JP2000334897A - Packaging material and package using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a packing material having a laminated film bonded and laminated by blocking, having necessary physical strength, generating no curling and having recycle properties, reuse properties and stable blocking adhesive strength. SOLUTION: A packaging material is constituted of a laminated film of two miltilayered coextrusion inflation films each having a high α-olefinic resin layer based on a high α-olefinic resin containing 1 wt.% or more of a 4 or more C α-olefin and a special ethylene copolymer resin layer based on a special ethylene copolymer resin containing 5-40 wt.% of one or more of vinyl acetate and acrylic acid. The special ethylene copolymer resin layers of two multilayered coextrusion inflation films are mutually bonded and laminated by blocking.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a packaging material provided with a laminated film bonded and laminated by blocking and a package using the same.

[0002]

2. Description of the Related Art Conventionally, various types of packaging materials for photographic photosensitive materials used for packaging bags for packaging photographic films have been proposed, and Japanese Patent Application Laid-Open No. 64-22444 discloses multilayer coextrusion. A packaging material in which the inner layers of an inflation film are pseudo-adhered by blocking each other has been proposed.

Japanese Patent Publication No. 2-2700 discloses that a polyethylene-based polymer and 1% by weight or more of a light-shielding substance are used, and 50% by weight or more of the total polyethylene-based polymer is L.
-A photosensitive material packaging film having at least one light-shielding film which is an LDPE resin has been proposed.

Further, Japanese Patent Publication No. 4-80373 proposes a packaging material for a photographic photosensitive material comprising a two-layer co-extruded blown film comprising a high-density polyethylene resin layer or a polypropylene resin layer and an L-LDPE resin layer. I have.

[0005]

However, the packaging materials proposed in the past have various problems and improvements have been desired. That is, the packaging material proposed in Japanese Patent Application Laid-Open No. Sho 64-22544 has very low curling, high physical strength, excellent recyclability and incineration suitability, and is extremely preferable. It is not sufficient, and it has been desired to further improve photographic properties and physical strength.

The photosensitive material packaging film proposed in Japanese Patent Publication No. 2-2700 is preferable because it has excellent physical strength even in a single layer. However, in order to use a single layer for a heavy material package having a large moisture-proof property, the thickness must be increased, and when the thickness is increased, the shear stress increases and a melt fracture occurs. . Therefore, it is difficult to constitute a packaging material for a photographic photosensitive material having a weight of 1 kg or more in a single layer, and it is necessary to laminate a metal layer or a flexible sheet having a Young's modulus of 50 kg / mm ² or more, which results in cost and incineration. Improvements in suitability and recyclability have been desired. Further, when the metal layers are laminated, there is a disadvantage that the physical strength (tear strength, impact piercing strength, gelbotest strength, etc.) is reduced.

The packaging material for photographic photosensitive materials proposed in Japanese Patent Publication No. 4-80373 is an improved version of the packaging film for photosensitive materials proposed in Japanese Patent Publication No. 2-2700, and has physical strength and suitability for recycling. And excellent incineration suitability, but curling, antistatic properties, physical strength, etc. are not sufficient, and further improvement has been desired.

In a photographic light-sensitive material package made of a wrapping material for photographic light-sensitive material using a laminated film laminated by blocking adhesion, the blocking adhesion is peeled off at the opening of the packaging bag, and when the photographic light-sensitive material is taken in and out. In some cases, a product or a hand gets into the inside, and the workability is sometimes deteriorated.

The present invention solves the above problems, and provides a physical strength required as a packaging material that can be used for a packaging bag of a weight product having a weight of 1 kg or more only by a multilayer coextrusion blown film forming process. Has no curling, has stable blocking adhesive strength, has excellent suitability for bag making and lamination with other flexible sheets, is flexible, has excellent long-term heat seal sealing properties, is suitable for recycling, and is reused. Excellent suitability and incineration suitability, 20
An object of the present invention is to provide a packaging material which is inexpensive and does not adversely affect the social environment and conforms to the Containers and Packaging Recycling Law which will be enforced from April 2000, and a package using the same.

[0010]

According to the present invention, there is provided a packaging material having a high α content of at least 1% by weight of an α-olefin having 4 or more carbon atoms.
A high α-olefin resin layer containing an olefin resin as a main component, and at least one of vinyl acetate and acrylic acid in an amount of 5 to 4
A two-layer co-extruded blown film comprising a special ethylene copolymer-based resin layer containing a special ethylene copolymer-based resin containing 0% by weight as a main component and two laminated co-extruded blown films. It is characterized by comprising a laminated film in which special ethylene copolymer resin layers are bonded and laminated by blocking.

In the packaging material of the present invention, the strength of blocking adhesion between special ethylene copolymer-based resins is improved by minimizing the influence of fluctuation factors of molding conditions, and
Physical strength, curling, etc. are improved.

A package according to the present invention is a package in which an article to be packaged is housed in a packaging bag manufactured using the above-mentioned packaging material, and a special ethylene copolymer-based resin in an opening portion for taking in and out the article to be packaged in the packaging bag. It is characterized in that the layers are bonded at one or more locations with a peel strength greater than the blocking adhesive strength.

In the package of the present invention, the special ethylene copolymer resin layers are bonded and laminated at one or more places with a peel strength larger than the blocking bonding.
Even if the adhesive due to blocking comes off, it does not come off over the entire surface. When removing or putting in a bag, the hand of a person trying to take out or put in a bag is a blocking adhesive. It does not penetrate between the laminated special ethylene copolymer resin layers.

[0014]

BEST MODE FOR CARRYING OUT THE INVENTION The packaging material of the present invention is formed of a laminated film in which special ethylene copolymer resin layers of a multilayer coextruded blown film are adhered and laminated by blocking. If necessary, at least one surface of the laminated film may be laminated with one or more flexible sheets via an adhesive layer or without an adhesive layer.

Even if the multilayer co-extruded blown film is composed of two special ethylene copolymer resin layers and a high α-olefin resin layer, the two special ethylene copolymer resin layers and the high α-olefin resin Even if it is composed of three layers (a structure in which a special ethylene copolymer resin layer sandwiches a high α-olefin resin layer from both sides), a special ethylene copolymer resin layer, an intermediate layer and a high α-olefin resin layer It may be composed of three layers including a resin layer, or may be composed of a multilayer composed of four or more layers composed of two or more intermediate layers.

The laminated film is formed by blocking and laminating the special ethylene copolymer resin layers of the multi-layer co-extruded blown film, and thus has a vertically symmetric structure. In order to pseudo-adhere the special ethylene copolymer-based resin layers of the multilayer co-extrusion blown film by blocking, for example, when forming a multilayer co-extrusion blown film by a multilayer co-extrusion blown film forming method, a nip roll for take-off or a nip roll for take-off The special ethylene copolymer-based resin layers of the multilayer co-extrusion blown film are pressed against each other with a pressure roll or an emboss roll newly provided at the subsequent stage. If necessary, the take-off nip roll or pressure roll may be heated. The round die (ring die) used for the multilayer coextrusion blown film molding machine
There are three types: a multi-manifold die of a die-inside lamination type, a multi-slot die of a die-outside lamination type, and a single-manifold die in which each material is combined before a die of a laminar flow supply type. A multi-manifold die of an in-die lamination type can be used because of a large interlayer adhesive force.

Further, in order to increase the blocking adhesive strength, before passing through each roll such as a nip roll, a pressure roll (or an emboss roll) or a heating roll, a far-infrared lamp, hot air, a nichrome wire heater or other Heating may be performed using a heating device. Further, immediately after forming a laminated film in which the special ethylene copolymer-based resin layers are bonded and laminated by blocking as described above (0 to 1).
It is preferable that the film be uniaxially stretched in the longitudinal direction at (5 seconds) because the adhesive strength is further improved.

The blocking adhesion of the special ethylene copolymer-based resin layer is not completely bonded and fixed so as to be bonded with an adhesive, but is performed in a somewhat flexible state by blocking without using any adhesive. Pseudo glued,
Curling is prevented while improving physical strength. Further, since it is not necessary to laminate the film through an adhesive layer which deteriorates the heat or adversely affects the photographic properties of the photographic light-sensitive material, the photographic properties are good and the recyclability is excellent.

From the viewpoint of improving the physical strength, the blocking adhesive strength is 0 to 300 g, preferably 0 to 200 k, as measured by a 180-degree folding peeling test (sample width 15 mm, peeling speed 50 mm / min) according to JIS K 6744.
g, more preferably 0.01 to 150 g, particularly preferably 0.02 to 100 g, and most preferably 0.05 to 50 g.
g.

The high α-olefin resin contains at least 1% by weight of α-olefin having 4 or more carbon atoms, preferably at least 1.5% by weight, more preferably at least 2% by weight,
Most preferably, it is at least 3% by weight. When the content of the α-olefin having 4 or more carbon atoms is less than 1% by weight, the heat seal strength over time or the physical strength cannot be sufficiently secured.

The α-olefin having 4 or more carbon atoms includes butene-1, 3-methylbutene-1, octene-
1, hexene-1, pentene-1, 3-methylpentene-1, 4-methylpentene-1, 4,4-dimethylpentene-1, heptene-1, heptene-1, nonene-1,
There are decene-1, dodecene-1, undecene-1, pentadecene-1, eicosene-1, tetradecene-1, octadecene-1, and the like, and α-olefins having 4 to 20 carbon atoms are preferable, and 4 to 12 carbon atoms. Α-olefins are more preferable, α-olefins having 4 to 8 carbon atoms are particularly preferable, and α-olefins having 6 to 8 carbon atoms are most preferable.

Examples of the high α-olefin resin include random and block copolymer resins of ethylene and one or more α-olefins, and random and block copolymer resins of propylene and one or more α-olefins. There are block copolymer resins, homo α-olefin copolymer resins, and the like. Specific representative examples include ethylene-butene-1 random copolymer resin, ethylene-hexene-1 random copolymer resin,
Ethylene-4-methylpentene-1 random copolymer resin, ethylene-octene-1 random copolymer resin, propylene-ethylene random copolymer resin, propylene-ethylene block copolymer resin, homopolypropylene resin, polybutene resin, Examples include poly-4-methylpentene-1 resin, homopolyethylene resins of various densities, various polyolefin-based thermoplastic elastomers, and the like.

As the copolymer resin of ethylene and one or more α-olefins, the most preferred resin in the present invention is an L-LDPE resin. This LL
DPE (L inear L ow D ensity P oly
e thylene) resin is called third polyethylene resin, medium low-pressure, low-cost, high-strength resin that meets the needs of the times that energy saving, resource saving having both the advantages of high-pressure two polyethylene resins. This resin is obtained by copolymerizing ethylene with the α-olefin (one or more) by a low-pressure method or a high-pressure improvement method using a multi-site catalyst (typically, a Ziegler catalyst) or a single-site catalyst (typically, a metallocene catalyst). It is a polymerized copolymer and a polyethylene resin having a linear linear structure with short branches.

LL using a typical multi-site catalyst
The polymerization process of DPE resin includes high-pressure conversion to obtain L-LDPE resin at high temperature and high pressure with Ziegler-based catalyst using gas phase method, solution method, liquid phase slurry method and improved high pressure method equipment using medium / low pressure equipment. There is a law.

Typical specific examples of L-LDPE resins produced by polymerization using a commercially available multi-site catalyst are shown below. (1) Ethylene / butene-1 copolymer resin G resin (UCC) Dourex (Dow Chemical) Screer (DuPont Canada) Marrex (Philips) Stamirex (DSM) Sumikasen L (Sumitomo Chemical) Neozex (Mitsui Petrochemical) Novatec-L (Mitsubishi Kasei) Yucaron-LL (Mitsubishi Yuka) Nisseki Linirex (Nippon Petrochemical) Shorex Linear (Showa Denko) NUC Polyethylene-LL (Nippon Unicar) Ube Polyethylene L (Ube Industries) Idemitsu Polyethylene L (Idemitsu Petrochemical) Nipolon L (Tosoh) (2) Ethylene-hexene-1 copolymer resin Exelene VL (Sumitomo Chemical) TUFLIN (UCC) NUC-FLX (Nack Flex) (UCC) TUFTHENE ( Nippon Unicar) Nipolon (Tosoh) (3) Ethylene / 4-methylpentene-1 copolymer resin Ultoxex (Mitsui Petrochemical) (4) Ethylene / octene-1 copolymer resin Stamilex (DSM) Dourex (Dow Chemical) Screa (Dupont Canada) MORETEC (Idemitsu Petrochemical)

Among these L-LDPE resins, they contain a light-shielding substance and are used for light-shielding hermetically sealed packaging bags for photographic light-sensitive materials in which complete light-shielding properties, heat-sealing suitability, tear strength and impact hole-piercing strength are particularly required. In this case, a preferred resin has a melt flow rate (hereinafter, referred to as MFR) of 0.1 to 10 g.
/ 10 min (Condition 4 of JIS K-7210 or ASTM D
Measured under condition E of 1238. Test temperature 190 ° C, test load 2.16kgf), density 0.870-0.940g
/ Cm ³ (JIS K-7112 or ASTM D150
5) and the α-olefin has 4 to 15 carbon atoms.
, Preferably 4 to 10, more preferably 6 to 8 obtained by the liquid phase process and the gas phase process.

Also, Sumikacene-L (Sumitomo Chemical), Nipolon L and Z (Tosoh), Ube polyethylene L (Ube Industries, Ltd.) obtained by the improved high pressure method process in which equipment costs were reduced by converting the conventional high pressure method manufacturing process. L-LDP such as
E resins are also preferred.

Preferred representative examples of the L-LDPE resin used in the high α-olefin resin layer of the present invention are listed below under trade names. Polyethylene is produced by polymerization using a multi-site catalyst (a typical example is a Ziegler catalyst). Ultzex manufactured by Mitsui Petrochemical Co., Ltd., into which 4-methylpentene-1 having 6 carbon atoms is introduced as an α-olefin side chain, and Idemitsu Petrochemical Company, into which octene-1 having 8 carbon atoms is introduced as an α-olefin side chain. MORETEC Co., Ltd., DSM's Stamirex and Dow Chemical's Dourex are available. (All four products are L-LDPE obtained by liquid phase process.)
Resin). Preferable typical examples obtained by the low-pressure gas phase process are listed below under trade names: TUFTHEN and UCC of Nippon Unicar Co., Ltd., in which hexene-1 having 6 carbon atoms is introduced as an α-olefin side chain. TUFLI
N.

The recently released density is 0.910 g.
/ Cm ³ ultra low density linear low density polyethylene resin such as NUC-FLX of UCC or Sumitomo Chemical Co., Ltd.
(The above two companies use hexene-1 whose α-olefin has 6 carbon atoms).

The outline of the features of the process for producing an L-LDPE resin using a multi-site catalyst (a typical example is a Ziegler catalyst) is shown below.

The relationship between the outline of a typical production process and the trade name of each resin manufacturer will be described below.

[1] Gas-phase method It is reported that the amount of energy required for polymerization is small.
In terms of quality, it is necessary to use a single component that is easy to volatilize as a comonomer, which is limited compared to the solution method. Recently, the choice of comonomer and the control range of the molecular weight distribution have been increasing.

[2] Slurry method The liquid phase polymerization method using a solvent is classified into a slurry method and a solution method. In the slurry method, a solvent is used, but a slurry (heterophase type) is used. Therefore, since the solution in the reaction vessel has a low viscosity, it can be produced with relatively compact equipment, and the solvent can be easily removed. There are advantages. On the other hand, regarding low density, the low molecular weight low density polymer dissolves in the solvent, the solution becomes high in viscosity, or the polymer expands and agglomerates, so that the LL having a density of 0.930 g / cm ³ or less is used.
DPE production is limited.

[3] Solution Method Polymerization in the solution method is performed in a solution. The reaction is performed at a high temperature to maintain a solution state. In terms of quality, the permissible range of the density reduction is wide, and the α-olefin having 4 or more carbon atoms, preferably 6 or more carbon atoms (butene-1, pentene-
1,3-methylpentene-1,4-methylhexene-
1,4,4-dimethylpentene-1, 4-methylpentene-1, hexene-1, heptene-1, heptene-1, nonene-1, octene-1, decene-1, undecene
1, eicosene-1, dodecene-1, hexadecene-
1, octadecene-1, tetradecene-1, etc.) and ethylene. Further, L-LDPE resin having a large α-olefin content (having a density of 0.1%) is used.
It is also optimal as a production process for an ultra-low density L-LDPE resin of 910 g / cm ³ or less.

[4] Improved high-pressure method A method for obtaining an L-LDPE resin at a high temperature and a high pressure using a Ziegler catalyst while using the conventional high-pressure method as it is, and its running cost is higher than that of the above-mentioned gas-phase method, slurry method and solution method. It is. Also called high pressure conversion method.

Table 1 shows these introduced manufacturing technologies, manufacturing companies, and trade names.

[0037]

[Table 1]

[Outline of a typical example of the above manufacturing process] Solution method: pressure: 450 to 650 PSi, temperature: 20
0 to 250 ° C. Slurry method: pressure: 400 to 500 PSi, temperature: 90
-100 ° C Gas phase method: pressure: 250-350PSi, temperature: 90
-100 ° C Improved high pressure method: Pressure: about 20,000 PSi, temperature: 2
Around 00 ℃

The ratio of ethylene to α-olefin is preferably 70% or more, more preferably 80% or more. When the ethylene content is less than 70%, the polymerization suitability deteriorates and the cost increases, and the obtained ethylene / α-olefin copolymer resin has high tackiness, low rigidity and poor film moldability, and the Blocking is large and practical use is difficult. However, in the case of using a laminated film in which the inner layers are laminated by blocking adhesion, it is preferable to use as the inner layer because a stable blocking adhesive lamination can be obtained regardless of the temperature and humidity in the film forming chamber.

Specific examples of currently commercially available L-LDPE resins produced by polymerization using a metallocene-based catalyst, which is a typical example of a single-site catalyst capable of reducing catalyst residues with high activity, are shown below. EXCEED (EXXon chemical) EXACT (EXXon chemical) AFFINITY (DOW chemical) ENGAGE (DOW chemical) LUFLEXENE (BASF) EVOLUE (Mitsui Petrochemical) Japan (Mitsubishi Chemical Rex) Catalocene (Tosoh)

As a polymerization method, a gas phase polymerization method is particularly preferable because it is inexpensive and has a small amount of catalyst residues that adversely affect photographic properties. A liquid phase polymerization method such as a suspension polymerization method or a solution polymerization method is also preferable in terms of ease of polymerization.

In order to prevent blocking and improve physical strength,
The molecular weight distribution (weight-average molecular weight / number-average molecular weight) by the GPC method is 5 or less, preferably 4 or less, more preferably 1.1 to 3, and most preferably 1.3 to 2.7.

Preferred as the ethylene / α-olefin copolymer resin is an ethylene / α-olefin random copolymer resin. The composition of the ethylene / α-olefin random copolymer resin is such that the α-olefin component is 0.1 to 99 mol%, preferably 0.2 to 80 mol%,
More preferably 0.5 to 60 mol%, particularly preferably 1 to 60 mol%.
４０40 mol%, most preferably 1-20 mol%,
The ethylene component is 1 to 99.9 mol%, preferably 20 to
It is 99.8 mol%, more preferably 40 to 99.5 mol%, particularly preferably 60 to 99 mol%, and most preferably 80 to 99 mol%. Representative examples of α-olefins include propylene, butene-1, hexene-1, pentene-1, 3-methyl-pentene-1, 4-methyl-hexene-1, 4-methyl-pentene-1,4,4 -Dimethylpentene-1, octene-1, nonene-1, decene-
1, dodecene-1, tetracene-1, hexadecene-
1, pentadecene-1, octadecene-1, heptene-
1, eicosene-1,4-methyl-hexene-1,4,
4-dimethylpentene-1 or the like having 3 to 20 carbon atoms;
It is preferably 4 to 15, more preferably 4 to 12, and most preferably 4 to 10, one or more α-olefins.

Further, an ethylene / α-olefin random copolymer resin produced by polymerization using a metallocene catalyst is preferable, and a specific example of a particularly preferable resin has an MFR of 0.1.
1 to 10 g / 10 min, density 0.870 to 0.940 g
L-LDPE resin obtained by copolymerizing ethylene and hexene-1, an α-olefin having 6 carbon atoms, by a gas phase polymerization process having a molecular weight distribution of 1.1 to 5 / cm ³ . These may be any method as long as the polymerization is carried out in the presence of a metallocene-based catalyst.For example, polymerization in an improved high-pressure polymerization method is to maintain the polymer in a solution state and to increase the polymerization activity. 120 ° C. or higher, at a temperature of 350 ° C. or lower, preferably 150 to 300 ° C., 400 kg / cm ² or higher, 500 to 2000 kg / at a temperature of 350 ° C. or lower, preferably 150 to 300 ° C. in order to suppress a chain transfer reaction that causes a decrease in molecular weight
It is preferably performed at a pressure of cm ² . Further, in the polymerization in the gas phase polymerization method, high temperature is not preferable because the copolymer is in a powder state, and is preferably 100 ° C. or lower,
The lower limit of the polymerization temperature is not particularly limited, but is preferably 50 ° C. or higher in order to increase the polymerization activity. In order to enhance the polymerization activity, it is preferable to use a catalyst component preliminarily polymerized with an olefin, an organic aluminum compound and an ionized ionic compound. In the polymerization in the solution polymerization method, the polymerization temperature needs to be 120 ° C. or higher in consideration of the fact that the copolymer is in a solution state and that the polymerization activity is increased. The upper limit of the polymerization temperature is not particularly limited, but is preferably 350 ° C. or lower in order to suppress a chain transfer reaction that causes a decrease in molecular weight and not to lower the catalyst efficiency. The pressure at the time of polymerization is not particularly limited, but is preferably at least atmospheric pressure and not more than 250 kg / cm ^{2 in} order to balance economy and polymerization activity.

In any case, the catalyst residue adversely affects the photographic properties of the photographic light-sensitive material. In addition, rust is generated at the resin contact portion of the mold or the extruder to deteriorate dimensional accuracy and appearance. In addition, since resin burning and spots are generated, it is preferable that the amount is small in the present invention.

In particular, 5 kg of L-LDPE per gram of catalyst
A metallocene-based catalyst capable of polymerizing a resin is preferable, and a metallocene-based catalyst using zirconium capable of polymerizing and manufacturing 10 kg of an L-LDPE resin per 1 g of the catalyst is most preferable.

In this case, polymerization can be effectively produced even in a gas phase process, and the molecular weight distribution (Mw / M
The ethylene-hexene-1 random copolymer resin having n) of 1.4 to 4 is the most preferable as the high α-olefin resin of the present invention from the comprehensive evaluation of physical properties, photographic properties, economy and the like.

Therefore, in order to maintain good photographic properties, the amount of residual halogen compounds (mainly halogen gas which adversely affects photographic properties) in the packaging material of the present invention is 40%.
0 ppm or less, preferably 200 ppm or less, more preferably 100 ppm or less, more preferably 1 to 80 pp
m, most preferably 4 to 60 ppm.

Halogen compound components which adversely affect photographic properties and cause rusting failures in extruders and dies include titanium halide compounds, silicon halide compounds, vanadium halide compounds, silicon halide compounds, and aluminum halide compounds. , Boron halide compounds and the like.

Specific examples include silicon tetrachloride, aluminum trichloride, aluminum tribromide, titanium trichloride, boron trichloride, titanium tetrabromide and the like.

These halogen compound components become halogen gas and exert the above-mentioned various adverse effects. Therefore, the catalyst residue is extracted by using a catalyst deactivator, or a pentant is provided on a pelletizer or a molding machine to remove the residual halogen compound. Although it is preferable to reduce the components, it is particularly preferable to include a halogen gas scavenger in the packaging material.

Preferred compounds as the halogen gas scavenger in the present invention are, for example, sulfide compounds, nitrites, semicarbazides, sulfites, hydroquinones, ethylenediamine, acetone semicarbazone,
p-Hydroxyphenylglycine. Particularly preferred compounds include compounds represented by the following general formula.

[0053]

Embedded image In the formula, R ₁ , R ₂ , R ₃ and R ₄ each represent a hydrogen atom or a group which can be substituted on a benzene nucleus.

In the general formula, substituents include a halogen atom (for example, fluorine, chlorine, bromine), an alkyl group (for example, methyl, ethyl, n-propyl, t-butyl, n-amyl, i-amyl, n-amyl) -Octyl, n-dodecyl, n-octadecyl, particularly preferably having 1 to 32 carbon atoms), alkenyl group, aryl group, acyl group, cycloalkyl group, alkoxy group, aryloxy group, alkylthio group, alkylthio group, arylthio group, alkylacylamino Group, arylacylamino group, alkylcarbamoyl group, arylcarbamoyl group, alkylcarbonamide group, arylcarbonamide group, alkylsulfonamide group, arylsulfonamide group, alkylsulfamoyl group,
Arylsulfamoyl group, alkylsulfonyl group, arylsulfonyl group, alkyloxycarbonyl group, aryloxycarbonyl group, alkylacyloxy group,
An arylacyloxy group is preferred.

These groups may be further substituted with the same substituents as described above.

Further, transition metals such as chromium, zirconium,
The residual amount of any one of titanium, hafnium, and vanadium is 400 ppm or less, preferably 200 ppm or less, more preferably 100 ppm or less, particularly preferably 60 ppm or less, and most preferably 40 ppm or less.

Particularly preferred ethylene / α in the present invention
-Olefin copolymer resin, in the presence of a catalyst comprising a transition metal compound of Group IV of the periodic table containing a ligand having a cyclopentadienyl skeleton and a co-catalyst, an organoaluminum compound, and a carrier if necessary, It is obtained by copolymerizing ethylene and an α-olefin having 3 to 20 carbon atoms. Further, a catalyst obtained by pre-polymerizing ethylene and an α-olefin into the above catalyst in advance may be used as the catalyst.

The cyclopentadienyl skeleton of the transition metal compound belonging to Group IV of the periodic table containing a ligand having a cyclopentadienyl skeleton, which is a catalyst for producing the ethylene / α-olefin copolymer, is a cyclopentadienyl skeleton. Pentadienyl group, substituted cyclopentadienyl group and the like. Examples of the substituted cyclopentadienyl group include a hydrocarbon group having 1 to 10 carbon atoms, a silyl group, a silyl-substituted alkyl group, a silyl-substituted aryl group, a cyano group, a cyanoalkyl group, a cyanoaryl group,
And a substituted cyclopentadienyl group having at least one substituent selected from a halogen group, a haloalkyl group, a halosilyl group and the like. The substituted cyclopentadienyl group may have two or more substituents, and the substituents may combine with each other to form a ring.

Examples of the hydrocarbon group having 1 to 10 carbon atoms include an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group and the like. Specific examples include a methyl group, an ethyl group, an n-propyl group and an isopropyl group. Group, n-butyl group,
Alkyl groups such as isobutyl group, sec-butyl group, t-butyl group, pentyl group, hexyl group, octyl group, 2-ethylhexyl group and decyl group; cycloalkyl groups such as cyclopentyl group and cycloalkyl group; phenyl group and tolyl Aryl groups such as groups; benzyl groups, neophyl groups and the like are preferred.

Preferred examples of the substituted cyclopentadienyl group include a methylcyclopentadienyl group, an ethylcyclopentadienyl group, an n-hexylcyclopentadienyl group, a 1,3-dimethylcyclopentadienyl group, 1,
3-n-butylmethylcyclopentadienyl group, 1,3
Specific examples include -n-propylmethylethylcyclopentadienyl group. As the substituted cyclopentadienyl group, among these, a cyclopentadienyl group substituted by an alkyl group having 3 or more carbon atoms is preferable.
A 3-substituted cyclopentadienyl group is preferred. When the substituents, that is, the hydrocarbons are bonded to each other to form one or more rings, the substituted cyclopentadienyl group includes an indenyl group, a hydrocarbon group having 1 to 8 carbon atoms (such as an alkyl group), and the like. A substituted indenyl group, a naphthyl group, a substituted naphthyl group substituted with a substituent such as a C1-C8 hydrocarbon group (such as an alkyl group), a C1-C8 hydrocarbon group ( Preferred examples thereof include a substituted fluorenyl group substituted by a substituent such as an alkyl group.

As the transition metal of the transition metal compound of Group IV of the periodic table containing a ligand having a cyclopentadienyl skeleton, zirconium, titanium, vanadium, hafnium and the like can be mentioned, and zirconium is particularly preferable.
The transition metal compound generally has 1 to 3 ligands having a cyclopentadienyl skeleton, and when having 2 or more ligands, they may be bonded to each other by a crosslinking group.
In addition, examples of such a crosslinking group include an alkylene group having 1 to 4 carbon atoms, an alkylsilanediyl group, and a silanediyl group.

Typical examples of the ligands other than those having a cyclopentadienyl skeleton in the transition metal compounds belonging to Group IV of the periodic table include hydrogen and carbon atoms having 1 to 20 carbon atoms.
(Alkyl group, alkenyl group, aryl group, alkylaryl group, aralkyl group, polyenyl group, etc.), halogen, methalkyl group, metaaryl group and the like.

As the co-catalyst in the present invention, a co-catalyst capable of effectively using the above-mentioned transition metal compound of Group IV of the periodic table as a polymerization catalyst or balancing a catalytically activated ionic charge can be used. Say. Examples of the co-catalyst used in the present invention include benzene-soluble aluminoxane, benzene-insoluble organic aluminum oxy compound, boron compound, lanthanide salts such as lanthanum oxide, and tin oxide of the organic aluminum oxy compound. Of these, aluminoxanes are most preferred.

The catalyst may be used by being supported on an inorganic or organic carrier. As this carrier, an inorganic or organic porous oxide is preferable, and specifically, SiO ₂ , Al ₂ O
₂ , MgO, ZrO ₂ , TiO ₂ , B ₂ O ₂ , CaO, Zn
O, BaO, ThO _{2 and the} like or a mixture thereof, and examples thereof include SiO ₂ —Al ₂ O ₂ , SiO ₂ —V ₂ O ₂ , and SiO ₂ —Ti.
Inorganic carriers such as O ₂ , SiO ₂ —MgO, SiO ₂ —Cr ₂ O ₂ and polyethylene, polypropylene, polybutene-1,
Organic carriers such as poly-4-methylpentene-1 and styrene-divinylbenzene are exemplified.

An organic carrier is preferred because of less generation of fish eyes and gels, and a carboxylic anhydride graft polymer of a polyolefin is particularly preferred.

Examples of the organic aluminum compound include trialkyl aluminum such as triethyl aluminum and triisopropyl aluminum; dialkyl aluminum halide; alkyl aluminum sesquihalide; alkyl aluminum dihalide; alkyl aluminum hydride; and organic aluminum alkoxide.

The ethylene / α-olefin copolymer is produced by a gas phase polymerization method, a slurry polymerization method, a solution polymerization method or the like in the absence of a solvent in the presence of the above-mentioned multi-site catalyst or single-site catalyst. In a state where oxygen, water, etc. are cut off, aliphatic hydrocarbons such as butane, pentane, hexane, and hebutane; aromatic hydrocarbons such as benzene, toluene, and xylene; alicyclic hydrocarbons such as cyclohexane and methylcyclohexane; It is produced in the presence of an inert hydrocarbon solvent exemplified in the above. The polymerization conditions are not particularly limited, but the polymerization temperature is usually 15 to 350 ° C, preferably 20 to
To 200 ° C, more preferably 50 to 110 ° C,
In particular, in the case of the improved high-pressure method using a Ziegler catalyst, 130
To 350 ° C., and the polymerization pressure is usually normal pressure to 70 kg / cm ² , preferably normal pressure to 20 kg /
cm ² , usually 1500 kg / c for the improved high pressure method.
m ² or less, particularly 400 to 900 kg / cm ^{2 in} the case of an improved high-pressure method using a Ziegler catalyst. The polymerization time is usually from 3 minutes to 10 hours, preferably from 5 minutes to 5 hours in the case of the low and medium pressure method. In the case of the improved high-pressure method, it is generally desirable that the heating time is about 1 minute to 30 minutes, preferably about 2 minutes to 20 minutes. In addition, the polymerization is not particularly limited to a single-stage polymerization method, as well as a multi-stage polymerization method of two or more stages in which polymerization conditions such as hydrogen concentration, monomer concentration, polymerization pressure, polymerization temperature, and catalyst are different from each other.

Another most preferred specific example is a resin obtained by copolymerizing ethylene and an α-olefin having 3 to 20 carbon atoms in the presence of various metallocene catalysts, most preferably in the presence of the above specific metallocene catalyst. To ethylene
30-150 ° C per kg of α-olefin copolymer
0.03 to ³ m ³ / h depending on the air or inert gas
r at a flow rate of 0.5 to 72 hours and / or with hot water having a flow rate of 0.001 to 0.5 m ³ / hr with hot water having a temperature of 30 ° C. or higher and lower than the melting point of the ethylene / α-olefin copolymer. An active gas is introduced, immersed for 0.5 to 30 hours, and the value (Q) before and after drying of the total amount (in terms of normal hexane) of volatile components having 12 or less carbon atoms measured by head space gas chromatography is calculated. This is a method for producing an ethylene / α-olefin copolymer of 200 or more.

The copolymer resin of propylene and α-olefin includes propylene-ethylene random copolymer resin, propylene-ethylene block copolymer resin, propylene / butene-1 random copolymer resin, propylene / butene -1 block copolymer resin, propylene / ethylene / butene-1 terpolymer resin, propylene / ethylene / diene terpolymer resin, propylene /
Hexene-1 random copolymer resin, propylene / hexene-1 block copolymer resin and the like.

The α-olefin in the copolymer resin of propylene and α-olefin is the same as the α-olefin used in the case of the copolymer of ethylene and α-olefin.

The homo α-olefin copolymer resin includes homopolybutene-1 copolymer resin, homopolyethylene resin, homopolypropylene resin, homo-4-methylpentene-1 resin, homohexene-1 resin, homomethylpentene resin. And a homopolybutene resin.

In the high α-olefin resin layer of the present invention,
The various high α-olefin resins described above can be used alone or in combination with two or more. Further, a thermoplastic resin other than the high α-olefin resin may be partially contained.

The high α-olefin resin has a melt flow rate (E condition of ASTM D1238) of 0.1 to 1
0 g / 10 min, preferably 0.2 to 8 g / 1.
The time is more preferably 0 minutes, particularly preferably 0.5 to 6 g / 10 minutes, and most preferably 0.8 to 5 g / 10 minutes. Melt flow rate is 0.1g
If the heating time is less than / 10 minutes, the fluidity of the resin is poor, the shear stress is increased, the melt fracture occurs frequently, and the appearance is deteriorated. On the other hand, if the melt flow rate exceeds 10 g / 10 minutes, bubbles become unstable, streaks and wrinkles are easily generated, film formation is difficult, and the physical strength of the film decreases.

The high α-olefin resin has a density of 0.8
7 to 0.94 g / cm ³ , preferably 0.88
０．９0.93 g / cm ³ , more preferably 0.8
Most preferably, it is 9 to 0.925 g / cm ³ .
When the density is less than 0.87 g / cm ³ , not only is polymerization difficult and expensive, but also the film formability is poor, the Young's modulus is extremely small, and blocking is liable to occur. If the density exceeds 0.94 g / cm ³ , molecular orientation tends to occur in the longitudinal direction, and the longitudinal and lateral strength balance of tear strength is lost. Further, the fluidity of the resin is deteriorated, and melt fracture is likely to occur.

Preferred examples of the high α-olefin resin in the present invention are described below. (1) containing 1% by weight or more of α-olefin having 4 to 8 carbon atoms, having a melt flow rate of 0.1 to 10 g / 10 minutes,
Homo α-olefin resin having a density of 0.87 to 0.94 g / cm ³ (2) containing 1% by weight or more of α-olefin having 4 to 8 carbon atoms, and having a melt flow rate of 0.1 to 10 g / 10 min. ,
Ethylene α-having a density of 0.87 to 0.94 g / cm ³
Olefin copolymer resin or propylene-α-olefin copolymer resin

In the high α-olefin resin layer of the present invention,
The following modifiers (hinder phenolic antioxidant, lubricating substance, anti-blocking) are used to improve photographic properties, anti-blocking properties, film forming suitability, thermal deterioration prevention, bag making suitability, and antistatic properties. Agents, hydrotalcite compounds, scavengers of hydrogen cyanide gas, scavengers of aldehyde gas, and antistatic agents).

Hindered phenolic antioxidants include 1,3,5-trimethyl 2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, tetrakis [methylene-3- (3 '・ 5'-di-te
rt-butyl-4'-hydroxyphenyl) propionate] methane, octadecyl-3,5-di-tert-butyl-4-hydroxy-hydrocinnamate, 2,2 ',
2'-tris [(3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxy] ethyl isocyanurate, 1,3,5-tris (4-tert-butyl-3-hydroxy-2,6- Di-methylbenzyl] isocyanurate, tetrakis (2,4-di-tert-butylphenyl) 4,4′-biphenylenediphosphite, 4,4′-thiobis- (6-tert-butyl-O—
Cresol), 2,2'-thiobis- (6-tert-
Butyl-4-methylphenol), tris- (2-methyl-4-hydroxy-5-tert-butylphenyl)
Butane, 2,2'-methylene-bis- (4-methyl-6-
tert-butylphenol), 4,4′-methylene-bis- (2,6-di-tert-butylphenol),
4'-butylidenebis- (3-methyl-6-tert-
Butylphenol), 2,6-di-tert-butyl-4
-Methylphenol, 4-hydroxymethyl-2,6
-Di-tert-butylphenol, 2,6-di-te
rt-4-n-butylphenol, 2,6-bis (2′-
(Hydroxy-3'-tert-butyl-5'-methylpentyl) -4-methylphenol, 4,4'-methylene-
Bis- (6-tert-butyl-O-cresol), 4,
4'-butylidene-bis (6-tert-butyl-m-cresol), 3,9-bis {1,1-dimethyl-2- [β
-(3-t-butyl-4-hydroxy-5-methylphenyl) propionyloxy] ethyl {2,4.8,10-
And tetraoxaspiro [5,5] undecane. Among them, the melting point is 100 ° C. or more, especially 120 ° C.
C. or higher is preferred. Further, it is effective to use it in combination with a phosphorus antioxidant. Furthermore, the combined use of at least one of phosphorus-based antioxidants, at least one of hindered phenol-based antioxidants, and at least one of hydrotalcite-based compounds makes it possible to improve photographic properties. It is particularly preferable from the viewpoint of preventing the resin and additives from being thermally degraded or decomposed, and preventing the molding machine from rusting. The total amount of these additives is preferably 0.01 to 6.5% by weight from the viewpoint of balance between economy, photographic properties, heat deterioration prevention properties and the like.

The lubricating substance is used in the high α-olefin resin layer to form a thermoplastic resin such as a high α-olefin resin.
It is contained in an amount of 0.01 to 50 parts by weight, preferably 0.02 to 40 parts by weight, more preferably 0.03 to 100 parts by weight.
To 30 parts by weight, particularly preferably 0.04 to 20 parts by weight,
Most preferably, it is contained in an amount of 0.04 to 10 parts by weight. By containing a lubricating substance, it is possible to prevent the thermoplastic resin films from blocking each other in a film forming step, a laminating step, a bag making step, etc., and to improve the handling suitability and lubricity of the thermoplastic resin film to improve wrinkles and streaks. Can be prevented. Furthermore, even if the multilayer coextruded film and the photosensitive material are stacked, no blocking occurs, and even if the photosensitive material is rubbed with a photographic photosensitive material as a packaging bag, scratches and static marks do not occur. it can. Further, the fluidity of the resin is improved, and the moldability is improved, and the lubricity of the molded product can be improved.

When the content of the lubricating substance is less than 0.01 part by weight based on 100 parts by weight of the thermoplastic resin, there is no effect of addition and only the kneading cost increases, and also 100 parts by weight of the thermoplastic resin. If it exceeds 50 parts by weight, foaming, white smoke and die lip streaks are likely to occur, or the slip between the molten resin and the screw of the extruder tends to occur,
The discharge amount of the resin becomes unstable. In addition, stickiness and bleed-out tend to occur with the passage of time after molding, which adversely affects the photographic material. Furthermore, when a thermoplastic resin film for a sealed packaging bag is used, the heat sealing strength over time is reduced, and the sealing property, moisture-proof property and oxygen barrier property are deteriorated. .

As the lubricating substance, JP-A-6-31788
One or more kinds of lubricants can be selected and used in an appropriate amount from the various lubricants described on page 5 [0032] to page 6 [0044] of JP-A No. 1 according to the purpose of use.

When dimethylpolysiloxane of various grades and modified products thereof (Shin-Etsu Silicone, Toray Silicone), especially various silicone oils, not only exert the effects of improving resin fluidity and lubricity, but also when used in combination with a light-shielding substance. Haze (A)
As a result of increasing STM D-1003), unexpected effects such as an improvement in coloring power and an improvement in light-shielding properties are exhibited.

The silicone oil preferably has a viscosity at room temperature (25 ° C.) of 50 to 100,000 centistokes, more preferably 5,000 to 100,000 centistokes.
A high viscosity of 30,000 centistokes is preferred.
Specific examples of silicone and silicone-modified products include polymethylphenylsiloxane, olefin-modified silicone, amide-modified silicone, polydimethylsiloxane,
Amino-modified silicone, carboxyl-modified silicone,
Silicone oil containing modified siloxane bonds such as α-methylstyrene-modified silicone, polyether-modified silicone modified with polyethylene glycol or polypropylene glycol, olefin / polyether-modified silicone, epoxy-modified silicone, amino-modified silicone, and alcohol-modified silicone. . Among the silicone oils, those which do not adversely affect the photographic light-sensitive material, have a large lubricating effect, and are preferable when applied to packaging materials include olefin-modified silicone, amide-modified silicone, polydimethylsiloxane, polyether-modified silicone, It is an olefin / polyether-modified silicone.

Silicone oil improves the coefficient of friction of a molding material, for example, a resin film in a heated state, reduces sliding resistance generated during hot plate sealing by an automatic packaging machine,
By preventing wrinkles from occurring, it is possible to form the basis for obtaining a resin film having a beautiful appearance, a high degree of sealing performance, and a performance that has tight adhesion to a package. In addition, it is possible to prevent a decrease in gloss due to sliding and obtain a beautiful seal portion. In the present invention in which silicone oil is used in combination, the coefficient of high-temperature friction can be set to 1.4 or less when performing sliding heat sealing.

The effects of adding silicone oil are as follows. (1) The surface of these materials is coated only by using the fibrous filler, the non-fibrous light-shielding substance, and the pigment together to improve dispersibility. (2) Improve the dispersibility of the resin, reduce the motor load on the screw, and prevent the occurrence of melt fracture. (3) Sufficient lubricity can be ensured without adding a fatty acid amide that bleeds out to form a white powder. (4) The coefficient of friction of the molding material in a heated state is reduced, the suitability for an automatic bag is improved, the generation of wrinkles during heat sealing and the decrease in gloss due to sliding can be prevented, and a beautiful sealed portion can be obtained. (5) When used in combination with a light-shielding substance, the thermoplastic resin becomes cloudy and the haze is increased. As a result, the coloring power can be improved and the light-shielding ability can be improved. Nature can be secured.

The anti-blocking agent is preferably contained in the high α-olefin resin layer in an amount of 0.01 to 30 parts by weight, more preferably 0.01 to 30 parts by weight, based on 100 parts by weight of a thermoplastic resin such as a high α-olefin resin. Is 0.02 to 2
0 parts by weight, particularly preferably 0.03 to 10 parts by weight, most preferably 0.05 to 5 parts by weight. By containing the anti-blocking agent, it is possible to prevent the films from adhering to each other or to prevent the film from adhering to the photosensitive material.

If the content of the anti-blocking agent is less than 0.01 with respect to 100 parts by weight of the thermoplastic resin, the anti-blocking effect cannot be exerted, and the cost of kneading only increases. If the amount exceeds 30 parts by weight with respect to 100 parts by weight of the resin, not only a large number of non-uniform failures (bulk) occur but also the physical strength and the heat sealability of the film decrease.

As the antiblocking agent, zeolite
(Including natural and synthetic zeolites), silica (including natural and synthetic silica), calcium carbonate, talc (magnesium silicate), aluminum silicate, calcium silicate, fatty acid amide-based lubricant, higher fatty acid polyvinyl ester, n-octadecyl urea , N, N'-dioleyl oxamide, N-ethanol stearic acid amide, dicarboxylic acid ester amide and the like. Among them, zeolite having various gas adsorbing and detoxifying effects which have an anti-blocking effect and adversely affect photographic properties. Silica is particularly preferred.

The zeolite is a natural zeolite (anal).
cime, chabazite, heulandite,
erionite, ferrierite, laumo
zeolites containing ntite, modernite, etc.), synthetic zeolites (A, NA, X, Y, hya)
droxy sodalite, ZK-5, B, R, D,
T, L, hydroxy, cancrinite, W,
There are various types of zeolites such as Zeolaon. Among these, A-type zeolites having a large harmful gas adsorption detoxifying ability which adversely affects photographic properties are particularly preferred. These zeolites function excellently as a metal carrier and as a metal-based inorganic antibacterial agent. For example, there is A-type synthetic zeolite supporting silver ions.

Further, since this zeolite functions excellently as a metal-based inorganic antibacterial agent (for example, an A-type synthetic zeolite carrying silver ions) as a metal carrier, when the antibacterial action is mainly intended, the zeolite is used in the inner surface layer. 0.001 to 10% by weight, preferably 0.002 to 8% by weight, particularly 0.005%
If it is contained in an amount of 5 to 5% by weight, it is suitable for a photographic light-sensitive material in which a hydrophilic polymer, such as gelatin, which is easily absorbed and easily blocks or biodegrades, is used for the photographic emulsion layer, protective layer, back layer and the like.

The above silica has an average particle diameter of 0.3 to 20.
μm is preferred, and 0.5 to 15 μm is more preferred. When the average particle size is less than 0.3 μm, the cohesiveness is strong, and lumps occur frequently, and the blocking prevention effect is small. On the other hand, when the average particle diameter exceeds 20 μm, not only silica is formed on the surface of the film, but the surface of the film becomes rough, and scratches and the like easily occur on the photographic light-sensitive material.

The hydrotalcite compound is preferably contained in the high α-olefin resin layer in an amount of 0.001 to 20 parts by weight based on 100 parts by weight of a thermoplastic resin such as a high α-olefin resin. More preferably 0.00
5 to 15 parts by weight, particularly preferably 0.01 to 10 parts by weight, most preferably 0.02 to 5 parts by weight. By containing hydrotalcite compounds, it neutralizes catalyst residues, detoxifies substances that adversely affect photographic properties by absorbing halogen compounds such as hydrochloric acid, and prevents mold rusting, It can prevent resin burning failure and the like.
In particular, one of phenolic antioxidants and phosphorus antioxidants
When used in combination with more than one species, photographic and thermoplastic resins, 1,2-
The polybutadiene-based thermoplastic elastomer and additives have a large effect of preventing thermal degradation and thermal decomposition, which is preferable.

If the content of the hydrotalcite compound is less than 0.001 part by weight with respect to 100 parts by weight of the thermoplastic resin, the effect of addition is not exhibited and only the kneading cost is increased. If the amount exceeds 20 parts by weight with respect to 100 parts by weight of the plastic resin, there is no effect of increasing the amount, and only the occurrence of bumps and an increase in cost will be caused.

Preferred specific examples are shown below. Mg _0.7 Al _0.3 (OH) ₂ (CO ₃ ) _0.15・ 0.54H ₂
O Mg _0.67 Al _0.33 (OH) ₂ (CO ₃ ) _0.165 · 0.5H ₂
O Mg _0.67 Al _0.33 (OH) ₂ (CO ₃ ) _0.165・ 0.2H ₂
O Mg _0.6 Al _0.4 (OH) ₂ (CO ₃ ) _0.2 · 0.42 H ₂ O Mg _0.75 Al _0.25 (OH) ₂ (CO ₃ ) _0.125 · 0.63
H ₂ O Mg _0.83 Al _0.17 (OH) ₂ (CO ₃ ) _0.085・ 0.4H ₂
O etc.

These hydrotalcite compounds are:
It may be a natural product or a synthetic product. These hydrotalcite compounds are mainly composed of magnesium, aluminum, etc., and have an adverse effect on the photographic properties of photographic light-sensitive materials and chlorine ions, which are considered to be a cause of rusting of metals used in molding machines. It is excellent in the ability to adsorb and neutralize halogenated ions to make it harmless. Further, it is presumed that substances that adversely affect photographic properties, such as monomers in thermoplastic resins and volatile substances in various additives, are adsorbed and fixed.

Further, the phosphorous antioxidant added to prevent the thermal degradation and thermal decomposition of the thermoplastic resin and additives is neutralized by phosphorous acid which is generated when the phosphorus is thermally decomposed and adversely affects the photographic properties of the photographic light-sensitive material. And has an unexpected effect of improving photographic properties (reducing fog). As a specific method for synthesizing the hydrotalcite compound, known methods disclosed in Japanese Patent Publication No. 46-2280, Japanese Patent Publication No. 50-30039 and the like can be used.

Examples of natural products of hydrotalcite compounds include hydrotalcite, stichtite, pyroaulite and the like. These hydrotalcite compounds may be used alone or in combination of two or more.
In particular, it is preferable to use together with various antioxidants and various fatty acid metal salts. Processability, dispersibility, below 20μm average secondary particle diameter in order to improve particular physical properties, etc., preferably 10μm or less, particularly preferably 5μm or less, BET specific surface area of 50 m ² / g or less, preferably 40 m ² / g or less,
In particular, it is preferably 30 m ² / g or less.

The hydrogen cyanide gas scavenger is used in the high α-olefin resin layer in an amount of 0.01 to 100 parts by weight of thermoplastic resin such as high α-olefin resin.
It is preferably contained in an amount of 10 to 10 parts by weight, more preferably 0.02 to 8 parts by weight, particularly preferably 0.03 to 6 parts by weight, and most preferably 0.04 to 5 parts by weight.
By containing the hydrogen cyanide gas scavenger, the hydrogen cyanide gas can be converted into a substance inert to the photosensitive material, so that the quality (mainly photographic properties) of the photosensitive material can be maintained well.

If the content of the hydrogen cyanide gas scavenger is less than 0.01 part by weight based on 100 parts by weight of the thermoplastic resin, there is no effect of addition and only the kneading cost is required. On the other hand, if the amount exceeds 10 parts by weight, there is no effect of increasing the amount and only the cost becomes high.

The aldehyde gas scavenger is used in the high α-olefin resin layer in an amount of 0.01 to 100 parts by weight of a thermoplastic resin such as a high α-olefin resin.
It is preferably contained in an amount of 10 to 10 parts by weight, more preferably 0.02 to 8 parts by weight, particularly preferably 0.03 to 6 parts by weight, and most preferably 0.04 to 5 parts by weight.
By including the aldehyde gas scavenger, the aldehyde gas can be converted into a substance which is inactive to the photosensitive material, so that the quality (mainly photographic properties) of the photosensitive material can be maintained well. In particular, formaldehyde gas not only has an adverse effect on the human body, but also has a strong irritating odor and gives users discomfort, so the effect of adding a scavenger also contributes to an increase in sales.

When the content of the scavenger of the aldehyde gas is less than 0.01 part by weight based on 100 parts by weight of the thermoplastic resin, there is no effect of addition and only kneading cost is required. If the amount exceeds 10 parts by weight with respect to part by weight, there is no effect of increasing the amount, and only the cost becomes high.

Examples of aldehyde gas scavengers include hydantoin compounds, hydrazine compounds, amide compounds, urethane compounds, pyridine compounds, pyrrolidone compounds, triazine compounds, amidine compounds, and urea compounds. Particularly effective when used in combination with zeolites that adsorb and detoxify aldehyde gas, the use of inexpensive materials containing aldehyde or recycled resins that are commercially available does not adversely affect photographic properties and gives users a bad smell or pungent odor. It is preferable because it gives no discomfort.

Among these aldehyde gas scavengers, dimer acid-based polyamides, melamine, guanamine, benzoguanamine, N-methylolated melamine, N-methylolated benzoguanamine, thermoplastic polyurethane, which are the most effective in improving photographic properties, are used. Resin, dicyandiamide, guanidine, poly (N-vinylpyrrolidone),
Poly (2-vinylpyridine, polyurea, melem, melam, nylon 6-6,6-6,10 terpolymer resin,
N, N'-diphenylurea is most preferred.

By including the antistatic agent in the high α-olefin resin layer, it is possible to prevent static failure and the like.

The content of the antistatic agent is preferably from 0.01 to 10% by weight, more preferably from 0.02 to 5% by weight.
0.03 to 3% by weight is most preferred. The total content is 0.
If it is less than 01% by weight, there is no effect of addition, and only kneading costs are required. On the other hand, when the total content exceeds 10% by weight, there is no effect of increasing the amount, and only the cost is increased. Furthermore, the amount of bleed-out increases over time,
The heat sealability is deteriorated, and the surface of the packaging material becomes sticky.

The antistatic agent will be described.

Typical examples of the nonionic surfactant-based antistatic agent are shown below. Polyethylene glycol fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene alkyl ether, polyoxyethylene alkylamine, polyoxyethylene alkylamine fatty acid ester, polyoxyethylene aliphatic alcohol ether, polyoxyethylene alkylphenyl ether, polyoxyethylene Glycerin fatty acid ester, polyoxyethylene aliphatic amine, sorbitan monofatty acid ester, fatty acid bentaerythrit, fatty alcohol ethylene oxide adduct, fatty acid ethylene oxide adduct, fatty acid amino or fatty acid amide ethylene oxide adduct, alkylphenol ethylene Oxide adduct, ethylene oxide adduct of alkyl naphthol, polyhydric alcohol part Ethylene oxide adducts of fatty acid esters, polyoxyethylene alkyl amide, alkyl derivatives, and other Japanese Patent Publication 63
Various nonionic antistatic agents described on page 120 of -26697.

Representative examples of the anionic surfactant-based antistatic agent are shown below. Ricinoleic acid sulfate soda salt,
Various fatty acid metal salts, silinoleic acid ester sulfate soda salt, sulfated ethyl aniline oleate, olefin sulfate salts, oleyl alcohol sulfate soda salt, alkyl sulfate ester, fatty acid ethyl sulfonate, alkyl sulfate, alkyl phosphate, Alkyl sulfonates, alkyl naphthalene sulfonates, alkyl benzene sulfonates,
Succinate sulfonate, phosphate ester salt and the like.

Typical examples of the cationic surfactant type antistatic agent are shown below. Primary amine salt, tertiary amine salt, quaternary amine salt
Representative examples of amphoteric surfactants such as quaternary ammonium salts, trialkylbenzylammonium salts and pyridine derivatives are shown below.

Among the above surfactant-based antistatic agents, a nonionic (nonionic) surfactant is used as an antistatic agent because it has a small adverse effect on photographic properties and human body and has a large static mark preventing effect. Is particularly preferred.

The special ethylene copolymer resin contains 5 to 40% by weight of one or more of vinyl acetate and acrylic acid, preferably 6 to 30% by weight, more preferably 7 to 28% by weight, particularly preferably 8 to 28% by weight. 25% by weight, most preferably 9%
２３23% by weight. If the content of at least one of vinyl acetate and acrylic acid is less than 5% by weight, sufficient blocking adhesion cannot be obtained, flexibility and extensibility are insufficient, and physical strength at low temperature is insufficient. In this case, the ability to prevent bag breakage decreases. On the other hand, if the content exceeds 40% by weight, the physical strength becomes insufficient, and it becomes difficult to obtain appropriate slipperiness and rigidity, the odor becomes strong, and film forming becomes difficult.

Examples of the special ethylene copolymer resin include ethylene-ethyl acrylate copolymer resin (“NUCEEA copolymer” of Nippon Unicar, “Evaflex EEA” of Mitsui / Dupont Polychemicals), and ethylene-methyl acrylate copolymer. Coalescing resin ("EMAC" of Nagase Sangyo),
Ethylene-acrylic acid copolymer resin (Dow Chemical's "Primacol", Mitsubishi Chemical's "Mitsubishi Polyethylene-EA"
A)), ethylene-vinyl acetate copolymer resin (Showa Denko's “Showrex EVA”, Tosoh's “Ultracene”, Nippon Unicar's “NUCEVA copolymer”, Mitsui Petrochemical's “Mirason EVA”, Mitsubishi Chemical's “Murason EVA” "Mitsubishi Polyethylene-EVA", Mitsui / Dupont Polychemical "Evaflex-EVA", Asahi Kasei "Suntec-EV"
A "," Evatate "of Sumitomo Chemical," Jerex EVA "of Nippon Polyolefin), etc.""indicates a trade name.

Other examples include ethylene-butyl acrylate copolymer resin and ethylene-acrylate 2-hydroxyethyl copolymer resin.

The melt flow rate of the special ethylene copolymer resin (E condition of ASTM D1238) is 0.1
10 to 10 g / 10 min is appropriate, preferably 0.2 to 9 g / 10 min, more preferably 0.3 to 8 g / 10 min,
Particularly preferred is 0.4 to 7 g / 10 min, and 0.5 to 6 g / min.
10 minutes is most preferred. Melt flow rate is 0.1g
If it is less than / 10 minutes, the fluidity of the resin is poor and melt fracture frequently occurs, and the melt flow rate is 10 g.
If the time exceeds / 10 minutes, the bubble becomes unstable, streaks and wrinkles are easily generated, film formation is difficult, and the physical strength of the film decreases.

The special ethylene copolymer resin preferably has a density of 0.90 to 0.96 g / cm ³ .
More preferably 0.91~0.95g / cm ^3, and most preferably 0.92~0.94g / cm ^3. When the density is less than 0.90 g / cm ³ , not only polymerization is difficult and expensive, but also blocking adhesion is deteriorated. On the other hand, when the density exceeds 0.96 g / cm ³ , the thermal stability deteriorates, and the polymerization becomes difficult and expensive.

Preferred examples of the special ethylene copolymer resin in the present invention are described below. (1) An ethylene vinyl acetate copolymer resin containing 6 to 30% by weight of vinyl acetate and having a melt flow rate of 0.1 to 10 g / 10 minutes. (2) Ethylene acrylic acid containing 6 to 30% by weight and a melt flow rate of 0.1 to 10 g / 10 min.
Ethyl acrylic acid copolymer resin.

The thickness of the special ethylene copolymer resin layer is as follows:
1 to 70 μm is suitable, 3 to 60 μm is preferable,
5 to 50 μm is more preferable, 7 to 40 μm is particularly preferable, and 9 to 30 μm is most preferable. When the thickness is less than 1 μm, the adhesive strength due to blocking may not be sufficient, and when the thickness exceeds 70 μm, the physical strength is reduced.

The special ethylene copolymer-based resin layer has at least one layer in the multilayer co-extruded blown film. However, the ratio to the total thickness (when there are two or more special ethylene copolymer-based resin layers, The total thickness ratio) is suitably from 10 to 90%, preferably from 20 to 80%, more preferably from 30 to 70%, particularly preferably from 35 to 65%, and most preferably from 40 to 60%. If the proportion of the special ethylene copolymer resin layer in the total thickness is less than 10%, the adhesive strength due to blocking may not be sufficiently ensured, and if it exceeds 90%, the physical strength is reduced. In addition, the amount of aldehyde generated due to thermal degradation of the resin increases, so that the pungent odor becomes strong and the commercial value decreases.

Further, when used as a packaging material for photographic light-sensitive materials, photographic properties are adversely affected, resulting in fogging, abnormal color formation,
Sensitivity abnormalities and the like are likely to occur.

It is preferable that the special ethylene copolymer resin layer of the present invention contains an aliphatic alcohol fatty acid ester. By containing the fatty acid fatty acid ester of the aliphatic alcohol resin, it is possible to prevent the adhesion of water droplets (providing suitability), improve the blocking adhesion, impart antistatic property when taken out at room temperature after storage in a low-temperature warehouse for a long time. Can be planned.

The content of the aliphatic alcohol fatty acid ester is suitably 0.01 to 5% by weight, and 0.05 to 5% by weight.
It is preferably 4.5% by weight, more preferably 0.1 to 4% by weight, particularly preferably 0.1 to 3.5% by weight, most preferably 0.1 to 3% by weight.

When the content of the aliphatic alcohol-based fatty acid ester is less than 0.01% by weight, the effect of addition is small and the cost is increased. When the content exceeds 5% by weight, only the amount is increased. The effect is small and only material cost is required.

Preferred examples of the aliphatic alcohol fatty acid ester are compounds of an aliphatic alcohol having 1 to 10 carbon atoms and a fatty acid having 10 to 20 carbon atoms, specifically, monoglycerin oleate and polyglycerin. Oleate, glycerin triricinoleate, glycerin acetyl ricinolate, methyl acetyl ricinolate, ethyl acetyl ricinolate, butyl acetyl ricinolate, propylene glycol oleate, propylene glycol laurate, pentaerythritol oleate,
Polyethylene glycol oleate, polypropylene glycol oleate, polyoxyethylene glycerin,
Examples include polyoxypropylene glycerin, sorbitan oleate, sorbitan laurate, polyethylene glycol sorbitan oleate, polyethylene glycol sorbitan laurate, and polyalkylene ether polyol.

It is preferred that at least one of the special ethylene copolymer resin layer, the high α-olefin resin layer, and the optional intermediate layer of the present invention contain a fatty acid metal salt as a dispersibility improver. . By adding a fatty acid metal salt, when a lubricant, a light-shielding substance, etc. are added,
These dispersibility can be improved.

Further, the film formability can be improved,
The catalyst residue can be neutralized to prevent adverse effects on photographic properties.

The content of the fatty acid metal salt is from 0.01 to 10
% By weight, more preferably 0.02 to 8% by weight, particularly preferably 0.05 to 4% by weight, and most preferably 0.1 to 2% by weight. When the content of the fatty acid metal salt is less than 0.01% by weight, the effect of addition is small and only the kneading cost is increased, and when the content exceeds 10% by weight,
The amount of resin extruded becomes unstable, film formation becomes difficult, and the heat-sealing strength decreases with time, and the sealing property, moisture-proof property and oxygen barrier property deteriorate.

Examples of the fatty acid metal salts include higher lauric acid, stearic acid, succinic acid, stearyl lactic acid, lactic acid, phthalic acid, benzoic acid, hydroxystearic acid, ricinoleic acid, naphthenic acid, oleic acid, palmitic acid and erucic acid. Fatty acids and Li, Na, Mg, Ca, Sr, B
a, a compound with a metal such as Zn, Cd, Al, Sn, Pb, and Cd, and preferred are magnesium stearate, calcium stearylate, sodium stearate, zinc stearate, zinc oleate, and magnesium oleate. Etc.

The names, molecular formulas, states and melting points of typical commercially available fatty acid metal salts are shown below.

[0128]

[Table 2]

In the special ethylene copolymer resin layer, a hindered phenol antioxidant, a hydrotalcite compound, and a scavenger of hydrogen cyanide gas described in detail as preferably contained in the high α-olefin resin layer are described. , An aldehyde gas scavenger, an antistatic agent and the following thermal deterioration inhibitor.
By including a thermal degradation inhibitor, thermal degradation of additives such as a resin and a light-shielding substance can be prevented. The content of the thermal deterioration inhibitor is preferably 0.001 to 5% by weight, more preferably 0.005 to 3% by weight, and 0.01 to 5% by weight.
1% by weight is particularly preferred and 0.02 to 0.5% by weight is most preferred. When the content is less than 0.001% by weight,
The effect of addition is small, and only kneading costs are required. When the content exceeds 5% by weight, the heat sealing strength with the lapse of time is reduced due to bleeding out, and the sealing property, moisture-proof property and oxygen barrier property are deteriorated.

When used as a packaging material for photographic light-sensitive materials, photographic properties are adversely affected. Further, there is no effect of increasing the amount, and the material cost increases.

Representative examples of the thermal deterioration inhibitor include pentaerythrityl-tetrakis [3- (3,5-di-t-butyl-4hydroxyphenyl) propionate and 3,9-
Bis [1,1-dimethyl-2-{(3-t-butyl-4-
(Hydroxy-5-methylphenyl) carbonyloxy}
Ethyl] -2,4,8,10-tetraoxalopyro [5,
5] undecane, 3,9-bis [1,1-dimethyl-2-
｛(3,5-di-t-butyl-4-hydroxyphenyl)
Carbonyloxydiethyl] -2,4,8,10-tetraoxaspiro [5,5] undecane, 3,9-bis [1,
1-dimethyl-2-{(3,5-diphenyl-4-hydroxyphenyl) carbonyloxy} ethyl] -2,4,
8,10-tetraoxapyrro [5,5] undecane, 3,
9-bis [1,1-dimethyl-2- {β- (3,5-dicyclohexyl-4-hydroxyphenyl) carbonyloxy} ethyl] -2,4,8,10-tetraoxaspiro [5,5] undecane Undecane compounds such as 1,3,5
-Tris [(3-methyl-5-t-butyl-4-hydroxyphenyl) carbonyloxyethyl] isocyanurate, 1,3,5-tris [(3,5-di-t-butyl-4
-Hydroxyphenyl) carbonyloxyethyl] isocyanurate, 1,3,5-tris [(3-methyl-5-
t-butyl-4-hydroxyphenyl) acetyloxyethyl] isocyanurate, 1,3,5-tris [(3,
5-di-t-butyl-4-hydroxyphenyl) acetyloxyethyl] isocyanurate compound.

One or more of the high α-olefin-based resin layer, the special ethylene copolymer-based resin layer, and the optional intermediate layer may contain a light-shielding substance.
By including a light-shielding substance, light-shielding properties can be ensured when packaging an object such as a photosensitive material that requires light-shielding properties.

The light-shielding substance will be described. (1) Inorganic compound A. Oxide: silica, diatomaceous earth, alumina, titanium oxide, iron oxide (iron black), zinc oxide, magnesium oxide, antimony oxide, barium ferrite, strontium ferrite, beryllium oxide, pumice, pumice balloon, alumina fiber, etc. Hydroxide: aluminum hydroxide, magnesium hydroxide, basic magnesium carbonate, etc. Carbonate: calcium carbonate, magnesium carbonate, dolomite, dawsonite, etc. (Sulfite): calcium sulfate, barium sulfate, ammonium sulfate, calcium sulfite, etc. Silicates: talc, clay, mica, asbestos,
F. Glass fiber, glass balloon, glass beads, calcium silicate, montmorillonite, bentonite, etc. Carbon: carbon black, graphite, carbon fiber, carbon hollow sphere, etc. Others: iron powder, copper powder, lead powder, aluminum powder, molybdenum sulfide, polon fiber, silicon carbide fiber, brass fiber,
Potassium titanate, lead zirconate titanate, zinc borate, barium metaborate, calcium borate, sodium borate, aluminum paste, various whiskers, etc. (2) Organic compounds wood flour (pine, oak, sawdust, etc.), shell fiber (Almonds, peanuts, fir husks, etc.), cotton, jute, paper chips, non-wood fibers (straw, kenaf, bamboo, esparto, pagas, moroheiya, smoke, etc.) cellophane pieces, nylon fibers, polypropylene fibers, starch (modified starch) , Including surface-treated starch), aromatic polyamide fibers, etc.

Among these light-shielding substances, inorganic compounds which do not adversely affect photographic properties and are stable to heat even at a temperature of 150 ° C. or higher and are opaque are preferable. Active materials, light absorbing carbon black, titanium nitride, graphite and iron black are preferred.

Most preferred are flaky graphite, bengala, talc, mica, barium ferrite, aluminum powder, aluminum paste, flaky metal powder, flakes and the like having an aspect ratio of 5 or more on light-absorbing carbon black or iron black. To improve dispersibility and light-shielding properties in combination with at least one of the above, or to improve dispersibility and light-shielding properties by using in combination with one or more carbon black and pigments having a Mohs hardness greater than that of carbon black (eg, titanium oxide). It has been improved.

Examples of classification according to the raw material of carbon black include gas black, furnace black, channel black, anthracene black, acetylene black, Ketjen carbon black, thermal black,
There are lamp black, oil smoke, pine smoke, animal black, vegetable black and the like.

Representative examples of preferable commercial products of carbon black include, for example, carbon black # 2 manufactured by Mitsubishi Kasei.
0 (B), # 30 (B), # 33 (B), # 40 (B), # 41
(B), # 44 (B), # 45 (B), # 50, # 55, # 1
00, # 600, # 950, # 1000, # 2200
(B), # 2400 (B), MA8, MA11, MA100
And the like.

Overseas products include, for example, Black Pearls 2, 46, 70, 71, 7 of Cabot Corporation.
4,80,81,607 etc., Regal 300,330,4
00, 660, 991, SRF-S etc., Vulcan 3,
6, Sterling 10, SO, V, S, FT-F
F, MT-FF and the like.

Further, Unit of Ashland Chemical Co., Ltd.
ed R, BB, 15,102,3001,3004,30
06,3007,3008,3009,3011,3012,
XC-3016, XC-3017, 3020, and the like, but are not limited thereto.

Channel black produced by contacting the back side of channel steel while incompletely burning a gas flame of natural gas or a gaseous or vaporous hydrocarbon in these various carbon blacks to precipitate carbon black. Although they have high coloring power, they have poor photographic properties and contaminate the air during production, and are not preferred in the present invention in terms of photographic properties and environmental problems.

The carbon black preferred in the present invention is produced by continuously burning or partially decomposing acetylene black and natural gas, hydrocarbon oil or a mixture thereof in a furnace at 1200 ° C. to 1700 ° C. Furnace black.

When the packaging material of the present invention is applied to a photographic photosensitive material package, at least one of creosote oil and ethylene bottom oil is used as a raw material oil so as not to adversely affect the photographic properties of the photographic photosensitive material. 1200 ° C to 170
Furnace carbon black produced by continuous partial combustion in a furnace at 0 ° C. or by thermal decomposition is preferred. By using such furnace carbon black, adverse effects on the photographic light-sensitive material can be further reduced.

ASTM D 1619-60 in packaging material
Is 0.9% or less, preferably 0.7% or less, particularly preferably 0.5% or less, and most preferably 0.1% or less. If the content is not limited to this range, adverse effects on the photographic properties of the photographic light-sensitive material, such as an increase in fog, abnormal sensitivity, abnormal occurrence, etc. In particular, a free sulfur component which has a great adverse effect on the photographic properties of the direct photographic light-sensitive material. Each sample is solidified by cooling with liquid nitrogen and then pulverized. 100 g of the pulverized sample is placed in a Soxhlet extractor and extracted with chloroform at 60 ° C. for 8 hours. The total volume is 100 ml. 10m of this solution
1 is injected into a high performance liquid chromatograph and sulfur is determined. High-performance liquid chromatographic separation conditions are column; ODS
Silica column (4.6φ × 150 mm), separation solution: methanol 95 and water 5 (acetic acid and triethylamine were each added to 0.1% each).
1%), flow rate: 1 ml / min, detection wavelength: 254n
m, Quantification is performed by the absolute calibration curve method. ｝ Is 0.1%
Or less, preferably 0.05% or less, particularly preferably 0.1% or less.
01% or less. Although expensive, acetylene black having a sulfur content of 0.1% or less has an ISO sensitivity of 100.
It is suitable for maintaining high photographic properties satisfactorily as described above for high-sensitivity photographic materials.

For this purpose, it is important to select a raw material. For example, the following explains the sulfur content. Raw material Oil name Sulfur content in feed oil Creosote oil ｛Coal-based feedstock｝ 0.3-0.6% Ethylene bottom oil ｛Naphtha feedstock (petroleum-based feedstock)｝ 0.05-0.1% Ethylene bottom oil ｛ Gas oil feedstock (petroleum-based feedstock)｝ 0.2-1.5% Fluid catalytic cracking residue oil ｛petroleum-based feedstock｝ 0.2-4.0%

Therefore, as the raw material oil, ethylene bottom oil derived from creosote oil and petroleum is preferable, and ethylene bottom oil derived from naphtha having a sulfur content of 0.05 to 0.1% was produced as a raw material. Carbon black is most preferred because it can reduce the sulfur content in carbon black to 0.1% by weight or less.

The production method is as follows.
00 ° C to 1700 ° C, preferably 1250 ° C to 1600
Furnace carbon black produced in a furnace at 0 ° C. is preferred.

In particular, free sulfur which has been found to have a direct adverse effect on the photographic properties of the photographic light-sensitive material (free sulfur)
hur) content (quantification according to JIS K 6350) is 100 ppm or less, preferably 50 ppm or less,
Particularly preferably 20 ppm or less, most preferably 10 p
pm or less of carbon black. In view of the fact that the free sulfur content is low, in the present invention, naphtha is used to produce ethylene bottom oil by continuous partial combustion in a furnace at 1250 ° C. to 1600 ° C. or by thermal decomposition. Furnace carbon black is most preferred.

The content of a cyan compound (particularly hydrogen cyanide gas) which deteriorates photographic properties (a value obtained by converting the amount of hydrogen cyanide determined by 4-pyridinecarboxylic acid / pyrazolone absorption spectrometry into a ppm unit relative to the weight of the light-shielding substance) is 20.
ppm or less, preferably 10 ppm or less, particularly preferably 5 ppm or less, most preferably 1 ppm or less,
In the case of a sensitized material such as gold sensitization, selenium sensitization, and dye sensitization, particularly sensitized gold, it is preferable to add a scavenger since photographic properties are easily affected by hydrogen cyanide gas.

In the present invention, a scavenger is a compound that converts hydrogen cyanide gas into a photographically inert substance. The scavenger should not release substances that adversely affect the silver halide photosensitive material as a result of capturing the hydrogen cyanide gas. Suitable hydrogen cyanide gas scavengers can be selected from inorganic or organic compounds of noble metals. Particularly preferred is palladium (II
Or IV; indicates an oxidation state. The same applies hereinafter), platinum (II or I
V) Compound. Gold (I or III) compounds are also preferred. Rhodium (III), iridium (III or IV) and osmium (II, III or IV) compounds are also effective, but higher amounts are required to achieve equivalent effects. Specific examples of useful inorganic or organic noble metal compounds include, for example, Gmelin Handb
and a commercially available product, a synthetic product and an in situ synthetic product can be used in such a purity as not to adversely affect the photographic light-sensitive material.

The amount of adsorbed iodine (measured by JIS K 6221) relating to the dispersibility, conductivity and light-shielding ability of carbon black is 20 mg / g or more, preferably 30 mg / g or more, particularly preferably 50 mg / g or more, and most preferably. Is 80 mg / g or more and dibutyl phthalate (DB
P), oil absorption (measured according to JIS K 6221) 50 ml
/ 100 g or more, preferably 60 mg / 100 g or more,
Particularly preferred is carbon black of 70 ml / 100 g or more, most preferably 100 ml / 100 g or more.

In the present invention, furnace carbon black is preferred for the purpose of improving light-shielding properties, cost and physical properties. Examples of expensive, light-shielding substances having an antistatic effect include various conductive carbon blacks and acetylene carbon blacks of various companies, Ketjen carbon black, which is a raw carbon black, is preferred. Particularly high sensitivity (ISO sensitivity 40
0 or more) 0.1% sulfur content for photographic materials
The following acetylene black and furnace carbon black produced by continuously partially burning or thermally decomposing ethylene bottom oil using naphtha as a raw material in a furnace at 1250 ° C. to 1600 ° C. are preferable.

The carbon black having an antistatic effect has an average particle diameter of 12 to 50 μm (= nm), DB
There are various conductive carbon blacks having a P oil absorption of 100 ml / 100 g or more. For example, acetylene black, conductive furnace black (CF), superconductive furnace black (SCF), extra conductive furnace black (XCF), and conductive channel black (CC) ) And 1500 ° C
Furnace black or channel black heat-treated at a moderately high temperature can be used. Specific examples of acetylene black include Denka acetylene black (manufactured by Denki Kagaku Co., Ltd.) and Shaunigan acetylene black (manufactured by Shaunigan Chemical Co., Ltd.). Specific examples of conductive furnace black include Continex CF (Continental Carbon). And Vulcan C (manufactured by Cabot Corporation). Examples of superconductive furnace black include Continex SCF (manufactured by Continental Carbon Co., Ltd.) and Vulcan SC (manufactured by Cabot Corporation). Specific examples of furnace black include Asahi HS-500 (manufactured by Asahi Carbon Co., Ltd.) and Vulcan XC-72 (manufactured by Cabot Corporation). Specific examples of conductive channel black include Kolux L. Degussa Co., Ltd.) there is like, can also be used Ketchen Black EC and Ketchen black EC-600JD, which is a kind of furnace black (made by Ketjen Black International Co., Ltd.).

Of these, acetylene black is particularly low in the content of impurities such as sulfur components and hydrogen cyanide, which adversely affect the photographic properties of the photographic light-sensitive material, and has a developed secondary structure structure. ,
Since it has excellent dispersibility and conductivity, it is preferably used.
Further, Ketjen Black EC, Ketjen Black EC-600JD, and the like, which have an excellent specific surface area and exhibit excellent conductivity even at a low filling amount, can also be preferably used.

The conductive carbon black may be added in an amount of 3 to 100 parts by weight, 5 to 80 parts by weight based on 100 parts by weight of the resin component.
The weight part is suitable, but it is particularly preferably from 10 to 60 parts by weight, most preferably from 15 to 50 parts by weight. If the amount is less than 3 parts by weight, the desired conductivity may not be obtained. If the amount exceeds 100 parts by weight, the physical strength, resin flowability and film formability of the film molded product may be reduced.

In order to impart conductivity to the packaging material of the present invention so as not to generate static marks on the photographic light-sensitive material or to prevent electric shock from being given to the user, the conductive carbon black ( If necessary, other conductive substances, for example, a surfactant-based antistatic agent or a metal filler, etc.) are added, and the volume resistivity (measured at 20 ° C. and 60% RH) is 1 × 10 ^12. it is preferred to below Omega · cm, more preferably 1 × ¹⁰ 10 Ω · cm or less, particularly preferably at most 1 × 10 ⁷ Ω · cm or less, is not more than 1 × 10 ⁶ Ω · cm Is most preferred. Volume resistivity (20 ° C, 60% R
(Measured by H) exceeds 1 × 10 ¹² Ω · cm, it is difficult to ensure sufficient antistatic properties, and static marks and the like are likely to be generated on the photographic material. In addition, an electric shock is applied during the packaging operation or during use by the user.

This volume specific resistance is a kind of electric resistance of a substance, and is an electric resistance indicated inside the sample. In other words, it is a value obtained by converting the volume resistance per unit volume,
K 6911 ".

A typical example when applied to a high α-olefin resin layer is as follows: 10% by weight of a 1,2-polybutadiene-based thermoplastic elastomer and 4 g of MFR polymerized and produced by a gas phase method using a metallocene catalyst. / 10 min, density 0.
An ethylene / hexene-1 random copolymer resin having a molecular weight distribution of 2.1 g at 91 g / cm ³ and a MFR having a crystallinity of 67% (E condition of ASTM D1238) of 2.5 g / 10 min; A low-density homopolyethylene resin having a density of 0.925 g / cm ³ , 21.8% by weight, and an antistatic agent master batch manufactured by Kao KK “Erest Master L-L-
10 "(trade name) 2% by weight, calcium stearate 0.1% by weight as a lubricating substance, bisfatty acid amide 0.05
Weight%, hindered phenolic antioxidant (trade name “Ireganox 1010” of Ciba-Geigy) 0.0
Resin consisting of 5% by weight, 1% by weight of zeolite A which is a volatile gas (hydrogen cyanide, aldehyde, sulfur, etc.) adsorbing substance and an anti-blocking agent which adversely affects the photographic properties of a photographic light-sensitive material, and 15% by weight of conductive carbon black Thickness 50 when the following carbon black is used as the composition
The volume specific resistance of the light-shielding high α-olefin resin film having a thickness of μm was as follows (the same resin composition was used except that the type of conductive carbon black was changed).

Light-shielding high α-olefin resin film containing 10% by weight of Ketjen Black EC 9.1 × 10 ¹ Ω · cm Light-shielding high α-olefin type resin containing 10% by weight of Ketjen Black EC600JD Resin film 1.8 × 10 ¹ Ω · cm Light-shielding high α-olefin resin film containing 10% by weight of acetylene black 5.8 × 10 ⁵ Ω · cm Light-shielding containing 10% by weight of Vulcan XC-72 High α-olefin resin film 4.3 × 10 ⁵ Ω · cm

This light-shielding high α-olefin resin film is excellent in conductivity, photographic properties, film formability, suitability for heat sealing, and the like.

The package of the present invention is a package in which a substance to be packaged is stored in a packaging bag manufactured using the above-mentioned packaging material. One or more special ethylene copolymer-based resin layers are adhered to each other with a peel strength greater than one or more blocking adhesions.

JIS Z of packaging materials used for packaging bags
0208 condition B (40 ℃, RH 90% ) moisture permeability as measured by, and preferably not more than 10g / m ² · 24 hours, more preferably at most 7g / m ² · 24 hours, 5 g / m ² · 24 hours or less, particularly preferably 3 g / m ² · 24 hours or less, and most preferably 1 g / m ² · 24 hours or less. When the water vapor transmission rate exceeds 10 g / m ² · 24 hours, in the case of a photographic light-sensitive material, an adhesive failure or adverse effect on photographic properties is caused. In particular, a photographic light-sensitive material containing a dye such as a sensitizing dye is susceptible to the influence of humidity, and a sensitivity abnormality occurs unless the moisture permeability is set to 7 g / m ² · 24 hours or less. Therefore, it is preferable to set it to 3 g / m ² · 24 hours or less.

The application to which the packaging material of the present invention can be applied will be described. (1) Moisture-proof / sealing packaging bag for packaging a transparent, colored or printed film unit with lens (Japanese Patent Publication No. 7-1380, Japanese Patent Application Laid-Open No. 3-243946, Japanese Patent Application Laid-Open No. 5-197)
087, JP-A-7-72593, JP-A-8
-248573, JP-A-8-254793, JP-A-8-334869, JP-A-9-157
No. 96, JP-A-9-54395, JP-A-9-54
120119, JP-A-9-244187,
JP-A-9-274288, JP-A-10-1865
86, JP-A-10-197994, etc.). (2) Transparent, colored or printed photographic film in a plastic container (JIS 135 film, APS
And a moisture-proof and sealed packaging bag (such as Japanese Patent Application Laid-Open No. 8-254793) for collectively packaging two or more films or microfilms. (3) Moisture-proof / sealing / light-shielding bags for sheet-like photographic light-sensitive materials such as photographic paper, film for printing plate making, cut film for photography, X-ray film, PS plate (JP-B 2-2700, JP-B-2 -2701, JP-A-8-25479
No. 3, JP-A-5-5972, etc.). (4) Light-shielding film for a belt-shaped photographic photosensitive material package (JP-A-2-72347, JP-A-6-214350, Japanese Utility Model Publication No. 5-29471, Japanese Utility Model Publication No. 6-8593)
Gazette, Japanese Utility Model Publication No. 7-50743, Japanese Utility Model Publication No. 8-10
812, JP-A-63-153255, etc.). (5) Moisture-proof sealed light-shielding bags for roll-shaped photographic light-sensitive materials such as photographic paper, movie films, micropositive films, printing plate-making films, and thermally developed diffusion transfer papers (JP-A-6-6735).
No. 8, etc.). (6) Moisture-proof / light-shielding film or leader film for light-room-packed packaging of strip-shaped photosensitive material such as photographic paper or photographic film (JP-A-62-172344, JP-A-2-723)
No. 47, Japanese Patent Application Laid-Open No. 5-72672, Japanese Patent Application Laid-Open
216176, JP-A-6-75341, JP-A-6-214350, JP-A-6-148820
JP, JP-A-7-257510 and JP-A-7-9
2618, JP-A-8-40468, JP-A-10-97030, JP-B-56-16608, JP-B-6-8593, JP-B-8-9725 and the like. (7) A moisture-proof and light-shielding film for packaging a bulk roll-shaped photographic light-sensitive material (JP-A-3-53243). (8) Instant film pack (JP-A-8-627)
82, JP-A-10-22879, JP-A-10-228080, and the like. (9) Shading paper for photographic film (US Pat. No. 5,790,9
12, JP-A-48-22020, JP-A-50-67644, JP-A-52-150016, JP-A-55-140835, and JP-A-58-158.
17434, JP-A-58-186744,
JP-A-59-68238, JP-A-60-3572
No. 8, JP-A-61-36216, JP-A-63
169,624, JP-A-4-136842, JP-A-4-296,849, JP-A-5-281
666, JP-A-9-80695, JP-A-9-80695
Japanese Patent Application Laid-Open Nos. 5-26585, 9-185151, 10-104803, and 10-2
No. 54102, Japanese Unexamined Patent Publication No. 10-254103,
JP-A-10-312042, JP-A-10-312
043, JP-A-10-319545, JP-A-10-325993, JP-A-11-38563
No.). (10) Shading bag for instant film pack
JP-A-186504, JP-A-10-221814, JP-A-10-228079, JP-A-10-208
JP-A-228080, JP-A-10-288810, JP-A-10-293359, JP-A-10-3
01199, JP-A-10-301248, etc.). (11) Packaging bags for substances requiring high airtightness, such as foods and pharmaceuticals.

The above-mentioned various sealing bags are formed by using a bottom sealing bag of a tubular film and the above-mentioned packaging material, and forming a sealing portion by superposing the surfaces of the heat-sealing resin layers so as to face each other. Sealed bags, three-sided sealed bags, four-sided sealed bags, gusset bags, envelope-attached seal bags, gasket-attached seal bags (pillow seal bags), fold-sealed seal bags, square-bottomed seal bags, and various other types of heat-sealed heat seals And the like.

Further, it can be used for various overwrapping packages. For example, Japanese Utility Model Publication No. 7-50743, Japanese Utility Model Publication 8-7398, Japanese Utility Model Publication 8-9723, Japanese Utility Model Publication 8-9724, Japanese Utility Model Publication No. 8-10812,
JP-A-6-148820, JP-A-6-21435
0, JP-A-7-257510, JP-A-7-257510
No. 287350, etc., on a moisture-proof light-shielding film or bag for a light-room-loaded package of a belt-shaped photosensitive material, overwrapping a carton or tray, overwrapping a caramel type, overwrapping a snack type, over a cigarette type There are wrapping packaging, roll wrapping packaging, stick-shaped wrapping packaging, twist wrapping packaging, etc.
Further, it can be used for various types of packages described in the Japan Packaging Technology Association, published on July 1, 1995, Handbook of Packaging Technology, pages 754 to 774.

The photographic light-sensitive materials applicable when the packaging material of the present invention is used for packaging materials for photographic light-sensitive materials are shown below. (1) Silver halide photographic materials (film for printing, color or black and white photographic paper, color or black and white negative film, master paper for printing, DTR (diffusion transfer) photosensitive material,
Computer typesetting film and paper, color or black-and-white positive film, color reversal film, microfilm, surveillance film, movie film, self-developing photographic photosensitive material, direct positive film and paper, etc.)
(JP-A-4-136838, JP-A-4-1723)
39, JP-A-5-113623, JP-A-9
-325450, JP-A-10-62901, JP-A-10-62903, JP-A-10-62
904, JP-A-10-62905, JP-A-10-62906, JP-A-10-62921, JP-A-10-142731, etc.) (2) Thermal developing photosensitive material (thermal developing color photosensitive material) Thermal development black-and-white light-sensitive materials (for example, JP-B-43-4921 and JP-B-43-4924), "Basics of photographic engineering", silver halide photography (published by Corona Co., Ltd., 1879), pages 553 to 555, and Research Tice. Closure Magazine June 1978 9
Pages 15 to 15 (RD-17029). Further, JP-A-59-12431 and JP-A-60-124
2950 and 61-52343,
-13295, 10-62898, 1
0-62899 and U.S. Pat. No. 3,457,07.
5, U.S. Pat. No. 3,574,627, U.S. Pat. No. 4,042,394, U.S. Pat.
84,267) (3) Photosensitive and heat-sensitive recording materials (photothermography (photosensitive material described in JP-A-3-72358) and the like.・ Recording material using thermal image formation method) (4) Diazonium photographic material (4-morpholinobenzenediazonium microfilm, microfilm, copy film, printing plate material, etc.) (5) Azide, diazide type photograph Photosensitive materials (photosensitive materials containing para-azidobenzoate, 4,4'diazidostilbene, etc., for example, copying films, printing plates, etc.) (6) Quinonediazide-based photographic photosensitive materials (orthoquinonediazide, orthonaphthoquinonediazide compounds, For example, a photograph containing benzoquinone (1,2) -diazide- (2) -4-sulfonic acid phenyl ether, etc. (7) Photopolymer (photosensitive material containing vinyl-based monomer, printing plate, adhesive film, etc.) (8) Polyvinylcinnamic acid Ester-based photosensitive material (for example, printing film, resist for IC, etc.) (9) Dry image forming material (having a layer having at least a photocurable compound, a photoinitiator and a dye precursor inside on a support, A recording material described in JP-A-11-2884 or the like having a color developer in a layer containing the microcapsules or an adjacent layer)

Particularly preferred representative examples of the layer constitution of the packaging material according to the present invention are shown below, but the present invention is not limited to these.

In the following examples of the layer structure, * indicates that the layers are directly laminated without an adhesive layer by co-extrusion, and / indicates that the layers are laminated with an adhesive layer interposed therebetween. * Indicates that the layers are stacked by blocking. In addition, it is described in order from the outermost layer to the innermost layer.

(1) High α-olefin resin layer containing light-shielding substance * Special ethylene copolymer resin layer containing light-shielding substance * Special ethylene copolymer resin layer containing light-shielding substance * Light-shielding property A four-layer laminated film comprising a high α-olefin resin layer containing a substance. (2) High α-olefin resin layer without light-shielding substance * Special ethylene copolymer resin layer without light-shielding substance * Special ethylene copolymer resin layer without light-shielding substance * Contains light-shielding substance A four-layer laminated film composed of a high α-olefin resin layer which is not used. (3) High α-olefin resin layer containing light-blocking substance * Special ethylene copolymer resin layer not containing light-blocking substance * Special ethylene copolymer resin layer not containing light-blocking substance * Contains light-blocking substance A four-layer laminated film comprising a high α-olefin-based resin layer. (4) High α-olefin resin layer not containing light-shielding substance * Special ethylene copolymer resin layer containing light-shielding substance * Special ethylene copolymer resin layer containing light-shielding substance * Contains light-shielding substance A four-layer laminated film composed of a high α-olefin resin layer which is not used. (5) Special ethylene copolymer resin layer containing light-shielding substance * High α-olefin resin layer containing light-shielding substance * Special ethylene copolymer resin layer containing light-shielding substance * Contains light-shielding substance A six-layer laminated film comprising a special ethylene copolymer resin layer * a high-α-olefin resin layer containing a light-shielding substance * a special ethylene copolymer resin layer containing a light-shielding substance. (6) Flexible sheet layer / high α-olefin resin layer containing light-shielding substance * Special ethylene copolymer resin layer containing light-shielding substance * Special ethylene copolymer resin layer containing light-shielding substance * Light shielding Α-
A six-layer laminated film comprising an olefin-based resin layer. (7) Flexible sheet layer / High α-olefin resin layer not containing light-blocking substance * Special ethylene copolymer resin layer not containing light-blocking substance * Special ethylene copolymer resin layer not containing light-blocking substance * Light blocking Six-layer laminated film comprising a high α-olefin resin layer containing no conductive substance. (8) Flexible sheet layer / High α-olefin resin layer containing light-shielding substance * Special ethylene copolymer resin layer not containing light-shielding substance * Special ethylene copolymer resin layer not containing light-shielding substance * Light shielding Six-layer laminated film composed of a high α-olefin resin layer containing a conductive substance. (9) Flexible sheet layer / High α-olefin resin layer not containing light-shielding substance * Special ethylene copolymer resin layer containing light-shielding substance * Special ethylene copolymer resin layer containing light-shielding substance * Light shielding Six-layer laminated film comprising a high α-olefin resin layer containing no conductive substance. (10) Flexible sheet layer / Special ethylene copolymer resin layer containing light-shielding substance * High α-olefin resin layer containing light-shielding substance * Special ethylene copolymer resin layer containing light-shielding substance * Light shielding Special ethylene copolymer resin layer containing conductive material * High α-
An eight-layer laminated film consisting of an olefin-based resin layer and a special ethylene copolymer-based resin layer containing a light-shielding substance. (11) High α-olefin resin layer containing light-blocking substance * High α-olefin resin layer containing light-blocking substance * Special ethylene copolymer resin layer containing light-blocking substance * Contains light-blocking substance A six-layer laminated film comprising a special ethylene copolymer-based resin layer, a high α-olefin resin layer containing a light-shielding substance, and a high α-olefin resin layer containing a light-shielding substance. (12) A laminated film having an eight-layer structure obtained by laminating a flexible sheet layer via an adhesive layer on (11). (13) A laminated film in which a heat seal resin layer is laminated on the innermost layer of the laminated film of (1) to (12) via an adhesive layer. (14) A laminated film in which a heat seal resin layer is directly laminated on the innermost layer of the laminated film of (1) to (12) without an adhesive layer.

As the adhesive using the adhesive layer, the flexible sheet layer, and the heat seal resin, various known ones can be used according to the intended use. For example, JP-A-1-316742 and JP-A-3-31642. -13465
No. 6, No. 6, etc. can be used.

An apparatus for manufacturing a packaging material according to the present invention will be described with reference to FIG. FIG. 1 is a schematic view of an apparatus for producing a packaging material. The apparatus shown in FIG. 1 is a two-layer co-extrusion comprising a special ethylene copolymer resin layer 1a and a high α-olefin copolymer resin layer 2a. Reference numeral 3 denotes a ring die for forming an inflation film, 4 denotes a pass roll, 5 denotes a nip roll (also referred to as a pinch roll), and 6 denotes a winding roll.

Next, the package according to the present invention will be described with reference to the drawings. FIG. 2 is a perspective view of a packaging bag used for the photographic photosensitive material package. The packaging bag stores the photographic photosensitive material in a packaging bag 11 made of the packaging material of the present invention. In the opening 12 for taking in and out the photosensitive material, four strong bonding portions 13 bonded at a peel strength larger than the blocking bonding are provided on both sides at substantially equal intervals. After such a configuration, as shown in FIG. 3, after the opening 12 is bent at least once with a width of 0.3 to 5 mm over the entire width, an adhesive tape (for example, Cellotape (registered trademark)) 14 (or hot tape) is used. The package is fixed and sealed with a melt adhesive.

FIG. 4 is a perspective view of a packaging bag used for a photographic photosensitive material package, in which a sheet-like photographic photosensitive material is stored in a packaging bag 21 made of the packaging material of the present invention. Opening 22 for loading and unloading sheet-like photosensitive material
Are provided with three strongly bonded portions 23 bonded on both sides at substantially equal intervals with a peel strength larger than the blocking bonding. After such a configuration, as shown in FIG.
After the opening 22 is bent at least once at a width of 0.3 to 5 mm over the entire width, a tape 24 (or a hot melt adhesive or the like) is used.
It is a package fixed and sealed with.

[0173]

[Example 1] The layer configuration corresponds to No. 1 in the representative example of the layer configuration.

<High α-Olefin Resin Layer> Metallocene-based catalyst containing bis (cyclopentadienyl) dimethylzirconium transition metal compound of a compound having cyclopentadienyl group of zirconium transition metal and aluminoxane as main components Ethylene-hexene-1 copolymer resin (ethylene content 8
Hexene-1 which is one of high α-olefins at 2% by weight
Content 18% by weight, crystallinity 22%, molecular weight distribution 1.
9, MFR 4.0 g / 10 min, density 0.911 g / c
m ³ , 80 parts by weight of 11600 g polymer / mg atom-zirconium activity per unit zirconium) and a propylene-ethylene-butene-1 copolymer resin (propylene content 80% by weight, ethylene content 5% by weight, 15% by weight of butene-1 which is a kind of high α-olefin, MFR of 6 g / 10 min, density of 0.880 g / cm ³ ) 20 parts by weight; Acetylene black (pH 7.5, oil absorption 125 cc / 100 g, average particle diameter 40 mμ, total sulfur content 0.1% or less) 2 as a substance / conductive substance 2
0 parts by weight, 1 part by weight of monoglycerin oleate, one of aliphatic alcohol fatty acid esters for improving drip-proof property, antistatic property and dispersibility of acetylene black, erucic acid as a film formability and lubricity improver 0.05 parts by weight of amide, 0.2 parts by weight of zinc stearate as a metallocene catalyst residue neutralizing agent, 0.1 parts by weight of vitamin E which functions to prevent heat deterioration of resin and additives and to improve light-shielding ability by coloring. Pentaerythrityl-tetrakis [3- (3,5-
[Di-t-butyl-4hydroxyphenyl)] propionate in an amount of 0.05 part by weight.

<Special Ethylene Copolymer Resin Layer> Ethylene / vinyl acetate copolymer resin (vinyl acetate content of 18
Weight%, MFR 2.5 g / 10 min) 94 parts by weight, and low density homopolyethylene resin (MFR 3.0 g / 10 min,
A density of 0.920 g / cm ³ ) A total of 100 parts by weight of 6 parts by weight, as a light-shielding substance, a total sulfur content starting from ethylene bottom oil of 0.1% or less, a pH of 8.0,
Furnace carbon black 4 having an average particle diameter of 25 μm
Parts by weight, specific gravity 2.7, oil absorption 60cc / 100
g, 0.1 part by weight of talc having a refractive index of 1.58, drip-proof,
Antistatic property, 1 part by weight of polypropylene glycol oleate which is one kind of aliphatic alcohol fatty acid ester for improving dispersibility of light-shielding substance, 0.2 parts by weight of calcium stearate as dispersibility improver of light-shielding substance, It consists of a resin composition containing 0.1 parts by weight of pentaerythrityl-tetrakis [3- (3,5-di-t-butyl-4hydroxyphenyl) propionate as a thermal degradation inhibitor for the resin and additives.

A special ethylene copolymer resin layer and a high α-olefin resin layer having the above resin composition are
Each was extruded from a ring die having a lip gap of 1.2 mm at a resin temperature of 185 ° C. and a blow-up ratio of 1.5 using two extruders each having a diameter of 50 mmφ and L / D = 25, and the thickness of each layer was 25 μm. The thickness is 50 μm (withdrawal rate =
(1200/50 = 24) to produce a two-layer co-extruded blown film.

Then, the two-layer co-extruded blown film is pressure-bonded with a pinch roll (also referred to as a nip roll) composed of a metal roll and a silicone rubber roll at a nip pressure (linear pressure) of 55 kg / cm and a take-up speed of 20 m / min. A 100 μm-thick laminated film having a four-layer structure in which special ethylene copolymer-based resin layers were laminated by blocking adhesion was produced. The moisture permeability of this laminated film is
3.8 g / m ² · 24 hours.

This packaging material has a blocking adhesion that is substantially uniform over the entire surface and is strong enough not to be peeled off in the laminating and laminating steps with another flexible sheet and in the bag making step. It had excellent properties, antistatic properties, suitability for bag making, photographic properties, anti-curl properties, appearance, dispersibility of light-shielding substances, drip-proof properties, lubricity and dust-free properties.

The light-shielding packaging bag produced using this packaging material has a sealing / light-shielding property, heat seal strength, antistatic property, lubricity, dustlessness, appearance, photographic property, drip-proof property, moisture-proof property, It is excellent in flexibility and the like, and because it is formed of a multi-layer co-extruded film mainly composed of polyolefin resin, it has excellent suitability for recycling and incineration. Since it was a laminated film manufactured in the above, it could be manufactured at low cost.

[Comparative product 1] This is a single-layered film having a thickness of 50 μm and consisting solely of a high α-olefin resin layer containing the ethylene-hexene-1 copolymer resin of Example 1 as a main component.

The film forming conditions were as follows: 50 mm diameter, L
The resin film extruded from a ring die having a lip gap of 1.2 mm with a resin temperature of 185 ° C. and a blow-up ratio of 1.5 using an extruder having a / D = 25 nip pressure of a pinch roll composed of a metal roll and a silicon roll Linear pressure) 55 kg
An attempt was made to produce at a take-off speed of 20 m / min at / m, but the motor load was very large, melt fracture was large, the appearance was poor and production was impossible. Also,
Although the take-off speed was reduced to 10 m / min, the motor load was large, the occurrence of melt fracture was large, and the appearance was poor, making it difficult to put into practical use as compared with Example 1.

Further, an attempt was made to produce a laminated film having a thickness of 100 μm as in Example 1 by performing blocking adhesion lamination, but it was difficult to perform blocking adhesion lamination. The nip pressure (linear pressure) was increased from 55 kg / cm to 80 kg / cm for blocking adhesion, but it was difficult to perform blocking adhesion lamination almost uniformly over the entire surface, and wrinkles and streaks were generated. Was difficult.

[Example 2] The layer structure corresponds to No. 1 in the representative example of the layer structure.

<High α-olefin resin layer>
80 parts by weight of hexene-1 copolymer resin and propylene
Total of 20 parts by weight of ethylene / butene-1 copolymer resin 1
Instead of 00 parts by weight, homopolybutene-1 copolymer resin (MFR 3.5 g / 10 min, density 0.910 g / cm ³ )
Example 1 is the same as Example 1 except that a total of 100 parts by weight of 60 parts by weight and 40 parts by weight of a recycled resin resin obtained by recycling the resin composition used in Example 1 was used.

<Special ethylene copolymer resin layer> This is the same as the special ethylene copolymer resin layer of Example 1. A laminated film having a thickness of 100 μm was formed of a four-layer structure in which special ethylene copolymer-based resin layers of a two-layer co-extruded blown film having a total thickness of 50 μm and molded under the same conditions as in Example 1 were bonded and laminated. . The moisture permeability of this laminated film was 4.3 g / m ² · 24 hours.

In this packaging material, the dispersibility of the light-shielding substance in the high α-olefin resin layer was improved, the generation of bumps (foreign hardening) was reduced, and the motor load was reduced. Was small, and no melt fracture occurred and the appearance was excellent. This is considered to be due mainly to the inclusion of 40 parts by weight of the recycled resin.

Example 3 The layer configuration corresponds to No. 5 in the representative example of the layer configuration.

<High α-olefin resin layer> The same as the high α-olefin resin layer of Example 1. However, the thickness was 20 μm.

<Special ethylene copolymer resin layer> This is the same as the innermost special ethylene copolymer resin layer in Example 1. The outermost special ethylene copolymer resin layer contained 1% by weight of a synthetic zeolite carrying silver ions in the innermost layer. However, the thickness of both layers was 15 μm.

The total thickness formed under the same conditions as in Example 1 was 5
A 100 μm-thick laminated film having a 6-layer structure in which special ethylene copolymer-based resin layers of a 3-layer co-extruded blown film of 0 μm were laminated by blocking adhesion was produced. The moisture permeability of this laminated film is 4.1 g / m
Was ² · 24 hours.

This packaging material was superior to the packaging material of Example 1 in that the package body was improved in preventing the collapse of the package and the bag breaking strength when dropped at a low temperature. The film formability was also excellent (the load on the motor was reduced, and the occurrence of melt fracture was reduced). Furthermore, the outermost layer had excellent antibacterial properties, antiblocking properties, low-temperature heat sealability, photographic properties, and the like.

[0192]

As described above, the present invention has the following advantages. (1) Stable overall blocking adhesion can be obtained. (2) Excellent physical strength, curl prevention, sealing, and film moldability. (3) Since the layer containing the light-shielding substance is a multilayer film having an even number of layers arranged vertically above and below the blocking adhesive laminated portion, very excellent light-shielding properties can always be ensured. Packaging material). (4) It has suitability for recycling and reuse, and there is little deterioration in quality. (5) Excellent flexibility. (6) Excellent transparency (when no light-shielding substance is contained in all layers). (7) Excellent heat seal suitability. (8) Excellent prevention of bag breakage when dropped at low temperatures. (9) It has excellent compatibility with recycled resin, and has little decrease in physical strength and appearance.

[Brief description of the drawings]

FIG. 1 is a schematic view of an apparatus for manufacturing a packaging material according to the present invention.

FIG. 2 is a perspective view of a packaging bag used for a photographic photosensitive material package according to the present invention.

FIG. 3 is a perspective view of a photographic photosensitive material package according to the present invention.

FIG. 4 is a perspective view of a packaging bag used for a photographic photosensitive material package according to the present invention.

FIG. 5 is a perspective view of a photographic photosensitive material package according to the present invention.

[Explanation of symbols]

 1a ... Special ethylene copolymer resin layer 2a ... High α-olefin resin layer 11 ... Packing bag 12 ... Opening 13 ... Strong adhesive part 14 ... Adhesive tape 21 ... Packing bag 22 ... Opening 23 ... Strong adhesive part 24 ... Adhesive tape

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI theme coat ゛ (Reference) B29C 47/56 B29C 47/56 B32B 27/28 101 B32B 27/28 101 B65D 65/40 B65D 65/40 D C08K 5/101 C08K 5/101 C08L 23/08 C08L 23/08 // C08J 5/18 CES C08J 5/18 CES B29K 23:00 33:00 B29L 7:00 9:00 F term (reference) 3E086 AD01 BA04 BA15 BB51 BB85 BB87 CA40 4F071 AA15X AA20X AA21 AA21X AA28X AA32X AA33X AA88 AC10 AH04 BB06 BB09 BC01 4F100 AA37H AH02B AH02D AH03H AK04 AK04J AK06 AK07 AK07A AK07C AK07J AK08A AK08C AK09 AK09J AK62A AK62C AK66A AK66C AK68B AK68D AK70B AK70D AK71B AK71D AK80 AL01 AL05A AL05B AL05C AL05D BA04 BA06 BA10A BA10C BA13 CA05 CA13 CA18 CA19 CA21 CA30 DA02 EH20 EJ19 GB17 JA05C JA06A JA06B J A06D JA13A JA13C JJ04 JK01 JK06 JK10 JK13 JL01 JL04 JL12 JL16 JN01 JN08H YY00A YY00B YY00C YY00D 4F207 AA03 AA04E AA10 AA21 AG01 AG03 AH54 KA01 KA17 KA19 KB26 KF01 BB19 E26

Claims (5)

[Claims] 1. A high α-olefin comprising as a main component a high α-olefin resin containing 1% by weight or more of an α-olefin having 4 or more carbon atoms.
-Multi-layer co-extruded blown film comprising an olefin resin layer and a special ethylene copolymer resin layer mainly containing a special ethylene copolymer resin containing 5 to 40% by weight of at least one of vinyl acetate and acrylic acid. A packaging material comprising: a laminate film obtained by laminating two special ethylene copolymer-based resin layers of two multi-layer coextrusion blown films by blocking with each other. 2. The high α-olefin resin contains at least 1% by weight of an α-olefin having 4 to 8 carbon atoms, a melt flow rate of 0.1 to 10 g / 10 min, and a density of 0.8.
7 to 0.94 g / cm ³ of homo α-olefin resin, propylene-α-olefin copolymer resin and ethylene α
The packaging material according to claim 1, wherein the packaging material is at least one kind of an olefin copolymer resin. 3. The special ethylene copolymer resin contains 6 to 30% by weight of vinyl acetate, and has a melt flow rate of 0.1 to 10 g / 10 min. The packaging material according to claim 1, which contains 6 to 30% by weight of the ethylene-ethylacrylic acid copolymer resin having a melt flow rate of 0.1 to 10 g / 10 minutes. 4. The special ethylene copolymer resin layer,
Aliphatic alcohol having 1 to 10 carbon atoms and 10 to 20 carbon atoms
The packaging material according to claim 1, which contains 0.1 to 5% by weight of an aliphatic alcohol fatty acid ester which is a compound with a fatty acid. 5. An opening for storing an article to be packaged in a packaging bag manufactured using the packaging material according to claim 1, wherein the article to be packaged is taken in and out of the packaging bag. Wherein the special ethylene copolymer-based resin layer is bonded with a peel strength greater than a blocking adhesive strength at one or more locations.