JP2000275784A - Production of photographic sensitive material support - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a process for production which enables a simultaneous wet-on-wet coating with an antistatic layer and a backing layer in the production of a photographic sensitive material having the antistatic layer and the backing layer contg. a gelatin layer on a support. SOLUTION: The process for producing a photographic sensitive material support having the antistatic layer and the backing layer containing gelatin successively from the side nearer to the support on the one surface of the support is a process for producing the photographic sensitive material support which is characterized in the simultaneous wet-on-wet coating with the antistatic layer containing a cationic antistatic polymer and the gelatin and backing layer containing the gelatin. The support of the recording material having the excellent antistatic performance can be obtained by one stage by the simultaneous wet-on-wet coating with the antistatic layer and the gelatin layer.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a photographic light-sensitive material support having antistatic ability.

[0002]

2. Description of the Related Art When a photographic material having a support such as a polyester film is produced, an antistatic process is generally performed for the purpose of preventing electrostatic damage.

[0003] Examples of the antistatic processing method include a method of applying an antistatic agent such as various surfactants, antistatic polymers, conductive carbon and metal oxides to the surface of the photographic material, or kneading the same into the interior. General.

[0004] Low molecular surfactants and the like have been widely used as antistatic agents in the past. However, problems such as stickiness of the surface of the photographic photosensitive material subjected to antistatic processing due to bleeding out of the antistatic agent and deterioration with time are considered. Had occurred.

[0005] Alternatively, antistatic processing of recording materials using conductive materials such as carbon black and metal oxides has also been performed. However, when these materials are used, the conductive materials must be in contact with each other. Since sufficient antistatic performance cannot be obtained, a certain amount of used amount is required. For this reason, coloring of the photographic light-sensitive material, reduction in transparency, and the like become problems, and the usage is limited.

[0006] As a method of obtaining a transparent and highly durable antistatic layer, attempts have been made on antistatic processing using an antistatic polymer. By coating the support with a combination of an antistatic polymer and an appropriate crosslinking agent, a transparent antistatic layer having excellent durability can be obtained.

Various gelatins are widely used as constituents of photographic light-sensitive materials. When an antistatic polymer is directly added to a gelatin layer for the purpose of performing antistatic processing of a photographic light-sensitive material containing such a gelatin layer,
Various additives contained in the gelatin layer and the antistatic polymer mutually affect each other, causing various obstacles. For example, when an ionic polymer is used as the antistatic polymer, it reacts with other ionic components in the gelatin layer, for example, polymer latex or filter dye, etc. It may cause obstacles such as deterioration. Further, when a nonionic polymer is used as the antistatic polymer, the reaction with the ionic component in the gelatin layer can be prevented, but there is a problem that the antistatic performance is lower than that of the ionic polymer.

For the above reasons, when performing antistatic processing of a photographic light-sensitive material, an antistatic polymer is not added directly to the photographic light-sensitive layer, but is added to the layers constituting the photographic light-sensitive material. In many cases, a method of providing an antistatic layer on the surface is adopted. However, when the antistatic layer is provided on the same surface as the photographic emulsion layer, the effect of the antistatic layer on the photographic emulsion layer is large,
The characteristics of the photographic light-sensitive material are greatly deteriorated. For this reason, it is common practice to provide an antistatic layer on the opposite side of the photographic emulsion layer, the so-called backing layer side.

However, if the gelatin layer and the antistatic polymer layer are to be simultaneously coated using a multilayer coating apparatus, the viscosity of the antistatic polymer layer is low, and the antistatic layer is blown off in the drying step, or the antistatic layer is blown off. Problems such as mixing of the two layers between the polymer layer and the gelatin layer occur. As a result, it becomes difficult to perform good coating, or the characteristics of the photographic material obtained by using such a coating method suffer some trouble. As described above, in order to make two layers difficult to perform simultaneous multilayer coating adjacent to each other, one layer is coated and then sufficiently dried,
It is necessary to adopt a method of applying another layer repeatedly, but this method has a problem that production efficiency is reduced due to an increase in the number of manufacturing steps.

As a means for coating a gelatin layer and an antistatic layer in a multi-layered manner, JP-A-7-120880 discloses a method in which an intermediate layer is provided between the two layers to prevent interfacial mixing between the two layers. In such a method, there is a problem that the antistatic performance is deteriorated because one more layer is added on the antistatic layer in addition to the gelatin layer constituting the photographic light-sensitive material.

Further, Japanese Patent Application Laid-Open Nos. Hei 6-130555 and 8
As described in -272014, a sol-gel conversion function is added to the antistatic polymer layer by adding a component that gels when cooled, such as gelatin, to the antistatic polymer layer. Attempts have been made to apply multiple layers. However, there is a problem that the addition of gelatin or the like leads to a decrease in antistatic performance, making it difficult to obtain sufficient antistatic performance.

As the antistatic polymer, cationic,
Alternatively, an anionic ionic polymer or a nonionic polymer can be used. For example, JP-A-53-1061
15, JP-A-60-250343, JP-A-61-223
736 and JP-A-62-9346 disclose photographic light-sensitive materials using an antistatic polymer containing a quaternary ammonium base.

The cationic antistatic polymer can obtain higher antistatic performance than the anionic or nonionic antistatic polymer. However, cationic polymers have a greater effect on photographic emulsions than anionic or nonionic polymers, and have the problem that the properties of photographic light-sensitive materials are greatly deteriorated.

JP-A-8-262629 discloses a photographic support using an anionic polystyrene sulfonic acid derivative as an antistatic polymer. Anionic polymers are widely used because their antistatic performance is slightly lower than that of cationic polymers, but have less effect on photographic materials. However, the viscosity tends to increase greatly when mixed with gelatin, and it is difficult to add gelatin to the antistatic layer or to simultaneously coat the antistatic layer and a layer containing gelatin.

[0015]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a photographic material having an antistatic layer and a backing layer containing a gelatin layer on a support. The object of the present invention is to provide a manufacturing method which enables the above.

[0016]

SUMMARY OF THE INVENTION The object of the present invention is to provide a method for producing a photographic light-sensitive material support having an antistatic layer and a gelatin-containing backing layer on one side of the support from the side closer to the support. Wherein the antistatic layer containing a cationic antistatic polymer and gelatin, and a backing layer containing gelatin are simultaneously coated in a multi-layered manner.

[0017]

BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, as the cationic antistatic polymer, a conventionally known cationic antistatic polymer can be used, but a polymer having a functional property represented by the following formula 2 is particularly preferable.

[0018]

Embedded image In Chemical Formula 2, R ₁ represents an alkyl group. Preferred examples of R ₁ include lower alkyl groups such as a methyl group and an ethyl group. Examples of monomers containing a functional group represented by Chemical Formula 2 are shown in Chemical Formulas 3 to 9.

[0019]

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[0020]

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[0021]

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[0022]

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[0023]

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[0024]

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[0025]

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A monomer having a functional group as shown in Chemical formula 2 functions as a crosslinking point for crosslinking polymers in the polymer. Such a polymer has reactivity with gelatin and also functions as a gelatin crosslinking agent. Therefore, an antistatic layer composed of a cationic antistatic polymer having a functional group as shown in Chemical formula 2 and gelatin has preferable characteristics that it exhibits excellent durability and water resistance without adding a crosslinking agent. Having. Also, in this case, the gelatin layer and the antistatic polymer, which are simultaneously coated on the antistatic layer, exhibit a cross-linking reaction at the interface between the layers, thereby exhibiting the property that the adhesion between the layers is extremely excellent. It is also preferable because it can be performed.

The cationic antistatic polymer in the present invention can be obtained by copolymerizing a monomer having a cationic functional group with a monomer having a functional group for crosslinking the polymers. As the monomer having a cationic functional group, a monomer having a quaternary ammonium base or a phosphonium base is preferable. Examples of the monomer having a quaternary ammonium base or a phosphonium base are shown in the following Chemical formulas 10 to 20, but are not limited thereto.

[0028]

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[0029]

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[0030]

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[0031]

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[0032]

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[0033]

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[0034]

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[0035]

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[0036]

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[0037]

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[0038]

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The cationic antistatic polymer exhibits high antistatic performance in a small amount as compared with the anionic antistatic polymer. Therefore, the content of the antistatic polymer in the antistatic layer can be reduced, and sufficient antistatic performance can be obtained even when gelatin is added to the antistatic layer. In addition, since the viscosity of the cationic antistatic polymer when mixed with gelatin is not as intense as that of the anionic polymer, multi-layer coating can be easily performed.

In the antistatic polymer used in the present invention, the amount of the monomer unit having a functional group for crosslinking the polymers is preferably from 0.1% by weight to 70% by weight in the polymer. When the monomer unit having a functional group for cross-linking the polymers is included in the polymer in an amount of more than 70% by weight, the antistatic performance is undesirably reduced. When the amount of the monomer unit having a functional group for crosslinking the polymers is 0.1% by weight or less, the portion where the polymers are crosslinked is small, and the durability of the antistatic layer is undesirably reduced.

The introduction of a functional group component other than a functional group for crosslinking the cationic functional group and the polymer into the antistatic polymer used in the present invention is also preferably carried out according to the purpose and application. That is, in addition to the various monomers according to the present invention as described above when forming the polymer, for example, styrene, 4-methylstyrene, 4-hydroxystyrene, 4-carboxystyrene, 4-aminostyrene, Chloromethylstyrene, 4-
Styrene derivatives such as methoxystyrene, methyl methacrylate, ethyl methacrylate, butyl methacrylate, hexyl methacrylate, 2-ethylhexyl methacrylate,
Cyclohexyl methacrylate, alkyl methacrylates such as dodecyl methacrylate, phenyl methacrylate, aryl methacrylate or alkyl aryl esters such as benzyl methacrylate, or
Monomers having a nitrogen-containing heterocycle such as 4-vinylpyridine, 2-vinylpyridine, N-vinylimidazole, N-vinylcarbazole, or acrylonitrile, methacrylonitrile, acrylamide, methacrylamide, dimethylacrylamide, diethylacrylamide, N Acrylamide or methacrylamide derivatives such as -isopropylacrylamide, diacetoneacrylamide, N-methylolacrylamide, N-methoxyethylacrylamide, and further acrylonitrile;
Methacrylonitrile, vinyl acetate, vinyl chloroacetate,
Vinyl esters such as vinyl propionate, vinyl butyrate, vinyl stearate, and vinyl benzoate; vinyl ethers such as methyl vinyl ether and butyl vinyl ether; and others, N-vinylpyrrolidone, acryloylmorpholine, tetrahydrofurfuryl methacrylate,
Various monomers such as vinyl chloride, vinylidene chloride, allyl alcohol, vinyltrimethoxysilane, and glycidyl methacrylate can be appropriately used as a copolymerization monomer.

When other copolymerizable monomers are further introduced into the polymer, the ratio of the other monomers in the polymer to be formed is limited. That is,
70% by weight of other monomers in the polymer
When it is introduced at a ratio exceeding the above range, the antistatic performance may be impaired, which is not preferable. It is necessary to secure at least 30% by weight of a portion relating to the original antistatic performance in the polymer.

As a crosslinking agent for crosslinking the polymers, various types of crosslinking agents can be used depending on the type of the functional group contained in the polymer. For example, in the application of an antistatic polymer containing a monomer unit having a functional group as shown in Chemical formula 2, an aldehyde-type crosslinking agent such as formaldehyde, glyoxal, succinaldehyde, glutaraldehyde, dialdehyde starch, polyacrolein, or dimethylol urea; Use N-methylol type crosslinking agents such as trimethylol melamine, dimethylol ethylene urea, hexamethylol melamine, dimethylol alkyl triazine, methylated dimethylol uron, dimethylol hydroxyethylene urea, dimethylol propylene urea, dimethylol carbamate and the like. be able to.

In the present invention, when the antistatic polymer has an amino group, a carboxyl group, or a hydroxyl group, when a crosslinking agent which reacts with these functional groups is used, the crosslinking agent is a crosslinking agent for gelatin. , Which is advantageous because both the antistatic polymer and gelatin can be cross-linked with one type of cross-linking agent.
For example, when an antistatic polymer containing an amino group is used, both an antistatic polymer and gelatin can be crosslinked by using an aldehyde-based crosslinking agent such as formalin or an epoxy-based crosslinking agent.

In the present invention, as the gelatin used in combination with the antistatic polymer in the antistatic layer, gelatin generally used in the production of photographic light-sensitive materials can be used. If the amount of gelatin used is small, the sol-gel conversion ability of the antistatic layer is reduced, and the coatability is deteriorated. In addition, when the amount is large, the content ratio of the antistatic polymer is reduced, and the antistatic performance is reduced. Therefore, the amount of gelatin used is 1 to the antistatic polymer.
It is preferably from 0% by weight to 150% by weight, and particularly preferably from 25% by weight to 60% by weight.

In the antistatic layer in the present invention, various additives can be preferably used in combination for the purpose of further improving the abrasion resistance, blocking resistance, water resistance and the like of the film. . Examples of such additives include polymer emulsions such as styrene-butadiene-based latex, styrene-acryl-based latex, various acrylic emulsions, vinyl acetate-based latex, and polyurethane-based emulsion, polyvinyl alcohol, hydroxyethyl cellulose, hydroxypropyl cellulose, and carboxy. Various cellulose derivatives such as methylcellulose, various water-soluble polymers such as chitosan, or inorganic fine particles such as silica, colloidal silica, titanium oxide, and zinc oxide, organic polymer fine particles such as polystyrene fine particles, polymethyl methacrylate fine particles, and silicone-based fine particles are added. By doing so, it is possible to preferably achieve the above object.

The ratio of the antistatic polymer to the entire coating layer in the coating layer for forming the antistatic layer is 10%.
It is preferable that the amount is not less than% by weight, and if it is less than this, antistatic performance may be insufficient.

As the gelatin layer coated on the antistatic layer, a layer containing gelatin generally used for a recording material can be used. A dye, a matting agent, a gelatin cross-linking agent, and the like can be added to the gelatin layer as needed.

The multilayer coating method of the antistatic layer and the gelatin layer includes a slide bead coating method, a curtain coating method,
In addition, a multilayer coating method used in the production of a photosensitive material such as an extrusion coating method can be used.

[0050]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples. % In the examples represents% by weight.

Synthesis Example 1 4-vinylbenzyl-trimethylammonium chloride (QBm, manufactured by Seimi Chemical) 64%, diallyldimethylammonium chloride (DADMAC, manufactured by Tokyo Chemical Industry) 27%, acetoacetoxyethyl methacrylate (AAEM, Nippon Synthetic Chemical Industry) 9% distilled water 20
The mixture was dissolved in 0%, and heated and stirred while purging with nitrogen in a four-necked flask equipped with a stirrer, thermometer, nitrogen inlet tube, and reflux condenser. By adding 1% of V-50 (2,2'-azobis (2-amidinopropane) dihydrochloride, manufactured by Wako Pure Chemical Industries) as a polymerization initiator when the temperature of the solution in the flask rises to 75 ° C. The polymerization was started. Polymerization was carried out at this temperature for 5 hours to obtain a cationic antistatic polymer solution.

Synthesis Example 2 55% of QBm, 36% of DADMAC and 9% of AAEM were dissolved in 150% of distilled water and 50% of isopropyl alcohol, and a polymerization reaction was carried out in the same procedure as in Synthesis Example 1 to obtain a cationic antistatic polymer solution. .

Comparative Synthesis Example 1 90% of styrenesulfonic acid sodium salt and 10% of 2-dimethylaminoethyl methacrylate were dissolved in 200% of distilled water, and a polymerization reaction was carried out in the same procedure as in Synthesis Example 1 to obtain an anionic antistatic polymer. I got

Examples 1 to 4 An antistatic layer solution having a composition as shown in Table 1 and a backing layer solution having a composition as shown in Table 2 were prepared, and an aqueous undercoating PET film was prepared using a slide bead coating apparatus. Simultaneous multilayer coating was performed thereon. The coating amount of the antistatic layer solution and the backing layer solution, 20 g / m ² in moisture each fraction, 40 g / m ²
And

Comparative Examples 1 to 3 Antistatic layer solutions having the compositions shown in Table 3 were prepared, and a multilayer coating was performed on the backing layer solution and the aqueous undercoating treated PET film. In Comparative Example 1, the antistatic layer solution was applied on a PET film using a wire bar and dried, and then the backing layer solution was applied on the antistatic layer with a wire bar. In Comparative Examples 2 and 3,
Simultaneous multilayer coating was performed using a slide bead coating device in the same manner as in Examples 1 to 4. The coating amount of the antistatic layer solution and the backing layer solution, 20 g / m ² in moisture each fraction, 40 g / m ²
And

[0056]

[Table 1]

[0057]

[Table 2]

[0058]

[Table 3]

Various evaluations as described later were performed on the samples coated simultaneously. Table 4 shows the results.

[0060]

[Table 4]

In Table 4, the surface resistance of the sample was measured by adjusting the humidity of the sample for about one hour at a temperature of 20 ° C. and a relative humidity of 30%, and then measuring the surface resistivity with a Mitsubishi High-Performance Co., Ltd. The measurement was performed using Hyresta IP.

In Table 4, the applicability of the sample was evaluated by judging the uniformity and transparency of the applied layer based on color unevenness.

In Table 4, the adhesion of the sample was evaluated by examining the degree of peeling of the film surface when the coated surface of the sample was scratched in a grid pattern with a cutter knife and the portion was rubbed with moistened tissue paper. Made by. Evaluation is ○
(No peeling at all), Δ (1% peeling), and × (whole surface peeling).

From the results of the evaluation in Table 4, it is found that the sample subjected to the simultaneous multi-layer coating by the method according to the present invention has a surface resistance of 10 ⁹ Ω.
This indicates that the adhesiveness and coatability of the coated surface were good. This result is not different from the sample of Comparative Example 1 in which the antistatic layer and the backing layer are separately applied, and when the simultaneous multilayer coating is performed by the method according to the present invention, mixing at the interlayer interface does not occur. Then, it was confirmed that each coating layer was uniformly applied. Further, when the antistatic layer containing only the antistatic polymer and containing no gelatin was coated simultaneously with the gelatin layer as in Comparative Examples 2 and 3, the coated surface was poor, and the antistatic performance and adhesion were also improved. It was worse than the samples of Examples 1 to 4.

[0065]

According to the method of the present invention, a recording material support having excellent antistatic performance can be obtained in one step by simultaneously coating an antistatic layer and a gelatin layer.

Claims (4)

[Claims] 1. A method for producing a photographic light-sensitive material support having an antistatic layer and a backing layer containing gelatin on one side of the support from the side closer to the support, comprising a cationic antistatic polymer and gelatin. A method for producing a support for photographic light-sensitive material, comprising simultaneously applying an antistatic layer containing a polymer and a backing layer containing a gelatin. 2. A method for producing a support for a photographic light-sensitive material, characterized in that the antistatic layer according to claim 1 contains a cationic antistatic polymer having a functional group represented by Chemical formula 1. ] In Chemical Formula 1, R ₁ represents an alkyl group. 3. A method for producing a photographic light-sensitive material support, comprising a polymer having an amino group, a carboxyl group or a hydroxyl group as an antistatic polymer in the antistatic layer according to claim 1. 4. A method for producing a photographic light-sensitive material according to claim 1, wherein a hardening agent which is effective against both an antistatic polymer and gelatin is used. Production method.