JPH06148817A - Packaging material for photographic sensitive material - Google Patents

Abstract

PURPOSE:To improve low temp. sealing property, heat seal strength and physical strength by forming a light shielding thermoplastic resin film layer containing thermoplastic resins having different charsacteristics and a light shielding material. CONSTITUTION:This packaging material has a light shielding thermoplastic resin film layer 1a containing three or more thermoplastic resins having different characteristics and the light shielding material. This packaging material for a photographic sensitive material consists of the single layer of the light shielding thermoplastic resin film layer 1a, or may consist of an extruded film IIa consisting of a light shielding thermoplastic reisn film layer 1a and a thermoplastic resin film layer 2a. Further, a lubricant may be added to the light shielding thermoplastic resin film to improve the fluidity of the resin, adaptability for extrusion, film forming property, lubricating property, antiblocking property, adaptability as a package of photographic sensitive material, antistatic property, wear resistance, dispersion property of light shielding material, etc.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photographic light-sensitive material packaging material for packaging a photographic light-sensitive material such as a photographic film or photographic paper.

[0002]

2. Description of the Related Art Conventionally, as a packaging material for a photographic light-sensitive material, a heat-sealing layer is formed on a cross-laminated film in which two layers of uniaxially stretched film made of high-density homopolyethylene resin are laminated so that the stretching axes of the stretched film intersect. As one example, there is a laminate of low-density homopolyethylene resin layers containing a light-shielding substance (Japanese Utility Model Publication No. 56-19087). In addition, there was also one containing a light-shielding film composed of 1% by weight or more of a light-shielding substance and 50% by weight or more of an L-LDPE resin (Japanese Patent Publication No. 2700/1990).

[0003]

However, the above-mentioned conventional packaging materials do not have all the properties required for photographic light-sensitive materials. That is, the packaging material disclosed in Japanese Utility Model Publication No. 56-19087 was insufficient in maintaining heat-sealing strength over time, foreign matter sealing property, flexibility and flatness (no curling). Moreover, the packaging material of Japanese Patent Publication No. 2-2700 has large tear strength, heat seal strength, and gelbotest strength even if it is a single-layer L-LDPE resin light-shielding film.
Moreover, it was inexpensive and extremely preferable as a packaging material for a photographic light-sensitive material, but the dispersibility and Young's modulus of the light-shielding substance were not sufficient. Also, when packaging photographic light-sensitive materials with sharp edges or heavy weight,
In some cases, the bag may be broken, the packaging material itself may be thin and thin, resulting in poor light-shielding properties, or the heat-sealed portion may be thinned to cause pinholes.

The present invention solves the above problems and provides a photographic material having sufficient characteristics that a packaging material for a photographic light-sensitive material should have even with a single layer of a light-shielding thermoplastic resin film layer. An object is to provide a packaging material for a photosensitive material.

[0005]

The present invention has been made in order to achieve the above object, and therefore, the packaging material for a photographic light-sensitive material of the present invention comprises three or more kinds of thermoplastic resins having different characteristics and a light-shielding substance. And a light-shielding thermoplastic resin film layer containing a.

The characteristics of three or more thermoplastic resins having different characteristics include low temperature heat sealability, heat seal strength retention with time, heat seal strength, high Young's modulus, pinhole resistance, abrasion resistance, tear strength, Anti-blocking,
It has many properties such as impact drilling strength, flexibility, gel votest strength, foreign matter sealing property, flatness (no curling), fluidity, and no adverse effect on photographic light-sensitive materials.

Examples of the thermoplastic resin include low density homopolyethylene resin, medium density homopolyethylene resin, high density homopolyethylene resin, ethylene / α-olefin copolymer resin (L-LDPE resin), poly-1-butene resin,
Polyisobutylene resin (synthetic rubber), propylene / ethylene elastomer (synthetic rubber), propylene / ethylene / diene elastomer (synthetic rubber), various polyamide resins (nylon 6, nylon 66, nylon 11, nylon 1)
2, nylon 610 etc.), homopolypropylene resin, propylene / α-olefin copolymer resin (eg propylene
Ethylene random copolymer resin, propylene / ethylene block copolymer resin, propylene / butene-1 copolymer resin, propylene / butene-1 block copolymer resin, etc.), various polyester resins, vinyl chloride resin, fluorine resin, Vinylidene chloride resin, polystyrene resin, impact-resistant polystyrene resin with synthetic rubber, ABS resin, methacrylic resin, polyacetal resin, polycarbonate resin, cellulose resin, polyvinyl alcohol resin, ethylene vinyl alcohol copolymer resin (EVOH resin), polyurethane elastomer ( Synthetic rubber), acrylonitrile resin, polyimide resin, plastic alloy, blended resin of two or more kinds of these, thermoplastic resin recycled (recycled) after using these resins as packaging materials, and thermoplastic resins thereof. There thermoplastic resin reinforced-modified by kneading auxiliary materials such as various additives.

[0008] Particularly preferred the L-LDPE used in the packaging material for photographic photosensitive materials (L inear L ow Density P oly e
thylene) resin is called the third polyethylene resin, and it is a low cost, high strength resin that meets the demands of the times of energy saving and resource saving, which has the advantages of medium / low density, high density and both homopolyethylene resins. . 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. Is a polyethylene resin. Suitable butene-1, octene-1, and α-olefin in terms of polymerization suitability, physical strength and cost.
Hexene-1,4-methylpentene-1, heptene-
1, decene-1, etc. are used.

The density is generally considered to be a low to medium density homopolyethylene resin, but 0.87 to 0.97 g / cm ³ is commercially available.
Many are within the range. Melt index is 0.1
Many are within the range of up to 50 g / 10 minutes. L-LDPE
As a resin polymerization process, 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 apparatus.

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)

Among these L-LDPE resins, the melt index (hereinafter referred to as MI) is particularly preferable in terms of physical strength, heat seal strength and film formability.
0.1-10g / 10min (JIS K-6760), density 0.870-
0.940 g / cm ³ (JIS K-6760), a flow ratio of 20 to 70, and an α-olefin having 6 to 8 carbon atoms, obtained by a liquid phase process and a gas phase process.

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 Idemitsu Petrochemical Co., Ltd. in which octene-1 having 8 carbon atoms is introduced as an α-olefin side chain.
Of MORETEC and Stamilex of DSM and Dowlex of Dow Chemical (the above are L-LDPE resins obtained by the co-liquid phase process of four products). Preferred typical examples obtained by the low-pressure vapor phase process are the trade names: TUFLIN of UCC Co. and Nippon Unicar Co., Ltd., in which hexene-1 having 6 carbon atoms is introduced as an α-olefin side chain. There is TUFTTHEN etc.

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 (above, butene-1, which is a product of two companies and has 4 carbon atoms of butene-1). use).

Representative examples of the ethylene copolymer resin are shown below. (1) ethylene-vinyl acetate copolymer 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 (7) ethylene-methyl acrylate copolymer resin (8) ethylene-ethyl acrylate copolymer resin (hereinafter
(Displayed as EEA resin) (9) Ethylene-acrylonitrile copolymer resin (10) Ethylene-acrylic acid copolymer resin (11) Ionomer resin (copolymer of ethylene and unsaturated acid is cross-linked with a metal such as zinc Resin) (12) Ethylene-α-olefin copolymer resin (L-LDP
E resin) (13) ethylene-propylene-butene-1 terpolymer resin (14) modified polyolefin resin (15) ethylene vinyl alcohol copolymer resin and the like.

The light-shielding substance can secure the light-shielding property, and has various properties such as antiblocking property, moldability, physical strength, dripproof property, antistatic property, and adsorption of substances that adversely affect the photographic light-sensitive material. The effect of can be exhibited.

Examples of the light-shielding substance are shown below. (1) Oxides: silica, diatomaceous earth, alumina, titanium oxide, iron oxide, zinc oxide, magnesium oxide, antimony oxide, barium ferrite, strontium ferrite, beryllium oxide, pumice, pumice balloon, alumina fiber, etc. (2) Water Oxide: Aluminum hydroxide, magnesium hydroxide, basic magnesium carbonate (3) Carbonate: Calcium carbonate, magnesium carbonate, dolomite, dawsonite, etc. (4) (Sulfite): Calcium sulfate, barium sulfate, ammonium sulfate, calcium sulfite Etc. (5) Silicates ... talc, clay, mica, asbestos,
Glass fibers, glass balloons, glass beads, calcium silicate, montmorillonite, bentonite, etc. (6) Carbon: carbon black, graphite, carbon fibers, carbon hollow spheres, etc. (7) 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.

It should be noted that, in particular, it has little adverse effect on the photographic light-sensitive material, has an effect of improving antistatic property, antiblocking property, physical strength, and antioxidant property, and has a large light-shielding ability and is inexpensive. Various carbon blacks are preferred. 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. Examples of commercially available products include carbon black # 20 (B), # 30 (B), # 33 (B), # 4 manufactured by Mitsubishi Kasei.
0 (B), # 44 (B), # 45 (B), # 50, # 55, # 100, # 600,
Examples include # 2200 (B), # 2400 (B), MA8, MA11, and MA100.

As an overseas product, for example, a product of Cabot
Black Pearls 2,46,70,71,74,80,81,607 etc., Re
gal 300, 330, 400, 660, 991, SRF-S, Vulcan
3, 6, etc., Sterling 10, SO, V, S, FT-FF,
MT-FF etc. are mentioned. Furthermore, United R, BB, 15,102,3001,3004,3006 of Ashland Chemical Co.,
3007, 3008, 3009, 3011, 3012, XC-3016, XC-30
17, 3020, etc., but not limited to these.

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 black which is a modified by-product carbon black are preferable as the expensive light-shielding substance having an antistatic effect. . If necessary, it is also preferable to mix the former and the latter according to the required characteristics. There are various forms of blending the light-shielding substance into the thermoplastic resin as described above, but the masterbatch method is preferable in terms of cost, workability, prevention of workplace pollution, and the like.

Among various light-shielding substances, pH is 4.
0-9.0, preferably 6.0-8.0, with an average particle size of 10-
120mμ, preferably 15-60mμ, volatile components 3.0% or less, preferably 1.0% or less, particularly preferably 0.8% or less, oil absorption 50ml / 100g or more, preferably 60ml / 100
g or more, particularly preferably 70 ml / 100 g or more, does not deteriorate photographic properties such as "fog" or "sensitivity abnormality" in the photographic light-sensitive material, and does not cause foaming or silver strip defects during film forming. In addition, the dispersibility is good and the generation of microgrids (aggregated impurities) is small, which is preferable.

The free sulfur content in the above carbon black is 0.6% or less, preferably 0.3% or less, and particularly preferably 0.1% so as not to adversely affect the photographic properties of the photographic light-sensitive material.
1% or less, the cyan compound content is 0.01% or less, preferably 0.005% or less, particularly preferably 0.001% or less, the aldehyde compound content is 0.1% or less, preferably
It is 0.05% or less, particularly preferably 0.01% or less. Care should be taken because these substances, even in small amounts, adversely affect the photographic properties.

The preferred light-shielding substance has a refractive index of 1.50 or more, preferably 1.55 or more, and particularly preferably 1.
There are over 60 various inorganic pigments and various metal powders, metal flakes, metal pastes, metal fibers and carbon fibers. Typical examples of the inorganic pigment and the metal powder having a preferable refractive index of 1.50 or more are shown below, but the present invention is not limited thereto. The numbers in parentheses indicate the refractive index (light wavelength 589 mμ) measured by the Larsen oil immersion method. Inorganic pigments with a refractive index of 1.50 or higher include rutile-type titanium oxide (2.76), anatase-type titanium oxide (2.52), zinc oxide (2.37), antimony oxide (2.35), lead white (2.09), zinc white (2.02) , Lithopone (1.84), carbon black (1.61), barite powder (1.64), barium sulfate (1.64), calcium carbonate (1.58), talc (1.58), calcium sulfate (1.56),
Silica anhydride (1.55), quartz powder (1.54), magnesium hydroxide (1.54), basic magnesium carbonate (1.52), alumina (1.50), etc.

Calcium silicate (1.
46), diatomaceous earth (1.45), hydrous silicic acid (1.44), etc. are not preferable because they have a small light-shielding ability and easily generate microgrids (aggregated impurities).

Typical examples of metal powder (including metal paste) include aluminum powder, copper powder, stainless powder, iron powder, silver powder, tin powder, zinc powder, steel powder, and the like, but aluminum powder and aluminum are particularly preferable. Paste is preferred.

The amount of the light-shielding substance added is preferably 0.01 to
It is 30% by weight, more preferably 0.1 to 20% by weight, and most preferably 1.0 to 10% by weight. The surface of the light-shielding substance is coated to improve dispersibility, improve resin fluidity, and prevent the formation of photographic fog, pressure fog, and scratches (foreign matter-like solidification) on the photographic light-sensitive material. It can be coated with a substance.

Typical examples of the surface coating substance are shown below. (1) Coupling agent Coupling agent containing azidosilanes (JP-A-62-62)
-32125, etc.) Silane coupling agent coating (aminosilane, etc.) Titanate coupling agent coating (2) Silica deposition followed by alumina deposition coating (3) Zinc stearate, magnesium stearate, steer Higher fatty acid metal salt coating such as calcium phosphate (4) Surfactant coating such as sodium stearate, potassium stearate, oxyethylene dodecyl amine etc. (5) Barium sulfide aqueous solution and sulfuric acid aqueous solution in the presence of excess barium ion The average particle size of 0.1-2.5μ
m barium sulphate is produced, an aqueous alkali silicate solution is added to this water slurry to produce barium silicate on the surface of barium sulphate, then mineral acid is added to the slurry to decompose the barium silicate into hydrous silica. Deposition and coating on barium sulfate surface (6) Metal hydrate oxide (one or more hydrate oxides of titanium, aluminum, cerium, zinc, iron, cobalt or silicon) and / or metal oxide (titanium). , Aluminum, cerium, zinc, iron, cobalt or silicon oxide, and a surface coating with a composition consisting only of (7) aziridine group, oxazoline group and N-hydroxyalkylamide group in the molecule. 1 selected from the group
(1) Surface coating with polyoxyalkyleneamine compound (8) Surface coating with polyoxyalkyleneamine compound (9) Surface coating with cerium cation, selected acid anion and alumina (10) Substituted α-hydroxy group Surface coating with an alkoxytitanium derivative having a carboxylic acid residue (11) Surface coating with polytetrafluoroethylene (12) Surface coating with polydimethylsiloxane or modified silicon (13) Surface coating with phosphate ester compound (14) 2 Surface coating with 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, zinc citrate, etc., or a combination of two or more). Surface coated with a hydrocarbon, etc.

The surface coating amount is preferably 0.001 to 5% by weight, more preferably 0.01 to 3% by weight, and most preferably 0.05 to 1.5% by weight with respect to the light-shielding substance.

The light-shielding thermoplastic resin film of the present invention has improved resin fluidity, extrusion suitability, film molding suitability, slipperiness, blocking prevention, packaging suitability of photographic light-sensitive material, prevention of static electricity generation, resistance to abrasion. A lubricant can be added for the purpose of improving the wear resistance and the dispersibility of the light-shielding substance.

The names of typical commercially available lubricants and manufacturers are listed below. (1) Silicone-based lubricants; various grades of dimethylpolysiloxane and its modified products (Shin-Etsu Silicone, Nippon Unicar, Toray Silicone), etc. (2) Oleic acid amide-based lubricants: Armoslip CP (Lion Akzo), fatty acid amide O ( Kao), Neutron (Nippon Seika), Neutron E-18 (Nippon Seika), Amide O (Nitto Kagaku), Alfuro E-10 (Nippon Yushi), Diamid O-200 (Nippon Kasei), Diamid G-200 (Nippon Kasei), etc. (3) Erucamide amide lubricants; Alfuro-P-10 (Nippon Yushi), Neutron-S (Nippon Seika), LUBROL
(I ・ C ・ I), Diamid L-200 (Nippon Kasei), etc. (4) Stearic acid amide lubricants; Alfro-S-10 (Nippon Yushi), Armide HT (Lion Yeast), Fatty Acid Amide S (Kao) , Diamid AP-1 (Nippon Kasei), Amide S (Nitto Kagaku), Neutron 2 (Nippon Seika), Diamid 200 Bis (Nippon Kasei), etc. (5) Bis fatty acid amide lubricant; Bisamid (Nippon Kasei) , Diamid NK screw (Nippon Kasei), Lubron O
(Nippon Kasei), Amide 60 (Kawaken Fine Chemicals),
Diamond Mid 200 screw (Nippon Kasei), Sripacks-K
N (Nippon Kasei), Armowax EBS (Lion Akzo), Hoechst Wax-C (Hoechst Japan),
Kemetrowax-100 (Nissan Ferrochemical) etc. (6) Alkylamine lubricants; Electrostripper-T
S-2 (Kao soap), etc. (7) Hydrocarbon lubricants; liquid paraffin {Unico H-15
0, Unico (Union Petroleum), Crystol-70 (Esso Standard Petroleum), Dufful Oil CP-50 (Idemitsu Kosan), etc.}, natural paraffin, micro wax, synthetic paraffin, polyethylene wax {Hoechst Wax A-520 (Hoechst Japan) ), AC polyethylene-6
A, AC Polyethylene-629 (Allied Chemical)
Etc., polypropylene wax, chlorinated hydrocarbons, fluorocarbon oils, etc. (8) Fatty acid-based lubricants; higher fatty acids (C ₁₂ or more are preferred), oxyfatty acids, etc. (9) Ester-based lubricants; butyl stearate (Kao soap,
Lower alcohol esters of fatty acids such as Nippon Oil & Fats, polyhydric alcohol esters of fatty acids such as Nissan Castor Wax A (Nippon Oil & Fats), diamond wax (Nippon Rika), polyglycol esters of fatty acids, fatty alcohol esters of fatty acids, etc. (10 ) Alcohol lubricants; polyhydric alcohols, polyglycols, polyglycerols, etc. (11) Metal soaps: higher fatty acids such as lauric acid, stearic acid, ricinoleic acid, naphthenic acid, oleic acid, and Li,
Mg, Ca, Sr, Ba, Zn, Cd, Al, Sn, P
Compounds with metals such as b (12) Partial ester of fatty acid and polyhydric alcohol; monoglyceride M (NOF Corporation), fatty acid monoglyceride R-60, fatty acid monoglyceride O-60 (Matsumoto Oil & Fats), ricinoleic acid monoglyceride, behenic acid monoglyceride , Oleic acid monoglyceride, erucic acid monoglyceride, liquemal S-300, liquemal PS-100 (RIKEN vitamin), monoglyceride S, monoglyceride NS (Kao Atlas), etc.

The amount of these lubricants added is 0.001 to 10.0% by weight, preferably 0.005 to 7.0% by weight, particularly preferably 0.01.
~ 5.0% by weight. If the amount added is less than 0.001% by weight, the effect of adding the lubricant will not be exhibited and only the kneading cost will increase. When the amount added exceeds 10.0% by weight, the slipperiness is excessively improved, slipping occurs between the resin and the screw of the extruder, and it becomes impossible to extrude a stable amount of resin. Further, bleed-out increases, which causes problems such as deterioration of appearance, stickiness, and adhesion of dust. Therefore, it is preferable to select the necessary minimum amount.

Silicone lubricants include various grades of dimethylpolysiloxane and its modified products (Shin-Etsu Silicone, Nippon Unicar, Dow Corning, UCC, Toray Silicone) and polymethylphenylsiloxane, α-methylstyrene-modified silicone, carboxyl-modified silicone, Fluorine modified silicone, alkyl modified silicone, alkylaryl modified silicone, olefin modified silicone, polyether modified silicone modified with polyethylene glycol or polypropylene glycol, olefin / polyether modified silicone, epoxy modified silicone, amino modified silicone, amide modified silicone, There is a silicone-based oil containing a modified siloxane bond such as alcohol-modified silicone. Among the silicone-based oils, particularly olefin-modified silicone, amide-modified silicone, polyether-modified silicone, olefin / polyether-modified silicone, etc. are excellent. In particular, when the packaging material for the photographic light-sensitive material is a single-layer or multi-layer film, the silicone oil improves the friction coefficient of the film in a heated state and reduces the sliding resistance generated during hot plate sealing by an automatic packaging machine. By preventing the occurrence of wrinkles, it is possible to form the basis for obtaining a film that retains the performance of having a beautiful appearance, a high degree of sealing property, and an adhesiveness that does not sag on the packaged object. 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 viscosity at room temperature is preferably in the range of 100 to 100,000 centistokes, more preferably 5,000 to 3
A high viscosity of 0,000 centistokes is recommended. The addition amount varies depending on the type and purpose of use, but preferably 0.01 to 5.
It is 0% by weight, more preferably 0.03 to 3.0% by weight, and most preferably 0.05 to 1.5% by weight.

The silicone-based lubricant may be used alone, in combination of two or more kinds, or in combination with other lubricants or plasticizers. In particular, it is preferable to use the above-mentioned silicone lubricant in combination with one or more of the various fatty acid amide lubricants (2) to (5).

Representative examples of the plasticizer are shown below. (1) Phthalate plasticizers Dibutyl phthalate, diheptyl 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-based plasticizers Alkyl epoxy stearate, 4,5-epoxytetrahydrophthalic acid diisodecyl, etc. (5) Other plasticizers Chlorinated paraffin, polyester, sucrose octaacetate, etc. 0.01-10.0% by weight, preferably 0.05-
It is 7.0% by weight, particularly preferably 0.1 to 5.0% by weight.

If it 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. 10.0% by weight
If it exceeds, slipping with the screw of the extruder occurs and it becomes impossible to extrude a stable resin amount, and the thickness unevenness of the multilayer coextrusion inflation film becomes large.

The effects of adding the silicon-based oil are as follows. (1) Improving the fluidity of the resin, reducing the motor load on the screw, and preventing the occurrence of melt fracture. (2) Sufficient lubricity can be ensured without adding a fatty acid amide that bleeds out to form a white powder. (3) The friction retention of the film in a heated state is reduced, the suitability for automatic bag making is improved, wrinkles at the time of heat sealing and the deterioration of gloss due to sliding are prevented, and a beautiful sealed portion can be obtained. (4) When used in combination with a light-shielding substance, the light-shielding ability can be improved, and the light-shielding property can be secured even if the amount of addition of the light-shielding substance that deteriorates the physical properties is reduced.

The above-mentioned metal soap is used to detoxify halogen compounds which adversely affect the photographic characteristics of photographic light-sensitive materials in thermoplastic resins, prevent the generation of microgrit, prevent die lip stains,
It is possible to improve the dispersibility of the light-shielding substance.

That is, in a thermoplastic resin such as an ethylene-α-olefin copolymer resin, a halogen compound such as a metal halide is usually used as a polymerization catalyst. These halogen compounds adversely affect the photographic properties of the photographic light-sensitive material, generate fog, and give abnormalities in sensitivity and gradation.
However, higher fatty acids such as lauric acid, stearic acid, ricinoleic acid, naphthenic acid, oleic acid, erucic acid, and behenic acid and Li, Mg, Ca, Sr, Ba, Zn, Cd,
It was found that the addition of a higher fatty acid metal salt (metal soap), which is a compound with a metal such as Sn or Pb, particularly zinc stearate, magnesium stearate, or calcium stearate improves the photographic properties and causes almost no fog. . For example, after the L-LDPE resin film containing 3% by weight of carbon black and 1.5% by weight of zinc stearate and the color photographic paper are contacted with each other at 50 ° C. and 80% RH for 5 days, the fog density when developed is 0.12 → It was found that the unexpected effect of decreasing to 0.02 was exhibited.
Furthermore, the dispersibility of carbon black, which has the drawback of being inexpensive as a light-shielding substance and having a large light-shielding ability, but having a large amount of agglomeration due to aggregation, improves the dispersibility of the carbon black, and the formation of a lump (foreign matter-like solidification)
It was found that the unexpected effect of decreasing to / 10 or less is exhibited at the same time.

When a hydrocarbon type low molecular weight thermoplastic resin (hydrocarbon type lubricant, etc.) is used in combination with an antioxidant, microgrit generation prevention, die lip stain prevention, dispersibility of light-shielding substances, film formability improvement, low temperature Heat sealability improvement, resin fluidity improvement, lubricity improvement, blocking prevention,
It is possible to improve the extrusion suitability and the packaging suitability of the photographic light-sensitive material.

In the light-shielding thermoplastic resin film of the present invention, decomposition products (for example, alcohols, aldehydes, ketones, carboxylic acids, etc.) that prevent oxidative decomposition of the resin and adversely affect the photographic properties of the photographic light-sensitive material are used. Antioxidants can be added to prevent the formation of Representative examples of antioxidants are shown below. (A) Phenolic antioxidant Vitamin E, vitamin E carboxylic acid ester, 6-t-
Butyl-3-methylphenyl derivative, 2.6-di-t
-Butyl-P-cresol, 2.2'-methylenebis-
(4-Ethyl-6-t-butylphenol), 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-butylphenyl), 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-based antioxidant 6-ethoxy-2,2,4-trimethyl-1,2-dihydroquinoline, polymer of 2,2,4-trimethyl-1,2-dihydroquinoline, Trimethyldihydroquinoline derivatives, etc. (c) Allylamine-based antioxidants 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-based antioxidant 2-mercaptobenzimidazole, zinc salt of 2-mercaptobenzimidazole, 2-mercaptomethylbenzimidazole, etc. ) Phosphite antioxidants Alkylated allyl phosphite, diphenylisodecyl phosphite, tris (nonylphenyl) phosphite sodium phosphite, trinonylphenyl phosphite, triphenyl phosphite, etc. (f) Thiourea antioxidant Agents Thiourea derivatives, 1,3-bis (dimethylaminopropyl) -2-thiourea, etc. (G) Other antioxidants useful for air oxidation Dilauryl thiodipropionate, etc. (H) Hindered phenolic antioxidants 1 , 3,5-Trimethyl 2,4,6-tris ( , 5-di -t
ert-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-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-tert-butylphenol), 2,6-di-tert-butyl-4-methylphenol, 4-hydroxy. Methyl-2,6-di-tert-butylphenol, 2,6-di-tert-4-n-butylphenol, 2,6-bis (2'-hydroxy-3'-ter
t-Butyl-5'-methylbenzyl) -4-methylphenol, 4,4'-methylene-bis- (6-tert-butyl-
O-cresol), 4,4'-butylidene-bis (6-tert.
-Butyl-m-cresol) and the like. The melting point (Melting point) is 1 because there is little bleed-out and thermal decomposition, and there is little adverse effect on the photographic properties of photographic light-sensitive materials.
A temperature of 00 ° C or higher is preferable, and a temperature of 120 ° C or higher is particularly preferable.

Representative commercial antioxidants are shown below. (1) Phenolic antioxidant; SUMILIZER B
HT (Sumitomo), IRGANOX 1076 (Ciba Geigy),
MARK AO-50 (Adeka Argus), SUMIL
IZER 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
LIZERS-6 (Ouchi Shinko), IRGANOX 142
5 WL (Chiba Geigy), MARKAO-80 (ADEKA ・
Argus), SUMILIZER GA-80 (Sumitomo),
TOPANOL CA (ICI), MARK AO-30
(Adeka Argus), MARK AO-20 (Adeka Argus)
Argus), IRGANOX 3114 (Ciba Geigy), M
ARK AO-330 (Adeka Argus), IRGANO
X 1330 (Ciba Geigy), CYANOX 1790 (AC
C), IRGANOX 1010 (Ciba Geigy), MARK
AO-60 (Adeka Argus), SUMILIZER
BP-101 (Sumitomo), TOMINOX TT (Yoshitomi), etc. (2) Phosphorus antioxidants; IRGAFOS 168 (Ciba Geigy), MARK 2112 (Adeka Argus), WESTO
N 618 (Borg Warner), MARK PEP-8 (Adeka Argus), ULTRANOX 626 (Borg Warner), MARK PEP-24G (Adeka Argus), MARK PEP-36 (Adeka Argus), H
GA (Sanko) etc. (3) Thioether antioxidant; DLTDP "YOSH
ITOMI "(Yoshitomi), SUMILIZER TPL (Sumitomo), ANTIOX L (NOF), DMTD" YOSH "
ITOMI "(Yoshitomi), SUMILIZER TPM (Sumitomo), ANTIOX M (NOF), DSTP" YOSH "
ITOMI "(Yoshitomi), SUMILIZER TPS (Sumitomo), ANTIOXS (NOF), SEENOX 412S
(Cipro), MARK AO-412S (Adeka Argus), SUMILIZER TP-D (Sumitomo), MAR
K AO-23 (Adeka Argus), SANDSTAB
P-EPQ (sand), IRGAFOS P-BPQ F
F (Ciba Geigy), IRGANOX 1222 (Ciba Geigy), MARK 329K (Adeka Argus), WEST
ON 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-102
4 (Ciba Geigy), CUNOX (Mitsui Toatsu), etc.

Preferred antioxidants are phenolic antioxidants, and hindered phenolic antioxidants are particularly preferred. Commercially available products include various Irganox products manufactured by Ciba-Geigy and Sumilizer BHT and Sumi manufactured by Sumitomo Chemical Co., Ltd.
lizer BH-76, Sumilizer WX-R, Sumilizer B
P-101 and the like.

Further, 2,6-di-t-butyl-p-cresol (BHT), a low volatility high molecular weight hindered phenol type antioxidant (trade name: Ireganox 1010, Irega
Nox1076, Topanol 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. However, the antioxidant is a reducing substance, which originally has a bad influence on the photographic light-sensitive material, and it is necessary to select the type and the addition amount in consideration of the effect balance with the action of suppressing thermal decomposition. Phenol-based and phosphorus-based antioxidants are preferable because they have less adverse effects on the photographic light-sensitive material such as fog and abnormal sensitivity. As the phenolic antioxidant, a hindered phenolic antioxidant is particularly preferable. Among the hindered phenolic antioxidants, those having a melting point of 100 ° C or higher, particularly 120 ° C or higher are preferable. Particularly, it is preferable to use two or more kinds of phenolic antioxidants and / or phosphorus antioxidants in combination.

Further, when used in combination with carbon black or the like, the antioxidant effect 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.) pages 327 to 329 of various antioxidants and PLASTICS AGE ENCYCLOPEDIA Advanced Edition 1986 (KK Plastic Age) pages 211 to 212 of various antioxidants, etc. Is possible.

A mechanism for preventing the above antioxidant from adversely affecting the photographic light-sensitive material will be described.
The oxidative decomposition of the thermoplastic resin is greater in the polyolefin resin having more CH ₃ branches. This is because the oxygen absorption amount is large, so that the oxidative decomposition is (high) polypropylene resin> homopolyethylene resin> ethylene / α-olefin copolymer resin (low).

Various polyethylene resins (including ethylene / α-olefin copolymer resin) and various polypropylene resins (including propylene / ethylene copolymer resin), which are typical thermoplastic resins of crystalline resins, are hydrocarbons. Yes,
It is considered that the autoxidation of hydrocarbons proceeds in a chain as follows, once free radicals are formed by dehydration in the presence of oxygen. RH → R ・ R ・ + O ₂ → ROO ・ ROO ・ + RH → ROOH + R ・ ROOH → RO ・ + ・ OH RO ・ + RH → ROH + R ・ ・ OH + RH → HOH + R ・ In this way, the oxidation of hydrocarbons is accelerated. A large amount of alcohol, aldehyde, acid, etc. are produced, 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.

As the radical scavenger used in the present invention, 1.1-diphenyl-2-bicrylhydrazyl,
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 1,000 to 10,000 ppm.

Antioxidants include free radical chain terminators that react with the free radicals (mainly ROO.) That are chain propagators to inactivate them, and hydroperoxide ROOH that is the main source of free radicals. There is a peroxide decomposer that decomposes and stabilizes this.

The former includes alkylphenol antioxidants and aromatic amine antioxidants. The latter includes sulfur-based antioxidants and phosphorus-based antioxidants.

Since various antioxidants are also reducing agents that adversely affect the photographic light-sensitive material, the quality deterioration of the photographic light-sensitive material becomes a serious problem unless the kind and the amount added are carefully examined.

An antistatic agent can be added to the light-shielding thermoplastic resin film of the present invention. Representative examples of the antistatic agent are shown below. I. Nonionic (= nonionic) (1) Alkylamine derivative: T-B103 (Matsumoto Yushi), T
-B104 (Matsumoto Yushi) Alkylamide type polyoxyethylene alkylamine: Armostat 31
0 (Lion oil / fat) Tertiary amine (lauryl amine): Armostat 400 (Lion oil / fat) N, N-bis (2-hydroxyethylcocoamine): Armostat 410 (Lion oil / fat) Tertiary amine: ANTISTATIC 273C, 273, 273E
(Fine Org. Chem) N-hydroxyhexadecyl-di-ethanol-amine: Belg.
P.654, 049 N-hydroxyoctadecyl-di-ethanol-amine: (Natio
nal Dist.) (2) Fatty acid amide derivative: TB-115 (Matsumoto Yushi), Elegan P100 (Nippon Yushi), Eleek SM-2 (Yoshimura Yushi Kagaku) Hydroxystearic acid amide Oxalic acid-N, N'-distearylamide Butyl ester: Hoechst polyoxyethylene alkylamide (3) Ether type polyoxyethylene alkyl ether RO (CH ₂ CH ₂ O) nH Polyoxyethylene alkylphenyl ether Special nonionic type: Resist 104, PE100, 116-118
(Daiichi Kogyo Seiyaku), Resist PE132,139 (Daiichi Kogyo Seiyaku), Elegan E115, Chemistat 1005 (Nippon Yushi), Eleek BM-1 (Yoshimura Yushi Kagaku), Electrostripper TS, TS2, 3, 5, 5. EA, EA2, 3
(Kao Soap) (4) Polyhydric alcohol ester type glycerin fatty acid ester: mono-, di-, or triglyceride such as stearic acid or hydroxystearic acid, monoglyceride (Japanese camphor), TB-123 (Matsumoto Yushi),
Resist 113 (Daiichi Kogyo Seiyaku Co., Ltd.) Sorbitan fatty acid ester Special ester: Elyk BS-1 (Yoshimura Yushi Kagaku) 1-Hydroxyethyl-2-dodecylglyoxazoline: British cellophane

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

III. Cation system (1) Amide type cation: Resist PE300, 401, 40
2,406,411 (Daiichi Kogyo Seiyaku Co., Ltd.) (2) Quaternary ammonium salt Quaternary ammonium chloride Quaternary ammonium sulfate Quaternary ammonium nitrate Katimin CSM-9 (Yoshimura Yushi Kagaku), CATANAC
609 (American cyanamide), Denon 314C (Maruhishi Yuka), Armostat 300 (Lion oil), 100V (Armor), Electrostriper-ES (Kao soap),
Chemistat 2009A (Nippon Yushi) Stearamido propyl-dimethyl-β-hydroxyethyl amm
onium nitrate: CATANAC SN (American
Dianamid)

IV. Zwitterion type (1) Alkyl petaine type (2) Imidazoline type Rheostat 53,532 (Lion oil), AMS 53 (Lion oil), AMS303,313 (Lion oil) Alkyl imidazoline type (3) Metal salt type AMS 576 ( Lion oil / fat Rheostat 826,923 (lion oil / fat) (RNR'CH ₂ CH ₂ CH ₂ NCH ₂ COO) ₂ Mg R ≧ C,
R '= H or (CH ₂₎ mCOO- (by Lion Yushi) R = C ₃ ~ ₈ hydrocarbon, A = oxygen or imino group, M =
Organic amines or metals (4) Alkylalanine type

V. Conductive resin Polyvinylbenzyl type cation Polyacrylic acid type cation

VI. Other Register 204, 205 (Daiichi Kogyo Seiyaku), Elegan 2
E, 100E (Nippon Yushi), Chemistat 1002, 1003, 201
0 (Nippon Yushi), Eleek 51 (Yoshimura Yushi Kagaku), ALRO
MINE RV-100 (Geigy) Among these antistatic agents, nonionic (nonionic) type antistatic agents are particularly preferable because they have little adverse effect on photographic properties and human body.

The total amount of one or more of the above lubricants and antistatic agents added is 0.001 to 5.0% by weight, preferably 0.005.
~ 3.0% by weight. If the amount added is less than 0.001% by weight, the antistatic effect and the effect of improving lubricity are hardly exhibited, and only the kneading cost increases. In addition, the addition amount is 5.0
If the amount exceeds 10% by weight, not only is there little effect of increasing the amount, but also bleed-out increases over time and the amount of resin extruded changes significantly due to slipping with the screw, causing problems such as large variations in layer thickness. To do.

To the light-shielding thermoplastic resin film of the present invention, various anti-drop agents can be added in order to prevent water droplets from being generated. Typical examples of the non-drip agent are shown below. Diglycerin monostearate, polyglycerin monopalmitate, sorbitan monolaurate, sorbitan monostearate, sorbitan monooleate, sorbitan monoerucate, polyoxyethylene sorbitan fatty acid ester, stearic acid monoglyceride, polyoxy Ethylene nonylphenol ether, sorbitan sesquipalmitate, diglycerin sesquioleate, sorbitol fatty acid ester, sorbitol fatty acid dibasic acid ester, diglycerin fatty acid dibasic acid ester, glycerine fatty acid dibasic acid ester, sorbitan fatty acid dibasic acid Ester, sorbitan palmitate,
Sorbitan stearate, sorbitan palmitate / propylene oxide 3 mol adduct, sorbitan palmitate / propylene oxide 2 mol adduct, sorbitol stearate, sorbitol stearate / ethylene oxide 3 mol adduct, diglycerin palmitate,
Glycerin palmitate, glycerin palmitate / ethylene oxide 2 mol adduct, and the like.

The amount of these non-dripping agents added is 0.01 to 5% by weight, preferably 0.1 to 3% by weight, particularly preferably 0.3 to 2%.
% By weight.

A conductive substance can be added to the light-shielding thermoplastic resin film of the present invention. Examples of the conductive substance include nonionic surfactants, anionic surfactants, amphoteric surfactants, alkylamine derivatives, conductive carbon black, metal surface coating pigments, metal powders, carbon fibers, metal fibers and the like. . The amount added is 0.01 to 5% by weight in the case of surfactants, and in the case of other conductive substances.
0.05 to 20% by weight is preferable.

A nucleating agent can be added to the light-shielding thermoplastic resin film of the present invention in order to improve crystallization rate, film forming rate, rigidity, physical strength and the like. Nucleating agents include organic nucleating agents and inorganic nucleating agents. Representative examples of these are shown below.

Organic nucleating agents 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, their aluminum salts, Aromatic metal phosphates, alkyl alcohols having 8 to 30 carbon atoms, condensation products of polyhydric alcohols and aldehydes, and alkylamines, such as pt-butyl aluminum benzoate.
1,3,2,4-dibenzylidene sorbitol, di-substituted benzylidene sorbitol compound represented by the following formula

[0065]

[Chemical 1]

(Wherein 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), stearyl lactic acid Calcium, magnesium and other metal salts, N-
A compound represented by the following formula, such as (2-hydroxyethyl) -stearylamine

[0067]

[Chemical 2]

(In the formula, R ₃ is an alkyl group having 8 to 30 carbon atoms, k and l are both 0 to 10, and k + l ≧
It is 1. ) 1,2-hydroxystearic acid lithium salts, sodium salts, potassium salts, calcium salts, metal salts such as magnesium salts, alkyl alcohols such as stearyl alcohol and lauryl alcohol, sodium benzoate, benzoic acid, sepatic acid, etc. Including.

The inorganic nucleating agent is an alkali metal hydroxide such as lithium hydroxide, sodium hydroxide or potassium hydroxide,
Alkali metal oxides such as sodium oxide, alkali metal carbonates such as lithium carbonate, sodium carbonate, potassium carbonate, sodium hydrogen carbonate and potassium hydrogen carbonate, alkaline earth metal waters such as calcium hydroxide, magnesium hydroxide and barium hydroxide. Examples thereof include oxides, alkaline earth metal oxides such as calcium carbonate and calcium oxide.

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.

As a nucleating agent, it has a great effect of promoting crystallization of resin as a nucleating agent, reduces molding failures, improves film forming speed, improves rigidity and physical strength, etc. without adversely affecting photographic light-sensitive materials.
Particularly preferable examples of the organic nucleating agent having a large addition effect are described below. di- (o-methylbenzylidene) sorbitol o-methylbenzylidene-p-methylbenzylidene sorbitol di- (m-methylbenzylidene) sorbitol m-methylbenzylidene-o-methylbenzylidene sorbitol di- (p-methylbenzylidene) sorbitol m-methylbenzylidene-p-methylbenzylidene sorbitol 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 1 ・ 3-benzylidenesorbitol 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) sorbitol 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.

Particularly preferred is a dibenzylidene sorbitol compound. In particular, the polyolefin resin which is the crystalline resin of the present invention (preferably propylene / α-olefin random copolymer resin, homopolyethylene resin having a density of 0.910 g / cm ³ or more, and ethylene / α having a density of 0.870 / cm ³ or more).
Olefin copolymer resin) physical strength improvement, rigidity improvement,
The following di-substituted benzylidene sorbitol compositions are particularly preferable in order to improve the film forming speed, reduce the molding failure, and improve the offensive odor and bleed-out which are the drawbacks of the conventional organic nucleating agents.

As an essential component of this di-substituted benzylidene sorbitol composition, a compound of the general formula (I)

[0074]

[Chemical 3]

[Wherein R and R'independently represent an atom or a group selected from the group consisting of a chlorine atom, a methyl group and an ethyl group] and a solid powder of the dibenzylidene sorbitol derivative of the formula (II )

[0076]

[Chemical 4]

[In the formula, n is 14 to 30, preferably 18 to 27,
Most preferably, it represents a number of 20 to 25], and a higher fatty acid is coated on the surface of the solid powder of the dibenzylidene sorbitol derivative, and the higher fatty acid is contained in the dibenzylidene sorbitol derivative composition. To be done.

General formula (II) 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-p ethylbenzylidene sorbitol and 1,3-
Examples thereof include p-chlorobenzylidene-2,4p-methylbenzylidenesorbitol and the like. 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 preferred dibenzylidene sorbitol derivatives are 1,3-2,4-dipmethylbenzylidene sorbitol, 1,3-p methylbenzylidene-2,4-p chlorobenzylidene sorbitol and 1,3-p chlorobenzylidene. -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 include 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.

The 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 higher fatty acid in the above proportion in the above proportion and stirred to obtain 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 a coating of higher fatty acids formed on the surface of the solid powder of dibenzylidene sorbitol derivative is also confirmed by observing the coating with a dye, as described in detail in the examples below. You can check.

A preferred organic nucleating agent composition of the present invention is
Examples of countermeasure polyolefin resins used as additives for improving physical strength, non-bleed-out property and odorless property include aliphatic mono-olefins having 2 to 6 carbon atoms and having a number average molecular weight of about 10,000 to 200,000, preferably Is 20,000 to 150,000
A high molecular weight homopolymer resin or copolymer resin, for example homopolypropylene resin, low density polyethylene resin,
Examples thereof include high-density polyethylene resin, linear polyethylene (= ethylene / α-olefin copolymer) resin and ethylene / propylene copolymer resin.

In the preferred organic nucleating agent composition of the present invention, 0.01 to 2 parts by weight, preferably 0.05 to 1 part by weight, of a higher fatty acid as a dibenzylidene sorbitol derivative component is added to 100 parts by weight of the polyolefin resin. 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 preferred organic nucleating agent composition of the present invention can be used as a masterbatch in a polyolefin resin containing the composition in a concentrated amount, 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 the 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, 0.01% of the above-mentioned di-substituted benzylidene sorbitol composition described in detail in the polyolefin resin composition of the present invention as the composition of the preferred organic nucleating agent of the present invention is used. After adding ~ 2.0% by weight, 2
The light-shielding polyolefin resin film may be molded using a pellet which is heated to 00 ° C. or higher, and the above-mentioned effect is achieved even if the resin temperature at this time is 180 ° C. or lower. By setting the resin temperature to 180 ° C. or higher during molding (which is expressed in the present invention 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 and wrinkles. It is possible to form a light-shielding thermoplastic resin film in which almost no streaks are observed.

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 are further improved, and at the same time, it has excellent odorlessness, and at the same time, wrinkles and streaks are less likely to appear on the film, and the film moldability is improved, the film molding speed can be improved, and molding failure occurs. It has an excellent effect of decreasing. That is,
By incorporating the above-mentioned di-substituted benzylidene sorbitol composition in the polyolefin resin composition of the present invention, a photographic light-sensitive material having excellent physical strength, rigidity, bleed-out resistance, odorlessness, film formability, and abrasion resistance. A packaging material for materials can be provided.

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. ) Tend to cause a strange odor of the light-shielding thermoplastic resin film, and dibenzylidene sorbitol (derivative) causes some decomposition even when the light-shielding thermoplastic resin film is formed using the thermoplastic resin composition. It is possible that it may cause an offensive odor. In the preferred organic nucleating agent composition of the present invention, solid particles of the specific dibenzylidene sorbitol derivative of the general formula (I) are used, and the particles are represented by the general formula
(II) coating with a specific higher fatty acid, and by simultaneously satisfying the requirements of and, the offensive odor presumed to be based on the raw material benzaldehyde or the benzaldehyde decomposed and produced is a shading effect using the thermoplastic resin composition. In the functional film, the effect of being remarkably reduced and having the above-mentioned various physical properties such as rigidity and physical strength at the same time exhibited. In particular, when carbon black is used as the light-shielding substance, the offensive odor is almost eliminated because the decomposition products such as benzaldehydes are adsorbed to the carbon black, and the deterioration of photographic properties is hardly observed.

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 nucleating agent can be coated with various fatty acids, lubricants such as fatty acid compounds and silicone, coupling agents, plasticizers, dispersants such as surfactants and wetting agents. In particular, when used in combination with a light-shielding substance such as carbon black having an adsorption effect on benzaldehydes, etc., the effect of preventing deodorization and deterioration of photographic properties is exhibited.

The amount of the nucleating agent added is 0.01 to 2.0% by weight, preferably 0.05 to 1.0% by weight, and particularly preferably 0.07 to 0.5% by weight. If the addition amount is less than 0.01% by weight, almost no effect is exhibited and only the blending cost is required, and if it exceeds 2.0% by weight, there is no effect of increasing the amount and the cost is increased.
In addition, depending on the type of the nucleating agent, it adversely affects the photographic light-sensitive material, generates a bad odor, adheres to the mold, and bleeds out, which is not preferable.

As a method for 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. 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 dispersants, various waxes, carboxylic acid anhydrides, higher fatty acids and the like are effective as dispersants, and various fatty acid metal salts, various silicones, oleic acid amides and other lubricants are particularly preferable. As the wetting agent, the above-mentioned plasticizers such as DOP and DHP can be used.

Further, it is also preferable to coat the surface of the organic nucleating agent with a pure product of a fatty acid or a fatty acid compound such as a higher fatty acid, a fatty acid amide or a fatty acid metal salt, or to improve the dispersion effect to prevent bleed-out. Further, it is preferable to use as a pellet kneaded with a polyolefin resin at a heat history of 180 ° C. or higher, preferably 190 ° C. or higher, and particularly 200 ° C. or higher from the viewpoint of exerting the effect of the nucleating agent. That is, by adding these additives, the physical strength is improved, the rigidity is increased and the generation of white powder due to wear is reduced, and the generation of white powder due to crystallization or bleed-out of the organic nucleating agent is reduced. 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 the present invention, the effect of the organic nucleating agent and the light-shielding substance can be improved by using one or more thermoplastic resins which have undergone a heat history of 120 to 400 ° C. twice or more, and particularly 140 to 350 ° C. three or more times. Uniform dispersibility can be achieved.

The amount of the nucleating agent added is preferably 0.01 to 2.0% by weight. If the amount added is less than 0.01% by weight, the effect of addition is hardly exerted and only the blending cost is required. Further, even if it exceeds 2.0% by weight, there is no effect of increasing the amount, which only increases the cost, and depending on the kind of the nucleating agent, it may adversely affect the photographic light-sensitive material, adhere to the mold, or bleed out. , Reduce the impact strength.

In the light-shielding thermoplastic resin film of the present invention, various kinds of additives can be selected and contained depending on the required characteristics and the purpose of use, in the kind and amount which do not adversely affect the photographic characteristics. Other additives are shown below. (Types of additives) (Representative examples) (1) Plasticizers; phthalates, glycol esters, fatty acid esters, phosphates, etc. (2) Stabilizers: lead-based, cadmium-based, zinc-based, alkaline earth (3) Flame retardants; Phosphates, halogenated phosphates, halides, inorganics, phosphorus-containing polyols, etc. (4) Fillers: alumina, kaolin, clay, calcium carbonate, mica , Talc, titanium oxide, silica, etc. (5) Reinforcing agent: glass roving, metal fiber, glass fiber, glass milled fiber, carbon fiber, etc. (6) Foaming agent: Inorganic foaming agent (ammonia carbonate, sodium bicarbonate), Organic foaming agents (nitroso type, azo type), etc. (7) Vulcanizing agents; Vulcanization accelerators, accelerator aids, etc. (8) Deterioration inhibitors; UV absorbers, metal deactivators, peroxide decomposers, etc. (9) Coupling agent; silane , Titanate, chromium-based, aluminum-based, etc. (10) Various thermoplastic resins, thermoplastic elastomers, synthetic rubber, etc. (11) Antioxidants (0.001 to 1.0 wt%)

Considering the case of landfill treatment as waste, degradable plastics that are currently being researched or are introduced into some markets may be used. For example, as a biodegradable polymer I
CI's "BIOPOL", UCC's "polycaprolactone", or the like, or a polymer that is indirectly disintegrated by adding a natural or synthetic polymer that is susceptible to biodegradation as an additive, or Starch-blended polyethylene or the like can also be used.

[0100] Particularly, "Bionore" manufactured by Showa High Polymer Co., Ltd., which was recently released as a chemically-synthesized biodegradable plastic that is decomposed into carbon dioxide and water by the action of microorganisms, is a special compound (chemically synthesized from dicarboxylic acid, etc.). Polyester resin)
50% by weight or more of "Matterby" manufactured by Novamont of Italy (polymer starch of corn starch and modified polyvinyl alcohol having biodegradability) in one or more layers of the photographic light-sensitive material packaging material of the present invention, Preferably 70
% Or more, particularly preferably 80% by weight, most preferably
90% by weight or more is preferable from the viewpoint of improving the processability of industrial waste. In particular, it is preferably used for one or more layers other than the layer that 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.

Details of the various thermoplastic resins, various essential additives, and other various additives are described in "Plastic Data Handbook, published by Industrial Research Institute Co., Ltd., July 5, 1980". From these, a combination of various characteristics essential for the photographic light-sensitive material packaging material of the present invention and types and amounts that do not adversely affect photographic characteristics is selected and used.

The packaging material for a photographic light-sensitive material of the present invention is formed of a laminated film of a light-shielding thermoplastic resin film and another flexible sheet even if it is formed of a single layer of the light-shielding thermoplastic resin film as described above. May be done. When it is formed of a laminated film, it may be laminated by coextrusion or by an adhesive.

Examples of the flexible sheet include thermoplastic resin films such as various polyethylene resins, ethylene copolymer resins, ethylene / vinyl acetate copolymers (EVO).
H) resin (ethylene content 70-99% by weight), polypropylene resin, propylene copolymer resin, polystyrene resin, polymethylmethacrylate resin, high impact polystyrene resin, polyvinyl alcohol (PVA) resin, polyvinyl chloride resin Known films such as polyvinylidene chloride resin, polyamide resin, polyacrylonitrile resin, ultra high molecular weight polyethylene resin, cross-linked polyethylene resin, polyethylene naphthalate resin, ethylene vinyl alcohol copolymer resin, polycarbonate resin, polyester resin and the like. There are modified resin films or uniaxially or biaxially stretched films thereof. Also, triacetate film, cellophane, regenerated cellulose film, EVOH resin film, paper, synthetic paper, non-woven fabric, metal foil, thermoplastic resin film and dust-free flexible sheet (dust-free paper, synthetic paper, non-woven paper, glassine There is a metal thin film processed flexible sheet in which a metal thin film processed layer is provided on paper, cellophane, surface size or surface coated paper).

Particularly preferred flexible sheets are various types of paper having a basis weight of 20 to 400 g / m ² that does not adversely affect photographic light-sensitive materials (waste paper, recycled paper, unbleached kraft paper, semi-bleached kraft paper, bleached kraft paper, Hinelli base paper, Kurpac paper, Duostress paper, white paperboard, photographic base paper, high-quality paper, medium-quality paper using high-yield pulp, pure white roll paper, coated paper, imitation paper,
Glassine paper), non-woven fabric, synthetic paper and biaxially stretched thermoplastic resin film. By embossing various shapes on these flexible sheets, the flexibility and stretchability are further improved.

The metal foil is a metal foil such as an aluminum foil, a lead foil, an iron foil, a tin foil, a zinc foil, an electrolytic iron foil, a copper foil, and a stainless steel foil. The thickness of the metal foil is
5 to 100 μm is preferable, 7 to 50 μm is particularly preferable, 9 to 20 μm in consideration of economical efficiency, handleability, and securing of characteristics.
Is most preferred.

When the laminated film is formed of an adhesive, the adhesive layer is preferably a solution type adhesive made of a polyester resin or a polyether resin having an isocyanate group at the terminal. This solution type adhesive layer is preferable because it has a large adhesive strength even if it is a thin layer, and can easily open and secure a substantially straight cut while securing flexibility. Further, since the reaction solidifies, the photographic light-sensitive material is not adversely affected.

The adhesive strength of the adhesive layer is the peel strength between two laminates (180 mm) when improving the physical strength such as tear strength in both vertical and horizontal directions, impact drilling strength, and gelbotest strength.
Peeling test, using ASTM D 903 testing machine)
Is 300g / 15mm width or less, preferably 100g / 15mm width or less,
Particularly preferably, the weak adhesive layer has a width of 50 g / 15 mm or less.
However, in the bag making process or laminating process, strength is required so that it does not peel off. 0.1g / 15mm width or more, preferably 1g / 15m
m width or more, particularly preferably 5 g / 15 mm width or more. The blocking adhesive strength is almost the same.

In order to obtain an adhesive layer having such an adhesive strength, the thickness of the adhesive layer is reduced, and the surface of the adherend is subjected to corona discharge treatment, flame (flame) treatment, plasma treatment, ultraviolet ray irradiation treatment, electronic treatment. Two or more poorly compatible resins, which are not subjected to surface treatment such as radiation treatment, preheat treatment, anchor coat treatment, etc., lower the temperature of the adhesive layer, and are an adhesive layer made of a weak adhesive strength resin composition One or a combination of two or more methods such as forming an adhesive layer composed of the composition, forming a multi-layer coextrusion extrusion laminate adhesive layer that facilitates delamination, and the like are used.

For the adhesive layer, an acid-modified polyolefin resin is particularly preferable, and the content in the adhesive layer is 1 which is economically advantageous because it can improve the adhesive strength without adversely affecting the photographic characteristics.
-50% by weight, preferably 5-40% by weight, particularly preferably 10-35% by weight. 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 a graft-modified polyethylene resin, a graft-modified polypropylene resin, and a graft-modified ethylene copolymer resin (EVA).
Resin, EEA resin, L-LDPE resin, EMA resin, etc.)
Etc.

The unsaturated carboxylic acids, including their derivatives, are generically named. 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.
The method disclosed in JP-B-15422, etc., the method disclosed in JP-B-43-18144 for reacting in a slurry state, the method disclosed in JP-B-50-77493 for reacting in a gas phase, etc. 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 accelerate 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 is 0.005 to 100 parts by weight of the polyolefin resin.
It is 5 parts by weight, preferably 0.01 to 1 part by weight.

Typical examples of commercially available acid-modified polyolefin resins are shown below. (1) Nippon Petrochemical KK "N Polymer" (2) Mitsui Petrochemical KK "ADMER" (3) Showa Denko KK "ER RESIN" (4) Mitsubishi Kasei KK "Novatech-AP" (5) Mitsubishi Petrochemical KK "MODIC" (6) Nippon Unicar KK "NUC-ACE" (7) Ube Industries KK "UBE BOND" (8) Tosoh KK "Mersen M" (9) Sumitomo Chemical KK "Bondayne" (10) Mitsui DuPont Chemical KK "CMPS" etc.

The amount of the acid-modified polyolefin resin contained in the adhesive layer is preferably 5% by weight or more, particularly preferably 10% by weight or more.

The packaging material for a photographic light-sensitive material of the present invention can be used as a packaging bag. Examples of the packaging bag include:
Unipack bag, seamless cylindrical bag, single flat bag, double flat bag, single gusset bag, double gusset bag, shrink packaging bag, bulk packaging bag (JP-A-3-53243, JP-A-3-71346) Issue gazette). As a concrete example,
Film with lens (moisture-proof bag for exhibition such as photo-run, 35mm
It is a moisture-proof bag for displaying a plurality of films (containing moisture-proof containers), a moisture-proof light-shielding bag for a bright-room loading belt-shaped container, and the like.

The packaging bag may be provided with characters or symbols necessary for its function, or may be printed to enhance the commercial value. As the ink used for these printings, those which are harmless to the light-sensitive material are selected and can be selected from commonly used offset printing inks, gravure printing inks, UV inks and the like.

The packaging material for the photographic light-sensitive material of the present invention is not only a packaging bag but also a light-shielding box or a light-shielding magazine for inside or outside attachment, a belt-shaped roll-shaped photographic light-sensitive material for sealing light-shielding, stretch packaging, shrink packaging. It can be used as a packaging material for a packaging body in various forms adapted to the shape and size of various photographic light-sensitive materials, such as for a collective packaging body such as.

Examples of the photographic light-sensitive material which is preferably packaged with the photographic light-sensitive material packaging material of the present invention are shown below. (1) Silver halide photographic light-sensitive material (printing film, color photographic paper, color film, printing master paper, DTR
Photosensitive materials, computer typesetting films and papers, microfilms, movie films, self-developing photographic photosensitive materials, direct positive type films and papers, etc. (2) Thermal development photosensitive materials (thermal development color photosensitive materials, thermal development black and white photosensitive materials) (For example, Japanese Examined Patent Publication No. 43-4921 and 43-4924.
No. 553 to 555 of "Golden salt photography edition" (published by Corona Publishing Co. in 1879) and Research Tis Closure magazine, June 1978, pages 9 to 15 (RD-17029). What has been done. Further, JP-A-59-12431,
60-2950, 61-52343 and U.S. Pat.
No. 84,267, a transfer type heat-developable color light-sensitive material, etc.) (3) Photosensitive / thermosensitive recording material (photothermographic (light-sensitive / thermosensitive image described in JP-A-3-72358) (4) Diazonium photographic light-sensitive material (4-morpholinobenzenediazonium microfilm, microfilm, copying film, printing plate material, etc.) (5) Azide, diazide photographic light-sensitive material ( Photosensitive materials containing para-azidobenzoate, 4,4'diazidostilbene, etc., such as copying films, printing plate materials, etc. (6) Quinonediazide photographic photosensitive materials (orthoquinonediazide, orthonaphthoquinonediazide compounds, such as benzoquinone ( 1,2) -diazide- (2) -4-sulfonic acid phenyl ether and other photosensitive materials, such as printing plates, (Transfer film, adhesion film, etc.) (7) Photopolymer (photosensitive material containing vinyl monomer, printing plate material, adhesion film, etc.) (8) Polyvinyl cinnamate photosensitive material (eg printing film, IC resist etc.)

[0124] In addition, other photosensitive substances which 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.

[0125]

In the packaging material for a photographic light-sensitive material of the present invention, by including a light-shielding substance, the complete light-shielding property essential for the packaging material for a photographic light-sensitive material is ensured and the antistatic property is improved and the physical strength is improved. Is improving. Further, by blending and using three or more kinds of thermoplastic resins having different characteristics, one or two kinds of thermoplastic resins can meet various strict characteristics required as a packaging material for a photographic light-sensitive material in a single-layer light-shielding property. Even a thermoplastic film layer alone can be secured in a well-balanced manner.

[0126]

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 9 are partial cross-sectional views showing the layer structure of the packaging material for a photographic light-sensitive material.

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

The photographic light-sensitive material packaging material shown in FIG. 2 is formed of a light-shielding two-layer coextrusion film IIa composed of a light-shielding thermoplastic resin film layer 1a and a thermoplastic resin film layer 2a containing a light-shielding substance. There is.

The packaging material for photographic light-sensitive material shown in FIG.
It is formed of a light-shielding two-layer coextrusion film IIa composed of two light-shielding thermoplastic resin film layers 1a.

The photographic light-sensitive material packaging material shown in FIG. 4 is formed of a light-shielding two-layer coextrusion film IIa comprising a light-shielding thermoplastic resin film layer 1a and a thermoplastic resin film layer 2.

The packaging material for photographic light-sensitive material shown in FIG. 5 is a light-shielding three-layer coextrusion film IIIa comprising a light-shielding thermoplastic resin film layer 1a, an intermediate layer 3 and a thermoplastic resin film layer 2a containing a light-shielding substance. Is formed by.

The photographic light-sensitive material packaging material shown in FIG. 6 is formed by laminating a light-shielding thermoplastic resin film layer 1a and a flexible sheet 4 with an adhesive layer 5 interposed therebetween.

The photographic light-sensitive material packaging material shown in FIG. 7 comprises a light-shielding two-layer coextrusion film IIa comprising a light-shielding thermoplastic resin film layer 1a and a thermoplastic resin film layer 2a containing a light-shielding substance, and a light-shielding property. The flexible sheet layer 4a containing the substance is laminated with the adhesive layer 5 in between.

The packaging material for photographic light-sensitive material shown in FIG. 8 is a light-shielding two-layer coextruded film IIa comprising a light-shielding thermoplastic resin film layer 1a and a thermoplastic resin film layer 2a containing a light-shielding substance. Plastic resin film layer 1a
And a flexible sheet layer 4a containing a light-shielding substance,
It is formed by laminating with the adhesive layer 5 interposed therebetween.

The packaging material for photographic light-sensitive material shown in FIG. 9 is a light-shielding two-layer coextruded film IIa, IIa composed of a light-shielding thermoplastic resin film layer 1a and a thermoplastic resin film layer 2a containing a light-shielding substance. It is formed by stacking the sheets by blocking adhesion B.

Next, the results of comparing the characteristics of the product of the present invention and the comparative product will be described. [Inventive Products 1 to 13] Packaging materials for photographic light-sensitive materials were prepared containing the following thermoplastic resins, light-shielding substances and lubricants in the following proportions. The characteristics of this packaging material are shown in Table 1.

[0137]

[Table 1]

The thermoplastic resins in Table 1 are as follows. Thermoplastic resin A: MI 2.0 g / 10 min, density 0.920 g /
cm ^3, a Vicat softening point of 100 ° C. Ethylene-4-methylpentene-1 copolymer resin thermoplastic resin B: MI is 2.5 g / 10 min, density of 0.923 g /
cm ^3, a Vicat softening point of 103 ° C. Ethylene-octene-1
Copolymer resin Thermoplastic resin C: MI 1.0 g / 10 min, density 0.905 g /
cm ^3, ultra-low density ethylene-butene-1 copolymer resin thermoplastic resin D Vicat softening point 84 ° C.: MI is 2.6 g / 10 min, density of 0.920 g /
cm ³ , low density homopolyethylene resin with Vicat softening point of 90 ° C Thermoplastic resin E: MI 8.0 g / 10 min, density 0.923 g /
cm ^3, a low density homopolyethylene resin thermoplastic resin F Vicat softening point 91 ° C.: MI is 1.2 g / 10 min, density of 0.951 g /
cm ^3, high density homopolyethylene resin thermoplastic resins G Vicat softening point 119 ° C.: MI is 1.8 g / 10 min, density of 0.937 g /
cm ^3, a Vicat softening point 113 ° C. of ethylene 4-methylpentene-1 copolymer resin thermoplastic resin H: MI is 6.0 g / 10 min, density of 0.930 g /
cm ^3, a Vicat softening point 56 ° C. of ethylene-ethyl acrylate copolymer resin thermoplastic resin I: MI is 15.6 g / 10 min, density of 0.940g
/ Cm ³ , ethylene / vinyl acetate copolymer resin with a Vicat softening point of 58 ° C Thermoplastic resin J: Acid-modified polypropylene resin (Admer manufactured by Mitsui Petrochemical Co., Ltd.) Thermoplastic resin K: Saturated alicyclic hydrocarbon resin (tackifying) Arakawa Hayashi Chemical's Alcon P-90 called a chemical agent Thermoplastic resin L: Low molecular weight polyethylene resin (molecular weight approx.
2000, softening temperature 107 ℃, density 0.930g / cm ³ ) Thermoplastic resin M: Low molecular weight polyethylene resin (molecular weight approx.
1500, softening temperature 105 ℃, density 0.928g / cm ³ )

The light-shielding substances in Table 1 are as follows. Light-shielding substance a: average particle size is 22 mμ, pH is 7.7, oil absorption is 92 ml / 100 g, and volatile components after drying at 110 ° C. for 2 hours are 0.8.
% Furnace Carbon Black Light-shielding substance b: average particle size 29 mμ, pH 3.2, oil absorption 71 ml / 100 g, volatile component 2.7 after drying at 110 ° C. for 2 hours
% Furnace carbon black Light-shielding substance c: average particle size 14 mμ, pH 7.0, oil absorption 150 ml / 100 g, volatile components 3.5 after drying at 110 ° C. for 2 hours
% Contact black (# 600 manufactured by Mitsubishi Kasei) Light-shielding substance d: average particle size 29 mμ, pH 5.0, oil absorption 125 ml / 100 g, volatile component 5.0 after drying at 110 ° C. for 2 hours 5.0
% Channel carbon black Light-shielding substance e: average particle size 40 mμ, pH 7.5, oil absorption 125 ml / 100 g, volatile component 0.2 after drying at 110 ° C. for 2 hours is 0.2
0% acetylene black

The lubricants in Table 1 are as follows. Lubricant a: Elucic acid amide Lubricant b: Oleic acid amide Lubricant c: Magnesium stearate Lubricant d: Calcium stearate Lubricant e: Dimethyl polysiloxane (viscosity 10,000 centistokes) Lubricant dimethyl polysiloxane (viscosity 5 million centistokes)

[Invention product 14] A light-shielding thermoplastic resin film corresponding to the invention product 4 having a thickness of 70 μm and having a thickness of 10 μm,
Propylene / ethylene random copolymer resin containing 5% by weight of furnace carbon black of the light-shielding substance a through a low-density homopolyethylene resin extrusion laminate adhesive layer having a 180 degree peeling adhesive strength of 25 g / 15 mm (MI is 5 g / 10 min, density 0.91 g / 10 min, ethylene content 5% by weight) A 20 μm thick light-shielding biaxially stretched polypropylene resin film is laminated to form a packaging material for photographic light-sensitive materials. This packaging material is for use in a photographic light-sensitive material capable of providing a moisture-proof and light-shielding packaging bag having excellent heat-sealing suitability, bag-manufacturing suitability, moisture resistance, oxygen barrier property, and excellent appearance, with substantially no decrease in physical strength as compared with the product 4 of the present invention. It was a packaging material.

[Invention product 15] A 20 μm thick light-shielding biaxially stretched polypropylene resin film of the invention product 14 was treated with corona discharge, coated with a polyethyleneimine anchor coating agent, and dried to give an invention product 4 of 17 μm in thickness. A packaging material for a photographic light-sensitive material having a thickness of 107 μm, in which a light-shielding thermoplastic resin film having a thickness of 70 μm and having the same resin composition as that of the product 4 of the present invention is laminated via the same low-density homopolyethylene resin adhesive layer.

This packaging material has a thickness of 7 compared with the product 14 of the present invention.
Despite the increase in μm, the adhesive strength is 25 → 758
Since the width was increased to g / 15mm, the physical strength such as tear strength and impact puncture strength decreased by about 20%, and curling became large, but it was a sealed packaging bag with fine notches formed in the heat-sealed part to be opened. Then, it can be opened easily by hand, and it was suitable as a packaging material used for a moisture-proof and light-shielding packaging bag for a photographic light-sensitive material that must be opened under a safelight.

[Product 16 of the present invention] A product obtained by coating a vinylidene chloride resin layer having a thickness of 1 μm in place of the light-shielding biaxially oriented polypropylene resin film having a thickness of 20 μm of Product 14 of the present invention.
A packaging material for a photographic light-sensitive material, which has the same layer structure as the product 14 of the present invention except that a biaxially oriented polypropylene film coated with vinylidene chloride resin having a thickness of 21 μm is used. The product 14 of the present invention was more excellent in moisture resistance and oxygen barrier property, and was suitable as a packaging material for a photographic light-sensitive material.

[Invention product 17] A light-shielding thermoplastic resin film made of the same resin composition as in the invention product 4 and having a thickness of 60 μm, and an ethylene / 4-methylpentene-1 copolymer resin of the thermoplastic resin G. 50% by weight, 44.75 parts by weight of the ethylene / 4 methylpentene-1 copolymer resin of the above-mentioned thermoplastic resin A, 5 parts by weight of titanium dioxide surface-treated with hydrous aluminum hydroxide as a light-reflecting light-shielding substance, hindered phenol Light-blocking L-LDPE with a thickness of 40 μm, containing 0.05 part by weight of antioxidant and 0.2 part by weight of magnesium stearate
A packaging material for a photographic light-sensitive material, which comprises a light-shielding two-layer coextruded film having a total thickness of 100 μm and comprising a resin film layer.

This packaging material is more moisture-proof than the product 4 of the present invention.
It was most suitable as a packaging material for a photographic light-sensitive material having excellent oxygen barrier properties, moisture-proof and light-shielding packaging bag suitability, tensile strength, bag-making suitability, and appearance, as well as front and back distinctiveness and printability.

[0147]

INDUSTRIAL APPLICABILITY According to the present invention, various characteristics required as a packaging material for photographic light-sensitive materials can be secured in a well-balanced manner even with a single-layer light-shielding thermoplastic resin film.

[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 of the present invention.

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

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

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

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

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

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

FIG. 8 is a partial sectional view showing the layer structure of another embodiment of the packaging material for photographic light-sensitive material of the present invention.

FIG. 9 is a partial cross-sectional view showing the layer structure of another embodiment of the photographic light-sensitive material packaging material of the present invention.

[Explanation of symbols]

 1a ... Light-shielding thermoplastic resin film layer 2, 2a ... Thermoplastic resin film layer 3 ... Intermediate layer 4 ... Flexible sheet 5 ... Adhesive layer

Claims (10)

[Claims] 1. A packaging material for a photographic light-sensitive material, comprising a light-shielding thermoplastic resin film layer containing three or more kinds of thermoplastic resins having different characteristics and a light-shielding substance. 2. The light-shielding thermoplastic resin film layer contains a lubricant.
The packaging material for photographic light-sensitive materials according to claim 1, containing 0.001 to 10.0% by weight. 3. The packaging material for a photographic light-sensitive material according to claim 1, wherein the light-shielding thermoplastic resin film layer contains 0.0005 to 1.0% by weight of a phenolic antioxidant. 4. The photographic light-sensitive material according to claim 1, 2 or 3, wherein one of the three or more thermoplastic resins having different characteristics is an ethylene copolymer resin and the content thereof is 5% by weight or more. Packaging material 5. The packaging material for a photographic light-sensitive material according to claim 1, 2, 3 or 4, wherein at least one layer contains at least one of an antistatic agent and a conductive substance. 6. The light-shielding thermoplastic resin film layer contains 50% by weight or more of a polyolefin resin, 0.1% by weight or more of a surface-coated light-shielding substance having a refractive index of 1.50 or more, and a nucleating agent. Packaging material for photographic light-sensitive material as described in 2, 3, 4 or 5. 7. One or more kinds of thermoplastic resin having 3 or more kinds of thermoplastic resin having a thermal history of 120 ° C. or more twice and 3% or more of different characteristics, and a light-shielding substance having a refractive index of 1.50 or more. And / or 0.1% by weight or more of metal powder, and an antioxidant of 0.0
A packaging material for a photographic light-sensitive material, comprising a light-shielding thermoplastic resin film layer containing 005 to 1.0% by weight and 0.001 to 10.0% by weight of a lubricant. 8. One or more kinds of polyolefin resin, which has been subjected to a heat history of 120 ° C. or more twice or more, 3% by weight or more, and three or more kinds of thermoplastic resins having different characteristics, containing 5% by weight or more of ethylene copolymer resin. , A light-shielding substance with a refractive index of 1.50 or higher and /
Or 0.1% by weight or more of metal powder and 0.0005 to 1.0 of antioxidant
A packaging material for photographic light-sensitive material, comprising a light-shielding thermoplastic resin film layer having a melt index of 0.01 to 15 g / 10 min. 9. The photograph according to claim 1, wherein the light-shielding thermoplastic resin film layer is layered so as to be the innermost surface. Packaging material for photosensitive materials 10. The light-shielding thermoplastic resin film layer,
The packaging material for a photographic light-sensitive material according to claim 9, comprising a light-shielding multilayer coextruded thermoplastic resin film layer having a thermoplastic resin layer directly on the upper layer without an adhesive layer.