JP2000056432A - Packaging material for photographic sensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide the packaging material for the photographic sensitive material superior in photographic properties, anti-electrification, physical strength, film forming aptitude, incineration aptitude, dispersibility of carbon black, and heat sealability at a low manufacturing cost. SOLUTION: This packaging material is made of a 3-laminated simultaneously coextruded film (IIIa) comprising an inside conductive thermoplastic resin layer (1a) containing a light-shielding material, an intermediate thermoplastic resin layer (2a) containing a light-shielding material, and an outside conductive thermoplastic resin layer (3a). It is preferred that the specific volume resistivities of the inside layer (1a) and the outside layer (3a) are <=1×1012 Ω.cm at 20 deg.C in 60% RH.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a packaging material for photographic light-sensitive materials provided with a simultaneous multilayer coextruded film having excellent light-shielding properties, antistatic properties, physical strength, photographic properties and the like.

[0002]

2. Description of the Related Art Various types of packaging materials for photographic light-sensitive materials have been widely put into practical use, and various performances are required according to their uses.

A wrapping material for photographic light-sensitive materials, which loses its quality value when exposed to light, is a wrapping material that completely blocks light. In this case, the required property is a wrapping material slit. Suitability, gas barrier properties, moisture resistance, rigidity, physical strength (rupture strength, tear strength, impact hole opening strength, gelbo test strength, abrasion strength, etc.), heat seal suitability (heat seal strength, cut sealability, hot tackiness, congestion) Material sealing properties), antistatic properties, flatness, sliding properties, etc. In order to satisfy these various properties, various packaging materials have been conventionally proposed.

For example, Japanese Patent Publication No. 2-2700 discloses that
50% by weight or more of L-LDPE resin and 1% by weight of light-shielding substance
A packaging material provided with a light-shielding film including the above is disclosed, and Japanese Patent Publication No. 4-80372 discloses L-LDP.
E resin 50 to 95% by weight, HDPE resin 5 to 49.5% by weight, carbon black 0.1 to 10% by weight and lubricant 0.1.
A packaging material comprising from 0.1 to 10% by weight;
Japanese Patent Publication No. 4-80373 discloses a packaging material provided with a two-layer co-extruded film composed of an HDPE resin layer or a PP resin layer and an L-LDPE resin layer, and Japanese Patent No. 2676258 discloses A laminate is disclosed in which the content of a surfactant-based antistatic agent in a surface layer constituting a multilayer coextruded film is 0.03 to 0.6% by weight.

[0005]

The above-mentioned conventional packaging materials have sufficient physical strength, heat sealing suitability and light-shielding properties, but have a metal foil or a metal thin film-processed flexible sheet layer with respect to antistatic properties. Necessary characteristics are ensured by using a multi-layer laminated structure in which the layers are laminated via an adhesive layer or by using a multi-layer laminated structure including a plastic film or black paper containing a large amount of a conductive substance.

[0006] However, a packaging material in which a metal foil or a metal thin film-processed flexible sheet is laminated is expensive, and lacks suitability for recycling and incineration. In addition, packaging materials containing a large amount of a conductive substance are expensive, and have problems not only in curl, heat sealing suitability, physical strength, etc., but also in poor dispersibility of the conductive substance, poor film formability, and There are many problems such as generation of pinholes, and the laminate disclosed in Japanese Patent No. 2676258 needs to further improve the heat sealing property and the antistatic property.

The present invention has solved these problems, and has antistatic properties, physical strength, suitability for film formation, suitability for recycling,
An object of the present invention is to provide a packaging material for photographic light-sensitive materials which has excellent suitability for incineration, dispersibility of carbon black, suitability for heat sealing, and physical strength, and can be produced at low cost.

[0008]

According to the present invention, there is provided a packaging material for a photographic light-sensitive material, comprising an inner conductive thermoplastic resin layer, an outer conductive thermoplastic resin layer, an inner conductive thermoplastic resin layer, and an outer conductive thermoplastic resin layer. A simultaneous multi-layer coextruded film having an intermediate thermoplastic resin layer laminated between the thermoplastic resin layer and the intermediate thermoplastic resin layer.

In the packaging material for photographic light-sensitive material of the present invention, since each layer is formed of a conductive thermoplastic resin without using a metal foil or the like, it is suitable for recycling while ensuring sufficient antistatic properties and the like. And good incineration suitability.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION The packaging material for photographic light-sensitive material of the present invention comprises a simultaneous multilayer co-extruded film, wherein the simultaneous multilayer co-extruded film comprises an inner conductive thermoplastic resin layer and an outer conductive heat It has a thermoplastic resin layer and an intermediate thermoplastic resin layer laminated between the inner conductive thermoplastic resin layer and the outer conductive thermoplastic resin layer. Each of the inner conductive thermoplastic resin layer, the outer conductive thermoplastic resin layer, and the intermediate thermoplastic resin layer may be formed as one layer or two or more layers.

That is, examples of the layer configuration include, for example, a mode in which each layer is composed of three layers, a mode in which the inner conductive thermoplastic resin layer is composed of two layers, and the other layer is composed of four layers; 2 thermoplastic resin layers and 1 other
A four-layer embodiment, a two-layer intermediate thermoplastic resin layer, and a four-layer intermediate layer, and the inner conductive thermoplastic resin layer and the outer conductive thermoplastic resin layer each have two layers. There is a mode in which the intermediate thermoplastic resin layer is composed of five layers, which is one layer, the inner conductive thermoplastic resin layer and the intermediate thermoplastic resin layer are each two layers, and the outer conductive thermoplastic resin layer is one layer. There is an embodiment composed of five layers, and an embodiment composed of five layers in which the intermediate thermoplastic resin layer and the outer conductive thermoplastic resin layer are each two layers, and the inner conductive thermoplastic resin layer is one layer.

The inner conductive thermoplastic resin layer, the outer conductive thermoplastic resin layer, and the intermediate thermoplastic resin layer can be formed of various thermoplastic resins. In this invention, photographic properties and suitability for disposal are excellent, and various properties are excellent.

Examples of the polyolefin resin include homopolyethylene resin, random and block copolymer resin of ethylene and α-olefin, homopolypropylene resin or random and block copolymer resin of propylene and α-olefin, and acid-modified polyolefin resin. ,ethylene·
There are acrylic ester copolymer resins, ethylene-vinyl acetate copolymer resins, and the like.

As the homopolyethylene resin, a radical initiator such as oxygen or peroxide is used.
A low-density branched polyethylene resin having a long-chain branching density of 0.910 to 0.925 g / cm ³ , which is produced by a method of polymerizing ethylene under a temperature and pressure condition of 1000 to 3000 kg / cm ^2. , Using a medium or low pressure Ziegler catalyst (Ti-based) or Phillips catalyst (Cr-based)
Linear high-density polyethylene having a linear density of 0.941 to 0.965 g / cm ³ , produced by a method of polymerizing ethylene at 50 to 250 ° C. and a temperature and pressure of 50 to 200 kg / cm ^2. Resin, a high-pressure method, a medium-low-pressure method, and a low-density polyethylene produced by blending the low-density polyethylene resin and the high-density polyethylene resin to a density of 0.926 to 0.940 g / cm ^3. There is a resin. Furthermore, there are homopolyethylene resins of various densities in which the molecular weight distribution has been reduced using a metal metallocene polymerization catalyst, which has recently been studied for practical use.

As the copolymer resin of ethylene and α-olefin, there is L-LDPE resin. This LL
DPE (L inear L ow D ensity P oly
e thylene) resin is called third polyethylene resin, medium low-pressure, low-cost, high-strength resin that meets the needs of the times that energy saving, resource saving having both the advantages of high-pressure two polyethylene resins. This resin is a copolymer obtained by copolymerizing ethylene and an α-olefin having 3 to 15 carbon atoms, preferably 4 to 10 carbon atoms by a low-pressure method or a high-pressure improvement method, and has a linear linear structure having a short branch. It is a polyethylene resin. Butene-1, octene-1, hexene-1,4-methylpentene-1, heptene-1 and the like are preferably used in terms of physical strength and cost. Particularly, an ethylene / α-olefin random copolymer resin is preferable in the present invention, but an ethylene / α-olefin block copolymer resin or a mixed resin of these two types can also be used.

Typical L-LDPE resin polymerization processes include 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 ( Dupo Canada Inc.) MORETEC (Idemitsu Petrochemical)

Among these L-LDPE resins, a resin preferable for use in a film-like packaging material particularly required for tear strength and impact piercing strength has a melt flow rate (hereinafter referred to as MFR) of 0.1. 1 to 40 g / 10 min (measured under condition 4 of JIS K-7210; test temperature 19)
0 ° C, test load 2.16kgf), density 0.870 ~
0.940 g / cm ³ (JIS K-7112), and the number of carbon atoms of the α-olefin is 3 to 15, preferably 4 to
Ten, particularly preferably six to eight, are obtained by a liquid phase process and a gas phase process. In addition, L of Sumikasen-L (Sumitomo Chemical), Nipolon L (Tosoh), Ubepolyethylene (Ube Industries) and the like obtained by the improved high pressure method process which reduced the equipment cost by converting the conventional high pressure method manufacturing process.
-LDPE resins are also preferred.

As a particularly preferred representative example by a trade name, polyethylene has 6 carbon atoms as an α-olefin side chain.
MULTEC of Mitsui Petrochemical Co., Ltd., into which 4-methylpentene-1 was introduced, and MORETEC of Idemitsu Petrochemical Co., Ltd., into which octene-1 having 8 carbon atoms was introduced as an α-olefin side chain. There are Stamirex and Dow Chemical Co., Ltd. (the above are L-LDPE resins obtained by a liquid phase process with four companies).
Preferable typical examples obtained by the low-pressure gas phase process are listed below under trade names: TU of Nippon Unicar Co., Ltd. in which hexene-1 having 6 carbon atoms is introduced as an α-olefin side chain.
FLIN and UCC's TUFTHENE.

The recently released density ranges from 0.87 to 0.8.
Ultra low density linear low density polyethylene resin of 910 g / cm ³ , for example, NUC-FLX of UCC or Sumitomo Chemical
Exelen VL of Co., Ltd. is also preferable (the above two products use butene-1 having 4 carbon atoms in the α-olefin).

The ratio of ethylene to α-olefin is preferably 70% or more, more preferably 80% or more. When the ethylene content is less than 70%, the polymerization suitability is deteriorated and the cost is high, and the obtained ethylene / α-olefin copolymer resin has a large tackiness and the film formability is deteriorated, and the blocking of the films is large and practical. Is difficult.

As the homopolypropylene resin, a Ziegler catalyst (Ti-based) is mainly used at 50 to 80 ° C. and 5 to 80 ° C.
A resin produced by polymerizing propylene at a temperature and pressure of 35 kg / cm ² and having a density of 0.890 to 0.910 g / cm ³ . Generally, it is an isotactic resin obtained by polymerizing propylene in the presence of a solvent using an aluminum alkyl / titanium tetrachloride Ziegler-Natta catalyst.

Examples of the copolymer resin of propylene and α-olefin include propylene / ethylene random copolymer resin, propylene / ethylene block copolymer resin, propylene / butene-1 random copolymer resin, and propylene / butene- 1-block copolymer resin, propylene / ethylene / butene-1 terpolymer resin, propylene / ethylene / diene terpolymer resin, propylene / hexene-1 random copolymer resin, propylene / hexene-
There is a one-block copolymer resin or the like. The amount of the α-olefin is 0.5 to 30% by weight, preferably 1 to 20% by weight, from the viewpoint of the balance between rigidity, physical strength and production suitability.

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

When the above-mentioned polyolefin resin is polymerized, it is preferable to use a polymerization catalyst containing a halogen compound or a metal compound since the amount of the polymerization catalyst having a large adverse effect on the photographic light-sensitive material can be reduced. Representative examples of the polymerization catalyst containing a halogen compound and / or a metal compound include a Ziegler catalyst of a black precipitate obtained when titanium tetrachloride and triethylaluminum are mixed in anhydrous hexane, titanium trichloride and triethylaluminum in anhydrous hexane. Consisting of a combination of a Ziegler-Natta catalyst, a black precipitate obtained by mixing in water, an organic alkyl compound of a Group I, II, or III metal, and a metal salt of a Group IV, V, VI, or VII. A regular polymerization catalyst, a natta catalyst comprising a mixture of trialkylaluminum and titanium trichloride, and SiO ₂ −
There are a Phillips catalyst comprising a mixture of Al ₂ O ₃ and chromium oxide, a catalyst comprising a reaction product of a magnesium compound and titanium halide, and an organic aluminum as a component. A special example is a catalyst using an organic aluminum compound as a cocatalyst with a solid catalyst component which is a reaction product of an oxygen-containing organic compound of magnesium, an oxygen-containing organic compound of titanium, and an aluminum halide compound.

Specific examples of the organoaluminum compound include triethylaluminum, triisobutylaluminum, tri-n-propylaluminum, diethylaluminum monochloride, diethylaluminum monobromide and the like. TiCl ₄ , T
iBr, titanium tetrahalide such as TiI ₄ , Ti (O
Trihalogenated alkoxytitanium such as CH ₃ ) Cl ₃ , Ti (OC ₂ H ₅ ) Cl ₃ , Ti (OCH ₃ ) ₂ Cl ₂ , Ti
(OC ₂ H ₅ ) ₂ Cl ₂ , dihalogenated alkoxytitanium such as Ti (OC ₂ H ₅ ) ₂ Br ₂ , Ti (OCH ₃ ) ₃ Cl, T
There are monohalogenated trialkoxy titanium such as i (OC ₂ H ₅ ) ₃ Cl and Ti (OC ₂ H ₅ ) ₃ Br.

Examples of the organomagnesium compound include ethylbutylmagnesium, diisobutylmagnesium, dihexylmagnesium, ethylmagnesium chloride, and MgF ₂ , MgCl ₂ , MgBr ₂ , and MgI ₂ . As a vanadium compound, vanadium tetrachloride, vanadium oxytrichloride, diethoxymonochloride vanadate,
And vanadate diethoxy dichloride. These halogen compounds and / or metal compounds adversely affect the photographic properties of silver halide photographic light-sensitive materials, but the total of fatty acid metal salts and / or zeolites and / or hydrotalcite compounds is 0.01 to 10% by weight, Preferably 0.0
Detoxification can be achieved by adding 5 to 7% by weight, particularly preferably 0.1 to 5% by weight.

In the case of molding with only a polyolefin resin, the molecular weight distribution is preferably from 1.5 to 7.0, more preferably from 2.0 to 7.0.
6.5 is more preferred, and 2.5 to 6.0 is most preferred. If the molecular weight distribution is less than 1.5, the fluidity of the resin deteriorates and molding failure frequently occurs. Further, the molecular weight distribution is 7.0.
If it exceeds, the dimensional accuracy deteriorates and the physical strength also decreases. The MFR (measured at a test temperature of 190 ° C. and a test load of 2.16 kgf under the E condition of ASTM D1238) is 0.0.
1 to 70 g / 10 min is preferable, and 0.02 to 50 g / 1.
0 minutes is more preferred, and most preferably 0.03 to 40 g.
/ 10 minutes, and less than 0.01 g / 10 minutes, the fluidity of the resin is poor, and the melt fracture (melt fracture)
ure) frequently occur and cannot be put to practical use. On the other hand, if the melt flow rate exceeds 70 g / 10 minutes, the fluidity of the resin becomes too large, the film moldability is deteriorated, and the physical strength is small, and practical use is difficult.

The most preferred olefin resin is a resin produced by polymerization using a single-site catalyst (a typical example is a metallocene catalyst).

L-LDPE resins produced by polymerization using a single-site catalyst include zirconium-based, titanium-based,
Copolymer resin of ethylene having a molecular weight distribution of 1.5 to 10 and an α-olefin having 3 to 12 carbon atoms produced by polymerization using a single-site catalyst containing at least one of a hafnium-based and a vanadium-based metallocene complex. It is preferable that the material is excellent in physical strength, has little residual metal component and residual halogen-based compound component, has little adverse effect on the photographic properties of the photographic photosensitive material, and has good heat sealability (heat sealability). Strength, low-temperature heat-sealing property, hot-tack property, contaminant-sealing property, heat-sealing strength after long-term aging, etc.). Further, it is possible to prevent rust and corrosion from occurring in the film forming machine.

A typical example of the single-site catalyst is 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 Japanese Patent Laid-Open No. 50
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. 300667 and the like.

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.

The polymerization method using the metallocene catalyst is disclosed in a number of 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-61-29609, 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.

Of the ethylene / α-olefin copolymer resins produced by polymerization using these metallocene catalysts, zirconium-based, hafnium-based, titanium-based, and vanadium-based copolymer resins having a small amount of catalyst residues that adversely affect the photographic properties of photographic light-sensitive materials. A resin of at least 10,000 g per g of the solid catalyst component using at least one metallocene catalyst is preferred. In particular, a metallocene catalyst comprising zirconocene dichloride and methylaluminoxane is preferred. The content of residual halogen component which adversely affects photographic properties in the resin is 400 pp
m or less, particularly preferably 150 ppm or less.
It is also possible to extract a catalyst residue using a catalyst deactivator in order to reduce the halogen content of the resin to 400 ppm or less,
Further, it is necessary and preferable to provide a vent in the pelletizer or the film forming machine in order to reduce the residual halogen compound component and to improve the rust prevention and photographic properties of the screws and dies of the extruder.

The most preferred polymerization method uses a metallocene catalyst at a polymerization temperature of 40 to 100 ° C. and a polymerization pressure of 5 to 50 kg.
Ethylene · alpha produced by gas phase polymerization method under the conditions of / cm ²
-An olefin copolymer resin.

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

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

Since these halogen compound components become halogen gas and exert the above-mentioned various adverse effects, the following halogen gas scavenger is contained in the inner conductive thermoplastic resin layer of the packaging material for photographic light-sensitive material of the present invention. It is particularly preferable to include them.

That is, preferred compounds as the halogen gas scavenger in the present invention are, for example, sulfide compounds, nitrites, semicarbazides, sulfites,
Hydroquinones, ethylenediamine, acetone semicarbazone, and p-hydroxyphenylglycine. Particularly preferred compounds include compounds represented by the following general formula.

[0041]

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

In the general formula (H), the substituent is
A halogen atom (e.g., fluorine, chlorine, bromine), an alkyl group (e.g., methyl, ethyl, n-propyl, t-butyl, n-amyl, i-amyl, n-octyl, n-dodecyl, n-octadecyl, Particularly preferably 1 to 32 carbon atoms), alkenyl group, aryl group, acyl group, cycloalkyl group, alkoxy group, aryloxy group, alkylthio group, arylthio group, alkylacylamino group,
Arylacylamino group, alkylcarbamoyl group, arylcarbamoyl group, alkylcarbonamide group, arylcarbonamide group, alkylsulfonamide group,
Preferred are an arylsulfonamide group, an alkylsulfamoyl group, an arylsulfamoyl group, an alkylsulfonyl group, an arylsulfonyl group, an alkyloxycarbonyl group, an aryloxycarbonyl group, an alkylacyloxy group, and an arylacyloxy group.

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

A 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.

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

The most preferred 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% by mole, particularly preferably from 2 to 80% by mole, most preferably from 2 to 50% by mole, and the ethylene component is preferably from 5 to 99% by mole, more preferably from 10 to 99% by mole, particularly preferably from 20 to 99% by mole. It is 98 mol%, most preferably 50 to 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. , Heptene-1, eicosene-1, 4-methyl-hexene-1, 4,4-dimethylpentene-1 and the like 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 most preferred resin constituting the inner conductive thermoplastic resin layer of the present invention is an ethylene / α-olefin copolymer resin produced by polymerization using a metallocene catalyst. This may be performed by any method as long as the polymerization is carried out in the presence of a metallocene catalyst.For example, polymerization in a high-pressure polymerization method is carried out at 120 ° C. in order to maintain a polymer in a solution state and increase polymerization activity. As described above, 500 kgf / cm at a temperature of 300 ° C. or less in order to suppress a chain transfer reaction that causes a decrease in molecular weight and not to lower polymerization activity.
^It is preferable to carry out at a pressure of ² G or more. In addition, in the polymerization in the gas phase polymerization method, a high temperature is not preferable because the copolymer is in a powder state, and it is necessary that the temperature be 100 ° C. or lower. To increase the temperature, 50 ° C. or higher is preferable. In order to increase the polymerization activity, it is preferable to use a catalyst component preliminarily polymerized with an olefin, an organic aluminum compound and an ionized ionic compound. In the polymerization in the solution polymerization method, the polymerization temperature is adjusted to 12 in consideration of the fact that the copolymer is in a solution state and increasing the polymerization activity.
The temperature must be 0 ° C. or higher. The upper limit of the polymerization temperature is not particularly limited, but is 300 ° C. in order to suppress a chain transfer reaction that causes a decrease in molecular weight and not to lower catalyst efficiency.
The following is preferred. The pressure during the polymerization is not particularly limited, but is preferably at least atmospheric pressure in order to increase the polymerization activity.

In any case, the catalyst residue adversely affects the photographic properties of the photographic light-sensitive material. In addition, rust is generated on the resin contact portion of the mold and the extruder to deteriorate the dimensional accuracy, and the resin is burnt or greasy. Therefore, a smaller amount is preferable in the present invention.

Therefore, in order to maintain good photographic properties, the amount of the residual halogen gas component in the photographic photosensitive material packaging material of the present invention is 400 ppm or less, preferably 200 ppm or less, more preferably 100 ppm or less, and particularly preferably 1 ppm or less. ８０80 ppm, most preferably 4-60 ppm.

The residual amount of any one of chromium, zirconium, titanium, hafnium and panadium is 200 p.
pm or less, preferably 200 ppm or less, more preferably 100 ppm or less, particularly preferably 60 ppm or less,
Most preferably, it is 40 ppm or less.

Particularly preferred ethylene / α in the present invention
-Olefin copolymer resin, ethylene in the presence of a catalyst containing a transition metal compound of Group IV of the periodic table containing a ligand having a cyclopentadienyl skeleton and optionally a cocatalyst, an organoaluminum compound, and a carrier. And 3 to 20 carbon atoms
Of α-olefins. Further, a catalyst obtained by pre-polymerizing ethylene and / or the α-olefin into the above catalyst may be used as the catalyst.

The α-olefin has 3 to 3 carbon atoms.
20, preferably 3 to 12, particularly preferably 3 to 8, specifically propylene, butene-1, 4-methylpentene-1, 3-methylpentene-1, hexene-1, pentene-1 Octene-1, nonene-1, decene-1, undecene-1, dodecene-1, tridecene
1, tetradecene-1, pentadecene-1, hexadecene-1, heptadecene-1, octadecene-1, nanodecene-1, eicosene-1 and the like. One or more of these can be used for copolymerization. Further, the content of these α-olefins is desirably selected in the range of 50 mol% or less, preferably 35 mol% or less, more preferably 1 to 25 mol%, and particularly preferably 3 to 20 mol%. .

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

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

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

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

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

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

The catalyst may be used by being supported on an inorganic or organic carrier. The carrier is preferably an inorganic or organic porous oxide, specifically, SiO ₂ , Al ₂
O ₃ , MgO, ZrO ₃ , TiO ₂ , B ₂ O ₃ , CaO, Z
nO, BaO, ThO _{2 and the} like or a mixture thereof, and examples thereof include SiO ₂ —Al ₂ O ₃ , SiO ₂ —V ₂ O ₃ , and SiO _2.
—TiO ₂ , SiO ₂ —MgO, SiO ₂ —Cr ₂ O _{3 and the} like.

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

The ethylene / α-olefin copolymer is produced by a gas phase polymerization method, a slurry polymerization method, a solution polymerization method or the like in the absence of a solvent in the presence of the above-mentioned catalyst. Inactive carbons exemplified by aliphatic hydrocarbons such as butane, pentane, hexane, and hebutane; aromatic hydrocarbons such as benzene, toluene, and xylene; alicyclic hydrocarbons such as cyclohexane and methylcyclohexane; Produced in the presence of a hydride solvent. Polymerization conditions are not particularly limited, the polymerization temperature is usually 15 ~ 350 ℃,
Preferably it is 20-200 ° C, more preferably 50-1.
10 ° C., and the polymerization pressure is usually from normal pressure to 7
0 kg / cm ³ G, preferably normal pressure to 20 kg / cm ³
G, and in the case of the high-pressure method, it is usually desirable to be 1500 kg / cm ² G or less. The polymerization time is usually 3 minutes to 1 in the case of the low and medium pressure method.
0 hours, preferably about 5 minutes to 5 hours. In the case of the high-pressure method, it is usually 1 minute to 30 minutes, preferably about 2 minutes to 20 minutes. In addition, the polymerization is of course a one-stage polymerization method,
There is no particular limitation on a multi-stage polymerization method of two or more stages in which polymerization conditions such as hydrogen concentration, monomer concentration, polymerization pressure, polymerization temperature, and catalyst are different from each other.

Other most preferred specific examples include, in the presence of various metallocene catalysts, most preferably in the presence of the specific metallocene catalyst, ethylene and α-C 3-20.
The resin obtained by copolymerizing olefin is ethylene-α-
Drying is performed at a flow rate of 0.03 to ³ m ³ / hr for 0.5 to 72 hours with air or an inert gas at 30 to 150 ° C. per kg of the olefin copolymer, and / or ethylene / α olefin copolymer at 30 ° C. or higher. Air or an inert gas at a flow rate of 0.001 to 0.5 m ³ / hr is introduced with hot water having a melting point lower than the melting point of the coalescence, immersed for 0.5 to ³⁰ hours, and carbon measured by head space gas chromatography. Total amount of volatile components of number 12 or less (normal hexane conversion)
Is a method for producing an ethylene / α-olefin copolymer in which the value (Q) before / after drying is 200 or more. that's all,
Although the copolymer resin of ethylene and α-olefin has been described as a representative, similarly, homopolyethylene resin, various polypropylene resins, and various ethylene copolymer resins can be produced by polymerization using the above metallocene catalyst.

The above-mentioned acid-modified polyolefin resin will be described.

The acid-modified polyolefin resin is a modified polyolefin resin obtained by graft-modifying a polyolefin resin and an unsaturated carboxylic acid, and examples thereof include a graft-modified polyethylene resin, a graft-modified polypropylene resin, and a graft-modified ethylene copolymer resin (EVA resin, EEA resin). Resin, L-LDPE resin, EMA resin, etc.).

Graft modification with a polyolefin resin.
Unsaturated carboxylic acids are generic names including their derivatives. Typical examples include acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, tetrahydrophthalic acid, mesaconic acid, angelic acid, citraconic acid, crotone. Acid, isocrotonic acid, nadic acid, (endocis-
Bicyclo [2,2,1] hept-5-ene-2,3-dicarboxylic acid), maleic anhydride, citraconic anhydride, itaconic anhydride, methyl acrylate, methyl methacrylate,
Ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, glycidyl acrylate, glycidyl methacrylate, monoethyl maleate, diethyl maleate, monomethyl fumarate, dimethyl fumarate, diethyl itaconate, Acrylamide, methacrylamide,
Maleic acid monoamide, maleic acid diamide, maleic acid-N-monoethylamide, maleic acid-N, N-diethylamide, maleic acid-N-monobutylamide, maleic acid-N, N-dibutylamide, fumaric acid monoamide, fumaric acid Acid diamide, fumaric acid-N-monoethylamide, fumaric acid-N, N-diethylamide, fumaric acid-N
-Monobutylamide, fumaric acid-N, N-diethylamide, fumaric acid-N-monobutylamide, fumaric acid-N,
N-dibutylamide, maleimide, monomethyl maleate, dimethyl maleate, potassium methacrylate, sodium acrylate, zinc acrylate, magnesium acrylate, calcium acrylate, sodium methacrylate, potassium acrylate, potassium methacrylate, N-
Butylmaleimide, N-phenylmaleimide, maleenyl chloride, glycidyl maleate, dipropyl maleate,
Aconitic anhydride, sorbic acid and the like can be mentioned, and they can be mixed with each other.

Among them, acrylic acid, maleic acid, maleic anhydride and nadic acid are preferred, and maleic anhydride is particularly preferred.

The method for graft-modifying unsaturated carboxylic acids in the acid-modified polyolefin resin is not particularly limited. For example, the reaction in the molten state
No. 421, etc., the method disclosed in Japanese Patent Publication No. 44-15422, which reacts in a solution state, the method disclosed in Japanese Patent Publication No. Tokubo 50-7 to react in the state
There is a method disclosed in, for example, US Pat.

Among these methods, the melt-kneading method using an extruder is preferred because it is simple in operation and inexpensive.

The amount of unsaturated carboxylic acids used is determined by the polyolefin resin base polymer (various polyethylene resins, various polypropylene resins, various polyolefin copolymer resins, polybutene-1 resin, poly-4-methylpentene-
It is 0.01 to 20 parts by weight, preferably 0.2 to 5 parts by weight, based on 100 parts by weight of an α-olefin copolymer resin such as 1 and the like.

Organic peroxides and the like are used to promote the reaction between the polyolefin resin and the unsaturated carboxylic acids.

Examples of the organic peroxide include benzoyl peroxide, lauroyl peroxide, azobisisobutyronitrile, dicumyl peroxide, α,
α'bis (t-butylperoxydipropyl) benzene, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, 2,5-dimethyl-2,5-di (t-butylperoxy) Oxy) hexyne, di-t-butyl peroxide, cumene hydroperoxide, t-butyl-hydroperoxide, dicumyl peroxide, t-butylperoxylaurate, t-butylperoxybenzoate, 1,3bis ( organic peroxides such as t-butylperoxyisopropyl) benzene, cumene hydroperoxide, di-t-butyl-diperoxyphthalate, t-butylperoxymaleic acid and isopropyl percarbonate; and azobisisobutyronitrile. Examples include azo compounds and inorganic peroxides such as ammonium persulfate.

These may be used alone or in combination of two or more. Particularly preferred is a decomposition temperature of 170 ° C.
Di-t-butyl peroxide which is between ２００200 ° C.
Di-cumyl peroxide, 2,5-dimethyl-2,5
Di (t-butylperoxy) hexane, 2,5-dimethyl-2,5 di (t-butylperoxy) hexyne, 1,
3-bis (t-butylperoxyisopropyl) benzene.

The addition amount of these peroxides is not particularly limited, but is 0.005 to 5 parts by weight, preferably 0.01 to 1 part by weight, per 100 parts by weight of the polyolefin resin.

Representative examples of commercially available acid-modified polyolefin resins are shown below. (1) Nippon Petrochemical KK “N Polymer” (2) Mitsui Petrochemical KK “ADMER” (3) Showa Denko KK “ER RESIN” (4) Mitsubishi Kasei Kogyo KK “NOVATEC-AP” (5) Mitsubishi Yuka KK “MODIC” (6) Nippon Unicar KK “NUC-ACE” (7) Ube Industries KK “UBE BOND” (8) Tosoh KK “Lusen M” (9) Sumitomo Chemical KK “Bondyne” (10) Mitsui Dupont Chemical KK "CMPS" etc. (11) Exxon "Dexon" (12) Toa Fuels Industry KK "HA Series" (13) Mitsui Toatsu Chemicals KK "MITSULO LONPLY" etc.

Further, the acid-modified polyolefin resin can coat and uniformly disperse the surface of a light-shielding substance such as carbon black or aluminum powder or a fibrous filler contained in the film, thereby reducing the generation of microgrids. By doing so, the physical strength of the film can be improved.

The inner conductive thermoplastic resin layer and the outer conductive thermoplastic resin layer are made of a thermoplastic elastomer, an ethylene copolymer resin having a crystallinity of 40% or less as measured by an X-ray diffraction method, and an acid-modified polyolefin resin. Is preferably contained in an amount of 3 to 49% by weight and carbon black in an amount of 0.1 to 60% by weight.

The thermoplastic elastomer (hereinafter referred to as TPE) can be roughly classified into styrene-based (hereinafter referred to as SBC),
Ester (hereinafter referred to as TPEE), olefin (hereinafter referred to as TPO), vinyl chloride (hereinafter referred to as TPVC), amide (hereinafter referred to as TPAE), crystalline 1,2
Polybutadiene (hereinafter referred to as RB), ionomer,
There are various chemical structures such as fluorine (hereinafter referred to as F-TPE), urethane (hereinafter referred to as TPU), isoprene, chlorinated polyethylene, and polyfluorocarbon. Table 1 shows typical commercially available TPEs.

[0078]

[Table 1]

The crystallinity measured by the X-ray diffraction method is 40
% Or less of the ethylene copolymer resin is more preferably 3% or less.
It is at most 5%, particularly preferably at most 30%, most preferably at most 25%. When the crystallinity exceeds 40%, it becomes difficult to efficiently improve the dispersibility of carbon black. Further, when carbon black is contained in an amount of 60% by weight or more, physical strength, suitability for heat sealing, and the like are deteriorated, and it is difficult to ensure complete light shielding properties and sealing properties.

In the case of a wrapping material for a photographic light-sensitive material requiring light-shielding properties, a light-shielding substance is added to at least one of the inner conductive thermoplastic resin layer, the outer conductive thermoplastic resin layer and the intermediate thermoplastic resin layer. To ensure light-shielding properties.

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) , Bagasse, moroheiya, smoke fire, etc.), 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 do not adversely affect photographic properties and are stable to heat even at 150 ° C. or more and are opaque are preferable. Active materials, light absorbing carbon black, titanium nitride, graphite and iron black are preferred.

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

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 feed oil Creosote oil ｛Coal-based feedstock｝ 0.3-0.6% Ethylene bottom oil ｛Naphtha feedstock (petroleum-based feedstock)｝ 0.05-0.1% Ethylene bottom oil ｛ Light oil feedstock (petroleum-based feedstock)｝ 0.2-1.5% Fluid catalytic cracking residue oil ｛petroleum-based feedstock ％ 0.2-4.0%

Therefore, as the raw material oil, ethylene bottom oil obtained from petroleum creosote oil is preferable. If ethylene bottom oil obtained from naphtha is used as raw material, the sulfur content in carbon black is reduced to 0.1% by weight. It is most preferable because the following can be achieved.

In particular, free sulfur which has been found to have a direct adverse effect on the photographic properties of photographic light-sensitive materials (free sulfur)
hus) (carbon black having a content of 100 ppm or less, preferably 50 ppm or less, particularly preferably 20 ppm or less, most preferably 10 ppm or less is used. In view of the low free sulfur content, carbon black produced using ethylene bottom oil from naphtha as the raw material 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 content of the aldehyde compound by the iodine method is preferably 0.1% by weight or less, particularly preferably 0.05% by weight or less, and most preferably 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.

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, # 55, # 1
00, # 600, # 950, # 1000, # 2200
(B), # 2400 (B), # 4000, # 4010, MA
7, MA8, MA11, MA100, MA100R, M
A220, MA230, # 3050, # 3150, # 3250, # 3600, # as Mitsubishi conductive carbon black
3750, # 3950 and the like.

Further, N110, N manufactured by Showa Cabot
134, N219, N220, N234, N326, N3
30, N330T, N339, N351, N550, M
AF, SRF and the like.

As overseas products, for example, Black Pearls L, 2, 46, 70, 7 of Cabot Corporation
1,74,80,81,130,280,430,46
0,480,607,800,880,900,100
0, 1100, 1300, 1400, etc., Regal 9
9,250,300,330,400,415,660,
991, SRF-S, etc., Vulcan 3,6, P, X
Sterling 10, SO, V, S, C-72, etc.
FT-FF, MT-FF, and the like.

Further, Unit of Ashland Chemical Co., Ltd.
ed R, BB, 15,102,3001,3004,3
006,3007,3008,3009,3011,301
2, XC-3016, XC-3017, 3020 and the like. Furthermore, Colombian Chemical's Con
ductex 975, SC, Raven C, H20, 4
10,420,430,450,460,500,52
0,760,790,850,890,1000,104
0,1060,1170,1190,1200,125
0,1255,2000,2500,3500,5000,5
250, 5750, 7000, and the like, but are not limited thereto.

In the present invention, furnace carbon black is preferable 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. Especially high sensitivity
(ISO sensitivity 400 or more) For photographic photosensitive materials, acetylene black having a sulfur content of 0.1% or less is preferable.
The volume resistivity (measured in a constant temperature and humidity room at 20 ° C. and 60% RH) is as follows: MFR: 0.3 g / 10 min, density: 0.958 g
/ Cm ³ density polyethylene resin 100 parts by weight of ² × 10 2 Ω · a was added 10 parts by weight of Ketjen black EC film against cm, Ketjenblack EC6
6 × 10 ¹ for a film containing 10 parts by weight of 00JD
Ω · cm, 3.1 × 10 ⁶ Ω · cm for a film containing 10 parts by weight of acetylene black, Vulcan XC-72
1.6 × 10 ⁶ Ω · c for a film containing 10 parts by weight of
m. If necessary, it is also preferable to mix the former carbon black for coloring and the latter carbon black in an appropriate ratio according to the required characteristics. The form in which the light-shielding substance is blended is roughly classified as follows.

(1) Uniformly colored pellets (most commonly used, called color compounds) (2) Dispersible powders (treated with various surface treatment agents, also called dry color, (3) Paste (Plasticizer etc. dispersed) (4) Liquid (Liquid dispersed in surfactant, also called liquid color) (5) Masterbatch pellets (a light-shielding substance is dispersed at high concentration in the plastic to be colored) (6) Moisturizing granular powder (after light-shielding substance is dispersed at high concentration in plastic (7) Dry powder (normal untreated dry powder)

Although there are various modes in which the light-shielding substance is mixed with the thermoplastic resin as described above, the masterbatch 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 light sensitivity and large light-shielding ability.
Even when the inner conductive thermoplastic resin layer and the like are molded with L-LDPE resin, the carbon black hardens (bubbles) and pinholes are less likely to be generated in the thermoplastic resin film such as fish eyes. Especially pH
(Measured by JIS K 6221): 6.0-9.0, average particle diameter (measured by electron microscopy): 10-120 mμ, especially 1
It is preferably from 0 to 80 mμ, and most preferably 10 μm.
６０60 mμ. Among these, volatile components (JI
SK6221) 2.0% or less, DBP oil absorption (measured by JIS K6221 oil absorption method A) 50 ml
Furnace carbon black of / 100 g or more is preferable in that it is inexpensive, does not adversely affect photographic properties, improves light-shielding properties, improves dispersibility, and causes little deterioration in physical properties.

Further, the AST in the packaging material for photographic light-sensitive materials
The sulfur component according to the measurement method of MD 1619-60 is 0.1%.
9% or less, preferably 0.7% or less, particularly preferably 0.7% or less.
If the content is not 5% or less, adverse effects on the photographic properties of the photographic light-sensitive material, such as an increase in fog, an abnormal sensitivity, an abnormal occurrence, etc. In particular, a free sulfur component which greatly adversely affects the photographic properties of a direct photographic light-sensitive material (each sample is cooled and solidified with liquid nitrogen, then pulverized, 100 g of the pulverized sample is put into a Soxhlet extractor, extracted with chloroform at 60 ° C. for 8 hours, and cooled. The total volume is set to 100 ml, 10 ml of this solution is injected into a high performance liquid chromatograph, and sulfur is quantified.The conditions for high performance liquid chromatograph are column; ODS silica column (4.6 φ × 150 m)
m), separation solution; 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 at most 0.1%, preferably at most 0.05%, particularly preferably at most 0.01%. Although expensive, a packaging material using acetylene black having a sulfur content of 0.1% or less is suitable for maintaining good photographic properties as a packaging material for a photographic photosensitive material having an ISO sensitivity of 100 or more. .

The content of a cyan compound which deteriorates 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, and most preferably 1 ppm or less. In particular, in the case of a gold-sensitized photographic material, unless it is 1 ppm or less, desensitization is large and practical application is difficult, and it is necessary to add a scavenger or the like.

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

Preferred palladium compounds include palladium (II) chloride, palladium (II) bromide, palladium (II) hydroxide, palladium (II) sulfate, palladium (II) thiocyanate, and tetrachloropalladium (II) acid salt. (Sodium salt, potassium salt, ammonium salt), hexachloropalladium (IV) salt, tetrabromopalladium
(II) acid salt, hexapromo palladium (IV) acid salt, bis (salicylate) palladium dimumate (II) acid salt, bis (dithiooxalato-S, S ') palladium (II) acid salt, trans-dichlorobis (thioether) palladium (II), tetraamminepalladium (II) salt, dichlorodiamminepalladium (II), dibromodiamminepalladium (II), oxalatodiamminepalladium (II), dinitrodiamminepalladium (II), bis (ethylenediamine) palladium (II) salt, Dichloroethylenediaminepalladium (II), bis (2,2'-pipyridine) palladium (II)
Salt, bis (1,10-phenanthroline) palladium (II) salt, tetranitropalladium (II) salt, bis (glycinato) palladium (II), tetrakis (thiocyanato) palladium (II) salt, dichlorobis (phosphine) palladium (II) acid salt, dichlorobis (phosphine) palladium (II), di-μ-chloro-bis [chloro (phosphine) palladium (II)], di-μ-chloro-
Bis [chloro (arsine) palladium (II)] and dinitrobis (arsine) palladium (II).

Preferred platinum compounds include platinum chloride (II), platinum chloride (IV) and hexafluoroplatinum (I
V), tetrachloroplatinate (II), hexachloroplatinate (IV), trichlorotrifluoroplatinate (IV), tetrabromoplatinate (II), hexabromoplatinate (IV), dibromodichloro Platinate (II), hexahydroxoplatinate (IV), bis (oxalato) platinate (II), dichlorobis (oxalatoplatinate (IV), bis (thiooxalato) platinate (II), bis ( Acetylacetonato) platinum (II), bis (1,1,1,5,
5,5-hexafluoro-2,4-pentanedionato) platinum (II), bis (1,1,1-trifluoro-2,4-pentanedionato) platinum (II), tetrakis (thiocyanato) platinum ( II), hexakis (thiocyanato) platinate (IV), bis {(Z) -1,2-dicyanoethylene-1,2-dithiolato} platinate (II), dichlorobis (diethylsulfide) platinum (II) ), Tetrachlorobis (diethylsulfide) platinum (IV), bis (glycinato) platinum (II), dichloroglycinatoplatinate (II),
Dichlorobis (triethylphosphine) platinum (II), chlorohydridobis (triethylphosphine) platinum (II),
Tetraammineplatinum (II) salt, tetrachloroplatinum (II)
Acid salt, dichlorodiammineplatinum (II), trichloroammineplatinum (II) salt, hexaammineplatinum (IV) salt, chloropentaammineplatinum (IV) salt, tetrachlorodiammineplatinum (IV), dinitrodiammineplatinum (II), Dichlorotetrakis (methylamine) platinum (IV) salt, dichloro (ethylenediamine) platinum (II), bis (ethylenediamine) platinum (II) salt, tris (ethylenediamine) platinum (IV) salt, dichlorobis (ethylenediamine) platinum (I
V) Salt, dichlorodihydroxo (ethylenediamine) platinum (IV), tetrakis (pyrimidine) platinum (II) salt, dichlorobis (pyridine) platinum (II), bis (2,2′-pipyridine) platinum (II) salt, tetranitro Platinum (II) acid salt,
Chlorotrinitroplatinate (II), dichlorodinitroplatinate (II), dibromodinitroplatinate (II), hexanitroplatinate (IV), chloropentanitroplatinate (IV)
Acid salt, dichlorotetranitroplatinate (IV), trichlorotrinitroplatinate (IV), tetrachlorodinitroplatinate (IV), dibromodichlorodinitroplatinate (IV), trichloro (ethylene) platinum (II ) Acid salt, di-μ-
Chloro-bis (chloro (ethylene) platinum (II), tra
ns-dichloro (ethylene) (pyridine) platinum (II),
Bis [bis (β-mercaptoethylamine) nickel (II) -S, S ″ -platinum (II) salt and dichlorodicarbonylplatinum (II).

Gold (I or III), Rhodium (III), Iridium (III or IV) and Osmium (II, III or IV)
Can also be used in the same manner, and as such an example, for example, potassium tetrachloroaurate (II
I), rhodium (III) chloride, potassium hexachloroiridate (IV), potassium tetrachloroylate (I
II) and potassium hexachloroosmate (IV). The inorganic or organic compound of the noble metal is not limited to the above specific examples as long as the effects of the present invention can be obtained.

The iodine adsorption amount (measured according to JIS K 6221) is 20 mg / g or more, preferably 30 mg / g or more, particularly preferably 50 mg / g or more, most preferably 80 mg / g or more, and dibutyl phthalate (DB
P), oil absorption (measured according to JIS K 6221) 50 ml
/ 100 g or more, preferably 60 mg / 100 g or more,
It is particularly preferably at least 70 ml / 100 g, most preferably at least 100 ml / 100 g.

Next to carbon black, the preferred light-shielding substance has a refractive index of 1.50 as measured by Larsen's oil immersion method.
The above 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 (2.75),
Silicon carbide (2.67), anatase type titanium oxide (2.5
2), zinc oxide (2.37), antimony oxide (2.35),
Lead white (2.09), zinc white (2.02), lithopone (1.8
4), 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 (1.54), magnesium hydroxide (1.54), magnesium chloride hydrochloride
(1.52) and alumina (1.50). Particularly preferred are light-shielding substances having a refractive index of 1.56 or more, most preferably 1.60 or more.

Calcium silicate having a refractive index of less than 1.50
(1.46), diatomaceous earth (1.45), hydrous silicic acid (1.4
4) and the like have a small light-shielding ability, so a large amount of addition is required, and use as a light-shielding substance 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.

Light-shielding substances having a specific gravity of 3.1 or more include silicon carbide, barium sulfate, molybdenum disulfide, and 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, iron whisker, nickel whisker, chrome whisker,
Examples include stainless steel powder and whisker, magnesite, apatite, spinel, corundum, zircon, antimony trioxide, barium carbonate, zinc white, chrominium oxide, tin powder, and mixtures thereof.

Particularly preferable light-shielding substances for imparting X-ray shielding properties are zircon, corundum, barium sulfate, barium chloride, barium titanate, lead powder, lead oxide, zinc powder, zinc white, tin powder, stainless 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 and the type and application of the resin, but the physical strength,
It is 0.1 to 80% by weight, preferably 0.3 to 60% by weight, more preferably 0.5 to 40% by weight, and most preferably 1.0 to 20% by weight in view of economy, production suitability and the like.

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

[0110]

[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.
It is used in a state of 0% by weight or less, more preferably 1.0% by weight or less, and most preferably 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, and adsorbing a deodorant, an aromatic agent, an oxygen scavenger, etc. Representative examples of oil-absorbing inorganic pigments preferably contained in the invention include zinc white (52), asbestin (50), clay (51), titanium oxide (56), kaolin
(60), talc (60), carbon black (60 or more),
There is activated carbon and the like. The figures in parentheses indicate the oil absorption (JIS K6
221 oil absorption measured by A method. (Unit: ml / 100 g).

Representative examples of metal powder (including metal paste) 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.

The term “aluminum powder” in the present invention includes both aluminum powder and aluminum paste. The aluminum powder whose surface is coated with a surface coating material and the aluminum paste whose low volatile substances are removed from a thermoplastic resin are referred to as 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 ball milling, stamp milling or atomizing. Originally made in paste form.

In the present invention, this aluminum paste and various aromatic monovinyl resins (polystyrene resin, rubber-containing polystyrene resin, etc.), polyolefin thermoplastic resins (various polypropylene resins, various polyethylene resins, acid-modified resins, EVE resins, EEA resins, EAAs) Resin),
Low molecular weight polyolefin resin, paraffin wax,
Heat-kneading of a tackifier, a dispersing agent such as metallic soap, etc., and the content of volatile substances (100 ° C, 5 hours at 100 ° C for 5 hours) by removing low volatile substances (mainly mineral spirits and white spirits with strong odor) with a vacuum pump etc. 3% or less
Preferably, 1% or less, particularly preferably 0.5% or less is used as the aluminum paste compound resin or the aluminum paste masterbatch resin.

It is particularly preferable to use the resin as an aluminum paste masterbatch resin in order to eliminate adverse effects and odor on the photographic 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, if the aluminum paste concentration in a photographic photosensitive material packaging material is to be 2% by weight. In this case, 19 parts by weight of a natural resin is kneaded with 1 part by weight of an aluminum paste masterbatch, and the mineral spirit content is reduced because some mineral spirits are removed as a gas by heating during molding. It becomes 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.

[0119] The aluminum powder is obtained by pulverizing molten aluminum into a powder by an atomizing method, a granulating method, a rotating disk dropping method, an evaporation method, or the like, and crushing aluminum foil by a ball mill method, a stamp mill method, 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 to m) is cut with a shredder or the like, and annealed to remove fatty acids. Thereafter, 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 50 μm using at least one of a pulverizer selected from a ball mill, a stamp mill, a vibration mill and an attritor.
m, an aluminum powder having an average thickness of 0.03 to 0.5 μm and a fatty acid content of 5% by weight or less is particularly preferable because of its excellent dispersibility, photographic properties and gloss, and low odor.

For practical use as the packaging material for photographic light-sensitive materials of the present invention, quality assurance, physical strength assurance, photographic performance assurance,
From the viewpoint of moldability and economy, the total content of the light-shielding substance in the inner conductive thermoplastic resin layer is 0.1 to 80% by weight, preferably 0.3 to 60% by weight, more preferably 0.5 to 40% by weight. %, But the content varies depending on the light-shielding ability, average particle diameter, and the like of the light-shielding substance. Carbon black, titanium oxide and aluminum powder having excellent light-shielding ability are used as light-shielding substances, and at least one of a thermoplastic elastomer, an ethylene copolymer resin having a crystallinity of 40% or less, and an acid-modified polyolefin resin is used in an amount of 3 to 3%. When 49% by weight is contained, the total content in the light-shielding layer is preferably from 0.1 to 60% by weight and from 0.3 to 40% by weight from the viewpoints of light-shielding properties, economy, film formability, and the like. 5-20% by weight is more preferable, and 1-10
% Is most preferred. If the content is less than 0.1% by weight, unless the thickness of the wrapping material for photographic light-sensitive materials 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 exceeds 60% by weight, it becomes expensive, dispersibility deteriorates, and microgrids (agglomerated impurities)
And the amount of water in the photographic material packaging material increases due to the increase in the amount of water adsorbed on the carbon black,
The photographic performance of the photographic material is adversely affected (fog generation, abnormal sensitivity, abnormal color formation, etc.). Furthermore, the moldability of the packaging material for photographic light-sensitive materials is deteriorated (foaming, silver stripes, pinholes, short shots, etc.) and the physical strength is reduced, which makes practical use difficult.

Resin of light-shielding substance (carbon black, aluminum powder, inorganic pigment having a refractive index of 1.50 or more, inorganic pigment having a specific gravity of 3.4 or more, and 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.

Representative examples of the surface coating material are shown below.

(1) Coupling agent i) Coating agent coating containing azidosilanes (disclosed in JP-A-62-32125) ii) Coating of silane coupling agent (aminosilane etc.) iii) Titanate coupling (2) Deposit silica, followed by alumina. (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 in the 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 0.001 to 20 parts by weight, preferably 0.01 to 15 parts by weight).

As a surface coating material of the light-shielding substance, the photographic light-sensitive material has little adverse effect such as fogging, and has excellent effects such as improvement in dispersibility of the light-shielding substance, reduction in occurrence of dust, and improvement in resin fluidity. ), (3), (12), (14), (15), (16), (1
In addition to 8) and (19), 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.
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, the effect of preventing the above problems can be exhibited. 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.

The ester used in the present invention includes 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, melisyl alcohol, racyl alcohol,
Seryl alcohol, brisyl alcohol and the like can be mentioned.

Since these improve the flowability of the thermoplastic resin and achieve uniform kneading, they are very excellent as a surface coating material of the light shielding material. 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 will increase with time and the slip between the resin and the screw will occur and the discharge amount will fluctuate.

The total sulfur content (AS) in all the light-shielding substances to be added
TM D-1619) is 0.9% or less, preferably 0.7% or less.
%, Particularly preferably 0.5% or less, and the free sulfur content is 150 ppm or less, preferably 50 ppm or less, particularly preferably 30 ppm or less.
The ash content according to 506 is less than 0.5%, preferably 0.4%
% Or less, particularly preferably 0.3% or less, and unless the aldehyde compound content is 0.2% or less, preferably 0.1% or less, particularly preferably 0.05% or less, adverse effects on photographic properties will occur. It is necessary to be careful.

Further, a cyanide compound also 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.
It is a light-shielding substance of not more than 10 ppm, preferably not more than 10 ppm, particularly preferably not more than 5 ppm.

The inner conductive thermoplastic resin layer, the outer conductive thermoplastic resin layer and the intermediate thermoplastic resin layer may contain one or more hydrotalcite compounds and zeolite. By containing at least one hydrotalcite compound and zeolite, catalyst residues can be neutralized, substances that adversely affect photographic properties by absorbing halogen compounds such as hydrochloric acid can be detoxified, resin burning failure, etc. Can be prevented.

The content of one or more hydrotalcite compounds and 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.

[0134] hydrotalcite compound, general formula MxRy (OH) 2x + 3y- 2z (A) z · aH 2 O {M is Mg, Ca or Zn, R is Al or 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, Mg ₆ A1 ₂ (O
_{H) 16 CO 3 · 4H 2} O, Mg 8 Al 2 (OH) 20 CO 3 · 5
_{H 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) · Alx · (OH) ₂ · Xx / n · mH ₂ O where M represents an alkaline earth metal and Zn. X represents an n-valent anion.

Then, x, m and n satisfy the following condition. 0 <x <0.5 0 ≦ m ≦ 2 屈折 n = 1 to 4. The refractive index (measured by an oil immersion method of Larsen) represented by an integer of 1.40 to 1.60, preferably 1.
Hydrotalcite compounds in the range of 45 to 1.55.

[0138] 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 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 surface coating materials, the above-mentioned surface coating materials (1) to (20) of light-shielding materials can be used. 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 suspension of the hydrotalcite compound 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.

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

Further, in order to improve the dispersion of the hydrotalcite compounds, for example, higher fatty acids, fatty acid amide-based lubricants, silicone oils, sorbitan fatty acid esters such as sorbitan monostearate, and glycerin monostearate. A total amount of 0.01 to 10% by weight, preferably 0% by weight, in the inner conductive thermoplastic resin layer, the outer conductive thermoplastic resin layer and the intermediate thermoplastic resin layer, using at least one kind of glycerin fatty acid ester or the like as a dispersant. .
05 to 8% by weight, particularly preferably 0.08 to 5% by weight,
Most preferably, 0.1 to 3% by weight may be added. By using in combination with hydrotalcite compounds, prevention of deterioration of photographic properties, processing stability, corrosion resistance of molding machine are improved,
The present invention synergistically improves the effects of preventing resin deterioration, preventing physical strength reduction, and preventing occurrence of spots and coloring failure due to resin burning. 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 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.

In addition, the total content of (1) + (2) + (3) is 0.5.
0015 to 6% by weight, preferably 0.002 to 5% by weight, particularly preferably 0.003 to 4% by weight, most preferably 0.005 to 3% by weight; It should be included in the resin layer (photosensitive material side). 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 light-sensitive material.

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

Typical 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.

Table 3 shows names, molecular formulas, states and melting points of typical commercially available fatty acid metal salts.

[0154]

[Table 3]

The zeolite is a natural zeolite (ana).
lcime, 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 affinity for the resin is further improved, and the suitability for film processing, physical strength, etc. are also improved.

A lubricant can be contained in the inner conductive thermoplastic resin layer, the outer conductive thermoplastic resin layer and the intermediate thermoplastic resin layer. By including a lubricant, the moldability, handling suitability and lubricity of the film can be improved, and wrinkles and streaks can be prevented. Furthermore, no blocking occurs even when stacked with photosensitive materials,
Even when used as a packaging bag or the like, even if it rubs against the photographic light-sensitive material, scratches and static marks can be prevented from occurring. Further, the fluidity of the resin can be improved, and the film formability can be improved.

The amount of the lubricant to be added varies depending on the kind. In the case of a lubricant having a small lubricating effect mainly for maintaining the photographic performance of a photographic light-sensitive material, such as a fatty acid metal salt, the amount is preferably 0.01 to 5% by weight. 0.03 to 3% by weight is more preferable,
0.05 to 1.5% by weight is particularly preferred, 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, foaming, white smoke and die lip streaks are likely to occur, and slipping between the molten resin and the screw of the extruder is likely to occur, and the discharge amount of the resin becomes unstable. In addition, stickiness and bleed-out tend to occur with the passage of time after molding, which adversely affects the photographic material. Furthermore, the heat-sealing strength with time is reduced, and the sealing property, moisture-proof property and oxygen barrier property are deteriorated, so that it is difficult to practically use as a packaging material for a photographic material.

[0159] In addition, a lubricant having a large lubricating effect, such as a fatty acid amide-based lubricant and a bisfatty acid amide-based lubricant, is liable to bleed out and has a bad influence on a photographic light-sensitive material. 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 amount exceeds the weight percentage, slip between the molten resin and the screw of the extruder is likely to occur, and the discharge amount of the resin becomes unstable. In addition, stickiness and bleed-out tend to occur with the lapse of time after film formation. Furthermore, the bleed-out lubricant is transferred to the photographic photosensitive layer to cause development inhibition, thereby causing quality defects such as development unevenness and color unevenness.

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. Stearamide-based lubricant; Armide HT (Lion fat), Alflow S-10 ( Nippon Oil & Fats), 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), Diamid (Nihon Kasei) [Unsaturated fatty acid amide lubricant] Erucamide amide lubricant; Alflow 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 acid amide lubricant;
Kbis (Nippon Kasei) and other methylene bisstearic amide lubricants; Diamid 200 bis (Nippon Kasei), Armowax (Lion Akzo), Bisamide (Nitto Kagaku), etc. Methylene bisoleic amide lubricants; Lubron O (Japan) Chemical formation), etc. Ethylene bisstearic acid amide lubricant; Armoslip EBS (Lion Akzo), etc. Hexamethylene bisstearic acid amide lubricant; Amid 65 (Kawaken Fine Chemical), etc. Hexamethylene bis oleamide amide lubricant; Ken Fine Chemicals)

(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, especially 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-based lubricants: polyhydric alcohols, polyglycols, polyglycerols, etc.

(7) Fatty acid metal salt-based lubricant (metal soap): 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 lubricant;

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

The silicone oil preferably has a viscosity at room temperature in the range of 50 to 100,000 centistokes, and 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 photosensitive material and have a large lubricating effect, and particularly preferred when applied to packaging materials for photographic photosensitive materials, It is a polyether-modified silicone. The silicone oil improves the coefficient of friction of a molding material, for example, a resin film in a heated state, reduces sliding resistance generated during hot plate sealing by an automatic packaging machine, and prevents wrinkles from forming, resulting in a beautiful appearance. And a basis for obtaining a resin film having a high sealing performance and an adhesive property without sagging of the packaged object.
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 that bleeds out to form a white powder. (4) The coefficient of friction of the molding material in a heated state is reduced, the suitability for an automatic bag is improved, the generation of wrinkles during heat sealing and the decrease in gloss due to sliding can be prevented, and a beautiful sealed portion can be obtained. (5) When used in combination with a light-shielding substance, the thermoplastic resin becomes cloudy and the haze is increased. As a result, the coloring power can be improved and the light-shielding ability can be improved. Nature can be secured.

An antioxidant can be contained in the inner conductive thermoplastic resin layer, outer conductive thermoplastic resin layer and intermediate thermoplastic resin layer. By containing an antioxidant, it prevents 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 and the like) which adversely affect the photographic light-sensitive material. Various known compounds (eg, hydantoin compounds, hydrazine compounds, urea compounds) that reduce, stabilize, stabilize the reaction, or stabilize the adsorption of pyrolytic substances (aldehydes, etc.) to an amount that does not adversely affect the photographic material. Is preferably added. 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.

The amount of the antioxidant added is 0.001-1.
5% by weight, preferably 0.005 to 0.7% by weight,
0.01 to 0.45% by weight is more preferable. The amount added is 0.
If the amount is less than 001% by weight, there is no effect of the addition and only the kneading cost increases. If the amount exceeds 1% by weight, the photographic properties of the photographic light-sensitive material utilizing the oxidation and reduction actions are adversely affected and molding is performed. Bleed out to the surface of the product and degrade the appearance.

Representative 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 antioxidant phenyl-α-naphthylamine, N-phenyl-β-naphthylamine, N-phenyl-N′-isopropylidyl-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, such as dilauryl thiodipropionate. Representative examples of the most preferred hindered phenolic antioxidants in 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-ter
t-butyl-3-hydroxy-2,6-di-methylbenzyl] isocyanurate, tetrakis (2,4-di-te
rt-butylphenyl) 4,4'-biphenylenediphosphite, 4,4'-thiobis- (6-tert-butyl-O-cresol), 2,2'-thiobis- (6-te
rt-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-t
tert-butylphenol), 2,6-di-tert-
Butyl-4-methylphenol, 4-hydroxymethyl-2,6-di-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 and the like. Melting point is 100 ° C
Above, especially those at 120 ° C. or higher are preferred. Further, it is effective to use it in combination with a phosphorus antioxidant. Furthermore, it is particularly preferable to use at least one of phosphorus-based antioxidants, at least one of hindered phenol-based antioxidants, and at least one of hydrotalcite compounds in total of three or more.

When at least one phosphorus-based antioxidant is contained, phosphorous acid generated by thermal decomposition greatly affects the photographic properties of the photographic light-sensitive material and generates fog, so that hydrotalcite neutralizes the phosphorous acid. Class compound.
It is preferably used in an amount of from 0.01 to 5.0% by weight, particularly from 0.05 to 3.0% by weight.

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 a film molded product to yellow, the light-shielding ability is reduced by carbon black. 10% more than the case of adding a light-shielding substance alone,
In addition, since the dispersibility is also improved, the amount of the light-shielding substance to be added is reduced to 1
Even if it is reduced by 0% or more, the same light shielding property can be obtained. As a result, various effects such as prevention of deterioration of photographic properties, improvement of physical strength, improvement of appearance, and reduction of material cost are exhibited.

Particularly preferred antioxidants are phenolic antioxidants, and commercially available products include various types of Irganox manufactured by Ciba-Geigy and Sumilize manufactured by Sumitomo Chemical Co., Ltd.
rBHT, Sumilizer BH-76, Sumi
lizer WX-R, Sumilizer BP-1
01 and so on. Also, 2,6-di-t-butyl-p-cresol (BHT), a low-volatility, high molecular weight phenolic antioxidant (trade name: Ireganox 1010, I
reganox 1076, TopanolCA, Io
nox 330). These phenolic antioxidants include phosphorus antioxidants (distearyl-pentaerythritol-diphosphite, tris (nonylphenyl) phosphite, bis (2,4, di-t-butylphenyl) pentaerythritol phosphite. , Dilaurylthiodipropionate, distearylthiopropionate, tetrakis (2,4-di-t-butylphenyl) 4,
4'-biphenylene-di-phosphonite, tris (2,
4-di-t-butyl-phenyl) phosphite, dialkyl phosphate, etc.), and in particular, the use of two or more thereof in combination is effective because it exhibits a surplus effect.

In particular, at least one of the above hindered phenolic antioxidants having a melting point of 100 ° C. or more, preferably 120 ° C. or more, which is a typical example of a free radical chain terminator, and a phosphorus 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 material of the present invention is particularly advantageous in that it has many excellent properties such as little adverse effect on the photographic properties of the photographic light-sensitive material, little thermal decomposition even at a resin melting temperature (130 to 400 ° C.), and little bleed-out over time. Preferred antioxidants are hindered phenolic antioxidants having a molecular weight of 200 or more, preferably 300 or more, particularly preferably 400 or more, and most preferably 500 or more.

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-phenyl) propionate] methane, n -Octadecyl-
3- (4'-Hydroxy-3 ', 5'-di-t-butylphenol) propionate and tris- (2,4-di-t-
(Butylphenyl) phosphite.

The volume specific resistance values of the inner conductive thermoplastic resin layer and the outer conductive thermoplastic resin layer (20 ° C., 60%
RH) is preferably 1 × 10 ¹² Ω · cm or less, more preferably 1 × 10 10 Ω · cm or less, particularly preferably 1 × 10 ⁷ Ω · cm or less, and 1 × 10 ⁵ Ω · cm. Most preferably, it is Ω · cm or less. Volume specific resistance (20 ° C., 60% RH) is 1 × 1
If it exceeds 0 ¹² Ω · cm, it is difficult to secure sufficient antistatic properties, and static marks and the like are likely to be generated on the photographic material.

The volume specific resistance is a kind of electric resistance of a substance, and is an electric resistance inside the sample. That is, it is a value obtained by converting the volume resistance per unit volume, and
6911.

The intermediate thermoplastic resin layer is preferably formed of an oxygen barrier thermoplastic resin. The intermediate thermoplastic resin layer molded with an oxygen barrier thermoplastic resin has impermeability to oxygen, improves physical strength, and impairs photographic properties, which is the most important quality of packaged photographic materials. As a result, a high-sensitivity photosensitive material having an ISO sensitivity of 400 or more can be maintained in good quality for a long period of two years or more. As the oxygen-barrier thermoplastic resin, ethylene-vinyl alcohol copolymer resin, high-density polyethylene resin, polypropylene resin, polyvinylidene chloride copolymer resin, polyethylene terephthalate resin, amorphous polyethylene terephthalate resin,
Examples include polyethylene naphthalate resin, polybutylene terephthalate resin, polyamide resin, polyacrylonitrile resin, and the like.

Oxygen permeability (JIS K-712) of an intermediate thermoplastic resin layer formed of an oxygen barrier thermoplastic resin
6 at 20 ° C., 0% RH) is 2000 cc / m ²
・ 24hrs ・ atm or less, 1500cc / m ²・ 24
hrs.atm or less, preferably 1000 cc / m ^2.
24 hrs.atm or less is more preferable, and 500 cc / atm.
m ² · 24 hrs · atm or less is particularly preferable, and 250
Most preferably, it is not more than cc / m ² · 24 hrs · atm.

The Young's modulus of the intermediate thermoplastic resin layer is preferably larger than the Young's modulus of the inner conductive thermoplastic resin layer and the outer conductive thermoplastic resin layer. By making the Young's modulus of the intermediate thermoplastic resin layer larger than the Young's modulus of the inner conductive thermoplastic resin layer and the outer conductive thermoplastic resin layer, the film forming suitability can be improved and curling can be prevented. be able to. Further, the impact drilling strength, bag breaking strength, pinhole resistance and the like can be improved.

Young's modulus in the longitudinal direction of the intermediate thermoplastic resin layer
(JIS K 7127) is 30 kgf / mm ² or more, 5
0 kgf / mm ² or more is preferable, and 100 kgf / mm ²
Or more, and particularly preferably 150 kgf / mm ² or more, 200 kgf / mm ² or more it is most preferred.
The longitudinal Young's modulus of the intermediate thermoplastic resin layer is preferably at least 10 kgf / mm ² greater than the longitudinal Young's modulus of the inner conductive thermoplastic resin layer and the outer conductive thermoplastic resin layer, and is preferably 20 kgf / mm ^2. it is more preferable mm ² or more greater, particularly preferably 40 kgf / mm ² or more large, and most preferably 80 kgf / mm ² or more greater.

The intermediate thermoplastic resin layer is formed by mixing recycled resin produced from the simultaneous multilayer co-extruded film with 5 to 5.
It is preferable to contain 100% by weight because the container and packaging recycling method can be cleared without deteriorating photographic properties. Furthermore, by using recycled resin manufactured from simultaneous multilayer co-extruded film for the intermediate thermoplastic resin layer, dispersibility of carbon black, film moldability,
The antistatic property, light-shielding property and photographic property can be improved, and as a result, the thickness can be reduced by 10% or more. It is considered that such an effect of improving the photographic properties is a result of a drastic reduction in volatile components that adversely affect the photographic properties, since the recycled resin has passed through three or more thermal histories.

The inner conductive thermoplastic resin layer and the outer conductive thermoplastic resin layer have conductivity when various additives are added. Among the additives for imparting conductivity, conductive inorganic pigments are used. , Conductive fibrous substances (such as fibers and whiskers),
It preferably contains at least one of a metal filler and a surfactant-based surfactant. By containing these substances, the antistatic property, the lubricating property, the bleed-out of the lubricant, the drip-proof property, the kneading property of the light-shielding substance and the additive, the fluidity of the resin composition, the blocking prevention are improved. Can be achieved.

The conductive inorganic pigment can be used by selecting from the inorganic pigments described in the description of the light-shielding substance.

Examples of the conductive fibrous substance include carbon whiskers, nickel whiskers, chromium whiskers, and iron whiskers, in addition to carbon fibers, alumina fibers, nickel fibers, surface metallized (such as Al coat, Ni coat, and Ag coat) fibers. Whisker (fine fibrous single crystal) such as copper whisker, alumina whisker, potassium titanate whisker, silicon carbide whisker, silicon nitride whisker
There is. Particularly preferred are carbon fibers, surface metallized fibers, and potassium titanate whiskers (typical examples are Otsuka Chemical's Tismo).

As the metal filler, the light-shielding substance
Aluminum, zinc, tin, iron,
Metal powder such as copper, nickel, silver, stainless steel, lead, etc., aluminum
Metals such as nickel, zinc, copper, nickel, silver, stainless steel
In addition to flakes, aluminum, zinc, iron, copper, nickel
Etc. There are metal ribbons. ZnO, TiO_Two, SnO
_Two, Al_TwoO_Three, In_TwoO_Three, SiO_Two, MgO, BaO, M
oO_Three, V_TwoO_FiveOr other crystalline metal oxides
Of the composite oxide.

Now, the surfactant will be described.

Representative examples of the nonionic surfactant are shown below. Polyethylene glycol fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene alkyl ether, polyoxyethylene alkylamine, polyoxyethylene alkylamine fatty acid ester, polyoxyethylene aliphatic alcohol ether, polyoxyethylene alkylphenyl ether, polyoxyethylene Glycerin fatty acid ester, polyoxyethylene fatty amine, sorbitan monofatty acid ester, fatty acid ventaerythrit, fatty alcohol ethylene oxide adduct, fatty acid ethylene oxide adduct,
Fatty acid amino or fatty acid amide ethylene oxide adduct, alkylphenol ethylene oxide adduct, alkyl naphthol ethylene oxide adduct,
An ethylene oxide adduct of a partial fatty acid ester of a polyhydric alcohol, polyoxyethylene alkyl amide,
Alkylamine derivatives, other JP-B-63-26697
No. 120, various nonionic antistatic agents and the like.

Representative examples of the anionic surfactant are shown below. Ricinoleic acid sulfate soda salt, various fatty acid metal salts, silinoleic acid ester soda ester salt, sulfated ethyl aniline sulfate, olefin sulfate salt, oleyl alcohol sulfate soda salt, alkyl sulfate ester salt, fatty acid ethyl sulfonate , Alkyl sulfate, alkyl phosphate, alkyl sulfonate, alkyl naphthalene sulfonate, alkyl benzene sulfonate, succinate sulfonate, phosphate ester salt and the like.

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

Representative examples of the amphoteric surfactant are shown below. Carboxylic acid derivatives, imidazoline derivatives, betaine derivatives and the like.

The amount of the surfactant added is preferably 0.01 to 5.0% by weight, more preferably 0.05 to 3.0% by weight, and most preferably 0.1 to 1.5% by weight. The amount added is 0.
If the amount is less than 01% by weight, the above-mentioned various effects of adding a surfactant cannot be exerted, and the cost of kneading only increases.
On the other hand, if the amount exceeds 5.0% by weight, foaming and pinholes are liable to occur, slipping between the molten resin and the screw of the extruder is liable to occur, and the amount of the resin discharged becomes unstable. The thickness fluctuation of the thickness increases. In addition, the bleed-out amount increases, stickiness and blocking easily occur, and practical use becomes difficult.

Draw ratio of the simultaneous multilayer co-extruded film (numerical value obtained by dividing the thickness of the opening of the die by the thickness of the film)
Is preferably 3 to 120, more preferably 5 to 100, particularly preferably 7 to 80, and most preferably 9 to 60. Draw ratio is 3
If the amount is less than the above, drawdown and cooling failure occur, and it is difficult to form a film. On the other hand, when the draw ratio exceeds 120, the molecular orientation becomes too large, and the variation in the film thickness becomes large, which makes practical use difficult.

A flexible sheet layer can be laminated on the outer conductive thermoplastic resin layer indirectly via an adhesive layer or directly without via an adhesive layer.

As the flexible sheet layer, various thermoplastic resin films, for example, various polyethylene resins,
Various ethylene copolymer resins, polypropylene resins, various propylene copolymer resins, polyvinyl chloride resins, various polyamide resins, polyacrylonitrile resins, ethylene
Vinyl alcohol copolymer resin, polycarbonate resin, various polyester resins (PET resin, PBT resin,
PEN resin) and modified resin films thereof, as well as uniaxially or biaxially stretched films of these various thermoplastic resin films. Also, triacetate film, cellophane, regenerated cellulose film,
There are paper, synthetic paper, nonwoven fabric, metal foil, metal-deposited film, inorganic substance-deposited film, metal-deposited paper, and the like.

A particularly preferred flexible sheet has a basis weight of 20 to 400 g / m which does not adversely affect the photographic light-sensitive material.
² Various neutral and acidic papers (waste paper, recycled paper, unbleached kraft paper, semi-bleached kraft paper, bleached kraft paper,
Biaxial drawing with clupak paper, duo stress paper, white paperboard, photographic base paper, high quality paper, medium paper using high yield pulp, pure white roll paper, coated paper, imitation paper, glassine paper), nonwoven fabric, synthetic paper It is a thermoplastic resin film.

These flexible sheets can be used singly or in combination of two or more kinds. The fact that the melting point is higher by 10 ° C. or more than that of the heat-sealed (inside conductive thermoplastic resin) layer improves bag suitability. Prevent wrinkles and tears,
It is preferable from the viewpoint of improving the appearance. Particularly preferred is a biaxially stretched thermoplastic resin film having a thickness of 5 to 70 μm, preferably 7 to 50 μm, and particularly preferably 10 to 35 μm. The Young's modulus of the flexible sheet is 50 kg /
mm ² or more, preferably 70 kg / mm ² or more, particularly preferably 90 kg / mm ² or more, and most preferably 100 k / mm ² or more.
g / mm ² or more, and is a sheet of the intermediate thermoplastic resin layer or more.

Examples of the metal foil include aluminum foil, lead foil, iron foil, tin foil, zinc foil, electrolytic iron foil, copper foil, and stainless steel foil.
The thickness is preferably from 5 to 100 μm, and particularly preferably from 7 to 50 μm in consideration of economy, handling, and securing characteristics.
0 μm is most preferred. In addition, thermoplastic resin films and dust-free flexible sheets (dust-free paper, synthetic paper, non-woven paper,
Glassine paper, cellophane, surface-size or surface-coated paper) and a flexible sheet made of a metal thin film obtained by further providing a metal thin film processing layer on these flexible sheets are also preferable.
Further, a flexible sheet processed with an inorganic oxide thin film provided with a layer processed with an inorganic oxide thin film such as glass or alumina is also preferable. Recently, a flexible sheet made of lead foil, iron foil, electrolytic iron foil, etc. with a thickness of 10 to 200 μm has been used to prevent X-ray irradiation on high-sensitivity photographic film during the baggage inspection of overseas travel and to prevent occurrence of cover. It is also preferable to laminate them.

The adhesive layer can be formed by a wet lamination method, a dry lamination method, a hot melt lamination method, an extrusion lamination method, a co-extrusion extrusion lamination method, or the like. Examples of the resin constituting the adhesive layer include various thermoplastic resins having a small amount of volatile substances which easily affect the photographic light-sensitive material, in particular, low-density homopolyethylene resin, L-LDPE resin, EEA resin, and EA.
A resin, EVA resin, acid-modified polyolefin resin, various polypropylene copolymer resins, and a blend resin mainly composed of these resins are preferable.

A flexible sheet layer can be laminated on the inner conductive thermoplastic resin layer indirectly via an adhesive layer or directly without via an adhesive layer. As the flexible sheet layer, a flexible sheet laminated on the outer conductive thermoplastic resin layer can be used, but a sheet having good heat resistance and dust resistance is preferable. Further, a flexible sheet excellent in printability and antistatic property is particularly preferable. Further, the same adhesive layer as that of the outer conductive thermoplastic resin layer can be used as the adhesive layer.

The application to which the packaging material for photographic light-sensitive 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, film for printing plate making, cut film for photographing, X-ray film, PS plate (Japanese Patent Laid-Open No. 8-254793)
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 overwrapping packages. 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.

The photographic light-sensitive materials to which the photographic light-sensitive material packaging material of the present invention can be applied are shown below.

(1) Silver halide photographic light-sensitive material (printing film, color or black-and-white photographic paper, color or black-and-white negative film, printing master paper, DTR (diffusion transfer)
Photosensitive material, computer typesetting film and paper, color or black-and-white positive film, color reversal film, microfilm, surveillance film, movie film, self-developing photographic photosensitive material, direct positive film and paper, etc.)

(2) Heat-developable light-sensitive materials (heat-developable color light-sensitive materials, heat-developable black-and-white light-sensitive materials (for example, JP-B-43-492)
Nos. 1 and 43-4924, "Basics of Photographic Engineering", pp. 553 to 555 of Silver halide photography (Corona Publishing Co., 1879), and Research Tis Closure Magazine 19
What is described in June, 1978, pages 9 to 15 (RD-17029). Further, a transfer type heat-developable color photographic light-sensitive material described in JP-A-59-12431, JP-A-60-2950, JP-A-61-52343 and U.S. Pat. No. 4,584,267. etc))

(3) Photosensitive / thermosensitive recording material (Japanese Unexamined Patent Publication No.
Recording material using photothermography (photosensitive / thermosensitive image forming method) described in, for example, US Pat.

(4) Diazonium photographic material (4-morpholinobenzenediazonium microfilm, microfilm, copy film, printing plate, etc.)

(5) Azide and diazide photographic light-sensitive materials (light-sensitive materials containing para-azide benzoate, 4,4'-diazidostilbene, etc., such as copying films and printing plates)

(6) Quinonediazide photographic light-sensitive materials (orthoquinonediazide, orthonaphthoquinonediazide compounds such as benzoquinone (1,2) -diazide-
(2) Photosensitive materials containing -4-sulfonic acid phenyl ether and the like, for example, printing plates, copying films, adhesion films, etc.)

(7) Photopolymer (photosensitive material containing vinyl monomer, etc., printing plate, adhesive film, etc.)

(8) Polyvinylcinnamate-based photosensitive materials (eg, printing films, IC resists, etc.)

The embodiment of the packaging material for photographic light-sensitive material according to the present invention will be described with reference to the drawings.

FIGS. 1 to 21 are partial cross-sectional views each showing a layer structure of an embodiment of a packaging material for a photographic light-sensitive material.

The packaging material for a photographic photosensitive material shown in FIG. 1 comprises an inner conductive thermoplastic resin layer 1a containing a light-shielding substance, an intermediate thermoplastic resin layer 2a containing a light-shielding substance, and an outer conductive thermoplastic resin layer 2a containing a light-shielding substance. It comprises a three-layer co-extruded film IIIa in which a plastic resin layer 3a is laminated by co-extrusion.

The packaging material for a photographic photosensitive material shown in FIG. 2 has an inner conductive thermoplastic resin layer 1a containing a light-shielding substance, an intermediate thermoplastic resin layer 2 containing no light-shielding substance, and an outer conductive resin layer containing a light-shielding substance. It is composed of a three-layer co-extruded film IIIa in which a thermoplastic resin layer 3a is laminated by co-extrusion.

The packaging material for a photographic photosensitive material shown in FIG. 3 has an inner conductive thermoplastic resin layer 1 containing no light-shielding substance, an intermediate thermoplastic resin layer 2a containing a light-shielding substance, and an outer conductive resin layer containing a light-shielding substance. It is composed of a three-layer co-extruded film IIIa in which a thermoplastic resin layer 3a is laminated by co-extrusion.

The packaging material for a photographic photosensitive material shown in FIG. 4 has two inner conductive thermoplastic resin layers 1a containing a light-shielding substance.
It comprises a simultaneous four-layer co-extruded film IVa in which an intermediate thermoplastic resin layer 2a containing a light-shielding substance and an outer conductive thermoplastic resin layer 3a containing a light-shielding substance are laminated by simultaneous co-extrusion.

The packaging material for a photographic photosensitive material shown in FIG. 5 includes an inner conductive thermoplastic resin layer 1a containing a light-shielding substance, an intermediate thermoplastic resin layer 2a containing a light-shielding substance, and an intermediate thermoplastic resin containing no light-shielding substance. It comprises a simultaneous four-layer coextruded film IVa in which a layer 2 and an outer conductive thermoplastic resin layer 3a containing a light-shielding substance are laminated by simultaneous coextrusion.

The packaging material for a photographic photosensitive material shown in FIG. 6 has an inner conductive thermoplastic resin layer 1 containing no light-shielding substance, an inner conductive thermoplastic resin layer 1a containing a light-shielding substance, and no light-shielding substance. A simultaneous five-layer co-extruded film Va in which an intermediate thermoplastic resin layer 2, an outer conductive thermoplastic resin layer 3a containing a light-shielding substance, and an outer conductive thermoplastic resin layer 3 not containing a light-shielding substance are laminated by co-extrusion. Consists of

The packaging material for photographic photosensitive material shown in FIG. 7 has an inner conductive thermoplastic resin layer 1 containing no light-shielding substance, an inner conductive thermoplastic resin layer 1a containing a light-shielding substance, and an intermediate layer containing a light-shielding substance. A five-layer co-extruded film Va in which a thermoplastic resin layer 2a, an intermediate thermoplastic resin layer 2 containing no light-shielding substance, and an outer conductive thermoplastic resin layer 3a containing a light-shielding substance are laminated by simultaneous co-extrusion. I have.

The packaging material for a photosensitive material shown in FIG. 8 has an inner conductive thermoplastic resin layer 1 containing no light-shielding substance, an inner conductive thermoplastic resin layer 1a containing a light-shielding substance, and an intermediate layer containing a light-shielding substance. From a simultaneous five-layer co-extruded film Va in which a thermoplastic resin layer 2a, an outer conductive thermoplastic resin layer 3a containing a light-shielding substance and an outer conductive thermoplastic resin layer 3 not containing a light-shielding substance are laminated by simultaneous co-extrusion. Has become.

The packaging material for a photographic photosensitive material shown in FIG. 9 has three layers of an inner conductive thermoplastic resin layer 1a containing a light-shielding substance, three intermediate thermoplastic resin layers 2 containing no light-shielding substance, and a light-shielding substance. The outer conductive thermoplastic resin layer 3a is formed of a simultaneous five-layer co-extruded film Va laminated by simultaneous co-extrusion.

The packaging material for photographic light-sensitive material shown in FIG.
The flexible sheet layer 4 is laminated in a separate step on the outer conductive thermoplastic resin layer 3 or 3a of the simultaneous three-layer co-extruded film IIIa (packaging material for photographic photosensitive material shown in FIGS. 1 to 3).

The packaging material for photographic light-sensitive material shown in FIG.
Outer conductive thermoplastic resin layer 3 of simultaneous four-layer co-extruded film IVa (packaging material for photosensitive material shown in FIGS. 4 and 5)
Alternatively, the flexible sheet layer 4 is laminated on 3a in a separate step.

The packaging material for photographic light-sensitive material shown in FIG.
A flexible sheet layer 4 is laminated in a separate step on the outer conductive thermoplastic resin layer 3 or 3a of the simultaneous five-layer co-extruded film Va (packaging material for photographic photosensitive material shown in FIGS. 6 and 9).

The packaging material for photographic light-sensitive material shown in FIG.
A flexible sheet layer 4 is provided on the outer conductive thermoplastic resin layer 3 or 3a of the simultaneous three-layer co-extruded film IIIa (the packaging material for photographic photosensitive materials shown in FIGS. 1 to 3) via an adhesive layer 5.
Are laminated in a separate step.

The packaging material for photographic light-sensitive material shown in FIG.
Outer conductive thermoplastic resin layer 3 of simultaneous four-layer co-extruded film IVa (packaging material for photosensitive material shown in FIGS. 4 and 5)
Alternatively, a flexible sheet layer 4 is laminated on 3a via an adhesive layer 5 in another step.

The packaging material for photographic light-sensitive material shown in FIG.
A flexible sheet layer 4 is provided on the outer conductive thermoplastic resin layer 3 or 3a of the simultaneous five-layer co-extruded film Va (packaging material for photographic photosensitive material shown in FIGS. 6 to 9) with an adhesive layer 5 interposed therebetween.
Are laminated in a separate step.

The packaging material for photographic light-sensitive material shown in FIG.
The flexible sheet layer 6 is laminated in a separate step on the inner conductive thermoplastic resin layer 1 or 1a of the simultaneous three-layer co-extruded film IIIa (packaging material for photographic photosensitive material shown in FIGS. 1 to 3).

The packaging material for photographic light-sensitive material shown in FIG.
Inside conductive thermoplastic resin layer 1 of simultaneous four-layer co-extruded film IVa (packaging material for photographic photosensitive material shown in FIGS. 4 and 5)
a, a flexible sheet layer 6 is laminated in a separate step.

The packaging material for photographic light-sensitive material shown in FIG.
The flexible sheet layer 6 is laminated in a separate step on the inner conductive thermoplastic resin layer 1 or 1a of the simultaneous five-layer co-extruded film Va (the packaging material for photographic photosensitive materials shown in FIGS. 6 to 9).

The packaging material for photographic light-sensitive material shown in FIG.
A flexible sheet layer containing a light-shielding substance via an adhesive layer 5 on an inner conductive thermoplastic resin layer 1 or 1a of a simultaneous three-layer co-extruded film IIIa (packaging material for photographic photosensitive material shown in FIGS. 1 to 3). 6a is laminated in a separate step.

The packaging material for photographic light-sensitive material shown in FIG.
Inside conductive thermoplastic resin layer 1 of simultaneous four-layer co-extruded film IVa (packaging material for photographic photosensitive material shown in FIGS. 4 and 5)
a, a flexible sheet layer 6a containing a light-shielding substance is laminated via an adhesive layer 5 in a separate step.

The packaging material for a photographic light-sensitive material shown in FIG.
A flexible sheet layer containing a light-shielding substance via an adhesive layer 5 on an inner conductive thermoplastic resin layer 1 or 1a of a five-layer coextruded film Va (packaging material for photographic photosensitive material shown in FIGS. 6 to 9). 6a is laminated in a separate step.

In the wrapping material for photographic light-sensitive material as described above, when wrapping the photographic light-sensitive material, the photographic light-sensitive material is placed on the lower side in the drawing, that is, the inner conductive thermoplastic resin layer 1 or 1a is added to the photographic light-sensitive material. It is arranged so that it may touch.

[0250]

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to the following examples unless it exceeds the gist of the present invention.

Example 1 The packaging material for photographic light-sensitive material of Example 1 was made of a simultaneous three-layer co-extruded blown film shown in FIG. 1 and had a thickness of 70 μm and an outer conductive thermoplastic resin layer 3a. Has an MFR of 0.9 g / 10 min polymerized using a Ziegler catalyst and a density of 0.9.
53 g / cm ³ , molecular weight distribution 25, crystallinity 82%
30 parts by weight of a high-density polyethylene resin having a MFR of 4 g / 10 produced by a gas phase method using a metallocene catalyst.
, An ethylene-hexene 1 copolymer resin having a density of 0.915 g / cm ³ , a crystallinity of 38% and a molecular weight distribution of 2.7, an MFR of 3 g / 10 min, and a density of 0.90.
0 g / cm ³ , molecular weight distribution of 2.1, low crystallinity ethylene-butene 1 copolymer resin having a crystallinity of 25%, 100 parts by weight of polyolefin resin having 30 parts by weight, DBP oil absorption of 168 cc / 100 g, average Particle size 40mμ, pH
Of 18% by weight of acetylene carbon black having a free sulfur content of 0.02% and a volatile matter content of 0.2%, a surface-coated titanium dioxide of 5 parts by weight, and a calcium stearate of 0.2 parts by weight; Dimethylpolysiloxane is 0.
1 part by weight, octadecyl-3- (3,5
0.1 part by weight of (-di-t-butyl-4-hydroxyphenyl) propionate, 0.9% by weight of a synthetic A-type zeolite supporting silver ions, having a specific surface area of 170 m ² / g and an average particle diameter of 1 μm. 20 μm thick resin layer made of a light-shielding / conductive polyolefin resin composition.

The intermediate thermoplastic resin layer 2a has an MFR produced by polymerization using a Ziegler catalyst of 0.06 g / 10 minutes,
35 parts by weight of a high-density polyethylene resin having a density of 0.951 g / cm ³ , a molecular weight distribution of 25, and a crystallinity of 81%,
MFR produced by polymerization using a Ziegler catalyst is 2 g / 1
0 min, density 0.920 g / cm ³ , molecular weight distribution 3.
7, based on 100 parts by weight of a polyolefin resin containing 65 parts by weight of an ethylene-butene 1 copolymer resin having a crystallinity of 51%, a DBP oil absorption of 124 cc / 100 g, an average particle diameter of 20 mμ, and a pH of 8.4; Free sulfur content of 0.05
%, 3 parts by weight of furnace carbon black having a volatile content of 0.8%, 0.1 part by weight of calcium stearate, 0.05 part by weight of erucamide, a hindered phenolic antioxidant (manufactured by Ciba Geigy) (Irganox 1010)) 0.1 part by weight of synthetic silica and 0.5 part by weight of a polyolefin resin composition having a thickness of 30
It is a resin layer of μm.

The inner conductive thermoplastic resin layer 1a is obtained by changing the content of 100 parts by weight of the polyolefin resin constituting the outer conductive thermoplastic resin layer 3a from 40 parts by weight of high-density polyethylene resin to 10 parts by weight. The ethylene-hexene copolymer resin was changed from 40 parts by weight to 70 parts by weight, and the low-crystalline ethylene-butene 1 copolymer resin was directly changed to 20 parts by weight. The type and amount of the additive and the thickness (20 μm) of the resin layer are the same.

In addition, this simultaneous three-layer co-extrusion blown film was formed at a film forming speed of 2 mm using a ring die having a lip gap (near the opening of the die) of 2.5 mm.
Molded to 70 μm at 0 m / min, draw ratio (ratio of die lip gap to actual thickness of film)
2500 μm (2.5 mm near the lip) / 70 μm was about 36.

The packaging material for a photographic light-sensitive material composed of the above-described three-layer simultaneous multi-layer co-extrusion blown film is suitable for film formability, antistatic property, light-shielding ability, physical strength, appearance, suitability for recycling, heat-sealing suitability. It has excellent sealing properties, bag breaking strength, carbon black dispersibility, incineration suitability, and moisture resistance, and can be used as it is without using a metal foil or the like as a packaging material for high-sensitivity photographic photosensitive materials having an ISO sensitivity of 100 or more. The cost was reduced by 40% or more compared to a comparative product in which layers were laminated.

Example 2 The packaging material for photographic light-sensitive material of Example 2 was formed of a simultaneous three-layer co-extruded blown film shown in FIG. 2 and had a thickness of 60 μm and an inner conductive thermoplastic resin layer 1a. The outer conductive thermoplastic resin layer 3a is a 20 μm thick resin layer made of the same light-shielding and conductive polyolefin resin composition as in Example 1.

The intermediate thermoplastic resin layer 2 has an MFR of 1 g /
10 minutes, density 0.935 g / cm ³ , molecular weight distribution 3.
5 0.3% by weight of maleic anhydride in a molten state in ethylene-4 methylpentene 1 copolymer resin having a crystallinity of 53%.
35 parts by weight of the grafted modified ethylene / α-olefin copolymer resin and a polyamide resin (“N
OVAMID # 1023 ") is a resin layer having a thickness of 20 μm and made of a polyamide resin-based oxygen barrier thermoplastic resin composed of 65 parts by weight.

Further, in this simultaneous three-layer co-extrusion blown film, the inside was cooled with a water-cooled mandrel cooled with cooling water at 10 ° C., and the outside was cooled by blowing air at 20 ° C.

The packaging material for photographic light-sensitive material comprising the above-described three-layer simultaneous multi-layer coextrusion blown film is superior to the photographic light-sensitive material packaging material of Example 1 in oxygen barrier properties and bag breaking strength. Excellent in gel-botest strength (pinhole resistance), Young's modulus, impact drilling strength, etc., especially, the quality of high-sensitivity photographic materials with ISO sensitivity of 400 or more and photographic materials using gold sensitization or sensitizing dyes Is an excellent packaging material that can be maintained well for a long period of two years or more.

[0260] This simultaneous three-layer co-extrusion blown film was formed to 60 µm at a film forming speed of 10 m / min using a ring die having a lip gap of 1.5 mm. The ratio (thickness ratio of the obtained film) of 1500 μm (1.5 mm near the lip) / 60 μm was 25.

Example 3 The packaging material for a photographic light-sensitive material of Example 3 was a co-extruded three-layer co-extruded blown film shown in FIG. 1 and had a thickness of 70 μm and an inner conductive thermoplastic resin layer 1a. The outer conductive thermoplastic resin layer 3a is a 20 μm thick resin layer made of the same light-shielding and conductive polyolefin resin composition as in Example 1.

The intermediate thermoplastic resin layer 2 was formed by recycling the pelletized inflation film of the three-layer co-extruded inflation film of Example 1 with a virgin polyolefin resin 1.
It contained 100 parts by weight (50% by weight) with respect to 00 parts by weight, and the other additives were the same as in Example 1.

The photographic light-sensitive material packaging material of Example 3 is a polyolefin-based resin composition obtained by recycling the entire photographic light-sensitive material packaging material of Example 1 into an intermediate thermoplastic resin layer 2 into pellets at least three times. Was used, which was more environmentally friendly than that of Example 1, and used carbon black dispersibility, antistatic property, light-shielding ability, and photographic properties. It is considered that the volatile components which adversely affect the photographic properties were largely reduced.)

Example 4 The packaging material for photographic light-sensitive material of Example 4 was a simultaneous three-layer co-extruded blown film having a thickness of 60 μm and an inner conductive thermoplastic resin layer 1a as shown in FIG. The outer conductive thermoplastic resin layer 3a is a 20 μm thick resin layer made of the same light-shielding and conductive polyolefin resin composition as in Example 2.

The intermediate thermoplastic resin layer 2 was formed by recycling the pelletized inflation film of the three-layer co-extruded inflation film of Example 2 with respect to 100 parts by weight of the same polyamide resin-based oxygen barrier thermoplastic resin as in Example 2. Fifteen
0 parts by weight (60% by weight).

The packaging material for photographic light-sensitive material of Example 4 is also a polyamide resin-based oxygen barrier obtained by recycling the entire photographic light-sensitive material packaging material of Example 2 into the intermediate thermoplastic resin layer 2 three times or more. Since the thermoplastic resin composition was used, it was environmentally friendly as compared with Example 2, and the dispersibility of carbon black, antistatic properties, light-shielding ability, and photographic properties (because a resin that passed through a heat history three times or more was used. It is considered that the volatile components which adversely affect the photographic properties of the photographic light-sensitive material were greatly reduced.)

[0267]

According to the present invention, the antistatic property, the physical strength and the light-shielding property can be improved even if it is constituted only by the simultaneous multi-layer co-extruded film mainly composed of the conductive thermoplastic resin. It can be used as a packaging material for photographic light-sensitive materials having excellent performance, curl, and manufacturing suitability, and also has excellent recyclability, incineration suitability, and reuse suitability. Furthermore, since it can be manufactured only by the simultaneous multilayer co-extrusion film forming step and can be formed by a manufacturing method having excellent productivity, the cost can be reduced by 40% or more.

[Brief description of the drawings]

FIG. 1 is a partial cross-sectional view showing a layer structure of an embodiment of a packaging material for a photographic photosensitive material according to the present invention.

FIG. 2 is a partial cross-sectional view showing a layer configuration of another embodiment of the packaging material for a photographic light-sensitive material according to the present invention.

FIG. 3 is a partial cross-sectional view showing a layer configuration of another embodiment of the packaging material for a photographic light-sensitive material according to the present invention.

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

FIG. 5 is a partial cross-sectional view showing a layer configuration of another embodiment of the packaging material for a photographic light-sensitive material according to the present invention.

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

FIG. 7 is a partial cross-sectional view showing a layer structure of another embodiment of the packaging material for a photographic light-sensitive material according to the present invention.

FIG. 8 is a partial cross-sectional view showing a layer structure of another embodiment of the packaging material for a photosensitive material according to the present invention.

FIG. 9 is a partial cross-sectional view showing a layer configuration of another embodiment of the packaging material for a photographic light-sensitive material according to the present invention.

FIG. 10 is a partial cross-sectional view showing a layer structure of another embodiment of the packaging material for a photographic light-sensitive material according to the present invention.

FIG. 11 is a partial cross-sectional view showing a layer structure of another embodiment of the packaging material for a photographic light-sensitive material according to the present invention.

FIG. 12 is a partial cross-sectional view showing a layer structure of another embodiment of the packaging material for a photographic light-sensitive material according to the present invention.

FIG. 13 is a partial cross-sectional view showing a layer structure of another embodiment of the packaging material for a photographic light-sensitive material according to the present invention.

FIG. 14 is a partial cross-sectional view showing the layer structure of another embodiment of the packaging material for a photosensitive material according to the present invention.

FIG. 15 is a partial cross-sectional view showing a layer structure of another embodiment of the packaging material for a photosensitive material according to the present invention.

FIG. 16 is a partial cross-sectional view showing a layer structure of another embodiment of the packaging material for a photographic light-sensitive material according to the present invention.

FIG. 17 is a partial cross-sectional view showing a layer structure of another embodiment of the packaging material for a photographic light-sensitive material according to the present invention.

FIG. 18 is a partial cross-sectional view showing a layer structure of another embodiment of the packaging material for a photographic light-sensitive material according to the present invention.

FIG. 19 is a partial cross-sectional view showing a layer structure of another embodiment of the packaging material for a photographic light-sensitive material according to the present invention.

FIG. 20 is a partial cross-sectional view showing a layer structure of another embodiment of the packaging material for a photographic light-sensitive material according to the present invention.

FIG. 21 is a partial cross-sectional view showing a layer configuration of another embodiment of the packaging material for a photosensitive material according to the present invention.

[Explanation of symbols]

 1, 1a Inner conductive thermoplastic resin layer 2, 2a Intermediate thermoplastic resin layer 3, 3a Outer conductive thermoplastic resin layer 4 Flexible sheet layer 5 Adhesive layer 6a Flexible sheet layer IIIa Simultaneous three-layer co-extruded film IVa Simultaneous 4 Layer co-extruded film Va Simultaneous five-layer co-extruded film

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification code FI Theme coat ゛ (Reference) G03C 3/00 560 G03C 3/00 560P

Claims (8)

[Claims] 1. An inner conductive thermoplastic resin layer, an outer conductive thermoplastic resin layer, and an intermediate thermoplastic laminated between the inner conductive thermoplastic resin layer and the outer conductive thermoplastic resin layer. A packaging material for a photographic light-sensitive material, comprising a simultaneous multilayer co-extruded film having a resin layer. 2. The volume specific resistance (20 ° C., 60 ° C.) of the inner conductive thermoplastic resin layer and the outer conductive thermoplastic resin layer.
% RH) is 1 × 10 ¹² Ω · cm or less. 3. The photographic photosensitive material according to claim 1, wherein the inner conductive thermoplastic resin layer, the outer conductive thermoplastic resin layer, and the intermediate thermoplastic resin layer are molded with a polyolefin resin as a main component. Packaging material. 4. The thermoplastic resin according to claim 1, wherein the inner conductive thermoplastic resin layer and the outer conductive thermoplastic resin layer are a thermoplastic elastomer, an ethylene copolymer resin having a crystallinity of 40% or less as measured by an X-ray diffraction method, and an acid-modified resin. 3. The packaging material for a photographic light-sensitive material according to claim 1, wherein the packaging material contains 3 to 49% by weight of at least one polyolefin resin and 0.1 to 60% by weight of carbon black. 5. The packaging material for a photographic photosensitive material according to claim 1, wherein the intermediate thermoplastic resin layer is formed of an oxygen barrier thermoplastic resin. 6. The Young's modulus of the intermediate thermoplastic resin layer is as follows:
The inner conductive thermoplastic resin layer and the outer conductive thermoplastic resin layer each have a Young's modulus larger than that of the first conductive thermoplastic resin layer.
6. The packaging material for a photographic light-sensitive material according to 4 or 5. 7. The intermediate thermoplastic resin layer is made of recycled resin produced from the simultaneous multilayer co-extruded film.
The packaging material for a photographic light-sensitive material according to claim 1, wherein the wrapping material comprises from 100 to 100% by weight. 8. The method according to claim 1, wherein the inner conductive thermoplastic resin layer and the outer conductive thermoplastic resin layer are each made of one of a conductive inorganic pigment, a conductive fibrous substance, a metal filler and a surfactant-based surfactant.
8. A packaging material for a photographic light-sensitive material according to claim 1, wherein the packaging material contains at least one species.