JP2002072419A - Method for recycling injection-molded article for photographic sensitive material and recycled parts fur photographic sensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To prevent the lowering of the photographic properties of recycled parts for a photographic sensitive material. SOLUTION: Resin parts such as the front and rear covers of a film unit with a lens and the base of the unit body are crushed, the crushed material is pelletized again and the resulting regenerated resin pellets are injection-molded as part of starting materials and used as recycled parts. When the crushed material is melted by heating in injection molding, the thermoplastic resin deteriorates or degenerates thermally and the performance and quality of recycled parts lower as compared with those of new parts. When the thermoplastic resin deteriorates thermally, a harmful gas that causes a chemical reaction with a photographic sensitive material to adversely affect its photographic properties is produced in larger quantities. An antioxidant is added so as to prevent the thermal deterioration and carbon black is added so as to adsorb the produced harmful gas. The carbon black and the antioxidant are added in the form of master batch resin pellets obtained by concentrating and mixing those with a thermoplastic resin.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for recycling an injection molded article for a photographic photosensitive material and a recycled part for a photographic photosensitive material. The present invention relates to a method and a recycled part recycled by this method.

[0002]

2. Description of the Related Art A film unit with a lens is well known as a packaging unit containing a photographic material. The lens-fitted photo film unit is composed of an unexposed photo film cartridge and a unit main body containing the photo film cartridge and having a simple photographing mechanism.

[0003] Since the photographic photosensitive material must be housed in a light-tight manner as a component constituting the unit body, a thermoplastic resin composition having a light-shielding property has conventionally been used as a main constituent material thereof. And formed by injection molding. Hereinafter, these plastic molded parts are referred to as injection molded articles for photographic photosensitive materials.

[0004] The quality and performance required of the injection molded article for photographic light-sensitive materials are described in A.A. B. Completely ensuring light-shielding properties; C. Excellent heat resistance and weather resistance, no dimensional change or shape change due to temperature change or aging change, D. having sufficient fracture resistance; E. high flame retardancy; F. good moldability and few molding defects;
Inexpensive, G. It does not adversely affect the human body.

[0005] When the quality and performance of A to E are low, photographic properties are adversely affected. In other words, the adverse effects on photographic properties include fog, abnormal sensitivity, abnormal gradation, abnormal color development, uneven density, etc., which occur in photographic films. The factors include physical factors such as deformation of injection molded products, and the like. There are chemical factors such as a chemical reaction between the gas generated from the injection molded product and the photographic film.

Physical factors include, for example, deformation of an injection-molded product and molding defects such as the occurrence of bumps such as resin on the surface of the molded product. These factors cause excessive pressure on the photographic film. Pressure fog and film flaws occur. Also, when the injection molded product is charged, static electricity is generated,
This static electricity generates static marks (dendritic or blurred circular fog). As a chemical factor, for example, there is a chemical reaction between a harmful gas such as an aldehyde compound, a ketone, a sulfur compound and a cyanide compound generated by the thermal decomposition of a thermoplastic resin and a photographic film.
Gas fog, sensitivity deterioration, abnormal sensitivity, etc. occur in the photographic film. Since the aldehyde compound is harmful to the human body, it is preferable to suppress the generation as much as possible.

In order to satisfy the above-mentioned quality and performance, a resin serving as a base of an injection molded product for a photographic photosensitive material is selected,
Various additives are added to this resin. First, as the resin, 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. Further, as the light-shielding substance, carbon black or the like is used.

However, a conventional homopolystyrene resin is
It has disadvantages such as insufficient erosion to a part of oils and organic solvents, physical strength such as weather resistance, heat resistance, and breaking strength, and easy charging. Among these disadvantages, a rubber-containing polystyrene resin (an impact-resistant polystyrene resin or a high-impact polystyrene resin) obtained by graft copolymerizing a synthetic rubber such as butadiene rubber as an impact-resistant substance with a styrene monomer in order to improve the fracture resistance Etc.) are commonly used.

As additives to compensate for other disadvantages, there are lubricants for increasing the fluidity of the thermoplastic resin to improve moldability, antioxidants for preventing the thermoplastic resin and other additives from being thermally degraded, UV absorber to prevent photo-deterioration of thermoplastic resin, nucleating agent that plays a role in improving surface hardness, rigidity, Izod impact strength, and abrasion resistance, and prevents deterioration of physical strength of thermoplastic resin due to aging For example, an antioxidant, an antistatic agent, and a dispersant of a light-shielding substance for improving the light-shielding property by dispersing the light-shielding substance in a resin are mixed. These additives are added when new resin pellets are produced.

A new injection molded article for a photographic photosensitive material is injection molded using the new resin pellet as a raw material. Since the new resin pellets are heated and melted during injection molding, some of the additives mixed with the new resin pellets are dissipated and reduced. For this reason, additives are mixed into the new resin pellets in an amount in consideration of the reduced amount. By doing so, a new injection-molded product for a photographic light-sensitive material exhibits predetermined performance and quality.

Incidentally, industrial products are recycled for environmental protection and reduction of industrial waste. As for photographic photosensitive material injection molded products, the collected molded products are crushed, the crushed crushed material is melted, extruded into a strand (twist) shape by an extruder, and cut into pellets of a certain size. The recycled resin pellets are recycled as a part of the raw material by re-injecting the recycled resin pellets into a production line to injection-mold recycled parts.

[0012]

However, when a performance test was conducted, the recycled product was found to be more likely to deteriorate due to heat, had a lower light-shielding property, and had poorer photographic properties as compared with a new product. There's a problem. Deterioration of photographic properties is more evident as the sensitivity of the photographic film increases, and in recent years, high-sensitivity photographic films have been used as photographic films stored in photographic film cartridges or film units with lenses. Is a particular problem.

When the cause was examined, it was found that the amount of carbon black in the recycled product was insufficient when compared with a new product. This is the recycling process
When the resin composition is re-pelletized, and when the recycled resin pellets are injection-molded as a raw material, the resin composition is heated and melted twice and a part of the various additives disappears. Conceivable.

[0014] It was also found that compared with a new product, the recycled product generates a larger amount of harmful gas that adversely affects photographic properties. This is the recycling process
It is considered that the resin composition is heated to cause deterioration and deterioration.

In order to solve the above problems, the method of recycling an injection molded article for a photographic photosensitive material and the recycled part for a photographic photosensitive material of the present invention reduce the photographic properties of the stored photographic photosensitive material as compared with a new one. The aim is to provide recyclable parts without any.

[0016]

In order to achieve the above object, the present invention provides a method for recycling an injection-molded article for a photographic photosensitive material, which comprises crushing a used resin part formed by injection-molding a thermoplastic resin. Then, using the crushed crushed material as at least a part of the raw material, in the method of recycling an injection molded article for a photographic photosensitive material to produce a recycled part by injection molding again, the thermoplastic resin, at least carbon as an additive A master batch resin pellet is formed by concentrating and mixing black and an antioxidant into a resin pellet by extrusion molding, and the master batch resin pellet is added together with the crushed material as a part of the raw material, and injection molded. It is characterized by the following.

Further, a recycled resin pellet obtained by crushing a used resin part and extruding the crushed crushed material into a resin pellet by extrusion may be used as at least a part of the raw material.

The average particle diameter of the carbon black is 10
It is preferably from about 80 nm. The content ratio of the carbon black is preferably 0.2 to 0.5% by weight based on the total weight of the raw materials including the additives. The content ratio of the antioxidant is preferably 0.02 to 0.3% by weight based on the total weight of the raw materials including the additives.

Further, the recycled part for photographic light-sensitive material of the present invention is obtained by crushing a used resin part formed by injection molding a thermoplastic resin, and using the crushed crushed material as at least a part of the raw material. In a recycled part for photographic light-sensitive materials reproduced by injection molding, the thermoplastic resin, at least carbon black and an antioxidant as additives are concentrated and mixed, and extruded to form master batch resin pellets. Then, the master batch resin pellets are added together with the crushed material as a part of the raw material and injection molded.

Further, a recycled resin pellet obtained by crushing a used resin part and extruding the crushed crushed material into a resin pellet by extrusion may be used as at least a part of the raw material.

[0021]

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 thermoplastic elastomer, a lubricant, an antistatic agent, a drip-proof agent, a flame retardant, an ultraviolet absorber, a metal deterioration inhibitor, a compatibilizer, an inorganic or organic pigment, a processing aid, an antioxidant Antioxidant, one of the substances,
A photographic material in which a variety of additives, such as fragrances, desiccants, hygroscopic agents, chelating agents, inorganic or organic nucleating agents, plasticizers, etc., which do not adversely affect the photographic properties of the photographic material are applied. May be included in the resin pellets singly or in combination of two or more.

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, a styrene-based resin having syndiotactic stereoregularity produced by polymerization using a single-site catalyst (typically a metallocene resin) having excellent heat resistance and solvent resistance is particularly preferred. Most preferred is a thermoplastic resin comprising 1 to 99% by weight of a styrene resin having syndiotactic stereoregularity and 1 to 99% by weight of one or more kinds of thermoplastic resin elastomers (others). A thermoplastic resin may be contained).

The term "single-site catalyst" as used herein refers to a catalyst having a uniform active site, unlike a conventional multi-site catalyst having non-uniform active site properties, and having substantially the same molecular weight (molecular weight distribution, composition distribution). (Narrow) refers to the most suitable catalyst for producing a thermoplastic resin. Particularly, in the case of a copolymer resin, when a single-site catalyst is used for the production, the amount of the catalyst used in the resin is small because it is a highly active catalyst. . When manufactured using a single-site catalyst, comonomer is evenly inserted into any molecular component, resulting in a thermoplastic resin with a small (narrow) molecular weight distribution and composition distribution, excellent dimensional accuracy, high physical strength, and anti-blocking. It will be excellent in property.

A styrene-based resin having syndiotactic stereoregularity is a non-crystalline resin because the styrene-based resin produced by a conventional radical polymerization method has an atactic three-dimensional structure, and is resistant to heat and solvents. 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, 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 Resins, 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, and the like. Can be

The styrenic resins, which are particularly preferred among the thermoplastic resins described above, 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, the thermoplastic resins particularly preferred in the present invention are excellent in various properties (physical strength, rigidity, heat resistance, abrasion resistance, etc.) and are particularly stable at high temperatures. If it is, any type may be used and is not limited. For example, polyethylene terephthalate (PET), polyethylene naphthalate (PEN),
Aromatic polyester resin composed of aromatic dicarboxylic acid such as polybutylene naphthalate (PBN) and diol or oxycarboxylic acid, nylon 6, nylon 6
6, polyamide 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 homopolymer resin or two or more copolymer resins as described above, 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, the thermoplastic elastomer will be described. Thermoplastic elastomers are impact resistant materials,
It has the function of improving the physical strength of injection molded articles for photographic photosensitive materials. Further, the thermoplastic elastomer has a function of improving the dispersibility of a light-shielding substance of an additive described later. By improving the dispersibility of the light-shielding substance, sufficient light-shielding properties can be secured without increasing the content of the light-shielding substance. Also, since the content of the light-shielding substance can be small,
There is no decrease in physical strength.

Representative examples of various thermoplastic elastomers having these functions will be described below. Thermoplastic elastomers (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 TPO), and vinyl chloride-based (hereinafter referred to as TPVC). ), Amide-based (hereinafter referred to as TPAE), crystalline 1,2 polybutadiene-based (hereinafter referred to as RB), ionomer-based, fluorine-based (hereinafter referred to as F-TPE), urethane-based (hereinafter referred to as TPU), isoprene-based There are various chemical structures.

[0034] Representative 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 will be described 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.

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

The monoolefins include, for example, ethylene, propylene, butene-1, hexene-1,
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, 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 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.

The typical styrene thermoplastic elastomers are listed below under trade names and manufacturers. 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 such as 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 modifiers 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. .

Next, a light-shielding substance that imparts a light-shielding property to a thermoplastic resin will be described. Representative examples are shown below. However, photographic properties are often adversely affected by the type of photographic light-sensitive material, ISO sensitivity, and the like.
Careful selection of concomitant additives and molding condition sugars is required. 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 the injection-molded article opaque are preferable. Light-absorbing carbon black, titanium nitride, graphite, and iron black are preferred because they are excellent in heat resistance, heat resistance, and light resistance and are relatively inert.

Among these, the most preferable light-shielding substances are inexpensive, have a large light-shielding ability, have little adverse effect on the photographic properties of photographic light-sensitive materials, are stable to heat even at 200 ° C. or higher, and are harmless to the human body. Can be incinerated,
In addition, it is a carbon black that has a thermal stabilizing effect of a thermoplastic resin and has an excellent effect that discoloration, surface change, and physical strength deterioration hardly occur in an injection molded product even when used for a long time under sunlight.

Carbon black is classified into furnace black, acetylene black, gas black, channel black, anthra black, Ketjen black, thermal black, lamp black, oil smoke, pine smoke, animal black, vegetable black, and the like, depending on the raw material. . Among these carbon blacks, furnace carbon black is preferable for the purpose of ensuring light-shielding properties, reducing costs, improving physical properties, etc., and is an acetylene carbon black or a modified auxiliary carbon black in that it is expensive but has an antistatic effect. Ketjen carbon black and conductive furnace carbon black (Vulcan X
C-72 etc.) are also preferred. It is also preferable to use the former and the latter in combination as needed.

As the light-shielding substance used in the resin material composition constituting the injection-molded article for a photographic light-sensitive material, fog is not generated in the photographic light-sensitive material, the increase / decrease in the photosensitivity is small, and the light-shielding ability is large. From the viewpoint that buttocks (lumps of light-shielding substance) are not easily generated when added to a thermoplastic resin,
H (measured by JIS K 6221) is 6.0 to 9.0, average particle diameter (measured by an electron microscope) is 10 to 120 nm, particularly 10 to 10 nm.
80 nm carbon black is preferred. Furthermore, among carbon blacks, volatile components (measured by JIS K 6221)
Is 2.0% or less, DBP oil absorption (oil absorption A of JIS K 6221)
Furnace carbon black (measured by a method) of 50 ml / 100 g or more is preferable in that it has good photographic properties, improves light-shielding properties, improves dispersibility, improves antistatic properties, and has little decrease in physical properties.

In order to suppress the adverse effect on the photographic properties of the photographic light-sensitive material, it is preferable that the content of the sulfur compound or the cyan compound in the injection molded article is as small as possible. The sulfur content of the carbon black (according to ASTM D 1619-60 measurement method) is 0.9% or less, preferably 0.6% or less, particularly preferably 0.4% or less, most preferably 0.2% or less. Good to do. In particular, the content of a free sulfur component that directly adversely affects the photographic properties of the photographic light-sensitive material (each sample was cooled and solidified with liquid nitrogen, and then pulverized. 100 g of the pulverized sample was placed 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 (containing 0.1% each of acetic acid and triethylamine); flow rate: 1 ml / min. Wavelength; 254mm,
Quantification is performed by the absolute calibration method. ) Is 0.1% or less,
Preferably 0.05% or less, particularly preferably 0.01%
Or less, most preferably 0.005% or less.

The content of the cyanide compound (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 50 ppm or less, preferably 20 ppm or less, particularly preferably 20 ppm or less. It is preferably at most 10 ppm, most preferably at most 5 ppm. Further, the iodine adsorption amount (measured by JIS K 6221) is 20
mg / g or more, preferably 30 mg / g or more, particularly preferably 5 mg / g or more.
0 mg / g or more, most preferably 80 mg / g or more, dibutyl phthalate (DBP) oil absorption (measured by JIS K 6221)
Is 50 ml / 100 g or more, preferably 60 ml / 100 g or more, particularly preferably 70 ml / 100 g or more, and most preferably 100 ml / 100 g or more.
ml / 100g or more.

Typical 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
However, the present invention is not limited to these.

The mode of kneading the light-shielding substance into the thermoplastic resin is roughly classified as follows. (1) Uniformly colored pellets; the most commonly used color compound, called (2) Dispersed raw powder; also called dry color, treated with various surface treatment agents, (3) Paste; dispersed in plasticizer, etc. (4) Liquid; also called liquid color, liquid dispersed in surfactant, etc. (5) Master batch pellets; Highly dispersed in the plastic to be colored (6) Hygroscopic granular powder; Highly dispersed in plastic and processed into granular powder (7) Drying Powder; ordinary untreated dry powder

Among the above-mentioned blending forms, the masterbatch method is preferred from the viewpoint of prevention of contamination of the work place and cost. The inventor of the present application also discloses, in Japanese Patent Publication No. 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.

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

An inorganic pigment having a refractive index of less than 1.50,
For example, calcium silicate (1.46), diatomaceous earth (1.45),
Since hydrous silicic acid (1.44) and the like have a small light-shielding ability, they need to be added in a large amount, and are preferred as a blocking inhibitor, but are not preferred as a light-shielding substance.

Further, due to the recent boom in overseas travel, when a high-sensitivity photographic film having an ISO sensitivity of 400 or more is passed through an inspection machine using X-rays in baggage inspection at an airport, fog is likely to occur due to X-rays. In order to prevent this, it is preferable to use a light-shielding substance having a specific gravity of 3.1 or more, preferably 3.4 or more. Specific gravity of 3.1 or more, preferably 3.
The form of the light-shielding substance having an X-ray shielding property other than the light-shielding property of 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.

As a light-shielding substance having a specific gravity of 3.1 or more,
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 whisker, iron whisker, nickel whisker, chromium whisker, stainless steel powder and whisker, magnesite, apatite, spinel, corundum, zircon, antimony trioxide, barium carbonate, zinc white, chrominium oxide, tin powder and mixtures thereof .

Among these light-shielding substances, a light-shielding substance that is particularly preferable for imparting X-ray shielding properties is zircon, corundum, barium sulfate, barium chloride, barium titanate, lead powder, lead oxide, zinc powder, or the like. Zinc white, tin powder, stainless steel 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 light-sensitive 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 3.1 or more. It is a light-shielding substance having a specific gravity of 1.56 or more and a specific gravity of 3.4 or more. The content of these light-shielding substances varies depending on the layer thickness and the type of resin used.
40% by weight is preferred.

The light-shielding substance has an effect of adsorbing a lubricant, an antioxidant, an organic nucleating agent, a surfactant, and an adsorbent of a deodorant, a fragrance, an oxygen scavenger, etc., which easily bleed out. It is also preferable to use an oil-absorbing inorganic pigment. Representative examples of oil-absorbing inorganic pigments include zinc white (52), asbestin (50), clay (51), titanium oxide (56),
Kaolin (60), talc (60), carbon black (60
Above) and activated carbon. The numbers in parentheses indicate the oil absorption (J
Measured by the oil absorption A method of IS K 6221. (Unit: ml / 100 g).

Representative examples of metal powder (including metal paste) include aluminum powder, aluminum paste,
Copper powder, stainless steel powder, iron powder, nickel powder, brass powder, silver powder, tin powder, zinc powder, steel powder and the like. 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 whose surface is coated with a surface coating material and the aluminum paste whose low volatile substances are removed from a thermoplastic resin are referred to as 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.

It is particularly preferable to use the resin as an aluminum paste masterbatch resin in order to eliminate adverse effects and odors on the photographic material. 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 a powder by an atomizing method, a granulating method, a rotating disk dropping method, an evaporation method, or the like, and pulverizing an 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.

In particular, 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.

From the viewpoints of improving injection moldability, securing the quality of the injection molded product, securing light-shielding properties, securing physical strength, securing photographic performance of the photographic photosensitive material, and economical efficiency, etc. The preferred total content is 0.05 to 40% by weight. However, this content varies as appropriate depending on the light-shielding ability of the light-shielding substance and the thickness of the injection-molded article. Therefore, the total content of the light-shielding substance may be appropriately adjusted according to the light-shielding ability of the light-shielding substance to be used. In the case of carbon black, titanium oxide, and aluminum powder having excellent light-shielding ability, light-shielding properties and economical efficiency are required. The total content is preferably 0.05 to 20% by weight, more preferably 0.1 to 15% by weight, and particularly preferably 0.15 to 10% by weight, from the viewpoint of the balance of physical strength, injection moldability and the like. %, Most preferably 0.2-5% by weight.

If the total content is less than 0.05% by weight, unless the thickness of the injection-molded article 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 40% by weight, the dispersibility deteriorates, the generation of microgrids (agglomerated impurities) increases, and pressure fog and scratches are generated on the photographic light-sensitive material. The amount of water in the material injection molded product increases due to the increase in the amount of water adsorbed on the carbon black,
The photographic properties of the photographic material are adversely affected (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.

The resin composition containing the light-shielding substance contains 0.50% by weight of a volatile component (mostly water) in the resin composition.
It is preferable to use the photographic material after drying as described below in order to suppress the adverse effect on the photographic properties of the photographic light-sensitive material and to suppress the occurrence of foaming and silver stripes to prevent the deterioration of the injection moldability. It is more preferably at most 0.40% by weight, particularly preferably at most 0.30% by weight, most preferably at most 0.20% by weight. The resin composition may be dried by heating, vacuuming, or heating and vacuuming (eg, drying at 70 ° C. for 3 hours).

Improvement of dispersibility of the light-shielding substance in resin, improvement of resin fluidity, friction fog and pressure fog on photographic photosensitive material,
In order to prevent the generation of micro grit that causes scratches, prevent the generation of volatile substances that are harmful to photographic properties, suppress moisture absorption, and prevent mold surface contamination, a surface coating material that coats the surface of the light shielding material Preferably, it is used. Representative examples of the surface coating material are shown below. The coating amount of the surface coating substance of the light-shielding substance is 0.1 to 200 with respect to 100 parts by weight of the light-shielding substance.
Parts by weight, preferably 0.5 to 150 parts by weight, more preferably 1 to 100 parts by weight, particularly preferably 2 to 80 parts by weight, most preferably 5 to 60 parts by weight.

(1) Coupling agent 1) Coupling agent coating containing azidosilanes
2) Coating of silane-based coupling agent (aminosilane, etc.) 3) Coating of titanate-based coupling agent (2) Deposition of silica, followed by deposition of alumina (3) Zinc stearate, Magnesium stearate,
Coating of higher fatty acid metal salt such as calcium stearate (4) Coating of surfactant such as sodium stearate, potassium stearate, oxyethylene dodecyl amine (5) Barium sulfide aqueous solution and sulfuric acid aqueous solution in the presence of excess barium ion With an average particle diameter of 0.1 to
Generate 2.5 μm barium sulfate, add alkali silicate aqueous solution to this water slurry to generate barium silicate on the surface of barium sulfate, and then add mineral acid to the slurry to decompose the barium silicate to hydrated silica. And coated on the barium sulfate surface.

(6) Metal hydrated oxides (one or more of hydroxides of titanium, aluminum, cerium, zinc, iron, cobalt, or silicon) and metal oxides (titanium,
Surface coating with one or two oxides of aluminum, cerium, zinc, iron, cobalt or silicon), or a composition comprising only one of the aforementioned metal hydrated oxides or metal oxides.

(7) Coating a polymer having one or more reactive groups selected from the group consisting of an aziridine group, an oxazoline group and an N-hydroxyalkylamide group in the molecule. (8) Polyoxyalkyleneamine (9) Surface coating with a cerium cation, selected acid anion and alumina (10) Surface coating with an alkoxytan derivative having an α-hydroxycarboxylic acid residue as a 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 coating with polyhydroxy saturated hydrocarbon (19) Surface coating with surfactant (cationic, nonionic, zwitterionic) (20) Organometal chelate compound (especially β-dititone chelate compound is It is preferable because the dispersibility is improved, etc.).

Among the surface coating substances of the light-shielding substance,
It has little adverse effect on the photographic characteristics (fog generation, abnormal sensitivity, abnormal color formation, etc.) of the photographic photosensitive material, improves the dispersibility of light-shielding substances,
Excellent effects such as reduced generation of bumps and improved fluidity of resin
(1), (3), (12), (15), (16), (18), (19) and (20) are particularly preferred.

In addition to the above-mentioned surface coating substance, a substance having an effect other than the surface coating effect, for example, various antistatic agents, lubricants, drip-proofing agents, etc., is used together with the light-shielding substance, so that the surface of the light-shielding substance is reduced. It is preferred to coat. In particular, an aliphatic monocarboxylic acid having 20 to 40 carbon atoms and 20 to 4 carbon atoms.
By adding an ester with an aliphatic monohydric alcohol of 0, it is possible to prevent adverse effects on the photographic properties of the photographic light-sensitive material, to improve the dispersibility of the light-shielding substance, to improve the fluidity of the resin, and to obtain an injection molding machine. In addition, the effect of improving the injection moldability by reducing the motor load and improving the appearance of the injection molded product can be exhibited.

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

[0086] Since these improve the flowability of the thermoplastic resin and achieve uniform kneading, they are very excellent as a surface coating material of the light-shielding substance. 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.

The addition amount of these surface coating substances is 0.1 to 50 parts by weight, preferably 0.5 to 40 parts by weight, more preferably 1 to 30 parts by weight, based on 100 parts by weight of the light-shielding substance. Most preferably, it is 1.5 to 20 parts by weight. If the amount of the surface coating substance is less than 0.1 part by weight, the coating effect is hardly exhibited. On the other hand, if the addition amount exceeds 50 parts by weight, the amount of bleed-out increases with time, and a slip occurs between the screw of the injection molding machine and the resin, and the discharge amount fluctuates. As a result, the thickness of the injection-molded product varies greatly, and short shots and the like are more likely to occur, which makes practical use difficult.

Further, a light-shielding substance for coloring may be added to the thermoplastic resin composition to color translucently or opaquely.
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. Furthermore, in containers for photographic film cartridges,
By coloring the container body or the container lid, it can be used to identify the type of photographic light-sensitive material in the container that is opaque, translucent, or transparent.
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, representative examples of the coloring light-shielding substance 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 blue, 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.

In addition to the above-mentioned light-shielding substances, known additives which are generally added to thermoplastic resins include:
That is, various antioxidants such as lubricants, antioxidants and radical scavengers, nucleating agents, antistatic agents, stabilizers such as ultraviolet absorbers and antiaging agents, flame retardants, coloring agents such as dyes and pigments, A mold agent and the like can be appropriately added according to the required performance.

[0093] Among these additives, the lubricant will be described first. By mixing the lubricant with the thermoplastic resin, the fluidity of the thermoplastic resin is improved, and as a result, the injection moldability is improved. Further, the dispersibility of the light-shielding substance can be improved by adding a lubricant. less than,
The names of typical commercially available lubricants and their manufacturers are also described.

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

[Hydroxystearic amide lubricant] (1) Palmitamide amide lubricant; Neutron S-18
(Nippon Seika), Amide P (Nitto Chemical), etc. (2) Lauric amide lubricants; Armide C (Lion Akzo), Diamond (Nippon Kasei), etc.

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

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

2. Hydrocarbon lubricants: liquid paraffin, natural paraffin, microwax, synthetic paraffin, polyethylene wax (number average molecular weight is 10,000 or less, preferably 8,000 or less, particularly preferably 6,000 or less), polypropylene wax (number average molecular weight is 10 or less) , 0
00 or less, preferably 8,000 or less, particularly preferably 6,000
It is as follows. ), Chlorinated hydrocarbon, fluorocarbon, etc.

3. 3. Fatty acid-based lubricants: higher fatty acids (preferably C ₁₂ or more, specifically caproic acid, stearic acid, oleic acid, erucic acid, partimic acid, etc.), oxy fatty acids, etc. 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. Alcohol-based lubricant: polyhydric alcohol, polyglycol, polyglycerol, etc.

6. Fatty acid metal salt lubricant (metal soap):
Caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, stearic acid, succinic acid, behenic acid, behenic acid, linoleic acid, stearyl lactic acid, lactic acid, phthalic acid, benzoic acid, hydroxystearic acid, ricinoleic acid, naphthenic acid Oleic acid, erucic acid, balmitic acid, montanic acid, erucic acid and the like having 6 to 50, preferably 10 to 40, particularly preferably 10 to 30 fatty acids and lithium, sodium, magnesium, calcium, Strontium, barium, zinc, cadmium,
Compounds with metals such as aluminum, tin, and lead are mentioned, and preferred are sodium stearate, magnesium stearate, calcium stearate, zinc stearate, magnesium oleate, calcium oleate, zinc oleate, calcium baltimate and the like. is there.

7. Silicone-based lubricants: various grades of dimethylpolysiloxane, polymethylphenylsiloxane, olefin-modified silicone, amide-modified silicone, amino-modified silicone, carboxyl-modified silicone, epoxy-modified silicone, α-methylstyrene-modified silicone, alcohol-modified silicone, polyethylene glycol, There are polyether-modified silicone modified with polypropylene glycol, olefin / polyether-modified silicone, polydimethylsiloxane, etc., and any of them can be used in the present invention.

Among the above-mentioned various lubricants, the one which is preferable when applied to an injection molded article for a photographic light-sensitive material is firstly a fatty acid metal salt-based lubricant. This has a small lubricating effect, but functions to neutralize catalyst residues and halogen compounds in the resin and improve the dispersibility of the light-shielding substance.
The fatty wire metal salt-based lubricant is preferred from the viewpoints of improving the photographic properties of the photographic light-sensitive material, the rust-preventing effect of the screws and cylinders and the mold of the injection molding machine, and preventing the occurrence of bumps.

Next, silicone-based lubricants can be mentioned. The silicone-based lubricant not only exerts effects such as improvement of resin fluidity, improvement of lubricity, improvement of physical strength and shortening of a molding cycle, but also does not adversely affect the photographic properties of the photographic light-sensitive material. When the silicone-based lubricant is used in combination with a light-shielding substance, the dispersibility of the light-shielding substance is improved, and the haze (ASTM D-1003) is increased by clouding the resin. It is preferable because it exhibits an unexpected effect.

Among these silicone-based lubricants, particularly preferred are dimethylpolysiloxane and polymethylphenylsiloxane mainly composed of linear diorganopolysiloxane. Among them, the viscosity at 23 ° C. is 50 in that many effects such as an improvement in physical strength, an improvement in light-shielding properties, an improvement in lubricity, and an improvement in injection moldability are exhibited without adversely affecting the photographic properties of the photographic light-sensitive material. More preferred is 1100,000 centistokes of dimethylpolysiloxane. Considering handleability, photographic properties and cost, the viscosity at 23 ° C is 50
Most preferred is a dimethylpolysiloxane of from 00 to 50,000 centistokes. If the viscosity at 23 ° C. is less than 50 centistokes, photographic properties are adversely affected and bleed-out becomes severe, making practical use difficult. On the other hand, if the viscosity exceeds 100,000 centistokes, the production becomes difficult and the cost increases, and the viscosity is too high to make the handling difficult.

Next, olefin-modified silicones, amide-modified silicones, polydimethylsiloxanes, polyether-modified silicones, and olefin / polyether-modified silicones, which do not adversely affect the photographic properties of the photographic light-sensitive material and have a large lubricating effect. There are silicone and carboxyl-modified silicone.

These silicone oils improve the physical strength of the injection molded product, improve the surface hardness, shorten the molding cycle, improve the coefficient of friction, reduce the sliding resistance, and reduce 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.

These silicone-based lubricants may be used alone, in combination of two or more, or in combination with other lubricants or plasticizers. The effects of such silicone oil addition are 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 amount of the above-mentioned various lubricants varies depending on the type of the resin or the 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.

Next, the antioxidant will be described. Antioxidants prevent thermal degradation of the thermoplastic resin and thermal decomposition of various additives, and improve the photographic properties by preventing the generation of thermal decomposition substances (aldehyde compounds) that adversely affect photographic properties. Has a function. By preventing the thermal deterioration of the thermoplastic resin, it is possible to prevent the fluidity of the thermoplastic resin from being significantly changed and the occurrence of bumps (foreign masses). As a result, it is possible to prevent pressure fog and film scratches on the photographic film. In addition, since aldehyde compounds emit a bad smell and also have a bad influence on the human body, the antioxidant also has a function of preventing the human body from being adversely affected.

This antioxidant includes, in addition to the antioxidant, a radical scavenger, a hydrotalcite compound, and an antioxidant synergistic agent which improves the antioxidant effect when used in combination with these antioxidants. is there. It is preferable to add at least one or more of these to the injection molded article for photographic photosensitive materials.

Various known compounds can be used to stabilize, decompose, stabilize, or stabilize pyrolysis products (such as aldehydes) in amounts that do not adversely affect the photographic properties of the photographic light-sensitive material. For example, it is preferable to add a hydrazine compound, a urea compound and the like together. The amount of the aldehyde measured by the acetylacetone method in the injection molded article for photographic photosensitive materials is 500 ppm or less, preferably 30 ppm or less.
By setting the content to 0 ppm or less, particularly preferably 150 ppm or less, and most preferably 75 ppm or less, good photographic properties can be maintained. 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.

The addition amount of the antioxidant is 0.001 to
1.0% by weight, preferably 0.005 to 0.7% by weight,
Particularly preferably, it is 0.01 to 0.45% by weight, most preferably 0.02 to 0.3% by weight. 0.00
If it is less than 1% by weight, there is no effect of addition and only the kneading cost increases. When the amount exceeds 1.0% by weight,
It adversely affects the photographic properties of the photographic light-sensitive material utilizing the oxidation / reduction action and bleeds 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.

Among the various antioxidants, first, representative examples of 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 antioxidant;
-Ethoxy-2,2,4-trimethyl-1,2-dihydroquinoline, polymers of 2,2.4-trimethyl-1,2-dihydroquinoline, trimethyldihydroquinoline derivatives and the like.

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

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

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

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

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

Among the above antioxidants, a phenolic antioxidant and a phosphite antioxidant are preferred because they have little adverse effect on the photographic properties of the photographic light-sensitive material and have an excellent antioxidant effect. . In addition, a phenolic antioxidant is particularly preferable, which has an unexpected effect that bleed-out is small, that it is colored by light and that the light-shielding ability is improved, and that it withstands high temperatures during molding and that the amount of smoke is small. In addition, there is little adverse effect on the photographic properties of the photosensitive material.

Of the phenolic antioxidants, various hindered phenolic antioxidants are particularly preferred.
The representative examples of the hindered phenol-based antioxidants are shown below. 1,3,5-trimethyl 2,4,6-tris (3,3
5-di-tert-butyl-4-hydroxybenzyl)
Benzene, tetrakis [methylene-3- (3'.5'-
Di-tert-butyl-4'-hydroxyphenyl) propionate] methane, octadecyl-3,5-di-t
ert monobutyl-4-hydroxy-hydrocinnamate, 2,2 ', 2'-tris [(3,5-di-tert
-Butyl-4-hydroxyphenyl) propionyloxy] ethyl isocyanurate, 1,3,5-tris (4
-Tert-butyl-3-hydroxy-2,6-di-methylbenzyl] isocyanurate, tetrakis (2,4
-Di-tert-butylphenyl) 4,4'-biphenylenediphosphite, 4,4'-thiobis- (6-
tert-butyl-O-cresol), 2,2′-thiobis- (6-tert-butyl-4-methylphenol), tris- (2-methyl-4-hydroxy-5-t)
tert-butylphenyl) butane, 2,2′-methylene-bis- (4-methyl-6-tert-butylphenol), 4,4′-methylene-bis- (2,6-di-te
rt-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'-tert-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-
And tetraoxaspiro [5,5] undecane.

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

Therefore, even if the amount of the light-shielding substance added 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.

Commercially available phenolic antioxidants include various types of Irganox manufactured by Ciba-Geigy (typically, Ireganox 1010 and Ireganox).
1076) and Sumilizer of Sumitomo Chemical Co., Ltd.
BH-T, SumilizerBH-76, Sumil
iser WX-R, Sumilizer BP-10
1 and the like. Also, 2,6-di-hybutyl-p-
Cresol (BHT), a low volatility high molecular weight phenolic antioxidant (trade names Ireganox 1010, I
reganox 1076, TopanolCA, Io
Nox 330), diuralyl thiodipropionate, distearyl thiopropionate, dialkyl phosphate, and the like are effective in combination.

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 improve the dispersibility of the light-shielding substance, neutralize the catalyst residue, and improve the photographic properties of the photographic light-sensitive material.
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 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 light-sensitive 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.

Next, a radical scavenger which is one of the antioxidants will be described. Examples of the radical scavenger preferably 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,
High valences such as 2,6,6-tetramethyl-4-piperidone-1-oxyl, N- (3-N-oxyanilino-1,3-dimethylbutylidene) -aniline oxide, ferric chloride and the like Metal salts, diphenylpicrylhydrazine, dibutylpicrylhydrazine, diphenylamine,
Hydroquinone, t-butyl catechol, dithiobenzoyl disulfide p. p'-ditolyl trisulfide,
Benzoquinone derivatives, nitro compounds, nitroso compounds and the like can be mentioned.

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.

Next, the antioxidant synergistic agent will be described. The antioxidant synergistic agent is used in combination with one or more of the above antioxidants, radical scavengers, and hydrotalcite compounds to form resins and low molecular weight additives (lubricants, antistatic agents, organic nucleating agents, (Dripproofing agents, compatibilizers, etc.) to prevent thermal deterioration and thermal decomposition, and prevent the physical strength from decreasing, the fluidity of the resin from remarkably changing, and preventing mold gate clogging, short shots, and bumps. it can. Further, generation of thermal decomposition substances (aldehydes and the like) which adversely affect the photographic light-sensitive material is prevented. 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 to 1.0% by weight, preferably 0.005 to 0.7% by weight, particularly preferably 0.01% by weight.
０．４0.45% 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.

Next, a hydrotalcite compound which is one of antioxidants will be described. In injection molded products for photographic light-sensitive materials, to neutralize catalyst residues, detoxify substances that adversely affect photographic properties by absorbing halogen compounds such as hydrochloric acid, and prevent resin burning failure etc. Hydrosite compounds represented by the following, and a fatty acid metal salt, or at least one of these, 0.
001 to 5.0% by weight, preferably 0.005 to 4.0% by weight, particularly preferably 0.01 to 3.0% by weight, most preferably 0.02 to
Add 2.0% by weight. If the content is less than 0.001% by weight, the effect of addition is not exhibited, and only the kneading cost is increased.
Even if the temperature exceeds the above, there is no effect of increased addition, and not only the generation of weld lines and lumps, 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. ｝

[0139] 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 specific 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.

Particularly, the above-mentioned hydrotalcite compounds are 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 kinds of fatty acid metal salts described below 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 40m
² / g, especially 30 m ² / g or less.

The hydrotalcite compound is preferably used after being treated with a surface coating substance, since this improves the dispersibility. By coating the surface, the dispersibility or affinity for the resin is further improved, and the suitability for injection molding, physical strength, and the like are also improved.

As examples of such a surface coating material, the above-mentioned surface coating materials (1) to (20) of the light-shielding material can be used. Has a function to detoxify catalyst residues and heavy metals that have an adverse effect or prevent the generation of rust, for example, sodium laurate, potassium laurate, sodium oleate, potassium oleate, zinc oleate, calcium oleate, calcium stearate, 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 represented by lauric acid, palmitic acid, oleic acid, stearic acid, capric acid, myristic acid, linoleic acid and the like; organic sulfonic acids such as calcium dodecylbenzenesulfonate and sodium dodecylbenzenesulfonate; Metal salts: isopropyl 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 the 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.

To further improve the dispersion of 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 anticorrosion (also referred to as rust-prevention) effect of an injection molding machine and a mold 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 not to adversely affect the photographic performance of the photographic light-sensitive material, (1) a phenolic antioxidant is added in an amount of 0.0005 to 0.5% by weight, preferably 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.

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

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 and 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.

Next, the nucleating agent will be described. The nucleating agent is divided into an inorganic nucleating agent and an organic nucleating agent. The injection-molded article for a photographic light-sensitive material of the present invention contains one of an inorganic nucleating agent and an organic nucleating agent.
Seeds or two or more can be added. 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, a polyolefin resin of a crystalline resin, particularly a homopolyethylene resin, ethylene-α
-When added to an olefin copolymer resin or a propylene-α-olefin copolymer resin, transparency, crystallization speed, and injection moldability (cycle shortening, molding failure reduction) can be improved in addition to the above characteristics.

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 content effect (no improvement in rigidity, productivity, heat resistance, hardness and the like is observed), and only the kneading cost is increased. Conversely, if the total content exceeds 10% by weight, there is no effect of increasing the amount (the rigidity and the like are not further improved), and the cost is merely increased. Furthermore, in the case of the organic nucleating agent, if the content is large, the amount of smoke generated during the injection molding increases, and the bleeding out to the surface of the injection molded product over time deteriorates 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.

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

Examples of the organic nucleating agent include carboxylic acids, dicarboxylic acids, salts and anhydrides thereof, salts and esters of aromatic sulfonic acids, aromatic phosphinic acids, aromatic phosphonic acids, aromatic carboxylic acids, and other aluminum salts. Salt, aromatic metal phosphate, alkyl alcohol having 8 to 30 carbon atoms,
Condensates of polyhydric alcohols and aldehydes, and alkylamines.

The carboxylic acids are generic names 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.

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.

Among these nucleating agents, there is no bad smell, little generation of aldehyde compounds, no adverse effect on the photographic properties of the photographic light-sensitive material, the highest nucleating effect, the shortest molding cycle, and the injection molding Sorbitol derivatives are preferred because they exhibit various effects, such as being able to minimize the occurrence of failure.

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.

Next, a surfactant-based antistatic agent will be described. In order to maintain the antistatic property of the injection molded article for photographic light-sensitive materials, it is preferable to include it in the resin composition. Hereinafter, typical examples of the surfactant-based antistatic agent are shown below.

1. Nonionic (= nonionic) (1) Alkylamine derivative; TB103, TB10
4 (Matsumoto oil and fat) Alkylamide type tertiary amine (laurylamine); Armostat 400
(Lion fat) N, N-bis (2-hydroxyethyl cocoamine); Armostat 410 (Lion fat) Tertiary amine; ANTISTATIC 273C, 273, 273E
(Fine Org. Chem) N-hydoroxyhexadecyl-di-ethanol-amine; Bel
g.P. 654, 049 N-hydoroxyoctadecyl-di-ethanol-amine; (N
ational Dist.)

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

(3) Ether type polyoxyethylene alkyl ether RO (CH ₂ CH ₂ O) nH polyoxyethylene alkyl phenyl ether special non-ion type; register 104, PE100, 1
16-118 (Daiichi Kogyo Pharmaceutical), Register PE13
2, 139, Elegan E115, Chemistat 113
(Daiichi Kogyo Pharmaceutical Co., Ltd.), Chemistat 1005 (Nippon Oil & Fats), Erik BM-1 (Yoshimura Oil Chemical), Electrostrippers TS-2B, TS-2PA, TS-3B, T
S-5, TS-6B, TS-7B, TS-8B, TS-
9B, HS-12N, HS-12PA, EA, etc. (Kao)

(4) Polyhydric alcohol ester type glycerin fatty acid ester; mono-, di-, or trigulariseride such as stearic acid or hydroxystearic acid, monoglyric (Nippon camphor), TB-123 (Matsumoto oil and fat), Register 113 (Daiichi Kogyo Pharmaceutical Co., Ltd.) Zorbitan fatty acid ester Special ester; Elique BS-1 (Yoshimura Oil Chemical) 1-hydroxyethyl-2-dodecylglyoxazoline; British cellophane

2. Anionic (1) Sulfonic acids Alkyl sulfonate RSO ₃ Na Alkylbenzene sulfonate Alkyl phosphate ROSO ₃ Na (2) Phosphate ester type alkyl phosphate

[0168] 3. Cationic (1) Amide-type cation; Resist PE300, 40
1, 402, 406, 411 (Daiichi Kogyo Pharmaceutical) (2) Quaternary ammonium salt quaternary ammonium chloride quaternary ammonium sulfate quaternary ammonium nitrate Katimine CSM-9 (Yoshimura Oil Chemical), CATANAC6
09 (American cyanamide), Denno 314C (Marubishi Yuka), Armostat 300 (Lion Fat), 1
00V (Armor), Electrostripper ES (Kao Soap), Chemistat 2009 (Nippon Yushi) Stearamido propyl-dimethyl-β-hydroxyethyl amm
onium nitratc; CATANAC SN (American
Dianamide)

4. Zwitterionic system (1) Alkyl petane type (2) Imidazoline type; Rheostat 53, 532, AM
S 53, AMS 303, 313 (by Lion Yushi) alkyl imidazoline type (3) a metal salt; AMS 576 (by Lion Yushi) Rheostat 826,923 (Lion _{oil) (RNR'CH 2 CH 2 CH 2} NCH 2 COO) 2 Mg ｛R ≧ C, R ′ ＝ H or (CH ₂ ) mCOO-｝ (lion oil) R is a C ₃ -C ₈ hydrocarbon, A is an oxygen or imino group, M is an organic amine or metal (4) alkyl Alanine type

[0170] 5. Others Register 204, 205 (Daiichi Kogyo Seiyaku), Elegan 2E: 100E (Nippon Yushi), Chemistat 100
2, 1003, 2010 (Nippon Oil & Fat), Erik 51
(Yoshimura Yuka), ALROMIME RV-100 (Geigy), and Plastic Data Handbook (K
776-77 of K Industry Research Committee (issued on April 5, 1984)
From the various antistatic agents and the like disclosed on page 8, it is possible to select and use types and addition amounts that do not adversely affect the photographic properties of the photographic light-sensitive material.

Among the above surfactants, nonionic (nonionic) surfactants are preferred from the following points. Nonionic (nonionic) surfactants have a small adverse effect on photographic properties and human body, have a large static mark prevention effect, and exhibit antistatic and antifogging effects.
It also has the function of improving the dispersibility of the light-shielding substance and the filler.

Examples of the nonionic surfactant 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, poly Oxyethylene dodecylamine, polyglycerin oleate and the like can be mentioned.

Among the nonionic surfactants described above, particularly, 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.

Next, the compatibilizer will be described. 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 compatibilizer includes 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 Compatibilizers] Anhydrous maleic oxide / propylene copolymer resin Anhydrous maleic styrene graft copolymer resin Anhydrous maleic styrene / butadiene / styrene copolymer resin Anhydrous maleic oxide styrene / ethylene・ Butadiene / styrene copolymer resin Ethylene / glycidyl methacrylate copolymer resin Ethylene / glycidyl methacrylate / styrene graft copolymer resin Ethylene / glycidyl methacrylate / methyl methacrylate graft copolymer resin Maleic anhydride graft polypropylene copolymer resin

Representative examples of the internal and external commercial 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 compounding amount of the compatibilizer in the injection molded article for a photographic light-sensitive material is preferably 0.5 to 45% by weight, and 1 to 40% by weight.
%, More preferably 2 to 35% by weight, most preferably 4 to 30% by weight.

If the amount of these compatibilizers is less than 0.5% by weight, it is not possible to effectively improve physical strength, appearance and 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.

Next, the anti-blocking agent will be described. Polyolefin resins, especially copolymer resins containing ethylene, tend to block due to their tackiness. Therefore, blocking occurs between the injection molded products made of polyolefin resin, and it becomes difficult to convey,
Static electricity may cause static mark failure in the photographic material.

When such blocking occurs, not only does the workability in the production of an injection molded article for a photographic light-sensitive material and the subsequent processing and packaging deteriorate, but also the photographic light-sensitive material can be used by using the injection molded article for a photographic light-sensitive material. 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, in the injection-molded article for a photographic light-sensitive material, a lubricant having a large anti-blocking effect and a lubricating substance having an anti-blocking action and a large anti-blocking effect are provided. To prevent these various troubles.

Typical examples of the anti-blocking agent which can be used in the present invention, which has a 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.

Next, the light-shielding substance dispersant will be described. The light-shielding substance dispersant is a substance for dispersing the light-shielding substance, and by containing the same, it is possible to secure the complete light-shielding property while keeping the amount of the light-shielding substance small.

Representative examples of preferable light-shielding substance dispersants which do not adversely affect the photographic properties of the light-sensitive material include low-molecular-weight styrene polymers having a weight-average molecular weight of 5,000 to 50,000, and weight-average molecular weights. Is 500-20
000 polyethylene wax or polypropylene wax, and derivatives thereof, fatty acid metal salts, ethylene bisamides, and the like.

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 Industry Co., Ltd.) (3) As a fatty acid metal salt and ethylene bisamides, "Armoslip EBS" (manufactured by Lion Akzo) "Electro stripper (TS- 2B, TS-3B,
TS-7B etc.) "(manufactured by Kao Soap Co., Ltd.)

Next, the light-reflective light-shielding substance will be described. It is preferable that the injection molded article for a photographic photosensitive material contains a light-reflective light-shielding substance in order to improve printability (appearance and appearance). Specific examples of such a light-reflective light-shielding substance include titanium dioxide (TiO ₂ ), calcium carbonate (CaCO ₃ ), aluminum powder, aluminum paste, zinc sulfide (ZnS), and zinc oxide (ZnO,
Barium sulfate (BaSO ₄ ), lead oxide (PbO) and the like can be mentioned. Titanium dioxide and aluminum paste having a refractive index of 2.5 or more 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.

Next, the ultraviolet absorbent will be described. An ultraviolet absorber is a substance for preventing photodeterioration of a thermoplastic resin. Injection molded products for photographic light-sensitive materials such as film units with lenses are required to be left in sunlight or to ensure good quality of photographic light-sensitive materials for a long period of time. For this reason, similarly to the antioxidant, the radical scavenger, the antioxidant synergistic agent, and the antioxidant, various polyolefin resins and homopolystyrene resins having a molecular weight distribution of 1.1 to 5 produced by polymerization using a single-site catalyst and various It is preferable to use ultraviolet absorbers such as various styrene resins such as rubber-containing aromatic vinyl resins and various polycarbonate resins. Hereinafter, typical examples of the ultraviolet absorbent will be described.

(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 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.

Next, the antioxidant will be described. Anti-aging agents are used in environments where thermoplastics are located (heat, sunlight,
It has a function of preventing an aging phenomenon in which the appearance (color, gloss, cracks, etc.), physical strength, and the like are deteriorated with the passage of time, such as rain, ozone, and sulfur dioxide.

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 various styrene resins such as various polyolefin resins and various rubber-containing aromatic vinyl resins, and various thermoplastic resins such as polycarbonate resins. 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.

Next, the deodorant and the fragrance will be described.
Representative examples of the deodorant and the fragrance will be 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 group at the end of the 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 terminal carboxyl group include 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, abies 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 microparticles of microcapsules. It is used after being encapsulated in dextrin, cyclodextrin, maltosyl cyclodextrin, cyclodextrin, zeolite, starch, talc and the like.

Further, the thermoplastic resin composition of the present invention comprises
In addition, various additives can be added. For details of this additive, please refer to the latest supplement manual
(Published by Seibundo Shinkosha Co., Ltd. on January 10, 1977) and 1994
“New Chemical Index” (July 23, 1993, published by The Chemical Daily) and “12394 Chemical Products” (January 26, 1994)
Japan, published by the Chemical Daily), "Plastic Data Handbook" (April 5, 1984, published by the Industrial Research Institute, Inc.) and "Practical Plastics Glossary 3rd Edition" (published by Plastic Age, Inc.) In addition, the types and additions satisfy the characteristics required from the examples of blending (additives) described in various documents and do not adversely affect the photographic light-sensitive material (physical failure such as photographic properties and blocking). Use of detoxification reactions etc. in combination with ingredients and other compounding agents,
By examining the resin composition, most of the compounding agents can be used for the injection molded article for photographic photosensitive materials of the present invention. 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 modifier (various elastomers, rubbers, L-LDPE resins, 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.

In injection molding using the thermoplastic resin composition of the present invention as described above, in order to prevent unexpected molding failures such as burning, silver stripes, foaming, weld lines, sink marks, and short shots, The water content in the thermoplastic resin composition is preferably 0.5% by weight or less, more preferably 0.4% by weight or less, particularly preferably 0.3% by weight, according to the ISO 2053-76 measurement method (105 ° ± 2 ° C., drying for 1 hour). % 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 manufacture of a new injection molded article for a photographic photosensitive material will be described. When manufacturing a new injection-molded product for a photographic photosensitive material, first, the thermoplastic resin composition to which the various additives described above have been added is supplied to a melt-extrusion molding machine, melted, and extruded to form a strand. It is formed in a shape. The strand-shaped thermoplastic resin composition is cut into pellets, and new resin pellets are produced. Next, the new resin pellets are put into a production line as raw materials, and injection molded articles for photographic photosensitive materials are produced by injection molding.

During the injection molding, the new resin pellets are heated and melted, so that the additives dissipate and decrease. For this reason, when producing new resin pellets, an additive is added in an amount obtained by adding a decrease in the additive during injection molding. As a result, a predetermined amount of additive is contained in the new injection-molded photographic light-sensitive material, and the necessary performance and quality are secured.

A new injection molded article for a photographic photosensitive material is supplied to a production line as a plastic part, and products such as a photographic film cartridge and a film unit with a lens are assembled. Used products used by the user are collected and recycled.

The procedure for recycling an injection molded product for a photographic material will be described below with reference to the flowcharts shown in FIGS. In FIG. 1, the recycling line includes a product disassembly line, a plastic parts recycling line, and a production line.

In the product disassembly line, parts other than plastic parts such as metal parts and electric parts are removed from the product, and the remaining plastic parts are sent to the plastic part recycling line. When the product is, for example, a lens-fitted film unit, the plastic part recycling line includes plastic parts such as a rear cover, a front cover, and a body base to which a light-shielding substance such as carbon black has already been added. The transparent (so-called skeleton specification) front cover, the finder lens that failed the inspection, etc.
A plastic component to which no light-blocking substance is added is supplied as a mixture.

As shown in FIG. 2, the first plastic part recycling line includes a raw material recycling line and a part molding line. In the raw material recycling line, plastic parts are crushed, and the crushed crushed material is re-pelletized to generate recycled resin pellets.

The raw material recycling line comprises a coarse crushing step, a dissimilar material separation step, a washing step, a drying step, a fine crushing step, a melt extrusion step, and a cutting step. In the coarse crushing process, the crusher crushes the plastic parts into relatively large grains. After the coarse crushing, the coarsely crushed material is sent to a dissimilar material separation step, and a material different from plastic such as a metal piece is separated by the dissimilar material separator. Thereafter, in the washing step, the coarsely crushed material is washed, dehydrated and dried in the drying step, and finely crushed in the fine crushing step. By washing the crushed material, substances harmful to the photographic film, for example, sand, iron powder, general dust, oil, adhesive of adhesive tape, magic ink, etc. are washed away.

The crushed material is melted by a melt extruder. The melted thermoplastic resin composition is extruded into a strand. This strand resin is cooled and solidified by cooling water. This solidified strand resin is cut into a predetermined size and pelletized,
Recycled resin pellets are produced.

The recycled resin pellets thus recycled are supplied as raw materials to a component molding line. In the component molding line, recycled components are made by mixing injection molding with recycled resin pellets and new resin pellets or using 100% recycled resin pellets as raw materials, and using these as raw materials by injection molding.

Also, as in the second plastic parts recycling line shown in FIG. 3, the crushed material is not formed into pellets, but is finely crushed, and the recycled crushed material that has been washed and dried is used as a part of the raw material. May be charged. Recycled crushed material is
It is used by mixing with other raw materials (recycled resin pellets or new resin pellets).

[0220] The use of recycled crushed material as a raw material has the advantage of reducing the recycling cost by omitting the pelletizing step. On the other hand, when the recycled crushed material is used, a granular mass of the recycled crushed material appears on the surface of the recycled component, which may form a convex portion.
For this reason, the recycled crushed material is preferably used as a raw material for a part that does not come into direct contact with the photographic film.

When injection molding is performed using these recycled resin pellets and crushed materials as raw materials, at least carbon black and an antioxidant are added as additives. When the crushed material is heated and melted by extrusion molding or injection molding, the thermoplastic resin is thermally decomposed and deteriorates or deteriorates, and the performance and quality of the thermoplastic resin deteriorate. Further, when the crushed material is heated and melted, additives such as carbon black added at the time of producing new resin pellets disappear, and, for example, the light shielding ability and the like are reduced. Further, when the thermoplastic resin is thermally decomposed, harmful gases such as aldehyde compounds, ketones, sulfur compounds and cyanide compounds which adversely affect the photographic properties of the photosensitive material are generated.

The antioxidant has an action of suppressing the generation of these harmful gases by preventing the deterioration of the thermoplastic resin.
However, due to the heating and melting of the crushed material, the antioxidant added during the production of new resin pellets also disappears and decreases like carbon black.
The harmful gas is generated in a large amount as compared with a new product. Carbon black and an antioxidant are added to prevent the performance and quality of the recycled parts from being deteriorated due to the heat melting.

Carbon black not only ensures the light-shielding properties of plastic parts, but also improves the moldability of thermoplastic resins. Further, the carbon black has a property of reducing the harmful gas generated from the crushed material by absorbing or capturing the harmful gas and preventing the harmful gas from leaking out of the injection molded product. In order to improve the ability to adsorb or capture this harmful gas, for example, carbon black having a large particle diameter and a low specific gravity is used. The fact that the particle diameter is large and the specific gravity is light means that the gap generated between the particles increases. Since the harmful gas enters the gap more, the larger the gap is, the more the adsorption or trapping ability is improved.

The types of carbon black include:
There are various types as described above. The carbon black to be added at the time of recycling is appropriately selected from among these various carbon blacks and those having different physical properties such as the particle size and specific gravity, and a mixture of these carbon blacks is used.

As described above, the antioxidant has a function of preventing the thermal deterioration of the thermoplastic resin and the additives, maintaining the performance and quality thereof, and preventing the generation of the harmful gas caused by the heat deterioration and the deterioration. Have. It is also known that the effect of preventing thermal degradation is further improved by using an antioxidant and carbon black in combination. Further, when used in combination with carbon black, the dispersibility of carbon black is improved, and the light shielding ability is improved.

There are various antioxidants as described above. As the antioxidant to be added at the time of recycling, similarly to carbon black, an antioxidant is appropriately selected from various antioxidants, and a mixture of a plurality of types of antioxidants is used.

Further, the types of carbon black and antioxidants added to the new resin pellets may be different depending on the production time of the product and the type of the product. Plastic parts used in used products are usually crushed by mixing those with different manufacturing times and product types.Therefore, carbon black and antioxidants contained in the crushed crushed materials are also various. Are mixed. Carbon black and antioxidants added at the time of recycling are required to have properties peculiar to recycled products, such as suppression of generation of harmful gases. A different type may be used, or the same type may be used as long as the carbon black and antioxidant already contained in the crushed material satisfy the properties.

The carbon black and the antioxidant are added in the form of a masterbatch resin pellet.
The masterbatch resin pellets are formed by extruding and forming a resin pellet by concentrating and mixing additives such as carbon black and an antioxidant and a thermoplastic resin,
The additive is contained in the masterbatch resin pellets in a highly concentrated state such that the ratio of the additive to the total weight of the resin pellets is, for example, 10% by weight.

The masterbatch resin pellets have higher compatibility with main raw materials such as new resin pellets, regenerated resin pellets, and crushed materials, and dispersibility of the additives, as compared with the case where additives are added as they are. improves. For this reason,
Since additives are evenly contained in the molded recycled parts, the quality variation between recycled parts molded from the same raw material and the quality variation between each part in one recycled part are affected. Disappears.

FIG. 4 shows an injection molding machine. Injection molding machine 6
As is well known, 1 is provided with a heating cylinder 63 provided with a nozzle 62 at the tip and a screw 64 in the heating cylinder 63. A heater 66 is arranged on the outer periphery of the heating cylinder 63. Raw materials are hopper 67 and sub hopper 6
8, is poured into the heating cylinder 63,
It is kneaded by the screw 64 while being heated and melted in 3. The kneaded raw material is supplied from the nozzle 62 to the mold 6.
9 is injected and filled at high pressure.

Recycled resin pellets, new resin pellets, and crushed materials are supplied from the hopper 67. The master batch resin pellets are supplied from the sub hopper 68. In this example, the sub-hopper 68 is used, and the master batch resin pellets are charged therefrom. However, the sub-hopper 68 may be charged from the hopper 67 similarly to other raw materials. The master batch resin pellets input from the sub hopper 68 are:
In the heating cylinder 63, it is kneaded with other raw materials and injected into a mold. The mold into which the molten raw material has been injected is cooled,
After this cooling, the mold is removed and a recycled part is completed.

The recycle parts injection-molded in this way are supplied to a production line to assemble products.
Recycled injection-molded products for photographic materials contain carbon black and an antioxidant, so they are not inferior in performance and quality, such as light-shielding ability, even when compared to new ones. Since generation of gas is also suppressed, photographic properties are not degraded.

As described above, injection molded articles for photographic photosensitive materials to which carbon black and an antioxidant have been added at the time of recycling include resin photographic film cartridges, (typically for APS) photographic disc film cartridges, and instant film units. , 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 cartridge, Sheet or roll photo-sensitive material loading Light-shielding magazines, roll cores, photo film cartridges, instant film packs, sheet film magazines, sheet film packs, sheet film pack holders, photo film photographing cameras, photo-sensitive material processing machines, sheet films Muyunitto like, used for packaging unit for various photographic light-sensitive material as essential to ensure the complete light-shielding property and good photographic properties.

As an example, a film unit with a lens will be described. As shown in FIG. 5, the lens-fitted film unit 11 includes a unit main body 12 and a label 13 that partially covers the outer periphery of the unit main body 12. The unit main body 12 is loaded with a photographic film in advance. ing. On the front surface of the lens-equipped film unit 11, an opening 16 for exposing the photographing lens 14, an opening 17 for exposing the finder lens, and an opening for exposing the strobe light emitting portion 18 are formed below the strobe light emitting portion 18. Is provided with a strobe charging operation member 19. A shutter button 21, a film counter window 22 and the like are formed on the upper surface, and a winding knob 23 is exposed from the upper surface to the rear surface.

As shown in FIG. 6, the unit main body 12
Main body base 26, strobe unit 27, exposure unit 2
8, a front cover 29 and a rear cover 31. The main body base 26, the front cover 29 and the rear cover 31 are plastic parts, and are recycled after being once returned to raw materials in a recycling line for hygiene and quality reasons.

An exposure frame 26a is formed in the center of the main body 26. A cartridge chamber 26b in which a cartridge 32 is loaded is provided on both sides of the exposure frame 26a, and a film roll in which a photographic film 33 drawn from the cartridge 32 is rolled. The film roll chamber 26c in which the film 34 is loaded is formed integrally. The exposure frame 26a limits the exposure range for one frame at the front of the photographic film 33 sent to the shooting position. A dark box base 26d protruding into a rectangular tube shape is integrally formed in front of the exposure frame 26a, and the exposure unit 28 is assembled to the main body base 26 to form a dark box in cooperation with the dark box 28a on the exposure unit 28 side. .

A film rail (not shown) is formed above and below the back surface of the exposure frame 26d. A film regulating surface 31a is formed on the front surface of the rear cover 31, and by attaching the rear cover 31 to the main body 26, a film feed path is formed by the film rail and the film regulating surface 31a. The photographic film 33 is wound up toward the cartridge 32 every time a photograph is taken. The photographic film 33 is fed while being in contact with the film rail and the film regulating surface 31a and supported by both surfaces. Since the main body base 26 and the rear cover 31 are parts that come into contact with the photographic film 33, it is preferable that they are once formed into recycled resin pellets and recycled in the first plastic parts recycling line.

The lower surfaces of the cartridge chamber 26b and the film roll chamber 26c are open, and these openings are closed by pull-top type bottom lids 31b, 31c formed by making a part of the rear cover 31 thin and openable. . Bottom lid 31b
Is a lid for taking out the cartridge 32 containing the photographed film.

The strobe unit 27 is a printed circuit board 3
Reference numeral 6 is a unit component to which a circuit element including a strobe charging circuit and the like, a strobe light emitting section 18, a synchro switch, a pair of battery contact pieces, and a main capacitor are mounted together. The strobe unit 27 is disposed between the exposure unit 28 and the film storage chamber 26c, and is detachably attached to the main body base 26 by claw engagement. The strobe circuit is
Power is supplied from the power supply battery 37.

The charging operation member 19 for turning on / off the charging of the strobe circuit is attached to the front surface of the printed circuit board 36 via the receiving plate 38. A metal switch piece is attached to the back surface of the charging operation member 19, and when the charging operation member 19 is slid, the switch piece becomes
The contact of No. 6 is turned on to activate the strobe circuit. The charging operation member 19 is a plastic part, which is a part to be touched by the user, and is recycled for hygienic reasons.

The exposure unit 28 has a finder lens 41, a film counter mechanism, a shutter mechanism, and a film unwinding mechanism on its upper part, and a shutter blade (not shown) and a shutter cover 42 on its front face, based on the dark box part 28a. It is a unit part that incorporates and integrates these. The photographing lens 14 is detached and inspected independently.
It is detachably attached to the shutter cover 42 so that cleaning can be performed. Regarding the exposure unit 28 and the photographing lens 14, those which have failed the inspection and cannot be reused are sent to the plastic parts recycling line at the time of recycling and are recycled.

A plurality of shafts and bearings are formed on the upper part of the dark box portion 28a. The film counter plate 43, the top plate 44, and the shutter drive lever 46 are provided on these shafts and bearings.
In addition, a locking lever, a cam member, a spring, and the like are attached. These parts are all made of plastic except for the spring.

A procedure for recycling a film unit with a lens will be described. In the used film unit 11 with a lens, the photographic film 33 and the cartridge 32 are taken out at a developing laboratory or the like, and the unit main body 12 is collected by a manufacturer. The collected unit bodies 12 are sorted for each unit type and sent to a product disassembly line.

In the product disassembly line, cosmetic labels 13
After being peeled off, first, in addition to the front cover 29, the charging operation member 19, the winding knob 23, and the like are removed, and these components are sent to a plastic component recycling line. After the front cover 29 is removed, the exposure unit 28, the power battery 37,
The strobe unit 27 is removed. The exposure unit 28 and the strobe unit 27 are inspected and cleaned and reused. The power supply battery 37 is collected by a battery collection company. Finally, the remaining main body base 26 and the rear cover 31 are separated,
Sent to plastic parts recycling line. In the plastic parts recycling line, carbon parts and an antioxidant are added by the above-described method, and the plastic parts are recycled.

In the above example, the description has been made of a film unit with a lens. However, the present invention is not limited to a film unit with a lens and a photographic film cartridge, but also an instant film unit, a spool and a cartridge for various roll films, a various sheet film pack, and the like. The present invention can be applied to a packaging unit for photographic photosensitive materials such as a sheet film pack holder, a sheet film unit, and a light-shielding magazine for loading a sheet-like or roll-like photographic photosensitive material into a bright room.

[0246]

As described in detail above, the present invention provides
A used resin part molded by injection molding of a thermoplastic resin is crushed, and a crushed crushed material or a recycled resin pellet obtained by extruding the crushed material into a resin pellet by extrusion is used as at least a part of the raw material. In the method of recycling an injection molded product for a photographic light-sensitive material, which is again subjected to injection molding to produce a recycled part, the thermoplastic resin, at least carbon black and an antioxidant as additives are concentrated and mixed, and the resin is extruded by extrusion molding. Pelletized masterbatch resin pellets are generated, and the masterbatch resin pellets are added to the crushed material and the reclaimed resin, and are injection-molded using these as raw materials. Recycled parts can be provided. In particular, since the carbon black and the antioxidant are added in the form of a masterbatch resin pellet, the dispersibility of the additive is improved,
Quality variability is reduced.

[Brief description of the drawings]

FIG. 1 is a flowchart showing a recycling procedure.

FIG. 2 is a flowchart showing a first plastic component recycling procedure.

FIG. 3 is a flowchart showing a second plastic component recycling procedure.

FIG. 4 is a sectional view of the injection molding machine.

FIG. 5 is an overall perspective view of a film unit with a lens.

FIG. 6 is an exploded perspective view of the film unit with a lens.

[Explanation of symbols]

 11 Film unit with lens 19 Charging operation member 27 Strobe unit 28 Exposure unit 29 Front cover 31 Rear cover 33 Photo film

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification code FI Theme coat ゛ (Reference) G03C 3/00566 G03C 3/00 566P B29B 17/00 B29B 17/00 B29C 45/00 B29C 45/00 C08J 3/22 CER C08J 3/22 CER C08K 3/04 C08K 3/04 5/00 5/00 C08L 101/00 C08L 101/00 F term (reference) 4F070 AA11 AA12 AA18 AC04 AC37 AC46 AC49 AC55 AE03 AE04 FB03 FB04 4F206 AB06 AB18 AH73 JA07 JF02 JF51 4F301 AA12 AA15 AB01 AB02 AB03 BF12 BF16 BF32 4J002 AA011 DA036 EJ037 EJ047 EJ067 EN067 EU117 EV127 EW067 FD077 FD096

Claims (7)

[Claims] 1. A used resin part formed by injection molding of a thermoplastic resin is crushed, and the crushed crushed material is used as at least a part of a raw material, and injection molded again to produce a recycled part. In a method of recycling an injection molded article for a photographic photosensitive material, the thermoplastic resin and at least carbon black and an antioxidant as additives are concentrated and mixed, and a master batch resin pellet is formed by extrusion molding to form a master batch resin pellet. A method for recycling an injection-molded article for a photographic photosensitive material, comprising adding a masterbatch resin pellet together with the crushed material as a part of the raw material and performing injection molding. 2. A recycled resin pellet obtained by crushing a used resin component formed by injection molding of a thermoplastic resin and extruding the crushed crushed material to form a resin pellet again at least as a part of a raw material. A method for recycling injection molded articles for photographic light-sensitive materials, wherein injection molding is performed again to produce recycled parts, wherein the thermoplastic resin, at least carbon black and an antioxidant as additives are concentrated and mixed, and the resin is extruded by extrusion molding. A method for recycling an injection-molded article for a photographic light-sensitive material, comprising: forming a pelletized master batch resin pellet; adding the master batch resin pellet together with the crushed material as a part of the raw material; and performing injection molding. 3. The carbon black has an average particle size of 1
3. The method for recycling an injection molded article for a photographic photosensitive material according to claim 1, wherein the thickness is from 0 to 80 nm. 4. The photograph according to claim 1, wherein the content ratio of the carbon black is 0.2 to 0.5% by weight based on the total weight of the raw materials including the additives. How to recycle injection molded products for photosensitive materials. 5. The composition according to claim 1, wherein the content of the antioxidant is 0.02 to 0.3% by weight based on the total weight of the raw materials including the additives. How to recycle injection molded products for photographic photosensitive materials. 6. A photographic photosensitive material regenerated by injection molding by crushing a used resin part formed by injection molding of a thermoplastic resin and using the crushed crushed material as at least a part of a raw material. In the recycled part, the thermoplastic resin, at least carbon black and an antioxidant as additives are concentrated and mixed to produce master batch resin pellets formed by extrusion molding, and the master batch resin pellets are crushed. A recycled part for photographic light-sensitive materials, characterized by being injection-molded together with a material as a part of the raw material. 7. A recycled resin pellet obtained by crushing a used resin component formed by injection molding of a thermoplastic resin and extruding the crushed crushed material into a resin pellet by at least part of the raw material. In the recycled part for photographic light-sensitive materials reproduced by injection molding, the thermoplastic resin and at least carbon black and an antioxidant as additives are concentrated and mixed, and a master batch resin pellet is formed by extrusion molding into a resin pellet. A recycled part for photographic light-sensitive materials, wherein the recycled resin pellet is produced and added together with the recycled resin pellet as a part of the raw material, followed by injection molding.