JP2002278009A - Silver halide photographic sensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a silver halide photographic sensitive material excellent in dryability in development while ensuring improved stability of a coating liquid of a silver halide emulsion in a stagnant state. SOLUTION: In the silver halide photographic sensitive material having at least one silver halide emulsion layer on the base, a polymer latex treated with an ultrafiltration membrane is contained in the silver halide emulsion layer and/or another hydrophilic colloidal layer.

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 material (hereinafter, also referred to as a "photosensitive material"), and more particularly to a silver halide photographic material for plate making.

[0002]

2. Description of the Related Art The photoengraving process includes a process of converting a continuous tone original into a halftone image. In this step, ultra-high contrast photographic characteristics are required to form sharper halftone dots. For this purpose, a so-called squirrel-type infectious development technique has been conventionally used in this step, but the developer used there has extremely poor preservation properties, and has recently been described in JP-A-56-106244. As described above, a method of obtaining ultra-high contrast photographic characteristics using a silver halide photographic light-sensitive material containing a hydrazine compound has become common.

In general, a polymer latex is used together with gelatin as a binder in a hydrophilic colloid layer constituting a silver halide photographic light-sensitive material. The main purpose of using polymer latex is to stabilize dimensional accuracy due to the effects of humidity, etc., to improve the adhesion between the coating film and the support, to suppress fog generated by external action,
For reducing silver sludge.

In the process of synthesizing a polymer latex,
A polymer is synthesized using various materials (surfactant, polymerization initiator, etc.). The polymer latex synthesized by the polymer contains components unnecessary for the photosensitive material, such as decomposed pieces of the polymerization initiator, inorganic salts mixed as impurities of the emulsifier, a pH adjuster, and ions (anions and cations). I have.

It has been known that when a polymer latex is used in a photosensitive material containing a hydrazine compound, development is suppressed to cause deterioration in photographic characteristics such as reduction in sensitivity and softening. Further, when a polymer latex is used in the silver halide emulsion layer, the unnecessary components as described above act, and there is a problem that the photographic properties are likely to fluctuate due to the stagnation of the coating solution. Usually, a silver halide emulsion is often kept at a relatively high temperature during preparation and stagnation, and it has been conventionally known to lower the pH of a coating solution or increase pAg as a method for stabilizing the stagnation of a coating solution. However, this method has a disadvantage that sensitivity is reduced.

On the other hand, in the field of recent printing and plate making, there is a demand for shortening the development processing time. Conventionally, the total processing time (Dry to Dry) from the insertion of the leading end of a film into an automatic developing machine having a developing tank, a fixing tank, a washing tank or a stabilizing tank until it comes out of a drying zone usually takes 90 seconds or more. However, in recent years, the total processing time (Dry
(Dry to dry) of 60 seconds or less has to be performed. When the total processing time is shortened, the drying time is inevitably shortened, so that it is necessary to improve the drying property of the photosensitive material. As means for improving the drying property of the photosensitive material, for example,
It is effective to reduce the thickness of the protective layer of the photosensitive material.
However, when the thickness of the protective layer is reduced, the amount of silver ions eluted into the developing solution increases, and the silver ion adheres to the developing tank and the developing roller, thereby contaminating the processed photosensitive material, which is referred to as silver stain. It is desired to consider a method.

[0007] The light-sensitive material is generally provided with a backing layer on the side opposite to the side having the silver halide emulsion layer, but improvement in drying properties after development processing is desired.

[0008]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to improve the coating solution stagnant stability of a silver halide emulsion, and particularly to the coating solution stagnant stability of a silver halide emulsion containing a hydrazine compound. It is to improve.
Another object of the present invention is to provide a silver halide photographic light-sensitive material which is excellent in drying property during development processing.

[0009]

The above object has been achieved by the present invention described below. (1) In a silver halide photographic material having at least one silver halide emulsion layer on a support, the silver halide emulsion layer and / or another hydrophilic colloid layer is processed by an ultrafiltration membrane. Silver halide photographic material containing a polymer latex. (2) The above (1), wherein the polymer latex treated by the ultrafiltration membrane is contained in a hydrophilic colloid located farther from the silver halide emulsion layer as viewed from the support.
3. The silver halide photographic light-sensitive material according to item 1. (3) A silver halide photographic material having at least one silver halide emulsion layer on one side of a support and a backing layer on the other side of the support, wherein the backing layer comprises A silver halide photographic material containing a polymer latex processed by an ultrafiltration membrane.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.
The polymer latex treated by the ultrafiltration membrane used in the silver halide photographic light-sensitive material of the present invention will be described. Polymer latex, in its synthesis process,
A polymer is synthesized using various materials (surfactant, polymerization initiator, etc.). The polymer latex obtained by polymer synthesis contains electrolytes such as decomposed pieces of a polymerization initiator, inorganic salts mixed as impurities of an emulsifier, a pH adjuster, and an ionic surfactant. By including a polymer latex in a silver halide emulsion layer and / or another hydrophilic colloid layer, the present inventors have found that these electrolyte components have an adverse effect on photographic characteristics and film characteristics. Found by experiment. And it turned out that it is effective to use an ultrafiltration membrane in order to remove the component which has this bad influence.

As the material used for the ultrafiltration membrane of the present invention, cellulose acetate and its derivatives, polyacrylonitrile, polysulfone, polyethersulfone, polymer electrolyte complex, aromatic polyamide, polyvinyl alcohol and the like are used. As the type of the module, a flat membrane type, a tube type, a spiral type, a hollow fiber type, and a pleated type are used. For more information on these materials, module types, and products, see “Film Processing Technology
(Supervised by Masayuki Nakagaki, published by Fuji Techno System (199
1)) ”, Chapter II, Chapter 2. The molecular weight cut-off of the preferred ultrafiltration membrane is preferably about 5,000 to 25,000, since the purification efficiency becomes poor when the molecular weight is small, and latex particles leak when the molecular weight is large.

In treating the polymer latex with an ultrafiltration membrane, the number of treatments is preferably plural or more in order to make the effect of the present invention more effective. By performing the treatment a plurality of times, the ionic conductivity decreases, and it is preferable to determine the number of times based on this numerical value. Further, since the ionic conductivity depends on the polymer concentration of the polymer latex, in the present invention, the polymer is diluted with distilled water to have a polymer concentration of 5 watts.
It was adjusted to t% and the temperature was also measured at 25 ° C. In the ionic conductivity measured under these measurement conditions, the preferable range in which the effect of the present invention appears is 0.1 to 1.0 mS / c.
m.

As the polymer latex used in the present invention, a wide range of polymer latex can be used. Examples of the polymer type used are described in Chapter 1 of “Application of Synthetic Latex (Edited by Takaaki Sugimura, Yasuo Kataoka, Soichi Suzuki, Keiji Kasahara, published by Kobunshi Kankokai (1993)). There are styrene-butadiene-based polymer, polystyrene, polyurethane, acrylate-based polymer, polyester, etc. The polymer may be either a homopolymer obtained by polymerizing a single monomer or a copolymer obtained by polymerizing two or more monomers.

Specific examples of the polymer latex used in the present invention include the following commercially available products. For example, as an example of a styrene-butadiene-based polymer, Dainippon Ink and Chemicals, Inc. LACSTAR 3307B,
7132C, 7440N, DS-203, DS-407
H, Nippon Zeon Co., Ltd. Nipol LX416, LX
Examples of polyurethane such as 430, 2507H and the like include HYDRAN AP-1 manufactured by Dainippon Ink and Chemicals, Inc.
0, -20, -30, -40, PATELACOL
As acrylate-based polymers such as H2050 and H2090, VONCOAT manufactured by Dainippon Ink and Chemicals, Inc.
AN155, SFA-33, DV-759, Nipol LX811H, LX814, L manufactured by Zeon Corporation
X857X2 and other polyesters such as FINITEXES650 and ES22 manufactured by Dainippon Ink and Chemicals, Inc.
00 and the like. These polymer latexes may be used alone or in combination of two or more. The amount of the polymer latex used is preferably from 5 to 400% by weight, particularly preferably from 10 to 200% by weight, based on the gelatin in the additive layer.

In the present invention, the coating latex stability of the silver halide emulsion is improved by incorporating the polymer latex treated with the ultrafiltration membrane into the silver halide emulsion layer. In particular, the above effect is remarkable when a hydrazine compound, and further, an amine compound or an onium salt that acts to promote high contrast is contained in the silver halide emulsion layer. Further, the polymer latex treated by the ultrafiltration membrane is applied to a support with a hydrophilic colloid layer on the silver halide emulsion layer (for example, the outermost layer or an intermediate layer between the silver halide emulsion layer and the outermost layer). And a back coat layer to improve the drying property during development processing.

In the silver halide photographic material of the present invention, a protective layer is provided on the silver halide emulsion layer. Alternatively, an intermediate layer may be further provided between the silver halide emulsion layer and the protective layer. When the polymer latex treated by the ultrafiltration membrane of the present invention is contained, it may be contained in either the protective layer or the intermediate layer, or may be contained in both layers. The protective layer and the intermediate layer of the present invention may contain various binders, surfactants, matting agents, slip agents, hardeners and the like.

In the silver halide photographic light-sensitive material of the present invention, a backing layer is provided on the other side of the support including the side including the silver halide emulsion layer and the support. The configuration of this backing layer is a single layer,
Alternatively, it may be a multilayer including a back coating protective layer. When the polymer latex treated by the ultrafiltration membrane of the present invention is contained in the backing surface having a multilayer structure, it is preferably the lowermost layer, but the backing layer, and both the backing protective layer and the backing layer You may make it contain. In the backing layer of the present invention,
It can contain various binders, surfactants, matting agents, slip agents, antihalation dyes, hardeners and the like.

The hydrazine compound used in the light-sensitive material of the present invention is not particularly limited, and is preferably one disclosed in Japanese Patent Application No. 11-246.
No. 323. Further, a compound having an effect of promoting a hardening effect in the presence of a hydrazine compound may be used. Examples of such compounds include JP-A-62-222241 and U.S. Pat. No. 4,975,35.
4, JP-A-8-171166, JP-A-8-19016
5, compounds described in JP-A-8-297339 and the like can be used.

The silver halide emulsion used in the silver halide photographic light-sensitive material of the present invention has a chloride content of 50 mol%.
That is all. Particularly preferably, the bromide content is at least 1 mol%. When it contains iodide, its content is at most 3 mol%, more preferably at most 1 mol%. The shape of the silver halide grains may be irregular or plate-like in addition to regular crystals such as cubic and octahedral, but cubic ones are particularly preferred.

The average size of the silver halide emulsion grains used in the present invention is a fine grain having a size of 0.3 μm or less, particularly preferably in a range of 0.15 to 0.25 μm.
Those having a coefficient of variation represented by {(standard deviation of particle size) / (average particle size)} × 100 are preferably 15% or less, more preferably 10% or less.

For the grain formation of the silver halide emulsion used in the present invention, methods known in the art such as forward mixing, reverse mixing, simultaneous mixing and the like are used. In particular, it is preferable to use a so-called controlled double jet method, which is one of the simultaneous mixing methods and maintains pAg in a liquid phase in which particles are formed at a constant level. In the process of particle formation or physical ripening, a sulfite, a lead salt, a thallium salt, a rhodium salt or a complex salt thereof, an iridium salt or a complex salt thereof may coexist.

The silver halide emulsion used in the present invention is:
It is preferable to sensitize with various chemical sensitizers, and common methods in the art such as sulfur sensitization, selenium sensitization, and noble metal sensitization can be used alone or in combination. For optimal sensitization, thiocyan compounds, thioether compounds, azaindene compounds,
A thiosulfonic acid compound may be present.

The silver halide emulsion used in the present invention is:
It may be spectrally sensitized by a sensitizing dye. As a sensitizing dye, Research Disclosure It
em18716 (p.647, November 1979), Item 308119, IV-A (December 1989)
Month p. 993) or in the cited document. In particular, cyanine, merocyanine, complex cyanine, and complex merocyanine dyes are useful, and these sensitizing dyes may be used alone or in combination of two or more.

As the various additives used in the light-sensitive material of the present invention, known photographic additives can be used. These are the Research Disclosure Items
m 17643 (December 1978) and 18716
(November 1979) 308119 (December 1989
) Or in the cited references.

As the support which can be used as the silver halide light-sensitive material of the present invention, any support known in the art can be used, and in particular, polyester films such as cellulose acetate and polyethylene terephthalate are exemplified. be able to. These supports are
If necessary, an undercoating process or an antistatic treatment may be performed.

There are no particular restrictions on the developer and developing method for developing the photosensitive material of the present invention.
Preferably, a developing solution and a developing method described in Japanese Patent Application No. 11-69353 are used.

[0027]

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is of course not limited by these descriptions.

Example 1 <Preparation of Silver Halide Emulsion Coating Solution> A cubic monodisperse having an average particle size of 0.20 μm was prepared by a pAg controlled double jet method while maintaining the mixing temperature at 60 ° C.
Silver iodobromide chloride grains containing 2.5 × 10 ⁻⁷ mol / mol Ag of rhodium chloride and 6.0 × 10 ⁻⁷ mol / mol Ag of iridium chloride (chloride content 70%, iodide content Rate 0.15%) in the presence of ion-exchanged lime-processed ossein gelatin. The emulsion was coagulated by flocculation using a styrene sulfonic acid-maleic anhydride copolymer and sodium sulfate as a coagulation aid, washed with water, re-dissolved by adding gelatin, and added to the emulsion with thiol per mole of silver. Sodium sulfate 6mg, chloroauric acid 8
mg, and heated at 55 ° C. for 60 minutes to perform chemical sensitization, and then 2-methyl-4-hydroxy-1,3,3a, 7
-100 mg of tetrazaindene per mole of silver, 1-
Phenyl-5-mercaptotetrazole was added at 60 mg per mole of silver. Furthermore, the following compound as a sensitizing dye (D-1) to 2.5 × 10 ^-5 mol / mol Ag was added, the following compounds as a surfactant (S-1) to 50 mg / m ^2, the Hairokinon 80 mg / m ² After adding 4 mg / m ^{2 of} the following compound (H-1) as a hydrazine compound and 15 mg / m ² of the following compound (CP-1) as a high contrast enhancer, the mixture was divided. As shown in Table 1, the polymer latex of the present invention was added to the divided emulsion at a polymer solid content of 0.5%.
g / m ^2, and further, a hardening agent 1,3-divinylsulfonyl-2-propanol was added at 40 mg / m ² , and then 3.5 g / m ² of silver and gelatin were added on the polyethylene terephthalate film. Coating was performed so as to be 2.0 g / m ² .

<Ultrafiltration of polymer latex> As a polymer latex, a carboxylated SBR latex LACSTAR 74 manufactured by Dainippon Ink and Chemicals, Inc.
Using 40N (polymer solid content 42 wt%) and a special modified urethane resin PATELACOL H2090 (polymer solid content 41 wt%) manufactured by the company, each was diluted with distilled water so that the polymer solid content was 5 wt%. ) Ultrafiltration was performed a plurality of times using an ultrafilter P0200 (fraction molecular weight: 20,000), and the ionic conductivity of each was set to 0.5 mS / cm. Incidentally, the conductivity of distilled water used as dilution water is 0.1.
46 μS / cm.

<Preparation of Emulsion Protective Layer Coating Solution> At the same time, a surfactant (S
-1) and (S-2), an amorphous silica matting agent, an acrylate latex, colloidal silica, and a hardening agent were added, and the mixture was coated so that the gelatin became 1.0 g / m ² .

[0031]

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The back of the support has a back layer and a back protective layer of the following formulation. <Adjustment of back layer coating solution> Amount per 1 m ² Gelatin 1.5 g Dye 1 100 mg Dye 2 30 mg Surfactant S-1 30 mg Acrylate latex 0.6 g 1,3-divinylsulfonyl-2-propanol 60 mg <Preparation of coating liquid for back protective layer> Amount per 1 m ² Gelatin 1.0 g Surfactant S-1 15 mg Surfactant S-2 3 mg Polystyrene fine particles (average particle diameter 6 μm) 30 mg 1,3 -Divinylsulfonyl-2-propanol 40 mg

[0033]

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<Evaluation of stagnation stability of silver halide emulsion coating liquid> The silver halide emulsion coating liquids prepared as described above were coated one hour, six hours, and 18 hours after the adjustment, respectively. One hour after the adjustment, the coated sample was evaluated for photographic properties (difference in relative sensitivity, fog) with the sample coated 6 hours and 18 hours later, based on the sample coated.

<Evaluation of photographic characteristics>
After annealing for 7 days, step wedge and 600n
m. Exposure for ^10-5 seconds with a xenon flash sensitometer through a color filter that transmits only wavelengths of at least m, and using a developer of the following composition and a CF-901 fixing solution manufactured by Mitsubishi Paper Mills, a roller transport type automatic developing machine (large The treatment was performed at 35 ° C. for 30 seconds using LDT-1060 manufactured by Nippon Screen Manufacturing Co., Ltd. In each sample, the sensitivity obtained by sensitometry of the sample applied 1 hour after the adjustment was relatively set to 100, and the relative sensitivity difference between the sample applied 6 hours after the adjustment and the sample applied 18 hours after the adjustment was expressed. did. The sensitivity is the reciprocal of the exposure amount that gives a transmission density of 3.0. Fog was evaluated in the same manner as the relative sensitivity difference, using the Dmin value of the developed sample as the fog value. Gamma was determined by tan θ of the linear portion where the transmission density of the developed sample was 1.0 to 2.5.

<Formulation of developer> Potassium sulfite 65 g Potassium carbonate 15 g Potassium hydroxide Amount required to adjust pH to 10.5 Diethylene glycol 35 g Hydroquinone 25 g 4-Methyl-4-human-peroxymethyl-1-phenyl-3-hydroxy-3-peritone 1 0.0 g diethylenetriaminepentaacetic acid 2.0 g potassium bromide 5.0 g 5-methylbenzotriazole 0.3 g The following compound (AS) 0.5 g Water was added to make 1 liter.

[0037]

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[0038]

[Table 1]

From the results shown in Table 1, it can be seen that the use of the polymer latex treated with the ultrafiltration membrane causes little change in photographic properties during stagnation of the silver halide emulsion coating solution and is excellent in stagnation stability. Understand.

Example 2 A silver halide emulsion coating solution was prepared in the same manner as in Example 1, and the formulation of the emulsion protective layer to be coated simultaneously was as follows. The same polymer latex as the emulsion protective layer was used for each sample in the silver halide emulsion layer. The back layer is the same as in the first embodiment.

<Preparation of Coating Solution for Emulsion Protective Layer> Amount per 1 m ² Gelatin 1.0 g Surfactant S-1 30 mg Surfactant S-2 5 mg Amorphous silica matting agent (average particle size 3.5 μm) 20 mg polymer latex (shown in Table 2) 0.2 g (solid content) colloidal silica 0.2 g 1,3-divinylsulfonyl-2-propanol 20 mg

<Evaluation of Drying Property> After coating and annealing at 40 ° C. for 7 days, a roller transport type automatic developing machine (CF-901 fixing solution manufactured by Mitsubishi Paper Mills, Inc.) and a developing solution having the same composition as in Example 1 were used. LDT-1 manufactured by Dainippon Screen Mfg. Co., Ltd.
060), the composition was processed under the following processing conditions, and the drying property when it came out of the automatic developing machine was evaluated by feeling to 5 ranks. A level of 2 or less was undried and not practical, and a level of 3 to 5 was practical and 5 was the best level that was completely dry.

[0043]

[0044]

[Table 2]

From the results shown in Table 2, it can be seen that the use of the polymer latex treated with the ultrafiltration membrane has superior drying properties as compared with the comparison.

Example 3 A silver halide emulsion coating solution was prepared in the same manner as in Example 1, and the formulation of the emulsion protective layer to be coated simultaneously and the intermediate layer provided between the emulsion protective layer and the silver halide emulsion layer were as follows. It is on the street. The polymer latex used for the silver halide emulsion layer was the same as the intermediate layer in each sample. The back layer is the same as in the first embodiment. For the evaluation method, the same dryness test as in Example 2 was performed.

<Preparation of Coating Solution for Emulsion Protective Layer> Amount per 1 m ² Gelatin 0.5 g Surfactant S-1 30 mg Surfactant S-2 5 mg Amorphous silica matting agent (average particle size 3.5 μm) 20 mg Colloidal silica 0.2 g 1,3-Divinylsulfonyl-2-propanol 20 mg <Preparation of coating liquid for intermediate layer> Amount per 1 m ² Gelatin 0.5 g Surfactant S-1 20 mg Polymer latex ( (Shown in Table 3) 0.2 g (solid content)

[0048]

[Table 3]

From the results shown in Table 3, it can be seen that the use of the polymer latex treated with the ultrafiltration membrane resulted in superior drying properties as compared with Example 2 as compared with Example 2.

Example 4 A silver halide emulsion coating solution was prepared in the same manner as in Example 1, and the emulsion protective layer to be coated simultaneously had the same formulation as in Example 2. The same polymer latex as used in Sample 2 of Example 2 was used for the silver halide emulsion layer and the emulsion protective layer.

A back layer and a back protective layer having the following formulation were provided on the back surface of the support, and a polymer latex used for a coating solution for the back layer was produced by Dainippon Ink and Chemicals, Inc.
AR7440N was treated with an ultrafiltration membrane and was not treated.
1,42.

<Preparation of Coating Solution for Back Layer> Amount per 1 m ² Gelatin 2.2 g Dye 1 100 mg Dye 2 30 mg Surfactant S-1 30 mg LACSTAR 7440N 0.5 g (solid content) 1,3- Divinyl sulfonyl-2-propanol 70 mg <Preparation of coating solution for back protective layer> Amount per 1 m ² Gelatin 1.2 g Surfactant S-1 15 mg Surfactant S-2 3 mg Polystyrene fine particles (average particle diameter 6 μm) ) 30 mg 1,3-divinylsulfonyl-2-propanol 45 mg

<Evaluation of Drying Property> Ten samples of A3 size samples were continuously processed under the same developing conditions as in Example 1, and the drying properties of the samples were evaluated. However, the environmental conditions of the test were evaluated at 25 ° C. and 80% RH assuming a hot and humid place. The results are as follows.

Sample 41 using the polymer latex in which the back layer of the present invention was treated with an ultrafiltration membrane was 10%.
The first sheet was completely dry, and the touch was good. However, the sample 42 using the polymer latex in which the back layer was not treated with the ultrafiltration membrane,
When the tenth sample was touched, it was clearly wet, and the continuous treatments were stuck together. From these results, it is understood that the drying property is improved even when the polymer latex of the present invention is used for the back layer.

[0055]

According to the present invention, it is possible to provide a silver halide photographic light-sensitive material having stable coating solution stagnation of a silver halide emulsion and excellent drying property during development processing.

Claims (5)

[Claims] 1. A silver halide photographic material having at least one silver halide emulsion layer on a support,
A silver halide photographic material comprising a polymer latex treated by an ultrafiltration membrane in the silver halide emulsion layer and / or another hydrophilic colloid layer. 2. The silver halide photographic material according to claim 1, wherein the silver halide emulsion layer contains a polymer latex treated with an ultrafiltration membrane. 3. The silver halide photographic material according to claim 2, wherein the silver halide emulsion layer contains a hydrazine compound. 4. The silver halide according to claim 1, wherein the hydrophilic latex contains a polymer latex treated by an ultrafiltration membrane in a hydrophilic colloid located farther from the silver halide emulsion layer as viewed from the support. Photosensitive material. 5. A silver halide photographic material having at least one silver halide emulsion layer on one side of a support and a backing layer on the other side of the support, wherein the backing layer A silver halide photographic light-sensitive material containing therein a polymer latex processed by an ultrafiltration membrane.