JPH0151824B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a silver halide photographic material containing a novel latex in its outermost layer, and more particularly to a silver halide photographic material having a latex impregnated with an antistatic agent in its outermost layer. Conventionally, in the production of silver halide photographic materials using plastic film as a support, there are various steps such as winding, winding,
During processes such as rewinding, coating various coating layers including the photosensitive layer, and transportation during drying, electricity is generated due to friction and peeling with other substances, and when this discharges, it becomes photosensitive. The photographic light-sensitive material coated with the layer is exposed to light, and after development, uneven exposure due to irregular static electricity called static marks occurs. Furthermore, when the manufactured photographic material is used or processed, if it is charged with static electricity, it similarly causes static mark failure and various other problems due to the adhesion of dust and the like. The more sensitive the photosensitive material is, the more this static mark occurs, but in addition to the recent increase in the sensitivity of photosensitive materials, there has been an increase in the number of opportunities for them to be subjected to harsh mechanical handling due to high-speed automatic processing. There is a tendency for this to occur even more frequently. In order to improve these static mark failures and other charging failures, methods have been taken to improve the conductivity of photographic light-sensitive materials and dissipate the stored charge within a short time before it is discharged. . For example, US Patent No. 2118059, US Patent No. 2139778, US Patent No. 2197998,
Surfactants described in specifications such as No. 2982651 and No. 2591590, or for example US patents
No. 3072484, No. 2725297, No. 3033679, No.
A method is known in which polymers and the like described in various specifications such as No. 2710402 are used as antistatic agents. However, although the antistatic agents that have been developed so far have an antistatic effect, they also have various drawbacks when applied to photographic materials. In other words, although deterioration of the most important photographic properties is out of the question, for example, when developing a photographic material, the antistatic agent added to the photographic material flows out into the processing solution and forms a film of oil on the surface of the processing solution. The phenomenon of so-called oil sludge, which causes uneven development on the photographic film, and the phenomenon that the adhesiveness of the tape deteriorates when the photographic film is adhered with tape after processing have been observed, and it is necessary to overcome these various drawbacks. was required. Therefore, a first object of the present invention is to provide a silver halide photographic material in which charging failures such as static marks are prevented without adversely affecting photographic performance such as sensitivity and fog. A second object of the present invention is to provide a silver halide film that does not cause the antistatic agent to leak into the processing solution during photographic processing, causing uneven development, or reducing the adhesion to the tape after processing. Our objective is to provide photographic materials. As a result of various studies to achieve the above objectives,
A silver halide photographic light-sensitive material characterized in that the outermost layer of the constituent layers contains an oil-in-water polymerization dispersion containing a repeating unit represented by the following general formula. [General formula] (In the formula, R and R′ each represent a hydrogen atom or a methyl group, R″ represents a hydrogen atom, an alkyl group, or an aryl group, and n represents a positive integer from 2 to 100. However, the oil droplet dispersion in water The monomer represented by the general formula used in the present invention can be synthesized by various methods, but for example, 1972
It can be synthesized by the method described in Publication No.-786. Examples of monomers represented by the general formula are shown below,
It is not limited to this. Compound example (1) CH ₂ = CH-COO (-CH ₂ CH ₂ O) - ₈ H (2) CH ₂ = CH-COO (-CH ₂ CH ₂ O) - ₃₀ H A latex using the monomer represented by the above general formula can be obtained by a commonly used so-called emulsion polymerization method. Of course, all of the monomers represented by the above general formula are water-soluble, so in order to obtain a latex, it is necessary to copolymerize monomers that become water-insoluble. Examples of the monomer include acrylic esters, methacrylic acids, vinyl esters, vinyl halides, vinyl ethers, and styrene. Of course, it is possible to copolymerize other water-soluble monomers as long as they have a composition that will form a latex. From the above, the copolymerization ratio etc. cannot be determined exactly depending on the type of monomer used, but it is preferable that the monomer represented by the above general formula accounts for 50% or less by weight,
In particular, a content between 30% and 1% seems to be preferable from the viewpoint of both latex stability and antistatic effect. The composition of the latex used will be listed below, but it is not limited thereto. Polymer example In the emulsion polymerization method for obtaining the latex described above, the emulsion polymerization can be carried out using less or no emulsifiers that are commonly used. Conventionally, when a latex produced using an emulsifier is added to a silver halide photographic material, the emulsifier causes fog and reduces sensitivity, which adversely affects photographic performance, and also reduces the antistatic effect. This phenomenon is likely to occur. Therefore, the ability to produce latexes without the use of emulsifiers is the most desirable requirement for obtaining antistatic effects. In addition, in the present invention, as a means to further improve the antistatic effect, a latex composition obtained by impregnating an antistatic agent into an oil-in-water polymer dispersion obtained by polymerizing monomers represented by the general formula is halogenated. It is most desirable to include it in the outermost layer of the silver photographic material. The above-mentioned antistatic agents include all known photographic antistatic agents such as anionic antistatic agents, cationic antistatic agents, amphoteric antistatic agents, and nonionic antistatic agents. Next, the method of impregnating the latex obtained from the monomer of the present invention with the above-mentioned antistatic agent can be roughly divided into the following five methods. 1. A solution of an antistatic agent dissolved in a water-soluble organic solvent is mixed with latex. Thereafter, the organic solvent is removed if necessary. 2. A solution of an antistatic agent dissolved in a substantially water-insoluble organic solvent is mixed with latex, and stirred vigorously if necessary. Thereafter, the organic solvent is removed if necessary. 3. Add the antistatic agent directly to the latex and mix, stirring vigorously if necessary. (iv) A solution obtained by dissolving a polymer obtained by a normal polymerization method in an appropriate organic solvent is mixed with a solution in which an antistatic agent is added to an appropriate aqueous solvent such as water, and a surfactant is added as necessary. The above polymer is emulsified and dispersed by stirring vigorously. after that,
Remove organic solvent if necessary. (v) When manufacturing latex, an antistatic agent is present and polymerized. By using the above-mentioned impregnation method, the polymer in the latex can be impregnated with one or more antistatic agents, and the latex composition used in the present invention can be obtained. The entire amount of the antistatic agent mixed in the latex of the present invention does not need to be impregnated into the polymer particles, but it may be partially impregnated and the remainder present in the dispersion medium of the latex. Preferably, the impregnation rate of antistatic agent (weight of antistatic agent impregnated into polymer particles in latex/weight of antistatic agent added to latex) is at least about 10%, and even more from 20 to 90%. preferable. In the above-mentioned impregnation method, examples of the organic solvent used to dissolve the antistatic agent and the polymer include those described in US Pat. No. 2,801,171 and the like. To give specific examples, examples of water-soluble organic solvents include acetone, methanol, ethanol, acetonitrile, dioxane,
Dimethylformamide, etc., and substantially water-insoluble organic solvents include ethyl acetate, butanol, chloroform, carbon tetrachloride, benzene,
Examples include hexane and ethyl ether. Each of these solvents can be used alone or in combination of two or more. Further, it is desirable that the concentration of the latex used in the above method etc. is 5 to 30% by weight. Further, the concentration of the organic solvent in the antistatic agent is arbitrary, but it is usually 1% or more, and preferably
10% or more. Furthermore, it is used in the fourth impregnation method. Although the concentration of the organic solvent solution of the polymer is arbitrary, it is preferably 10% or more. In the latex composition used in the present invention, the concentration of antistatic agent in the latex is 10
~200% by weight, preferably 20-100% by weight,
The above object of the present invention can be achieved within this range. Next, a method for producing a latex polymer [Production method-1] used in the present invention and a typical method for producing a latex composition impregnated with an antistatic agent will be described, but the present invention is not limited to these. [Production method-1] Synthesis of polymer example-1 Pour 400 ml of water into a 500 ml four-necked reactor, add a stirrer, reflux condenser, thermometer, nitrogen gas suction pipe,
and a dropping funnel. After flowing nitrogen gas for about 30 minutes, the temperature was raised to 70°C, 0.5 g of ammonium persulfate was added, and a mixture of compound example (4) and acrylic acid ethyl ester was immediately poured into the dropping funnel.
Drop 100g over approximately 1 hour. After the dropwise addition, heating and stirring were continued for about 3 hours, and then the mixture was cooled to room temperature. The solid concentration was 19.5% and the molecular weight was 100,000. As shown in this example, it is possible to produce a stable latex without using any emulsifier that is normally used in emulsion polymerization, and all of the polymer examples listed can be produced without using an emulsifier. [Manufacturing method-2] Manufacturing example of the latex of the present invention impregnated with the following antistatic agent. Add 10 ml of a methanol solution containing 20% of the following antistatic agent to 50 ml of latex containing 10% (weight %; the same applies hereinafter) of the above polymer [2].
Gradually add dropwise and stir using a magnetic stirrer for 10 minutes. Next, methanol is removed using a rotary evaporator to obtain the desired latex of the present invention. (Antistatic agent) C ₁₈ H ₃₇ O (CH ₂ CH ₂ O) ₁₀ H [Production method-3] Production example of the latex of the present invention impregnated with the following antistatic agent. 30 ml of an ethyl acetate solution containing 20% of the specific example [1] of the above polymer and 30 ml of an ethanol solution containing 10% of the following antistatic agent were added to 60 ml of a 1% aqueous solution of sodium dodecylbenzenesulfonate. and treat for 15 minutes using an ultrasonic disperser. Next, the organic solvent is removed using a rotary evaporator to obtain the desired product. (Antistatic agent) [Production method-4] Production example of the latex of the present invention impregnated with the following antistatic agent. Sodium dodecyl sulfate was added to 50 ml of latex containing 10% of the specific example [5] of the above polymer.
After dissolving 0.05 g, add 5.0 g of the antistatic agent described below and stir for 20 minutes using a magnetic stirrer to obtain the desired product. (Antistatic agent) (However, n ₁ + n ₂ + n ₃ = 12) [Production method-5] Production example of the latex of the present invention impregnated with the following antistatic agent. After adding 20 ml of acetone to 50 ml of latex containing 10% of the above polymer example [4], 3.5 g of the antistatic agent described below is gradually added and stirred for 10 minutes using a magnetic stirrer. The obtained composition is subjected to water dialysis for 24 hours using a cellophane dialysis membrane to obtain the desired product. (Antistatic agent) (However, n ₁ + n ₂ = 12) [Manufacturing method-6] A manufacturing example of the latex of the present invention impregnated with the following antistatic agent. 3 g of gelatin is dissolved in 100 ml of latex containing 8% of the above polymer example [6]. Then 20ml of methanol solution containing 20% of the following antistatic agent
and the above latex solution and stir vigorously for 5 minutes to obtain the desired product. (Antistatic agent) C ₁₂ H ₂₅ COO(CH ₂ CH ₂ O) ₆ H [Production method-7] Production example of the latex of the present invention impregnated with the following antistatic agent. 20% acetone solution of specific example [7] of the above polymer
100 ml and 50 ml of a 20% methanol solution of the following antistatic agent were simultaneously added to 200 ml of a 2% aqueous solution of sodium triisobutylnaphthalene sulfonate,
Perform ultrasonic dispersion treatment for 10 minutes. The organic solvent was then removed using a rotary evaporator.
get the object. (Antistatic agent) HO (CH ₂ CH ₂ O) _o1 − (CH ₂ CH ₂ CH ₂ CH ₂ O) ₁₅ − (CH ₂ CH ₂ O) _o2 H (However, n1 + n2 = 24) [Manufacturing method-8] Below This invention relates to a method of impregnating a latex polymer with an antistatic agent in the presence of a monomer mixture during the polymerization process by the method of Production Method-1. In this case, the mixing ratio may be 50 g of the monomer mixture to 50 g of the antistatic agent. (Antistatic agent) C ₁₂ H ₂₅ COO(CH ₂ CH ₂ O) ₆ H [Manufacturing method-9] Synthesis of polymer example-8 Using the method according to manufacturing method-1, substitute compound example (4) with compound example Polymer Example 8 was synthesized by mixing (5) with acrylic acid ethyl ester. The latex of the present invention is incorporated into a coating composition for an outer layer constituting a silver halide photographic light-sensitive material, and applied to the photographic light-sensitive material. The silver halide photographic material according to the present invention, that is, the silver halide photographic material having a layer coated with a coating composition for an outer layer containing the latex of the present invention is a photographic light-sensitive material as a finished product. It also includes photographic materials as so-called intermediate products. More specifically, in the present invention, the silver halide photographic light-sensitive material refers to a support used for the silver halide photographic light-sensitive material, a support subjected to subbing processing, and a support coated with a packing layer. A silver halide photographic material as an intermediate product in which one or more constituent layers of a photographic light-sensitive material are coated on a support that has been subjected to undercoating as necessary; It refers to all silver halide photographic materials as finished products coated with constituent layers of photographic materials such as pulling layers, intermediate layers, filter layers, antihalation layers, protective layers, and packing layers. Therefore, in the present invention, having a layer coated with an outer layer coating composition containing the latex of the present invention means that the latex of the present invention is coated on the surface of the photographic material in the above sense. , the case where it is applied directly to the surface of the support of the photographic light-sensitive material, and the case where it is applied indirectly to the support through one or more of the above-mentioned constituent layers of the photographic light-sensitive material. From the above-mentioned meaning, the coating composition for an outer layer containing the latex of the present invention is usually a coating composition for forming a subbing layer, an intermediate layer, a filter layer, an antihalation layer, a protective layer, a packing layer, etc. However, it may also be a coating composition for forming a silver halide emulsion layer. As a method for applying the outer layer coating composition containing the latex of the present invention, a conventional method for applying a photographic coating liquid can be adopted. For example, super coat, roller coat, dip coat, spray coat, slide hopper method, etc. can be adopted. The coating amount of the latex of the present invention is determined by the type of photographic material, the type of coating composition for the outer layer containing the latex of the present invention, the type of support, the type and amount of the antistatic agent impregnated into the polymer of the latex, etc. Generally, it is desirable to apply the antistatic agent impregnated into the polymer of the latex of the present invention in an amount of 10 mg to 1 g per square meter of the photographic light-sensitive material, although this varies depending on the type of material used. The outer layer coating composition containing the latex of the present invention can contain various photographic additives depending on the type of the outer layer coating composition. Furthermore, various layers may be further provided on the layer formed by coating the outer layer coating composition containing the latex of the present invention. Examples of such a layer include a slippery layer, a matte layer containing silicon dioxide particles, and a layer containing an anionic material or a fluorine-based material. Supports that can be used in the silver halide photographic material of the present invention include, for example, cellulose triacetate films, polyester films such as polyethylene terephthalate, polycarbonate films, polystyrene films, polyolefin films, polyethylene laminate papers, and other hydrophobic materials. All in film or sheet. Silver halide photographic materials to which the present invention can be applied include all silver halide photographic materials that use a hydrophobic film or sheet as a support. This silver halide photographic light-sensitive material includes general black-and-white light-sensitive materials, special black-and-white light-sensitive materials,
Examples include various intermediate products and finished products such as color photosensitive materials, printing photosensitive materials, and X-ray photosensitive materials. In the present invention, the latex of the present invention can be coated on the outermost layer of a silver halide photographic light-sensitive material, or the latex of the present invention can be applied to a silver halide emulsion layer that is a constituent layer of a silver halide photographic light-sensitive material. At least one of a subbing layer, an intermediate layer, a filter layer, an antihalation layer, a protective layer, a backing layer, etc.
By indirectly adhering the silver halide photographic material to the support of the silver halide photographic material, it is possible to obtain a silver halide photographic material free from charging failures such as static mark failures. . Moreover, the use of the latex of the present invention does not have any adverse effect on photographic properties such as sensitivity, gradation, fog, etc. of silver halide photographic materials. Furthermore, it is possible to obtain an excellent silver halide photographic material that is free from the risk of adhesion or transfer to other adjacent surfaces even in a high-humidity environment, and does not cause sweating even under high temperatures. In addition, there is no opacity or deterioration of antistatic performance due to non-uniform dispersion of the antistatic agent, and the antistatic agent in the photographic light-sensitive material does not dissolve into the processing solution during the processing process. A silver photographic material is obtained. Furthermore, according to the present invention, compared to the conventional method in which antistatic agent is used without impregnating latex, it exhibits remarkable antistatic performance with a small amount of antistatic agent, so the physical properties of the film of photographic light-sensitive materials are greatly improved. You can also do so. Furthermore, in the case of conventional antistatic agents with strong hydrophobicity, uniform dispersion was difficult and coating spots were observed, but according to the present invention, the antistatic agent is added to the polymer in the latex. Since the coating is impregnated, the coating property is greatly improved, coating spots and coating liquid are not repelled, and it is easy to disperse the coating liquid uniformly in the layer. The present invention will now be illustrated by examples, but the embodiments of the present invention are not limited thereto. Example 1 A silver iodobromide gelatin high-sensitivity emulsion containing 1.5 mol % of silver iodide was subjected to gold sensitization and sulfur sensitization during the second ripening, and then 4-hydroxy- as a stabilizer was applied.
6-Methyl-1,3,3a,7-tetrazaindene, mucohalogenic acid as a hardening agent, and saponin as a coating aid were added to give a dry film thickness of 6 microns on a polyethylene terephthalate film subjected to subbing treatment. It was coated and dried. Next, a 2% aqueous gelatin solution 2 containing a hardening agent and a coating aid and having the following composition was prepared. [Gelatin aqueous solution composition] Gelatin 20g Water 500ml 20% saponin 1ml 2% mucochloric acid 5ml Adjust the volume to 1 with water. Next, the sample was divided into four 200 ml portions, and no antistatic agent was added to the first sample, and 1 portion of the latex produced according to Manufacturing Method-1 was added to the second, third, and fourth samples. After adding 200 mg, 1 g, and 2 g of each of the four components, each of the four components was coated as a protective layer on the silver iodobromide emulsion layer to a dry film thickness of 1.5 microns, and dried to prepare a sample. These samples were conditioned for 3 hours at 25℃ and 20% relative humidity, and under the same air conditioning conditions,
After rubbing with a rubber in a dark room, perform normal development processing and observe the occurrence of static marks. The evaluation was divided into five stages: , [maximum occurrence]. The results were as shown in Table 1 below.

[Table] This table shows that the latex obtained from the monomer of the present invention has an antistatic effect. Example 2 A photographic emulsion was prepared and coated in the same manner as in Example 1. Next, gelatin aqueous solution 2 was prepared in the same manner as in Example 1, divided into 9 portions of 200 ml each, and 1
No antistatic agent was added in the 2nd and 3rd cases, 2g and 3g of the following antistatic agent was added in the 4th and 5th cases. What was dispersed in the latex of example 5,
The antistatic agent was added in an amount of 2 g to 3 g per coat, and was coated and dried to prepare a sample. (Antistatic agent-A) (However, n1+n2+n3=12) The thus obtained sample was evaluated for the occurrence of static marks in exactly the same manner as in Example 1. In addition, with the remainder of the sample, in order to examine the precipitation in the developing solution, we processed 10 quarter-cut sheets per one developing solution for a normal automatic processing machine (processing time 30 seconds, temperature 35°C), and then Observe and check the degree of precipitation [no precipitation],
The evaluation was divided into four stages: [small precipitation], [medium precipitation], and [large precipitation]. The results are shown in Table 2. For the automatic processing, a continuous roller conveyance type automatic developing machine was used, which can perform development, fixing, washing, and drying all at once. The composition of the treatment liquid used was as follows. Hydroquinone 10g Anhydrous sodium sulfite 70g Boric anhydride 1g Sodium carbonate (monohydrate) 20g 1-phenyl-1,3-pyrazolidone 0.35g Sodium hydroxide 5g 5-methylbenzotriazole 0.05g Potassium bromide 15g Glutaraldehyde bisulfite 15g Glacial acetic acid 8g Add water to make 1.

[Table] As is clear from Table 2, samples according to the present invention
It can be seen that No. 4 and No. 5 have improved the drawback of precipitation of the antistatic agent into the developer when a large amount of the antistatic agent is used. It can also be seen that the antistatic performance is also extremely good. Example 3 A photographic emulsion was prepared and coated in the same manner as in Example 1. Next, gelatin aqueous solution 2 was prepared in the same manner as in Example 1, and divided into nine portions of 200 ml each.
In the first case, no antistatic agent was added, in the second and third cases, antistatic agent-B was added at a rate of 2g or 3g per unit, and in the fourth and fifth cases, antistatic agent -C was added in 1 part.
(Antistatic agent-B) C ₁₈ H ₃₇ O (CH ₂ CH ₂ O) ₁₀ H (Antistatic agent-C) 6 and 7, antistatic agent-B was dispersed in the latex of polymer example 2, and the amount of antistatic agent was 1.
In the 8th and 9th stages, antistatic agent-C was dispersed in the latex of polymer 1 to give an amount of antistatic agent of 2g or 3g per polymer.
A total of 3 g was added, coated, and dried to prepare a sample. The obtained samples were divided into 2 pieces each with a size of 35 mm x 70 mm.
After cutting the films one by one and leaving them in an air-conditioned room at a temperature of 23°C and a relative humidity of 55% for 24 hours, these film samples were brought into contact with similar films with their silver halide emulsion sides facing each other, and then the top Approximately 1Kg
The sample was left in the air-conditioned room for an additional 24 hours under a load of . The film was peeled off after being left to stand, and the adhesiveness of the film was calculated from the ratio of the total area to the area where the emulsion surface adhered. On the other hand, the photographic properties of these films were determined in Example 2 by using a new sample and subjecting it to white light wedge exposure using a KS-1 sensitometer (manufactured by Konishiroku Photo Industry Co., Ltd.) based on the JIS method. Processing was performed using the automatic processor shown. These results are shown in Table 3. However, the sensitivities in the table are expressed as relative sensitivities, with Sample No. 1 being 100.

[Table] As is clear from Table 3, the samples according to the present invention (Nos. 6 to 9) not only suppress the occurrence of fog, but are also extremely effective when stored in high humidity conditions. It can be seen that mutual adhesion is suppressed. Example 4 Even when Polymer Examples 4 and 8 were used in place of Latex 1 used in Example 1, almost the same results as with the latex of Example 1 were obtained. Example 5 Even if a latex using Polymer Examples 4 and 8 was used in place of the latex of Polymer Example 5 used in Example 2, the same results as Sample No. 4 of the present invention shown in Table 2 were obtained. Ta. Embodiments of the invention are described below. 1 A patent characterized in that the outermost layer contains a polymer latex polymer composition in which an oil-in-water polymer dispersion obtained by polymerizing monomers represented by the general formula is impregnated with an antistatic agent. A silver halide photographic material according to the claims.

Claims (1)

[Scope of Claims] 1. A silver halide photographic light-sensitive material characterized in that an oil-in-water polymerization dispersion containing a repeating unit represented by the following general formula is contained in the gelatin-containing outermost layer of the constituent layers. [General formula] (In the formula, R and R′ each represent a hydrogen atom or a methyl group, R″ represents a hydrogen atom, an alkyl group, or an aryl group, and n represents a positive integer from 2 to 100. However, the oil droplet dispersion in water are substantially free of hydrophobic substances, or if they are, include antistatic agents.)