JPH1010683A - Injection molded article for photographic sensitive material and its injection molding method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide injection molded articles for photographic sensitive materials having excellent injection moldability, appearance, physical strength, dimensional accuracy, perfect light shieldability, lubricity, antistatic property and heat resistance. SOLUTION: The injection molded articles are injection molded by using a styrene resin compsn. consisting of >=50wt.% content of styrene resin having a melt flow index of 3.0 to 40.0g/10min, Rockwell hardness M of >=38, Izod impact strength of >=2.0kg.cm/cm, modulus of bending elasticity of >=20,000kg/cm<2> and a Vicat softening point of >=78 deg.C, 0.01 to 20wt.% total content of >=2 kinds selected from lubricants or surfactants, >=3wt.% thermoplastic resin subjected to >=2 times heat history at >=150 deg.C and 0.01 to 20wt.% total content of at least >=1 kinds among antioxidant, deodorant and aromatic.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a spool for a photographic film, a cartridge for a photographic film cartridge, a core for a belt-shaped photosensitive material such as a movie film, an instant film unit,
The present invention relates to an injection molded article for photographic photosensitive materials such as a photographic film cartridge, a film unit with a lens, and a resin photographic film cartridge (such as an advanced photo system), and an injection molding method therefor.

[0002]

2. Description of the Related Art Conventionally, a 135 type photographic film spool, a core for a band-shaped photosensitive material such as a movie film, a simple filming mechanism, a film unit with a lens having a built-in photographic film in advance, and a resin molded product including an outer case. Injection molded products for photographic photosensitive materials such as resin photographic film patrone (Advanced Photo System, hereinafter referred to as APS) composed of various resin compositions for enhancing light-shielding properties, impact resistance, abrasion resistance, etc. Injection molded.

The photographic film spool uses a polystyrene resin or an impact-resistant polystyrene resin, so that the locking force when the film claw provided on the photographic film spool locks the end of the film is 11.3 kg. Japanese Patent Publication No. 61-36995 discloses that excellent values can be obtained.

The core for the belt-shaped photosensitive material is formed by using an impact-resistant polystyrene resin containing a rubber-like substance in a styrene resin, among thermoplastic resins such as a polypropylene resin, a polystyrene resin, and an ABS resin. It is described in Japanese Utility Model Publication No. 2-37799 that by limiting, a weld line can be formed with a small weld line and improved in compressive strength and injection moldability (no gate processing is required).

A film unit with a lens is formed of a resin composition obtained by adding carbon black to an impact-resistant polystyrene resin having a low melt flow index so that a necessary and sufficient light-shielding property can be obtained. -2
No. 26643, and the like.

Resin photographic film patrone (APS)
Japanese Patent Application Laid-Open No. 1-3125 discloses an outer case made of a resin composition obtained by adding carbon black to an impact-resistant polystyrene resin so that a necessary and sufficient light-shielding property can be obtained.
No. 38 publication.

[0007]

However, when a photographic film spool is formed from the above-described resin composition, variations are likely to occur due to the formation of the photographic film spool, resulting in several times differences in locking force and physical strength. Injection moldability, heat resistance,
Dimensional accuracy, lubricity, antistatic properties, abrasion resistance are not sufficient,
In addition, there are many cases where there is a problem in the photographic properties, and it has been difficult to put it to practical use.

When a belt-shaped photosensitive material core is injection-molded with a resin composition to which a rubber-like substance or the like is added, the wound photosensitive material roll becomes less slippery due to the nature of the rubber-like substance, and good winding is possible. On the other hand, the frictional force on the surface of the belt-shaped photosensitive material core is increased, so that the injection moldability and the wear resistance are not sufficient. Further, when a lubricant, a surfactant and the like are added thereto to make the surface of the belt-shaped photosensitive material slippery, the winding of the roll film is deteriorated, and at the same time, good winding properties, injection moldability and wear resistance are simultaneously obtained. It was difficult.

The above-described film unit with a lens is
Since carbon black is added to conventional low melt flow index impact resistant polystyrene resin, the fluidity of the resin decreases and the resin temperature must be increased, resulting in thermal decomposition of the resin and additives. Good photographic properties were difficult to obtain. Moreover, the molding cycle was long, and the appearance of the weld line was poor due to the large number of weld lines, and the physical strength was low. This is because there is insufficient study on the resin composition, and further improvement is desired.

[0010] The resin composition used in a resin photographic film cartridge (such as an advanced photo system) can provide sufficient light-shielding properties, but requires a long molding cycle and is expensive. Improvements in photographic properties, heat resistance, appearance, physical strength, and the like have been demanded, and many weld lines have occurred.

The present invention solves the above problems, does not adversely affect photographic properties, is excellent in injection moldability, improves dispersibility and fluidity of a light-shielding substance, and improves appearance, physical strength and dimensional accuracy. An object of the present invention is to provide an injection molded article for a photographic photosensitive material having excellent light-shielding properties, lubricity, antistatic properties, and heat resistance, and an injection molding method for obtaining the injection molded article for the photographic photosensitive material.

[0012]

In order to solve the above problems, the injection molded article for photographic photosensitive materials according to the first invention has a melt flow index of 3.0 to 40.0 g / m.
10 minutes, Rockwell hardness of M38 or more, Izod impact strength of 2.0 kg · cm / cm or more, flexural modulus of 20,000
The content of a styrene resin having a Vicat softening point of 78 ° C. or more is 50% by weight or more, and the total content of two or more kinds selected from lubricants or surfactants is 0.01 to 100 kg / cm ² or more.
20% by weight, 3% by weight or more of a thermoplastic resin having passed through a heat history of 150 ° C. or more twice or more, and a total content of at least one kind of an antioxidant, a deodorant, and an aromatic is 0.01 to 20%.
It was obtained by injection molding using a styrene-based resin composition in a percentage by weight.

In the method for producing an injection-molded product for photographic light-sensitive material according to the second invention, in order to obtain the injection-molded product for photographic light-sensitive material of the present invention, the wall temperature of the core and cabin in the mold is set to 100 to 200. ° C, the molten styrene-based resin composition was injected and filled in a mold, and the injection-molded product was taken out after the wall temperature of the core / cavity portion fell below the Vicat softening point of the styrene-based resin composition. Things.

Typical styrene resins include styrene resins and ABS resins. Styrene resins include a transparent general-purpose polystyrene (GPPS) resin, which is a homopolystyrene resin obtained by polymerizing only a styrene monomer, and a high-impact polystyrene (HIPS) resin, which is a rubber-containing polystyrene resin reinforced with a rubber-like substance. These polystyrene moieties are linear and amorphous. The use of a Natta catalyst gives isotactic polystyrene, which is opaque and has a heat distortion temperature of 200.
° C, resin photo film patrone (A
It is most suitable for colored injection molded products used under sunlight such as PS) and film units with lenses.

The characteristic properties of styrene resin are listed as follows: (1) Specific gravity is small. (2) It is tasteless, odorless and non-toxic. (3) Low hygroscopicity. (4) Excellent electrical insulation and high-frequency insulation. (5) Good colorability and paintability. (6) Excellent moldability. (7) Good dimensional stability of molded products. (8) Relatively cheap. Etc., but has the following disadvantages depending on the application. (1) Insufficient impact resistance. (2) Attacks by some oils and organic solvents. (3) Insufficient heat resistance. (4) Easy to burn. (5) Insufficient weather resistance. (6) Easily charged.

Most of the styrene resin is produced by a continuous bulk polymerization method in which a polymerization step, a degassing / monomer recovery step, and a granulation step are continuously combined, and a part is produced by a suspension batch polymerization method. ing. In the present invention, an impact-resistant polystyrene resin containing 0.5 to 15% by weight of a synthetic rubber produced by a continuous bulk polymerization method is preferred in view of photographic properties, quality, cost, and the like. These are all typical radical polymerization methods.

Asahi Kasei Kogyo, Idemitsu Petrochemical, Nippon Steel Corporation,
Dainippon Ink and Chemicals, Electrochemical, Nippon Polystyrene, Mitsui Toatsu, Mitsubishi Monsanto Kasei.

A rubber-containing polystyrene resin (rubber-containing aromatic monovinyl resin) is a polymer of a rubbery substance and an aromatic monovinyl, a mixture of a rubbery substance and an aromatic monovinyl in a kneaded state, or a rubbery substance. There are three embodiments of a mixture of a polymer with an aromatic monovinyl resin and a mixture of an aromatic monovinyl resin. The impact resistance is increased by containing a rubber-like substance.

Examples of the rubbery substance include an ethylene / propylene copolymer, an ethylene / propylene / non-conjugated diene terpolymer, an isoprene copolymer, a polyisoprene, a styrene-isoprene copolymer, a polybutadiene, and a styrene / butadiene. A high cis polybutadiene having a high cis content (preferably 70 mol% or more, preferably 90 mol% or more) and a low cis polybutadiene having a low cis content. Can be The average particle size of this rubber-like substance is suitably from 0.1 to 10 μm, preferably from 0.2 to 7 μm.
μm, more preferably 0.5 to 5 μm. 0.1μ
If it is less than m, impact strength is reduced, abrasion frequently occurs, and the cost is high. If it exceeds 10 μm, the appearance is deteriorated and the commercial value is reduced. In order to obtain a high-gloss injection molded product having high commercial value, it is necessary to use a rubbery substance having an average particle diameter of 0.1 to 1.5 μm to improve the antireflection property and prevent light fog. . 1.5 to 10 μm, preferably 1.7 to 8 μm when used as a spool for a photo film,
More preferably, it is preferable to use a rubber-like substance having an average particle diameter of 2 to 6 μm.

Examples of the aromatic monovinyl include styrene and a nucleus alkyl-substituted styrene such as o-methylstyrene, p-methylstyrene, m-methylstyrene, 2,4-dimethylstyrene, ethylstyrene and p-tert-butylstyrene; 2,4,6-tribromostyrene, 2,4,6
-Nuclear halogenated styrene such as trichlorostyrene and α-
Α-alkyl-substituted styrenes such as methylstyrene and α-methyl-p-methylstyrene are used. In addition, methacrylates, acrylates, acrylonitriles, and maleic anhydride copolymerizable with styrene monomers are also included.

When the rubber-containing aromatic monovinyl resin is a polymer of a rubbery substance and aromatic monovinyl, the polymerization is carried out by a radical polymerization method (badge bulk polymerization method, continuous bulk polymerization method, continuous solution polymerization method, suspension solution polymerization method, suspension polymerization method). Polymerization method, emulsion polymerization method, etc.) or ionic polymerization method. From the economic viewpoint of these polymerization methods, a bulk polymerization method and a bulk-suspension polymerization method in which a styrene monomer is reacted with a radical in the presence of a rubbery polymer are preferable, and a continuous bulk polymerization method is particularly preferable. In addition, suspension polymerization (batch type) is advantageous in that there are few residual monomers, excellent heat resistance, and small turnaround.
Is preferred.

The ABS resin is acrylonitrile (A),
A thermoplastic resin containing butadiene (B) and styrene (S) as main components, and containing polybutadiene as a rubbery substance. This is because the dispersed polybutadiene particles
Since the S copolymer is grafted, the compatibility between the polybutadiene particles and the surrounding AS continuous phase is good, and no aggregation of the polybutadiene particles is observed. ABS resin is a graft rubber particle dispersion system similar to high-impact polystyrene (also referred to as high-impact polystyrene and abbreviated as HIPS) resin, and its viscoelastic temperature characteristics are as high as that of polybutadiene rubber. It is divided into dispersion absorption around + 120 ° C. by the AS copolymer.

The ABS resin has an excellent impact strength, which is the most significant feature. This is based on the absorption of the impact energy due to the deformation of the polybutadiene particles and the generation of the craze generated from the polybutadiene particle interface. Craze theory by absorption is supported. It has been reported that, in order to further increase the impact strength, a mechanism for suppressing the propagation and destruction of craze in addition to the occurrence of craze is important.

Other characteristics include good injection molding workability, and excellent rigidity and chemical resistance. In addition, coloring with a light-shielding substance is free, and secondary workability such as painting, printing, hot stamping, vacuum deposition, plating and the like is also good. A blend system with another resin such as a polycarbonate resin or a polyvinyl chloride resin forms a molding group characteristic of an ABS alloy. The only drawbacks are the deterioration of photographic properties and poor weather resistance. However, this is also due to the selective addition of specific types of additives such as carbon black and antioxidants, which will be described later, and the study of resin compositions. It is now possible.

As a production method, recently, a polybutadiene lantex is reacted with an AN / ST (styrene) monomer to produce ABS having a high rubber content, and this is blended with a separately produced AS resin copolymer resin. Method is often used.

The uncrosslinked rubber is dissolved in ST (abbreviation of styrene) monomer, preliminarily bulk polymerization is performed in a rubber matrix state, and when a phase transition to a rubber dispersion state occurs, a suspension Kraft reaction is performed. There is a bulk / suspension method for obtaining ABS resin. In addition, AN / ST monomer, ABS latex with high rubber content made by emulsion polymerization method,
And an electrolyte were added and mixed, and AN / ST monomer was added to the ABS crumb formed by removing the separated water to obtain AB.
By using the emulsification / continuous bulk polymerization method of obtaining an ABS resin by performing continuous bulk polymerization as an S-dope, it is possible to reduce costs by eliminating the coagulation, washing and drying steps of ABS powder without deteriorating photographic properties. Therefore, the present invention is particularly preferable.

Domestic manufacturers of ABS resin using any of the above-mentioned methods include Asahi Kasei, Ube Sicon, Toray, Mitsubishi Rayon, Nippon Synthetic Rubber, Kyodo Polymer, Mitsubishi Monsanto, Sumitomo Nogatack, and Electrochemical. .

The content of the rubbery substance in such a styrenic resin is 0.5 to 15% by weight, preferably 1 to 12% by weight, more preferably 1.5 to 10% by weight,
Most preferably, it is 2-3% by weight. When the content of the rubber-like substance is less than 0.5% by weight, the physical strength becomes small,
In the case of a photo film spool, resin photo film cartridge (APS system), instant film unit, camera body, photo film cartridge, lens film unit with a lens, etc. Practical use is difficult due to insufficient strength and wear resistance. In addition, the content is 15% by weight.
Is exceeded, fog can be increased by 0.03 or more or the sensitivity can be partially increased by 20% or more over a period of 3 months or more in a sealed state of the photographic light-sensitive material. is there. Not only becomes more expensive, but also the flexural modulus becomes smaller.

The styrene resin has a melt flow index (hereinafter referred to as MFI; ASTM D-1238-88).
G strip elongation, temperature 200 ° C, piston load 5kg. Or JI
SK-6870) is 3.0 to 40.0 g / 10 min, preferably 5.0 to 35.0 g / 10 min, more preferably 7.0 to 30.0 g / 10 min, and most preferably 1 to 30.0 g / 10 min.
0.0 to 25.0 g / 10 minutes. MFI is 3.0g
If it is less than / 10 minutes, the fluidity of the resin is poor, and molding failures such as short shots and weld lines occur frequently, and the molding cycle becomes long, which makes practical use difficult. On the other hand, if the MFI exceeds 40 g / 10 min, the physical strength is low, burrs are generated frequently, and thermal deterioration is liable to occur and practical use is difficult.

The flexural modulus of styrene resin (JIS K
-7203) is 20,000 kg / cm ^TwoOver and preferred
Or 22,000 kg / cm^TwoAbove, more preferably 2
3,000kg / cm^TwoAbove, most preferably 25,000
kg / cm^TwoThat is all. Flexural modulus of 20,000 kg / cm
^TwoIf it is less than 10 mm, it will be easily deformed when external force is applied.
It becomes impossible to secure the total light shielding property. Especially used in cameras
Photo film spools and resin photo film pats
Rohne (APS system) exterior, photo film car
Tridge (K16 film, K35 film) and sheet
If the film pack is deformed, it becomes difficult to load it into the camera.
Shooting becomes impossible.

Vicat softening point of styrene resin (JIS
K-6870) is at least 78 ° C., preferably 8 ° C.
It is at least 2 ° C, particularly preferably at least 85 ° C, most preferably at least 87 ° C. When the temperature is lower than 78 ° C, injection moldings for photographic light-sensitive materials, which often ensure complete light-shielding properties by being blackened, are softened and deformed when left in sunlight for 1 hour or more, and become unusable or completely unusable. The light-shielding property is reduced. Spools for photo films, photo film cartridges made of resin (APS system), film units with lenses, and the like are deformed and lose their suitability for the camera, making it impossible to feed the photo film smoothly.

Rockwell hardness (AS) of styrene resin
TM D-785) requires M38 or more as a minimum,
It is preferably at least 40, more preferably at least M45, and M5
0 or more is particularly preferable, and M55 or more is most preferable. If the Rockwell hardness is less than M38, scratches occur due to friction with metal or photographic film, dimensional accuracy cannot be ensured, and in photographic film cartridges, abrasion dust adheres to the photographic photosensitive material, causing spot failure. Might be.

Izod impact strength of styrene resin (J
IS K-6871) is 2.0 kg · cm / cm or more, preferably 2.5 kg · cm / cm or more, more preferably 3.0 kg · cm / cm or more.
cm / cm or more, most preferably 3.5 kg · cm / cm or more. If the Izod impact strength is less than 2.0 kg · cm / cm,
Spool for photo film, resin photo film cartridge (APS system), camera body, which has low physical strength and is often used under the condition of 0 ° C or less.
It is difficult to commercialize a film unit with a lens, a photographic film cartridge or the like due to insufficient strength when dropped.

The injection molded article for a photographic light-sensitive material of the present invention includes:
The styrene resin having the above characteristics is contained in an amount of 50% by weight or more. It is preferably at least 60% by weight, more preferably at least 65% by weight, particularly preferably at least 70% by weight, most preferably at least 80% by weight. If the content is less than 50% by weight, the dimensional accuracy cannot be secured, and the physical strength is small.
Cracks and breakage occur due to insufficient strength when dropped, making it impossible to ensure complete light-shielding properties. In particular, when the temperature is 0 ° C. or lower, the decrease in physical strength is large. In addition, wear resistance is insufficient, and practical use is difficult.

In order to prevent shine and light fogging of the photographic light-sensitive material, the following light-shielding substances may be appropriately added to the styrene resin. The addition amount of the light-shielding substance is 0.1 to 20% by weight, preferably 0.15 to 15% by weight, more preferably 0.2 to 10% by weight, and particularly preferably 0.25 to 5% by weight. When the addition amount is less than 0.1% by weight, the light-shielding property is insufficient, and light fog occurs. On the other hand, if the amount exceeds 20% by weight, the dispersibility of the light-shielding substance is deteriorated and the fluidity of the resin is reduced, so that injection molding becomes difficult. Further, the physical strength of the injection-molded article is greatly reduced, and the wear resistance is also reduced, which makes it difficult to put into practical use. Therefore, it is essential to add a necessary amount.

Hereinafter, representative examples of the light-shielding substance will be described.

1. Inorganic compounds (1) oxides: 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 (2) water Oxide: aluminum hydroxide, magnesium hydroxide, basic magnesium carbonate (3) Carbonate: calcium carbonate, magnesium carbonate, dolomite, dawsonite (4) (Sulfite): calcium sulfate, barium sulfate, ammonium sulfate, calcium sulfite ( 5) Silicate: talc, clay, mica, asbestos, glass fiber, glass balloon, glass beads, calcium silicate, montmorillonite, bentonite (6) Carbon: carbon black, graphite, carbon fiber, carbon hollow sphere (7) Other: iron Powder, copper powder, lead powder, tin powder, Stainless powder,
Pearl pigment, aluminum powder, aluminum flake,
Molybdenum sulfide, boron fiber, silicon carbide fiber, aluminum fiber, stainless steel fiber, nickel fiber, brass fiber,
Potassium titanate, lead zirconate titanate, zinc borate,
Barium metaborate, calcium borate, sodium borate,
Aluminum paste, talc

2. Organic compounds Wood flour (pine, oak, sawdust, etc.), shell fiber (almond, peanut, fir shell, etc.), various colored fibers (cotton, jute, paper strip, cellophane strip, nylon fiber, polypropylene fiber, starch, aroma) Group polyamide fiber, etc.)

Among these light-shielding substances, carbon black which can reduce the amount of bleed-out such as a lubricant and a surfactant is preferable. Among the classifications (carbon black, furnace black, channel black, vegetable black, etc.) based on the raw material of carbon black, furnace carbon black is particularly preferred. Among them, low cost, less fogging of photographic light-sensitive material, less occurrence of increase / decrease in photosensitivity, large light-shielding ability, generation of carbon black lump (fish), fish eye, etc. PH (JIS)
K-6221) is 4.0 to 9.0, preferably 5.5.
~ 8.0, volatile component (JIS K-6221) is 3.0
%, Preferably 2.0% or less, having an average particle size (electron microscopy) of 10 to 120 mμ, preferably 15 to 80 m
μ, total sulfur content (ASTM D-1619) is 1.0
%, Preferably 0.5% or less, free sulfur (JIS
K-6350) is 0.1% or less, preferably 0.05%
Hereinafter, the cyan compound content (4-pyridinecarboxylic acid-
DBP oil absorption (ASTM D-24) of 0.3% or less, preferably 0.1% or less by a pyrazolone method.
14) is 50 ml / 100 g or more, preferably 60 ml / 100 g
100 g of furnace carbon black is preferred. Among the furnace carbon blacks, oil furnace carbon black is particularly preferable in the present invention because it does not adversely affect the photographic properties of the photographic light-sensitive material, has excellent light-shielding ability, has good dispersibility, and is inexpensive. Although it is expensive, the total sulfur content of the acetylene carbon black is also preferably _^1/10 of the furnace carbon black with 0.05% or less.

Further, acetylene carbon black which is a light-shielding substance having an antistatic effect, which is expensive, Ketjen carbon black which is a modified by-product carbon black, and conductive carbon black are required. It is also preferable to mix them.

In order to improve the uniform dispersibility of the light-shielding substance, it is preferable to add a plasticizer. Representative examples of the plasticizer are shown below.

(1) Phthalate plasticizer: diheptyl phthalate, dioctyl phthalate, diisodecyl phthalate, butyl lauryl phthalate, ditridecyl phthalate, butyl benzyl phthalate, butyl phthalyl butyl glycolate, etc. (2) phosphoric acid Plasticizers: tricresyl phosphate, trioctyl phosphate, etc. (3) Fatty acid-based plasticizers: tri-n-butyl citrate, dioctyl adipate, dioctyl azelate, dioctyl sebacate, methyl acetyl ricinoleate, etc. (4) Epoxy plasticity Agents: alkyl epoxy stearate, diisodecyl 4,5-epoxytetrahydrophthalate, etc. (5) Other plasticizers: chlorinated paraffin, polyester, sucrose octaacetate, etc.

The amount of the plasticizer added is 0.01 to 10.0% by weight.
Is preferred, more preferably 0.05 to 7.0% by weight,
0.1 to 5.0% by weight is most preferred. 0.0
When the amount is less than 1% by weight, the effect of improving the uniform dispersibility of the light-shielding substance is hardly exhibited, and only the kneading cost is increased.
If the addition amount exceeds 10.0% by weight, a slip between the screw of the extruder and the resin composition occurs, and it becomes impossible to extrude a stable resin amount.

Two or more kinds of lubricants and / or surfactants selected from the following are added to the styrene resin composition. This reduces the friction between the moving parts,
It has great effects on reducing wear, reducing powder generation, improving durability, reducing unpleasant noise, and improving injection moldability. The names of typical lubricants on the market and the names of their manufacturers are described below.

1. Fatty acid amide-based lubricant: [Saturated fatty acid amide-based lubricant] (1) Behenic acid amide-based lubricant: Diamit KN (Nippon Kasei), etc. (2) Stearamide-based lubricant: Armide HT (Lion fat), Alflow S-10 (Nippon Yushi), fatty acid amide S (Kao), Diamond 200 (Nippon Kasei),
Diamid AP-1 (Nippon Kasei), Amide S. Amide T (Nitto Chemical), Neutron-2 (Nippon Seika), etc.

[Unsaturated fatty acid amide lubricant] (1) Erucamide amide lubricant: Alflow P-10 (Nippon Oil & Fat), Neutron-S (Nippon Seika), LUBROL
(ICI), Diamid L-200 (Nippon Kasei), etc. (2) Oleic amide-based lubricants: Armoslip CP (Lion Akzo), Neutron (Nippon Seika), Neutron E-18 ( Nippon Seika Co., Ltd., Amide O (Nitto Chemical), Diamid O-200 ・ Diamid G-200
(Nippon Kasei), Alflo E-10 (Nippon Oil & Fats), fatty acid amide O (Kao), etc.

[Bis fatty acid amide-based lubricant] (1) Methylene bis-hexenamide amide-based lubricant: Diamid NK bis (Nippon Kasei) etc. (2) Methylene bis-stearic amide-based lubricant: Diamid 200 bis (Nippon Kasei) , Armowax (Lion Akzo), Bisamide (Nitto Chemical), etc. (3) Methylenebisoleic amide lubricant: Lubron O
(Nippon Kasei) etc. (4) Ethylenebisstearic acid amide lubricant: Armoslip EBS (Lion Aguzo) etc. (5) Hexamethylene bisstearic acid amide lubricant: Amide 65 (Kawaken Fine Chemical) etc. (6) Hexamethylene Bisoleic acid amide lubricant: Amide 60 (Kawaken Fine Chemical), etc.

2. Nonionic surfactant lubricant: Electroslipper TS-2, Electroslipper TS-3
(Kao Soap) and the like.

3. Hydrocarbon lubricants: liquid paraffin, heaven
Natural paraffin, micro wax, synthetic paraffin, po
Polyethylene wax, polypropylene wax, chlorinated charcoal
Hydrogen, fluorocarbon and the like. C in these₁₆
~ C₄₀, Preferably C₂₀~ C ₃₀Paraffin wax
And a weight average molecular weight of 1,000 to 12,000, preferably 1,50
0 to 10,000, particularly preferably 2,000 to 8,000
Pyrene wax and polyethylene wax.

4. Fatty acid lubricants: higher fatty acids (C ₁₂ or more preferably, specifically caproic acid, stearic acid, oleic acid, erucic acid, palmitic acid), oxy fatty acids.

5. Ester-based lubricants: lower alcohol esters of fatty acids, polyhydric alcohol esters of fatty acids, polyglycol esters of fatty acids, fatty alcohol esters of fatty acids, and the like.

6. Alcohol-based lubricant: polyhydric alcohol,
Silicone oil containing a modified siloxane bond such as polyglycol, amino-modified silicone, and alcohol-modified silicone.

7. Fatty acid metal salt lubricant (metal soap):
Caproic acid, caprylic acid, capric acid, myristic acid,
Lauric acid, stearic acid, succinic acid, behenic acid, behenic acid, linoleic acid, stearyl lactic acid, lactic acid, acetic acid, oxalic acid, citric acid, phthalic acid, benzoic acid, hydroxystearic acid, erucic acid, montanic acid, ricinoleic acid,
Fatty acids having 6 to 50, preferably 10 to 40, and particularly preferably 11 to 35 carbon atoms such as naphthenic acid, oleic acid, balmitic acid and erucic acid, and Li, Na, Mg, K, Mn, C
a, Sr, Ba, CO, NI, Zn, Cd, Al, S
Compounds of metals such as n, Pb, Cd and the like can be mentioned. Preferred are magnesium stearate, zinc stearate, calcium Baltimate, magnesium oleate and the like.

8. Silicone lubricant: Polymethylphenylsiloxane, olefin-modified silicone, amide-modified silicone, amino-modified silicone, polydimethylsiloxane, diphenylpolysiloxane, amino-modified silicone, carboxyl-modified silicone, α-methylstyrene-modified silicone, modified with polyethylene glycol or polypropylene glycol Silicone oil containing modified siloxane bonds, such as modified polyether-modified silicone, olefin polyether-modified silicone, epoxy-modified silicone, amino-modified silicone, etc.

Among the above lubricants, various saturated fatty acid amide-based lubricants and various unsaturated fatty acid amide-based lubricants are preferable for the purpose of improving lubrication. Among silicone lubricants,
Olefin-modified silicone, polydimethylsiloxane,
Amide-modified silicones and the like are preferred because they do not adversely affect the photographic properties of the photographic light-sensitive material and have an excellent lubricating effect.

For the purpose of improving the dispersibility of the light-shielding substance, imparting the effect of decreasing the hygroscopicity, and improving the flowability, ester lubricants, fatty acid metal salts, alcohol lubricants, hydrocarbon lubricants, and fatty acid lubricants are preferred. In particular, fatty acid metal salts are preferable because they have a neutralizing effect on halogen compounds and metal compounds that adversely affect photographic properties in addition to the above effects. Among fatty acid metal salts, magnesium stearate and zinc stearate are
It is particularly excellent for neutralizing halogen compounds and metal compounds (including polymerization catalysts) that adversely affect the photographic properties of photographic light-sensitive materials, and rendering them harmless to photographic properties. Further, such a fatty acid metal salt has a total content of the above-mentioned styrene resin of 50%.
When used in a styrene-based resin composition in an amount of not less than 10% by weight, in addition to the functions of releasing the injection-molded product and preventing the rust of the mold, the injection-molded product for photographic light-sensitive materials can be used in a good condition for a long period of time. Quality can be maintained.

Representative examples of the surfactant are shown below. [Nonionic] (= nonionic) Alkylamine derivatives: T-B103 (Matsumoto Yushi), T-B104 (Matsumoto Yushi) Alkylamide tertiary amine (laurylamine): Armostat 400
(Lion fat) N, N-bis (2-hydroxyethylcocoamine): Armostat 410 (Lion fat) Tertiary amine: ANTISTATIC 273C, 273, 273E
(Fine Org. Chem) N-hydoroxyhexadecyl-di-ethanol-amine: Bel
g.P. 654, 049 N-hydoroxyoctadecyl-di-ethanol-amine: (N
ational Dist.)

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

3. Ether type polyoxyethylene alkyl ether RO (CH ₂ CH ₂ O) nH polyoxyethylene alkyl phenyl ether Special non-ion type: Resistat 104, PE100, 1,
16-118 (Daiichi Kogyo Pharmaceutical), Register PE13
2, 139, Elegan E115, Chemistat 113
(Daiichi Kogyo Pharmaceutical Co., Ltd.), Chemistat 1005 (Nippon Oil & Fats), Erik BM-1 (Yoshimura Oil Chemical), Electrostrippers TS, TS2, 3, 5, EA, EA2, 3
(Kao soap)

4. Polyhydric alcohol ester type glycerin fatty acid ester: mono-, di-, or trigularicide such as stearic acid or hydroxystearic acid, monoglycol (Nippon camphor), TB-123 (Matsumoto Yushi), Register 113 (Daiichi Kogyo Seiyaku) Sorbitan fatty acid ester Special ester: Elique BS-1 (Yoshimura Oil Chemical) 1-hydroxyethyl-2-dodecylglyoxazoline: British cellophane

[Anion type] Sulfonic acids: alkyl sulfonate, RSO ₃ N
1. a, alkyl benzene sulfonate, alkyl sulfate, ROSO ₃ Na Phosphate ester type: alkyl phosphate

[Cation] 1. Amide type cation: Resist PE300, 40
1, 402, 406, 411 (Daiichi Kogyo Seiyaku) 2.4 Quaternary ammonium salt: Quaternary ammonium chloride Quaternary ammonium sulfate Quaternary ammonium nitrate Katimine CSM-9 (Yoshimura Oil Chemical), CATANAC6
09 (American cyanamide), Denno 314C (Marubishi Yuka), Armostat 300 (Lion Fat), 1
00V (Armor), Electrostripper ES (Kao Soap), Chemistat 2009 (Nippon Yushi) Stearamido propyl-dimethyl-β-hydroxyethyl am
monium nitratc: CATANAC ・ SN (American dianamid)

[Amphoteric ion system] 1. Alkyl petane type: Imidazoline type: rheostat 53, 532 (lion fat), AMS 53 (lion fat), AMS3
03, 313 (lion fat) alkyl imidazoline type 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−} (Lion fat) R = C ₃ -C ₈ hydrocarbon, A = oxygen or imino group, M =
3. Organic amine or metal Alkylanine type:

[Others]: Register 204, 205
(Daiichi Kogyo Seiyaku Co., Ltd.), Elegan 2E: 100E (Nippon Oil & Fat), Chemistat 1002, 1003, 2010 (Nippon Oil & Fat), Erik 51 (Yoshimura Oil Chemical), ALROMI
MERV-100 (Geigy), Plastic Data Handbook (KK Industrial Research Council, April 5, 1984)
It is possible to select and use from among the various antistatic agents disclosed on pages 776 to 778 of Jpn.

Among the above surfactants, nonionic surfactants are particularly preferred because they have little effect on photographic properties and human heart and have a large effect of preventing stitch marks.

The addition amount of two or more selected from lubricants or surfactants is in the range of 0.01 to 20% by weight, preferably 0.05 to 15% by weight, more preferably 0.1 to 15% by weight. -10% by weight, most preferably 0.2-5% by weight
It is. When the addition amount of two or more of the lubricant and / or the surfactant is less than 0.01% by weight, there is almost no effect of addition and the kneading cost is increased. Moldability deteriorates and molding becomes difficult. In addition, slippage is poor, and many troubles occur in the processing process. When the addition amount of two or more of the lubricant and / or the antistatic agent exceeds 20% by weight, the effect of increasing the amount is hardly exhibited and the material cost increases. Further, stickiness increases, and dust easily adheres. In addition, bleed-out occurs, or a slip between the resin composition and the screw occurs, the discharge amount becomes unstable, and not only do injection molding failures frequently occur, but also it becomes difficult to perform uniform kneading.

Examples of the thermoplastic resin include the above-mentioned styrene resin, ABS resin, styrene resin and synthetic rubber, polyester resin, copolymer of styrene resin and synthetic rubber, and the like. A product that passes through a heat history of 150 ° C twice or more, which is optimal for use in products, includes styrene resin containing 50% by weight or more of styrene resin.
Butadiene block copolymer resins are preferred. After two or more heat histories, the fluidity of the resin is improved, the dispersibility of the light-shielding substance is improved, and the substance that has a bad effect on the photographic material is thermally decomposed or removed by heating to remove photographic properties. Is good. Such a thermoplastic resin is contained in an amount of 3% by weight or more. If the content is less than 3% by weight, the effect of improving the dispersibility of the light-shielding substance, the flowability of the resin, the photographic properties, and the like is scarcely obtained, and the number of steps is increased to increase the cost.

By containing one or more of an antioxidant, a deodorant, and an fragrance, good odors due to additives in the photographic light-sensitive material filled in the hermetically sealed package, and a thermal decomposition product of the resin and the additives are excellent. Function can be obtained. By containing an antioxidant, it is possible to prevent oxidative decomposition of a resin or an additive due to heat, to prevent a decrease in physical strength, or to decompose a product as an adverse substance on the photographic properties of a photographic photosensitive material (for example,
The formation of alcohol, aldehyde, ketone, carboxylic acid, etc.) is prevented, and black spots (agglomeration of foreign substances) due to resin burning are prevented. By containing a deodorant and an aromatic, the odor generated from the photographic light-sensitive material in the hermetically sealed package or the odor generated from the thermoplastic resin composition by heating can be eliminated, and the fragrance preferable for the user can be eliminated. Instead, the commercial value can be improved.

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-
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-tert-butyl-4-hydroxybenzyl) benzene, tetrakis [methylene-3 (3.5-di-tert-butyl-4-)
Hydroxyphenyl) propionate] methane, etc.

(Ii) Ketone amine condensation antioxidant: 6
-Ethoxy-2,2,4-trimethyl-1,2-dihydroquinoline, polymer of 2,2.4-trimethyl-1,2-dihydroquinoline, trimethyldihydroquinoline derivative, etc.

(C) Allylamine antioxidants: phenyl-α-naphthylamine, N-phenyl-β-naphthylamine, N-phenyl-N′-isopropyl-P-phenylenediamine, NN′-diphenyl-P-phenylene Diamine, NN'-di-β-naphthyl-P-phenylenediamine, N- (3'-hydroxybutylidene)-
1-naphthylamine, etc.

(D) Imidazole antioxidants: 2-mercaptobenzimidazole, zinc salt of 2-mercaptobenzimidazole, 2-mercaptomethylbenzimidazole, etc.

(E) Phosphite antioxidants: alkylated allyl phosphite, diphenylisodecyl phosphite, tris (nonylphenyl) phosphite sodium phosphite, trinonylphenyl phosphite, triphenyl phosphite, etc.

(F) Thiourea-based antioxidant: Thiourea derivative, 1,3-bis (dimethylaminopropyl) -2-
Thiourea, etc.

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

Representative commercial antioxidants and their suppliers are shown below.

(1) Phenolic antioxidant: SUMI
LIZER BHT (Sumitomo), IRGANOX 107
6 (Ciba Geigy), MARK AO-50 (ADEKA
Argus), SUMILIZER BP-76 (Sumitomo), TOMINOX SS (Yoshitomi), IRGANOX
565 (Ciba Geigy), NONOX WSP (IC
I), SANTONOX (Monsauto), SUMILIZ
ER WX R (Sumitomo), ANTAGECRYSTAL
(Kawaguchi), IRGANOX 1035 (Ciba Geigy), ANTAGE W-400 (Kawaguchi), NOCLI
ZERN-6 (Ouchi Shinko), IRGANOX 142
5 WL (Ciba Geigy), MARKAO-80 (Adeka Argus), SUMILIZER GA-80 (Sumitomo), TOPANOL CA (ICI), MARK A
O-30 (ADEKA Argus), MARKAO-20
(Adeka Argus), IRGANOX 3114 (Ciba Geigy), MARK AO-330 (Adeka Argus), IRGANOX 1330 (Ciba Geigy),
CYANOX 1790 (ACC), IRGANOX
1010 (Ciba Geigy), MARK AO-60 (Adeka Argus), SUMILIZER BP-101
(Sumitomo), TOMINOX TT (Yoshitomi), etc.

(2) Phosphorus antioxidant: IRGAFOS
168 (Ciba Geigy), MARK 2112 (ADEKA
Argus), Weston 618 (BorgWarner), MARK PEP-8 (Adeka Argus), U
LTRANOX 626 (BorgWarner), MARK
PEP-24G (ADEKA Argus), MARK P
EP-36 (Adeka Argus), HCA (Sanko), etc.

(3) Thioether-based antioxidant: DLT
DP "YOSHITOMI" (Yoshitomi), SUMILIZ
ER TPL (Sumitomo), ANTIOX L (NOF), D
MTD "YOSHITOMI" (Yoshitomi), SUMILI
ZER TPM (Sumitomo), ANTIOX M (NOF),
DSTP "YOSHITOMI" (Yoshitomi), SUMIL
IZER TPS (Sumitomo), ANTIOX S (NOF), SEENOX 412S (Cipro), MARK
AO-412S (ADEKA Argus), SUMILIZ
ER TP-D (Sumitomo), MARK AO-23S (Adeka Argus), Sandstab P-EPQ (Sand), IRGAFOS P-EPQ FF (Ciba Geigy), IRGANOX 1222 (Ciba Geigy),
MARK 329K (Adeka Argus), WESTO
N 399 (BorgWarner), MARK 260 (Adeka Argus), MARK 522 (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.

Among these, particularly preferred antioxidants are phenolic antioxidants, and commercially available products include various types of Irganox (eg, Irganox 1010, Irganox 1076) manufactured by Ciba-Geigy and Sumitomo Chemical Co., Ltd. Sumilizer BH-76, Sumilizer WX-R,
Sumilizer BP-101 and the like. Furthermore, it is preferable to use a phenolic antioxidant, a phosphorus antioxidant and carbon black in combination, since the antioxidant effect is particularly effectively exhibited. Hindered phenolic antioxidants are particularly preferred because they have a high molecular weight and a high melting point and do not adversely affect the photographic properties of the photographic material. Representative commercially available hindered phenolic antioxidants are shown below.

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-te
rt-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′-
Biphenylenediphosphite, 4,4′-thiobis- (6-tert-butyl-O-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'-butylidenebis- (3-methyl-6-tert-butylphenol), 2,6-di-tert-butyl-4-methylphenol, 4-hydroxymethyl-2,6 -Ji-te
rt-butylphenol, 2,6-di-tert-4-
n-butylphenol, 2,6-bis (2′-hydroxy-3′-tert-butyl-5′-methylbenzyl) -4-methylphenol, 4,4′-methylene-bis- (6-tert-butyl- O-cresol), 4,
4 ′ butylidene-bis (6-tert-butyl-m-cresol) and the like. Two or more antioxidants may be used in combination depending on the characteristics of the antioxidant. Furthermore, the use of an antioxidant and a hydrotalcite compound in combination is particularly preferable in the present invention because they exhibit an antioxidant effect, a rust preventive effect of a mold, and a neutralizing effect of a substance which adversely affects photographic properties. Furthermore, the combined use of an antioxidant, a hydrotalcite compound and carbon black further enhances the synergistic effect, and is therefore more preferable.

In addition, various antioxidants and plastic additives disclosed on pages 794 to 795 of the Plastic Data Handbook (KK Industry Survey), pages 327 to 329 of the Plastic Additives Data Book (KK Chemical Industry Co., Ltd.) Antioxidants and PLASTICS AGE ENC
There are various antioxidants disclosed on pages 211 to 212 of YCLOPEDIA Progress Theory 1986 (KK Plastic Age), which can be selected from photographic properties, antioxidant effects and the like.

Examples of the deodorant include an organic carboxylic acid, a mixture of an organic carboxylic acid and a zinc compound, and a mixture of an organic carboxylic acid, a zinc compound and an aluminum compound.

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

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

The aromatic polycarboxylic acids include phthalic acid, terephthalic acid, isophthalic acid, trimellitic acid, pyromellitic acid, benzenehexatricarboxylic acid, naphthalenedicarboxylic acid, naphthalenetricarboxylic acid, naphthalenetetracarboxylic acid, azobenzenetetracarboxylic acid And benzenetricarboxylic acid and trimellitic acid. Particularly preferred are benzenetricarboxylic acid and trimellitic acid.

Examples of the acidic polyester compound having a carboxyl group at the terminal include a polyester having a carboxyl group at the terminal where a polycarboxylic acid such as phthalic acid is reacted with a polyhydric alcohol such as ethylene glycol or diethylene glycol, or an acidic cellulose derivative modified with a polycarboxylic acid. Etc. Zinc compounds used in combination with the organic carboxylic acid include zinc oxide, zinc chloride, zinc sulfate, zinc phosphate,
There are inorganic zinc salts of zinc carbonates and organic zinc such as zinc citrate and zinc fumarate.

The fragrance includes natural fragrance components such as lilac flower oil, jasmine, avies oil, cinnamon oil, lavender oil, lemon oil, geraniol, eugenol, n-
Octyl alcohol, carbitol, cis-chasmon, lemon terpene, menthone, methyl salicylate, methylphenylcarbinol, triethyl citrate,
Synthetic aromatic components such as benzyl benzoate, citral, d-linemon, geraniol, ethyl cinnamate, octanol, benzyl benzoate, alkylene glycol, benzyl salicylate, linalool, vanillin, coumarin, methyl naphthyl ketone, and rosephenone are microcapsule particles. It is used after being encapsulated in dextrin, cyclodextrin, maltosyl cyclodextrin, cyclodextrin, zeolite, starch, talc and the like.

The injection molded article for a photographic light-sensitive material of the present invention includes:
One or more of the above-described antioxidants, deodorants and fragrances are contained in a total amount of 0.01 to 20% by weight, preferably 0.0 to 20% by weight.
It is 5 to 17% by weight, preferably 0.1 to 15% by weight, more preferably 0.5 to 12% by weight. Content 0.0
If the amount is less than 1% by weight, the effect of addition is hardly exhibited, and the cost of kneading only increases. On the other hand, when the content exceeds 20% by weight, the effect of increasing the amount is hardly exhibited, and only the material cost increases. Depending on the type, the photographic properties of the photographic light-sensitive material are adversely affected, and the physical strength of an injection-molded product for a photographic light-sensitive material is reduced.

Examples of the injection molded article for a photographic photosensitive material of the present invention include a resin photographic film cartridge, a photographic disk film cartridge, an instant film unit,
Film unit with lens, Spool for photo film, Shading container, Patrone for photo film, Light-shielding magazine for sheet or roll photo-sensitive material loading in bright room, Core, Photo film cartridge, Instant film pack, Magazine for sheet film, The present invention can be applied to various types of injection molded products for photographic photosensitive materials, such as sheet film holders, photographic film photographing cameras, photographic photosensitive material development processors, sheet film units, and the like, which must ensure complete light-shielding properties and photographic properties.

Representative examples of the injection molded article for photographic light-sensitive materials of the present invention are shown below, but the present invention is not limited to these. (1) Photo disc film cartridge: Shokai 6
(2) Film unit with lens: JP-A-63-22
No. 6643, JP-A-8-114891, etc. (3) Photo film spool: JP-A-1-25103
0, Japanese Patent Application Laid-Open No. 57-196218, Japanese Patent Application Laid-Open
No. 9-15049, Japanese Utility Model Application Laid-Open No. 63-73742, U.S. Pat.
No. 73742, Japanese Utility Model Application Laid-Open No. 54-120931,
JP-A-58-178139-178145, JP-A-55-31541, and JP-A-58-203436.
JP-A-58-82237 and JP-A-58-82237.
JP-A-82236, JP-B-44-16777, JP-A-63-73742, JP-A-62-24095.
7, JP-A-62-284355, JP-A-4
JP-A-335638, JP-A-8-110614, UK Patent No. 2,199,805, etc.

(4) Patrone for photographic film: JP-A-54-111822, JP-B-45-6991, JP-B-55-21089, and JP-A-50-33
JP-A-831, JP-A-56-87039, JP-A-55-97738, JP-A-1-313538, JP-A-57-190948, JP-A-4-27
3240, JP-A-4-320258, JP-A-4-335344, JP-A-4-33539, JP-A-4-343353, JP-A-4-34
No. 9454, US Pat. No. 4,846,418, US Pat. No. 4,848,693, US Pat. No. 4,887,776, etc.

(5) Container for photographic film cartridge: JP-A-61-250639, JP-A-61-7394
No. 7, JP-A-60-153451, USP
4,801,011, JP-A-63-12104
7, Japanese Unexamined Patent Publication No. Sho 62-291639,
JP-A-113235, JP-A-1-152337, JP-A-2-33236, JP-A-3-4858
No. 1, Japanese Patent Publication No. 2-38939, U.S. Pat. No. 4,639,386, U.S. Pat.
No. 011, US Pat. No. 4,979,351, EP 237,062, EP 280,065, EP 298,3.
No. 75 published specification

(6) Winding core, core for belt-shaped photosensitive material, reel: Japanese Utility Model Application Laid-Open No. 60-107848, US Pat.
809,923, UK Patent 2,033,87
No. 3 publication specification etc. (7) Sheet film pack or sheet film unit: JP-A-5-341379, JP-A-8-110
No. 568, JP-A-8-110569, JP-A-8-110570, etc. (8) Photographic film cartridge: JP-B-56-166
No. 10, JP-A-2-24846, JP-A-2-24846
No. 29041, Japanese Utility Model Publication No. 60-120448,
(9) Photo film case: U.S. Pat. No. 4,779,7
No. 56, Japanese Utility Model Application Laid-Open No. 54-100617, Japanese Utility Model Application No. 64-32343, Japanese Utility Model Application No. 1-94258, Japanese Utility Model Application No. 2-56139, European Patent No. 242,
No. 905, Japanese Patent Publication No. 2-54934, etc.

(10) Instant film pack: Japanese Utility Model Laid-Open No. 61-41248, Japanese Patent Laid-Open No. 50-33831
JP, JP-A-57-19048, JP-A-62-19048
No. 240961, Japanese Unexamined Patent Publication No. 1-312538,
JP-B-57-190948, JP-A 1-3125
No. 38, Japanese Unexamined Patent Application Publication No.
-159932, JP-A-7-159933, Japanese Utility Model Laid-Open No. 55-97738, U.S. Pat.
No. 34,306, U.S. Pat. No. 4,846,418
No., U.S. Pat. No. 4,887,776, etc.

(11) Resin photographic film patrone (APS, etc.): JP-A-50-33831, JP-A-57-190948, JP-A-1-313538, JP-B-45-6991; Japanese Patent Publication 55-21
No. 089, Japanese Utility Model Laid-Open No. 55-97738, U.S. Pat. No. 4,834,306, U.S. Pat.
No. 6,418, U.S. Pat. No. 4,887,776, etc.

The photographic light-sensitive material to which the injection-molded article for a photographic light-sensitive material of the present invention can be applied is shown below.

(1) Silver halide photographic light-sensitive materials (printing film, color or black-and-white photographic paper, color or black-and-white negative film, photographic paper master paper, diffusion transfer (DTR) light-sensitive material, computer-printed film and computer-printed paper, Microfilm, color or black-and-white positive film, movie film, self-developing photographic light-sensitive material, direct positive film and paper, etc.)

(2) Heat-developable light-sensitive materials (heat-developable color light-sensitive materials, heat-developable black-and-white light-sensitive materials (for example, JP-B-43-492)
No. 1, No. 43-4924, "Basics of photographic optics", 553- of silver halide photography (published in 1879 by Corona).
555 pages and Research Disclosure Magazine 197
Those described in June, 1988, pages 9 to 15 (RD-17029). Furthermore, JP-A-59-12431,
JP-A-60-2950, JP-A-61-52343, and U.S. Pat. No. 4,584,267 which are described in U.S. Pat. No. 4,584,267).

(3) Photosensitive / thermosensitive recording material (Japanese Unexamined Patent Publication No.
Recording materials using photothermography (photosensitive / thermosensitive image forming method) described in JP-A-72358, etc.) (4) Diazonium photographic photosensitive material (4-morpholinobenzenediazonium microfilm, microfilm, copy film, printing) (5) Azide and diazide photographic light-sensitive materials (light-sensitive materials containing para-azide benzoate, 4,4'diazidostilbene, etc., such as copy films and printing plate materials)

(6) Quinonediazide-based photographic materials (orthoquinonediazide, orthonaphthoquinoneazide compounds such as benzoquinone (1,2) -diazide-
(2) Photosensitive materials containing -4-sulfonic acid phenyl ether, etc., for example, printing plates, copying films, contacting films, etc. (7) Photopolymers (photosensitive materials containing vinyl monomers, etc., printing plates) (8) polyvinyl cinnamate-based photosensitive materials (eg, printing films, IC resists, etc.)

Further, in the method for producing an injection-molded product for a photographic photosensitive material according to the present invention, the wall temperature of the core and cabin in the mold is set to 100 to 200 ° C., and the styrene resin composition melted in the mold is used. An injection-molded product is injected, and the injection-molded product is taken out when the wall temperature of the core / cavity portion falls below the Vicat softening point of the styrenic resin composition.

In the method for producing an injection molded article for a photographic photosensitive material according to the present invention, first, the wall temperature of the core cavity in the mold is set to 100 to 200 ° C., and the styrene resin melted in this state is injected. Fill. However, if the wall surface temperature is 100 ° C. or lower in this state, the fluidity of the resin is reduced, short shots and weld lines are easily generated, and the impact strength of the injection molded product is reduced. On the other hand, when the wall surface temperature exceeds 200 ° C., the thermal deterioration of the resin becomes large, and a substance which adversely affects the photographic properties of the photographic light-sensitive material is generated. Care must be taken because the surface becomes soiled and continuous injection molding for a long time becomes difficult.

When the wall temperature of the core cavity portion in the mold becomes lower than the Vicat softening point of the styrenic resin, preferably lower than 50 ° C., more preferably lower than 40 ° C. Take out the injection molded product for photosensitive material. If the resin is taken out at a temperature higher than the Vicat softening point, deformation occurs, the dimensional accuracy deteriorates, and a good injection molded product for photographic photosensitive materials cannot be obtained. Therefore, it is important to control the wall surface temperature in the mold.

[0107]

In the injection-molded article for photographic light-sensitive materials of the present invention, the styrene resin secures physical strength and bending elastic strength. Lubricity or a surfactant is used to improve lubricity so as to prevent generation of stitch marks on the photographic material. The plastic resin reduces weld line generation and improves compressive strength. The antioxidant and / or the deodorant and / or the fragrance improve the photographic properties of the photographic material and the suitability for the user (removal of bad smell, etc.).

In the method for producing an injection molded article for a photographic photosensitive material of the present invention, the fluidity of the resin is improved, the occurrence of short shots and weld lines is prevented, the molding failure is reduced, and the physical strength is improved. I have.

[0109]

DESCRIPTION OF THE PREFERRED EMBODIMENTS A typical embodiment of an injection molded article for a photographic light-sensitive material of the present invention will be described with reference to FIGS. 1 to 11, but the present invention is not limited thereto.

FIG. 1 is a front view of a photographic film spool as an injection molded product for a photographic light-sensitive material of the present invention. The photographic film spool 10 is an integrally formed product comprising a winding shaft 11 and disks 12 provided at both ends thereof.
One end of the photographic film is inserted into a slit hole 13 extending along the axial direction of the winding shaft 11 and is engaged with an engaging claw 14 provided on the inner wall of the slit hole 13 to be wound into a roll and used. .

This photographic film spool 10 has a butadiene rubber content of 5% by weight and a styrene content of 95%.
And the melt flow index is 16.2 g / 10
Min, Rockwell hardness is M42, density (JIS K-6
871) is 1.04 g / cm ³ , and the Vicat softening point is 85 °.
C, a styrene-butadiene block copolymer resin pellet having an Izod impact strength of 6.5 kg · cm / cm and a flexural modulus of 22,500 kg / cm ² (a cylindrical pellet having a diameter of 3 mm and a length of 5 mm, which will be described below at 220 ° C. The glass transition temperature of about 98 ° C.), which was pelletized in 81% by weight,
5% by weight of magnesium stearate as a lubricant and polydimethylchirosan 10 having a viscosity of 20,000 centistokes
% By weight and the average particle diameter of the light-shielding substance is 25 mμ, p
H is 8.1, ash content is 0.03%, sulfur content is 0.05
3% by weight of furnace carbon black having an oil absorption of 82 ml / 100 g and a cyan compound content of 10 ppm, and tetrakis [methylene-3- (3 ′ · 5′-di-tert-), a hindered phenolic antioxidant. Butyl-4'-
Hydroxyphenyl) propionate] methane 1% by weight
15 parts by weight of master batch pellets (blended and pelletized at 200 ° C.)
85 parts by weight of a natural pellet of a butadiene block copolymer resin (3 mm in diameter, 5 mm in length and pelletized at 220 ° C.) were uniformly mixed with an automatic weighing and mixing machine manufactured by Matsui Manufacturing Co., Ltd. Using a heavy machine “Nestal (trade name)” molding machine (mold clamping pressure 150 tons), the resin temperature is set to 190 ° C, and the core / cavity in the mold of a semi-hot runner type mold with 24 pieces. The wall temperature of the part was set at 135 ° C. during injection and filling, and was cooled to 35 ° C. immediately after completion of filling, and then the photographic film spool 10 was taken out of the mold (the molding cycle was about 7 seconds).

The spool 10 for a photo film is
12.15% by weight of a styrene / butadiene block copolymer resin in a masterbatch that has passed through a heat history of 0 ° C. or more three times, and styrene / butadiene that has passed through a heat history of 150 ° C or more twice to dilute the masterbatch pellets 85% by weight of natural pellets of a block copolymer resin, 0.75% by weight of magnesium stearate as a lubricant, 1.5% by weight of polydimethylsiloxane as a lubricant, 0.15% by weight of a hindered phenolic antioxidant And 0.45% by weight of furnace carbon black.

The photographic film spool 10 has no abnormal photographic properties for two years, the winding torque of the photographic film is small, the winding failure during photographing is 0%, and the photographic film spool 10 remains in the patrone under the sunlight of midsummer. No thermal deformation and no light fogging occurred even if left inside. Furthermore, there was almost no bad smell even when taken out after storage for 1 year in a sealed packaging state in a photographic film cartridge.

Further, a specific styrene-butadiene block copolymer resin pellet having a high melt flow index is mixed with a specific furnace carbon black, a specific lubricant, and a specific hindered phenolic antioxidant during the production of a master batch pellet. Since it is melt-kneaded at about 200 ° C and pelletized, the surface of the specific furnace carbon black is coated with magnesium stearate and dimethylpolysiloxane, and is not only uniformly dispersed in polystyrene resin but also air. Since the moisture in the resin was hardly adsorbed, the occurrence of failures such as silver, foaming, and short shots due to the moisture in the resin during the injection molding became zero. In addition, neutralization of halogen compounds with magnesium stearate, prevention of thermal decomposition of lubricant and polystyrene resin by hindered phenolic antioxidant,
It prevents photographic deterioration and odor.

FIGS. 2 and 3 are perspective views showing a band-shaped photosensitive material core as an injection molded product for a photographic photosensitive material of the present invention. The band-shaped photosensitive material core 20 winds a band-shaped film such as a movie film. FIG. 2 shows a case where the resin injection port 21 is upward, and FIG. 3 shows a case where the resin injection port side 21 is downward. This core 2 for a belt-shaped photosensitive material
A plurality of annular convexes having a height of 0.02 to 0.7 mm are provided on the inner surface of the outer cylinder 22 having a good injection moldability, physical strength and appearance of the belt-shaped photosensitive material core 20. Is being converted. The band-shaped photosensitive material core 20 is formed of the resin composition of the present invention.

The belt-shaped photosensitive material core 20 had a butadiene rubber content of 6% by weight, a styrene content of 94% by weight, a melt flow index of 12 g / 10 min, a density of 1.05 g / 10 min, and Rockwell Hardness is M53, Izod impact strength is 6.5 kg / cm · cm, flexural modulus is 2
Styrene-butadiene block copolymer resin pellets (200 kg / cm ² , Vicat softening point of 85 ° C.)
A cylindrical pellet having a diameter of 3 mm and a length of 3 mm having undergone a thermal history at 8 ° C.) of 84.9% by weight, magnesium stearate as a lubricant of 1.0% by weight, and a polyethylene wax having a molecular weight of 3500 and a total content of 2% by weight of 2% 3% by weight, melt flow index 7.5 g / 10 min, density 0.920
g / cm ³ of ethylene / 4-methylpentene-1 copolymer resin pellets (diameter 2.5 after passing through a heat history of 200 ° C. twice).
mm, 5 mm long cylindrical pellet) 10% by weight, anatase type TiO ₂ 2% by weight, tetrakis [methylene 3- (3.5-di-tert-butyl-4-hydroxyphenyl) propionate] methane as an antioxidant 0.05% by weight, n-octadexyl-3- (4 ′) as an antioxidant
-Hydroxy 3'.5'-di-tert-butyl-phenol) propionate 0.05% by weight of a styrene resin composition was injected from the resin inlet 21 at a resin temperature of 190 ° C, and a mold temperature of 110 ° C. Was injection molded.

Since the belt-shaped photosensitive material core 20 is provided with three annular convexes 23 having a height of 0.1 mm on the inner surface of the outer cylinder 22 on the side opposite to the resin injection port, fluidization of the resin is improved. The occurrence of weld lines is small and hardly found. The moldability was excellent, there was almost no molding failure, and the abrasion resistance was excellent. Further, the Izod impact strength and the compressive strength were excellent, and the film was sufficiently practical for use in 10,000-foot positive films for movies.

With the wall temperature of the core cavity of the mold set to 100 to 200 ° C., a molten styrene resin is injected and filled into the mold, and the wall temperature of the core cavity is adjusted to the temperature of the styrene resin. When the injection-molded product is taken out at a temperature lower than the Vicat softening point, the weld line hardly occurs, and the Izod strength can be more than doubled as compared with the conventional condition in which the mold temperature is 90 ° C or less. Injection molding can be performed at an injection pressure of 300 kg / cm ² or less, which is half or less of the conventional pressure, and an unexpected effect such as less deformation and improved dimensional accuracy can be obtained.

Hereinafter, other examples of the injection-molded product for a photographic material of the present invention will be described. FIG. 4 is an exploded perspective view of a film unit with a lens used as an injection molded product for a photographic photosensitive material of the present invention. The film unit with a lens is sold pre-loaded with a photographic film, and enables anyone to easily take a picture.Also, most of the parts are made using the resin composition of the present invention, and have excellent impact resistance and good Recyclability and reusability are obtained.

The lens-fitted film unit 40 has a front cover 42 which covers the front surface of a main body base 41 in which a simple photographing mechanism and a film wrapping mechanism are incorporated, and a cartridge room 41a and a film roll chamber formed in the main body base 41. After storing the patrone 50 and the rolled-out photo film 53 from each of them, the rear cover 45 is attached to the back side of the main body base 41, so that the patrone room 41a and the film roll room 41b are light-tight. Closures are available on the market with paper boxes decorated with decorative prints or packaged with adhesive labels. here,
Although a type incorporating a resin-made photographic film cartridge (APS), which will be illustrated and described later, is illustrated, a type incorporating a 135-type photographic film cartridge that has been widely and conventionally known may be used. Further, a film roll may be provided in the film roll chamber 41b.

FIG. 5 is an exploded perspective view of a resin photographic film cartridge (APS) as an injection molded product for a photographic light-sensitive material of the present invention. This resin photographic film patrone (APS) is characterized in that even the velvet of the photographic film is housed in the patrone main body, and that the photographic film can be sent out by rotating the spool. This resin photographic film cartridge (APS) 50 is composed of an upper case 51a and a lower case 51b constituting a patrone body, a spool 52 rotatably incorporated therein, and a rear end 53a fixed to the spool 52 by a spool. Photo film 5 wound around 52
3, and each part except the photographic film 53 is formed of the resin composition of the present invention.

The spool 52 is bent on the spool shaft 52a in a direction in which the outer peripheral edges are opposed to each other, and at the bent portion, the outermost periphery of the photographic film 53 wound on the spool 52 is suppressed to prevent the pair of disks 52b, The disk 52c is fixed only when the spool 52 is rotated in the film feeding direction (clockwise in the drawing) by engaging the locking teeth 52d acting as a stopper for rotating the spool shaft 52a with the disk 52c. A retaining ring 52f integrally provided with a locking claw 52e that rotates in the same direction is fixed.

A light shielding cover 54 and a lock lever 55 are incorporated in the lower case 51b. The light-shielding cover 54 is located in a film passage formed at the joint when the upper and lower cases 51a and 51b are combined, and rotates between a shielding position for closing the film passage in a light-tight manner and an opening position for opening the film passage. It is free. When the light shielding cover 54 is at the shielding position, the lock lever 55 engages with the locking teeth 52d to engage with the spool shaft 52a.
The rotation of the spool shaft 52a is prohibited, and when the light shielding cover 54 is rotated to the open position, the locking is released to enable the rotation of the spool shaft 52a. Reference numeral 56 denotes a label sticker on which the type of the photographic film 53, the number of images that can be taken, and the like are printed.
Pasted after bonding 1b.

FIG. 6 is an exploded perspective view of a photographic film cartridge 60 as an injection molded product for a photographic photosensitive material of the present invention. This is a cartridge type having a built-in 110 (commonly known as One Ten) type photo film. The photographic film cartridge 60 includes a lower case 61 and an upper case 62, and a spool 63 loaded therein.
And the lower case 61 and the upper case 6
No. 2 is formed of the resin composition of the present invention.

FIG. 7 is a front view of a sheet film unit as an injection molded product for a photographic light-sensitive material of the present invention. This is used for instant type cameras,
The sheet film unit 70 is an injection-molded product for a photographic photosensitive material of the present invention, in which a light-shielding bag 71 is formed.
Is formed with a mesh-shaped heat seal portion 72 at one end thereof, and a sheet film 73 is incorporated therein. This sheet film unit 70 is formed of the resin composition of the present invention.

FIG. 8 is a perspective view of a sheet film pack as an injection molded product for a photographic light-sensitive material of the present invention. This is a sheet film pack 80 in which a plurality of sheet film units 80 each containing a sheet film 73 stored in a sheath 81 are stacked and stored in a resin pack main body 84, and are loaded into a pack holder 85 attached to a camera. used. The pack body 84 has an opening 84a for exposing the sheet film 73 laminated on the uppermost layer.
And a lid 8 for opening and closing the opening 84a therein.
6 are provided. Further, a spring member (not shown) for pressing the sheet film unit 70 from the back side toward the opening 84a is provided in the pack body 84.

When the sheet film pack 80 is loaded into the pack holder 85 and the lid 87 of the pack holder 85 is closed,
The opening 84a of the pack body 84 is exposed from the exposure opening 87a formed in the lid 87. Lid 8 of film pack 80
When the sheet film unit 6 is pulled to a predetermined position, the uppermost sheet film unit 70 is pushed out of the opening 84a, and moves to an exposure position for closing the exposure opening 87a of the lid 87.

When the lid 86 is returned to the original position, the lid 86 is inserted between the uppermost sheet film unit 70 and the next sheet film unit. Thereafter, after the photographing operation is performed and the lid 86 is pulled, the pack holder 85 is pulled.
Is pulled out while holding the pack main body 84 with the middle frame 88 provided inside. At this time, since the exposed sheet film unit 70 remains stopped at the exposure position, when the pack main body 84 is pulled out, the exposed sheet film unit 70 is connected to four leaf springs provided on the inner wall of the lid 87. 89 pushes the pack holder 85 against the inner wall of the rear surface.

Subsequently, when the lid 86 is pushed back to the original position,
The pack body 84 returns to the original position in the pack holder 85 together with the middle frame 88. At this time, the exposed sheet film unit 70 enters the pack body 84 from the opening 84b formed on the lower side wall with respect to the moving direction of the pack body 84, and is stored in the lowermost layer of the stacked sheet film units 70. Is done. By repeating the above operation, all the sheet film units 70 stored in the pack body 84 can be continuously photographed.

FIGS. 9 and 10 are cross-sectional views of a container (P case) for a photographic film cartridge of a separate lid type and an integrated lid type as an injection molded product for a photographic photosensitive material of the present invention.
This protects the 35 type photo film patrone, the resin photo film patrone (APS) 50 described above, and the like from dust and external light. The container 90 for a photo film patrone having a lid separately comprises a container body 91 and a lid 92 fitted on the upper part thereof, and these are injection molded articles for photographic photosensitive materials of the present invention. The photo film patrone container 100 with the integrated lid is composed of a container body 101 and a lid 1.
02 is made of an integrally molded product.

FIG. 11 is a cross-sectional view of a square-shaped photographic film case with an integrated lid as an injection-molded product for a photographic photosensitive material of the present invention, in which a microfilm or the like is stored. In this photo film case 110, a container body (body) 111 and a lid 112 are formed as an integral product.

[0132]

According to the injection molded article for photographic photosensitive material of the present invention, the photographic properties are not adversely affected, and the physical strength,
Injection moldability and the like can be improved.

According to the method of the present invention for producing an injection molded article for a photographic light-sensitive material, the hygroscopicity is reduced, weld lines, silver, foaming, etc. are reduced, and an excellent appearance is obtained.
Since Izod impact strength can be improved and injection pressure can be reduced, deformation can be suppressed.

[Brief description of the drawings]

FIG. 1 is a front view of a photographic film spool as an injection molded product for a photographic photosensitive material of the present invention.

FIG. 2 is a top perspective view of a belt-shaped photosensitive material core as an injection molded product for a photographic photosensitive material of the present invention.

FIG. 3 is a bottom perspective view of a belt-shaped photosensitive material core as an injection molded product for a photographic photosensitive material of the present invention.

FIG. 4 is an exploded perspective view of a film unit with a lens as an injection molded product for a photographic photosensitive material of the present invention.

FIG. 5 is an exploded perspective view of a resin photographic film cartridge (APS) as an injection molded product for a photographic photosensitive material of the present invention.

FIG. 6 is an exploded perspective view of a photographic film cartridge as an injection molded product for a photographic photosensitive material of the present invention.

FIG. 7 is a front view of a sheet film unit as an injection molded product for a photographic light-sensitive material of the present invention.

FIG. 8 is a perspective view of a sheet film pack as an injection molded product for a photographic photosensitive material of the present invention.

FIG. 9 is a cross-sectional view of a container for a photographic film cartridge of a separate body type as an injection molded product for a photographic photosensitive material of the present invention.

FIG. 10 is a cross-sectional view of a lid-integrated photographic film cartridge container as an injection-molded product for a photographic light-sensitive material of the present invention.

FIG. 11 is a cross-sectional view of a hood-integrated photographic film case as an injection molded product for a photographic light-sensitive material of the present invention.

[Explanation of symbols]

 Reference Signs List 10 Spool for photo film 20 Core for belt-shaped photosensitive material 40 Film unit with lens 50 Photo film cartridge (APS) made of resin 60 Photo film cartridge 70 Sheet film unit 80 Sheet film pack 90 Container for photo film cartridge 100 Container for photo film cartridge 110 Photo film case

Claims (2)

[Claims] 1. A melt flow index of 3.0 to 4
0.0g / 10 min, Rockwell hardness of M38 or more, Izod impact strength of 2.0 kg · cm / cm or more, flexural modulus of 20,000 kg / cm ² or more, Vicat softening point of 78 °
The content of the styrene resin of C or more is 50% by weight or more, the total content of two or more kinds selected from lubricants or surfactants is 0.01 to 20% by weight, and the heat history of 150 ° C or more is twice. 3% by weight or more of the thermoplastic resin passed through above, and the total content of at least one of antioxidant, deodorant, and fragrance is 0.1% or more.
An injection-molded article for a photographic photosensitive material, which is injection-molded using a styrene resin composition in an amount of from 0.01 to 20% by weight. 2. The styrene melted in the mold, wherein the wall temperature of the core cavity in the mold is 100 to 200 ° C. in order to obtain the injection molded article for a photographic photosensitive material according to claim 1. Injection molding of a styrene resin composition, and removing the molded product after the wall temperature of the core / cavity portion falls below the Vicat softening point of the styrene resin composition. Injection molding method.