JP2002072417A - Packaging material for photosensitive material and photosensitive material packaged body using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a packaging material for a photosensitive material excellent in moisture-proof property, oxygen barrier property, sealing performance, antistatic performance, photographic properties and suitability to incineration and adaptable to the Containers and Packaging Recycling Law. SOLUTION: The packaging material has a high Young's modulus heat resistant thermoplastic resin film layer having >=50 kg/mm2 Young's modulus in the longitudinal direction (ASTM D 882), >=130 deg.C melting point by DSC (differential scanning calorimetry) and 5-70 μm thickness, a barrier film layer disposed on one face or both faces of the thermoplastic resin film layer, having 50-3,000 Å(5-300nm) thickness and comprising a metallic thin film layer and/or a thin film layer of an inorganic material and a heat sealable layer disposed on the inside (photosensitive material side) of the barrier film layer optionally by way of an adhesive layer and based on an ethylene/α-olefin copolymer resin to be a main component obtained by polymerization with a single-site catalyst.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photosensitive material packaging material having excellent moisture proofing properties, oxygen barrier properties, sealing properties, antistatic properties, photographic properties and incineration properties, and a photosensitive material packaging using the same.

[0002]

2. Description of the Related Art Various types of packaging materials have been proposed as packaging materials for packaging photographic photosensitive materials such as photographic paper and photographic film. For example, Japanese Utility Model Publication No. Sho 61-20590 discloses that an HDPE resin film containing carbon black is uniaxially stretched at a stretching ratio of 2.2 to 4.2, and the stretching axis is four.
A cross-laminated film in which two or more layers are laminated so as to cross at an angle of 5 to 90 degrees has been proposed.

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

Japanese Utility Model Publication No. 2-19226 discloses that an anchor coat layer is formed on an inner light-shielding heat-sealing film layer containing a lubricant, a light-shielding substance and 50% by weight or more of an LDPE resin, and the aluminum foil has a peel strength of 400 g. / 15
Packaging materials laminated with a width of not less than mm have been proposed.

Japanese Patent Publication No. 63-26697 discloses that from the outside, a PET layer / aluminum layer / a PO-based resin layer containing a light-shielding material and a nonionic antistatic agent has an optical density of 7.5 or more. Packaging materials have been proposed.

[0006]

However, the above-mentioned conventional packaging materials do not have all functions sufficiently as packaging materials for photographic light-sensitive materials, and each has problems. That is, the packaging material proposed in Japanese Utility Model Publication No. 61-20590 is expensive and has insufficient antistatic properties, heat sealing suitability, and moisture proof properties.

[0007] The photosensitive material packaging film proposed in Japanese Patent Publication No. 2-2700 is insufficient in antistatic properties, moisture proof properties, oxygen barrier properties and Young's modulus. If it is laminated and covered, it is expensive and there is a problem in physical strength and the like.

The packaging material proposed in Japanese Utility Model Publication No. 2-19226 has problems in photographic properties, sealing properties by heat sealing, physical strength and the like.

The packaging material proposed in Japanese Patent Publication No. 63-26697 is expensive, has anti-blocking properties, photographic properties,
There were problems such as insufficient sealing properties and physical strength by heat sealing.

Although the homopolyethylene resin alone is insufficient in the sealing property by heat sealing (especially after a lapse of one month or more), when a light-shielding substance is contained, the sealing property is further deteriorated, and the lubricant, the charge When an additive that bleeds out such as an antioxidant or an antioxidant is contained, it was difficult to ensure complete sealing by heat sealing after one year or more. Further, aluminum foil has a problem that it is difficult to completely remove the rolling oil used during rolling by annealing, thereby deteriorating photographic properties.

Further, the above-mentioned conventional packaging materials have been proposed mainly for achieving the purpose of maintaining good quality of photographic light-sensitive materials for a long period of time, and have been in effect since April 1, 2000. It did not take into account compliance with the Act on the Promotion of Separate Collection and Recycling of Containers and Packaging (hereinafter referred to as the Containers and Packaging Recycling Act). For example, metal foils, such as aluminum foils, lacked incineration suitability, and it was difficult to clear the “Container and Packaging Recycling Law”.

Therefore, the above-mentioned conventional packaging material is
In some cases, the quality of photographic light-sensitive materials cannot be maintained for a long period of time, or the provisions of the Containers and Packaging Recycling Law cannot be satisfied.

The present invention solves the above problems and uses a barrier film layer obtained by depositing a metal thin film and / or an inorganic thin film layer on a high Young's modulus and heat resistant thermoplastic resin film layer. It is an object of the present invention to provide a photosensitive material packaging material that can improve various properties that have been insufficient and that can comply with the Containers and Packaging Recycling Law.

[0014]

The packaging material for a photosensitive material according to the present invention has a Young's modulus in the longitudinal direction (ASTM D882).
Is 50 kg / mm ² or more, the melting point of the DSC method is 130 ° C. or more, and the thickness is 5 to 70 μm. A high Young's modulus and heat resistant thermoplastic resin film layer, and one surface of the high Young's modulus and heat resistant thermoplastic resin film layer Or thickness 50-3 laminated on both sides
A barrier film layer composed of a metal thin film layer and / or an inorganic substance thin film layer having a thickness of 000 ° (5 to 300 nm), and an adhesive layer on the inner side of the barrier film layer (on the photosensitive material side) or via an adhesive layer. And a heat seal layer mainly composed of an ethylene / α-olefin copolymer resin polymerized by using a single-site catalyst laminated without interposition.

[0015]

BEST MODE FOR CARRYING OUT THE INVENTION The packaging material for photosensitive material according to the present invention has a barrier film layer, and the barrier film layer has a metal film layer on one or both sides of a high Young's modulus and heat resistant thermoplastic resin film layer. And / or an inorganic material thin film layer is laminated.

[0016] The high Young's modulus and heat resistant thermoplastic resin film layer includes a biaxially stretched polyamide resin film layer such as nylon 6 or nylon 66 copolymer, a biaxially stretched polyethylene terephthalate resin film layer, and a biaxially stretched polyethylene naphthalate resin layer. In addition to a film layer, a biaxially stretched ethylene / vinyl alcohol copolymer resin film layer, and the like, a thermoplastic resin film described in Table 1 can be used. When these high Young's modulus and heat resistant thermoplastic resin film layers are used, oxygen barrier properties, low temperature strength, heat resistance, suitability for bag making, bag breaking strength and the like are improved. Further, the uniaxially or biaxially stretched polypropylene resin film is inexpensive and has a high Young's modulus.

[0017]

[Table 1]

Representative examples of the polyamide resin (commonly called a nylon resin) used in the biaxially stretched polyamide resin film layer, classified according to the polymerization mode, are shown below. (1) Ring-opening polymerization of lactam Polyamide 6 resin, Polyamide 12 resin (2) Polycondensation of aminocarboxylic acid Polyamide 11 resin (3) Polycondensation of diamine and dicarboxylic acid Polyamide 6-6 resin, Polyamide 6-10 resin, Polyamide 6-12 resin, polyamide MXD6 resin (4) polyamide 3 resin, polyamide 4 resin, polyamide 4-6 resin, polyamide 7 resin, polyamide 9 resin, etc.

The results of comparing various properties of a biaxially oriented polyethylene terephthalate (PET) resin film and a biaxially oriented polyethylene naphthalate (PEN) resin film having the same film thickness are described below. In addition, the value of the biaxially stretched polyethylene naphthalate resin film when the biaxially stretched polyethylene terephthalate resin film is set to “1” is 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)

The biaxially stretched polyethylene naphthalate resin film has excellent heat resistance, moisture resistance and gas barrier properties,
Also, since it has ultraviolet absorption properties, it is most suitable as the outermost layer of a packaging material for photosensitive materials.

In addition, a biodegradable resin film can be used for the high Young's modulus and heat resistant thermoplastic resin film layer, and typical biodegradable resins that can be used for such a biodegradable resin film can be used. Table 2 shows the manufacturers and types.

[0023]

[Table 2]

The Young's modulus (ASTMD 882) in the longitudinal direction of the high Young's modulus and heat resistant thermoplastic resin film layer is 50.
kg / mm ² or more, preferably 80 kg / mm ² or more, more preferably 100 kg / mm ² or more.
kg / mm ² or more is most preferable. If the Young's modulus of the vertical method is less than 50 kg / mm ² , sufficient oxygen barrier properties, low-temperature strength, suitability for bag making, breaking strength of bags, and the like cannot be ensured.

The melting point of the high Young's modulus and heat resistant thermoplastic resin film layer measured by the DSC method is 130 ° C. or more, and 135 ° C.
Or higher, preferably 140 ° C. or higher, and 160 ° C. or higher.
C or higher is most preferred. When the melting point is less than 130 ° C,
Lack of suitability for bag making, lack of sealing properties of the heat-sealed portion, and insufficient heat resistance.

The thickness of the high Young's modulus and heat resistant thermoplastic resin film layer is 5 to 70 μm, preferably 6 to 60 μm, more preferably 7 to 50, and most preferably 8 to 40 μm. If the thickness is less than 5 μm, sufficient oxygen barrier properties, bag breaking strength, and the like cannot be ensured. On the other hand, if the thickness exceeds 70 μm, the cost becomes high and the suitability for bag making cannot be sufficiently ensured.

In the present invention, the most preferred embodiment of the high Young's modulus and heat resistant thermoplastic resin film layer is a biaxially stretched polyamide resin having a Young's modulus in the longitudinal direction of 130 kg / mm ² or more and a melting point of 160 ° C. or more by the DSC method. Film layer,
Biaxially stretched polyethylene terephthalate resin film layer,
It is at least one selected from the group consisting of a biaxially stretched polyethylene naphthalate resin film layer and a biaxially stretched ethylene / vinyl alcohol copolymer resin film layer.

A metal thin film layer and / or an inorganic substance thin film layer are laminated on one or both surfaces of the high Young's modulus and heat resistant thermoplastic resin film layer as described above. By laminating a metal thin film layer and / or an inorganic substance thin film layer,
It has improved antistatic properties, sealing properties, moisture proofing properties and the like.

As the metal thin film layer, aluminum, titanium, selenium, magnesium, barium, indium, calcium, zirconium, thorium, thallium, tantalum, zinc or the like can be used.

As the inorganic substance thin film layer, silicon oxide, aluminum oxide, titanium oxide, tin oxide, zinc oxide, isodium oxide, magnesium oxide, barium sulfate and the like can be used.

Aluminum, silicon oxide, magnesium oxide and aluminum oxide are preferred among the above-mentioned metal thin film layers and inorganic thin film layers. By forming these thin film layers, antistatic properties, sealing properties, and oxygen barrier properties are obtained. sex,
It is possible to improve the moisture resistance and the like, and the quality of the photosensitive material can be maintained satisfactorily for a long time. In particular, chemical sensitization and / or
The present inventor has recently found that it is possible for the first time to maintain the quality of a photosensitive material in good condition for a long period of time by hermetically packaging the dye-sensitized photosensitive material.

The most preferred thin film layer is a thin film layer in which silicon oxide and aluminum oxide are mixed from the viewpoint of comprehensive evaluation such as strength, ease of formation, price, photographic properties, moisture resistance, oxygen barrier property, and the like.

The metal thin film layer and the inorganic substance thin film layer can be 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 thicknesses of the metal thin film layer and the inorganic substance thin film layer are as follows:
50 to 3000 (5 to 300 nm) and 100
~ 2,000 °, preferably 200 ~ 1,5
The angle is more preferably 00 ° (20 to 150 nm), most preferably 400 to 1,000 ° (40 to 100 nm). When the thickness is less than 50 mm, the antistatic property, moisture-proof property and oxygen barrier property may not be sufficiently secured, and when the thickness exceeds 3,000 mm,
In addition to the problem of thermal deterioration and thermal shrinkage of the base material, there are also problems in quality, cost, and productivity, and practical use is difficult.

On one or both sides of the high Young's modulus and heat resistant thermoplastic resin film layer as described above, a metal thin film layer and / or
Alternatively, the barrier film layer on which the inorganic substance thin film layer is laminated is provided with one layer or two or more layers, and a protective layer or various flexible sheets can be laminated on the outside of the barrier film layer. Is preferably a high Young's modulus and heat resistant thermoplastic resin film layer used for the barrier film layer. Further, a heat seal layer is laminated inside the barrier film layer via an adhesive layer or without an adhesive layer.

The heat seal layer is mainly composed of an ethylene / α-olefin copolymer resin polymerized using a single-site catalyst. Such a heat seal layer is necessary for ensuring long-term sealing performance, and can ensure long-term physical strength, heat sealing strength, and sealing performance. Further, the photographic properties of the photosensitive material are not adversely affected, the suitability for recycling and the suitability for incineration are good, and the "Container and Packaging Recycling Law" can be satisfied.

As an ethylene / α-olefin copolymer resin
The most preferred resin in the present invention is L-LDPE
There is a resin. This L-LDPE (LinearLow
DefficiencyPolye(thylene) resin
3 polyethylene-based resin, the conventional medium-low pressure method, high
Energy saving with the advantages of both pressure process polyethylene resins
ー Low cost, high strength to meet the demands of the age of resource saving
Degree of resin. This resin is a multi-site catalyst (typical example)
Is a Ziegler catalyst) or a single-site catalyst (preferred in the present invention).
A typical example is a metallocene catalyst and a post-metallocene catalyst.
Inexpensive, high-activity phenoxy
Low-pressure method or high-pressure improvement using simine complex polymerization catalyst)
Ethylene and one or more α-olefins (described below)
Short branches into linear chains with copolymers obtained by copolymerizing
It is a polyethylene resin having a structure with
To maintain good long-term photographic and sealing properties.
The one polymerized using a single site catalyst is used.

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

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 (weight-average molecular weight / number-average molecular weight) by the GPC method is 5 or less, preferably 4 or less, more preferably 1.1 to 3, and most preferably 1.3 to 2.7.

Preferred as the ethylene / α-olefin copolymer resin is an ethylene / α-olefin random copolymer resin. The composition of the ethylene / α-olefin random copolymer resin is such that the α-olefin component is 0.1 to 9%.
9 mol%, preferably 0.2 to 80 mol%, more preferably 0.5 to 60 mol%, particularly preferably 1 to 40 mol%, most preferably 1 to 20 mol%, and the ethylene component is 1 to It is 99.9 mol%, preferably 20 to 99.8 mol%, more preferably 40 to 99.5 mol%, particularly preferably 60 to 99 mol%, and most preferably 80 to 99 mol%. Representative examples of α-olefins include propylene, butene-1, hexene-1, pentene-1, 3-methyl-pentene-1, 4-methyl-hexene-1, 4-
Methyl-pentene-1,4,4-dimethylpentene-
1, octene-1, nonene-1, decene-1, dodecene-1, tetracene-1, hexadecene-1, pentadecene-1, octadecene-1, heptene-1, eicosene-1, 4-methyl-hexene-1, The number of carbon atoms of 4,4-dimethylpentene-1 or the like is 3 to 20, preferably 4 to
15, more preferably 4-12, most preferably 4-1
0 or one or more α-olefins.

Further, an ethylene / α-olefin random copolymer resin produced by polymerization using a metallocene catalyst is preferable, and a specific example of a particularly preferable resin has an MFR of 0.1.
10 to 10 g / 10 min, density 0.870 to 0.940 g /
It is an L-LDPE resin obtained by copolymerizing ethylene and hexene-1, which is an α-olefin having 6 carbon atoms, by a gas phase polymerization process having a cm ³ and a molecular weight distribution of 1.1 to 5. These may be any method as long as the polymerization is carried out in the presence of a metallocene-based catalyst.For example, polymerization in an improved high-pressure polymerization method is to maintain the polymer in a solution state and to increase the polymerization activity. 120 ° C. or higher, 3920 N / cm ² (400 kg / cm ² ) or higher at a temperature of 350 ° C. or lower, preferably 150 to 300 ° C. or lower in order to suppress a chain transfer reaction that causes a decrease in molecular weight and not to lower polymerization activity.
4900 to 19600 N / cm ² (500 to 2000 k
g / cm ² ).

In the polymerization in the gas phase polymerization method, a high temperature is not preferable because the copolymer is in a powder state.
The polymerization temperature is preferably 0 ° C. or lower, and the lower limit of the polymerization temperature is not particularly limited, but is preferably 50 ° C. or higher in order to increase polymerization activity. 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. Further, in the polymerization in the solution polymerization method, the polymerization temperature needs to be 120 ° C. or more in consideration of the fact that the copolymer is in a solution state and that the polymerization activity is increased. The upper limit of the polymerization temperature is not particularly limited, but is preferably 350 ° C. or lower in order to suppress a chain transfer reaction that causes a decrease in molecular weight and not to lower the catalyst efficiency. The pressure at the time of polymerization is not particularly limited. However, in order to balance economy and polymerization activity, the pressure is higher than atmospheric pressure.
It is preferably 50 N / cm ² (250 kg / cm ² ) or less.

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

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

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

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

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

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

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

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

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

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

The catalyst is supported on an inorganic or organic carrier.
May be used. This carrier can be inorganic or
The porous oxide of the machine is preferred, and specifically, SiO 2₂, A
l₂O₂, MgO, ZrO₂, TiO₂, B₂O₂, C
aO, ZnO, BaO, ThO₂Etc. or a mixture of these
And SiO 2₂-Al₂O₂, SiO₂-V ₂
O₂, SiO₂-TiO₂, SiO₂-MgO, SiO
₂−Cr₂O₂And inorganic carriers such as polyethylene and polypropylene
Pyrene, polybutene-1, poly-4-methylpentene-
1, organic carriers such as styrene-divinylbenzene and the like.
It is.

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

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

The ethylene / α-olefin copolymer is
In the presence of a single-site catalyst, virtually no solvent is present.
Manufactured by gas phase polymerization, slurry polymerization, solution polymerization, etc.
In a state in which oxygen, water, etc. are substantially refused, or butane,
Aliphatic hydrocarbons such as pentane, hexane,
Aromatic hydrocarbons such as benzene, toluene, xylene,
Alicyclic hydrocarbons such as hexane and methylcyclohexane
Manufactured in the presence of an inert hydrocarbon solvent exemplified in
You. The polymerization conditions are not particularly limited, but the polymerization temperature is usually 1
5 to 350 ° C, preferably 20 to 200 ° C, more preferably
Or 50-110 ° C, especially using a Ziegler catalyst
In the case of the improved high-pressure method, 130 to 350 ° C. is preferable,
The polymerization pressure is usually normal pressure to 686 N / cm in the case of the low and medium pressure method.²
(70kg / cm²), Preferably normal pressure to 196 N / c
m²(20kg / cm²).
Always 14,700 N / cm²(1500kg / cm²)
Below, especially in the case of the improved high-pressure method using a Ziegler catalyst, 3
920-8820 N / cm ²(400-900kg / c
m²) Is desirable. The polymerization time is usually 3 minutes for the low and medium pressure method.
10 to 10 hours, preferably about 5 minutes to 5 hours.
In the case of the improved high-pressure method, usually 1 minute to 30 minutes, preferably 2 minutes
About 20 minutes is desirable. In addition, the polymerization is a one-stage polymerization method.
Of course, hydrogen concentration, monomer concentration, polymerization pressure, polymerization temperature
Multi-stage of two or more stages with different polymerization conditions such as temperature and catalyst
There is no particular limitation on the polymerization method and the like.

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

In a preferred embodiment, the ethylene / α-olefin copolymer resin has a molecular weight distribution of 1.1 to 5.
0, MFR 0.1 to 10 g / 10 min, density 0.85
A copolymer of ethylene and an α-olefin having 3 to 12 carbon atoms, using a catalyst comprising a metallocene transition metal compound having a melting point of 80 to 120 ° C. and an organoaluminum compound having a melting point of 0 to 0.940 g / cm ³ . is there. By using such an ethylene / α-olefin copolymer resin,
It has effects such as being able to provide a sealed package which is inexpensive, has little catalyst residue, does not adversely affect photographic properties, and has excellent physical strength and heat sealability.

Table 3 shows the MFR measurement conditions for various thermoplastic resins.

[0061]

[Table 3]

The heat sealing layer may contain a light-shielding substance. By including a light-shielding substance, light-shielding properties can be imparted and physical strength can be increased. Representative examples of the light-shielding substance are described below.

(1) Inorganic Compound 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 strips, non-wood fibers (straw, kenaf, bamboo, esparto, pagas, moloheiya, smoke, etc.) cellophane pieces, nylon fibers, polypropylene fibers, starch (modified starch) , Including surface-treated starch), aromatic polyamide fibers, etc.

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

Most preferably, the aspect ratio is 3.5.
The following light-absorbing carbon black and iron black have an aspect ratio of 5 or more flaky graphite, bengala, talc,
Used together with one or more of mica, barium ferrite, aluminum powder, aluminum paste, flaky metal powder, flakes, etc. to improve dispersibility, moisture proofness, light-shielding properties, appearance, antistatic properties, etc. It is used in combination with one or more pigments having a Mohs hardness higher than carbon black (for example, titanium oxide) to improve dispersibility and light-shielding properties.

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 preferred commercial products of carbon black include, for example, carbon black # 2 manufactured by Mitsubishi Kasei.
0 (B), # 30 (B), # 33 (B), # 40 (B), # 41
(B), # 44 (B), # 45 (B), # 50, # 55, # 1
00, # 600, # 950, # 1000, # 2200
(B), # 2400 (B), 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 contacting the back side of channel steel while incompletely burning a gas flame of natural gas or a gaseous or vaporous hydrocarbon in these various carbon blacks to precipitate carbon black. Although they have high coloring power, they have poor photographic properties and contaminate the air during production, and are not preferred in the present invention in terms of photographic properties and environmental problems.

When applied to the packaging material for photosensitive material according to the present invention, one or more of creosote oil and ethylene bottom oil are used as raw material oil in order to prevent adverse effects on the photographic properties of the photographic material. ℃ ~ 1700 ℃
Furnace carbon black produced by continuous partial combustion in a furnace or thermal decomposition is preferred. By using such a furnace carbon black, the amount of free sulfur components is small, so that the adverse effect on the photographic material can be reduced. In particular, furnace carbon black having a free sulfur content of 100 ppm or less is preferable.

The sulfur content according to ASTM D 1619-60 is 0.9% or less, preferably 0.1% or less.
It is at most 7%, particularly preferably at most 0.5%, most preferably at most 0.1%. If the content is not limited to this range, adverse effects on the photographic properties of the photographic light-sensitive material, such as an increase in fog, abnormal sensitivity, abnormal coloring, etc. In particular, the content of free sulfur components which greatly adversely affects the photographic properties of direct photographic light-sensitive materials. 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. After cooling, the total volume is made up to 100 ml. 10m of this solution
1 is injected into a high performance liquid chromatograph and sulfur is determined. High-performance liquid chromatography separation conditions are column; ODS
Silica column (4.6φ × 150 mm), separation liquid; methanol 95 and water 5 (containing 0.1% each of acetic acid and triethylamine), flow rate: 1 ml / min, detection wavelength: 2
The quantification is performed by the absolute calibration method at 54 nm. ｝
It is at most 0.1%, preferably at most 0.05%, particularly preferably at most 0.01%. Although expensive, acetylene black having a sulfur content of 0.1% or less is suitable for use in high-speed photographic light-sensitive materials having an ISO sensitivity of 100 or more for maintaining good photographic properties.

In order to maintain good photographic properties, it is important to select carbon black raw materials. For example, Carbon Black Handbook (Apr. 15, 1995, published by The Carbon Black Association), p. First, as sulfur in carbon black, most of the sulfur comes from the feedstock,
It is specified to contain about 2.5% by mass. Therefore, the content of the sulfur component for maintaining good photographic properties 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 feedstock)} 0.05-0.1% Ethylene bottom Oil ｛Light oil feedstock (petroleum-based feedstock)｝ 0.2-1.5% Fluid catalytic cracking residue oil ｛petroleum-based feedstock０．２0.2-4.0%

Therefore, as the raw material oil for carbon black, creosote oil and ethylene bottom oil derived from petroleum are preferable, and the sulfur component content is 0.05 to 0.1%.
Carbon black produced from ethylene bottom oil using naphtha as a raw material is most preferable because the sulfur component content in the carbon black can be 0.1% or less.

The production method is as follows.
00 ° C to 1700 ° C, preferably 1250 ° C to 1600
Furnace carbon black produced in an oven at ℃ is preferred.

In particular, a free sulfur component (free su) which has been found to have a direct adverse effect on the photographic properties of the photographic light-sensitive material
lphr) 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 1 ppm or less.
Use 0 ppm or less of carbon black. In view of the low content of the free sulfur component, the present invention uses ethylene naphtha-based ethylene bottom oil at 1250 ° C. to 16 ° C.
Furnace carbon black produced by continuous partial combustion or thermal decomposition in a furnace at 00 ° C. is most preferred.

Particularly preferred as carbon black is an iodine adsorption amount (measured according to JIS K 6221) relating to the dispersibility, conductivity, and light-shielding ability of 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.

Furnace carbon black is preferred for the purpose of improving light-shielding properties, cost, and physical properties. Ketjen, which is an expensive but various conductive carbon black and acetylene carbon black of various companies having an antistatic effect, and a modified by-product carbon black. Carbon black is preferred.
In particular, for photographic materials having high sensitivity (ISO sensitivity of 400 or more), acetylene black having a sulfur content of 0.1% or less and ethylene bottom oil made of naphtha as a raw material are used in an amount of 125%.
Continuous partial combustion in a furnace at 0 ° C. to 1600 ° C.,
Alternatively, furnace carbon black produced by thermal decomposition is preferable.

The conductive carbon black has an average particle diameter of 12 to 50 nm (= mμ) and a DBP oil absorption of 10
There are various types of conductive carbon blacks of 0 ml / 100 g or more, such as acetylene black, conductive furnace black (CF), superconductive furnace black (SCF), extra conductive furnace black (XCF), conductive channel black (CC), and 1500 ° C. Furnace black or channel black heat-treated at a moderately high temperature can be used. Specific examples of acetylene black include Denka acetylene black (manufactured by Denki Kagaku Co., Ltd.) and Shaunigan acetylene black (manufactured by Shaunigan Chemical Co., Ltd.). Specific examples of the conductive furnace black include Continex CF.
(Continental Carbon Co., Ltd.), Vulcan C
(Manufactured by Cabot Corporation) and the like, and specific examples of superconductive furnace black include Continex SCF (manufactured by Continental Carbon Co., Ltd.) and Vulcan SC (manufactured by Cabot Corporation). Specific examples of the superconductive furnace black include: , Asahi HS-500 (manufactured by Asahi Carbon Co., Ltd.), Vulcan XC
-72 (manufactured by Cabot Corporation) is a specific example of the conductive channel black.
(Made by Degussa K.K.), and Ketjen Black EC and Ketjen Black EC-600JD (Ketjen Black International), which are a kind of furnace black, can also be used.

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

A preferred conductive carbon black is a carbon black which, when kneaded with a thermoplastic resin, can impart sufficient conductivity while having good film processability, and has a total oxygen content before heat treatment of 25 mg / kg. g of furnace carbon black of 18 g or less under an inert atmosphere.
By performing a heat treatment at 0 to 750 ° C, preferably 200 to 700 ° C, more preferably 250 to 650 ° C, the total oxygen content is reduced to 3 to 60%, preferably 5 to 50%, more preferably 5 to 40%. The carbon black is reduced. By using such carbon black,
A wrapping material for a photosensitive material having excellent antistatic properties can be provided with almost no adverse effect on the photographic properties of the photographic photosensitive material having excellent film formability.

Here, the term "inert atmosphere" refers to an atmosphere in which oxygen molecules are not present or is present in an extremely small amount, and is an atmosphere substantially composed of argon, nitrogen, carbon dioxide and the like.

When the heat treatment temperature is lower than 180 ° C., the oxygen functional group is hardly released, and when the heat treatment temperature is higher than 750 ° C., the phenomenon of burning on the surface of the carbon black particles and on the aggregates and agglomerates occurs, the aggregation unit becomes hard, and the carbon black is hardened. Dispersibility in thermoplastic resin becomes worse.

The heating time is 10 to 700 minutes, preferably 15 to 600 minutes, more preferably 20 to 500 minutes, depending on the heating temperature.

The total oxygen content before the heat treatment was 25 mg / g
Preferred as the following furnace carbon blacks are those having a specific surface area of 20 to 7 obtained by an oil furnace method.
00m ² / g, DBP oil absorption 30-500ml / 10
0 g, furnace carbon black having an ash content of 0.001 to 0.8%.

[0086] Oxygen functional groups such as hydroxyl groups and carbonyl groups are present on the surface of the carbon black particles, and the amount of these groups greatly changes the resistance value when blended in a thermoplastic resin.
The oxygen functional group is measured by the volatile component composition, the amount of the hydroxyl group and the carbonyl group can be quantified as CO, the amount of the carbonyl group can be quantified as CO ₂ , and the total oxygen amount is converted from CO and CO ₂ . The volatile matter composition is obtained by putting a certain amount of dry carbon black into a heat-resistant test tube, and placing the carbon black at 1.33 Pa (10 ⁻² mmH).
g) After reducing the pressure to the following, 3
After heating and desorbing for 0 minutes, collect and mix in a total volume tank, measure the composition and amount of gas by gas chromatography,
From this result, the total oxygen amount is calculated.

The content of the light-shielding substance is preferably from 0.5 to 40% by mass, more preferably from 1 to 30% by mass, and
0 mass% is particularly preferable, and 2.5 to 10 mass% is most preferable. If the content is less than 0.5% by mass, a desired light-shielding property may not be obtained in some cases. If the content exceeds 40% by mass, the effect of increasing the amount is not exhibited and the cost is increased. Further, physical strength, resin fluidity and film moldability may deteriorate, and foaming may occur due to moisture absorption.

In order to improve the dispersibility of carbon black and the like and improve the photographic properties, it is preferable to include a fatty acid metal salt as a dispersant. Fatty acid metal salts include higher fatty acids such as lauric acid, stearic acid, succinic acid, stearyl lactic acid, lactic acid, phthalic acid, benzoic acid, hydroxystearic acid, ricinoleic acid, naphthenic acid, oleic acid, palmitic acid, erucic acid and Li , Na, M
g, Ca, Sr, Ba, Zn, Cd, Al, Sn, P
Compounds with metals such as b, Cd and the like are mentioned, and preferred are magnesium stearate, calcium stearylate, sodium stearate, zinc stearate, zinc oleate, magnesium oleate and the like.

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

[0090]

[Table 4]

The above-mentioned light-shielding substance can be added to the high Young's modulus and heat resistant thermoplastic resin film layer in addition to the heat seal layer.

A gas adsorbing substance can be added to the heat seal layer. By adding a gas adsorbent,
A substance that adversely affects photographic properties can be adsorbed, and photographic properties can be favorably maintained. The addition amount of the gas adsorbing substance is 0.
001 to 40% by mass is preferred, and 0.01 to 30% by mass.
Is more preferable, 0.05 to 20% by mass is particularly preferable, and 0.1 to 15% by mass is most preferable. The amount added is 0.
If it is less than 001% by mass, it is difficult to exhibit a sufficient effect, and if it exceeds 40% by mass, physical strength is reduced, heat sealability is deteriorated, and not only appearance is deteriorated, but also film formability is deteriorated. However, it is expensive and difficult to put into practical use.

Examples of the gas adsorbent include zeolite (including natural and synthetic zeolites), talc (magnesium silicate), silica (including natural and synthetic silica), calcium carbonate, aluminum silicate, calcium silicate, and fatty acid amide. Lubricants, higher fatty acid polyvinyl esters, n-octadecyl urea, N, N'-dioleyl oxamide, N-ethanol stearamide, dicarboxylic ester amide, etc., among them, have an adverse effect on anti-blocking action and photographic properties. Zeolite, talc and silica, which have various gas adsorption and detoxifying effects, are preferred.

The zeolite is a natural zeolite (an
alcime, chabazite, heulandi
te, erionite, ferrierite, la
zeolites containing ummonite, modernite, etc.), synthetic zeolites (A, NA, X, Y,
hydroxy sodalite, ZK-5, B,
R, D, T, L, hydroxy, cancrinit
and various types of zeolites such as e, W, and Zeolaon). Among these, A-type zeolites having a large harmful gas adsorption detoxifying ability which adversely affects photographic properties are particularly preferred.
These zeolites function excellently as a metal carrier and as a metal-based inorganic antibacterial agent. For example, there is an A-type synthetic zeolite carrying silver ions.

Further, since this zeolite functions excellently as a metal-based inorganic antibacterial agent (for example, an A-type synthetic zeolite carrying silver ions) as a metal carrier, 0.001 to 0.001 is mainly used for antibacterial action. The content is 10% by mass, preferably 0.002 to 8% by mass, particularly 0.005 to 5% by mass.

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

The above gas adsorbing substance can be added to the high Young's modulus and heat resistant thermoplastic resin film layer in addition to the heat sealing layer.

A lubricant can be added to the heat seal layer. By incorporating a lubricant, the resin fluidity is improved and the film formability is improved, and at the same time, blocking in the film forming step, laminating step, bag making step, etc. is prevented, and handling suitability and lubricity are improved. Wrinkles and streaks can be prevented. Further, it is possible to prevent blocking from occurring, and also to prevent scratches and static marks from being generated even when the photographic photosensitive material is rubbed as a packaging bag or the like. Further, the addition of the lubricant improves the fluidity of the resin and improves the film formability.

The amount of the lubricant to be added differs depending on the kind. In the case of a lubricant having a small lubricating effect, such as a fatty acid metal salt, whose main purpose is to maintain the photographic performance of the photographic light-sensitive material and to improve the dispersibility of the light-shielding substance, the amount is not limited to 0.1. 01-5 mass% is preferable, and 0.03-
3 mass% is more preferable, 0.05 to 1.5 mass% is particularly preferable, and 0.07 to 1 mass% is most preferable. 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 added amount exceeds 5% by mass, foaming, white smoke and die lip streaks are likely to occur, and the slip between the molten resin and the screw of the extruder is likely to occur. Become. 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 seal strength with time is reduced, and the sealing property, moisture-proof property and oxygen barrier property are deteriorated, so that it is difficult to put it into practical use as a packaging material for photosensitive materials.

Further, it has a large lubricating effect like a fatty acid amide-based lubricant and a bisfatty acid amide-based lubricant, but easily bleeds out and generates aldehydes upon thermal decomposition to adversely affect the photographic properties of the photographic light-sensitive material. For lubricants that give
It is preferably 0.01 to 1% by mass, more preferably 0.03 to 0.5% by mass, and most preferably 0.05 to 0.3% by mass. 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 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, resulting in quality defects such as development unevenness and color unevenness. In addition, aldehydes are generated by thermal decomposition, which adversely affects the photographic properties of the photographic light-sensitive material.

In the present invention, various lubricants described on page 5 [0032] to page 6 [0044] of JP-A-6-317883, etc. have good photographic properties.
More than one kind of lubricant can be selected and used in the minimum amount corresponding to the purpose of use.

Dimethylpolysiloxanes of various grades and modified products thereof (Shin-Etsu Silicone, Toray Silicone),
In particular, various silicone oils not only exert the effects of improving the resin fluidity and the lubricity, but also improve the dispersibility of the light-shielding substance when used together with the light-shielding substance, make the resin cloudy, and reduce the haze (ASTM D-1003). As a result of the increase, unexpected effects such as improvement in coloring power and light-shielding properties are exhibited, and therefore, it is particularly preferable as the lubricant used in the present invention.

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 40,000 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,
If it is less than 000 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 large and the handling property is poor, so that it may not be able to be taken out by adhering to a container, or the flowability of the resin may be reduced to cause molding failure.

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 silicones, amide-modified silicones, polydimethylsiloxanes, and the like, which do not adversely affect the photographic light-sensitive material and have a large lubricating effect and are preferable when applied to packaging materials, are preferred. Polyether-modified silicone and olefin / polyether-modified silicone.

The addition of silicone oil improves the fluidity of the resin, and, as unexpected effects, improves the physical strength and lowers the surface reflection gloss. Furthermore, lubricity can be improved.
Further, when used in combination with a light-shielding substance, the dispersibility of the light-shielding substance is improved, and the resin becomes opaque to haze (ASTMD).
As a result of increasing (-1003), it is possible to improve the coloring power and the light-shielding property.

Further, the silicone oil 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 molding material in the heated state. (5) When used in combination with a light-shielding substance, the thermoplastic resin becomes cloudy and the haze is increased. As a result, the coloring power can be improved and the light-shielding ability can be improved. Nature can be secured.

In the heat seal layer of the present invention, ethylene-
Preferably, the silicone oil contains 0.1 to 10 parts by mass, more preferably 0.2 to 8 parts by mass, based on 100 parts by mass of the α-olefin copolymer resin.
More preferably, the content is 0.4 to 6 parts by mass.
It is particularly preferable to contain 5 to 4 parts by mass, and 0.6 to 3 parts by mass.
Most preferably, it is contained by mass.

When the content of the silicone oil is less than 0.1 part by mass, the above-mentioned effects cannot be exhibited effectively. On the other hand, when the amount exceeds 10 parts by mass, not only the effect of increasing the amount is not exhibited, but also bleed-out increases and the commercial value is reduced.

The lubricant described above can be added to the high Young's modulus and heat resistant thermoplastic resin film layer in addition to the heat seal layer.

A hydrotalcite compound can be contained in the heat seal layer. By containing hydrotalcite compounds, neutralize catalyst residues that adversely affect the photographic properties of photographic light-sensitive materials, or detoxify substances that adversely affect photographic properties by absorbing halogen compounds such as hydrochloric acid, Rust of the mold can be prevented, and resin burning failure can be prevented. In particular, when used in combination with one or more of a phenolic antioxidant and a phosphorus-based antioxidant, the effect of preventing thermal degradation and thermal decomposition of the thermoplastic resin, the 1,2-polybutadiene-based thermoplastic elastomer and the additives is increased, which is preferable.

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

As a typical example of the specific example, Mg ₆ A1
_{2 (OH) 16 CO 3 ·} 4H 2 O, Mg 8 Al 2 (OH) 2
_{0CO 3 · 5H 2 O, Mg} 5 Al 2 (OH) 14 CO 3 ·
_{4H 2 O, Mg 10 Al 2} (OH) 22 (CO 3) 2 · 4H
_{2 O, Mg 6 Al 2 (} OH) 16 HPO 4 · 4H 2 O, C
_{a 6 Al 2 (OH) 16} CO 3 · 4H 2 O, Zn 6 Al 2
_{(OH) 16 CO 3 · 4H} 2 O, Mg4.5Al 2 (OH)
There are ₁₃ CO ₃ · 3.5H ₂ O and the like.

Alternatively, the general formula is M _(1-x) · Al _x · (OH) ₂ · X _{x / n} · mH ₂ O where M represents an alkaline earth metal and Zn. X represents an n-valent anion.

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

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

Preferred specific examples of the hydrotalcite compound are shown below. Mg _0.7 Al _0.3 (OH) ₂ (CO ₃ ) _0.150.0 .
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・ 0.4
2H 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 Japanese Patent Publication No. 46-2280, Japanese Patent Publication No. 50-30039 and the like can be used.

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

The content of the hydrotalcite compound in the heat seal layer is preferably 0.01 to 30% by mass.
0.02 to 20% by mass is more preferable, and 0.05 to 10% by mass.
% Is particularly preferred, and 0.1 to 5% by weight is most preferred.

When the content of the hydrotalcite compound is less than 0.01% by mass, the effect of addition is not exhibited and only the kneading cost is increased. However, this only lowers the physical strength and heat sealing suitability, and causes the occurrence of bumps and an increase in cost.

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

Particularly preferred examples of such surface coating materials include, for example, sodium laurate, potassium laurate, sodium oleate, potassium oleate, calcium oleate, magnesium stearate, sodium stearate, and stearic acid. Metal salts of higher fatty acids such as zinc, potassium stearate, sodium palmitate, potassium palmitate, sodium caprate, potassium caprate, sodium myristate, potassium myristate, sodium linoleate, potassium linoleate; lauric acid, Palmitic acid, oleic acid, stearic acid,
Higher fatty acids such as capric acid, myristic acid, and linoleic acid; metal salts of organic sulfonic acids such as calcium dodecylbenzenesulfonate and sodium dodecylbenzenesulfonate; isopropyl triisostearoyl titanate; isopropyl tris (dioctyl pyrophosphate) titanate; Coupling agents such as isopropyl bis (dioctyl phosphite) titanate, vinyl triethoxy silane, gamma methacryloxypropyl trimethoxy silane, gamma glycidoxy propyl trimethoxy silane, higher fatty acid amides,
Examples include various lubricants such as higher fatty acid esters, silicones, and waxes.

The surface coating with these surface coating substances can be performed, for example, by adding an aqueous solution of an alkali metal salt of a higher fatty acid to a suspension of a hydrotalcite compound or zeolite in warm water with stirring. ,
The hydrotalcite compound powder or zeolite powder can be added by dropping a melt of a higher fatty acid or a diluent of a coupling agent while stirring with a mixer such as a Henschel mixer. The amounts of these surface coating substances can be appropriately selected and changed.
About 0.01 to 50 parts by mass, preferably 0.05 to 35 parts by mass, particularly preferably 0.1 to 20 parts by mass, based on 0 parts by mass.
Parts by weight, most preferably 0.5 to 10 parts by weight.

The above-mentioned hydrotalcite compounds can be added to the high Young's modulus and heat resistant thermoplastic resin film layer in addition to the heat seal layer.

An antioxidant can be contained in the heat seal layer. Substances (such as aldehyde compounds and cyanide compounds) that prevent the deterioration of physical strength by increasing the effect of preventing heat degradation and thermal decomposition of resins and additives by incorporating antioxidants, and also reduce photographic properties. Can be prevented.

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′-biphenylenediphosphite, 4,4′-thiobis- (6-ter
t-butyl-O-cresol), 2,2'-thiobis-
(6-tert-butyl-4-methylphenol), tris- (2-methyl-4-hydroxy-5-tert-
Butylphenyl) butane, 2,2'-methylene-bis-
(4-methyl-6-tert-butylphenol),
4,4'-methylene-bis- (2,6-di-tert-butylphenol), 4,4'-butylidenebis- (3-methyl-6-tert-butylphenol), 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-tert-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 dinonyl phenyl) phosphite, and cyclic neopentane tetrayl bis (2.6-di-t-butyl-4-). Methylphenyl) phosphite, diphenylisodecylphosphite, tris (nonylphenyl) phosphite sodium phosphite, tris (nonylphenyl) phosphite,
2,2-methylenebis (4.6-di-tert-butylphenyl) octyl phosphite, tris (2.4-di-tert-butyl)
(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 in combination with an inorganic pigment such as carbon black, the light-shielding ability is improved by 10% or more compared to 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. preferable.

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.

The content of the antioxidant ranges from 0.001 to 1.
5 mass% is preferable, 0.005 to 0.7 mass% is more preferable, and 0.01 to 0.45 mass% is most preferable.
When the content is less than 0.001% by mass, there is no effect of addition and only the kneading cost increases, and when the content exceeds 1% by mass, the photographic properties of the photographic light-sensitive material utilizing oxidation and reduction actions are reduced. It has an adverse effect and bleeds out to the surface to deteriorate the appearance.

The above-mentioned antioxidant can be added to the high Young's modulus and heat resistant thermoplastic resin film layer in addition to the heat seal layer.

An antistatic agent can be contained in the heat seal layer. By containing an antistatic agent,
It improves the dispersibility of the light-shielding substance and the film formability, and prevents the occurrence of static failure and the like.

The antistatic agent will be described. (1) Representative examples of the nonionic surfactant-based antistatic agent are shown below. Polyethylene glycol fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene alkyl ether, polyoxyethylene alkylamine, polyoxyethylene alkylamine fatty acid ester, polyoxyethylene aliphatic alcohol ether, polyoxyethylene alkylphenyl ether, polyoxyethylene Glycerin fatty acid ester, polyoxyethylene aliphatic amine, sorbitan monofatty acid ester, fatty acid bentaerythrit, fatty alcohol ethylene oxide adduct, fatty acid ethylene oxide adduct, fatty acid amino or fatty acid amide ethylene oxide adduct, alkylphenol ethylene Oxide adduct, ethylene oxide adduct of alkyl naphthol, polyhydric alcohol part Ethylene oxide adducts of fatty acid esters, polyoxyethylene alkyl amide, alkyl derivatives, and other Japanese Patent Publication 63-26
Various nonionic antistatic agents described on page 120 of JP-A-697. (2) 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 soda ester salt, sulfated ethyl aniline sulfate, olefin sulfate salt, oleyl alcohol sulfate soda salt, alkyl sulfate ester salt, fatty acid ethyl sulfonate , Alkyl sulfate, alkyl phosphate, alkyl sulfonate, alkyl naphthalene sulfonate, alkyl benzene sulfonate, succinate sulfonate, phosphate ester salt and the like. (3) Representative examples of the cationic surfactant-based antistatic agent are shown below. Representative examples of amphoteric surfactants such as primary amine salts, tertiary amine salts, quaternary ammonium salts, trialkylbenzylammonium salts, and pyridine derivatives are shown below.

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

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

The above-mentioned antistatic agent can be added to the high Young's modulus and heat resistant thermoplastic resin film layer in addition to the heat seal layer.

The barrier film layer and the heat seal layer are laminated via an adhesive layer or without an adhesive layer. As the adhesive layer, various known adhesive layers can be used according to required characteristics. Examples of the adhesive used for this adhesive layer include various polyethylene (LDPE, L-LDPE, MDPE, and HDPE) resins, various polypropylene resins, and other polyolefin-based thermoplastic resins, ethylene-propylene copolymer resins, and ethylene-acetic acid. Heat of special thermoplastic resins such as vinyl copolymer resin, ethylene-ethyl acrylate copolymer resin and other ethylene copolymer resin, ethylene-acrylic acid copolymer resin, ionomer resin, acid-modified ethylene copolymer resin There is a melt type adhesive (extrusion laminate type adhesive). There are other hot-melt type rubber-based adhesives, and as a solution adhesive, there is an adhesive for wet lamination,
It is 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 copolymer, acryl copolymer, ethylene-acryl There are emulsions such as acid copolymers. Representative examples of latex-type adhesives include natural rubber and styrene-butadiene rubber (SB
R), rubber latex such as acrylonitrile butadiene rubber (NBR) and chloroprene rubber (CR).

The adhesive for dry laminating is described in, for example, pages 859 to 862 of “Plastic Film and Resin Materials Overview '95” published by the Processing Technology Research Group on October 30, 1995. Two-component curing type, solvent type, non-solvent type, aqueous type, two-component solvent type, one-component non-solvent type, two-component non-solvent type, emulsion type, etc., acrylic adhesive, polyether adhesive, poly Ether- and polyurethane-based adhesives, polyester- and polyurethane-based adhesives, polyester- and isocyanate-based adhesives, aromatic polyester-based adhesives, aliphatic polyester-based adhesives, and aromatic polyether-based adhesives Agents, aliphatic polyether adhesives, polyester adhesives, isocyanate adhesives, polyurethane adhesives and the like. Among them, a two-component reaction solvent type polyester adhesive and a two-component reaction solvent type polyurethane adhesive are particularly preferable for the present invention. The dry thickness is 0.5-8 μm, preferably 1-5 μm. Other hot melt laminating adhesives blending paraffin wax, microcrystalline wax, ethylene-vinyl acetate copolymer resin, ethylene / α-olefin copolymer resin, tackifier resin, ethylene-ethyl acrylate copolymer resin, etc., reaction Known adhesives such as a hot-melt adhesive, a pressure-sensitive adhesive, and a heat-sensitive adhesive can be used.

The polyolefin 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, and an ethylene copolymer (EVA resin, EEA resin) of various densities. Resin, EAA resin, etc.) resin, such as L-LDPE resin, which is obtained by copolymerizing ethylene with some other monomer (α-olefin), Dup
Single or two or more ionomer resins (ionic copolymers) such as "Surlyn" of Ont, "Hyramin" of Mitsui Polychemicals, and acid-modified polyolefin resins such as "Admer" of Mitsui Petrochemicals Co., Ltd. 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. To improve the adhesive strength, add 1 acid-modified polyolefin resin.
It is preferable to use it in a blend of about 50% by weight. Also, 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. In particular, blending an LDPE resin or L-LDPE resin with an acid-modified polyolefin resin at an appropriate ratio can provide an arbitrary adhesive strength, and is particularly preferable in the present invention. The delamination strength of the laminated film is 350 g / 15 mm width or more, particularly preferably 500 g / 15 mm width or more, and most preferably 600 g / 15 mm or more.
In order to improve the easy-openability with a width of 15 mm or more,
The dry laminating adhesive, the solventless adhesive or the polyolefin resin adhesive for extrusion lamination containing 5% by weight or more of the acid-modified polyolefin resin is particularly preferable.

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, nonwoven fabric, synthetic paper, cellophane, etc. 3) Stable reaction and strong adhesive force can be obtained 4) Peeling strength can be increased to 400g / 15mm width or more, so easy-opening property is good 5) Heat resistance is excellent 6) Reactive type, main material / Pot life (possible use time) after mixing with curing agent and solvent. 7) Solid content application amount is 0.5 to 10 g / m ² , preferably 1 to 8 g / m ² , particularly preferably 1. 5-6 g / ^{m 2} and with a gravure method (smoothing bar combination) as thinning can 8) coating method, 1-5 the coating amount accurately controllable However, at 30 to 65 ° C. until the complete cure During aging is required.

Recently, a one-pack type non-solvent type dry laminating adhesive for the purpose of preventing pollution of the dry laminating adhesive is preferred in the present invention since it does not adversely affect photographic properties. This adhesive for dry lamination is mainly composed of a polyurethane-based adhesive. Since it is necessary to have a low viscosity of 3000 CPS or less in order to minimize the amount of application, a hot melt method of heating to 60 to 110 ° C. And it is necessary to reduce the molecular weight and the coating amount. In addition, it is possible to achieve higher speed than the dry lamination method, drying is easy (sometimes unnecessary), and the coating amount is 5 g / m ² or less, preferably 3 g / m ² or less, particularly preferably 0.3 to ² g / m ^2. , Most preferably 0.5
Since a very small amount of 1.5 g / m ² is required, control accuracy of the coating amount is required. Therefore, it is preferable to use a multi-roll coating method of three or more rolls, preferably four or more rolls.

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

Particularly, the following uses are preferable. It is preferably applied to a packaging material for loading a X-ray film in a bright room and a package using the same. For example, Japanese Patent Publication No. 267993, Japanese Patent Publication No. 2572221,
-83543, JP-A-7-287329,
JP-A-11-237713, JP-B-7-3137
No. 6, JP-B-7-31377. Moisture-proof pillow package of film unit with lens (Fuji Photo Film, "Sharunudes" etc.). Two or more collectively sealed packages of 35 mm photographic film (negative and reversal black and white and color photographic films).

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

The present invention 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-packed package of a belt-shaped photosensitive material, overwrapping a carton or tray, overwrapping a caramel type, overwrapping a snack type, over a cigarette type There are wrapping packaging, roll wrapping packaging, rod-shaped wrapping packaging, twist wrapping packaging, etc., and various types described in the Japan Packaging Technology Association, published on July 1, 1995, "Handbook of Packaging Technology", pages 754 to 774. It can be used for packaging.

The light-sensitive material package of the present invention is obtained by sealingly wrapping a chemically sensitized and / or dye-sensitized light-sensitive material using the above-described light-sensitive material packaging material. The form of the sealed packaging is not particularly limited, and various packaging forms as described above can be adopted.

In the package for photosensitive material of the present invention, at least one selected from the group consisting of a heat-sealing layer of the package for photosensitive material, the photosensitive material, and a packaging material containing paper as a main component in the sealed package. It is preferable that one type contains a photographic improving substance (including coating, spraying, printing, etc.). Examples of the photographic property improving substance include the above gas adsorbing substances (zeolite, talc, silica, calcium carbonate, aluminum silicate, calcium silicate, fatty acid amide-based lubricant, etc.), the above fatty acid metal salts, formaldehyde scavenger (polyamide resin, Amide compounds, urethane compounds, vinyl alcohol copolymer resins, pyridine derivatives, pyrrolidone derivatives, urea derivatives, triazine derivatives, hydrazine derivatives, hydantoin derivatives, imide compounds, etc.) and hydrogen cyanide gas scavengers (palladium compounds, platinum compounds, rhodium compounds, Iridium compounds, osmium compounds, etc.), and halogen scavengers (fatty acid metal salts, hydrotalcite compounds, metal hydroxides, metal carbonates, epoxy compounds, etc.).

The photographic light-sensitive materials applicable to the light-sensitive material packaging material 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-4-136838, JP-A-4-1723
39, JP-A-5-113623, JP-A-9
-325450, JP-A-10-62901, JP-A-10-62903, JP-A-10-62
904, JP-A-10-62905, JP-A-10-62906, JP-A-10-62921, JP-A-10-142731, etc.) (2) Heat-developable photographic material (heat-developable color photosensitive material) 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 salt photography, published by Corona Co., Ltd., 1879), pages 553 to 555.
And pages 9 to 15 (RD-17029), June 1978, Research Tis Closure, and the like. 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 / thermosensitive recording materials (photothermography (photosensitive / thermosensitive images) described in JP-A-3-72358, etc.) (4) Diazonium photographic light-sensitive material (4-morpholinobenzenediazonium microfilm, microfilm, copy film, printing plate material, etc.) (5) Azide, diazide photographic light-sensitive material ( Photosensitive materials containing para-azide benzoate, 4,4'-diazidostilbene, etc., for example, copying films, printing plates, etc. (6) Quinonediazide-based photographic materials (orthoquinonediazide, orthonaphthoquinonediazide compounds, for example, benzoquinone ( 1,2) -diazide- (2) -4-
Photosensitive materials containing sulfonic acid phenyl ether, etc.
(7) Photopolymers (photosensitive materials containing vinyl monomers, printing plates, adhesive films, etc.) (8) Polyvinylcinnamic acid ester photosensitive materials 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 developer in an adjacent layer)

The most suitable photographic light-sensitive material to which the wrapping material for a light-sensitive material of the present invention is applied is 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 papers, 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. Their structures, materials used, and techniques used are described, for example, in Research Disclosure (hereinafter abbreviated as RD) No. 17643 (19
1978), pp. 22-23, "I. Emulsion Production (Em
ulsion preparation and type
es) ", 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 (V.C.
L. Zelikman, et al. , Making a
nd Coating Photographic Em
ulsion, Focal Press, 1964).

The silver halide emulsion and other materials (additives, etc.) and photographic constituent layers (layer arrangement, etc.) applied to the photographic light-sensitive material according to the present invention, and also applied to process this photographic light-sensitive material Examples of processing methods and processing additives include EP 0,355,660 A2, JP-A-2-33144 and JP-A-62-215272.
The ones described in the specification of Japanese Patent Application Laid-Open Publication or the following are preferably used, but the present invention is not limited to these.

[0160]

[Table 5]

The layer structure of the packaging material for photosensitive material according to the present invention will be described with reference to the drawings. 1 to 4 are partial cross-sectional views of a packaging material for a photosensitive material.

The packaging material for photosensitive material shown in FIG. 1 has a metal thin film layer and / or an inorganic substance thin film layer on the outside (opposite to the photosensitive material) of the high Young's modulus and heat resistant thermoplastic resin film layer 1 (or 1a). 2 has a processed barrier film layer 3, and a high Young's modulus and heat resistant thermoplastic resin film layer 1 (or 1 a) is laminated on the outside of the barrier film layer 3 via an adhesive layer 4, and the inside ( A heat seal layer 5 (or 5a) is laminated on the photosensitive material side) via an adhesive layer 4.

The packaging material for a photosensitive material shown in FIG. 2 has both a high Young's modulus and heat resistant thermoplastic resin film layer 1 (or 1a) on the outside (the side opposite to the photosensitive material) and inside (on the photosensitive material side). It has a barrier film layer 3 on which a metal thin film layer and / or an inorganic substance thin film layer 2 are processed, and has a high Young's modulus and heat resistance via an adhesive layer 4 on the outside of the barrier film layer 3 (the side opposite to the photosensitive material). A thermoplastic resin film layer 1 (or 1a) is laminated, and a heat seal layer 5 (or 5a) is laminated on the inner side (on the photosensitive material side) via an adhesive layer 4.

The packaging material for a photosensitive material shown in FIG. 3 has a metal thin film layer and / or an inorganic thin film layer on the outside (opposite side of the photosensitive material) of the high Young's modulus and heat resistant thermoplastic resin film layer 1 (or 1a). 2 has a processed barrier film layer 3, and a high Young's modulus and heat resistant thermoplastic resin film layer 1 (or 1 a) is laminated on the outside of the barrier film layer 3 via an adhesive layer 4, and the inside ( The heat seal layer 5 (or 5a) is directly laminated on the photosensitive material side).

The packaging material for photosensitive material shown in FIG. 4 has a metal thin film layer and / or an inorganic substance thin film layer on the outside (opposite side of the photosensitive material) of the high Young's modulus and heat resistant thermoplastic resin film layer 1 (or 1a). 2 has a processed barrier film layer 3 and a high Young's modulus and heat resistant thermoplastic resin film layer 1 on the outside of the barrier film layer 3 as the outermost layer.
(Or 1a), a barrier film layer 3 on which a metal thin film layer and / or an inorganic substance thin film layer 2 are processed, and the barrier film layer 3 is formed of an adhesive layer 4
The heat seal layer 5 (or 5a) is laminated on the inner side (on the photosensitive material side) of the barrier film layer 3 with the adhesive layer 4 interposed therebetween.

In the above layer structure, a indicates that a light-shielding substance is contained.

[0167]

Example 1 A laminated film having a layer structure shown in FIG. 4 and having a moisture permeability of 0.1 g / m ² · 24 hours or less.

<Outer Barrier Film Layer 3> High Young's modulus / heat-resistant thermoplastic resin film layer 1: The Young's modulus in the vertical direction is 826 kg / mm ² , which is an oxygen barrier property and is also moisture-proof, and the melting point according to the DSC method. Is a biaxially stretched polyethylene naphthalate resin film layer having a thickness of 12 μm at 272 ° C. Thin film layer 2: A vacuum deposited thin film layer made of an inorganic compound of a metal having a thickness of 400 ° made of aluminum oxide.

<Adhesive Layer> Two-component reaction polyester-based dry laminating adhesive layer of diisocyanate and polyester polyol (solid content of 2.5 to 4.0 g /
m ² ).

<Inner Barrier Film Layer 3> High Young's Modulus / Heat-Resistant Thermoplastic Resin Film Layer 1: Oxygen barrier property and pinhole resistance, Young's modulus in the vertical direction of 220 kg / mm ² , DSC method It is a biaxially stretched nylon 6 resin film layer having a melting point of 220 ° C. and a thickness of 15 μm. Thin film layer 2: A vacuum deposited thin film layer made of aluminum having a purity of 99.8% and having a thickness of 400 °.

<Adhesive Layer> Two-component polyester dry laminate type adhesive layer of diisocyanate and polyester polyol (solid content of 3.0 to 4.5 g /
m ² ).

<Heat seal layer> A blown film layer having a thickness of 50 μm and having the following resin composition. Polyolefin resin: ethylene-hexene-1 copolymer resin (MFR 2.0 g / 10 min, density 0.925 g / cm ³ , polymerized by a gas phase method using one type of metallocene type catalyst of a single site catalyst, GPC molecular weight distribution is 2.5, Vicat softening point is 106 ° C, melting point is 123 ° C,
High-density polyethylene resin (MFR: 0.4 g / 10 min, density: 0.960 g / cm ³⁾ polymerized by a low-pressure method using one kind of a multi-site catalyst of a Ziegler type catalyst; GPC molecular weight distribution is 2
5, Vicat softening point of 125 ° C., melting point of 133 ° C., Shore hardness of 65 D) 30 parts by mass; low-density homopolyethylene resin (MFR 2 g) polymerized by a radical polymerization method of a high pressure method
/ 10 min, density 0.920 g / cm ³ , molecular weight distribution by GPC method 5.5, Vicat softening point 92 ° C., melting point 1
10 ° C., Shore hardness: 52D) 10 parts by mass Gas adsorbent: 0.1 part by mass of A-type zeolite which also has an anti-blocking action; 0.05 part by mass of talc;
Synthetic silica 0.05 parts by mass 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 photosensitive material; Having a number average molecular weight of 35, which also has the effect of improving
0.2 parts by mass of polypropylene wax of 0.05; 0.05 parts by mass of erucamide which plays an important role of improving resin fluidity, preventing blocking and improving lubricity Hydrotalcite compounds: BET specific surface area is 64 m
² / g, represented by the following formula having an average secondary particle diameter of 16 μm. Mg _0.7 Al _0.3 (OH) ₂ (CO ₃ ) _0.150.0 .
50H ₂ O 1.5 parts by mass Light-shielding substance: pH 7.0, average particle diameter 20 mμ, D
BP oil absorption is 67cc / 100g, sulfur content is 0.0
5%, nitrogen adsorption surface area 130 m ² / g, ash content 0.2
3 parts by mass of furnace carbon black having a tinting strength of 130% and a volatile content of 0.8% Antioxidant: tetrakis [methylene-3- (3 ′, 5′-) which is a hindered phenolic antioxidant J-ter
t-butyl-4'-hydroxyphenyl) propionate] methane 0.05 parts by mass Antistatic agent: antistatic agent masterbatch 2 manufactured by Kao KK
Parts by mass

A light-room-loaded package was manufactured using the above-described layered packaging material for photosensitive material. The procedure for manufacturing the package is shown below.

First, as shown in FIG. 5, an X-ray film 11 obtained by coating a biaxially stretched polyester resin film with an X-ray photosensitive layer and having a B4 size (257.times.364 mm) corner cut at four corners was used. 150 sheets are stacked on top to form a stack 12 of the X-ray film 11, and this stack 12 is, as shown in FIG. 6, a ball 13 made of a white multilayer paperboard having a notch for detection. To the fin side.

Next, as shown in FIG. 7, using the moisture-proof light-shielding bag 14 formed of the wrapping material for the photosensitive material of the first embodiment, an automatic wrapping machine is used to load the ball 13 into a bright room.
Then, as shown in FIG. 8, both ends of the moisture-proof light-shielding bag 14 are bent toward the BC surface side, and then, as shown in FIG. Attach the patch 15 so as to straddle it. The processing and packaging work is 6
The operation is performed at 0 ± 5% RH, and the water content of the ball 13 is set to 5% or less. Thereby, the humidity in the packaging bag can be maintained at 50% RH or less for a long time (one year or more).

As shown in FIG. 10, the packaging bag 14 containing the X-ray film 1 is put into the
6 (the zipper is indicated by the reference numeral 17).
As shown in the figure, a tape (or label) 18 for securing the original sealability and opening and a label 1 for quality indication
9 is attached. Note that the decorative box 16 with zipper is made of E cardboard (the front and back liners are made of unbleached kraft pulp, paperboard having a basis weight of 210 g / m ² , the middle E flute is made of semi-crafted pulp, and has a basis weight of 180 g / m ^2. Paperboard).

Then, as shown in FIG. 12, the decorative box 16 with the zipper is packed in five cardboard boxes 20, and as shown in FIG. 9, the flap of the cardboard box 20 is sealed with a hot melt adhesive. , Expiration date, production number, and product abbreviation are displayed.

[Comparative Example 1] Outside of a 7 µm thick aluminum foil (opposite side of the photosensitive material), a 15 µm thick high-density low-density homopolyethylene resin extrusion lamination type adhesive layer was used to form a 60 µm thick aluminum foil. Kraft paper is laminated, and an ethyleneimine-based anchor coat layer is applied to the inside of the aluminum foil (photosensitive material side) and dried, and then the thickness is 15
This is a packaging material for a photosensitive material in which a low-density homopolyethylene resin film layer containing furnace carbon black having a thickness of 50 μm is laminated via a high-pressure low-density homopolyethylene resin extrusion laminate type adhesive layer of μm. Using the packaging material for a photosensitive material having the above-described layer configuration, a light-room-loaded package having the same form as in Example 1 was manufactured in the same procedure as in Example 1.

[Comparative Results of Each Property of Example 1 and Comparative Example 1] In Example 1, the physical strength, the bag breaking strength, the pinhole resistance, and the photographic properties (rolling used for aluminum foil which adversely affects the photographic properties) Since no oil is used, and the bag breaking strength and the pinhole resistance are significantly improved as compared with the aluminum foil, a high gas barrier property and a high moisture-proof property can be secured during transportation.), And the appearance was superior to that of Comparative Example 1. Furthermore, the metal residue when incinerated was also reduced to 1/20 or less of Comparative Example 1, and the incineration suitability was excellent.

Further, since the innermost layer is provided with a heat seal layer containing an ethylene / hexene-1 copolymer resin polymerized using a single-site catalyst as a main component (60 parts by mass), photographic properties are improved. Good (highly active catalyst is used, so there are few catalyst residues that adversely affect photographic properties,
And low-molecular-weight components that generate aldehydes that have a bad effect on the photographic properties of photographic light-sensitive materials by thermal decomposition),
Low-temperature heat sealing is possible (there is little generation of harmful gas that adversely affects photographic properties), good hot-tack property, good sealing of foreign substances, and excellent long-term sealing and light-shielding properties. Chemical sensitization with severe quality deterioration and / or
Or, it is most suitable as a package for a silver halide photographic light-sensitive material which is a dye-sensitized ultra-precision product.

Further, since 10 parts by mass of the low-density polyethylene resin is contained, the film formability, the decrease in the thickness of the heat-sealed portion is small, and the light-shielding property, moisture-proof property, oxygen barrier property, heat-sealing strength, and sealing property are improved. The heat seal layer made of only an ethylene / α-olefin copolymer resin polymerized using a single-site catalyst is much better.

The ethylene / hexene-1 copolymer resin obtained by the gas phase method has better photographic properties (the effect of less catalyst residue), lower polymerization energy and lower cost than the ethylene / α-olefin copolymer resin obtained by other polymerization methods. And physical strength is excellent.

The biaxially stretched polyethylene naphthalate resin film layer has a small curl and excellent physical strength, ultraviolet shielding property, gas barrier property, light shielding property, suitability for bag making, bag breaking strength, moisture resistance, oxygen barrier property and appearance. I have.

Further, an aluminum oxide deposited thin film layer having more excellent crack resistance than a silicon oxide deposited thin film layer, and an aluminum deposited thin film layer which is slightly inferior in moisture resistance but has excellent crack resistance, light-shielding properties, antistatic properties and appearance. Is laminated via a two-component reaction type polyester dry laminating adhesive layer, so it has excellent crack resistance, moisture resistance, gas barrier properties, physical strength, and pinhole resistance. .

Example 2 A packaging material for a photosensitive material having a moisture permeability of 0.25 g / m ² · 24 hours or less, which is a laminated film having the layer structure shown in FIG.

<High Young's Modulus / Heat-Resistant Thermoplastic Resin Film Layer> This is the same as the high Young's modulus / heat-resistant thermoplastic resin film layer made of PEN resin in Example 1.

<Adhesive layer> The MFR was 4.8 g / 10 min.
Density: 0.920 g / cm ³ , Vicat softening point: 99
C., 65 parts by mass of a high-pressure radical polymerization low-density homopolyethylene resin having a molecular weight distribution of 6.8, 20 parts by mass of an ethylene / butene-1 copolymer resin polymerized by a low-pressure / gas phase method, and an unsaturated carboxylic acid-modified resin It is an ethylene-based resin extrusion laminate adhesive layer (resin temperature 330 ° C., thickness 15 μm) composed of 15 parts by mass of a high-pressure radical polymerization low-density homopolyethylene resin. In addition, high Young's modulus
The heat-resistant thermoplastic resin film layer and the adhesive layer are laminated by a tandem lamination method.

<Barrier film layer 3> High Young's modulus and heat-resistant thermoplastic resin film layer 1: High Young's modulus and heat-resistant thermoplastic resin film made of the same nylon 6 resin as inner barrier film layer 3 in Example 1. Same as layer. Thin film layer 2: Same as the aluminum oxide thin film layer in the outer barrier film of Example 1.

<Adhesive layer> The MFR was 4.8 g / 10 min.
Density: 0.920 g / cm ³ , Vicat softening point: 99
C., 65 parts by mass of a high-pressure radical polymerization low-density homopolyethylene resin having a molecular weight distribution of 6.8, 20 parts by mass of an ethylene / butene-1 copolymer resin polymerized by a low-pressure / gas phase method, and an unsaturated carboxylic acid-modified resin It is an ethylene-based resin extrusion laminate adhesive layer (resin temperature 330 ° C., thickness 15 μm) composed of 15 parts by mass of a high-pressure radical polymerization low-density homopolyethylene resin. Note that the heat seal layer and the adhesive layer are laminated by a tandem lamination method.

<Heat seal layer> This is the same as the heat seal layer of Example 1.

Using the wrapping material for a photographic material having the above-mentioned layer structure, the same photographic material wrapping body as in Example 1 was manufactured, and each characteristic was compared. Example 2 is excellent in physical strength, pinhole resistance, and bag breaking strength except that it has a higher moisture permeability than Example 1, and has no metal residue when incinerated, has excellent incineration suitability, and generates loss. Low, high productivity, 20
% Inexpensive and preferred.

Since the biaxially stretched polyethylene naphthalate resin film layer having high moisture resistance and gas barrier properties and having a high Young's modulus and heat resistance was provided on the outermost layer, curling was small, the peeling of the vacuum-deposited thin film layer did not occur, and , Light shielding properties, suitability for bag making, and pinhole resistance were excellent.

[0193] [Example 3] In the laminated film having a layer constitution shown in FIG. 1, the moisture permeability is 0.15g ^{/ m} 2 · 24 hr g
/ ^M 2 · 24 hours or less of a light-sensitive material for packaging material.

<High Young's Modulus / Heat-Resistant Thermoplastic Resin Film Layer> This is the same as the high Young's modulus / heat-resistant thermoplastic resin film layer of PEN resin in Example 1.

<Adhesive Layer> This is the same as the adhesive layer of Example 2.

<Barrier film layer 3> High Young's modulus heat-resistant thermoplastic resin film layer 1: High Young's modulus heat-resistant thermoplastic resin film made of the same nylon 6 resin as inner barrier film layer 3 in Example 1. Same as layer. Thin film layer 2: A vapor-deposited thin film layer having a thickness of 400 ° and made of two kinds of inorganic compounds and metal oxides made of a mixture of aluminum oxide and silicon dioxide.

<Adhesive Layer> The adhesive layer of Example 2 is the same.

<Heat Seal Layer> This is the same as the heat seal layer of Example 1.

The same photosensitive material package as in Example 2 was manufactured using the photosensitive material packaging material having the above-described layer structure, and each characteristic was compared. Example 3 was more excellent in moistureproofness than Example 2, and had no metal residue when incinerated, and was excellent in incineration suitability. When a package of silver halide photographic light-sensitive material, which is an ultra-precision product subjected to chemical sensitization and / or dye sensitization, was used, the quality was excellent for a long period of time.

Since the biaxially stretched polyethylene naphthalate resin film layer of high Young's modulus and heat resistance having a moisture-proof property and a gas barrier property is provided on the outermost layer, the curl is small, the vacuum-deposited thin film layer does not peel off, and the moisture-proof property does not occur. It was excellent in light-shielding properties, suitability for bag making, and pinhole resistance.

[0201] [Example 4] In the laminated film having a layer constitution shown in FIG. 1, the moisture permeability is 0.15g ^{/ m} 2 · 24 hr g
/ ^M 2 · 24 hours or less of a light-sensitive material for packaging material.

<High Young's Modulus / Heat-Resistant Thermoplastic Resin Film Layer> This is the same as the high Young's modulus / heat-resistant thermoplastic resin film layer of PEN resin in Example 1.

<Adhesive Layer> This is the same as the adhesive layer of Example 2.

<Barrier Film Layer 3> High Young's modulus heat-resistant thermoplastic resin film layer 1: High Young's modulus heat-resistant thermoplastic resin film made of the same nylon 6 resin as inner barrier film layer 3 in Example 1. Same as layer. Thin film layer 2: A vapor-deposited thin film layer having a thickness of 400 ° and made of two kinds of inorganic compounds and metal oxides made of a mixture of aluminum oxide and silicon dioxide.

<Adhesive Layer> The adhesive layer of Example 2 is the same.

<Heat-seal layer> The same polyolefin resin composition as that of the heat-seal layer of Example 3 was used except that the resin composition of the heat-seal layer of Example 3 further contained 5 parts by mass of aluminum hydroxide. It is a blown film layer having a thickness of 50 μm.

Using the wrapping material for a photographic material having the above-mentioned layer structure, the same photographic material wrapping body as in Example 3 was manufactured, and each characteristic was compared. In Example 4, there was no metal residue when incinerated after adsorbing and stabilizing metal ions than in Example 3, and dioxin in exhaust gas was adsorbed and stabilized to reduce environmental pollution and was excellent in incineration suitability. Was. This effect is thought to be due to the aluminum hydroxide contained in the heat seal layer.

That is, aluminum hydroxide is Al ₂
Consists of the chemical formula of O ₃ .3H ₂ O, 250-1200 ° C.
When heated, the water of crystallization is released and activated alumina (Al ₂
O ₃ ). This activated alumina is 80 to 250
m ² / g, preferably 90~230m ² / g, particularly preferably from 100 to 200 m ² / g, most preferably 110
It has a specific surface area of 190 m ² / g and, as described above, is a substance that functions as an adsorbent and a combustion promoter for various chemical substances and gases that adversely affect photographic properties. When a package of silver halide photographic light-sensitive material, which is an ultra-precision product subjected to chemical sensitization and / or dye sensitization, was used, the quality was excellent for a long period of time.

In addition, since the biaxially stretched polyethylene naphthalate resin film layer having high moisture resistance and gas barrier properties and a high Young's modulus and heat resistance is provided on the outermost layer, the curl is small and the vacuum deposited thin film layer does not peel off. It was excellent in moisture proof, light shielding, suitability for bag making, and pinhole resistance.

[0210]

The present invention has the following effects by adopting the above-mentioned structure. (1) Humidity, oxygen gas, sulfurous acid gas, formalin gas,
Photosensitive materials that are adversely affected by hydrogen cyanide gas, halogen compound gas, and the like, especially silver halide photographic materials that are fatally adversely affected by photographic properties, can be used for a long time (1
Years) good quality can be maintained. (2) The heat seal layer has excellent photographic properties, lubricity, physical strength, and heat seal suitability. (3) It is superior in photographic properties, physical strength, bag breaking strength, pinhole resistance, incineration suitability, and the like, as compared with packaging materials laminated with aluminum foil. (4) The outermost layer has a longitudinal Young's modulus of 50 kg / mm ² or more,
The melting point of SC method is 130 ° C or more, and the moisture permeability is 20 g / m
Placing the following ^2-24 hours a high Young's modulus, heat-resistant thermoplastic resin film layer, it is possible to reduce the curl. (5) When used as a packaging bag for loading into a light room, the pull-out resistance is small and the opening workability is excellent.

[Brief description of the drawings]

FIG. 1 is a partial cross-sectional view illustrating a layer configuration of an embodiment of a photosensitive material packaging material according to the present invention.

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

FIG. 3 is a partial cross-sectional view illustrating a layer configuration of another embodiment of the packaging material for a photosensitive material according to the present invention.

FIG. 4 is a partial cross-sectional view illustrating a layer configuration of another embodiment of the packaging material for a photosensitive material according to the present invention.

FIG. 5 is a perspective view of a stack of X-ray films used in a bright-room-packed X-ray film package which is an embodiment of a sheet-like photographic film package according to the present invention.

FIG. 6 is a perspective view showing a state in which a stack of X-ray films is wrapped with a contact ball in an X-ray film light-room packed package which is an embodiment of the sheet-like photographic film package according to the present invention.

FIG. 7 shows an X-ray film light-room packed package which is an embodiment of a sheet-shaped photographic film package according to the present invention, in which a stack of X-ray films wrapped with balls is packed in a moisture-proof light-shielding bag. It is a perspective view of a state.

FIG. 8 is a perspective view showing a state in which both ends of a moisture-proof light-shielding bag are folded in an X-ray film light-room packed package which is an embodiment of a sheet-shaped photographic film package according to the present invention.

FIG. 9 is a perspective view showing a state in which an emblem is affixed to a moisture-proof light-shielding bag in an X-ray film light-room packed package which is an embodiment of a sheet-shaped photographic film package according to the present invention.

FIG. 10 is a perspective view showing a state in which a moisture-proof light-shielding bag is packed in a decorative box with a zipper in an X-ray film light-room packed package which is an embodiment of a sheet-shaped photographic film package according to the present invention.

FIG. 11 is a perspective view showing a state in which an opening tape or a label is attached to a decorative box with a zipper in an X-ray film light-room packed package which is an embodiment of the sheet-shaped photographic film package according to the present invention.

FIG. 12 is a perspective view of an X-ray film light-room-packed package that is an embodiment of a sheet-shaped photographic film package according to the present invention, with a zipper-equipped cosmetic box housed in a cardboard box.

FIG. 13 is a perspective view showing a state in which a cardboard box is sealed in an X-ray film light-room packed package which is an embodiment of the sheet-shaped photographic film package according to the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 11 ... X-ray film 12 ... Stack of X-ray film 13 ... This ball 14 ... Moisture-proof light-shielding bag 15 ... Patch 16 ... Makeup box with zipper 17 ... Zipper 18 ... Opening tape or label 19 ... Label for quality display 20 ... Corrugated cardboard box

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) G03C 3/00565 G03C 3/00 565K 585 585B 599 599A

Claims (5)

[Claims] 1. A longitudinal Young's modulus (ASTM D88)
2) is 50 kg / mm ²As described above, the melting point of the DSC method was 130.
High Young's modulus and heat resistant heat with a temperature of ℃ or more and thickness of 5 to 70 μm
Plastic resin film layer, high Young's modulus, heat resistant thermoplastic
Thickness 50 laminated on one or both sides of resin film layer
A metal thin film layer of up to 3000
Or a barrier film layer comprising an inorganic substance thin film layer,
An adhesive layer inside the barrier film layer (the photosensitive material side)
Layered through or without an adhesive layer
Ethylene / α-olefin polymerized using Lucite catalyst
And a heat seal layer mainly composed of copolymer resin.
A packaging material for photosensitive materials, characterized in that: 2. The biaxially stretched polyamide resin film layer, wherein the high Young's modulus and heat resistant thermoplastic resin film layer has a Young's modulus in the longitudinal direction of 130 kg / mm ² or more and a melting point of 160 ° C. or more by a DSC method. At least one selected from a stretched polyethylene terephthalate resin film layer, a biaxially stretched polyethylene naphthalate resin film layer, and a biaxially stretched ethylene / vinyl alcohol copolymer resin film layer
The packaging material for a photosensitive material according to claim 1, which is a seed. 3. The packaging material for a photosensitive material according to claim 1, wherein the metal thin film layer and the inorganic substance thin film layer are made of at least one selected from aluminum, silicon oxide, magnesium oxide and aluminum oxide. 4. The ethylene / α-olefin copolymer resin has a molecular weight distribution of 1.1 to 5.0 and an MFR of 0.1 to 5.0.
10 g / 10 min, density 0.850-0.940 g / c
m ^3, a melting point of 80 to 120 ° C., according to claim 1 is obtained by copolymerizing α-olefins and having 3 to 12 carbon atoms using a catalyst comprising a metallocene transition metal compound and an organoaluminum compound Packaging materials for photosensitive materials. 5. A photosensitive material package, wherein the photosensitive material subjected to chemical sensitization and / or dye sensitization is hermetically sealed using the packaging material for photosensitive material according to claim 1, 2, 3, or 4.