JPH0659395A - Packing bag for photographic sensitive material - Google Patents

Abstract

PURPOSE:To provide a packing bag housing a photographic sensitive material, perfectly shielding X-rays and preventing interlayer exfoliation, the occurrence of pinholes and the exfoliation of the heat sealed part. CONSTITUTION:This packing bag for a photographic sensitive material is made of a laminate obtd. by laminating a wear resistant flexible sheet 1, X-ray shielding metallic foil 2 and a polyolefin resin layer 3 not contg. a light shielding material while interposing modified adhesive layers 4 so that the flexible sheet 1 is positioned at the outside of this bag. The modified adhesive layers 4 contain an acid modified thermoplastic resin and the polyolefin resin layer 3 contains >=5wt.% ethylene copolymer resin.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a packaging bag for a photographic light-sensitive material having a good X-ray shielding property for containing a roll-shaped or sheet-shaped photographic light-sensitive material such as a photographic film and a photographic printing paper.

[0002]

2. Description of the Related Art Since the quality of a photographic light-sensitive material is impaired by slight light, gas and humidity, a perfect light-shielding property, a sealing property, a gas barrier property and a moisture-proof property are required as a packaging material. , Storage, distribution process, etc.
In order to prevent pinholes, tears, punctures, etc., it is required to have sufficient heat seal strength and physical strength.

Conventionally, as a packaging material having such various characteristics, a cross-laminated film using a uniaxially stretched high-density polyethylene resin film or (Jitsuko Sho 61-19087) is used.
There is a packaging material for a photographic light-sensitive material using a linear low-density polyethylene resin film (Japanese Patent Publication No. 2-27).
No. 00 bulletin).

Recently, more than 10 million overseas travelers have taken the opportunity to take photographic film abroad to take commemorative photographs. However, this photographic film is stored in a plastic container. Therefore, during the X-ray inspection to prevent hijacking, the photographic film may be exposed to X-rays and exposed to light to cause fog. In particular, recently, high-sensitivity films have come into general use, and ISO
Since there are many occasions when a photographic film having an ISO speed of 400 is used rather than a speed of 100, the problem becomes serious.

In particular, most of the film with lens (for example, a photo-run) that is popular for amateurs is I
A photographic film with an SO speed of 400 is used. Therefore, conventionally, in order to prevent the photographic film from being exposed to light by an X-ray inspection, the photographic film is stored in a carrier case in which a lead sheet is internally attached to the inside of an aluminum case, or a bag having an X-ray blocking property laminated with lead foil. Was. The bag having the X-ray blocking property is composed of a layer structure of paper / low density homopolyethylene extrusion laminate adhesive layer / lead foil / low density homopolyethylene extrusion laminate adhesive layer / carbon black-containing low density homopolyethylene film. There was something.

[0006]

However, the above-mentioned conventional carrier case is very expensive, and X
In the bag in which the lead foil having the wire blocking property is laminated, delamination, lead foil pinholes, peeling or pinholes of the heat-sealed portion occur, and the inner and outer surfaces are significantly worn or soiled.

The present invention solves the above problems, completely blocks X-rays, does not generate dust or delamination, and
An object of the present invention is to provide a packaging bag for a photographic light-sensitive material, which can secure the photographic property of the stored photographic light-sensitive material.

[0008]

That is, the packaging bag for a photographic light-sensitive material of the present invention comprises an abrasion resistant flexible sheet, a modified adhesive layer, an X-ray blocking metal foil layer, a modified adhesive layer, and a polyolefin resin layer. Are laminated in this order, the modified adhesive layer contains an acid-modified thermoplastic resin, and the polyolefin resin layer contains 5% by weight or more of an ethylene copolymer resin.

Examples of the abrasion-resistant flexible sheet include non-woven fabric, synthetic paper, surface-treated paper, coated paper, glassine paper, thermoplastic resin film, dust-free paper, cellulose acetate film, regenerated cellulose film and Eval resin film. Can be mentioned. Preferred are thermoplastic resin film, synthetic pulp paper, synthetic paper, dust-free paper, non-woven fabric and dust-free film.

The thermoplastic resin film has heat resistance (DSC melting point) of 110 ° C. or higher and Young's modulus (ASTM D 88).
2) is 50kg / mm ² or more, melt index (MI) is 10g
A thermoplastic resin film having a molecular weight of 20,000 to 800,000 for 10 minutes or less is preferable. Specifically, various polyethylene resins, ethylene copolymer resins, polypropylene resins, polyvinyl chloride resins, polyvinylidene chloride resins, polyamide resins,
Known resin films such as polycarbonate resins and polyester resins, polyolefin resin films, modified resins thereof, and uniaxially or biaxially molecularly oriented (including stretched) films thereof are available.

Examples of the dust-free paper include coated papers obtained by coating or impregnating a base paper with a resin, or applying a coating liquid containing lacquer, latex or pigment. As the base paper, various papers having a low basis weight, a high Young's modulus, excellent heat resistance, and a basis weight of 20 to 400 g / m, which does not adversely affect the photographic material, specifically, unbleached kraft paper and semi-bleached kraft paper ,
Bleached kraft paper, Hinelli base paper, Kurupack paper, Duostress paper, High-yield pulp paper, White paperboard, Photographic base paper, Pure white roll paper, Coated paper, Imitation paper, Glassine paper, Synthetic pulp paper, Synthetic paper, Non-woven paper , Cellophane and the like.

In the flexible sheet, the metal thin film processed layer can be provided on both sides or one side. For the metal thin film processing layer, simple metals such as Al, Sn, Zn, Co, Cr, Ni, Fe and Cu, alloys, and other metals capable of forming a thin film can be used, but aluminum is used in terms of cost and processability. (Al) is most suitable. In particular, the aluminum vacuum vapor-deposited biaxially stretched nylon resin film and the aluminum vacuum vapor-deposited biaxially stretched polyester resin film ensure a high Young's modulus and do not generate pinholes, which is preferable. As a method for processing the metal thin film processing layer into a thin film, a vacuum vapor deposition method, a sputtering method, an ion plating method, an electron beam vapor deposition method or the like is used. The equipment is relatively inexpensive and has excellent workability,
The vacuum deposition method, which has a low thin film processing cost, is particularly preferable.

The metal thin film processing layer preferably has a thickness of 55 to 1200 Å from the viewpoints of physical strength reduction prevention, light shielding property, antistatic property, gas barrier property improvement, moisture proof property improvement, and cost. For normal use, a thickness of 80 to 800Å is preferable, and 100 to 600Å is more preferable.
If the thickness is less than 55Å, the anti-electrostatic property, the moisture-proof property, and the light-shielding property cannot be sufficiently obtained, because the cost for vacuum evaporation of aluminum increases. If the thickness exceeds 1200Å, antistatic property, moistureproof property,
Although the light-shielding property can be secured, it is difficult to put it into practical use due to problems such as cost and the vacuum vapor deposition method in that the flexible sheet is deteriorated by heating and the physical strength of the finished packaging bag for photographic light-sensitive material is lowered.

If necessary, a protective layer may be further provided on the metal thin film. Acrylic resin as the metal thin film protective layer,
Appropriate resins such as cellulose resins such as fibrin acetate, urethane resins, epoxy resins, polyester resins, ionomer resins, nitrocellulose, EEA resins, acrylic resins, various polyethylene resins and polypropylene resins can be used. Various waxes, gelatin, polyvinyl alcohol, etc. can also be used. The protective layer of the metal thin film is preferably formed with an extremely thin thickness. Even if it is produced by the extrusion laminating method, the removal of static electricity becomes insufficient unless the thickness is 50 μm or less.

When the thickness is 5 μm or less by a known solution coating method or spray coating method, the metal thin film can be protected and the effect of removing static electricity is great. It is also possible to mix an antistatic agent, metal powder such as carbon black, aluminum powder, aluminum paste, or a conductive substance such as carbon fiber into the flexible sheet, the adhesive layer described later, and the metal thin film protective layer. If this is done, the removal of static electricity will be even more thorough.

The above flexible sheets can be used in combination of one or more kinds, and a thermoplastic resin film having a melting point of 10 ° C. or more higher than that of the polyolefin resin film layer, surface-coated paper, synthetic paper, dust-proof paper, or non-woven fabric is suitable for bag making. It is preferable in terms of improvement, pinhole resistance, and appearance.

The modified adhesive layer contains an acid-modified thermoplastic resin. Among the acid-modified thermoplastic resins, modified polyolefin resin is particularly inexpensive and has excellent adhesive strength,
The most preferable example of the present invention includes a modified polyolefin resin obtained by graft-modifying a polyolefin resin and unsaturated carboxylic acids. Examples of the modified polyolefin resin include graft modified polyethylene resin, graft modified polypropylene resin, graft modified ethylene copolymer resin and the like.

Unsaturated carboxylic acids, including their derivatives, are generically named. Typical examples are acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, tetrahydrophthalic acid, mesaconic acid, angelic 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, acrylic acid Methyl, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, glycidyl acrylate, glycidyl methacrylate, maleic acid monoethyl ester, maleic acid diethyl ester, fumaric acid monomethyl 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 macrylate, sodium acrylate, zinc acrylate, magnesium acrylate, calcium acrylate , Sodium methacrylate, potassium acrylate, potassium methacrylate, N-butyl maleimide, N-phenyl maleimide, maleenyl chloride, glycidyl maleate, dipropyl maleate, aconitic acid anhydride, sorbic acid, etc. Mixed use is also possible. Of these, acrylic acid, maleic acid, maleic anhydride and nadic acid are preferable, and maleic anhydride is particularly preferable.

The method for graft-modifying the unsaturated carboxylic acids in the modified polyolefin resin is not particularly limited. For example, the melt-kneading method disclosed in Japanese Examined Patent Publication No. 27421/43, etc. for reacting in the molten state, the method disclosed in Japanese Examined Patent Publication No. 14422/44 for reacting in the solution state, or the Japanese Patent Publication No. There is a method disclosed in Japanese Patent Publication No. 18144, etc., a method disclosed in Japanese Patent Publication No. 50-77493, etc. in which a reaction is carried out in a gas phase state, and the like. Of these methods, the melt-kneading method using an extruder is preferable because it is simple and inexpensive in operation.

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) in order to secure adhesive strength.
-Α-olefin copolymer resin such as methylpentene-1 and its copolymer resin) 0.01 to 20 parts by weight, preferably 0.2 to 5 parts by weight, per 100 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-butylperoxy) hexyne, di-t-butylperoxide, cumene hydroperoxide , T-butyl-hydroperoxide, dicumyl peroxide, t-butylperoxylaurate, t-butylperoxybenzoate, 1,3-bis (t-butylperoxyisopropyl)
Benzene, cumene hydroperoxide, di-t-
There are organic peroxides such as butyl-diperoxyphthalate, t-butylperoxymaleic acid and isopropyl percarbonate, azo compounds such as asobisisobutyronitrile, and inorganic peroxides such as ammonium persulfate.

These may be used in combination of one or more kinds. Particularly preferred are di-t-butyl peroxide, di-cumyl peroxide, 2,5-dimethyl-2,5 di (t-butylperoxy) hexane, whose decomposition temperature is between 170 ° C and 200 ° C, It is 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 0.005 to 5 parts by weight, preferably 0.1 part by weight with respect to 100 parts by weight of the polyolefin resin.
01 to 1 part by weight.

Representative examples of commercially available acid-modified thermoplastic 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) Sumitomo Chemical KK "Bondyne" (9) Tosoh KK "Mersen M" (10) Mitsui DuPont Chemical KK "CMPS" etc.

The content of the acid-modified thermoplastic resin in the modified adhesive layer is preferably 5 to 50% by weight, more preferably 10 to 30% by weight.
As the matrix resin of the modified adhesive layer, the following various ethylene copolymer resins, low density homopolyethylene resin, medium density homopolyethylene resin, homopolypropylene resin,
Propylene / α-olefin copolymer resins, various paraffin waxes, various tackifying resins (alicyclic saturated hydrocarbon resins, hydrogenated rosins, terpene modified resins) and the like are preferable.

Examples of the X-ray shielding metal foil layer include lead foil, electrolytic iron foil, rolled iron foil, stainless steel foil, tin foil, copper foil and the like. Preferred are electrolytic iron foil, lead foil, and stainless steel foil. The density of these metal foils depends on the metal species,
It is preferably 5 g / cm ³ or more, particularly preferably 7 g / cm ³ or more. Therefore, the aluminum foil has a density of 2.7 g / cm ³ and has almost no X-ray blocking effect.

The thickness of the X-ray shielding metal foil layer is 7 to 200 μm.
m, preferably 10 to 100 μm, particularly preferably 15 to 80 μm
m. When the thickness is 7 μm or less, not only the X-ray blocking property is insufficient, but also many pinholes are generated in the metal foil layer, which is not preferable. If it exceeds 200 μm, there are problems in manufacturing suitability, cost, and suitability for use.

The polyolefin resin layer contains 5% by weight or more of ethylene copolymer resin. Representative examples of the ethylene copolymer resin are shown below. (1) ethylene-vinyl acetate copolymer 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 (8) Ethylene-ethyl acrylate copolymer resin (hereinafter referred to as EEA resin) (9 ) Ethylene-acrylonitrile copolymer resin (10) Ethylene-acrylic acid copolymer resin (11) Ionomer resin (resin obtained by crosslinking a copolymer of ethylene and an unsaturated acid with a metal such as zinc) (12) Ethylene- α-olefin copolymer resin (L-LDPE resin) (13) Ethylene-propylene-butene-1 terpolymer resin

Among the ethylene copolymer resins, L-LDPE resin and EEA resin are preferable because they have good film moldability and heat seal suitability, and have high bag breaking strength, impact punching strength and tear strength.

[0029] The L-LDPE (L iner L ow D enaity P ol
y e tyiene) resin is called low density polyethylene resin. The L-LDPE resin is called the third polyethylene resin, and has the advantages of both medium- and low-pressure method and high-pressure method polyethylene resin. It is energy-saving, resource-saving, low cost, foreign matter sealing, and hot tacking. It is a high-strength resin having excellent heat-sealing strength and physical strength. This resin is a copolymer obtained by copolymerizing ethylene and an α-olefin having 3 to 13 carbon atoms, preferably 4 to 10 carbon atoms by a low pressure method or a high pressure improvement method, and has a linear straight chain with a short branch structure. It is a polyethylene resin. Preferred α-olefins in terms of physical strength and cost include butene-1, octene-1, hexene-1, 4-methylpentene-1,
Heptene-1, decene-1 and the like are used.

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 . Melt index is 0.1-50g / 1
Many are in the range of 0 minutes.

As the polymerization process of the 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. These L-LDPE
Among the resins, particularly preferable from the viewpoint of physical strength, heat seal strength and film moldability, the melt index (hereinafter referred to as “MI”) is 0.8 to 10 g / 10 minutes (JIS K-6760),
It has a density of 0.870 to 0.940 g / cm ³ (JIS K-6760), and is obtained by a liquid phase process and a gas phase process with an α-olefin having 6 to 8 carbon atoms.

Specific examples of commercially available L-LDPE resins are shown below. Ethylene / Butene-1 Copolymer Resin G Resin and NUC-FLX (UCC Company) Dourex (Dow Chemical Company) Sclear (Dupont Canada Company) Marlex (Philips Company) Stamilex (DSM Company) Excellen VL (Sumitomo Chemical Co., Ltd.) 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.) Screamer DuPont Canada Inc.) MORETEC (Idemitsu Petrochemical)

A particularly preferred representative example is the trade name, in which polyethylene has 6 carbon atoms as an α-olefin side chain.
Mitsui Petrochemical Introducing 4-Methylpentene-1
Urutozekusu of Co., Ltd. and MORETEC of Idemitsu Petrochemical Co., Ltd. which introduced octene-1 having 8 carbon atoms as a side chain of α-olefin, Stamilex of DSM, and Dourex of Dow Chemical (above, It is an L-LDPE resin obtained by a co-liquid phase method process manufactured by four companies.). A preferred representative example obtained by the low-pressure vapor-phase process is the trade name of TUFTH of Nippon Unicar Co., Ltd. in which hexene-1 having 6 carbon atoms is introduced as an α-olefin side chain.
There are TUFLIN of ENE and UCC. In addition, recently released ultra-low density linear low-density polyethylene resin having a density of less than 0.910 g / cm ³ , such as UCC's NUC-FL.
X and Excellen VL from Sumitomo Chemical Co., Ltd. are also preferable (above,
Products of both companies use butene-1 with α-olefin having 4 carbon atoms).

The EEA resin includes Union Carbide (USA), Nippon Unicar Co., Ltd., Mitsubishi Petrochemical Co., Ltd., Sumitomo Chemical Co., Ltd., Mitsui Polychemical Co., Ltd., etc. as typical manufacturers. . As a specific example, representative brand names of EEA resins currently marketed by Nippon Unicar Co., Ltd., and their comonomer content, melt index, and density are shown in the table below (comonomer content of 6% or more by NUC test method). thing).

[0035]

[Table 1]

The polyolefin resin layer contains the ethylene copolymer resin in an amount of 5% by weight or more, preferably 20% by weight or more, and most preferably 50% by weight or more. When the ethylene copolymer resin resin is less than 5% by weight, heat sealability (especially heat seal strength over time, hot tack property, etc.) and physical strength cannot be improved. In particular, it is necessary to improve the heat-sealing property when a substance such as a lubricant or an antistatic agent is apt to be bleeded out, and to prevent the physical strength from decreasing when the substance contains 3% by weight or more of a light-shielding substance.
In addition, it is also preferable to blend with other various thermoplastic resins, thermoplastic resin elastomers, synthetic rubbers, various additives, and modifiers in order to adapt to the required characteristics.

Another packaging bag for photographic light-sensitive material of the present invention has an X-ray blocking polyolefin resin layer containing an X-ray blocking filler, and thermoplastic resin layers laminated on both sides thereof.
In addition, at least one of the X-ray blocking polyolefin resin and the thermoplastic resin layer contains an acid-modified thermoplastic resin.

The density of the X-ray blocking filler is preferably 3.40 g / cm ³ or more, particularly 4.0 g / cm ³ or more. The average particle size or average diameter (in the case of whiskers, fibers, etc.) of the X-ray blocking filler is 50 μm or less, preferably 40 μm or less, and particularly preferably 30 μm or less. Further, it is preferable to coat the surface of the particles with a surface treatment agent described later (for example, a lubricant, a surfactant, a coupling agent, a metal, etc.). When 10% by weight or more of X-ray blocking filler is added, the fluidity of the resin decreases and the dispersibility of X-ray blocking filler deteriorates, so the particle surface is coated with a surface treatment agent (can be kneaded) Will be required.

Specific examples of the X-ray blocking filler are given below. The form of the X-ray blocking filler is not limited to the exemplified form, and may be any form such as pigment, powder, flake, whisker, fiber and the like. Barium sulfate, molybdenum disulfide, lead oxide (white lead), iron oxide, titanium oxide, magnesium oxide, barium titanate, copper powder, iron powder, silver powder, lead powder, steel powder, zinc powder, tungsten whiskers, silicon nitride Whiskers, copper whiskers, iron whiskers, nickel whiskers, chrome whiskers, stainless powder and whiskers, antimony trioxide, barium carbonate, zinc white, chrome oxide, tin powder and mixtures thereof.

Particularly preferred are barium sulfate, barium chloride, barium titanate, lead powder, lead oxide, zinc powder,
Zinc white, tin powder, stainless powder, stainless whiskers, iron oxide, tungsten whiskers, nickel whiskers.

The content of the X-ray blocking filler is preferably 5 to 80% by weight, more preferably 10 to 70% by weight, and most preferably 20 to 60% by weight. Further, the X-ray blocking filler does not adversely affect the photographic light-sensitive material and does not deteriorate the film moldability, so that the loss on drying at 100 ° C. for 5 hours is preferably 2.0% by weight or less, more preferably 1.0% by weight. % Or more, most preferably 0.5% by weight or less before use.

The above X-ray blocking filler improves the dispersibility in the resin, improves the fluidity of the resin, prevents the generation of microgrids that cause photographic fog, pressure fog, scratches, etc. on the photographic light-sensitive material, and causes harmful volatilization. It is preferable to perform surface treatment with a surface treatment agent in order to prevent the generation of volatile substances. Examples of such surface treatment agents and surface treatment methods include those exemplified below, and one or more of these may be used. (1) Coupling agent Coupling agent containing azidosilanes (JP-A-62-62)
-32125, etc.) Silane coupling agent coating (aminosilane etc.) Titanate coupling agent coating (2) Silica deposition followed by alumina deposition coating (3) Zinc stearate, magnesium stearate, calcium stearate Higher fatty acid metal salt coating such as (4) Surfactant coating of sodium stearate, potassium stearate, oxyethylene dodecyl amine etc. (5) Barium sulfide aqueous solution and sulfuric acid aqueous solution in the presence of excess barium ion React, average particle size 0.1-2.5μ
m barium sulphate is produced, an aqueous alkali silicate solution is added to this water slurry to produce barium silicate on the surface of barium sulphate, then mineral acid is added to the slurry to decompose the barium silicate into hydrous silica. Deposition and coating on barium sulfate surface (6) Metal hydrate oxide (one or more hydrate oxides of titanium, aluminum, cerium, zinc, iron, cobalt or silicon) and / or metal oxide (titanium). , Aluminum, cerium, zinc, iron, cobalt or silicon oxide, and a surface coating with a composition consisting only of (7) aziridine group, oxazoline group and N-hydroxyalkylamide group in the molecule. 1 selected from the group
(1) Surface coating with polyoxyalkyleneamine compound (8) Surface coating with polyoxyalkyleneamine compound (9) Surface coating with cerium cation, selected acid anion and alumina (10) Substituted α-hydroxy group Surface coating with an alkoxytitanium derivative having a carboxylic acid residue (11) Surface coating with polytetrafluoroethylene (12) Surface coating with polydimethylsiloxane or modified silicon (13) Surface coating with phosphate ester compound (14) 2 Surface coating with tetrahydric alcohol (15) Surface coating with olefin wax (polyethylene wax, polypropylene wax) (16) Surface coating with aluminum hydroxide oxide (17) Silica or zinc compound (zinc chloride, zinc hydroxide, zinc oxide, zinc sulfate) , Zinc nitrate, zinc acetate, zinc citrate, etc., or a combination of two or more). Surface coated with a hydrocarbon, etc.

The coating amount of the above surface treatment agent is preferably 0.001 to 5% by weight, more preferably 0.01 to 3% by weight, and most preferably 0.05 to 1.5% by weight, based on the X-ray blocking filler. If the coating amount exceeds 5% by weight, not only the occurrence of bleed-out will increase over time, but also slippage with the screw will occur and the discharge amount will fluctuate. As a result, the variation in layer thickness will become too large and practical application will be difficult. Becomes

The layer thickness of the X-ray blocking polyolefin resin layer is preferably 15 to 500 μm, more preferably 25 μm.
˜400 μm, most preferably 35-300 μm. The polyolefin resin used for the X-ray blocking polyolefin resin layer is the same as that described for the polyolefin resin layer.

The thermoplastic resin layers laminated on both sides of the X-ray blocking polyolefin resin layer may be laminated alone or as a part of a coextrusion film. As the resin used for this thermoplastic resin layer, all the polyolefin resins used for the X-ray blocking polyolefin resin layer can be used. The thermoplastic resin layer laminated on the photographic light-sensitive material side (inner side) ensures heat seal strength over time and is completely sealed.
The ethylene copolymer resin is contained in an amount of 5% by weight or more, preferably 10% by weight or more, particularly preferably 20% by weight or more, and most preferably 50% by weight or more from the viewpoints of securing the light-shielding property and securing the physical strength. Among the ethylene copolymer resins, L-LDPE resin and E which are excellent in the above characteristics without adversely affecting the photographic light-sensitive material
EA resin and EVA resin are preferable, and the density is particularly 0.87-0.
95 g / cm ³ of L-LDPE resin is preferred. The outermost layer is a polyamide resin, polyester resin, polypropylene resin, high-density homopolyethylene resin with a pinhole resistance, abrasion resistance, heat resistance, dust resistance, physical strength, etc.
L-LDPE resin, polycarbonate resin, EVOH resin and the like having a weight of 5 g / cm ³ or more are preferable. In particular, a uniaxially or biaxially stretched thermoplastic resin film having a metal thin film processed uniaxially or biaxially stretched thermoplastic resin film or a moisture barrier / gas barrier resin layer such as vinylidene chloride resin coated on the surface is preferable (the outer surface is uniaxially or biaxially stretched thermoplastic resin film). It is preferable to have a layer structure in which a plastic resin film is arranged in order to protect the metal thin film processing layer, the moisture-proof and the gas barrier resin layer.

The acid-modified thermoplastic resin contained in at least one of the X-ray blocking polyolefin resin layer and the thermoplastic resin is as described above. In the packaging bag for a photographic light-sensitive material having at least 5 layers and the packaging bag for a photographic light-sensitive material having at least 3 layers described above, a lubricant can be added to each layer. By adding the lubricant, the effects of improving the dispersibility of the solid particles in the resin composition and preventing static electricity can be achieved. Typical commercial lubricant names and manufacturer names are listed, but not limited to these.

(1) Silicone lubricant; various grades of dimethylpolysiloxane (Shin-Etsu Silicone, Toray Silicone), etc. (2) Oleic acid amide lubricant; Armoslip CP (Lion Akzo), Neutron (Nippon Seika), Neutron E-18 (Nippon Seika), Amide O (Nitto Kagaku),
Alfro E-10 (Nippon Oil and Fats), Diamid O-200 (Nippon Kasei), Diamid G-200 (Nippon Kasei), etc. (3) Erucamide amide lubricant; Alflo-P-10 (Nippon Oil and Fats), etc. (4) ) Stearamide-based lubricants; Alfro-S-10 (Nippon Yushi), Neutron 2 (Nippon Seika), DIAmid
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 -T
S-2 (Kao soap) etc. (7) Metal soap etc. are mentioned.

The above-mentioned silicone lubricant is the second most preferable after the fatty acid amide lubricant. As such silicone lubricants, various grades of dimethylpolysiloxane and its modified products (Shin-Etsu Silicone, Toray Silicone) and polymethylphenylsiloxane, olefin-modified silicone, polyether modified silicone modified with polyethylene glycol or polypropylene glycol, olefin /
Examples thereof include silicone modified oils containing modified siloxane bonds such as polyether modified silicone, epoxy modified silicone, amino modified silicone, alcohol modified silicone and the like. Among the silicone-based oils, olefin-modified silicone, polyether-modified silicone, olefin / polyether-modified silicone and the like are particularly excellent.

The silicone oil as described above improves the coefficient of friction of the film in the heated state, reduces the sliding resistance generated during the hot plate sealing by the automatic packaging machine, and prevents the formation of wrinkles. It is possible to form the basis for obtaining a film that retains the performance of having a beautiful appearance, a high degree of sealing property, and an adhesiveness that does not sag on the body to be packaged. In addition, it is possible to prevent deterioration of gloss due to sliding and obtain a beautiful seal portion. In the present invention in which silicone oil is also used, the high temperature friction coefficient can be 1.4 or less when sliding heat sealing is performed.

The viscosity at room temperature is preferably in the range of 50 to 100,000 centistokes, more preferably 5,000 to 30,
High viscosity of 000 centistokes is recommended. The addition amount varies depending on the type and purpose of use with respect to the resin composition, but 0.01
~ 1.0 wt% is preferred. It is more preferably 0.03 to 0.5% by weight, and most preferably 0.05 to 0.3% by weight.

The silicon-based lubricant may be used alone, in combination of two or more kinds, or in combination with other lubricants or plasticizers. The effects of adding silicone-based oil have many applications as follows. It improves the fluidity of the resin, reduces the motor load on the screw, and prevents melt fracture. Sufficient lubricity can be ensured without adding a fatty acid amide that bleeds out to form a white powder. It is possible to reduce the friction retention of the film in the heated state, improve the suitability for automatic bag making, prevent wrinkles from occurring during heat sealing and decrease in gloss due to sliding, and obtain a beautiful sealed portion. When used in combination with the light-shielding substance, the light-shielding ability can be improved, and the light-shielding property can be secured even if the amount of the light-shielding substance that deteriorates the physical properties is reduced.

Examples of the metal soap include metal salts of higher fatty acids. As the higher fatty acid, a fatty acid having 8 or more carbon atoms, preferably 10 or more carbon atoms, more preferably 12 or more carbon atoms, specifically, lauric acid, stearic acid, ricinoleic acid, naphthenic acid, oleic acid, erucic acid Acid, behenic acid, etc. are mentioned. The metal species of the metal salt include alkali metals (eg Li), alkaline earth metals (eg Mg, Ca, Sr, Ba), Zn, Cd, Al,
Examples include Sn and Pb. As a preferred metal soap,
Specific examples include zinc stearate, magnesium stearate, calcium stearate and the like.

Other lubricants include the following. (1) Hydrocarbon lubricants; liquid paraffin, natural paraffin, microwax, synthetic paraffin, polyethylene wax, polypropylene wax, chlorinated hydrocarbons,
Fluorocarbon etc. (2) Fatty acid type lubricant; higher fatty acid (C ₁₂ or more is preferable), oxy fatty acid etc. (3) Ester type lubricant; lower alcohol ester of fatty acid, polyhydric alcohol ester of fatty acid, polyglycol ester of fatty acid, fatty acid (4) Alcohol-based lubricants; polyhydric alcohols, polyglycols, polyglycerols, etc.

In the packaging bag for photographic light-sensitive materials having at least 5 layers and the packaging bag for photographic light-sensitive materials having at least 3 layers, an interfacial lubricant can be added to each layer. By adding an interfacial slip agent, antistatic property can be achieved.

Typical examples of the nonionic surfactant are shown below. Polyethylene glycol fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene fatty alcohol ether, polyoxyethylene alkylphenyl ether, polyoxyethylene glycerin fatty acid ester, polyoxyethylene fatty amine,
Sorbitan monofatty acid ester, fatty acid benthaelisitol, ethylene oxide adduct of fatty alcohol, fatty acid ethylene oxide adduct, fatty acid amino or fatty acid amide ethylene oxide adduct, alkylphenol ethylene oxide adduct, alkylnaphthol ethylene oxide adduct , Ethylene oxide adducts of partial fatty acid esters of polyhydric alcohols, and various nonionic antistatic agents described in JP-B No. 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, Olefin Sulfate Ester, Oleyl Alcohol Sulfate Soda Salt, Alkyl Sulfate Ester, Fatty Acid Ethyl Sulfonate , Alkyl sulfonate, alkyl naphthalene sulfonate, alkylbenzene sulfonate, succinate sulfonate, phosphate ester and the like.

Typical examples of the cationic surfactant are shown below. Primary amine salts, tertiary amine salts, quaternary ammonium salts, pyridine derivatives and the like.

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

Another additive is a coupling agent. Examples of the coupling agent include those exemplified for the surface treatment agent, and chromium-based and aluminum-based coupling agents. The addition of these coupling agents further improves the dispersibility of the X-ray blocking filler in the resin, the resin fluidity, and the like.

In the packaging bag for photographic light-sensitive materials having at least 5 layers and the packaging bag for photographic light-sensitive materials having at least 3 layers, an antioxidant can be added to each layer. By adding an antioxidant, it is possible to prevent spots, microgrids, coloring troubles and the like.
Representative examples of antioxidants are shown below. (A) Phenolic antioxidant Vitamin E, 6-t-butyl-3-methylphenyl derivative, 2-6-di-t-butyl-P-cresol, 2
2'-methylenebis- (4-ethyl-6-t-butylphenol), 4'-butylidenebis (6-t-butyl-m-cresol), 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) propinate, 2.2'-methylenebis (4-methyl-6-t-
Butylphenol), 4.4'-thiobis (3-methyl-6-t-butylphenyl), 4.4'-butylidenebis (3-methyl-6-t-butylphenol), stearyl-β (3.5-di-). 4-Butyl-4-hydroxyphenyl) propionate, 1.1 / 3-tris (2-
Methyl-4hydroxy-5-t-butylphenyl) butane, 13.5 trimethyl-24.6-tris (3.
5-di-t-butyl-4hydroxybenzyl) benzene, tetrakis [methylene-3 (3'.5'-di-t-butyl-4'-hydroxyphenyl) propionate] methane, etc. (b) Ketoneamine condensation system antioxidant Agent 6-ethoxy-2,2,4-trimethyl-1,2-dihydroquinoline, polymer of 2,2,4-trimethyl-1,2-dihydroquinoline, trimethyldihydroquinoline derivative, etc. (c) Allylamine antioxidant Agent 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, etc. (d) Imidazole-based antioxidant 2-mercaptobenzimidazole, zinc salt of 2-mercaptobenzimidazole, 2-mercaptomethylbenzimidazole, etc. ) Phosphite antioxidants Alkylated allyl phosphite, diphenylisodecyl phosphite, tris (nonylphenyl) phosphite sodium phosphite, trinonylphenyl phosphite, triphenyl phosphite, etc. (f) Thiourea antioxidant Agents Thiourea derivatives, 1,3-bis (dimethylaminopropyl) -2-thiourea, etc. (G) Other antioxidants useful for air oxidation Dilauryl thiodipropionate, etc.

Representative commercial antioxidants are shown below. (1) Phenolic antioxidant; SUMILIZER BHT (Sumitomo),
IRGANOX 1076 (Ciba-Geigy), MARK AO-50 (Adeka
Argus), SUMILIZER BP-76 (Sumitomo), TOMINOX SS (Yoshitomi), IRGANOX 565 (Ciba Geigy), NONOX WSP (IC
I), SANTONOX (Monsanto), SUMILIZER WX R (Sumitomo),
ANTAGEGRYSTAL (Kawaguchi), IRGANOX 1035 (Ciba-Geigy), ANTAGE W-400 (Kawaguchi), NOCLIZER NS-6 (Ouchi Shinko), IRGANOX 1425 WL (Ciba-Geigy), MARK AO-80
(Adeka Argus), SUMILIZER GA-80 (Sumitomo), TOPA
NOL CA (ICI), MARK AO-30 (Adeka Argus),
MARK AO-20 (Adeka Argus), IRGANOX3114 (Ciba Geigy), MARK AO-330 (Adeka Argus), IRGANO
X 1330 (Ciba Geigy), CYANOX 1790 (ACC), IRGA
NOX 1010 (Ciba Geigy), MARK AO-60 (Adeka Argus), SUMILIZER BP-101 (Sumitomo), TOMINOX TT (Yoshitomi), etc. (2) Phosphorus antioxidants; IRGAFOS 168 (Ciba Geigy), MA
RK 2112 (Adeka Argus), WESTON 618 (Borg Warner), MARK PEP-8 (Adeka Argus), ULTRANOX 6
26 (Borg Warner), MARK PEP-24G (Adeka Argus), MARK PEP-36 (Adeka Argus), HGA (Sanko), etc. (3) Thioether antioxidant; DLTDP "YOSHITOMI" (Yoshitomi), SUMILIZER TPL (Sumitomo), ANTIOX L (NOF), DMTD
"YOSHITOMI" (Yoshitomi), SUMILIZER TPM (Sumitomo), ANTIOX
M (NOF), DSTP "YOSHITOMI" (Yoshitomi), SUMILIZER TPS
(Sumitomo), ANTIOX S (NOF), SEENOX 412S (Cypro), M
ARK AO-412S (Adeka Argus), SUMILIZER TP-D
(Sumitomo), MARK AO-23 (Adeka Argus), SANDSTAB
P-EPQ (sand), IRGAFOS P-BPQ FF (Ciba Geigy), IRGANOX 1222 (Ciba Geigy), MARK 329K (Adeka Argus), WESTON 399 (Borg Warner), MA
RK 260 (Adeka Argus), MARK 522A (Adeka Argus), etc. (4) Metal deactivator NAUGARD XL-1 (Uniroyal), MARK CDA-1 (Adeka Argus)
Argus), MARK CDA-6 (Adeka Argus), LRGANO
X MD-1024 (Ciba Geigy), CUNOX (Mitsui Toatsu), etc.

Particularly preferred antioxidants are hindered phenolic antioxidants, and commercially available products include various Irganox products manufactured by Ciba-Geigy and Sumilize manufactured by Sumitomo Chemical Co., Ltd.
r BHT, Sumilizer BH-76, Sumilizer WX-R, Sumilizer
BP-101 etc. The hindered phenol antioxidant prevents generation of compounds such as aldehyde and cyan due to thermal decomposition of the resin, and rarely affects photographic properties.

Also, 2,6-di-hibutyl-p-cresol (BHT), a low-volatile high molecular weight phenolic antioxidant (trade name: Ireganox 1010, Ireganox 1076, T
opanol CA, Ionox 330, etc.), dilauryl thiodipropionate, distearyl thiopropionate, dialkyl phosphate and the like, and it is effective to use one or more, particularly two or more, in combination.

Other Plastics Data Handbook (published by the KK Industrial Research Group), pages 794 to 799, data collection of various antioxidants and plastic additives (KK
Chemical Industry Co., Ltd.) pages 327 to 329 of various antioxidants and PLASTICS AGE ENCYCLOPEDIA Advanced Edition 1986 (KK Plastic Age) pages 211 to 212 of various antioxidants, etc. Is possible.

A light-shielding substance can be added to each of the above layers. By adding the light-shielding substance, the light-shielding property can be secured, and the conductivity and the physical characteristics can be improved. 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 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, 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. In particular, since it is a substance which is excellent in heat resistance and light resistance and is relatively inactive, it is a light-absorbing carbon black, titanium nitride and graphite. Is preferred.

Examples of carbon black materials classified by 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.

Examples of actual products include 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, etc.
Regal 300, 330, 400, 660, 991, SRF-S, Vul
can3, 6 etc., Sterling 10, SO, V, S, FT-F
F, MT-FF, etc. are mentioned. Furthermore, Ashland Chemical Company's United R, BB, 15, 102, 3001, 3004, 3
006, 3007, 3008, 3009, 3011, 3012, XC-3016, X
Examples thereof include C-3017 and 3020, but the invention is not limited thereto.

In the present invention, furnace carbon black is desirable for the purpose of improving the light-shielding property, cost and physical properties, and acetylene carbon black and Ketjen carbon which is a modified by-product carbon black are expensive as the light-shielding substance having an antistatic effect. Black is desirable. If necessary, it is also desirable to mix the former and the latter according to the required characteristics.

There are various forms of incorporating the light-shielding substance into the resin composition, but the masterbatch method is preferable in terms of cost, prevention of contamination of the workplace, and the like. Published Japanese Patent Publication No. 40-26196
Japanese Patent Publication No. 43-10362 discloses a method of preparing a polymer-carbon black masterbatch by dispersing carbon black in a solution of a polymer dissolved in an organic solvent. Describes how to make a masterbatch.

When used as a packaging bag for a photographic light-sensitive material of the present invention, it does not cause fog, has little increase or decrease in photosensitivity, and has a large light-shielding ability. Among carbon blacks, pH 6.0-9.0, especially because of the occurrence of stiffening (hard spots) and pinholes in the film such as fish eyes are less likely to occur.
Furnace carbon black having an average particle size of 10 to 120 mμ, a volatile component of 2.0% or less, and an oil absorption of 50 ml / 100 g or more is preferable in terms of improvement of light-shielding property, improvement of dispersibility, and less deterioration of physical properties.

Further, typical examples of other additives will be described below, but the present invention is not limited thereto.
It can be selected from all known ones. (Types of additives) (Representative examples) (1) Plasticizers; phthalates, glycol esters, fatty acid esters, phosphates, etc. (2) Stabilizers: lead-based, cadmium-based, zinc-based, alkaline earth (3) Flame retardants; phosphoric acid esters, halogenated phosphoric acid esters, halides, inorganic substances, phosphorus-containing polyols, etc. (4) Reinforcing agents: glass roving, metal fibers, glass fibers, glass Milled fiber, carbon fiber, etc. (5) Foaming agents; inorganic foaming agents (ammonia carbonate, sodium bicarbonate), organic foaming agents (nitrone-based, azo-based), etc. (6) Vulcanizing agents; vulcanization accelerators, accelerating aids Etc. (7) Deterioration inhibitors; UV absorbers, metal deactivators, peroxide decomposers, etc. (8) Various thermoplastic resins, rubbers, etc. (9) Nucleating agents: Organic nucleating agents (dibenzylidene sorbitol) Compounds, etc., inorganic nucleating agents (calcium carbonate ) (10) Filling agent;

As the above-mentioned filler, inorganic and organic fillers are used, and as the inorganic filler, calcium carbonate,
Talc, clay, kaolin, silica, diatomaceous earth, magnesium carbonate, barium carbonate, magnesium sulfate, barium sulfate, calcium sulfate, aluminum hydroxide, zinc oxide, magnesium hydroxide, calcium oxide, magnesium oxide, titanium oxide, alumina, mica, asbestos Powder, glass powder, shirasu balloon, zeolite, carbon black, silicate clay, etc. are used, and calcium carbonate, talc, clay, silica, diatomaceous earth, barium sulfate, etc. are particularly preferable.

As the organic filler, cellulosic powder such as wood powder and bulb powder is used. These may be used alone or in combination of two or more.

The average particle size of the filler is preferably 30 μm or less, more preferably 10 μm or less,
It is most preferably 1 to 5 μm. If the average particle size is too large, for example, pinholes or holes are likely to occur in the resin layer, and if the particle size is too small, dispersibility in the resin is poor and microgrit is generated, resulting in poor moldability.

The filler does not adversely affect the photographic light-sensitive material,
In order not to deteriorate the film moldability, the weight loss upon drying at 100 ° C. for 5 hours is 2.0% by weight, preferably 1.0% by weight or less, and particularly preferably 0.5% by weight or less. Further, in order not to adversely affect the photographic light-sensitive material, the free sulfur content in the filler 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. The amount of filler is preferably 0.005% or less, particularly preferably 0.001% or less, and the aldehyde compound is 0.1% or less, preferably 0.05% or less, and particularly preferably 0.01% or less.

Any of the above additives may be added to any layer as required. However, particularly preferred specific embodiments are exemplified below. A thermoplastic resin layer (for example, an L-LDPE film, specifically, a flexible sheet using such a resin film, a polyolefin resin layer, an X-ray) containing one or more of the above-mentioned lubricant, surfactant and coupling agent. It is preferable to mix it in the barrier resin layer and the thermoplastic resin layer).

For example, a thermoplastic resin layer (specifically, a polyolefin resin layer, an X-ray blocking resin layer, or the like) serves as a heat-sealing portion of a packaging bag as described later, and 5% by weight is contained in these layers. Since the above ethylene copolymer resin is contained, good heat seal characteristics can be obtained even if the lubricant is added.

By blending a metal soap among the lubricants into the thermoplastic resin film, the fog of the photographic light-sensitive material (particularly the silver halide photographic light-sensitive material) is prevented and abnormalities in sensitivity and gradation are prevented. The content of the metal soap is preferably 0.001 to 10.0% by weight, more preferably 0.005 to 5.0% by weight, and most preferably 0.01 to 3.0% by weight based on the resin film.
Is. In addition, metal soap (that is, higher fatty acid metal salt)
The metal content therein is appropriately selected. For example, the amount of calcium in calcium stearate is preferably 5 to 10%, and the amount of zinc in zinc stearate is preferably 8 to 15% by weight.

As a concrete example, for example, L-containing 3% by weight of carbon black and 1.5% by weight of zinc stearate was added.
In case of LDPE resin film, color photographic paper and 50 ℃, 80
It has been found that the development effect after the contact for 5 days in% RH has an unexpected effect of reducing the fog density from 0.12 to 0.02. Further, it was found that the dispersibility of carbon black and the like was improved, and the unexpected effect that the generation of lumps (hardness like foreign matter) was reduced to 1/10 or less was simultaneously exhibited. The above-mentioned other lubricants also have the effect of adding dispersibility of the light-shielding substance and resin extrudability.

The above-mentioned other lubricants are preferably 0.01 to 1
0.0% by weight, more preferably 0.05 to 6.0% by weight, most preferably 0.1 to 3.0% by weight. Further, it is preferable that the surfactant and the coupling agent are contained in the thermoplastic resin film, particularly in the polyolefin resin layer or the X-ray blocking polyolefin resin layer. The surfactant is preferably added in an amount of 0.01 to 3.0% by weight in the resin composition. Furthermore, it is preferable to contain the antioxidant in the flexible sheet, the polyolefin resin layer or the X-ray blocking polyolefin resin layer.

The addition amount is, for example, preferably 0.0005 to 0.5% by weight when added to the polyolefin resin adhesive layer,
More preferably 0.001-0.3% by weight, most preferably 0.00
5 to 0.2% by weight. If the amount added is less than 0.001% by weight, there is almost no effect. On the other hand, if the addition amount exceeds 2.0% by weight, the photographic light-sensitive material utilizing the oxidation and reduction effects may be adversely affected and abnormal photographic performance (fog or sensitivity fluctuation) may occur. For this reason, the antioxidant is the thermal decomposition of the resin,
It is preferable to add the minimum amount that does not cause resin coloration failure or spotting. In addition, vitamin E and its compounds (for example, vitamin E carboxylic acid ester), which have no adverse effect on the human body, have a large antioxidant effect on various thermoplastic resins, and can improve the light-shielding property, are particularly preferable.

Further, when used in combination with carbon black or the like, the antioxidant exhibits a synergistic effect. The combined use of a phenol-based antioxidant, a phosphorus-based antioxidant and carbon black is preferable because the antioxidant effect is particularly exhibited.

Further, an antiblocking agent may be added to the innermost layer (for example, polyolefin resin layer). This antiblocking agent includes silica, calcium carbonate, talc (magnesium silicate), aluminum silicate, calcium silicate, dicarboxylic acid ester amide, etc. Among them, silica is preferable, and the preferable addition amount is 0.01
~ 5.0% by weight. If it is less than 0.01% by weight, the antiblocking effect is small and only the kneading cost increases. 5.0
If the content exceeds 10% by weight, not only lumpy non-uniform failures occur, but also the physical strength and heat sealability of the film deteriorate.

This silica has an average particle size of 0.3 to 20.
It is preferably μm. If it is less than 0.3 μm, cohesiveness is strong and many spots occur. In addition, the antiblocking effect is also small. If it exceeds 20 μm, not only the surface of the film is roughened with silica but also the surface of the film is rough and scratches are likely to occur on the photosensitive material.

A preferred embodiment of the film forming method for the X-ray blocking polyolefin resin layer will be illustrated below. X
Line blocking filler 15-70% by weight, antioxidant 0.0005-0.2
A resin composition for an X-ray blocking resin layer containing wt%, a lubricant and / or a surfactant is melt-kneaded and then extruded in a strand shape, and cut into resin pellets having a volume of 0.25 cm ³ or less,
A film having a thickness of 35 to 200 μm is extruded at a resin temperature of 150 ° C. or higher alone or after being mixed with other resin pellets.

When the films are laminated stepwise by successive molding or the like, the film adhesive surface may be surface-treated in order to enhance the adhesive strength between the adjacent film layers. For example, physical surface treatment or AC agent treatment may be performed to improve the adhesive strength between the flexible sheet and the metal foil layer, between the metal foil layer and the polyolefin resin layer, or between the flexible sheet and the X-ray blocking resin layer.

Typical examples of the physical surface treatment are shown below. Flame (flame) treatment; running cost is high and there is a risk of fire. Plasma processing method; converting argon gas into plasma,
Treat the adhesive surface. The physical strength is several times that of corona discharge treatment, but the equipment cost is also several tens of times that of corona discharge treatment equipment. Corona discharge treatment: The substrate that can be treated is 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. Sandplast treatment: The surface is roughened by spraying silica gel, etc. at high pressure. Chemical treatment: Surface treatment with dichromic acid solution, etc. Ozone treatment: Surface treatment is performed in a box filled with ozone. The adhesive strength is improved even if the resin temperature for extrusion lamination is lowered. Preheat treatment: The film to be extrusion laminated is heat-treated with a heater drum or hot air.

Besides, 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 (Anc agent) which is a general term for an adhesion promoter or a cross-linking agent used in the laminating industry.
hor Coating Agent). This A
The agent C is different from a mere adhesive and is also called a primer, a fixing agent, or the like, which is distinguished from the adhesive in the sense of chemically adhering. Representative examples of AC agents are shown below. (1) Organic titanate (titanium-based) AC 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) 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 the adhesive effect appears. The disadvantage is that pot life is short and 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-based AC agent (6) Polybutadiene-based AC agent

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

The packaging bag for the photographic light-sensitive material of the present invention includes:
For example, a unipack bag, a single flat bag, a double flat bag, a single gusset bag, a double gusset bag, a shrink wrapping bag, and a bulk wrapping bag (JP-A-3-53243, JP-A-3-71346, etc.). There is.

Examples of the photographic light-sensitive material that can be packaged in the photographic light-sensitive material packaging bag of the present invention are shown below. Silver halide photographic light-sensitive material (printing film, color photographic paper, color film, master paper for printing, DTR light-sensitive material, computer typesetting film and paper, microfilm, movie film, self-developing photographic light-sensitive material, direct positive type Films and papers, etc. Thermal development photosensitive materials (thermal development color photosensitive materials, thermal development black-and-white photosensitive materials (for example, Japanese Patent Publication Nos. 43-4921 and 43-4924, "Basics of Photographic Engineering") 553 to 555 (published by Corona Publishing Co., Ltd.) and Research Tis Closure magazine, June 1978, pages 9 to 15 (RD-17029), etc. Further, JP-A-59-12431. , 6
0-2950 publication, 61-52343 publication and U.S. Pat.
Photothermographic color photosensitive material of transfer type described in the specification No. 267)) Photosensitive / thermosensitive recording material (photothermography (photosensitive / thermosensitive image forming method) described in JP-A-3-72358) Recording material using a) diazonium photographic light-sensitive material (4-morpholinobenzenediazonium microfilm, microfilm,
Copying film, printing plate material, etc. Photosensitive material containing azide and diazide (paraazidobenzoede, 4,4'diazidostilbene, etc.,
For example, copying film, printing plate material, etc. Photosensitizing material containing quinonediazide photographic light-sensitive material (orthoquinonediazide, orthonaphthoquinonediazide compound, such as benzoquinone (1,2) -diazide- (2) -4-sulfonic acid phenyl ether) Materials such as printing plates, copying films, adhesion films, etc. Photopolymers (photosensitive materials containing vinyl monomers, printing plates, adhesion films, etc.) Polyvinyl cinnamate photosensitive materials (for printing, for example) Films, IC resists, etc.)

[0094]

Embodiments of the packaging bag for photographic light-sensitive material of the present invention will be described with reference to the drawings. 1 to 4 are partial cross-sectional views showing a layer structure of a packaging bag for photographic light-sensitive materials, and FIG. 5 is a side view in which a central portion of a laminated film used for manufacturing a packaging bag for photographic light-sensitive materials is omitted. 6 is a perspective view showing the state of the laminated film during the manufacturing process of the packaging bag for photographic photosensitive materials, FIG. 7 is a perspective view of the packaging bag for photographic photosensitive materials, and FIG. 8 is a perspective view of another packaging bag for photographic photosensitive materials. Is.

In the packaging bag for photographic light-sensitive material shown in FIG. 1, the abrasion-resistant flexible sheet 1, the X-ray shielding metal foil layer 2 and the polyolefin resin layer 3 containing no light-shielding substance are modified from the outer surface side of the bag. It is laminated via the adhesive layers 4 and 4.

The packaging bag for photographic light-sensitive material shown in FIG. 2 uses a polyolefin resin layer 3a containing a light-shielding substance, except that
This is the same as the example shown in FIG.

The packaging bag for photographic light-sensitive material shown in FIG. 3 has an X-ray blocking polyolefin resin layer 5a containing an X-ray blocking filler.
And a thermoplastic resin layer 6, 6 located on both sides thereof, a three-layer coextruded film IIIa.

The packaging bag for photographic light-sensitive material shown in FIG. 4 is a two-layer coextruded film IIa comprising an X-ray blocking polyolefin resin layer 5a containing an X-ray blocking filler and a thermoplastic resin layer 6.
Two pieces of the thermoplastic resin layer 6 laminated with the adhesive layer 7 are prepared, and the thermoplastic resin layers 6 are adhered by blocking.

Next, the process of manufacturing the packaging bag for photographic light-sensitive materials will be described. First, the laminated film 10 as shown in FIG.
To prepare. This laminated film 10 has a layer structure shown in FIG.
Wear-resistant flexible sheet 1,
It is composed of an X-ray shielding metal foil layer 2, a polyolefin resin layer 3a containing a light-shielding substance, and modified adhesive layers 4 and 4. At both ends in the longitudinal direction, the X-ray shielding metal foil layer 2 is shortened and the abrasion-resistant flexible sheet 1 and the polyolefin resin layer 3 are bonded by the modified adhesive layers 4 and 4. Therefore, the X-ray shielding metal foil layer 2 is not exposed on the end surface 11 (which becomes the end surface of the opening when storing a stored item during bag making).

As shown in FIG. 6, such a laminated film 10 is folded back in two in the longitudinal direction, and both side ends thereof are heat-sealed to form a heat-sealed portion as shown in FIG.
12 is formed and the bag closed on three sides is completed.

FIG. 8 is a perspective view of another embodiment of the packaging bag for photographic light-sensitive material. In this packaging bag for photographic light-sensitive materials, a cylindrical laminated film was prepared from the three-layer coextrusion inflation film shown in FIG. 3, and one opening (bottom) of this cylindrical laminated film was sealed by heat sealing. It is the heat seal portion 13.

Example 1 The layer structure is the same as that shown in FIG. As the heat-resistant flexible sheet 1, a 70 μm-thick spunbond nonwoven fabric (D
"TYVEK (registered trademark) 1444A" manufactured by Uppont was used. As the X-ray shielding metal foil layer 2, an electrolytic iron foil (made by Toyo Kohan) having a density of 8.0 g / cm ³ and a thickness of 30 μm was used. The polyolefin resin layer 3 has an MI of 2.0 g / 10 minutes and a density of 0.920.
79.9% by weight of ethylene / octene-1 copolymer resin of g / cm ³ , MI of 1.5 g / 10 minutes, 20% of homopolyethylene resin of 0.960 g / cm ³ density, phenolic antioxidant (IRGANOX 1010 ) 0.05% by weight, erucic acid amide 0.05% by weight
An inflation film having a thickness of 50 μm was used. The modified adhesive layer 4 has an MI of 5.1 g / 10 minutes and a density of
80% by weight of low-density homopolyethylene resin 0.920 g / cm ³ , MI modified with maleic anhydride 5.5 g / 10 minutes, density 0.93 g
An extrusion lamination adhesive layer having a thickness of 20 μm and made of 20% by weight of a low-density homopolyethylene resin having a density of / cm ³ was used. A B5 size gusset bag having the shape shown in FIG. 7 was prepared from the laminated film having the above-mentioned layer structure.

Example 2 The same layer structure as in Example 1 was used as the X-ray shielding metal foil layer 2, except that a lead foil having a density of 11.4 g / cm ³ and a thickness of 20 μm was used instead of the electrolytic iron foil. It is a B5 size gusset bag.

Example 3 As the X-ray shielding metal foil layer 2, a stainless foil having a density of 8.0 g / cm ³ and a thickness of 30 μm was used instead of the electrolytic iron foil.
It is a B5 size gusset bag having the same layer configuration as in Example 1.

Comparative Example 1 Instead of the electrolytic iron foil as the X-ray blocking metal foil layer 2, the thickness was changed.
Aluminum foil, which is an X-ray transparent metal of 30 μm (density is
B5 having the same layer structure as in Example 1 except that 2.7 g / cm ³ ) was used.
It is a size gusset bag.

Example 4 The layer structure is the same as that shown in FIG. As the thermoplastic resin layer 6 on the outer side (upper side in the figure), a 10-μm-thick abrasion-resistant film made of nylon resin (“Novamide” manufactured by Mitsubishi Kasei) was used. As the X-ray blocking polyolefin resin layer 5a containing an X-ray blocking filler, a maleic anhydride modified ethylene having a thickness of 70 μm containing 40% by weight of lead powder having a surface of an acid-modified polyolefin resin and having a density of 6.6 g / cm ^3. -4 Methylpentene-1 copolymer resin layer was used. The inner thermoplastic resin layer 6 (lower in the figure) has an MI of 2.0 g / 10 minutes and a density of 0.9.
70% by weight of 20 g / cm ³ ethylene / 4-methylpentene-1 copolymer resin, 2.0 g / 10 min of MI, 24.85% by weight of homopolyethylene resin with a density of 0.965 g / cm ³ , 5% by weight of paraffin wax, phenol Antioxidant (IRGANOX 10
75) A polyolefin resin layer having a thickness of 50 μm and composed of 0.05% by weight and 0.1% by weight of tocopherol was used. The light-shielding three-layer coextrusion film IIIa having the above layer structure was used to prepare a tubular packaging bag shown in FIG.

Example 5 As an X-ray blocking filler, a density of 40% by weight of lead powder was used instead of 40% by weight of lead powder.
A tubular packaging bag shown in FIG. 8 using the same three-layer coextrusion film IIIa as in Example 4 except that 50% by weight of 4.3 g / cm ³ barium sulfate was used.

Comparative Example 2 The same procedure was carried out except that, instead of using 40% by weight of lead powder as an X-ray blocking filler, 50% by weight of an X-ray transparent filler having a density of 2.5 g / cm ³ was used. It is the tubular packaging bag shown in FIG. 8 which used the same three-layer coextrusion film as in Example 4.

Comparative Example 3 Instead of using 40% by weight of lead powder as the X-ray blocking filler, 50% by weight of furnace carbon black having a density of 1.9 g / cm ³ which is an X-ray transmitting filler was used. It is the tubular packaging bag shown in FIG. 8 using the same three-layer coextrusion film as in Example 4.

Evaluation of characteristics: In the packaging bags of Examples 1 to 5, I
After sealing a color negative film with an SO sensitivity of 400, a wavelength of 0.01 to 100Å and an intensity of 1 from an X-ray tube (80kv, 10mA) separated by 1 m.
The color negative film was developed by irradiating it with X-rays of 0 milli- roentgen and the fog density was measured. All were 0.02 or less, and there was no actual harm. However, Comparative Examples 1 to 3 were all practically impractical because the fog density of the photographic light-sensitive material was 0.06 or more and the actual damage was great. In addition, in all of Examples 1 to 5, the delamination strength is high, the heat seal suitability (heat seal strength, hot tack property, heat seal strength retention property over time) is excellent, the physical strength is large, and the abrasion resistance is also excellent. It was a hermetically sealed bag capable of ensuring a moisture-proof property and a light-shielding property without causing pinholes, heat seal peeling, damage, dust adhesion, etc. even when used.

Example 6 The layer structure is the same as that shown in FIG. As the abrasion-resistant flexible sheet layer 1, a nonwoven fabric made of a spunbonded polyolefin resin having a thickness of 90 μm and a Young's modulus of 70 kg / mm ² or more (trade name “TYVEK (registered trademark) manufactured by Dupont, USA)
1059B ″ was used. The same X-ray shielding metal foil layer 2 as in Example 1 was used. As the light-shielding polyolefin resin layer 3a, MI was 2.0 g / 10 minutes and density was 0.92 g / cm ^3. Of ethylene 4-methylpentene-1 copolymer resin 66.3% by weight, MI of 0.9 g / 10 minutes, homopolyethylene resin of density 0.950 g / cm ³ 30% by weight, phenolic antioxidant (IRGANOX 1010 ) Is 0.05% by weight, vitamin E carboxylic acid ester is 0.10% by weight, oleic acid amide is 0.05% by weight, pH is 7.7, furnace carbon black having an average particle diameter of 21 mμ is 3.0% by weight, and magnesium stearate is
A light-shielding inflation film having a thickness of 70 μm and containing 0.5% by weight was used. Example 1 was used as the modified adhesive layer 4.
The same one was used. As shown in FIG. 5, the laminated film having the above-mentioned layered structure encloses the X-ray shielding metal foil layer 2 with the abrasion-resistant flexible sheet layer 1 and the light-shielding polyolefin resin layer 3a as shown in FIG. It has a structure. Then, a flat bag having a shape shown in FIG. 7 whose side end portions were heat-sealed with such a laminated film was prepared.

Evaluation of characteristics: After sealing a color negative film having an ISO sensitivity of 400, an X-ray tube (80 kv, 10 mA) distant from 1 m was irradiated with X-rays having a wavelength of 0.01 to 100 Å and an intensity of 10 mm, and the color negative film was developed and fogged. The concentration was measured, but it was 0.02 or less, and there was no problem. Further, since there is no X-ray blocking metal foil layer having a sharp edge in the opening of the bag, the X-ray blocking metal foil layer does not rust or corrode due to oxygen or water without damaging the hand. It was flexible and easy to put in and take out the color negative film. Furthermore, it has excellent physical strength under all conditions, delamination strength, heat seal strength (especially heat seal strength over time), moisture resistance, complete light-shielding property, antistatic property, photographic property, gas barrier property. However, it was useful as a packaging bag for various photographic light-sensitive materials.

[0113]

INDUSTRIAL APPLICABILITY The present invention is a packaging bag having excellent suitability for use, which has a large X-ray blocking property, a large interlayer adhesive strength and a heat seal strength, and can prevent pinholes and peeling. .

[Brief description of drawings]

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

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

FIG. 4 is a partial cross-sectional view showing the layer structure of the packaging bag for photographic light-sensitive materials of the present invention.

FIG. 5 is a side view in which a central portion of a laminated film used in the packaging bag for a photographic light-sensitive material of the present invention is omitted.

FIG. 6 is a perspective view showing the middle of the manufacturing process of the packaging bag for the photographic light-sensitive material of the present invention.

FIG. 7 is a perspective view of a photographic photosensitive material packaging bag of the present invention.

FIG. 8 is a perspective view of another embodiment of the packaging bag for photographic light-sensitive material of the present invention.

[Explanation of symbols]

 1 ... Abrasion resistant flexible sheet 2 ... X-ray blocking metal foil layer 3 ... Polyolefin resin layer 4 ... Modified adhesive layer 5 ... X-ray blocking polyolefin resin layer 6 ... Thermoplastic resin layer 7 ... Adhesive layer a ... Light blocking property Indicates that the substance is contained.

Claims (7)

[Claims] 1. A structure having a wear-resistant flexible sheet, a modified adhesive layer, an X-ray shielding metal foil layer, a modified adhesive layer, and a polyolefin resin layer laminated in this order, wherein the modified adhesive layer is acid-modified. A packaging bag for a photographic light-sensitive material, which contains a thermoplastic resin, and the polyolefin resin layer contains 5% by weight or more of an ethylene copolymer resin. 2. The opening during bag making is in a state in which the heat-resistant flexible sheet and the polyolefin resin layer are formed longer than the X-ray blocking metal foil layer, and the X-ray blocking metal foil layer does not exist. The packaging bag for a photographic light-sensitive material according to claim 1. 3. An X-ray blocking polyolefin resin layer containing an X-ray blocking filler, and a thermoplastic resin layer laminated on both sides thereof, and one or more of an X-ray blocking polyolefin resin layer and a thermoplastic resin layer. Packaging bag for photographic light-sensitive material, characterized in that acid-modified thermoplastic resin is contained in 4. The packaging bag for a photographic light-sensitive material according to claim 3, wherein the surface of the X-ray blocking filler is surface-treated with a surface treatment agent. 5. The packaging bag for a photographic light-sensitive material according to claim 3, wherein the thermoplastic resin layer is a part of a multilayer coextrusion film. 6. The packaging bag for a photographic light-sensitive material according to claim 3, wherein the X-ray blocking polyolefin resin layer contains at least one of a lubricant, a surfactant and a coupling agent, and an antioxidant. 7. The X-ray blocking polyolefin resin layer has a melt index of 0.8 to 10 g / 10 minutes and a density of 0.870 to 0.940 g / c.
An ethylene / α-olefin copolymer resin of m ³ of 20 wt% or more and an X-ray blocking filler of 5 to 80 wt% are contained.
Or the packaging bag for photographic light-sensitive material as described in 6 above.