JP2002139819A - Method for recycling resin molding for photographic material and recycled parts for photographic material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To prevent the lowering of the photographic properties of recycled parts for a photographic material. SOLUTION: Resin parts of a lends-fitted photographic film unit, e.g. the front and rear covers and the body base are crushed once, the crushed material is palletized again and the regenerated resin pellets are regenerated as part of staring materials by injection molding and used as recycled parts. When the crushed material is melted by heating in the injection molding, the thermoplastic resin deteriorates or degenerates thermally and the performance and quality of the recycled parts lower as compared with those of new parts. When the thermoplastic resin deteriorates thermally, it causes a chemical reaction with a photographic material and generates a larger amount of a decomposition product that adversely affects photographic properties. An antioxidant is added so as to prevent the thermal deterioration and carbon black is added so as to adsorb the generated decomposition product.

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 a resin molded product for a photographic material and a recycled part for a photographic 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. It is formed by molding this, for example, by injection molding. Hereinafter, these plastic molded parts are referred to as resin molded articles for photographic photosensitive materials.

The quality and performance required of the resin molded product 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. That is, the adverse effects on the photographic properties include fog, abnormal sensitivity, abnormal gradation, abnormal coloring, uneven density, etc., which occur in the photographic film.

The causes include, for example, deformation of a resin molded product and molding defects such as occurrence of bumps such as resin on the surface of the molded product. Fog and film flaws occur. Also, when the resin molded product is charged, static electricity is generated, and this static electricity generates a static mark (dendritic or blurred circular fog). In addition to these physical factors,
There are chemical factors such as a chemical reaction between a decomposition product such as a gas generated from a resin molded product and a photographic film.

A resin serving as a base of a resin molded product for a photographic light-sensitive material is selected so as to satisfy the above-mentioned quality and performance,
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 and are inexpensive. Further, as the light-shielding substance, carbon black or the like is used.

[0008] However, ordinary polystyrene resins have insufficient physical strength such as erosion to a part of oils and organic solvents, weather resistance, heat resistance, and breaking strength, and are liable to be charged. There are disadvantages. 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.

[0010] A new resin molded product for a photographic light-sensitive material is molded using the new resin pellet as a raw material. Since the new resin pellets are heated and melted at the time of molding, the additives mixed with the new resin pellets are partially dissipated and may be reduced or denatured. 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 resin molded product for a photographic photosensitive material is designed to exhibit predetermined performance and quality.

Incidentally, industrial products are recycled for environmental protection and reduction of industrial waste. Regarding the resin molded product of the photosensitive material, the collected molded product is crushed, the crushed crushed material is melted, extruded into a strand (twist) shape, and cut into pellets of a predetermined size. Recycling is carried out by re-injecting the recycled resin pellets as a part of raw materials into a production line to form recycled parts.

[0012]

However, when a performance test was conducted, it was found that the recycled product was inferior in photographic properties as compared with a new product. In particular, it has been found that fogging is more likely to occur on a photographic film in the case of a recycled product than in a new product. This deterioration in photographic properties is more evident as the photographic film becomes higher in sensitivity. Therefore, high-sensitivity photographic films have come to be used as photographic films stored in photographic film cartridges or film units with lenses. In recent years, it has become a particular problem.

In the recycling step, the resin composition is heated and melted once and returned to the raw materials. Due to this heat melting, thermal deterioration of the thermoplastic resin proceeds,
It is considered that an additive such as an antioxidant for preventing thermal deterioration partially undergoes some modification, resulting in deterioration in performance as compared with a new product.

In order to solve the above-mentioned problems, a method for recycling a resin molded product for a photographic light-sensitive material and a recycled part for a photographic light-sensitive material according to the present invention reduce the photographic properties of the stored photographic light-sensitive material as compared with a new one. The purpose is to prevent.

[0015]

In order to achieve the above object, a method of recycling a resin molded product for a photographic light-sensitive material according to the present invention comprises crushing a used resin part formed of a thermoplastic resin and crushing the crushed resin part. Using the crushed material as at least a part of the raw material, and re-molding the resin molded product for photographic light-sensitive material to form a recycled part by adding at least carbon black and an antioxidant as additives at the time of recycling. It is characterized by being molded.

In addition, a used resin part formed of a thermoplastic resin is crushed, and the crushed crushed material is re-formed into a resin pellet. In the method of recycling resin molded products for photographic photosensitive materials that produce parts,
It is characterized by adding at least carbon black and an antioxidant as additives at the time of recycling and molding.

Further, a resin for a photographic photosensitive material, wherein a used resin part formed of a thermoplastic resin is crushed, and the crushed crushed material is used as at least a part of a raw material to be molded again to produce a recycled part. In the method for recycling molded articles, in order to reduce decomposition products which are generated from the crushed material by causing the crushed material to be deteriorated or deteriorated by heating during the molding and adversely affect the photographic properties of the photographic light-sensitive material, Adsorbing or capturing the decomposition products,
Alternatively, a decomposition product suppressing additive for suppressing generation of the decomposition product is added during the recycling.

In addition, a used resin part formed of a thermoplastic resin is crushed, and the crushed crushed material is again formed into a resin pellet. In the method of recycling resin molded products for photographic photosensitive materials that produce parts,
The crushed material is degraded or deteriorated by heating during the molding, and is generated from the crushed material, so as to reduce decomposition products that adversely affect the photographic properties of the photographic light-sensitive material. Alternatively, an additive for suppressing a decomposition product which captures or suppresses generation of the decomposition product is added at the time of the recycling.

It is preferable to use carbon black and an antioxidant as additives for suppressing the decomposition products.

The average particle size of the carbon black is preferably 10 to 80 nm, and the mixing ratio of the carbon black is 0.2 to 1.2 with respect to the total weight of the raw materials including the additives. % By weight.

The mixing 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.

In addition, a used resin part formed of a thermoplastic resin is crushed, and the crushed crushed material is used as at least a part of the raw material. It is characterized by adding at least carbon black and an antioxidant as an agent and molding.

In addition, a recycled resin part obtained by crushing a used resin part formed of a thermoplastic resin and re-pulverizing the crushed crushed material into a resin pellet is used as at least a part of a raw material. Characterized in that at least carbon black and an antioxidant are added as additives at the time of recycling, and molding is performed.

Further, in a method of recycling a resin molded product for a photographic light-sensitive material, a used resin part molded with a thermoplastic resin is crushed, and the crushed material is used as at least a part of a raw material to produce a recycled part. At the time of recycling, at least a new resin containing rubber, carbon black, and an antioxidant are added to the crushed material to be molded.

Further, a photographic light-sensitive material for producing a recycled part by using a recycled resin pellet obtained by crushing a used resin part molded from a thermoplastic resin and re-pulverizing the crushed material into a resin pellet at least as a part of the raw material. In the recycling method for molded resin products, at the time of recycling, at least a new resin containing rubber, carbon black,
It is characterized in that an antioxidant is added to the recycled resin pellets and then molded. The average particle diameter of the carbon black is preferably 16 nm to 24 nm.

In addition, a used resin part molded with a thermoplastic resin is crushed, and the crushed material is used as at least a part of a raw material. A new resin containing rubber, carbon black, and an antioxidant are added to the crushed material to be molded.

Further, a used resin part molded with a thermoplastic resin is crushed, and the crushed material is heated and melted, and then re-formed into a resin pellet. A recycled part for a photographic photosensitive material is characterized in that, at the time of recycling, at least a new resin containing rubber, carbon black, and an antioxidant are added to the recycled resin pellets and molded. The average particle diameter of the carbon black is preferably 16 nm to 24 nm.

[0028]

DESCRIPTION OF THE PREFERRED EMBODIMENTS First, a resin material used in a resin molded product for a photographic light-sensitive material of the present invention will be described. As the resin material constituting the resin molded product for a photographic photosensitive material, a thermoplastic resin is preferably used, and it is preferable to add a light-shielding substance for imparting a light-shielding property to the thermoplastic resin.

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 Agents, air fresheners, desiccants, hygroscopic agents,
Various other additives, such as chelating agents, inorganic or organic nucleating agents, plasticizers, etc., are selected alone or in accordance with the type and amount of additive that do not adversely affect the photographic properties of the photographic material. Two or more kinds may be used in combination in a resin pellet.

The thermoplastic resin used for the resin material of the resin 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.

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 high-impact polystyrene resin, which is particularly preferred among the thermoplastic resins described above, is inexpensive and has excellent moldability. Such a styrenic resin contains 0.01 to 5% by weight of a lubricant, 1.0 to 10% by weight of a synthetic rubber having an average particle size of 1.5 to 5 μm, and 0.001 to 1.0% of an antioxidant. 0% by weight and a light-shielding substance in the range of 0.1 to 10% by weight, respectively.

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

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

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

Next, the thermoplastic elastomer will be described. Thermoplastic elastomers are impact resistant materials,
It has the function of improving the physical strength of resin molded products 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.

[0038] 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
Not only has excellent compatibility with other thermoplastic resins and other conventional thermoplastic resins, but also has 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, a resin 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 resin, polyacetal resin, polyamide resin, polyvinylidene chloride 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 monomers include, 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 obtained by subjecting the above-mentioned suitable monomers to a known suitable method, 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 the styrene-based thermoplastic elastomer include, for example, a styrene-butadiene-styrene block copolymer resin and its hydrogenated styrene-ethylene-butylene-styrene block copolymer resin, and styrene-butadiene copolymer. 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 trade names and the names of manufacturers of typical styrene-based thermoplastic elastomers are shown below. Kraton (or Califlex TR), Kraton G (or Elexar) (Shell Chemical), Solpre
ne T (Phillips Petroleum), Europrene
SOL T (ANIC), Solprene T (Petroc
hi), Tufprene (Asahi Kasei), Solprene T, Asaprene T (Nippon Elastomer), Clearen (Electrochemical), JSR, SBR (Nippon Synthetic Rubber), etc.

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

Unsaturated carboxylic acids 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 opaque resin molded articles are preferable, and particularly, light-shielding substances. 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,
Moreover, it is a carbon black which 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 a resin molded product even when used for a long time under sunlight.

Carbon black is classified into, for example, 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 resin molded product for a photographic light-sensitive material, fog is not generated in the photographic light-sensitive material, the sensitivity does not increase or decrease, 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 resin molded product 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.

High-performance liquid chromatographic separation conditions are 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, detection 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.

Representative examples of preferable commercial products of carbon black include, for example, acetylene black manufactured by Denki Kagaku and carbon black # 20 (B) and # 3 manufactured by Mitsubishi Chemical.
0 (B), $ 33 (B), $ 40, $ 41 (B), $ 4
4 (B), $ 45 (B), $ 50, $ 55, $ 100,
$ 600, $ 950, $ 1000, $ 2200, $ 22
00 (B), $ 2400 (B), MA8, MA11, MA
However, the present invention is not limited to these.

The manner in which the light-shielding substance is kneaded with 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 modes, the masterbatch method is preferable from the viewpoint of prevention of contamination of the work place and cost. JP-B-63-186740 discloses 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, various metal powders, metal flakes, metal pastes, metal fibers and carbon fibers. Preferred refractive index is 1.
Representative examples of 50 or more inorganic pigments and metal powders are shown below,
The present invention is not limited to these. ()
The numbers in the parentheses indicate the refractive index.

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

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 the 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 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 particularly preferable as a resin molded product 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 a deodorant, a fragrance, an oxygen scavenger, etc. 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 the photographic material, so be careful when using it as a resin molded product for direct contact with the photographic material. is necessary.

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

In particular, it is preferable to use the resin as an aluminum paste masterbatch resin in order to eliminate adverse effects and odors on the photographic light-sensitive 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 content of the aluminum paste in a resin molded product for photographic light-sensitive materials is reduced to 2%.
If it is attempted to make the weight percent, 19 parts by weight of a natural resin (resin for dilution) will be kneaded with 1 part by weight of the aluminum paste masterbatch. Mineral spirit content is 0.
05% by weight or less. As a result, the photographic properties of the photographic material are not adversely affected, and the odor is reduced.

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

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

The preferable total amount of the light-shielding substance in the resin molded article is from the viewpoint of improving the moldability, securing the quality of the molded article, securing the light-shielding property, securing the physical strength, securing the photographic performance of the photographic light-sensitive material, economy, and the like. The 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 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 balance of physical strength, 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 molded product is extremely large, the light-shielding ability is insufficient and light fog is generated. In addition, if the thickness of the resin molded product for a photographic material is increased in order to obtain a sufficient light-shielding property with this content, the molding cycle of the resin molded product for a photographic material becomes longer (because the cooling time becomes longer). , Sink mark (S
(ink mark), warping and twisting 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 occur on the photographic light-sensitive material. The amount of water in the resin molding for materials 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.). Furthermore, the moldability of the resin molded product for photographic photosensitive materials deteriorates (molding failures such as foaming, silver strips, burns, pinholes, and short shots occur) and the physical strength decreases, making practical use difficult.

The resin composition containing the light-shielding substance contains 0.50% by weight of volatile components (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 formability. More preferably 0.40% by weight or less, particularly preferably 0.30% by weight or less, most preferably 0.20% by weight.
It is as follows. In addition, the drying of the resin composition may be performed by heating,
Vacuum or heating / vacuum (for example,
Drying at 70 ° C. for 3 hours).

Improvement of dispersibility of a light-shielding substance in resin, improvement of resin fluidity, friction fog and pressure fog on a 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, dripproofing agents and the like can be used in combination 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 this case, the motor load can be reduced to improve the moldability, and the effect of improving the appearance of the resin molded product can be exhibited.

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

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

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 molded product varies greatly, and short shots and the like are more likely to occur, which makes practical use difficult.

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

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

Red; red bengara, disazo pigment, berlene pigment, monoazo lake pigment, condensed azo pigment, cadmium red, bon red 2B, carmine 6B, pyrazolone red, lake red C, lead red, permanent red 4
R, etc. Blue; Cobalt blue, ultramarine, navy blue, phthalocyanine blue, cyanine blue, indanthrene blue, indigo, cyanine blue, etc. Green; chrome oxide green, titanium green, zinc green, emerald green, cobalt green, pigment green, phthalocyanine green , Cyanine green, etc. Silver; aluminum powder, aluminum paste, tin powder, 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. A camera that is a resin molded product for photographic photosensitive materials that can be used for a long time under sunlight, left for a long time under sunlight, or used in deserts, a resin photographic film cartridge for APS, and a photographic film spool 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.

First, among these additives, the lubricant will be described. By mixing the lubricant with the thermoplastic resin, the fluidity of the thermoplastic resin is improved, and as a result, the moldability is improved. Further, the dispersibility of the light-shielding substance can be improved by adding a lubricant. Below, the names of typical commercially available lubricants and the names of their manufacturers are described together.

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 lubricant] (1) Erucamide amide 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) Methylenebishevenenamide 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 hydrocarbons, fluorocarbons, 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. Lower alcohol esters of ester-based lubricant fatty acids,
4. Polyhydric alcohol esters of fatty acids, polyglycol esters of fatty acids, fatty alcohol esters of fatty acids, etc. 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 various lubricants, the one which is preferably applied to a resin molded product 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 may 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 to 50 in that many effects such as improvement of physical strength, improvement of light-shielding property, improvement of lubricity, improvement of moldability, etc. are obtained without adversely affecting the photographic properties of the photographic light-sensitive material. More preferred is 100000 centistokes of dimethylpolysiloxane. Considering handleability, photographic properties and cost, the viscosity at 23 ° C is 5000-50
000 centistokes of dimethylpolysiloxane is most preferred. 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.

[0110] These silicone oils improve the physical strength of the molded product, improve the surface hardness, shorten the molding cycle, improve the friction coefficient, reduce the sliding resistance, and generate weld lines and short shots. It is possible to obtain a resin molded product for a photographic photosensitive material having a beautiful appearance which is not excellent, 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 resin molded product 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. The antioxidant prevents thermal degradation of the thermoplastic resin and thermal decomposition of various additives. 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.

The 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 that at least one or more of these are added to the resin molded product for photographic photosensitive materials.

Various known compounds such as hydrazine compounds can be used to reduce and stabilize the pyrolyzate to an amount that does not adversely affect the photographic properties of the photographic material, to stabilize the reaction, or to stabilize the adsorption. , A urea compound and the like are preferably added together.

The amount of the antioxidant added 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 type antioxidant;
-Ethoxy-2,2,4-trimethyl-1,2-dihydroquinoline, polymers of 2,2.4-trimethyl-1,2-dihydroquinoline, trimethyldihydroquinoline derivatives and the like.

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

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

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

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

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

Among the above antioxidants, a phenolic antioxidant and a phosphite antioxidant are preferable because they have little adverse effect on the photographic properties of the photographic light-sensitive material and have excellent antioxidant effects. . 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.

Among 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.

It is effective to use the above-mentioned antioxidant in combination with a phosphorus-based antioxidant. Furthermore, at least one of phosphorus-based antioxidants, at least one of hindered phenol-based antioxidants, and at least one of water-containing double salt compounds such as hydrotalcite compounds are used in total of three or more. Is particularly preferred.

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

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

Commercially available phenolic antioxidants include various types of Irganox from 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 kinds of antioxidants include a combination of a hindered phenol-based antioxidant and a pentaerythritol phosphite compound-based antioxidant, and a combination of a hindered phenol-based antioxidant and a 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, hindered antioxidants are liable to be thermally degraded, but improve the dispersibility of light-shielding substances, neutralize catalyst residues, and improve the photographic properties of photographic light-sensitive materials.
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 resin molded product for a photographic light-sensitive material 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 effect 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 a thermal decomposition substance which adversely affects 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 amount of addition
0.001 to 1.0% by weight, preferably 0.005 to
It is 0.7% by weight, particularly preferably 0.01 to 0.45% by weight. Less than 0.001% by weight has no effect.
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 resin molded products for photographic photosensitive 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. ｝

[0143] 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.

In particular, 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. In addition, in order to particularly improve the processability such as molding, physical properties, etc., the average secondary particle diameter is 20 μm or less,
Preferably 10 μm or less, particularly preferably 5 μm or less, B
ET specific surface area of 50 m ² / g or less, preferably 40 m ² /
g, especially 30 m ² / g or less.

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

As examples of such a surface coating material, the above-mentioned surface coating materials (1) to (20) of a light-shielding material can be used. 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.

Also, higher fatty acids represented by lauric acid, palmitic acid, oleic acid, stearic acid, capric acid, myristic acid, linoleic acid and the like; organic sulfonic acids such as calcium dodecylbenzenesulfonate and sodium dodecylbenzenesulfonate; Metal salts: isopropyl 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 with stirring. It can be carried out by dropping a solution of a higher fatty acid or a diluting solution of a coupling agent while stirring the talcite compound powder with a mixer such as a Henschel mixer.

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

In order to further disperse the hydrotalcite compounds, for example, 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 prevention of deterioration of photographic properties, the stability of molding, and the effect of preventing corrosion (also referred to as rust prevention) of an injection molding machine or a mold are improved, and the coloring of a resin molded product is improved. In addition to preventing deterioration of the resin, the transparency of a transparent molded product is improved, the physical strength is prevented from lowering, and the effect of preventing the occurrence of spots and coloring failure due to burning of the resin 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 the resin molded article for a photographic light-sensitive material 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 resin molded product 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 resin 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, in addition to the above properties, transparency, crystallization speed, and moldability (cycle shortening, molding failure reduction) can be improved.

The total content of one or more of the inorganic nucleating agent and the organic nucleating agent in the resin molded product is from 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 molded article with the passage of 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, bentonite, calcium silicate, magnesium silicate, calcium sulfate, barium sulfate, lithium carbonate, and carbonate. Inorganic salts such as sodium, sodium hydrogen carbonate, potassium hydrogen carbonate, calcium carbonate, magnesium carbonate, lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide, magnesium hydroxide, barium hydroxide, etc., sodium oxide, calcium oxide And metal chlorides such as magnesium oxide, alumina, titanium oxide, iron oxide and zinc oxide.

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

The carboxylic acids are generic names including their derivatives, and typical examples are acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, tetrahydrophthalic acid, mesaconic acid, angelic acid, 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, the generation of the decomposition products is small and the photographic properties of the photographic material are not adversely affected, the nucleating effect is the highest, and the molding cycle can be shortened most. Sorbitol derivatives are preferred because they exhibit various effects such as minimizing the occurrence of molding 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) sorbitolaluminu
mbenzoate, etc.

Next, a surfactant-based antistatic agent will be described. In order to maintain the antistatic property of the resin molded product for a photographic light-sensitive material, 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 Yuka Chemical) hydroxystearic acid amide oxalic acid-N, N'-distearylamide butyl ester; Hoechst polyoxyethylene alkylamide

(3) Ether type polyoxyethylene alkyl ether RO (CH ₂ CH ₂ O) nH polyoxyethylene alkyl phenyl ether Special non-ion type; Register 104, PE100, 1
16-118 (Daiichi Kogyo Pharmaceutical), Register PE13
2, 139, Elegan E115, Chemistat 113
(Daiichi Kogyo Pharmaceutical Co., Ltd.), Chemistat 1005 (Nippon Oil & Fats), Erik BM-1 (Yoshimura Oil Chemical), Electrostrippers TS-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, monogly (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

[0171] 2. Anionic (1) Sulfonic acids Alkyl sulfonate RSO ₃ Na Alkylbenzene sulfonate Alkyl phosphate ROSO ₃ Na (2) Phosphate ester type alkyl phosphate

[0172] 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
S53, AMS 303, 313 (lion fat) Alkyl imidazoline type (3) Metal salt type; AMS 576 (lion fat) Leostat 826, 923 (lion fat) (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

[0174] 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, 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.

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

[Representative Examples of Reactive Compatibilizers] Anhydrous maleic oxide / propylene copolymer resin Anhydrous maleic styrene graft copolymer resin Anhydrous maleic styrene / butadiene / styrene copolymer resin Anhydrous maleic oxide / 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 commercially available internal and external 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 resin molded product for photographic light-sensitive materials 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 the physical strength, the appearance, and the compatibility. Also,
If the amount is more than 45% by weight, the rigidity may be insufficient or the photosensitive material may be adversely affected.
The cost is high because of the high cost, and it is difficult to commercialize it economically.

Next, the anti-blocking agent will be described. Polyolefin resins, especially copolymer resins containing ethylene, tend to block due to their tackiness. For this reason, blocking occurs between the molded products made of polyolefin resin, making it difficult to convey, or generating static electricity to cause a static mark failure in the photographic photosensitive material.

When the blocking occurs as described above, not only does the workability in the production of a resin molded product for a photographic photosensitive material and the subsequent processing and packaging deteriorate, but also the use of the resin molded product for a photographic photosensitive material causes When trying to manufacture a package, blocking occurs between the photosensitive material and the resin 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 a resin molded product for a photographic light-sensitive material, a light-blocking substance having an anti-blocking action and a lubricant having a large effect of improving the lubricity of the photographic light-sensitive material and having a large anti-blocking effect, and an anti-blocking agent To prevent these various troubles.

Typical examples of the antiblocking agent which can be used in the present invention, which has a particularly large antiblocking effect and does not adversely affect the photographic properties of the photographic 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.

Further, among the preferred light-shielding substance dispersants,
The following are typical examples of commercially available products. (1) Examples of low molecular weight styrenic polymers having a weight average molecular weight of 5,000 to 50,000 are “Hymer SB”,
"Regit S" (manufactured by Sanyo Kasei Kogyo Co., Ltd.) "Erastyrene", "Picolastic D" (manufactured by Shell Chemical Co., Ltd.) (2) Polyethylene wax or polypropylene wax having a weight average molecular weight of 500 to 20,000, and derivatives thereof. And (they are modified with unsaturated acids such as maleic acid, acrylic acid, maleic anhydride, or unsaturated acid anhydrides, or those obtained by subjecting these metal salts or oxidation treatments to AC AC polyethylene) (Manufactured by Aland Chemical Co., Ltd.) "High Wax" (manufactured by Mitsui Petrochemical 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. The resin molded product for a photographic photosensitive material preferably 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 examples of the yellow pigment include titanium yellow, chrome yellow, cadmium yellow, oil yellow, chromophtal yellow GR, quinophthalone, and benzidine yellow.

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;
A light-reflective resin molded product for a photographic photosensitive 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. A resin molded product for a photographic photosensitive material such as a film unit with a lens is required to be left under sunlight or to ensure good quality of the photographic photosensitive material 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 this ultraviolet absorber is based on 100 parts by weight of various polyolefin resins, homostyrene resins, polyamide resins, various rubber-containing aromatic vinyl resins and other styrene resins, and various polycarbonate resins and other thermoplastic 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.

If 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 reaction products of these aliphatic and aromatic polycarboxylic acids with polyhydric alcohol compounds and acidic polyester compounds having a carboxyl group at the end. There is.

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

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

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

The fragrance includes natural flavor components such as lilac flower oil, jasmine, avies oil, cinnamon oil, lavender oil, lemon oil, geraniol, eugenol, n-
Octyl alcohol, carbitol, cis-chasmon, lemon terpene, menthone, methyl salicylate, methylphenylcarbinol, triethyl citrate,
Synthetic aromatic components such as benzyl benzoate, citral, d-linemon, geraniol, ethyl cinnamate, octanol, benzyl benzoate, alkylene glycol, benzyl salicylate, linalool, vanillin, coumarin, methyl naphthyl ketone, and rosephenone are 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 resin molded product for a photographic light-sensitive material 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 resistance modifier (various elastomers, rubber, L-LDPE resin, etc.) b. Filler, reinforcement c. Colorant d. Plasticizer e. Foaming agent f. Crosslinking agent (organic oxide) g. Nucleating agent 2-3 Function modifier (function imparting agent) a. Conductive agent, magnetic agent b. Antistatic agent (also called antistatic agent) c. Fluorescent whitening agent 2-4 Decomposition accelerator a. Biodegradation b. Photolysis c. Thermal decomposition, etc.

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

When molding using the thermoplastic resin composition of the present invention as described above, an ISO molding method is used to prevent unexpected molding failures such as burning, silver strip, foaming, weld lines, sink marks and short shots. The amount of water 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 2053-76 measurement method (105 ° ± 2 ° C., drying for 1 hour).
Use as follows (heat, vacuum, heat vacuum and dry).

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

Next, the production of a new resin molded product for a photographic light-sensitive material will be described. When manufacturing a new resin 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 extruder and melted, and is extruded into a strand shape by extrusion. It is formed. The strand-shaped thermoplastic resin composition is cut into pellets, and new resin pellets are produced. next,
New resin pellets are input to a production line as raw materials, and a resin molded product for photographic photosensitive materials is manufactured 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 an additive is contained in a new resin molded article of a photographic photosensitive material that has been injection-molded, and required performance and quality are secured.

A new resin molded product for a photographic light-sensitive 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.

Hereinafter, the procedure for recycling the resin molded product for a photographic photosensitive material will be described with reference to the flowcharts shown in FIGS. The recycling line consists of a product disassembly line, a plastic parts recycling line, and a production line.

In the product disassembly line, reused parts such as metal parts and electric parts are removed from the product, and the remaining parts including plastic are sent to the plastic part recycling line. If the product is, for example, a film unit with a lens, this plastic parts recycling line
Parts including plastic, such as a rear cover, a front cover, and a main body base, to which a light-shielding substance such as carbon black is already added, are supplied.

As shown in FIG. 2, the first plastic part recycling line is composed of 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 separating 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 separating step, and a material different from plastics such as metal pieces and a plastic having different specific gravity are 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, aqueous magic ink (registered trademark) and the like 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. The solidified strand-shaped resin is cut into a predetermined size and pelletized, thereby producing recycled resin pellets.

When the crushed material is heated and melted by melt extrusion or injection molding, the thermoplastic resin is thermally decomposed and deteriorates or deteriorates, thereby deteriorating the performance and quality of the thermoplastic resin. Further, when the crushed material is heated and melted, additives such as carbon black added at the time of producing new resin pellets undergo some modification, and for example, the light shielding ability and the like are reduced.

The antioxidant has a function of preventing the deterioration of the thermoplastic resin, but the antioxidant added at the time of producing the new resin pellets may disappear and decrease due to the heating and melting of the crushed material. . In order to prevent the performance and quality of the recycled parts from being deteriorated due to the heating and melting, carbon black and an antioxidant are added when the recycled resin pellets are formed.

[0224] Carbon black secures the light-shielding properties of plastic parts. Further, carbon black has a function of adsorbing or capturing decomposition products generated during molding or holding of the thermoplastic resin. In order to improve the ability to adsorb or capture this decomposition product, for example, carbon black having a small particle size is used. If the particle size is small, the surface area for adsorption increases,
The adsorption or trapping ability is improved. The average particle size of the carbon black is preferably from 10 to 80 nm, and particularly preferably from 16 to 24 nm. Of course, it is not limited to this average particle diameter, and particles having other diameters may be used.

Further, 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. The mixing ratio of the carbon black can be appropriately changed according to the performance required for the resin composition. However, a preferable ratio is 0.2 to 1.2 with respect to the weight of the entire resin composition. % By weight.

As described above, the antioxidant functions to prevent the thermal degradation of the thermoplastic resin and the additives and maintain the performance and quality thereof, and also to prevent the generation of the decomposition products caused by the thermal degradation and 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. The mixing ratio of the antioxidant can be appropriately changed according to the performance required of the resin composition. However, a preferable ratio is 0.02 to 0. 3% by weight.

Further, the types of carbon black and antioxidant 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 the generation of the decomposition products. Therefore, carbon black and antioxidants already contained in the crushed material are required. A different type of agent may be used, or the same type may be used if the carbon black or antioxidant already contained in the crushed material satisfies the property. Good.

[0229] The recycled resin pellets thus recycled are supplied to a component molding line as raw materials. 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. The recycled parts are supplied to a production line to assemble a product. Since the recycled resin molded product for photographic light-sensitive material contains carbon black and an antioxidant, it is not inferior in performance and quality, such as light-shielding ability, even when compared with a new one, and Since generation of decomposition products is also suppressed, photographic properties are not degraded. Further, as shown in the test results described later, by additionally adding a new resin pellet containing rubber, it is possible to suppress a decrease in impact resistance of the recycled component.

In the above example, the carbon black and the antioxidant are added at the time of producing the recycled resin pellets. However, the carbon black and the antioxidant may be added at the time of injection molding, not at the time of producing the recycled resin pellets. Further, carbon black and an antioxidant may be added in two stages, that is, during the production of the recycled resin pellets and during the injection molding.

In the first plastic part recycling line shown in FIG. 2, the crushed material is again pelletized by an extruder to produce recycled resin pellets, and the recycled resin pellets are formed into parts or all of the raw materials. This is an example where the recycled crushed material that has been washed and dried after fine crushing without pelletizing the crushed material, as in the second plastic parts recycling line shown in FIG. 3, is part of the raw material. May be put into the part molding line. The recycled crushed material is used by being mixed with other raw materials (recycled resin pellets or new resin pellets). When using recycled crushed materials as raw materials, the addition of carbon black and antioxidants
Performed during injection molding. Further, when the recycled crushed material is used as a raw material, there is an advantage that the recycling cost can be reduced by omitting the pelletizing step.

As described above, resin molded articles for photographic photosensitive materials to which carbon black and an antioxidant are added at the time of recycling include photographic film cartridges made of resin, (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. 4, 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. 5, 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, and a cartridge chamber 26b in which a cartridge 32 is loaded on both sides thereof, and a film roll formed by rolling a photographic film 33 drawn from the cartridge 32. 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.

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 is based on a dark box 28a, and 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. 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 in 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, the cosmetic label 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.

Next, the results of the first and second photographic tests comparing the new resin and the recycled resin are shown. First, the first photographic test will be described. The first photographic property test method is to put a sample resin pellet to be tested and a photographic film in one container, leave it in that state for one week, develop the photographic film taken out of the container, and remove fog. The change in sensitivity was measured. The temperature inside the container is 50
It is maintained at 60 ° C and 60% humidity. The weight of the sample resin pellets to be put in the container was 500 g, and as a photographic film, a 135-color negative color film of ISO sensitivity of 800 was used.

The extruder used to produce the sample resin pellets is a well-known vent-type single-screw extruder. The diameter D of the screw diameter is 100 mm. The one having a ratio L / D of 28 was used, and the extrusion temperature was 230 ° C. Sample resin pellets are formed into pellets by this extruder.

Next, five sample resin pellets 1 to 5 used in the first photographic test will be described. The sample resin pellet 1 is used as a new resin model, and is obtained by mixing a new resin obtained by mixing butadiene rubber with a polystyrene resin and carbon black, and extruding the resin once to form a resin pellet. . The mixing method of carbon black is to produce a carbon masterbatch resin in which a thermoplastic resin contains carbon black at a ratio of 24.5% by weight, and mix the carbon masterbatch resin with the new resin at a weight ratio of 1:35. And mixed. The carbon black used here has an average particle diameter of 24 nm, a PH (hydrogen ion index) of 8.0, and a nitrogen adsorption specific surface area of 110 m ² / g. This carbon black is hereinafter referred to as C1, and this C1 is hereinafter referred to as C1. The carbon masterbatch resin contained is referred to as CM1.

The carbon master batch resin CM1
Was produced by a known method described below. That is, first, 49% by weight of carbon black C1, 1% by weight of zinc stearate, and 50% by weight of a polystyrene resin are mixed and kneaded by a Banbury mixer, and a horn-like high-concentration carbon-containing resin is produced via a mixing roll. Next, the high-concentration carbon-containing resin and the new resin were mixed at a weight ratio of 1: 1 and melted and kneaded by a vent-type extruder to obtain a cylindrical carbon master batch resin CM1.

Each of the sample resin pellets 2 to 5 is a recycled resin model for imitating the recycled resin, and is compared with the sample resin pellet 1 which is a new resin model. The sample resin pellet 2 is produced in the same mixture and the same mixing ratio as the sample resin pellet 1, and is different from the sample resin pellet 1 in the number of times of being extruded. The sample resin pellet 2 is obtained by repeating the heating and melting five times in an extruder. Recycled resin is generated after a used resin part is heated and melted again to return to a raw material once. In order to simulate this regenerated resin, the sample resin pellet 1 is repeatedly heated and melted to form a sample resin pellet 2.

[0249] The sample resin pellets 3 were fed to an extruder at the same mixture and the same mixing ratio as the sample resin pellets 1.
Sprinkle, add 1/30 of the amount of the carbon master batch resin CM1 initially mixed (the amount mixed with the sample resin pellet 1) to the generated resin, and further extrude them. Generated once. The number of times of extruding was set to 5 times (4 times + 1 time), and the number of times of repetition of heating and melting was the same as that of the sample resin pellet 2.

The sample resin pellets 4 were fed to the extruder with the same mixture and the same mixing ratio as the sample resin pellets 1.
Spun, a carbon masterbatch resin CM2 containing a carbon black C2 different from the carbon black C1 is added to the produced resin, and these are produced once by an extruder. This carbon black C2 has an average particle diameter of 16 nm, a pH of 7.5, and a nitrogen adsorption specific surface area of 260 m ² / g. Carbon masterbatch resin CM2 is a mixture of carbon black C2 at 24.5% by weight. The amount of the carbon masterbatch resin CM2 to be mixed was 1/30 of the amount mixed with the sample resin pellet 1 as in the case of the sample resin pellet 3. Carbon masterbatch resin CM
2 is based on the carbon masterbatch resin C described above.
Same as M1.

The sample resin pellets 5 were fed to the extruder at the same mixture and the same mixing ratio as the sample resin pellets 1.
The carbon masterbatch resin CM2 and the antioxidant are added to the produced resin, mixed, and mixed, and the mixture is extruded once to produce the resin. The mixing ratio of the carbon master batch resin CM2 is the same as that of the sample resin pellet 4, and the mixing ratio of the antioxidant is
0.05% by weight. The antioxidant is a phenolic antioxidant, IRAGANOX1076.
(Trade name: Ciba-Geigy) was used.

FIG. 6 shows the test results of the first photographic test.
(Table 1). The evaluation shows the performance of each of the sample resin pellets 2 to 5 as the recycled resin model with reference to the sample resin pellet 1 as the new resin model.

The following can be seen from Table 1. From the evaluation of the sample resin pellet 2, it is found that the photographic properties deteriorate when the resin is repeatedly heated and melted. From the evaluation of the sample resin pellets 3 and 4, it can be seen that when carbon black is additionally added during the heating and melting, the photographic properties are improved. Further, the sample resin pellets 4 containing carbon black C2 rather than carbon black C1 were added.
The higher the degree of improvement, the higher the degree of improvement depending on the type of carbon black. From the evaluation of the sample resin pellets 5, it can be seen that the addition of an antioxidant in addition to carbon black further improves photographic properties.

Next, the second photographic test will be described. In the second photographic test, the unit body of the above-mentioned lens-fitted film unit is formed of a sample molded product to be tested in order to make the test environment closer to a real form as compared with the first photographic test. The photographic film is loaded in the unit body, and the fog and the change in sensitivity of the photographic film are measured.

In the second photographic test method, first, a front cover, a body base, and a rear cover of the unit main body are manufactured by injection molding using the resin pellets a to e as raw materials. The molded products obtained from these resin pellets a to e are referred to as sample molded products 1 to 5. Then, the photographic film is loaded into the unit body constituted by the sample molded products 1 to 5. The film unit with the lens is packaged with a packaging material made by laminating an aluminum foil and a polyethylene film together with a mounting sheet for an instruction, using a packaging machine.
Leave for 30 days at 60% humidity. After 30 days had elapsed, the photographic film was taken out of the lens-fitted film unit, and the photographic film was developed in the same manner as in the first photographic test to measure fog and change in sensitivity. The package is a well-known pillow package, which is formed into a bag with a heat-sealing seal to prevent invasion of the outside air.

Next, sample molded products 1 to 5 used in the second photographic test will be described. The sample molded product 1 is used as a new part model that simulates a new resin molded product.
The sample molded product 5 is used as a reproduced part model that simulates a reproduced resin molded product.

The sample molded product 1 is formed by injection molding using the resin pellet a as a raw material. The resin pellet a is composed of the same mixture and the same mixing ratio as the sample resin pellet 1 of the first photographic test, and is pelletized once by an extruder. The sample molded product 1 is formed by injection molding using the resin pellet a as a raw material.

The sample molded article 2 is formed by injection molding using the resin pellet b as a raw material. The resin pellet b is composed of the same mixture and the same mixing ratio as the resin pellet a, and is different from the resin pellet a in the number of times of extruding. The resin composition b is extruded four times, and is repeatedly heated and melted into pellets.

The sample molded product 3 is formed by injection molding using the resin pellet c as a raw material. The resin pellet c was formed by mixing the same mixture and the same mixing ratio as the above resin pellet b with an extruder three times to heat and melt. Then, the carbon master batch resin CM2 used in the first photographic test was used. Are additionally added, and the resin pellets are further heated and melted once in an extruder. The reason why the carbon master batch resin CM2 was used as the additional carbon master batch resin was that the carbon master batch resin CM 2 was used based on the results of the first photographic test.
This is because 2 is considered to have a higher degree of improvement in photographic properties. The amount of the carbon master batch resin CM2 added was set to be the same as 1/30 of the amount of the carbon master batch resin CM1 mixed in the sample molded article 1.

The sample molded article 4 is formed by injection molding using the resin pellet d as a raw material. The resin pellet d was prepared by mixing the same mixture and the same mixture ratio as the above resin pellet b with an extruder three times and melting by heating.
Resin pellets obtained by additionally adding a carbon masterbatch resin CM3 different from No. 2 and further heating once by extruder.

The carbon master batch resin CM3 is a carbon master batch resin obtained by mixing 1.5% by weight of an antioxidant with the carbon master batch resin CM2. The amount of the carbon masterbatch resin CM3 added was the same as 1/30 of the amount of the carbon masterbatch resin CM1 mixed in the sample molded product 1 as in the case of the sample molded product 3. The carbon masterbatch resin CM3 is obtained by producing 49% by weight of carbon black C2, 48.5% by weight of a new resin, and 1.5% by weight of an antioxidant in the same manner as the above-mentioned carbon masterbatch resin CM1. . Carbon masterbatch resin CM3
Is 1.5% by weight, the carbon masterbatch resin CM3 is 1/30
Therefore, the mixing ratio of the antioxidant to the entire resin pellet d is 0.05% by weight.

The sample molded article 5 is formed by injection molding using the resin pellet e as a raw material. This resin pellet e was heated and melted in an extruder three times using the same mixture and the same mixing ratio as the resin pellet d, and then mixed with 10% by weight of a new resin. It was heated and melted once.

The results of the second photographic test are shown in FIG.
(Table 2). The evaluation shows the performance of each of the sample molded products 1 to 5 which are the recycled component models based on the sample molded product 1 which is the new part model.

[0264] From Table 2, it can be seen that the addition of carbon black can suppress a decrease in photographic properties. Further, it can be seen that the addition of an antioxidant in addition to the carbon black can further suppress the decrease in photographic properties. The sample molded article 5 is mixed with a new resin. The purpose is to suppress the deterioration of impact resistance due to the additional addition of carbon black. That is, by additionally adding carbon black, deterioration in photographic properties can be suppressed. However, on the other hand, an increase in the content of carbon black deteriorates the impact resistance of the molded article. To suppress this, a new resin containing rubber is additionally added to suppress the deterioration of impact resistance.

FIG. 7 (Table 3) shows the results of an impact resistance test conducted on the above-mentioned sample molded product 2, sample molded product 4, and sample molded product 5. From this test result, by adding carbon black,
It can be seen that the impact resistance of the recycled resin decreases, and that the impact resistance is restored by adding a new resin.

Next, the photographic properties and tensile strength of a new film unit with lens actually produced at present, and a film unit with lens obtained by recycling a product collected from the market of the film unit with lens through the above-mentioned recycling line will be described. A comprehensive performance test in which physical properties such as impact resistance, heat resistance and the like are tested will be described.

The new lens-fitted film unit is composed of new parts 1 using 100% new resin for all parts. The regenerated film unit with lens has a front cover, a rear cover, and a main body base, which are configured using recycled parts 2 to 5. The overall performance test was performed in the same manner as in the second photographic test. For the photographic test, each of the assembled new film unit with a lens and the regenerated film unit with a lens was wrapped, and a temperature of 45 ° C. ,
The film was allowed to stand for 30 days at a humidity of 60%, and then the fogged film and the change in sensitivity were measured. Regarding the physical property test, a tensile strength test, an Izod impact test, and a heat resistance test were performed on each injection molded part.

In the part 1, various additives are added to a thermoplastic resin containing butadiene rubber based on a polystyrene resin, in addition to carbon black and an antioxidant.

For the parts 2 to 5, the used lens-fitted film unit recovered from the market is disassembled in a recycling line, and the plastic parts are crushed, and the crushed material is heated and melted and returned to recycled resin pellets. This regenerated resin pellet is produced by injection molding as a raw material. No new resin or various additives are added to the part 2 at the time of recycling.

The part 3 is obtained by additionally adding the carbon masterbatch resin CM2 at the time of recycling to an amount of 1/30 of the amount of the carbon masterbatch resin added at the time of manufacturing a new article.

The part 4 was obtained by adding the same amount of the carbon master batch resin CM2 as the carbon master batch resin CM2 added to the part 3 to the carbon master batch resin CM3 obtained by mixing an antioxidant in addition to the carbon black C2 at the time of recycling. is there.

The part 5 is obtained by adding a new resin by 10% by weight in addition to the carbon master batch resin CM3 at the time of recycling.

FIG. 7 (Table 4) shows the results of the comprehensive performance test. The evaluation indicates the performance of each of the components 2 to 5 as the recycled components based on the component 1 as the new component.

As can be seen from these test results, by adding carbon black to the recycled resin at the time of recycling, decomposition products are adsorbed / captured, and adverse effects on photographic properties can be reduced. Furthermore, by using an antioxidant in combination, generation of decomposition products is suppressed, and adverse effects on photographic properties can be further reduced.
Further, by additionally adding a new resin, it is possible to suppress a decrease in impact resistance caused by additionally adding carbon black.

In the above example, an antioxidant is used as an additive for suppressing the generation of decomposition products. However, the above-mentioned antioxidants other than the antioxidant may be used instead of the antioxidant or , May be used in combination with an antioxidant.

In the above example, carbon black is
Although used as a substance that adsorbs decomposition products, other than carbon black, a substance that does not affect photographic properties may be used in combination without significantly lowering the performance of the resin such as light-shielding properties and impact resistance. . Examples of this are alumina,
There is titanium oxide and the like.

In the above example, a new resin is used in order to prevent a decrease in the performance of the resin other than the photographic properties due to the additional addition of the additive. It may be the same type as the resin used,
Different types may be used as long as they are compatible with this resin.

Further, the mixing ratio of the additive and the new resin added additionally is not limited to those in the above-mentioned examples, but may be changed as appropriate. In addition, since the carbon black preferably has a high adsorption ability, it is preferable that the carbon black has a small average particle diameter and is porous.

The location where the additive or new resin is added may be the point at which the crushed material is re-pelletized, or the point at which it is mixed with the recycled resin pellet, the crushed material, and the new resin pellet. The molding method may be vacuum molding, blow molding, extrusion molding, or the like, in addition to injection molding.

[0280] The method of adding the additive may be a method of preparing a masterbatch resin containing the additive at a high concentration and then adding the additive, or a method of adding the additive in the form of fine powder and adding the additive. Good. In addition, ease of mixing work,
The method of adding a masterbatch resin is preferable from the viewpoint that the surroundings are less likely to be contaminated during operation. Further, when an additive is added with a masterbatch resin when a new part is manufactured, a method of adding the additive with a masterbatch resin is preferable because the equipment can be used as it is.

As additives, in addition to carbon black and an antioxidant, silicone oil added for reducing friction, fatty acid metal salt for improving mold release,
The various additives described above such as a surfactant for preventing static charge may be used in combination.

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

[0283]

As described in detail above, the present invention provides
Crush used resin parts molded with thermoplastic resin,
Use of crushed crushed material or regenerated resin pellets obtained by re-forming the crushed material into resin pellets at least as a part of raw materials. As described above, since molding is performed by adding at least carbon black and an antioxidant, it is possible to prevent a decrease in photographic properties.

Further, by adding a new resin containing rubber at the time of recycling, it is possible to prevent a decrease in impact resistance.

[0285] Even if used transparent or colored resin parts other than black are used as crushing materials, carbon black is additionally added, so that the carbon black functions as a colorant, thereby turning black. A colored recycled part can be obtained.

[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 an overall perspective view of the film unit with a lens.

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

FIG. 6 is a table showing the results of first and second photographic tests.

FIG. 7 is a table showing the results of an impact resistance test and an overall performance test.

[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

Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat II (Reference) C08L 101/00 C08L 101/00 G03B 15/00 G03B 15/00 X (72) Inventor Kazuo Kamada 210 Nakanuma, Minamiashigara-shi, Kanagawa Address Fuji Photo Film Co., Ltd. F-term (reference) 4J002 AA011 BB031 BB121 BB161 BC031 BC041 BC061 BC071 BD121 BG041 BG101 BN071 BN121 BN151 BP011 CB001 CF061 CF071 CF081 CG001 CH071 CH01 EJ011 CN013 CN011 FD077

Claims (16)

[Claims] 1. A resin for a photographic photosensitive material, wherein a used resin part formed of a thermoplastic resin is crushed, and the crushed crushed material is used as at least a part of a raw material to be re-formed to produce a recycled part. A method for recycling a molded resin article for a photographic light-sensitive material, wherein the molded article is formed by adding at least carbon black and an antioxidant as additives at the time of recycling. 2. A used resin part formed of a thermoplastic resin is crushed, and the crushed crushed material is again formed into a resin pellet. A method for recycling a resin molded article for a photographic photosensitive material for producing a part, wherein at least carbon black and an antioxidant are added as additives at the time of recycling to mold the molded article. 3. A resin for photographic light-sensitive materials, wherein a used resin part formed of a thermoplastic resin is crushed, and the crushed crushed material is used as at least a part of a raw material, and is formed again to produce a recycled part. In the method for recycling a molded article, in order to reduce decomposition products which are generated from the crushed material by causing the crushed material to deteriorate or degrade due to heating during the molding and adversely affect the photographic properties of the photographic photosensitive material. A method for adsorbing or capturing the decomposition product, or an additive for suppressing the decomposition product, which suppresses the generation of the decomposition product, is added at the time of the recycling. Recycling method. 4. A used resin part formed of a thermoplastic resin is crushed, and the crushed crushed material is re-formed into a resin pellet. In the method of recycling a resin molded product for a photographic light-sensitive material that produces a part, the crushed material is generated from the crushed material by causing deterioration or deterioration due to heating during the molding, which adversely affects the photographic properties of the photographic light-sensitive material In order to reduce the amount of decomposition products exerted, the decomposition products are adsorbed or captured, or an additive for suppressing decomposition products that suppresses the generation of decomposition products is added at the time of the recycling. To recycle resin molded products for photographic photosensitive materials. 5. An additive for suppressing the decomposition product,
5. The method according to claim 3, wherein carbon black and an antioxidant are used. 6. The carbon black has an average particle size of 1
The method for recycling a resin molded product for a photographic photosensitive material according to any one of claims 1 to 5, wherein the thickness is from 0 to 80 nm. 7. The photograph according to claim 1, wherein the mixing ratio of the carbon black is 0.2 to 1.2% by weight based on the total weight of the raw materials including the additives. How to recycle resin molded products for photosensitive materials. 8. The mixing ratio of the antioxidant is 0.02 to 0.3% by weight based on the total weight of the raw materials including the additives.
The method for recycling a resin molded product for a photographic light-sensitive material according to any one of claims 1 to 7, wherein: 9. A used resin part molded from a thermoplastic resin is crushed, and the crushed crushed material is used as at least a part of a raw material, and is added to a recycled photographic photosensitive material recycled part at the time of recycling. A recycled part for photographic light-sensitive materials, wherein the recycled part is formed by adding at least carbon black and an antioxidant as an agent. 10. Recycled recycled plastic parts obtained by crushing a used resin part formed of a thermoplastic resin and re-pelling the crushed crushed material into resin pellets at least as a part of raw materials. 3. A recycled part for a photographic light-sensitive material according to claim 1, wherein at least carbon black and an antioxidant are added as additives during recycling. 11. A method of recycling a resin molded product for a photographic light-sensitive material, wherein a used resin component molded with a thermoplastic resin is crushed, and the crushed material is used as at least a part of a raw material to produce a recycled component. A method of recycling a resin molded product for a photographic light-sensitive material, wherein at least a new resin containing rubber, carbon black, and an antioxidant are added to the crushed material at the time of recycling. 12. A photographic light-sensitive material in which a used resin part formed of a thermoplastic resin is crushed, and the crushed material is re-pelletized into a resin pellet, and at least a part of the raw material is used to produce a recycled part. A method of recycling a resin molded product for a photographic photosensitive material, wherein at least a new resin containing rubber, carbon black, and an antioxidant are added to the recycled resin pellets at the time of recycling. Recycling method. 13. The method according to claim 11, wherein the average particle diameter of the carbon black is 16 nm to 24 nm. 14. A used resin part formed of a thermoplastic resin is crushed, and the crushed material is used as at least a part of a raw material. A recycled part for photographic light-sensitive materials, characterized by being molded by adding a new resin containing rubber, carbon black, and an antioxidant to the crushed material. 15. A used resin part molded with a thermoplastic resin is crushed, and the crushed material is heated and melted and re-formed into a resin pellet. What is claimed is: 1. A recycled part for a photographic material, wherein at least a new rubber-containing resin, carbon black, and an antioxidant are added to said recycled resin pellets during recycling. 16. The recycled part for a photographic light-sensitive material according to claim 14, wherein the average particle diameter of the carbon black is 16 nm to 24 nm.