JP2001026690A - Injection molded article for photographic sensitized material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To have excellent photographic properties, dimension precision, physical strength, injection moldability, mar resistance and the like, and also good sliding properties and to prevent light fogging by reflected light in injection molded articles for photographic sensitized materials such as photographic film spools. SOLUTION: Injection molded articles have a melt flow rate (under the condition of ASTM D 1238G) of 2-40 g/10 min, a flexural modulus (JIS K 7203) of at least 18,000 kg/cm2, and a molecular distribution of at most 5, and contain 100 pts.wt. rubbery polymer-containing aromatic monovinyl resin containing 1-40 wt.% rubbery polymer and 0.1-10 pts.wt. silicone resin and are allowed to have a surface reflective glossiness of at most 45%.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention has excellent dimensional accuracy, physical strength, light-shielding properties (when light-shielding properties are required), excellent photographic properties, etc., and has a cartridge body for APS films, a spool for photographic films, and a film unit with a lens. The present invention relates to an injection molded product for a photographic photosensitive material used for a camera body and the like.

[0002]

2. Description of the Related Art Various types of injection molded articles for photographic photosensitive materials used in photographic film cartridges, photosensitive strips, film units with lenses, instant film units, and the like have been proposed. JP-A-1-187
Japanese Patent No. 547 discloses a photosensitive strip which is cut into a strip and wound into a roll, such as a microfilm, a microfilm for computer output, a film for computer printing, and the like, which is incorporated into an exposure apparatus in a light room. A strip material container (having a weight product of 1 kg or more) has been proposed.

Japanese Patent Application Laid-Open No. 2-64533 discloses that a light-tight cartridge is loaded into a loading chamber and the loading lid is closed to open and close the light-tight cartridge opening / closing lid. A light-tightness device comprising: an opening / closing non-operating means for closing the opening / closing lid light-tightly by performing an unlocking operation; and a means for pulling out the film in the light-tight cartridge in conjunction with the formation of the film entrance / exit. Cameras that use a sex cartridge have been proposed.

Japanese Patent Application Laid-Open No. 6-67348 discloses that a resin molded part constituting a patrone main body is made of a resin material having excellent suitability for ultrasonic welding, while maintaining a state where the patrone main body and the photographic film are not in direct contact with each other. A photographic film cartridge has been proposed in which resin molded parts are assembled by ultrasonic welding to each other.

Japanese Patent Application Laid-Open No. 9-80693 proposes a molded article for photographic light-sensitive materials containing a thermoplastic resin having a specific value of a molecular weight distribution and a melt flow rate, and a lubricant.

[0006]

Incidentally, injection molded articles used for photographic photosensitive materials and the like are considered to have a high-grade appearance with a high gloss appearance. It was made of a graft-modified rubber-containing polystyrene resin, a resin containing a nitrile group and a styrene group, and the like.

However, when such a resin is used, the physical strength is reduced, light absorption is insufficient and light fog is generated due to reflected light, the surface of an injection-molded product is damaged, and harmful light is generated during reflected light and thermal decomposition. There have been problems such as deterioration of photographic properties due to generation of gas (hydrogen cyanide gas, aldehyde gas, sulfur compound gas, etc.).

Further, the photosensitive band container proposed in Japanese Patent Application Laid-Open No. 1-187547 can be formed of an ABS resin composition containing a nitrile group in order to ensure drop strength, light-shielding properties and dimensional accuracy. In many cases, when formed of an ABS resin composition containing a nitrile group, photographic properties deteriorate due to generation of harmful gases such as hydrogen cyanide gas which adversely affect the photographic properties of photographic light-sensitive materials. In the case of a package hermetically sealed with a moisture-proof packaging material of 10 g / m ² · 24 hours or less, the deterioration was further worsened.

A camera using a light-tight cartridge proposed in Japanese Patent Laid-Open No. 2-64533 is used for a long time and all over the world.
It is made of an ABS resin composition containing a nitrile group so that the drop strength and the dimensional accuracy can be secured. When this ABS resin composition is used, photographic properties are deteriorated by hydrogen cyanide gas or the like as described above. In particular, it has been found that, in a sealed package, the photographic properties are further deteriorated. In addition, it was found that if the patrone with the photographic film was kept in the camera for three months or more, the photographic properties were further deteriorated.

The photographic film cartridge proposed in JP-A-6-67348 has a cyan compound content of 10%.
Even when formed from a resin composition containing 0.01 to 10 wt% of furnace carbon black of not more than ppm / carbon weight, photographic properties may be deteriorated.

The present invention solves these problems, has excellent photographic properties, dimensional accuracy, physical strength, injection moldability, scratch resistance, etc., has good slidability, and prevents light fog due to reflected light. Still another object of the present invention is to provide an injection molded article for photographic photosensitive materials, which can prevent deterioration of photographic properties due to harmful gas.

[0012]

According to the present invention, there is provided an injection molded article for a photographic light-sensitive material, which has a melt flow rate (ASTM D1).
238 G condition) 2 to 40 g / 10 min, flexural modulus
(JIS K 7203) A rubbery polymer-containing aromatic monovinyl resin containing 1 to 40% by weight of a rubbery polymer having a molecular weight distribution of 18,000 kg / cm ² or more and a molecular weight distribution of 5 or less.
It is characterized by containing 0.1 to 10 parts by weight of a silicone resin with respect to 0 parts by weight and having a surface reflection glossiness of 45% or less.

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION The injection molded article for a photographic light-sensitive material according to the present invention contains an aromatic monovinyl resin containing a rubbery polymer. Graft polymer of styrene and aromatic monovinyl, mixture of rubbery polymer and aromatic monovinyl resin simply kneaded, graft polymer of rubbery polymer and aromatic monovinyl and aromatic monovinyl resin There are three aspects of the mixture.

The rubbery polymer-containing aromatic monovinyl resin contains 1 to 40% by weight, preferably 1.5% by weight of the rubbery polymer.
-35% by weight, more preferably 2-30% by weight, most preferably 2.5-25% by weight. When the content of the rubbery polymer is less than 1% by weight, the abrasion resistance is inferior, the physical strength is low, and in particular, the spool for photographic film, which is often used under the condition of 0 ° C. or less, is made of resin. Photo film cartridges (eg, APS film cartridges), instant film units, camera bodies, photographic film cartridges, photographic film magazines, and photographic film units with lenses have insufficient strength when dropped and insufficient wear resistance. It is difficult to put into practical use. If the content exceeds 40% by weight, the photographic light-sensitive material (photographic film) is left in a room with the patrone alone for at least 3 months (for example, with the photographic film-containing patrone loaded in the camera). ). As a result,
Over time, fog is increased by 0.03 or more, or sensitivity is partially increased by 20% or more, and density unevenness and color unevenness occur in photographic prints, which makes practical use difficult. Further, the bending elastic modulus becomes small and the glass is easily deformed, so that the suitability for the camera is lost or the light shielding property is poor.

Examples of the rubbery polymer include ethylene / propylene copolymer rubber, ethylene / propylene / non-conjugated diene terpolymer rubber, isoprene copolymer rubber, polyisobutylene rubber, and styrene-isoprene copolymer rubber. , Polybutadiene rubber, butadiene-styrene copolymer rubber, acrylonitrile-butadiene copolymer rubber, and the like. As the polybutadiene rubber, a high cis polybutadiene rubber having a high cis content (preferably, the cis 1,4 bond is 70 mol% or more, Low cis polybutadiene rubber having a low cis content is used together.

Among these rubbery polymers, it is preferable to use one or a mixture of two or more selected from polybutadiene rubber, butadiene-styrene random copolymer rubber and acrylonitrile-butadiene copolymer rubber. By using these rubbery polymers, there is little adverse effect on the photographic properties of the photographic light-sensitive material, and the physical strength can be greatly improved. Further, the surface reflection glossiness of the injection molded product can be reduced.

The average particle size of the rubbery polymer is 0.1
10 to 10 μm is suitable, preferably 0.2 to 7 μm,
More preferably from 0.5 to 5 μm, most preferably from 0.7 to 5 μm.
3.5 μm. When the average particle size is less than 0.1 μm, the surface reflection glossiness increases, the cost increases, the impact strength decreases, and the number of scratches increases. . On the other hand, when the average particle diameter exceeds 10 μm, the surface has large irregularities, and the tensile strength and the like are reduced, which makes it difficult to put into practical use.

When the average particle diameter is small, an injection molded article having a high gloss and a smooth surface can be obtained, but is easily damaged and the polymerization cost is increased. On the other hand, it has been found that when the average particle size is large, reflection is reduced and glossiness is reduced.
Therefore, when trying to obtain a high gloss injection molded product,
Average particle size is 0.1 to 1.5 μm, preferably 0.2 to 1.5 μm
When using a 1.0 μm rubbery polymer resin and trying to obtain a mat-like low gloss injection molded product for anti-reflection,
Average particle size is 1.5 to 10 μm, preferably 1.7 to 7 μm
m, more preferably a rubbery polymer resin of 2.0 to 5 μm. As described above, when an injection molded product having an average particle size of 1.5 to 10 μm is used, light fogging due to light reflection can be prevented without embossing the surface. Further, if embossing is applied, light fogging due to light reflection can be more completely prevented, and therefore, it is preferable to use it for a photographic film spool, a photographic film cartridge made of resin, a film unit with a lens, a camera body, and the like.

The average particle size of the rubbery polymer was calculated by the following equation by cutting out an ultrathin slice with a microtome and photographing it with a transmission electron micrograph, measuring the particle size of 600 rubbery polymers in the photograph. Things. Average particle diameter = {nD ₂ / {nD} where n is the particle diameter, and D is the number of particles of the rubbery polymer.

The average particle size of the rubbery polymer can be adjusted by the stirring conditions during polymerization, the solution viscosity of the rubbery polymer, and the like.

Examples of the aromatic monovinyl resin in the rubbery polymer-containing aromatic monovinyl resin include styrene and o-methylstyrene, p-methylstyrene, m-methylstyrene, p-methylstyrene, m-methylstyrene,
2,4-dimethylstyrene, ethylstyrene, p-te
Nuclear alkyl-substituted styrenes such as rt-butylstyrene, nuclear halogenated styrenes such as 2,4,6-tribromostyrene and 2,4,6-trichlorostyrene, α-methylstyrene, α-methyl-p-methylstyrene, etc. Α-alkyl-substituted styrene and the like are used. In addition, methacrylates, acrylates, acrylonitriles, and maleic anhydride copolymerizable with styrene monomers are also included.

When the rubber-containing aromatic monovinyl resin is a polymer of a rubbery polymer and an aromatic monovinyl (mostly graft polymerization), the polymerization can be carried out by the following polymerization method.

[Radical polymerization method] (1) Batch bulk polymerization method Advantages: Easy production. Disadvantages: Difficult to disperse heat on a large scale. Wide molecular weight distribution and excellent moldability. (2) Continuous bulk polymerization method Advantages: The product quality is uniform. Low production cost. Disadvantage: High viscosity reaction liquid transport. Channeling development in the reaction tower. (3) Continuous solution polymerization method Advantage: Easy to control polymerization heat. Disadvantages: Desolvation is required. The stirring method is difficult. (4) Suspension polymerization method Advantages: Removal of polymerization heat is possible. A granular polymer is obtained. Low residual monomer. Disadvantages: Stain caused by water or stabilizer. Requires devolatilization. Requires drying and pelletizing. (5) Emulsion polymerization method Advantages: High reaction rate. Polymerization heat can be removed. Continuous polymerization is also possible. A latex-like polymer is obtained. Disadvantages: Stain caused by water and emulsifiers Requires drying and pelletizing

[Ion polymerization method] (1) Ion polymerization method Advantages: High reaction rate. Heat of polymerization can be controlled. Disadvantages: Solvent and catalyst powder need to be removed. Requires freezing.

Among these polymerization methods, from the viewpoint of economy, a bulk polymerization method and a bulk-suspension two-stage polymerization method in which a styrene monomer is polymerized by a radical reaction in the presence of a rubbery polymer are preferable, and particularly a continuous polymerization method. The bulk polymerization method is preferable because it is inexpensive and contains little substance that adversely affects the photographic light-sensitive material. Further, suspension polymerization (batch type) is preferred from the viewpoint that the amount of residual monomer is small, the heat resistance is excellent, and the turn is small. In the present invention, those obtained by polymerization by a continuous bulk polymerization method are particularly preferable from the viewpoint of photographic properties, economy and quality stability.

The aromatic monovinyl resin containing a rubbery polymer has a melt flow rate (G condition of ASTM D1238) of 2 to 40 g / 10 min and 2.5 to 35 g / 1.
0 minutes is preferable, 3 to 30 g / 10 minutes is more preferable,
Most preferably, it is 3.5 to 25 g / 10 minutes. If the melt flow rate is less than 2 g / 10 minutes, the fluidity of the resin is poor and short shots and weld lines are often generated.
The molding cycle becomes long and practical use is difficult. Also, 40
If it exceeds g / 10 minutes, physical strength is low, burrs are generated frequently, and thermal deterioration is liable to occur and practical use is difficult.

The rubbery polymer-containing aromatic monovinyl resin has a flexural modulus (JIS K 7203) of 18,000.
And at 0 kg / cm ² or more, preferably 19,000kg / cm ² or more, more preferably 20,000 kg / cm ² or more, 21,000 kg / cm ² or more is most preferable. If the flexural modulus is less than 18,000 kg / cm ² , sufficient rigidity and physical strength cannot be ensured, so that it is easily deformed when an external force is applied, and dimensional accuracy and complete light-shielding properties cannot be secured. Particularly, in the case of a photographic film spool, a photographic film cartridge made of resin, a photographic film cartridge (K16 film, K35 film, etc.) to be used in the camera, if it is deformed, it becomes difficult to load the camera and the photographing cannot be performed.

The aromatic monovinyl resin containing a rubbery polymer has a molecular weight distribution of 5 or less, preferably 4.5 or less, more preferably 4 or less, and most preferably 1.1 to 3.5. If the molecular weight distribution exceeds 5, the dimensional accuracy may deteriorate, and the physical strength may decrease, which may make practical use difficult.

The aromatic monovinyl resin containing a rubbery polymer has an Izod impact strength (JIS K-6871) of 2.
0 kg · cm / cm or more, preferably 2.5 kg · cm / cm or more, more preferably 3.0 kg · cm / cm,
3.5 kg · cm / cm or more is particularly preferable, and 4 kg · cm / cm or more is preferable.
cm / cm is most preferred. 1. Izod impact strength.
When it is less than 0 kg · cm / cm, the physical strength is low, and in particular, there are many opportunities for use in photographic film spools, resin photographic film cartridges,
Instant film units, camera bodies, photographic film units with lenses, sheet photographic film holders, photographic film cartridges, and the like are difficult to put into practical use due to insufficient strength when dropped.

The rubbery polymer-containing aromatic monovinyl resin of the present invention, ABS (acrylonitrile)
The e-butadiene-styrene resin will be described.

(1) Molecular Structure and Characteristic Properties ABS resin is a thermoplastic resin containing acrylonitrile (A), butadiene (B), and styrene (S) as main components. Since the AS copolymer is grafted on the dispersed polybutadiene particles, the polybutadiene particles and the surrounding AS
The compatibility with the continuous phase is good, and no aggregation of the polybutadiene particles is observed.

Since the ABS resin is a graft rubber particle dispersion system similar to the high impact polystyrene (HIPS) resin, the viscoelastic temperature characteristics are as follows.
Divided into dispersion absorption around 0 ° C.

The impact strength, which is the greatest characteristic of the ABS resin, is due to the absorption of impact energy due to deformation of polybutadiene particles and the absorption of impact energy due to formation of craze generated from polybutadiene particle interfaces. In addition to the occurrence of craze, a mechanism for suppressing the propagation of the craze and the destruction of the craze is also important for increasing the impact strength.

In addition to good injection molding processability, rigidity,
Excellent chemical resistance. In addition, coloring with a light-shielding substance is free, and secondary processing properties such as painting, printing, hot stamping, vacuum deposition, and plating are also good. The blend system with other resins such as polycarbonate resin and polyvinyl chloride resin is A
It forms a distinctive product group as a BS alloy. The only drawbacks are that they adversely affect the photographic properties and are inferior in weather resistance. It has been improved by the addition of a modifier and by studying the resin composition, and has become practically usable as an injection molded article of a photographic light-sensitive material.

(2) Production method 1) Graft blending method A polybutadiene latex is reacted with an AN / ST monomer to produce an ABS resin having a high rubber content and a high impact strength, though it has a bad effect on photographic properties when used alone. A predetermined ABS resin is obtained by blending an AS copolymer resin which does not adversely affect the photographic properties of a separately prepared photographic light-sensitive material. Recently, this graft blending method is common. Above, 20 to 45 parts by weight of ABS resin and weight average molecular weight of 1
27.5 to 40 parts by weight of AS copolymer resin of 100,000 or more;
AS copolymer resin having a weight average molecular weight of less than 100,000
A blend of 27.5 parts by weight to give a predetermined ABS resin has good photographic properties, and has an extremely high impact strength, which is preferable as the injection molded article for photographic photosensitive materials of the present invention. 2) Bulk / suspension polymerization method Uncrosslinked rubber is dissolved in ST monomer to perform preliminary bulk polymerization in a rubber matrix state, and when a phase transition to a rubber dispersion state occurs, a suspension-based graft reaction is performed to perform ABS. Obtain resin. Since it is difficult to produce an ABS resin having a high rubber content by this method, the desired ABS resin may be blended with an ABS resin and an AS copolymer resin produced by another method. 3) Emulsion / continuous bulk polymerization method An AN / ST monomer and an electrolyte are added to and mixed with an ABS latex having a high rubber content produced by an emulsion polymerization method, and separated water is removed to form an ABS crumb.
Add the AN / ST monomer to this ABS crumb and add ABS
An ABS resin is obtained by performing continuous bulk polymerization as a dope.
It is said that this method does not require coagulation, washing and drying steps of the ABS resin powder, so that a great cost reduction can be achieved.

(3) Domestic manufacturing car Asahi Kasei Ube Sicon Toray Mitsubishi Rayon Nippon Synthetic Rubber Cooperative Polymer Mitsubishi Monsanto Sumitomo Nogatac Electrochemistry

The rubbery polymer-containing aromatic monovinyl resin as described above is preferably contained in an injection molded article for a photographic light-sensitive material in an amount of 20% by weight or more, more preferably 4% by weight.
It is at least 0% by weight, particularly preferably at least 60% by weight, most preferably at least 80% by weight. If the content of the rubbery polymer-containing aromatic monovinyl resin is less than 20%, dimensional accuracy, physical strength, injection moldability, scratch resistance, slidability, light-shielding properties, and the like cannot be sufficiently exhibited.

Preferred examples of the aromatic monovinyl resin containing a rubbery polymer include those described below. (1) A rubbery polymer-containing aromatic monovinyl resin comprising 20 to 50 parts by weight of a rubbery polymer-containing ABS resin and 80 to 50 parts by weight of an aromatic monovinyl resin. (2) 20 to 45 parts by weight of a rubbery polymer-containing ABS resin (preferably a graft polymer) and 55 to 55 parts of an AS copolymer resin
A rubbery polymer-containing aromatic monovinyl resin composed of 75 parts by weight. (3) 55 to 80 parts by weight of the AS copolymer resin of (2) is an AS copolymer resin having a weight average molecular weight of 100,000 or more 27.5 to 27.5.
A rubbery polymer-containing aromatic monovinyl resin comprising a blend of 40 parts by weight and 40 to 27.5 parts by weight of an AS copolymer resin having a weight average molecular weight of less than 100,000.

The injection molded article for a photographic light-sensitive material according to the present invention comprises the above-mentioned aromatic monovinyl resin containing rubbery polymer 1
The silicone resin is contained in an amount of 0.1 to 10 parts by weight, preferably 0.2 to 8 parts by weight, more preferably 0.4 to 6 parts by weight, particularly preferably 100 parts by weight. 0.5 to 4 parts by weight, most preferably 0.6 to 3 parts by weight. By including the silicone resin, the fluidity of the rubbery polymer-containing aromatic vinyl resin is improved, and as an unexpected effect, the physical strength of the injection molded article for photographic light-sensitive materials of the present invention is improved, Reduces surface reflection gloss. Furthermore, lubricity can be improved. In addition, when used in combination with a light-shielding substance, the dispersibility of the light-shielding substance is improved, and the resin becomes clouded to increase the haze (ASTMD-1003). As a result, the coloring power is improved and the light-shielding property can be improved.

When the content of the silicone resin is less than 0.1 part by weight, the above-mentioned effects cannot be exhibited effectively. On the other hand, when the amount exceeds 10 parts by weight, not only the effect of increasing the amount is not exhibited, but also bleed-out increases and the commercial value decreases.

The most problematic point is that the occurrence of slip with the screw during injection molding increases, making it difficult to inject a fixed amount, causing many short shots, reducing dimensional accuracy, and making it difficult to put into practical use.

Among the silicone resins, silicone oils are preferred because they have the effects described below. (1) The surface of these materials is coated only by using the fibrous filler, the non-fibrous light-shielding substance, and the pigment together to improve dispersibility. (2) Improve the dispersibility of the resin, reduce the motor load on the screw, and prevent the occurrence of melt fracture. (3) Sufficient lubricity can be ensured without adding a fatty acid amide that bleeds out to form a white powder. (4) Reduce the coefficient of friction of the molding material in the heated state. (5) When used in combination with a light-shielding substance, the thermoplastic resin becomes turbid and the haze is increased. As a result, the coloring power can be improved and the light-shielding ability can be improved. Nature can be secured.

The silicone oil preferably has a viscosity at 25 ° C. in the range of 5,000 to 50,000 centistokes, more preferably 7,000 to 40,000 centistokes, and more preferably 9,000. ~ 35,
Particularly preferred are those in the range of 2,000 centistokes,
Most preferred is in the range of 10,000 to 30,000 centistokes. The viscosity of silicone oil is 5,
If it is less than 000 centistokes, there are many unreacted low-molecular-weight substances, which may deteriorate photographic properties (increase in fogging, etc.). On the other hand, if it exceeds 50,000 centistokes, the viscosity is so large that the handleability is poor, so that the resin adheres to the container and cannot be taken out, or the flowability of the resin is reduced, and molding failure may occur.

Examples of the silicone oil include polymethylphenylsiloxane, olefin-modified silicone, amide-modified silicone, polydimethylsiloxane, amino-modified silicone, carboxyl-modified silicone, α-methylstyrene-modified silicone, and polyether modified with polyethylene glycol or polypropylene glycol. Modified silicone, olefin / polyether modified silicone,
It is a silicone oil containing a modified siloxane bond such as an epoxy-modified silicone, an amino-modified silicone, and an alcohol-modified silicone.

Among these silicone oils, olefin-modified silicone, amide-modified silicone, polydimethylsiloxane, olefin-modified silicone, amide-modified silicone, Polyether-modified silicone and olefin / polyether-modified silicone.

An injection molded article for a photographic light-sensitive material containing a rubbery polymer-containing aromatic monovinyl resin and a silicone resin as described above has a surface reflection glossiness (JIS Z 87).
(Measured at an incident angle of 60 degrees and a light receiving angle of 60 degrees according to 41) is 4
It is at most 5%, preferably at most 40%, more preferably at most 35%, particularly preferably at most 30%, most preferably at most 25%. If the surface reflection glossiness exceeds 45%, light fog due to reflected light may occur.

The injection-molded article for a photographic light-sensitive material according to the present invention can contain a black light-shielding substance. By including a black light-shielding substance, light-shielding properties can be imparted to the injection molded article for photographic photosensitive materials, and physical strength can be increased.

The black light-shielding substance preferably contains 0.05 to 10 parts by weight of the black light-shielding substance with respect to 100 parts by weight of the rubbery polymer-containing aromatic monovinyl resin.
More preferably, the content is 0.1 to 8 parts by weight.
It is particularly preferable to contain 5 to 6 parts by weight, and 0.2 to 4 parts by weight.
Most preferably, it is contained by weight.

If the content of the black light-shielding substance is less than 0.05 parts by weight, the effect of addition is small and sufficient light-shielding properties may not be ensured unless the thickness is increased. If the content is more than 10 parts by weight, the fluidity of the resin will be deteriorated, the effect of adding the resin will not be obtained, and the cost will only increase, and silver, short shots and bumps may be generated. .

Examples of the black light-shielding substance include carbon black, graphite, black iron oxide, carbon fiber, carbon hollow sphere, and the like. Among these black light-shielding substances, carbon black is preferable because it hardly adversely affects photographic properties, is stable to heat even at 150 ° C. or higher, and has excellent heat resistance and light resistance.

Examples of classification based on the raw material of carbon black include gas black, furnace black, channel black, anthracene black, acetylene black, Ketjen carbon black, thermal black,
There are lamp black, oil smoke, pine smoke, animal black, vegetable black and the like.

Representative examples of preferred commercial products of carbon black include, for example, carbon black # 2 manufactured by Mitsubishi Kasei.
0 (B), # 30 (B), # 33 (B), # 40 (B), # 41
(B), # 44 (B), # 45 (B), # 50, # 55, # 1
00, # 600, # 950, # 1000, # 2200
(B), # 2400 (B), MA8, MA11, MA100
And the like.

Overseas products include, for example, Black Pearls 2, 46, 70, 71, 7 of Cabot Corporation.
4,80,81,607 etc., Regal 300,330,4
00, 660, 991, SRF-S etc., Vulcan 3,
6, Sterling 10, SO, V, S, FT-F
F, MT-FF and the like.

Further, Unit of Ashland Chemical Co., Ltd.
ed R, BB, 15,102,3001,3004,30
06,3007,3008,3009,3011,301
2, XC-3016, XC-3017, 3020, etc., but are not limited thereto.

Channel black produced by contacting the back side of channel steel while incompletely burning a gas flame of natural gas or gaseous or vaporous hydrocarbon in these various carbon blacks to precipitate carbon black. Although they have high coloring power, they have poor photographic properties and pollute the air during production, and are not preferred in the present invention in terms of photographic properties and environmental problems.

The preferred carbon black in the present invention is a partially blackened or thermally decomposed acetylene black and a natural gas, a hydrocarbon oil or a mixture thereof in a furnace at 1200 ° C. to 1700 ° C. Furnace black manufactured by the company.

When applied to the injection molded product for photographic light-sensitive material according to the present invention, at least one of creosote oil and ethylene bottom oil is used as a raw material oil so as not to adversely affect the photographic properties of the photographic light-sensitive material. 1200 ℃ -17
Furnace carbon black produced by continuous partial combustion in a furnace at 00 ° C. or by thermal decomposition is preferred. By using such a furnace carbon black, since the sulfur component is small, the adverse effect on the photographic material can be reduced.

ASTM D 1619-6 in injection molded articles
The sulfur content by the measurement method of 0 is 0.9% or less, preferably 0.7% or less, particularly preferably 0.5% or less, and most preferably 0.1% or less. If the content is not limited to this range, adverse effects on the photographic properties of the photographic light-sensitive material, such as an increase in fog, abnormal sensitivity, abnormal occurrence, etc. In particular, a free sulfur component which has a great adverse effect on the photographic properties of the direct photographic light-sensitive material. Each sample is solidified by cooling with liquid nitrogen and then pulverized. 100 g of the pulverized sample is placed in a Soxhlet extractor and extracted with chloroform at 60 ° C. for 8 hours. The total volume is 100 ml. 10m of this solution
1 is injected into a high performance liquid chromatograph and sulfur is determined. High-performance liquid chromatographic separation conditions are column; ODS
Silica column (4.6φ × 150 mm), separation solution: methanol 95 and water 5 (acetic acid and triethylamine were each added to 0.1% each).
1%), flow rate: 1 ml / min, detection wavelength: 254n
m, Quantification is performed by the absolute calibration curve method. ｝ Is 0.1%
Or less, preferably 0.05% or less, particularly preferably 0.1% or less.
01% or less. Although expensive, acetylene black having a sulfur content of 0.1% or less has an ISO sensitivity of 100.
It is suitable for maintaining high photographic properties satisfactorily as described above for high-sensitivity photographic materials.

For this purpose, the selection of the raw material is important. For example, the above-mentioned sulfur content is as follows. Raw material Oil name Sulfur content in feed oil Creosote oil ｛Coal-based feedstock｝ 0.3-0.6% Ethylene bottom oil ｛Naphtha feedstock (petroleum-based feedstock)｝ 0.05-0.1% Ethylene bottom oil ｛ Gas oil feedstock (petroleum-based feedstock)｝ 0.2-1.5% Fluid catalytic cracking residue oil ｛petroleum-based feedstock｝ 0.2-4.0%

Therefore, as the raw material oil, ethylene bottom oil derived from creosote oil and petroleum is preferable, and ethylene bottom oil derived from naphtha having a sulfur content of 0.05 to 0.1% is produced. Carbon black is most preferred because it can reduce the sulfur content in carbon black to 0.1% by weight or less.

The production method is as follows.
00 ° C to 1700 ° C, preferably 1250 ° C to 1600
Furnace carbon black produced in a furnace at 0 ° C. is preferred.

In particular, free sulfur which has been found to have a direct adverse effect on the photographic properties of photographic light-sensitive materials (free sulfur)
hur) content (quantification according to JIS K 6350) is 100 ppm or less, preferably 50 ppm or less,
Particularly preferably 20 ppm or less, most preferably 10 p
pm or less of carbon black. In view of the fact that the free sulfur content is low, in the present invention, naphtha is used to produce ethylene bottom oil by continuous partial combustion in a furnace at 1250 ° C. to 1600 ° C. or by thermal decomposition. Furnace carbon black is most preferred.

The content of cyanide (particularly hydrogen cyanide gas) which deteriorates the photographic properties (the value obtained by converting the amount of hydrogen cyanide determined by 4-pyridinecarboxylic acid / pyrazolone absorption spectrometry into ppm unit based on the weight of the light-shielding substance) is 20.
ppm or less, preferably 10 ppm or less, particularly preferably 5 ppm or less, most preferably 1 ppm or less,
Chemically sensitized materials such as gold sensitization, selenium sensitization, and dye sensitization, particularly gold-sensitized photographic materials, are susceptible to adverse effects on photographic properties due to hydrogen cyanide gas and the like. (Indicated as a scavenger).

Hydrogen cyanide gas scavengers are compounds that convert hydrogen cyanide gas to an adsorbed or photographically inert substance. The hydrogen cyanide gas scavenger should not release substances that adversely affect the silver halide photosensitive material as a result of capturing the hydrogen cyanide gas. Suitable hydrogen cyanide gas scavengers can be selected from inorganic or organic compounds of noble metals. Particularly preferred are palladium (II or IV; oxidation state; the same applies hereinafter) and platinum (II or IV) compounds. Gold (I or III) compounds are also preferred. rhodium
(III), iridium (III or IV) and osmium (I
Compounds of the type I, III or IV) are also effective, but higher amounts are required to achieve an equivalent effect. Specific examples of useful inorganic or organic noble metal compounds include, for example, Gmelin Handbook.
Commercial, synthetic and ins
Itu synthetic products can be used with a purity that does not adversely affect the photographic light-sensitive material.

Preferred palladium compounds include palladium (II) chloride, palladium (II) bromide, palladium (II) hydroxide, palladium (II) sulfate, palladium (II) thiocyanate, and tetrachloropalladium (II) acid salt. (Sodium salt, potassium salt, ammonium salt), hexachloropalladium (IV), tetrabromopalladium (II), hexapromoparadymate (IV), bis (salicylate) paradimum (II), bis (Dithiooxalato-
S, S ′) palladium (II) salt, trans-dichlorobis (thioether) palladium (II), tetraamminepalladium (II) salt, dichlorodiamminepalladium (II),
Dibromodiammine palladium (II), oxalatodiammine palladium (II), dinitrodiammine palladium (I
I), bis (ethylenediamine) palladium (II) salt, dichloroethylenediaminepalladium (II), bis (2,2′-
Pyridine) palladium (II) salt, bis (1,10-phenanthroline) palladium (II) salt, tetranitropalladium (II) salt, bis (glycinato) palladium (II), tetrakis (thiocyanato) palladium (II) salt , Dichlorobis (phosphine) palladium (II), dichlorobis (phosphine) palladium (II), di-μ-chloro-bis [chloro (phosphine) palladium (II)], di-μ-chloro-bis [chloro (arsine ) Palladium (II)] and dinitrobis (arsine) palladium (II).

Preferred platinum compounds include platinum chloride (I
I) acid salt, platinum chloride (IV), hexafluoroplatinate (IV),
Tetrachloroplatinate (II), hexachloroplatinate (IV), trichlorotrifluoroplatinate (IV), tetrabromoplatinate (II), hexabromoplatinate (IV), dibromodichloroplatinate (II) Salt, hexahydroxoplatinate (IV), bis (oxalato) platinate (II), dichlorobis (oxalatoplatinate (IV), bis (thiooxalato) platinum
(II) acid salt, bis (acetylacetonato) platinum (II), bis (1,1,1,5,5,5-hexafluoro-2,4-pentanedionato) platinum (II), bis (1 , 1,1-trifluoro-2,4-pentanedionato) platinum (II), tetrakis (thiocyanato) platinate (II), hexakis (thiocyanato) platinate (IV), bis (Z) -1 2,2-dicyanoethylene-1,2-dithiolatoplatinum (II), dichlorobis (diethylsulfide) platinum (II), tetrachlorobis (diethylsulfide) platinum (IV), bis (glycinato) platinum (II), Dichloroglycinatoplatinate (II), dichlorobis (triethylphosphine) platinum (II), chlorohydridobis (triethylphosphine) platinum (II), tetraammineplatinum (II) salt, tetrachloroplatinate (II) salt, dichlorodiammine Platinum (II), trichloroammineplatinum (II)
Salt, hexaammineplatinum (IV) salt, chloropentaammineplatinum (IV) salt, tetrachlorodiammineplatinum (IV), dinitrodiammineplatinum (II), dichlorotetrakis (methylamine) platinum (IV) salt, dichloro (ethylenediamine) platinum
(II), bis (ethylenediamine) platinum (II) salt, tris (ethylenediamine) platinum (IV) salt, dichlorobis (ethylenediamine) platinum (IV) salt, dichlorodihydroxo (ethylenediamine) platinum (IV), tetrakis (pyrimidine) platinum (II) salt, dichlorobis (pyridine) platinum (II), bis (2,2′-pipyridine) platinum (II) salt, tetranitroplatinum
(II), chlorotrinitroplatinate (II), dichlorodinitroplatinate (II), dibromodinitroplatinate (II),
Hexanitroplatinate (IV), chloropentanitroplatinum (I
V), dichlorotetranitroplatinate (IV), trichlorotrinitroplatinate (IV), tetrachlorodinitroplatinum
(IV), dibromodichlorodinitroplatinate (IV), trichloro (ethylene) platinate (II), di-μ-chloro-
Bis (chloro (ethylene) platinum (II), trans-dichloro (ethylene) (pyridine) platinum (II), bis [bis (β-
Mercaptoethylamine) nickel (II) -S, S "-platinum
(II) salts and dichlorodicarbonylplatinum (II).

Gold (I or III), rhodium (III), iridium (III or IV) and osmium (II, III or
The compound of the formula IV) can be used in the same manner. For example, potassium tetrachloroaurate (I
II), rhodium (III) chloride, potassium hexachloroiridate (IV), potassium tetrachloroylate
(III) and potassium hexachloroosmate (IV). The inorganic or organic compound of the noble metal is not limited to the above specific examples as long as the effects of the present invention can be obtained.

The content of the hydrogen cyanide scavenger is preferably 0.01 to 10 parts by weight, more preferably 0.02 to 8 parts by weight, per 100 parts by weight of the rubbery polymer-containing aromatic monovinyl resin. Particularly preferably, it is 0.03 to 6 parts by weight, most preferably 0.04 to 5 parts by weight. If the content of the hydrogen cyanide scavenger is less than 0.01 parts by weight, the hydrogen cyanide cannot be effectively adsorbed and removed. On the other hand, if it exceeds 10 parts by weight, the effect of increasing the amount is not exhibited, and it is only expensive. Further, the fluidity of the resin is deteriorated, a weld line (also referred to as a weld mark) is strongly generated, and the impact strength is reduced.

Particularly preferred carbon blacks have an iodine adsorption amount (measured according to JIS K 6221) relating to the dispersibility, conductivity and light-shielding ability of carbon black of 20.
mg / g or more, preferably 30 mg / g or more, particularly preferably 50 mg / g or more, and most preferably 80 mg / g.
Above, and dibutyl phthalate (DBP), oil absorption
(Measured by JIS K 6221) is 50 ml / 100 g or more, preferably 60 mg / 100 g or more, particularly preferably 70 ml / 100 g or more, and most preferably 100 ml.
/ 100 g or more of carbon black.

In the present invention, furnace carbon black is preferred for the purpose of improving light-shielding properties, cost, and physical properties. Examples of expensive light-shielding substances having an antistatic effect include various conductive carbon blacks and acetylene carbon blacks of various companies. Ketchen carbon black, which is a by-product carbon black, is preferred. Particularly, for a high-sensitivity (ISO sensitivity of 400 or more) photographic light-sensitive material, the sulfur content is set to 0.1.
Furnace carbon black produced by continuously partially burning or thermally decomposing 1% or less of acetylene black and ethylene bottom oil from naphtha as raw materials in a furnace at 1250 ° C. to 1600 ° C. is preferable.

The carbon black having an antistatic effect has an average particle size of 12 to 50 μm (= nm), DB
There are various conductive carbon blacks having a P oil absorption of 100 ml / 100 g or more, such as acetylene black, conductive furnace black (CF), superconductive furnace black (SCF), extra conductive furnace black (XCF), and conductive channel black (CC). ) And 1500
Furnace black or channel black heat-treated at a high temperature of about ° C can be used. Specific examples of acetylene black include Denka acetylene black (manufactured by Denki Kagaku) and Shaunigan acetylene black (manufactured by Shaunigan Chemical Co., Ltd.). Specific examples of the conductive furnace black include Continex CF (Continental Carbon). Co., Ltd.),
Specific examples of Vulcan C (manufactured by Cabot Corporation) and Super Conductive Furnace Black are specific examples of Continex SCF (manufactured by Continental Carbon Co., Ltd.) and Vulcan SC (manufactured by Cabot Corporation). Examples thereof include Asahi HS-500 (manufactured by Asahi Carbon Co., Ltd.) and Vulcan XC-72 (manufactured by Cabot Corporation). Specific examples of the conductive channel black include Kolux L (manufactured by Degussa Corporation). Ketjen Black EC and Ketjen Black EC-600JD (Ketjen Black International Co., Ltd.), which are a kind of furnace black, can also be used.

Among them, acetylene black is particularly low in the content of impurities such as sulfur component and hydrogen cyanide which adversely affect the photographic properties of the photographic light-sensitive material, and has a developed secondary structure structure. ,
Since it has excellent dispersibility and conductivity, it is preferably used.
Further, Ketjen Black EC, Ketjen Black EC-600JD, and the like, which have an excellent specific surface area and exhibit excellent conductivity even at a low filling amount, can also be preferably used.

The conductive carbon black is added in an amount of 0.05 to 10 parts by weight, preferably 0.1 to 10 parts by weight, per 100 parts by weight of the resin component.
The amount is preferably from 1 to 8 parts by weight, particularly preferably from 0.15 to 6 parts by weight, most preferably from 0.2 to 4 parts by weight. If the amount is less than 0.05 part by weight, desired light-shielding properties and conductivity may not be obtained. If the amount exceeds 10 parts by weight, the effect of increasing the amount is not exhibited and the cost is increased. Further, physical strength, resin flowability and injection moldability may be reduced, or weld lines may be generated.

In order to improve the dispersibility of carbon black and the like and to improve the photographic properties, it is preferable to include a fatty acid metal salt as a dispersant. Fatty acid metal salts include higher fatty acids such as lauric acid, stearic acid, succinic acid, stearyl lactic acid, lactic acid, phthalic acid, benzoic acid, hydroxystearic acid, ricinoleic acid, naphthenic acid, oleic acid, palmitic acid, erucic acid and Li , Na, M
g, Ca, Sr, Ba, Zn, Cd, Al, Sn, P
Compounds with metals such as b, Cd and the like are mentioned, and preferred are magnesium stearate, calcium stearylate, sodium stearate, zinc stearate, zinc oleate, magnesium oleate and the like.

The names, molecular formulas, states and melting points of typical commercially available fatty acid metal salts are shown below.

[0076]

[Table 1]

It is preferable that the injection molded article for photographic light-sensitive materials according to the present invention contains an aliphatic alcohol fatty acid ester. By containing an aliphatic alcohol fatty acid ester, it should have a moderate slipperiness, prevent water droplets from adhering at room temperature after storage in a low-temperature warehouse for a long period of time, and provide antistatic properties. Can be.

This aliphatic alcohol fatty acid ester is composed of an aliphatic alcohol having 1 to 10 carbon atoms and an aliphatic alcohol having 10 to 10 carbon atoms.
Compounds with 20 fatty acids, specifically, monoglycerin oleate, polyglycerin oleate, glycerin triricinoleate, glycerin acetyl resinolate, methyl acetyl resinolate, ethyl acetyl resinolate, butyl acetyl resinolate, propylene Glycol oleate, propylene glycol laurate, pentaerythritol oleate, polyethylene glycol oleate, polypropylene glycol oleate, polyoxyethylene glycerin, polyoxypropylene glycerin, sorbitan oleate, sorbitan laurate, polyethylene glycol sorbitan oleate, polyethylene glycol Sorbitan laurate,
And polyalkylene ether polyols.

The content of the aliphatic alcohol fatty acid ester is preferably 0.1 to 5 parts by weight, more preferably 0.2 to 4 parts by weight, based on 100 parts by weight of the rubbery polymer-containing aromatic monovinyl resin. Is more preferable, and 0.
The amount is particularly preferably 3 to 3 parts by weight, most preferably 0.4 to 2 parts by weight.

When the content of the aliphatic alcohol fatty acid ester is less than 0.1 part by weight, the effects such as slipperiness and antistatic property cannot be exhibited effectively. On the other hand, if the amount exceeds 5 parts by weight, the effect of increasing the amount is hardly exhibited, and only the material cost increases.

Depending on the type, the slip between the resin composition and the screw of the extruder becomes large, so that a certain amount of injection cannot be secured, or the bleed-out to the surface of the injection-molded product over time lowers the commercial value. .

The injection-molded article for a photographic light-sensitive material according to the present invention preferably contains a 1,2-polybutadiene-based thermoplastic elastomer. By incorporating a 1,2-polybutadiene-based thermoplastic elastomer, it is possible to compatibilize a plurality of different types of thermoplastic resins including a rubbery polymer-containing aromatic monovinyl resin.

The content of the 1,2-polybutadiene-based thermoplastic elastomer is preferably 0.05 to 100 parts by weight, more preferably 0.1 to 80 parts by weight, based on 100 parts by weight of the rubbery polymer-containing aromatic monovinyl resin. Is more preferable, and 0.2 to
Particularly preferred is 60 parts by weight, most preferably 0.5 to 40 parts by weight.

When the content of the 1,2-polybutadiene-based thermoplastic elastomer is less than 0.05 part by weight, the compounding effect is not obtained and only the cost is increased. On the other hand, if it exceeds 100 parts by weight, there is no effect of increasing the amount, and only the material cost increases. Further, problems such as insufficient rigidity also occur.

The photographic light-sensitive material injection molded article according to the present invention preferably contains a formaldehyde scavenger. Formaldehyde scavengers
A compound that can absorb (capture) formaldehyde by reacting with formaldehyde, and can prevent the adverse effects of formaldehyde (a large irritating odor, harmful to the human body, and deteriorating photographic properties). Particularly effective when used in combination with zeolites that adsorb and detoxify aldehyde gas, the use of inexpensive materials containing aldehyde or recycled resins that are commercially available does not adversely affect photographic properties and gives users a bad smell or pungent odor. It is preferable because it gives no discomfort.

As the formaldehyde scavenger, polyamide resin, amide compound, urethane compound,
Examples include ethylene / vinyl alcohol copolymer, pyridine derivative, pyrrolidone derivative, urea derivative, triazine derivative, hydrazine derivative, organic amino compound, imide compound, and amidine compound. As a specific example, N,
N-dimethylformamide, N, N-dimethylacetamide, N, N-diphenylformamide, N, N-diphenylacetamide, N, N-diphenylbenzamide,
N, N, N ', N'-tetramethylazibamide, oxalic acid dianilide, adipic acid dianilide, N-phenylacetanilide, nylon 6, nylon 66, nylon 66 /
6 binary copolymer, nylon 6/10 binary copolymer, nylon 66/10 binary copolymer, nylon 6/66 binary copolymer, nylon 6/12 binary copolymer, nylon 6 /
66/10 terpolymer, nylon 6/66/10/1
Lactams such as quaternary copolymer, nylon 66/66/10 terpolymer, nylon 11, nylon 12, etc., homopolymer or copolymer, adipic acid, sebacic acid,
Decanedicarboxylic acid, dicarboxylic acid such as dimeric acid and ethylenediamine, tetramethylenediamine, hexamethylenediamine, homopolymer or copolymer of polyamide derived from diamine such as metaxylylenediamine, lactams and dicarboxylic acid and Polyamide copolymer derived from diamine, polyacrylamide,
Polymethacrylamide, N, N-bis (hydroxymethyl) suberamide, poly (γ-methylglutamate),
Amide compounds such as poly (γ-ethylglutamate), poly (N-vinyllactam) and poly (N-vinylpyrrolidone); diisocyanates such as toluene diisocyanate and diphenylmethane diisocyanate; and glycols such as 1,4-butanediol and poly (tetra) Methylene oxide) glycol, polybutylene adipate,
Polyurethanes derived from high molecular weight glycols such as polycaprolactone, melamine, benzoguanamine, acetoguanamine, N-butylmelamine, N-phenylmelamine, N, N'-diphenylmelamine, N, N ', N''-triphenylmelamine , N-methylolmelamine, N, N '
-Dimethylolmelamine, N, N ', N''-trimethylolmelamine, 2,4-diamino-6-benzyloxytriazine, 2,4-diamino-6-butoxytriazine, 2,4-diamino-6-cyclohexyl Triazine derivatives such as triazine, melem, melam, N-phenylurea, N, N'-diphenylurea, thiourea, 1-hydroxyurea, 1-methylurea, 1-ethylurea, 1-
Acetyl-3-methylurea, 1,1-diphenylurea,
1- (4-ethoxyphenyl) urea, methylurea, ethylurea, dimethylurea, diethylurea, ethyleneurea,
Guanylurea, guanylthiourea, acetylurea, propyleneurea, 5-hydroxypropyleneurea, 5-methoxypropyleneurea, 5-methylpropyleneurea,
Urea derivatives such as 4,5-dimethoxyethylene urea, N-phenylthiourea, N, N'-diphenylthiourea, nonamethylene polyurea, phenylhydrazine, diphenylhydrazine, methylhydrazine, ethylhydrazine, n
-Propylhydrazine, n-butylhydrazine, ethylene-1,2-dihydrazine, propylene-1,2-dihydrazine, butylene-1,4-dihydrazine, hydrazine of benzaldehyde, semicarbazone of benzaldehyde, 1-methyl of benzaldehyde Hydrazine derivatives such as 1-phenylhydrazine, thiosemicarbazone, hydrazine of 4- (dialkylamino) benzaldehyde, imides such as succinimide, phthalimide, succinimide, hydantoin, 1-methylol-5,5-dimethylhydantoin and isocyanuric acid Compound, dicyandiamide, pyrrolidine, piperidine, morpholine,
Guanamine, guanidine, guanidine, aminoguanidine, guanine, guanacrine, guanochlor, guanoxane, guanosine, amiloride, N-amidino-3
Amidine compounds such as -amino-6-chloropyrazinecarboxamide, poly (2-vinylpyridine), poly (2-methyl-5-vinylpyridine), poly (2-ethyl-5-vinylpyridine), 2-vinylpyridine -2-
Pyridine derivatives such as methyl-5-vinylpyridine copolymer and 2-vinylpyridine-styrene copolymer. Among them, polyamide such as terpolymer of nylon 6/66/610, quaternary copolymer of nylon 6/66/610/12, dimer acid polyamide, melamine,
Guanamine, benzoguanamine, acetoguanamine, N
-Methylol melamine, N, N'-dimethylol melamine, N, N ', N''-trimethylol melamine, N-methylol benzoguanamine, thermoplastic polyurethane resin,
Dicyandiamide, guanidine, poly (N-vinylpyrrolidone), poly (2-vinylpyridine), N, N'-diphenylurea, polyurea, melem, and melam are preferred.

The content of the formaldehyde scavenger is 0.001 to 40 parts by weight, based on 100 parts by weight of the rubbery polymer-containing aromatic monovinyl resin.
Preferably 5 to 30 parts by weight, more preferably 0.01 to 20 parts by weight, particularly preferably 0.05 to 10 parts by weight,
Most preferred is 0.1 to 5 parts by weight. 0.001 content
When the amount is less than parts by weight, there is almost no effect of addition,
If the amount exceeds 40 parts by weight, the effect of increasing the amount is small, and the cost is merely increased.

[0088] The zeolite is aluminosilicate having a three dimensional skeletal structure is represented by _{XM 2 / n O · Al 2} O 2 · YSiO 2 · ZH 2 O as a general formula. (M is an ion-exchangeable ion, generally a monovalent or divalent metal ion; n is the valence of the metal ion; X and Y are the coefficients of the respective metal oxides and silica; and Z is the water of crystallization. Is a number.)

Specific examples of the zeolite include A-type zeolite, B-type zeolite, D-type zeolite, L-type zeolite, NA-type zeolite, PC-type zeolite, R-type zeolite, T-type zeolite, W-type zeolite, and X-type zeolite. Examples include zeolites, Y-type zeolites, ZK-5-type zeolites, high silica zeolites, hydroxycanclinite, analcyme, chabazite, faujasite, mordenite, sodalite, hydroxysodalite, erionite, clinobutyrolite and the like. Among these, harmful gases (free sulfur gas,
Hydrogen cyanide gas, formaldehyde gas, chlorine gas,
A-type zeolite having a large adsorption and detoxifying ability is preferred.

The zeolites include natural zeolites (analcime, chabazite, heula).
ndite, erionite, ferrierit
zeolites containing e, laumontite, and moderatenite), synthetic zeolites (A, NA,
X, Y, hydroxyl sodalite, ZK-
5, B, R, D, T, L, hydroxy, cancrin
various types of zeolites such as ITE, W, Zeolaon, etc.).

The zeolite used in the present invention may be either a natural zeolite or a synthetic zeolite.
It is indispensable that it is inexpensive, has a low impurity content that adversely affects the photographic properties of the photosensitive material, has good dispersibility, and has a primary average particle size of 20 μm or less by electron microscopy, and 0.1 to 10 μm. Is preferred, preferably 0.2 to 8 μm, more preferably 0.3 to 8 μm.
-6 μm, particularly preferably 0.4-5 μm, most preferably 0.5-4 μm. It is essential that the secondary average particle diameter by electron microscopy be 50 μm or less.

A metal ion-containing zeolite obtained by adding a metal ion to zeolite is preferable. The metal ion-containing zeolite is an ion-exchangeable ion in zeolite,
For example, one obtained by substituting a part or all of sodium ions, potassium ions and the like with one or more ions among metal ions such as silver ions, manganese ions, nickel ions, and copper ions.

By using metal ion-containing zeolites, an action as an antibacterial agent can be exerted. In particular, hydrophilic biodegradable materials such as gelatin and polyvinyl alcohol which are easily absorbed due to water absorption and are easily biodegradable. The quality of a photographic material using a photographic emulsion layer, a protective layer and a back layer containing a molecule as a main component can be maintained well for a long period of time.

Among the above metal ion-containing zeolites, silver ion-containing zeolites (hereinafter referred to as silver zeolites) are preferable. Silver ions are contained in the zeolite in an amount of 0.01 to 30 in view of improving photographic properties (to make the sulfur compound harmless) and antibacterial properties.
%, Preferably 0.05 to 25% by weight, more preferably 0.1 to 20% by weight, particularly preferably 0.5 to 15% by weight, most preferably 1 to 10% by weight. If the silver ion content is less than 0.01% by weight, there is no effect of the content, and only the production cost increases. Content is 30% by weight
Beyond this, there is no effect of increasing the amount, but only an increase in material costs and an increase in manufacturing costs.

Further, a zeolite containing a total of two or more metal ions of silver ions and at least one metal ion selected from the group consisting of manganese, nickel and copper is particularly preferred. By using such a zeolite containing two or more kinds of metal ions, various photographic hazardous compounds (for example, gases such as formaldehyde, chlorine, hydrogen chloride, hydrogen sulfide, sulfurous acid, and hydrogen cyanide) contained in the air can be used. Detoxification can be promoted, and the photosensitive material, which is an ultra-fine chemical product, can be maintained in good quality for a long period of time (2 years or more). The content of at least one metal ion selected from the group consisting of manganese, nickel and copper is 0.01 to 15% by weight, preferably 0.05 to 13% by weight, more preferably 0.1 to 11% by weight.
%, Particularly preferably 0.5 to 9% by weight, most preferably 1 to 7% by weight.

Therefore, silver ion, manganese ion,
A zeolite having a large milliequivalent (hereinafter referred to as meq) having an ion exchange capacity capable of exchanging one or more metal ions in nickel ions and copper ions is preferable. Particularly, an aluminosilicate of A-type zeolite crystal having an ion exchange capacity of 2 meq / g or more is preferable. Illustrating the ion exchange capacity of a zeolite of 2 meq or more (meq = milliquivalent), the leader write is 11.5 me
q / g, 7 meq / g for A-type zeolite, 3.5 meq / g for T-type zeolite, 6.5 me for X-type zeolite
q / g, 5 meq / g for Y-type zeolite, 5 meq / g for analcyme, 5 meq / g for chabazite, 4 meq / g for erionite, 2.5 meq / g for mordenite, and 2.5 meq / g for clinobutylite.

The most preferred zeolites among these are:
Reader light with an ion exchange capacity of 5 meq / g or more, A
Zeolite, T-type zeolite, X-type zeolite, Y-type zeolite, analcyme and chabazite.

The most preferred zeolites are inexpensive, have good manufacturability, are easily available, and adsorb harmful gases such as sulfur compound gas, free sulfur gas, aldehyde compound gas such as formaldehyde gas, and cyanide compound gas which adversely affect photographic properties. It is an A-type zeolite having a large detoxification capacity and a large metal ion exchange capacity (7 meq / g).

The production of the zeolite containing silver ions used in the present invention is carried out by bringing the zeolite into contact with a mixed aqueous solution containing silver ions prepared in advance and metal ions such as manganese ions, nickel ions, and copper ions as required, and adding sodium ions in the zeolite. An ion-exchangeable ion such as an ion or a potassium ion is replaced with the metal ion. The contact is performed at 10 to 100 ° C, preferably 20 to 90 ° C, more preferably 30 to 80 ° C, particularly preferably 35 to 70 ° C,
Most preferably, at a temperature of 40 to 60 ° C, for 1 to 28 hours, preferably 2 to 26 hours, more preferably 4 to 24 hours.
It is carried out for a time, most preferably for 6 to 22 hours, in a batch or continuous manner.

The pH of the mixed aqueous solution is 3 to 10,
It is preferably adjusted to 4 to 9, particularly preferably 5 to 8.
By adjusting the pH in this manner, precipitation of silver oxide or the like on the zeolite surface or in pores can be prevented. Each metal ion in the mixed aqueous solution is supplied as a salt. For example, silver ions are supplied as silver nitrate, silver acetate, silver sulfate, silver perchlorate, etc., manganese ions are supplied as manganese nitrate, manganese sulfate, manganese acetate, etc., and nickel ions are nickel nitrate, nickel perchlorate, acetic acid. Copper ions are supplied as nickel and the like, and copper ions are supplied as copper nitrate, copper acetate, copper sulfate, copper perchlorate and the like. After the ion-exchanged zeolite is sufficiently washed with water, it is dried at, for example, normal pressure of 120 to 500 ° C. or reduced pressure (1 to 50 torr) at 100 to 300 ° C. so that the water content becomes 15% or less.

The above-mentioned zeolite and / or zeolite containing metal ions have a water content of 15% or less, preferably 1% or less.
It is at most 3%, more preferably at most 11%, particularly preferably at most 9%, most preferably at most 7%. If it exceeds 15%, molding failure frequently occurs. The content of the metal ion-containing zeolite and / or zeolite in the injection molded article is 0.1 to 40% by weight, preferably 0.2 to 35% by weight, more preferably 0.4 to 30% by weight, and particularly preferably. 0.8 to 25% by weight, most preferably 1.5 to 20% by weight. If the content is less than 0.1% by weight, the effect of addition is small and the kneading cost increases, and if it exceeds 40% by weight, there is no effect of increasing the amount and the material cost increases.

The injection molded article for photographic light-sensitive materials according to the present invention preferably contains an antioxidant. By including an anti-aging agent, it is possible to prevent aging of the thermoplastic resin used such as an aromatic monovinyl resin containing a rubbery polymer.

The injection-molded article for a photographic light-sensitive material of the present invention is characterized in that the antioxidant is added in an amount of 0.0 to 100 parts by weight of a thermoplastic resin containing a rubbery polymer-containing aromatic monovinyl resin or the like.
01 to 10 parts by weight, preferably 0.005 to 8
Parts by weight, more preferably 0.01 to 6 parts by weight, particularly preferably 0.02 to 4 parts by weight, most preferably 0.03 to 3 parts by weight.
2 parts by weight are contained.

When the content of the antioxidant is 100 thermoplastic resin,
If the amount is less than 0.001 part by weight relative to 100 parts by weight of a thermoplastic resin (excluding a thermoplastic elastomer), the composition will not have a sufficient antiaging effect. Vulcanization disorders and significant bleed-out occur in the product.

Examples of the antioxidant include naphthylamines such as phenyl-β-naphthylamine, N, N′-diphenylethylenediamine, dialkyldiphenylamine,
Diphenylamines such as N, N'-diphenyl-p-phenylenediamine and N-phenyl-N'-isopropyl-p-phenylenediamine; N, N'-diphenyl-p-
P-phenylenediamines such as phenylenediamine,
6-ethoxy-2,2,4-trimethyl-1,2-dihydroquinaline, poly (2,2,4-trimethyl-1,2-dihydroquinoline, 6-ethoxy-1,2-dihydro-
Hydroquinone derivatives such as 2,2,4-trimethylquinoline, monophenols such as 2,6-di-t-butyl-4-methylphenol, 2,2′-methylene-bis- (4-
Ethyl-6-t-butylphenol), 2,2'-methylene-bis- (4-methyl-6-t-butylphenol), 4,4'-butylidene-bis- (6-t-butyl-
Polyphenols such as 3-methylphenol), 4,
There are thiobisphenols such as 4′-thiobis- (6-t-butyl-3-methylphenol), 2-mercaptobenzimidazole, zinc salt of 2-mercaptobenzimidazole, 2-mercaptomethylbenzimidazole and the like. It is arbitrarily compounded according to each characteristic.

Further, various oxidation disclosed in Antioxidant Handbook (published on October 25, 1977 by KK Taiseisha) and Plastic Data Handbook (published on April 5, 1984 by the KK Industrial Research Association) at pages 794 to 799. Antioxidants and various antioxidants disclosed on pages 327 to 329 of the Plastic Additives Data Collection (published by KK Chemical Industry Co., Ltd.) and PLASTICS AGE ENCYCLOPE
When various antioxidants disclosed on pages 211 to 212 of DIA Advanced Edition, 1986 (published by KK Plastic Age) are used together with an antioxidant, the effects of preventing heat deterioration and thermal decomposition are increased, and physical strength is reduced. This is preferable because it can prevent the occurrence of substances that adversely affect photographic properties.

Among the antioxidants which are preferably used together with the above-mentioned antioxidants, hindered phenol-based antioxidants are preferable. Representative examples of the hindered phenol-based antioxidants 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-ter
t-butyl-3-hydroxy-2,6-di-methylbenzyl] isocyanurate, tetrakis (2,4-di-te
rt-butylphenyl) 4,4'-biphenylenediphosphite, 4,4'-thiobis- (6-tert-butyl-O-cresol), 2,2'-thiobis- (6-te
rt-butyl-4-methylphenol), tris- (2
-Methyl-4-hydroxy-5-tert-butylphenyl) butane, 2,2'-methylene-bis- (4-methyl-6-tert-butylphenol), 4,4'-methylene-bis- (2,6 -Di-tert-butylphenol), 4,4'-butylidenebis- (3-methyl-6-t
tert-butylphenol), 4-hydroxymethyl-2,6-di-tert-butylphenol, 2,6-di-tert-4-n-butylphenol, 2,6-bis
(2'-Hydroxy-3'-tert-butyl-5'-methylpentyl) -4-methylphenol, 4,4'-methylene-bis- (6-tert-butyl-O-cresol), 4,4'- Butylidene-bis (6-tert-butyl-m-cresol), 3,9-bis {1,1-dimethyl-2- [β- (3-tert-butyl-4-hydroxy-5-
Methylphenyl) propionyloxy] ethyl {2,4
8,10-tetraoxaspiro [5,5] undecane and the like.

Among them, those having a melting point of 100 ° C. or higher, particularly 120 ° C. or higher are preferable. Further, it is effective to use it in combination with a phosphorus antioxidant. Furthermore, the combined use of at least one of phosphorus-based antioxidants, at least one of hindered phenol-based antioxidants, and at least one of hydrotalcite-based compounds makes it possible to improve photographic properties. Prevents thermal degradation and decomposition of resins and additives,
It is particularly preferable from the viewpoint of preventing the molding machine from rusting.

The total content of the antioxidant is 0.1 to 100 parts by weight of the rubbery polymer-containing aromatic monovinyl resin.
001 to 5 parts by weight, preferably 0.005 to 4 parts by weight,
0.01 to 3 parts by weight is more preferable, 0.02 to 2 parts by weight is particularly preferable, and 0.03 to 1 part by weight is most preferable.

When the content of the antioxidant is less than 0.001 part by weight, a sufficient antioxidant effect cannot be obtained.
It only increases kneading costs. On the other hand, if it exceeds 5 parts by weight, the effect of increasing the amount is not exhibited, and only the material cost increases. Furthermore, white smoke and bad odor often occur during injection molding, which adversely affects the photographic properties of the photosensitive material.

The application to which the injection molded article for photographic photosensitive materials according to the present invention can be applied will be described. Photographic disc film cartridges, photographic film spools, photographic film units with lenses, photographic film cartridge containers, light-shielding containers, resin-made photographic film cartridges, light-shielding magazines for loading sheet-shaped or roll-shaped photographic photosensitive materials into light rooms, Cores, photographic film cartridges, instant photographic film packs, sheet-like photographic film holders, photographic film photographing cameras, cut film packs, photographic light-sensitive material processing machines, ensuring dimensional accuracy, complete light shielding and photographic properties It can be applied to various injection-molded products for photographic light-sensitive materials that must be performed.

1) Photographic disc film cartridge; Japanese Utility Model Application Laid-Open No. Sho 60-21743, etc. 2) Film unit with lens;
43, JP-A-3-129341, JP-A-6
JP-A-11798, JP-A-7-295150,
JP-A-10-62910, JP-B-5-2919, JP-B-2-32615, U.S. Pat.
No. 73,205, etc. 3) Spool for photographic film;
No. 1, JP-A-58-178139-178145, JP-A-63-73742, JP-A-57-1.
96218, JP-A-58-82236, JP-A-58-82237, and JP-A-58-20343.
No. 6, JP-A-59-15049, JP-A-62
-240957, JP-A-3-129341, JP-A-4-33538, JP-A-7-295
No. 150, JP-A-9-319034, JP-A-10-83044, JP-B-44-16777, JP-B-55-31541, U.S. Pat.
0144, British Patent No. 2199805A, etc. 4) Patrone for photographic film made of resin;
No. 7738, JP-A-50-33831, JP-A-54-111822, JP-A-56-87039
JP-A-57-190948, JP-A-57-190948,
JP-A-251030, JP-A-1-313538,
JP-A-2-181141, JP-A-2-22195
No. 6, JP-A-3-116136, JP-A-3-116136
JP-A-129341, JP-A-4-37844, JP-A-4-115251, JP-A-4-273240
JP, JP-A-4-320258, JP-A-4-3258
JP-A-35344, JP-A-4-33539, JP-A-4-343353, JP-A-4-349454
JP, JP-A-7-295150, JP-A-9-3
19037, JP-A-9-329869, JP-A-10-62908, JP-A-10-62910
JP, JP-A-10-83042, JP-A-10-83042
JP-A-123668, JP-A-10-123669, JP-B-45-6991, JP-B-55-210
No. 89, U.S. Pat. No. 4,846,418,
U.S. Pat. No. 4,848,693; U.S. Pat.
No. 887,776 5) Container for photographic film patrone;
No. 3451, Japanese Utility Model Application Laid-Open No. 1-88940, Japanese Utility Model Application Laid-Open No. 1-113235, Japanese Utility Model Application Laid-Open No. 1-152337, Japanese Patent Application Laid-Open No. 61-73947, Japanese Patent Application Laid-Open No. 61-25 / 1986
JP-A-639, JP-A-62-291639, JP-A-63-121047, JP-A-2-21485
No. 5, JP-A-2-247640, JP-A-3-27640
No. 91741, JP-A-3-129341, JP-A-6-19054, JP-A-10-62912, JP-B-2-33236, JP-B-3-485
No. 81, Japanese Patent Publication No. 2-38939, U.S. Pat. No. 4,801,011, U.S. Pat.
386, U.S. Pat. No. 4,979,351, EP 02377062 A2, EP 2800065 A1, EP 09833
No. 75A2, etc. 6) Core, reel; Japanese Utility Model Laid-Open No. 60-107848,
U.S. Pat. No. 4,809,923; British Patent No. 2
No. 033873 7) Magazine for sheet photographic film; JP-A-56-51
No. 41, etc. 8) Photographic film cartridge;
6, JP-A-2-29041, JP-A 1-3
No. 12537, Japanese Utility Model Publication No. 56-16610, Japanese Utility Model Application Publication No. 60-120448, etc. 9) Photographic film case;
Gazette, Japanese Utility Model Application Laid-Open No. 64-34343, Japanese Utility Model Application Laid-Open No. 1-9
No. 4258, Japanese Utility Model Laid-Open No. 2-56139, Japanese Patent Publication No. 2-54934, U.S. Pat. No. 4,779,756.
Specification, European Patent No. 0 242 905 A1, etc. 10) Instant film pack;
No. 248, JP-A-62-240961, etc. 11) Packs and holders for sheet photographic films; JP-A-4-238331, JP-A-4-247440, JP-A-4-335334, JP-A-4 −34
9449, JP-A-4-350634, JP-A-5-341378, JP-A-5-341379, JP-A-5-341380, JP-A-5-34
1381, JP-A-6-75291, JP-A-6-75292, JP-A-6-75293,
JP-A-8-110568 and JP-A-8-11056
9, JP-A-8-110570 and JP-A-8-110570
No. 201982, Japanese Unexamined Patent Publication No. Hei 8-201983,
JP-A-8-201984, JP-A-8-26255
7, Japanese Patent Application Laid-Open No. 8-262558, Japanese Patent Application Laid-Open
179248, JP-A-10-104737, JP-A-10-104801, JP-T-Hei 4-50
4014, U.S. Pat. No. 4,725,865, and U.S. Pat. No. 4,821,055 12) Resin photographic film cartridge;
JP-A-831, JP-A-57-190948, JP-A-1-313538, JP-B-45-6991, JP-B-55-21089, and JP-A-55-97.
738, US Pat. No. 4,834,306, US Pat. No. 4,846,418, US Pat. No. 4,887,776, etc. 13) Camera; No. 191836,
Cameras using a light-tight cartridge described in JP-A-2-64533 and the like, simple-loading cameras described in JP-A-6-8886, JP-A-6-99908 and the like; No. 57398, JP-A-6-101135
Automatic winding camera described in each publication such as
Japanese Patent Application Laid-Open No. Hei 5-29331, which discloses a camera capable of taking out and replacing the type of film in the middle of shooting as described in JP-A-205690.
No. 38, Japanese Patent Application Laid-Open No. 5-283382, etc., at the time of shooting, for example, a camera capable of magnetically recording on a film magnetic recording of panoramic shooting, high vision shooting, normal shooting (print aspect ratio can be selected). JP-A-6-101194 describes a camera having a double exposure prevention function, JP-A-5-150577 describes a camera having a function of displaying the use state of a photographic film, and JP-A-10-55012. 14) Self-developing machine; JP-A-6-222514, JP-A-6-222514
-222545 publication etc.

The photographic light-sensitive material to which the injection molded article for a photographic light-sensitive material according to the present invention is applicable is shown below. (1) Silver halide photographic materials (film for printing, color or black and white photographic paper, color or black and white negative film, master paper for printing, DTR (diffusion transfer) photosensitive material,
Computerized typesetting film and paper, color or black-and-white positive film, color reversal film, microfilm, surveillance film, cinema film, self-developing photographic light-sensitive material, direct positive film and paper, etc. (JP-A-4-13638, JP-A-4-1723
39, JP-A-5-113623, JP-A-9
JP-A-325450, JP-A-10-62901, JP-A-10-62903, JP-A-10-62
904, JP-A-10-62905, JP-A-10-62906, JP-A-10-62921, JP-A-10-142731, etc.) (2) Thermal developing photosensitive material (thermal developing color photosensitive material) Thermal development black-and-white light-sensitive materials (for example, JP-B-43-4921 and JP-B-43-4924), "Basics of photographic engineering", silver halide photography (published by Corona Co., Ltd., 1879), pp. 553 to 555 and Research Tice. Closure magazine, June 1978, pages 9 to 15 (RD-17029), etc. Further, JP-A-59-12431, JP-A-60-123, and JP-A-59-12431.
-2950, 61-52343, JP-A-7-13295, 10-62898, 10-62899, and U.S. Pat. No. 3,457,0.
No. 75, U.S. Pat. No. 3,574,627,
U.S. Pat. No. 4,042,394; U.S. Pat.
(3) Photosensitive / thermosensitive recording materials (photothermography (photosensitive materials described in JP-A-3-72358) and the like.・ Recording material using thermal image formation method) (4) Diazonium photographic material (4-morpholinobenzenediazonium microfilm, microfilm, copy film, printing plate material, etc.) (5) Azide, diazide type photograph Photosensitive materials (photosensitive materials containing para-azidobenzoate, 4,4'diazidostilbene, etc., for example, copying films, printing plate materials, etc.) (6) Quinonediazide photographic photosensitive materials (orthoquinonediazide, orthonaphthoquinonediazide compounds, For example, a photograph containing benzoquinone (1,2) -diazide- (2) -4-sulfonic acid phenyl ether, etc. (7) Photopolymer (photosensitive material containing vinyl monomer, etc., printing plate, adhesive film, etc.) (8) Polyvinyl cinnamon Acid ester photosensitive material (eg, printing film, resist for IC, etc.) (9) Dry image forming material (having a layer having at least a photocurable compound, a photoinitiator and a dye precursor inside on a support) A recording material described in JP-A-11-2884 having a color developer in a layer containing the microcapsules or an adjacent layer)

An embodiment of an injection molded product for a photographic light-sensitive material according to the present invention will be described with reference to the drawings. FIG. 1 is a front view of a photographic film spool 10 as an injection molded product for a photographic photosensitive material according to the present invention. The entire photographic film spool 10 is formed of the resin composition specified in the present invention.

FIG. 2 is a perspective view of the belt-shaped photosensitive material core 20 as an injection-molded article for a photographic photosensitive material according to the present invention on the side opposite to the resin injection port. Formed of the composition. The inner surface of the outer cylinder 21 of this band-shaped photosensitive material core has a height of 0.0001 to
A plurality of 0.07 mm annular ridges 22 are provided to improve the injection moldability, physical strength, and appearance of the belt-shaped photosensitive material core.

FIG. 3 is an exploded perspective view of a photosensitive band container 20 as an injection-molded product for a photographic photosensitive material according to the present invention. The photosensitive band container 30 includes a roll 3 made of a photosensitive band.
And a slot 34 for taking out the leader portion 32 when the roll 31 is housed.
And a cover 36 for closing the opening of the main body 35 after the roll 31 is accommodated therein, and a closing member 3 for closing the slot 34 in conjunction with a projection 37 provided on the cover 36.
And 8.

FIG. 4 is an exploded perspective view of a photosensitive band container 40 as an injection molded product for a photographic photosensitive material according to the present invention.
2, a cover 43, and a closing member 44, and the closing member 44 is provided to be fitted inside the main body 42.
A concave rib 46 is provided on a side wall 45 of the main body 42.

FIG. 5 is an exploded perspective view of a photographic film cartridge 50 as an injection-molded product for a photographic photosensitive material according to the present invention. The photographic film cartridge 50 includes a lower case 51 and an upper case 52, and the upper case 52 The lower case 51 and the upper case 52 are formed of the resin composition specified in the present invention.

FIG. 6 is an exploded perspective view of a film unit with a lens 60 as an injection molded product for a photographic light-sensitive material according to the present invention. It comprises a lower case 63 for further storing the photographic film cartridge 62 to be stored in a light-tight manner, and an upper case 64 for sealing the lower case 63 from light. These lower case 63 and upper case 64 are the present invention. However, the conventional resin composition is formed of a light-shielding thermoplastic resin composition such as a polystyrene resin containing carbon black, a polymethyl methacrylate resin, and a polycarbonate resin.

On the other hand, the lens 65 and the finder 66 are made of a transparent thermoplastic resin composition such as a non-colored polycarbonate resin (displayed as PC), a polystyrene resin (displayed as PS resin), and a polymethyl methacrylate resin (displayed as PMMA resin). It is formed of things.

FIG. 7 is an exploded perspective view of a patrone for a photographic film as an injection-molded product for a photographic photosensitive material according to the present invention, FIG. 8 is a side view of the same, FIG. FIG. 3 is a partial sectional view of a disk used.

7 and 8, the patrone main body 70 has an upper case 71 made of plastic,
The lower case 72 is configured. Patrone body 70
A spool 73 is rotatably accommodated in the inside, and a photographic film 74 is wound around the spool 73 in a roll shape.

Each of the upper and lower cases 71 and 72 has a substantially semi-cylindrical shape, and a port portion 75 is formed to project from a part thereof. Upper case 71 and lower case 72
The light-shielding lid 76 is rotatably fitted into the port 75 when the two are fitted. A flat film passage 77 is formed in the light-shielding lid 76, and when the light-shielding lid 76 is rotated to the open position, it becomes a passage for the photographic film 74 sent out from the inside of the cartridge body 70. When the light-shielding lid 76 is rotated to the closed position, the opening (the entrance and exit of the photographic film) formed at the end of the port 75 is completely closed, and the inside of the cartridge body 70 is in a light-shielding state.

A projection 78 is formed at the back of the port portion 75 of the lower case 72. This projection 78 is
3 is a guide for picking up the leading end of the photographic film 74 wound around 3 and guiding it to the film passage 77.

The disks 79 and 80 have openings 7 respectively.
9a and 80a are formed. The spool 73 is fitted into a predetermined position of the spool 73 by being inserted into the openings 79a and 80a, and is rotatably mounted on the spool 73. Lips protrude from the outer circumferences of the disks 79 and 80 so as to face each other, and partially wrap the outermost circumference of the photographic film 74 wound on the spool 73 from both end faces.

When the use indicator 83 is fitted into the spool 73, the clutch claw 84 and the locking hole 85 of the disk 80 are locked to each other when the spool 73 is rotated in the film feeding direction. Disk 80
Can be forcibly rotated. When the spool 73 is rotated in the film winding direction, the disk 80 can rotate freely without engaging the clutch claws 84 with the engagement holes 85 of the disk 80. Also, the other disk 7
9 remains rotatable with respect to the spool 73. In addition,
The used display component 83 is integrated with a fan-shaped display plate 83a, and the use state of the photographic film cartridge can be determined by checking its position through a display window formed in the cartridge body 70.

Side ribs 86 are provided on the inner walls of the side surfaces of the upper case 71 and the lower case 72 to regulate the disks 79 and 80 from spreading out. A sector plate 87 is fixed to the spool 73, and a data flange label 88 is affixed to the surface thereof. A bar code is radially written on the label 88, and the bar code is photoelectrically detected through a window formed on a side surface of the cartridge body 70 when the spool 73 is rotated. This makes it possible to electrically detect the type information, the number of shots, and the like of the photographic film 74 stored in the cartridge body 70. In addition,
On a label 90 attached to the patrone main body 70, a film type indication, a unique number of the patrone, and the like are displayed.

The spool lock component 91 locks the spool 73 so that it does not rotate when the light shielding cover 76 is turned to the closed position. This lock is released when the light shielding cover 76 moves to the open position. Reference numeral 92 denotes a lock pole integrally formed with the upper case 71, and the light shielding cover 76 is locked by the lock pole 92 when the cover 76 is turned to the closed position. When the photographic film cartridge is set in a device such as a camera or a display device, the lock is provided by a light-shielding cover 76 provided in these devices.
Is disclosed by the opening mechanism. Instead of using the light-shielding lid 76, a film passage may be formed on the inner wall of the port portion 75, and the inside of the patrone main body 70 may be kept light-tight by attaching a telemump to the film passage.

As shown in FIG. 9, when the photographic film 74 is completely wound in the cartridge body 70, the outermost periphery of the photographic film 74 is partially wrapped by the lips 81, 81 of the disks 79, 80. Thus, loosening of the winding from the spool 73 is prevented. This allows
When the spool 73 rotates in the feeding direction of the photographic film 74, the photographic film 74 rotates integrally with the spool 73.

The side ribs 86 provided on the inner walls of the side surfaces of the upper and lower cases 71 and 72 restrict the disks 79 and 80 from spreading out from each other. , Facing side ribs 86
The spacing between them has been increased. For this reason, when the leading edge of the photographic film 74 is scooped up by the projection 78 and the disk 79, 80 is slightly spread outward when going to the film path 77, the photographic film 74 is lip 81, 8
A gutter-shaped curl is made and sent out from between the two.

The same effect can be expected even if the side ribs 86 are provided on only one side. Further, as a method of releasing the film winding looseness of the lip 81, a pair of separation claws are provided on both sides in the film width direction, and the pair of lips are partially separated from each other on the outer surfaces of the pair of separation claws in a direction away from each other. You may make it always deform.

When the photographic film cartridge is loaded into the camera, the lock pole 92 is driven by the mechanism on the camera side.
After the lock of the light-shielding lid 76 is released, the light-shielding lid 76 is rotated in the opening direction. Thereafter, the spool 73 is driven in the feeding direction, and feeding of the photographic film 14 is started. Lip 8 formed on the outer circumference of disks 79 and 80
Since the reference numerals 1 and 81 prevent the photographic film 74 from loosening, the photographic film 74 rotates integrally with the spool 73. During this rotation, the leading end of the photographic film 74 is picked up by the protrusion 78 and guided to the film passage 77.

When the leading end of the photographic film 74 is guided to the film passage 77 in this way, the lips 81, 81 are pushed out on both sides by the photographic film 74, so that the wrapping of the photographic film 74 is released behind the film passage 77. The one disc 80 is forcibly rotated in the feeding direction by the engagement between the clutch claws 84 and the locking holes 85, so that the force for feeding the photographic film 74 is increased.
Thus, the photographic film 74 is fed out of the cartridge body 70.

At the time of rewinding, the spool 73 is rotated in the reverse direction. Since the rear end of the photographic film 74 is locked to the spool 73, the photographic film 74 is wound into the cartridge body 70 by the reverse rotation of the spool 73. At this time, the discs 79 and 80 are spread behind the film passage 77, and the photographic film 74 is drawn between the discs 79 and 80 and wound around the spool 73.

As shown in FIG. 10, the disks 79, 80
Have the same contour shape. Openings 79a, 8
0 a is formed on a surface 99 that is one step lower than the surface 98 on which both ends of the photographic film 74 are aligned. The lip 81 protrudes from the outer periphery of the surface 98 so as to face the other disks 79 and 80, respectively, and partially wraps the outermost periphery of the photographic film 74 wound on the spool 73 from both end surfaces.

A flange 82 is provided integrally on the outer periphery of the lip 81. The flange 82 functions to reinforce the lip 81 so as not to spread. Also, in order to have a function of guiding the photographic film 74 to easily enter the inside of the lip 81 at the time of film winding,
The flange 82 has a cross-sectional shape that is inclined such that the tips of the opposing surfaces 82a are separated from each other.

FIG. 11 is a perspective view of a light-tight cartridge 100 as an injection-molded product for a night photographic light-sensitive material according to the present invention.
Opening / closing is performed by opening / closing a back cover 103 which is provided on the back of the unit 1 via a hinge 102 so as to be openable / closable. The light-tight cartridge 100 is used by loading 135 film.

FIG. 12 is a perspective view of a packaged sheet photographic film holder 110 as an injection-molded product for a photographic light-sensitive material according to the present invention. The pack 111 is put in and taken out.

FIG. 13 shows a holder 12 for a bag-containing sheet film as an injection-molded product for a photosensitive material according to the present invention.
In a perspective view 0, the sheet film holder 120 is mounted on the back of the camera, and a photographic film in a bag is put in and out.

[0141]

EXAMPLES [Product 1 of the Invention] The photographic film spool shown in FIG. 1 was injection-molded using a toggle type molding machine, Nestal (trade name; mold clamping pressure: 150 tons) manufactured by Sumitomo Heavy Industries, Ltd. (surface reflection gloss). A flat plate having a thickness of 3 mm was injection-molded for measuring the degree and the coefficient of static friction.)

The resin composition is as follows. Impact-resistant butadiene rubber-modified polystyrene resin having an average particle size of 5.5 μm butadiene rubber content of 6% by weight and styrene content of 94% by weight [MFR (temperature of 200 ° C. under G conditions of ASTM D1238, piston load) (Measured at 5 kg) is 8 g / 10 min, and the flexural modulus (JIS K 7203) is 2
4,600 kg / cm ² , molecular weight distribution 2.1, notched Izod impact strength (JIS K 6871) 6.3 k
g · cm / cm, the Vicat softening point is 95 ° C.].
2 parts by weight of 8,500 centistoke polydimethylsiloxane, 0.4 parts by weight of furnace carbon black using ethylene bottom oil as a black light-shielding substance,
As a dispersant for furnace carbon black, 0.2 part by weight of calcium stearate and 0.1 part of paraffin wax were used.
Parts by weight, an antistatic agent, 0.5 parts by weight of an aliphatic alcohol fatty acid ester as a drip-proof and lubricity improving substance, and 6-ethoxy-1,2-dihydro-2,2,4 as an anti-aging agent
0.1 parts by weight of trimethylquinoline and tetrakis [methylene-bis-3- (3 ′, 5′-di-tert-butyl-4′-hydroxyphenyl) propionate] methane as a hindered phenol antioxidant. The resin composition contains 0.05 parts by weight, 20 parts by weight of a 1,2-polybutadiene-based thermoplastic elastomer as a compatibilizer, and 2 parts by weight of synthetic silica.

This photographic film spool had no light cover, had a small last torque, and had no failures to stop halfway during the photographing operation. The Izod impact strength is from 6.3 kg · cm / cm of the base resin to 7.8 kg ·
cm / cm, an improvement of 20% or more.

By adding polydimethylsiloxane, the butadiene rubber of large particles became cloudy and the hindered phenolic antioxidant was colored by light, and the light-shielding ability was improved by 20% or more due to the additive effect of these. As a result, even when the amount of carbon black added was reduced by 20% or more, the same light-shielding property could be secured, so that the occurrence of weld lines and bumps could be suppressed.

The surface reflection glossiness was 6.5%, the static friction coefficient was 0.10, and the characteristics were almost the same as those of a photographic film spool in which large irregularities were formed on the outer surface of the flange. Therefore, it rotates smoothly like a photographic film spool in which a large uneven shape is imprinted.However, it does not cause shaving during rotation, and the powder due to the shaving does not adhere to the photographic film and cause a white dropout failure. Was something.

Further, the drip-proof property, the lubricity and the antistatic property could be achieved by using the aliphatic alcohol-based fatty acid ester and the silicone resin together without causing any other problems.

[Product 2 of the Present Invention] The photosensitive band container corresponding to FIG. 2 was dried at 80 ° C. for 4 hours using a direct pressure injection molding machine with a mold clamping pressure of 180 tons as a molding machine. Injection molding was performed at 235 ° C. and a mold temperature of 20 ° C.

The resin composition is as follows. AS resin having a weight average molecular weight (Mw) of 50,000 [MFR (ASTM D
1238 G condition temperature 200 ° C, piston load 5kg
3.5 g / 10 min, flexural modulus (JIS K)
7203) is 35,700 kg / cm ² , the molecular weight distribution is 1.5, and the notched Izod impact strength (JIS K 711)
0) is 2.5 kg · cm / cm and the Vicat softening point (JI
(Measured under a load of 5 kgf of SK 7206) is 105 ° C] 3
0 parts by weight, butadiene rubber graft polymerized ABS resin having an average particle size of 5 μm and a butadiene rubber content of 20% by weight [MFR (temperature of 200 under G conditions of ASTM D1238).
° C, measured at a piston load of 5 kg) is 4.3 g / 10 min.
Flexural modulus (JISK 7203) is 26,000kg
/ Cm ² , molecular weight distribution of 1.7, notched Izod impact strength (JIS K 7110) of 21 kg · cm / c
m, Vicat softening point is 94 ° C] 35 parts by weight, AS resin having a weight average molecular weight (Mw) of 300,000 [MFR (ASTM)
200 ° C, piston load 5 under G condition of D 1238
2.2 g / 10 min, flexural modulus (JIS)
K 7203) is 39,000 kg / cm ² , the molecular weight distribution is 1.8, the notched Izod impact strength (JIS K 7203).
110) is 2.6 kg · cm / cm, and the Vicat softening point (measured under a load of 5 kg according to JIS K 7206) is 106
[C]] 100 parts by weight of a rubbery polymer-containing aromatic monovinyl resin consisting of 35 parts by weight, as a silicone resin, 1 part by weight of polydimethylsiloxane having a viscosity of 20,000 centistokes at 25 ° C, and as a black light-shielding substance. 0.4 parts by weight of furnace carbon black made from ethylene bottom oil, 0.1 part by weight of zinc stearate and 0.1 part by weight of polypropylene wax as dispersants for furnace carbon black, 6 parts as antioxidant
-Ethoxy-1,2-dihydro-2,2,4-trimethylquinoline 0.1 part by weight, tetrakis [methylene-bis-3- (3 ′,
5'-di-t-butyl-4'-hydroxyphenyl) propionate] methane 0.1 part by weight, as a compatibilizer,
10% by weight of 1,2-polybutadiene-based thermoplastic elastomer, 35% of sodium ion of A-type zeolite which is a harmful gas adsorbing substance which adversely affects photographic properties such as hydrogen cyanide gas, free sulfur and formalin gas and also acts as a matte, is replaced with barium ion And a resin composition containing 5 parts by weight of an aluminosilicate which has been non-crystallized by substitution with palladium chloride as a hydrogen cyanide scavenger.

The photosensitive band container has no light fog and has a high-grade appearance on a matte surface. Less noticeable scratches, high physical strength (no weld lines)
Was something.

Even if the ABS resin-containing resin composition had a problem with photographic light-sensitive materials, especially injection-molded products for sensitized gold-sensitized light-sensitive materials due to liberation of hydrogen cyanide gas, an alumino compound which adsorbs and holds hydrogen cyanide gas Silicate and palladium chloride combined and AS resin blend amount 50wt%
By the above, an injection molded article for photographic photosensitive materials having excellent dimensional accuracy, physical strength, injection moldability, and excellent photographic properties in appearance can be provided.

[0151]

As described above, the present invention has the following advantages. (1) Excellent physical strength. (2) The occurrence of weld lines is reduced. (3) Good photographic properties. (4) The surface is matte, and light fog due to reflected light can be prevented. (5) The appearance is beautiful with few scratches and no noticeable scratches. (6) Excellent lubricity. (7) Excellent injection moldability.

[Brief description of the drawings]

FIG. 1 is a cross-sectional view of a photographic film spool which is an embodiment of an injection molded product for a photographic photosensitive material according to the present invention.

FIG. 2 is a perspective view of a belt-shaped photosensitive material core which is an embodiment of an injection molded product for a photosensitive material according to the present invention.

FIG. 3 is an exploded perspective view of a photosensitive band container which is an embodiment of an injection molded product for a photographic photosensitive material according to the present invention.

FIG. 4 is an exploded perspective view of a photosensitive band container which is an embodiment of an injection molded product for a photographic photosensitive material according to the present invention.

FIG. 5 is an exploded perspective view of a photographic film cartridge which is an embodiment of an injection molded product for a photographic photosensitive material according to the present invention.

FIG. 6 is an exploded perspective view of a film unit with a lens, which is an embodiment of an injection molded product for a photographic photosensitive material according to the present invention.

FIG. 7 is an exploded perspective view of a resin-made photographic film cartridge which is an embodiment of the injection-molded product for photographic photosensitive materials according to the present invention.

FIG. 8 is a side view of a resin-made photographic film cartridge which is an embodiment of an injection-molded product for a photographic photosensitive material according to the present invention.

FIG. 9 is a cross-sectional view of a resin photographic film cartridge which is an embodiment of an injection molded product for a photographic photosensitive material according to the present invention.

FIG. 10 is a partial cross-sectional view of a disk used in a photographic film cartridge made of resin, which is an embodiment of an injection molded product for a photographic photosensitive material according to the present invention.

FIG. 11 is a perspective view of a camera using a resin cartridge containing a photographic film, which is an embodiment of an injection molded product for a photographic photosensitive material according to the present invention.

FIG. 12 is a perspective view of a packaged sheet photographic film holder which is an embodiment of an injection molded product for a photographic photosensitive material according to the present invention.

FIG. 13 is a perspective view of a holder for a bag-containing sheet film, which is an embodiment of an injection-molded product for a photosensitive material according to the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 10 ... Spool for photographic films 20 ... Core for belt-shaped photosensitive material 30 ... Sensitive band material container 40 ... Sensitive band material container 50 ... Photo film cartridge 60 ... Film unit with a lens 70 ... Photo film cartridge 100 ... Light tight cartridge 120: Holder for sheet photographic film in a pack 130 ... Holder for sheet film in a bag

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) G03C 3/00 560 G03C 3/00 560S 566 566P F-term (Reference) 4F206 AA13C AA33 AH81 JA07 4J002 AC031 AC071 AC081 BC051 BG101 BN151 CP032 DA066 DD026 DG046 EH027 EH157 EZ006 FD107 FD206 GP00

Claims (5)

[Claims] 1. Melt flow rate (ASTM D 12
38 conditions) 2 to 40 g / 10 min, flexural modulus (J
IS K 7203) is 18,000 kg / cm ² or more, the molecular weight distribution is 5 or less, and the rubbery polymer-containing aromatic monovinyl resin 1 contains 1 to 40% by weight of the rubbery polymer.
An injection-molded product for photographic photosensitive materials, comprising 0.1 to 10 parts by weight of a silicone resin with respect to 00 parts by weight, and having a surface reflection glossiness of 45% or less. 2. The rubbery polymer according to claim 1, wherein the rubbery polymer is one or a mixture of two or more selected from polybutadiene rubber, butadiene-styrene random copolymer rubber, and acrylonitrile-butadiene copolymer rubber. Injection molded products for photographic photosensitive materials. 3. The injection molded article for a photographic photosensitive material according to claim 1, wherein the silicone resin is a silicone oil having a viscosity at 25 ° C. of 5,000 to 50,000 centistokes. 4. The rubbery polymer-containing aromatic monovinyl resin comprises 20 to 50 parts by weight of a rubbery polymer-containing ABS resin and 80 to 50 parts by weight of an aromatic monovinyl resin. 2. The injection-molded article for a photographic light-sensitive material according to claim 1, further comprising 0.001 to 20 parts by weight of a hydrogen cyanide gas-adsorbing substance which adsorbs and holds hydrogen cyanide gas per 100 parts by weight of the aromatic monovinyl resin. 5. The injection-molded product for a photographic light-sensitive material according to claim 1, which comprises 0.1 to 5 parts by weight of an aliphatic alcohol fatty acid ester based on 100 parts by weight of the rubbery polymer-containing aromatic monovinyl resin. .