate-acrylic acid) copolymers, (methyl acrylate-acrylic acid) copolymers, (ethyl acrylate-acrylic acid) copolymers,
(Butyl acrylate-itaconic acid) copolymer, (ethyl acrylate-methacrylic acid) copolymer, (propyl acrylate-acrylic acid) copolymer, (butyl acrylate-styrene sulfonic acid) copolymer, (ethyl acrylate-styrene sulfonic acid) copolymer,
(Methyl acrylate-sulfopropyl acrylate)
Copolymer, (ethyl acrylate-acrylic acid-2-
Acetoacetoxy-ethyl methacrylate) copolymer, (methyl methacrylate-acrylic acid) copolymer, (methyl methacrylate-itaconic acid) copolymer and the like.

Synthetic polymer latices are used with binders such as gelatin which make up the photographic layer. In the light-sensitive material of the present invention, the polymer latex is preferably contained in the silver halide emulsion layer, but may be contained in any other hydrophilic colloid layer. Since the content of the polymer latex of the present invention in the layer depends on the characteristics of the silver halide emulsion used, the chemical structure of the compound and the development conditions, a suitable content may vary over a wide range, but the solid content may vary. A converted amount of 2 g or less per square meter is practically useful, and a range of 0.1 to 1 g is more preferable. If the amount is more than this range, the hard photographic characteristics using the hydrazine derivative, which is a feature of the present invention, cannot be obtained and the physical properties of the film are adversely affected. Moreover, the effect of the present invention cannot be obtained in a small range. The content of this polymer latex defines the amount on the side of the photosensitive layer as viewed from the support, and the content on the back side is not affected by these, and the amount required for the purpose of improving dimensional stability, etc. Can be included.

The technique of incorporating a polymer latex into a silver halide photographic light-sensitive material containing a hydrazine derivative is as follows:
Japanese Unexamined Patent Publication Nos. 2-41, 2-18134, and 4-5114
2, the same 4-106542 (hereinafter referred to as patent A, patent B, patent C, and patent D, respectively). Among them, Patents A, B, and D are examples in which a polymer latex is added as a means for preventing black spots peculiar to a light-sensitive material containing a hydrazine derivative. Patent C is an example in which the matte property is improved by combining a polymer latex and a matting agent. On the other hand, the present inventors have added to a silver halide photographic light-sensitive material containing a hydrazine derivative,
It was confirmed that even if a general polymer latex is added to the emulsion layer as shown in the above-mentioned patent, the contrast enhancement effect of the hydrazine derivative is hindered, and there is no point in adding the hydrazine derivative. are doing. Further, when the surfactant of the present invention is not added, the maximum concentration is lowered due to the aggregation of the hydrazine derivative. For the above reasons, the hydrazine derivative and the polymer latex are contained at the same time, and the maximum concentration is high and the adhesiveness cannot be enhanced without impairing the photographic performance. The effect is completely different, and it is a completely new technology that cannot be expected from the conventional technology.

The hydrazine derivative of the present invention includes all hydrazine derivatives known to those skilled in the art, preferably JP-A-62-178246 and JP-A-62-18036.
1, Dosho 62-275247, Dosho 63-253357
The hydrazine derivatives disclosed in et al. Specifically, those represented by Chemical formula 5 are preferable.

[0019]

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[Wherein Ar represents an aryl group,
R is a group represented by -OR ₁ or -N, (R ₂₎ (R
₃ ) represents a group represented by. R ₁ represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted heterocyclic group, or a substituted or unsubstituted aryl group. R ₂ and R ₃ each independently represent a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, or a substituted or unsubstituted pyridinium group. Further, R ₂ and R ₃ may be linked to each other to form a ring. ]

The chemical formula 5 will be described in detail below.

In the chemical formula 5, the aryl group represented by Ar is specifically a phenyl group which may have a substituent, or a naphthyl group, and examples of the substituent include an alkyl group, Aryl group, hydroxyl group, halogen atom, alkoxy group, alkylthio group, aryloxy group, alkenyl group, amino group, acylamino group, sulfonamide group, alkylideneamino group, ureido group, thiourea group, thioamide group, heterocyclic group, or These combinations and the like can be mentioned. Furthermore, Ar may have a ballast group incorporated therein which is practically used in a non-moving photographic additive such as a color coupler. What is a ballast group?
It is a group having 8 or more carbon atoms, which is relatively inert to photographic properties and can be selected from, for example, an alkyl group, an alkoxy group, a phenyl group, a phenoxy group and the like.

In Chemical formula 5, R represents a group represented by —OR ₁ or a chemical group represented by Chemical formula 6.

[0024]

[Chemical 6]

R ₁ represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted heterocyclic group, or a substituted or unsubstituted aryl group.

R ₂ and R ₃ are each independently a hydrogen atom,
It represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, or a pyridinium group represented by Chemical formula 7. Also, R
₂ and R ₃ may combine with each other to form a ring.

[0027]

[Chemical 7]

R ₄ represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted aralkyl group, or a substituted or unsubstituted alkenyl group. R ₅ represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted alkoxy group. X ₁ represents an anion.

Specific examples of the compound represented by Chemical formula 7 are shown below. However, the present invention is not limited to the following compounds.

[0030]

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[0031]

[Chemical 9]

[0032]

[Chemical 10]

[0033]

[Chemical 11]

[0034]

[Chemical 12]

[0035]

[Chemical 13]

[0036]

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[0037]

[Chemical 15]

[0038]

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[0039]

[Chemical 17]

[0040]

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[0041]

[Chemical 19]

[0042]

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[0043]

[Chemical 21]

[0044]

[Chemical formula 22]

[0045]

[Chemical formula 23]

[0046]

[Chemical formula 24]

[0047]

[Chemical 25]

[0048]

[Chemical formula 26]

[0049]

[Chemical 27]

[0050]

[Chemical 28]

[0051]

[Chemical 29]

[0052]

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[0053]

[Chemical 31]

[0054]

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[0055]

[Chemical 33]

[0056]

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[0057]

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[0058]

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[0059]

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[0060]

[Chemical 38]

[0061]

[Chemical Formula 39]

[0062]

[Chemical 40]

[0063]

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[0064]

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[0065]

[Chemical 43]

[0066]

[Chemical 44]

[0067]

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[0068]

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[0069]

[Chemical 47]

[0070]

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[0071]

[Chemical 49]

[0072]

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[0073]

[Chemical 51]

[0074]

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[0075]

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[0076]

[Chemical 54]

[0077]

[Chemical 55]

[0078]

[Chemical 56]

[0079]

[Chemical 57]

[0080]

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[0081]

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[0082]

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[0083]

[Chemical formula 61]

[0084]

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[0085]

[Chemical formula 63]

[0086]

[Chemical 64]

[0087]

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[0088]

[Chemical formula 66]

[0089]

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[0090]

[Chemical 68]

[0091]

[Chemical 69]

[0092]

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[0093]

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[0094]

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[0095]

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[0096]

[Chemical 74]

[0097]

[Chemical 75]

[0098]

[Chemical 76]

[0099]

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[0100]

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[0101]

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[0102]

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[0103]

[Chemical 81]

[0104]

[Chemical formula 82]

[0105]

[Chemical 83]

[0106]

[Chemical 84]

[0107]

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[0108]

[Chemical 86]

[0109]

[Chemical 87]

[0110]

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[0111]

[Chemical 89]

[0112]

[Chemical 90]

[0113]

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[0114]

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[0115]

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[0116]

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[0117]

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[0118]

[Chemical 96]

[0119]

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[0120]

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In the light-sensitive material of the present invention, the hydrazine derivative is preferably contained in the silver halide emulsion layer.
It may be contained in other hydrophilic colloid layers. Since the content of the hydrazine derivative of the present invention in the layer depends on the characteristics of the silver halide emulsion used, the chemical structure of the compound and the development conditions, the appropriate content can vary over a wide range, A range of about 5 × 10 ^-6 to 8 × 10 ^-2 moles is practically useful per mole of silver in the silver emulsion, more preferably 5 × 10 ^-5 to 1 × 10 ^-2 moles. .

In the surfactant represented by Chemical Formula 3 of the present invention, n is preferably 10 or less. When n becomes 11 or more,
Significant effect on photographic characteristics. Particularly, 3 to 9 are preferable.
X represents a C5 to C15 alkyl group or an aryl group represented by Chemical formula 4, and when the alkyl group is C4 or less, it does not serve as a surfactant. On the other hand, when it is C16 or more, the lipophilicity is too strong, which has a large adverse effect on coatability. X
1 is a C5 to C15 alkyl group. The correlation between the number of carbon atoms and the performance as a surfactant is the same as that of the alkyl group of X. X2 represents a C1 to C3 alkyl group, a hydrogen atom, or a halogen atom. When it is C4 or more, the photographic characteristics are adversely affected. M represents a hydrogen atom or an alkali metal atom such as sodium or potassium.

Specific examples of the compound represented by Chemical formula 3 are shown below. However, the present invention is not limited to the following compounds.

[0124]

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[0125]

[Chemical 100]

[0126]

[Chemical 101]

[0127]

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[0128]

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[0129]

[Chemical 104]

[0130]

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[0131]

[Chemical formula 106]

[0132]

[Chemical formula 107]

The surfactant represented by Chemical formula 3 of the present invention is a hydrazine compound represented by Chemical formula 4 in the coating liquid applied as a silver halide emulsion layer or other hydrophilic colloid layer. It is contained at least in the coating liquid contained, and can be contained in other coating liquids. The amount added is
It may vary within the range of 0.1 g to 10 g per liter of coating liquid.
More preferably, the amount is 0.5 g to 5 g.

The silver halide used in the photosensitive silver halide emulsion layer of the light-sensitive material of the present invention is not particularly limited, but particularly preferably silver chloride or silver chlorobromide in which at least 90 mol% is silver chloride, It is preferable to use silver chlorobromoiodide or silver chloroiodide, more preferably silver chloride, silver chlorobromide containing 5 mol% or less of silver bromide, or silver chloroiodide containing 1 mol% or less of silver iodide. . The form and crystal habit of the silver halide grains are not particularly limited, but the silver halide grains that can be used in the present invention are monodisperse grains having an average grain size of 0.2 μm or less. Here, a monodisperse emulsion means 90% of the total number of grains.
The above shows particles having a particle size within the range of ± 10% of the average particle size. The method for preparing the silver halide emulsion may be any of known methods such as forward mixing, reverse mixing, and simultaneous mixing.

In the present invention, in order to obtain a low-sensitivity emulsion that can be used in a bright room for a long time, it is desirable to include a water-soluble rhodium salt such as rhodium monochloride, rhodium dichloride, rhodium trichloride, rhodium ammonium chloride. In general, the water-soluble rhodium salt is preferably used at the time of silver halide precipitation or physical ripening, but may be at any time thereafter. Water-soluble rhodium salt is 5 × 10 5 per mol of silver halide.
The range of ^{-7 to} 2 x 10 ^-4 mol is effective, and the range of 1 x 10 ^-6 to 1 x 10 ^-4 mol per mol of silver halide is preferable. If the amount is smaller than this, it is difficult to obtain the safelight safety sufficient for handling in bright room light, and if the amount is larger than this, the contrast is softened and the effect of the present invention cannot be obtained.

In addition to the rhodium salt, an iron compound such as a salt of a noble metal such as an iridium salt or a red blood salt may be allowed to be present at the time of physical ripening or nucleation of silver halide grains.

The emulsion that had been physically ripened was desalted and then
It is preferable that the necessary additives are added before coating, but the desalting treatment can be omitted.

In the light-sensitive material of the present invention, in addition to the light-sensitive emulsion layer and the overcoat layer, an intermediate layer, a backcoat layer, an undercoat layer and other hydrophilic colloid layers can be provided. A matting agent may be contained in these layers.

As the binder or protective colloid that can be used in the emulsion layer, overcoat layer, intermediate layer, backcoat layer and the like of the light-sensitive material of the present invention, it is advantageous to use gelatin, but other hydrophilic substances are used. A sex colloid can also be used. For example, gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein; cellulose derivatives such as hydroxyethyl cellulose, carboxymethyl cellulose, and cellulose sulfates; sugar derivatives such as sodium alginate and starch derivatives; polyvinyl alcohol. It is possible to use various kinds of synthetic hydrophilic polymer substances such as a partial or acetal of polyvinyl alcohol, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinyl imidazole, and other single or copolymers. . Examples of gelatin include lime-processed gelatin, acid-processed gelatin, Bull.Soc.Sci.Phot.Japan, No. 16, P30 (19).
Enzyme-treated gelatin as described in 66) may be used, and a hydrolyzate or enzymatic degradation product of gelatin can also be used.

The photographic emulsion used in the present invention may contain various compounds for the purpose of preventing fog during the production process of the light-sensitive material, during storage or during photographic processing, or stabilizing the photographic performance. . The photographic light-sensitive material of the present invention may contain an inorganic or organic hardener in the photographic emulsion layer or other hydrophilic colloid layer. For example, chromium salts (such as chrome alum), aldehydes (such as formaldehyde and glyoxal), N-methylol compounds,
Dioxane derivatives (e.g., 2,3-dihydroxydioxane), active vinyl compounds, active halogen compounds (2,4
-Dichloro-6-hydroxy-S-triazine etc.),
Etc. can be used alone or in combination.

The photographic emulsion used in the present invention includes an emulsion layer, an overcoat layer, a backing layer, etc. for the purpose of enhancing the image quality due to irradiation, halation and the like, the character removal performance and other performances required in the printing plate making industry. Other hydrophilic colloid layers of can include filter dyes known to those skilled in the art.

Further, in the photographic emulsion layer or other hydrophilic colloid layer of the light-sensitive material produced by using the present invention, a coating aid, an antistatic agent, an improvement in slipperiness, an emulsion dispersion, an adhesion prevention and an improvement in photographic characteristics (eg, , Other surface active agents may be included for various purposes such as acceleration of development, hardening, and sensitization. Nonionics such as saponins (steroids), alkylene oxide derivatives (polyethylene glycol, polyethylene glycol alkyl ethers, etc.), glycidol derivatives (alkenyl succinic acid polyglyceride, etc.), fatty acid esters of polyhydric alcohols, alkyl esters of sugars, etc. Surface active agents; carboxyl groups, sulfo groups, phospho groups, sulfate groups, such as alkyl carboxylates, alkyl sulfates, alkyl esters, etc.
Anionic surfactants containing acidic groups such as phosphoric acid ester groups; amphoteric surfactants such as amino acids, aminoalkyl sulfonic acids, aminoalkyl sulfuric acid or phosphoric acid esters; aliphatic or aromatic quaternary ammonium salts, pyridinium , Cationic surfactants such as heterocyclic quaternary ammonium salts such as imidazolium can be used.

Any support known in the art can be used in the photographic light-sensitive material used in the present invention. Examples of the support include glass, cellulose acetate film, polyethylene terephthalate film, paper, baryta coated paper, polyolefin (for example, polyethylene and polypropylene) laminated paper, polystyrene film, polycarbonate film, and metal plate such as aluminum. 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.

To obtain ultrahigh contrast photographic characteristics using the silver halide light-sensitive material of the present invention, a conventional lith developer or pH 13 described in US Pat. No. 2,419,975 is used.
It is not necessary to use a highly alkaline developing solution close to the above, and a stable developing solution can be used. That is, for the silver halide photographic light-sensitive material of the present invention, a developer containing a sufficient amount of sulfite ion as a preservative (especially 0.15 mol / l or more) can be used, and a pH of 9.5 or more, Especially 10.5-1
With the developer of 2.3, a super-high contrast negative image can be sufficiently obtained. There is no particular limitation on the developing agent, and dihydroxybenzenes, 3-pyrazolidones, aminophenols and the like can be used alone or in combination. In addition to the above, the developer contains a pH buffer such as alkali metal sulfite, carbonate, borate, and phosphate, bromide, iodide, and organic antifoggant (particularly preferably,
(Nitroindazoles or benzotriazoles), or a development inhibitor or an antifoggant. Further, if necessary, a water softener, a dissolution aid, a color tone agent, a development accelerator, a surfactant, a defoaming agent, a film hardener, a silver stain preventing agent for the film and the like may be contained. Specific examples of these additives are described in Research Disclosure No. 176, 17643 and the like.

In particular, in order to obtain super-high contrast photographic characteristics, the developing solution is disclosed in JP-A-56-106244 and 61-26775.
9, the above-mentioned 61-230145, the above-mentioned 62-211647, and the amine compounds described in JP-A Nos. 2-50150 and 2-208652 can be added. The representative ones are listed below.

A-1) Nn-butyldiethanolamine A-2) 3-diethylamino-1,2-propanediol A-3) 2-diethylamino-1-ethanol A-4) 2-diethylamino-1-butanol A -5) 3-Diethylamino-1-propanol A-6) Triethanolamine A-7) 3-Dipropylamino-1,2-propanediol A-8) 2-Dioctylamino-1-ethanol A-9 ) 3-Amino-1,2-propanediol A-10) 1-diethylamino-2-propanol A-11) n-propyldiethanolamine A-12) 2-di-isopropylaminoethanol A-13) N, N-di -N-butylethanolamine A-14) 3-di-propylamino-1,2-propanediol A-15) 2-me Luamino-1-ethanol A-16) 3-Diethylamino-1,2-propanediol A-17) 4-Diethylamino-1-butanol A-18) 1-Diethylamino-2-butanol A-19) 1-Diethylamino-2 -Hexanol A-20) 5-diethylamino-1-pentanol A-21) 6-diethylamino-1-hexanol A-22) 1-diethylamino-2-octanol A-23) 6-diethylamino-1,2-hexanediol

The amount added may be any amount as long as it enhances the contrast.
Generally, an amount of 0.005-1.0 mol / l can be added.

In the present invention, a method may be adopted in which a developing agent is incorporated in the light-sensitive material and the processing is carried out with an alkaline activator solution. (JP-A-57-129436, 57-129433, 57-129434, 5)
7-129435, U.S. Pat. No. 4,323,643, etc.). The treatment temperature is usually selected between 18 ° C and 50 ° C, but may be lower than 18 ° C or higher than 50 ° C. It is preferable to use an automatic processor for photographic processing. In the present invention, the total processing time from when the photosensitive material is put into the automatic developing machine until it comes out is 60 seconds to 120 seconds.
Even if it is set to seconds, a photographic characteristic of a negative tone of a super-high contrast can be sufficiently obtained.

[0149]

【Example】

Example 1 2 oxonol yellow from Hoechst in a gelatin solution
00 mg / m ² , a surfactant and a matting agent were added, a hardener was added, and gelatin was applied to a polyethylene terephthalate film so as to be 3 g / m ^2, and this was used as a back coating.

On the other hand, 6.4 × 10 ^-6 rhodium dichloride consisting of cubic crystals having an average particle size of 0.13 micron was used.
A gelatin silver chloride emulsion containing mol / mol Ag was prepared by the double jet method, desalted, washed with water and redissolved by the flocculation method to prepare an emulsion of hydrazine derivative of 89 × 2 × 10 ⁻³ mol / mol Ag, 0.2 g / m ² of the polymer latex of A and 4 × 10 ⁻³ of the compound of Chemical formula 108
Mol / mole Ag, 6 × 10 5
^-3 mol / mol Ag, 1-phenyl-5-mercaptotetrazole 4 × 10 ^-3 mol / mol Ag, 2-hydroxy-4,6-dichloro-1,3,5-triazine sodium salt, After adding a surfactant, silver nitrate was applied on the above-mentioned back-coated film so that the amount of gelatin was 5 g / m ² and the amount of gelatin was 3 g / m ² .

[0151]

[Chemical 108]

[0152]

[Chemical 109]

On this, as a protective layer, 1 g / m of gelatin was used.
^2. A coating liquid containing a surfactant, a hardener and a matting agent was applied to prepare the samples shown in Table 1. Further, as shown in Table 1, a sample in which the polymer latex was changed, a sample containing no polymer latex, a sample containing no hydrazine derivative,
A sample in which the surfactant of Chemical formula 105 was changed to Chemical formula 110 was also prepared at the same time. The minimum film formation temperature was measured by the above-mentioned temperature gradient plate method.

[0154]

[Chemical 110]

A: Present Invention Mitsui Toatsu Chemical Co., Ltd. Bonron S119 (minimum film formation temperature 0 ° C. or lower) (acrylic copolymer) B: Comparative Example Mitsui Toatsu Chemical Co., Ltd. Bonron S415 (minimum film formation temperature 10 ° C or less) (Acrylic copolymer) C: The present invention Hoechst Synthetic Co., Ltd. Movinyl 084E (minimum film forming temperature 0 ° C or less) (Vinyl acetate ethylene copolymer) D: Comparative example Hoechst Synthetic Co., Ltd. Movinyl 880 (Minimum film forming temperature 20 ° C or less) (Acrylic styrene copolymer)

These films were exposed with a bright room printer (P-627FM manufactured by Dainippon Screen Mfg. Co., Ltd.) through a wedge for sensitometry, and then developed with a developer having the following composition at 38 ° C. for 20 seconds. Fixing, washing with water,
Dried. An automatic processor (Dainippon Screen Mfg. Co., Ltd., LD-221QT) was used for this treatment. From this, sensitivity and gamma were measured. The sensitivities of the samples containing no latex, which is a comparative example, are relatively expressed with the sensitivity being 100. Gamma was measured by tan θ of the linear part where the optical density was 1.0 to 2.5.

<Developer> Hydroquinone 50.0 g N-methyl-p-aminophenol 1 / 2H ₂ SO ₄ 0.3 g Sodium hydroxide 18.0 g 5-Sulfosalicylic acid 55.0 g Potassium sulfite 110.0 g EDTA · 2Na 1 0.0 g Potassium bromide 10.0 g 5-Methylbenzotriazole 0.4 g 2-Mercaptobenzene imidazole-5-sulfonic acid 0.2 g 3- (5-Mercaptotetrazole) benzene sulfonate 0.2 g N-n-butyldiethanolamine 12.0 g sodium toluenesulfonate 8.0 g Water was added and adjusted to pH 11.8 with 1 l potassium hydroxide.

Further, after developing these films in the same manner as above without exposing them, a knit lithographic tape (polyester tape for plate making) manufactured by Nitto Denko Corporation was applied to the emulsion surface for 2 days. After standing at room temperature, the tape was peeled off, and the rate at which the photographic constituent layer on the emulsion side was peeled off at the same time as the tape was evaluated.

The results are shown in Table 1.

[0160]

[Table 1]

From the results of Table 1, when the polymer layer of the present invention was contained in the emulsion layer as shown in the present invention, the maximum density was higher than that in Comparative Example without impairing the contrast enhancement by the hydrazine derivative, Moreover, it can be seen that the adhesion of the photographic constituent layers onto the support is improved.

Example 2 A sample was prepared in the same manner as in Example 1 except that the amount of the above-mentioned latex polymer A contained was changed as shown in Table 2. In addition, samples were prepared as shown in Table 2 as a comparative example in which the amount of latex polymer B was changed in the same manner.

These films were processed in the same manner as in Example 1 and evaluated for sensitivity, gamma and peeling rate. Table 2 shows the results.

[0164]

[Table 2]

From the results in Table 2, it can be seen that when the polymer latex of the present invention is contained, the adhesion of the photographic constituent layer onto the support is improved without impairing the contrast enhancement by the hydrazine derivative. .

[0166]

According to the present invention, it is possible to stably produce a light-sensitive material for a bright room, which has a high contrast and is excellent in the adhesion of the photographic constituent layers to the support.

Claims (2)

[Claims] 1. A hydrazine derivative in a hydrophilic colloid layer on the same surface of the photosensitive layer or the support as the photosensitive layer or at least one photosensitive layer having silver halide grains on the support. A silver halide photographic light-sensitive material comprising a compound represented by the following chemical formula 1 and a water-dispersible fine particle polymer having a minimum film formation temperature of 0 ° C. or less. Embedded image [In chemical formula 1, n is a natural number from 1 to 10. M represents a hydrogen atom or an alkali metal. X represents a C5 to C15 alkyl group or a substituent represented by Chemical formula 2. In Chemical Formula 2, X1 represents a C5 to C15 alkyl group, and X2 represents a C1 to C3 alkyl group, a hydrogen atom, or a halogen atom. ] [Chemical 2] 2. A photosensitive layer having at least a silver halide grain containing 90 mol% of silver chloride and containing 5 × 10 ⁻⁷ to 2 × 10 ⁻⁴ mol of a water-soluble rhodium salt per mol of silver halide. The silver halide photographic light-sensitive material according to claim 1, which has one layer.