JPH0627566A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To provide a silver halide photographic sensitive material excellent in dimensional stability, physical properties of the film and reducibility. CONSTITUTION:This silver halide photographic sensitive material has at least one photosensitive silver halide emulsion layer and a non-photosensitive hydrophilic colloidal layer on one side of the base and at least one backing layer on the other side. At least one of the constituent layers contains polymer latex stabilized with gelatin and the hydrophilic colloidal layer has been hardened with a vinyl-sulfone hardening agent.

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 silver halide photographic light-sensitive material excellent in dimensional stability and reducing power.

[0002]

BACKGROUND OF THE INVENTION In silver halide photographic light-sensitive materials (hereinafter simply referred to as "light-sensitive materials"), gelatin is often used as a binder. Gelatin has high swelling property and gelling ability, and can be easily cross-linked by various hardeners. By adjusting the physical properties of the coating liquid, materials such as photosensitive silver halide that dislike high temperature can be widely used. It is an extremely excellent binder for uniform application over the area.

However, in the light-sensitive material, the silver halide grains change into extremely hard metallic silver in a state where the gelatin layer absorbs water sufficiently and swells during development, so that the emulsion layer is restored to its original state even after drying. However, even if the same light-sensitive material is used, the dimensions may differ before and after processing.

To improve this, a technique is known in which a polymer latex is contained in a silver halide emulsion layer and a backing layer. For example, Research Disclosure (RD) 1995
No. 1, JP-B 39-4272, 39-17702, 43-13482,
U.S. Patents 2,376,005, 2,763,625, 2,772,166
No. 2,852,386, 2,853,457, 3,397,988, etc. Also, JP-A-59-38741 and JP-A-61-29634
No. 8, No. 61-284756, No. 61-285446 and the like disclose a method of incorporating fine oil droplets of paraffin or vinyl polymer.

However, the conventional latex has drawbacks that when it is added to gelatin in a large amount, the latex forms a film (aggregates), and further addition does not show the effect, or the physical properties of the film deteriorate. It was also found that the reduction performance is significantly deteriorated by adding a large amount of latex. Therefore, it is desired to develop a light-sensitive material having improved dimensional stability and film physical properties in such a state.

On the other hand, in obtaining a final halftone image or line image, the photosensitive material for plate making is subjected to a process called a reduction process in order to satisfy subtle tone reproduction and artistic expression, and the image is processed. Often fine-tuned partially or entirely. Therefore, it is extremely important for the photosensitive material for plate-making to have a reducing property.

In the printing plate making process, a method of expressing the gradation (tone) of the original image by the size of the area of minute dots, that is, a halftone dot image is often adopted.

In order to reduce the strength of the photosensitive material for plate making on which a halftone dot image or a line image has been formed through exposure / development treatment, a method of bleaching the metallic silver forming the halftone dot or line image with an oxidizing agent, etc. It has been known. For example, Mies: The Theory of the Photographic Process 3rd Edition "The Theo
ry of the Photographic Process 3rd. Ed. '' 738-739
Page (1954 published by Macmillan), permanganate, second
There is described a reducing solution using a reducing component such as an iron salt, a cerium cerium salt, a red blood salt, a dichromate and a persulfate.

In the reduction processing, the larger the amount of silver per unit area that oxidizes and dissolves the silver image, the wider the range in which the image can be corrected by the reduction processing. That is, when the halftone image is subjected to a reduction process, it is general that the blackening density per halftone dot decreases in parallel with the decrease in the halftone dot area. The smaller the decrease in the blackening density per piece, the wider the range in which the reduction can be corrected. In other words, the measure of the correctable range of the halftone image can be expressed by indicating how much the halftone dot area could be reduced by keeping the blackening density per halftone dot above a certain value.

In the present invention, when the blackening density of the halftone dots is reduced to the bare minimum value required in the plate making process by the reduction processing, the halftone dot area is less than the halftone dot area before the treatment. It will be indicated by the term "reduction width".

As described above, the greater the amount of silver forming an image, the greater the reduction range, and thus the greater the degree to which the image can be corrected by the reduction process. For that purpose, it is sufficient to increase the amount of silver halide per unit area of the light-sensitive material, but as is well known, silver is extremely expensive, and it is not necessary to increase the amount of silver coated to reduce the cost of the light-sensitive material for plate making. This is not preferable from the point of view of resource saving.

Therefore, it is necessary to produce a photosensitive material for plate-making having the necessary reducing characteristics by using as little silver as possible.
It is one of the important issues in this industry, and silver saving is still in progress. It is also possible to increase the reduction width by increasing the coating amount of gelatin per unit area while keeping the amount of coated silver as it is, but increasing the amount of gelatin delays initial development, poor fixing, poor washing, poor drying, etc. However, this causes various problems in the processing steps and goes against the rapid processing that has been increasingly required in recent years.

Therefore, it has been strongly desired to develop a photosensitive material for plate making which has excellent reducing power characteristics without increasing the amount of coated silver and the amount of coated gelatin.

[0014]

SUMMARY OF THE INVENTION It is, therefore, an object of the present invention to provide a silver halide photographic light-sensitive material having excellent dimensional stability and good film properties even when a large amount of latex is added to the gelatin layer. Another object is to provide a silver halide photographic light-sensitive material excellent in reducing property.

[0015]

The above object of the present invention is to have at least one light-sensitive silver halide emulsion layer and a non-light-sensitive hydrophilic colloid layer on a support, and at least one layer on the opposite side of the support. A silver halide photographic light-sensitive material having a backing layer, wherein at least one of the constituent layers contains a gelatin-stabilized polymer latex, and a hydrophilic colloid layer is hardened with a vinyl sulfone type hardener. This is achieved by a photographic light-sensitive material.

The present invention will be described in more detail below.

In the present invention, the object of the present invention can be achieved by using a latex stabilized with gelatin. That is, the ordinary latex is dispersed in water by a surfactant, but the latex that can be used in the present invention is characterized in that the surface and / or the inside of the polymer latex is dispersed and stabilized by gelatin. The polymer constituting the latex and gelatin may have some kind of bond. In this case, the polymer and gelatin may be bound directly or may be bound via a crosslinking agent. Therefore, the monomers constituting the latex include carboxyl group, amino group, amide group,
It is desirable to include those having a reactive group such as an epoxy group, a hydroxyl group, an aldehyde group, an oxazoline group, an ether group, an ester group, a methylol group, a cyano group, an acetyl group, and an unsaturated carbon bond. When a cross-linking agent is used, those known as ordinary gelatin cross-linking agents can be used. For example, an aldehyde-based, glycol-based, triazine-based, epoxy-based, vinyl sulfone-based, oxazoline-based, acrylic-based, or other crosslinking agent can be used.

The gelatin-stabilized polymer latex of the present invention (referred to as the latex of the present invention) is characterized in that at least a part of the polymerization reaction of the polymer is carried out in a solvent containing at least gelatin. .

The present inventor has found that, in the course of continuing to study the above problems, there is a preferable range for the ratio of the addition amount of gelatin and latex during synthesis. The weight ratio of gelatin to polymer at the time of synthesis (finally obtained as latex) is preferably Gel / Poly = 1/100 to 2/1, particularly preferably 1/50 to 1/2. The effect of the present invention is that the addition amount of the polymer component of the latex is
Particularly preferable results are obtained when the content of gelatin in the layer to which the latex is added is 20% or more.

The addition amount of the polymer is 0.05-5 g / m ^2, particularly preferably 0.1~2.5g / m ^2.

The polymer latex used in the present invention can change the MFT (minimum film forming temperature) depending on the composition of the monomer, but it is particularly effective when the MFT is 60 ° C. or lower, more preferably 50 ° C. or lower. Is.

Further, in the present invention, the particle size of the latex is preferably 0.3 μm or less. A large particle size increases the devitrification after processing, so a particularly preferred particle size is 0.01 to 0.27 μm.
Is.

Examples of the constitution of the monomer of the polymer latex contained in the light-sensitive material of the present invention include, for example, US Pat. Nos. 2,772,166, 3,325,286, 3,411,911,
Examples thereof include hydrates of vinyl polymers such as acrylic acid esters, methacrylic acid esters, and styrene, which are described in Nos. 3,311,912, 3,525,620 and RD19551 (supra).

Examples of gelatin used for stabilizing the latex of the present invention include gelatin and gelatin derivatives, cellulose derivatives, graft polymers of gelatin and other polymers,
Other hydrophilic colloids such as proteins, sugar derivatives, cellulose derivatives, and synthetic hydrophilic polymer substances such as single or copolymers can also be used in combination.

Examples of gelatin include lime-processed gelatin, acid-processed gelatin, and Bulletin of Society of Japan (Bull.Soc.Sci.Phot.Japan) No. 16,30.
Acid-treated gelatin as described on page (1966) may be used, or a hydrolyzed product or an enzymatically decomposed product of gelatin may also be used. Examples of the gelatin derivative include gelatin such as acid halides, acid anhydrides, isocyanates, bromoacetic acid, alkane sultones, vinyl sulfonamides,
Those obtained by reacting various compounds such as maleinimides, polyalkylene oxides, and epoxy compounds are used. A specific example is U.S. Pat.
3,132,945, 3,186,846, 3,312,553, British Patents 861,414, 1,033,189, 1,005,784, Japanese Patent Publication 4
2-26845 etc.

The proteins include albumin and casein;
As the cellulose derivative, hydroxyethyl cellulose, carboxymethyl cellulose, or a sulfuric acid ester of cellulose; or as the sugar derivative, sodium alginate or a starch derivative may be used in combination with gelatin.

As the graft polymer of gelatin and other polymers, gelatin is acrylic acid, methacrylic acid,
Those obtained by grafting derivatives thereof such as esters and amides, and homopolymers or copolymers of vinyl monomers such as acrylonitrile and styrene can be used. In particular, a graft polymer of a polymer having a certain compatibility with gelatin, for example, a polymer such as acrylic acid, acrylamide, methacrylamide, hydroxyalkyl methacrylate or the like is preferable. Examples of these are described in US Pat. Nos. 2,763,625, 2,831,767, and 2,956,884.

The latex used in the present invention must be added to at least one hydrophilic colloid layer. Further, it may be added in any other layer (a plurality of non-photosensitive hydrophilic colloid layers and / or photosensitive hydrophilic colloid layers). It may be contained on only one side of the support, or may be contained on both sides.

A conventionally known latex may be added to the layer to which the latex of the present invention is added and / or not added. When contained on both sides of the support, the type and / or amount of the polymer latex contained on each side may be the same or different.

The latex of the present invention is present on the support outside at least one silver halide emulsion layer,
It is particularly preferably added to at least one non-photosensitive hydrophilic colloid layer.

The latex polymer component contained in the light-sensitive material of the present invention is, for example, US Pat.
No. 166, No. 3,325,286, No. 3,411,911, No. 3,311,912
Nos. 3,525,620 and RD No. 19551 (supra), there are hydrates of vinyl polymers such as acrylic acid esters, methacrylic acid esters and styrene. Specifically, acrylic acid, methacrylic acid or salt, maleic acid or salt, fumaric acid or salt, acrylic acid alkyl ester such as methyl acrylate and ethyl acrylate, methacrylic acid alkyl ester such as methyl methacrylate and ethyl methacrylate, styrene and styrene sulfone. Any compound having a double bond such as an acid or a salt, N-substituted or unsubstituted acrylamide, vinyl alcohols, hydroxyalkyl methacrylates and butadiene can be selected as a homopolymer or a copolymerization component.

Specific examples of preferable monomers are given below. As the latex of the present invention, any combination (type, composition ratio) of these monomers can be adopted. Of course, the invention is not limited to these monomers.

[0033]

[Chemical 1]

[0034]

[Chemical 2]

[0035]

[Chemical 3]

Next, the vinyl sulfone type hardener used in the present invention will be explained.

The vinyl sulfone type hardener is a compound having a vinyl group bonded to a sulfonyl group or a group capable of forming a vinyl group, preferably a vinyl group bonded to a sulfonyl group or a group capable of forming a vinyl group. Have at least two. For example, the compound represented by the following general formula [VS-I] is preferably used in the present invention.

General formula [VS-I] L- (SO ₂ -X) m L represents an m-valent linking group, and X is -CH = CH ₂ or -CH ₂ CH ₂ Y.
And Y represents a group which can be eliminated in the form of HY by a base, such as a halogen atom, a sulfonyloxy group, a sulfooxy group (including a salt), a residue of a tertiary amine and the like. m is 2-10
Represents an integer, m is 2 or more when -SO ₂ -X may be different from each other the same.

The m-valent linking group L is, for example, an aliphatic hydrocarbon group (eg, alkylene, alkylidene, alkylidyne, etc., or a group formed by combining these), an aromatic hydrocarbon group (eg, arylene, etc.), or , A group formed by combining these), --O--, --NR '-(R' represents a hydrogen atom or an alkyl group having preferably 1 to 15 carbon atoms), --S--, --N =, -CO-, -SO-, -SO ₂ -or -SO _3- is an m-valent group formed by combining one or more bonds, and -NR'- is two or more. When included, these R's may combine with each other to form a ring. The linking group L further includes those having a substituent such as a hydroxyl group, an alkoxy group, a carbamoyl group, a sulfamoyl group, an alkyl group or an aryl group.

Specific examples of X include -CH = CH ₂ or -CH
₂ CH ₂ Cl and the like are preferable.

Representative examples of vinyl sulfone type hardeners are shown below.

[0042]

[Chemical 4]

[0043]

[Chemical 5]

[0044]

[Chemical 6]

[0045]

[Chemical 7]

[0046]

[Chemical 8]

[0047]

[Chemical 9]

[0048]

[Chemical 10]

[0049]

[Chemical 11]

The vinyl sulfone type hardener used in the present invention is, for example, German Patent 1,100,942 and US Patent 3,490,9.
Aromatic compounds such as those described in No. 11 etc., Japanese Patent Publication No. 44
-29622, 47-25373, 47-24259 and the like, alkyl compounds bonded with a heteroatom as described in, for example, Japanese Patent Publication No. 47-8736 sulfonamide as described,
Ester compounds, 1,3,5-tris [β- (vinylsulfonyl) propionyl] -hexahydro-s-triazine as described in JP-A-49-24435 or JP-B-50-3
5807, alkyl compounds as described in JP-A-51-44164 and the like and compounds described in JP-A-59-18944 and the like.

These vinyl sulfone type hardeners are dissolved in water or an organic solvent and used in an amount of 0.005 to 20% by weight, preferably 0.02 to 10% by weight, based on the binder (eg gelatin).

For addition to the photographic layer, a batch method, an in-line addition method or the like is adopted.

There are no particular restrictions on the layer in which these hardeners are added to the photographic layer. For example, the uppermost layer 1 and the lowermost layer 1 may be used.
You may add to a layer or all layers.

There are no particular restrictions on the general additives of the present invention, known contrast-increasing agents, methods for producing silver halide grains, sensitization methods, etc., and examples thereof include JP-A Nos. 1-230035 and 3 -127049 etc. can be referred to.

In the present invention, one or more antistatic layers may be provided on the backing side and / or emulsion layer side of the support for the purpose of antistatic property which is another physical property of the light-sensitive material. In this case, the surface resistivity on the side provided with the antistatic layer is preferably 1.0 × 10 ¹² Ω or less at 25 ° C. and 50% RH, and particularly preferably 8 × 10 ¹¹ Ω or less.

The antistatic layer is preferably an antistatic layer containing a reaction product of a water-soluble conductive polymer, hydrophobic polymer particles and a curing agent, or an antistatic layer containing a metal oxide.

Examples of the water-soluble conductive polymer include polymers having at least one conductive group selected from a sulfo group, a sulfate ester group, a quaternary ammonium salt, a tertiary ammonium salt, a carboxyl group and a polyethylene oxide group. . Among these groups, a sulfo group, a sulfate ester group and a quaternary ammonium salt group are preferred. The conductive group needs to be 5% by weight or more per molecule of the water-soluble conductive polymer.

Further, the water-soluble conductive polymer contains a carboxyl group, a hydroxyl group, an amino group, an epoxy group, an aziridine group, an active methylene group, a sulfinic acid group, an aldehyde group, a vinyl sulfone group and the like. During,
It preferably contains a carboxyl group, a hydroxyl group, an amino group, an epoxy group, an aziridine group, and an aldehyde group. 5% by weight of these groups per polymer molecule
The above must be included. The number average molecular weight of the water-soluble conductive polymer is 3,000 to 100,000, preferably 3500 to 50,000.

Examples of the metal oxide include tin oxide, indium oxide, vanadium oxide, antimony oxide, zinc oxide, or a metal oxide, metal phosphorus, metal silver, or metal indium doped with these metal oxides. It is preferably used. The average particle size of these metal oxides is preferably 1 to 0.01 μm.

As the undercoat layer which can be used in the present invention, an undercoat layer containing an organic solvent containing polyhydroxybenzenes described in JP-A-49-3972, JP-A-49-11118,
52-104913, 59-19941, 59-19940, 59-18
945, 51-112326, 51-117617, 51-58469
No. 51, No. 51-114120, No. 51-121323, No. 51-123139,
51-114121, 52-139320, 52-65422, 52-1
09923, 52-119919, 55-65949, 57-128332
No. 59-19941 and the like water-based latex undercoating layer, and U.S. Patent Nos. 2,698,235 and 2,779,684.
No. 4,254,210, No. 4,645,731 and the like, and vinylidene chloride-based undercoating and the like.

The surface of the undercoat layer can be chemically or physically treated. Examples of the treatment include chemical treatment, mechanical treatment, corona discharge treatment, flame treatment, ultraviolet treatment, high frequency treatment, glow discharge treatment, active plasma treatment, laser treatment, mixed acid treatment, and surface activation treatment such as ozone oxidation treatment. .

The subbing layer is distinguished from the coating layer according to the present invention, and there is no limitation on the coating timing or conditions.

In the present invention, in addition to the usual water-soluble dye, a solid-dispersed dye may be contained in any of the hydrophilic colloid layers. The layer may be the outermost layer on the emulsion surface side, or may be added below the emulsion layer and / or on the backing surface side for the purpose of preventing halation.
Further, an appropriate amount may be added to the emulsion layer for adjusting the irradiation. Of course, plural kinds of solid disperse dyes may be contained in plural layers.

The addition amount of the solid disperse dye is preferably 5 mg to 1 g / m ² per type, particularly preferably 10 to 800 mg.
/ M ² .

The fine particles of the solid dispersion used are obtained by pulverizing the dye with a dispersing machine such as a ball mill or a sand mill,
It can be obtained by dispersing with water or a hydrophilic colloid such as gelatin, a surface active agent such as sodium dodecylbenzene sulfonate, sodium fluorinated octylbenzene sulfonate, saponin, nonylphenoxy polyethylene glycol.

The general formula for solid disperse dyes is as follows:
Examples thereof include those described in No. 4,857,446, and for example, those represented by the general formulas [I] to [V] are preferably used.

The present invention can be applied to various photosensitive materials for printing, X-ray, general negative, general reversal, general positive, direct positive, etc., but requires extremely high dimensional stability. When it is applied to a photosensitive material for printing, a particularly remarkable effect is obtained.

The development temperature of the light-sensitive material according to the present invention is preferably 50 ° C. or lower, and particularly preferably around 25 to 40 ° C. Generally, the development processing time is completed within 2 minutes.
It is particularly preferable to carry out rapid processing for 5 to 60 seconds.

[0069]

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

Example 1 (Latex Synthesis Method Lx-1) Gelatin was added to 40 liters of water.
To a solution containing 0.125 kg and ammonium persulfate 0.05 kg was added sodium dodecylbenzenesulfonate 7.5 g, and the solution temperature was adjusted.
While stirring at 50 ° C, a mixed liquid (35 ° C) of the monomers (a) to (c) (or (a) and (d)) shown below under a nitrogen atmosphere has an average particle size of 0.10 μm. At a similar rate and after stirring for an additional 3 hours, ammonium persulfate
0.005 kg was added and stirred for 1.5 hours. 1 more after the reaction
After removing the residual monomer by steam distillation for an hour, the mixture was cooled to room temperature and adjusted to pH 6.0 with aqueous ammonia. The obtained latex liquid was adjusted to 75.0 kg with water.

(Comparative Latex Synthesis Method Lx-2) Lx
-1, Meito Sangyo KMDS (dextran sulfate ester sodium salt) was used in place of gelatin in the system before polymerization.
Latex Lx-2 was synthesized in the same manner as Lx-1, except that 25 kg was added.

(Emulsion preparation) A silver nitrate solution and an aqueous solution of sodium chloride and potassium bromide were mixed with 8 × of rhodium hexachloride complex.
The solution added to 10 ^-5 mol / Agmol was simultaneously added to the gelatin solution while controlling the flow rate.
A cubic crystal, monodispersed silver chlorobromide emulsion containing 1 μm of silver bromide was obtained.

This emulsion was sulfur-sensitized by a conventional method, and 6-methyl-4-hydroxy-1,3,3a, 7-tetrazaindene was added as a stabilizer, and then the following additives (coating sample 1 m ² ) are added to prepare emulsion coating solutions E-1 to E-14, followed by emulsion protective layer coating solution P-0 and backing layer coating solution B-.
0, a backing protective layer coating solution BP-0 was prepared with the following composition.

(Emulsion coating liquid) Compound (a) 1 mg Sodium hydroxide (0.5N aqueous solution) Adjusted to pH 5.6 Compound (b) 40 mg Compound (c) 30 mg Saponin (20% aqueous solution) 0.5 cc. Sodium dodecylbenzenesulfonate 20 mg 5-methylbenzotriazole 10 mg Compound (d) 2 mg Compound (e) 10 mg Compound (f) 6 mg Latex LX Amount shown in Table 1 Styrene-maleic acid copolymer (thickener) 90 mg Vinyl sulfone type hardener Table 1 Amount shown in

[0075]

[Chemical 12]

[0076]

[Chemical 13]

(Emulsion Protective Layer Coating Solution P-0) Gelatin 1.1 g Compound (g) (1% aqueous solution) 25 cc. Compound (h) 120 mg Compound (Fa) 2 mg Spherical monodispersed silica (8 μm) 20 mg Spherical monodispersed silica ( 3 μm) 10 mg Compound (i) 100 mg Citric acid
Adjusted to pH 6.0 Styrene-maleic acid copolymer (thickener) 100 mg Latex LX Amount shown in Table 1 Vinyl sulfone hardener Amount shown in Table 1 (Backing layer coating solution B-0) Gelatin 1.9 g Compound ( j) 100mg Compound (k) 18mg Compound (l) 100mg Saponin (20% aqueous solution) 0.6cc. Latex (m) 300mg 5-Nitroindazole 20mg Styrene-maleic acid copolymer (thickener) 45mg Glyoxal 4mg Compound (n) ) Epoxy curing agent 10 mg (Backing protective layer coating liquid BP-0) Gelatin 0.7 g Compound (g) (1% aqueous solution) 2 cc. Spherical polymethylmethacrylate (4 μm) 25 mg Sodium chloride 70 mg Glyoxal 22 mg Compound (o) 100 mg

[0078]

[Chemical 14]

[0079]

[Chemical 15]

[0080]

[Chemical 16]

On the emulsion surface side, a corona discharge was applied at 10 W / m ² · min on a polyethylene terephthalate base having a thickness of 100 μm, which was subjected to the undercoating shown in JP-A-59-19941. It was applied using a roll-fit coating pan and air knife. The drying was carried out for 30 minutes at 90 ° C. under a parallel flow drying condition with an overall heat transfer coefficient of 25 Kcal (m ² · hr · ° C.), and subsequently at 140 ° C. for 90 seconds. The thickness of the dried layer was 1 μm, and the surface specific resistance of the layer was 1 × 10 ⁸ Ω at 23 ° C. and 55% RH.

[0082]

[Chemical 17]

Ammonium sulfate 0.5 g / l Polyethylene oxide compound (average molecular weight 6000) 6 g / l Curing agent 12 g / l

[0084]

[Chemical 18]

While adding the hardener solution (shown in Table 1) on this base by the slide hopper method while maintaining the emulsion layer and the emulsion protective layer in this order from the side closer to the support as the emulsion surface side, while maintaining at 35 ° C. After simultaneous multi-layer coating and passing through a cold air set zone (5 ° C.), the backing layer and the backing protective layer were applied while adding a film hardening agent with an arrow stretch slide hopper, and set in cold air (5 ° C.). The coating liquid showed sufficient setting properties when passing through each set zone. Subsequently, both sides were simultaneously dried in the drying zone under the following drying conditions. In addition, after coating the backing surface side, the film was conveyed until it was wound up in a roller, without any contact with other parts. At this time, the coating speed was 150 m / min.

(Drying conditions) After setting, the product was dried with a drying air at 30 ° C. until the weight ratio of water / gelatin reached 800%, and the temperature was adjusted to 800 to 20.
Dry 0% with 35 ° C (30%) dry air, apply the air as it is, and after 30 seconds from the time when the surface temperature reaches 34 ° C (it is considered that the drying is completed), use 48 ° C / 2% RH air. It was dried for 1 minute. At this time, the drying time is 50 seconds from the start of drying to 800% of water / Gel ratio,
It takes 35 seconds from 800% to 200% and 5 seconds from 200% to the end of drying.

This light-sensitive material was wound up at 23 ° C. and 40% RH, then cut under the same environment, and placed in a barrier bag that was conditioned for 3 hours under the same environment (at 40 ° C. and 10% RH for 8 hours. After that, 23 ℃
It was sealed with cardboard which had been conditioned at 40% RH for 2 hours.

The coated silver amount of the light-sensitive material produced as described above was 3.5 g / m ² . The amount of gelatin is 1.2 g / m ^{2 in the} emulsion layer
Met.

The latex in Table 1 is as follows. (Unit: Kg) (1) (A) Butyl acrylate 4.51 (B) Styrene 5.49 (C) Acrylic acid 0.1 (2) (A) Ethyl acrylate 3.52 (B) Methyl methacrylate (two-component system) 5.1 (3) (A) ) Ethyl acrylate 3.52 (ii) Methyl methacrylate 4.9 (iii) Ethylene glycol 0.2 (4) (ii) Ethyl acrylate 3.52 (ii) Methyl methacrylate 4.9 (iii) Styrene 0.1 (5) (ii) Ethyl acrylate 3.0 (ii) Methyl methacrylate 4.0 (C) Styrene 3.0 (D) 2-Acrylamido-2-methylpropanesulfonic acid 0.8 The properties of Samples 1 to 14 obtained as described above were evaluated as follows.

<Dimensional Stability> A sample is cut into a size of 30 cm × 60 cm, two thin lines are imagewise exposed with a bright room printer P-627FM (manufactured by Dainippon Screen Co., Ltd.) at intervals of about 56 cm, and developed. What I did was the manuscript.

This original, unexposed sample (the same size as the original), printer and automatic developing machine were used at 23 ° C. and 20% RH for 2 days.
After the humidity was adjusted for time, the unexposed sample was contact-exposed (face-to-face) to the original and processed by an automatic processor. 2 samples processed
After time humidity adjustment, it was overlaid on the original document, and how much the distance between the fine lines was shifted was measured with a loupe with a scale.

The measurement was carried out at n = 6, and the average was taken.
[(A) Value] The same experiment was conducted at 23 ° C. and 60% RH, and the difference from the value of the dimensional difference before and after the treatment under 20% RH (indicating the dependency on environmental humidity) was taken. [(B) value] When the (a) value exceeds ± 20 μm, dimensional deviation is conscious,
Further, when the value (b) exceeds 20 μm, it is conscious that the dimensional difference before and after the treatment has changed due to the change in environmental humidity, and it is a level at which some working condition setting change is required.

<Film Strength> A sample immersed in a developing solution at 28 ° C. for 30 seconds was crimped to the emulsion surface of the sample with a needle having a sapphire ball with a radius of 0.25 mm at its tip, and moved parallel on the surface at a speed of 5 mm per second. It was evaluated by continuously changing the load applied to the needle in the range of 0 to 200 g weight while performing the measurement, and measuring the load at which damage started on the sample surface.

<Reducing Power> A sample was exposed to light through a wedge for sensitometry using a 150-line contact screen and developed.

The developing treatment was carried out at 28 ° C. for 30 seconds with an automatic developing machine GR-27 (manufactured by Konica) using the following developing solutions and fixing solutions.

The halftone dot strips thus obtained were immersed in a reducing solution having the following composition at 20 ° C. for 20 to 100 seconds and washed with water.

The change in halftone dot area and the change in density per halftone dot of the halftone dot strips thus obtained were measured with a microdensitometer.

After the halftone dots having a halftone dot area of 50% in the halftone dot strips term are subjected to the reduction treatment, the halftone dot area and the required reduction time and the reduction width are obtained when the density of each halftone dot becomes 2.5. Was measured.

Reducer solution ceric sulfate 25 g concentrated sulfuric acid 30 g Water is added to make 1 liter.

Standard processing conditions in the automatic processor are as follows.

Development 28 ° C. 30 sec Fixing 28 ° C. 20 sec Washing with water 15 sec at room temperature Dry 40 ° C. 35 sec Developer formulation (composition A) Pure water (ion exchanged water) 150 cc. Ethylenediaminetetraacetic acid disodium salt 2 g Diethylene glycol 50 g Potassium sulfite ( 55% W / V aqueous solution) 100cc. Potassium carbonate 50g Hydroquinone 15g 5-Methylbenzotriazole 200mg 1-Phenyl-5-mercaptotetrazole 30mg Potassium hydroxide Amount to make the pH of the used solution 10.9 Potassium bromide 4.5g (Composition B) Pure water (ion-exchanged water) 3 cc. Diethylene glycol 50 mg Ethylenediaminetetraacetic acid disodium salt 25 mg Acetic acid (90% aqueous solution) 0.3 cc. 5-Nitroindazole 110 mg 1-Phenyl-3-pyrazolidone 500 mg The above composition in 500 cc. Of water when used The composition A and the composition B were melted in this order and finished to 1 liter for use.

[0102] fixer formulation (Composition A) Ammonium thiosulfate (72.5% W / V aqueous solution) 230 cc. Sodium sulfite 9.5g Sodium acetate trihydrate 15.9g Boric acid 6.7g citric acid sodium dihydrate 2g acetate (90% W / V aqueous solution) 8.1 cc. (Composition B) Pure water (ion exchanged water) 17 cc. Sulfuric acid (50% W / V aqueous solution) 5.8 g Aluminum sulphate (Al ₂ O ₃ equivalent content is 8.1% W / V aqueous solution) 26.5 g When using the fixing solution, dissolve the above composition A and composition B in 500 cc. Of water in this order. It was used after finishing to 1 liter. This fixer pH
Was about 4.3.

The results are summarized in Table 1.

[0104]

[Table 1]

As is clear from Table 1, the samples of the present invention are excellent in dimensional stability, film strength and reducing power.

[0106]

According to the present invention, even when a large amount of latex is added to the gelatin layer, the dimensional stability is excellent, the physical properties of the film are good, and the reducing property is excellent. Material can be provided.

Claims (1)

[Claims] 1. A silver halide having at least one light-sensitive silver halide emulsion layer and a non-light-sensitive hydrophilic colloid layer on a support, and at least one backing layer on the opposite side of the support. In the photographic light-sensitive material, at least one of the constituent layers contains a gelatin-stabilized polymer latex, and the hydrophilic colloid layer is hardened with a vinyl sulfone type hardener, which is a silver halide photographic light-sensitive material. material.