JP2514081B2 - Resin composition for photosensitive material - Google Patents

Description

TECHNICAL FIELD The present invention relates to a resin composition for a photosensitive material suitable for a packaging material such as an injection-molded article or film for a photosensitive material, a light-shielding bag, a support and the like. is there.

[Conventional technology]

Generally, packaging materials that completely block light are used for those that lose their quality value when exposed to light, such as photosensitive materials. In addition to the above light-shielding property, the packaging material must have sufficient physical strength according to the size and weight of the packaged object,
In addition, the packaging material using the light-shielding film needs to be heat-seal suitable because the opening is sealed by heat-sealing. Further, it is also necessary to have a property of preventing charging due to friction with a photosensitive material.

Conventionally, as a packaging material using such a light-shielding film, there has been one as shown in FIG.

In the laminated film shown in FIG. 6, a resin layer 7b of a low-density polyethylene (hereinafter referred to as LDPE) resin composition to which a light-shielding substance is added, a metal foil layer 8, and a flexible sheet layer 6 are sequentially laminated with an adhesive layer 5. It is a thing.

The present applicant has already proposed to use a resin composition in which a barium compound, zinc, tin, lead and at least one of these compounds are added to a thermoplastic resin in a film case (Japanese Patent Laid-Open No. 60-14237). ).

In addition, a photo of a blended resin of polypropylene resin (hereinafter referred to as PP resin) and linear low-density polyethylene (hereinafter referred to as L-LDPE resin) to which a light-shielding substance, a reinforcing material, a lubricant, and an antioxidant is added. It has been proposed to use it in an injection molded article for a light-sensitive material (JP-A-63-215748).

In addition, it was proposed to use a resin obtained by adding a light-shielding substance, a lubricant, and an antioxidant to a blend resin of a specific PP resin and a specific L-LDPE resin in a film cartridge (Japanese Patent Application No. 62).
-309404 (JP-A-1-152145).

Further, a resin composition most suitable for a light-shielding film and an injection-molded article for a light-sensitive material containing an ethylene copolymer resin, a coupling agent, an aluminum feeler, carbon black, and an antioxidant is proposed (Japanese Patent Application No. 63- 69674 (JP-A-1-243050)).

[Problems to be Solved by the Invention]

However, a composite laminate film of a film using a conventional LDPE resin composition and a flexible sheet such as aluminum foil, paper or cellophane is inferior in physical strength, so that it is used as a thick film and is heavy and expensive.

Further, the resin composition disclosed in Japanese Patent Application Laid-Open No. 60-14237 by the present applicant has a problem in injection moldability and the like because it is a packaging material mainly considering the X-ray blocking property.

The resin composition used in the invention disclosed in JP-A-63-215748 and the invention in Japanese Patent Application No. 62-309404 is a resin composition containing a polypropylene resin and is excellent in physical strength and injection moldability. However, the antistatic property was insufficient.

Further, the invention according to Japanese Patent Application No. 63-69674 is suitable as a polyolefin resin composition containing an aluminum filler for packaging a photosensitive material, but is limited to a polyolefin resin only, and is not limited to other thermoplastic resins. The aluminum filler was not well dispersed, and eye grease failure occurred, so that it could not be put into practical use as a resin composition for a photosensitive material.

The present invention solves the above-mentioned problems by using polystyrene resin, AB
Provide a relatively inexpensive resin composition that satisfies all the properties required for a photosensitive material such as injection moldability, light shielding property, antistatic property, film moldability even with thermoplastic resins such as S resin, polyamide resin, and polyester resin Is intended.

[Means for solving the problem]

The present invention has been made to achieve the above object,
Improvement of dispersibility of metal powder and moldability, improvement of antistatic property,
And fatty acids, fatty acid compounds, to prevent blocking,
Improving the dispersibility of one or more of the surfactants, and an antioxidant to prevent resin burn and the formation of spots.
The problem was solved by using silica white for preventing the occurrence of eye oil failure, improving the light-shielding property, and preventing blocking.

That is, the resin composition for a photosensitive material of the present invention contains a thermoplastic resin as a main component, and 100 parts by weight of a metal powder having an average particle diameter of 0.5 to 60 μm, and one or more of a fatty acid, a fatty acid compound and a surfactant. 0.05 to 70 parts by weight, 0.01 to 20 parts by weight of antioxidant, and 0.2 to 20 parts by weight of silica white having an average particle diameter of 0.3 to 20 μm.

The metal powder in the present invention includes copper, nickel, silver, tin,
It is a powder of a metal such as aluminum, lead, iron or an alloy such as stainless, and a powder of copper, tin, nickel, aluminum or stainless is preferable in terms of quality, price and availability. In particular, aluminum filler is preferable in terms of quality, price and ease of processing and handling.

This aluminum filler includes aluminum short fibers produced by the crack vibration cutting method, aluminum flakes produced by the cutting method, aluminum short fibers produced by the melting method and aluminum powder, aluminum paste, aluminum flakes obtained by crushing aluminum foil by the stamp mill method, the ball mill method, etc. It is a known fine aluminum product.

Is in the range of 0.5 to 60 μm.

The metal powder may have various shapes such as a granular shape, a scale shape, and a comet shape.

The resin composition for a photosensitive material of the present invention contains 0.05 to 70 parts by weight of one or more of fatty acids, fatty acid compounds and surfactants based on 100 parts by weight of metal powder.

When the content of at least one of the fatty acid, the fatty acid compound and the surfactant is less than 0.05 part by weight, the dispersibility of the metal powder is poor and many lumps occur. Further, the antistatic property is not sufficient, blocking is likely to occur, and slipperiness is insufficient. If it exceeds 70 parts by weight, bleed out tends to occur and stickiness tends to occur, resulting in blocking. In addition, the extrudability of the resin is poor (the slip with the screw is large), making it difficult to use.

Representative saturated fatty acids and unsaturated fatty acids include caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, palmitooleic acid, linoleic acid, linolenic acid, ricinoleic acid, erucic acid, etc. There is.

Representative fatty acid compounds include oleic acid amide,
Examples include erucic acid amide, stearic acid amide, bis fatty acid amide, magnesium stearate, calcium stearate, zinc stearate, aluminum stearate, barium stearate, calcium laurate, zinc octylate, butyl oleate, and butyl stearate.

8 carbon atoms in terms of affinity with metal powder and silica white
-25 saturated fatty acids, unsaturated fatty acids and fatty acid compounds of these fatty acids are preferred.

 Examples of the surfactant are shown below.

Nonionic surfactant (typical component polyoxyethylene glycols) Anionic surfactant (typical component polyoxyethylene glycols) Cationic surfactant (typical component quaternary ammonium salt) Amphoteric surfactant Representative examples of ionic surfactants are shown below.

Polyethylene glycol fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene aliphatic alcohol ether, polyoxyethylene alkylphenyl ether, polyoxyethylene glycerin fatty acid ester, polyoxyethylene aliphatic amine, sorbitan monofatty acid ester, fatty acid pentaerythritol , Ethylene oxide adduct of fatty alcohol, ethylene oxide adduct of fatty acid, ethylene oxide adduct of fatty acid amino or fatty acid amide, ethylene oxide adduct of alkylphenol, ethylene oxide adduct of alkylnaphthol, partial fatty acid ester of polyhydric alcohol Ethylene oxide adduct, and various nonionic antistatic agents described in JP-B-63-26697, page 120.

 Representative examples of the anionic surfactant are shown below.

Ricinoleic Acid Sulfate Sodium Salt, Various Fatty Acid Metal Salts, Silinoleic Acid Sulfate Sodium Salt,
Sulfated ethylaniline oleate, olefin sulfate salts, oleyl alcohol sulfate ester soda salt, alkyl sulfate ester salt, fatty acid ethyl sulfonate, alkyl sulfonate, alkyl naphthalene sulfonate, alkylbenzene sulfonate, succinate Representative examples of the above-mentioned cationic surfactants are shown below.

Primary amine salt, tertiary amine salt, quaternary ammonium salt, pyridine derivative, etc. Representative examples of the amphoteric surfactant are shown below.

Carboxylic acid derivative, imidazoline derivative, petaine derivative, etc. In the resin composition for a photosensitive material of the present invention, 0.01 to 20 parts by weight of the antioxidant is contained with respect to 100 parts by weight of the metal powder.

If it is less than 0.01 part by weight, the antioxidant effect is small and only the kneading cost increases.

If the amount exceeds 20 parts by weight, bleed-out tends to occur, which deteriorates the quality of products such as photographic light-sensitive materials that utilize the oxidation / reduction effect. Moreover, the effect of increasing the amount is small and the cost is increased.

 Representative examples of this antioxidant are shown below.

(A) Phenolic antioxidant 6-t-butyl-3-methylphenyl derivative, 2.
6-di-t-butyl-p-cresol, 2.2'-methylenebis- (4-ethyl-6-t-butylphenol), 4'-butylidenebis (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'-thiobis (3-methyl-)
6-t-butylphenol), 4.4'-butylidene bis (3-methyl-6-t-butylphenol), stearyl-β (3.5-di-4-butyl-4-hydroxyphenyl) propionate, 1.1 3-tris (2-methyl-4hydroxy-5-t-butylphenyl) butane, 13.5 trimethyl-24.6-tris (3.
5-di-t-butyl-4hydroxybenzyl) benzene, tetrakis [methylene-3 (3'.5'-di-t-
Butyl-4'-hydroxyphenyl) propionate]
Methane, etc. (B) Ketone amine condensation-type antioxidant 6-ethoxy-2,2,4-trimethyl-1,2-dihydroquinoline, polymer of 2,2,4-trimethyl-1,2-dihydroquinoline, trimethyldihydro Quinoline derivatives, etc. (c) Allylamine-based antioxidants Phenyl-α-naphthylamine, N-phenyl-β-
Naphthylamine, N-phenyl-N'-isopyropyr-
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. 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), etc. (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
PEP-36 (Adeka Argus), HCA (Sanko), etc. (3) Thioether antioxidants; DLTDP “YOSHITOMI” (Yoshitomi), SUMILIZER TPL (Sumitomo), ANTIOX L (NOF), DMTD “YOSHITOMI” (Yoshitomi) ),
SUMILIZER TPM (Sumitomo), ANTIOX M (NOF), DSTP “YOS
HITOMI "(Yoshitomi), SUMILIZER TPS (Sumitomo), ANTIOX S
(NOF), SEENOX 412S (Cipro), MARK AO-412S
(Adeka Argus), SUMILIZER TP-D (Sumitomo), MA
RK AO-23 (Adeka Argus), SANDSTAB P-EPQ (Sand), IRGAFOS P-EPQ FF (Ciba Geigy), IRGANOX
1222 (Ciba Geigy), MARK 329K (Adeka Argus), WES TON399 (Borg Warner), MARK 260 (Adeka Argus), MARK 522A (Adeka Argus), etc. (4) Metal deactivator NAUGARD XL-1 ( Uniroyal), MARK CDA-1 (Adeka Argus), MARK CDA-6 (Adeka Argus), LRGANOX MD-1024 (Ciba Geigy), CUNOX (Mitsui Toatsu) etc. Particularly preferred antioxidants are phenolic antioxidants. It is an agent, and as commercial products, various Irganox of Ciba-Geigy and Sumilizer BHT, Sumilizer BH of Sumitomo Chemical Co., Ltd.
-76, Sumilizer WX-R, Sumilizer BP-101, etc.

In addition, 2.6-di-t-butyl-p-cresol (BH
T), low-volatile high molecular weight phenolic antioxidant (trade name: Ireganox 1010, Ireganox 1076, Topanol CA, Ionox 3
30 etc.), dilauryl thiodipropionate, distearyl thiopropionate, dialkyl phosphate and the like, and it is effective to use one or more, particularly two or more thereof in combination.

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

In the resin composition for a photosensitive material of the present invention, silica white (also known as white carbon) is 0.2 per 100 parts by weight of metal powder.
~ 20 parts by weight are included.

The silica white may be a natural product or a synthetic product, and an average particle size of 0.3 to 20 μm is used.

If it is less than 0.3 μm, the cohesiveness is strong, and lumps (lumps) are likely to occur.

If it exceeds 20 μm, white silica will appear on the product surface and the product surface will be rough, reducing the commercial value.

The thermoplastic resin which is the main component of the resin composition for a photosensitive material of the present invention may be any resin as long as it is a resin that can be injection-molded or film-molded, and examples thereof include polyethylene resin, ethylene-modified resin and ethylene. Examples thereof include copolymer resins, polyolefin resins such as polypropylene resins, polystyrene resins, acrylonitrile / butadiene / styrene resins, polyamide resins, and polyester resins. Among them, polyolefin resin, especially polypropylene resin and L-LDPE resin, are highly moisture-proof, waterproof, injection moldable and film moldable, and inexpensive, and polystyrene resin and ABS resin are excellent in injection moldability and dimensional stability. It is preferable because it is inexpensive.

Polypropylene resins include homo-type polypropylene resins, random-type polypropylene resins which are propylene-ethylene copolymer resins, and block-type polypropylene resins.

As a polymerization method, a method using a composite catalyst (Ziegler catalyst) obtained by mixing titanium tetrachloride (TiCl ₄ ) and triethylaluminum (AlEt ₃ ) in a saturated hydrocarbon solvent,
Titanium trichloride (TiCl ₃ ) and triethylaluminum (AlE
A typical example is a method using a composite catalyst (Natta catalyst) combining t ₃ ). Other polymerization methods include a standard oil method, a Phillips method, and a 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.

The polypropylene resin preferable for injection molding in the present invention is a copolymer resin of propylene and ethylene, and particularly preferably a propylene-ethylene random copolymer resin composed of 90 to 99% by weight of propylene and 1 to 10% by weight of ethylene. Melt index (MI = ASTM-D1238) is 10-80g
/ 10 minutes is suitable, and especially when 20 to 60 g / 10 minutes is used, the dimensional accuracy is high.

The content of the polypropylene resin in the injection molded product using the resin composition of the present invention is 50 to 90% by weight, preferably about 60 to 80% by weight.

The L-LDPE (Liner Low Density Polyetylene) resin is referred to as a third polyethylene resin, and is energy-saving, which has the advantages of both medium- and low-pressure polyethylene resins.
It is a low-cost, high-strength resin that meets the demands of the age of resource saving. 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 linear short-chain structure. It is a polyethylene resin. The preferred α-olefin in terms of physical strength and cost is butene-
1, octene-1, hexene-1, 4-methylpentene-1, heptene-1 and the like are used.

Although the density is generally considered to be about the same as that of a low-medium density polyethylene resin, many commercial products have a density in 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) Dow Rex (Dow Chemical Company) Clearer (DuPont Canada Company) Marrex (Phillips Company) Stamilex (DSM Company) Excellen VL (Sumitomo Chemical Co., Ltd.) NeoZex (Mitsui Petrochemical) Mitsubishi Polyethylene-LL (Mitsubishi Petrochemical) Nisseki Linilixusku (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.) Screer ( DuPont Canada) MORETEC (Idemitsu Petrochemical) These L-LDPE Preferred from the viewpoint of physical strength and heat seal strength and film formability in the butter, melt index (hereinafter MI and display) is 0.8~10g / 10 min (JIS K-
6760), a density of 0.870 to 0.940 g / cm ³ (JIS K-6760), 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 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. MORETE of Idemitsu Petrochemical Co., Ltd. in which octene-1 having 8 carbon atoms is introduced as a chain
C and DSM's Stamilex and Dow Chemical's Dowlex (these four products were obtained by the co-liquid phase process L
-LDPE resin. ).

A preferred representative example obtained by the low-pressure vapor phase process is the trade name of Nippon Unicar Co., Ltd. in which hexene-1 having 6 carbon atoms is introduced as an α-olefin side chain.
TUFLIN and UCC's TUFTHENE are available.

In addition, recently released ultra-low density linear low density polyethylene resin with a density of less than 0.910 g / cm ³ , such as UCC's NUC-FL.
X and Sumitomo Chemical Co., Ltd.'s Excellen VL are also preferable (2
(Butene-1 with 4 carbon atoms is used as α-olefin).

The amount of metal powder contained in the thermoplastic resin varies depending on the intended molded product, but is preferably in the range of 0.1 to 20% by weight. If it is less than 0.1% by weight, the coloring effect and the light-shielding effect are small and only the kneading cost increases, while if it exceeds 20% by weight, the occurrence of lumps (lumps) increases and the physical strength decreases, making practical application difficult. Become.

In the resin composition of the present invention, the light-shielding property can be ensured without adding a black pigment such as carbon black or graphite, but when used in combination with carbon black, the antioxidant property, antistatic property, light-shielding property can be further improved. It is improved by exerting a synergistic effect on sex.

Carbon black is classified into gas black, oil furnace black, anthracene black, acetylene black, furnace black, channel black, thermal black and lamp black depending on the raw material,
Depending on the raw materials, gas black, oil furnace black, anthracene black, acetylene black,
It is classified into oil smoke, pine smoke, animal black, vegetable black, and the like.

Among these carbon blacks, PH5-9, especially P
H6 ~ 8, average particle size 10 ~ 200mμ is preferred, especially
PH6 to 9 and average particle size of 15 to 50 mμ are preferable. By using such a PH and an average particle size, the photographic light-sensitive material is not adversely affected, the fog is less likely to occur, the increase or decrease in the photosensitivity is less likely to occur, the light-shielding ability is large, and the carbon black particles ( It is possible to prevent lumps, fisheyes, and pinholes from occurring.

Furnace carbon black is preferable for the purpose of improving light-shielding properties, costs, and physical properties, and Ketjen carbon black, acetylene carbon black, and graphite are preferable for the purpose of improving antistatic properties.

The content of carbon black is preferably in the range of 0.05 to 15.0% by weight.

If it is less than 0.05% by weight, it is necessary to stack another light-shielding layer in order to secure the light-shielding property.

If it exceeds 15.0% by weight, the physical strength and heat sealability of the film are deteriorated and the cost is increased.

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

The resin composition of the present invention is used for an inflation method film, a T-die method film, an extrusion melt extrusion coating film, or a cast film.

Further, the resin composition of the present invention includes injection molding, blow molding, JP-B-43-2837, JP-B-44-8856, JP-B-60-35068, JP-B-61-9401, and JP-A-61-9401. Sho 5
8-203436, JP 58-203437, JP 59
-15019 and other photographic film spools, JP-B-56-16609 and JP-B-56-16610, film cartridges disclosed in JP-A-60-163045
Japanese Patent Laid-Open Publication No. 63-204252, a photographic film cartridge case disclosed in Japanese Laid-Open Patent Publication No. 63-204252, and Japanese Laid-Open Patent Publication No. 62-210457.
Patrone case cap for photographic film disclosed in JP-A-63-113453, plastic case for instant film and pack for instant film disclosed in JP-A-59-77144, JP-A-54-100617 , A plastic case for a microfilm disclosed in JP-A-62-360664 and USP 4,678,080,
JP-B-56-16608, JP-A-63-65439, USP
4,616,914 magazine for strip-shaped photosensitive material, roll film cartridge disclosed in Japanese Utility Model Publication No. 61-36835, packaging material for magnetic material (bookcase for VTR, VTR cassette, audio cassette, VTR cassette storage Case, reel, disc, friction sheet,
Floppy envelopes, etc.), automobile parts, parts for home electric appliances, etc.

[Action]

In the present invention, the metal powder improves the antistatic property and the light shielding property, and the light shielding property can be secured even if the black pigment is not added. In addition, it provides heat resistance under sunlight.

Furthermore, it has a low hygroscopicity and does not have pinholes or foaming when forming a film.

〔Example〕

Example 1 An example of a film-like packaging material using the resin composition of the present invention will be described with reference to FIGS. 1 to 5.

1 to 5 are partial cross-sectional views showing the layer structure of a film-like packaging material for a photosensitive substance.

The packaging material of FIG. 1 is composed of a single film of a resin film 1a made of the resin composition of the present invention.

The packaging material of FIG. 2 is composed of a two-layer coextruded film in which a resin film 1a made of the resin composition of the present invention and a thermoplastic resin film 2 are laminated.

The packaging material of FIG. 3 is composed of a three-layer coextrusion film in which a thermoplastic resin film 2 is laminated with a resin film 1a made of the resin composition of the present invention via an intermediate layer 3.

The packaging material of FIG. 4 is a four-layer blocking laminate in which a two-layer coextruded film Ia comprising a resin film 1a made of the resin composition of the present invention and a blocking generation film 4 is further adhered by blocking between the blocking generation films 4. It is made of film.

The packaging material of FIG. 5 is composed of a three-layer laminated film in which the flexible sheet 6 is laminated on the resin film 1a made of the resin composition of the present invention with the adhesive layer 5 interposed therebetween.

Next, the experimental results showing the characteristics of the products I and II of the present invention will be described.

Inventive Product I As a thermoplastic resin, an L-LDPE resin (MI2.0g / 1, which is a copolymer of ethylene and hexene-1 produced by a gas phase method.
0 minutes, density (according to ASTM D-1505) 0.920 g / cm ³ ) 86.35% by weight, nickel powder as metal powder (Carbon Nickel #
287, average particle size 4 μm, Fukuda metal foil powder KK) 10% by weight
(100 parts by weight as metal powder), oleic acid amide (Alfro-E-10, manufactured by NOF Corporation KK) as a fatty acid compound.
15% by weight (1.5 parts by weight with respect to the metal powder), 0.2% by weight of phenolic antioxidant (Irganox 1010, manufactured by Ciba-Geigy) as an antioxidant (2 parts by weight with respect to the metal powder), composition formula SiO as silica white Hydrous silicic acid represented by ₂ · nH ₂ O (Syloid 244, average particle size 3.3 μm, manufactured by Fuji Devison KK) 0.3% by weight (3 parts by weight based on metal powder), oil furnace carbon black (furnace carbon black # 44B, Using a blown film molding machine, a resin composition having an average particle diameter of 21 mμ and 3% by weight of Mitsubishi Kasei KK) was formed into a light-shielding inflation film having a thickness of 70 μm, a blow ratio of 2.0, and a folding diameter of 785 mm.

This light-shielding inflation film was a light-shielding film having excellent light-shielding properties, antistatic properties, blown film moldability, and good moisture-proof properties with no blocking.

Inventive product II As a thermoplastic resin, ethylene and 4-methylpentene-
83.5% by weight of L-LDPE resin (MI 2.1 g / 10 min, density 0.920 g / cm ³ ) produced by the solution method which is a copolymer of 1, aluminum powder as a metal powder (aluminum paste, average particle diameter 2 μm, Asahi Kasei KK) 5% by weight (100 parts by weight as metal powder), stearic acid as fatty acid (NOF K)
K) 3 parts by weight (60 parts by weight based on metal powder), phenolic antioxidant (Irganox 1010,
0.2% by weight (made by Ciba-Geigy) (4% by weight based on the metal powder), the same hydrous silicic acid as the product I of the present invention as silica white.
2% by weight (4 parts by weight with respect to metal powder), structural formula The resin composition containing 0.1% by weight of a silane coupling agent and 8% by weight of carbon black (Ketjen Carbon Black EC, manufactured by Lion Akzo KK) represented by A fold-diameter light-shielding inflation film was prepared.

This light-shielding blown film is the product I of the present invention.
Similarly to the above, it was an excellent film satisfying all the properties required for a light-shielding film for a light-sensitive material.

Example 2 As a thermoplastic resin, a polypropylene resin which is a propylene / ethylene random copolymer having an ethylene content of 3.0% by weight (MI 40 g / 10 minutes, Izod impact strength (ASTM D
4.5 kg · cm / cm) 77.5 wt% and L-LDPE resin (MI 8 g / 10 min, density 0.920 g / cm ³ ) produced by the low pressure method, which is a copolymer of ethylene and 4-methylpentene-1. 15% by weight, aluminum powder (aluminum paste, average particle size 2 μm, manufactured by Asahi Kasei KK) 5% by weight (100 parts by weight as metal powder), stearic acid (manufactured by NOF Corporation KK) 3% by weight (metal powder) as metal powder 60 parts by weight), 0.1% by weight of phenolic antioxidants (Irganox 1010, Irganox 1076, both manufactured by Ciba-Geigy) as antioxidants, 0.2% by weight in total (4 parts by weight with respect to the metal powder), As silica white, the same hydrous silicic acid as the product I of the present invention 0.2% by weight (4 parts by weight with respect to the metal powder), dimethylpolysiloxane (silicon KF96, viscosity 1
Man Stokes, manufactured by Shin-Etsu Chemical KK) 0.1% by weight of a resin composition, a case for a photographic film patrone disclosed in JP-A-63-204252 by an injection molding method, a real-life Sho-60-1338.
Magazine side plate disclosed in Japanese Patent Publication No. 51-10061
No. 7, the plastic case for a microfilm disclosed in Japanese Utility Model Publication No. 59-77144, and the plastic case for an instant photographic film disclosed in Japanese Utility Model Publication No. 59-77144, and JP-A-60-16.
The VTR cassette storage case disclosed in Japanese Patent No. 2636 was created.

These products were excellent in injection molding suitability, had few molding failures, were excellent in light-shielding property, appearance, antistatic property, and physical strength, and had high commercial value. In addition, because the appearance is silver and it is light-reflective, both the surface temperature and the internal temperature of the container do not rise even when left in the sunlight, and when used as a sealed container for photographic light-sensitive materials, it ensures photographic performance. There is no failure like a conventional carbon black-filled light-shielding container that absorbs sunlight and is deformed by heating, or the sealing lid is broken due to vapor pressure due to water evaporation in the photographic photosensitive material due to temperature rise in the sealed container. .

Moreover, unlike carbon black, which does not absorb much moisture, pinholes and silver strips do not occur even if it is not dried. Further, the quality of the photographic light-sensitive material was not adversely affected and the quality could be ensured even during summer storage.

The resin composition of the present invention is a polystyrene resin or
Spool for photographic film using ABS resin, cartridge for film, pack for instant film, light-shielding sheet for instant film, audio cassette, VT
With respect to the R cassette and the like, it was possible to obtain an injection-molded article having the same excellent characteristics as in Example 2 above.

〔The invention's effect〕

Since the present invention is configured as described above, polyethylene resin, polypropylene resin, ethylene copolymer resin (L-
LDPE resin, EEA resin, EVA resin, etc.), polystyrene resin,
Even if a thermoplastic resin such as an acrylonitrile / butadiene / styrene resin, a polyamide resin, or a polyester resin is used, the injection moldability, light shielding property, appearance, antistatic property, physical strength, film moldability and the like can be improved.

[Brief description of drawings]

FIG. 1 to FIG. 5 are partial cross-sectional views showing the layer structure of an example of a packaging material for a photosensitive substance using the resin composition for a photosensitive substance of the present invention. FIG. 6 is a partial cross-sectional view showing the layer structure of a conventional packaging material for a photosensitive substance. 1a ... Resin film containing metal powder 2 ... Thermoplastic resin film 3 ... Intermediate layer 4 ... Blocking generation film 5 ... Adhesive layer 6 ... Flexible sheet

 ─────────────────────────────────────────────────── --- Continued from the front page (56) Reference JP-A 63-215748 (JP, A) JP-A 59-177541 (JP, A) JP-A 53-69630 (JP, A) JP-A 62- 104879 (JP, A) JP-B 6-15226 (JP, B2) JP-B 7-101294 (JP, B2) "Rubber-Plastic compounded chemicals", 2nd revision, page 231, Rubber Digest Co., Ltd. , 1993

Claims (1)

(57) [Claims] 1. To 100 parts by weight of a metal powder having an average particle diameter of 0.5 to 60 .mu.m, 0.05 to 70 parts by weight of at least one of fatty acid, fatty acid compound and surfactant and 0.05 to 70 parts by weight of antioxidant.
01 to 20 parts by weight of silica white with an average particle size of 0.3 to 20 μm
Resin composition for a photosensitive material containing a thermoplastic resin as a main component, characterized in that it is contained in a proportion of 0.2 to 20 parts by weight.