JPH06118566A - Antistaticized silver halide photographic sensitive film material - Google Patents

Abstract

PURPOSE:To improve antistatic characteristic and film strength and to obtain a backing layer uniform in a coating surface by incorporating an epoxy compound and a specified surfactant in an electrically conductive polymer layer. CONSTITUTION:The conductive polymer layer is formed between the backing layer containing gelatin and a film base and comprises a copolymer of dialkylaminoalkyl (meth)acrylate and styrenesul-fonic acid or its alkali metal salt, and the conductive polymer layer contains the epoxy compound and the surfactant represented by formula I in which n is an integer of 1-20; M is H or an alkali metal atom: R is 5-15C alkyl or a group of formula II; R1 is 1-15C alkyl; and R2 is l-3C alkyl or H or halogen.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a silver halide photographic light-sensitive material, and more particularly to an antistatic backing layer.

[0002]

2. Description of the Related Art Films, papers and the like are used as bases for silver halide photographic materials, but these have low conductivity and have caused various problems.

One of these problems is that when a coating solution containing silver halide is applied to a film, paper or the like, it is applied at a high speed with a coater, but it is charged while being rubbed and rubbed by a roller. However, this is a problem that the silver halide is fogged when it is discharged (electrostatic fog).
If the backing layer is made highly conductive and antistatic, it is usually applied before the silver halide emulsion is coated, so this backing layer should be applied through the base to the opposite emulsion coating surface. The antistatic property is also improved and electrostatic fog can be prevented.

Secondly, when a user uses a photosensitive material, if they are charged, dust and dirt adhere to the photosensitive material, forming undesired images such as pinholes in the process of exposure and photographic processing. However, there is a problem that the photosensitive materials stick to each other and workability is poor. Further, there is a problem that these photosensitive materials are discharged through human hands. What is important in these problems is that the charging characteristics must be good both before and after the treatments of development, fixing and washing.

JP-A-56-92535 and JP-A-61-1.
According to 74542, an antistatic layer is provided between a backing layer and a base, and an aziridine hardener is used to enhance antistatic properties through this layer and to improve the adhesion between this layer and the backing layer. Is listed. However, the aziridine hardener causes skin irritation and is not preferable for safety and hygiene. Further, since the antistatic layer is provided between the base and the base, the backing layer is not sufficiently adhered and the drying property is poor.

[0006]

SUMMARY OF THE INVENTION An object of the present invention is to provide a backing layer which has good antistatic properties and film strength and has a uniform coated surface.

[0007]

The present invention provides a silver halide film light-sensitive material having a conductive polymer layer between a backing layer containing gelatin and a film base, wherein the conductive polymer is a dialkylaminoalkyl (meth). It is achieved by comprising a copolymer of acrylate and styrene sulfonic acid or an alkali metal salt thereof, and containing the epoxy compound and the surfactant of Chemical formula 1 in the conductive polymer layer. It is also achieved when the conductive polymer is a copolymer of dialkylaminoalkyl (meth) acrylate and styrene sulfonic acid or its alkali metal salt grafted onto gelatin or other water-soluble polymer.

The conductive polymer used in the present invention is a copolymer of dialkylaminoalkyl (meth) acrylate and styrenesulfonic acid or its alkali metal salt, which is crosslinked with an epoxy compound. The proportion of dialkylaminoalkyl (meth) acrylate in the copolymer is preferably 0.3% by weight or more and 45% by weight or less.
If the ratio is less than 0.3% by weight, the epoxy compound does not sufficiently crosslink and cannot withstand alkaline or acidic photographic processing. On the other hand, if the proportion exceeds 45% by weight, the proportion of styrene sulfonic acid or its alkali metal salt relating to the antistatic property is relatively lowered, so that sufficient antistatic property cannot be obtained.

The conductive polymer of the present invention can be produced by polymerizing P-styrenesulfonic acid or its alkali metal salt and dialkylaminoalkyl (meth) acrylate in an arbitrary ratio. Examples of the dialkylaminoalkyl (meth) acrylate include 2-dimethylaminoethyl methacrylate, 2-diethylaminoethyl methacrylate, 2-dimethylaminomethyl methacrylate and the like.

Further, in the present invention, in addition to styrenesulfonic acid or its alkali metal salt and dialkylaminoalkyl (meth) acrylate, various monomers can be copolymerized as the third component. For example, styrene and its derivatives, (meth) ) Acrylic acid esters and their derivatives, vinyl acetate and the like. The copolymerization ratio of the third component monomer is preferably in the range of about 0.1% by weight to 45% by weight.

When synthesizing the above-mentioned copolymer, various water-soluble polymers are previously dissolved or dispersed, and radical polymerization is carried out in the presence of these, so that the copolymer is grafted to these water-soluble polymers. A polymerized graft copolymer composition can be obtained.

Preferred examples of the water-soluble polymer to be added in advance during the polymerization include gelatin and its modified products, and various other water-soluble polymers such as modified starch and polyvinylpyrrolidone are also available. Can be used.

The counter ion of styrene sulfonic acid is preferably an alkali metal ion such as sodium ion or potassium ion. Examples of synthesis are shown below, but the invention is not limited thereto.

Synthesis Example 1 Gelatin 10 g, sodium p-styrenesulfonate 90 g, and 2-dimethylaminoethyl methacrylate 10 g were placed in a 500 ml four-necked flask equipped with a stirrer, a thermometer, a nitrogen introduction tube and a reflux condenser, and distilled water was added. 300 g was added and heated to 80 ° C. Polymerization was started by adding 1 g of potassium persulfate under a nitrogen atmosphere, and the mixture was heated and stirred for 3 hours to carry out polymerization to obtain a polymer solution.

Synthesis Example 2 In the same manner as in Synthesis Example 1, 80 g of sodium p-styrenesulfonate and 20 g of 2-dimethylaminoethyl methacrylate were used.
After adding 300 g of distilled water and neutralizing with hydrochloric acid aqueous solution,
Heated to 80 ° C. 1 g potassium persulfate under nitrogen atmosphere
Polymerization was started by adding, and the mixture was heated and stirred for 3 hours to carry out polymerization to obtain a polymer solution.

Synthesis Example 3 As in Synthesis Example 1, 7 g of polyvinylpyrrolidone, 15 g of styrene, 80 g of sodium p-styrenesulfonate,
10 g of 2-dimethylaminoethyl methacrylate was added to 300 g of distilled water, neutralized with a hydrochloric acid aqueous solution, and then heated to 80 ° C. Polymerization was started by adding 1 g of potassium persulfate under a nitrogen atmosphere, and the mixture was heated and stirred for 3 hours to carry out polymerization to obtain a polymer solution.

The conductive polymer obtained by the present invention is
By adding an epoxy compound to this, a film is formed on a support such as a film and completely crosslinked within a few hours under a heating condition of about 50 ° C.

The conductive polymer of the present invention is preferably applied in an amount of 0.1 to 5 g as a solid content per 1 m ² . 0.1 g
If less than 5g, good antistatic properties cannot be obtained and
If it is larger than the above range, the amount of water absorption increases and the drying property deteriorates. If necessary, the conductive polymer layer may contain other binder.

Specific examples of the epoxy compound used in the present invention are shown below, but the invention is not limited thereto.

[0020]

[Chemical 3]

[0021]

[Chemical 4]

[0022]

[Chemical 5]

[0023]

[Chemical 6]

[0024]

[Chemical 7]

[0025]

[Chemical 8]

[0026]

[Chemical 9]

[0027]

[Chemical 10]

[0028]

[Chemical 11]

[0029]

[Chemical 12]

[0030]

[Chemical 13]

[0031]

[Chemical 14]

[0032]

[Chemical 15]

The amount of the epoxy compound added is 1 mg to 1 g, and particularly preferably 50 mg to 300 mg, per 1 g of the conductive polymer. If added too much, the backing layer, which is the upper layer of the antistatic layer, is affected, and the dye removal becomes worse. If it is too small, the film of the antistatic layer becomes weak.

The surfactant of the general formula 1 used in the present invention is described in USP 3,026,201, but no description is given regarding matching with the conductive polymer and epoxy compound of the present invention.

The surfactant of the present invention exhibits excellent coatability in matching the conductive polymer of the present invention with the epoxy compound, and a transparent and uniform coating surface can be obtained. In addition, good film characteristics are obtained, and the surface resistance value is relatively low.

When other surfactants are used, the coated surface becomes cloudy or uneven coating is observed. Also, there are many things that affect the surface resistance value.

In the chemical formula 1, n is preferably 20 or less.
When it is 21 or more, the coating property becomes poor. Particularly, 3 to 15 is preferable. Alkyl group R is not play a role as a C ₅ -C ₁₅ a and C ₄ is not more than a surfactant, and poor coating properties, causing a practical problem. When it is C ₁₆ or more, the lipophilic property is too strong, causing uneven coating. Especially C _{8 to} C ₁₂
Is preferred. R ₁ is the same as the alkyl group of R. M is H or an alkali metal. Particularly, sodium and potassium ions are preferable. R ₂ is a C ₁ -C ₃ alkyl group,
H, a halogen atom.

The amount of these surfactants added is preferably 0.05 to 10 g per liter of the coating liquid. The time of addition may be any time.

Specific examples of the surfactant used in the present invention are shown below, but the surfactant is not limited thereto.

[0040]

[Chemical 16]

[0041]

[Chemical 17]

[0042]

[Chemical 18]

[0043]

[Chemical 19]

[0044]

[Chemical 20]

[0045]

[Chemical 21]

The conductive polymer layer used in the present invention is located between the backing layer containing gelatin and the film base, and is not preferred at other positions. For example, when an antistatic layer is provided on the side opposite to the base via the backing layer, the backing layer generally contains a filter dye, which is not preferable because the dye loss is poor. Further, when an antistatic layer is provided between the emulsion layer and the film base, it is generally disadvantageous that the emulsion layer is required to have stronger adhesion on the emulsion side than on the back side by sticking a stripping film or the like. Further, providing an antistatic polymer layer between the emulsion layer and the protective layer or on the outer side of the protective layer with respect to the film base is disadvantageous in view of development progress and fixing speed. Therefore, it is most reasonable to position the antistatic polymer between the film base and the backing layer containing gelatin.

The amount of gelatin in the backing layer is 1 to 1 m ²
8 g, preferably 1-5 g. The backing layer may further contain the above-mentioned conductive polymer, other conductive polymer, water-soluble polymer, hardener, matting agent, antihalation dye, surfactant and the like, if necessary.

The film base used in the present invention is mainly a polyethylene terephthalate film, but other polyester bases are also included.

[0049]

【Example】

Example 1 To 500 ml of distilled water was added 500 ml of a 10% solution of sodium polystyrene sulfonate having 10% by weight of 2-dimethylaminoethyl methacrylate, and 50 ml of a 10% aqueous solution of the epoxy compound of Chemical formula 3 was added. Five solutions were prepared.

10 ml of a 10% solution of various surfactants was added to each solution. The surfactants added are shown in Table 1.

[0051]

[Table 1]

Next, each solution was coated on a 100-micron polyethylene terephthalate film which had been subbed by a roll-fit coating pan and an air knife coater so that the coating amount was 20 ml / m ² . After the application, it was heated at 50 ° C. for 24 hours.

The gelatin solution used as the backing layer was prepared by dissolving 50 g of inert gelatin in 950 ml of distilled water, and 20 ml of 10% air roll OP was added as a surfactant. 25 ml of 2,4-dichloro-6-hydroxy-s-triazine was added as a hardener, and the coating amount was 50 ml / m ² on the conductive polymer layer, and the mixture was heated at 50 ° C. for 24 hours.

The sample after heating was cut, and GR- manufactured by Konishi Rokusha Co., Ltd. was cut.
Processed using 14 automated developers. Development is MRA CD-111 manufactured by Mitsubishi Paper Mills Co., Ltd. at 35 ° C. for 20 seconds, and fixing is CF-711 at 35 ° C. for 20 seconds.

The antistatic ability of the sample before and after the treatment was 2
It was left for 2 hours in an atmosphere of 5 ° C. and 30% RH (relative humidity), and its surface resistance value was measured by a Hiresta surface resistance meter, Model HT-210 manufactured by Mitsubishi Petrochemical Co., Ltd. As a measure of the surface resistance, 10 ¹² Ω or more is impossible, and 10 ¹¹ or less is a good level.

The film strength was obtained by scratching the surface of the sample with a knife in a square shape at intervals of 5 mm, immersing the sample in water at 30 ° C. for 30 seconds, and then rubbing the surface with a tissue. It was evaluated by. The circles are those that do not peel at all, the triangles are those that peel slightly, and the crosses are those that peel considerably. The coating properties were evaluated as × when the coating unevenness was noticeable or when the coated surface was turbid, Δ when the coating surface was light, and ◯ when the coated surface was uniform and had no turbidity. The results are shown in Table 2.

[0057]

[Table 2]

As can be seen from Table 2, in the case of using the air roll OP, the coating property is slightly uneven and the coated surface is cloudy, which is not possible. The coating using Actinol K has good coatability, but the coating strength is rather weak and the resistance after treatment is rather high. In the case of using Zontes TL, coating unevenness is observed and the film strength is slightly inferior. In the case of using Sunstat 1007, the polymer layer is slightly cloudy and the film strength is slightly weak. From these results, it can be seen that the backing layer using the surfactant of the present invention in the conductive polymer layer is excellent in surface resistance value, film strength and coatability.

Example 2 A conductive polymer was prepared by grafting sodium polystyrene sulfonate having 5% by weight of 2-diethylaminoethyl methacrylate onto water-soluble gelatin at a weight ratio of 10: 1 (gelatin = 1). Distilled water was added to this polymer to prepare 1000 ml of a 5% aqueous solution, and 30 ml of a 10% aqueous solution of the epoxy compound of Chemical formula 15 was added. Five solutions were prepared.

20 ml of 10% solutions of various surfactants were added to each solution. Table 3 shows the added surfactants.

[0061]

[Table 3]

In the same manner as in Example 1, the surface resistance value, film strength and coatability were examined. The results are shown in Table 4.

[0063]

[Table 4]

As can be seen from Table 4, in the case of using the air roll OP, some coating unevenness was observed, and the coated surface was clouded, which is not possible. The one using Actinol K has good coatability and film strength, but the resistance value after treatment is rather high. The one using Zontes TL shows uneven coating.
In the case of using Sunstat 1007, the polymer layer is slightly clouded and the film strength is slightly inferior to the others. On the other hand, in the case of using the surface active agent 16 of the present invention, the surface resistance value, the film strength and the coating property were good.

[0065]

The silver halide light-sensitive material of the present invention has an antistatic layer excellent in conductivity, film strength and coatability.

Claims (2)

[Claims] 1. A silver halide film light-sensitive material having a conductive polymer layer between a backing layer containing gelatin and a film base, wherein the conductive polymer is dialkylaminoalkyl (meth) acrylate and styrenesulfonic acid or a compound thereof. A silver halide film light-sensitive material comprising a copolymer with an alkali metal salt and containing an epoxy compound and a surfactant represented by Chemical Formula 1 in the conductive polymer layer. [Chemical 1] [Chemical 2] In the chemical formula 1, n is a natural number of 1 to 20, M is H or an alkali metal, R is a C _{5 to} C ₁₅ alkyl group, or a group represented by the chemical formula 2. R _{1 in} Chemical Formula 2 is a C ₁ -C ₁₅ alkyl group, R 1
₂ is an alkyl group or H or a halogen atom, a C ₁ -C _3. 2. A silver halide film light-sensitive material having a conductive polymer layer between a backing layer containing gelatin and a film base, wherein the conductive polymer is dialkylaminoalkyl (meth) acrylate and styrenesulfonic acid or a compound thereof. It is characterized in that a copolymer with an alkali metal salt is grafted to gelatin or other water-soluble polymer, and that the conductive polymer layer contains an epoxy compound and a surfactant shown in Chemical formula 1. Silver halide film photosensitive material.