JPH10221815A - Photo film cartridge - Google Patents

Abstract

(57) [Summary] [Problem] By examining the resin material of a disk which is a component part of a photographic film cartridge, it is excellent in abrasion suitability, high in durability and high in feeding power, and reduces noise during photographic film feeding. Provided is a reduced photographic film cartridge. SOLUTION: A pair of disks 22 attached to both ends of a spool 15 of a photo film cartridge 10,
No. 23 is formed by injection molding of a nylon-modified polyphenyl ether containing 0.5 to 7% by weight of molybdenum disulfide and 0.5 to 3% by weight of silicone oil.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photographic film cartridge in which a photographic film is stored in a roll, and more particularly, to a material of a disk fixed or rotatably attached to both ends of a spool. is there.

[0002]

2. Description of the Related Art Recently, for the purpose of simplifying the loading of a photographic film cartridge into a camera, improving the working efficiency in a photo lab, improving the handling of a photographic film cartridge, and the like.
For example, U.S. Pat.
No. 32275, No. 5296887, Japanese Patent Application Laid-Open No. 2-18545, Japanese Patent Application Laid-Open No. 3-37645, Japanese Patent Application Laid-Open No. 4-320258, and the like. A photographic film cartridge has been proposed in which a photographic film is stored in a main body, and when the photographic film is mounted on a camera and a spool is rotated, the photographic film is sent out from an opening provided in the cartridge main body.

All of the photographic film cartridges described above are devised in the structure of a cartridge main body and a spool made as a resin molded product, and a disk fixed or rotatably attached to both ends of the spool. When the spool is rotated, the rotation of the spool is transmitted to the photo film so that the photo film is not loosened in the cartridge body.

The above-mentioned pair of discs is provided with a tongue-like lip which sandwiches both side edges of the photographic film between inner surfaces facing each other, or which is slightly projected on the outer peripheral edge of each disc in a direction facing each other. By wrapping the outermost periphery of the photo film roll, the photo film is prevented from becoming loose. And in the cartridge body,
At the back of the opening, the tip separation claw and the side regulating rib are provided integrally, and by scooping up the tip of the photo film with the tip separation claw, the photo film partially deforms a pair of discs in the direction away from each other. However, the leading end of the photographic film can be easily moved from between the discs toward the opening.

[0005] On the inner wall of the side surface of the cartridge body, a side rib for regulating the disk from the side surface is provided. Depending on the position of the side ribs, the amount of deformation of the disk and the amount of deformation of the photographic film differ. In particular, the distance between the side ribs on the film passage side affects generation of powder, feeding force, or durability. When the rib interval is large, the force for sandwiching the photographic film is small, and the durability is improved, but the feeding force is reduced. On the other hand, if the rib interval is small, the photographic film is strongly sandwiched, and the feeding force is improved, but the durability is reduced.

The photographic film cartridge disk described above has heretofore been obtained as a molded product of high impact polystyrene (HIPS) resin or high-density polyethylene resin in consideration of moldability. Regarding the material and molding method of such a disc, see, for example, Japanese Unexamined Patent Publication No.
In Japanese Unexamined Patent Application Publication No. 6-148808,
It is described that a polyethylene-based resin sheet is thermoformed by vacuum or pressure molding, and a disc is formed by punching after the molding.

However, the disk of the photographic film cartridge is extremely worn because it always rubs strongly against the above-mentioned side ribs. Further, the end face of the photographic film and the disk are pressed and rubbed with each other. It was found that molding was not practical in terms of durability.

Further, when the photographic film is fed or rolled in, the inner surface thereof is constantly rubbed against the end face of the photographic film and is liable to abrasion, and powder is generated by the abrasion, and is sent out of the cartridge together with the photographic film to contaminate the camera. , Was sometimes imprinted on the image. Further, such a powder sometimes damages the photographic film or generates fogging.

Further, in order to increase the feeding force of the photographic film, it is necessary to sandwich the photographic film with a disk and attach a gutter-like curl. When the disk becomes flexible, the gutter-like curl becomes smaller, and the feeding force decreases. Further, when the disk becomes hard, the gutter-shaped curl becomes large and comes into contact with the film passage of the cartridge, the camera, the pressure plate of the film observation device, and the like, thereby generating scratches and powder. In addition, since the disc and the photographic film come into strong contact with each other, it may cause deterioration of the feeding durability and may cause unpleasant noise. On the other hand, the flexibility of a photographic film can be said to be the same as that of a disk. However, the photographic film varies depending on the type and thickness of a support used, the type of photosensitive material, and the like, and furthermore, greatly changes depending on temperature and humidity.

Further, such a disk is preferably thinned in order to make the photographic film cartridge compact, but it is liable to be thermally deformed in a high temperature environment. For example, in a car in the middle of summer, the temperature inside the car is 80 ° C.
In such a case, a disk made of a resin material as described above may not be able to obtain the expected function due to thermal deformation.

[0011] Against this background, the applicant of the present invention has also proposed, for example, Japanese Patent Application No. 5-49662 to solve the above-mentioned problems such as the durability of the disk. A photographic film cartridge using a mixed resin in which a copolymer of styrene and synthetic rubber and a modified polyphenylene ether resin are mixed in a ratio of 3: 7 to 8: 2 has been proposed. Also, JP-A-8-1
Japanese Patent No. 46562 discloses that a disk is injection-molded using polyacetal, olefin-modified polyphenyl ether, or nylon-modified polyphenyl ether as a means for reducing equipment costs and material costs and improving dimensional accuracy. Is described.

[0012]

However, in a system in which a developed photographic film is wound into the above-described cartridge and returned to a user, which is assumed as a use form of such a photographic film cartridge, a photographed image is taken. Is often observed on a display device or the like, so that it is sufficiently conceivable to repeatedly put the photographic film in and out of the cartridge many times. In view of such a usage form, as described above, a material that can sufficiently withstand a large number of feedings is obtained only by changing the mixing ratio of the copolymer of styrene and synthetic rubber and the modified polyphenylene ether resin. However, a disk material with higher durability is required.

For example, in a photographic film cartridge using discs molded of three kinds of resins, as described in Japanese Patent Application Laid-Open No. 8-146562, the photographic film is repeatedly drawn and unwound 100 times. As a result, between the three types of photographic film cartridges using the three types of resin disks, the photographic film cartridge was attached to a plate attached to provide smoothness to the film and a magnetic head for recording photographing information and the like. It has been found that there is a difference in the manner in which dirt such as shaving powder of a photographic film adheres.

Further, a photographic film cartridge using the above-described disk can be used for feeding a photographic film,
Alternatively, when the film is rewound, an unpleasant rubbing sound is generated due to the sliding between the photographic film and the disc, which causes a problem that the sound is extremely unpleasant. Furthermore, such a disk is very thin and lightweight, so the cylinder of the molding machine,
If the residence time of the resin in the hot runner portion is long, there is also a problem that the strength of the molded product is significantly reduced due to thermal degradation of the resin.

The present invention has been made in view of the above circumstances, and by examining the resin material of a disc which is a component of a photographic film cartridge, it has excellent abrasion suitability.
It is an object of the present invention to provide a photographic film cartridge that has high durability and a high feeding force and that reduces noise during photographic film feeding.

[0016]

According to the present invention, there is provided a photographic film cartridge according to the present invention, wherein the photographic film cartridge is fixed or rotatably attached to both ends of a spool rotatably housed in a cartridge body. A disc that is in contact with the side edge of the photographic film roll wound around the spool or the outermost periphery of the photographic film roll to prevent the photographic film roll from loosening is used. 0.5 to 7% by weight of molybdenum disulfide and 0% of silicone oil are used. It is formed by injection molding of nylon-modified polyphenyl ether containing 0.5 to 3% by weight.

According to a second aspect of the present invention, the nylon-modified polyphenyl ether forming the disk is loaded with a load of 1%.
0 Kg, a load of 10 K with respect to the value of the melt index 5 minutes after being put into the melt indexer at 280 ° C.
g into the melt indexer at 280 ° C and 30
The value of the melt index after 1.2 minutes is 1.2 times or less,
And the value of the melt index after 5 minutes is 100 g.
/ 10 minutes. Claim 3
In the above, the nylon constituting the nylon-modified polyphenyl ether is an aliphatic nylon.

[0018]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS First, the construction of the photographic film cartridge of the present invention will be described. FIG. 1 is an external perspective view showing a photographic film cartridge, and FIG. 2 is an exploded perspective view thereof. The photo film cartridge 10
"AdvancedPhoto System" proposed by the applicants
And the resin cartridge body 13
A spool 15 rotatably mounted on the cartridge body 13 and a photographic film 14 which is provided with two perforations 14b in one photographing frame and one end of which is locked on the spool 15 and wound. Be composed.

The cartridge body 13 comprises an upper case 11 and a lower case 12 each having a substantially semi-cylindrical shape, and these are formed by injection molding of a thermoplastic resin. The upper case 11 and the lower case 12 are formed with projecting port portions 11b and 12b, respectively. When the upper case 11 and the lower case 12 are combined, the port portions 11b and 1b are formed.
A film passage 17 for letting the photo film 14 in and out is formed at the joint of 2b. Upper and lower case 1
After the two are combined, ultrasonic welding is applied to the engaging portions of the first and second members 12 so as to be integrated.

A cover member 18 for preventing light from entering the film passage 17 is mounted on the shaft. A separating claw 19 for separating the leading end of the photographic film 14 is provided at the back of the film passage 17. Are provided. The cover member 18 has key grooves 18a and 18b formed at both ends thereof, and the film passage 17 is formed by rotation of a camera-side opening / closing drive shaft which engages with the key grooves 18a and 18b when the cover member 18 is loaded into the camera. And the open position allowing the photo film 14 to enter and exit.

The spool 15 has a pair of lip-attached disks 22, 23 attached to both ends of a spool shaft 21,
A data disk 24 is provided outside these disks 22 and 23.
And a use indicating member 25 are attached, and are housed so that both ends of the spool shaft 21 are exposed on the side surface of the cartridge body 13. The data disk 24 has a bar code label 2 having a similar shape to the data disk 24.
6 is adhered, and the use display member 25 is integrally formed with a gear 27. The data disk 24 and the use indicating member 25 are attached so as to rotate integrally with the spool shaft 21.

A slit 28 for locking the rear end 14a of the photo film 14 is formed in the spool shaft 21, and key holes 29a and 29b are provided at both ends. A drive shaft on the camera side is engaged with the key grooves 29a and 29b when the photographic film cartridge 10 is loaded in the camera, and the rotation of the drive shaft causes the spool shaft 2 to rotate.
1 is rotated.

The pair of disks 22 and 23 have a thin cup shape in cross section, and when attached to the spool shaft 21, the opening edges 22a and 23a face each other and are wound between them. Wrap both sides of the photo film 14 (see FIG. 3A). Opening edges 22a, 23
“a” transmits the rotation of the spool shaft 21 to the photographic film 14 wound around the outermost periphery and prevents the photographic film 14 from being loosened.

In the disk 23, holes 31 are formed at a predetermined pitch. In these holes 31, the spool shaft 21 is provided.
Is rotated in the film feeding direction (clockwise in the drawing), the ratchet pawl 32 of the use indicating member 25 is engaged. Thereby, the rotation of the spool shaft 21 is transmitted to the disk 23, and the disk 23 rotates integrally with the spool shaft 21. When the spool shaft 21 rotates in the film winding direction (counterclockwise in the drawing), the ratchet pawl 32 of the use indicating member 25 gets over the hole 31, and the rotation of the spool shaft 21 is not transmitted to the disk 23.

A bar code 26a is printed on a bar code label 26 attached to the data disk 24. The bar code 26a indicates various information, for example, the type and sensitivity of the photographic film 14 to be stored. When the spool shaft 21 is rotated in the film feeding direction, this information is transmitted to the opening 3 formed on one side surface of the upper case 11.
The image data is read by a reading sensor provided on the camera side via the reference numeral 5, and is used for calculating an exposure value, counting the number of exposures of the stored photographic film, and the like.

A spool lock 38 is housed inside the cartridge body 13 so as to mesh with the gear 27 of the use indicating member 25. The spool lock 38 engages with the gear 27 when the cover member 18 is in the closed position to lock the rotation of the spool shaft 21 to prevent the photograph film 14 from being sent out carelessly. When in the open position, the engagement with the gear 27 is released.

From the cartridge body 13, the photographic film 1
When sending out 4, the spool 15 is rotated in the film sending direction. When the spool 15 is rotated in the film feeding direction, the leading end of the photographic film 14 comes into contact with the separation claw 19 and is separated from the portion wound inside.
When the spool 15 is subsequently rotated, the leading end of the separated photographic film 14 is brought into contact with the open edges 22 of the disks 22, 23.
The discs 22 and 23 having a small thickness and flexibility are pushed outward by both side edges of the photographic film 14 (see FIG. 3B).

Thus, the leading end of the photo film 14 is
The discs 22, 23 are released from being wrapped by the opening edges 22a, 23a, and are sent out of the cartridge body 13 through the film passage 17. At this time, both side edges of the photo film 14 and the discs 22 and 23 are always in sliding contact with each other, but since the discs 22 and 23 have high flexibility,
Due to the feeding force of the photo film 14, the disc 22,
23 flexes outward, frictional resistance between the two is suppressed, and the photographic film 14 is fed with low torque.

When the spool 15 rotates in the film winding direction, the disks 22, 23 do not rotate integrally with the spool shaft 21. Therefore, when winding the photo film 14, the disc 2
The opening edges 22a and 23a of the photo film 14
To prevent the photographic film 14 from becoming loose.

As the resin material constituting the disks 22, 23 of the photographic film cartridge 10 of the present invention, nylon-modified polyphenyl ether is used. The nylon-modified polyphenyl ether used in the present invention has been alloyed by blending, and further by a compatibilizer or reactive processing.

The composition ratio of such a nylon-modified polyphenyl ether is preferably 30 to 70% by weight of nylon, 20 to 60% by weight of polyphenyl ether (PPE), and 0 to 20% by weight of a thermoplastic elastomer. Is
40 to 65% by weight of nylon, 25 to 55% by weight of polyphenyl ether (PPE), 3 to 15% by weight of a thermoplastic elastomer, particularly preferably 45 to 60% by weight of nylon, and polyphenyl ether (PPE). ) Is 30 to 50% by weight, and the thermoplastic elastomer is 5 to 13% by weight. In addition to the nylon-modified polyphenyl ether having such a composition, 0.5% of molybdenum disulfide is further added.
-7% by weight, and 0.5-3% by weight of silicone oil.

From the viewpoint of moldability, the type of nylon constituting the nylon-modified polyphenyl ether is 6
-Nylon, 66-nylon, 46-nylon, 11-
Aliphatic nylons such as nylon and 12-nylon are preferred. In particular, among these aliphatic nylons, 12-nylon, which has a low melting point, has a large difference between the melting point temperature and the melting point of nylon, and can set a wide range of molding conditions, is preferred.
Nylon changes its physical properties and dimensions due to water absorption.
-Nylon has low water absorption and is also preferred in this regard.

As the thermoplastic elastomer constituting the nylon-modified polyphenyl ether, ethylene propylene rubber and styrene butadiene rubber are preferable. It is desirable that these nylons and thermoplastic elastomers have a low content of low molecular weight components in order to keep good thermal stability.

The molybdenum disulfide added to the nylon-modified polyphenyl ether preferably has a particle size of 1 to 15 μm. When the particle size is smaller than 1 μm, there is no effect of reducing generation of powder due to sliding at the time of drawing and rewinding the photographic film. On the other hand, if the particle size is larger than 15 μm, the weld portion becomes brittle, and the strength of the molded product decreases. Further, when surface treatment is performed with a silane-based coupling agent, a titanate-based coupling agent, an aluminum-based coupling agent, etc. to improve the dispersibility of molybdenum disulfide, the impact resistance of the base resin can be improved. Can and is effective. From the viewpoint of maintaining the thermal stability of the entire resin, it is desirable to use such a coupling agent having excellent thermal stability.

The amount of the silicone oil added to the nylon-modified polyphenyl ether is 0.5 to 3% by weight, preferably 1 to 3% by weight. 3% by weight
If it exceeds, the weld strength of the molded product is reduced, and the disk is cracked by dropping or the like. If the addition amount is less than 0.5% by weight, the effect of reducing noise when winding the photographic film is not seen. It is desirable that such a silicone oil has heat resistance. In order to suppress thermal decomposition, it is desirable to use a silicone oil to which a heat stabilizer has been added and a silicone oil from which a low molecular weight component having poor heat stability has been removed.

The physical properties of the nylon-modified polyphenyl ether used for molding the discs 22 and 23 of the photographic film cartridge 10 of the present invention are as follows.
g, a load of 10 Kg with respect to the value of the melt index 5 minutes after being put into the melt indexer at 280 ° C.
The value of the melt index after 30 minutes from the introduction into the melt indexer at 280 ° C. is 1.2 times or less, and the value of the melt index after 5 minutes is 100 g /
What is 10 minutes is used.

On the other hand, the cartridge body 13 composed of the upper case 11 and the lower case 12 is preferably made of a thermoplastic resin. A light-shielding substance for imparting a light-shielding property to the thermoplastic resin and a fibrous filler are used. It is preferable to use a thermoplastic resin composition obtained by kneading If necessary, lubricants, antistatic agents, drip-proof agents, flame retardants, ultraviolet absorbers, metal deterioration inhibitors, compatibilizers, thermoplastic elastomers, inorganic or organic pigments, processing aids, antioxidants, nuclei Various other additives such as an agent and a plasticizer may be contained in the resin.

The thermoplastic resin used for the resin material of the cartridge body 13 is particularly preferable.
Polyethylene, polypropylene, styrene resin, ABS
Resin, acrylonitrile-styrene resin, AAS (A
SA) resin, AES resin (weather resistance, impact resistance resin), syndiotactic polystyrene, polyethylene produced by polymerization using a single-site catalyst, and polypropylene produced by polymerization using a single-site catalyst.

Other thermoplastic resins include vinyl chloride resin, polyvinyl alcohol, acrylic resin, vinylidene chloride resin, cellulose derivative resin, thermoplastic polyurethane, polyvinyl butyral, poly-4-methylpentene-1, polybutene-1 and the like. Is mentioned.

Among the above-mentioned thermoplastic resins, particularly preferred are low cost, high physical strength, excellent rigidity, heat resistance and abrasion resistance, good photographic properties, and excellent high density injection molding. Polyethylene has a molecular weight of 50
000 to 400,000, preferably 100,000 to 40
0000, particularly preferably 120,000 to 300,000
It is. The density is 0.941 (g / cm ³ ) or more,
It is preferably at least 0.950 (g / cm ³ ). If the molecular weight is less than 50,000, the resulting molded article has insufficient abrasion resistance, and if the molecular weight exceeds 400,000, molding becomes difficult and a good appearance is hardly obtained, which is not preferable.

Such a high-density polyethylene may contain other monomers such as propylene, butene-1, pentene, 4-methylpentene-1, 4-methylpentene-1 as long as its performance is not impaired.
Α-olefins such as hexene, octene and decene, butenes such as butadiene and isoprene, cyclopentene,
Cycloolefins such as cyclohexene and cyclopentadiene and acrylates such as methyl acrylate, ethyl acrylate and butyl acrylate may be copolymerized.

In addition to those described above, the thermoplastic resins particularly preferred in the present invention are excellent in various properties (physical strength, rigidity, heat resistance, abrasion resistance, etc.) and are particularly stable at high temperatures. If it is, any type may be used and is not limited. For example, polyethylene terephthalate (PET), polyethylene naphthalate (PEN),
Aromatic polyester resin composed of aromatic dicarboxylic acid such as polybutylene naphthalate (PBN) and diol or oxycarboxylic acid, nylon 6, nylon 6
6, polyamide resins such as nylon 6-10, nylon 12, nylon 46, olefin resins mainly containing ethylene, propylene, butene, etc., styrene resins such as polystyrene, polystyrene-acrylonitrile, ABS, etc., polycarbonate, polyphenylene Oxide, polyalkyl acrylate, polyacetal, polysulfone,
Examples thereof include polyether sulfone, polyether imide, polyether ketone, and fluororesin. Further, these thermoplastic resins may be used by mixing two or more kinds of arbitrary resins.

A polycarbonate resin having excellent properties (physical strength, rigidity, heat resistance, abrasion resistance, etc.), good photographic properties, and excellent injection moldability, or a polycarbonate resin and another thermoplastic resin. The PC resin that can be used in the mixture is not particularly limited, and widely used conventionally known PC resins such as a resin produced by reacting an aromatic phenol compound with phosgene or a carbonic acid diester are used. Can be. Further, in the present invention, a branched PC resin can also be used.

The PC resin can be used alone or in combination with one or more other resins. The resin that can be used by mixing with the PC resin is not particularly limited as long as it is a resin that can be mixed with the PC resin. For example, an aromatic polyester resin, a polystyrene resin, a polyethylene resin, a polypropylene resin,
Examples thereof include a polyamide resin, a polyether resin, a polysulfone resin, and a polyphenylene sulfide resin.

The aromatic polycarbonate resin used as a component of the thermoplastic resin is a resin usually used as an engineering resin, and is an aromatic polycarbonate resin obtained by reacting a dihydric phenol with a carbonate precursor.

Representative examples of the above-mentioned dihydric phenols include, for example, 2,2-bis (4-hydroxyphenyl) propane (commonly called bisphenol A), bis (4-hydroxyphenyl) methane, 1,1
-Bis (4-hydroxyphenyl) ethane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 2,2
-Bis (4-hydroxy-3,5-dimethylphenyl)
Propane, 2,2-bis (4-hydroxy-3,5-dibromophenyl) propane, 2,2-bis (4-hydroxy-3-methylphenyl) propane, bis (4-hydroxyphenyl) ether, 4,4 -Dihydroxydiphenyl, bis (4-hydroxyphenyl) sulfite, and bis (4-hydroxyphenyl) sulfone.

Among the above-mentioned various dihydric phenols, bis (4-hydroxyphenyl) alkane is particularly preferable, and 2,2-bis (4
-Hydroxyphenyl) propane is particularly preferred. As the carbonate precursor, carbonyl halide, carbonate ester or haloformate is used,
Specific examples include phosgene, diphenyl carbonate, and dihaloformate of dihydric phenol.

In producing the aromatic polycarbonate resin by reacting the above-mentioned various dihydric phenols with the carbonate precursor, the dihydric phenol can be used alone or in combination of two or more. Catalysts, molecular weight regulators, antioxidants and the like. Further, the aromatic polycarbonate resin may be a branched polycarbonate resin obtained by copolymerizing a trifunctional or higher polyfunctional aromatic compound, or a mixture of two or more aromatic polycarbonate resins.

Among the thermoplastic resins, the polyamide resin which is an engineering plastic includes a semi-crystalline resin and a non-crystalline resin, and what is generally called a nylon resin can be used. The polyamide resin is a polyamide obtained by a lactam ring-opening polymerization reaction, a saturated dicarboxylic acid having 4 to 12 carbon atoms, and a polyamide having 4 to 12 carbon atoms.
And polyamides obtained by subjecting 12 diamines to condensation polymerization in an equimolar amount. These may use an excess of diamine or dicarboxylic acid so that the terminal of the polyamide has an excess of amine groups over carboxyl groups, or vice versa.

Specifically, polycaprolactam (nylon 6), polylaurin lactam (nylon 12), poly-11-amino-undecanoic acid (nylon 11), bis (p-aminocyclohexyl) methane dodecanoamide,
Polyhexamethylene adipamide (6,6 nylon), polymethaxylylene adipamide (MXD-6 nylon),
Examples include polyhexamethylene aceramide (6,9 nylon) and polyhexamethylene dodecanoamide (6,12 nylon). In addition, two or more copolymers of each polymer as described above, or two or more copolymers of these polymers,
A blend of more than one type may be used.

Examples of the polystyrene resin include, for example, general-purpose polystyrene, impact-resistant polystyrene, styrene-acrylonitrile resin, styrene-acrylonitrile-butadiene resin, AES resin, styrene-methyl methacrylate-acrylonitrile resin, acrylonitrile-acrylic resin. Rubber-styrene resins, styrene-butadiene block copolymers, styrene-maleic anhydride copolymers and the like can be mentioned.

As the polyethylene resin, for example, high density polyethylene resin (HDPE), low density polyethylene resin (LDPE), linear low density polyethylene resin, ethylene-vinyl acetate copolymer, ethylene-propylene copolymer, ethylene -Acrylate copolymers, ethylene-glycidyl (meth) acrylate and the like.

As the polypropylene resin, for example,
Examples thereof include a polypropylene resin, a propylene-vinyl acetate copolymer, and a propylene-vinyl chloride copolymer. Examples of the polyamide resin include, for example, those obtained by ring-closing polymerization of an aminocarboxylic acid compound alone or a condensation polymer of a dicarboxylic acid compound and a diamine compound, α-caprolactam, or ω-caprolactam. it can.

Examples of the polyether-based resin include a polyphenylene ether (co) polymer and a polyetherimide polymer. Examples of the polysulfonic acid resin include polysulfone and polyether sulfone.

Representative examples of a homopolymer of a polyphenylene ether-based resin, which is one of engineering plastics, include, for example, poly (2,6-dimethyl-1,4)
-Phenylene) ether, poly (2-methyl-6-ethyl-1,4-phenylene) ether, poly (2,6-diethyl-1,4-phenylene) ether, poly (2-ethyl-6-n-propyl) -1,4-phenylene) ether, poly (2,6-di-n-propyl-1,4-phenylene) ether, poly (2-methyl-6-n-butyl-
1,4-phenylene) ether, poly (2-ethyl-6)
-Isopropyl-1,4-phenylene) ether, poly (2-methyl-6-chloroethyl-1,4-phenylene) ether, poly (2-methyl-6-hydroxyethyl-1,4-phenylene) ether, poly ( Homopolymers such as 2-ethyl-6-chloroethyl-1,4-phenylene) ether and the like can be mentioned.

Representative examples of the polyphenylene ether copolymer include, for example, 2,6-dimethylphenol and 2,6-dimethylphenol.
A copolymer with 3,6-trimethylphenol, or o
-A copolymer with cresol, or a copolymer with 2,3,6-trimethylphenol and o-cresol,
It includes a polyphenylene ether copolymer having a polyphenylene ether structure as a main component.

Next, representative examples of light-shielding substances for imparting light-shielding properties to the thermoplastic resin constituting the cartridge body 13 will be described below. 1. Inorganic compounds A. Oxides: silica, diatomaceous earth, alumina, titanium oxide, iron oxide (iron black), zinc oxide, magnesium oxide, antimony oxide, barium ferrite, strontium ferrite, beryllium oxide, pumice, pumice balloon, alumina fiber, etc. Hydroxide; aluminum hydroxide, magnesium hydroxide, basic magnesium carbonate, etc. Carbonate; calcium carbonate, magnesium carbonate, dolomite, dawsonite, etc. (Sulfite) calcium sulfate, barium sulfate,
E. ammonium sulfate, calcium sulfite, etc. Silicates; talc, clay, mica, asbestos, glass fiber, glass balloon, glass beads, calcium silicate, montmorillonite, bentonite, etc. Carbon; carbon black, graphite, carbon fiber, carbon hollow sphere, etc. Others: iron powder, copper powder, lead powder, aluminum powder, molybdenum sulfide, polon fiber, silicon carbide fiber, brass fiber, potassium titanate, lead zirconate titanate, zinc borate, barium metaborate, calcium borate, borate Sodium acid, aluminum paste, talc, etc.

2. Organic compounds Wood flour (pine, oak, sawdust, etc.), shell fibers (almonds, peanuts, cashew nuts, hazelnuts, macadamia nuts, fir shells, etc.), cotton, jute, paper chips, cellophane pieces, nylon fibers, polypropylene fibers,
Starch (including modified starch and surface-treated starch),
Aromatic polyamide fiber, etc.

Among these light-shielding substances, inorganic compounds which do not adversely affect photographic properties, are stable to heat even at 150 ° C. or higher, and are opaque are preferable, and are particularly excellent in heat resistance and light resistance. Light-absorbing carbon black, titanium nitride, graphite, and iron black are preferred.

Examples of the classification according to the raw material of carbon black include gas black, furnace black, channel black, anthra black, acetylene black, Ketchen carbon black, thermal black, lamp black, oil smoke, pine smoke, animal black, vegetable black and the like. There is.

Representative examples of preferable commercial products of carbon black include, for example, carbon black manufactured by Mitsubishi Chemical Corporation.
20 (B), ♯30 (B), ♯33 (B), ♯40 (B), ♯41 (B), ♯44 (B), ♯45
(B), ♯50, ♯55, ♯100, ♯600, ♯950, ♯1000, ♯2200
(B), $ 2200 (B), $ 2400 (B), MA8, MA11, and MA100.

As overseas products, for example, Black Pearls 2, 46, 70, 71,
74, 80, 81, 607 etc., Regal 300, 3
30, 400, 660, 991, SRF-S, etc., Vul
can 3, 3, etc., Sterling 10, SO,
V, S, FT-FF, MT-FF and the like.

Further, United by Ashland Chemical Co., Ltd.
R, BB, 15, 102, 3001, 3004, 3006, 3007, 3008, 3
009, 3011, 3012, XC-3016, XC-3017, 3020 and the like, but are not limited thereto.

Of these, furnace carbon black is preferred for the purpose of improving light-shielding properties, cost, and physical properties, and acetylene carbon black and Ketjen, a modified by-product carbon black, are expensive light-shielding substances having an antistatic effect. Carbon black is preferred. If necessary, it is also preferable to mix the former and the latter according to required characteristics. The form in which the shading raw material is mixed with the thermoplastic resin is roughly classified as follows. (1) Uniformly colored pellets (the most commonly used ones called color compounds) (2) Dispersed raw powders (treated with various surface treatment agents, also called dry colors) (3) Paste (dispersed in plasticizer etc.) (4) Liquid (liquid dispersed in surfactant etc. also called liquid color) (5) Masterbatch pellets (a light-shielding substance is dispersed at a high concentration in the plastic to be colored) (6) Moisturizing granular powder (a light-shielding substance is dispersed at a high concentration in the plastic and then a granular powder (7) Dry powder (normal untreated dry powder)

Of these, carbon black is preferred because it does not cause fogging in the photographic material, causes little increase or decrease in sensitivity, and has a large light-shielding ability. The next preferable light-shielding substances after carbon black are inorganic pigments having a refractive index of 1.50 or more, various metal powders, metal flakes, metal pastes, metal fibers and carbon fibers. Representative examples of inorganic pigments and metal powders having a preferable refractive index of 1.50 or more are shown below, but the present invention is not limited thereto. The numbers in parentheses indicate the refractive index.

Examples of the inorganic pigment having a refractive index of 1.50 or more include rutile type titanium oxide (2.75) and silicon carbide (2.6%).
7), anatase type titanium oxide (2.52), zinc oxide (2.3
7), antimony oxide (2.35), lead white (2.09), zinc white (2.02), lithopone (1.84), zircon (1.80), corundum (1.77), spinel (1.73), apatite (1.
64), barite powder (1.64), barium sulfate (1.64), magnesite (1.62), dolomite (1.59), calcium carbonate (1.58), talc (1.58), calcium sulfate (1.5
6), silicic anhydride (1.55), quartz powder (1.54), magnesium hydroxide (1.54), hydrochloric magnesium carbonate (1.5
2) and alumina (1.50). Particularly preferred are light-shielding substances having a refractive index of 1.56 or more, most preferably 1.60 or more.

Calcium silicate having a refractive index of less than 1.50 (1.
46), diatomaceous earth (1.45), hydrous silicic acid (1.44), etc., have a small light-shielding ability and need to be added in large amounts, and are not preferred as light-shielding substances. In addition, due to the recent boom in overseas travel, when a high-sensitivity photographic film having an ISO sensitivity of 400 or more is passed through an inspection machine using X-rays in baggage inspection at an airport, fog is likely to occur due to X-rays. In order to prevent this, it is preferable to use a light-shielding substance having a specific gravity of 3.1 or more, preferably 3.4 or more. The form of the light-shielding substance having an X-ray shielding property other than the light-shielding property having a specific gravity of 3.1 or more, preferably 3.4 or more, particularly preferably 4.0 or more is not limited to those exemplified below, and any form, for example, pigment , Powder, flakes, whiskers, fibers and the like.

Examples of the light-shielding substance having a specific gravity of 3.1 or more include, for example, silicon carbide, barium sulfate, molybdenum disulfide,
Lead oxide (lead white), iron oxide, titanium oxide, magnesium oxide, barium titanate, copper powder, iron powder, brass powder, nickel powder, silver powder, lead powder, steel powder, zinc powder, tungsten whisker, silicon nitride whisker , Copper whiskers, iron whiskers, nickel whiskers, chrome whiskers, stainless steel powder and whiskers, magnesite, apatite, spinel, corundum, zircon,
Examples include antimony trioxide, barium carbonate, zinc white, chrominium oxide, tin powder, and mixtures thereof.

Particularly preferable light-shielding substances for imparting X-ray shielding properties are zircon, corundum, barium sulfate, barium chloride, barium titanate, lead powder, lead oxide, zinc powder, zinc white, tin powder, stainless powder, Stainless whisker, iron oxide, tungsten whisker, nickel whisker. A light-shielding substance which is particularly preferable as an injection molded product for an ultra-high-sensitivity photographic photosensitive material having an ISO sensitivity of 400 or more has a refractive index of 1.50 or more and a specific gravity of 3.1 or more, and most preferably has a refractive index of 1.56 or more and a specific gravity of 3.4 or more. Is a light-shielding substance.

The light-shielding substance kneaded in the thermoplastic resin is as follows:
In order to properly maintain fluidity during injection molding, a powdery light-shielding substance having an aspect ratio of particles of 3 or less is preferable. Such a powdery light-shielding substance having an aspect ratio of 3 or less is shown below.

Representative examples of powdery light-shielding substances having an aspect ratio of 3 or less: carbon black, fused silica, crystalline silica, quartz powder, glass beads, glass powder, calcium silicate, aluminum silicate, kaolin, talc, clay, silicon Alkaline earth, silicates such as wollastonite, iron oxide, iron black, titanium oxide, zinc oxide, metal oxides such as alumina, calcium carbonate, metal carbonates such as magnesium carbonate, calcium sulfate, Sulfates of metals such as barium sulfate, as well as silicon carbide, boron nitride, and various metal powders.

When the thermoplastic resin has an X-ray shielding property, the content of the light-shielding substance which can be kneaded with the resin is 3 to 80% by weight, preferably 7 to 70% by weight, more preferably 10 to 70% by weight. 6060% by weight, most preferably 20-50% by weight. Less than 5% by weight has almost no X-ray shielding effect,
If the content exceeds 10% by weight, production is difficult, and physical strength and injection moldability are lacking, and practical use is difficult.

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

Representative examples of metal powder (including metal paste) include aluminum powder, aluminum paste,
Copper powder, stainless steel powder, iron powder, nickel powder, brass powder, silver powder, tin powder, zinc powder, steel powder and the like.

The term “aluminum powder” as used in the present invention includes both aluminum powder and aluminum paste. A powder obtained by coating the surface of an aluminum powder with a surface coating substance and a powder obtained by removing a low-volatile substance from the aluminum paste are treated with a thermoplastic resin. What is kneaded is preferable.

In the thermoplastic resin composition used for the cartridge body 13, this aluminum paste and various aromatic monovinyl resins (polystyrene resin, rubber-containing polystyrene resin, etc.) and polyolefin thermoplastic resins (various polypropylene resins, various polyethylene resins, Acid-modified resin, EVE resin, EEA resin, EAA resin, etc.),
Low molecular weight polyolefin resin, paraffin wax,
A viscosity imparting agent, a dispersing agent such as metallic soap, etc. are heated and kneaded, and low volatile substances (mainly mineral spirits and white spirits having strong odor) are removed by a vacuum pump or the like. The content of volatile substances is 3% or less, preferably 1% or less. %, Particularly preferably 0.5% or less, is preferably used as an aluminum paste compound resin or an aluminum paste masterbatch resin.

The aluminum powder is obtained by pulverizing molten aluminum into powder by an atomizing method, a granulating method, a rotating disk dropping method, an evaporation method or the like, and crushing aluminum foil by a ball mill method, a stamp mill method or the like. Including Since aluminum powder alone is unstable, various known surface coating treatments for inactivating the aluminum powder surface are performed.

Improvement of dispersibility of the light-shielding substance in resin, improvement of resin fluidity, friction fog and pressure fog on photographic photosensitive material,
It is preferable to coat the surface with a surface coating material in order to prevent the generation of micro grit that causes abrasion and the like, the generation of volatile substances harmful to photographic properties, the reduction of moisture absorption, and the prevention of die lip stains. Representative examples of the surface coating material are shown below.

(1) Coupling agent Coating agent coating containing azidosilanes
62-32125). 2. Coating of silane coupling agent (aminosilane, etc.) Coating of titanate-based coupling agent (2) Deposition of silica, followed by deposition of alumina (3) Coating of higher fatty acid metal salts such as zinc stearate, magnesium stearate, calcium stearate, etc. (4) Sodium stearate, potassium stearate Surfactant coating such as oxy, ethylene, dodecyl, amine

(5) An aqueous barium sulfide solution and an aqueous sulfuric acid solution are reacted in the presence of an excess amount of barium ion to produce barium sulfate having an average particle diameter of 0.1 to 2.5 μm. In addition, barium silicate is formed on the surface of barium sulfate, and then a mineral acid is added to the slurry to decompose the above barium silicate into hydrated silica and deposit it on the surface of barium sulfate for coating. (6) Metal hydrated oxides (one or more of hydroxides of titanium, aluminum, cerium, zinc, iron, cobalt or silicon) and metal oxides (titanium, aluminum,
One of oxides of cerium, zinc, iron, cobalt or silicon
Species and two types), or a surface coating with a composition comprising only one of the aforementioned metal hydrated oxides or metal oxides.

(7) Coating a polymer having one or more reactive groups selected from the group consisting of an aziridine group, an oxazoline group and an N-hydroxyalkylamide group in the molecule. (8) Polyoxyalkyleneamine (9) Surface coated with cerium cation, selected acid anion and alumina (10) Surface coated with alkoxytan derivative having α-hydroxycarboxylic acid residue in the substituent. (11) Surface coating with polytetrafluoroethylene (12) Surface coating with polydimethylsiloxane or modified silicone (13) Surface coating with phosphate ester compound (14) Surface coating with 2- to 4-hydric alcohol

(15) Surface coating with olefin wax (polyethylene wax, polypropylene wax). (16) Surface coating with hydrous aluminum hydroxide (17) Silica or zinc compound (zinc chloride, zinc hydroxide,
One or a combination of two or more of zinc oxide, zinc sulfate, zinc nitrate, zinc acetate, zinc citrate, etc.). (18) Surface coated with polyhydroxy saturated hydrocarbon (19) Surface coated with surfactant (cationic, nonionic, zwitterionic) (20) Organometal chelate compounds (especially β-dititon chelate compounds It is preferable because the dispersibility is improved, etc.).

As a surface coating material of the light-shielding substance, the photographic properties (fog generation, abnormal sensitivity, abnormal coloration, etc.) of the photographic light-sensitive material are less adversely affected, the dispersibility of the light-shielding substance is improved, the occurrence of bumps is reduced, and the resin flows. (1)
(3), (12), (15), (16), (18), (19) and (20) are particularly preferred. In addition, various antistatic agents, lubricants, and drip-proofing agents having effects other than the surface coating effect are also preferable.

The thermoplastic resin forming the cartridge body 13 may be colored translucently or opaquely by adding a coloring light-shielding substance. As a result, the light-shielding property is improved, the rigidity is increased, and the injection moldability is improved. Further, it is preferable because it can be used to identify the type of photographic material in a translucent or transparent container. Examples of the light-shielding substance for coloring include a dye, a colored pigment, a white pigment, a metal powder, a metal fiber, a metal flake, and carbon black.

Next, representative examples of coloring light-shielding substances for each color will be described. Black; carbon black, iron black (iron sesquioxide), graphite (graphite), mineral black, aniline black, etc. White; titanium oxide, calcium carbonate, mica, zinc white,
Clay, barium sulfate, calcium sulfate, antimony white, lead white, lithopone, magnesium silicate, etc. Yellow; titanium yellow, yellow iron oxide, chrome yellow, chromium titanium yellow, disazo pigment, bat pigment, quinophthalene pigment, isoindolinone, zinc Yellow, Cadmium Yellow, Loess, Pigment Yellow L, Hansa Yellow 3G, etc.

Red; red bengara, disazo pigment, berlene pigment, monoazo lake pigment, condensed azo pigment, cadmium red, bon red 2B, carmine 6B, pyrazolone red, lake red C, lead red, permanent red 4
R, etc. Blue; Cobalt blue, ultramarine, navy blue, phthalocyanine blue, cyanine blue, indanthrene blue, indigo, cyanine blue, etc. Green; chrome oxide green, titanium green, zinc green, emerald green, cobalt green, pigment green, phthalocyanine green , Cyanine green, etc. Silver; Aluminum powder, aluminum paste, tin powder are available, but carbon black is particularly inexpensive, resin spot coloring failure and lumps (foreign-like lump) are not conspicuous, light shielding ability is excellent, and photographic properties are excellent. It is preferable in that it is good and has a synergistic effect of preventing oxidation. When color printing is performed on a package, a cartridge body, or the like, it is preferable that the color be colored white, gray, yellow, or silver from the viewpoint of appearance, luminosity of printing, and the like.

Representative examples of lubricants that can be kneaded with the thermoplastic resin constituting the cartridge body 13 are described below. (1) Fatty acid amide-based lubricant (saturated fatty acid amide-based lubricant) Behenic acid amide-based lubricant; Diamid KN (Nippon Kasei) and the like. Stearamide amide-based lubricants: Armide HT (Lion Oil), Alflo S-10 (Nippon Oil & Fats), Fatty Acid Amamid AP-1 (Nippon Kasei), Amide S. Amide T (Nitto Chemical), Neutron-2 (Nippon Seika) )etc. (Hydroxystearic amide-based lubricant) Palmitic amide-based lubricant; Neutron S-18
(Nippon Seika), Amide P (Nitto Chemical), etc. Lauric amide lubricant; Armide C (Lion
Akzo), Diamond (Nippon Kasei) and others. (Unsaturated fatty acid amide-based lubricant) Erucamide amide-based lubricant; Alflo P-10 (Nippon Oil & Fats), 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 Chemical),
Diamid O-200 / Diamid G-200 (Nippon Kasei), Alflo E-10 (Nippon Oil & Fats), fatty acid amide O (Kao) and the like. (Bis fatty acid amide lubricant) Methylene bisbehenic amide lubricant; Diamid NK bis (Nippon Kasei) and the like. Methylene bisstearic acid amide lubricants such as Diamid 200 Bis (Nippon Kasei), Armowax (Lion Akzo), Bisamide (Nitto Chemical) and the like. Methylenebisoleic amide lubricant; Lubron O
(Nippon Kasei) and others. Ethylene bisstearic acid amide lubricant; Armoslip EBS (Lion Akzo) and the like. Hexamethylene bisstearic acid amide-based lubricant; Amide 65 (Kawaken Fine Chemical) and the like. Hexamethylenebisoleic amide-based lubricant; Amide 60 (Kawaken Fine Chemical) and the like.

(2) Nonionic surfactant lubricant; Electrostripper TS-2, Electrostripper T
S-3 (Kao soap) and the like. (3) hydrogen carbonate-based lubricant; liquid paraffin, natural paraffin, microwax, synthetic paraffin, polyethylene wax (number average molecular weight is 10,000 or less, preferably 8,000 or less, particularly preferably 6,000 or less), polypropylene wax (number average molecular weight is 10,000) Or less, preferably 8000 or less, particularly preferably 6000 or less), chlorinated hydrocarbons, fluorocarbons and the like. (4) fatty acid lubricants; higher fatty acids (C ₁₂ or more, specifically, Kaburon acid, stearic acid, oleic acid, erucic acid, palmitic acid and the like), hydroxy fatty acid and the like.

(5) Ester lubricants: lower alcohol esters of fatty acids, polyhydric alcohol esters of fatty acids, polyglycol esters of fatty acids, fatty alcohol esters of fatty acids, and the like. (6) alcohol-based lubricants: polyhydric alcohols, polyglycols, polyglycerols and the like. (7) Metal soaps; higher fatty acids such as lauric acid, stearic acid, succinic acid, stearyl lactic acid, benzoic acid, hydroxystearic acid, lactic acid, phthalic acid, ricinoleic acid, naphthenic acid, oleic acid, palmitic acid, erucic acid and lithium And compounds with metals such as sodium, magnesium, calcium, strontium, barium, zinc, cadmium, aluminum, tin, lead, etc., and preferred are magnesium stearate, calcium stearate, zinc stearate, magnesium oleate and the like. . (8) Partially saponified montanic acid ester (9) Silicone lubricant; various grades of dimethylpolysiloxane and modified products thereof (Shin-Etsu Silicone, Toray Silicone), especially various silicone oils improve resin fluidity, lubricity, etc. When used in combination with a light-shielding substance, the dispersibility of the light-shielding substance is improved, and the resin is made cloudy to increase the haze (ASTM D-1003). It is preferable because it exhibits unexpected effects such as improvement.

As described above, the silicone-based lubricant which does not adversely affect the photographic properties of a photographic light-sensitive material and has an effect of improving a light-shielding property and a coloring property in addition to an improvement in lubricity will be described in more detail below. .

Various grades of dimethylpolysiloxane,
And modified products thereof (Shin-Etsu Silicone, Toray Silicone), polymethylphenylsiloxane, carboxyl-modified silicone, olefin-modified silicone, polyether-modified silicone modified with polyethylene glycol or polypropylene glycol, olefin / polyether-modified silicone, amide-modified silicone, A silicone oil containing a modified siloxane bond, such as polydimethylsiloxane, amino-modified silicone, carboxyl-modified silicone, α-methylstyrene-modified silicone, epoxy-modified silicone, amino-modified silicone, and alcohol-modified silicone.

Among the silicone oils, olefin-modified silicones and amides which have little adverse effect on the photographic properties of the photographic light-sensitive material and have a large lubricating effect, particularly when applied to injection molded articles for photographic light-sensitive materials, are preferred. Modified silicone, polydimethylsiloxane, polyether-modified silicone, olefin / polyether-modified silicone, and carboxyl-modified silicone.

The silicone oil improves the coefficient of friction of a molding material, for example, a resin film in a heated state, reduces sliding resistance generated during sealing of a hot plate by an automatic packaging machine, and prevents wrinkles from occurring. As a result, an injection molded product for a photographic light-sensitive material can be obtained, which has a beautiful appearance, a high sealing property, and a performance that has tight adhesion to a package. In addition, it is possible to prevent a decrease in gloss due to sliding and obtain a beautiful seal portion.

The silicone-based lubricant may be used alone or in combination of two or more, or may be used in combination with another lubricant or plasticizer. The effect of such silicone oil addition is
It is as follows. (1) Improve the fluidity of the resin, reduce the motor failure of the screw, and prevent the occurrence of melt fracture. (2) Sufficient lubricity can be ensured without adding a lubricant such as fatty acid amide which bleeds out to form a white powder.

One or more antioxidants are added to the thermoplastic resin used for the cartridge body 13 for the purpose of preventing thermal deterioration of the thermoplastic resin such as polyolefin resin or olefin-based thermoplastic elastomer and improving photographic properties. Is preferred. By adding at least one of an antioxidant and a radical scavenger, it is possible to prevent heat deterioration and thermal decomposition of additives such as thermoplastic resins, lubricants, fatty acids, organic nucleating agents, and interfacial lubricants. It is possible to prevent the fluidity of the plastic resin composition from being remarkably changed and the occurrence of bumps (foreign masses). Further, it is possible to prevent the generation of thermal decomposition products (aldehydes and the like) which adversely affect the photographic properties of the photographic light-sensitive material.

Such antioxidants include antioxidants, radical scavengers, and antioxidant synergists. Hereinafter, typical antioxidants will be exemplified. (A) phenolic antioxidants; vitamin E (tocopherol), tocopherol dimers (α-tocopherol, β-tocopherol, 5,7-dimethyltocol, etc.), 6-tert-butyl-3-methylphenyl derivative, 2,6-di-tert-butyl-P-cresol-
tert-butylphenol, 2.2′-methylenebis- (4-ethyl-6-tert-butylphenol),
4.4'-butylidenebis (6-tert-butyl-m
-Cresol), 4,4'-thiobis (6-tert-
Butyl-m-cresol), 4,4-dihydroxydiphenylcyclohexane, alkylated bisphenol, styrenated phenol, 2,6-di-tert-butyl-
4-methylphenol, n-octadecyl-3- (3 ′
.5'-di-tert-butyl-4'-hydroxyphenyl) propinate, 2.2'-methylenebis (4-methyl-6-tert-butylphenol), 4.4'-
Thiobis (3-methyl-6-tert-butylphenyl), 4,4′-butylidenebis (3-methyl-6-t
tert-butylphenol), stearyl-β (3.5)
-Di-4-butyl-4-hydroxyphenyl) propionate, 1,1.3-tris (2-methyl-4hydroxy-5-tert-butylphenyl) butane, 1.3.
5-trimethyl-2.4.6-tris (3.5-di-te)
rt-butyl-4hydroxybenzyl) benzene, tetrakis [methylene-3 (3 ′ · 5′-di-tert-butyl-4′-hydroxyphenyl) propionate] methane.

(B) ketone amine condensation type antioxidant;
-Ethoxy-2,2,4-trimethyl-1,2-dihydroquinoline, polymers of 2,2.4-trimethyl-1,2-dihydroquinoline, trimethyldihydroquinoline derivatives and the like.

(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 and the like.

(D) Imidazole antioxidants: 2-mercaptobenzimidazole, zinc salt of 2-mercaptobenzimidazole, 2-mercaptomethylbenzimidazole and the like.

(E) Phosphite antioxidants: alkylated allyl phosphite, tris (mono and / or dinonylphenyl) phosphite, cyclic neopentanetetraylbis (2.6-di-tert-butyl-) 4
-Methylphenyl) phosphite, diphenylisodecylphosphite, tris (nonylphenyl) phosphite sodium phosphite, tri (nonylphenyl) phosphite, 2.2-methylenebis (4.6-di-ter
t-butylphenyl) octyl phosphite, tris (2.4-di-tert-butylphenyl) phosphite, triphenyl phosphite and the like.

(F) Thiourea-based antioxidants; thiourea derivatives, 1,3-bis (dimethylaminopropyl) -2-
Thiourea and the like.

(G) Other antioxidants useful for air oxidation: dilauryl thiodipropionate and the like.

Representative examples of hindered phenolic antioxidants which are preferably added are shown below. 1,3,5-
Trimethyl 2,4,6-tris (3,5-di-tert
-Butyl-4-hydroxybenzyl) benzene, tetrakis [methylene-3- (3'.5'-di-tert-butyl-4'-hydroxyphenyl) propionate] methane, octadecyl-3,5-di-tert-butyl −
4-hydroxy-hydrocinnamate, 2,2 ', 2'
-Tris [(3,5-di-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′-biphenylenediphosphite, 4,4′-thiobis- (6-tert-butyl-
O-cresol), 2,2′-thiobis- (6-ter
t-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-t
tert-butylphenol), 2,6-di-tert-
Butyl-4-methylphenol, 4-hydroxymethyl-2,6-di-tert-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-te
rt-butyl-m-cresol), 3,9-bis [1.
1-dimethyl-2- [β- (3-t-butyl-4-hydroxy-5-methylphenyl) propionyloxy] ethyl] 2,4.8,10-tetraoxaspiro [5
5] Undecane and the like.

Among the above-mentioned antioxidants, those having a melting point of 100 ° C. or more, preferably 120 ° C. or more are preferable. Further, it is effective to use it in combination with a phosphorus antioxidant. Furthermore, at least one phosphorus antioxidant,
It is particularly preferable to use at least one kind of a hindered phenolic antioxidant and at least one kind of a hydrous double salt compound in total of three or more kinds.

The above-mentioned vitamin E (tocopherol) and dimeric tocopherols (α-tocopherol, β-tocopherol, 5,7-dimethyltocol, etc.) not only have an excellent antioxidant effect, but also give a molded product a yellow color. When used together with a light-shielding substance such as carbon black, the light-shielding ability can be improved as compared with the case where a light-shielding substance such as carbon black is solely added, and the dispersibility can also be improved.

Therefore, even if the addition amount of the light-shielding substance is reduced by 10% or more, it is possible to obtain an injection-molded article having the same light-shielding property as in the case where the light-shielding substance such as carbon black is added alone. . As a result, effects such as prevention of deterioration of photographic properties, improvement of physical strength, improvement of appearance, and reduction of material cost are exhibited.

Particularly preferred antioxidants are phenolic antioxidants, and commercially available products include, for example, various types of Irganox manufactured by Ciba-Geigy (typically Iregaox).
Nox 1010, Irganox 1076, etc.) and Sumilizer BH-T, Su of Sumitomo Chemical Co., Ltd.
milizer BH-76, SumilizerWX
-R, Sumilizer BP-101 and the like. Also, 2,6-di-dibutyl-p-cresol (BH
T), low volatility, high molecular weight phenolic antioxidants (trade names Ireganox 1010, Ireganox)
1076, Topanol CA, Ionox 330
Etc.), diuraryl thiodipropionate, distearyl thiopropionate, dialkyl phosphate, etc.
It is effective to use two or more kinds, particularly two or more kinds in combination.

Examples of the combination of two or more antioxidants include a combination of a hindered phenol-based antioxidant and a pentaerythritol phosphite compound-based antioxidant, and a combination of a hindered phenol-based antioxidant and a diorganic antioxidant. Combination with a pentaerythritol diphosphite compound-based antioxidant, such as a combination of a hindered phenol-based antioxidant and a phosphite-based antioxidant,
Alkyl-substituted monophenol-based antioxidants, alkyl-substituted polyhydric phenol-based antioxidants, and organic phosphite compound-based antioxidants, and organic phosphite-based antioxidants, or any one or two of these Some are selected from the above combinations. Among these, hindered antioxidants can prevent thermal degradation of zinc stearate, which is susceptible to thermal degradation, not only can significantly reduce the occurrence of bumps, but also improve the photographic properties of photographic photosensitive materials. It is particularly preferred because it can be converted to

In particular, at least one of the above hindered phenolic antioxidants having a melting point of 100 ° C. or more, preferably 120 ° C. or more, which is a typical example of a free radical chain terminator, and a phosphorus-based peroxide decomposing agent It is preferable to use the antioxidant in combination with at least one of the antioxidants because the effect of preventing the resin and additives from thermal deterioration can be enhanced without deteriorating photographic properties.

The most preferred antioxidants to be contained in the thermoplastic resin include, for example, various hindered phenolic antioxidants, more specifically, tetrakis [methylene-3- (3,5-di- t-butyl-4-hydroxyphenyl) propionate] methane, n-octadecyl-3- (4'-hydroxy-3'5'-di-t-butylphenol) propionate, tris- (2,4-di-t-butyl) Phenyl) phosphite, 1,3,5-tris- (2-butyl-4-hydroxy-5-di-t-butyl) butane and the like.

Examples of the radical scavenger preferably contained in the thermoplastic resin include, for example, 1.1-diphenyl-
2-picrylhydrazyl, 1.3.5-triphenylferdazyl, 2,2,6,6-tetramethyl-4-piperidone-1-oxyl, N- (3-N-oxyanilino-1.3- Dimethylbutylidene) -aniline oxide,
High-valent metal salts such as ferric chloride, diphenylpicrylhydrazine, dibutylpicrylhydrazine, diphenylamine, hydroquinone, t-butylcateco-
Dithiobenzoyl disulfide p. p′-ditolyl trisulfide, a benzoquinone derivative, a nitro compound,
And nitroso compounds.

Among these, it is particularly preferable to use hydroquinone. Further, the above radical scavengers may be used alone or in combination of several kinds. Further, it is also preferable to use together with one or more of various antioxidants, antioxidant synergistic agents and antioxidants.

The antioxidant synergistic agent can be used in combination with one or more of the above-mentioned antioxidants, radical scavengers and hydrotalcite compounds to form resins or low molecular weight additives (lubricants, antistatic agents, organic additives). Nucleating agents, drip-proofing agents, compatibilizers, etc.) to prevent thermal degradation and thermal decomposition, resulting in a decrease in physical strength, a significant change in resin fluidity, mold gate clogging, short shots, and bumps. Can be prevented. Thermal decomposition substances (aldehydes, etc.) that further affect photographic light-sensitive materials
To prevent the occurrence of Examples of the antioxidant synergistic agent having such an action include phosphoric acid, citric acid, a phosphoric acid compound, and a citric acid compound. Particularly, metal phosphate and metal citrate are preferred.

Further, by being contained in a thermoplastic resin, catalyst residues can be neutralized, substances which adversely affect photographic properties by absorbing halogen compounds such as hydrochloric acid can be prevented, and resin burning failure can be prevented. It is preferable to add a hydrotalcite compound and a fatty acid metal salt. The hydrotalcite compound is preferably used after being treated with a surface coating substance, since this improves the dispersibility. By coating the surface, the dispersibility or affinity for the resin is further improved, and the suitability for injection molding, physical strength, and the like are also improved.

Particularly preferable examples of such a surface coating material include, for example, sodium laurate, potassium laurate, sodium oleate, potassium oleate, calcium oleate, magnesium stearate, sodium stearate, zinc stearate. Metal salts of higher fatty acids such as, potassium stearate, sodium palmitate, potassium palmitate, sodium caprate, potassium caprate, sodium myristate, potassium myristate, sodium linoleate, potassium linoleate, and the like. it can.

Also, higher fatty acids represented by lauric acid, palmitic acid, oleic acid, stearic acid, capric acid, myristic acid, linoleic acid and the like; organic sulfonic acids such as calcium dodecylbenzenesulfonate and sodium dodecylbenzenesulfonate; Metal salts: isopropyl triimestearoyl titanate, isopropyl tris (dioctyl pyrophosphate) titanate, tetraisopropyl bis (dioctyl phosphite) titanate, vinyl triethoxy silane, gamma methacryloxypropyl trimethoxy silane, gamma glycidoxy propyl trimethoxy silane, etc. And various lubricants such as higher fatty acid amides, higher fatty acid esters, silicones and waxes.

The surface coating with these surface coating substances can be performed, for example, by adding an aqueous solution of an alkali metal salt of a higher fatty acid to a suspension of the hydrotalcite compound in warm water with stirring. It can be carried out by dropping a solution of a higher fatty acid or a diluting solution of a coupling agent while stirring the talcite compound powder with a mixer such as a Henschel mixer.

To further improve the dispersion of the hydrotalcite compounds, higher fatty acids, fatty acid amide-based lubricants, sorbitan fatty acid esters such as silicone oil and sorbitan monostearate, and glycerin fatty acids such as glycerin monostearate can be used. One or more of esters and the like may be added as a dispersant.

When used in combination with a hydrotalcite compound, the photographic properties are prevented from deteriorating, the stability of injection molding is improved, and the anticorrosion (also referred to as rustproof) effect of an injection molding machine or a mold is improved. In addition to preventing deterioration of the resin, the effect of improving transparency, preventing a decrease in physical strength, and preventing the occurrence of spots and coloring failure due to resin burning are synergistically improved. Phenolic antioxidants and phosphorus (phosphite)
When used in combination with one or more stabilizers selected from the group consisting of a series of antioxidants and fatty acid metal salts, there is almost no deterioration in the photographic properties of the photographic light-sensitive material, and corrosion of injection molding machines and molds (also referred to as rust prevention). This is particularly preferable because the effect and the antioxidant effect are increased.

Fatty acids which are preferably used in combination with hydrotalcite compounds and exhibit not only the same excellent effects as hydrotalcite compounds but also the effect of dispersibility of lubricants and light-shielding substances The metal salt (also called metal soap) will be described.

Representative examples of fatty acid metal salts include lauric acid, stearic acid, succinic acid, stearyl lactic acid, lactic acid,
Higher fatty acids such as phthalic acid, benzoic acid, hydroxystearic acid, ricinoleic acid, naphthenic acid, oleic acid, palmitic acid, erucic acid and lithium, sodium, magnesium, calcium, strontium, barium, tin, cadmium, aluminum, zinc, Examples include compounds with metals such as lead, and preferred examples include magnesium stearate, calcium stearate, sodium stearate, zinc stearate, calcium oleate, zinc oleate, and magnesium oleate.

Further, one or more of inorganic nucleating agent and organic nucleating agent can be added to the thermoplastic resin. By adding one or more of an inorganic nucleating agent and an organic nucleating agent, surface hardness, rigidity, Izod impact strength, abrasion resistance, and the like can be improved. Further, when it is added to a polyolefin resin of a crystalline resin, particularly a homopolyethylene resin, an ethylene-α-olefin copolymer resin, or a propylene-α-olefin copolymer resin, in addition to the above properties, transparency and injection moldability ( Cycle and molding failure).

Examples of the organic nucleating agent 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, and other aluminum compounds. Salt, aromatic metal phosphate, alkyl alcohol having 8 to 30 carbon atoms,
Condensates of polyhydric alcohols and aldehydes, and alkylamines.

The carboxylic acids are a generic term including their derivatives. Representative examples thereof include acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, tetrahydrophthalic acid, mesaconic acid, angelic acid, and citraconic acid. Acid, crotonic acid, isocrotonic acid, nadic acid,
(Endosis-bicyclo [2,2,1] hept-5-ene-2,3-dicarboxylic acid), maleic anhydride, citraconic anhydride, itaconic anhydride, methyl acrylate, butyl methacrylate, ethyl acrylate, methacrylic acid Ethyl acrylate, butyl acrylate, butyl methacrylate, glycidyl acrylate, glycidyl methacrylate, monoethyl maleate, diethyl maleate, monomethyl fumarate, dimethyl fumarate,
Itaconic acid diethyl ester, acrylic acid amide, methacrylamide, maleic acid monoamide, maleic acid diamide, maleic acid-N-monoethylamide, maleic acid-N, N-diethylamide, maleic acid-N-monobutylamide, maleic acid- N, N-dibutylamide, fumaric acid monoamide, fumaric acid diamide, sumaric acid-N-monoethylamide, fumaric acid-N, N-diethylamide,
Fumaric acid-N-monobutylamide, fumaric acid-N, N-
Diethylamide, fumaric acid-N-butyramide, fumaric acid-N, N-dibutylamide, maleimide, monomethyl maleate, dimethyl maleate, potassium methacrylate, sodium acrylate, zinc acrylate, magnesium acrylate, calcium acrylate, Examples thereof include sodium methacrylate, potassium acrylate, potassium methacrylate, N-butylmaleimide, N-phenylmaleimide, maleenyl chloride, glycidin maleate, dipropyl maleate, aconitic anhydride, and sorbic acid.

Representative examples of particularly preferred sorbitol compounds among the organic nucleating agents are shown below. di- (o-methylbenzylidene) sorbitol o-methylbenzylidene-p-methylbenzylidenesorbitol di- (o-methylbenzylidene) sorbitol m-methylbenzylidene-o-methylbenzylidenesorbitol di- (o-methylbenzylidene) sorbitolh m-methylbenzylidene-p-methylbenzylidenesorbitol 1.3-heptanylidenesorbitol 1,3,2,4-diheptanylidenesorbitol 1,3,2,4-di (3-nony1-3-pentenylidene) sorbito
l 1,3-cyclohexanecarbylidenesorbitol 1,3,2,4-dicyclohexanecarbylidenesorbitol 1,3,2,4-di (p-methylcyclohexanecarbylidene) s
orbitol Aromatic hybrocarbon groups or derivatives there 1,3-benzylidenesorbitol 1,3,2,4-dibenzylidene-D-sorbitol 1,3,2,4-di (m-methylbenzylidene) sorbitol 1,3,2,4-di ( p-methylbenzylidene) sorbitol 1,3,2,4-di (p-hexylbenzylidene) sorbitol 1,3,2,4-di (l-naphthalenecarbylidene) sorbito
l 1,3,2,4-di (phenylacetylidene) sorbitol 1,3,2,4-di (methylbenzylidene) sorbitol 1,3,2,4-di (ethylbenzylidene) sorbitol 1,3,2,4-di ( propylbenzyledene) sorbitol 1,3,2,4-di (methoxybenzylidene) sorbitol 1,3,2,4-di (ethoxybenzylidene) sorbitol 1,3,2,4-di (P-methylbenzylidene) sorbitol 1,3,2 ・4-di (P-chlorbenzylidene) sorbitol 1,3,2,4-di (P-methoxybenzylidene) sorbitol 1,3,2,4-di (alkilbenzylidene) sorbitol 1,3,2,4-di (methybenzylidene) sorbitol aluminumbenzoate, etc.

Among the above-mentioned organic nucleating agents, the most suitable resin to which the dibenzylidene sorbitol compound particularly preferred in the present invention is added is a polyolefin resin, for example, a homopolypropylene resin, a propylene / α-olefin copolymer (block type And polyolefin resins such as low-density homopolyethylene resin, high-density homopolyethylene resin, linear polyethylene (ethylene / α-olefin copolymer) resin and ethylene / propylene copolymer resin Resin. In particular, a crystalline polyolefin resin having a high crystallinity is preferable.

Specific examples of the polyolefin resin, various thermoplastic elastomers, and various compatibilizing resins described above are shown below. Representative examples of the polyolefin resin include high-density homopolyethylene resin, medium-density homopolyethylene resin, low-density homopolyethylene resin, homopolypropylene resin, propylene / α-olefin copolymer resin, and various ethylene copolymer resins. is there.

Typical examples of various ethylene copolymer resins are shown below. (1) Ethylene-vinyl acetate copolymer (hereinafter referred to as “EV
A)) (2) ethylene-propylene copolymer resin (3) ethylene-1-butene copolymer resin (4) ethylene-butadiene copolymer resin (5) ethylene-vinyl chloride copolymer resin (6) ) Ethylene-methyl methacrylate copolymer (hereinafter, referred to as
(Referred to as “EMMA”) resin (7) Ethylene-methyl acrylate copolymer (hereinafter, referred to as “EMMA”)
(Referred to as “EMA”) resin (8) Ethylene-ethyl acrylate copolymer (hereinafter, referred to as “EMA”)
(Referred to as “EEA”) resin (9) ethylene-acrylonitrile copolymer resin (10) ethylene-acrylic acid copolymer (hereinafter referred to as “EA”)
A)) (11) ionomer resin (resin obtained by crosslinking a copolymer of ethylene and an unsaturated acid with a metal such as zinc) (12) ethylene-α-olefin copolymer (hereinafter, referred to as “A”)
(Referred to as “L-LDPE”) resin (13) Ethylene-propylene-butene-1 ternary copolymer resin, etc.

The details of the above-mentioned L-LDPE resin are shown below. L-LDPE (Linear Low D)
(Energy Polyethylene) resin is referred to as a third polyethylene resin, and has a medium / low density, a high density,
Energy saving, combining the advantages of both polyethylene resins
It is a low-cost, high-strength resin that meets the resource-saving era. This resin is a copolymer obtained by copolymerizing ethylene and an α-olefin having 3 to 20, preferably 3 to 13, more preferably 4 to 10, and particularly preferably 5 to 9 carbon atoms. Is a polyethylene resin having a short branch structure.

Preferred α-olefins in terms of physical strength and cost include butene-1, pentene-1 and octene-1.
1, hexene-1,4-methyl-pentene-1, heptene-1,3-methyl-pentene-1, 4,4-dimethyl-pentene-1, heptene-1, nonene-1, undecene-1, dodecene- 1, decene-1 and the like are used. In the present invention, preferably, the α-olefin is butene-1,
Hexene-1,4-methylpentene-1, octene-1
And the content of these α-olefins is 0.1 to 1
5 mol% of L-LDPE resin, most preferred is L-LDPE resin in which the α-olefin is butene-1 and the content of butene-1 is 1 to 8 mol%.

Commercial L-LD polymerized and produced with a conventional catalyst
Specific examples of the PE resin are shown below. Ethylene butene-1
Copolymer resin: G resin and NUC-FLX (UCC),
Dourex (Dow Chemical), Scrair (DuPont Canada), Marlex (Philips), Stamirex (DSM), Exelen VL (Sumitomo Chemical), Neozex (Mitsui Petrochemical), Yucalon-LL
(Mitsubishi Yuka), Nisseki Linirex (Nippon Petrochemical), N
Ethylene-hexene-1 copolymer resins such as UC polyethylene-LL (Nihon Unicar), Nipolonm (Tosoh), Shorex Linear (Showa Denko), Ube polyethylene L (Ube Industries), Idemitsu polyethylene L (Idemitsu Petrochemical)
TUFLIN (UCC), TUFTHENE (Nippon Unicar), etc., ethylene / 4-methylpentene-1 copolymer resin: Ultrazex (Mitsui Petrochemical), etc., ethylene / octene-1 copolymer resin: Stamirex (DSM),
Dourex (Dow Chemical Co.), Screa (DuPont Canada), MORETEC (Idemitsu Petrochemical) and the like.

Representative examples of various thermoplastic elastomers are described below. Thermoplastic elastomers (hereinafter referred to as TRE) can be roughly classified into styrene-based (hereinafter referred to as SBC),
Ester type (hereinafter referred to as TPEE), olefin type (hereinafter referred to as TPO), vinyl chloride type (hereinafter referred to as TPVC), amide type (hereinafter referred to as TPAE), crystalline 1,2
There are various chemical structures such as polybutadiene (hereinafter referred to as RB), ionomer, fluorine (hereinafter referred to as F-TPE), urethane (hereinafter referred to as TPU) and isoprene.

The following are typical commercially available TPEs. TP
R (Uniroyal), TPNor Somel
(EI du Pont de Nemours),
Telcar. Estane (BF Goodric)
h Chemical), Vistaflex (Exx
on Chemical), Visalon (Esso)
Chemical), Pro-fax (Hercule)
s), ET (Allied Chemical), Re
n flex (Ren Plastics), Sant
oprene (Monsanto), Keltan-T
P (Naamlozen Vennotescap D
SM), Unprene (Internationa
l Synthetic Rubber), Dutra
l TP (Montedison), Dual T
P (Montedison), Esplen EPR (or Sumitomo TPE) (Sumitomo Chemical), Mirastomer (Mitsui Petrochemical), JSR-Thermolan (Nippon Synthetic Rubber)
etc.

The details of the styrene-based thermoplastic elastomer will be described below. A styrene-based heat-exchanger which not only has excellent compatibility with the thermoplastic resin used for molding the cartridge 13 of the photographic film cartridge 10 of the present invention and other various thermoplastic resins, but also has excellent dispersibility of the light-shielding substance. Thermoplastic resins containing a plastic elastomer are preferred. In particular, when a styrene-based thermoplastic elastomer is used for a masterbatch resin pellet containing a high concentration of a light-shielding substance, an injection-molded product for a colored photographic light-sensitive material having excellent dispersibility, physical strength, and appearance, and having less occurrence of failure in injection molding can be obtained. It is preferable because it can be obtained.

When the resin composition of the masterbatch resin pellets contains a styrene-based thermoplastic elastomer, the resin composition for dilution contains a crystalline resin (polyolefin-based resin,
Polyacetal resin, polyamide resin, polyvinylidene chloride resin, linear polyester resin, etc. or non-crystalline resin (polystyrene resin, polycarbonate resin, polyvinyl alcohol resin, polyvinyl chloride resin, methacrylic resin) , Vinyl acetate-based resin, etc.), or a mixture of both resins, and even if a recycled resin is mixed in, a well-compatibilized colored resin composition for injection molding can be obtained. .

Here, the styrene-based thermoplastic elastomer refers to a random, block, or the like of a styrene-based monomer (hard segment) and another monomer (soft segment) such as a monoolefin or diolefin copolymerizable with the styrene-based monomer. Copolymers such as grafts (particularly preferably Brook copolymers), and hydrogenated products of these copolymers.

Examples of the styrene monomer include styrene, α-chlorostyrene, 2,4-dichlorostyrene, p-methoxystyrene, p-methylstyrene, p-phenylstyrene, p-divinylbenzene,
-(Chloromethoxy) -styrene, α-methylstyrene, o-methyl-α-methylstyrene, m-methyl-α
-Methylstyrene, p-methyl-α-methylstyrene,
p-methoxy-α-methylstyrene and the like. Among these, styrene is particularly preferred. Examples of the diolefin include dicyclopentadiene,
Examples include non-conjugated dienes such as 4-hexadiene, cyclooctadiene, and methylnorbornene, and conjugated dienes such as butadiene and isoprene. Of these, butadiene is particularly preferred.

The monoolefins include, for example, ethylene, propylene, butene-1, hexene-1, 3-
Α having 3 or more carbon atoms, such as methylbutene-1, 4-methylpentene-1, heptene-1, octene-1, and decene-1
-Olefins. Of these, ethylene and propylene are particularly preferred. Examples of the structure of the block copolymer include a so-called ABA type in which hard segments are bonded to both ends of a soft segment, a multi-block type having a repeating structure of both blocks, and a radial block type in which both blocks are radially bonded. In the operating temperature range, the polystyrene block forms a glassy domain and is dispersed in the segment with a size of several tens of nanometers, thereby forming a physical cross-linking point by constraining the soft segment.

Such a styrene-based thermoplastic elastomer can be prepared by subjecting the above-mentioned suitable monomers to a suitable method known in the art, for example, anionic living polymerization, batch bulk polymerization, continuous bulk polymerization, suspension polymerization, continuous solution polymerization, or the like. It can be obtained by copolymerization by a radical polymerization method such as an emulsion polymerization method. Among such polymerization methods, anionic living polymerization is particularly preferable, and an organolithium compound is generally used as an initiator in order to regulate the microstructure of the diene polymer. The polymerization method includes a method of sequentially polymerizing both components (sequential polymerization method) and a method of coupling molecules by a coupling reaction after the sequential polymerization. The latter method using a polyfunctional coupling agent is used for the radial block type. Manufactured in.

Specific examples of such a styrene-based thermoplastic elastomer include, for example, styrene-butadiene-styrene block copolymer resin and its hydrogenated styrene-ethylene-butylene-styrene block copolymer resin, styrene-butadiene copolymer resin. Styrene-ethylene-butylene block copolymer resin which is a coalesced resin and a hydrogenated product thereof, styrene-isoprene copolymer resin and styrene-ethylene-propylene block copolymer resin which is a hydrogenated product thereof, styrene-isoprene-styrene Block copolymer resins and their hydrogenated styrene-ethylene-propylene-styrene block copolymer resins. Among such styrene-based thermoplastic elastomers, styrene-butadiene copolymer resins and hydrogenated products thereof are particularly preferred.

[0141] The trade names and manufacturers of typical styrene-based thermoplastic elastomers are shown below. Kraton (or Califlex TR), Kraton G (or Elexar) (Shell Chemical), Solpre
ne T (Phillips Petroleum), Europrene
SOL T (ANIC), Solprene T (Petroc
hi), Tufprene (Asahi Kasei), Solprene T, Asaprene T (Nippon Elastomer), Clearen (Electrochemical), JSR, SBR (Nippon Synthetic Rubber) and the like.

Further, instead of the styrene-based thermoplastic elastomer or together with the styrene-based thermoplastic elastomer, a modified styrene-based thermoplastic elastomer may be used. Although any method may be used to modify the styrene-based thermoplastic elastomer, it may be modified using, for example, an unsaturated carboxylic acid or a derivative thereof as a modifier.

Unsaturated carboxylic acids, for example acrylic acid,
Methacrylic acid, maleic acid, endobicyclo [2.
2.1] Unsaturated mono- or dicarboxylic acids such as -5-heptene-2,3-dicarboxylic acid (endic acid), fumaric acid, tetrahydrophthalic acid, itaconic acid, citraconic acid, crotonic acid, isocrotonic acid, or the like Derivatives include, for example, acids, halides, amides, imides, anhydrides, esters and the like. Specific examples of the derivative include maleenyl chloride, maleimide, maleic anhydride, endic anhydride, methyl acrylate, methyl methacrylate, citraconic anhydride, monomethyl maleate, dimethyl maleate and the like.

The following are representative examples of various compatibilizers. Compatibilizers are the same type of thermoplastic resin with different properties, recycled thermographic plastic resin and virgin thermoplastic resin, master batch thermoplastic resin blended with high concentration of light-shielding resin, and heat-dense resin for dilution or these. Like a combined resin, it is a substance that can achieve compatibilization when trying to develop new properties and performance not found in a single thermoplastic resin.

As the compatibilizer, there are a non-reactive compatibilizer and a reactive compatibilizer. Specific representative examples of the compatibilizer are shown below. [Typical non-reactive compatibilizers] Styrene / ethylene / butadiene block copolymer resin polyethylene / polystyrene graft copolymer resin polyethylene / polymethyl methacrylate graft copolymer resin polyethylene / polymethyl methacrylate block copolymer resin ethylene・ Propylene / diene copolymer resin Ethylene / propylene copolymer resin Polystyrene ・ Low density homopolyethylene graft copolymer resin Polystyrene ・ High density homopolyethylene graft copolymer resin Hydrogenated styrene / butadiene copolymer resin Styrene / ethylene ・Butadiene / styrene copolymer resin Styrene / butadiene / styrene copolymer resin Chlorinated polyethylene resin Polypropylene / polyamide graft copolymer resin Polypropylene / ethylene / propylene Diene copolymer resin polystyrene polyacrylate ethyl graft copolymer resin polystyrene-polybutadiene graft copolymer resin polystyrene polymethyl methacrylate block copolymer resin

[Representative Examples of Reactive Type Compatibilizers] Anhydrous maleic oxide / propylene / copolymer resin Anhydrous maleic oxide / styrene graft copolymer resin Anhydrous maleic oxide / butadiene / styrene copolymer resin Anhydrous maleic oxide / styrene / ethylene・ Butadiene / styrene copolymer resin Ethylene / glycidyl methacrylate copolymer resin Ethylene / glycidyl methacrylate / styrene graft copolymer resin Ethylene / glycidyl methacrylate / methyl methacrylate graft copolymer resin Maleic anhydride graft polypropylene copolymer resin, etc.

Representative examples of internal and external commercially available compatibilizers are shown below. Kroton G (composition: hydrogenated SBS, hydrogenated SEBS and maleated compound, Shell) Royallt (composition: EPDM / styrene graft copolymer resin, maleated EPDM, EPDM / acrylonitrile copolymer resin, Uniroyal) Modiper (modiper) ( Composition: block or graft copolymer resin of two kinds of resins, Nippon Oil & Fat) Paraloid (composition: maleated EPDM, core
Shell type block copolymer resin, Rohm an
d Haas) Reseda (Composition: Styrene / methyl methacrylate graft copolymer resin, Toagosei) Bond First (Composition: Ethylene / Glinidyl methacrylate copolymer resin, Sumitomo Chemical) EXXelor (Composition: Maleated EPDM, EXXXo)
n Chem) Tuftec (composition: SBS, SEBS and its maleated compound, Asahi Kasei) Bennet (composition: EVA / EPDM / polyolefin graft copolymer resin, High Tech Pla)
Dics (composition: styrene / maleic anhydride copolymer resin, ARCO) Lexpearl (composition: ethylene / glycidyl methacrylate copolymer resin, Nippon Petrochemical) VMX (composition: 50 parts of EVA impregnated with 50 parts of styrene (Mitsubishi Yuka) (SBS / abbreviation for styrene / butadiene / styrene copolymer resin SEBS / abbreviation for styrene / ethylene / butadiene / styrene copolymer resin EPDM / abbreviation for ethylene propylene / diene copolymer resin EVA / ethylene / Abbreviation for vinyl acetate copolymer resin)

The various organic nucleating agents can be used alone or in combination with various inorganic nucleating agents or in combination of two or more organic nucleating agents. Further, the organic nucleating agent and the inorganic nucleating agent, or one of these surfaces of various fatty acids, lubricants such as fatty acid compounds and silicones, coupling agents, plasticizers, the various light-shielding substances such as surfactants and the like. It can be coated with a dispersant containing a surface coating agent or the like, a wetting agent or the like. Particularly preferred are dibenzylidene sorbitol compounds whose surface is coated with one or more of higher fatty acids, higher fatty acid compounds (preferably higher fatty acid metal salts) and a plasticizer.

Representative inorganic nucleating agents include, for example, viscosities such as talc, clay, mica, montmorillonite and bentonite, calcium silicate, magnesium silicate, calcium sulfate, barium sulfate, lithium carbonate, carbonate Inorganic salts such as sodium, sodium hydrogen carbonate, potassium hydrogen carbonate, calcium carbonate, magnesium carbonate, lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide, magnesium hydroxide, barium hydroxide, etc., sodium oxide, calcium oxide And metal chlorides such as magnesium oxide, alumina, titanium oxide, iron oxide and zinc oxide.

An anti-blocking agent can be preferably added to the thermoplastic resin. When blocking occurs, blocking with the photosensitive material occurs, and the photosensitive layer of the photographic film 14 is damaged, static marks are generated, the insertability of the photosensitive material is reduced, and it becomes difficult to rewind the film. I do.

Representative examples of the antiblocking agent, which have a particularly large antiblocking effect and do not adversely affect the photographic properties of the light-sensitive material, include amorphous zeolites, finely divided silica, natural or synthetic silicon dioxide. ,clay,
Calcium carbonate, natural or synthetic zeolite, amorphized aluminosilicate, anhydrous amorphous aluminosilicate, titanium white (titanium dioxide), diatomaceous earth, mixture of amorphous aluminosilicate and fine amorphous silica , Fine powder of fine calcium carbonate deposited on zeolite particles, metal-substituted crystalline aluminosilicate, metal-substituted zeolite A, asbestos, silicate gel, aluminum silicate, hydroxysodalite, kaolinite,
Examples include talc, magnesium oxide, fibrous magnesium oxysulfate (basic magnesium sulfate), synthetic aluminum magnesium silicate, lithium fluoride and the like.

Representative examples of the surfactant for ensuring the antistatic property, which is preferably contained in the thermoplastic resin, are shown below. [Nonionic] (= nonionic) (1) Alkylamine derivative; T-B103 (Matsumoto Yushi), T-B104 (Matsumoto Yushi) Alkylamide tertiary amine (laurylamine); Armostat 400
(Lion fat) N, N-bis (2-hydroxyethyl cocoamine); 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; Register 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 trigulariseride, such as stearic acid or hydroxystearic acid, monoglycol (Nippon camphor), TB-123 (Matsumoto oil and fat), register 113 (Daiichi Kogyo Pharmaceutical Co., Ltd.) Zorbitan fatty acid ester Special ester; Elique BS-1 (Yoshimura Oil Chemical) 1-hydroxyethyl-2-dodecylglyoxazoline; British cellophane

[Anionic System] (1) Sulfonic acids; alkyl sulfonate RSO ₃ Na alkylbenzene sulfonate alkyl sulfate ROSO ₃ Na

(2) Phosphate ester type; alkyl phosphate

[Cation] (1) Amide-type cation;
1,402,406,411 (Daiichi Kogyo Pharmaceutical)

(2) 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）

[Zwitterionic system] (1) Alkyl petaine type;

(2) imidazoline type; rheostat 53,
532 (lion fat), AMS Lion oils and fats, AMS303, 313 (Lion oils and fats) Alkyl imidazoline type

(3) Metal salt type; AMS 576 (lion fat) rheostat 826, 923 (lion fat) (RNR′CH ₂ CH ₂ CH ₂ NCH ₂ COO) ₂ Mg 2R ≧ C, R ′ = H or ( CH ₂ ) mCOO-｝ (lion fat) R = C ₃ -C ₈ hydrocarbon, A = oxygen or imino group, M =
Organic amine or metal

(4) Alkyl alanine 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 a small adverse effect on photographic properties and human body and have a large effect of preventing stitch marks.

Representative examples of the deodorant and the fragrance which are preferably contained in the thermoplastic resin forming the cartridge body 13 will be described below.

Examples of the deodorant include organic carboxylic acids, mixtures of organic carboxylic acids and zinc compounds, and mixtures of organic carboxylic acids, zinc compounds and aluminum compounds.

Examples of the organic carboxylic acids include aliphatic polycarboxylic acids, aromatic polycarboxylic acids, and acidic polyester compounds having a carboxyl-terminated terminal product of a reaction product of these aliphatic or aromatic polycarboxylic acids with a polyhydric alcohol compound. There is.

Examples of 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.

Examples of the aromatic polycarboxylic acids include phthalic acid, terephthalic acid, isophthalic acid, trimellitic acid, pyromellitic acid, benzenehexatricarboxylic acid, naphthalenedicarboxylic acid, naphthalenetricarboxylic acid, naphthalenetetracarboxylic acid, and 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 terminal carboxyl group obtained by reacting a polycarboxylic acid such as phthalic acid 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 flavor 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.

As the thermoplastic resin, it is preferable to use an ultraviolet absorber for preventing photodeterioration, like the antioxidant, the radical scavenger, the antioxidant synergistic agent and the antioxidant. Representative examples of the ultraviolet absorber are shown below.

(1) Salicyloxidized ultraviolet absorber The main ones are as follows. Phenylsalicylate pt-Butylphenylsalicylate p-Octylphenylsalicylate (2) Benzophenone UV absorber The main ones are as follows. 2,4-Dihydroxybenzophenone 2-Hydroxy-4-methoxybenzophenone 2-Hydroxy-4-octoxybenzophenone 2-Hydroxy-4-dodecyloxybenzophenone 2,2'-Dihydroxy-4-methoxybenzophenone 2,2'-Dihydroxy-4,4'-dimethoxybenzophenone 2 -Hydroxy-4-methoxy-5-sulfobenzophenone (3) Benzotriazole UV absorber The main ones are as follows. 2- (2'-Hydroxy-5'-methylphenyl) benzotriazole 2- (2'-Hydroxy-5'-t-butylphenyl) benzotriazole 2- (2'-Hydroxy-3 ', 5'-di-t-butylphenyl) benzotriazole 2- (2'-Hydroxy-3'-t-butyl-5'-methylphenyl) -5-chloro
benzotriazole 2- (2'-Hydroxy-3 ', 5'-di-t-butylphenyl) -5-chlorobenz
otriazole 2- (2'-Hydroxy-3 ', 5'-di-t-amylphenyl) benzotriazole 2- (2'-Hydroxy-4'-octoxyphenyl) benzotriazole 2- [2'-Hydroxy-3'-(3 " , 4 ", 5", 6 "-tetrahydrophthal im
idemethyl) -5'-methylphenyl] -benzotriazole 2,2-Methylene-bis [4- (1,1,3,3-tetramethylbutyl) -6
-(2H-benzotriazole-2-il) phenol] (4) Cyanoacrylate UV absorber 2-Ethylhexyl-2-cyano-3,3'-di-phenylacrylate Ethyl-2-cyano-3,3'-diphenylate

Further, the aging phenomenon that the appearance (color, gloss, cracks, etc.), physical strength, etc., deteriorates due to the environment (heat, sunlight, rain, ozone, sulfur dioxide, etc.) and the passage of time is prevented. It is preferable to use an anti-aging agent.

Representative examples of such antioxidants are shown below. Naphthylamines such as phenyl-β-naphthylamine diphenylamines such as NN′-diphenylethylenediamine p-phenylenediamines such as N, N′-diphenyl-p-phenylenediamine 6-ethoxy-2,2,4-trimethyl- 1,2-
Hydroquinone derivatives such as dihydroquinaline Monophenols such as 2,6-di-tert-butyl-4-methylphenol 2,2′-methylene-bis- (4-ethyl-6-t
-Butylphenol) and the like thiobisphenols such as 4,4'-thiobis- (6-t-butyl-3-methylphenol) 2-mercaptobenzimidazole and the like

[0177] These antioxidants are arbitrarily added according to the required properties, the effects on photographic properties, and the antiaging effects.

[0178]

EXAMPLE Next, a photographic film cartridge using a disk formed of a resin material having a composition in the range according to the present invention, and a disk formed of a resin material having a composition in the other range were used as comparison objects. An example of a test for the winding noise of the photographic film, the generation of shavings, the drop durability, and the change of the melt index in the photographic film cartridge will be described below.

Table 1 shows the test results of photographic film cartridges using disks formed of resin materials of various compositions. The conditions of each test item, the resin composition of the disk of each test sample, and the like are described after the table.

[0180]

[Table 1] The photo film used for each test sample was “nexi
a "(trade name) A 40 shots (manufactured by Fuji Photo Film Co., Ltd.) were used. (1) Sample: Ethylene-modified polyphenyl ether having a composition of 1 to 1112 nylon at 55% by weight, polyphenyl ether at 35% by weight, and ethylene propylene rubber at 10% by weight. Ethylene-modified polyphenyl ether having a composition of 1266 nylon 55% by weight, polyphenyl ether 35% by weight, and ethylene propylene rubber 10% by weight. 136 nylon 55% by weight, polyphenyl ether 35% by weight, ethylene propylene rubber 10% by weight
An ethylene-modified polyphenyl ether having the following composition. 14. Ethylene-modified polyphenyl ether having a composition of 46% nylon, 55% by weight, 35% by weight of polyphenyl ether, and 10% by weight of ethylene propylene rubber. 15 An ethylene-modified polyphenyl ether having a composition of 55% by weight of aromatic nylon, 35% by weight of polyphenyl ether, and 10% by weight of ethylene propylene rubber. 16 Ethylene-modified polyphenyl ether having a composition of 55% by weight of polypropylene, 40% by weight of polyphenyl ether, and 5% by weight of ethylene propylene rubber. 17 Polyacetal 100% by weight (2) Molybdenum disulfide: "Moricoat Z Powder" (trade name) manufactured by Dow Corning was used. (Unit in the table: weight%) (3) Silicone oil: "KF968 10000cs" manufactured by Shin-Etsu Chemical Co., Ltd. was used. (Unit in the table: weight%) (4) Film take-up sound: An operation of rewinding the entire photographic film to a photographic film cartridge manufactured by using a disk injection-molded using the resin of each composition described above is performed. , The maximum value of the volume was measured. (Unit in the table: d
b) (5) Evaluation of shavings: Using an apparatus simulating an actual camera, the entire amount of the photographic film was drawn out from a photographic film cartridge manufactured using a disk injection-molded using the resin of each composition described above. Later, the rewind action
One photo film per cartridge
The test was performed 0 times on 10 photographic films. Then, the plate for imparting the smoothness of the photographic film was visually inspected after the test, and those in which no shavings could be confirmed were evaluated as "O". The sample that was not found was marked with "●", and the sample whose shavings were confirmed and had a problem in practical use was marked "x". (6) Drop durability: A state in which the entire photographic film is wound into a photographic film cartridge manufactured using a disk injection-molded using the resin of each composition described above.
After leaving at −20 ° C. for 2 hours, the disc was dropped freely from a height of 2 m, and the state of the disc after the drop was observed. And
Out of 10 sample photo film cartridges,
The number of disk failures such as cracks was counted. (Unit in the table: pieces) (7) Melt index ratio: Electric furnace temperature is 2
The resin constituting the disk of each sample was put into a melt indexer at 80 ° C., and the melt index value (MI5min) after 5 minutes and the melt index value (MI30min) after 30 minutes were measured. (MI30mi
n / MI5min).

From the results shown in Table 1, 12
Ethylene-modified polyphenyl ether having a composition of 55% by weight of nylon, 35% by weight of polyphenyl ether, and 10% by weight of ethylene propylene rubber, 1 to 7% by weight of molybdenum disulfide, and 0.5 to 3% of silicone oil. It turns out that it is preferable to add in the range of weight%.

[0182]

As described above in detail, according to the photographic film cartridge of the present invention, the photographic film cartridge is fixed or rotatably attached to both ends of a spool rotatably housed in the cartridge body and wound around the spool. A disc that contacts the side edge of the photographic film roll or the outermost periphery of the photographic film roll to prevent the photographic film roll from loosening is used. 0.5 to 7% by weight of molybdenum disulfide and 0.5 to 3% by weight of silicone oil %, Because it is formed by injection molding with a nylon-modified polyphenyl ether containing each, it is excellent in abrasion suitability, high in both durability and feeding power, and provides a photographic film cartridge with reduced noise when feeding the photographic film. Will be possible.

[Brief description of the drawings]

FIG. 1 is an external perspective view of a photographic film cartridge embodying the present invention.

FIG. 2 is an exploded perspective view of a photographic film cartridge embodying the present invention.

FIG. 3 is an explanatory view of the vicinity of a spool and a disk in FIG. 1;

[Explanation of symbols]

 Reference Signs List 10 photo film cartridge 11 upper case 12 lower case 14 photo film 22, 23 disc

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code FI // B29K 71:00 B29L 31:00

Claims (3)

[Claims] 1. A photographic film cartridge in which a photographic film wound in a roll form on a spool is sent out from the opening of the cartridge body to the outside from the leading end by rotating a spool rotatably housed in the cartridge body. A molybdenum disulfide, which is fixed or rotatably attached to both ends of the spool and contacts a side edge of the photo film roll wound around the spool or an outermost periphery of the photo film roll to prevent the photo film roll from loosening; 0.5 to 7% by weight, silicone oil 0.5 to
A photographic film cartridge formed by injection molding with a nylon-modified polyphenyl ether containing 3% by weight. 2. The nylon-modified polyphenyl ether forming the disk is charged at a load of 10 kg and a load of 280 ° C. with respect to the value of the melt index 5 minutes after being put into the melt indexer at a load of 10 kg and 280 ° C. The value of the melt index after 30 minutes from the introduction into the melt indexer is 1.2 times or less, and the value of the melt index after 5 minutes is 100 g / 10 minutes. The photographic film cartridge according to 1. 3. The photographic film cartridge according to claim 1, wherein the nylon constituting the nylon-modified polyphenyl ether is an aliphatic nylon.