JPH0667358A - Packing material for photographic sensitive material and light shielding bag using the same - Google Patents

Abstract

PURPOSE:To surely carry out heat sealing with a simple heat sealer such as a heat bar or a heat belt while maintaining such physical strength as to prevent tearing even when a photographic film having sharp edges and a specified weight or above is housed. CONSTITUTION:A heat sealable wear resistant flexible sheet 3a having 50kg/mm<2> or a higher Young's modulus is laminated on one side of a foamed sheet 1 with an adhesive layer 2 in-between. A flexible sheet 6 obtd. by sticking a thin metal film 5 to a wear and heat resistant flexible sheet 4 having 50kg/mm<2> or a higher Young's modulus is laminated on the other side with an adhesive layer 2 in-between.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a packaging material for a photographic light-sensitive material used for packaging a sheet-shaped or roll-shaped photographic film or photographic printing paper having a sharp edge and a weight of 500 g or more, and a light-shielding bag using the same. It is about.

[0002]

2. Description of the Related Art Conventionally, as a light-shielding bag for a photographic light-sensitive material,
As disclosed in JP-A-56-161948, the optical density of the PET film layer / adhesive layer / aluminum foil / PO-based resin layer containing a light-shielding substance and a nonionic antistatic agent is 7.5 from the outside. There was more than that. However, this light-shielding bag has not only poor heat sealability and poor sealing performance, but also physical strength (tear strength, impact drilling strength, etc.).
However, when a sheet-shaped photographic film having a sharp edge and not using the ball or a roll-shaped photographic light-sensitive material having a weight of 1 kg or more was stored, the bag was broken and the light-shielding property could not be completely secured.

Further, as disclosed in Japanese Patent Publication No. 2700/1990, a light-shielding film containing 50% by weight or more of all polyethylene-based polymers is L-LDPE resin and containing 1% by weight or more of a light-shielding substance. There was a packaging material for photographic light-sensitive materials having at least one layer. This packaging material for photographic light-sensitive materials has excellent physical strength and heat-sealing suitability, but it is a state in which sheet-shaped or roll-shaped photographic film or photographic printing paper with a sharp edge and a weight of 500 g or more is hermetically packaged. If dropped or repeatedly vibrated, the bag may be broken due to cutting or abrasion.

Further, as disclosed in Japanese Utility Model Publication No. 2-736, a packaging material for a photographic light-sensitive material is obtained by laminating a uniaxial molecularly oriented polyolefin resin film on both sides of a void sheet so that the molecular orientation axes intersect. there were. This packaging material for a photographic light-sensitive material is preferable because the bag does not break even when a photographic film of 500 g or more having a sharp edge as described above is stored.

[0005]

[Problems to be Solved by the Invention] However, the fairness 2-73
Since the packaging material for photographic light-sensitive material disclosed in Japanese Patent Publication No. 6 must cross-laminate a uniaxial molecular orientation film, two film forming devices for uniaxial molecular orientation are required, and there are many alignment losses and the cost is high. It was a thing. Further, since both sides of the packaging material for the photographic light-sensitive material are the same uniaxial molecular oriented film, heat sealing suitability is poor, automatic bag making is not possible, and an impulse sealer must be used for heat sealing, and heat It was necessary to cover the heat-sealing heating bar with heat-resistant Teflon tape so that pinholes were not generated at the seal boundary, and to cool with cold water immediately after sealing. For this reason, the heating efficiency is low, and further, the continuous bag making is impossible, resulting in a very expensive moisture-proof and light-shielding bag (however, the cost is half that of a conventional package packaged in a metal can). Further, there are problems that the heat seal strength is deteriorated with time, static electricity is generated, the surface temperature of the bag rises to 70 ° C. or more when left in sunlight, and it is difficult to distinguish between the front and back sides in a dark room operation.

The present invention solves all the above problems,
While maintaining the physical strength, continuous automatic bag making is possible with an electric heater such as a heat seal bar, a heat seal roller, a heat seal belt and a general-purpose simple heat seal device that uses the pressure part as a living body, which is highly productive and inexpensive. Therefore, it is possible to ensure perfect sealing under the use conditions of photographic photosensitive material packaging materials that can be completely sealed by heat sealing and all photographic photosensitive materials using the same, no pinholes are generated, and less static electricity is generated. The purpose of the present invention is to provide a moisture-proof, light-shielding bag that has a small increase in surface temperature of the bag even when left in the sunlight, can distinguish between the front and back in a dark room, has an excellent appearance, and has little strength reduction at the boundary of the heat seal. And

[0007]

The present invention has been made to achieve the above object, and a packaging material for a photographic light-sensitive material of the present invention comprises a cushioning sheet and a Young's sheet provided on one side of the cushioning sheet. The rate (according to ISO R 1184-1970) is 50kg
Abrasion-resistant / heat-resistant flexible sheet having heat resistance of 1 / mm ² or more, and abrasion-resistant flexible sheet having Young's modulus of 50 kg / mm ² or more provided on the other side of the cushioning sheet, and the other The layer provided on the outermost side has a heat-sealing property, and further has a complete light-shielding property as a whole.

In the present invention, Young's modulus means ISO R
The value of Young's modulus in at least one direction (longitudinal direction, lateral direction, diagonal direction, or multiaxial direction) as measured by the method according to 1184-1970 is 50 kg.
/ Mm ² or more, preferably 60 kg / mm ² or more, particularly preferably
It is essential that the pressure is 70 kg / mm ² or more, and most preferably 80 kg / mm ² or more. By using a flexible sheet having such a Young's modulus value, curling does not occur, it is used for packaging photographic light-sensitive materials such as sheet-shaped or roll-shaped photographic film or photographic paper with a sharp edge and a weight of 500 g or more. Even if a wrapping material for a photographic light-sensitive material and a light-shielding bag using the same that can secure a completely sealed light-shielding property without tearing or pinholes, can be provided at low cost.

As the buffer sheet, paper, non-woven fabric, synthetic paper having a density of 0.8 g / cm ³ or less, preferably 0.5 g / cm ³ or less,
There are foamed sheets and the like, and among these, the foamed sheets are preferable because their quality is stable, they have little adverse effect on the photographic properties of the photographic light-sensitive material, they have a large buffering effect, they are flexible, and they are inexpensive.

This foamed sheet is obtained by foaming a thermoplastic resin with a foaming agent and has a density of 0.5 g / cm ³ or less, preferably 0.2 g / cm ³ or less, and particularly preferably 0.1 g / cm ³ or less. , more preferably 0.05 g / cm ³ or less, 0.04 g / cm ³ or less is most preferred. The thickness is preferably 100 μm or more, more preferably 300 μm or more, and most preferably 500 μm or more, from the viewpoint of improving physical strength and securing buffering properties. However, it is 5 mm or less, preferably 3 mm or less, and particularly preferably 2 mm or less in view of prevention of delamination, suitability for lamination, cost, and suitability for bag making. The foaming ratio is 2 from the viewpoint of improving physical strength and ensuring buffering properties.
Double or more (density 0.5g / cm ³ or less), 10 times or more (density 0.1g / cm 3
³ or less) is preferable, and 20 times or more (density 0.05 g / cm ³ or less)
Is more preferable, and 25 times or more (density of 0.04 g / cm ³ or less) is most preferable.

However, it is preferably 50 times or less (density 0.02 g / cm ³ or more) from the viewpoints of cost, prevention of delamination, suitability for lamination and suitability for bag making.

The foam shape may be closed cells in which the cells are completely partitioned by a resin film or continuous cells (also referred to as air-permeable cells) in which the cells are continuous. Foamed sheets are preferred in the present invention.

As the thermoplastic resin used for the foamed sheet, LDPE resin, L-LDPE resin, MDPE resin, HDPE resin, EEA resin, EMA resin, EVA resin, ionomer resin, PP resin, styrene resin, vinyl chloride resin, There are polyurethane resins, phenol resins, urea resins, epoxy resins, synthetic rubbers, acid-modified resins, propylene copolymer resins, ethylene copolymer resins, polyolefin elastomers, etc. and mixed resins with one or more of these resins, Ethylene copolymer resin and homopolyethylene resin are preferable, LDPE resin, L-LDPE
A resin composition containing 50% by weight or more of one or more of resin, EVA resin and EEA resin is more preferable.

It is preferable to improve the physical strength and elasticity of the foamed sheet by crosslinking or modifying these resins. The interlayer peel strength of the foam sheet
To obtain a width of 50 g / 300 mm or more, the degree of crosslinking is 10% or more, preferably 30% or more, particularly preferably 50% or more, and most preferably 60 to 85%.

There are roughly two types of crosslinking methods. One is a method of irradiating various polyethylene resins, ethylene copolymer resins, etc. with electron beams or high-energy radiation (beta rays, comma rays, etc.). Typically, electron accelerators such as Dynatron, Linac, and Van De Graaf are used. The other is a method in which an organic peroxide that decomposes at the processing temperature of the resin is blended, and the crosslinking reaction is completed simultaneously with molding or by heating under pressure after molding.

The organic peroxide that decomposes at the processing temperature of the resin may be selected from the organic peroxides that accelerate the reaction between the polyolefin resin and unsaturated carboxylic acids described below. Typical examples are tert-butyl hydroperoxide, cumene hydroperoxide, di-tert-butyl peroxide, dicumyl peroxide, peroxyacetic acid, peroxyacetate-tert-butyl, acetyl peroxide, benzoyl peroxide, methyl ethyl ketone peroxide. There are oxides and the like.

The foaming agent is not particularly limited as long as it does not adversely affect the photographic properties of the photographic light-sensitive material and the human body, and so-called volatile foaming agents such as propane, butane, pentane, hexane and other aliphatic hydrocarbons, trichloromonofluoro. Fluorinated chlorinated hydrocarbons such as methane, dichlorotetrafluoroethane, dichloromonofluoromethane and trichlorotrifluoroethane, alcohols such as methanol and ethanol, and mixtures thereof can be used.

In addition, a heat-decomposable foaming agent having a decomposition point near the softening point of the thermoplastic resin, which does not adversely affect the photographic properties of the photographic light-sensitive material, is selected according to the softening point of the thermoplastic resin and the purpose of use. It is also possible to select and use a decomposable foaming agent.

The decomposition temperature of these pyrolyzable foaming agents is 58-
320 ° C, preferably 80-300 ° C, particularly preferably 90-290
C, most preferably 100-280 C (for polyolefin resin and polystyrene resin foam sheets).

[0020]

[Table 1]

In particular, one or a mixture of two or more polyisopropylene polyureas represented by the following formula is less likely to adversely affect the quality (photographic performance) of the photographic light-sensitive material, and is a mixture of several compounds. And the decomposition temperature
It can be arbitrarily set in the range of 130 ° C. to 280 ° C., and it is preferable because the decomposition temperature can be around the softening point of the resin used.

[0022]

[Chemical 1] {N is an integer from 1 to 5}

Furthermore, azodicarbonamide also has a wide decomposition temperature range of 190 to 230 ° C. and a gas generation amount of 190 cc / g.
It is preferable because it has a large value and does not adversely affect the quality of the photographic light-sensitive material. The quality of the photographic light-sensitive material is slightly adversely affected (fogging occurs), but the amount of gas generated is extremely large (240
cc / g) The added amount can be reduced, so that the finished buffer sheet has almost no adverse effect on the quality of the photographic light-sensitive material, and the decomposition temperature is wide in the range of 160 to 200 ° C.
N'-dinitroso-N, N'-dimethylterephthalamide is also preferred. In order to prevent the photographic properties of the photographic light-sensitive material from being adversely affected, it is preferable that the expansion ratio is high even if the amount of the thermally decomposable foaming agent used is small. Therefore, the gas generation amount is preferably 100 cc / g or more, Is 135 cc / g or more, particularly preferably 170 cc / g or more, most preferably 190 cc / g
It is a pyrolytic foaming agent of g or more. Particularly preferred representative examples are ammonium carbonate (933) and sodium bicarbonate (26
6), DNPT (240), terephthalazide (205), azodicarbonamide (190), N, N'-dinitroso-N, N '
-Dimethyl terephthalamide (180), benzene-1,3
There is disulfohydrazide (170). The numbers in parentheses indicate the gas generation rate cc / g.

The amount of the foaming agent added to the thermoplastic resin composition, preferably the polyolefin resin composition, varies depending on the type of resin, but is 0.1 to 15% by weight, preferably 0.5 to 10%.
%, Particularly preferably 1 to 7% by weight. The resin composition, in addition to the foaming agent, a foaming aid, a plasticizer,
Stabilizers, antioxidants, fillers and the like can be appropriately added according to the purpose of use.

Particularly, the foaming aid is preferably added in order to produce a foamed sheet having excellent quality. This foaming aid can freely control the decomposition temperature of the foaming agent. Typical examples of the foaming aid include a foaming accelerator and a foaming inhibitor which will be described in detail below.

When the thermoplastic resin is foamed, the thermoplastic resin has an appropriate melting temperature range, and the foaming agent must be efficiently decomposed within the temperature range. Therefore, foaming accelerators (inorganic salts, metallic soaps such as calcium stearate and magnesium stearate, organic and inorganic acids, etc.) and foaming inhibitors (organic acids, halogenated organic acids, anhydrides of organic acids, polyhydric alcohols) , Nitrogen compounds, sulfur compounds, phosphates, tin compounds) and the like. The foaming accelerator reduces the decomposition temperature of the foaming agent, and the foaming inhibitor suppresses the decomposition rate.

When the polyolefin resin is foamed while being cross-linked, it is possible to obtain a cushioning sheet having a large physical strength and excellent elasticity even if the foamed sheet has a high magnification. Since closed cells have a larger buffering effect, they are preferable as the buffer sheet used in the present invention.

The foamed sheet may be produced by a known method. Usually, a molten thermoplastic resin and a foaming agent are mixed under pressure,
It is manufactured by extrusion from a die.

Examples of wear-resistant and heat-resistant flexible sheets having Young's modulus of 50 kg / mm ² or more and wear-resistant flexible sheets include various polyethylene resins, ethylene copolymer resins, polypropylene resins, polyvinyl chloride resins, polychlorinated resins. Vinylidene resin, polyamide resin, polystyrene resin, polycarbonate resin, methacrylic resin,
Thermoplastic resin films such as polyester resins (polyethylene terephthalate resin and polyethylene naphthalate resin), modified resin films of these thermoplastic resins, films obtained by adding various feelers to these thermoplastic resins, uniaxial or biaxial of these resins. Axial stretched film, metal thin film processed film such as aluminum vacuum deposition film, cellulose acetate film, cellophane film, regenerated cellulose film, Eval resin film,
Thermosetting resins such as phenolic resins, urea resins, melamine resins, unsaturated polyester resins, epoxy resins, diallyl phthalate resins, and silicon resins, and glass fibers, α-cellulose, reinforcing inorganic pigments, etc. to these thermosetting resins. There are added sheets, coated papers, various metal foils, synthetic papers, and non-woven fabrics. Preferably, they are inexpensive, have a high Young's modulus, have excellent heat resistance, and have a basis weight of 20 to 400 g / m that does not affect the photosensitive substance. Paper (unbleached kraft paper, semi-bleached kraft paper, bleached kraft paper, hineri base paper, Kurupack paper, Duostress paper,
White paperboard, photographic base paper, pure white roll paper, coated paper, imitation paper, glassine paper) coated with resin, impregnated with resin, lacquered dust-free paper, light-shielding, moisture-proof, antistatic, etc. The thermoplastic resin film has a metal thin film processed flexible sheet provided with a metal thin film processed layer. The wear-resistant / heat-resistant flexible sheet and the wear-resistant flexible sheet having a Young's modulus of 50 kg / mm ² or more may have two or more layers with or without an adhesive layer. It may be a laminated body or a simultaneous multilayer coextrusion film obtained by simultaneously melt coextruding two or more thermoplastic resin film layers.

The Young's modulus of the flexible sheet is 50 kg / mm
^When it is less than ² , scraps are likely to be generated, and when it comes into contact with the photographic light-sensitive material, it may be cut at the sharp edge of the photographic light-sensitive material. Sex is deteriorated. Via Bum Scratch Hardness (ASTM D-
1526) is preferably 3 or more, particularly preferably 5 or more, and most preferably 7 or more. Particularly preferred representative examples include vinylidene chloride resin film (5-9), cellophane (8-16), rigid vinyl chloride resin film (9-10), polystyrene resin film (9
~ 11), polyester resin film (9-15), polyamide resin film (9-14), polymethylmethacrylate resin film (15-19), phenol resin sheet (17)
~ 22) etc.

The heat resistance of the abrasion-resistant and heat-resistant flexible sheet having a Young's modulus of 50 kg / mm ² or more may be higher than that of the heat-sealing layer, and the melting point is preferably 20 ° C. or more, more preferably Is higher than 40 ℃.
Particularly preferably, it is higher than 60 ° C. Considering photographic characteristics, pinhole resistance, heat resistance, and Young's modulus, non-stretched nylon resin film, which is one kind of polyamide resin film, uniaxially or biaxially stretched nylon resin film, polyester resin film is particularly preferable. , Ethylene vinyl alcohol copolymer resin film. In particular, a metal thin film processed thermoplastic resin film in which a metal thin film processed layer is provided on these thermoplastic resin films is preferable.

The metal thin film processed flexible sheet will be described. Al, Sn, Zn, and
Although simple metals such as Co, Cr, Ni, Fe, and Cu, alloys, and other metals capable of forming a thin film can all be used, aluminum (Al) is most suitable in terms of cost and workability, and aluminum purity is 95% or more, preferably 97% or more, particularly preferably 99% or more, most preferably
It is more than 99.5%. Especially aluminum vacuum vapor deposition biaxially stretched nylon resin film, biaxially stretched ethylene vinyl alcohol copolymer resin film and biaxially stretched polyester resin film, biaxially stretched polypropylene resin film ensure wear resistance, heat resistance and high Young's modulus, It is preferable because no pinhole is generated.

As a method for processing the metal thin film processing layer into a thin film, a vacuum evaporation method, a sputtering method, an ion plating method, an electron beam evaporation method or the like is used. The vacuum deposition method is particularly preferable because the equipment is relatively inexpensive, the workability is excellent, and the thin film processing cost is low.

The metal thin film processed layer preferably has a thickness of 55 to 1200 Å from the viewpoints of physical strength, light shielding property, antistatic property and moistureproof property as a laminate, cost and quality. That is, the thickness is 55Å
When the thickness is less than the above, the thin film processed flexible sheet layer alone cannot reduce the charge generated on both surfaces of the metal thin film processed layer, and does not increase the thickness of the flexible sheet layer and the light shielding layer on both sides of the metal thin film processed layer. In addition, it is impossible to secure the moisture-proof property and light-shielding property required as a packaging material for photosensitive materials. If the thickness exceeds 1200Å, antistatic property, moistureproof property, and light shielding property can be secured, but problems such as cost and deterioration of flexible sheet due to heating due to vacuum deposition method, deterioration of physical strength of finished laminated film, etc. However, it is difficult to put into practical use. In the case of aluminum vapor deposition film, 70 Å or more, 80 ~ 800 Å thickness is preferable for normal use, more preferably 100 Å
It is ~ 600Å. If necessary, a protective layer may be provided on the metal thin film processed layer.

As the metal thin film protective layer, an acrylic resin, an ultraviolet curable resin, a cellulose resin such as a fibrin acetate, a melamine / alkyd resin, a urethane resin, an alkyd resin, an epoxy resin, a polyester resin, an ionomer resin, an EEA resin, various polyethylenes. Appropriate resins such as resins and polypropylene resins can be used. Also wax, silicone paint, gelatin, lacquer, acrylic lacquer,
Polyvinyl alcohol and the like can also be used. Thickness is 0.1-50
μm, preferably 0.2 to 40 μm, particularly preferably 0.3 to 30
μm, most preferably 0.5 to 20 μm.

The protective layer of the metal thin film processing layer is preferably formed to have an extremely thin thickness. Even if it is produced by the extrusion laminating method, the removal of static electricity becomes insufficient unless the thickness is 50 μm or less.
If the thickness is 5 μm or less by a known solution coating method or spray coating method, the metal thin film processed layer can be protected and the effect of removing static electricity is great. It is also preferable to apply an ultraviolet-curable resin layer or a thermosetting resin layer having excellent wear resistance without heating, in a thickness of 5 μm or less. Known resins can be used for these resins and devices.

The flexible sheet processed with a metal thin film as described above has an oxygen permeability of 50 cc / m ² , 24 hours, 1 atm, 20 ° C. or less measured by the MOCON method (the same pressure method based on ASTM D-3985). Determined by the JIS Z-0208 cup method (measured at 40 ° C and 90% R) with a moisture vapor transmission rate of 5 g / m ²・ 2
It is less than 4 hours, and the quality of the photographic light-sensitive material can be maintained for a long time. Especially when the aluminum vapor deposition film is 400 liters or more, the oxygen permeability is 35 cc / m ² · 24 hours · 1 atm · 20
It is especially effective for photographic light-sensitive materials and high-sensitivity photographic light-sensitive materials containing sensitizing dyes, which have a moisture permeability of 3 g / m ² · 24 hours or less at a temperature of ℃ or less, and whose quality deteriorates due to oxygen and humidity. (More than a year) quality can be maintained. Oxygen permeability of 20cc / m ² · 24 hours · 1 atm · 20 ° C or less, moisture permeability of 2
When the packaging material has a g / m ² · 24 hours or less, an ISO sensitivity of 100 or more and a high-sensitivity photographic light-sensitive material containing various couplers and various dyes can maintain good quality for two years or more. Oxygen permeability is 15cc / m ² · 24 hours · 1atm · 20
When the packaging material has a moisture permeability of 1.5 g / m ² · 24 hours or less at a temperature of ℃ or less, even a high-sensitivity photographic light-sensitive material having an ISO sensitivity of 400 or more can maintain good quality for two years or more.

In the packaging material for a photographic light-sensitive material of the present invention, the layer provided on the other outermost layer (layer on the photographic light-sensitive material side) has a heat-sealing property. The outermost layer having the heat-sealing property may be provided only for heat-sealing, or may be used as the above-mentioned abrasion-resistant flexible sheet. As the layer having this heat-sealing property, a polyolefin resin layer can be used, which hardly affects the photographic light-sensitive material, and has heat-sealing suitability (heat-sealing strength over time, foreign matter-sealing property, pinhole prevention, etc.). Considering the fact that the ethylene copolymer resin is excellent and has a large physical strength, the ethylene copolymer resin is preferably 5% by weight or more, preferably 10% by weight or more.
It is a polyolefin resin layer containing not less than 20% by weight, particularly preferably not less than 20% by weight, most preferably not less than 50% by weight.

Representative examples of the above ethylene copolymer resin are shown below. (1) Ethylene-vinyl acetate copolymer resin (hereinafter EVA
(Represented as 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 (hereafter referred to as EMM resin) (7) Ethylene-methyl acrylate copolymer resin (hereafter
(Displayed as EMA resin) (8) Ethylene-ethyl acrylate copolymer resin (hereinafter,
(Displayed as EEA resin) (9) Ethylene-acrylonitrile copolymer resin (10) Ethylene-acrylic acid copolymer resin (hereinafter referred to as EAA
(Indicated as resin) (11) Ionomer resin (resin obtained by crosslinking a copolymer of ethylene and an unsaturated acid with a metal such as zinc) (12) Ethylene-α-olefin copolymer resin (hereinafter referred to as L-
(Displayed as LDPE resin) (13) Ethylene-propylene-butene-1 terpolymer resin (14) Ethylene elastomer

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

It is also preferable to blend with other thermoplastic resins, various thermoplastic resin elastomers, various additives and modifiers in order to adapt to the required characteristics.

Among the ethylene copolymer resins, an ethylene / α-olefin copolymer resin is particularly preferable, and a linear low-density polyethylene resin (hereinafter abbreviated as L-LD) is generally used.
It is a resin called as PE resin).

[0043] L-LDPE (L inear L ow D ensity P
oly e thylene) resin is called third polyethylene resin, medium and low density, energy conservation has both the advantages of high density both homo polyethylene resins, low cost to meet the needs of the times that resource saving, high-strength resin Is. This resin is a copolymer obtained by copolymerizing ethylene and an α-olefin having 3 to 13 carbon atoms, preferably 4 to 10 carbon atoms by a low pressure method or a high pressure improvement method, and has a linear straight chain with a short branch structure. It is a polyethylene resin. Butene-1, octene-1, hexene-1, 4-methylpentene-1, heptene-1, decene-1 and the like are used as α-olefins which are preferable in terms of physical strength and cost.

The density is generally considered to be low or medium density polyethylene resin, but most of the commercially available products have a density in the range of 0.87 to 0.95 g / cm ³ . Melt index is 0.1-5
Many are in the range of 0 g / 10 minutes.

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

Among these L-LDPE resins, those having a melt index (hereinafter referred to as MI) of 0.8 to 10 g / 10 min are particularly preferable in terms of physical strength, heat seal strength, polymerization suitability and blown film moldability. , Preferably 1.0 to 7 g / 10 minutes (JISK-6760, temperature 190 ° C., load 2.16 kgf), density 0.870 to 0.940 g / cm ³ (JI
SK-6760), and the carbon number of the α-olefin is 4 to
It was obtained by eight liquid phase process and gas phase process.

Specific examples of commercially available L-LDPE resins are shown below. Ethylene / Butene-1 Copolymer Resin G Resin and NUC-FLX (UCC Company) Dourex (Dow Chemical Company) Sclear (Dupont Canada Company) Marlex (Philips Company) Stamilex (DSM Company) Excellen VL (Sumitomo Chemical Co., Ltd.) NeoZex (Mitsui Petrochemical) Mitsubishi Polyethylene-LL (Mitsubishi Petrochemical) Nisseki Linilex (Nippon Petrochemical) NUC Polyethylene-LL (Nippon Unicar) Idemitsu Polyethylene L (Idemitsu Petrochemical) Ethylene / Hexene-1 Copolymer Resin TUFLIN ( UCC) TUFTHENE (Nippon Unicar) Ethylene / 4-methylpentene-1 copolymer resin Ultzex (Mitsui Petrochemical) Ethylene / octene-1 copolymer resin Stamirex (DSM) Dourex (Dow Chemical Co.) Screamer Du Nkanada Inc.) MORETEC (Idemitsu Petrochemical)

A particularly preferred representative example is Mitsui Petrochemical Co., Ltd. in which 4-methylpentene-1 having 6 carbon atoms as an α-olefin side chain is introduced into polyethylene.
Ultozex Co., Ltd. and octene-1 having 8 carbon atoms as an α-olefin side chain are introduced into Idemitsu Petrochemical Co., Ltd.
Morerec and Stamilex of DSM and Dowlex of Dow Chemical Co., Ltd. (these are L-LDPE resins obtained by the co-liquid phase process of four companies). A preferred representative example obtained by the low-pressure vapor-phase process is the trade name, which has 6 carbon atoms as the α-olefin side chain.
TUF of Nippon Unicar Co., Ltd. which introduced 1 hexene-1
THEN and TUFLIN of UCC.

The recently released density is 0.910 g / cm ^3.
Ultra low density linear low density polyethylene resin of less than, for example, NUC-FLX of UCC and Excellen VL of Sumitomo Chemical Co., Ltd. are also preferable because they have excellent pinhole resistance, tear strength, and heat sealability (above, Products of both companies use butene-1 with α-olefin having 4 carbon atoms).

Representative manufacturers of the EEA resin are Union Carbide (USA), Nippon Unicar Co., Ltd., Mitsubishi Petrochemical Co., Ltd., Sumitomo Chemical Co., Ltd. and Mitsui Polychemical Co., Ltd. . As specific examples, representative brand names of EEA resins currently marketed by Nippon Unicar Co., Ltd., and their comonomer content, melt index, and density are shown (comonomer content 6% or more by NUC test method).

[0051]

[Table 2]

2% by weight or more of these ethylene copolymer resins, particularly preferably L-LDPE resin which is a copolymer resin of ethylene and an α-olefin having 4 to 10 carbon atoms,
When a heat-sealing layer comprising a polyolefin resin composition containing preferably 5% by weight or more, particularly preferably 10% by weight or more, and most preferably 20% by weight or more is provided, the heat-sealing strength is less deteriorated with time and the sealing and light-shielding properties are excellent. It becomes a light-shielding bag for photographic light-sensitive materials.

In the present invention, various known thermoplastic elastomers, preferably polyolefin resin-based elastomers, are contained in the resin composition in an amount of 3% by weight or more, preferably 6 to 70% by weight, particularly preferably 10 to 60% by weight, and flexible. It is also preferable to add it for the purpose of improvement and impact strength improvement at low temperature.

Among the polyolefin resin type elastomers, ethylene / propylene rubber (hereinafter referred to as EPM) is preferable because it is inexpensive and does not adversely affect the photographic properties. A typical example of ethylene / propylene rubber is EPM, which is a copolymer of ethylene and propylene, and EPDM, which is a terpolymer of ethylene, propylene and a diene monomer for crosslinking (ethylidene norbornene etc.).
There are types. EPM and EPDM are particularly preferable because they have excellent heat resistance and weather resistance because they do not have an unsaturated bond in the polymer main chain and do not adversely affect the photographic light-sensitive material.

An antioxidant can be added to the packaging material for a photographic light-sensitive material of the present invention. Addition of an antioxidant prevents the generation of decomposed substances that adversely affect the photographic properties due to the thermal deterioration of resins and various additives, the generation of lumps (foreign matter-like solidification) and microgrids, and coloring failures. can do.

The oxidative decomposition of the resin due to heat is greater in the polyolefin resin having more CH ₃ branches. This is because it absorbs a large amount of oxygen, so the degree of oxidative decomposition due to heat is polypropylene resin> homopolyethylene resin> ethylene.
It becomes an α-olefin copolymer resin. Polyethylene resins (including ethylene / α-olefin copolymer resins) and various polypropylene resins (including propylene / ethylene random copolymer resins), which are typical thermoplastic resins of crystalline resins, are hydrocarbons, It is believed that the autoxidation of hydrocarbons progresses in the chain as follows once dehydration occurs in the presence of oxygen to produce free radicals.

RH → R • R • + O ₂ → ROO • ROO • + RH → ROOH + R • ROOH → RO • + • OH RO • + RH → ROH + R •• OH + RH → HOH + R • Thus, the oxidation of hydrocarbons is accelerated To produce a large amount of alcohol, aldehyde, acid, etc., which adversely affects the photographic properties of the photographic light-sensitive material, and these react with each other to form a polymer.

In order to prevent the oxidation of hydrocarbons, it is necessary to go through the above chain reaction, and therefore an antioxidant is used. In addition, it is also preferable to add the radical scavenger described below.

The radical scavenger used in the present invention is 1,1-diphenyl-2-picrylhydrazyl,
1,3,5-Triphenylferdazyl, 2,2,6
6-Tetramethyl-4-piperidone-1-oxyl, N
-(3-N-oxyanilino-1 .3-dimethylbutylidene) -aniline oxide, high valent metal salts such as ferric chloride, diphenylpicrylhydrazine, diphenylpicrylhydrazine, diphenylamine, hydroquinone, t- Examples thereof include butyl catechol, dithiobenzoyl disulfide, p · p′-ditolyl trisulfide, benzoquinone derivative, nitro compound, and nitroso compound. Among these, it is particularly preferable to use hydroquinone. The above radical scavengers may be used alone or in combination of several kinds. The content of the radical scavenger in the slippery thermoplastic resin layer is 100 to 10,000 ppm, preferably 500 to
It is 5,000 ppm.

Phosphoric acid, citric acid, phosphoric acid compounds, citric acid compounds and the like described as antioxidant synergistic agents in the present invention which synergistically improve the antioxidant action when used in combination with an antioxidant It is particularly preferable to use in combination with at least one of the agent and the radical scavenger. The content of these antioxidant synergists is 0.001 to 2.0% by weight, preferably 0.
It is 005 to 1.5% by weight, particularly preferably 0.01 to 1.0% by weight.

In order to prevent the oxidation of hydrocarbons, it is necessary to break through the above chain reaction, and therefore an antioxidant is used. That is, the antioxidant decomposes the free radical chain terminator that reacts with the free radicals (mainly ROO.) That are chain propagators to inactivate them and the hydroperoxide ROOH that is the main source of free radicals. Then, there is a peroxide decomposing agent which stabilizes this. The former includes alkylphenol antioxidants and aromatic amine antioxidants. The latter includes sulfur antioxidants and phosphorus antioxidants. It is preferable to use a free-radical chain-stopping antioxidant and a peroxide decomposition antioxidant together to prevent yellowing or browning due to heat deterioration of the thermoplastic resin and the occurrence of lumps (foreign matter-like black solidification). . Since various antioxidants are also reducing agents that adversely affect the photographic light-sensitive materials, carefully study the addition amount and keep it to the necessary minimum amount for a long period (one year or more).
The quality deterioration of the photographic light-sensitive material becomes large during the storage of, which becomes a problem.

In order to prevent thermal deterioration of the thermoplastic resin, particularly the polyolefin resin, the organic cyclic phosphorus compound is contained in an amount of 0.001 to 1% by weight, preferably 0.005 to 0.8% by weight, particularly preferably 0.
It is preferable to use 01 to 0.5% by weight alone or in combination with other antioxidants. As an antioxidant to be used in combination, a phenolic antioxidant, especially a hindered phenolic antioxidant, which has a free radical chain terminating action different from the peroxide decomposing action of a cyclic phosphorus compound and has little adverse effect on a photographic light-sensitive material. 0.001 to 1% by weight, preferably 0.005 to 0.8% by weight,
It is particularly preferable to use together 0.01 to 0.5% by weight.

When these radical scavengers and / or the antioxidant synergists such as phosphoric acid and citric acid are also used in combination with these, the generation of substances adversely affecting the photographic light-sensitive material and the heat of resins and additives It is preferable because yellowing, browning, and spotting due to deterioration are reduced and continuous molding is possible for a long time.

A typical general formula of the organic cyclic phosphorus compound of the present invention is described below.

[0065]

[Chemical 2] {In the formula, R ₁ represents a tertiary butyl group or a tertiary amyl group, R ₂ represents an alkyl group having 1 to 9 carbon atoms, and R ₃ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. Shows,
R ₄ represents an alkyl group having 1 to 30 carbon atoms or an aryl group having 6 to 15 carbon atoms. }

[0066]

[Chemical 3] {In the formula, R ₁ represents a tertiary butyl group or a tertiary amyl group, R ₂ represents an alkyl group having 1 to 9 carbon atoms, and R ₃ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. Shows,
R ₄ represents an alkyl group having 1 to 30 carbon atoms or an aryl group having 6 to 15 carbon atoms. }

[0067]

[Chemical 4] {In the formula, R ₂ represents an alkyl group having 1 to 9 carbon atoms,
R ₃ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and M represents an alkali metal. }

[0068]

[Chemical 5] {In the formula, R ₃ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ₅ and R ₆ are each a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group, an aryl group or aralkyl. represents a group, X is -OH group or -O ^-
Indicates NH ₄ ⁺ . }

Representative examples of the antioxidant are shown below. (A) Phenolic antioxidant (t is an abbreviation for tert.) 6-t-butyl-3-methylphenyl derivative, vitamin E (tocopherol), 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'-butylidene bis (6
-T-butyl-m-cresol), 4.4'-thiobis (6-t-butyl-m-cresol), 4.4-dihydroxydiphenylcyclohexane, alkylated bisphenol, styrenated phenol, 2.6-di- t-butyl-4-methylphenol, 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-butylphenol), 4.4 '
-Butylidene bis (3-methyl-6-t-butylphenol), stearyl-β (3.5-di-4-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-t-butyl-4hydroxybenzyl) benzene, tetrakis [methylene-3 (3'-5'-
Di-t-butyl-4'-hydroxyphenyl) propionate] methane, etc.

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

(C) Allylamine Antioxidant Phenyl-α-naphthylamine, N-phenyl-β-naphthylamine, N-phenyl-N'-isopropyl-P
-Phenylenediamine, N.N'-diphenyl-P-phenylenediamine, N.N'-di-β-naphthyl-P-
Phenylenediamine, N- (3'-hydroxybutylidene) -1-naphthylamine, etc.

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

(E) Phosphite antioxidants Alkylated allyl phosphite, diphenylisodecyl phosphite, tris (nonylphenyl) phosphite sodium phosphite, trinonylphenyl phosphite, triphenyl phosphite, etc.

(F) Thiourea type antioxidant Thiourea derivative, 1.3-bis (dimethylaminopropyl) -2-thiourea, etc.

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

Typical examples of the hindered phenolic antioxidants most preferable 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 (3,5-di-tert-butyl-4-hydroxy-hydrocinnamate)] methane, octadecyl-3,5-di-
tert-butyl-4-hydroxy-hydrocinnamate,
2,2 ', 2'-tris [(3,5-di-tert-butyl-4
-Hydroxyphenyl) propionyloxy] ethyl isocyanurate, 1,3,5-tris (4-tert-butyl-3-hydroxy-2,6-di-methylbenzyl) isocyanurate, tetrakis (2,4-di-tert) -Butylphenyl) 4,4'-biphenylene diphosphite,
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'-butylidene bis- (3-
Methyl-6-tert-butylphenol), 2,6-di-te
rt-Butyl-4-methylphenol, 4-hydroxy
Methyl-2,6-di-tert-butylphenol, 2,6-
Di-tert-4-n-butylphenol, 2,6-bis (2'-hydroxy-3'-tert-butyl-5'-methylpentyl) -4-methylphenol, 4,4'-methylene-bis- (6 -Tert-butyl-O-cresol),
4,4′-butylidene-bis (6-tert-butyl-m-cresol) and the like can be mentioned. Among these, the melting point is 10
It is preferably 0 ° C or higher, particularly 120 ° C or higher. Further, it is effective to use it in combination with a phosphorus-based antioxidant.

Vitamin E (tocopherol) has carbon black, calcium carbonate,
When used in combination with a light-shielding substance such as titanium oxide or metal powder, the light-shielding ability is improved by about 20% compared to the case of using the light-shielding substance alone, and the same light-shielding property is obtained even if the amount of the light-shielding substance added is reduced by about 15%. Therefore, various effects such as physical strength improvement, appearance improvement, and material cost saving are exhibited, which is preferable.

Representative commercial antioxidants are shown below. (1) Phenolic antioxidant; SUMILIZER B
HT (Sumitomo), IRGANOX 1076 (Ciba Geigy),
MARK AO-50 (Adeka Argus), SUMILI
ZER BP-76 (Sumitomo), TOMINOX SS (Yoshitomi), IRGANOX 565 (Ciba Geigy), NONO
X WSP (ICI), SANTONOX (Monsant
o), SUMILIZER WX R (Sumitomo), ANTA
GEGRYSTAL (Kawaguchi), IRGANOX 1035 (Ciba Geigy), ANTAGE W-400 (Kawaguchi), NOC
LIZER NS-6 (Ouchi Shinko), IRGANOX 14
25 WL (Ciba Geigy), MARK AO-80 (Adeka Argus), SUMILIZER GA-80 (Sumitomo), TOPANOLCA (ICI), MARK AO
-30 (Adeka Argus), MARK AO-20 (Adeka Argus), IRGANOX 3114 (Ciba Geigy), MARK AO-330 (Adeka Argus), IR
GANOX 1330 (Ciba Geigy), CYANOX 1790
(ACC), IRGANOX 1010 (Ciba Geigy), M
ARK AO-60 (Adeka Argus), SUMILI
ZER BP-101 (Sumitomo), TOMINOX TT (Yoshitomi), etc.

(2) Phosphorus antioxidant; IRGAFOS 168
(Ciba Geigy), MARK 2112 (Adeka Argus), Weston 618 (Borg Warner), MARK
PEP-8 (Adeka Argus), ULTRANOX
626 (Borg Warner), MARK PEP-24G (Adeka Argus), MARK PEP-36 (Adeka Argus), HGA (Sanko), etc.

(3) Thioether type antioxidant; DLTD
P "YOSHITOMI" (Yoshitomi), SUMILIZER
TPL (Sumitomo), ANTIOX L (NOF), DMTD
"YOSHITOMI" (Yoshitomi), SUMILIZER
TPM (Sumitomo), ANTIOX M (NOF), DSTP
"YOSHITOMI" (Yoshitomi), SUMILIZER T
PS (Sumitomo), ANTIOXS (NOF), SEENOX
412S (Cipro), MARK AO-412S (Adeka Argus), SUMILIZER TP-D (Sumitomo), M
ARK AO-23 (Adeka Argus), SANDST
AB P-EPQ (sand), IRGAFOS P-BP
QFF (Ciba Geigy), IRGANOX 1222 (Ciba Geigy), MARK 329K (Adeka Argus), W
ESTON 399 (Borg Warner), MARK 260
(Adeka Argus), MARK 522A (Adeka Argus), etc.

(4) Metal deactivator NAUGARD XL-1 (Uniroyal), MARK
CDA-1 (Adeka Argus), MARK CDA-
6 (Adeka Argus), LRGANOX MD-1024
(Ciba Geigy), CUNOX (Mitsui Toatsu), etc. Particularly preferred antioxidants are phenolic antioxidants, and commercially available products include Irganox of Ciba Geigy and Sumilizer BHT and Sumilizer of Sumitomo Chemical Co., Ltd.
BH-76, Sumilizer WX-R, Sumilizer BP-10
It is 1 mag.

Further, 2,6-di-hibutyl-p-cresol (BHT), a low volatility high molecular weight phenolic antioxidant (trade name: Ireganox 1010, Ireganox 1076, T
opanol CA, Ionox 330, etc.), dilauryl thiodipropionate, distearyl thiopropionate, dialkyl phosphate and the like, and it is effective to use one or more, particularly two or more, in combination.

The addition amount of the antioxidant is 0.0005 to 1.5% by weight, preferably 0.0005 to 0.8% by weight, and 0.001 to 0.5% by weight.
Is more preferable, and 0.002-0.3% by weight is the most preferable. If the amount added is less than 0.0005% by weight, there is almost no effect of addition.
On the other hand, if the addition amount exceeds 0.8% by weight, the photographic light-sensitive material utilizing the oxidation and reduction effects may be adversely affected, and abnormalities in photographic performance (fogging and sensitivity fluctuation) may occur. For this reason, it is preferable to add the antioxidant in the minimum amount that does not cause coloring failure or spots.

Vitamin E (tocopherol), which has no adverse effect on the human body, has a large antioxidant effect on various thermoplastic resins, and can improve the light-shielding property, has an antioxidant effect.
When used in combination with a light-shielding substance, the light-shielding ability is improved by about 20% compared to the case where the light-shielding substance is used alone. Therefore, even if the amount of the light-shielding substance added is reduced by about 15%, a packaging material having the same light-shielding property can be obtained, and various effects such as improvement in physical properties, appearance improvement, and material cost reduction can be obtained, which is particularly preferable. Further, when used in combination with carbon black or the like, antioxidation exerts a synergistic effect. The combined use of a phenol-based antioxidant, a phosphorus-based antioxidant and carbon black is preferable because the antioxidant effect is particularly exhibited.

Other Plastics Data Handbook (published by the KK Industrial Research Group), pages 794 to 799, data collection of various antioxidants and plastic additives [KK
Chemical Industry Co., Ltd.] various antioxidants disclosed on pages 327 to 329 and various antioxidants disclosed on pages 211 to 212 of PLASTICS AGE ENCYCLOPEDIA Advance 1986 (KK Plastic Age), etc. Is possible.

In order to prevent photo-deterioration of the packaging material for photographic light-sensitive materials, various ultraviolet absorbers are contained in an amount of 0.001 to 5% by weight, preferably 0.005 to 3% by weight, particularly preferably 0.01 to 1% by weight. Particularly preferred as the ultraviolet absorber is a hindered amine type ultraviolet absorber (2.2,6.6-tetramethyl-4-piperidinol, 2.2,6.6-tetramethyl-4-piperidylbenzoate, 2.2,6). .6-Tetramethyl-4-piperidinol, etc.) and benzophenone-based UV absorbers.

A light-shielding substance can be added to the packaging material for a photographic light-sensitive material of the present invention. By adding the light-shielding substance, the light-shielding property can be secured, and the conductivity and the physical characteristics can be improved.

Typical examples of the light-shielding substance are shown below. (1) Inorganic compound A. Oxide: silica, diatomaceous earth, alumina, titanium oxide, iron oxide (iron black), zinc oxide, magnesium oxide, antimony oxide, barium ferrite, strontium ferrite, beryllium oxide, pumice, pumice balloon, alumina fiber, etc. B. Hydroxide ... Aluminum hydroxide, magnesium hydroxide, basic magnesium carbonate C.I. Carbonate ... Calcium carbonate, magnesium carbonate, dolomite, dawsonite, etc. D. (Sulfite) ... Calcium sulfate, barium sulfate, ammonium sulfate, calcium sulfite, etc. E. Silicates ... Talc, clay, mica, asbestos,
Glass fiber, glass balloon, glass beads, calcium silicate, montmorillonite, bentonite, etc. F. Carbon ... Carbon black, graphite, carbon fiber, carbon hollow sphere, etc. G. 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 powder (pine, oak, sawdust, etc.), shell fiber (almond, peanut, fir shell, etc.), cotton, jute, paper strip, cellophane strip, nylon fiber, polypropylene fiber,
Starch (including modified starch and surface-treated starch),
Aromatic polyamide fiber, etc.

Among these light-shielding substances, an opaque inorganic compound is preferable, and in particular, since it is a substance which is excellent in heat resistance and light resistance and is relatively inactive, carbon black, titanium nitride and graphite, which are light-absorbing substances, are preferable. Is preferred.

Examples of classification based on carbon black raw materials include gas black, furnace black, channel black, anthracene black, acetylene black, Ketjen carbon black, thermal black,
Lamp black, oil smoke, pine smoke, animal black, vegetable black, etc. are available.

As an actual product, for example, carbon black # 20 (B), # 30 (B), # 33 (B), # 40 manufactured by Mitsubishi Kasei
(B), # 41 (B), # 44 (B), # 45 (B), # 50, # 55, # 10
0, # 600, # 950, # 1000, # 2200 (B), # 2400 (B), M
A8, MA11, MA100 and the like.

As overseas products, for example, Cabot's Black Pearls 2,46,70,71,74,80,81,607, etc.
Regal 300, 330, 400, 660, 991, SRF-S, Vul
can3, 6 etc., Sterling 10, SO, V, S, FT-F
F, MT-FF, etc. are mentioned.

Further, United of Ashland Chemical Co.
R, BB, 15, 102, 3001, 3004, 3006, 3007, 3008, 3
Examples include, but are not limited to, 009, 3011, 3012, XC-3016, XC-3017, and 3020.

In the present invention, furnace carbon black is preferable for the purpose of improving the light-shielding property, cost and physical properties, and acetylene carbon black and Ketjen carbon which is a modified by-product carbon black are expensive as the light-shielding substance having an antistatic effect. Black is preferred. If necessary, it is also preferable to mix the former and the latter according to the required characteristics. The form in which the light-shielding substance is mixed with the thermoplastic resin is roughly classified as follows.

(1) Uniformly colored pellets (the most commonly used ones called color bound) (2) Dispersible powders (also called dry color, treated with various surface treatment agents, Further, a powdery material obtained by adding a dispersion aid and pulverizing it into fine particles) (3) Paste (dispersed in a plasticizer etc.) (4) Liquid (liquid dispersed in a surfactant etc. also called liquid color) (5) Masterbatch pellets (high-dispersion of light-shielding substances in the plastic to be colored) (6) Wet-grain powder (high-concentration of light-shielding substances in plastic) After that, processed into granular powder) (7) Dry powder (ordinary untreated dry powder)

There are various forms of blending the light-shielding substance with the thermoplastic resin as described above, but the masterbatch method is preferable in terms of cost, prevention of contamination of the workplace, and the like. In Japanese Patent Publication No. 40-26196, which is a publicly known document, a method of dispersing a carbon black in a solution of a polymer dissolved in an organic solvent to prepare a polymer-carbon black masterbatch is disclosed in Japanese Patent Publication No. 43-10362. Describes a method of dispersing carbon black in polyethylene to form a masterbatch. The present inventor also discloses in JP-A-63-186740 a resin composition for a colored masterbatch in which a light-shielding substance is dispersed in a specific ethylene / ethyl acrylate copolymer resin.

When used as a packaging material for a photographic light-sensitive material of the present invention, fog does not occur in the photographic light-sensitive material, the increase or decrease in the photosensitivity is small, and the light-shielding ability is large.
Thermoplastic resins, especially the most preferred L-LDPE in the present invention
Even when added to a resin film, carbon black has a pH (measured according to JIS K 6221) of 6.0 to 9.0 because carbon black is hard to be generated and pinholes are less likely to occur in the film such as fish eyes. , Average particle size (measured by electron microscopy) 10-120mμ, volatile component (measured by JIS K 6221) 2.0% or less, DBP oil absorption
Furnace carbon black having an oil absorption amount A method of JIS K 6221 of 50 ml / 100 g or more is preferable because it improves the light-shielding property, the dispersibility, and the deterioration of physical properties.

Further, if the sulfur component measured by ASTM D 1619-50 is 0.9% or less, preferably 0.7% or less, particularly preferably 0.5% or less, the photographic properties are adversely affected. In particular, it is necessary to select a light-shielding substance having a free sulfur component which directly affects the photographic properties of the photographic light-sensitive material in an amount of 0.1% or less, preferably 0.05% or less, and particularly preferably 0.01% or less.

The amount of the light-shielding substance added is 0.05 to 50.0% by weight.
Is preferred, 0.1-30.0 wt% is more preferred, 0.5-1
5.0% by weight is most preferred. If the added amount is less than 0.05% by weight, the layer thickness must be 2 mm or more to secure the light-shielding property required as a packaging material for a photographic light-sensitive material, which is difficult to put into practical use in terms of cost and flexibility. The addition amount is 5
If it exceeds 0.0% by weight, it is difficult to put it into practical use due to moisture absorption of the light-shielding substance, foaming, generation of pinholes or fish eyes, and reduction in physical strength. Inflation film, in particular, cannot be manufactured because the bubble becomes unstable.

The second preferred light-shielding substance after carbon black is an inorganic pigment having a refractive index of 1.50 or more as measured by the Larsen oil immersion method, and various metal powders, metal flakes, metal pastes, metal fibers and carbon fibers. The preferred refractive index is 1.
Representative examples of 50 or more inorganic pigments and metal powders are shown below,
The present invention is not limited to these. The number in parentheses indicates the refractive index. Inorganic pigments with a refractive index of 1.50 or higher include rutile titanium oxide (2.75) and silicon carbide (2.6
7), anatase type titanium oxide (2.52), zinc oxide (2.3
7), antimony oxide (2.35), lead white (2.09), zinc white (2.02), lithopone (1.84), zircon (1.80), corundum (1.77), spinel (1.73), apatite (1.
64), barite powder (1.64), barium sulfate (1.64), magnesite (1.62), dolomite (1.59), calcium carbonate (1.58), talc (1.58), calcium sulfate (1.5
6), silicic acid anhydride (1.55), quartz powder (1.54), magnesium hydroxide (1.54), hydrochloric acid magnesium carbonate (1.5
2), alumina (1.50), etc. Particularly preferred is a light-shielding substance having a refractive index of 1.56 or more, and 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 (1.44), etc. have a small light-shielding ability, and therefore a large amount needs to be added, and use as a light-shielding substance is not preferable. In addition, due to the recent boom in overseas travel, ISO has become an inspection machine that uses X-rays for baggage inspection at airports.
X when passed through high-speed photographic film with sensitivity of 400 or more
Fogging tends to occur due to the lines. 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, preferably 3.4
Above, particularly preferably, the form of the light-shielding substance having an X-ray blocking property other than the light-shielding property of 4.0 or more is not limited to the following representative examples, and any form such as pigment, powder,
It may be flakes, whiskers, fibers and the like. Light-shielding substances with 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 whiskers, silicon nitride whiskers, copper whiskers, iron whiskers, nickel whiskers , Chromium whiskers, stainless powder and whiskers, magnesite, apatite, spinel, corundum, zircon, antimony trioxide, barium carbonate, zinc white, chromium oxide, tin powder and mixtures thereof.

Particularly preferred light-shielding substances for imparting X-ray blocking properties are zircon, corundum, barium sulfate, barium chloride, barium titanate, lead powder, lead oxide, zinc powder, zinc white, tin powder, stainless powder, These are stainless steel whiskers, iron oxide, tungsten whiskers, and nickel whiskers. The light-shielding substance particularly preferable as a packaging material for an ultra-high-sensitivity photographic 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 a refractive index of 1.56 or more and a specific gravity of 3.4 or more. It is a light-shielding substance. Table 3 shows the refractive index and the specific gravity of the light-shielding substance.

[0104]

[Table 3]

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.

Further, the X-ray shielding light-shielding substance does not adversely affect the photographic light-sensitive material and does not deteriorate the film moldability, so that the loss on drying at 100 ° C. for 5 hours is preferably 2.0% by weight or less, It is preferably used in an amount of 1.0% by weight or less, and most preferably 0.5% by weight or less.

As a typical example of an oil-absorbing inorganic pigment having an effect of adsorbing a lubricant, an antioxidant or an organic nucleating agent which easily bleeds out, and adsorbing a deodorant, an aromatic agent, an oxygen scavenger, etc. 52), asbestine (50), clay (51), titanium oxide (56), kaolin (60), talc (60), carbon black (60 or more), activated carbon, etc. The numbers in parentheses indicate the oil absorption (measured by the oil absorption A method of JIS K 6221. Unit: ml / g).

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

In the present invention, the aluminum powder is meant to include aluminum powder and aluminum paste. The aluminum powder whose surface is coated with a surface-coating substance and the aluminum paste whose low-volatile substance is removed are thermoplastic resins. What is kneaded in is preferable.

[0110] Here, the aluminum paste means the presence of mineral spirits and a small amount of higher fatty acids such as stearic acid or oleic acid when aluminum powder is produced by a known method such as a ball mill method, a stamp mill method or an atomizing method. It was originally made into a paste. In the present invention, the aluminum paste and various aromatic monovinyl resins (polystyrene resin, rubber-containing polystyrene resin, etc.), polyolefin thermoplastic resins (various polypropylene resins, various polyethylene resins, acid-modified resins, EVE resins, EEA resins, EAA resins, etc.) , Low molecular weight polyolefin resin, paraffin wax, tackifier, dispersant such as metallic soap, etc. are heated and kneaded, and low volatile substances (mineral spirit, white spirit with strong malodor)
It is preferable to use a volatile substance having a content of 3% or less, preferably 1% or less, particularly preferably 0.5% or less, which has been removed by a vacuum pump or the like, as the aluminum paste compound resin or aluminum paste masterbatch resin.

It is particularly preferable to use it as an aluminum paste masterbatch resin in order to eliminate adverse effects and odors on the photographic light-sensitive material. For example, even if the content of mineral spirits in the master batch resin having an aluminum paste content of 40% by weight is 1.0% by weight, if the aluminum paste concentration in the molded product for photographic light-sensitive material is set to 2% by weight, aluminum 19 parts by weight of natural resin will be kneaded with 1 part by weight of paste masterbatch, and mineral spirits may be removed as a gas during heating during molding, so the content of mineral spirits is 0.05 parts by weight. % Or less. As a result, the photographic light-sensitive material is not adversely affected, and the odor is reduced.

The aluminum powder is not only the molten aluminum made into powder by atomization method, granulation method, rotary disc dropping method, evaporation method, etc., but also aluminum foil is crushed by a ball mill method, a stamp mill method or the like to form flakes. Including those in the shape. Since the aluminum powder alone is unstable, various known surface coating treatments for inactivating the surface of the aluminum powder are performed.

In order to put it into practical use as a molded article for a photographic light-sensitive material of the present invention, the total content of the light-shielding substance is 0.01 to 30% by weight from the viewpoint of quality assurance, photographic performance assurance, moldability and economy.
It changes depending on the shading ability. The total content of carbon black and aluminum powder with excellent light-shielding ability is 0.05 to 20.
Wt% is preferred, 0.1-10 wt% is more preferred, 0.2
~ 7 wt% is most preferred. If the content is less than 0.01% by weight, the light-shielding property will be insufficient and light fog will occur unless the thickness of the molded product for a photographic light-sensitive material is increased. For this reason, the molding speed of the molded product for a photographic light-sensitive material becomes slow (because the cooling time becomes long), and the amount of resin used becomes large, so that it becomes expensive and difficult to put into practical use. When the content exceeds 30% by weight, the dispersibility deteriorates, the generation of microgrids (aggregated impurities) increases, pressure fog and scratches occur on the photographic light-sensitive material, and moisture in the molded product for photographic light-sensitive material The amount increases due to an increase in the amount of water adsorbed on the carbon black, which adversely affects the photographic performance of the photographic light-sensitive material (fogging, abnormal sensitivity, abnormal color development, etc.). Furthermore, the moldability of a molded product for a photographic light-sensitive material is deteriorated (foaming, silver strips, pinholes, short shots, etc.) and the physical strength is lowered, which makes practical application difficult.

Dispersion of a light-shielding substance (carbon black, aluminum powder, an inorganic pigment having a refractive index of 1.50 or more, an inorganic pigment having a specific gravity of 3.4 or more, an inorganic pigment having an oil absorption of 50 ml / 100 g or more) in a resin Properties, improvement of resin fluidity, prevention of generation of microgrit that causes friction fog, pressure fog, and scratches on photographic photosensitive materials, prevention of volatile substances harmful to photographic properties, reduction of moisture absorption, prevention of die lip stains, etc. For this reason, it is preferred that the surface is coated with a surface coating material. Representative examples of surface coating materials are shown below.

(1) Coupling agent Coupling agent coating containing azidosilanes (JP-A-62-62)
-32125, etc.) Silane-based coupling agent coating (aminosilane, etc.) Titanate-based coupling agent coating

(2) Deposit silica and then deposit alumina.

(3) Higher fatty acid metal salt coating such as zinc stearate, magnesium stearate, calcium stearate, etc.

(4) Coating with surfactants such as sodium stearate, potassium stearate, oxyethylene dodecyl amine

(5) A barium sulfide aqueous solution and a sulfuric acid aqueous solution are reacted in the presence of an excess amount of barium ions to produce barium sulfate having an average particle diameter of 0.1 to 2.5 μm, and an aqueous alkali silicate solution is added to this water slurry. To form barium silicate on the surface of barium sulfate, then add mineral acid to the slurry, decompose the barium silicate into hydrous silica and deposit on the surface of barium sulfate to coat

(6) Hydrated metal oxide (one or more hydrated oxides of titanium, aluminum, cerium, zinc, iron, cobalt or silicon) and / or metal oxide (titanium, aluminum, cerium) Surface coating with a composition consisting only of one, two or more of oxides of zinc, iron, cobalt or silicon)

(7) Coating with a polymer having one or more reactive groups selected from the group consisting of aziridine group, oxazoline group and N-hydroxyalkylamide group in the molecule

(8) Surface coating with polyoxyalkylene amine compound

(9) Surface coating with cerium cation, selected acid anion and alumina

(10) Surface coating with an alkoxytitanium derivative having an α-hydroxycarboxylic acid residue as a substituent

(11) Surface coating with polytetrafluoroethylene

(12) Surface coating with polydimethylsiloxane or modified silicon

(13) Surface coating with phosphoric acid ester compound

(14) Surface coating with dihydric or tetrahydric alcohol

(15) Surface coating with olefin wax (polyethylene wax, polypropylene wax)

(16) Surface coating with aluminum hydroxide oxide

(17) Silica or zinc compound (zinc chloride, zinc hydroxide, zinc oxide, zinc sulfate, zinc nitrate, zinc acetate,
One or a combination of two or more such as zinc citrate)
With surface coating

(18) Surface coating with polyhydroxy saturated hydrocarbon, etc.

As a surface coating substance for the above-mentioned light-shielding substance, there are few adverse effects such as fog on the photographic characteristics of the photographic light-sensitive material,
Improves the dispersibility of light-shielding substances, reduces the generation of spots, and improves the fluidity of resin (1), (3), (12), (14), (15),
In addition to (16) and the like, organometallic chelate compounds, various antistatic agents, lubricants, drip-proofing agents, and surfactants are preferable.

Particularly, 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 0.001 to 2% by weight, preferably 0.005 to 1% by weight, particularly preferably By adding 0.01-0.5% by weight,
It has been found that the effect of preventing the above problems can be exhibited. In particular, it not only reduces the adverse effect on the photographic properties of the photographic light-sensitive material but also reduces the motor load, improves the dispersibility of the light-shielding substance, improves the moldability, and makes the appearance of the molded product excellent.

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

Examples of the above monocarboxylic acid include montanic acid, melissic acid, cerotic acid, brisic acid, laxeric acid and the like.

Examples of monohydric alcohols include montyl alcohol, melysyl alcohol, lacsyl alcohol,
Examples include ceryl alcohol and brisyl alcohol.

Since these improve the fluidity of the thermoplastic resin and achieve uniform kneading, they are also very excellent as a surface coating substance for the light-shielding substance. 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 coverage of these light-shielding substances is preferably 0.001 to 5% by weight, more preferably 0.001 to 5% by weight, based on the light-shielding substances such as carbon black or aluminum powder.
It is 0.01 to 3% by weight, most preferably 0.05 to 1.5% by weight. When the coating amount is 0.001% by weight or less, the coating effect is hardly exhibited. If the coating amount exceeds 5% by weight, bleed-out increases with time and slip between the resin and the screw occurs and the discharge amount fluctuates, resulting in large variation in thickness and difficulty in practical application.

The total sulfur content (AST
MD-1619) is 1.0% or less, preferably 0.8% or less, particularly preferably 0.5% or less, and the free sulfur content is 150 ppm or less, preferably 50 ppm or less, particularly preferably 30 ppm or less, according to ASTM D-1506. The ash content is 0.5% or less, preferably 0.4% or less, particularly preferably 0.3% or less,
Aldehyde compound content is 0.2% or less, preferably 0.1%
It is necessary to note that the photographic properties are adversely affected unless the content is controlled below 0.05%.

Further, since cyanide compounds also adversely affect the photographic performance of photographic light-sensitive materials, 4-pyridinecarboxylic acid.
The light-shielding substance has a value of 20 ppm or less, preferably 10 ppm or less, particularly preferably 5 ppm or less, obtained by converting the amount of hydrogen cyanide quantified by the pyrazolone absorption spectrometry into the unit of ppm with respect to the weight of the light-shielding substance.

A lubricant may be added to the packaging material for a photographic light-sensitive material of the present invention. By adding a lubricant,
It is possible to improve film formability, lubricity, dispersibility of a light-shielding substance, and prevent static electricity.

Typical commercially available lubricant names and manufacturer names that do not adversely affect the light-sensitive material are listed below.

(1) Silicone-based lubricant; various grades of dimethylpolysiloxane and its modified products (Shin-Etsu Silicone, Toray Silicone) Silicone-based oil is the second most preferred lubricant after the fatty acid amide-based lubricant. Although this silicone-based oil is expensive, it is optimal as a lubricant added to the heat-sealing layer of the light-sealing bag for photographic light-sensitive materials, which requires complete light-shielding properties, for the following reasons. In particular, as a measure for deteriorating the heat-sealing property such as a lubricant, the ethylene copolymer resin is 5% by weight or more, preferably 20% by weight, particularly preferably 50% by weight (even among ethylene copolymer resins, it is an inexpensive and foreign matter seal The most preferable is ethylene / α-olefin copolymer resin, which has excellent heat resistance, hot tack property, heat seal strength, and physical strength.) The following is added to the thermoplastic resin film layer provided on the inner and outer surfaces of the added abrasion resistant flexible sheet or light shielding bag. Addition of the silicone-based oil described above exerts excellent characteristics not found in conventional packaging materials for photographic light-sensitive materials. That is, in addition to exhibiting the same effects as other lubricity such as improved resin fluidity and lubricity, when used in combination with a light-shielding substance, the dispersibility of the light-shielding substance is improved, and the resin becomes cloudy and haze (ASTM D- 1003) has an effect of increasing the size, and an unexpected effect such as an improvement of the light-shielding ability (20% or more) (the effects of (to be described later) are exhibited).

The silicone oil will be described in detail below. Dimethylpolysiloxane of various grades and its modified products (Shin-Etsu Silicone, Toray Silicone) and polymethylphenylsiloxane, carboxyl modified silicone, olefin modified silicone, polyether modified silicone modified with polyethylene glycol or polypropylene glycol, olefin / polyether modified It is a silicon-based oil containing a modified siloxane bond such as silicone, α-methylstyrene-modified silicone, epoxy-modified silicone, amide-modified silicone, amino-modified silicone and alcohol-modified silicone. In the silicone-based oil, an olefin-modified silicone that has a large effect of lubricating and light-shielding (opacity) with little adverse effect on a photographic light-sensitive material,
Polyether modified silicone, dimethylpolysiloxane,
Amide-modified silicone, carboxyl-modified silicone, olefin / polyether-modified silicone, etc. are excellent. The silicone-based oil improves the friction coefficient of the wear resistant flexible sheet in a heated state, reduces the sliding resistance generated during hot plate sealing by an automatic packaging machine, and prevents wrinkles, thereby providing a beautiful appearance. It is possible to obtain a wear-resistant flexible sheet that has a high degree of sealing performance and an adhesiveness that does not cause slack in the packaged object while maintaining its performance. In addition, it is possible to prevent deterioration of gloss due to sliding and obtain a beautiful seal portion. In the present invention in which silicone oil is also used, the high temperature friction coefficient can be 1.4 or less when sliding heat sealing is performed.

The silicone oil preferably has a viscosity at room temperature in the range of 1000 to 100,000 centistokes, more preferably 5,000 to 30,000 centistokes. The addition amount varies depending on the type and purpose of use, but is 0.01 to 5.0% by weight. It is preferably 0.03 to 3.0% by weight, particularly preferably 0.05 to 1.5% by weight.

The silicone-based lubricant may be used alone or in combination of two or more, or may be used in combination with another lubricant or plasticizer.

The effects of the addition of silicone oil are many as follows for the use of the present invention. It improves the fluidity of the resin, reduces the motor load on the screw, and prevents melt fracture. Sufficient lubricity can be ensured without adding a fatty acid amide that bleeds out to form a white powder. Abrasion resistance flexible sheet in heated condition can reduce friction retention and improve suitability for automatic bag making, prevent wrinkles from occurring during heat sealing and decrease in gloss due to sliding, and obtain beautiful sealing part. . When used in combination with a light-shielding substance, the light-shielding ability can be improved, and the light-shielding property can be ensured even if the amount of the light-shielding substance that reduces the physical properties is reduced.

(2) Oleic acid amide lubricants; Armoslip CP (Lion Akzo), Neutron (Nippon Seika), Neutron E-18 (Nippon Seika), Amide O
(Nitto Kagaku), Alfro E-10 (Nippon Yushi), Diamid O-200 (Nippon Kasei), Diamid G-200 (Nippon Kasei), etc.

(3) Elucic acid amide lubricant; Alfro-P
-10 (Nippon Yushi) etc.

(4) Stearic acid amide lubricants; Alflo-S-10 (Nippon Yushi), Neutron 2 (Nippon Seika),
Diamond Mid 200 screw (Nippon Kasei) etc.

(5) Bis fatty acid amide lubricants; methylenebisbehenic acid amide lubricants, methylenebisstearic acid amide lubricants, methylenebisoleic amide lubricants,
Ethylenebisstearic acid amide lubricant, hexamethylenebisstearic acid amide lubricant, etc. Bisamide (Nippon Kasei), Diamid 200 bis (Nippon Kasei), Armowax EBS (Lion Akzo)
etc

(6) Nonionic surfactant lubricants: Electrostripper-TS-2 (Kao), Electrostripper-TS-3 (Kao), etc.

(7) Hydrocarbon lubricants; liquid paraffin, natural paraffin, microwax, synthetic paraffin, polyethylene wax (number average molecular weight is 10,000 or less, preferably 8,000 or less, particularly preferably 6,000 or less), polypropylene wax (number average) Molecular weight 10,000 or less, preferably 8,000 or less, particularly preferably 6,000 or less), chlorinated hydrocarbon, fluorocarbon, etc.

(8) Fatty acid type lubricant; higher fatty acid (preferably C ₁₂ or more), oxy fatty acid, etc.

(9) 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.

(10) Alcohol lubricants; polyhydric alcohols,
Polyglycol, polyglycerol, etc.

(11) Metal soap; higher fatty acids such as lauric acid, stearic acid, succinic acid, stearyl lactic acid, lactic acid, phthalic acid, benzoic acid, hydroxystearic acid, ricinoleic acid, naphthenic acid and oleic acid, and Li, Na, Mg,
Ca, Sr, Ba, Zn, Cd, Al, Sn, Cd, P
Examples thereof include compounds with a metal such as b, and those particularly preferred in the present invention are metal stearate compounds such as magnesium stearate, zinc stearate, and calcium stearate.

In addition, there are the following lubricants which have a small effect of improving the lubricity but have an effect of improving the dispersibility of the light-shielding substance and the resin extrudability.

Hydrocarbon lubricants; liquid paraffin, natural paraffin, microwax, synthetic paraffin, polyethylene wax (number average molecular weight of 10,000 or less, preferably 8,000 or less, particularly preferably 6,000 or less), polypropylene wax (number average molecular weight of 10,000) Below, preferably
8,000 or less, particularly preferably 6,000 or less), fluorocarbon, etc.

Fatty acid type lubricants; higher fatty acids (preferably having 12 or more carbon atoms), oxyfatty acids, etc.

Ester lubricants; lower alcohol esters of fatty acids, polyhydric alcohol esters of fatty acids, polyglycol esters of fatty acids, fatty acid alcohol esters of fatty acids, etc.

Alcoholic lubricants; polyhydric alcohols, polyglycols, polyglycerols, etc.

The amount of the lubricant added is preferably 0.001 to 5.0% by weight, more preferably 0.01 to 3.0% by weight, and most preferably 0.03 to 2.0% by weight. If the amount added is less than 0.001% by weight, the above-mentioned effect of adding the lubricant cannot be obtained and only the kneading cost increases. On the other hand, if the amount added exceeds 5.0% by weight, slippage between the molten resin and the screw of the extruder is likely to occur, the discharge amount of the resin becomes unstable, and the layer thickness varies greatly. In addition, stickiness and bleed-out easily occur, which makes practical application difficult.

A fatty acid metal salt may be added to the packaging material for a photographic light-sensitive material of the present invention for the purpose of inactivating a substance which adversely affects photographic performance. By adding the fatty acid metal salt, bleed-out can be reduced, the organic nucleating agent can be prevented from scattering, and the dispersibility of the organic nucleating agent can be improved. Further, this fatty acid metal salt improves the dispersibility and moldability of the light-shielding substance, and further neutralizes and harmless halides contained in the resin, which adversely affect the photographic properties of the photographic light-sensitive material. The quality is also improved. Examples of the fatty acid metal salt include higher fatty acids such as lauric acid, stearic acid, lactic acid, succinic acid, stearyl lactic acid, hydroxystearic acid, ricinoleic acid, naphthenic acid, oleic acid and erucic acid, and Li, Na, Mg, Ca and Sr. , Ba, Z
There are compounds with metals such as n, Cd, Al, Sn and Pb.

The amount of the fatty acid metal salt added is 100
0.01 to 10.0 parts by weight, preferably 0.1 to
5.0 parts by weight is more preferred. The amount added to the entire molded product is preferably 0.01 to 5.0% by weight, more preferably 0.03 to 3.0% by weight, and most preferably 0.05 to 1.5% by weight.

If the amount added is less than 0.01% by weight, there is almost no effect of addition and only the kneading cost increases. If it exceeds 5.0% by weight, bleed out may occur, or the resin and screw may slip, resulting in unstable discharge.
In addition to frequent molding failures, it lacks uniform kneading properties.

A surfactant may be added to the packaging material for a photographic light-sensitive material of the present invention. By adding a surfactant, the antistatic property is improved, the lubricity is improved, the bleed-out of the lubricity is suppressed, the drip-proof property is improved, the kneading property of the light-shielding substance and the additive is improved, the fluidity of the resin composition is improved, and blocking is performed. Prevention can be improved.

Typical examples of the nonionic surfactant are shown below. Polyethylene glycol fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene fatty alcohol ether, polyoxyethylene alkylphenyl ether, polyoxyethylene glycerin fatty acid ester, polyoxyethylene fatty amine,
Sorbitan monofatty acid ester, fatty acid benthaelisitol, ethylene oxide adduct of fatty alcohol, fatty acid ethylene oxide adduct, fatty acid amino or fatty acid amide ethylene oxide adduct, alkylphenol ethylene oxide adduct, alkylnaphthol ethylene oxide adduct , Ethylene oxide adducts of partial fatty acid esters of polyhydric alcohols, alkylamine derivatives, and various nonionic antistatic agents described in JP-B No. 63-26697, page 120.

Typical examples of the anionic surfactant are shown below. Ricinoleic Acid Sulfate Sodium Salt, Various Fatty Acid Metal Salts, Silinoleic Acid Sulfate Sulfate Sodium Salt, Sulfated Ethylaniline Oleate, Olefin Sulfate Ester, Oleyl Alcohol Sulfate Soda Salt, Alkyl Sulfate Ester, Fatty Acid Ethyl Sulfonate , Alkyl sulfonate, alkyl naphthalene sulfonate, alkylbenzene sulfonate, succinate sulfonate, phosphate ester and the like.

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

Typical examples of the amphoteric surfactant are shown below. Carboxylic acid derivatives, imidazoline derivatives, betaine derivatives, etc.

The amount of the surfactant added is 0.01 to 5.0% by weight.
Is preferable, 0.05 to 3.0% by weight is more preferable, and 0.1 to 1.
Most preferred is 5% by weight. If the addition amount is less than 0.01% by weight, the above-mentioned various effects of addition of the surfactant cannot be exhibited and only the kneading cost increases. Also, the addition amount is 5.
If it exceeds 0% by weight, foaming and pinholes are likely to occur, slipping between the molten resin and the screw of the extruder is likely to occur, the discharge amount of the resin becomes unstable, and the fluctuation of the layer thickness becomes large. In addition, the amount of bleed-out increases and stickiness and blocking easily occur, which makes practical application difficult.

[0173] The packaging material for a photographic light-sensitive material of the present invention is prevented from being exposed to dew, and the additives such as a nucleating agent, a lubricant and an antioxidant which are easy to bleed out are prevented from precipitating in a white powder form. Contains drop material. This drip-proof substance includes all substances that make the contact angle of water 45 degrees or less, preferably 35 degrees or less. Particularly preferred representative antidrip agents are shown below, but the present invention is not limited thereto. Further, any two or more of a water-absorbing substance, a hygroscopic substance and a drip-proofing agent can be mixed and used.

Further, when a container for photographic film containing a drip-proof substance is subjected to surface activation treatment such as corona discharge treatment, ozone contact treatment, plasma treatment or the like, the anti-fog action and drip-proof action will be more effectively exhibited. preferable.

Representative examples of preferred drip-proofing agents are described below. Diglycerin monostearate, polyglycerin monopalmitate, sorbitan monolaurate, sorbitan monostearate, sorbitan monooleate, sorbitan monoerucate, polyoxyethylene sorbitan fatty acid ester, stearic acid monoglyceride, palmitic acid Monoglyceride, oleic acid monoglyceride, lauric acid monoglyceride, polyoxyethylene nonylphenol ether, sorbitan sesquipamitate, diglycerin sesquioleate, sorbitol fatty acid ester, sorbitol fatty acid / dibasic acid ester, diglycerine fatty acid / dibasic acid ester, glycerin fatty acid・ Dibasic acid ester, sorbitan fatty acid, dibasic acid ester, sorbitan pal Mitate, sorbitan stearate, sorbitan palmitate / propiolene oxide 3 mol adduct, sorbitan palmitate / propiolene oxide 2 mol adduct, sorbitol stearate, sorbitol stearate / ethylene oxide 3 mol adduct, diglycerin palmitate, Glycerin palmitate, glycerin palmitate / ethylene oxide 3 mol adduct, etc.

The amount of the drip-proof substance added is 0.01 to
5.0% by weight is preferred. Particularly, 0.1 to 3.0% by weight is preferable. If the addition amount is less than 0.01% by weight, the antifogging effect is hardly exhibited and only the kneading cost increases. Also,
Additives such as lubricants and antioxidants that easily bleed out cannot be prevented from being deposited in the form of white powder.

When the amount added exceeds 5.0% by weight, the antifogging effect is sufficiently exhibited, but the effect of increasing the amount is almost lost, and the cost is increased. The problem is that the surface of the container tends to be sticky, dusty and dusty, and if it adheres to the photograph, uneven development speed occurs.

An antiblocking agent may be added to the packaging material for a photographic light-sensitive material of the present invention. Blocking can be prevented by adding an antiblocking agent.

As the antiblocking agent, higher fatty acid polyvinyl ester, n-octadecylurea, N, N '
-Dioleyl oxamide, N-ethanol stearic acid amide, silica (including natural and synthetic silica), calcium carbonate, talc (magnesium silicate), aluminum silicate, calcium silicate, dicarboxylic acid ester amide, and the like. And silica is preferred. This silica has an average particle size of 0.3 to 20 μm, especially 0.5 to 15 μm.
It is preferably μm. If it is less than 0.3 μm, cohesiveness is strong and many spots occur. In addition, the antiblocking effect is also small. When it exceeds 20 μm, silica is exposed on the surface of the resin film and the surface of the resin film is not only rough, but also scratches are likely to occur on the photographic light-sensitive material.

The amount of antiblocking agent added is 0.01 to 5.
0 wt% is preferable, 0.05 to 3.0 wt% is more preferable,
Most preferred is 0.1 to 2.0% by weight. If the addition amount is less than 0.01% by weight, the antiblocking effect is small and only the kneading cost increases, and if the addition amount exceeds 5.0% by weight,
Occurrence of lump-shaped non-uniform failures (bugs) increases, and not only the photographic light-sensitive material is subject to pressure damage and scratches, but also the physical strength and heat sealability of the resin film deteriorate.

An organic nucleating agent and an inorganic nucleating agent can be added to the packaging material for a photographic light-sensitive material of the present invention. By adding a nucleating agent, it is possible to improve properties such as Young's modulus, cooling effect, rigidity, and film moldability by promoting crystallization.

Examples of the organic nucleating agent include carboxylic acids, dicarboxylic acids, their salts and anhydrides, salts and esters of aromatic sulfonic acids, aromatic phosphinic acids, aromatic phosphonic acids, aromatic carboxylic acids, and other aluminum. Salt, aromatic metal phosphate, alkyl alcohol having 8 to 30 carbon atoms,
Condensates of polyhydric alcohols and aldehydes, alkylamines, etc., such as aluminum p-t-butylbenzoate, 1,2,3,4-dibenzylidene sorbitol, disubstituted benzylidene sorbitol compounds represented by the following formula

[0183]

[Chemical 6] {In the formula, R ₁ and R ₂ are alkyl, alkoxy or halogen having 1 to 8 carbon atoms, m and n are both 0 to 3 and m + n ≧ 1. }, A metal salt of stearyl lactic acid such as calcium or magnesium, or a compound represented by the following formula such as N- (2-hydroxyethyl) -stearylamine.

[0184]

[Chemical 7] {In the formula, R ₃ is an alkyl group having 8 to 30 carbon atoms, and k
And l are both 0 to 10 and k + 1 ≧ 1. }, 1,2-hydroxystearic acid lithium salt, sodium salt, potassium salt, calcium salt, magnesium salt and other metal salts, stearyl alcohol, lauryl alcohol and other alkyl alcohols, sodium benzoate,
Examples include benzoic acid and sebacic acid.

Representative examples of particularly preferable sorbitol compounds among the organic nucleating agents are shown below. di- (o-methylbenzylidene) sorbitol o-methylbenzylidene-p-methylbenzylidenesorbitol di- (m-methylbenzylidene) sorbitol m-methylbenzylidene-o-methylbenzylidenesorbitol di- (p-methylbenzylidene) sorbitol m-methylbenzylidene-p-methylbenzylidenesorbitol 1 ・ 3-heptanylidenesorbitol 1,3,2,4-diheptanylidenesorbitol 1,3,2,4-di (3-nonyl-3-pentenylidene) sorbitol 1,3-cyclohexanecarbylidenesorbitol 1,3,2,4-dicyclohexanecarbylidenesorbitol 1,3,2,4- di (p-methylcyclohexanecarbylidene) sorbitol Aromatic hybrocarbon groups or derivatives thereof 1 ・ 3-benzylidene sorbitol 1 ・ 3,2 ・ 4-dibenzylidene-D-sorbitol 1 ・ 3,2 ・ 4-di (m-methylbenzylidene) sorbitol 1 ・ 3, 2 ・ 4-di (p-methylbenzylidene) sorbitol 1 ・ 3,2 ・ 4-di (p-hexylbenzylidene) sorbitol 1 ・ 3,2 ・ 4-di (l-naphthalenecarbylidene) sorbitol 1 ・ 3,2 ・ 4-di (phenylacetylidene) sorbitol 1 ・ 3 ・ 2 ・ 4-di (methylbenzylidene) sorbitol 1 ・ 3 ・ 2 ・ 4-di (ethylbenzylidene) sorbitol 1 ・ 3 ・ 2 ・ 4-di (propylbenzyledene) sorbitol 1 ・ 3 ・ 2 ・ 4 -di (methoxybenzylidene) sorbi tol 1 ・ 3 ・ 2 ・ 4-di (ethoxybenzylidene) sorbitol 1 ・ 3 ・ 2 ・ 4-di (P-methylbenzylidene) sorbitol 1 ・ 3 ・ 2 ・ 4-di (P-chlorbenzylidene) sorbitol 1 ・ 3 ・ 2 ・4-di (P-methoxybenzylidene) sorbitol 1 ・ 3 ・ 2 ・ 4-di (alkilbenzylidene) sorbitol 1 ・ 3 ・ 2 ・ 4-bis (methylbenzylidene) sorbitol aluminum benzoate, etc.

Among the organic nucleating agents, the following dibenzylidene sorbitol compounds are particularly preferable. Particularly preferred in the present invention is a polyolefin resin which is a crystalline resin (preferably a homopolypropylene resin, a propylene / α-olefin block copolymer resin, a propylene / α-olefin random copolymer resin, a density of 0.910 g / cm ³ or more. Homo-polyethylene resin and ethylene / α-olefin copolymer resin with a density of 0.870 g / cm ³ or more) improve Young's modulus, physical strength, rigidity, film molding speed, and reduce molding failures. In addition, the following di-substituted benzylidene sorbitol composition which can improve the offensive odor and the bleed-out, which are the drawbacks of the conventional organic nucleating agents, is particularly preferable. As an essential component of the di-substituted benzylidene sorbitol composition, the compound represented by the general formula (I)

[0187]

[Chemical 8] {In the formula, R and R ′ are each independently a chlorine atom,
Represents an atom or a group selected from the group consisting of a methyl group and an ethyl group}, and a solid powder of a dibenzylidene sorbitol derivative of the formula (II)

CH ₃ (CH ₂ ) nCOOH (II) (wherein n represents 14 to 30, preferably 18 to 27, most preferably 20 to 25) higher fatty acid, Provided is a dibenzylidene sorbitol derivative composition in which a higher fatty acid is contained by coating the surface of a solid powder of the dibenzylidene sorbitol derivative.

General formula (I) preferably used in the present invention
The dibenzylidene sorbitol derivative of
-2,4-di-p-methylbenzylidene sorbitol, 1,3
-2,4-di-p-ethylbenzylidene sorbitol, 1,3
-P-methylbenzylidene-2,4-p-chlorobenzylidene-sorbitol, 1,3-p-methylbenzylidene-2,4
Examples thereof include -p ethylbenzylidene sorbitol and 1,3-p chlorobenzylidene-2,4p methylbenzylidene sorbitol.

In a preferred embodiment of the organic nucleating agent of the present invention, a dibenzylidene sorbitol derivative in which R and R'in the general formula (I) each independently represent a methyl group or a chlorine atom is used.

Particularly suitable dibenzylidene sorbitol derivatives are 1,3-2,4-dipmethylbenzylidene sorbitol, 1,3-p methylbenzylidene-2,4-p chlorobenzylidene sorbitol and 1,3-p chloro. Benzylidene-2,4-p-methylbenzylidene sorbitol.

Preferred examples of the higher fatty acid of the formula (II) preferably used as the organic nucleating agent in the present invention are behenic acid and
Of the stearic acid and palmitic acid, behenic acid is most preferred, and stearic acid is the second most preferred.

The particle size of the solid powder of the dibenzylidene derivative used in the organic nucleating agent composition of the present invention does not need to be particularly limited, and a particle size distribution of 30 to 100 mesh is preferably used.

The preferable organic nucleating agent composition of the present invention is 95 to 50 parts by weight, preferably 90 to 50 parts by weight of the dibenzylidene derivative.
5 to 50 parts by weight of higher fatty acid, preferably 10 parts by weight
In the range of up to 50 parts by weight, the content of both components is 100 parts by weight.

A preferred organic nucleating agent composition of the present invention is a solid emulsion of the dibenzylidene sorbitol derivative which is added to an aqueous emulsion containing the above fatty acid in the above proportion in the above proportion and stirred to form a solid powder of the dibenzylidene sorbitol derivative. It can be prepared by forming a coating layer of higher fatty acid on the surface, filtering the dibenzylidene sorbitol derivative powder having the higher fatty acid coating, and then washing and drying.

The aqueous emulsion of higher fatty acid used in the above method is, for example, a solution of a higher fatty acid in an organic solvent solution having a concentration of 5 to 50% by weight, preferably 10 to 50% by weight, and a small amount of a surfactant such as 100% of higher fatty acid. 1 to parts by weight
It can be easily obtained by dispersing in water using 10 to 10 parts by weight, preferably 2 to 5 parts by weight.

The presence of the higher fatty acid coating formed on the surface of the solid powder of the dibenzylidene sorbitol derivative can be confirmed by observing the coating by dyeing it.

A preferred organic nucleating agent composition of the present invention is
Examples of the polyolefin resin effectively used as an additive for improving physical strength, non-bleed-out property and odorless property include aliphatic monoolefins having 2 to 6 carbon atoms and having a number average molecular weight of 10,000 to 1,000,000, Preferably 150,000-80
Homopolymers or copolymers of high molecular weight of 0,000, particularly preferably 20,000 to 600,000, particularly preferably 30,000 to 400,000, such as homopolypropylene resin, low density homopolyethylene resin, high density homopolyethylene resin, linear polyethylene (ethylene -Α-olefin copolymer resin and ethylene-propylene copolymer resin. Particularly, a crystalline polyolefin resin having a high crystallinity is preferable, and the crystallinity is 50% or more, preferably 70% or more, particularly preferably 80% because the addition effect of the organic nucleating agent is effectively exhibited.
As described above, most preferably 90% or more of the polyolefin resin. The molecular weight distribution (weight average molecular weight / number average molecular weight) of these polyolefin resins is 2 to 20, preferably 3 to
15, particularly preferably 3.5 to 12, most preferably 4
Is ~ 10. Here, the molecular weight distribution is obtained from the molecular weight measured by the GPC method.

In a preferred organic nucleating agent composition of the present invention, 0.005 to 5.0 parts by weight, preferably 0.01 to 3.0 parts by weight, of a higher fatty acid corresponding to 100 parts by weight of a polyolefin resin as a dibenzylidene sorbitol derivative component. A dibenzylidene sorbitol derivative coated with is preferably used.

The preferred organic nucleating agent composition of the present invention can be blended with the polyolefin resin by mixing by any known mixing means. The preferable organic nucleating agent composition of the present invention can be used as a masterbatch in a polyolefin resin containing a high concentration of the organic nucleating agent, if necessary.

In the preferred organic nucleating agent composition of the present invention, it is important that the surface of the solid particles of the dibenzylidene sorbitol derivative is coated with a higher fatty acid, and the dibenzylidene sorbitol derivative and the higher fatty acid are simply added to the polyolefin resin. Even if added and mixed, the effects described above cannot be achieved. Further, 180 ° C or higher, preferably 190 ° C or higher,
Particularly preferably, the above-mentioned effects cannot be achieved unless the heat history of 200 ° C. or higher is passed.

This heat history may be carried out once. For example, the above-mentioned di-substituted benzylidene sorbitol composition described in detail in the polyolefin resin composition of the present invention as a preferred organic nucleating agent composition of the present invention is 0.01 After adding ~ 2.0% by weight, 1
80 ° C or higher, preferably 190 ° C or higher, particularly preferably 200 ° C
The light-shielding polyolefin resin film may be molded by using the above pelletized by heating, and the above-mentioned effects can be achieved even if the resin temperature at this time is 180 ° C. or less. Also, by setting the resin temperature to 180 ° C or higher (in the present invention, it is expressed as having undergone a heat history of 180 ° C or higher twice), the physical properties and rigidity are extremely excellent, and the film surface has high gloss, wrinkles and stripes. It is possible to mold a thermoplastic resin film in which appearance defects such as the above are hardly observed.

In order to maximize the effect of the addition of the nucleating agent, the polyethylene resin, in particular, the molecular weight distribution (weight average molecular weight / number average molecular weight) is 1.5 to 12, preferably 2 to 10,
It is particularly preferable to apply it to a polyethylene resin of 2.5 to 7.

The preferred organic nucleating agent composition of the present invention does not impair physical properties, bleed-out resistance, rigidity and other characteristics when blended with a polyolefin resin composition as compared with the prior art. In some cases, these properties can be further improved, and at the same time, it has excellent odorlessness, and at the same time, appearance defects such as wrinkles and streaks are less likely to occur on the film, and the film formability can be improved to improve the film forming speed. ,
It has an excellent effect of reducing molding failures. That is, in the polyolefin resin composition of the present invention,
By including the above-mentioned di-substituted benzylidene sorbitol composition, it is possible to provide a packaging material for a photographic light-sensitive material having excellent physical strength, rigidity, bleed-out resistance, odorlessness, film moldability, and abrasion resistance. .

The reason why the preferable organic nucleating agent composition of the present invention exerts the above excellent effects is not always clear, but
Conventional benzaldehyde, which is a raw material for producing dibenzylidene sorbitol, and benzaldehyde derivatives, such as p-substituted benzaldehyde, which is a raw material for producing the dibenzylidene sorbitol derivative of the present invention, have an odor, and both of them are inevitable after purification. ) Tends to remain in a small amount to cause an offensive odor of the light-shielding thermoplastic resin film, and dibenzylidene sorbitol (derivative) causes a slight decomposition even when the thermoplastic resin film is formed using the thermoplastic resin composition to cause an offensive odor. It can be a cause. In a preferred organic nucleating agent composition of the present invention, solid particles of a specific dibenzylidene sorbitol derivative of general formula (I) are used and the particles are coated with a specific higher fatty acid of general formula (II), and By simultaneously satisfying the requirements of, the offensive odor presumed to be based on the raw material benzaldehyde or decomposed benzaldehyde, is significantly reduced in the thermoplastic resin film using the thermoplastic resin composition, and the rigidity, At the same time, the above-mentioned physical properties such as physical strength are excellent.

The various organic nucleating agents may be used alone, in combination with various inorganic nucleating agents, or in combination of two or more of the organic nucleating agents. Further, the surface of the organic and / or inorganic nucleating agent may be coated with various fatty acids, fatty acid compounds, lubricants such as silicon,
It can be coated with a dispersant such as a coupling agent, a plasticizer and a surfactant, a wetting agent and the like.

The total amount of the nucleating agent added is 0.005 to 5.0% by weight,
0.01-3.0% by weight is preferred, 0.03-2.0% by weight is more preferred, and 0.05-1.0% by weight is most preferred. Addition amount is 0.0
If it is less than 05% by weight, almost no effect is exerted and only the blending cost is required, and if it exceeds 5.0% by weight, there is no effect of increasing the amount and only the cost is increased. It is not preferable because it may have an adverse effect, generate a bad smell, adhere to a ring die or the like, bleed out, or reduce the physical strength.

As a method of blending the nucleating agent, there are a compound method, a dry blend method, a master batch method and the like, but the master batch method is preferable because it has good workability and does not cause environmental pollution. In particular, it is preferable to prepare it simultaneously with the production of the colored masterbatch containing the light-shielding substance, because it is economical and the workability is good. Since it has a high dryness and is easily scattered, it is difficult to mix it as it is. It is advisable to add a small amount of a dispersant or a wetting agent to mix it. Various lubricants with a number average molecular weight of 500 are effective as dispersants.
~ 10,000 various low molecular weight polyolefin resins, various waxes, various carboxylic anhydrides, various higher fatty acids, etc.,
Lubricants such as various fatty acid metal salts, various silicones and various oleic acid amides are particularly preferable. As a wetting agent, DOP,
Various plasticizers such as DHP can be used.

Also, various higher fatty acids, fatty acid amides,
It is also preferable to coat a pure product of a fatty acid such as a fatty acid metal salt or a fatty acid compound on the surface of the organic nucleating agent or blend it to enhance the dispersion effect and prevent bleed-out. Furthermore, the polyolefin resin and 180 ° C. or higher, preferably 190
It is preferable to use it as pellets kneaded at a heat history of not less than 0 ° C, particularly not less than 200 ° C from the viewpoint of exerting the effect of the nucleating agent. That is, by adding these additives,
It improves physical strength, increases rigidity, and reduces generation of white powder due to abrasion, and also reduces generation of white powder due to crystallization or bleed-out of the organic nucleating agent. Further, it is possible to prevent the foul odor of the organic nucleating agent, and to prevent the generation of static electricity and the blocking prevention property.
In this case, in order to prevent deterioration, oxidative decomposition and coloration of the above various organic nucleating agents, various dispersants and various thermoplastic resins, the various antioxidants, radical scavengers and antioxidants such as citric acid, phosphoric acid, etc. It is preferable to add one or more agents.

The addition amount of the sorbitol-based organic nucleating agent is 0.01
~ 5.0 wt%, 0.01 ~ 3.0 wt% is preferred, 0.03 ~ 2.0
% By weight is more preferred, and 0.05 to 1.0% by weight is most preferred. If the amount added is less than 0.01, the effect of adding the organic nucleating agent is small and only the kneading cost increases. On the other hand, if the amount added exceeds 3.0% by weight, there is almost no effect of increasing the amount, resulting in cost increase, and bleed-out or precipitation at the die exit of the film forming machine, causing streak failure.

Examples of the inorganic nucleating agent include alkali metal hydroxides such as lithium hydroxide, sodium hydroxide and potassium hydroxide, alkali metal oxides such as sodium oxide, lithium carbonate, sodium carbonate, potassium carbonate and sodium hydrogen carbonate. , An alkali metal carbonate such as potassium hydrogen carbonate, an alkaline earth metal hydroxide such as calcium hydroxide, magnesium hydroxide and barium hydroxide, an alkaline earth metal oxide such as calcium carbonate and calcium oxide, and the like.

The nucleating agent is not limited to these, and other known nucleating agents can be used. Needless to say, the nucleating agent is not limited to a single type and two or more types can be used in combination. The amount of the inorganic nucleating agent added is preferably 0.01 to 5.0% by weight, more preferably 0.05 to 3.0% by weight.

In order to sufficiently exert the effect of the nucleating agent, the resin temperature at the time of kneading with a crystalline resin (particularly preferably a polyolefin resin) is 170 ° C. or higher, preferably 185 ° C. or higher,
Particularly preferably, the temperature is 195 ° C. or higher (passes heat history). It is preferable that the heat history at 170 ° C. or higher is performed once or more, preferably twice (at least twice for pelletizing and molding).

During this heat history, an antioxidant and / or
Alternatively, it is preferably used in combination with at least one radical scavenger.

When the above organic nucleating agent and inorganic nucleating agent are used in combination with various fatty acid metal salts, the dispersibility is improved, the halogen compounds which adversely affect the photographic properties are neutralized, and the addition effect is further improved. In addition, bleed-out is also reduced, which is preferable. The amount of the various fatty acid metal salts (particularly, higher fatty acid metal salts having C ₈ or more) added is preferably 0.01 to 2.0% by weight, more preferably 0.03 to 1.0% by weight, and 0.0
Most preferred is 5 to 0.5% by weight. This fatty acid metal salt also improves the photographic property because it neutralizes the halides contained in the resin, which adversely affect the photographic light-sensitive material, and renders them harmless.

The following plasticizers can be added to the packaging material for photographic light-sensitive materials of the present invention in order to improve the uniform dispersibility of the nucleating agent and the light-shielding substance.

Representative examples of the plasticizer are shown below. (1) Phthalic acid-based plasticizers Dibutyl phthalate, Dihebutyl phthalate, Dioctyl phthalate, Diisodecyl phthalate, Butyl lauryl phthalate, Ditridecyl phthalate, Butyl benzyl phthalate,
Butylphthalyl butyl glycolate, etc. (2) Phosphate plasticizer, tricresyl phosphate, trioctyl phosphate, etc. (3) Fatty acid plasticizer, tri-n-butyl citrate, dioctyl adipate, dioctyl azelate, dioctyl sebacate, acetyl Methyl ricinoleate, etc. (4) Epoxy plasticizer, alkyl epoxy stearate, 4,5-epoxytetrahydrophthalic acid diisodecyl, etc. (5) Other plasticizers, chlorinated paraffin, polyester, sucrose octaacetate, etc.

The addition amount of the plasticizer is preferably 0.01 to 10.0% by weight, more preferably 0.05 to 7.0% by weight, and most preferably 0.1 to 5.0% by weight. If the added amount is less than 0.01% by weight,
The effect of improving the uniform dispersibility of the light-shielding substance and the effect of improving the blocking adhesion are hardly exhibited, and only the kneading cost increases. If the addition amount exceeds 10.0% by weight, slipping with the screw of the extruder occurs and it becomes impossible to extrude a stable resin amount.

A deodorant can be included in the packaging material for a photographic light-sensitive material of the present invention and the light-shielding bag using the same.

Examples of the deodorant include organic carboxylic acids, mixtures of organic carboxylic acids and zinc compounds, and mixtures of organic carboxylic acids, zinc compounds and aluminum compounds.

Examples of the organic carboxylic acid include aliphatic polycarboxylic acids, aromatic polycarboxylic acids, reaction products of these aliphatic or aromatic polycarboxylic acids with polyhydric alcohol compounds, and acidic polyester compounds having a carboxyl group at the end. There is.

Examples of the aliphatic polycarboxylic acid include oxalic acid, malonic acid, succinic acid, adipic acid, fumaric acid, methylfumaric acid, maleic acid, methylmaleic acid, itaconic acid, acetylenic acid, malic acid, methylmalic acid and citric acid. There are di- or tricarboxylic acids such as acids, isocitric acid, mesaconic acid and citraconic acid, or salts thereof, and particularly preferred are citric acid, fumaric acid or salts thereof.

Examples of the aromatic polycarboxylic acid include phthalic acid, terephthalic acid, isophthalic acid, trimellitic acid, pyromellitic acid, benzenehexatricarboxylic acid, naphthalenedicarboxylic acid, naphthalenetricarboxylic acid, naphthalenetetracarboxylic acid and azobenzenetetracarboxylic acid. And aromatic anhydrides thereof and the like, and particularly preferred are benzenetricarboxylic acid and trimellitic acid.

As the acidic polyester compound having a carboxyl group at the terminal, a polyester having a terminal carboxyl group obtained by reacting a polycarboxylic acid such as phthalic acid with a polyhydric alcohol such as ethylene glycol or diethylene glycol, or an acidic cellulose derivative modified with a polycarboxylic acid Etc.

Examples of the zinc compound used in combination with the organic carboxylic acid include zinc oxide, zinc chloride, zinc sulfate, zinc phosphate, inorganic zinc salts of zinc carbonates and zinc citrate, and organic zinc of zinc fumarates. Salts and the like, preferably in the range of organic carboxylic acid: zinc compound = 1: 0.1 to 3.0 parts by weight.

The aluminum compound used in combination with the organic carboxylic acid and the zinc compound is aluminum sulfate, potassium, etc., and organic carboxylic acid: zinc compound: aluminum compound = 1: 0.1: 0.1 to 1: 3:
A range of 3 parts by weight is preferred.

Other deodorants include iron II compounds and L
-Ascorbic acid, iron II compound and L-ascorbic acid and alum, metal phthalocyanine, activated carbon fiber, metal porphyrins, aliphatic polycarboxylic acid (tricarboxylic acid, citric acid, oxalic acid, malonic acid, malic acid, succinic acid, etc. ), Metal porfurazines, organic acid-based composites (Dainichi Seika Kogyo's dim shoe, etc.), activated carbon,
Natural organic substances extracted from plants (flavanols, flavanols, organic polymers, etc.), polyphenols, glyoxal-impregnated cellulose acetate, oxycarboxylic acid compounds and ferrous salts, oxycarboxylic acid compounds having two or more carboxyl groups in the molecule Ferrous salt and sulfate or sulfite,
L-ascorbic acid and ferrous salt, oxycarboxylic acid compound and L-ascorbic acid and ferrous salt, ascorbic acid and humic acid and iron salt, iron and vitamin C, iron compound, iron salt of inorganic acid, organic acid Iron salt, a mixture of iron citrate, silicic acid, aluminum, calcium and potassium, deo crystal, cristobalite (a kind of silicate mineral), sodium alumina silicate (zeolite), Cu, Zn, Al, F
e, Ni, Sn, Pb, Ti, Mn, Co and Ag sulfates, chlorides, nitrates and acetates. And you may use these in multiple numbers.

The amount of deodorant added is 0.01 to 30% by weight.
The flexible sheet layer is selected according to the type, shape and composition of the flexible sheet layer. It is preferably 0.05 to 20% by weight, particularly preferably 0.1 to 10% by weight. These deodorants are preferably used as a deodorant flexible sheet contained in various flexible sheets.

As the deodorant flexible sheet, for example, a deodorant is applied and / or impregnated and / or kneaded and / or
Or evaporated cellophane, various films, paper, adhesive layer,
A metal foil, a metal thin film processed flexible sheet, a non-woven fabric, a foamed sheet, a fiber, and a rubber sheet are preferable.

The thickness of the deodorant flexible sheet is not particularly limited, but from the viewpoints of bag-making suitability, stacking suitability, cost, deodorizing ability, etc., it is 1 to 100 μm, preferably 10 to 50 μm, and deodorizing in the case of an adhesive layer. In the case of spray coating, solution coating, powder spraying, or electrostatic attachment of the agent, the thickness is 1 to 50 μm in terms of the thickness of the deodorant alone, and 6 μm to 3 mm, preferably 10 to 500 μm when using a general flexible sheet.
This thickness varies greatly depending on the concentration of the deodorant and the density of the flexible sheet, but if it is too thick, the rigidity of the packaging bag becomes too high, the suitability for bag making becomes poor, and it becomes expensive, making it difficult to put into practical use.

The packaging material for photographic light-sensitive materials of the present invention and the light-shielding bag using the same may contain an oxygen scavenger.

The oxygen scavenger includes sulfite, bisulfite, nithionate, hydroquinone, catechol, resorcin, pyrogallol, erosion salt, ascorbic acid, and / or
Or a salt thereof, isoascorbic acid and / or a salt thereof, glucose, lignin, dibutylhydroxytoluene, butylhydroxyanisole, ferrous salt, a metal powder-containing oxygen scavenger such as iron powder, carbon dioxide-generating oxygen scavenger, carbonic acid Gas absorption type oxygen absorber, Crispearl, Zeolite, Hytrosulfite, Glucose oxidase, Salcomine, Alkali metal sulfide, Alkali carbonate, Sodium thiosulfate,
Examples include sodium alum, disodium hydrogen phosphate dodecahydrate, sodium silicate hydrate, sodium borate hydrate, ferrous silicate sulfate 7 hydrate, activated clay and mordenite.
Then, one or more of these oxygen scavengers are selected and used.

Preferably, one containing hydrosulfite as a main component, one containing an organic substance such as L-alcorbic acid as a main component, one containing iron powder as a main component, iron and silicic acid.
Mixed composition with at least one selected from the group consisting of ferrous sulfate heptahydrate, sodium alum, disodium hydrogen phosphate dodecahydrate, sodium silicate hydrate, and sodium borate hydrate, hydrosulfite And calcium hydroxide or sodium bicarbonate and activated carbon, iron powder and accelerating salts and hydrous substances, oxidizable metal powder and sodium thiosulfate and solid reaction aids, iron powder and sodium thiosulfate and activated carbon, activated iron oxide, Metal oxides, palladium, sugars, and enzyme systems. Commercially available products include "Ageless" manufactured by Mitsubishi Gas Chemical Co., Inc., "Keplon" manufactured by Kepron Co., Ltd., and "Tamotsu" manufactured by Toyo Pulp Co., Ltd.

A hygroscopic agent may be contained in the paving material for photographic light-sensitive material of the present invention and the light-shielding bag using the same.

The hygroscopic agent is, for example, a water-absorbing resin containing a carboxylate group, a crosslinkable polyacrylic acid alkali metal salt,
Carboxylate-containing ethylene copolymer resin, acrylic acid acrylic metal graft starch cross-linking agent, cross-linked polyvinyl alcohol-alkali metal acrylate copolymer, cross-linked polyvinyl alcohol / maleic anhydride copolymer, cellulose modified product, cross-linking of water-soluble polymer Agent, self-crosslinking alkali metal acrylate polymer, polyacrylic acid or its alkali salt, polyacrylamide or its partial hydrolyzate, polyvinylpyrrolidone, sulfonated polystyrene, sodium polyacrylamide 2-methylpropanesulfonate, starch-acrylonitrile Graft polymer of or its hydrolyzate, Polyacrylonitrile hydrolyzate, Copolymer of acrylamide and acrylic acid, Carboxymethyl cellulose, Vinyl styrene sulfonic acid, Polyacryloyl Mannich reaction product of amide, polyacrylamine, homopolymer of dimethylaminoethyl methacrylate or copolymer with acrylamide, homopolymer of dimethylaminoethyl methacrylate converted to quaternized ammonium salt with methyl chloride, or copolymerization thereof with acrylamide Substance, polydimethylallylamine quaternary ammonium salt, quaternized vinylbenzylamine polymer, chitosan acetylating agent, condensation reaction product of epichlorohydrin with polyvalent amine or monoamine, polyamide polyamine epichlorohydrin system on super absorbent polymer particle surface After adsorbing thermosetting resin, thermosetting resin, copolymer of hydrophilic vinyl monomer (derivative of acrylamide etc.) and hydrophobic vinyl monomer (derivative of methacrylate), isobutylene-maleic anhydride Sodium salt of acid copolymer, sodium salt of starch and graft copolymer of acrylic acid and acrylic acid derivative, partially crosslinked carboxymethyl cellulose polybasic acid, partially crosslinked polyethylene oxide, partially crosslinked polyacrylic acid, high water absorption Coating of water-soluble polymer, mixture of super-absorbent polymer and inorganic substances (attapulgite, kaolin, talc, diatomaceous earth, etc.), super-absorbent resin having anionic dissociative group and super-absorbent resin having cationic dissociative group , A mixture of starch acrylic acid, sodium acrylate copolymer,
Sodium starch acrylate copolymer, activated carbon, silica gel, calcium chloride and the like.

Of these, starch or cellulose or a synthetic polymer is preferably used as the raw material having a large water absorbing ability.

The water absorbent resin has a water absorption capacity of 30 g / g or more, preferably 50 g / g or more, particularly preferably 80 g / g.
As described above, most preferably 100 g / g or more.

An ion exchange function is provided for the purpose of adsorbing a gas that adversely affects the photographic properties of the photographic light-sensitive material to render it harmless, improve dispersibility in combination with a light-shielding substance, and react with a foul-smelling substance to eliminate odor. An inorganic substance having is added.

The packaging material for a photographic light-sensitive material of the present invention and the light-shielding bag using the same may contain an inorganic substance having an ion exchange function.

As an inorganic substance having an ion exchange function, zeolite (natural zeolite analcime, erioni
te, mordenite, etc. as components) (synthetic zeolites A, NA, X, Y, hydroxy sodallte, B, R, T,
various types such as hydroxy cancrinite), the average particle diameter is 0.1 to 7 μm, preferably 0.1 to 5 μm, particularly preferably 0.1 to 3.5 μm, and 0.1 to 10% by weight in the resin composition, preferably 0.2 to 8% by weight, particularly preferably 0.3-6
% By weight. When used in combination with a light-shielding substance, it exhibits dispersibility improvement, deodorizing effect, adsorption of gases harmful to photographic properties, diatomaceous earth, activated clay, synthetic aluminum silicate, synthetic calcium silicate, synthetic magnesium silicate, There are chelating substances such as mica.

As the chelating substance, carboxylic acid type phthalocyanine type metal complexes (metal phthalocyanine tetracarboxylic acid, metal phthalocyanine octacarboxylic acid etc.), iminodiacetic acid type chelate resin, aminocarboxylic acid type chelate resin (EDTA = ethylenediaminetetraacetic acid etc.) , Polyamine type chelate resin, glucamine type chelate resin, supported chelate resin, 4-dimethylamino-2,6-pyridinedicarboxylic acid chelate resin and the like.

The addition amount of the inorganic substance having an ion exchange function is 0.01 to 10% by weight, preferably 0.05 to 8% by weight, and more preferably 0.1 to 6% by weight. If the addition amount is less than 0.01% by weight, the effect of addition is hardly exerted and only the kneading cost increases. On the other hand, if the addition amount exceeds 10% by weight, the effect of increasing the amount is hardly exhibited, not only the material cost is increased, but also the physical strength of the molded product for a photographic light-sensitive material is lowered and the appearance is deteriorated.

The packaging material for a photographic light-sensitive material of the present invention and the light-shielding bag using the same may contain an aromatic agent.

The fragrances include natural aroma components such as lilac flower essential oil, jasmine, abies oil, cinnamon oil, lavender oil and lemon oil, geraniol, eugenol, n-.
Octyl alcohol, carbitol, cis-chasmon, lemon terpene, menthone, methyl salicylate, methylphenylcarbinol, triethyl citrate,
Benzoic acid prenyl ester, benzoic acid methyl ester,
Microcapsule microparticulation of synthetic aroma components such as benzyl benzoate, citral, d-limonene, geraniol, ethyl cinamate, octanol, benzyl benzoate, alkylene glycol, benzyl salicylate, linalool, vanillin, coumarin, methylnaphthyl ketone, rosephenone. And cyclodextrin, maltosyl cyclodextrin, cyclodextrin, zeolite, starch, talc, etc.

One or more kinds of the above-mentioned deoxidants, deodorants, hygroscopic agents, aromatic agents and inorganic substances (including chelating substances) having an ion exchange function are contained in an amount of 0.01 to 30% by weight, preferably 0.05 to 20. % By weight, more preferably 0.1-10% by weight
Is. If the content is less than 0.01% by weight, the effect of addition is not exhibited and the cost only increases. If the content exceeds 20% by weight, the photographic light-sensitive material will be adversely affected and the material cost will increase, so that it cannot be put to practical use.

A buffer sheet or adhesive layer having a density of 0.8 g / cm ³ or less, preferably 0.5 g / cm ³ or less of the present invention is an oxygen scavenger, a deodorant, a moisture absorbent, an aromatic and an inorganic material having an ion exchange function. 0.01 to 30% by weight of one or more substances or chelating substances is provided and provided on one side of the buffer sheet (atmosphere side = anti-photosensitive material side) with Young's modulus of 50 kg / mm ² or more and heat resistance Oxygen permeability (measured by the same pressure method conforming to ASTM D-3985 of MOCON method) of wear-resistant and heat-resistant flexible sheet is 50cc / m ² · 24 hours · 1 atmosphere · 20
℃ or less, preferably 35cc / m ² · 24 hours · 1 atmosphere · 20 ° C
Below, especially preferably 20cc / m ² · 24 hours · 1 atmosphere · 20
Determined by the cup method of JIS Z-0208 at 40 ° C or lower (40
Single layer sheet or composite laminated sheet having moisture permeability of 10 g / m ² · 24 hours or less, preferably 5 g / m ² · 24 hours or less, particularly preferably 2 g / m ² · 24 hours or less) (Including simultaneous co-extrusion multilayer film), the abrasion resistant flexible sheet with Young's modulus of 50 kg / mm ² or more provided on the other side of the cushioning sheet (photosensitive material side) Oxygen permeability and moisture permeability is 10% or more, preferably 20% or more, particularly preferably 40% or more, most preferably 100% larger than that of heat-resistant flexible sheet (including co-extruded multilayer film) ), The photographic property of the photographic light-sensitive material can be maintained in a state of excellent performance for a long period of time, and the photographic light-sensitive material of high commercial value does not cause discomfort when used by the user. It is possible to provide a light-shielding bag.

On the other hand, considering the case of landfill treatment as waste, degradable plastics which are currently being researched or are introduced into some markets may be used. For example, as a biodegradable polymer I
CI "BIOPOL", UCC "Polycaprolactone"
Etc. or natural that is susceptible to biodegradation,
Alternatively, a polymer that is indirectly disintegrated by adding a synthetic polymer as an additive, or a starch-containing polyethylene or the like can be used.

[0248] In particular, "Bionore" manufactured by Showa Highpolymer Co., Ltd. (chemically synthesized from dicarboxylic acid, etc., which was recently released as a chemically synthesized biodegradable plastic that decomposes into carbon dioxide and water by the action of microorganisms Special polyester resin) or "Matterby" (corn starch and biodegradable modified polyvinyl alcohol polymer alloy) manufactured by Novamont of Italy are used as one or more layers of the packaging material for the photographic light-sensitive material of the present invention. 50% by weight or more, preferably
From the viewpoint of improving the industrial waste treatability, it is preferable to contain 70% by weight or more, particularly preferably 80% by weight, and most preferably 90% by weight or more. In particular, it is preferably used in one or more layers other than the layer which comes into contact with the photographic light-sensitive material to be heat-sealed.

It is also possible to use a photodegradable polymer. For example, an ECO copolymer obtained by copolymerizing ethylene and carbon monoxide in which a carbonyl group is introduced as a photosensitizing group in the main chain during polymerization of polyethylene is used, or a transition metal salt, an oxidation accelerator, a photosensitizer is added as an additive. It is possible to use a material obtained by adding a material or the like to the base polymer and imparting photodegradability thereto.

Furthermore, one or more kinds of degradable polymers such as biodegradable polymers, photodegradable polymers and water-soluble polymers may be used in combination (JP-A-3-1293).
(See Japanese Patent No. 41).

When considering recycling, it is preferable that the cushioning sheet, the abrasion-resistant flexible sheet having a Young's modulus of 50 kg / mm ² or more, and the adhesive layer provided as necessary, are all made of polyolefin resin, particularly polyethylene resin of the same kind. It is preferable to manufacture. When incinerating, use calcium carbonate, clay, titanium oxide, etc. that suppress heat generation.
The amount added is 0.1 to 60% by weight, preferably 0.5 to 50% by weight, and particularly preferably 1 to 30% by weight.

The density is 0.8 g / cm ³ or less, preferably 0.5 g
/ Cm ³ or less, a wear-resistant / heat-resistant flexible sheet having a Young's modulus of 50 kg / mm ² or more and heat resistance provided on one side of the cushioning sheet, and a cushioning sheet provided on the other side of the cushioning sheet. The present invention is a laminated film in which a wear-resistant flexible sheet having a Young's modulus of 50 kg / mm ² or more and a metal layer or various flexible sheets provided as necessary are directly laminated with or without an adhesive layer. The packaging material for photographic light-sensitive material is manufactured.

In the present invention, various known adhesive layers can be used as the adhesive layer in accordance with the required characteristics.
Adhesives used for this adhesive layer include various polyethylenes (LDPE, L-LDPE, MDPE, HDP
E) Resins, various thermoplastic resins of polyolefin such as polypropylene resins, ethylene-propylene copolymer resins, ethylene-vinyl acetate copolymer resins, ethylene-copolymer resins such as ethylene-ethyl acrylate copolymer resins, ethylene -Acrylic acid copolymer resin, ionomer resin, ethylene copolymer resin, or other thermoplastic resin hot-melt adhesive (extrusion lamination adhesive). There are other heat-melting type rubber adhesives, solution adhesives include wet laminating adhesives, emulsions,
It is a latex adhesive. Representative examples of emulsion adhesives are polyvinyl acetate, vinyl acetate-ethylene copolymers, vinyl acetate and acrylic ester copolymers,
There are emulsions of vinyl acetate and maleic acid ester copolymers, acrylic copolymers, ethylene-acrylic acid copolymers, and the like. Typical examples of the latex type adhesive are natural rubber, styrene butadiene rubber (SBR), acrylonitrile butadiene rubber (NBR), chloroprene rubber (C
There are rubber latexes such as R). As an adhesive for dry lamination, there is an isocyanate adhesive urethane adhesive or the like. Other known adhesives such as paraffin wax, microcrystalline wax, ethylene-vinyl acetate copolymer resin, ethylene-ethyl acrylate copolymer resin blended hot melt laminate adhesive, pressure-sensitive adhesive, heat-sensitive adhesive, etc. Can be used. More specifically, the polyolefin type adhesive for extrusion lamination which is particularly preferable in the present invention includes various polyethylene resins, polypropylene resins, polybutylene resins, and ethylene copolymer (EVE, EEA, etc.) resins, as well as L-LDPE resins. , A part of ethylene with another monomer (α-olefin) copolymerized, Dupon
There are ionomer resins (ionic copolymers) such as "Surrin" manufactured by t company, "Hilamin" manufactured by Mitsui Polychemical Co., Ltd., and acid-modified resins such as "Admer" manufactured by Mitsui Petrochemical Co., Ltd.
Other UV curable adhesives have also begun to be used recently.

Particularly, LDPE resin and L-LDPE resin or blend resin of LDPE resin and L-LDPE resin are preferable because they are inexpensive and have excellent laminating suitability. Acid-modified resins are preferred for improving the adhesive strength. Further, a mixed resin in which two or more of the above-mentioned resins are blended to cover the defects of each resin is particularly preferable because it has excellent laminating suitability. In particular, blending the LDPE resin or L-LDPE resin and the acid-modified polyolefin resin in an appropriate amount ratio makes it possible to obtain an arbitrary adhesive strength, which is particularly preferable in the present invention.

The thickness of the adhesive layer formed by the extrusion laminating method using a thermoplastic resin is usually 6 μm to 10 μm.
0 μm, preferably 7 μm to 50 μm, particularly preferably 9
However, since it is determined based on the cost, the adhesive strength, the laminating speed, the total thickness of the laminated body, etc., the numerical value is not particularly limited.

The adhesive strength of the adhesive layer is to improve the physical strength such as the tear strength of both vertical and horizontal, impact punching strength, gelbotest strength, etc. Peel strength between two laminated materials (180 degree peeling test, ASTM D 903 testing machine used) is 30
A weak adhesive layer having a width of 0 g / 15 mm or less, preferably 100 g / 15 mm or less, and particularly preferably 50 g / 15 mm or less. However, in the bag making process or the laminating process, the strength is such that it does not peel off, and the width is 0.1 g / 15 mm width or more, preferably 1 g / 15 mm width or more, particularly preferably 5 g / 15 mm width or more. The blocking adhesive strength is almost the same (about 30 times the width when the width is 30 mm).

In order to form an adhesive layer having such a weak adhesive strength, the thickness of the adhesive layer is reduced, and the surface of the adherend is subjected to corona discharge treatment, flame treatment, plasma treatment, ultraviolet ray irradiation treatment, electron beam irradiation. Two or more types of poorly compatible resin compositions, which are not subjected to surface treatment such as heat treatment, preheat treatment, anchor coat treatment, etc., and which lower the temperature of the adhesive layer, and form an adhesive layer made of a weak adhesive strength resin composition Or a combination of two or more of the following methods: forming an adhesive layer consisting of 1), forming a multi-layer coextrusion extrusion laminating adhesive layer that facilitates delamination, and the like.

When the packaging material for the photographic light-sensitive material has an easily openable property or when peeling is to be prevented, the adhesive strength is
(180-degree peeling test, using ASTM D 903 tester) 350g / 15mm width or more, preferably 500g / 15mm width or more, particularly preferably 700g / 15mm width or more are laminated via a strong adhesive layer (30mm In the case of the width, the strength is about double).
In order to obtain an adhesive layer having such a strong adhesive strength (in the present invention, referred to as a strong adhesive layer), the reverse of the above-mentioned weak adhesive layer may be performed. An acid-modified polyolefin resin is a preferred adhesive resin for forming a strong adhesive layer.

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

The unsaturated carboxylic acids, including their derivatives, are collectively referred to. Typical examples are acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, tetrahydrophthalic acid, mesaconic acid, angelic acid and citracone. 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, methacryl Ethyl acid, butyl acrylate, butyl methacrylate, glycidyl acrylate, glycidyl methacrylate, maleic acid monoethyl ester, maleic acid diethyl ester, fumaric acid monomethyl ester, fumaric acid dimethyl ester,
Itaconic acid diethyl ester, acrylic acid amide, methacrylamide, maleic acid monoamide, maleic acid diamide, maleic acid-N-monoethylamide, maleic acid-N, N-diethylamide, maleic acid-N-monobutylamide, maleic acid- N, N-dibutylamide, fumaric acid monoamide, fumaric acid 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 matacrylate, sodium acrylate, zinc acrylate, magnesium acrylate, calcium acrylate , Sodium methacrylate, potassium acrylate, potassium methacrylate, N-butyl maleimide, N-phenyl maleimide, maleenyl chloride, glycidyl maleate, dipropyl maleate, aconitic acid anhydride, sorbic acid, etc. Mixed use is also possible.

Of these, acrylic acid, maleic acid, maleic anhydride, and nadic acid are preferable, and maleic anhydride is particularly preferable.

The method for graft-modifying the unsaturated carboxylic acids in the modified polyolefin resin is not particularly limited. For example, the method disclosed in Japanese Examined Patent Publication (Kokoku) No. 43-21421 and the like which react in a molten state, and the Japanese Examined Patent Publication No.
-15422 and the like, the method disclosed in JP-B-43-18144 and the like to react in a slurry state, the method disclosed in JP-B-50-77493 and the like to react in a gas phase is there.

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

The amount of the unsaturated carboxylic acids used is a polyolefin resin base polymer (various polyethylene resins, various polypropylene resins, various polyolefin copolymer resins, polybutene-1 resin, poly-4) in order to secure adhesive strength.
-Α-olefin copolymer resin such as methylpentene-1 and its copolymer resin) 0.01 to 20 parts by weight, preferably 0.2 to 5 parts by weight, per 100 parts by weight.

An organic peroxide or the like is used to promote the reaction between the polyolefin resin and the unsaturated carboxylic acid.

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-butylper) (Oxy) hexyne, di-t-butylperoxide, cumene hydroperoxide, t-butyl-hydroperoxide, dicumyl peroxide, t-butylperoxylaurate, t-butylperoxybenzoate, 1,3-bis ( t-butylperoxyisopropyl) benzene, cumene hydroperoxide, di-
Examples thereof include organic peroxides such as t-butyl-diperoxyphthalate, t-butylperoxymaleic acid and isopropyl percarbonate, azo compounds such as asobisisobutyronitrile, and inorganic peroxides such as ammonium persulfate.

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

The addition amount of these peroxides is not particularly limited, but 0.005 to 100 parts by weight of the polyolefin resin is added.
It is 5 parts by weight, preferably 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 KK “NOVATEC-A”
P ”(5) Mitsubishi Yuka KK“ MODIC ”(6) Nippon Unicar KK“ NUC-ACE ”(7) Ube Industries KK“ UBE BOND ”(8) Tosoh KK“ Mersen M ”(9) Sumitomo Chemical KK“ Bondine (10) Mitsui DuPont Chemical KK "CMPS" etc. (11) Exxon's "Dexon" (12) Toa Fuel Industry KK "HA Series" (13) Mitsui Toatsu Chemical KK "MITSUI LO"
NPLY ”etc.

The amount of the acid-modified polyolefin resin contained in the adhesive layer is 3 to 90% by weight, preferably 5 to 70% by weight, particularly preferably 7 to 60% by weight, most preferably 10 to 50% by weight. If it is less than 3% by weight, there is almost no effect of improving the adhesive strength. Even if it exceeds 90% by weight, there is no effect of increasing the amount and only the cost increases.

This adhesive layer may contain various known additives. Especially various light-shielding substances, deodorants,
It is preferable to include a deodorant, a fragrance, an oxygen scavenger, etc. according to the purpose.

In the packaging material for photographic light-sensitive material of the present invention,
Furthermore, the following may be added as other additives.

<Examples of Other Additives> (Types of Additives) (Examples of Representatives) (1) Stabilizers: lead-based, cadmium-based, zinc-based, alkaline earth metal-based, organic tin-based, etc. (2) Difficult Combustion agents; phosphoric acid esters, halogenated phosphoric acid esters, halides, inorganic substances, phosphorus-containing polyols, etc. (3) Fillers: alumina, kaolin, clay, zeolite, calcium carbonate, mica, talc, titanium oxide,
Silica, etc. (4) Reinforcing agent; glass roving, metal fiber, glass fiber, glass milled fiber, carbon fiber, etc. (5) Foaming agent: Inorganic foaming agent (ammonia carbonate, sodium bicarbonate), organic foaming agent (nitroso type, azo (6) Vulcanizing agent; Vulcanization accelerator, accelerating aid, etc. (7) Degradation inhibitor: Metal deactivator, peroxide decomposing agent, etc. (8) Coupling agent: Silane-based, titanate-based , Chrome, aluminum, etc. (9) Various thermoplastic resins, polyolefin elastomers, synthetic rubber, etc.

By heat-melt-adhering the heat-sealing layer of the packaging material for a photographic light-sensitive material as described above,
Create a light-shielding bag for photographic material. The form of the light-shielding bag for the photographic light-sensitive material is not particularly limited, and examples thereof include a single flat bag, a double flat bag, and a single gusset bag. As a method of heat melting, a hot plate bonding method, an impulse bonding method,
There are ultrasonic bonding method and high frequency bonding method.

On the surface of the abrasion-resistant and heat-resistant flexible sheet of the packaging material for photographic light-sensitive material of the present invention and the light-shielding bag using the same, a bar code, a CI mark, a product name, a handling instruction, a product identification mark, a product identification It is possible to print characters or symbols necessary for the function such as color, or to enhance the commercial value. Alternatively, in order to improve the printability, the abrasion resistance, and the commercial value, the coating layer may be applied to the whole surface or a part thereof. An ink that is harmless to the photographic light-sensitive material is selected as the ink used for these printings, and can be selected from commonly used offset printing inks, gravure printing inks, UV inks and the like. The coating material used for the coating layer can be selected from various types of resins and resin solutions in which lacquer is made into a solution, an ultraviolet curable resin, an electron beam curable resin, and the like.

Typical synthetic resins used in these printing inks or coating layers are copolymer resins mainly composed of vinyl chloride, vinyl-amino resins, alkyd-vinyl resins, oil-free alkyd resins, and salt vinegar. Bi-based, nitrified cotton, polyester resin, polyamide urethane resin, polyacrylic resin, ethylene vinyl acetate resin, vinyl ether resin, urethane vinyl acetate resin, vinyl chloride vinyl urethane resin, modified alkyd resin, melamine / alkyd resin, modified phenolic resin, high Molecular polyester / amino resin, low molecular polyester / amino resin, alkali-soluble resin (rosin-modified maleic acid resin, styrene-maleic acid resin, styrene-acrylic acid resin, acrylic ester acrylic acid resin, methacrylic ester acrylic acid resin), Hydrosol type resin (styrene malein Resin, styrene acrylic acid resin, α-methylstyrene acrylic acid resin, acrylic acid ester acrylic acid resin, methacrylic acid ester acrylic acid resin), emulsion type resin (styrene resin, styrene acrylic acid ester resin, acrylic acid ester copolymer resin, As a resin for a methacrylic acid ester copolymer resin) or VU ink, a polymer having an acrylic unsaturated group is generally used. Typical examples are polyester / acrylic acid ester, polyester / urethane resin / Acrylic ester, epoxy resin / acrylic ester, pentaerythritol triacrylate, trimethylolpropane triacrylate, hexanediol diacrylate, neopentyl glycol diacrylate, triethylene glycol diacrylate And hydroxyethylenemethacrylate.

Various commonly known coloring agents are used in combination with these printing inks or coating liquids for coating layers.
Examples of the colorant used include various pigments and azo pigments (azo lakes; disclosed in JP-A-63-44653).
Carmine 6B, red 2B, insoluble azo; monoazo yellow (PY-1, 3), disazo yellow (PY-12, 13,
14, 17, 83), pyrazolo orange (PO-B-34), vulcan orange (PO-16), condensed azo type; chromophtal yellow (PY-93, 95), chromophtal red (PR)
-144, 166), polycyclic pigments (phthalocyanine type; copper phthalocyanine blue (PB-15, 15-1, 15-3), copper phthalocyanine green (PG-7), cioxazine type;
Dioxazine violet (PV-23), isoindolinone type; isoindolinone yellow (PY-109, 110),
Slen-based; perylene, perinone, flavantron, thioindigo, lake pigments (malachite green, rhodamine B, rhodamine G, Victoria blue B) and inorganic pigments (oxides: titanium dioxide, red iron oxide, sulfates; precipitated barium sulfate, carbonates) Settling calcium carbonate, silicate;
Examples thereof include hydrous silicate, anhydrous silicate, metal powder; aluminum powder, bronze powder, zinc powder, other carbon black, yellow lead, ultramarine blue, and navy blue). Further, these pigments may be added as a light-shielding substance to the above-mentioned resin layer or the like. In addition to these, oil-soluble dyes and dispersible dyes are also used. Other solvents, dispersants, wetting agents, defoamers, leveling agents, thickeners, etc.
Additives such as stabilizers, crosslinking agents and waxes are used. Synthetic resins and colorants used as these printing ink compositions are applied as coating materials for coating layers on the surface of packaging materials and light-shielding bags using them to improve commercial value, improve printability, and improve abrasion resistance. It is also preferable to use it for the purpose of improving the light-shielding property and improving the photographic property. The thickness of printing ink and coating layer can be freely selected according to the method and purpose, but the photographic property,
It is preferable to make a decision based on total evaluation such as economic efficiency and product value.

Further, a coating material for forming various coating layers as a base coat or a top coat so that the packaging value of the photographic light-sensitive material of the present invention and the light-shielding bag using the same can be improved in commercial value and printing of printing ink can be beautiful and colored. Can be applied. As the paint resin and pigment, those for printing inks described above can be used, but UV paint, melamine / alkyd paint, urethane paint and melamine paint are particularly preferable. The top coat is preferably a transparent lacquer coating, silicone coating, urethane coating, acrylic lacquer coating applied in a thin layer of 0.1 to 30 μm, preferably 0.3 to 20 μm, particularly preferably 0.5 to 10 μm.

Further, the packaging material for photographic light-sensitive material of the present invention can be used not only for the above-mentioned light-shielding bag for photographic light-sensitive material but also for packaging various forms of photographic light-sensitive material. For example, shrink packaging, collective packaging, JP-A-63-287848, JP-A-56-40535, JP-A-57-121941, JP-A-5
Light-shielding bag of sheet film package for light room loading such as JP-A-121942 and JP-B-61-20593, JP-B-63-1
5872, Jikken 3-36993, Jikken 3-42437
It can be used as a packaging film for an X-ray film used for dentistry, such as Japanese Patent Publication No. 63-78948 and Japanese Utility Model Publication No. 63-200837.

[0280] Also, alternative applications of light-shielding paper for roll-shaped photographic film (110 size, 126 size, 120 size, 220 size), JP-A-59-55756, JP-A-60-13386, and JP-A-Sho. No. 60-26051, No. 60-167796, No. 63-6449, No. 63-6452, No. 3-47547, No. 3-54937 Kaihei 3-86358 Publication, Actual Kaihei 3-96648 Publication, Actual Fairness 2-
6444, U.S. Pat. No. 4,911,299, JP 2-7
There are applications such as light-shielding materials (guides, etc.) for daytime loading packages of strip-shaped photosensitive materials such as JP 2347, and applications for light-shielding materials of photosensitive material packages such as JP-A-3-43651 and JP-A-3-53243. .

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

(1) Silver halide photographic light-sensitive material (printing film, color photographic paper, color film, master paper for printing, DTR light-sensitive material, computer typesetting film and paper, microfilm, movie film, self-developing photograph Photosensitive materials, direct positive film and paper, etc.)

(2) Heat-developable photographic light-sensitive material (heat-developable color light-sensitive material, heat-development black-and-white light-sensitive material (for example, Japanese Examined Patent Publication Nos. 43-4921 and 43-4924, "Basics of photographic engineering", silver salt photography) Pages 553 to 555 (published by Corona Publishing Co., 1879) and Research Tis Closure, June 1978, pages 9 to 15 (RD
-17029) etc. Furthermore, JP-A-59-
No. 12431, No. 60-2950, No. 61-52343 and U.S. Pat. No. 4,584,267, a transfer type heat-developable color light-sensitive material)))

(3) Photosensitive / thermosensitive recording material (JP-A-3-72)
Recording material using photothermography (photosensitive / thermosensitive image forming method) described in Japanese Patent No. 358, etc.

(4) Diazonium photographic light-sensitive material (4-morpholinobenzenediazonium microfilm, microfilm, copying film, printing plate material, etc.)

(5) Azide- and diazide-based photographic light-sensitive materials (light-sensitive materials containing para-azidobenzoed, 4,4'diazidostilbene, etc., eg copying films, printing plate materials, etc.)

(6) Quinonediazide photographic light-sensitive material (orthoquinonediazide, orthonaphthoquinonediazide compound, such as benzoquinone (1,2) -diazide-
(2) Photosensitive materials containing 4-phenylsulfonic acid phenyl ether, etc., such as printing plates, copying films, adhesion films, etc.)

(7) Photopolymers (photosensitive materials containing vinyl monomers, printing plate materials, adhesion films, etc.)

(8) Polyvinylcinnamic acid ester-based photographic light-sensitive material (eg printing film, IC resist, etc.)

[0290] In addition, photosensitive substances that are altered or deteriorated by various kinds of light, oxygen, sulfurous acid gas, etc., such as foods (butter, peanut bags, margarine, snack products, knobs, confectionery, tea, paste, etc.), pharmaceuticals (gastrointestinal drug) , Powdered medicines such as cold medicine, granular medicines), dyes, pigments, photographic developing chemicals,
It can also be applied to photographic fixing chemicals, toner, etc.

[0291]

In the packaging material for photographic light-sensitive materials of the present invention, the abrasion-resistant and heat-resistant flexible sheet withstands heat when heat-sealing the layer having heat-sealing property.

[0292]

Embodiments of the packaging material for a photographic light-sensitive material of the present invention will be described with reference to the drawings. 1 to 7 are partial cross-sectional views showing the layer structure of the packaging material for a photographic light-sensitive material.

The photographic photosensitive material packaging material shown in FIG. 1 has a Young's modulus of 50 kg / mm which can be heat-sealed to one side (photosensitive material side) of the foamed sheet 1 as a buffer sheet via the adhesive layer 2. ² or more abrasion resistant flexible sheet layers 3
a is laminated, and this abrasion-resistant flexible sheet 3a has heat sealability. On the other side, the adhesive layer 2 is used to provide abrasion resistance with a Young's modulus of 50 kg / mm ² or more.
A metal thin film processed flexible sheet 6 obtained by processing the metal thin film layer 5 is laminated on the heat resistant flexible sheet layer 4.

[0294] The packaging material for photographic photosensitive materials shown in Figure 2, instead Young's modulus with heat sealing of 50 kg / mm ² or more wear-resistant flexible sheet layer 3a, a Young's modulus of 50 kg / mm ² with a heat-sealing It is the same as the packaging material for a photographic light-sensitive material shown in FIG. 1 except that the multilayer coextrusion film 8a composed of the abrasion-resistant / heat-resistant flexible sheet layer 3a and the thermoplastic resin layer 7a is laminated.

The packaging material for photographic light-sensitive material shown in FIG. 3 is the same as the packaging material for photographic light-sensitive material shown in FIG. 2 with the adhesive layer 2 and the thermoplastic resin layer between the foamed sheet 1 and the metal thin film processed flexible sheet 6. 7'is laminated.

The photographic light-sensitive material packaging material shown in FIG. 4 has a Young's modulus of 50 kg which is heat-sealed on one side (the photographic light-sensitive material side) of the foamed sheet 1 as a buffer sheet via the adhesive layer 2. / Mm ² or more flexible sheet layer 3a
And a thermoplastic resin layer 7a, a multilayer blocking laminated film 9a obtained by blocking and adhering two multilayer coextruded films 8a is laminated on the other side, and the Young's modulus is 50 kg / mm ² or more through the adhesive layer 2a. -The heat resistant flexible sheet layer 4 is laminated.

The packaging material for the photographic light-sensitive material shown in FIG. 5 has a heat-resistant seal on one side (the photographic light-sensitive material side) of the foamed sheet 1 as a cushioning sheet and has a Young's modulus of 50 kg / mm ² or more and is abrasion-resistant and flexible. Seat layer 3a and Young's modulus 50kg
A three-layer coextruded film 10a comprising a wear-resistant and heat-resistant flexible sheet layer 4 having a thickness of at least 1 / mm ² .

The photographic light-sensitive material packaging material shown in FIG. 6 has a heat-sealing Young's modulus of 50 kg / mm ² instead of the wear resistant flexible sheet layer 3a having a Young's modulus of 50 kg / mm ² or more. 1 shown in FIG. 1 except that a five-layer coextruded resin film 13a composed of a wear resistant flexible sheet layer 3a having a size of mm ² or more, a modified resin layer 11, an intermediate layer 12, a modified resin layer 11 and a thermoplastic resin layer 7a is laminated. It is the same as the packaging material for photographic light-sensitive materials.

In the packaging material for photographic light-sensitive material shown in FIG. 7, the metal thin film processed flexible sheet 6 and the heat-sealing layer 14 are provided as adhesive layers on one side (on the photographic light-sensitive material side) of the foamed sheet 1 as a buffer sheet. Stacked over two,
The metal thin film processed flexible sheet 6 is laminated on the other side with the adhesive layer 2 interposed therebetween.

Next, an embodiment of the light-shielding bag for a photographic light-sensitive material of the present invention will be described with reference to FIGS. 8 and 9.

FIG. 8 is a perspective view of a light-shielding bag for a photographic light-sensitive material. In FIG. 8, reference numeral 15 is a light-shielding bag for photographic light-sensitive material,
This light-shielding bag 15 for photographic light-sensitive material is made by heat-sealing two wrapping materials 16, 16 for photographic light-sensitive material. The packaging material 16 for a photographic light-sensitive material is arranged such that the layers having a heat-sealing property are opposed to each other, and the edges of the three sides of the packaging material 16 are heat-sealed sealing portions 17.

FIG. 9 is also a perspective view of a light-shielding bag for a photographic light-sensitive material. The photographic photosensitive material packaging bag 15 shown in FIG. 9 is made by folding a sheet of photographic photosensitive material packaging material 16 and heat-sealing both side edges of the packaging material 16 to form seal portions 17. The heat seal has a shape that has unevenness in the vertical direction and does not enter from both ends.

FIG. 10 is a schematic side view of an automatic bag making apparatus for producing a flat bag having two sides heat-sealed, and FIG. 11 is a schematic plan view of the automatic bag making apparatus.

The automatic bag-making apparatus shown in these figures is provided with a roll 22 for feeding the packaging material 21 for photographic light-sensitive material, and is for holding the packaging material 21 for photographic light-sensitive material fed from the roll 22 at a predetermined position. A packaging material guide board 23 having a space formed in the center through which a conveyer for conveying products can pass.
The cutter 24 is provided at the base end of the packaging material guide substrate 23, and the sensor 25 for detecting the tip of the packaging material 21 for the photographic photosensitive material is provided at the tip. Further, a pair of heat sealing devices 26 are provided above and below the left and right sides corresponding to the central conveyor of the substrate 23.

In such an automatic bag-making apparatus, the packaging material 21 for photographic light-sensitive material is pulled out from the roll 22 and cut by the cutter 24, and the packaging material 21 for photographic light-sensitive material of a predetermined length along the packaging material guide substrate 23. And hang it vertically. Then, the photosensitive material 27 is pushed while folding the packaging material 21 for photographic photosensitive material, and both ends of the overlapping packaging material 21 for photographic photosensitive material are heat-sealed.

An example of the photographic photosensitive material package will be described with reference to FIGS. 12 and 13. FIG. 12 is a diagram showing a process for producing a conventional photographic light-sensitive material package. In the photographic light-sensitive material package shown in this figure, a photographic light-sensitive material 31 is stored in a 5-layer laminated packaging bag 32. It is housed in a metal can 34 sealed with a tape 33, and three metal cans 34 are housed in a corrugated cardboard box 35.

FIG. 13 is also a diagram showing a process of producing a photographic light-sensitive material package of the present invention product and a comparative product. The photographic light-sensitive material package shown in this figure is a packaging bag in which the photographic light-sensitive material 41 is sealed with a tape 47. An outer package (Box) that includes a lower lid 43, an outer box 44, and an upper lid 45 in a state of being housed in 42 and 20 of the packaging bags 42 being stacked.
It is collectively referred to as Bin in the art). Note that reference numeral 46 is a pallet for a forklift during transportation.

[Inventive Product 1] A roll-shaped packaging material for a photographic light-sensitive material having a width of 1200 mm and having a layer structure sectional view corresponding to FIG. 2 was used.

The foamed sheet 1 has a foaming ratio of 3 with a thickness of 1.0 mm.
It is a closed-cell type cross-linked low-density homopolyethylene resin foam sheet having a 0-fold cross-linking degree of 45%.

Flexible sheet 3a having a heat-sealing property on the photographic light-sensitive material and having a Young's modulus of 50 kg / mm ² or more
Has a MI of 0.8 g / 10 minutes, a density of 0.955 g / cm ³ , a crystallinity of 93%, a melting point of 132 ° C., a Vicat softening point of 125 ° C., and is 86.9% by weight of a low-pressure homopolyethylene resin, and a MI of 7 g / Ten
Ethylene acrylate with a density of 0.930 g / cm ³ , a Vicat softening point of 58 ° C and an ethyl acrylate comonomer content of 20% by weight
Ethyl acrylate copolymer resin 5% by weight, calcium stearate 3% by weight, tetrakis [methylene-3 (3.
5-di-tert-butyl-4-hydroxyphenyl) propionate] methane 0.05% by weight, 2.6-di-tert-butyl-para-cresol 0.05% by weight, pH as a light-shielding substance is 7.0, carbon black 100% by weight Volatile content is 0.
6% by weight (0.05% by weight of free sulfur), oil absorption is 105 ml / 1
00g, 5% by weight of furnace carbon black with an average particle diameter of 25mμ, thickness 25μm, Young's modulus 52kg / mm
^{2 is} a light-shielding polyolefin resin layer.

Light-shielding thermoplasticity in two-layer coextruded film
The resin layer 7a has an MI of 2.0 g / 10 minutes and a density of 0.905 g / cm.
³, Low-pressure solution with a crystallinity of 43% and a Vicat softening point of 72 ° C
Ethylene butene containing 15% by weight of butene-1 in the polymerization method
-1 copolymer resin 84.7% by weight, tocopherol 0.1 weight
%, Tetrakis [methylene-3 (3.5-di-tert-
Butyl-4-hydroxyphenyl) propionate]
Tan 0.05% by weight, magnesium stearate 2% by weight,
Erucic acid amide 0.05% by weight, synthetic silica 0.2% by weight, before
The same ethylene / ethyl acrylate copolymer tree as in item 1a
From 8% by weight of fat and 5% by weight of furnace carbon black
, Thickness is 25μm, Young's modulus is 27kg / mm ²The light-shielding effect of
It is a ren copolymer resin layer.

The two-layer coextrusion light-shielding film layer 8a composed of the above two layers has a resin temperature of the flexible sheet 3a of 200 ° C. and a resin temperature of the light-shielding thermoplastic resin layer 7a of 180 °.
Blow-up ratio after melt-kneading separately by two extruders at
Total thickness 5 by blown film molding method at 1.3
It is a 0 μm light-shielding two-layer coextrusion blown film.

The metal thin film processed flexible sheet 6 is a vacuum deposited aluminum biaxially stretched nylon resin film,
Flexible sheet 4 is 15μm thick, Young's modulus is 175kg
/ Mm ² , a melting point of 163 ° C, a Vicat softening point of 150 ° C is a biaxially stretched nylon 6 resin film, and the metal layer 5 is a vacuum-deposited aluminum layer having a thickness of 400Å.

The adhesive layer 2 had MI of 5.6 g.
/ 10 minutes, consisting of 97.92% by weight of high-pressure homopolyethylene resin having a density of 0.920 g / cm ³ , 2% by weight of magnesium stearate, and 0.08% by weight of 2,6-di-tert-butyl-para-cresol (abbreviation BHT). Using the homopolyethylene resin composition layer, the foamed sheet 1, the metal-working thin film flexible sheet 6 and the two-layer coextruded film 8a were adhered to each other at a resin temperature of 310 ° C. with an air gap of 110 mm by an extrusion laminating method to a thickness of 17 μm.

A roll-shaped packaging material obtained by dividing the packaging material for photographic light-sensitive material into 600 mm widths was equally sealed on both sides with a belt-shaped heat sealer at a width of 11.5 mm.
The bottom seal is a bar sealer with a width of 15 mm.
While making a three-sided seal flat bag of 580 mm, horizontal dimension 480 mm
One roll of 35 mm width x 3000 ft long positive-type photographic film for movies was hermetically sealed, and the upper opening was double folded with a width of 15 mm and then sealed with a cellophane tape having a width of 2 cm. Then, this packaging bag was placed in an octagonal lid-fitting type cardboard box to complete the packaging body.

The product I of the present invention has pinhole properties, abrasion resistance,
Impact perforation strength, tear strength, etc. are larger than those of Comparative Product I, and fog is less likely to occur.
There were few eye blemishes and die slip streaks, and the surface smoothness was excellent.

[Invention Product II] A roll-shaped packaging material for a photographic light-sensitive material having a width of 1200 mm and having a layered sectional view corresponding to FIG. 2 was used.

The metal thin film processed flexible sheet 6 is an aluminum vacuum-deposited spunbonded non-woven fabric, and the flexible sheet 4 has a thickness of 70 μm and a Young's modulus of 138 kg / mm ^{2 and} is made of Spanbonded Olefin non-woven fabric “TYVEK” manufactured by Dupont, USA.
Spunbond non-woven fabric made of 1444A ”(registered product)
The metal layer 5 is a vacuum-deposited aluminum layer having a thickness of 500Å. Other configurations and bag making methods are the same as those of the product I of the present invention.

The product II of the present invention has pinhole properties, abrasion resistance,
Impact perforation strength, tear strength, etc. were higher than those of Comparative Product I.

[Invention Product III] A roll-shaped packaging material for a photographic light-sensitive material having a width of 1200 mm and having a layer structure sectional view corresponding to FIG. 4 was used.

The foam sheet 1 has a foaming ratio of 3 with a thickness of 1.0 mm.
It is a closed-cell type cross-linked low-density homopolyethylene resin foam sheet having a 0-fold cross-linking degree of 60%.

The flexible sheet 4 has a thickness of 80 μm, Young's modulus of 138 kg / mm ² , and is Spanbonded Olef of Dupont, USA
It is a spunbonded nonwoven fabric made of in-woven fabric "TYVEK 1444A" (registered product).

In the multilayer blocking laminated film 9a, the heat-sealable flexible sheet 3a having a Young's modulus of 50 kg / mm ² or more has an MI of 2.1 g / 10 minutes and a density of 0.930 g.
/ Cm ³ , crystallinity 68%, Vicat softening point 125 ° C, low-pressure method ethylene-hexene-1 copolymer resin 20% by weight, M
I is 0.7 g / 10 min, density is 0.945 g / cm ³ , and crystallinity is 67.
%, 69.35 wt% of ethylene / 4 methylpentene-1 copolymer resin by low pressure method having a Vicat softening point of 102 ° C., MI of 5.0
g / 10 minutes, density 0.932 g / cm ³ , Vicat softening point 62 ° C
5% by weight of ethylene / ethyl acrylate copolymer resin having an ethyl acrylate comonomer content of 16% by weight, zinc stearate 0.5% by weight, tetrakis [methylene-3 (3 ′ · 5′-di- tert-butyl-4'-
Hydroxyphenyl) propionate] methane 0.05% by weight, vitamin E 0.10% by weight, volatile matter as a light-shielding substance
Light-shielding polyolefin with a thickness of 25 μm and Young's modulus of 62 kg / mm ² , consisting of 0.5% by weight or less of 3% by weight of aluminum powder whose surface is coated with stearic acid and 2% by weight of titanium oxide whose surface is coated with dihydric alcohol. In the resin layer, the thermoplastic resin layer 7a has an MI of 1.0 g / 10 minutes and a density of 0.905 g.
/ Cm ³ , crystallinity 38%, Vicat softening point 83 ° C. 60% by weight of low-pressure ethylene / butene-1 copolymer resin, MI
2.0 g / 10 minutes, density 0.920 g / cm ³ , crystallinity 58%,
Vicat softening point 106 ° C low pressure method ethylene octene-
1 copolymer resin 21.9% by weight, furnace carbon black 3% by weight, which is the same light-shielding substance as the product I of the present invention, MI
Of 6 g / 10 min, density of 0.930 g / cm ³ , Vicat softening point
78 ° C, 5% by weight of ethylene vinyl acetate copolymer resin having a comonomer content of 15% by weight, 2.6-di-tert-butyl-
It is a thermoplastic resin layer mainly composed of an ethylene copolymer resin having a thickness of 20 μm and composed of 0.1% by weight of para-cresol. Then, the above two layers are pressure-bonded with a squeeze roll and are blocking-adhered with a peel strength of 5 g / 15 mm width.

Then, the adhesive layer 2 has a MI of 2.4 g.
/ 10 min, 60% by weight of high-pressure homopolyethylene resin with a density of 0.920 g / cm ³ , MI 6 g / 10 min, density 9.30 g / c
m ^3, ethyl acrylate comonomer content of 18 wt% of ethylene-ethyl acrylate copolymer resin 5 wt% of zinc stearate 0.5 wt%, 2-6-di -tert- butyl -p
ara-cresol 0.1 wt%, pH 7.7, carbon black 100 wt% volatile matter 0.6 wt% (the amount of free sulfur is 0.
08% by weight), oil absorption 76ml / 100g, average particle size 21m
3% by weight of furnace carbon black and MI of 20
Air gap of extrusion laminating method at a resin temperature of 305 ° C. using a polyethylene resin composition layer consisting of 36.4% by weight of ethylene / butene-1 copolymer resin of low pressure method having a density of 0.920 g / cm ³ and a density of 0.9 / 10 g / cm ^3. Bonded with a thickness of 110 μm and a thickness of 20 μm.

Using the packaging material for photographic light-sensitive material as described above, the same package was prepared by the same method as the product I of the present invention.

The product III of the present invention had larger pinhole properties, wear resistance, impact drilling strength, tear strength, etc. than the comparative product I.

[Invention Product IV] A roll-shaped packaging material for a photographic light-sensitive material having a width of 1200 mm and having a layer structure sectional view corresponding to FIG. 1 was used.

The same as the product I of the present invention except that a flexible sheet 3a was used instead of the two-layer coextrusion film 8a. MI is 2.0 as this flexible sheet 3a.
g / 10 minutes, density 0.905 g / cm ³ , crystallinity 43%, Vicat softening point 72 ° C. low-pressure solution polymerization method butene-1 content 15 wt% ethylene-butene-1 copolymer Resin 84.7% by weight, tocopherol 0.1% by weight, tetrakis [methylene-3 (3.5-di-tert-butyl-4-hydroxyphenyl) propionate] methane 0.05% by weight, magnesium stearate 2% by weight, erucic acid amide 0.05% by weight %, Synthetic silica 0.2% by weight, the same ethylene / ethyl acrylate copolymer resin as 1a 8% by weight, furnace carbon black 5% by weight, and a thickness 25 μm, Young's modulus 27 kg / mm ² light-shielding ethylene A copolymer resin layer was used. Other configurations and bag making methods are the same as those of the product I of the present invention.

The product IV of the present invention has pinhole property, wear resistance,
Impact perforation strength, tear strength, etc. were higher than those of Comparative Product I.

[Invention Product V] A roll-shaped packaging material for a photographic light-sensitive material having a width of 1200 mm and having a layer structure sectional view corresponding to FIG. 7 was used.

The cushioning sheet 1 has a foaming ratio of 2 with a thickness of 0.5 mm.
Closed-cell type cross-linked ethylene with 0 times 70% cross-linking degree
It is a butene-1 copolymer resin foam sheet.

The heat seal layer 14 has an MI of 0.9 g / 10
Min, density 0.950 g / cm ³ , crystallinity 89%, Vicat softening point 123 ° C. 20% by weight of low-pressure homopolyethylene resin,
Ethylene / butene-1 copolymer resin with MI 4.0g / 10min, density 0.935g / cm ³ , Vicat softening point 126 ° C 71.4
% By weight, MI 2.5 g / 10 min, density 0.920 g / cm ³ , crystallinity 62%, Vicat softening point 107 ° C. high pressure radical polymerization low density homopolyethylene resin 5% by weight, magnesium stearate 0.5 % By weight, 0.1% by weight of vitamin E, 3% by weight of the same furnace carbon black as the product I of the present invention
Is a light-shielding polyolefin resin layer having a thickness of 100 μm and a Young's modulus of 67 kg / mm ² .

The metal thin film processed flexible sheet 6 and the adhesive layer 2 are the same as those of the product I of the present invention. The bag making method is also the same as that of the product I of the present invention.

The product V of the present invention has pinhole property, wear resistance,
Impact perforation strength, tear strength, etc. were higher than those of Comparative Product I.

[Product VI of the Invention] A roll-shaped packaging material for a photographic light-sensitive material having a width of 1400 mm and having a layered sectional view corresponding to FIG. 3 was used.

The cushioning sheet 1 has a thickness of 0.5 mm and an expansion ratio of 3
0% (density 0.03 g / cm ³ ) closed cell type cross-linking degree of 75%
Is a crosslinked low-density polyethylene resin foam sheet.

The abrasion-resistant and heat-resistant flexible sheet 6 having a Young's modulus of 50 kg / mm ² or more and heat resistance provided on one side of the buffer sheet is an aluminum vacuum-deposited biaxially stretched polyester resin film having a thickness of 13 μm. , The flexible sheet 4 has a thickness of 12 μm, Young's modulus of 215 kg / mm ² ,
A polyethylene terephthalate resin film having a melting point of 260 ° C., and the metal layer 5 is a vacuum-deposited aluminum layer having a thickness of 350 Å.

The light-shielding thermoplastic resin layer 7a, which is laminated between the buffer sheet 1 and the abrasion-resistant and heat-resistant flexible sheet 6 having heat resistance with the adhesive layers 2 and 2, has an MI of 2.5.
g / 10 min, density 0.920 g / cm ³ , crystallinity 35%, melting point 105 ° C, Vicat softening point 96 ° C 96.85% by weight ethylene-octene-1 copolymer resin, erucic acid amide as a lubricant 0.05% by weight, Irgnox 1010 and 1076 as antioxidants
0.05% by weight, 3% by weight of the same furnace carbon black as the product I of the present invention, thickness 35 μm, Young's modulus 35
It is a light-shielding ethylene / α-olefin copolymer resin layer of kg / mm ² .

The other side of the buffer sheet 1 (photosensitive material
Side) has a Young's modulus of 50 kg / mm ²More wear resistance
Flexible sheet with heat sealability
Flexible sheet 3a has a MI of 0.4 g / 10 minutes and is dense.
The degree is 0.960 g / cm³, Crystallinity 95%, melting point 138 ℃,
High-density homopolyethylene resin with a cut softening point of 130 ° C 91.
7% by weight, MI 2.4 g / 10 min, density 0.925 g / cm³, Yui
Crystallinity is 62%, melting point is 101 ℃, Vicat softening point is 92 ℃
Low-density homopolyethylene resin 5% by weight, L as lubricant
0.05% by weight of carboxylic acid amide, tetrakis as antioxidant
[Methylene-3- (3.5-di-tert-butyl-4-hi
Droxyphenyl) propionate] methane 0.05 weight
%, 1,3,2,4-di-p-methylpropyl as an organic nucleating agent
Njilidene sorbitol 0.2% by weight, as a light-shielding substance
pH 7.0, volatile matter 0.5% by weight, oil absorption 93ml / 100
Furnace carbon black with an average particle size of 21 mμ
3% by weight, thickness 30μm, Young's modulus 61kg / mm²
Is a light-shielding high-density homopolyethylene resin layer.

The light-shielding thermoplastic resin layer 7a in the two-layer coextrusion blown film has an MI of 2.0 g / 10 min.
Density 0.920 g / cm ³ , crystallinity 45%, Vicat softening point 98 ° C ethylene 4-methylpentene-1 copolymer resin 91.65% by weight, antioxidant tocopherol 0.05
Wt% and tetrakis [methylene-3- (3.5-di-te
rt-Butyl-4-hydroxyphenyl) propionate] 0.05% by weight of methane, 0.2% by weight of zinc stearate as a lubricant and 0.05% by weight of erucic acid amide, and 5% by weight of the same low-density homopolyethylene resin as the flexible sheet 3a. Is a light-shielding ethylene / α-olefin copolymer resin layer having a thickness of 25 μm and Young's modulus of 38 kg / mm ² . The two-layer coextrusion light-shielding film layer 8a consisting of the above two layers is
The flexible sheet 3a has a resin temperature of 205 ° C., the light-shielding thermoplastic resin layer 7a has a resin temperature of 190 ° C., and the two sheets are melted separately by two extruders.
A light-shielding two-layer coextrusion inflation film having a total thickness of 55 μm formed by a multi-layer coextrusion inflation film molding method with a blow-up ratio of 1.2 after being introduced into a die.

As the adhesive layer 2, the two adhesive layers 2 and 2 for laminating the metal layer 5, the light-shielding thermoplastic resin layer 7a and the buffer sheet 1 have an MI of 5.6 g / 10 minutes and a density of 0.920.
99.95% by weight of low-density homopolyethylene resin with g / cm ³ and 2
-6-di-tert-butyl-para-cresol 0.05% by weight
A low-density homopolyethylene resin melt-extruded laminating adhesive layer having a thickness of 15 μm was applied at a resin temperature of 315 ° C. and an air gap of 110 mm.

The adhesive layer for laminating the light-shielding two-layer coextrusion film 8a and the buffer sheet 1 has MI of 5.6 g / 10.
Minute density, 0.920 g / cm ³ low density homopolyethylene resin
Low density homo-polyethylene resin melt extruded laminating adhesive layer consisting of 99.95 wt% and 2.6-di-tert-butyl-para-cresol 0.05 wt% with a resin temperature of 15 μm.
It was applied at 310 ° C and an air gap of 110 mm.

This packaging material for photographic light-sensitive materials was vertically hung down by 1480 mm using a roll-shaped packaging material that was divided into two 700 mm widths, and then a roll-shaped motion picture color positive film of 35 mm width × 6000 ft was moved to the central portion, A belt-shaped heat sealer is used to heat seal each side with a width of 15 mm, and the vertical dimension is 740 m.
While making a two-sided heat-sealed flat bag with m and width of 670 mm, a roll of color positive film for movie was hermetically sealed and wrapped, and the upper opening was bent and sealed with scotch tape to block light. The thus completely sealed package was stacked 20 times in the BOX Bin placed on the pallet and fixed to the pallet with a plastic band to obtain a collective package.

The product VI of the present invention is superior in pinhole resistance, abrasion resistance, heat resistance, impact puncture strength, tear strength, etc. to the packaging material of the comparative product I, and fog is not generated in the photographic light-sensitive material. In addition, it was excellent in bag-making suitability, surface smoothness, smoothness with a photographic light-sensitive material, and antistatic property. Since it has less curl and excellent heat sealing suitability, it has high speed automatic bag making suitability and can be provided at a cost of 1/2 or less as compared with the conventional impulse seal type packaging bag.

[Inventive Product VII] A roll-shaped packaging material for a photographic light-sensitive material having a width of 1400 mm and having a layer structure sectional view corresponding to FIG. 2 was used.

The buffer sheet 1 has a thickness of 0.5 mm and an expansion ratio of 3
0 times (density 0.03g / cm ³ ) as a closed cell type pyrolyzable foaming agent with a decomposition temperature of 190-230 ℃ and a gas generation of 190cc
It is a cross-linked ethylene / butene-1 copolymer resin foamed sheet having a cross-linking degree of 80% using / g of azodicarbonamide.
A wear-resistant and heat-resistant flexible sheet 6 having a Young's modulus of 50 kg / mm ² or more and heat resistance provided on one side (atmosphere side) of the buffer sheet is a 15 μm thick aluminum vacuum-deposited biaxially stretched polyamide (nylon 6 ) It is a resin film, and the flexible sheet 4 has a thickness of 15 μm and a Young's modulus of
195kg / mm ² , polyamide with melting point of 218 ℃ (nylon 6)
As the resin film, the metal layer 5 is a vacuum-deposited aluminum layer having a thickness of 400 Å.

The other side of the buffer sheet (photosensitive material side)
The flexible sheet 3a provided on the innermost side of which has a Young's modulus of 50 kg / mm ² or more and has heat sealability has a MI of 0.65 g / 10.
Min, density 0.952 g / cm ³ , crystallinity 92%, melting point 138
86.85% by weight of high-density homopolyethylene resin with a Vicat softening point of 126 ° C, MI of 2.0 g / 10 min, density of 0.922 g
/ Cm ³ , crystallinity 36%, melting point 116 ° C, Vicat softening point 105 ° C 10% by weight ethylene / butene-1 copolymer resin, erucamide amide 0.05% by weight, antioxidant hinder Tetrakis [methylene-3- (3.5-di-tert-butyl-4], which is a dephenol antioxidant.
-Hydroxyphenyl) propionate] methane (Cib
a Geigy, Irganox 1010, molecular weight 1177) 0.05% by weight, as a phosphorus-based antioxidant, stearyl-β (3.5-
Di-tert-butyl-4-hydroxyphenyl) propionate (Ciba Geigy, Irganox 1076, molecular weight 530)
0.05% by weight, pH 7.0 as a light-shielding substance, volatile content 0.5
Wt%, oil absorption 93ml / 100g, average particle size is made up of 3% by weight of furnace carbon black 21mμ, thickness 25
It is a light-shielding high-density homopolyethylene resin layer having a μm and Young's modulus of 56 kg / mm ² .

The light-shielding thermoplastic resin layer 7a in the two-layer coextrusion blown film has MI of 2.0 g / 10 min,
91.5% by weight of ethylene-4-methylpentene-1 copolymer resin having a density of 0.920 g / cm ³ , a crystallinity of 45%, a Vicat softening point of 98 ° C., and the above stearyl-
0.05% by weight of β (3.5-di-tert-butyl-4-hydroxyphenyl) propionate, tetrakis [methylene-3-
0.05% by weight of (3.5-di-tert-butyl-4-hydroxyphenyl) propionate] methane was used in combination with 0.2% by weight of zinc stearate as a lubricant and 0.05% of erucic acid amide.
%, Polyoxyethylene glycerin fatty acid ester 0.15% by weight as an antistatic agent, low density homopolyethylene resin 5% by weight which is the same as the flexible sheet 3a and furnace carbon black 3% by weight and a thickness of 25μ
m, Young's modulus 38 kg / mm ² light-shielding ethylene / α-olefin copolymer resin layer. 2 consisting of the above two layers
The layer coextrusion light-shielding film layer 8a has a resin temperature of the flexible sheet 3a of 200 ° C. and a light-shielding thermoplastic resin layer 7a.
Resin temperature of 190 ℃, melted separately by two extruders, introduced into a circular die of adhesive type in die, and then blown up with a ratio of 1.2 to form a multilayer coextrusion by blown film It is a 50 μm light-shielding bilayer coextrusion blown film. Then, as the adhesive layer 2, as an adhesive layer for laminating the metal layer 5 and the buffer sheet 1, the MI is 6.2 g / 10 minutes and the density is 0.918.
95.95% by weight of low-density homopolyethylene resin with g / cm ³ and 2
A light-shielding low-density homopolyethylene resin melt-extruded laminate adhesive layer having a thickness of 20 μm and made of 0.05% by weight of 6-di-tert-butyl-para-cresol and 5% by weight of the same furnace carbon black as that of the flexible sheet 3a is used as the resin temperature. Applied at 315 ℃, 110mm air gap. The peel strength between the flexible sheet 4 and the buffer sheet 1 at this time was 12 g / 30 mm width.

The adhesive layer 2 for laminating the light-shielding two-layer coextrusion film 8a and the buffer sheet 1 has an MI of 5.6.
99.95% by weight of low-density homopolyethylene resin having a density of 0.920 g / cm ³ and a density of 0.920 g / cm ³ and 2.6-di-tert-butyl-para.
A 15 μm thick low density homopolyethylene resin melt extruded laminating adhesive layer consisting of 0.05 wt% cresol was applied at a resin temperature of 310 ° C. and an air gap of 110 mm. At this time, the peel strength between the two-layer coextrusion film 8a and the buffer sheet 1 was 556 g / 30 mm width, and the flexible sheet 4
It was 46.3 times the peel strength between the buffer sheet and the buffer sheet.

[0350] This packaging material for photographic light-sensitive materials was vertically hung down by 1480 mm using a roll-shaped packaging material divided into 700 mm width, and then a roll-shaped color positive film of 35 mm width x 6000 ft was moved to the central portion, A belt-shaped heat sealer is used to heat seal each side with a width of 15 mm, and the vertical dimension is 740 m.
While making a two-sided heat-sealed flat bag with m and width of 670 mm, a roll of color positive film for movie was hermetically sealed and wrapped, and after bending the upper opening, it was hermetically sealed with cellophane tape. The thus completely sealed package was stacked 20 times in a BOX Bin placed on a pallet and fixed to the pallet with a plastic band to obtain a collective package.

The product VII of the present invention is superior in pinhole resistance, abrasion resistance, heat resistance, buffer piercing strength, tear strength and the like to the packaging material of the comparative product I, and fog is not generated in the photographic light-sensitive material. In addition, it was excellent in bag-making suitability, surface smoothness of packaging material, lubricity with photographic light-sensitive material, and antistatic property. The curl is small and the heat sealing suitability is excellent, so the suitability for high-speed automatic bag making is excellent, and it can be provided at a cost of 1/2 or less compared to the conventional impulse seal type packaging bag.

Further, the peel strength between the flexible sheet 4 and the buffer sheet 1 is weaker than the width of 300 g / 30 mm and 12 g / 30 mm width (peeling between the flexible sheet 4 and the metal layer 5), and two layers are opposite. The peel strength between the co-extruded film 8a and the buffer sheet 1 is 556g / 30mm width, which is very strong, so it has excellent pinhole resistance, perfect sealing property, heat sealing suitability, perfect light shielding property, impact strength, and bag breaking strength. , No complaints about the quality of photographic light-sensitive materials such as light fog and static fog in US exports.

The above-mentioned melt index, density and Vicat softening point are measured values defined by JIS K 6760.
The melting point is the melting end temperature of a differential scanning calorimeter (abbreviation DSC).

[Invention Product VIII] A roll-shaped packaging material for a photographic light-sensitive material having a width of 1400 mm and having a layer structure sectional view corresponding to FIG. 3 was used. Using a roll-shaped packaging material obtained by dividing the packaging material for photographic light-sensitive material into 700 mm widths, a hermetically sealed package is placed in a two-way heat-sealed flat bag having the same dimensions as the product of the invention VI.
The same package was used.

As the packaging material for the photographic light-sensitive material, the abrasion-resistant and heat-resistant flexible sheet 6 is used from the outside (atmosphere side).
(Aluminum vacuum deposition biaxially stretched nylon resin film: Thickness 15μm ± 3μm, Aluminum vacuum deposition thickness 400Å ± 5
0Å), LDPE adhesive layer 2 (thickness 13 ± 2 μm), light-shielding thermoplastic resin layer 7a ′ (carbon 3 wt%, thickness 30 μm ± 5 μm
m), LDPE adhesive layer 2 (thickness 13 ± 2 μm), buffer sheet 1 (non-crosslinked, closed-cell type foamed polyethylene sheet: thickness 0.5 mm ± 0.1 mm), abrasion-resistant flexible sheet 8a (strengthening simultaneous two layers) Co-extrusion light-shielding film: thickness 50 μm
± 5 μm), light-shielding thermoplastic resin layer 7a (L-LDPE
System resin layer, carbon black 3wt% included, thickness 25μm ± 5
and a heat-sealable light-shielding flexible sheet 3a (molecularly oriented HDPE resin layer, the ratio of coextrusion thickness of 7a and 3a is 50:50, that is, 7a and 3a have a thickness of 25μ).
A laminated film having a thickness of m ± 5 μm) was used.

[0356] The above abrasion-resistant and heat-resistant flexible sheet 6
Was different from the product VI of the present invention. That is, an aluminum vacuum-deposited biaxially stretched nylon resin film having an anchor coat layer and an undercoat layer for improving the adhesive strength on the surface of the biaxially stretched nylon resin film 4 to improve the peel strength from the aluminum vacuum deposition layer 5 is used. I was there.

As the buffer sheet, a non-crosslinked, closed-cell type foamed polyethylene sheet (thickness 0.5 mm) was used.
Others have the same resin composition as the product VI of the present invention (however, the thickness is different)
It is a packaging material in which the flexible sheets of are laminated via an adhesive layer.

Measuring Method: Using Toyo Seiki's Stro R Tester Then, using the automatic bag-making device shown in FIG. 10, two heat-sealable flexible sheets of this laminated film were heat-sealed together to form a flat bag. .

Abrasion resistance / heat resistance Peel strength between the flexible sheet and the black polyethylene film and peel strength between the cushioning sheet and the black polyethylene film (otherwise, the peel strength is 500 g / 15 mm width = 1000 g / 30 mm width or more. Measurement is impossible).

[0360] According to JIS K 6744 (ASTM D-903), when the partially peeled ends are mounted on a chuck of a tensile tester and an angle peeling test of 180 ° is performed under the right measurement conditions. The maximum load of was measured.

Range (full scale) 500g Pulling speed 300mm / min Chart speed 100mm / M Chuck interval 150mm Sample width 15mm N number 4 Result:

[0362]

[Table 4]

[0363] This light-shielding bag hardly curls,
Young's modulus of 50kg / mm ² on the cushioning sheet and both sides
The above high Young's modulus flexible sheet is provided, and a low-density light-shielding polyethylene-based resin layer having a Young's modulus of 50 kg / mm ² or less but having a large elongation and less likely to cause holes or tears is provided on the side close to the buffer sheet. Since it is provided, it is a light-shielding bag with high commercial value, which has excellent bag making suitability, physical strength, and bag breaking strength, and can be distinguished from the front and back even under a safelight.

Effect of applying a light-shielding bag using the packaging material for a photographic light-sensitive material of the present invention to a roll-shaped photographic positive film for movies. (1) Regardless of the roll length of the rolled photographic film, the reinforced light-shielding bag in which the conventional metal can can be abolished can be provided at low cost by using the packaging material having the same laminated structure and only changing the seal dimension. (2) Even with a packaging material that includes a cushioning sheet, high-speed automatic bag making is possible and the bag cost can be reduced by 70% or more (no curling occurs, and the heat resistance of both outermost flexible sheets ( Results of selective use so that the difference in melting point or Vicat softening point) is 40 ° C or more. (3) Simplified packaging work and process (metal cans can be abolished, and automatic bag making and packaging are possible). (4) Handling of rolled photographic film (opening and taking out)
Became easier. (5) Appropriate mechanical transportation is provided in large quantities at one time, and physical suitability is further improved. (6) Combined with shipping packaging and reduced volume to reduce distribution costs (The development of a reinforced light-shielding bag that can eliminate metal cans can greatly reduce the volume of export packaging and make it compact without degrading quality protection. Can be wrapped).

[Comparative Product I] Two uniaxially stretched high density polyethylene resin films each having a thickness of 45 μm and containing 3.0% by weight of carbon black, which are equivalent to the laminated sheet described in Japanese Utility Model Publication No. 2-736. Two uniaxially stretched high-density polyethylene resin films with a 90 ° stretching axis on both sides of a 1 mm-thick polyethylene foam sheet (foaming ratio 50 times) with a 20 μm-thick extrusion laminate adhesive layer made of low-density homopolyethylene resin A packaging material having a total thickness of about 250 μm, which is laminated so as to cross at an angle of, was used. An attempt was made to make a flat bag having the same dimensions as the product I of the present invention by the same bag-making method, but not only heat sealing was not possible and light entered the bag for practical use, but also a portion in contact with the heat sealing bar. Was melted to form pinholes, the physical strength was significantly lowered, and bag breakage was easily caused.

[0366]

[Preferred Embodiment]

(1) The decomposition temperature is preferably as a thermally decomposable foaming agent.
58 to 320 ° C, preferably 80 to 300 ° C, particularly preferably 90 to
290 ° C., most preferably 100 to 280 ° C., and the gas generation rate is 100 cc / g or more, preferably 135 cc / g or more, particularly preferably 170 cc / g or more, most preferably 190 cc / g
The packaging material for a photographic light-sensitive material according to claim 1, which has a weight of at least g.

(2) Density is 0.8 g / cm ³ , preferably 0.5 g
/ Cm ³ or less cushioning sheet, Young's modulus on both sides of the cushioning sheet is 50 kg / mm ² or more, wear-resistant and heat-resistant flexible sheet with heat resistance, and Young's modulus 50 kg / mm ²
Peel strength with at least one of the above abrasion resistant flexible sheets is 0.01 to 450 g / 30 mm width, preferably 0.1 to 30
The packaging material for a photographic light-sensitive material according to claim 1, 2, 3 or 4, which has a width of 0 g / 30 mm, particularly preferably 0.5 to 200 g / 30 mm.

(3) Density is 0.8 g / cm ³ , preferably 0.5 g
/ Cm ³ or less The peel strength between the inner side of the cushioning sheet and the abrasion-resistant flexible sheet laminated on the side of the photographic light-sensitive material via the adhesive layer is 6 g / 30 mm or more, preferably 25 g / 30 mm
Width or more, particularly preferably 50 g / 30 mm width or more, most preferably 100 g / 30 mm width or more, and a wear-resistant and heat-resistant flexible sheet laminated with an adhesive layer on the atmosphere side outside the buffer sheet and a buffer Peel strength between the sheet and 5
The packaging material for a photographic light-sensitive material according to claim 1, 2, 3 or 4, which is at least 10 times, preferably at least 10 times, more preferably at least 15 times.

(4) Density is 0.8 g / cm ³ , preferably 0.5 g
/ Cm ³ or less, particularly preferably 0.2 g / cm ^3, most preferably 0.1 g / cm ³ or less of a buffer outer wear and heat resistance flexible sheet having a heat resistance of the flexible sheet of the outermost layer of the atmosphere side of the sheet Melting point 120 ° C or higher, preferably 150
℃ or more, particularly preferably 180 ℃ or more, most preferably 200
℃ or more, or the Vicat softening point is 110 ℃ or more, preferably 140 ℃ or more, particularly preferably 170 ℃ or more, most preferably 190 ℃ or more, or a flexible sheet that does not melt or soften, the photographic exposure inside the buffer sheet. The melting point or Vicat softening point of the flexible sheet having the heat-sealing property of the innermost layer on the material side) 10 ° C. or more, preferably 20 ° C. or more, particularly preferably 40 ° C. or more, most preferably 80 than the wear-resistant and heat-resistant flexible sheet. The packaging material for a photographic light-sensitive material according to claim 1, 2, 3 or 4, which has a low temperature of ℃ or more.

(5) The flexible sheet having heat sealability provided on the other outermost side (photosensitive material side) of the buffer sheet comprises at least one thermoplastic resin layer having a Young's modulus of 50 Kg / mm ² or more. The light-shielding bag according to claim 1, which is a light-shielding multi-layer coextrusion film having at least one thermoplastic resin light-shielding layer and having a heat-sealing layer as an outermost layer.

(6) Thickness 20 μm to 5 mm, preferably 100 μ
The interlayer peel strength of the buffer sheet of m to 3 mm, particularly preferably 300 μm to 2 mm is 400 g / 30 mm width or less, preferably 60
The light-shielding bag according to claim 1, which has a width of ˜300 g / 30 mm, particularly preferably a width of 50-250 g / mm.

(7) The light-shielding bag has a flexible sheet with Young's modulus of 50 kg / mm ² or more on both sides of the cushioning sheet,
The thickness between the buffer sheet and the flexible sheet having a Young's modulus of 50 kg / mm ² or more is 7 to 150 μm, preferably 10 to 120 μm.
m, particularly preferably 20-100 μm, most preferably 30-9
The light-shielding bag according to claim 1, comprising a light-shielding laminated film provided with a light-shielding thermoplastic resin layer having a thickness of 0 μm.

(8) The front and back sides can be identified in the safelight chamber in which the photographic light-sensitive material is packaged. For example, one of the front and back sides is a light-reflecting flexible sheet (a flexible sheet whose surface color is colored, printed or applied in white, silver, yellow, gray, etc.), and the other is a light-absorbing flexible sheet ( The surface color is black, red, blue, brown, etc., colored similar to safelight light or a color whose existence is difficult to identify,
The packaging material for a photographic light-sensitive material according to claim 1, which has a laminated structure composed of a flexible sheet which is printed or applied.

(9) The packaging material for a photographic light-sensitive material according to claim 1, wherein the minimum position of the interlayer peel strength between the laminates is the interlayer peel strength of the buffer sheet.

(10) A light-reflecting abrasion-resistant and heat-resistant flexible sheet having a Young's modulus of 50 kg / mm ² or more provided on one side (atmosphere side) of the buffer sheet and a buffer sheet. The packaging material for a photographic light-sensitive material according to claim 1, further comprising a light-absorptive abrasion-resistant flexible sheet provided on the other side (the photographic light-sensitive material side).

(11) The light shielding bag has a heat seal width of 3 to 30 mm,
The light-shielding bag according to claim 1, which is preferably a two-side completely heat-sealed flat bag, a gusset bag or a three-way completely heat-sealed bag having a thickness of preferably 5 to 25 mm, particularly preferably 7 to 20 mm, and most preferably 9 to 18 mm.

(12) The interlayer peel strength of the thermoplastic resin foam sheet is 50 g / 300 mm width or more, the degree of crosslinking is 10% or more,
The packaging material for a photographic light-sensitive material according to claim 1, which comprises a crosslinked thermoplastic resin foam sheet of preferably 30% or more, particularly preferably 50% or more, and most preferably 60 to 85%.

[0378]

The packaging material for a photographic light-sensitive material and the light-shielding bag using the same according to the present invention are simple heat sealers generally used while maintaining physical strength such as improved pinhole resistance and impact resistance. It can be heat-sealed at high speed with high commercial value and excellent appearance.

[Brief description of drawings]

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

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

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

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

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

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

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

FIG. 8 is a perspective view of an embodiment of a light-shielding bag for a photographic light-sensitive material according to the present invention.

FIG. 9 is a perspective view of an embodiment of a light-shielding bag for a photographic light-sensitive material according to the present invention.

FIG. 10 is a schematic side view of the automatic bag making device.

FIG. 11 is a schematic plan view of an automatic bag making device.

FIG. 12 is a diagram showing a process of making a photographic light-sensitive material package.

FIG. 13 is a diagram showing a process of making a photographic light-sensitive material package.

[Explanation of symbols]

1 ... Foamed sheet (buffer sheet) 2 ... Adhesive layer 3a ... Heat-sealable flexible sheet with Young's modulus of 50 kg / mm ² or more (wear resistance) 4 ... Flexible sheet with Young's modulus of 50 kg / mm ² or more (resistance Abrasion / heat resistance) 5 ... metal layer 6 ... metal thin film processed flexible sheet 7, 7a, 7a '... thermoplastic resin layer 8a ... two-layer coextrusion film 9a ... multi-layer blocking laminated film 10a ... three-layer coextrusion film 11 ... modified Resin layer 12a ... Intermediate layer 13a ... 5-layer coextrusion film 15 ... Shade bag for photographic light-sensitive material

Claims (23)

[Claims] 1. A cushioning sheet, a wear-resistant / heat-resistant flexible sheet having a Young's modulus of 50 kg / mm ² or more and heat resistance provided on one side of the cushioning sheet, and provided on the other side of the cushioning sheet. And a wear resistant flexible sheet having a Young's modulus of 50 kg / mm ² or more, and the other outermost layer has a heat-sealing property and further has a complete light-shielding property. Packaging material for photographic light-sensitive material characterized in that 2. A thickness of 5 to 180 μm from the side of the photographic light-sensitive material.
m, a Young's modulus of at least 50 kg / mm ^{2 and} a thermoplastic resin layer and an ethylene / α-olefin copolymer resin having a resin layer of at least 50% by weight, and a multilayer coextrusion film having a thickness of 20 to 200 μm, an adhesive layer, Thickness is 50μm-5mm, density is 0.
8 g / cm ³ or less of the buffer sheet, the adhesive layer, the thickness 7~200μ
m, a wrapping material for a photographic light-sensitive material, characterized in that a wear-resistant and heat-resistant flexible sheet having a heat resistance of 50 kg / mm ² or more is laminated in this order. ^3. A buffer sheet having a density of 0.5 to 0.01 g / cm ³ , and a thickness of 5 to 50 μm provided on one side of the buffer sheet.
m, Young's modulus of 50 kg / mm ² or more of aluminum vacuum vapor-deposited biaxially stretched thermoplastic resin film, and a light-shielding substance with a refractive index of 1.50 or more and a specific gravity of 1.50 or more provided on the other side of the buffer sheet. 20% by weight Young's modulus is 50 kg / mm ² or more and has a thickness of 10 to 200 μm and wear-resistant flexible sheet, and the other outermost layer has heat sealability, A wrapping bag for photographic light-sensitive material, which has a perfect light-shielding property 4. A cushioning sheet, and Young's modulus of 50 kg / mm laminated on the atmosphere side outside the cushioning sheet via an adhesive layer.
A metal thin film processed flexible sheet layer having a heat resistance of ² or more and an oxygen permeability of 50 cc / m ² · 24 hours · 1 atm or less and a moisture permeability of 5 g / m ² · 24 hours or less, and the buffer sheet. 0.1 to 30% by weight of a light-shielding substance and 0.01 to 10% by weight of a lubricant and / or an antistatic agent, which are laminated on the inner side of the photographic light-sensitive material via an adhesive layer, and have a Young's modulus of 50 kg / mm ² or more. A thermoplastic resin film layer, and the innermost layer provided on the side of the photographic light-sensitive material has a heat-sealing property, and the laminated film as a whole has an optical density of 7 or more and a complete light-shielding property. Packaging material for photographic light-sensitive materials 5. A foamed polyolefin resin sheet having a thickness of 0.3 to 3 mm and a foaming ratio of 5 to 50 times, a wear-resistant cushioning sheet.
The heat-resistant flexible sheet is a metal thin film processed flexible sheet having heat resistance higher than that of the layer provided on the other side, and the abrasion-resistant flexible sheet provided on the photographic photosensitive material side has heat sealability. Packaging material for photographic light-sensitive material according to 2, 3 or 4 6. The packaging material for a photographic light-sensitive material according to claim 1, wherein a layer having a light-shielding property is provided on both sides of the buffer sheet. 7. Young's modulus capable of heat sealing is 50 kg / mm
^The packaging material for photographic light-sensitive materials according to claim 1, 2, 3 or 4, wherein ^two or more flexible sheets contain a silicone oil. 8. The method according to claim 1, 2, 3 or 4, wherein at least one or more layers contain 50% by weight or more of a chemically synthetic biodegradable plastic which is decomposed into carbon dioxide and water by the action of microorganisms. Packaging materials for photographic materials 9. The metal layer is provided between the cushioning sheet and the abrasion-resistant / heat-resistant flexible sheet,
Packaging material for photographic light-sensitive material according to 2, 3 or 4 10. The wear-resistant and heat-resistant flexible sheet,
Oxygen permeability with a thickness of 5 to 100 μm and Young's modulus in the longitudinal direction of 50 kg / mm ² or more and a uniaxially or biaxially molecularly oriented (including stretched) thermoplastic resin film with an aluminum vacuum deposition film at a thickness of 80 to 800 Å Is made of aluminum vacuum-deposited thermoplastic resin film of 50 cc / m ² · 24 hours · 1 atmosphere · 20 ° C or less and moisture vapor transmission rate of 5 g / m ² · 24 hours or less. Thickness including 0.1-30% by weight 1
The packaging material for photographic light-sensitive materials according to claim 1, 2, 3 or 4, comprising a polyolefin resin film having a thickness of 5 to 200 µm and having a Young's modulus of 50 kg / mm ² or more. 11. At least one of the delamination strengths of the respective layers is
The packaging material for a photographic light-sensitive material according to claim 1, 2, 3 or 4, which has a width of 0.1 to 300 g / 30 mm. 12. The abrasion resistant flexible sheet is one layer of a multilayer coextruded film, 1, 2, 3 or 4.
Packaging material for photographic light-sensitive materials described in 13. The packaging material for a photographic light-sensitive material according to claim 9, wherein the abrasion-resistant flexible sheet is an outermost layer of a laminated film obtained by blocking and laminating inner layers of a multilayer coextrusion film. 14. The cushioning sheet is a polyolefin resin foamed sheet, which is foamed with a pyrolytic foaming agent having a decomposition temperature of 80 to 300 ° C. to a foaming ratio of 5 times or more.
Packaging material for photographic light-sensitive material according to 2, 3 or 4 15. The packaging material for a photographic light-sensitive material according to claim 11, wherein the cushioning sheet has an expansion ratio of 10 times or more. 16. The wear-resistant flexible sheet is provided on the outside thereof,
Young's modulus is 50 kg / mm ²Heat with the above heat sealability
A plastic resin layer is laminated, and the plastic resin layer is laminated | stacked.
Packaging material for photographic light-sensitive materials described in 17. A cushioning sheet, a wear-resistant / heat-resistant flexible sheet and a wear-resistant flexible sheet having a thickness of 7 to
The packaging material for a photographic light-sensitive material according to claim 1, 2, 3 or 4, which is laminated via a polyolefin resin adhesive layer for extrusion lamination having a thickness of 50 µm. 18. The packaging material for a photographic light-sensitive material according to claim 1, 2, 3 or 4, wherein at least one layer of the packaging material contains 0.1 to 20% by weight of a light-shielding substance having a refractive index of 1.50 or more. 19. The layer having heat sealability has a density of 0.
940 to 0.985 g / cm ³ , melt index 0.01 to 2.0 g
/ 10 minutes homopolyethylene resin and / or ethylene
50% by weight or more of α-olefin copolymer resin, 0.01 to 30% by weight of light-shielding substance, and lubricant and / or antistatic agent
The packaging material for a photographic light-sensitive material according to claim 1, which contains at least 0.01 to 10% by weight, and a light-shielding bag using the same. 20. The heat-sealing layer is one layer of a multi-layer coextrusion film, the heat-sealing layer has a density of 0.940 to 0.985 g / cm ³ and a melt index of 0.01 to 2.0 g / 10. Minute homopolyethylene resin and /
Or 50% by weight of ethylene / α-olefin copolymer resin
An abrasion-resistant layer containing the above, the remaining at least one layer having a density of 0.870 to 0.935 g / cm ³ and a melt index of 0.1 to 10 g / 10 min ethylene / α-olefin copolymer resin and / or polyolefin The pinhole resistant layer containing 10% by weight or more of an elastomer, and the light blocking multilayer coextrusion film containing 0.1 to 30% by weight of a light blocking substance in at least one layer or more. Packaging material for photographic materials 21. The thickness of the wear-resistant layer of the heat-sealing layer is less than the total thickness of the light-shielding multilayer coextruded film.
30 to 90% occupy, and 5 to 180 μm.
Or packaging material for photographic light-sensitive material as described in 4 above 22. The peel strength between the cushioning sheet and the abrasion / heat resistant flexible sheet is 0.1 to 300 g / 30 mm width, and the peeling strength between the cushion sheet and the abrasion resistant flexible sheet is 6 g.
The packaging material for photographic light-sensitive materials according to claim 1, 2, 3 or 4, which has a width of / 30 mm or more and is 5 times or more the peel strength between the abrasion-resistant and heat-resistant flexible sheet and the buffer sheet. 23. A light-shielding bag for a photographic light-sensitive material, which is formed by heat-melting and bonding layers having heat-sealability of the packaging material for a photographic light-sensitive material according to claim 1, 2 or 3.