JPH0990553A - Silver halide photographic sensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To enhance the dimensional stability, chargeability and dryability after development processing by interposing a specified polymer between a nonphotosensitive hydrophilic colloidal layer and a support. SOLUTION: The photosensitive material has a hydrophilic colloidal layer containing dispersed solid dye particles between a silver halide photosensitive layer and the support and the nonphotosensitive hydrophilic colloidal layer and a hydrophobic polymer layer farther apart from the support than this hydrophilic layer on the same side of the support but reverse to the photosensitive layer, and between the support and the nonphotosensitive hydrophilic colloidal layer, the polymer represented mainly by the formula is interposed. In the polymer, A is a repeating unit having 2 copolymerizable ethylenically unsaturated groups, one on the side chain; B is a repeating unit having an copolymerizable ethylenically unsaturated group; R<1> is H atom or a lower alkyl group; each of R<2> -R<4> is an alkyl or aralkyl group or the like; L<1> is a divalent group; X<1> is an anion; and each of x1 , y1 , and z1 is a mol fraction and each is 0-20, 0-70, and 30-100, respectively.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a silver halide photographic light-sensitive material having a light-sensitive silver halide emulsion layer on one side of a support and a non-light-sensitive back layer on the other side. Relates to a technique for applying a support having excellent transparency, adhesiveness, antistatic property, drying property after development processing, and further excellent dimensional stability to a silver halide photographic light-sensitive material.

[0002]

2. Description of the Related Art Recently, in the photographic industry, it has been desired to speed up the development processing of silver halide photographic light-sensitive materials.

Development processing of a silver halide photographic light-sensitive material is usually carried out by the steps of development-fixing-washing-drying. In order to speed up the development process, it is necessary to reduce the time involved in this step.
Since fixing-washing is greatly related to image quality, it is effective to shorten the time required for the drying process. In order to shorten the drying time, it is necessary to improve the photosensitive material side.

By the way, a silver halide photographic light-sensitive material usually has a photosensitive silver halide emulsion layer coated on a hydrophobic polymer film, paper, or paper coated with plastic, and is subjected to development processing. In order to shorten the drying time of the light-sensitive material, it is effective to reduce the amount of hydrophilic colloid used in the light-sensitive material. However, when the hydrophilic colloid on the side of the photosensitive layer is reduced, there is a problem that the information recording function of the silver halide photographic light-sensitive material is impaired because scratches and roller marks are generated due to a decrease in mechanical strength of the layer.

Further, in order to suppress the swelling of the hydrophilic colloid layer, a means for increasing the amount of the hardener in the layer to increase the degree of crosslinking is also effective, but the means was subjected to rapid treatment. At this time, there is a problem that photographic characteristics vary greatly due to delay in development progress, residual color of sensitizing dyes and antihalation dyes, and residual silver due to delay in fixing occur, and the price paid for improving drying properties. Is too big.

Further, by removing the hydrophilic colloid layer on the non-photosensitive surface of the silver halide photographic light-sensitive material or providing a hydrophobic polymer layer in place of the non-photosensitive hydrophilic colloid layer (referred to as a back layer), the drying property is improved. Techniques for improving the properties are also known, but in this case, curling of the photosensitive material is remarkable and there is a practical problem.

Japanese Patent Laid-Open No. 63-304249 discloses that
A technique for providing a polyvinyl chloride barrier layer to reduce the dimensional change due to moisture absorption of the support is disclosed.
However, when a polyvinylidene chloride layer is provided on the support, dechlorination proceeds gradually due to long-term storage, which causes the image to turn yellow, and when collecting and recycling the edges during film formation. In addition, there is a problem that the support itself becomes yellow due to dechlorination.

On the other hand, JP-A-3-131843 discloses that a styrene-based polymer having a syndiotactic polystyrene structure in which the main chain of the main chain is racemo is used as a photographic support having excellent mechanical properties and dimensional stability. Photographic films have been proposed which consist of coalesced or compositions containing them.
However, when used as a support for a photographic light-sensitive material, there is a problem that the dielectric loss characteristic of polystyrene is lower than that of polyester that has been practically used in the past, so that it is more likely to be charged than a polyester support. .

In a silver halide photographic light-sensitive material, charging is a fatal problem in terms of quality. For example, if light emission occurs due to static electricity before development processing, the product value is lost by itself. If it does, it will not be able to be unrolled if it is a roll, and if it is a sheet, it will pull out how many sheets at a time and there will be a problem in handling, and dust in the air will adhere. Therefore, there is also a problem that the image quality is degraded.

In order to prevent such troubles caused by electrification, a method of providing a conductive layer containing a conductive substance on a photosensitive material has been publicly known and put into practical use.

JP-A-6-138581 discloses that a hydrophobic polymer layer is provided on a non-photosensitive hydrophilic colloid layer on the non-photosensitive surface of a back layer, and a photosensitive silver halide emulsion layer and a support are provided. A technique for improving the drying property after development processing by providing a layer having a solid dispersible dye between them has been proposed, and a method for forming a conductive layer of crystalline tin oxide as an antistatic means is described. There is. However, when such inorganic fine particles are used, cracks easily occur in a layer containing the inorganic fine particles, and thus the adhesiveness is impaired, and the particle size is rather large, which is observed as a high haze and has a slightly high haze syndiotactic. The problem with polystyrene films is that they are quite noticeable.

[0012]

SUMMARY OF THE INVENTION A first object of the present invention is to provide a silver halide photographic light-sensitive material having high dimensional performance, improved chargeability and dryness after development processing, and halogenated material with improved chargeability. It is to provide a silver photographic light-sensitive material.

A second object of the present invention is to provide a silver halide photographic light-sensitive material which is excellent in transparency and in which the adhesiveness of the back layer and the drying property after development processing are improved.

[0014]

The above object of the present invention is to provide at least one silver halide photosensitive layer on one surface of a support, and to solid-disperse a dye between the silver halide photosensitive layer and the support. In the form of a hydrophilic colloid layer, the non-photosensitive hydrophilic colloid layer on the side opposite to the silver halide photographic photosensitive layer and the hydrophobic polymer at a position farther from the support than the non-photosensitive hydrophilic colloid layer. In the silver halide photographic light-sensitive material having a layer, a polymer represented by the following general formula [1], [2], [3] or [4] is provided between the non-photosensitive hydrophilic colloid layer and the support. It is achieved by a silver halide photographic light-sensitive material characterized by having.

[0015]

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In the formula, A represents a repeating unit having at least two copolymerizable ethylenically unsaturated groups and containing at least one of them in a side chain, and B represents a copolymerizable ethylenically unsaturated group. Represents a repeating unit having a group. R ¹ represents a hydrogen atom or a lower alkyl group, and R ² , R ³ and R ⁴ each represent an alkyl group, an aralkyl group, an alkenyl group or an allyl group. R ^2, R ³ and R ⁴ may be the same as or different from each other, and, R ^2, R ^3, even if two of R ⁴ is to form a 5- or 6-membered ring together with the nitrogen atom linked Good.
L ¹ represents a divalent group, and X ¹ represents an anion. x _1, y ₁ and z ₁ each represent a mole fraction, x ₁ is 0 to 20%, y ₁ is 0 to 70%, z ₁ is 30% to 100%.

[0017]

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In the formula, A, B and R ⁵ have the same meanings as A, B and R ¹ in the general formula [1]. R ⁶ represents an alkyl group, an alkenyl group, an aralkyl group or an allyl group. D represents a divalent 5- or 6-membered heterocyclic residue having 1 or 2 nitrogen atoms, and the heterocyclic ring may have a substituent. X ² represents an anion. x ₂ , y ₂ and z
₂ represents a mole fraction having the same meaning as x ₁ , y ₁ and z ₁ in the general formula [1].

[0019]

[Chemical 6]

In the formula, A and B have the same meanings as A and B in the general formula [1]. R ⁸ , R ⁹ and R
Each ¹⁰ has the same meaning as R ¹ in the general formula [1]. L ² represents a divalent group having an ionene chain, and L ³ represents a monovalent group having an ionene chain. x ₃ and x ₄ are respectively x ₁ in the general formula [1], y ₃ and y ₄ are y ₁ in the general formula [1], and z ₃ and z ₄ are respectively the general formula [1]. 1] represents the same mole fraction as z ₁ .

With the above-mentioned constitution, the electrification property when a support obtained by stretching a composition containing polystyrene as a main component having a syndiotactic structure having good dimensional stability as a support is used. The problems of adhesiveness and haze of the back layer are solved.

The silver halide photographic light-sensitive material is coated at 45 ° C. to 100 ° C. after being coated with the hydrophobic polymer layer.
The object of the present invention can be achieved to a higher degree by performing the heat treatment at the temperature of 0.1 minutes or more and 1500 hours or less.

The present invention will be described in detail below.

In the silver halide photographic light-sensitive material of the present invention, the non-photosensitive hydrophilic colloid layer provided on the surface opposite to the silver halide photosensitive layer side is a curl containing a hydrophilic colloid such as gelatin as a binder. A known backing layer such as can be applied.

From the viewpoint of curling, it is preferable that the hydrophilic colloid used in the layer has a moisture absorption rate and a moisture absorption rate close to those of the binder of the photographic layer on the surface coated with the silver halide emulsion layer. The most preferable hydrophilic colloid is gelatin. As gelatin, so-called lime-processed gelatin, acid-processed gelatin, enzyme-processed gelatin, gelatin derivatives, modified gelatin, and the like commonly used in the art can be used. Among these gelatins, lime-treated gelatin and acid-treated gelatin are most preferably used.

As hydrophilic colloids other than gelatin, colloidal albumin, proteins such as casein, agar, sodium alginate, sugar derivatives such as starch derivatives, cellulose compounds such as carboxymethyl cellulose and hydroxymethyl cellulose, polyvinyl alcohol, poly-N.
Examples thereof include synthetic hydrophilic compounds such as vinylpyrrolidone and polyacrylamide.

The non-photosensitive hydrophilic colloid layer of the present invention comprises
In addition to the binder, a photographic additive such as a matting agent, a surfactant, a dye, a cross-linking agent, a thickener, a preservative, a UV absorber, and inorganic fine particles such as colloidal silica may be added. Regarding these additives, for example, the description of Research Disclosure Vol. 176, Item 17643 (December 1978) can be referred to.

A polymer latex may be further added to the layer. The polymer latex used is an aqueous dispersion of a water-insoluble polymer having an average particle size of 20 mμ to 200 mμ, and the preferable amount used is 0.01 to 1.0 in terms of dry weight ratio to 1.0 of the binder, and particularly preferably 0. 1 to 0.
8 Preferred examples of the polymer latex used are acrylic acid alkyl ester, hydroxyalkyl ester or glycidyl ester, or methacrylic acid alkyl ester, hydroxyalkyl ester, or glycidyl ester as a monomer unit, and have an average molecular weight of 100,000 or more, Particularly preferably 30
10,000 to 500,000 polymers.

The non-photosensitive hydrophilic colloid layer of the present invention comprises 1
It may be a layer or two or more layers. The thickness of the layer is not particularly limited, but from the viewpoint of curling, it is preferably about 0.2 to 20 μm, and particularly preferably 0.5 to 10 μm.

Next, the hydrophobic polymer layer located farther from the support than the non-photosensitive hydrophilic colloid layer will be described.

The above-mentioned hydrophobic polymer layer is a layer formed by latex, and examples of the latex that can be used for the layer include polyethylene, polyvinyl chloride, polyurethane, polyvinylidene chloride, natural rubber and styrene. There are rubber compounds such as butadiene-based copolymers, acrylic or methacrylic amides, esters of acrylic acid or methacrylic acid, and latexes of copolymers containing styrene-based monomers as main components. It is preferable that the latex contains such components and acid components such as acrylic acid, methacrylic acid, and itaconic acid. Further, in order to three-dimensionally crosslink the inside of the latex particles, divinylbenzene or an acrylic acid ester or a methacrylic acid ester having a glycidyl group may be contained. The latex used for forming the hydrophobic polymer layer preferably has an average particle size of 0.01 to 0.2 μm.

The glass transition temperature of this latex is not particularly limited, but is preferably 10 to 150 ° C. Further, in the layer formed from the latex, it is preferable to use an organic compound having a boiling point of 250 ° C. or higher, such as a phthalic acid ester, a glycol derivative, or a phosphoric acid ester ketone, as a plasticizer. The amount of the plasticizer added is preferably 3 to 10 parts by weight based on 100 parts by weight of the latex solid content. Further, alcohols, glycols and their derivatives having a boiling point of less than 250 ° C. may be used as a film forming aid.

In the above-mentioned hydrophobic polymer layer, a matting agent, a UV absorber, a surfactant, a dye, a slip agent, a cross-linking agent described in Research Disclosure, Vol. 176, p. 17643,
Photographic additives such as thickeners and inorganic fine particles can be added.

In the present invention, the solid dispersible dye which can be used in the hydrophilic colloid layer containing the dye in a solid dispersion form is described in JP-A-6-138581 [0.
It is possible to use those described in detail in [024] to [0094].

Such a solid disperse dye can be dispersed by a known disperser. Specifically, a ball mill, a sand mill, a colloid mill, an ultrasonic dispersion, a jet mill, a high speed impeller disperser, etc. may be mentioned. Among these, a sand mill using beads is preferably used. Upon dispersion, it is preferable to allow a surfactant to coexist, and in the dispersion, it is preferable to add a trace amount of polybasic acid.

A support obtained by stretching a composition containing syndiotactic polystyrene as a main component, which is a preferable support in the silver halide photographic light-sensitive material of the present invention, will be described.

In the present invention, syndiotactic polystyrene means that the stereoregular structure (tacticity) is mainly a syndiotactic structure, that is, carbon-carbon bond-
Styrene-based polymers (including copolymers) having a steric structure in which phenyl groups and substituted phenyl groups, which are side chains with respect to the formed main chain, are alternately located in opposite directions are referred to as "syndiotactic polystyrene-based polymer". And a composition containing polystyrene having a syndiotactic polystyrene structure as a main component means a composition containing a syndiotactic polystyrene polymer as a main component, that is, the main chain of the main chain is a racemo chain. Is a styrene-based polymer or a composition containing the same.

The tacticity of the syndiotactic polystyrene polymer is quantified by a nuclear magnetic resonance method (13C-NMR method) using isotope carbon. 13C-NM
The tacticity measured by the R method can be indicated by the abundance ratio of a plurality of continuous structural units, for example, diad in the case of 2, triad in the case of 3, and pentad in the case of 5. The polystyrene having a syndiotactic structure referred to in the invention is usually 75% or more, preferably 85% or more, or 60% or more, racemic triad, preferably 75% or more, or 30% or more, racemic pentad, preferably 50% or more in racemic dyad. It has a stereoregularity of not less than%.

Specific monomers of the polymer constituting the syndiotactic polystyrene composition include alkylstyrene such as styrene and methylstyrene, halogenated (alkyl) styrene such as chloromethylstyrene and chlorostyrene, alkoxystyrene, and the like. A single or a mixture containing vinyl benzoate as a main component. In particular, a copolymer of alkyl styrene and styrene has a
This is a preferable combination for obtaining a film having a thickness of at least m. Further, other monomers copolymerizable with these can be copolymerized to the extent that the effects of the present invention are not impaired.

The syndiotactic polystyrene-based polymer is a transition metal compound and (a) transition metal compound described in JP-A-5-320448, pages 4 to 10 in which the above raw material monomers are used as a catalyst for polymerization. Polymerization using (b) a compound containing aluminoxane as a main component or (b) a compound containing (a) a transition metal compound and (c) a compound capable of reacting with a transition metal compound to form an ionic complex as a main component Can be manufactured.

To produce the syndiotactic polystyrene polymer, first the styrene monomer is thoroughly purified and then polymerized in the presence of any of the above catalysts. At this time, the polymerization method, polymerization conditions (polymerization temperature, polymerization time), solvent, etc. may be appropriately selected. Usually from -50
At a temperature of 200 ° C, preferably 30-100 ° C,
Polymerization is carried out for 1 second to 10 hours, preferably 1 minute to 6 hours. As the polymerization method, any of a slurry polymerization method, a solution polymerization method, a bulk polymerization method, a gas phase polymerization method and the like can be used, and either continuous polymerization or discontinuous polymerization may be used. Here, in solution polymerization, as a solvent, for example, an aromatic hydrocarbon such as benzene, toluene, xylene, or ethylbenzene, an aliphatic hydrocarbon such as cyclopentane, hexane, heptane, or octane is used.
It is possible to use one kind or a combination of two or more kinds. In this case, the monomer / solvent (volume ratio) can be arbitrarily selected. The molecular weight and composition of the polymer may be controlled by a commonly used method. The molecular weight can be controlled by, for example, hydrogen, temperature, monomer concentration and the like.

Regarding the polymerization of syndiotactic polystyrene polymers, styrene homopolymers are disclosed in JP-A-62-117708, and other polymers are disclosed in JP-A-1-46912 and 1-. 17850
Each publication of No. 5 can be referred to.

The molecular weight of the syndiotactic polystyrene polymer is not limited as long as it is formed into a film,
The weight average molecular weight is preferably 10,000 or more, more preferably 30,000 or more. Weight average molecular weight is 100
If it is less than 00, the film may not be excellent in strength characteristics and heat resistance. The upper limit of the weight average molecular weight is not particularly limited, but is 1500000
With the above, there is a possibility that breakage may occur due to an increase in the drawing tension. Also, its molecular weight distribution (number average molecular weight /
The weight average molecular weight) is preferably in the range of 1.5-8. This molecular weight distribution can be adjusted by mixing different molecular weights.

Further, in the production of the syndiotactic polystyrene-based polymer, the syndiotactic polystyrene-based pellets are heated at 120 to 180 ° C. for 1 to 24 hours under a vacuum or normal pressure under an inert gas atmosphere such as air or nitrogen. It is preferably dried. The target moisture content is not particularly limited, but is 0.05% or less, preferably 0.01% or less from the viewpoint of preventing reduction in mechanical strength and the like due to hydrolysis.
Hereafter, 0.005% or less is more preferable. However, it is not limited to these methods as long as the object of the present invention can be achieved.

The high molecular polymer constituting the support of the silver halide photographic light-sensitive material of the present invention is preferably syndiotactic polystyrene alone made from styrene, and further, syndiotactic polystyrene has a main chain. The crystallization rate can be controlled by mixing a styrene polymer (IPS) having an isotactic structure in which is a meso chain, and a stronger film can be obtained.

The composition containing a syndiotactic polystyrene-based polymer as a main component contains inorganic fine particles, an antioxidant, a UV absorber and an antistatic agent for imparting functionality within a range not impairing the object of the present invention. , Dyes, pigments, pigments, etc. can be contained.

A known method can be applied to the method of extruding the support during film formation, but a preferable method is, for example, a method of extruding with a T-die. In the film forming by the T-die method, syndiotactic polystyrene pellets are melted and extruded at 280 to 350 ° C., and cooled and solidified on a casting roll while being electrostatically applied to produce an unstretched film. Next, this unstretched film is biaxially stretched and biaxially oriented. As a stretching method, a known method, for example, a sequential biaxial stretching method in which longitudinal stretching and transverse stretching are sequentially performed, a sequential biaxial stretching method of transverse stretching / longitudinal stretching, a transverse / longitudinal / longitudinal stretching method, a longitudinal / transverse stretching method.・ Longitudinal stretching method, longitudinal / longitudinal / horizontal stretching method, or simultaneous 2
An axial stretching method or the like can be adopted and can be appropriately selected according to various characteristics such as required mechanical strength and dimensional stability.

Generally in continuous production, the longitudinal direction means the above-mentioned longitudinal stretching, and the width direction means the above-mentioned transverse stretching. That is, in continuous production, a sequential biaxial stretching method in which stretching is first performed in the longitudinal direction and then in the width direction is preferable. In this case, the stretching ratio in the longitudinal and transverse directions is 2.5 to 6 times, and the longitudinal stretching temperature is the polymer. Although it depends on the glass transition temperature (Tg), the stretching is usually performed in the temperature range of (Tg + 10) ° C. to (Tg + 50) ° C. In the case of a syndiotactic polystyrene film, it is preferably carried out at 110 to 150 ° C. The stretching temperature in the width direction is slightly higher than that in the longitudinal direction and is 115 to 1
It is preferable to carry out at 60 ° C. Next, this stretched film is heat-treated. The heat treatment temperature in this case can be appropriately changed depending on the application. For photography, printing, and medical applications that require dimensional stability, 150 to 2 depending on the purpose.
A temperature of 70 ° C is adopted.

The heat treatment time is not particularly limited, but is usually 1
About 2 to 2 minutes are adopted. It goes without saying that vertical heat relaxation, horizontal heat relaxation treatment and the like may be performed as necessary.

After this, the film may be rapidly cooled and wound up, but the temperature is between 100 ° C. and the heat treatment temperature for 0.1 minutes to 15 minutes.
Gradually cool over 00 hours and wind on a large diameter core 40 ℃ ～
It is preferable to cool at 100 ° C. at an average cooling rate of −0.01 to −20 ° C./min because it has an effect of making it difficult to curl the support. 40 ℃ -100
The heat treatment at a temperature of between 0 ° C. is preferably carried out in a constant temperature bath for 0.1 minutes to 1500 hours from the time when the support is wound to the time when the emulsion is coated and the production product is cut.

In addition to the above film forming method, slipperiness, adhesiveness,
In order to impart various properties such as antistatic performance, at least one surface of the film obtained by stretching the composition containing syndiotactic polystyrene as the main component, the main component is syndiotactic polystyrene having the above properties and the like. It is also possible to produce a laminated film in which films are laminated. The lamination method is such that the resin is melted in a laminar flow and then extruded from a die, or cooled and solidified on a syndiotactic polystyrene unstretched support or a syndiotactic polystyrene uniaxially stretched support, and melted syndiotactic. Extruded and laminated with tic polystyrene, then stretched in both longitudinal and transverse directions, or in the direction perpendicular to the uniaxial stretching direction,
Obtained by heat setting. Extrusion conditions, stretching temperature, stretching ratio, heat setting temperature, etc. of the syndiotactic polystyrene resin differ slightly depending on the combination of the syndiotactic polystyrene laminated support, but it is sufficient to make fine adjustments to select the optimum conditions, and drastically change. It doesn't.

Needless to say, the laminate is composed of two or more layers, and may be a combination of the same kind of polymers (including a combination of copolymerized polymers) or a different kind of polymers.

The above-mentioned film forming method can be appropriately changed according to its use and purpose, and the present invention is not limited to these methods for any reason.

Next, the polymer represented by the general formula [1], [2], [3] or [4] will be described.

[0055]

[Chemical 7]

In the formula, A represents a repeating unit having at least two copolymerizable ethylenically unsaturated groups and containing at least one of them in a side chain, and B represents a copolymerizable ethylenically unsaturated group. Represents a repeating unit having a group. R ¹ represents a hydrogen atom or a lower alkyl group, and R ² , R ³ and R ⁴ each represent an alkyl group, an aralkyl group, an alkenyl group or an allyl group. R ^2, R ³ and R ⁴ may be the same as or different from each other, and, R ^2, R ^3, even to form a 5- or 6-membered ring together with the nitrogen atom two are linked among R ⁴ Good.
L ¹ represents a divalent group, and X ¹ represents an anion. x _1, y ₁ and z ₁ each represent a mole fraction, x ₁ is 0 to 20%, y ₁ is 0 to 70%, z ₁ is 30% to 100%.

In the general formula [1], the lower alkyl group represented by R ¹ is preferably a methyl group or an ethyl group.

The alkyl group represented by R ² , R ³ and R ⁴ is preferably an alkyl group having 1 to 8 carbon atoms or a cycloalkyl group, the aralkyl group is preferably a benzyl group, and the alkenyl group has a carbon number. 2 to 8 alkenyl groups. Examples of the 5- or 6-membered ring formed by connecting two of R ² , R ³ and R ⁴ together with the nitrogen atom include pyrrole, pyrroline, pyrrolidine, piperidine and morpholine.

The divalent group represented by L ¹ is, for example, an alkylene group having 1 to 6 carbon atoms, a phenylene group, an alkenylene group, an aralkylene group having 7 to 18 carbon atoms, or --COO--Y.
Examples thereof include groups represented by —, —CONR ⁷ —Y—. R ⁷
Represents an alkyl group (preferably an alkyl group having 1 to 6 carbon atoms), and Y represents an aralkylene group having 7 to 18 carbon atoms. X
^The anions represented by ¹ include Cl ⁻ , Br ⁻ , I ⁻ , SO
₃ ⁻ , ClO ₄ ⁻ , BF ₄ ^{− and the} like.

[0060]

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In the formula, A, B and R ⁵ have the same meanings as A, B and R ¹ in the general formula [1]. R ⁶ represents an alkyl group, an alkenyl group, an aralkyl group or an allyl group. D represents a divalent 5- or 6-membered heterocyclic residue having one or two nitrogen atoms, and the heterocyclic ring may have a substituent. X ² represents an anion. x ₂ , y ₂ and z
₂ represents a mole fraction having the same meaning as x ₁ , y ₁ and z ₁ in the general formula [1].

In the general formula [2], examples of the lower alkyl group represented by R ₅ include the same groups as those described for R ¹ in the general formula [1].

Examples of the alkyl group, alkenyl group and aralkyl group represented by R ⁶ include the same groups as those described for R ^{2 to} R ⁴ in the general formula [1].

D is a 5- or 6-membered heterocycle having one or two nitrogen atoms, preferably imidazolidine, pyridine, piperidine, triethylenediamine, 4,4 '.
-Bispyridine, 1,3-bis (4-pyridyl) propane, 4,4'-bispiperidine, 1-benzyl-triethylenediamine and the like can be mentioned. Examples of the anion represented by X ² include the same groups as those described for X ¹ in the general formula [1].

[0065]

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In the formula, A and B have the same meanings as A and B in the general formula [1]. R ⁸ , R ⁹ and R
Each ¹⁰ has the same meaning as R ¹ in the general formula [1]. L ² represents a divalent group having an ionene chain, and L ³ is 1
Represents a valent group. x ₃ and x ₄ are x ₁ in the general formula [1], y ₃ and y ₄ are y ₁ in the general formula [1], and z ₃ and z ₄ are the general formula [1]. 1] represents the same mole fraction as z ₁ .

In the general formulas [3] and [4], R ⁸ ,
Examples of the lower alkyl group represented by R ⁹ and R ¹⁰ include the same groups as those described for R ¹ in the general formula [1]. L ₂ represents a divalent group having an ionene chain, and preferably contains at least one straight chain represented by the following general formulas [5], [6] and [7].

[0068]

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In the general formula [5], Z ¹ and Z ² each represent an alkylene group having 1 to 7 carbon atoms, and R ¹¹ and R ¹²
Each represents an alkyl group having 1 to 10 carbon atoms, an alkenyl group, a benzyl group or an allyl group. Z ¹ , Z ² , R ¹¹ and R ¹² may have at least one substituent selected from an alkyl group, a cycloalkyl group, a hydroxyalkyl group and an alkenyl group. R ¹¹ and R ¹² may be linked to form a ring. W ¹ represents a divalent group, and X ³ represents an anion.
n ₁ is an integer of ₁ to 100.

In the general formula [6], Z ³ and Z ⁴ each contain a nitrogen quaternary cation and have 3 to 10 carbon atoms forming a ring.
Represents the atomic group of. When an aromatic ring is formed by Z ³ and Z ⁴ , R
¹³ and R ¹⁴ are not necessary. When Z ³ and Z ⁴ do not form an aromatic ring, R ¹³ and R ¹⁴ represent an alkyl group, an alkenyl group or a benzyl group having 1 to 10 carbon atoms, and at least an alkyl group, a cycloalkyl group or a hydroxyalkyl group. It may have one substituent. Q ¹ and W ² represent a divalent group.
Q ¹ represents an alkylene group, an alkenylene group or an aralkylene group. X ⁴ represents an anion. n ₂ is an integer of 1 to 100, and a is 0 or 1.

In the general formula [7], R ¹⁵ and R ¹⁶ are each an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group,
It represents a hydroxyalkyl group, an alkenyl group, a benzyl group, an allyl group, and may have at least one substituent consisting of an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group, a hydroxyalkyl group, and an alkenyl group. X ⁵ represents an anion, and n ₃ is an integer of 1-100.

In the general formulas [5] to [7], W ¹ ,
As W ² and W ³ , an alkylene group having 1 to 10 carbon atoms, an alkenylene group, and an aralkylene group are preferable. Two X ³ ,
X ⁴ may be the same or different.

Since actual n ₁ , n ₂ and n ₃ have distributions, the average values are shown in the preferable compound examples. The distribution width depends on the compound.

In the general formulas [1] to [4], A is divinylbenzene, 1,3-butylene diacrylate, diethylene glycol dimethacrylate, ethylene diacrylate, 1,6-hexanediacrylate,
Examples include N, N'-methylenebisacrylamide, triethylene glycol diacrylate, ethylene glycol dimethacrylate and the like.

Further, as B, olefins such as ethylene and butadiene, vinyl esters such as vinyl acetate, styrenes such as styrene and α-methylstyrene, acrylic acid esters such as ethyl acrylate and butyl acrylate, methyl methacrylate and butyl. Examples thereof include methacrylic acid esters such as methacrylate, and acids such as itaconic acid, maleic acid, acrylic acid, and methacrylic acid.

Two or more kinds of A and B may be used.

The method for producing the copolymer of the present invention is described in JP-B-60-51693, JP-A-58-56853, and JP-A-6-56.
2-9346, 55-67746, 55-65.
The method described in No. 950 can be referred to.

The polymers of the present invention (general formula [1],
Specific examples of [2]) will be given, but the invention is not limited thereto.

[0079]

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[0080]

[Chemical 12]

[0081]

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[0082]

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[0083]

[Chemical 15]

Next, the polymer of the present invention (general formula [3],
Specific examples of [4]) will be given.

[0085]

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[0086]

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[0087]

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These polymers can be used alone or in combination with other binders for coating. Furthermore, a curing agent can be used together with these binders.

The content of the polymer of the present invention is preferably 0.005 to 5 g / m ² , more preferably 0.0
1 to 3 g / m ^2, more preferably from 0.02 to 1 g / m ^2. When other binders are used in combination, the ratio of the polymer of the present invention to the other binder is 99: 1 to 1 by weight.
0:90 is preferable, 80:20 to 20:80 is more preferable, and 70:30 to 30:70 is particularly preferable.

In the silver halide photographic light-sensitive material of the present invention, the subbing layer provided on the support containing syndiotactic polystyrene as a main component may be a single subbing layer, but it should be a subbing layer of a multilayer method. Is preferred.

In the subbing layer of the multilayer method, the subbing first layer (the subbing layer on the side of the support) is preferably a layer that adheres well to the support, and the material is methacrylic acid, acrylic acid, or the like. Unsaturated carboxylic acid or its ester, a polymer or copolymer obtained from a synthetic resin monomer such as styrene, a water-dispersed polyester, polyurethane,
Examples thereof include polyethyleneimine and epoxy resin.

As the monomer of the synthetic resin used for the first subbing layer, styrene and its derivatives, unsaturated carboxylic acids such as methacrylic acid, acrylic acid, itaconic acid, their esters such as alkyl acrylate and alkyl methacrylate (as the alkyl group, Methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, 2-ethylhexyl group, cyclohexyl group, phenyl group, benzyl group, phenylethyl group, etc.); 2-hydroxy Hydroxy-containing monomers such as ethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate; acrylamide, methacrylamide, N-methylmethacrylamide, N-methylacrylamide, N- Chi methacrylamide, N-
Amido group-containing monomers such as methylolacrylamide, N, N-dimethylolacrylamide and N-methoxymethylacrylamide; amino group-containing monomers of N, N-diethylaminoethyl acrylate and N, N-diethylaminomethacrylate; glycidyl acrylate, glycidyl methacrylate and the like Epoxy group-containing monomer; Acrylic acid, methacrylic acid salt (sodium salt, potassium salt, ammonium salt), or other carboxyl group-containing monomer; Styrene sulfonic acid, vinyl sulfonic acid and their salts (sodium salt, potassium salt) (Salts, ammonium salts) and the like, monomers containing sulfonic acid groups or salts thereof; carboxyl groups such as itaconic acid, maleic acid, fumaric acid salts (sodium salt, potassium salt, ammonium salt) or the like Monomers containing; maleic acid, monomers containing an acid anhydride such as itaconic anhydride;
Examples thereof include vinyl isocyanate, allyl isocyanate, vinyl methyl ether, vinyl ethyl ether, acrylonitrile, vinyl acetate and the like. The above-mentioned monomers can be copolymerized by using one kind or two or more kinds.

A rubber-like substance may be used as the synthetic resin for the first undercoat layer. The rubber-like substance is generally composed of a vinyl monomer-diolefin, but as the vinyl monomer, styrene, acrylonitrile, methacrylonitrile, methyl methacrylate, methyl acrylate, vinyl acetate or the like is preferably used, and as the diolefin. Preferably, butadiene, isoprene and chloroprene are used. In addition to these components, acrylic acid, methacrylic acid, itaconic acid, maleic anhydride as unsaturated carboxylic acid,
Alternatively, these alkyl esters, acrolein, methacrolein, glycidyl acrylate, glycidyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, allyl acrylate, allyl methacrylate, N-methylol acrylamide, N-methylol methacryl It is advisable to add a crosslinkable component such as amide, vinyl isocyanate or allyl isocyanate. The content of diolefin is 10 to 60% by weight.
Is preferred.

Preferred polymers which are commercially available and easily available include styrene-butadiene, styrene-isoprene, styrene-chloroprene, methylmethacrylate-butadiene and acrylonitrile-butadiene.

It is preferable that the working liquid for the first subbing layer further contains a surfactant or a cellulose compound such as methyl cellulose in order to improve the coating property.

The second subbing layer is preferably a hydrophilic resin layer which adheres well to a hydrophilic colloid layer such as a silver halide emulsion layer. As the binder that constitutes the hydrophilic resin layer, water-soluble polymers such as gelatin, gelatin derivatives, casein, agar, sodium alginate, starch, polyvinyl alcohol, polyacrylic acid copolymers, carboxymethyl cellulose, hydroxyethyl cellulose, etc. Examples include a combination of a rylene sulfonic acid sodium copolymer and a hydrophobic latex, and gelatin is preferable. It is preferable to add a hardener described below to the second undercoat layer.

The second subbing layer preferably contains inorganic fine particles such as silicon dioxide and titanium dioxide, and an organic matting material (having a particle size of about 1 to 10 μm) such as polymethylmethacrylate. .

The second subbing layer may contain various additives other than those mentioned above, such as an antihalation agent and a coloring dye, if necessary.
A pigment, a coating aid, etc. can be contained.

The halogen composition of silver halide in the silver halide emulsion used in the silver halide sensitive layer of the silver halide photographic light-sensitive material of the present invention is not particularly limited, but when the processing is carried out with a small replenishment amount, For rapid processing, it is preferable to use a silver halide emulsion having a composition of silver chloride, silver chlorobromide containing 60 mol% or more of silver chloride, and silver chloroiodobromide containing 60 mol% or more of silver chloride. preferable.

The average grain size of silver halide is 1.2 μm.
m or less, and particularly 0.8 to 0.1 μm
Is preferred. The average particle size is a term that is commonly used by experts in the field of photographic science and is easily understood. The particle size means a particle diameter when the particles are spherical or spherical particles. If the particles are cubic, they are converted into spheres, and the diameter of the sphere is defined as the particle size. For details of the method for determining the average particle size, see Mies, James: The Theory of the Photographic Process (CE.
Mees & T. H. By James: The theor
y of the photographic pro
ccs), 3rd edition, pp. 36-43 (1966 (published by Macmillan "Mcmilllan")).

The shape of the silver halide grains is not limited,
The shape may be flat, spherical, cubic, tetrahedral, octahedral, or any other shape. Further, the grain size distribution is preferably narrow, and a so-called monodisperse emulsion in which 90%, preferably 95% of the total grain number falls within the grain size range of ± 40% of the average grain size is particularly preferable.

As the method for reacting the soluble silver salt and the soluble halogen salt in the present invention, any of a one-sided mixing method, a simultaneous mixing method, a combination thereof and the like may be used. A method of forming grains in the presence of excess silver ions (so-called reverse mixing method) can also be used. As one type of simultaneous mixing method, a method of keeping pAg constant in a liquid phase in which silver halide is formed, that is, a so-called controlled double jet method can be used. Gives a silver halide emulsion having a substantially uniform grain size.

As the silver halide emulsion of the silver halide sensitive layer of the present invention, an emulsion layer in which at least one silver halide emulsion of the silver halide emulsion layer contains tabular grains and tabular grains are used. 5 of the total projected area of all particles of
An emulsion in which 0% or more is a tabular grain having an aspect ratio of 2 or more can be used. The aspect ratio represents the ratio of the diameter of a circle having the same area as the projected area of a tabular grain to the distance between two parallel planes. The tabular grain may be a tabular grain having a (100) plane having a silver chloride content of 50 mol% or more as a main plane, and these are disclosed in US Pat. Nos. 5,264,337, 5,314,798 and US Pat. No. 5,320,958, etc., and the target tabular grain can be easily obtained. In the tabular grains, silver halides having different compositions can be epitaxially grown or shelled at specific surface portions. Further, in order to control the photosensitizing nucleus, a transition line can be provided on the surface or inside of the tabular grains. In order to have a transition line, fine grains of silver iodide can be present during chemical sensitization or can be formed by adding iodide ions. The silver halide grains are prepared by the acidic method,
A neutral method, an ammonia method or the like can be appropriately selected. When the metal is doped, it is preferable to form particles under acidic conditions of pH 1 to 5. Ammonia, thioethers, thiourea compounds, thione compounds and the like can be used as a silver halide solvent in order to control grain growth during formation of tabular grains. As the thioether compound, 3,6,9,15,18,21-hexoxa-12-thiatricosane and 3,9,15-trioxa-6,12- described in German Patent 1,147,845 are described.
Dithiaheptadecane, 1,17-dioxy-3,9-1
5-trioxa-6,12-dithiaheptadecane-4,
14-dione, 1,20-dioxy-3,9,12,1
8-Tetroxa-6,15, -dithiaeicosan-4,
17-dione, 7,10-dioxa-4,13-dithiahexadecane-2,15-dicarboxamide.
6-94347, oxathioether compounds described in JP-A-1-121847, JP-A-63-25965.
And cyclic oxathioether compounds described in No. 3 and No. 63-301939. Especially as thiourea, those described in JP-A-53-82408 are useful. Specifically, tetramethylthiourea, tetraethylthiourea, dimethylpiperidinothiourea, dimorpholinothiourea, 1,3-methylimidazole-2-thione, 1,3-dimethylimidazole-4-phenyl-
2-thione, tetrapropyl thiourea, etc. are mentioned.

During physical ripening or chemical ripening, metal salts such as zinc, lead, thallium, iridium, rhodium, ruthenium, osmium, palladium and platinum can be made to coexist. Doping of iridium in the range of 10 ^-9 to 10 ^-3 mol per mol of silver halide for obtaining high illuminance characteristics is often used in silver halide emulsions. In the present invention, in order to obtain a high-contrast emulsion, it is preferable to dope rhodium, ruthenium, osmium and / or rhenium in the range of 10 ⁻⁹ to 10 ⁻³ mol per mol of silver halide.

When the metal compound is added to the particles,
Metals include halogen, carbonyl, nitrosyl, thionitrosyl, amine, cyan, thiocyan, ammonia, tellurocyan, selenocyan, dipyridyl, tripyridyl,
Phenanthroline or a combination of these compounds can be coordinated. The oxidation state of the metal can be arbitrarily selected from the highest oxidation level to the lowest oxidation level. Preferred ligands are described in JP-A No. 2-20.
No. 82, No. 2-20853, No. 2-20854, No. 2-20855, 6-dentate ligands,
As the alkali complex salt, there are general sodium salt, potassium salt, cesium salt, or primary, secondary, and tertiary amine salts. Moreover, what formed the transition metal complex salt in the form of an aco complex can be used. Examples of these include, for example, K ₂ [RuCl ₆ ], (NH ₄ ) ₂ [RuCl ₆ ], K ₂
[Ru (NO) Cl ₄ (SCN)], K ₂ [RuCl
₅ (H ₂ O)], etc., and these Ru moieties are replaced by Rh, O
Substituted with s, Re, Ir, Pd and Pt can be used.

Rhodium, ruthenium, osmium and /
Alternatively, the rhenium compound can be added during silver halide grain formation. As the addition position, there is a method of distributing uniformly in the particles, a method of forming a core-shell structure, and a method of localizing a large amount in the core portion or the shell portion. It is often better to have more of them in the shell. Also,
In addition to localizing in a discontinuous layer structure, a method of increasing the existing amount continuously outside the particles may be used. The addition amount can be appropriately selected within the range of 10 ⁻⁹ mol to 10 ⁻³ mol per mol of silver halide.

The silver halide emulsion and its preparation method are described in detail in Research Disclosure (Res).
(Earth Disclosure) 176 No. 1764
3, pages 22 to 23 (December 1978).

The silver halide emulsion may or may not be chemically sensitized. As chemical sensitization methods, sulfur sensitization, selenium sensitization, tellurium sensitization, reduction sensitization and noble metal sensitization are known, and any of these may be used alone or in combination. As the sulfur sensitizer, known sulfur sensitizers can be used. Preferred sulfur sensitizers include, in addition to the sulfur compounds contained in gelatin, various sulfur compounds such as thiosulfates, thioureas, Rhodanins, polysulfide compounds and the like can be used. As the selenium sensitizer, a known selenium sensitizer can be used. For example, U.S. Pat. No. 1,623,499, JP-A-50-
The compounds described in JP-A-71325, JP-A-60-150046 and the like can be preferably used.

The silver halide photographic light-sensitive material of the present invention comprises
In order to prevent fogging during the manufacturing process, storage or photographic processing of photosensitive materials, or to stabilize photographic performance,
Various compounds can be included. That is, azoles such as benzothiazolium salts, nitroindazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, aminotriazoles , Benzotriazoles, nitrobenzotriazoles, mercaptotetrazole (especially 1-phenyl-5-mercaptotetrazole)
Etc .; mercaptopyrimidines, mercaptotriazines; thioketo compounds such as oxazolinethione; azaindenes, such as triazaindenes, tetrazaindenes (especially 4-hydroxy-substituted-1,3,3
a, 7-Tetrazaindenes), pentazaindenes, etc .; benzenethiosulfonic acid, benzenesulfinic acid,
Many compounds known as antifoggants or stabilizers, such as benzene sulfonic acid amide, can be added.

Gelatin is advantageously used as the binder or protective colloid for the silver halide sensitive layer, but other hydrophilic colloids 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, cellulose sulfates, sugar derivatives such as sodium alginate and starch derivatives; polyvinyl alcohol. , Polyvinyl alcohol partial acetal,
Various kinds of synthetic hydrophilic high-molecular substances such as homo- or copolymers such as poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, and polyvinylpyrazole can be used.

As gelatin, in addition to lime-processed gelatin,
Acid-treated gelatin may be used, gelatin hydrolyzate,
Enzymatic degradation products of gelatin can also be used.

The photographic emulsion of the present invention may contain a dispersion of a water-insoluble or hardly soluble synthetic polymer for the purpose of improving dimensional stability and the like. For example, alkyl (meth) acrylate, alkoxyacryl (meth) acrylate, glycidyl (meth) acrylate, (meth) acrylamide,
Vinyl ester (for example, vinyl acetate), acrylonitrile, olefin, styrene or the like alone or in combination;
Alternatively, it is possible to use a polymer having a monomer component of a combination of these with acrylic acid, methacrylic acid, α, β-unsaturated dicarboxylic acid, hydroxyalkyl (meth) acrylate, sulfoalkyl (meth) acrylate, styrenesulfonic acid, or the like. it can.

An inorganic or organic hardener is preferably added to the silver halide sensitive layer and the non-photosensitive hydrophilic colloid layer of the present invention as a crosslinking agent for hydrophilic colloid such as gelatin. For example, chromium salts (chromium alum, chromium acetate, etc.), aldehydes (formaldehyde, glyoxal, glutaraldehyde, etc.), N-methylol compounds (dimethylol urea, methylol dimethylhydantoin, etc.), dioxane derivatives (2,3-dihydroxydioxane, etc.), Active vinyl compounds (1,3,5-triacryloyl-hexahydro-s-triazine, bis (vinylsulfonyl) methyl ether, N, N'-methylenebis- [β- (vinylsulfonyl) propionamide]
Etc.), active halogen compounds (2,4-dichloro-6-hydroxy-s-triazine etc.), mucohalogen acids (mucochloric acid, phenoxymucochloric acid etc.) isoxazoles, dialdehyde starch, 2-chloro-6- Hydroxytriazinylated gelatin, a carboxyl group-activating type hardener and the like can be used alone or in combination.
These hardeners are Research Disclosure (Re
search Disclosure) Volume 176 176
43 (issued December 1978), page 26, paragraphs AC.

Various other additives are used in the light-sensitive material used in the present invention. For example, a desensitizer, a plasticizer, a slipping agent, a development accelerator, an oil and the like can be mentioned.

In the present invention, the compounds described below are preferably contained in the constituent layers of the silver halide photographic light-sensitive material.

(1) Compound having an acid group Compounds described in JP-A-62-237445, page 292 (8), lower left column, line 11 to page 309 (25), lower right column, line 3 (2) acidic polymer Kaihei 6-186659, page (10) [0036]
(3) Sensitizing dye JP-A-5-224330, page (3) [0017] to (17)
(13) Compound described on page [0040] JP-A-6-194777 (page 11) [0042]
Compound described in [0094] to page (22) [0015] to page (2) in JP-A-6-242533
(8) Compound described on page [0034] JP-A-6-337492 (3) page [0012]-
Compounds described on page (34), page [0056], JP-A-6-337494, page (4), page [0013] to
(14) Compound described on page [0039] (4) Supersensitizer JP-A-6-347938 (3) page [0011] to
(16) compound described on page [0066] (5) hydrazine derivative JP-A-7-114126, page (23) page [0111]
-(32) page [0157] described compound (6) Nucleation accelerator JP-A-7-114126, page (32) page [0158]
-(36) page [0169] described compound (7) tetrazolium compound JP-A-6-208188 (8) page [0059]-
(10) Compound described on page [0067] (8) Pyridinium compound JP-A-7-110556, page (5) [0028] to
(29) page [0068] described compound (9) redox compound JP-A-4-245243, 235 (7) -250.
Compounds described on page (22) The above-mentioned additives and other known additives are described, for example, in Research Disclosure No. 17643
No. (December 1978). 18716 (1979
No.) and the same No. 308119 (December 1989
Month). The following table shows the types and locations of the compounds shown in these three research disclosures.

[0117]

[Table 1]

The silver halide photographic light-sensitive material of the present invention is preferably subjected to photographic processing after exposure by an automatic processor having at least four processes of development, fixing, washing (or stabilizing bath) and drying.

Known developing agents can be used in the developer used in the silver halide photographic light-sensitive material of the present invention. Specifically, dihydroxybenzenes (such as hydroquinone and hydroquinone monosulfonate) and 3-pyrazolidones (such as 1-phenyl-3-).
Pyrazolidone, 1-phenyl-4-methyl-3-pyrazolidone, 1-phenyl-4,4-dimethyl-3-pyrazolidone, 1-phenyl-4-ethyl-3-pyrazolidone, 1-phenyl-5-methyl-3- Pyrazolidone, etc.), aminophenols (for example, o-aminophenol, p-aminophenol, N-methyl-o-aminophenol, N-methyl-p-aminophenol, 2,4
-Diaminophenol, etc.), ascorbic acids (ascorbic acid, sodium ascorbate, erythorbic acid, etc.) and metal complex salts (EDTA iron salt, DTPA iron salt, DTP)
A nickel salt, etc.) can be used alone or in combination.

As a combination of developing agents, a developing agent of ascorbic acid and its derivative and 3-pyrazolidones (for example, 1-phenyl-3-pyrazolidone, 1-phenyl-
4-methyl-3-pyrazolidone, 1-phenyl-4,4
-Dimethyl-3-pyrazolidone, 1-phenyl-4-ethyl-3-pyrazolidone, 1-phenyl-5-methyl-
3-pyrazolidone etc.) and aminophenols (eg o
-Aminophenol, p-aminophenol, N-methyl-o-aminophenol, N-methyl-p-aminophenol, 2,4-diaminophenol, etc.) or dihydroxybenzenes substituted with a hydrophilic group (for example, hydroquinone mono). Sulfonate, hydroquinone monosulfonic acid sodium salt, 2,5-hydroquinone disulfonic acid potassium salt, etc.) can be applied.
When used in combination, the developing agent of 3-pyrazolidones, aminophenols or dihydroxybenzenes substituted with a hydrophilic group is usually used in an amount of 0.01 or more and less than 0.2 mol per liter of the developing solution. Is preferred. In particular, a combination of ascorbic acid and its derivative with 3-pyrazolidones, and a combination of ascorbic acid and its derivative with 3-pyrazolidones and dihydroxybenzenes substituted with a hydrophilic group are preferably used.

An alkaline agent (sodium hydroxide, potassium hydroxide, etc.) and a pH buffering agent (eg carbonate, phosphate, borate, boric acid, acetic acid, oxalic acid, alkanolamine, etc.) are added to the developer. Preferably. As the pH buffering agent, carbonate is preferable, and the addition amount thereof is preferably 0.5 mol or more and 2.5 mol or less, and more preferably 0.75 mol or more and 1.5 mol or less, per liter. If necessary, a solubilizing agent (for example, polyethylene glycols, their esters, alkanolamines, etc.), a sensitizer (for example, nonionic surfactants containing polyoxyethylenes, quaternary ammonium compounds, etc.), surfactants, Antifoaming agents, antifoggants (for example, halides such as potassium bromide and sodium bromide, nitrobenzindazole, nitrobenzimidazole, benzotriazole, benzothiazole, tetrazoles, thiazoles, etc.), chelating agents (for example ethylenediamine tetrachloride). Acetic acid or its alkali metal salts, nitrilotriacetic acid salts, polyphosphate salts, etc., development accelerators (eg US Pat. No. 2,304,025)
No. 1, No. 47-45541), a hardener (for example, glutaraldehyde or its bisulfite adduct), or a defoaming agent. It is preferable that the pH of the developer is usually adjusted to 7.5 or more and less than 10.5.

As the fixing solution, those having a generally used composition can be used. Fixers generally have a pH of 3
~ 8. As a fixing agent, sodium thiosulfate, potassium thiosulfate, thiosulfates such as ammonium thiosulfate, sodium thiocyanate, potassium thiocyanate,
In addition to thiocyanates such as ammonium thiocyanate, organic sulfur compounds capable of forming a soluble stable silver complex salt and known as a fixing agent can be used.

The fixing solution contains a water-soluble aluminum salt which acts as a hardening agent, such as aluminum chloride, aluminum sulfate, potassium alum, and aldehyde compounds (eg, glutaraldehyde and a sulfite adduct of glutaraldehyde).
Etc. can be added. If desired, the fixer may
A compound such as a preservative (eg, sulfite, bisulfite), a pH buffer (eg, acetic acid, citric acid), a pH adjuster (eg, sulfuric acid), and a chelating agent having a water softening ability can be included. The ammonium ion concentration in the fixer is preferably 0.1 mol or less per liter of fixer.

The ammonium ion concentration is particularly preferably in the range of 0 to 0.05 mol per liter of the fixing solution. As the fixing agent, sodium thiosulfate may be used instead of ammonium thiosulfate, or ammonium thiosulfate and sodium thiosulfate may be used in combination.

In the present invention, the concentration of acetate ion in the fixing solution is preferably less than 0.33 mol / liter. The type of the acetate ion is arbitrary, and the present invention can be applied to any compound that dissociates the acetate ion in the fixing solution. However, acetic acid and lithium, potassium, sodium, and ammonium salts of acetic acid are preferably used, and particularly sodium salt. Salts and ammonium salts are preferred. The acetate ion concentration is more preferably 0.22 mol or less per liter of the fixing solution,
Particularly preferably, the amount is 0.13 mol or less, whereby the acetic acid gas generation amount can be highly reduced. Most preferably, it is substantially free of acetate ions.

The fixer contains citric acid, tartaric acid, malic acid,
Salts such as succinic acid and optical isomers thereof are included. As salts of citric acid, tartaric acid, malic acid, succinic acid, etc., these lithium salts, potassium salts, sodium salts, ammonium salts, etc., such as lithium hydrogen tartaric acid, potassium hydrogen, sodium hydrogen, ammonium hydrogen, potassium potassium tartaric acid, tartaric acid Sodium potassium and the like may be used. Of these, more preferred are citric acid, isocitric acid, malic acid, succinic acid and salts thereof. Most preferably, malic acid and its salt.

After the fixing treatment, it is washed with water and / or treated in a stabilizing bath. As a stabilizing bath, for the purpose of stabilizing an image, inorganic and organic acids and salts thereof, or alkali agents and salts thereof for adjusting the film pH (to adjust the film surface pH after treatment to 3 to 8) ( For example, borate, metaborate, borax, phosphate, carbonate, potassium hydroxide, sodium hydroxide,
Ammonia water, monocarboxylic acid, dicarboxylic acid, polycarboxylic acid, citric acid, oxalic acid, malic acid, acetic acid, etc. are used in combination, aldehydes (eg, formalin, glyoxal, glutaraldehyde, etc.), chelating agents (eg, ethylenediaminetetraacetic acid) Or an alkali metal salt thereof,
Nitrilotriacetate, polyphosphate, etc.), anti-binders (for example, phenol, 4-chlorophenol, cresol, O-
Phenylphenol, chlorophene, dichlorophene,
Formaldehyde, P-hydroxybenzoic acid ester,
2- (4-thiazoline) -benzimidazole, benzisothiazolin-3-one, dodecyl-benzyl-methylammonium chloride, N- (fluorodichloromethylthio) phthalimide, 2,4,4'-trichloro-2'-hydroxy Diphenyl ether, etc.), a color tone adjuster and / or a residual color improver (for example, a nitrogen-containing heterocyclic compound having a mercapto group as a substituent;
-Sodium mercapto-5-sulfonate-benzimidazole, 1-phenyl-5-mercaptotetrazole, 2-mercaptobenzthiazole, 2-mercapto-5-propyl-1,3,4-triazole, 2-mercaptohypoxanthine, etc.) Is contained. Among them, it is preferable that the stabilizing bath contains an anti-binder. These may be replenished in liquid or solid form.

In order to reduce the amount of waste liquid, the present invention is processed while fixing and replenishing a fixed amount proportional to the area of the photosensitive material. The fixing replenishment amount is 300 ml or less per m ² . Preferably 30 to 25 per 1 m ² respectively
0 ml.

In order to reduce the amount of waste liquid, the development replenishment amount is 1
It is preferably 250 ml or less per m ² , and more preferably 30 to ²⁰⁰ ml per 1 m ² . The fixing replenishment amount and the development replenishment amount here indicate the amounts to be replenished. Specifically, it is the replenishing amount of each liquid when replenishing the same liquid as the developing mother liquor and the fixing mother liquor, and each concentrating liquid when replenishing with the developer concentrated liquid and the fixing concentrated liquid diluted with water. And the total amount of water and the total amount of the solid processing agent volume and the water volume when the solid development processing agent and the solid fixing processing agent are replenished with a liquid dissolved in water. And the total amount of the solid processing agent volume and the water volume when the solid fixing processing agent and water are separately replenished. When replenished with a solid processing agent, the volume of the solid processing agent directly charged into the processing tank of the automatic processor,
It is preferable to express the sum of the volumes of the replenishment water added separately. The developing replenisher and the fixing replenisher are the same as the developing mother liquor and the fixing mother liquor in the tank of the automatic developing machine, respectively.
Different liquid or solid processing agents may be used.

The temperature of the developing, fixing, washing and / or stabilizing bath is preferably between 10 and 45 ° C., and the temperature of each may be adjusted separately.

In the present invention, in order to shorten the developing time, the total processing time from the insertion of the leading edge of the film into the automatic developing machine until the film comes out of the drying zone (so-called "Dry to Dry") is used. ) Is 60 seconds or less 1
It is preferably 0 seconds or more. The term "total processing time" as used herein includes the total process time required for processing the black-and-white photosensitive material, and specifically includes processing, such as development, fixing, bleaching, washing, stabilization, and drying. This is a time including all the time of the process, that is, a time of Dry to Dry. If the total processing time is less than 10 seconds, satisfactory photographic performance cannot be obtained due to desensitization and softening. More preferably, the total processing time (Dry
to Dry) is 15 to 50 seconds. Also, 100
The development time is preferably 18 seconds or less and 2 seconds or more for stable running processing of a large amount of light-sensitive material of m ² or more.

In order to bring out the effect of the present invention remarkably, a heat transfer member having a temperature of 60.degree.
~ 130 ° C heat roller etc.) or radiant object above 150 ° C (for example, tungsten, carbon, nichrome, a mixture of zirconium oxide / yttrium oxide / thorium oxide, silicon carbide, etc.) Heat energy of copper, stainless steel,
Those which transmit infrared rays by transmitting heat to a radiator such as nickel or various ceramics) and have a zone for drying are preferably used.

As the heat transfer body having a temperature of 60 ° C. or higher,
A heat roller is mentioned as an example. The heat roller preferably has an aluminum hollow roller whose outer peripheral portion is covered with silicon rubber, polyurethane, or Teflon. Both ends of the heat roller are preferably disposed inside the vicinity of the transport port of the drying unit by bearings made of a heat-resistant resin (for example, Lulon), and are rotatably supported on the side wall.

Further, it is preferable that a gear is fixed to one end of the heat roller, and the gear is rotated in the carrying direction by the drive means and the drive transmission means. A halogen heater is inserted in the roller of the heat roller, and the halogen heater is preferably connected to a temperature controller provided in the automatic developing machine. Further, a thermistor placed in contact with the outer peripheral surface of the heat roller is connected to the temperature controller, and the temperature controller detects the temperature from the thermistor at 60 ° C to 1 ° C.
It is preferable to control the halogen heater on and off so as to be 50 ° C., preferably 70 ° C. to 130 ° C.

The following examples can be given as examples of the radiation object that emits a radiation temperature of 150 ° C. or higher. (Preferably 250 ° C
Tungsten, carbon, tantalum, nichrome, a mixture of zirconium oxide, yttrium oxide, and thorium oxide, silicon carbide, molybdenum disilicide, lanthanum chromate are directly heated and radiated to control the radiation temperature or resistance. There is a method to control by transmitting heat energy from the heating element to the radiator, but copper,
Examples include stainless steel, nickel, and various ceramics.

In the present invention, a heat transfer material having a temperature of 60 ° C. or higher and a temperature of 150 ° C.
Radiating objects having the above reflection temperatures may be combined. or,
You may combine the conventional warm air of 60 degrees C or less.

Further, an automatic processor having the method and mechanism described below can be preferably used in the present invention.

(1) Deodorizing device: JP-A-64-37560
No. 544 (2), upper left column to page 545 (3), upper left column.

(2) Washing water regeneration purifying agent and apparatus: JP-A-6-250352, page (3), page "0011" to page (8), page "0058".

(3) Waste liquid treatment method: JP-A-2-6463
No. 8, 388 (2) lower left column to 391 (5) lower left column.

(4) Rinse bath between developing bath and fixing bath: JP-A-4-313749, page (18), "0054" to (2)
1) Page "0065".

(5) Water replenishing method: JP-A-1-28144
No. 6, page 250 (2), lower left column to lower right column.

(6) Method of controlling the drying air of the automatic developing machine by detecting the outside air temperature and humidity: JP-A-1-315745 49
Lower right column on page 6 (2) to lower right column on page 501 (7)
-108051, 588 (2) page, lower left column to 589 (3)
Lower left column of the page.

(7) Method for recovering silver from fixing waste liquid: JP-A-6-
No. 27623, page (4) “0012” to page (7) “00”
71 ".

[0145]

The present invention will be described in detail below with reference to examples, but the present invention is not limited thereto.

Production of Syndiotactic Polystyrene Polymer Syndiotactic polystyrene pellets were produced according to the method described in JP-A-3-131843. From the preparation of the catalyst to the polymerization reaction, all were performed in a dry argon stream. 17.8 g (71 mmol) of copper sulfate pentahydrate (CuSO ₄ .5H ₂ O) in a glass container having an internal volume of 500 ml.
200 ml of purified benzene and trimethylaluminum 2
4 ml was added and stirred at 40 ° C. for 8 hours to prepare a catalyst. This was placed under an argon gas flow. After filtering through 3 glass filters, the filtrate was freeze-dried. Take this out,
It was placed in a 2 l stainless steel container, and tributylaluminum and pentacyclopentadiethyl titanium methoxide were further mixed therein, and heated to 90 ° C.

1 liter of purified styrene was put in this,
Further, add 70 ml of purified p-methylstyrene,
The polymerization reaction was continued at this temperature for 8 hours. Thereafter, the mixture was cooled to room temperature, 1 l of methylene chloride was added, and a methanol solution of sodium methylate was added to the catalyst to deactivate the catalyst while further stirring. The contents were gradually dropped into 20 l of methanol, filtered through a glass filter, washed with methanol three times, and then dried. The weight average molecular weight of this polymer was 415,000, which was obtained from the results of GPC measurement using standard polystyrene at 135 ° C. using 1,2,4-trichlorobenzene as a solvent. Further, the melting point of this polymer was 245 ° C., and it was confirmed that the polymer obtained from the measurement of 13 C-NMR had a syndiotactic structure. After pelletizing this with an extruder,
Dried at 0 ° C.

Production of Syndiotactic Polystyrene Polymer Film At 330 ° C., the syndiotactic polystyrene pellets obtained by the polymerization example were melt extruded in an extruder. The molten polymer was extruded through a pipe into an extrusion die. Then, the film thickness of 1 is obtained by extruding and cooling while electrostatically applying to the casting drum cooled from the die slit.
An unstretched sheet of syndiotactic polystyrene of 000 μm was obtained.

The produced sheet was preheated at 115 ° C. and then stretched 3.3 times in the machine direction. After preheating at 100 ° C in a stenter, the film was stretched 3.3 times in the transverse direction at 130 ° C. Heat it at 225 ° C while relaxing it slightly in the lateral direction.
A 0 μm thick syndiotactic polystyrene film was obtained.

On the obtained syndiotactic polystyrene film (a-side), corona discharge of 23 W min / m ² was applied, and further, an ionic wind was blown, and then the undercoating liquid 1
Was provided at a dry film thickness of 1 μm and dried at 140 ° C.

Undercoating liquid 1 Styrene-butadiene latex (No. 619 made by Japan Synthetic Rubber) 40 parts by weight Styrene butadiene latex (No. 640 made by Japan Synthetic Rubber) 50 parts by weight Polystyrene matting agent (average particle size 3 μm) 5 parts by weight 2,4-dichloro-1,3,5-triazine soda salt 3 parts by weight sodium dodecylbenzene sulfonate 2 parts by weight After further corona discharge of 18 W min / m ² was applied, gelatin 80 parts by weight methyl cellulose 15 parts by weight Solid disperse dye of Dye AD-1 4 parts by weight Sodium dodecylbenzene sulfonate 3 parts by weight 2,4-dichloro-1,3,5-triazine sodium 2 parts by weight Dried processing liquid finished to 100 g with pure water Film thickness is 0.1μ
m, and further dried at 140 ° C.

Next, 23 W / m on the back layer surface (b surface)
After performing corona discharge ² and further blowing an ionic wind, the following undercoating processing liquid 2 was provided so as to have a dry film thickness of 1 μm and dried at 140 ° C.

Undercoat processing liquid 2 Styrene-butadiene type latex (No. 619 made by Japan Synthetic Rubber) 50 parts by weight Styrene-butadiene type latex (No. 640 made by Japan Synthetic Rubber) 40 parts by weight Polystyrene matting agent (average particle size 3 μm) 5 parts by weight 2,4-dichloro-1,3,5-triazine soda salt 3 parts by weight sodium dodecylbenzene sulfonate 2 parts by weight After further applying a corona discharge of 18 W min / m ² , gelatin 20 parts by weight methyl cellulose 5 parts by weight Antistatic agent listed in Table 1 Listed in Table 1 Sodium dodecylbenzene sulfonate 3 parts by weight 2,4-dichloro-1,3,5-triazine soda 2 parts by weight Working fluid finished to 100 g with pure water Dry film thickness 0.1μ
m, and further dried at 140 ° C.

Further, this undercoated support was subjected to 40c at 80 ° C.
It was wound around an m-diameter core and heat-treated at this temperature for 3 days.

For comparison, JP-A-3-13184 is used.
A support provided with an undercoat layer described in Example 3 was also prepared.

(Preparation of silver halide emulsion A) A silver chlorobromide core grain having an average thickness of 0.05 μm and an average diameter of 0.15 μm, which is composed of 70 mol% of silver chloride and the rest is silver bromide, is prepared by a double-mixing method. Prepared. At the time of mixing the core particles, 8 × 10 ⁻⁸ mol of K ₃ RuCl ₆ was added per mol of silver. The core particles were shelled using a double jet method. At that time, K ₂ I
3 × 10 ⁻⁷ mol of rCl ₆ was added per mol of silver. The obtained emulsion has an average thickness of 0.10 μm and an average diameter of 0.25.
μm core / shell monodisperse (variation coefficient 10%) (1
Chloroiodobromide (silver chloride 90
Mol%, silver iodobromide 0.2 mol% and the rest silver bromide). Then, JP-A-2-280
Modified gelatin described in JP-A-139 (a gelatin in which an amino group in gelatin is substituted with phenylcarbamyl, for example, Japanese Patent Laid-Open No. 2-53967).
-280139, Exemplified compound G-8 on page 287 (3))
It was desalted using. EAg after desalting is 190 mv at 50 ° C
Met.

4-Hydroxy-6-methyl-1,3,3a7-tetrazaindene was added to the resulting emulsion at 1 × 10 ^-3 mol per mol of silver, and potassium bromide and citric acid were further added to adjust the pH to 5. .6, adjust to EAg123mv,
After adding 2 × 10 ^-5 mol of chloroauric acid, add 3 × of inorganic sulfur
Chemical ripening was performed at a temperature of 60 ° C. until the maximum sensitivity was obtained by adding 10 ⁻⁶ mol. After completion of ripening, 4-hydroxy-6-methyl-1,3,3a7-tetrazaindene was used in an amount of 2 × 10 ^-3 mol, 1-phenyl-5-mercaptotetrazole and 3 × 10 ^-4 mol per mol of silver and gelatin. Was added.

(Preparation of Silver Halide Emulsion B) 60 mol% of silver chloride, 2.5 mol% of silver iodide, the rest of which is silver bromide, having an average thickness of 0.05 μm and an average diameter of 0.
15 μm silver chloroiodobromide core grains were prepared. At the time of mixing the core particles, K ₃ Rh (H ₂ O) Br ₅ was added in an amount of 2 × 1 per mole of silver.
^0-8 moles were added. The core particles were shelled using a double jet method. At that time, K ₂ IrCl ₆ was added in an amount of 3 × 10 ⁻⁷ mol per mol of silver. The resulting emulsion was a core / shell type monodisperse (coefficient of variation: 10%) silver chloroiodobromide (90 mol% silver chloride, 0.5 mol silver iodobromide) having an average thickness of 0.10 μm and an average diameter of 0.42 μm. %, The rest consisting of silver bromide)
The emulsion was a tabular grain emulsion. Then, JP-A-2-28013
No. 9 described in Japanese Unexamined Patent Publication (Kokai) No. 2-2 (the modified gelatin wherein the amino group in the gelatin is substituted with phenylcarbamyl).
Desalting was carried out using the exemplified compound G-8) of No. 80139, page 287 (3). The EAg after desalting was 180 mv at 50 ° C.

4-Hydroxy-6-methyl-1,3,3a7-tetrazaindene was added to the resulting emulsion at 1 × 10 ^-3 mol per mol of silver, and potassium bromide and citric acid were further added to adjust the pH to 5. .6, adjust to EAg123mv,
After adding 2 × 10 ⁻⁵ mol of chloroauric acid, N, N, N′-
3 × 1 of trimethyl-N′-heptafluoroselenourea
0 ^-5 mol added to up sensitivity out at a temperature 60 ° C. chemically ripened. After completion of ripening, 4-hydroxy-6-methyl-1,3,3a7-tetrazaindene was added in an amount of 2 × 10 ^-3 mol, 1-phenyl-5-mercaptotetrazole in an amount of 3 × 10 ^-4 mol, and gelatin in each mol of silver. Was added.

Preparation of silver halide photographic light-sensitive material On the surface a of the support described above, the undercoat processing liquid 1 was applied, and a gelatin undercoat layer of the following Formulation 1 was used at a gelatin amount of 0.5 g /
such that m ^2, amount of silver 1.5 g / m ² of silver halide emulsion layers 1 formulation 2 thereon, the amount of gelatin 0.5 g / m ²
And a coating solution of the following formulation 3 as an intermediate protective layer on the upper layer so that the amount of gelatin is 0.3 g / m ² , and on the upper layer thereof a silver halide emulsion layer 2 of the formulation 4
Was simultaneously multi-layered so that the amount of silver was 1.4 g / m ² , the amount of gelatin was 0.4 g / m ^2, and the coating solution of the following formulation 5 was 0.6 g / m ² . A backing layer having the following formulation 6 was formed on the opposite undercoat layer so that the amount of gelatin was 0.6 g / m ² and the following formulation 7
A sample was obtained by applying the above hydrophobic polymer layer (1) and a backing protective layer having the following formulation 8 simultaneously on the emulsion layer side so that the amount of gelatin was 0.4 g / m ² .

Formulation 1 (Gelatin undercoat layer composition) Gelatin 0.5 g / m ² Solid dispersion fine particles of dye (average particle size 0.1 μm) 25 mg / m ² Sodium polystyrene sulfonate 10 mg / m ² S-1 (Sodium- Iso-amyl-n-decyl sulfosuccinate) 0.4 mg / m ² Formulation 2 (composition of silver halide emulsion layer 1) Silver halide emulsion A Solid dispersion fine particles of dye so that the amount of silver is 1.5 g / m ^2. (Average particle size 0.1 μm) 20 mg / m ² cyclodextrin (hydrophilic polymer) 0.5 g / m ² sensitizing dye 5 mg / m ² sensitizing dye 5 mg / m ² hydrazine derivative 20 mg / m ² redox compound 20 mg / m ² compound 100 mg / m ² latex polymer 0.5 g / m ² hardener ^{5mg / m 2 S-1 0.7mg} / m 2 2- mercapto-6-hydroxy purine 5mg m ² EDTA 30mg / m ² Colloidal silica (average particle size 0.05 .mu.m) 10 mg / m ² Formulation 3 (intermediate layer composition) Gelatin ^{0.3g / m 2 S-1 2mg} / m 2 Formulation 4 (silver halide emulsion layer 2 composition) silver halide emulsion B sensitizing dye 3 mg / m ² sensitizing dye 3 mg / m ² hydrazine derivative 20 mg / m ² nucleation accelerator 40 mg / m ² redox compound so that the amount of silver is 1.4 g / m ² . 20 mg / m ² 2-mercapto-6-hydroxypurine 5 mg / m ² EDTA 20 mg / m ² latex polymer 0.5 g / m ² S-1 1.7 mg / m ² formulation 5 (emulsion protective layer composition) gelatin 0.6 g / m ² solid dispersion dye (average particle size ^{0.1μm) 40mg / m 2 S-} 1 12mg / m 2 matting agent: monodisperse silica having an average particle diameter of 3.5 [mu] m 25 mg / m ² nucleation accelerator 40m / M ² 1,3-vinylsulfonyl-2-propanol 40 mg / m ² Surfactant 1 mg / m ² Colloidal silica (average particle size 0.05μm) 10mg / m ² hardener 30 mg / m ² formulation 6 (backing layer Composition) Gelatin 0.6 g / m ² S-1 5 mg / m ² Latex polymer 0.3 g / m ² Colloidal silica (average particle size 0.05 μm) 70 mg / m ² Sodium polystyrene sulfonate 20 mg / m ² compound 100 mg / m ² Formulation 7 (coating liquid composition for hydrophobic polymer layer) Described in Table 1 Formulation 8 (backing protective layer) Gelatin 0.4 g / m ² Matting agent: Monodisperse polymethylmethacrylate 50 mg / m ² sodium with an average particle size of 5 μm di - (2-ethylhexyl) - sulfosuccinate 10 mg / m ² surfactant 1 mg / m ² dye 20mg / m ² H- (O _{H 2 CH 2) 68 -OH 50mg} / m 2 hardener 20 mg / ^{m 2}

[0162]

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[0163]

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[0164]

[Chemical 21]

[0165]

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[0166]

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[0167]

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The silver halide photographic light-sensitive material samples prepared as described above were evaluated as described below.
The results are shown in Table 2.

Development Processing Developer Part 1 Potassium hydroxide 150 g Potassium sulfite 1290 g Sodium carbonate 450 g L Ascorbic acid 75 g Potassium bromide 15 g Diethylene glycol 150 g Diethylenetriamine pentaacetic acid 30 g 1- (N, N-diethylamino) ethyl-5-mercaptrazol 1 0.5g Hydroquinone 405g 4-Hydroxymethyl-4-methyl-1-phenyl-3-pyrazolidone 30g Finish with pure water to 4500ml Developer Part 2 Triethylene glycol 750g 3,3'-Dithiobishydrocinnamic acid 3g Glacial acetic acid 75g 5 -Nitroindazole 4.5 g 1-Phenyl-3-pyrazolidone 67.5 g Finish with pure water to 1000 ml Acetate 54 g Potassium bromide 5.5 g as starter in development processing tank Put those finished 300ml with water, further satisfying the developing tank of the developing solution Part placed in a mixing ratio of less water.

Part 1 30 vol% Part 2 6.7 vol% Water 63.3 vol% pH 10.5 at this time Also, 200 ml of this mixed solution is replenished after passing 8 sheets in four-piece cut size conversion.

Fixing solution parts Ammonium thiosulfate (70 wt / vol%) 3000 ml Ethylenediaminetetraacetic acid disodium dihydrate 0.45 g Sodium sulfite 225 g Boric acid 60 g 1- (N, N-diethylamino) ethyl-5-mercaptrazole 15 g Tartaric acid 48 g Glacial acetic acid 675 g Sodium hydroxide 225 g Sulfuric acid (36N) 58.5 g Aluminum sulfate 150 g Finish with pure water to 6000 ml pH 4.68 The fixing solution layer was filled with a mixture of the above fixing solution parts and water in the following proportions.

Fixing liquid parts 40 vol% water 60 vol% pH 4.62 Further, after passing 8 sheets in 4 cut size, 200 ml of this mixed solution is replenished.

Evaluation Method Transparency after Development The unexposed product was developed, 10 sheets were overlaid and placed on a 10-point Mincho typeface, and the appearance of the typeface was evaluated according to the following criteria.

Evaluation 5: Characters can be read without problems 4: Bounced parts of characters are fainted 3: Bounced parts of characters cannot be discerned 2: Whole characters are fainted 1: Characters cannot be discriminated If haze is less than 5% , Which is an allowable value in terms of product quality.

Adhesiveness to Support After conditioning the subbed support for 24 hours at 23 ° C. in an atmosphere of 55% RH, the B side was scratched in a grid pattern with a razor, and the cellophane tape was applied to it. It was pressed onto the scratch and peeled off vigorously.

Evaluation Criteria Evaluation Peeling Situation 5: None at all 4: Peeling below 5% 3: Peeling above 5% to less than 20% 2: Peeling above 20% to less than 50% 1: 50% to less than 100% No peeling 0: 100% peeling If the evaluation is 4 or more, there is no practical problem.

Evaluation of cracks in undercoat layer 3: No cracks at all 2: Cracks visible with a magnifying glass 10 times 1: Cracks visible with naked eyes 0: Large cracks Evaluation must be 3 for practical use.

Generation of Static Marks Evaluation Method A sample finished as a light-sensitive material was conditioned under an atmosphere of 23 ° C. and 10% RH for 24 hours, and then a stainless steel roll and a natural rubber roll were faced to each other in a line. Pressure 50 kg /
The sample was passed by rotating the roll at m. The feeling of touching the sample after passing the roll and the state of static marks generated by developing the sample after that were evaluated according to the following criteria.

Evaluation Criteria Evaluation 5: None at all 4: A shock is felt when the sample is touched after passing the paper.
No static mark 3: Slightly generated at the edge part 2: Small static mark generated on the entire surface 1: Large sticky mark generated on the entire surface Drying property in a developing machine Automatic development of 4-cut size sample without exposure Machine (FG
-710: made by Fuji Photo Film Co., Ltd.), the drying temperature is set to 50 ° C., and the drying time is changed by changing the conveying speed. I asked.

[0180]

[Table 2]

* 1 Methyl methacrylate / butyl acrylate / methacrylic acid 1 g / m ² (weight ratio 54/41/5) Dioctyl phthalate 50 mg / m ² Hardener 6 mg / m ² * 2 Methyl methacrylate / acrylic 2-ethylhexyl acrylate / styrene 1 g / m ² (weight ratio 61/29/10) dioctyl phthalate 30 mg / m ² butyl cellosolve 50 mg / m ² hardener 7 g / m ² * 3 methyl methacrylate / butyl acrylate / Methacrylic acid 1 g / m ² (weight ratio 45/50/5) triethylene glycol acetate 50 mg / m ² sec-pentanol 150 mg / m ² hardener

[0182]

According to the present invention, there is provided a silver halide photographic light-sensitive material having high dimensional performance, improved chargeability and dryability after development, and good dimensional stability. Provided is a silver halide photographic light-sensitive material which is excellent and has improved back layer adhesion and dryness after development.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Office reference number FI technical display location G03C 1/83 G03C 1/83 1/89 1/89

Claims (3)

[Claims] 1. A support having at least one silver halide photosensitive layer on one surface thereof, and a hydrophilic colloid layer containing a dye in a solid dispersion state between the silver halide photosensitive layer and the support. A silver halide photographic light-sensitive material having a non-photosensitive hydrophilic colloid layer on the side opposite to the silver halide photographic light-sensitive layer and a hydrophobic polymer layer at a position farther from the support than the non-light-sensitive hydrophilic colloid layer, Between the non-photosensitive hydrophilic colloid layer and the support, the following general formulas [1], [2],
A silver halide photographic light-sensitive material comprising a polymer represented by [3] or [4]. Embedded image [In the formula, A represents a repeating unit having at least two copolymerizable ethylenically unsaturated groups and containing at least one of them in a side chain, and B represents a copolymerizable ethylenically unsaturated group. Represents a repeating unit having R ¹ represents a hydrogen atom or a lower alkyl group, and R ² , R ³ and R ⁴ each represent an alkyl group, an aralkyl group, an alkenyl group or an allyl group.
R ^2, R ³ and R ⁴ may be the same as or different from each other, and, R ^2, R ^3, even if two of R ⁴ is to form a 5- or 6-membered ring together with the nitrogen atom linked Good. L ¹ represents a divalent group, and X ¹ represents an anion. x ₁ , y ₁ and z ₁ each represent a mole fraction, x ₁ is 0 to 20%, y ₁ is 0 to 70%,
z ₁ is 30 to 100%. ] [Chemical 2] [In the formula, A, B and R ⁵ are each represented by the general formula [1].
Has the same meaning as A, B and R ¹ in. R ⁶ represents an alkyl group, an alkenyl group, an aralkyl group or an allyl group.
D represents a divalent 5- or 6-membered heterocyclic residue having 1 or 2 nitrogen atoms, and the heterocyclic ring may have a substituent. X ² represents an anion. x ₂ , y ₂ and z ₂ represent the same mole fractions as x ₁ , y ₁ and z ₁ in the above general formula [1]. ] [Chemical 3] [In formula, A and B are synonymous with A and B in the said General formula [1], respectively. R ⁸ , R ⁹ and R ¹⁰ each have the same meaning as R ¹ in the general formula [1]. L ² represents a divalent group having an ionene chain, and L ³ represents a monovalent group having an ionene chain. x ₃ and x ₄ are respectively x ₁ in the general formula [1], y ₃ and y ₄ are y ₁ in the general formula [1], and z ₃ and z ₄ are respectively the general formula [1]. 1] represents the same mole fraction as z ₁ . ] 2. A silver halide photographic light-sensitive material, wherein the support according to claim 1 is a support obtained by stretching a composition containing polystyrene having a syndiotactic structure as a main component. 3. The silver halide photographic light-sensitive material according to claim 1 or 2 is coated with a hydrophobic polymer layer at 45.degree.
A silver halide photographic light-sensitive material, which is heat-treated at a temperature of 100 ° C. for 0.1 minutes or more and 1500 hours or less.