JPH05281665A - Packaging material for photographic sensitive material and packaging bag formed by using the same - Google Patents

Abstract

PURPOSE:To improve heat sealability, moistureproofness, oxygen barrier property, dustproofness, etc., while well maintaining a tearing property. CONSTITUTION:A heat resistant flexible sheet 2 is laminated via an adhesive layer 3 on one surface of a metallic layer 1. A nonstretched polyolefinic resin film layer 4a contg. >=1 kinds of an antioxidant, conductive material and lubricant, >=10wt.% ethylene copolymer resin and a light shieldable material is laminated via the adhesive layer 3 on the other surface of the metallic layer 1. The strength of adhesion between the respective layers is >=100g/15mm width and the difference in the vertical and horizontal tearing strength is >=1.5 times.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION The present invention relates to a moisture-proof property, an oxygen barrier property,
The present invention relates to a packaging material for a photographic light-sensitive material, which has excellent antistatic properties and heat-sealing properties, complete light-shielding properties, complete sealing properties, and excellent openability, and a packaging bag using the same.
In the present invention, the perfect light-shielding property means that there is no pinhole and that light having all wavelengths can be blocked.

[0002]

2. Description of the Related Art Conventionally, as an easy-open packaging material for photographic light-sensitive materials, an inner layer containing a lubricant, a light-shielding substance and 50 wt% or more of LDPE resin, and an aluminum foil layer (intermediate layer) having an anchor coat layer formed thereon have been used. There was an easily openable packaging material for photographic light-sensitive materials, which was laminated with a peel strength of 400 g / 15 mm width or more and an outer layer having a heat resistance of 5 ° C. or more than an inner layer (Japanese Utility Model Publication No. 2-19226).

[0003]

However, the above-mentioned conventional packaging materials for photographic light-sensitive materials do not have sufficient antistatic agents, complete light-shielding properties, and heat-sealing properties, and as a result, pinholes are likely to occur, and dustproofing is also required. It has also been desired to improve properties, physical strength and the like.

In particular, when a surfactant-based electrically conductive substance or an additive such as a lubricant or an antioxidant which easily bleeds out is contained, the heat-sealing strength is lowered, and the heat-sealing strength is further greatly lowered. There was a case where it was peeled off and a light exposure failure occurred. Therefore, unless the above conductive substance, lubricant, or antioxidant is added, as a result of poor dispersion of the light-shielding substance, spots (lumps of foreign matter) are generated, and spot-like fog is generated on the photographic light-sensitive material in contact with the spots. There was a problem that it was generated or scratches were generated. In particular, if an antioxidant is not added, aldehyde compounds (formaldehyde, acetaldehyde, etc.) and cyan compounds, which adversely affect the photographic light-sensitive material, are generated due to thermal decomposition of the resin, and microgrids (aggregated impurities) and stains on the die lip are generated. There was a problem that occurred.

The present invention solves the above problems, is excellent in antistatic properties, and is free from fluctuations in photographic characteristics and hard spots (lumps of foreign matter).
To provide a packaging material for a photographic light-sensitive material, which is less likely to generate, has good tearability, and can always ensure complete light-shielding property with improved heat-sealing property even when it contains an antioxidant, a conductive substance or a lubricant. With the goal.

[0006]

The present invention has been made in order to achieve the above-mentioned object, and has a heat-resistant flexible sheet layer arranged on one surface, and an antioxidant and a conductive material arranged on the other surface. Of a polyolefin-based resin film containing one or more of a polymerizable substance and a lubricant and 10% by weight or more of an ethylene copolymer resin, and a metal layer or a polyamide resin film layer disposed between the flexible sheet and the polyolefin-based resin film , An ethylene / vinyl alcohol copolymer resin film layer or a polyacrylonitrile resin film layer, and the difference in tear strength between the longitudinal and lateral directions is 1.5 times or more.

As the heat resistant flexible sheet, there are used thermoplastic resin films such as various polyethylene resins, ethylene copolymer resins, polypropylene resins, propylene copolymer resins, polyvinyl chloride resins, polyvinylidene chloride resins, polyamide resins, polyacrylics. Known films of nitrile resin, polycarbonate resin, polyester resin and the like, modified resin films thereof, and uniaxially or biaxially stretched films thereof are available. Also, triacetate film, cellophane, regenerated cellulose film, EV
OH (Eval) resin film, paper, synthetic paper, non-woven fabric, etc.

A particularly preferable heat-resistant flexible sheet has a basis weight of 20 to 400 g / m which does not adversely affect the photographic light-sensitive material.
² types of paper (waste paper, recycled paper, unbleached kraft paper, semi-bleached kraft paper, bleached kraft paper, hineri base paper, Kurpac paper,
Duostress paper, white paperboard, photographic base paper, high-quality paper, medium-quality paper using high-yield pulp, pure white roll paper, coated paper, imitation paper, glassine paper), non-woven fabric, synthetic paper and biaxially stretched thermoplastic resin It is a film. It is preferable that these heat-resistant flexible sheets contain a conductive substance described below in order to prevent the generation of static marks in the photographic light-sensitive material.

These heat-resistant flexible sheets may be used alone or in combination of two or more, and have a melting point of 10 ° C. or more higher than that of the polyolefin-based resin film used as the heat-sealing layer to improve suitability for bag making. It is preferable from the standpoint of preventing appearance of wrinkles and tears and improving the appearance.
Particularly preferred is a biaxially stretched thermoplastic resin film having a thickness of 5 to 70 μm, preferably 7 to 50 μm, and particularly preferably 10 to 35 μm.

The polyolefin resin film layer contains 10% by weight or more of an ethylene copolymer resin. Representative examples of the ethylene copolymer resin are shown below. (1) Ethylene-vinyl acetate copolymer resin (hereinafter EVA
(Represented as resin) (2) Ethylene-propylene copolymer resin (3) Ethylene-1-butene copolymer resin (4) Ethylene-butadiene copolymer resin (5) Ethylene-vinyl chloride copolymer resin (6) Ethylene-methyl methacrylate copolymer resin (7) Ethylene-methyl acrylate copolymer resin (hereinafter,
(Displayed as EMA resin) (8) Ethylene-ethyl acrylate copolymer resin (hereinafter,
(Indicated as EEA resin) (9) Ethylene-acrylonitrile copolymer resin (10) Ethylene-acrylic acid copolymer resin (hereinafter referred to as EAA
(Displayed as resin) (11) Ionomer resin (resin obtained by crosslinking a copolymer of ethylene and unsaturated acid with a metal such as zinc) (12) Ethylene-α-olefin copolymer resin (L-LDPE resin) (13) Ethylene-propylene-butene-1 terpolymer resin (14) Ethylene-propylene-diene terpolymer resin (15) Ethylene-propylene rubber and other elastomers

In the ethylene copolymer resin, film moldability and heat seal suitability, heat seal strength, foreign matter sealability, heat seal strength over time, etc. are good, and bag breaking strength,
L-LDPE resin and EEA resin are preferred because of their high impact puncture strength and tear strength.

[0012] L-LDPE (L iner L ow D ensity P oly e tylene)
The resin is called the third polyethylene resin, which has medium and low density,
It is a low-cost, high-strength resin that meets the demands of the times of energy saving and resource saving, which has the advantages of high density and both homopolyethylene resins. This resin has ethylene and 3 to 13 carbon atoms, preferably 4 to 10 carbon atoms by the low pressure method or the high pressure improvement method.
This is a polyethylene-based resin having a structure in which a linear straight chain has a short branch, which is a copolymer obtained by copolymerizing individual α-olefins. Butene-1, octene-1, hexene-1,4-methylpentene-1, heptene-1 and the like are used as α-olefins which are preferable in terms of physical strength and cost. The density is generally considered to be a low-medium density polyethylene resin, but many commercial products have a density within the range of 0.87 to 0.95 g / cm ³ . The melt index is often in the range of 0.1 to 50 g / 10 minutes, but in the present invention, it is 0.5 to 2 from the viewpoint of the balance of film moldability, physical strength, resin fluidity, dispersibility of a conductive substance and the like.
0 g / 10 minutes is preferable.

As the polymerization process of L-LDPE resin, there are a gas phase method using a medium / low pressure apparatus, a liquid phase method and an ionic polymerization method using a high pressure improving apparatus. Among these L-LDPE resins, particularly preferable in terms of physical strength, heat seal strength and film formability, melt index (hereinafter, referred to as MI) is 0.8 to 10 g / 10 minutes (JIS K-6760), Density 0.870-0.9
40 g / cm ³ (JIS K-6760), and α-olefin obtained by a liquid phase process having 6 to 8 carbon atoms and a vapor phase process.

Specific examples of the L-LDPE resin are shown below. Ethylene / Butene-1 Copolymer Resin G Resin and NUC-FLX (UCC) Dow Rex (Dow Chemical Co.) Screamer (DuPont Canada) Marrex (Phillips) Stamilex (DSM) Excellen VL (Sumitomo Chemical) Neozex (Mitsui Petrochemical) Mitsubishi Polyethylene-LL (Mitsubishi Petrochemical) Nisseki Linilex (Nippon Petrochemical) NUC Polyethylene-LL (Nippon Unicar) Idemitsu Polyethylene L (Idemitsu Petrochemical) Ethylene / Hexene-1 Copolymer Resin TUFLIN ( UCC) TUFTHENE (Nippon Unicar) Ethylene / 4-methylpentene-1 copolymer resin Ultzex (Mitsui Petrochemical) Ethylene / octene-1 copolymer resin Stamirex (DSM) Dourex (Dow Chemical Co.) Screer ( DuPont Canada) M RETEC (Idemitsu Petrochemical)

[0015] A particularly preferred representative example is a trade name, in which polyethylene has 6 carbon atoms as an α-olefin side chain.
Of Mitsui Petrochemical Co., Ltd. in which 4 pieces of 4-methylpentene-1 were introduced, and 8 carbon atoms as an α-olefin side chain
MORE of Idemitsu Petrochemical Co., Ltd. which introduced 1 octene-1
There are TAC and DSM's Stamilex and Dow Chemical's Dourex (these are L-LDPE resins obtained by the co-liquid phase process of four companies). A preferred representative example obtained by the low-pressure vapor phase process is the product name: α
-TUFTHENE of Nippon Unicar Co., Ltd. and TUFLIN of UCC Co., etc., in which hexene-1 having 6 carbon atoms is introduced as an olefin side chain.

In addition, recently released ultra low density linear low density polyethylene resin having a density of less than 0.910 g / cm ³ , for example U.
NUC-FLX from CC and Excellen V from Sumitomo Chemical Co., Ltd.
L and Mitsubishi Yuka Co., Ltd.'s Very Low Density Polyethylene are also preferred (above, the products of all three companies use butene-1 having 4 carbon atoms as the α-olefin).

Representative manufacturers of the EEA resin are Union Carbide (USA), Nippon Unicar Co., Ltd., Mitsubishi Petrochemical Co., Ltd., Sumitomo Chemical Co., Ltd. and Mitsui Polychemical Co., Ltd. .. As specific examples, representative brand names of EEA resins currently marketed by Nippon Unicar Co., Ltd., and their comonomer content, melt index and density are shown (comonomer content 6% or more by NUC test method).

[0018]

[Table 1]

If the ethylene copolymer resin is less than 10% by weight as described above, heat sealability, particularly heat seal strength over time, is deteriorated and sealing performance is secured (including moisture proof property and light shielding property).
Becomes difficult.

In particular, when one or more of a conductive substance and a lubricant is contained, the heat seal strength with time is lowered, pinholes and peeling of the heat seal portion are likely to occur, and the hermeticity cannot be secured. In addition, the polyolefin resin film layer generates static marks on the photographic light-sensitive material due to static electricity, prevents impact on the human body due to static electricity when the photographic light-sensitive material is put in and taken out of the packaging bag, and prevents dust from surrounding. In order to prevent dust and dirt from being adsorbed, it contains one or more of a conductive substance and a lubricant.

Representative examples of conductive materials are shown below. (1) Nonionic surfactant (representative component polyoxyethylene glycols) (2) Anionic surfactant (representative component alkyl sulfonate) (3) Cationic surfactant (representative component quaternary ammonium) (Salt) (4) Amphoteric surfactant (5) Alkylamine derivative (6) Fatty acid derivative (7) Various lubricants (8) Carbon black, graphite (9) Metal surface coating pigment (10) Metal powder, metal flake (11) Carbon fiber (12) Metal fiber (13) Whiskers (potassium titanate, alumina nitride, alumina)

Typical examples of the nonionic surfactant are shown below. Polyethylene glycol fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene aliphatic alcohol ether, polyoxyethylene alkylphenyl ether, polyoxyethylene glycerin fatty acid ester, polyoxyethylene aliphatic amine, sorbitan monofatty acid ester, fatty acid pentaerythritol Ethylene oxide adduct of fatty alcohol, ethylene oxide adduct of fatty acid, ethylene oxide adduct of fatty acid amino or fatty acid amide, ethylene oxide adduct of alkylphenol, ethylene oxide adduct of alkylnaphthol, partial fatty acid of polyhydric alcohol Ethylene oxide adducts of esters and other various nonionic antistatic agents described in JP-B-63-26697, page 120.

Typical examples of the anionic surfactant are shown below. Ricinoleic Acid Sulfate Sodium Salt, Various Fatty Acid Metal Salts, Silinoleic Acid Sulfate Sulfate Sodium Salt, Sulfated Ethylaniline Oleate, Sulfonate of Olefin, Oleyl Alcohol Sulfate Soda Salt, Alkyl Sulfate, Fatty Acid Sulfonate , Alkyl sulfonate, alkyl naphthalene sulfonate, alkylbenzene sulfonate, succinate sulfonate, phosphate ester salt, etc.

Typical examples of the cationic surfactant are shown below. Primary amine salt, tertiary amine salt, quaternary ammonium salt, pyridine derivative, etc.

Typical examples of the amphoteric surfactant are shown below. Carboxylic acid derivatives, imidazoline derivatives, betaine derivatives, etc.

These conductive substances do not adversely affect the photographic light-sensitive material and have a surface electric resistance value of 1.0 × 1 according to JIS C-2318.
It is preferable to add by selecting the kind (two or more kinds can be used in combination) and the addition amount so as to be not more than ¹³ Ω, preferably not more than 1.0 × 10 ¹⁰ Ω. The above conductive materials are 0.01-3.
It is preferable to add 0% by weight.

Listed below are representative names of commercially available lubricants and manufacturers. (1) Silicon lubricants; various grades of dimethylpolysiloxane and its modified products (Shin-Etsu Silicone, Toray Silicone), etc. (2) Oleic acid amide lubricants: Armoslip CP (Lion Akzo), Neutron (Nippon Seika) , Neutron E-18 (Nippon Seika), Amide O (Nitto Kagaku),
Alflo E-10 (Nippon Yushi), Diamond O-200
(Nippon Kasei), Diamid G-200 (Nippon Kasei), etc. (3) Erucic acid amide lubricant; Alflo P-10 (Nippon fat and oil), etc. (4) Stearic acid amide lubricant; Alflo S-10 (Nippon fat and oil) , Neutron 2 (Nippon Seika), Diamond
200 Bis (Nippon Kasei) etc. (5) Bis fatty acid amide lubricants; Bisamide (Nippon Kasei), Diamid 200 bis (Nippon Kasei), Armowax EBS (Lion Akzo), etc. (6) Alkylamine lubricants: Electrostripper TS
-2 (Kao soap), etc. (7) Hydrocarbon lubricants; liquid paraffin, natural paraffin, microwax, synthetic paraffin, polyethylene wax, polypropylene wax, chlorinated hydrocarbon,
Fluorocarbon etc. (8) Fatty acid type lubricant; higher fatty acid (C ₁₂ or more is preferable), oxy fatty acid etc. (9) Ester type lubricant; lower alcohol ester of fatty acid, polyhydric alcohol ester of fatty acid, polyglycol ester of fatty acid, fatty acid (10) Alcohol lubricants; polyhydric alcohols, polyglycols, polyglycerols, etc. (11) Metal soaps; higher fatty acids such as lauric acid, stearic acid, ricinoleic acid, naphthenic acid, oleic acid and Li,
Compounds with metals such as Mg, Ca, Sr, Ba, Zn, Cd, Al, Sn and Pb

The above-mentioned lubricant is preferably added in an amount of 0.01 to 5.0% by weight, and in the case of a fatty acid amide type lubricant which has a great effect of improving lubricity and easily bleeds out, 0.01 to 1.
It is preferable to add 0% by weight. Further, the polyolefin resin film layer can be used by blending it with other thermoplastic resins, elastomers, rubbers, various additives and modifiers in order to improve various properties.

The metal layer may be a metal foil or a metal thin film processed into a flexible sheet. Examples of the metal foil include aluminum foil, iron foil, tin foil, lead foil, electrolytic iron foil, stainless steel foil, copper foil and the like. In the case of a metal foil, the thickness is preferably 5 to 50 μm, particularly preferably 6 to 30 μm, most preferably 7 to 20 μm, and particularly preferably an aluminum foil having a thickness of 6 to 15 μm. In the case of a metal thin film, the thickness is preferably 50 to 1500Å, particularly preferably 100 to 800Å, most preferably 200 to 600Å.

As a result of laminating the above metal layers and laminating a heat resistant flexible sheet layer having excellent pinhole resistance and a polyolefin resin film layer on both sides, MOCO
Oxygen permeability measured by N method (same pressure method according to ASTM D-3985) is 50 cc / m ^{2 for} 24 hours at 1 atm or less, JIS Z-02
The moisture permeability determined by the cup method of 08 (measured at 40 ° C. and 90% R) is 5 g / m ² · 24 hours or less, and the quality of the photographic light-sensitive material can be maintained for a long time. Especially when the aluminum foil is 7 μm or more and the aluminum vapor deposition film is 400 Å or more, the oxygen permeability is 35 cc / m ² · 24 hours · 1 atm or less, and the moisture permeability is 3 g / m ² · 24.
It is possible to maintain the quality for a long time (more than 2 years) even with a photographic light-sensitive material or a high-sensitivity photographic light-sensitive material containing a sensitizing dye that deteriorates in quality due to oxygen or humidity when the time becomes less than the time.

In order to improve the adhesive strength between the metal thin film and the flexible sheet and the adhesive strength between the metal foil and the polyolefin resin film, a physical surface treatment or an AC agent treatment may be performed.

Typical examples of the physical surface treatment are shown below. Flame (flame) treatment; high running cost and risk of fire. Plasma treatment: Argon gas or the like is converted into plasma to treat the surface. The physical strength is several times that of corona discharge treatment, but the equipment cost is several tens of times that of corona discharge treatment equipment. Corona discharge treatment: Treatable substrates are paper, various polymer films, sheets, aluminum foil, aluminum vacuum deposition film and the like. It is the most widely used, inexpensive and highly effective process. Sand blasting: Blasting silica with high pressure to roughen the surface. Chemical treatment: Surface treatment with dichromic acid solution, etc. Ozone treatment: Surface treatment is performed in a box filled with ozone. Preheat treatment: A flexible sheet such as film or paper is heat-treated with a heater drum or hot air.

In addition, there are ultraviolet irradiation treatment, high frequency heating treatment, electric induction heating treatment, microwave treatment and the like.

The AC agent treatment is an AC agent (Ancho) which is a general term for adhesion promoters or crosslinking agents used in the laminating industry.
r Coating Agent) is applied. This AC agent is different from a mere adhesive, and is also called a Primer or an Adhesive Promoter, etc., in the sense of chemically adhering, in distinction from an adhesive. Representative examples of AC agents are shown below. (1) Organic titanate (titanium-based) AC agent Tetra-propyl-titanate or Tetra-iso-butyl-titan
ate as the main component, Tetra-stearyl as a hydrolysis regulator
-Use by adding titanate. (2) Polyethyleneimine (imine type) AC agent Polyethyleneimine (—CH ₂ —CH ₂ —NH—n) having a relatively high degree of polymerization is used. It is particularly preferable because it is easy to manage and has a long pot life (shelf life). (3) Isocyanate-based AC 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). A chemical reaction occurs and an adhesive effect appears. The disadvantage is that it has a short pot life and is expensive. (4) Polyester-based and urethane-based AC agents Saturated polyester resin and urethane resin are used by dissolving them in a solvent such as ethyl acetate and toluene. (5) Polyolefin AC agent (6) Polybutadiene AC agent (7) Epoxy AC agent

The AC agent layer is preferably formed to have an extremely thin thickness. As the coating method of the AC 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, an air knife coating method and the like are used. Two or more of the physical surface treatments may be used in combination, or the physical surface treatment and AC agent treatment may be combined.

The polyamide resin film layer is a polymer compound having an acid amide bond, and is a film layer having an excellent oxygen barrier property that causes the greatest deterioration in the quality of a photographic light-sensitive material having an excellent pinhole resistance. Synthetic polyamide resin is generally called nylon, and the type is nylon 1
There are various homopolyamide resins and copolymerized polyamide resins such as 9 to 11, 11, 12, 13, 6-6 and 6-10.

The ethylene / vinyl alcohol copolymer resin film layer has the highest oxygen gas barrier property among various plastic films. At present, it is generally called EVOH resin. It is a film made of thermoplastic resin manufactured and sold by Kuraray Co., Ltd. and Nippon Synthetic Chemical Industry Co., Ltd. in Japan.

The polyacrylonitrile resin film layer is
Acrylonitrile, methacrylonitrile, fumaronitrile, maleonitrile nitrile components as main components
A film using a resin containing 50% by weight or more and having an oxygen gas barrier property. Generally called PAN resin. It is a film made of the thermoplastic resin currently manufactured and sold by Mitsui Toatsu Chemicals, Inc. and Asahi Kasei Co., Ltd. in Japan.

Each of the above layers is preferably laminated as a solution type adhesive layer made of a polyester resin or a polyether resin having an isocyanate group at the terminal. This solution-type adhesive layer is preferable because it has a large adhesive strength even if it is a thin layer and can easily open and secure a substantially straight cut while securing flexibility. Further, since the reaction solidifies, the photographic light-sensitive material is not adversely affected.

It is also preferable that each of the above layers is laminated by a polyolefin resin extrusion lamination adhesive layer containing an adhesive resin in an amount of 5 to 40% by weight.

The adhesive resin is a modified polyolefin resin obtained by graft-modifying a polyolefin resin and an unsaturated carboxylic acid. For example, a graft-modified polyethylene resin, a graft-modified polypropylene resin, a graft-modified ethylene copolymer resin (EVA resin, EEA). Resin, L-LDPE
Resin, EMA resin, etc.).

The unsaturated carboxylic acids, including their derivatives, are collectively referred to. Typical examples are acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, tetrahydrophthalic acid, mesaconic acid, angelic acid and citracone. 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, Monoethyl maleate, Diethyl maleate, Monomethyl fumarate 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- Monobutyramide, 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, matacryl Potassium acid, sodium acrylate, zinc acrylate, magnesium acrylate, calcium acrylate, sodium methacrylate, potassium acrylate, potassium methacrylate, N-butyl maleimide, N-phenyl maleimide, maleenyl chloride, glycidyl maleate, maleic acid Dipropyl, aconitic acid anhydride, sorbic acid, etc. can be mentioned, and they can also be used as a mixture with each other.

Of these, acrylic acid, maleic acid, maleic anhydride, and nadic acid are preferable, and maleic anhydride is particularly preferable.

The method of graft-modifying the unsaturated carboxylic acids in the modified polyolefin resin is not particularly limited. For example, the method disclosed in JP-B-43-27421, which reacts in a molten state, and JP-B-44-1 which reacts in a solution state
There is a method disclosed in Japanese Patent Publication No. 5422, etc., a method disclosed in Japanese Patent Publication No. 43-18144, etc. in which the reaction is carried out in a slurry state, a method disclosed in Japanese Patent Publication No. 50-77493, etc. which is carried out in the gas phase state, etc. .. Of 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 a polyolefin resin base polymer (various polyethylene resins, various polypropylene resins, various polyolefin copolymer resins, polybutene-1 resin, poly-4-methylpentene-1) for securing adhesive strength. (Alpha) -olefin copolymer resin and its copolymer resin) of 0.01 to 20 parts by weight, preferably 0.2 to 5 parts by weight.

An organic peroxide or the like is used to accelerate the reaction between the polyolefin resin and the unsaturated carboxylic acid.

Examples of the organic peroxide include benzoyl peroxide, lauroyl peroxide, azobisisobutyronitrile, dicumyl peroxide, α,
α'bis (t-butylperoxydipropyl) benzene, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, 2,5-dimethyl-2,5-di (t-butylper) (Oxy) hexyne, di-t-butyl peroxide, cumene hydroperoxide, t-butyl-hydroperoxide, dicumyl peroxide, t-butyl peroxylaurate,
t-butylperoxybenzoate, 1,3 bis (t-butylperoxyisopropyl) benzene, cumene hydroperoxide, di-t-butyl-diperoxyphthalate,
There are organic peroxides such as t-butyl peroxymaleic acid and isopropyl percarbonate, azo compounds such as asobisisobutyronitrile, and inorganic peroxides such as ammonium persulfate.

These may be used alone or in combination of two or more. Particularly preferred is a decomposition temperature of 170 ° C to 2
Di-t-butyl peroxide, di-cumyl peroxide, 2,5-dimethyl-2,5di (t-butylperoxy) hexane, which is between 00 ° C, 2,5-dimethyl-2,5di ( 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 adhesive polyolefin resins are shown below. (1) Nippon Petrochemical KK "N Polymer" (2) Mitsui Petrochemical KK "ADMER" (3) Showa Denko KK "ER RESIN" (4) Mitsubishi Kasei KK "Novatech-AP" (5) Mitsubishi Petrochemical KK "MODIC" (6) Nippon Unicar KK "NUC-ACE" (7) Ube Industries KK "UBE BOND" (8) Tosoh KK "Mersen M" (9) Sumitomo Chemical KK "Bondayne" (10) Mitsui DuPont Chemical KK "CMPS" etc.

The amount of the adhesive polyolefin resin contained in the adhesive layer is preferably 5% by weight or more, and particularly preferably 10% by weight or more.

A light-shielding substance may be added to the polyolefin resin film layer, the heat-resistant flexible sheet layer, etc. in order to secure light-shielding properties. Typical examples of the light-shielding substance are shown below. (1) Inorganic compound A. Oxide: silica, diatomaceous earth, alumina, titanium oxide, iron oxide, zinc oxide, magnesium oxide, antimony oxide, barium ferrite, strontium ferrite, beryllium oxide, pumice, pumice balloon, alumina fiber, etc. B. Hydroxide ... Aluminum hydroxide, magnesium hydroxide, basic magnesium carbonate, etc. C.I. Carbonate ... Calcium carbonate, magnesium carbonate, dolomite, dawsonite, etc. D. (Sulfite) ... Calcium sulfate, barium sulfate, ammonium sulfate, calcium sulfite, etc. E. Silicates ... Talc, clay, mica, asbestos,
Glass fiber, glass balloon, glass beads, calcium silicate, montmorillonite, bentonite, etc. F. Carbon ... Carbon black, graphite, carbon fiber, carbon hollow sphere, etc. G. Others: Iron powder, copper powder, lead powder, aluminum powder, molybdenum sulfide, polon fiber, silicon carbide fiber, brass fiber,
Potassium titanate, lead zirconate titanate, zinc borate, titanium nitride, barium metaborate, calcium borate, sodium borate, aluminum paste, talc, etc. (2) Organic compounds Wood powder (pine, oak, sawdust, etc.), Shell fiber (almond, peanut, fir shell, etc.), cotton, jute, paper strip, cellophane strip, nylon fiber, polypropylene fiber,
Starch, aromatic polyamide fiber, etc.

Among these light-shielding substances, an opaque inorganic compound is preferable, and since it is a substance relatively excellent in heat resistance and light resistance and relatively inactive, it is a light-absorbing carbon black, titanium nitride and graphite. Is preferred.

Examples of classification by carbon black raw material include gas black, furnace black, channel black, anthracene black, acetylene black, Ketjen carbon black, thermal black,
Lamp black, oil smoke, pine smoke, animal black, vegetable black, etc. are available.

As actual products, for example, carbon black # 20 (B), # 30 (B), # 33 (B), # 40 manufactured by Mitsubishi Kasei
(B), # 44 (B), # 45 (B), # 50, # 55, # 100, # 600,
Examples include # 2200 (B), # 2400 (B), MA8, MA11, and MA100. Overseas products include, for example, Cabot's Black Pearls 2, 46, 70, 71, 74, 80, 81, 607, R, etc.
egal 300, 330, 400, 660, 991, SRF-S, Vulcan 3,
6 etc., Sterling 10, SO, V, S, FT-FF, MT-FF and the like. Furthermore, Unit of Ashland Chemical
ed R, BB, 15, 102, 3001, 3004, 3006, 3007, 3008, 3
Examples include, but are not limited to, 009, 3011, 3012, XC-3016, XC-3017, and 3020.

When used as the packaging bag for the photographic light-sensitive material of the present invention, no fog is generated, the increase or decrease in the photosensitivity is small, the light-shielding ability is large, and even when it is added to the L-LDPE resin film, carbon black of Among the carbon blacks, pH 6.0-9.0, average particle size 10-120 mμ, volatile components 2.0% or less, oil absorption amount, because it is hard to generate stiff (pins) and pinholes in the film such as fish eyes Is 50
Furnace carbon black of ml / 100 g or more is preferable because it does not adversely affect the photographic properties so much and the light-shielding property is improved, the dispersibility is improved, and the physical strength is not lowered. In any case, as various carbon blacks used for packaging materials for photographic light-sensitive materials,
The pH is 4.0 to 9.0, preferably 6.0 to 8.0, the average particle size is 10 to 20 mμ, preferably 15 to 60 mμ, and the volatile component is 3.0.
% Or less, preferably 1.0% or less, particularly preferably 0.8% or less, and oil absorption of 50 ml / 100 g or more, preferably 60 ml / 10
0 g or more, particularly preferably 70 ml / 100 g or more does not deteriorate the photographic properties such as "fog" and "sensitivity abnormality" in the photographic light-sensitive material, and does not cause defects such as foaming and silver strips during film formation, Good dispersibility and micro grid (aggregated impurities)
It is preferable because there are few occurrences of the like.

In addition to the above, the free sulfur content which adversely affects the photographic light-sensitive material is 0.6% or less, preferably 0.3% or less, particularly preferably 0.1% or less, and the cyan compound is 0.01% or less, preferably 0.005% or less. , Particularly preferably 0.001% or less, the aldehyde compound is 0.1% or less, preferably
Care must be taken because carbon black of 0.05% or less, particularly preferably 0.01% or less is not carefully selected, because it affects the photographic properties.

Further, on one side of the metal layer, for example, on the side of the flexible sheet, the metal layer is prevented from glare, the printability is improved, it can be identified under a safelight, and the temperature rise in the bag is small even if left in the sun. Translucent, white, etc.
It is preferable to have an appearance such as yellow or silver.

The adhesive strength between the layers is 100 g / 15 mm width or more, preferably 300 g / 15 mm width or more, and particularly preferably 500 g /
Make the width 15 mm or more. If the adhesive strength is less than 100 g / 15 mm width, it is difficult to open by hand even if an opening notch (cutout) is formed, and in particular, it becomes impossible to tear the cut end in a straight line. Adhesive strength is delaminated at the adhesive layer part to be measured, and the tensile tester used in JIS P-8113 is used.
Measure the load when pulled at 180 degrees.

To increase the adhesive strength to 100 g / 15 mm width or more,
One or more of the following means for improving the adhesive strength are used in combination. For example, a resin-based resin or a polyether-based resin having an isocyanate group at the terminal may be used to bond with a solution-type adhesive layer, or an adhesive resin 5-40
Adhesion is performed with a polyolefin resin extrusion laminate adhesive layer containing a weight percent. Alternatively, a physical surface treatment or an AC agent treatment is performed to improve the above-described various adhesive strengths. Furthermore, the resin temperature is raised or the adherend is heated to 50 ° C or higher.

The difference in tear strength between the longitudinal direction and the lateral direction of the packaging material for a photographic light-sensitive material of the present invention is 1.5 times or more. The difference in tear strength
If it is less than 1.5 times, it becomes difficult to tear in a straight line. Tear strength is measured according to JIS P-8116.

In order to increase the difference in tear strength between the longitudinal and lateral directions by 1.5 times or more, a thermoplastic resin film is uniaxially stretched or a thermoplastic resin having a high molecular weight and a low MI is extruded at a high speed from a narrow extrusion port, thereby uniaxially stretching. This is achieved by molecular orientation in the direction (longitudinal direction) or by imparting a strength difference by a method such as changing the thickness of the film in one direction.

The packaging material for the photographic light-sensitive material of the present invention is, for example, Brownie film, K-16 film, K-35 film, disk film, film unit with lens,
Light room loading package (for example, roll-shaped color photographic paper with a magazine for a mini lab, magazine λ computer typesetting film,
Magazine λ computer film, X ray film,
For hermetic packaging (pillow packaging, replacement of conventional light-shielding paper and leader paper) for light-sensitive materials such as printing films, etc.
Light-room loading packaging material for roll-shaped photosensitive material, gazette bag, flat bag, etc. described in Japanese Patent No. 347, Japanese Utility Model Publication No. 3-47547, etc.)
Used for. It can also be used for moisture-proof bags such as packaging for displays (for example, film units with lenses “Sharing Run Hi,” “Shaking Run Flash,” “Shaking Run Panorama,” etc.). As for slipperiness, the outer layer is made to be slippery so that it does not collapse when stacked, and the inner side is made slippery to improve the packaging suitability of the photographic light-sensitive material and facilitate the smooth loading and unloading of the light-shielding bag. Is preferred.

The packaging bag for photographic light-sensitive material of the present invention is produced by heat-sealing the above-mentioned packaging material for photographic light-sensitive material, and is easily opened (cut) in the heat-sealing portion of the packaging bag in the direction of low tear strength. Commonly called a notch or open notch).

As the easy-opening process, notches, cutting lines,
V-notches, weakening lines, perforations, opening cut lines, notches like saw teeth, serrations parallel to the opening direction, etc. are used.

The form of the photographic photosensitive material packaging bag includes, for example, a single flat bag, a double flat bag, a single gusset bag, and a double gusset bag. It is classified into a one-sided seal bag, a three-sided seal bag, and a central joint seal bag. The method for making the bag is a conventionally known method for adhering a plastic film such as a hot plate adhering method, an impulse adhering method, a fusing adhering method, an ultrasonic adhering method, a high frequency adhering method.
It is also possible to make a bag by an adhesive method using an adhesive or a pressure-sensitive adhesive, an adhesive method using a heat-sensitive or pressure-sensitive adhesive, and the like.

[0066]

In the packaging material for photographic light-sensitive materials of the present invention, the heat-resistant flexible sheet layer improves heat seal suitability,
The pinhole resistance is ensured and the heat seal reduces melting to improve the appearance. Further, the wear resistance is also improved. A uniaxially stretched or biaxially stretched film or cellophane improves the unsealing property. The polyolefin-based resin film layer improves heat sealability, secures hermeticity and improves conductivity, and prevents static marks from being generated when the photographic light-sensitive material is packaged.
Further, it also improves the lubricity in the packaging process of the photographic light-sensitive material. Furthermore, it is less likely to adversely affect the photographic light-sensitive material (vinyl chloride resin or the like deteriorates photographic properties and causes disposal problems).

By significantly improving the moisture resistance and the oxygen barrier property of the metal layer, the deterioration of the quality of the photographic light-sensitive material under long-term storage can be prevented, the openability can be improved, and the conductivity can be improved to improve the packaging material. The antistatic property of is also improved. Furthermore, when a semitransparent flexible sheet layer is laminated on one side of the metal layer, a packaging material having a silvery high-class appearance is obtained.

Further, the polyimide resin film layer, the saponified ethylene / vinyl acetate copolymer film layer (EVOH resin film layer) or the acrylonitrile resin film layer is
By significantly improving the pinhole resistance and the oxygen barrier property, the quality deterioration of the photographic light-sensitive material during long-term storage is prevented. By uniaxially or biaxially stretching these films, the above properties are improved and the unsealing property is improved even if they are thin layers. In particular, biaxial stretching provides many excellent properties such as improved Young's modulus, improved openability in all directions, and improved pinhole resistance.

[0069]

Embodiments of the packaging material for a photographic light-sensitive material according to the present invention will be described with reference to the drawings. 1 to 3 are partial cross-sectional views showing the layer structure of the packaging material for a photographic light-sensitive material of the present invention.

In the packaging material for photographic light-sensitive material shown in FIG. 1, the flexible sheet 2 is provided on one side of the metal foil 1 with the adhesive layer 3.
A polyolefin resin film layer 4a (hereinafter, simply referred to as a light-shielding substance, an antioxidant, a conductive substance, one or more kinds of lubricants, and 10% by weight or more of an ethylene copolymer resin) laminated on the other side. A polyolefin resin film layer) is laminated via an adhesive layer 3.

In the packaging material for a photographic light-sensitive material shown in FIG. 2, the flexible sheet 2 has the adhesive layer 3 on the side of the metal thin film 6 of the metal thin film processed flexible sheet layer 7 in which the metal thin film 6 is processed. A polyolefin resin film layer 4a to which the light-shielding substance is added is laminated on the other flexible sheet layer 2 side via the adhesive layer 3.

The photographic light-sensitive material packaging material shown in FIG. 3 has a polyamide resin film layer, an ethylene / vinyl acetate copolymer saponified film layer (EVOH resin film layer) or a polyacrylonitrile resin film layer 8 on one side. The flexible sheet 2 is laminated via the adhesive layer 3, and the polyolefin resin film layer 4a to which the light-shielding substance is added is laminated on the other side via the adhesive layer 3.

FIG. 4 is a plan view of an embodiment of a packaging bag for photographic light-sensitive material, which is made of the packaging material for photographic light-sensitive material of the present invention. The photographic photosensitive material packaging bag shown in FIG. 4 is heat-sealed around the periphery thereof to form a heat-sealing portion 11, and the photographic photosensitive material 12 is housed therein. In addition, a notch 13 as an easy-opening process is continuously formed at both ends as a trigger for opening.

Example 1 A packaging material for a photographic light-sensitive material having a layer structure corresponding to the partial sectional view shown in FIG. Outer layer is 15μm thick, biaxially stretched nylon resin film with sliding angle of 75 degrees, middle layer is 7μm thick
Soft aluminum foil (matte side is outer layer side), inner layer is M
I is 2 g / 10 min, a density of 0.920 g / cm ³ ethylene butene-1
50% by weight of copolymer resin (C ₄ L-LDPE resin) and MI of 1.1 g
/ 10 minutes, 45.3% by weight of high-density homopolyethylene resin polymerized by the low-pressure method using a Ziegler catalyst with a density of 0.954 g / cm ³ , oil furnace carbon black 3% by weight, lubricant zinc stearate 1.0% by weight, conductivity Nonionic type surfactant (monoglyceride type antistatic agent) 0.1% by weight, antioxidant tetrakis [methylene]
-3 (3 '・ 5'-di-t-butyl-4'-hydroxyphenyl) propionate] 0.1% by weight of methane and 0.5% by weight of dimethylpolysiloxane having a lubricant viscosity of 20,000 centistokes. A blown film molding machine was used to form a film with a blow ratio of 1.2 and a thickness of 50μ.
It is a light-shielding polyolefin resin film having a sliding angle of m of 26 degrees. The outer layer and the middle layer, and the middle layer and the inner layer each have a MI of 20 μm of 20 g / 10 minutes, a density of 0.921 g / cm ³ of ethylene / butene-1 copolymer resin 30% by weight, and a MI of 5.18 g / 10.
Min., High density low density homopolyethylene resin 59.85% by weight with density of 0.919 g / cm ³ , unsaturated carboxylic acid graft polymerization adhesive resin (Novatech AP manufactured by Mitsubishi Kasei) 10% by weight, 5.8 Dime
nthyl-tocotrienol 0.05% by weight, synthetic silica 0.1% by weight
The polyolefin resin composition consisting of was laminated by an extrusion laminator at a resin temperature of 310 ° C. with an adhesive layer applied by hot melt extrusion. Each adhesive layer was hot melt extruded and coated in the same process by a tandem laminator (extrusion lamination speed 100 m /
Minutes). The inner (aluminum foil side) surface of the outer layer was subjected to corona discharge treatment, and the aluminum foil of the intermediate layer was preheated with a heating roll at 100 ° C. to improve the adhesive strength with each hot-melt extruded coating layer.

The adhesive strength between the outer layer and the intermediate layer is 472 g / 15 mm width, and the adhesive strength between the intermediate layer and the inner layer is 635 g / 15 mm width.
The tear strength in the machine direction is 218 g and the tear strength in the cross direction is 683 g. Therefore, the difference in tear strength between vertical and horizontal is 6
83 g / length 218 g ≈ 3.1 times.

Using this packaging material, the inner layer was used as a heat-sealing layer to prepare the light-shielding bag for the sheet-shaped photographic light-sensitive material of FIG. This completely sealed and completely light-shielding bag has excellent pinhole resistance, and can secure the perfect light-shielding property. Even under a safelight that processes and packages photographic light-sensitive materials, the front and back sides can be distinguished (silver on the outside, black on the inside) and packaging. The presence of the body can be easily discriminated, and by forming a notch (opening notch), it can be easily torn by hand. Moreover, since the difference in tear strength between the vertical and horizontal directions was 3.1, the cut was straight. It was also excellent in dust resistance. Further, it was possible to provide a light-shielding bag having an appearance with little glare even under sunlight and having an effect of making it difficult to see irregularities due to scratches and foreign matter (such as a mass of insoluble matter) in the laminated film.

Great light-shielding ability (5 ・ 8 Dimenthyl-tocotr
ienol, dimethylpolysiloxane addition effect), the screw load on the inner layer was reduced, and the generation of insoluble matter due to resin burning was reduced. Further, the effect of adding an antioxidant and zinc stearate improved the photographic properties (reduction of fog) and significantly reduced the occurrence of lumps (lumps of foreign matter).

By using an inner layer containing 10% by weight or more of an ethylene copolymer resin, it is possible to prevent the heat seal suitability from being deteriorated by bleeding out by adding one or more of an antioxidant, a lubricant and a conductive substance. it can. In particular, it is possible to provide a packaging material having a perfect light-shielding property that is excellent in hermeticity for a long period. Adhesive strength of 10 even for laminated films using ethylene / α-olefin copolymer resin with high tear strength
By laminating with a width of 0 g / 15 mm or more and making the difference in tear strength between the vertical and horizontal directions 1.5 times or more, a hand tearable packaging material can be obtained.

An adverse effect on the photographic performance is small (a matte surface of soft aluminum is arranged on the outer layer side, and three kinds of resins are blended in the adhesive layers of the outer layer and the intermediate layer to prevent thermal decomposition of the resin. The effect of using a resin composition containing zinc stearate that does not adversely affect the photographic properties of the halogen compound in the resin) is a packaging material having an unexpected effect. In addition, by increasing the sliding angle of the heat-resistant flexible sheet layer of the outer layer and decreasing the sliding angle of the polyolefin resin film layer of the inner layer, it will be less likely to slip off even if a complete light-shielding bag is stacked, making it a bag of photographic light-sensitive material. Can be put in and taken out smoothly. The unevenness is 1 μm or less, preferably 0.5 μm or less when the heat resistant flexible sheet is a film.

Example 2 Aluminum vapor deposition with an outer layer having a thickness of 30 μm and a sliding angle of 37 ° (deposition thickness 400 Å) Vertical uniaxially stretched synthetic rubber-containing high density polyethylene resin film, intermediate layer having a thickness of 30 μm unstretched ethylene vinyl Alcohol copolymer resin (EVOH resin) film, MI of inner layer is 2.1g / 10min, density is 0.920g /
cm ³ ethylene-butene-1 copolymer resin 60% by weight, MI
Is 0.7 g / 10 minutes, the density is 0.959 g / cm ³ , the low-pressure method high-density homopolyethylene resin 10% by weight, the MI is 2.4 g / 10 minutes, the density is 0.9
23 g / cm ³ high-pressure low-density homopolyethylene resin 26.15% by weight, oil furnace carbon black 3% by weight, dimethylpolysiloxane with a viscosity of 20,000 centistokes as a lubricant 0.2% by weight, phenolic antioxidant 0.05% by weight, non- A polyolefin resin film with an ionic surfactant (Electro Stripper TS made by Kao Soap) of 0.6% by weight and a sliding angle of 18 degrees. High-pressure low-density homopolyethylene resin with an outer layer and an intermediate layer, and an intermediate layer and an inner layer each having a thickness of 20 μm, an MI of 6.3 g / 10 minutes, and a density of 0.920 g / cm ^3.
8.4% by weight, titanium oxide 1% by weight, 5.8 Dimenthyl-tocot
rienol 0.1% by weight, magnesium stearate 0.5% by weight, and an unsaturated carboxylic acid graft-polymerized polyolefin adhesive resin (Mitsui Petrochemical Admer) 20% by weight through an adhesive layer made of a polyolefin resin composition. (Adhesion by tandem laminating method in the same process,
The resin temperature was 315 ° C).

The adhesive strength between the outer layer and the intermediate layer is 250 g / 15 mm width, and the adhesive strength between the intermediate layer and the inner layer is 736 g / 15 mm width.
The tear strength in the longitudinal direction is 153g, and the tear strength in the lateral direction is 8g.
It is 57 g. Therefore, the difference between the vertical and horizontal tear strength is 857
g / vertical 153 g ≈5.6 times.

Using this packaging material, the complete light-shielding bag for the sheet-shaped photographic light-sensitive material of FIG. 4 was prepared. This completely sealed completely light-shielding bag makes it easy to distinguish the front and back (silver on the outside, black on the inside and different colors on the front and back) and the presence of the package even under a safelight when processing and packaging photographic light-sensitive materials. By forming the (opening notch), it can be easily torn in a straight line shape by hand. Dustproof, moistureproof,
We were able to provide a complete light-shielding bag with excellent oxygen barrier properties, light-shielding properties, gelbotest strength, and excellent photographic performance retention. In addition, by increasing the sliding angle of the outer layer, it is possible to prevent slipping even when stacked, and by decreasing the sliding angle of the inner layer, products can be taken in and out smoothly.

The light-shielding polyolefin resin film of the inner layer has a large light-shielding ability (5. 8 Dimenthyl-tocotrieno
1, the effect of adding dimethylpolysiloxane), and by adding a lubricant and an antioxidant, the screw load was small, and it was possible to obtain it while reducing the generation of insoluble matter due to resin burning. Further, it was a packaging material having an unexpected effect of improving photographic properties.

The inner layer containing 10% by weight or more of an ethylene copolymer resin covers the deterioration of heat seal suitability due to bleeding out due to the addition of one or more of an antioxidant, a lubricant and a conductive substance. it can. In particular, it is possible to provide a packaging material having a perfect light-shielding property that is excellent in hermeticity for a long period. It is a laminated film that uses ethylene / α-olefin copolymer resin with high tear strength, but has an adhesive strength of 100 g / 15 mm width or more and a vertical and horizontal tear strength of 1.5.
By stacking so as to be doubled or more, a packaging material which can be torn by hand in a shape close to a straight line from an easy opening processing port (generally called a notch or opening notch) can be obtained.

In Examples 1 and 2, the "sliding angle" means a portion of the packaging material to be tested, which is cut vertically.
Stick with double-sided tape on the bottom of a stainless steel block of 75 mm x 35 mm and a load of 200 g. On the other hand, a part of the above-mentioned packaging material to be tested is similarly cut and attached to the inclined surface,
This is a value obtained by placing the packaging material surface of the block on an inclined surface, changing the inclination angle of the inclined surface, and reading the angle when the block starts to slide. "Adhesive strength" is a value measured by delamination at the adhesive layer part to be measured, and the load when pulled at an angle of 180 degrees using the tensile test used in JIS P-8113 (180 degree peel method ). "Tear strength" is a value measured by JIS P-8116.

[0086]

INDUSTRIAL APPLICABILITY The present invention provides heat-sealing suitability, bag suitability, photographic photosensitive material loading / unloading property, moisture resistance, oxygen barrier property while maintaining good light-shielding property, photographic property, and tear property.
The dustproof property can be improved.

[Brief description of drawings]

FIG. 1 is a partial sectional view showing a layer structure of a packaging material for a photographic light-sensitive material of the present invention.

FIG. 2 is a partial cross-sectional view showing the layer structure of the packaging material for a photographic light-sensitive material of the present invention.

FIG. 3 is a partial cross-sectional view showing the layer structure of the packaging material for a photographic light-sensitive material of the present invention.

FIG. 4 is a plan view of a packaging bag made of the packaging material for a photographic light-sensitive material of the present invention.

[Explanation of symbols]

1 ... Metal foil 2 ... Heat resistant flexible sheet layer 3 ... Adhesive layer 4 ... Polyolefin resin film layer 6 ... Metal thin film 7 ... Metal thin film processed flexible sheet layer 8 ... Polyamide resin film layer, saponified ethylene / vinyl acetate copolymer Film layer or polyacrylonitrile resin film layer 13 Notch (opening notch) a: Indicates that a light-shielding substance is contained.

Claims (9)

[Claims] 1. A heat-resistant flexible sheet layer disposed on one surface, one or more of an antioxidant, a conductive substance, and a lubricant disposed on the other surface, and 10% by weight or more of an ethylene copolymer resin. A polyolefin-based resin film layer containing,
A packaging material for a photographic light-sensitive material, which has a metal layer disposed between the flexible sheet and a polyolefin resin film, and has a tear strength difference between a longitudinal direction and a lateral direction of 1.5 times or more. 2. A heat-resistant flexible sheet layer disposed on one surface, one or more of an antioxidant, a conductive substance and a lubricant disposed on the other surface, and 10% by weight or more of an ethylene copolymer resin. A polyolefin-based resin film layer containing,
One or more layers of a polyamide resin film layer, an ethylene / vinyl alcohol copolymer resin film layer and a polyacrylonitrile resin film layer, which are arranged between the flexible sheet and the polyolefin resin film, Packaging material for photographic light-sensitive materials, characterized in that the difference in tear strength is 1.5 times or more 3. The packaging material for a photographic light-sensitive material according to claim 1, wherein the flexible sheet layer and / or the polyolefin resin film layer is uniaxially molecularly oriented. 4. The flexible sheet layer, the metal layer and the polyolefin resin film layer are adhered to each other by a solution type adhesive layer made of a polyester resin or a polyether resin having an isocyanate group at an end. Packaging materials for photographic light-sensitive materials described 5. The flexible sheet layer, the polyamide resin film layer, the ethylene / vinyl alcohol copolymer resin film layer, the polyacrylonitrile resin film layer and the polyolefin resin film are polyester resin or poly having an isocyanate group at the end. The packaging material for a photographic light-sensitive material according to claim 2, wherein the packaging material is a solution type adhesive layer made of an ether resin. 6. The flexible sheet layer, the metal layer, and the polyolefin-based resin film layer contain an adhesive resin in an amount of 5 to 5.
The packaging material for a photographic light-sensitive material according to claim 1 or 3, which is bonded with a polyolefin resin extrusion laminate adhesive layer containing 40% by weight. 7. A polyolefin containing 5 to 40% by weight of an adhesive resin in the flexible sheet layer, the polyamide resin film layer, the ethylene / vinyl alcohol copolymer resin film layer, the polyacrylonitrile resin film layer or the polyolefin resin film. The packaging material for a photographic light-sensitive material according to claim 2, wherein the packaging material is a resin-based extrusion lamination adhesive layer. 8. The method of claim 1, 2, 3, 4, 5, 6 or 7 wherein one or more of the layers on one side of the metal layer is white, yellow, silvery or translucent. Packaging materials for photographic photosensitive materials 9. A packaging material for a photographic photosensitive material according to claim 1, 2, 3, 4, 5, 6, 7 or 8 is formed into a bag by a heat-sealing method, and heat is applied in a direction in which the tear strength of the packaging bag is small. A packaging bag for photographic light-sensitive materials, characterized in that the seal-sealing portion is subjected to an easy-opening process (opening notch).