JP3055582B2 - Molded article for photographic light-sensitive material and photographic light-sensitive material package using the same - Google Patents

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 more particularly to a molded article for a photographic light-sensitive material containing at least a surface-treated light-shielding substance, a phenolic antioxidant and at least one thermoplastic resin. The present invention relates to a molded article for photographic photosensitive materials having excellent light-shielding properties and appearance.

[0002]

2. Description of the Related Art Conventionally, molded articles for photographic photosensitive materials include:
A container body for a film cartridge has been proposed (Japanese Utility Model Publication No. 2-33236). The above-mentioned container body is a film cartridge container body containing 0.1 to 3% by weight of a light-shielding substance in a polypropylene resin having special physical properties. It is an excellent thing that can be greatly improved.

As another molded article for photographic photosensitive materials, a film for packaging a photosensitive material has been proposed (Japanese Patent Publication No. 2-2700).
No.). This film is a photosensitive material packaging film comprising a polyethylene-based polymer and 1% by weight or more of a light-shielding substance, and having at least one layer of a light-shielding film in which 50% by weight or more of the total polyethylene-based polymer is L-LDPE resin. , Physical strength, heat sealing suitability and the like.

[0004]

However, when the amount of the light-shielding substance is increased, the film body of the container for the film partrone generates butters (insoluble clusters) due to poor dispersion of the light-shielding substance and lowers the drop strength. And photographic properties are further deteriorated (fog and sensitization are caused), and it has been particularly difficult to put into practical use as a container body for a recent high-speed photographic negative film (ISO speed of 100 or more). Further, in the photosensitive material packaging film, when the content of the light-shielding substance is increased, adverse effects on the photographic properties occur and the occurrence of irregularities due to poor dispersion increases, and the light-shielding failure due to pinholes due to vibration or the like during the transportation process is reduced. There was a problem in point.

The present invention provides a molded article described in Japanese Utility Model Publication No. 2-33236 and Japanese Examined Patent Publication No. 2-2700, while protecting the molded article from light even when the amount of the light-shielding substance added is increased. For photosensitive materials with good dispersibility of active substances, small decrease in physical strength, good photographic properties, and excellent appearance with no light spots (film molded products, injection molded products, vacuum (A molded article, etc.).

[0006]

Means for Solving the Problems The inventors of the present invention have made intensive studies to achieve the above-mentioned object, and it has been found that an excellent effect can be obtained if a light-shielding substance is surface-treated with a specific surface-treating substance and an antioxidant is used in combination. It has been found that the present invention has an effect, and the present invention has been completed. That is, the molded article for a photographic light-sensitive material of the present invention has an organometallic chelate compound as a surface treatment substance and a concentration at ordinary temperature.
5,000 to 30,000 centistokes of high viscosity
1 of corn oil, drip-free agent and organoaluminum compound
0.01 % of light-shielding substance surface-treated with one or more
The light-shielding thermoplastic resin composition contains at least about 30% by weight and at least 0.01% to 2.0 % by weight of an antioxidant.

[0007] Examples of the surface treating substance include a lubricant, an antistatic agent, hydrous aluminum hydroxide, hydrous silicon dioxide,
To 4-valent alcohols, surfactants, organometal chelate compounds, coupling agents, hydrocarbons having a softening point of 90 ° C. or lower, silicone oils, and the like. One of these types or a combination of a plurality of types may be used.

[0008] Specifically, the following are examples of the surface treatment substances. [Lubricant] The names of typical commercially available lubricants and manufacturers are described below. (1) Fatty acid amide-based lubricant (saturated fatty acid amide-based lubricant) Behenic acid amide-based lubricant; Diamid KN (Nippon Kasei), etc. Stearamide-based lubricant; Armide HT (Lion fat), Alflow S-10 (Nippon fat) Fatty acid amide S (Kao), Diamid 200 (Nippon Kasei), Diamid AP-1 (Nippon Kasei), Amide S. Amide T
(Nitto Kagaku), Neutron-2 (Nippon Seika), etc. Hydroxystearic amide lubricant Palmitic amide lubricant; Neutron S-18 (Nippon Seika), Amide P (Nitto Chemical), etc. Lauric amide lubricant Armid C (Lion
(Akzo), Diamid (Nippon Kasei), etc. (Unsaturated fatty acid amide lubricant) Erucamide amide lubricant; Alflow P-10 (Nippon Oil & Fats), Neutron-S (Nippon Seika), LUBROL (IC)
・ I), Diamid L-200 (Nippon Kasei), etc. Oleic acid amide lubricants; Armoslip CP (Lion Akzo), Neutron (Nippon Seika), Neutron E-18 (Nippon Seika), Amide O (Nitto Kagaku), Diamid O-200, Diamid G-200 (Nippon Kasei), Alflo E-10 (Nippon Yushi), fatty acid amide O (Kao), etc. (Bis fatty acid amide lubricant) Methylene bisbehenic acid Amide lubricants; Diamid NK bis (Nippon Kasei), etc. Methylene bisstearic acid amide lubricants; Diamid 200 bis (Nippon Kasei), Armowax (Lion
Akzo), bisamide (Nitto Kagaku), etc. Methylene bisoleic amide lubricant; Lubron O
(Nippon Kasei) etc. Ethylene bisstearic amide lubricant; Armoslip EBS (Lion Akzo), etc. Hexamethylene bisstearic amide lubricant; Amide 65 (Kawaken Fine Chemical), etc. Hexamethylene bis oleamide amide lubricant; Amide 60 (Kawaken Fine Chemical), etc. (2) Nonionic surfactant-based lubricant; electro stripper
-TS-2, Electrostripper-TS-3 (Kao soap), etc. (3) Hydrocarbon lubricants; liquid paraffin, natural paraffin, microwax, synthetic paraffin, polyethylene wax (molecular weight of 6000 or less is preferred), polypropylene wax ( . 6000 molecular weight or less are preferred), chlorinated hydrocarbons, fluoro carboxylic, etc. (4) fatty acid lubricants; higher fatty acids (C ₁₂ or more are preferred,
(Specifically, caproic acid, stearic acid, oleic acid, erucic acid, palmitic acid, etc.), oxy fatty acids, 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 lubricants; polyhydric alcohols, polyglycols, polyglycerols (7) Metallic soaps; lauric acid, stearic acid, succinic acid, stearyl lactic acid, benzoic acid, hydroxystearic acid, lactic acid, phthalate Acid, ricinoleic acid, naphthenic acid, oleic acid, palmitic acid, higher fatty acids such as erucic acid and L
i, K, Na, Mg, Ca, Sr, Ba, Zn, Cd,
Examples thereof include compounds with metals such as Al, Sn, Pb, and Cd, and preferred are magnesium stearate, calcium stearate, zinc stearate, and magnesium oleate. (8) Partially saponified montanic acid ester (9) Silicone-based lubricant; various grades of dimethylpolysiloxane and its modified products (Shin-Etsu Silicone, Toray Silicone), especially various silicones have the effect of improving resin fluidity and lubricity. In addition to exhibiting the effect, it is preferable to use it in combination with a coloring substance because unexpected effects such as an improvement in coloring power and an improvement in light-shielding properties can be exhibited as a result of improving the dispersibility of the coloring substance and increasing the haze by making the resin cloudy.

The amount of the lubricant to be added differs depending on the kind. Among the lubricants most suitable for the molded article for photographic light-sensitive materials of the present invention, a lubricant having a small lubricating effect, such as a fatty acid metal salt, is used in an amount of 0.1.
03-5% by weight, preferably 0.05-3% by weight, particularly preferably 0.1-1.5% by weight. Lubricants such as fatty acid amide and bis fatty acid amide-based lubricants have a large lubricating effect, easily bleed out, and affect the photosensitive material.
It is 0.01 to 1% by weight, preferably 0.03 to 0.5% by weight, particularly preferably 0.05 to 0.3% by weight.

[Antistatic agent] Nonionic (= nonionic) (1) Alkylamine derivative: T-B103 (Matsumoto Yushi), T
-B104 (Matsumoto Yushi) Alkylamide type polyoxyethylene alkylamine: Armostat 31
0 (lion fat) Tertiary amine (lauryl amine): Armostat 400 (lion fat) N, N-bis (2-hydroxyethyl cocoamine): Armostat 410 (lion fat) Tertiary amine: ANTISTATIC 273C, 273, 273E (FineOrg. Ch
em) N-hydroxyhexadecyl-di-ethanol-amine: Belg. P. 654,
049 N-hydroxyoctadecyl-di-ethanol-amine: (National Dis
t.) (2) Fatty acid amide derivative: TB-115 (Matsumoto Yushi), Elegan P100 (Nippon Yushi), Erik SM-2 (Yoshimura Oil Chemical) hydroxystearic acid amide oxalic acid-N, N'-distearylamidobutyl Ester: Hoechst polyoxyethylene alkyl amide (3) Ether type polyoxyethylene alkyl ether RO (CH ₂ CH ₂ O) nH polyoxyethylene alkyl phenyl ether Special non-ion type: Register 104, PE 100, 116-118
(Daiichi Kogyo Pharmaceutical Co., Ltd.), Resistat PE 132, 139 (Daiichi Kogyo Pharmaceutical Co., Ltd.), Elegan E115, Chemistat 1005 (Nippon Oil & Fats), Erik BM-1 (Yoshimura Oil Chemical), Electrostripper TS, TS2, 3, 5, 5. EA, EA2,3
(Kao Soap) (4) Polyhydric alcohol ester type glycerin fatty acid ester: mono-, di- or triglyceride such as stearic acid or hydroxystearic acid, monogly ((Nippon camphor), TB-123 (Matsumoto oil and fat),
RESORT 113 (Daiichi Kogyo Seiyaku) Sorbitan fatty acid ester Special ester: Elique BS-1 (Yoshimura Oil Chemical) 1-hydroxyethyl-2-dodecylglyoxazoline: British cellophane

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

III. Cationic (1) Amide-type cation: Resistet PE300, 401, 40
2, 406, 411 (Daiichi Kogyo Seiyaku) (2) Quaternary ammonium salt quaternary ammonium chloride quaternary ammonium sulfate quaternary ammonium nitrate Katimine CSM-9 (Yoshimura Oil Chemical), CATANAC 609 (American cyanamide) ), Denon 314C (Marubishi Yuka), Armostat 300 (Lion Fat), 100V (Armor), Electrostripper-ES (Kao Soap), Chemistat 20
09A (Nippon Yushi) Stearamido propyl-dimethyl-β-hydroxyethyl ammoniu
m nitrate: CATANAC / SN (American dianamid)

IV. Zwitterionic (1) Alkyl petane type: (2) Imidazoline type: Rheostat 53, 532 (Lion fat), AMS 53 (Lion fat), AMS 303, 313 (Lion fat) Alkyl imidazoline type (3) Metal salt type : AMS 576 (lion fat) Rheostat 826, 923 (lion fat) (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: Registerat 204, 205 (Daiichi Kogyo Seiyaku), Elegan 2E, 100E (Nippon Yushi), Chemistat 1002, 1003, 2010 (Nippon Yushi), Elique 51
(Yoshimura Oil Chemical), ALROMINE RV-100 (Geigy)

Among the above antistatic agents, nonionic (nonionic) antistatic agents are particularly preferred because of their small adverse effects on photographic properties and human body.

[Hydrous aluminum oxide] Alumina and the like.

[Containing silicon oxide] Natural silica, synthetic silica and the like.

[2-4 alcohols] Ethylene glycol, propylene glycol, 1,3-dihydroxybutane, heptamethylene glycol, trimethylolethane, glycerin, 1,2,6-hexanetriol and the like.

[Surfactants] Nonionic surfactants, anionic surfactants, cationic surfactants, zwitterionic surfactants and the like.

[Amine compounds] Primary amines such as ethanolamine, laurylamine and butatriamine. Secondary amines such as diethanolamine and N-methylethanolamine. A tertiary amine such as triethanolamine or N.N-dimethyllaurylamine is coated on the light-shielding substance at 0.01 to 5% by weight.

[Organic Metal Chelate Compound] Ethylenediaminetetraacetic acid, N-hydroxyethyl-ethylenediamine-
N, N ^′ , N ^″ -triacetic acid, diethylenetriaminepentaacetic acid, β-diketone chelate, nitrilotriacetic acid, potassium sodium tartrate and the like.

[Coupling agent] Silanes (vinyltrichlorosilane, vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, etc.) and titanates (isopropyl-triisostearoyl-titanate, etc.).

[Hydrocarbons having a softening point of 90 ° C. or less] EVA resin, EEA resin, EM having a comonomer content of 5% by weight or more
A resin, EAA resin, density 0.92 g / cm ³ less than the homo polyethylene resin, density 0.915 g / cm ³ less than the ethylene · alpha-olefin copolymer resins, acid-modified polyolefin resin, polyethylene wax, polypropylene wax, cyclopentadiene Resins and modified hydrocarbon resins.

[Silicone oil] Various silicones not only exert the effects of improving resin fluidity and lubricity, but also improve the dispersibility of light-shielding substances, make the thermoplastic resin opaque, and increase the haze, resulting in coloring. It is preferable because unexpected effects such as improvement in force and improvement in light-shielding properties are exhibited. Silicone oil has a viscosity at room temperature of 50-100,
It is preferably in the range of 000 centistokes, and more preferably in the range of 5,000 to 30,000 centistokes. Specifically, silicone oils are polydimethylsiloxane, polymethylphenylsiloxane, olefin-modified silicone, amide-modified silicone, amino-modified silicone, carboxyl-modified silicone, α-methylstyrene-modified silicone, polyether-modified with polyethylene glycol or polypropylene glycol. Silicone, olefin / polyether modified silicone,
It is a silicone oil containing a modified siloxane bond such as an epoxy-modified silicone, an amino-modified silicone, and an alcohol-modified silicone. Among the silicone oils, olefin-modified silicone, amide-modified silicone, polydimethylsiloxane, polyether-modified silicone, olefin / polyether-modified silicone, and the like are particularly excellent. The silicone oil improves the coefficient of friction of a molding material such as a film in a heated state, reduces sliding resistance generated during sealing of a hot plate by an automatic wrapping machine, and prevents wrinkles from forming. It is possible to create a basis for obtaining a film that retains performance having high sealing properties and tight adhesion to a package. In addition, it is possible to prevent a decrease in gloss due to sliding and obtain a beautiful seal portion. In the present invention in which silicone oil is used in combination, when performing sliding heat sealing, the high temperature friction coefficient is 1.4.
It can be:

The amount of addition varies depending on the type and purpose of use, but is preferably 0.01 to 5.0% by weight, more preferably 0.0 to 5.0% by weight.
It is 3 to 3.0% by weight, most preferably 0.05 to 1.0% by weight.

The effect of the addition of silicone oil is as follows: simply by using together with fibrous fillers, non-fibrous light-shielding substances and pigments, coats these surfaces to improve dispersibility; Improves lubricity, reduces screw motor load and prevents melt fracture; Sufficient lubricity can be ensured without the addition of fatty acid amide that bleeds out and forms white powder; It can reduce the coefficient of friction, improve the suitability of automatic bags, prevent wrinkles during heat sealing and decrease the gloss due to sliding, and obtain a beautiful sealed part; when used together with a light-shielding substance, thermoplastic resin can be used As a result of increasing turbidity and haze, coloring ability can be improved and light-shielding ability can be improved, and light-shielding properties can be ensured even when the amount of a light-shielding substance that reduces physical properties is reduced.

Other surface-treating substances include non-dropping agents. Photosensitive materials are usually stored in low-temperature warehouses and household refrigerators for long-term quality assurance, and are taken out at normal temperature when used. Water droplets are generated on a photographic film spool injection molded product around which a photographic photosensitive material is wound or a photographic film patrone container main body injection molded product sealingly packaging a photographic film patrone. Therefore, a drip-free agent may be added to prevent water droplets from being generated on the surface of the molded product even if the ambient temperature changes rapidly and greatly. The drip-free agent also suppresses and makes uniform the bleed-out of the lubricant, an antioxidant and an organic nucleating agent described below. Representative examples of the drip-free agent are shown below. Diglycerin monostearate, polyglycerin monopalmitate, sorbitan monolaurate, sorbitan monostearate, sorbitan monooleate, sorbitan monoerucate, polyoxyethylene sorbitan fatty acid ester, stearic acid monoglyceride, polyoxy Ethylene nonyl phenol ether, sorbitan sesquipalmitate, diglycerin sesquioleate, sorbitol fatty acid ester, sorbitol fatty acid dibasic acid ester, diglycerin fatty acid dibasic acid ester, glycerin fatty acid dibasic acid ester, sorbitan fatty acid dibasic acid Ester, sorbitan palmitate, sorbitan stearate, sorbitan palmitate propylene oxide 3 mol Addendum, sorbitan palmitate propylene oxide 2 mol adduct, sorbitol stearate, sorbitol stearate ethylene oxide 3
Mole adducts, diglycerin palmitate, glycerin palmitate, glycerin palmitate / ethylene oxide 2 mol adduct, and the like.

The addition amount of the drip-free agent is 0.03 to 5% by weight, preferably 0.1 to 3% by weight, particularly preferably 0.2 to 1.5% by weight.

Other surface treating agents include organoaluminum compounds (specifically, aluminum ethylate,
Aluminum monoacetylacetonate, bisethylacetoacetate, aluminum trisacetylacetonate, etc.), organosiloxane (dimethylsiloxane,
Diethylsiloxane, methylethylsiloxane, diphenylsiloxane, methylphenylsiloxane, ethylphenylsiloxane, methylhydrogensiloxane,
Ethyl hydrogendiene siloxane, phenylhydrodiene siloxane, etc.) and acrylic acid compounds (ethylene acrylic acid copolymer resin, ethylene / ethyl acrylate copolymer resin, ethylene / methyl acrylate copolymer resin) and the like.

As the surface treatment method, for example, a surface coating treatment (dipping or spraying in a solution state and then removing a solvent by drying or the like), a direct mixing treatment of the surface treatment substance and a light-shielding substance (particularly, the surface treatment substance Liquid or pasty, which is optimal ) . Specifically, the surface coating treatment is a method in which a light-shielding substance is immersed in a solution of the surface treatment substance in a solvent, and then the solvent is evaporated and dried. A method in which a solution obtained by dissolving the surface treatment substance in a solvent is sprayed on a light-shielding substance, and then the solvent is removed and dried. Or, the surface treatment agent and a wetting agent and / or a plasticizer and / or a method of mixing a light-shielding material and flow liquid substance such as a lubricant. In the case of a fluid liquid surface treatment substance (lubricant, surfactant, coupling agent, antistatic agent, etc.), the method is directly mixed with a light-shielding substance.

In the present invention, the light-shielding substance is subjected to the above-mentioned surface treatment. Representative examples of the light-shielding substance used in the present invention are described 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. Hydroxide: aluminum hydroxide, magnesium hydroxide, basic magnesium carbonate, etc. Carbonate: calcium carbonate, magnesium carbonate, dolomite, dawsonite, etc. (Sulfite): calcium sulfate, barium sulfate, ammonium sulfate, calcium sulfite, etc. Silicates: talc, clay, mica, asbestos,
F. Glass fiber, glass balloon, glass beads, calcium silicate, montmorillonite, bentonite, etc. Carbon: carbon black, graphite, carbon fiber, carbon hollow sphere, etc. 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 flour (pine, oak, sawdust, etc.), shell fiber (almond, peanut, fir shell, etc.), various colored fibers such as cotton, jute, paper chips, cellophane chips, nylon fibers, polypropylene fibers , Starch (including modified starch and surface-treated starch), aromatic polyamide fiber, etc.

Among these light-shielding substances, carbon black is preferred because the amount of bleed-out such as a lubricant or a surfactant can be reduced. 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 and the like. In the present invention, furnace carbon black is desirable for the purpose of ensuring light-shielding properties, improving cost and physical properties, and not adversely affecting photographic characteristics. Ketjen carbon black, which is carbon black, is desirable. If necessary, it is also desirable to mix the former and the latter according to required characteristics. There are various forms in which the light-shielding substance is mixed into the resin composition, but the masterbatch method is desirable in terms of cost, prevention of workplace contamination, and the like. Japanese Patent Publication No. 40-26196 discloses a method of preparing a polymer-carbon black masterbatch by dispersing carbon black in a solution of a polymer dissolved in an organic solvent.
JP-A-43-10362 describes a method for preparing a masterbatch by dispersing carbon black in polyethylene.

As a light-shielding substance of the molded article for a photographic light-sensitive material of the present invention, a polyolefin resin injection molding is used which does not generate fog on the photographic light-sensitive material, causes little increase / decrease in sensitivity, and has a large light-shielding ability. Pinholes in injection-molded products and light-shielding films, such as hardening of carbon black and fish eyes, even when added to molded products, polystyrene resin injection molded products, L-LDPE resin films, etc. In carbon black, pH (JIS K
6.02-19.0, preferably 6.5-8.5, average particle size (measured by electron microscopy) 10-120 mμ, especially 12-7
Of these, a volatile component (measured by JIS K 6221) is particularly preferably 3.5% or less, and most preferably 1.5% or less.
% Or less, and a DBP oil absorption (measured by the oil absorption A method of JIS K 6221) of 50 ml / 100 g or more, most preferably 70 ml / 100 g or more. Channel carbon blacks are expensive and most of them have a volatile component of more than 5.0%. Most lamp blacks having a pH of 5.0 or less adversely affect photographic properties. Therefore, even when it is necessary to use lamp black, the influence on photographic properties should be investigated and selected. In addition, the sulfur content according to the measurement method of ASTM D 1619-60 is 0.9% or less, preferably 0.7%
Failure to do so adversely affects photographic properties. In particular, it is preferable to select a free sulfur component having an adverse effect on the photographic properties of the photographic material of 0.1% or less, most preferably 0.05% or less.

Preferred carbon black actual products include, 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,
# 2200 (B), # 2400 (B), MA8, MA11, MA100 and the like. Overseas products include, for example, Cabot Black Pearls 2, 46, 70, 71, 74, 80, 81, 607, etc.
egal 300, 330, 400, 660, 991, SRF-S, etc., Vulcan
3, 6, etc., Sterling 10, SO, V, S, FT-FF,
MT-FF and the like. In addition, Ashland Chemical's UnitedR, BB, 15, 102, 3001, 3004, 300
6, 3007, 3008, 3009, 3011, 3012, XC-3016, XC
-3017, 3020 and the like, but are not limited thereto.

The amount of the light-shielding substance is preferably 0.01 to
It is in the range of 30% by weight, more preferably 0.05-20% by weight, most preferably 0.1-10% by weight. The combined effect with substances colored by light, such as vitamin E, photosensitive resin, etc. (improvement of coloring density, decrease of physical strength decrease, improvement of melt sealing property, improvement of moldability, improvement of resin fluidity) is greatly exhibited. . In particular, when the thickness is 10.0 μm or less, the addition amount of the light-shielding substance is 0.1 to 15% by weight, preferably 0.5 to 10% by weight, particularly preferably 1.0 to 7.
The range is 0% by weight.

An antioxidant is used in the molded article for a photographic light-sensitive material of the present invention. The oxidative decomposition of the resin is higher for polyolefin resins having more CH ₃ branches. This is because the amount of oxygen absorption is large, and thus the degree of oxidative decomposition is as follows: polypropylene resin> homopolyethylene resin> ethylene / α-olefin copolymer resin. Various polyethylene resins (including ethylene / α-olefin copolymer resins) and various polypropylene resins (including propylene / ethylene random copolymer resins) which are typical thermoplastic resins of crystalline resins
And the like are hydrocarbons, and it is thought that the autoxidation of hydrocarbons proceeds in a chain-like manner once a free radical is generated by dehydration in the presence of oxygen. 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 rapidly stopped. As a result, a large amount of alcohols, aldehydes, acids, etc. which affect the photographic properties of the photographic light-sensitive material are produced, and these react with each other to form a polymer.

In order to prevent the oxidation of hydrocarbons, it is necessary to complete the above-mentioned chain reaction, for which an antioxidant is used. That is, the antioxidant reacts with a free radical (mainly ROO.) As a chain propagator to decompose a free radical chain terminator which inactivates the free radical and a hydroperoxide ROOH which is a main source of free radicals. Then, there is a peroxide decomposer that stabilizes this. The former includes an alkylphenol-based antioxidant and an aromatic amine-based antioxidant. The latter includes sulfur-based antioxidants and phosphorus (phosphorus)
There are antioxidants. Since various antioxidants are also reducing agents that have an adverse effect on the photographic light-sensitive material, the quality degradation of the photographic light-sensitive material becomes a serious problem unless the addition amount is carefully examined.

Representative examples of the antioxidant used in the present invention are shown below. (A) Phenolic antioxidant Vitamin E, 6-t-butyl-3-methylphenyl derivative, 2
・ 6-di-t-butyl-P-cresol, 2.2′-methylenebis- (4-
Ethyl-6-t-butylphenol), 4.4'-butylidenebis
(6-t-butyl-m-cresol), 4,4'-thiobis (6-t-butyl-m-cresol), 4,4-dihydroxydiphenylcyclohexane, alkylated bisphenol, styrenated phenol, 2,6- Di-t-butyl-4-methylphenol, n-octadecyl-3- (3 ′ · 5′-di-t-butyl-4′-hydroxyphenyl) propinate, 2.2′-methylenebis (4-methyl-6 -
t-butylphenol), 4.4'-thiobis (3-methyl-6-t-
Butylphenyl), 4.4'-butylidenebis (3-methyl-
6-t-butylphenol), stearyl-β (3 ・ 5-di-4-butyl-4-hydroxyphenyl) propionate, 1.1 ・ 3-
Tris (2-methyl-4hydroxy-5-t-butylphenyl)
Butane, 1,3,5 trimethyl-2,4,6-tris (3.5-di-t-butyl-4hydroxybenzyl) benzene, tetrakis [methylene-3 (3.5-di-t-butyl-4 -Hydroxyphenyl) propionate] methane, etc. (b) Ketone amine condensation antioxidant 6-ethoxy-2,2,4-trimethyl-1,2-dihydroquinoline,
Polymers of 2,2,4-trimethyl-1,2-dihydroquinoline, trimethyldihydroquinoline derivatives, etc. '-Isopropyl-P-phenylenediamine, N ・ N'-Diphenyl-P-phenylenediamine, N ・ N'
-Di-β-naphthyl-P-phenylenediamine, N- (3'-hydroxybutylidene) -1-naphthylamine, etc. (d) Imidazole antioxidant 2-mercaptobenzimidazole, zinc salt of 2-mercaptobenzimidazole, 2-mercaptomethylbenzimidazole, etc. (e) Phosphite antioxidant alkylated allyl phosphite, diphenylisodecyl phosphite, tris (nonylphenyl) phosphite sodium phosphite, trinonyl phenyl phosphite, triphenyl phosphite (F) Thiourea antioxidants Thiourea derivatives, 1,3-bis (dimethylaminopropyl)-
(2) Other antioxidants useful for air oxidation, such as dilauryl thiodipropionate

Representative commercial antioxidants are shown below. (1) Phenolic antioxidants: SUMILIZER BHT (Sumitomo), IRGANOX 1076 (Ciba Geigy), MARK AO-50 (Adeka Argus), SUMILIZER B
P-76 (Sumitomo), TOMINOX SS (Yoshitomi), IRGANOX 565 (Ciba Geigy), NONOX WSP (ICI), SANTONOX (Monsanto),
SUMILIZER WX R (Sumitomo), ANTAGECRYSTAL (Kawaguchi), IRGA
NOX 1035 (Ciba Geigy), ANTAGE W-400 (Kawaguchi), NO
CLIZER NS-6 (Ouchi Emerging), IRGANOX 1425 WL (Ciba Geigy), MARKAO-80 (Adeka Argus), SUMILIZER
GA-80 (Sumitomo), TOPANOL CA (ICI), MARK AO-30 (Adeka Argus), MARK AO-20 (Adeka Argus), I
RGANOX3114 (Ciba Geigy), MARK AO-330 (ADEKA
Argus), IRGANOX 1330 (Ciba Geigy), CYANOX 1
790 (ACC), IRGANOX 1010 (Ciba Geigy), MARK AO-6
0 (Adeka Argus), SUMILIZER BP-101 (Sumitomo), T
OMINOX TT (Yoshitomi), etc. (2) Phosphorus antioxidants; IRGAFOS 168 (Ciba Geigy), MARK 2112 (Adeka Argus), WESTON 618 (Borg Warner), MARK PEP-8
(Adeka Argus), ULTRANOX 626 (Borg Warner), MARK PEP-24G (Adeka Argus), MARK PEP-
36 (Adeka Argus), HCA (Sanko), etc. (3) Thioether antioxidants; DLTDP "YOSHITOMI" (Yoshitomi), SUMILIZER TPL (Sumitomo), AN
TIOX L (NOF), DMTD "YOSHITOMI" (Yoshitomi), SUMILIZER
TPM (Sumitomo), ANTIOX M (NOF), DSTP "YOSHITOMI"
(Yoshitomi), SUMILIZER TPS (Sumitomo), ANTIOX S (NOF),
SEENOX 412S (Cipro), MARK AO-412 S (Adeka Argus), SUMILIZER TP-D (Sumitomo), MARK AO-23 (Adeka Argus), SANDSTAB P-EPQ (Sand), IRGAFOS
P-EPQ FF (Ciba Geigy), IRGANOX 1222 (Ciba Geigy), MARK 329K (Adeka Argus), WES TON399
(Borg Warner), MARK 260 (Adeka Argus), MARK 522A (Adeka Argus), etc. (4) Metal deactivator NAUGARD XL-1 (Uniroyal), MARK CDA-1 (Adeka
Argus), MARK CDA-6 (Adeka Argus), LRGANO
Particularly preferred antioxidants such as X MD-1024 (Ciba Geigy) and CUNOX (Mitsui Toatsu) are phenolic antioxidants, and commercially available products include Irganox of Ciba Geigy and Sumilizer BHT of Sumitomo Chemical Co., Ltd. Sumilizer BH-76,
Sumilizer WX-R, Sumilizer BP-101 and the like. Also, 2,6-di-butyl-p-cresol (BHT), a low volatility high molecular weight phenolic antioxidant (trade name Iregano)
x1010, Ireganox 1076, Topanol CA, Ionox 330 etc.),
It is effective to use one or more, particularly two or more of dilauryl thiodipropionate, distearyl thiopropionate, dialkyl phosphate and the like. In particular, it is effective to use two or more kinds having different actions such as a combination of a hindered phenol antioxidant and a phosphorus antioxidant.

However, since the antioxidant is also a substance which affects the photographic properties of the photographic light-sensitive material utilizing the oxidation / reduction action, the addition amount of the antioxidant is preferably 0.01 to 2.0.
%, More preferably 0.02 to 1.0% by weight, most preferably 0.03 to 0.8% by weight. If the addition amount is less than 0.1% by weight, the addition effect is hardly obtained. On the other hand, the addition amount is 2.0% by weight
Exceeding the range adversely affects photosensitive materials that utilize oxidation and reduction. Further, when used in combination with carbon black or the like, antioxidation exerts an additive effect. It is preferable to use a phenolic antioxidant, a phosphorus-based antioxidant, and carbon black in combination because the antioxidant effect is particularly synergistically exhibited.

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
Various chemical antioxidants and PLASTICS AGE ENCYCLOPEDIA Progress Edition, pp. 327-329 of K Chemical Industry Co., Ltd., 1986 (K
There are various antioxidants disclosed on pages 211-212 of K Plastics Age. The use of these antioxidants alone or in combination of two or more is essential in the present invention so as not to adversely affect the photographic properties. It is preferable to maintain

Representative thermoplastic resins that can be used in the present invention are shown below. Low-density polyethylene (high-pressure branched homopolyeletin)
(LDPE) resin Linear low-density polyethylene (low-pressure method or high-pressure improvement method ethylene / α-olefin copolymer) (L-LDPE) resin High-density polyethylene (HDPE) resin Ethylene-vinyl acetate copolymer (EVA) resin Polypropylene ( Homo, random, block) (PP)
Resin Polyethylene terephthalate (polyester) (PE
T) Resin Polyamide (PA) resin Polyvinyl chloride (PVC) resin Vinylidene chloride / vinyl chloride copolymer (PVDC) resin Ethylene / vinyl alcohol copolymer (EVOH) resin Polyvinyl alcohol (PVA) resin Polystyrene (PSA) resin Impact polystyrene resin (high impact polystyrene HIPS) acrylonitrile / styrene / butadiene terpolymer resin (ABS)

Among the thermoplastic resins, ethylene copolymer resins are preferred (for film molded products) because of their high physical strength, excellent heat sealing properties, and excellent dispersibility of light-shielding substances. In addition, various polypropylene resins, polystyrene resins, impact-resistant polystyrene resins, and ABS resins are preferable because of their excellent rigidity, dimensional accuracy, and excellent injection molding suitability (for injection molded products).

Representative examples of the ethylene copolymer resin are shown below. (1) Ethylene-vinyl acetate copolymer resin (hereinafter EVA
(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 (7) Ethylene-methyl acrylate copolymer resin
(Indicated as EMA resin) (8) Ethylene-ethyl acrylate copolymer resin
(Indicated as EEA resin) (9) Ethylene-acrylonitrile copolymer resin (10) Ethylene-acrylic acid copolymer resin (hereinafter EAA)
(11) Ionomer resin (resin obtained by crosslinking a copolymer of ethylene and unsaturated acid with a metal such as zinc) (12) Ethylene-α-olefin copolymer resin (hereinafter referred to as L-
(Indicated as LDPE resin) (13) Ethylene-propylene-butene-1 terpolymer resin

In an ethylene copolymer resin, when used as a film for packaging photographic light-sensitive materials, it has good film formability and heat-sealing suitability, does not adversely affect the photographic light-sensitive material, and has bag breaking strength and impact punching strength. L-LDPE resin and EEA resin are preferred because of their high tear strength. Also, in order to meet the required properties, other thermoplastic resins, various synthetic rubbers, various additives, various elastomers,
It is also preferable to use it by blending with a modifier.

[0047] L-LDPE (L iner L ow D ensity P oly e tylene)
The resin is called the third polyethylene resin, which has medium / low density,
It is a low-cost, high-strength resin that meets the needs of the era of energy and resource saving, combining the advantages of both high-density polyethylene resins. This resin is obtained by low-pressure method or high-pressure improvement method by using ethylene and α-alkyl having 3 to 13, preferably 4 to 10 carbon atoms.
It is a copolymer of olefins and is a polyethylene resin having a linear linear structure with short branches. Preferred α-olefins in terms of physical strength and cost include butene-1, octene-1, hexene-1,4-methylpentene-1,
Heptene-1, decene-1 and the like are used. The density is generally about low to medium density polyethylene resin, but many commercial products have a density in the range of 0.87 to 0.97 g / cm ³ . The melt index is often in the range of 0.1 to 80 g / 10 minutes. As the polymerization process of L-LDPE resin, there are a gas phase method using a medium / low pressure apparatus, a solution method, a liquid phase slurry method, and an ionic polymerization method using a high pressure improvement method apparatus.

Specific examples of commercially available L-LDPE resins are shown below. Ethylene-butene-1 copolymer resin G resin and NUC-FLX (UCC) Dourex (Dow Chemical) Screer (DuPont Canada) Marlex (Philips) Stamilex (DSM) Exelen VL (Sumitomo Chemical) Neozex (Mitsui Petrochemical) Mitsubishi Polyethylene-LL (Mitsubishi Yuka) Nisseki Linirex (Nippon Petrochemical) NUC Polyethylene-LL (Nippon Unicar) Idemitsu Polyethylene L (Idemitsu Petrochemical) Ethylene / hexene-1 copolymer resin TUFLIN ( UCC) TUFTHENE (Nihon Unicar) Ethylene / 4-methylpentene-1 copolymer resin Ultoxex (Mitsui Petrochemical) Ethylene / octene-1 copolymer resin Stamirex (DSM) Dourex (Dow Chemical) Screa ( DuPont Canada MORETEC (Idemitsu Petrochemical)

Among these L-LDPE resins, particularly preferred in terms of physical strength, heat seal strength and film formability are those having a melt index (hereinafter referred to as MI) of 0.8 to 1
0 g / 10 min (JIS K-6760), density 0.870~0.940g / cm ³ (JI
SK-6760), and an α-olefin having 6 to 8 carbon atoms obtained by a liquid phase slurry process and a gas phase process.

A particularly preferred representative example is given by a trade name, wherein polyethylene has 6 carbon atoms as an α-olefin side chain.
Of 4-Methylpentene-1 introduced by Mitsui Petrochemical Co., Ltd.
MORE of Idemitsu Petrochemical Co., Ltd.
There are TEC and Stamirex from DSM and Dowrex from Dow Chemical (these are the L-LDPE resins obtained by a liquid phase slurry process using a common product of four companies). Preferable typical examples obtained by the low-pressure gas-phase process include trade names such as hexene having 6 carbon atoms as an α-olefin side chain.
UCC's TUFLIN and Nippon Unicar which introduced -1
And TUFTHENE.

Further, recently released ultra low density linear low density polyethylene resin having a density of less than 0.910 g / cm ³ , for example, U
NUC-FLX of CC Company and Excelen V of Sumitomo Chemical Co., Ltd.
L is also preferable (both two products use butene-1 having 4 carbon atoms in the α-olefin).

Representative EEA resins include Union Carbide (USA), Nippon Unicar Co., Ltd., Mitsubishi Yuka Co., Ltd., Sumitomo Chemical Co., Ltd., Mitsui Polychemical Co., Ltd., and the like. . As specific examples, representative brand names of EEA resins currently marketed by Nippon Unicar Co., Ltd., and their comonomer contents, melt indexes and densities (comonomer contents of 6% or more by NUC test method) are shown.

[0053]

[Table 1]

In the molded article of the present invention, only one kind of the above-mentioned thermoplastic resins may be used, but two or more kinds of the above-mentioned thermoplastic resins, particularly two or more kinds of thermoplastic resins having a difference of 10 ° C. or more, are used. It is preferred to use. As described above, by using thermoplastic resins having different softening points, effects such as improvement in dispersibility of a light-shielding substance, improvement in resin fluidity, improvement in melt adhesion, and improvement in moldability can be obtained. Specifically, as a preferable combination of resins, the amount of comonomer is 5 for polyolefin resins such as L-LDPE resin, various polypropylene resins (including propylene / α-olefin copolymer resin), and homopolyethylene resins of various densities. % Of EVA resin, EEA resin, EMA resin and various waxes, EAA resin, acid-modified polyolefin resin, tackifying resin, etc., and the comonomer content is 7% with respect to various polyethylene resins and non-crystalline resins such as ABS resin. The above EVA resin, EEA resin, EM
A resin and various low molecular weight polyolefin resins, various waxes, EAA resins, acid-modified polyolefin resins, tackifier resins, various elastomers and the like.

The resin composition used in the present invention may contain a nucleating agent as another additive. 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 aromatic salts. Group metal phosphates, alkyl alcohols having 8 to 30 carbon atoms, condensates of polyhydric alcohols and aldehydes, and alkylamines,
For example, pt-butyl aluminum benzoate, 1,2,3,4-dibenzylidene sorbitol, a di-substituted benzylidene sorbitol compound represented by the following formula

[0056]

Embedded image

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

[0058]

Embedded image

Wherein R ₃ is an alkyl group having 8 to 30 carbon atoms, k and l are each 0 to 10, and k + 1 ≧
It is one. ], Metal salts such as lithium salt, sodium salt, potassium salt, calcium salt and magnesium salt of 1,2-hydroxystearic acid, stearyl alcohol, alkyl alcohol such as lauryl alcohol, sodium benzoate,
Contains benzoic acid, sebacic acid, etc.

Among the organic nucleating agents, the following are typical examples of sorbitol compounds which have a large crystallization promoting effect, reduce molding failure, shorten molding cycles, improve rigidity and improve colored appearance. 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 there 1,3-benzylidenesorbitol 1,3,2,4-dibenzylidene-D-sorbitol 1,3,2,4-di (m-methylbenzylidene) sorbitol 1・ 3,2 ・ 4-di (p-methylbenzylidene) sorbitol 1 ・ 3,2 ・ 4-di (p-hexylbenzylidene) sorbitol 1.3 4-di (phenylacetylidene) sorbitol

Among the above organic nucleating agents, the sorbitol compound has a large effect of addition, and does not adversely affect the photographic properties of the photographic material. The amount of the sorbitol-based organic nucleating agent added is preferably 0.01 to 3.0% by weight, more preferably 0.03 to 2.0% by weight, and most preferably 0.05 to 1.0% by weight.

Since organic nucleating agents, especially sorbitol compounds, have a bulk specific gravity of 0.1 ± 0.02 and are easily scattered,
In particular, it is preferable to use together with various fatty acid metal salts, because scattering can be prevented and dispersibility can be improved, the addition effect can be further improved, and bleed out can be reduced.
The amount of addition of these various fatty acids (particularly, metal salts of higher fatty acids having at least C ₈ is preferable) is preferably 0.01 to 5.
0% by weight, more preferably 0.03 to 3.0% by weight, most preferably 0.05 to 1.5% by weight. This fatty acid metal salt improves the dispersibility of the light-shielding substance and also improves the moldability. Furthermore, it has been found that the halide contained in the resin, which adversely affects the photographic properties of the photographic light-sensitive material, is neutralized and rendered harmless, so that the photographic properties are also improved.

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. And alkaline earth metal hydroxides such as calcium hydroxide, magnesium hydroxide and barium hydroxide, and alkaline earth metal oxides such as calcium carbonate and calcium oxide.

The nucleating agent is not limited to these, and other known nucleating agents can be used. In addition, it goes without saying that the nucleating agent is not limited to a single nucleating agent, and two or more nucleating agents can be used in combination. The addition amount of the inorganic nucleating agent is preferably 0.01 to 5.0% by weight, particularly preferably 0.05 to 3.0% by weight.

Various effects can be obtained by adding a nucleating agent. For example, haze (HAZ) is obtained by adding 0.1 parts by weight of pt-butylbenzoic acid as a nucleating agent to 100 parts by weight of a random copolymer of propylene and ethylene as a polymer.
E) can be reduced from 40% to 21%, and can be further reduced to 12% by adding 0.2 parts by weight.
The tensile yield point stress is, for example, 380 kg / cm ² when 0.1 parts by weight is added.
To 420 kg / cm ² , but hardly increases after adding more. The flexural modulus is, for example, 500 kg / cm ² to 60 when 0.1 part by weight is added.
Although it can be improved by 0 kg / cm ² , even if added more, it hardly improves thereafter.

Various types of molding (injection molding, blown film molding, extrusion lamination molding, extrusion sheet molding, blow molding, injection blow molding, rotation molding, vacuum molding, etc.) Various methods have been employed in order to solve various problems in molding.

For example, there are a method of increasing the resin temperature to improve the fluidity of the resin, a method of using a die having a multi-spiral structure, and the like. Various problems such as occurrence occur. In the case of the latter, not only cannot it be used for various resins because it is a special equipment, but also L-LDPE resin etc. have problems such as heat generation and decrease in resin discharge amount, and the equipment is expensive and the production cost of the product increases. There are problems such as.

Therefore, in the present invention, fatty acid amides, lower alcohol esters of fatty acids, polyhydric alcohol esters of fatty acids, polyglycol esters of fatty acids, various silicone oils, various coupling agents, various fatty acid metal salts, various antistatic agents, various lubricants , 0.001 ~
The addition of 5% by weight, preferably 0.005 to 3% by weight, particularly preferably 0.01 to 1% by weight, and most preferably 0.03 to 0.5% by weight solves the above-mentioned problems, and furthermore, the addition of a light-shielding substance essential for the present invention. Improves the dispersibility, prevents the occurrence of blemishes together with the improvement of the light shielding ability, the prevention of deterioration of the photographic properties of the photographic photosensitive material (prevention of fog and sensitivity abnormalities, prevention of frictional fog, etc.), prevention of abrasion, prevention of melt fracture, Attempts are made to prevent the occurrence of die lip stains and die lip streaks, the generation of wrinkles, the prevention of static marks, the improvement of moldability, and the like.

In particular, by adding 0.001 to 0.5% by weight of an ester of an aliphatic monocarboxylic acid having 20 to 40 carbon atoms and an aliphatic monohydric alcohol having 20 to 40 carbon atoms, the effect of preventing the above problems can be prevented. Was found to be able to demonstrate.
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 improves the appearance of the molded article.

The ester used in the present invention includes an aliphatic monocarboxylic acid having 20 to 40, preferably 25 to 35 carbon atoms and an aliphatic monohydric alcohol having 20 to 40, preferably 25 to 35 carbon atoms. It is an ester. Examples of the above-mentioned monocarboxylic acids include montanic acid, melicic acid, cerotic acid, bricinic acid, lacceric acid and the like. Examples of monohydric alcohols include montyl alcohol, melisyl alcohol,
Lacsil alcohol, seryl alcohol, brisyl alcohol and the like.

Since these improve the fluidity of the thermoplastic resin and achieve uniform kneading, they are very excellent as surface treatment substances 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 following may be further added to the resin composition as other additives. [Examples of other additives] (Types of additives) (Typical examples) (1) Plasticizer; phthalate ester, glycol ester, fatty acid ester, phosphate ester, etc. (2) Stabilizer: Lead-based, cadmium-based , Zinc-based, alkaline earth metal-based, organotin-based, etc. (3) Flame retardant; phosphoric acid ester, halogenated phosphoric acid ester, halide, inorganic substance, phosphorus-containing polyol, etc. (4) Filler: alumina, kaolin, clay , Zeolite, calcium carbonate, mica, talc, titanium oxide,
Silica, etc. (5) Reinforcing agent; glass roving, metal fiber, glass fiber, glass milled fiber, carbon fiber, etc. (6) Foaming agent: inorganic foaming agent (ammonia carbonate, sodium bicarbonate), organic foaming agent (nitroso, azo (7) Vulcanizing agents; vulcanization accelerators, accelerators, etc. (8) Deterioration inhibitors; UV absorbers, antioxidants, metal deactivators, peroxide decomposers, etc. (9) Cups Ring agent: silane, titanate, chromium, aluminum, etc. (10) Various thermoplastic resins, polyolefin elastomers, synthetic rubbers, etc.

On the other hand, considering the case of landfill treatment as waste, it is only necessary to use a degradable plastic which is currently under study or is partially introduced into the market. For example, as a biodegradable polymer, I
CI "BIOPOL", UCC "Polycaprolactone"
Or natural, which is susceptible to biodegradation,
Alternatively, a polymer that is indirectly disintegrated by blending a synthetic polymer as an additive, or a starch-blended polyethylene can be used.

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

Representative examples of the molded article for a photographic light-sensitive material of the present invention obtained by molding the above-mentioned light-shielding thermoplastic 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. 2-2700, etc. Multi-layer co-extruded film molded product (Figs. 2 and 3); Single-layer film molded product or multilayer co-extruded film molded product (FIG. 4); JP-B-63-26697, JP-B-2-2701, JP-B-2-13774, JP-B-2-19225, etc. The above-mentioned flexible sheets were used. Packaging materials; packaging bags (unipack bags, single flat bags, double flat bags, single gusset bags, double gusset bags, etc.), shring packages, bulk packages (Japanese Unexamined Patent Publication No. 3-53243, Japanese Utility Model Application Laid-Open No. 3) Japanese Patent Application Laid-Open Nos. 71346/71) and 55/113543, 60-13386, and 60-167796. JP-A-2-72347, JP-A-3-47547, JP-A-3-54937, JP-A-3
JP-86358, JP-A-3-96648, etc. (2) Vacuum molded product (3) Injection molded product Spool for photographic film, film unit with lens,
Containers for photographic film patrones, light-shielding containers, patrones for plastic photographic films, light-shielding magazines for loading in bright rooms, cores, photographic film cartridges, packs for instant film, etc. Disc film cartridges; Attached film unit (FIG. 9); JP-A-63-226643, etc. Spool for photographic film (FIG. 7); JP-A-1-251030, JP-A-57-196218, JP-A-59-15049 Gazette, USP 1930144, Jpn 63-7374
No. 2, JP-A-54-120931, JP-A-58-178139
No. 178145, Japanese Utility Model Publication No. 55-31541, Japanese Patent Laid-Open No. 58-2
JP 03436, JP-A-58-82237, JP-A-58-8223
No. 6, JP-B-44-16777, JP-A-63-73742, JP-A-62-240957, GB2199805A, etc. Patrones for photographic films (FIG. 8); No. 111822, JP-B-45-6991, JP-B-55-21089, JP-A-50-33831, JP-A-56
-87039, Japanese Utility Model Laid-Open No. 55-97738, JP-A-1-31
No. 2538, JP-A-57-190948, USP 4,846,41
8, USP 4,848,693, USP 4,887,776, etc. Containers for photographic film patrone (FIGS. 5 and 6); JP-A-61-250639; , USP 4,801,011, JP-A-63-1
No. 21047, JP-A-62-291639, and Japanese Utility Model Application No. 1-889
No. 40, JP-A-1-113235, JP-A-1-152337
JP-B, JP-B-2-33236, JP-B-3-48581, JP-B-2-38939, USP 4,639,386,
USP 4,801,011, USP 4,979,351, EP 0
237062 A2, EP 0280065 A1, EP 029
No. 8375A2, etc. Core and reel; Japanese Utility Model Publication No. 60-107848, US Pat.
No. 33873 B, a magazine for sheet films, etc .; JP-A-56-5141, etc .; Photographic film cartridge (FIG. 11); JP-B-56-16610, JP-A-2-24846, JP-A-2-29041, JP-A-60-120448, JP-A-1-312537, etc. Photographic film case (FIG. 10); USP 4,779,756, JP-A-54-100617, JP-A-64-32343, JP-A JP-A-1-94258, JP-A-2-56139, EP 0242905A1, JP-B-2
-54934

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

The molded article of the present invention can be subjected to printing in order to increase the value of characters or symbols necessary for the function or the commercial value. The ink used for these printings is selected from those which are harmless to the photosensitive material, and can be selected from commonly used offset printing inks, gravure printing inks, or UV inks.

Typical synthetic resins used in these inks are copolymer resins mainly composed of vinyl chloride, vinyl amino resins, alkyd vinyl resins, oil-free alkyd resins, vinyl chloride vinyl chloride, and nitrated cotton. , Polyester, polyamide urethane, polyacrylic, rosin-modified maleic acid,
Ethylene vinegar, vinyl ether, urethane vinegar, salt vinegar biurethane resin, modified alkyd resin, modified phenol resin, high-molecular and low-molecular polyester amino resin,
Alkali-soluble resins (rosin-modified maleic resin, styrene maleic resin, styrene acrylic resin, acrylate acrylic resin, methacrylic ester acrylic resin), hydrosol resins (styrene maleic resin, styrene acrylic resin) , Α-methylstyrene acrylic acid resin, acrylic acid ester acrylic acid resin,
As a resin for the VU ink, an acrylic unsaturated group is used as a resin for a VU ink, a methacrylate acrylic resin, an emulsion resin (styrene resin, a styrene acrylic resin, an acrylic copolymer resin, a methacrylic copolymer resin). Polymers are generally used, and typical examples are polyester / acrylate, polyester / urethane resin / acrylate, epoxy resin / acrylate, pentaerythritol triacrylate, trimethylolpropane triacrylate, Examples include hexanediol diacrylate, neopentyl glycol diacrylate, triethylene glycol diacrylate, and hydroxyethylene methacrylate.

Further, a generally known coloring agent is used in combination with these inks. Examples of the coloring agent used include 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 type; Chromophthaliero (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), cyoxazine type; dioxazine violet (PV-23), isoindolinone type; isoindolinone yellow (PY-109, 11)
0), sulene; perylene, perinone, flavanthrone, thioindigo, lake pigment (malachite green,
Rhodamine B, rhodamine G, Victoria blue B) and inorganic pigments (oxide, titanium dioxide, red iron oxide, sulfate);
Precipitated barium sulfate, carbonate; precipitated calcium carbonate,
Silicate; hydrous silicate, anhydrous silicate, metal powder; aluminum powder, bronze powder, zinc dust, carbon black, graphite,
Ultramarine, navy blue, etc.). These pigments may be added to the above-mentioned resin layer or the like as a light-shielding substance. In addition, oil-soluble dyes, dispersible dyes and the like are also used. Various other solvents as necessary as raw materials constituting the ink,
Additives such as dispersants, wetting agents, defoamers, leveling agents, thickeners, stabilizers, crosslinking agents, waxes and the like are used. The synthetic resin and colorant used as these inks are applied as a paint on the front and back surfaces of molded articles and packages using them to improve product value, improve abrasion resistance, improve light-shielding properties, improve photographic properties, etc. It is also preferable to use it for the purpose.

The photosensitive material to which the molded article for photographic photosensitive material of the present invention can be applied is shown below. Silver halide photographic materials (film for printing, color or black and white photographic paper, color or black and white negative film, color or black and white positive film, printing master paper, color reversal film, D
TR (diffusion transfer) photosensitive material, computerized typesetting film and paper, microfilm, movie film, self-developing photographic photosensitive material, direct positive film and paper, etc.)
Heat-developable light-sensitive materials (heat-developable color light-sensitive materials, heat-developable black-and-white light-sensitive materials (for example, JP-B-43-4921 and JP-B-43-4924, "Basics of photographic engineering", silver halide photography, published by Corona in 1879) 553-555 and Research Tis Closure, June 1978, pp. 9-15 (RD-17029), and JP-A-59-12431 and 60-2.
No. 950, No. 61-52343 and U.S. Pat.No.4,584,267
Transfer-type heat-developable color light-sensitive material described in Japanese Patent Application Laid-Open No. 3-72358).
Material using photothermography (photosensitive / thermosensitive image forming method) described in Japanese Patent Application Publication No. H10-103, etc.) Diazonium photographic photosensitive material (4-morpholinobenzenediazonium microfilm, microfilm, copy film, printing plate material, etc.) ) Azide and diazide-based photographic materials (photosensitive materials containing para-azide benzoate, 4,4'-diazidostilbene, etc., such as copying films and printing plate materials) quinonediazide-based photographic materials (orthoquinonediazide, orthonaphthoquinonediazide) Photo-sensitive materials containing compounds such as benzoquinone (1,2) -diazide- (2) -4-sulfonic acid phenyl ether, such as printing plates, copying films, and adhesion films) Photopolymers (vinyl monomers Photosensitive materials, printing plates, adhesive films, etc.) Ester-based photosensitive materials (eg, printing films, IC resists, etc.)

In addition, photosensitive substances which are altered or degraded by various kinds of light, oxygen or sulfur dioxide, such as foods (butter, peanut bags, margarine, snack products, knobs, confectionery, tea, glue, etc.), pharmaceuticals (gastrointestinal drugs) , Powdered and granular medicines such as case medicines), dyes, pigments, photographic developing chemicals,
It can also be applied to photographic fixing chemicals, toner and the like.

[0082]

The dispersibility of the light-shielding substance in the resin composition is improved by applying the surface-treating substance of the present invention to the light-shielding substance. As a result, the photographic properties of the photographic light-sensitive material are prevented from being adversely affected, the light-shielding ability is drastically increased, and the occurrence of bumps is reduced. In the present invention, an antioxidant is further used. As a result, the oxidative decomposition of the resin can be suppressed, and the occurrence of coloring failure can be prevented, and adverse effects on the photographic properties of the photographic light-sensitive material, such as increase / decrease in sensitivity and fog, can be reduced.

[0083]

DESCRIPTION OF THE PREFERRED EMBODIMENTS An embodiment of a molded article for a photographic light-sensitive material of the present invention will be described with reference to the drawings. 1 to 4 are partial cross-sectional views of a light-shielding film for a photographic light-sensitive material.

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

The light-shielding film for photographic light-sensitive material shown in FIG. 2 is formed by co-extrusion of two layers of a light-shielding thermoplastic resin film layer 1a and a light-shielding thermoplastic resin film layer 2a as molded articles for photographic light-sensitive material of the present invention. It is formed of film IIa.

The light-shielding film for a photographic light-sensitive material shown in FIG. 3 has three layers of a light-shielding thermoplastic resin film layer 1a, an intermediate layer 3, and a thermoplastic resin film layer 2 as a molded article for a photographic light-sensitive material of the present invention. It is formed of a co-extruded film IIIa.

The light-shielding film for a photographic light-sensitive material shown in FIG. 4 is the same as the two-layer coextruded film IIa shown in FIG.
Is formed of a laminated film IVa adhered by blocking.

FIG. 5A is a cross-sectional view of a photographic film cartridge container 4 as a molded product for a photographic photosensitive material of the present invention. The container body 5 and the lid 6 are both molded articles of the present invention. Fig. 5 (b)
Is a cross-sectional view of the photographic film cartridge container main body 5 as a molded product for a photographic light-sensitive material of the present invention. It is a molded product for a photographic light-sensitive material of the present invention. FIG. 6 is a perspective view of a photographic film cartridge container 4 as a molded product for a photographic photosensitive material of the present invention. The photographic film cartridge container 5 includes a container body 5 and a lid 6.
Are formed integrally, and these are formed of the light-shielding thermoplastic resin composition of the present invention.

FIG. 7 is a front view of a photographic film spool 10 as a molded product for a photographic light-sensitive material of the present invention. I have.

FIG. 8 is an exploded perspective view of a patrone for photographic film as a molded product for a photographic photosensitive material of the present invention. The patrone for photographic film 7 includes an upper case 8 and a lower case 9 constituting a patrone main body. And a spool 10 around which a photographic film to be loaded is wound.
Then, the upper case 8, the lower case 9, and the spool 10
Is formed of the light-shielding thermoplastic resin composition of the present invention.

FIG. 9 is an exploded perspective view of a film unit 11 with a lens as a molded product for a photographic light-sensitive material of the present invention.
This film unit 11 with a lens is a lower case for storing the photographic film cartridge 7 in a light-tight manner, in which the spool 10 around which the photographic film is wound is stored in a light-tight manner.
12 and an upper case for sealing the lower case 12 from light.
The spool 10, the lower case 12, and the upper case 13 are formed of the light-shielding thermoplastic resin composition of the present invention.

FIG. 10 is a cross-sectional view of a light-shielding case 14 for a photographic film as a molded product for a photographic light-sensitive material of the present invention. The light-shielding thermoplastic resin composition of the invention is formed.

FIG. 11 is an exploded perspective view of a photographic film cartridge 15 as a molded product for a photographic material of the present invention.
The photographic film cartridge 15 includes a lower case 16 and an upper case 17 and a spool 18 loaded in the lower case 16 and the upper case 17, and the spool 18, the lower case 16 and the upper case 17 are made of the light-shielding thermoplastic resin composition of the present invention. It is formed of things.

FIG. 12 is a view showing a packaging process of a belt-shaped photographic photosensitive material package using a light-shielding thermoplastic resin film layer as a molded product for a photographic photosensitive material of the present invention. In this figure, reference numeral 19 denotes a belt-shaped photographic photosensitive material, reference numeral 20 denotes a thermoplastic resin film guide member, reference numeral 21 denotes a light-shielding thermoplastic resin resin film cover member, reference numeral 22 denotes a bonding portion, reference numeral 23 denotes a core, and reference numeral 24 denotes a core. It is a bush for hermetic packaging.

Example 1 A two-layer co-extruded inflation light-shielding film molded product corresponding to FIG. Molecular weight distribution (weight average molecular weight (MW)
/ Number average molecular weight (MN)) is 7.6, MI (melt index) is 0.6 g / 10 min, density is 0.925 g / cm ³ , and crystallinity is 71.
18% by weight homopolyethylene resin, MI 5.0g / 10
Min, density 0.88 g / cm ³ , molecular weight distribution (MW / MN) 3.6, crystallinity 35%, ethylene unit content 80 mol%, butene-1
76.7% by weight of an ethylene / butene-1 random copolymer resin with a unit content of 20 mol%, pH 7.0 surface-treated with magnesium stearate, average particle size of 25mμ, and 0.08% by weight loss on drying under absolutely dry conditions Furnace carbon black 3
Wt%, erucamide 0.05 wt%, vitamin E 0.05 wt%, tetrakis [methylene-3- (3,5-di-tert-butyl-4)
-Hydroxyphenyl) propionate] A light-shielding thermoplastic resin film layer having a thickness of 50 μm and made of an L-LDPE-based resin composition containing 0.05% by weight of methane and having a molecular weight distribution (M
(W / MN) is 7.6, MI is 1.0 g / 10 min, density is 0.945 g / cm ³ , crystallinity is 78%, homopolyethylene resin 20% by weight, MI is
2.5 g / 10 min, density 0.92 g / cm ³ , crystallinity 53%, molecular weight distribution (MW / MN) 3.3, ethylene unit content is 95 mol%,
Octene-1 Ethylene octene with a unit content of 5 mol%
-1 copolymer resin at 73.5% by weight, loss on drying under absolutely dry conditions
6% by weight of titanium dioxide surface-treated with 0.15% by weight of dihydric alcohol, 0.05% by weight of silica, 0.2% of zinc stearate
A 50-μm thick, light-shielding thermoplastic resin film layer made of an L-LDPE resin composition containing 0.1% by weight of vitamin E and 0.1% by weight of vitamin E. Molded. The molded article for a photographic light-sensitive material of the present invention is a molded article of a light-shielding blown film having two layers coextruded at the same time and having a thickness of 100 μm in which the colors of the inner and outer layers and the resin composition are different. This two-layer co-extruded blown film molded product is excellent in physical strength, heat sealing suitability, photographic properties, light shielding properties, flatness, moldability, and appearance, can be distinguished from front and back, and has a white and black appearance The sealed bag made by heat sealing the inner layer of the bag is identifiable even under a safelight for wrapping the photosensitive material, and the bag can be stacked without leaving the temperature inside and outside the bag even when left in sunlight. Was. In addition, the outer layer is white and can be identified under safelight, and the temperature rise on the surface of the bag and inside the bag is small even if it is left under sunlight, and the quality of the photosensitive material is not degraded.
Vitamin E and light-shielding substance are used together to improve light-shielding ability
Since the physical strength and heat seal strength were high and the decomposition of the resin could be prevented, adverse effects such as abnormal photographic sensitivity of the photographic light-sensitive material and occurrence of fogging could be reduced.

Example 2 This is a photographic film cartridge container body corresponding to FIG. 5A in which the inner wall portion of the container body is cut off by 0.3 mm and the side wall thickness is reduced from 1 to 0.7 mm. 0.5% by weight of calcium stearate, 3% by weight of titanium dioxide having a loss on drying under absolute dry conditions of 0.2% by weight, 0.15% by weight of di- (p-methylbenzylidene) sorbitol, and 0.01% by weight of o-methylbenzylidene-p-methylbenzylidenesorbitol 0.01 Master batch (total amount 8.66) coated on a surface by weight and dispersed in 5% by weight of a low density homopolyethylene resin and a polyethylene wax mixed resin.
Wt%, 35% titanium oxide master batch) and MI
(ASTM D-1238) 40g / 10min, density (ASTM D-1505) 0.90
g / cm ³ , flexural modulus (ASTM D-790) 10,700 kg / cm ² , Rockwell hardness (ASTM D-785) 88R, propylene content 96.7% by weight, ethylene content 3.3% by weight, average 90.54% by weight of a propylene / ethylene random copolymer resin having a molecular weight (weight average molecular weight (MW) / number average molecular weight (MN)) of 3.7, oleic acid amide 0.05% by weight, and a hindered phenolic antioxidant tetrakis [methylene- 3- (3.5-di-ter
t-butyl-4-hydroxyphenyl) propionate] methane 0.10% by weight, phosphorus-based antioxidant trinonylphenylphosphite 0.05% by weight, ultraviolet absorber 2-hydroxy-4-octoxybenzophenone 0.1% by weight, drip-proof Using a propylene ethylene random copolymer resin composition containing 0.5% by weight of diglycerin monostearate as an agent, an injection molding machine of a photographic film cartridge container body corresponding to FIG. Using a 24-cavity hot runner type mold, it was produced in a molding cycle of 7 seconds under the injection molding conditions of a resin temperature of 220 ° C. and a cooling water temperature of 20 ° C. Even when the container body was taken out at a temperature of 45 ° C., there was no deformation or abrasion such as buckling or sink marks, and the container body for photographic film patrone was excellent in white appearance and capable of unmanned continuous molding for a long period of time.

The photographic film cartridge container body having a white appearance, which is an injection-molded product, has an extremely high productivity of 7 seconds despite the number of molding cycles of 24 and has excellent productivity. Even when the take-out temperature was as high as about 45 ° C., there was no deformation, so the crystallinity was increased, and the Rockwell hardness was improved to 98R. As a result, no abrasion or abrasion dust is generated even when the sheet is fed at high speed by air or when a cartridge for photographic film is inserted and sealed and sealed with a lid. Furthermore, bleed-out was hardly observed even after storage in a low-temperature warehouse at 18 ° C. for one year, and no adhesion of water droplets was observed. No thermal deformation of the container body or thermal deformation of the spool around which the photographic film in the container was wound was observed even when the container was left in a car under sunlight. Further, the suitability for printing on the container main body was excellent, and even when the container main body was displayed at a store as it was, there was no discoloration or thermal deformation, and there was little adhesion of dust. The photographic properties were good, and the fog was greatly reduced from 0.07 to 0.02 without surface treatment.

Further, since the inner wall portion was shaved off by 0.3 mm to make it thinner, the tongue portion of the photographic film surely entered the container main body, and the patrone for photographic film was excellent in automatic insertion suitability. In addition, the resin injection port is 30% thicker than the average thickness of the bottom, so even if the resin injection port is removed from the mold, it can have a thickness almost equivalent to the bottom, ensuring moisture resistance and light shielding. It was an excellent photographic film patrone container body that could ensure the properties. Furthermore, the Rockwell hardness has been greatly improved, and not only the occurrence of abrasion and abrasion has been reduced, but also the cooling time has been shortened, and the container body (molded product) can be taken out even at around 40 ° C. Could be shortened. There was almost no molding failure such as deformation or gate residue, and unmanned molding was possible.

Example 3 The outer wall of the container body was cut off by 0.3 mm, and the inner diameter of the side wall near the bottom was reduced to a thickness of 1 → 0.7 mm. And the inner diameter of the upper opening is 1.
Fig. 5 that can be stacked with a 5mm larger taper
It is a container body for photographic film patrone corresponding to (b).

The melt index is 30 g / 10 minutes (ASTM D-12
38), density 0.900g / cm ³ (ASTM D-1505), crystallinity 87
% Propylene / ethylene random copolymer resin (ethylene content: 3.5 mol%) 77.5% by weight, fatty acid amide 0.05
2.0% by weight of aluminum powder surface-treated with 0.2% by weight of magnesium stearate and 0.2% by weight of magnesium stearate. (Hydroxyphenyl) propionate] using a mixture of 0.05% by weight of methane and 0.05% by weight of n-octadecyl-3- (4′-hydroxy-3 ′, 5′-di-tert-butylphenol) propionate,
20% by weight of an ethylene / butene-1 copolymer resin having a low crystallinity of 23 g / 10 min MI (ASTM D-1238), a density (ASTM D-1505) of 0.905 g / cm ³ and a crystallinity of 23% %, 1,3,2,4-di-treated with magnesium stearate as organic nucleating agent
Using a propylene resin composition containing 0.15% by weight of-(methylbenzylidene) sorbitol, using an injection molding apparatus (24 cavities, mold clamping pressure 150t), resin temperature 210 ° C
Cycle 8 for photographic film patrone container body
This is an injection molded product for photographic photosensitive materials, which is injection molded in seconds. This injection-molded product hardly caused fatal molding failures such as coloring failures and short shots, and did not undergo deformation, so that continuous unmanned injection molding was possible for a long period of time.

The container body for photographic film patrone, which is an injection-molded product, has a rapid molding cycle, has good lubricity between the container bodies, has excellent suitability for high-speed pneumatic conveyance, is unlikely to cause abrasion, has excellent antistatic properties, and has excellent dust resistance. And the suitability for taking the photographic film cartridge into and out of the container body was excellent. Furthermore, the appearance is silver and very good, 5m
Drop strength from concrete height to concrete floor is very high, especially drop impact strength at low temperature below 0 ° C is 0% due to combined phase effect of aluminum powder and ethylene butene-1 copolymer resin Thus, the container body for photographic film patrone of Comparative product 1 in which aluminum powder and ethylene / butene-1 copolymer resin were not added was extremely excellent in that 6% cracks occurred. In addition, even after storage at 18 ° C for one year, the bleed-out of lubricants such as oleic amide and magnesium stearate to the surface of the container body is small, and there is little stickiness, adhesion of dust and generation of white powder, excellent appearance, impact strength. It was a container body for photographic film patrone which had excellent lubricity and antistatic properties.

As an unexpected effect, it was found that the molding shrinkage due to the progress of crystallization of the polypropylene resin with the lapse of time was reduced by the effect of adding the surface-treated aluminum powder and the ethylene / butene-1 copolymer resin. Furthermore, even if the container was left in the sealed container under sunlight for 5 hours, there was almost no heat absorption, there was no deformation, there was little temperature rise in the container, and there was no quality deterioration of the photographic film.

Example 4 This is a photographic film cartridge container main body corresponding to FIG. The ethylene / butene-1 copolymer resin of the propylene-based resin composition of Example 3 was changed from 20 to 19% by weight, and instead of 2% by weight of aluminum powder, the average particle diameter of the surface treated with fatty acid amide and magnesium stearate was 20 mμ. , PH
Using a light-shielding propylene random copolymer resin composition to which 3% by weight of furnace carbon black of 7.0 was added, using the same injection molding apparatus and the same mold as in Example 2, at a resin temperature of 210 ° C. for a colored photographic film cartridge This is an injection-molded product for a photographic photosensitive material obtained by injection-molding a container body in a molding cycle of 6 seconds. This container body for photographic film patrone had no appearance of fatal molding failure, and had an excellent appearance capable of continuous unmanned injection molding for a long period of time.

The container body for photographic film patrone, which is an injection-molded product, has no deformation such as buckling or sink mark even if the molding cycle is shortened by 9 seconds compared to the comparative product 1, and hardly any coloring failure occurs. Also, the drop strength was much higher than that of the comparative product 1, and cracking was 0% at room temperature (20 ° C.). 0
The drop strength under a low temperature condition of not more than 0 ° C. was higher than that of the comparative product 1, and the cracking rate was good, being reduced from 6 → 0%.

Further, although it is black and opaque, no thermal deformation occurs even if it is left in the sunlight for 3 hours while keeping the container body,
It was heat-insulating, the temperature rise in the container was not so large as in Comparative Example 2, the spool of the patrone for straight film did not undergo thermal deformation, and the photographic film was hardly deteriorated. Furthermore, since it was colored in black, it had excellent light-shielding properties, and there was no light penetration from the outlet (port opening) of the photographic film of patrone. After storage in a low-temperature warehouse at 18 ° C for one year, there was no generation of substances that could adversely affect the photographic film, and there was little occurrence of fog and a feeling of fluctuation, and it was a container body for photographic film cartridges that could maintain excellent photographic properties. . In addition, substances that easily bleed out, such as a lubricant, an antioxidant, and a nucleating agent, are also adsorbed on the carbon black, resulting in less bleed-out, stickiness, adhesion of dust, and generation of white powder. It was an excellent one that was little and could hardly be recognized by the eyes due to the synergistic effect with the black appearance.

Example 5 FIG. 6 shows a container for a rectangular photographic film cartridge with a lid and a body integrated with a hinge, which corresponds to FIG. Using the same propylene / ethylene random copolymer resin as in Example 3, one container body for a rectangular photographic film cartridge with a lid corresponding to FIG.

The characteristics are almost the same as those of the third embodiment. Further, since they are square, they have suitability for stacking and display at stores, so that the decorative box made of paper can be removed. Various printings are colored as white opaque ground color, and as described in Example 3, the white opaque ground color reflects sunlight and does not cause thermal deformation of the container even when displayed at a store, The temperature rise in the container is also small, so the deformation of the spool under high temperature and the deterioration of the photographic properties of the photographic film are also small, the antistatic property is excellent, the bleed out of the lubricant, antioxidant, nucleating agent to the container surface is small, It is an excellent product that has little dust adhesion, reduces industrial waste, and has many after-use applications. Further, the present invention is a high-quality container which prevents thermal decomposition of a resin or an additive by adding an appropriate amount of an antioxidant, and hardly generates a substance having a bad effect on a photographic film.

Comparative Example 1 A photographic film cartridge container body corresponding to FIG. Example 2 0.1% by weight of two kinds of hindered phenolic antioxidants, 0.05% by weight of oleic amide and 0.2% by weight of magnesium stearate for surface treatment of aluminum powder and nucleating agent, ethylene butene-1 copolymer Using the same propylene ethylene random copolymer resin composition as in Example 2 except that 20 parts by weight of the resin was removed and the propylene / ethylene random copolymer resin was changed from 77.5 to 97.85% by weight, the same molding apparatus and the same metal were used. This is an injection-molded product for a photographic photosensitive material obtained by injection-molding a container body for photographic film cartridge prepared using a mold in a molding cycle of 8 seconds. The container body for photographic film patrone, which is an injection-molded product, is an excellent material having almost the same characteristics and dimensional accuracy as Example 2 except that the drop strength and the appearance under low temperature conditions of 0 ° C. or less are inferior immediately after molding. there were.

However, after storage in a low-temperature warehouse at 18 ° C. for one year, crystallization progressed, so that the drop strength at room temperature was worse than that of Example 2. Then, 6% cracks occurred. The first problem is that the dispersibility of the aluminum powder is poor, and as a result, the appearance is poor. The molding cycle was 15 seconds or more, twice as long as that of Example 2, and buckling, short shots, and sink marks were sporadic.

Further, since the amount of the hindered phenolic antioxidant added is 0 parts by weight, the resin is decomposed in a stagnant portion of a mold or the like to generate aldehydes and the like when a continuous molding is performed for a long period of time. Adverse effects such as fog and a feeling of fluctuation,
Resin burns occur, causing coloring failures and blemishes, resulting in gate clogging, and short shots are likely to occur, making unattended continuous molding difficult.

Example 6 This is a photographic film spool corresponding to FIG. MI
40 g / 10 min, density 0.90 g / cm ³ , crystallinity 95%, flexural modulus (ASTM D-790) 12,500 kg · cm / cm, molecular weight distribution (weight average molecular weight / number average molecular weight) 4.5 98 of propylene
70% by weight of a propylene ethylene random copolymer resin consisting of 2% by weight of ethylene and 2% by weight of ethylene, MI of 25 g / 10 min, density of 0.925 g / cm ³ , and Olsen rigidity of 2,800 kg / cm ² (JIS K-71
06), the molecular weight distribution (weight average molecular weight / number average molecular weight)
Low-pressure vapor-phase ethylene / butene-1 copolymer resin 26.85 consisting of 96% by weight of 3.5 ethylene and 4% by weight of butene-1
The average particle size of the light-shielding substance surface-treated with 0.1% by weight of erucamide, 0.10% by weight of erucamide, 0.2% by weight of calcium hydroxystearate, and 0.2% by weight of monoglyceride containing 95% of antiglyceride as antistatic agent is 20mμ, pH Is 0.07% by weight of vitamin E (α-tocopherol) as an antioxidant, and 2,6-di-tert-butyl-p-cresol which is a hindered phenolic antioxidant (generally BHT)
Propylene-ethylene random copolymer resin composition consisting of 0.3% by weight of calcium carbonate surface-treated with 0.2% by weight of dimethylpolysiloxane as an inorganic nucleating agent. Photo-sensitive material obtained by injection molding a photographic film spool equivalent to that shown in FIG. 7 in a hot runner type mold with a cavity of 24 and a resin temperature of 205 ° C. in a molding cycle of 8 seconds using an injection molding machine with a mold clamping pressure of 150 tons. It is an injection molded product.

This photographic film spool has a coloring failure.
Fatal molding failures such as short shots and poor light-shielding properties rarely occur, very good lubricity, good take-out from the mold, no deformation, and long-term continuous unmanned injection molding possible became. To reduce the pull-out torque of photographic film with conventional polystyrene resin,
Compared to photographic film spools that have a surfactant applied to the flange, this photographic film spool, which is an injection molded product, has a faster molding cycle, less abrasion and abrasion, and has better lubricity, The film pull-out torque was small, and it was particularly effective in an automatic photographic film wind-up type camera. The winding stop during photographing was greatly reduced, and the battery consumption was greatly reduced. Furthermore, it has excellent chemical resistance and solvent resistance, and has been greatly improved. Therefore, it is preferable for a photographic film used in a developing lab handling various chemicals and worldwide in a wide temperature range from high to low temperatures.

As an unexpected effect, the fogging of the photographic film is reduced (the density is reduced by 0.03), and the light-shielding ability is improved by 15% (almost the same light-shielding property is obtained even when the light-shielding substance is reduced by 15%). And the uniform dispersibility of the light-shielding substance is improved, and there is no problem with sink marks in the thick part, warpage of the flange, and a large molding shrinkage caused when a conventional propylene / ethylene random copolymer resin is used. Has improved.

As described above, while the various properties were improved, the lubricant and the antistatic property did not bleed out. This is due to the surplus effect of the combination of special furnace carbon black and vitamin E, which reduces the generation of aldehydes and the like which adversely affect the photographic film generated when the resin is decomposed in the presence of heat or oxygen, and is shaded by coloring. Injection molding with improved capacity, combined use of a propylene / ethylene random copolymer resin with a small molecular weight distribution and an ethylene / butene-1 copolymer resin to reduce molding shrinkage and reduce sink marks and warpage of flanges This is probably due to the effect of the product.

Example 7 This is a resinous photographic film cartridge corresponding to FIG. Using the resin composition of Example 6, a patrone for a photographic film made of a polypropylene resin as shown in FIG. 8 was prepared by an injection molding method. Was. In particular, it was excellent in lubricity and injection moldability, and the torque for feeding and winding the photographic film was small, and there was no failure to stop during photographing.

Example 8 MI was 0.3 g / 10 min, density was 0.95 g / cm ³ , and Vicat softening point was
81.62% by weight of high-density homopolyethylene resin powder at 128 ° C,
Melosyl cellotate 0.05% by weight, magnesium stearate 0.3% by weight, pH 7.0, average particle size (microscopic measurement method) 20mμ, oil absorption 80ml / 100g, volatile component 0.
3% by weight of furnace carbon black containing 7% of sulfur component and 0.61% of sulfur component (0.02% of free sulfur component) and tetrakis [methylene-3- (3.5-di-
-tert-butyl-4-hydroxyphenyl) propionate] methane 0.03% by weight, MI 0.7 g / 10 min, density 0.92 g
/ cm ³ , 15% by weight of ethylene / butene-1 random copolymer resin powder having a softening point of 100 ° C. was added, and the mixture was sufficiently mixed using a Henschel mixer. After extruding into a strand at a resin temperature of 210 ° C., columnar pellets having a diameter of 3 mm and a length of 6 mm were obtained with a pelletizer. As the molded article of the present invention, using the pellets, an inflation film molding machine (200
(mmφ ring die, lip clearance 1.1mm), molding a 100μm thick light-shielding inflation film as the guide member of Fig. 12 with a blow ratio of 1.2, and forming a 70μm thick light-shielding inflation film as a film cover member Used. This is a light room loaded package using color photographic paper as the belt-shaped photographic photosensitive material. This 70μm
The light-shielding film of (1) has a molecular orientation in the vertical direction (horizontal tear strength / vertical tear strength = 967 g / 136 g = 7.
1) By arranging the vertical direction in the direction of the arrow (⇔) in Fig. 12, the sealed package for loading the light room having the structure shown in Fig. 12 is loaded into an automatic developing machine (minilab), and the cover member is automatically developed with the guide member. By pulling it out of the machine, it can be torn in a straight line from the end of the joint.

The cover member and the guide member using the light-shielding blown film of the present invention are made of the same resin composition, and the joining portion can be welded, and the belt-shaped photosensitive material and the guide member can also be welded. Yes, the sealed light-shielding package can be easily formed. In addition, as a result of using the meristyl ester of cellotate, the motor load was reduced by 20%, the film formability was improved, and the difference in wall thickness of the blown film was 6 μm for the product of the present invention as compared with 22 μm for the non-added product.
The number was reduced to 3 or less, wrinkles were not generated at all, and the light-shielding properties, physical strength, and appearance were excellent.

Example 9 Ethylene butene having an MI of 20 g / 10 min, a density of 0.950 g / cm ³ , an Izod impact strength of 9 kg · cm / cm, an Olsen stiffness of 7,500 kg / cm ² and a Vicat softening point of 115 ° C. -1 random copolymer resin 94.55% by weight, methanyl montanate 0.0
5% by weight, zinc stearate 0.2% by weight, titanium dioxide surface-coated with hydrous aluminum hydroxide 5% by weight,
Using a white ethylene / butene-1 random copolymer resin composition composed of 0.2% by weight of 2,4-diheptany lidenesorbitol, a photographic film case with an integral lid and corresponding to FIG. 10 was molded by an injection molding method. This container has excellent drop impact strength without adversely affecting the photographic properties of the photographic light-sensitive material, and its white appearance makes it identifiable even under a safelight. Of the photographic light-sensitive material did not deteriorate, and almost no water droplets were observed in the container. Also,
The motor load on the screw was reduced by more than 20%, and the variation in thickness was small. Furthermore, the sealability and the fitting property are excellent, and the printability is also excellent, and it is possible to abolish the cosmetic small box using various original sealing methods. Even after use as a container for photographic films, it can be used as various kinds of accessories. In addition, it is also possible to reuse, if the pellets are recycled for reuse, the lid is the same ethylene-butene-1 random copolymer resin composition, so the selection of the lid is unnecessary and the physical strength decrease is small. , Which was particularly excellent. Example 10 Melt flow rate (ASTM D-1238) was 20 g / 10 min, density (A
STM D-1505) is 0.963 g / cm ³ of high-density homopolyethylene resin, and pentaerythrityltetrakis [3- (3.5-di-
-t-butyl-4-hydroxyphenyl) propionate] methane 0.1% by weight and phosphorus-based antioxidant tris (2,4-di-t-
Butylphenyl) phosphite 0.05% by weight, 1.3,2.4-di (paramethylbenzylidene) sorbitol (manufactured by Nippon Rika KK, Gelol MD) as an organic nucleating agent 0.2% by weight, calcium stearyl lactate 0.1% by weight as a lubricant and erucic acid Amide 0.05% by weight, zinc stearate 0.2% by weight, average particle diameter 21mμ, pH 8.0, oil absorption 87ml / 100g, sulfur content 0.3% by weight, volatile component 0.3
1% by weight of oil furnace carbon black by weight
A homopolyethylene resin composition comprising 0.2% by weight of zeolite A was used. A toggle type injection molding machine with a mold clamping pressure of 150 tonnes (Nestal, manufactured by Sumitomo Heavy Industries, Ltd. and a hot runner type mold having 24 cavities, using a photographic film shown in Fig. 5 (a) at a resin temperature of 200 ° C) A container body for patrone was prepared: a vertical streak-like rough surface having a height difference of 0.25 μm was formed on the inner wall surface of the container body, and a lattice-like rough surface having a height difference of 0.15 μm was formed on the outer wall surface of the container body. The container body of the present invention has improved carbon black uniform dispersibility, good photographic properties of the photographic light-sensitive material (less fogging and less sensitivity fluctuation),
The light-shielding ability was excellent, there was no coloring failure, there was almost no occurrence of bumps, no fatal molding failure occurred, and the appearance was excellent for continuous unmanned injection molding for a long time. In addition, the effect of forming a vertical streaky rough surface with a height difference of 0.25 μm on the inner wall surface of the container body is added, there is no occurrence of buckling or bottom sink, and sound is generated even when the core comes off from the container body Did not.

[0119]

According to the present invention, the uniform dispersibility of the light-shielding substance is improved, the adverse effect on the photographic properties of the photographic light-sensitive material can be prevented, the light-shielding ability can be improved, and the coloring failure can be reduced. The appearance can be improved because the occurrence of bumps is reduced.

[Brief description of the drawings]

FIG. 1 is a partial cross-sectional view of a wrapping film for a photographic light-sensitive material which is an example of a molded article for a photographic light-sensitive material of the present invention.

FIG. 2 is a partial cross-sectional view of a packaging film for a photographic light-sensitive material, which is an example of a molded article for a photographic light-sensitive material of the present invention.

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

FIG. 4 is a partial cross-sectional view of a packaging film for a photographic light-sensitive material, which is an example of a molded article for a photographic light-sensitive material of the present invention.

FIG. 5 is a cross-sectional view of a photographic film container which is an example of a molded article for a photographic photosensitive material of the present invention. (B) is a sectional view of a photographic film container main body having a taper in which the inner diameter of the upper opening is larger than the inner diameter of the bottom by α.

FIG. 6 is a cross-sectional view of a photographic film container integral with a lid, which is an embodiment of a molded article for a photographic light-sensitive material of the present invention.

FIG. 7 is a sectional view of a photographic film spool which is an embodiment of the molded article for photographic photosensitive materials of the present invention.

FIG. 8 is an exploded perspective view of a resin-made photographic film cartridge which is an example of the molded article for a photographic photosensitive material of the present invention.

FIG. 9 is an exploded perspective view of a film unit with a lens which is an embodiment of the molded product for a photographic photosensitive material of the present invention.

FIG. 10 is a cross-sectional view of a photographic film case integral with a lid, which is an example of a molded article for a photographic light-sensitive material of the present invention.

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

FIG. 12 is a perspective view showing a packaging process of a belt-shaped photographic photosensitive material package using a light-shielding film provided with a light-shielding thermoplastic resin film layer, which is an embodiment of the molded article for a photographic photosensitive material of the present invention.

[Explanation of symbols]

1a: light-shielding thermoplastic resin film layer (molded article for photographic light-sensitive material) 2, 2a: thermoplastic resin film layer 3a: intermediate layer a: light-shielding substance is included.

────────────────────────────────────────────────── ─── front page continued (51) Int.Cl. ⁷ identifications FI B65D 85/84 B65D 85/84 (56) references Patent Rights 2-178657 (JP, a) Patent Rights 2-48654 (JP JP-A-3-129341 (JP, A) JP-A-2-278256 (JP, A) JP-A-2-235048 (JP, A) JP-A-62-283331 (JP, A) JP-A-2-64537 (JP, A) JP-A-1-243050 (JP, A) JP-A-3-124767 (JP, A) JP-A-63-215748 (JP, A) JP-A-2-115836 (JP, A) A) JP-A-4-121733 (JP, A) JP-A-3-62342 (JP, U) (58) Fields investigated (Int. Cl. ⁷ , DB name) G03C 3/00

Claims (7)

(57) [Claims] 1. Organometal chelation as a surface treatment substance
The mixture has a viscosity at room temperature of 5,000 to 30,000
Anti-Stokes high viscosity silicone oil, no drip agent, yes
0.01 to 30% by weight of a light-shielding substance surface-treated with one or more aluminum compounds ,
Molded article for photographic light-sensitive material comprising a light-shielding thermoplastic resin composition containing at least 0.01 to 2.0% by weight 2. The method according to claim 1, wherein the surface treatment comprises a light-shielding substance and a surface treatment.
Mixing with substances, shading substance, flowing liquid substance and surface treatment
Mixing with physical substances, surface treatment substances dissolved in solvents
Immersion treatment in which a light-shielding substance is immersed inside, or surface treatment
Spray spraying a substance dissolved in a solvent onto a light-shielding substance
2. The molded article for a photographic light-sensitive material according to claim 1, which is a processing. 3. The substance which is colored by vitamin E and light.
3. The composition for a photographic light-sensitive material according to claim 1, which is contained.
Shape 4. A photographic described two or more thermoplastic resin softening point having a difference of more than 10 ° C. to including請 Motomeko 1, 2 or 3 photosensitive material for moldings 5. The light-shielding substance has a sulfur content of 0.2%.
Below, carbon black with a free sulfur component of 0.1% or less
The photographic light-sensitive material according to claim 1, 2, 3, or 4,
Molding 6. wherein the ester of an aliphatic monohydric alcohol fatty monocarboxylic acid and 20 to 40 carbon atoms from 20 to 40 carbon atoms in the 0.001 wt% including claim 1
Moldings for photographic photosensitive materials 7. A light-shielding thermoplastic resin set according to claim 1.
It is one that is formed by deposition thereof, the light-shielding film provided with the <br/> molecular orientation shielding thermoplastic resin film is a tear strength ≧ 2 molecular orientation direction perpendicular to the direction of the tear strength / molecular alignment direction A photographic light-sensitive material package for charging a strip-shaped light-sensitive material, which is used as an easy-opening cover member.