JPH0610740B2 - Resin coated paper for photography - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a photographic resin-coated paper in which paper is used as a substrate and both surfaces thereof are coated with a resin capable of forming a film,
More specifically, it relates to a photographic resin-coated paper in which the photographic processing solution is prevented from permeating through the cut surface of the edge of the support and the coloring of the edge of the photograph after development is improved.

Conventionally, paper is often used as a photographic support because of its advantages such as appearance, waist, strength, and price.

However, since the photographic support is required to absorb the photographic processing solution (hereinafter sometimes simply referred to as a processing solution) as little as possible during the development processing, the biggest drawback of the paper as a support is that the photographic processing solution does not absorb the processing solution. It is highly absorbable. In particular, from the viewpoint of rapid development processing, it is less preferable that the processing solution be absorbed in the support. Therefore,
For the purpose of lowering the absorbability of a processing liquid, resin-coated paper having both surfaces coated with a resin capable of forming a film such as polyolefin is widely used as a photographic support. This completely prevents absorption of the treatment liquid from the front and back of the support, but cannot prevent permeation from the cut surface of the end of the support. The processing liquid that has penetrated 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 stains on the white spots in the photograph (hereinafter sometimes simply referred to as edge stains). Therefore, the value as a photograph is significantly impaired.

In order to prevent the permeation of the treatment liquid from the end cut surface of the resin-coated paper, a sizing agent is added to paper (hereinafter sometimes simply referred to as base paper) as a substrate of the resin-coated paper. However, since the sizing agent that can be used has a special use as a photographic support, it requires the following performances. That is, it has a high size effect even for an alkaline and low surface tension developer, does not hinder the adhesion between the base paper and the resin capable of forming a film, does not reduce the whiteness of the base paper, and adversely affects the photograph. It requires things such as not giving.

However, as the sizing agent contained in the base paper of the resin-coated paper, the sizing agent of the type used in general paper, which is fixed by an acid such as rosin and petroleum resin, hardly contributes to the reduction of the permeability to the treatment liquid. . Further, even a resin acid soap such as sodium stearate shown in Japanese Patent Publication No. 47-26961 cannot obtain sufficient resistance to permeation of the treatment liquid. In recent years, alkyl ketene dimers (hereinafter sometimes simply referred to as AKD) as disclosed in JP-A-51-132822 have been used as a sizing agent for base paper. However, an ordinary polyolefin resin such as low-, medium-, high-density polyethylene or a resin composition obtained by simply combining two or more of them is melt-extruded and coated on the front and back layers of the base paper containing AKD by a melt extruder or the like, (Of course, it does not matter if the surface resin layer contains a titanium dioxide pigment)
Even if a photographic resin-coated paper is manufactured, it has not been obtained that the edge stain is sufficiently suppressed.

Furthermore, as disclosed in JP-A-54-147032, AK
In the method using D, the adhesion between the resin film such as polyolefin and the base paper is poor, and there is a problem that another step is required to improve the adhesion.

It is an object of the present invention to provide a photographic resin-coated paper which has excellent adhesion to a resin layer while using AKD-containing photographic base paper and has very little edge stain.

As a result of various studies, the present inventor has found that in a photographic support using AKD-containing paper as a support, at least one surface of the paper has a resin composition containing at least a carboxy-modified polyethylene and a titanium dioxide pigment. It has been found that the object of the present invention can be achieved by coating with an object.

Examples of the AKD used in the practice of the present invention include Accorpel 360XC (manufactured by Deck Hercules), and the addition amount thereof is usually 0.05 to 50% by weight of pulp.
3%, preferably 0.1-1.5%.

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 is usually bleached with chlorine, hypochlorite, chlorine dioxide bleaching, alkali extraction or alkali treatment and, if necessary, peroxide bleaching with hydrogen peroxide, peracetic acid, etc., and combinations thereof. Wood pulp of softwood pulp, hardwood pulp and mixed hardwood mixed pulp that have been subjected to is advantageously used, and also various pulps such as kraft pulp, sulfite pulp, soda pulp, and pulp using anthraquinone compound as a cooking aid. Can be used.

The base paper containing natural pulp as a main component used in the practice of the present invention may contain various polymer compounds and additives in addition to AKD when preparing a stock slurry. For example, water-soluble polymer compounds such as anionized polyacrylamide and cationized starch, wet paper strength enhancers such as polyaminopolyamide epichlorohydrin resin, melamine resin and urea resin, and fillers such as clay, kaolin, calcium carbonate and barium sulfate. It is advantageous to incorporate caustic soda, sodium carbonate, etc., as well as a dye, a fluorescent whitening agent, etc., as a pH adjusting agent such as titanium oxide, in an appropriate combination. For making the base paper, a commonly used paper machine such as a Fourdrinier paper machine and a round net paper machine is used. AKD is usually carried out by an internal addition method into a pulp slurry, but it may be carried out by a spray method or a tab size pressing method.

The base paper used for carrying out the present invention may contain various water-soluble polymer compounds and additives by an internal addition method, but it is advantageous to contain them by a spray or a 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 sulfonate sodium, styrene-butadiene copolymer,
Latex, emulsions such as ethylene-vinyl acetate copolymer, polyethylene, vinylidene chloride copolymer,
As a hygroscopic substance, glycerin, polyethylene glycol, etc., as a pigment, clay, kaolin, talc, barium sulfate, titanium oxide, etc., as a pH adjuster, hydrochloric acid,
It is advantageous to contain a combination of additives such as phosphoric acid, caustic soda, sodium carbonate, etc., such as dyes and optical brighteners.

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 calendar after paper making, and the basis weight is 40 g / m ²
˜250 g / m ² is preferred.

The carboxy-modified polyethylene resin in the present invention,
In the polyethylene molecular structure A polyethylene having a group, for example, polyethylene modified by grafting an unsaturated carboxylic acid on polyethylene is meant. The unsaturated carboxylic acid, α, β-unsaturated carboxylic acid such as maleic acid, acrylic acid, methacrylic acid or alicyclic polycarboxylic acid having an unsaturated bond in the ring, etc.,
Anhydrides, amides, esters and the like of these acids are used.

The carboxy-modified polyethylene resin in the present invention has various densities and melt viscosity indexes (melt index:
(Hereinafter sometimes abbreviated as MI) can be used alone or as a mixture thereof, and low-density carboxy-modified polyethylene is particularly preferable. Further, other resins such as low-density polyethylene, medium-density polyethylene, and high-density polyethylene are appropriately mixed and used as long as the adhesiveness is not impaired.

In the resin layer of the photographic resin-coated paper according to the present invention, in addition to the titanium dioxide pigment, white pigments such as oxidous acid, talc, and calcium carbonate, fatty acid amides such as stearic acid amide and arachidic acid amide, zinc stearate, and steer. Calcium phosphate, 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-hydroxy] (Phenyl) propionate] methane, 2,6-di-tert-butyl-4-methylphenol, 1,3,5-tris (4-tert-
Butyl-3-hydroxy-2,6-di-methylbenzyl)
Antioxidants such as isocyanurate, cobalt blue,
Blue pigments and dyes such as navy blue, ultramarine blue, cerulean blue and phthalocyanine blue, magenta pigments and dyes such as cobalt violet, fast violet and manganese purple, bis (tert-butyl-benzoxazole) thiophenine, bis (methylbenzoxa) Zol) optical brighteners such as naphthalene, Tinuvin 320, Tinuvin 32
6. Chinubin 328 (above the Ciba-Geigy product name)
It is preferable to add various additives such as an ultraviolet absorber and the like in an appropriate combination. As a method of adding these additives to the resin, a melt mixing method using a heating kneading roll, a Banbury mixer, a kneader, an extruder for kneading, or the like is most suitable, and all the components were contained in a desired composition ratio from the beginning. A compound may be prepared and used, or a masterbatch containing each component in a high concentration may be prepared for each component and mixed in a desired ratio for use.

The titanium dioxide pigment used in the practice of the present invention,
Either the rutile type or the anatase type can be used, but it is advantageous to use the anatase type from the viewpoint of whiteness. Further, so-called untreated titanium dioxide which is not subjected to any surface treatment with respect to titanium dioxide, or surface treatment with various organic surface treatment agents such as various alcohols, surfactants, siloxanes, silane coupling agents, etc. It may be applied, or various inorganic surface treatment agents such as aluminum oxide hydroxide, silicon oxide hydroxide, titanium oxide hydroxide, zirconium oxide hydroxide, zinc hydroxide, magnesium hydroxide, manganese compound, phosphoric acid compound or several kinds thereof. A so-called inorganic surface-treated titanium dioxide which is surface-treated by a combination of

The treatment amount of these inorganic surface treatment agents is preferably 0.2 to 1.2% by weight, and particularly preferably 0.2 to 0.6% by weight (calculated in the form of anhydride), based on titanium dioxide.

As the inorganic surface treating agent for the titanium dioxide pigment used in the practice of the present invention, hydrous aluminum hydroxide is preferable, and the treatment amount thereof is 0.2 to 1.2% by weight with respect to titanium dioxide.
0.2 to 0.6% by weight (calculated in the form of Al ₂ O ₃ )
Is particularly preferable.

The content of the titanium dioxide pigment to be contained in the resin layer of the photographic resin-coated paper in the present invention, relative to the resin,
If it is 5% by weight or less, the hiding power as a photographic support is insufficient, while if it is 40% by weight or more, the fluidity is lowered, which is not preferable, and particularly preferably in the range of 7.5% by weight to 25% by weight. is there.

The resin-coated paper using the paper as a substrate in the present invention is produced by a so-called extrusion coating method in which a heat-melted resin is cast on a normally running base paper, and preferably both surfaces thereof are coated with the resin. Further, it is preferable that the base paper is subjected to an activation treatment such as a corona discharge treatment or a flame treatment before the base paper is coated with the resin. The emulsion side surface of resin coated paper is
Depending on the application, it has a glossy surface, a matte surface, a matte surface, etc., the back surface is usually a matte surface, and the front surface or both front and back surfaces are subjected to activation treatment such as corona discharge treatment and flame treatment as necessary. be able to. The thickness of the resin layer of the resin-coated paper is not particularly limited, but it is generally 5 μm to 5 μm.
It is advantageous to extrusion coat to a thickness of about 0 micron.

The resin-coated paper of the present invention can be provided with various silver halide photographic emulsion layers. For example, a silver chloride, silver bromide, silver chlorobromide, silver iodobromide, or silver chloroiodobromide agent layer can be provided. Further, a color coupler may be incorporated in the silver halide photographic emulsion layer to provide a multilayer silver halide photographic constituent layer. As a binder for these silver halide emulsion 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 silver halide emulsion layer may contain various additives. For example, as a sensitizing dye, a cyanine dye, a merocyanine dye, a chemical sensitizer,
Water-soluble gold compounds, sulfur compounds, etc., as antifoggants or stabilizers, hydroxy-triazolopyrimidine compounds, mercapto-heterocyclic compounds, etc., as hardeners, formalin, vinyl sulfone compounds, aziridine compounds, etc., as coating aids , Benzene sulfonate, sulfosuccinate, etc., as anti-fouling agents, such as dialkyl hydroquinone compounds, etc., as well as optical brighteners, sharpness improving dyes, antistatic agents, pH control agents,
In addition, water-soluble iridium during the production and dispersion of silver halide,
A water-soluble rhodium compound or the like can be contained in an appropriate combination.

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.
Processes such as development, stoppage, fixing, bleaching, and stabilizing are carried out. Particularly, a multi-layer silver halide color photographic material which undergoes a one-bath bleach-fixing process after color development includes CD-III and CD-IV (the above two compounds). Can be processed with a color developing solution of any main agent such as Kodak's trade name), Droxychrome (May and 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 promoters (e.g., mercaptocarboxylic acids described in U.S. Pat. No. 3,512,979, mercapto-carboxylic acids described in Belgian Patent 682,426).
Heterocyclic compounds, etc.), antifouling agents, pH control or P
Various compounds such as an H buffer, a hardener (eg, magnesium sulfate, aluminum sulfate, potassium alum, etc.) and a surfactant can be contained in combination. Also, although such a one-bath bleach-fix solution can be used in a variety of PH's, the useful PH range is PH 6.0-8.0.

Example 1 50 parts by weight of hardwood bleached kraft pulp and 50 parts by weight of softwood bleached sulfite pulp were mixed with Canadian
Standard freeness was beaten to 310 ml, and further 3 parts by weight of cationized starch, 0.2 parts by weight of anionized polyacrylamide, AKD emulsion (as ketene dimer content) and 1 part by weight of polyamino acid as a ketene dimer content based on pulp parts by weight. 0.4 parts by weight of polyamide epichlorohydrin resin was added to produce paper having a basis weight of 160 g / m ² .

The obtained wet paper is dried at 110 ° C., and subsequently 3 parts by weight of carboxy-modified polyvinyl alcohol, 0.05 part by weight of optical brightener, 0.002 part by weight of blue dye, 0.2 part by weight of citric acid and 9 parts of water.
The impregnating liquid consisting of 7 parts by weight was impregnated with 25 g / m ² and
After drying with hot air at 0 ° C. and calendering at a linear pressure of 90 kg / cm, both sides were subjected to corona discharge treatment to produce a base paper of photographic resin coated paper.

On the other hand, in a Banbury mixer, 70 parts by weight of carboxy-modified polyethylene (MI5, density 0.94 g / m ² ), 30 parts by weight of anatase-type untreated titanium dioxide and 1.5 parts by weight of zinc stearate were added, and well kneaded at 150 ° C., A masterbatch was obtained. This is designated as A masterbatch.

Separately, 70 parts by weight of low-density polyethylene (MI5, density 0.92 g / m ² ) was added to a Banbury mixer, and a comparative masterbatch was obtained by the same procedure as above. This is designated as B masterbatch.

Next, a 1: 1 mixture of high-density polyethylene (MI7, density 0.96 g / m ² ) and low-density polyethylene (MI5, density 0.92) was melted at a resin temperature of 320 ° C. on the back surface of the base paper of the photographic resin-coated paper described above. It was coated to a thickness of 30 μ using an extrusion coating machine. Next, 30 parts by weight of A masterbatch and a resin for dilution (same as the resin used for A masterbatch) on the surface 7
After mixing with 0 part by weight, the resin was applied at a resin temperature of 300 ° C. to a thickness of 30 μ using a melt extrusion coating machine.

For comparison, 30 parts by weight of B masterbatch and a diluting resin (same as the resin used for B masterbatch) 70
After mixing with 1 part by weight, the resin was coated at a temperature of 300 ° C. to a thickness of 30 μ using a melt extrusion coating machine.

Then, after subjecting the surface of polyethylene containing titanium dioxide 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 with water (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 Optical brightener 0.5 g Benzyl alcohol 12 cc Diethylene glycol 10 cc Hydroxide Adjust the pH to 10.2 with sodium, and add 1 with water.
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.

From Table 1, when the carboxy-modified polyethylene of the present invention is used as a masterbatch resin and a diluting resin in a base paper containing AKD, good photographic resin coated papers with less penetration from the edges are obtained. It turns out that it can be obtained.

On the other hand, when ordinary low-density polyethylene, which is outside the scope of the present invention, is used in the same manner as described above, it is understood that only the resin-coated paper for photographic use which has a large amount of penetration from the edge can be obtained.

Example 2 Low density polyethylene (MI9,
Density 0.92) 50 parts by weight, 0.5 parts by weight (calculated in the form of Al ₂ O ₃ ) 50 parts by weight of hydrous aluminum oxide treated anatase type titanium oxide and 1.5 parts by weight of zinc stearate are added and kneaded well at 150 ° C. , Got a masterbatch.

This masterbatch was combined so as to have the resin composition shown in Table 2 and melt-extrusion coating was carried out at 320 ° C. to obtain a photographic resin-coated paper by the same procedure as in Example 1 and dipping from the edge. I got an inclusive result.

From Table 2, in the case of blending the resin of the present invention using carboxy-modified polyethylene as a diluting resin, it is possible to obtain good photographic resin-coated paper with less penetration from the edges in both 20 and 45 parts by weight. Understand. Also, the amount of AKD added is 0.3-
It can be seen that 1.0 wt% (vs pulp) is particularly good.

On the other hand, it can be seen that, in the case of the resin mixture of the present invention, the penetration from the edge is poor.

Example 3 A base paper was made into paper by the same procedure as in Example 1 so that the AKD addition amount shown in Table 3 was obtained, and the same master batch as in Example 2 was used to combine so as to obtain the resin composition shown in Table 3. A photographic resin-coated paper was obtained by the same procedure as in Example 1 except that melt extrusion coating was performed at 330 ° C., and the results of immersion from the edges were obtained.

From Table 3, when only 70 parts by weight of carboxy-modified polyethylene was used as the diluting resin, good penetration was obtained at the AKD addition amount of 0.05 to 3.0%, and 0.1 to 3.0%. Particularly good results were obtained in the range of 1.5%.

Example 4 In Example 1, instead of the mixture of high-density polyethylene and low-density polyethylene 1: 1 which is a resin composition on the back surface,
Same as Example 1 except that melt extrusion coating is applied to the backside of No. 1 to No. 5 (invention) and No. 6 to No. 10 (outside of the invention) only with carboxy-modified polyethylene (MI4, density 0.91). The photographic resin-coated paper was obtained by various procedures, and the results of immersion from the edge were obtained. As a result, No. 1 to No. 5 were all good with less penetration from the edge as in Example 1, but No. 6 to No. 10 were all inferior as in Example 1. Sufficient and only unsuitable as a resin coated paper for photographic use.

Claims (1)

[Claims] 1. A photographic support using a paper containing an alkyl ketene dimer as a support, wherein at least one surface of the paper is coated with a resin composition comprising at least a carboxy-modified polyethylene and a titanium dioxide pigment. A photographic resin-coated paper characterized in that