JP2000010243A - Packaging material for photographic sensitive materials and packaged body of photographic sensitive materials using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To make it possible to impart high physical strengths, freeness from curling, excellent film formability, shieldability for a long period of time, improved recycling suitability and improved incineration suitability to the packaging material used for packaging photographic sensitive materials such as photographic films by only multilayer co-extrusion inflation film forming process. SOLUTION: The packaging material is constituted of two layer co-extrusion inflation films IIa comprising the innermost layer 1a containing a light shielding material and the outermost layer 2a containing a light shielding material. The innermost layers, 1a and 1a are bonded B each other by blocking. The innermost layer 1a contains, as a main component, a polyolefinic resin prepared by polymerization in the absence of single-site catalysts and the most outer layer 2a contains, as a main component, a polyolefinic resin prepared by polymerization in the presence of a single-site catalyst.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photographic photosensitive material packaging material suitable for packaging photographic photosensitive materials such as photographic film and photographic printing paper, and a photographic photosensitive material package using the same.

[0002]

2. Description of the Related Art Japanese Patent Application Laid-Open No. 64-22444 proposes a packaging material having a pseudo-adhesion layer in which inner layers of a multilayer co-extruded blown film are adhered to each other by blocking.

Japanese Patent Publication No. 2-2700 discloses a polyethylene-based polymer and 1% by weight or more of a light-shielding substance.
A photosensitive material packaging film having at least one light-shielding film in which 50% by weight or more of the total polyethylene polymer is an ethylene / α-olefin copolymer resin has been proposed.

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 ethylene / α-olefin copolymer resin layer. Have been.

[0005]

However, the above-mentioned conventional packaging materials have various problems. That is, the packaging material proposed in JP-A-64-22544 is preferable because it has no curling, has high physical strength, and is excellent in recyclability and incineration suitability. It needed to be improved.

[0006] The photosensitive material packaging film proposed in Japanese Patent Publication No. 2-2700 is preferable because of its excellent physical strength even in a single layer, but the single layer has a poor moisture resistance unless the film thickness is increased. To be large and have a small tensile modulus in the vertical direction, the thickness must be increased in order to be used for packaging heavy substances. However, if the thickness is increased, melt fracture occurs. Therefore, it is necessary to laminate a metal layer, and it is necessary to improve cost and recyclability.

The photographic photosensitive material packaging material proposed in Japanese Patent Publication No. 4-80373 is an improved version of the photosensitive material packaging film proposed in Japanese Patent Publication No. 2-2700, and has moisture-proof properties and physical strength. And excellent in recyclability and incineration suitability, which were preferable. However, it was necessary to further improve curling, antistatic properties, physical strength and the like.

The present invention solves the above problems, and adversely affects the photographic properties of a photographic material which is indispensable as a wrapping material for a photographic material only by a multilayer co-extrusion blown film forming process (fog, abnormal sensitivity, gradation, etc.). (Abnormal, coloring interface, density unevenness, etc.), high physical strength, no curling, excellent film formability, flexibility,
Inexpensive packaging material for photographic photosensitive materials with low loss, long-term moisture-proof / sealing performance, excellent recyclability and incineration suitability, conforming to the Containers and Packaging Recycling Law, and excellent appearance. An object of the present invention is to provide a photosensitive material package.

[0009]

According to the present invention, there is provided a packaging material for a photographic light-sensitive material, wherein the innermost layers of a multilayer co-extruded blown film having an outermost layer and an innermost layer (or a plurality of intermediate layers) may be provided. In a packaging material for a photographic light-sensitive material having a laminated film bonded and laminated by blocking, the outermost layer is mainly composed of a polyolefin resin produced by polymerization using a single-site catalyst, and the innermost layer is produced by polymerization without using a single-site catalyst. It is characterized by containing a polyolefin resin as a main component.

The wrapping material for a photographic light-sensitive material of the present invention is a wrapping material for a photographic light-sensitive material having a laminated film in which the innermost layers of a multilayer co-extruded inflation film having an outermost layer and an innermost layer are bonded and laminated by blocking. Wherein the outermost layer is composed mainly of an ethylene / α-olefin copolymer resin having a molecular weight distribution of 1.0 to 5 produced by polymerization using a single-site catalyst, and the innermost layer is produced by polymerization using a multi-site catalyst. Is an ethylene / α-olefin copolymer resin having a crystallinity by X-ray method of 2% or more and 60% or less as a main component, and a fatty acid metal salt of 0.01 to
It is characterized by containing 5% by weight.

The photographic material package of the present invention is a package in which the photographic material is sealed and housed in a packaging bag manufactured using the photographic material packaging material. The outer layer of the packaging bag has a sliding friction. The coefficient (measured with a load area of 42 cm ² and a load of 200 g by a method according to ASTM D-1894) is 0.
48 (slip start angle 40 degrees) or more, and contains a lubricant.

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION The packaging material for photographic light-sensitive material of the present invention comprises a laminated film in which the innermost layers of a multilayer co-extruded inflation film are adhered and laminated by blocking each other. Some include two layers, an inner layer and an outermost layer, and some include one or two or more intermediate layers between the innermost layer and the outermost layer.

The two or more intermediate layers may be the same resin composition or different resin compositions, and the two or more intermediate layers may have the same or different thicknesses. The layer may have or may not have a light-shielding property.

The adhesive lamination by blocking the innermost layer is as follows.
This is performed by superposing the innermost layers and applying pressure, and can be performed in the production process of the blown film without using an adhesive or applying heat. As a method of applying pressure, a nip roll (such as a pinch roll) made of a pair of elastic rolls (rubber rolls, cotton rolls, etc.) and a metal roll
And so on. In the case where the adhesive strength is strong, the adhesive strength is weak, or the adhesive strength is partially improved in a dot or grid pattern, an embossing roll or a heating roll may be used.

When the innermost layers are bonded and laminated by blocking by the pressure of the nip roll in the blown film forming step, the film is in contact with the film in order to prevent wrinkles and streaks from occurring and to surely perform the bonding and lamination by blocking. When the pressing pressure at that time is divided by the area of the pressing surface, the pressure is 1 to 100 kg / cm ² ,
It is preferably 1 to 80 kg / cm ² , particularly preferably 1 to 80 kg / cm ² .
60 kg / cm ² , most preferably 1 to 40 kg / cm ²
It is. The peel strength is 300 g / 15 mm width or less, preferably 100 g / 15 mm width or less.

The polyolefin copolymer resin produced by polymerization using a single-site catalyst contained in the outermost layer (hereinafter referred to as “single-site type” produced by polymerization using a single-site catalyst) is at least 20% by weight. And 4
The content is preferably 0% by weight or more, more preferably 50% by weight or more, particularly preferably 70% by weight or more, and most preferably 90% by weight or more.

When the content of the single-site polyolefin copolymer resin is less than 20% by weight, physical strength,
It is difficult to provide a packaging material for photographic light-sensitive materials having excellent heat-sealing suitability and photographic properties, and a photographic light-sensitive material package using the same.

Representative examples of the single-site catalyst include a metallocene catalyst comprising zirconocene dichloride and methylaminoxan having a uniform active site and discovered by Prof. Kaminsky of Germany. It has been announced. A typical example is JP-A-60
JP-A-350007, JP-A-60-35008,
JP-A-60-35009, JP-A-3-20770
No. 3, JP-A-3-234711, JP-A-4-234.
No. 300887.

The ethylene / α-olefin copolymer resin produced by polymerization using a metallocene catalyst has the following characteristics as compared with an ethylene / α-olefin copolymer resin produced by polymerization using a conventional Ziegler catalyst. . It has 2-3 times the impact strength and tear strength. Excellent transparency and gloss. Excellent blocking resistance (less low-molecular-weight, low-density components called stickiness components) Low melting point and excellent low-temperature heat sealability. Excellent flexibility.

Currently commercially available L produced by polymerization using a metallocene catalyst which is a typical example of a single-site catalyst.
-Specific examples of the LDPE resin include: EXCEED (EXXon chemical) EXACT (EXXon chemical) AFFINITY (DOW chemical) ENGAGE (DOW chemical) LUFLEXENE (BASF) Evolu Chemical Co., Ltd. Rex (Japanese polyolefin) Catalocene (Tosoh), etc.

As a polymerization method, a gas phase polymerization method is particularly preferable because it is inexpensive and has few 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 from the viewpoint of ease of polymerization.

From the viewpoint of the antiblocking property and the improvement of physical strength, the molecular weight distribution (weight average molecular weight / number average molecular weight) measured by GPC method is 5 or less, preferably 4 or less, particularly preferably 1.1 to 3, and most preferably. 1.3 to 2.7.

As a method for producing a polymer using a metallocene catalyst, which is a typical single-site catalyst, for example, a radical initiator such as oxygen or peroxide is used at a temperature of 150 to 350 ° C. and a pressure of 1000 to 3500 kg. / C
High-pressure method for polymerizing ethylene under m ² conditions, Ziegler catalyst (titanium-based) or Phillips catalyst (chromium-based)
Etc., temperature 50 ~ 250 ℃, pressure 50 ~ 250k
Medium / low pressure method of copolymerizing ethylene and ethylene and a small amount of α-olefin under the condition of g / cm ² , ethylene alone at high pressure or medium / low pressure using metallocene catalyst (compounds such as zirconium, haunium, titanium, vanadium) Polymerization and a method of copolymerizing ethylene with one or more α-olefins are available.

Most preferred as the ethylene / α-olefin copolymer resin is an ethylene / α-olefin random copolymer resin. The composition of the ethylene / α-olefin copolymer resin is such that the α-olefin component is 1 to 99.
Mol%, preferably 1 to 95 mol%, more preferably 1 to 95 mol%.
From 90 to 90 mol%, particularly preferably from 2 to 80 mol%, most preferably from 2 to 50 mol%, and the ethylene component is preferably from 5 to 99 mol%, more preferably from 10 to 99 mol%, particularly preferably from 20 to ９８98 mol%, most preferably 50-98 mol%. Representative examples of α-olefins include propylene, butene-1, hexene-1, 4-methyl-pentene-1, octene-1, decene-1, dodecene-1, tetracene-1, hexadecene-1, and octadecene-1. , Hebutene-1, eicosene-1, 4-methyl-hexene-1, 4,4-dimethylpentene-1, etc., having 3 to 20, preferably 4 to 15, particularly preferably 4 to 12, and most preferably, 4 to 12 carbon atoms. Is one of 4 to 10 or 2
At least one α-olefin.

The polymerization method using a metallocene catalyst is disclosed in many patent publications as exemplified below.

JP-A-58-19309, JP-A-6-19309
0-862, JP-A-60-35006, JP-A-60-35007, JP-A-60-35008
JP-A-60-106008, JP-A-60-106008,
-137911, JP-A-61-31404, JP-A-61-108610, JP-A-61-2
No. 21207, JP-A-61-264010,
JP-A-61-296008, JP-A-63-610
No. 10, JP-A-63-152608, JP-A-63-178108, JP-A-63-222177
JP, JP-A-63-222178, JP-A-63-222178
JP-A-222179, JP-A-63-264606, JP-A-63-28070, JP-A-63-50
No. 1369, Japanese Patent Application Publication No. 64-6003, Japanese Patent Application Publication No. 64-45406, Japanese Patent Application Laid-Open No. 64-74202, Japanese Patent Application Laid-Open No. 1-1407, and Japanese Patent Application Laid-Open No. 1-9511.
0, JP-A-1-101315, JP-A-1-101315
129003, JP-A-1-207248,
JP-A-1-210404, JP-A-1-25140
No. 5, JP-A-1-259004, JP-A-1-259004
275609, JP-A-1-301704,
JP-A-1-319489, JP-A-2-22307
JP, JP-A-2-41303, JP-A-2-17
3110, JP-A-2-302410, JP-A-3-56508, JP-A-3-62806, JP-A-3-66710, JP-A-3-7070
No. 8, JP-A-3-70709, JP-A-3-7
0710, JP-A-3-74412, JP-A-4-8704, JP-A-4-11604, JP-A-4-25514, JP-A-4-213305, JP-A-5-310829 Gazette, JP-A-5-32
0242, JP-A-6-228222, JP-A-9-40793, U.S. Pat.
No. 82, U.S. Pat. No. 4,530,914 and the like.

Among the ethylene / α-olefin copolymer resins produced by polymerization using these metallocene catalysts, zirconium-based, hafnium-based, titanium-based, and vanadium-based catalyst residues have few catalyst residues that adversely affect the photographic properties of photographic light-sensitive materials. The resin is preferably 10,000 g or more per 1 g of the solid catalyst component using at least one metallocene catalyst. In particular, a metallocene catalyst comprising zirconocene dichloride and methylaluminoxane is preferred. Resin halogen content which adversely affects photographic properties in resin is 100p
pm or less, particularly preferably 50 ppm or less.
In order to reduce the halogen content in the resin to 100 ppm or less, it is necessary to extract a catalyst residue using a catalyst deactivator in order to improve the rust prevention and photographic properties of the extruder screw and die. preferable.

The polyolefin resin is a general term for olefin homopolymer resins or copolymer resins having relatively simple structures such as ethylene, propylene, butene, pentene and methylpentene. In a broad sense, ethylene
It also includes vinyl acetate copolymer resins, ethylene-ethyl acrylate copolymer resins, ionomer resins, terpolymers of ethylene-propylene-dienes, and the like. The general characteristics of polyolefin resin are low specific gravity, chemical resistance,
It has excellent water resistance and low dielectric constant and dielectric power factor, so it has excellent high-frequency insulation.

The polyethylene resin is a milky white opaque or translucent thermoplastic obtained by polymerizing ethylene and has a specific gravity of less than 1. nCH ₂ = CH ₂ →-(-CH ₂ -CH ₂ -)-n

Polyethylene resins obtained by different polymerization methods also have different properties, and are classified according to production methods such as a high pressure method (ICI method), a medium pressure method (Philips method), and a low pressure method (Ziegler method). However, the difference in essential properties is related to the density, and low density (0.910 to 0.925 g /
cm ^3), medium density (0.926~0.940g / cm ^3), are classified as high density (0.941~0.965g / cm ^3). FIG. 8 schematically shows the relationship between the density and the properties of the polyethylene resin. A polyethylene resin having a density of less than 0.910 g / cm ³ is called an ultra-low density polyethylene resin,
It is a copolymer resin of ethylene and α-olefin (containing 5% by weight or more).

The polyethylene resin is roughly classified into a high-density polyethylene resin and a low-density polyethylene resin according to its density. A high-density polyethylene resin has a linear molecular structure with few branches and a high degree of crystallinity, whereas a low-density polyethylene resin has many branches and a low degree of crystallinity. The higher the crystallinity, that is, the higher the density of the polyethylene resin, the higher the melting point and the higher the rigidity, but the lower the transparency. In addition, even with the same low-density polyethylene resin, a linear low-density polyethylene resin having a short-chain branch (a typical example is an ethylene / α-olefin copolymer resin) has a lower branched-density having a long-chain branch. Compared with polyethylene resin, the degree of crystallinity is higher and the number of tie molecules is larger, so that the melting point is higher and the mechanical strength is better. Therefore, the film formability is poor.

The method for producing the polyethylene resin includes a high pressure method,
The method can be roughly divided into the medium pressure method and the low pressure method. The high-pressure method uses a radical initiator such as oxygen or peroxide,
A branched low-density polyethylene resin having a long-chain branch can be obtained by a method of polymerizing ethylene under a temperature and pressure condition of 1000 to 3000 kg / cm ² .

The medium pressure method and the low pressure method use a Ziegler catalyst (T
i) or a Phillips catalyst (Cr system)
A linear high-density polyethylene resin is obtained by a method in which ethylene is polymerized under a temperature and pressure condition of 0 to 250 ° C and 50 to 200 kg / cm ² . In the medium pressure method and the low pressure method, the average molecular weight of the polyethylene resin is adjusted by using hydrogen as a chain transfer agent. In addition, using a Ziegler catalyst or a Phillips catalyst, a small amount of α-
When olefin is copolymerized, the density and melting point decrease as the α-olefin content in the produced polyethylene resin (ethylene / α-olefin copolymer resin) increases, and linear medium and low density with short chain branches A polyethylene resin is obtained.

Examples of the ethylene · alpha-olefin copolymer resin, L-LDPE (L inear L ow D ens
There are ity P olyethylene) resin, the L-LDPE resin is called third polyethylene resin,
It is a low-cost, high-strength resin that meets the demands of energy-saving and resource-saving times that combine the advantages of both medium-, low-, and high-density polyethylene resins. This resin is obtained by low pressure method or high pressure improvement method with ethylene and carbon number of 3 to 15, preferably 4 to 4.
It is a polyethylene resin having a structure obtained by copolymerizing 10 to 10, particularly preferably 4 to 8 α-olefins, and having a linear linear structure with short branches.

Representative examples of such α-olefins include propylene, butene-1, hexene-1, 4-methylpentene-1, octene-1, heptene-1, decene-
1, nonene-1, dodecene-1, tetracene-1, hexadecene-1, octadecene-1, heptene-1, eicosene-1 and the like. And α-olefin is 1 to 5
The content is preferably 0 mol%, particularly preferably 1 to 30 mol%. When the amount of the α-olefin is less than 1 mol%, not only the heat sealability, especially the heat seal strength maintenance with time deteriorates, and not only the complete sealability cannot be ensured, but also
Physical strength such as tear strength and impact drilling strength is also reduced. When the amount of the α-olefin exceeds 50 mol%, polymerization becomes difficult and expensive unless a single-site catalyst is used.
Further, the Young's modulus is extremely small, blocking is liable to occur, and the film formability is poor, so that it is difficult to put into practical use as a film for packaging photographic light-sensitive materials.

The density (JIS K-7112) is generally about low to medium density polyethylene resin, but many commercial products have a density in the range of 0.87 to 0.95 g / cm ³ . Melt flow rate (measured under condition 4 of JIS K-7210, temperature 190 ° C, load 2.16 kgf) is 0.1.
Many are in the range of 1 to 50 g / 10 minutes.

As the polymerization process of the L-LDPE resin, there are a gas phase method using a medium / low pressure apparatus, a solution method, a liquid phase slurry method, and an ionic polymerization method using a high pressure improvement apparatus.

Specific examples of the L-LDPE resin are shown below. Ethylene / butene-1 copolymer resin G resin and NUC-FLX (UCC) Dourex (Dow Chemical) Screer (DuPont Canada) Marlex (Philips) Stamirex (DSM) Exelen VL (Sumitomo Chemical) Neozex (Mitsui Petrochemical) Mitsubishi Polyethylene-LL (Mitsubishi Yuka) Nisseki Linirex (Nippon Petrochemical) NUC Polyethylene-LL (Nippon Unicar) Idemitsu Polyethylene L (Idemitsu Petrochemical) Ethylene-hexene-1 copolymer resin TUFLIN ( (UCC) TUFTHENE (Nihon Unicar) Ethylene / 4-methylpentene-1 copolymer resin Ultzex (Mitsui Petrochemical) Ethylene / octene-1 copolymer resin Stamirex (DSM) Dourex (Dow Chemical) Screer ( Du Nkanada Inc.) MORETEC (Idemitsu Petrochemical)

As a particularly preferred representative example by a trade name, polyethylene has 6 carbon atoms as an α-olefin side chain.
Petrochemical Co., Ltd. introduced 4-methylpentene-1
MORETEC of Idemitsu Petrochemical Co., Ltd., which introduced octene-1 having 8 carbon atoms as an α-olefin side chain, Stamirex of DSM, and Dourex of Dow Chemical Co., Ltd. It is an L-LDPE resin obtained by the company liquid phase process.) Preferable representative examples obtained by the low-pressure gas phase process are listed below under trade names. TUFLIN of UCC and Nippon Unicar Co., Ltd., in which hexene-1 having 6 carbon atoms is introduced as an α-olefin side chain. TUFTHENE and the like. High pressure improvement method
A typical example of (ion polymerization method) is CDF chimie.
Rotorex of Sumitomo Chemical Co., Ltd., Sumikasen L, T of Sumitomo Chemical Co., Ltd.
There are Nipolon-L of OSO Corporation, Ube Polyethylene of Ube Industries, Ltd. and the like.

Further, an ultra-low-density linear low-density polyethylene resin having a density of less than 0.910 g / cm ³ , for example, NUC-FLX of UCC and Exelen VL of Sumitomo Chemical Co., Ltd. are also preferable (the above two products are common). α-olefin uses butene-1 having 4 carbon atoms).

Polymerization was carried out using a metallocene catalyst (hereinafter simply referred to as a metallocene catalyst) which is a typical example of the single-site catalyst.

The density of the ethylene / α-olefin copolymer resin is preferably 0.860 to 0.95.
0 g / cm ³ , more preferably 0.870 to 0.940
g / cm ³ , most preferably 0.880-0.930 g / cm ³
cm ³ . When the density is less than 0.860 g / cm ³ , not only polymerization is difficult and expensive, but also the Young's modulus becomes extremely small, and blocking occurs, which makes it difficult to put into practical use as a film for packaging a photographic photosensitive material. The density is 0.
If it exceeds 950 g / cm ³ , molecular orientation tends to occur in the vertical direction, and the vertical and horizontal strength balance of tear strength is lost. Furthermore, the fluidity of the resin is deteriorated and melt fracture is likely to occur, and it is difficult to put the resin into practical use as a film for packaging photographic light-sensitive materials.

The melt flow rate of the ethylene / α-olefin copolymer resin produced by polymerization using a metallocene catalyst is preferably from 0.1 to 80 g / 10 minutes, more preferably from 0.5 to 60 g / 10 minutes, and particularly preferably from 0.5 to 60 g / 10 minutes. Preferably 1.0 to
40 g / 10 min, most preferably 1.7-20 g / 10
Minutes. If the melt flow rate is less than 0.1 g / 10 minutes, the fluidity of the resin is poor and melt fracture occurs frequently, making it difficult to put the film into practical use as a film for packaging photographic light-sensitive materials. If the melt flow rate exceeds 80 g / 10 minutes, bubbles become unstable, and streaks and wrinkles are likely to occur, making film formation difficult. It is difficult to put into practical use as a film for packaging a photographic light-sensitive material in which the physical strength of the film is small and perfect sealing property must always be ensured.

The Olsen stiffness (AS) of an ethylene / α-olefin copolymer resin produced by polymerization using a metallocene catalyst
TM D 747) is 1000 kg / cm ² or more, preferably 1300 kg / cm ² or more, more preferably 16 kg / cm ² or more.
00 kg / cm ² or more, particularly preferably 1900 kg / cm ²
cm ² or more, most preferably 2200 kg / cm ² or more.

If it is less than 1000 kg / cm ² , film formability is poor, and wrinkles and streaks are easily generated in the film.
It is easy to stretch, it is difficult to secure light-shielding properties and moisture-proof properties, and practical use is difficult in terms of protecting the quality of photographic light-sensitive materials.

The Shore hardness of the ethylene / α-olefin copolymer resin produced by polymerization using a metallocene catalyst (AST
MD D 2240) is preferably 40D or more, more preferably 44D or more, particularly preferably 48D or more,
Most preferably, it is 50D or more. Shore hardness is 40D
If it is less than one, the resin pellets tend to solidify,
Even if the film formability is deteriorated, or even if the film surface is embossed, the lubricity is poor, the flaw is easily generated, the light-shielding property and the moisture-proof property are also deteriorated, and practical use is difficult.

The Vicat softening point (A) of the ethylene / α-olefin copolymer resin produced by polymerization using a metallocene catalyst
STM D 1525) is preferably 70 ° C. or higher, more preferably 80 ° C. or higher, and particularly preferably 85 ° C.
Above, most preferably 90 ° C. or higher. If the Vicat softening point is less than 70 ° C., the package is blocked and adhered by frictional heat during transportation, or is thinned, or a pinhole or tear occurs or the package is left in sunlight,
Even when the surface temperature becomes 70 ° C. or higher, the same problems as described above occur, and it is difficult to put it to practical use.

The melting point of an ethylene / α-olefin copolymer resin produced by polymerization using a metallocene catalyst (ASTM D
(Measured at 2117) is preferably 80 ° C. or higher, more preferably 90 ° C. or higher, particularly preferably 95 ° C. or higher, and most preferably 100 ° C. or higher. If the melting point is less than 80 ° C,
The same problem as in the case where the Vicat softening point is less than 70 ° C. occurs and it is difficult to put into practical use.

The molecular weight distribution of the ethylene / α-olefin copolymer resin produced by polymerization using a metallocene catalyst is as follows.
0 to 5.0 is preferable, and 1.1 to 4.0 are more preferable.
5, particularly preferably 1.2 to 4.0, most preferably 1.3 to 3.5. When the molecular weight distribution is less than 1.0, polymerization production is difficult, and the resin becomes very expensive and practical use is difficult. When the molecular weight distribution exceeds 5.0, there is no quality difference from the ethylene / α-olefin copolymer resin produced by polymerization using a conventional inexpensive polymerization catalyst, despite the use of an expensive metallocene catalyst. It is difficult to put it to practical use because it is only expensive.

Molecular weight distribution refers to the spread of molecular weight. That is, a high molecular substance is generally a mixture of homologous series of polymerizations, and is composed of a large number of molecules having different degrees of polymerization or molecular weights. The spread of the molecular weight is called a molecular weight distribution, and the degree of spread is shown by a molecular weight distribution curve. The average molecular weight includes a weight average molecular weight (Mw) and a number average molecular weight (Mn) depending on the measurement method, and the ratio Mw / Mn shows a large value when the molecular weight distribution is wide. It is a guide. In the case of polyethylene resin, even materials with the same average molecular weight have a wide molecular weight distribution, but stress cracking and creep resistance are good, but impact resistance is slightly inferior, and this width is narrow when subjected to high shear force during processing. Those exhibit higher melt viscosities. Thus, the influence of the molecular weight distribution on the processability and properties of the plastic cannot be ignored.

The molecular weight distribution in the present invention is determined by gel permeation chromatography (hereinafter referred to as GPC).
Is used to determine the molecular weight distribution curve, using a monodisperse polystyrene having a known molecular weight as a standard, and the value calculated from the weight average molecular weight (hereinafter, referred to as MW) / number average molecular weight (hereinafter, referred to as Mn) by the universal calibration method. . A small value indicates that the molecular weights are uniform, and a large value indicates that those having a wide molecular weight ranging from a low molecular weight to a high molecular weight are mixed.

The crystallinity (measured by X-ray diffraction method) of the ethylene / α-olefin copolymer resin produced by polymerization using a metallocene catalyst is preferably 20% or more, more preferably 30% or more, and particularly preferably 40% or more. % Or more, most preferably 50% or more. When the crystallinity is less than 20%,
Even a single-site ethylene / α-olefin copolymer resin having a small molecular weight distribution deteriorates in heat resistance, anti-blocking property, and lubricity, and is difficult to put into practical use as the resin for the outermost layer of the present invention.

The resins other than the single-site ethylene / α-olefin copolymer resin contained in the outermost layer include:
Polymerized without using a single-site catalyst (typical example is a metallocene catalyst) (hereinafter, polymerized without using a single-site catalyst is referred to as “non-single-site type”)
Polyolefin resins are preferred.

The innermost layer is composed mainly of a non-single-site polyolefin resin. The single-site polyolefin resin preferably contains 0 to 45% by weight, more preferably 0 to 35% by weight, 25
% Is particularly preferred, and 0 to 15% by weight is most preferred. The polyolefin resin is the same as that described in the outermost layer.

When the content of the single-site polyolefin resin contained in the innermost layer (hereinafter referred to as a resin produced by polymerization using a single-site catalyst) exceeds 45% by weight, blocking is less likely to occur, especially in winter. In this case, it becomes difficult to form an adhesive layer by blocking. It also becomes expensive. Furthermore, film formability deteriorates and the film forming speed also decreases.

The innermost layer preferably contains 100 to 55% by weight of a non-single site polyolefin resin, more preferably 100 to 65% by weight, and more preferably 100 to 75% by weight.
% Is particularly preferred, and 100-85% by weight is most preferred. The polyolefin resin is the same as that described in the outermost layer, and among these polyolefin resins, an ethylene copolymer resin is preferable because of excellent photographic properties, physical strength, lamination property of blocking adhesion, and the like.

When the content of the non-single-site polyolefin resin contained in the innermost layer is less than 55% by weight,
Blocking is less likely to occur, film formability is deteriorated, film forming speed is reduced, the cost becomes high, and practical use is difficult.

The preferred resin used in the present invention for the innermost layer is
Among non-single site polyolefin resins, LL
DPE resins are preferred. This L-LDPE ( L inea
r L ow D ensity P oly e thylene)
The resin is referred to as a third polyethylene resin, and is a low-cost, high-strength resin that meets the demands of the era of energy saving and resource saving combining the advantages of medium / low density, high density, and both homopolyethylene resins. This resin is obtained by low pressure method or high pressure improvement method using a multi-site catalyst (Ziegler catalyst or the like) and has ethylene and carbon number of 3-20, preferably 4-15.
, Particularly preferably 5 to 10, most preferably 6 to 8
It is a polyethylene-based resin having a structure obtained by copolymerizing two α-olefins and having a linear linear structure with short branches. As the α-olefin, various ones such as linear or branched aliphatic ones, alicyclic ones, and aromatic ones such as styrene can be used.

Preferred aliphatic α-olefins in terms of physical strength and cost include propene-1 and butene-
1, octene-1, hexene-1,4-methylpentene-1, heptene-1, decene-1, undecene-1, dodecene-1 and the like are used. These α-olefins copolymerized with ethylene may be used alone or in combination of two or more. Density (ASTM D-1
505) is 0.86 to 0.935 g / sec so as to ensure the adhesion and lamination by blocking the innermost layer.
cm ^3, preferably is 0.87~0.925g / cm ^3, particularly those in the range of 0.88~0.920g / cm ³ preferred. Melt flow rate (ASTM D-1238
E) of 0.1 to 80 g / 10 min, preferably 0.2
Those within the range of ２０20 g / 10 min, especially 0.3〜6 g / 10 min are preferred. The crystallinity by X-rays is 60% or less, preferably 56% or less, particularly preferably 51% or less, and most preferably 46% from the suitability for blocking adhesion lamination.
It is as follows.

As the polymerization process of the L-LDPE resin, there are a gas phase method using a medium / low pressure apparatus, a solution method, a liquid phase slurry method, and an ionic polymerization method using a high pressure improvement apparatus.

The molecular weight distribution (weight-average molecular weight / number-average molecular weight) measured by the GPC method is 2 or more, preferably 2.5 or more, particularly preferably 3 or more, and most preferably 3 or more, based on suitability for film formation and blocking adhesion lamination. .5 or more.

The non-single-site polyolefin resin preferably has a molecular weight distribution larger than that of the outermost single-site polyolefin resin by 0.5 or more, more preferably 1 or more, particularly preferably 1.5 or more.

What was unexpected was that the addition of the higher fatty acid metal salt to the innermost layer improved not only the film forming suitability but also the blocking adhesive lamination suitability. In particular, 0.01 to 5% by weight of a higher fatty acid metal salt such as calcium stearate or zinc stearate having a melting point of 160 ° C. or lower,
Preferably 0.03 to 3% by weight, particularly preferably 0.03% by weight.
When added in an amount of 5 to 2% by weight, most preferably 0.07 to 1% by weight, blocking adhesive lamination can be surely performed.

Specific examples of the L-LDPE resin produced by polymerization using a commercially available multi-site catalyst are shown below. Ethylene / butene-1 copolymer resin G resin and NUC-FLX (UCC) Dourex (Dow Chemical) Screer (DuPont Canada) Marlex (Philips) Stamirex (DSM) Exelen VL (Sumitomo Chemical) Neozex (Mitsui Petrochemical) Mitsubishi Polyethylene-LL (Mitsubishi Yuka) Nisseki Linirex (Nippon Petrochemical) NUC Polyethylene-LL (Nippon Unicar) Outgoing Polyethylene L (Outgoing Petrochemical) Ethylene / hexene-1 copolymer resin TUFLIN ( UCC) TUFTHENE (Nihon Unicar) Ethylene / 4-methylpentene-1 copolymer resin Ultoxex (Mitsui Petrochemical) Ethylene / octene-1 copolymer resin Stamilex (DSM) Dourex (Dow Chemical) Screer ( Dupontka Da Corporation) MORETEC (out Petrochemical)

In the packaging material for a photographic light-sensitive material of the present invention, various flexible sheets can be laminated on the outermost layer of the multilayer co-extruded film via an adhesive layer. Properties and printability, and heat resistance, abrasion resistance, and physical strength can be increased. Further, a surface coating layer can be provided.

Examples of the flexible sheet include various nonwoven fabrics, various papers, various plastic films, various metal foils, various metal-deposited plastic films,
There are plastic films on which various inorganic substances are deposited, various functional films, various synthetic papers, and the like. Among them, various plastic films and synthetic papers are preferable because they are excellent in dustproofness, moistureproofness, gas barrier properties, physical strength, printability, heat resistance, abrasion resistance and the like. In particular, there is compatibility with the polyolefin resin of the present invention, excellent recyclability is inexpensive,
Polyolefin resin films that have little adverse effect on photographic properties are preferred.

Although not suitable for recycling, the packaging material for photographic light-sensitive materials of the present invention has improved light-shielding properties, improved moisture-proof properties,
A polyethylene-2,6-naphthalate resin film excellent in many properties such as physical strength, bag breaking strength, curl prevention, and abrasion resistance is particularly preferable. Polyethylene-
Since the 2,6-naphthalate resin film itself absorbs a considerable amount of ultraviolet light, it is possible to block ultraviolet light without forming a layer containing an ultraviolet absorbent, which has been conventionally used for a polyethylene terephthalate resin film, and to block light. This is because the ability can be improved. Demonstration materials that can improve this ultraviolet blocking ability are shown below.

Polyethylene-2,6-naphthalate resin film (hereinafter referred to as PEN resin film: thickness 10
FIG. 7 shows the transmittance in the ultraviolet region of a polyethylene terephthalate resin film (hereinafter referred to as a PET resin film: thickness of 10 μm) conventionally used as a transparent flexible sheet.

As is clear from FIG. 7, the PET resin film transmits about 80% from ultraviolet rays having a longer wavelength than around 310 mμ, while the PEN resin film transmits about 80% from ultraviolet rays having a longer wavelength than around 380 mμ. ing. That is, the PEN resin film completely blocks ultraviolet light having a short wavelength of around 380 mμ or less, which indicates that the ultraviolet absorption function is large. The ultraviolet absorber used for the ultraviolet absorber-containing layer usually formed on the PET resin film also shows a UV spectrum almost similar to that of the above-mentioned PEN resin film, but has a little absorption around 400 mμ, so that the transmitted light is yellow. There is a problem with taste. PE
In the case of an N resin film, the PEN resin film is more excellent as the transparent support because there is almost no absorption near 400 mμ and transmitted light hardly takes on a yellow tint. In addition, P having an ultraviolet absorbent layer
The ET resin film requires the formation of an ultraviolet absorber layer, but the ultraviolet absorber layer may be peeled off during long-term storage, and has disadvantages such as being expensive.

The polyethylene-2,6 used in the present invention
The naphthalate resin is a polymer whose main constituent monomer is ethylene-2,6-naphthalate. In this case, the constituent units of other components may be contained by copolymerization in a range of 10 mol% or less. Examples of the bifunctional carboxylic acid component that can be a copolymerized unit include, for example, isophthalic acid, terephthalic acid, aromatic dicarboxylic acids such as 5-sodium sulfoisophthalic acid, 1,4-cyclohexanedicarboxylic acid, adipic acid, and sebacic acid. Examples thereof include aliphatic dicarboxylic acids and their alkyl esters, and polyfunctional carboxylic acids such as trimellitic acid and pyromellitic acid, and their alkyl esters. On the other hand, examples of glycol components other than ethylene glycol which can also be copolymerized units include diethylene glycol, butanediol, polyalkylene glycol 1,4-cyclohexanedimethanol having a molecular weight of 150 to 20,000, and an ethylene oxide adduct of bisphenol A. Can be.

The esterification catalyst, transesterification catalyst and polycondensation catalyst used in the production of polyethylene-2,6-naphthalate resin are titanium compounds, manganese compounds, zinc compounds and antimony compounds which are conventionally known. , Magnesium compound, calcium compound,
A germanium compound or the like can be used as appropriate.
The addition amount of the catalyst is 50 to 500 p with respect to the polyester.
pm is common, and 100-200 ppm is preferable. Further, other metal compounds, nitrogen-containing basic compounds, antioxidants, antistatic agents, ultraviolet absorbers, fluorescent brighteners, dyes and the like may be used according to the purpose. Further, the polyester can be produced by a conventionally known ordinary method. That is, any of a batch system, a counter-batch system, and a continuous system may be used, and a transesterification method or a direct esterification method may be used.

The polyethylene-2,6- used in the present invention
The naphthalate resin film is preferably a biaxially oriented film. Known methods can be used as a method for producing the film. For example, a polyethylene-2,6-naphthalate resin is dried in advance, melt-extruded into a sheet at 275 ° C to 350 ° C (preferably 280 to 320 ° C), and then cooled and solidified at 45 to 110 ° C to produce an amorphous sheet. I do. Then, 80 ° C. to 19
After stretching 2-5 times in the longitudinal direction (long direction) and then in the horizontal direction (width direction) at a temperature of 0 ° C., 165
By performing heat treatment at 290 to 290C (preferably 165 to 270C), a biaxially stretched polyethylene-2,6-naphthalate resin film can be obtained. Further, the obtained film may be subjected to an annealing treatment at a temperature equal to or lower than the glass transition temperature of the polyethylene-2,6-naphthalate resin. The thickness of the film is 4 to 100 μm, preferably 5 to 80 μm, more preferably 6 to 60 μm, particularly preferably 7 to 40 μm, and most preferably 7 to 30 μm.
It is.

From the PET resin film (the number on the left), P
The EN resin film (the number on the right) shows excellent properties.

[Film having a thickness of 25 μm] Tensile modulus (vertical direction) 500 → 650 kgf / mm ² Vertical direction heat shrinkage rate (150 ° C. × 30 minutes) 2.2 → 0.9% Glass transition temperature 70 → 115 ° C. Heat resistance 120 → 155 ° C Moisture permeability 26 → 7g / m ²・ 24 hours O ₂ permeability 3.5 × 10 ^-12 → 0.9 × 10 ^-12 cm ² / cm ²・ se
c ・ cmHg Oligomer amount 15 → 12mg / m ²・ hour

Further, ASTM D 1619-6 in the resin layer on the side of the photographic material constituting the packaging material for the photographic material.
The sulfur content by the measuring method of 0 is set to 0.6% or less, preferably 0.4% or less, particularly preferably 0.2% or less, and most preferably 0.1% or less. If the amount of the sulfur component is not reduced, the photographic properties of the photographic light-sensitive material are adversely affected, such as an increase in fog, abnormal sensitivity, abnormal color formation, and the like. In particular, a free sulfur component which greatly adversely affects the photographic properties of the direct photographic light-sensitive material (each sample is cooled and solidified with liquid nitrogen and then pulverized. 10 ml of this solution was injected into a high-performance liquid chromatograph to determine the amount of sulfur.The high-performance liquid chromatographic separation conditions were as follows: ODS silica column (4.6 φ × 150 m).
m), separation liquid: methanol 95 and water 5 (containing 0.1% of acetic acid and triethylamine each), flow rate: 1 ml / min,
Detection wavelength: 254 nm, quantification is performed by the absolute calibration curve method. ) Is less than 0.1%, preferably less than 0.05%, particularly preferably less than 0.005%, most preferably 0.002.
% Or less. Although expensive, the content of sulfur component is 0.1.
Acetylene black of 1% or less is suitable for a photographic material having an ISO sensitivity of 100 or more for maintaining good photographic properties.

Further, in particular, the content of a cyanide compound that deteriorates photographic properties (the amount of hydrogen cyanide determined by 4-pyridinecarboxylic acid / pyrazolone absorption spectrometry) is determined by measuring the amount of the cyanide compound on the photographic photosensitive material side constituting the photographic photosensitive material packaging material. (In terms of ppm with respect to the weight of the layer) is 10 ppm or less, preferably 5 ppm or less, particularly preferably 2.5 ppm or less, and most preferably 1 ppm or less.

Even if free formaldehyde (which is contained in a light-shielding substance or due to thermal decomposition of a resin) which adversely affects the photographic properties of this photographic light-sensitive material is contained in the photographic light-sensitive material packaging material in a problem amount, a urea compound or 0.001 to 5% by weight, preferably 0.005 to 4% by weight, more preferably 0.01% by weight of thiourea, hydrazine compound, dicyandiamide, hydroxyamine, hydroxylamine hydrochloride, hydantoin compound, hydroxylamine sulfate and formamide.
If it is contained in an amount of 0.02 to 3% by weight, particularly preferably 0.02 to 2% by weight, and most preferably 0.03 to 1% by weight, it can be improved to a practical level. In particular, a hydantoin compound, a hydrazine compound and a hydroxylamine compound have excellent improvement effects.

When at least one of the hydrazine compound and the hydroxylamine compound is contained in an amount of 0.01 to 1% by weight, the problem of photographic properties due to free formaldehyde can be substantially solved.

The outermost layer of the multilayer co-extruded blown film may contain one or more hydrotalcite compounds and zeolite. By containing one or more of hydrotalcite compounds and zeolites, catalyst residues can be neutralized, substances that adversely affect photographic properties by absorbing halogen compounds such as chlorine and hydrochloric acid can be eliminated, and gold can be used. Rust of the mold can be prevented, and resin burning failure can be prevented.

The content of at least one of the hydrotalcite compound and the zeolite is preferably 0.1 to 30% by weight, more preferably 0.2 to 20% by weight, and 0.3 to 10% by weight.
% Is particularly preferred, and 0.4-5% by weight is most preferred. If the content is less than 0.1% by weight, the effect of addition is not exhibited and only the cost of kneading increases, and if the content exceeds 30% by weight, there is no effect of the addition and the generation of dust. It only increases the cost.

The hydrotalcite compound has a general formula of M _x R _y (OH) _{2x + 3y-2z} (A) _z · aH ₂ O where M is Mg, Ca or Zn, and R is Al, Cr or F
e and A are CO ₃ or HPO ₄ , and x, y, z and a are double salts represented by a positive number｝.

As a typical example of the specific example, Mg ₆ A ₁₂ (O
H) ₁₆ CO ₃ .4H ₂ O, Mg ₈ Al ₂ (OH) ₂₀ CO _{3.
5H 2 O, Mg 5 Al 2} (OH) 14 CO 3 · 4H 2 O, Mg 10
Al ₂ (OH) ₂₂ (CO ₃ ) ₂ .4H ₂ O, Mg ₆ Al ₂ (O
_{H) 16 HPO 4 · 4H 2} O, Ca 6 Al 2 (OH) 16 CO 3 ·
4H ₂ O, Zn ₆ Al ₂ (OH) ₁₆ CO ₃ .4H ₂ O, Mg
_4.5 there are _{Al 2 (OH) 13 CO 3} · 3.5H 2 O and the like.

Alternatively, the general formula is M _(1-x) · Al _x · (OH) ₂ · X _{x / n} · mH ₂ O where M represents an alkaline earth metal and Zn. X represents an n-valent anion. And x and m,
n satisfies the condition of the following equation. 0 <x <0.5 0 ≦ m ≦ 2｝ n = 1 to 4. The refractive index (measured by Larsen's oil immersion method) is an integer of 1.40 to 1.60, preferably 1.40.
Hydrotalcite compounds in the range of 45 to 1.55.

[0084] Examples of n-valent anion represented by X in the above ^{formula, Cl -, Br -, I} -, NO 3 -, Cl
O ₄ ⁻ , SO ₄ ²⁻ , CO ₃ ²⁻ , SiO ₃ ²⁻ , HPO ₄ ²⁻ , HB
_{^{O 3 2-, PO 4 3-,}} Fe (CN) 6 3-, Fe (CN) 4 4-,
CH ₃ COC ⁻ and C ₆ H ₄ (OH) COO ⁻ .

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 thermal degradation and thermal decomposition of the thermoplastic resin and additives is neutralized with phosphorous acid which is generated when the phosphorus is 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 compounds, known methods disclosed in JP-B-46-2280 and JP-B-50-30039 can be used.

Examples of natural products of the hydrotalcite compounds include hydrotalcite, stichitite, 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.

In the present invention, the hydrotalcite compound is preferably used after being treated with a surface coating material. By coating the surface, the dispersibility or affinity for the resin is further improved, and the suitability for film processing, physical strength, and the like are also improved.

As examples of such a surface coating material, the above-mentioned surface coating materials (1) to (20) of the light-shielding material can be used, and particularly preferred are, for example, sodium laurate and lauryl. Potassium acid, sodium oleate, potassium oleate, calcium oleate, magnesium stearate, sodium stearate, zinc stearate, potassium stearate, sodium palmitate, potassium palmitate, sodium caprate, potassium caprate, sodium myristate Metal salts of higher fatty acids such as sodium, potassium myristate, sodium linoleate, potassium linoleate; higher fatty acids such as lauric acid, palmitic acid, oleic acid, stearic acid, capric acid, myristic acid, linoleic acid; dodecyl Calcium benzenesulfonate Organic sulfonic acid metal salts such as sodium silbenzenesulfonate; isopropyl triisostearoyl titanate, isopropyl tris (dioctyl pyrophosphate) titanate, tetraisopropyl bis (dioctyl phosphite) titanate, vinyl triethoxy silane, gamma methacryloxypropyl trimethoxy silane , Coupling agents such as gamma glycidoxypropyltrimethoxysilane,
Examples include various lubricants such as higher fatty acid amides, higher fatty acid esters, silicones, and waxes.

The surface coating with these surface coating substances can be performed, for example, by adding an aqueous solution of an alkali metal salt of a higher fatty acid to a state where the hydrotalcite compound is suspended in warm water with stirring. It can be carried out by dropping a melt of a higher fatty acid or a diluent of a coupling agent while stirring the talcite compound powder with a mixer such as a Henschel mixer. The amount of these surface coating substances can be selected and changed as appropriate, but is preferably about 0.01 to 100 parts by weight of the hydrotalcite compound.
50 parts by weight, preferably 0.05 to 35 parts by weight, particularly preferably 0.1 to 20 parts by weight, most preferably 0.5 to 35 parts by weight.
10 parts by weight.

Further, a small amount of other impurities such as metal oxides may be contained in the above hydrotalcite compound as long as the gist of the present invention is not impaired.

In order to further improve the dispersion of the hydrotalcite compounds, for example, higher fatty acids, fatty acid amide-based lubricants, silicone oil, sorbitan fatty acid esters such as sorbitan monostearate, and glycerin fatty acids such as glycerin monostearate One or more esters or the like as a dispersant in the resin composition in a total amount of 0.01
10 to 10% by weight, preferably 0.05 to 8% by weight, particularly preferably 0.08 to 5% by weight, most preferably 0.1 to 10% by weight.
3% by weight may be added. By using in combination with hydrotalcite compounds, photographic properties are prevented from deteriorating, processing stability, the corrosion resistance of the molding machine is improved, resin deterioration is prevented, physical strength is prevented from decreasing, The effect of preventing the occurrence of coloring failure is synergistically improved. When used in combination with one or more stabilizers selected from the group consisting of phenolic antioxidants, phosphorus (phosphite) -based antioxidants and fatty acid metal salts, the photographic performance of the photographic material is hardly degraded and oxidation is prevented. It is particularly preferable because the effect is increased.

In this case, in order not to adversely affect the photographic performance of the photographic light-sensitive material, (1) a phenolic antioxidant is added in an amount of 0.001 to 1.5% by weight, preferably 0.005 to 0% by weight. 0.7% by weight, particularly preferably 0.01 to 0.45% by weight. (2) 0.001 to 1.5% by weight, preferably 0.005 to 0.7% by weight, particularly preferably 0.0% by weight of a phosphorus-based antioxidant;
1-0.45% by weight is added. (3) 0.01 to 5% by weight, preferably 0.03 to 4% by weight, particularly preferably 0.05 to 3% by weight, most preferably, a hydrotalcite compound and / or a fatty acid metal salt (metal soap). Is added at 0.06 to 2% by weight.

The total content of (1) + (2) + (3) is 0.0015 to 6% by weight, preferably 0.002 to 5%.
% By weight, particularly preferably 0.003 to 4% by weight, and most preferably 0.005 to 3% by weight. It is contained in the innermost layer (photosensitive material side) of the packaging material for photographic photosensitive material.
In any case, it is preferable to add the minimum amount that can prevent the deterioration of the resin from the viewpoint of not deteriorating the photographic performance and suppressing the cost increase.

The phosphorus antioxidant is preferably used in combination with a hydrotalcite compound in order to improve the photographic properties of the photographic material.

Fatty acid metal salts which exhibit not only the excellent effect of improving the photographic properties of a photographic light-sensitive material similar to the hydrotalcite compound but also the effect as a dispersant of a lubricant and a light-shielding substance ( Metal soap).

Representative examples of fatty acid metal salts include lauric acid, stearic acid, succinic acid, stearyl lactic acid, lactic acid,
Higher fatty acids such as phthalic acid, benzoic acid, hydroxystearic acid, ricinoleic acid, naphthenic acid, oleic acid, palmitic acid, erucic acid and Li, Na, Mg, Ca, Sr,
Examples thereof include compounds with metals such as Ba, Zn, Cd, Al, Sn, Pb, and Cd, and preferred are magnesium stearate, calcium stearylate, sodium stearate, zinc stearate, zinc oleate, and magnesium oleate. And so on.

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

[0100]

[Table 1]

Zeolite is natural zeolite (anal).
cime, chabazite, heulandit
e, erionite, ferrierite, lau
zeolites containing montite, modernite, etc.), synthetic zeolites (A, NA, X, Y, h)
yadoxy sodalite, ZK-5, B,
R, D, T, L, hydroxy, cancrinit
and various types of zeolites such as e, W, and Zeolaon). This zeolite not only functions as excellently as the above-described hydrotalcite compound, but also functions as a metal-based inorganic antibacterial agent as a metal carrier described later.

Further, by coating the surface with the same amount of the same surface coating substance as the hydrotalcite compound, the dispersibility or freshness with respect to the resin is further improved, and the suitability for film processing and the physical strength are also improved.

In the packaging material for a photographic material of the present invention, at least two of the layers constituting the packaging material for a photographic material contain a light-shielding substance. That is, when contained in the innermost layer of the multilayer coextruded blown film, when contained in the outermost layer, and when the multilayer coextruded film is contained in the intermediate layer when the multilayer coextruded film has the intermediate layer, the innermost layer and the innermost layer are contained. If it is contained in both the outer layer, if it is contained in both the innermost layer and the middle layer,
When it is contained in both the outermost layer and the intermediate layer, it may be contained in all of the innermost layer, the outermost layer and the intermediate layer.

The light-shielding substance will be described. (1) Inorganic compound A. Oxides: 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, talc, etc.

(2) Organic compounds Wood flour (pine, oak, sawdust, etc.), shell fiber (almond, peanut, fir shell, etc.), cotton, jute, paper strip, non-wood fiber (straw, kenaf, bamboo, esparto) Cellophane pieces, nylon fiber, polypropylene fiber, starch (including modified starch and surface-treated starch), aromatic polyamide fiber, etc.

Among these light-shielding substances, inorganic compounds which have little adverse effect on photographic properties and are stable to heat even at 150 ° C. or higher and are opaque are preferable. The active materials black light absorbing carbon black, titanium nitride, graphite and iron black are preferred.

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 preferred 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, # 5
5, # 100, # 600, # 950, # 1000, # 2
200 (B), # 2400 (B), MA8, MA11, M
A100 and the like. In particular, # 41 (B), which is inexpensive, has low impurity content, and has good photographic properties, is preferable as the light-shielding substance of the present invention.

Overseas products include, for example, Black Pearls 2, 46, 70, 71, and Cabot.
74, 80, 81, 607 etc., Regal 300, 3
30,400,660,991, SRF-S etc., Vul
Can 3, 6, etc., Sterling 10, SO,
V, S, FT-FF, MT-FF and the like.

Further, Unit of Ashland Chemical Co., Ltd.
ed R, BB, 15,102,3001,3004,30
06,3007,3008,3009,3011,301
2, XC-3016, XC-3017, 3020, etc., but are not limited thereto.

In the present invention, furnace carbon black is preferred for the purpose of improving light-shielding properties, cost and physical properties. As expensive light-shielding substances having an antistatic effect, acetylene carbon black and ketjen carbon which is a modified by-product carbon black are preferred. Black is preferred.

In order not to adversely affect the photographic properties of the photographic light-sensitive material, the sulfur content in the carbon black (according to ASTM D-1619 measurement method) should be 0.6.
The content is preferably not more than 0.3% by weight, particularly preferably not more than 0.3% by weight, most preferably not more than 0.1% by weight.

For this purpose, the selection of the raw material is important. For example, the above-mentioned sulfur content is as follows. Raw material Oil name Sulfur content in raw oil Creosote oil (coal-based raw material) 0.3-0.6% Ethylene bottom oil (naphtha raw material (petroleum-based raw material)) 0.05-0.1% Ethylene bottom oil ( Diesel feedstock (petroleum-based feedstock) 0.2-1.5% Fluid catalytic cracking residue (petroleum-based feedstock) 0.2-4.0%

Therefore, as a raw material oil, ethylene bottom oil obtained from creosote oil and petroleum is preferable. If ethylene bottom oil obtained from naphtha is used as a raw material, the sulfur content in carbon black is reduced to 0.1 wt. % Is most preferable.

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 low free sulfur content, carbon black produced using ethylene bottom oil from naphtha is most preferred in the present invention.

The content of the cyanide compound by 4-pyridinecarboxylic acid / pyrazolone absorption spectrometry is 0.01% by weight or less, particularly preferably 0.005% by weight or less, most preferably 0.001% by weight or less. The content is good. Further, the aldehyde compound content by the iodine method is 0.1% by weight or less, particularly preferably 0.05% by weight.
Hereafter, it is most preferable to use carbon black having a content of 0.01% by weight or less. Attention should be paid to the fact that even small amounts of these substances adversely affect the photographic properties of the photographic light-sensitive material.

Particularly for photographic materials having high sensitivity (ISO sensitivity of 400 or more), acetylene black having a sulfur content of 0.1% or less, which has a good dispersibility and a large antistatic effect, is preferred. If necessary, acetylene black, furnace carbon black and Ketjen carbon black
It is also preferred to mix more than one species according to the required properties. The form in which the light-shielding substance is blended is roughly classified as follows. (1) Uniformly colored pellets (the most commonly used ones called color compounds) (2) Dispersible powders (treated with various surface treatment agents, also called dry colors, and a dispersing aid (3) Paste (dispersed plasticizer etc.) (4) Liquid (liquid dispersed in surfactant etc. also called liquid color) (5) ) Masterbatch pellets (light-shielding substance dispersed in plastic to be colored in high concentration) (6) Hygroscopic granular powder (dispersed light-shielding substance in plastic at high concentration (7) Dry powder (ordinary untreated dry powder)

Although there are various modes in which the light-shielding substance is mixed with the thermoplastic resin as described above, the master batch method is preferable in terms of cost, prevention of workplace contamination, and the like. The present inventor has also disclosed in JP-A-63-186740 a colored masterbatch resin composition in which a light-shielding substance is dispersed in a specific ethylene / ethyl acrylate copolymer resin.

When used as a packaging material for a photographic light-sensitive material of the present invention, fog does not occur in the photographic light-sensitive material, and there is little occurrence of increase / decrease in photosensitivity and large light-shielding ability.
Even when added to the innermost layer, carbon black is hard to generate and pinholes are less likely to occur in films such as fish eyes.
(Measured by JIS K 6221) 6.0 to 9.0, average particle diameter (measured by electron microscopy) of 10 to 120 mμ, particularly preferably 10 to 80 mμ, and most preferably 1 to 80 mμ.
0 to 60 mμ. Among them, volatile components (J
DBP oil absorption (measured according to JIS K6221 oil absorption method A) is 50 m or less.
Furnace carbon black of 1/100 g or more is preferable in that it is inexpensive, does not adversely affect photographic properties, improves light-shielding properties, improves dispersibility, and hardly deteriorates physical properties. In particular, those obtained from ethylene bottom oil or creosote oil as the raw material oil are preferable, and the most preferable in the present invention is furnace carbon black using ethylene bottom oil obtained from naphtha.

Also, ASTM D 1619 in the packaging material
Unless the sulfur component is determined to be 0.9% or less, preferably 0.7% or less, particularly preferably 0.5% or less, the photographic light-sensitive material of the photographic light-sensitive material may have an increased fog, abnormal sensitivity, or abnormal development. Affects photographic properties. In particular, a free sulfur component directly affecting the photographic properties of a photographic light-sensitive material (each sample was cooled and solidified with liquid nitrogen and then pulverized, and 100 g of the pulverized sample was placed in a Soxhlet extractor and mixed with chloroform.
After extraction cooling at 0 ° C. for 8 hours, the total volume is made up to 100 ml. 10 ml of this solution is injected into a high performance liquid chromatograph, and sulfur is quantified. High-performance liquid chromatography separation conditions are as follows: column; ODS silica column (4.6 φ × 150 mm), separation solution; methanol 95 and water 5 (containing 0.1% each of acetic acid and triethylamine), flow rate: 1 ml / min, detection wavelength; The determination at 254 nm is performed by the absolute calibration method. )
Is 0.1% or less, preferably 0.05% or less, particularly preferably 0.01% or less, and most preferably 0.005% or less. Expensive, but the sulfur content is 0.1%
The following acetylene blacks are suitable for photographic materials having an ISO sensitivity of 100 or more for maintaining good photographic properties.

The content of a cyan compound which deteriorates the photographic properties in the light-shielding substance (a value obtained by converting the amount of hydrogen cyanide determined by 4-pyridinecarboxylic acid / pyrazolone absorption spectrometry into a ppm unit based on the weight of the light-shielding substance) is 20 ppm Or less, preferably 10 ppm or less, particularly preferably 5 pp
m or less, most preferably 1 ppm or less, and an iodine adsorption amount (measured by JIS K 6221) of 20 mg / g or more,
Preferably 30 mg / g or more, particularly preferably 50 mg / g
/ G, more preferably 80 mg / g or more, and dibutyl phthalate (DBP), oil absorption (JIS K 622).
1) is 50 ml / 100 g or more, preferably 60 ml / 100 g or more.
mg / 100 g or more, particularly preferably 70 ml / 100
g, most preferably 100 ml / 100 g or more.

The next preferred light-shielding substance after carbon black has a refractive index of 1.5 as measured by Larsen's oil immersion method.
Zero or more inorganic pigments and various metal powders, metal flakes, metal pastes, metal fibers and carbon fibers. Representative examples of the inorganic pigment and the metal powder having a preferable refractive index of 1.50 or more are shown below, but the present invention is not limited to these. The numbers in parentheses indicate the refractive index. As the inorganic pigment having a refractive index of 1.50 or more, rutile type titanium oxide (2.7)
5), silicon carbide (2.67), anatase type titanium oxide
(2.52), zinc oxide (2.37), antimony oxide (2.3
5), lead white (2.09), zinc white (2.02), lithopone (1.84), zircon (1.80), corundum (1.
77), spinel (1.73), apatite (1.64),
Barite powder (1.64), barium sulfate (1.64), magnesite (1.62), dolomite (1.59), calcium carbonate (1.58), talc (1.58), calcium sulfate (1 .56), silicic anhydride (1.55), quartz powder (1.5
4), magnesium hydroxide (1.54), hydrochloric magnesium carbonate (1.52), alumina (1.50) and the like. Particularly preferred are light-shielding substances having a refractive index of 1.56 or more, most preferably 1.60 or more.

Calcium silicate (1.46), diatomaceous earth (1.45), hydrated silica (1.4) having a refractive index of less than 1.50
4) and the like have a small light-shielding ability, so a large amount of addition is required, and their use as light-shielding substances is not preferred. In addition, due to the recent overseas travel boom, when a high-sensitivity photographic film having an ISO sensitivity of 400 or more is passed through an inspection machine using X-rays in baggage inspection at an airport, fog is likely to occur due to the X-rays. To prevent this, the specific gravity is 3.1 or more, preferably 3.
It is preferable to use four or more light-shielding substances. The form of the light-shielding substance having an X-ray shielding property other than the light-shielding property having a specific gravity of 3.1 or more, preferably 3.4 or more, particularly preferably 4.0 or more is not limited to those exemplified below. ,
It may be in any form, for example, pigments, powders, flakes, whiskers, fibers and the like.

The light-shielding substance having a specific gravity of 3.1 or more includes
Silicon carbide, barium sulfate, molybdenum disulfide, lead oxide (lead white), iron oxide, titanium oxide, magnesium oxide, barium titanate, copper powder, iron powder, brass powder, nickel powder, silver powder, lead powder, steel powder , Zinc powder, tungsten whisker, silicon nitride whisker, copper whisker,
Examples include iron whiskers, nickel whiskers, chromium whiskers, stainless steel powders and whiskers, magnesite, apatite, spinel, corundum, zircon, antimony trioxide, barium carbonate, zinc white, chromium oxide, tin powder, and mixtures thereof.

Particularly preferable light-shielding substances for imparting X-ray shielding properties include zircon, corundum, barium sulfate, barium chloride, barium titanate, lead powder, lead oxide, zinc powder, zinc white, tin powder, and stainless steel powder. , Stainless whisker, iron oxide, tungsten whisker, nickel whisker. A light-shielding substance particularly preferable as a packaging material for an ultra-high-sensitivity photographic light-sensitive material having an ISO sensitivity of 400 or more has a refractive index of 1.50 or more and a specific gravity of 3.1 or more, and most preferably has a refractive index of 1.56 or more. , A light-shielding substance having a specific gravity of 3.4 or more. The content of these light-shielding substances varies depending on the layer thickness, the type of the resin and the application, but is preferably from 0.1 to 80% by weight, preferably from 0.3 to 60% by weight in view of physical strength, economy, production suitability, and the like. More preferably 0.5 to 4
0% by weight, most preferably 1.0 to 20% by weight.

Table 2 shows the refractive index and specific gravity of the light-shielding substance.

[0127]

[Table 2]

The content of the X-ray shielding light-shielding substance is preferably 5 to 80% by weight, more preferably 10 to 70% by weight, and most preferably 20 to 60% by weight. 5% by weight
When the amount is less than the above, there is almost no X-ray blocking effect, and when the amount exceeds 80% by weight, the production is difficult, and the physical strength and the heat sealing property are lacking, so that it is difficult to put to practical use.

The above-mentioned various light-shielding substances do not adversely affect the photographic light-sensitive material and do not deteriorate the film formability. More preferably 1.0% by weight or less,
Most preferably, it is used in a state of 0.5% by weight or less.

The present invention improves the photographic properties of a photographic material having the effect of adsorbing a lubricant, an antioxidant or an organic nucleating agent which is easy to bleed out, or adsorbing a deodorant, an aromatic agent, an oxygen scavenger and the like. Representative examples of oil-absorbing inorganic pigments preferably contained in the present invention include zinc white (52), asbestin (50), clay (51), titanium oxide (56), kaolin (60), talc (60), and carbon black. (60 or more) and activated carbon. The figures in parentheses indicate the oil absorption (measured by the oil absorption A method of JIS K 6221. Unit ml /
100 g).

Representative examples of metal powders (including metal pastes) include aluminum powder, aluminum paste, copper powder, stainless steel powder, iron powder, nickel powder, brass powder, silver powder, tin powder, zinc powder, steel powder and the like. There is.

In the present invention, the aluminum powder includes the aluminum powder and the aluminum paste. The aluminum powder is obtained by coating the surface of the aluminum powder with a surface coating material, or the aluminum paste obtained by removing the low volatile substances from the thermoplastic resin. What is kneaded is preferable. The average particle size is 0.3 to 50 μm to make aluminum powder excellent in uniform dispersibility, moldability, photographic properties, appearance and low odor.
m, preferably 0.5 to 45 μm, particularly preferably 0.
8 to 40 μm, average thickness of 0.03 to 0.5 μm, preferably 0.05 to 0.4 μm, particularly preferably 0.08 to
It is an aluminum powder having 0.35 μm and a fatty acid content of 5% by weight or less, preferably 4% by weight or less, particularly preferably 3% by weight or less.

Here, the aluminum paste refers to the presence of mineral spirit and a small amount of higher fatty acids such as stearic acid or oleic acid when aluminum powder is prepared by a known method such as a ball mill method, a stamp mill method, or an atomizing method. Originally made in paste form. In the present invention, this aluminum paste and various aromatic monovinyl resins (polystyrene resin, rubber-containing polystyrene resin, etc.), and polyolefin thermoplastic resins (various polypropylene resins, various polyethylene resins, acid-modified resins, EVE resins, EEA resins, EAA resins, etc.) , Low molecular weight polyolefin resin, paraffin wax, tackifier, dispersing agent such as metal soap, etc. by heating and kneading, low volatile substances (mainly mineral spirits and white spirits with strong odor)
Was removed by a vacuum pump or the like.
3% or less, preferably 1%
Hereinafter, it is particularly preferable to use one having 0.5% or less as an aluminum paste compound resin or an aluminum paste masterbatch resin.

It is particularly preferred to use the resin as an aluminum paste masterbatch resin in order to eliminate adverse effects and odors on the photographic light-sensitive material. For example, even if the mineral spirit content in a masterbatch resin having an aluminum paste content of 40% by weight is 1.0% by weight, the concentration of the aluminum paste in the packaging material for photographic light-sensitive materials is adjusted to 2% by weight. Then, 19 parts by weight of the natural resin is kneaded with respect to 1 part by weight of the aluminum paste masterbatch. Since some mineral spirits are removed as a gas by heating during molding in the packaging material, the mineral spirit content is reduced. Is 0.05% by weight or less. As a result, there is no adverse effect on the photographic light-sensitive material, and the odor is reduced.

The aluminum powder refers to a powder of molten aluminum obtained by atomizing, granulating, rotating disk dropping, evaporation, or the like, and flakes obtained by grinding aluminum foil by a ball mill, stamp mill, or the like. Including Since aluminum powder alone is unstable, various known surface coating treatments for inactivating the aluminum powder surface are performed. In particular, a specific thickness (5-20 μm,
Preferably 6 to 15 μm, particularly preferably 7 to 10 μm
m), the aluminum foil rolled in step m) is cut with a shredder or the like, annealed and fatty acids are removed, and then 5% by weight or less of fatty acids having 8 or more carbon atoms (including compounds) in the cut aluminum foil. And an average particle size of 0.3 to 5 using at least one of a pulverizer selected from a ball mill, a stamp mill, a vibration mill and an attritor.
Aluminum powder having a thickness of 0 μm, an average thickness of 0.03 to 0.5 μm, and a fatty acid content of 5% by weight or less is particularly preferred in the present invention because of its excellent dispersibility, photographic properties, and low gloss.

For practical use as the packaging material for a photographic light-sensitive material of the present invention, the total content of the light-shielding substance is from 0.1 to 80 in view of quality assurance, physical strength assurance, photographic performance assurance, moldability and economy. Although it is% by weight, the content varies depending on the light-shielding ability, average particle size, and the like of the light-shielding substance. In the case of carbon black, titanium oxide and aluminum powder having excellent light-shielding ability, the total content in the light-shielding layer is from 0.1 to 60% by weight, from 0.3 to 0.3% in view of light-shielding properties, economy, film formability and the like.
It is preferably 40% by weight, more preferably 0.5 to 20% by weight, most preferably 1 to 10% by weight. Content is 0.1
If the amount is less than 10% by weight, unless the thickness of the packaging material for a photographic photosensitive material is increased, the light-shielding ability becomes insufficient and light fog occurs.
For this reason, the molding speed of the packaging material for photographic light-sensitive materials becomes slow (because the cooling time becomes long), and the amount of resin used becomes large, so that it becomes expensive and is difficult to be put into practical use. If the content is more than 60% by weight, it becomes expensive, dispersibility deteriorates, microgrids (agglomerated impurities) increase, pressure fog and abrasion are generated on the photographic material, and packaging for the photographic material is performed. The amount of water in the material increases due to an increase in the amount of water adsorbed on the carbon black, and adversely affects the photographic performance of the photographic light-sensitive material (fog generation, abnormal sensitivity, abnormal coloring, etc.). Further, the moldability of the packaging material for photographic light-sensitive materials is deteriorated (foaming, silver stripes, pinholes, breakage, etc.) and the physical strength is reduced, which makes practical use difficult.

Resin of a light-shielding substance (carbon black, aluminum powder, an inorganic pigment having a refractive index of 1.50 or more, an inorganic pigment having a specific gravity of 3.4 or more, and an inorganic pigment having an oil absorption of 50 ml / 100 g or more are particularly preferable) Improvement of dispersibility in the inside, improvement of resin fluidity, prevention of generation of micro grit that generates friction fog, pressure fog, abrasion, etc. on photographic photosensitive materials, prevention of generation of volatile substances harmful to photographic properties, reduction of moisture absorption, It is preferable to coat the surface with a surface coating material to prevent die lip contamination.

The following are typical examples of the surface coating material. (1) Coupling agent Coupling agent coating containing azidosilanes
Silane-based coupling agent coating (aminosilane, etc.) titanate-based coupling agent coating (2) silica is deposited, followed by alumina deposition coating (3) zinc stearate, magnesium stearate,
Higher fatty acid metal salt coating such as calcium stearate (4) Surfactant coating such as sodium stearate, potassium stearate, oxyethylene dodecyl amine (5) Barium sulfide aqueous solution and sulfuric acid aqueous solution in the presence of excess barium ion With an average particle diameter of 0.1 to
An aqueous solution of alkali silicate is added to the water slurry to form barium silicate on the surface of barium sulfate, and then mineral acid is added to the slurry to decompose the barium silicate to hydrated silica. (6) Metal hydrated oxide (one or more hydrated oxides of titanium, aluminum, cerium, zinc, iron, cobalt or silicon) and / or metal oxide (One or two or more oxides of titanium, aluminum, cerium, zinc, iron, cobalt or silicon) Surface coated with a composition consisting only of (7) Aziridine group, oxazoline group and N-
Coated with a polymer having one or more reactive groups selected from the group consisting of hydroxyalkylamide groups (8) coated with a polyoxyalkyleneamine compound (9) cerium cation, selected acid anion and alumina (10) Surface coated with an alkoxytitanium derivative having an α-hydroxycarboxylic acid residue as a substituent (11) Surface coated with polytetrafluoroethylene (12) Surface coated with polydimethylsiloxane or modified silicone (13) (14) Surface coating with 2- to 4-hydric alcohol (15) Surface coating with olefin wax (polyethylene wax, polypropylene wax) (16) Surface coating with hydrous aluminum oxide (17) Silica or zinc compound ( Zinc chloride, zinc hydroxide,
(18) Surface coating with polyhydroxy saturated hydrocarbon (19) Surfactant (cationic type) (18) Surface coating with zinc oxide, zinc sulfate, zinc nitrate, zinc acetate, zinc acetate, zinc citrate, etc.) (20) Organometal chelate compounds (especially β-diketone chelate compounds are preferred because they are excellent in photographic properties and dispersibility, etc.) The surface coating amount is 100 parts by weight of a light-shielding substance (Preferably 0.001 to 20 parts by weight, preferably 0.01 to 15 parts by weight) and a surface coating (21) an aliphatic monocarboxylic acid having 20 to 40 carbon atoms and an aliphatic monocarboxylic acid having 20 to 40 carbon atoms. (22) Surface coating with metal salt of partially saponified fatty acid ester having 20 to 50 carbon atoms, etc.

As the surface coating material of the light-shielding material, there is little adverse effect such as fogging on the photographic characteristics of the photographic material.
(1), (3), (12), (14), (1)
In addition to 5), (16), (18), (19), (21), and (22), organometal chelate compounds, various antistatic agents, lubricants, and drip-proof agents are preferable.

In particular, an ester of an aliphatic monocarboxylic acid having 20 to 40 carbon atoms and an aliphatic monohydric alcohol having 20 to 40 carbon atoms is used in an amount of 0.0 to 100 parts by weight of the light-shielding substance.
It has been found that the effect of preventing the above problems can be exhibited by adding 0.01 to 20 parts by weight, preferably 0.005 to 10 parts by weight, particularly preferably 0.01 to 5 parts by weight. In particular, it not only reduces the adverse effect on the photographic properties of the photographic light-sensitive material but also reduces the motor load, improves the dispersibility of the light-shielding substance, improves the moldability, and improves the appearance of the molded article.

As the ester used in the present invention, an aliphatic monocarboxylic acid having 20 to 40 carbon atoms, preferably 25 to 35 carbon atoms, and 20 to 40 carbon atoms, preferably 25 to 3 carbon atoms.
5 is an ester of an aliphatic monohydric alcohol.

Examples of the above-mentioned monocarboxylic acids include montanic acid, melicic acid, cerotic acid, bricinic acid, lacceric acid and the like.

Examples of the monohydric alcohol include montyl alcohol, merisyl alcohol, lacsyl alcohol,
Seryl alcohol, brisyl alcohol and the like can be mentioned.

These are very excellent as surface coating materials for the light-shielding substance, since they improve the fluidity of the thermoplastic resin and achieve uniform kneading. further,
When used as a dispersant for the inorganic and / or organic nucleating agent in the surface coating, various excellent effects such as scattering prevention, bleed-out prevention, uniform dispersibility improvement, and resin fluidity improvement are exhibited.
The surface coating amount of the light-shielding substance is 0.001 to 20 parts by weight, preferably 0.001 to 5 parts by weight, based on 100 parts by weight of the light-shielding substance such as carbon black, titanium oxide or aluminum powder. Parts by weight, more preferably 0.01 to 3 parts by weight, most preferably 0.05 to 1.
5 parts by weight. When the coating amount is 0.001 part by weight or less, the coating effect is hardly exhibited. If the coating amount exceeds 20 parts by weight, the occurrence of bleed-out increases with time.

The total sulfur content in the above total light-shielding substance (AST
MD-1619) is at most 0.9%, preferably at most 0.7%, particularly preferably at most 0.5%, and the free sulfur content is at most 150 ppm, preferably at most 50 ppm, particularly preferably at most 30 ppm. , ASTM D-150
6, the ash content is not more than 0.5%, preferably not more than 0.4%, particularly preferably not more than 0.3%, and the aldehyde compound content is not more than 0.2%, preferably not more than 0.1%,
It is particularly necessary to take care that if the content is not less than 0.05%, the photographic properties will be adversely affected.

Further, a cyanide compound adversely affects the photographic performance of a photographic light-sensitive material.
The value obtained by converting the amount of hydrogen cyanide quantified by pyrazolone absorption spectrometry into ppm unit based on the weight of the light-shielding substance is 20.
A light-shielding substance of at most 10 ppm, preferably at most 10 ppm, particularly preferably at most 5 ppm, most preferably at most 1 ppm is used.

A lubricant can be contained in the innermost layer, the outermost layer, and the like of the packaging material for a photographic light-sensitive material of the present invention. By containing a lubricant, the suitability for handling and lubricity of the film can be improved, and wrinkles and streaks can be prevented. Furthermore, even if it rubs against a photographic material as a packaging bag or the like, scratches and static marks can be prevented from occurring.

The amount of the lubricant to be added varies depending on the kind, and a small lubricating effect such as a fatty acid metal salt (same as a metal soap described later) mainly for maintaining the photographic performance of the photographic material in a good state is small. In the case of a lubricant, it is preferably 0.01 to 5% by weight, more preferably 0.03 to 3% by weight,
Particularly preferred is 5 to 1.5% by weight, and 0.07 to 1% by weight.
Is most preferred. If the addition amount is less than 0.01% by weight, there is no effect of addition and only the kneading cost increases. If the addition amount exceeds 5% by weight, the heat seal strength with time decreases, and the sealing property, moisture-proof property and oxygen barrier property deteriorate, and it is difficult to put it to practical use as a packaging material for photographic materials.

The lubricant has a large lubricating effect, such as a fatty acid amide-based lubricant and a bisfatty acid amide-based lubricant. However, in the case of a lubricant which easily bleeds out and adversely affects a photographic light-sensitive material, 0.01 to 1% by weight is used. Is preferably 0.03-0.5.
% By weight is more preferable, and 0.05 to 0.3% by weight is most preferable. If the addition amount is less than 0.01% by weight, there is no effect of addition and only the kneading cost increases. Addition amount is 1
If the content is more than 10% by weight, stickiness and bleed-out are likely to occur with the lapse of time after film formation. Further, the bleed-out lubricant is transferred to the photographic photosensitive layer to cause development inhibition, thereby causing quality failures such as uneven development and uneven coloring.

The names of typical commercially available lubricants and manufacturers are described below. (1) Fatty acid amide-based lubricant; [Saturated fatty acid amide-based lubricant] Behenic acid amide-based lubricant; Diamid KN (Nippon Kasei), etc. Stearic amide-based lubricant; Armide HT (Lion Oil), Alflo S-10
(Nippon Yushi), fatty acid amide S (Kao), Diamid 200 (Nippon Kasei), Diamid AP-1 (Nippon Kasei), Amide S. Amide T (Nitto Chemical), Neutron-2 (Nippon Seika), etc. [Hydroxystearic amide lubricant] Palmitic amide lubricant; Neutron S-18 (Nippon Seika), Amide P (Nitto Chemical), etc. Lauric amide lubricant; Armide C (Lion Akzo), Diamond (Japan) [Unsaturated fatty acid amide lubricant] Erucamide amide lubricant; Alflo P-10 (Nippon Oil & Fats), Neutron-S (Nippon Seika), LUBROL
(I ・ C ・ I), Diamid L-200 (Nippon Kasei)
Oleic amide lubricants; Armoslip CP (Lion Akzo), Neutron (Nippon Seika), Neutron E-18 (Nippon Seika), Amide O (Nitto Chemical), Diamid O-200, Diamid G-200 (Nippon Kasei), Alflo E-10 (Nippon Oil & Fats), fatty acid amide O (Kao), etc. [Bis fatty acid amide lubricant] Methylene bisbehenic amide lubricant; Diamid NK bis (Nippon Kasei) Methylenebisstearic acid amide lubricant; Diamid 200 bis (Nippon Kasei), Armowax (Lion Akzo), bisamide (Nitto Chemical), etc. Methylenebisoleic amide lubricant; Lubron O (Nippon Kasei), etc. Ethylene bisstearic acid Amide-based lubricants: Armoslip EBS (Lion Akzo) etc. Hexamethylene bisstearic acid De lubricants; Amide 65 (Kawaken Fine Chemicals) or the like hexamethylene bis oleic acid amide lubricants; Amide 60 (Kawaken Fine Chemicals) or the like

(2) Nonionic surfactant lubricant; Electrostripper-TS-2, Electrostripper-T
S-3 (Kao soap) etc.

(3) Hydrocarbon lubricant; liquid paraffin,
Natural paraffin, microwax, isoparaffinic synthetic petroleum hydrocarbon, synthetic paraffin (C16 to 49, preferably C20 to 30), polyethylene wax (number average molecular weight of 10,000 or less, preferably 8,000 or less, particularly 6,000 or less) The following are preferred), polypropylene wax (number average molecular weight is 10,000 or less, preferably 8,000 or less, particularly preferably 6,000 or less), chlorinated hydrocarbon, fluorocarbon, etc.

(4) Fatty acid-based lubricants; higher fatty acids (C12
To 35 are preferred, specifically, caproic acid, stearic acid, oleic acid, erucic acid, palmitic acid, etc.), oxy fatty acids, etc.

(5) Ester lubricants: lower alcohol esters of fatty acids, polyhydric alcohol esters of fatty acids, polyglycol esters of fatty acids, fatty alcohol esters of fatty acids, etc.

(6) Alcohol lubricants: polyhydric alcohols, polyglycols, polyglycerols, etc.

(7) Fatty acid metal salt lubricants (metal soaps): 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 Acids, higher fatty acids such as erucic acid and Li, Na, M
g, Ca, Sr, Ba, Zn, Cd, Al, Sn, P
Compounds with metals such as b, Cd and the like are mentioned, and preferred are magnesium stearate, calcium stearate, sodium stearate, zinc stearate, calcium oleate, zinc oleate, magnesium oleate and the like.

(8) Partially saponified montanic acid ester;

(9) Silicone-based lubricants: Various grades of dimethylpolysiloxane and modified products thereof (Shin-Etsu Silicone, Toray Silicone), in particular, 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, the dispersibility of the light-shielding substance is improved,
As a result of making the resin cloudy and increasing the haze (ASTM D-1003), unexpected effects such as improvement in coloring power and improvement in light-shielding properties are exhibited, which is preferable.

The silicone oil preferably has a viscosity at room temperature in the range of 50 to 100,000 centistokes, more preferably 5,000 to 30,000 centistokes.
A high viscosity of 0 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, α-methylstyrene-modified silicone, polyethylene glycol and polypropylene glycol. It is a silicone oil containing a modified siloxane bond such as polyether-modified silicone, olefin / polyether-modified silicone, epoxy-modified silicone, amino-modified silicone, and alcohol-modified silicone. In the silicone oil,
Olefin-modified silicones, amide-modified silicones, polydimethylsiloxanes, polyether-modified silicones, and olefins, which do not adversely affect the photographic light-sensitive material and have a large lubricating effect, and are particularly preferable when applied to packaging materials for photographic light-sensitive materials / Polyether-modified silicone. The silicone oil improves the coefficient of friction of a molding material in a heated state, for example, a resin film, reduces sliding resistance generated during hot plate sealing by an automatic packaging machine,
By preventing wrinkles from occurring, it is possible to form a basis for obtaining a resin film having a beautiful appearance, a high level 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 effect of the addition of silicone oil is 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-based lubricant that bleeds out to form a white powder. (4) The coefficient of friction of the packaging material in a heated state is reduced, the suitability for automatic bag making is improved, wrinkles during heat sealing and gloss reduction due to sliding are prevented, and a beautiful sealed portion can be obtained. (5) When used in combination with a light-shielding substance, the dispersibility is improved and the thermoplastic resin becomes cloudy and the haze is increased. As a result, the coloring power can be improved, the light-shielding ability can be improved, and the added amount of the light-shielding substance decreases physical properties. Even if the weight is reduced, the shielding property can be secured.

An antioxidant can be contained in the innermost layer, the outermost layer, and the like of the packaging material for a photographic light-sensitive material of the present invention. By containing an antioxidant, it prevents the thermal degradation and thermal decomposition of additives such as thermoplastic resins and fatty acids, lubricants, organic nucleating agents, and surfactants, and significantly changes the fluidity of the thermoplastic resin composition. And the occurrence of bumps can be prevented.
Further, it is possible to prevent the generation of thermal decomposition substances (aldehydes, cyanide compounds, sulfur compounds, etc.) which adversely affect the photographic light-sensitive material. Various known compounds that reduce and stabilize pyrolytic substances (aldehydes, cyanide compounds, sulfur compounds, etc.) to an amount that does not adversely affect the photographic light-sensitive material, stabilize the reaction, or stabilize the adsorption (for example, hydantoin compounds, It is preferable to add a hydrazine compound, a urea compound, a noble metal such as palladium, gold or platinum, or a noble metal compound, or a metal such as rhodium or iridium. By controlling the amount of formaldehyde in the packaging material for photographic light-sensitive material to 500 PPM or less, preferably 300 PPM or less, particularly preferably 150 PPM or less, and most preferably 75 PPM or less, good photographic properties can be maintained. In addition, when the content of the cyanogen compound determined by 4-pyridinecarboxylic acid / pyrazolone absorption spectrometry is 10 PPM or less, preferably 5 PPM or less, particularly preferably 1 PPM or less, good photographic properties can be maintained.

The amount of one or more antioxidants added is 0.0
0.01 to 1.5% by weight, 0.005 to 0.7% by weight
Is preferable, and 0.01 to 0.45% by weight is more preferable. When the addition amount is less than 0.001% by weight, there is no addition effect and only the kneading cost increases, and the addition amount is 1% by weight.
Exceeding the range adversely affects the photographic properties of the photographic light-sensitive material utilizing the oxidizing and reducing actions and bleeds out to the surface of the packaging material to deteriorate the appearance and heat sealability.

Typical examples of the antioxidant used in the present invention are shown below. (A) Phenolic antioxidants (t is an abbreviation for tert) Vitamin E (tocopherol), tocopherol dimer (α-tocopherol, β-tocopherol, 5,7
-Dimethyltocol, etc.), 6-t-butyl-3-methylphenyl derivative, 2,6-di-t-butyl-P-cresol, 2,6-di-t-butyl-phenol, 2.6
-Di-t-butyl-α-dimethylamino-p-cresol, 2.6-di-t-butyl-p-ethylphenol,
2,2'-methylenebis- (4-ethyl-6-t-butylphenol), 4,4'-butylidenebis (6-t-butyl-m-cresol), 4,4'-thiobis (6-t
-Butyl-m-cresol), 4,4-dihydroxydiphenylcyclohexane, butylated hydroxyanisole, alkylated bisphenol, styrenated phenol, 2,6-di-t-butyl-4-methylphenol,
2,6-di-t-butyl-4-ethylphenol, n-
Octadecyl-3- (3'.5'-di-t-butyl-4 '
-Hydroxyphenyl) propinate, 2.2′-methylenebis (4-methyl-6-t-butylphenol),
4.4'-thiobis (3-methyl-6-t-butylphenyl), 4,4'-butylidenebis (3-methyl-6-t
-Butylphenol), 4.4′-thiobis (3-methyl-6-t-butylphenol), stearyl-β (3.
5-di-t-butyl-4-hydroxyphenyl) propionate, 1.1.3-tris (2-methyl-4hydroxy-5-t-butylphenyl) butane, 1.3.5 trimethyl-2.4.4. 6-tris (3.5-di-tert-butyl-4-hydroxybenzyl) benzene, tetrakis [methylene-3 (3.5-di-tert-butyl-4-hydroxyphenyl) propionate] methane, etc.

(B) Ketone amine condensation antioxidant 6-ethoxy-2,2,4-trimethyl-1,2-dihydroquinoline, polymer of 2,2.4-trimethyl-1,2-dihydroquinoline, trimethyl Dihydroquinoline derivatives, etc.

(C) Allylamine antioxidants phenyl-α-naphthylamine, N-phenyl-β-naphthylamine, N-phenyl-N′-isopropylpropyl-P
-Phenylenediamine, NN'-diphenyl-P-phenylenediamine, NN'-di-β-naphthyl-P-
Phenylenediamine, N- (3'-hydroxybutylidene) -1-naphthylamine and the like

(D) Imidazole antioxidants 2-mercaptobenzimidazole, zinc salt of 2-mercaptobenzimidazole, 2-mercaptomethylbenzimidazole, etc.

(E) Phosphite antioxidants Alkylated allyl phosphite, tris (mono and / or dinonylphenyl) phosphite, cyclic neopentanetetraylbis (2.6-di-t-butyl-4)
-Methylphenyl) phosphite, diphenylisodecylphosphite, tris (nonylphenyl) phosphite sodium phosphite, tris (nonylphenyl) phosphite, 2.2-methylenebis (4.6-di-t-butylphenyl) Octyl phosphite, Tris (2.4
-Di-t-butylphenyl) phosphite, triphenyl phosphite, etc.

(F) Thiourea-based antioxidants Thiourea derivatives, 1,3-bis (dimethylaminopropyl) -2-thiourea, etc.

(G) Other antioxidants useful for air oxidation: dilauryl thiodipropionate

Representative examples of the most preferred hindered phenolic antioxidants for the present invention are shown below. 1,3,5-trimethyl 2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, tetrakis [methylene-3- (3 ′ · 5′-di-tert-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'-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), 4,4'-butylidenebis- (3-methyl-6-tert-butylphenol), 2,6-di-tert-butyl-4-methylphenol, 4-hydroxymethyl-2 , 6-di-t
tert-butylphenol, 2,6-di-tert-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-tetraoxaspiro [5,5] undecane. Among them, the melting point is 100 ° C. or more, especially 120 ° C.
The above are preferred. Further, it is effective to use it in combination with a phosphorus antioxidant. Furthermore, at least one of a phosphorus-based antioxidant, at least one of a hindered phenol-based antioxidant, and at least one of a water-containing double salt compound (a typical example is a hydrotalcite compound); It is particularly preferable to use a combination of these because the photographic properties are improved, and lumps, resin burning and coloring can be prevented.

At least one of the phosphorus antioxidants is used in an amount of 0.0
When the content is from 0.01 to 1.5% by weight, preferably from 0.005 to 0.7% by weight, and more preferably from 0.01 to 0.45% by weight, phosphorous acid generated by thermal decomposition may affect the photographic properties of the photographic material. Hydrotalcite compounds which neutralize phosphorous acid because they have a bad influence and generate fog are added in an amount of 0.1%.
It is preferably added in an amount of from 0.01 to 5.0% by weight, more preferably from 0.03 to 4% by weight, particularly preferably from 0.05 to 3.0% by weight. In particular, in the case of a high-sensitivity photographic material having an ISO sensitivity of 50 or more, the combined use of a phosphorus-based antioxidant and a hydrotalcite compound is necessary to maintain good photographic properties.

The above-mentioned vitamin E (tocopherol) and tocopherol dimer have an excellent antioxidant effect and, when used in combination with a light-shielding substance such as carbon black by coloring the film yellow, the light-shielding ability of carbon black or the like. Since the light-shielding substance is improved and the dispersibility is improved as compared with the case of adding the light-shielding substance alone, a film having the same light-shielding property can be obtained even when the addition amount of the light-shielding substance is reduced by 10% or more. As a result, various effects such as prevention of deterioration of photographic properties, improvement of light-shielding ability, improvement of physical strength, improvement of appearance, and reduction of material cost are exhibited, and therefore it is particularly preferable as the packaging material for photographic photosensitive materials of the present invention.

Particularly preferred antioxidants are phenolic antioxidants, and commercially available products include Irganox 1010 of Ciba-Geigy and Sumil of Sumitomo Chemical Co., Ltd.
iser BHT, Sumilizer BH-76, S
umilizer WX-R, Sumilizer BP
−101 and the like. Also, 2,6-t-hybutyl-p-
Cresol (BHT), a low volatility, high molecular weight phenolic antioxidant (trade name: Ireganox 1010,
Ireganox 1076, Topanol CA, I
onox 330, etc.) and phosphorus antioxidants (distearyl-pentaerythritol-diphosphite, dilaurylthiodipropionate, distearylthiopropionate, tris (2,4-di-t-butyl-phenyl)) Phosphite, dialkyl phosphate, etc.)
It is effective to use two or more kinds, particularly two or more kinds in combination.

In particular, at least one of the above hindered phenolic antioxidants having a melting point of at least 100 ° C., preferably at least 120 ° C., which is a typical example of a free radical chain terminator, and a phosphorus-based oxidizing agent which is a peroxide decomposing agent It is preferable to use at least one of the inhibitors in combination, because the effect of preventing the resin and the additives from being thermally degraded can be enhanced without deteriorating the photographic properties. Most preferably, the total of 0.001 to 1.5% by weight of one or more of the phosphorus-based antioxidant and one or more of the hindered phenol-based antioxidant is generated by thermal decomposition of the phosphorus-based antioxidant. At least three kinds of hydrotalcite compounds 0.01 to 5.0% by weight, which function as a neutralizing agent for phosphorous acid to prevent fogging of a photographic light-sensitive material, are used in combination.

The photographic light-sensitive material has little adverse effect on photographic properties, is colored when exposed to light to improve the light-shielding ability, has little thermal decomposition even at a resin melting temperature (130 to 400 ° C.), and has little bleed-out due to aging. The molecular weight is 200 or more, preferably 300 or more from the viewpoint of having excellent characteristics of,
Particularly preferred are hindered phenolic antioxidants of 400 or more, most preferably 500 or more.

In particular, without adversely affecting the photographic properties of the photographic light-sensitive material, it is safe for the human body, prevents thermal decomposition and thermal degradation of resins and additives, and is colored when exposed to light to improve the light-shielding ability. Vitamin E and tocopherol dimers are preferred.

The most preferred antioxidant to be contained in the packaging material of the present invention is tetrakis [methylene-3 (3,5-di-tert-butyl-4-hydroxy-hydroxy).
Phenyl) propionate] methane, n-octadecyl-3- (4'-hydroxy-3 ', 5'-di-t-butylphenol) propionate and tris- (2,4-di-
(t-butylphenyl) phosphite.

A compatibilizer can be contained in the outermost layer, the innermost layer, etc. of the multilayer co-extruded blown film. The content of the compatibilizer is 1 to 50% by weight, preferably 2 to 45% by weight, more preferably 5 to 40% by weight, and most preferably 8 to 35% by weight. If it is less than 1% by weight, there is no effect of addition and only the kneading cost is increased. Further, even if it exceeds 50% by weight, there is no effect of increasing the amount and the cost is increased. Further, the physical strength also decreases. This compatibilizer is effective when the content of the recycled resin is 30% by weight or more.

The compatibilizer is generally a thermoplastic resin of the same type but having different properties, two or more types of thermoplastic resins, a recycled thermoplastic resin and a virgin thermoplastic resin (which have never been used in molded articles in the past). Resin, that is, a resin used for the first time in a molded article. The same applies hereinafter), a masterbatch thermoplastic resin containing a light-shielding substance at a high concentration, and a thermoplastic resin for dilution (light-shielding from the other resin to be blended). A resin with low or no concentration of aggressive substances. The same applies hereinafter) or when a new thermoplastic resin is used to develop new properties and performances that are not available in a single thermoplastic resin, such as a resin combining these. A substance that can achieve compatibilization of multiple resins.

The compatibilizer includes a non-reactive compatibilizer and a reactive compatibilizer. Specific representative examples of the compatibilizer are shown below.

Representative examples of non-reactive compatibilizers Styrene / ethylene / butadiene block copolymer resin Polyethylene / polystyrene graft copolymer resin Polyethylene / polymethyl methacrylate graft copolymer resin Polyethylene / polymethyl methacrylate block copolymer resin Ethylene / propylene / diene copolymer resin Ethylene / propylene copolymer resin Polystyrene / low density homopolyethylene graft copolymer resin Polystyrene / high density homopolyethylene graft copolymer resin Hydrogenated styrene / butadiene copolymer resin Styrene / ethylene , Butadiene / styrene copolymer resin Styrene / butadiene / styrene copolymer resin Chlorinated polyethylene resin Polypropylene / polyamide graft copolymer resin Polypropylene / ethylene / Propylene / diene copolymer resin polystyrene / polyethyl acrylate graft copolymer resin polystyrene / polybutadiene graft copolymer resin polystyrene / polymethyl methacrylate block copolymer resin etc. Typical examples of reactive compatibilizers Anhydrous ethylene oxide・ Propylene copolymer resin Maleic anhydride styrene graft copolymer resin Maleic anhydride styrene / butadiene / styrene copolymer resin Maleic anhydride styrene / ethylene / butadiene / styrene copolymer resin ethylene / glycidyl methacrylate copolymer resin ethylene・ Glycidyl methacrylate / styrene graft copolymer resin Ethylene / glycidyl methacrylate / methyl methacrylate graft copolymer resin Maleic anhydride graft polypropylene Combined resin
etc

Table 3 shows typical examples of the internal and external commercially available compatibilizers.

[0183]

[Table 3] SBS: Abbreviation of styrene-butadiene-styrene copolymer resin SEBS: Abbreviation of styrene-ethylene-butadiene-styrene copolymer resin EPDM: Abbreviation of ethylene-propylene-diene copolymer resin EVA: Ethylene-vinyl acetate copolymer Abbreviation of resin

An antimicrobial agent is added to at least one of the innermost layer, the outermost layer and the intermediate layer of the multilayer co-extruded blown film, and to the flexible sheet layer and the surface coating layer (such as a non-slip layer and an antimicrobial-containing coating layer). (Including a bactericide, a fungicide, etc.). By containing an antibacterial agent, it is possible to suppress the occurrence of various bacteria such as bacteria and mold which have an adverse effect on gelatin and the like constituting the photographic light-sensitive material.

The content of the antibacterial agent is generally 0.001 to 20% by weight based on the resin composition constituting the resin layer.
However, 0.001 to 10% by weight is preferable, and 0.001 to 10% by weight is preferable.
01 to 7% by weight is more preferable, and 0.005 to 5% by weight.
Is particularly preferable, and 0.01 to 2% by weight is most preferable.
If the content is less than 0.0001% by weight, an effective antibacterial effect cannot be obtained. On the other hand, if the content exceeds 20% by weight, not only the effect of increasing the amount is not obtained but also the cost becomes high, the appearance of the inflation film is deteriorated, and the photographic properties of the photographic material are adversely affected.

The antibacterial agents are roughly classified into organic antibacterial agents, metal-based inorganic antibacterial agents and natural antibacterial agents. Examples of the organic antibacterial agents include 1,2-benzisothiazolin-3-one and N-antibacterial agent. Fluorodichloromethylthio-phthalimide,
2,3,5,6-tetrachloroisophthalonitrile (hereinafter referred to as TPN), N-trichloromethylthio-4-
Cyclohexene-1,2-dicarboximide, copper 8-quinolinate, bis (tributyltin) oxide, 2- (4
-Thiazolyl) benzimidazole (hereinafter referred to as TBZ), methyl 2-benzimidazolecarbamate (hereinafter referred to as BCM), 10,10'-oxybisphenoxyarsine (hereinafter referred to as OBPA), 2,3,5 , 6-
Tetrachloro-4- (methylsulfone) pyridine, bis (2-pyridylthio-1-oxide) zinc <hereinafter Z
PT, and N, N-dimethyl-N '-(fluorodichloromethylthio) -N'-phenylsulfamide <dichlorofluanid>, but not limited thereto. Among organic antibacterial agents, TPN, TBZ, BCM, OBPA, ZP
T is preferred. Particularly, an organic antibacterial agent having a decomposition temperature of 240 ° C. or more is preferable.

As metal-based inorganic antibacterial agents, for example, silver,
Zeolite-based antibacterial agents, silica gel-based antibacterial agents, zirconium phosphate-based antibacterial agents, activated carbon-based antibacterial agents, titanium oxide-based agents in which metals such as copper, zinc, and nickel are supported on silicate-based carriers and phosphate-based carriers Antibacterial agents, titania-based antibacterial agents, glass-based antibacterial agents, organometallic antibacterial agents, calcium phosphate-based antibacterial agents, ion-exchange ceramics-based antibacterial agents, and the like, but are not limited thereto. Since these are not transpirable, the effects can be maintained for a long period of time and do not affect the human body. Further, it can be stably dispersed in the resin or the paint, and the resin or the paint does not deteriorate.

As the metal-based inorganic antibacterial agent, an inorganic antibacterial agent carrying a metal ion having antibacterial properties is preferable because it hardly adversely affects the photographic properties, physical properties and appearance of the photographic light-sensitive material.

Typical metal ions having antibacterial properties include silver ions, zinc ions, nickel ions, tin ions, bismuth ions, copper ions, manganese ions, cobalt ions, lead ions and the like.

Among these, silver ions and zinc ions, which have excellent antibacterial properties and do not adversely affect the photographic properties of the photographic light-sensitive material, are preferred, and silver ions are particularly preferred.

It is preferable that these metal ions are supported on the above-mentioned zeolite, silica gel, zirconium phosphate, activated carbon, titanium oxide, and the like. In particular, those supported on zeolite include aldehydes which adversely affect the photographic properties of photographic light-sensitive materials. Adsorbs free sulfur, ammonia, mercaptan, hydrogen sulfide, etc. to reduce the adverse effect on photographic properties, and also works with packaging materials or between packaging materials and the photosensitive layer composed of gelatin or hydrophilic polymer of photographic photosensitive materials. Is most preferred because it also has an anti-blocking effect.

Currently, over 100 types of zeolites including natural products and synthetic products are commercially available, and the chemical composition is Si.
O ₂ , AlO ₃ , H ₂ O, Na ₂ O, K ₂ O, and CaO, the proportion of which depends on the production area for natural products and various synthetic methods for synthetic products. It is a crystalline aluminosilicate and generally has a three-dimensionally developed skeletal structure.

Generally, xM _{2 / n based} on Al ₂ O _{3
O · Al 2 O 3 · ySiO} 2 · zH 2 O (M is a monovalent can usually be ion exchange or divalent metal ion, n represents the valence of M, x, y and z represent the mole ratios of each component ). In the present invention, either a natural product or a synthetic product can be used, but a synthetic zeolite is particularly preferable because the content of impurities that adversely affects the photographic properties of the photographic light-sensitive material is small.

The inorganic antibacterial zeolite in which zeolite, which is particularly preferable in the present invention, carries a metal ion having antibacterial properties will be described in detail. The antibacterial agent in which one or more of the above metal ions are supported on zeolite has antibacterial properties such as antibacterial properties and antifungal properties. Therefore, it is composed of gelatin, a hydrophilic polymer, a surfactant and the like. It is most suitable for antibacterial and antifungal treatment of a light-sensitive layer and a backing layer provided for curl balance and the like. Inorganic antibacterial zeolite has excellent antibacterial properties even in powder form by incorporating metal ions into the zeolite skeleton structure, as well as long-lasting antibacterial properties, as well as excellent safety and heat resistance, as described above It has an unexpected effect of improving photographic properties and anti-blocking properties.

The inorganic antibacterial zeolite can be produced by a known method. For example, silver nitrate, silver sulfate, silver perchlorate, silver acetate, zinc sulfate, zinc perchlorate, a method of supporting by an ion exchange reaction using an aqueous solution of a zinc salt such as zinc acetate, the metal is supported by physical adsorption It can be manufactured by a method or the like. The amount of the inorganic antibacterial zeolite is 0.0001 to 15 parts by weight, preferably 0.0005 to 10 parts by weight, more preferably 0.001 to 10 parts by weight as anhydrous zeolite based on 100 parts by weight of the resin composition for forming the resin layer. 7 parts by weight, particularly preferably 0.001 to
5 parts by weight. The most preferred inorganic antibacterial zeolite is a silver-based antibacterial zeolite in which silver ions are supported on a synthetic zeolite, and commercially available products include, for example, zeomic (trademark of Shinagawa Fuel KK), and most preferable in consideration of photographic properties and cost. The amount is 0.001 to 5 parts by weight. In particular, a silver-based inorganic antibacterial agent is preferable because it has a large antibacterial effect and does not adversely affect the photographic properties of the photographic light-sensitive material.

In particular, silver zeolite in which silver ions are supported on zeolite, which is a silicate-based carrier, as described above, is preferred. Particularly preferred commercially available silver zeolite-based antibacterial agents include "Zeomic" (trade name of Shinagawa Fuel KK).
In addition, "Toyagosei KK Novalon" (trade name) in which silver ions are supported on an inorganic ion exchanger ceramic is also preferable.

As a natural antibacterial agent, there is chitosan which is a basic polysaccharide obtained by hydrolyzing chitin contained in crab and shrimp shell. Although its safety is excellent, its heat resistance is inferior, so its use is limited.

For application to the packaging material for photographic light-sensitive materials of the present invention, "Holon Killer Bees Sera" manufactured by KK Nippon Mining Co., Ltd. comprising amino metal in which a metal is compounded on both sides of an amino acid is preferable.

However, most of the antibacterial agents have some adverse effect on the photographic properties of the photographic light-sensitive material. It is preferred to include a small amount.

Various additives can be added to the photographic light-sensitive material packaging material of the present invention. For details of this additive, refer to the revised and supplemented “Latest Pigment Handbook” (January 10, 1977, published by Seibundo Shinkosha Co., Ltd.) and the 1994 edition of “New Chemical Index” (July 23, 1993, Published by Kogyo Nipposha) and "Chemical products of 12394" (1994
January 26, 1984, published by The Chemical Daily), “Plastic Data Handbook” (April 5, 1984, published by the Industrial Research Institute, Inc.)
Detoxification by combining types and amounts of additives (additives) described in various documents such as (Plastic Age Co., Ltd.) and other additives so as not to adversely affect photographic light-sensitive materials Most of the compounding agents can be used for packaging materials for photographic light-sensitive materials by utilizing a reaction or the like, or examining the layer structure and resin composition. Representative examples are described below, but the present invention is not limited to these.

A. Class 1 (Classification by performance for needs) Processing aids a. Processing stabilizer (antioxidant, heat stabilizer) (PVC stabilizer) b. Flow control agents (plasticizers, lubricants) c. 1. Shape retention aid (release agent, anti-shrinkage agent) Modified compounding agent 2-1 Stabilizer (life control agent) a. Antioxidants b. Lightfast stabilizer c. Flame retardant d. Biostabilizers e. Metal deactivators f. (Degradation repairing agent) 2-2 Performance modifier (physical property controlling agent) a. Impact resistance modifier (various elastomers, L-LDPE resin) b. Filler, reinforcement c. Colorant d. Plasticizer e. Foaming agent f. Crosslinking agent (organic peroxide) g. Nucleating agent 2-3 Function modifier (function imparting agent) a. Conductive agent, magnetic agent b. Antistatic agent c. Fluorescent whitening agent 2-4 Decomposition accelerator a. Biodegradation b. Photolysis c. Thermal decomposition, etc.

B. Class 2 (Classification by attribute of compounding agent) Powder modifier a. Reinforcement / filler b. Nucleating agent c. Processing aids d. 1. Powder / powder special structure Reactivity modifier a. Crosslinking agent b. Macromonomer c. Stabilizers (heat, light, radiation, organisms) d. 2. Decomposition accelerator (biology, light, heat) Interfacial modifier a. Coupling agent b. Compatibilizer c. 3. plasticizer / solvent Polymer Modifier a. Processability improver, performance modifier b. Alloys, blends (performance modification), etc.

ASTM D 16 in the outermost layer of the multilayer coextruded film constituting the packaging material for photographic light-sensitive materials
The sulfur content by the measurement method of 19-60 is set to 0.6% or less, preferably 0.4% or less, more preferably 0.2% or less, and most preferably 0.1% or less. If the amount of the sulfur component is not reduced, the photographic properties of the photographic light-sensitive material such as an increase in fog, an abnormal sensitivity, and an abnormal color development are adversely affected. In particular, free sulfur components that directly affect the photographic properties of photographic light-sensitive materials directly (each sample is cooled and solidified with liquid nitrogen and then crushed,
100 g of the pulverized sample is put into a Soxhlet extractor, extracted with chloroform at 60 ° C. for 8 hours, cooled, and
ml. 10 ml of this solution is injected into a high performance liquid chromatograph, and sulfur is quantified. High-performance liquid chromatography separation conditions are as follows: column; ODS silica column (4.6φ × 1
50 mm), separation solution; methanol 95 and water 5 (containing 0.1% each of acetic acid and triethylamine), flow rate: 1 m
1 / min, detection wavelength; 254 nm, quantification is performed by the absolute calibration method. ) Is 0.1% or less, preferably 0.05%
Or less, particularly preferably 0.005% or less, most preferably 0.002% or less.

Further, in particular, the content of a cyanide compound that deteriorates photographic properties (the amount of hydrogen cyanide determined by 4-pyridinecarboxylic acid / pyrazolone absorption spectrometry) is determined for the resin layer on the photographic light-sensitive material side constituting the photographic light-sensitive material packaging material. Is 10 ppm or less, preferably 5 ppm or less, particularly preferably 2.5 ppm or less,
Most preferably, it is 1 ppm 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 Laid-Open No. 8-254793)
No.). (2) Transparent, colored or printed photographic film in a plastic container (JIS 135 film, APS
And moisture-proof and sealed packaging bags (for example, 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, printing plate-making films, cut films for photography, X-ray films, PS plates, etc.
254793, FIGS. 2-3, JP-A-5-5972, etc.). (4) A light-shielding film for a belt-shaped photographic photosensitive material package (JP-A-2-72347, JP-B-7-50743, JP-B-6-8593, JP-A-6-21435)
No. 0, Japanese Utility Model Publication No. 8-10812). (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 heat-developed diffusion transfer papers (JP-A-6-6735).
No. 8, etc.). (6) A moisture-proof / light-shielding film or a leader film for a light-room packed package of a photographic material such as a photographic paper or a 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, JP-A-7-9-9
No. 2618, JP-A-8-40468, Japanese Utility Model Publication No. 56-16608, Japanese Utility Model Publication No. 6-8593,
Japanese Utility Model Publication No. 8-9725, etc.). (7) Moisture-proof / light-shielding film for bulk roll-shaped photographic photosensitive material packaging.

The above-mentioned various sealing bags include a bottom sealing bag of a tubular film, a two-side sealing bag, a three-side sealing bag, a four-side sealing bag, a gusset bag and the like.

Also, it can be used for various overwrap packaging. For example, there are carton or tray overwrapping, caramel overwrapping, snack overwrapping, cigarette overwrapping, roll overwrapping, bar overwrapping, twist overwrapping, and the like. Further, it can be used as various packaging bodies described in the Japan Packaging Technology Association, published on July 1, 1995, Handbook of Packaging Technology, pages 754 to 774.

Typical examples of the photographic light-sensitive material to which the packaging material for a photographic light-sensitive material of the present invention can be applied are shown below.

(1) Silver halide photographic light-sensitive material: printing film, black and white and color photographic paper, radiographic film,
Master paper for printing color film (negative and reversal), DTR photosensitive material, computerized typesetting film and paper,
Microfilm, surveillance film, movie film, self-developing photographic light-sensitive material, full-color thermal paper, direct positive film and paper, etc.

(2) Heat-developable photographic light-sensitive material: heat-developable color light-sensitive material, heat-developable black-and-white light-sensitive material (for example, JP-B-43-43)
No. 4921, Japanese Patent Publication No. 43-4924, “Basics of Photographic Engineering”, pp. 553 to 555 of Silver halide photography (published by Corona Co., Ltd., 1979), and Research Disclosure Magazine, June 1978, ninth. Page to page 15 (RD-170
29) and the like. Further, Japanese Unexamined Patent Publication No.
No. 12431, No. 60-2950, No. 61-
Transfer-type heat-developable color light-sensitive materials described in US Pat. No. 52,343 and US Pat. No. 4,584,267.

(3) Photosensitive / thermosensitive recording material: JP-A-59
-190886, JP-A-61-40192, JP-A-61-40193, JP-A-3-723
No. 58, JP-A-3-288688 and JP-A-4
And recording materials (including full-color thermal paper) using photothermography (photosensitive / thermosensitive image forming method) described in JP-A-28585.

(4) Diazonium photographic light-sensitive material: 4-morpholinobenzenediazonium microfilm, microfilm, transfer film, printing plate material and the like.

(5) Azide and diazide photographic light-sensitive materials:
Photosensitive materials containing para-azide benzoate, 4,4'-diazidostilbene and the like, for example, a copy film m, a printing plate material and the like.

(6) Quinonediazide-based photographic materials: Orthoquinonediazide, orthonaphthoquinonediazide-based compounds such as benzoquinone (1,2) '-diazide- (2) -4-sulfonic acid phenyl ether, such as , Printing plates, copying films, adhesion films, etc.

(7) Photopolymer: a photosensitive material containing a vinyl monomer, a printing plate, a contact film, and the like.

(8) Polyvinylcinnamate-based photographic light-sensitive materials: printing films, resists for ICs, etc.

Preferred embodiments of the packaging material for a light-sensitive material of the present invention are described below. A: Aspect in which blocking adhesive lamination property is preferred The innermost layer has a crystallinity of 60% or less, preferably 56%.
%, More preferably 51% or less, most preferably 4% or less.
6. The photographic light-sensitive material according to claim 1, comprising an ethylene copolymer resin composition containing as a main component an ethylene copolymer resin produced and produced without using a 6% or less single-site catalyst (for example, using a multi-site catalyst). Packaging material. In the outermost layer, one or more kinds of antiblocking agents
The packaging material for photographic light-sensitive material as described above, which contains 30% by weight. The antiblocking agent content in the outermost layer ≧ the antiblocking agent content in the innermost layer, wherein the packaging material for a photographic light-sensitive material according to the above or in the above, the lubricant content in the outermost layer ≧ the content of the lubricant in the innermost layer amount,
Or the packaging material for a photographic photosensitive material according to the above or the above. It also has the effect of improving the suitability of the photographic material for packaging and preventing scratches and static marks. The packaging material for a photographic light-sensitive material according to the above or the above, wherein the relationship of light-shielding substance content in the outermost layer ≧ light-shielding substance content in the innermost layer is satisfied. Note that there is also an effect of preventing light intrusion by light piping. The packaging material for a photographic light-sensitive material as described in the above, wherein the content of zeolite in the outermost layer ≧ the content of zeolite in the innermost layer. The zeolite-based antibacterial agent content in the outermost layer ≧ the zeolite-based antibacterial agent content in the innermost layer, the above,
Or a packaging material for a photographic light-sensitive material according to any one of the above. In addition, there is an effect of preventing deterioration of gelatin, polyvinyl alcohol, and the like used in the photographic photosensitive layer. In the relationship of α-tocopherol content in the outermost layer ≧ α-tocophenol content in the innermost layer,
Or a packaging material for a photographic light-sensitive material according to any one of the above.

B: Mode for Enhancing the Photographic Properties of the Packaging Material The packaging material for photographic photosensitive materials according to A, wherein the content of the antioxidant in the outermost layer ≧ the content of the antioxidant in the innermost layer. The packaging material for photographic light-sensitive material according to A, wherein the relation of the content of the recycled resin in the outermost layer ≧ the content of the recycled resin in the innermost layer is satisfied. The packaging material for a photographic light-sensitive material according to A, wherein the relationship of the content of the compatibilizer in the outermost layer ≧ the content of the compatibilizer in the innermost layer is satisfied.

C: An aspect in which production suitability, physical strength, tensile strength, abrasion resistance, etc. are improved. In the claims, the laminated film is provided with an adhesive layer and has a tensile elastic modulus in the vertical and horizontal directions (ASTM D8).
82) Packaging materials for photographic photosensitive materials in which flexible sheets of 100 kgf / mm ² or more are laminated. A wrapping material for a photographic light-sensitive material, wherein the flexible sheet used in C has a light-shielding property. A packaging material for photographic light-sensitive materials, wherein the flexible sheet used in C or C is a multilayer co-extruded film. A packaging material for a photographic light-sensitive material, wherein the flexible sheet used in the above C, C or C is a biaxially stretched polyethylene-2,6-naphthalate resin film.

D: Others A package of a photographic light-sensitive material, characterized in that the heat-sealable layer (layer on the photographic light-sensitive material side) of the packaging bag according to the above-mentioned claim contains an inorganic antibacterial zeolite. Molecular weight distribution, composition distribution, of ethylene-α-olefin copolymer resin produced by polymerization using single-site catalyst,
The packaging material for a photographic light-sensitive material according to claim 1, wherein the low-molecular weight resin is smaller than the ethylene / α-olefin copolymer resin produced by polymerization using a multi-site catalyst. The packaging material for a photographic light-sensitive material according to claim 1, wherein the outermost layer of the multilayer co-extruded blown film contains an antibacterial agent. 2 of a laminated film obtained by bonding and laminating the innermost layers of a multilayer co-extruded blown film by blocking
The packaging material for a photographic light-sensitive material according to claim 1, wherein the light-shielding substance is contained in one or more resin layers. The packaging material for a photographic photosensitive material according to claim 1, wherein the moisture permeability of the packaging material measured according to JIS K 7129 is 5 g / m ² · 24 hours (40 ° C, 90% RH) or less.

The photographic light-sensitive material package of the present invention is manufactured using the photographic light-sensitive material packaging material as described above, and is provided outside the packaging bag in which the photographic light-sensitive material is hermetically sealed (the side opposite to the photographic light-sensitive material side). ) Has a sliding friction coefficient (ASTM D-
Load area 42 cm ² , load 20
(Measured at 0 g) is 0.48 or more (sliding start angle 40 degrees) or more and contains a lubricant, and the coefficient of sliding friction is preferably 0.50 or more, more preferably 0.52 or more.

When the coefficient of sliding friction is less than 0.48, the packages tend to slip off when many packages are stacked.

To adjust the coefficient of sliding friction to a predetermined range, a fatty acid metal salt-based lubricant or the like is added, a tackifier is added, a resin having a low Vicat softening point is added,
In addition to the method of adding a filler, a method of printing or applying a resin solution containing a foaming agent or a non-slip agent on the outside of the packaging bag is used. Further, a method of applying a pressure-sensitive adhesive or a hot-melt adhesive may be used (application and printing may be performed on the entire surface or in a dot shape).

More specifically, the particle size is 1 to 100.
mμ colloidal silica dispersed in a water-soluble polymer compound (polyvinylpyrrolidone, sodium polyacrylate, copolymer of sodium polyacrylate and acrylate, cellulose derivative, gelatin, casein, polyvinyl alcohol, etc.) Or an emulsion polymer resin layer of an unsaturated carboxylic acid or an ester thereof and colloidal silica is formed on the surface. This lubricant is
As described above.

It is preferable that the innermost layers at the upper end of the opening of the packaging bag used for the package are welded to each other at two or more places by a heat sealing method. By fusing at two or more places by heat sealing, it is possible to prevent blocking adhesion from coming off while maximizing light-shielding properties and physical strength.

The layer structure of the packaging material for a photographic light-sensitive material of the present invention will be described with reference to the drawings. 1 to 6 are partial cross-sectional views of a packaging material for a photosensitive material. The packaging material for a photosensitive material shown in FIG. 1 comprises an innermost layer 1a containing a light-shielding substance and an outermost layer 2a containing a light-shielding substance.
The two-layer co-extruded blown film IIa has the innermost layers 1a adhered to each other by blocking B.

The packaging material for photographic light-sensitive material shown in FIG. 2 has a two-layer co-extruded blown film IIa comprising an innermost layer 1 not containing a light-shielding substance and an outermost layer 2a containing a light-shielding substance. The innermost layers 1 are bonded by blocking.

The packaging material for photographic light-sensitive material shown in FIG. 3 has a two-layer co-extruded blown film IIa comprising an innermost layer 1a containing a light-shielding substance and an outermost layer 2 not containing a light-shielding substance. The innermost layers 1a are bonded to each other by blocking B.

The packaging material for a photographic light-sensitive material shown in FIG. 4 has an innermost layer 1a containing a light-shielding substance, an outermost layer 2a containing a light-shielding substance, and an intermediate layer containing a light-shielding substance provided therebetween. The three-layer co-extruded inflation film IIIa consisting of 3a and 3a has the innermost layers 1a bonded together by blocking B.

The packaging material for a photographic light-sensitive material shown in FIG. 5 comprises an innermost layer 1 containing no light-shielding substance, an outermost layer 2a containing the light-shielding substance, and an intermediate layer provided between these layers containing the light-shielding substance. The three-layer co-extruded blown film IIIa composed of 3a and 3a has the innermost layers 1 bonded together by blocking B.

The packaging material for photographic light-sensitive material shown in FIG. 6 is obtained by laminating a flexible sheet layer 5a containing a light-shielding substance via an adhesive layer 4 on one outermost layer 2a in the layer structure shown in FIG. It is.

[0233]

EXAMPLES Example I The layer configuration corresponds to FIG. The contents of the resin used for each layer are as follows.

<Contents of Ethylene / α-olefin Copolymer Resin A Polymerized and Produced Using Single-Site Catalyst> A1: MFR: 4 g / 10 min, density: 0.920 g / c
m ³ , an ethylene / hexene-1 random copolymer resin having a Vicat softening point of 99 ° C., a melting point of 115 ° C., a Shore hardness of 56D, and a molecular weight distribution (Mw / Mn) of 2.2 (polymerized by a gas phase method). A2: MFR 3 g / 10 min, density 0.909 g / c
m ³ , an ethylene-hexene-1 random copolymer resin having a Vicat softening point of 97 ° C., a melting point of 112 ° C., a Shore hardness of 53 D and a molecular weight distribution (Mw / Mn) of 1.8 (polymerized by a gas phase method). A3: MFR 2.5 g / 10 min, density 0.930 g
/ Cm ³ , Vicat softening point 104 ° C, melting point 120
C., a Shore hardness of 59D, and a molecular weight distribution (Mw / Mn) of 2.0, an ethylene-hexene-1 random copolymer resin (polymerized by a solution method).

<Contents of Polyolefin Resin B Polymerized and Produced Without Using a Single-Site Catalyst> B1: MFR: 2 g / 10 min, Density: 0.920 g / c
m ³ , Vicat softening point 112 ° C., melting point 123 ° C., Shore hardness 55D, molecular weight distribution (Mw / Mn) 3.5
Ethylene-octene-1 random copolymer resin polymerized and produced by the solution method of (1). B2: MFR is 2 g / 10 min, density is 0.900 g / c
An ethylene / butene-1 random copolymer resin produced by a gas phase method having m ³ , a Vicat softening point of 80 ° C., a melting point of 113 ° C., a Shore hardness of 46D, and a molecular weight distribution (Mw / Mn) of 2.8. B3: MFR 2.5 g / 10 min, density 0.920 g
/ Cm ³ , Vicat softening point is 93 ° C, melting point is 112 ° C,
4. Shore hardness is 50D and molecular weight distribution (Mw / Mn) is 5.
8. A homopolyethylene resin polymerized and produced by the high-pressure ionic polymerization method of 8. B4: MFR 0.8 g / 10 min, density 0.955 g
/ Cm ³ , Vicat softening point 126 ° C., melting point 137
C., a low pressure polymerization-produced homopolyethylene resin using a titanium-based Ziegler catalyst having a Shore hardness of 67D and a molecular weight distribution (Mw / Mn) of 4.6. B5: An ethylene / vinyl acetate copolymer resin having a VA content of 15% by weight.

<Contents of Homopolyethylene Resin C Polymerized and Produced Using Single Site Catalyst> C1: MFR 1.6 g / 10 min, density 0.956 g
/ Cm ³ , Vicat softening point 127 ° C., melting point 139
A low-pressure polymerization-produced homopolyethylene resin using a zirconium-based metallocene catalyst having a temperature of 66 ° C, a Shore hardness of 66D and a molecular weight distribution (Mw / Mn) of 2.6.

Tables 4 and 5 show the results.

[0238]

[Table 4]

[0239]

[Table 5]

The evaluation is as follows. ◎… Excellent ○ …… Excellent ● …… Practical limit ▲… Problem (improvement required) × …… Not practical

<Blocking Failure of Packaging Material> Packaging materials obtained by blocking and laminating the innermost layers with each other were stacked between 10 stainless steel plates (weight 1 kg), and were heated at 20 ° C. and 60% R
H was left for one week, and evaluated by the blocking state between the outermost layers when peeling off each sheet.

<Blocking Adhesive Laminating Properties of Inner Layers> Comprehensive evaluation was made of the blocking adhesive stability of inner layers (with respect to temperature and seasonal variations), peeling prevention during bag making, and peeling prevention during lamination.

<Photographic Properties> A color photographic paper is hermetically sealed in a moisture-proof and light-shielding bag prepared by using each laminated film by a heat sealing method, and then left for 3 days in a constant temperature / humidity room at a temperature of 40 ° C. and a relative humidity of 80%. After that, evaluation was made based on the degree of photographic change such as fogging, sensitivity, gradation, and color development with the type (blank) during normal development processing.

<Inflation film moldability> [0244] Blocking of resin pellets when forming each film, current load of extruder during film formation, stability of bubbles, prevention of generation of streaks, white powder and wrinkles, winding Comprehensive evaluation of suitability (meandering prevention, antistatic, etc.).

<Heat seal suitability> Overall evaluation of sealing heat sealability, heat seal strength, heat seal stability, hot tack property, temporal heat seal strength, and the like.

<Antistatic Property> An endless belt having a width of 35 mm and a length of 1350 mm was made from the laminated film to be tested, and this endless belt was SUS with a load of 500 g.
A strip voltage was measured by a voltmeter when the paper was sent between a (stainless steel) roll and a SUS roll at a speed of 12 m / min (a measuring device manufactured by Shinto Kagaku KK).

<Physical strength> The tear strength, impact hole punching strength, bag breaking strength, etc. were comprehensively evaluated.

<Light-shielding property> Vibration test method for packaged cargo (JIS
Peak acceleration of method B of Z 0232 ± 4.90 m /
(S ² , shaking time 15 minutes) The light-shielding property of the packaging bag was evaluated from the degree of light leakage.

In Example I, calcium stearate, a fatty acid metal salt, which is a dispersion-improving substance of furnace carbon black, which is a light-shielding substance, and a film-forming property improving substance, has a number average molecular weight of 10,000.
Since it was a resin composition containing a low-molecular-weight polyethylene resin that is a low-molecular-weight polyolefin resin of 0 or less, excellent film moldability, less occurrence of bumps and microgrit,
There were no wrinkles or streaks.

Example II The layer configuration corresponds to FIG.

<Innermost layer containing light-shielding substance 1a> MFR is 2 g / 10 min, density is 0.900 g / cm ³ , Vicat softening point is 80 ° C., melting point is 113 ° C., Shore hardness is 46D,
Ethylene butene having a molecular weight distribution (Mw / Mn) of 2.8 and produced by polymerization in the gas phase method without using a single-site catalyst.
(1) 71.85% by weight of the random copolymer resin (B2), MFR of 2.5 g / 10 min, density of 0.920 g / c
m ³ , a homopolyethylene resin having a Vicat softening point of 93 ° C., a melting point of 112 ° C., a Shore hardness of 50 D and a molecular weight distribution of 5.8, produced by high-pressure ion polymerization (B3 above)
Is 20% by weight, calcium stearate 0.1% by weight,
The light-shielding polyolefin resin layer is composed of 0.05% by weight of a hindered phenolic antioxidant, 3% by weight of furnace carbon black, and 5% by weight of a low-molecular-weight polyethylene resin having a number average molecular weight of 3,000 and a thickness of 20 μm.

<Outermost layer 2a containing light-shielding substance> MFR is 2.5 g / 10 min, density is 0.930 g / cm ³ , Vicat softening point is 104 ° C., melting point is 120 ° C., Shore hardness is 59D, molecular weight distribution An ethylene / hexene-1 random copolymer resin (A3 above) produced by a solution method using a single-site catalyst having a (Mw / Mn) of 2.0 was 86.
80% by weight, MFR 2.5 g / 10 min, density 0.9
20 g / cm ³ , Vicat softening point 93 ° C., melting point 11
5% by weight of a homopolyethylene resin (B3) polymerized and produced by a high-pressure ionic polymerization method without using a single-site catalyst having a temperature of 2 ° C., a Shore hardness of 50D, and a molecular weight distribution of 5.8, 0.1% by weight of calcium stearate, Erucamide 0.0
5% by weight, 0.05 hindered phenolic antioxidant
It is a light-shielding polyolefin resin layer having a thickness of 20 μm, comprising 5% by weight, 3% by weight of furnace carbon black, and 5% by weight of a low molecular weight polyethylene resin having a number average molecular weight of 3,000.

The light-shielding two-layer co-extruded blown film IIa having a total thickness of 40 μm and having the two-layer structure of the innermost layer 1a and the outermost layer 2a is connected to each other by a pinch roll formed of a metal roll and a rubber roll. (Nip linear pressure 60 kg / cm = approximately the same as the pressing pressure kg / cm ² ) and blocking (adhesive strength 5 g / 15)
mm width) to form a four-layer light-shielding laminated film having a total thickness of 80 μm.

Next, on the outer side of the light-shielding laminated film (on the side opposite to the photographic light-sensitive material), a 40 μm-thick (30 μm-thick light-shielding intermediate layer containing 5% by weight of furnace carbon black) was coated on both sides with a 5 μm-thick transparent inner layer. A biaxially stretched polypropylene resin film composed of an outer layer) and a 15 μm thick MFR
Is a polyolefin resin extrusion laminate adhesive layer having a resin temperature of 320 ° C. containing, as a main component, a homopolypropylene resin having 5.1 g / 10 min, a density of 0.919 g / cm ³ , and a molecular weight distribution (Mw / Mn) of 6.3. To form a packaging material for a photographic light-sensitive material.

In Example II, a light-shielding biaxially stretched three-layer co-extruded polypropylene resin film was laminated as the flexible sheet 5a, so that the Young's modulus, heat resistance, and impact piercing strength were large, and light-shielding, moisture-proof and hermetic sealing were achieved. The properties and suitability for bag making were very excellent. In addition, physical strength is improved,
It has good suitability for bag making, roll-shaped color photographic paper with a sharp edge of 10 kg or more (8.9 cm wide x 180 m long), photographic film (35 mm wide x 3000 feet long) or sheet film (A2 size x 50 sheets) Even if it is packed and sealed and transported for 100 km or more, pinholes will not occur in the sealed packaging bag, and the thinning phenomenon due to elongation observed when using a laminated film with blocking adhesion and lamination will not occur due to product weight. The light-shielding property could be secured in a state of 100% good.

The outer surface has a large tensile modulus of elasticity.
(Vertical direction 215 kgf / mm ² , horizontal direction 425 kgf
/ Mm ² ) Since the biaxially stretched three-layer co-extruded polypropylene resin film is laminated via the polyethylene resin adhesive layer, the surface strength is large and the abrasion resistance and tape aptitude are very excellent. Breakage and pinholes due to collision with the product have been eliminated. 3 g / m ² moisture permeability
・ 24 hours (40 ° C, 90% RH) or less (JIS K7
129), and since the main component of the packaging material is composed of a polyolefin resin that does not adversely affect the photographic light-sensitive material, the quality of the photographic light-sensitive material can be favorably maintained for two years or more without laminating an aluminum foil or an aluminum vapor-deposited film. It became so. In addition, since it is entirely composed of polyolefin resin, it was a packaging material that could clear the Containers and Packaging Recycling Law, such as suitability for recycling and incineration.

Example III Using the photographic photosensitive material packaging materials of Examples I and II, a single gazette bag consisting of only inner paper (Japanese Patent Publication No. 4-80373, page 14, page 10)
(Corresponding to the figure), and the innermost layer at the upper end of the opening is formed into a square shape (area 5 mm in width and 5 mm in length) at the opening of the single gusset bag serving as the entrance for inserting the photosensitive material. At 25 mm ² ), two portions were welded by heat sealing at an interval of 5 cm (heat sealing strength of 300 g or more).

A photographic photosensitive material is inserted into the single gusset bag, the opening is bent twice at a width of 2 cm, and then bonded with an adhesive tape having a width of 3 cm. did.

In Example III, the adhesive and laminated peeling strength by blocking is 300 g / 15 mm width or less, and most of the peeling strength is 50 g / 15 mm width or less. , The physical strength is very good. When the photosensitive material is taken in and out of the opening of the moisture-proof and light-shielding bag while securing this property, the heat-sealing is performed at two places so that the blocking adhesive portion having a small peel strength is not removed, so that the blocking adhesive portion does not come off. The workability in the dark room was excellent, and even if it was a single gusset bag, it had strength higher than the physical strength of the conventional double gusset bag.

[0260]

The present invention is configured as described above.
It has the effects described below. i) Excellent flexibility and anti-curl properties. ii) Excellent physical strength. iii) Excellent heat sealability. iv) The photographic properties of the photographic light-sensitive material can be favorably maintained during the effective period (a long one is approximately two years). v) Various characteristics required as a packaging material for photographic light-sensitive materials can be produced only by a blown film forming step. vi) A packaging material for a photographic light-sensitive material satisfying the above iv can be manufactured with a configuration containing a polyolefin resin as a main component and having suitability for recycling and incineration. vii) A package of a photographic light-sensitive material which satisfies the above conditions i to vi, has excellent handleability of the photographic light-sensitive material, and has excellent suitability for hermetic packaging can be provided at low cost. viii) A packaging material in which a heat-resistant, high Young's modulus, easy-to-print flexible sheet is laminated via an adhesive layer has a small curl, excellent flexibility and physical strength, and is most excellent in bag-making suitability.

[Brief description of the drawings]

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

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

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

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

FIG. 5 is a partial cross-sectional view showing a layer structure of a packaging material for a photographic light-sensitive material of the present invention.

FIG. 6 is a partial cross-sectional view showing a layer structure of a packaging material for a photographic light-sensitive material of the present invention.

FIG. 7 is a diagram showing the transmittance of a PET resin film and a PEN resin film.

FIG. 8 is a diagram showing a general relationship between density and properties of polyethylene.

[Explanation of symbols]

 1, 1a Innermost layer 2, 2a Outermost layer 3, 3a Intermediate layer 4, 4a Adhesive layer 5, 5a Flexible sheet II, IIa Two-layer co-extrusion blown film III, IIIa Three-layer co-extrusion blown film B Adhesive part by blocking Shows a that contains a light-shielding substance

 ──────────────────────────────────────────────────続 き Continuing on the front page F term (reference) 4F100 AA37 AK01E AK03A AK03B AK03C AK03D AK04B AK04C AK04J AK07 AK07G AK62A AK62D AK62J AK63 AK65 AK68 AL02B AL02C BA04 BA05 EC02 BA02 EC07 GB17 GB27 JA11B JA11C JB16E JD09E JK01 JK02E JK07E JK17 JL04 JL12 JL16 YY00B YY00C YY00E

Claims (8)

[Claims] 1. A packaging material for a photographic light-sensitive material comprising a laminated film in which the innermost layers of a multilayer co-extruded inflation film having an outermost layer and an innermost layer are adhered and laminated by blocking each other, wherein the outermost layer uses a single-site catalyst. Mainly composed of polyolefin resin produced by polymerization,
A packaging material for photographic light-sensitive materials, characterized in that the innermost layer is mainly composed of a polyolefin resin produced by polymerization without using a single-site catalyst. 2. The packaging material for a photographic light-sensitive material according to claim 1, wherein the outermost layer of the multilayer co-extruded blown film mainly comprises an ethylene / α-olefin copolymer resin produced by polymerization using a metallocene catalyst. 3. The packaging material for a photosensitive material according to claim 1, wherein the innermost layer of the multilayer co-extruded blown film mainly comprises an ethylene copolymer resin produced by polymerization using a multi-site catalyst. 4. The packaging material for a photographic light-sensitive material according to claim 3, wherein said ethylene copolymer resin has a crystallinity of 60% or less by an X-ray method. 5. A tensile modulus in the vertical direction of blocking ultraviolet rays through an adhesive layer on a laminated film obtained by bonding and laminating innermost layers of the multilayer co-extruded inflation film by blocking (measured according to ASTM D882). 6. A packaging material for a photographic light-sensitive material according to claim 1, further comprising a laminated thermoplastic resin film of 100 kgf / mm ² or more. 6. A packaging material for a photographic light-sensitive material comprising a laminated film in which the innermost layers of a multi-layer co-extruded inflation film having an outermost layer and an innermost layer are bonded and laminated by blocking each other, wherein the outermost layer uses a single-site catalyst. The molecular weight distribution produced by polymerization is mainly composed of an ethylene / α-olefin copolymer resin having a molecular weight distribution of 1.0 to 5, and the innermost layer has a molecular weight distribution produced by polymerization using a multi-site catalyst of 2 or more, and has a crystallinity by an X-ray method. Is less than 60% ethylene α
A wrapping material for a photographic light-sensitive material, comprising an olefin copolymer resin as a main component and 0.01 to 5% by weight of a fatty acid metal salt. 7. A packaging bag manufactured by using the packaging material for a photographic photosensitive material according to claim 1, wherein the photographic photosensitive material is hermetically stored in the packaging bag. Has a coefficient of sliding friction (measured with a load area of 42 cm ² and a load of 200 g according to ASTM D-1894) of 0.4.
A photographic light-sensitive material package, which is not less than 8 (slip start angle: 40 degrees) and contains a lubricant. 8. A photographic light-sensitive material package characterized in that at least two innermost layers at the upper end portion of an opening portion of a packaging bag are welded to each other by a heat sealing method.