JP2001296639A - Packaging material for photographic sensitve material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a packaging material for a photographic sensitive material, which has superior heat sealability and physical strength, improves aptitude for film shaping and appearance and does not adversely affect the photographic properties of the photographic sensitive material. SOLUTION: The packaging material has a light shielding polyolefin resin film layer, containing 0.01-20 parts (by mass) gas-adsorbing material which adsorbs gases, each having a harmful effect on photographic properties, 0.01-2 parts lubricant, 0.01-25 parts hydrotalcite compound and 0.1-40 parts light- shielding material, with respect to 100 parts polyolefin resin.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a heat-sealing suitability, film moldability, physical strength and appearance, and
The present invention relates to a packaging material for photographic light-sensitive materials that does not adversely affect the photographic properties of the photographic light-sensitive material.

[0002]

2. Description of the Related Art Conventionally, as a packaging material for packaging a photographic photosensitive material such as a photographic film, those having various resin compositions have been used. For example, Japanese Patent Publication No. 2-2700 proposes a packaging film provided with a light-shielding film containing 1% by mass or more of a light-shielding substance and 50% by mass or more of an L-LDPE resin. Also, JP-A-8-17
No. 9473 proposes a polymer resin packaging material for a photographic photosensitive material formed of a polymer material having a low molecular weight polymer content of 3% by mass or less produced using a metallocene catalyst.

[0003]

However, when the packaging film proposed in Japanese Patent Publication No. 2-2700 mentioned above contains a light-shielding substance, the physical strength and heat-sealing suitability are extremely excellent, and the thickness of the film can be reduced. Although it became possible, when the thickness was 50 μm or more, the melt viscosity increased, and it was difficult to increase the film forming speed.

A polymer resin packaging material for photographic light-sensitive materials proposed in Japanese Patent Application Laid-Open No. 8-179473 has a narrow molecular weight distribution and excellent physical strength and anti-blocking properties. The melt viscosity was higher than that of the L-LDPE resin produced using the Ziegler catalyst, and melt fracture occurred unless the film forming speed was reduced. When the resin temperature is increased to increase the film forming speed, an aldehyde compound is generated due to thermal deterioration, and photographic properties are deteriorated (abnormal occurrence of sensitivity, gradation, coloring, etc., and increase in fogging).

[0005] As described above, polyolefin resins produced by various polymerization methods have advantages and disadvantages, and it has been difficult to ensure the most desirable properties required for packaging materials for photographic photosensitive materials.

The present invention has excellent heat sealing suitability and physical strength as a packaging material for photographic photosensitive materials by maximizing the advantages of polyolefin resins produced by various polymerization methods and minimizing the disadvantages. Further, it is an object of the present invention to provide a packaging material for photographic light-sensitive materials which has good film forming suitability and appearance and does not adversely affect the photographic properties of the photographic light-sensitive material.

[0007]

The packaging material for photographic light-sensitive material of the present invention is based on 100 parts by mass of a polyolefin resin.
0.01 to 20 parts by mass of a gas adsorbing substance that adsorbs a gas that adversely affects photographic properties, 0.01 to 2 parts by mass of a lubricant, 0.01 to 25 parts by mass of a hydrotalcite-based compound, 0.1 to 25 parts by mass of a light shielding material A light-shielding polyolefin resin film layer containing 40 parts by mass is provided.

In the packaging material for a photographic light-sensitive material of the present invention, the heat-sealing suitability, physical strength, film forming suitability, appearance, etc. are greatly improved by a light-shielding polyolefin resin film layer having a specific composition. The ultra-precision quality can be stored in a good state for a long time without adversely affecting the photographic properties of the film.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION The packaging material for a photographic light-sensitive material of the present invention has a light-shielding polyolefin resin film layer, and this light-shielding polyolefin resin film adversely affects photographic properties with respect to 100 parts by mass of the polyolefin resin. 0.01 to 20 parts by mass of a gas adsorbing substance for adsorbing gas, 0.01 to 2 parts by mass of a lubricant, and 0.1 to 2 parts by mass of a hydrotalcite compound.
It contains 0.1 to 25 parts by mass and 0.1 to 40 parts by mass of a light-shielding substance.

Examples of polyolefin resins include homopolyethylene resins, random and block copolymer resins of ethylene and one or more α-olefins, homopolypropylene resins, and propylene with one or more α-olefins.
-Random and block copolymer resin with olefin, acid-modified polyolefin resin, ethylene-acrylic acid copolymer resin, ionomer resin, ethylene-acrylate copolymer resin, ethylene-vinyl acetate copolymer resin, ethylene- There are propylene-butene-1 terpolymer resin, polyolefin-based thermoplastic elastomer and the like.

Of these polyolefin resins, ethylene resins, propylene resins, acid-modified polyolefin resins and polyolefin thermoplastic elastomers are preferred, ethylene copolymer resins and polyolefin thermoplastic elastomers are more preferred, and ethylene / α −
Olefin copolymer resins are most preferred.

A polyolefin resin produced by polymerization using a polymerization catalyst containing at least one selected from the group consisting of halogen compounds and metal compounds is preferred. By using such a catalyst, it is possible to reduce the amount of the polymerization catalyst that has a large adverse effect on the photographic properties of the photographic light-sensitive material.

Typical examples of the polymerization catalyst containing a halogen compound or a metal compound include a Ziegler catalyst of a black precipitate obtained when titanium tetrachloride and triethylaluminum are mixed in anhydrous hexane, and titanium trichloride and triethylaluminum in anhydrous hexane. Ziegler-Natta catalyst of black precipitate obtained by mixing in hexane, organic alkyl compounds of metals of groups I, II, III and IV, V, VI, VII
Family stereoregular polymerization catalyst comprising a combination of a metal salt of a trialkyl aluminum and a three-Natta catalyst comprising a mixture of titanium chloride, Phillips catalyst and the magnesium compound composed of a mixture of SiO ₂ -Al ₂ O ₃ -based and chromium oxide There are catalysts containing a reaction product with titanium halide and organoaluminum as components. 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.

As the organoaluminum compound, trie
Chill aluminum, triisobutyl aluminum, tri
-N-propyl aluminum, diethyl aluminum
Nochloride, diethylaluminum monobromide, etc.
There is. TiCl as titanium compound₄, TiBr,
TiI₄Such as titanium tetrahalide, Ti (OCH ₃)
Cl₃, Ti (OC₂H₅) Cl₃Trihalogenated
Lucoxy titanium, Ti (OCH₃)₂Cl₂, Ti (O
C₂H₅)₂Cl₂, Ti (OC₂H₅)₂Br₂Etc.
Dihalogenated alkoxytitanium, Ti (OCH₃)₃C
l, Ti (OC₂H₅)₃Cl, Ti (OC₂H₅)₃
Monohalogenated trialkoxy titanium such as Br
You.

Examples of the organomagnesium compound include ethylbutylmagnesium, diisobutylmagnesium, dihexylmagnesium, ethylmagnesium chloride and MgF ₂ , MgCl ₂ , MgBr ₂ , MgI _{2 and the} like. Examples of the vanadium compound include vanadium tetrachloride, vanadium oxytrichloride, diethoxymonochloride vanadate, and diethoxydichloride vanadate.

These halogen compounds and metal compounds remaining in the polyolefin resin as catalyst residues adversely affect the photographic properties of the silver halide photographic light-sensitive material, but one of fatty acid metal salts, silica, zeolites and hydrotalcite compounds. Species, preferably the sum of two or more
Addition of 1 to 20% by mass, preferably 0.05 to 15% by mass, particularly preferably 0.1 to 10% by mass can render the composition harmless. Most preferred is a polyolefin resin composition containing an ethylene / α-olefin copolymer resin to which at least one of synthetic zeolite and synthetic silica is added in an amount of 0.01 to 20% by mass.

Examples of the homopolyethylene resin (including an ethylene / α-olefin copolymer resin having an α-olefin content of less than 0.5% by mass in the present invention) include radical initiators such as oxygen and peroxide. Used, 150-300
A low-density branched polyethylene resin having a long-chain branching density of 0.910 to 0.925 g / cm ³ , produced by a method of polymerizing ethylene under a temperature and pressure condition of 1000 to 3000 kg / cm ^2. Manufactured by a method of polymerizing ethylene at a temperature and pressure of 50 to 250 ° C. and 50 to 200 kg / cm ² using a medium / low pressure Ziegler catalyst (Ti system) or a Phillips catalyst (Cr system) or the like.
A high-density polyethylene resin having a linear density of 0.941 to 0.985 g / cm ³ and a high-pressure method or a medium / low-pressure method can be obtained. There is a medium density polyethylene resin having a density of 0.926 to 0.940 g / cm ³ being manufactured. Further, there are homopolyethylene resins of various densities in which the molecular weight distribution and the composition distribution are reduced using a metallocene polymerization catalyst.

As the copolymer resin of ethylene and one or more α-olefins, a preferred resin in the present invention is an L-LDPE resin. This L-LDP
E (L inear L ow D ensity P oly e
Tilene resin is referred to as a third polyethylene resin, and has low cost and high strength that meet the demands of the times of energy saving, resource saving and prevention of global warming, combining the advantages of both the medium / low pressure method and the high pressure method. Resin.
This resin has ethylene and carbon number of 3-20, preferably 3-12, more preferably 4 by low pressure method or high pressure improvement method.
A copolymer obtained by copolymerizing from one to two or more α-olefins (one or two or more types) having a structure having a short linear-linear short-branched structure. It is a polyethylene resin.

Preferred α-olefins in terms of physical strength, production suitability and cost include propylene and butene
1, octene-1, hexene-1, pentene-1, 3-
Methylpentene-1, 4-methylpentene-1, 4-methylhexene-1, 4-dimethylpentene-1, heptene-1, nonene-1, decene-1, dodecene-1, tetracene-1, hexadecene-1, There are pentadecene-1, octadecene-1, eicosene-1 and the like. In particular, α-
Since the ethylene / α-olefin random copolymer resin having 4 to 8 carbon atoms in the olefin is excellent in photographic properties, film moldability, physical strength, and inexpensively polymerized and produced worldwide, the present invention preferable. In addition, ethylene
The olefin block copolymer resin is particularly preferable when light-shielding properties are required as in the present invention because of its excellent physical strength and excellent light-shielding ability due to cloudiness. These two kinds of mixed resins can also be used.

Typical polymerization processes of L-LDPE resin include a gas phase method using a medium / low pressure apparatus, a solution method, a liquid phase slurry method, and a high pressure improvement method using a Ziegler catalyst while using a high pressure improvement apparatus. -There is a high pressure conversion method for obtaining an LDPE resin.

Typical specific examples of L-LDPE resins produced by polymerization using commercially available multi-site catalysts (typical examples are Ziegler catalysts) are shown below.

(1) Ethylene / butene-1 copolymer resin G resin (UCC) Dourex (Dow Chemical) Scrair (DuPont Canada) Marlex (Philip) Stamirex (DSM) Sumikasen L (Sumitomo) Chemicals) Neozex (Mitsui Petrochemical) Novatec-L (Mitsubishi Kasei) Yucaron-LL (Mitsubishi Yuka) Nisseki Linirex (Nippon Petrochemical) Shorex Linear (Showa Denko) NUC Polyethylene-LL (Nippon Unicar) Ube Polyethylene L ( Ube Industries) Idemitsu Polyethylene L (Idemitsu Petrochemical) Nipolon L (Tosoh) (2) Ethylene / Hexene-1 copolymer resin Exelen VL (Sumitomo Chemical) TUFLIN (UCC) NUC-FLX (Nack Flex) (UCC) TUFTTHENE (Nihon Unicar) Nipolon Z (Tosoh) (3) Ethylene / 4-methylpentene-1 copolymer resin Ultzex (Mitsui Petrochemical) (4) Ethylene / octene-1 copolymer resin Stamirex (DSM) Dourex (Dow Chemical) ) SCURE (Dupont Canada) MORETEC (Idemitsu Petrochemical)

Among these L-LDPE resins, they contain a light-shielding substance and are preferred for use in packaging materials for photographic light-sensitive materials, in which complete light-shielding properties, suitability for heat sealing, tear strength, and impact piercing strength are particularly required. The resin has a melt flow rate (hereinafter referred to as MFR) of 0.1 to 40 g / 10 min (condition 4 of JIS K-7210 or ASTM D12).
Measured under condition E of 38. 1. Test temperature 190 ° C, test load
16kgf), density 0.870 ~ 0.940g / cm
³ (measured by JIS K-7112 or ASTM D 1505), and the α-olefin has 3 to 15 carbon atoms,
Preferably, 4 to 10, more preferably 6 to 8 are obtained by the liquid phase process and the gas phase process.

Sumikasen-L (Sumitomo Chemical), Nipolon L and Z (Tosoh), Ube polyethylene L (Ube Industries) obtained by an improved high-pressure process with reduced equipment costs by converting the conventional high-pressure process. L-LDP such as
E resins are also preferred.

In the packaging material for a photographic light-sensitive material of the present invention, preferred representative examples of the L-LDPE resin are listed below by trade name. When a multi-site catalyst (a typical example is a Ziegler-based catalyst) is used to polymerize α into polyethylene. -Ultzex of Mitsui Petrochemical Co., Ltd. having introduced 4-methylpentene-1 having 6 carbon atoms as an olefin side chain, and Idemitsu Petrochemical Corporation having introduced octene-1 having 8 carbon atoms as an α-olefin side chain ( Co., Ltd., MORETEC Co., Ltd., DSM Co., Ltd.'s Stamirex Co., Ltd. and Dow Chemical Co., Ltd.'s Dourex Co., Ltd.
PE resin). Preferable typical examples obtained by a low-pressure gas phase process are listed below under trade names: TUFTHEN and UCC of Nippon Unicar Co., Ltd., in which hexene-1 having 6 carbon atoms is introduced as an α-olefin side chain. TU
FLIN and the like.

Also, an ultra-low-density linear low-density polyethylene resin having a density of less than 0.910 g / cm ³ , for example, UCC
NUC-FLX manufactured by Sumitomo Chemical Co., Ltd. and Exelen VL manufactured by Sumitomo Chemical Co., Ltd. are also preferable.
Hexene-1).

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

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

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

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

[3] Solution Method Polymerization in the solution method is performed in a solution. The reaction is performed at a high temperature to maintain a solution state. In terms of quality, the permissible range of the density reduction is wide, and the α-olefin having 4 or more carbon atoms, preferably 6 or more carbon atoms (butene-1, pentene-
1,4-methylhexene-1, 4,4-dimethylpentene-1, 4-methylpentene-1, hexene-1, heptene-1, octene-1, decene-1, eicosene-1,
Dodecene-1, hexadecene-1, octadecene-1,
This is the most suitable production process for copolymerization of ethylene with tetradecene-1). It is also optimal as a process for producing an L-LDPE resin having a large α-olefin content (ultra-low density L-LDPE resin having a density of 0.910 g / cm ³ or less).

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

Table 1 shows these introduced manufacturing technologies, manufacturers, and product names.

[0034]

[Table 1]

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

When the L-LDPE resin is used as the matrix resin, 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, the cost becomes high, and the obtained ethylene-α-
The olefin copolymer resin has high tackiness, low rigidity, poor film moldability, large blocking between films, and is difficult to put into practical use. However, it is preferable to form a laminated film in which the inner layers are laminated by blocking adhesion, since a stable blocking adhesion and lamination can be obtained regardless of the temperature and humidity in the film forming chamber.

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

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

In order to prevent blocking and improve physical strength,
The molecular weight distribution (mass average molecular weight / number average molecular weight) by the GPC method is 5 or less, preferably 1.1 to 4, more preferably 1.2 to 3, and most preferably 1.3 to 2.7.

As an ethylene / α-olefin copolymer resin produced by polymerization using a metallocene catalyst, which is a typical example of a single site catalyst, ethylene / α-olefin copolymer resin is preferable.
It is an olefin random or block copolymer resin. The composition of the ethylene / α-olefin random or block copolymer resin is such that the α-olefin component is 1 to
99 mol%, preferably 1 to 95 mol%, more preferably 1 to 90 mol%, particularly preferably 2 to 80 mol%, most preferably 2 to 50 mol%, and the ethylene component is 1
-99 mol%, preferably 5-99 mol%, more preferably 10-99 mol%, particularly preferably 20-98 mol%, most preferably 50-98 mol%. Representative examples of α-olefins include propylene, butene-1, hexene-1, pentene-1, 3-methyl-pentene-
1,4-methyl-pentene-1, octene-1, nonene-1, decene-1, dodecene-1, tetracene-1, hexadecene-1, pentadecene-1, octadecene-
1, heptene-1, eicosene-1, 4-methyl-hexene-1, 4,4-dimethylpentene-1 or the like having 3 to 20, preferably 4 to 15, more preferably 4 to 15 carbon atoms.
To 12, most preferably 4 to 10, one or more α-olefins.

Particularly preferred specific examples of ethylene / α-olefin random or block copolymer resins produced by polymerization using a metallocene catalyst are ethylene and α-olefins having 6 carbon atoms by a gas phase polymerization process. L-LDPE resin obtained by copolymerizing hexene-1. If these are polymerized in the presence of a metallocene catalyst,
Either method may be used, for example, polymerization in the improved high-pressure polymerization method is to maintain the polymer in a solution state, and to increase the polymerization activity at 120 ° C. or higher, and suppress the chain transfer reaction that causes a decrease in molecular weight. And at a temperature of 350 ° C. or lower, preferably 150 to 300 ° C., at a temperature of 400 kg / cm ² or more and 500 to 2000 kg so as not to lower the polymerization activity.
/ Cm ² is preferably performed. Further, 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 preferably 100 ° C. or lower. The lower limit of the polymerization temperature is not particularly limited, but in order to increase the polymerization activity. The temperature is preferably 50 ° C. or higher. 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 needs to be 120 ° C. or higher in consideration of the fact that the copolymer is in a solution state and that the polymerization activity is increased. Although the upper limit of the polymerization temperature is not particularly limited, it is preferably 300 ° C. or lower in order to suppress a chain transfer reaction that causes a decrease in molecular weight and not to lower catalyst efficiency. The pressure at the time of polymerization is not particularly limited, but is preferably at least atmospheric pressure and not more than 250 kg / cm ^{2 in} order to balance economy and polymerization activity.

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

Therefore, in order to maintain good photographic properties, the amount of residual halogen compounds (mainly halogen gas which adversely affects photographic properties) in the packaging material for photographic light-sensitive materials of the present invention is 400 ppm or less, preferably 200 pp.
m, more preferably 100 ppm or less, particularly preferably 1 to 80 ppm, and most preferably 4 to 60 ppm.

For this purpose, a metallocene-based catalyst containing at least one of zirconium-based, hafnium-based, titanium-based and vanadium-based catalysts having a high catalytic activity is used. L
DPE resins are preferred. The residual halogen content in the L-LDPE resin that adversely affects photographic properties is 400 ppm.
Or less, particularly preferably 150 ppm or less. It is also possible to extract a catalyst residue using a catalyst deactivator in order to make the halogen content in the resin 400 ppm or less, or to provide a vent in a pelletizer or a film forming machine to reduce the residual halogen compound component, It is necessary and preferable in order to improve the rust prevention and photographic properties of the screw and die of the extruder.

A preferred polymerization method is obtained as a hydrocarbon-insoluble precipitate or an oily product by reacting at least one metallocene of a metal selected from the group consisting of zirconium, hafnium, titanium and vanadium with an excess of alumoxane. Polymerizing ethylene alone or ethylene and α-olefin or diolefin at a temperature of 0 ° C. to 200 ° C. in the presence of a catalyst containing a reaction product having an aluminum / transition metal molar ratio of 10 to 120 separated from the reaction mixture The produced homopolyethylene resin or ethylene copolymer resin. A particularly preferred polymerization method is that the above catalyst has a transition metal content of 0.00001 to 0.02% by mass.
(G transition metal / g diluent).

A particularly preferred polymerization method is a polymerization temperature of 40 to 100 ° C. and a polymerization pressure of 5 to 50 using the above metallocene catalyst.
kg / cm ² of a gas phase polymerization method, and an ethylene / α-olefin copolymer resin produced by the polymerization method.
Specifically, an ethylene / hexene-1 copolymer resin is preferable. A phenoxyimine complex catalyst, which is a “post metallocene catalyst” which is cheaper than a recently expensive metallocene catalyst, is a polyolefin resin having extremely high activity and a small amount of catalyst residues, and is therefore most preferable because it has good photographic properties.

The acid-modified polyolefin resin refers to a modified polyolefin resin obtained by graft-modifying a polyolefin resin and an unsaturated carboxylic acid, such as a graft-modified polyethylene resin, a graft-modified polypropylene resin, and a graft-modified ethylene copolymer resin (EVA resin). ,
EEA resin, L-LDPE resin, EMA resin, etc.). The details of the acid-modified polyolefin resin are the same as those of the acid-modified polyolefin resin described later as the polyolefin type adhesive for extrusion lamination.

The polyolefin-based thermoplastic elastomer exhibits a rubber elasticity at room temperature with a Shore hardness of 60 A to 95 A and a density of 0.9 g / cm ³ or less using polypropylene as a hard segment and ethylene / propylene rubber as a soft segment. However, it is a polymer material that can be plasticized and molded at high temperatures. Representative examples include an ethylene-propylene thermoplastic elastomer and an ethylene-propylene-diene thermoplastic elastomer.

The content of the polyolefin resin in the light-shielding polyolefin resin film layer is preferably at least 50% by mass, more preferably at least 65% by mass, and preferably at least 80% by mass.
The above is most preferred. When an ethylene / α-olefin copolymer resin is used, the ethylene / α-olefin copolymer resin is used to maintain the heat seal strength over time, secure physical strength, improve film formability, and not adversely affect photographic properties. The combined resin is preferably contained in an amount of 20% by mass or more, more preferably 35% by mass or more, and most preferably 50% by mass or more.

The light-shielding polyolefin resin film layer contains a gas-adsorbing substance, and when the gas-adsorbing substance is contained, a gas which adversely affects photographic properties, for example, free sulfur gas, hydrogen cyanide gas, formaldehyde gas, chlorine gas Gas, sulfurous acid gas, hydrogen chloride gas, hydrogen sulfide gas, acetaldehyde gas, ammonia gas, mercaptan gas, etc. can be adsorbed and made harmless, and catalyst residue can be made harmless.

The gas adsorbing material is polyolefin resin 10
The content is preferably 0.01 to 20 parts by mass, more preferably 0.02 to 15 parts by mass, and most preferably 0.05 to 10 parts by mass with respect to 0 parts by mass. When the amount of the gas adsorbing substance is less than 0.01 part by mass, the gas which adversely affects the photographic properties of the photographic light-sensitive material cannot be effectively adsorbed. In addition, the film formability, physical strength, appearance, and heat sealability deteriorate, and the cost increases.

Examples of the gas-adsorbing substance for adsorbing such a gas that adversely affects photographic properties include natural zeolites, synthetic zeolites, natural silica, synthetic silica, talc, activated carbon, neutral activated carbon, silica gel, activated clay, calcium chloride and the like. There is.

[0053] Zeolites are aluminosilicates having a three dimensional skeletal structure is represented by _{XM 2 / n O · Al 2} O 2 · YSiO 2 · ZH 2 O as a general formula. (M is an ion-exchangeable ion, generally a monovalent or divalent metal ion; n is the valence of the metal ion; X and Y are the coefficients of the respective metal oxides and silica; and Z is the water of crystallization. Is a number.)

Specific examples of the zeolite include A-type zeolite, B-type zeolite, D-type zeolite, L-type zeolite, NA-type zeolite, PC-type zeolite, R-type zeolite, T-type zeolite, W-type zeolite and X-type zeolite. Examples include zeolites, Y-type zeolites, ZK-5-type zeolites, high-silica zeolites, hydroxycanclinite, analcyme, chabazite, faujasite, mordenite, sodalite, hydroxysodalite, erionite, and clinobutyrolite. Among these, harmful gases (free sulfur gas,
Hydrogen cyanide gas, formaldehyde gas, chlorine gas,
A-type zeolite having a large adsorption and detoxifying ability is preferred. Synthetic zeolites are preferred over natural zeolites because of their low impurity content that adversely affects photographic properties, and synthetic A-type zeolites, which are inexpensive and have a high ability to adsorb and detoxify harmful gases, are most preferred.

In particular, an A-type zeolite containing at least one ion-exchangeable ion of sodium, barium, calcium, potassium and magnesium is preferred, and more than 20% of sodium ions are replaced by barium ions to form amorphous. Aluminosilicates are most preferred. This aluminosilicate preferably has a crystallinity of 30% or more.

The zeolites include natural zeolites (analcime, chabazite, heula).
ndite, erionite, ferrierit
e, laumontite, modernite, etc.), synthetic zeolites (A, NA,
X, Y, hydroxyl sodalite, ZK-
5, B, R, D, T, L, hydroxy, cancr
various types of zeolites, such as inite, W, Zeolaon, etc.).

The zeolite used in the present invention may be either a natural zeolite or a synthetic zeolite.
It is indispensable that it is inexpensive, has a low impurity content that adversely affects the photographic properties of the photographic light-sensitive material, has good dispersibility, and has a primary average particle size of 20 μm or less by electron microscopy. A 10 μm synthetic zeolite is suitable, preferably 0.2 to 8 μm, more preferably 0.1 μm.
It is a synthetic zeolite of 3 to 6 μm, particularly preferably 0.4 to 5 μm, most preferably 0.5 to 4 μm. It is essential that the secondary average particle diameter by electron microscopy be 50 μm or less.

A metal ion-containing zeolite obtained by adding a metal ion to zeolite is preferred. The metal ion-containing zeolite is an ion-exchangeable ion in zeolite,
For example, sodium ions, silver ions, manganese ions, nickel ions, part or all of potassium ions,
It is one substituted by one or more ions among metal ions such as copper ions.

By using metal ion-containing zeolites, an action as an antibacterial agent can be exerted. In particular, hydrophilic biodegradable materials such as gelatin, polyvinyl alcohol, etc. are easily absorbed due to water absorption and are easily biodegradable. The quality of a photographic light-sensitive material using a photographic emulsion layer, a protective layer and a back layer containing a molecule as a main component can be maintained well for a long period of time.

Among the above metal ion-containing zeolites, silver ion-containing zeolites (hereinafter referred to as silver zeolites) are preferable. Silver ions are contained in the zeolite in an amount of 0.01 to 30 from the viewpoint of improving photographic properties (to make the sulfur compound harmless) and antibacterial properties.
% By mass, preferably 0.05 to 25% by mass, more preferably 0.1 to 20% by mass, particularly preferably 0.5 to 15% by mass.
%, Most preferably 1 to 10% by weight. When the content of silver ions is less than 0.01% by mass, there is no effect of the content, and only the production cost is increased. If the content exceeds 30% by mass, there is no effect of increasing the amount, and only the material cost and the production cost increase.

Further, a zeolite containing a total of two or more metal ions of silver ions and at least one metal ion selected from the group consisting of manganese, nickel and copper is particularly preferred. By using such a zeolite containing two or more kinds of metal ions, various photographic hazardous compounds (for example, gases such as formaldehyde, chlorine, hydrogen chloride, hydrogen sulfide, sulfurous acid, and hydrogen cyanide) contained in the air can be used. Detoxification can be promoted, and a photographic photosensitive material, which is an ultra-fine chemical product, can be maintained in good quality for a long period of time (2 years or more). The content of at least one metal ion selected from the group consisting of manganese, nickel and copper is 0.01 to 15% by mass, preferably 0.05 to 13% by mass, more preferably 0.1 to 1% by mass.
It is 1% by weight, particularly preferably 0.5 to 9% by weight, most preferably 1 to 7% by weight.

Therefore, silver ion, manganese ion,
A zeolite having a large milliequivalent (hereinafter referred to as meq) having an ion exchange capacity capable of exchanging one or more metal ions in nickel ions and copper ions is preferable. Particularly, an aluminosilicate of A-type zeolite crystal having an ion exchange capacity of 2 meq / g or more is preferable. Illustrating the ion exchange capacity of a zeolite of 2 meq or more (meq = milliquivalent), the leader write is 11.5 me
q / g, 7 meq / g for A-type zeolite, 3.5 meq / g for T-type zeolite, 6.5 me for X-type zeolite
q / g, 5 meq / g for Y-type zeolite, 5 meq / g for analcyme, 5 meq / g for chabazite, 4 meq / g for erionite, 2.5 meq / g for mordenite, and 2.5 meq / g for clinobutylite.

The most preferred zeolites among these are:
Reader light with an ion exchange capacity of 5 meq / g or more, A
Zeolite, T-type zeolite, X-type zeolite, Y-type zeolite, analcyme and chabazite.

The most preferred zeolite is inexpensive, has good productivity, is easily available, and adsorbs harmful gases such as sulfur compound gas, free sulfur gas, aldehyde compound gas such as formaldehyde gas and cyanide gas which adversely affect photographic properties. It is an A-type zeolite having a large detoxification capacity and a large metal ion exchange capacity (7 meq / g).

The silver ion-containing zeolite used in the present invention is produced by bringing the zeolite into contact with a mixed aqueous solution containing silver ions prepared in advance and metal ions such as manganese ions, nickel ions, and copper ions as required, and adding sodium ions in the zeolite. An ion-exchangeable ion such as an ion or a potassium ion is replaced with the metal ion. The contact is performed at 10 to 100 ° C, preferably 20 to 90 ° C, more preferably 30 to 80 ° C, particularly preferably 35 to 70 ° C,
Most preferably, at a temperature of 40 to 60 ° C, for 1 to 28 hours, preferably 2 to 26 hours, more preferably 4 to 24 hours.
It is carried out for a time, most preferably for 6 to 22 hours, in a batch or continuous manner.

The pH of the mixed aqueous solution is 3 to 10,
It is preferably adjusted to 4 to 9, particularly preferably 5 to 8.
By adjusting the pH in this manner, precipitation of silver oxide or the like on the zeolite surface or in pores can be prevented. Each metal ion in the mixed aqueous solution is supplied as a salt. For example, silver ions are supplied as silver nitrate, silver acetate, silver sulfate, silver perchlorate, etc., manganese ions are supplied as manganese nitrate, manganese sulfate, manganese acetate, etc., and nickel ions are nickel nitrate, nickel perchlorate, acetic acid. Copper ions are supplied as nickel and the like, and copper ions are supplied as copper nitrate, copper acetate, copper sulfate, copper perchlorate and the like. After the ion-exchanged zeolite is sufficiently washed with water, it is dried at, for example, normal pressure of 120 to 500 ° C. or reduced pressure (1 to 50 torr) at 100 to 300 ° C. so that the water content becomes 15% or less.

The water content of the above zeolite and zeolite containing metal ions is 15% or less, preferably 13% or less, more preferably 11% or less, particularly preferably 9% or less, and most preferably 7% or less. If it exceeds 15%, molding failure frequently occurs. The content of the metal ion-containing zeolite and / or zeolite in the packaging material for photographic light-sensitive materials is 0.1 to 40% by mass, preferably 0.2 to 3% by mass.
5% by weight, more preferably 0.4 to 30% by weight, particularly preferably 0.8 to 25% by weight, most preferably 1.5 to 25% by weight.
20% by mass. If the content is less than 0.1% by mass, the effect of addition is small and the kneading cost increases, and if it exceeds 40% by mass, there is no effect of increasing the amount and the material cost increases.

The light-shielding polyolefin resin film layer contains a lubricant, and by containing the lubricant,
Enables low-temperature film molding, and as a result, prevents thermal degradation of the resin, improves photographic properties, improves handling suitability and lubricity of the light-shielding polyolefin resin film layer, and prevents wrinkles and streaks, No blocking occurs even when the light-shielding polyolefin resin film layer and the photographic material are stacked, and no scratches or static marks occur even when rubbed with the photographic material as a packaging bag. Can be. Further, the fluidity of the resin is improved, the film moldability is improved, the film productivity is improved, and the lubricity of the film molded product can be improved.

The lubricant is used in an amount of 0.005 to 5 parts by mass, preferably 0.01 to 5 parts by mass, per 100 parts by mass of the polyolefin resin.
To 3 parts by mass. The content is more preferably 0.02 to 1.5 parts by mass, and most preferably 0.03 to 1 part by mass. When the amount of the lubricant is less than 0.005 parts by mass, there is no effect of addition, and only the kneading cost increases. If the amount exceeds 2 parts by mass, foaming, white smoke and die lip streaks tend to occur, and stickiness and bleed-out tend to occur over time after film formation, which adversely affects the photographic light-sensitive material. Furthermore, the heat-sealing strength with time decreases, and the sealing property, moisture-proof property and oxygen barrier property deteriorate, and it is difficult to put it into practical use as a packaging material for photosensitive materials.

Examples of the lubricant include a saturated fatty acid amide lubricant such as behenic acid amide, stearic acid amide, palmitic acid amide and lauric acid amide; an unsaturated fatty acid amide lubricant such as erucic acid amide and oleic acid amide; Bis fatty acid amide lubricants such as ninamide, methylenebisstearic acid amide, methylenebiooleic acid amide, ethylenebisstearic acid amide, hexamethylenebisstearic acid amide, hexamethylenebisoleic acid amide, silicone resin, nonionic surfactant Lubricants, liquid paraffin, natural paraffin, microwax, synthetic paraffin, polyethylene wax, polypropylene wax, hydrocarbon lubricants such as chlorinated hydrocarbons, fluorocarbons, and fatty acids such as higher fatty acids (preferably C12 or higher). Agent, lower alcohol ester of fatty acid, ester lubricant such as polyglycol ester of fatty acid, alcoholic lubricant such as polyhydric alcohol, polyglycol, polyglycerol, lauric acid, stearic acid, ricinoleic acid, naphthenic acid, oleic acid, etc. Higher fatty acids and Li, Mg, Ca, Sr, Ba, Zn, Cd, A
There are metal salts of fatty acids such as compounds with metals such as l, Sn and Pb. These lubricants may be used alone or, if necessary, in combination of two or more. Saturated and unsaturated fatty acid amide-based lubricants, bisfatty acid amide-based lubricants, fatty acid metal salts, silicone resins, polypropylene wax, and the like are preferable because the effect of including the above lubricant can be maximized.

Further, among the various lubricants described on page 5 [0032] to page 6 [0044] of JP-A-6-317881, the photographic properties are good,
More than one kind of lubricant can be selected and used in an amount suitable for the purpose of use.

Representative examples of the fatty acid amide-based lubricant are described below. [Saturated fatty acid amide lubricant] Behenic acid amide lubricant; Diamid KN (Nippon Kasei), etc. Stearamide amide lubricant; Armide HT (Lion fat), Alflow S-10 (Japan fat), Fatty acid amide S (Kao), Diamid 200 (Nippon Kasei), Diamid AP-1 (Nippon Kasei), Amide S. Amide T (Nitto Kagaku), Neutron-2 (Nippon Seika), etc.

[Hydroxystearic amide lubricant] Palmitic amide lubricant; Neutron S-18 (Nippon Seika), Amide P (Nitto Chemical), etc. Lauric amide lubricant; Armide C (Lion Akzo), diamond Mid (Nihon Kasei) etc.

[Unsaturated fatty acid amide lubricant] Erucamide amide lubricant; Alflow P-10 (Nippon Oil & Fats), Neutron-S (Nippon Seika), LUBROL (I
・ CI), Diamid L-200 (Nippon Kasei), etc. 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 acid amide-based lubricants; Diamid 200 bis (Nippon Kasei), Armowax (Lion
Methylenebisoleic amide lubricants; Lubron O (Nippon Kasei), etc. ethylene bisstearic acid amide lubricants; Armoslip EBS (Lion Akzo), etc. hexamethylenebisstearic amide lubricants; Amide 65 (Kawaken Fine Chemical), etc. Hexamethylenebisoleic amide-based lubricant; Amide 60 (Kawaken Fine Chemical), etc.

The amount of the lubricant to be added varies depending on the kind, and is preferably 0.01 to 5% by mass in the case of a lubricant having a small lubricating effect mainly for maintaining the photographic performance of the photographic material, such as a fatty acid metal salt. 0.03 to 3% by mass is more preferable,
0.05 to 1.5% by mass is particularly preferred, and 0.07 to 1% by mass.
% By weight is most preferred. When the addition amount is less than 0.01% by mass, there is no effect of addition and only the kneading cost increases. If the addition amount exceeds 5% by mass, foaming, white smoke and die lip streaks are likely to occur, or 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 passage of time after molding, which adversely affects the photographic material. Furthermore, the heat-sealing strength with time decreases, and the sealing property, moisture-proof property and oxygen barrier property deteriorate, and it is difficult to put it into practical use as a packaging material for photosensitive materials.

Although the lubricant has a large lubricating effect like a fatty acid amide-based lubricant and a bisfatty acid amide-based lubricant, in the case of a lubricant which easily bleeds out and adversely affects a photographic light-sensitive material, 0.005 to 1% by mass is used. Is preferred, and
0.5 mass% is more preferable, and 0.03 to 0.3 mass%.
Is most preferred. When the addition amount is less than 0.005% by mass, there is no effect of addition and only the kneading cost increases. If the addition amount exceeds 1% by mass, 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.

As the lubricant, it is preferable to use a fatty acid metal salt which neutralizes the catalyst residue, improves the photographic properties of the photographic light-sensitive material, and also has a rust-preventing effect on film forming equipment. Representative examples of this fatty acid metal salt 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 include compounds with metals such as Ba, Zn, Cd, Al, Sn, Pb, and Cd, and among these, magnesium stearate, calcium stearate, sodium stearate, zinc stearate, zinc oleate and Magnesium oleate is more preferred, calcium stearate and zinc stearate are particularly preferred,
Most preferred is zinc stearate.

This zinc stearate has a melting point of 117 as compared with barium stearate (melting point of 225 ° C. or more) and calcium stearate (melting point of 148 to 155 ° C.).
It is as low as ~ 125 ° C and melts at a low temperature to improve the dispersibility of light-shielding substances, gas-adsorbing substances and hydrotalcite compounds.

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

[0081]

[Table 2]

Among the above silicone resins, silicone oil is preferable because it has the following effects. (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) Reduce the coefficient of friction of the film molded product in the heated state. (5) When used in combination with a light-shielding substance, the thermoplastic resin becomes turbid and the haze is increased. As a result, the coloring power can be improved and the light-shielding ability can be improved. Nature can be secured.

The silicone oil preferably has a viscosity at 25 ° C. in the range of 5,000 to 50,000 centistokes, more preferably in the range of 7,000 to 40,000 centistokes, and more preferably 9,000 to 4,000 centistokes. 35,
Particularly preferred are those in the range of 2,000 centistokes,
Most preferred is in the range of 10,000 to 30,000 centistokes. The viscosity of silicone oil is 5,0
If it is less than 00 centistokes, there are many unreacted low molecular weight substances, which may deteriorate photographic properties (increase in fogging, etc.). On the other hand, if it exceeds 50,000 centistokes, the viscosity is so large that the handleability is poor, so that the resin adheres to the container and cannot be taken out, or the flowability of the resin is reduced, and molding failure may occur.

Examples of the silicone oil include polymethylphenylsiloxane, olefin-modified silicone, amide-modified silicone, polydimethylsiloxane, amino-modified silicone, carboxyl-modified silicone, α-methylstyrene-modified silicone, and polyether-modified with polyethylene glycol or polypropylene glycol. It is a silicone oil containing a modified siloxane bond such as silicone, olefin / polyether-modified silicone, epoxy-modified silicone, amino-modified silicone, and alcohol-modified silicone.

Among these silicone oils, olefin-modified silicone, amide-modified silicone, polydimethylsiloxane, olefin-modified silicone, amide-modified silicone, and polydimethylsiloxane are preferable when they have little adverse effect on photographic light-sensitive materials and have a large lubricating effect. Polyether-modified silicone and olefin / polyether-modified silicone.

The content of the silicone oil is from 0.01 to
5% by mass is preferable, 0.03 to 3% by mass is more preferable, 0.05 to 1.5% by mass is particularly preferable, and 0.07% by mass is preferable.
~ 1% by weight is most preferred. If the content of the silicone resin is less than 0.01% by mass, the effect cannot be exhibited effectively. On the other hand, if the content exceeds 5% by mass, not only the effect of increasing the amount is not exhibited, but also the material cost is increased, and bleed-out is increased to lower the commercial value.

The light-shielding polyolefin resin film layer contains a hydrotalcite compound. When the hydrotalcite compound is contained, phosphorus phosphite which adversely affects the photographic properties of a photographic light-sensitive material generated by thermal decomposition is contained. Neutralizes acids, neutralizes catalyst residues, absorbs halogen compounds such as hydrochloric acid, renders harmless substances that adversely affect photographic properties, prevents mold rusting, resin burning failure, etc. Can be prevented. In particular, when used in combination with one or more phenolic antioxidants and phosphorus-based antioxidants,
The photographic properties and the thermoplastic resin, the 1,2-polybutadiene-based thermoplastic elastomer, and the additives have a large effect of preventing thermal degradation and thermal decomposition, which is preferable.

The hydrotalcite compound is preferably contained in an amount of 0.01 to 25 parts by mass, more preferably 0.02 to 20 parts by mass, and more preferably 0.05 to 10 parts by mass, based on 100 parts by mass of the polyolefin resin. It is particularly preferred that the content be contained by mass, more preferably 0.1 to 5 parts by mass. If the content is less than 0.01 part by mass, the effect of addition is not exhibited, and only the kneading cost is increased. It just becomes.

Preferred specific examples of the hydrotalcite compound 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 ·
0.42H ₂ O Mg _0.75 Al _0.25 (OH) ₂ (CO ₃ )
_0.125 · 0.63H ₂ O Mg _0.83 Al _0.17 (OH) ₂ (CO ₃ )
_0.085・ 0.4H ₂ O etc.

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

Further, the phosphorous antioxidant added to prevent the thermal degradation and thermal decomposition of the thermoplastic resin and additives is neutralized with phosphorous acid which is generated when the phosphorous antioxidant is thermally decomposed and adversely affects the photographic properties of the photographic light-sensitive material. And has an unexpected effect of improving photographic properties (reducing fog). As a specific method for synthesizing the hydrotalcite compound, known methods disclosed in JP-B-46-2280, JP-B-50-30039 and the like can also be used.

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

The light-shielding polyolefin resin film layer contains a light-shielding substance. By including a light-shielding substance, light-shielding properties can be ensured,
The rigidity is increased, the film formability is improved, the coloring failure of the resin and the spots are less noticeable, and the commercial value is increased.

The content of the light-shielding substance is preferably 0.1 to 40 parts by mass with respect to 100 parts by mass of the polyolefin resin.
The amount is more preferably 0.5 to 30 parts by mass, particularly preferably 1 to 20 parts by mass, and most preferably 2 to 10 parts by mass. When the content is less than 0.1 part by mass, the light-shielding property cannot be sufficiently secured unless the effect of addition is small and the film is made thick. Further, if it exceeds 40 parts by mass, the fluidity of the resin is deteriorated, the physical strength and the heat sealability are deteriorated,
The effect of adding only cannot be obtained, and only the cost increases.

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

Examples in which light-shielding substances are classified by color are described below. White: titanium oxide, calcium carbonate, mica, zinc white, clay, barium sulfate, calcium sulfate, magnesium silicate, etc. Yellow: titanium yellow, yellow iron oxide, chromium titanium yellow, disazo pigment, bat pigment, quinophthalene pigment, isoindolinone, etc. Red: Bengala, disazo pigment, berlene pigment, monoazo lake pigment, condensed azo pigment, etc. Blue: Cobalt blue, ultramarine, cyanine blue, etc. Green: Chromium oxide green, titanium green, cyanine green, etc. Black: Carbon black, black iron oxide, etc. Silver: Aluminum powder, aluminum powder, powder, etc.

Examples of the black light-shielding substance include carbon black, graphite, black iron oxide, carbon fiber, carbon hollow sphere, and the like. Among these black light-shielding substances, carbon black is preferable because it hardly adversely affects photographic properties, is stable to heat even at 150 ° C. or higher, and has excellent heat resistance and light resistance.

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

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

Overseas products include, for example, Black Pearls 2, 46, 70, 71, 7 of Cabot Corporation.
4,80,81,607 etc., Regal 300,33
0, 400, 660, 991, SRF-S, etc., Vulc
an 3, 6, etc., Sterling 10, SO, V,
S, FT-FF, MT-FF and the like.

Further, Unit of Ashland Chemical Co., Ltd.
ed R, BB, 15, 102, 3001, 3004
3006, 3007, 3008, 3009, 3011
3012, XC-3016, XC-3017, 3020
And the like, but are not limited thereto.

Channel black produced by bringing a gas flame of natural gas or a gaseous or vaporous hydrocarbon into contact with the back surface of a channel steel in incomplete combustion in carbon black to precipitate carbon black is colored. Although the power is large, the photographic properties are poor and the air is polluted during the production, which is not preferable in the present invention.

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

In the present invention, furnace carbon black is preferred for the purpose of improving the light-shielding property, cost and physical properties. Examples of the expensive but light-shielding substance having an antistatic effect include various conductive carbon blacks and acetylene carbon blacks of various companies, and modified secondary carbon black. Ketjen carbon black, which is a raw carbon black, is preferred. Particularly high sensitivity (ISO sensitivity 40
0 or more) For photographic materials, the sulfur content is 0.1
% Of acetylene black and 1250 ° C. to 1600
Furnace carbon black produced in a furnace at 0 ° C. is preferred.

When used in the packaging material for a photographic light-sensitive material of the present invention, the photographic light-sensitive material does not generate fog.
Among carbon blacks, pH (JIS K6221) is particularly preferred in that there is little occurrence of increase / decrease in photosensitivity, large light-shielding ability, hardening of carbon black (pollution), and generation of pinholes in films such as fish eyes. Measurement)
Is 6.0 to 9.0, average particle diameter (measured by electron microscopy)
Is preferably from 10 to 120 mμ, particularly preferably from 10 to 80 mμ, and most preferably from 10 to 60 mμ. Among these, furnace carbon black having a volatile component (measured by JIS K 6221) of 2.0% or less and a DBP oil absorption (measured by the oil absorption A method of JIS K 6221) of 50 ml / 100 g or more is inexpensive, This is preferred because it does not adversely affect the properties, improves light-shielding properties, improves dispersibility, and causes little deterioration in physical properties.

ASTM D in packaging materials for photographic light-sensitive materials
The sulfur component according to the measurement method of 1619-60 is 0.9% or less, preferably 0.7% or less, particularly preferably 0.5% or less.
Below, most preferably, if it is not 0.1% or less, photographic properties of the photographic light-sensitive material such as increase in fog, abnormal sensitivity and abnormal occurrence are adversely affected. In particular, a free sulfur component which greatly adversely affects the photographic properties of a photographic light-sensitive material directly. ｛Each sample is cooled and solidified with liquid nitrogen and then pulverized. 100 g of the pulverized sample is placed in a Soxhlet extractor and extracted with chloroform at 60 ° C. for 8 hours. Bring the total volume to 100 ml. 10 ml of this solution is injected into a high performance liquid chromatograph, and sulfur is quantified. High-performance liquid chromatography separation conditions are as follows: column; ODS silica column (4.6 φ × 150 mm), separation solution: methanol 95 and water 5 (containing 0.1% each of acetic acid and triethylamine), flow rate: 1 ml / min, detection wavelength; The determination at 254 nm is performed by the absolute calibration method. ｝ Is 0.1% or less, preferably 0.05% or less, particularly preferably 0.01% or less. Therefore, although expensive, acetylene black having a sulfur component content of 0.1% or less has an ISO sensitivity of 10%.
It is suitable for maintaining a good photographic property for photographic photosensitive materials of 0 or more.

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

Therefore, as the raw material oil, ethylene bottom oil derived from creosote oil and petroleum is preferable, and ethylene bottom oil derived from naphtha having a sulfur content of 0.05 to 0.1% is produced as a raw material. Carbon black is most preferred because the sulfur content in carbon black can be reduced to 0.1% by mass or less. As the production method, furnace carbon black produced by continuous partial combustion in a furnace at 1200 ° C. to 1700 ° C., preferably 1250 ° C. to 1600 ° C., or thermal decomposition using the above-mentioned raw materials is preferable. The addition amount of the carbon black produced from the ethylene bottom oil to the thermoplastic resin film is preferably 0.1 to 60% by mass, and 0.3 to 40% by mass in order to secure light-shielding properties and antistatic properties. 0.5-20 mass% is more preferable, and 1.0
-20% by weight is particularly preferred, and 1.0-10% by weight is most preferred.

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)
hur) content (quantification according to JIS K 6350) is 100 ppm or less, preferably 50 ppm or less,
Particularly preferably 20 ppm or less, most preferably 10 p
pm or less of carbon black. In view of the low free sulfur content, in the present invention, naphtha is used to produce ethylene bottom oil by continuous partial combustion in a furnace at 1250 ° C. to 1600 ° C. or by thermal decomposition. Furnace carbon black is most preferred.

In the carbon black, the content of a cyanide compound (4-pyridinecarboxylic acid.
The value obtained by converting the amount of hydrogen cyanide quantified by pyrazolone absorption spectrometry into ppm unit based on the mass of the light-shielding substance)
It is at most 20 ppm, preferably at most 10 ppm, particularly preferably at most 5 ppm, most preferably at most 1 ppm.

In carbon black, the amount of adsorbed iodine (measured by JIS K 6221) relating to the dispersibility, conductivity and light-shielding ability of carbon black is 20 mg /
g, preferably 30 mg / g or more, particularly preferably 50 mg / g or more, most preferably 80 mg / g or more, and dibutyl phthalate (DBP), oil absorption (JI
SK6221) is 50 ml / 100 g or more,
It is preferably at least 60 mg / 100 g, particularly preferably 7 mg / 100 g.
0 ml / 100 g or more, most preferably 100 ml / 1
It is carbon black of 00 g or more.

The total sulfur content in carbon black,
Preferred examples of the hydrogen cyanide gas content and the volatile component ratio include carbon black having a total sulfur content of 0.9% or less, a hydrogen cyanide gas content of 0.001% or less, and a volatile component ratio of 1% or less, and 0.7 sulfur content
% Or less, a hydrogen cyanide gas content of 0.0005% or less, and a volatile component rate of 0.8% or less, most preferably a total sulfur content of 0.1% or less and a hydrogen cyanide gas content of 0.0001%. Hereinafter, when the volatile component ratio is 0.
There is less than 5% carbon black.

For practical use as a packaging material for a photographic light-sensitive material of the present invention, quality assurance, physical strength, photographic performance assurance, etc.
From the viewpoint of moldability and economy, the total content of the light-shielding substance in the light-shielding polyolefin resin film layer is 0.1 to 60% by mass.
However, the content varies depending on the light-shielding ability, average particle size, and the like of the light-shielding substance. In the case of carbon black, titanium oxide and aluminum powder having excellent light-shielding ability, the total content in the light-shielding polyolefin resin film layer is 0.1 to 60% by mass from the viewpoint of light-shielding properties, economy, film formability, and the like. It is preferably from 0.3 to 40% by mass, more preferably from 0.5 to 20% by mass, most preferably from 1 to 10% by mass.
If the content is less than 0.1% by mass, the light-shielding ability becomes insufficient unless the thickness of the packaging material for a photographic light-sensitive material is increased, thereby causing light fog. If the thickness is increased, melt fracture is likely to occur,
In addition, the molding speed of the packaging material for photographic light-sensitive materials is slow (because the cooling time is long), and the amount of resin used is large. If the content exceeds 60% by mass, the cost becomes high, the dispersibility deteriorates, the generation of microgrids (agglomerated impurities) increases, the pressure fog and abrasion on the photographic light-sensitive material are generated, and the photographic light-sensitive material packaging is used. The amount of water in the material increases due to an increase in the amount of water adsorbed on the carbon black, and adversely affects the photographic performance of the photographic light-sensitive material (fog generation, abnormal sensitivity, abnormal coloring, etc.). further,
Deterioration of manufacturing suitability for packaging materials for photographic photosensitive materials (foaming, silver strip,
Pinholes and the like) and physical strength are reduced, which makes practical use difficult.

Particularly preferable carbon blacks have an iodine adsorption amount (measured according to JIS K 6221) relating to the dispersibility, conductivity and light-shielding ability of the carbon black.
0 mg / g or more, preferably 30 mg / g or more, particularly preferably 50 mg / g or more, and most preferably 80 mg / g.
g or more, dibutyl phthalate (DBP), oil absorption (measured by JIS K 6221) is 50 ml / 100 g or more, preferably 60 mg / 100 g or more, particularly preferably 70 ml / 100 g or more, and most preferably 100 ml.
/ 100 g or more of carbon black.

In the present invention, furnace carbon black is preferred for the purpose of improving light-shielding properties, cost, and physical properties. Examples of expensive light-shielding substances having an antistatic effect include various conductive carbon blacks and acetylene carbon blacks of various companies. Ketchen carbon black, which is a by-product carbon black, is preferred. Particularly, for a high-sensitivity (ISO sensitivity of 400 or more) photographic light-sensitive material, the sulfur content is set to 0.1.
Furnace carbon black produced by subjecting 1% or less of acetylene black and ethylene bottom oil made from naphtha to continuous partial combustion in a furnace at 1250 ° C. to 1600 ° C. or thermal decomposition is preferable.

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

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

The addition amount of the conductive carbon black is preferably 0.05 to 40 parts by mass, more preferably 0.5 to 35 parts by mass with respect to 100 parts by mass of the polyolefin resin.
The amount is particularly preferably 1 to 30 parts by mass, and most preferably 2 to 25 parts by mass. If the added amount is less than 0.05 parts by mass, desired light-shielding properties or conductivity may not be obtained in some cases. If the added amount exceeds 40 parts by mass, the effect of increasing the amount is not exhibited and the cost is increased. Furthermore, physical strength, resin fluidity, and film moldability may deteriorate.

Light-shielding substances having an antistatic effect include, in addition to the above-described conductive carbon black, carbon fibers, metal fibers, Al-doped, TiO ₂ , SnO ₂ , metal-coated fibers,
Conductive substance-containing fiber, metal powder, graphite, various metal salts, metal adsorption fiber, polyaniline, polypyrrole, polyacetylene, polydiacetylene, polyparaphenylene,
There is graphite powder and the like. The total content of these light-shielding polyolefin resin film layers is such that the volume resistivity measured according to JIS K 6911 is 1 × 10 ¹² Ω · cm or less (20
(Measured at 60 ° C. and 60% RH) in the present invention.

In order to improve the dispersibility of carbon black and the like and to improve the photographic properties, it is preferable to include a fatty acid metal salt as a dispersant. As the fatty acid metal salt, as described above, lauric acid, stearic acid,
Higher fatty acids such as succinic acid, stearyl lactic acid, lactic acid, phthalic acid, benzoic acid, hydroxystearic acid, ricinoleic acid, naphthenic acid, oleic acid, palmitic acid, erucic acid and Li, Na, Mg, Ca, Sr, Ba, Zn , C
Examples thereof include compounds with metals such as d, Al, Sn, Pb, and Cd. Preferred examples include magnesium stearate, calcium stearylate, sodium stearate, zinc stearate, zinc oleate, and magnesium oleate. Particularly preferred fatty acid metal salts are calcium stearate and zinc stearate (preferably a combination of the two), and the most preferred fatty acid metal salt is zinc stearate.

The form in which the light-shielding substance is blended is roughly classified as follows. (1) Uniformly colored pellets (the most commonly used ones called color compounds) (2) Dispersible powders (treated with various surface treatment agents, also called dry colors, and a dispersing aid) (3) Petate (Plasticizer etc. dispersed) (4) Liquid (Liquid dispersed in surfactant etc.) (5) ) Masterbatch pellets (a light-shielding substance is dispersed at a high concentration in the plastic to be colored) (6) Hygroscopic granular powder (a light-shielding substance is dispersed at a high concentration in the plastic, (7) Dry powder (Normal untreated dry powder)

There are various modes in which the light-shielding substance is mixed with the thermoplastic resin as described above, but the master batch method is preferred in terms of cost, prevention of contamination of the work place, 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.

Light-shielding substance (carbon black, aluminum powder, an inorganic pigment having a refractive index of 1.50 or more, an inorganic pigment having a specific gravity of 3.4 or more when an X-ray shielding property is required, and an oil absorption of 50 ml / 100 g or more of an inorganic pigment is particularly preferable), to improve the dispersibility in a resin, to improve the flowability of a molten resin, to prevent the occurrence of microgrit which causes friction fog, pressure fog, abrasion, etc. on a photographic photosensitive material, and to improve photographic properties. It is preferable to coat the surface of the light-shielding substance with a surface coating substance in order to prevent generation of harmful volatile substances, decrease moisture absorption, prevent dilip stains, and the like.

Representative examples of the surface coating material are shown below. (1) Coupling agent i) Coupling agent coating containing azidosilanes (disclosed in JP-A-62-32125, etc.) ii) Coating of silane coupling agent (such as aminosilane) iii) Coating of titanate coupling agent ( 2) deposit silica, followed by alumina coating (3) zinc stearate, magnesium stearate,
Higher fatty acid metal salt coating such as calcium stearate (4) Surfactant coating such as sodium stearate, potassium stearate, oxyethylene dodecyl amine (5) Barium sulfide aqueous solution and sulfuric acid aqueous solution in the presence of excess barium ion With an average particle diameter of 0.1 to
Generating 2.5 μm barium sulfate, adding an aqueous alkali silicate solution to this water slurry to generate barium silicate on the surface of barium sulfate, then adding mineral acid to the slurry,
The above barium silicate is decomposed into hydrated silica and deposited on the surface of barium sulfate for coating. (6) Metal hydrated oxide (one or two hydrated oxides of titanium, aluminum, cerium, zinc, iron, cobalt or silicon) And / or a metal oxide (one or two or more oxides of titanium, aluminum, cerium, zinc, iron, cobalt or silicon) and (7) an aziridine group in the molecule; Oxazoline group and N
A polymer having one or more reactive groups selected from the group consisting of -hydroxyalkylamide groups; (8) a surface coating of a polyoxyalkyleneamine compound; (9) a cerium cation, a selected acid anion and Surface coating with alumina (10) Surface coating with an alkoxytitanium derivative having an α-hydroxycarboxylic acid residue as a substituent (11) Surface coating with polytetrafluoroethylene (12) Surface coating with a modified polydimethylsiloxane or silicone (13 ) Surface coating with phosphate ester compound (14) Surface coating with dihydric 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 preferable because of their excellent photographic properties and dispersibility). The surface coating amount is 100 parts by mass of a light-shielding substance. (Preferably 0.001 to 20 parts by mass and 0.01 to 15 parts by mass with respect to the surface). (21) Aliphatic monocarboxylic acid having 20 to 40 carbon atoms and aliphatic monocarboxylic acid having 20 to 40 carbon atoms. (22) Surface coating with a metal salt of a partially saponified fatty acid ester having 20 to 50 carbon atoms, etc.

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

In particular, an ester of an aliphatic monocarboxylic acid having 20 to 40 carbon atoms and an aliphatic monohydric alcohol having 20 to 40 carbon atoms is used in an amount of 0.0
It has been found that the effect of preventing the above problems can be exerted by adding 0.01 to 20 parts by mass, preferably 0.005 to 10 parts by mass, particularly preferably 0.01 to 5 parts by mass. 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 an aliphatic monocarboxylic acid having 20 to 40 carbon atoms, preferably 25 to 3 carbon atoms.
5 is an ester of an aliphatic monohydric alcohol.

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

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

[0130] 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 an inorganic and / or organic nucleating agent for 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 surface coating substance in these light-shielding substances is based on 100 parts by mass of the light-shielding substance such as carbon black, titanium oxide or aluminum powder.
The amount is 0.001 to 20 parts by mass, preferably 0.001 to 5 parts by mass, more preferably 0.01 to 3 parts by mass, and most preferably 0.05 to 1.5 parts by mass. Coating amount is 0.00
When the amount is less than 1 part by mass, the coating effect is hardly exhibited. If the coating amount exceeds 20 parts by mass, the occurrence of bleed-out increases with time and the slip between the resin and the screw occurs, resulting in a change in the discharge amount.

It is preferable that the light-shielding polyolefin resin film layer contains an antioxidant. By containing an antioxidant, preventing thermal degradation of the resin and additives, increasing the effect of preventing thermal decomposition, preventing a decrease in physical strength,
Generation of substances (aldehyde compounds, cyanide compounds, etc.) which adversely affect photographic properties can be prevented.

The content of the antioxidant is preferably 0.01 to 1 part by mass, more preferably 0.02 to 0.5 part by mass, and more preferably 0.03 to 0.5 part by mass, per 100 parts by mass of the polyolefin resin.
~ 0.25 parts by weight is most preferred. When the content is less than 0.01 part by mass, there is no effect of addition and only the kneading cost is increased. At the same time, it bleeds out to the surface of the packaging material to deteriorate the appearance.

Examples of the antioxidant include an antioxidant handbook (published on October 25, 1977 by KK Taiseisha) and a plastic data handbook (KK Industrial Research Institute 198).
Various antioxidants disclosed on pages 794 to 799 of Apr. 5, 2004), various antioxidants disclosed on pages 327 to 329 of Plastic Additives Data Collection (published by KK Chemical Industry Co., Ltd.), PLASTICS AGE E
There are various antioxidants disclosed on pages 211 to 212 of NCYCLOPEDIA Advanced Edition, 1986 (published by KK Plastic Age).

Among the various antioxidants, hindered phenol-based antioxidants are preferred, and representative examples of the hindered phenol-based antioxidants are shown below. 1,3,5-trimethyl 2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, tetrakis [methylene-3- (3 ′ · 5′-di-tert-butyl) −
4'-hydroxyphenyl) propionate] methane,
Octadecyl-3,5-di-tert-butyl-4-hydroxy-hydrocinnamate, 2,2 ', 2'-tris [(3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxy] ethyl Isocyanurate, 1,3,5-tris (4-tert-butyl-3-hydroxy-2,6-di-methylbenzyl) isocyanurate, tetrakis (2,4-di-tert-butylphenyl) 4,4 ′ -Biphenylene phosphite, 4,
4′-thiobis- (6-tert-butyl-O-cresol), 2,2′-thiobis- (6-tert-butyl-4-methylphenol), tris- (2-methyl-4)
-Hydroxy-5-tert-butylphenyl) butane, 2,2'-methylene-bis- (4-methyl-6-te
rt-butylphenol), 4,4'-methylene-bis-
(2,6-di-tert-butylphenol), 4,4 '
-Butylidenebis- (3-methyl-6-tert-butylphenol), 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.

Among these hindered phenolic antioxidants, those having a melting point of 100 ° C. or more are preferable.
Those having a temperature of 0 ° C. or higher are more preferable. When the melting point is less than 100 ° C., the composition is liable to be thermally decomposed, emits a large amount of smoke, not only reduces the effect of addition, but also deteriorates the environment in the film forming chamber and the photographic properties of the photosensitive material.

Among the hindered phenolic antioxidants, those having an average molecular weight of 400 or more are preferable, and
More than 00 is more preferable, and more than 600 is most preferable. When the molecular weight is less than 400, thermal decomposition easily occurs and smoke is increased. Further, not only does the effect of addition decrease, but also the environment in the film forming chamber and the photographic properties of the photographic light-sensitive material deteriorate.

Of the various antioxidants, phosphoric acid antioxidants are also preferred.

Examples of the phosphoric acid-based antioxidant include alkylated allyl phosphite, tris (mono and / or dinonylphenyl) phosphite, and 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 and the like can be used.

Vitamin E is also preferred as an antioxidant. This vitamin E (tocopherol) and tocopherol dimer, in addition to having an excellent antioxidant effect, cause a film molded product to be colored yellow to produce light-shielding properties. Therefore, when used together with an inorganic pigment such as carbon black, the light-shielding ability is improved by 10% or more as compared with the case of adding an inorganic pigment such as carbon black alone, and the dispersibility is also improved, so that the content of the inorganic pigment is reduced by 10% or more. Even if it does, it can have the same light shielding property. As a result, various effects such as prevention of deterioration of photographic properties, improvement of physical strength, improvement of appearance, reduction of material cost are exhibited, and it is safe for the human body. Most preferred.

It is preferable to use a phosphoric acid-based antioxidant in combination with the hindered phenol-based antioxidant. By using these together, it is possible to enhance the effect of preventing the resin and additives from thermally deteriorating without deteriorating photographic properties. it can. When a phosphoric acid-based antioxidant is contained, it is preferable to use a hydrotalcite compound in combination. By containing a hydrotalcite compound, it is possible to neutralize phosphorous acid generated by thermal decomposition and adversely affecting the photographic properties of the photographic material.

Most preferred are specific furnace carbon blacks which have little adverse effect on the photographic properties and which prevent the occurrence of static marks and light fog which are fatal to the quality of the photographic material. It is a combination of at least one of conductive carbon black and acetylene carbon black and a phenolic antioxidant having an antioxidant property and a light-shielding property-improving action.

A hydrogen cyanide gas scavenger can be contained in the light-shielding polyolefin resin film layer. That is, the content of cyanide (particularly hydrogen cyanide gas) which deteriorates photographic properties (a value obtained by converting the amount of hydrogen cyanide determined by 4-pyridinecarboxylic acid / pyrazolone absorption spectrometry into a ppm unit based on the mass of the light-shielding substance) is 20 ppm or less. , Preferably 10 ppm or less, particularly preferably 5 ppm or less, most preferably 1 ppm or less. Chemical sensitization such as gold sensitization, selenium sensitization and dye sensitization,
Particularly, in the case of a gold-sensitized photographic light-sensitive material, a hydrogen cyanide gas or the like is liable to adversely affect the photographic properties. Is preferred.

The content of the hydrogen cyanide scavenger was 0.00.0 parts by mass based on 100 parts by mass of the polyolefin resin.
It is preferably from 0.01 to 20 parts by mass, more preferably from 0.005 to 15 parts by mass, particularly preferably from 0.01 to 20 parts by mass.
It is 10 parts by mass, most preferably 0.05 to 5 parts by mass. Hydrogen cyanide scavenger content 0.00
If the amount is less than 1 part by mass, hydrogen cyanide cannot be effectively adsorbed and removed. Also, if it exceeds 20 parts by mass,
The effect of increasing the amount is not exhibited, and only the cost is increased. Further, the fluidity of the resin is deteriorated, a weld line (also referred to as a weld mark) is strongly generated, and the impact strength is reduced.

A hydrogen cyanide gas scavenger is a compound that converts hydrogen cyanide gas to an adsorbed or photographically inert substance. The hydrogen cyanide gas scavenger should not release substances that adversely affect the silver halide photosensitive material as a result of capturing the hydrogen cyanide gas. Suitable hydrogen cyanide gas scavengers can be selected from inorganic or organic compounds of noble metals. Particularly preferred are palladium (II or IV; oxidation state; the same applies hereinafter) and platinum (II or IV) compounds. Gold (I or III) compounds are also preferred. rhodium
(III), iridium (III or IV) and osmium (I
Compounds of the type I, III or IV) are also effective, but higher amounts are required to achieve an equivalent effect. Specific examples of useful inorganic or organic noble metal compounds include, for example, Gmelin Handbook.
Commercial, synthetic and ins
Itu synthetic products 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 and palladium thiocyanate.
(II), tetrachloropalladium (II) (sodium salt, potassium salt, ammonium salt), hexachloropalladium (IV), tetrabromopalladium (II), hexabromopalladium (IV), Bis (salicylato) paradimum (II) acid salt, bis (dithiooxalato-S, S ')
Palladium (II) acid salt, trans-dichlorobis (thioether) palladium (II), tetraamminepalladium
(II) salt, dichlorodiammine palladium (II), dibromodiammine palladium (II), oxalatdiammine palladium (II), dinitrodiammine palladium (II), bis (ethylenediamine) palladium (II) salt, dichloroethylenediaminepalladium (II) , Bis (2,2′-pipyridine) palladium (II) salt, bis (1,10-phenanthroline) palladium (II) salt, tetranitropalladium (I
I) acid salt, bis (glycinato) palladium (II), tetrakis (thiocyanato) palladium (II), dichlorobis (phosphine) palladium (II), 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 (I
I) acid salt, platinum chloride (IV), hexafluoroplatinate (IV),
Tetrachloroplatinate (II), hexachloroplatinate (IV), trichlorotrifluoroplatinate (IV), tetrabromoplatinate (II), hexabromoplatinate (IV), dibromodichloroplatinate (II) Salt, 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-pentane Dionato) platinum (II), tetrakis (thiocyanato) platinate (II), hexakis (thiocyanato) platinate (IV), bis {(Z) -1,2-dicyanoethylene-1,2-dithiolat} platinum (II) acid salt, dichlorobis (diethylsulfide) platinum (II), tetrachlorobis (Diethyl sulfide) platinum (IV), bis (glycinato) platinum (II), dichloroglycinatoplatinum (II), dichlorobis (triethylphosphine) platinum (II), chlorohydridobis (triethylphosphine) platinum (II), tetraammine Platinum (II) salt, Tetrachloroplatinum (II) 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 (IV) salt, dichlorodihydroxo (ethylenediamine) platinum (IV), tetrakis (pyrimidine)
Platinum (II) salt, dichlorobis (pyridine) platinum (II), bis (2,2′-pipyridine) platinum (II) salt, tetranitroplatinum
(II), chlorotrinitroplatinate (II), dichlorodinitroplatinate (II), dibromodinitroplatinate (II),
Hexanitroplatinate (IV), chloropentanitroplatinum (I
V), dichlorotetranitroplatinate (IV), trichlorotrinitroplatinate (IV), tetrachlorodinitroplatinum
(IV), dibromodichlorodinitroplatinate (IV), trichloro (ethylene) platinate (II), di-μ-chloro-
Bis (chloro (ethylene) platinum (II), trans-dichloro (ethylene) (pyridine) platinum (II), bis [bis (β-mercaptoethylamine) nickel (II) -S,
S "-platinum (II) salt and dichlorodicarbonylplatinum (II)
And the like.

Gold (I or III), rhodium (III), iridium (III or IV) and osmium (II, III or
The compound of the formula IV) can be used in the same manner. For example, potassium tetrachloroaurate (I
II), rhodium (III) chloride, potassium hexachloroiridate (IV), potassium tetrachloroylate
(III) 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 light-shielding polyolefin resin film layer may contain an antistatic agent. By including an antistatic agent, a static failure or the like can be prevented.

The content of the antistatic agent is preferably from 0.01 to 10 parts by mass, more preferably from 0.05 to 5 parts by mass, and preferably from 0.1 to 3 parts by mass, per 100 parts by mass of the polyolefin resin.
Part by weight is particularly preferred, and 0.2 to 1.5 part by weight is most preferred. When the content is less than 0.01 part by mass, there is no effect of addition and only the cost of kneading is increased. On the other hand, if it exceeds 10 parts by mass, there is no effect of increasing the amount and only the cost is increased. Furthermore, the amount of bleed-out increases with time, and the heat-sealing property deteriorates and the surface of the packaging material becomes sticky.

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

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

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

As a method of including an antistatic agent in a light-shielding polyolefin resin film, the antistatic agent is used in the form of a masterbatch resin pellet and a masterbatch resin pellet of a light-shielding substance and at least one natural (non-colored) material for dilution. After mixing the matrix resin pellets, the mixture can be melted and kneaded and then formed into a film. In the present invention, it is preferable to use in the form of a masterbatch resin pellet because of excellent handling properties and antistatic properties.

In the present invention, an antistatic masterbatch which does not adversely affect the photographic properties of the photographic light-sensitive material and has an excellent antistatic effect is preferable. , Erosmaster 1 made by Kao KK for polypropylene resin
215, 326, 320 and PP-425, and as a high-density polyethylene resin, Erestmaster HE-11
0, HE-510, and Eresmaster LL-10 for L-LDPE resin.

It is preferred that the light-shielding polyolefin resin film layer contains an aliphatic alcohol fatty acid ester. By containing aliphatic alcohol-based fatty acid esters, after storing in a low-temperature warehouse for a long period of time, preventing dropping of water when taken out at room temperature (improving suitability), improving blocking adhesion, imparting antistatic properties, etc. Can be.

The content of the aliphatic alcohol fatty acid ester is 0.1 to 100 parts by mass of the polyolefin resin.
005 to 10 parts by mass is suitable, 0.01 to 8 parts by mass is preferable, 0.02 to 5 parts by mass is more preferable, and 0.1 to 10 parts by mass is more preferable.
The amount is particularly preferably from 0.5 to 2.5 parts by mass, most preferably from 0.1 to 1 part by mass. When the content of the aliphatic alcohol-based fatty acid ester is less than 0.005 parts by mass, the effect of addition is small and costs are high.
When the content exceeds 10 parts by mass, the effect of increasing the content is small and only the material cost is required.

Preferred examples of the aliphatic alcohol fatty acid ester are compounds of an aliphatic alcohol having 1 to 10 carbon atoms and a fatty acid having 10 to 20 carbon atoms. Eate, glycerin triricinolate, glycerin acetyl ricinolate, methyl acetyl ricinolate, ethyl acetyl ricinolate, butyl acetyl ricinolate,
Propylene glycol oleate, propylene glycol laurate, pentaerythritol oleate, polyethylene glycol oleate, polypropylene glycol oleate, polyoxyethylene glycerin, polyoxypropylene glycerin, sorbitan oleate,
Sorbitan laurate, polyethylene glycol sorbitan oleate, polyethylene glycol sorbitan laurate, polyalkylene ether polyol and the like.

A formaldehyde scavenger can be contained in the light-shielding polyolefin resin film. A formaldehyde scavenger is a compound that can absorb (capture) formaldehyde by reacting with formaldehyde, and can prevent the adverse effects of formaldehyde (a large irritating odor. Particularly effective when used in combination with zeolites that adsorb and detoxify aldehyde gas, the use of inexpensive materials containing aldehyde or recycled resins that are commercially available does not adversely affect photographic properties and gives users a bad smell or pungent odor. It is preferable because it gives no discomfort.

The content of the formaldehyde scavenger in the light-shielding polyolefin resin film layer is 0.001 to 40 parts by mass, preferably 0.005 to 30 parts by mass, based on 100 parts by mass of the polyolefin resin.
The amount is more preferably from 01 to 20 parts by mass, particularly preferably from 0.05 to 10 parts by mass, most preferably from 0.1 to 10 parts by mass. When the content is less than 0.001 part by mass, there is almost no effect of addition, and when it exceeds 40 parts by mass, the effect of increasing the amount is small, the physical strength and appearance are deteriorated, and the cost is increased.

[0161] Formaldehyde scavengers include polyamide resins, amide compounds, urethane compounds,
Examples include ethylene / vinyl alcohol copolymer, pyridine derivative, pyrrolidone derivative, urea derivative, triazine derivative, hydrazine derivative, organic amino compound, imide compound, and amidine compound. As a specific example, N,
N-dimethylformamide, N, N-dimethylacetamide, N, N-diphenylformamide, N, N-diphenylacetamide, N, N-diphenylbenzamide,
N, N, N ', N'-tetramethylazibamide, oxalic acid dianilide, adipic acid dianilide, N-phenylacetanilide, nylon 6, nylon 66, nylon 66 /
6 binary copolymer, nylon 6/10 binary copolymer, nylon 66/10 binary copolymer, nylon 6/66 binary copolymer, nylon 6/12 binary copolymer, nylon 6 /
66/10 terpolymer, nylon 6/66/10/1
Lactam homo- or copolymers such as quaternary copolymer, nylon 66/66/10 terpolymer, nylon 11, nylon 12, adipic acid, sebacic acid,
Decanedicarboxylic acid, dicarboxylic acid such as dimeric acid and ethylenediamine, tetramethylenediamine, hexamethylenediamine, homopolymer or copolymer of polyamide derived from diamine such as metaxylylenediamine, lactams and dicarboxylic acid and Polyamide copolymer derived from diamine, polyacrylamide,
Polymethacrylamide, N, N-bis (hydroxymethyl) suberamide, poly (γ-methylglutamate),
Amide compounds such as poly (γ-ethylglutamate), poly (N-vinyllactam) and poly (N-vinylpyrrolidone); diisocyanates such as toluene diisocyanate and diphenylmethane diisocyanate; and glycols such as 1,4-butanediol and poly (tetra) Methylene oxide) glycol, polybutylene adipate,
Polyurethanes derived from high molecular weight glycols such as polycaprolactone, melamine, benzoguanamine, acetoguanamine, N-butylmelamine, N-phenylmelamine, N, N′-diphenylmelamine, N, N ′, N ″ -triphenylmelamine; N-methylolmelamine, N, N '
-Dimethylolmelamine, N, N ', N "-trimethylolmelamine, 2,4-diamino-6-benzyloxytriazine, 2,4-diamino-6-butoxytriazine, 2,4-diamino-6-cyclohexyltriazine , Melem, triazine derivatives such as melam, N-phenylurea, N, N'-diphenylurea, thiourea, 1-hydroxyurea, 1-methylurea, 1-ethylurea, 1-
Acetyl-3-methylurea, 1,1-diphenylurea,
1- (4-ethoxyphenyl) urea, methylurea, ethylurea, dimethylurea, diethylurea, ethyleneurea,
Guanylurea, guanylthiourea, acetylurea, propyleneurea, 5-hydroxypropyleneurea, 5-methoxypropyleneurea, 5-methylpropyleneurea,
Urea derivatives such as 4,5-dimethoxyethylene urea, N-phenylthiourea, N, N'-diphenylthiourea, nonamethylene polyurea, phenylhydrazine, diphenylhydrazine, methylhydrazine, ethylhydrazine, n
-Propylhydrazine, n-butylhydrazine, ethylene-1,2-dihydrazine, propylene-1,2-dihydrazine, butylene-1,4-dihydrazine, hydrazine of benzaldehyde, semicarbazone of benzaldehyde, 1-methyl of benzaldehyde Hydrazine derivatives such as 1-phenylhydrazine, thiosemicarbazone, hydrazine of 4- (dialkylamino) benzaldehyde, and imides such as succinimide, phthalimide, succinimide, hydantoin, 1-methylol-5,5-dimethylhydantoin and isocyanuric acid Compound, dicyandiamide, pyrrolidine, piperidine, morpholine,
Guanamine, guanidine, guanidine, aminoguanidine, guanine, guanacrine, guanochlor, guanoxane, guanosine, amiloride, N-amidino-3
Amidine compounds such as -amino-6-chloropyrazinecarboxamide, poly (2-vinylpyridine), poly (2-methyl-5-vinylpyridine), poly (2-ethyl-5-vinylpyridine), 2-vinylpyridine -2-
Pyridine derivatives such as methyl-5-vinylpyridine copolymer and 2-vinylpyridine-styrene copolymer. Among them, polyamide such as terpolymer of nylon 6/66/610, quaternary copolymer of nylon 6/66/610/12, dimer acid polyamide, melamine,
Guanamine, benzoguanamine, acetoguanamine, N
-Methylol melamine, N, N'-dimethylol melamine, N, N ', N "-trimethylol melamine, N-methylol benzoguanamine, thermoplastic polyurethane resin,
Dicyandiamide, guanidine, poly (N-vinylpyrrolidone), poly (2-vinylpyridine), N, N'-diphenylurea, polyurea, melem, and melam are preferred. Also, U.S. Pat. No. 4,411,987 and U.S. Pat.
No. 503, compounds which can be reacted with formaldehyde and solidified can also be used.

The light-shielding polyolefin resin film layer may contain a halogen gas scavenger. By containing a halogen gas scavenger, it is possible to detoxify a gas of a halogen compound component which adversely affects photographic properties and causes rusting failure in an extruder or die. As the halogen compound component,
For example, there are titanium halide compounds, silicon halide compounds, vanadium halide compounds, silicon halide compounds, aluminum halide compounds, boron halide compounds, and the like. Specifically, silicon tetrachloride, aluminum trichloride, and tribromide Aluminum, titanium trichloride, boron trichloride, titanium tetrabromide and the like.

Since these halogen compound components become various kinds of adverse effects as a halogen gas, the catalyst residue is extracted by using a catalyst deactivator, or the residual halogen compound component is provided by providing a vent in a pelletizer or a molding machine. Is preferably reduced, but it is particularly preferable to include it in a light-shielding polyolefin resin film layer in a packaging material for a photographic photosensitive material.

The content of the halogen gas scavenger was 0.0 to 100 parts by mass of the polyolefin resin.
It is preferably from 0.01 to 10 parts by mass, more preferably from 0.005 to 5 parts by mass, particularly preferably from 0.01 to 3 parts by mass,
Most preferably, the amount is 0.02 to 1.5 parts by mass. Content is 0.
If the amount is less than 001 parts by mass, the halogen gas cannot be sufficiently removed. On the other hand, when the content exceeds 10 parts by mass, there is no effect of increasing the content, and only the kneading cost is required.

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

[0166]

Embedded image In the formula, R ₁ , R ₂ , R ₃ and R ₄ each represent a hydrogen atom or a group capable of substituting for a benzene nucleus.

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

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

The residual amount of any one of chromium, zirconium, titanium, hafnium, and vanadium is 200 ppm or less, preferably 200 ppm or less, more preferably 100 ppm or less, particularly preferably 60 pp or less.
m, most preferably 40 ppm or less.

The light-shielding polyolefin resin film layer may contain an anti-fogging agent. By containing the antifogging agent, it is possible to prevent the same effects as those of the aliphatic alcohol-based fatty acid ester, particularly, to prevent water droplets from adhering when left in the atmosphere from a low-temperature warehouse.

The content of the anti-fogging agent is as follows.
With respect to 00 parts by mass, 0.01 to 5 parts by mass is preferable,
0.1 to 3 parts by mass is more preferable, and 0.3 to 2 parts by mass is most preferable. When the content of the antifogging agent is less than 0.01 parts by mass, the effect of addition is not exhibited, and only the kneading cost is increased. Further, when the content of the antifogging agent exceeds 5 parts by mass,
The effect of increasing the amount is hardly exhibited, and only the material cost increases. Also, depending on the type of antifogging agent, it is not possible to secure a stable discharge amount by increasing the slip of the thermoplastic resin and the screw, or bleed out over time on the surface of the packaging film and stickiness occurs, and dust adheres And the like.

Typical examples of the antifogging agent are shown below. Diglycerin monostearate, polyglycerin monopalmitate, sorbitan monolaurate, sorbitan monostearate, sorbitan monooleate, sorbitan monoerucate, polyoxyethylene sorbitan fatty acid ester,
Stearic acid monoglyceride, polyoxyethylene nonylphenol ether, sorbitan sesquipalmitate, diglycerin sesquioleate, sorbitol fatty acid ester, sorbitol fatty acid / dibasic acid ester,
Diglycerin fatty acid dibasic acid ester, glycerin fatty acid dibasic acid ester, sorbitan fatty acid dibasic acid ester, sorbitan palmitate, sorbitan stearate, sorbitan palmitate propylene oxide 3 mol adduct, sorbitan palmitate propylene oxide 2 mol adduct, sorbitol stearate,
Sorbitol stearate / ethylene oxide 3 mol adduct, diglycerin palmitate, glycerin palmitate, glycerin palmitate / ethylene oxide 2 mol adduct and the like.

It is preferable that the light-blocking polyolefin resin film layer contains a 1,2-polybutadiene-based thermoplastic elastomer. By incorporating a 1,2-polybutadiene-based thermoplastic elastomer, it is possible to compatibilize a plurality of different types of thermoplastic resins including a rubbery polymer-containing aromatic monovinyl resin.

The content of the 1,2-polybutadiene-based thermoplastic elastomer is preferably 0.05 to 100 parts by mass, and more preferably 0.1 to 100 parts by mass based on 100 parts by mass of the polyolefin resin.
80 parts by mass is more preferable, 0.2 to 60 parts by mass is particularly preferable, and 0.5 to 40 parts by mass is most preferable. When the content is less than 0.05 mass, there is no compounding effect and the cost is merely increased. When the content exceeds 100 parts by mass,
There is no bulking effect and only the material cost increases. further,
Problems such as insufficient rigidity also occur.

The packaging material for a photographic light-sensitive material of the present invention has a light-shielding polyolefin resin film layer as described above, but various film layers may be laminated on this light-shielding polyolefin resin film layer. The lamination of these various film layers is performed in a separate process, even if a multi-layer co-extrusion blown film molding method or a multilayer co-extrusion T-die film molding method in which two or more layers are laminated by co-extrusion simultaneously with the light-shielding polyolefin resin film layer. A flexible sheet obtained by laminating via an adhesive layer may be used.

Examples of the flexible sheet include various thermoplastic resin films, for example, various polyethylene resins, various ethylene copolymer resins, homopolypropylene resins, various propylene copolymer resins, polyvinyl chloride resins, various polyamide resins, polyacrylic resins. Nitrile resin, ethylene-vinyl alcohol copolymer resin, polycarbonate resin, various polyester resins (PET resin, PBT resin,
A-PET resin, PEN resin, etc.), a single thermoplastic resin film, a mixed resin film of two or more of these thermoplastic resins, a polymer alloy film or a modified resin film, and further, these various thermoplastic resin films. Examples include a uniaxially or biaxially stretched (including molecular orientation) film. Further, there are a triacetate film, a cellophane, a regenerated cellulose film, a paper, a synthetic paper, a nonwoven fabric, and an inorganic substance vapor-deposited film obtained by vapor-depositing an inorganic substance on the above-mentioned various thermoplastic resin films.

Examples of the deposited film of the inorganic substance deposited film include an aluminum deposited film, silicon oxide, aluminum oxide, titanium oxide, photoactive titanium oxide, photoactive zinc oxide, tin oxide, zinc oxide, isodium oxide, and the like. There is a vapor-deposited film in which one or more kinds of magnesium oxide or the like are mixed. As the transparent inorganic vapor-deposited film, a single or a composite vapor-deposited film of silicon oxide and aluminum oxide is particularly preferable from the viewpoints of vapor deposition suitability, quality, cost, and photographic properties. These deposited films are preferably formed by a vacuum deposition method, a sputtering method, an ion plating method, an electron beam method, a plasma spraying method, or the like.

The thickness of this deposited film is 50 to 3,000 °
Is preferably 100 to 2,000, more preferably 200 to 1,500, and most preferably 400 to 1,000.
If the thickness is less than 50 mm, the moisture-proof property and the oxygen barrier property may not be sufficiently secured, and the thickness may be 3,000 mm.
If it exceeds, there are problems in terms of quality, cost, and productivity, in addition to the problem of thermal deterioration and heat shrinkage of the base material, and it is difficult to put it to practical use.

In order to improve the adhesive strength between the flexible sheet layer and the deposited film, at least one of an anchor coat layer treatment of polyethyleneimine, alkyl titanate, polyurethane or the like, a corona discharge treatment, a glow discharge treatment, an ultraviolet irradiation treatment, etc. It is preferable to perform some kind of treatment.

The thickness of the flexible sheet layer is preferably 5 to 500 μm, more preferably 6 to 400 μm, and more preferably 7 to 300 μm in the case of a film which has not been stretched.
Is most preferred. When the flexible sheet layer is a uniaxially or biaxially stretched thermoplastic resin film, the thickness of the film is preferably from 5 to 70 μm, more preferably from 7 to 50 μm, and most preferably from 9 to 30 μm.

The Young's modulus of the flexible sheet is
50kg / mm²(490 N / mm ²) Or more preferred
70kg / mm²(586 N / mm²More than
Preferably, 90 kg / mm²(882 N / mm²)that's all
Is particularly preferred, and 100 kg / mm²(980 N / mm
²) Is most preferred.

A particularly preferred flexible sheet of the present invention has a longitudinal Young's modulus (ASTM D882) of 70 kg / m.
It is a biaxially stretched thermoplastic resin film having a melting point of at least 130 ° C. as measured by the DSC method, which is not less than m ² (586 N / mm ² ). Specific examples of this particularly preferred thermoplastic resin film are shown below.

Further, aluminum, silicon oxide, aluminum oxide, titanium oxide, titanium oxide having photoactivity, zinc oxide having photoactivity, zinc oxide having photoactivity were added to a thermoplastic resin film having a high melting point and a high Young's modulus as shown in Table 3. , Tin oxide or the like, and a vapor-deposited film obtained by mixing one or two or more thereof by a vacuum vapor deposition method, a sputtering method, an ion plating method, an electron beam method, a plasma spraying method or the like to have a thickness of 50 to 3,000.
Å, preferably 100 to 2,000Å, particularly preferably 200 to 1,500Å, most preferably 300 to 1,0Å
When provided at 00 °, the water vapor transmission rate can be reduced to 1 g / m ² · 24 hours or less, so that it is most suitable for a hermetically sealed and light-shielding bag for chemically and / or dye sensitized photographic photosensitive materials.

[0184]

[Table 3]

A flexible sheet (preferably a uniaxially or biaxially stretched thermoplastic resin film) on which an inorganic substance vapor-deposited film is processed is preferable because of excellent photographic properties, moisture-proof properties and antistatic properties.

As the adhesive layer for laminating the flexible sheet, various known adhesive layers can be used according to required characteristics. As the adhesive used for this adhesive layer, various polyethylenes (LDPE, L-LDPE, MD
PE, HDPE) resins, various polypropylene resins, etc., polyolefin-based thermoplastic resins, ethylene-propylene copolymer resins, ethylene-vinyl acetate copolymer resins, ethylene copolymer resins such as ethylene-ethyl acrylate copolymer resins And a special thermoplastic resin such as an ethylene-acrylic acid copolymer resin, an ionomer resin and an acid-modified ethylene copolymer resin. In addition, there is a hot-melt type rubber-based adhesive, and as a solution adhesive, there is an adhesive for wet lamination, and an emulsion or latex adhesive. Representative examples of emulsion adhesives include polyvinyl acetate, vinyl acetate-ethylene copolymer, vinyl acetate and acrylate copolymer, vinyl acetate and maleate ester copolymer, acryl copolymer, ethylene-
There are emulsions such as acrylic acid copolymers. Representative examples of latex-type adhesives include rubber latex such as natural rubber, styrene butadiene rubber (SBR), acrylonitrile butadiene rubber (NBR), and chloroprene rubber (CR). As the adhesive for dry laminating, as described in pages 859 to 862 of “Plastic Film and Resin Materials Overview '95” published by the Processing Technology Research Group on October 30, 1995, etc. Type, solvent type, solventless type, aqueous type, two-component solvent type, one-component non-solvent type, two-component non-solvent type, emulsion type, etc., and acrylic adhesive, polyether adhesive, polyether type Polyurethane-based adhesives, polyester- and polyurethane-based adhesives, polyester- and isocyanate-based adhesives, aromatic polyester-based adhesives, aliphatic polyester-based adhesives, aromatic polyether-based adhesives, fats Group adhesives, polyester-based adhesives, isocyanate-based adhesives, polyurethane-based adhesives and the like. Among these, a two-component solvent type polyurethane adhesive is particularly preferable. The dry thickness is 0.5-8 μm, preferably 1-5 μm. Other paraffin wax, microcrystalline wax, ethylene-vinyl acetate copolymer resin, ethylene / α-olefin copolymer resin,
Known adhesives such as a hot-melt laminate adhesive, a pressure-sensitive adhesive, and a heat-sensitive adhesive in which a tackifier resin, an ethylene-ethyl acrylate copolymer resin, or the like is blended can be used.

The polyolefin type adhesive for extrusion lamination, which is preferable as the adhesive layer of the present invention, is more specifically a homopolyethylene resin, a polypropylene resin, a polybutylene resin having various densities, and an ethylene copolymer (EVA resin, EEA resin). Resin, EAA resin, etc.) resin, and a copolymer of ethylene with some other monomer (α-olefin), such as L-LDPE resin, Du.
Ionomer resins (ionic copolymers) such as "Surlyn" by Pont and "Hyramin" by Mitsui Polychemicals
Single or blend (mixture) of two or more acid-modified polyolefin resins such as "Admer" of Mitsui Petrochemical Co., Ltd.
There are resins and the like. In addition, UV curable adhesives and the like have recently been used.

In particular, an LDPE resin, an L-LDPE resin, or a blend resin of an LDPE resin and an L-LDPE resin is preferable because it is inexpensive and has excellent laminating suitability. When improving the adhesive strength, acid-modified polyolefin resin
50% by mass, preferably 2 to 45% by mass, more preferably 4 to 40% by mass, particularly preferably 6 to 35% by mass, and most preferably 10 to 30% by mass.

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

The acid-modified polyolefin resin refers to a modified polyolefin resin obtained by graft-modifying a polyolefin resin and an unsaturated carboxylic acid, such as 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.).

Unsaturated carboxylic acids graft-modified with polyolefin resins are generically referred to, including their derivatives. Typical examples thereof include acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, tetrahydrophthalic acid, and mesacon acid. Acid, angelic acid, citraconic acid, crotonic acid, isocrotonic acid, nadic acid, (endocis-bicyclo [2,2,1] hept-5-ene-2,3-dicarboxylic acid), maleic anhydride, citraconic anhydride, Itaconic anhydride, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, glycidyl acrylate, glycidyl methacrylate, monoethyl maleate,
Maleic acid diethyl ester, fumaric acid monomethyl ester, fumaric acid dimethyl ester, itaconic acid diethyl ester, acrylamide, methacrylamide, maleic monoamide, maleic diamide, maleic acid
N-monoethylamide, maleic acid-N, N-diethylamide, maleic acid-N-monobutylamide, maleic acid-N, N-dibutylamide, fumaric acid monoamide, fumaric 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, maleic Monomethyl acrylate, dimethyl maleate, potassium matacrylate, 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, etc.
Mixed use with each other is also possible.

Of these, 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.

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

The amount of the unsaturated carboxylic acid to be used is not particularly limited, but may be a polyolefin resin base polymer (various polyethylene resins, various polypropylene resins, various polyolefin copolymer resins, polybutene-1 resin, poly-
Α-olefin copolymer resin such as 4-methylpentene-1 and the like) and 0.0
It is 1 to 20 parts by weight, preferably 0.2 to 5 parts by weight.

An organic peroxide or the like is 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) hexyne, di-t-butyl peroxide, cumene hydroperoxide, t-butyl-hydroperoxide, dicumyl peroxide, t-
Butylperoxylaurate, t-butylperoxybenzoate, 1,3 bis (t-butylperoxyisopropyl) benzene, cumene hydroperoxide,
Organic peroxides such as di-t-butyl-diperoxyphthalate, t-butylperoxymaleic acid, and isopropyl percarbonate; azo compounds such as azobisisobutyronitrile; 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 or higher.
Di-t-butyl peroxide, di-cumyl peroxide, 2,5-dimethyl-2,5di (t-butylperoxy) hexane, 2,5-dimethyl-2,5di (200 ° C.) 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.

Typical 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 RESI”
N ”(4) Mitsubishi Chemical Industry KK“ NOVATEC-
AP ”(5) Mitsubishi Yuka KK“ MODIC ”(6) Nippon Unicar KK“ NUC-ACE ”(7) Ube Industries KK“ UBE BON ”
D ”(8) Tosoh KK“ Lusen M ”(9) Sumitomo Chemical KK“ Bondane ”(10) Mitsui / DuPont Chemical KK“ CMPS ”etc. (11) Exxon“ Dexon ”(12) Toa Fuel Industries KK“ HA ” Series ”(13) Mitsui Toatsu Chemicals KK“ MITSUI L
ONLY ”etc.

Further, a mixed (blended) resin in which two or more of the above-described resins are blended to cover the defects of each resin is particularly preferable because of its excellent laminating suitability. Especially LD
It is particularly preferable in the present invention to blend the PE resin or the L-LDPE resin and the acid-modified polyolefin resin in an appropriate ratio, since the desired adhesive strength can be obtained. In order to improve the easy-openability by setting the delamination strength of the laminated film to 350 g / 15 mm width or more, particularly preferably 500 g / 15 mm width or more, and most preferably 600 g / 15 mm width or more, it is necessary to use the dry laminating adhesive or A solvent type adhesive or a polyolefin resin type adhesive for extrusion lamination containing at least 5% by mass of an acid-modified polyolefin resin is particularly preferred.

The resin temperature of the polyolefin resin-type adhesive layer for extrusion lamination is from 150 to 400 ° C., preferably from 180 to 380 ° C., more preferably from the viewpoint of the balance between securing the interlayer peel strength of the laminated film and preventing the resin from being thermally degraded. Is from 210 to 360 ° C, particularly preferably from 240 to 360 ° C.
350 ° C, most preferably 280-340 ° C. The thickness of the adhesive layer is from 7 to 50 μm, preferably from 9 to 40 μm, more preferably from 10 to 30 μm, and particularly preferably from 11 to 2, from the viewpoint of ensuring the delamination strength and economy.
0 μm, most preferably 13 to 17 μm.

The characteristics of the adhesive for dry lamination can be summarized as follows: 1) Since it is used after being dissolved in a solvent, the substrate has good wettability. 2) Various materials such as paper, thermoplastic resin film, non-woven fabric, synthetic paper, cellophane, etc. 3) Stable reaction and strong adhesive strength can be obtained 4) Peeling strength can be increased to 400g / 15mm width or more, so easy-opening property is good 5) Excellent heat resistance 6) Reactive type, main material / Pot life (possible use time) after mixing with curing agent and solvent. 7) Solid content is 0.5 to 10 g / m ² , preferably 1 to 8 g / m ² , particularly preferably 1. using a gravure method (smoothing bar combination) and 5-6 g / m ² as a thin layer capable 8) coating method, precisely controllable coating amount

However, 30-65 ° C. until complete curing.
Requires aging for 1-5 days.

[0205] Recently, the public
One-component non-solvent type
Adhesive for lye laminating adversely affects photographic properties
This is preferable in the present invention because there is no such a material. This dry laminate
Adhesive is based on polyurethane adhesive
3,000 CPS or less to minimize coating amount
Heat to 60-110 ° C to lower viscosity below
It is a kind of hot-melt method.
It is necessary to change the amount of cloth. Also higher than dry lamination method
Speedy drying, easy drying (unnecessary in some cases)
The amount of cloth is also 5g / m ²Or less, preferably 3 g / m²Below,
Preferably 0.3 to 2 g / m², Most preferably 0.
5 to 1.5 g / m²And the amount of application is very small.
3 rolls or more, preferably because roll accuracy is required
Use a multi-stage roll coating method with four or more rolls
preferable.

To manufacture the packaging material for a photographic light-sensitive material of the present invention, for example, one of a gas adsorbing substance, a lubricant, a hydrotalcite compound, a light-shielding substance, a hindered phenolic antioxidant and an antistatic agent After mixing master batch resin pellets containing the above at a high concentration of 3 to 30 times the concentration in the light-shielding polyolefin resin film layer and one or more natural (non-colored) matrix resin pellets for dilution, the extruder screw Using an extruder having a ratio (L / D) of the effective length L to the outer diameter D of 10 to 50, the melt temperature is kneaded at a resin temperature of 130 to 270 ° C, and the lip clearance is 0.7 to 5 mm. And a draw ratio (ratio of lip clearance to film thickness) of 3 to 100.

In the above-mentioned method for producing a packaging material for a photographic light-sensitive material, the molecular orientation and the prevention of the occurrence of melt fracture are balanced by the lip clearance of the ring die, and the kneadability, exothermicity, and extrudability are determined by L / D. Is balanced. The balance between thermal degradation and the fluidity of the resin is determined by the resin temperature, and the molecular orientation and the occurrence of melt fracture are prevented and the productivity is balanced by the draw ratio.

When laminating via an adhesive layer, various anchor coat layer treatments, corona discharge treatments, ozone treatments, ultraviolet irradiation treatments described in JP-A-3-125138 and the like can be used to improve the adhesive strength. It is preferable to perform a surface activation treatment such as a flame treatment or a glow discharge treatment.

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 / sealed packaging bags for packaging a transparent, colored or printed film unit with a lens (Japanese Patent Publication No. 7-1380, Japanese Patent Application Laid-Open No. 3-243946, Japanese Patent Application Laid-Open No. 5-19)
7087, JP-A-7-72593, JP-A-8-248573, JP-A-8-254793, JP-A-8-334869, JP-A-9-157
No. 96, JP-A-9-54395, JP-A-9-54
120119, JP-A-9-244187,
JP-A-9-274288, JP-A-10-1865
86, JP-A-10-197994, etc.). (2) Photographic film for photography in a transparent, colored or printed plastic container (JIS 135 film, AP
Moisture-proof / sealing packaging bags (for example, JP-A-8-254793) for collectively packaging two or more of S films, microfilms and the like. (3) Moisture-proof / sealing / light-shielding bags for sheet-like photographic photosensitive materials such as photographic paper, film for printing plate making, cut film for photographing, X-ray film, PS plate (JP-B 2-2700, JP-B-2) -2701, JP-A-8-25479
No. 3, JP-A-5-5972, etc.). (4) Light-shielding films for belt-shaped photographic photosensitive material packages (JP-A-2-72347, JP-A-6-214350, Japanese Utility Model Publication No. 5-29471, Japanese Utility Model Application Publication No. 6-8593)
Gazette, Japanese Utility Model Publication No. 7-50743, Japanese Utility Model Publication No. 8-10
812, JP-A-63-153255, etc.). (5) Moisture-proof sealed light-shielding bags for roll-shaped photographic light-sensitive materials such as photographic paper, movie films, micropositive films, printing plate-making films, and thermally developed diffusion transfer papers (JP-A-6-6735).
No. 8). (6) A moisture-proof / light-shielding film or a leader film for a light-room-packed package of a belt-shaped photosensitive material such as photographic paper, photographic film or the like (Japanese Patent Application Laid-Open Nos. 62-172344 and 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
2618, JP-A-8-40468, JP-A-10-97030, JP-B-56-16608, JP-B-6-8593, JP-B-8-9725 and the like. (7) A moisture-proof and light-shielding film for packaging a photographic photosensitive material in the form of a bulk roll (JP-A-3-53243). (8) Instant film pack (JP-A-8-627)
82, JP-A-10-228079, JP-A-10-228080, etc.). (9) Shading paper for photographic film (US Pat. No. 5,790,9
12, JP-A-48-22020, JP-A-50-67644, JP-A-52-150016, JP-A-55-140835, and JP-A-58-158.
17434, JP-A-58-186744,
JP-A-59-68238, JP-A-60-3572
No. 8, JP-A-61-36216, JP-A-63
169,624, JP-A-4-136842, JP-A-4-296,849, JP-A-5-281
666, JP-A-9-80695, JP-A-9-80695
Japanese Patent Application Laid-Open Nos. 5-26585, 9-185151, 10-104803, and 10-2
No. 54102, Japanese Unexamined Patent Publication No. 10-254103,
JP-A-10-312042, JP-A-10-312
043, JP-A-10-319545, JP-A-10-325993, JP-A-11-38563
No.). (10) Shading bag for instant film pack
0-186504, JP-A-10-221814, JP-A-10-228079, JP-A-10-208
JP-A-228080, JP-A-10-288810, JP-A-10-293359, JP-A-10-3
01199, JP-A-10-301248, etc.). (11) Packaging bags for substances requiring high airtightness, such as foods and pharmaceuticals.

[0210] The above-mentioned various sealing bags are formed by using a bottom sealing bag of a tubular film and the above-mentioned packaging material, and forming a sealing portion by superposing the surfaces of the heat-sealing resin layers so as to face each other. Sealed bags, three-sided sealed bags, four-sided sealed bags, gusset bags, envelope-attached seal bags, gasket-attached seal bags (pillow seal bags), fold-sealed seal bags, square-bottomed seal bags, and other heat-sealed various heat-sealed forms And the like.

[0211] It can also be used for various overwrapping packages. For example, Japanese Utility Model Publication No. 7-50743, Japanese Utility Model Publication 8-7398, Japanese Utility Model Publication 8-9723, Japanese Utility Model Publication 8-9724, Japanese Utility Model Publication No. 8-10812,
JP-A-6-148820, JP-A-6-21435
0, JP-A-7-257510, JP-A-7-257510
No. 287350, etc., on a moisture-proof light-shielding film or bag for a light-room-loaded package of a strip-shaped photosensitive material, overwrapping a carton or tray, overwrapping a caramel type, overwrapping a snack type, over a cigarette type There are wrapping packaging, roll wrapping packaging, rod-shaped wrapping wrapping, twist wrapping wrapping, and the like. Also, various types described in the Packaging Technology Handbook, pages 754 to 774, published on July 1, 1995 by the Japan Packaging Technology Association. It can be used for packaging.

The photographic light-sensitive materials applicable to the packaging material for photographic light-sensitive materials of the present invention are shown below. (1) Silver halide photographic materials (film for printing, color or black and white photographic paper, color or black and white negative film, master paper for printing, DTR (diffusion transfer) photosensitive material,
Computerized typesetting film and paper, color or black-and-white positive film, color reversal film, microfilm, surveillance film, movie film, self-developing photographic light-sensitive material, direct positive film and paper, etc. (JP-A-4-13638, JP-A-4-17
2339, JP-A-5-113623, JP-A-9-325450, JP-A-10-62901, JP-A-10-62903, JP-A-10-6
2904, JP-A-10-62905, JP-A-10-62906, JP-A-10-62921, JP-A-10-142731 and the like) (2) Photothermographic materials Materials, heat-developable black-and-white light-sensitive materials (for example, JP-B-43-4921 and JP-B-43-4924, "Basics of photographic engineering", silver halide photography, published by Corona Co., Ltd., 1879), pages 553 to 555.
And pages 9 to 15 (RD-17029), etc., June 1978, Research Tis Closure Magazine. Further, JP-A-59-12431,
JP-A-60-2950, JP-A-61-52343,
JP-A-7-13295, JP-A-10-62898, JP-A-10-62899, JP-A-10-1865
No. 67, JP-A-10-268465, JP-A-10-339934, JP-A-10-52509, U.S. Pat. No. 3,457,075, U.S. Pat. No. 3,574,627 Specification, U.S. Pat.
No. 42,394, U.S. Pat. No. 4,584,267.
(3) Photosensitive and thermosensitive recording materials (photothermography (photosensitive and thermosensitive images) described in JP-A-3-72358, etc. (4) Diazonium photographic material (4-morpholinobenzenediazonium microfilm, microfilm, copy film, printing plate, etc.) (5) Azide, diazide photographic material ( Photosensitive materials containing para-azide benzoate, 4,4'-diazidostilbene, etc., for example, copying films, printing plate materials, etc. 1,2) -diazide- (2) -4-
Photosensitive materials containing sulfonic acid phenyl ether, etc.
(7) Photopolymer (photosensitive material containing vinyl monomer, etc., printing plate, adhesive film, etc.) (8) Polyvinylcinnamic acid ester photosensitive material Material (for example, printing film, resist for IC, etc.) (9) Dry image forming material (on a support, at least a layer containing at least a photocurable compound, a photoinitiator and a dye precursor is contained, and the microcapsules are formed. Or a recording material described in JP-A-11-2884 having a color developer in an adjacent layer or a layer adjacent thereto

In particular, the present invention is preferably applied to a packaging material and a package for loading a X-ray film in a bright room. For example, JP-A-2679993, JP-A-11-237713,
JP-B-7-31376, JP-B-2572221, JP-A-2-83543, JP-B-7-31377, JP-A-7-287329, and the like.

The photographic light-sensitive materials to which the packaging material of the present invention is applied include black-and-white and color photographic light-sensitive materials in general. Therefore, regardless of whether it is for photography or printing, and for black-and-white and color negative films, black-and-white and color reversal films, black-and-white and color photographic paper, and for general, movie and professional The present invention can be applied to a packaging material for storing a photosensitive material.

The photographic light-sensitive materials according to the present invention are all new, known, and general-purpose materials. 17643 (197
December 2008, p. 22-23, "I. Emulsion products (Emu
Lsion preparation and type
s) "and No. 18716 (November 1979)
Mon.), p. 648, ibid. 307105 (1989, 1
Jan.), pages 863 to 865, and Grafkid, "Physics and Chemistry of Photography", published by Paul Montell (P. Glafk)
ides, Chemie et Physique Ph
autographique, Paul Montel,
1967), "Photographic Emulsion Chemistry" by Duffin, published by Focal Press, Inc. (GF Duffin, Photograph)
phy Emulsion Chemistry, Fo
cal Press, 1966), "Production and Coating of Photographic Emulsions" by Zeligman et al., published by Focal Press (VL.
Zelikman, et al. , Making and
Coating Photographic Emul
Sion, Focal Press, 1964).

The silver halide emulsion and other materials (additives and the like) and the photographic constituent layers (layer arrangement and the like) applied to the photographic light-sensitive material according to the present invention, and the photographic light-sensitive material are applied for processing. European Patent EP 0,355,660 A2, Japanese Unexamined Patent Publication No.
Those described in the specifications of JP-A-33144 and JP-A-62-215272 or those listed in the following table are preferably used, but the present invention is not limited thereto.

[0219]

[Table 4]

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

[0219] In the following examples of the layer structure, the mark / indicates that the layers were laminated via an adhesive layer (a surface activation treatment or an undercoat layer or an anchor coat layer may be applied).
The mark indicates that the layers were directly laminated without interposing the adhesive layer by coextrusion. 1 indicates a light-shielding polyolefin resin film layer, 2 indicates a flexible sheet layer, and a indicates that the layer has light-shielding properties. In addition, it is described in order from the outermost layer to the innermost layer.

[Single-layer film structure] Single-layer structure of light-shielding polyolefin resin film layer 1a [2-layer film structure] 1 * 1, 1 * 1a, 1a * 1, 1
a * 1a, 2 * 1, 2a * 1, 2 * 1a, 2a * 1a [Three-layer film configuration] 2/1, 2a / 1, 2 / 1a, 2
a / 1a, 1/2, 1 / 2a, 1a / 2, 1a / 2a,
1 * 1 * 1, 1 * 1 * 1a, 1 * 1a * 1a, 1a * 1
a * 1a, 1a * 1 * 1, 1a * 1a * 1, 1 * 1a *
1, 2 * 1 * 1, 2 * 2 * 1, 2 * 2a * 1, 2a * 2
a * 1, 2 * 1a * 1, 2 * 1a * 1a, 2a * 1a *
1a, 1 * 2 * 1, 1a * 2 * 1, 1a * 2a * 1, 1
a * 2a * 1a, 1 * 1 * 2, 1 * 1 * 2a, 1a * 1
* 2a, 1a * 1a * 2a, 2 * 1a * 2a, 1/2,
1a / 2, 1a / 2a, 1/1, 1a / 1, 1a / 1
a, 1 / 1a, 2/1, 2a / 1, 2a / 1a [four-layer film configuration] 1 * 1 * 1 * 1, 1a * 1 * 1 *
1, 1a * 1a * 1 * 1, 1a * 1a * 1a * 1a, 1
* 1a * 1a * 1, 1 * 1 * 1a * 1a, 1 * 1a * 1
a * 1a, 1a * 1a * 1a * 1a, 2 * 1a * 1a *
1a, 2 * 2 * 1a * 1a, 2 * 2 * 2 * 1a, 2 / the above two-layer film configuration, 2a / the above two layer film configuration, the above two layer film configuration / 2, the above two layer film Configuration / 2a [Five-layer film configuration] Five-layer co-extruded film composed of five layers of 1, 1a, 2, and 2a, the single-layer film configuration described above,
A five-layer film configuration that can be made into a five-layer film configuration by combining a three-layer film configuration, a three-layer film configuration, and a four-layer film configuration

[0221]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below with reference to embodiments. However, the present invention is not limited to these embodiments, but may be modified within the scope of the invention described in the appended claims. All are included.

[Product 1 of the Invention] A packaging material for a photographic photosensitive material comprising a single layer of a light-shielding polyolefin resin film.

<Polyolefin resin> An ethylene-hexene-1 copolymer resin (MFR of 2.0) polymerized by a gas phase method using one type of metallocene catalyst as a single site catalyst.
g / 10 minutes, density: 0.925 g / cm ³ , molecular weight distribution by GPC method: 2.5, Vicat softening point: 106 ° C., melting point: 123 ° C., Shore hardness: 56D) 60 parts by mass; High-density polyethylene resin (MFR 0.4 g /
10 minutes, density: 0.960 g / cm ³ , molecular weight distribution by GPC method: 25, Vicat softening point: 125 ° C., melting point: 13
30 ° C .; 3 ° C., Shore hardness: 65 D) 30 parts by mass; low-density homopolyethylene resin (M
FR: 2 g / 10 min, density: 0.920 g / cm ³ , G
The molecular weight distribution of the PC method is 5.5, and the Vicat softening point is 92.
° C, melting point 110 ° C, Shore hardness 52D) 10 parts by mass;

<Gas adsorbing substance> 0.1 part by mass of A-type zeolite which also has an anti-blocking action; 0.05 part by mass of talc; 0.05 part by mass of synthetic silica;

<Lubricant> 0.05 parts by mass of zinc stearate which also has a function of neutralizing the polymerization catalyst residue of the polyolefin resin and improving the photographic properties of the photographic light-sensitive material; improving the dispersibility of the light-shielding substance 0.2 parts by mass of a polypropylene wax having a number average molecular weight of 3500, which also has an effect of causing the resin to flow; 0.05 parts by mass of erucamide, which plays an important role of improving resin fluidity, preventing blocking and improving lubricity;

<Hydrotalcite compounds> Mg _0.7 Al _0.3 (OH) ₂ (CO ₂ ) having a BET specific surface area of 64 m ² / g and an average secondary particle diameter of 16 μm represented by the following formula:
₃ ) 1.5 parts by mass of _0.15 · 0.50 H ₂ O;

<Light-shielding substance> pH 7.0, average particle size 20 mμ, DBP oil absorption 67 cc / 100 g, sulfur content 0.05%, nitrogen adsorption surface area 130 m ² /
g, ash content: 0.2%, tinting strength: 130%, volatile content: 0.1%.
3 parts by mass of 8% furnace carbon black;

Among these, the aspect ratios of the inorganic pigments such as furnace carbon black and silica are 3.5 or less, and the aspect ratio of talc is 5 or more. The appearance improves.

<Antioxidant> Tetrakis [methylene-3- (3 ′,
5'-di-tert-butyl-4'-hydroxyphenyl) propionate] methane 0.05 part by mass;

<Antistatic Agent> An antistatic agent masterbatch manufactured by Kao KK (Erestmaster LL-1 manufactured by Kao KK)
0) 2 parts by mass;

Using the ethylene resin composition as described above,
Under the following blown film molding conditions, a thickness of 70
forming a light-shielding polyolefin resin film layer of μm,
A packaging material for a photographic light-sensitive material was composed of only a single layer of the light-shielding polyolefin resin film layer.

Film forming machine: MODERN MACH
INERY CO. The ratio of the effective length L of the extruder screw to the outer diameter D (hereinafter referred to as
L / D): 28 (outer diameter D is 55 mmφ) Ring die diameter: 175 mmφ Ring die lip clearance: 2.5 mm Blow-up ratio: 2.0 Resin temperature: 195 ° C Cooling method: Air cooling around 25 ° C Draw ratio: about 37

[Products of the Invention 2 to 8 and Comparative Products 1 to 5] Under the same blown film molding conditions as those of the product 1 of the present invention, the use and amount of various additives of the present invention 1 and the composition of the polyolefin resin were changed. A light-shielding polyolefin resin film layer having a thickness of 70 μm was formed.

Table 5 shows the results of comparing the resin compositions and various properties of the products 1 to 8 of the present invention and the comparative products 1 to 5.

[0235]

[Table 5]

The evaluation in the table is based on the following. ◎: Very good. ：: Excellent. ●: Within practical limits. ▲: Practical use difficult, need improvement. ×: Not practical.

The evaluation method of the characteristics is as follows. <Film Formability> Comprehensive evaluation was conducted on the bubble stability, the degree of melt fracture, the degree of wrinkles and streaks, the degree of bumps and microgrids, the degree of heat generation during extrusion, and the power load when the film was formed. <Photographic Properties> A color photographic paper is hermetically sealed in a moisture-proof and light-shielding bag made of a light-shielding polyolefin resin film by a heat sealing method, and then left for 3 days in a constant temperature / humidity room at a temperature of 40 ° C. and a relative humidity of 80%. Thereafter, evaluation was made based on the degree of photographic change such as fogging, sensitivity, gradation, and color development with the type (blank) during normal development processing. <Bulletin (Solid Foreign Material)> The degree of difficulty in producing bumps when a light-blocking polyolefin resin film was produced using a film forming machine was evaluated by visual inspection of the light-blocking polyolefin resin film. <Suitability for heat sealing> Evaluation was made based on the total suitability of heat seal strength, heat seal strength retention with time, contaminant sealability, and hot tack property when a light-shielding polyolefin resin film was bonded by heat sealing. <Physical strength> The physical strength was evaluated based on the tear strength and impact drilling strength of the light-shielding polyolefin resin film. <Antistatic property> An endless belt having a width of 35 mm and a length of 1350 mm was made of a packaging material to be tested, and this endless belt was fed between a SUS (stainless steel) roll having a load of 500 g and a SUS roll at a speed of 12 m / min. The strip voltage was measured with a voltmeter (Shinto Kagaku KK
Measuring instrument). <Easy Opening Property> A V-notch was formed in the longitudinal direction of the packaging material to be tested, and this portion was evaluated for ease of tearing when trying to tear by hand and straight-line tearing. <Moisture resistance> Measured at a temperature of 40 ° C and a relative humidity of 90% by a bag method according to ASTM D895-79.

The products 1 to 8 of the present invention have photographic properties, light-shielding properties, heat-sealing suitability, various physical strengths, film moldability, moisture resistance, abrasion resistance, lubricity, antistatic properties, anti-blocking properties, and easy-openability. Various properties essential for packaging materials for photographic photosensitive materials, such as moisture-proof, light-tight sealing, suitability for manufacturing photographic light-sensitive material packaging, suitability for sealing photographic materials and taking them in and out of light-shielding bags, suitability for long-term storage, etc. It was excellent in reuse and recyclability that could be secured at a reasonable price, was easily available in overseas producing countries, and cleared the Containers and Packaging Recycling Law that was enforced in Japan in April 2000.

[Product 9 of the Present Invention] Product 9 of the present invention contains 2 parts by mass of iron oxide in addition to the same furnace carbon black as products 1 to 8 of the present invention as a light-shielding substance.
Due to the combined effect with 5 parts by mass of the type zeolite, the generation of dioxin was almost zero. This is because the combustion temperature of the light-shielding polyolefin resin film layer can be raised by the catalytic action of the iron oxide, and oxygen of the iron oxide is released at the time of combustion, and this oxygen is bonded to the benzene nucleus generated by the burning of the dust. Then, chlorine generated by the combustion of the chlorine compound in the catalyst residue is bonded to the benzene nucleus (this is dioxin).
In addition to this, dioxin and A-type zeolite, which is a gas adsorbing substance that adversely affects photographic properties, eliminates the generation of dioxins, thereby providing excellent photographic properties.

[Products of the Invention A to E and Comparative Product A] Product of the Invention 1
80 parts by mass of low density homopolyethylene resin and acid-modified L
-15 μm thick composed of 20 parts by mass of LDPE resin
This is a packaging material for a photographic light-sensitive material comprising a laminated film in which various flexible sheet layers shown in Table 6 are laminated via an extrusion laminate adhesive layer.

[0241]

[Table 6] (Comparison of Laminated Films) The product A of the present invention is particularly inexpensive, having good moisture-proofing properties, light-shielding properties and lubricity. The product B of the present invention has particularly good moisture-proof properties and physical strength and is inexpensive. The product C of the present invention is particularly excellent in oxygen barrier properties, bag breaking strength and heat resistance, but is expensive. The product D of the present invention is particularly excellent in oxygen barrier properties, heat resistance and suitability for bag making, and is inexpensive. The product E of the present invention has more excellent properties than the product D of the present invention (see comparative values below). In particular, it is most preferable because it is excellent in various properties required for packaging materials for photographic light-sensitive materials, such as light-shielding properties (small ultraviolet transmittance), moisture-proof properties, oxygen barrier properties, heat resistance, and physical strength. Comparative product A is an unstretched low-density polyethylene resin film used in large quantities as a flexible sheet in agricultural films and the like, but has poor heat resistance and physical strength, is more expensive than Product 1 of the present invention, Was not preferred.

The products A to E of the present invention are more excellent in photographic properties, anti-collapse properties, suitability for bag making, suitability for heat sealing, bag breaking strength, finger slip resistance, dust resistance, moisture resistance, heat resistance, and the like than the product 1 of the invention. It is a packaging material which is more excellent in printability, physical properties, appearance, etc., and is preferable as a packaging material for photographic photosensitive materials. Moisture proof,
In order to further improve oxygen barrier properties and appearance, aluminum, silicon oxide, aluminum oxide, titanium oxide as a photocatalyst, or the like may be deposited by various methods.

In particular, a biaxially stretched polyethylene naphthalate resin film having various properties superior to that of a biaxially stretched polyester resin film is the most preferable as the packaging material for a photographic light-sensitive material of the present invention.

The results of comparing the properties of a biaxially stretched polyester (PET) resin film with the same film thickness and a biaxially stretched polyethylene naphthalate (PEN) resin film are described below.

The values of the biaxially stretched polyethylene naphthalate resin film when the biaxially stretched polyester resin film [1] is used are described.

Properties (excellent properties of PEN resin film) Refractive index 1 → 1.06 (excellent light blocking ability) Longitudinal Young's modulus 1 → 1.20 (excellent bag breaking strength and curl prevention) Longitudinal breaking Strength 1 → 1.22 (excellent bag breaking strength) Longitudinal breaking elongation 1 → 0.75 (excellent anti-curl property of laminated film) Melting point 1 → 1.08 (excellent suitability for bag making and appearance) Glass transition temperature 1 → 1.55 (excellent suitability for bag making, excellent appearance) 150 ° C x 30 min heat shrinkage 1 → 0.27 (excellent suitability for bag making, excellent appearance) Water vapor transmission rate 1 → 0.31 (improves photographic properties) Oxygen gas permeability 1 → 0.38 (maintain good photographic properties) Carbon dioxide gas permeability 1 → 0.28 (maintain good photographic properties) 25 ° C. surface electrical resistivity 1 → 0.33 (Excellent antistatic properties) 360nm UV transmission Rate 1 → 0.10 (Excellent light blocking ability)

[0247]

(1) The photographic performance can be maintained for a long period of time (one year Above) can be maintained well. (2) It is inexpensive, has a very low content of substances that adversely affect the photographic properties of the photographic light-sensitive material, and does not generate substances that adversely affect the photographic properties even when heated or aged. (3) Use an inflation film molding machine that is inexpensive to form a film and can be of any thickness, width (variable blow ratio) and molecular orientation (variable draw ratio) with a single molding machine.
A light-shielding polyolefin resin film having an arbitrary width and molecular orientation can be produced and used. (4) Excellent reusability and recycle suitability 2000
Clears the Containers and Packaging Recycling Law, which came into effect in April of the year, and does not generate harmful properties such as dioxin and chlorine gas when incinerated. (5) Flexibility, light-shielding properties, photographic properties, physical strength, heat-sealing suitability, appearance, antistatic properties, easy-openability, moisture-proof properties, long-term sealing, light-shielding properties, lubricity, etc., are essential as packaging materials for photographic photosensitive materials. Various characteristics can be secured.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08K 3/26 C08K 3/26 3/34 3/34 3/36 3/36 5/00 5/00 5 / 098 5/098 5/13 5/13 C08L 23/00 C08L 23/00 F term (reference) 4J002 BB031 BB032 BB051 BB061 BB071 BB081 BB121 BB141 BB151 BB201 BB231 BP021 CP032 DA016 DD066 DE049 DE219 DE288 DG0DJDJ006 EH047 EJ019 EP017 FD079 FD099 FD172 FD177 FD206 FD209 GG02

Claims (5)

[Claims] 1 to 100 parts by mass of a polyolefin resin, 0.01 to 20 parts by mass of a gas adsorbing substance for adsorbing a gas that adversely affects photographic properties, 0.01 to 2 parts by mass of a lubricant, and 0.1 to 2 parts by mass of a hydrotalcite compound. A packaging material for a photographic light-sensitive material, comprising a light-shielding polyolefin resin film layer containing from 0.1 to 25 parts by mass and from 0.1 to 40 parts by mass of a light-shielding substance. 2. The packaging material according to claim 1, wherein the polyolefin resin is a polyolefin resin produced with a Ziegler catalyst or a metallocene catalyst. 3. The packaging material for a photographic light-sensitive material according to claim 2, wherein said gas-adsorbing substance is at least one of synthetic zeolite and synthetic silica. 4. The packaging material for a photographic light-sensitive material according to claim 1, wherein the lubricant is at least one kind of a metal salt of a higher fatty acid having 10 to 25 carbon atoms. 5. The photographic light-sensitive material according to claim 1, wherein the light-shielding polyolefin resin film layer contains a hindered phenolic antioxidant in an amount of 0.01 to 1 part by mass based on 100 parts by mass of the polyolefin resin. Packaging material.