JPH05281664A - Packaging material for photosensitive material and light shielding bag formed by using the same - Google Patents

Abstract

PURPOSE:To provide the packaging material for photosensitive materials and the light shielding bag which is formed by using this packaging material and has a perfect light shielding property and is so formed as to have an easy unsealing property and not to generate pinholes and curls. CONSTITUTION:This packaging material is constituted by laminating a vapor deposited aluminum flexible sheet 4 formed by vapor deposition of a vapor deposited aluminum film 3 on a dustless flexible sheet layer 2 via an adhesive layer 5 on one surface of a reinforcing sheet 1 in such a manner that the vapor deposited aluminum film 3 is positioned on the dustless flexible sheet layer 2 side and directly laminating a heat sealing layer 6 on the other surface. The reinforcing sheet 1 is formed by vertically and horizontally disposing band materials of a thermoplastic resin having sizes of a relation of a length/width >=3. The peeling strength of the reinforcing sheet 1 and the vapor deposited aluminum sheet 3 is >=300g/15mm width.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a packaging material for a photosensitive material in which pinholes and curls are less likely to occur and a complete light-shielding bag using the packaging material.

[0002]

2. Description of the Related Art Conventionally, as a packaging material for photosensitive materials, carbon black has been added in an amount of 3% by weight or more, and a plurality of high density polyethylene resin films uniaxially stretched at a stretch ratio of 2.2 to 4.2 times have been used. There was a laminate in which the angle was 45 to 90 degrees (Jitsuko Sho 61-20590).

Further, two uniaxially stretched high-density polyethylene resin films having a high stretching ratio are laminated so that the stretching axes cross each other at an angle of 45 to 90 °. There has been a laminate of low-density polyethylene films containing at least one of antistatic agents (Japanese Utility Model Publication No. 56-19087). Furthermore, there was one in which a bleached kraft paper was laminated on the outside of an aluminum foil, and a light-shielding linear low-density polyethylene resin (hereinafter referred to as L-LDPE resin) film was laminated on the inside with an adhesive layer (special feature). Hei 2-2700).

[0004]

However, the above-mentioned conventional packaging materials for photosensitive materials have a large longitudinal and lateral tear strength, but a large tensile elongation at break and a relatively small Young's modulus and are flexible. It was Therefore, when it is used for packaging a roll-shaped or sheet-shaped photographic light-sensitive material having a sharp edge and a weight of 5 kg or more, the edge portion or the corner portion may be cut and a hole or a pinhole may occur. Nevertheless, even if the opening notch was formed, it was difficult to open, and the opening could not be performed in a straight line. Also,
Even with a light-sensitive material having a weight of 5 kg or less, pinholes sometimes occurred due to folding or wrinkling during the packaging process or the transportation process. When a pinhole is generated, moisture permeability and oxygen permeability increase, the quality of the photographic light-sensitive material deteriorates, dust adheres, and the complete light-shielding property essential for the photographic light-sensitive material packaging material cannot be secured. It was something to do. Here, the perfect light-shielding property means that there is no pinhole and that it has a property of blocking not only visible light but also light of all wavelengths such as infrared rays and ultraviolet rays.

Further, the above-mentioned conventional packaging material for a photosensitive material is liable to be curled, and its handling is troublesome.

The present invention solves the above problems and can always ensure the complete light-shielding property essential for packaging materials for photographic light-sensitive materials.
An object of the present invention is to provide a packaging material for a photosensitive material, which has excellent openability when a notch is formed even though the pinhole is hard to occur and has a large physical strength, and has a small curl, and a light-shielding bag using the same. ..

[0007]

The present invention has been made to achieve the above object, and a packaging material for a light-sensitive material of the present invention comprises a metal layer and a metal layer laminated on one surface of the metal layer. A dusty flexible sheet and a reinforced sheet laminated on the other surface of the metal layer via an adhesive layer, and the reinforced sheet is a thermoplastic resin having dimensions of length / width ≧ 3. It is formed by arranging strips made of (1) vertically and horizontally, and the peel strength between the reinforcing sheet and the metal layer is 300 g / 15 mm width or more. When the metal layer is a metal thin film processed flexible sheet, the peel strength refers to any peel strength between the metal thin film processed layer and the reinforced sheet or between the flexible sheet and the reinforced sheet.

As the metal layer, aluminum foil, lead foil,
There are metal foils such as iron foil, tin foil, zinc foil, electrolytic iron foil, copper foil, and stainless steel foil, and the thickness of the metal foil is 5-10.
0 μm is preferable, 7 to 50 μm is particularly preferable, and 9 to 20 μm is most preferable, in consideration of economical efficiency, handleability, and securing of characteristics. In addition, thermoplastic resin films and dust-free flexible sheets (dust-free paper, synthetic paper, non-woven paper, glassine paper,
A metal thin film processed flexible sheet in which a metal thin film processed layer is provided on cellophane, surface size or surface coated paper) is also preferable.

The metal thin film processing layer provided on the flexible sheet such as a film will be described below. 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, and aluminum vacuum-deposited biaxially stretched nylon resin film and biaxially stretched polyester resin film are preferable because they ensure a high Young's modulus and pinholes do not occur.

As a method for processing the metal thin film processing layer into a thin film, a vacuum evaporation method, a sputtering method, an ion plating method, an electron beam evaporation method or the like is used. The vacuum deposition method is particularly preferable because the equipment is relatively inexpensive, the workability is excellent, and the thin film processing cost is low. 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, moisture resistance improvement, and cost. The thickness is preferably 800Å, more preferably 100 to 600Å.

The metal thin film processed flexible sheet will be described in detail below. As a method for processing a metal thin film, it is provided on both sides or one side (for example, one side on the photosensitive material side) of a flexible sheet by a conventionally known thin film forming method such as a vacuum vapor deposition method, a sputtering method, an ion plating method, an electron beam vapor deposition method. it can.

Al, Sn, Zn, Co, Cr, and
Although simple metals such as Ni, Fe and Cu, alloys and other metals capable of forming a thin film can be used, aluminum (Al) is most suitable in terms of cost and workability.

The metal thin film is a laminated body in terms of physical strength, light-shielding property, antistatic property and moisture-proof property, cost and quality.
A thickness of 55 to 1200Å is preferred. That is, if the thickness is less than 55 Å, it is not possible to reduce the charge generated on both sides of the metal thin film with the metal thin film processed flexible sheet layer alone, and increase the thickness of the flexible sheet layer and the light shielding layer on both sides of the metal thin film. If it is not, it is impossible to secure the moisture-proof property and the light-shielding property required for the packaging material for the photosensitive material.

If the thickness exceeds 1200 Å, the antistatic property, the moistureproof property and the light shielding property can be secured, but the cost and the deterioration of the flexible sheet layer due to heating due to the vacuum deposition method, the deterioration of the physical strength of the finished laminated film, etc. There is a problem in that it is difficult to put into practical use. In the case of an aluminum vapor-deposited film, the thickness is 70 Å or more, and for normal use, the thickness is preferably 80 to 800 Å, more preferably 100 to 600 Å. If necessary, a protective layer may be provided on the metal thin film.

As the metal thin film protective layer, an acryl resin, a cellulose resin such as a fibrin acetate, a urethane resin, an epoxy resin, a polyester resin, an ionomer resin, EEA.
Appropriate resins such as resins, various polyethylene resins and polypropylene resins can be used. Also, wax, gelatin, polyvinyl alcohol and the like can be used.

The protective layer of the metal thin film is preferably formed to have an extremely thin thickness. 50μ even when made by extrusion lamination method
If it is not less than m, the removal of static electricity will be insufficient. 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. The flexible sheet layer, the light shielding layer, the adhesive layer, and the metal thin film protective layer may be mixed with an antistatic agent, metal powder such as carbon black, aluminum powder, aluminum paste, and a conductive substance such as carbon fiber. If so, the removal of static electricity will be more thorough.

The above metal layers (metal foil, thin film processed flexible sheet layer such as vacuum deposited film) are laminated, and a heat resistant flexible sheet layer excellent in pinhole resistance and a polyolefin resin film layer are laminated on both sides. As a result, MO
Oxygen permeability measured by CON method (same pressure method based on ASTM D-3985) is 50cc / m ² · 24 hours · 1atm or less.
The moisture permeability determined by the cup method of S Z-0208 (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 aluminum foil is 7
Oxygen permeability of 35 cc / m ² , 24 hours, 1 atm or less, and water vapor permeability of 3 g /
The quality can be maintained 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 becomes less than m ² · 24 hours and deteriorates in quality by oxygen and humidity.

The film for processing the metal thin film may be a single layer film or a multi-layer coextrusion film. As a single layer film, polyester resin film, polyamide resin (nylon 6 resin, nylon 6.6 resin, nylon 12 resin, etc.) film, polypropylene resin film, polyethylene resin film, polyacrylonitrile resin film, ethylene / α-olefin copolymer A combined resin film, a propylene / α-olefin copolymer resin film, a polystyrene resin film, a polycarbonate resin film, an EVOH resin film, a film in which two or more kinds of resins are blended, and the like can be used.

The above-mentioned film may be a non-stretched film, a uniaxially stretched film or a biaxially stretched film, but a biaxially stretched film is preferable since it has a large Young's modulus and can improve heat resistance.

As the dust-free flexible sheet, dust-free paper, synthetic paper, non-woven fabric, glassine paper, cellophane, cellulose acetate film, regenerated cellulose film, EV
There are OH (Eval etc.) resin film and thermoplastic resin film. As the thermoplastic resin film, polyethylene resin film, ethylene copolymer resin film, polypropylene resin film, propylene copolymer resin film, polyvinyl chloride resin film, polyvinylidene chloride resin film, polyamide resin film, E
VOH resin film Polycarbonate resin film, polyester resin film, modified resin film thereof,
A film obtained by blending two or more of these resins and elastomer resins (including synthetic rubber) can be used. These films may be unstretched films, uniaxially stretched films or biaxially stretched films. In particular, a polyamide resin film and a polyester resin film having excellent pinhole resistance are preferable.

Polyamide resin (nylon 6 resin, nylon 6/6 resin, nylon 12
Resin, etc.) film, polyacrylonitrile resin film, polyester resin film, non-woven fabric, synthetic paper, especially biaxially stretched polyamide resin film and polyester resin film or spun metal-deposited (aluminum vacuum deposition is preferable because it is cheap and has excellent characteristics). When bonded non-woven fabric is used, it has excellent pinhole resistance, heat resistance, and a high Young's modulus, its appearance is beautiful, and the surface temperature of the packaging material does not rise even if it is left in the sunlight. The temperature inside the bag hardly rises even when formed, and there is almost no generation of dust, and there is almost no deterioration in quality when packaging photographic light-sensitive materials, especially high-sensitivity silver halide photographic light-sensitive materials containing sensitizing dyes. .. Further, when cellophane having a haze of 98% or less is used, it is easily visible even under a safelight and the workability is improved. Further, when the stretched film is used on the outside of the bag, Young's modulus, heat resistance and hardness are improved, so that the heat-sealing layer inside the bag can be satisfactorily heat-sealed.

The reinforcing sheet is formed by vertically and horizontally arranging strips made of a thermoplastic resin having dimensions of length / width ≧ 3, and preferably length / width ≧ 5, particularly preferably length / width.
The width is ≧ 10. When the length / width of the strip material is less than 3, the pinhole resistance is reduced and the curl is increased, and a packaging material for a photosensitive material that can always ensure complete light shielding property and a light shielding bag using the same are provided. Becomes difficult. For example, length 30
Use a strip of 0 mm or more and a width of 2 to 20 mm. Preferably width 5
Use strips of ~ 10mm and length of 500mm or more.

The reinforcing sheet is formed by arranging the strips in the vertical and horizontal directions. Even if the strips are formed in a knitted state without adhering to each other, the strips are bonded together by heat welding or an adhesive. You may form it. For example, a long fiber nonwoven fabric, a net, or a film in which a film is vertically stretched, finely split and woven and laminated vertically and horizontally (a product name of a nonwoven fabric manufactured by Nippon Petrochemical KK) and the like.

As the thermoplastic resin forming the strip material, a crystalline thermoplastic resin in which the molecules are easily oriented in the longitudinal direction is preferable. If the thermoplastic resin has a tear strength of lateral tear strength / longitudinal tear strength ≧ 1.2, it may be a single resin, a mixed resin of two or more kinds, or a crystalline resin. Even an amorphous resin can be used. If the relationship between the transverse tear strength / longitudinal tear strength is less than 1.2, it is easy to cut when manufacturing the strip and when performing the strip with tension applied in the vertical and horizontal directions. Therefore, it is a resin capable of producing a strip material having a value of tear strength in the transverse direction / tear strength in the longitudinal direction of 1.2 or more, preferably 2.0 or more, particularly preferably 5.0 or more.

The adhesive layer preferably contains an acid-modified polyolefin resin. This acid-modified polyolefin resin is a modified polyolefin resin obtained by graft-modifying a polyolefin resin and an unsaturated carboxylic acid, and examples thereof include a graft-modified polyethylene resin, a graft-modified polypropylene resin, and a graft-modified ethylene copolymer resin.

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. , Citraconic acid, crotonic acid, isocrotonic acid, nadic acid (endocis-bicyclo [2,2,1] hept-5-ene
-2,3-dicarboxylic acid), maleic anhydride, citraconic anhydride, itaconic anhydride, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, glycidyl acrylate, methacryl Acid glycidyl, 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 matacrylate, sodium acrylate, zinc acrylate, magnesium acrylate, calcium acrylate, sodium methacrylate, potassium acrylate,
Potassium methacrylate, N-butyl maleimide, N-phenyl maleimide, maleenyl chloride, glycidyl maleate,
Mention may be made of dipropyl maleate, aconitic acid anhydride, sorbic acid and the like, and it is possible to use them in 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 for graft-modifying the unsaturated carboxylic acids in the modified polyolefin resin is not particularly limited. For example, the method disclosed in Japanese Examined Patent Publication (Kokoku) No. 43-21421 and the like which react in a molten state, and the Japanese Examined Patent Publication No.
The method disclosed in JP-B-15422, etc., the method disclosed in JP-B-43-18144 for reacting in a slurry state, the method disclosed in JP-B-50-77493 for reacting in a gas phase, etc. is there. Of these methods, the melt-kneading method using an extractor is preferable because it is simple and inexpensive in operation.

The amount of the unsaturated carboxylic acids used is the polyolefin resin base polymer (various polyethylene resins, various polypropylene resins, various polyolefin copolymer resins, polybutene-1 resin, poly-4-methylpentene-1) for securing the adhesive strength. Α-olefin copolymer resin such as and its copolymer resin) 0.01 to 20 parts by weight per 100 parts by weight,
It is 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, and 2,5-dimethyl. -2,5-di (t-butylperoxy) hexane, 2,5-
Dimethyl-2,5-di (t-butylperoxy) hexine, di-
t-Butyl peroxide, cumene hydroperoxide, t-butyl-hydroperoxide, dicumyl peroxide, t-butylperoxylaurate, t-butylperoxybenzoate, 1,3 bis (t-butylperoxyisopropyl) ) Benzene, cumene hydroperoxide, di-t-butyl-diperoxyphthalate, t-butyl peroxymaleic acid, organic peroxides such as isopropyl percarbonate, azo compounds such as asobisisobutyronitrile, ammonium persulfate, etc. Inorganic peroxide, etc.

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-butylperoxide, di-cumylperoxide, 2,5-dimethyl-2,5di (t-butylperoxy) hexane, 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 acid-modified 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) Sumitomo Chemical KK “Bondaine” (9) Tosoh KK “Mersen M” (10) Mitsui DuPont Chemical KK "CMPS" etc. The amount of acid-modified polyolefin resin contained in the adhesive layer is
It is preferably 5% by weight or more, and particularly preferably 10% by weight or more.

The peel strength between the metal layer and the reinforcing sheet is
300g / 15mm width or more, preferably 500g
/ 15 mm width or more, particularly preferably 600 g / 15 mm width or more.
When the peel strength is less than 300 g / 15 mm width, the physical strength is excellent, pinholes are less likely to occur, and a curl with a small curl can be obtained, but even if an opening notch is formed, opening by hand becomes difficult. Further, peeling occurs between the layers, which makes practical application difficult.

The packaging material for a light-sensitive material of the present invention preferably contains a light-shielding substance in one or more layers. 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, 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 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 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.

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. Although there are various forms of blending the light-shielding substance with the polyethylene-based polymer as described above, the masterbatch method is preferable in terms of cost, prevention of contamination of the workplace, and the like. In the publicly known Japanese Patent Publication No. 26196/1988, there is disclosed a method of preparing a polymer-carbon black masterbatch by dispersing carbon black in a solution of a polymer dissolved in an organic solvent.
43-10362 describes a method of dispersing carbon black in polyethylene to form a masterbatch.

It is preferable that a heat seal layer containing at least one of a lubricant, an antistatic agent and a conductive substance is laminated on the reinforced sheet. As the resin forming this heat seal layer, ethylene / α-olefin copolymer resin, low-density homopolyethylene resin, medium-density homopolyethylene resin, high-density homopolyethylene resin, homopolypropylene resin, propylene / α-olefin copolymer resin (Including random and block), terpolymers,
Elastomer resin, ethylene / vinyl acetate copolymer (E
VA), resin, polyester resin, ionomer resin, ethylene / acrylic acid copolymer (EAA and hereinafter) resin, ethylene / ethyl acrylate copolymer (EEA and hereinafter) resin, ethylene / methyl acrylate copolymer Resins (hereinafter referred to as EMA), single resins such as acid-modified polyolefin resins, and mixed resins of two or more kinds are available. Among these, it is preferable to include the L-LDPE resin.

[0038] L-LDPE (L iner L ow D enaity P oly e tyiene)
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, as preferable α-olefins in terms of production suitability and physical strength and cost,
4-methylpentene-1, heptene-1, etc. are used.

The density is generally considered to be a low / medium density homopolyethylene resin, but 0.87 to 0.95 g / cm ³ is commercially available.
Many are within the range. Melt index is 0.1
Many are within the range of ~ 50g / 10min.

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 0.870-0.94
It was obtained by a liquid phase process and a gas phase process in which the carbon number of α-olefin was 6 to 8 (0 g / cm ³ (JIS K-6760)).

Specific examples of commercially available L-LDPE resins 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 Inc. ) MORETEC (Idemitsu Petrochemical)

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 is also preferable (these two products both use butene-1 having an α-olefin of 4 carbon atoms). Commercially available lubricants that do not adversely affect the photographic properties that can be added to the heat seal layer are described below.

Fatty Acid Amide Lubricants [Saturated Fatty Acid Amide Lubricants] Behenic Acid Amide Lubricants: Diamit KN (Nippon Kasei), etc. Stearic Acid Amide Lubricants: Armide HT (Lion Oil), Alfro-S-10 (Nippon Oil) , Fatty Acid Amide S (Kao), Diamid 200 (Nippon Kasei), Diamid AP-1 (Nippon Kasei), Amide S, Amide T
(Nitto Kagaku), Neutron-2 (Nippon Seika), etc. Palmitamide amide lubricant: Neutron S-18 (Nippon Seika), Amide P (Nitto Kagaku), etc. Laurate amide lubricant: Armide C (Lion. Akzo), Diamond (Nihon Kasei), etc.

[Unsaturated Fatty Acid Amide Lubricants] Erucamide amide lubricants: Alfuro-P-10 (Nippon Yushi), Neutron-S (Nippon Seika), LUBROL (IC)
・ I), Diamid L-200 (Nippon Kasei), etc. Oleic acid amide lubricants: Armoslip CP (Lion Akzo), Neutron (Nippon Seika), Neutron E-18 (Nippon Seika), Amide O (Nitto Kagaku), Diamond O-200, Diamond G-200 (Nippon Kasei),
Alfro-E-10 (NOF), fatty acid amide O (Kao), etc.

[Bis Fatty Acid Amide Lubricant] Methylenebisbehenic acid amide lubricant: Diamid N
K-bis (Nippon Kasei) etc. Methylenebis stearic acid amide lubricant: Diamid
200 Bis (Nippon Kasei), Armowax (Lion Akzo), Bisamide (Nitto Kasei), etc. Methylenebisoleic amide lubricant: Lubron O (Nippon Kasei), etc. Ethylenebisstearic amide lubricant: Armoslip EBS (Lion Hexamethylenebisstearic acid amide lubricant: Amide 65 (Kawaken Fine Chemicals) Hexamethylenebisoleic acid amide lubricant: Amide
60 (Kawaken Fine Chemicals), etc. [Monoalkylolamide lubricant] N- (2-hydroxyethyl) lauric acid amide lubricant: Tohoru N130 (Toho Chemical), etc. N- (2-hydroxyethyl) stearic amide lubricant:
Amizole (Kawaken Fine Chemicals), etc. N- (2-hydroxymethyl) stearic amide lubricants:
Methylol Amide (Nitto Kagaku) etc.

The amount of the above fatty acid amide-based lubricant added is 0.001 to 2% by weight, preferably 0.005 to 1% by weight, and particularly preferably 0.01 to 0.5% by weight. The second preferred lubricant after the fatty acid amide lubricant is a silicone lubricant. Although this silicon-based lubricant is expensive, it is optimal as a lubricant to be added to the heat-sealing layer of a light-shielding bag for photographic light-sensitive materials, which requires complete light-shielding properties for the following reasons. In particular, as a measure for deteriorating the heat-sealing property like a lubricant, the ethylene copolymer resin is 5% by weight or more, preferably 20% by weight, particularly preferably 50% by weight (even among the ethylene copolymer resins, it is an inexpensive and foreign substance). Ethylene / α-olefin copolymer resin, which has excellent sealing properties, hot tack properties, heat sealing strength, and physical strength, is the most preferable.) Addition of a heat sealing layer, heat resistance, and low Young's modulus to ensure high Young's modulus When the following silicone-based lubricant is added to the thermoplastic resin film layer provided on the outer surface of the molecular weight light-shielding bag, it exhibits excellent properties that conventional packaging materials for photographic light-sensitive materials do not have.

The silicone lubricant will be described in detail below.
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 / polyether-modified silicone, epoxy-modified silicone A silicone-based oil containing a modified siloxane bond such as amino-modified silicone, alcohol-modified silicone, and the like. Of these silicone-based oils, olefin-modified silicone, polyether-modified silicone, olefin / polyether-modified silicone and the like are particularly excellent. The silicone-based oil improves the coefficient of friction of the film in a heated state, reduces the sliding resistance generated during hot plate sealing by an automatic packaging machine, and prevents wrinkles from occurring, resulting in a beautiful appearance and a high degree of sealing. It is possible to form a basis for obtaining a film that retains the performance of the film and the adhesion that does not sag on the packaged object. 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 good. The addition amount varies depending on the type and purpose of use, but is 0.01 to 1.0% by weight. Preferably 0.03 to 0.5% by weight, particularly preferably 0.05
~ 0.3% by weight.

The effects of the addition of silicone oil are many as follows for the use of the present invention. 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 a 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.

Although the effect of improving lubricity is small, a polymerization catalyst for thermoplastic resins such as α-olefin resins is disclosed in JP-A-54-31.
A halogen compound is used as described in JP-A-84. As a result, halogen compounds remain in the resins used as the packaging material for the light-sensitive material of the present invention, particularly in the ethylene / α-olefin copolymer resin particularly preferably contained in the heat-sealing layer in contact with the photographic light-sensitive material. There is. As a result, it has been found that in a silver halide photographic light-sensitive material containing silver halide, these halogen compounds adversely affect the photographic properties, causing fog and abnormal sensitivity and gradation.

However, higher fatty acids such as lauric acid, stearic acid, ricinoleic acid, naphthenic acid, oleic acid, erucic acid and behenic acid and Li, Mg, Ca, Sr, Ba, Zn, C
0.001 to 10 of higher fatty acid metal salt (metal soap) which is a compound with a metal such as d, Sn and Pb, particularly zinc stearate, magnesium stearate and calcium stearate.
Addition of 0% by weight, preferably 0.005 to 5.0% by weight, particularly preferably 0.01 to 3.0% by weight improved the photographic properties (it was found that almost no fog occurred). For example, carbon black 3% by weight and zinc stearate 1.
By using L-LDPE resin film containing 5% by weight, after contacting with color photographic paper at 50 ° C and 80% RH for 5 days,
It was found that the unexpected effect that the fog density when developed was reduced from 0.12 to 0.02.

Furthermore, it has been found that the dispersibility of carbon black is improved, and the unexpected effect that the generation of lumps (foreign matter-like lumps) is reduced to 1/10 or less is simultaneously exhibited. Other lubricants which have a small effect of improving the lubricity but have the effects of improving the dispersibility of the light-shielding substance and the resin extrudability include the following. Hydrocarbon lubricants; liquid paraffin, natural paraffin, microwax, synthetic paraffin, polyethylene wax, polypropylene wax, fluorocarbon, etc. Fatty acid lubricants; higher fatty acids (preferably having 12 or more carbon atoms), oxyfatty acids, etc. ester lubricants; fatty acids Lower alcohol ester, polyhydric alcohol ester of fatty acid, polyglycol ester of fatty acid, fatty acid alcohol ester of fatty acid, etc. Alcohol-based lubricant; polyhydric alcohol, polyglycol,
Polyglycerol and the like, which have a small effect of improving the lubricity, are 0.01 to 10.0% by weight, preferably 0.05 to 6.0% by weight, particularly preferably 0.1% by weight.
Add ~ 3.0% by weight.

Examples of antistatic agents that can be added to the heat seal layer are shown below. I. Nonionic (= nonionic) (1) Alkylamine derivative: T-B103 (Matsumoto Yushi), T-B1
04 (Matsumoto Yushi) Alkylamide type polyoxyethylene alkylamine: Armostat 31
0 (Lion oil) Tertiary amine (lauryl amine): Armostat 400 (Lion oil) N, N-bis (2-hydroxyethyl cocoamine): Armostat
410 (Lion oil and fat) Tertiary amine: ANTISTATIC 273C, 273, 273E (FineOrg. Che
m) N-hydroxyhexadecyl-di-ethanol-amine: Belg. P. 654,
049 N-hydroxyoctadecyl-di-ethanol-amine: (National Dis
t.) (2) Fatty acid amide derivative: TB-115 (Matsumoto Yushi), Elegan P100 (Nippon Yushi), Eleek SM-2 (Yoshimura Yushi Kagaku) Oxalic acid-N, N'-distearylamide butyl ester: Hoechst poly Oxyethylene alkylamide (3) Ether type polyoxyethylene alkyl ether RO (CH ₂ CH ₂ O) nH Polyoxyethylene alkylphenyl ether Special nonionic type: Resistant 104, PE100, 116 ~ 118
(Daiichi Kogyo Seiyaku), Register PE132, 139 (Daiichi Kogyo Seiyaku), Elegan E115, Chemistat 1005 (Nippon Yushi), Eleek BM-1 (Yoshimura Yushi Kagaku), Electrostripper TS, TS2, 3,5, EA, EA2, 3 (Kao Soap) (4) Polyhydric alcohol ester type glycerin fatty acid ester: Monoguri ((Nippon camphor), TB
-123 (Matsumoto Yushi), Resist 113 (Daiichi Kogyo Seiyaku) Sorbitan fatty acid ester Special ester: Eleek BS-1 (Yoshimura Yushi Kagaku) 1-Hydroxyethyl-2-dodecylglyoxazoline: British cellophane

II. Anionic (1) Sulfonic acids Alkyl sulfonate RSO ₃ Na Alkylbenzene sulfonate Alkyl sulphate ROSO ₃ Na (2) Phosphate ester type alkyl phosphate

III. Cation system (1) Amide type cation: Resist PE300, 401, 402,
406, 411 (Daiichi Kogyo Seiyaku Co., Ltd.) (2) Quaternary ammonium salt Quaternary ammonium chloride Quaternary ammonium sulfate Quaternary ammonium nitrate Katimin CSM-9 (Yoshimura Oil Chemical), CATANA C609 (American cyanamide), Denon 314C (Maruhishi Yuka), Armostat 300 (Lion oil), 100V (Armor), Electrostripper-ES (Kao soap), Chemistat 20
09A (Nippon Yushi) Stearamido propyl-dimethyl-β-hydroxyethyl ammoniu
m nitrate: CATANAC / SN (American Theanamid)

IV. Zwitterion type (1) Alkyl petaine type: (2) Imidazoline type: Rheostat 53, 532 (Lion oil), AMS 53 (Lion oil), AMS 303, 313 (Lion oil) Alkyl imidazoline type (3) Metal salt: AMS 576 (Lion oil) Rheostat 826, 923 (Lion oil) (RNR'CH ₂ CH ₂ CH ₂ NCH ₂ COO) ₂ Mg R ≧ C, R ′ = H or (CH
₂₎ MCOO-: by Lion Yushi R = C ₃ ~ ₈ hydrocarbon, A = oxygen or imino group, M = organic amine or metal (4) alkylalanine type:

V. Conductive resin Polyvinylbenzyl type cation Polyacrylic acid type cation VI. Others: Register 204, 205 (Daiichi Kogyo Seiyaku),
Elegan 2E, 100E (Nippon Yushi), Chemistat 1002,
1003, 2010 (Nippon Yushi), Eleek 51 (Yoshimura Yushi Kagaku), ALROMINE RV-100 (Geigy) Above all non-ionic (nonionic) type antistatic agents as they have little adverse effect on photographic properties and human body. Is particularly preferable.

The antistatic agent will be specifically described. As the internal antistatic agent, any of a nonionic type, anionic type and a zwitterionic type may be used. Specifically, as the nonionic system, higher alcohol ethylene oxide adduct, alkylphenol ethylene oxide adduct,
Effective with esters (eg, esters of higher fatty acids and polyhydric alcohols, polyethylene-glycol esters of higher fatty acids, etc.), polyethers, amides (eg, higher fatty acid amides, dialkylamides, ethylene oxide adducts of higher fatty acid amides, etc.) Target.

Examples of the anionic system include alkylallylphosphonic acid, adipic acid, glutamic acid, alkylsulfonates, alkyl sulfates, polyoxyethylene alkyl phosphates, fatty acid salts, alkylbenzene sulfonates, alkylnaphthalene sulfonates, and sodium dialkyl. Sulfosuccinate is effective.

As the cationic system, amines (eg, alkylamine phosphate, Schiff base, amidoamine, polyethyleneimine, amidoamine / metal salt complex, amino acid alkyl ester, etc.), imidazolines, amine ethylene oxide adducts. , Quaternary ammonium salts and the like are preferable.

As for the zwitterionic system, N-acyl sarcosinate, aminocarboxylic acid derivatives, alanine type metal salt, imidazoline type metal salt, carboxylic acid type metal salt, dicarboxylic acid type metal salt, diamine type metal salt, A metal salt having an ethylene oxide group is preferable.

Inorganic electrolytes, metal powders, metal oxides, kaolins, silicates, carbon powders, and carbon fibers are also effective as the substances that do not fall into the above-mentioned categories. Graft polymerization and polymer blending are also effective.

Typical examples of the antistatic agent for external use include nonionic polyhydric alcohols (eg, glycerin, sorbit, polyethylene glycol, polyethylene oxide), polyhydric alcohol esters, and higher alcohol ethylene. -Oxide adducts, alkylphenol ethylene oxide adducts,
There are fatty acid ethylene oxide adducts, amides, amide oxide ethylene adducts, amine oxide ethylene adducts, and the like. In amphoteric systems, carboxylic acids (for example, alkylalanine) and sulfonic acids are effective. .

For the anionic type, a carboxylate, a sulfuric acid derivative (for example, an alkyl sulfonate, etc.) and a phosphoric acid derivative (for example, a phosphonic acid, a phosphoric acid ester, etc.) polyester derivative are preferable.

In the cationic system, amines (eg, alkylamine, amidoamine, esteramine, etc.), vinyl nitrogen derivative, quaternary ammonium salt (eg, ammonium salt containing amide group, ammonium salt containing ethylene oxide), acrylic acid There are ester derivatives, acrylic acid amide derivatives, vinyl ether derivatives and the like.

The addition amount of the antistatic agent as described above is 0.005
˜5.0 wt% is preferred and 0.01-2.0 wt% is especially preferred.

Examples of conductive materials that can be added to the heat seal layer are shown below. (1) Nonionic surfactant (representative component polyoxyethylene glycols) (2) Anionic surfactant (representative component polyoxyethylene glycols) (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 fibers (12) Metal fibers (13) Whiskers (potassium titanate, alumina nitride, alumina) (14) Inorganic compounds

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 ester of polyhydric alcohol Ethylene oxide adduct, and 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, 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 salt, etc.

Representative 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. Specific examples of particularly preferable conductive inorganic compounds such as carboxylic acid derivatives, imidazoline derivatives and petaine derivatives are described in JP-B-1-60815.

Representative examples of inorganic compounds are shown below. It is an inorganic salt compound consisting of a salt of at least one element selected from lithium, sodium, potassium, magnesium, calcium, lead, iron copper, zinc, aluminum, tin, strontium and manganese, and among them, in terms of effect and economy. Particularly preferably used from, sodium chloride, potassium chloride, magnesium chloride, calcium chloride, hydrochlorides such as iron chloride and copper chloride, nitrates such as potassium nitrate, magnesium nitrate, nitrates and zinc nitrate, sodium nitrate, aluminum sulfate, Examples thereof include sulfates such as magnesium sulfate and iron sulfate, acid salts such as potassium hydrogen phosphate and sodium phosphate, borate salts such as potassium borate, and bromides such as sodium bromide and lithium bromide. The compound may have water of crystallization.

The amount of the conductive substance added is preferably 0.005 to 30% by weight for the solid substance, 0.005 to 5.0% by weight for the substance easily bleeding out, and 0.01% for the solid substance.
~ 20% by weight, 0.01 ~ 2 for substances that easily bleed out.
0% by weight is particularly preferred. In addition, an antioxidant can be added to the packaging material for a light-sensitive material of the present invention in order to prevent the generation of substances that adversely affect the photographic properties (aldehyde and the like due to oxidative decomposition) and prevent coloring troubles. Representative examples of this antioxidant are shown below.

(A) Phenolic antioxidant 6-t-butyl-3-methylphenyl derivative, 2.6-di-t-butyl-P-cresol, t-butylphenol), 2.2'-methylenebis- (4 -Ethyl-6-t-butylphenol), 4.4'-butylidene bis (6-t-butyl-m-cresol), 4.4'-thiobis (6-t-butyl-m-cresol), 4.4- Dihydroxydiphenylcyclohexane, alkylated bisphenol,
Styrenated phenol, 2,6-di-t-butyl-4-methylphenol, n-octadecyl-3- (3 '・ 5'-di-t-butyl-4'-hydroxyphenyl) propinate, 2.2' -Methylenebis (4-methyl-6-t-butylphenol), 4.4'-thiobis (3-methyl-6-t-butylphenyl), 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, 1,3,5 trimethyl-2,4,6-tris (3,5-di-t-butyl-4hydroxybenzyl) benzene, tetrakis [methylene-3 (3 ', 5'-di- t-butyl-4'-
(Hydroxyphenyl) propionate] methane, etc. (b) Ketone amine condensation-type antioxidant 6-ethoxy-2 ・ 2 ・ 4-trimethyl-1,2-dihydroquinoline,
Polymers of 2,2,4-trimethyl-1,2-dihydroquinoline, trimethyldihydroquinoline derivatives, etc. (c) Acrylic amine antioxidants 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) Phosphite-based antioxidants, etc.

The amount of the above antioxidant added is 0.00
1 to 1.0% by weight is preferable, and 0.005 to 0.25% by weight is particularly preferable. If the antioxidant having a reducing action exceeds 1.0% by weight, a problem occurs in photographic properties.

In order to improve the adhesive strength between the metal vapor deposition film and the film for processing the metal vapor deposition film, the adhesive strength between the metal foil and the dust-free flexible sheet, etc., physical surface treatment or AC agent treatment is performed. You can

Representative examples of physical surface treatment are shown below. Flame (flame) treatment; high running cost and 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 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. The adhesive strength is improved even if the resin temperature for the extrusion laminate 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 (Anch) which is a general term for adhesion promoters or crosslinking agents used in the laminating industry.
or Coating Agent) is applied. This AC agent is different from a simple adhesive and is also called a Primer or an Adhesine Promoter, etc., in the sense that it is chemically bonded and is distinguished from the adhesive. Representative examples of AC agents are shown below. (1) Organic titanate (titanium-based) AC agent Tetra-propyl-titanate or Tetra-isobutyl-titana
te as the main component, Tetra-stearyl- as a hydrolysis regulator
Use by adding titanate. (2) a relatively high polymerization degree polyethylene imine (imine) AC agent polyethyleneimine (-CH ₂ -CH ₂ -NH-n) 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 those that use a polymer having an isocyanate group alone (one-pack type) and those that use it in combination with a polyester having an OH group (two-pack type), both of which are chemicals such as crosslinking. The 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 the coating method of the AC agent, a gravure roll coating method, a kiss roll coating method, a bar coating method,
It may be selected from various conventionally known coating methods such as an air knife coating method and a slide coating method.

A light-shielding bag having a complete light-shielding property is made by using the packaging material for the photosensitive material as described above. The completely light-shielding light-shielding bag may be a light-shielding bag having any known shape and size, such as a single flat bag, a double flat bag, a single gusset bag, and a double gusset 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 or a high frequency adhering method. It is also possible to make a bag by combining an adhesive method using an adhesive or a pressure-sensitive adhesive, an adhesive method using a pressure-sensitive / heat-sensitive adhesive, or a combination of two or more of these adhesive methods. In addition, the light-sensitive material packaging material of the present invention is a completely light-shielding leader paper.
It can be used for various light-sensitive material packaging applications such as the packaging material for bright room loading described in Japanese Patent No. 72347.

Photosensitive materials that can be used for packaging the packaging material for photosensitive materials 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. Photothermographic materials: photothermographic color photographic materials, photothermographic black and white photographic materials, such as Japanese Patent Publication No. 43-4921, No. 43-4924, "Basics of Photographic Engineering", Silver Salt Photograph (1879) 553 to 555, published by Corona Publishing Co., Ltd., and Research Tis Closure, June 1978, pages 9 to 15 (RD-17029). Further, JP-A-59-12431 and JP-A-6-12431
0-2950, 61-52643 and U.S. Pat.
Transfer-type heat-developable color light-sensitive material described in 4,267 Specification Photosensitive / thermosensitive recording material: Photothermography (light-sensitive thermal image forming method) described in JP-A-3-72358 Recording materials Diazonium photographic light-sensitive material: 4-morpholinobenzenediazonium chloride film, microfilm, copying film, printing plate material, etc.Azide, diazide photographic light-sensitive material: para-azidobenzoede, 4,4'diazidostilbene, etc. Photosensitive materials containing, for example, copying films, printing plates, etc.Quinonediazide photographic photosensitive materials: ortho-quinonediazide, ortho-naphthoquinonediazide compounds, such as benzoquinone (1,2) -diazide- (2) -4-phenyl sulfonate Photosensitive materials containing ether, etc., such as printing plates, copying films, adhesion films, etc. Photopolymers -: Photosensitive material containing vinyl monomer,
Printing plate material, adhesion film, etc. Polyvinyl cinnamate type: For example, printing plate film, photosensitive resist for IC, etc. Further, various bags that require sealing property, such as rice bags, cement bags, feed bags, fertilizer bags, Applicable to grocery bags.

[0083]

In the present invention, the reinforced sheet mainly improves the easy-opening property when the opening notch is formed and also improves the contradictory physical strength to prevent the occurrence of pinholes and curls. Further, the metal has improved antistatic property, moisture proof property, gas barrier property, and light shielding property. By setting the peel strength between the reinforcing sheet and the metal layer to 300 g / 15 mm width or more, the pinhole resistance is improved and the contradictory easy-opening property is improved.

[0084]

EXAMPLE An example of a packaging material for a photosensitive material according to the present invention will be described with reference to FIGS. 1 to 3 are partial cross-sectional views showing a layer structure of a packaging material for a photosensitive material, and FIGS. 4 and 5 are plan views of a reinforcing sheet used for the packaging material for a photosensitive material.

In the packaging material for a photosensitive material shown in FIG. 1, an aluminum vapor-deposited flexible sheet 4 obtained by vapor-depositing an aluminum vapor-deposited film 3 as a metal layer on a dust-free flexible sheet layer 2 is formed on one surface of a reinforced sheet 1. , Adhesive layer 5
The aluminum vapor deposition film 3 is laminated so as to be on the dust-free flexible sheet layer 3 side, and the heat seal layer 6 is directly laminated on the other surface.

The photosensitive material packaging material shown in FIG. 2 is obtained by laminating a heat-sealing layer 6a containing a light-shielding substance via an adhesive layer 7 instead of directly laminating the heat-sealing layer in FIG. Is.

In the packaging material for a photosensitive material shown in FIG. 3, the metal layer 9 and the dust-free flexible sheet layer 2 are laminated on one surface of the reinforcing sheet 1 with the adhesive layers 5 and 5, and the other side. The heat-sealing layer 6a containing a light-shielding substance is directly laminated on the surface.

In the reinforced sheet 1 shown in FIG. 4, the vertical strips 11 are arranged in parallel at intervals of 1 mm or more, and the horizontal strips 11 are used.
The vertical strips 11 are arranged in parallel with each other at intervals of 1 mm or more, and are formed in a lattice shape as a whole, and the overlapping portions of the vertical strips 11 and the horizontal strips 12 are melt-bonded to each other.

The reinforcing sheet 1 shown in FIG. 5 is formed in a knitted shape by alternately stacking the vertical strips 11 and the horizontal strips 12.

FIG. 6 is a plan view of an embodiment of a light-shielding bag having a perfect light-shielding property according to the present invention. The light-shielding bag 20 having a completely light-shielding property shown in this figure has two heat-sealing packaging materials superposed on each other and heat-sealed around each other to form a heat-sealing portion 21, in which the photographic light-sensitive material 22 is stored. There is. In addition, triangular notches (opening notches) 23 are formed continuously at both ends for triggering opening. This light-shielding bag is excellent in easy-opening property in spite of its excellent physical strength, and is most suitable for a light-shielding bag that requires complete light-shielding property for a photosensitive material having two contradictory properties at the same time. It was an excellent product that was not put into practical use in the past or even now.

Example 1 The layer structure is as shown in FIG. 1 and the reinforcing sheet is as shown in FIG. The reinforced sheet 1 has the same vertical and horizontal strips, and the vertical strip 11 having a horizontal tear strength / vertical tear strength of 2 is a width 6 mm, a length 500,000 mm, and a horizontal strip 12 Is a uniaxially stretched high-density polyethylene resin film with a width of 6 mm, a laminate width of 1,000 mm, and a thickness of 20 μm. The intervals between the strips are 1 mm or more. The vertical strip 11 and the horizontal strip 12 Has an adhesive strength of 30 g / 15 cm width.

Aluminum vapor-deposited flexible sheet 4
Is formed of an aluminum vacuum-deposited biaxially stretched polyester resin film, the dust-free flexible sheet layer 2 is formed of a 12 μm-thick biaxially stretched polyester resin film, and the aluminum vapor deposition film 3 is formed by a vacuum vapor deposition method. It is formed with a thickness of 600Å.

The adhesive layer 5 was composed of a urethane type adhesive which is an adhesive for dry lamination, and the peel strength between the aluminum vapor deposition film 3 and the reinforcing sheet 1 was 478 g / 15 cm.
The heat seal layer 6 is a polyolefin resin composition comprising 79.7% by weight of a high-pressure low-density homopolyethylene resin, 20% by weight of an acid-modified L-LDPE resin, and 0.3% by weight of a nonionic antistatic agent at a resin temperature of 310 ° C. Thickness of 30μ using T-die
m is formed by extrusion lamination.

The light-shielding bag using the packaging material for the photosensitive material as described above does not cause pinholes even when it is bent, dropped, pulled, etc. in the packaging process, the transportation process, etc., and
Almost no dust or curl was generated. In addition, when the notch (opening notch) was formed, it could be easily torn in a straight line.

Example 2 The layer structure is as shown in FIG. 2 and the reinforcing sheet is as shown in FIG. The reinforcing sheet 1, the aluminum vapor-deposited flexible sheet 4 (the dust-free flexible sheet layer 2 and the aluminum vapor-deposited film 3) and the adhesive layer 5 are the same as those in Example 1.
Is the same as

The heat seal layer 6a comprises 86.5% by weight of ethylene-4 methylpentene-1 copolymer resin, 10% by weight of acid-modified high-pressure low-density homopolyethylene resin, 3% by weight of carbon black, and 0.1% by weight of antioxidant. An ethylene copolymer resin containing 0.3% by weight of calcium stearate and 0.1% by weight of erucic acid amide was formed at a resin temperature of 190 ° C. by an inflation film forming method to a thickness of 50 μm.

The adhesive layer 7 is composed of 50% by weight of a high-pressure low-density homopolyethylene resin and an ethylene / butene-1 copolymer resin.
A polyolefin resin composition consisting of 40% by weight and 10% by weight of acid-modified high-pressure low-density homopolyethylene resin was formed by extrusion lamination at a resin temperature of 320 ° C. to a thickness of 30 μm using a T-die.

The light-shielding bag using the packaging material for the photosensitive material as described above does not cause pinholes even when it is bent, dropped, pulled, etc. in the packaging process, the transportation process, etc., and
Almost no dust or curl was generated. Further, when the notch (opening notch) was formed, it could be easily torn in a straight line.

Example 3 The layer structure is as shown in FIG. 1 and the reinforcing sheet is as shown in FIG. The adhesive layer 5 comprises 79.9% by weight of a high-pressure low-density homopolyethylene resin, 20% by weight of an acid-modified high-pressure low-density homopolyethylene resin, and 0.1% by weight of a phenolic antioxidant.
A resin composition consisting of wt% was formed by extrusion lamination at a resin temperature of 320 ° C. using a T-die to a thickness of 20 μm.

The other structure is the same as that of the first embodiment.
The light-shielding bag using the packaging material for photosensitive materials as described above does not generate pinholes even when bent, dropped, pulled, etc. in the packaging process, transportation process, etc., and hardly generates dust or curl. It was Further, when the notch (opening notch) was formed, it could be easily torn in a straight line.

Example 4 The layer structure is as shown in FIG. 3 and the reinforcing sheet is as shown in FIG. Reinforcement sheet 1, vertical strip 11 has a transverse tear strength / longitudinal tear strength of 25, width 7 mm, length
Uniaxially stretched high density polyethylene resin of 500,000 mm, thickness of 35 μm, horizontal strip 12 with transverse tear strength / longitudinal tear strength of 10 and width of 5 mm, length of laminate width of 10,000 mm and thickness of 20 μm. It is made of film.

The dust-free flexible sheet layer 2 has a thickness of 12
It is formed of a biaxially stretched polyester resin film of μm. The metal layer 9 is formed of an aluminum foil having a thickness of 9 μm. The adhesive layer 10 is 15% by weight of acid-modified high-pressure low-density homopolyethylene resin, MI is 5.2 g / 10 minutes, and has a density of 0.9.
High density low density homopolyethylene resin of 1g / cm ³ 84.9% by weight
A resin composition comprising 0.05% by weight of a phenol-based antioxidant and 0.05% by weight of a phosphorus-based antioxidant was formed by extrusion lamination to a thickness of 15 μm using a T-die at a resin temperature of 320 ° C.

The heat seal layer 6a is made of an ethylene / butene-1 copolymer resin 40 having an MI of 15 g / 10 minutes and a density of 0.92 g / cm ^3.
% By weight, MI of 5.2 g / 10 min, density of 0.917 g / cm ³ of high-pressure low-density homopolyethylene resin 56.9% by weight, furnace carbon black 3% by weight, phenolic antioxidant 0.05
A resin composition composed of 50% by weight and 0.05% by weight of synthetic silica was formed by extrusion lamination at a resin temperature of 320 ° C. to a thickness of 30 μm using a T-die.

The light-shielding bag using the packaging material for the photosensitive material as described above does not generate pinholes even when it is bent, dropped, pulled, etc. in the packaging process, the transportation process, etc., and
Almost no dust or curl was generated. Further, when the notch (opening notch) was formed, it could be easily torn in a straight line (a light-shielding bag having a notch (opening notch) in the longitudinal direction was particularly excellent in easy-opening property.

Example 5 Except that the reinforced sheet 1 was made into a wallif (made by Nisseki Chemical KK),
Same as Example 2. The light-shielding bag using the packaging material for photosensitive materials as described above does not generate pinholes even when folded, dropped, pulled, etc. in the packaging process, transportation process, etc. Did not occur. Moreover, when a notch (opening notch) was formed, it could be easily torn.

Example 6 The same as Example 1 except that the reinforcing sheet 1 was a spunbond nonwoven fabric having a thickness of 50 μm (Tyvek manufactured by UCC, USA). The light-shielding bag using the packaging material for photosensitive materials as described above does not generate pinholes even when bent, dropped, pulled, etc. in the packaging process, transportation process, etc., less dust is generated, and almost no curling occurs. Did not occur.

[0107]

The present invention makes it possible to prevent pinholes from being generated, and to prevent dusting and curling even when subjected to extremely rough handling in a packaging process, a transportation process and the like. Moreover, by forming a notch (opening notch), it has an easy opening property. Therefore, the light-sensitive material to be packaged can always be kept in a good condition.

[Brief description of drawings]

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

FIG. 2 is a partial cross-sectional view showing the layer structure of another embodiment of the packaging material for photosensitive material of the present invention.

FIG. 3 is a partial cross-sectional view showing the layer structure of another embodiment of the packaging material for photosensitive material of the present invention.

FIG. 4 is a partial plan view of a reinforcing sheet used in an example of the packaging material for a photosensitive material of the present invention.

FIG. 5 is a partial plan view of a reinforcing sheet used in another embodiment of the packaging material for photosensitive material of the present invention.

FIG. 6 is a plan view of an embodiment of a completely light-shielding bag of the present invention.

[Explanation of symbols]

1 ... Reinforcement sheet 2 ... Dust-free flexible sheet layer 3 ... Aluminum vapor deposition film (metal layer) (metal thin film processing layer) 4 ... Aluminum vapor deposition flexible sheet (metal thin film processing flexible sheet) 5 ... Adhesive layer 6, 6a ... Heat Seal layer 7 ... Adhesive layer 9 ... Metal layer 11 ... Vertical strip 12 ... Horizontal strip 20 ... Shade bag 23 ... Notch (opening notch)

Claims (5)

[Claims] 1. A metal layer, a dust-free flexible sheet laminated on one surface of the metal layer, and a reinforcing sheet laminated on the other surface of the metal layer via an adhesive layer. The reinforcing sheet is formed by vertically and horizontally arranging strips made of a thermoplastic resin having dimensions of length / width ≧ 3.
A packaging material for a photosensitive material, characterized in that the peel strength between the reinforcing sheet and the metal layer is 300 g / 15 mm width or more. 2. The packaging material for a photosensitive material according to claim 1, wherein the reinforced sheet is laminated with a heat seal layer containing at least one of a lubricant, an antistatic agent and a conductive substance. 3. The packaging material for a photosensitive material according to claim 1, wherein at least one layer contains a light-shielding substance. 4. The value of the tear strength in the transverse direction / the tear strength in the longitudinal direction of the strip material of the reinforcing sheet is 1.2 or more.
2. Packaging material for photosensitive material according to 2 or 3 5. A light-shielding bag for a light-sensitive material, characterized in that it is made of the packaging material for a light-sensitive material according to claim 1, 2, 3 or 4.