JPH0667357A - Molded article for photographic sensitive material and photographic sensitive material-packed body using the same - Google Patents

Abstract

PURPOSE:To inhibit the bleeding-out of an antistatic agent and a lubricant and the decomposition of a thermoplastic resin in a molded article for a photographic sensitive material such as a packing film for a photographic sensitive material or the body of a vessel for a photographic film cartridge and to prevent the occurrence of white powder, the lowering of transparency and coloring. CONSTITUTION:A packing film for a photographic sensitive material is formed with a monolayer film made of a light shielding thermoplastic resin film 1a. This film la is made from a molding resin compsn. consisting of 100 pts.wt. crystalline resin compsn. contg. a crystalline resin and a lubricant and/or an antistatic agent, 0.001-2.0 pts.wt. antioxidant and 5-90 pts.wt. acrylic acid copolymer resin.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a molded article for a photographic light-sensitive material and a photographic light-sensitive material package using the same, and more specifically to prevent migration of a lubricant and an antistatic agent to the surface of the molded article. The present invention relates to a molded product for a photographic light-sensitive material, which is excellent in quality and appearance, and which prevents stickiness and generation of white powder over time, and a photographic light-sensitive material package using the same.

[0002]

2. Description of the Related Art Conventionally, as a packaging film for a photographic light-sensitive material, as disclosed in Japanese Patent Publication No. 63-26697, a polyester layer, an adhesive layer, an aluminum foil, a light-shielding substance and a nonionic material are applied from the outside. Some have a polyolefin resin layer containing an antistatic agent.

Further, conventionally, as a container body for a photographic film cartridge, as disclosed in JP-A-61-73947, a resin composition in which a fatty acid amide lubricant is contained in a polypropylene resin in an amount of 0.05 to 1% by weight. Things were being used. This photographic film cartridge container body was extremely suitable because the injection molding cycle could be greatly shortened, molding failures could be greatly reduced, and the container bodies would slide well and scratches would not easily occur.

[0004]

However, since the conventional packaging film and the container body for the cartridge described above use the crystalline resin, the antistatic agent or the lubricant migrates to the surface of the molded article. It had various problems. In addition, the container body for photographic film cartridges, which requires transparency, was improved by adding an organic nucleating agent.
No. 58616), but it has various problems because it migrates to the surface and is thermally decomposed.

That is, the packaging film for the photographic light-sensitive material is inferior in antistatic durability, and the antistatic agent bleeds out with the lapse of time, resulting in stickiness, blocking, poor heat-sealing and the like. .

Further, in a conventional transparent photographic film cartridge container body, a fatty acid amide lubricant bleeds out on the surface with the lapse of time, and as a result, the transparency may be lowered or white powder may be generated. .

In the high temperature molten resin, the organic nucleating agent, the antistatic agent and the lubricant are more easily oxidized than the resin and thermally decomposed, so that the photographic light-sensitive material may be adversely affected such as fog and increased / decreased sensitivity. Occasionally, hard spots (solid foreign matter) or coloring defects that deteriorate the appearance of molded products were generated.

The present invention solves the above problems, suppresses bleed-out of antistatic agents and lubricants, and also suppresses thermal decomposition of crystalline resins, organic nucleating agents, antistatic agents and lubricants. With the object of providing a molded article for a photographic light-sensitive material and a package using the same, which is capable of preventing the adverse effects associated with the phenomenon of (1) and maintaining good quality of the photographic light-sensitive material for a long period of time and has excellent suitability for user use. To do.

[0009]

The present invention has been made to achieve the above object, and a molded article for a photographic light-sensitive material of the present invention is a crystal containing a crystalline resin and a lubricant and / or an antistatic agent. Resin composition 100 parts by weight, antioxidant 0.001-2.0
It is composed of a molding resin composition composed of 5 parts by weight and 5 to 90 parts by weight of an acrylic acid copolymer resin.

The crystalline resin used in the present invention is homopolyethylene resin, homopolypropylene resin, propylene / α.
One type of olefin copolymer resin, ethylene copolymer resin, polyacetal resin, polyamide resin, polyester resin such as polyethylene terephthalate resin and polyethylene naphthalate resin, polytetrafluoroethylene resin, polyvinyl alcohol resin, isotactic polystyrene resin Alternatively, it is a resin containing 50% by weight or more of two or more kinds. Preferably a polyethylene resin and a polypropylene resin, particularly preferably a low density homopolyethylene resin (hereinafter LD
PE resin), high-density homopolyethylene resin (hereinafter referred to as HDPE resin), L-LDPE resin, homopolypropylene resin, and propylene / ethylene copolymer resin. Representative examples of ethylene copolymer resins that can be used in the present invention are shown below.

(1) ethylene-vinyl acetate copolymer resin (hereinafter referred to as EVA resin) (2) ethylene-propylene copolymer resin (3) ethylene-1-butene copolymer resin (4) ethylene-butadiene Copolymer resin (5) Ethylene-vinyl chloride copolymer resin (6) Ethylene-methyl methacrylate copolymer resin (hereinafter referred to as EMM resin) (7) Ethylene-methyl acrylate copolymer resin (hereinafter,
(Displayed as EMA resin) (8) Ethylene-ethyl acrylate copolymer resin (hereinafter,
(Displayed as EEA resin) (9) Ethylene-acrylonitrile copolymer resin (10) Ethylene-acrylic acid copolymer resin (hereinafter referred to as EAA
(Indicated as resin) (11) Ionomer resin (resin obtained by crosslinking a copolymer of ethylene and an unsaturated acid with a metal such as zinc) (12) Ethylene-α-olefin copolymer resin (hereinafter referred to as L-
LDPE resins display) (13) Ethylene - propylene - butene-1 ternary copolymer resin (14) ethylene - propylene elastomers the L-LDPE (L inear L ow D ensity P oly e thyl
The ene) resin is called the third polyethylene resin, and is a low-cost, high-strength resin that meets the needs of the times of energy-saving and resource-saving, which has the advantages of medium / low density, high density, and both polyethylene resins. . This resin has ethylene and 3 to 13 carbon atoms, preferably 4 to 10 carbon atoms by the low pressure method or the high pressure improvement method.
This is a polyethylene-based resin having a structure in which a linear straight chain has a short branch, which is a copolymer obtained by copolymerizing individual α-olefins. Preferred α-olefins in terms of physical strength and cost are butene-1, octene-1, and hexene-1,4-.
Methylpentene-1, heptene-1, decene-1 and the like are used. The density is generally considered to be a low-medium density polyethylene resin, but most commercial products have a density within the range of 0.87 to 0.97 g / cm ³ . Melt flow rate is 0.1-80
Many are in the range of g / 10 minutes. As a polymerization process of L-LDPE resin, a gas phase method using medium and low pressure equipment,
There are a solution method, a liquid phase slurry method, an ionic polymerization method using a high-pressure improvement method apparatus, and the like.

Specific examples of commercially available L-LDPE resins are shown below. Ethylene / Butene-1 Copolymer Resin G Resin and NUC-FLX (UCC Company) Dourex (Dow Chemical Company) Sclear (Dupont Canada Company) Marlex (Philips Company) Stamilex (DSM Company) Excellen VL (Sumitomo Chemical Co., Ltd.) Neozex (Mitsui Petrochemical) Mitsubishi Polyethylene-LL (Mitsubishi Petrochemical) Nisseki Linilex (Nippon Petrochemical) NUC Polyethylene-LL (Nippon Unicar) Idemitsu Polyethylene L (Idemitsu Petrochemical) Ethylene / Hexene-1 Copolymer Resin TUFLIN ( UCC) TUFTHENE (Nippon Unicar) Ethylene / 4-methylpentene-1 copolymer resin Ultzex (Mitsui Petrochemical) Ethylene / octene-1 copolymer resin Stamirex (DSM) Dourex (Dow Chemical Co.) Screamer Dupo Canada Inc.) MORETEC (Idemitsu Petrochemical)

Of these L-LDPE resins, those having a melt flow rate (hereinafter referred to as MFR) of 0.8 to 10 g / 10 are particularly preferable as a film molded product in view of physical strength, heat seal strength and film moldability. Min, preferably 1.0 to 7 g / 10 min (JIS K-6760 test temperature 190 ° C,
Test load 2.16kgf), density 0.870-0.940g / cm
³ , preferably 0.890 to 0.930 g / cm ³ (JIS K-676
0), and α-olefins obtained by the liquid phase slurry method process and the gas phase method process having 6 to 8 carbon atoms. In the case of an injection-molded product, it is particularly preferable that the MFR is 2 to 80 g / in terms of the balance between improvement of physical strength and injection moldability.
10 minutes, preferably 5 to 50 g / 10 minutes, density 0.890 to 0.980
g / cm ³ , preferably 0.900 to 0.970 g / 10 minutes, and α
-Olefins obtained by a liquid-phase slurry process and a gas-phase process having 3 to 8 carbon atoms.

A typical example of a particularly preferable film molded product is the product name, Ult of Mitsui Petrochemical Co., Ltd., in which 4-methylpentene-1 having 6 carbon atoms as an α-olefin side chain is introduced into polyethylene. There are MORETEC of Idemitsu Petrochemical Co., Ltd. and Stamilex of DSM, and Dourex of Dow Chemical Co., which introduces octene-1 having 8 carbon atoms as ZEX, etc. L obtained by co-liquid phase slurry process
-LDPE resin. ). Preferred representative examples obtained by the low-pressure vapor phase process are given by trade names: TUFLIN manufactured by UCC Co. and Nippon Unicar Co., Ltd. in which hexene-1 having 6 carbon atoms is introduced as an α-olefin side chain. TU
There is FTHENE etc.

The recently released density is 0.910 g / cm ^3.
Ultra low-density linear low-density polyethylene resin of less than, for example, NUC-FLX of UCC and Excellen VL of Sumitomo Chemical Co., Ltd. are also preferable (above, butene-1, which is a product of two companies and has 4 carbon atoms of butene-1). use).

The names of typical commercially available lubricants and the names of manufacturers are listed below. (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 fats and oils), Alflo S-10 (Nippon fats and oils) , 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.

[Hydroxystearic acid amide lubricant] Palmitic acid amide lubricant; Neutron S-18
(Nippon Seika), Amide P (Nitto Kagaku), etc. Lauric acid amide lubricants; Armide C (Lion Akzo), Diamid (Nippon Kasei), etc.

[Unsaturated Fatty Acid Amide Lubricants] Erucamide amide lubricants; Alflo P-10 (Nippon Yushi), Neutron-S (Nippon Seika), LUBROL
(I ・ C ・ I), Diamid L-200 (Nippon Kasei), etc. Oleic acid amide lubricants; Armoslip CP (Lion Akzo), Neutron (Nippon Seika), Neutron E-18 (Nippon Seika) ), Amide O (Nitto Kagaku),
Diamond Mid O-200, Diamond Mid G-200 (Nippon Kasei), Alflo E-10 (Nippon Yushi), Fatty Acid Amide O (Kao), etc.

[Bis-fatty acid amide lubricant] Methylene bis-behenic acid amide lubricant; Diamid NK bis (Nippon Kasei), etc. Methylene bis-stearic amide lubricant; Diamid 200 bis (Nippon Kasei), Armowax (Lion)・
Akzo), bisamide (Nitto Kagaku), etc. Methylenebisoleic acid amide lubricant; Lubron O
(Nippon Kasei) etc. Ethylenebisstearic acid amide lubricants; Armoslip EBS (Lion Akzo) etc. Hexamethylenebisstearic acid amide lubricants; Amide 65 (Kawaken Fine Chemicals) etc. Hexamethylenebisoleic acid amide lubricants; Amide 60 (Kawaken Fine Chemicals) etc.

(2) Nonionic surfactant lubricants; Electrostripper-TS-2, Electrostripper-TS
-3 (Kao soap)

(3) Hydrocarbon lubricants; liquid paraffin, natural paraffin, microwax, synthetic paraffin, polyethylene wax (number average molecular weight is 10,000 or less, preferably 8,000 or less, particularly 6,000 or less), polypropylene wax (number) An average molecular weight of 10,000 or less, preferably 8,000 or less, particularly preferably 6,000 or less.), Chlorinated hydrocarbon, fluorocarbon, etc.

(4) Fatty acid type lubricant; higher fatty acid (C ₁₂ or more is preferable, specifically caproic acid, stearic acid, oleic acid, erucic acid, palmitic acid, etc.), oxy fatty acid, etc.

(5) Ester lubricants; lower alcohol esters of fatty acids, polyhydric alcohol esters of fatty acids, polyglycol esters of fatty acids, fatty alcohol esters of fatty acids, etc.

(6) Alcohol-based lubricant; polyhydric alcohol,
Polyglycol, polyglycerol, etc.

(7) Metal soap; higher grades such as lauric acid, stearic acid, succinic acid, stearyl lactic acid, lactic acid, phthalic acid, benzoic acid, hydroxystearic acid, ricinoleic acid, naphthenic acid, oleic acid, palmitic acid and erucic acid Fatty acids and Li, Na, Mg, Ca, Sr, Ba, Zn, C
Examples thereof include compounds with metals such as d, Al, Sn, Pb, and Cd, and preferred are magnesium stearate, calcium stearate, zinc stearate, magnesium oleate, and the like.

(8) partially saponified montanic acid ester;

(9) Silicone-based lubricants; various grades of dimethylpolysiloxane and its modified products (Shin-Etsu Silicone, Toray Silicone), especially various silicone oils not only exert the effect of improving resin fluidity and lubricity, etc. , When used together with a light-shielding substance, it improves the dispersibility of the light-shielding substance
As a result of making the resin cloudy and increasing the haze (ASTM D-1003), unexpected effects such as improvement in coloring power and light-shielding property are exhibited, which is preferable.

The silicone oil preferably has a viscosity in the range of 50 to 100,000 centistokes at room temperature, more preferably a high viscosity of 5,000 to 30,000 centistokes. Specific examples of silicone and silicone modified products include polymethylphenyl siloxane,
Olefin-modified silicone, amide-modified silicone, polydimethylsiloxane, amino-modified silicone, carboxyl-modified silicone, α-methylstyrene-modified silicone, polyether-modified silicone modified with polyethylene glycol or polypropylene glycol, olefin / polyether-modified silicone, epoxy-modified silicone, It is a silicone oil containing a modified siloxane bond such as amino-modified silicone and alcohol-modified silicone. Among the silicone oils, the ones which have less adverse effect on the photographic light-sensitive material and have a large slipping effect, particularly when applied to a molded article for a photographic light-sensitive material, are preferably olefin-modified silicone, amide-modified silicone, polydimethylsiloxane, poly These are ether-modified silicone and olefin / polyether-modified silicone. The silicone oil improves the friction coefficient of a molding material, for example, a resin film in a heated state, reduces sliding resistance generated during hot plate sealing by an automatic wrapping machine, and prevents wrinkles from generating a beautiful appearance. And, it is possible to form a basis for obtaining a resin film having a high sealing property and an adhesion property without sagging on a packaged object. Further, it is possible to prevent the deterioration of gloss due to sliding and obtain a beautiful seal portion.
In the present invention in which silicone oil is also used, the high temperature friction coefficient can be 1.4 or less when sliding heat sealing is performed.

The effects of adding silicone oil are as follows. (1) By only using the fibrous filler, the non-fibrous light-shielding substance, and the pigment in combination, the surface of these is covered and the dispersibility is improved. (2) Improve the dispersibility of the resin, reduce the motor load on the screw, and prevent melt fracture. (3) Sufficient lubricity can be ensured without adding a fatty acid amide that bleeds out to form a white powder. (4) The friction coefficient of the molding material in the heated state can be reduced, the suitability for an automatic bag can be improved, wrinkles at the time of heat sealing and the deterioration of gloss due to sliding can be prevented, and a beautiful sealed portion can be obtained. (5) When used in combination with a light-shielding substance, it makes the thermoplastic resin cloudy and increases haze, resulting in improved coloring power and improved light-shielding ability. You can secure the sex.

The amount of the lubricant added varies depending on the type, and among the lubricants most suitable for the molded product of the photographic light-sensitive material of the present invention, a lubricating effect mainly for maintaining the photographic performance of the photographic light-sensitive material such as a fatty acid metal salt is obtained. In the case of a small lubricant, 0.03-5% by weight, preferably 0.05-3% by weight, particularly preferably 0.1-
It is 1.5% by weight. In the case of a lubricant such as a fatty acid amide type lubricant and a bis fatty acid amide type lubricant, which has a large lubricating effect and easily bleeds out, and which affects the photographic light-sensitive material, 0.01 to 1% by weight, preferably 0.03 to 0.5% by weight, It is particularly preferably 0.05 to 0.3% by weight.

Typical examples of the antistatic agent are shown below. I. Nonionic (= nonionic) (1) Alkylamine derivative: T-B103 (Matsumoto Yushi), T
-B104 (Matsumoto Yushi) Alkylamide type polyoxyethylene alkylamine: Armostat 31
0 (Lion oil and fat) Tertiary amine (lauryl amine): Armostat 400 (Lion oil and fat) N, N-bis (2-hydroxyethylcocoamine): Armostat 410 (Lion oil and fat) Tertiary amine: ANTISTATIC 273C, 273, 273E
(Fine Org. Chem) N-hydroxyhexadecyl-di-ethanol-amine: Belg.
P. 654, 049 N-hydroxyoctadecyl-di-ethanol-amine: (Natio
nal Dist.)

(2) Fatty acid amide derivative: TB-115 (Matsumoto Yushi), Elegan P100 (Nippon Yushi), Eleek SM-
2 (Yoshimura Oil Chemistry) Hydroxystearic acid amide Oxalic acid-N, N'-distearylamide butyl ester: Hoechst polyoxyethylene alkylamide

(3) Ether type polyoxyethylene alkyl ether RO (CH ₂ CH ₂ O) nH polyoxyethylene alkylphenyl ether Special nonionic type: Resist 104, PE100, 116 to 118
(Daiichi Kogyo Seiyaku), Resist PE132, 139 (Daiichi Kogyo Seiyaku), Elegan E115, Chemistat 1005 (Nippon Yushi), Eleek BM-1 (Yoshimura Yushi Kagaku), Electrostripper TS, TS2, 3, 5, 5. EA, EA2, 3
(Kao soap)

(4) Polyhydric alcohol ester type glycerin fatty acid ester: mono-, di-, or triglycerides such as stearic acid or hydroxystearic acid, monoglyceride ((Japanese camphor), TB-123 (Matsumoto Yushi),
Resist 113 (Daiichi Kogyo Seiyaku Co., Ltd.) Sorbitan fatty acid ester Special ester: Elyk BS-1 (Yoshimura Yushi Kagaku) 1-Hydroxyethyl-2-dodecylglyoxazoline: British cellophane

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

III. Cation system (1) Amide type cation: Resist PE300, 401, 40
2, 406, 411 (Daiichi Kogyo Seiyaku Co., Ltd.) (2) Quaternary ammonium salt Quaternary ammonium chloride Quaternary ammonium sulfate Quaternary ammonium nitrate Katimin CSM-9 (Yoshimura Yushi Kagaku), CATANAC60
9 (American Cyanamide), Denon 314C (Maruhishi Yuka), Armostat 300 (Lion oil), 100V (Armor), Electrostripper-ES (Kao soap),
Chemistat 2009A (Nippon Yushi) Stearamido propyl-dimethyl-β-hydroxyethyl amm
onium nitrate: CATANAC SN (American
Dianamid)

IV. Zwitterion type (1) Alkyl petaine type: (2) Imidazoline type: Rheostat 53, 532 (Lion oil), AMS 53 (Lion oil), AMS303, 313 (Lion oil) Alkyl imidazoline type (3) Metal salt type: AMS 576 (by Lion Yushi) rheostat 826, 923 (by Lion _{Yushi) (RNR'CH 2 CH 2 CH 2} NCH 2 COO) 2 Mg {R ≧ C, R '= H or (CH ₂₎ mCOO -} (by Lion Yushi) R = C ₃ ~ ₈ hydrocarbon, A = oxygen or imino group, M = organic amine or metal (4) alkylalanine type:

V. Conductive resin Polyvinyl benzyl type cation Polyacrylic acid type cation VI. Others: Register 204, 205 (Daiichi Kogyo Seiyaku),
Elegan 2E, 100E (Nippon Yushi), Chemistat 1002,
1003, 2010 (Nippon Yushi), Eleek 51 (Yoshimura Yushi Kagaku),
ALROMINE RV-100 (Geigy) Among the above antistatic agents, nonionic (nonionic) type antistatic agents are particularly preferable because they have little adverse effect on photographic properties and human body and have a great effect of preventing static marks.

The amount of antistatic agent added depends on the crystalline resin composition.
0.01 to 5.0 parts by weight is preferable with respect to 100 parts by weight, and 0.05 to 5.0 parts by weight.
3.0 parts by weight is more preferable, and 0.1 to 1.5 parts by weight is the most preferable. If the addition amount is less than 0.01 parts by weight, the effect of addition cannot be exhibited and only the kneading cost increases. In addition, the addition amount is 5.0
If it exceeds the weight part, slipping between the molten resin and the screw of the extruder is likely to occur, and the discharge amount of the resin becomes unstable. Further, stickiness and bleed-out easily occur with the passage of time after molding.

A crystalline resin composition is composed of the crystalline resin, a lubricant and an antistatic agent, and the crystalline resin composition 100
The addition amount of various substances described below is determined with respect to parts by weight.

An antioxidant is used in the molded article for photographic light-sensitive material 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 resin) and various polypropylene resins (including propylene / ethylene random copolymer resin), which are typical thermoplastic resins of crystalline resins
Etc. are hydrocarbons, and it is believed 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. To produce a large amount of alcohol, aldehyde, acid, etc., which adversely affects the photographic properties of the photographic light-sensitive material, and these react with each other to form a polymer.

In order to prevent the oxidation of hydrocarbons, it is necessary to go through the above chain reaction, and therefore an antioxidant is used. In addition, it is also preferable to add the radical scavenger described below.

The radical scavenger used in the present invention is 1,1-diphenyl-2-picrylhydrazyl,
1,3,5-Triphenylferdazyl, 2,2,6
6-Tetramethyl-4-piperidone-1-oxyl, N
-(3-N-oxyanilino-1 .3-dimethylbutylidene) -aniline oxide, high valent metal salts such as ferric chloride, diphenylpicrylhydrazine, diphenylpicrylhydrazine, diphenylamine, hydroquinone, t- Examples thereof include butyl catechol, dithiobenzoyl disulfide, p · p′-ditolyl trisulfide, benzoquinone derivative, nitro compound, and nitroso compound. Among these, it is particularly preferable to use hydroquinone. The above radical scavengers may be used alone or in combination of several kinds. The content of the radical scavenger in the slippery thermoplastic resin layer is 100 to 10,000 ppm, preferably 500 to
It is 5,000 ppm.

Phosphoric acid, citric acid, phosphoric acid compounds, citric acid compounds, etc. described as antioxidant synergistic agents in the present invention which synergistically improve the antioxidant action when used in combination with an antioxidant It is particularly preferable to use in combination with at least one of the agent and the radical scavenger. The content of these antioxidant synergists is 0.001 to 2.0% by weight, preferably 0.
It is 005 to 1.5% by weight, particularly preferably 0.01 to 1.0% by weight.

In order to prevent the oxidation of hydrocarbons, it is necessary to go through the above chain reaction, and therefore 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 decomposing agent which stabilizes this. The former includes alkylphenol antioxidants and aromatic amine antioxidants. The latter includes sulfur antioxidants and phosphorus antioxidants. It is preferable to use a free-radical chain-stopping antioxidant and a peroxide decomposition antioxidant together to prevent yellowing or browning due to heat deterioration of the thermoplastic resin and the occurrence of lumps (foreign matter-like black solidification). . 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 unless it is carefully examined for the amount to be added, which becomes a problem.

In order to prevent thermal deterioration of a thermoplastic resin, particularly a polyolefin resin which is a crystalline resin, 0.001 to 1% by weight, preferably 0.005 to 0.8% by weight, of an organic cyclic phosphorus compound,
It is particularly preferable to use 0.01 to 0.5% by weight alone or in combination with another antioxidant. As an antioxidant to be used in combination, a phenolic antioxidant, especially a hindered phenolic antioxidant, which has a free radical chain terminating action different from the peroxide decomposing action of a cyclic phosphorus compound and has little adverse effect on a photographic light-sensitive material. 0.001 to 1% by weight, preferably 0.0
It is preferable to use it in an amount of from 05 to 0.8% by weight, particularly preferably from 0.01 to 0.5% by weight.

When these radical scavengers and / or antioxidant synergists such as phosphoric acid and citric acid are also used in combination with these, the generation of substances adversely affecting the photographic light-sensitive material and the heat of the resin and the additives. It is preferable because yellowing, browning, and spotting due to deterioration are reduced and continuous molding is possible for a long time.

Representative general formulas for the organic cyclic phosphorus compounds of the present invention are described below.

[0050]

[Chemical 1] {In the formula, R ₁ represents a tertiary butyl group or a tertiary amyl group, R ₂ represents an alkyl group having 1 to 9 carbon atoms, and R ₃ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. Shows,
R ₄ represents an alkyl group having 1 to 30 carbon atoms or an aryl group having 6 to 15 carbon atoms. }

[0051]

[Chemical 2] {In the formula, R ₁ represents a tertiary butyl group or a tertiary amyl group, R ₂ represents an alkyl group having 1 to 9 carbon atoms, and R ₃ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. Shows,
R ₄ represents an alkyl group having 1 to 30 carbon atoms or an aryl group having 6 to 15 carbon atoms. }

[0052]

[Chemical 3] {In the formula, R ₂ represents an alkyl group having 1 to 9 carbon atoms,
R ₃ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and M represents an alkali metal. }

[0053]

[Chemical 4] {In the formula, R ₃ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ₅ and R ₆ are each a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group, an aryl group or aralkyl. represents a group, X is -OH group or -O ^-
Indicates NH ₄ ⁺ . }

In order to prevent photodegradation of the photographic film container, various ultraviolet absorbers are contained in an amount of 0.001 to 5% by weight, preferably 0.005 to 3% by weight, and particularly preferably 0.01 to 1% by weight. Particularly preferred as the ultraviolet absorber is a hindered amine type ultraviolet absorber (2.2,6.6-tetramethyl-4-piperidinol, 2.2,6.6-tetramethyl-
4-piperidyl benzoate, 2.2,6.6-tetramethyl-4-piperidinol, etc.) and a benzophenone-based UV absorber.

Typical examples of the antioxidant used in the present invention are shown below. (A) Phenolic antioxidant (t is an abbreviation for tert) Vitamin E (tocopherol), 6-t-butyl-3-
Methylphenyl derivative, 2,6-di-t-butyl-P
-Cresol, 2,6-di-t-butyl-phenol,
2,6-di-t-butyl-α-dimethylamino-p-cresol, 2,6-di-t-butyl-p-ethylphenol, 2,2′-methylenebis- (4-ethyl-6-t
-Butylphenol), 4,4'-butylidene bis (6
-T-butyl-m-cresol), 4.4'-thiobis (6-t-butyl-m-cresol), 4.4-dihydroxydiphenylcyclohexane, butylated hydroxyanisole, alkylated bisphenol, styrenated phenol, 2 -6-di-t-butyl-4-methylphenol, 2,6-di-t-butyl-4-ethylphenol, n-octadecyl-3- (3'-5'-di-t-butyl-4 ' -Hydroxyphenyl) propinate, 2.2 '
-Methylenebis (4-methyl-6-t-butylphenol), 4.4'-thiobis (3-methyl-6-t-butylphenyl), 4.4'-butylidenebis (3-methyl-6-t-butylphenol) 4,4'-thiobis (3-methyl-6-t-butylphenol), stearyl-β (3,5-di-t-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 type antioxidant 6-ethoxy-2,2,4-trimethyl-1,2-dihydroquinoline, polymer of 2,2,4-trimethyl-1,2-dihydroquinoline, trimethyl Dihydroquinoline derivative, etc.

(C) Allylamine Antioxidant Phenyl-α-naphthylamine, N-phenyl-β-naphthylamine, N-phenyl-N'-isopyropyr-P
-Phenylenediamine, N.N'-diphenyl-P-phenylenediamine, N.N'-di-β-naphthyl-P-
Phenylenediamine, N- (3'-hydroxybutylidene) -1-naphthylamine, etc.

(D) Imidazole type antioxidant 2-mercaptobenzimidazole, zinc salt of 2-mercaptobenzimidazole, 2-mercaptomethylbenzimidazole, etc.

(V) Phosphite type antioxidants Alkylated allyl phosphite, tris (mono and / or dinonylphenyl) phosphite, cyclic neopentanetetraylbis (2.6-di-t-butyl-4)
-Methylphenyl) phosphite, diphenylisodecylphosphite, tris (nonylphenyl) phosphite sodium phosphite, tris (nonylphenyl) phosphite, 2.2-methylenebis (4.6-di-t-butylphenyl) Octyl phosphite, Tris (2.4
-Di-t-butylphenyl) phosphite, triphenylphosphite, etc.

(F) Thiourea type antioxidant Thiourea derivative, 1.3-bis (dimethylaminopropyl) -2-thiourea, etc.

(G) Other antioxidants useful for air oxidation Dilauryl thiodipropionate, etc.

Typical examples of the hindered phenolic antioxidants most preferable for the present invention are shown below. 1,3,5-Trimethyl 2,4,6-tris (3,5-di-tert-butyl-
4-hydroxybenzyl) benzene, tetrakis [methylene-3- (3'.5'-di-tert-butyl-4'-hydroxyphenyl) propionate] methane, octadecyl-3,5-di-tert-butyl-4- Hydroxy-hydrocinnamate, 2,2 ', 2'-tris [(3,5-di-t
ert-Butyl-4-hydroxyphenyl) propionyloxy] ethyl isocyanurate, 1,3,5-tris (4-tert-butyl-3-hydroxy-2,6-di-methylbenzyl] isocyanurate, tetrakis (2, Four
-Di-tert-butylphenyl) 4,4'-biphenylene diphosphite, 4,4'-thiobis- (6-tert-butyl-O-cresol), 2,2'-thiobis- (6-te
rt-butyl-4-methylphenol), tris- (2-
Methyl-4-hydroxy-5-tert-butylphenyl)
Butane, 2,2'-methylene-bis- (4-methyl-6-
tert-butylphenol), 4,4'-methylene-bis-
(2,6-di-tert-butylphenol), 4,4′-butylidenebis- (3-methyl-6-tert-butylphenol), 2,6-di-tert-butyl-4-methylphenol, 4-hydroxy. Methyl-2,6-di-tert-butylphenol, 2,6-di-tert-4-n-butylphenol, 2,6-bis (2'-hydroxy-3'-ter
t-Butyl-5'-methylpentyl) -4-methylphenol, 4,4'-methylene-bis- (6-tert-butyl-
O-cresol), 4,4'-butylidene-bis (6-te
rt-butyl-m-cresol), 3.9-bis {1.1
-Dimethyl-2- [β- (3-t-butyl-4-hydroxy-5-methylphenyl) propionyloxy] ethyl} 2,4,8,10-tetraoxaspiro [5,5] undecane and the like. . Among these, the melting point is 100 ℃
Above, especially above 120 ° C. is preferable. Further, it is effective to use it in combination with a phosphorus-based antioxidant.

Vitamin E (tocopherol), in addition to its antioxidative effect, improves its light-shielding ability when used in combination with a light-shielding substance such as carbon black, as compared with the case where a light-shielding substance such as carbon black is added alone, and has dispersibility. Since the molded product having the same light-shielding property can be obtained even if the amount of the light-shielding substance added is reduced by 10% or more, various effects such as physical property improvement, appearance improvement, and material cost reduction are exhibited. Therefore, it is preferable.

Representative commercially available antioxidants are shown below. (1) Phenolic antioxidant; SUMILIZER B
HT (Sumitomo), YOSHINOX BHT (Yoshitomi), I
RGANOX 1076 (Ciba Geigy), MARK AO-5
0 (Adeka Argus), SUMILIZER BP-76
(Sumitomo), TOMINOX SS (Yoshitomi), IRGAN
OX 565 (Ciba Geigy), NONOX WSP (IC
I), SANTONOX (Monsanto), SUMILIZE
ER WX R (Sumitomo), ANTAGECRYSTAL
(Kawaguchi), IRGANOX 1035 (Ciba Geigy), AN
TAGE W-400 (Kawaguchi), NOCLIZER NS-6
(Ouchi Shinko), IRGANOX 1425 WL (Ciba Geigy), MARK AO-80 (Adeka Argus), SUM
ILIZER GA-80 (Sumitomo), TOPANOL CA
(ICI), MARK AO-30 (Adeka Argus),
MARK AO-20 (Adeka Argus), IRGAN
OX3114 (Ciba Geigy), MARK AO-330 (Adeka Argus), IRGANOX 1330 (Ciba Geigy),
CYANOX 1790 (ACC), IRGANOX 1010
(Ciba Geigy), MARK AO-60 (Adeka Argus), SUMILIZER BP-101 (Sumitomo), TO
MINOX TT (Yoshitomi) etc.

(2) Phosphorus antioxidant; IRGAFOS 168
(Ciba Geigy), MARK 2112 (Adeka Argus), WESTON 618 (BorgWarner), MARK
PEP-8 (Adeka Argus), ULTRANOX 626
(Borg Warner), MARK PEP-24G (Adeka Argus), MARK PEP-36 (Adeka Argus), HCA (Sanko), etc.

(3) Thioether type antioxidant; DLTD
P "YOSHITOMI" (Yoshitomi), SUMILIZER
TPL (Sumitomo), ANTIOX L (NOF), DMTD "Y
OSHITOMI "(Yoshitomi), SUMILIZER TP
M (Sumitomo), ANTIOX M (NOF), DSTP "Y
OSHITOMI "(Yoshitomi), SUMILIZER TP
S (Sumitomo), ANTIOX S (NOF), SEENOX
412S (Cipro), MARK AO-412S (Adeka Argus), SUMILIZER TP-D (Sumitomo), M
ARK AO-23 (Adeka Argus), SANDST
AB P-EPQ (Sand), IRGAFOS P-EP
Q FF (Ciba Geigy), IRGANOX 1222 (Ciba Geigy), MARK 329K (Adeka Argus), W
ESTON 399 (Borg Warner), MARK 260 (Adeka Argus), MARK 522A (Adeka Argus), etc.

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

Particularly preferred antioxidants are phenolic antioxidants, and commercially available products include various Irganox products manufactured by Ciba Geigy and Sumilizer BHT manufactured by Sumitomo Chemical Co., Ltd.
Sumilizer BH-76, Sumilizer WX-R, Sumili
zer BP-101 and the like. In addition, 2,6-di-butyl-
p-cresol (BHT), low-volatile high molecular weight phenolic antioxidant (trade name: Ireganox 1010, Iregano
x 1076, Topanol CA, Ionox 330 etc.), dilauryl thiodipropionate, distearyl thiopropionate, dialkyl phosphate and the like, and it is effective to use one or more kinds thereof, particularly two or more kinds in combination.

In particular, at least one of the above-mentioned hindered phenolic antioxidants having a melting point of 100 ° C. or higher, preferably 120 ° C. or higher, which is a typical example of a free-radical chain terminator, and a phosphorus-based oxidation agent which is a peroxide decomposing agent. It is preferable to use it in combination with at least one kind of inhibitor because the effect of preventing heat deterioration of the resin and the additive can be enhanced without deteriorating the photographic property.

In addition, a collection of data on various antioxidants and plastic additives disclosed on pages 794 to 799 of the Plastic Data Handbook (published by the KK Industrial Research Association) (K
K Chemicals Co., Ltd.), various antioxidants and PLASTICS AGE ENCYCLOPEDIA, published on pages 327-329, 1986 (KK
There are various antioxidants disclosed on pages 211 to 212 of "Plastic Age", and it is possible to select and use them from photographic properties, antioxidant effects and the like. These antioxidants are
It is essential in the present invention to use one kind or a combination of two or more kinds so as not to adversely affect the photographic properties, but it is preferable to use the minimum amount necessary for maintaining good photographic properties.

The antioxidant is the crystalline resin composition 100 described above.
It is added in a proportion of 0.0005 to 2.0 parts by weight with respect to parts by weight,
Preferably 0.001 to 1.0 parts by weight, more preferably 0.
The ratio is 005 to 0.45 parts by weight. The amount added to the entire molded product is particularly preferably 0.0008 to 0.8% by weight, most preferably 0.0015 to 0.4% by weight.

If the amount is less than 0.0005 parts by weight, there is no effect of addition and only the kneading cost increases. On the other hand, if it exceeds 2.0 parts by weight, it adversely affects the photographic light-sensitive material utilizing oxidation and reduction effects and bleeds out on the surface of the molded product to deteriorate the appearance.

Representative examples of the acrylic acid copolymer resin are shown below. Ethylene / acrylic acid copolymer resin Ethylene / methyl acrylate copolymer resin Ethylene / ethyl acrylate copolymer resin Ethylene / butyl acrylate copolymer resin Ethylene / acrylic acid-2-ethylhexyl copolymer resin etc. Methacrylic acid copolymer resin Ethylene / methyl methacrylate copolymer resin Ethylene / ethyl methacrylate copolymer resin Styrene / methyl acrylate copolymer resin Styrene / methyl acrylate copolymer resin Styrene / ethyl acrylate copolymer resin Combined resin Styrene / butyl acrylate copolymer resin Styrene / propyl acrylate copolymer resin Styrene / 2-ethylhexyl acrylate copolymer resin, etc.

Particularly preferred is an ethylene / ethyl acrylate copolymer resin (EEA) having an MFR of 1 to 25.
It is 0 g / 10 minutes, preferably 2 to 50 g / 10 minutes, and particularly preferably 3 to 30 g / 10 minutes. Ethyl acrylate content is 3
-50% by weight, preferably 5-40% by weight, particularly preferably 7-25% by weight. Union Carbide (USA), Japan Unicar Co., Ltd.
Mitsubishi Petrochemical Co., Ltd., Sumitomo Chemical Co., Ltd., Mitsui Polychemical Co., Ltd.
Etc.

The amount of the acrylic acid copolymer resin added is 5 to 90 parts by weight, preferably 10 to 80 parts by weight, more preferably 15 to 70 parts by weight, based on 100 parts by weight of the crystalline resin composition. Is. The amount of addition to the entire molded product is preferably 8 to 70% by weight, more preferably 12 to 60% by weight.

The photographic light-sensitive material molded article according to the second invention has a polyolefin resin of 50% by weight or more, a lubricant and / or an antistatic agent of 0.01 to 5.0% by weight, an antioxidant of 0.001 to 2.0% by weight, and an ion exchange function. It is characterized by comprising a polyolefin resin composition containing 0.01 to 10% by weight of an inorganic substance.

The polyolefin resin is a homopolyethylene resin, a homopolypropylene resin, a propylene / α-olefin copolymer resin, an ethylene copolymer resin (L-LDP).
The E resin, the EVA resin, the EEA resin, the acid-modified homopolyethylene resin, the acid-modified homopropylene resin, the acid-modified ethylene copolymer resin, the acid-modified propylene copolymer resin, and the like are used alone or in combination of two or more kinds.

When the content of the polyolefin resin is less than 50% by weight, solvent resistance, oil resistance and other properties of the polyolefin resin are lost.

The lubricant and / or antistatic agent are contained in an amount of 0.01 to 5.0% by weight. If it is less than 0.01% by weight, the effect of adding a lubricant and / or an antistatic agent to improve the lubricity and the effect of preventing static marks will not be exhibited, and only the kneading cost will increase. If it exceeds 5.0% by weight, the effect of increasing the amount is hardly exerted, and the material cost only increases. Further, slippage between the molten resin and the screw of the extruder is likely to occur, and the discharge amount of the resin becomes unstable. In addition, stickiness and bleed-out easily occur with the passage of time after molding. These lubricants and antistatic agents are the same as those described in the first invention.

0.01 to 2.0% by weight of antioxidant is contained. If it is less than 0.01% by weight, there is no effect of addition and only the kneading cost increases. If it exceeds 2.0% by weight, oxidation,
It adversely affects the photographic light-sensitive material that utilizes the reducing action, and bleeds out on the surface of the molded product over time to deteriorate the appearance. This antioxidant is the same as that explained in the first invention.

An inorganic substance having an ion exchange function adsorbs a gas that adversely affects the photographic properties to render it harmless, and is used in combination with a light-shielding substance to improve dispersibility. It reacts with a malodorous substance to deodorize it. There is.

As an inorganic substance having an ion exchange function, zeolite (natural zeolite analcime, erioni
te, mordenite, etc. as components) (synthetic zeolites A, NA, X, Y, hydroxy sodalite, B, R, T,
various types such as hydroxy cancrinite), the average particle diameter is 0.1 to 7 μm, preferably 0.1 to 5 μm, particularly preferably 0.1 to 3.5 μm, and 0.1 to 10% by weight in the resin composition, preferably 0.2 to 8% by weight, particularly preferably 0.3-6
% By weight. When used in combination with a light-shielding substance, it exhibits dispersibility improvement, deodorizing effect, adsorption of gases harmful to photographic properties, diatomaceous earth, activated clay, synthetic aluminum silicate, synthetic calcium silicate, synthetic magnesium silicate, There are chelating substances such as mica.

As the chelating substance, carboxylic acid type phthalocyanine type metal complexes (metal phthalocyanine tetracarboxylic acid, metal phthalocyanine octacarboxylic acid, etc.), iminodiacetic acid type chelating resin, aminocarboxylic acid type chelating resin (EDTA = ethylenediaminetetraacetic acid disodium salt) Etc.), polyamine type chelate resin, glucamine type chelate resin, supported chelate resin, 4-dimethylamino-
There are 2,6-pyridinedicarboxylic acid chelate resins and the like.

The addition amount of the inorganic substance having an ion exchange function is 0.01 to 10% by weight, preferably 0.05 to 8% by weight, and more preferably 0.1 to 6% by weight. If the addition amount is less than 0.01% by weight, the effect of addition is hardly exerted and only the kneading cost increases. On the other hand, if the addition amount exceeds 10% by weight, the effect of increasing the amount is hardly exhibited, not only the material cost is increased, but also the physical strength of the molded product for a photographic light-sensitive material is lowered and the appearance is deteriorated.

The molded photographic material of the third invention of the present invention comprises a polyolefin resin of 50% by weight or more, a lubricant and / or an antistatic agent of 0.01 to 5.0% by weight, an antioxidant of 0.001 to 2.0% by weight,
It is characterized by comprising a polyolefin resin composition containing 0.01 to 30% by weight of an oil absorbing substance having an oil absorption of 50 ml / 100 g or more.

The polyolefin resin, the lubricant, the antistatic agent and the antioxidant are the same as in the second invention.

Representative examples of the oil absorbing substance having an oil absorbing amount (measured by the oil absorbing amount A method of JIS K 6221) of 50 ml / 100 g or more are activated carbon, carbon black, talc, titanium oxide, zinc white,
Examples include clay, asbestine and kaolin. Oil absorption is 50
If the amount is less than 100 ml / ml, the effect of adsorbing additives such as lubricants, antistatic agents, and antioxidants, which tend to bleed out over time, on the surface of the oil-absorbing substance is small and the object of the present invention cannot be achieved.

When the content of the oil-absorbing substance is less than 0.01% by weight, the effect of containing the oil is not exhibited, and the content cost only increases. If it exceeds 30% by weight, the effect of increasing the amount is not exhibited and only the material cost is increased. Further, problems such as deterioration of physical strength and deterioration of appearance also occur.

The molded photographic material of the fourth present invention comprises a polyolefin resin 40% by weight or more, a lubricant and / or an antistatic agent 0.01 to 5.0% by weight, an antioxidant 0.001 to 2.0% by weight,
It is characterized by comprising a polyolefin resin composition containing 5 to 45% by weight of an acrylic acid copolymer resin.

When the content of the polyolefin resin is less than 40% by weight, rigidity, solvent resistance, oil resistance and other properties of the polyolefin resin are lost. This polyolefin resin is the same as that described in the second invention.

The acrylic acid copolymer resin is contained in an amount of 5 to 45% by weight. 5% by weight of acrylic acid copolymer resin
If the amount is less than the above, the effect of reducing bleed-out of the lubricant and / or antistatic agent with time is small, and the object of the present invention is not achieved, but only the kneading cost increases. When the acrylic acid copolymer resin exceeds 45% by weight, rigidity, solvent resistance, oil resistance, and other properties of the polyolefin resin are lost, and the offensive odor of the acrylic acid comonomer is strong, which makes the user uncomfortable. Further, blocking is likely to occur, which makes practical application difficult. This acrylic acid copolymer resin is the same as that described in the first invention.

The lubricant, antistatic agent and antioxidant are secondarily
Is the same as that described in the present invention.

The molded article for photographic light-sensitive material of the fifth invention is
Polyolefin resin 20% by weight or more, lubricant and / or antistatic agent 0.01 to 5.0% by weight, antioxidant 0.001 to 2.0% by weight, acrylic acid copolymer resin 5 to 75% by weight, light-shielding substance
It is characterized by comprising a polyolefin resin composition containing 0.01 to 30% by weight.

When the content of the polyolefin resin is less than 20% by weight, rigidity and other properties of the polyolefin resin are lost, and blocking is likely to occur even if a light-shielding substance is contained, resulting in lack of lubricity and for photographic light-sensitive materials. It is difficult to put into practical use as a molded product. This polyolefin resin is the same as that described in the second invention.

Further, the acrylic acid copolymer resin is contained in an amount of 5 to 75% by weight. 5% by weight of acrylic acid copolymer resin
If the amount is less than the above, the effect of reducing bleed-out of the lubricant and / or antistatic agent with time is small, and the object of the present invention is not achieved, but only the kneading cost increases. If the acrylic acid copolymer resin exceeds 75% by weight, the odor of acrylic acid monomer becomes strong and the photographic properties of the photographic light-sensitive material may be adversely affected. Further, it becomes more expensive and blocking is more likely to occur, making it difficult to put into practical use as a molded article for a photographic light-sensitive material. This acrylic acid copolymer resin is the same as that described in the first invention.

If the light-shielding substance is contained in an amount of 0.01 to 30% by weight, and if the light-shielding substance is less than 0.01% by weight, the effect of addition is hardly exerted, and the light-shielding property required for the photographic light-sensitive material cannot be secured. It only increases kneading costs. The light-shielding substance
If it exceeds 30% by weight, the effect of increasing the amount is not exhibited and only the material cost is increased. Further, problems such as deterioration of physical strength and deterioration of appearance also occur.

Typical examples of the light-shielding substance are shown below. (1) Inorganic compound A. Oxide: Silica, diatomaceous earth, alumina, titanium oxide, iron oxide, zinc oxide, magnesium oxide, antimony oxide, barium ferrite, strontium ferrite, beryllium oxide, pumice, pumice balloon, alumina fiber, etc. B. Hydroxide ... Aluminum hydroxide, magnesium hydroxide, basic magnesium carbonate, etc. C.I. Carbonate ... Calcium carbonate, magnesium carbonate, dolomite, dawsonite, etc. D. (Sulfite) ... Calcium sulfate, barium sulfate, ammonium sulfate, calcium sulfite, etc. E. Silicates ... Talc, clay, mica, asbestos,
Glass fiber, glass balloon, glass beads, calcium silicate, montmorillonite, bentonite, etc. F. Carbon ... Carbon black, graphite, carbon fiber, carbon hollow sphere, etc. G. Others: Iron powder, copper powder, lead powder, tin powder, stainless powder,
Pearl pigment, aluminum powder, molybdenum sulfide, zeolite, polon fiber, silicon carbide fiber, brass fiber, potassium titanate, lead zirconate titanate, zinc borate, barium metaborate, calcium borate, sodium borate, aluminum paste, etc.

(2) Organic compounds Wood powder (pine, oak, sawdust, etc.), shell fibers (almonds, peanuts, fir shells, etc.), various colored fibers such as cotton, jute, paper strips, cellophane strips, nylon fibers , Polypropylene fiber, starch (including modified starch and surface-treated starch), aromatic polyamide fiber, etc.

Of these light-shielding substances, various carbon blacks are preferable because they can adsorb a lubricant, a surfactant, etc. on the surface to reduce the amount of bleed-out.

[0100] Examples of classification by carbon black raw material include gas black, furnace black, channel black, anthracene black, acetylene black, Ketjen carbon black, thermal black,
Lamp black, oil smoke, pine smoke, animal black, vegetable black, etc. are available. In the present invention, furnace carbon black is preferable for the purpose of ensuring light-shielding properties, improving cost, physical properties, and not adversely affecting photographic properties, and acetylene carbon black and modified by-products are used as light-shielding substances that are expensive but have an antistatic effect. Ketjen carbon black, which is carbon black, is preferred. If necessary, it is also preferable to mix the former and the latter according to the required characteristics. Although there are various forms of incorporating the light-shielding substance into the resin composition, the masterbatch method is preferable in terms of cost, prevention of contamination of the workplace, and the like. In Japanese Patent Publication No. 40-26196, which is a publicly known document, a method of dispersing a carbon black in a solution of a polymer dissolved in an organic solvent to prepare a polymer-carbon black masterbatch is disclosed in Japanese Patent Publication No. 43-10362. Describes a method of dispersing carbon black in polyethylene to form a masterbatch.

As a light-shielding substance of a molded product for a photographic light-sensitive material of the present invention, when used, there is no fog on the photographic light-sensitive material, little increase or decrease in photosensitivity, and a large light-shielding ability. Products, polystyrene resin injection-molded products, L-LDPE resin films, etc., pinholes are less likely to occur in injection-molded products and light-shielding films, such as carbon black solidification (fish) and fish eyes. So, the pH of carbon black
(Measured by JIS K 6221) is 6.0 to 9.0, preferably 6.5
~ 8.5, average particle size (measured by electron microscopy) 10-120m
μ, particularly 12 to 70 μm is preferable, and among them, volatile components (measured by JIS K 6221) are 3.5% or less,
Most preferably 1.5% or less, DBP oil absorption (JIS K 6
221 is a furnace carbon black having an oil absorption amount of 221) of 50 ml / 100 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 many cause fog on the photographic light-sensitive material. Most of the lamp blacks also have a pH of 5.0 or less and adversely affect the photographic properties, so even if it is absolutely necessary to use it, it will react so as not to adversely affect the photographic properties,
Only those that can be used should be selected in combination with the substance to be adsorbed and the effect on photographic properties should be investigated. Also, A
Sulfur content measured by STM D 1619-60 is 0.9%
If it is not below 0.7%, the photographic properties may be adversely affected. In particular, it is preferable to select a free sulfur component having an adverse effect on the photographic properties of the photographic light-sensitive material of 0.1% or less, most preferably 0.05% or less.

Practical carbon black products are, for example, carbon black # 20 manufactured by Mitsubishi Kasei.
(B), # 30 (B), # 33 (B), # 40 (B), # 41 (B), # 44 (B),
# 45 (B), # 50, # 55, # 100, # 600, # 950, # 1000,
Examples include # 2200 (B), # 2400 (B), MA8, MA11, MA100. Overseas products include, for example, Cabot's Black Pearls 2,46,70,71,74,80,81,607.
Etc., Regal 300, 330, 400, 660, 991, SRF-S, etc.
Vulcan 3, 6 etc., Sterling 10, SO, V, S, FT
-FF, MT-FF, etc. are mentioned. In addition, Ashland Chemical Company's United R, BB, 15, 102, 3001, 3
004, 3006, 3007, 3008, 3009, 3011, 3012, XC-301
6, XC-3017, 3020 and the like, but not limited thereto.

The second preferred light-shielding substance after carbon black is an inorganic pigment having a refractive index of 1.50 or more as measured by the Larsen oil immersion method, and various metal powders, metal flakes, metal pastes, metal fibers and carbon fibers. The preferred refractive index is 1.
Representative examples of 50 or more inorganic pigments and metal powders are shown below,
The present invention is not limited to these. The number in parentheses indicates the refractive index. Inorganic pigments with a refractive index of 1.50 or higher include rutile titanium oxide (2.75) and silicon carbide (2.6
7), anatase type titanium oxide (2.52), zinc oxide (2.3
7), antimony oxide (2.35), lead white (2.09), zinc white (2.02), lithopone (1.84), zircon (1.80), corundum (1.77), spinel (1.73), apatite (1.
64), barite powder (1.64), barium sulfate (1.64), magnesite (1.62), dolomite (1.59), calcium carbonate (1.58), talc (1.58), calcium sulfate (1.5
6), silicic acid anhydride (1.55), quartz powder (1.54), magnesium hydroxide (1.54), hydrochloric acid magnesium carbonate (1.5
2), alumina (1.50), etc. Particularly preferred is a light-shielding substance having a refractive index of 1.56 or more, and most preferably 1.60 or more.

Calcium silicate having a refractive index of less than 1.50 (1.
46), diatomaceous earth (1.45), hydrous silicic acid (1.44), etc. have a small light-shielding ability, and therefore a large amount needs to be added, and use as a light-shielding substance is not preferable. In addition, due to the recent boom in overseas travel, ISO has become an inspection machine that uses X-rays for baggage inspection at airports.
X when passed through high-speed photographic film with sensitivity of 400 or more
Fogging tends to occur due to the lines. In order to prevent this, it is preferable to use a light-shielding substance having a specific gravity of 3.1 or more, preferably 3.4 or more. Specific gravity of 3.1 or more, preferably 3.4
Above, particularly preferably, the form of the light-shielding substance having an X-ray blocking property other than the light-shielding property of 4.0 or more is not limited to the following representative examples, and any form such as pigment, powder,
It may be flakes, whiskers, fibers and the like. Light-shielding substances with a specific gravity of 3.1 or more include silicon carbide, barium sulfate, molybdenum disulfide, lead oxide (lead white), iron oxide,
Titanium oxide, magnesium oxide, barium titanate, copper powder, iron powder, brass powder, nickel powder, silver powder, lead powder, steel powder, zinc powder, tungsten whiskers, silicon nitride whiskers, copper whiskers, iron whiskers, nickel whiskers , Chromium whiskers, stainless powder and whiskers, magnesite, apatite, spinel, corundum, zircon, antimony trioxide, barium carbonate, zinc white, chromium oxide, tin powder and mixtures thereof.

Particularly preferable light-shielding substances for imparting X-ray shielding properties are zircon, corundum, barium sulfate, barium chloride, barium titanate, lead powder, lead oxide (iron black etc.), zinc powder, zinc white, tin. Powder, stainless powder, stainless whiskers, iron oxide, tungsten whiskers, nickel whiskers. Particularly preferred as a light-shielding substance as a molded product for high-sensitivity photographic film having an ISO sensitivity of 400 or more is a light-shielding substance having a refractive index of 1.50 or more and a specific gravity of 3.1 or more, and most preferably a light-shielding property having a refractive index of 1.56 or more and a specific gravity of 3.4 or more. It is a substance. Table 1 shows the refractive index and the specific gravity of the light-shielding substance.

[0106]

[Table 1]

The content of the X-ray shielding light-shielding substance is preferably 5 to 80% by weight, more preferably 10 to 70% by weight, and most preferably 20 to 60% by weight.

Further, the X-ray shielding light-shielding substance does not adversely affect the photographic light-sensitive material and does not deteriorate the film moldability, so that the loss on drying at 100 ° C. for 5 hours is preferably 2.0% by weight or less, It is preferably used in an amount of 1.0% by weight or less, and most preferably 0.5% by weight or less.

A typical example of an oil-absorbing inorganic pigment having the effect of adsorbing a lubricant, an antioxidant, an organic nucleating agent, etc., which easily bleeds out, and adsorbing a deodorant, an aromatic agent, an oxygen scavenger, etc. 52), asbestine (50), clay (51), titanium oxide (56), kaolin (60), talc (60 or more), carbon black (60 or more), activated carbon, etc. The numbers in parentheses indicate the oil absorption (measured by the oil absorption A method of JIS K 6221. Unit: ml / 100 g).

Typical examples of metal powder (including metal paste) include aluminum powder, aluminum paste,
There are copper powder, stainless powder, iron powder, nickel powder, brass powder, silver powder, tin powder, zinc powder, steel powder and the like.

In the present invention, the term "aluminum powder" is meant to include both aluminum powder and aluminum paste. The aluminum powder whose surface is coated with a surface coating substance and the aluminum paste whose low-volatile substance is removed are thermoplastic resins. What is kneaded in is preferable.

Here, the aluminum paste means the presence of mineral spirits and a small amount of higher fatty acids such as stearic acid or oleic acid when producing aluminum powder by a known method such as a ball mill method, a stamp mill method, or an atomizing method. It was originally made into a paste. In the present invention, the aluminum paste and various aromatic monovinyl resins (polystyrene resin, rubber-containing polystyrene resin, etc.), polyolefin thermoplastic resins (various polypropylene resins, various polyethylene resins, acid-modified resins, EVE resins, EEA resins, EAA resins, etc.) , Low molecular weight polyolefin resin, paraffin wax, tackifier, dispersant such as metallic soap, etc. are heated and kneaded, and low volatile substances (mineral spirit, white spirit with strong malodor)
It is preferable to use a volatile substance having a content of 3% or less, preferably 1% or less, particularly preferably 0.5% or less, which has been removed by a vacuum pump or the like, as the aluminum paste compound resin or aluminum paste masterbatch resin.

It is particularly preferable to use as an aluminum paste masterbatch resin in order to eliminate adverse effects on photographic light-sensitive materials and odors. For example, even if the content of mineral spirits in the master batch resin having an aluminum paste content of 40% by weight is 1.0% by weight, if the aluminum paste concentration in the molded product for photographic light-sensitive material is set to 2% by weight, aluminum 19 parts by weight of natural resin will be kneaded with 1 part by weight of paste masterbatch, and mineral spirits may be removed as a gas during heating during molding, so the content of mineral spirits is 0.05 parts by weight. % Or less. As a result, the photographic light-sensitive material is not adversely affected, and the odor is reduced.

The aluminum powder is not only the molten aluminum made into powder by atomization method, granulation method, rotary disc dropping method, evaporation method, etc., but also aluminum foil is crushed by a ball mill method, a stamp mill method or the like to form flakes. Including those in the shape. Since the aluminum powder alone is unstable, various known surface coating treatments for inactivating the surface of the aluminum powder are performed.

In order to put it into practical use as a molded article for a photographic light-sensitive material of the present invention, the total content of the light-shielding substance is 0.01 to 30% by weight from the viewpoint of quality assurance, photographic performance assurance, moldability, and economical efficiency.
It changes depending on the shading ability. The total content of carbon black and aluminum powder with excellent light-shielding ability is 0.05 to 20.
Wt% is preferred, 0.1-10 wt% is more preferred, 0.2
~ 7 wt% is most preferred. If the content is less than 0.01% by weight, the light-shielding property will be insufficient and light fog will occur unless the thickness of the molded product for a photographic light-sensitive material is increased. For this reason, the molding speed of the molded product for a photographic light-sensitive material becomes slow (because the cooling time becomes long), and the amount of resin used becomes large, so that it becomes expensive and difficult to put into practical use. When the content exceeds 30% by weight, the dispersibility deteriorates, the generation of microgrids (aggregated impurities) increases, pressure fog and scratches occur on the photographic light-sensitive material, and moisture in the molded product for photographic light-sensitive material The amount increases due to an increase in the amount of water adsorbed on the carbon black, which adversely affects the photographic performance of the photographic light-sensitive material (fogging, abnormal sensitivity, abnormal color development, etc.). Furthermore, the moldability of a molded product for a photographic light-sensitive material is deteriorated (foaming, silver strips, pinholes, short shots, etc.) and the physical strength is lowered, which makes practical application difficult.

Dispersion of a light-shielding substance (carbon black, aluminum powder, an inorganic pigment having a refractive index of 1.50 or more, an inorganic pigment having a specific gravity of 3.4 or more, an inorganic pigment having an oil absorption of 50 ml / 100 g or more) in a resin Properties, improvement of resin fluidity, prevention of generation of microgrit that causes friction fog, pressure fog, and scratches on photographic photosensitive materials, prevention of volatile substances harmful to photographic properties, reduction of moisture absorption, prevention of die lip stains, etc. For this reason, it is preferred that the surface is coated with a surface-coating substance. Representative examples of surface coating materials are shown below.

(1) Coupling agent Coupling agent coating containing azidosilanes (JP-A-62-62)
-32125, etc.) Silane-based coupling agent coating (aminosilane, etc.) Titanate-based coupling agent coating

(2) Deposit silica and then deposit alumina.

(3) Coating with higher fatty acid metal salt such as zinc stearate, magnesium stearate, calcium stearate

(4) Surfactant coating of sodium stearate, potassium stearate, oxyethylene dodecyl amine, etc.

(5) A barium sulfide aqueous solution and a sulfuric acid aqueous solution are reacted in the presence of an excessive amount of barium ions to produce barium sulfate having an average particle diameter of 0.1 to 2.5 μm, and an aqueous alkali silicate solution is added to this water slurry. To form barium silicate on the surface of barium sulfate, then add mineral acid to the slurry, decompose the barium silicate into hydrous silica and deposit it on the surface of barium sulfate

(6) Hydrated metal oxide (one or more kinds of hydrated oxide of titanium, aluminum, cerium, zinc, iron, cobalt or silicon) and / or metal oxide (titanium, aluminum, cerium) Surface coating with a composition consisting only of one, two or more of oxides of zinc, iron, cobalt or silicon)

(7) A polymer having one or more reactive groups selected from the group consisting of aziridine group, oxazoline group and N-hydroxyalkylamide group in the molecule is coated.

(8) Surface coating with polyoxyalkylene amine compound

(9) Surface coating with cerium cation, selected acid anion and alumina

(10) Surface coating with an alkoxytitanium derivative having an α-hydroxycarboxylic acid residue as a substituent

(11) Surface coating with polytetrafluoroethylene

(12) Surface coating with polydimethylsiloxane or modified silicon

(13) Surface coating with phosphoric acid ester compound

(14) Surface coating with dihydric or tetrahydric alcohol

(15) Surface coating with olefin wax (polyethylene wax, polypropylene wax)

(16) Surface coating with aluminum hydroxide oxide

(17) Silica or zinc compound (zinc chloride, zinc hydroxide, zinc oxide, zinc sulfate, zinc nitrate, zinc acetate,
One or a combination of two or more such as zinc citrate)
With surface coating

(18) Surface coating with polyhydroxy saturated hydrocarbon, etc.

As a surface coating substance for the above-mentioned light-shielding substance, the photographic characteristics of the photographic light-sensitive material are less adversely affected by fogging and the like,
Improves the dispersibility of light-shielding substances, reduces the generation of spots, and improves the fluidity of resin (1), (3), (12), (14), (15),
In addition to (16) and the like, organometallic chelate compounds, various antistatic agents, lubricants, drip-proofing agents, and surfactants are preferable.

Particularly, an ester of an aliphatic monocarboxylic acid having 20 to 40 carbon atoms and an aliphatic monohydric alcohol having 20 to 40 carbon atoms is 0.001 to 2% by weight, preferably 0.005 to 1% by weight, and particularly preferably By adding 0.01-0.5% by weight,
It has been found that the effect of preventing the above problems can be exhibited. In particular, it not only reduces the adverse effect on the photographic properties of the photographic light-sensitive material but also reduces the motor load, improves the dispersibility of the light-shielding substance, improves the moldability, and makes the appearance of the molded product excellent.

The ester used in the present invention includes an aliphatic monocarboxylic acid having 20 to 40 carbon atoms, preferably 25 to 35 carbon atoms and an aliphatic monohydric alcohol having 20 to 40 carbon atoms, preferably 25 to 35 carbon atoms. It is an ester.

Examples of the above-mentioned monocarboxylic acid include montanic acid, melissic acid, cerotic acid, brisic acid, laxeric acid and the like.

Examples of monohydric alcohols are montyl alcohol, melysyl alcohol, lacsyl alcohol,
Examples include ceryl alcohol and brisyl alcohol.

Since these improve the fluidity of the thermoplastic resin and achieve uniform kneading, they are also very excellent as a surface coating substance for the light-shielding substance. further,
When used as a dispersant for the inorganic and / or organic nucleating agent in the surface coating, various excellent effects such as scattering prevention, bleed-out prevention, uniform dispersibility improvement, and resin fluidity improvement are exhibited.
The surface coverage of these light-shielding substances is preferably 0.001 to 5% by weight, more preferably 0.001 to 5% by weight, based on the light-shielding substances such as carbon black or aluminum powder.
It is 0.01 to 3% by weight, most preferably 0.05 to 1.5% by weight. When the coating amount is 0.001% by weight or less, the coating effect is hardly exhibited. If the coating amount exceeds 5% by weight, bleed-out increases with time and slip between the resin and the screw occurs and the discharge amount fluctuates, resulting in large variation in thickness and difficulty in practical application.

The total amount of sulfur in the above total light-shielding substance (AST
MD-1619) is 1.0% or less, preferably 0.8% or less, particularly preferably 0.5% or less, and the free sulfur content is 150 ppm or less, preferably 50 ppm or less, particularly preferably 30 ppm or less, according to ASTM D-1506. The ash content is 0.5% or less, preferably 0.4% or less, particularly preferably 0.3% or less,
Aldehyde compound content is 0.2% or less, preferably 0.1%
It is necessary to note that the photographic properties are adversely affected unless the content is controlled below 0.05%.

Further, since cyanide compounds also adversely affect the photographic performance of photographic light-sensitive materials, 4-pyridinecarboxylic acid.
The light-shielding substance has a value of 20 ppm or less, preferably 10 ppm or less, particularly preferably 5 ppm or less, obtained by converting the amount of hydrogen cyanide quantified by the pyrazolone absorption spectrometry into the unit of ppm with respect to the weight of the light-shielding substance.

The amount of the light-shielding substance added is preferably 0.01 to
The range is 30% by weight, more preferably 0.05 to 20% by weight, and most preferably 0.1 to 10% by weight. Effect of combined use with substances that are colored by light, such as vitamin E and photosensitive resin (Since the light-shielding ability is improved by improving the coloring concentration, it is possible to reduce the amount of light-shielding substances added, resulting in a decrease in physical strength. The degree is reduced, the melt sealing property is improved, the moldability is improved, and the resin fluidity is improved). Particularly when the thickness is 100 μm or less, the amount of the light-shielding substance added is 0.1 to 15% by weight, preferably 0.5 to 10% by weight, particularly preferably 1.0 to 7.0% by weight, from the viewpoint of ensuring light-shielding property and physical strength. It is a range.

Lubricants, antistatic agents and antioxidants are secondarily
Is the same as that described in the present invention.

The photographic light-sensitive material molded article of the sixth present invention has a polyolefin resin of 50% by weight or more, a refractive index (measured by the Larsen oil immersion method) of 1.50 or more, and an oil absorption of 50 ml / 0.01 to 30% by weight of 100g or more light-shielding substance,
A polyolefin resin composition comprising 0.001 to 2.0% by weight of one or more of an antioxidant, a radical scavenger and an antioxidant synergist, and 0.01 to 5.0% by weight of a lubricant and / or an antistatic agent. Has been done.

The molded article of the photographic light-sensitive material according to the sixth aspect of the present invention comprises one of an antioxidant, a radical scavenger and an antioxidant synergistic effect agent.
It contains 0.001 to 2.0% by weight of seeds or more. 0.001% by weight
If the amount is less than the above, there is almost no effect of addition and only the kneading cost increases. If it exceeds 2.0% by weight, not only the effect of increasing the amount is not exhibited, but also the material cost is increased and the photographic light-sensitive material utilizing the oxidation and reduction effects is adversely affected.

The radical scavenger is the same as described above.

Antioxidant synergists are similar to those described above.

The polyolefin resin, lubricant and antistatic agent are the same as those described in the second invention.

In the molded photographic material of the seventh aspect of the present invention, the container body has a melt flow rate (measured at ASTM D-1238, temperature 190 ° C., load 2.16 kg) of 5 to 60 g / 10.
Min, density (ASTM D-1505) is 0.941g / cm ³ ~ 0.985
g / cm ³ , crystallinity of 75% or more by X-ray diffraction method, flexural rigidity (ASTM D-747) of 6000 kg / cm ² or more, Shore hardness (ASTM D-2240) of 60 D or more, notched at 23 ° C Izod impact strength (ASTMD-256) is 2.0kg ・ cm / c
50% by weight or more of homopolyethylene resin and / or ethylene / α-olefin copolymer resin having m or more, Vicat softening point (ASTM D-1525) of 110 ° C or more and melting point (ASTM D-2117) of 120 ° C or more, inorganic And a container for a photographic film formed of a polyethylene resin composition containing 0.01 to 2% by weight of one or more organic nucleating agents and 0.001 to 2% by weight of one or more antioxidants and radical scavengers. It is configured to be there.

When the melt flow rate is less than 5 g / 10 minutes, the fluidity of the resin is poor and molding failures such as short shots and weld lines occur frequently, making it difficult to put into practical use. When the melt flow rate exceeds 60 g / 10 minutes, the molecular weight is small, the physical properties are deteriorated, and it is difficult to put it into practical use as a container for photographic film which requires sealing property and physical strength.

If the density is less than 0.941 g / cm ³ , the rigidity is insufficient, the material is easily deformed, the suitability for protecting the photographic film is insufficient, and it is difficult to put it into practical use as a photographic film container. If the density exceeds 0.985 g / cm ³ , polymerization will be difficult and expensive, and practical application will be difficult.

If the crystallinity is less than 75%, the rigidity is insufficient and the solvent resistance, oil resistance, heat resistance, etc. are reduced, making practical application difficult.

If the flexural rigidity is less than 6000 kg / cm ² , the rigidity is insufficient and the film is easily deformed, and the suitability for protecting the photographic film is lacking, and it is difficult to put it into practical use as a photographic film container.

If the Shore hardness is less than 60 D, scratches are likely to occur on the surface, abrasion debris is likely to occur when it comes into contact with other substances, the external appearance is deteriorated, and the commercial value is reduced, making it difficult to put into practical use. .

If the Izod impact strength is less than 2.0 kg · cm / cm, cracks and damages are likely to occur when the photographic film container in which the photographic film is hermetically packed and dropped from a height of 1 m or more onto a concrete floor or the like. Therefore, it becomes difficult to ensure a hermetically sealed state, which makes it difficult to put into practical use.

If the Vicat softening point is less than 110 ° C., it will be deformed or it will be difficult to secure hermeticity because it will lack heat resistance if left in sunlight.

If the melting point is less than 120 ° C., the same problems as in the case where the Vicat softening point is less than 110 ° C. occur and it is difficult to put it into practical use.

Content of inorganic and organic nucleating agents is 0.01% by weight
If the amount is less than the above, the effect of addition is hardly exhibited and only the kneading cost increases. If it exceeds 2% by weight, there is almost no effect of increasing the amount and the material cost only increases. Further, problems such as an increase in malodor during molding and bleeding out with the passage of time after molding occur.

When the amount of one or more of the antioxidant and the radical scavenger is less than 0.001% by weight, there is almost no effect of addition and only the kneading cost increases. If it exceeds 2% by weight, not only the effect of increasing the amount is not exhibited, but also the material cost is increased and the photographic light-sensitive material utilizing the oxidation and reduction action is adversely affected.

In the molded article of the photographic light-sensitive material of the eighth invention, the container body has a melt flow rate of 5 to 80 g / 10 minutes and a density of
^{0.941g / cm 3 ~0.985g / cm 3} , crystallinity by X-ray diffractometry of 75% or more, the bending rigidity 6000 kg / cm ² or more homopolyethylene resin and / or an ethylene · alpha-olefin copolymer resin 50 weight % Or more and a carboxylic acid having 3 or more carbon atoms and a nitrogen-containing heterocyclic compound having an amino group or a hydroxyl group at the α-position, and / or an alicyclic carboxylic acid amide compound of a divalent or more aliphatic amine And a haze containing 0.01 to 5% by weight of an organic nucleating agent comprising 50% or less of a polyethylene resin composition.

When the melt flow rate is less than 5 g / 10 minutes, the fluidity of the resin is poor and molding failures such as short shots and weld lines occur frequently, making it difficult to put into practical use. When the melt flow rate exceeds 80 g / 10 minutes, the molecular weight is small, the physical properties are deteriorated, and it is difficult to put it into practical use as a photographic film container requiring sealing property and physical strength. density,
The crystallinity and flexural rigidity are the same as in the seventh invention.

In the molded article for photographic light-sensitive material of the present invention, various thermoplastic elastomers are contained in an amount of 3% by weight or more, preferably 3 to.
50% by weight, more preferably 5 to 40% by weight, and most preferably 7 to 35% by weight can be contained for the purpose of improving flexibility and improving impact strength at low temperature. Ethylene / propylene rubber is particularly preferable. Ethylene / propylene rubber includes EPM, which is a copolymer of ethylene and propylene,
EP which is a terpolymer of ethylene, propylene and a diene monomer for crosslinking (ethylidene norbornene etc.)
There are two types of DM. Since EPM and EPDM have no unsaturated bond in the polymer main chain, they have excellent heat resistance,
It is particularly preferable because it has weather resistance and does not adversely affect the photographic light-sensitive material.

It is preferable to add an antiblocking agent to the molded article for photographic light-sensitive material of the present invention in order to prevent blocking. This antiblocking agent includes silica (including natural and synthetic silica), calcium carbonate, talc (magnesium silicate), aluminum silicate, calcium silicate, fatty acid amide lubricant, higher fatty acid polyvinyl ester, n-octadecyl urea, N, N. '-
There are dioleyl oxamide, N-ethanol stearic acid amide, dicarboxylic acid ester amide and the like. Among them, silica is preferable, the preferable addition amount is 0.01 to 5.0% by weight, and the particularly preferable addition amount is 0.05 to 3.5% by weight. 0.0
If it is less than 1% by weight, the antiblocking effect is small and only the kneading cost increases. If it exceeds 5.0% by weight, not only lump-like non-uniform failures (bugs) occur, but also the physical strength and heat sealability of the film deteriorate.

This silica has an average particle size of 0.3 to 20.
μm, particularly 0.5 to 15 μm is preferable. 0.3 μm
If it is less than the above, cohesiveness is strong and many spots occur. In addition, the antiblocking effect is also small. If it exceeds 20 μm, not only the surface of the film becomes silica and the surface of the film becomes rough, but also scratches and the like are likely to occur on the photographic light-sensitive material.

The molded article for a photographic light-sensitive material of the present invention is a drip-proof substance because it prevents dew condensation and the like, and prevents additives such as lubricants and antioxidants, which easily bleed out, from depositing in a white powder form. Can be included. This drip-proof substance includes all substances that make the contact angle of water 45 degrees or less, preferably 35 degrees or less. Particularly preferred representative antidrip agents are shown below, but the present invention is not limited thereto. Further, any two or more of a water-absorbing substance, a hygroscopic substance and a drip-proofing agent can be mixed and used.

Representative examples of the anti-drip agent are shown below. Diglycerin monostearate, polyglycerin monopalmitate, sorbitan monolaurate, sorbitan monostearate, sorbitan monooleate, sorbitan monoerucate, polyoxyethylene sorbitan fatty acid ester,
Stearic acid monoglyceride, palmitic acid monoglyceride, oleic acid monoglyceride, lauric acid monoglyceride, polyoxyethylene nonylphenol ether, sorbitan sesquipamitate, 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 3mol adduct, diglycerin palmite , Glycerin palmitate, glycerin palmitate / ethylene oxide 3 mol adduct, etc.

The amount of the above-mentioned drip-proof substance added is 0.01 to
5.0% by weight is preferred. Particularly, 0.1 to 3.0% by weight is preferable. If 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.

When the amount added exceeds 5.0% by weight, the antifogging effect is sufficiently exhibited, but the effect of increasing the amount is almost lost and the cost is increased. 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.

Further, it is preferable to subject the molded article containing the drip-proof substance to surface activation treatment such as corona discharge treatment, ozone contact treatment, plasma treatment or the like, because the antifogging action and the dripproofing action can be more effectively exhibited.

A fatty acid metal salt may be added to the molded article for photographic light-sensitive material of the present invention for the purpose of inactivating a substance which adversely affects photographic performance. 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. Further, this fatty acid metal salt improves the dispersibility and moldability of the light-shielding substance, and further neutralizes and harmless halides 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, lactic acid, succinic acid, stearyl lactic acid, hydroxystearic acid, ricinoleic acid, naphthenic acid, oleic acid and erucic acid, and Li, Na, Mg, Ca and Sr. , Ba, Z
There are compounds with metals such as n, Cd, Al, Sn and Pb.

The amount of the fatty acid metal salt added is preferably 0.01 to 10.0 parts by weight, relative to 100 parts by weight of the crystalline resin composition,
0.1 to 5.0 parts by weight is more preferable. The amount added to the entire molded product is preferably 0.01 to 5.0% by weight, more preferably 0.03 to 3.0% by weight, and most preferably 0.05 to 5.0% by weight.
It is 1.5% by weight.

If the amount added is less than 0.01% by weight, there is almost no effect of the addition and only the kneading cost increases. If it exceeds 5.0% by weight, bleed out may occur, or the resin and screw may slip, resulting in unstable discharge.
In addition to frequent molding failures, it lacks uniform kneading properties.

A nucleating agent may be added as another additive to the resin composition used in the present invention. 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, other aluminum salts, and aromatics. Group phosphate metal salts, alkyl alcohols having 8 to 30 carbon atoms, condensation products of polyhydric alcohols and aldehydes, and alkylamines,
For example, aluminum p-t-butylbenzoate, 1, 2,
3,4-dibenzylidene sorbitol, a di-substituted benzylidene sorbitol compound represented by the following formula

[0175]

[Chemical 5] {In the formula, 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. }, A metal salt of stearyl lactic acid such as calcium or magnesium, or a compound represented by the following formula such as N- (2-hydroxyethyl) -stearylamine.

[0176]

[Chemical 6] {In the formula, R ₃ is an alkyl group having 8 to 30 carbon atoms, and k
And l are both 0 to 10 and k + 1 ≧ 1. }, 1,2-hydroxystearic acid lithium salt, sodium salt, potassium salt, calcium salt, magnesium salt and other metal salts, stearyl alcohol, lauryl alcohol and other alkyl alcohols, sodium benzoate,
Including benzoic acid and sebacic acid.

Among the organic nucleating agents, typical examples of sorbitol compounds which have a particularly large crystallization promoting effect, reduce molding failures, shorten molding cycle, improve rigidity, and improve coloring appearance are shown 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 Aromatic hybrocarbon groups or derivatives thereof 1 ・ 3-benzylidene sorbitol 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 (me thoxybenzylidene) 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.

Among the above organic nucleating agents, the sorbitol compound has a great addition effect and rarely exerts an adverse effect on the photographic properties of the photographic light-sensitive material. The amount of the sorbitol-based organic nucleating agent added is 0.005 to 5.0% by weight, preferably 0.01 to 3.0% by weight, more preferably 0.03 to 2.0% by weight, and most preferably
It is 0.05 to 1.0% by weight.

Examples of the inorganic nucleating agent include alkali metal hydroxides such as lithium hydroxide, sodium hydroxide and potassium hydroxide, alkali metal oxides such as sodium oxide, lithium carbonate, sodium carbonate, potassium carbonate and sodium hydrogen carbonate. , An alkali metal carbonate such as potassium hydrogen carbonate, an alkaline earth metal hydroxide such as calcium hydroxide, magnesium hydroxide and barium hydroxide, an alkaline earth metal oxide such as calcium carbonate and calcium oxide, and the like.

The nucleating agent is not limited to these, and other known nucleating agents can be used. Needless to say, the nucleating agent is not limited to a single type and two or more types can be used in combination. The amount of the inorganic nucleating agent added is preferably 0.01 to 5.0% by weight, more preferably 0.05 to 3.0% by weight.

Among the nucleating agents, the dibenzylidene sorbitol compound which is an organic nucleating agent is particularly preferable. Particularly preferred in the present invention is a polyolefin resin which is a crystalline resin (preferably homopolypropylene resin, propylene / α).
Olefin block copolymer resin, Young propylene · alpha-olefin random copolymer resin, density 0.910 g / cm ³ or more homo polyethylene resin and density 0.870 g / cm ³ or more ethylene · alpha-olefin copolymer resin) The following di-substituted benzylidene that can improve the rate, physical strength, rigidity, molding speed, decrease molding failure, etc., and can improve the offensive odor and bleed-out which were the drawbacks of conventional organic nucleating agents. Sorbitol compositions are particularly preferred. As an essential component of the di-substituted benzylidene sorbitol composition, the compound represented by the general formula (I)

[0183]

[Chemical 7] {In the formula, R and R ′ are each independently a chlorine atom,
Represents an atom or a group selected from the group consisting of a methyl group and an ethyl group}, and a solid powder of a dibenzylidene sorbitol derivative of the formula (II)

CH ₃ (CH ₂ ) nCOOH (II) (wherein n represents 14 to 30, preferably 18 to 27, most preferably 20 to 25) higher fatty acid, Provided is a dibenzylidene sorbitol derivative composition in which a higher fatty acid is contained by coating the surface of a solid powder of the dibenzylidene sorbitol derivative.

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

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 suitable dibenzylidene sorbitol derivatives are 1,3-2,4-dipmethylbenzylidene sorbitol, 1,3-p methylbenzylidene-2,4-p chlorobenzylidene sorbitol and 1,3-p chloro. Benzylidene-2,4-p-methylbenzylidene sorbitol.

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

Preferred representative examples of the molded article for a photographic light-sensitive material containing an organic grading agent are described below.

(1) 0.01 to 5% by weight of an organic nucleating agent composed of a diacetal composition having a composition of 0.3 ≦ Z ≦ 0.8 (weight basis), which is a mixture of compounds represented by the following general formula: Molded articles for photographic light-sensitive materials preferably containing 0.03 to 3% by weight.

[0191]

[Chemical 8] Z = A / (A + B + C) {wherein p represents 0 or 1}

Here, A to C represent the following compounds in the above general formula. That is, A is a compound in which R ¹ is a methyl group, R ² is a hydrogen atom, and m is 2 or 3,
Alternatively, it represents a compound in which R ¹ is a hydrogen atom, R ² is a methyl group, and n is 2 or 3. B represents a compound in which both R ¹ and R ² are hydrogen atoms. C represents a compound in which both R ¹ and R ² are methyl groups, and m and n are the same and are 2 or 3.

(2) A molded product for a photographic light-sensitive material, which contains 0.01 to 5% by weight of an organic nucleating agent consisting of a sorbitol derivative represented by the following general formula.

[0194]

[Chemical 9] {In the formula, m and n are the same or different and represent an integer of 1 to 10}

(3) A molded product for a photographic light-sensitive material, containing 0.01 to 5% by weight of an organic nucleating agent consisting of a monoacetal represented by the general formula [A] or [B] or a mixture thereof.

[0196]

[Chemical 10] {In the formula, R represents -COOR ¹ or -CONR ² R ³ .
R ¹ represents an alcohol residue, R ² and R ³ are the same or different and represent a hydrogen atom or an amine residue. n is 1
~ 3 and p is 0 or 1}

[0197]

[Chemical 11] {In the formula, R, n and p are the same as those in the general formula [A]}

(4) A molded product for a photographic light-sensitive material, containing 0.01 to 5% by weight of an organic nucleating agent consisting of a sorbitol derivative represented by the following general formula.

[0199]

[Chemical 12] {In the formula, R represents an alkyl group having 1 to 4 carbon atoms}

(5) At least one organic nucleating agent selected from the group consisting of 1,3-benzylidene 2,4-para-methylbenzylidene sorbitol and 1,3-para-methylbenzylidene 2,4-benzylidene sorbitol To 0.01
Molded article for photographic light-sensitive material containing up to 5% by weight.

(6) A benzylidene sorbitol derivative obtained by adding 0.01 to 10 parts by weight of a phenolic antioxidant represented by the general formula [II] to 100 parts by weight of the benzylidene sorbitol derivative represented by the general formula [I]. Composition from 0.01 to
Molded product for photographic light-sensitive material containing 5% by weight

[0202]

[Chemical 13]

[0203]

[Chemical 14] {In the formula, R ₁ is a hydrogen atom, a halogen atom, or a carbon atom number 1
To 8 alkyl groups or alkoxy groups and hydroxyl groups, which may be different in the same compound, A represents a monohydric to tetrahydric alcohol residue, and n is 1 to 4
Indicates the integer of

(7) A molded article for a photographic light-sensitive material containing 0.01 to 5% by weight of an organic nucleating agent composition comprising a dibenzylidene sorbitol compound containing 0.001 to 10% by weight of an alkaline compound and / or a radical inhibitor.

(8) 100 parts by weight of the crystalline resin, 0.02 to 5 parts by weight of an organic carboxylic acid amide compound of a divalent or higher aliphatic amine, an organic phosphate compound represented by the following general formula or an ammonium salt thereof. A molded product for a photographic light-sensitive material, which contains 0.01 to 5 parts by weight and 0.01 to 5 parts by weight of an organic carboxylic acid metal salt having 7 or more carbon atoms.

[0206]

[Chemical 15] {In the formula, R ₁ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ₂ and R ₃ are each a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group, an aryl group or aralkyl. Represents a group, and X is an -OH group or-
Indicates O ^- NH ₄ ⁺ }

(9) A co-crystal compound of a carboxylic acid having 3 or more carbon atoms and a nitrogen-containing heterocyclic compound having an amino group or a hydroxyl group at the α-position with respect to 100 parts by weight of the crystalline resin.
Molded product for photographic light-sensitive material containing 01 to 5 parts by weight.

(10) Aliphatic carboxylic acid amide compound of divalent or higher aliphatic amine based on 100 parts by weight of crystalline resin.
There is a molded product for photographic light-sensitive material containing 01 to 5% by weight.

The particle size of the solid powder of the dibenzylidene derivative used in the organic nucleating agent composition of the present invention does not need to be particularly limited, and a particle size distribution of 30 to 100 mesh is preferably used.

The preferable organic nucleating agent composition of the present invention is 95 to 50 parts by weight, preferably 90 to 50 parts by weight of the dibenzylidene derivative.
5 to 50 parts by weight of higher fatty acid, preferably 10 parts by weight
In the range of up to 50 parts by weight, the content of both components is 100 parts by weight.

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

The aqueous emulsion of higher fatty acid used in the above method is, for example, a solution of a higher fatty acid in an organic solvent having a concentration of 5 to 50% by weight, preferably 10 to 50% by weight, and a small amount of a surfactant such as 100 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 the higher fatty acid coating formed on the surface of the solid powder of the dibenzylidene sorbitol derivative can be confirmed by observing the coating with a dye.

A preferred organic nucleating agent composition of the present invention is
Examples of the polyolefin resin effectively used as an additive for improving physical strength, non-bleed-out property and odorless property include aliphatic monoolefins having 2 to 6 carbon atoms and having a number average molecular weight of 10,000 to 1,000,000, Preferably 15,000-80
High molecular weight homopolymers or copolymers of 0,000, particularly preferably 20,000 to 600,000, most preferably 30,000 to 400,000, such as homopolypropylene resin, low density homopolyethylene resin, high density homopolyethylene resin, linear polyethylene (ethylene -Α-olefin copolymer resin and ethylene-propylene copolymer resin. In particular, a crystalline polyolefin resin having a high crystallinity is preferable, and the crystallinity is 50% or more, preferably 70% or more, particularly preferably 80% or more, since the effect of adding the organic nucleating agent is effectively exhibited. Most preferably, it is 90% or more of a polyolefin resin. The molecular weight distribution (weight average molecular weight / number average molecular weight) of these polyolefin resins is 2 to 20, preferably 3 to 15, particularly preferably 3.5 to 12, and most preferably 4 to 10. Here, the molecular weight distribution is measured by the GPC method.

In the preferred organic nucleating agent composition of the present invention, 0.005 to 5.0 parts by weight, preferably 0.01 to 3.0 parts by weight, of a higher fatty acid corresponding to 100 parts by weight of the polyolefin resin as a dibenzylidene sorbitol derivative component. A dibenzylidene sorbitol derivative coated with is preferably used.

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

In the preferable 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 or the like, and the dibenzylidene sorbitol derivative and the higher fatty acid are added to the polyolefin resin. The effect described above cannot be achieved by simply adding and mixing. Further, the effects described above cannot be achieved unless the heat history is 180 ° C. or higher, preferably 190 ° C. or higher, and particularly preferably 200 ° C. or higher.

This heat history may be carried out only once. For example, the above-mentioned di-substituted benzylidene sorbitol composition described in detail as a preferable composition of the organic nucleating agent of the present invention in the polyolefin resin composition of the present invention is 0.01 After adding ~ 2.0% by weight, 1
80 ° C or higher, preferably 190 ° C or higher, particularly preferably 200 ° C
The molded product may be molded by using the above-mentioned pellet which is heated and pelletized, and the effect described above is achieved even when the resin temperature at this time is 180 ° C. or lower, but also when molding this molded product. Set the resin temperature to 180 ° C or higher (heat history above 180 ° C is 2
In the present invention, the term "passage" is used. By doing so, it is possible to mold a molded product for a photographic light-sensitive material, which has extremely excellent physical properties and rigidity, a high surface gloss, and almost no appearance failure is observed.

The preferred organic nucleating agent composition of the present invention does not impair physical properties, bleed-out resistance, rigidity and other characteristics when blended with a polyolefin resin composition as compared with the prior art. In some cases, these properties are further improved, and at the same time, they have excellent odorlessness, and at the same time, appearance failure is less likely to occur, and moldability is improved, molding speed can be improved, and molding failure is reduced. It is effective. That is, by incorporating the above-mentioned di-substituted benzylidene sorbitol composition in the polyolefin-based resin composition of the present invention, a photograph excellent in physical strength, rigidity, bleed-out resistance, odorlessness, moldability, and abrasion resistance is obtained. It is possible to provide a molded product for a photosensitive material.

Although the reason why the preferable organic nucleating agent composition of the present invention exerts the above-mentioned excellent effects is not always clear,
Conventional benzaldehyde, which is a raw material for producing dibenzylidene sorbitol, and benzaldehyde derivatives, such as p-substituted benzaldehyde, which is a raw material for producing the dibenzylidene sorbitol derivative of the present invention, have an odor, and both of them are inevitable after purification. ) Tend to cause a strange odor of the light-shielding thermoplastic resin film, and dibenzylidene sorbitol (derivative) causes some decomposition even when the light-shielding thermoplastic resin film is formed using the thermoplastic resin composition. It is possible that it may cause an offensive odor. In the preferred organic nucleating agent composition of the present invention, solid particles of the specific dibenzylidene sorbitol derivative of the general formula (I) are used, and the particles are represented by the general formula
(II) coating with a specific higher fatty acid, and by simultaneously satisfying the requirements of and, the offensive odor presumed to be based on the raw material benzaldehyde or the benzaldehyde decomposed and produced is a shading effect using the thermoplastic resin composition. In this case, it is possible to significantly reduce the properties of injection molded products and light-shielding film molded products, and at the same time, to provide the above physical properties such as rigidity and physical strength.

Each of the various organic nucleating agents may be used alone, in combination with various inorganic nucleating agents, or in combination of two or more of the organic nucleating agents. Further, the surface of the organic and / or inorganic nucleating agent may be coated with various fatty acids, fatty acid compounds, lubricants such as silicon,
It can be coated with a dispersant such as a coupling agent, a plasticizer and a surfactant, a wetting agent and the like.

The total amount of the nucleating agent added is 0.005 to 5.0% by weight,
0.01-3.0% by weight is preferred, 0.03-2.0% by weight is more preferred, and 0.05-1.0% by weight is most preferred. Addition amount is 0.0
If the amount is less than 05% by weight, the addition effect is hardly exhibited and only the blending cost is required. If the amount exceeds 5.0% by weight, the amount is not increased and the cost is increased. Are adversely affected, generate a bad odor, adhere to the mold, bleed out, and reduce the drop strength, which is not preferable.

As a method for blending the nucleating agent, there are a compound method, a dry blending method, a master batch method and the like, but the master batch method is preferable because it has good workability and does not cause environmental pollution. In particular, it is preferable to prepare it simultaneously with the production of the colored masterbatch containing the light-shielding substance, because it is economical and the workability is good. Since it has a high dryness and is easily scattered, it is difficult to mix it as it is. It is advisable to add a small amount of a dispersant or a wetting agent to mix it. Various lubricants with a number average molecular weight of 500 are effective as dispersants.
~ 10,000 various low molecular weight polyolefin resins, various waxes, various carboxylic anhydrides, various higher fatty acids, etc.,
Lubricants such as various fatty acid metal salts, various silicones and various oleic acid amides are particularly preferable. As a wetting agent, DOP,
Various plasticizers such as DHP can be used (see typical examples of plasticizers described later).

Also, various higher fatty acids, fatty acid amides,
It is also preferable to coat a pure product of a fatty acid such as a fatty acid metal salt or a fatty acid compound on the surface of the organic nucleating agent or blend it to enhance the dispersion effect and prevent bleed-out. Furthermore, the polyolefin resin and 180 ° C. or higher, preferably 190
It is preferable to use it as pellets kneaded at a heat history of not less than 0 ° C, particularly not less than 200 ° C from the viewpoint of exerting the effect of the nucleating agent. That is, by adding these additives,
It improves physical strength, increases rigidity, and reduces generation of white powder due to abrasion, and also reduces generation of white powder due to crystallization or bleed-out of the organic nucleating agent. Further, it is possible to prevent the foul odor of the organic nucleating agent, and to prevent the generation of static electricity and the blocking prevention property.
In this case, in order to prevent deterioration, oxidative decomposition and coloration of the above various organic nucleating agents, various dispersants and various thermoplastic resins, the various antioxidants, radical scavengers and antioxidants such as citric acid, phosphoric acid, etc. It is preferable to add one or more agents.

Various effects can be obtained by adding the nucleating agent. For example, a crystalline thermoplastic resin, propylene
100 parts by weight of ethylene copolymer resin as a nucleating agent pt
By adding 0.1 part by weight of -butylbenzoic acid, the haze can be reduced from 40% to 21%, and by adding 0.2 part by weight, it can be further reduced to 12%. Tensile yield stress, can improve adding 0.1 parts by weight, for example from 380 kg / cm ² to 420 kg / cm ^2, then be added more is not improved hardly.
Further, the bending elastic modulus is, for example, 500 when adding 0.1 part by weight.
It is possible to improve kg / cm ² or 600 kg / cm ² ,
Even if added more than that, there is little improvement thereafter.

In order to sufficiently exert the effect of the nucleating agent, the resin temperature at the time of kneading with the crystalline resin (particularly preferably polyolefin resin) is 170 ° C. or higher, preferably 185 ° C. or higher,
Particularly preferably, the temperature is 195 ° C. or higher (passes heat history). It is preferable that the heat history at 170 ° C. or higher is performed once or more, preferably twice (at least twice for pelletizing and molding). When this heat history is passed, it is preferable to use it in combination with at least one kind of antioxidant and / or radical scavenger.

The following plasticizers may be added to the molded product for photographic light-sensitive material of the present invention in order to improve the uniform dispersibility of the nucleating agent and the light-shielding substance.

Representative examples of the plasticizer are shown below. (1) Phthalic acid-based plasticizers Dibutyl phthalate, Dihebutyl phthalate, Dioctyl phthalate, Diisodecyl phthalate, Butyl lauryl phthalate, Ditridecyl phthalate, Butyl benzyl phthalate,
Butylphthalyl butyl glycolate, etc. (2) Phosphate plasticizer, tricresyl phosphate, trioctyl phosphate, etc. (3) Fatty acid plasticizer, tri-n-butyl citrate, dioctyl adipate, dioctyl azelate, dioctyl sebacate, acetyl Methyl ricinoleate, etc. (4) Epoxy plasticizers Alkyl epoxy stearate, 4,5-epoxy tetrahydrophthalic acid diisodecyl, etc. (5) Other plasticizers Chlorinated paraffin, polyester, sucrose octaacetate, etc. 0.01-10.0% by weight is preferable, 0.05-
7.0 wt% is more preferable, and 0.1 to 5.0 wt% is the most preferable. If the addition amount is less than 0.01% by weight, the effect of improving the uniform dispersibility of the light-shielding substance and the effect of improving the blocking adhesion are hardly exhibited, and only the kneading cost increases. If the addition amount exceeds 10.0% by weight, slipping with the screw of the extruder occurs and it becomes impossible to extrude a stable resin amount.

The molded article for photographic light-sensitive material of the present invention may contain a deodorant. Examples of the deodorant include organic carboxylic acids, mixtures of organic carboxylic acids and zinc compounds, and mixtures of organic carboxylic acids, zinc compounds and aluminum compounds.

Examples of the organic carboxylic acid include aliphatic polycarboxylic acids, aromatic polycarboxylic acids and reaction products of these aliphatic or aromatic polycarboxylic acids with polyhydric alcohol compounds, and acidic polyester compounds having a carboxyl group at the end. There is.

Examples of the aliphatic polycarboxylic acid include oxalic acid, malonic acid, succinic acid, adipic acid, fumaric acid, methylfumaric acid, maleic acid, methylmaleic acid, itaconic acid, acetylenic acid, malic acid, methylmalic acid and citric acid. There are di- or tricarboxylic acids such as acids, isocitric acid, mesaconic acid and citraconic acid, or salts thereof, and particularly preferred are citric acid, fumaric acid or salts thereof.

Examples of the aromatic polycarboxylic acid include phthalic acid, terephthalic acid, isophthalic acid, trimellitic acid, pyromellitic acid, benzenehexatricarboxylic acid, naphthalenedicarboxylic acid, naphthalenetricarboxylic acid, naphthalenetetracarboxylic acid and azobenzenetetracarboxylic acid. And aromatic anhydrides thereof and the like, and particularly preferred are benzenetricarboxylic acid and trimellitic acid.

Examples of the acidic polyester compound having a carboxyl group at the terminal include a polyester having a terminal carboxyl group obtained by reacting a polycarboxylic acid such as phthalic acid with a polyhydric alcohol such as ethylene glycol and diethylene glycol, and an acidic cellulose derivative modified with a polycarboxylic acid. Etc.

Examples of the zinc compound used in combination with the organic carboxylic acid include zinc oxide, zinc chloride, zinc sulfate, zinc phosphate, inorganic zinc salts of zinc carbonates, and zinc citrate, and organic zinc of zinc fumarates. Salts and the like, preferably in the range of organic carboxylic acid: zinc compound = 1: 0.1 to 3.0 parts by weight.

The aluminum compound used in combination with the organic carboxylic acid and the zinc compound is aluminum sulfate, potassium, etc., and organic carboxylic acid: zinc compound: aluminum compound = 1: 0.1: 0.1 to 1: 3:
A range of 3 parts by weight is preferred.

The molded article for photographic light-sensitive material of the present invention may contain an oxygen scavenger. The oxygen scavenger is a sulfite, a hydrogen sulfite, a nithionite, a hydroquinone, a catechol, a resorcin, a pyrogallol, an erosion salt, an ascorbic acid, and / or a salt thereof, isoascorbic acid and / or
Or a salt thereof, glucose, lignin, dibutylhydroxytoluene, butylhydroxyanisole, ferrous salt,
Deoxidizer containing metal powder such as iron powder, carbon dioxide generating oxygen absorber, carbon dioxide absorbing oxygen absorber, Crispearl, zeolite, hytrosulfite, glucose oxidase,
Salcomine, alkali metal sulfide, alkali carbonate, sodium thiosulfate, sodium alum, disodium hydrogen phosphate dodecahydrate, sodium silicate hydrate, sodium borate hydrate, ferrous silicate sulphate heptahydrate, activated clay , Mordenite, etc.

Preferably, one containing hydrosulfite as a main component, one containing an organic substance such as L-alcorbic acid as a main component, one containing iron powder as a main component, iron and silicic acid.
A mixed composition with at least one selected from the group consisting of ferrous sulfate heptahydrate, sodium alum, disodium hydrogen phosphate dodecahydrate, sodium silicate hydrate, sodium borate hydrate, hydrosulfite, and Calcium hydroxide or sodium bicarbonate and activated carbon, iron powder and accelerating salts and hydrous substances, oxidizable metal powder and sodium thiosulfate and solid reaction aid, iron powder and sodium thiosulfate and activated carbon, activated iron oxide, metal Oxides, palladium, sugars, enzyme systems.

The molded article for photographic light-sensitive material of the present invention may contain a moisture absorbent. Hygroscopic agents include, for example, carboxylate group-containing water-absorbent resin, crosslinkable polyacrylic acid alkali metal salt, carboxylate-containing ethylene copolymer resin, acrylic acid acrylic metal graft starch cross-linking agent, cross-linked polyvinyl alcohol-alkali metal acrylate. Salt copolymer, polyvinyl alcohol / maleic anhydride copolymer cross-linked product, cellulose modified product, water-soluble polymer cross-linking agent, self-crosslinking alkali metal acrylate polymer, polyacrylic acid or its alkali salt, polyacrylamide or its partial hydrolysis Thing, polyvinylpyrrolidone,
Sulfonated polystyrene, sodium polyacrylamide 2-methylpropanesulfonate, starch-acrylonitrile graft polymer or its hydrolyzate, polyacrylonitrile hydrolyzate, acrylamide-acrylic acid copolymer, carboxymethylcellulose, vinylstyrene sulfone Acid, Mannich reaction product of polyacrylamide, polyacrylamine, homopolymer of dimethylaminoethyl methacrylate or copolymer with acrylamide, homopolymer of dimethylaminoethyl methacrylate quaternized ammonium salt with methyl chloride or its acrylamide Copolymer, quaternary ammonium salt of polydimethylallylamine, polymer of quaternized vinylbenzylamine, acetylating agent of chitosan, polyvalent of epichlorohydrin Condensation reaction product with min or monoamine, polyamide polyamine epichlorohydrin thermosetting resin adsorbed on the surface of super absorbent polymer particles, then thermoset resin, hydrophilic vinyl monomer (acrylamide derivative etc.) and hydrophobic vinyl Copolymer with monomer (derivative of methacrylate), sodium salt of isobutylene-maleic anhydride copolymer, sodium salt of starch and acrylic acid and graft copolymer of acrylic acid derivative, partially crosslinked carboxymethylcellulose polybasic acid, poly Partially cross-linked ethylene oxide, partially cross-linked polyacrylic acid, surface coating of superabsorbent polymer, mixture of superabsorbent polymer and inorganic substances (attapulgite, kaolin, talc, diatomaceous earth, etc.), high water absorption with anionic dissociative groups Having a cationic resin and a cationic dissociative group Mixture of the water-absorbing resin, starch acrylic acid, sodium copolymers of acrylic acid, sodium copolymers of starch acrylate, and the like.

Of these, preferred is a starch or cellulose or synthetic polymer as the raw material having a high water absorption capacity.

An aromatic agent may be contained in the molded article for photographic light-sensitive material of the present invention. The fragrance is lilac flower essential oil,
Jasmine, abies oil, cinnamon oil, lavender oil,
Natural aroma components such as lemon oil, geraniol, eugenol, n-octyl alcohol, carbitol, cis-chasmon, lemon tempene, menthone, methyl salicylate, methylphenylcarbinol, triethyl citrate, benzyl benzoate, citral, d-limonene. ,
Geraniol, ethyl cinnamate, octanol, benzyl benzoate, alkylene glycol, benzyl salicylate, linalool, vanillin, coumarin, methyl naphthyl ketone, rosephenone, etc. , Cyclotextulin, zeolite, starch, talc, etc.

One or more kinds of the above-mentioned deoxidants, deodorants, hygroscopic agents, aromatic agents and inorganic substances (including chelating substances) having an ion exchange function are contained in an amount of 0.01 to 20% by weight, preferably 0.05 to 10%. % By weight, more preferably 0.1-5% by weight
Is. If the content is less than 0.01% by weight, the effect of addition is not exhibited and the cost only increases. If the content exceeds 20% by weight, the photographic light-sensitive material will be adversely affected and the material cost will increase, so that it cannot be put to practical use.

The buffer sheet or adhesive layer having a density of 0.5 g / cm ³ or less according to the present invention contains at least one of an oxygen absorber, a deodorant, a moisture absorbent, an aromatic agent and an inorganic or chelating substance having an ion exchange function. Oxygen is added to the wear-resistant and heat-resistant flexible sheet containing 0.01 to 30% by weight and provided on one side of the buffer sheet (atmosphere side = anti-photosensitive material side) with Young's modulus of 50 kg / mm ² or more and heat resistance. Transparency (AST of MOCON method
50cc / m ² measured by the same pressure method based on MD-3985
・ 24 hours ・ 1 atmosphere ・ 20 ℃ or less, preferably 35cc / m ²・ 2
4 hours, 1 atmosphere, 20 ° C or less, particularly preferably 20 cc / m ² ·
Moisture permeability of 10g determined by the cup method of JIS Z-0208 for 24 hours at 1 atmosphere at 20 ℃ or less (measured at 40 ℃ and 90% RH)
/ M ² · 24 hours or less, preferably 5 g / m ² · 24 hours or less, particularly preferably 2 g / m ² · 24 hours or less as a single-layer sheet or a composite laminated sheet (including co-extruded multilayer film), and buffer A wear-resistant flexible sheet having a Young's modulus of 50 kg / mm ² or more provided on the other side (photosensitive material side) of the sheet has higher oxygen permeability and moisture permeability than the wear-resistant and heat-resistant flexible sheet having the above heat resistance. The photographic property of a photographic light-sensitive material is 10% or more, preferably 20% or more, particularly preferably 40% or more, and most preferably 100% larger single layer sheet or composite laminated sheet (including co-extruded multilayer film). It is possible to provide a light-shielding bag for photographic light-sensitive materials, which has a high commercial value and can be maintained in an excellent performance state for a long period of time and which does not cause discomfort when used by a user.

On the other hand, considering the case of landfill treatment as waste, degradable plastics which are currently being researched or are introduced into some markets may be used. For example, as a biodegradable polymer I
CI "BIOPOL", UCC "Polycaprolactone"
Etc. or natural that is susceptible to biodegradation,
Alternatively, a polymer that is indirectly disintegrated by adding a synthetic polymer as an additive, or a starch-containing polyethylene or the like can be used.

[0244] Particularly, "Bionol" manufactured by Showa Highpolymer Co., Ltd. (chemically synthesized from dicarboxylic acid, etc., which was recently released as a chemically synthesized biodegradable plastic that decomposes into carbon dioxide and water by the action of microorganisms 10% by weight or more of a special polyester resin) or "Matterby" (polymer starch of corn starch and biodegradable modified polyvinyl alcohol) manufactured by Novamont of Italy is added to the resin composition for molded articles of the present invention. Doing so is also preferable from the viewpoint of improving the processability of industrial waste.

In the case of a molded article having a multi-layered structure, it is particularly preferable that the layer not directly contacting the photographic light-sensitive material contains 50% by weight or more of the biodegradable plastic from the viewpoint of improving the industrial waste disposal property.

It is also possible to use a photodegradable polymer. For example, an ECO copolymer obtained by copolymerizing ethylene and carbon monoxide in which a carbonyl group is introduced as a photosensitizing group in the main chain during polymerization of polyethylene is used, or a transition metal salt, an oxidation accelerator, a photosensitizer is added as an additive. It is possible to use a material obtained by adding a material or the like to the base polymer and imparting photodegradability thereto.

Furthermore, one or more kinds of degradable polymers such as biodegradable polymers, photodegradable polymers and water-soluble polymers may be used in combination (JP-A-3-1293).
(See Japanese Patent No. 41).

When recycling is considered, the molded article for photographic light-sensitive material is made of the same or similar resin composition. For example, a patrone for photographic film (Fig. 11 (a), (b))
All of the cartridge, spool, and label with print that make up the product are made of polystyrene resin or polypropylene resin, and the spool 20, upper case 23, and lower case 22 of the film-equipped lens unit (Fig. 12) are completely shielded from light. It is preferable to use a polystyrene-based resin or a polypropylene-based resin that it has.

The following may be further added to the molded photographic light-sensitive material of the present invention as other additives.

<Examples of Other Additives> (Types of Additives) (Examples of Representatives) (1) Stabilizers: lead-based, cadmium-based, zinc-based, alkaline earth metal-based, organotin-based, etc. (2) Difficult Combustion agents; phosphoric acid esters, halogenated phosphoric acid esters, halides, inorganic substances, phosphorus-containing polyols, etc. (3) Fillers: alumina, kaolin, clay, zeolite, calcium carbonate, mica, talc, titanium oxide,
Silica, etc. (4) Reinforcing agent; glass roving, metal fiber, glass fiber, glass milled fiber, carbon fiber, etc. (5) Foaming agent: Inorganic foaming agent (ammonia carbonate, sodium bicarbonate), organic foaming agent (nitroso type, azo (6) Vulcanizing agents; Vulcanization accelerators, accelerating aids, etc. (7) Deterioration inhibitors; UV absorbers, antioxidants, metal deactivators, peroxide decomposers, etc. (8) Cups Ring agent: Silane-based, titanate-based, chromium-based, aluminum-based, etc. (9) Various thermoplastic resins, polyolefin-based elastomers, synthetic rubber, etc.

Typical examples of the molded article for photographic light-sensitive material of the present invention obtained by molding the above-mentioned molding resin composition are shown below, but the present invention is not limited thereto.

(1) Film molded product Single layer film molded product (FIG. 1); Japanese Patent Publication No. 2700/1990, etc. Multi-layer coextrusion film molded product (FIGS. 2 and 3); Single layer film molded product or multilayer coextrusion product Laminated film using a film molded product (FIG. 4, FIG. 5, FIG. 6 and FIG. 7);
Japanese Examined Patent Publication No. 63-26697, Japanese Examined Patent Publication No. 2-2701, Japanese Examined Patent Publication No. 2-13774, Japanese Examined Patent Publication No. 2-19225, etc. A packaging material using the flexible sheet described above;
Packaging bags (Unipack bag, single flat bag, double flat bag, single gusset bag, double gusset bag, etc.), shredding package, bulk package (JP-A-3-53243, JP-A-3-71346) (Gazettes, etc.) Packing body for light-room loading of collective packaging, etc. and strip-shaped photosensitive material JP-A-55-113543, JP-A-60-13386, JP-A-60-167796, JP-A-2-72347 Publication, Japanese Utility Model Publication No. 3-47547, Japanese Utility Model Publication No. 3-54937, and Japanese Utility Model Publication No. 3
-86358, Japanese Utility Model Publication No. 3-96648, etc.

(2) Vacuum formed product

(3) Injection molded product Spool for photographic film, film unit with lens,
Containers for photographic film cartridges, light-shielding containers, plastic photographic film cartridges, light-shielding magazines for loading light chambers, cores, photographic film cartridges, instant film packs, etc.

Cartridge for disc film; Japanese Utility Model Publication No. 60-21743, etc.

Film unit with lens (FIG. 12); JP-A-63-226643

Spool for photographic film (FIG. 10); JP-A-1-251030, JP-A-57-196218, JP-A-SHO
No. 59-15049, USP No. 1930144, No. 63-73742
Publication, Japanese Utility Model Publication No. 54-120931, Japanese Utility Model Publication No. 58-178139-
178145, JP-B-55-31541, JP-A-58-203
436, JP-A-58-82237, JP-A-58-82236
JP-B-44-16777, JP-B-63-73742, JP-A-62-240957, GB 2199805A, etc.

A photographic film cartridge (Fig. 11); JP-A-54-111822, JP-B-45-6991, and JP-B-58
55-21089, JP-A-50-33831, JP-A-56-
87039, Japanese Utility Model Laid-Open No. 55-97738, Japanese Patent Laid-Open No. 1-3125
38, JP-A-57-190948, USP 4,846,418
Specification, USP 4,848,693 Specification, USP 4,887,7
No. 76, etc.

Containers for photographic film cartridges (FIGS. 8 and 9); JP-A-61-250639 and JP-A-61-73947.
Publication No. 60-163451, USP 4,801,011
JP-A-63-121047, JP-A-62-291639, JP-A-1-88940, JP-A-1-113235, JP-A-1-152337, JP-B2-33236. Publication, Japanese Utility Model Publication No. 3-48581 Publication, Japanese Patent Publication No. 2-38939 Publication,
USP 4,639,386 specification, USP 4,801,011 specification, USP 4,979,351 specification, EP 0237062A2 specification, EP 0280065A1 specification, EP 0298375A2 specification and the like.

Cores, reels; Jitsukai Sho 60-107848, USP 4809923, GB 2033873 B, etc.

Magazine for sheet film; Sho 56-5141
Issue bulletin etc.

Photographic film cartridge (FIG. 14); JP-B-56-16610, JP-B-2-24846, JP-B-2-29041, JP-B-60-120448, JP-A-1
−312537 publication

Photographic film case (Fig. 13); USP
4,779,756, JP 54-100617, JP 6
4-32343 gazette, Kaikaihei 1-94258 bulletin, Kaikaihei 2-5
6139, EP 0242905A1, specification, Japanese Examined Patent Publication 2-54
No. 934 bulletin

The method for forming a molded article for a photographic light-sensitive material is as follows:
Depending on the form of each molded product, it is formed by, for example, inflation film molding, injection molding, vacuum molding, sheet molding, T-die flat film molding, pressure molding, rotational molding, in-mold vacuum injection molding or the like.

The molded product of the present invention has a CAS code (camera automatic detection code), a bar code, a CI mark, a product name,
It is possible to print characters or symbols necessary for the function, such as a handling instruction, a product identification mark, and a product identification color, or printing to enhance the product value. Alternatively, a shrink film, a label, or a label that has been subjected to these printings and stretched in at least the longitudinal direction may be attached to the molded product of the present invention, or may be a heat-shrinkable package for a photographic light-sensitive material. An ink that is harmless to the photographic light-sensitive material is selected as the ink used for these printings, and can be selected from commonly used offset printing inks, gravure printing inks, UV inks and the like.

Typical synthetic resins used for these inks are vinyl chloride-based copolymer resins, vinyl-amino resins, alkyd-vinyl resins, oil-free alkyd resins, vinyl chloride-based vinyl chloride, and nitrified cotton. , Polyester, polyamide urethane, polyacrylic, rosin-modified maleic acid,
Ethylene vinyl acetate, vinyl ether, urethane vinyl acetate, vinyl chloride vinyl urethane resin, modified alkyd resin, modified phenolic resin, high molecular polyester / amino resin, low molecular polyester / amino resin, alkali soluble resin (rosin modified maleic acid resin, Styrene maleic acid resin, styrene acrylic acid resin, acrylic acid ester acrylic acid resin, methacrylic acid ester acrylic acid resin), hydrosol type resin (styrene maleic acid resin, styrene acrylic acid resin, α-methylstyrene acrylic acid resin, acrylic acid ester) Acrylic acid resin, methacrylic acid ester acrylic acid resin), emulsion type resin (styrene resin, styrene acrylic acid ester resin, acrylic acid ester copolymer resin, methacrylic acid ester copolymer resin), resin for VU ink, Polymers having a curly unsaturated group are generally used, and typical examples include polyester / acrylic acid ester, polyester / urethane resin / acrylic acid ester, epoxy resin / acrylic acid ester, pentaerythritol triacrylate, Examples include trimethylolpropane triacrylate, hexanediol diacrylate, neopentyl glycol diacrylate, triethylene glycol diacrylate, and hydroxyethylene methacrylate.

A commonly known coloring agent is used in combination with these inks. As the colorant to be used, various pigments and azo pigments described in JP-A-63-44653 (azo lake; carmine 6B, red 2B, insoluble azo; monoazo yellow (PY-1, 3), disazo yellow ( PY-12, 13, 14, 17, 83), pyrazolo orange (PO-B-34), vulcan orange (PO-16), condensed azo system; chromophthal yellow (PY-93, 95), chromophthal red (PR-144, 166), polycyclic pigment (phthalocyanine type; copper phthalocyanine blue (PB-15, 15)
-1,15-3), copper phthalocyanine green (PG-
7), cioxazine type; dioxazine violet (P
V-23), isoindolinone type; isoindolinone yellow (PY-109, 110), slene type; perylene, perinone, flavantron, thioindigo, lake pigment (malachite green, rhodamine B, rhodamine G, Victoria blue B). Inorganic pigments (oxides: titanium dioxide, red iron oxide, sulfates; precipitated barium sulfate, carbonates; precipitated calcium carbonate, silicates; hydrous silicates, anhydrous silicates, metal powders; aluminum powders, bronze powders, zinc dust , Other carbon black, yellow lead, ultramarine, navy blue) and the like.
Further, these pigments may be added as a light-shielding substance to the above-mentioned resin layer or the like. In addition to these, oil-soluble dyes and dispersible dyes are also used. In addition, various kinds of solvents, dispersants, wetting agents, defoaming agents, leveling agents, thickeners, stabilizers, crosslinking agents, waxes and other additives are used as necessary as raw materials for the ink. Synthetic resins and colorants used as these ink compositions should be applied as paints on the surface of molded products for the purpose of improving commercial value, improving abrasion resistance, improving light-shielding properties, improving photographic properties, etc. Is also preferable.

Further, various paints can be applied as a base coat or a top coat so as to improve the commercial value of the molded product for a photographic light-sensitive material of the present invention and to make printing of printing ink beautiful and colorful. As the paint resin and pigment, those for the ink described above can be used, but UV paint, melamine alkyd paint, urethane paint and melamine paint are particularly preferable. The top coat is preferably a transparent lacquer coating, silicone coating, urethane coating, acrylic lacquer coating applied in a thin layer of 0.1 to 30 μm, preferably 0.3 to 20 μm, particularly preferably 0.5 to 10 μm.

The photographic light-sensitive materials to which the molded product for photographic light-sensitive materials of the present invention can be applied are shown below. (1) Silver halide photographic light-sensitive materials (printing film, color or black and white photographic paper, color or black and white negative film,
Master paper for printing, DTR (diffusion transfer) photosensitive material, computer typesetting film and paper, color or black and white positive film, color reversal film, microfilm,
Films for movies, self-developing photographic light-sensitive materials, direct positive films and papers, etc.)

(2) Heat-developable light-sensitive material (heat-developable color light-sensitive material, heat-development black-and-white light-sensitive material (for example, Japanese Examined Patent Publication Nos. 43-4921 and 43-4924, "Basics of Photographic Engineering", Silver Salt Photo Edition ( Published by Corona in 1879), pages 553-555 and research
Tis Closure Magazine, June 1978, pages 9-15 (RD
-17029) etc. Furthermore, JP-A-59-
12431, 60-2950, 61-52343 and U.S. Pat. No. 4,584,267, a transfer type heat-developable color photographic light-sensitive material)))

(3) Photosensitive / thermosensitive recording material (JP-A-3-72)
Recording material using photothermography (photosensitive / thermosensitive image forming method) described in Japanese Patent No. 358, etc.

(4) Diazonium photographic light-sensitive material (4-morpholinobenzenediazonium microfilm, microfilm, copying film, printing plate material, etc.)

(5) Azide- and diazide-based photographic light-sensitive materials (light-sensitive materials containing para-azidobenzoate, 4,4'diazidostilbene, etc., such as copying films, printing plate materials, etc.)

(6) Quinonediazide photographic light-sensitive material (orthoquinonediazide, orthonaphthoquinonediazide compound, for example, benzoquinone (1,2) -diazide-
(2) Photographic light-sensitive material containing 4-phenylsulfonic acid phenyl ether, etc., such as printing plates, copying films, adhesion films, etc.)

(7) Photopolymers (photosensitive materials containing vinyl monomers, printing plate materials, adhesion films, etc.)

(8) Polyvinylcinnamic acid ester-based photosensitive material (eg, printing film, IC resist, etc.)

In order to maintain these photographic light-sensitive materials in a good photographic property for a long period (6 months or more), when the photographic light-sensitive material molded article of the present invention is used as a package, the photographic light-sensitive material is Water vapor transmission rate (measured under JIS Z 0208 condition B) is 10 g / m ² · 24 hours or less, preferably 5 g / m ² · 24
Time or less, particularly preferably 2 g / m ² · 24 hours or less, oxygen permeability of 50 cc / m ² · 24 hours · 1 atmosphere · 20 ° C or less, preferably 35 cc / m ² · 24 hours · 1 atmosphere · 20 ° C or less It is particularly preferable to use a hermetically sealed package at 20 cc / m ² , 24 hours, 1 atmospheric pressure, and 20 ° C. or less.

[0278] In addition, photosensitive substances that are altered or deteriorated by various kinds of light, oxygen, sulfurous acid gas, etc., such as foods (butter, peanut bags, margarine, snack products, knobs, confectionery, tea, paste, etc.), pharmaceuticals (gastrointestinal drug) , Powdered medicines such as cold medicine, granular medicines), dyes, pigments, photographic developing chemicals,
It can also be applied to photographic fixing chemicals, toner, etc.

In the photographic light-sensitive material package of the present invention, the moisture permeability (measured under the condition B of JIS Z 0208) of the photographic light-sensitive material using the above-mentioned molded product for photographic light-sensitive material is 10 g / m ² · 24 hours or less, Oxygen permeability (measurement method for Mokon pressure) is 50cc / m ²
-It is configured to be hermetically sealed at 24 hours, 1 atmosphere and 20 ° C or less.

When the water vapor permeability exceeds 10 g / m ² · 24 hours,
The photographic properties of a photographic light-sensitive material containing many sensitizing dyes and various additives that deteriorate due to moisture cannot be maintained in good condition for a long time (6 months or more). Further, when a moisture is absorbed, a gelatin layer that is likely to be blocked is present on at least one of the front and back sides of the support, and thus blocking is likely to occur, which makes practical application difficult.

When the oxygen permeability exceeds 50 cc / m ² , 24 hours, 1 atmosphere, and 20 ° C., sensitizing dyes, couplers, and other additives in the emulsion coating layer of the photographic light-sensitive material which are easily oxidized are deteriorated by oxygen. It is difficult to put into practical use because it deteriorates and the photographic property deteriorates. In particular, it cannot be put to practical use for color photographic light-sensitive materials (negative film, positive film, photographic paper, reversal film, instant film, etc.) that require color balance.

The molded article for a photographic light-sensitive material of a photographic light-sensitive material package may contain, adhere to or be coated with the above-mentioned deodorant, aromatic, hygroscopic agent or oxygen absorber.

[0283]

In the molded article for photographic light-sensitive material of the present invention, the acrylic acid copolymer resin delays the bleed-out of lubricants and antistatic agents. Further, the oil-absorbing substance adsorbs a lubricant and an antistatic agent to prevent bleed-out. Antioxidants prevent the generation of substances that adversely affect the photographic properties of photographic light-sensitive materials due to thermal decomposition of resins and additives. Further, it prevents the spots and coloring troubles (including the spotted coloring due to the dark brown charring, etc. in addition to coloring the entire molded product in yellow, etc.) caused by the thermal deterioration of the resin and the additives.

[0284]

EXAMPLES Examples of molded articles for photographic light-sensitive materials of the present invention will be described based on the drawings. 1 to 7 are partial cross-sectional views of a packaging film for a photographic light-sensitive material which is one of molded products for a photographic light-sensitive material.

The photographic light-sensitive material packaging film shown in FIG. 1 is formed of a single-layer film consisting only of the light-shielding thermoplastic resin film layer 1a as the photographic light-sensitive material molded article of the present invention.

The photographic light-sensitive material packaging film shown in FIG. 2 (a) is a two-layer coextruded film comprising a light-shielding thermoplastic resin film layer 1a and a thermoplastic resin layer 2 as a photographic light-sensitive material molded article of the present invention. It is formed of IIa.

The packaging film for photographic light-sensitive material shown in FIG. 2 (b) comprises a light-shielding thermoplastic resin film layer 1a and a light-shielding thermoplastic resin layer 2a as a molded product for photographic light-sensitive material of the present invention. It is formed of a layer coextruded film IIa.

The packaging film for a photographic light-sensitive material shown in FIG. 3 is a light-shielding thermoplastic resin film layer 1a, an intermediate layer 3, and a thermoplastic resin 2 as a molded product for a photographic light-sensitive material of the present invention.
And a two-layer coextruded film IIIa.

The packaging film for a photographic light-sensitive material shown in FIG. 4 (a) is obtained by adhering the two-layer coextrusion film IIa shown in FIG. 2 (a) to the thermoplastic resin layers 2 and 2 with blocking B. It is formed of the laminated film IVa.

The packaging film for a photographic light-sensitive material shown in FIG. 4 (b) is formed by adhering the two-layer coextrusion film IIa shown in FIG. 2 (b) to the thermoplastic resin layers 2a, 2a by blocking B. It is formed of the laminated film IVa.

The packaging film for a photographic light-sensitive material shown in FIG. 5 has an adhesive layer 4 on the light-shielding thermoplastic resin film layer 1a.
It is formed of a laminated film in which the flexible sheet layer 5 is laminated via the.

The packaging film for a photographic light-sensitive material shown in FIG. 6 is a metal vapor deposition film obtained by processing the light-shielding thermoplastic resin film layer 1a, the biaxially stretched film layer 6 and the metal vacuum vapor deposition layer 8 via the anchor coat layer 7. The axially stretched film layer 9 and the lexible sheet layer 5 are formed of a laminated film laminated via an adhesive layer 4.

The packaging film for photographic light-sensitive material shown in FIG. 7 has the above-mentioned light-shielding thermoplastic resin film layer 1a and metal foil 10.
Also, the flexible sheet layer 5 is formed of a laminated film laminated via the adhesive layer 4.

FIG. 8 (a) is a sectional view of a photographic film cartridge container 14 as a molded article for a photographic light-sensitive material of the present invention, and this photographic film cartridge container 14 comprises a container body 15 and a lid 16. Both of the container body 15 and the lid 16 are the molded product for photographic light-sensitive material of the present invention.

FIG. 8 (b) is a sectional view of an embodiment of another container 14 for a photographic film cartridge as a molded article for a photographic light-sensitive material of the present invention. This container 14 for a photographic film cartridge has a container body 15 and a lid 16. The container body 15 has a taper in which the inner diameter (A + a) of the upper opening is larger than the inner diameter (A) of the bottom by a. The value of this a is 0.
001 to 2 mm, preferably 0.01 to 1.5 mm, particularly preferably 0.
02 to 1 mm, most preferably 0.05 to 0.5 mm. This container body 15 is a molded product for a photographic light-sensitive material of the present invention.

FIG. 9 is a perspective view of a container 14 for a photographic film cartridge as a molded product for a photographic light-sensitive material of the present invention. The container 14 for a photographic film cartridge has a container body 15 and a lid 16.
Are integrally formed, and these are formed of the light-shielding thermoplastic resin composition of the present invention.

FIG. 10 is a front view of a spool 20 for a photographic film as a molded article for a photographic light-sensitive material of the present invention. The spool 20 for a photographic film is entirely formed of the light-shielding thermoplastic resin composition of the present invention. There is.

11 (a) and 11 (b) show a crystalline resin photographic film cartridge as a molded article for the photographic light-sensitive material of the present invention.
17 is an exploded perspective view of this patrone for photographic film.
Is composed of an upper case 18 and a lower case 19 which constitute the main body of the cartridge, and a spool 20 around which the photographic film to be loaded is wound. The upper case 18, the lower case 19 and the spool 20 are formed of the light-shielding thermoplastic resin composition of the present invention. Considering recyclability, it is preferable that all of the spool 20, the upper case 18, and the lower case 19 are formed of the same or the same resin composition.

FIG. 12 is an exploded perspective view of the film unit with lens 21 as a molded product for photographic light-sensitive material of the present invention.
The lens-equipped film unit 21 is a lower case for further tightly storing the photographic film cartridge 17 that tightly houses the spool 20 around which the photographic film is wound.
22 and an upper case that shields the lower case 22 from light.
23, and the spool 20, the lower case 22 and the upper case 23 are formed of the light-shielding thermoplastic resin composition of the present invention. Spool 2 considering recycling suitability
It is preferable that 0, the upper case 23, and the lower case 22 are all made of the same or the same kind of resin composition.

FIG. 13 is a sectional view of a light-shielding case 24 for a photographic film as a molded article for a photographic light-sensitive material of the present invention. The light-shielding case 24 for a photographic film comprises a container body 15 and a lid 16 which are integrally formed. It is formed of the light-shielding thermoplastic resin composition of the invention.

FIG. 14 is an exploded perspective view of a photographic film cartridge 25 as a molded product for photographic light-sensitive material of the present invention.
The photographic film cartridge 25 is composed of a lower case 26 and an upper case 27, and a spool 28 loaded therein, and the spool 28, the lower case 26 and the upper case 27 are the light-shielding thermoplastic resin composition of the present invention. It is made of things. Considering recyclability, it is preferable that the spool 28, the lower case 26, and the upper case 27 are all formed of the same or the same resin composition.

FIG. 15 is a view showing a packaging process of a strip-shaped photographic light-sensitive material package using a light-shielding thermoplastic resin film layer as a molded product for photographic light-sensitive material of the present invention. In this figure, reference numeral 29 is a belt-shaped photographic photosensitive material, reference numeral 30 is a thermoplastic resin film guide member, reference numeral 31 is a light-shielding thermoplastic resin film cover member, reference numeral 32 is a heat seal, an adhesive, a bonding tape, etc. Joint, code 33 is core, code
34 is a bush for hermetic packaging.

[Example 1] A light-shielding inflation film molded article for a photographic light-sensitive material corresponding to FIG. Melt flow rate as a crystalline resin (hereinafter, MFR is the value according to JIS K 6760, and when a load of 2.16 kg is applied at 190 ± 0.5 ° C, it is extruded from an orifice with a diameter of 2.095 mm and a length of 8.0 mm for 10 minutes. Polyethylene (indicated in g) is 2.0 g / 10 min, and density (value according to JIS K 6760) is
0.920 g / cm ³ , 70% by weight of ethylene / 4-methylpentene-1 copolymer resin having a crystallinity of 45% and MFR of 14 g / 10 minutes,
10 parts by weight of homopolyethylene resin having a density of 0.950 g / cm ³ and a crystallinity of 83%, MFR of 2.0 g / 10 minutes, and density of 0.925 g
/ Cm ^3, a mixed resin 99.75 parts by weight of a crystallinity of 67% homo-polyethylene resin 19.50 parts by weight, 0.05 parts by weight of erucamide as a lubricant, glycerin monostearate nonionic antistatic agent as an antistatic agent 100 parts by weight of a polyolefin-based resin composition containing 0.2 part by weight, and tetrakis [methylene-3 (3.5-di-tert-butyl-) which is a hindered phenolic antioxidant as an antioxidant.
4-hydroxyphenyl) propionate] methane 0.10
Parts by weight and n-octadecyl-3- (4'-hydroxy-
A mixture of 0.05 parts by weight of 3 ', 5'-di-tert-butylphenol) propionate was used as an ethylene / acrylic acid copolymer resin having an MFR of 5.5 g / 10 minutes and a density of 0.932.
30 parts by weight of ethylene / acrylic acid copolymer resin having g / cm ³ and an acrylic acid content of 6.5% by weight, pH as a light-shielding substance
, A volatile matter content of 0.8 parts by weight, an oil absorption amount of 76 ml / 100 g, and an average particle size of 21 mμ of furnace carbon black.
1.1mm, ring die with diameter 50cmφ)
A light-shielding polyolefin resin inflation film having a blow-up ratio of 1: 1.2 at 90 ° C. and a thickness of 70 μm was molded.

This light-shielding blown film is
The antistatic property and the lubricity were excellent, the bleed-out of the antistatic agent and the lubricant with the passage of time was small, stickiness and blocking did not occur, and the heat sealability was also good.

Comparative Example 1 Instead of 30 parts by weight of ethylene / acrylic acid copolymer resin of the polyolefin resin composition of Example 1, MFR was 5.0 g / 10 minutes and density was 0.919 g / cm 3.
^{3. The} molding apparatus and molding conditions were the same as in Example 1 except that 30 parts by weight of homopolyethylene resin having a crystallinity of 65% was added and the addition amount of the two kinds of antioxidants was changed to 0 parts by weight. It is a light-shielding polyolefin resin inflation film molded product for photographic light-sensitive materials having a thickness of 70 μm.

This light-shielding blown film is
Bleed-out of antistatic agents and lubricants was large with the passage of time, stickiness and blocking occurred, and heat sealability was also poor. Furthermore, it adversely affects photographic properties (increased fogging), and many spots such as microgrit frequently occur,
It was difficult to put it into practical use as a film molded product for a photographic light-sensitive material.

[Prior Art Example 1] 99.75 parts by weight of homopolyethylene resin having MFR of 2.0 g / 10 minutes, density of 0.925 g / cm ³ , and crystallinity of 67%, erucamide amide as a lubricant of 0.05 parts by weight, antistatic agent As glycerin monostearate 0.2
A light-shielding low-density polyethylene resin inflation film molded product having a thickness of 70 μm was produced using the same inflation film molding apparatus as in Example 1 using a polyolefin resin composition containing parts by weight and under the same molding conditions.

This blown film had large bleed-out of the antistatic agent and lubricant with the passage of time, stickiness and blocking occurred, and the heat sealability was also poor.

Example 2 A laminated film shown in FIG. Using the 70 μm thick light-shielding polyolefin resin inflation film molded product 1a of Example 1, an unbleached kraft paper having a basis weight of 70 g / m ² as a flexible sheet layer 5 which does not adversely affect the photographic light-sensitive material from the outside is prepared. Thickness 13
Extrusion lamination low-density homo-polyethylene resin adhesive layer (resin temperature 305 ° C) 4 μm thickness 15 μm
The aluminum vacuum-deposited biaxially stretched film layer 9 obtained by processing the aluminum vacuum-deposited layer 8 having a thickness of 400 Å after the anchor coat layer 7 having a thickness of 2 μm is applied to the biaxially stretched nylon resin film 6 having a thickness of 13 μm Rouge laminate Low density homopolyethylene resin adhesive layer (resin temperature 3
15 ° C.) 4 to prepare a laminated film in which the light-shielding polyolefin resin inflation film layer 1a having a thickness of 70 μm of Example 1 is laminated, and two sheets of Example 1 having a thickness of 70 are formed.
A roll-shaped color photographic paper (outside 7.6 cm) with an emulsion layer of 8.9 cm width and a roll length of 180 m on the outside in a sealed light-shielding bag produced by heat-sealing the μm light-shielding polyolefin resin inflation film layers 1a, 1a. Rolled to a thickness of 8 mm
Was used as a gusset bag having a center seal and a gusset to form a package.

This package has excellent sealing light-shielding property, antistatic property, and physical strength. After being stored at 18 ° C. for 1 year, it has excellent sealing light-shielding property, little decrease in heat seal strength, good antistatic property, and erucic acid. Bleedout of the amide and glycerin monostearate to the surface of the light-shielding inflation film layer is also moderate, and there is no blocking with the emulsion layer or development inhibition due to transfer to the emulsion layer or adhesion of white powder, and roll color printing. The outermost peripheral portion of the paper (generally, a portion not used for quality assurance as a guide) also had an unexpected effect of being usable as a print photograph.

Example 3 A laminated film shown in FIG. Aluminum vacuum-deposited biaxially stretched nylon film layer obtained by applying a 400-Å-thick aluminum vacuum deposition layer 8 to the 15 μm-thick biaxially stretched nylon resin film layer 6 of Example 2 through the anchor coat layer 7 having a thickness of 2 μm. A laminated film having the same layer structure as in Example 2 except that an aluminum foil having a thickness of 7 μm, which is a metal foil 10, was used instead of 9, and a roll-shaped color photographic paper package having the same shape as in Example 2 was prepared. And Similar to Example 2, this package also had an unexpected effect with excellent properties after one year.

[Example 4] A biaxially stretched polyester resin film layer 1a having a thickness of 12 µm was used as the innermost layer in place of the unbleached kraft paper having a basis weight of 70 g / m ² which was the flexible sheet 5 of Example 2. 70 μm thick light-shielding polyolefin resin inflation film layer 1a of Example 1
A laminated film having the same layer structure as in Example 2 except that was used to prepare a roll-shaped color photographic paper package having the same shape as in Example 2. Similar to Example 2, this package also had an unexpected effect with excellent properties after one year. Since a dust-free biaxially stretched polyester resin film was used for the outermost layer as compared with Example 2, it was preferable because no dust was generated.

Comparative Example 2 Instead of the 70 μm thick light-shielding polyolefin resin inflation film molded product 1a of Example 1 which is the innermost layer of Example 2, a 70 μm thick light-shielding polyolefin resin of Comparative Example 1 was used. A laminated film having the same layer structure as in Example 4 was prepared except that a resin blown film molded product was used to obtain a roll-shaped color photographic paper package having the same shape as in Example 2. Initially, this package had substantially the same characteristics as those of Example 2 (however, there were many defects that the innermost layer had spots), but after one year, erucic acid amide and glycerin monostea were formed. There is a lot of bleeding out on the surface of the plate, transfer to the photosensitive emulsion layer of roll-shaped color photographic paper with the emulsion layer on the outside, and not only static marks occur when taking out from the bag due to blocking with the emulsion layer. However, uneven development occurred due to development inhibition due to transfer of erucic acid amide and glycerin monostearate, and the outermost peripheral portion could not be used as a print photograph.

Conventional Example 2 Instead of the 70 μm thick light-shielding polyolefin resin inflation film molded article 1a of Example 1 which is the innermost layer of Example 2, 70 μm thick light-shielding low density of Conventional Example 1 was used. A laminated film having the same layer structure as in Example 2 was prepared except that a homopolyethylene resin blown film molded product was used to obtain a roll-shaped color photographic paper package having the same shape as in Example 2. From the beginning of preparation, this package had a sealing light-shielding property, a heat-sealing strength, a hot tack property, etc. which were far inferior to those of Example 2. However, after one year, the erucic acid amide and glycerin monostearate were mixed with each other. There is a lot of bleed-out on the surface of the inner layer, and not only the heat seal strength is reduced to half, but also the weight of the contents may cause peeling of the heat seal part. There was a problem as a light-shielding bag for photographic light-sensitive materials. Further, bleed-out was large, and when the emulsion was transferred to a photosensitive emulsion layer of a roll-shaped color photographic paper and blocking with the emulsion layer occurred, a static mark was generated when the bag was taken out from the bag. Further, uneven development progress occurred due to uneven transfer of erucic acid amide and glycerin monostearate to the photosensitive emulsion layer, and the outermost peripheral portion could not be used as a printed photograph.

Next, the features and effects of the present invention will be described with reference to examples of injection-molded articles which are one of the molded articles for photographic light-sensitive materials, but the examples are representative examples and the present invention is not limited thereto. It goes without saying that the invention includes all those that can be easily inferred by those skilled in the art from the contents described in the claims and the description.

[Example A] A container main body for a photographic film cartridge corresponding to FIG. MI as a crystalline resin
35g / 10min (ASTM D-1238, temperature 230 ℃, load 2.16)
(measured in kgf), density 0.900 g / cm ³ (ASTM D-150
5), a polypropylene resin composition containing 99.85 parts by weight of a propylene / ethylene random copolymer resin having a crystallinity of 93%, 0.05 parts by weight of oleic acid amide as a lubricant, and 0.1 parts by weight of polyoxyethylene sorbitan stearate as an antistatic agent. 100 parts by weight of the compound, 0.10 parts by weight of tetrakis [methylene-3 (3.5-di-tert-butyl-4-hydroxyphenyl) propionate] methane, which is a hindered phenolic antioxidant as an antioxidant, and n-octadecyl. A mixture of 0.10 parts by weight of 3- (4'-hydroxy-3 ', 5'-di-tert-butylphenol) propionate was used, and MFR (ASTM D-1238, temperature 190 was used as an ethylene / acrylic acid copolymer resin. ℃, load 2.16kgf
13 g / 10 min, density (ASTM D-1505) is 0.
940 g / cm ³ , 20 parts by weight of ethylene acrylic acid copolymer resin having a comonomer content of 8% by weight, and surface-treated with magnesium stearate as an organic nucleating agent 1, 3, 2.4-
A container for a photographic film cartridge at a resin temperature of 220 ° C. using a propylene resin composition consisting of 0.15 parts by weight of di- (methylbenzylidene) sorbitol and an injection molding device (24 cavities, mold clamping pressure 150 t). It is an injection-molded article for a photographic light-sensitive material obtained by injection-molding a main body in a molding cycle of 8 seconds. This injection-molded product does not have a coloring failure, does not adversely affect the photographic properties of the photographic light-sensitive material, has no failure due to bleed-out of a lubricant, an antistatic agent or an antioxidant, and has a fatal molding failure such as a short shot. Since almost no deformation occurred and no deformation occurred, continuous unmanned injection molding became possible for a long time.

The container body for photographic film cartridges, which is an injection-molded product, has a fast molding cycle, good lubricity between the container bodies, excellent suitability for high-speed air delivery, less scratches, and excellent antistatic properties. The adhesion of the film was small and the suitability for putting the photographic film cartridge in and out of the container body was excellent. In addition, the appearance is very good, the drop strength of the concrete from the height of 5m to the floor is very large,
In particular, the drop impact strength under low temperature conditions of 0 ° C. or less was twice or more that of the container main body for the photographic film cartridge of Comparative Example A to which the ethylene / acrylic acid copolymer resin was not added, which was preferable.

Even after storage at 18 ° C for 1 year, oleic acid amide as a lubricant and polyoxyethylene sorbitan stearate as an antistatic agent had little bleed-out on the surface of the container body, resulting in stickiness, adhesion of dust and generation of white powder. It was a container body for photographic film cartridges with excellent appearance, impact strength, lubricity, and antistatic properties.

As an unexpected effect, the molding shrinkage due to the progress of crystallization of the polypropylene resin with the passage of time
It was found that the effect was reduced due to the effect of adding the acrylic acid copolymer resin.

Example B A photographic film cartridge main body corresponding to FIG. Same as Example A except that 5 parts by weight of titanium dioxide inorganic pigment surface-treated with zinc stearate as a light-shielding substance was added to the propylene-based resin composition of Example A in a light-shielding propylene / ethylene random copolymer resin. Injection molding equipment, using the same mold,
An injection-molded article for a photographic light-sensitive material, which is obtained by injection-molding a container body for a colored photographic film cartridge at a resin temperature of 220 ° C in a molding cycle of 7 seconds. This photographic film cartridge container body had an excellent appearance capable of continuous unmanned injection molding for a long time without causing a fatal molding failure.

The container body for photographic film cartridges, which is an injection-molded product, does not cause buckling or deformation such as bottom sink even if the molding cycle is shortened by 1 second as compared with Example A, and hardly causes coloring failure. The drop strength was also much larger than that of Example A, and the crack generation was 0% at room temperature (20 ° C.). The drop strength under the low temperature condition of 0 ° C. or less was also larger than that of the comparative product A, and the crack occurrence rate was also reduced to less than half.

Furthermore, although it is white and opaque, no thermal deformation occurs even if the container body is left in sunlight for 3 hours,
It was excellent in heat resistance, the temperature rise in the container was not so large as in Example A, thermal deformation of the spool of the photographic film cartridge was not caused, and the photographic property of the photographic film was hardly deteriorated. Furthermore, since it is a white background color, it has excellent suitability for transfer printing, and transfer printing was beautiful and of high commercial value. Further, the suitability for a curved surface high-speed printing machine was also excellent.

Even after being stored at 18 ° C for 1 year, oleic acid amide as a lubricant and polyoxyethylene sorbitan stearate as an antistatic agent did not bleed out to the surface of the container body, and stickiness, dust adhesion, and white powder were generated. Since the substance, titanium dioxide, was included, the amount was even smaller than in Example A, and due to the synergistic effect with the white appearance, almost no white powder could be aggregated, which was excellent.

[Example C] A container for a rectangular photographic film cartridge in which the body and the lid are integrated by a hinge and which corresponds to FIG.

Using the same propylene / ethylene random copolymer resin as in Example B, one container body for a rectangular photographic film patrone corresponding to FIG. 9 was prepared by injection molding method using a trial mold. did.

With regard to the characteristics, the characteristics are excellent as in Example B. Further, since it has a square shape, it has stackability and displayability at stores, so that it is possible to remove a small cosmetic box made of paper, CI mark and Since various prints are colored because they are white and opaque, and as described in Example B, because they are white and opaque, they do not cause thermal deformation of the container even when they reflect sunlight and are displayed in stores. There is little temperature rise in the container, therefore there is little deformation of the spool and deterioration of the photographic property of the photographic film, it has excellent antistatic properties, and since it contains titanium dioxide which is an oil absorbing substance, it can be applied to the container surface of lubricant, antioxidant, nucleating agent It has less bleed-out and less dust adherence, is excellent and has many industrial waste reduction and after-use applications.

[Comparative Example A] A container body for a photographic film cartridge corresponding to FIG. The same propylene ethylene random copolymer resin composition as in Example A except that 0.2 parts by weight of the two hindered phenolic antioxidants from Example A and 20 parts by weight of the ethylene / acrylic acid copolymer resin were removed. Molding cycle of a container body for photographic film cartridges made by using the same molding device and mold using
It is an injection-molded article for photographic light-sensitive material, injection-molded in seconds.

The container body for a photographic film cartridge, which is an injection-molded product, has the same characteristics, dimensional accuracy, and transparency as those of Example A except that the drop strength at low temperature of 0 ° C. or less is poor immediately after molding. It was excellent.

However, after being stored in a low temperature warehouse at 18 ° C. for 1 year, crystallization proceeded, so that the drop strength at room temperature was worse than that of Example A, and the surface of the lubricant was oleic acid amide and the antistatic agent of poly Oxyethylene sorbitan stearate bleeded out and some white powder adhered to the photographic film.

Further, since the addition amount of the hindered phenolic antioxidant is 0 part by weight, the resin is decomposed in the retained portion of the mold or the like to generate an aldehyde or the like when continuously molded for a long period of time, so that a photographic light-sensitive material is obtained. Adverse effects such as fog and increase / decrease
Unburnt continuous molding is difficult because the resin is burnt to cause coloring failure or lumps (black solid) to cause gate clogging or short shots.

Example D A photographic film container body corresponding to FIG. 8 (transparent container body). MFR (ASTM
D-1238, temperature 190 ℃, load 2.16kgf) 9g /
10 minutes, density (ASTM D-1505) 0.973 g / cm ³ , crystallinity (X-ray diffraction method) 97%, haze (ASTM D-100
3) 72%, flexural modulus (ASTM D-790) 15,600k
g / cm ² , Shore hardness (ASTM D-2240) 74D, 23 ° C
Notched Izod impact strength (ASTM D-256)
4.1kgcm / cm, Vicat softening point (ASTM D-1525)
Is 131 ° C, melting point (ASTM D-2117) is 140 ° C, elongation at break (ASTMD-638) is 358% 98.8% by weight of ultra-high density homopolyethylene resin, and 1.1 as a radical scavenger.
0.1% by weight of diphenyl-2-bicrylhydrazyl, pentaerythrityl-tetrakis [3- (3.5-di-t-butyl) which is a hindered phenolic antioxidant having a melting point of 100 ° C. or more as an antioxidant. -4-Hydroxyphenyl) propionate] Methane 0.1% by weight and a general formula of a phosphorus-based antioxidant

[0332]

[Chemical 16]

[In the formula, R ₁ represents a tertiary butyl group or a tertiary amyl group, R ₂ represents an alkyl group having 1 to 9 carbon atoms, R ₃ represents a hydrogen atom or 1 to 4 carbon atoms. an alkyl group, R ₄ represents an aryl group an alkyl group or having 6 to 15 carbon atoms having 1 to 30 carbon atoms. } Organic cyclic phosphorus compound of 0.05% by weight, as an organic nucleating agent 1, 3, 2.4
0.2% by weight of di (paramethylbenzylidene) sorbitol (manufactured by Shin Nippon Rika KK, Gelol MD), 0.1% by weight of glycerin monostearate ester as a drip-proof agent, 0.1% by weight of calcium stearyl lactate and 0.05% by weight of erucic acid amide as a lubricant. A homopolyethylene resin composition containing 0.3% by weight of magnesium stearate and 0.2% by weight of A-type zeolite was used.

A toggle injection molding machine with a mold clamping pressure of 150 tons {made by Sumitomo Heavy Industries, Nestal (trade name)} and a hot runner mold with 24 cavities were used, and the resin temperature was 20
At 0 ° C., the photographic film container body shown in FIG. 8 was prepared.

The inner wall surface of the container body has vertical streaky rough surfaces having a height difference of 0.25 μm, and the outer wall surface of the container body has a grid rough surface having a height difference of 0.15 μm. There is.

The container body of the present invention had a good haze of 31%, and it was possible to observe good color and clear printing in a state where the design and printing of the photographic film cartridge in the container body were sealed in the container body. In addition, the photographic properties of the photographic light-sensitive material are good (the occurrence of fog is small and the sensitivity does not fluctuate), the heat deterioration of the resin and the additive is small, and the coloring failure and the spots (blackish brown solid of foreign matter) are also generated. Almost gone. No fatal molding failure occurred, continuous unmanned injection molding was possible for a long time, and the appearance was excellent. Also, because a resin with a high crystallinity of 97% is used, the rigidity is high, the wear resistance is excellent, the cooling time can be greatly shortened, and 6 seconds molding is possible. In addition, the effect of forming a vertical streak-like rough surface with a height difference of 0.25 μm on the inner wall surface of the container body is also added, and there is no occurrence of buckling or bottom sink,
No sound was produced when the core came out of the container body.

Drop strength at low temperature is also improved, and 36 photo negative films of ISO 400 are taken from a height of 0 ° C.) There is no crack even if dropped from a height of 5 m in a sealed state to a concrete floor ( It was 0%). Furthermore, even after taking out the photographic film cartridge from the container body after storing it in a low temperature warehouse for one year, the conventional offensive odor is reduced to a level that is not noticeable, and water droplets are no longer observed on the peripheral wall of the container body. The deterioration of photographic performance was within 5%, which was excellent without any trouble in photographing.

Example E A photographic film container body corresponding to FIG. 8 (light-shielding container body). MFR (AST
MD-1238, temperature 190 ℃, load 2.16kgf) 18g
/ 10 minutes, density (ASTM D-1505) 0.963 g / cm ³ , crystallinity (X-ray diffraction method) 92%, haze (ASTM D-1)
003) is 65%, flexural modulus (ASTM D-790) is 12,80
0kg / cm ² , Shore hardness (ASTM D-2240) 70D, 23
Izod impact strength with notch at ℃ (ASTM D-256)
Is 4.7 kg / cm / cm, Vicat softening point (ASTM D-152
5) 122 ° C, melting point (ASTM D-2117) 133 ° C, elongation at break (ASTM D-638) 500% or more high density homopolyethylene resin, and 0.3 weight of A-type zeolite as an inorganic substance having an ion exchange function. %, Pentaerythrityl-tetrakis [3- (3.5-di-t-butyl-4-), which is a hindered phenolic antioxidant as an antioxidant.
Hydroxyphenyl) propionate] methane 0.1% by weight, phosphorus antioxidant tris (2,4-di-t-butylphenyl) phosphite 0.05% by weight, 1 as an organic nucleating agent
-0.2% by weight of 3,2.4-di (paramethylbenzylidene) sorbitol (manufactured by Shin Nippon Rika KK, Gelol MD),
Glycerin monostearate ester 0.1 as drip-proof agent
% By weight, calcium stearyl lactate as a lubricant 0.1% by weight, erucic acid amide 0.05% by weight, zinc stearate 0.2
The average particle size is 21m, which is an oil-absorbing substance whose surface is coated by weight.
μ, pH 8.0, oil absorption 87 ml / 100 g, sulfur content 0.
A homopolyethylene resin composition containing 3% by weight and 0.8% by weight of an oil furnace carbon black containing 0.3% by weight of a volatile component was used.

Then, using a toggle type injection molding machine with a mold clamping pressure of 150 tons {made by Sumitomo Heavy Industries, Nestal (trade name)} and a hot runner type mold with 24 cavities, the resin temperature
The photographic film container body shown in FIG. 8 was prepared at 200 ° C.

A vertical streak-like rough surface having a height difference of 0.25 μm is formed on the inner wall surface of the container body, and a grid-like rough surface having a height difference of 0.15 μm is formed on the outer wall surface of the container body. There is.

The container body of the present invention has improved uniform dispersibility of carbon black, good photographic properties of the photographic light-sensitive material (less fog generation and less sensitivity fluctuation), high resin haze and high density. Since it uses a homopolyethylene resin, it has excellent light-shielding ability, there is no coloring failure, there are almost no spots, and there is no fatal molding failure.
The appearance was excellent and continuous unmanned injection molding was possible for a long period of time. In addition, since a resin with a high crystallinity of 92% was used, the rigidity was high, the abrasion resistance was excellent, the cooling time could be shortened, and molding for 7 seconds became possible. In addition, the effect of forming a vertical streak-like rough surface with a height difference of 0.25 μm on the inner wall surface of the container body is added, buckling and sink marks are not generated, and sound is generated even when the core comes off from the container body. I didn't.

[Embodiment F] A spool for photographic film corresponding to FIG. MFR 40g / 10min, density 0.90g
/ Cm ³ , crystallinity 95%, flexural modulus (ASTM D-79
0) is 12,500 kg · cm / cm, the propylene content is 98% by weight with a molecular weight distribution (weight average molecular weight / number average molecular weight) of 4.5,
70 parts by weight of propylene-ethylene random copolymer resin having an ethylene content of 2% by weight, MFR of 25 g / 10 minutes,
Density 0.925g / cm ³ , Olsen rigidity 2,800kg / cm ² (J
IS K-7106), molecular weight distribution (weight average molecular weight / number average molecular weight) of 3.5, ethylene content of 96 parts by weight, butene-
19.5 parts by weight of low-pressure vapor phase ethylene / butene-1 copolymer resin containing 4% by weight, 0.10 part by weight of erucic acid amide as a lubricant, and calcium hydroxystearate.
2 parts by weight and the content of monoglyceride in the antistatic agent is 95
% Stearic acid monoglyceride 0.2 wt% propylene ethylene random copolymer resin 100 parts by weight,
Vitamin E (α-tocopherol) as an antioxidant 0.
10 parts by weight of hindered phenolic antioxidant 2,6-di-tert-butyl-p-cresol (generally B
(Known as HT), a propylene / ethylene random copolymer resin composition comprising 0.3 parts by weight of calcium carbonate surface-treated with 0.2 parts by weight of dimethylpolysiloxane as an inorganic nucleating agent is used. Using an injection molding machine with a mold clamping pressure of 150 tons, a hot runner type mold with 24 cavities and a resin temperature of 205 ° C
Molding cycle 8 for photographic film spools equivalent to 0
It is an injection-molded article for photographic light-sensitive material, injection-molded in seconds.

This photographic film spool has a coloring failure,
Almost no fatal molding failures such as short shots and poor light-shielding properties, very good lubricity, good removability from the mold, no deformation, and long-term continuous unmanned injection molding is possible. became. In order to reduce the drawing torque of photographic film made of conventional polystyrene resin,
Compared to photographic film spools that have been coated with a surfactant on the flange, this photographic film spool, an injection-molded product, has a faster molding cycle, less scratches and abrasions, and better lubricity. The film draw-out torque is small, and it is particularly effective for cameras that use a battery-powered automatic photographic film winding system.The winding stop during shooting is greatly reduced, and battery consumption is greatly reduced. It was It is also excellent in chemical resistance and solvent resistance, and it is preferable as a spool for photographic film used all over the world under a wide temperature range from high temperature to low temperature in a laboratory handling various chemicals. Met.

As an unexpected effect, the fog of the photographic film is reduced (the density is reduced by 0.03), and the light-shielding ability is improved by 15% (even if the light-shielding substance is reduced by 15%, the light-shielding property is substantially the same). The uniform dispersibility of the light-shielding substance is improved, and the sink marks in the thick part, warpage of the flange, and large molding shrinkage that occur when the conventional crystalline resin propylene / ethylene random copolymer resin is used. The rate has improved to the point where there is no problem.

[0345] As described above, it was excellent in that various properties were improved and the occurrence of lubricant and antistatic bleed out was small. This is due to the additive effect of using special furnace carbon black and vitamin E in combination to reduce the generation of aldehydes, etc., which adversely affect the photographic film that occurs when the resin is decomposed in the presence of heat and oxygen.
The propylene / ethylene random copolymer resin with a small molecular weight distribution and the ethylene / butene-1 copolymer resin are used in combination to improve the light-shielding ability by coloring and reduce the molding shrinkage rate, and reduce sink marks and flange warpage. This is probably due to the reduced effect of injection molded products.

Example G A resin photographic film cartridge corresponding to FIG. Using the resin composition of Example D, the polypropylene resin photographic film cartridge shown in FIG. 11 was prepared by the injection molding method. However, as in Example F, it was an injection molded product for photographic light-sensitive materials having various excellent characteristics. It was In particular, it has excellent lubricity, wear resistance, and injection moldability, and the torque for feeding and winding the photographic film is small, and there are no failures that stop during shooting.

The preferred embodiments will be described below. (1) Melt flow rate (AST
(MD-1238, temperature 190 ℃, load 2.16kgf)
Of 5 to 40 g / 10 minutes, density of 0.950 to 0.985 g / cm ³ , crystallinity of 80% or more by X-ray diffraction method, flexural rigidity (ASTM
D-747) is 8000kg / cm ² or more, Vicat softening point (AST
MD-1525) 50% by weight of homopolyethylene resin and / or ethylene / α-olefin copolymer resin having a temperature of 115 ° C or higher.
The above is preferable, 70 wt% is particularly preferable, and 90 wt% or more is the most preferable.

(2) 0.001 of antioxidant in the resin for the container body
~ 2 wt%, nucleating agent 0.01-2 wt%, lubricant 0.001 ~
It is preferable to contain 5% by weight from the viewpoints of improving transparency, preventing thermal deterioration of resins and nucleating agents, improving injection moldability, preventing the generation of substances that adversely affect the photographic properties of photographic films, and preventing the generation of colored substances.

(3) In order to prevent the residual polymerization catalyst from adversely affecting the photographic properties of the photographic film, metal soap (preferably stearyl emulsion calcium, calcium stearate, zinc stearate, magnesium stearate, sodium palmitate, Sodium benzoate, etc.)
A container body injection-molded from a polyolefin resin composition containing 0.001 to 5% by weight, preferably 0.01 to 2% by weight, and particularly preferably 0.05 to 1% by weight.

(4) A container body composed of a polyolefin resin composition containing 0.01 to 2% by weight of an organic nucleating agent and 0.001 to 2% by weight of an antioxidant and having been subjected to a heat history of 190 ° C. or more once or more.

(5) Haze of container body (ASTM D-1003
The value when the average thickness of the container body peripheral wall and / or bottom is 0.4 to 1.2 mm) measured in accordance with
% Or less, particularly preferably 40% or less, most preferably 30%
The following is preferable as the transparent container body that allows the characters and marks printed on the photographic film cartridge in the container body to be visually confirmed from the outside of the container body (the haze of the present invention complies with ASTM D-1003). The value measured with the thickness of the peripheral wall portion and the bottom portion measured as is.

(6) As an antioxidant, the melting point is 100 ° C. or higher,
A container body made of a polyolefin resin composition preferably containing 0.001 to 2% by weight of a total content of at least one kind of hindered phenol antioxidant and / or phosphorus antioxidant at 120 ° C. or higher.

(7) A molded product for a photographic light-sensitive material, wherein the crystalline resin is a polyolefin resin.

(8) Molded article for photographic light-sensitive material containing at least vitamin E as an antioxidant

(9) Molded article for photographic light-sensitive material, wherein the molded article is a resin film molded article

(10) Molded article for photographic light-sensitive material, wherein the molded article is an injection molded article

(11) Molded article for photographic light-sensitive material, containing 0.001 to 2% by weight in total of one or more phenolic antioxidants and one or more phosphorus antioxidants as antioxidants

(12) Molded article for photographic light-sensitive material which is a photographic film container having a haze (ASTM D-1003) of 80% or less, preferably 60% or less, particularly preferably 40% or less, and most preferably 30% or less.

(13) Haze containing 0.01 to 5.0% by weight of a nucleating agent and 70% by weight or more of a homopolyethylene resin and / or an ethylene / α-olefin copolymer resin having a crystallinity of 75% or more by an X-ray diffraction method. (ASTM D-1003) 80% or less, preferably 60% or less, particularly preferably 40% or less, most preferably 30% or less.

(14) A molded article for a photographic light-sensitive material, which is a photographic film container containing 5 to 45% by weight, preferably 7 to 40% by weight, particularly preferably 10 to 35% by weight of an acrylic acid copolymer resin.

[0361]

INDUSTRIAL APPLICABILITY Since the present invention can reduce the bleed-out of lubricants and antistatic agents over time, the lubricity and antistatic property can be maintained for a long time, and the generation of white powder due to bleed-out can be reduced. Can be made. Further, it is possible to prevent the occurrence of spots and coloring defects due to the thermal deterioration of the resin and the additives, and to reduce the fog increase and the sensitivity fluctuation of the photographic light-sensitive material.

[Brief description of drawings]

FIG. 1 is a partial cross-sectional view of a packaging film for a photographic light-sensitive material, which is an example of a molded product for a photographic light-sensitive material according to the present invention.

2 (a) and (b) are partial cross-sectional views of a packaging film for a photographic light-sensitive material, which is an example of a molded product for a photographic light-sensitive material of the present invention.

FIG. 3 is a partial sectional view of a packaging film for a photographic light-sensitive material, which is an example of a molded product for a photographic light-sensitive material of the present invention.

4A and 4B are partial cross-sectional views of a packaging film for a photographic light-sensitive material, which is an example of a molded product for a photographic light-sensitive material of the present invention.

FIG. 5 is a partial sectional view of a packaging film for a photographic light-sensitive material, which is an example of a molded product for a photographic light-sensitive material of the present invention.

FIG. 6 is a partial cross-sectional view of a packaging film for a photographic light-sensitive material, which is an example of a molded product for a photographic light-sensitive material of the present invention.

FIG. 7 is a partial cross-sectional view of a packaging film for a photographic light-sensitive material, which is an example of a molded product for a photographic light-sensitive material of the present invention.

FIG. 8 (a) is a cross-sectional view of a photographic film container of a body-separated body type which is an embodiment of the molded product for photographic light-sensitive material of the present invention. (b) is a cross-sectional view of another container for photographic film of a body-separated body type which is an example of the molded article for photographic light-sensitive material of the present invention.

FIG. 9 is a cross-sectional view of a rectangular lid-integrated photographic film container which is an embodiment of a molded product for a photographic light-sensitive material of the present invention.

FIG. 10 is a front view of a photographic film spool which is an example of a molded product for a photographic light-sensitive material of the present invention.

FIG. 11A is an exploded perspective view of a resin photographic film cartridge that is an example of a molded product for a photographic light-sensitive material of the present invention. (b) is a perspective view of a resin photographic film cartridge which is an example of a molded product for a photographic light-sensitive material of the present invention.

FIG. 12 is an exploded perspective view of a film unit with a lens, which is an example of a molded product for a photographic photosensitive material of the present invention.

FIG. 13 is a cross-sectional view of a body-integral prismatic photographic film case that is an example of a molded product for a photographic light-sensitive material of the present invention.

FIG. 14 is an exploded perspective view of a photographic film cartridge that is an embodiment of a molded product for photographic light-sensitive material of the present invention.

FIG. 15 is a perspective view showing a packaging process of a band-shaped photographic light-sensitive material package using a light-shielding film having a light-shielding thermoplastic resin film layer, which is an example of the molded product for photographic light-sensitive material of the present invention.

[Explanation of symbols]

1a ... Light-shielding thermoplastic resin film layer (molded product for photographic photosensitive material) 2, 2a ... Thermoplastic resin film layer 3a ... Intermediate layer 4 ... Adhesive layer 5 ... Flexible sheet 9 ... Metal vapor deposition biaxially stretched film layer 10 ... Metal Foil

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁵ Identification code Office reference number FI technical display location B32B 15/08 103 7148-4F B65D 1/09 85/672 7445-3E

Claims (17)

[Claims] 1. A crystalline resin composition containing 100 parts by weight of a crystalline resin and a lubricant and / or an antistatic agent, and 0.001 of an antioxidant.
Molded article for photographic light-sensitive material, comprising a molding resin composition composed of 1 to 2.0 parts by weight and acrylic acid copolymer resin 5 to 90 parts by weight. 2. A polyolefin resin 50% by weight or more, a lubricant and / or an antistatic agent 0.01 to 5.0% by weight, and an antioxidant 0.0.
01 ~ 2.0wt%, Inorganic substance with ion exchange function 0.0
Molded article for photographic light-sensitive material comprising polyolefin resin composition containing 1 to 10% by weight 3. Polyolefin resin 50% by weight or more, lubricant and / or antistatic agent 0.01 to 5.0% by weight, antioxidant 0.0
01 to 2.0% by weight, oil absorbing substance with oil absorption of 50ml / 100g or more 0.
Molded article for photographic light-sensitive material comprising polyolefin resin composition containing 01 to 30% by weight 4. A polyolefin resin 40% by weight or more, a lubricant and / or an antistatic agent 0.01 to 5.0% by weight, and an antioxidant 0.0.
01-2.0% by weight, acrylic acid copolymer resin 5-45% by weight
Molded article for photographic light-sensitive material comprising polyolefin resin composition containing 5. A polyolefin resin 20% by weight or more, a lubricant and / or an antistatic agent 0.01 to 5.0% by weight, and an antioxidant 0.0.
Molded article for photographic light-sensitive material comprising a polyolefin resin composition containing 01 to 2.0% by weight, acrylic acid copolymer resin 5 to 75% by weight, and light shielding substance 0.01 to 30% by weight 6. A light-shielding substance 0.01 to 30% by weight having a polyolefin resin of 50% by weight or more, a refractive index (measured by Larsen oil immersion method) surface-treated with a surface-treating substance of 1.50 or more, and an oil absorption of 50 ml / 100 g or more Molded article for photographic light-sensitive material containing 0.001 to 2.0% by weight of at least one of antioxidant, radical scavenger and antioxidant synergist, and 0.01 to 5.0% by weight of lubricant and / or antistatic agent 7. A light-shielding substance having a pH of 6.0 to 9.0, an average particle size of 10 to 120 mμ, a volatile component of 2.0% or less, and an oil absorption amount of 50 ml /
A molded article for a photographic light-sensitive material according to claim 5, which is 100 g or more of furnace carbon black. 8. A molded product for a photographic light-sensitive material according to claim 1, which contains 0.01 to 2.0% by weight of a fatty acid metal salt. 9. A molded product for a photographic light-sensitive material according to claim 1, which contains 3 to 50% by weight of ethylene / propylene rubber. 10. The molded article for photographic light-sensitive material according to claim 1, 2, 3, 4, 5 or 6, which contains a silicone oil. 11. The container body has a melt flow rate (AST
(MD-1238, temperature 190 ℃, load 2.16kgf)
Is 5 to 60g / 10 minutes, and the density (ASTM D-1505) is 0.941g
/ Cm ^{3 to} 0.985 g / cm ³ , crystallinity by X-ray diffraction method is 75
% Or more, flexural rigidity (ASTM D-747) is 6000 kg / cm ²
Above, Shore hardness (ASTM D-2240) is 60D or more, 2
3 ° C notched Izod impact strength (ASTM D-25
6) is 2.0 kg ・ cm / cm or more, Vicat softening point (ASTM
D-1525) has a melting point (ASTM D-2117) of 110 ° C or higher.
50% by weight or more of homopolyethylene resin and / or ethylene / α-olefin copolymer resin at 120 ° C or higher, 0.01 to 2% by weight of one or more inorganic and organic nucleating agents, and antioxidant and radical scavenger Molded article for photographic light-sensitive material, which is a container for photographic film formed of a polyethylene resin composition containing 0.001 to 2% by weight of one or more kinds 12. The container body has a melt flow rate of 5 to 80.
g / 10 min, density of ^{0.941g / cm 3 ~0.985g / cm 3} , crystallinity by X-ray diffractometry of 75% or more, the bending rigidity 6000 kg / cm
² or more homopolyethylene resins and / or ethylene / α
Of an olefin copolymer resin 50% by weight or more, a carboxylic acid having 3 or more carbon atoms and a nitrogen-containing heterocyclic compound having an amino group or a hydroxyl group at the α-position, and / or a divalent or more aliphatic amine Molded article for photographic light-sensitive material, which is a photographic film container formed of a polyethylene resin composition containing 0.01 to 5% by weight of an organic nucleating agent composed of an alicyclic carboxylic acid amide compound and having a haze of 80% or less 13. The container body is an organic cyclic phosphorus compound, melting point 80 ° C.
13. A polyolefin resin composition containing one or more of the above hindered phenolic antioxidants, radical scavengers and antioxidant synergists.
Molded product for photographic light-sensitive material 14. The composition according to claim 1, 2, 3, 4, 5, 6, 11 or 12, containing at least one of an oxygen scavenger, a deodorant, a hygroscopic agent, a dripproofing agent and an inorganic substance having an ion exchange function. Molded articles for photographic light-sensitive materials described 15. Claims 1, 2, 3, 4, 5, 6, 11 or
Using the molded article for a photographic light-sensitive material described in 12, the photographic light-sensitive material has a moisture permeability (measured under condition B of JIS Z 0208) of 10 g / m ^2.
・ Oxygen permeability (ASTM D-3985) is 50cc for 24 hours or less
/ M ² · 24 hours · 1 atmosphere · 20 ° C or less sealed package, photographic material packaging material 16. A CAS code, a bar code, a CI mark, a product name, an instruction manual, on the surface of a molded product for a photographic light-sensitive material.
16. The photographic light-sensitive material package according to claim 15, wherein at least one of the product identification mark and the product identification color is printed or a label printed with these is attached. 17. The photographic light-sensitive material package according to claim 15, wherein the photographic light-sensitive material contains a deodorant, an aromatic agent, a moisture absorbent and an oxygen absorber, and is printed, attached or coated.