JPH06118554A - Substrate for photographic printing paper and its production - Google Patents

Abstract

PURPOSE:To produce a low-cost substrate for photographic printing paper saving resources and capable of increasing the sharpness and production speed of an image. CONSTITUTION:This substrate for photographic printing paper consists of a base and resin layers coating both sides of the base and further contains middle layers interposed between the base and each of the resin layers if necessary. At least the resin layer coating the emulsion layer side is made of a resin compsn. contg. >=40wt.% ethylene.alpha-olefin copolymer resin having 0.870-0.915g/cm<3> density and 5-60wt.% inorg. pigment and/or metal powder.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photographic printing paper support provided with a water resistant resin coating layer on both sides of a substrate, and more particularly to improving the sharpness of an image and saving the photographic printing paper support. The present invention relates to a support for photographic printing paper, which is suitable for increasing resource utilization and manufacturing speed, and a manufacturing method thereof.

[0002]

The essential construction of photographic paper supports is already known and, for example, as disclosed in U.S. Pat. No. 3,501,298, both sides of a paper substrate are coated with a water resistant resin. It is known that the water-resistant resin coating layer on the side of coating and emulsion coating contains a pigment such as titanium dioxide, a bluing agent (including a blue pigment), a fluorescent brightening agent and the like. A polyolefin resin is usually used as the water resistant resin.

Such a photographic printing paper support does not adversely affect the photographic emulsion, has good adhesion between the paper or synthetic paper and the water resistant resin coating layer, and has excellent dimensional stability. In addition to the characteristics such as high hiding property and less penetration of the developing solution from the edge, it is required that the curl balance after coating the emulsion is good and the smoothness is excellent.

It is known that the pigment contained in the water-resistant resin coating layer on the emulsion coating layer side affects the resolution of the photographic paper, and it is particularly preferable to use titanium dioxide as the pigment. . Therefore, a method of highly filling titanium dioxide has been developed (Japanese Patent Application Laid-Open No. 57-358).
No. 55), the high cost of titanium dioxide increases the cost, and since the fluidity deteriorates, the resin coating layer has to be thick.

In order to solve such a problem, as a polyolefin resin used as a water resistant resin, 0.915 to
It has been proposed to use a low-density polyethylene resin having a density of 0.935 g / cm ³ (Japanese Patent Laid-Open No. 2-7).
3246), and the use of a linear polyethylene resin as the low-density polyethylene has been proposed (JP-A-2-308158).

As a result of further studies on the water-resistant resin, the inventors of the present invention have found that when a resin having a density of 0.915 g / cm ³ or more is used, when the pigment is contained at a high density, film breakage or pigment dispersion occurs. In addition to the occurrence of defects, when the melt coating is applied to the substrate, the motor load becomes excessive, so high-speed coating becomes impossible and productivity deteriorates, and the density is 0.87 g.
In the case of using less than 1 / cm ³ , a large amount of expensive α-olefin must be used in order to make up for the deteriorating polymerizability, which increases the cost of the resin and also from the cooling roll at the time of production. It was found that the peeling of No. 1 deteriorates. On the other hand, when the ethylene-α-olefin copolymer resin having a density of 0.870 to 0.915 g / cm ³ is used in a certain amount or more, not only high-speed coating becomes possible but also the resin coating layer We found that the thickness can be reduced,
The present invention has been reached.

[0007]

SUMMARY OF THE INVENTION Therefore, the first object of the present invention is to reduce the thickness of the water resistant resin coating layer coated on the surface of the substrate on the emulsion layer side, which is inexpensive and capable of improving the sharpness of an image. An object is to provide a support for photographic printing paper. A second object of the present invention is to provide a resource-saving support for photographic printing paper, which can improve not only the sharpness of images but also the production speed. A third object of the present invention is to provide a method of manufacturing a support for photographic printing paper, which can improve the sharpness of an image, save resources and improve the manufacturing speed.

[0008]

The above objects of the present invention are to provide a substrate, a resin layer coated on both sides of the substrate, and, if necessary, an intermediate layer provided between the substrate and the resin layer. In the support for photographic printing paper, the resin layer of which at least the emulsion layer side is covered with ethylene / α- having a density of 0.870 to 0.915 g / cm ^3. 40% by weight of olefin copolymer resin
The present invention has been accomplished by the above, and a support for photographic paper and a method for producing the same, which comprises a resin composition containing 5 to 60% by weight of an inorganic pigment and / or a metal powder.

0.870 to 0.91 used in the present invention
The ethylene-α-olefin copolymer resin having a density of 5 g / cm ³ has a lower density than any of the ethylene-α-olefin copolymer resins conventionally used for photographic printing paper, It should be called low density polyethylene resin.

As is well known, the low-density polyethylene resin has the advantages of both polyethylene resins produced by the medium-low pressure method or the high-pressure method, and meets the requirements of the times of energy saving and resource saving, low cost, It is a high-strength resin excellent in foreign matter sealing property, hot tack property and the like, and also excellent in heat seal strength and physical strength, and is called a third polyethylene resin.

When ethylene and α-olefin are copolymerized by the low pressure method or the high pressure improvement method, a copolymer having a linear straight chain with a short branch is obtained, and the density of this copolymer is generally It is about the same as low-medium density polyethylene resin. By the way, the commercially available products are 0.920 to 0.960 g / cm
Many are in the range of ³ , with a melt index of 0.1
Many are within the range of up to 50 g / 10 minutes.

On the other hand, the ethylene-α-olefin copolymer resin used in the present invention has a density of 0.8.
It is 70 to 0.915 g / cm ^3, which is regarded as an ultra low density polyethylene copolymer in comparison with the conventional one. The above ultra-low density polyethylene copolymer can be produced by a gas phase method using a medium / low pressure apparatus, a liquid phase method, an ionic polymerization method using a high pressure apparatus, or the like.

The α-olefin used has 3 carbon atoms.
The number of carbon atoms is preferably from 4 to 13, and particularly preferably from 4 to
It is preferable that the number is 10. From the viewpoint of physical strength and cost, specific examples of preferable α-olefins include, for example, propylene, butene-1, octene-1, hexane-1,4-methylpentene-1, heptene-1 and decene-1. Can be mentioned.

As is clear from the above description, the ultra-low density polyethylene copolymer used in the present invention is preferably a polyethylene resin having a linear linear chain with a short branch. From the viewpoint that a thin layer is possible even when a high concentration of pigment is contained, Japanese Industrial Standard (JIS), K-6
Melt index (MI) and density according to 760 are 0.8-10 g / 10 min and 0.880-0.
910 g / cm ³ is preferable, and the number of carbon atoms is 3 to
It is particularly preferable that it is obtained by a liquid phase process or a gas phase process using a medium / low pressure apparatus using 8 α-olefins.

The content of α-olefin is 5 to 35 mol%.
Is preferable, and particularly preferably 7 to 30 mol%. Specific examples of the ultra-low density ethylene-α-olefin copolymer that can be used in the present invention include NUC-FLX (US U.C.
Trade name of C (UCC) Co., Ltd. and Excelen ・
Buell L (Excellen VL: trade name manufactured by Sumitomo Chemical Co., Ltd.) and the like can be mentioned. Ultra low density ethylene in the resin layer covering at least the emulsion layer side of the substrate
The content of the α-olefin copolymer is 40% by weight or more, preferably 50% by weight or more, and particularly preferably 70% by weight or more.

As a resin that can be used in combination with the ultra-low density ethylene-α-olefin copolymer resin of the present invention, various known polyolefin resins can be mentioned as preferable ones. Representative examples of preferable resins are shown below. Low-density homopolyethylene resin (branched low-density polyethylene that is usually called low-density polyethylene resin produced by high-pressure method), medium-density homopolyethylene resin, high-density homopolyethylene resin, homopolypropylene resin, homopolybutene resin , Homopolypentene resins, etc. homopolymers;

An acid-modified polyolefin resin described below, ethylene-α-having a density of 0.916 to 0.960 g / cm ³ .
Olefin copolymer resin (ethylene / propylene copolymer resin, ethylene / butene-1 copolymer resin, etc.), ethylene / vinyl acetate copolymer resin, ethylene / methyl methacrylate copolymer resin, ethylene / methyl acrylate Copolymers of copolymer resins, ethylene / ethyl acrylate copolymer resins, ethylene / acrylic acid copolymer resins, ethylene / propylene / butene-1 terpolymer resins, ionomer resins, and the like. These polyolefin resins can be used alone or in combination of two or more.

The resin layer which covers the surface opposite to the emulsion layer (back surface) may be the same as the resin layer which covers the surface on the emulsion layer side, but is appropriately selected from known resin layers. Is also good.
However, at least the resin component is preferably the same as the resin component in the resin layer on the emulsion layer side from the viewpoint of production. The resin layer on the back side is formed, for example, by Japanese Patent Laid-Open No. 3-2497.
It may have a multilayer structure as described in No. 53.

The pigment used in the present invention can be appropriately selected from known white pigments as long as it achieves the purpose of imparting high reflectance and hiding power, and titanium dioxide, zinc oxide and It is preferable to use at least one kind of talc, and it is particularly preferable to use titanium dioxide. The form of titanium oxide may be either anatase type or rutile type, but its average particle size is 0.1
It is preferably 0.8 μm.

When it is 0.1 μm or less, it becomes difficult to mix and disperse it in the resin layer, and when it is 0.8 μm or more, the smoothness of the surface of the photographic printing paper support cannot be obtained. Whiteness becomes insufficient. The content of titanium oxide in the composition is preferably 2 to 20% by weight. Details of preferable titanium dioxide, a method for producing the same, a method for incorporating the same in a resin layer, and the like are described in, for example, JP-A-3-2749 and JP-A-4-52639.

Further, for the purpose of visually making the photographic paper appear white (blueing), as is well known, coloring pigments or dyes such as blue, magenta and purple, or fluorescent agents (for example,
(See Japanese Patent Application Laid-Open No. 2-71256) and the like may be appropriately used together. As such a color pigment, it is particularly preferable to use ultramarine having excellent heat resistance. The ultramarine blue has a surface that is surface-treated with silica or a zinc compound, or has a particle size of 0.2 to 8 μm and has a liquid conductivity of 200 μm / cm or less. It is preferable to have one. Details of such a preferable ultramarine are described in Japanese Patent Publication No. 4-2174 and No. 4-26098.

In the present invention, metal powder may be added to the resin layer for the purpose of improving the sharpness of the image by imparting the concealing property and the second type diffuse reflection property. The metal powder used in the present invention includes powders of aluminum, silver, gold, copper, chromium, nickel, platinum or alloys thereof, and among these, aluminum powder is particularly preferable.

The addition amount of the above-mentioned inorganic pigment and / or metal powder can be appropriately adjusted according to their kind and purpose, but generally, the addition amount thereof is a composition for forming the resin layer. 5 to 60% by weight, preferably 7 to 2
Add 5% by weight. The resin layer coated on at least the emulsion layer side of the present invention may appropriately contain at least one selected from the group consisting of known antioxidants, lubricants, surfactants and non-dripping agents. it can. The above-mentioned antioxidant is used in order to prevent the resin from being oxidatively decomposed to generate an aldehyde, a ketone or the like, thereby causing fogging or abnormal sensitivity in the photographic film, or the generation of a non-soluble foreign substance or From the viewpoint of preventing coloring failure and the like, addition is preferable. Representative examples of such antioxidants are shown below.

(A) Phenolic antioxidant 6-t-butyl-3-methylphenol derivative, 2.6
-Di-t-butyl-p-cresol, t-butylphenol, 2.2'-methylenebis- (4-ethyl-6-t
-Butylphenol), 4,4'-butylidene bis (6
-T-butyl-m-cresol), 4.4'-thiobis (6-t-butyl-m-cresol), 4.4'-dihydroxydiphenylcyclohexane, alkylated bisphenol, styrenated phenol, 2.6-di -T-butyl-4-methylphenol, n-octadecyl-3-
(3'.5'-di-t-butyl-4'-hydroxyphenyl) propionate, 2.2'-methylenebis (4-
Methyl-6-t-butylphenol), 4 · 4′thiobis (3-methyl-6-t-butylphenol), 4 ·
4′-butylidene bis (3-methyl-6-t-butylphenol), stearyl-β (3.5-di-4-butyl-4-hydroxyphenyl) propionate, 1.1 ·
3-tris (2-methyl-4-hydroxy-5-t-butylphenyl) butane, 1,3,5-trimethyl-2.
4.6-Tris (3.5-di-t-butyl-4-hydroxybenzyl) benzene, tetrakis [methylene-3
(3 ′ · 5′-di-t-butyl-4′-hydroxyphenyl) propionate] methane and the like.

(B) Ketone amine condensation-type antioxidant 6-ethoxy-2,2,4-trimethyl-1,2-dihydroquinoline, a polymer of 2,2,4-trimethyl-1,2-dihydroquinoline, trimethyl Dihydroquinoline derivatives and the like. (C) Allylamine Antioxidant Phenyl-α-naphthylamine, N-phenyl-β-naphthylamine, N-phenyl-N′-isopropyl-p
-Phenylenediamine, N.N'-diphenyl-p-phenylenediamine, N.N'-di-β-naphthyl-p-
Phenylenediamine, N- (3′-hydroxybutylidene) -1-naphthylamine and the like.

(D) Imidazole type antioxidants 2-mercaptobenzimidazole, zinc salt of 2-mercaptobenzimidazole, 2-mercaptomethylimidazole and the like.

(E) Phosphite type antioxidants Alkylated allyl phosphite, diphenylisodecyl phosphite, tris (nonylphenyl) phosphite sodium phosphite, trinonylphenyl phosphite, triphenyl phosphite and the like. (F) Thiourea-based antioxidants Thiourea derivatives, 1,3-bis (dimethylaminopropyl) -2-thiourea and the like. (G) Other antioxidants useful for air oxidation, such as dilauryl thiodipropionate.

Next, typical antioxidants which are commercially available are shown below. (1) Phenolic antioxidant; Sumilizer BHT,
BP-76, BP-101, GA-80, and WX R (above, trade name of Sumitomo Chemical Co., Ltd.); Irganox 56
5, 1010, 1035, 1076, 133
0, 1425WL and 3114 (all trade names manufactured by Ciba-Geigy Co., Ltd.); Marc AO-20, 30, 30, 50, 60, 80 and 330 (all trade names manufactured by Adeka Argus Co., Ltd.) Tominox SS and TT (trade name of Yoshitomi Pharmaceutical Co., Ltd.); Topanol CA and Nonnox WSP (trade name of UK IC Co., Ltd.); Sandton-OX (product of Monsanto Co., Ltd.) Name); Antage Crystal and Antage W
-400 (above, product name of Kawaguchi Industry Co., Ltd.); Noclyzer NS-6 (product name of Ouchi Shinko Co., Ltd.);
Cyanox 1790 (trade name of American ACC) etc.

(2) Phosphorus antioxidant: Irgafos 168
(Trade name of Ciba-Geigy Co., Ltd.); Marc 2112,
Marc PEP-8, -24G and 36 (above Adeka Argus Co., Ltd. product name); Weston 618 and Ultranox 626 (above BorgWarner Co., Ltd. product name); HCA (Sanko Co., Ltd. product First name) etc.

(3) Thioether type antioxidant; DLTDP
Yoshitomi, DMTD Yoshitomi and DSPT Yoshitomi (the above trade name of Yoshitomi Pharmaceutical Co., Ltd.); Sumilizer TPL, the same TP
M, TPS and TPD (all trade names manufactured by Sumitomo Chemical Co., Ltd.); Antiox M and S (all trade names manufactured by NOF Corporation); Synox 4125 (trade name manufactured by Zypro Co., Ltd.); Mark AO-412 S, Mark AO-23, Mark 26
0, 329K and 522A (all product names manufactured by Adeka Argus Co., Ltd.); Sandstab P-EPQ (product name manufactured by Sandstub Co., Ltd.); Irgaphos P-EPQ FF and Irganox 1222 (all Ciba Geigy Co., Ltd. Product name);
Weston 399 (trade name of Borg Warner Co., Ltd.); etc.

(4) Metal deactivator Naugard XL-1 (trade name of Uniroyal Co., Ltd.);
Marc CDA-1 and CDA-6 (trade names of Adeka Argus Co., Ltd.); Irganox MD-1024 (trade name of Ciba Geigy Co., Ltd.); CU- Knox (trade name of Mitsui Toatsu Co., Ltd. )etc.

Particularly preferred antioxidants are phenolic antioxidants, and hindered phenolic antioxidants are particularly effective. Commercially available products include various Irganox manufactured by Ciba Geigy and Sumitizer Chemical Co., Ltd. Sumitizer BHT, BH-76, WX-R, and BP-101. Also, 2,6-di-t-butyl-p-cresol (B
HT), low-volatile high molecular weight phenolic antioxidants (trade name: Irganox 1010, 1076, Topanol CA, Ionox 330, etc.), dilauryl thiodipropionate, distearyl thiopropionate, dialkyl phosphate, etc. It is also effective to use one or more types, especially two or more types in combination.

The addition amount is 0 in terms of weight with respect to the resin layer.
˜8,000 ppm, preferably in the range of 20 to 3,000 ppm. Addition amount is 8,000ppm
If it exceeds, the photographic film utilizing the oxidation / reduction effect may be adversely affected, and the photographic performance may be abnormal, and the adhesiveness between the substrate and the resin layer tends to be deteriorated. For this reason, it is preferable to add the antioxidant in the minimum amount that does not cause coloring failure, adhesion failure, or spots.

In addition, various antioxidants disclosed on pages 794 to 799 of the Plastic Data Handbook (published by the KK Industrial Research Association) and pages 327 to 329 of Plastic Additives Data Collection (published by KK Chemical Industry Co., Ltd.). Various Antioxidants or Plastic Ages Encyclopedia Advances 1986 (KK Plastics
It is possible to select and use various antioxidants and the like disclosed on pages 211 to 212 of "Age Co., Ltd.".

In the present invention, it is preferable to add a lubricant in order to improve the kneading properties of other additives. Representative examples of preferred lubricants in the present invention are described below. (1) Fatty acid amide type lubricant Saturated fatty acid amide type lubricant Behenic acid amide type lubricant; Diamid KN (trade name of Nippon Kasei Co., Ltd.) and the like.

Stearamide amide lubricants: Armide HT (trade name of Lion Oil & Fat Co., Ltd.), Alflo S-10 (trade name of Nippon Oil & Fat Co., Ltd.), fatty acid amide S (trade name of Kao Corporation), Diamond 20
0, Diamid AP-1 (both trade names manufactured by Nippon Kasei Co., Ltd.), Amide S. Amide T (trade name manufactured by Nitto Kagaku Co., Ltd.), Neutron-2 (trade name manufactured by Nippon Seika Co., Ltd.) )etc. Palmitate amide lubricant; Neutron S-18
(Trade name of Nippon Seika Co., Ltd.), Amide P (trade name of Nitto Kagaku Co., Ltd.) and the like. Lauric acid amide lubricant; Armide C (Lion
Akzo Co., Ltd. product name), Diamid (Nippon Kasei Co., Ltd. product name)

Unsaturated fatty acid amide type lubricant erucic acid amide type lubricant; Alflo P-10 (trade name manufactured by NOF Corporation), Neutron-S (trade name manufactured by NIPPON SEIKA CO., LTD.), Lubrol (eye. Product name manufactured by C.I. Co., Ltd., Diamid L-200 (product name manufactured by Nippon Kasei Co., Ltd.) and the like. Oleic acid amide lubricant; Armoslip CP (trade name of Lion Akzo Co., Ltd.), Neutron and E-18 (trade name of Nippon Seika Co., Ltd.), Amide O (product of Nitto Kagaku Co., Ltd.) Name), Diamond O-
200 and G-200 (trade name of Nippon Kasei Co., Ltd.), Alflo E-10 (trade name of NOF CORPORATION), fatty acid amide O (trade name of Kao Co., Ltd.)
etc.

Bis fatty acid amide lubricant Methylene bisbehenamide lubricant; Diamid N
K-bis (trade name of Nippon Kasei Co., Ltd.). Methylenebisstearic acid amide-based lubricants; Diamid 200 bis (trade name, manufactured by Nippon Kasei Co., Ltd.), Armowax (trade name, manufactured by Lion Akzo Co., Ltd.), bisamide (trade name, manufactured by Nitto Kagaku Co., Ltd.) and the like. Methylenebisoleic acid amide lubricant; Lubron O
(Product name of Nippon Kasei Co., Ltd.) etc.

Ethylenebisstearic acid amide lubricants; Armoslip EBS (trade name of Lion Akzo Co., Ltd.) and the like. Hexamethylenebisstearic acid amide lubricant; Amide 65 (trade name of Kawaken Fine Chemicals Co., Ltd.)
etc. Hexamethylene bisoleic acid amide lubricant; Amide 60 (trade name of Kawaken Fine Chemicals Co., Ltd.)
etc.

(2) Silicone-based lubricants Various grades of dimethylpolysiloxane, modified products thereof, and other modified products of silicone (representative example: siloxane). Typical examples are carboxyl-modified silicone, α
-Methylstyrene modified silicone, α-oleic acid silicone, polyether modified silicone, fluorine modified silicone, hydrophilic special modified silicone, olefin polyether modified silicone, epoxy modified silicone, amide modified silicone, alcohol modified silicone, alkyl modified silicone, alkyl Aryl-modified silicone,
Examples thereof include amino-modified silicone and alkyl hydrogen-modified silicone (manufactured by Shin-Etsu Silicone Co., Ltd., Toray Silicone Co., Ltd.). In particular, various silicones not only exhibit the effects of improving resin fluidity and lubricity, but also improve the dispersibility of the light-shielding substance and the coloring substance and the coloring power when used in combination with the light-shielding substance and the coloring substance. It is preferable because it exerts an unexpected effect.

(3) Nonionic Surfactant Lubricants Electrostripper TS-2, Electrostripper TS-3 (trade name of Kao Corporation) and the like. (4) Hydrocarbon lubricants Liquid paraffin, natural paraffin, micro wax,
Synthetic paraffin, polyethylene wax, polypropylene wax, chlorinated hydrocarbon, fluorocarbon, etc.

(5) Fatty Acid Lubricants Higher fatty acids (preferably C ₁₂ ), oxy fatty acids and the like. (6) Ester-based lubricants Lower alcohol esters of fatty acids, polyhydric alcohol esters of fatty acids, polyglycol esters of fatty acids, fatty alcohol esters of fatty acids, etc. (7) Alcohol-based lubricant Polyhydric alcohol, polyglycol, polyglycerol and the like.

(8) Metal soaps Higher fatty acids such as lauric acid, stearic acid, ricinoleic acid, naphthenic acid, oleic acid and Li, Mg, Ca, S
Compounds with metals such as r, Ba, Zn, Cd, Al, Sn and Pb. These lubricants may be used alone or in combination of two or more if necessary.

In the present invention, it is preferable to use a surfactant for the purpose of improving the dispersibility of the inorganic pigment, metal powder, and other additives in the resin, and preventing static electricity. These surfactants can be appropriately selected and used from nonionic surfactants, anionic surfactants, cationic surfactants and amphoteric surfactants known in the art.

Typical examples of the nonionic surfactant include polyethylene glycol fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene aliphatic alcohol ether, polyoxyethylene alkylphenyl ether, polyoxyethylene glycerin fatty acid ester, and polyoxyethylene glycerin fatty acid ester. Oxyethylene aliphatic amine,
Sorbitan monofatty acid ester, fatty acid pentaerythritol, ethylene oxide addition product of fatty alcohol, ethylene oxide addition product of fatty acid, ethylene oxide addition product of fatty acid amine or fatty acid amide, ethylene oxide addition product of alkylphenol, ethylene oxide addition product of alkylnaphthol Examples thereof include ethylene oxide adducts of partial fatty acid esters of polyhydric alcohols, and various nonionic antistatic agents described in JP-B-63-26697, page 120.

Typical examples of the anionic surfactant include, for example, sodium ricinoleic acid sulfate ester sodium salt, various fatty acid metal salts, sodium ricinoleic acid ester sulfate ester sodium salt, sulfated ethylaniline oleate, olefin sulfate ester salts, and oleyl alcohol sulfate. Ester soda salt, alkyl sulfate ester salt, fatty acid ethyl sulfonate, alkyl sulfonate, alkyl naphthalene sulfonate, alkylbenzene sulfonate, succinate sulfonate, phosphate ester salt and the like.

Typical examples of the cationic surfactants include primary amine salts, tertiary amine salts, quaternary ammonium salts, pyridine derivatives and the like. Representative examples of the amphoteric surfactant include carboxylic acid derivatives, imidazoline derivatives, betaine derivatives and the like. The above-mentioned surfactant is added in an amount of 0 to 7.0% by weight, preferably 0.01 to 3.0% by weight.

In the present invention, it is preferable to use a non-dripping agent for the purpose of preventing dew condensation during storage of the support for photographic printing paper and improving coatability of the undercoat layer and emulsion layer. Typical examples of the non-drip agent are shown below. Stearic acid monoglyceride, glycerin palmitate, glycerin palmitate / ethylene oxide 2 mol adduct, diglycerin monostearate, diglycerin sesquioleate, diglycerin palmitate, polyglycerin monopalmitate, diglycerin fatty acid / diester Basic acid ester, glycerin fatty acid / dibasic acid ester;

Sorbitan monolaurate, sorbitan monostearate, sorbitan monooleate, sorbitan monoerucate, sorbitan palmitate, sorbitan stearate, sorbitan palmitate / propylene oxide / 3 mol adduct, sorbitan palmitate / Propylene oxide / 2 mol adduct, polyoxyethylene sorbitan fatty acid ester, sorbitan sesquipalmitate, sorbitan fatty acid / dibasic acid ester;

Sorbitol fatty acid ester, sorbitol fatty acid / dibasic acid ester, sorbitol stearate, sorbitol stearate / ethylene oxide /
3 mol addition product, polyoxyethylene nonylphenol ether, etc. The amount of these non-dripping agents added is 0 to 5% by weight, preferably 0.1 to 3% by weight, and particularly preferably 0.3 to 2% by weight, based on the resin layer.

In the present invention, in order to improve the adhesion of the resin layer to the substrate, it is preferable to add an acid-modified thermoplastic resin, particularly an acid-modified polyolefin resin, to the resin layer. The above acid-modified polyolefin resin is, for example, a resin obtained by graft-modifying a polyolefin resin with unsaturated carboxylic acids, and specifically, a graft-modified polyethylene resin, a graft-modified polypropylene resin and a graft-modified ethylene copolymer resin. Can be mentioned.

The above-mentioned unsaturated carboxylic acid includes its derivative, and typically, acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, tetrahydrophthalic acid, mesaconic acid, angelica. Acid, citraconic acid, crotonic acid, isocrotonic acid, nadic acid (endocis-bicyclo [2,2,1] hept-5-ene-2,3-dicarboxylic acid), maleic anhydride, citraconic anhydride, itaconic anhydride, Methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, glycidyl acrylate, glycidyl methacrylate;

Maleic acid monoethyl ester, maleic acid diethyl ester, fumaric acid monoethyl ester, fumaric acid dimethyl ester, itaconic acid diethyl ester, acrylic acid amide, methacrylamide, maleic acid monoamide, maleic acid diamide, maleic acid-N- Monoethylamide, maleic acid-N, N-diethylamide, maleic acid-N-monobutylamide, maleic acid-N, N-dibutylamide, fumaric acid monoamide, fumaric acid diamide, fumaric acid-N-monoethylamide, Fumaric acid-N, N-diethylamide, fumaric acid-N-monobutylamide, fumaric acid-N, N-diethylamide, fumaric acid-N-monobutylamide, fumaric acid-N, N-dibutylamide, maleimide,

Monomethyl maleate, dimethyl maleate, potassium acrylate, sodium acrylate, zinc acrylate, magnesium acrylate, calcium acrylate, sodium methacrylate, potassium acrylate, potassium methacrylate, N-butyl maleimide, N
-Phenylmaleimide, maleenyl chloride, glycidyl maleate, dipropyl maleate, aconitic anhydride,
Examples thereof include sorbic acid, of which acrylic acid, maleic acid, maleic anhydride, and nadic acid are preferable, and maleic anhydride is particularly preferable. The unsaturated carboxylic acid may be used as a mixture of two or more kinds.

The method for graft-modifying the unsaturated carboxylic acids in the modified polyolefin resin is not particularly limited, and, for example, the reaction is carried out in a molten state in JP-B-43-274.
No. 21, for example, the melt-kneading method disclosed in JP-B-44-
A method of reacting in a solution state disclosed in Japanese Patent No. 15422, etc., a method of reacting in a slurry state disclosed in Japanese Patent Publication No. 43-18144, or Japanese Patent Publication No. 50-774.
For example, the method of reacting in a gas phase state disclosed in Japanese Patent No. 93, etc. can be used. Among these methods, the melt-kneading method using an extruder is preferable because it is simple in operation and inexpensive.

The amount of the unsaturated carboxylic acids used is from the viewpoint of securing the adhesive strength, a polyolefin resin base polymer (various polyethylene resins, various polypropylene resins, various polyolefin copolymer resins, polybutene-1 resin,
The amount is 0.01 to 20 parts by weight, preferably 0.2 to 5 parts by weight, based on 100 parts by weight of α-olefin copolymer resin such as poly-4-methylpentene-1 and the copolymer resin thereof.

In order to promote the reaction between the polyolefin resin and the unsaturated carboxylic acid, an organic peroxide or the like may be used. Examples of the organic peroxide include benzoyl peroxide, lauroyl peroxide, azobisisobutyronitrile, dicumyl peroxide, α, α′-
Bis (t-butylperoxydiisopropyl) benzene, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, 2,5-dimethyl-2,5-di (t-)
Butylperoxy) hexyne, di-t-butyl peroxide, cumene hydroperoxide, t-butyl-hydroperoxide, dicumyl peroxide, t-
Butyl peroxy laurate, t-butyl peroxy benzoate, 1,3 bis [t-butyl peroxy isopropyl) benzene, cumene hydroperoxide,
Organic peroxides such as di-t-butyl-di-peroxyphthalate, t-butylperoxymaleic acid, isopropyl percarbonate, azo compounds such as asobisisobutyronitrile, inorganic peroxides such as ammonium persulfate, etc. is there.

These organic peroxides may be used in combination of two or more kinds. Particularly preferred are di-t-butyl peroxide, di-cumyl peroxide, and 2,5-dimethyl-2,5-di (t-butylperoxy) hexane having a decomposition temperature of 170 ° C to 200 ° C. ,
2,5-dimethyl-2,5-di (t-butylperoxy) hexyne and 1,3-bis (t-butylperoxyisopropyl) benzene. The addition amount of these peroxides is not particularly limited, but is 0.005 to 5 parts by weight, preferably 0.01 to 1 part by weight, relative to 100 parts by weight of the polyolefin resin.

Representative examples of commercially available acid-modified thermoplastic resins are as follows. (1) "N Polymer" manufactured by Nippon Petrochemical Co., Ltd. (2) "AD" manufactured by Mitsui Petrochemical Co., Ltd.
MER (3) Shower Denko KK "ER
RESIN ”(4) Mitsubishi Kasei Kogyo Co., Ltd.“ Novatech-AP ”(5) Mitsubishi Petrochemical Co., Ltd.“ MO
DIC "(6)" NU "made by Nippon Unicar Co., Ltd.
C-ACE (7) Ube Industries, Ltd. “UB
E BOND ”(8)“ Bondyne ”manufactured by Sumitomo Chemical Co., Ltd. (9)“ Mersen M ”manufactured by Toyo Soda Co., Ltd. (10)“ CM ”manufactured by Mitsui DuPont Chemical Co., Ltd.
PS "etc.

The content of the acid-modified thermoplastic resin in the resin layer is preferably 0 to 40% by weight, more preferably 10 to 30% by weight. Other resins can be used together with the acid-modified resin. As these resins that can be used in combination, various known polyethylene resins are preferable, and as typical examples thereof, among the above-mentioned resins that can be used in combination with the ultra-low density ethylene-α-olefin copolymer resin, particularly preferable resins are given. The examples can be mentioned.

In the present invention, from the viewpoint of improving the crystallization rate, rigidity, transparency, physical strength, etc., it is preferable that at least the emulsion layer side surface of the resin layer contains a nucleating agent. . Nucleating agents include organic nucleating agents and inorganic nucleating agents. Representative examples of these are shown below.

Examples of the organic nucleating agent include carboxylic acids, dicarboxylic acids, salts and anhydrides thereof, salts and esters of aromatic sulfonic acids, aromatic phosphinic acids, aromatic phosphonic acids, aromatic carboxylic acids and aluminum salts thereof. , An aromatic phosphoric acid metal salt, an alkyl alcohol having 8 to 30 carbon atoms, a condensation product of a polyhydric alcohol and an aldehyde, an alkylamine, and the like, such as aluminum p-t-butylbenzoate,
1,3,2,4-dibenzylidene sorbitol,

Di-substituted benzylidene sorbitol compound represented by the following formula

Embedded image (in the formula, R ₁ and R ₂ are alkyl, alkoxy or halogen having 1 to 8 carbon atoms, m and n are both 0 to 3 and m + n ≧ 1), and stearyl. Metal salts of lactic acid such as calcium and magnesium, N-
A compound represented by the following formula, such as (2-hydroxyethyl) -stearylamine

[0064]

(Wherein R ₃ is an alkyl group having 8 to 30 carbon atoms, k and 1 are both 0 to 10 and k + 1
(L) ≧ 1. ), 1,2-hydroxystearic acid lithium salts, sodium salts, potassium salts, calcium salts, metal salts such as magnesium salts, stearyl alcohol, alkyl alcohols such as lauryl alcohol, sodium benzoate, benzoic acid, sebacic acid, etc. is there.

Examples of the inorganic nucleating agent include alkali metal hydroxides such as lithium hydroxide, sodium hydroxide and potassium hydroxide, alkali metal oxides such as sodium oxide, lithium carbonate, sodium carbonate, potassium carbonate and sodium hydrogen carbonate. , An alkali metal carbonate such as potassium hydrogen carbonate, an alkaline earth metal hydroxide such as calcium hydroxide, magnesium hydroxide and barium hydroxide, an alkaline earth metal oxide such as calcium carbonate and calcium oxide, and the like.

The nucleating agent is not limited to these, and other known nucleating agents can be used. Needless to say, the nucleating agent is not limited to a single type, and two or more types can be used in combination. It does not adversely affect the photographic film, has a great effect of promoting crystallization of the resin as a nucleating agent, reduces molding failures, shortens the molding cycle,
Particularly preferable examples of the organic nucleating agent having a large addition effect such as improvement in rigidity and transparency will be described below.

Di (o-methylbenzylidene) sorbitol, di (m-methylbenzylidene) sorbitol, di (p-methylbenzylidene) sorbitol, o-methylbenzylidene-p-methylbenzylidene sorbitol,
m-methylbenzylidene-o-methylbenzylidene sorbitol, m-methylbenzylidene-p-methylbenzylidene sorbitol, 1,3-heptanylidene sorbitol, 1,3,2,4-diheptanylidene sorbitol, 1,3,2 , 4-di (3-nonyl-3-pentylidene) sorbitol, 1,3-cyclohexanecarbylidenesorbitol, 1,3,2,4-dicyclohexanecarbylidenesorbitol, 1,3,2,4-di (m-) Methylbenzylidene) sorbitol, 1,3,2,4-di (p-methylbenzylidene) sorbitol, 1,3
2,4-di (p-hexylbenzylidene) sorbitol, 1,3,2,4-di (phenylacetylidene) sorbitol, 1,3,2,4-di (methylbenzylidene)
Sorbitol, 1,3,2,4-di (ethylbenzylidene) sorbitol, 1,3,2,4-di (propylbenzylidene) sorbitol, 1,3,2,4-di (methoxybenzylidene) sorbitol, 1,3 , 2,4-di (ethoxybenzylidene) sorbitol, 1,3,2,
4-di (p-methylbenzylidene) sorbitol, 1,
3,2,4-di (p-chlorobenzylidene) sorbitol, 1,3,2,4-di (p-methoxybenzylidene)
Sorbitol, 1,3,2,4-di (alkylbenzylidene) sorbitol, 1,3,2,4-bis (methylbenzylidene) sorbitol, aluminum benzoate and the like. Particularly, a dibenzylidene sorbitol compound is preferable.

In the resin composition constituting the resin layer of the present invention, for various purposes such as neutralizing halogen compounds contained in the residue of the polymerization catalyst or as impurities in the additive,
It is preferable to add a fatty acid metal salt. By adding the fatty acid metal salt, bleed-out can be reduced, the organic nucleating agent can be prevented from scattering, and the dispersibility of the organic nucleating agent can be improved. In addition, this fatty acid metal salt improves the dispersibility and moldability of the light-shielding substance, and further neutralizes and harms the halogen compound contained in the resin, which adversely affects the photographic properties of the photographic light-sensitive material. It can also improve the sex.

Examples of such fatty acid metal salts include higher fatty acids such as lauric acid, stearic acid, ricinoleic acid, naphthenic acid, oleic acid and erucic acid, and Li, Mg, Ca,
There are compounds with metals such as Sr, Ba, Zn, Cd, Al, Sn and Pb. Further, a hydrotalcite compound may be used for the purpose of neutralizing a halogen compound contained in the resin and having a bad effect on the photographic property of the photographic light-sensitive material to render it harmless. The amount of the fatty acid metal salt and / or the hydrotalcite compound added is 0 to 10.0% by weight, preferably 0.05 to 5.0% by weight, based on 100 parts by weight of the resin component.

The substrate used in the present invention is not particularly limited, and the base paper mainly made of natural pulp is also a base paper in which natural pulp and synthetic fiber or synthetic pulp are mixed in an arbitrary ratio as required. In addition to paper, it is also possible to use plastic films or plates such as polycarbonate, polystyrene, polyacrylate, polymethacrylate, PET, and metal plates. A particularly preferred base paper is described in, for example, JP-A-4-69648.

As the natural pulp, wood kraft pulp such as softwood kraft pulp, hardwood kraft pulp, and mixed softwood kraft pulp is preferable. These kraft pulps may be produced by any one of polysulfide, batch, and continuous cooking methods, and may be produced with an appropriate degree of curing or a kappa number. Further, it may be produced by the oxygen pulping method described in JP-B-59-38575.

A particularly preferred wood kraft pulp is one in which wood chips are digested by turbidity containing sodium hydroxide and sodium sulfide as chemical components to remove lignin, and then pulp fibers are added in the presence of an antifoaming agent or a defoaming agent. And the cooking residual liquid (black liquor) are separated and washed, and then bleached. As the chemical components in the cooking liquor,
In addition to sodium hydroxide and sodium sulfide, it may further contain salts such as sodium carbonate, sodium sulfate, slaked lime and calcium carbonate, and cooking aids such as sodium borohydride and anthraquinone compounds.

Natural pulp is preferred as the pulp to be used in combination with natural kraft pulp, and softwood sulfide "pulp, hardwood sulfide" pulp and softwood mixed sulfide "pulp wood sulfide" pulp are particularly preferred. Further, wood soda pulp, wood dissolving pulp and the like can also be used.

The defoaming agent or defoaming agent used in the bleaching treatment of pulp can be appropriately selected from known ones. For example, JP-A-54-59404 and JP-A-5-59404.
8-220896, JP-A-61-245391, JP-A-61-245319, and U.S. Pat. No. 3,923,6.
No. 38, US Pat. No. 4,107,073 and the like, higher fatty acid alcohol ester compounds, mineral oils or liquid hydrocarbon oils, silicone oils and the like can be used.

Of these, mineral oil or liquid hydrocarbon oil is the main component, especially from the viewpoint of defoaming property or foam suppressing property,
Aqueous-based or oil-based defoamers or defoamers are preferred. The defoaming agent or defoaming agent may contain components such as hydrophobic silica, ethylene bis higher alkyl amide and silicone oil. As a method of allowing these defoaming agents or defoaming agents to exist during the washing step of unbleached kraft pulp,
It is preferred to add an antifoam or defoamer to the unbleached kraft pulp slurry or thickener at any stage during the washing process.

Chlorine gas or water is used for chlorine bleaching during the production of natural pulp. Also, chlorine dioxide may be used together. It is advantageous to use caustic soda for the alkaline treatment or extraction, but it is also possible to use calcium hydroxide, ammonia and the like and mixtures thereof.
For bleaching of hypozinc acid salt, bleaching powder made by reacting solid slaked lime with chlorine, particularly industrially, bleaching powder of hypozinc acid prepared by blowing chlorine into lime milk or dilute caustic soda solution. (So-called calcium-hypo exposure liquid or sodium-hypo exposure liquid) is preferable.

For chlorine dioxide bleaching, the Matisson method, the new Mathison method, the Elst method, C.I. I. Sulfurous acid method such as P method,
Chlorine dioxide prepared by a hydrochloric acid method such as the Kesting method, the Nisso method, or the Solvay method is advantageously used. Also, as the peroxide used for alkaline bleaching of peroxide,
Hydrogen peroxide, sodium peroxide, peroxide exposure liquid (mixed aqueous solution consisting of hydrogen peroxide, caustic soda, sodium silicate, and magnesium sulfate added as necessary), peracetic acid, 1-
Inorganic or organic peroxides such as butyl hydroperoxide and mixtures thereof are preferred. As the alkali, alkali hydroxides or alkaline earth hydroxides such as caustic soda, potassium hydroxide, aqueous ammonia, magnesium hydroxide and calcium hydroxide, and mixtures thereof are suitable. The bleaching condition can be appropriately selected from the conditions described in "Pulping and Bleaching" (published on January 27, 1968) edited by Japan Paper and Pulp Technology Association, and Japanese Patent Publication No. 58-43732. .

The base material of the present invention may contain various additives when preparing the stock slurry. In particular,
As a sizing agent, a fatty acid metal salt and / or a fatty acid, an alkyl ketene dimer emulsion described in Japanese Patent Publication No. 62-7534 or an epoxidized higher fatty acid amide, an alkenyl or alkyl succinic anhydride emulsion, a rosin derivative, etc .;

As the dry paper strengthening agent, anionic, cationic or amphoteric polyacrylamide, polyvinyl alcohol, cationized starch (for example, JP-A-3-171)
No. 042), vegetable galactomannan, etc .; as a wet paper strength enhancer, polyamine polyamide epichlorohydrin resin, etc .; as a filler, clay, kaolin, calcium carbonate, titanium oxide, etc .;

As a fixing agent, water-soluble aluminum salts such as aluminum chloride and vanadium sulfate; as a pH adjusting agent, caustic soda, sodium carbonate, sulfuric acid, etc.
It is preferable that the color pigments, color dyes, fluorescent whitening agents and the like described in JP-A-04251 and JP-A-1-266537 are appropriately combined and contained. In the substrate,
Additives such as various water-soluble polymers and antistatic agents can be incorporated by spraying or tab size pressing.

As the water-soluble polymer, JP-A-1-26 can be used.
No. 6537, starch-based polymers, polyvinyl alcohol-based polymers, gelatin-based polymers, polyacrylamide-based polymers, cellulose-based polymers and the like; as antistatic agents, nonionic surfactants typified by polyoxyethylene glycols and the like. , Anionic surfactant,
Cationic surfactants represented by quaternary ammonium salts, amphoteric surfactants, alkylamine derivatives, fatty acid derivatives, various lubricants, carbon black, graphite, metal surface coating pigments, metal powders, metal flakes, carbon fibers,
There are conductive materials such as metal fibers and whiskers (potassium titanate, alumina nitride, alumina). Specific compounds include alkali metal salts such as sodium chloride and potassium chloride, alkaline earth metals such as calcium chloride and barium chloride. Salt, colloidal metal oxide such as colloidal silica,
Examples thereof include organic antistatic agents such as polystyrene sulfonate.

As latexes and emulsions, petroleum resin emulsion, styrene-acrylic acid-acrylic acid ester copolymer, styrene-acrylic acid-butadiene copolymer, ethylene-vinyl acetate copolymer, styrene-
Latex such as maleic acid-acrylic acid ester copolymer; clay as pigment, kaolin, talc, barium sulfate, titanium oxide, etc., pH adjusting agent such as hydrochloric acid, phosphoric acid, citric acid, caustic soda, etc. It is preferable to add additives such as coloring dyes and optical brighteners in an appropriate combination.

As a particularly preferable base paper, paper is made from a stock containing an epoxidized fatty acid amide and having a pH adjusted to 5.5 to 6.5, and then the water content thereof is 1 to 4
An example is a base paper (Japanese Patent Application No. 4-97365) in which the pH of the paper surface is adjusted to 7 to 8 by adjusting the surface size with an aqueous alkali solution after adjusting the content to wt%.

The substrate used in the present invention is JIS
A base paper having a smooth surface having a Beck's smoothness of 100 seconds or more defined by P8119 is preferable, and one having a smooth surface of 200 seconds or more is particularly preferable. Beck's smoothness is 1
As a method of producing a base paper of 00 or more, generally,
A large amount of hardwood pulp, which is short-fiber and easily smooth, is used, and beaten with a beater to reduce the long-fiber content as much as possible.

In this case, the beating of the pulp is preferably such that the fiber length of the pulp after beating is such that the 42 mesh residue is 20 to 45% and the freeness is 20 to 350 CSF. Next, with respect to a paper stock slurry to which internal additives are added, see, for example, JP-A-58-37642 and JP-A-61-161.
A suitable papermaking method such as those described in JP-A No. 260240 and JP-A No. 61-284762 is adopted, and a uniform formation is obtained by using a papermaking machine which is normally used such as a Fourdrinier paper machine and a round net paper machine. Beck smoothness 1 is obtained by performing papermaking as obtained, and then performing calendering using a machine calender, super calender, thermal calender, etc. after papermaking.
It is possible to manufacture a base paper of 00 seconds or more.

The thickness of the substrate is not particularly limited,
Its basis weight is preferably ^{40g / m 2 ~250g / m 2} . In the present invention, when the resin layer covering the substrate has a multi-layered structure, the resin of the outermost layer is, for example, MFR.
Is 5 g / 10 min to 20 g / 10 min, and the resin of the lower layer has, for example, MFR of 2 g / 10 min to 10 g / 10 min. You can also

The composition of the intermediate layer provided as necessary in the present invention may be basically the same as the composition of the resin layer provided thereon, but in particular, an acid-modified polyolefin resin,
It is preferable to contain at least one kind of tackifier or epoxy compound, and it is preferable that the neck-in of the resin composition of the intermediate layer is smaller than the neck-in of the resin composition of the resin layer provided thereon. Further, the content of the inorganic pigment and / or the metal powder in the intermediate layer is preferably 10% by weight or less, and particularly preferably 5% by weight or less.

Further, the resin layer and the intermediate layer are preferably provided on the substrate at the same time by the simultaneous melt coextrusion coating method, and the thickness of the resin layer is preferably larger than the thickness of the intermediate layer. When melt-extruding a resin layer (intermediate layer if necessary) on a substrate, a masterbatch containing additives such as pigments at a fixed concentration is usually prepared and diluted with a diluting resin to a desired ratio. The mixed composition is melt-coated, or a compound in which an additive such as a pigment is contained in a resin so as to have a desired composition ratio is prepared and used.

In the present invention, particularly for the resin layer provided on the surface on which the emulsion is coated, a high-concentration masterbatch containing 30 to 90% by weight of the inorganic pigment and / or metal powder is oxidized to 5 to 5,000 ppm. Adjusted in the presence of inhibitors,
This is diluted with a diluent resin containing an ethylene-α-olefin copolymer having a density of 0.870 to 0.915 g / cm ³ , and the content of the copolymer is 40% by weight or more, Content of inorganic pigment and / or metal powder is 5-5
It is preferable that the content of the inorganic pigment and / or the metal powder is 10% in the case of the intermediate layer.
It is preferable to adjust the content to be not more than 5% by weight, preferably not more than 5% by weight.

Further, the diluent resin for the intermediate layer is preferably selected so that the neck-in of the resin composition is smaller than the neck-in of the resin composition of the resin layer provided on the intermediate layer. Melt extrusion temperature is 200 ° C to 350 ° C
Is preferred. The thickness of the resin layer and the intermediate layer is not particularly limited, but generally a thickness of about 5 μm to 50 μm is preferable, and the thickness of the resin layer provided thereon is larger than the thickness of the intermediate layer. Is preferred.

When coating the substrate with the resin composition,
In order to improve the adhesive strength, it is preferable to previously subject the substrate to a physical surface treatment or a chemical surface treatment. Typical examples of the physical surface treatment include flame (flame) treatment, plasma treatment, corona discharge treatment, sandblast treatment and the like, but the corona discharge treatment is most preferable from the viewpoint of being inexpensive and highly effective. The distance between the electrode and the substrate during the corona discharge treatment is preferably 0.5 to 5 mm, and the temperature / humidity at the location of discharge is preferably 10% to 30 ° C. and 60% RH or less.

As the chemical surface treatment, there are a method using a dichromic acid solution, a treatment using ozone, and a treatment applying an anchor agent. The anchor agent is a general term for an adhesion promoter and a cross-linking agent used in the laminating industry, and is also called a primer or an adhesion promoter, etc., in distinction from the adhesive.

Representative examples of such anchor agents are shown below. (1) Organic titanate (titanium-based) anchor agent Tetrapropyl titanate or tetraisobutyl titanate is used as a main component, and tetrastearyl titanate is added as a hydrolysis modifier for use. (2) Polyethyleneimine (imine-based) anchoring agent Polyethyleneimine (—CH ₂ —CH ₂ —NH—) _{n having} a relatively high degree of polymerization is used. It is a particularly preferred anchor agent because it is easy to manage and has a long pot life (shelf life).

(3) Isocyanate-based anchoring agent: There are one that uses a polymer having an isocyanate group alone (one-pack type) and one that uses it in combination with a polyester having an OH group (two-pack type), both of which are crosslinked. Adhesive effect appears due to chemical reactions such as. The disadvantage is that it has a short pot life and is expensive.

(4) Polyester-based and urethane-based anchor agents Saturated polyester resins and urethane resins are used after being dissolved in a solvent such as ethyl acetate or toluene. (5) Polyolefin-based anchor agent (6) Polybutadiene-based anchor agent

The anchor agent layer is preferably formed to have an extremely thin thickness. As the coating method of the anchor agent, a gravure roll coating method, a kiss roll coating method, a drop coating method, a bar coating method, a reverse roll coating method, a direct roll coating method,
The air knife coating method or the like is used. Two or more of the physical surface treatments may be used in combination, and the physical surface treatment and the anchor agent treatment may be combined.

As another method for increasing the adhesive strength between the substrate and the coating layer, the temperature of the resin for extrusion lamination is lowered, or the film to be extrusion laminated is heat treated with a heater drum or hot air. Preheating treatment, ultraviolet irradiation treatment, high-frequency heating treatment, electric induction heating treatment, microwave treatment, or the like may be performed.

The backside coating layer preferably contains an antiblocking agent in order to prevent blocking. Examples of the antiblocking agent include calcium carbonate, talc (magnesium silicate), aluminum silicate, calcium silicate, dicarboxylic acid ester amide, and the like, and among these, silica is particularly preferable.

The preferable addition amount is 0.01 to 0.01% of the resin layer.
It is 5.0% by weight. If it is less than 0.01% by weight, the antiblocking effect is small and only the kneading cost increases.
If it exceeds 5.0% by weight, not only lumpy non-uniform failures occur, but also the physical strength and heat sealability of the film deteriorate. The average particle size of the silica is 0.3 to 20 μm.
Is preferred. When it is less than 0.3 μm, the cohesiveness is strong and many spots are generated, and the blocking preventing effect is small.
When it exceeds 20 μm, silica appears on the film surface and the film surface is not only rough, but also scratches and the like are likely to occur on the photosensitive material.

Various back coat layers can be coated on the photographic support of the present invention for the purpose of preventing static charge, improving writing performance or preventing curling. Further, the back coat layer is provided in Japanese Patent Publication No. 52-18020 and Japanese Patent Publication No. 57-9.
059, Japanese Patent Publication 57-53940, Japanese Patent Publication 58-5
6859, JP-A-59-214849, JP-A-58.
Inorganic antistatic agents, organic antistatic agents, hydrophilic binders, latexes, curing agents, pigments, surfactants and the like described in JP-A-184144 and JP-A-4-34138 may be appropriately combined and contained. .

The support of the present invention can be widely used as a photographic reflection support. For example, a silver halide emulsion layer for black-and-white photographic paper can be provided and a protective layer can be provided thereon. Similarly, for ordinary color photographic paper, each has a different spectral sensitivity, each has a different color, and contains a coupler. It is also possible to prepare a color photographic paper light-sensitive material by providing two or more light-sensitive silver halide emulsion layers.

It is also possible to prepare a color reversal light-sensitive material, a direct positive type color printing paper or a direct positive type color copy material using an optical fog method, which has different spectral sensitivities on the support of the present invention. SDB is provided with a red-sensitive, green-sensitive and blue-sensitive silver halide emulsion layer containing silver halide grains and a dye used in the silver die bleach (SDB) method.
It is also possible to produce a type of print photosensitive material.

Further, it is also applicable to reflective disc plates, disc films and recording materials using silver halide, and Japanese Patent Application Nos. 61-168802 and 61-16.
8803, 61-168804, 61-168
No. 805, Japanese Patent Application Nos. 61-249873 and 61-25
It can also be widely applied to the light-sensitive materials described in JP-A-9794, JP-A-61-275572 and the like.

A mordant layer is provided on the support of the present invention to diffuse a color-development type dye and used as a material for forming a color image, or a physical development nucleus is provided on the support of the present invention. It can also be used as a material for forming a silver diffusion transfer type silver image by providing an undercoat layer. Further, development inhibitors or desilvering inhibitory substances such as those described in JP-B-59-3737 and JP-A-50-65230, such as iodide ion, bromide ion,
It is also possible to provide an adsorption layer (ADL) for a heterocyclic compound having a mercapto group or a heterocyclic compound having a possibility of producing imino silver. The photographic support of the present invention is disclosed in U.S. Pat. No. 4,500,626 and JP-A-60-13344.
No. 9, 59-218443, Japanese Patent Application No. 60-7970.
It can also be applied to a photothermographic material and / or a dye fixing material (image receiving material) described in No. 9 and the like.

[0105]

As described in detail above, the support for photographic printing paper of the present invention uses an ultra-low density ethylene-α-olefin copolymer resin having a density of 0.80 to 0.915 g / cm ^3. Therefore, the content concentration of the inorganic pigment and / or the metal powder can be increased, and as a result, the resin layer can be thinned, the sharpness of the image can be improved, and the resource-saving support for photographic printing paper can be achieved. It is the body. Further, since it can be coated at a high speed, it is excellent in productivity.

[0106]

The present invention will be further described below with reference to Reference Examples and Examples, but the present invention is not limited thereto. Reference Examples 1 to 5 and Comparative Reference Examples 1 to 2 In order to demonstrate the density dependence of the film-forming properties of ethylene-α-olefin copolymers, various density of ethylene-α-olefin copolymers were used as typical examples. Using ethylene / butene-1 copolymer, titanium oxide of 15% by weight and 20%
Drawdown property when the film is formed with the content of 50% by weight (molten resin is extruded from T die at 300 ° C.,
When the film was wound and molded in minutes, the film thickness at which the film was cut was evaluated) and the presence or absence of film cracking was examined. The results are shown in Table 1.
As shown in.

[0107]

[Table 1]

Example 1 The basis weight was 170 g / m ² and the density was 1.06 g / cm ^3.
Of 50 parts by weight of LBKP and 50 parts by weight of LBSP, and the three-dimensional center plane average roughness (SRa) measured by the method according to the description of JP-A-3-259144 is 1.0.
The surface (emulsion layer side) of the base paper, which is μm, does not contain TiO ₂ and has an MFR of 4 g / 10 minutes and a density of 0.920 g / cm.
15μm using ³ low density polyethylene (LDPE)
An intermediate layer of thickness was formed.

Next, an upper resin layer having a TiO ₂ content of 15% by weight and an ultramarine blue content (total of blue and purple) of 0.32% by weight and having the following composition was formed on the intermediate layer. 1
It was coated to a thickness of 5 μm. MFR of density 2.5 g / 10 min is 0.908 g / cm ³ ethylene-butene - 1 copolymer resin: 48 wt%, zinc stearate: 2.0% by weight, the coating of Al ₂ O ₃ is Titanium oxide masterbatch consisting of 0.7% by weight and a coating amount of methylolethane of 1% by weight, and TiO ₂ : 50% by weight of TiO ₂ having an average particle diameter of major axis and minor axis of 0.20 μm measured by an electron microscope. 30 parts by weight of pellets;

Blue-margin blue: 2.3% by weight, purple-margin blue: 5.7% by weight, low molecular weight polyethylene resin: 5.7% by weight, LDPE having an MFR of 3 g / 10 minutes and a density of 0.927 g / cm ³ . Ultramarine blue masterbatch pellets consisting of resin: 86.3% by weight: 4 parts by weight; and ethylene / butene-1 copolymer resin pellets having an MFR of 2.5 g / 10 minutes and a density of 0.908 g / cm ^3. Resin layer with 66 parts well mixed.

On the other hand, on the back surface side, as an intermediate layer, MFR
Is 8 g / 10 minutes and the density is 0.96 g / cm ³ and 70 parts by weight of high density polyethylene (HDPE) and the MFR are 8 g /
20 μm layer consisting of 30 parts by weight of low density polyethylene (LDPE) having a density of 0.918 g / cm ³ in 10 minutes, and MFR of 0.918 g / cm in 8 g / 10 minutes.
The outermost layer of ³ of low density polyethylene alone and 10 μm were melt extrusion coated using a black box type two-layer coextrusion die.

Next, the surface of the resin coating layer on the front surface side of the obtained support was subjected to corona discharge treatment at 15 kilovolts / ampere, and then 10 mg / m ² of gelatin was applied onto the surface using a gravure coater. Dried. Thus, the gelatin coating surface provided on the support was coated with the emulsion for color photographic paper by the slide bead coating method to prepare a color photographic photographic paper.

A resolution test chart was brought into close contact with the obtained color photographic printing paper, exposed to green light, and subjected to color image processing to obtain a test sheet. The obtained test sheet
The sharpness of the printed image was measured by measuring with a microdensitometer and using a personal computer according to a conventional method to obtain the contrast transfer function (CTF) at 5 lines / mm as the image sharpness of the magenta layer. Was measured. The results are shown in Table 2.

Example 2. As the resin for the intermediate layer, the titanium oxide masterbatch pellets used in Example 1 had a density of 0.90 so that the content of titanium oxide was 5% by weight.
Using a black box type two-layer co-extrusion laminator together with the resin composition of the upper layer used in Example 1, using the one diluted with 8 g / cm ³ of ethylene / butene-1 copolymer, A color photographic printing paper was prepared in the same manner as in Example 1 except that the intermediate layer and the upper layer were provided on the same base paper surface as that used in Example 1, and the CTF value was obtained in the same manner as in Example 1. . The results are shown in Table 2.

Example 3. As the resin layer of the intermediate layer, MFR
Of 4 g / 10 min and a density of 0.920 g / cm ³ is used, and the master batch pellets used in Example 1 and the density of 0.
Using a composition containing 20% by weight of titanium oxide and 0.4% by weight of ultramarine blue, which was prepared by blending 908 g / cm ³ of ethylene / butene-1 copolymer, and further,
As the resin layer on the back surface side, a melt blend having a HDPE / LDPE ratio of 50/50 by weight, an MFR of 8 g / 10 min and a density of 0.948 g / cm ³ was provided with a thickness of 27 μm. A color photographic printing paper was produced in exactly the same manner as in Example 1 except for the above. Using the obtained color photographic paper, the CTF value was measured in exactly the same manner as in Example 1, and the results are shown in Table 2.

Example 4. No intermediate layer was provided on one surface (emulsion layer side) of the same base paper as that used in Example 1,
58.47% by weight of ethylene / butene-1 copolymer resin having a density of 0.908 g / cm ³ , acid-modified polyolefin resin (Novatech AP: trade name of Mitsubishi Kasei Co., Ltd.) 20% by weight and trihydric alcohol Surface treated titanium oxide 20% by weight, zinc stearate 1.0% by weight, hindered phenolic antioxidant 0.03% by weight, 1,
An upper resin layer composed of 0.2% by weight of 3,2,4-di (p-methylbenzylidene) sorbitol, 0.1% by weight of ultramarine blue and 0.2% by weight of monoglyceride stearate,
A support was obtained in exactly the same manner as in Example 1 except that the coating was carried out at a resin temperature of 300 ° C. to a thickness of 30 μm.

The support thus obtained had no film cracking, had a large adhesive strength with the base paper, had very little generation of microgrit or fish eyes, and had good peeling from the cooling roll. . A gelatin undercoat layer and a color photographic paper emulsion layer were provided on the emulsion layer side surface of this support under exactly the same conditions as in Example 1 to produce a color photographic paper. The results of measuring the CTF value in exactly the same manner as in Example 1 are as shown in Table 2, and the CTF value was unexpectedly significantly improved. This is considered to be because the uniform dispersibility of titanium oxide in the upper layer of the support was improved and the crystallization was promoted by the addition of the nucleating agent.

Example 5. The amount of the ethylene / butene-1 copolymer resin having a density of 0.908 g / cm ³ used in the upper layer of Example 1 was reduced by 20% by weight, and the reduced amount was added to an acid-modified polyolefin resin (Mitsubishi Kasei Kogyo Co., Ltd.). A photographic printing paper support was obtained in exactly the same manner as in Example 1 except that it was supplemented with 20% by weight of Novatec AP manufactured by the company), no intermediate layer was provided, and only the upper layer had a thickness of 30 μm.

The support was not only free from film cracking, but also had a very high adhesive strength between the resin and the substrate, and had little generation of microgrit or fish eyes. Using the obtained support, a color photographic printing paper was prepared in exactly the same manner as in Example 1, and the CTF value was measured in the same manner. The results are shown in Table 2. As is clear from the results in Table 2, since the CTF value of this color photographic printing paper is large, it was demonstrated that the support of the present invention is excellent as a support for photographic printing paper.

Comparative Example 1. A color photographic printing paper was prepared and CTF was measured in exactly the same manner as in Example 5 except that an ethylene-α-olefin copolymer resin having a density of 0.930 was used instead of the resin having a density of 0.908. The results are shown in Table 2.

[0121]

[Table 2]

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[Procedure amendment]

[Submission date] October 28, 1992

[Procedure Amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0063

[Correction method] Change

[Correction content]

Di-substituted benzylidene sorbitol compound represented by the following formula

[Chemical 1] (In the formula, R ₁ and R ₂ are alkyl having 1 to 8 carbons, alkoxy or halogen, and m and n are both 0 to 3
And m + n ≧ 1. ), Metal salts of stearyl lactic acid such as calcium and magnesium, N- (2-hydroxyethyl) -stearylamine and the like, and compounds represented by the following formula

[Procedure Amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0064

[Correction method] Change

[Correction content]

[0064]

[Chemical 2] (In the formula, R ₃ is an alkyl group having 8 to 30 carbon atoms,
k and l are both 0 to 10, and k + 1 (L) ≧
It is 1. ), 1,2-hydroxystearic acid lithium salts, sodium salts, potassium salts, calcium salts, metal salts such as magnesium salts, stearyl alcohol, alkyl alcohols such as lauryl alcohol, sodium benzoate, benzoic acid, sebacic acid, etc. is there.

[Procedure 3]

[Document name to be amended] Statement

[Correction target item name] 0109

[Correction method] Change

[Correction content]

Next, an upper resin layer having a TiO ₂ content of 15% by weight and an ultramarine blue content (total of blue and purple) of 0.32% by weight and having the following composition was formed on the intermediate layer. 1
It was coated to a thickness of 5 μm. MFR of density 2.5 g / 10 min is 0.908 g / cm ³ ethylene-butene - 1 copolymer resin: 48 wt%, zinc stearate: 2.0% by weight, the coating of Al ₂ O ₃ is a Koti ring weight 1% by weight of trimethylol ethane 0.7% by weight, average particle diameter of the major axis and the minor axis was measured by electron microscope TiO of 0.20 [mu] m _2: 50 wt%, titanium oxide consisting of Masterbatch pellet 30 parts by weight;

Claims (8)

[Claims] 1. A support for photographic printing paper comprising a substrate, a resin layer coated on both sides of the substrate, and an intermediate layer provided between the substrate and the resin layer, if necessary.
Among the resin layers, at least the emulsion layer side surface of the resin layer is coated with an ethylene / α-olefin copolymer resin having a density of 0.870 to 0.915 g / cm ^3.
0% by weight or more, and inorganic pigment and / or metal powder 5
A photographic paper support comprising a resin composition containing 60 to 60% by weight. 2. The resin layer coated on at least the emulsion layer side contains at least one selected from the group consisting of an antioxidant, a lubricant, a surfactant and a non-dripping agent. The support for photographic printing paper according to 1. 3. The resin layer coated on at least the emulsion layer side is 5-40% by weight of an acid-modified polyolefin resin.
The support for photographic printing paper according to claim 1 or 2, which contains. 4. The photographic paper support according to claim 1, wherein at least the emulsion layer side surface of the resin layer contains a nucleating agent. 5. The support for photographic printing paper according to claim 1, wherein at least the resin layer coated on the side opposite to the emulsion layer side contains a nucleating agent. 6. 0.870 to 0.915 g / c between at least the resin layer for covering at least the emulsion layer side and the substrate.
The photograph according to claim 1, wherein an intermediate layer containing 40% by weight or more of an ethylene-α-olefin copolymer resin having a density of m ³ and 10% by weight or less of an inorganic pigment and / or a metal powder is provided. Support for photographic paper. 7. The photographic printing paper according to claim 1, wherein at least the emulsion layer-side surface of the resin layer contains a fatty acid metal salt and / or a hydrotalcite compound. Support. 8. A method for producing a support for photographic printing paper according to claim 1 or 6, wherein the resin layer covering at least the emulsion layer side has an antioxidant of 5 to 5,000 ppm. A high-concentration masterbatch containing 30 to 90% by weight of an inorganic pigment and / or a metal powder prepared in the presence of an agent was treated with ethylene-α having a density of 0.870 to 0.915 g / cm ^3. -Using a diluting resin containing an olefin copolymer, the content of the ethylene-α-olefin copolymer is 40% by weight or more, and the inorganic pigment and /
Alternatively, a method for producing a support for photographic printing paper, which comprises diluting the metal powder to a content of 5 to 50% by weight and then extruding the metal powder on the surface of the substrate.