JPH05107691A - Production of base material for photography - Google Patents

Abstract

PURPOSE:To produce the film base material for photography which is subjected to an antistatic treatment in a manner as not to adversely affect photosensitive layers at all, withstands chemical processing, such as developing and washing, is not degraded in the antistatic effect by a change in environment, such as temp. and humidity, and is highly transparent, inexpensive and highly economical. CONSTITUTION:This production process consists of a stage for previously providing water-insoluble and water-absorptive resin layers on at least one surface of a film base body and a stage for diffusing a water dispersion which does not substantially contain the resin of a colloidal conductive metal oxide contg. at least one kind of Zn, Sn and In as cations from the surface layer part of the water-insoluble and water-absorptive resin layers.

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 film support having excellent antistatic properties, and particularly to a method for producing a photographic film support in which the antistatic property does not deteriorate due to environmental changes such as temperature and humidity. It is about. Further, the present invention relates to a method for producing an inexpensive and highly transparent photographic film support which is free from physical and chemical adverse effects as a photographic support.

[0002]

BACKGROUND OF THE INVENTION In the field of photographic materials, photographic materials are generally manufactured by coating a light-sensitive silver halide-gelatin emulsion on a plastic support or a paper-plastic composite support in multiple layers. These plastic supports generate static electricity due to surface friction or peeling with substances of the same kind or different in dielectric properties during the production or use of the material, and accumulate on the surface of the material. The accumulated static electricity may cause the photosensitive layer to be exposed to light before exposure and development of the material, thereby causing exposure noise (static marks) in the form of dots or feathers. Further, after the material is exposed and developed, the dust existing around the material is attracted and foreign matter is attached to the film original. As described above, in the field of photographic light-sensitive materials, antistatic treatment has become an indispensable treatment, and progress in transport technology such as high sensitivity of materials, high-speed manufacturing, high-speed exposure, and high-speed development has become even more difficult. There is a demand for a film support having excellent preventive properties.

A number of patents have been filed to prevent static electricity, but the technique for making plastic conductive can be divided into the following three techniques. 1) Making the plastic support itself conductive. 2) Dispersion of conductive material on plastic support. 3) Coating of the conductive material on the surface of the plastic support. Of the above, 1) is the fact that sufficient material development has not yet been made, and in 2) most of them are mixed with coarse conductive fillers, and a transparent support is required. For example, it is not a preferable technique in the field of photographic materials. Therefore, in the field of photographic materials, the method 3) for producing an antistatic support by coating a conductive substance on the surface of a plastic substrate has been investigated.
For example, JP-A-55-84658, JP-A-61-174542 and JP-A-64-65180 disclose a water-soluble electrically conductive polymer having a carboxyl group, a hydrophobic polymer having a carboxyl group and a polyfunctional compound. Conducting polymers derived from aziridines are described. In addition, JP-A-61-174543
The publication describes an antistatic layer consisting of a conductive polymer (eg poly (sodium styrene sulfonate)) and gelatin. Further, in Japanese Patent Laid-Open No. 64-68751,
Certain polyphosphazene compounds have been described. Furthermore, U.S. Pat.Nos. 2982651, 3428456, 3457076,
Many surfactants are described in the specifications of No. 3454625, No. 3552972 and No. 3655387. However, these conductive compositions have a serious adverse effect on the photosensitive layer of the photographic material, the effects thereof are drastically reduced under environmental changes during use, particularly under low humidity, and further, they are washed out by developing water washing treatment. The effect has disappeared, and it is not a sufficient technique. On the other hand, Japanese Examined Patent Publication No. 35-6616, U.S. Pat.No. 30,62700, Japanese Unexamined Patent Publication No. 52-113224,
55-12927, Japanese Patent Publication 3-24656 and 3
No. 24657 and the like propose a technique in which a metal oxide such as Zn, Ti, In, or Si is dispersed in a resin and applied on a plastic support to form an antistatic layer. However, these techniques require a large amount of metal oxides, have problems in effectiveness and cost, and expose and develop photographic materials,
If you want to use the obtained image as a manuscript to form further images,
It has been found that the light transmittance of the non-image area is reduced, which is a serious drawback particularly when a plurality of sheets are overlapped to form a printed document.

[0004]

SUMMARY OF THE INVENTION The present invention has been made to remedy the above-mentioned drawbacks of the known art, the first purpose of which is to provide an antistatic photograph which does not adversely affect the photosensitive layer. To produce a film support for use. A second object of the present invention is to produce a photographic film support which withstands chemical treatments such as development and washing, and whose antistatic effect does not deteriorate due to environmental changes such as temperature and humidity. Third of the present invention
The purpose of is to produce a photographic film support having excellent transparency. A fourth object of the present invention is to produce an inexpensive and economically excellent photographic film support.

[0005]

The object of the present invention is to: 1) provide a water-insoluble and water-absorbent resin layer on at least one surface of a film substrate in advance; and 2) at least one of Zn, Sn, and In is a cation. And a substantially resin-free aqueous dispersion of the colloidal conductive metal oxide described above are diffused from the surface layer of the water-insoluble and water-absorbent resin layer. did it.

The water-insoluble and water-absorbent resin layer used in the present invention is made of various water-soluble resins alone or 2
A layer in which two or more kinds are mixed is water-insolubilized, and if necessary, two or more kinds of resin layers may have a multilayer structure. Specific preferred examples of the resin used in the resin layer of the present invention include gelatin, polyvinyl alcohol, polyvinylpyrrolidone, hydroxyethyl cellulose, styrene-maleic anhydride copolymer, polyacrylamide, polydimethylaminoethyl methacrylate, casein, polyacrylic acid copolymer. Examples thereof include polymers, agar, sodium alginate, starch derivatives and the like. Examples of particularly preferable resins are gelatins such as lime-processed gelatin, acid-processed gelatin and enzyme-processed gelatin. Among these water-soluble resins, the water-soluble resin having an active hydrogen group (hydroxyl group, carboxyl group, amino group, etc.) is water-insolubilized with a crosslinking agent. As the cross-linking agent, an inorganic cross-linking agent such as chrome alum or aluminum alum, formaldehyde, glyoxal, succinaldehyde, glutaraldehyde, dialdehyde-
Organic aldehyde type cross-linking agents such as starch and polyacrolein, N, N'-dimethylol urea, organic N-methylols such as condensates of ethylene glycol and glyoxal, condensates of succinaldehyde and ethanol, and acetal type cross-linking agents, bis Organic epoxy type cross-linking agents such as (2,3-epoxypropyl) methylpropylammonium-p-toluenesulfonic acid and 1,4-bis (2 ', 3'-epoxypropyloxy) butane, 2,4,6-tri Ethyleneimino-S-
Organic aziridine type crosslinking agents such as triazine, 1,6-hexamethylene-N, N'-bisethyleneurea, bis-β-ethyleneiminoethylthioether, etc., organic mucohalogenic acids such as mucochromic acid, mucobromic acid, mucophenoxycycloric acid, etc. -Type cross-linking agent, 2,4-dichloro-6-hydroxy-S-triazine sodium salt, 2,4-dichloro-6- (4-sulfoanilino) -S-triazine sodium salt, 2,4
-Dichloro-6- (2-sulfoethylamino) -S-triazine and other active halogen type crosslinking agents, vinyl sulfone,
Examples thereof include an active olefin type crosslinking agent having an acryloyl group, a carbodiimide type crosslinking agent, an isoxazolium type crosslinking agent, a methanesulfonic acid ester type crosslinking agent, and an active ester type crosslinking agent. The amount of the crosslinking agent used is usually 0.002 to 20% by weight, preferably 0.01 to 20% by weight, based on the resin.
At 10% by weight, the crosslinking conditions range from room temperature to 90 ° C for a few minutes to 72 hours, preferably at a temperature of 30 ° C to 60 ° C for 30 minutes to 48 hours.

In the water-insoluble and water-absorbent resin of the present invention, it is preferable to use a highly water-absorbent polymer compound together in order to uniformly and quickly diffuse a dispersed aqueous solution of a conductive metal oxide described below. Preferred examples of the highly water-absorbing polymer compound include JP-A-52-14689, JP-A-53-50290, and JP-A-51-16.
0387, 53-65597, 53-82666, 53-1046
No. 52, No. 53-104691, No. 53-105589, Japanese Patent Publication No. 53-13
Saponification products of copolymers composed of at least vinyl ester and ethylenically unsaturated carboxylic acid or its derivative, as described in JP-A No. 495, 53-13678 and the like, JP-A-53-80.
493, 53-60985, 53-63486, etc., and hydrolysates of acrylonitrile polymers. In the above, examples of the vinyl ester include vinyl acetate, vinyl propionate, vinyl stearate and the like (preferably vinyl acetate). As the ethylenically unsaturated carboxylic acid or its derivative, for example, acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, maleic anhydride, itaconic anhydride and their esters, acrylamide, methacrylamide, preferably Are acrylic acid, methacrylic acid and their methyl-, ethyl-, n-propyl-, isopropyl-, n-butyl-, t-butyl-esters, acrylamide, methacrylamide and the like. The molar ratio of the vinyl ester component (x) and the ethylenically unsaturated carboxylic acid component (y) is x: y = 10: 100 to 80:20, preferably x: y = 0: 100 to 70:30, and particularly Preferably, x: y =
It is 0: 100 to 60:40. Other ethylenic components may be contained in the copolymer in an amount of 1 to 10 mol%, preferably 3 to 7 mol%. The degree of saponification is preferably 30 mol% or more of the vinyl ester component in the above copolymer, and 30 mol% or more (particularly 70 mol% or more) when the ethylenically unsaturated carboxylic acid ester is copolymerized. .. Specifically, a saponified product of a copolymer of vinyl acetate and methyl acrylate having a methyl acrylate content of 62 mol% (saponification degree: 90 mol%), vinyl acetate and a methyl acrylate having a methyl acrylate content of 20 mol%. Examples include saponified copolymers (saponification degree 98 mol%), saponified copolymers of vinyl acetate and methyl acrylate having a methyl acrylate content of 48 mol% (saponification degree 98.3 mol%).

Next, the hydrolyzate of the acrylonitrile polymer will be described. The acrylonitrile-based polymer is a general term for polymers containing acrylonitrile as a copolymerization component, and specifically, acrylonitrile homopolymer or acrylonitrile and another one or two or more ethylenically unsaturated compounds Or a graft polymer of acrylonitrile and another polymer such as starch or polyvinyl alcohol.
The content of acrylonitrile is 30% by weight, preferably 50% by weight or more. The saponified product of an acrylonitrile polymer is a polymer containing an acrylate and acrylamide produced by hydrolysis of an acrylonitrile part. Specifically, saponified copolymer of acrylonitrile and methyl acrylate with 90% acrylonitrile content, saponified graft copolymer of starch and acrylonitrile, 85
Examples include saponified copolymers of mol% acrylonitrile-6.2% methyl acrylate-8.8% vinylidene chloride.

Other superabsorbent polymers include cellulosic superabsorbent polymers. Specifically, there are carboxymethyl celluloses, such as Hercules's Aqualon and Enka.
Akucell, Daicel Chemical Industries, Ltd.
Commercially available products such as Gel Fine of No. 6 can be used.
The amount of the super absorbent polymer used is usually in the range of 1 to 60% by weight, preferably 5 to 30% by weight, based on the resin such as gelatin.
The range is. If it is out of this range, that is, if it is less than 1% by weight, the effect is not exerted, and if it exceeds 60% by weight, the film strength is impaired.

The resin layer of the present invention may be colored to serve also as an antihalation layer. For example, pigments such as carbon black and phthalocyanine, oxol dyes, azo dyes, styryl dyes, anthraquinone dyes, merocyanine dyes, diallylmethane dyes, Examples thereof include triallyl dyes, cyanine dyes, hemicyanine dyes and arylidene dyes. If necessary, a matting agent such as silica, titanium oxide, and polymer beads, a polymer latex as a dimensional stabilizer, a plasticizer such as a high boiling solvent for improving the coating property, an ultraviolet absorber, a softening agent, and a thickening agent. A resin having a known surfactant such as a coating aid, a whitening agent, a lubricant and an antistatic aid and an alkali salt of a carboxylic acid can be used.

The colloidal metal oxide selected from Zn, Sn and In of the present invention preferably has an average particle size of 200 mμ or less,
It is particularly preferably 50 mμ or less, and is dispersed in a dispersion medium mainly composed of water. Further, in the present invention, coarse particles having a particle size other than the above-mentioned particle size may be used in combination to localize the particles inside the resin layer and the surface layer portion. As the metal oxide, Zn
Oxides of O ₂ , SnO ₂ and In ₂ O ₃ are preferred. Further, it is preferable to contain a small amount of a different kind of atom for the purpose of improving the conductive properties of these oxides, and examples thereof include Al, Nb, Ta, Sb,
Halogen etc. can be mentioned. The volume resistance value of the colloidal metal oxide used in the present invention is preferably 10 ¹⁰ Ω · cm or less, particularly preferably 10 ⁸ Ω · cm or less. When forming the conductive layer of the colloidal metal oxide of the present invention, a resin and a surfactant may be used if necessary for the purpose of assisting the stability of the colloidal solution and uniform coating and diffusion. Examples of the resin that can be used include known water-soluble electrically conductive polymers, nonions, and anionic surfactants in addition to the water-soluble resins exemplified as the resin layer. The ratio of the colloidal metal oxide to those auxiliary agents is preferably 0.1 part by weight or less relative to 1 part by weight of the colloidal metal oxide, and the minimum amount is used so that the colloidal metal oxide does not aggregate and precipitate.

Suitable film substrates for providing the water-insoluble and water-absorbent resin layer and the conductive layer of the present invention include polyethylene terephthalate film, polystyrene film, polycarbonate film, cellulose acetate film, cellulose nitrate film and cellulose acetate propionate. Films, films such as polyvinylidene chloride film, synthetic papers, and laminated films thereof. Further, resin-coated paper obtained by coating or laminating α-olefin polymers on pulp paper such as Paraita paper is also included. The above-mentioned substrate of the present invention can be provided with an easy-adhesion layer for the purpose of assisting adhesion with a water-insoluble and water-absorbent resin. For example, a mixed solution of a water-soluble resin and an oil-soluble resin may be previously applied or a hydrophobic layer may be formed. A copolymer having a group and a hydrophilic group is previously coated to form an easily adhesive layer. The surface of the film is usually modified by chemical or physical treatment such as chemicals, heat rays, ultraviolet rays, radiation or electric discharge treatment.

Next, an example of a preferred manufacturing process of the present invention will be shown, but the present invention is not limited to this embodiment. A mixed aqueous solution of a water-soluble resin / superabsorbent polymer / crosslinking agent is uniformly applied onto a film substrate (for example, polyethylene terephthalate) provided with an easy-adhesion layer in advance. The coating method can be arbitrarily selected from air doctor coating, blade coating, rod coating, knife coating, squib coating, reverse roll coating, gravure coating, kiss coating, spray coating and the like. The layer thickness when coating and drying is
It is not particularly limited, and it is applied according to its purpose. For example, if the purpose is simply a conductive layer, the effect can be sufficiently obtained with about 0.5 μm. If the purpose is to also serve as a curl prevention layer or an antihalation layer as a photographic material, it is usually in the range of 2 to 10 µ, and the effects of the present invention can be sufficiently exhibited. As the properties of the resin layer of the present invention,
When the following aqueous solution of conductive colloidal metal oxide is applied and diffused, the resin layer must not be redissolved. Therefore, in the present invention, it is preferable to heat the crosslinking agent for a certain period of time so that the crosslinking agent can sufficiently act. Next, by a similar coating method, the water-insoluble and water-absorbent resin layer provided in advance is absorbed and diffused and dried. The coating method is selected from the same methods as described above. The coating amount varies depending on the thickness of the resin layer. A small amount is required when the resin layer is thin, and a large amount is required when the resin layer is thick, but preferably 0.03 parts by weight or more of metal oxide per 1 part by weight of the resin layer. 0.25 parts by weight or less, more preferably 0.08 parts by weight or more 0.15
It is less than or equal to parts by weight. If it is out of this range, that is, if it is less than 0.03 parts by weight, the sufficient conductivity effect cannot be expected, and if it exceeds 0.25 parts by weight, the cost becomes unnecessary.

In order to apply the support prepared according to the present invention to a photographic material, a photosensitive layer may be provided on the side opposite to the conductive layer described above. Specific examples of the photographic material relating to the present invention include general and industrial photography black-and-white light-sensitive materials, printing and other commercial black-and-white light-sensitive materials, ordinary black-and-white light-sensitive materials such as medical black-and-white light-sensitive materials such as X-ray, and color negatives. Photosensitive material, color reversal photosensitive material, printing photosensitive material,
In addition to the usual multi-layer color light-sensitive materials such as instant color light-sensitive materials, it can be applied to the heat-developable light-sensitive materials described in JP-B-43-4924. For details of the photographic material to which the support of the production method of the present invention is applied, see TH James, "The Theory of".
The Photographic Process "3rd edition, published by MacMillan, edited by The Photographic Society of Japan," Basics of Photographic Engineering-Silver Salt Photo- ", published by Corona, and Akira Sasai," The Chemistry of Photography, "published by Photo Industry Publishing. ..

[0015]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these embodiments.

Example 1 A polyethylene terephthalate film having a thickness of 100 μm was subjected to corona discharge treatment (Kasuga Denki HF-403 type), and then a styrene-butadiene-acrylic acid copolymer latex was applied as an easy-adhesion layer to a thickness of 0.1 μm when dried. I worked. Next, the following resin composition liquid was applied so as to have a thickness of 3.5 μm when dried. Resin composition liquid 1) 90 parts by weight of water 2) 4 parts by weight of gelatin 3) Sumika gel L-5 (H) (water-absorbing polymer, manufactured by Sumitomo Chemical Co., Ltd.) 2 parts by weight (as solid content) 4) 1 % Sodium dodecylbenzene sulfonate aqueous solution 1 part by weight 5) 5% saponin aqueous solution 2 parts by weight 6) 10% formalin aqueous solution 1 part by weight Next, this coated film is heated at 50 ° C. for 2 hours to be water-insoluble and water-absorbing. A resin layer was formed. Next, (a), (b),
(C) and (d) Four kinds of stannic chloride (antimony treated) solutions were prepared. (A) 90 parts by weight of water 30% by weight of a stannous oxide (antimony treated) colloidal solution with an average particle size of 15 mμ 10 parts by weight of an aqueous solution Megafac F-120 (fluorine-based surfactant, Dainippon Ink and Chemicals Co., Ltd. ) 5 × 10 ^-5 parts by weight (b) ・ 90 parts by weight of water ・ 30% by weight of colloidal stannic oxide (antimony-treated) colloid solution having an average particle diameter of 200 mμ 10 parts by weight aqueous solution ・ Megafuck F-120 5 × 10 ^-5 parts by weight (c) 90 parts by weight of water 7 parts by weight of the stannic oxide colloidal solution used in (a) 3 parts by weight of the stannic oxide colloidal solution used in (b) Megafac F- 120 5 × 10 ^-5 parts by weight (d) ・ 80 parts by weight of water ・ 10 parts by weight of 15% by weight gelatin aqueous solution ・ 10 parts by weight of the stannic oxide colloid solution used in (a) ・ Megafuck F-120 5 × 10 ^-5 parts by weight or more of the stannic oxide colloidal dispersion liquid is applied on the resin layer prepared in advance as a coating solution of about 10 g / m ² A film support provided with a coated and dried conductive resin layer was prepared. Samples (A), (B), (C), which correspond to stannic oxide solutions respectively,
(D). These samples were placed in an atmosphere of 25 ° C. and 25% RH for 5 hours, and a TR8611A type digital super insulation resistance / micro ammeter (manufactured by Takeda Riken Co., Ltd.) was applied to 250 V to measure the surface resistance value. Cut the sample into a circle with a diameter of 10 cm, attach it to a rubber plate that rotates at a speed of 45 RPM, and heat-resistant nylon fiber and a neoprene plate Press for 60 seconds with a pressure of 50 g / cm ² to generate static electricity at a surface temperature of 50 ° C. , And was measured with a static electricity meter (Statylon-M, manufactured by Shishido Electrostatics Co., Ltd.). The results are shown in Table 1. Incidentally, the sample (E) was a measurement of only the water-insoluble and water-absorbent resin layer which was not subjected to the conductive treatment.

[0017]

[Table 1]

Further, the cross sections of the samples (A), (B), (C), and (D) were observed with a transmission electron microscope (× 5000), and the results shown in Table 2 were obtained.

[0019]

[Table 2]

From the results shown in Tables 1 and 2, the surface resistance value can be reduced by forming a continuous layer on the surface layer, while the triboelectrification is water insoluble and the conductive metal in the water absorbent resin layer is reduced. It can be seen that it is prevented by the oxide. Further, it is understood that the one in which the conductive metal oxide is mixed with the resin in advance cannot exert its effect.

Claims (4)

[Claims] 1. A step of 1) previously providing a water-insoluble and water-absorbent resin layer on at least one surface of a film substrate, and 2) a colloidal conductive metal oxide containing at least one of Zn, Sn and In as a cation. A method for producing a photographic support, comprising the step of diffusing a water dispersion substantially free of resin from the surface layer of the water-insoluble and water-absorbent resin layer. 2. The method for producing a photographic support according to claim 1, wherein the water-insoluble and water-absorbent resin layer is a crosslinked gelatin layer. 3. The method for producing a photographic support according to claim 1, wherein the water-insoluble and water-absorbent resin layer contains a highly water-absorbent polymer compound in the layer. 4. The method for producing a photographic support according to claim 1, wherein the colloidal conductive metal oxide is fine particles having an average particle diameter of 50 mμ or less.