JP2000147716A - Injection-molded product for packaging of photographic sensitive material and packaged body of photographic sensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an injection-molded product for packaging of a photographic sensitive material, the product which has excellent impact resistance and rigidity and which does not deteriorate the photographic sensitivity of the photosensitive material even when the photosensitive material is stored for a long time, by controlling the hydrogen cyanide content of the injection-molded product to a specified value or smaller. SOLUTION: This injection-molded product for packaging of a photographic sensitive material contains an ABS resin prepared by graft polymn, by 25 to 45 wt.% and has >=10 kg.cm/cm Izod impact strength. The hydrogen cyanide content of the injection-molded product is controlled to <=0.2 mg/kg. When the proportion of the graft ABS resin ranges from 25 to 45 wt.%, enough Izod impact strength can be obtd., and the proportion is preferably from 27 to 40 wt.%, and more preferably from 31 to 35 wt.%. Preferably, the graft ABS resin consists of the polymers of 10 to 40 pts.wt. of acrylonitrile monomers, 80 to 110 pts.wt. of butadiene monomers and 60 to 80 pts.wt. of styrene monomers.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an injection molded product for packaging photographic photosensitive material and a photographic photosensitive material package in which the photographic photosensitive material is packaged by using an injection molded product for packaging photographic photosensitive material.

[0002]

2. Description of the Related Art Conventionally, as a material for a packaging container for accommodating a photographic photosensitive material formed by injection molding or a core for winding a long photosensitive material sheet (hereinafter referred to as an injection molded product for packaging a photographic photosensitive material). Various plastic materials are being studied. In general, the performance required for injection-molded products for packaging photographic light-sensitive materials, in addition to not adversely affecting photographic properties, dimensional accuracy, physical strength, abrasion resistance, lubricity,
Moldability and the like. In addition, injection-molded articles for packaging photographic light-sensitive materials that require light-shielding properties require complete light-shielding properties as properties other than those described above. In particular, it is desired that physical properties such as impact resistance and rigidity be excellent so as not to be deformed or damaged even when subjected to an impact such as a drop.

An ABS (acrylonitrile-butadiene-styrene) resin (hereinafter, referred to as an ABS) produced by graft polymerization is used as a material for forming an injection molded product for packaging a photographic photosensitive material.
It is generally known that blended resins (including graft ABS resins) exhibit high impact resistance. For example, JP-A-9-80693 proposes a blend resin of a polycarbonate resin or a vinyl chloride resin and a graft ABS resin.

[0004]

SUMMARY OF THE INVENTION The present inventor has focused on a blend resin of a graft ABS resin and an AS (acrylonitrile-styrene) resin, and as a result,
It was found that the Izod strength of the blend resin increased as the content of the S resin increased. Further studies have shown that the Izod impact strength is 10 kg. cm / c
In the case of a photosensitive material package in which a photosensitive material is packaged in an injection-molded product for packaging a photosensitive material comprising a blend resin of at least m and having a total weight of about 50 g (for example, 135 type photographic film cartridge). , The impact resistance is such that the photographic photosensitive material package is hardly damaged even if dropped.
It has been found that rigidity can be obtained.

However, the Izod impact strength is 10 kg.
Photosensitive material packaged in an injection-molded article made of a blended resin material containing a graft ABS resin so as to have a density of at least cm / cm has a large decrease in sensitivity, particularly when a photosensitive material sensitized with gold is packaged. It was found that the decrease in sensitivity was large. The inventors of the present invention have examined the cause of this. When kneading the graft ABS resin and another resin, the nitrile group in the graft-polymerized ABS resin is decomposed to hydrogen cyanide, and this hydrogen cyanide is contained in the injection molded product. It was revealed that the release was due to a sharp reaction with gold used for gold sensitization in the photographic light-sensitive material.

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide an injection molded article for packaging photographic light-sensitive material which has excellent impact resistance and rigidity and which does not deteriorate the photographic sensitivity of the photographic light-sensitive material even when the photographic light-sensitive material is stored for a long period of time. Is to provide.

[0007]

According to the present invention, an ABS resin produced by graft polymerization is contained in the range of 25 to 45% by weight, and the Izod impact strength is 10 kg · cm / cm.
The injection molded article for packaging a photographic photosensitive material described above, wherein the hydrogen cyanide content of the injection molded article is 0.2 mg / kg or less. The above-described injection molded product for packaging photographic light-sensitive materials has photographic properties, compatibility, physical strength (rigidity, impact strength, etc.), moldability,
In order to maintain good dimensional accuracy, it is preferable to contain the AS resin in the range of 55 to 75% by weight, or the AS resin having a weight average molecular weight of 100,000 or more in the range of 27.5 to 40% by weight. It is preferable that an AS resin having a weight average molecular weight of less than 100,000 is contained in a range of 27.5 to 40% by weight. Further, it is preferable that the plastic container for packaging a photographic photosensitive material contains a substance that adsorbs and holds hydrogen cyanide.

In the present invention, the amount of the ABS resin powder produced by graft polymerization is 25 to 45% by weight, the amount of the AS resin having a weight average molecular weight of 100,000 or more is 27.5 to 40% by weight, and the weight average molecular weight is The amount of AS resin powder of less than 100,000 is 27.5 to 40% by weight, the total amount of these resin powders is 100% by weight, and the weight average molecular weight is 10%.
A mixed powder having a weight ratio of at least 10,000 AS resin powders and an AS resin powder having a weight average molecular weight of less than 100,000 in a ratio of 1: 0.8 to 1.1 is kneaded by an extruder into pellets, which are then injected. Izod impact strength of 10kg ・ c
m / cm or more of an injection molded product for packaging a photographic photosensitive material, wherein the injection molded product has a hydrogen cyanide content of 0.2 mg.
/ Kg or less.

According to the present invention, a gold-sensitized photographic material is provided.
There is also a photographic light-sensitive material package characterized by being packaged using the above-mentioned injection molded product for photographic light-sensitive material packaging. It is preferable that the photographic photosensitive material package is sealed in a moisture-proof packaging material having a moisture permeability of 10 g / m ² · 24 hours or less.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION The Izod impact strength of an injection-molded product for packaging photographic light-sensitive material of the present invention is 10 cm / cm or more, preferably 15 kg / cm / cm or more, more preferably 20 kg / cm / cm or more. More preferably 25K
g · cm / cm or more. The higher the Izod impact strength, the stronger the injection molded article for photographic photosensitive material packaging is against external impacts and impacts such as dropping, and is less likely to be deformed or damaged. The upper limit of the Izod impact strength is 50 kg.
cm / cm. If the amount of the graft ABS resin is too large in order to increase the Izod impact strength, it is difficult to suppress the generation of hydrogen cyanide, and the photographic light-sensitive material cannot be stored for a long time.

When the content of the graft ABS resin contained in the injection molded article for packaging photographic light-sensitive material of the present invention is in the range of 25 to 45% by weight, the above-mentioned Izod impact strength can be obtained. It is more preferably in the range of 40% by weight, and still more preferably in the range of 31 to 35% by weight. The graft ABS resin is composed of 10 to 4 acrylonitrile monomers.
It is preferable that 0 parts by weight, butadiene monomer be 80 to 110 parts by weight, and styrene monomer be 60 to 80 parts by weight.

The content of hydrogen cyanide in the injection molded article for packaging photographic light-sensitive materials of the present invention is 0.2 mg / kg or less, more preferably 0.15 mg / kg or less, and further preferably 0.1 mg / kg or less. . The lower the content of hydrogen cyanide, the less photographic sensitivity of the photographic light-sensitive material is likely to deteriorate. The amount of hydrogen cyanide in the injection molded article for photographic photosensitive material packaging is determined by finely pulverizing the injection molded article for photographic photosensitive material packaging or the resin pellet before forming the injection molded article for photographic photosensitive material packaging described below with a phosphoric acid aqueous solution. EDT
A. Aqueous solution A is heated and distilled, and the cyanide in the extract is developed by pyridine-pyrazolone spectrophotometry described in JIS K 0102 (Factory wastewater test method) 38, section of cyanide. The absorbance at 638 nm can be read and quantified.

In the injection-molded article for packaging photographic light-sensitive material of the present invention, the resin component other than the graft ABS resin is preferably an AS resin. From the balance of photographic properties, physical strength, and moldability, the AS resin has an AS resin having a weight average molecular weight of 100,000 or more (hereinafter, referred to as a high molecular weight AS resin) and an AS resin having a weight average molecular weight of less than 100,000 (hereinafter, a low molecular weight AS resin). (Referred to as resin). The high molecular weight AS resin preferably has a weight average molecular weight in the range of 100,000 to 500,000. The low molecular weight AS resin preferably has a weight average molecular weight in the range of 30,000 to 90,000. The mixing ratio of the high molecular weight AS resin to the low molecular weight AS resin is such that the high molecular weight AS resin 1 is mixed with the low molecular weight AS resin 0.8.
It is preferably from 1.1 to 1.1. The high molecular weight AS resin and the low molecular weight AS resin have an acrylonitrile monomer of 20 to
It is preferable that 40 parts by weight and 60 to 80 parts by weight of the styrene monomer are used. If the amount of the high molecular weight AS resin is too large, the moldability decreases, and if the amount of the low molecular weight AS resin is too large, the rigidity of the injection molded product decreases.

The injection-molded article for packaging photographic light-sensitive materials of the present invention contains two or more, preferably three or more, of an antioxidant, a fatty acid metal salt, carbon black, and a substance (hydrogen cyanide gas scavenger) that adsorbs and retains hydrogen cyanide. It is preferable to mold the blended resin. If necessary, an antioxidant, an ultraviolet absorber and a radical scavenger may be added. By adding these additives, it is possible to suppress the decomposition of acrylonitrile, that is, the generation of hydrogen cyanide, or to prevent the generated hydrogen cyanide from being adsorbed and held in the resin so as not to adversely affect the photographic properties. it can.

Examples of the antioxidants used in the present invention include phenolic antioxidants, ketone amine condensation antioxidants, imidazole antioxidants, and phosphite-based antioxidants described in JP-A-9-80693. Examples include an antioxidant and a thiourea-based antioxidant, and a hindered phenol-based antioxidant is particularly preferable. The amount of antioxidant added
Although it varies depending on the content of the graft ABS resin, the amount of other additives, and the like, it is preferable to add it within the range of 0.001 to 2 parts by weight based on 100 parts by weight of the blend resin component.

Examples of the fatty acid metal salt used in the present invention include caproic acid, caprylic acid, capric acid, myristic acid, lauric acid, stearic acid, hydroxystearic acid, linoleic acid described in JP-A-9-80693. Fatty acids such as acid, stearyl acid, lactic acid, succinic acid, beheric acid, linoleic acid, stearyl lactic acid, hydroxystearic acid, ricinoleic acid, naphthenic acid, oleic acid, montanic acid, erucic acid, palmitic acid, erucic acid and calcium And compounds with metals such as magnesium, zinc, and sodium. Specific examples thereof include calcium stearate, magnesium stearate, and zinc stearate. The amount of the fatty acid metal salt varies depending on the content of the graft ABS resin, the amount of other additives, and the like.
It is preferable to add within the range of 0.01 to 5 parts by weight based on parts by weight.

It is already known that carbon black having a large DBP oil absorption generates a small amount of hydrogen cyanide. The carbon black used in the present invention is DBP
The oil absorption is preferably at least 75 cc per 100 g, more preferably at least 105 cc, even more preferably at least 115 cc. The carbon black is preferably a furnace carbon black produced by a furnace method. The addition amount of carbon black varies depending on the DBP oil absorption. For example, if the DBP oil absorption is 75 cc or more, 0.3 to 100 parts by weight of the blend resin component is used.
It is preferably in the range of 5 parts by weight, more preferably in the range of 0.9 to 3 parts by weight.

The substance that adsorbs and holds hydrogen cyanide (also referred to as scavenging) may be any substance that physically adsorbs hydrogen cyanide or one that coordinates with hydrogen cyanide. For example, elemental group VIII chlorides such as palladium chloride, rhodium chloride, nickel chloride, and cobalt chloride, or representative palladium compounds, rhodium compounds, iridium compounds, osmium compounds, and the like described in JP-A-5-341450. No. The amount of the substance that adsorbs and retains hydrogen cyanide varies depending on the content of the graft ABS resin, the amount of other additives, and the like.
01 to 0.05 part by weight, preferably 0.002 to 0.0
It is more preferable to add 1 part by weight, within the range of 0.003 to 0.005 parts by weight from an economic viewpoint.

The injection molded article for packaging a photographic light-sensitive material of the present invention comprises a graft ABS resin powder, a high molecular weight AS resin powder,
The mixture can be produced using a blended resin obtained by adding the above additive to a mixed powder obtained by mixing a low-molecular-weight AS resin powder and kneading (melt kneading). An extrusion method is preferred as a kneading method. When the mixed powder and the additive are kneaded by an extrusion method, they are melt-kneaded by an extruder, the extruded strand-shaped blended resin is put into water, cooled, cut by a cutting machine (pelletizer), and pelletized (hereinafter, referred to as pelletized). (Referred to as resin pellets). The obtained resin pellets can be injection-molded by a known injection molding method to produce an injection-molded product for packaging photographic light-sensitive materials.

The grafted ABS resin powder is obtained by emulsion polymerization of polybutadiene monomer to form a polybutadiene latex, graft polymerization of acrylonitonyl monomer and styrene monomer, and then coagulating and drying the obtained ABS latex to form a powder. And can be manufactured.

The high molecular weight AS resin powder and the low molecular weight AS resin powder are produced by subjecting acrylonitrile monomer and styrene monomer to suspension polymerization to form a styrene / acrylonitrile copolymer, and then dehydrating and drying to produce powder. Can be. By powdering the high molecular weight AS resin and the low molecular weight AS resin, the high molecular weight AS resin and the low molecular weight
The mixing ratio with the S resin can be adjusted.

By melt-kneading the mixed powder and the additive with an extruder, the mixture can be melt-kneaded in a continuous process. The extruder is preferably a single or twin screw extruder. When melt-kneading with a single-screw extruder, the ratio (L / D) of the length (L) of the extrusion screw to its diameter (D) is preferably in the range of 15 to 70, and preferably in the range of 20 to 50. More preferably within 2
More preferably, it is in the range of 5 to 40. Also,
The temperature of the resin at the time of melt-kneading is preferably set in the range of 180 to 280 ° C, preferably 200 to 250 ° C.

FIG. 1 shows an example of the photographic light-sensitive material package of the present invention.
Shown in The photographic photosensitive material package 1 is a photographic film magazine for a camera for special use such as a security camera (hereinafter, referred to as a film magazine for surveillance camera). A photographic photosensitive material roll in which a long photographic photosensitive material 3 is formed into a roll is accommodated in the container 2. The weight of the film magazine for surveillance cameras is about 500 g. For example, since the weight is heavy as compared with the 135-type photographic film cartridge described above, the film magazine is easily damaged by impact such as dropping. Therefore, the Izod impact strength of the container 2 is 15 kg ·
cm / cm or more is preferable, 20 kg / cm / cm or more is more preferable, and 25 kg / cm / cm or more is further preferable.

In addition to the film magazine for surveillance cameras shown in FIG. 1, the injection molded article for packaging photographic light-sensitive material of the present invention can be used to protect a sheet-shaped photographic light-sensitive material or a photographic light-sensitive material wound in a roll shape from light-shielding properties. The shape is not particularly limited as long as it is a photographic photosensitive material packaging container or a photosensitive material core for winding a long photosensitive material sheet for storing while securing. Examples of containers for photographic photosensitive material packaging include cartridges for photographic disc films, film units with lenses, patrones for photographic films, containers for photographic film patrones, magazines for sheet films,
Examples include a photographic film cartridge, an instant film pack, a resin photographic film cartridge, a camera, and a self-developing machine.

(1) Photographic disc film cartridges, for example, those described in Japanese Utility Model Unexamined Publication No. Sho 60-21743.

(2) A film unit with a lens; for example, a film unit with a lens described in JP-A-9-80693 shown in FIG.
80693) and JP-A-63-22664.
No. 3 publication.

(3) Patrone for photographic film; for example, Japanese Patent Laid-Open No. 54-111822, Japanese Patent Publication No. 45-6
No. 991, JP-B-55-21089, JP-A-50-33831, JP-A-56-87039, JP-A-55-97738, JP-A-1-312
538, JP-A-57-190948, JP-A-4-273240, JP-A-4-320258, JP-A-4-335344, JP-A-4-33
No. 5639, JP-A-4-343353, JP-A-4-349454, U.S. Pat.
8, US Pat. No. 4,848,693, and US Pat. No. 4,887,776.
Further, a cartridge for an APS film composed of the components described in JP-A-9-80693 shown in FIG. 3 (refer to JP-A-9-80693 for description of the drawing and assembling method). Discs used for APS film cartridges, for example, include those disclosed in JP-A-8-314069, JP-A-10-90893, and JP-A-10-90839.

(5) Container for photographic film cartridge; for example, JP-A-61-250639, JP-A-61-1
73947, JP-A-61-73947, JP-A-60-163451, U.S. Pat.
No. 011, JP-A-63-121047, JP-A-62-291639, and Japanese Utility Model Laid-Open No. 1-88940.
Gazette, Japanese Utility Model Publication No. 2-3236, Japanese Utility Model Publication No. 3-48
No. 581, Japanese Patent Publication No. 2-38939, U.S. Pat. No. 4,639,386, U.S. Pat.
No. 11, U.S. Pat. No. 4,979,351,
EP 0 370 62 A2, EP 028
0065A1 and EP0298375A2.

(6) Sheet film magazines: those described in, for example, JP-A-56-5141. A holder for a photo film containing a pack described in JP-A-9-80693 shown in FIG.
No. 80693 also includes a sheet film holder described in JP-A-9-80693.

(7) Photographic film cartridge; for example, a photographic film cartridge described in JP-A-9-80693 shown in FIG. 6 (the illustration is described in JP-A-9-8
No. 0693), JP-B-56-16610, JP-A-2-24846 and JP-A-64-32.
No. 343, No. 1-94258, No. 2
-56139, Japanese Utility Model Laid-Open No. 2-56139, European Patent 0242905, Japanese Patent Publication No. 2-54934.
No. described in Japanese Patent Publication No. JP-A-1-187 shown in FIG.
No. 547, a photosensitive material container for a microfilm, a computer-printing typesetting film, a COM film, etc., and FIG.
US Pat. No. 4,272,035, which is described as a conventional example in the above-mentioned Japanese Patent Application Laid-Open No. 1-187547, a film for computer-photography, C
A photosensitive band container for an OM film or the like (the illustration is described in JP-A-1-18747, U.S. Pat. No. 4,272,03).
No. 5).

(8) Instant film pack; see, for example, Japanese Utility Model Laid-Open No. 61-41248, Japanese Patent Laid-Open No. 62-24
0961 etc.

(9) Photographic film cartridge made of resin; for example, JP-A-50-33831, JP-A-57-1
No. 90948, Japanese Patent Application Laid-Open No. 1-312538, Japanese Patent Publication No. Sho 45-6991, Japanese Patent Publication No. Sho 55-21089, Japanese Utility Model Publication No. Sho 55-97738, U.S. Pat.
No. 834,306, U.S. Pat. No. 4,846,41
No. 8 and U.S. Pat. No. 4,8887,776.

(10) Camera; for example, a camera using a light-tight cartridge described in Japanese Patent Application Laid-Open No. 2-64533 shown in FIG.
And Japanese Patent Application Laid-Open No. H6-1191836.
No. 8886, etc., a simple loading type camera, JP-A-6-101135, etc., an automatic winding type camera, and JP-A-6-205690, etc., taking out and replacing the type of film during shooting. Cameras that can be used, JP-A-5-293138, JP-A-5-283
No. 382, for example, a camera capable of magnetically recording on a film a panoramic image, a high-definition image, and a normal image (magnetic recording capable of selecting a print aspect ratio), described in JP-A-6-101194. Camera having double exposure prevention function
A camera having a function of displaying a use state, such as a photographic film described in JP-A-05577, and a camera described in JP-A-10-55012.

(11) Self-developing machine;
And JP-A-6-222545.

Examples of the photosensitive material core include a photographic film spool, a core, and a reel. (1) Spool for photographic film: For example, a spool for photographic film described in JP-A-9-80693 shown in FIG. 10 (see JP-A-9-80693 for description of the figure), and Japanese Patent Publication No.
196218, JP-A-59-15049, U.S. Pat. No. 1,930,144,
3-73742, Japanese Utility Model Application Laid-Open No. 54-120931, Japanese Utility Model Application Laid-Open No. 58-178139-178145,
JP-B-55-31541, JP-A-58-2034
No. 36, Japanese Unexamined Patent Publication No. 58-82236, and No. 4
4-16777, JP-A-63-73742, JP-A-62-240957, JP-A-63-7
No. 3,742, JP-A-62-240957, JP-A-4-335638, JP-A-9-18515, British Patent No. 2,199,805, and the like.

(2) Core, reel;
No.-107848, U.S. Pat. No. 4,809,923.
And those described in UK Patent No. 2,033,873B. JP-A-9-80693 shown in FIG.
Japanese Patent Application Laid-Open No. 9-80693 also includes a band-shaped photosensitive material core described in Japanese Patent Application Laid-Open No. 9-80693.

It is preferable that the photographic light-sensitive material package in which the light-sensitive material is wrapped in the above-described injection molded product for wrapping the light-sensitive material is stored in a moisture-proof packing material. In particular, the photographic light-sensitive material package in which the gold-sensitized photographic light-sensitive material is packaged has a moisture permeability of 10 g / m ² · 24 hours or less, preferably 6 g / m ^2.
It is preferable to store in a moisture-proof material of 24 hours or less, more preferably 3 g / m ² · 24 hours or less, particularly preferably 1 g / m ² · 24 hours or less. The moisture permeability is a value measured under the condition B of JIS Z0208. If the moisture permeability of the packaging material is high, a photographic light-sensitive material containing a large number of sensitizing dyes, couplers, antihalation dyes, various additives, etc., which deteriorates due to moisture, cannot be maintained in a good state for a long time (6 months or more).

Examples of the photographic light-sensitive material packaged in the injection molded article for wrapping the photographic light-sensitive material of the present invention include the following. (1) silver halide photographic materials (printing film, color or black and white photographic paper, color or black and white negative film, printing master paper, diffusion transfer (DTR) photosensitive material,
Computer typesetting film and computer typesetting paper, microfilm,
Color or black-and-white positive film, movie film, self-developing photographic material, direct positive film and paper)

(2) Heat-developable light-sensitive material (heat-developable color light-sensitive material, heat-developable black-and-white light-sensitive material (for example, JP-B-43-49)
Nos. 21 and 43-4929, "Basics of photographic optics", pages 553 to 555 of silver halide photography (Corona Co., Ltd., 1879) and Research Disclosure Magazine 197.
What is described on June 9 pp. 9-15 (RD-17029). Further, JP-A-59-12431,
Nos. 60-2950, 61-52343 and U.S. Pat. No. 4,584,267, which are transfer type heat-developable color photosensitive materials described in U.S. Pat. No. 4,584,267.

(3) Photosensitive / thermosensitive recording material
Recording material using photothermography (photosensitive / thermosensitive image forming method) described in, for example, US Pat.

(4) Diazonium photographic light-sensitive material (4-morpholinobenzenediazonium microfilm, microfilm, copying film, printing plate, etc.)

[0042] (5) azido, diazide photographic photosensitive material (p-azido-benzo Aid, ^4,4, photosensitive material containing a diazide stilbene and the like, for example, copying films, printing plate etc.)

(6) Quinonediazide-based photographic materials (orthoquinonediazide, orthonaphthoquinonediazide compounds such as benzoquinone (1,2) -diazide- (2) -4-sulfonic acid phenyl ether, etc., for example, printing) Plate material, copy film, adhesion film, etc.)

(7) Photopolymer (photosensitive material containing vinyl monomer, etc., printing plate, adhesive film, etc.)

[0045]

EXAMPLES (Production of Resin Pellets) [Example 1] (Sample 1-1) 35 parts by weight of low molecular weight AS resin powder and 35 parts by weight of high molecular weight AS resin powder, A obtained by graft polymerization
To 100 parts by weight of the mixed powder (A) obtained by mixing 30 parts by weight of the BS resin powder, 1.0 part by weight of furnace carbon black (DBP oil absorption: 75 mL / 100 g), 0.05 part by weight of calcium stearate, 0.1 part by weight of a hindered phenolic antioxidant was added. Next, the mixed powder to which the additive was added was extruded using a single screw extruder having an extrusion screw L / D of 25 and a resin temperature of 23.
The mixture was melt-kneaded while being adjusted to 5 ° C. The kneaded blended resin is extruded into water in the form of a strand and solidified, and then cut with a pelletizer to have a diameter of 3 mm.
It was a resin pellet having a thickness of 3 mm.

(Sample 1-2) To 100 parts by weight of the mixed powder (A), 1.0 part by weight of furnace carbon black (DBP oil absorption: 75 mL / 100 g), 0.05 part by weight of calcium stearate, hindered phenol Resin pellets were produced in the same manner as in Sample 1-1 except that 0.1 part by weight of a system antioxidant and 0.01 part by weight of palladium chloride were added.

(Sample 1-3) To 100 parts by weight of the mixed powder (A), 1.0 part by weight of furnace carbon black (DBP oil absorption: 75 mL / 100 g), 0.05 part by weight of calcium stearate, hindered phenol Resin pellets were produced in the same manner as in Sample 1-1 except that 0.1 part by weight of a system antioxidant and 0.03 part by weight of palladium chloride were added.

Example 2 (Sample 2-1) 35 parts by weight of low molecular weight AS resin powder, 40 parts by weight of high molecular weight AS resin powder, graft polymerized A
0.3 parts by weight of furnace carbon black (DBP oil absorption: 75 mL / 100 g) and 0.05 parts by weight of calcium stearate are added to 100 parts by weight of the mixed powder (B) obtained by mixing the BS resin powder to 25 parts by weight. And 0.1 parts by weight of a hindered phenolic antioxidant.
Then, the mixed powder to which the additive was added was extruded using a single screw extruder having an L / D of an extrusion screw of 25 and a resin temperature of 2: 1.
The mixture was melt-kneaded while adjusting to 35 ° C. The kneaded blended resin is extruded into water in the form of a strand and solidified, and then cut with a pelletizer to a diameter of 3 m.
m, resin pellets having a thickness of 3 mm.

(Sample 2-2) With respect to 100 parts by weight of the mixed powder (B), 1.0 part by weight of furnace carbon black (DBP oil absorption: 75 mL / 100 g), 0.05 part by weight of calcium stearate, hindered phenol Sample 2 above except that 0.1 part by weight of the system antioxidant was added.
Resin pellets were produced in the same manner as in Example 1.

(Sample 2-3) To 100 parts by weight of the mixed powder (B), 1.0 part by weight of furnace carbon black (DBP oil absorption: 75 mL / 100 g), 0.05 part by weight of calcium stearate, hindered phenol Resin pellets were produced in the same manner as in Sample 2-1 except that 0.1 part by weight of the system antioxidant and 0.01 part by weight of palladium chloride were added.

(Sample 2-4) To 100 parts by weight of the mixed powder (B), 1.0 part by weight of furnace carbon black (DBP oil absorption: 75 mL / 100 g), 0.05 part by weight of calcium stearate, hindered phenol Resin pellets were produced in the same manner as in Sample 2-1 except that 0.1 part by weight of the system antioxidant and 0.03 part by weight of palladium chloride were added.

Example 3 (Sample 3-1) 30 parts by weight of a low molecular weight AS resin powder, 30 parts by weight of a high molecular weight AS resin powder, and grafted A
1.0 part by weight of furnace carbon black (DBP oil absorption: 75 mL / 100 g) and 0.05 part by weight of calcium stearate based on 100 parts by weight of the mixed powder (C) obtained by mixing the BS resin powder to 40 parts by weight. , 0.1 parts by weight of a hindered phenolic antioxidant and 0.01 parts by weight of palladium chloride. Next, the mixed powder to which the additive was added was melt-kneaded using a single screw extruder having an L / D of an extrusion screw of 25 while adjusting the resin temperature to 235 ° C. The kneaded blended resin was extruded into water in the form of a strand to be solidified, and then cut by a pelletizer into resin pellets having a diameter of 3 mm and a thickness of 3 mm.

(Sample 3-2) To 100 parts by weight of the mixed powder (C), 1.0 part by weight of furnace carbon black (DBP oil absorption: 75 mL / 100 g), 0.05 part by weight of calcium stearate, hindered phenol Resin pellets were produced in the same manner as in Sample 3-1 except that 0.1 part by weight of the system antioxidant and 0.03 part by weight of palladium chloride were added.

Comparative Example 1 (Sample 1-4) Resin pellets were produced in the same manner as in Example 1 (Sample 1-1) except that nothing was added to 100 parts by weight of the mixed powder (A). .

(Sample 1-5) Example 1 (Sample 1) except that 1.0 part by weight of furnace carbon black (DBP oil absorption: 75 mL / 100 g) was added to 100 parts by weight of the mixed powder (A). Resin pellets were produced in the same manner as in -1).

(Sample 1-6) Except that 1.0 part by weight of furnace carbon black (DBP oil absorption: 75 mL / 100 g) and 0.05 part by weight of calcium stearate were added to 100 parts by weight of the mixed powder (A). Example 1
Resin pellets were produced in the same manner as in (Sample 1-1).

(Sample 1-7) Based on 100 parts by weight of the mixed powder (A), 0.3 parts by weight of furnace carbon black (DBP oil absorption: 75 mL / 100 g), 0.05 parts by weight of calcium stearate, hindered phenol Example 1 (1) except that 0.1 part by weight of the antioxidant was added.
Resin pellets were produced in the same manner as in -1).

(Sample 1-8) To 100 parts by weight of the mixed powder (A), 1.0 part by weight of furnace carbon black (DBP oil absorption: 75 mL / 100 g), 0.05 part by weight of calcium stearate, hindered phenol 0.1 part by weight of a system antioxidant was added. Next, the mixed powder (A) to which this additive was added was melt-kneaded at a melting temperature of 235 ° C. using a Banbury mixer to produce resin pellets.

Comparative Example 2 Sample 2-5: 100 parts by weight of mixed powder (B)
Furnace carbon black (DBP oil absorption 75mL
Example 2 except that 0.3 parts by weight was added.
Resin pellets were produced in the same manner as (Sample 2-1).

(Sample 2-6) Except that 0.3 parts by weight of furnace carbon black (DBP oil absorption: 75 mL / 100 g) and 0.05 parts by weight of calcium stearate were added to 100 parts by weight of the mixed powder (B). Example 2
Resin pellets were produced in the same manner as (Sample 2-1).

Comparative Example 3 1.0 part by weight of furnace carbon black (DBP oil absorption: 75 mL / 100 g), 0.05 part by weight of calcium stearate, hindered phenol based on 100 parts by weight of mixed powder (C) Sample 3-1 above except that 0.1 part by weight of antioxidant was added.
In the same manner as in the above, resin pellets were produced.

(Production of Container for Packaging Photosensitive Material) The resin pellets produced in the above Examples and Comparative Examples were mixed at 80 ° C. for 4 hours.
Dried for hours. Next, using a direct pressure injection molding machine with a mold clamping pressure of 180 tons, the container for packaging photographic photosensitive material shown in FIG. 1 was manufactured under the conditions of a resin temperature of 235 ° C. and a mold temperature of 20 ° C.

(Evaluation and Results) 1) Measurement of Izod Impact Strength Resin pellets produced in Example 1 (Sample 1-1), Example 2 (Sample 2-1), and Example 3 (Sample 3-1) were prepared. Specimens for measuring Izod impact strength were manufactured using the same. Using this Izod impact strength measurement sample piece, JIS K68
The Izod impact strength was measured by the method described in No. 71.

2) Drop strength test Photosensitive material packaging manufactured using the resin pellets manufactured in Example 1 (Sample 1-1), Example 2 (Sample 2-1) and Example 3 (Sample 3-1) A roll of the sensitized gold-sensitized photographic material was accommodated in a container for the production of the film magazine for surveillance cameras shown in FIG. The film magazine for surveillance camera was allowed to fall naturally once from a height of 2 m onto an iron plate having a thickness of 10 mm, and the state of damage was visually observed. The weight of the film magazine for surveillance cameras subjected to the drop test was 500 g. Each test was performed 10 times. Table 1 shows the number of damaged film magazines for surveillance cameras that could not be used (light shielding properties could not be secured).

3) Determination of Hydrogen Cyanide Content Resin pellets produced in the above Examples and Comparative Examples were
g, weighed into a 500 mL flask, and extracted hydrogen cyanide in the resin pellets by the method described above.
In the section of cyanide described in K0102 (Factory drainage test method) 38, 38.1.2 Pyridine-pyrazolone absorptiometry operation was performed, and the absorbance at 638 nm was measured using an absorptiometer (V3210, Hitachi, Ltd.) And the amount of hydrogen cyanide was determined. Table 2 shows the results.

4) Evaluation of Influence on Photosensitive Material Photosensitive material packaging containers produced using the resin pellets produced from the resin pellets of the above Examples and Comparative Examples were
A film magazine for a surveillance camera shown in FIG. 1 was manufactured by accommodating a roll of photographic light-sensitive material in which the sensitized gold-sensitized material was rolled. This film magazine for surveillance camera was prepared by using ethylene / 1-hexene copolymer resin (furnace carbon black 3% by weight, calcium stearate 0.1% by weight, erucamide amide 0.05% by weight, hindered phenolic antioxidant 0.1%). 05% by weight
Was sealed in a sealable light-shielding bag having a thickness of 100 μm and a moisture permeability of 3 g / m ² , and the container was closed for 3 days while maintaining the temperature at 50 ° C. After the standing, the film magazine for surveillance camera was taken out of the light-shielding bag, and the amount of decrease in sensitivity of the photographic photosensitive material contained in the film magazine for surveillance camera was measured. The amount of decrease in sensitivity is determined by measuring the color density of an image obtained by exposing a photographic photosensitive material contained in a film magazine for surveillance cameras to continuous tone exposure, developing the photographic photosensitive material, and calculating gamma (exposure / density). A relational graph is created, and the sensitivity when the density is 0.2 is read from the graph to make it photographic (sensitivity 0.2). Then, the value obtained by subtracting the value of the photographic property (sensitivity 0.2) of the blank sample (the photographic photosensitive material before being accommodated in the film magazine for surveillance camera) from the obtained value of the photographic property (sensitivity 0.2), The sensitivity was reduced by the influence of hydrogen cyanide gas.
The results are also shown in Table 2.

[0067]

[Table 1] Table 1 ────────────────────────────────── Izod impact strength Number of breaks (Kg · cm / cm) (pieces / 10 pieces) １ Example 1 Sample 1-116 0 Example Sample 2-1 11 5 Example 3 Sample 3-1 480 ──

[0068]

[Table 2] ────────────────────────────────── Hydrogen cyanide content (mg / kg) Decrease in sensitivity Amount ────────────────────────────────── Example 1 Sample 1-1 0.15 -0.03 Sample 1-2 0.05-0.01 Sample 1-3 0.01 or less 0 Example 2 Sample 2-1 0.25-0.03 Sample 2-2 0.10-0.02 Sample 2-40 05-0.01 Sample 2-5 0.01 or less 0 Example 3 Sample 3-1 0.20 -0.03 Sample 3-2 0.01 or less 0 ───────────────────── Comparative Example 1 Sample 1-4 0.80 -0.12 Sample 1-5 0.35 -0.07 Sample 1-6 0.25 -0.05 Sample 1-7 0.30- 0.06 Sample 1-8 1.00 -0.22 Comparative Example 2 Sample 2-5 0.35 -0.06 Sample 2-6 0.30 -0.05 Comparative Example 3 0.35 -0.07 ─────────────────────────────────

[0069]

As described above, the injection-molded photographic material of the present invention can store the photographic material for a long period of time without lowering its sensitivity. The injection molded article of the photographic material of the present invention is less likely to be damaged when dropped, and is therefore advantageous for accommodating a large and heavy photographic material.

[Brief description of the drawings]

FIG. 1 is a perspective view showing an example of a photographic light-sensitive material package of the present invention.

FIG. 2 is an exploded perspective view of a film unit with a lens described in Japanese Patent Application Laid-Open No. 9-80693.

FIG. 3 is an exploded perspective view of a resin photographic film cartridge described in JP-A-9-80693.

FIG. 4 is a perspective view of a holder for a packed photographic film film described in JP-A-9-80693.

FIG. 5 is a perspective view of a holder for a packaged sheet film described in Japanese Patent Application Laid-Open No. 9-80693.

FIG. 6 is an exploded perspective view of a photographic film cartridge described in JP-A-9-80693.

FIG. 7 is a perspective view of a photosensitive band container for a microfilm, a computer-printing / planting film, a COM film, etc., described in JP-A-1-187747.

FIG. 8 shows a conventional microfilm, computer-printing film, and CO described in JP-A-1-187747.
It is a perspective view of the photosensitive band container for M films etc.

FIG. 9 is a perspective view of a camera using a light-tight cartridge described in JP-A-2-64533.

FIG. 10 is a cross-sectional view of a photographic film spool described in JP-A-9-80693.

FIG. 11 is a perspective view of a belt-shaped photosensitive material core described in JP-A-9-80693.

[Explanation of symbols]

 1 Film magazine for surveillance camera 2 Container 3 Photosensitive material

Claims (7)

[Claims] 1. An injection-molded article for packaging a photographic photosensitive material having an ABS resin produced by graft polymerization in a range of 25 to 45% by weight and having an Izod impact strength of 10 kg · cm / cm or more. An injection molded article for packaging photographic photosensitive materials, characterized in that the molded article has a hydrogen cyanide content of 0.2 mg / kg or less. 2. The injection-molded article for packaging photographic light-sensitive material according to claim 1, comprising an AS resin in a range of 55 to 75% by weight. 3. An AS resin having an average weight molecular weight of 100,000 or more is in a range of 27.5 to 40% by weight, and an AS resin having an average weight molecular weight of less than 100,000 is in a range of 27.5 to 40% by weight. The injection-molded article for packaging photographic light-sensitive material according to claim 1, characterized in that: 4. The injection molded article for packaging a photographic photosensitive material according to claim 1, wherein the injection molded article contains a substance that adsorbs and holds hydrogen cyanide. 5. The amount of an ABS resin powder produced by graft polymerization is 25 to 45% by weight, the amount of an AS resin having a weight average molecular weight of 100,000 or more is 27.5 to 40% by weight, and the weight average molecular weight is less than 100,000. AS resin powder amount of 27.5-4
0% by weight, the total amount of these resin powders is 100% by weight, and the weight average molecular weight is 100,000 or more.
A mixed powder having a weight ratio of the resin powder to the AS resin powder having a weight-average molecular weight of less than 100,000 in a ratio of 1: 0.8 to 1.1 is kneaded by an extruder, pelletized, and injection molded. An injection molded article for packaging a photographic photosensitive material having an Izod impact strength of 10 kg · cm / cm or more, wherein the hydrogen cyanide content of the injection molded article is 0.2 mg / kg or less. Injection molded products for packaging. 6. The method of claim 1, wherein the sensitized photographic material is gold-sensitized.
6. A photographic light-sensitive material package, which is packaged using the injection-molded product for photographic light-sensitive material packaging according to any one of the above items 5 to 5. 7. The photographic light-sensitive material package according to claim 6, wherein the package is sealed in a moisture-proof packaging material having a moisture permeability of 10 g / m ² · 24 hours or less.