JPH02186338A - Packing material for photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain a low-cost packing material having high physical strength and superior light shielding property by laminating a biaxially stretched thermoplastic resin film with vapor-deposited Al, a light shielding polyolefin resin film and a heat resistant flexible sheet having a high Young's modulus. CONSTITUTION:A biaxially stretched thermoplastic resin film I with vapor- deposited Al is formed by vapor-depositing an Al film 2 on a biaxially stretched thermoplastic resin film 1. A light shielding polyolefin resin film 5a is laminated on the film 1 side of the film I with an adhesive layer 3 in-between and a flexible sheet 6 is laminated on the Al film 2 side of the film I with a light shielding polyolefin resin adhesive layer 4a in-between. Since the layer 4a is hardly damaged by shock and a sharp edge, it can be formed by a tandem lamination system. A low-cost tough packing material having superior antistatic and light shielding properties is obtd.

Description

[Detailed description of the invention] [Industrial application field] The present invention relates to packaging materials for photographic materials.

[Conventional technology]

Various types of packaging materials for photographic materials have been widely put into practical use, and various performances are required depending on the intended use.

In addition to completely blocking light, packaging materials for photographic materials that lose their quality value when exposed to light include photographic properties, packaging material slit suitability, gas barrier properties,
Light blocking properties, moisture proof properties, rigidity, physical strength (breaking strength, tear strength, impact drilling strength, gelbo test strength, abrasion strength, etc.)
, heat sealability (heat seal strength, hot tack property, contaminant sealing property, etc.), antistatic property, flatness, sliding property, etc.

However, it is extremely difficult to provide all of these characteristics with a single film material, and conventionally packaging materials consisting of multiple layers have been used.
The invention disclosed in Publication No. 00 is a packaging bag made of a packaging material in which a polyester film layer is placed on the outside of an aluminum layer, and a polyolefin resin layer containing a light shielding material and a nonionic antistatic agent is placed inside.

In addition, the present inventor also provided water-absorbing, dust-free, and heat-resistant flexible sheet layers on both sides of the metal layer via adhesive layers, carbon black, antioxidant, and linear low-density polyethylene (hereinafter referred to as L-LDPE). proposed a gusset bag using a packaging material laminated with a polyolefin resin film layer containing resin (denoted as ) (Japanese Unexamined Patent Publication No. 63-272668).

[Problem to be solved by the invention]

However, conventional packaging materials are prone to breakage and pinholes due to impacts and photosensitive materials with sharp edges, especially in areas where pressure is applied more than other areas, such as the gusset of the bottom heat-sealed part of a gusset bag. However, since heat seal breakage easily occurs, folding is required, and the MIIi antistatic properties of the outer layer are not perfect.

SUMMARY OF THE INVENTION An object of the present invention is to solve the above-mentioned problems, and to provide a packaging material that has physical strength that can be used without folding the bottom seal of a gazette bag, has excellent light-shielding properties, and is inexpensive.

[Means for Solving the Problems] In order to achieve the above object, the present invention provides a packaging material in which an aluminum vapor-deposited biaxially stretched thermoplastic resin film, a light-shielding polyolefin resin film, and a heat-resistant high Young's modulus flexible sheet are laminated. The problem was solved by using .

That is, the packaging material for photographic light-sensitive materials of the present invention includes an aluminum vapor-deposited biaxially stretched thermoplastic resin film, which is laminated on one side of the aluminum vapor-deposited biaxially stretched thermoplastic resin film, and is laminated with an ethylene copolymer resin, carbon black, and blocking material. a light-shielding polyolefin resin film containing a light-blocking substance; a flexible sheet layer laminated on the other side of the aluminum vapor-deposited biaxially stretched thermoplastic resin film and having heat resistance and a high Young's modulus; and an aluminum vapor-deposited biaxial It is characterized by comprising a light-shielding polyolefin resin adhesive layer containing a light-shielding substance to which a stretched thermoplastic resin film is adhered.

Various commercially available aluminum vapor-deposited biaxially stretched thermoplastic resin films used in the present invention can also be used. An aluminum vapor-deposited film is deposited on a biaxially stretched thermoplastic resin film with excellent physical strength. It is processed.

This aluminum vapor-deposited biaxially stretched thermoplastic resin film has excellent light-shielding properties, moisture-proofing properties, gas barrier properties, impact puncture strength, and bursting strength, and has a higher Young's modulus than the light-shielding polyolefin resin adhesive layer, and is used as an intermediate layer on the outside of packaging materials. It also has excellent resistance to damage from internal impacts and objects with sharp edges.

The biaxially stretched thermoplastic resin film is subjected to a known biaxial stretching method such as simultaneous biaxial stretching or sequential biaxial stretching.
This film has a higher Young's modulus than the light-shielding polyolefin resin adhesive layer that has been stretched 1.5 to 20 times, preferably 3 to 15 times, in the longitudinal direction (MD force direction and horizontal direction (CD direction). Thermoplastic resins used include polyester resin, polyamide (nylon) resin, polyethylene resin, polystyrene resin, polypropylene resin, polyolefin copolymer resin, polyvinyl chloride resin, polyvinylidene chloride resin, EVAL resin, vinylon resin, and these resins. Copolymer resins of resins and other resins (including not only binary copolymer resins but also tertiary or more copolymer resins, the copolymer type may be either random copolymerization or block copolymerization, ), mixed resins of the above resins and other resins, etc.

The polyester resins include resins synthesized from dimethyl terephthalate and ethylene glycol, dimethyl terephthalate and 1,4-cyclohexanedimethanol, dimethyl terephthalate, dimethyl isophthalate, and the like. Polyamide resins include nylon 6, nylon 66, nylon 12, nylon 11, and nylon 6-6.
6 copolymer resin, etc.

Then, these resins are biaxially stretched using a T-die film molding machine or an inflation silane film molding machine to form a film.

This biaxially oriented thermoplastic resin film has a thickness of 5 to 50% in order to reduce the thickness of the packaging material, reduce costs, and ensure physical strength.
A thickness of 70 is preferable; if the thickness is less than 5, wrinkles or cuts will easily occur during the lamination process, and if it exceeds 70, the rigidity will be too high, resulting in poor bag-making properties, Gelbo test strength, and handling, as well as being expensive. This makes it undesirable as a packaging material for photographic materials.

In addition, biaxially stretched thermoplastic resin film can be used as a single layer as well.
It may be a multilayer coextruded film with two or more layers, vertical,
It is desirable that the difference in elongation at break in the horizontal direction is within 2 times, preferably within 1.5 times, in order to make it easy to tear by hand without any difference in the length and width.

The thickness of the aluminum vapor-deposited film is preferably 55 to 1,200 people from the viewpoint of physical strength as a laminate, light shielding property, antistatic property, moisture proofing property, gas barrier property, cost, and quality. It is not possible to reduce the electrification generated on both sides of the aluminum vapor deposited film, and if the thickness exceeds 1,200 mm, the antistatic, gas barrier properties,
Moisture-proofing and light-shielding properties can be ensured, but there are problems in terms of cost and vacuum deposition methods such as deterioration of the biaxially stretched thermoplastic resin film due to heating and reduction in physical strength of the finished laminated film. In particular, the thickness is preferably 80 to 800 thickness, more preferably 100 to 600 thickness for use as a packaging material for ordinary photographic materials.

The aluminum evaporation film is deposited by a vacuum evaporation method, a sputtering method, an ion blating method, an electron beam evaporation method, or the like.

In addition, the aluminum vapor-deposited film may be vapor-deposited not only on one side but also on both sides of the biaxially stretched thermoplastic resin film. An anchor coating agent may be applied to the surface of the biaxially stretched thermoplastic resin film on which the aluminum vapor-deposited film is deposited, or a corona discharge It is preferable to perform treatment, frame treatment, etc. because it can also increase the adhesive strength of the aluminum vapor-deposited film.

A protective layer can be provided on the aluminum vapor-deposited film to prevent scratching and peeling. This protective layer may be suitably used such as butyral resin, acrylic resin, cellulose resin such as cellulose acetate, urethane resin, epoxy resin, polyester resin, ionomer resin, ethylene-ethyl acrylate copolymer resin, various polyethylene resins, polypropylene resin, etc. Resins can be used.

Further, wax, gelatin, polyvinyl alcohol, etc. can also be used.

The protective layer is preferably formed with an extremely thin thickness, and even when it is formed by extrusion lamination, if the thickness is not less than 50, static electricity will not be removed satisfactorily.

When the thickness is reduced to 5β or less by a known solution coating method, spray coating method, etc., the aluminum vapor deposited film can be protected and the effect of removing static electricity is also great.

A light-shielding polyolefin resin film is laminated on one side of the aluminum vapor-deposited biaxially stretched thermoplastic resin film. This light-shielding polyolefin resin film contains ethylene copolymer resin, carbon black, and a profking prevention substance, and prevents light from entering due to the piping effect from the cross section and poor light-shielding properties due to the generation of pinholes.
This is to improve heat sealing properties (heat sealing strength, heat sealing strength retention over time, hot tack properties, contaminant sealing properties) and physical strength.

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 camellia butter (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 (1) Ionomer resin (resin in which a copolymer of ethylene and unsaturated acid is cross-linked with metal such as zinc) (12) Ethylene-α-olefin copolymer resin (hereinafter referred to as L) -LDPE resin) (13) Ethylene-propylene-butene-1 terpolymer resin Among ethylene copolymer resins, film formability and heat sealability are good, and bag-breaking strength, impact puncturing strength, and tearing strength is large, so L-LDPE resin and EEA resin are preferred.

L-L D P E (Liner Low Den
Polyethylene resin is called the third polyethylene resin, and is a low-cost, high-strength resin that meets the demands of the times for energy and resource conservation, combining the advantages of both medium-low pressure and high-pressure polyethylene resins. .

This resin is a copolymer obtained by copolymerizing ethylene with an α-olefin having 3 to 13 carbon atoms, preferably 4 to 10 carbon atoms, using a low-pressure method or a high-pressure modification method, and has a linear structure with short branches in a linear chain. It is a polyethylene resin. Preferred α-olefins in terms of physical strength and cost include 1-butene, 1-octene, 1-hexene-1,4-methylpentene, and 1-heptene.

The density is generally considered to be that of low-medium density polyethylene resin, but commercially available products are often in the range of 0.87 to 0.95 g/d, and the melt index is 0.1 to 50 g.
/10 minutes.

The polymerization process for L-LDPE resin includes a gas phase method using a medium/low pressure device, a liquid phase method, and an ionic polymerization method using a high pressure improving device.

Specific examples of L-LDPE resin are shown below.

Ethylene-butene-1 copolymer resin G resin and NUC-FLX (UCC) Dowlex (Dow Chemical) Sflare
(Dupont Canada) Marex
(Philips) Stamilex (DSM)
Company) F-selen VL (Sumitomo Chemical) Neozex (Mitsui Petrochemical) Mitsubishi Polyethylene L
L (Mitsubishi Petrochemical) 8 stone Nilex (Nippon Petrochemical) NUC polyethylene-LL (Nippon Unicar) Idemitsu polyethylene L (Idemitsu Petrochemical) Ethylene-hexene-1 copolymer resin TUFLIN (UCC) TUFTI (
ENE (Nippon Unicar) Ethylene/4-methylpentene-1 copolymer resin Urtozex (
Mitsui Petrochemical) Ethylene-octene-1 copolymer resin Stamilefx (DSM) Dowlex (Dow Chemical) Sflare (DuPont Canada) MORETEC (Idemitsu Petrochemical) Among these L-LDPE resins, physical strength and Particularly preferred from the viewpoint of heat seal strength and film formability are those with a melt index (hereinafter referred to as M1) of 0.8 to 10 g.
/10 minutes (JIS K-6760), density is 06870
~0.940g/cdcJ1s K-6760), and α-olefins having 6 to 8 carbon atoms were obtained by a liquid phase process and a gas phase process.

Particularly preferred representative examples include product names such as Mitsui Petrochemicals Shino Urtozex, in which 4-methylpentene-1 having 6 carbon atoms is introduced into polyethylene as an α-olefin side chain, and α-olefin [carbon as 111N]. Idemitsu Petrochemical's MORET introduced several 8 octene-1
There are EC and DSM's Stamilex and Dow Chemical's Dowlex (all of the above four companies' products are LDPE resins obtained by a liquid phase process).

A typical example of a preferred product obtained by a low-pressure gas phase process is Nippon Unicar's TUF, which has hexene-1 with 6 carbon atoms introduced as an α-olefin side chain.
Examples include LIN and UCC's TUFTHENE.

In addition, recently released ultra-low density linear low density polyethylene resins with a density of less than 0.910 g/d, such as UCC's NUC-FLX and Sumitomo Chemical's F-selen VL, are also preferable (both of the above two companies' products are α-olefins). (using butene-1 having 4 carbon atoms).

Typical manufacturers of the EEA resin include Union Carbide (USA), Nippon Unicar (2), Mitsubishi Yuka (2), Sumitomo Chemical (2), and Mitsui Polychemical (2).

As a specific example, EEA currently on the market at Nippon Unicar ■
Representative brand names of resins, their comonomer content, melt index, and density are shown (Comonomer content NUC
6% or more according to the test method).

Nippon Unicar - List of commercially available EEA resins The above-mentioned carbon black is mainly used to ensure light-shielding properties, as well as to prevent oxidation and improve the physical strength of the resin.

Depending on the raw material, this carbon black can include gas black, oil furnace black, ketschen black, anthracene black, acetylene black, oil smoke, pine smoke, furnace black, channel black, graphite,
It is classified into thermal black, lamp black, etc.

In the packaging material of the present invention, furnace carbon black is preferable for the purpose of improving light-shielding properties, cost, and physical properties, and acetylene carbon black and Ketchiene carbon black are preferable as light-shielding substances that are expensive but have an antistatic effect.The former may be used if necessary. It is also preferable to mix the latter according to the required characteristics.However, Ketchiene carbon black tends to cause fogging (so, countermeasures may be necessary in the selection of raw materials and photographic emulsions.On the other hand, when using these carbon blacks, Among them, pH6.O~8.5,
Acetylene carbon black or furnace carbon black with an average particle size of 15 to 50 W, a volatile content of 3% or less, and an oil absorption of 60 cc/100 g or more is particularly preferred. By using such carbon black, fogging can be reduced. It is possible to produce a packaging material that has a number of advantages, such as less increase or decrease in photosensitivity, high light-shielding ability, excellent dispersibility, and less occurrence of spots, fish eyes, and pinholes.

Carbon black can be used in various forms such as dry color liquid color, paste color, masterbatch pellet, compound color pellet, and granular color pellet, but masterbatch pellets are most preferable in terms of usability and cost.For example, coloring is done using the masterbatch method. When a masterbatch pellet with a carbon concentration of 40% is used as a pellet to color a light-shielding polyolefin resin film and a light-shielding polyolefin resin adhesive, it can be produced at a cost of 30% or more compared to coloring using a compound method.

Mitsubishi Chemical Industries KK and Asahi Carbon KK are major domestic carbon black suppliers.

Tokai Carbon KK, Showa Cabot KK, Electrochemical KK
, Hokutan Carbon KK, Nippon Steel Chemical Industry KK.

Examples include Toyo Continental Carbon Co., Ltd.

Representative commercial product names of anti-blocking substances are shown below.

(1) Inorganic (a) Silica: Thyroid 244 (Fuji Davison), Thyroid 978
(Davison), Celite High Flow Floss (J-ohns-Manville Ie), Celite Super Floss (Johns-Manville), AER
OSIL 200 (Japan Aerosil), AEROSIL
300 (Japan Aerosil), Super Light (Konno Shoten), Snow Light (Mouri Shoten), Radio Light W (Showa Kagaku) (b) Calcium silicate; Microcell C (Jobns-Manvil Ie),
Microcell T-38 (Johns4anville)
(c) Aluminum silicate; P-820 (Deggossa), Perlite 54 (Toi Pearlite), magnesium gayate in talc) (d)
Talc; PKN (Hayashi Kasei), Micro White (Hayashi Kasei) (e) Calcium carbonate: Softon SS (DOW) (2) Organic higher fatty acid polyvinyl ester, dicarboxylic acid ester amide, n-octadecyl urea, Eagle, "-Geo" Railoxamide In addition, typical examples of surfactants that have an anti-bronching effect and are preferably incorporated from the viewpoint of preventing static include, as cationic surfactants, primary amine salts, tertiary amine salts, , quaternary ammonium compounds, and pyridine derivatives; anionic activators include fatty acid metal salts, alkyl sulfate ester salts, alkylnaphthalene sulfonates, and succinate sulfonates; nonionic activators include many There are partial fatty acid esters of alcohols, ethylene oxide adducts of fatty alcohols, ethylene oxide adducts of fatty acids, ethylene oxide adducts of fatty aminos or fatty acid amide, ethylene oxide adducts of alkylphenols, and ethylene oxide adducts of alkylnaphthols. Examples of amphoteric active agents include carboxylic acid derivatives and imidacillin derivatives.

A heat-resistant and high Young's modulus flexible sheet is laminated on the other side of the aluminum-bound biaxially stretched thermoplastic #M resin film, and this flexible sheet has the following properties:
It has excellent bag-making suitability and curling prevention, and provides resistance to external impacts and sharp edges.

As this flexible sheet, there are known films made of various thermoplastic resin films, such as various polyethylene resins, polyvinyl chloride resins, polyvinylidene chloride resins, polyamide resins, polycarbonate resins, fluorocarbon resins, polyester resins, etc., and modified films thereof. A resin film is used.

Further, known flexible sheets such as cellulose acetate film, cellophane, polyvinyl alcohol film, various papers, various nonwoven fabrics, and warif can also be used.

When forming the outermost layer of packaging materials for photosensitive materials, bleached kraft paper, synthetic paper, nonwoven fabric, cellophane, etc. are suitable for printing and writing, and have strong physical strength (and excellent bag-making suitability). It is particularly preferable because it does not melt and does not generate pinholes.

The heat resistance of this flexible sheet should be at least as high as not melting during heat sealing, preferably 10°C higher than that of the light-shielding polyolefin resin film.
This is a flexible sheet with a melting point as high as above.

In addition, in the present invention, the high Young's modulus of the flexible sheet means that the flexible sheet has a higher Young's modulus than that of the light-shielding polyolefin resin adhesive layer.
Preferably, the Young's modulus is 1.5 times or more, and the temperature is 20℃65
It refers to the property expressed in units of 47115 g in the machine direction (MD), determined by a measuring method according to ASTM D-882 under the measurement conditions of %RH.

Specifically, 60kg/sn' or more, preferably 90K
g/+u+” or more.

The aluminum vapor-deposited biaxially stretched thermoplastic resin film and the flexible sheet are bonded together with a light-shielding polyolefin resin adhesive layer containing a light-shielding substance.

This light-shielding polyolefin resin adhesive layer is mainly composed of polyolefin resin, and for example, various polyethylene resins, various ethylene copolymer resins, various modified polyolefin resins, etc. are used, and in particular, LDPE resin, L-
LDPE resins and mixed resins of these and other polyolefin resins are preferred.

In addition, the light-shielding polyolefin resin adhesive layer preferably has a thickness in the range of about 10 to about 60 ttm from the viewpoint of securing adhesive strength and light-shielding properties. It is difficult to ensure light-shielding properties with only a resin adhesive layer, pinholes are likely to occur, and the adhesive strength is insufficient, so interlayer peeling is likely to occur. Also, the thickness is about 60mm! ! I
If A is exceeded, the flexible sheet and the aluminum-deposited biaxially oriented thermoplastic resin film may be deteriorated by heat, or heat-shrinked, resulting in increased curling, and the adhesive strength increases, causing the notch effect to be lost and tearing strength to decrease. let Furthermore, the lamination speed is reduced, and the amount of resin used is large, making it expensive.

Examples of light-shielding substances contained in the light-shielding polyolefin resin adhesive layer are shown below.

(1) Inorganic compounds A, oxides: silica, diatomaceous earth, alumina, titanium oxide, iron oxide, zinc oxide, magnesium oxide, antimony oxide, barium ferrite, strontium ferrite, beryllium oxide, pumice, pumice balloon, alumina Fibers etc. B, hydroxides...aluminum hydroxide, magnesium hydroxide, basic magnesium carbonate C1 carbonate...calcium carbonate, magnesium carbonate,
Dolomite, dawsonite, etc., (sulfite)...calcium sulfate, barium sulfate, ammonium sulfate, calcium sulfite, etc.E, silicates...talc, clay, mica, asbestos, glass fiber, glass balloon, glass peas, Calcium silicate, montmorillonite, bentonite, etc.F, carbon...carbon black, graphite, carbon fiber, carbon hollow spheres, etc.G, others...iron powder, copper powder, lead powder, aluminum powder,
Molybdenum sulfide, boron 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 compound wood Flour (pine, oak, sawdust), shell fiber (almond, peanut, rice husk), cotton, jute, paper strips, cellophane strips, nylon fiber, polypropylene fiber,
Among these light-shielding substances such as starch and aromatic polyamide fibers, inorganic compounds that have excellent thermal stability, are relatively inert to photographic light-sensitive materials, and have the ability to make them opaque are preferred. Preferred are light-absorbing carbon black, titanium nitride, and graphite, which are relatively inert substances with excellent properties.

The lubricant is used to improve handling of photographic materials (easier to put them in and out of light-shielding bags), improve extrusion suitability and film formability,
Approximately 0.01 to prevent static electricity, proshing, etc.
It is preferred to add up to about 1.0% by weight.

Typical commercially available lubricants and manufacturer's salts that do not adversely affect photographic film are listed below.

(1) Silicone lubricants; various grades of dimethylpolysiloxane and their modified products (Shin-Etsu Silicone, Toshi Silicone), etc. (2) Oleic acid amide lubricants Nearmoslip CP (Lion Akzo), Neutron (Nippon Rukka) , Neutron E-18 (Nippon Rukka),
Amide 0 (Nitto Chemical), Alflo E-10 (NOF) 1. Diamit 0-200 (Nippon Kasei), Diamit G-200 (Nippon Kasei), etc. (3) Erucic acid amide lubricant; Alflo P-10 (NOF), etc. (4) Stearic acid amide lubricant; Alflo S-10 ( (5) Bis fatty acid amide lubricants; Bisamide (Nippon Kasei), Diamit 200 Bis (Nippon Kasei), etc.
Nippon Kasei), Armowax I! BS (Lion Akzo), etc. (6) Alkylamine-based lubricants; Electro Stripper TS-2 (Kao Soap), etc. (7)
Hydrocarbon lubricant; liquid paraffin, natural paraffin, microwax,
Synthetic barifin, polyethylene wax, polypropylene wax, chlorinated hydrocarbon, fluorocarbon, etc. (8) Fatty acid-based lubricant: Higher fatty acid (preferably Crt or higher), oxyfatty acid, etc. (9) Ester-based lubricant: Lower alcohol ester of fatty acid, fatty acid Aω alcohol-based lubricants such as polyhydric alcohol esters, polyglycol esters of fatty acids, fatty alcohol esters of fatty acids; 00 metal soaps such as polyhydric alcohols, polyglycols, polyglyol, etc.; lauric acid, stearic acid, ricinoleic acid, naphthenic acid, Higher fatty acids such as oleic acid and Li, Mg, Ca, 5
rSBa, Zn%Cd5Aj! It is preferable to add an antioxidant such as a compound with a metal such as , 5nSPb, etc. in order to prevent the occurrence of spots and fish eye and to prevent color failure. 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-
1-butyl-m-cresol), 4,4゛-thiobis(
6-L-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'-
Butylidene bis(3-methyl-6-t-butylphenol), stearyl-β(3,5-di-4-butyl-4-
hydroxyphenyl) propionate, l.l.3-tris(2methyl-4hydroxy-5-t-butylphenyl)butane, 1.3.5 trimethyl-2.4.6-tris(3.5-di-t) -7'thyl-4hydroxybenzyl)benzene, tetrakis[methylene-3(3゛・5°-
Di-t-butyl-4'-hydroxyphenyl)propionate comethane, etc. (0) Ketone amine condensation antioxidant 6-nitoxy 2,2,4-trimethyl-2-dihydroquinoline, 2,2,4-trimethyl- Polymers of 1,2-dihydroquinoline, trimethyldihydroquinoline derivatives, etc. (c) Allylamine antioxidants Phenyl-α-naphthylamine, N-phenyl-β-naphthylamine, N-phenyl-No-isopropyl-P
-phenylenediamine, N-N'-diphenyl-P-phenylenediamine, N-N'-di-β-naphthyl-P-
(d)imidazole antioxidants such as phenylenediamine, N-(3°-hydroxybutylidene)-1-naphthylamine, etc. 2-mercaptobenzimidazole, zinc salt of 2-mercaptobenzimidazole, 2-mercaptomethylbenzimidazole, etc. ) Phosphite-based antioxidants Alkylated allyl phosphite, diphenylisodecylphosphite, tris(nonylphenyl)phosphite Sodium phosphite, trinonylphenylphosphite, triphenylphosphite, etc. (to) Thiourea-based antioxidants Thiourea derivatives, 1,3-bis(dimethylaminopropyl)-2-thiourea, etc. (g) Other antioxidants useful for air oxidation (h) Sulfur-based antioxidants dilauryl thiodipropionate, simiristyl Thiodipropionate, laurylstearylthiodipropionate, distearylthiodipropionate Typical commercially available antioxidants are shown below.

(1) Phenolic antioxidant; SLlMILIZERBHT (resident), IRGANOX
1016 (Ciba Geigy), MARK AO-50 (
Adeka Argus), SUM [L-IZERBP-76
(Resident), TOMINOX SS (Yoshitomi), IRGAN
O-X 565 (Ciba Geigy), N0NOX WSP
(ICI), SANTONOx (Monsan to)
, SU[LIZI! R14X R (resident), ANTAG
IIC-RYSTAL (Kawaguchi), IRGANOX 10
35 (Ciba Geigy), A-NTAGB N-400 (
Kawaguchi), N0CLIZERN5-6 (Iriuchi Shinko), IR
GANOX 1425 #4L (Ciba Geigy), HA
RK AO-80 (Ateca Argus), SUMILI
ZERGA-80 (resident), TOPANOL CA (I
CI), MARK^0-30 (Adeka Argus), M
ARK AO-20 (7 Deka Argus), IRGAN
OX3114 (Ciba Geigy), MARX AO-33
0 (ADEKA ARGUS), IRGANOX 1330 (
Ciba Geigy), CYANOX1790 (ACC),
IRGANOX 1010 (Ciba Geigy), MARK
AO-60 (7 decal 7-gas), S[IMILIZE
RBP-101 (Resident), TO-MINOX TT (Yoshitomi), etc. (2) Phosphorous antioxidant; rRGAPO5168 (Ciba Geigy), MAR 21
12 (7 Deca Argus), I#ESTON 618 (
BorgWarner), MARK PEP-8 (7 Teka・7
- Gas), (ILTRANOX 626 (Boulder Warner), MARK PEP-24G (Adeka Argus), MARK PI!P-36 (Adeka Argus),
flcA (ternary) etc. (3) Thioether antioxidant; DLTDP YO5HI70MI” (Yoshitomi), S(+
MILIZI! RTPL (resident), ANTIOX L (
8 oil), DI'lTO''YOS old ↑ON1'' (Yoshitomi),
SUMILIZERTPM (resident), ANTIOX M
(8 oil), DSTP “YOSIII TOMI” (Yoshitomi)
, SUMILIZERTPS (resident), ANT-10X
S (8 oil), 5EBNOX 4125 (shibu mouth), M
ARK AO-412S (ADEKA ARGUS), SUM
ILIZERTP-DC resident, MARK AO-23
(ADEKA ARGUS), 5ANDSTABP-EPQ
(Sand), II? GAFO3P-EPQ FF (Ciba Geigy), IRGANOX 1222 (Ciba Geigy), 329K to MAR (Adeca Argus), ES
TON399 (Boulder Warner), )26 to JAR
0 (Adeka Argus), MARK 522A (Adeka Argus), etc. (4) Metal deactivator NAUCARD XL-1 (uni o ear), MARK
C[1A-1 (ADEKA ARGUS), MARK CD
A-6 (ADEKA ARGUS), LRGANOX? l0
-1024 (Ciba Geigy), CUNOX (Mitsui Toatsu)
Particularly preferred antioxidants are phenolic antioxidants, and commercially available products include various Irganox products from Ciba Geigy, Su*fIizer B)tT from Susumu Kagaku ■,
5uvilizer BH-76, Sus+1lize
r-χ-R, Sumi-lizer BP-101, etc.

In addition, 2,6-shihibutyl p-cresol (BIT
), low volatility high molecular weight phenolic antioxidant (trade name 1reganox 1010. Ireganox
1076゜Topanol CA, Ionox 33
It is effective to use one or more, especially two or more, of dilauryl thiodipropionate, distearyl thiopropionate, dialkyl phosphate, etc.

It is preferable to use a phenolic antioxidant and a phosphorus antioxidant in combination because the antioxidant effect becomes particularly excellent.

For example, when added to a polyolefin resin adhesive layer or a light-shielding polyolefin resin film, the amount added is approximately 0.
．． 003 to about 2.0% by weight.

If the amount added is less than about 0.003% by weight, there is almost no effect of the addition, while if the amount added exceeds about 2.0% by weight, it will have a negative effect on photographic films that utilize oxidation and reduction effects, causing abnormalities in photographic performance. There are cases where

For this reason, it is preferable to add the antioxidant in the minimum amount that will not cause color failure, blistering, or fisheye.

Furthermore, when used in combination with carbon black etc., the oxidation prevention effect is synergistically exerted. In particular, it is preferable to use a phenolic antioxidant, carbon black, and a phosphorus antioxidant in combination because the antioxidant effect is synergistically exhibited.

Other various antioxidants disclosed on pages 794 to 799 of Plus Deck Data Handbook (published by KK Industrial Research Association) and various antioxidants disclosed on pages 327 to 329 of Plastic Additive Data Collection (published by KK Chemical Industry Co., Ltd.) PLASTIC5AGE ENCYC-LOP
It is possible to select and use various antioxidants and the like disclosed in pages 211 to 212 of E-guchi IA Progress 111986 (published by KK Plastic Age Co., Ltd.).

Next, typical examples of additives are described below, but the present invention is not limited thereto, and additives can be selected from all known additives.

(Additive types) (Representative examples) (1) Plasticizers: Phthalate esters, glycol esters, fatty acid esters, phosphate esters, etc. (2) Stabilizers: Lead-based, cadmium-based, zinc-based, alkaline earth metal-based , organic tin-based, etc. (3) Flame retardants; phosphoric acid esters, halogenated phosphoric acid esters, halides, phosphorus-containing polyols, etc. (4) Fillers; alumina, kaolin, clay calcium carbonate, mica, tar, oxidation Titanium, silica, etc. (5) Reinforcing agents; Glass roving, metal fibers, glass fibers, glass milled fibers, carbon fibers, etc. (6) Foaming agents; Inorganic blowing agents (ammonia carbonate, heavy R
(acid soda), organic blowing agents (nitrone type, azo type), etc. (7) Vulcanizing agents; vulcanization accelerators, accelerators, etc. (8) Deterioration inhibitors; UV absorbers, metal deactivators, peroxidation (9) Coupling agents; Silane-based, titanate-based, chromium-based, aluminum-based, etc. (0) Various thermoplastic resins, rubber, etc. (11) Nucleating agents; Organic nucleating agents (dibenzylidene sorbitol) Compounds, etc.), inorganic nucleating agents (calcium carbonate, etc.) Photographic materials to which the packaging material for photographic materials according to the present invention can be applied are shown below.

O Silver halide photographic materials (X-ray film, printing film, color photographic paper, color film, printing master paper, DTR photosensitive material, computer typesetting film and paper, microfilm, motion picture film, self-developing photographic material) Materials, heat-developable photographic materials, direct positive film and paper, etc.) O diazonium photographic materials (4-morpholinobenzenediazonium chlorofilm, microfilm, copying film, printing plate materials, etc.) O azide,
Diazide-based photographic material (Balaazide Benshade, 4)
, 4'' diazidostilbene, etc., such as copying films, printing plates, etc.) O-quinonediazide photographic materials (ortho-quinonediazide, ortho-naphthoquinonediazide-based compounds, such as benzoquinone (1,2)-diazide) -(2) Photosensitive materials containing -4-sulfonic acid phenyl ether, etc., such as printing plates, copying films, adhesion films, etc.) O Photopolymers (photosensitive materials containing vinyl monomers, etc., printing plates, etc.) Adhesion film, etc.) 0 Polyvinyl cinnamic acid ester type (e.g. printing film, IC resist, etc.) In addition, photosensitive materials that change or deteriorate due to various types of light, oxygen, sulfur dioxide, etc., such as food (Butterbee nut bags, etc.)
margarine, snack products, snacks, sweets, tea, seaweed, etc.), pharmaceuticals (powdered and granular medicines such as gastrointestinal medicines and cold medicines), dyes, pigments, photographic developing chemicals, photographic fixing chemicals,
It can be applied to toner, etc.

[Function] In the packaging material for photographic materials of the present invention, the heat-resistant, high Young's modulus flexible sheet provides excellent bag-making suitability, appearance, and curling, and also protects against external impacts. As a result, pinholes and tears are less likely to occur in the inner light-shielding polyolefin resin adhesive layer. The intermediate layer aluminum-deposited biaxially stretched thermoplastic resin film has excellent light shielding properties, moisture proofing properties, gas barrier properties, antistatic properties, impact puncturing strength, and bursting strength, and is resistant to external and internal impacts and has sharp edges. To have excellent resistance to damage caused by objects.

Since the light-shielding polyolefin resin adhesive layer is a thin layer, there is no ring (which maintains the notch effect and increases tear strength. Also, the light-shielding polyolefin resin film is
Contains light-absorbing carbon black, which prevents light from penetrating through the cross section and poor light-shielding properties due to pinholes, and provides excellent physical strength such as tear strength and heat-sealing suitability. .

〔Example〕

Examples of the packaging material for photographic materials of the present invention will be described with reference to FIGS. 1 to 8.

1 to 8 are partial cross-sectional views showing the layer structure of the packaging material for photographic materials.

The packaging material for photographic light-sensitive materials shown in FIG. , a light-shielding polyolefin resin film 5a is laminated via an adhesive layer 3,
A flexible sheet 6 is laminated on the side of the aluminum vapor-deposited film 2 of the aluminum vapor-deposited biaxially stretched thermoplastic resin film (1) via a light-shielding polyolefin resin adhesive layer 4a.

The packaging material for photographic light-sensitive materials shown in FIG. 2 is an aluminum vapor-deposited film 2 of an aluminum vapor-deposited biaxially stretched thermoplastic resin film Ia, in which an aluminum vapor-deposited film 2 is vapor-deposited on a biaxially-stretched thermoplastic resin film 1a containing a light-shielding substance. A light-shielding polyolefin resin film 5a is laminated on the side via an adhesive N3a containing a light-shielding substance, and a light-shielding polyolefin resin film 5a is laminated on the biaxially stretched thermoplastic resin film laO side of the aluminum-deposited biaxially stretched thermoplastic resin film Ia. Flexible sheets 6 are laminated with a resin adhesive layer 4a interposed therebetween.

The packaging material for photographic light-sensitive materials shown in FIG.
are directly laminated, and a flexible sheet 6 is laminated on the side of the biaxially stretched thermoplastic resin film I of the aluminum vapor-deposited biaxially stretched thermoplastic resin film I via a light-shielding polyolefin resin adhesive layer 4a.

The packaging material for photographic light-sensitive materials shown in FIG. A light-shielding two-layer coextruded film Ila of and a light-shielding polyolefin resin film 5a is laminated, and a light-shielding polyolefin resin adhesive layer 4a is placed on the side of the aluminum vapor-deposited film 2 of the aluminum vapor-deposited biaxially stretched thermoplastic resin film I. Flexible sheets 6 are laminated with each other interposed therebetween.

The packaging material for photographic light-sensitive materials shown in FIG. 5 has the layer structure shown in FIG.
A two-layer coextruded light-shielding polyolefin resin adhesive layer (a) consisting of a and 4B is used.

The packaging material for photographic light-sensitive materials shown in FIG. 6 has a thermoplastic resin containing no light-shielding substance in place of the light-shielding thermoplastic resin film 7a of the light-shielding multilayer coextruded polyolefin resin film Ua in the layer structure shown in FIG. In place of the film 7 and the adhesive layer 3, an adhesive layer 3a containing a light-shielding substance is used.

The packaging material for photographic light-sensitive materials shown in FIG. 7 has a two-layer coextruded film of light-shielding polyolefin resin films 5a, 5a instead of the light-shielding multilayer coextruded polyolefin resin film Ua in the layer configuration shown in FIG. A blocking adhesive light-shielding multilayer coextruded polyolefin resin film IVa to which a certain light-shielding multilayer coextruded polyolefin resin film Ma is bonded is laminated.

The packaging material for photographic light-sensitive materials shown in FIG. 8 has a light-shielding polyolefin resin film 5a and a light-shielding thermoplastic resin film 7a instead of the light-shielding multilayer coextruded polyolefin resin film lla in the layer configuration shown in FIG. Light-shielding multilayer coextruded polyolefin resin film I
la and Ila are light-shielding thermoplastic resin films 7a, ?
A blocking adhesive light-shielding multilayer coextruded polyolefin resin film ①a is laminated between ``a'' and ``a''.

Although it is possible to use various known adhesive layers as the adhesive layer 3, it is preferable to use a polyolefin resin adhesive layer that can be tandem laminated and has a low lamination cost. or 7
Although various thermoplastic resin films can be used as a, a polyolefin resin film is preferable from the viewpoint of physical strength, film formability, cost, etc.

Next, the experimental results of the invention products I and (2) will be explained.

Invention product I The layer structure corresponds to that shown in FIG.

The flexible sheet 6 contains aluminum sulfate and polyacrylamide, but does not contain substances that adversely affect photographic materials such as chlorine, propylene oxide, and ethylene oxide as antifoaming agents.The flexible sheet 6 has a Young's modulus of 428 kg/as" and a basis weight of 5.
Use unbleached kraft paper of 0g/rrf.

The light-shielding polyolefin resin adhesive layer 4a has a Ml content of 5.1 g/10 minutes containing 3% by weight of carbon black,
20-thick extrusion with a density of 0.919 g/cm
The Dishin LDPE resin adhesive layer was used in tandem lamination with the LDPE resin adhesive layer described below.

The aluminum vapor-deposited biaxially stretched thermoplastic resin film I is
A biaxially stretched nylon resin film with a thickness of 15 mm was used as the biaxially stretched thermoplastic resin film 1, and
An aluminum vacuum-deposited biaxially stretched nylon film on which the aluminum-deposited film 2 was vacuum-deposited was used.

The adhesive layer 3 has a thickness of 15 and an MI of 5.1 g/10 min.
An LDPE resin adhesive layer with a density of 0.919 g/d was used. The light-shielding multilayer coextruded polyolefin resin film Ila is made of M
H with l of 1.1 g/10 min and density of 0.954 g/cj
DPE resin 20% by weight, Ml 2.1 g/10 min, density 0.920 g/d ethylene/4 methylpentene-1
Copolymer tree D 72.25% by weight, Ml 2.4g/1
0 minutes, LDPE resin 4.5 with density 0.926 g/cj
Weight%, Furnace carbon black 3% by weight (using 7.5% by weight of LDPE resin masterbatch containing 400% carbon black), Synthetic silica 0.1% by weight
, thickness 40I, consisting of 0.05% by weight of erucic acid amide and 0.1% by weight of phenolic antioxidant! Light-shielding polyolefin resin film 5a using a film of m
CMI is 2.1g/10min, density is 0.920
g/cd (D ethylene/4 methylpentene-1 copolymer resin 92, 25 wt%, Ml 2.4 g/10 min, density 0.926 g/cta' LDPE resin 4.5 wt%
, 3% by weight of furnace carbon black (using 7.5% by weight of LDPE resin masterbatch containing 40% by weight of furnace carbon black), 0.1% by weight of synthetic silica, 0.05% by weight of erucic acid amide, phenolic oxidation A light-shielding two-layer coextruded blown film with a thickness of 80 nm was made using a film with a thickness of 40 nm containing 0.1% by weight of an inhibitor.

Using the above laminated film, the bottom heat seal width is 10
A single-layer gusset bag (3) was made, and a roll of color photographic paper with a width of 89 m and a length of 180 m was sealed and packaged. As a result, pinholes and bag breakage did not occur even though the bottom was not bent and secured with adhesive as in the past.

Invented product... The layer structure corresponds to that shown in FIG.

The flexible sheet 6, the light-shielding polyolefin resin adhesive layer 4a, the aluminum vapor-deposited biaxially stretched thermoplastic resin film 1, and the adhesive layer 3 are the same as those of the product I of the present invention.

The blocking adhesive light-shielding multilayer coextruded polyolefin resin film fVa uses a 20 tsa thick film having the same resin composition as the light-shielding thermoplastic resin film 7a of the invention product I as the outer light-shielding polyolefin resin film 5a, The inner light-shielding polyolefin resin film 7a has an Ml of 2.1 g/10 min and a density of 0.
920g/cffl of ethylene 4-methylpentene-1
Copolymer resin 84.5! [i lid%, Ml is 0.4g/1
0 minutes, density 0.900g/cd, molecular weight distribution 8.3
12.2% by weight of ethylene-butene-1 copolymer resin,
A 40-thick film using a 20-thick film consisting of 3% by weight of furnace carbon black, 0.1% by weight of silica, 0.05% by weight of oleic acid amide, and 0.15% by weight of phenolic antioxidant. The light-shielding two-layer coextruded blown film of 58.7a was bonded between 7a and 7a using a nip roll, and the thickness was 804.
This is a blocking adhesive light-shielding multilayer coextruded polyolefin resin film.

Using the above-mentioned laminated film, a single-layer gusset bag similar to Invention Product (2) was made, and color photographic paper was sealed and packaged. As a result, as with Inventive Product 1, no pinholes or bag breakage occurred.

〔Effect of the invention〕

Since the present invention is configured as described above, the light-shielding polyolefin resin adhesive layer is not easily damaged by impacts or sharp edges, the light-shielding layer can be formed by a tandem lamination method, and it is inexpensive, durable, and non-static. The packaging material has excellent light-blocking and light-blocking properties.

[Brief explanation of the drawing]

1 to 8 are partial cross-sectional views showing the layer structure of an embodiment of the packaging material for photographic materials of the present invention. 1.1a... Biaxially stretched thermoplastic resin film 2...
Aluminum vapor deposited film 3.3a...Adhesive layer 4.4a, 4a...Light-shielding polyolefin resin adhesive layer 5a...Light-shielding polyolefin resin film 6.6
a... Flexible sheet 7. 7a... Thermoplastic resin film l, Ta... Aluminum evaporated biaxially stretched thermoplastic resin film Ua... Light-shielding multilayer coextruded polyolefin resin film IVa... Blocking adhesive Light-shielding multilayer coextruded polyolefin resin film a: Indicates that light-shielding substance is contained. B... Indicates blocking adhesion. Patent applicant: Fuji Photo Film Co., Ltd. Agent
Patent Attorney Yamanaka Politics Figure 1

Claims (1)

[Claims] An aluminum vapor-deposited biaxially stretched thermoplastic resin film, a light-shielding polyolefin resin film laminated on one side of the thermoplastic resin film and containing an ethylene copolymer resin, carbon black, and an antiblocking substance, and the thermoplastic resin A flexible sheet laminated on the other side of the film and having heat resistance and a high Young's modulus, and a polyolefin resin adhesive layer containing a light-shielding substance bonding the flexible sheet and the thermoplastic resin film. A packaging material for photographic materials characterized by