JP2000162737A - Packaging material for photographic sensitive material and photographic sensitive material packaged body using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a packaging material for a photographic sensitive material which has good heat sealing property and physical strength without producing a lump of carbon black, microgrids or the like, and to provide a photographic packaged body using this packaging material. SOLUTION: The packaging material for a photographic sensitive material is made of a light-shielding resin film layer 1a consisting of a resin compsn. containing >=5 wt.% of a thermoplastic elastomer having <=30% crystallization degree measured by an X-ray diffraction method, a lubricant, and 0.1 to 60 wt.% of carbon black. The thermoplastic elastomer is a polyolefin elastomer and has >=16 mol% α-olefin unit content excluding ethylene and propylene.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photographic material packaging material and a photographic material package using the same.

[0002]

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

A wrapping material for photographic light-sensitive materials, which loses its quality value when exposed to light, is a wrapping material that completely blocks light. In this case, the required property is a wrapping material slit. Suitability, gas barrier properties, moisture resistance, rigidity, physical strength (rupture strength, tear strength, impact hole opening strength, gelbo test strength, abrasion strength, etc.), heat seal suitability (heat seal strength, cut sealability, hot tackiness, congestion) Material sealing properties), antistatic properties, flatness, sliding properties, etc. In order to satisfy these various properties, various packaging materials have been conventionally proposed. Injection molded products (light-shielding magazines, light-shielding cartridges, light-shielding patrones, etc.) that can completely block light, such as photographic films with patrone, photographic film units with lenses, and new photographic system (APS) films. As for the packaging body using, a transparent packaging material with a completely sealed print is proposed.

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

[0005] Japanese Patent Publication No. 4-80372 discloses LL
50-95% by weight of DPE resin and 5-49% of HDPE resin.
0.1 to 10% by weight of carbon black and 0.01 to 1% of lubricant in a polyolefin resin composition consisting of 5% by weight.
Packaging materials for photographic light-sensitive materials containing 0% by weight have been proposed.

Japanese Patent Publication No. 4-80373 discloses HDP.
There has been proposed a packaging material for photographic light-sensitive materials comprising a two-layer co-extruded blown film comprising an E layer or a PP layer and an L-LDPE layer.

[0007] Japanese Patent Application Laid-Open No. 9-80695 discloses a paper made from a mixed pulp of 30% softwood pulp and 70% hardwood pulp, having a thickness of 75 to 80 μm and a basis weight of 80 g / m ^2. A light-shielding LDPE inflation film layer containing 18% by weight of 20 μm acetylene black is adhered via a polyurethane-based dry laminating adhesive, and a light-shielding paper provided with a printing layer and a protective layer on the other side is joined. 120 size and 22 barcodes on the tape printed with a barcode that allows the camera to automatically detect the sensitivity etc.
A 0-size roll film package for photography has been proposed.

[0008]

However, the above-mentioned conventional packaging materials for photographic light-sensitive materials are insufficient in dispersibility of light-shielding substances such as carbon black, and the generation of bumps and microgrids is improved in many cases. It was desired. In particular, when packaging a high-sensitivity photographic light-sensitive material having an ISO sensitivity of 100 or more, if the high-sensitivity photographic light-sensitive material is used in contact with a packaging material in which lumps or microgrids are generated, the photographic light-sensitive layer is Scratches, friction fog, pressure fog, and the like occurred, and the fatal failure as a photographic photosensitive material could not be achieved. Furthermore, when the content of the light-shielding substance is increased, there is a problem that physical strength and heat sealing suitability are deteriorated.

In addition, if a recent disposal method of containers and packaging materials is to be cleared, it is impossible to use a metal-deposited flexible sheet layer provided with a metal foil or a metal-deposited film as in the prior art. As a solution to this problem, it is conceivable to add 10% by weight or more of conductive carbon black or graphite. However, the dispersibility of these is further insufficient, so that lumps and microgrit frequently occur, which is fatal to photographic light-sensitive materials. Failures occur frequently and cannot be put to practical use. In addition, deterioration of heat seal suitability and deterioration of physical strength and the like occur, and there is a problem as a packaging material for photographic light-sensitive materials that are precision chemical products, and improvement has been desired. It is conceivable to use various rubbers that require sulfur crosslinking, but this has an adverse effect on the photographic properties of photographic light-sensitive materials and is difficult to put into practical use.

The present invention solves the above problems and does not adversely affect the photographic properties of a photographic light-sensitive material.
No bumps or micro grids occur, and
An object of the present invention is to provide a packaging material for photographic light-sensitive materials having good heat sealability and physical strength, and a photographic light-sensitive material package using the same.

[0011]

The wrapping material for photographic light-sensitive material of the present invention has a crystallinity of 30 as measured by an X-ray diffraction method.
% Of a thermoplastic elastomer of 5% by weight or less, a lubricant, and 0.1 to 60% by weight of carbon black.

In the packaging material for photographic light-sensitive material of the present invention, the photographic properties of the photographic light-sensitive material are adversely affected by containing 5% by weight or more of a thermoplastic elastomer having a crystallinity of 30% or less as measured by an X-ray diffraction method. Without affecting
It improves the dispersibility of carbon black, prevents occurrence of bumps, microgrids, and the like, and prevents a decrease in physical strength and deterioration in heat seal suitability.

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION The packaging material for a photographic light-sensitive material of the present invention has a light-shielding resin film layer, and the light-shielding resin film layer has a crystallinity of 3 measured by an X-ray diffraction method.
It is composed of a resin composition containing 5% by weight or more of a thermoplastic elastomer of 0% or less, a lubricant, and 0.1 to 60% by weight of carbon black.

The thermoplastic elastomer contained in the resin composition used for the light-shielding resin film layer has a crystallinity of 30% or less, preferably 25% or less, more preferably 20% or less, as measured by an X-ray diffraction method. %, Particularly preferably at most 15%, most preferably at most 10%. If the crystallinity exceeds 30%, the physical strength decreases, and it becomes difficult to efficiently improve the dispersibility of carbon black and the like.

The crystallinity measured by the X-ray diffraction method is 30
% Or less of the thermoplastic elastomer is 5% in the resin composition.
% By weight, preferably at least 10% by weight, more preferably at least 15% by weight, particularly preferably at least 20% by weight.
As described above, the content is most preferably 25% by weight or more. When the content of the thermoplastic elastomer is less than 5% by weight, it becomes difficult to improve the dispersibility of carbon black and the like.

Thermoplastic elastomers (hereinafter, referred to as TPE) can be roughly classified into styrene-based (hereinafter, referred to as SBC),
Ester (hereinafter referred to as TPEE), olefin (hereinafter referred to as TPO), vinyl chloride (hereinafter referred to as TPVC), amide (hereinafter referred to as TPAE), crystalline 1,2
Polybutadiene type (hereinafter referred to as RB), ionomer type, fluorine type (hereinafter referred to as F-TPE), urethane type (hereinafter referred to as TPU), isoprene type, chlorinated polyethylene type, polyfluorocarbon type, etc. There is. Table 1 shows typical commercially available TPEs.

[0017]

[Table 1]

Among the above thermoplastic elastomers, polyolefin-based elastomers are preferable, and among these polyolefin-based elastomers, the content of α-olefin units other than ethylene or propylene is 16 mol%.
The above is appropriate, preferably at least 18 mol%, more preferably at least 20%, particularly preferably at least 25%.
Above, most preferably 30% or more.

The α-olefin has 3 to 20, preferably 3 to 17, more preferably 3 to 15, particularly preferably 3 to 12, and most preferably 3 to 9 carbon atoms. Things. Specifically, propylene, butene-1, hexene-1, 4-methylpentene-1, octene-1, decene-1, heptene-1, nonene-1,
Pentadecene-1, octadecene-1, eicosene-
1, dodecene-1, hexadecene-1, octadecene-
1 mag.

The resin composition used for the light-shielding resin film layer contains 0.1 to 60% by weight of carbon black, preferably 0.5 to 50% by weight, more preferably 1 to 40% by weight, particularly Preferably, the content is 2 to 30% by weight, most preferably 3 to 20% by weight.

The content of carbon black is 0.1% by weight
If the thickness is less than 300 μm,
If it is not more than m, it is difficult to secure the light shielding property,
On the other hand, if the content exceeds 60% by weight, the kneading cost is increased and the cost is increased. In addition, lumps and the like are liable to be generated, and the physical strength and heat sealing suitability are deteriorated. It is difficult to secure the airtightness and the sealing performance.

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

Representative examples of preferred commercial products of carbon black include, for example, carbon black # 2 manufactured by Mitsubishi Kasei.
0 (B), # 30 (B), # 33 (B), # 40 (B), # 41
(B), # 44 (B), # 45 (B), # 50, # 55, # 1
00, # 600, # 950, # 1000, # 2200
(B), # 2400 (B), # 4000, # 4010, MA
7, MA8, MA11, MA100, MA100R, M
A220, MA230, # 3050, # 3150, # 3250, # 3600, # as Mitsubishi conductive carbon black
3750, # 3950 and the like.

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

Overseas products include, for example, Black Pearls L, 2, 46, 70, 71, 7 of Cabot Corporation.
4,80,81,130,280,430,460,4
80,607,800,880,900,1000,11
00, 1300, 1400, etc., Regal 99, 25
0,300,330,400,415,660,99
1, SRF-S etc., Vulcan 3,6, P, XC-72
Etc., Sterling 10, SO, V, S, FT-F
F, MT-FF and the like.

Further, Unit of Ashland Chemical Co., Ltd.
ed R, BB, 15,102,3001,3004,30
06,3007,3008,3009,3011,3012,
XC-3016, XC-3017, 3020 and the like. In addition, Columbia Chemical's Cond
octex 975, SC, Raven C, H20, 4
10,420,430,450,460,500,52
0,760,790,850,890,1000,104
0,1060,1170,1190,1200,125
0,1255,2000,2500,3500,5000,5
250, 5750, 7000, and the like, but are not limited thereto.

A channel black produced by contacting the back surface of a channel steel while incompletely burning a gas flame of natural gas or a gaseous or vaporous hydrocarbon in these various carbon blacks to precipitate carbon black. Are not preferred in the present invention because they have high coloring power but poor photographic properties and pollute the air during production. The preferred carbon black in the present invention is acetylene black, natural gas, hydrocarbon oil or a mixture thereof.
Furnace black produced by continuous partial combustion in a furnace at 00 ° C to 1700 ° C or by thermal decomposition.

In the present invention, furnace carbon black is preferred for the purpose of improving light-shielding properties, cost and physical properties. As expensive light-shielding substances having an antistatic effect, acetylene carbon black and ketjen carbon which is a modified by-product carbon black are preferred. Black is preferred. In particular, furnace carbon black and acetylene black having a sulfur content (ASTM D 1619) of 0.1% or less are preferable for photographic photosensitive materials having a high sensitivity (ISO sensitivity of 400 or more). If necessary, it is also preferable to mix the former and the latter according to required characteristics.

Particularly preferred conductive carbon blacks in the present invention include, for example, acetylene black, conductive furnace black (CF), superconductive furnace black (SCF), extra conductive furnace black (XCF), conductive channel black (CC) and 1500. Furnace black or channel black heat-treated at a high temperature of about ° C can be used. Specific examples of acetylene black include Denka acetylene black (manufactured by Denki Kagaku) and Shaunigan acetylene black (manufactured by Shaunigan Chemical Co., Ltd.). Specific examples of conductive furnace black include Continex CF.
(Continental Carbon Co., Ltd.), Vulcan C
(Manufactured by Cabot Corporation) and the like. Examples of the superconductive furnace black include Continex SCF (manufactured by Continental Carbon Co., Ltd.) and Vulcan SC (manufactured by Cabot Corporation). Specific examples of the extra conductive furnace black include Asahi. HS
-500 (manufactured by Asahi Carbon Co., Ltd.), Vulcan XC-72
(Manufactured by Cabot Corporation), and Colux L (manufactured by Degussa Co., Ltd.) as the conductive channel black. Ketchen Black EC and Ketjen Black EC-600JD (Ketjen), which are a kind of furnace black, are exemplified. Black International Co., Ltd.) can also be used. Among these, acetylene black is particularly excellent in conductivity because it has a low impurity content and has a developed secondary structure, and is particularly preferably used in the present invention. In addition, Ketjen Black EC has excellent specific surface area and therefore exhibits excellent conductivity even at low loadings.
And Ketjen Black EC-600JD can also be preferably used. The amount of the conductive carbon black to be added is preferably 3 to 100 parts by weight and 5 to 60 parts by weight, particularly preferably 10 to 50 parts by weight, and more preferably 15 to 40 parts by weight based on 100 parts by weight of the thermoplastic resin component. Most preferably. If the amount is less than 3 parts by weight, desired conductivity may not be obtained. If the amount exceeds 100 parts by weight, the physical strength, resin flowability and moldability of a film molded product may be reduced.

In order to impart conductivity to the light-shielding resin film layer of the present invention so as not to generate static marks on the photographic light-sensitive material or to prevent a shock to the user, these conductive carbons are used. Preferably, black is contained to make the volume resistivity (measured at 20 ° C. and 60% RH) 1 × 10 ¹² Ω · cm or less, preferably 1 × 1 ¹² Ω · cm.
It is more preferably 0 ¹⁰ Ω · cm or less, and 1 × 1
0 ⁷ Ω · cm or less is particularly preferable.
Most preferably, it is ⁵ Ω · cm or less. The volume resistivity (measured at 20 ° C. and 60% RH) is 1 × 10 ¹² Ω ·
If it exceeds cm, it is difficult to ensure sufficient antistatic properties, and static marks and the like are likely to be generated on the photographic material.

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

A typical example is as follows: 20% by weight of an ethylene / propylene copolymer resin having a crystallinity of 15% as measured by an X-ray diffraction method, and an MFR (A) having a crystallinity of 67%.
(E condition of STM D 1238) is 2.5 g / 10 min, and the density is 0.925 g / cm ^3.
% By weight, 2% by weight of an antistatic agent master batch Kao KK's Erestmaster LL-10 (trade name), 0.1% by weight of calcium stearate as a lubricant, 0.05% by weight of a bisfatty acid amide, and as an antioxidant Hindered phenolic antioxidant (trade name Irega of Ciba Geigy)
Nox 1010) 0.05% by weight, 1% by weight of A-type zeolite which is a volatile gas (hydrogen cyanide, aldehyde, sulfur, etc.) adsorbing substance which adversely affects the photographic properties of a photographic light-sensitive material, and 10% by weight of the following conductive carbon black Is a conductive light-shielding resin film having a thickness of 50 μm and comprising a resin composition containing

The following volume specific resistance values were obtained when the following carbon black was used as the conductive carbon black at 10% by weight (the same composition except for the conductive carbon black). Light-shielding resin film containing 10% by weight of Ketjen Black EC 1.6 × 10 ² Ω · cm Light-shielding resin film containing 10% by weight of Ketjen Black EC600JD 4.5 × 10 ¹ Ω · cm 10 of acetylene black 2.3 × 10 ⁶ Ω · cm Light-shielding resin film containing 10% by weight Vulcan XC-72 1.2 × 10 ⁶ Ω-cm

This light-shielding resin film was excellent in conductivity, photographic properties, film formability, heat sealing suitability, and the like.

Instead of the above low density homopolyethylene resin, high density homopolyethylene resin, ethylene / α-olefin copolymer resin, propylene / α-olefin copolymer resin, homopolypropylene resin, acid-modified polyolefin resin, ethylene / acrylic resin The same applies when using a polyolefin resin containing at least one of an acid copolymer resin, an ethylene / ethyl acrylate copolymer resin, an ethylene / methyl acrylate copolymer resin, and an ethylene / vinyl acetate copolymer resin. A light-shielding resin film having preferable characteristics was obtained.

When used as a packaging material for a photographic light-sensitive material of the present invention, fog does not occur in the photographic light-sensitive material, and there is little occurrence of increase and decrease in photosensitivity and large light-shielding ability.
Even when added to the innermost layer (photosensitive material side), carbon black hardens (fuzziness) and pinholes are less likely to occur in light-shielding resin films such as fish eyes. The average particle size (measured by electron microscopy) is preferably from 6.0 to 9.0, more preferably from 10 to 80 mμ, and most preferably from 10 to 60 mμ. Among them, volatile components (measured according to JIS K 6221)
Is less than 2.0%, furnace carbon black having a DBP oil absorption (measured by the oil absorption A method of JIS K6221) of 50 ml / 100 g or more and an ash content (JIS K6221) of 1.0% or less is inexpensive and has low photographic properties. This is preferable since it does not adversely affect the light-shielding property, improves the light-shielding property, improves the dispersibility, and causes little deterioration in physical properties.

Further, ASTM D 1619 in the packaging material
The sulfur content measured by the method of measurement at −60 is 0.9% or less, preferably 0.7% or less, particularly preferably 0.5% or less, and most preferably 0.1% or less unless the fog increase, sensitivity abnormality, and color development. Irregularities adversely affect the photographic properties of the photographic material. In particular, a free sulfur component which greatly adversely affects the photographic properties of the direct photographic light-sensitive material (each sample is cooled and solidified with liquid nitrogen and then pulverized. The total volume is made up to 100 ml, 10 ml of this solution is injected into a high performance liquid chromatograph, and sulfur is quantified.The conditions for high performance liquid chromatograph are column: ODS silica column (4.6φ).
× 150 mm), separation solution; methanol 95 and water 5 (containing 0.1% of acetic acid and triethylamine each), flow rate: 1
ml / min, detection wavelength; 254 nm, quantification is performed by the absolute calibration curve method. ) Is 0.1% or less, preferably 0.05%
%, Particularly preferably 0.01% or less, most preferably 0.001% or less. Although expensive, furnace carbon black and acetylene black having a sulfur component content of 0.1% or less are suitable for use in photographic materials having an ISO sensitivity of 100 or more for maintaining good photographic properties. In particular, furnace carbon black produced by continuous partial combustion in a furnace at 1250 ° C. to 1600 ° C. using ethylene bottom oil or creosote oil as a raw material oil or by thermal decomposition is inexpensive and has good photographic properties. So preferred.

The content of a cyanide compound deteriorating photographic properties (the amount of hydrogen cyanide determined by 4-pyridinecarboxylic acid / pyrazolone absorption spectrometry is expressed as p to the weight of the light-shielding substance.
pm) is 20 ppm or less, preferably 10 ppm or less, particularly preferably 5 ppm or less, and most preferably 1 ppm or less. In particular, in the case of a photographic light-sensitive material which has been chemically sensitized such as gold sensitization or dye sensitization, 5 ppm or less is essential, and the combined use of a scavenger is preferable.

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

Preferred palladium compounds include palladium (II) chloride, palladium (II) bromide, palladium (II) hydroxide, palladium (II) sulfate, palladium (II) thiocyanate, and tetrachloropalladium (II) acid salt. (Sodium salt, potassium salt, ammonium salt), hexachloropalladium (IV), tetrabromopalladium (II), hexapromoparadymate (IV), bis (salicylate) paradimum (II), bis (Dithiooxalato-
S, S ′) palladium (II) salt, trans-dichlorobis (thioether) palladium (II), tetraamminepalladium (II) salt, dichlorodiamminepalladium (II),
Dibromodiammine palladium (II), oxalatodiammine palladium (II), dinitrodiammine palladium (I
I), bis (ethylenediamine) palladium (II) salt, dichloroethylenediaminepalladium (II), bis (2,2′-
Pyridine) palladium (II) salt, bis (1,10-phenanthroline) palladium (II) salt, tetranitropalladium (II) salt, bis (glycinato) palladium (II), tetrakis (thiocyanato) palladium (II) salt , Dichlorobis (phosphine) palladium (II), dichlorobis (phosphine) palladium (II), di-μ-chloro-bis [chloro (phosphine) palladium (II)], di-μ-chloro-bis [chloro (arsine ) Palladium (II)] and dinitrobis (arsine) palladium (II).

Preferred platinum compounds include platinum chloride (II), platinum chloride (IV), hexafluoroplatinate (IV), tetrachloroplatinate (II), and hexachloroplatinate (IV).
Acid salt, trichlorotrifluoroplatinate (IV), tetrabromoplatinate (II), hexabromoplatinate (IV), dibromodichloroplatinate (II), hexahydroxoplatinate (IV), bis (oxalato ) Platinate (II), dichlorobis (oxalatoplatinate (IV), bis (thiooxalato) platinum (II)
Acid salt, bis (acetylacetonato) platinum (II), bis (1,1
1,1,5,5,5-hexafluoro-2,4-pentanedionato) platinum (II), bis (1,1,1-trifluoro-2,
4-pentanedionato) platinum (II), tetrakis (thiocyanato) platinate (II), hexakis (thiocyanato) platinate (IV), bis (Z) -1,2-dicyanoethylene-
1,2-dithiolatoplatinum (II), dichlorobis (diethylsulfide) platinum (II), tetrachlorobis (diethylsulfide) platinum (IV), bis (glycinato) platinum (I
I), dichloroglycinatoplatinate (II), dichlorobis
(Triethylphosphine) platinum (II), chlorohydridobis (triethylphosphine) platinum (II), tetraammineplatinum (II) salt, tetrachloroplatinum (II) salt, dichlorodiammineplatinum (II), trichloroammineplatinum (II) Salt, hexaammineplatinum (IV) salt, chloropentaammineplatinum (IV)
Salt, tetrachlorodiammineplatinum (IV), dinitrodiammineplatinum (II), dichlorotetrakis (methylamine) platinum (IV) salt, dichloro (ethylenediamine) platinum (II), bis (ethylenediamine) platinum (II) salt, tris ( Ethylenediamine) platinum (IV) salt, dichlorobis (ethylenediamine) platinum (IV) salt, dichlorodihydroxo (ethylenediamine) platinum (IV), tetrakis (pyrimidine) platinum (II) salt,
Dichlorobis (pyridine) platinum (II), bis (2,2′-pipyridine) platinum (II) salt, tetranitroplatinate (II), chlorotrinitroplatinate (II), dichlorodinitroplatinum (II)
Acid salt, dibromodinitroplatinate (II), hexanitroplatinate (IV), chloropentanitroplatinate (IV), dichlorotetranitroplatinate (IV), trichlorotrinitroplatinate (IV), Tetrachlorodinitroplatinate (IV), dibromodichlorodinitroplatinate (IV), trichloro (ethylene) platinate (II), di-μ-chloro-bis (chloro (ethylene) platinum (II), trans- Examples include dichloro (ethylene) (pyridine) platinum (II), bis [bis (β-mercaptoethylamine) nickel (II) -S, S "-platinum (II) salt and dichlorodicarbonylplatinum (II).

Compounds of gold (I or III), rhodium (III), iridium (III or IV) and osmium (II, III or IV) can likewise be used. Chloroaurate (III), rhodium (III) chloride, potassium hexachloroiridate
(IV), potassium tetrachloroylate (III) and potassium hexachloroosmate (IV). The inorganic or organic compound of the noble metal is not limited to the above specific examples as long as the effects of the present invention can be obtained.

The amount of adsorbed iodine (measured according to JIS K 6221) is 20 mg / g or more, preferably 30 mg / g or more, particularly preferably 50 mg / g or more, most preferably 80 mg / g or more, and dibutyl phthalate (DB
P), oil absorption (measured according to JIS K 6221) 50 ml
/ 100 g or more, preferably 60 mg / 100 g or more,
Particularly preferred is carbon black of 70 ml / 100 g or more, most preferably 100 ml / 100 g or more.

The resin composition used for the light-shielding resin film layer contains a lubricant. The inclusion of a lubricant prevents blocking of the light-shielding resin films in the film forming step, laminating step, bag-making step, etc., and also improves the handling suitability and lubricity of the light-shielding resin film to generate wrinkles and streaks. Can be prevented. Furthermore, even if the light-shielding resin film and the photosensitive material are stacked, no blocking occurs, and even if the photosensitive material is rubbed as a packaging bag or the like, scratches and static marks can be prevented. Furthermore, the fluidity of the resin composition can be improved, the film moldability can be improved, and the lubricity of the light-shielding resin film can be improved.

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

The lubricant has a large lubricating effect, such as a fatty acid amide lubricant and a bisfatty acid amide lubricant. However, in the case of a lubricant which easily bleeds out and adversely affects the photosensitive material, 0.01 to 1% by weight is used. Preferably, the content is 0.03 to 0.5% by weight, most preferably 0.05 to 0.3% by weight. If the addition amount is less than 0.01% by weight, there is no effect of addition and only the kneading cost increases. If the amount exceeds 1% by weight, slip between the molten resin and the screw of the extruder is likely to occur, and the amount of resin discharged becomes unstable. In addition, stickiness and bleed-out tend to occur with the lapse of time after film formation. Furthermore, the bleed-out lubricant is transferred to the photographic photosensitive layer to cause development inhibition, thereby causing quality defects such as development unevenness and color unevenness.

Representative commercial lubricant names and manufacturer names are described below. (1) Fatty acid amide-based lubricant; [Saturated fatty acid amide-based lubricant] Behenic acid amide-based lubricant; Diamid KN (Nippon Kasei), etc. Stearamide amide-based lubricant; Armide HT (Lion fat), Alflow S-10 (Nippon fat and oil) , Fatty Acid Amide S (Kao), Diamid 200 (Nippon Kasei), Diamid AP-1 (Nippon Kasei), Amide S. Amide T
(Nitto Chemical), Neutron-2 (Nippon Seika), etc. [hydroxystearic amide lubricant] Palmitic amide lubricant; Neutron S-18 (Nippon Seika), Amide P (Nitto Chemical), etc. Lauric amide Alumide C (Lion Akzo), Diamid (Nippon Kasei), etc. [Unsaturated fatty acid amide lubricant] Erucamide amide lubricant; Alflow P-10 (Nippon Oil & Fats), Neutron-S (Nippon Seika) , LUBOL
(I ・ C ・ I), Diamid L-200 (Nippon Kasei)
Oleic amide lubricants; Armoslip CP (Lion Akzo), Neutron (Nippon Seika), Neutron E-18 (Nippon Seika), Amide O (Nitto Chemical), Diamid O-200, Diamid G-200 (Nippon Kasei), Alflo E-10 (Nippon Oil & Fats), fatty acid amide O (Kao), etc. [Bis fatty acid amide lubricant] Methylene bisbehenic acid amide lubricant;
Kbis (Nippon Kasei) and other methylene bisstearic amide lubricants; Diamid 200 bis (Nippon Kasei), Armowax (Lion Akzo), Bisamide (Nitto Kagaku), etc. Methylene bisoleic amide lubricants; Lubron O (Japan) Chemical conversion) etc. Ethylene bisstearic acid amide lubricant; Armoslip EBS (Lion Akzo) etc. Hexamethylene bisstearic acid amide lubricant; Amid 65 (Kawaken Fine Chemical) etc. Hexamethylene bis oleamide amide lubricant; (2) Nonionic surfactant-based lubricant; Electrostripper-TS-2, Electrostripper-TS-3 (Kao Soap), etc. (3) Hydrocarbon lubricant; Liquid paraffin, natural paraffin, microwax, Isoparaffinic synthetic petroleum hydrocarbons Synthetic paraffin (C16~49, preferably C2
0-30), polyethylene wax (number average molecular weight is 1
Not more than 000, preferably not more than 8,000, in particular not more than 6.0
00 or less is preferable. ), Polypropylene wax (number average molecular weight of 10,000 or less, preferably 8,000
Below, especially 6,000 or less is preferable. ), Chlorinated hydrocarbons, fluorocarbons, etc. (4) Fatty acid-based lubricants; higher fatty acids (preferably C12-35, specifically caproic acid, stearic acid, oleic acid, erucic acid, palmitic acid, etc.), oxy fatty acids, etc. 5) Ester lubricants; lower alcohol esters of fatty acids, polyhydric alcohol esters of fatty acids, polyglycol esters of fatty acids, fatty alcohol esters of fatty acids, etc. (6) Alcohol lubricants: polyhydric alcohols, polyglycols, polyglycerols, etc. ) Fatty acid metal salt lubricant (metal soap); lauric acid, stearic acid, succinic acid, stearyl lactic acid, lactic acid,
Higher fatty acids such as phthalic acid, benzoic acid, hydroxystearic acid, ricinoleic acid, naphthenic acid, oleic acid, palmitic acid, erucic acid and Li, Na, Mg, Ca, Sr,
Compounds with metals such as Ba, Zn, Cd, Al, Sn, Pb, and Cd are preferred, and preferred are magnesium stearate, calcium stearate, sodium stearate, zinc stearate, calcium oleate,
Zinc oleate, magnesium oleate and the like. (8) Partially saponified montanic acid ester; (9) Silicone-based lubricant; Various grades of dimethylpolysiloxane and its modified products (Shin-Etsu Silicone, Toray Silicone), especially various silicone oils improve resin fluidity, lubricity, etc. In addition to exhibiting effects, when used in combination with a light-shielding substance, unexpected effects such as an improvement in dispersibility of the light-shielding substance, an increase in haze (ASTM D-1003) due to clouding of the resin, and an improvement in coloring power and light-shielding properties. Is particularly preferred as the lubricant used in the present invention.

The above silicone oil preferably has a viscosity at room temperature (25 ° C.) of 50 to 100,000 centistokes, and more preferably 5,000 to 3 centistokes.
A high viscosity of 000 centistokes is preferred. Specific examples of silicone and silicone-modified products include polymethylphenylsiloxane, olefin-modified silicone, amide-modified silicone, polydimethylsiloxane,
Amino-modified silicone, carboxyl-modified silicone,
Silicone oil containing modified siloxane bonds such as α-methylstyrene-modified silicone, polyether-modified silicone modified with polyethylene glycol or polypropylene glycol, olefin / polyether-modified silicone, epoxy-modified silicone, amino-modified silicone, and alcohol-modified silicone. . Among the silicone oils, olefin-modified silicones, amide-modified silicones, polydimethylsiloxanes, and polyether-modified silicone oils which have little adverse effect on the photosensitive material and have a large lubricating effect, and are particularly preferable when applied to packaging materials for photosensitive materials. Silicone, olefin / polyether modified silicone. The silicone oil improves the coefficient of friction of a molding material, for example, a resin film in a heated state, reduces sliding resistance generated during hot plate sealing by an automatic packaging machine, and prevents wrinkles from forming, resulting in a beautiful appearance. And a basis for obtaining a resin film having a high sealing performance and an adhesive property without sagging of the packaged object. In addition, it is possible to prevent a decrease in gloss due to sliding and obtain a beautiful seal portion. In the present invention in which silicone oil is used in combination, the coefficient of high-temperature friction can be set to 1.4 or less when performing sliding heat sealing.

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

The light-shielding resin film layer may contain an antioxidant. Prevents the thermal degradation and thermal decomposition of additives such as thermoplastic resins, fatty acids, lubricants, organic nucleating agents, and surfactants, and prevents the fluidity of the thermoplastic resin composition from significantly changing and generating lumps. Can be prevented. Further, it is possible to prevent the generation of thermal decomposition substances (aldehydes and the like) which adversely affect the photographic light-sensitive material. Various known compounds (eg, hydantoin compounds, hydrazine compounds, urea compounds) that reduce, stabilize, stabilize the reaction, or stabilize the adsorption of pyrolytic substances (aldehydes, etc.) to an amount that does not adversely affect the photographic material. Is preferably added. The amount of formaldehyde measured by the acetylacetone method in the packaging material for photographic light-sensitive materials is 500 ppm or less, preferably 300 ppm or less, particularly preferably 150 pp.
m or less, and most preferably 75 ppm or less, good photographic properties can be maintained.

The amount of the antioxidant added is 0.001 to 1.5.
% By weight, preferably 0.005 to 0.7% by weight,
0.01 to 0.45% by weight is more preferable. The amount added is 0.
If the amount is less than 001% by weight, there is no effect of the addition and only the kneading cost increases. If the amount exceeds 1% by weight, the photographic properties of the photographic light-sensitive material utilizing the oxidation and reduction actions are adversely affected and molding is performed. Bleed out to the surface of the product and degrade the appearance.

Representative examples of the antioxidant used in the present invention are shown below. (A) Phenolic antioxidants (t is an abbreviation for tert) Vitamin E (tocopherol), tocopherol dimer (α-tocopherol, β-tocopherol, 5.7)
-Dimethyltocol, etc.), 6-t-butyl-3-methylphenyl derivative, 2,6-di-t-butyl-P-cresol, 2,6-di-t-butyl-phenol, 2.6
-Di-t-butyl-α-dimethylamino-p-cresol, 2.6-di-t-butyl-p-ethylphenol,
2,2'-methylenebis- (4-ethyl-6-t-butylphenol), 4,4'-butylidenebis (6-t-
Butyl-m-cresol), 4,4′-thiobis (6-t
-Butyl-m-cresol), 4,4-dihydroxydiphenylcyclohexane, butylated hydroxyanisole, alkylated bisphenol, styrenated phenol, 2,6-di-t-butyl-4-methylphenol,
2,6-di-t-butyl-4-ethylphenol, n-
Octadecyl-3- (3'.5'-di-t-butyl-4 '
-Hydroxyphenyl) propinate, 2.2′-methylenebis (4-methyl-6-t-butylphenol),
4.4'-thiobis (3-methyl-6-t-butylphenyl), 4,4'-butylidenebis (3-methyl-6-t
-Butylphenol), 4.4′-thiobis (3-methyl-6-t-butylphenol), stearyl-β (3.
5-di-t-butyl-4-hydroxyphenyl) propionate, 1.1.3-tris (2-methyl-4hydroxy-5-t-butylphenyl) butane, 1.3.5 trimethyl-2.4.4. 6-tris (3.5-di-tert-butyl-4-hydroxybenzyl) benzene, tetrakis [methylene-3 (3.5-di-tert-butyl-4-hydroxyphenyl) propionate] methane, etc.

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

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

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

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

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

(G) Other antioxidants useful for air oxidation: Dilauryl thiodipropionate, etc. Representative examples of the most preferred hindered phenolic antioxidants for the present invention are shown below.

1,3,5-trimethyl 2,4,6-tris
(3,5-di-tert-butyl-4-hydroxybenzyl) benzene, tetrakis [methylene-3- (3 ′ · 5 ′)
-Di-tert-butyl-4'-hydroxyphenyl)
Propionate] methane, octadecyl-3,5-di-
tert-butyl-4-hydroxy-hydrocinnamate, 2,2 ′, 2′-tris [(3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxy] ethyl isocyanurate, 1,3,5 -Tris (4-ter
t-butyl-3-hydroxy-2,6-di-methylbenzyl] isocyanurate, tetrakis (2,4-di-te
rt-butylphenyl) 4,4'-biphenylenediphosphite, 4,4'-thiobis- (6-tert-butyl-O-cresol), 2,2'-thiobis- (6-te
rt-butyl-4-methylphenol), tris- (2
-Methyl-4-hydroxy-5-tert-butylphenyl) butane, 2,2'-methylene-bis- (4-methyl-6-tert-butylphenol), 4,4'-methylene-bis- (2,6 -Di-tert-butylphenol), 4,4'-butylidenebis- (3-methyl-6-t
tert-butylphenol), 2,6-di-tert-
Butyl-4-methylphenol, 4-hydroxymethyl-2,6-di-tert-butylphenol, 2,6-
Di-tert-4-n-butylphenol, 2,6-bis (2'-hydroxy-3'-tert-butyl-5'-
Methylpentyl) -4-methylphenol, 4,4′-methylene-bis- (6-tert-butyl-O-cresol), 4,4′-butylidene-bis (6-tert-butyl-m-cresol), 3 , 9-bis {1,1-dimethyl-2- [β- (3-t-butyl-4-hydroxy-5-
Methylphenyl) propionyloxy] ethyl {2,4
8,10-tetraoxaspiro [5,5] undecane and the like. Among them, those having a melting point of 100 ° C. or higher, particularly 120 ° C. or higher are preferable. Further, it is effective to use it in combination with a phosphorus antioxidant. Furthermore, it is particularly preferable to use at least one phosphorus antioxidant, at least one hindered phenol antioxidant, and at least one hydrated double salt compound in total of three or more.

When at least one of the phosphorus-based antioxidants is contained, phosphorous acid generated by thermal decomposition has a large adverse effect on the photographic light-sensitive material, and fog is generated. 0.01 ~
It is preferable to add 5.0% by weight, particularly 0.05 to 3.0% by weight.

The above-mentioned vitamin E (tocopherol) and tocopherol dimer have not only an excellent antioxidant effect, but also have a light-shielding ability which can be improved by coloring a molded article yellow and using the same with a light-shielding substance such as carbon black. And the dispersibility is improved as compared with the case where the light-shielding substance alone is added, so that a molded article having the same light-shielding property can be obtained even when the addition amount of the light-shielding substance is reduced by 10% or more. As a result, various effects such as prevention of deterioration of photographic properties, improvement of physical strength, improvement of appearance, and reduction of material cost are exhibited, and thus it is particularly preferable as the photographic photosensitive material packaging material of the present invention.

Particularly preferred antioxidants are phenolic antioxidants, and commercially available products include various types of Irganox manufactured by Ciba-Geigy and Sumilize manufactured by Sumitomo Chemical Co., Ltd.
rBHT, Sumilizer BH-76, Sumi
lizer WX-R, Sumilizer BP-10
1 mag. Also, 2,6-di-butyl-p-cresol (BHT), a low-volatility, high-molecular-weight phenolic antioxidant (trade name: Ireganox 1010, Ireg)
anox 1076, Topanol CA, Iono
x330 etc.), and a phosphorus-based antioxidant (distearyl-
At least one of pentaerythritol-diphosphite, dilauryl thiodipropionate, distearyl thiopropionate, tris (2,4-di-t-butyl-phenyl) phosphite, dialkyl phosphate, etc. It is effective to use more than one species in combination.

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

The molecular weight is 200 or more in that it has many excellent properties such as little adverse effect on the photographic properties of the photographic light-sensitive material, little thermal decomposition even at a resin melting temperature (130 to 400 ° C.), and little bleed-out over time. , Preferably 3
The hindered phenolic antioxidant is preferably at least 00, particularly preferably at least 400, most preferably at least 500.

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

The light-shielding resin film layer may contain an antistatic agent. The incorporation of an antistatic agent prevents or suppresses the generation of static electricity generated by friction with the photographic light-sensitive material, thereby preventing the generation of static marks on the photographic light-sensitive material.

The addition amount of the antistatic agent is preferably 0.01 to 10% by weight, more preferably 0.05 to 7% by weight.
0.1 to 5% by weight is most preferred. If the addition amount is less than 0.01% by weight, the effect of addition is not sufficient, and only the kneading cost increases. On the other hand, if the addition amount exceeds 10% by weight, slip between the molten resin and the screw of the extruder tends to occur, and the discharge amount of the resin becomes unstable. Further, stickiness and bleed-out tend to occur with the passage of time after molding.

Various surfactants can be used as the antistatic agent.

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

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

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

Representative examples of the amphoteric surfactant are shown below. Various known antistatic agents can be used in the present invention by adjusting the type and amount of addition so as not to adversely affect the photographic properties of the photographic light-sensitive material, or by combining with other additives. For example, the Plastic Data Handbook (KK
Various types of antistatic agents disclosed on pages 776 to 778 of the Industrial Research Council) and various types of antistatic agents and antistatic agents disclosed on pages 123 to 151 of the Plastic Data Collection (published by KK Chemical Industry Co.) Surface modification of molecules-(KK Kashobo, March 25, 1972, supplementary edition), various antistatic agents and the like.

Among the above antistatic agents, nonionic (nonionic) antistatic agents are particularly preferred because they have a small adverse effect on photographic properties and human body and have a large effect of preventing static marks. Also, an antistatic agent master batch, for example, Kao KK's Erest Master 1215, 326, 32
0, PP-425 (above, suitable for PP resin), Erestmaster HE-110, HE-510 (above, HDPE
Suitable for resin), Erestmaster LL-10 (L-LD
And the like are also preferable. The amount of various estmasters (trade names) manufactured by Kao KK is 0.1 to 10% by weight, preferably 0.2 to 8% by weight, more preferably 0.1 to 8% by weight.
3 to 6% by weight, particularly preferably 0.4 to 4.5% by weight,
Most preferably, it is 0.5 to 3% by weight.

The resins other than the thermoplastic elastomer that can be used in the light-shielding resin film layer of the present invention include:
Polyolefin resins that are inexpensive, have good photographic properties, suitability for disposal, and suitability for recycling, are readily available worldwide, and have excellent various properties can be used. As the polyolefin resin, homopolyethylene resin, homopolybutene-1 resin, homopoly-4-methylpentene-1 resin,
Random and block copolymer resin of ethylene and α-olefin, homopolypropylene resin or random and block copolymer resin of propylene and α-olefin, acid-modified polyolefin resin, ethylene / acrylic acid copolymer resin, ethylene There are propylene / butene-1 copolymer resin, ethylene / acrylate copolymer resin, ethylene / vinyl acetate copolymer resin, various polyolefin elastomers and the like. Even when used alone 2
You may mix and use more than one kind.

As the homopolyethylene resin, a radical initiator such as oxygen or peroxide may be used.
A low-density branched polyethylene resin having a long-chain branching density of 0.910 to 0.925 g / cm ³ , produced by a method of polymerizing ethylene under a temperature and pressure condition of 1000 to 3000 kg / cm ^2. Manufactured by a method in which ethylene is polymerized under conditions of 50 to 250 ° C. and 50 to 200 kg / cm ² using a medium / low pressure Ziegler catalyst (Ti system) or a Phillips catalyst (Cr system).
A linear high-density polyethylene resin having a linear density of 0.941 to 0.985 g / cm ³ and a high-pressure method or a medium / low-pressure method can be obtained. There is a medium density polyethylene resin having a density of 0.926 to 0.940 g / cm ³ manufactured by blending. Furthermore, there are homopolyethylene resins of various densities in which the molecular weight distribution and the composition distribution have been reduced using a metallocene polymerization catalyst, which has recently been studied for practical use.

The packaging material for a photographic light-sensitive material of the present invention may be formed as a single layer composed of only a light-shielding resin film layer or as a multilayer. That is, even if it is formed by a multi-layer co-extruded film comprising two or more light-shielding resin film layers, or by a multi-layer co-extruded film of a light-shielding resin film layer and a thermoplastic resin film layer, A flexible sheet layer may be laminated directly on the extruded film or indirectly via an adhesive layer.

As the flexible sheet layer, various thermoplastic resin films, for example, various polyethylene resins,
Various ethylene copolymer resins, homopolypropylene resins,
Various propylene copolymer resins, polyvinyl chloride resins, various polyamide resins, polyacrylonitrile resins, ethylene / vinyl alcohol copolymer resins, polycarbonate resins, various polyester resins (PET resin, PBT resin, A-PET resin, PEN resin And the like, a mixed or polymer alloy or modified resin film thereof, and a monoaxially or biaxially stretched (including molecular orientation) film of these various thermoplastic resin films. Further, there are triacetate film, cellophane, regenerated cellulose film, paper, synthetic paper, nonwoven fabric, metal foil, metal-deposited film, inorganic substance-deposited film, metal-deposited paper, and the like.

A particularly preferred flexible sheet has a basis weight of 20 to 400 g / m which does not adversely affect the photographic light-sensitive material.
² Various neutral and acidic papers (waste paper, recycled paper, unbleached kraft paper, semi-bleached kraft paper, bleached kraft paper, Hineri base paper, Clupak paper, Duostress paper, white board paper, photographic base paper,
Fine paper, non-wood (kenaf, bagasse, straw, bamboo, corn stalk, sugar cane, papyrus, etc.), pulp paper, medium paper using high yield pulp, pure white roll paper, coated paper, imitation paper, glassine paper ), Nonwoven fabric, synthetic paper and uniaxially or biaxially stretched (including molecular orientation) thermoplastic resin films, and inorganic oxide deposited uniaxially or biaxially stretched (including molecular orientation) thermoplastic resin films.

These flexible sheets can be used singly or in combination of two or more kinds. The fact that the melting point is higher by at least 10 ° C. than that of the heat-sealed (inside conductive thermoplastic resin) layer improves bag-making suitability. Prevent wrinkles and tears,
It is preferable from the viewpoint of improving the appearance. Particularly preferred is a biaxially stretched thermoplastic resin film having a thickness of 5 to 70 μm, preferably 7 to 50 μm, and particularly preferably 10 to 35 μm. In addition, the Young's modulus (A
STM D 882) is at least 50 kg / mm ² , preferably at least 70 kg / mm ² , particularly preferably 90 kg / m 2
m ² or more, most preferably 100 kg / mm ² or more, and is a flexible sheet larger than the longitudinal Young's modulus of the intermediate thermoplastic resin layer.

The application to which the packaging material of the present invention can be applied will be described. (1) Moisture-proof / sealing packaging bag for packaging a transparent, colored or printed film unit with a lens (Japanese Patent Publication No. 7-1380, Japanese Patent Application Laid-Open No. 5-1970087, Japanese Patent Application Laid-Open No. 7-725)
No. 93, JP-A-8-248573, JP-A-8-248573
JP-A-254793, JP-A-8-334869, JP-A-9-15796, JP-A-9-5439
No. 5, JP-A-9-120119, JP-A-9-119
244187, JP-A-9-274288,
JP-A-10-186586, JP-A-10-197
994, etc.). (2) Transparent, colored or printed photographic film in a plastic container (JIS 135 film, APS
And moisture-proof and sealed packaging bags (for example, Japanese Patent Application Laid-Open No. 8-254793) for collectively packaging two or more films or microfilms. (3) Moisture-proof / sealing / light-shielding bags for sheet-like photographic photosensitive materials such as photographic paper, film for printing plate making, cut film for photographing, X-ray film, PS plate (JP-B 2-2700, JP-B-2) -2701, JP-A-8-25479
3, JP-A-5-5972, etc.). (4) Light-shielding film for a belt-shaped photographic photosensitive material package (JP-A-2-72347, JP-A-6-214350, Japanese Utility Model Publication No. 5-29471, Japanese Utility Model Publication No. 6-8593)
Gazette, Japanese Utility Model Publication No. 7-50743, Japanese Utility Model Publication No. 8-10
812, JP-A-63-153255, etc.). (5) Moisture-proof sealed light-shielding bags for roll-shaped photographic light-sensitive materials such as photographic paper, movie films, micropositive films, printing plate-making films, and heat-developed diffusion transfer papers (JP-A-6-6735).
No. 8, etc.). (6) A moisture-proof / light-shielding film or a leader film for a light-room packed package of a photographic material such as a photographic paper or a photographic film (JP-A-62-172344, JP-A-2-723).
No. 47, Japanese Patent Application Laid-Open No. 5-72672, Japanese Patent Application Laid-Open
216176, JP-A-6-75341, JP-A-6-214350, JP-A-6-148820
JP, JP-A-7-257510, JP-A-7-9-9
2618, JP-A-8-40468, JP-A-10-97030, JP-B-56-16608, JP-B-6-8593, JP-B-8-9725 and the like. (7) A moisture-proof and light-shielding film for packaging a photographic photosensitive material in the form of a bulk roll (JP-A-3-53243). (8) Instant film pack (Japanese Patent Laid-Open No. 8-627)
82, JP-A-10-22879, JP-A-10-228080, and the like. (9) Shading paper for photographic film (Japanese Patent Laid-Open No. 48-22020)
JP, JP-A-50-67644, JP-A-52-67644
JP-A-150016, JP-A-55-140835, JP-A-58-17434, JP-A-58-18
6744, JP-A-59-68238, JP-A-60-35728, JP-A-61-36216, JP-A-4-136842, and JP-A-9-80.
No. 695). (10) Shading bag for instant film pack
JP-A-221814, JP-A-10-22879, JP-A-10-228080, JP-A-10-208
No. 293359).

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

Further, it can be used for various overwrapping packages. For example, Japanese Utility Model Publication No. 7-50743, Japanese Utility Model Publication 8-7398, Japanese Utility Model Publication 8-9723, Japanese Utility Model Publication 8-9724, Japanese Utility Model Publication No. 8-10812,
JP-A-6-148820, JP-A-6-21435
0, JP-A-7-257510, JP-A-7-257510
No. 287350, etc. Moisture-proof light-shielding film or bag for a light-room-loaded package of a band-shaped photosensitive material, overwrapping packaging in a carton or tray, overwrapping caramel type, overwrapping snack type, over cigarette type There are wrapping packaging, roll wrapping packaging, stick-shaped wrapping packaging, twist wrapping packaging, etc.
Further, it can be used for various packaging bodies described in the Japan Packaging Technology Association, published on July 1, 1995, Handbook of Packaging Technology, pp. 754-774.

The photographic light-sensitive materials to which the photographic light-sensitive material packaging material of the present invention can be applied are shown below. (1) Silver halide photographic materials (film for printing, color or black and white photographic paper, color or black and white negative film, master paper for printing, DTR (diffusion transfer) photosensitive material,
Computer typesetting film and paper, color or black-and-white positive film, color reversal film, microfilm, surveillance film, movie film, self-developing photographic photosensitive material, direct positive film and paper, etc.)
(JP-A-4-136838, JP-A-4-1723)
39, JP-A-5-113623, JP-A-9
JP-A-325450, JP-A-10-62901, JP-A-10-62903, JP-A-10-62
904, JP-A-10-62905, JP-A-10-62906, JP-A-10-62921, JP-A-10-142731, etc.) (2) Thermal developing photosensitive material (thermal developing color photosensitive material) Thermal development black-and-white photosensitive materials (for example, JP-B-43-4921 and JP-B-43-4924), "Basics of photographic engineering", silver salt photography (ed. 1879, published by Corona Co., Ltd.), pages 553 to 555, and Research Tice. Closure Magazine June 1978 Issue 9
Pages 15 to 15 (RD-17029). Further, JP-A-59-12431 and JP-A-60-124
2950 and 61-52343,
-13295, 10-62898, 1
0-62899 and U.S. Pat. No. 3,457,075.
No. 3,574,627, U.S. Pat. No. 4,042,394, U.S. Pat.
(3) Photosensitive / thermosensitive recording materials (photothermography (photosensitive materials described in JP-A-3-72358) and the like.・ Recording material using thermal image formation method) (4) Diazonium photographic material (4-morpholinobenzenediazonium microfilm, microfilm, copy film, printing plate material, etc.) (5) Azide, diazide type photograph Photosensitive materials (photosensitive materials containing para-azidobenzoate, 4,4'diazidostilbene, etc., for example, copying films, printing plates, etc.) (6) Quinonediazide-based photographic materials (orthoquinonediazide, orthonaphthoquinonediazide compounds, For example, a photographic image containing benzoquinone (1,2) -diazide- (2) -4-sulfonic acid phenyl ether or the like. (7) Photopolymer (photosensitive material containing vinyl-based monomer, printing plate, adhesive film, etc.) (8) Polyvinylcinnamic acid Ester-based photosensitive materials (eg, printing films, IC resists, etc.)

The photographic light-sensitive material package of the present invention is manufactured using the photographic light-sensitive material packaging material as described above, and has a moisture permeability (measured under the condition B of JIS Z 0208) of 10 g / m ^2. · 24 hours or less, preferably 5 g / m ² · 2
The photographic light-sensitive material is sealed and packaged for 4 hours or less, more preferably 3 g / m ² · 24 hours or less, particularly preferably 1 g / m ² · 24 hours or less.

If the water vapor transmission rate exceeds 10 g / m ² · 24 hours, the moisture affects the photographic light-sensitive material and adversely affects the sensitivity, color development and the like. In particular, when a silver halide photographic material which has been chemically sensitized with a sensitizing dye is hermetically sealed and packaged, the moisture permeability needs to be 10 g / m ² · 24 hours or less.

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

FIGS. 1 to 7 are partial cross-sectional views showing the layer structure of a packaging material for a photographic light-sensitive material.

The photographic photosensitive material packaging material shown in FIG. 1 is a single layer of the light-shielding resin film layer 1a.

The packaging material for photographic light-sensitive material shown in FIG. 2 comprises a two-layer coextruded film IIa of a light-shielding resin film layer 1a and a thermoplastic resin film 2a containing a light-shielding substance.

The packaging material for photographic light-sensitive material shown in FIG.
Coextruded film of two light-shielding resin film layers 1a
IIa.

The packaging material for photographic light-sensitive material shown in FIG. 4 is a two-layer coextruded film IIa of a light-shielding resin film layer 1a and a thermoplastic resin film 2 containing no light-shielding substance.
It consists of

The packaging material for photographic light-sensitive material shown in FIG. 5 is obtained by laminating a flexible sheet layer 3a containing a light-shielding substance via an adhesive layer 4 on a light-shielding resin film layer 1a.

The packaging material for photographic light-sensitive material shown in FIG.
Three-layer coextruded film of two light-shielding resin film layers 1a and a flexible sheet layer 3a containing a light-shielding substance II
It consists of Ia.

The packaging material for photographic light-sensitive material shown in FIG. 7 has a two-layer co-extruded film IIa of a light-shielding resin film layer 1a and a thermoplastic resin film 2a containing a light-shielding substance,
A flexible sheet 3 containing no light-shielding substance is laminated via an adhesive layer 4.

Next, an embodiment of a photographic light-sensitive material package according to the present invention will be described with reference to the drawings.

8 to 11 are plan views of a packaging bag as a photographic photosensitive material package viewed from a slightly oblique angle.

The packaging bag 10 shown in FIG. 8 is a three-side sealed bag having a heat seal portion 11 formed on the bottom and both sides. After the photographic photosensitive material is inserted through the opening, the opening is folded and sealed, and the folded portion is fixed with an adhesive tape or the like such as cellophane tape to form a sealed package.

The packaging bag 10 shown in FIG. 9 has heat seal portions 11 formed on four sides, that is, a bottom side, both sides and an upper side.

The packaging bag 10 shown in FIG. 10 has a heat seal portion 11 formed substantially at the center of the bottom and side surfaces.
After the photographic photosensitive material is inserted through the opening, the opening is folded and sealed, and the folded portion is fixed with an adhesive tape or the like such as cellophane tape to form a sealed package.

The packaging bag 10 shown in FIG. 11 has a heat seal portion 11 formed substantially at the center of the bottom, top, and side surfaces.

[0101]

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

Example 1 As shown in FIG. 1, Example 1 is a single-layer wrapping material for a photographic light-sensitive material comprising only a light-shielding resin film layer.

The crystallinity measured by the X-ray diffraction method was 8
%, MFR is 3 g / 10 min, and 4
15% by weight of a propylene / ethylene copolymer elastomer containing 40 mol% of butene-1 having two carbon atoms, a crystallinity of 68% as measured by an X-ray diffraction method, MF
R is 2.5 g / 10 min, density is 0.925 g / cm ³ ,
20% by weight of the homopolyethylene resin produced by the high-pressure radical polymerization method has a crystallinity of 3 as measured by X-ray diffraction.
5%, MFR 4 g / 10 min, density 0.915 g / c
At m ³ , an ethylene-hexene-1 random copolymer resin containing 6 mol% of hexene-1 having 6 carbon atoms as an α-olefin produced using a metallocene catalyst (main component of a zirconium compound) is 47 0.7% by weight, 15% by weight of acetylene black having a sulfur content of 0.02%, 0.2% by weight of zinc stearate as a lubricant, 0.05% by weight of bisfatty acid amide, a hindered phenolic antioxidant As tetrakis [methylene-3 (3,5
-Di-t-butyl-4-hydroxyphenyl) propionate] methane in an amount of 0.05% by weight and a nonionic antistatic agent master batch (Electmaster 11-, manufactured by Kao Corporation)
This is a light-shielding polyolefin-based resin film formed to a thickness of 80 μm by an inflation film molding method under the following conditions using an olefin-based resin composition containing 2% by weight of (ID). The blown film forming conditions are as follows.

<Inflation Film Molding Conditions> Cooling; Air cooling (20 ° C.) Screw; Mixing type L / D; 25 Lip clearance; 1.0 mm Blow ratio; 1.5 Resin temperature; 175 ° C. Draw ratio;

Example 2 As shown in FIG. 1, Example 2 is a single-layer wrapping material for a photographic light-sensitive material comprising only a light-shielding resin film layer.

The crystallinity measured by the X-ray diffraction method was 16
%, MFR 5 g / 10 min, density 0.890 g / cm ³
15% by weight of an ethylene / butene-1 random copolymer elastomer having a crystallinity of 6 as measured by an X-ray diffraction method.
3%, MFR 20 g / 10 min, density 0.920 g /
25% by weight of a homopolyethylene resin having a cm ³ of 46% and a MFR of 2.5 g as measured by X-ray diffraction.
/ 10 min, 44.8% by weight of an ethylene / hexene-1 random copolymer resin having a density of 0.920 g / cm ³ , 15% by weight of acetylene black and 0.1% of zinc stearate.
This is a light-shielding olefin-based resin film formed to a thickness of 80 μm by an inflation film molding method using the olefin-based resin composition containing 2% by weight under the same conditions as in Example 1.

Comparative Example 1 The crystallinity measured by the X-ray diffraction method was 63%, the MFR was 20 g / 10 min, and the density was 0.1%.
25% by weight of a 920 g / cm ³ homopolyethylene resin, a crystallinity of 46% as measured by X-ray diffraction,
R is 2.5 g / 10 min and the density is 0.920 g / cm ³ .
8% by weight, 15% of the same acetylene black as in Example 1
Using an olefin-based resin composition containing 0.2% by weight of calcium stearate and a thickness of 80 μm by a blown film molding method under the same conditions as in Example 1.
m is a light-blocking olefin-based resin film.

Comparative Example 2 Instead of the total amount of 82.7% by weight of the three resins used in Example 1, the crystallinity measured by the X-ray diffraction method was 68%, and the MFR was 2.5 g /. 10
This is a light-shielding polyolefin-based resin film having the same contents as in Example 1 except that 82.7% by weight of a low-density homopolyethylene resin having a density of 0.925 g / cm ³ is used.

In Examples 1 and 2, as compared with Comparative Examples 1 and 2, the dispersibility of acetylene black was good, and the occurrence of bumps and microgrids was significantly reduced.

[Example A] In Example A, as shown in FIG. 2, a photograph formed of a two-layer co-extruded blown film composed of a light-shielding resin film layer 1a and a thermoplastic resin film layer 2a. It is a packaging material for photosensitive materials.

The light-shielding resin film layer 1a was made of the same olefin resin composition as in Example 1, and had a thickness of 50 μm.
Is a light-shielding polyolefin-based resin film formed on the substrate.

The thermoplastic resin film layer 2a has a crystallinity of 79% and an MFR of 0.05 as measured by an X-ray diffraction method.
g / 10 minutes, a density of 0.951 g / cm ³ , a molecular weight distribution of 25, a high-density polyethylene resin of 60% by weight, a crystallinity measured by an X-ray diffraction method of 66%, and an MFR of 20 g /
10 minutes, 10% by weight of a homopolyethylene resin having a density of 0.920 g / cm ³ , a crystallinity of 40% measured by an X-ray diffraction method, an MFR of 4.0 g / 10 minutes, and a gaseous concentration using a single-site catalyst. 24.8% by weight of ethylene-hexene 1 copolymer resin polymerized and produced by the phase method, 5% by weight of acetylene black, 0.15% by weight of calcium stearate, 0.05% by weight of a hindered phenolic antioxidant It is made of the contained resin composition and has a thickness of 30 μm.
It is formed in.

The packaging material for a photographic light-sensitive material comprising a light-shielding two-layer co-extruded blown film having a thickness of 80 μm is a photographic light-sensitive material comprising a single-layer light-shielding polyolefin resin film having a thickness of 80 μm in Examples 1 and 2. Packaging strength, light blocking ability, film formability,
The appearance, suitability for bag making, and suitability for sealing were excellent, and no melt fracture (irregular irregularities were generated on the film surface) even when the molding speed was increased, and the productivity was good and preferred. Furthermore, since the whole is made of a polyolefin-based resin composition that is stable and has light-shielding properties, the photographic properties are good and the suitability for recycling is excellent.

Example B As shown in FIG. 3, Example B is a packaging material for a photographic photosensitive material comprising a two-layer co-extruded blown film composed of two light-shielding resin film layers 1a.

The light-shielding resin film layer 1a was made of the same olefin resin composition as in Example 2 and had a thickness of 40 μm.
Is a light-shielding polyolefin-based resin film formed on the substrate.

In Example B, the thickness (80 μm) and the resin composition were the same as those in Example 2, but in Example B, the thickness of 80 μm as the whole packaging material was changed to a film layer having a thickness of 40 μm.
Equally divided into two layers and co-extruded to form a blown film, so that no pinholes are generated (even if a pinhole or a thin portion occurs in one light-shielding resin film layer, the other light-shielding resin film layer Ensures light-blocking properties),
Inspection-free continuous molding became possible, and the speed of the resin composition flowing into the ring die orifice was also reduced to about half of that in Example 2. As a result, parallel streamlines were easily formed in the die land. There was no outbreak. Therefore, no irregularities were generated on the film surface, and the film was excellent in appearance with no gloss unevenness and high in commercial value. Unexpected effects such as improvement in film formability and improvement in film productivity also occurred.

Further, scratches and pressure fog were not generated on the photographic light-sensitive material. An unexpected effect that the light-shielding ability and the physical strength were also superior to that of Example 2 also occurred. Melt fracture did not occur even when the resin temperature was lowered by 10 ° C. or more than in Example 2. As a result, low-temperature film molding became possible. The occurrence of thermal degradation and thermal decomposition of the additives was significantly reduced, and the generation of malodors and aldehyde compounds which adversely affected the photographic properties of the photographic light-sensitive material were reduced. As a result, the odor was small and the photographic properties were good.

[0118]

According to the present invention, the above-described configuration has the following effects. i) The dispersibility of the carbon black is improved (reduction of bumps and micro grids and improvement in light blocking ability), and the occurrence of bumps and micro grids is reduced, and the light blocking ability is improved. ii) Heat sealability is improved. iii) The physical strength reduction rate decreases. Therefore, the physical strength is improved as compared with the conventional packaging material, so that the thickness can be reduced. iv) Since compatibility with many thermoplastic resins is improved, suitability for recycling and suitability for incineration are improved. v) Even if a large amount of the conductive substance is contained, the decrease in physical strength and film formability is small, so that the conductive substance can be contained in a large amount and the conductivity is improved. vi) The low temperature bag breaking prevention property is improved.

[Brief description of the drawings]

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

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

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

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

FIG. 6 is a partial cross-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. 7 is a partial cross-sectional view showing a layer structure of an embodiment of the packaging material for a photographic light-sensitive material according to the present invention.

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

FIG. 9 is a plan view of an embodiment of a photographic photosensitive material package according to the present invention.

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

FIG. 11 is a plan view of an embodiment of a photographic photosensitive material package according to the present invention.

[Explanation of symbols]

 1a ... light-shielding resin film layer 2, 2a ... thermoplastic resin film layer 3, 3a ... flexible sheet layer 4, 4a ... adhesive layer IIa ... ... light-shielding multilayer co-extruded film 10 ... ... light-shielding bag 11 ... …… Heat seal part a ……… Shows light-shielding properties

Claims (3)

[Claims] 1. The crystallinity measured by the X-ray diffraction method is 3
A light-shielding resin film layer comprising a resin composition containing 5% by weight or more of a thermoplastic elastomer of 0% or less, a lubricant, and 0.1 to 60% by weight of carbon black; Packaging material. 2. The packaging material according to claim 1, wherein the thermoplastic elastomer is a polyolefin-based elastomer, and the content of α-olefin units other than ethylene and propylene is 16 mol% or more. 3. The photographic photosensitive material according to claim 1, wherein the photographic photosensitive material has a moisture permeability (JIS Z0).
208) (measured under the condition B of No. 208) in a sealed package of 10 g / m ² · 24 hours or less.