JP2000098546A - Packaging material for photographic sensitive material and photographic sensitive material packaged body using same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To produce a packaging material for photographic sensitive materials only by a multilayer co-extrusion inflation film forming process so that the packaging material does not give bad influences on the photographic properties of the photographic sensitive material, that the packaging material has large physical strength, does not curl, has large blocking adhesion strength and excellent film forming properties, that the material is flexible with little loss and maintains sealing properties for a long time, and that the material meets the Container Packaging Recycling Law. SOLUTION: This packaging material is a laminated film produced by adhering and laminating the innermost layers 1a of multilayered co-extrusion inflation films IIa by blocking, each of films IIa having two or more layers. The innermost layer 1a contains >=50 wt.% polyolefin resin polymerized by using a single site catalyst and 0.1 to 50 wt.% blocking adhesion reinforcing resin.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION The present invention relates to a packaging material for a photographic light-sensitive material, comprising a laminated film in which the innermost layers are bonded and laminated by blocking, which was conventionally regarded as a major drawback of the film, without using an adhesive layer. The present invention relates to a photographic photosensitive material package using the same.

[0002]

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

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

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

[0005]

However, the packaging materials proposed in the past have various problems and improvements have been desired. That is, the packaging material proposed in JP-A-64-22544 has low curling, high physical strength, excellent recyclability and incineration suitability,
Although it was extremely preferable, low-temperature heat sealability was not sufficient, and further improvement in photographic properties and physical strength was desired.

The photosensitive material packaging film proposed in Japanese Patent Publication No. 2-2700 is preferable because it has excellent physical strength even in a single layer. However, in order to use a single layer for a heavy substance package having a high moisture-proof property, the thickness must be increased, and when the thickness is increased, a melt fracture occurs. Therefore, a packaging material for a photographic light-sensitive material cannot be constituted by a single layer, and it is necessary to laminate a metal layer, and it has been desired to improve the cost, incineration suitability and recycling suitability. Further, when the metal layers are laminated, there is a disadvantage that the physical strength (tear strength, impact piercing strength, gelbotest strength, etc.) is reduced.

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

In a photographic light-sensitive material package made of a wrapping material for photographic light-sensitive material using a laminated film laminated by blocking adhesion, the blocking adhesion is peeled off at the opening of the packaging bag, and when the photographic light-sensitive material is taken in and out. In some cases, hands may get inside and the workability may deteriorate.

The present invention solves the above-mentioned problems, and adversely affects the photographic properties of a photographic material which is indispensable as a packaging material for a photographic material (fog, abnormal sensitivity, gradation, etc.) only by a multilayer co-extrusion blown film forming process. It does not cause abnormalities, abnormal coloring, or uneven density, etc., has high physical strength, does not cause curling, has high blocking adhesive strength, film formability, heat sealability (long-term heat seal sealability) , Contaminant sealing properties, etc.)
Flexible, low loss, long-term sealability to maintain good photographic properties of photographic light-sensitive materials, excellent recyclability and incineration suitability, for containers and packaging recycling law An object of the present invention is to provide a packaging material and a photographic photosensitive material package using the same.

[0010]

The packaging material for a photographic light-sensitive material of the present invention is a laminated film in which the innermost layers of a multi-layer co-extruded blown film having two or more layers are bonded and laminated by blocking. The inner layer is characterized in that the polyolefin resin produced by polymerization using a single-site catalyst is 50% by weight or more, and the blocking adhesion reinforcing resin is 0.1 to 50% by weight.

In the packaging material for a photographic light-sensitive material of the present invention, the innermost layer contains 50% by weight or more of a polyolefin resin produced by polymerization using a single-site catalyst, and 0.1 to 50% by weight of a blocking adhesion reinforcing resin. %, The physical strength is large, the occurrence of curling is small, the film formability is excellent, and the innermost layers are sufficiently free from blocking adhesion, so that they are not peeled off.

A photographic photosensitive material package according to the present invention comprises a photographic photosensitive material housed in a packaging bag manufactured by using the photographic photosensitive material packaging material, and an opening through which the photographic photosensitive material is put in and taken out of the packaging bag. Are characterized in that the innermost layers are bonded at one or more locations with a peel strength greater than the blocking adhesion.

In the photographic light-sensitive material package of the present invention,
Since the innermost layers are bonded at one or more locations with a peel strength greater than the blocking adhesion, even if the adhesion due to the blocking is released, it will not be peeled over the entire surface. In such a case, the hand of the person trying to take out or put in the bag does not enter the innermost layer to which the blocking adhesion is applied.

[0014]

BEST MODE FOR CARRYING OUT THE INVENTION The packaging material for photographic light-sensitive materials of the present invention is formed of a laminated film in which the innermost layers of a multilayer co-extruded blown film are adhered and laminated by blocking. This multilayer co-extruded blown film has an intermediate layer of two or more layers, even if it is composed of two layers of an innermost layer and an outermost layer, or three layers of an innermost layer, an intermediate layer and an outermost layer. It may be composed of four or more layers. If necessary, at least one surface of the laminated film may be laminated with one or more flexible sheets via an adhesive layer or without an adhesive layer (see, for example, FIG. 6).

Since the laminated film is formed by blocking and laminating the innermost layers of a multilayer co-extruded blown film, the laminated film has a vertically symmetric structure. In order to pseudo-adhere the innermost layers of the multilayer co-extrusion blown film by blocking, for example, when forming a multilayer co-extrusion blown film by the multilayer co-extrusion inflation method, a new nip roll for take-off or a new stage provided after the nip roll for take-off is provided. This is performed by pressing the innermost layers of the multilayer co-extruded blown film with a pressure roll. If necessary, the take-off nip roll or pressure roll may be heated. Round die method A round die (ring die) used in a multilayer coextrusion blown film forming machine is roughly divided into a multi-manifold die of a die internal lamination type, a multi-slot die of a die external lamination type, and a die before a die of a laminar flow supply type. There are three types of single-manifold dies for merging materials, but any type can be used in the present invention, but a round die of a die-in-layer type is preferable because it has a large interlayer adhesive force.

In order to further increase the blocking adhesive strength, a far-infrared lamp, a hot air or a dichrome wire heater is used before passing through each roll such as a nip roll, a pressure roll (which may form an emboss), a heating roll and the like. Or other heating devices. Furthermore, it is preferable to stretch uniaxially in the vertical direction immediately after forming the laminated film in which the innermost layers are bonded and laminated by blocking as described above (0 to 15 seconds), because the bonding strength is further improved.

In the blocking bonding of the innermost layer, instead of being completely bonded and fixed so as to be bonded with an adhesive, pseudo bonding is performed in a somewhat flexible state by blocking without using any adhesive, and physical bonding is performed. It improves strength and prevents curling. In addition, since there is no need to laminate via an adhesive layer which deteriorates by heat or adversely affects the photographic properties of the photographic light-sensitive material, recyclability is excellent.

In the packaging material for a photographic light-sensitive material of the present invention, the innermost layer of the multilayer co-extruded blown film comprises 50% by weight of a polyolefin resin produced by polymerization using a single-site catalyst (hereinafter referred to as a single-site polyolefin resin). At least 60% by weight, more preferably at least 70% by weight, particularly preferably at least 80% by weight, and most preferably at least 90% by weight.
It contains the above.

If the content of the single-site polyolefin resin is less than 50% by weight, the physical strength is reduced and the amount of catalyst residue is increased, which adversely affects the photographic properties of the photographic light-sensitive material. It is necessary to add a metal salt, and the blocking adhesive strength varies.

A typical example of a single-site catalyst is a metallocene catalyst comprising zirconocene dichloride and methylaminoxan having a uniform active site, discovered by Professor Kaminsky of Germany, and various patents have been published. Have been. A representative example is JP-A-60-3
JP-A-5007, JP-A-60-35008, JP-A-60-35009, JP-A-3-207703, JP-A-3-234711, JP-A-4-30
No. 0887 and the like.

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

The polymerization method using the metallocene catalyst has been disclosed in a number of patent publications as exemplified below.

JP-A-58-19309, JP-A-6-19309
0-862, JP-A-60-35006, JP-A-60-35007, JP-A-60-35008
JP-A-60-106008, JP-A-60-106008,
-137911, JP-A-61-31404, JP-A-61-108610, JP-A-61-2
No. 21207, JP-A-61-264010,
JP-A-61-29609, JP-A-63-610
No. 10, JP-A-63-152608, JP-A-63-178108, JP-A-63-222177
JP, JP-A-63-222178, JP-A-63-222178
JP-A-222179, JP-A-63-264606, JP-A-63-28070, JP-A-63-50
No. 1369, Japanese Patent Application Publication No. 64-6003, Japanese Patent Application Publication No. 64-45406, Japanese Patent Application Laid-Open No. 64-74202, Japanese Patent Application Laid-Open No. 1-1407, and Japanese Patent Application Laid-Open No. 1-9511.
0, JP-A-1-101315, JP-A-1-101315
129003, JP-A-1-207248,
JP-A-1-210404, JP-A-1-25140
No. 5, JP-A-1-259004, JP-A-1-259004
275609, JP-A-1-301704,
JP-A-1-319489, JP-A-2-22307
JP, JP-A-2-41303, JP-A-2-17
3110, JP-A-2-302410, JP-A-3-56508, JP-A-3-62806, JP-A-3-66710, JP-A-3-7070
No. 8, JP-A-3-70709, JP-A-3-7
0710, JP-A-3-74412, JP-A-4-8704, JP-A-4-11604, JP-A-4-25514, JP-A-4-213305, JP-A-5-310829 Gazette, JP-A-5-32
0242, JP-A-6-228222, JP-A-9-40793, U.S. Pat.
No. 82, U.S. Pat. No. 4,530,914 and the like.

Specific examples of commercially available L-LDPE resins polymerized and produced using a metallocene catalyst, which is a typical example of a single-site catalyst, include EXCEED (EXXon chemical) EXACT (EXXon chemical) AFFINITY (DOW chemical) ENGAGE ( DOW chemical) LUFLEXENE (BASF) Evolu (Mitsui Petrochemical) Kernel (Mitsubishi Chemical) Yumerit (Ube Industries) Harmolex (Nippon Polyolefin) Catalocene (Tosoh).

The polyolefin resin is a generic term for homopolymers or copolymers of olefins having a relatively simple structure such as ethylene, propylene, butene, pentene and methylpentene. In a broad sense, ethylene-vinyl acetate copolymer, ethylene-ethyl acrylate copolymer,
Also included are ionomers, terpolymers of ethylene-propylene-dienes, and the like. The general characteristics of polyolefins are low specific gravity, excellent chemical resistance and water resistance, and excellent in high-frequency insulation because of low dielectric constant and dielectric power factor.

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

Since the polyethylene resins obtained by different polymerization methods have different properties, they are also classified according to production methods such as the high pressure method (ICI method), the medium pressure method (Philips method), and the low pressure method (Ziegler method). However, the essential difference in properties is related to the density, and low density (0.910 to 0.925 g /
cm ^3), medium density (0.926~0.940g / cm ^3), high density (0.941~0.965g / cm ^3, ultra-high density (0.966 g / cm ³ or higher)) classified as Have been. Table 1 shows the approximate relationship between the density and the properties of the polyethylene resin.

[0028]

[Table 1]

The polyethylene resin, which is one of the polyolefin resins, is roughly classified into a high-density polyethylene resin and a low-density polyethylene resin according to its density. A high-density polyethylene resin has a linear molecular structure with few branches and a high degree of crystallinity, whereas a low-density polyethylene resin has many branches and a low degree of crystallinity. Higher crystallinity, that is, higher density polyethylene resin has higher melting point and higher rigidity,
Transparency is reduced. In addition, even for the same low-density polyethylene resin, the linear low-density polyethylene resin having short-chain branches has higher crystallinity and the number of tie molecules than the branched low-density polyethylene resin having long-chain branches. Because of the large number, the melting point is high and the mechanical strength is excellent, but since the entanglement of the molecular chains at the time of melting is small, the melt tension is low and the film formability is poor.

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

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

The molecular weight distribution refers to the spread of the molecular weight. That is, a high molecular substance is generally a mixture of homologous series of polymerizations, and is composed of a large number of molecules having different degrees of polymerization or molecular weights. The spread of the molecular weight is called a molecular weight distribution, and the degree of spread is shown by a molecular weight distribution curve. The average molecular weight includes a weight average molecular weight (Mw) and a number average molecular weight (Mn) depending on the measurement method, and the ratio Mw / Mn shows a large value when the molecular weight distribution is wide. It is a guide. In the case of polyethylene resin, even with a material with the same average molecular weight, a material with a wide molecular weight distribution has good stress cracking properties and creep resistance, but its impact resistance is slightly inferior. The higher the melt viscosity, the longer it takes to relax the internal stress, indicating that melt fracture is likely to occur. In this way, the molecular weight distribution shows the processability of plastic,
The effect on physical strength and properties cannot be ignored.

Preferably, at least 50% by weight of the single-site polyolefin resin is an ethylene copolymer resin, more preferably at least 60% by weight.
Particularly preferred is 70% by weight or more, and 80% by weight
It is most preferred that this is the case. If the proportion of the ethylene copolymer resin is less than 50% by weight, it may not be possible to ensure sufficient hot tack properties, foreign substance sealing properties, heat sealing strength, physical strength, and the like.

Representative examples of the ethylene copolymer resin are shown below. (1) Ethylene-vinyl acetate copolymer resin (hereinafter referred to as EV
(Indicated as A resin) (2) Ethylene-propylene copolymer resin (3) Ethylene-1-butene copolymer resin (4) Ethylene-butadiene copolymer resin (5) Ethylene-vinyl chloride copolymer resin (6 ) Ethylene-methyl methacrylate copolymer resin (hereinafter referred to as EMM resin) (7) Ethylene-methyl acrylate copolymer resin (hereinafter referred to as EMA resin) (8) Ethylene-ethyl acrylate copolymer resin (Hereinafter referred to as EEA resin) (9) Ethylene-acrylonitrile copolymer resin (10) Ethylene-acrylic acid copolymer resin (hereinafter referred to as EA resin)
(Indicated as A resin) (11) Ionomer resin (resin obtained by crosslinking a copolymer of ethylene and unsaturated acid with a metal such as zinc) (12) Ethylene / α-olefin copolymer resin (hereinafter referred to as L
(Shown as LDPE resin) (13) Ethylene-propylene-butene-1 terpolymer resin (14) Polyolefin elastomer (15) Ethylene-propylene-diene terpolymer resin

Among the ethylene copolymer resins, L-LDP
E resin, propylene-α-olefin copolymer resin, EE
A resin, EVA resin, EAA resin, and ethylene-based elastomer are preferred, and L-LDPE resin, propylene-α-olefin copolymer resin, and ethylene-based elastomer are particularly preferred, and a copolymer resin of ethylene and a C4-10 α-olefin is preferred. Alternatively, a polyolefin-based elastomer in which the hard segment is polypropylene and the soft segment is ethylene-propylene rubber is most preferred.

The innermost layer of the multilayer co-extruded blown film has a blocking adhesion reinforcing resin content of 0.1.
-50% by weight, preferably 0.5-45% by weight, more preferably 1-40% by weight, particularly preferably 2-35% by weight, most preferably 4-30% by weight.

When the content of the blocking adhesion reinforcing resin is 0.
When the amount is less than 1% by weight, the blocking adhesive strength is not effectively improved, the blocking adhesive portion is peeled off, making it difficult to put into practical use, and only the kneading cost is increased. The blocking adhesion between them becomes too large, and it becomes difficult to supply the resin pellets to the extruder, so that it cannot be performed smoothly in the process of manufacturing the film by the blown film forming method.

In addition, since the amount of the expensive blocking adhesion reinforcing resin increases, the film becomes expensive and there is a problem in terms of economy.

Examples of the blocking adhesion reinforcing resin include a low polymerization degree polyolefin resin, a low softening point resin, a low crystallinity polyolefin resin, and tackifier.
r), and the low-polymerization degree polyolefin resin has a number average molecular weight of 300 to 7000, preferably 50 to 7000.
0-6000, most preferably 1000-4000. Typical examples of polyolefin resins include polyethylene resin, ethylene copolymer resin, polypropylene resin, ethylene-propylene copolymer resin, propylene
There is an α-olefin copolymer resin.

When the number average molecular weight is less than 300, the film formability deteriorates or bleeds out on the film surface with the passage of time. Therefore, various problems such as transfer to a photographic light-sensitive material, development inhibition, developer contamination and the like occur. Generate. In addition, there is much heat deterioration and smoke generation during film formation, and the physical strength of the film is also reduced. When the number average molecular weight exceeds 7000, the effect of improving film formability, blocking adhesiveness, and the like is reduced. In addition, it is difficult to improve the dispersibility of a light-shielding substance or a coloring substance such as titanium oxide or aluminum powder and carbon black added according to the necessity in the innermost layer of the multilayer co-extruded blown film.

The low-polymerized polyolefin resin having a number average molecular weight of 300 to 7000 is preferably contained in the innermost layer in an amount of 0.1 to 50% by weight, more preferably 1 to 40% by weight, and more preferably 2 to 35% by weight. It is particularly preferably contained, and most preferably 4 to 30% by weight. However, the total content of the above-mentioned blocking adhesion reinforcing resin is 0.1.
Adjustment within the range of 1 to 50% by weight is essential in the present invention.

If it is less than 0.1% by weight, the film formability,
The effect of improving blocking adhesion, lubricity and the like is small, and only the kneading cost increases. If it exceeds 50% by weight, the melt flow rate of the thermoplastic resin composition (hereinafter referred to as M
(Indicated by FR) becomes too large, the valve tends to sway when forming an inflation film having a large thickness of the innermost layer, and bleed-out increases, so that it becomes too slippery and cannot be wound well. In addition, a large amount of heat is generated during the film forming process and a large amount of smoke is generated, which not only deteriorates the manufacturing environment but also lowers the physical strength of the film.

Further, it is difficult to improve the dispersibility of a light-shielding substance or a coloring substance such as carbon black, titanium oxide and aluminum powder added according to the necessity in the innermost layer of a multilayer co-extruded blown film.

As the blocking adhesion reinforcing resin used in the present invention, a tackifier (tackifier) is used.
r)), and examples of the tackifier are described below.

Natural products and derivatives thereof Resins containing polar groups (1) Rosin resin Rosin gum rosin Tall oil rosin Wood rosin Modified rosin Hydrogenated rosin Disproportionated rosin Polymerized rosin rosin ester Essam gum (rosin glycerin ester) Hydrogenated rosin (pentaerythritol ester, etc.) (2) Terpene phenol Resin 2. 2. A resin containing no polar group (1) Terpene resin α-pinene-based β-pinene-based dipentene (limonene) -based (2) hydrocarbon-modified terpene resin Polymerized resin (1) Petroleum resin Aliphatic hydrocarbon resin Aromatic hydrocarbon resin Alicyclic hydrocarbon resin (2) Coumarone indene resin (3) Styrene resin Styrene resin Substituted styrene, etc. (4 3.) Coumarone resin 4. Condensation resin (1) Phenol resin Alkyl phenol resin Rosin modified phenol resin (2) Xylene resin Xylene resin Modified xylene resin Mineral oil Mineral spirit

The tackifier is preferably contained in the innermost layer in an amount of 0.1 to 50% by weight, more preferably 1 to 40% by weight, particularly preferably 2 to 35% by weight. Most preferably, it is contained in an amount of about 30% by weight. However, it is essential in the present invention that the total content of the above-mentioned blocking adhesion reinforcing resin is adjusted within the range of 0.1 to 50% by weight.

When the amount is less than 0.1% by weight, the effect of adding the tackifier is not exhibited, and when the amount exceeds 50% by weight, blocking between pellets, heat deterioration during film forming and smoking are large, and film formability deteriorates. And at the same time, reduce the strength of the film. Further, since the content of the expensive tackifier is increased, the film becomes expensive, and practical use is difficult.

There is a low softening point resin as a blocking adhesion reinforcing resin, and the resin having a low softening point will be described.

In the low softening point resin, the softening point is
Vicat softening point (ASTM D 1525). The low softening point resin, the Vicat softening point is 110 ℃ or less, preferably 105 ℃ or less, more preferably 100 ℃ or less,
Most preferably, it is a polyolefin resin having a temperature of 95 ° C. or lower.

Among the polyolefin resins, preferred resins are non-polluting (no oxidant, chlorine gas, halogen compound, formalin gas, phenol gas, sulfur compound gas, cyanide compound gas, etc.), Is an ethylene copolymer resin which has little adverse effect on the properties, is inexpensive, is easily available worldwide, and is excellent in dispersibility, heat sealability, physical strength and the like of a light-shielding substance.

Representative examples of the ethylene copolymer resin which is a resin having a low softening point which can be used as the blocking adhesion reinforcing resin are described below. (1) Ethylene-vinyl acetate copolymer resin (hereinafter referred to as EV
(Indicated as A resin) (2) Ethylene-propylene copolymer resin (3) Ethylene-1-butene copolymer resin (4) Ethylene-butadiene copolymer resin (5) Ethylene-vinyl chloride copolymer resin (6 ) Ethylene-methyl methacrylate copolymer resin (hereinafter referred to as EMM resin) (7) Ethylene-methyl acrylate copolymer resin (hereinafter referred to as EMA resin) (8) Ethylene-ethyl acrylate copolymer resin (Hereinafter referred to as EEA resin) (9) Ethylene-acrylonitrile copolymer resin (10) Ethylene-acrylic acid copolymer resin (hereinafter referred to as EA resin)
(Indicated as A resin) (11) Ionomer resin (resin obtained by crosslinking a copolymer of ethylene and unsaturated acid with a metal such as zinc) (12) Ethylene-α-olefin copolymer resin (hereinafter referred to as L
(Shown as LDPE resin) (13) Acid-modified polyolefin resin (14) Ethylene-propylene-butene-1 terpolymer resin (15) Olefin thermoplastic elastomer

Among the ethylene copolymer resins, L-LDPE resin and EEA resin are most preferable because they have good film formability and heat sealing suitability, and have high bag breaking strength, impact punching strength and tear strength.

It is also preferred to blend with other thermoplastic resins, thermoplastic elastomers, synthetic rubbers, various additives and various modifiers in order to meet the required properties.

Particularly preferred ethylene copolymer resins are the Vicat softening points (ASYMD 1525) described below.
(A) L-LDPE resin, (B) EMA resin and EEA resin, (C) EVA resin, (D) acid-modified polyolefin resin having a Shore hardness (ASTM D 2240) of 5 to 60 D E) It is an olefin-based thermoplastic elastomer.

(A) The L-LDPE resin will be described. Melt flow rate (hereinafter referred to as MFR. ASTM D
(E condition of -1238) is 0.1 to 20 g / 10 min, preferably 0.5 to 10 g / 10 min, and the density (ASTMD-1)
505) is 0.870~0.927g / cm ^3, preferably 0.880~0.920g / cm ^3, particularly preferably L-LDPE resin 0.885~0.910g / cm ³ are preferred.

The L-LDPE resin is composed of ethylene and butene.
1, octene-1, hexene-1, 4-methylpentene-
1, a copolymer with an α-olefin having 3 to 20 carbon atoms such as heptene-1. MFR of L-LDPE resin
Is less than 0.1 g / 10 minutes, the motor load of the screw is large in blown film molding, the molding speed is reduced, and melt fracture is liable to occur. If it exceeds 20 g / 10 minutes, the physical strength of the film tends to decrease and drawdown tends to occur.

The density of the L-LDPE resin is 0.870 g /
If it is less than ³ cm3, drawdown tends to occur, and even if an anti-blocking substance is added, pellets are blocked or biting into the screw is deteriorated, which not only makes blown film molding difficult, but also makes the film thick and thin uneven. Occurs and the molding speed decreases.

If it exceeds 0.927 g / cm ³ , the film becomes thinner, the cooling effect becomes better, and in winter, the adhesion due to blocking becomes non-uniform, and the film peels off, entrains air, and generates wrinkles. When the sheet is laminated with another flexible sheet, wrinkles or voids are generated or peeling occurs, resulting in frequent loss.

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

A typical example of a resin having high physical strength, easy to adhere by blocking, and particularly preferable as the resin for the innermost layer is listed below as a trade name. Polyethylene having a carbon number of 6 as an α-olefin side chain by polymerization using a multisite catalyst can be mentioned. Mitsui Petrochemical Co., Ltd. introduced four 4-methylpentene-1
Of Idemitsu Petrochemical Co., Ltd., into which Ultzex of No. 1 was introduced and octene-1 having 8 carbon atoms as an α-olefin side chain.
There are STARECLEX of ORETEC and DSM, and DOWLEX of Dow Chemical Co. (all four products are L-LDPE resins obtained by a liquid phase process). Preferable typical examples obtained by a low-pressure gas phase process are listed below under trade names. TUFT of Nippon Unicar Co., Ltd. in which hexene-1 having 6 carbon atoms is introduced as an α-olefin side chain.
HEN and UCC's TUFLIN.

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

The outline of the features of the production process of L-LDPE resin using a multi-site catalyst and the trade names of the respective resin manufacturers are shown below.

[1] Gas-phase method It has been reported that the amount of energy required for polymerization is small.
In terms of quality, it is necessary to use a single component that is easy to exhibit as a comonomer, which is limited compared to the solution method. In recent years, it seems that the selection range of the comonomer and the control range of the molecular weight distribution are also increasing.

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

[3] Solution Method Polymerization in the solution method is performed in a solution. The reaction is performed at a high temperature to maintain a solution state. In terms of quality, it has a wide range of tolerance for lowering the density and is the most suitable for the polymerization of ethylene with C ₆ or more α-olefins (4-methylpentene-1, hexene-1, octene-1, decene-1, etc.) Process. Further, L-LDPE resin having a high α-olefin content (ultra-low density L-LDP having a density of 0.910 g / cm ³ or less)
It is also optimal as a manufacturing process for (E resin).

[4] Improved High-Pressure Method An L-LDPE resin is obtained at a high temperature and a high pressure using a Ziegler-based melting medium while using the conventional high-pressure method as it is. The running cost is higher than the above-mentioned gas-phase method, slurry method and solution method. It is. Also called high pressure conversion method.

[0067]

[Table 2]

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

Further, the density produced by polymerization using a single-site catalyst represented by a metallocene catalyst is 0.9%.
20 g / cm ³ or less, preferably 0.915 g / cm ³ or less, particularly preferably 0.910 g / cm ³ or less of L-LD
It is also preferable to use a PE resin.

(B) The EEM resin and the EEA resin will be described. The EEM resin and the EEA resin are ethylene acrylate resins having a content of methyl acrylate and / or ethyl acrylate of 7% by weight or more. Preferably, these resins are 50% by weight or more and the antioxidant is 0.01 to 2.
It is an ethylene acrylate copolymer resin containing 0% by weight. If the content of the ethylene acrylate copolymer resin is less than 50% by weight, flexibility is lacking, blocking does not easily occur, and the antistatic effect and the physical strength are reduced.

If the content of methyl acrylate and / or ethyl acrylate contained in the ethylene acrylate copolymer resin is less than 7% by weight, blocking hardly occurs, lacks flexibility, physical strength is low, and antistatic properties are reduced. Less effective.

EE currently marketed by Nippon Unicar Co., Ltd.
The representative brand name of resin A and its comonomer content, melt index, and density are shown (comonomer content NU
Only those with 6% or more in the C test method are described).

[0073]

[Table 3]

(C) The EVA resin will be described. The EVA resin preferably has a vinyl acetate content of 5% by weight or more. If the vinyl acetate content is less than 5% by weight, blocking hardly occurs, and it is close to a homopolyethylene resin, and the lamination of the blocking adhesive layer tends to be peeled off at the time of bag making or the like.

(D) The acid-modified polyolefin resin will be described. Acid-modified polyolefin resins are preferred because they are particularly excellent in recyclability, compatibility with other polyolefin resins, dispersibility of light-shielding substances, and the like.

The acid-modified polyolefin resin is a modified resin obtained by graft-modifying a polyolefin resin and an unsaturated carboxylic acid, and examples thereof include a graft-modified polyethylene resin, a graft-modified resin, an ethylene / ethyl acrylate copolymer resin, and a graft-modified ethylene / acetic acid. Vinyl copolymer resin,
Graft-modified polypropylene resin and polybutene
1, an α-olefin such as poly-4-methylpentene-1, an L-LDPE resin, and a resin obtained by graft-modifying an olefin-based thermoplastic elastomer with an unsaturated carboxylic acid or the like. Preferred is a graft-modified polyolefin resin obtained by grafting an unsaturated carboxylic acid such as acrylic acid, maleic acid, or maleic anhydride to a polyolefin resin.

The graft ratio of the unsaturated carboxylic acids is 0.1%.
It is preferably from 01 to 20%. Unsaturated carboxylic acids are generic names including their derivatives, and representative examples include acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, tetrahydrophthalic acid, mesaconic acid, angelic acid, citraconic acid, Crotonic acid, isocrotonic acid, nadic acid (endocis-bicyclo [2,2,
1] Hept-5-ene-2,3-dicarboxylic acid), maleic anhydride, citraconic anhydride, itaconic anhydride, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, methacrylic acid Butyl, glycidyl acrylate, glycidyl methacrylate, monoethyl maleate, diethyl maleate, monomethyl fumarate, dimethyl fumarate, diethyl itaconate, acrylamide, methacrylamide, monoamide maleate, diamide maleate , Maleic acid-N-monoethylamide, maleic acid-N, N-diethylamide, maleic acid-N-monobutylamide, maleic acid-N, N-
Dibutylamide, fumaric acid monoamide, fumaric acid diamide, fumaric acid-N-monoethylamide, fumaric acid-N,
N-diethylamide, fumaric acid-N-monobutylamide, fumaric acid-N, N-diethylamide, fumaric acid-N
-Monobutylamide, fumaric acid-N, N-dibutylamide, maleimide, monomethyl maleate, dimethyl maleate, potassium methacrylate, sodium acrylate, zinc acrylate, magnesium acrylate, calcium acrylate, sodium methacrylate, acrylic Potassium acrylate, potassium methacrylate, N-butylmaleimide, N-phenylmaleimide, maleenyl chloride, glycidyl maleate, dipropyl maleate, aconitic anhydride, sorbic acid, etc., and can be mixed with each other . Among these, acrylic acid, maleic acid,
Maleic anhydride and nadic acid are preferred, and maleic anhydride is particularly preferred.

The method for graft-modifying unsaturated carboxylic acids in the acid-modified polyolefin resin is not particularly limited. For example, the reaction in the molten state
No. 7421, a method disclosed in Japanese Patent Publication No. 44-15422, which reacts in a solution state, a method disclosed in Japanese Patent Publication No. 43-18144, a reaction in a slurry state, and a gas phase. Tokubo 50-
There is a method disclosed in, for example, Japanese Patent No. 77493. Among these methods, the melt kneading method using an extruder is preferable because the operation is simple and inexpensive.

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

A peroxide can be used to promote the reaction between the polyolefin resin and the unsaturated carboxylic acids.

Examples of the organic peroxide include benzoyl peroxide, lauroyl peroxide, azobisisobutyronitrile, dicumyl peroxide, α, α ′
Bis (t-butylperoxydipropyl) benzene,
2,5-dimethyl-2,5-di (t-butylperoxy) hexane, 2,5-dimethyl-2,5-di (t-butylperoxy) hexyne, di-t-butyl peroxide, cumenehydro Peroxide, t-butyl-hydroperoxide, dicumyl peroxide, t-butylperoxylaurate, t-butylperoxybenzoate, 1,3 bis (t-butylperoxyisopropyl) benzene, cumene hydroperoxide, Examples include di-t-butyl-diperoxyphthalate, t-butylperoxymaleic acid, and isopropyl percarbonate. Examples of the inorganic peroxide include azo compounds such as azobisisobutyronitrile, and ammonium persulfate.

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

The amount of these peroxides to be added is not particularly limited, but may be 0.1 to 100 parts by weight of the polyolefin resin.
It is preferably from 005 to 5 parts by weight, particularly preferably from 0.01 to 1 part by weight.

Representative examples of commercially available acid-modified polyolefin resins are shown below. (1) Nippon Petrochemical KK “N polymer” (2) Mitsui Petrochemical KK “ADMER” (3) Showa Denko KK “ER RESIN” (4) Mitsubishi Kasei Kogyo KK “Novatech-AP” (5) Mitsubishi Yuka KK “MODIC” (6) Nippon Unicar KK “NUC-ACE”

(E) The olefin-based thermoplastic elastomer will be described. The olefin-based thermoplastic elastomer is particularly preferable because it has excellent compatibility with other polyolefin resins, very good dispersibility of the light-shielding substance, and improved physical strength.

[0086] Typical commercial products of the olefin-based thermoplastic elastomer include, for example, the following. "TPR" manufactured by Uniroyal Inc. "TPR" manufactured by EI du Pont de Nemours
PN or Somel ", manufactured by BF Goodrich Chemical Company," T
elcar. Estane "Exxon Chemical Co., Ltd.," Vistfle
x "manufactured by Esso Chemical," Vistflo
n "manufactured by Hercules," Pro-fax "manufactured by Allied Chemical," ET "manufactured by Ren Plastics," Ren flex "manufactured by Monsanto," Santoprene "Namaze Ventostrap, and TP-Kel-National Rental-Kel-Net-Rel-National-Kel-In-National-Kel-National-Kel-National-Kel-National-Kel-National-Kelsen
Bber, "Unprene" Montedison, "Dutral TP" Sumitomo Chemical Co., Ltd., "Esprene EPR or Sumitomo TPE" Mitsui Petrochemical Co., Ltd., "Milastomer" Nippon Synthetic Rubber Co., Ltd., "JSR-Thermolan""

The above (A) L-LDPE resin, (B) EM
A resin and EEA resin, (c) EVA resin, (d) acid-modified polyolefin resin, (e) olefin thermoplastic elastomer, excellent compatibility with other polyolefin resins, blocking adhesion and light-shielding substance The most preferred ethylene copolymer resin is a low-crystalline ethylene copolymer resin because of its good uniform dispersibility and excellent physical strength, flexibility, gelbotest strength, suitability for heat sealing, and the like. That is, the crystallinity measured by the X-ray diffraction method is 60% or less, preferably 50% or less, more preferably 40% or less, particularly preferably 30% or less, and most preferably 10% or less.
The ethylene copolymer resin contains at least 20% by weight, preferably at least 30% by weight, and particularly preferably at least 40% by weight of the following α-olefin of at least one of ethylene, propylene and butene.

As the outermost layer of the multilayer co-extruded blown film, various thermoplastic resins can be used. However, the use of a polyolefin resin produced by polymerization using a single-site catalyst as described above is not suitable for the innermost layer. It is preferable because it has good solubility, good physical strength, good photographic properties, good heat sealability (low-temperature heat sealability, seal strength, foreign matter sealability, etc.), good recyclability, and the like.

The content of the polyolefin resin produced by polymerization using the single-site catalyst is preferably 3 to 99.95% by weight, more preferably 5 to 99% by weight, and more preferably 10 to 99% by weight.
-98% by weight is particularly preferred, and 20-97% by weight is most preferred. When the content of the polyolefin resin produced by polymerization using a single-site catalyst is less than 3% by weight, it is not possible to maintain heat seal strength for a long period of time, physical strength, photographic properties, and contaminant sealability. Also, 9
If the content exceeds 9.95% by weight, problems occur in photographic properties and film formability (resin deterioration and thermal decomposition occur due to generation of melt fracture and increase in melt viscosity), which makes practical use difficult. In the outermost layer, at least one of an antioxidant, a hydrotalcite compound, and a lubricant is used for improving photographic properties.
Preferably, two or more kinds are contained.

Intermediate layer of the multilayer co-extruded blown film (one layer or two or more layers)
It is preferable to include a recycled thermoplastic resin in at least one of the innermost layers in order to improve photographic properties and clear the container and packaging recycling method. Examples of the recycled resin include a resin obtained by pelletizing a loss generated in a multilayer co-extrusion blown film forming process of the present invention and a pellet formed by recovering after use as a packaging material for a photographic photosensitive material (in particular, the packaging material of the present invention is preferable). And resin pellets collected after use in applications other than packaging materials for photosensitive materials. Since the intermediate layer and the innermost layer do not come into direct contact with the photographic material (the outermost layer comes into contact with the photographic material), a resin having poor photographic properties can be used as the laminated film adhered and laminated by blocking according to the present invention.

By using the recycled resin produced from the multilayer co-extruded blown film of the present invention, photographic properties, dispersibility of light-shielding substances such as carbon black (in the case of packaging materials requiring light-shielding properties), film The moldability, the antistatic property, the light-shielding property and the photographic property can be improved. As a result, in the case of a light-shielding film, the light-shielding ability is improved and the thickness can be reduced by 10% or more. It is considered that such an effect of improving the photographic properties is a result of a drastic reduction in volatile components that adversely affect the photographic properties, since the recycled resin has passed through three or more thermal histories. By including a recycled resin, resources can be reused and the Containers and Packaging Recycling Law can be cleared.

The content of the recycled resin is preferably at least 20% by weight, more preferably at least 30% by weight, more preferably at least 40% by weight, particularly preferably at least 50% by weight from the viewpoint of film formability, various performances and cost. 60% by weight is most preferred. When the content of the recycled resin is less than 20% by weight, not only the effect of the property improvement by recycling is reduced, but also the kneading cost is increased.

A recycled thermoplastic resin can be used for one or more of the innermost layer and the intermediate layer of the multilayer co-extruded blown film.

The outermost layer of the multilayer coextruded blown film preferably contains an anti-blocking substance. By containing the anti-blocking substance, it is possible to prevent blocking, prevent generation of static marks, prevent generation of scratches, and prevent adhesion between the photosensitive material and the packaging material for the photosensitive material.

Examples of the antiblocking substance include silica (including natural and synthetic silica), calcium carbonate, magnesium carbonate, talc (magnesium silicate), and various zeolites (including natural and synthetic zeolites) described later. Aluminum acid, calcium silicate,
Fatty acid amide-based lubricant, higher fatty acid polyvinyl ester,
There are n-octadecyl urea, N, N'-dioleyl oxamide, N-ethanol stearamide, synthetic wax, dicarboxylic ester amide and the like, and among them, calcium carbonate, zeolite and silica are preferable. In particular, synthetic zeolites and synthetic silica are preferred, and synthetic zeolites which adsorb and detoxify photographic hazardous substances are most preferred.

The above silica has an average particle diameter of 0.3 to 20.
μm is preferred, and 0.5 to 15 μm is more preferred. When the average particle size is less than 0.3 μm, the cohesiveness is strong, and lumps occur frequently, and the blocking prevention effect is small. On the other hand, if the average particle diameter exceeds 20 μm, not only silica will be formed on the surface of the film and the film surface will be rough, but also the photographic material will be liable to suffer from pressure flaws and scratches.

The addition amount of the anti-blocking substance is 0.0
1 to 5.0% by weight is preferred, and 0.05 to 3.5% by weight.
Is more preferable, and 0.05 to 3.0% by weight is most preferable. When the addition amount is less than 0.01% by weight, the effect of preventing blocking is small, and only the kneading cost is increased. Also,
If the addition amount exceeds 5.0% by weight, not only the occurrence of bulky non-uniform failures (bubbles) increases, but also the physical strength and heat sealability of the film decrease.

The innermost layer of a multilayer co-extruded blown film may be used for the purpose of imparting light-shielding properties, printability and the like.
In the case of three or more outermost layers, a light-shielding substance can be contained in the intermediate layer and the like.

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

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

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

Representative examples of preferable commercial products of carbon black include, for example, carbon black # 2 manufactured by Mitsubishi Kasei.
0 (B), # 30 (B), # 33 (B), # 40
(B), # 41 (B), # 44 (B), # 45 (B), # 5
0, # 55, # 100, # 600, # 950, # 100
0, # 2200 (B), # 2400 (B), MA8, MA1
1, MA100 and the like.

Overseas products include, for example, Black Pearls 2,46,70,71,
74, 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, 15,102,3001,3004,3
006,3007,3008,3009,3011,301
2, XC-3016, XC-3017, 3020, etc., but are not limited thereto.

In the present invention, furnace carbon black is preferable for the purpose of improving light-shielding properties, cost and physical properties. Examples of expensive light-shielding substances having an antistatic effect include various conductive carbon blacks, acetylene black, and modified by-product carbon blacks. Is preferred. In particular, the sulfur content (ASTM D-1619) for photographic materials having high sensitivity (ISO sensitivity of 400 or more).
0.1% or less, particularly free sulfur (JIS K6350), which most adversely affects the photographic properties of photographic light-sensitive materials.
Acetylene black and furnace carbon black having a content of less than 50 ppm. If necessary, it is also preferable to mix the former and the latter according to required characteristics.

The light-shielding substance having an antistatic effect has an average particle diameter of 12 to 50 μm and a DBP oil absorption of 100 ml / ml.
100 g or more of various carbon blacks, specifically, various conductive carbon blacks (specifically, conductive furnace black such as Continex CF and Parcan C, superconductive furnace black such as Continex SCF and Vulcan SC, etc. Mitsubishi conductive carbon black # 3050, # 3150, # 3250, manufactured by Mitsubishi Kasei KK, such as Asahi HS-500 black, Vulcan XC-72, and Colux L conductive channel black.
# 3600, # 3750, # 3950 etc.), acetylene carbon black (e.g. electrified acetylene black, Shaunigan acetylene black), Ketjen carbon black (EC and EC-600JD etc.), carbon fiber, metal fiber, Al-doped, TiO ₂ , SnO ₂ , metal coated fiber, conductive material containing fiber, metal powder, graphite, various metal salts, metal adsorption fiber, polyaniline, polypyrrole, polyacetylene, polydiacetylene, polyparaphenylene,
Graphite powder and the like.

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

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

When used as a packaging material for a photographic light-sensitive material of the present invention, fog is not generated in the photographic light-sensitive material, the occurrence of increase / decrease in photosensitivity is small, the light-shielding ability is large,
Even when added to the innermost layer, carbon black is hard to generate and pinholes are less likely to occur in films such as fish eyes.
(Measured by JIS K 6221) 6.0 to 9.0, average particle diameter (measured by electron microscopy) of 10 to 120 mμ, particularly preferably 10 to 80 mμ, and most preferably 1 to 80 mμ.
0 to 60 mμ. Among them, volatile components (J
ISP 6221) 2.0% or less, DBP oil absorption (measured by JIS K 6221 oil absorption A method) 50 ml
Furnace carbon black and acetylene black of / 100 g or more are preferable in that they are inexpensive, do not adversely affect photographic properties, are improved in light shielding properties, are improved in dispersibility, and are hardly deteriorated in physical properties.

Further, ASTM D 1619 in the packaging material
The sulfur content by the measurement method of −60 is 0.9% or less, preferably 0.7% or less, particularly preferably 0.5% or less, and most preferably 0.1% or less unless the fog increase, sensitivity abnormality, and generation occur. Irregularities adversely affect the photographic properties of the photographic material. In particular, a free sulfur component which greatly adversely affects the photographic properties of the direct photographic light-sensitive material (each sample is cooled and solidified with liquid nitrogen and then pulverized. The total volume is made up to 100 ml, 10 ml of this solution is injected into a high performance liquid chromatograph, and sulfur is quantified.The conditions for high performance liquid chromatograph are column: ODS silica column (4.6φ).
× 150 mm), separation solution; methanol 95 and water 5 (containing 0.1% of acetic acid and triethylamine each), flow rate: 1
ml / min, detection wavelength; 254 nm, quantification is performed by the absolute calibration curve method. ) Is 0.1% or less, preferably 0.05%
%, Particularly preferably 0.01% or less, most preferably 0.005.

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

The next preferred light-shielding substance after carbon black has a refractive index of 1.5 as measured by Larsen's oil immersion method.
Zero or more inorganic pigments and various metal powders, metal flakes, metal pastes, metal fibers and carbon fibers. Representative examples of the inorganic pigment and the metal powder having a preferable refractive index of 1.50 or more are shown below, but the present invention is not limited to these. The numbers in parentheses indicate the refractive index.

Examples of inorganic pigments having a refractive index of 1.50 or more include rutile-type titanium oxide (2.75) and silicon carbide (2.6).
7), anatase type titanium oxide (2.52), zinc oxide (2.
37), antimony oxide (2.35), lead white (2.0
9), zinc white (2.02), lithopone (1.84), zircon (1.80), corundum (1.77), spinel (1.73), apatite (1.64), barite powder (1 .64), barium sulfate (1.64), magnesite (1.62), dolomite (1.59), calcium carbonate (1.58), talc (1.58), calcium sulfate (1.56), Silicic anhydride (1.55), quartz powder (1.54), magnesium hydroxide (1.54), hydrochloric magnesium carbonate (1.52), alumina (1.50)
Etc. Particularly preferred are light-shielding substances having a refractive index of 1.56 or more, most preferably 1.60 or more.

Calcium silicate having a refractive index of less than 1.50
(1.46), diatomaceous earth (1.45), hydrous silicic acid (1.4
Since 4) and the like have a small light-shielding ability and thus need to be added in a large amount and are effective as a blocking inhibitor, use as a light-shielding substance is not preferred. In addition, due to the recent overseas travel boom, baggage inspection at airports has been changed to an inspection machine using X-rays.
When passing through a high-sensitivity photographic film having an O-sensitivity of 400 or more, fog is easily generated by X-rays. In order to prevent this, it is preferable to use a light-shielding substance having a specific gravity of 3.1 or more, preferably 3.4 or more. Specific gravity of 3.1 or more,
The form of the light-shielding substance having an X-ray shielding property in addition to the light-shielding property of preferably 3.4 or more, particularly preferably 4.0 or more is not limited to those exemplified below, and any form,
For example, pigments, powders, flakes, whiskers, fibers and the like may be used.

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

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

Table 4 shows the refractive index and specific gravity of the light-shielding substance.

[Table 4]

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

The above-mentioned various light-shielding substances do not adversely affect the photographic light-sensitive material and do not deteriorate the film formability, so that the loss on drying at 100 ° C. for 5 hours is preferably 2.0% by weight or less. More preferably 1.0% by weight or less,
Most preferably, it is used in a state of 0.5% by weight or less.

It has the effect of adsorbing lubricants, antioxidants and organic nucleating agents which are easy to bleed out, adsorbing deodorants, fragrances, oxygen scavengers, etc., and improves the photographic properties of photographic light-sensitive materials. Representative examples of the oil-absorbing inorganic pigment which is preferably contained in the present invention include zinc white (52), asbestin (50), clay (51), titanium oxide (56), kaolin (60), and talc. (60), carbon black (60 or more), activated carbon and the like. The number in parentheses is the oil absorption (measured by the oil absorption A method of JIS K 6221. Unit: ml)
/ 100g).

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

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

Here, the aluminum paste refers to the presence of mineral spirit and a small amount of higher fatty acids such as stearic acid or oleic acid when aluminum powder is prepared by a known method such as a ball mill method, a stamp mill method, or an atomizing method. Originally made in paste form. In the present invention, this aluminum paste and various aromatic monovinyl resins (polystyrene resin, rubber-containing polystyrene resin, etc.), and polyolefin thermoplastic resins (various polypropylene resins, various polyethylene resins, acid-modified resins, EVE resins, EEA resins, EAA resins, etc.) Heat-knead various thermoplastic resin elastomers, various compatibilizers, various low molecular weight polyolefin resins, paraffin wax, tackifiers, dispersants such as metal soaps, etc., and mix them with low volatile substances (mainly mineral spirits with strong odor, white The content of volatile substances (100 ℃, spirit) removed by vacuum pump etc.
It is preferable to use an aluminum paste compound resin or aluminum paste masterbatch resin having a loss on drying (5 hours) of 3% or less, preferably 1% or less, particularly preferably 0.5% or less.

It is particularly preferable to use the resin as an aluminum paste masterbatch resin in order to eliminate adverse effects on the photographic properties of the photographic light-sensitive material (development, abnormal sensitivity, abnormal color formation, etc.) and odor. For example, even if the mineral spirit content in a master batch resin having an aluminum paste content of 40% by weight is 1.0% by weight, the concentration of the aluminum paste in the packaging material for photographic light-sensitive materials is set to 2% by weight. Then, 1 part by weight of the aluminum paste masterbatch is diluted and kneaded with 19 parts by weight of the natural resin, and some of the packaging material contains mineral spirits which are removed as a gas by heating during molding. The amount will be less than 0.05% by weight. As a result, the photographic properties of the photographic material are not adversely affected, and the odor is reduced.

[0125] The aluminum powder is obtained by pulverizing molten aluminum into powder by an atomizing method, a granulating method, a rotating disk dropping method, an evaporation method or the like, and crushing aluminum foil by a ball mill method, a stamp mill method or the like. Including Since aluminum powder alone is unstable, various known surface coating treatments for inactivating the aluminum powder surface are performed. In particular, a specific thickness (5-20 μm,
Preferably 6 to 15 μm, particularly preferably 7 to 10 μm
m), the aluminum foil rolled in step m) is cut with a shredder or the like, annealed and fatty acids are removed, and then 5% by weight or less of fatty acids having 8 or more carbon atoms (including compounds) in the cut aluminum foil. And an average particle size of 0.3 to 5 using at least one of a pulverizer selected from a ball mill, a stamp mill, a vibration mill and an attritor.
Aluminum powder having a thickness of 0 μm, an average thickness of 0.03 to 0.5 μm, and a fatty acid content of 5% by weight or less is particularly preferred in the present invention because of its excellent dispersibility, photographic properties, and low gloss.

For practical use as the packaging material for photographic light-sensitive materials of the present invention, the total amount of the light-shielding materials is required for the purpose of ensuring quality, securing physical strength, ensuring good photographic performance, and improving moldability and economy. Although the content is 0.1 to 80% by weight, the content varies depending on the thickness of the packaging material, the layer structure, the light-shielding ability of the light-shielding substance, the average particle diameter, and the like. In the case of carbon black, titanium oxide and aluminum powder having excellent light-shielding ability, the total content in the light-shielding layer is from 0.1 to 80% by weight, from 0.3 to 80% from the viewpoint of light-shielding properties, economy, film formability and the like. 60% by weight is preferable, and 0.5 to 40% by weight is more preferable.
Particularly preferred is 1 to 20% by weight, most preferably 1.5 to 10% by weight. If the content is less than 0.1% by weight, unless the thickness of the packaging material for photographic light-sensitive material is increased, the light-shielding ability becomes insufficient and light fog is generated. For this reason, the molding speed of the packaging material for photographic light-sensitive materials becomes slow (because the cooling time becomes long), and the amount of resin used becomes large, so that it becomes expensive and is difficult to be put into practical use. If the content exceeds 80% by weight, it becomes expensive,
The dispersibility deteriorates, the generation of microgrids (aggregated impurities) increases, pressure fog and scratches occur on the photosensitive material, and the amount of moisture in the packaging material for the photosensitive material increases due to the increase in moisture adsorbed on the carbon black. Adversely affect the photographic performance of photographic photosensitive materials (fog generation, abnormal sensitivity,
Coloring abnormalities). Furthermore, the moldability of the packaging material for photographic light-sensitive materials is deteriorated (foaming, generation of silver stripes, pinholes, etc.) and the physical strength is reduced, which makes practical use difficult.

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

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

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

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

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

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

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

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

The total sulfur content in the above total light-shielding substance (AST
MD-1619) is at most 0.9%, preferably at most 0.7%, particularly preferably at most 0.5%, and the free sulfur content (JISK 6350) is at most 150 ppm, preferably at most 50 ppm, particularly preferably ASTM D-1 is at most 30 ppm, most preferably at most 10 ppm.
The ash content by 506 is less than 0.5%, preferably 0.4%
Or less, particularly preferably 0.3% or less, and the aldehyde compound content is 0.2% or less, preferably 0.1% or less, particularly preferably 0.05% or less, most preferably 0.01% or less. Care must be taken if not suppressed, as it will adversely affect photographic properties.

Further, a cyanide compound adversely affects the photographic performance of a photographic light-sensitive material.
The value obtained by converting the amount of hydrogen cyanide quantified by pyrazolone absorption spectrometry into ppm unit based on the weight of the light-shielding substance is 20.
It is a light-shielding substance of not more than 10 ppm, preferably not more than 10 ppm, particularly preferably not more than 5 ppm, most preferably not more than 1 ppm.

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

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

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

In particular, free sulfur which has been found to have a direct adverse effect on the photographic properties of photographic light-sensitive materials (Free sulfur)
ur) A carbon black having a content (quantification according to JIS K 6350) of 100 ppm or less, preferably 50 ppm or less, particularly preferably 20 ppm or less, most preferably 10 ppm or less is used. In view of the low free sulfur content, carbon black produced using ethylene bottom oil from naphtha as the raw material is most preferred in the present invention.

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

Further, AST in packaging materials for photographic light-sensitive materials
The value obtained by converting the amount of sulfur component into a weight by a measuring method in accordance with MD 1619-60 is 0.9% by weight or less, preferably 0.6% by weight or less, more preferably 0.4% by weight or less, particularly preferably It is at most 0.2% by weight, most preferably at most 0.1% by weight.

In particular, the amount of free sulfur component which greatly affects the photographic properties of the photographic light-sensitive material. Each sample was cooled and solidified with liquid nitrogen and then pulverized. 100 g of the pulverized sample was placed in a Soxhlet extractor at 700 ° C. and 60 ° C. After extraction and cooling for 8 hours, the total volume is made up to 100 ml. 100 ml of this solution is injected into a high performance liquid chromatograph, and sulfur is quantified. High-performance liquid chromatography separation conditions are as follows:
Using an S silica column (size 4.5φ × 150mm),
Methanol 95 and water 5 (containing 0.1% each of acetic acid and triethylamine) as separation liquid, flow rate: 1 ml / min,
Detection wavelength: 254 mm, quantification is performed by the absolute calibration curve method. Δ is 0.1% by weight or less, preferably 0.05% by weight or less, more preferably 0.05% by weight or less, particularly preferably 0.03% by weight, Most preferably, it is 0.01% by weight or less.

Furthermore, the amount of free formaldehyde which has a significant adverse effect on the photographic properties of the photographic light-sensitive material in the photographic light-sensitive material packaging material (described in "Polymer Analysis Handbook, KK Asakura Shoten, March 1, 1986, p. 375") The value obtained by converting the value of the free formaldehyde determination method into a weight is 0.2% by weight or less, preferably 0.1% by weight or less,
The content is more preferably 0.07% by weight or less, particularly preferably 0.04% by weight or less, and most preferably 0.01% by weight or less. .).

Even if free formaldehyde which adversely affects the photographic properties of this photographic light-sensitive material is contained in the photographic light-sensitive material packaging material in a problem amount, a urea compound, thiourea, hydrazine compound, dicyandiamide, hydroxyamine, hydroxylamine hydrochloride, Hydantoin compound, hydroxylamine sulfate, formamide 0.001 to 5% by weight,
Preferably it is 0.005 to 4% by weight, more preferably 0.1 to 4% by weight.
01 to 3% by weight, particularly preferably 0.02 to 2% by weight,
Most preferably, if the content is 0.03 to 1% by weight, it can be improved to a practically usable level. In particular, a hydantoin compound, a hydrazine compound and a hydroxylamine compound have excellent improvement effects.

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

An antioxidant can be contained in the innermost layer, outermost layer, intermediate layer and the like of the multilayer co-extruded blown film. By containing an antioxidant, it prevents thermal degradation and thermal decomposition of additives such as thermoplastic resins and fatty acids, lubricants, organic nucleating agents and surfactants, and significantly changes the fluidity of the thermoplastic resin composition. And the occurrence of bumps can be prevented. Further, it is possible to prevent the generation of thermal decomposition substances (aldehydes and the like) which adversely affect the photographic light-sensitive material. Various known compounds (eg, hydantoin compounds, hydrazine compounds, urea compounds) that reduce, stabilize, stabilize the reaction, or stabilize the adsorption of pyrolytic substances (aldehydes, etc.) to an amount that does not adversely affect the photographic material. Is preferably added. The amount of formaldehyde in the packaging material for photographic light-sensitive materials measured by the acetylacetone method is 50.
Satisfactory photographic properties can be maintained by adjusting the content to 0 PPM or less, preferably 300 PPM or less, particularly preferably 150 PPM or less, and most preferably 75 PPM or less.

The amount of the antioxidant added is 0.001-1.
5% by weight, preferably 0.005 to 0.7% by weight,
0.01 to 0.45% by weight is more preferred. If the addition amount is less than 0.001% by weight, there is no addition effect and only the kneading cost increases, and if the addition amount exceeds 1% by weight,
It adversely affects the photographic properties of the photographic light-sensitive material utilizing the oxidation and reduction actions and bleeds out to the surface of the molded article to deteriorate the appearance.

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

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

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

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

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

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

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

Representative examples of the most preferred hindered phenolic antioxidants for the present invention are shown below. 1,3,5-trimethyl 2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, tetrakis [methylene-3- (3 ′ · 5′-di-tert-butyl) -4 '
-Hydroxyphenyl) propionate] methane, octadecyl-3,5-di-tert-butyl-4-hydroxy-hydrocinnamate, 2,2 ′, 2′-tris [(3,
5-di-tert-butyl-4-hydroxyphenyl)
Propionyloxy] ethyl isocyanurate, 1,3,
5-tris (4-tert-butyl-3-hydroxy-
2,6-di-methylbenzyl] isocyanurate, tetrakis (2,4-di-tert-butylphenyl) 4,
4'-biphenylenediphosphite, 4,4'-thiobis- (6-tert-butyl-O-cresol),
2,2′-thiobis- (6-tert-butyl-4-methylphenol), tris- (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, 2,2′-
Methylene-bis- (4-methyl-6-tert-butylphenol), 4,4'-methylene-bis- (2,6-di-tert-butylphenol), 4,4'-butylidenebis- (3-methyl-6 -Tert-butylphenol), 2,6-di-tert-butyl-4-methylphenol, 4-hydroxymethyl-2,6-di-ter
t-butylphenol, 2,6-di-tert-4-n
-Butylphenol, 2,6-bis (2'-hydroxy-3'-tert-butyl-5'-methylpentyl)-
4-methylphenol, 4,4'-methylene-bis-
(6-tert-butyl-O-cresol), 4,4'-
Butylidene-bis (6-tert-butyl-m-cresol), 3,9-bis {1.1-dimethyl-2- [β-
(3-t-butyl-4-hydroxy-5-methylphenyl) propionyloxy] ethyl {2,4.8,10-
And tetraoxaspiro [5,5] undecane. Among them, the melting point is 100 ° C. or more, especially 120 ° C.
C. or higher is preferred. Further, it is effective to use it in combination with a phosphorus antioxidant. Furthermore, it is particularly preferable to use at least one of phosphorus-based antioxidants, at least one of hindered phenol-based antioxidants, and at least one of hydrotalcite compounds in total of three or more.

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

The above-mentioned vitamin E (tocopherol) and tocopherol dimer have an excellent antioxidant effect and, when used in combination with a light-shielding substance such as carbon black by coloring a film molded article to yellow, the light-shielding ability is reduced by carbon black. 10% more than the case of adding a light-shielding substance alone,
In addition, since the dispersibility is also improved, the amount of the light-shielding substance to be added is reduced to 1
Even if it is reduced by 0% or more, the same light shielding property can be obtained. As a result, various effects such as prevention of deterioration of photographic properties, improvement of physical strength, improvement of appearance, and reduction of material cost are exhibited.

[0159] Particularly preferred antioxidants are phenolic antioxidants, and commercially available products include various types of Irganox manufactured by Ciba-Geigy and Sumilize manufactured by Sumitomo Chemical Co., Ltd.
rBHT, Sumilizer BH-76, Sumi
lizer WX-R, Sumilizer BP-1
01 and so on. Also, 2,6-di-t-butyl-p-cresol (BHT), a low-volatility, high-molecular-weight phenolic antioxidant (trade name: Ireganox 1010, Ir)
eganox 1076, Topanol CA, Iono
x 330 etc.). These phenolic antioxidants include phosphorus antioxidants (distearyl-pentaerythritol-diphosphite, tris (nonylphenyl)).
Phosphite, bis (2,4-di-t-butylphenyl) pentaerythritol phosphite, dilaurylthiodipropionate, distearylthiopropionate, tetrakis (2,4-di-t-butylphenyl)
4,4′-biphenylene-di-phosphonite, tris (2,
4-di-t-butyl-phenyl) phosphite, dialkyl phosphate, etc.), and in particular, the use of two or more thereof in combination is effective because it exhibits a surplus effect.

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

The photographic material of the present invention is particularly advantageous in that it has many excellent properties such as little adverse effect on the photographic properties of the photographic light-sensitive material, little thermal decomposition even at a resin melting temperature (130 to 400 ° C.), and little bleed-out over time. Preferred antioxidants are hindered phenolic antioxidants having a molecular weight of 200 or more, preferably 300 or more, particularly preferably 400 or more, and most preferably 500 or more.

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

A lubricant may be contained in the innermost layer, the outermost layer and the like of the multilayer co-extruded blown film. By containing a lubricant, the suitability for handling and lubricity of the film can be improved, and wrinkles and streaks can be prevented. Further, even when the photosensitive material is stacked on the photosensitive material, no blocking occurs, and even when the material is rubbed with the photosensitive material as a packaging bag, scratches and static marks can be prevented. Further, the flowability of the resin can be improved, and the moldability can be improved.

The amount of the lubricant to be added varies depending on the kind. For a lubricant having a small lubricating effect mainly for maintaining the photographic performance of the photographic light-sensitive material, such as a fatty acid metal salt (same as the metal soap described below), the amount is 0.1%. 0.01 to 5% by weight, preferably 0.03 to 3% by weight.
%, More preferably 0.05 to 1.5% by weight, most preferably 0.07 to 1% by weight. If the addition amount is less than 0.01% by weight, there is no effect of addition and only the kneading cost increases. If the addition amount exceeds 5% by weight, foaming, white smoke and die lip streaks are likely to occur, and slipping between the molten resin and the screw of the extruder is likely to occur, and the discharge amount of the resin becomes unstable. Also,
With the passage of time after molding, stickiness and bleed-out tend to occur, which adversely affects the photographic light-sensitive material.
Furthermore, the heat-sealing strength with time decreases, and the sealing property, moisture-proof property and oxygen barrier property deteriorate, and it is difficult to put it into practical use as a packaging material for photosensitive materials.

Further, although the lubricating effect is large like a fatty acid amide type lubricant and a bis fatty acid amide type lubricant, in the case of a lubricant which easily bleeds out and adversely affects a photographic light-sensitive material, 0.01 to 1% by weight. Is preferably 0.03-0.5.
% By weight is more preferable, and 0.05 to 0.3% by weight is most preferable. If the addition amount is less than 0.01% by weight, there is no effect of addition and only the kneading cost increases. Addition amount is 1
If the amount exceeds the weight percentage, slip between the molten resin and the screw of the extruder is likely to occur, and the discharge amount of the resin becomes unstable. In addition, stickiness and bleed-out tend to occur with the lapse of time after film formation. Furthermore, the bleed-out lubricant is transferred to the photographic photosensitive layer to cause development inhibition, thereby causing quality defects such as development unevenness and color unevenness.

The names of typical commercially available lubricants and the names of manufacturers are described below. (1) Fatty acid amide-based lubricant; [Saturated fatty acid amide-based lubricant] Behenic acid amide-based lubricant; Diamid KN (Nippon Kasei), etc. Stearic amide-based lubricant; Armide HT (Lion Fat), Alflow S-10 (Nippon Fat) , Fatty Acid Amide S (Kao), Diamid 200 (Nippon Kasei), Diamid AP-1 (Nippon Kasei), Amide S. Amide T
(Nitto Chemical), Neutron-2 (Nippon Seika), etc. [hydroxystearic amide lubricant] Palmitic amide lubricant; Neutron S-18 (Nippon Seika), Amide P (Nitto Chemical), etc. Lauric amide Alumide C (Lion Akzo), Diamid (Nippon Kasei), etc. [Unsaturated fatty acid amide lubricant] Erucamide amide lubricant; Alflow P-10 (Nippon Oil & Fats), Neutron-S (Nippon Seika) , LUBOL
(I ・ C ・ I), Diamid L-200 (Nippon Kasei)
Oleic acid amide lubricants; Armoslip CP (Lion Akzo), Neutron (Nippon Seika), Neutron E-18 (Nippon Seika), Amide O (Nitto Chemical), Diamid O-200, Diamid G-200 (Nippon Kasei), Alflo E-10 (Nippon Oil & Fats), fatty acid amide O (Kao), etc. [Bis fatty acid amide lubricant] Methylene bisbehenic acid amide lubricant;
Kbis (Nippon Kasei) and other methylene bisstearic amide lubricants; Diamid 200 bis (Nippon Kasei), Armowax (Lion Akzo), Bisamide (Nitto Kagaku), etc. Methylene bisoleic amide lubricants; Lubron O (Japan) Chemical formation), etc. Ethylene bisstearic acid amide lubricant; Armoslip EBS (Lion Akzo), etc. Hexamethylene bisstearic acid amide lubricant; Amid 65 (Kawaken Fine Chemical), etc. Hexamethylene bis oleamide amide lubricant; Ken Fine Chemicals)

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

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

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

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

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

(7) Fatty acid metal salt-based lubricant (metal soap); lauric acid, stearic acid, succinic acid, stearyl lactic acid, lactic acid, phthalic acid, benzoic acid, hydroxystearic acid, ricinoleic acid, naphthenic acid, oleic acid, palmitic acid Acids, higher fatty acids such as erucic acid and Li, Na, M
g, Ca, Sr, Ba, Zn, Cd, Al, Sn, P
Compounds with metals such as b, Cd and the like are mentioned, and preferred are magnesium stearate, calcium stearate, sodium stearate, zinc stearate, calcium oleate, zinc oleate, magnesium oleate and the like.

(8) Partially saponified montanic acid ester;

(9) Silicone-based lubricants: Various grades of dimethylpolysiloxane and modified products thereof (Shin-Etsu Silicone, Toray Silicone), especially various silicone oils, not only exert the effects of improving resin fluidity, lubricity, etc. When used in combination with a light-shielding substance, the dispersibility of the light-shielding substance is improved,
As a result of making the resin cloudy and increasing the haze (ASTM D-1003), unexpected effects such as improvement in coloring power and improvement in light-shielding properties are exhibited, which is preferable.

The silicone oil preferably has a viscosity at room temperature of 50 to 100,000 centistokes, more preferably 5,000 to 30,000 centistokes.
A high viscosity of 0 centistokes is preferred. Specific examples of silicone and silicone-modified products include polymethylphenylsiloxane, olefin-modified silicone, amide-modified silicone, polydimethylsiloxane, amino-modified silicone, carboxyl-modified silicone, α-methylstyrene-modified silicone, polyethylene glycol and polypropylene glycol. It is a silicone oil containing a modified siloxane bond such as polyether-modified silicone, olefin / polyether-modified silicone, epoxy-modified silicone, amino-modified silicone, and alcohol-modified silicone. In the silicone oil,
Olefin-modified silicones, amide-modified silicones, polydimethylsiloxanes, polyether-modified silicones, and olefins, which do not adversely affect the photographic light-sensitive material and have a large lubricating effect, and are particularly preferable when applied to packaging materials for photographic light-sensitive materials / Polyether-modified silicone. The silicone oil improves the coefficient of friction of a molding material in a heated state, for example, a resin film, reduces sliding resistance generated during hot plate sealing by an automatic packaging machine,
By preventing wrinkles from occurring, it is possible to form a basis for obtaining a resin film having a beautiful appearance, a high level of sealing performance, and a performance that has tight adhesion to a package. In addition, it is possible to prevent a decrease in gloss due to sliding and obtain a beautiful seal portion. In the present invention in which silicone oil is used in combination, the coefficient of high-temperature friction can be set to 1.4 or less when performing sliding heat sealing.

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

An antistatic agent can be added to the innermost layer, outermost layer, intermediate layer and the like of the multilayer co-extruded blown film. By adding an antistatic agent, static failure, molding failure, and aluminum powder (including aluminum powder and aluminum paste) are scaly, so there is little generation of microgrit, so light shielding ability and physical strength are excellent. However, when used in combination with spherical or powdery carbon black, white carbon, titanium yellow, titanium oxide, lithopone, ultra-fine calcium carbonate, which tends to generate microgrit, the dispersibility of all pigments becomes good, light shielding ability, It is particularly preferable because of its excellent physical strength.
In this case, it is preferable that the amount of the flaky pigment is larger than that of the spherical or powdery pigment. In addition, poor dispersion of the light-shielding substance can be prevented.

The addition amount of the antistatic agent is preferably 0.01 to 5.0% by weight, more preferably 0.05 to 3.5% by weight, and most preferably 0.1 to 2.0% by weight. The amount added is 0.
If it is less than 01% by weight, the effect of addition is not sufficient, and only the kneading cost increases. On the other hand, if the addition amount exceeds 5.0% by weight, slipping of the molten resin with the screw of the extruder tends to occur, and the discharge amount of the resin becomes unstable. Further, stickiness and bleeding tend to occur with the passage of time after molding.

Representative examples of the antistatic agent are shown below. I. Nonionic (= non-ionic) (1) Alkylamine derivative: T-B103 (Matsumoto Yushi), T-B104 (Matsumoto Yushi) Alkylmid type polyoxyethylene alkylamine: Armostat 3
10 (lion oil) Tertiary amine (laurylamine): Armostat 400
(Lion fat) N, N-bis (2-hydroxyethylcocoamine): Armostat 410 (Lion fat) Tertiary amine: ANTISTATIC 273C, 273;
273E (Fine Org. Chem) N-hydroxyhexadecyl-di-ethanol-amine: Berg.
P. 654,049 N-hydroxyoctadecyl-di-ethanol-amine: (Natio
nal Dist.) (2) Fatty acid amide derivative: TB-115 (Matsumoto Yushi), Elegan P100 (Nippon Yushi), Erik SM-
2 (Yoshimura Oil Chemical) hydroxystearic acid amide oxalate -N, N'-distearyl amide-butyl ester: Hoechst polyoxyethylene alkyl bromide (3) ether type polyoxyethylene alkyl ethers _{RO (CH 2 CH 2 O)} n H Polyoxyethylene alkyl phenyl ether Special non-ion type: Resistat 104, PE100, 1
16-118 (Daiichi Kogyo Pharmaceutical), Register PE13
2,139 (Daiichi Kogyo Seiyaku Co., Ltd.), Elegan E115, Chemistat 1005 (Nippon Oil & Fats), Erik BM-1 (Yoshimura Oil Chemical), Electrostripper TS, TS2
3,5, EA, EA2,3 (Kao Soap) (4) Polyhydric alcohol ester type glycerin fatty acid ester: mono-, di-, or triglyceride such as stearic acid or hydroxystearic acid, monoglycol (Japanese camphor), TB-123 ( Matsumoto Yushi), Resistat 113 (Daiichi Kogyo Pharmaceutical Co., Ltd.) Sorbitan fatty acid ester Special ester: Elique BS-1 (Yoshimura Oil Chemical) 1-hydroxyethyl-2-dodecylglyoxazoline: (British cellophane)

II. Anionic (1) Sulfonic acids Alkyl sulfonate RSO ₃ Na Alkylbenzene sulfonate Alkyl sulfate ROSO ₃ Na (2) Phosphate ester type alkyl phosphate

III. Cationic (1) Amide-type cation: resist PE300,4
01, 402, 406, 411 (Daiichi Kogyo Seiyaku) (2) Quaternary ammonium salt quaternary ammonium chloride quaternary ammonium sulfate quaternary ammonium nitrate Katimine CSM-9 (Yoshimura Oil Chemical), CATANAC6
09 (American cyanamide), Denone 314C (Marubishi Yuka), Armostat 300 (Lion Fat), 1
00V (Armor), Electrostripper-ES (Kao Soap), Chemistat 2009A (Nippon Yushi) Stearamido propyl-dimethyl-β-hydroxyethyl ammoniu
m nitrate: CATANAC ・ SN (Alican / Dianamide)

IV. Zwitterionic system (1) Alkyl petaine type: (2) Imidazoline type: Rheostat 53,532 (lion fat), AMS 53 (lion fat), AMS 303,313 (lion fat) Alkyl imidazoline type (3) Metal salt type : AMS 576 (Lion fat) Rheostat 826,923 (Lion fat) (RNR'CH ₂ CH ₂ CH ₂ NCH ₂ COO) ₂ Mg ≧ R ≧
C, R ′ = H or (CH ₂ ) mCOO-｝ (lion fat) R = C3-8 hydrocarbon, A = oxygen or imino group, M =
Organic amine or metal (4) alkylalanine type:

V. Conductive resin Polyvinyl benzyl type cation Polyacrylic acid type cation

VI. Others: Register 204, 205
(Daiichi Kogyo Seiyaku Co., Ltd.), Elegan 2E, 100E (Nippon Yushi), Chemistat 1002, 1003, 2010 (Nippon Yushi), Erik 51 (Yoshimura Oil Chemical), ALROMI
NE RV-100 (Geigy)

Among the above antistatic agents, nonionic (nonionic) type antistatic agents are particularly preferable because they have a small adverse effect on photographic properties and human body and a large effect of preventing static marks.

In addition, "Handbook: Rubber / Plastic Compounding Chemicals Revised Second Edition" (published by KK Rubber Digest)
Pp. 381-388 and "Augmented Antistatic Agents-Surface Modification of Polymers" (published on March 25, 1972, KK Koshobo), pp. 64-104 and 236-.
From the antistatic agent described on page 266 and the antistatic agent described on pages 117 to 153 of "Sekkabun Kogyo Kogyo Kogyo Plastic Additives Data Book" (published on October 1, 1968 by KK Kagaku Kogyo Co., Ltd.) to photographic photosensitive materials It is preferable to select and use a kind and an addition amount which do not adversely affect a photosensitive material packaging material composed of only a thermoplastic resin which easily generates a static mark in a photographic photosensitive material by charging.

The outermost layer, innermost layer, intermediate layer and the like of the multilayer co-extruded blown film may contain one or more hydrotalcite compounds and zeolite. By containing at least one of hydrotalcite compounds and zeolites, catalyst residues can be neutralized, substances that adversely affect photographic properties by absorbing halogen compounds such as hydrochloric acid can be detoxified, Can be prevented from rusting, and resin burning failure can be prevented.

The content of one or more hydrotalcite compounds and zeolite is preferably 0.1 to 30% by weight, more preferably 0.2 to 20% by weight, and 0.3 to 1% by weight.
0% by weight is particularly preferred, and 0.4-5% by weight is most preferred. If the content is less than 0.1% by weight, the effect of addition is not exhibited and only the cost of kneading increases, and if the content exceeds 30% by weight, there is no effect of the addition and the generation of dust. It only increases the cost.

The hydrotalcite compound has a general formula of M _x R _y (OH) _{2x + 3y-2z} (A) _z · aH ₂ O where M is Mg, Ca or Zn, and R is Al, Cr or F
e and A are CO3 or HPO4, x, y, z and a are positive numbers.
Is a double salt represented by

[0190] When a representative example of embodiment, Mg ₆ A1 ₂ (O
_{H) 16 CO 3 · 4H 2} O, Mg 8 Al 2 (OH) 20 CO 3 · 5
_{H 2 O, Mg 5 Al 2} (OH) 14 CO 3 · 4H 2 O, Mg 10
Al ₂ (OH) ₂₂ (CO ₃ ) ₂ .4H ₂ O, Mg ₆ Al ₂ (O
_{H) 16 HPO 4 · 4H 2} O, Ca 6 Al 2 (OH) 16 CO 3
.4H ₂ O, Zn ₆ Al ₂ (OH) ₁₆ CO ₃ .4H ₂ O, Mg
_4.5 there are _{Al 2 (OH) 13 CO 3} · 3.5H 2 O and the like.

Alternatively, the general formula is M _(1-x) · 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.

[0193] Examples of n-valent anion represented by X in the above ^{formula, 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-, C
H ₃ COC ⁻ and C ₆ H ₄ (OH) COO ⁻ .

Preferred specific examples are shown below. Mg _0.7 Al _0.3 (OH) ₂ (CO ₃ ) _0.15・ 0.54H ₂
O Mg _0.67 Al _0.33 (OH) ₂ (CO ₃ ) _0.165 · 0.5H ₂
O Mg _0.67 Al _0.33 (OH) ₂ (CO ₃ ) _0.165・ 0.2H ₂
O Mg _0.6 Al _0.4 (OH) ₂ (CO ₃ ) _0.2 · 0.42 H ₂ O Mg _0.75 Al _0.25 (OH) ₂ (CO ₃ ) _0.125 · 0.63
H ₂ O Mg _0.83 Al _0.17 (OH) ₂ (CO3) _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 thermal decomposition decomposes and adversely affects the photographic properties of the photographic light-sensitive material. And has an unexpected effect of improving photographic properties (reducing fog). As a specific method for synthesizing the hydrotalcite compounds, known methods disclosed in JP-B-46-2280 and JP-B-50-30039 can be used.

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

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

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

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

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

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

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

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

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

The zeolite is a natural zeolite (anal).
cime, chabazite, heulandite,
erionite, ferrierite, laumo
zeolite containing ntite, modernite, etc.), synthetic zeolite (A, NA, X, Y, hya)
droxy sodalite, ZK-5, B, R,
D, T, L, hydroxy, cancrinite,
Zeolite of various types such as W, Zeolaon, etc.). This zeolite not only functions as excellently as the above-described hydrotalcite compound, but also functions as a metal-based inorganic antibacterial agent as a metal carrier described later.

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

An antimicrobial agent (including a bactericide, a fungicide, etc.) can be contained in the innermost layer, the outermost layer, the intermediate layer and the like of the multilayer co-extruded blown film. By containing an antibacterial agent, it is possible to suppress the occurrence of various bacteria such as bacteria and mold which have an adverse effect on gelatin and the like constituting the photographic light-sensitive material.

The content of the antibacterial agent is generally 0.001.
The content is preferably from 0.005 to 5% by weight, more preferably from 0.01 to 3% by weight, and more preferably from 0.02 to 10% by weight.
Particularly preferred is 1.5% by weight, most preferably 0.05 to 1% by weight. When the content is less than 0.001% by weight,
No effective antibacterial effect can be obtained. On the other hand, when the content exceeds 10% by weight, not only the effect of increasing the amount is not
It becomes expensive, deteriorates the appearance of the blown film, and adversely affects the photographic properties of the photographic material.

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

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

As the metal-based inorganic antibacterial agent, a silver-based inorganic antibacterial agent is preferable because it has a large antibacterial effect and does not adversely affect the photographic properties of the photographic material.

In particular, silver zeolite in which silver is supported on zeolite, which is a silicate carrier, is preferred. Particularly preferred commercially available silver zeolite-based antibacterial agents include "Zeomic" (trade name of Shinagawa Fuel KK). In addition, "Tokyo Synthetic KK Novalon" in which silver is supported on inorganic ion exchanger ceramics is also preferable.

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

[0215] In the present invention, KK Nippon Mining Co., Ltd., "Holon Killer Beescela", which is composed of an aminometal in which a metal is compounded on both sides of an amino acid, is preferable.

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

In the photographic light-sensitive material packaging material of the present invention, various flexible sheets can be laminated on the outermost layer. It is also preferable that the flexible sheet contains the above-mentioned various antibacterial agents (including those in the surface print layer and the coating layer).

As the flexible sheet, various thermoplastic resin films, for example, various polyethylene resins, various ethylene copolymer resins, polypropylene resins,
Films of various propylene copolymer resins, polyvinyl chloride resins, various polyamide resins, polyacrylonitrile resins, ethylene / vinyl alcohol copolymer resins, polycarbonate resins, various polyester resins (PET resin, PBT resin, PEN resin, etc.) And modified resin films thereof, and further, uniaxially or biaxially stretched films of these thermoplastic resin films. In addition, triacetate film, cellophane, regenerated cellulose film, various nonwoven fabrics, various papers, various metal foils, various metal-deposited thermoplastic resin films, various inorganic substance-deposited thermoplastic resin films, various metal depositions There is paper etc.

Among these flexible sheets, particularly preferred flexible sheets are various kinds of neutral and acidic papers having a basis weight of 20 to 400 g / m ² (waste paper, recycled paper, unbleached paper, etc.) which do not adversely affect the photographic light-sensitive material. Kraft paper, semi-bleached kraft paper, bleached kraft paper, Hineri base paper, Clupak paper, Duostress paper, white paperboard, photographic base paper, high quality paper, medium paper using high yield pulp, pure white roll paper, coated paper, Imitation paper, glassine paper), non-woven fabric, synthetic paper and biaxially stretched thermoplastic resin film.

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

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

The application to which the packaging material for a photographic light-sensitive material of the present invention can be applied will be described. (1) Moisture-proof / sealing packaging bag for packaging a transparent, colored or printed film unit with a lens (Japanese Patent Publication No. 7-1380, Japanese Patent Application Laid-Open No. 5-1970087, Japanese Patent Application Laid-Open No. 7-725)
No. 93, JP-A-8-248573, JP-A-8-248573
JP-A-254793, JP-A-8-334869, JP-A-9-15796, JP-A-9-5439
No. 5, JP-A-9-120119, JP-A-9-119
244187, JP-A-9-274288, etc.). (2) Transparent, colored or printed photographic film in a plastic container (JIS 135 film, APS
And a moisture-proof and sealed packaging bag (such as Japanese Patent Application Laid-Open No. 8-254793) for collectively packaging two or more films or microfilms. (3) Moisture-proof / sealing / light-shielding bags for sheet-like photographic light-sensitive materials such as photographic paper, film for printing plate making, cut film for photography, X-ray film, PS plate (Japanese Patent Publication No. 2-2700, JP-A No. 254793, FIG. 2-3, 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 packed package of a photographic material such as a photographic paper or a photographic film (JP-A-62-172344, JP-A-2-723).
No. 47, Japanese Patent Application Laid-Open No. 5-72672, Japanese Patent Application Laid-Open
216176, JP-A-6-75341, JP-A-6-214350, JP-A-6-148820
JP, JP-A-7-257510, JP-A-7-9-9
2618, JP-A-8-40468, JP-A-10-97030, JP-B-56-16608, JP-B-6-8593, JP-B-8-9725 and the like. (7) A moisture-proof and light-shielding film for packaging a photographic photosensitive material in the form of a bulk roll (JP-A-3-53243).

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

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

The photographic material to which the packaging material for photographic material of the present invention can be applied is 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.) Developed color light-sensitive materials, heat-developable black-and-white light-sensitive materials (for example, JP-B-43-4921 and JP-B-43-4924, pages 553 to 555 of "Basics of photographic engineering", silver halide photography, published by Corona Co., 1879). And Research Tis Closure Magazine, June 1978, 9
Pages 15 to 15 (RD-17029). Further, JP-A-59-12431 and JP-A-60-124
Nos. 2950 and 61-52343 and U.S. Pat. No. 4,584,267) (transfer type heat-developable color photographic materials, etc.)) (3) Photosensitive and heat-sensitive recording materials Recording materials using photothermography (photosensitive / thermosensitive image forming method) described in JP-A-3-72358) (4) Diazonium photographic photosensitive material (4-morpholinobenzenediazonium microfilm, microfilm, for copying) (5) Azide and diazide-based photographic light-sensitive materials (photosensitive materials containing para-azide benzoate, 4,4'-diazide stilbene, such as copy films and printing plate materials) (6) ) Quinonediazide-based photographic materials (orthoquinonediazide, orthonaphthoquinonediazide compounds such as benzoquinone (1,2) Photosensitive materials containing -diazide- (2) -4-sulfonic acid phenyl ether and the like, for example, printing plates, copying films, adhesive films, etc. (7) Photopolymers (Photosensitive materials containing vinyl monomers and the like) (8) Polyvinylcinnamate-based photosensitive materials (eg, printing films, resists for ICs, etc.)

The photographic light-sensitive material package of the present invention comprises a photographic light-sensitive material stored in a packaging bag manufactured by using the photographic light-sensitive material packaging material as described above. The innermost layers of the openings to be bonded are bonded to each other at one or more locations with a peel strength larger than the blocking bonding.

Then, the coefficient of sliding friction of the outer peripheral surface of this packaging bag (load area of 4 was determined by a method according to ASTM D-1894).
2 cm ² , measured with a load of 200 g) is preferably 0.4 or more, more preferably 0.45 or more,
It is particularly preferably 0.50 or more, and most preferably 0.55 or more. If the coefficient of sliding friction of the outer peripheral surface is less than 0.4, the package is likely to slip off when many packages are stacked.

In order to adjust the coefficient of sliding friction to a predetermined range, an ethylene copolymer resin having a crystallinity of not more than 60% as measured by an X-ray diffraction method containing no antiblocking substance in the resin layer on the outer peripheral surface is used. Required amount, or adding an outer peripheral tackifier, adding a synthetic rubber or a thermoplastic elastomer, adding a resin having a low Vicat softening point,
In addition to the method of adding a filler, a non-slip agent (non-slip varnish, foamed microcapsules, rubber latex (may be used alone or as a mixture of two or more types), a polyester resin solution or an emulsion polyurethane resin) Various methods for printing or applying a solution or emulsion, an acrylic resin solution or emulsion, an acrylate copolymer resin emulsion, and other known non-slip agents) are used. Further, a method of applying or printing a pressure-sensitive adhesive or a hot-melt adhesive may be used (application and printing may be performed on the entire surface or in a dot shape). In particular, it is particularly preferable to use an ink or a coating liquid using a urethane rubber, a urethane paint, or a polyurethane resin because both photographic properties and non-slip properties are good.

More specifically, the most preferred example is described below. Colloidal silica having a particle size of 1 to 100 μm is mixed with a water-soluble polymer compound (polyvinyl pyrrolidone, sodium polyacrylate, a copolymer of sodium polyacrylate and acrylate, A layer dispersed in cellulose derivative, gelatin, casein, polyvinyl alcohol, etc.) is formed on the surface, or an emulsion polymer resin layer of unsaturated carboxylic acid or its ester and colloidal silica is formed on the surface.

In addition, the photographic material packaging material used for the packaging bag, the condition B of JIS Z 0208 (40 ° C., 90
% RH) is preferably 10 g / m ² · 24 hours or less, more preferably 7 g / m ² · 24 hours or less, and preferably 5 g / m ² · 24 hours or less. Is particularly preferred, and most preferably 3 g / m ² · 24 hours or less. Moisture permeability of 10g / m ² · ²
If the time exceeds 4 hours, the photographic properties of the photographic material are adversely affected. In particular, a photographic light-sensitive material containing a dye such as a sensitizing dye is susceptible to the influence of humidity, and a sensitivity abnormality occurs unless the moisture permeability is set to 7 g / m ² · 24 hours or less. Therefore, it is preferable to set it to 3 g / m ² · 24 hours or less.

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

FIGS. 1 to 6 are partial cross-sectional views of the packaging material for photographic light-sensitive material of the present invention.

The packaging material for photographic light-sensitive material shown in FIG. 1 has a two-layer co-extruded blown film IIa comprising an innermost layer 1a containing a light-shielding substance and an outermost layer 2a containing a light-shielding substance. The innermost layers 1a are bonded to each other by blocking B.

The packaging material for photographic light-sensitive material shown in FIG. 2 has a two-layer co-extruded blown film IIa comprising an innermost layer 1 containing no light-shielding substance and an outermost layer 2a containing a light-shielding substance. The innermost layers 1 are bonded to each other by blocking B.

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

The packaging material for a photographic light-sensitive material shown in FIG. 4 has an innermost layer 1a containing a light-shielding substance, an outermost layer 2a containing a light-shielding substance, and an intermediate layer containing a light-shielding substance provided therebetween. The three-layer co-extruded blown film IIIa composed of 3a and 3a has innermost layers 1a adhered to each other by blocking B.

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

The packaging material for photographic light-sensitive material shown in FIG. 6 has a flexible film layer 5a containing a light-shielding substance via an adhesive layer 4 on one outermost layer 2a in the laminated film having the layer structure shown in FIG. It is a laminate.

Next, the photographic photosensitive material package according to the present invention will be described with reference to the drawings.

FIG. 7 is a perspective view of a packaging bag used for a photographic photosensitive material package, in which a roll-shaped photographic photosensitive material is stored in a packaging bag 11 made of the photographic photosensitive material packaging material of the present invention. In the opening 12 of the packaging bag 11 through which the roll-shaped photographic light-sensitive material is put in and taken out, four strongly bonded portions 13 are provided on both sides at substantially equal intervals and bonded at a peel strength larger than blocking bonding. After such a configuration, FIG.
As shown in FIG.
After being bent at least once in the width, the package is fixed and sealed with a tape 14 (or a hot melt adhesive or the like).

FIG. 9 is a perspective view of a packaging bag used for a photographic photosensitive material package. The wrapping bag 21 made of the photographic photosensitive material packaging material of the present invention contains a sheet-like photographic photosensitive material. In the opening 22 of the packaging bag 21 through which the sheet-shaped photographic photosensitive material is discharged, three strong bonding portions 23 bonded at a peel strength larger than blocking bonding are provided at substantially equal intervals on both sides. After such a configuration, FIG.
0, the opening 22 is 0.3 to 5 m across the entire width.
After being bent at least once with a width of m, the package is fixed and sealed with a tape 24 (or a hot melt adhesive or the like).

[0242]

EXAMPLES [Product 1 of the Invention] The layer configuration corresponds to FIG.

The innermost layer 1a is formed using a metallocene catalyst.
The molecular weight distribution (Mw / Mn measured by GPC method)
2.1, MFR 4 g / 10 min, density 0.920 g /
cm ^ThreeEthylene-hexene-1 copolymerized by the gas phase method
90 parts by weight of coalescing resin and MFR of high-pressure radical polymerization
2.0g / 10min, density 0.920g / cm^ThreeHomopo
100 parts by weight in total consisting of 10 parts by weight of ethylene resin
On the other hand, 0.1 parts by weight of zinc stearate as a lubricant,
Alkylene bis higher fatty acid amide lubricant methylene bis
0.1 parts by weight of stearic acid amide adversely affects photographic properties
Volatile substances (aldehyde, cyanide, free sulfur)
Yellow, mercaptan, etc.)
1 part by weight of light and 0.2 parts of hydrotalcite compound
Parts, silver antibacterial agent (Gel Technology KK
Bactenone AZ) 0.2 parts by weight, as antistatic agent
Boric acid ester of stearic acid monoglyceride 0.1 weight
Parts, hindered phenolic antioxidant as antioxidant
Stopper (Irganox 107 manufactured by Ciba-Geigy KK)
6) 0.05 parts by weight of a phosphorus-based antioxidant (Ciba Geigy K
K, Irgafos 168) 0.05 parts by weight, light shielding
3 parts by weight of carbon black and titanium oxide 1
Parts by weight, Coumarone-in as a blocking adhesive reinforcement resin
25% thick light-shielding L-
This is an LDPE resin-based film layer.

The outermost layer 2a had the same thickness as that of the innermost layer 1a except that 10 parts by weight of a coumarone indene resin as a blocking adhesion reinforcing resin was removed (0 parts by weight).
Is a light-shielding L-LDPE resin-based film layer.

A 50 μm thick light-shielding two-layer co-extruded blown film IIa composed of two layers, an innermost layer 1a and an outermost layer 2a, was placed at a resin temperature of 180 ° C. and a slit gap of a 1 mm ring die (also referred to as lip clearance). ), A blow ratio of 1.5, a take-up speed of 10 m / min, a pinch roll composed of a rubber roll and a metal roll, and a nip pressure (linear pressure) of 50 kg / cm. Humidity 4.8g /
It is a packaging material for photographic photosensitive materials consisting of a laminated film of m ² · 24 hours.

The blocking adhesion of the packaging material is substantially uniform over the entire surface and has a strength not to be peeled off even in the laminating step and the bag making step. Film forming properties, bag making suitability, antistatic properties, physical strength, photographic properties, The anti-curl property, the dispersibility of carbon black, the appearance and the like were excellent.

Further, a photographic photosensitive material package in a light-shielding bag using this packaging material has a sealing / light-shielding property, heat seal strength, handleability, antistatic property, anti-collapse property, deodorizing property, antibacterial property, appearance. It is an inexpensive product with excellent properties such as recyclability and incineration suitability because it is composed of a four-layer laminated film produced only by the multilayer co-extrusion blown film forming process. . Also, it has excellent recyclability and incineration suitability.

[Comparative product 1] The same layer configuration as the product 1 of the present invention except that the innermost layer 1a of the product 1 of the present invention was obtained by removing 10 parts by weight (0 parts by weight) of the blocking adhesion reinforcing resin from the innermost layer 1a. And a laminated film having the same resin composition.

This packaging material for photographic light-sensitive materials had insufficient blocking adhesion, and was difficult to be put into practical use as a blocking adhesive laminated film.

[Comparative product 2] A single-layer light-shielding layer L having the same resin composition as the outermost layer 2a of the product 1 of the present invention and having a thickness of 100 μm.
-An LDPE resin film was obtained.

This packaging material for photographic light-sensitive materials had melt fracture, unstable frost lines, and had a large motor load, making it difficult to put it to practical use.

[Product A of the Present Invention] The layer constitution corresponds to FIG.
The innermost layer 1a is composed of 50 parts by weight of the resin composition of the innermost layer of the product 1 of the present invention and a recycled resin 5 obtained by recycling the product 1 of the present invention.
With respect to a total of 100 parts by weight of 0 parts by weight, a light-shielding L-LDPE resin-based film layer having a thickness of 25 μm containing 10 parts by weight of a coumarone indene resin as a blocking adhesion reinforcing resin added to the innermost layer of the product 1 of the present invention. is there.

The outermost layer 2a has the same thickness 2 as that of the product 1 of the present invention.
5 μm light-shielding L-LDPE resin-based film layer.
The innermost layer 1a and the outermost layer 2a each having a resin temperature of 185 ° C.
After shaping a 50 μm thick light-shielding two-layer co-extruded blown film composed of two layers under the same conditions using the same film forming machine as that of the product 1 of the present invention, the nip pressure of a pinch roll composed of a rubber roll and a metal roll ( Linear pressure) 60k
This is a packaging material for a photographic photosensitive material comprising a laminated film having a thickness of 100 μm and a moisture permeability of 4.6 g / m ² · 24 hours, which is formed by blocking adhesion and lamination at 4 g / cm.

The blocking adhesion of the packaging material for photographic light-sensitive materials is substantially uniform over the entire surface, is stronger than that of the product 1 of the present invention, does not peel off in the laminating step and the bag making step, and does not involve air in the film forming step. No wrinkles or streaks occur.

Further, physical strength, appearance, antistatic properties, photographic properties, sealing / light shielding properties, suitability for heat sealing, suitability for bag making, dispersibility of carbon black, and the like were excellent. The photographic photosensitive material packaging bag, in which the photographic photosensitive material is hermetically sealed in a light-shielding bag using the photographic photosensitive material packaging material, is sealed.
Light shielding properties, heat seal strength, handling properties, antistatic properties, physical strength, cargo collapse prevention properties, deodorizing properties, antibacterial properties, appearance, etc. were also excellent. In addition, since a laminated film having a four-layer structure can be manufactured only by the multilayer co-extrusion blown film forming step, the loss is small and an inexpensive packaging material for photographic light-sensitive materials can be easily obtained.

Further, it is possible to use a recycled resin for the multilayer co-extruded blown film, and it is possible to make the innermost layer contain 100% of the recycled resin.

In the case where another tackifier is used in place of the coumarone indene resin as the tackifier, the packaging material for a photographic light-sensitive material has substantially the same effect as the product I of the present invention and the product A of the present invention. Was.

[Product A of the Present Invention] A package containing roll-shaped color photographic paper corresponding to FIG. 7, and a packaging bag 11 is a packaging bag made using the packaging material for photographic photosensitive material of Product I of the present invention. In the opening 12 through which the roll-shaped color photographic paper is put in and taken out, there are four strong adhesive portions 13 which are heat-sealed with a peel strength larger than blocking adhesive at substantially equal intervals on both sides (size: width 20 mm, length 15 mm). ) Is provided. As a result, the suitability for taking the roll-shaped color photographic paper out of the packaging bag under the safelight is good.

The opening 12 of the packaging bag 11 is filled with the roll-shaped color photographic paper in order to secure the light shielding property and the sealing property, and then the opening 12 is overlapped as shown in FIG. By bending twice with a width of 15 mm and fixing with cellophane tape to form a sealed package, it is possible to maintain good quality for a long period of time, about 2 years. Various sheet-like or roll-shaped photographic materials described above can be stored instead of roll-shaped color photographic paper.

[Product of the invention b] When a packaging bag for a photographic photosensitive material of the product A of the invention is used as a packaging bag, colloidal silica having an average particle diameter of 30 mμ is added to one side serving as the outer peripheral surface with sodium polyacrylate and acrylate. After applying a non-slip agent dispersed in an aqueous solution consisting of a copolymer having a dry thickness of 5 μm by gravure coating, a packaging bag of the product (a) of the present invention was produced.

The coefficient of sliding friction (AS) of the outer peripheral surface of this packaging bag
Load area 42 cm ² by a method according to TM D-1894,
(Measured under a load of 200 g) is 0.65, which corresponds to FIG. 10 after storing 50 sheets of X-ray film in a U-shaped paperboard (this cardboard is called in the photographic industry). After the inner peripheral surfaces of the openings 22 are overlapped as described above, the package is bent two times with a width of 20 mm over the entire width, and fixed and fixed with cellophane tape to form a sealed package. Was successfully maintained.

Good results were also obtained when the above-mentioned sheet-like or roll-like various photographic photosensitive materials were stored in place of the sheet-like X-ray film.

[Product C of the Present Invention] The present invention is also applicable to a package using a non-slip agent consisting of an aqueous solution in which colloidal silica having an average particle diameter of 25 mμ is dispersed in a cellulose derivative instead of the non-slip agent of the product b of the present invention. It became a good package equivalent to the product b.

[Product D of the Present Invention] A packaging material for a photographic light-sensitive material having a layer constitution corresponding to FIG. 6, wherein the innermost layers 1a of two two-layer co-extruded blown films IIa of Product I of the present invention were adhered to each other by blocking. On one side of the four-layer laminated film, a 13 μm-thick polyolefin resin-based extrusion laminate adhesive layer 4 composed of 90 parts by weight of a low-density homopolyethylene resin and 10 parts by weight of an acid-modified L-LDPE resin was applied (resin temperature). 345 ° C., laminating speed 200 m / min), 40 μm thick carbon black 4
9% isotactic index by weight
An isotactic index having a thickness of 5 μm was formed on both sides of an intermediate layer made of a homopolypropylene resin having a thickness of 9.0.
A 50-μm-thick, biaxially stretched, three-layer co-extruded, light-shielding polypropylene resin film 5 (T-die film) having an inner / outer layer of 5.0 was laminated.
It is composed of a laminated film having a layer structure and has a moisture permeability of 2.1 g / m ^2.
-The sliding friction coefficient of the three-layer co-extruded light-shielding polypropylene resin film on the outer peripheral surface of the packaging bag is 0.6 for 24 hours.
No. 0, and various characteristics were the most excellent. The package using this was also the best.

[0265]

The present invention is configured as described above.
It has the effects described below. i) Stable whole-surface blocking adhesive A multilayer film laminated and laminated can be manufactured at low cost only by a multilayer co-extrusion blown film process. ii) The physical strength, the curl-preventing property, and the light-shielding property are extremely excellent, and the innermost layer is excellent in the dispersibility of the light-shielding substance. iii) It has suitability for recycling, and there is little deterioration in quality when recycled. iv) Excellent flexibility. v) It has excellent load collapse prevention. vi) Excellent dustlessness. vii) Excellent film formability. viii) Good photographic properties. ix) The innermost layer has excellent compatibility with other resins and recycled resins. x) Excellent heat seal suitability. xi) It has good take-out properties from the photographic photosensitive material packaging bag.

[Brief description of the drawings]

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

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

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

FIG. 4 is a partial cross-sectional view showing a layer structure of a packaging material for a photosensitive material according to the present invention.

FIG. 5 is a partial cross-sectional view showing a layer structure of a packaging material for a photosensitive material according to the present invention.

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

FIG. 7 is a perspective view of a packaging bag used for a photographic photosensitive material package according to the present invention.

FIG. 8 is a perspective view of a photographic photosensitive material package according to the present invention.

FIG. 9 is a perspective view of a packaging bag used for a photographic photosensitive material package according to the present invention.

FIG. 10 is a perspective view of a photographic photosensitive material package according to the present invention.

[Explanation of symbols]

 1, 1a ... innermost layer 2, 2a ... outermost layer 3, 3a ... intermediate layer 4, 4a ... adhesive layer 5, 5a ... flexible sheet 11 ... packaging bag 12 ... opening 13 ... strong adhesive part 14 ... tape 21 ... packaging Bag 22: Opening 23: Strongly bonded portion 24: Tape II, IIa: Two-layer co-extruded inflation film III, IIIa: Three-layer co-extruded inflation film B: Indicates an adhesive portion by blocking a: Contains a light-shielding substance Is shown.

Claims (8)

[Claims] 1. A multilayer film in which the innermost layers of a multi-layer co-extruded inflation film having two or more layers are bonded and laminated by blocking, wherein the innermost layer is
A packaging material for photographic light-sensitive materials, wherein the polyolefin resin produced by polymerization using a single-site catalyst is 50% by weight or more, and the blocking adhesion reinforcing resin is 0.1 to 50% by weight. 2. The packaging material according to claim 1, wherein 50% by weight or more of the polyolefin resin produced by polymerization using the innermost single-site catalyst is an ethylene copolymer resin. 3. The packaging material for a photographic light-sensitive material according to claim 1, wherein the outermost layer of the multilayer co-extruded blown film contains a polyolefin resin produced by polymerization using a single-site catalyst and an anti-blocking substance. 4. The packaging material for a photographic light-sensitive material according to claim 1, wherein at least one layer of the multilayer co-extruded blown film contains carbon black and an antioxidant. 5. The packaging material for a photographic photosensitive material according to claim 1, wherein at least one of an intermediate layer and an innermost layer of the multilayer co-extruded blown film contains a recycled thermoplastic resin. 6. A photographic photosensitive material stored in a packaging bag manufactured using the photographic photosensitive material packaging material according to claim 1, wherein the photographic photosensitive material is contained in a packaging bag. Characterized in that the innermost layers of the openings into and out of which are bonded at one or more locations with a peel strength greater than blocking adhesion. 7. The coefficient of sliding friction (A) of the outer peripheral surface of the packaging bag.
Load area 42c by the method according to STM D-1894
m ² , measured under a load of 200 g) is 0.4 or more.
A photographic light-sensitive material package according to the above. 8. JIS for packaging material for photographic photosensitive material
The moisture permeability measured under the condition B of Z 0208 is 10 g / m ^2.
The photographic light-sensitive material package according to claim 6 or 7, wherein the time is 24 hours or less.