JPH06118570A - Core for photographic sensitive material - Google Patents

Abstract

PURPOSE:To prevent scratching or pressure fog even when dust deposits on a core or a winding surface of the core used for photographic sensitive material on which a photographic film or photographic paper is wound. CONSTITUTION:An outer cylinder 1 and an inner cylinder 4 are formed in one body with an annular plate 2 and libs 3 inside of the outer cylinder 1. The surface of the outer cylinder 1 (winding surface) has a rugged part 5 where almost hemisphere projections are formed in the longitudinal and transverse directions with specified interval. The max. roughness of the rugged part 5 is about <=40mum and the center line roughness is about 0.1-10mum. The inside of the outer cylinder 1 in the resin injection side has an undercut projection (not shown in the figure) to fix the core for a photographic sensitive material when a movable core is detached. Moreover, this core has a resin injection port 7.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a core for a photographic light-sensitive material for winding a photographic film, a photographic printing paper or the like in a roll.

[0002]

2. Description of the Related Art As cores for photographic light-sensitive materials on which photographic films are wound, there are various shapes according to the type of the photographic films to be wound.
No. 8, gazette of Japanese Utility Model Publication No. 51-279, gazette of Japanese Utility Model Publication No. 63-148940, gazette of Japanese Utility Model Publication No. 61-36995, etc.).

[0003]

However, in the above-mentioned conventional core for photographic light-sensitive material, since the winding surface around which the photographic film or the like is wound is formed smoothly,
When dust adhered, the dust caused pressure fog. Also, when scratches occur on the winding surface,
The scratches sometimes caused pressure fog. SUMMARY OF THE INVENTION It is an object of the present invention to solve the above problems and to provide a core for a photographic light-sensitive material that does not cause pressure fog.

[0004]

Means for Solving the Problems The present inventor has conducted extensive studies in order to achieve the above object and found that it is preferable to form irregularities having a predetermined roughness on the winding surface. The present invention has been made based on the above findings, and the core for a photographic light-sensitive material of the present invention has a cylindrical winding surface around which a belt-shaped photographic light-sensitive material is wound with a maximum roughness of 40 μm or less and a center line average roughness. Is formed to have unevenness of 0.1 to 10 μm.

The center line average roughness is JIS-B06.
According to the method specified in the section of surface roughness of 01-1976. The measurement was carried out with a surface roughness measuring instrument "Surfcoder" manufactured by KK Kosaka Laboratory at a cutoff value of 0.25 mm, and the maximum roughness is 5 mm of a roughness curve measured at a cutoff value of 0.25 mm. The distance (distance) between the highest peak and the deepest valley in (measurement length). The content of the center line average roughness is described in detail on page 22 of the surface roughness inspection method (June 17, 1959, published by KK Corona Co.).

The maximum roughness of irregularities on the winding surface is 40 μm or less,
It is preferably 30 μm or less, more preferably 20 μm or less. If it exceeds 40 μm, pressure fog prevention and pressure damage prevention cannot be effectively performed. Centerline average roughness (average roughness in the circumferential direction at the center of the core) is 0.1 to 10 μm, preferably 0.2 to
It is 7 μm, more preferably 0.3 to 5 μm.

The center line average roughness of the irregularities must be 10 μm or less. An attempt was also made to form irregularities having a center line average roughness of more than 10 μm, which is generally called embossing.
If it exceeds, the winding property of the photographic light-sensitive material (adhesion between the winding surface and the photographic light-sensitive material) is poor, and pressure fog occurs due to unevenness on the photographic light-sensitive material. Therefore, it is necessary that the center line average roughness of the irregularities is 10 μm or less. Further, the depth of the unevenness is 0.1 μm or more, and if it is less than 0.1 μm, it is impossible to prevent the harmful effects due to dust adhesion.

The interval (maximum roughness) between the top and bottom of the unevenness is preferably 30 μm or less, more preferably 20 μm or less. Typical shapes of irregularities are equilateral triangles, pointed combs, rounded combs, corrugations, sawtooth shapes, trapezoids, cloth-like shapes,
There are pear terrain, silk shape, parallel lines, etc.

In order to form the unevenness on the winding surface, a cavity mold having an uneven shape to be obtained is used, bite machining, buffing, sandblasting or both are used, or electrical discharge machining is performed. .

The resin forming the core for the photographic light-sensitive material may be a crystalline resin, an amorphous resin or a blended resin thereof, but it does not contain residual monomer or solvent. It is necessary not to affect the photographic quality. The MI of the resin is preferably 4 g / 10 minutes or more, more preferably 7 g / 10 minutes or more, and most preferably 9 g / 10 minutes or more from the viewpoint of injection molding suitability.

Typical examples of preferred resins for the core of the present invention include MFR (JIS K 6870) of 4 to 30 g / 10 minutes,
Preferably 7 to 20 g / 10 minutes, particularly preferably 9 to 17 g / 10
Min, Vicat softening point (JIS K 6870) is 85 ° C or higher, preferably 88 ° C or higher, particularly preferably 90 ° C or higher, and tensile yield strength (JIS K 6871) is 300 kg / cm ² or higher, preferably 330 kg / cm ²
Or more, particularly preferably 350 kg / cm ² or more, flexural modulus (AST
MD 638) is 25000kg / cm ² or more, preferably 28000kg / cm ²
Or more, particularly preferably 30,000 kg / cm ² or more, gas chromatographic volatile content is 1500 ppm or less, preferably 1000 ppm or less, particularly preferably 500 ppm or less, M scale Rockwell hardness (ASTM
D 785) is 40 M or more, preferably 50 M or more, particularly preferably 60 M or more, and the heat distortion temperature (JIS K 6871 (18.6 kg load)) is 70 ° C or more, preferably 75 ° C or more, particularly preferably 80 ° C or more, Izod Impact strength (JIS K6871) is 1.5kg
A polystyrene resin containing 0.1 to 10% by weight of a synthetic rubber of cm / cm or more, preferably 1.8 kg / cm / cm or more, and particularly preferably 2.0 kg / cm / cm or more.

The spool for photographic film of the present invention is preferably made of ABS, which is an amorphous polymer light-shielding polystyrene resin composition containing at least a synthetic rubber, a lubricant and a light-shielding substance.
It is made by injection molding of a resin composition. The polystyrene resin referred to here has a polystyrene content of 50% by weight.
The above-mentioned resins are meant, and those having a polystyrene content of 70% by weight or more, particularly 90% by weight or more are preferable. If the polystyrene content is less than 50% by weight, the dimensional accuracy, rigidity, suitability for ultrasonic welding, etc. are insufficient, and camera suitability, photographic film running performance, and complete light-shielding properties cannot be secured, making it impractical. Other than the polystyrene resin, it is preferable to blend various synthetic rubbers, various waxes, various acid-modified resins, ethylene copolymer resins and the like. In addition, depending on the required characteristics, it is preferable to use the following crystalline polymer because it has excellent wear resistance and heat resistance.

Further, Japanese Patent Application Laid-Open Nos. 4-67035 and 4
-116549, Japanese Patent Laid-Open No. 4-143749, and U.S. Pat.
No. 4,834,306, No. 4,846,418, further disclosed in JP-A-3-37645 by the present applicant, the photographic film patrone is stored in the patrone body even the tip of the photographic film in the unused state. Every time, by rotating the spool, it has a function of sending the leading edge of the photographic film out of the cartridge body. In such a photographic film cartridge, the cartridge body is also constructed by combining two or more resin molded parts.
In this case, as the thermoplastic resin used for the spool 3,
Low density polyethylene resin, medium density polyethylene resin, high density polyethylene which is a crystalline polymer having completely different characteristics from polystyrene resin and ABS resin which are excellent in ultrasonic welding suitability which are amorphous polymers used for the main body 2 of the cartridge. Resin, ultra-high molecular weight polyethylene resin, polypropylene resin, propylene / α-olefin copolymer resin, polyamide resin, polyacetal resin may be used to form the Patrone body 2 by ultrasonic welding at least two light-shielding polystyrene resin molded parts. It is preferable that the spool 3 and the cartridge body 2 are prevented from being welded when they are joined.

The term "substantially composed of a crystalline polymer" means that the thermoplastic resin constituting the spool is 50% by weight or more, preferably 70% by weight or more, and particularly preferably 90% by weight.
The above is meant to be the crystalline polymer.

In order to secure the light-shielding property of the above-mentioned amorphous polymer or thermoplastic resin which is a crystalline polymer, which is the resin material of the spool of the present invention, the following light-shielding substances are used. It is preferable to perform injection molding by using pellets obtained by kneading the above with polystyrene resin or thermoplastic resin.

[Typical example of light-shielding substance] (1) Inorganic compound A. Oxide Silica, diatomaceous earth, alumina, titanium oxide, iron oxide, zinc oxide, magnesium oxide, antimony oxide, barium ferrite, strontium ferrite, beryllium oxide, pumice, pumice balloon, alumina fiber, etc. B. Hydroxide Aluminum hydroxide, magnesium hydroxide, basic magnesium carbonate, etc. C.I. Carbonate calcium carbonate, magnesium carbonate, dolomite, dawsonite, etc. D. (Sulfite) Calcium sulfate, barium sulfate, ammonium sulfate, calcium sulfite, etc. E. Silicate talc, clay, mica, asbestos, glass fiber, glass balloon, glass beads, calcium silicate, montmorillonite, bentonite, etc. F. Carbon Carbon black, graphite, carbon fiber, carbon hollow sphere, etc. G. Other iron powder, copper powder, lead powder, aluminum powder, molybdenum sulfide,
Polon fiber, silicon carbide fiber, brass fiber, potassium titanate, lead zirconate titanate, zinc borate, barium metaborate, calcium borate, sodium borate, aluminum paste, talc, etc. (2) Organic compound Wood powder (pine , Oak, sawdust, etc.), shell fiber (almond, peanut, fir shell, etc.), cotton, jute, paper strip, cellophane strip, nylon fiber, polypropylene fiber,
Starch, aromatic polyamide fiber, etc.

Among these light-shielding substances, an opaque inorganic compound is preferable. Particularly, since it is a substance which is excellent in heat resistance and light resistance and is relatively inactive, it is a light-absorbing carbon black, titanium nitride and graphite. Is preferred. Gas black is an example of the classification by the raw material of carbon black.
Furnace black, channel black, anthracene black, acetylene black, ketjen carbon black, thermal black, lamp black, oil smoke,
There are pine smoke, animal black, vegetable black, etc.

Examples of commercially available products include carbon black # 20 (B), # 30 (B), # 33 (B), # 40 (B), # manufactured by Mitsubishi Kasei.
44 (B), # 45 (B), # 50, # 55, # 100, # 600, # 2200
(B), # 2400 (B), MA8, MA11, MA100 and the like. As an overseas product, for example, Cabot Bla
ck Pearls 2,46,70,71,74,80,81,607 etc., Reg
al 300, 330, 400, 660, 991, SRF-S, Vulcan
3, 6, etc., Sterling 10, SO, V, S, FT-FF,
MT-FF etc. are mentioned. Furthermore, Ashland Chemical Company's United R, BB, 15, 102, 3001, 3004, 300
6,3007,3008,3009,3011,3012, XC-3016, XC
-3017, 3020, etc. are mentioned, but not limited to these.

In the present invention, furnace carbon black is desirable for the purpose of improving light-shielding property, cost and physical properties, and acetylene carbon black and Ketjen carbon black which is a modified rigid carbon black are expensive as light-shielding substances having an antistatic effect. desirable. If necessary, it is also desirable to mix the former and the latter according to the required characteristics. Although there are various forms of blending the light-shielding substance with the polymer as described above, the masterbatch method is preferable in terms of cost and prevention of contamination of the workplace. Japanese Patent Publication No. 40-
In Japanese Patent Publication No. 26196, a method of preparing a polymer-carbon black masterbatch by dispersing carbon black in a solution of a polymer dissolved in an organic solvent is disclosed in JP-B-43-10.
Japanese Patent No. 362 describes a method of dispersing carbon black in polyethylene to form a masterbatch.

Although the amount of the above-mentioned light-shielding substance added varies depending on the type, it is possible to secure the properties required for the cartridge body, such as securing the light-shielding property and the amount that does not adversely affect the photographic properties and physical strength. The amount should be adjusted. Furnace carbon black is preferable as a light-shielding substance that is inexpensive, has a large light-shielding ability, and has a relatively small adverse effect on photographic properties, and when using this, carbon is used in order to prevent it from adversely affecting the photographic film. After refluxing in the presence of hydrogen cyanide, the generated hydrogen cyanide was trapped with an aqueous 0.1N sodium hydroxide solution, and the cyanide content was calculated by converting the amount of hydrogen cyanide based on the weight of carbon determined by 4-pyridinecarboxylic acid / pyrazolone absorption spectrometry into ppm unit. The amount is 10 ppm / carbon weight or less, preferably 5 ppm / carbon weight or less, and the average particle size is 10 to 120 mμ, preferably 15
˜70 mμ, pH 6 to 9, preferably 6.5 to 8.5, oil absorption of 50 ml / 100 g or more, preferably 70 ml / 100 g or more, and its addition amount is 0.01 to 10% by weight, preferably 0.05 to It is 5% by weight.

Among the light-shielding substances, various inexpensive carbon blacks having a large light-shielding ability have a pH of 4.0 to 9.0, preferably 6.0 to 8.0, and an average particle diameter of 10 to 120 mμ.
Preferably 15 to 60 μm, volatile component is 3.0% or less, preferably 1.0% or less, particularly preferably 0.8% or less, oil absorption is 50 ml / 100 g or more, preferably 60 ml / 100 g or more, particularly preferably 70 ml / 100 g or more Does not deteriorate the photographic properties such as “fog” and “abnormal sensitivity” in the photographic light-sensitive material,
This is preferable because it does not cause foaming or troubles such as silver strips during film formation, has good dispersibility, and generates few microgrids (aggregated impurities).

In addition to the above, the free sulfur content which adversely affects the photographic light-sensitive material is 0.6% or less, preferably 0.3% or less, particularly preferably 0.1% or less, and the cyan compound is 0.01% or less, preferably 0.005% or less, Particularly preferably 0.001% or less, the aldehyde compound is 0.1% or less, preferably
Care must be taken because carbon black of 0.05% or less, particularly preferably 0.01% or less is not carefully selected, since it adversely affects the photographic properties.

[Typical examples of surface-treating substances for light-shielding substances] Hydroxystearic acid triglyceride Various fatty acid metal salts (higher fatty acids such as stearic acid, oleic acid, palmitic acid, erucic acid, and lauric acid, and Zn, Mg, Ca, N)
Compounds with metals such as a, Sn, Al, Cd, and Ba. Preferred are magnesium stearate, calcium stearate, zinc stearate and magnesium oleate. ) Various fatty acid amides (oleic acid amide, erucic acid amide, stearic acid amide, bisoleic acid amide, etc.) Polyethylene wax (molecular weight 6000 or less) Polypropylene wax (molecular weight 6000 or less) Ethylenebisstearic acid amide montanic acid ester partially saponified hydroxystearin Acid amide Ethylenebishydroxystearic acid amide Hydroxide containing aluminum oxide (alumina, etc.) Polyolefin resin modified with unsaturated carboxylic acid or its derivative Titanate coupling agent (isopropyl-triisostearoyl-titanate, etc.) Silane coupling agent (vinyltrichlorosilane) , Vinyltrimethoxysilane, vinyltriethoxysilane, etc.) Higher fatty acids (caproic acid, stearic acid, oleic acid, erucic acid,
Palmitic acid, etc.) 2 to 4 valent alcohol (ethylene glycol, propylene glycol, 1.3
-Dihydroxybutane, heptamethylene glycol, trimethylolethane, glycerin, 1.2.6-hexanetriol, etc.) Organic aluminum compounds (aluminum ethylate, aluminum monoacetylacetonate, bisethylacetoacetate, aluminum trisacetylacetonate, etc.) Silica (natural silica, synthetic silica) Organoshiroki (dimethylsiloxane, diethylsiloxane, methylethylsiloxane, diphenylsiloxane, methylphenylsiloxane, ethylphenylsiloxane, methylhydrodienesiloxane, ethylhydrodienesiloxane, phenylhydrodienesiloxane, etc.) Acrylic acid Compound (Ethylene acrylic acid copolymer resin, ethylene ethyl acrylate copolymer resin, ethylene acrylic acid Methyl copolymer resin) Organic metal chelate compound (ethylenediaminetetraacetic acid, N-hydroxyethyl-ethylenediamine-NN'.N'-triacetic acid, diethylenetriaminepentaacetic acid, nitrilotriacetic acid, potassium sodium tartrate, etc.)

In the present invention, in order to prevent the generation of static marks and the like on the photographic film, it is preferable to further add various antistatic agents as described below. (1) Nonionic surfactant (typical component: polyoxyethylene glycols) (2) Anionic surfactant (typical component: polyoxyethylene glycols) (3) Cationic surfactant (typical component: Quaternary ammonium salt) (4) Amphoteric surfactant (5) Alkylamine derivative (6) Fatty acid derivative (7) Various lubricants (8) Carbon black, graphite (9) Metal surface coating pigment (10) Metal powder, metal Flakes (11) Carbon fibers (12) Metal fibers (13) Whiskers (potassium titanate, alumina nitride, alumina)

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

Typical examples of the anionic surfactant are shown below. Ricinoleic acid sulfate sodium salt, various fatty acid metal salts, ricinoleic acid ester sulfate sodium salt, sulfated ethylaniline oleate, olefin sulfate ester salts, oleyl alcohol sulfate ester sodium salt, alkyl sulfate ester salt, fatty acid ethylsulfonate salt , Alkyl sulfonate, alkyl naphthalene sulfonate, alkylbenzene sulfonate, succinate sulfonate, phosphate ester and the like.

Typical examples of the cationic surfactant are shown below. Primary amine salts, tertiary amine salts, quaternary ammonium salts, pyridine derivatives and the like.

Typical examples of the amphoteric surfactant are shown below. Carboxylic acid derivatives, imidazoline derivatives, betaine derivatives, etc.

The above antistatic agent is preferably added in an amount of 0.01 to 3.0% by weight.

A lubricant is preferably added in order to reduce the feeding and winding torque of the photographic film, improve the injection moldability of the spool, and improve the kneading properties of other additives. Representative examples of commercially available lubricants preferable in the present invention and names of manufacturers are described below. (1) Fatty Acid Amide Lubricants Saturated Fatty Acid Amide Lubricants Behenic Acid Amide Lubricants; Diamid KN (Nippon Kasei), etc. Stearic Acid Amide Lubricants; Armide HT (Lion Oil), Alflo S-10 (Nippon Oil), Fatty Acid Amide S (Kao), Diamond Mid 200 (Nippon Kasei), Diamond Mid AP-1 (Nippon Kasei), Amide S Amide T
(Nitto Kagaku), Neutron-2 (Nippon Seika), etc. Palmitamide amide lubricant; Neutron S-18 (Nippon Seika), Amide P (Nitto Kagaku), etc. Laurate amide lubricant; Armide C (Lion.
Akzo), Diamid (Nippon Kasei), etc. Unsaturated fatty acid amide lubricants, erucic acid amide lubricants; Alflo P-10 (Nippon Yushi), Neutron-S (Nippon Seika), LUBROL
(I ・ C ・ I), Diamid L-200 (Nippon Kasei), etc. Oleic acid amide lubricants; Armoslip CP (Lion Akzo), Neutron (Nippon Seika), Neutron E-18 (Nippon Seika) ), Amide O (Nitto Kagaku), Diamid O-200, Diamid G-200 (Nippon Kasei), Alflo E-10 (Nippon Oil & Fats), Fatty Acid Amide O (Kao), etc. Bis fatty acid amide lubricant Methylenebisbeh Nitric acid amide lubricants; Diamid NK bis (Nippon Kasei), etc. Methylene bis stearic amide lubricants: Diamid 200 bis (Nippon Kasei), Armowax (Lion
Akzo), bisamide (Nitto Kagaku), etc. Methylenebiooleic acid amide lubricant; Lubron O
(Nippon Kasei) etc. Ethylenebisstearic acid amide lubricants; Armoslip EBS (Lion Akzo) etc. Hexamethylenebisstearic acid amide lubricants; Amide 65 (Kawaken Fine Chemicals) etc. Hexamethylenebisoleic acid amide lubricants; Amide 60 (Kawaken Fine Chemicals) etc.

(2) Silicone-based lubricants Various grades of dimethylpolysiloxane and modified products thereof, and other modified products of silicon (typical example: siloxane). Typical examples are carboxyl modified silicone, α-methylstyrene modified silicone, α-olefin modified silicone, polyether modified silicone, fluorine modified silicone,
Hydrophilic special modified silicone, olefin polyether modified silicone, epoxy modified silicone, amide modified silicone, alcohol modified silicone, alkyl modified silicone,
Alkylaryl modified silicone, amino modified silicone,
Alkylhydrogen-modified silicone (Shin-Etsu Silicone, Toray Silicone), etc. In particular, various silicones not only exert the effects of improving resin fluidity and lubricity, but also when used in combination with light-shielding substances and coloring substances, light-shielding substances and coloring substances It is preferable because it exhibits unexpected effects such as improved dispersibility and improved coloring power.

(3) Nonionic surfactant type lubricant Electrostripper-TS-2, Electrostripper-TS-3 (Kao soap), etc.

(4) Hydrocarbon lubricants Liquid paraffin, natural paraffin, microwax,
Synthetic paraffin, polyethylene wax, polypropylene wax, chlorinated hydrocarbon, fluorocarbon, etc.

(5) Fatty acid type lubricant Higher fatty acid (preferably C ₁₂ or more), oxy fatty acid, etc.

(6) Ester lubricants Lower alcohol esters of fatty acids, polyhydric alcohol esters of fatty acids, polyglycol esters of fatty acids, fatty alcohol esters of fatty acids, etc.

(7) Alcohol-based lubricant Polyhydric alcohol, polyglycol, polyglycerol, etc.

(8) Metal soaps Higher fatty acids such as lauric acid, stearic acid, ricinoleic acid, naphthenic acid and oleic acid, and Li, Mg, Ca, S
Compounds with metals such as r, Ba, Zn, Cd, Al, Sn and Pb

These lubricants may be used alone or in combination of two or more if necessary.

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

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

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

The amount of the above lubricant added is 0.01 to 5.0.
Weight percent is preferred. If the addition amount is less than 0.01% by weight, there is almost no addition effect, and only the kneading cost increases.
If it exceeds 0% by weight, bleed-out will occur, or screw slip will occur, resulting in unstable discharge rate and frequent molding failures, as well as deterioration of kneading properties with polystyrene-based resin, polyolefin-based resin, etc. To do. 0.01 to 3.0% by weight is preferable in the case of a fatty acid amide lubricant, which is inexpensive and does not have a bad influence such as fogging or sensitivity abnormality on the photographic film, and has a great effect of improving the lubricity and shortening the injection molding cycle, and particularly 0.02 to 1.0% by weight. % Is preferable from the standpoints of greatly reducing molding failures and preventing bleed-out. Also,
Although the effect of improving lubricity is small, it improves the dispersibility of various additives and improves the fluidity of polystyrene resins and polyolefin resins. It can be used up to the amount that does not occur.

A drip-proofing agent can be added to the core for a photographic light-sensitive material of the present invention. Table 1 shows examples of the drip-proof agent. Diglycerin monostearate, polyglycerin monopalmitate, sorbitan monolaurate, sorbitan monostearate, sorbitan monooleate, sorbitan monoerucate, polyoxyethylene sorbitan fatty acid ester, stearic acid monoglyceride, palmitic acid Monoglyceride, oleic acid monoglyceride, lauric acid monoglyceride, polyoxyethylene nonylphenol ether, sorbitan sesquipalmitate, diglycerin sesquioleate, sorbitol fatty acid ester, sorbitol fatty acid / dibasic acid ester, diglycerine fatty acid / dibasic acid ester, glycerin fatty acid・ Dibasic acid ester, sorbitan fatty acid, dibasic acid ester, sorbitanpa Miteto, sorbitan stearate, sorbitan palmitate, propylene Oren oxide 3 moles adduct, sorbitan palmitate, propylene Oren oxide 2 mol adduct, sorbitol stearate,
Sorbitol stearate / ethylene oxide 3 mol adduct, diglycerin palmitate, glycerin palmitate, glycerin palmitate / ethylene oxide 2 mol adduct and the like.

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

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

An antioxidant is used to prevent the fog and abnormal sensitivity of the photographic film such as aldehydes and ketones from being caused by resin oxidative decomposition, and to prevent the formation of spots (insoluble foreign matter-like solid). It is preferable to add it in order to prevent coloring failure and the like. Representative examples of this antioxidant are shown below. (A) Phenolic antioxidant 6-t-butyl-3-methylphenyl derivative, 2.6
-Di-t-butyl-P cresol, t-butylphenol), 2.2'-methylenebis- (4-ethyl-6-t
-Butylphenol), 4,4'-butylidene bis (6
-T-butyl-m-cresol), 4.4'-thiobis (6-t-butyl-m-cresol), 4.4-dihydroxydiphenylcyclohexane, 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 '
-Butylidene bis (3-methyl-6-t-butylphenol), stearyl-β (3.5-di-4-butyl-4)
-Hydroxyphenyl) propionate, 1.1 / 3-
Tris (2-methyl-4hydroxy-5-t-butylphenyl) butane, 1.3.5 trimethyl-2.4.6-
Tris (3.5-di-t-butyl-4hydroxybenzyl) benzene, tetrakis [methylene-3 (3'-5'-
Di-t-butyl-4′-hydroxyphenyl) propionate] methane, etc. (b) Ketoneamine condensation-type antioxidant 6-ethoxy-2,2,4-trimethyl-1,2-dihydroquinoline, 2,2.4- Polymers of trimethyl-1,2-dihydroquinoline, trimethyldihydroquinoline derivatives, etc. (c) Allylamine antioxidants Phenyl-α-naphthylamine, N-phenyl-β-naphthylamine, N-phenyl-N′-isopropyl-P
-Phenylenediamine, N.N'-diphenyl-P-phenylenediamine, N.N'-di-β-naphthyl-P-
Phenylenediamine, N- (3'-hydroxybutylidene) -1-naphthylamine, etc. (d) Imidazole-based antioxidant 2-mercaptobenzimidazole, zinc salt of 2-mercaptobenzimidazole, 2-mercaptomethylbenzimidazole, etc. ) Phosphite antioxidants Alkylated allyl phosphite, diphenylisodecyl phosphite, tris (nonylphenyl) phosphite sodium phosphite, trinonylphenyl phosphite, triphenyl phosphite, etc. (f) Thiourea antioxidant Agents Thiourea derivatives, 1,3-bis (dimethylaminopropyl) -2-thiourea, etc. (to) Other antioxidants useful for air oxidation Dilauryl thiodipropionate, etc.

Representative commercial antioxidants are shown below. (1) Phenolic antioxidant; SUMILIZER B
HT (Sumitomo), IRGANOX 1076 (Ciba Geigy),
MARK AO-50 (Adeka Argus), SUMIL
IZER BP-76 (Sumitomo), TOMINOX SS (Yoshitomi), IRGANOX 565 (Ciba-Geigy), NONO
X WSP (ICI), SANTONOX (Monsant
o), SUMILIZER WX R (Sumitomo), ANTA
GEGRYSTAL (Kawaguchi), IRGANOX 1035 (Ciba Geigy), ANTAGE W-400 (Kawaguchi), NOC
LIZER NS-6 (Ouchi Shinko), IRGANOX 14
25 WL (Ciba Geigy), MARKAO-80 (Adeka Argus), SUMILIZER GA-80 (Sumitomo), TOPANOL CA (ICI), MARK AO
-30 (Adeka Argus), MARK AO-20 (Adeka Argus), IRGANOX 3114 (Ciba Geigy), MARK AO-330 (Adeka Argus), IR
GANOX 1330 (Ciba Geigy), CYANOX 1790
(ACC), IRGANOX 1010 (Ciba Geigy), M
ARK AO-60 (Adeka Argus), SUMILI
ZER BP-101 (Sumitomo), TOMINOX TT (Yoshitomi), etc. (2) Phosphorus antioxidants; IRGAFOS 168 (Ciba Geigy), MARK 2112 (Adeka Argus), WESTO
N 618 (Borg Warner), MARK PEP-8 (Adeka Argus), ULTRANOX 626 (Borg Warner), MARK PEP-24G (Adeka Argus), MARK PEP-36 (Adeka Argus), H
GA (Sanko) etc. (3) Thioether antioxidant; DLTDP "YOSH
ITOMI "(Yoshitomi), SUMILIZER TPL (Sumitomo), ANTIOX L (NOF), DMTD" YOSH "
ITOMI "(Yoshitomi), SUMILIZER TPM (Sumitomo), ANTIOX M (NOF), DSTP" YOSH "
ITOMI "(Yoshitomi), SUMILIZER TPS (Sumitomo), ANTIOXS (NOF), SEENOX 412S
(Cipro), MARK AO-412 S (Adeka Argus), SUMILIZER TP-D (Sumitomo), MAR
K AO-23 (Adeka Argus), SANDSTAB
P-EPQ (sand), IRGAFOSP-BPQ F
F (Ciba Geigy), IRGANOX 1222 (Ciba Geigy), MARK 329K (Adeka Argus), WEST
ON 399 (Borg Warner), MARK 260 (Adeka Argus), MARK 522A (Adeka Argus)
Etc. (4) Metal deactivator NAUGARD XL-1 (Uniroyal), MARK
CDA-1 (Adeka Argus), MARK CDA-
6 (Adeka Argus), LRGANOX MD-1024
(Ciba Geigy), CUNOX (Mitsui Toatsu), etc. Particularly preferred antioxidants are phenolic antioxidants, and commercially available products include Irganox of Ciba Geigy and Sumilizer BHT and Sumilizer of Sumitomo Chemical Co., Ltd.
BH-76, Sumilizer WX-R, Sumilizer BP-10
It is 1 mag.

Also, 2,6-di-hibutyl-p-cresol (BHT), a low-volatile high molecular weight phenolic antioxidant (trade name: Ireganox 1010, Ireganox 1076, T
opanol CA, Ionox 330, etc.), dilauryl thiodipropionate, distearyl thiopropionate, dialkyl phosphate and the like, and it is effective to use one or more, particularly two or more, in combination.

The addition amount is, for example, 0.001 to 2.0% by weight when added to the polyolefin resin adhesive layer. If the amount added is less than 0.001% by weight, there is almost no effect. On the other hand, if the addition amount exceeds 2.0% by weight, the photographic light-sensitive material utilizing the oxidation and reduction effects is adversely affected, and abnormalities in photographic performance (fogging and sensitivity fluctuation) may occur. For this reason, it is preferable to add the antioxidant in the minimum amount that does not cause coloring failure or spots. Vitamin E, which has no adverse effect on the human body, has a large antioxidant effect on various thermoplastic resins, and can improve the light-shielding property, is particularly preferable.

Further, when used in combination with carbon black or the like, the antioxidant exhibits a synergistic effect. The combined use of a phenol-based antioxidant, a phosphorus-based antioxidant and carbon black is preferable because the antioxidant effect is particularly exhibited.

Others Plastics Data Handbook (published by KK Industrial Research Institute), pages 794 to 799, data on various antioxidants and plastic additives (KK
Chemical Industry Co., Ltd.) pages 327 to 329 of various antioxidants and PLASTICS AGE ENCYCLOPEDIA Advanced Edition 1986 (KK Plastic Age) pages 211 to 212 of various antioxidants, etc. Is possible.

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

The hindered phenolic antioxidant used in the present invention is a commercially available antioxidant, and when applied to a resin composition for a photographic film container, the occurrence of fogging on the photographic film Any hindered phenolic antioxidant described below can be used, as long as it does not cause an increase / decrease sensation. For example, 1.3.5-trimethyl-2.4.6-tris (3.
5-di-tert-butyl-4-hydroxybenzyl) benzene, tetrakis [methylene (3.5-di-tert-butyl-4-hydroxy-hydrocinnamate)] methane,
Octadecyl-3.5-di-tert-butyl-4-hydroxy-hydrocinnamate, 2.2'.2 ''-tris [3.
5-di-tert-butyl-4-hydroxyphenyl) propionyloxy] ethyl isocyanurate, 1.3.5-
Tris (4-tert-butyl-3-hydroxy-2.6-
Di-methylbenzyl) isocyanurate, tetrakis (2.4-di-tert-butylphenyl) 4.4'-biphenylene diphosphite, 4.4'-thiobis (6-te
rt-butyl-0-cresol), 2.2'-thiobis-
(6-tert-butyl-4-methylphenol), tris- (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, 2.2'-methylene-bis- (4-methyl-6-tert) -Butylphenol), 4.4'-methylene-bis- (2.6-di-tert-butylphenol), 4.
4'-butylidene bis- (3-methyl-6-tert-butylphenol), 2.6-di-tert-butyl-4-methylphenol, 4-hydroxymethyl-2.6-di-t
ert-butylphenol, 2.6-di-tert-butyl-4
-N-butylphenol, 2.6-bis (2'-hydroxy-3'-tert-butyl-5'-methylbenzyl) -4
-Methylphenol, 4.4'-methylene-bis- (6-
tert-butyl-0-cresol), 4.4'butylidene-
Bis (6-tert-butyl-m-cresol) and the like.

Since there is little bleed-out or thermal decomposition and the adverse effect on the photographic light-sensitive material is small, the melting point (Melting)
The point) is preferably 100 ° C. or higher, particularly preferably 120 ° C. or higher. In order to prevent the oxidative decomposition of the polyolefin resin of the present invention, it is particularly preferable to use a mixture of phenolic and phosphorus antioxidants.

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

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

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

[0058]

[Chemical 1]

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

[0060]

[Chemical 2]

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

The inorganic nucleating agent is an alkali metal hydroxide such as lithium hydroxide, sodium hydroxide or potassium hydroxide,
Alkali metal oxides such as sodium oxide, alkali metal carbonates such as lithium carbonate, sodium carbonate, potassium carbonate, sodium hydrogen carbonate and potassium hydrogen carbonate, alkaline earth metal waters such as calcium hydroxide, magnesium hydroxide and barium hydroxide. Examples thereof include oxides, alkaline earth metal oxides such as calcium carbonate and calcium oxide.

The nucleating agent is not limited to these, and other known nucleating agents can be used. Needless to say, the nucleating agent is not limited to a single type, and two or more types can be used in combination.

An organic nucleating agent which has a great effect of adding a crystallization-accelerating effect of a resin as a nucleating agent, has a great effect on a photographic film, reduces molding failures, shortens a molding cycle, and improves rigidity and transparency. A particularly preferable example is described below. di- (o-methylbenzylidene) sorbitol o-methylbenzylidene-p-methylbenzylidenesorbitol di- (m-methylbenzylidene) sorbitol m-methylbenzylidene-o-methylbenzylidenesorbitol di- (p-methylbenzylidene) sorbitol m-methylbenzylidene-p-methylbenzylidenesorbitol 1 ・ 3-heptanylidenesorbitol 1,3,2,4-diheptanylidenesorbitol 1,3,2,4-di (3-nonyl-3-pentenylidene) sorbitol 1,3-cyclohexanecarbylidenesorbitol 1,3,2,4-dicyclohexanecarbylidenesorbitol 1,3,2,4- di (p-methylcyclohexanecarbylidene) sorbitol Aromatic hybrocarbon groups or derivatives thereof 1 ・ 3-benzylidene sorbitol 1 ・ 3,2 ・ 4-dibenzylidene-D-sorbitol 1 ・ 3,2 ・ 4-di (m-methylbenzylidene) sorbitol 1 ・ 3, 2 ・ 4-di (p-methylbenzylidene) sorbitol 1 ・ 3,2 ・ 4-di (p-hexylbenzylidene) sorbitol 1 ・ 3,2 ・ 4-di (l-naphthalenecarbylidene) sorbitol 1 ・ 3,2 ・ 4-di (phenylacetylidene) sorbitol

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

[0066]

[Chemical 3]

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

[0068]

[Chemical 4]

[Wherein n is 14 to 30, preferably 18 to 27,
Most preferably, it represents a number of 20 to 25], and a higher fatty acid is provided by coating the surface of the solid powder of the dibenzylidene sorbitol derivative with the higher fatty acid to provide a dibenzylidene sorbitol derivative composition. To be done.

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

In a preferred embodiment of the organic nucleating agent of the present invention, a dibenzylidene sorbitol derivative in which R and R'in the general formula (I) each independently represent a methyl group or a chlorine atom is used.

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

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

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

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

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

The aqueous emulsion of higher fatty acid used in the above method is, for example, an organic solvent solution having a concentration of higher fatty acid of 5 to 50% by weight, preferably 10 to 50% by weight, and a small amount of a surfactant, for example, 100% by weight of higher fatty acid. 1-1 for parts
It can be easily obtained by dispersing in water using 0 part by weight, preferably 2 to 5 parts by weight.

The presence of a coating of higher fatty acid formed on the surface of the solid powder of dibenzylidene sorbitol derivative can be determined by observing the coating by dyeing it with a dye, as described in detail in Examples below. You can check.

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

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

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

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

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

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

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

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

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

As a method for blending the nucleating agent, there are a compound method, a dry blend method, a master batch method and the like, but the master batch method is preferable. Since the dryness is high and the particles are easily scattered, it is difficult to mix them as they are. A small amount of a dispersant should be mixed with a wetting agent.
Various dispersants, various waxes, carboxylic acid anhydrides, higher fatty acids and the like are effective as dispersants, and various fatty acid metal salts, various silicones, oleic acid amides and other lubricants are particularly preferable. As the wetting agent, a plasticizer such as DOP or DHP can be used.

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

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

The core for the photographic light-sensitive material of the present invention is a so-called Brownie type roll such as a core for winding a motion picture film, a spool for winding a 35 mm film, a spool for a film with a lens, 120 size, 220 size, etc. In addition to spools for films, spools for 110 films, etc.,
There are various types of winding cores used in reels for photographic printing paper, minilab magazines, and magazines for light-room loading of roll-shaped photographic photosensitive materials. Further, Japanese Patent Laid-Open No. 4-67035 and Japanese Patent Publication No.
In the unused state disclosed in Japanese Unexamined Patent Publication No. 116549 and Japanese Unexamined Patent Publication No. 4-143749, even the tip of the photographic film is stored in the cartridge body, and the spool is rotated so that the tip of the photographic film is outside the cartridge body. There is a spool to send to.

[0092]

In the core for a photographic light-sensitive material of the present invention, the dust having irregularities on the winding surface is taken in and the dust is not largely projected from the winding surface.

[0093]

Embodiments of the core for a photographic light-sensitive material of the present invention will be described with reference to the drawings. 1 is a plan view of a core for a photographic light-sensitive material, FIG. 2 is a sectional view taken along the line AA in FIG. 1, FIG. 3 is a perspective view of the core for a photographic light-sensitive material seen from the gate side, and FIG. FIG. 5 is a perspective view seen from the side opposite to the gate, and FIG. 5 is a cross-sectional view of a mold for manufacturing a core for a photographic light-sensitive material.

In these figures, reference numeral 1 is an outer cylinder,
An inner cylinder 4 is integrally formed inside the outer cylinder 1 with an annular plate 2 and ribs 3 interposed therebetween. Then, the surface (winding surface) of the outer cylinder 1 is formed into a concavo-convex portion 5 by forming substantially hemispherical convex portions vertically and horizontally at predetermined intervals. The unevenness 5 has a maximum roughness of about 40 μm or less and a center line roughness of about 0.1 to 10 μm.
It is formed in m. An undercut convex portion 6 is formed on the inner surface of the outer cylinder 1 on the side opposite to the gate for fixing the core for the photographic material when the movable core is removed. Reference numeral 7 is a resin injection port (gate).

To manufacture the core for photographic light-sensitive material as described above, the mold shown in FIG. 5 is used. In the mold shown in this figure, reference numeral 11 is a fixed core, reference numeral 12 is a cavity, reference numeral 13 is a movable core, and reference numeral 14 is an inner core. The unevenness in the shape of is formed.

FIG. 6 is a perspective view of another embodiment of the core for photographic light-sensitive material of the present invention, and FIG. 7 is a side view of another embodiment of the core for photographic light-sensitive material of the present invention. The core for photographic light-sensitive material shown in these figures is a core for winding color photographic paper, and is formed by a core body 21 having a cylindrical shape, and an uneven portion 22 is formed on the surface (winding surface) of this core body 21. Has been done.
The unevenness 22 has a maximum roughness of about 40 μm or less and a centerline roughness of about 0.1 to 10 μm. Reference numeral 23 is a resin injection part.

FIG. 8 is a perspective view of another embodiment of the core for a photographic light-sensitive material of the present invention, and FIG. 9 is a sectional view taken along line AA in FIG.
The core for photographic light-sensitive material shown in these figures is a spool for photographic film, and this spool is composed of a substantially cylindrical spool body 31 and flanges 32 integrally formed near both sides of the spool body 31. There is. A concavo-convex portion 33 is formed on the surface (winding surface) of the spool body 31, and the concavo-convex portion 33 has a maximum roughness of about 40 μm or less and a center line roughness of about 0.1 to 10 μm. .

FIG. 10 is a perspective view of another embodiment of the core for a photographic light-sensitive material of the present invention. The core for a photographic light-sensitive material shown in this figure is for a motion picture film, and a flange 42 is formed on the outer peripheral edge of a core body 41, and an uneven portion 43 is formed on the surface (winding surface) of the core body 41. There is. The uneven portion 33 is
Maximum roughness is about 40μm or less, center line roughness is about 0.1-10μ
It is formed in m.

11 to 13 are partial sectional views showing the shapes of the concave and convex portions of the core for the photographic light-sensitive material. Figure 11
The concavo-convex portion 5 shown in is formed in a waveform having a wave height longer than the wavelength. The uneven portion 5 shown in FIG. 12 is formed in a waveform whose wave height is shorter than the wavelength. The uneven portion 5 shown in FIG.
A trapezoidal convex portion and a triangular concave portion are repeatedly formed.

Example 1 A core for a photographic light-sensitive material shown in FIG. This photographic material core has an outer diameter of 3 inches.
The film is for 3,000 feet of motion picture film (positive film) with a width of mm. The outer cylinder 1 has a wall thickness of 2.1 mm, the inner cylinder 4 has a wall thickness of 2.05 mm, and the annular plate 2 has a wall thickness of 2.2. mm, rib 3
Thickness is 2.0 mm, outer diameter of outer cylinder 1 is 76.2 mmφ, inner cylinder 4
Has an inner diameter of 25.9 mm and the length of both cylinders is 34.5 mm. The height of the undercut convex portion 6 is 0.1 mm, and the maximum roughness of the concave and convex portion 5 on the surface of the outer cylinder 1 is 3.5 μ.
m, and the center line average roughness is 0.5 μm.

This core is made of high impact polystyrene resin 30.
It is produced by an injection molding method using a polystyrene resin containing 1% by weight of surface-treated titanium dioxide and 69% by weight of polystyrene resin, and 1% by weight of a polystyrene resin. The two resin injection ports 7 and 7 are formed by cutting out the central portions of the outer edges of the two ribs that are symmetrical with respect to the center of the core so that a weld line is substantially generated in the rib portion.

This core has excellent injection moldability, the injection molding cycle is 7.2 seconds, the occurrence of scratches on the outer cylindrical surface is small, and the scratches are hard to see, and the wrapping property of the movie film is good. However, the occurrence of pressing marks and pressure fog due to the adhesion of dust almost disappeared. Further, the unevenness provided on the outer cylindrical surface of the core was also appropriate, and there was no occurrence of pressing marks or pressure fog caused by this unevenness formation that would affect the quality and cause a problem.

Further, since the weld line can be slightly generated on the two ribs equidistant from the two ribs provided with the resin injection port 7, the compressive strength is 265 kg → 329 kg.
It was possible to improve by about 24%. Further, the work of removing the remaining traces (gate traces) of the resin injection port (generally called post-processing) is unnecessary, and a large cost reduction can be achieved.

[Embodiment 2] Concavo-convex portion 5 on the surface of the outer cylinder 1.
However, except that the maximum roughness is 9.8 μm and the centerline average roughness is 2.5 μm, the core is the same material, the same injection molding method, the same size, and the same shape as those of the first embodiment. . This core had the same effect as in Example 1. The injection molding cycle was 7 seconds.

[Embodiment 3] Concavo-convex portion 5 on the surface of the outer cylinder 1.
However, except that the maximum roughness is 18 μm and the center line average roughness is 4.8 μm, the core is the same material as in Example 1, the same injection molding method, the same size, and the core used for the motion picture film. This core had the same effect as in Example 1. The injection molding cycle was 7 seconds.

[Prior Art Example 1] A core used for a motion picture film of the same material, the same injection molding method, and the same size and shape as in Example 1, except that the surface of the outer cylinder 1 is substantially flat. The roughness of the surface of the outer cylinder 1 has a maximum roughness of 0.8 μm,
The center line average roughness was 0.06 μm.

This core had a slightly poor releasability during injection molding, and the injection molding cycle had to be 8.5 seconds, which was longer than that of Example 1 by 20% or more. Further, the outer cylinder surface was frequently scratched due to contact with other cores after injection molding, and the difference in gloss due to the scratches was large, and the scratches were conspicuous and the commercial value was poor. The slipperiness was small and the wrapping property of the motion picture film was inferior to that of the example, and it was easy for spatter marks and pressure fog to be scattered due to dust adhesion.

Comparative Example 1 The surface of the outer cylinder 1 has a maximum roughness of
A core used for a motion picture film of the same material, the same injection molding method, and the same size and shape as in Example 1 except that the core is 44 μm and the center line average roughness is 11 μm.

This core is slightly better than Example 1 in that it is excellent in mold releasability from the mold at the time of injection molding, few scratches are generated on the outer cylindrical surface, and scratches are hard to see, but it is injection molded. The failure rate increases a little, film film for film is difficult to wrap, and it is easy for press marks and pressure fog to occur.
In particular, from the beginning of winding of the outer cylindrical surface to the 6th circumferential surface, the level was unusable as a product.

[Example 4] A core for a photographic light-sensitive material shown in Fig. 6. This photographic material core has an inner diameter of 76 mmφ,
It is for a roll length of 110 m of color photographic paper with a width of 89 mm and has a wall thickness of 5.0 mm. The maximum roughness of the uneven portion is 3.2 μm, and the center line average roughness is 0.3 μm. An impact-resistant polystyrene resin containing surface-treated calcium carbonate in an amount of 5% by weight is used and is manufactured by an injection molding method.

The core for a photographic light-sensitive material had excellent injection moldability, had a molding cycle of 10 seconds, had few scratches on the surface of the cylindrical core, and was hardly visible.
Also, it is easy to fix the tip of color photographic paper with adhesive tape,
It is easy to peel off, wrinkles and streaks do not occur even at the beginning of winding, the wrapping property is good, the generation of paper powder is eliminated and the generation of pressing marks and pressure fog due to the adhesion of dust is greatly reduced,
Moreover, there was almost no problem. Furthermore, the unevenness provided on the cylindrical surface of the core is moderate, and since it is formed in a roughly regular uneven shape, the quality of the color printing paper is affected by the impression marks and pressure fog caused by the uneven shape of the core surface. However, there was no problem. It also has suitability for reuse and suitability for use of recycled resin. Since the resin injection port 23 is provided at two symmetrical positions with respect to the center on the outer edge of the core, a resin confluence portion called a weld line, which is called a weld line, is lightly formed near the center between the resin injection ports 23. There was an occurrence.

When the tip of the photographic light-sensitive material is wrapped around the core with an adhesive tape, it exhibits a large adhesive strength when stopped, and conversely, when it is peeled from the core, it does not easily damage the core surface. It can be peeled off without any adhesive residue.

[Embodiment 5] The same material, the same injection molding method, and the same dimensions as in Embodiment 4, except that the surface of the core body 21 has a maximum roughness of 7.6 μm and a center line average roughness of 1.6 μm. , A core for photographic light-sensitive material used for color photographic paper having the same shape. This core for a photographic light-sensitive material had substantially the same effect as in Example 4.

[Embodiment 6] The same material, the same injection molding method, and the same dimensions as in Embodiment 4 except that the surface of the core body 21 has a maximum roughness of 12 μm and a center line average roughness of 3.7 μm. , A core for photographic light-sensitive material used for color photographic paper having the same shape. This core for a photographic light-sensitive material had substantially the same effect as in Example 4.

[Prior Art 2] A core for a photographic light-sensitive material for color photographic paper shown in FIG. 14, which is formed by Langston winding a base paper 51 for a winding core, and has a spiral groove 52. Formed on the surface.

The core of this photographic light-sensitive material has an inner diameter of 76 mm.
It is for 110 m roll of φ, width 89 mm color photographic paper,
It has a wall thickness of 8.0 mm and is made of neutral high-yield pulp paper. The surface has a maximum roughness of 36 μm and a centerline average roughness of 8.5.
The groove 52 had a depth of 108 μm and the groove 52 had a width of 1500 μm.

The core of this photographic light-sensitive material was likely to have scratches and irregularities on the surface thereof, and paper dust was likely to be generated. Further, it was difficult to stop the front end of the color photographic paper with an adhesive tape, and when it was peeled off, paper wasted on the core surface, and it could not be reused. Further, it is difficult to separate the resin and the paper, and the recyclability is insufficient. Furthermore, if it is not dried for several days, the moisture in the core will adversely affect the photographic properties (fogging and abnormal sensitivity will occur), as well as it will be pushed by the grooves with large irregularities, and groove marks and pressure fog will occur. The quality of color photographic paper 50 cm or more from the surface of the core was deteriorated.

[Embodiment 7] A spool for 35 mm photographic film corresponding to FIG. 8 is injection molded from a polystyrene resin composition in which a synthetic rubber, a lubricant and a light-shielding substance are mixed in a polystyrene resin. . As the polystyrene resin composition, 70% by weight of HI (impact-resistant) polystyrene resin having 6% by weight of butadiene synthetic rubber, GP
Pellets made of polystyrene resin 30% by weight 85% by weight
And 87% by weight of HI polystyrene resin, 3% by weight of furnace carbon black as a light-shielding substance, dimethylpolysiloxane with a silicone lubricant viscosity of 20,000 centistokes 1
It is preferable to use a mixture of 0% by weight of masterbatch pellets and 15% by weight of an automatic weighing machine. For molding the spool, a "Nestal (trade name)" molding machine manufactured by Sumitomo Heavy Industries was used (clamping pressure 150 tons), and the maximum roughness of the outer cylinder 31 surface was 7 μm and the center line average roughness was 1.8 μm We used a semi-hot runner type mold with 24 picks so that a satin-like embossing could be formed.

This core for a photographic light-sensitive material had excellent injection moldability, had a molding cycle of 7 seconds, had few scratches on the surface of the cylindrical core, and was hardly visible.
There were no traces of pressure or fog caused by the adhesion of dust.

The polystyrene resin composition has a MFR of
(Melt flow rate) is 12g / 10 minutes, Vicat softening point is
93 ℃, tensile yield strength 370kg / cm ² , flexural modulus 32000kg
/ cm ² , Izod impact strength is 3.2 kgcm / cm, total amount of volatile matter measured by gas chromatography is 587 ppm, and total amount of sulfur content is 0.1% by weight. Therefore, fog and abnormal sensitivity do not occur on photographic film.

The light-shielding substance added to the polystyrene resin composition used for the 35 mm film spool containing the cartridge defined in the above (ISO: 1007 to 1979) is
It is preferably an opaque inorganic compound, and various carbon blacks, graphite, titanium nitride, etc., which are particularly excellent in heat resistance and light resistance, may be used. In addition, the addition amount at this time should be adjusted so that the characteristics required for the spool can be secured without adversely affecting the photographic properties and physical strength.

In order to reduce the take-up torque and the feed-out torque of the photographic film, the inside of the flange and / or
Alternatively, it is preferable to form irregularities on the outside or to add various lubricants and surfactants to improve the lubricity.

As the spool material, a polyolefin resin composition may be used in addition to the polystyrene resin composition. Particularly, a resin composition containing 70% by weight or more of a propylene / α-olefin copolymer resin having a high MFR (16 g / 10 minutes or more) is preferable. However, the polyolefin resin is easily oxidized, and aldehydes and ketones generated by the oxidative decomposition of the resin may cause fog and sensitivity abnormalities on the photographic film, or insoluble foreign matters may be generated. Therefore, when using a polyolefin resin, in addition to adding a lubricant and a light-shielding substance as an additive,
It is preferable to add an antioxidant.

[0124]

According to the present invention, since the roughness of the core surface is set within a specific range, the occurrence of pressure scratches and pressure fog is reduced even if dust is attached, and the pressure scratches are reduced.
Further, the wound surface of the core for a photographic light-sensitive material is less likely to be scratched, and even if scratched, it is hard to see.
Furthermore, it has excellent injection moldability (especially good releasability).
ing.

[Brief description of drawings]

FIG. 1 is a plan view of an embodiment of a core for a photographic light-sensitive material according to the present invention.

FIG. 2 is a sectional view taken along the line AA in FIG.

FIG. 3 is a perspective view of one embodiment of a core for a photographic light-sensitive material according to the present invention, viewed from the gate side.

FIG. 4 is a perspective view of an embodiment of a core for a photographic light-sensitive material according to the present invention as seen from the side opposite to the gate.

FIG. 5 is a sectional view of a mold for manufacturing a core for a photographic light-sensitive material according to the present invention.

FIG. 6 is a perspective view of another embodiment of the core for a photographic light-sensitive material according to the present invention.

FIG. 7 is a sectional view of another embodiment of the core for a photographic light-sensitive material according to the present invention.

FIG. 8 is a perspective view of another embodiment of the core for a photographic light-sensitive material according to the present invention.

FIG. 9 is a perspective view of another embodiment of the core for a photographic light-sensitive material according to the present invention.

FIG. 10 is a partial perspective view of another embodiment of the core for a photographic light-sensitive material according to the present invention.

FIG. 11 is a partial cross-sectional view showing the shape of the uneven portion of the core for a photographic light-sensitive material according to the present invention.

FIG. 12 is a partial cross-sectional view showing the shape of an uneven portion of the core for a photographic light-sensitive material according to the present invention.

FIG. 13 is a partial cross-sectional view showing the shape of an uneven portion of the core for a photographic light-sensitive material according to the present invention.

FIG. 14 is a perspective view of a conventional core for a photographic light-sensitive material.

[Explanation of Codes] 1 ... Outer cylinder 2 ... Annular plate 3 ... Rib 4 ... Inner cylinder 5, 22, 33, 43 ... Uneven portion 6 ... Undercut convex portion 7 ... Resin injection port (gate)

Claims (4)

[Claims] 1. A cylindrical winding surface around which a belt-shaped photographic light-sensitive material is wound is formed with irregularities having a maximum roughness of 40 μm or less and a center line average roughness of 0.1 to 10 μm. Photosensitive material core 2. A core for a photographic light-sensitive material according to claim 1, which is formed of a thermoplastic resin composition containing at least one of an antistatic agent, a lubricant, a surfactant, a drip-proofing agent and a conductive substance. 3. The method according to claim 1, which is formed by an injection molding method using a thermoplastic resin composition containing a light-shielding substance.
Photosensitive material core described in 4. The thermoplastic resin composition has a melt flow rate of 5 to 30 g / 10 minutes, a Vicat softening point of 85 ° C. or higher, a bending elastic modulus of 25000 kg / cm ² or higher, and an Izod impact strength of 1.5 kg.
The core for a photographic light-sensitive material according to claim 2 or 3, which is formed of a resin composition containing 70% by weight or more of a polystyrene resin containing 0.1 to 10% by weight of a synthetic rubber having a cm / cm or more.