JPH0635097A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To provide a silver halide photographic sensitive material for print which is free from contamination of residual color due to dyes after development and excellent in quality of a void character. CONSTITUTION:In the silver halide photographic sensitive material has a silver halide emulsion layer and a nonphotosensitive hydrophilic colloid layer on a supporting body, the silver halide emulsion layer and the nonphotosensitive hydrophilic colloid layer contain at least one kind of polymer latex stabilized with gelatine and the silver halide emulsion layer and/or the nonphotosensitive hydrophilic colloid layer contain at least one kind of water-soluble dye having the max. absorption wavelength in 400-500nm range.

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 for printing which is excellent in character extraction and has no residual color contamination.

[0002]

BACKGROUND OF THE INVENTION In a silver halide photographic light-sensitive material,
For the purpose of adjusting the sensitivity in a specific wavelength range, the emulsion layer or the adjacent layer is often colored with a water-soluble dye.

For example, the spectral sensitivity of the silver halide emulsion layer is controlled, fogging due to light emitted from an unnecessary light source is prevented, and further the sensitivity is adjusted so that it can be handled in a bright room. Can be mentioned.

Such a coloring layer may be a so-called filter layer provided on the side farther from the support than the silver halide emulsion layer, or may be a silver halide emulsion layer directly in some cases. .

It is an essential requirement that the colored layer is such that the dye is decolorized or dissolved in the course of photographic processing and does not remain as color contamination on the processed light-sensitive material.

Therefore, many efforts have been made to date,
Many dyes having no residual color have been proposed, for example, U.S. Pat. No. 3,247,127, Japanese Patent Publication No. 39-22069, and Japanese Patent Laid-Open No. 50-91627.
No. 5, oxonol dyes described in JP-A No. 52-34716, styryl dyes represented by US Pat. No. 1,845,404,
Merocyanine dye represented by U.S. Patent 2,493,747,
Cyanine dyes represented by US Pat. No. 2,843,486 are disclosed. However, it cannot be said to be sufficient because it has drawbacks that the spectral characteristics or photographic performance as a dye is not excellent, and that the color remains after rapid processing.

In particular, in order to prepare a plate for a blank character (printing a negative character on a plate having a solid background or halftone) necessary for a photosensitive material for printing, it is easy to adjust the sensitivity and the residual color There has been a strong demand for a silver halide photographic light-sensitive material that is free from defects and has a good finished quality.

[0008]

SUMMARY OF THE INVENTION It is, therefore, an object of the present invention to provide a silver halide photographic light-sensitive material which is excellent in extraction character performance for printing, has no residual color contamination, and has a good finished quality. Other objects will be apparent from the following specification.

[0009]

The above object of the present invention is to provide at least one gelatin-stabilized polymer latex in a light-sensitive silver halide emulsion layer and a non-light-sensitive hydrophilic colloid layer coated on a support. The silver halide photographic light-sensitive material contains a non-photosensitive hydrophilic colloid layer containing at least one water-soluble dye having an absorption maximum of 400 nm to 500 nm.

The present invention will be described in detail below.

First, the polymer latex contained in the photosensitive silver halide emulsion layer and the non-photosensitive hydrophilic colloid layer in the present invention will be described.

Usually, the latex is dispersed in water by a surfactant, whereas the latex used in the present invention is characterized in that the surface and / or the inside of the polymer latex is dispersion-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 directly bonded or may be bonded via a crosslinking agent.

Therefore, the monomers constituting the latex include carboxyl group, amino group, amide group, epoxy group, hydroxyl group, aldehyde group, oxazoline group, ether group, ester group, methylol group, cyano group, acetyl group and unsaturated carbon. It is desirable to include those having a reactive group such as a bond.

When a cross-linking agent is used, for example, an aldehyde-based agent which is used as a cross-linking agent for ordinary gelatin,
A cross-linking agent such as glycol-based, triazine-based, epoxy-based, vinyl sulfone-based, oxazoline-based, methacrylic-based, acrylic-based or the like can be used.

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

Incidentally, US Pat. No. 5,026,632 has a Tg of 25.
Disclosed is a technique for improving pressure resistance by adding particles having a hard shell of gelatin hardened with a crosslinking agent to pre-polymerized polymer particles at a temperature of ℃ or below in a silver halide photographic material layer. .

Further, US Pat. Nos. 4,920,004 and 4,855,219 disclose a technique for improving adhesiveness by using a prepolymerized polymer particle covalently bound to gelatin as a matting agent.

Further, US Pat. No. 2,852,382 describes synthesizing a polymer in the presence of gelatin, or US Pat.
No. 787,545 discloses a method for desalting a silver halide emulsion using a graft polymer of gelatin and acrylic acid.

However, these polymers did not contribute to the residual color contamination after the processing of the light-sensitive material by the dye, which is the object of the present invention, and the improvement of the blank character performance required for the light-sensitive material for printing.

The present inventor has found that in the course of continuing various studies on polymer latex, there is a preferable range for the ratio of the amount of gelatin and latex added during synthesis.

That is, the weight ratio of gelatin to polymer at the time of synthesis (finally obtained as latex) is Gel: Po.
ly = 1: 100 to 2: 1 is preferable, and particularly preferably 1:50 to
It is 1: 2. The average particle size of the polymer latex of the present invention is
It is preferably 0.3 μm or less. Particularly preferred particle size is
It is 0.01 to 0.27 μm.

In the present invention, the total amount of the hydrophilic binder on the side having the light-sensitive silver halide emulsion layer and the non-light-sensitive hydrophilic colloid layer on the support is 3 g / m ² or less. It is a preferred embodiment of the invention that at least 30% contains a polymer latex stabilized with gelatin.

The non-photosensitive hydrophilic colloid layer of the present invention is
A hydrophilic colloid layer that does not substantially contribute to the photosensitivity or the concentration even if it contains silver halide.

Specific examples of the non-photosensitive hydrophilic colloid layer containing a polymer latex include photosensitive layers such as a protective layer, an antistatic layer, a development control layer, an ultraviolet absorbing layer, a filter layer, an antihalation layer and an intermediate layer. Alternatively, a layer other than the backing layer may be used.

The amount of the polymer latex used is 0.05 g based on the silver halide emulsion layer or the non-photosensitive hydrophilic colloid layer.
It is above, and preferably 0.1 g to 2.5 g / m ² .

The polymer latex used in the present invention can change the MFT (minimum film forming temperature) depending on the composition of the monomers, but an MFT of 60 ° C. or lower is effective, and particularly 50 ° C. or lower. Is preferred.

Examples of the constitution of the monomer of the polymer latex used in the present invention include, for example, US Pat. No. 2,772,166.
No., No. 3,325,286, No. 3,411,911, No. 3,311,912,
No. 3,525,620, Research Disclosure No.195
19551 (July 1980) and the like, acrylates, methacrylic acid esters, hydrates of vinyl polymers such as styrene, and the like.

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 proteins, sugar derivatives, cellulose derivatives,
A hydrophilic colloid such as a synthetic hydrophilic polymer substance such as a single or a copolymer can also be used in combination.

As the gelatin, in addition to lime-processed gelatin, acid-processed gelatin or a hydrolyzed product or enzymatically decomposed product of gelatin can be used. As the gelatin derivative, for example, various compounds such as acid halide, acid anhydride, isocyanates, bromoacetic acid, alkanesaltones, vinyl sulfonamides, maleinimide compounds, polyalkylene oxides, and epoxy compounds are reacted with gelatin. What is obtained is used.

Specific examples thereof include US Pat. No. 2,61
4,928, 3,132,945, 3,186,846, 3,312,553
No., British Patents 861,414, 1,033,189, 1,005,784
And Japanese Examined Patent Publication No. 42-26845.

As the above proteins, albumin, casein and the like, cellulose derivatives such as hydroxyethyl cellulose, carboxymethyl cellulose and sulfates of cellulose, and sugar derivatives such as sodium alginate and starch derivatives may be used in combination with gelatin.

As a graft polymer of gelatin and other polymers, gelatin is a homopolymer or homopolymer of gelatin such as acrylic acid, methacrylic acid, derivatives thereof such as esters and amides, and vinyl monomers such as acrylonitrile and styrene. What grafted the polymer can be used. In particular, a graft polymer with a polymer such as acrylic acid, acrylamide, methacrylamide, or hydroxyalkyl methacrylate is preferable as a polymer having some compatibility with gelatin. Examples of these are described in US Pat. Nos. 2,763,625, 2,831,767 and 2,956,884.

The polymer latex used in the present invention must be added to at least one non-photosensitive hydrophilic colloid layer, but if necessary, a plurality of non-photosensitive hydrophilic colloid layers and / or photosensitive layers can be used. It may be added to the hydrophilic colloid layer. Further, 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 polymer latex of the present invention is added and / or the layer to which the polymer latex of the present invention is not added.
When incorporated on both sides of the support, the type and amount of polymer latex incorporated on each side may be the same or different.

The polymer component of the polymer latex contained in the non-photosensitive layer of the present invention is, for example, US Pat.
2,772,166, 3,325,286, 3,411,911, 3,31
1,912, 3,525,620, Research Disclosure No. 195 19551 (July 1980) and the like, and 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, alkyl acrylate such as methyl acrylate and ethyl acrylate, and metaalkyl acrylate such as methyl methacrylate and ethyl methacrylate. Any compound having a double bond such as styrene, styrene sulfonic acid or a salt thereof, N-substituted or unsubstituted acrylamide, vinyl alcohols, hydroxyalkyl methacrylates and butadiene may be selected as a single or copolymerization component. it can.

Specific examples of preferable monomers are given below.

It goes without saying that the latex of the present invention can take any combination (type, composition ratio) of these monomers, and the present invention is not limited to the monomers shown below.

[0039]

[Chemical 1]

[0040]

[Chemical 2]

[0041]

[Chemical 3]

[0042]

[Chemical 4]

[0043]

[Chemical 5]

[0044]

[Chemical 6]

Next, the water-soluble dye having a maximum absorption wavelength in the range of 400 to 500 nm in the silver halide emulsion layer and / or the non-photosensitive hydrophilic colloid layer of the present invention will be described.

The dye according to the present invention has a maximum absorption of 400 to 500.
Any dye may be used as long as it is in the range of nm, but the dye represented by the following general formula [1] or general formula [2] preferably exhibits the desired effects of the present invention.

[0047]

[Chemical 7]

In the general formula [1], R ₁ is a carboxyl group,
Alkyl group (preferably having 1 to 3 carbon atoms), substituted alkyl group (preferably having 1 to 3 carbon atoms, preferable substituents are halogen atom, hydroxy group, etc.), aryl group (preferably phenyl group), alkoxycarbonyl group (alkyl The moiety preferably represents a group selected from a carbon number of 1 to 3) and an aryloxycarbonyl group (preferably a phenyloxycarbonyl group), and R ₂ is an alkyl group (preferably having a carbon number) substituted with a sulfonic acid group or a carboxyl group. 1 to
3) and an aryl group (preferably a phenyl group) substituted with a sulfonic acid group or a carboxyl group, wherein R ₃ , R ₄ , R ₅ and R ₆ are a hydrogen atom, an alkyl group (preferably a carbon group). Formula 1 to 3) and a substituted alkyl group (preferably having 1 to 3 carbon atoms, a preferable substituent is a halogen atom, a hydroxyl group, etc.) is represented by a group or atom.

The synthesis of these dyes is carried out, for example, in Japanese Examined Patent Publication No. 31-1.
It can be synthesized by the method described in No. 0578.

Specific examples of the dye represented by the general formula [1] are shown below, but the invention is not limited thereto.

[0051]

[Chemical 8]

[0052]

[Chemical 9]

[0053]

[Chemical 10]

R ₁ and R _{2 in} the general formula [2] are each a carboxyl group, an alkyl group (preferably an alkyl group having 1 to 3 carbon atoms), a substituted alkyl group (preferably 1 to 3 carbon atoms).
An alkyl group of, a preferred substituent is a halogen atom,
A hydroxyl group), an aryl group (preferably a phenyl group), an alkoxycarbonyl group (the alkyl part preferably has 1 to 3 carbon atoms) and an aryloxycarbonyl group (preferably a phenyloxycarbonyl group), ₃ and R ₄ are each an alkyl group substituted with a sulfonic acid group or a carboxyl group (preferably an alkyl group having 1 to 3 carbon atoms) and an aryl group substituted with a sulfonic acid group or a carboxyl group (preferably a phenyl group) Represents a selected group.

Specific examples of the dye represented by formula (I) are shown below, but the invention is not limited thereto.

[0056]

[Chemical 11]

[0057]

[Chemical 12]

The amount of the above-mentioned dyes to be used varies depending on the kind of the compound and the purpose, but it is usually 5 mg to 1 g, preferably 10 mg to 800 mg per 1 m ² of the light-sensitive material.

The above dye is dissolved in water or a hydrophilic organic solvent such as methanol or ethanol and added. The addition step may be optional, but when it is added to the silver halide emulsion layer, it is preferably added after the completion of chemical ripening or immediately before coating. The silver halide photographic light-sensitive material according to the present invention is not particularly limited with respect to a general additive, a known contrast-increasing agent, a method for producing silver halide grains, a sensitizing method, and the like. No. 230035 and Japanese Patent Application No. 1-266640 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 as a 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%, and particularly preferably 8 × 10 ¹¹ Ω or less.

The antistatic layer is preferably an antistatic layer containing a water-soluble conductive polymer, hydrophobic polymer particles and a reaction product of 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 sulfonic acid group, a sulfuric acid ester group, a quaternary ammonium salt, a tertiary ammonium salt, a carboxyl group and a polyethylene oxide group. To be Sulfonic acid group among these groups,
Sulfate groups and quaternary ammonium bases 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 hydroxy 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. Of these, a carboxyl group, a hydroxy group, an amino group, an epoxy group, an aziridine group, and an aldehyde group are preferably contained. 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.

As the metal oxide, tin oxide, indium oxide, antimony oxide, zinc oxide, or a substance obtained by doping these metal oxides with metal phosphorus or metal indium is preferably used. The average particle size of these metal oxides is preferably 1 μ to 0.01 μ.

Although a matting agent is preferably used, any known matting agent can be used. For example, silica described in Swiss Patent 330,158, glass powder described in French Patent 1,296,995, British Patent 1,173,181
Inorganic particles such as alkaline earth metals or carbonates such as cadmium and zinc described in US Pat. No. 2,322,037, starch described in US Pat. No. 2,322,037, Belgian patent 625,451 or British patent 981,1
Starch derivative described in 98, polyvinyl alcohol described in JP-B-44-3643, polystyrene or polymethylmethacrylate described in Swiss Patent 330,158, polyacrylonitrile described in U.S. Patent 3,079,257, U.S. Patent 3,022,169 Organic particles such as the polycarbonates described in 1. can be included. The matting agents may be used alone or in combination. The shape of the matting agent is preferably spherical as a regular matting agent, but may be other shapes such as flat plate and cubic. The size of the matting agent is represented by the diameter when the volume of the matting agent is converted into a spherical shape. In the present invention, the matte particle size refers to the spherically converted diameter.

In a preferred form, the outermost layer on the emulsion surface side preferably contains 4 to 80 mg / m ² of at least one fixed and / or irregular matting agent having a matting particle size of 4 μm or more. More preferably, a regular particle size of less than 4 μm and / or
Or, at least one type of irregular matting agent is 4 mg / m ^{2 to} 80 m
It is to contain g / m ² together.

The fact that the matting agent is contained in the outermost layer means that
At least one part of the matting agent is preferably contained in the outermost layer, and one part of the matting agent may reach a layer below the outermost layer.

In order to fulfill the basic function of the matting agent,
It is desirable that a part of the matting agent is exposed on the surface.
Further, the matting agent exposed on the surface may be a part of the added matting agent or all. The method of adding the matting agent is
It may be a method of dispersing in a coating liquid in advance and coating, or a method of spraying a matting agent after coating the coating liquid and before completion of drying. When adding a plurality of different matting agents, both methods may be used in combination. Manufacturing techniques for more effectively adding these matting agents to the light-sensitive material are described in Japanese Patent Application No. 1-228762.

As the undercoat layer that can be used in the present invention, an undercoat layer containing an organic solvent system containing polyhydroxybenzenes described in JP-A-49-3972, JP-A-49-11118.
No. 52, No. 52-104913, No. 59-19941, No. 59-19940, No. 5
9-18945, 51-112326, 51-117617, 51-5846
No. 9, 51-114120, 51-121323, 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, but also U.S. Patent Nos. 2,698,235 and 2,779,6.
And vinylidene chloride-based subscripts described in Nos. 84 and 4,645,731.

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 undercoat layer is distinguished from the coating layer according to the present invention, and there is no restriction on the coating timing or conditions.

[0073]

EXAMPLES Examples of the present invention will be specifically shown below, but it goes without saying that the present invention is not limited to these examples.

Example 1 (Synthesis of latex Lx-2) 0.125 gelatin was added to 40 l of water.
Liquid temperature 80 in a liquid containing Kg and 0.05 Kg ammonium persulfate.
While stirring at ℃ under a nitrogen atmosphere, (a) n-butyl acrylate 4.51Kg, (a) styrene 5.49Kg, (c) acrylic acid 0.1Kg mixture was added over 1 hour, then 1.5
After stirring for 1.25 hours, gelatin 1.25 kg and ammonium persulfate 0.00
After adding 5 kg and stirring for 1.5 hours, after completion of the reaction, steam distillation was carried out for another hour to remove residual monomers, and after cooling to room temperature, pH was adjusted to 6.0 using ammonia. The obtained latex liquid was adjusted to 50.5 Kg with water.

As described above, a monodisperse latex having an average particle size of 0.25 μm and Tg of about 0 ° C. was obtained.

(Synthesis of Comparative Latex Lx-1) Lx-
1, in the system before polymerization, instead of gelatin, Meito Sangyo
KMDS (dextran sulfate sodium salt) 0.25
Latex Lx-1 was synthesized in the same manner as Lx-1, except that Kg was added and gelatin addition after the monomer addition was eliminated.

(Synthesis of Latex Lx-3) To 60 liters of water, 1.0 kg of gelatin, 0.01 kg of sodium dodecylbenzenesulfonate and 0.05 kg of ammonium persulfate were added, and the mixture was stirred at a liquid temperature of 60 ° C. under a nitrogen atmosphere. (A) Styrene 3.
0 kg (a) A mixture of 3.0 kg of methyl methacrylate and 3.2 kg of (u) ethyl acrylate, and 0.8 kg of sodium salt of 2-acrylamido-2-methylpropanesulfonic acid were added over 1 hour, and the mixture was further stirred for 1.5 hours and then 1 more. After steam distillation was carried out for an hour to remove residual monomers, 0.5 kg of gelatin was added, and an appropriate amount of the bactericide described later was added, and after cooling to room temperature, the pH was adjusted to 6.0 with ammonia.

The latex solution obtained was made up to 75 kg with water. Thus, a monodisperse latex Lx-3 having an average particle size of 0.1 μm was obtained.

(Emulsion preparation) A silver sulfate solution and an aqueous solution of sodium chloride and potassium bromide were mixed with 8 × rhodium hexachloride complex.
The solution added to 10 ^-5 mol / Agmol was simultaneously added to the gelatin solution while controlling the flow rate, and after desalting, the particle size was adjusted to 0.
A cubic crystal, monodisperse, silver chlorobromide emulsion containing 13 μm and 1 mol% of silver bromide was obtained.

This emulsion was subjected to sulfur sensitization by a conventional method, 6-methyl-4-hydroxy-1,3,3a, 7-tetrazaindene was added as a stabilizer, and then the following additives were added to the emulsion. A coating solution was prepared, and then an emulsion protective layer coating solution P-0, a backing layer coating solution B-0, and a backing protective layer coating solution BP-0 were prepared with the following compositions.

(Preparation of Emulsion Coating Solution) Compound (a) 1 mg / m ² NaOH (0.5N) adjusted to pH 5.6 Compound (b) 40 mg / m ² Compound (c) 30 mg / m ² saponin (20%) 0.5 cc / m ² sodium dodecylbenzenesulfonate 20 mg / m ² 5-methylbenzotriazole 10 mg / m ² compound (d) 2 mg / m ² compound (e) 10 mg compound (f) 6 mg / m ² polymer latex (Lx-1 or Lx-2) Amount shown in Table 1 Styrene-maleic acid copolymer hydrophilic polymer (thickener) 90 mg / m ²

[0082]

[Chemical 13]

[0083]

[Chemical 14]

(Emulsion protective layer coating solution P-0) Gelatin 0.5 g / m ² Compound (g) (1%) 25 cc / m ² Spherical monodisperse silica (8 μm) 20 mg / m ² 〃 (3 μm) 10 mg / m ² Compound (h) 100 mg / m ² Citric acid adjusted to pH 6.0 Polymer latex (Lx-1 or Lx-2, Lx-3) Amount shown in Table 1 Water-soluble dye Amount shown in Table 1 (Backing layer coating liquid B- 0) Gelatin 1.0 g / m ² compound (i) 100 mg / m ² compound (j) 18 mg / m ² compound (k) 100 mg / m ² saponin (20%) 0.6 cc / m ² latex (l) 300 mg / m ² 5-nitroindazole 20 mg / m ² styrene-maleic acid (thickener) 45 mg / m ² glyoxal 4 mg / m ² compound (n) 100 mg / m ² (backing protective layer coating solution BP-0) gelatin 0.5 g / m ² compound (g) (1%) 2cc / m ² spherical polymethylmethacrylate (4μm) 25mg / m ² sodium chloride 70mg / m ² Glyoxal 22mg / m ² Compound (o) 10mg / m ²

[0085]

[Chemical 15]

[0086]

[Chemical 16]

[0087]

[Chemical 17]

Each of the coating solutions prepared as described above was used in
10W / (m ² · mi on a 100 μm thick polyethylene terephthalate base with undercoating shown in No. 9-19941
After the corona discharge was applied in n), it was applied with the following composition using a roll-fit coating pan and an air knife. In addition, drying is 90 ℃, overall heat transfer coefficient 25 Kcal (m ² · hr ·
(° C) parallel flow drying conditions for 30 minutes, followed by 140 ° C for 90 seconds. The thickness of this layer after drying was 1 μm, and the surface specific resistance of this layer was 1 × 10 ⁸ Ω at 23 ° C. and 55%.

[0089]

[Chemical 18]

Ammonium sulfate 0.5 g / l Polyethylene oxide compound (average molecular weight 600) 6 g / l Curing agent 12 g / l

[0091]

[Chemical 19]

On this base, the emulsion layer and the emulsion protective layer were coated in this order from the side closer to the support as the emulsion side, at the same time while maintaining the temperature at 35 ° C., while simultaneously adding a hardener solution by the slide hopper method, and setting with cold air. After passing through the zone (5 ° C.), the backing layer and the backing protective layer were coated by the slide hopper while adding the hardening agent, and set with 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 100 m / min.

(Drying condition) After setting, the product was dried with a dry air at 30 ° C. until the weight ratio of H ₂ O / gelatin reached 800%, and then 800 to 20.
0% was dried with 35 ° C, RH30% dry air, and the air was blown as it was, and after 30 seconds from the time when the surface temperature reached 34 ° C (which is regarded as the end of drying), it was dried with 48 ° C, RH16% air for 1 minute. . At this time, the drying time is from the start of drying to the H ₂ O / Gel ratio of 800%
Was 50 seconds, 800% to 200% was 35 seconds, and 200% to completion of drying was 5 seconds.

This photosensitive material was wound up at 23 ° C. and RH 40%,
Then, it was cut in the same environment and placed in a barrier bag that had been conditioned for 3 hours in the same environment (after conditioned for 8 hours at 40 ° C and RH 10%, 23
Sealed with cardboard at 40 ° C. and RH 40% for 2 h).

In the light-sensitive material produced as described above, the coated silver amount was 3.2 g / m ² and the gelatin amount was 2.
It was 34 g / m ² .

For the emulsion layers, three levels were prepared: a system containing the gelatin-stable polymer latexes (Lx-2 and 3) according to the present invention and a system containing (Lx-1) for comparison. did.

For the protective layer on the emulsion layer, as shown in the table below, the levels of the system with latex added and the system without latex were prepared to prepare 59 kinds of samples.

Standard processing conditions (using Konica's automatic developing machine GR-27) Development 28 ° C 30 seconds Fixing 28 ° C 20 seconds Washing at room temperature 15 seconds Drying 40 ° C 35 seconds [Developer formulation] (Composition A) Pure water (ion exchange Water) 150 ml Ethylenediaminetetraacetic acid disodium salt 2 g Diethylene glycol 50 g Potassium sulfite (55% W / V aqueous solution) 100 ml Potassium carbonate 50 g Hydroquinone 15 g 5-Methylbenzotriazole 200 mg 1-Phenyl-5-mercaptotetrazole 30 mg Potassium hydroxide pH To 10.9 Potassium bromide 4.5g (Composition B) Pure water (ion exchanged water) 3ml Diethylene glycol 50mg Ethylenediaminetetraacetic acid disodium salt 25mg Acetic acid (90% aqueous solution) 0.3ml 5-Nitroindazole 110mg 1-Phenyl-3- When using a pyrazolidone 500 mg developer, the above composition A and composition B are added to 500 ml of water.
Were melted in this order and finished to 1 l for use.

[Fixing solution formulation] (Composition A) Ammonium thiosulfate (100% conversion) 168.2g Pure water 5.0g Sodium sulfite 5.63g Boric acid 9.78g Sodium citrate dihydrate 2.0g Sodium acetate trihydrate 27.8g Acetic acid (90% W / W%) 6.4g (Composition B) Pure water 2.82g Sulfuric acid (50% W / W%) 6.74g Aluminum sulphate (Al ₂ O ₃ equivalent content is 8.1% W / W%) 25.31g Fixing When the liquid was used, the above composition A and composition B were dissolved in this order in 800 ml of pure water, and the solution was finished to 1 l for use. PH of this fixer
Was about 4.38.

The following evaluation was performed on the obtained sample.

(1) Evaluation of Color Remaining Property The obtained film sample was subjected to the following treatment by post-exposure.

Development process at 28 ° C for 30 seconds, fixing process at 28 ° C, 20
Seconds, washing with water at room temperature for 15 seconds, and drying at about 40 ° C. for 35 seconds to prepare samples. This sample was visually evaluated on a 5-point scale.

5 indicates colorless and no residual color, and 1 indicates strong residual color. A level of 3 or less is a residual color level that cannot be generally used.

(2) Evaluation of quality of blank characters When a portion having a halftone dot area of the halftone film is appropriately exposed so that the halftone dot area of the return light-sensitive material becomes 50%,
It is preferable that the image quality reproduces a line width of 50 μm on a line drawing film.

Evaluation was carried out on a scale of 5 with a very good extracted character quality of 5 and a worst level of 1.

[0106]

[Table 1]

[0107]

[Table 2]

[0108]

[Table 3]

As is apparent from the table, the sample according to the present invention has less residual color stain of the dye than the comparative sample and is excellent in quality of blank characters.

Each of these samples of the present invention
In terms of photographic performance, no difference was observed.

[0111]

As described above, according to the present invention, a silver halide photographic light-sensitive material having less residual color stain of a dye after development processing and excellent in clear character quality can be obtained.

Claims (1)

[Claims] 1. A silver halide photographic light-sensitive material having at least one silver halide emulsion layer and a non-photosensitive hydrophilic colloid layer on a support, the silver halide emulsion layer and the non-photosensitive hydrophilic colloid. A water solution containing at least one polymer latex stabilized with gelatin in the layer and having a maximum absorption wavelength between 400 and 500 nm in the silver halide emulsion layer and / or the non-photosensitive hydrophilic colloid layer. A silver halide photographic light-sensitive material containing at least one functional dye.