JPS63285539A - Photographic supporting body - Google Patents

Abstract

PURPOSE:To prevent the penetration of a developer at the end of the titled body, and to lessen the stain of an edge by impregnating with a mixture of polyvinyl alcohol and barium chloride in an original paper incorporated a sizing agent. CONSTITUTION:The titled body is formed by treating with the sizing agent on the both surfaces of the original paper. The mixture of polyvinyl alcohol and barium chloride is impregnated or applied with the titled body. The polyvinyl alcohol is exemplified by a partially saponified polyvinyl alcohol, a completely saponified polyvinyl alcohol and a cation modified polyvinyl alcohol. And, the barium chloride is incorporated in the polyvinyl alcohol in an amount of about 5-200pts.wt. based on 100pts.wt. of said polyvinyl alcohol. Accordingly, as said mixture is impregnated or applied on the titled body, the penetration of the developer to the end of the titled body and the stain of the edge are prevented, thereby improving the titled body.

Description

[Detailed Description of the Invention] [Field of Industrial Application] The present invention relates to a photographic support that uses paper as a substrate (hereinafter, the paper serving as the substrate is referred to as base paper) and coats both sides with resin. The present invention relates to a photographic support which prevents edge staining caused by penetration of a developing solution (hereinafter referred to as developer) from the cut surface of the edge of the support.

[Prior art]

Traditionally, photographic supports other than film-sensitive materials include:
So-called baryta paper, in which one side of the paper was coated with a baryta layer mainly composed of barium sulfate, was used, but recently, in order to automate and speed up the development process, waterproof supports in which both sides of the base paper are coated with resin have been used. has come to be used. However, even when the above-mentioned waterproof support is used, it is not possible to prevent the developer from penetrating through the cut surface of the end of the support. The developer that permeates through the cut edges cannot be removed by short-term photographic processing, and will turn brown due to heat or over time, staining the etched areas of the photograph, and significantly reducing the value of the photograph. . In order to prevent this edge staining, attempts have been made to provide a high size property to the base paper layer.

Fatty acid soap type sizing agents as shown in Japanese Patent Publication No. 47-26961 and alkyl ketene dimers as shown in % Patent Publication No. 51-132822 have been used as sizing agents for photographic paper, but each has drawbacks. , is not enough. In other words, the fat mirror soap type sizing agent has a low sizing effect on the alkali in the developer,
When producing base paper, there are drawbacks such as the fact that it is easily affected by the hardness of the water used. On the other hand, in the case of alkyl ketene dimer, the sizing effect is low against the alcohol in the developer, and sufficient sizing properties cannot be obtained unless a relatively large amount of polyamitopo IJ amine epichlorohydrin resin, which is known as a fixing agent, is used. None of the sizing agents are sufficiently satisfactory for use in photographic base paper.

[Problem that the invention seeks to solve]

Therefore, an object of the present invention is to prevent a developer from seeping into the edges of a photographic support whose base paper is coated with resin on both sides, thereby preventing etch stains.

[Ninth means and action for solving the problem] As a result of the inventors' extensive research to overcome the above-mentioned drawbacks, polyvinyl alcohol It has been found that the objects of the present invention can be achieved by impregnating or coating base paper with a mixture consisting of barium chloride and barium chloride.

The effects of the present invention are obtained by impregnating or coating base paper to which a sizing agent has been added with a mixture of polyvinyl alcohol and barium chloride.

In the present invention, base paper is impregnated or coated with a mixture of polyvinyl alcohol and barium chloride, for example, as an aqueous solution.

The polyvinyl alcohol used in the present invention is preferably unmodified polyvinyl alcohol with a degree of saponification of 80% or more or cationically modified polyvinyl alcohol which is polyvinyl alcohol having a cationic structural unit. The polyvinyl alcohol having a cationic structural unit referred to herein refers to polyvinyl alcohol having a structural unit containing amino diaminochloride or quaternary ammonium nitrate.

The amount of impregnation or coating of the mixture consisting of polyvinyl alcohol and barium chloride used in the present invention is 0.5 f/
rr? The above is preferable, and if it is less than 0.51β, the effect of preventing penetration of the developer is poor.

In the present invention, a mixture is prepared by adding barium chloride in an amount within the range of 5 to 200 parts by weight per 100 fifi parts of polyvinyl alcohol to prepare a mixture for surface treatment.

When the amount of barium chloride is less than 5 parts by weight, the effect of preventing penetration of the developer is poor. Also, the amount of barium chloride is 200
If the amount exceeds 1 part by weight, no improvement in the surface strength of the base paper is observed, which is not preferable.

Sizing agents used in the practice of the present invention include fatty acid metal salts and/or fatty acids, alkyl ketene dimers,
Alkenyl or alkylconolic acid anhydride, JP-A-5
Epoxidized higher fatty acid amides described in No. 4-147211 and organic fluoro compounds described in JP-A-56-109343 are suitable.

In order to effectively achieve the object of the present invention, sizing agents that are advantageously used include fatty acid metal salts fixed to the pulp with water-soluble aluminum salts such as aluminum chloride, sulfuric acid, and polyaluminum chloride. Alternatively, an alkyl ketene dimer or a combination sizing agent of an alkyl ketene dimer and an epoxidized higher fatty acid amide may be used, which is fixed to the pulp with or without a fatty acid and a water-soluble aluminum salt.

The higher fatty acid salts and/or higher fatty acids that are advantageously used in the practice of the present invention have a carbon number of 12 to 22.
Preferably. The amount added is 0.5 to 0.5 to 1.0% per absolute dry weight of the pulp in order to prevent penetration of the developer at the edge of the support.
A range of 4.0% by weight 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 determined based on the solid weight relative to the fatty acid metal salt and/or fatty acid from the viewpoint of preventing penetration of the developer at the edge of the support. The standard range is 1/20 to 4/1, especially 1/10.
A range of 1/1 to 1/1 is preferable.

Examples of the alkyl ketene dimer advantageously used in carrying out the present invention include JP-A No. 51-132822, Tappi
Vol. 39.41 (195'6) etc., and the alkyl group has 8 to 30 carbon atoms, preferably 12 to 18 carbon atoms. Alkyl ketene dimers are usually commercially available as emulsions thereof; specific examples include Deitzk Herkiereth Co. Accobel 360XC
and so on. The amount of the alkyl ketene dimer added is preferably in the range of 0.2 to 4.0% by weight based on the absolute dry weight of the bulb in view of the effect of preventing penetration of the developer into the edge of the support.

In order to significantly achieve the object of the present invention, that is, to prevent developer solution from seeping into the edges of a photographic support whose base paper is coated with resin on both sides, and to prevent etch stains. Preferably, a cationic wet strength agent is added to the sizing system. As the cationic wet paper strength agent advantageously used in carrying out the present invention, polyamine polyamide epichlorohydrin resin is preferable, and the amount added is in the range of O,OS to 4.0 [1 H] based on the absolute dry weight of the pulp. But especially 0.1
A range of 5 to 1.5% by weight is preferred.

Natural pulp is mainly used as the pulp used in carrying out the present invention, but synthetic pulp and synthetic fibers other than natural pulp may be used as necessary. Natural pulp is subjected to conventional bleaching treatments such as chlorine, hypochlorite, and chlorine dioxide bleaching, alkali extraction or alkaline treatment, and oxidative bleaching treatment using peroxide ice cream, oxygen, etc. depending on the conditions, and combinations thereof. Advantageously, wood pulps of softwood pulp, Cantonese wood pulp, needle T4 broadwood [8 mixed bulbs] are used, and also those of qh polarity such as kraft pulp, sulfide pulp, soda pulp, etc. can be used.

The base paper used in the practice of the present invention can contain various polymeric compounds and additives during the preparation of the paper 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 regulator, as a coloring pigment, such as caustic soda, carbonate, etc. , Japanese Patent Publication No. 54-147
Fluorescent brighteners such as those described in No. 033, Whitex series manufactured by Sumitomo Chemical, Kikool series manufactured by Nippon Sokako, Brancophor series manufactured by Bayer Japan, and other dyes, etc. can be contained in appropriate combinations.

It is advantageous for the base paper used in the practice of the present invention to contain various water-soluble polymer compounds and additives in addition to the polyvinyl alcohol and barium chloride in the present invention by spraying or tab size pressing. Examples of such water-soluble polymer compounds and additives include cationic starch, carboxymethyl cellulose, hydroxyethyl cellulose, cellulose sulfate, gelatin, casein, sodium polyacrylate, styrene-maleic anhydride sodium salt, and polystyrene. Latex and emulsions such as sodium sulfonate, petroleum resin emulsion, ammonium salt of styrene-maleic anhydride copolymer alkyl ester, styrene-butadiene copolymer, ethylene-vinyl acetate copolymer, polyethylene, Pigments such as vinylidene chloride copolymer, clay, kaolin, Merck, barium sulfate, titanium oxide, etc. Antistatic salts such as sodium chloride, potassium chloride, lithium chloride, sodium citrate, lithium citrate, etc., pH adjustment As an agent,
It is advantageous to contain a combination of hydrochloric acid, phosphoric acid, caustic soda, sodium carbonate, and other additives such as the above-mentioned color pigments, optical brighteners, and dyes.

There are no particular restrictions on the thickness of the base paper, but it is preferable to use paper with good surface smoothness, such as by compressing the paper by applying pressure in a calendar after papermaking, and its basis weight is 4 Of/
W? ~250% is preferred.

The base paper coating resin used in the practice of the present invention includes:
A polyolefin resin or a resin that is cured by an electron beam can be used. Polyolefin resins include homopolymers of olefins such as low-density polyethylene, high-density polyethylene, polyglopylene, polybutene, and polybentene, copolymers of two or more olefins such as ethylene-propylene copolymers, and mixtures thereof. Aυ, materials with various densities and melt viscosity indices (melt index) can be used singly or in combination.

In addition, the base paper JLA contains white pigments such as titanium oxide, zinc oxide, Merck, and calcium carbonate, fatty acid amides such as stearic acid amide and araxic acid amide, zinc stearate, calcium stearate, aluminum stearate, Fatty acid metal salts such as magnesium stearate, zirconium octylate, sodium balmitate, calcium valmitate, and sodium laurate, tetrakis[methylene-3 (3,5-di-te)
r tert-butyl-4-hydroxyphenyl)gropionate] methane, antioxidants such as 2,6-tert-butyl-4-methylphenol, cobalt blue, m
Blue pigments and dyes such as v, at, cerulean blue, and phthalocyanine blue, magenta pigments and dyes such as cobalt violet, 7 asto violet, and manganese violet, and bis(teri-butyl-benzoxazole).
Optical brighteners such as thiophene, bis(methylbenzoxazole)naphthalene, Tinuvin 320, Tinuvin 32
6. Tinuvin 328 (all Ciba-Geigy products)
It is preferable to add various additives such as ultraviolet absorbers and the like in appropriate combinations.

In the case of a polyolefin resin, the photographic support produced according to the present invention is coated on a running base paper by heating and melting the resin.
It is manufactured by a so-called extrusion coating method using T-casting, and both sides thereof are coated with resin. In the case of a resin that can be cured by electron beams, the resin is applied with a commonly used coater such as a gravure coater or a blade coater, and then irradiated with electron beams to cure the resin and cover the resin. Furthermore, before coating the base paper with the resin, it is preferable to subject the base paper to an activation treatment such as a corona discharge treatment or a flame treatment.

The emulsion side surface of a photographic support has a glossy surface, a matte surface, a silky surface, etc. depending on the use, and the long surface is usually a matte surface, and if necessary, the surface or both the front and back surfaces have corona. Activated treatments such as electrical discharge treatment and flame treatment can be applied.

Further, there is no particular restriction on the thickness of the resin layer of the resin board paper, but it is generally advantageous to coat the resin layer with a thickness of about 5 to 50 microns.

The photographic support in the present invention can be coated with various types of coatings for antistatic, curl prevention, etc. In addition, for the back coat layer,
No. 20, Special Publication No. 57-9059, Special Publication No. 57-539
No. 40, Japanese Patent Publication No. 58-56859, Japanese Patent Publication No. 59-21
Inorganic antistatic agents, organic antistatic agents, hydrophilic binders, latexes, curing agents, pigments, surfactants, etc. described or exemplified in No. 4849, JP-A No. 58-184144, etc. can be contained in appropriate combinations. .

For example, styrene/acrylic latex (e.g., Bonron 8X-224 manufactured by Mitsui Toatsu Co., Ltd.), styrene/
Latex such as butadiene latex (e.g. JAR-0642 manufactured by Nippon Gosei Kagaku Co., Ltd.), acrylic latex (e.g. AE-944 manufactured by Nippon Gosei Kagaku Co., Ltd.) and JP-A-56-19043, JP-A-56- 190
47, etc., in any proportion, and more preferably colloidal silica (for example, Snowtex C manufactured by Nissan Chemical Co., Ltd.)
A bank coat layer T-coating can be applied by mixing 50 to 200% by weight of solids with respect to latex.

The photographic support in the present invention is provided with various photographic constituent layers and is suitable for color photographic paper, black and white photographic paper, typesetting photographic paper, copying photographic paper, reversal photographic material, silver salt diffusion transfer. It can be used for various purposes such as for negatives and positives, and as a printing material layer. For example, a silver chloride, silver bromide, silver chlorobromide, silver iodobromide, or silver chloroiodromide emulsion layer can be provided. By incorporating a color fogger into the silver halide photographic emulsion layer,
Multiple silver halide constituent layers can be provided.

Further, a silver salt diffusion transfer image-receiving layer can be provided by containing physical development nuclei. As the binder for these photographic constituent layers, in addition to ordinary gelatin, hydrophilic polymeric substances such as vorivinyl pyrrolidone, polyvinyl alcohol, and polysaccharide sulfate ester compounds can be used. Also,
The above-mentioned photographic constituent layer may contain additives such as those described above.

For example, as background dyes, cyanine dyes, merocyanine dyes, etc., as chemical sensitizers, water-soluble gold compounds, sulfur compounds, etc., as anti-capri agents or stabilizers, hydroxy-triazolopyrimidine compounds, mercap) -
Hardeners such as 4i ring compounds, formalin, vinyl sulfone compounds, aziridine compounds, coating aids, benzene sulfonates, sulfosuccinate salts, anti-staining agents, dialkylnohydroquinones, etc. Compounds, etc., as well as optical brighteners, sharpness-improving dyes, antistatic agents, pH regulators, fogging agents, and furthermore, water-soluble iridium, water-soluble rhodium compounds, etc. may be included in appropriate combinations during the production and dispersion of silver halide. Can be done.

The silver halide photographic material according to the present invention can be exposed to light as described in "Photographic Light-sensitive Materials and Handling Methods" (Kyoritsu Shuppan, written by Gobe Miyamoto, Photographic Technology Preface 2), depending on the photographic material.
Processes such as development, stopping, fixing, bleaching, and stabilization are performed, but multilayer silver halide color photographic materials that undergo bath bleach-fixing treatment after color development are CD-1it and CD-IV.
Compounds of C or higher can be processed with any crude drug color developer such as Kodak (trade name), droxychrome (May & Baker). A developing solution containing such crude drugs may contain a development accelerator such as benzyl alcohol, thallium salt, or phenidone. Also,
Useful one-bath bleach-fix solutions are solutions of metal salts of aminopolycarboxylic acids (e.g., ferric complex salts such as ethylenediaminetetraacetic acid, propylenediaminetetraacetic acid, etc.); fixing agents include sodium thiosulfate, ammonium thiosulfate, etc. is useful. Such a bath bleach-fix solution can contain various additives. For example, desilvering promoters (e.g., mercaptocarboxylic acids as described in U.S. Pat. No. 3,512,979, mercapto-heterocyclic compounds as described in Belgian Patent No. 682,426, etc.), stain inhibitors,
PHa 14 or PH buffering agent, hardening agent (e.g.
Various compounds such as magnesium sulfate, aluminum sulfate, potassium alum, etc.), surfactants, etc. can be contained in combination. 1 liter, such a bath bleach-fix solution can be used in the PR, but the useful PH range is PH 6.0.
~8.0.

Next, examples will be described in order to explain the present invention more specifically.

〔Example〕

A mixed paper stock of 50 parts by weight of hardwood bleached kraft pulp and 50 parts of softwood sulfite halgh was beaten to Canadian Standard Freeness 310d, and the following internal additions were made to 170 f/rr? paper was made. (Numbers in the formulation indicate parts by weight.) - Alkyl ketene dimer size internal addition compounding valve (LBKP/NBKP=1/1) 10
0 Fluorescent brightener 0.15 Blue dye o,oooooshtct
, 0.7(AtCts
If added, adjust to P) 16°0 with caustic soda) Alkyl ketene dimer emulsion 0.4 (as ketene dimer content) Polyamine polyamide epichlorohydrin resin 0.4
・Fatty acid soap size internal addition combination valve (LBKP/NBKP=1/1) 100
Fluorescent brightener 0.15 Blue dye o,oooos Fatty acid soap 1.0 Pan sulfate±
1.0 Polyamine polyamide epichlorohydrin resin O14 The obtained wet paper was heated to 110℃
Dry on a heated grate. This paper was impregnated with 20 η of the impregnating liquid having the composition shown in Table 1, and dried in a constant temperature hot air dryer at 110°C.

The impregnated and dried paper was subjected to supercalender treatment at a linear pressure of 90 Ky/m, and then corona discharge treatment was performed on both sides. Next, apply high-density polyethylene (density 0.96 seam,
MI5) and low density polyethylene (density 0.92 C, M
A 1:1 mixture of I5) was coated to 30μ J≠ using a melt extrusion coater at a resin temperature of 330°C. Next, low-density polyethylene containing 10% anatase pot titanium oxide on the surface (polyethylene before pigment addition has a density of 0.
92f/-1Ml5) and high-density polyethylene (polyethylene before pigment addition has a density of 0.96t/ett1.M
A resin composition consisting of 7:3 of Is) was heated to a resin temperature of 330
-Ting to 30μ JIL at ℃. - Next, after corona discharge treatment is applied to the surface of the polyethylene containing titanium oxide, adjacent to the support, in order, a blue-sensitive silver halide emulsion JFM containing a yellow color-forming coupler, an intermediate layer, and a green-sensitive silver halide emulsion containing a magenta color-forming coupler. An emulsion layer, an ultraviolet absorbing layer, a red-sensitive silver halide emulsion layer containing a cyan coloring coverr, and a belly retention layer were coated to obtain a color photographic paper. This color photographic paper is developed using a continuous automatic development @ (manufactured by FC Seisakusho, Color Roll Processor).

The setting processing time is as follows.

Color development (33℃, 3 minutes 30 seconds) → Bleach fixing (1 minute 30 seconds)
seconds)→washing with water (3 minutes) The composition of each treatment is as follows.

Color developer sodium carbonate (monohydrate) 46. OfAnhydrous Sodium Sulfite 2.01Potassium Bromide
o652CD-1114,5f Sodium hexametaphosphate 0.5f Hydroxylamine sulfate 260? optical brightener
0.5t benzyl alcohol
12CC diethylene glycol
Adjust the pH to 10.2 with 10cc of sodium hydroxide, and adjust the pH to 10.2 with water.

Bleach-fix solution Ferric complex salt of ethylenediaminetetraacetic acid 561 Disodium salt of ethylenediaminetetraacetic acid 2t Ammonium thiosulfate salt 602 Anhydrous sodium sulfite 201 Sodium sulfite
5t disodium phosphate
, 12? Adjust the total volume to t-IA with water.

After the color photographic paper was developed, the depth of penetration of the liquid from the green color was read using a magnifying Ti-.

Obtained results f: are shown in Table 1.

(See the margins below.) As is clear from the results in Table 1, the supports manufactured according to the present invention have improved etch stains and are excellent as photographic supports.

Claims (2)

[Claims] (1) A photographic support comprising a base paper coated on both sides with a resin, characterized in that the base paper is impregnated or coated with a mixture of polyvinyl alcohol and barium chloride. (2) The photographic support according to claim 1, wherein the polyvinyl alcohol is partially saponified polyvinyl alcohol, completely saponified polyvinyl alcohol, or cation-modified polyvinyl alcohol.