JP2907601B2 - Support for photosensitive material - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a paper substrate (hereinafter referred to as "base paper") on which a photosensitive layer is provided, which is coated with a polyolefin resin, and the other side of which is coated with a resin capable of forming a film. More specifically, the present invention relates to a resin-coated paper-type photosensitive material support in which the storage stability of a silver halide photosensitive layer (hereinafter simply referred to as storage stability) is improved. It is.

[0002]

2. Description of the Related Art As a support for a photosensitive material, a resin-coated paper-type support for a photosensitive material in which at least one surface of a substrate is coated with a resin capable of forming a film is well known. For example, Japanese Patent Publication No. 55-12584 discloses a technique for a support for a photosensitive material in which a base paper is coated with a resin capable of forming a film, preferably a polyolefin resin. U.S. Pat. No. 3,501,298 discloses a technique for a support for a photosensitive material in which both sides of a base paper are coated with a polyolefin resin. In addition, since the rapid photographic development processing method of silver halide photographic light-sensitive materials was applied, supports for light-sensitive materials in which both sides of a base paper were coated with a polyethylene resin have been mainly used for photographic printing paper. In order to impart sharpness to the resin layer on one image forming side, if necessary,
Usually contains titanium dioxide pigment.

However, a support for a resin-coated paper-type photosensitive material in which the surface on which the photosensitive layer is provided of a base paper, in particular, a base paper mainly composed of natural pulp, is coated with a polyolefin resin is still in contact with the silver halide photosensitive layer. It had a serious problem in terms of storage.

[0004] That is, a silver halide photosensitive material using a resin-coated paper as a support, in which the photosensitive layer of the base paper, especially a base paper mainly composed of natural pulp, on which the photosensitive layer is provided is coated with a polyolefin resin, is stored after its production. In such a case, as the storage is continued for a long time, particularly when stored under high temperature and high humidity, the unexposed portion of the photosensitive material called fog becomes more prone to develop during the development process, and There has been a problem that the tone of the photosensitive material changes and the tone becomes soft. In addition, there is another problem that the sensitivity of the photosensitive material is unduly increased or decreased.

Until now, various stabilizers or antifoggants have been proposed for preventing a change in photographic characteristics during storage of a silver halide light-sensitive material, that is, for improving storage stability of a so-called silver halide light-sensitive material. I have. For example, U.S. Patent No.
Hydroxy-substituted-triazolopyrimidine compounds described in JP-A No. 2,944,900 and JP-B-34-5647;
No. 621 and the like have been proposed. However, even if various stabilizers or antifoggants are contained in the emulsion layer of the silver halide photosensitive material having a support coated with a polyolefin resin on the base paper surface on which the photosensitive layer is provided, the sensitivity can be improved. Decline,
In addition to causing considerable photographic adverse effects such as softening of the tone, storage stability could not be effectively and significantly improved.

[0006] German Patent 1,171,266 proposes another type of stabilizer. According to this, a compound of the type of dioxybenzolcarboxylic acid or dioxybenzolsulfonic acid such as gentisic acid, tiron or α-resorcinol carboxylic acid or a salt thereof is added to the photographic emulsion layer or the protective layer, and the photographic emulsion layer is formed. Are disclosed for stabilizing. However, these compounds are simply applied to the polyolefin resin surface of a resin-coated paper-type support in which the base paper surface on which the photosensitive layer is provided is coated with a polyolefin resin and the opposite base paper surface is coated with a film-forming resin. Even if an undercoat layer containing the resin-coated paper was provided, the storage stability of the silver halide light-sensitive material having the resin-coated paper as a support was extremely poor or considerably insufficient.

There are also several proposals relating to the photographic properties of a support for a photosensitive material. JP-B-49-30446 and JP-B-50
In JP-33652, the resin layer on the side where the photosensitive layer is provided has a two-layer structure, because decomposition products and oxides of the resin generated during melt extrusion coating cause fogging in the emulsion of photographic paper, and the photosensitive layer and the photosensitive layer There has been proposed a resin-coated paper-type photographic paper support in which an adjacent upper resin layer is melt-extruded and coated at a low temperature and the generation of fog is small. However,
The silver halide light-sensitive material having the support has an extremely poor preservability, and it has been revealed that deterioration of the preservability is caused by a mechanism completely different from the mechanism described in these specifications. . Further, in JP-B 54-98 8 No. 4, hydroxy - substituted - were coated base paper with a polyolefin resin containing the triazolopyrimidine compounds, antifogging property of the resin-coated paper type photosensitive material support is proposed But
Even with the use of such a support, improvement in the storage stability of the silver halide light-sensitive material has been quite insufficient.

Further, regarding photographic paper, Japanese Patent Application Laid-Open No. 52-65423
And JP-B-58-43730 propose to remove the adverse effect on the photographic properties due to the decomposition of the cationic electrolyte and the paper additive, respectively. Even when used, the storage stability of the silver halide light-sensitive material could not be improved at all, and it was clarified that deterioration of the storage stability was caused by a mechanism completely different from the mechanism described in these specifications. In addition, JP-A-2-96741
JP-A-2-99689 and JP-A-2-99693 propose a technique for improving the photographic properties of unbleached kraft paper. According to them, the photographic properties of bleached kraft paper are good,
Unbleached kraft paper has poor photographic properties, because propylene oxide and / or silicon, which is a defoaming agent component used in the unbleached stage, remains, and an antifoaming agent containing those components and cold water extraction pH It has been proposed to improve the photographic properties of unbleached kraft paper by specifying. However, even if a resin-coated paper consisting of a base paper mainly composed of bleached natural pulp to which the technology is applied is used as a support, the storage stability of the silver halide light-sensitive material cannot be improved at all, and the storage stability is not deteriorated. It has been clarified that it is generated by a mechanism completely different from the mechanism described in these specifications. In addition, Japanese Patent Publication No. 58-43732 describes a technology for improving the storage stability of silver halide photographic materials by using resin-coated paper consisting of a base paper mainly composed of natural pulp bleached with an alkaline peroxide. Has been proposed,
Even with the use of this technique, it has not been sufficient to improve the preservability.

As described above, storage of a silver halide photosensitive material using a resin-coated paper whose surface on the side on which the photosensitive layer is provided with a photosensitive layer of a base paper, particularly a base paper mainly composed of natural pulp, is coated with a polyolefin resin. mechanism or cause of sexual deterioration, do not been known at all, also could not at all be effectively and remarkably improve the storage stability using a conventional technique.

[0010]

Accordingly, an object of the present invention is to provide a base paper on which a photosensitive layer is provided, which is remarkably improved in storage stability with respect to a silver halide photosensitive layer, and which is coated with a polyolefin resin. The object of the present invention is to provide a support for a photosensitive material, the base paper surface of which is coated with a resin capable of forming a film. Other objects of the present invention will become apparent from the following description.

[0011]

In order to solve the above-mentioned problems, the present inventors have made intensive studies and as a result, the base paper surface on which the photosensitive layer is provided is coated with a polyolefin resin, and the opposite side is provided with a polyolefin resin. In a support for a light-sensitive material, the base paper surface of which is coated with a resin capable of forming a film, the polyolefin resin surface has a polymer and a —COOM group or —SO ₃ M group (M represents a hydrogen atom or a metal atom).
It has been found that the object of the present invention can be achieved by providing an undercoat layer containing a-or o-dihydroxybenzene compound and a polyvalent metal compound.

According to the study of the present inventors, a support for a photosensitive material in which the base paper surface on which the photosensitive layer is provided is coated with a polyolefin resin and the opposite base paper surface is coated with a film-forming resin. Even if an undercoat layer containing a polymer and the above-mentioned p- or o-dihydroxybenzene compound or an undercoat layer containing a polymer and a polyvalent metal compound is provided on the surface of the polyolefin resin, the silver halide photosensitive material having the support can be used. Has a fairly or extremely poor shelf life,
When an undercoat layer containing a polymer, the above-mentioned p- or o-dihydroxybenzene compound and a polyvalent metal compound in combination is provided, a synergistic effect of the undercoat layer makes it possible to obtain a silver halide photosensitive material having the support. It has been found that the preservability is effectively and significantly improved, and the present invention has been achieved. On the other hand, when an undercoat layer containing a polymer, an m-dihydroxybenzene compound such as α-resorcinol carboxylic acid, and a polyvalent metal compound was provided, strangely, the effect of the present invention was not obtained at all.

The support for a light-sensitive material according to the present invention comprises a polymer and a -COOM group or -SO ₃ M on the surface of the polyolefin resin on the side on which the silver halide photosensitive layer is provided on the support.
Having a group (M represents a hydrogen atom or a metal atom), p
- or o- dihydroxybenzene compound and a polyvalent metallized
An undercoat layer containing a compound is provided.

The method of providing the undercoat layer on the surface of the polyolefin resin used in the practice of the present invention is as follows: after the running base paper surface is coated with the polyolefin resin, the silver halide photosensitive layer is provided before winding. On the resin surface of, the undercoat coating solution of the present invention is applied and dried to provide an undercoat layer,
It is preferable to use a so-called on-machine method. Alternatively, the resin-coated paper may be wound up, and if necessary, stored after winding up, and a new undercoat layer may be provided, that is, a so-called off-machine method. As an apparatus for applying the undercoat coating liquid,
Examples include air knife coaters, roll coaters, bar coaters, wire bar coaters, blade coaters, slide hopper coaters, curtain coaters, gravure coaters, flexographic gravure coaters, and combinations thereof. Prior to the application, it is desirable that the resin surface be subjected to an activation treatment such as a corona discharge treatment or a flame treatment. Various drying devices such as hot air dryers such as linear tunnel dryers, arch dryers, air loop dryers, sine curve air float dryers, etc., drying devices using infrared rays, heating dryers, microwaves, etc. Can be given.
Drying conditions are arbitrary, but generally, 60 ° C to 15 ° C.
It is performed at 0 ° C. for several seconds to 10 minutes.

The polymer contained in the undercoat layer used in the practice of the present invention is not particularly limited, but various hydrophilic polymers are preferred. For example,
Gelatin, polyvinyl alcohol, starch and the like can be used, but gelatin is particularly preferred from the viewpoints of coatability of the undercoating solution and film formation between the support for the photosensitive material and the silver halide photosensitive layer. As the gelatin preferably used,
Examples include lime-processed gelatin, acid-processed gelatin, enzyme-processed gelatin, and gelatin derivatives, such as gelatin reacted with dibasic acid anhydride. The coating amount of the undercoat layer is not particularly limited, but the coating amount of the hydrophilic polymer, preferably gelatin, is 0.1%.
% To 10 wt% of the water-based coating solution well it is to apply ^{1g / m 2 ~40g / m 2} , at a solid weight in terms of the layer to the storage stability and the support of the silver halide photosensitive material and the photosensitive layer 0.005g /
m ² ~2.0g / m ² range is preferred, 0.01g / m ² ~1.
A range of 0 g / m ² is particularly preferred. The pH of the undercoating liquid is not particularly limited, but is preferably pH 8 or less from the viewpoint of improving the storage stability of the silver halide light-sensitive material.
The following are more preferred.

[0016] -COOM group or -SO ₃ M group is the additional inclusion in the subbing layer employed in the practice of the present invention (M represents a hydrogen atom or a metal atom) having, p- or o-
The dihydroxybenzene compound is not particularly limited as long as it is a benzene compound having at least two hydroxyl groups and a -COOM group or a -SO ₃ M group,
Further, for example, they may have other substituents such as a halogen atom, an alkyl group, an allyl group, an alkoxy group, and an acetyl group. Specific examples of the dihydroxybenzene compound used in the practice of the present invention include the following, but the present invention is not limited thereto.

(A) 2,3-dihydroxybenzoic acid (B) 3,4-dihydroxybenzoic acid (C) 2,5-dihydroxybenzoic acid (D) hydroquinone-2,5-dicarboxylic acid (E) pyrocatequinone-4 -Potassium sulfonate (F) 1,2-dioxybenzene-3,5-sodium disulfonate (G) potassium hydroquinone sulfonate (H) disodium hydroquinone-2,5-disulfonate

These compounds can also be synthesized according to the method described in "Large Organic Chemistry, Aromatic Compounds I and II" (published by Asakura Shoten, supervised by Kouji Takeshi, Volumes 9 and 10) and the like. And can also be obtained from the general market. As a method for incorporating these compounds into the undercoat layer, a method in which the compound is dissolved in an appropriate solvent such as water, methanol, ethanol or the like and included in the undercoat coating liquid is preferable.
When the amount of the dihydroxybenzene compound used in the practice of the present invention is too small, the effect of improving the storage stability of the silver halide light-sensitive material becomes insufficient, and when it is too large, the adhesion between the photosensitive layer and the support becomes insufficient. Since the properties tend to deteriorate and the sensitivity immediately after this tends to decrease, 6.5 × 10 ⁻⁷ mol / m ^2-
The range is preferably 1 × 10 ⁻³ mol / m ² , and more preferably 1.5 × 10 ⁻⁶ mol / m ^{2 to} 3 × 10 ⁻⁴ mol / m ^2.
0 ^-6 mol / m ² to 1 × 10 ^-4 mol / m ² range is particularly preferred.

Examples of the polyvalent metal compound contained in the undercoat layer used in the practice of the present invention include magnesium,
Calcium, barium, zinc, aluminum, chromium,
It is selected from hydrated colloids of salts, complexes, hydroxides or oxides of zirconium, tin, silicon and the like, and a water-soluble or colloidal polyvalent metal compound is easily prepared for the undercoating liquid. And the effect of improving the storage stability of the silver halide photosensitive material. As specific examples of them,
Preferred are salts of magnesium, calcium, barium, zinc, aluminum, chromium, zirconium, tin and the like with organic acids such as acetic acid and citric acid, and inorganic acids such as hydrochloric acid, carbonic acid, nitric acid and sulfuric acid, and more specifically. Contains chrome alum, chromium sulfate, potassium alum, calcium chloride,
Barium chloride, magnesium sulfate, zirconium nitrate and the like can be mentioned. Examples of the complex include a complex with a complexing agent such as ethylenediaminetetraacetic acid. Specific examples of the hydroxide or colloidal polyvalent metal compound include aluminum hydroxide, magnesium hydroxide, and colloidal polyvalent metal compound. Alumina and the like can be given.
As a method for incorporating the polyvalent metal compound in the undercoat layer, a method of preparing an aqueous solution or a colloidal solution thereof and incorporating it in the undercoat coating liquid is preferable. When the coating amount of these polyvalent metal compounds is too small, the effect of improving the storage stability of the silver halide light-sensitive material becomes insufficient, and when too large, the adhesion between the light-sensitive layer and the support deteriorates, Since the coating properties of the coating solution are deteriorated, 3 × 10 ⁻⁸ as metal atoms
Mol / m ² to 1 × 10 ⁻⁴ mol / m ² , preferably 1 × 10 ⁴ mol / m ^2.
-7 mol / m ² to 4 × 10 ^-5 mol / m ² is more preferable.
The range of × 10 ⁻⁷ mol / m ² to 1 × 10 ⁻⁵ mol / m ² is particularly preferred.

In the undercoat layer used in the practice of the present invention,
Various additives can be included. As a preservative, a p-hydroxybenzoate compound described in or exemplified in JP-A-1-102551, a benzisothiazolone compound, an isothiazolone compound, etc., and as a surfactant, an alkylbenzene sulfonate, an anionic interface such as a sulfosuccinate salt, etc. Surfactants, nonionic surfactants such as saponins, alkylene oxides, etc.
-9303, U.S. Pat. No. 3,589,906, etc., fluorinated surfactants, amino acids, amphoteric surfactants described and exemplified in JP-A-1-92740, etc., and amphoteric surfactants such as esters of amino alcohols As hardeners, hardeners such as active halogen compounds, vinylsulfone compounds, aziridine compounds, epoxy compounds, acryloyl compounds, isocyanate compounds, as well as toning agents, fluorescent brighteners, matting agents, antifoggants or stable Agents, pH adjusters and the like can be incorporated in appropriate combinations.

The base paper used in the practice of the present invention includes:
Paper mainly composed of natural pulp (hereinafter simply referred to as base paper)
Is advantageously used, but so-called synthetic paper in which synthetic fibers or synthetic resin films are made into pseudo paper may be used.

Pulp constituting base paper which is advantageously used in the practice of the present invention is described in JP-A-58-37642 and JP-A-60-6
No. 7940, JP-A-60-69649, it is advantageous to use an appropriately selected natural pulp as described or exemplified in JP-A-61-35442, etc. Other synthetic pulp and synthetic fiber may be used. Natural pulp was subjected to normal bleaching treatment of chlorine, hypochlorite, chlorine dioxide bleaching and alkali extraction or alkali treatment and, if necessary, oxidative bleaching treatment with hydrogen peroxide, oxygen, etc., and a combination treatment thereof Wood pulp of softwood pulp, hardwood pulp, and softwood pulp mixed pulp is advantageously used, and various pulp such as kraft pulp, sulfite pulp, and soda pulp can be used.

Various additives can be incorporated into the base paper used in the practice of the present invention when preparing the stock slurry. Examples of the sizing agent include fatty acid metal salts and / or fatty acids, alkyl ketene dimer emulsions described or exemplified in JP-B-62-7534, epoxidized higher fatty acid amides, alkenyl or alkyl succinic anhydride emulsions, rosin derivatives, etc. As a paper strength enhancer, anionic, cationic or amphoteric polyacrylamide, polyvinyl alcohol, cationized starch, vegetable galactomannan, etc., as a wet strength agent, polyamine polyamide epichlorohydrin resin, etc., as a filler, clay, kaolin, Calcium carbonate, titanium oxide, etc .; water-soluble aluminum salts such as aluminum chloride and bansulfate as fixing agents; caustic soda, sodium carbonate, sulfuric acid, etc. as pH regulators;
It is advantageous to incorporate color pigments, coloring dyes, fluorescent brighteners and the like described or exemplified in 1-266537 and the like in an appropriate combination.

In the base paper which is advantageously used in the practice of the present invention, various water-soluble polymers, antistatic agents and additives can be contained by spraying, size press or tab size press. Examples of water-soluble polymers include starch-based polymers, polyvinyl alcohol-based polymers, gelatin-based polymers, polyacrylamide-based polymers, and cellulose-based polymers described and exemplified in JP-A 1-266537, and sodium chloride, potassium chloride, and the like as antistatic agents. Emulsions such as alkali metal salts, alkaline earth metal salts such as calcium chloride and barium chloride, colloidal metal oxides such as colloidal silica, organic antistatic agents such as polystyrene sulfonate, and petroleum resin emulsions as latex , Ethylene-vinyl acetate copolymer, JP-A-55-4027, JP-A-1-80538
Emulsions or latexes of a copolymer to be described or exemplified ethylene and acrylic acid (or methacrylic acid) and the least even components No., as a pigment, clay, kaolin, talc, barium sulfate, titanium oxide, pH It is advantageous to add, as a regulator, an appropriate combination of additives such as hydrochloric acid, phosphoric acid, citric acid, and caustic soda, and the above-mentioned coloring pigments, coloring dyes, and optical brighteners.

The base paper advantageously used in the practice of the present invention preferably has a smooth surface having a Beck smoothness of 100 seconds or more as defined by JIS P8119.
Those having a smooth surface of 00 seconds or more are more preferable. As a method for producing a base paper having a Beck smoothness of 100 seconds or more,
Generally, hardwood pulp, which is short fiber and easily smooth, is often used, and beaten by a beater so that the long fiber content is reduced as much as possible. Specifically, the beating of the pulp is preferably performed so that the fiber length of the pulp after the beating has a mesh length of 42 to 20 to 45% and a freeness of 200 to 350 CSF. Next, regarding the stock chiller to which the internal additive was added, JP-A-58-37642, JP-A-61-260240, and JP-A-61-260240
No. -284762 No. etc. by adopting an appropriate papermaking method as described or exemplified, a Fourdrinier paper machine, a papermaking machine so as to obtain a uniform formation by a commonly used paper machine such as a round net paper machine, After the papermaking, the paper is subjected to calendering using a machine calender, a super calender, a heat calender, or the like, and a base paper having a Beck smoothness of 100 seconds or more can be produced. Regarding the thickness of the base paper is not particularly limited, the basis weight preferably from ^{40g / m 2 ~250g / m 2} .

The surface of the support for the photosensitive material of the present invention on the side of the base paper on which the photosensitive layer is provided is coated with a polyolefin resin. Examples of the polyolefin resins include homopolymers such as polyethylene, polypropylene, polybutene and polypentene; copolymers composed of two or more α-olefins such as ethylene-butylene copolymer; and mixtures thereof. Polyethylene resins are particularly preferred from the viewpoint of coating properties and adhesion to base paper. As those polyethylene resins, low density polyethylene, medium density polyethylene, high density polyethylene,
Linear low-density polyethylene, copolymers of ethylene with α-olefins such as propylene and butylene, carboxy-modified polyethylene and the like, and mixtures thereof; various densities, melt flow rates (hereinafter simply abbreviated as MFR), molecular weights Although a material having a molecular weight distribution can be used, usually, the density is in the range of 0.90 to 0.97 g / cm ³ , the MFR is 0.1 g / 10 min to 50 g / 10 min, and the MFR is preferably 0.3 g / 10 min to 40 g.
Those having a range of g / 10 minutes can be advantageously used alone or as a mixture. When the resin has a multi-layer structure, the outermost layer resin may be, for example, MFR 5 g / 10 min to 20 g / 10 min, and the lower layer resin may be, for example, MFR 2 g / 10 min to 10 g / 10 min. Resins having the properties and constitutions described above can also be used.

The surface of the support for the photosensitive material of the present invention opposite to the side on which the photosensitive layer is provided is coated with a resin capable of forming a film. Polyolefin resins, polycarbonate resins, polyester resins, and thermoplastic resins such as polyamide resins are preferable as the resins capable of forming the film, among which the above-mentioned polyolefin resins are more preferable from the viewpoint of melt extrusion coating properties, and polyethylene resins are particularly preferable. . Further, it may be coated with an electron beam curable resin described or exemplified in JP-B-60-17104.

In the present invention, a method for coating a base paper surface of a support for a light-sensitive material with a resin is as follows.
Preferably, in the case of a polyolefin resin, particularly preferably a polyethylene-based resin, a thermoplastic resin composition is cast on a running base paper by using a melt extruder, and is cast from a slit die into a film to cover the same. It is preferred to coat by an extrusion coating method. At that time, the temperature of the molten film is preferably 280 to 340 ° C. As a slit die, T-type die,
L-die, flat die are preferred Fi Tsu Shuteiru die, it is desirable that the slit opening diameter is 0.1mm to 2 mm. Before coating the resin composition on the base paper, the base paper is preferably subjected to an activation treatment such as a corona discharge treatment or a flame treatment. Further, as described in JP-B-61-42254, it is preferable to coat a resin layer on a running base paper after spraying an ozone-containing gas on a molten resin composition in contact with the base paper. Further, it is preferable that the front and back resin layers are successively, preferably continuously, extruded and coated on the base paper by a so-called tandem extrusion coating method. Further, the surface resin layer surface of the support for the photosensitive material on which the photosensitive layer is coated can be processed into a glossy surface, a finely rough surface described in JP-B No. 62-19732, a matte surface or a silk surface, The back resin layer on the opposite side is usually preferably processed to a matte surface. Also, the thickness of the resin layer on the front and back
Although there is no particular limitation, a range of 7 μm to 60 μm is generally preferable.
Or a thickness in the range of 10 μm to 45 μm is advantageous.
is there.

Various additives can be contained in the resin layer of the support for a light-sensitive material in the present invention. JP-B-60-3430, JP-B-63-11655, JP-B1-38291
No. 1-38292, JP-A-1-105245 and the like or white pigments such as titanium oxide, zinc oxide, talc, calcium carbonate, etc., fatty acid amides such as stearamide, arachidic amide, stearic acid Fatty acid metal salts such as zinc, calcium stearate, aluminum stearate, magnesium stearate, zinc palmitate, zinc myristate and calcium palmitate;
Hindered phenol, hindered amine, phosphorus-based, various antioxidants such as sulfur-based, etc. described in No. 1-105245, blue-based pigments and dyes such as cobalt blue, ultramarine, celian blue, phthalocyanine blue, cobalt violet, fast violet, magenta pigments and dyes such as manganese violet, a fluorescent whitening agent according or exemplified in Japanese Patent Laid-Open 2-25 4 440 No., various additives as appropriate combination can be incorporated such as an ultraviolet absorber. These additives are preferably contained as a resin masterbatch or compound.

The surface of the backing resin layer of the support for a light-sensitive material according to the present invention is subjected to an activation treatment such as a corona discharge treatment or a flame treatment, and thereafter various back coat layers are coated for antistatic treatment or the like. be able to. The back coat layer includes JP-B-52-18020, JP-B-57-9059, and JP-B-57-5
No. 3940, JP-B-58-56859, JP-A-59-214849, and inorganic antistatic agents described or exemplified in JP-A-58-184144, organic antistatic agents, hydrophilic binders, latexes,
A curing agent, a pigment, a surfactant and the like can be appropriately combined and contained.

The support for the photosensitive material in the present invention is coated with various photosensitive material constituent layers and is used for color photographic printing paper, black-and-white photographic printing paper, photolithographic printing paper, computerized photolithographic printing paper, laser light exposure. It can be used for various purposes such as photographic paper, copy photographic paper, reversal photographic material, silver salt diffusion transfer method negative and positive, and printing material. For example, a silver chloride, silver bromide, silver chlorobromide, silver iodobromide, silver chloroiodobromide photosensitive emulsion layer can be provided. By incorporating a color coupler into the silver halide light-sensitive emulsion layer, a multilayer silver halide color photographic constituting layer can be provided. Further, a light-sensitive material constituting layer for a silver salt diffusion transfer method can be provided. As a binder for the light-sensitive material constituting layer, hydrophilic polymer substances such as polyvinylpyrrolidone, polyvinyl alcohol, and a sulfate compound of a polysaccharide can be used in addition to ordinary gelatin. In addition, the above-mentioned light-sensitive material constituting layer can contain various additives. For example, as a sensitizing dye, a cyanine dye, a merocyanine dye, etc., as a chemical sensitizer, a water-soluble gold compound, a sulfur compound, etc., as an antifoggant or stabilizer, a hydroxy-triazolopyrimidine compound, a mercapto heterocyclic compound, etc. Hardeners such as formalin, vinyl sulfone compounds and aziridine compounds, and coating aids such as alkylbenzene sulfonates and sulfosuccinates, as well as fluorescent whitening agents, sharpness improving dyes, antistatic agents, pH adjusters, and more. Water-soluble iridium, a water-soluble rhodium compound and the like can be incorporated in a suitable combination during the formation and dispersion of silver halide.

The light-sensitive material according to the present invention may be exposed, developed, and stopped in accordance with the light-sensitive material as described in "Photosensitive Material and Handling Method" (Kyoritsu Shuppan, Goro Miyamoto, Photographic Technology Course 2). , Fixing, bleaching, and stabilization. Also, multilayer silver halide color photographic materials are
The treatment may be carried out with a developer containing a development accelerator such as benzyl alcohol, thallium salt or phenidone, or with a developer substantially free of benzyl alcohol.

[0033]

EXAMPLES Next, in order to explain the present invention more specifically,
An embodiment will be described.

Example 1 A mixed pulp of a hardwood bleached sulphite pulp and a hardwood bleached kraft pulp was beaten to 320 ml of Canadian Standard Freeness. Further, 100 parts by weight of pulp, 3 parts by weight of a cationized starch, and anion 0.2 parts by weight of fluorinated polyacrylamide, 0.4 parts by weight of an alkyl ketene dimer emulsion (as a ketene dimer component) and 0.4 parts by weight of a polyaminopolyamide epichlorohydrin resin were added to obtain a basis weight of 76 g / m ² as an absolute dry weight. Paper was manufactured. The obtained wet paper was dried at 110 ° C., and subsequently 3 parts by weight of carboxy-modified polyvinyl alcohol, 0.05 parts by weight of fluorescent whitening agent, 0.002 parts by weight of blue dye, 4 parts by weight of sodium chloride, 0.2 parts of citric acid An impregnating solution comprising 25 parts by weight of water and 93 parts by weight of water was impregnated with 25 g / m ² , dried with hot air at 110 ° C., and further subjected to supercalendering at a linear pressure of 90 kg / cm to produce a base paper for a support for a photosensitive material. . At this time, the Bekk smoothness of the base paper was 200 seconds.

Next, after the base paper surface (back surface) opposite to the side on which the photosensitive layer is coated is subjected to corona discharge treatment, a low-density polyethylene resin (density 0.92 g / cm ³ , MFR = 2 g / 10 min) 2
5 parts by weight and high density polyethylene resin (density 0.96g / cm
³ , MFR = 20 g / 10 min) A resin composition consisting of 75 parts by weight was applied at a resin temperature of 320.degree.
Melt extrusion coating was performed at 40 m / min.

Subsequently, the surface of the base paper was subjected to a corona discharge treatment, and then a low-density polyethylene resin (density 0.92
0 g / cm ³ , MI = 8.5 g / 10 min) 47.5 wt%, anatase type titanium dioxide surface-treated with hydrous aluminum hydroxide (0.75 wt% as Al ₂ O _{3 based} on titanium dioxide) 20 parts by weight of a master batch of titanium dioxide pigment comprising 50% by weight of pigment and 2.5% by weight of zinc stearate, a low-density polyethylene resin (density 0.920 g / cm
³ , MI = 4.5 g / 10 min) 65 parts by weight and high density polyethylene resin (density 0.970 g / cm ³ , MI = 7.0 g / 10)
Min) a resin composition consisting of 15 parts by weight at a resin temperature of 325 ° C.
At a running speed of the base paper of 140 m / min. In addition, the melt extrusion coating of the front and back polyethylene resins was performed by a so-called tandem method in which extrusion coating was performed sequentially.
At that time, the surface of the resin layer containing the titanium dioxide pigment of the resin-coated paper was processed into a finely rough surface, and the surface quality of the resin layer on the back was processed into a matte surface such as paper.

Further, a corona discharge treatment is applied to the resin surface on the front side of the support before the front and back resins are processed and wound up.
2.5% by weight of gelatin, the amount of 2,5-
Dihydroxybenzoic acid or a dihydroxybenzene compound for comparison, a 2% chromium alum aqueous solution in an amount corresponding to the coating amount shown in Table 1 as a polyvalent metal compound, methanol and water of sulfosuccinic acid-2-ethylhexyl ester salt
0.5% by weight of a mixed solution, 0.3% by weight of a 5% methanol solution of p-hydroxybenzoic acid butyl ester, p of a coating solution
An undercoating solution consisting of an aqueous solution of caustic soda to an H of 6.0 and the remaining weight% of water was applied on-machine so as to have a gelatin coating amount of 0.1 g / m ² .

After that, the backside resin layer of the resin-coated paper was subjected to a corona discharge treatment, and thereafter, an epoxy-based resin comprising gelatin: silicon dioxide matting agent (average particle diameter: 2 μm) = 3: 1 as a dry weight, and 15% by weight of gelatin. A backcoat coating solution containing an appropriate amount of a coating aid and an inorganic antistatic agent in addition to the hardener was applied in a coating amount of 3 g / m ² minutes in terms of gelatin to obtain a support for a photosensitive material.

Next, an emulsion layer and its protective layer were provided on the undercoat layer on the front side of the support for a light-sensitive material to obtain a black-and-white photographic printing paper. The emulsion layer was prepared by dispersing 19.2 g of silver halide grains with silver nitrate in 14.4 g of gelatin in the presence of 1.2 × 10 ^-5 g of potassium hexachloroiridate (III). Prepared ArBr / AgCl / AgI = 95/4.
It consists essentially of [1,0,0] face in combination sensitized by 5 / 0.5 Sulfur sensitization optimal sensitivity of the average particle diameter of 0.6μ with a (mol%) consisting halogen composition and a gold sensitizer Includes neutral silver halide photographic emulsions, and in addition to gelatin necessary for film formation, appropriate amounts of stabilizers, sensitizing dyes, coating aids, hardeners, fluorescent brighteners, thickeners, filter dyes, etc. hints, 2.2 g / m ² silver nitrate were multilayer coating with a protective layer in a coating amount equivalent to 4.4 g / m ² gelatin. The protective layer contains a coating aid and a hardener in addition to gelatin corresponding to ² g / m ² .

The coated and dried sample was dried at 35 ° C. and under normal humidity.
After storage for 4 days and at 55 ° C. for 4 days, the film was exposed to flash light for sensitometry, stopped after development, fixed, washed with water, and dried, and the photographic characteristics were examined, and the storage stability was examined.

Table 1 shows the obtained results.

[0042]

[Table 1]

Note that (Note 1) to (Note 5) in Table 1 are as follows.

(Note 1) ○ indicates the sample No. according to the present invention. Represents

(Note 2) (C): Compound (C) described in the text of the specification was added to an undercoating solution with a methanol solution of 2,5-dihydroxybenzoic acid at an appropriate concentration. The dihydroxybenzene compounds (I) to (M) for comparison are as follows. (I): Haidoroki Bruno emissions, (J): catechol, (K): 3,5- dihydroxybenzoic acid, (L):
2,5-dihydroxyacetophenone, (M): methylhydroquinone. These comparative compounds were added to the undercoating solution in an appropriate concentration of a methanol solution.

(Note 3) Immediately after the measurement, the sensitivity S of the silver image of the sample stored at 35 ° C. and normal humidity for 1 day was D = 1 . 1 represents the relative sensitivity.

(Note 4) Regarding the storability, the reflection density of the silver image D = 1 . 1 and relative exposure latitude L (smaller numbers indicate higher contrast, D = 0.21 and D = 0.75
(Expressed as the logarithmic difference of the exposure amount) giving 35
The differences between the relative sensitivities S and L of the sample stored at 55 ° C. for 4 days with respect to the sample stored at 1 ° C. and normal humidity for 1 day are indicated as ΔS and ΔL. + In ΔS indicates sensitization and − indicates desensitization, the value of ΔL indicates the degree of softening, and ΔF indicates the increase in fog.

(Note 5) For samples with an emulsion film, the samples stored at 35 ° C. for 1 day were developed and then nailed vertically and horizontally.
The emulsion surface was scratched at cm intervals to make a grid-like scratch, and then the surface was rubbed with a fingertip in running water to evaluate the degree of peeling of the emulsion layer. The evaluation criteria were as follows: ：: no emulsion layer peeling, good film adhesion, △ to Δ: slight peeling of emulsion layer, but no problem in practical use, Δ: slight peeling of emulsion layer, but practical To some extent within the upper limit, x: The emulsion layer was peeled so much that the film was attached, which indicates some practical problems.

From the results shown in Table 1, gelatin was used as the polymer and 2,5 as the dihydroxybenzene compound of the present invention.
-A silver halide photosensitive material having a support for a photosensitive material according to the present invention coated with an undercoat layer containing dihydroxybenzoic acid and chromium alum as a polyvalent metal compound has good storage stability and little change in sensitivity. The softening of the tone is remarkably suppressed and the fog is also remarkably suppressed, the sensitivity is not immediately reduced, and the emulsion film is well provided. The support for a photosensitive material according to the present invention is excellent. You can see that there is.

The coating amount of the dihydroxybenzene compound for use in the present invention contained in the undercoat layer is preferably 1.5 × 10 ⁻⁶ from the viewpoints of sensitivity immediately after the light-sensitive material, storage stability and the presence of an emulsion film. It is understood that the range of mol / m ^{2 to} 3 × 10 ⁻⁴ mol / m ² is more preferable, and the range of 3 × 10 ⁻⁶ mol / m ² to 1 × 10 ⁻⁴ mol / m ² is particularly preferable.

On the other hand, a support for a light-sensitive material in which an undercoat layer containing no dihydroxybenzene compound or polyvalent metal compound in the undercoat layer, or a -COOM for use in the present invention.
Photosensitive to (M is a hydrogen atom or represents a metal atom) group or -SO ₃ M group was coated with a subbing layer was allowed containing dihydroxybenzene compounds for comparative instead of having, p- or o- dihydroxybenzene compound The material support is
It can be seen that there is a problem in that the photographic material having the support has poor preservability and causes a decrease in sensitivity immediately after.

Example 2 In place of the 2% chromium alum aqueous solution used in Sample No. 5 of Example 1, an appropriate concentration of chromium alum aqueous solution having a coating amount shown in Table 2 was used. Sample N of Example 1
Performed similarly to o, 5.

Table 2 shows the obtained results.

[0054]

[Table 2]

Note that (Note 6) to (Note 8) in Table 2 are as follows.

(Note 6) ○ indicates a sample according to the present invention.

(Note 7) Same as Table 1.

(Note 8) Regarding the application state of the undercoat layer, the application state at the time of applying the undercoat coating liquid was evaluated. The evaluation criteria are as follows: ：: the coating state is uniform and good, and △: the coating surface is slightly uneven and non-uniform, but indicates a degree that there is no practical problem.

From the results shown in Table 2, the addition amount of the polyvalent metal compound contained in the undercoat layer was determined to be 1 × 10 ⁻⁷ mol / m from the viewpoint of the storage stability of the light-sensitive material and the applicability of the undercoat coating solution. m ² to 4
The range of × 10 ⁻⁵ mol / m ² is more preferable, and the range of 4 × 10 ⁻⁷ mol / m ² is more preferable.
It is understood that the range of ² to 1 × 10 ⁻⁵ mol / m ² is particularly preferable.

Example 3 A sample was prepared in the same manner as in Sample No. 5 of Example 1 except that the amount of gelatin shown in Table 3 was used instead of the amount of gelatin used in Sample No. 5 of Example 1. .

Table 3 shows the obtained results.

[0062]

[Table 3]

Note that (Note 9) to (Note 10) in Table 3 are as follows.

(Note 9) Same as ΔF in Table 1.

(Note 10) Same as (Note 5) in Table 1.

From the results shown in Table 3, the amount of gelatin, which is a polymer, contained in the undercoat layer is preferably 0.005 g / m ² to 0.005 g / m ^{2 in view} of the storability of the light-sensitive material and the presence of an emulsion film.
It turns out that the range of 2.0 g / m ² is particularly preferable.

Example 4 In place of (C) 2,5-dihydroxybenzoic acid, which is the dihydroxybenzene compound for use in the present invention, which was used in sample Nos. 5 and 5 of Example 1, compound (A) described in the present specification,
Samples Nos. 5 and 5 of Example 1 except that (B), (D), (E), (F), (G), and (H) were used in the same molar amount as (C) as a methanol solution or aqueous solution having an appropriate concentration. Was performed in the same manner as described above. Further, for comparison, the samples No. 1 and
Was performed in the same manner as described above.

As a result, when the compound (A), (B) or (D) was used, the same result as that of Sample No. 5 was obtained. Further, ΔF in the case of using the compound (E), (F), (G) or (H) was higher by 0.01 to 0.02 than that in the case of using the compound (C). The increase in fog was remarkably suppressed as compared with the test sample.

Example 5 Instead of the aqueous solution of chromium alum used as the polyvalent metal compound of Sample Nos. 5 and 5 of Example 1, potassium alum and barium chloride were applied so that the coating amount was the same as the metal atom. The operation was performed in the same manner as in Sample No. 5 of Example 1 except that an aqueous solution of magnesium sulfate or zirconium nitrate having an appropriate concentration was used. As a result, the same result as that of Sample Nos. 5 and 5 of Example 1 was obtained.

[0070]

According to the present invention, the base paper on which the photosensitive layer is provided is coated with a polyolefin resin, and the base paper on the opposite side has a film-forming ability, in which the storage stability with respect to the silver halide photosensitive layer is remarkably improved. An excellent support for a photosensitive material coated with a resin can be provided.

Continuation of the front page (56) References JP-A-62-260149 (JP, A) JP-A-62-173460 (JP, A) JP-A-62-195649 (JP, A) JP-A-3-167544 (JP) JP-A-61-35441 (JP, A) JP-A-1-130156 (JP, A) JP-A-58-221839 (JP, A) JP-A-63-163337 (JP, A) (58) Field surveyed (Int.Cl. ⁶ , DB name) G03C 1/91 G03C 1/79

Claims (6)

(57) [Claims] 1. A support for a photosensitive material, wherein a base paper surface on which a photosensitive layer is provided is coated with a polyolefin resin, and a base paper surface on the opposite side is coated with a film-forming resin.
A polymer and a —COOM group or a —SO ₃ M group (M represents a hydrogen atom or a metal atom) on the polyolefin resin surface
A support for a light-sensitive material, comprising a subbing layer containing a p- or o-dihydroxybenzene compound and a polyvalent metal compound, the subbing layer comprising: 2. The support according to claim 1, wherein the polymer is gelatin. 3. The coating amount of the polymer is 0.01 g / m ^{2 to} 1 g /
Claim 1 or 2 light-sensitive material support according a m ^2. 4. The photosensitive material according to claim 1, wherein the amount of the dihydroxybenzene compound applied is 1.5 × 10 ⁻⁶ mol / m ^{2 to} 3 × 10 ⁻⁴ mol / m ² . Support. 5. The support for a light-sensitive material according to claim 1, wherein the polyvalent metal compound is water-soluble or colloidal. 6. The method according to claim 1, wherein the coating amount of the polyvalent metal compound is 1 × 10 ⁻⁷ mol / m ² to 4 × 10 ⁻⁵ mol / m ² as metal atoms. Support for photosensitive materials.