JP2797156B2 - Photo film container - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photographic film container.

[0002]

2. Description of the Related Art In the early days, containers for photographic film patrone did not adversely affect photographic films and were excellent in moisture barrier and gas barrier properties.
However, when used in large quantities, the production is troublesome and expensive, so that it has been produced by injection molding using a thermoplastic resin. As the thermoplastic resin, a high-rigidity thermoplastic resin (ie, a polystyrene resin or a homopolypropylene resin having a low melt flow rate) has been used in view of a substitute for a metal.

However, in recent years, improvement of impact strength, securing of rigidity,
From the viewpoint of improving transparency by using a transparent container,
A propylene / ethylene random copolymer resin having a low flow rate has come to be used, and containers for photographic film cartridges having various resin compositions have been proposed. For example,
The inventor of the present invention has proposed a container body capable of shortening the molding cycle and eliminating molding failure (Japanese Patent Laid-Open No. 60-163045). In order to make the fatty acid amide-based lubricant 0.05-
A container body containing 1% by weight was proposed (JP-A-61-7394).
No. 7).

In addition, as a form of the photographic film patrone container, a container in which the container body and the lid are integrally formed by a hinge is proposed in addition to the container body and the lid which are formed separately. (JP-A-63-223640,
JP-A-1-88940).

[0005]

However, there are cases where the above-mentioned photo film container cannot be reliably detected when it is detected by the photoelectric tube. In addition, scratches and dust were conspicuous and were not preferable in appearance. Further, further improvement in drop strength and Izod impact strength has been desired.

SUMMARY OF THE INVENTION The present invention solves the above-mentioned problems and provides a photo film container which can be reliably detected by a photoelectric tube, can also see a photo film cartridge housed therein, and can maintain or improve physical strength. The purpose is to provide.

[0007]

Means for Solving the Problems The present invention has been studied diligently to achieve the above object, and found that the haze (thickness: 1.0 m, conforming to ASTM D-1003) that cannot be detected by a phototube is too small. It has been found that if the haze is in an appropriate range, the detection by the phototube can be surely performed, and the stored photographic film can be seen well. Further, the present invention has been further studied, and it has been found that, when the resin composition is a predetermined one, impact whitening is small, the haze is in a predetermined range, and the drop strength is improved, and the present invention has been completed. It has also been found that the addition of a coloring substance to the resin composition significantly improves the drop strength.

That is, the container for a photographic film of the present invention comprises 65 to 95% by weight of a propylene / ethylene random copolymer resin having an ethylene content of 0.3 to 8% by weight and a flexural modulus of 5000 kg / cm ² or more; Propylene with a melt flow rate of 5 to 80 g / 10 min and a notched Izod impact strength of 4 kg · cm / cm ² or more at 23 ° C.
Ethylene block copolymer resin 5 to 35% by weight, nucleating agent 0.01 to 2.0% by weight, lubricity improving substance 0.01 to 10
The haze containing 20% to 65% by weight and the antioxidant in an amount of 0.01 to 1.0% by weight is configured.

The photographic film container of the present invention has an ethylene content of 0.3 to 8% by weight and a flexural modulus of 500.
Propylene ethylene random copolymer resin of 0 kg / cm ² or more 65 to 95% by weight, melt flow rate 5 to 80 g / 10 min, notched izod impact strength at 23 ° C. of 4 kg · cm / cm ² or more 5 to 35% by weight of ethylene block copolymer resin, nucleating agent 0.0
Haze containing 1 to 2.0% by weight, a lubricity improving substance 0.01 to 10% by weight, an antioxidant 0.01 to 1.0% by weight and a coloring substance 0.01 to 29% by weight is 20 to 65
%.

The photographic film container of the present invention contains 65 to 95% by weight of a propylene / ethylene random copolymer resin. This propylene / ethylene random copolymer resin is a polypropylene resin obtained by copolymerizing ethylene having a propylene content of 90% by weight or more and an ethylene content of 10% by weight or less in a random structure (one of polypropylene resins).

Polymerization suitability, rigidity, drop impact strength, transparency,
In terms of the balance between wear resistance and moldability, the ethylene content is
It is preferably from 0.3 to 8% by weight, particularly preferably from 1.0 to 6.5% by weight, most preferably from 1.5 to 5.0% by weight. If the content is less than 0.3% by weight, the drop impact strength is insufficient and the transparency is not improved. If the content is more than 8% by weight, polymerization suitability is deteriorated, Rockwell hardness is small, white powder is easily generated by abrasion, and rigidity is high. And it is easy to cause scratches, deformation, buckling, etc.

The melt flow rate (JIS K7210, hereinafter referred to as MFR) of the propylene / ethylene random copolymer resin is preferably 5 to 80 g / 10 minutes, particularly preferably 10 to 60 g / 10 minutes, and more preferably 15 to 50 g / 10 minutes. Minutes is most preferred. If it is less than 5 g / 10 minutes, the fluidity of the resin is poor and molding failure frequently occurs. 80g / 10
If the amount exceeds the above range, the molecular weight decreases, the surface hardness decreases, the inner and outer walls are easily worn, and white powder frequently occurs.

The propylene / ethylene random copolymer resin has a flexural modulus (JIS K 7203) of preferably 5000 kg / cm ² or more, particularly preferably 8000 kg / cm ² or more, and 10,000 kg / cm ^2.
The above is most preferred. If the flexural modulus is less than 5000 kg / cm ² , denaturation, buckling and the like are likely to occur, and the molding cycle becomes longer. In addition, since the patrone cannot be protected due to its low compression resistance during transportation, and the cap comes off, many failures occur.

The propylene / ethylene random copolymer resin as described above is contained in an amount of 65 to 95% by weight. If the propylene / ethylene random copolymer resin is less than 65% by weight, the rigidity and surface hardness are small, and the white powder easily adheres to the perforated portion and the tip of the photographic film due to friction with the photographic film. Izod impact strength is reduced, and cracks and cracks are likely to occur.

The photographic film container of the present invention contains 5-35% by weight of a propylene / ethylene block copolymer resin. This propylene / ethylene block copolymer resin is a polypropylene resin obtained by copolymerizing ethylene having a propylene content of 60% by weight or more and an ethylene content of 40% by weight or less in a block structure (one of polypropylene resins).

The ethylene content is preferably 1 to 30% by weight in terms of balance of polymerization suitability, rigidity, drop impact strength, abrasion resistance, moldability, impact whitening, mixing with coloring substances, and the like.
Particularly preferred is 2 to 20% by weight, most preferably 3 to 10% by weight. When the content is less than 1% by weight, the effect of improving the drop impact strength is small, and the haze control allowable range becomes small.

On the other hand, if the content exceeds 30% by weight, the suitability for polymerization is deteriorated, the Rockwell hardness is low, white powder is easily generated by abrasion, the rigidity is low, and scratches, deformation, buckling and the like are liable to occur.

The melt flow rate (JIS K7210, hereinafter referred to as MFR) of the propylene / ethylene block copolymer resin is preferably from 5 to 80 g / 10 minutes, particularly preferably from 10 to 60 g / 10 minutes, and particularly preferably from 15 to 50 g / 10 minutes. Minutes is most preferred. If it is less than 5 g / 10 minutes, the fluidity of the resin is poor and molding failure frequently occurs. 80g / 10
If the amount exceeds the above range, the molecular weight decreases, the surface hardness decreases, the inner and outer walls are easily worn, and white powder frequently occurs. The ratio between the MFR of the propylene / ethylene random copolymer resin and the MFR of the propylene / ethylene block copolymer resin is preferably within ± 90%.

The propylene-ethylene block copolymer notched Izod impact strength of 23 ° C. of the resin (JIS K 7110) is preferably 3 kg · cm / cm ² or more, particularly preferably 4 kg · cm / cm ² or more, 5 kg · cm / cm ² or more is most preferable. When the notched Izod impact strength at 23 ° C. is less than 3 kg · cm / cm ² , the effect of improving the impact strength is small, and it is difficult to put into practical use as a photographic film container of the present invention containing 65 to 95% by weight of an ethylene / random copolymer resin. In particular, the impact strength under low temperature conditions (10 ° C. or less) becomes small, and practical use becomes difficult.

The above propylene / ethylene block copolymer resin is contained in an amount of 5 to 35% by weight. If the propylene / ethylene block copolymer resin is less than 5% by weight, the effect of improving the Izod impact strength is small, and cracks and cracks are likely to occur. If it exceeds 35% by weight, the rigidity and the surface hardness are small, and the white powder tends to adhere to the perforated portion and the tip of the photographic film due to friction with the photographic film. The worst problem is the whitening caused by the impact, the poor appearance, and a significant decrease in commercial value.

The nucleating agent is used for improving the crystallization speed, shortening the molding cycle, improving the rigidity, improving the transparency, preventing deformation and the generation of white powder, and improving the physical properties.

The nucleating agent includes an organic nucleating agent and an inorganic nucleating agent. Representative examples of these are shown below.

Organic nucleating agents include carboxylic acids, dicarboxylic acids, salts and anhydrides thereof, salts and esters of aromatic sulfonic acids, aromatic phosphinic acids, aromatic phosphonic acids, aromatic carboxylic acids, aluminum salts thereof, Metal salts of aromatic phosphates, alkyl alcohols having 8 to 30 carbon atoms, condensates of polyhydric alcohols and aldehydes, and alkylamines, such as aluminum pt-butyl benzoate, 1,3 ·
2,4-dibenzylidene sorbitol, a di-substituted benzylidene sorbitol compound represented by the following formula

[0024]

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(Wherein R ₁ and R ₂ are alkyl, alkoxy or halogen having 1 to 8 carbon atoms, m and n are each 0 to 3 and m + n ≧ 1), stearyl lactic acid Metal salts such as calcium and magnesium, N- (2-
Compounds represented by the following formula, such as (hydroxyethyl) -stearylamine

[0026]

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(Wherein R ₃ is an alkyl group having 8 to 30 carbon atoms, k and l are each 0 to 10 and k + 1 ≧
It is one. ), 1,2-hydroxystearic acid lithium salts, sodium salts, potassium salts, calcium salts, metal salts such as magnesium salts, stearyl alcohol, alkyl alcohols such as lauryl alcohol, sodium benzoate,
Includes benzoic acid, sepatin acid and the like.

Inorganic nucleating agents include alkali metal hydroxides such as lithium hydroxide, sodium hydroxide and potassium hydroxide;
Alkali metal oxides such as sodium oxide; alkali metal carbonates such as lithium carbonate, sodium carbonate, potassium carbonate, sodium bicarbonate, and potassium bicarbonate; and alkaline earth metal water such as calcium hydroxide, magnesium hydroxide, and barium hydroxide Oxides, alkaline earth metal oxides such as calcium carbonate and calcium oxide, and the like.

The nucleating agent is not limited to these, and other known nucleating agents can be used. Further, it goes without saying that the nucleating agent is not limited to a single nucleating agent, and two or more nucleating agents can be used in combination.

Preferred examples of the organic nucleating agent which does not adversely affect the photographic film and has a large effect as a nucleating agent are described below.

1,3,2,4-di (methylbenzylidene) sorbitol, 1,3,2,4-di (ethylbenzylidene) sorbitol, 1,3,2,4-di (propylbenzylidene) 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-chlorobenzylidene) sorbitol, 1,3,2,4-di (P-methoxybenzylidene) sorbitol, 1,3,2,4-di (alkylbenzylidene) sorbitol, 1,3 ・ 2 ・4-bis (methylbenzylidene) sorbitol, aluminum benzoate and the like.

Particularly, dibenzylidene sorbitol compounds are preferred.

The organic nucleating agent can be used alone or in combination with an inorganic nucleating agent or in combination of two or more organic nucleating agents. Further, the surface of the organic nucleating agent is preferably coated with various fatty acids, fatty acid compounds, coupling agents, surfactants and the like.

The addition amount of the nucleating agent is 0.01 to 2.0% by weight. If the amount added is less than 0.01% by weight, the effect is hardly exhibited and only the cost of blending is increased. If the amount exceeds 2.0% by weight, the effect is not increased and the cost is increased. It is not preferable because it adversely affects the film, adheres to the mold, bleeds out, or significantly lowers the drop strength.

As a method of blending the nucleating agent, there are a compound system, a dry blend system, a master batch system and the like, but a master batch system is preferable. It is difficult to mix it as it is because of its high bulk and easy to scatter. It is better to mix a small amount of dispersant or wetting agent.
Carboxylic anhydrides are effective as dispersants,
There are higher fatty acids and the like, and fatty acid amide-based lubricants such as oleic acid amide are particularly preferable. DOP, D as wetting agents
A plasticizer such as HP can be used.

In addition, pure products of fatty acids and fatty acid compounds such as higher fatty acids, fatty acid amides and fatty acid metal salts are coated or blended on the surface of the organic nucleating agent to enhance the dispersing effect,
It is also preferable to prevent bleed-out. That is, by adding these additives, the rigidity is increased and the generation of white powder due to abrasion is reduced, and the generation of white powder due to bleed out of the organic nucleating agent is reduced. Further, the odor of the organic nucleating agent can be prevented, and the releasability from the mold, the prevention of generation of static electricity, and the anti-blocking property can be improved.

The lubricity improving substance improves the formability, facilitates the loading and unloading of the photographic film into and out of the container, and improves the air transportability and the suitability for processing and packaging. Further, the mold releasability from the mold, the prevention of generation of static electricity, the anti-blocking property, and the like are improved. Further, the nucleating agent, the antioxidant, the two kinds of polypropylene resins, and the dispersing and kneading properties of the coloring substance essential for the present invention are improved.

For example, there are various lubricants, various surfactants, various antistatic agents, various granular resins and the like.

The names of typical commercial lubricants and the names of manufacturers are described below. (1) Fatty acid amide lubricant; Saturated fatty acid amide lubricant Behenic acid amide lubricant; Diamid KN (Nippon Kasei), etc. Stearamide amide lubricant; Armide HT (Lion fat), Alflow S-10 (Nippon fat), Fatty acid Amide S (Kao), Diamid 200 (Nippon Kasei), Diamid AP-1 (Nippon Kasei), Amide S. Amide T
(Nitto Kagaku), Neutron-2 (Nippon Seika), etc. Palmitic acid amide-based lubricants; Neutron S-18 (Nippon Seika), Amide P (Nitto Chemical), etc. Lauric amide-based lubricants;
Akzo), Diamond (Nippon Kasei), etc.

Unsaturated fatty acid amide lubricant Erucamide amide lubricant; Alflow P-10 (Nippon Oil & Fats), Neutron-S (Nippon Seika), LUBROL (IC)
・ I), Diamid L-200 (Nippon Kasei), etc. Oleic acid amide lubricants; Armoslip CP (Lion Akzo), Neutron (Nippon Seika), Neutron E-18 (Nippon Seika), Amide O (Nitto Chemical), Diamid O-200, Diamid G-200 (Nippon Kasei), Alflo E-10 (Nippon Oil & Fats), fatty acid amide O (Kao), etc.

Bis fatty acid amide-based lubricant Methylene bis-behenic acid amide-based lubricant; Diamid NK bis (Nippon Kasei), etc. Methylene bis-stearic acid amide-based lubricant; Diamid 200 bis (Nippon Kasei), Armowax (Lion
Akzo), Bisamide (Nitto Kagaku), etc. Methylene biooleic amide lubricant; Lubron O
(Nippon Kasei) etc. Ethylene bisstearic amide lubricant; Armoslip EBS (Lion Akzo), etc. Hexamethylene bisstearic amide lubricant; Amide 65 (Kawaken Fine Chemical), etc. Hexamethylene bisoleic amide lubricant; Amide 60 (Kawaken Fine Chemical), etc.

(2) Silicone lubricants; various grades of dimethylpolysiloxane and its modified products (Shin-Etsu Silicone, Toray Silicone)

In particular, various types of silicon not only exhibit effects such as improvement in resin fluidity and lubricity, but also when used in combination with a coloring substance, exhibit unexpected effects such as improvement in dispersibility and coloring power of the coloring substance. .

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

(4) Hydrocarbon lubricants; liquid paraffin, natural paraffin, microwax, synthetic paraffin, polyethylene wax, polypropylene wax, chlorinated hydrocarbon, fluorocarbon

(5) Fatty acid-based lubricants; higher fatty acids (preferably C ₁₂ or more), oxy fatty acids

(6) Ester lubricants: lower alcohol esters of fatty acids, polyhydric alcohol esters of fatty acids, polyglycol esters of fatty acids, fatty alcohol esters of fatty acids

(7) alcohol-based lubricants: polyhydric alcohols,
Polyglycol, polyglycerol

(8) Metallic soap; higher fatty acids such as lauric acid, stearic acid, ricinoleic acid, naphthenic acid, oleic acid and the like, Li, Mg, Ca, Sr, Ba, Zn, Cd, Al, S
Compounds with metals such as n and Pb

The addition amount of the above-mentioned lubricity improving substance is 0.01
If the amount is less than 0.01% by weight, there is almost no effect of the addition and only the kneading cost is increased.
If the amount is more than 10% by weight, even if the fatty acid or the fatty acid metal salt has a small lubricity improving effect, the slip of the screw occurs and the kneading with the resin is deteriorated. In particular, in the case of a substance having a large lubricating effect, such as fatty acid amide, if the content is not less than 1.0% by weight, screw slip occurs or trouble occurs due to bleed out.

The antioxidant prevents heat-induced deterioration of two kinds of polypropylene resins and a lubricity improving substance such as a lubricant or a surfactant.

Representative examples of the antioxidant are described below. (A) phenolic antioxidant 6-t-butyl-3-methylphenyl derivative, 2,6-di-t-butyl-P-cresol tt-butylphenol), 2.2′-methylenebis- (4-ethyl-6) -t-butylphenol), 4.4'-butylidenebis (6-t-butyl-m-cresol), 4.4'-thiobis (6-t-butyl-m-cresol), 4.4-dihydroxydiphenylcyclohexane, Alkylated bisphenol styrenated phenol, 2,6-di-t-butyl-4-methylphenol, n-octadecyl-3- (3'.5'-di-t-butyl-4'-hydroxyphenyl) propinate, 2・ 2'-methylene bin (4
-Methyl-6-t-butylphenol), 4.4'-thiobis (3-
Methyl-6-t-butylphenyl), 4.4'-butylidenebis (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 antioxidant 6-ethoxy-2,2,4-trimethyl-1・ 2-dihydroquinoline,
Polymers of 2,2,4-trimethyl-1,2-dihydroquinoline, trimethyldihydroquinoline derivatives, etc. (c) Allylamine antioxidants phenyl-α-naphthylamine, N-phenyl-β-naphthylamine, N-phenyl-N '-Isopropyl-P-phenylenediamine, NN'-Diphenyl-P-phenylenediamine, NN'
-Di-β-naphthyl-P-phenylenediamine, N- (3'-hydroxybutylidene) -1-naphthylamine, etc. (d) Imidazole antioxidant 2-mercaptobenzimidazole, zinc salt of 2-mercaptobenzimidazole, (E) Phosphite antioxidant Alkylated allyl phosphite, diphenylisodecyl phosphite, tris (nonylphenyl) phosphite, sodium phosphite, trinonyl phenyl phosphite, triphenyl phosphite (E) Thiourea-based antioxidants Thiourea derivatives, 1,3-bis (dimethylaminopropyl)-
2-thiourea, etc. (g) Other useful antioxidants for air oxidation dilauryl thiodipropionate, etc. (h) Sulfur-based antioxidants dilauryl thiodipropionate, simiristil thiodipropionate, lauryl stearyl thiodipropion , Distearyl thiodipropionate, etc.

Next, typical commercial antioxidants are listed below. (1) Phenolic antioxidants; SUMILIZER BHT (Sumitomo),
IRGANOX 1076 (Ciba Geigy), MARK AO-50 (ADEKA
Argus), SUMILIZER BP-76 (Sumitomo), TOMINOX SS (Yoshitomi), IRGANOX 565 (Ciba Geigy), NONOX WSP (IC
I), SANTONOX (Monsanto), SUMILIZER WX R (Sumitomo), ANTAGECRYSTAL (Kawaguchi), IRGANOX 1035 (Chiba Geigy), ANTAGE W-400 (Kawaguchi), NOCLIZER NS-6 (Ouchi Emerging), IRGANOX 1425 WL (Chiba Geigy) , MARKAO-80
(Adeka Argus), SUMILIZER GA-80 (Sumitomo), TOPA
NOL CA (ICI), MARK AO-30 (Adeka Argus),
MARKAO-20 (Adeka Argus), IRGANOX3114 (Ciba Geigy), MARK AO-330 (Adeka Argus), IRGANOX
1330 (Ciba Geigy), CYANOX 1790 (ACC), IRGANO
X 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), WESTON 618
(BorgWarner), MARK PEP-8 (Adeka Argus), ULTRANOX 626 (Borg Warner), MARK PEP-2
4G (Adeka Argus), MARK PEP-36 (Adeka Argus), HCA (Sanko), etc.

(3) Thiol ether antioxidant; DLTDP "Y
OSHITOMI "(Yoshitomi), SUMILIZER TPL (Sumitomo), ANTIOX L
(NOF), DMTD "YOSHITOMI" (Yoshitomi), SUMILIZER TPM
(Sumitomo), ANTIOX M (NOF), DSTP "YOSHITOMI" (Yoshitomi), SUMILIZER TPS (Sumitomo), ANTIOX S (NOF), SEEN
OX 412S (Cipro), MARK AO-412S (Adeka Argus), SUMILIZER TP-D (Sumitomo), MARK AO-23 (Adeka
Argus), SANDSTAB P-EPQ (sand), IRGAFOS P-EP
Q FF (Ciba Geigy), IRGANOX 1222 (Ciba Geigy), MARK 329K (Adeka Argus), WES TON399 (Borg Warner), MARK 260 (Adeka Argus), MA
RK 522A (Adeka Argus) etc.

(4) Metal deactivator; NAUGARD XL-1 (Uniroyal), NARK CDA-1 (Adeka Argus), MARK C
DA-6 (Adeka Argus), LRGANOX MD-1024 (Ciba Geigy), CUNOX (Mitsui Toatsu), etc.

The amount of the antioxidant added is 0.01
~ 1.0% by weight. If the added amount is less than 0.01% by weight, it is difficult to prevent the two kinds of polypropylene resins and the lubricity improving substance from being deteriorated by heat.

On the other hand, if the content exceeds 1.0% by weight, the photographic film utilizing the oxidizing and reducing actions is adversely affected, and quality defects such as fogging and abnormal sensitivity occur.

The coloring substance is mainly for improving the drop strength of the photographic film container. Representative examples of the coloring substance used in the present invention are described below.

(1) Inorganic compounds A. Oxides: silica, diatomaceous earth, alumina, titanium oxide, iron oxide, zinc oxide, magnesium oxide, antimony oxide, barium ferrite, strontium ferrite, beryllium oxide, pumice, pumice balloon, A. Alumina fiber, etc. B. Hydroxide: Aluminum hydroxide, magnesium hydroxide, basic magnesium carbonate, etc. C. Carbonate: Calcium carbonate, magnesium carbonate, dolomite, dawsonite, etc. D. (Sulfite): Calcium sulfate, barium sulfate , Ammonium sulfate, calcium sulfite, etc. E. Silicates ... talc, clay, mica, asbestos,
Glass fiber, glass balloon, glass beads, calcium silicate, montmorillonite, bentonite, etc. F. Carbon: carbon black, graphite, carbon fiber, carbon hollow sphere, etc. G. Others: iron powder, copper powder, lead powder, tin powder, stainless steel powder,
Pearl pigment, aluminum powder, molybdenum sulfide, polon fiber, silicon carbide fiber, brass fiber, potassium titanate,
Lead zirconate titanate, zinc borate, barium metaborate, calcium borate, sodium borate, aluminum paste, talc, etc.

(2) Organic Compounds Wood flour (pine, oak, sawdust, etc.), shell fiber (almond, peanut, fir shell, etc.), various colored fibers such as cotton, jute, paper strip, cellophane pieces, nylon fiber , Polypropylene fiber, starch, aromatic polyamide fiber, etc.

Among these coloring substances, carbon black is preferred because it can reduce the amount of bleed-out such as a lubricant and a surfactant. Gas black, furnace black, channel black, anthracene black,
Examples include acetylene black, Ketjen carbon black, thermal black, lamp black, oil smoke, pine smoke, animal black, vegetable black, and the like. In the present invention, furnace carbon black is desirable for the purpose of improving light-shielding properties, cost, and physical properties, and acetylene carbon black and Ketjen carbon black, which is a modified by-product carbon black, are desirable as coloring materials which are expensive but have an antistatic effect. If necessary, it is also desirable to mix the former and the latter according to required characteristics. As described above, there are various modes in which the coloring substance is blended with the polyethylene-based polymer. Japanese Patent Publication No. 40-26196 discloses a method for preparing a polymer-carbon black masterbatch by dispersing carbon black in a solution of a polymer dissolved in an organic solvent. It describes how to make a masterbatch by dispersing black in polyethylene.

Further, no fogging occurs on the photographic film, there is little occurrence of increase / decrease in the photosensitivity, the light-shielding ability is large, and even when added to the L-LDPE resin film, hardening of carbon black (dust) occurs. In the point that pinholes are unlikely to occur in films such as fish eyes, especially among carbon blacks, pH 6.0 to 9.0, average particle diameter 10 to 120 mμ,
Furnace carbon black having a volatile component of 2.0% or less and an oil absorption of 50 ml / 100 g or more is preferable. Channel carbon black is expensive and often causes fogging of the photographic film, which is not preferable. Even when absolutely necessary, the effect on photographic properties should be investigated and selected.

Preferable actual carbon black products include, for example, carbon black # manufactured by Mitsubishi Kasei.
20 (B), # 30 (B), # 33 (B), # 40 (B), # 44 (B), # 45
(B), # 50, # 55, # 100, # 600, # 2200 (B), # 2400
(B), MA8, MA11, MA100 and the like.

As overseas products, for example, Cabot Black Pearls 2, 46, 70, 71, 74, 80, 81, 607, etc.
egal 300, 330, 400, 660, 991, SRF-S, etc., Vulcan 3,
6, Sterling 10, SO, V, S, FT-FF, MT-FF and the like.

Further, United States of Ashland Chemical Co., Ltd.
R, BB, 15, 102, 3001, 3004, 3006, 3007, 3008, 300
9, 3011, 3012, XC-3016, XC-3017, 3020, and the like, but are not limited thereto.

The amount of the coloring substance added is 0.01 to 29% by weight, preferably 0.05 to 15% by weight, particularly preferably 0.1 to 5% by weight.
Range. If the added amount is less than 0.01% by weight, the drop strength is not significantly improved, the coloring concentration is small and the effect of adding a colored substance does not occur, and if the added amount exceeds 29% by weight, the flowability of the resin deteriorates. As a result, the occurrence of short shots and weld lines increases. The appearance also deteriorates, and the drop impact strength also deteriorates.

The photographic film container of the present invention, which can detect the phototube and allows the contents to be seen, has a haze of 17 to 17.
It is 70%, preferably 20 to 65%, particularly preferably 25 to 60%.

The photographic film container of the present invention preferably has a flexural modulus of 5,000 to 25,000 kg / cm ² .

The photographic film container of the present invention is, for example,
A container for a photo film cartridge in which a lid as shown in FIG. 1 is fitted to the container body, a container for a photo film cartridge in which a lid as shown in FIG. 2 is fitted to the container body, as shown in FIG. A container for a photo film cartridge of a type in which a lid and a container body are integrated with a hinge (the container for a photo film cartridge shown in FIG. 3 may be covered with a shrink film as shown in FIG. 4), FIG. 7. A photo film container having a lid and a container body integrated with a hinge as shown in FIG. 6, a light-shielding container for a microfilm having a lid and a container body integrated with a hinge as shown in FIG. 6, and FIG. A light-shielding container for a photo film in which a lid and a container body are lock-fitting type as shown in FIG. 8, a container for a photo film cartridge having a rectangular outer surface and a circular inner surface as shown in FIG. 8,
The present invention is applied to a container for a photographic film cartridge in which the tip of the photographic film as shown in FIG. 9 is wound in a plastic cartridge body.

In the case of a photo film patrone container in which the lid and the container main body are integrated by a hinge, the ratio of the average height between the container main body and the lid is 5: 5 to 50: 1, particularly 6: 4.
A ratio of ~ 9.5: 0.5 is preferred. In the case of a container for a photo film cartridge, the photo film cartridge may be, for example, JIS in which the front end of the photo film is exposed.
Patrone of photographic film and JP-A-2-272538, JP-A-3-37645, JP-A-3-126029, U.S. Patent Nos. 4,634,306 and 4,832,275,
No. 4,887,776, etc., in the unused state, even the tip of the photographic film was wound into the plastic cartridge body, and when used, the photographic film was sent out by rotating the spool. There is a patrone.

When the container for photographic film patrone is wrapped with shrink film, the impact strength is high, so that damage during transportation can be prevented, and the contents can be reliably protected. Furthermore, since the shrink film itself has a cushioning property, the contents are protected against an external impact.
Also, when enclosing the container for photo film patrone with shrink film, the area covering the bottom surface of the container body and the top surface of the lid is shrunk to 98% or less of the cross-sectional area of the container, and the container body and the lid have original sealing characteristics. It is preferable to provide an easy-opening portion, a typical example of which is shown in FIG.

Further, the resin composition of the photographic film container of the present invention can be used as a developing plate for a VTR book case, a developing plate for a floppy disk case, a pack for an instant film, a magazine for loading in a bright room, a plastic patrone, or a belt-like product. , Core, disk, cartridge, food container,
It can be used for electrical products, automobile parts, spools for photographic films, housing materials, and the like.

[0074]

In the photo film container of the present invention, the propylene / ethylene random copolymer resin is improved in transparency and the effect of adding a nucleating agent (improved transparency, improved crystallization speed, shorter molding cycle, improved rigidity, improved surface hardness, etc.). ), Improves impact drop strength, suppresses impact whitening, etc., propylene / ethylene block copolymer resin improves impact drop strength, impact drop strength at low temperatures, haze control, rigidity, and improves kneading suitability of colored substances Let me.

The nucleating agent improves transparency, rigidity, crystallization speed, abrasion resistance, and surface hardness, prevents deformation and buckling, and shortens the molding cycle.

The lubricity improving substance improves the releasability from the mold, the antistatic property, the antiblocking property, etc. and shortens the molding cycle. Further, the nucleating agent, the antioxidant, the two kinds of polypropylene resins, the surface coating of a coloring substance, and the like are used to improve the dispersing and kneading properties, and further improve the abrasion resistance and packaging workability.

An antioxidant prevents quality deterioration due to heating of two kinds of polypropylene resins and a lubricity improving substance such as a lubricant, an interfacial lubricating agent and an antifogging substance.

Further, the coloring substance improves the light-shielding property, the printability, and the discriminability (the contents can be discriminated by the color without opening the container, and the physical strength such as the drop strength).

[0079]

【Example】

Example 1 0.1% by weight of erucamide (0.0% based on the whole container body)
8% by weight), 1,3,2,4 di (methylbenzylidene) sorbitol 0.15% by weight (0.12% by weight based on the entire container body) and phenolic antioxidant 0.1% by weight (based on the entire container body) 0.08% by weight) and MFR is 35g / 10
Min, density (JIS K 7112) 0.90 g / cm ³ , flexural modulus 10300
kg / cm ² , 80% by weight of a propylene / ethylene random copolymer resin having an Izod impact strength of 3.5 kg · cm / cm ^{2 at} 23 ° C., a haze of 13%, an ethylene content of 2.1% by weight, and MF
R is 27 g / 10 min, density of 0.90 g / cm ^3, flexural modulus 12100kg
propylene / ethylene copolymer weight of 20% by weight of a propylene / ethylene block copolymer resin having an Izod impact strength of 5.7 kg · cm / cm ^{2, a} haze of 83% and an ethylene content of 3.7% by weight at 23 ° C / cm ² , A united resin composition was used.

A toggle-type injection molding machine (Nestal (trade name) manufactured by Sumitomo Heavy Industries, Ltd.) with a mold clamping pressure of 150 t and the number of cavities
Using 24 hot runner molds, resin temperature 220
At ℃, the container body for photographic film cartridge shown in FIG. 1 was prepared. The thickness of the peripheral wall was set to 0.7 mm.

In this container body, the haze of the peripheral wall was 46%, the passage could be detected by the photoelectric tube, and the printing of the photographic film cartridge stored inside could be seen from the outside. In addition, after storing 36 pieces of 35mm photographic film, with a low density polyethylene cap fitted,
The drop strength was tested by dropping the concrete floor from a height of 5 m (100 times), but no crack was found. further,
Even if the molding cycle is set to 10 seconds or less, almost no molding failure occurs, there is no whitening phenomenon even when strongly pressed with nails, scratches after transport are not noticeable, fitting strength, compressive strength and moisture resistance are also comparative examples described below. Better than one.

Example 2 The mixing ratio of the propylene / ethylene random copolymer resin (including erucamide) and the propylene / ethylene block copolymer resin of Example 1 was changed to propylene / ethylene random copolymer resin 90. The propylene / ethylene copolymer resin composition was changed to 10% by weight and the propylene / ethylene block copolymer resin to 10% by weight. And the same molding conditions (molding machine, mold, resin temperature) as in Example 1
Thus, a photographic film container body shown in FIG. 1 was prepared.

In this container body, the haze of the peripheral wall portion was 32%, the passage could be detected by the photoelectric tube, and the printing of the photographic film cartridge stored inside could be seen from the outside. In addition, after storing 36 pieces of 35mm photographic film, with a low density polyethylene cap fitted,
The drop strength was tested by dropping the concrete floor from a height of 5 m (100 times), but no crack was found. further,
Even if the molding cycle is set to 10 seconds or less, almost no molding failure occurs, there is no whitening phenomenon even when strongly pressed with nails, scratches after transport are not noticeable, fitting strength, compressive strength and moisture resistance are also comparative examples described below. Better than one.

Reference Example 1 Propylene comprising 94.7% by weight of the propylene / ethylene random copolymer resin of Example 1, 5% by weight of the propylene / ethylene block copolymer resin of Example 1, and 0.3% by weight of aluminum paste -An ethylene copolymer resin composition was used. Then, under the same molding conditions (molding machine, mold, resin temperature) as in Example 1, the container for a photographic film shown in FIG. 1 was produced.

This container body 2 had a haze of 100%. In addition, after storing 36 pieces of 35mm photographic film and dropping it onto a concrete floor from a height of 5m with a low density polyethylene cap fitted, the drop strength was tested.
(100 times), nothing was broken. Further, even when the molding cycle was set to 10 seconds or less, almost no molding failure occurred.
The container body had an excellent appearance and excellent curved surface printability, and even when left in sunlight for a long time, a temperature rise in the container was small, and no thermal deformation occurred.

Reference Example 2 85% by weight of the propylene / ethylene random copolymer resin of Example 1, 13.8% by weight of the propylene / ethylene block copolymer resin of Example 1, 1% by weight of titanium oxide, and 0% of erucamide A propylene / ethylene copolymer resin composition comprising 0.1% by weight and 0.1% by weight of a phenolic antioxidant was used.

Then, using a toggle-type injection molding machine {Nestal (trade name) manufactured by Sumitomo Heavy Industries, Ltd.) with a mold clamping pressure of 150 t, a square-shaped photographic film container integrated with a lid shown in FIG. 3 was prepared.
The thickness of the peripheral wall is 0.7 mm, the thickness of the hinge is 0.5 mm,
The length ratio between the container body and the lid was 8: 2. Further, in order to secure the moisture proof property and the original sealing property, as shown in FIG. 4, it was covered with a shrink film made of vinylidene chloride-coated polypropylene resin on which a description of handling, precautionary statements, CI mark and the like were printed.

This photo film container has a haze of 100
%Met. Further, in a state where the 35-mm photographic film of 36 shots was stored, the film was dropped on a concrete floor from a height of 5 m to test the drop strength (100 times), but no crack was found. In addition, even when strongly pressed with nails, there was no whitening phenomenon, and compression resistance, moisture resistance and heat resistance were good. This container body
It requires a conventional paper-made small box that is white in appearance, has excellent printability, has a small temperature rise in the container even when left in sunlight for a long time, maintains the quality of the photographic film, and does not generate heat denaturation. Not excellent.

Reference Example 3 85% by weight of the propylene / ethylene random copolymer resin of Example 1, 13.8% by weight of the propylene / ethylene block copolymer resin of Example 1, 1% by weight of furnace carbon black, erucamide Propylene comprising 0.1% by weight and 0.1% by weight of a phenolic antioxidant
An ethylene copolymer resin composition was used.

Then, a toggle-type injection molding machine (Nestal, trade name, manufactured by Sumitomo Heavy Industries, Ltd.) with a mold clamping pressure of 150 t was used to prepare a light shielding container for a microfilm integrated with a lid shown in FIG.
The thickness of the peripheral wall is 1.2 mm, the thickness of the hinge is 0.6 mm,
The ratio between the length of the container body and the length of the lid was 85:15. Furthermore, in order to secure the moisture-proof property and the original sealing property, the product was covered with a shrink film made of vinylidene chloride-coated biaxially stretched polypropylene resin on which the contents of the product, handling instructions, precautionary notes, CI mark, etc. were printed.

The package did not crack even when dropped from a height of 1 m onto a concrete floor. Also,
Since the moisture-proof property, the original sealing property, etc. were improved, and the whole was made of the same resin composition, it could be recycled.

REFERENCE EXAMPLE 4 Using the same propylene / ethylene copolymer resin composition as in Reference Example 2, under the same injection molding conditions as in Reference Example, the outer surface shown in FIG. Unexamined Japanese Patent Application Publication No. Hei 3-126, in which the leading end of the film is wound into the plastic cartridge body, and the photographic film is fed out by rotating the spool in use.
No. 029, Japanese Patent Application Laid-Open No. 3-177835, and the like, a patrone-shaped photographic film container of the type disclosed in JP-A-3-177835 was manufactured. The ratio of the length (thickness) of the container body to the lid was 50: 2. Further, Reference Example 2 in which handling instructions having original moisture-proof sheet properties are printed
And wrapped in the same shrink film. This photo film container had a haze of 100%. In addition, a drop speed was tested by dropping from a height of 5 m onto a concrete floor in a state in which a 36-shot photograph film was stored (1).
00), there was no crack. Also, there was no whitening phenomenon even when strongly pressed with nails, and the compression resistance, moisture resistance and heat resistance were good. This container body is white in appearance and has excellent printability.The temperature rise inside the container is small even when left in sunlight for a long time. It was an excellent container that could be maintained and did not generate thermal deformation of the container body.

Furthermore, since the body-lid joint resin composition is used, it can be collected and recycled, and does not require a conventional expensive paper small cosmetic box.
It has stackability and is printable. Instead of printing on the container body, printing may be performed on the shrink film as in the embodiment. ) It is an excellent container that can solve the current industrial waste problem.

Further, since the inner surface has a space in the form of a photographic film patrone, the photographic film patrone has little rattling and does not rotate in the container as in a conventional container due to vibration during transportation. Therefore, it is an excellent container with less occurrence of white powder and scratches. Claims as a container in which the body and the lid are separated, a container in which the outer surface is made into a rectangular shape of another shape (one with a right-angled corner, one with an R, and a octagon with a corner cut) and a resin composition 1 to
6, as well as a high-density polyethylene resin having a density of 0.940 g / cm ³ or more (including an ethylene / α-olefin copolymer resin) and a propylene / α-olefin copolymer resin (α-olefin is ethylene, butene-1, Hexene
Even in a polyolefin-based resin composition containing at least one kind of 1,4 methylpentene-1, octene-1 or the like in an amount of 70% by weight or more, the outer surface used in Reference Example 4 had a rectangular shape and the inner surface had the shape of a photographic film cartridge (at least the photographic film cartridge). (It is necessary to have a space that can accommodate the photo film cartridge. If the size is larger than the photo film cartridge, a projection may be provided to suppress the function of the photo film cartridge.)
In the case of, the structure can absorb shocks, so it can be used sufficiently.

Comparative Example 1 Using the propylene / ethylene random copolymer resin of Example 1, the same photographic film container body was produced under the same molding conditions as in Example 1.

This container body had a haze of 9% in the peripheral wall portion, and the printing of the photographic film patrone stored in the inside could be seen from the outside, but the passage could not be detected by the photoelectric tube. In addition, after storing 36 pieces of 35mm photographic film, with a low density polyethylene cap fitted,
Drop strength was tested by dropping the concrete floor from a height of 5 m (100 times), and cracks of 5% occurred. further,
Scratch and adhesion of dust after transportation were noticeable.

Comparative Example 2 Using the propylene / ethylene block copolymer resin of Example 1, the same photographic film container body was produced under the same molding conditions as in Example 1.

This container body had a haze of 66% in the peripheral wall portion, and the passage of the photo film could be detected by the photoelectric tube. However, the printing of the photographic film cartridge stored inside could not be seen from the outside. In addition, after storing 36 pieces of 35mm photographic film, with a low density polyethylene cap fitted,
Drop strength was tested by dropping from a height of 5 m onto a concrete floor (100 times). No cracking occurred, but whitening occurred frequently and the product had no commercial value. Moreover, when it pressed strongly with the pawl, it turned white. In addition, molding failure often occurred.

[0099]

According to the present invention, the detection by the photoelectric tube can be surely performed while maintaining or improving the drop impact strength.
The stored items can be seen from the outside. When a coloring substance is added, the drop strength can be extremely increased.

[Brief description of the drawings]

FIG. 1 is a cross-sectional view of a lid-fit type photo film patrone container to which the photo film container of the present invention is applied.

FIG. 2 is a cross-sectional view of another lid-fitting type photo film cartridge to which the photo film container of the present invention is applied.

FIG. 3 is a cross-sectional view of a container for a photographic film cartridge in which a lid to which the container for a photographic film of the present invention is applied is integrated with a hinge.

FIG. 4 is a perspective view of a package in which a photographic film patrone container to which a photographic film container of the present invention is applied is integrated with a hinge by a shrink film;

FIG. 5 is a cross-sectional view of a photographic film container in which a body to which the photographic film container of the present invention is applied is integrated with a hinge.

FIG. 6 is a cross-sectional view of a light shielding container for a microfilm in which a lid to which the container for a photofilm of the present invention is applied is integrated with a hinge.

FIG. 7 is a perspective view of a lid lock-fit type light shielding container to which the photo film container of the present invention is applied.

FIG. 8 is a perspective view of a cartridge body for a photo film cartridge having a rectangular outer surface and a circular inner surface to which the photo film container of the present invention is applied.

FIG. 9 is a perspective view of a photographic film container of the type in which the tip of the photographic film to which the photographic film container of the present invention is applied is wound into a plastic patrone main body.

Continuation of the front page (56) References JP-A-2-221957 (JP, A) JP-A-2-247640 (JP, A) JP-A-64-9445 (JP, A) JP-A-3-81766 (JP) , A) JP-A-2-310556 (JP, A) (58) Fields investigated (Int. Cl. ⁶ , DB name) G03C 3/00

Claims (7)

(57) [Claims] An ethylene content of 0.3 to 8% by weight,
65-95 wt% lower elastic modulus 5000 kg / cm ² or more propylene-ethylene random copolymer resin having a melt
Notch at 23 ° C with flow rate of 5 to 80 g / 10 min
5-35% by weight of a propylene / ethylene block copolymer resin having an Izod impact strength of 4 kg · cm / cm ² or more, 0.01-2.0% by weight of a nucleating agent, and a lubricity improving substance 0 .
A haze containing from 0.01 to 10% by weight and from 0.01 to 1.0% by weight of an antioxidant, from 20 to 65%. 2. An ethylene content of 0.3 to 8% by weight,
65-95 wt% lower elastic modulus 5000 kg / cm ² or more propylene-ethylene random copolymer resin having a melt
Notch at 23 ° C with flow rate of 5 to 80 g / 10 min
5-35% by weight of a propylene / ethylene block copolymer resin having an Izod impact strength of 4 kg · cm / cm ² or more, 0.01-2.0% by weight of a nucleating agent, and a lubricity improving substance 0 .
01 to 10% by weight, antioxidant 0.01 to 1.0% by weight
And haze included coloring substance from 0.01 to 29 wt%
20 to 65% 3. The container for a photographic film according to claim 1, wherein the nucleating agent is a sorbitol-based organic compound. 4. The container for a photographic film according to claim 1, wherein the lubricity improving substance is at least one kind of lubricant. 5. The photographic film container according to claim 1, wherein the ratio of the melt flow rate of the propylene / ethylene random copolymer resin and the propylene / ethylene block copolymer resin is within ± 90%. 6. The container body has a flexural modulus of 5,000 to 25.
3. The photographic film container according to claim 1, wherein the weight is 000 kg / cm ^2. 7. The container for a photographic film according to claim 1, wherein the outer surface is rectangular and the inner surface is substantially in the shape of a photographic film cartridge.