JPH0271256A - Photographic base - Google Patents

Abstract

PURPOSE:To obtain the whiteness of a resin surface and to obtain the photographic base which is vividly white by incorporating a titanium oxide pigment and specific fluorescent agent into the resin layer on the side where images are formed. CONSTITUTION:The photographic base formed by coating both surfaces of base paper with a polyolefin resin has the titanium oxide and the fluorescent agent expressed by the formula I in the resin layer of the surface on the side where the images are formed. In the formula, I, R1, R2, R3, and R4 denote hydrogen or residual org. group. The titanium oxide pigment to be used may be of a rutile type or anatase type and is more preferably the rutile type titanium oxide pigment in terms of sharpness and resolving power. The yellowishness occurring in the titanium oxide incorporated at a high concn. in the resin is eliminated in this way and the resin coated type photographic base which has visually no coloration, has high lightness and is vividly white is obtd.

Description

[Detailed Description of the Invention] [Field of Industrial Application] The present invention relates to a photographic support using paper as a substrate (hereinafter, the paper serving as the substrate is referred to as base paper) and coated on both sides with polyolefin resin. relates to a photographic support in which the whiteness of the resin surface on which an image is formed is improved. More specifically, the present invention uses a fluorescent agent to reduce the yellowish tendency caused by titanium oxide, especially rutile titanium oxide, contained in a high concentration in the resin layer on the image forming side of a resin-coated paper-type photographic support. The present invention relates to a photographic support whose whiteness is significantly reduced and improved by adding it to a resin layer.

[Prior art]

Recently, as photographic supports other than film-sensitive materials,
The mainstream is a waterproof support made of a base paper with high sizing property coated on both sides with a polyolefin resin, particularly a polyethylene resin. The reason for this is that the resin-coated waterproof support meets the demands for automation and speeding up the development process of photosensitive materials, especially photographic paper.

However, the resin layer on the image-forming side of the resin-coated paper photographic support contains titanium oxide mainly for the sake of image sharpness and other photographic performance requirements. Since the titanium oxide pigment has a yellowish tinge, if it is used as it is, the whiteness of the white background of the photographic image will be insufficient.

Particularly in the case of color photographic paper, which has been widely used in recent years, faithful color reproduction and vivid colors are required. Whiteness is required.

In addition, while the technology related to titanium oxide pigments and resins has progressed, there has been a strong demand for improved sharpness of color images and black and white images, and the resin layer on the image forming side of the resin-coated paper-type photographic support has become stronger. The concentration of titanium oxide pigments in the materials tends to increase more and more, and techniques for improving visual whiteness are becoming more and more important.

Conventionally, several techniques are known for improving the whiteness of a resin layer containing titanium oxide on the image forming side of a resin-coated paper-type photographic support.

U.S. Patent No. 3,501,298 discloses that in addition to titanium oxide, blue-tinted inorganic pigments such as ultramarine and cobalt blue are added to the resin layer.
Cobalt oxide phosphate (Ferro C) is a reddish inorganic pigment.
o1ors Cup Ra5pbe+ "yV -626
0), containing quinacridone red which is a reddish organic pigment, and Uvifex OB (CI BA
It is known to contain an optical brightener having a bis(alkyl-substituted benzoxacylyl)thiophene structure represented by GE I GY (trade name).

JP-A No. 53-1.9021 contains cosmetic ultramarine called ultramarine, which is a bluish inorganic pigment, Daiichi Pink DP1, which is a reddish inorganic pigment, and Daiichi Violet D■-1 (all manufactured by Dai-Kasei Kogyo). It is disclosed that it will encourage you to do so. Further, Japanese Patent Publication No. 56-51336 discloses that a fluorescent brightener having a bis(alkyl-substituted benzoxacylyl)naphthalene structure is contained in a resin layer. Tokukai Showa 6
No. 175341 discloses a technique for incorporating a quinacridone-based reddish organic pigment into a resin.

However, each of these techniques has drawbacks.

That is, an inorganic or organic coloring pigment is contained in the resin on the image forming side of the resin-coated paper-type photographic support to neutralize the yellowing tendency caused by the titanium oxide pigment contained in a high concentration. As for the technology to improve visual whiteness, after all, it is colored to make it look whiter.
The problem is that the brightness decreases and clear whiteness cannot be obtained.

Furthermore, in the case of inorganic colored pigments, they generally tend to contain a large amount of water, and will carry a large amount of water into the resin composition. If the water content in the resin composition increases, a problem arises in that the resin film is more likely to crack due to water vapor blowing out during melt extrusion coating. Furthermore, ultramarine and cobalt-based inorganic coloring pigments deteriorate the heat resistance of the resin due to their chemical activity, and degraded resin compositions adhere to and accumulate at the opening of the extrusion coating machine's grip, creating icicle-like formations. Encourage the tendency to grow. When this icicle-like adhered deposit is generated, there is a problem in that it causes streak-like scratches on the resin film and significantly impairs the commercial value of the resin-coated paper-type photographic support. On the other hand, with regard to the technology of adding known optical brighteners such as bis(alkyl-substituted benzoxacylyl)thiophene to resin compositions to improve whiteness, the optical brightener tends to bleed out from the resin. However, not only is there a problem in the stability of color tone, but also there is a problem in adhesion to the photographic emulsion layer. In addition, when a fluorescent whitening agent is included in a resin composition to make it white, the stability of the whiteness is poor, so-called weather resistance such as light resistance and dark fading is poor, and the resin composition gradually turns yellow over time. It also became clear that there was a problem. Furthermore, in the case of resin-coated paper in which a fluorescent brightener with a bis(alkyl-substituted benzoxacylyl)thiophene structure, such as Ubitex OB, is added to the resin layer, the photographic material using the coated paper as a support is acidified. When treated with a hardening fixer, there was a problem in that the whiteness did not improve but instead turned yellow.

[Problem that the invention seeks to solve]

Therefore, an object of the present invention is to eliminate the yellow tinge caused by the titanium oxide contained in the resin at a high concentration, thereby producing a resin-coated paper-type photographic support that is visually uncolored and therefore bright and bright. The goal is to provide the following. Another object of the present invention is to have no resin cracking, no problem with heat resistance, no bleed-out phenomenon, good weather resistance and therefore good whiteness preservation, and furthermore, is free from yellowing caused by photographic processing solutions. To provide a resin-coated paper-type photographic support with high brightness and bright white color. Another object of the present invention is to provide a resin-coated paper-type photographic support that has particularly good sharpness and resolution, and is bright and white with high brightness.

[Means and effects for solving the problem] In order to solve the above-mentioned problem, the present inventors conducted intensive research and found that an image can be formed on a photographic support in which both sides of base paper are coated with polyolefin resin. It has been found that the object of the present invention can be achieved by containing at least titanium oxide and a fluorescent agent represented by the following structural formula [I] in the resin layer on the side to be exposed.

(In the formula, R1, R2, R3 and R4 represent hydrogen or an organic residue.) Furthermore, an object of the present invention is to provide at least one resin layer in the resin layer on the side on which an image is formed in the resin-coated paper-type photographic support. This can be significantly achieved by containing a rutile-type titanium oxide pigment and a fluorescent agent represented by the structural formula [I]. That is, a resin-coated paper-type photographic support using a rutile-type titanium oxide pigment is
Although the sharpness and resolution are better than when using anatase-type titanium oxide, it is extremely difficult to obtain a photographic support with excellent whiteness due to the strong yellow tinge caused by titanium oxide. However, according to the present invention, it is possible to provide a resin-coated paper-type photographic support that has good sharpness and resolving power, is free from the above-mentioned problems, and is bright and bright in color.

The titanium oxide pigment used in the present invention may be of rutile type or anatase type, but rutile type titanium oxide pigment is preferable from the viewpoint of sharpness and resolution. As described in Japanese Patent Publication No. 56-5987, a rutile type titanium oxide pigment and anatase type titanium oxide pigment can also be used together.

Further, as titanium oxide pigments that are advantageously used in the practice of the present invention, those coated with various inorganic oxides or hydrous inorganic oxides, such as those coated with various inorganic oxides or hydrous inorganic oxides, such as
Those described or exemplified in JP-A-52-35625, JP-A-63-11655, those coated with various organic compounds, such as JP-A-55-10865, JP-A-55-113040, JP-A-55-113040, No. 57-35855, JP-A-57-36156, JP-A-61-26652,
JP 58-75151, JP 58-58542, JP 58-17433, JP 59-37304
No., JP-A-62-25753, JP-A-62-1415
No. 44, JP-A-61-148946, JP-A-62-1
61147, those described or exemplified in British Patent No. 1,164.849, and other suitable photographic titanium oxide pigments, such as JP-A-57-32442 and JP-A-57-4.
No. 6818, JP-A-58-220140, JP-A-59
Various materials such as those described or exemplified in JP-A-1.544, JP-A-59-121329, JP-A-59-215344, and JP-A-62103635 can be used.

However, as a titanium dioxide pigment, a rutile type titanium dioxide pigment surface-treated with hydrated aluminum oxide of 0.2% to 2% by weight (calculated in the form of AA 203) based on titanium dioxide is used in a polyolefin resin layer. The object of the present invention can be significantly achieved by containing the -layer in the -layer. That is, if the amount of surface treatment with hydrated aluminum oxide is less than 0.2% by weight, the resin layer containing the titanium dioxide pigment and the fluorescent agent of the present invention will be seriously degraded by light and is not practical.

On the other hand, the amount of surface treatment by hydrous aluminum oxide was 1.2
If it exceeds % by weight, icicle-like deposits (hereinafter referred to as die lip stains) tend to occur at the opening of the extruder die lip during melt extrusion coating of a polyolefin resin composition containing the titanium dioxide pigment. Furthermore, it was found that the tendency for Grip stain to occur is even greater when a resin composition containing the titanium dioxide pigment and the fluorescent agent of the present invention is applied by melt extrusion. However, in the most preferred embodiment of the present invention, 0.2% to 12% by weight of titanium dioxide (in the form of Al2O2) is added to the polyolefin resin layer on the image forming side of the resin-coated paper-type photographic support. By incorporating the rutile-type titanium dioxide pigment surface-treated with hydrous aluminum oxide (calculated) and the fluorescent agent of the present invention, the sharpness of the printed image is high,
Provides an excellent photographic support that has high brightness and looks white, has good weather resistance of the resin layer, and generates very little gripp stain during manufacturing of the photographic support, and therefore has good surface quality. It turns out it can be done.

In addition, if the content of titanium oxide pigment in the resin composition is less than 5% by weight, the sharpness and resolution of the photographic support will decrease, which is a problem, and if it exceeds 40% by weight, the fluidity will decrease. A range of 9 to 30% by weight is preferred, and a range of 9 to 25% by weight is particularly preferred. A method for incorporating titanium oxide pigment into the resin composition of a photographic support is to prepare a so-called masterbatch in which titanium dioxide is contained in a polyolefin at a certain concentration in advance, and then dilute it with a diluent resin to the desired ratio. Usually, they are used as a mixture, or a so-called compound is prepared by containing a titanium dioxide pigment in a polyolefin in a desired composition ratio from the beginning. To create these masterbatches and compounds, a Banbury mixer, an extruder for kneading, a two-roll kneading machine, a three-roll kneading machine, etc. are usually used, but a Banbury mixer and an extruder for kneading are advantageously used. used. Further, two or more of these various kneading machines may be used in combination.

Specific examples of masterbatch manufacturing methods include methods described or exemplified in, for example, JP-A-60-1.1841, JP-A-60-75832, and JP-A-60-181131.

Specific examples of the fluorescent agent represented by the structural formula [D] used in the practice of the present invention include those represented by the following formula. They can also be used in mixtures.

・・・・・・・・・ (n) ・・・・・・・・・ (III ・・・・・・・・・ [■] ・・・・・・・・・ [V] These fluorescence The agent is stilbene-4,4' dicarboxylic acid as described or exemplified in JP-A-48-6080.
It is produced by condensing -amino-2-hydroxy-4 and 10+5-substituted benzene. Among these fluorescent agents, structural formulas [■] to (VI) are preferable in terms of bleed-out resistance and weather resistance, and particularly structural formulas [■] to (V
l'l is preferred.

The content of these fluorescent agents in the resin composition is set at 0.000000000000000000000000000000000000000000000000000000000. ], mg/d~50m
g/rrf, particularly preferably from 0.5 g/rrf to 10 mg/rrf.

Further, as a method of incorporating the fluorescent agent in the resin composition in the present invention, when producing a masterbatch or compound of titanium oxide pigment, the fluorescent agent is also included, and the titanium oxide pigment, fluorescent agent, polyolefin resin, and dispersion are mixed. A masterbatch or compound of the agent, such as a fatty acid metal salt, can be prepared and included in the resin composition. In addition, a fluorescent agent that has a softening point lower than that of the main polyolefin resin and is a solid at room temperature, a low molecular weight polyolefin or/and a dispersant, such as a fluorescent agent premixed with a fatty acid metal salt, is dispersed in the main polyolefin. A masterbatch can be prepared and included in the resin composition.

On the other hand, JP-A No. 48-6080 discloses an aqueous dispersion of a fluorescent agent represented by the structural formula CI), but this dispersion cannot be incorporated into a polyolefin resin, and it is not suitable for photographic use. Even if an attempt is made to produce an effect by adding it to the undercoat layer of the support, there are problems in that the adhesion with the photographic constituent layers deteriorates and the photographic properties are adversely affected. It has been discovered that by using a fluorescent agent represented by the structural formula CI], many problems can be overcome and the objects of the present invention can be achieved.

The pulp constituting the base paper used in the practice of the present invention includes Japanese Patent Application Laid-open Nos. 58-37642 and 60-6794.
No. 0, JP-A-60-69649, JP-A-61-354
Although it is advantageous to use appropriately selected natural pulp as described or exemplified in No. 42, synthetic pulp or synthetic fibers other than natural pulp may be used if necessary. Natural pulp is subjected to conventional bleaching treatments such as chlorine, hypochlorite, and chlorine dioxide bleaching, as well as alkali extraction or alkali treatment and, if necessary, oxidative bleaching treatment using hydrogen peroxide, oxygen, etc., and combinations thereof. Wood pulps such as softwood pulp, hardwood pulp, and softwood hardwood mixed pulp are advantageously used, and various pulps such as kraft pulp, sulfide pulp, and soda pulp can also be used.

The base paper used in the practice of the present invention can contain various sizing agents, polymer compounds, and additives at the time of preparing the paper stock slurry.

Sizing agents that can be advantageously contained in the base paper used in the present invention include fatty acid metal salts and/or fatty acids, alkyl ketene dimers, alkenyl or alkyl succinic anhydrides, and the epoxy resin described in JP-A-54-147211. Chemical higher fatty acid amide, JP-A-56-1093
Examples include organic fluoro compounds described in No. 43.

Examples of sizing agents that can be advantageously included in the base paper used in the practice of the present invention include aluminum chloride, sulfuric acid,
Fatty acid metal salts and/or fatty acids in an embodiment fixed to the pulp with a water-soluble aluminum salt such as polyaluminum chloride, an alkyl ketene dimer or alkyl ketene dimer in an embodiment fixed to the pulp with or without a water-soluble aluminum salt. Examples include a sizing agent in combination with an alkyl ketene dimer and an epoxidized higher fatty acid amide. The fatty acid metal salt and/or fatty acid preferably have 12 to 22 carbon atoms, and the amount added is preferably in the range of 5 to 4.0% by weight based on the absolute dry weight of the bulb. In addition, the amount of water-soluble aluminum salt added as needed is 1 % on a solid weight basis with respect to the sizing agent.
The range of /20 to 4/1 is particularly preferred, and the range of 1/10 to 1/I is particularly preferred. In addition, as an alkyl ketene dimer,
The number of carbon atoms in the alkyl group is 8 to 30, preferably 12 to 18
The one is good. Alkyl ketene dimers are usually commercially available as emulsions thereof, and specific examples include Acopel 360XC manufactured by Dick Vercules. The amount added is 0.0% as alkyl ketene dimer per absolute dry weight of pulp. A range of 2 to 4.0% by weight is preferred.

Examples of polymer compounds that can be advantageously incorporated into the base paper used in the present invention during the preparation of the paper stock slurry include cationic wet strength agents, cationic, anionic, or amphoteric strength agents.

As the cationic wet paper strength agent, polyamine polyamide epichlorohydrin resin is preferable, and the amount added is in the range of 0.05 to 4.0% by weight, particularly 0.15 to 1.5% by weight, based on the dry weight of the pulp. A weight percent range is preferred.

A specific example is Kaimen 557H manufactured by Dick Percules ■.

Examples include Kaimen 5-25 and Evinox P-130.

Examples of cationic, anionic or amphoteric paper strength enhancers include cationic starch described or exemplified in Japanese Patent Publication No. 60-17103, cationic polyvinyl alcohol described or exemplified in Japanese Patent Application No. 6249699, and cationic polyvinyl alcohol described or exemplified in Japanese Patent Application No. 1983-1983. -185432, cationic polyacrylamide described or exemplified in JP-A-57-1.97539,
Anionic polyacrylamide described or exemplified in Japanese Patent Publication No. 62-23119 and Japanese Patent Publication No. 62-31118,
Examples include amphoteric polyacrylamide described or exemplified in JP-A-61-37613 and JP-A-59-31949, and vegetable galactomannan as described or exemplified in JP-A-59-125731. The addition amount thereof is preferably in the range of 0.05 to 8% by weight, particularly preferably in the range of 0.15 to 4% by weight, based on the dry weight of the pulp.

Furthermore, various additives can be added to the base paper used in the practice of the present invention when preparing the paper stock slurry. As fillers, clay, kaolin, calcium carbonate, barium sulfate, magnesium silicate, titanium oxide, etc.
As an H regulator, caustic soda, soda carbonate, etc., as a coloring pigment, a coloring dye, as a fluorescent whitening agent, JP-A-54-147
No. 033, Patent Application No. 1982-37555, Patent Application No. 1983-9
The materials described or exemplified in No. 6516 may be contained in appropriate combinations.

Various water-soluble polymers, antistatic agents, and additives can be added to the base paper used in the present invention by spraying or tab size pressing. Water-soluble polymers include starch polymers, polyvinyl alcohol polymers, gelatin polymers, polyacrylamide polymers, cellulose polymers, etc. as described or exemplified in Japanese Patent Application No. 63-96516. Alkali metal salts such as sodium chloride and potassium chloride, alkaline earth metal salts such as calcium chloride and barium chloride, colloidal metal oxides such as colloidal silica, and JP-A-58-82
Examples of latex and emulsions include organic antistatic agents described or exemplified in No. 242, petroleum resin emulsions, styrene-acrylic acid-acrylic acid ester copolymers, styrene-acrylic acid-butadiene copolymers, and ethylene-vinyl acetate copolymers. Polymers, latex such as styrene-maleic acid-acrylic acid ester copolymer, pigments such as clay, kaolin, talc, barium sulfate, titanium oxide, etc., and pH regulators such as hydrochloric acid, phosphoric acid, citric acid,
It is advantageous to contain additives such as caustic soda, soda carbonate, and the above-mentioned color pigments, color dyes, and optical brighteners in appropriate combinations.

For the production of the base paper used in the practice of the present invention, commonly used paper machines such as Fourdrinier paper machines and circular net paper machines are used.
It is advantageous to employ suitable papermaking methods, such as those described or exemplified in No. 0, JP-A-61-284762. There are no particular restrictions on the thickness of the base paper, but after making the base paper,
Preferably, the base paper is calendered as described or exemplified in No. 26397, and its basis weight is 40 g.
/ffl to 250 g/rd is preferred.

Polyolefin resins used in the practice of the present invention include homopolymers of olefins such as low-density polyethylene, high-density polyethylene, polypropylene, polybutene, and polypentene, or copolymers of two or more olefins such as ethylene-propylene copolymers. These include coalescence and mixtures thereof, and those having various densities and melt viscosity indices (melt index) can be used alone or in combination. In addition, when the resin has a multilayer structure, the outermost layer resin has a melt index (hereinafter abbreviated as MI) of 5 to 20, and the lower layer resin has a melt index (MI) of 5 to 20, for example.
It is also possible to use resins of other properties, such as those of 10.

In the present invention, the resin layer on the image forming side of the photographic support contains 9 to 20% by weight of titanium dioxide pigment, but in the case of multilayer resin-coated paper, the lower resin layer contains titanium dioxide pigment in an amount of 9 to 20% by weight. may or may not contain a titanium dioxide pigment. In addition, polyolefin resins contain white pigments such as zinc oxide, talc, and calcium carbonate, fatty acid amides such as stearic acid amide and alaxic acid amide,
Fatty acid metal salts such as zinc stearate, calcium stearate, aluminum stearate, magnesium stearate, zirconium octylate, sodium palmitate, calcium palmitate, sodium laurate, tetrakis[methylene-3(3,5-di1e+
Antioxidants such as 4-butyl-4-hydroxyphenyl)propionate comethane, 2゜6-te11-butyl-4-methylphenol, cobalt blue, navy blue,
Blue pigments and dyes such as ultramarine, cerulean blue, and phthalocyanine blue, magenta pigments and dyes such as cobalt violet, fast violet, and manganese violet, Tinuvin 320, Tinuvin 326, Tinuvin 328 (
It is preferable to add an appropriate combination of various additives such as ultraviolet absorbers such as Ciba Geigy (trade name).

The photographic support produced according to the present invention is produced by a so-called extrusion coating method in which heated and melted polyolefin resin is cast onto a running base paper, and both sides of the support are coated with the resin. In this case, in the case of a multilayer structure, the outermost resin layer on the front side of the photographic support and the inner resin layer are extrusion coated one after another, preferably continuously, in a so-called tandem extrusion system or the outermost resin layer. It is preferable to use a so-called co-extrusion coating system in which the inner resin layer and the inner resin layer are simultaneously extrusion coated. Furthermore, before coating the base paper with the polyolefin resin, it is preferable to subject the base paper to an activation treatment such as a corona discharge treatment or a flame treatment. The surface of the emulsion side of the photographic support is a glossy surface or a surface of JP-A-55-265 that does not affect the gloss of the surface of the photographic paper when it is made into photographic paper.
It has a finely rough surface, a matte surface, a silky surface, etc. as described in No. 07, and the back side is usually a matte surface, and if necessary, the front surface or both the front and back surfaces are subjected to activation treatment such as corona discharge treatment or flame treatment. can be administered. Further, after the activation process, a subtraction process as described in Japanese Patent Application Laid-Open No. 61-8464'3 can be performed. The thickness of the resin layer on the front and back sides of the resin-coated paper is not particularly limited, but is generally 10μ to 50μ.
Advantageously, extrusion coatings are applied to a certain thickness.

The photographic support in the present invention can be coated with various back coat layers for antistatic purposes, anti-calming, and the like. In addition, for the back coat layer,
No. 20, Special Publication No. 57-9059, Special Publication No. 57-539
No. 40, Special Publication No. 5856859, Special Publication No. 5! IJ-2
Inorganic antistatic agents, organic antistatic agents, hydrophilic binders, latexes, curing agents, pigments, surfactants, etc. described or exemplified in No. 14849, JP-A-58-184144, etc. can be contained in appropriate combinations. .

The photographic support in the present invention is coated with various photographic constituent layers, and is used 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 for printing materials. For example, silver chloride, silver bromide, silver chlorobromide, silver iodobromide, and silver chloroiodobromide emulsion layers can be provided. A color coupler is contained in 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 polyvinylpyrrolidone, polyvinyl alcohol, and polysaccharide sulfate ester compounds can be used. Also,
The photographic constituent layer described above may contain various additives.

For example, sensitizing dyes include cyanine dyes and merocyanine dyes, chemical sensitizers include water-soluble gold compounds and sulfur compounds, and antifoggants or stabilizers include hydroxy-triazolopyrimidine compounds and mercapto-heterocyclic compounds. Hardeners: Formalin, vinyl sulfone compounds, aziridine compounds, etc. Coating aids: Benzene sulfonate, sulfosuccinate salts, etc. Anti-staining agents: Dialkylhydroquinone compounds, etc. Other optical brighteners, sharpness An improving dye, an antistatic agent, a pH adjuster, a fogging agent, and further a water-soluble iridium, a water-soluble rhodium compound, etc. can be contained in appropriate combinations during the production and dispersion of silver halide.

The silver halide photographic material according to the present invention may be exposed, developed, and processed as described in "Photographic Light-sensitive Materials and Handling Methods" (Kyoritsu Shuppan, written by Gobe Miyamoto, Photographic Technology Lecture 2) in accordance with the photographic material. Treatments such as stopping, fixing, bleaching, stabilization, etc. are carried out, and multilayer silver halide color photographic materials that undergo bath bleach-fixing treatment after color development are particularly suitable for CD-m, CD-IV (
The above two compounds can be processed with any herbal 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. It is also possible to process with a developer substantially free of benzyl alcohol. Additionally, useful one-bath bleach-fix solutions include metal salts of aminopolycarboxylic acids (e.g., ferric complex salts such as ethylenediaminetetraacetic acid and propylenediaminetetraacetic acid).
It is a solution, and sodium thiosulfate, ammonium thiosulfate, etc. are useful as fixing agents. Such -bath bleach-fix solutions can contain various additives. For example, desilvering accelerators (e.g., U.S. Patent Box 3,512,979
Mercaptocarboxylic acid described in Bengie Patent No. 68
mercapto-heterocyclic compounds described in No. 2,426, etc.)
, antifouling agent, pH adjusting or pH buffering agent, hardening agent (
For example, various compounds such as magnesium sulfate, aluminum sulfate, potassium alum, surfactants, etc. can be contained in combination. Also, although such -bath bleach-fix solutions can be used at a variety of pHs, the useful pH range is p.
H6.0 to 8.0.

〔Example〕

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

Example 1 A mixed stock of 50 parts by weight of hardwood bleached kraft pulp and 50 parts by weight of softwood sulfide pulp was beaten to 31.0 ml of Canadian Standard Freeness, and
0.00 parts by weight, 3 parts by weight of cationized starch, 0.2 parts by weight of anionized polyacrylamide, 0.4 parts by weight of alkyl ketene dimer emulsion (as ketene dimer content), 0.0 parts by weight of polyamide polyamine epichlorohydrin resin.
4 parts by weight was added to produce paper with a basis weight of 60 g/11f. The obtained wet paper paper was dried at 110°C, and then added with 3 parts by weight of carboxy-modified polyvinyl alcohol, 0.05 parts by weight of optical brightener, 0.002 parts by weight of blue dye, and 0.5 parts by weight of citric acid. 25 parts by weight of an impregnating solution consisting of 2 parts by weight and 97 parts by weight of water.
g/rrf impregnation, drying with hot air at 110° C., calendering at a linear pressure of 90 kg/cm, and corona discharge treatment on both sides to produce base paper for photographic resin-coated paper.

Next, high-density polyethylene (density 0, 9
6 g/cu+”, M I = 5) and low density polyethylene (density 0.92 g/c+r+3, M I =
The 1°:1 mixture of 5) was coated to a thickness of 30μ using a melt extrusion coater at a resin temperature of 330°C. Next, after thoroughly mixing each of the resin compositions listed in Table 1 on the surface of the base paper, a screw extruder with an extrusion port diameter of 65 mm was used.
Using a melt extruder with a T-die of 0 mm dl, coating was carried out to a thickness of 30 μm at a resin temperature of 320° C. to produce photographic supports containing titanium oxide pigments and the like. At that time, the surface resin layer containing titanium oxide pigment etc. is formed into a flat glossy surface.
The real fat layer was processed into a paper-like matte surface. Note that the numbers in the table represent parts by weight.

(Left below) Note 3: All resins used in the bottom column have a density of 0.918 MI.
9 polyethylene.

Note 4: Polyethylene with density 0.92 Ml5.

Note 5: The 5hapa+d ColorCom
Contains 10% by weight of Cobalt Blue #3 manufactured by Pany and 0.5% by weight of zinc stearate.

Note 6: Chromophthal Blue ASR (manufactured by Ciba Geigi)
is a masterbatch with the following structure Note 1: 50 parts by weight of niltile titanium oxide, 2.5 parts by weight of zinc stearate, and 47.5 parts by weight of polyethylene with a density of 0.918 Ml9.

Note 2: 50 parts by weight of niltile titanium oxide, 1°25 parts by weight of ultramarine blue, 2.5 parts by weight of zinc stearate, density 0.918
Masterbatch consisting of 46.25 parts by weight of polyethylene with Ml 9.

Contains 0.1% by weight of chromophthal blue A3R and 0.1% by weight of low molecular weight polyethylene.

Note 7: Contains no other additives.

Note 8: 0.4% by weight of fluorescent agent and 0.4% by weight of low molecular weight polyethylene.
Contains 4% by weight.

Note 9: 0.1% by weight of fluorescent agent and 0.1% by weight of low molecular weight polyethylene.
Contains 1% by weight. The same goes for the next two types of fluorescent agents.

A portion of each of the resulting photographic supports was made into black and white photographic paper. The remaining portion was coated with the same amount of gelatin as that contained in the black and white photographic paper.

Whitening effect evaluation method: The color tone of samples coated with gelatin was evaluated. The evaluation criteria are white → 01, \yellow → △, yellow → ×.

Processing solution resistance evaluation method: Black and white photographic paper was treated with an acid hardening fixer (Kodak formulation F-5) at 20° C. for 5 minutes and washed with water. The color tone of this surface was compared to an untreated gelatin-coated sample. Evaluation criteria: No change → ○, ＼Yellowing - △, Yellowing → ×
.

Dark fading property evaluation method: A sample coated with gelatin was heated to 50°C in a dark place and stored for one week, and changes in color tone before and after that were examined. The criteria are the same as in the previous section.

Sunlight fading evaluation method: A sample coated with gelatin was exposed to sunlight for two months, and changes in color tone before and after exposure were examined. The criteria are the same as in the previous section.

Bleed-out evaluation method: Lay the rough resin surface of non-fluorescent resin-coated paper on the front resin surface of an uncoated sample, and store the sample at a load of 50 g/cJI for 3 days at 50°C. The non-fluorescent resin-coated paper that was in contact with the resin surface was irradiated with an ultraviolet lamp and observed. The evaluation criteria were: no glow at all → ○, a small amount of the fluorescent agent transferred and glowed → △, most of the fluorescent agent transferred and the entire surface glowed → ×. The results are shown in Table 2.

(Margins below) Samples ■ to ■ that were color-corrected with colored pigments have low brightness and <
You can feel the corner. Sample ■ is bright white, but has problems with processing solution resistance, storage stability, and bleed-out properties. Sample ■ has a problem with bleed-out properties. In addition, icicle-like deposits were generated at the die lip opening during the production of sample (1).

Example 2 A photographic support was produced by replacing Table 1 of Example 1 with Table 3. Note that the numbers in the table are parts by weight.

(Left below) Note 10 = Alumina coverage vs. titanium oxide 0.5% CAB
50 parts by weight of rutile titanium oxide (as 203), 2.5 parts by weight of zinc stearate, density 0.918, MI 9
A masterbatch consisting of 47.5 parts by weight of polyethylene.

Attention = 50 parts by weight of titanium oxide as above, 1.25 parts by weight of ultramarine, 2.5 parts by weight of zinc stearate, 4 parts by weight of polyethylene as above
A masterbatch consisting of 6.25 parts by weight.

Note 12 = Polyethylene with density 0.92 MI 5.

Note 13 = Polyethylene with density 0.96 MI 7.

Note 14: Cosmetic Gunjo Daiichi Pink DP manufactured by Dai-Kasei Kogyo ■
- A masterbatch consisting of 99 parts by weight of polyethylene of 31 parts by weight, density 0.918, MI 9.

Note 15 = Same as Note 9.

Note 16: Same as Note 6.

Note 17: Hoechsl AG Hostapalm Pink E (quinacridone magenta pigment) 0.1 part by weight, low molecular weight wax 0.1 part by weight, density 0.918 Ml
A resin composition comprising 99.8 parts by weight of polyethylene No. 9.

A part of each of the resulting photographic supports includes a blue-sensitive emulsion layer containing a yellow color-forming coupler and an intermediate layer, a green-sensitive emulsion layer containing a magenta color-forming coupler, an ultraviolet absorption layer containing an ultraviolet absorber, and a cyan color-forming coupler. A color photographic paper was manufactured by sequentially applying a red-sensitive emulsion layer containing a coupler and a protective layer. The remaining portion was coated with the same amount of gelatin as used for color photographic paper.

Evaluation was carried out in the same manner as in Example 1, except that unexposed color photographic paper was subjected to the following treatment instead of the acid hardening fixer treatment in Example 1. The results are shown in Table 4. process.

Color development 3 minutes 30 seconds, bleach fixing 1 minute 30 seconds, washing with water 3 minutes 3
0 seconds (33°C) Color developer Sodium carbonate (monohydrate) 46.0g Anhydrous sodium sulfite 2.0g Potassium bromide
0.5g CD-m
4. 5g sodium hexametaphosphate
0.5 g Hydroxylamine sulfate 2.0 g Optical brightener 0.5 g Benzyl alcohol 12 cc Diethylene glycol 10 cc Adjust the total volume to II with water and pH 10.2 with sodium hydroxide.

Bleach-fix solution Ferric complex salt of ethylenediaminetetraacetic acid 6g Disodium salt of ethylenediaminetetraacetic acid g Ammonium thiosulfate 60g Anhydrous sodium sulfite 20g Sodium acid sulfite 5g Disodium phosphate
Adjust the total amount to 11 with 12g water.

(The following is a blank space) Example 3 The results in Table 6 were obtained in exactly the same manner as in Example 2, except that Table 5 was used in place of Table 3 in Example 2.

Note that the numbers in Table 5 represent parts by weight.

(The following is a blank space) Example 4 The same procedure as in Example 1 was carried out except that anatase-type titanium oxide was used in place of the rutile-type titanium oxide in Example 1.

The same results as Example J were obtained, except that the color was not so yellow even without the fluorescent agent, and the whiteness was even brighter when the fluorescent agent was used.

Example 5 The fluorescent agent of Example 2 was changed from Nα■ to No, V,
The procedure was carried out in exactly the same manner as in Example 2, except that Nα■ was used, and the same results were obtained.

Example 6 Same as Notes 1 and 2 of Example 1, except that the titanium dioxide pigment listed in Table 7 is used instead of the titanium dioxide pigment used in Notes 1 and 2 of Example 1, but does not contain ultramarine blue. A masterbatch containing a masterbatch and ultramarine was created.

Thereafter, in place of the resin composition used in Example 1, 20.8 parts by weight of the masterbatch not containing ultramarine prepared as described above, 2 parts by weight of the masterbatch containing ultramarine 5°-17°, and 2 parts by weight of the masterbatch containing ultramarine blue were added. Same as Example 1 except that 10 parts by weight of the resin containing 0.1% by weight of the Nα■ fluorescent agent described in the text, which is the same as described in Sample No. 9, and 64 parts by weight of the diluted resin, which is the same as in Example 1, are used. A resin-coated paper-type photographic support was produced by carrying out the following procedure.

The results obtained are shown in Table 7, and the sharpness of the printed image, the number of die lip stains, and the light resistance as noted in the table were evaluated as follows.

(Evaluation of Sharpness of Printed Images) In order to measure the sharpness of printed images, color photographic paper was produced using the above photographic resin-coated paper as a support. First, a back coat layer having a composition of colloidal silica and styrene acrylic latex = 1:1 was coated at 0.4 g/rrf on the back side of photographic resin-coated paper after corona discharge treatment. Next, after corona discharge treatment, a blue-sensitive emulsion layer containing a yellow color-forming coupler, an intermediate layer containing a color mixing preventive agent, and a green-sensitive emulsion layer containing a magenta color-forming coupler are applied to the front resin surface containing titanium dioxide pigment of the photographic resin-coated paper. ,
A color photographic paper was obtained by providing an ultraviolet absorbing layer containing an ultraviolet absorber, a red-sensitive emulsion layer containing a cyan color-forming coupler, and a protective layer. Each color-sensitive emulsion layer contained silver chlorobromide equivalent to 0.6 g/rd of silver nitrate. In addition to gelatin necessary for silver halide production, dispersion, and film formation, it also contains appropriate amounts of antifoggants, sensitizing dyes, coating aids, hardeners, thickeners, and appropriate amounts of filter dyes.

The resolution chart is closely attached to the obtained color photographic paper,
A test sheet was obtained by exposure to green light and color development. This test sheet was measured with a microdensitometer, and the sharpness of the image of the magenta layer was calculated using a personal computer according to a conventional method.
The sharpness of the printed image on the photographic resin-coated paper was determined by calculating the contrast transfer function.The larger the CTF value, the higher the sharpness of the printed image. There is.

(Evaluation of die lip stains) The number of die lip stains in each sample was counted 2 hours after the start of melt extrusion. At that time, the total number of die lip stains generated on the front and rear sides of the die was counted. .

(Evaluation of light resistance) Fade meter manufactured by Suga Test Instruments (1; 'AL-25X-
The graph shows the Y concentration measured using a Macbeth densitometer (model RD-519) on the sample surface after 80 hours of irradiation with HCL type. The lower the value, the better the light resistance.

(Left below) As shown in Table 7, when a titanium dioxide pigment surface-treated with hydrated alumina and a fluorescent agent are used together (sample No. 2
9), a sample other than the present invention that does not contain a fluorescent agent (sample Nα23
) It can be seen that the formation of gripp stains is promoted compared to the case of .). However, in a preferred embodiment of the present invention, 0.2% to 1.2% by weight (A
When a fluorescent agent was used in combination with a rutile-type titanium dioxide pigment surface-treated with hydrated aluminum (calculated in the form of 12O3) (samples Nα26 to 28), no die lip stain occurred, and the surface quality was good. It can be seen that it is an excellent photographic support with high sharpness of printed images and good light resistance.

〔Effect of the invention〕

By carrying out the present invention, a photographic support with clear whiteness can be obtained without any other problems.

Claims (4)

[Claims] (1) In a resin-coated paper-type photographic support made of paper as a substrate and coated on both sides with polyolefin resin, the resin layer on the side on which the image is formed contains at least a titanium oxide pigment and is represented by the following structural formula [I]. A photographic support comprising a fluorescent agent. ▲There are mathematical formulas, chemical formulas, tables, etc.▼・・・・・・・・・
[I] (In the formula, R_1, R_2, R_3 and R_4 represent hydrogen or an organic residue.) (2) The fluorescent agent is R_1, R_2 in the structural formula [I]
The photographic support according to claim 1, wherein at least one of R_3 and R_4 is an alkyl group having 12 or less carbon atoms, and the remainder is hydrogen or an alkyl group having 12 or less carbon atoms. (3) Claim 1 in which the titanium oxide is rutile-type titanium oxide.
or the photographic support described in 2. (4) The rutile type titanium dioxide pigment is surface-treated with 0.2% to 1.2% by weight (calculated in the form of Al_2O_3) of hydrated aluminum oxide based on titanium dioxide. Photographic support as described.