JPH0791412B2 - Resin composition used for packaging material for photographic light-sensitive material - Google Patents

Description

TECHNICAL FIELD The present invention relates to a resin composition used for a packaging material such as an injection molded article, an inflation film, an extruded sheet, or the like for packaging a photographic light-sensitive material.

[Conventional technology]

Generally, for a photographic light-sensitive material that loses its quality value when exposed to light, a packaging material that completely blocks light is used. In addition to the above-mentioned light-shielding property, the packaging material needs to have sufficient physical strength according to the size and weight of the object to be packaged. In the packaging material using the light-shielding film, the opening is sealed by heat sealing. Heat seal suitability is required. Further, it is also necessary to have a property of preventing electrification caused by friction with a photosensitive material.

Conventionally, the present applicant has proposed various packaging materials for such a purpose, for example, a resin composition of a linear low-density polyethylene resin (hereinafter, referred to as L-LDPE resin) and a high-density polyethylene resin. Japanese Patent Laid-Open No. 62-18546 discloses a mixture of carbon black and a lubricant.

Also disclosed is a resin composition of polypropylene resin and L-LDPE resin mixed with a light-shielding substance, an auxiliary agent, a lubricant, and an antioxidant (JP-A-63-215748).

Further, a resin composition for a molded product obtained by mixing a lubricant, an antioxidant, and a light-shielding substance in a resin composition of a polypropylene resin having a specific performance and an L-LDPE resin is also disclosed (JP-A-1-152145). Gazette).

Also disclosed is a resin composition for a molded product and a film, which further comprises any one of metal powder, fatty acid or fatty acid compound and a surfactant, and an antioxidant and silica white (Japanese Patent Application No. 63-332032). issue).

In order to ensure antistatic properties, these injection-molded products and resin films may have an antistatic agent added to the resin or applied to the surface of the molded product, and the resin film may have conductivity. Antistatic was performed by laminating a metal foil or a metal vapor deposition film.

[Problems to be Solved by the Invention]

However, when an antistatic agent is added to the resin,
With the passage of time, the antistatic agent bleeds out, causing various problems such as blocking and poor heat-sealing properties, development inhibition due to transfer to a photographic light-sensitive material, and developer contamination.

In addition, coating the surface of a molded product with an antistatic agent or laminating a metal foil or a metal vapor deposition film has caused various problems such as an increase in cost, a decrease in physical strength, warpage and curling.

The present invention solves the above problems and provides a resin composition used for a packaging material for a photographic light-sensitive material, which secures antistatic property without deteriorating the appearance due to bleed-out or deteriorating the quality of the photographic light-sensitive material. The purpose is to do.

[Means for solving problems]

The present inventor has conducted extensive studies in order to solve the above problems, found out that the problem can be solved by using a specific conductive carbon black and a lubricant together, and completed the present invention.

That is, the resin composition used for the packaging material for the photographic light-sensitive material of the present invention has a DBP oil absorption (ASTM D-2414) of 300 ml / 100 g.
Above, BET specific surface area of 900 m ² / g or more, heavy metal content of 80
Polyolefin resin, polystyrene resin, acrylonitrile-butadiene-styrene resin, polyamide resin and polyester containing 1 to 20% by weight of conductive carbon black having an average particle size of 0 ppm or less and 10 to 60 mμ and 0.01 to 5.0% by weight of a lubricant. It is characterized in that it is made of one kind or two or more kinds of resins.

The resin composition used for the packaging material for the photographic light-sensitive material of the present invention is composed of a thermoplastic resin containing conductive carbon black and a lubricant, and has antistatic performance and light shielding property even if it does not contain an antistatic agent that easily bleeds out. Retains sex. That is, since the electrical volume specific resistance is small and the charging is small, the static mark failure is small. Further, it has good slipperiness and releasability, no blocking failure, and good film moldability, injection moldability, and sheet extrusion moldability. Then, by selecting a thermoplastic resin, it is molded into a resin film, an injection molded product, an extruded sheet or the like.

The electrically conductive carbon black used in the present invention has a good dispersibility, unlike carbon black that has been generally used from the past, resulting in a decrease in the physical strength and heat sealability of the resin composition, and a deterioration in the film moldability. Less likely to invite. Further, it has an antistatic property like Ketjen carbon black, but it does not contain much impurities causing fog or sensitivity abnormality in the photographic light-sensitive material.

DBP oil absorption of conductive carbon black (ASTM D2414) is
It is 300 ml / 100 g or more, preferably 400 ml / 100 g or more. If the DBP oil absorption is less than 300 ml / 100 g, it is necessary to mix a large amount in the resin composition, and moisture absorption, pinholes due to foaming, physical strength reduction, deterioration of heat sealability, etc. occur and practical application is possible. Have difficulty.

The BET specific surface area of the conductive carbon black is 900 m ² / g or more. If the BET specific surface area is less than 900 m ² / g, it is necessary to mix a large amount in the resin composition, and moisture absorption, generation of pinholes due to foaming, deterioration of physical strength, deterioration of heat sealability, etc. occur. Practical application is difficult.

The conductive carbon black has a heavy metal content of 800 ppm or less. When the heavy metal content exceeds 800 ppm, not only the photographic material is adversely affected by spots, increase / decrease, fog, etc., but also the resin is affected by heavy metal ions and the dispersibility of the conductive carbon black in the resin deteriorates. However, the moldability of the resin composition is significantly deteriorated. Therefore, it is preferable that the content of heavy metals is low, preferably 500 ppm or less, and particularly preferably 300 ppm or less.

Examples of the heavy metal include iron, vanadium, manganese, nickel, cobalt, copper and the like, which adversely affect the photographic light-sensitive material.

The average particle size of the conductive carbon black is in the range of 10 to 60 mμ, preferably 20 to 50 mμ. When the average particle diameter is less than 10 mμ, the resin composition is apt to solidify, and when it exceeds 60 mμ, the light-shielding ability is deteriorated. Therefore, when the addition amount is increased, the physical strength of the resin composition is decreased.

The conductive carbon black as described above is contained in an amount of 1 to 20% by weight, preferably 3 to 15% by weight.

If the amount added is less than 1% by weight, the light-shielding property and antistatic property of the resin composition are insufficient, and if it exceeds 20% by weight, the photographic light-sensitive material is contaminated in black and the physical strength of the resin composition is lowered, resulting in light-shielding. Appropriate heat sealing of the film and decrease physical strength.

The lubricant improves antistatic properties, extrudability of the resin composition and film moldability, and when used in combination with conductive carbon black, synergistically improves antistatic properties.

This lubricant is contained in the thermoplastic resin in an amount of 0.01 to 5.0% by weight. Especially in the case of fatty acid amide lubricants, which have a great lubricating effect,
Since there is a tendency to bleed out, it is preferable to add 0.01 to 1.0% by weight.

When the amount added is less than 0.01% by weight, the effect of addition is small and slipperiness and antistatic properties are not obtained. When the amount added exceeds 0.5% by weight, slipping with the screw occurs, and quantitative extrusion becomes difficult. Further, bleeding out occurs with the passage of time, causing various problems such as blocking, poor heat sealability, development inhibition due to transfer to a photographic light-sensitive material, and developer contamination.

The names of typical commercially available lubricants and the names of manufacturers are listed below.

(1) Silicone-based lubricants; various grades of dimethylpolysiloxane and its modified products (Shin-Etsu Silicone, Toray Silicone), etc. (2) Oleic acid amide-based lubricants: Armoslip CP (Lion Akzo), Neutron (Nippon Seika) , Neutron E-18 (Nippon Seika), Amide O (Nitto Kagaku), Alfuro E-10 (Nippon Oil & Fats), Diamid O-200 (Nippon Kasei), Diamid G-200
(Nippon Kasei) etc. (3) Erucic acid amide lubricant; Alfro-P-10 (NOF Corporation), etc. (4) Stearic acid amide lubricant; Alfuro-S-10 (NOF Corporation), Neutron 2 (Nippon Seika) ), Diamid 200 bis (Nippon Kasei), etc. (5) Bis fatty acid amide lubricants; Bisamide (Nippon Kasei), Diamid 200 bis (Nippon Kasei), Armowax EBS (Lion Akzo), etc. (6) Alkylamine-based Lubricant: Electrostripper-TS-2, Electrostripper-TS-3 (Kao soap), etc. (7) Hydrocarbon lubricants: Liquid paraffin, natural paraffin, micro wax,
Synthetic parisine, polyethylene wax, polypropylene wax, chlorinated hydrocarbons, fluorocarbons, etc. (8) Fatty acid-based lubricants; higher fatty acids (C ₁₂ or more are preferred), oxyfatty acids, etc. (9) Ester-based lubricants; lower alcohol esters of fatty acids, Polyhydric alcohol esters of fatty acids, polyglycol esters of fatty acids, fatty alcohol esters of fatty acids, etc. (10) Alcohol lubricants; polyhydric alcohols, polyglycols, polyglycerols, etc. (11) Metal soaps: lauric acid, stearic acid, ricinoleic acid Higher fatty acids such as naphthenic acid, oleic acid and Li, Mg, Ca, Sr, Ba,
Compounds with metals such as Zn, Cd, Al, Sn, Pb, etc.The thermoplastic resin which is the main component of the resin composition used in the packaging material for the photographic photosensitive material of the present invention may be an injection-molded product or a film-moldable resin. Examples thereof include polyolefin resins such as various polyethylene resins, ethylene-modified resins, ethylene copolymer resins, and various polypropylene resins, polystyrene resins, acrylonitrile / butadiene / styrene resins, polyamide resins, and polyester resins.
Of these, polyolefin resins, especially polypropylene resin and L-LDPE resin, are preferable because they have good moisture resistance, waterproofness, injection moldability, film moldability, and are inexpensive. Further, polystyrene resins and ABS resins are preferable because they are excellent in injection moldability and dimensional stability and are inexpensive.

The polypropylene resin includes a homotype polypropylene resin, a random type polypropylene resin which is a propylene-ethylene copolymer resin, and a block type polypropylene resin.

As a polymerization method, titanium tetrachloride (Ti
Cl ₄ ) and triethylaluminum (AlEt ₃ ) mixed catalyst method (Ziegler catalyst), titanium trichloride (TiCl ₃ ) and triethylaluminum (AlEt ₃ ).
A typical example is a method using a composite catalyst (Natta catalyst) in which the above are combined. Other polymerization methods include the standard oil method, the Phillips method and the sun oil method.

Specific examples of product names are Nisseki Polypro (Nippon Petrochemical), UBE Polypro (Ube Industries), Show Allomer (Showa Denko), Sumitomo Noblen (Sumitomo Chemical), Chisso Polypro (Chisso), Mitsubishi Noblen (Mitsubishi Oil). Tokuyama Polypro (Tokuyama Soda), Mitsui Petrochemical Polypro (Mitsui Petrochemical), Mitsui Noblen (Mitsui Toatsu Chemical) and the like.

A preferred polypropylene resin for injection molding is a copolymer resin of propylene and ethylene, particularly propylene 90-
Propylene containing 99% by weight and 1 to 10% by weight of ethylene
Ethylene random copolymer resins are preferred. A melt index (according to MI-ASTM-D1238) of 10 to 80 g / 10 min is suitable, and a dimensional accuracy of 20 to 60 g / 10 min is particularly high.

The content of the polypropylene resin in the injection-molded product requiring strength is preferably 50 to 90% by weight, particularly preferably about 60 to 80% by weight, and other polyethylene resins, particularly L
-Used by mixing with LDPE resin and elastomer.

The L-LDPE (Liner Low Density Polyetylene) resin is referred to as a third polyethylene resin, and has the advantages of both medium- and low-pressure method and high-pressure method polyethylene resins. It is a strong resin. This resin is a copolymer obtained by copolymerizing ethylene and an α-olefin having 3 to 13 carbon atoms, preferably 4 to 10 carbon atoms by a low pressure method or a high pressure improvement method, and has a linear straight chain with a short branch structure. It is a polyethylene resin. Butene is a preferable α-olefin in terms of physical strength and cost.
1, octene-1, hexene-1, 4-methylpentene-1, heptene-1 and the like are used.

The density is generally considered to be a low-medium density polyethylene resin, but most commercial products have a density within the range of 0.87 to 0.95 g / cm ³ . The melt index is often within the range of 0.1 to 50 g / 10 minutes.

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

Representative 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 Methyl Pentene-1 Copolymer Resin Ultzex (Mitsui Petrochemical) Ethylene Octene-1 Copolymer Resin Stamirex (DSM Company) Dourex (Dow Chemical Company) SCLEAR ( DuPont Canada Ltd.) MORETEC (Idemitsu Petrochemical) Physical among these L-LDPE resins Particularly preferred from the viewpoint of degree and heat seal strength and film moldability, the melt index (hereinafter MI and display) is 0.8~10g / 10 min (JIS K
−6760), density 0.870 to 0.940 g / cm ³ (JIS K-6760),
And it was obtained by the liquid phase process and the gas phase process in which the carbon number of the α-olefin is 6 to 8.

A particularly preferred representative example is the trade name of Wurtzex of Mitsui Petrochemical Co., Ltd. in which 4-methylpentene-1 having 6 carbon atoms as an α-olefin side chain is introduced into polyethylene, and α-olefin side. MORETEC of Idemitsu Petrochemical Co., Ltd. in which octene-1 having 8 carbon atoms is introduced as a chain
DSM's Stamilex and Dow Chemical's Dourex are available.
-LDPE resin. ).

Preferred typical examples obtained by the low-pressure vapor phase process are trade names. TUFLIN of UCC Co. and Nihon Unicar Co., Ltd. in which hexene-1 having 6 carbon atoms is introduced as an α-olefin side chain. There is TUF THENE etc.

Also recently released ultra low density linear low density polyethylene resin with a density of less than 0.910 g / cm ³ , such as NUC-FLX from UCC.
And Excellen VL manufactured by Sumitomo Chemical Co., Ltd. are also preferable (the above two products both use butene-1 in which the α-olefin has 4 carbon atoms).

A participation inhibitor may be added to the resin composition of the present invention in order to prevent coloring failure and the like. Representative examples of antioxidants are described below.

(A) Phenolic antioxidant 6-t-butyl-3-methylphenyl derivative, 2.6
-Di-t-butyl-P cresol, 2.2'-methylenebis (4-methyl-6-t-butylphenol), 2.
2'-methylenebis- (4-ethyl-6-t-butylphenol), 4'-butylidenebis (6-t-butyl-m-cresol), 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, erakis [methylene-3 (3 ′ · 5′-
Di-t-butyl-4'-hydroxyphenyl) propionate] methane, etc. (b) Ketoneamine condensation-type antioxidant 6-ethoxy-2,2,4-trimethyl-1,2-dihydroquinoline, 2,2.4- Polymers of trimethyl-1,2-dihydroquinoline, trimethylhydroquinoline derivatives, etc. (c) Allylamine 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, trinonyl phenyl phosphite, triphenyl phosphite (f) thiourea antioxidants Thiourea derivative, 1,3-bis (dimethylaminopropyl) -2-thiourea (to) Other antioxidants useful for air oxidation Dilauryl thiodipropionate Representative commercially available antioxidants are shown below.

(1) Phenolic antioxidants: SUMILIZER BHT (Sumitomo), IRGANOX 1076 (Ciba Geigy), MARK AO-50 (Adeka Argus), SUMILIZER B
P-76 (Sumitomo), TOMINOX SS (Yoshitomi), IRGANOX 565 (Ciba Geigy), NONOX WSP (ICI), SANTONOX (Monsant)
o), SUMILIZER WX R (Sumitomo), ANTAGE CRYSTAL (Kawaguchi), IRGANOX 1035 (Ciba Geigy), ANTAGE W-400
(Kawaguchi), NOCLIZER NS-6 (Ouchi Shinko), IRGANOX 142
5 WL (Ciba Geigy), MARK AO-80 (Adeka Argus), SUMILIZER GA-80 (Sumitomo), TOPANOL CA (IC
I), MARK AO-30 (Adeka Argus), MARK AO-20
(Adeka Argus), IRGANOX 3114 (Ciba Geigy), MARK AO-330 (Adeka Argus), IRGANOX 13
30 (Ciba Geigy), CYANOX 1790 (ACC), IRGANOX 10
10 (Ciba Geigy), MARK AO-60 (Adeka Argus), SUMILIZER BP-101 (Sumitomo), TO-MINOX TT (Yoshitomi) (2) Phosphorus antioxidants; IRGAFOS 168 (Ciba Geigy), MARK 2112 (Adeka Argus), WESTON 618 (BorgWarner), MARK PEP-
8 (Adeka Argus), ULTRANOX 626 (Borg Warner), MARK PEP-24G (Adeka Argus), MARK PE
P-36 (Adeka Argus), HCA (Sanko) (3) Thioether antioxidant; DLTDP "YOSHITOMI" (Yoshitomi), SUMILIZER TPL (Sumitomo),
ANTIOX L (NOF), DMTD “YOSHITOMI” (Yoshitomi), SUMILI
ZER TPM (Sumitomo), ANTIOX M (NOF), DSTP “YOSHITOM
I "(Yoshitomi), SUMILIZER TPS (Sumitomo), ANTIOX S (NOF), SEENOX 412S (Cipro), MARK AO-412 S (Adeka Argus), SUMILIZER TP-D (Sumitomo), MARK AO
-23 (Adeka Argus), SANDSTAB P-EPQ (Sand), IRGAFOS P-EPQ FF (Ciba Geigy), IRGANOX 1
222 (Ciba Geigy), MARK 329K (Adeka Argus), WES TON399 (Borg Warner), MARK 260 (Adeka Argus), MARK 522A (Adeka Argus) (4) Metal deactivator NAUGARD XL-1 (Uni) Royal), MARK CDA-1 (Adeka Argus), MARK CDA-6 (Adeka Argus),
LRGANOX MD-1024 (Ciba Geigy), CUNOX (Mitsui Toatsu) Particularly preferred antioxidants are phenolic antioxidants. Commercially available products include Irganox of Ciba Geigy and Sumitizer Chemicals' Sumilizer BHT, Sumilizer. BH-
76, Sumilizer WX-R, and Sumilizer BP-101.

In addition, 2,6-di-t-butyl-p-cresol (BHT), a low-volatile high molecular weight phenolic antioxidant (trade name Ireg
anox 1010, Ireganox 1076, Topanol CA, Ionox 330 etc.),
It is effective to use one or more of dilauryl thiodipropionate, distearyl thiopropionate, dialkyl phosphate and the like, especially two or more thereof in combination.

The added amount is, for example, 0.005 to 1.0% by weight.

If the amount added is less than 0.05% by weight, there is almost no effect of addition.
On the other hand, if the amount added exceeds 1.0% by weight, the photographic film utilizing the oxidation and reduction effects may be adversely affected and the photographic performance may be abnormal. For this reason, it is preferable to add the antioxidant in the minimum amount that does not cause coloring failure, fisheyes, or lumps (lumps).

Furthermore, when used in combination with carbon black, it exerts a synergistic antioxidant effect.

Other Plastic Data Handbook (published by KK Industry Research Committee), pages 794 to 799 of various antioxidants and plastic additives data collection (KK Chemical Industry Co., Ltd.)
Antioxidants and PLASTICS disclosed on pages 327-329
It is possible to select and use various antioxidants and the like disclosed on pages 211 to 212 of AGE ENCYCLOPEDIA Advanced Edition 1986 (KK Plastic Age).

Further, a nucleating agent can be added in order to improve the crystallization rate, rigidity and moldability. As this nucleating agent, both an organic nucleating agent and an inorganic nucleating agent can be used. In particular dibenzylidene sorbitol compounds such as 1,3,2,4 di (methylbenzylidene) sorbitol,
Organic nucleating agents such as 1,3,2,4 bis (methylbenzylidene) sorbitol and aluminum benzoate are preferable.

Next, typical examples of other additives will be described below, but the present invention is not limited thereto and can be selected from all known ones.

(Types of Additives) (Representative Examples) (1) Antistatic Agent; Nonionic Surfactant, Anionic Surfactant, Cationic Surfactant, Amphoteric Surfactant, Metal Powder, Metal Flake, Metal Surface Coated Pigment , Whiskers, etc. (2) Antiblocking agents; silicon dioxide, higher fatty acid polyvinyl esters, aluminum silicates, calcium silicates, etc. (3) Plasticizers: phthalic acid esters, glycol esters, fatty acid esters, phosphoric acid esters, etc. (4) Stable Agents: lead-based, cadmium-based, zinc-based, alkaline earth metal-based,
Organotin, etc. (5) Flame retardant; Phosphate ester, halogen lubricant Phosphate ester, halide, inorganic substance, phosphorus-containing polyol, etc. (6) Filler: Alumina, kaolin, clay, calcium carbonate, mica, talc, titanium oxide, silica Etc. (7) Reinforcing agent: glass roving, metal fiber, glass fiber, glass milled fiber, carbon fiber, etc. (8) Foaming agent: Inorganic foaming agent (ammonia carbonate, sodium bicarbonate), organic foaming agent (nitroso type, azo type), etc. (9) Vulcanizing agent; Vulcanization accelerator, accelerating aid, etc. (10) Deterioration inhibitor; UV absorber, antioxidant, metal deactivator, peroxide decomposing agent, etc. (11) Coupling agent; Silane-based, titanate-based, chromium-based, aluminum-based, etc. (12) Various thermoplastic resins, rubber, etc. The resin composition used for the packaging material for the photographic light-sensitive material of the present invention is an inflation type ® down method films, extrusion melt extrusion coating or cast film as JP 60-196335, JP-Sho 62-18546, JP-,
It is used as a packaging material for photographic light-sensitive materials such as laminated films and light-shielding films disclosed in JP-A-62-18547 and JP-A-62-53829.

The resin composition used in the packaging material for the photographic light-sensitive material of the present invention is used in injection molding and blow molding as disclosed in JP-B-56-16414.
JP-A-57-207248, JP-A-58-203437, JP-A-60-14237, JP-A-61-48841, JP-A-61-86367, JP-A-61-86367 Injection-molded articles for photographic light-sensitive materials disclosed in JP-A-62-284355, JP-A-61-128256, JP-A-63-72742 and the like, and
63-124050, JP-A-63-186237, JP-A-1
It is used for a light-shielding magazine for assembling a photographic light-sensitive material disclosed in Japanese Unexamined Patent Publication No. 187547.

[Action]

In the resin composition used for the packaging material for the photographic light-sensitive material of the present invention, the conductive carbon black and the lubricant ensure antistatic property without using an antistatic agent. In the present invention, it is possible to use an antistatic agent together.

〔Example〕

A packaging material using an example of the resin composition used for the packaging material for the photographic light-sensitive material of the present invention is shown in FIGS. 1 to 3.

1 and 2 are partial sectional views of a packaging material for a photographic light-sensitive material.

The packaging material shown in FIG. 1 is a single layer inflation film formed by an inflation film molding method.

The packaging material shown in FIG. 2 is a one-sided embossed light-shielding one-sided matte embossed light-shielding sheet molded by an extrusion molding method.

The packaging material shown in FIG. 3 is a light-shielding case for a movie formed by an injection molding method, and includes a main body 1 and a lid body 2.

Invention product I DBP oil absorption is 420 ml / 100 g, specific surface area (BET) is 1200 m ² / g,
4 wt% conductive carbon black with a heavy metal content of 180 ppm and an average particle size of 40 mμ, 0.2 wt% calcium stearate and 0.05 wt% erucic acid amide as a lubricant, MFR 2.1 g / 10 min, density 0.920 g / cm ³ of ethylene
Using an ethylene copolymer resin composition consisting of a 4-methylpentene-1 copolymer resin, a thickness of 100 μm shown in FIG.
A single-layer blown film was prepared.

Invention product II DBP oil absorption 480ml / 100g, specific surface area (BET) 1300m ² / g,
4 wt% conductive carbon black with a heavy metal content of 180 ppm and an average particle size of 40 mμ, calcium stearate 0.3 wt% as a lubricant and oleic acid amide 0.05 wt% were added, MFR 2.1 g / 10 min, density 0.920 g / cm ³ ethylene
Using an ethylene copolymer resin composition consisting of a 4-methylpentene-1 copolymer resin, a thickness of 100 μm shown in FIG.
A single-layer blown film was prepared.

Comparative product I DBP oil absorption 325ml / 100g, specific surface area (BET) 950m ² / g,
Add 4% by weight of Ketjenblack EC (manufactured by Lion Axo) with a heavy metal content of 2300ppm and an average particle size of 40mμ, ethylene 4 with MFR 2.1g / 10min and density 0.920g / cm ^3.
An ethylene copolymer resin composition comprising a methylpentene-1 copolymer resin was used to prepare a single-layer inflation film having a thickness of 100 μm shown in FIG.

Conventional product I DBP oil absorption of 76 ml / 100 g, specific surface area (BET) of 125 m ² / g, heavy metal content of 890 ppm, average particle size of 21 mμ Furnace carbon black (Mitsubishi Kasei carbon black ^# 44) 4% by weight, Using an ethylene copolymer resin composition consisting of an ethylene / 4 methylpentene-1 copolymer resin having an MFR of 2.1 g 10 minutes and a density of 0.920 g / cm ³ , the thickness shown in FIG.
A 100 μm monolayer blown film was prepared.

Invention product III DBP oil absorption of 420 ml / 100 g, specific surface area (BET) of 1200 m ² / g,
4% by weight of conductive carbon black having a heavy metal content of 180 ppm and an average particle of 40 mμ, 0.2% by weight of oleic acid amide as a lubricant and 0.15% by weight of calcium stearate, 0.1% by weight of phenolic antioxidant, 1, as a nucleating agent,
0.2% by weight of 3,2,4 dibenzylidene sorbitol, 15% by weight of talc having an average particle size of 2.7 μm, MFR added for improving low temperature impact strength of 10 g / 10 minutes, density of ethylene tetramethyl of 0.925 g / cm ^3. Using a propylene / ethylene random copolymer resin composition (ethylene content 3.5% by weight) of MFR 400/10 min, which was added with 20% by weight of pentene-1 copolymer resin,
Pellets were manufactured by kneading with a twin-screw kneader manufactured by Ikegai Tekko. After drying the pellets, a light-shielding case for movie film shown in FIG. 3 was molded by using an injection molding machine manufactured by Sumitomo Heavy Industries with a mold clamping pressure of 150 t.

Invention product IV DPE oil absorption 480 ml / 100 g, specific surface area (BET) 1300 m ² / g,
4 wt% conductive carbon black with a heavy metal content of 180 ppm and an average particle size of 40 mμ, 0.2 wt% calcium stearate and 0.1 wt% oleic acid amide as a lubricant, 0.1 wt% phenolic antioxidant, 7.5 g / 10 MFR Propylene / ethylene block copolymer resin (Ethylene ・ 4methylpentene-1 copolymer resin with a density of 0.925 g / cm ³ 15% by weight, synthetic silica 0.1% by weight, MFR of 10 g / min (ethylene A resin composition having a content of 0.5% by weight) was used to form a single-sided matte-embossed light-shielding sheet having a thickness of 1.5 mm shown in FIG.

The light-shielding sheet was useful for a 12000-ft movie film separator, a vacuum-molded light-shielding tray, a magazine for loading a light-sensitive material in a bright room, and the like.

The test results are shown in Table 1.

The evaluation is as follows.

◎… very good ○… excellent ●… possible (within practical limits) ▲… problem (need improvement) ×… not practical test method * 1 Volume resistivity Azumi Electric KK VMG-1000 type super insulation resistance It was measured with a meter.

* 2 Photographic characteristics: Sealed in a moisture-proof, light-shielding bag, and stored at 50 ° C for 3 days.

* 3 Static mark prevention A three-sided seal bag is made from each packaging material, and the photographic emulsion surface is placed outside (outer roll) in and out of the electrophotographic roll film in a dark room at 20 ° C and 30% RH. The evaluation was made based on the development processing result after two times of development.

* 4 Static mark prevention The development processing after the vibration test of the corrugated cardboard film of movie film, which was packaged under the conditions of 20 ° C and 30% RH, under the conditions of JIS Z-0232 using each molded product. The results were evaluated.

* 5 Ease of putting the photographic photosensitive material in and out of the bag * 3 The ease of putting in and taking out the roll film for electro-plantation was evaluated from the experimental results.

〔The invention's effect〕

Since the resin composition used for the packaging material for the photographic light-sensitive material of the present invention is configured as described above, the obtained resin film, injection molded product, molded product such as extruded sheet has excellent antistatic performance, and bleed out and blocking. Generation, development inhibition, and developer contamination do not occur. Further, it does not require lamination with a metal layer, and therefore warpage or curling does not occur, and it can be manufactured at low cost.

[Brief description of drawings]

FIG. 1 is a partial cross-sectional view of a film-like packaging material using an example of a resin composition used for the packaging material for photographic light-sensitive material of the present invention, and FIG. 2 is a packaging material for photographic light-sensitive material of the present invention. FIG. 3 is a partial cross-sectional view of a sheet-shaped packaging material using an example of the resin composition used, and FIG. 3 is an injection molding packaging material using an example of the resin composition used in the packaging material for the photographic light-sensitive material of the present invention. It is a perspective view of (light-shielding case for movies).

Claims (2)

[Claims] 1. DBP oil absorption (ASTM D-2414) is 300ml / 100g
Above, BET specific surface area of 900 m ² / g or more, heavy metal content of 80
Polyolefin resin, polystyrene resin, acrylonitrile-butadiene-styrene resin, polyamide resin and polyester containing 1 to 20% by weight of conductive carbon black having an average particle size of 0 ppm or less and 10 to 60 mμ and 0.01 to 5.0% by weight of a lubricant. Resin composition for use in packaging material for photographic light-sensitive material, comprising one or more resins 2. A resin composition used in a packaging material for a photographic light-sensitive material according to claim 1, wherein the lubricant is one or more of fatty acid amide lubricants and metal soaps.