JPH0648362B2 - Method for producing photographic support - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application] The present invention relates to a photographic support in which paper is used as a substrate (hereinafter, the substrate paper is referred to as base paper), and both surfaces thereof are coated with a resin. The present invention relates to a photographic support in which edge stains due to penetration after development processing (hereinafter referred to as a developer) from the cut surface of the edge of the support are prevented.

[Prior art]

Conventionally, as a photographic support excluding film photosensitive materials,
So-called baryta paper was used in which one side of the paper was coated with a baryta layer mainly composed of barium sulfate, but recently, in order to speed up the automation of development processing, a waterproof support with both sides of the base paper coated with resin was used. It has come to be used. However, even when the above waterproof support is used, permeation of the developing solution from the cut surface of the end of the support cannot be prevented. The developer that has permeated from the cut surface of the edge cannot be removed by a short-time photographic processing, and it turns brown due to heat or aging, and becomes a stain on the edge portion of the photograph, significantly impairing its value as a photograph. In order to prevent this edge stain, a method of giving a high sizing property to the base paper layer has been attempted.

Fatty acid soap type sizing agents as shown in Japanese Examined Patent Publication No. 47-26961 and alkyl ketene dimers as shown in JP-A No. 51-132822 are used as sizing agents for photographic base paper, but they have their respective drawbacks. , Not enough. That is, the fatty acid soap type sizing agent has a small size effect on the alkali in the developer,
When manufacturing base paper, there is a drawback that it is easily affected by the hardness of water. On the other hand, in the case of an alkyl ketene dimer, the size effect is low with respect to the alcohol in the developing solution, and sufficient sizeability cannot be obtained unless a known polyamide polyamine epichlorohydrin resin as a fixing agent is used in a relatively large amount. However, none of these sizing agents are sufficiently satisfactory for photographic base paper.

[Problems to be solved by the invention]

Therefore, an object of the present invention is to prevent permeation of a developing solution into the end portion of a photographic support having both sides of a base paper coated with a resin, and to prevent edge stains.

[Means and Actions for Solving Problems]

The present inventors have conducted extensive studies to overcome the above-mentioned drawbacks, and as a result, in a method for producing a photographic support in which both sides of a raw paper are coated with a resin, a polyvinyl alcohol-based resin having a cationic structural unit and a size It has been found that the object of the present invention can be achieved by using as a substrate a base paper which is prepared by adding a chemical agent and paper.

The effect of the present invention can be obtained only by using a polyvinyl alcohol-based resin having a cationic structural unit and a sizing agent together, and cannot be obtained by the addition of each of them.

The polyvinyl alcohol (hereinafter abbreviated as PVA) -based resin having a cationic structural unit used in the practice of the present invention includes a PVA-based resin and a PVA-based resin having a structural unit containing amino nitrogen or quaternary ammonium nitrogen as one component. Refers to a copolymer of As a typical example thereof, as a PVA-based resin, quaternized PVA obtained by reacting PVA with a cationizing agent such as 3-chloro-2-hydroxypropyltrimethylammonium chloride, N-
(3-dimethylaminopropyl) methacrylamide,
Resin obtained by saponifying a copolymer of vinyl acetate and an acrylamide type cationic monomer such as trimethyl-3- (1-methacrylamido-propyl) ammonium chloride, N- (3-allyloxy-2-hydroxypropyl) Resin obtained by saponifying a copolymer of vinyl acetate and an allyl ether type cationic monomer such as dimethylamine and N- (4-allyloxy-3-hydroxybutyl) dimethylamine, and a cationic monomer and vinyl acetate are required. In addition, there are resins obtained by saponifying copolymers with other copolymerizable monomers such as acrylamide and vinyl ether. Further, a copolymer having a PVA-based resin as one component is obtained by reacting PVA having a mercapto group at a terminal or carboxy-modified PVA with a cationic monomer of acrylamide type and another copolymerizable monomer such as acrylamide. Examples thereof include copolymers and copolymers obtained by reacting cationized PVA having a mercapto group at the terminal with acrylamide and / or acrylic acid. Specific synthetic methods of PVA-based resins having these cationic structural units include JP-A-56-118997 and JP-A-56-88413.
JP-A-59-192799 and JP-A-60-173.
See 198 and JP-A-60-215899. The content of the cationic structural unit of the PVA-based resin having the cationic structural unit used in the practice of the present invention is 0.01 to 18 mol%, preferably 0.1 to 10 mol%.
The range is good. If it is less than 0.01 mol%, the yield in the stock slurry will be poor, and if it exceeds 18 mol%, the effect of preventing the permeation of the developer from the edge of the support will be poor, such being undesirable.

The amount of the PVA-based resin having a cationic structural unit used in the practice of the present invention is usually 0.
It is 1 to 10%, preferably 0.5 to 5.0%. If the addition amount is small, the effect of preventing the permeation of the developer from the edge of the support is poor,
Even if the amount is too large, the improvement of the penetration preventing effect is not recognized.

Examples of sizing agents used in the practice of the present invention include fatty acid metal salts and / or fatty acids, alkyl ketene dimers,
Alkenyl or alkyl succinic anhydride, JP-A-54
Examples include epoxidized higher fatty acid amides described in JP-A-147211 and organic fluoro compounds described in JP-A-56-109343.

In order to effectively achieve the object of the present invention, a sizing agent that is advantageously used is a fatty acid metal salt in a mode in which it is fixed to the pulp with a water-soluble aluminum salt such as aluminum chloride, vanadium sulfate, and polyaluminum chloride. Alternatively, and / or an alkylketene dimer or a combination sizing agent of an alkylketene dimer and an epoxidized higher fatty acid amide in a mode of being fixed to pulp with or without a fatty acid and a water-soluble aluminum salt can be used.

The higher fatty acid salt and / or higher fatty acid advantageously used in the practice of the present invention has a carbon number of 12 to 22.
Are preferred. The amount added is 0.5 to 4.0 per absolute dry weight of pulp from the viewpoint of the effect of preventing the permeation of the developer at the edge of the support.
A weight% range is preferred. In addition, the amount of the water-soluble aluminum salt added when used in combination with the fatty acid metal salt and / or fatty acid is a solid weight relative to the fatty acid metal salt and / or fatty acid from the viewpoint of the effect of preventing permeation of the developer at the edge of the support. The range of 1/20 to 4/1 is particularly preferable, and the range of 1/10 to 1/1 is particularly preferable.

Alkyl ketene dimers that are advantageously used in the practice of the present invention include those disclosed in JP-A-51-132822, Tappi Vol.
39, No. 1 (1956), etc.,
The alkyl group has 8 to 30 carbon atoms, preferably 12 to 18 carbon atoms.
The ones are good. Alkyl ketene dimer is usually commercially available as its emulsion, and specific examples thereof include Accorpel 360XC of Dick Hercules Co. and the like.
The amount of the alkyl ketene dimer added is 0.2 to the dry weight of pulp based on the effect of preventing the permeation of the developer at the edge of the support.
A range of 4.0% by weight is preferred.

In order to remarkably achieve the object of the present invention, that is, to prevent the permeation of the developing solution into the edges of the photographic support having resin coated on both sides of the base paper and to prevent edge stain, It is preferable to add a cationic wet strength agent to the PVA-based resin having a cationic structural unit and the sizing system. As the cationic wet strength agent which is advantageously used in the practice of the present invention, a polyamine polyamide epichlorohydrin resin is preferable, and the addition amount thereof is preferably in the range of 0.05 to 4.0% by weight based on the pulp dry weight. 0.15-1.5
A weight% range is preferred.

Further, in order to more remarkably achieve the object of the present invention, it is advantageous that the base paper contains a divalent metal salt by spraying or a tab size press. As the divalent metal salt, an alkaline earth metal salt such as calcium or magnesium or a transition metal such as zinc or nickel as a cation, while a salt having a halogen element such as chlorine or a sulfate ion as an anion is used. I can give you. Particularly preferred metal salts are calcium chloride, magnesium chloride and barium chloride. The content of the divalent metal salt, from the viewpoint of preventing penetration of the developer from the support end, the range of 0.1g / m ² ~5.0g / m ^2, in particular 0.5 g / m ² to 2.5 g / m ²
Is preferred.

As the pulp used in the practice of the present invention, natural pulp is mainly used, but synthetic pulp or synthetic fiber other than natural pulp may be used if necessary. Natural pulp was subjected to usual bleaching treatment such as chlorine, hypozinc salt, chlorine dioxide bleaching, alkali extraction or alkali treatment and, if necessary, oxidative bleaching treatment with hydrogen peroxide, oxygen, etc., and a combination thereof. Wood pulp such as softwood pulp, hardwood pulp, and mixed hardwood pulp is advantageously used, and various types such as kraft pulp, sulfite pulp and soda pulp can be used.

The base paper used in the practice of the present invention may contain various polymer compounds and additives in addition to the PVA-based resin and sizing agent of the present invention when preparing a stock slurry. For example, as a water-soluble polymer compound, anionized polyacrylamide, cationized starch, etc., as a filler,
Clay, kaolin, calcium carbonate, barium sulfate, titanium oxide, etc., as a pH adjusting agent, caustic soda, sodium carbonate, etc., as a coloring pigment, JP-A-54-147033.
As whitening agents such as those listed in No. 1, Whitetex series manufactured by Sumitomo Chemical Co., Ltd., Shin Nisso Kako Co., Ltd.
Kay Coal series manufactured by Bayer Japan Co., Ltd., Blancophore series manufactured by Bayer Japan KK, and other dyes may be appropriately combined and contained.

It is advantageous that the base paper used for carrying out the present invention contains various water-soluble polymer compounds and additives by spraying or tab size press. Examples of such water-soluble polymer compounds and additives include, as water-soluble polymer compounds, cationic starch, polyvinyl alcohol, carboxy-modified polyvinyl alcohol, carboxymethyl cellulose, hydroxyethyl cellulose, cellulose sulfate, gelatin, casein, sodium polyacrylate, styrene. -Maleic anhydride sodium salt, polystyrene polystyrene sulfonate, etc., latex, emulsion as petroleum resin emulsion, styrene-
Pigments such as styrene-butadiene copolymer, ethylene-vinyl acetate copolymer, polyethylene, vinylidene chloride copolymer, etc. as pigments such as clay, kaolin, talc, barium sulfate and titanium oxide. As an antistatic salt,
Sodium chloride, potassium chloride, lithium chloride, sodium citrate, lithium citrate, etc. as pH adjusters, hydrochloric acid, phosphoric acid, caustic soda, sodium carbonate, etc.
In addition, it is advantageous that the color pigment, the fluorescent whitening agent, the dye and the like additives described above are contained in combination.

The thickness of the base paper is not particularly limited, but it is preferable that the paper has good surface smoothness, such as being compressed by applying pressure with a calender after paper making, and the basis weight is 40 g / m ² ~
250 g / m ² is preferred.

The resin for coating the base paper used in the practice of the present invention,
A polyolefin resin or a resin that is cured by an electron beam can be used. Examples of the polyolefin resin include homopolymers of olefins such as low density polyethylene, high density polyethylene, polypropylene, polybutene, and polypentene, copolymers of two or more olefins such as ethylene-propylene copolymers, and mixtures thereof. Those having various densities and melt viscosity indexes (melt indexes) can be used alone or as a mixture thereof.

Further, in the resin for coating the base paper, white pigments such as titanium oxide, zinc oxide, talc, calcium carbonate, stearic acid amide, fatty acid amides such as arachidic acid amide,
Zinc stearate, calcium stearate, aluminum stearate, magnesium stearate, zirconium octylate, sodium palmitate, calcium palmitate, fatty acid metal salts such as sodium laurate, tetrakis [methylene-3 (3,5-di-tert- Butyl-4-hydroxyphenyl) propionate] methane, 2,6-di-tert-butyl-4-methylphenol and other antioxidants, cobalt blue, navy blue, ultramarine blue, cerulean blue, phthalocyanine blue and other blue pigments and dyes , Cobalt violet, fast violet, manganese purple and other magenta pigments and dyes, bis (te
fluorescent brighteners such as rt-butyl-benzoxazole) thiophene and bis (methylbenzoxazole) naphthalene, Tinuvin 320, Tinuvin 326, Tinuvin 32
It is preferable to add various additives such as an ultraviolet absorber such as 8 (above trade name of Ciba-Geigy Co., Ltd.) in an appropriate combination.

The photographic support produced by the present invention is produced by a so-called extrusion coating method in which a heat-melted resin is cast in the case of a polyolefin resin on a running base paper, and both surfaces thereof are coated with the resin. Further, in the case of a resin that is cured by an electron beam, the resin is applied by a commonly used coater such as a gravure coater or a blade coater, and then the resin is irradiated with an electron beam to cure and coat the resin. Further, it is preferable that the base paper is subjected to activation treatment such as corona discharge treatment or fire treatment before the base paper is coated with the resin. The emulsion side surface of the photographic support has a glossy surface, depending on the application.
It has a matte surface, a silky surface, etc., and the back surface is usually a matte surface, and the front surface or both front and back surfaces can be subjected to activation treatment such as corona discharge treatment or fire treatment as required. The thickness of the resin layer of the resin-coated paper is not particularly limited, but it is generally advantageous that the resin-coated paper is extrusion-coated to a thickness of about 5 to 50 microns.

Various back coat layers can be coated on the photographic support in the invention for the purpose of preventing electrification and curling. In addition, the backcoat layer is Japanese Patent Publication No.
No. 20, JP-B-57-9059, JP-B-57-539
40, JP-B-58-56859, JP-A-59-21
Inorganic antistatic agents, organic antistatic agents, hydrophilic binders, latexes, curing agents, pigments, surfactants and the like described or exemplified in JP-A-4849 and JP-A-58-184144 can be contained in appropriate combination. .

The photographic support according to the present invention is coated with various photographic constituent layers, for color photographic printing paper, black-and-white photographic printing paper, typesetting printing paper, copy printing paper, reversal photographic material, silver salt diffusion transfer It can be used for various negative and positive applications, printing materials, and various other applications. For example, silver chloride, silver bromide, silver chlorobromide, silver iodobromide, and silver chloroiodobromide emulsion layers can be provided. By incorporating a color coupler in the silver halide photographic emulsion layer,
Multilayer silver halide constituent layers can be provided. Also,
A silver salt diffusion transfer image-receiving layer can be provided by containing physical development nuclei. As the binder for the photographic constituent layers, in addition to ordinary gelatin, hydrophilic polymer substances such as polyvinylpyrrolidone, polyvinyl alcohol, and sulfate ester compounds of polysaccharides can be used. Further, the above-mentioned photographic constituent layers can contain various additives. For example, as a sensitizing dye, a cyanine dye, a merocyanine dye, a chemical sensitizer, a water-soluble gold compound,
Antifoggants or stabilizers such as sulfur compounds, hydroxy-triazolopyrimidine compounds, mercapto-heterocyclic compounds, etc., as hardeners, formalin,
Vinyl sulfone compounds, aziridine compounds, etc. as coating aids, benzene sulfonates, sulfosuccinate salts, etc., antifouling agents, dialkyl hydroquinone compounds, etc. A pH adjusting agent, a fogging agent, a water-soluble iridium compound, a water-soluble rhodium compound, and the like can be contained in an appropriate combination during the production and dispersion of silver halide.

The silver halide photographic material according to the present invention has an exposure as described in "Photosensitive Material and Handling Method" (Kyoritsu Shuppan, Goro Miyamoto, Photographic Technology Course 2) according to the photographic material.
Processing such as developing, stopping, fixing, bleaching, stabilizing, etc. are carried out. In particular, multi-layer silver halide color photographic materials which are subjected to one-bath bleach-fixing processing after color development include CD-III and CD-IV (the above two kinds of materials are used. The compound can be processed with a color developing solution of any main agent such as Kodak's trade name), Droxychrome (May &Baker's trade name). A developing solution containing such a main agent may contain a development accelerator such as benzyl alcohol, thallium salt or phenidone. Further, a useful one-bath bleach-fixing solution is a solution of a metal salt of aminopolycarboxylic acid (for example, a ferric complex salt of ethylenediaminetetraacetic acid, propylenediaminetetraacetic acid, etc.), and a fixing agent such as sodium thiosulfate or thiosulfate. Ammonium sulfate and the like are useful. Various additives can be contained in the one-bath bleach-fixing solution. For example, desilvering accelerators (for example, mercaptocarboxylic acid described in US Pat. No. 3,512,979, mercapto-heterocyclic compound described in Belgian patent 682,426, etc.), antifouling agent, pH adjusting agent or pH buffering agent. , Various hardeners (eg, magnesium sulfate, aluminum sulfate, potassium alum, etc.) and surfactants may be contained in combination. Also, although such a one-bath bleach-fix solution can be used at various pH's, the useful pH range is pH 6.0-8.0.

Next, examples will be described to more specifically describe the present invention.

〔Example〕

A mixed stock of 50 parts by weight of hardwood bleached kraft pulp and 50 parts by weight of softwood sulfite pulp was beaten to 310 ml of Canadian Standard Freeness, and 170 g / m ² of paper was made with the following internal addition composition. (Numerical values in the formulation indicate parts by weight.) ・ Internal addition formulation of alkylketene dimer size Pulp (LBKP / NBSP = 1/1) 100 Fluorescent brightener 0.15 Blue dye 0.00005 Polymer 3.0 AlCl shown in Table 1. ₃ 0.7 (Adjust pH to 6.0 with caustic soda when adding AlCl ₃ ) Alkyl ketene dimer emulsion 0.4 (as ketene dimer content) Polyamine polyamide epichlorohydrin resin 0.4 ・ Internal addition of fatty acid soap size Pulp (LBKP / NBSP = 1 / 1) 100 Fluorescent whitening agent 0.15 Blue dye 0.00005 Polymer shown in Table 3.0 Fatty acid soap 1.0 Bansulfate 1.0 Polyamine polyamide epichlorohydrin resin 0.4 The obtained wet paper was dried on a heating plate at 110 ° C. This paper is impregnated with the impregnating liquid of the following composition at 30 g / m ² and 1
It was dried with a hot air constant temperature dryer at 10 ° C. (Values in the formulation indicate parts by weight.) Carboxy-modified polyvinyl alcohol 4.0 Diaminostilbene disulfonate type fluorescent whitening agent 0.05 Blue dye 0.002 (Calcium chloride 4.0) 100 sheets of water impregnated and dried is lined. After supercalendering at a pressure of 90 Kg / cm, both sides were subjected to corona discharge treatment. Next, on the back side, high density polyethylene (density 0.96 g / cm ³ , M
I5) and low density polyethylene (density 0.92 g / cm ³ , MI
The 1: 1 mixture of 5) was coated at a resin temperature of 330 ° C. to a thickness of 30 μ using a melt extrusion coating machine. Next, low-density polyethylene containing 10% anatase type titanium oxide on the surface (polyethylene before pigment addition has a density of 0.92 g / cm
³ , MI5) and high-density polyethylene (polyethylene before addition of pigment has a density of 0.96 g / cm ³ , MI5) of 7: 3 were coated at a resin temperature of 330 ° C. to a thickness of 30 μ.

Then, after subjecting the surface of polyethylene containing titanium oxide to corona discharge treatment, a blue-sensitive silver halide emulsion layer containing a yellow color-forming coupler, an intermediate layer, and a green-sensitive silver halide emulsion containing a magenta color-forming coupler in order adjacent to the support. A layer, an ultraviolet absorbing layer, a red-sensitive silver halide emulsion layer containing a cyan color coupler and a protective layer were coated to obtain a color photographic paper. This color photographic paper is developed by a continuous automatic developing machine (FC Co., Ltd., color roll processor).

The setting processing time is as follows.

Color development (33 ° C, 3 minutes 30 seconds) → bleach-fixing (1 minute 30
Second) → Washing (3 minutes) The composition of each treatment is as follows.

Color developer Sodium carbonate (monohydrate) 46.0 g Anhydrous sodium sulfite 2.0 g Potassium bromide 0.5 g CD-III 4.5 g Sodium hexametaphosphate 0.5 g Hydroxylamine sulfate 2.0 g Fluorescent brightener 0.5 g Benzyl alcohol 12c.c .Diethylene glycol 10c.c. Adjust the pH to 10.2 with sodium hydroxide and add water to bring the total volume to 1
Adjust to.

Bleach-fixing solution Ferric complex salt of ethylenediaminetetraacetic acid 56 g Disodium salt of ethylenediaminetetraacetic acid 2 g Ammonium thiosulfate salt 60 g Anhydrous sodium sulfite 20 g Sodium acid sulfite 5 g Disodium phosphate 12 g The total amount is adjusted to 1 with water.

With respect to the color photographic paper which had been subjected to the development treatment, the penetration depth of the liquid from the edge was read using a magnifying glass.

The results obtained are shown in Table 1.

As is clear from Table 1, a sample according to the present invention (No. 6) in which a PVA resin having a cationic structural unit as an internally added polymer and an alkyl ketene dimer as a sizing agent were added.
(F) is a sample to which no internally added polymer is added (No. a), and a sample other than the present invention to which cationized starch or anionic polyacrylamide is added as an internally added polymer (No. b, N)
It can be clearly seen that the penetration of the developing solution from the edge of the support is greatly improved as compared with o.e), and as a result, coloring of the edge of the printing paper is considerably prevented. In addition, a sample according to the present invention in which a PVA-based resin having a cationic structural unit as an internally added polymer and a fatty acid soap as a sizing agent are added (No.
H) is a sample (N of the present invention) to which cationized starch was added.
It can be clearly seen that the penetration of the developing solution from the edge of the support is greatly improved as compared with o. c), and as a result, coloring of the edge of the photographic paper is considerably prevented. Further, it is well understood that the effect of the present invention is remarkable when the base paper contains a divalent metal salt such as calcium chloride (Sample No. G and No. G).

〔The invention's effect〕

According to the present invention, it is possible to provide an excellent photographic material in which the permeation of the developing solution from the edges of a photographic support having both sides of a base paper coated with a resin is greatly improved, and thus edge stains are prevented.

 ─────────────────────────────────────────────────── --- Continuation of the front page (56) References JP-A-60-217357 (JP, A) JP-A-58-80637 (JP, A) JP-A-55-95943 (JP, A) JP-A-54- 109428 (JP, A)

Claims (4)

[Claims] 1. A method for producing a photographic support in which both sides of a base paper are coated with a resin, wherein a base paper produced by adding a sizing agent and a polyvinyl alcohol resin having a cationic structural unit is used. A method for producing a photographic support. 2. The photographic support according to claim 1, wherein the base paper is made by adding 0.2 parts by weight or more of alkyl ketene dimer as a sizing agent (based on the weight of pulp) to a paper stock. Body manufacturing method. 3. The base paper comprises fatty acids and / or sizing agents.
Alternatively, the paper is made by adding 0.5 parts by weight or more of a salt thereof (based on the weight of pulp) to the paper stock, and the paper is made.
A method for producing the photographic support according to the item. 4. The method for producing a photographic support according to claim 1, 2, or 3, wherein the base paper contains a divalent metal salt compound.