JPH05210217A - Photographic film container - Google Patents

Abstract

PURPOSE:To prevent the generation of waterdrops on the surface of a container by incorporating a water drip-proof material which has an antifogging action or a water drip-proof action, a lubricant, an antioxidant and a polyolefin resin having a specific weight% or above. CONSTITUTION:The lid 1 of the container and a main body 2 consist of the polyolefin composition incorporating at least 4 kinds consisting of a material having the antifogging action or the water drip-proof action, the lubricant, the antioxidant and the 50wt.% or more polyolefin resin. The polyolefin resin is selected from a low density-, middle density-, high density-homopolyethylene resin, ethylene.alpha-olefin copolymer resin, homopolypropylene resin, propylene.alpha- olefin copolymer resin, polybutene-1 resin and polyolefin elastomer, etc. The polyolefin resin is preferable to have a thermal history at >=180 deg.C, preferably at >=190 deg.C, especially at >=200 deg.C in the time of uniformly mixing various additives. The pellets having the thermal history at >=190 deg.C is preferable to be used, in the polyolefin resin especially incorporating an organic nuclear forming agent.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a plastic container for containing a photographic film.

[0002]

2. Description of the Related Art A container for a photographic film cartridge has been formed of a thin metal sheet material that does not adversely affect the photographic film and has excellent moisture-proof and gas barrier properties. When it came to be used in large quantities, it came to be formed of thermoplastic resin.
As the thermoplastic resin, a polystyrene resin or a homopolypropylene resin having a low melt flow rate (hereinafter referred to as MFR) and a high rigidity was initially used because it is considered to replace the metal.

However, at present, due to the necessity of impact strength and transparency, a low MFR propylene / ethylene random copolymer resin has come to be used. The inventor of the present invention is also able to shorten the molding cycle and reduce molding failures, and has a film cartridge main body mainly made of propylene resin having high rigidity and high MFR (Japanese Patent Laid-Open No. 60-16).
No. 3045) and a container body containing a fatty acid amide-based lubricant in an amount of 0.05 to 1% by weight, which is improved in air-feeding property and injection moldability immediately after molding (JP-A-61-73947). In addition, various forms of photographic film containers have been proposed in Japanese Patent Application Laid-Open No. 63-223640, Japanese Utility Model Laid-Open No. 1-88940 and Japanese Patent Publication No. 4-118645.

[0004]

By the way, the photographic film deteriorates in photographic property (sensitivity, gradation, fog, stain, color balance, etc.) when it is stored in a high temperature environment for a long period of time even if moisture resistance is secured. Therefore, it is stored in a cool and dark place. In general households, a plurality of plastic bags are sealed in a plastic container and stored in transparent or opaque plastic bags, and stored in a refrigerator in this state.

However, in the conventional transparent photographic film container, when the container was taken out of the refrigerator and loaded into the camera at the time of use, the container was clouded with water drops and it was difficult to distinguish the product type. If you leave the photographic film in the sunlight for 10 minutes or more (especially when left in a car at high temperature in summer), the water contained in the photographic film or the light-shielding telem will be absorbed into the inner wall of the plastic container. Attached,
The container body was fogged to make it difficult to see the characters, CI mark, etc. printed on the photographic film cartridge, and the suitability for use and the commercial value were reduced.

On the other hand, even in the case of a colored container which does not have the purpose of seeing the type of the container in which a light-shielding substance has been added or printed or the characters printed on the photographic film cartridge, water drops are formed on the surface of the user and To worsen the texture of
In some cases, water droplets adhered to the photosensitive layer of the photographic film to cause the photographic film to adhere to the photographic film.

Hereinafter, in the present invention, the action of preventing water droplets from adhering to a transparent or semi-transparent photographic film container and fogging is referred to as an antifogging action, and a substance having this antifogging action is referred to as a dripproof substance. Express. In addition, the action of preventing water droplets from adhering to a semi-transparent, opaque, or colored photographic film container in which it is difficult to tell whether or not fog has occurred is expressed as a drip-proof action, and substances with this drip-proof action are protected. Expressed as a drop substance. From the appearance, the antifogging action and the dripproofing action are distinguished from each other, but both actions are the actions to prevent water droplets and are considered to be substantially the same action.

It is an object of the present invention to solve the above-mentioned problems and to provide a container for photographic film having a drip-proof property such that water droplets do not adhere to it as much as possible, and particularly a container for photographic film cartridge having a high commercial value. And Furthermore, it aims at providing the container for photographic films which can be recycled as needed.

[0009]

The present invention has been made in order to achieve the above-mentioned object, and has a substance having an antifogging action or a dripproof action, a lubricant, an antioxidant and a polyolefin resin.
It is characterized by comprising a polyolefin resin composition containing at least 50% by weight of four kinds.

The polyolefin resin has low density, medium density,
Examples include high-density homopolyethylene resin, ethylene / α-olefin copolymer resin, homopolypropylene resin, propylene / α-olefin copolymer resin, polybutene-1 resin, and polyolefin elastomer.

It is preferable that the polyolefin resin has a heat history of 180 ° C. or higher, preferably 190 ° C. or higher, and particularly 200 ° C. or higher in terms of uniform kneading of various additives. In particular, for a polyolefin resin containing an organic nucleating agent, it is preferable to use pellets that have undergone a heat history of 190 ° C or higher. Further, among the above-mentioned polyolefin resins, a propylene / α-olefin copolymer for securing impact resistance, abrasion resistance, moisture resistance, lubricity, rigidity, gas barrier properties, moldability, etc. required for a photographic film container. Resin, high-density polyethylene resin, polyolefin elastomer, ethylene
A resin containing 50% by weight or more of one or more α-olefin copolymer resins is preferable.

In particular, MFR of 5 to 80 g / 10 minutes and density of 0.935 can secure characteristics required for a photographic film container such as transparency, rigidity, impact strength, glossiness, moisture resistance, impact whitening resistance and injection moldability. g / cm ³ or more homopolyethylene resin and ethylene
An α-olefin copolymer resin and a propylene / α-olefin random copolymer resin having an MFR of 5 to 80 g / 10 min are preferable. The polyolefin-based resin composition that has undergone a heat history of 190 ° C. or higher, which consists of pellets that have been kneaded and extruded at a temperature of 190 ° C. or higher, is most suitable after adding necessary amounts of a drip-proof substance, a lubricant, an antioxidant, and a nucleating agent to the resin. preferable.

As the α-olefin, those having 3 to 10 carbon atoms are preferable because they are easily polymerized and are relatively inexpensive. Preferred representative examples of the ethylene / α-olefin copolymer resin include ethylene / butene-1 random copolymer resin, ethylene / 4methylpentene-1 random copolymer resin, ethylene / hexene-1 random copolymer resin, Examples thereof include ethylene / octene-1 random copolymer resin. The content of α-olefin in the ethylene / α-olefin copolymer resin is 0.1 to 20 mol%, preferably 0.5 to 10 mol%. In order to secure homopolyethylene resin, ethylene / α-olefin copolymer resin, injection molding suitability, and properties required for a photographic film container body, MFR (A
STM D 1238, measured at 190 ° C.) is 5 to 80 g / 10 minutes, preferably 8 to 60 g / 10 minutes, particularly preferably 10 to 50 g / 10 minutes, and most preferably 11 to 35 g / 10 minutes. Density (ASTM D 150
5) 0.925 g / cm ³ or higher, preferably 0.935 g / cm ³ or more, and particularly preferably 0.940 g / cm ³ or more, and most preferred are
It is 0.941 to 0.965 g / cm ³ . In the present invention, even if the rigidity is small by increasing the average thickness of the bottom and integrating with the lid, it can be put to practical use, but from the viewpoints of ensuring compression resistance, preventing deformation, etc. 3500 kg of ethylene / α-olefin copolymer resin (ASTM D 747)
/ cm ² or more, preferably 4500 kg / cm ² or more, particularly preferably
It is 5000 kg / cm ² or more, and most preferably 6000 kg / cm ² or more. Vicat softening temperature (ASTM D 1525) is 95 ° C or higher, preferably 100 ° C from the viewpoint of preventing thermal deformation under sunlight.
More preferably, it is 110 ° C. or higher. The crystallinity by X-ray is preferably large from the viewpoint of ensuring rigidity, but is preferably small from the viewpoint of ensuring transparency, but in the present invention, it is 40 to 98%, preferably from the viewpoint of these balances.
50 to 95%, particularly preferably 60 to 93%.

The number average molecular weight is 10,000 to 1,000,000, preferably 20, in order to secure the rigidity and impact strength and to exert the effect of adding the organic nucleating agent (improvement of transparency, rigidity, etc.) to a great extent.
000 to 800,000, particularly preferably 25,000 to 600,000.

In order to secure rigidity and dimensional accuracy and to exert the effect of adding an organic nucleating agent (improvement of transparency, improvement of rigidity, etc.), a molecular weight distribution curve (gel permeation chromatography is used to obtain a molecular weight distribution curve, and a known molecular weight is obtained). Obtained from weight average molecular weight and number average molecular weight by universal calibration method using monodisperse polystyrene as standard) Mw / Mn (Mw: weight average molecular weight, Mn: number average molecular weight) is 1.5 to 25, preferably 2 to 20, injection molding In consideration of suitability, it is particularly preferably 2.5 to 15. By setting the hardness (Rockwell R) of the bottom of the container measured by ASTM D 785 to 45R or higher, preferably 50R or higher, particularly preferably 55R or higher, excellent abrasion resistance and scratch resistance can be prevented. ..

In order to allow the photographic film cartridge in the container to be observed from the outside of the container, the haze (%) measured by ASTM D 1003 is 50% or less, preferably 30% or less, and particularly preferably 10% or less. Is. The degree of cloudiness is an organic nucleating agent,
In particular, the di-substituted benzylidene sorbitol composition described below
By adding 0.01 to 2.0% by weight, it is possible to reduce by 15% or more and improve the transparency.

One of homopolyethylene resin and / or ethylene / α-olefin copolymer resin having these characteristics
It is preferable that the polyolefin-based resin composition of the present invention contains at least 50% by weight, preferably 70% by weight or more, and more preferably 85% by weight or more.

The above is the fact that the lid and the container body are integrally formed by a hinge or the like, as disclosed in JP-A-63-223640, Japanese Utility Model Laid-Open No. 1-88.
It can also be applied to the resins used for the photographic film containers of FIGS. 940, JP-A-4-118645, FIGS. 3 to 6, and FIG. 9. In this case, the recyclability is particularly excellent because the lid and the container body are the same. Further, since the lid and the container body are integrated, there is also an advantage that various polyolefin resins having rigidity less than half that of JP-A-60-163045 can be used.

With respect to polypropylene resin having excellent heat resistance and injection moldability, it is difficult to put the homopolypropylene resin into practical use in terms of impact strength, and in terms of impact whitening, the propylene / α-olefin block copolymer resin alone cannot be used. It is difficult to put into practical use, and it is put into practical use as a mixed resin with another resin or a thermoplastic elastomer, or a mixed resin with various fillers or reinforcing materials.

Therefore, the polypropylene resin which can be used alone as a container body is preferably a propylene / α-olefin random copolymer resin, specifically, a propylene / ethylene random copolymer resin or propylene / butene-1. It is a random copolymer resin or the like. The content of α-olefin in the propylene / α-olefin random copolymer resin is 0.1 to 20 mol%, preferably 0.5 to 10 mol%.

As physical properties, MFR (ASTM D 1238,
230 ℃ measurement) is 5-80g / 10 minutes, preferably 8-60g / 10
Min, particularly preferably 10 to 50 g / 10 min, and the initial flexural modulus (ASTM D 790) is 5000 kg / cm ² or more, preferably 7000 kg
/ cm ² or more, particularly preferably 9000 kg / cm ² or more. It is essential that the photographic film container of the present invention (including both the container body and the lid) further contains a polyolefin resin further containing a drip-proof substance having an antifogging action or a dripproof action, a lubricant and an antioxidant. In particular, in a transparent container body having a haze of ASTM D 1003 of 50% or less, these addition effects are greatly exerted. As the container body, the homopolyethylene resin, the ethylene / α-olefin random copolymer resin, and the propylene / α-olefin random copolymer resin described above are nucleating agents, and in particular, the rigidity and transparency can be obtained by adding a di-substituted benzylidene sorbitol composition described below. Has a great effect of improving, the molding failure is greatly reduced, and the molding cycle is significantly shortened.

Further, when a light-reflecting and / or light-absorbing, light-shielding substance or a coloring substance is added, the surface gloss (surface luster) is excellent, the color is dull and the appearance is beautiful, so that the coloring is of high commercial value. A photographic film container can be provided.

As a polyolefin resin, the density is 0.935 g / c
Homopolyethylene resin with m ³ or more and / or density of 0.935g
Preferred embodiments using a ethylene / α-olefin random copolymer resin of / cm ³ are shown below. (1) MFR of 8 to 60 g / 10 minutes, Olsen rigidity (ASTM D 7
47) 4500 kg / cm ² or more of ethylene / α-olefin (butene-1 is particularly preferable) 70% by weight or more of random copolymer resin and / or homopolyethylene resin, and drip-proof with anti-fogging or drip-proofing action. A photographic film container using a polyolefin resin composition containing at least 0.01 to 5.0% by weight of a substance, 0.01 to 5.0% by weight of a lubricant, and 0.01 to 2.0% by weight of an antioxidant has good injection moldability and has no molding failure. It is less and can improve transparency and drip-proof property. (2) More preferably, in the polyolefin resin composition of (1) above, a photographic film container using a polyolefin resin composition further containing 0.01 to 2.0 wt% of a nucleating agent is significantly improved in rigidity and transparency. However, the molding cycle can be shortened and molding failures can be greatly reduced. (3) In the polyolefin resin composition according to the above (1) or (2),
Further, a photographic film container using a polyolefin resin composition containing a light-reflecting and / or light-absorbing light-shielding substance (preferably a light-reflecting light-shielding substance) and / or a coloring substance (coloring dye) has an impact strength. And the recyclability is improved.

Preferred embodiments in which a propylene / α-olefin random copolymer resin is used are shown below. (1) MFR of 8 to 60 g / 10 minutes, initial flexural modulus (ASTM D 7
90) propylene / α-olefin (preferably ethylene) random copolymer resin of 7,000 kg / cm ² or more 85% by weight or more, drip-proof substance 0.01 to 3.0% by weight, lubricant 0.01 to 5.0% by weight,
A container for a photographic film using a polyolefin resin composition containing at least 0.01 to 2.0% by weight of an antioxidant. (2) More preferred is a photographic film container using the polyolefin resin composition of (1) above, which further contains 0.01 to 2.0% by weight of a nucleating agent. (3) In the polyolefin resin composition according to the above (1) or (2),
Further, it is a container for a photographic film using a polyolefin resin composition containing a light-shielding substance (preferably a light-reflecting light-shielding substance) and / or a coloring substance (coloring dye etc.).

The above-mentioned polyolefin resin is 50% by weight or more, preferably 70% by weight or more, particularly preferably 85% by weight.
It is contained by weight% or more. When the content of the polyolefin resin is less than 50% by weight, the moisture resistance and the gas barrier properties such as sulfur dioxide, formalin gas, chlorine gas, and oxygen gas, which adversely affect the photographic film, are insufficient, and the impact strength and abrasion resistance are further reduced. It is difficult to secure the properties and compressive strength. It is preferable to incorporate various thermoplastic elastomers and synthetic rubbers into the polyolefin resin composition of the present invention for the purpose of improving low temperature impact strength. In particular, ethylene / propylene rubber or ethylene / propylene / genterpolymer is preferable because it does not adversely affect the photographic film and improves impact strength.

Examples of the drip-proof substance having the anti-fogging action or drip-proof action include water-absorbing or hygroscopic substances (polyvinyl alcohol, starch, surface-treated starch or modified starch, hydroxyl group, carbonyl group, carboxyl group in polymer chain or side chain). , A hydrophilic polymer or a water-absorbing polymer containing a hydrophilic group consisting of a polar group such as an amino group, an amide group, an imide group, a sulfonyl group, or an ionic group, and the like, specifically, starch-acrylonite hydrolyzate, acetic acid Vinyl-methyl acrylate copolymer oxide, cross-linked polyacrylamide,
Polyacrylamide-acrylic acid copolymer, polyacrylic acid-diacrylate copolymer, polyethylene oxide, polyvinylpyrrolidone, crosslinked polyvinyl alcohol, polyethylene glycol, etc.) and a drip-proofing agent. Of these, starch is also biodegradable, which is preferable in terms of waste disposal suitability.

In the present invention, the drip-proof agent means that when blended in a container for photographic film in an amount of 0.01 to 3.0% by weight, the contact angle of pure water to this container is 50 degrees or less, preferably 45 degrees or less, and particularly preferably 35 degrees. All substances listed below are included. Particularly preferred representative antidrip agents are shown below, but the present invention is not limited thereto. Also a water-absorbing substance,
It is also possible to mix and use any two or more of a hygroscopic substance and a drip-proofing agent. Furthermore, it is preferable to subject the photographic film container containing the drip-proof substance to surface activation treatment such as corona discharge treatment, ozone contact treatment, and plasma treatment, because the antifogging action and the dripproofing action can be more effectively exhibited.

[Representative Examples of Particularly Preferred Dripproofing Agent] Diglycerin monostearate, polyglycerin monopalmitate, sorbitan monolaurate, sorbitan monostearate, sorbitan monooleate, sorbitan monoerucate, Polyoxyethylene sorbitan fatty acid ester,
Stearic acid monoglyceride, palmitic acid monoglyceride, oleic acid monoglyceride, lauric acid monoglyceride, polyoxyethylene nonylphenol ether, sorbitan sesquipalmitate, diglycerin sesquioleate, sorbitol fatty acid ester, sorbitol fatty acid dibasic acid ester, diglycerin fatty acid diester Basic acid ester, glycerin fatty acid / dibasic acid ester, sorbitan fatty acid / dibasic acid ester, sorbitan palmitate, sorbitan stearate, sorbitan palmitate / propiolene oxide 3 mol adduct, sorbitan palmitate / propiolene oxide 2 mol addition , Sorbitol stearate, sorbitol stearate / ethylene oxide 3 mol adduct, diglycerin palmiate Over DOO, glycerine palmitate, glycerine palmitate ethylene oxide 2 moles adduct.

The amount of the drip-proof substance as described above is 0.01 to
3.0% by weight is preferred. Particularly, 0.1 to 2.0% by weight is preferable. When the addition amount is less than 0.01% by weight, the antifogging effect is hardly exhibited and only the kneading cost increases. Also,
Additives such as lubricants and antioxidants that easily bleed out cannot be prevented from being deposited in the form of white powder.

On the other hand, if the amount added exceeds 3.0% by weight, the antifogging effect is sufficiently exerted, but the effect of increasing the amount is almost eliminated, and the cost only increases. The problem is that the surface of the container tends to be sticky, dusty and dusty, and when it adheres to photographic film, uneven development speed occurs.

Lubricants are used to improve lubricity, injection moldability,
It makes it easier to put the photographic film in and out of the container, improves the slipperiness during idling, prevents scratches from occurring, and improves the suitability for processing and packaging. Furthermore, it is possible to prevent mold release, prevent static electricity from occurring, and prevent blocking (both pellets and containers) from occurring. Furthermore, the dispersion and kneading properties of the antioxidant essential to the present invention are improved. In addition, as a representative example of a lubricant preferable in the present invention, for improving the dispersion and kneading properties of a nucleating agent and a light-shielding substance that are added if necessary,
For example, there are silicone, fatty acid amide, wax, fatty acid metal salt and the like.

Listed below are representative names of commercially available lubricants and manufacturer names. (1) Fatty Acid Amide Lubricants Saturated Fatty Acid Amide Lubricants Behenic Acid Amide Lubricants; Diamid KN (Nippon Kasei), etc. Stearic Acid Amide Lubricants; Armide HT (Lion Oil), Alflo S-10 (Nippon Oil), Fatty Acid Amide S (Kao), Diamid 200 (Nippon Kasei), Diamid AP-1 (Nippon Kasei), Amide S / Amid T (Nitto Kagaku), Neutron-2 (Nippon Seika), etc. Palmitic acid amide lubricants; New TRON S-18 (Nippon Seika), Amide P (Nitto Kagaku), etc. Lauric acid amide lubricant; Armide C (Lion
Akzo), Diamid (Nippon Kasei), etc. Unsaturated fatty acid amide lubricants, erucic acid amide lubricants; Alflo P-10 (Nippon Yushi), Neutron-S (Nippon Seika), LUBROL
(IC), 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 Kagaku), Diamid O-200, Diamid G-200 (Nippon Kasei), Alflo E-10 (Nippon Oil & Fats), Fatty Acid Amide O (Kao), etc. Bis fatty acid amide lubricant Methylenebisbeh Nitric acid amide type lubricant; Diamid NK bis (Nippon Kasei) etc. Methylene bis stearic acid amide type lubricant; Diamid 200 bis (Nippon Kasei), Armowax (Lion
Akzo), bisamide (Nitto Kagaku), etc. Methylenebiooleic acid amide lubricant; Lubron O
(Nippon Kasei) etc. Ethylenebisstearic acid amide lubricant; Armoslip EBS (Lion Akzo) etc. Hexamethylenebisstearic acid amide lubricant; Amide 65 (Kawaken Fine Chemicals) etc. Hexamethylenebisoleic acid amide lubricant; Amide 60 (Kawaken Fine Chemicals), etc. (2) Silicone-based lubricants Various grades of dimethylpolysiloxane and its modified products, and various modified products of silicon (typical example: siloxane). Typical examples are carboxyl modified silicone, α-methylstyrene modified silicone, α-olefin modified silicone, polyether modified silicone, fluorine modified silicone,
Hydrophilic special modified silicone, olefin polyether modified silicone, epoxy modified silicone, amide modified silicone, alcohol modified silicone, alkyl modified silicone,
Alkylaryl modified silicone, amino modified silicone,
Alkylhydrogen-modified silicone (Shin-Etsu Silicone, Toray Silicone), etc. In particular, various silicones not only exert the effects of improving resin fluidity and lubricity, but when used in combination with light-shielding substances and coloring substances, light-shielding substances and coloring substances It is preferable because it exhibits unexpected effects such as improved dispersibility and improved coloring power. (3) Nonionic surfactant 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 hydrocarbons, fluorocarbons, etc. (5) Fatty acid-based lubricants Higher fatty acids (C ₁₂ or higher is preferred), oxyfatty acids, etc. (6) Ester-based lubricants Lower alcohol esters of fatty acids, Polyhydric alcohol ester, fatty acid polyglycol ester, fatty acid fatty alcohol ester, etc. (7) Alcohol-based lubricant Polyhydric alcohol, polyglycol, polyglycerol, etc. (8) Metal soap Lauric acid, stearic acid, ricinoleic acid, naphthenic acid, olein Higher fatty acids such as acids and Li, Mg, Ca, Sr,
Compounds with metals such as Ba, Zn, Cd, Al, Sn and Pb These lubricants may be used alone or in combination of two or more if necessary.

In the polyolefin resin composition of the present invention, a halogen compound is contained in the form of a residue of a polymerization catalyst or as an impurity in an additive. It is preferable to neutralize the halogen compound or to add a fatty acid metal salt to the polyolefin resin composition of the present invention for various purposes. By adding the fatty acid metal salt, bleed-out can be reduced, the organic nucleating agent can be prevented from scattering, and the dispersibility of the organic nucleating agent can be improved. In addition, this fatty acid metal salt improves the dispersibility and moldability of the light-shielding substance, and further neutralizes and harms the halogen compounds contained in the resin, which adversely affect the photographic properties of the photographic light-sensitive material. The quality is also improved. Examples of the fatty acid metal salt include higher fatty acids such as lauric acid, stearic acid, ricinoleic acid, naphthenic acid, oleic acid and erucic acid, and Li, Mg, Ca, Sr, Ba, Zn and C.
There are compounds with metals such as d, Al, Sn and Pb.

The amount of the fatty acid metal salt added is preferably 0.01 to 10.0 parts by weight, more preferably 0.1 to 5.0 parts by weight, based on 100 parts by weight of the polyolefin resin. The addition amount to the container made of the polyolefin resin composition is preferably 0.01 to 8.0% by weight, more preferably 0.03.
~ 5.0 wt%, most preferably 0.05-3.0 wt%.

Among the above-mentioned lubricants, nonionic surfactant lubricants are preferable because they do not adversely affect the photographic film such as fogging and sensitivity abnormalities, are harmless to the human body, and exhibit an antistatic effect.

The amount of the above lubricant added is 0.01 to 5.0.
Weight percent is preferred. If the addition amount is less than 0.01% by weight, there is almost no addition effect, and only the kneading cost increases.
If it exceeds 0% by weight, bleed-out occurs or screw slips occur, the discharge amount becomes unstable, molding failures frequently occur, and the kneadability with the polyolefin resin deteriorates. 0.01 to 3.0% by weight is preferable in the case of a fatty acid amide lubricant that is inexpensive and does not adversely affect the occurrence of fog or sensitivity abnormality on the photographic film, and has a large effect of improving lubricity and shortening the injection molding cycle, and particularly 0.02 to 1.0% by weight. %
Is preferable from the viewpoint of greatly reducing molding failures and preventing bleed-out. Also, although the effect of improving lubricity is small, it improves the dispersibility of various additives and improves the fluidity of the polyolefin resin. Hydrocarbon-based lubricants, fatty acid-based lubricants, metallic soaps, etc. do not cause a problem at 20% by weight or less. It can be used up to the amount.

An antioxidant is used in the photographic film container of the present invention. The oxidative decomposition of the resin is greater in the polyolefin resin having more CH ₃ branches. This is because the oxygen absorption amount is large, and therefore the degree of oxidative decomposition is polypropylene resin> homopolyethylene resin> ethylene / α-olefin copolymer resin. Various polyethylene resins (including ethylene / α-olefin copolymer resins) and various polypropylene resins (including propylene / ethylene random copolymer resins), which are typical thermoplastic resins of crystalline resins
Etc. are hydrocarbons, and it is considered that the autoxidation of hydrocarbons proceeds in the following chain-like manner once dehydration occurs in the presence of oxygen to generate free radicals.

RH → R ・ R ・ + O ₂ → ROO ・ ROO ・ + RH → ROOH + R ・ ROOH → RO ・ + ・ OH RO ・ + RH → ROH + R ・ ・ OH + RH → HOH + R ・ In this way, the oxidation of hydrocarbons is accelerated. Alcohol, aldehydes, ketones, acids, etc., which are adversely affected by the reaction, produce a polymer by reacting with each other.

In order to prevent the oxidation of hydrocarbons, it is necessary to go through the above chain reaction, and therefore various antioxidants are used. That is, the antioxidant decomposes the free radical chain terminator that reacts with the free radicals (mainly ROO.) That are chain propagators to inactivate them and the hydroperoxide ROOH that is the main source of free radicals. Then, there is a peroxide decomposer which stabilizes this. As the former,
There are phenolic antioxidants and aromatic amine antioxidants. The latter includes sulfur-based antioxidants and phosphorus-based antioxidants. For these reasons, it is preferable to mix and use a phenolic antioxidant and a phosphorus antioxidant. Since various antioxidants are also reducing agents that adversely affect the photographic light-sensitive material, the quality deterioration of the photographic light-sensitive material becomes large and becomes a problem unless the addition amount is carefully examined.

In the present invention, the antioxidant is not only for preventing thermal deterioration of the polyolefin resin but also for preventing oxidation of the drip-proof substance and the lubricant. Examples of antioxidants are listed 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
4'-butylidene bis (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'-methylenebin (4-methyl-6-t-butylphenol), 4.4'-thiobis (3-methyl-6-t-butylphenyl), 4.4'- Butylidene bis (3-methyl-6-t-butylphenol), stearyl-β (3
-5-di-4-butyl-4-hydroxyphenyl) propionate, 1.1 / 3-tris (2-methyl-4hydroxy-5-t-butylphenyl) butane, 1.3 / 5
Trimethyl-2,4,6-tris (3,5-di-t-butyl-4hydroxybenzyl) benzene, tetrakis [methylene-3 (3 ', 5'-di-t-butyl-4'-hydroxyphenyl) Propionate] Methane, etc. (b) Ketone amine condensation-based antioxidant 6-ethoxy-2,2,4-trimethyl-1,2-dihydroquinoline, polymer of 2,2,4-trimethyl-1,2-dihydroquinoline, Trimethyldihydroquinoline derivatives, etc. (c) Allylamine-based antioxidants Phenyl-α-naphthylamine, N-phenyl-β-naphthylamine, N-phenyl-N′-isopropyl-P
-Phenylenediamine, N.N'-diphenyl-P-phenylenediamine, N.N'-di-β-naphthyl-P-
Phenylenediamine, N- (3′-hydroxybutylidene) -1-naphthylamine, etc. (d) Imidazole-based antioxidants 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 oxidation Antioxidants Thiourea derivatives, 1,3-bis (dimethylaminopropyl) -2-thiourea, etc. (to) Other antioxidants useful for air oxidation Dilauryl thiodipropionate, etc. (h) Sulfur-based antioxidant, dilauryl Thiodipropionate, Similistil Thiodip Ropionate, lauryl stearyl thiodipropionate, distearyl thiodipropionate, etc.

Next, typical commercial products of antioxidants are listed below. (1) Phenolic antioxidant; 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 (Ciba Geigy), ANTAGE W-400 (Kawaguchi), NOCLIZER NS-6 (Ouchi Shinko), IRGANOX 1425 WL (Ciba 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), MA
RK 2112 (Adeka Argus), WESTON 618 (Borg Warner), MARK PEP-8 (Adeka Argus), ULTRANOX 6
26 (Borg Warner), MARK PEP-24G (Adeka Argus), MARK PEP-36 (Adeka Argus), HCA (Sanko)
Etc. (3) Thioether antioxidant; DLTDP "YOSHITOMI" (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), SEENOX 412S (Cypro), M
ARK AO-412S (Adeka Argus), SUMILIZER TP-D
(Sumitomo), MARK 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), MA
RK 260 (Adeka Argus), MARK 522A (Adeka Argus), etc. (4) Metal deactivator NAUGARD XL-1 (Uniroyal), NARK CDA-1 (Adeka Argus)
Argus), MARK CDA-6 (Adeka Argus), LRGANO
X MD-1024 (Ciba Geigy), CUNOX (Mitsui Toatsu), etc.

Among the above antioxidants, phenolic and phosphorus antioxidants are preferable because they are less likely to cause adverse effects such as fog and abnormal sensitivity on the photographic film.
As the phenolic antioxidant, a hindered phenolic antioxidant is particularly preferable. Particularly, it is preferable to use two or more kinds of hindered phenol-based antioxidants and / or phosphorus-based antioxidants in combination.

The hindered phenol-based antioxidant used in the present invention is a commercially available antioxidant, and when applied to a resin composition of a photographic film container, it causes fog on the photographic film. Any hindered phenol-based antioxidant can be used as long as it does not cause an increase / decrease sensation. For example, 1.3.5-trimethyl-2.4.6-tris (3.
5-di-tert-butyl-4-hydroxybenzyl) benzene, tetrakis [methylene (3.5-di-tert-butyl-4-hydroxy-hydrocinnamate)] methane,
Octadecyl-3.5-di-tert-butyl-4-hydroxy-hydrocinnamate, 2.2'.2 ''-tris [3.
5-di-tert-butyl-4-hydroxyphenyl) propionyloxy] ethyl isocyanurate, 1.3.5-
Tris (4-tert-butyl-3-hydroxy-2.6-
Di-methylbenzyl) isocyanurate, tetrakis (2.4-di-tert-butylphenyl) 4.4'-biphenylene diphosphite, 4.4'-thiobis (6-te
rt-butyl-0-cresol), 2.2'-thiobis-
(6-tert-butyl-4-methylphenol), tris- (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, 2.2'-methylene-bis- (4-methyl-6-tert) -Butylphenol), 4.4'-methylene-bis- (2.6-di-tert-butylphenol), 4.
4'-butylidene bis- (3-methyl-6-tert-butylphenol), 2.6-di-tert-butyl-4-methylphenol, 4-hydroxymethyl-2.6-di-t
ert-butylphenol, 2.6-di-tert-butyl-4
-N-butylphenol, 2.6-bis (2'-hydroxy-3'-tert-butyl-5'-methylbenzyl) -4
-Methylphenol, 4.4'-methylene-bis- (6-
tert-butyl-0-cresol), 4.4'butylidene-
Bis (6-tert-butyl-m-cresol) and the like. The melting point (Melting point) is preferably 100 ° C. or higher, and more preferably 120 ° C. or higher, because bleeding out and thermal decomposition are small and adverse effects on the photographic light-sensitive material are small. To prevent oxidative decomposition of the polyolefin resin of the present invention,
Particularly, it is preferable to use a mixture of phenolic and phosphorus antioxidants.

The above-mentioned antioxidant is added in an amount of 0.001
~ 2.0% by weight, especially 0.01-0.5% by weight is preferred, most not more than 0.
03 to 0.3% by weight is preferable. If the amount added is less than 0.001% by weight, there is almost no effect of addition and only the kneading cost increases. On the other hand, if the amount added exceeds 2.0% by weight, the photographic film utilizing the oxidation and reduction effects will be adversely affected by fog and abnormal sensitivity.

The nucleating agent is for improving crystallization speed, shortening molding cycle, improving rigidity, improving transparency and preventing deformation, improving physical strength and the like. Nucleating agents include organic nucleating agents and inorganic nucleating agents. Representative examples of these are shown below.

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

[0047]

[Chemical 1]

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

[0049]

[Chemical 2]

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

The inorganic nucleating agent is an alkali metal hydroxide such as lithium hydroxide, sodium hydroxide or potassium hydroxide,
Alkali metal oxides such as sodium oxide, alkali metal carbonates such as lithium carbonate, sodium carbonate, potassium carbonate, sodium hydrogen carbonate and potassium hydrogen carbonate, alkaline earth metal waters such as calcium hydroxide, magnesium hydroxide and barium hydroxide. Examples thereof include oxides, alkaline earth metal oxides such as calcium carbonate and calcium oxide. The nucleating agent is not limited to these, and other known nucleating agents can be used. Needless to say, the nucleating agent is not limited to a single type, and two or more types can be used in combination.

An organic nucleating agent which has a great effect of adding crystallization to a photographic film, has a great effect of promoting crystallization of a resin as a nucleating agent, reduces molding failures, shortens a molding cycle, and improves rigidity and transparency. Particularly preferable examples are described below. di- (o-methylbenzylidene) sorbitol o-methylbenzylidene-p-methylbenzylidene sorbitol di- (m-methylbenzylidene) sorbitol m-methylbenzylidene-o-methylbenzylidene sorbitol di- (p-methylbenzylidene) sorbitol m-methylbenzylidene-p-methylbenzylidene sorbitol 1 3-heptanylidenesorbitol 1 ・ 3,2 ・ 4-diheptanylidenesorbitol 1 ・ 3,2 ・ 4-di (3-nonyl-3-pentenylidene) sorbitol 1 ・ 3-cyclohexanecarbylidenesorbitol 1 ・ 3,2 ・ 4-dicyclohexanecarbylidenesorbitol 1 ・ 3,2・ 4-di (p-methylcyclohexanecarbylidene) sorbitol 1 ・ 3-benzylidenesorbitol 1 ・ 3,2 ・ 4-dibenzylidene-D-sorbitol 1 ・ 3,2 ・ 4-di (m-methylbenzylidene) sorbitol 1 ・ 3,2 ・ 4 -di (p-methylbenzylidene) sorbitol 1 ・ 3,2 ・ 4-di (p-hexylbenzylidene) sorbitol 1 ・ 3,2 ・ 4-di (l-naphthalenecarbylidene) sorbitol 1 ・ 3,2 ・ 4-di (phenylacetylidene) sorbitol 1 ・ 3 ・ 2 ・ 4-di (methylbenzylidene) sorbitol 1 ・ 3 ・ 2 ・ 4-di (ethylbenzylidene) sorbitol 1 ・ 3 ・ 2 ・ 4-di (propylbenzyledene) sorbitol 1 ・ 3 ・ 2 ・ 4-di ( methoxybenzylidene) sorbitol 1 ・ 3 ・ 2 ・ 4-di (ethoxybenzylidene) sorbitol 1 ・ 3 ・ 2 ・ 4-di (P-methylbenzylidene) sorbitol 1 ・ 3 ・ 2 ・ 4-di (P-chlorbenzylidene) sorbitol 1 ・ 3 ・ 2 ・ 4-di (P-methoxybenzylidene) sorbitol 1 ・ 3 ・ 2・ 4-di (alkilbenzylidene) sorbitol 1 ・ 3 ・ 2 ・ 4-bis (methylbenzylidene) sorbitol aluminum benzoate, etc.

Particularly preferred is a dibenzylidene sorbitol compound. In particular, a polyolefin resin which is a crystalline resin of the present invention (preferably a propylene / α-olefin random copolymer resin, a density of 0.935 g / cm ³ or more homopolyethylene resin and a density of 0.935 g / cm ³ or more ethylene / α In order to improve transparency, rigidity, shorten molding cycle, decrease molding failure, and improve off-odor and bleed-out, which are the drawbacks of conventional organic nucleating agents, the following di-substituted benzylidene Sorbitol compositions are particularly preferred. As an essential component of the di-substituted benzylidene sorbitol composition, the compound represented by the general formula (I)

[0054]

[Chemical 3]

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

[0056]

[Chemical 4]

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

General formula (II) preferably used in the present invention
The dibenzylidene sorbitol derivative of
-2,4-di-p-methylbenzylidene sorbitol, 1,
3-, 2,4-di-p-ethylbenzylidene sorbitol,
1,3-p-methylbenzylidene-2,4-p-chlorobenzylidenesorbitol, 1,3-p-methylbenzylidene
2,4-p ethylbenzylidene sorbitol and 1,3-
Examples thereof include p-chlorobenzylidene-2,4p-methylbenzylidenesorbitol and the like.

In a preferred embodiment of the organic nucleating agent of the present invention, a dibenzylidene sorbitol derivative in which R and R'in the general formula (I) each independently represent a methyl group or a chlorine atom is used. Particularly preferred dibenzylidene sorbitol derivatives are 1,3-2,4-dipmethylbenzylidene sorbitol, 1,3-p methylbenzylidene-2,4-p chlorobenzylidene sorbitol and 1,3-p chlorobenzylidene-2. , 4-p-methylbenzylidene sorbitol.

Preferred examples of the higher fatty acid of the formula (II) preferably used as the organic nucleating agent in the present invention are behenic acid and
Among the stearic acid and palmitic acid, behenic acid is most preferable, and stearic acid is the second most preferred.

The particle size of the solid powder of the dibenzylidene derivative used in the organic nucleating agent composition of the present invention does not need to be particularly limited, and a particle size distribution of 30 to 100 mesh is preferably used. The preferred organic nucleating agent composition of the present invention is 95 to 50 parts by weight of the dibenzylidene derivative, preferably
In the range of 5 to 50 parts by weight, preferably 10 to 50 parts by weight, higher fatty acid to 90 to 50 parts by weight, the total of both components is 100.
It is contained at a ratio of becoming parts by weight.

The preferred organic nucleating agent composition of the present invention is a solid emulsion of the dibenzylidene sorbitol derivative, which is added to an aqueous emulsion containing the above fatty acid in the above proportion in the above proportion and stirred to obtain a solid powder of the dibenzylidene sorbitol derivative. It can be prepared by forming a coating layer of higher fatty acid on the surface, filtering the dibenzylidene sorbitol derivative powder having the higher fatty acid coating, and then washing and drying.

The higher fatty acid aqueous emulsion used in the above method is, for example, a solution of a higher fatty acid in an organic solvent solution having a concentration of 5 to 50% by weight, preferably 10 to 50% by weight, and a small amount of a surfactant, for example, higher fatty acid 100. 1 to parts by weight
It can be easily obtained by dispersing in water using 10 to 10 parts by weight, preferably 2 to 5 parts by weight. The presence of a coating of higher fatty acid formed on the surface of the solid powder of dibenzylidene sorbitol derivative should be confirmed by observing the coating with a dye, as described in detail in Examples below. You can

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

In the preferred organic nucleating agent composition of the present invention, 0.01 to 2 parts by weight, preferably 0.05 to 1 part by weight, as a dibenzylidene sorbitol derivative component, is equivalent to 100 parts by weight of the polyolefin resin. A dibenzylidene sorbitol derivative coated with is preferably used.

The preferred organic nucleating agent composition of the present invention can be blended with the polyolefin resin by mixing by any known mixing means. Further, the preferable organic nucleating agent composition of the present invention can be used as a masterbatch in a polyolefin resin containing the composition in a concentrated amount, if necessary.

In the preferred organic nucleating agent composition of the present invention, it is important that the surface of the solid particles of the dibenzylidene sorbitol derivative is coated with a higher fatty acid. Even if added and mixed, the effects described above cannot be achieved. Also, 180 ° C or higher, preferably 190 ° C or higher,
Particularly preferably, the above-mentioned effects cannot be achieved unless the heat history of 200 ° C. or higher is passed.

This heat history may be carried out once. For example, the above-mentioned di-substituted benzylidene sorbitol composition described in detail in the polyolefin-based resin composition of the present invention as a preferred organic nucleating agent composition of the present invention is 0.01 After adding ~ 2.0% by weight, 2
The container for photographic film may be injection-molded by using the pelletized product by heating it to 00 ° C or higher. Even if the resin temperature at this time is 180 ° C or lower, the above-mentioned effects are achieved, but this injection Keep the resin temperature above 180 ℃ during molding (180
In the present invention, it is expressed as having undergone a heat history of ℃ or more twice. By doing so, it is possible to injection-mold a container for photographic film having excellent transparency and rigidity, a high gloss on the container surface, and almost no weld lines observed.

The preferred organic nucleating agent composition of the present invention does not impair various properties such as transparency, bleed-out resistance and rigidity when blended with a polyolefin resin composition as compared with the prior art. In some cases, these properties are further improved, and at the same time it has excellent odorlessness, and at the same time white spots are less likely to appear inside the molded product, and the injection moldability is improved and the molding cycle can be shortened, resulting in molding failure. It has an excellent effect of decreasing. That is, by including the above-mentioned di-substituted benzylidene sorbitol composition in the polyolefin resin composition of the present invention, transparency,
It is possible to provide a photographic film container having excellent rigidity, bleed-out resistance, odorlessness, injection moldability, and abrasion resistance.

The reason why the preferable organic nucleating agent composition of the present invention exerts the above excellent effects is not always clear, but
Conventional benzaldehyde, which is a raw material for producing dibenzylidene sorbitol, and benzaldehyde derivatives, such as p-substituted benzaldehyde, which is a raw material for producing the dibenzylidene sorbitol derivative of the present invention, have an odor, and both dibenzylidene sorbitol (derivative) are unavoidable after purification. ) Tends to cause an offensive odor in a photographic film container, which is a polyolefin resin molded product, and dibenzylidene sorbitol (derivative) is also used during injection molding of a photographic film container using a polyolefin resin composition. It is possible that it may decompose slightly and cause an offensive odor.
In a preferred organic nucleating agent composition of the present invention, solid particles of (1) the specific dibenzylidene sorbitol derivative of the general formula (I) are used, and (2) the particles are the higher fatty acid of the general formula (II). By satisfying the requirements of (1) and (2) at the same time, such as coating with, the offensive odor presumed to be based on the raw material benzaldehyde or decomposed benzaldehyde is used for photographic film using a polyolefin resin composition. Significantly reduced and stiff in the container,
At the same time, the above-mentioned physical properties such as transparency are excellent.

The various organic nucleating agents may be used alone, in combination with various inorganic nucleating agents, or in combination of two or more kinds of organic nucleating agents. Further, the surface of the organic nucleating agent can be coated with various fatty acids, lubricants such as fatty acid compounds and silicon, coupling agents, plasticizers, dispersants such as surfactants and wetting agents.

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

As a method of blending the nucleating agent, there are a compound method, a dry blend method, a master batch method and the like, but the master batch method is preferable. Since it has a high dryness and is easily scattered, it is difficult to mix it as it is. It is advisable to add a small amount of a dispersant or a wetting agent to mix it.
As the dispersant, various lubricants, various waxes, carboxylic acid anhydrides, higher fatty acids and the like are available, and lubricants such as various fatty acid metal salts, various silicones and oleic acid amides are particularly preferable. As the wetting agent, a plasticizer such as DOP or DHP can be used.

Further, it is also preferable to coat the surface of the organic nucleating agent with a pure product of a fatty acid or a fatty acid compound such as a higher fatty acid, a fatty acid amide or a fatty acid metal salt, or blend them to enhance the dispersion effect and prevent bleed-out. Further, it is preferable to use as a pellet kneaded with a polyolefin resin at a heat history of 180 ° C. or higher, preferably 190 ° C. or higher, and particularly 200 ° C. or higher from the viewpoint of exerting the effect of the nucleating agent. That is, by adding these additives, the transparency is improved, the rigidity is increased and the generation of white powder due to abrasion is reduced, and the generation of white powder due to crystallization or bleed-out of the organic nucleating agent is reduced. Further, the malodor of the organic nucleating agent can be prevented, and the mold releasability from the mold, the prevention of static electricity generation, and the prevention of blocking can be improved.

The amount of the nucleating agent added is preferably 0.01 to 2.0% by weight. If the amount added is less than 0.01% by weight, the effect of addition is scarcely exhibited and only the blending cost is required. In addition, even if it exceeds 2.0% by weight, there is no effect of increasing the amount, it only increases the cost, and depending on the type of nucleating agent, it adversely affects the photographic film, adheres to the mold, bleeds out, It may reduce the drop impact strength.

The light-reflecting light-shielding substance has the effects of improving printability, improving appearance, preventing thermal deformation under sunlight, and preventing temperature change in the container. Aluminum powder, aluminum paste, aluminum flakes, titanium oxide, Calcium sulfate, barium sulfate, talc, clay, mica, stainless powder, starch, tin powder, pearl pigment, zinc oxide,
Examples include potassium titanate and glass beads. These light-reflecting light-shielding substances may be used alone or in combination of two or more, or in combination with a dye or the like. The light-reflecting light-shielding substance may be subjected to various surface treatments. The amount of the light-reflecting light-shielding substance added is 0.01
-30% by weight is preferred. If the amount added is less than 0.01% by weight, there is almost no effect of addition and only kneading costs are required.

Further, even if it exceeds 30% by weight, there is almost no effect of increasing the amount, and only the cost is increased. In addition, the fluidity of the resin is deteriorated, and short shots and weld lines frequently occur. The appearance also deteriorates, and the drop impact strength also decreases. If necessary, a light-absorbing light-shielding substance such as carbon black or graphite may be included in the polyolefin resin composition of the present invention.

As a typical example of the light-absorbing light-shielding substance used in the container for photographic film of the present invention, there is no fog on the photographic film in use, little increase or decrease in photosensitivity, and a large light-shielding ability. , Even when added to the polyolefin-based resin composition of the present invention, the occurrence of solidification (butsu) of carbon black, fish eyes, weld lines,
Among carbon blacks, the pH (measured with JIS K 6221) is 6.0 to 9.0, preferably pinholes, etc., preferably
6.5-8.5, average particle size (measured by electron microscopy) 10-12
Those having a particle size of 0 mμ, preferably 12 to 100 mμ, and particularly 15 to 70 mμ are preferable. Among them, volatile components (JIS K 6221
3.5% or less, most preferably 1.5% or less, DB
P oil absorption (measured by the oil absorption A method of JIS K 6221) is 50 ml / 100
It is a furnace carbon black of g or more, most preferably 70 ml / 100 g or more. Channel carbon black is expensive, and most of them have a volatile component of more than 5.0%, which is not preferable because they often cause fog on the photographic film. Most of the lamp blacks also have a pH of 5.0 or less, which adversely affects the photographic properties, so even if it is absolutely necessary to use them, the effects on the photographic properties should be investigated and selected. Further, the sulfur component measured by ASTM D 1619 is 0.9% or less, preferably 0.7% or less, and particularly 0.5%.
If you do not do the following, it adversely affects the photographic properties. In particular, the free sulfur component, which adversely affects the photographic properties of photographic film, is 0.1%.
Hereafter, it is preferable to select the most preferably 0.05% or less.

A practical carbon black product is, for example, carbon black # 20 manufactured by Mitsubishi Kasei.
(B), # 30 (B), # 33 (B), # 40 (B), # 44 (B), # 45 (B),
# 50, # 55, # 100, # 600, # 2200 (B), # 2400 (B), M
Examples include A8, MA11, MA100. Overseas products include, for example, Cabot's Black Pearls 2,46,7
0, 71, 74, 80, 81, 607, etc., Regal 300, 330, 400, 66
0, 991, SRF-S, Vulcan 3, 6 etc., Sterling
10, SO, V, S, FT-FF, MT-FF and the like can be mentioned. In addition, Ashland Chemical's United R,
BB, 15, 102, 3001, 3004, 3006, 3007, 3008, 3009,
Examples include 3011, 3012, XC-3016, XC-3017, and 3020, but are not limited thereto.

When the average thickness of the container is 0.5 to 2.0 mm, the amount of the light absorbing and light shielding substance added is preferably 0.01 to 30% by weight, more preferably 0.05 to 20% by weight, and most preferably 0.
It is in the range of 1 to 10% by weight. When used in combination with substances that are colored by light, such as vitamin E, vitamin E carboxylic acid ester, and photosensitive resin, the coloring effect (improvement of coloring density, decrease of physical strength decrease, improvement of moldability, improvement of resin fluidity) is great. To be demonstrated. In particular, the average thickness of the container is 0.5-1.5 mm
In this case, the amount of the light-absorbing light-shielding substance added is 0.01 to 25% by weight, preferably 0.05 to 15% by weight, particularly preferably 0.1 to 8% by weight, from the viewpoint of coloring and securing physical strength.

On the other hand, considering the case of landfill treatment as waste, a degradable polymer which is currently being researched or has been introduced into some markets may be used. For example, as a biodegradable polymer, ICI
Polymers or starches that indirectly disintegrate by using "BIOPOL" manufactured by U.S.A., "polycaprolactone" manufactured by UCC, etc., or by blending natural or synthetic polymers susceptible to biodegradation as additives. A compounded polyolefin resin or the like can also be used.

Particularly, "Bionol" manufactured by Showa Highpolymer Co., Ltd. (chemically synthesized from dicarboxylic acid, etc.) which was recently released as a chemically synthesized biodegradable polymer which is decomposed into carbon dioxide and water by the action of microorganisms Special polyester resin)
It is also possible to add 10% by weight or more of "Matterby" (corn starch and biodegradable modified polyvinyl alcohol polymer alloy) manufactured by Novamont of Italy to the resin composition for molded articles of the present invention. It is preferable in terms of improving processability. In the case of a molded article having a multi-layered structure, the layer that does not directly contact the photographic film contains
The amount of 50% by weight or more is particularly preferable from the viewpoint of improving the processability of industrial waste.

It is also possible to use a photodegradable polymer. For example, an ECO copolymer obtained by copolymerizing ethylene and carbon monoxide into which a carbonyl group is introduced as a photosensitizing group in the main chain during polyethylene polymerization is used, or a transition metal salt, an oxidation accelerator, and a photosensitizer are used as additives. It is possible to use a material obtained by adding a material or the like to the base polymer and imparting photodegradability thereto. Further, one or more kinds of degradable polymers such as biodegradable polymers, photodegradable polymers and water-soluble polymers may be used in combination (see JP-A-3-129341).

Biodegradable additives that can be contained in the polyolefin resin composition include starch, modified starch, surface-coated starch, skin powder, micronized cellulose,
Examples include polyvinyl alcohol and polyethylene glycol. Examples of the photodegradable additive that can be contained in the polyolefin resin composition include cerium stearate, cerium caprylate, a combination of iron stearate and 4-chlorobenzophenone, an iron compound, a nickel compound and the like.

When imparting a radiopaque function, barium compounds, zinc or zinc compounds, tin or tin compounds,
The object can be achieved by injection-molding a resin in which at least one of lead and a lead compound is contained in the polyolefin resin composition of the present invention in an amount of 10 to 50% by weight to obtain a photographic film container. However, the appearance and drop impact strength decrease unless the wall thickness is increased.

The photographic film container of the present invention is, for example,
It can be applied to the photographic film container shown in FIGS. The photographic film container shown in FIG. 1 is of a type in which a lid 1 is fitted in a container body 2. The photographic film container shown in FIG. 2 is of a type in which the lid 1 is fitted on the container body 2. In the photographic film container shown in FIG. 3, a lid 1 and a container body 2 are integrally connected by a hinge portion 3 (JP-A-63-223640, etc.). Also in the photographic film container shown in FIG. 4, the lid 1 and the container body 2 have hinge portions 3.
It is integrally connected (not shown) and is further sealed with a shrink film with print 4 (Japanese Utility Model Laid-Open No. 1-88940, etc.). The photographic film container shown in FIG. 5 also has a lid 1 and a container body 2 integrally connected by a hinge portion 3. Also in the photographic film container shown in FIG. 6, the lid 1 and the container body 2 have hinge portions 3 (not shown).
It is for microfilms that are integrally connected with each other. In the photographic film container shown in FIG. 7, the lid 1 and the container body 2 are of a lock fitting type. In the photographic film container shown in FIG. 8, the container body 2 has a quadrangular outer surface and a circular inner surface. The container for photographic film shown in FIG. 9 has a photographic film cartridge in which the front end of the photographic film is wound inside a plastic cartridge body, and the outer surface is rectangular. Figure
In the photographic film container shown in 10, the lid 1 and the container body 2 are integrally connected by a hinge portion 3, and a sealing label 5 is attached from the lid 1 to the container body 2.

In addition, various magnetic material molded products (VTR book case, floppy disk case, cassette storage container, cartridge, etc.), various photosensitive material molded products (light chamber loading magazine, core, spool, cartridge, plastic) It can also be applied to patrones, disc films and microfilms, lid-joint integrated light-shielding cases, film packs, bushes, etc., and molded products for various purposes (food, electrical products, automobile parts, housing parts, etc.). ..

The photographic film to be stored in each of the containers is a 35 mm negative film of the type in which the tip of the photographic film is exposed from the most commercially available metallic cartridges at the present time. As described in Kaihei 3-37645, Japanese Patent Laid-Open No. 3-126029, U.S. Pat. No. 4,634,306, etc., in the unused state, even the tip of the photographic film should be wound into the plastic cartridge body. 35mm negative film, micro film (negative and positive) of the type in which the tip of the photographic film is stored in a plastic patrone in an unexposed and light-shielded state by rotating the spool during use. Film (negative and positive).

The photographic film container of the present invention has an initial flexural modulus (ASTM D when the average thickness of the container is 1.0 mm or less).
790) is preferably 5000 kg / cm ² or more. If the flexural modulus is less than 5000 kg / cm ² , deformation often occurs during injection molding, the molding cycle becomes very long, and the productivity is greatly reduced. In particular, injection molding is difficult without a lubricant. When a lubricant other than fatty acid amide lubricant is used,
If it is not added in an amount of 0.2% by weight or more, multi-shot injection molding is impossible, and even in this case, there are many deformations and it is difficult to put it into practical use. However, as shown in FIG. 3 to FIG. 6 and FIG. 9, the average thickness of the photographic film container or the container in which the lid is integrated by the hinge is 1.0 mm or more, or the average thickness of the bottom of the container is 1.0 mm or more. In this case, the Olsen flexural modulus (ASTM D 747) is 3500 kg.
/ cm ² or more, preferably a is 4500 kg / cm ² or more, the upper limit in view from the hinge characteristics and fit sealability 17,000Kg / cm ² or less, preferably 15,000 kg / cm ² or less.

[0090]

In the photographic film container of the present invention, the drip-proof substance and the like prevent water droplets from forming in the container as much as possible.

[0091]

【Example】

Example 1 MFR (ASTM D 1238) 35 g / 10 min, density (ASTM D 1505)
Is 0.90 g / cm ³ , initial flexural modulus (ASTM D 790) is 11,300 k
g / cm ^2, 23 ℃ Izod impact strength with notch (ASTM D 25
6) is 3.6 kgcm / cm ² , Rockwell hardness (ASTM D 785)
Is 88R, 99.27% by weight of propylene / ethylene random copolymer resin having an ethylene content of 2.7% by weight, 0.05% by weight of bis fatty acid amide, 0.33% by weight of a mixture of glycerin monostearate and glycerin distearate, N, N'- Bis (2-hydroxyethyl) stearylamine 0.15% by weight, 1,3,2,4-di (methylbenzylidene) sorbitol 0.1% by weight, tetrakis [methylene-3- (3 ',
5'-di-tert-butyl-4'-hydroxyphenyl) propionate] Methane 0.1% by weight was used as a polypropylene resin composition.

A closed system type Nestal (trade name) manufactured by Sumitomo Heavy Industries is used as a molding machine (mold clamping pressure 150 t), a cavity having 24 cavities and a hot runner type mold are used to form the lid shown in FIG. A container body of a fitting type photographic film cartridge was made by injection molding at a resin temperature of 210 ° C.

The container body for the photographic film cartridge has excellent transparency so that the photographic film cartridge can be observed in a beautiful color even from the outside of the container. After being left for a long time (a low-temperature warehouse for ensuring photographic film performance, a low-temperature container, a refrigerator for general households, etc.), even when it was taken out into the open air above 20 ° C, it did not generate water droplets and did not lose its transparency. . Further, it was excellent in physical strength, rigidity and wear resistance, the injection molding cycle could be greatly shortened, and it had antistatic property.

Example 2 MFR 10 g / 10 minutes, density 0.90 g / cm ³ , flexural modulus 15,
200kg / cm ² , Izod impact strength with notch at 23 ℃ 1.9kg
Cm / cm ² , 82.6% by weight of homopolypropylene resin with Rockwell hardness of 95R, 0.1% by weight of oleic acid amide, 0.2% by weight of glycerin monostearate, 5% by weight of silicon surface treated starch, MFR of 25 g / 10 minutes, density Is 0.91 g / cm
³ , propylene block copolymer resin with flexural modulus of 8900 kg / cm ² , notched Izod impact strength of 6.2 kg · cm / cm ² at 23 ° C. 10% by weight, tetrakis [methylene-3- (3 ′,
5'-di-tert-butyl-4'-hydroxyphenyl) propionate] methane 0.1% by weight, titanium oxide 2
A white polypropylene resin composition consisting of wt% was used. Then, a container main body for a photographic film cartridge having the same shape (FIG. 1) was prepared using the same molding machine and mold as in Example 1.

This container body does not generate water droplets on the inner surface of the container body even when left in sunlight, and
After storage under conditions of 15 ° C or lower for a long period of time, water droplets did not occur even when taken out in the atmosphere of 20 ° C or higher.

Further, this container body is excellent in physical strength, rigidity, whiteness, abrasion resistance, low temperature impact strength, etc. without causing fog or increase / decrease in sensitivity on the photographic film, and has a short molding cycle. However, there were few molding failures. Also, because it is white, it is printable (including transfer),
It had an excellent appearance and was suitable for disposal so that it could naturally disintegrate if left for a long time after use.

Example 3 Using the polypropylene resin composition of Example 2, a lid-integrated type photographic film container shown in FIG. 9 was prepared, and in this container, even the tip of the photographic film was made of plastic. Be sure to roll it up inside the Patrone body,
At the time of use, a 35 mm negative film containing a photographic film cartridge was sealed by rotating the spool when the photographic film was sent out. Then, as shown in FIG. 4, a shrink film made of polypropylene resin in which the product type, CI mark, instruction manual, bar code, etc. are multi-color printed, and has an original sealability, aesthetics, commercial value, gas barrier property, moisture resistance, and sealability. Etc. were covered so that they could be secured.

This package does not deform even when left in the sunlight, no water droplets are generated on the container surface, and
Water droplets did not occur even after taking out after storage for a long time in a low temperature warehouse of around 10 ° C. Therefore, this package is inexpensive because it does not require a cosmetic case unlike the conventional packages, and the waste can be greatly reduced.

Furthermore, this package was able to be blended with the shrink film for recycling, and also had a suitability for disposal such that it could be spontaneously disintegrated by leaving it for a long time after use.

Comparative Example 1 Propylene / ethylene random copolymer resin of Example 1
99.85% by weight, bis fatty acid amide 0.05% by weight, 1,3,2
A photograph of the same shape as in Example 1 was obtained using a polypropylene-based resin composition containing 0.1% by weight of 4-di (methylbenzylidene) sorbitol, using the same molding machine and mold as in Example 1, and at a resin temperature of 190 ° C. A container body for a film cartridge was created.

When the container body for a photographic film cartridge was taken out from the condition of 15 ° C. or lower to the atmosphere of 20 ° C. or higher, the inner surface became cloudy with water droplets, and the display of the photographic film cartridge was difficult to see. In addition, coloring, resin burning, static electricity and the like were likely to occur.

Example 4 MFR 45 g / 10 minutes, density 0.90 g / cm ³ , flexural modulus 890
60 kg by weight of propylene / ethylene random copolymer resin with an ethylene content of 0 kg / cm ² of 3.2% by weight, MFR of 20 g / 10
Min, density 0.90 g / cm ³ , bending elastic modulus 13,200 kg / cm ² ethylene content 2.1% propylene / ethylene block copolymer resin 38.9% by weight, oleic acid amide 0.10% by weight as a lubricant, Stearic acid monoglyceride 0.2% by weight as drops, organic nucleating agent 1.3,2,4-di (methylbenzylidene) sorbitol 0.1% by weight, inorganic nucleating agent and light-reflecting light-shielding substance fine particle calcium carbonate 0.2% by weight , Titanium oxide 0.3 as a light-reflecting light-shielding substance
% By weight, 0.10% by weight of a phenolic antioxidant (manufactured by Ciba-Geigy: trade name IRGANOX 1010) as an antioxidant, phosphorus-based antioxidant (manufactured by Ciba-Geigy: trade name I)
A propylene / ethylene copolymer resin composition containing 0.10% by weight of RGANOX 168) was used.

Then, using the same molding machine as in Example 1, the container for photographic film of the body-lid type shown in FIG. 3 was prepared at a resin temperature of 200 ° C., and this container was the most commercially available metal at present. A 35 mm negative film containing a photographic film cartridge in which the front end of the photographic film is exposed from the cartridge was sealed. Then, as shown in FIG.
It was covered with a shrink film made of polyester resin with multi-color printing of CI mark, instruction manual, bar code, etc. so as to secure the original sealing property, aesthetics, commercial value, gas barrier property, moisture resistance, sealing property, and the like.

[0104] This package does not deform even when left in the sunlight, no water drops are generated on the container surface, and the temperature is 10 ° C.
Water droplets did not occur on the container surface even after taking out after storage for a long time in low temperature warehouses around. There is little deterioration of the quality of photographic film under any of the above conditions. Therefore, unlike the conventional packaging, this packaging does not require a container for photographic film in a small cosmetic box, and it is inexpensive and significantly reduces industrial waste. It could be reduced. Furthermore, this photographic film container was recyclable because the container body and lid were made of the same resin composition.

Furthermore, the container for photographic film is
Even if the photographic film cartridge was dropped from a height of 5 m on a concrete floor under the condition of -5 ° C in a sealed state, it was not damaged. Whitening was not noticeable, so there was no problem in practical use.

The injection moldability was excellent, and the molding cycle could be shortened to 1/5 of that of Comparative Example 2 containing no additives essential to the present invention.
It could be reduced to less than 1/100.

Comparative Example 2 Propylene / ethylene random copolymer resin of Example 4
60 wt% and propylene / ethylene block copolymer resin
A propylene / ethylene copolymer resin composition containing only 40% by weight of an additive required for the present invention was used. Then, using the same molding machine and mold as in Example 4, the lid-integrated photographic film container shown in FIG.
A 35 mm negative film containing the same type of photographic film cartridge was sealed at 200 ° C. Then, as shown in FIG. 4, it was covered with a polyester resin shrink film that was multicolor printed.

This package was not deformed even when left in sunlight for a long time, but the photographic film cartridge in the container was heated and water droplets were generated on the inner surface of the container, resulting in deterioration of the quality of the photographic film. In addition, water drops were generated on both the inside and outside surfaces of the container when it was taken out after being stored in a low temperature warehouse at around 10 ° C for a long time.

Further, this photographic film container is -5.
If a photographic film cartridge is dropped from a height of 5 m on a concrete floor under the condition of ℃, it will be damaged by about 3% and the whitening of the strong drop impact part will occur 100% and the commercial value cannot be secured. Met. Injection molding also has problems, blocking of resin pellets and blocking of containers occur, and the molding cycle is five times that of Example 4, and molding failures such as deformation and short shots occur in Example 4.
It was 100 times more than that, which was impossible to put into practical use.

Example 5 100 parts by weight of the polypropylene resin composition of Example 1 was added,
A black polypropylene resin composition was used in which 10 parts by weight of a carbon masterbatch resin consisting of 40% by weight of furnace carbon black and 60% by weight of a modified ethylene / butene-1 copolymer resin graft-polymerized with an unsaturated carboxylic acid were blended. Then, using the same molding machine and mold as in Example 1, a container body of a container for a photographic film cartridge was prepared at a resin temperature of 210 ° C.

This photographic film cartridge container body had excellent drip-proof property as in Example 1, and even if dropped from a height of 5 m to a concrete floor at 5 ° C., damage was 5%. (25% in Example 1), which is 1/5 of that in Example 1, the abrasion resistance is improved, and the lubricant, the antioxidant, and the nucleating agent that easily bleed out are adsorbed by the carbon black. The generation of white powder due to the bleeding out was also reduced to an unobservable level. It was a container body for photographic film cartridges, which was ideal for high-sensitivity photographic film, because the injection molding cycle could be greatly shortened, and antistatic properties and light-shielding properties were excellent.

Comparative Example 3 The same resin composition, molding machine and mold as those of Example 1 were used. However, only the resin temperature was set to 170 ° C. and the body of the photographic film cartridge container body of the body fitting type shown in FIG.

However, since the resin composition has not been subjected to a heat history of 180 ° C. or higher, the nucleating effect of the organic nucleating agent 1,3,2,4-di (methylbenzylidene) sorbitol is not exhibited, and the molten resin Liquidity has deteriorated. As a result, the crystallization speed becomes slower, the transparency becomes lower, the rigidity becomes smaller, and it is impossible to mold a good product unless the injection pressure is increased by 20%.
The molding cycle was 1.5 times that of Example 1, and molding failures such as deformation, short shots, and gate residuals increased to 10 times or more that of Example 1. The strength of the drop from a height of 5 m was greatly increased due to the strong weld line, resulting in 42% damage. The Rockwell hardness was also lowered, the bleed out of the additive was increased, and white powder was generated, which was not preferable as a photographic film container.

Next, a representative example of an example of a photographic film container using a homopolyethylene resin having a density of 0.935 g / cm ³ or more will be described.

Example 6 MFR (ASTM D 1238, measured at 190 ° C.) was 15 g / 10 minutes and density (AS
TM D 1505) is 0.960 g / cm ³ , Olsen stiffness (ASTM D 74
7) is 11,000 kg / cm ² , Izod impact strength is 3.5 kgcm / c
Homopolyethylene resin with m, Rockwell hardness (ASTM D 785) of 60R, and Vicat softening point (ASTM D 1525) of 120 ° C 9
9.5% by weight, oleic acid amide 0.05% by weight, glycerin distearate 0.2% by weight, hindered phenolic antioxidant tetrakis [methylene-3- (3 ', 5'-di-tert-butyl-4'-hydroxy] Phenyl) propionate] methane 0.05% by weight, 0.2% by weight of 1,3,2,4, di-P-methylbenzylidene sorbitol whose surface is solid powder coated with behenic acid was well mixed in a mixer, and then twin-screw extruded at a resin temperature of 220 ° C. After extruding into a strand shape with a machine and cooling with water, using a cutter, granulated into cylindrical pellets with a diameter of 2 mm and a length of 3 mm and dried, a closed system type Nestal (trade name) manufactured by Sumitomo Heavy Industries is used (mold) A photographic film cartridge with an average thickness of 1.0 mm at the bottom of the lid-fitting type shown in Fig. 1 using a hot runner type mold with a clamping pressure of 150 t) and 24 cavities. The container body of the container was prepared by injection molding at a resin temperature of 190 ° C.
This container body for photographic film cartridge has a Rockwell hardness of 60R → 67 at the bottom as compared with the container body for photographic film cartridge using only the homopolyethylene resin.
Improved to R, the Vicat softening point improved from 120 ° C to 124 ° C,
The transparency is improved (haze is reduced by 9%), the print color and print characters of the photographic film patrone can be clearly observed even from the outside of the container body, and it can be left in the sunlight for a long time, 15 ° C
After being stored for a long time under the following conditions, even when it was taken out into the open air at 20 ° C or higher, neither water droplets nor loss of transparency was observed. In addition, physical strength, rigidity, wear resistance, antistatic property and lubricity are excellent, and the molding cycle can be shortened by 30%.
Almost no generation of white powder due to an offensive odor or bleeding out over time was observed.

Example 7 MFR 10 g / 10 minutes, density 0.957 g / cm ³ , Olsen rigidity 8200 kg / cm ² , Izod impact strength 4.3 kg · cm / cm, Rockwell hardness 58R, Vicat softening point Is 117.degree. C. homopolyethylene resin 98.63% by weight, average particle size is 21 mμ,
Volatile content 0.8%, pH 7.7, oil absorption 112 ml / 100g, ash 0.2%, sulfur content 0.51%, furnace carbon black 0.3% by weight, dimethylpolysiloxane 0.2% by weight, vitamin E carboxylic acid ester 0.1 Wt%, hindered phenolic antioxidant octadecyl-3-
0.05% by weight of (3 ', 5'-di-tert-butyl-4'-hydroxyphenyl) propionate, 0.3% by weight of calcium stearate and 0.3% by weight of monoglyceride oleate.
And 0.3% by weight of 1,3-P-methylbenzylidene-2,4-P-chlorobenzylidene-sorbitol whose solid powder surface has been pre-coated with stearic acid in a mixer and then at a resin temperature of 220 ° C using a twin-screw extruder Extruded in a strand shape, water-cooled, and then granulated into a cylindrical pellet having a diameter of 2 mm and a length of 3 mm by a cutter and dried, and the same injection molding machine and hot runner mold as in Example 6 were used. The average thickness of the bottom of the lid-fitting type shown in is 1.0 mm
The container body for the photographic film cartridge was prepared by injection molding at a resin temperature of 185 ° C. Compared to the homopolyethylene resin alone, this photographic film cartridge container body has a black appearance and has a light-shielding property, so that the light-shielding telem performance of the photographic film cartridge and the sticking to the port opening may occur. Even if light fogging can be prevented, 0 ° C
Even if the photographic patrone wrapped with 35 mm film of 36 sheets taken from a height of 5 m under temperature was dropped on the concrete floor in a sealed state, the occurrence of cracks was 0%. Since the variety of photographic film cartridges cannot be observed from the outside of the container body, peeling did not easily occur even if a label printed with the variety, cautionary notes, or CI mark was attached to the outer side wall of the container body. . Rockwell hardness of the bottom is 58
R → 65R, Olsen rigidity is 8200kg / cm ² → 9500
It had improved to kg / cm ² . After being left in the sunlight for a long time or stored under conditions of 15 ° C or lower for a long time, no water droplets were generated even when taken out into the open air of 20 ° C or higher. further,
It has excellent physical strength, abrasion resistance, antistatic properties and lubricity, and the molding cycle could be shortened by 35%. Unlike the conventional container body for photographic film cartridges using an organic nucleating agent, no offensive odor was generated and white powder was not generated due to bleeding out with time.

Examples using an ethylene / α-olefin copolymer resin are shown below.

Example 8 MFR (ASTM D 1238, measured at 190 ° C.) of 30 g / 10 minutes, density (AS
TM D 1505) is 0.952 g / cm ³ , Olsen stiffness (ASTM D 74
7) is 7100kg / cm ² , and Izod impact strength (ASTMD 256) is
3.1 kg · cm / cm, Shore hardness (ASTM D 2240) 62D, Vicat softening point 112 ° C ethylene / butene-1 copolymer resin 99.35% by weight, erucic acid amide 0.05% by weight, sorbitan monoerucic acid ester 0.3% by weight, tetrakis [methylene-3- of hindered phenolic antioxidant
(3 ', 5'-di-tert-butyl-4'-hydroxyphenyl) propionate] methane 0.05% by weight, surface-coated di- (P-methylbenzylidene) sorbitol 95% by weight with calcium stearate 0.1% by weight and O- Methylbenzylidene-O-Methylbenzylidene sorbitol 0.25% by weight of dibenzylidene sorbitol mixed with 5% was well mixed with a mixer, and then extruded in a strand form at a resin temperature of 220 ° C. using a twin-screw extruder, water-cooled, and then with a cutter, a diameter of 2 mm,
An average thickness of the bottom part of the lid-fitting type shown in FIG. 1 was obtained by using the pellets dried after granulation into cylindrical pellets having a length of 3 mm and using the same injection molding machine and hot runner type mold as in Example 6. A container body for a photographic film cartridge having a size of 1.0 mm was prepared at a resin temperature of 190 ° C. by an injection molding method. Compared to that using only the ethylene-butene-1 copolymer resin, improves the bottom of the Shore hardness 62D → 68D, Olsen stiffness is improved to ^{7100kg / cm 2 → 9200kg / cm} 2, Vicat softening The point improved from 112 ℃ to 120 ℃. Further, the transparency is close to that using the propylene / ethylene random copolymer resin of Example 1 (haze is reduced by 20%), and the printing color of the photographic film cartridge can be observed in a beautiful color even from the outside of the container body, and it is fine. It was possible to clearly read the explanation, the CI mark, the kind display, etc.

In addition, if it is left in the sunlight for a long time,
After being stored for a long time under the condition of ℃ or less, even when taken out to the atmosphere of 20 ℃ or more, no water droplets were generated and the transparency was not lost. In addition, it has excellent physical strength, abrasion resistance, antistatic properties and lubricity, and the molding cycle could be shortened by 25%.

Furthermore, the generation of white powder due to an offensive odor and bleeding out over time was greatly reduced, as compared with the conventional container body for a photographic film cartridge containing an organic nucleating agent and an antioxidant. Gloss and transparency are significantly superior to those of the homopolyethylene resin of Example 6.

Example 9 MFR 15 g / 10 minutes, density 0.945 g / cm ³ , Olsen rigidity 6500 kg / cm ² , Izod impact strength 4 kg · cm / cm, Shore hardness 60 D, Vicat softening point 112 ° C ethylene
Butene-1 copolymer resin 91.1% by weight, dimethylpolysiloxane 0.3% by weight, vitamin E carboxylic acid ester 0.0
5% by weight, hindered phenolic antioxidant octadecyl-3- (3 ', 5'-di-tert-butyl-4'-hydroxyphenyl) propionate 0.05% by weight, silicon surface treated starch 3% by weight, light reflection As a light-shielding substance, 5% by weight of titanium oxide surface-coated with dihydric alcohol, 0.3% by weight of monoglyceride stearate, 1,3,2,4-diP-ethylbenzylidene sorbitol in which the surface of solid powder was previously coated with magnesium stearate 0.
After thoroughly mixing 2% by weight with a mixer, extruded into a strand shape at a resin temperature of 220 ° C using a twin-screw extruder, water-cooled and then granulated into a cylindrical pellet having a diameter of 2 mm and a length of 3 mm with a cutter, and then dried pellets Using the same injection molding machine and hot runner type mold as in Example 4, the container for photographic film cartridge of the lid-integrated type shown in FIG.
In this container, a 35 mm negative film containing a photographic film cartridge in which the tip of the photographic film is exposed is sealed from the metal cartridge which is most commercially available at present. This container is printed with a UV curable ink, such as product type, CI mark, instruction manual, bar code, etc., which were conventionally printed on a small cosmetic box, with the container body heated to 60 ° C and printed by UV irradiation. It was forcibly fixed. Sealing label 5 was attached as shown in FIG. 10 in order to secure the original sealing property. Compared to the ethylene / butene-1 copolymer resin alone, this package does not deform even when left in the sun and also has a light-shielding property, and contains titanium oxide which is a light-reflecting and light-shielding substance. There was almost no temperature rise in the container, and it was excellent in ensuring the performance of photographic film. In addition, no water droplets were generated on the container surface. In addition, the hardness of the bottom was improved, and the rigidity, wear resistance, antistatic properties and lubricity were excellent, and the molding cycle was shortened by 25%. This container does not have an offensive odor, does not generate white powder due to bleeding out over time, does not require a container for photographic film in a small cosmetic box unlike conventional containers, and is an inexpensive one that can significantly reduce industrial waste. It was Further, since the container body and the lid are made of the same resin composition, the suitability for recycling is excellent.

Example 10 MFR 7 g / 10 minutes, density 0.944 g / cm ³ , Olsen rigidity 6100 kg / cm ² , Izod impact strength 7 kg · cm / cm, Shore hardness 60D, Vicat softening point 115 ° C ethylene
8 Methyl pentene-1 copolymer resin 86.1% by weight, lubricant,
The type and amount of the antioxidant, drip-proof substance, and nucleating agent were the same as in Example 9, except that 5% by weight of titanium oxide surface-coated with dihydric alcohol as a light-reflecting and light-shielding substance was used, and surface-coated with calcium stearate. After thoroughly mixing the polyolefin resin composition containing 10% by weight of talc with a mixer, extruding it into a strand shape at a resin temperature of 220 ° C using a twin-screw extruder and cooling with water, and then using a cutter, cylindrical pellets having a diameter of 2 mm and a length of 3 mm After granulating, the dried pellets were used to prepare the container body for the photographic film cartridge shown in FIG. 1 using the same injection molding machine and hot runner type mold as in Example 6 for resin temperature.
Created at 200 ° C. Compared with ethylene / 4-methylpentene-1 copolymer resin alone, this container body has a Rockwell hardness of 68R and an Orsen rigidity of 6100 kg / c.
m ² → 9500kg / cm ² , Vicat softening point is 115 ℃ → 122 ℃
It was improved to. Also, after leaving it in the sun for a long time or storing it for a long time under the condition of 15 ° C or less,
No water droplets were generated even when taken out into the open air above ℃. Furthermore, the physical strength, wear resistance and lubricity were excellent, and the molding cycle could be shortened by 30%. In particular, as a user suitability, it was white and had an excellent appearance, and the impact strength was extremely excellent while ensuring rigidity, and the occurrence of a strange odor and the bleed-out of additives was small.

Among the above embodiments, the lid (cap) used in the embodiment (1, 2, 5, 6, 7, 8 or 10) of the body (container body) lid-fitting type is the MFR having the structure shown in FIG. (ASTM D 1238, 19
35 ℃ / 10min., Density (ASTM D 1505) 0.920g / cm
³ of homopolyethylene resin amide lubricant of oleic acid 0.0
Using a low density homopolyethylene resin composition containing 5% by weight and 0.05% by weight of a phenolic antioxidant, Nestal (trade name) manufactured by Sumitomo Heavy Industries was used as a molding machine (mold clamping pressure
150t), the number of cavities is 24, and it is made by the injection molding method using a hot runner type mold.

As a concrete example of a preferred embodiment, the scope of claims is satisfied, and reduction or recycling of industrial waste has recently become an important subject. From this viewpoint, the resin composition of the container body and the lid of the photographic film container of the present invention is a) the same resin composition. b) Polyolefin resin (homopolypropylene resin, propylene / ethylene random or block copolymer resin, propylene / α-olefin (C ₄ -C ₁₂ ) copolymer resin, homopolyethylene resin (low / medium / high density polyethylene resin) , Ethylene / α-olefins (C ₃ ~
C ₁₂ ) copolymer resin, polyolefin elastomer, poly α-olefin (C ₄ -C ₁₂ ) resin, ethylene vinyl acetate copolymer resin, ethylene / alkyl ester copolymer resin alone or as a blend resin of two or more kinds) 50% by weight or more, preferably 60% by weight or more, particularly preferably 70% by weight
The above is a polyolefin resin composition containing the necessary additives. c) Satisfies a) or b), and unifies the coloring to uncolored or white or silvery or yellow or green or black. d) When changing the resin composition of the container body and the lid,
To protect the photographic film cartridge and to improve the sealing performance, the rigidity of the container body should be ≧ the rigidity of the lid. Preferably, the rigidity of the container body is 1.5 times or more the rigidity of the lid, and particularly preferably 2.0 times or more. e) Add known additives for facilitating microbial decomposition, thermal decomposition or ultraviolet decomposition when disposed of.

The external shape of the container is as follows: 1) A bottomed cylindrical container body and a lid which is fitted into the container body to seal the container body. 2) It consists of a quadrangular prismatic container body and a lid that fits into this and seals the container body. 3) It consists of a polygonal columnar container body and a lid that fits into the container body and seals the container body.

In order to abolish the conventional cosmetic small box only for the containers of the shapes 1), 2) and 3), a) cover the container body and the lid with a shrink film (original seal is secured or moisture proof, gas barrier is provided). In order to achieve the objectives of improving properties, blocking ultraviolet rays, blocking light, or reducing the amount of transmitted light, coloring or printing, or coating or vapor deposition of a substance having the above action). B) Sensitivity, number of shots, CI mark, barcode, explanatory note, white background for memos, etc. on the container body. A sheet-made label (even if it is a non-foamed sheet) made of a polyolefin-based resin composition conforming to an adhesive paste for sticking (when it needs to be peeled from the container body like a paper label) or a heat-sensitive paste (above, a) to b) A foamed sheet, non-woven fabric or synthetic paper may be blended together with the container body such as), and the like, and is heat-bonded to the container body in a printed label coated with the like or a resin composition according to the above a) to b). A possible polyolefin resin label (multilayer structure is also possible) is attached by a labeling machine having an automatic label correction device. C) Print or transfer print directly on the container body instead of the label. D) Labels that have adhesive or heat-sensitive adhesive applied to paper, plastic, synthetic paper, non-woven fabric, or foamed sheets or labels that exhibit adhesiveness by heating are applied across both the container body and the lid (the above-mentioned label on the printed label). In addition to b, it has original sealing properties, moisture resistance, waterproof properties, gas barrier properties, etc.).

Shrink films (shrink single-layer film, shrink multi-layer film, shrink laminated film, shrink foam sheet, shrink metal vapor deposition film, etc.) and labels have various known processes (in the case of shrink film, for easy peeling). (For perforations, notches, knobs, etc., labels do not have glue applied, knobs, etc.)
May be given.

[0128]

EFFECTS OF THE INVENTION According to the present invention, water droplets are not generated on the container surface even when the environment is rapidly changed from a low temperature environment to a normal temperature environment or left in the sunlight. Therefore, it is possible to surely recognize the type of the stored photographic film.

[Brief description of drawings]

FIG. 1 is a cross-sectional view of a lid-fitting type photographic film cartridge container to which the photographic film container of the present invention is applied.

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

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

FIG. 4 is a cross-sectional view of a container for a photographic film cartridge in which a body lid to which the photographic film container of the present invention is applied is integrated by a hinge.

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

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

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

FIG. 8 is a perspective view of a photographic film cartridge container body to which the photographic film container of the present invention is applied.

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

FIG. 10 is a perspective view of a photographic film cartridge container to which the photographic film container of the present invention is applied.

[Explanation of symbols]

 1 ... Lid 2 ... Container body 3 ... Hinge part

Claims (13)

[Claims] 1. A photographic film comprising a polyolefin resin composition containing a drip-proof substance having an antifogging action or a dripproof action, a lubricant, an antioxidant, and 50% by weight or more of a polyolefin resin. Container 2. The polyolefin resin composition comprises 0.01-3.0% by weight of a drip-proof substance, 0.01-3.0% by weight of a lubricant, 0.01-3.0% by weight of an antioxidant and 0.01-3.0% of a phenol-based and / or phosphorus-based antioxidant.
The photographic film container according to claim 1, wherein the polyolefin resin is 0.5% by weight and the propylene / α-olefin random copolymer is 50% by weight or more. 3. The polyolefin resin composition has a temperature of 180 ° C.
The photographic film container according to claim 1 or 2, which has undergone the above heat history. 4. The photographic film container according to claim 1, wherein the drip-proof substance is contained at least in the same amount as the lubricant. 5. The nonionic surfactant lubricant is 0.01 to 2.0.
The photographic film container according to claim 1 or 2, wherein the photographic film container contains 20% by weight. 6. The container for photographic film according to claim 1, which contains 0.01 to 2.0% by weight of a nucleating agent. 7. The photographic film container according to claim 1, wherein the light-reflecting light-shielding substance is contained in an amount of 0.01 to 30% by weight. 8. The polyolefin resin composition comprises 0.01 to 3.0% by weight of a drip-proof substance, 0.01 to 5.0% by weight of a lubricant, and a phenol-based and / or phosphorus-based antioxidant as an antioxidant of 0.
001 to 2.0% by weight, density of polyolefin resin is 0.93
5 g / cm ³ or more claims ethylene · alpha-olefin random copolymer resin and / or density contains 0.935 g / cm ³ or more homo polyethylene resin at least 50% by weight or more 1,3,
The container for photographic film as described in 4, 5, 6 or 7. 9. A drip-proof substance having an antifogging action or a dripproof action, a lubricant, an antioxidant, a nucleating agent and a melt flow rate of 5
〜80g / 10min, Olsen rigidity 3500kg / cm ² or more, Vicat softening temperature 95 ℃ or more 70% by weight of polyolefin resin
A photographic film container comprising a polyolefin resin composition containing the above 10. A drip-proof substance, a silicon lubricant and / or a fatty acid amide lubricant of 0.01 to 5.0% by weight, a hindered phenolic antioxidant of 0.0005 to 1.0% by weight, and a di-substituted benzylidene sorbitol composition of 0.01. ~ 2.0 wt%
And a number average molecular weight of 20,000 to 800,000, molecular weight distribution (Mw
/ Mn) is a polyolefin resin composition having a thermal history of 180 ° C or higher containing 50% by weight or more of a polyolefin resin having a Mn of 2 to 20, and a container for photographic film. 11. The container body and the polyolefin resin composition of the lid are the same kind or the same, and is composed of a recyclable resin composition, 1, 2, 3,
Container for photographic film according to 4, 5, 6, 7, 8, 9 or 10 12. The polyolefin-based resin composition contains a biodegradable additive, a photodegradable additive, a biodegradable polymer or a photodegradable polymer, as claimed in any one of claims 1, 2, 3, 4, 5, 6, 7,
Container for photographic film according to 8, 9, 10 or 11 13. The anti-drip substance is 0.01 to 3.0% by weight, the silicone lubricant and / or the fatty acid amide lubricant is 0.01 to 5.0% by weight, the antioxidant is 0.0005 to 1.0% by weight, and the di-substituted benzylidene sorbitol is used. 0.01-2.0% by weight of composition
And melt flow rate of 5 to 80 g / 10 minutes, Orsen rigidity of 3500 kg / cm ² or more (for homopolyethylene resin and ethylene / α-olefin copolymer resin), initial flexural modulus of 5000 kg / cm ² or more ( In the case of homopolypropylene resin and propylene / α-olefin copolymer resin), a polyolefin resin composition containing at least 70% by weight or more of a polyolefin resin having a Vicat softening point of 95 ° C or higher is used, and gold with 12 or more cavities is used. Injection molded using a mold, the bottom Rockwell hardness is 40R or more, the Vicat softening point is 105 ℃
Above, the container for photographic film, characterized in that the average thickness of the bottom is 0.5 to 2.0 mm