JPH1115112A - Injection molded product for photographic sensitive material and its manufacture - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide injection molded products for a photographic sensitive material which have excellent external appearance with high commercial value, which is excellent in heat resistance, by which size change is reduced, which can improve flame-retardant, and which can perfectly secure light shielding ability, and by which the suitability for photographic use of a photographic film is not adversely affected. SOLUTION: Resin composition which is put in a cylinder 61 and melted is kneaded within the temperature range of 160 to 250 deg.C. As to a screw; a screw whose L/D expressing the rate of effective length L and diameter D is within the range of 15 to 70, for example, is selected. The melted resin composition reaching the leading end 61a of the cylinder 61 is consecutively extruded from a die 65 in a strand-state through an aperture end 65a. The size reduction rate being the ratio of the diameter of the die 65 and the diameter of the resin composition molded in the strand-state is selected within the range of 0.7 to 1.4.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an injection molded article for a photographic material which is most suitable for use in a photographic material and a method for producing the same.

[0002]

2. Description of the Related Art For example, U.S. Pat. No. 5,317,355 discloses that a photographic film is wound around a spool to the tip and stored in a resin cartridge body. A resin photographic film cartridge used in an advanced photo system (hereinafter referred to as APS), which is a new photographic system in which a photographic film is fed out from an opening provided in a cartridge body, is described.

[0003] For example, Japanese Utility Model Publication No. 5-2919 discloses a unit formed of a polystyrene resin composition containing carbon black and rubber, containing an unexposed photographic film cartridge, provided with a simple photographing mechanism. A film unit with a lens composed of a main body is described.

Further, Japanese Patent Application Laid-Open No. Hei 5-341378,
Japanese Patent Application Laid-Open No. Hei 5-341379 discloses a sheet photo film pack for accommodating a plurality of sheet-shaped photo films in a light-shielded state, and a sheet photo film pack mounted on the back of a camera with the sheet photo film pack stored. The holder is listed.

Conventionally, a light-shielding resin composition has been used as a main constituent material of the cartridge body, the unit body, the sheet photo film pack, and the sheet photo film pack holder. As such a resin composition, for example, a polystyrene resin is generally used. Polystyrene resins are produced in large quantities because molded products have good dimensional stability, are tasteless, odorless and nontoxic, and are inexpensive.

However, ordinary homopolystyrene resins are:
Due to the fact that it is easily attacked by some of oils and organic solvents, the weather resistance and heat resistance are insufficient, it is easy to be charged, and the breakdown strength is inferior. In light-shielding injection-molded products containing light-shielding substances such as carbon black, the breaking strength is superior to that of homopolystyrene resin, but it is easily attacked by a part of oils and organic solvents, and the heat resistance is insufficient. A rubber-containing polystyrene resin obtained by graft copolymerizing a synthetic rubber such as butadiene rubber with a styrene monomer (generally referred to as an impact-resistant polystyrene resin) is used.

[0007]

However, as described above, the conventional resin material constituting the cartridge body, the unit body, the sheet photographic film pack, the photographic film pack holder and the like has a pellet shape supplied to an injection molding machine. The orientation of the resin molecules and the light-shielding substance in the flow direction of the resin is different, and the dimensional accuracy in the vertical and horizontal directions of the injection molded product changes due to the distortion of the molecular structure. There is a problem that the dimensional accuracy, heat resistance, physical strength, and rigidity required for the product are insufficient.

In particular, in a photosensitive material package using such an injection molded product for a photographic photosensitive material, which is often used outdoors or the like where the temperature changes drastically, the deformation and dimensional change of the injection molded product become large, and Warpage and torsion also occur in the injection molded product,
Problems such as poor feeding of photosensitive materials such as light fog and photographic films have often occurred. Also, if the external environment is below freezing in winter, etc., the impact strength will be greatly deteriorated, and if a molded product is accidentally dropped, it will be easily damaged or deformed, and optical fog or photographic film will be fed. There is also a problem that defects and the like occur. In particular, a resin photographic film cartridge and a lens-equipped film unit, which are frequently used outdoors in the world, need to solve the above problem.

Further, since the dispersibility of the light-shielding substance is not good, it is necessary to increase the amount of the light-shielding substance to maintain the light-shielding property. As a result, the physical strength of the injection-molded article is reduced. Also occurs. Furthermore, there is a problem in that the occurrence of bumps and weld lines increases, and the moisture absorption increases, and molding troubles such as silver stripes and short shots often occur.

The present invention has been made in consideration of the above-mentioned problems of the prior art, and has an excellent appearance having high commercial value,
Excellent heat resistance, little dimensional change, improved flame retardancy, no warpage or twisting, perfect light-shielding properties, bad influence on photographic film photographic properties (fog generation, abnormal sensitivity, abnormal gradation, An object of the present invention is to provide an injection-molded product for a photographic light-sensitive material that does not give abnormal coloring or uneven density.

[0011]

In order to achieve the above object, in the injection molded article for a photographic material according to claim 1, the diameter of a die of an extruder for molding a thermoplastic resin into a strand shape; The withdrawal ratio, which is the ratio of the strand-shaped resin formed by this extruder to the diameter of the resin, is 0.7 to
It is injection-molded using a cylindrical resin pellet formed by cutting a strand-shaped thermoplastic resin extruded in the range of 1.4.

According to a second aspect of the present invention, there is provided a method for producing an injection-molded article for a photographic light-sensitive material, comprising 0.01 to 5% by weight of a lubricant and 0.1 to 10% by weight of a synthetic rubber having an average particle size of 1.5 to 5 μm. % Of the styrenic resin composition containing
The draw-down ratio, which is the ratio of the diameter of the die of an extruder for melting and kneading in a temperature range of 250 ° C. to form a strand shape, and the diameter of the strand-shaped resin molded by this extruder, is 0.7. The styrenic resin composition in the form of a strand extruded so as to be in the range of ~ 1.4 to 0.2
It is injection-molded at a temperature range of 160 to 250 ° C. using cylindrical resin pellets formed by cutting to a length of up to 6 mm.

According to a third aspect of the present invention, there is provided a method for producing an injection molded article for a photographic light-sensitive material, wherein 0.01 to 5% by weight of a lubricant and 0.1 to 10% by weight of a synthetic rubber having an average particle size of 1.5 to 5 μm. %, A styrene resin composition containing 0.001 to 1.0% by weight of an antioxidant and 0.1 to 10% by weight of a light-shielding substance is melt-kneaded in a temperature range of 160 to 250 ° C. to obtain a strand shape. The L / D ratio, which is the ratio of the effective length L of the screw of the extruder to the outer diameter D, is in the range of 15 to 70, and the diameter of the die of the extruder and the molding by this extruder. The strand-shaped styrenic resin composition extruded so that the draw-down ratio, which is the ratio to the diameter of the formed strand-shaped resin, is in the range of 0.7 to 1.4, is 0.2 to 6 mm. Cylindrical shape formed by cutting to length The resin pellets moisture content 0.5
% And dried by injection molding in a temperature range of 160 to 250 ° C.

According to a fourth aspect of the present invention, there is provided a method for producing an injection-molded article for a photographic light-sensitive material, comprising 0.01 to 5% by weight of a lubricant and 50% of a polystyrene resin having a syndiotactic structure.
The diameter of a die of an extruder for melting and kneading a styrene-based resin composition containing at least 160% by weight in a temperature range of 160 to 350 ° C. to form a strand shape, and the shape of the strand shape formed by the extruder. The strand-shaped styrene resin composition extruded so that the draw-down ratio, which is the ratio to the diameter of the resin, falls in the range of 0.7 to 1.4 is cut to a length of 0.2 to 6 mm. 230-350 ° C. using the cylindrical resin pellets
Injection molding in the temperature range of

According to a fifth aspect of the present invention, there is provided a method for producing an injection-molded article for a photographic light-sensitive material, comprising 0.01 to 5% by weight of a lubricant and 50% of a polystyrene resin having a syndiotactic structure.
% By weight or more, 0.001 to 1.0% by weight of an antioxidant,
The effective length L and the outer diameter D of a screw of an extruder for melting and kneading a styrene-based resin composition containing a light-shielding substance in an amount of 0.1 to 10% by weight in a temperature range of 160 to 350 ° C. to form a strand shape. L / D ratio, which is 15 to
In addition to the range of 70, the draw-down ratio, which is the ratio of the diameter of the die of the extruder to the diameter of the strand-shaped resin formed by the extruder, is in the range of 0.7 to 1.4. The thus obtained extruded strand-shaped styrene-based resin composition is cut into a length of 0.2 to 6 mm to form a cylindrical resin pellet until the water content becomes 0.5% or less. Dry, 230-350 ° C
Injection molding in the temperature range of

[0016]

DESCRIPTION OF THE PREFERRED EMBODIMENTS First, an injection molded article for a photographic light-sensitive material of the present invention and a resin material used in a method for producing the same will be described. It is preferable to use a thermoplastic resin as a resin material constituting an injection molded product for a photographic photosensitive material, and a thermoplastic material obtained by kneading a light-shielding substance for imparting light-shielding properties to the thermoplastic resin and a fibrous filler. It is preferable to use a resin composition.

If necessary, a lubricant, an antistatic agent, a drip-proof agent, a flame retardant, an ultraviolet absorber, a metal deterioration inhibitor, a compatibilizer, a thermoplastic elastomer, an inorganic or organic pigment, a processing aid, an antioxidant Photographs that apply various kinds of additives such as agents, fragrances, desiccants, desiccants, chelating agents, inorganic or organic nucleating agents, plasticizers, etc. that do not adversely affect the photographic properties of photographic materials. It may be contained alone or in combination of two or more kinds in the cylindrical resin pellet of the present invention in accordance with the photosensitive material.

The thermoplastic resin used for the resin material of the injection molded product for photographic photosensitive materials is preferably
Various homopolyethylene resins, various ethylene copolymer resins, homopolypropylene resins, propylene / α-olefin copolymer resins, homopolystyrene resins, synthetic rubber-containing polystyrene resins produced by polymerization using a multisite polymerization catalyst by a conventionally known method. , ABS resin, acrylonitrile-styrene resin, AAS (ASA) resin, AES resin (weather-resistant and impact-resistant resin), syndiotactic polystyrene resin, various polyethylene resins polymerized using single-site catalyst, polyolefin-based heat Homopolypropylene resin, propylene / α-olefin copolymer resin (random or block type), homopolyethylene resin of various densities, ethylene / α-olefin of various densities Polymeric resins, polystyrene-based resins.

Of these, styrene resins having syndiotactic stereoregularity produced by polymerization using a single-site catalyst (typically a metallocene resin) having excellent heat resistance and solvent resistance are particularly preferred. Most preferred is a thermoplastic resin comprising 1 to 99% by weight of a styrene resin having syndiotactic stereoregularity described in detail below and 1 to 99% by weight of one or more kinds of thermoplastic resin elastomers. (Other thermoplastic resins may be contained).

The styrenic resin having syndiotactic stereoregularity is a non-crystalline resin because the styrenic resin produced by the conventional radical polymerization method has an atactic three-dimensional structure, and is resistant to heat and solvent. It is a crystalline polystyrene resin with improved disadvantages of poor properties. The glass transition temperature (abbreviation Tg) is 90 ° C. or higher, preferably 95 ° C. or higher, more preferably 100 ° C. or higher, and particularly preferably 10 ° C. or higher.
5 ° C. or higher. Inorganic compounds, metal salts of ionic hydrocarbon copolymers in this syndiotactic styrene resin,
A nucleating agent, a crystallization accelerator, and a paragraph “013” described later
It is preferable to further improve various properties by adding a thermoplastic resin elastomer described in 3) to 0145.

Examples of the styrene resin include general-purpose polystyrene resin, impact-resistant polystyrene resin (also referred to as synthetic rubber graft-polymerized polystyrene resin or high-impact polystyrene resin and abbreviated as HI polystyrene resin), styrene-acrylonitrile Resin, styrene-acrylonitrile-butadiene resin, AES resin, styrene-methyl methacrylate-acrylonitrile resin, acrylonitrile-acrylic rubber-styrene resin, styrene-butadiene block copolymer resin, styrene-maleic anhydride copolymer resin, etc. Can be

Among the thermoplastic resins mentioned above, the styrene-based resins which are particularly preferred are inexpensive, have high physical strength, are excellent in rigidity, heat resistance and abrasion resistance, and have good photographic properties. Excellent injection moldability. Such a styrenic resin contains 0.01 to 5% by weight of a lubricant,
Synthetic rubber having an average particle size of 1.5 to 5 μm is 0.1 to 10
% By weight, 0.001 to 1.0% by weight of an antioxidant, and 0.1 to 10% by weight of a light-shielding substance.

The styrenic resin used in the present invention may contain other monomers such as propylene, butene-1, pentene and 4-methylpentene as long as their performance is not impaired.
Α-olefins such as 1, hexene, octene and decene, dienes such as butadiene and isoprene, cycloolefins such as cyclopentene, cyclohexene and cyclopentadiene, and acrylates such as methyl acrylate, ethyl acrylate and butyl acrylate are copolymerized. May be.

In addition to those described above, thermoplastic resins particularly preferred in the present invention are excellent in various properties (physical strength, rigidity, heat resistance, abrasion resistance, etc.) and are particularly stable at high temperatures. If it is, any type may be used and is not limited. For example, polyethylene terephthalate (PET), polyethylene naphthalate (PEN),
Aromatic polyester resin composed of aromatic dicarboxylic acid such as polybutylene naphthalate (PBN) and diol or oxycarboxylic acid, nylon 6, nylon 6
6, polyamide 6-10, nylon 12, polyamide resin such as nylon 46, ethylene, propylene, olefin resin containing butene as a main component, homopolystyrene,
Styrene-butadiene copolymer, styrene-acrylonitrile copolymer, styrene resins such as ABS, polycarbonate resin, polyphenylene oxide resin, polyalkyl acrylate resin, polyacetal resin, polysulfone resin, polyether sulfone resin, polyphenylene sulfide resin, Examples thereof include a polyetherimide resin, a polyetherketone resin, and a fluorine resin. Further, these thermoplastic resins may be used by mixing two or more kinds of arbitrary resins. Especially good compatibility 2
A polymer alloy obtained by melt-kneading at least one kind of thermoplastic resin is particularly preferable because of its excellent physical properties and good appearance.

In the present invention, each of the above homopolymer resins, two or more copolymer resins, or
A blend of two or more of these homopolymers and copolymer resins may be used, or a polymer alloy may be used, but the invention is not limited thereto. Polymer blending methods are classified into physical Brent, chemical Brent, and polymer complex, and may be a blend blended by any method.

Next, representative examples of light-shielding substances for imparting light-shielding properties to the thermoplastic resin used in the present invention are shown below. However, photographic properties are often adversely affected by the type of photographic light-sensitive material, ISO sensitivity, and the like. Therefore, it is necessary to carefully select the type, the amount added, the additive used in combination, and the molding condition sugar. 1. Inorganic compounds A. Oxides: silica, diatomaceous earth, alumina, titanium oxide, iron oxide (iron black), zinc oxide, magnesium oxide, antimony oxide, barium ferrite, strontium ferrite, beryllium oxide, pumice, pumice balloon, alumina fiber, etc. Hydroxide; aluminum hydroxide, magnesium hydroxide, basic magnesium carbonate, etc. Carbonates; calcium carbonate, magnesium carbonate, dolomite, dawsonite, etc.

D. (S) sulfite; calcium sulfate, barium sulfate, ammonium sulfate, calcium sulfite, etc. Silicates; talc, clay, mica, asbestos, glass fiber, glass balloon, glass beads, calcium silicate, montmorillonite, bentonite, etc. Carbon; carbon black, graphite, carbon fiber, carbon hollow sphere, etc. Others: iron powder, copper powder, lead powder, aluminum powder, molybdenum sulfide, polon fiber, silicon carbide fiber, brass fiber, potassium titanate, lead zirconate titanate, zinc borate, barium metaborate, calcium borate, borate Sodium acid, aluminum paste, etc.

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

Among these light-shielding substances, inorganic compounds which have little adverse effect on photographic properties, are stable to heat even under injection molding at 150 ° C. or higher, and make opaque injection molded articles are preferred. Light-absorbing carbon black, titanium nitride, graphite, and iron black, which are relatively inert substances having excellent light-shielding properties, heat resistance, and light resistance, are preferred. The most preferable light-shielding substance is inexpensive, has a large light-shielding ability, and does not adversely affect the photographic properties of the photosensitive material.
It is stable to heat even at 00 ° C or higher, is harmless to the human body, can be incinerated, and has a thermal stabilizing effect of thermoplastic resin. And an excellent action of hardly causing physical strength deterioration in an injection molded article.

Examples of the classification of carbon black, which is the most preferable light-shielding substance in the present invention, according to the raw material include gas black, furnace black, channel black, anthra black, acetylene black, Ketchen carbon black, thermal black, lamp black, Oil smoke, pine smoke, animal black, vegetable black and the like are available.

Representative examples of preferable commercial products of carbon black include, for example, acetylene black manufactured by Denki Kagaku and carbon black # 20 (B) and # 3 manufactured by Mitsubishi Chemical.
0 (B), $ 33 (B), $ 40, $ 41 (B), $ 4
4 (B), $ 45 (B), $ 50, $ 55, $ 100,
$ 600, $ 950, $ 1000, $ 2200, $ 22
00 (B), $ 2400 (B), MA8, MA11, MA
100 and the like.

As overseas products, for example, Black Pearls 2, 46, 70, 71, manufactured by Cabot Corporation,
74, 80, 81, 607 etc., Regal 300, 3
30, 400, 660, 991, SRF-S, etc., Vul
Sterling 1 such as can 3, 6, XC-72
0, SO, V, S, FT-FF, MT-FF and the like.

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

In the present invention, there is little adverse effect on the photographic properties of the photographic light-sensitive material, it can withstand a molding temperature of 180 ° C. or more (300 ° C. or more for some engineering plastics), has a large light-shielding ability, and is low in cost. Furnace carbon black which causes a small decrease in the physical properties of molded articles is preferable. As the carbon black having an antistatic effect, acetylene carbon black, ketjen carbon black which is a modified by-product carbon black, and conductive furnace carbon black (Vulcan XC- 72 etc.) are preferred. If necessary, the former and the latter are preferably used in combination of two or more kinds according to the required characteristics. The form in which the light-shielding substance is blended with the thermoplastic resin is roughly classified as follows.

(1) Uniformly colored pellets (most commonly used as color compounds) (2) Dispersed raw powders (treated with various surface treatment agents also called dry color, and further dispersed (3) Paste (dispersed in plasticizer, etc.) (4) Liquid (liquid dispersed in surfactant, also called liquid color) (5) Masterbatch pellet (a light-shielding substance is dispersed at high concentration in plastic to be colored) (6) Hygroscopic powder (a light-shielding substance is dispersed at high concentration in plastic, (7) Dry powder (Normal unprocessed dry powder)

Although there are various modes in which the light-shielding substance is mixed with the thermoplastic resin as described above, a master batch is preferable in terms of cost, prevention of contamination of the work place, and the like. The present applicant also discloses in JP-B-63-186740 a resin composition for a colored masterbatch in which a light-shielding substance is dispersed in a specific ethylene / ethyl acrylate copolymer resin.

When used as an injection molded product for a photographic material of the present invention, the photographic material does not cause fogging, the sensitivity does not increase or decrease, and the light shielding ability is large.
Even when added to a thermoplastic resin, hardening of the carbon black (dust) is unlikely to occur. Therefore, among carbon blacks, particularly, pH (measured by JIS K6221) is 6.0 to 9.0.
, Average particle size (measured by electron microscope) is 10 ~ 120n
m, particularly preferably 10 to 80 nm, and among these, the volatile component (measured by JIS K6221) is 2.0% or less, and the DBP oil absorption (measured by the oil absorption A method of JIS K6221) is 50 ml / 100 g or more. Furnace carbon black is preferred in that it is low in cost, has good photographic properties, improves light-shielding properties, improves antistatic properties, improves dispersibility, and causes little deterioration in physical properties of injection molded articles.

Cyan compounds and sulfur compounds in injection-molded articles deteriorate photographic properties (such as fogging, a sense of increase or decrease, and abnormal coloring). Agents need to be carefully selected. After trapping with 1N sodium hydroxide of hydrogen cyanide generated by refluxing in the presence of sulfuric acid, the amount of hydrogen cyanide quantified by pyrazolone 4-pyridinecarboxylate absorption spectrometry is 50 ppm or less, preferably 50 ppm or less. Is 20
ppm or less, particularly preferably 10 ppm or less. Furthermore, the sulfur content by a measuring method according to ASTM D 1619-60 is 0.9% or less, preferably 0.6% or less, particularly preferably 0.4% or less, particularly preferably 0.1% or less.
If the content is not less than 2%, the photographic properties of the photographic light-sensitive material are adversely affected, such as increased fog, sensitivity and abnormal coloring.

In particular, a free sulfur component which greatly adversely affects the photographic properties of the photographic light-sensitive material directly (each sample was cooled and solidified with liquid nitrogen, then pulverized, and 100 g of the pulverized sample was put in a Soxhlet extractor at 700 ° C. and 60 ° C. After extraction and cooling for 8 hours, the total volume is made up to 100 ml, and 10 ml of this solution is injected into a high performance liquid chromatograph to quantify sulfur.

The conditions for high-performance liquid chromatography separation were as follows: column; ODS silica column (4.5 φ × 150 mm), separation solution: methanol 95 and ice 5 (acetic acid and triethylamine were each 0.1%).
%) Flow rate; 1 ml / min, detection wavelength; 254 mm, quantification is performed by the absolute calibration method. ) Is 0.1% or less, preferably 0.0%
5% or less, particularly preferably 0.01% or less, most preferably
0.005% or less. Further, the content of the free formaldehyde quantification method described on page 375 of Polymer Analysis Handbook (KK Asakura Shoten, published March 1, 1986) which deteriorates photographic properties is 0.2% or less, preferably 0.1% or less, particularly Preferably it is 0.05% or less, most preferably 0.01% or less.

The content of a cyanide compound that deteriorates photographic properties (a value obtained by converting the amount of hydrogen cyanide determined by 4-pyridinecarboxylic acid / pyrazolone absorption spectrometry into a PPM unit based on the weight of the light-shielding substance) is preferably 50 ppm or less. Is 2
0 PPM or less, particularly preferably 10 PPM or less, most preferably 5 PPM or less, iodine adsorption amount (measured by JIS K 6221)
Is at least 20 mg / g, preferably at least 30 mg / g, particularly preferably
50 mg / g or more, most preferably 80 mg / g or more, and a dibutyl phthalate (DBP) oil absorption (measured by the method A of JIS K 6221) of 50 ml / 100 g or more, preferably 60 ml / 100 g or more, particularly preferably 70 ml / g / 100g or more, most preferably 10
0ml / 100g or more carbon black.

Next to carbon black, preferred light-shielding substances are inorganic pigments having a refractive index of 1.50 or more as measured by Larsen's oil immersion method, various metal powders, metal flakes, metal pastes, metal fibers and carbon fibers. Preferred refractive index is 1.
Representative examples of 50 or more inorganic pigments and metal powders are shown below,
The present invention is not limited to these. ()
The numbers in the parentheses indicate the refractive index.

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

Calcium silicate having a refractive index of less than 1.50 (1.
46), diatomaceous earth (1.45), hydrated silicic acid (1.44), etc. have a small light-shielding ability and need to be added in large amounts, and are effective as blocking inhibitors, but are not preferred as light-shielding substances. In addition, due to the recent overseas travel boom, the inspection equipment using X-rays for baggage inspection at the airport
X when passed through a high-sensitivity photographic film with a sensitivity of 400 or more
Lines tend to cause fog. In order to prevent this, it is preferable to use a light-shielding substance having a specific gravity of 3.1 or more, preferably 3.4 or more. Specific gravity of 3.1 or more, preferably
The form of the light-shielding substance having an X-ray shielding property other than the light-shielding property of 3.4 or more, particularly preferably 4.0 or more is not limited to those exemplified below as typical examples, and any form, for example, pigment, powder, flake, whisker, It may be a fiber or the like.

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

Particularly preferable light-shielding substances for imparting X-ray blocking properties are zircon, corundum, barium sulfate, barium chloride, barium titanate, lead powder, lead oxide, zinc powder, zinc white, tin powder, stainless powder, Stainless whisker, iron oxide, tungsten whisker, nickel whisker. A light-shielding substance which is particularly preferable as an injection molded article for an ultra-high-sensitivity photographic photosensitive material having an ISO sensitivity of 400 or more has a refractive index of 1.50 or more and a specific gravity of 3.1 or more, and most preferably has a refractive index of 1.56 or more and a specific gravity of 3.4 or more. Is a light-shielding substance. The content of these light-shielding substances varies depending on the layer thickness and the type of resin used, but is preferably 0.1 to 10% by weight.

Further, the thermoplastic resin composition of the present invention comprises
Known additives generally added to thermoplastic resins, namely stabilizers such as antioxidants and ultraviolet absorbers, antistatic agents,
Flame retardants, coloring agents such as dyes and pigments, lubricants, mold release agents, and the like can be appropriately added according to the required performance.

Exerts effects such as antistatic action and antifogging property,
In addition, nonionic surfactants that also function to improve the dispersibility of the light-shielding substance and the filler used in the present invention include, for example, polyoxyethylene tridecyl ether,
Polyoxyethylene oleyl ether, polyethylene glycol, polyoxyethylene nonyl phenyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene polyoxypropylene block polymer, sorbitan monolaurate, sorbitan monooleate, polyoxyethylene dodecylamine, polyglycerin Oleic acid esters and the like can be mentioned.

Among the nonionic surfactants as described above, in particular, polyoxyethylene tridecyl ether,
Polyoxyethylene nonylphenyl ether, polyoxyethylene polyoxypropylene block polymer, polyoxyethylene dodecylamine, polyethylene glycol, polypropylene glycol, etc., which are liquid at 1 atmosphere and 30 ° C., especially prevent whitening of lubricant. It has an excellent antistatic effect, has little adverse effect on the photographic properties of a photographic light-sensitive material, has an excellent antifogging property, and has a high effect of preventing sticking to a mold. The addition amount of these nonionic surfactants is 0.01 to 5% by weight, preferably 0.05 to 4% by weight, more preferably 0.1 to 3% by weight, and particularly preferably 0.1 to 2% by weight. It is. 0.01
If the amount is less than 5% by weight, the effect of addition is not obtained. If the amount exceeds 5% by weight, not only the effect of increasing the amount is not obtained, but also the smoke and the appearance and feel of the molded product are deteriorated.

Representative examples of oil-absorbing inorganic pigments having the effect of adsorbing lubricants, antioxidants, organic nucleating agents, and surfactants which are easy to bleed out, and adsorbing deodorants, fragrances, oxygen scavengers, etc. These include zinc white (52), asbestin (50), clay (51), titanium oxide (56), kaolin (60), talc (60), carbon black (60 or more),
There is activated carbon and the like. The figures in parentheses indicate the oil absorption (JIS K
Measured by the oil absorption A method of 6221. (Unit: ml / 100 g).

Representative examples of metal powder (including metal paste) include aluminum powder, aluminum paste,
Copper powder, stainless steel powder, iron powder, nickel powder, brass powder, silver powder, tin powder, zinc powder, steel powder and the like. However, besides aluminum powder, aluminum paste, stainless steel powder, and silver powder may adversely affect the photographic properties of photographic materials, so be careful when using them as injection molded products for direct contact with photographic materials. is necessary.

In the present invention, the term “aluminum powder” includes both aluminum powder and aluminum paste. The aluminum powder is obtained by coating the surface of the aluminum powder with a surface coating material, or by removing the aluminum paste from the aluminum paste and removing a low volatile substance from a thermoplastic resin. What is kneaded is preferable. For an aluminum powder with excellent uniform dispersibility, moldability, photographic properties and appearance, and low odor, the average particle size should be 0.3-50μ
m, preferably 0.5 to 45 μm, particularly preferably 0.8 to 40
μm, average thickness 0.03 to 0.5 μm, preferably 0.05 to
The aluminum powder is 0.4 μm, particularly preferably 0.08 to 0.35 μm, and the content of various fatty acids is 5% by weight or less, preferably 4% by weight or less, particularly preferably 3% by weight or less.

Here, the aluminum paste refers to a mineral spirit and a small amount of a higher fatty acid such as stearic acid, palmitic acid or oleic acid when an aluminum powder is prepared by a known method such as a ball mill method, a stamp mill method or an atomizing method. It was made into a paste in the presence of

In the thermoplastic resin composition used in the present invention, this aluminum paste and a styrene-based resin (polystyrene resin,
Rubber-containing polystyrene resin, ABS resin, etc.), polyolefin thermoplastic resin (various polypropylene resin, propylene-α-olefin copolymer resin, various polyethylene resins, acid-modified resin, ethylene-α-olefin copolymer resin, EVE resin, EEA resin , EAA resins, etc.), low molecular weight polyolefin resins, various thermoplastic elastomers (ThermoPlastic elastomer,
Hereinafter, it is referred to as TPE, and typical examples are a polystyrene-based TPE, a polyolefin-based TPE, and a block copolymer including a soft segment of polybutadiene or polyisoprene and a hard segment of polystyrene.
2 Polybutadiene TPE, polyurethane TPE, polyester TPE, polyamide TPE, chlorinated polyethylene TPE, polyfluorocarbon TPE, etc.
In particular, polystyrene-based TPE, polyolefin-based TPE, and polyester-based TPE are preferred. ), Paraffin wax, tackifier (terpene resin, coumarone indene resin, petroleum resin, mineral oil, etc.), fungicide (copper-8-)
Dispersing agents such as quinolinolate, bis (tributyltin) oxide, tributyltin acetate, bis (tributyltin) trisulfide, tributyltin laurate, etc., and metallic soap are heated and kneaded, and low volatile substances (mainly mineral spirits with strong odor, White spirit can be used as an aluminum paste compound resin or an aluminum paste masterbatch resin having a volatile matter content of 3% or less, preferably 1% or less, particularly preferably 0.5% or less, removed by a vacuum pump or the like. preferable.

In particular, use as an aluminum paste masterbatch resin is preferred in order to eliminate adverse effects and odor on photographic light-sensitive materials. For example, even if the mineral spirit content in a masterbatch resin having an aluminum paste content of 40% by weight is 1.0% by weight, the concentration of the aluminum paste in an injection molded product for a photographic light-sensitive material is reduced to 2%.
In order to make the weight percentage, 19 parts by weight of a natural resin (resin for dilution) is kneaded with 1 part by weight of the aluminum paste masterbatch. Mineral spirit content is 0.
05% by weight or less. As a result, the photographic properties of the photographic material are not adversely affected, and the odor is reduced.

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

Particularly, an aluminum foil rolled to a predetermined thickness (5 to 20 μm, preferably 6 to 15 μm, particularly preferably 7 to 10 μm) using a rolling oil which does not adversely affect the photographic properties of the photographic light-sensitive material is shredded. Then, annealing is performed and fatty acids are removed, and then 5% by weight or less of a fatty acid having 8 or more carbon atoms (including a compound) is added to the cut aluminum foil. Then, the average particle diameter is 0.3 to 50 μm using at least one of a pulverizer selected from a ball mill, a stamp mill, a vibration mill and an attritor.
m, an average thickness of 0.03 to 0.5 μm and an aluminum powder having a fatty acid content of 5% by weight or less. In the present invention, this aluminum powder is particularly preferable because it has excellent dispersibility, photographic properties, and gloss and has little odor.

For practical use as the injection molded product for photographic light-sensitive materials of the present invention, in order to improve the quality, physical strength, photographic performance, light-shielding property, injection moldability, economy, etc. Although the preferable total content of the light-shielding substance in the molded article is 0.1 to 10% by weight, the content is appropriately changed depending on the light-shielding ability of the light-shielding substance and the thickness of the injection molded article. In the case of carbon black, titanium oxide, and aluminum powder having excellent light-shielding ability, the total content in the injection-molded product is 0.1 to 10% by weight from the viewpoint of ensuring light-shielding properties, economy, securing physical strength, and injection moldability. % Is preferred, and 0.3
-8% by weight is more preferable, 0.5-6% by weight is particularly preferable, and 0.7-4% by weight is most preferable.

If the total content is less than 0.1% by weight, unless the thickness of the injection-molded product is made very large, the light-shielding ability becomes insufficient and light fog occurs. In addition, if the thickness of the injection molded product for a photographic photosensitive material is increased in order to obtain a sufficient light-shielding property with this content, the injection molding cycle of the injection molded product for a photographic photosensitive material becomes longer (because the cooling time becomes longer). ), Sink mark (sink mark), warpage and torsion are likely to occur, and the amount of resin used is large and expensive, so that practical use is difficult.

On the other hand, if the content exceeds 10% by weight, the dispersibility deteriorates, the generation of microgrids (aggregated impurities) increases, and pressure fog and abrasion occur on the photographic light-sensitive material. The amount of water in the injection molded article increases due to an increase in the amount of water adsorbed on the carbon black, and adversely affects the photographic properties of the photographic light-sensitive material (fog generation, abnormal sensitivity, abnormal coloring, etc.). Further, the injection moldability of the injection molded product for photographic photosensitive materials is deteriorated (molding failure such as foaming, silver stripes, burning, pinholes, short shots, etc. is caused) and the physical strength is reduced, and practical use is difficult.

Light-shielding substances (light-absorbing light-shielding substances such as carbon black and iron black, light-absorbing light-shielding substances such as aluminum powder and titanium oxide, inorganic pigments having a refractive index of 1.50 or more, and specific gravity of 3.4 or more) (Inorganic pigments, inorganic pigments having an oil absorption of 50 ml / 100 g or more are particularly preferred.) The use of microgrit that improves dispersibility in resin, improves resin fluidity, and causes friction fog, pressure fog, and scratches on photographic photosensitive materials. The surface is preferably coated with a surface coating material to prevent generation thereof, prevent generation of volatile substances harmful to photographic properties, suppress moisture absorption, and prevent mold surface contamination. Representative examples of the surface coating material are shown below. The coating amount of the surface coating material of the light-shielding substance is 0.1 to 200 parts by weight, preferably 0.5 to 150 parts by weight, more preferably 1 to 100 parts by weight, particularly preferably 100 parts by weight of the light-shielding substance. It is 2 to 80 parts by weight, most preferably 5 to 60 parts by weight.

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

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

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

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

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

Examples of the monocarboxylic acid include montanic acid, melicic acid, serotonin, bricinic acid, laccellic acid and the like. Examples of the monohydric alcohol include montyl alcohol, melisyl alcohol, racyl alcohol, seryl alcohol, brisyl alcohol and the like.

These are very excellent as a surface coating material of the light-shielding material because they improve the fluidity of the thermoplastic resin and achieve uniform kneading. further,
When used as an inorganic or organic nucleating agent or one of these dispersants for surface coating, various excellent effects such as scattering prevention, bleedout prevention, uniform dispersibility improvement, and resin fluidity improvement are exhibited.

In the present invention, the light-shielding substance for coloring may be added to the thermoplastic resin composition constituting the injection-molded article of the present invention, so as to be translucent or opaque. As a result, the light-shielding property is improved, the rigidity is increased, and the injection moldability is improved, the coloring failure of the resin and the lumps are less noticeable, the appearance is beautiful, and the commercial value is increased. Further, in the case of a container for photographic film patrones or the like, it is preferable to color the container main body or the container lid so that it can be used to identify the type of the photographic photosensitive material in the opaque, translucent or transparent container (for example, the container lid). Coloring: red-reversal film, green-ISO speed 400 color negative film, black-ISO speed 800 color negative film, white-micro film). Examples of the light-shielding substance for coloring include a dye, a colored pigment, a white pigment, a metal powder, a metal fiber, a metal flake, and carbon black.

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

Red; red bengara, disazo pigment, berlene pigment, monoazo lake pigment, condensed azo pigment, cadmium red, bon red 2B, carmine 6B, pyrazolone red, lake red C, lead red, permanent red 4
R, etc. Blue; Cobalt blue, ultramarine, navy blue, phthalocyanine blue, cyanine blue, indanthrene blue, indigo, cyanine blue, etc. Green; chrome oxide green, titanium green, zinc green, emerald green, cobalt green, pigment green, phthalocyanine green , Cyanine green, etc. Silver; aluminum powder, aluminum paste, tin powder, etc. Gold; copper powder, copper alloy powder, aluminum powder and yellow pigment, aluminum paste and yellow pigment, etc. In particular, carbon black and iron black are inexpensive, and spot-like coloring failure of resin and lumps (foreign-like lump) are not conspicuous, light shielding ability is excellent, photographic properties are good, antioxidant synergistic effect, etc. It is preferred in that respect.

When color printing is performed on a package, a cartridge body, or the like, white, grey,
It is preferable to color yellow, gold or silver. Cameras that are injection molded products for photographic photosensitive materials that are used for a long time under sunlight, left for a long time under sunlight, or used even in deserts, resin photographic film cartridges for APS, and spools for photographic films In the case of sheet photo film packs, sheet photo film pack holders, film units with lenses, etc., light-reflecting materials such as white, silver, yellow and gold can be used alone or in combination of two or more. It is preferable to color it.

Representative examples of the lubricant which can improve the injection moldability, improve the dispersibility of the light-shielding substance and improve the lubricity by kneading with the thermoplastic resin of the present invention are shown below. (1) Fatty acid amide-based lubricant (saturated fatty acid amide-based lubricant) Behenic acid amide-based lubricant Stearamide-based lubricant (hydroxystearic amide-based lubricant) Palmitic amide-based lubricant Lauric amide-based lubricant (unsaturated fatty acid amide-based lubricant) Elucamide amide lubricant Oleic amide lubricant

(Bis fatty acid amide lubricant) Methylene bisbehenamide amide lubricant Methylene bis stearamide amide lubricant Methylene bis oleamide amide lubricant Ethylene bis stearamide amide lubricant Hexamethylene bis stearamide amide lubricant Hexamethylene Bisoleic acid amide lubricant

(2) Bicarbonate lubricant; liquid paraffin,
Natural paraffin, micro wax, synthetic paraffin,
Polyethylene wax (having a number average molecular weight of 10,000 or less, preferably 8,000 or less, particularly preferably 6000 or less)
Below), polypropylene wax (number average molecular weight is 10
000 or less, preferably 8000 or less, particularly preferably 6000 or less), chlorinated hydrocarbons, fluorocarbons and the like. (3) fatty acid lubricants; higher fatty acids (C ₁₂ or more, specifically, Kaburon acid, stearic acid, oleic acid, erucic acid, palmitic acid and the like), hydroxy fatty acid and the like. (4) Ester lubricants: lower alcohol esters of fatty acids, polyhydric alcohol esters of fatty acids, polyglycol esters of fatty acids, fatty alcohol esters of fatty acids, and the like. (5) alcohol-based lubricants: polyhydric alcohols, polyglycols, polyglycerols and the like.

(6) Fatty acid metal salt lubricant (metal soap);
Lauric acid, stearic acid, caproic acid, capric acid,
Caprylic acid, myristic acid, succinic acid, stearyl lactic acid, benzoic acid, hydroxystearic acid, lactic acid, phthalic acid, ricinoleic acid, naphthenic acid, oleic acid, palmitic acid, and erucic acid have 6 to 50 carbon atoms, preferably 1
0 to 40, particularly preferably 10 to 30, higher fatty acids and lithium, sodium, magnesium, calcium,
Compounds with metals such as strontium, barium, zinc, cadmium, aluminum, tin, lead, etc., which neutralize catalyst residues to improve the photographic properties of photographic materials and prevent mold rust. Preferable ones having the function of improving the dispersibility of the light-shielding substance include, for example, magnesium stearate, calcium stearate, zinc stearate, magnesium oleate and the like. Particularly preferred are calcium stearate and zinc stearate, and most preferred is zinc stearate.

(7) Silicone-based lubricants: Various grades of dimethylpolysiloxane and modified products thereof (Shin-Etsu Silicone, Toray Silicone), especially various silicone oils, only exert the effects of improving resin fluidity and lubricity. However, when used in combination with a light-shielding substance, the dispersibility of the light-shielding substance is improved, and the resin is opaque to haze (ASTM D-10).
03) is preferable because unexpected effects such as an improvement in coloring power and an improvement in light-shielding properties can be obtained as a result of increasing 03).

The amount of the above-mentioned various lubricants varies depending on the type of the resin or lubricant and the purpose of use.
0% by weight, preferably 0.02 to 4.0% by weight, more preferably 0.03 to 3.0% by weight, particularly preferably 0.
04-2.0% by weight, most preferably 0.05-1.0%
% By weight.

As described above, in addition to the improvement of the lubricity, the photographic light-sensitive material has various effects such as improvement of light-shielding property, improvement of resin fluidity, improvement of physical strength, shortening of molding cycle, improvement of coloring property, and the like. The silicone lubricant which does not adversely affect the photographic properties will be described in more detail below.

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

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

The silicone oil improves the physical strength of the injection molded product, improves the surface hardness, shortens the molding cycle, improves the coefficient of friction, reduces the sliding resistance, reduces the weld line and short shot. It is possible to obtain an injection-molded product for a photographic photosensitive material having a beautiful appearance which does not occur, excellent dimensional accuracy, abrasion resistance and scratch resistance, and excellent characteristics for a small film winding resistance and excellent camera suitability. In addition, it is possible to obtain a molded article for a photographic light-sensitive material having a beautiful appearance by preventing a decrease in gloss due to sliding.

The viscosity of the silicone oil at room temperature is preferably in the range of 1,000 to 100,000 centistokes, particularly preferably 3000 to 60,000 centistokes, and most preferably 5000 to 30,000 centistokes. The amount of addition is
Although it depends on the purpose of use, it is 0.01 to 5.0% by weight, preferably 0.02 to 4.0% by weight. More preferably 0.03-3.0% by weight, particularly preferably 0.04-3.0% by weight.
2.0% by weight.

The silicone-based lubricant may be used alone or in combination of two or more, or may be used in combination with another lubricant or plasticizer. The effect of such silicone oil addition is
It is as follows. (1) Improve the fluidity of the resin, reduce the motor failure of the screw, and prevent the occurrence of melt fracture. (2) Sufficient lubricity can be ensured without adding a lubricant such as fatty acid amide which bleeds out to form a white powder. (3) The injection molded product can be made cloudy, and the light shielding ability can be improved. (4) The physical strength of the injection molded product can be improved. (5) The surface hardness of the injection molded article can be improved, and the wear resistance and scratch resistance can be improved.

The injection-molded product for a photographic light-sensitive material of the present invention contains a heat-resistant thermoplastic resin such as a polyacetal resin, a polyolefin resin, or an olefin-based thermoplastic elastomer, which has a bad influence on the photographic properties of the photographic light-sensitive material. An antioxidant is used for the purpose of preventing the generation of heat decomposable substances (aldehyde compounds etc.)
It is preferable to add more than one kind. By adding one or more kinds of antioxidants, such as antioxidants, radical scavengers, hydrotalcite compounds, and antioxidant synergists, thermoplastic resins, lubricants, fatty acids, organic nucleating agents, Prevents thermal degradation and thermal decomposition of additives such as lubricants,
It is possible to prevent the fluidity of the thermoplastic resin composition from being remarkably changed and the occurrence of bumps (foreign masses). Further, it is possible to prevent the generation of thermal decomposition products (aldehydes and the like) which adversely affect the photographic properties of the photographic light-sensitive material.

Various known compounds for reducing, stabilizing, stabilizing the reaction, or stabilizing the adsorption of thermally decomposed substances (aldehydes, etc.) so as not to adversely affect the photographic properties of the photographic light-sensitive material, for example, hydrazine compounds , A urea compound or the like is preferably added. The amount of aldehyde measured by the acetylacetone method in injection molded products for photographic photosensitive materials is
500 ppm or less, preferably 300 ppm or less, particularly preferably 150 ppm or less, most preferably 75 pp
By setting it to m or less, the photographic properties can be maintained well.
However, the content of the aldehyde having an offensive odor and an adverse effect on the human body in the injection molded article for photographic light-sensitive materials should be 50 ppm or less, and if possible, the substantial content should be close to zero.

Among the antioxidants, one or more of the particularly preferred antioxidants are added in an amount of 0.001 to 1.0% by weight, preferably 0.005 to 0.7% by weight, particularly preferably 0.01% by weight. ~ 0.45% by weight, most preferably 0.02-
0.3% by weight is added. If the added amount is less than 0.001% by weight, the effect of addition is not obtained and only the kneading cost is increased.
On the other hand, if the amount exceeds 1.0% by weight, the photographic properties of the photographic light-sensitive material utilizing oxidation / reduction are adversely affected, and bleed out to the surface of the injection-molded article to deteriorate the appearance. Further, the molded product is plated out on the surface of the mold to deteriorate the appearance of the injection-molded product, and smoke is increased to deteriorate the environment at the injection molding site.

Such antioxidants include antioxidants, radical scavengers, hydrotalcite compounds, and antioxidant synergists. Hereinafter, typical examples of antioxidants which are typical antioxidants will be described. (A) phenolic antioxidants; vitamin E (tocopherol), tocopherol dimers (α-tocopherol, β-tocopherol, 5,7-dimethyltocol, etc.), 6-tert-butyl-3-methylphenyl derivative, 2,6-di-tert-butyl-P-cresol,
2.2'-methylenebis- (4-ethyl-6-tert
-Butylphenol), 4.4'-butylidenebis (6
-Tert-butyl-m-cresol), 4,4′-thiobis (6-tert-butyl-m-cresol), 4
.4-Dihydroxydiphenylcyclohexane, alkylated bisphenol, styrenated phenol, 2.6
Di-tert-butyl-4-methylphenol, n-octadecyl-3- (3 ′ · 5′-di-tert-butyl-4′-hydroxyphenyl) propinate, 2.2 ′
-Methylenebis (4-methyl-6-tert-butylphenol), 4,4'-thiobis (3-methyl-6-t
tert-butylphenyl), 4,4′-butylidenebis (3-methyl-6-tert-butylphenol),
Stearyl-β (3,5-di-4-butyl-4-hydroxyphenyl) propionate, 1,1.3-tris (2-methyl-4hydroxy-5-tert-butylphenyl) butane, 1.3.5 Trimethyl-2.4.6.
Tris (3.5-di-tert-butyl-4hydroxybenzyl) benzene, tetrakis [methylene-3 (3 ′
-5'-di-tert-butyl-4'-hydroxyphenyl) propionate] methane and the like.

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

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

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

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

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

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

Representative examples of the most preferred hindered phenolic antioxidants for the present invention, which have an unexpected effect of coloring upon exposure to light and improving the light-shielding ability, 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-ter
t-butyl-4-hydroxy-hydrocinnamate,
2,2 ', 2'-tris [(3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxy]
Ethyl isocyanurate, 1,3,5-tris (4-t
tert-butyl-3-hydroxy-2,6-di-methylbenzyl] isocyanurate, tetrakis (2,4-di-tert-butylphenyl) 4,4′-biphenylenediphosphite, 4,4′- Thiobis- (6-te
rt-butyl-O-cresol), 2,2′-thiobis- (6-tert-butyl-4-methylphenol),
Tris- (2-methyl-4-hydroxy-5-tert
-Butylphenyl) butane, 2,2′-methylene-bis- (4-methyl-6-tert-butylphenol),
4,4'-methylene-bis- (2,6-di-tert-
Butylphenol), 4,4'butylidenebis- (3-
Methyl-6-tert-butylphenol), 2,6-
Di-tert-butyl-4-methylphenol, 4-hydroxymethyl-2,6-di-tert-butylphenol: 2,6-di-tert-4-n-butylphenol, 2,6-bis (2′- Hydroxy-3'-te
rt-butyl-5-methylbenzyl) -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-t-butyl-4-hydroxy-5-methylphenyl) propionyloxy] ethyl] 2,4.8,10-tetraoxaspiro [5,5 ] Undecane and the like.

Among the above-mentioned antioxidants, those having a melting point of at least 100 ° C., preferably at least 120 ° C. are particularly preferred. Further, it is effective to use it in combination with a phosphorus antioxidant. Furthermore, at least one phosphorus antioxidant and at least one hindered phenol antioxidant
It is particularly preferable to use a combination of at least three of a species and at least one of a hydrous double salt compound such as a hydrotalcite compound.

The above-mentioned vitamin E (tocopherol) and dimeric tocopherols (α-tocopherol, β-tocopherol, 5,7-dimethyltocol, etc.) not only have an excellent antioxidant effect, but also cause the molded article to be colored yellow. When used together with a light-shielding substance such as carbon black, the light-shielding ability can be improved as compared with the case of adding a light-shielding substance such as carbon black alone, and unexpected effects such as improving dispersibility can be exhibited. it can.

For this reason, even if the addition amount of the light-shielding substance is reduced by 10% or more, it is possible to obtain an injection-molded article having the same light-shielding properties as in the case of adding a light-shielding substance such as carbon black alone. . As a result, effects such as prevention of deterioration of photographic properties, improvement of physical strength, improvement of appearance, and reduction of material cost are exhibited, and it is particularly preferable as the injection molded article for photographic photosensitive materials of the present invention.

Particularly preferred antioxidants are low volatility, high molecular weight phenolic antioxidants (trade name Ireganox).
1010, Ireganox 1076, Topan
olCA, Ionox 330, etc.), diuralyl thiodipropionate, distearyl thiopropionate, dialkyl phosphate and the like.

It is preferable to use a phenolic antioxidant, a phosphorus antioxidant and carbon black in combination, since the antioxidant effect is particularly exhibited. In addition, 794-79 of Plastic Data Handbook (published by KK Industrial Research Council)
Various antioxidants disclosed on page 9 and 327 to 329 of Plastic Additives Data Collection (KK Chemical Industry Co., Ltd.)
Various antioxidants disclosed on the page and PLASTIC
S AGE ENCYCLOPEDIA Progress 198
6 (KK Plastic Age), pp. 211-212, can be used by selecting the kind and the amount of addition so as not to adversely affect the photographic properties of the photographic material.

Examples of the combination of two or more antioxidants include a combination of a hindered phenol antioxidant and a pentaerythritol phosphite compound antioxidant, and a combination of a hindered phenol antioxidant and a diorganopentane. In combination with an erythritol diphosphite compound-based antioxidant, a combination of a hindered phenol-based antioxidant and a phosphite-based antioxidant,
Alkyl-substituted monophenol-based antioxidants, alkyl-substituted polyhydric phenol-based antioxidants, and organic phosphite compound-based antioxidants, and organic phosphite-based antioxidants, or any one or two of these Some are selected from the above combinations.

Among these, the hindered antioxidants are liable to be thermally degraded, but the dispersibility of the light-shielding substance is improved, the catalyst residue is neutralized, and the photographic properties of the photographic light-sensitive material are improved.
It can prevent thermal deterioration of fatty acid metal salts such as zinc stearate and calcium stearate that prevent rust from occurring in metal equipment containing iron in the mold, and can not only greatly reduce the occurrence of bumps It is particularly preferable because the photographic properties of the photographic light-sensitive material can be improved.

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

The molecular weight of the photographic material is low because it has many excellent properties, such as little adverse effect on the photographic properties of the photographic material, little thermal decomposition even at the resin melting temperature (130 to 400 ° C.), and little bleed-out over time. 200 or more, preferably 300 or more, particularly preferably 400 or more, most preferably 500 or more hindered phenolic antioxidants and phosphorus-based antioxidants are good.

The most preferred antioxidants to be contained in the injection molded article for photographic light-sensitive materials of the present invention include, for example, various hindered phenolic antioxidants, more specifically tetrakis [methylene-3- (3,5-di-t
-Butyl-4-hydroxyphenyl) propionate]
Methane, n-octadecyl-3- (4′-hydroxy-
3'5'-di-t-butylphenol) propionate, tris- (2,4-di-t-butylphenyl) phosphite, 1,3,5-tris- (2-butyl-4-hydroxy-5-di- t-butyl) butane and the like.

Examples of the radical scavenger which can be contained in the injection molded article for photographic light-sensitive materials of the present invention include, for example, 1.1-diphenyl-2-picrylhydrazyl,
1.3.5-Triphenylferdazyl, 2,2,6
6-tetramethyl-4-piperidone-1-oxyl, N
-(3-N-oxyanilino-1,3-dimethylbutylidene) -aniline oxide, high valent metal salts such as ferric chloride, diphenylpicrylhydrazine, dibutylpicrylhydrazine, diphenylamine, hydroquinone, t- Butyl catechol, dithiobenzoyl disulfide p. p'-ditolyl trisulfide, a benzoquinone derivative, a nitro compound, a nitroso compound, and the like.

Among these, it is particularly preferable to use hydroquinone. Further, the above radical scavengers may be used alone or in combination of several kinds. The amount of addition is 0.001 to 1.0% by weight, preferably 0.005 to 0.7% by weight, particularly preferably 0.0 to 1.0% by weight.
1 to 0.45% by weight. Further, it is also preferable to use together with one or more of various antioxidants, antioxidant synergistic agents and antioxidants.

The antioxidant synergistic agent can be used in combination with one or more of the above-mentioned antioxidants, radical scavengers and hydrotalcite compounds to produce resins and low molecular weight additives (lubricants, antistatic agents, organic additives). Nucleating agents, drip-proofing agents, compatibilizers, etc.) to prevent thermal degradation and thermal decomposition, resulting in a decrease in physical strength, a significant change in resin fluidity, mold gate clogging, short shots, and bumps. Can be prevented. Thermal decomposition substances (aldehydes, etc.) that further affect photographic light-sensitive materials
To prevent the occurrence of Examples of the antioxidant synergistic agent having such an action include phosphoric acid, citric acid, a phosphoric acid compound, and a citric acid compound. Particularly, metal phosphate and metal citrate are preferred. The addition amount is 0.001-1.0% by weight,
It is preferably 0.005 to 0.7% by weight, particularly preferably 0.01 to 0.45% by weight. If it is less than 0.001% by weight, there is no effect of addition, and if it exceeds 1.0% by weight, the effect of increasing the amount is small and only the material cost increases.

In the injection-molded article for a photographic light-sensitive material of the present invention, a catalyst residue may be neutralized, or a substance which adversely affects photographic properties by absorbing a halogen compound such as hydrochloric acid may be used.
In order to prevent a resin burning failure or the like, at least 0.001 to 5.0% by weight, preferably 0.005 to 4.0% by weight, particularly at least 0.001 to 5.0% by weight of a hydrosite compound represented by the following and / or a fatty acid metal salt. Preferably 0.
01 to 3.0% by weight, most preferably 0.02 to 2.0% by weight. If the amount is less than 0.001% by weight, the effect of addition is not exhibited, and only the kneading cost is increased. If the amount exceeds 5.0% by weight, the effect of the added amount is not increased, and not only weld lines and lumps are generated but also the cost is increased.

The hydrotalcite compound has the general formula
But M_XR_Y(OH)_{2x + 3y-2z}(A)_z・ AH_TwoO ｛M is Mg, Ca or Zn, R is Al or Cr or F
e, A is CO_ThreeOr HPO _Four, X, y, z, a are positive numbers.
Is a double salt represented by

As a specific representative example, Mg ₆ Al
_{2 (OH) 16 CO 3 ·} 4H 2 O, Mg 8 Al 2 (OH)
_{20 CO 3 · 5H 2 O,} Mg 5 Al 2 (OH) 14 CO 3 ·
_{4H 2 O, Mg 10 Al 2} (OH) 22 (CO 3) 2 · 4H
_{2 O, Mg 6 Al 2 (} OH) 16 HPO 4 · 4H 2 O, C
a ₆ Al ₂ (OH) ₁₆ CO ₃ .4H ₂ O, Zn ₆ Al _{2
(OH) 16 CO 3 · 4H} 2 O, Mg 4.5 Al 2 (OH)
There is a ₁₃ · 3.5H ₂ O and the like.

Alternatively, when the general formula is M _(1-X) . _{Al x · (OH) 2 X} x / n · mH 2 O { However Shikichu, M is an alkaline earth metal and Zn. X represents an n-valent anion. And x and
m and n satisfy the following conditions. 0 <x <0. 0 ≦ m ≦ 2 A hydrotalcite compound having a refractive index (measured by Larsen's oil immersion method) in the range of 1.40 to 1.55 represented by an integer of n = 1 to 4. ｝

[0113] Examples of n-valent anion represented by X in the above ^{formula, Cl -, Br -, I} -, NO 3 -, C
10 ₄ ⁻ , SO ₄ ²⁻ , CO ₃ ²⁻ , SiO ₃ ²⁻ , HPO _{4
^{2-, HBO 3 2-, PO 4}} 3-, Fe (CN) 6 3-, Fe
(CN) ₄ ^4- , CH ₃ COC ⁻ , C ₆ H ₄ (OH) CO
O ^- it is.

Preferred examples are shown below. Mg _0.7 Al _0.3 (OH) ₂ (CO ₃ ) _0.15・ 0.54H ₂
O Mg _0.67 Al _0.33 (OH) ₂ (CO ₃ ) _0.165・ 0.54H
_{2 O Mg 0.67 Al 0.33 (OH} ) 2 (CO 3) 0.155 · 0.54H
₂ O Mg _0.6 Al _0.4 (OH) ₂ (CO ₃ ) _0.2・ 0.54H ₂
O Mg _0.75 Al _0.25 (OH) ₂ (CO ₃ ) _0.125・ 0.54
H ₂ O Mg _0.83 Al _0.17 (OH) ₂ (CO ₃ ) _0.085・ 0.54
H ₂ O, etc.

The hydrotalcite compounds as described above may be natural products or synthetic products. These hydrotalcite compounds are mainly composed of magnesium, aluminum, etc., and have an adverse effect on the photographic properties of photographic light-sensitive materials and chlorine ions, which are considered to be a cause of rusting of metals used in molding machines. Is excellent in the ability to adsorb and detoxify halide ions. Further, it is presumed that it stabilizes the adsorption of substances that adversely affect photographic properties, such as monomers in thermoplastic resins and volatile substances in various additives. As a specific method of synthesizing the hydrotalcite compound, for example, known methods disclosed in Japanese Patent Publication No. 46-2280 and Japanese Patent Publication No. 50-30039 can be used.

In the present invention, the above-mentioned hydrotalcite compounds are particularly preferable, and they can be used without being limited by their crystal structure and crystal particle diameter. Natural products of hydrotalcite compounds include hydrotalcite, stichtite, pyroaulite and the like. These hydrotalcite compounds may be used alone or in combination of two or more.

In particular, it is preferable to use in combination with the above-mentioned various antioxidants and various fatty acid metal salts from the viewpoint of improving the dispersibility of the light-shielding substance and the hydrotalcite compound without deteriorating the photographic properties. Further, in order to particularly improve the processability and physical properties of injection molding and the like, the average secondary particle diameter is 20 μm or less, preferably 10 μm or less, particularly preferably 5 μm or less, and the BET specific surface area is 50 m ² / g or less, preferably 40 m ² / g, especially
It is 30 m ² / g or less.

In the present invention, it is preferable to use the hydrotalcite compound after treating it with a surface coating substance, since this improves the dispersibility. By coating the surface, the dispersibility or affinity for the resin is further improved, and the suitability for injection molding, physical strength, and the like are also improved.

As examples of such a surface coating material, the above-mentioned surface coating materials (1) to (20) of a light-shielding material can be used. For example, sodium laurate, potassium laurate, sodium oleate, potassium oleate, zinc oleate, zinc oleate, calcium oleate, calcium stearate, which has a function of detoxifying catalyst residues and heavy metals that have an adverse effect and preventing the generation of rust. Magnesium stearate, sodium stearate, zinc stearate, potassium stearate, calcium palmitate, sodium palmitate, potassium palmitate, sodium caprate, potassium caprate, sodium myristate, potassium myristate, sodium linoleate, linoleic acid Gold of higher fatty acids such as potassium A genus salt can be exemplified.

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

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

The amount of these surface coating substances can be appropriately selected and changed, but is preferably about 0.01 to 50 parts by weight, preferably 0.05 to 35 parts by weight, per 100 parts by weight of the hydrotalcite compound.
Particularly preferably, 0.1 to 20 parts by weight, most preferably 0.5 to 20 parts by weight.
About 10 parts by weight is appropriate. Furthermore, a small amount of other impurities such as metal oxides may be contained as long as the gist of the present invention is not impaired.

In order to further disperse the hydrotalcite compounds, higher fatty acids, fatty acid amide-based lubricants, silicone oils, sorbitan fatty acid esters such as sorbitan monostearate, and glycerin fatty acids such as glycerin monostearate can be used. One or more kinds of esters or the like as a dispersant in the resin composition in a total amount of 0.01 to
5% by weight, preferably 0.05-4% by weight, particularly preferably
0.08 to 3% by weight, most preferably 0.1 to 2% by weight may be added.

When used in combination with a hydrotalcite compound, the photographic properties are prevented from deteriorating, the stability of injection molding is improved, and the corrosion resistance (also referred to as rust prevention) of injection molding machines and molds is improved, and the color of injection molded products is improved. In addition to preventing deterioration of the resin, the transparency of the transparent molded product is improved, the physical strength is prevented from lowering, and the action of preventing the occurrence of spots and coloring failure due to resin burning is synergistically improved. When used in combination with at least one stabilizer selected from the group consisting of a phenolic antioxidant, a phosphorus (phosphite) antioxidant and a fatty acid metal salt, the photographic properties of the photographic material are hardly deteriorated, and injection molding is performed. It is particularly preferable because the corrosion-proof (also referred to as rust-proof) effect and the anti-oxidation effect of the machine and the mold are increased.

In this case, in order to prevent the photographic performance of the photographic material from being adversely affected, (1) a phenolic antioxidant is added in an amount of 0.0005 to 0.5% by weight, preferably in the injection molded product for the photographic material. 0.001 to 0.4% by weight, particularly preferably 0.002 to
Add 0.3% by weight. (2) Phosphorus antioxidant 0.0005 to 0.5% by weight, preferably
0.001 to 0.4% by weight, particularly preferably 0.002 to 0.1% by weight. (3) Hydrotalcite compounds and fatty acid metal salts (metal soaps), or any one or more of them
01 to 5% by weight, preferably 0.005 to 4% by weight, particularly preferably 0.01 to 3% by weight. And (1) + (2) +
The total content of (3) is 0.0015 to 6% by weight, preferably 0.005 to 6% by weight.
2 to 5% by weight, particularly preferably 0.003 to 4% by weight, most preferably 0.005 to 3% by weight is contained in the injection molded article for photographic light-sensitive materials. In any case, it is preferable to add these additives in the minimum amount capable of preventing the deterioration of the resin, from the viewpoint of not deteriorating the photographic performance, preventing bleed-out, and suppressing cost increase.

The hydrotalcite compound is preferably used in combination, and not only exhibits the same excellent effects as the hydrotalcite compound, but also improves the fluidity of the resin and disperses the lubricant and the light-shielding substance. A fatty acid metal salt (also referred to as a metal soap) that exerts an effect as a property will be described.

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

One or more inorganic nucleating agents and organic nucleating agents can be added to the injection molded article for photographic light-sensitive materials of the present invention. By adding one or more of an inorganic nucleating agent and an organic nucleating agent, surface hardness, rigidity, Izod impact strength, abrasion resistance, and the like can be improved.
Further, when added to a polyolefin resin of a crystalline resin, particularly a homopolyethylene resin, an ethylene-α-olefin copolymer resin, and a propylene-α-olefin copolymer resin, transparency, crystallization speed, Injection moldability (cycle reduction, molding failure reduction) can be improved.

The total content of one or more of the inorganic nucleating agent and the organic nucleating agent in the injection molded article is 0.001 to 10%.
% By weight, more preferably 0.005 to 8% by weight, and most preferably 0.01 to 5% by weight. When the total content is less than 0.001% by weight, there is no effect of the content and only the kneading cost is increased. On the other hand, when the total content exceeds 10% by weight, there is no effect of increasing the amount, and only the cost increases. Furthermore, in the case of an organic nucleating agent, smoke is increased during injection molding, and bleeds out to the surface of the injection-molded product over time to deteriorate the appearance. Further, it becomes a white powder and adheres to the photosensitive layer of the photographic light-sensitive material to cause a problem of inhibiting development.

Examples of the organic nucleating agent that can be used in the present invention include:
Carboxylic acids, dicarboxylic acids, salts and anhydrides thereof, salts and esters of aromatic sulfonic acids, aromatic phosphinic acids, aromatic phosphonic acids, aromatic carboxylic acids, other aluminum salts, metal salts of aromatic phosphates, carbon Examples include alkyl alcohols of Formulas 8 to 30, condensates of polyhydric alcohols and aldehydes, and alkylamines.

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

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

Representative examples of various thermoplastic elastomers having the function of improving the dispersibility of the light-shielding substance and the fibrous filling of the present invention and improving the physical strength of injection-molded articles are described below. Thermoplastic elastomer (hereinafter referred to as TRE)
Can be roughly classified into styrene-based (hereinafter referred to as SBC), ester-based (hereinafter referred to as TPEE), olefin-based (hereinafter referred to as TBC).
PO), vinyl chloride (hereinafter referred to as TPVC),
Amide type (hereinafter referred to as TPAE), crystalline 1,2 polybutadiene type (hereinafter referred to as RB), ionomer type, fluorine type (hereinafter referred to as F-TPE), urethane type (hereinafter referred to as TP)
U) and isoprene-based compounds.

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

The details of the styrene-based thermoplastic elastomer are shown below. The molecular weight distribution (weight average molecular weight Mw / number average molecular weight Mn determined by the GPC method) produced by polymerization using the single-site catalyst of the present invention is 1.1 to 1.
0, preferably 1.3-8, particularly preferably 1.5-5
Injection molded products for light-shielding photographic photosensitive materials containing styrene-based thermoplastic elastomers that not only have excellent compatibility with thermoplastic resins and other conventional thermoplastic resins, but also have excellent dispersibility of light-shielding substances, Particularly preferred for the present invention. In particular, when a styrene-based thermoplastic elastomer is used for a masterbatch resin pellet containing a high concentration of a light-shielding substance, an injection-molded product for a colored photographic light-sensitive material having excellent dispersibility, physical strength, and appearance with less occurrence of injection molding failure can be obtained. It is preferable because it can be obtained.

When the resin composition of the masterbatch resin pellets contains a styrene-based thermoplastic elastomer, the resin composition for dilution contains a crystalline resin (olefin-based resin, polyacetal-based resin, polyamide-based resin, polyvinylidene chloride-based resin, Linear resin, etc.) or non-crystalline resin (styrene resin, polycarbonate resin, polyvinyl alcohol resin, methacrylic acid resin, vinyl acetate resin, etc.), or a mixture of both resins Even if a recycled resin is mixed, a colored resin composition for injection molding which is well compatible even if a recycled resin is mixed is obtained. Here, the styrene-based thermoplastic elastomer refers to a random, block, graft or the like of a styrene-based monomer (hard segment) and another monomer (soft segment) such as a monoolefin or diolefin copolymerizable with the styrene-based monomer. Copolymers (particularly preferably Brook copolymers), and hydrogenated products of these copolymers.

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

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

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

The content of the other monomer such as a monoolefin or diolefin copolymerizable with the styrene monomer in the styrene monomer is 1 to 12% by weight, preferably 1.5 to 10% by weight, particularly preferably. Is 2 to 8% by weight
Of any quantity. If the content of the other monomer such as a monoolefin or diolefin copolymerizable with the styrene monomer in the styrene monomer is 1 to 12% by weight, it is used under low temperature conditions of, for example, 0 ° C. or less. Photo film spools, photo film cartridges, instant film units, camera bodies, sheet photo film pack holders, photo film magazines, photo film units with lenses, etc.
Insufficient impact strength when dropped from a height of 0 cm or more can be prevented, and it has excellent abrasion resistance. It is possible to prevent an increase in fogging or a partial increase in sensitivity.

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

[0142] The trade names and manufacturers of typical styrene-based thermoplastic elastomers are shown below. Kraton (or Califlex TR), Kraton G (or Elexar) (Shell Chemical), Solpre
ne T (Phillips Petroleum), Europrene
SOL T (ANIC), Solprene T (Petroc
hi), Tufprene (Asahi Kasei), Solprene T, Asaprene T (Nippon Elastomer), Clearen (Electrochemical), JSR, SBR (Nippon Synthetic Rubber), etc.

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

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

These modifying agents can be used alone or in combination of two or more. The content of the unsaturated carboxylic acid or a derivative thereof as the above-mentioned modifier varies depending on the type of the styrene-based thermoplastic elastomer and cannot be unconditionally described, but is generally about 0.1 to 15% by weight based on the styrene-based thermoplastic elastomer. %, Preferably about 0.1 to 10
% By weight. The modified styrene-based thermoplastic elastomer can be obtained by copolymerizing the raw material styrene-based thermoplastic elastomer and the unsaturated carboxylic acid or a derivative thereof using a known modification method such as a solution method or a solution kneading method. .

The following are representative examples of various compatibilizers. The compatibilizer is the same kind of thermoplastic resin with different properties, recycled thermoplastic resin and virgin thermoplastic resin, master batch thermoplastic resin blended with high concentration of light-shielding resin and thermoplastic resin for dilution or a combination of these Like resin, it is a substance that can achieve compatibilization when trying to develop new properties and performance not found in a single thermoplastic resin. The compounding amount of the compatibilizer in the injection-molded article for a photographic light-sensitive material of the present invention is preferably 0.5 to 45% by weight, more preferably 1 to 40% by weight.
Is more preferable, and 2 to 35% by weight is particularly preferable.
30% by weight is most preferred.

If the amount of the compatibilizer is less than 0.5% by weight, it is not possible to effectively improve the physical strength, the appearance, and the compatibility. Also,
If the amount is more than 45% by weight, the rigidity may be insufficient or the photosensitive material may be adversely affected.
The cost is high because of the high cost, and it is difficult to commercialize it economically.

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

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

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

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

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

The compounding amount of these organic nucleating agents and inorganic nucleating agents is 0.01 to 5% by weight, preferably 0.3 to 3.5% by weight, particularly preferably 0.06% by weight in the resin composition. ２2% by weight, most preferably 0.1-1% by weight. If the amount is less than 0.01% by weight, the rigidity, productivity, heat resistance, hardness and the like are not improved. On the other hand, if the blending amount is more than 5% by weight, the rigidity and the like are not further improved, bleed-out and coloring failure are increased, and only the material cost is increased.

Among these nucleating agents, there is no bad smell, the generation of aldehyde compounds is small, the photographic properties of the photographic material are not adversely affected, the nucleating effect is the highest, the molding cycle can be shortened most, and the injection molding is possible. Sorbitol derivatives are preferred because they exhibit various effects, such as being able to minimize the occurrence of failure.

In the present invention, an anti-blocking agent can be preferably added to the injection-molded article for a photographic light-sensitive material. Polyolefin resins, especially copolymer resins containing ethylene, tend to block due to their tackiness. For this reason, blocking occurs between the injection molded articles made of polyolefin resin, making it difficult to convey, or generating static electricity to cause a static mark failure in the photographic photosensitive material.

When such blocking occurs, not only does the workability of the production of an injection molded article for a photographic light-sensitive material and subsequent work and packaging is impaired, but also the use of the injection-molded article for a photographic light-sensitive material causes When attempting to manufacture a package, blocking occurs between the photosensitive material and the injection molded product for the photosensitive material, and the photosensitive layer is damaged,
Static marks are generated, the insertability of the photographic light-sensitive material is deteriorated, and it is difficult to rewind the photographic film.

For this reason, in the present invention, the injection molded article for a photographic light-sensitive material contains a light-shielding substance having an anti-blocking effect and a lubricant having a large effect of improving the lubricity of the photographic light-sensitive material, and a blocking inhibitor. To prevent these various troubles.

Typical examples of the anti-blocking agent which can be used in the present invention, which has a particularly large anti-blocking effect and does not adversely affect the photographic properties of the photographic light-sensitive material, include hydrotalcite compounds, amorphous Zeolites, finely divided silica, natural or synthetic silicon dioxide, clay, calcium carbonate, natural or synthetic zeolites,
Amorphized aluminosilicate, anhydrous amorphous aluminosilicate, titanium white (titanium dioxide), diatomaceous earth, mixture of amorphous aluminosilicate and fine amorphous silica, fine calcium carbonate on zeolite particles Fine powder, metal-substituted crystalline aluminosilicate, metal-substituted zeolite A, asbestos, silica gel,
Examples thereof include aluminum silicate, hydroxysodalite, kaolinite, talc, magnesium oxide, fibrous magnesium oxysulfate (basic magnesium sulfate), synthetic aluminum magnesium silicate, and lithium fluoride.

In the injection molded article for a photographic light-sensitive material of the present invention, it is preferable that the injection molded article for a photographic light-sensitive material contains the following light-shielding substance dispersants in order to ensure complete light-shielding properties.

In the present invention, representative light-shielding substance dispersants which do not adversely affect the photographic properties of the light-sensitive material are typically those having a weight average molecular weight of 5,000 to 5,000.
0000 low molecular weight styrene polymers, polyethylene wax or polypropylene wax having a weight average molecular weight of 500 to 20,000, and derivatives thereof, fatty acid metal salts, ethylene bisamides, and the like.

Further, among the preferred light-shielding substance dispersants,
The following are typical examples of commercially available products. (1) Examples of low molecular weight styrenic polymers having a weight average molecular weight of 5,000 to 50,000 are “Hymer SB”,
"Regit S" (manufactured by Sanyo Kasei Kogyo Co., Ltd.) "Erastyrene", "Picolastic D" (manufactured by Shell Chemical Co., Ltd.) (2) Polyethylene wax or polypropylene wax having a weight average molecular weight of 500 to 20,000, and derivatives thereof. And (they are modified with unsaturated acids such as maleic acid, acrylic acid, maleic anhydride, or unsaturated acid anhydrides, or those obtained by subjecting these metal salts or oxidation treatments to AC AC polyethylene) (Manufactured by Aland Chemical Co., Ltd.) "High Wax" (manufactured by Mitsui Petrochemical Industries, Ltd.) (3) As fatty acid metal salts and ethylenebisamides, "Armoslip EBS" (manufactured by Lion Akzo) "Electro stripper (TS- 2B, TS-3B,
TS-7B etc.) "(manufactured by Kao Soap Co., Ltd.)

The injection molded article for a photographic light-sensitive material of the present invention includes:
In order to improve printability (appearance and appearance), it is preferable to include a light-reflective light-shielding substance. A specific example of such a light-reflective light-shielding substance is titanium dioxide (TiO 2).
₂ ), calcium carbonate (CaCO ₃ ), aluminum powder, aluminum paste, zinc sulfide (ZnS), zinc oxide (ZnO, barium sulfate (BaSO ₄ ), lead oxide (PbO), etc. The refractive index is 2.5. The above titanium dioxide and aluminum paste are particularly preferred.
This is because the larger the refractive index, the greater the amount of light scattered by the white pigment, and the greater the shielding power.

The average particle size of titanium dioxide is 0.01 to
1.0 μm, preferably 0.05-0.8 μm, more preferably 0.10-0.6 μm, most preferably 0.1
5 to 0.40 μm. Fine powder having an average particle diameter of less than 0.01 μm is expensive, easily agglomerated, and easily generates microgrit, which poses a practical problem. On the other hand, if the average particle diameter exceeds 1.0 μm, the effect of scattering visible light is reduced, and the surface irregularities are increased, which is not preferable.

Preferred as yellow pigments are titanium yellow, chrome yellow, cadmium yellow, oil yellow, chromophtal yellow GR, quinophthalone, benzidine yellow and the like.

Examples of the silver pigment include aluminum powder, aluminum paste, and synthetic pearl powder. With almost no adverse effect on the photographic properties of photographic light-sensitive materials,
Aluminum powder and aluminum paste are preferred in that they are inexpensive and have a large light-shielding ability, and the total amount of thermoplastic resin is 1
In particular, 0.01 to 5 parts by weight of one or more of a fatty acid, a fatty acid compound, and a surfactant, 0.01 to 2 parts by weight of an antioxidant, silica, titanium dioxide, and calcium carbonate with respect to 00 parts by weight. One or more of 0.01 to 40 parts by weight;
An injection molded article for a light-reflective photographic material using a light-reflective light-shielding resin composition containing 0.1 to 30 parts by weight of at least one of aluminum powder and aluminum paste is preferable.

Representative examples of surfactant-based antistatic photographic light-sensitive materials for ensuring antistatic properties, which are preferably contained in the injection-molded product for photographic light-sensitive materials of the present invention, are shown below. [Nonionic] (= nonionic) (1) Alkylamine derivative N, N-bis (2-hydroxyethylcocoamine) N-hydoroxyhexadecyl-di-ethanol-amine

(2) Fatty acid amide derivative hydroxystearic acid amide oxalic acid-N, N'-distearylamide butyl ester: Hoechst polyoxyethylene alkylamide

(3) Ether type polyoxyethylene alkyl ether polyoxyethylene alkyl phenyl ether electrostripper [TS-2B, TS-2PA,
TS-3B, TS-5, TS-6B, TS-7B, TS
-8B, TS-9B, HS-12N, EA] (Kao Soap) is particularly preferred in the present invention because it has little adverse effect on photographic properties and is excellent in antistatic properties.

(4) Polyhydric alcohol ester type glycerin fatty acid ester; mono-, di-, or triglyceride sorbitan fatty acid ester such as stearic acid or hydroxystearic acid 1-hydroxyethyl-2-dodecylglyoxazoline

[Anionic] (1) Sulfonic acids; alkyl sulfonate alkylbenzene sulfonate alkyl sulfate

(2) Phosphate ester type; alkyl phosphate

[Cation] (1) Amide-type cation

(2) Quaternary ammonium salt; quaternary ammonium chloride, quaternary ammonium sulfate, quaternary ammonium nitrate, stearamidopropyl-dimethyl-β-hydroxyethyl am
monium nitratc

[Zwitterionic system] (1) Alkyl petaine type;

(2) Imidazoline type Alkyl imidazoline type

(3) Metal salt type;

(4) alkylalanine type;

[Others]; 77 of Plastic Data Handbook (published on April 5, 1984 by the KK Industrial Research Council)
From the various surfactant-based antistatic agents and the like disclosed on pages 6 to 778, it is possible to select and use types and addition amounts that do not adversely affect the photographic properties of the photographic material.

Among the above surfactant-based antistatic agents,
An antistatic agent of a nonionic surfactant is particularly preferable because it has a small adverse effect on photographic properties and human body and has a large effect of preventing a stitch mark. The content of the above-mentioned surfactant antistatic agent in the injection-molded article for a photographic light-sensitive material is 0.1%.
It is preferably from 0.01 to 5% by weight, more preferably from 0.05 to 4% by weight, particularly preferably from 0.1 to 3% by weight, and preferably from 0.2 to 5% by weight.
2% by weight is most preferred.

Representative examples of the deodorant and the fragrance which are preferably contained in the injection molded article for a photographic light-sensitive material of the present invention are described below.

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

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

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

Examples of the aromatic polycarboxylic acid include phthalic acid, terephthalic acid, isophthalic acid, trimellitic acid, pyromellitic acid, benzenehexatricarboxylic acid, naphthalenedicarboxylic acid, naphthalenetricarboxylic acid, naphthalenetetracarboxylic acid, azobenzene There are aromatic carboxylic acids such as tetracarboxylic acid or anhydrides thereof, and particularly preferred are benzenetricarboxylic acid and trimellitic acid.

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

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

In the injection molded article for a photographic light-sensitive material of the present invention,
Since it is essential to leave the product in the sun or to ensure the quality of the photographic material for a long period of time, as with antioxidants, radical scavengers, antioxidant synergists and antioxidants, single site Photo-degradation of thermoplastic resins such as various polyolefin resins, homopolystyrene resins, various rubber-containing aromatic vinyl resins, etc., and various polycarbonate resins, etc., having a molecular weight distribution of 1.1 to 5 produced by polymerization using a catalyst. It is preferable to use an ultraviolet absorber for preventing the occurrence. Representative examples of the ultraviolet absorber which can be used for the injection molded article for a photographic light-sensitive material of the present invention are shown below.

(1) Salicyloxidized ultraviolet absorber The main ones are as follows. Phenylsalicylate p-t-Butylphenylsalicylate p-Octylphenylsalicylate (2) Benzophenone UV absorber The main ones are as follows. 2,4-Dihydroxybenzophenone 2-Hydroxy-4-methoxybenzophenone 2-Hydroxy-4-octoxybenzophenone 2-Hydroxy-4-dodecyloxybenzophenone 2,2'-Dihydroxy-4-methoxybenzophenone 2,2'-Dihydroxy-4,4'-dimethoxybenzophenone 2 -Hydroxy-4-methoxy-5-sulfobenzophenone

(3) Benzotriazole UV absorber The main ones are as follows. 2- (2'-Hydroxy-5'-methylphenyl) benzotriazole 2- (2'-Hydroxy-5'-t-butylphenyl) benzotriazole 2- (2'-Hydroxy-3 ', 5'-di-t-butylphenyl) benzotriazole 2- (2'-Hydroxy-3'-t-butyl-5'-methylphenyl) -5-chloro
benzotriazole 2- (2'-Hydroxy-3 ', 5'-di-t-butylphenyl) -5-chlorobenz
otriazole 2- (2'-Hydroxy-3 ', 5'-di-t-amylphenyl) benzotriazole 2- (2'-Hydroxy-4'-octoxyphenyl) benzotriazole 2- [2'-Hydroxy-3'-(3 " , 4 ", 5", 6 "-tetrahydrophthal im
idemethyl) -5'-methylphenyl] -benzotriazole 2,2-Methylene-bis [4- (1,1,3,3-tetramethylbutyl) -6
-(2H-benzotriazole-2-il) phenol] (4) Cyanoacrylate UV absorber 2-Ethylhexyl-2-cyano-3,3'-di-phenylacrylate Ethyl-2-cyano-3,3'-diphenylate

The compounding amount of the ultraviolet absorber is based on 100 parts by weight of thermoplastic resins such as various styrene resins such as various polyolefin resins, homopolystyrene resins, polyamide resins and various rubber-containing aromatic vinyl resins, and various polycarbonate resins. If it is less than 0.01 part by weight, sufficient ultraviolet absorbing effect is not provided, and if it exceeds 10 parts by weight, bleed out occurs,
Since it adversely affects the photographic performance of photographic light-sensitive materials,
Must be in the range of 10 parts by weight. The preferred range is 0.05
To 5 parts by weight, and a particularly preferred range is 0.1 to 3 parts by weight. In addition, you may use these ultraviolet absorbers in combination of 2 or more types.

In the present invention, various styrene resins such as various polyolefin resins, homopolystyrene resins and various rubber-containing aromatic vinyl resins, various polycarbonate resins and the like, as well as antioxidants, radical scavengers and antioxidant synergists. The appearance (color, color, etc.) of the environment (heat, sunlight, rain, ozone, sulfur dioxide, etc.)
It is preferable to use an anti-aging agent that prevents an aging phenomenon that deteriorates physical properties and the like.

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

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

When the amount of the antioxidant is less than 0.01 part by weight based on 100 parts by weight of thermoplastic resins such as various styrene resins such as various polyolefin resins and various rubber-containing aromatic vinyl resins, and various polycarbonate resins, it is sufficient. If it does not provide an anti-aging effect and exceeds 10 parts by weight, significant bleed-out occurs in this resin composition. Therefore, it is necessary to be in the range of 0.01 to 10 parts by weight, but the preferred range is 0.05 to 5 parts by weight.
Parts by weight, and a particularly preferred range is 0.1 to 3 parts by weight.

Further, the thermoplastic resin composition of the present invention includes:
Various additives can be added. For details of this additive, please refer to the revised and supplemented “Latest Pigment Handbook” (January 10, 1977)
Japan, published by Seibundo Shinkosha Co., Ltd.) and the 1994 edition of the “New Chemical Index” (July 23, 1993, published by The Chemical Daily) and “12394 Chemical Products” (January 26, 1994, Published by Kogyo Nippo) or "Plastic Data Handbook"
(Published by the Industrial Research Institute, Inc. on April 5, 1984) and in the formulation examples (additives) described in various documents such as "Practical Plastics Glossary of Terms Third Edition" (published by Plastic Age Co., Ltd.) In addition to satisfying the characteristics required from the above, the detoxification reaction, etc., by the combination of types, additives and other compounding agents, etc. is performed so as not to adversely affect the photographic light-sensitive material (physical failure such as photographic properties and blocking). Most of the compounding agents can be used for the injection molded article for photographic light-sensitive materials of the present invention by utilizing or examining the resin composition. Representative examples are described below, but the present invention is not limited to these.

A. Class 1 (Classification by performance for needs) Processing aids a. Processing stabilizer (antioxidant, heat stabilizer) (PVC stabilizer) b. Flow control agent (plasticizer, lubricant) c. 1. Shape retention aids (release agents, anti-shrinkage agents) Modified compounding agent 2-1 Stabilizer (life control agent) a. Antioxidants b. Lightfast stabilizer c. Flame retardant d. Biostabilizers e. Degradation repair agent 2-2 Performance modifier (physical property control agent) a. Impact resistance modifier (various elastomers, rubber, L-LDPE resin, etc.) b. Filler, reinforcement c. Colorant d. Plasticizer e. Foaming agent f. Crosslinking agent (organic oxide) g. Nucleating agent 2-3 Function modifier (function imparting agent) a. Conductive agent, magnetic agent b. Antistatic agent (also called antistatic agent) c. Fluorescent whitening agent 2-4 Decomposition accelerator a. Biodegradation b. Photolysis c. Thermal decomposition, etc.

B. Class 2 (Classification by attribute of compounding agent) Powder modifier a. Reinforcement / filler b. Nucleating agent c. Processing aids d. 1. Powder / powder special structure Reaction modifier a. Crosslinking agent b. Macromonomer c. Stabilizers (heat, light, radiation, organisms) d. 2. Decomposition accelerator (biology, light, heat) Interfacial modifier a. Coupling agent b. Compatibilizer c. 3. plasticizer and solvent, plasticizer or solvent Polymer Modifier a. Processability improver, performance modifier b. Polymer alloys, blends (performance modification), etc.

When injection molding is performed using the thermoplastic resin composition of the present invention as described above, it may cause unexpected molding troubles such as burning, silver strips, foaming, weld lines, sink marks, and short shots. , ISO 2053
The water content in the thermoplastic resin composition measured by the -76 measuring method (105 ° C ± 2 ° C, drying for 1 hour) is preferably 0.5% by weight or less, more preferably 0.4% by weight or less, particularly preferably 0.3% by weight or less. (Heat, vacuum, heat vacuum and dry).

In the case of pellets made of a thermoplastic resin composition containing a substance which easily absorbs water, such as carbon black, for example, 50 to 150 ° C., preferably 55 to 130 ° C.
° C, particularly preferably 60-110 ° C, most preferably 6 ° C.
0.5 to 24 hours at 5 to 100 ° C, preferably 1 to 20 hours
Hours, particularly preferably 2 to 15 hours, most preferably 3 hours
Dry the pellet for 〜１０10 hours. In particular, the use of a hopper dryer or the like enables continuous work, which is preferable in terms of workability and economy. In particular, it is preferable to use a vent type extruder, a vent type injection molding machine, or a vacuum heating type hopper dryer.

Next, the production of a resin composition as a raw material when producing an injection-molded article using the above-described thermoplastic resin and various additives will be described. In producing the injection molded article for a photographic photosensitive material of the present invention, a pellet-shaped thermoplastic resin composition is supplied to an injection molding machine as a raw material. Such a pellet-shaped thermoplastic resin composition (hereinafter, referred to as resin pellets) is produced by a pellet production apparatus shown in FIG. The pellet manufacturing device 51 includes:
It is composed of an extruder 52, a cooling tank 53, an air knife 54 for draining water, a pelletizer 55, a dryer 56 and the like.

As shown in FIG. 1, an extruder 52 for forming a resin composition into a strand comprises a supply tank 58 for supplying the resin composition, a screw 59 for extruding the resin composition, and a screw 59 for extruding the resin composition. A cylinder 61 and a motor 62 that are rotatably housed, and a reduction gear 63 and a cylinder 6 that reduce the rotation of the motor 62 and transmit the rotation to the screw 59.
It comprises a heater 64 for heating the resin composition 1 to melt the resin composition, a die 65 attached to the tip 61a of the cylinder 61, and for feeding the resin composition in a strand shape, a base 60 for supporting these.

The resin composition supplied to the supply tank 58 may contain, for example, 0.01 to 5% by weight of a lubricant and an average particle size of 1.5 to 1.5.
0.1 to 10% by weight of synthetic rubber of 0.1 to 5 μm, 0.001 to 1.0% by weight of antioxidant, and 0.1 to 1% of light-shielding substance
These are pellets of a styrene resin composition containing 0% by weight. The heater 64 heats the cylinder 61 to a temperature range of, for example, 160 to 250 ° C., and melts the resin composition entering the rear end side of the cylinder 61 from the supply tank 58. A heat insulating material (not shown) is provided at a connection portion between the cylinder 61 and the supply tank 58, and the cylinder 6
The heat of No. 1 is prevented from being transmitted to the supply tank 58 and the resin composition pellets are melted in the supply tank 58.

The resin composition melted in the cylinder 61 is sent to the tip 61a side by a screw 59 rotated by a motor 62 via a speed reducer 63, and the resin composition is dispersed in 160-160 so that each component is uniformly distributed. 250 ° C
Is kneaded in the temperature range described above. In addition, the screw 59 in the present invention has a ratio L / D representing the ratio between the effective length L and the diameter D.
A screw having a ratio in the range of, for example, 15 to 70 is selected.

The melted resin composition which reached the tip 61a of the cylinder 61 while being kneaded by the screw 59 enters the die 65 attached to the tip 61a.
It is formed into a strand and continuously extruded from the open end 65a. At this time, since the molten resin composition has elasticity, a phenomenon (die swell) occurs when the resin composition comes out of the opening end 65a of the die 65, so that the die 6
Although the inner diameter of 5 is selected according to the diameter of the resin strand to be molded, in the present invention, the diameter R of the die 65 of the extruder shown in FIG. Withdrawal rate r / R, which is the ratio of
1.4, preferably 0.8 to 1.35, more preferably 0.9 to 1.30, particularly preferably 0.95 to 1.2
0, most preferably in the range of 0.95 to 1.15. If it is less than 0.7, small resin pellets that are easy to melt can be produced with good production efficiency. However, molecules and additives (particularly light-shielding substances, polyolefin resins with a crystallinity of 60% or more, and syndiotactic polystyrene resins) are produced in the longitudinal direction. ) Is oriented, and it is difficult to put into practical use due to a decrease in physical strength and a decrease in dimensional accuracy. If it exceeds 1.4, it is difficult to manufacture.

The resin composition formed into a strand by the extruder 52 (hereinafter, referred to as a resin strand) is completely cooled and solidified through a cooling tank 53 in which cooling water is stored. At both ends of the cooling tank 53, feed rollers 53a and 53b for feeding the resin strand are provided.

[0206] The resin strand cooled by passing through the cooling tank 53 is sent to a pelletizer 55 after water adhering to the surface is removed by an air knife 54. The pelletizer 55 is for cutting a long resin strand into short pellets, and is provided with a draw-in roller pair 66 and a rotary blade 67. And the air knife 54
The resin strand from which the moisture has been removed is drawn into the roller pair 6
6, the resin strand is cut in a predetermined length in order from the tip by the rotation of the rotary blade 67 provided with a sickle-shaped blade at regular intervals on the outer periphery of the drum.

At this time, the rotation speed of the rotary blade 67 is such that the length of the resin pellet formed by cutting the resin strand is
0.2-6 mm, preferably 0.4-5 mm, more preferably 0.6-4.5 mm, particularly preferably 0.8-4
mm, most preferably 1 to 4 mm (less than 0.2 mm, the resin pellets have excellent thermal fusibility, but the transportability deteriorates, the thermal degradation increases, and practical application is difficult. If it exceeds 6 mm, the thermal fusibility deteriorates. However, the occurrence of bumps and weld lines increases, which makes it difficult to put into practical use.) Therefore, in the present invention, the length P of one resin pellet is 0.2 to 6 mm. (Fig. 1
reference).

The resin pellets cut and formed by the pelletizer 55 are collected on the conveyor 68 and discharged from the pelletizer 55. And the pelletizer 55
Of the resin pellets discharged from the dryer 56 has a residual moisture content of preferably 0.5% by weight or less, more preferably 0.4% by weight or less.
It is dried to less than 0.3% by weight, particularly preferably less than 0.3% by weight, most preferably less than 0.2% by weight.

The resin pellets formed as described above are used as molding materials for various injection molded articles for photographic photosensitive materials described later. In the case of a styrene-based resin composition or a polyolefin resin composition, the molding temperature at the time of injection molding is 170 to 250 ° C., preferably 175, from the viewpoint of securing the fluidity of the resin, preventing thermal deterioration, and productivity.
To 245C, more preferably 180 to 240C, particularly preferably 185 to 235C, and most preferably 190 to 235C.
It is carried out in the range of 30 ° C.

The injection-molded articles for photographic photosensitive materials of the present invention, which are injection-molded using the resin pellets formed as described above, include resin photographic film cartridges,
(Typical examples are for APS) Photo disc film cartridge, instant film unit, film unit with lens, photo film cartridge container body, photo film cartridge container cap, photo film container, photo film spool, light shielding container, photo Film cartridges, light-shielding magazines for loading light-sensitive sheets or rolls of photographic material into light rooms, cores, photographic film cartridges, instant film packs, magazines for sheet films, sheet film packs, holders for sheet film packs, photo film photography The present invention can be applied to various injection-molded products for photographic light-sensitive materials, such as cameras, photographic light-sensitive material developing machines, sheet film units, and the like, for which complete light-shielding properties and good photographic properties are essential.

[0211] Representative examples of the injection molded product for photographic light-sensitive materials of the present invention are shown below together with the document names, but the present invention is not limited to these. (1) Photo disc film cartridge: Shokai 6
(2) Film unit with lens: JP-A-63-22
No. 6643, JP-A-8-114891, JP-A-8-227122, etc.

(3) Spool for photographic film:
JP-A-251030, JP-A-57-196218, JP-A-59-15049, and JP-A-63-73.
No. 742, U.S. Pat. No. 1,930,144, Japanese Utility Model Laid-Open No. 63-73742, Japanese Utility Model Laid-Open No. 54-12093.
No. 1, JP-A-58-178139-178145, JP-B-55-31541, and JP-A-58-2.
03436, JP-A-58-82237, JP-A-58-82236, and JP-B-44-16777.
JP, JP-A-63-73742, JP-A-62-273,
JP-A-240957, JP-A-62-284355, JP-A-4-33538, JP-A-8-110
614, JP-A-8-118406, JP-A-8-201986, UK Patent No. 2,199,80
No. 5 published specification

(4) Photographic film (APS etc.) cartridge: JP-A-54-111822, JP-B-45
-6991, JP-B-55-21089, JP-A-50-33831, JP-A-56-87039.
Gazette, Japanese Utility Model Laid-Open No. 55-97738,
No. 12538, JP-A-57-190948,
JP-A-4-273240, JP-A-4-32025
8, JP-A-4-335344, JP-A-4-335344.
No. 335639, JP-A-4-343353,
JP-A-4-349454, JP-A-8-12297
No. 6, JP-A-8-179469, JP-A-8-179469
179470, JP-A-8-179471,
JP-A-8-179472, U.S. Pat.
No. 6,418, U.S. Pat. No. 4,848,693, U.S. Pat. No. 4,887,776, etc.

(5) Photographic film cartridge container:
JP-A-61-250639, JP-A-61-739
No. 47, Japanese Utility Model Publication No. 60-153451, USP
4,801,011, JP-A-63-1210
No. 47, Japanese Unexamined Patent Publication No. Sho 62-291639, Japanese Utility Model Laid-Open No. 1-113235, Japanese Utility Model Laid-Open No. 1-152337, Japanese Utility Model Publication No. 2-3236, Japanese Utility Model Publication No. 3-4858.
No. 1, Japanese Patent Publication No. 2-38939, U.S. Pat. No. 4,639,386, U.S. Pat.
No. 011, US Pat. No. 4,979,351, EP 237,062, EP 280,065, EP 298,3.
No. 75 published specification

(6) Winding core, core for belt-shaped photosensitive material, reel: Japanese Utility Model Application Laid-Open No. 60-107848, US Pat.
809,923, UK Patent 2,033,87
No. 3 publication specification, etc. (7) Sheet film pack, sheet film pack holder and sheet film unit: JP-A-5-3413
No. 79, JP-A-8-110568, JP-A-8-110568
JP-A-110569, JP-A-8-201982, JP-A-8-201983, JP-A-8-201
No. 984, JP-A-8-262557, JP-A-8-262558, JP-A-8-110570 and the like.

(8) Photographic film cartridge: JP-A-56-16610, JP-A-2-24846, JP-A-2-29041, JP-A-60-120
No. 448, Japanese Unexamined Patent Publication No. 1-312537, etc. (9) Photographic film case: U.S. Pat. No. 4,779,7
No. 56, Japanese Utility Model Application Laid-Open No. 54-100617, Japanese Utility Model Application No. 64-32343, Japanese Utility Model Application No. 1-94258, Japanese Utility Model Application No. 2-56139, European Patent No. 242,
No. 905, Japanese Patent Publication No. 2-54934, etc.

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

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

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

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

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

(3) Photosensitive / thermosensitive recording material (Japanese Unexamined Patent Publication No.
No. 72358, etc., recording materials using photothermography (photosensitive / thermosensitive image forming method), etc. (4) diazonium photographic photosensitive material (4-morpholinobenzenediazonium microfilm, microfilm, copy film, (5) azide and diazide photographic photosensitive materials (photosensitive materials containing para-azide benzoate, 4,4'diazidostilbene, etc., for example, copy films, printing plate materials, etc.)

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

[0224]

EXAMPLES Table 1 shows the results of tests performed on several items such as the Izod impact strength of test pieces formed by injection molding of the thermoplastic resin composition as described above.
Shown in The description of each item is given after the table.

[0225]

[Table 1]

Resin composition: [A] Melt flow rate (A
STM-D1238G) 9.58 / 10 minutes, density (A
1.05 g / cm ³ , flexural modulus (according to ASTM-D790) 29500 kg / cm ² , Rockwell surface hardness (according to ASTM-D785) 84 L,
Vicat softening point (according to ASTM-D1525) is 970
° C, water absorption (according to ASTM-D570) 0.12%, linear expansion coefficient (according to ASTM-D696) 7 × 10 ^-5 cm / c
m / ° C, volume resistivity (according to ASTM-D257) is 1 ×
With respect to 2.5 parts by weight of 10 ¹⁶ Ω · cm butadiene rubber and 100 parts by weight of a block type rubber-containing polystyrene resin containing 800 ppm of styrene monomer, 0.7 parts by weight of furnace carbon black powder and 20 parts by weight 1 part by weight of a silicone having a dimethylpolysiloxane structure having a viscosity at 2000 ° C. of 20,000 centistokes and 0.1% of zinc stearate.
2 parts by weight, 2 parts by weight of low-molecular-weight propylene having a number average molecular weight of 1000, and 0.1 part of hindered phenolic antioxidant.
It is a resin mixture consisting of 05 parts by weight.

Resin composition: [B] A resin mixture comprising 100 parts by weight of a rubber-containing polystyrene resin and 0.7 parts by weight of furnace carbon black powder. Specimen preparation conditions: Single screw extruder (screw diameter 25m
m, L / D ratio 32), and extruding the resin mixture of each composition of A and B into a strand in cooling water of 20 ° C. at a resin temperature of 210 ° C. and a screw rotation speed of 80 rpm. Then, using a pelletizer, the strand-shaped resin is cut into a length of 3.5 mm to obtain colored pellets of a resin mixture of each composition of A and B. Then, using these colored pellets, a test piece having a size of 125 mm × 63 mm × 4 mm was prepared by an injection molding method at a resin temperature of 190 ° C.

[0228]

The first injection molded article for a photographic light-sensitive material of the present invention, which was injection molded using such a thermoplastic resin composition.
As an example, a photographic film cartridge will be described. FIG. 4 is an external perspective view showing the photographic film cartridge, and FIG. 5 is an exploded perspective view thereof. The photographic film cartridge 10 can be used as the “Ad
vanced Photo System ", and a resin cartridge body 13 and the cartridge body 13
A spool 15 is rotatably mounted on a shaft, and a photographic film 14 is provided with two perforations 14b in one photographing frame.

[0230] The cartridge body 13 is composed of an upper case 11 and a lower case 12 each having a substantially semi-cylindrical shape, and these are injection-molded with a thermoplastic resin. The upper case 11 and the lower case 12 are formed with projecting port portions 11b and 12b, respectively. When the upper case 11 and the lower case 12 are combined, the port portions 11b and 1b are formed.
A film passage 17 for letting the photo film 14 in and out is formed at the joint of 2b. After the upper and lower cases 11 and 12 are combined, the engagement portions are subjected to ultrasonic welding to be integrated. In the case of providing recyclability, it is preferable that the upper and lower cases 11 and 12 be brought into the same state as before use, while ensuring complete light-shielding properties. .

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

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

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

The pair of flanges 22 and 23 has a thin cup shape in cross section. When the flanges 22 and 23 are attached to the spool shaft 21, the opening edges 22a and 23a face each other and are wound between them. Enclose both side edges of the photo film 14 (see FIG. 6A). Opening edges 22a, 23
“a” transmits the rotation of the spool shaft 21 to the photographic film 14 wound around the outermost periphery and prevents the photographic film 14 from being loosened.

The flange 23 has four holes 31 formed at a predetermined pitch. When the spool shaft 21 rotates in the film feeding direction (clockwise direction in the drawing), the ratchet claws 32 of the use indicating member 25 engage with these holes 31. As a result, the rotation of the spool shaft 21
And the flange 23 rotates integrally with the spool shaft 21. When the spool shaft 21 rotates in the film winding direction (counterclockwise direction in the drawing), the use indicating member 25
Ratchet claw 32 gets over the hole 31 and the spool shaft 2
The rotation of 1 is not transmitted to the flange 23.

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

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

From the cartridge body 13, the photographic film 1
When sending out 4, the spool 15 is rotated in the film sending direction. When the spool 15 is rotated in the film feeding direction, the leading end of the photographic film 14 comes into contact with the separation claw 19 and is separated from the portion wound inside.
When the spool 15 is subsequently rotated, the leading end of the separated photo film 14 is brought into contact with the opening edges 22 of the flanges 22 and 23.
The flanges 22 and 23 having a small thickness and flexibility are pushed outward by both side edges of the photographic film 14 (see FIG. 6B).

As a result, the tip of the photo film 14
The wrapping of the flanges 22, 23 by the opening edges 22 a, 23 a is released, and the paper is sent out of the cartridge body 13 through the film passage 17. At this time, both side edges of the photographic film 14 and the flanges 22 and 23 are always in sliding contact with each other, but since the flanges 22 and 23 have high flexibility,
Flange 22, due to the feeding force of photo film 14,
23 flexes outward, frictional resistance between the two is suppressed, and the photographic film 14 is fed with low torque.

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

The upper case 11 and the lower case 12 constituting the cartridge body 13 are manufactured by injection molding using a resin having a light-shielding property. The resin material constituting the upper case 11 and the lower case 12 includes 0.01 to 5% by weight of a lubricant, 0.1 to 10% by weight of synthetic rubber having an average particle diameter of 1.5 to 5 μm, and an antioxidant. 0.001
Polystyrene-based resin composition containing 0.1 to 1.0% by weight and 0.1 to 10% by weight of a light-shielding substance, respectively.
The L / D ratio, which is the ratio between the effective length and the outer diameter of the screw of the extruder for melting and kneading in a temperature range of 0 ° C. to form a strand, is set in the range of 15 to 70, and the die of the extruder is used. And the ratio of the diameter of the strand-shaped resin molded by this extruder is 0.7 to 0.7%.
By cutting a strand-shaped polystyrene-based resin composition extruded in the range of 1.4 into a length of 0.2 to 6 mm, the water content of the cylindrical resin pellets formed is reduced to zero. It is formed by drying until it becomes 0.5% or less and injection molding in a temperature range of 170 to 230 ° C.

The upper case 11 and the lower case 1
The light-shielding substance contained in the resin material constituting No. 2 is added for ensuring light-shielding properties, and for example, carbon black is selected. Examples of the classification by carbon black manufacturing method include furnace method carbon black, channel method carbon black, thermal method carbon black, etc., but photographic adverse effects (abnormality such as generation of fog, decrease in sensitivity or increase in sensitivity, abnormal coloring) Etc.),
Alternatively, in terms of light shielding properties, the average particle diameter is 10 to 80 nm, PH5
Furnace carbon black of from 9 to 9 is preferred, and especially 15
Furnace carbon black having a thickness of 50 nm and a pH of 6-8 is preferred.

As commercially available products, for example, carbon black # 20 (B), # 30 (B), # 33 (B), # 40, # 40 manufactured by Mitsubishi Chemical Corporation
(B), # 41 (B), # 44 (B), # 45 (B), # 50, # 55, # 100, # 600, # 2200
(B), # 2400 (B), MA8, MA11, MA100, etc. Overseas products include, for example, Cabot Black Pearls 2,
46,70,71,74,80,81,607 etc., Regal 300,330,400,660,99
1, SRF-S, Sterling 10, SO, V, S, FT-FF, MT-FF, etc. In addition, Ashland Chemical's Uniteel
R, BB, 15,102,3001,3004,3006,3007,3008,3009,3011,301
2, XC-3016, XC-3017, 3020 and the like, but are not limited thereto. In particular, acetylene carbon black manufactured by Electrochemical Co., Ltd. is expensive, but has a very low content of sulfur components and cyanide compounds that adversely affect the photographic properties of photographic photosensitive materials, and has excellent antistatic properties and dispersibility. Therefore, it is most preferable in terms of quality.

The particle size of the furnace carbon black is 1
If it is less than 0 nm, the kneading property with the resin is poor, and the light-shielding property and the physical strength are deteriorated. Conversely, if it exceeds 100 nm, the light-shielding ability is inferior at best even if the dispersion is good, and if the carbon concentration is increased to secure the light-shielding property, the physical strength is reduced and the moldability is deteriorated, so that it cannot be put to practical use. Many of the carbon blacks having a pH exceeding the range of 5 to 9 were apt to cause photographic adverse effects and could not be used.

In order not to adversely affect the photographic properties of the photographic film 14, the free sulfur content in the carbon black should be 0.1% or less, preferably 0.05% or less.
Particularly preferably 0.01% or less, most preferably 0.0% or less.
It is good to make it below 05%. The content of the cyanide compound is 0.01% or less, preferably 0.005% or less, particularly preferably 0.001% or less, and most preferably 0.001% or less.
It is good to make it below 05%. Further, the content of the aldehyde compound is preferably 0.2% or less, more preferably 0.1% or less, particularly preferably 0.05% or less, and most preferably 0.01% or less. Since even small amounts of these substances have an adverse effect on photographic properties, care must be taken to select carbon black with as small a content as possible.

The amount of carbon black to be added has a wide range because the physical strength is less deteriorated than the other light-shielding substances and the hiding power is excellent, so that the light-shielding properties, injection moldability, and physical strength of the cartridge body are ensured. , 0.05 to 15% by weight,
Preferably 0.1 to 10% by weight, more preferably 0.2
-8% by weight, particularly preferably 0.3-5% by weight, most preferably 0.35-3% by weight. If the added amount of carbon black is less than 0.05% by weight, the light-shielding property is insufficient, and if it exceeds 15% by weight, the physical strength of injection molded articles such as a resin photo film cartridge main body, a photo film spool, a camera, etc. is reduced. In addition, due to the increased water absorption, injection molding failures such as weld line marks, burn marks, sink marks, and silver stripes occur during the injection molding, resulting in poor appearance, physical strength, and deterioration in surface strength. As a light-shielding substance,
When used together with carbon black, inorganic pigments such as iron black (Fe ₃ O ₄ ) having a Mohs hardness higher than carbon black, titanium dioxide, calcium carbonate, etc., aggregates of carbon black are finely pulverized, dispersibility is improved, and light shielding properties are improved. (Hiding power) is greatly improved by 20% or more. Especially Mohs hardness is 3
Inorganic pigments having a refractive index of 1.6 or more and a refractive index of 1.6 or more are preferable from the viewpoint of improving light-shielding properties (Mohs hardness of carbon black is 2.0, refractive index is 1.60, Mohs hardness of titanium oxide is 6.0, refraction) The rate is 2.76). The addition amount of this high Mohs hardness is 1 to 100 parts by weight of carbon black.
It is 500 parts by weight, preferably 5 to 400 parts by weight, particularly preferably 7 to 100 parts by weight, most preferably 10 to 50 parts by weight.

On the other hand, the cartridge body 13 and the lid member 1
8. Methods for imparting lubricity to the spool shaft 21 and the flanges 22 and 23 include a method of adding a lubricant to a resin for molding them and a method of applying a lubricant to a molded product. Examples of the lubricant include silicone oils, higher fatty acid amides such as oleic acid amide, erucic acid amide, and bis fatty acid amide, metal salts of higher fatty acids such as zinc stearate, higher alcohol esters, fatty acid esters of polyhydric alcohol esters, and the like. However, there is no particular limitation.

The silicone oil added to the cartridge body 13 and the lid member 18 is disclosed in
JP-A-2-286043 or JP-A-62-284.
No. 355, dimethylpolysiloxane and carboxyl-modified silicone oil are preferred.

The addition amount of the silicone oil is from 0.05% by weight to 5.0% by weight, preferably from 0.1% by weight to 3.0% by weight.
% By weight, particularly preferably between 0.2% and 2.5% by weight. If the content is less than 0.05% by weight, the desired lubricating effect cannot be obtained, and if the added weight exceeds 5.0% by weight, the resin slips in the screw of the injection molding machine, which not only lengthens the molding cycle but also increases the molding cycle. The amount of silicone bleeding out to the surface of the molded article increases, and the bleed-out silicone oil is transferred to the photographic film 14 in the cartridge body 13 to prevent diffusion of the developing solution into the photographic film 14 during photographic film development. Photographic adverse effects occur. Also, in the ultrasonic seal, the upper case 11
And the lower case 12 is reduced in adhesion.

Silicone oil has a viscosity at 25 ° C. of 1,000 to 100,000 centistokes (hereinafter CS).
), Preferably 2000 to 80000 CS, particularly preferably 3000 to 60000 CS, and most preferably 5000 to 30000 CS. If the viscosity at 25 ° C. is less than 1000 CS, bleed out is severe and adversely affects photographic performance. If it exceeds 100,000 CS, the handleability is poor, and the kneadability with the resin is poor, so that it cannot be used. In addition, various modified silicone oils such as fluorine-modified silicone oil are commercially available in addition to the above, but most of them have an adverse effect on the photographic properties of photographic films. It is.

Next, as a second embodiment of the injection molded article for photographic photosensitive materials, a film pack containing a plurality of sheet-like photographic films will be described. FIG. 7 is an exploded perspective view of a film pack in which a plurality of sheet-shaped photographic films for loading into a bright room are stored when light is shielded, and a film pack holder used for the film pack. The film pack 70 is formed by stacking a plurality of sheet film units 71 each containing a sheet film 71b in a sheath 71a in a resin pack body 72, and is used by being loaded into a film pack holder 75 attached to a camera.

An opening 72a for exposing a sheet film 71b laminated on the uppermost layer is provided in the pack body 72.
And a lid 7 for opening and closing the opening 72a therein.
6 are provided. Further, a spring member (not shown) for pressing the sheet film unit 71 from the back side toward the opening 72a is provided in the pack body 72.

When the film pack 70 is loaded in the film pack holder 75 and the lid 77 of the film pack holder 75 is closed, the opening 72a of the pack body 72 is exposed from the exposure opening 77a formed in the lid 77. Film Pack 7
0 is pulled to a predetermined position, the uppermost sheet film unit 71 is pushed out of the opening 72a, and
7 is moved to an exposure position for closing the exposure opening 77a.

When the lid 76 is returned to the original position, the lid 76 is inserted between the uppermost sheet film unit 71 and the next sheet film unit. Thereafter, when the photographing operation is performed and the lid 76 is pulled, the middle frame 78 provided inside the film pack holder 75 is moved to the pack body 72.
Is pulled out while holding. At this time, since the exposed sheet film unit 71 remains stopped at the exposure position, when the pack main body 72 is pulled out, the exposed sheet film unit 71 is connected to four leaf springs provided on the inner wall of the lid 77. By 79, the film pack holder 75 is pressed against the inner wall on the back side.

Subsequently, when the lid 76 is pushed back to the original position,
The pack main body 72 returns to the original position in the film pack holder 75 together with the middle frame 78. At this time, the exposed sheet film unit 71 enters the pack body 72 from the opening 72b formed on the lower side wall with respect to the moving direction of the pack body 74, and is stored in the lowermost layer of the stacked sheet film units 71. Is done. By repeating the above operation, all the sheet film units 71 stored in the pack main body 72 can be continuously photographed.

The pack body 72 and the lid 76 of the film pack 70 having the above-described structure are manufactured by injection molding of a thermoplastic resin composition having a light-shielding property.
The pack body 72 and the lid 76 are, for example, 0.01 to 5% by weight of a lubricant, 0.1 to 10% by weight of a synthetic rubber having an average particle diameter of 1.5 to 5 μm, and 0.1 to 10% by weight of an antioxidant. 001
Polystyrene-based resin composition containing 0.1 to 1.0% by weight and 0.1 to 10% by weight of a light-shielding substance, respectively.
The L / D ratio, which is the ratio between the effective length and the outer diameter of the screw of the extruder for melting and kneading in a temperature range of 0 ° C. to form a strand, is set in the range of 15 to 70, and the die of the extruder is used. And the ratio of the diameter of the strand-shaped resin molded by this extruder is 0.7 to 0.7%.
By cutting a strand-shaped polystyrene-based resin composition extruded in the range of 1.4 into a length of 0.2 to 6 mm, the water content of the cylindrical resin pellets formed is reduced to zero. It is formed by drying until it becomes 0.5% or less and injection molding in a temperature range of 170 to 230 ° C.

As described above, in any of the above-described embodiments, according to the present invention, an excellent appearance having a high commercial value,
An injection-molded article for photographic light-sensitive materials can be manufactured which has excellent heat resistance, has little dimensional change, can completely secure light-shielding properties, and does not adversely affect photographic films.

In addition to the resin compositions described in the above Examples, typical examples of resins suitable for molding injection molded articles for photographic photosensitive materials include polystyrene resins, impact-resistant polystyrene resins, and styrene-based resins. Acrylonitrile copolymer resin, styrene-acrylonitrile-butadiene copolymer resin, polypropylene resin, high-density polyethylene resin, polyethylene terephthalate resin, polybutylene terephthalate resin, polycarbonate resin, polyvinyl chloride resin, or modified resins thereof are preferable. It is. In particular, a high-density homopolyethylene resin having a molecular weight distribution of 1.1 to 5 polymerized using a single-site catalyst (a typical example is a metallocene catalyst), a high-density ethylene-α-olefin copolymer resin, a homopolypropylene resin, Alpha olefin copolymer resins and crystalline syndiotactic polystyrene resins are preferred, and most preferred are crystalline syndiotactic polystyrene resins.

The crystalline syndiotactic polystyrene resin has extremely high crystallinity, high specific gravity and high mechanical strength, as compared with polymer resins having other bonding modes. In the present invention, a particularly preferable injection molding material has a melt flow rate (G condition of ASTM D1238-88; measured at a temperature of 200 ° C. and a piston load of 5 kg) of 1 to 50 g.
By using a thermoplastic resin composition containing at least 10% by weight of a crystalline syndiotactic polystyrene resin having a molecular weight distribution of 1.1 to 10% by weight, injection moldability and dimensional accuracy are improved, heat resistance, The purpose is to improve chemical resistance, abrasion resistance, and scratch resistance.

Also, among the syndiotactic polystyrene resins, a styrene monomer produced by polymerization using a single-site catalyst and having a melting point of 220 to 310 ° C. measured by GPC is carefully selected and used. Heat resistance can be improved without lowering the physical strength of the molded article. As a result, deformation of the injection molded product due to heat and impact is prevented, and failures such as light fogging, abrasion, pushing, and abrasion debris that deteriorate the photographic properties of the photographic photosensitive material can be prevented.

The syndiotactic polystyrene resin referred to in the present invention is a styrenic polymer resin having a syndiotactic structure, which is 70% or more, preferably 80% or more, particularly preferably 85% or more in racemic dyad, or 30% or more, preferably 4% with a racemic pentahead
It is a styrene polymer having a stereoregularity of 0% or more, particularly preferably 50% or more.

Specifically, stereoregular polystyrene resin, poly (alkylstyrene) resin, poly (halogenated styrene) resin, poly (halogenated alkylstyrene)
Resins, poly (alkoxystyrene) resins, poly (vinyl benzoate) resins, and copolymer resins thereof,
And a mixture thereof, or a copolymer resin containing these structural units.

Representative examples of the poly (alkylstyrene) resin include, for example, poly (methylstyrene) resin, poly (ethylstyrene) resin, poly (propylstyrene) resin, poly (butylstyrene) resin, poly (phenylstyrene) And poly (vinylstyrene) resin. Representative examples of poly (halogenated styrene) resin include, for example, poly (chlorostyrene) resin, poly (bromostyrene) resin, poly (fluorostyrene) resin and the like. Can be

Representative examples of the poly (alkoxystyrene) resin include, for example, poly (methoxystyrene) resin, poly (ethoxystyrene) resin and the like. Among these resins, poly (styrene) resin and poly (methylstyrene) resin are particularly preferable, and poly (styrene) resin is most preferable. These syndiotactic polystyrene resins may be copolymer resins other than the above-mentioned homopolymers, and when impact strength is required, copolymer resins are preferred.

Representative examples of the comonomer component of such a copolymer resin include, in addition to the above-mentioned monomers forming the styrene copolymer resin, olefin monomers such as ethylene, propylene, butene, hexene and octene; Examples include diene monomers such as butadiene and isoprene, cyclic olefin monomers, cyclic diene monomers, and polar vinyl monomers such as methyl methacrylate, maleic anhydride, and acrylonitrile.

Of these, styrene as a main component and those obtained by copolymerizing synthetic rubber, alkyl styrene, hydrogenated polystyrene, and halogenated polystyrene are preferable. Among them, butadiene rubber, isoprene rubber, isobutylene rubber, and para-methyl are preferable. Styrene, meta-methylstyrene, para-tert-butylstyrene, para-chlorostyrene, and hydrogenated polystyrene are more preferred, butadiene rubber, para-methylstyrene, and para-tert-butylstyrene are particularly preferred.

The amount of these comonomers is at most 30 mol%, preferably at most 20 mol%, more preferably at most 15 mol%, particularly preferably at most 10 mol%, most preferably at most 7 mol%. 30% by mole comonomer
If it exceeds, not only the rigidity is insufficient, but also the photographic properties of the photographic light-sensitive material will be adversely affected (increase in fog, abnormal sensitivity, abnormal coloring, etc.), and it will be expensive and difficult to put to practical use.

A syndiotactic polystyrene resin may be blended with another thermoplastic resin. Preferred thermoplastic resin components for Brent include the above-mentioned syndiotactic polystyrene resin, a polystyrene resin having an atactic structure, a general homopolystyrene resin, a conventional impact-resistant polystyrene resin, a rubber-containing polystyrene resin, A saturated carboxylic acid graft-modified thermoplastic resin and a polystyrene resin-based compatibilizer are preferable from the viewpoint of compatibility.

Particularly preferred are 50% by weight of a polystyrene resin having a syndiotactic structure, which is superior in heat resistance, chemical resistance and abrasion resistance to a conventional styrene resin which is an amorphous resin, and less than 50% by weight. It is a mixed resin of at least one of a polystyrene resin having an atactic structure, an impact resistant polystyrene resin containing a non-crystalline conventional polystyrene resin synthetic rubber, and an unsaturated carboxylic acid graft-modified thermoplastic resin. The amount of the styrene resin mixed with the polystyrene resin having a syndiotactic structure is less than 50% by weight, preferably 40% by weight or less, particularly preferably 30% by weight or less, and most preferably 2% by weight or less.
0% by weight or less. If the content of the syndiotactic polystyrene resin is not 50% by weight or more, it is impossible to provide an injection-molded article having excellent characteristics such as heat resistance, chemical resistance, and wear resistance.

The heat- and chemical-resistant syndiotactic polystyrene resin has a weight average molecular weight of 2 to 1,000,000, preferably 5 to 900,000, more preferably 100 to 800,000, particularly preferably 150,000 to 700,000, and most preferably. 200,000 to 600,000. The molecular weight distribution (weight average molecular weight M'w / number average molecular weight M'n) is 1.1 to 10, preferably 1.3 to 8, more preferably 1.3 to ensure the excellent characteristics and dimensional accuracy as described above. Is from 1.5 to 6, particularly preferably from 1.7 to 5,
Most preferably, it is 1.9-4.

Such a syndiotactic polystyrene resin can be produced, for example, by polymerizing a styrene monomer described below using a titanium compound and a condensation product of water and a trialkylaluminum as a catalyst. Further, it can be produced by polymerizing a compound comprising a titanium compound and a cation and an anion in which a plurality of groups are bonded to an element as a catalyst. The most preferred polymerization method has high polymerization activity, and as a result,
A styrene monomer is produced by polymerization using a single-site catalyst (typically, a metallocene catalyst) capable of reducing catalyst residues.

Representative examples of such a single-site catalyst include bis (cyclopentagenenyl) zirconium chloride, bis (cyclopentagenenyl) zirconium dichloride, bis (cyclopentagenenyl) titanium dichloride, and bis (cyclopentagenenyl). Le) hafnium dichloride, bis (methylcyclopentagenenyl) zirconium dichloride, bis (methylcyclopentagenenyl) titanium dichloride, bis (butylcyclopentagenenyl) zirconium dichloride, bis (pentamethylcyclopentagenenyl) zirconium dichloride, Methylene bis (butylcyclopentagenenyl) zirconium dichloride and the like can be mentioned.

Examples of the method for producing the styrene monomer include decomposition distillation of meat silicic acid, reduction and dehydration of acetophenone, dehydrochlorination of ethylbenzol, dehydration of phenyl alcohol, and synthesis and dehydrogenation of ethylbenzol. The synthesis of ethyl benzene and the dehydrogenation method are most preferred because they have little adverse effect on the photographic properties of the photographic light-sensitive material and are inexpensive. In this production method, ethyl benzene (ethyl benzene) is synthesized from benzene and ethylene, a styrene monomer is generated by dehydration of the ethyl benzene, and then purified (98% or more in purity and 1% or less as an impurity).

Further, without lowering the injection moldability,
In order to obtain an injection molded product having high heat resistance and excellent wear resistance and scratch resistance, it is preferable to increase the resin temperature and the mold temperature during injection molding. In this regard, the crystalline syndiotactic polystyrene resin has a higher melting point than other resins, and can increase the resin temperature during injection molding. In the present invention, the resin temperature during injection molding is set to 230 to 35.
By setting the mold temperature at 0 ° C. and the mold temperature at 50 to 200 ° C., the flowability of the resin is increased and the injection moldability is improved, and the physical strength is large, the wear resistance and the scratch resistance are excellent, and the chemical resistance and An injection-molded article having excellent heat resistance can be obtained.

Further, the injection moldability is improved, the dimensional accuracy is improved, the catalyst residue which adversely affects the photographic properties of the photographic photosensitive material is made harmless, and the generation of rust on the screws and cylinders of the injection molding machine and the mold is reduced. It also works to suppress. In the present invention, it is particularly preferable to contain a fatty acid metal salt-based lubricant in an amount of 0.01 to 10% by weight.

Further, injection molded articles for which complete light-shielding properties are essential from the application, such as a resin photographic film cartridge used for an advanced photo system (APS) which is a new photographic system, a photographic film, and the like. In the case of a spool, a film unit with a lens, an instant film unit, a sheet film pack, a sheet film holder, a camera, etc., the melt flow rate is 1 to 50 g / 10 min, and the molecular weight distribution is 1.1 to 10.
A thermoplastic resin composition containing at least 50% by weight, preferably at least 65% by weight, particularly preferably at least 80% by weight, and at least 0.05 to 40% by weight of a light-shielding substance. While being used as a molding material, the water content in the thermoplastic resin composition is 0.50% by weight or less, preferably 0.30% by weight or less,
Particularly preferably, it is dried to 0.10% by weight or less, and then injection-molded at a resin temperature of 230 to 350 ° C. to prevent occurrence of silver stripes, foaming, weld lines, short shots, and the like. Good injection molded products can be obtained.

In this case, it is preferable to contain 0.01 to 10% by weight of one or more kinds of various lubricants which function to improve the flowability of the thermoplastic resin composition and improve the injection moldability. For the purpose of improving the fluidity of the resin, shortening the molding cycle, improving the physical strength, improving the light shielding ability, and improving the injection moldability, it is most preferable to include the silicone-based lubricant described below. For the purpose of improving photographic properties, rust prevention, and dispersibility of a light-shielding substance, it is most preferable to include a fatty acid metal salt-based lubricant.

In particular, in consideration of securing dimensional accuracy, securing physical strength, improving the suitability for ultrasonic welding, etc., the melt flow rate is 1.0 to 50 g / 10 minutes, preferably 2.0 to 30 g / 10 minutes.
g / 10 minutes, more preferably 2.2 to 20 g / 10 minutes,
Particularly preferably, synthetic rubber (natural rubber has a high impurity content and is poor in photographic properties and is unsuitable in the present invention) is preferably from 0.1 to 10 g / 10 min, most preferably from 2.7 to 7 g / 10 min.
15% by weight, preferably 0.2 to 13% by weight, more preferably 0.3 to 10% by weight, particularly preferably 0.5 to 8%
By weight, most preferably 0.7 to 6% by weight is a high impact polystyrene resin containing synthetic rubber.

Other desirable necessary characteristics of this resin include:
Flexural modulus of 15000 Kg / cm ² from the point of prevention of deformation
Or more, preferably 18000 Kg / cm ² or more, particularly preferably 20000 Kg / cm ² , most preferably 22 kg / cm ² .
000 Kg / cm ² or more, and the Vicat softening point (15
kg load) is 80 ° C. or higher, preferably 85 ° C. or higher, particularly preferably 90 ° C. or higher, and most preferably 95 ° C. or higher.

The present invention relates to a photographic film cartridge made of resin, a photographic film cartridge, a film unit with a lens, an instant film unit, a spool and a cartridge for various roll films, various sheet film packs, a sheet film pack holder, and a sheet film unit. The present invention can be applied to a roll-type photosensitive material magazine (such as a photographic film, a photographic paper, and a full-color thermal paper) for loading in a bright room. Hereinafter, typical examples of the configuration to which the present invention is preferably applied will be described. However, the present invention is not limited to these, and can be used in combination with any known configuration.

A photographic light-sensitive material (silver halide light-sensitive material) carrying a magnetic recording layer is disclosed in JP-A-6-35118,
Japanese Patent Application Laid-Open No. Hei 6-17528, Published by Hatsumei Kyokai 94-
As described in detail in No. 6023 and the like, a thin layer support of a polyester which has been heat-treated in advance, for example, a polyethylene aromatic dicarboxylate-based polyester support is used, and its thickness is 50 to 300 μm, preferably 50 to 2 μm.
Those having a thickness of 00 μm, more preferably 80 to 115 μm, and particularly preferably 85 to 105 μm, are subjected to a heat treatment (annealing) at a temperature of 40 ° C. or more and a glass transition temperature or less for 1 to 1500 hours. -2
No. 604, JP-B-45-3828, etc., and UV irradiation, JP-B-48-5043, JP-A-51
Corona discharge described in JP-A-131576, etc.
No. 5,757,578, JP-B-46-43480, and the like, and a surface treatment is performed by glow discharge or the like, and an undercoat described in U.S. Pat. No. 5,326,689 is performed.
If necessary, an undercoat layer described in U.S. Pat. No. 2,761,791 or the like may be provided.
JP, JP-A-4-195726, JP-A-6-5
No. 9357 and the like.

The magnetic layer described above is disclosed in
No. 4,642, JP-A-4-124645 or the like. Further, if necessary, an antistatic treatment described in JP-A-4-62543 or the like may be performed, and finally, a silver halide emulsion may be coated. The silver halide emulsion used here is described in
166,932, JP-A-3-41436,
Those described in JP-A-3-41437 are preferred.

Such photographic light-sensitive materials are disclosed in
It is preferable to manufacture by the manufacturing control method described in Japanese Patent No. 6817 and the like and record the manufacturing data by the method described in Japanese Patent Publication No. 6-87146. Thereafter or before that, according to the method described in Japanese Patent Application Laid-Open No. 4-125560, the film is cut into a narrower band than the conventional 135-size film, and one side edge is defined to be smaller than the conventional one. Two perforations are perforated corresponding to each of the exposure screens.

[0284] The photographic film thus produced can be used in a cartridge package (patrone main body) described in Japanese Patent Application Laid-Open No. 4-157559 or a cartridge shown in FIG. Alternatively, a patrone body such as U.S. Pat. No. 4,221,479, or U.S. Pat. No. 4,834,306, U.S. Pat. No. 4,834,366, or U.S. Pat.
No. 6,613 and U.S. Pat. No. 4,846,418.

As described in US Pat. No. 4,848,693 and US Pat. No. 5,317,355, the cartridge or patrone main body used here may be a tip portion of a photographic film. What can be completely stored is preferable from the viewpoint of ensuring light-shielding properties. Further, a device having a lock mechanism as described in U.S. Pat. No. 5,296,886 or the like, or a device as described in U.S. Pat. No. 5,347,334 is used. It is preferable that the status is displayed or that the double exposure prevention function is provided. Further, as described in JP-A-6-85128 or the like, a device in which a photographic film can be easily mounted simply by inserting the photographic film into a cartridge may be used.

The thus-prepared photographic film cartridge can be suitably used for photography, development processing, and various ways of enjoying photographs by using a camera, a developing machine, and laboratory equipment described below. For example, JP-A-6-8886, JP-A-6-886
No. 99908, a self-loading camera described in JP-A-6-57398, and an automatic winding camera described in JP-A-6-101135.
Japanese Patent Application Laid-Open No. 5-293138 discloses a camera described in Japanese Patent Application Laid-Open No. 5-293138, in which a photographic film cartridge is taken out during photographing and can be replaced with another photographic film cartridge.
Japanese Patent Application Laid-Open No. 5-283382 discloses a camera capable of magnetically recording information at the time of photographing, for example, panoramic photographing, high-vision photographing, normal photographing (magnetic recording capable of selecting a print aspect ratio) on a film, −
If a camera having a double exposure prevention function described in Japanese Patent Application Laid-Open No. 101194 or a camera having a use state display function such as a film described in Japanese Patent Application Laid-Open No. 5-150577 is used, the function of a film cartridge (patrone) will be sufficient. Can demonstrate.

The film photographed in this way is processed by an automatic developing machine described in JP-A-6-222514 and JP-A-6-222545, or before, during or after the processing. JP-A-6-95265, JP-A-4-95
You may use the aspect ratio selection function described in each of the gazettes. At the time of development processing, if it is a cine type development, it is spliced and processed by the method described in JP-A-5-119461. At the time of or after the development process, the attach and detach processes described in JP-A-6-148805 are performed.

[0288] After such processing is performed, the method disclosed in
84835, JP-A-4-186335, JP-A-6-635
The film information may be converted into a print via a back print and a front print on color paper by the respective methods described in each of the publications 79968 and 79968. Further, it may be returned to the customer together with the index print and return cartridge described in JP-A-5-11353 and JP-A-5-223594. These photographic film cartridges are disclosed in Japanese Patent Application Nos. 5-327194 and 6-90.
It is also possible to enjoy using the image input device described in each of the 63 publications.

[0289]

As described above in detail, in the injection molded article for photographic light-sensitive material of the present invention, the diameter of the die of the extruder for molding the thermoplastic resin into a strand shape,
The extruded strand-shaped thermoplastic resin is cut so that the draw-down ratio, which is the ratio to the diameter of the strand-shaped resin molded by this extruder, is in the range of 0.7 to 1.4. Injection molding using cylindrical resin pellets molded by this means, excellent appearance with high commercial value, excellent heat resistance, little dimensional change, flame retardancy can be improved, light shielding property can be completely secured, It is possible to provide an injection molded product for a photographic photosensitive material which does not adversely affect the photographic properties of the photographic film (such as generation of fog, abnormal sensitivity, abnormal gradation, abnormal color development, and uneven density).

[Brief description of the drawings]

FIG. 1 is an explanatory view showing an example of an extrusion molding machine used in the present invention.

FIG. 2 is an explanatory view showing a process for producing a resin pellet used for an injection molded product for a photographic photosensitive material according to the present invention.

FIG. 3 is an explanatory view showing the vicinity of a die in FIG. 1;

FIG. 4 is an external perspective view showing a resin photographic film cartridge as an example of an injection molded product for a photographic photosensitive material of the present invention.

FIG. 5 is an exploded perspective view of FIG.

FIG. 6 is an explanatory view showing the vicinity of a spool in FIG. 4;

FIG. 7 is an exploded perspective view showing a sheet film pack as an example of an injection molded product for a photographic photosensitive material of the present invention.

[Description of Signs] 51 Pellet manufacturing apparatus 52 Extruder 53 Cooling tank 55 Pelletizer 56 Dryer 59 Screw 61 Cylinder 65 Die 69 Cylindrical resin pellet

Continuation of the front page (51) Int.Cl. ⁶ identification code FI G03C 3/00 560 G03C 3/00 560J 560L 560S 566 566P 575 575F B29B 11/02 B29B 11/02 B29C 45/00 B29C 45/00 // B29K 25:00 B29L 31:00

Claims (5)

[Claims] 1. A draw-down ratio, which is a ratio of a diameter of a die of an extruder for forming a thermoplastic resin into a strand shape and a diameter of a strand-shaped resin formed by the extruder, is 0.7 to 0.7. Injection molding using a cylindrical resin pellet formed by cutting a strand-shaped thermoplastic resin extruded in the range of 1.4. Goods. 2. A styrenic resin composition containing 0.01 to 5% by weight of a lubricant and 0.1 to 10% by weight of a synthetic rubber having an average particle diameter of 1.5 to 5 μm at 160 to 250 ° C.
The draw-down ratio, which is the ratio of the diameter of the die of the extruder for melting and kneading in the temperature range of 1 to 3 and forming the strand shape, and the diameter of the strand-shaped resin molded by the extruder, is 0.7 to 1 0.2 to 6 m of a strand-shaped styrenic resin composition extruded in the range of 0.4
A method for producing an injection-molded article for a photographic photosensitive material, comprising performing injection molding at a temperature range of 160 to 250 ° C. using a cylindrical resin pellet formed by cutting to a length of m. 3. A lubricant of 0.01 to 5% by weight, a synthetic rubber having an average particle size of 1.5 to 5 μm of 0.1 to 10% by weight, an antioxidant of 0.001 to 1.0% by weight, An effective length L and an outer diameter D of a screw of an extruder for melting and kneading a styrene-based resin composition containing a light-shielding substance in an amount of 0.1 to 10% by weight in a temperature range of 160 to 250 ° C. to form a strand shape. L / D ratio in the range of 15 to 70, and the draw-down ratio which is the ratio of the diameter of the die of the extruder to the diameter of the strand-shaped resin molded by the extruder. Is cut to a length of 0.2 to 6 mm from a strand-shaped styrene resin composition extruded so that the resin resin is in the range of 0.7 to 1.4. Dry until the water content is below 0.5%, Method for producing an injection molded article for photographic photosensitive materials, which comprises injection molding at a temperature range of 60 to 250 ° C.. 4. A styrenic resin composition containing 0.01 to 5% by weight of a lubricant and 50% by weight or more of a polystyrene resin having a syndiotactic structure is used in an amount of 160 to 50% by weight.
The draw-down ratio, which is the ratio of the diameter of a die of an extruder for melting and kneading in a temperature range of 350 ° C. to form a strand shape, and the diameter of a strand-shaped resin molded by this extruder, is 0.7. The styrenic resin composition in the form of a strand extruded so as to be in the range of ~ 1.4 to 0.2
A method for producing an injection-molded article for a photographic photosensitive material, comprising performing injection molding in a temperature range of 230 to 350 ° C. using a cylindrical resin pellet formed by cutting into a length of up to 6 mm. 5. A lubricant of 0.01 to 5% by weight, a polystyrene resin having a syndiotactic structure of 50% by weight or more, an antioxidant of 0.001 to 1.0% by weight, and a light-shielding substance of 0.1%. The ratio of the effective length L and the outer diameter D of the screw of an extruder of an extruder for melting and kneading a styrenic resin composition containing 10 to 10% by weight in a temperature range of 160 to 350 ° C. to form a strand shape. The D ratio is in the range of 15 to 70, and the drawdown ratio, which is the ratio of the diameter of the die of the extruder to the diameter of the strand-shaped resin molded by the extruder, is 0.7 to 1. 4 is cut to a length of 0.2 to 6 mm from the strand-shaped styrene-based resin composition extruded to form a cylindrical resin pellet having a water content of 0.5. %
A method for producing an injection-molded article for photographic light-sensitive materials, wherein the molded article is dried until the temperature becomes the following, and injection-molded in a temperature range of 230 to 350C.