Blow-molded article, method for producing toner bottle and blow-molded article, molded article, and pellet

Abstract

This blow-molded article includes: at least one substance selected from the group consisting of an inorganic layered double hydroxide and a zeolite; polyethylene or polypropylene; and a wax.

Description

Blow molded product, toner bottle and method for manufacturing blow molded product, molded product, and pellets

[0001] The present disclosure relates to a blow-molded article, a toner bottle, and a method for manufacturing the blow-molded article. The present disclosure also relates to a molded article and a pellet.

[0002] Toner bottles that contain toner to be supplied to electrophotographic image forming apparatuses are required to have high strength, such as the ability to withstand being dropped. For this reason, molded articles obtained by blow molding polypropylene (hereinafter sometimes referred to as "PP") are sometimes used. Patent Document 1 discloses a container that is a blow-molded article from PP. Also, molded articles obtained by blow molding polyethylene (hereinafter sometimes referred to as "PE") are sometimes used. Patent Document 3 discloses a toner container that is a blow-molded article from PE.

[0003] In recent years, from the viewpoint of environmental protection, it has become common to collect thermoplastic resin products and their parts, then regenerate and recycle them by temporarily changing their original shape. Here, as described in paragraph

[0002] of Patent Document 2, chemical recycling and material recycling are known as methods for recycling thermoplastic resins such as PE and PP.

[0004] JP 2000-178390 A JP 2009-001693 A JP 2010-260638 A

[0005] However, as disclosed in Patent Document 2, chemical recycling requires multiple steps, including the need for decomposition and purification equipment, resulting in high recycling costs. It also places a heavy burden on the environment. Meanwhile, material recycling generally involves a process of washing bottles. However, bottle washing may involve multiple cycles using water, acid, alkali, etc., and also requires a drying process. Therefore, bottle washing can also increase the environmental burden.

[0006] From the viewpoint of reducing environmental impact, the inventors simplified or omitted the cleaning of toner bottles to be recycled, and produced new toner bottles using PE or PP obtained from toner bottles with toner still attached inside. When toner was then placed in the toner bottles obtained in this way, they found that the surfaces of the toner particles sometimes deformed at the points of contact between the toner in the toner bottle and the inner surface of the toner bottle. Toner particles with deformed surfaces can cause development defects, which can cause density unevenness in electrophotographic images.

[0007] At least one aspect of the present disclosure is directed to providing a blow-molded article that can prevent wax migration to the surface of the blow-molded article, assuming that wax-containing polyethylene or polypropylene is used as a raw material. At least one aspect of the present disclosure is directed to providing a toner bottle that can prevent deterioration of the toner contained therein. Furthermore, at least one aspect of the present disclosure is directed to providing a method for manufacturing a blow-molded article that can prevent wax migration to the surface of the blow-molded article, assuming that wax-containing polyethylene or polypropylene is used as a raw material. At least one aspect of the present disclosure is directed to providing a molded article that can prevent wax migration to the surface, assuming that wax-containing polyethylene or polypropylene is used as a raw material. Still further, at least one aspect of the present disclosure is directed to providing pellets that contribute to suppressing wax migration to the surface of a molded article.

[0008] According to at least one embodiment of the present disclosure, there is provided a blow-molded article comprising: at least one selected from the group consisting of an inorganic layered double hydroxide and a zeolite; polyethylene or polypropylene; and a wax.

[0009] According to at least one embodiment of the present disclosure, there is provided a toner bottle comprising: at least one selected from the group consisting of an inorganic layered double hydroxide and a zeolite; polyethylene or polypropylene; and a wax.

[0010] According to at least one aspect of the present disclosure, there is provided a method for producing the blow-molded article, the method comprising the steps of: preparing a preform containing at least one selected from the group consisting of the inorganic layered double hydroxide and the zeolite, the polyethylene or polypropylene, and the wax; and stretch-blow-molding the preform to obtain the blow-molded article.

[0011] Furthermore, according to at least one aspect of the present disclosure, there is provided a method for producing the blow-molded article, the method comprising the steps of: preparing pellets containing at least one selected from the group consisting of the inorganic layered double hydroxide and the zeolite, the polyethylene or polypropylene, and the wax; and blow-molding the pellets to obtain the blow-molded article.

[0012] Furthermore, according to at least one embodiment of the present disclosure, there is provided a molded article, the molded article comprising at least one selected from the group consisting of an inorganic layered double hydroxide and a zeolite, polyethylene or polypropylene, and a wax.

[0013] Furthermore, at least one embodiment of the present disclosure provides pellets containing at least one selected from the group consisting of inorganic layered double hydroxides and zeolites, polyethylene or polypropylene, and wax.

[0014] According to at least one aspect of the present disclosure, a blow-molded article can be obtained that can prevent wax from migrating to the surface of the blow-molded article, provided that wax-containing polyethylene or polypropylene is used as a raw material. Furthermore, according to at least one aspect of the present disclosure, a toner bottle can be obtained that can prevent deterioration of the toner contained therein. Furthermore, according to at least one aspect of the present disclosure, a method for producing a blow-molded article can be obtained that can prevent wax from migrating to the surface of the blow-molded article, provided that wax-containing polyethylene or polypropylene is used as a raw material. Furthermore, according to at least one aspect of the present disclosure, a molded article in which wax migration to the surface is prevented can be obtained. Furthermore, according to at least one aspect of the present disclosure, a pellet that contributes to suppressing wax migration to the surface of a molded article is provided.

[0015] 1 is a schematic diagram of an image forming apparatus; 2 is a schematic diagram showing a preform molding method; 3 is a schematic diagram showing a blow molding method; 4 is a schematic diagram of one-stage blow molding; 5 is a schematic diagram showing migration of wax-derived components; 6 is a schematic diagram of a blown bottle; 7 is a schematic diagram of a blown bottle; 8 is a schematic diagram showing a blow molding method;

[0016] Hereinafter, with reference to the drawings, exemplary embodiments for carrying out the present disclosure will be described in detail. However, the scope of the present invention is not limited to the following embodiments. In this disclosure, unless otherwise specified, the expressions "XX or more and YY or less" and "XX to YY" representing a numerical range mean a numerical range including the lower and upper limits, which are the endpoints. When a numerical range is described in stages, any combination of the upper and lower limits of each numerical range is also disclosed. In addition, in this disclosure, for example, a description such as "at least one selected from the group consisting of XX, YY, and ZZ" means any of XX, YY, ZZ, a combination of XX and YY, a combination of XX and ZZ, a combination of YY and ZZ, or a combination of XX, YY, and ZZ.

[0017] As described above, when toner is stored in a toner bottle (hereinafter also referred to as a recycled toner bottle) molded using material recycled PE (hereinafter also referred to as "MR-PE") or material recycled PP (hereinafter also referred to as "MR-PP") obtained from a toner bottle with toner still attached, deformation of the surface of the stored toner may occur. The inventors speculate that the reason for this is as follows. It is believed that the recycled toner bottle is contaminated with wax contained in the toner remaining in the toner bottle before recycling. Furthermore, the recycled toner bottle may also contain low-molecular-weight decomposition products, such as wax pyrolysis products caused by the heat received during the recycling process or blow molding, and, depending on the type of wax, hydrolysis products caused by moisture. Hereinafter, compounds derived from wax, such as wax pyrolysis products and hydrolysis products, including wax, are also referred to as wax-derived components. It is believed that at least a portion of the wax-derived components is present on the inner surface of the recycled toner bottle. In particular, when wax contains decomposition products, they tend to migrate to the surface due to their low molecular weight. It is believed that the toner particles in the recycled toner bottle come into contact with the wax-derived components exposed on the inner surface, causing deformation of the toner particle surfaces. This phenomenon of deformation of the toner particle surfaces due to wax is hereinafter sometimes referred to as chemical attack.

[0018] As described above, wax-derived components derived from recycled polypropylenes such as MR-PP, or wax-derived components derived from wax mixed into recycled polyethylenes such as MR-PE, are thought to cause chemical attack. As shown in Figure 5, during the toner bottle molding process, when PE or PP resin 201 reaches or exceeds its glass transition temperature, wax-derived components 202 migrate to the bottle surface. Above the glass transition temperature of PE or PP resin, thermal motion of the PE or PP resin becomes active. This causes wax-derived components to migrate through gaps in the PE or PP resin to the bottle surface. As described above, wax-derived components have a low molecular weight and therefore tend to migrate to the surface of molded products. Therefore, the present inventors recognized the need for technological development to obtain blow-molded products that are less likely to cause chemical attack on toner that comes into contact with their surfaces, even when the blow-molded products are made from a resin mixture containing recycled polyethylene or recycled polypropylene derived from toner bottles. Based on this recognition, the present inventors have conducted extensive research and found that the following blow-molded article is less likely to cause chemical attack by toner that comes into contact with its surface: That is, the blow-molded article according to at least one embodiment of the present disclosure includes at least one selected from the group consisting of inorganic layered double hydroxides and zeolites, polyethylene or polypropylene, and wax.

[0019] As a result of investigations by the present inventors, it was found that chemical attack can be prevented by adding at least one selected from the group consisting of inorganic layered double hydroxides and zeolites to polyethylene or polypropylene containing wax. The reason for this is believed to be that at least one selected from the group consisting of inorganic layered double hydroxides and zeolites (hereinafter also referred to as zeolite, etc.) adsorbs wax, thereby suppressing the migration of wax-derived components to the surface of the toner bottle.

[0020] In particular, since toner is easily charged by friction with other components, it is believed that at least a portion of the toner remaining in the toner bottle is electrically charged. It is believed that the charged state of the toner is maintained even after the toner becomes MR-PE or MR-PP, and that at least a portion of the wax contained in the MR-PE or MR-PP is also electrically charged. It is believed that such electrically charged wax is easily adsorbed by zeolite and the like.

[0021] Therefore, the blow-molded article, molded article, and pellets according to the present disclosure contain at least one selected from the group consisting of an inorganic layered double hydroxide and a zeolite, polyethylene or polypropylene, and wax. The blow-molded article can be obtained, for example, by stretch-blow molding a preform as a molded article molded from a resin mixture containing at least one selected from the group consisting of an inorganic layered double hydroxide and a zeolite, polyethylene or polypropylene, and wax. The blow-molded article can also be obtained, for example, by blow molding pellets as a molded article molded from a resin mixture containing at least one selected from the group consisting of an inorganic layered double hydroxide and a zeolite, polyethylene or polypropylene, and wax.

[0022] (Preform, Pellets) Preforms (or pellets) used in blow molding preferably contain at least the following (a), (b) and (c): (a) wax; (b) at least one selected from the group consisting of inorganic layered double hydroxides and zeolites; and (c) polyethylene or polypropylene.

[0023] Zeolite and the like are covered with a polyethylene or polypropylene skin layer during molding of the bottle precursor preform (or pellets), making it difficult for them to precipitate on the bottle surface, thereby inhibiting the migration of adsorbed wax to the bottle surface, which helps to prevent chemical attack by wax.

[0024] The polypropylene is not particularly limited, and known polypropylenes can be used. The polypropylene may be a homopolymer, or a copolymer such as a random copolymer or a block copolymer. Examples of copolymers include a copolymer of ethylene and propylene. Recycled PP such as MR-PP may also be used, or virgin PP that has not undergone molecular weight reduction may also be used. However, the effects of the present disclosure are more pronounced when the PP is MR-PP obtained by recycling toner bottles. Therefore, it is preferable that the polypropylene be material-recycled polypropylene.

[0025] The PE is not particularly limited, and known polyethylenes can be used. Examples of polyethylene include at least one selected from the group consisting of HDPE (high density polyethylene), LDPE (low density polyethylene), and LLDPE (linear low density polyethylene). Preferably, the polyethylene includes HDPE (high density polyethylene). Examples of polyethylene that can be used include KEIYO B5804 (trade name, Keiyo Polyethylene Co., Ltd.).

[0026] The polyethylene may be recycled PE such as MR-PE, or may be virgin PE that has not undergone molecular weight reduction. However, the effects of the present disclosure are more pronounced when the PE is MR-PE obtained by recycling toner bottles. Therefore, it is preferable that the PE be material-recycled polyethylene.

[0027] The content of polyethylene or polypropylene in the blow-molded article, molded article, pellets, or preform is not particularly limited, but is preferably 80% by mass or more, more preferably 90% by mass or more, based on the mass of the blow-molded article, molded article, pellets, or preform. It is also preferably 99.9% by mass or less, more preferably 99.5% by mass or less. For example, the range of 80 to 99.9% by mass or 90 to 99.5% by mass is preferred.

[0028] The melt flow rate (MFR) of the polyethylene or polypropylene is preferably 0.1 g / min or more and 1.0 g / 10 min or less, and particularly preferably 0.1 g / 10 min or more and 0.5 g / 10 min or less, at a temperature of 200°C under measurement conditions in accordance with Japanese Industrial Standards (JIS) K7210-1:2014. When the MFR is 0.1 g / 10 min or more, the polyethylene or polypropylene tends to be sufficiently filled during blow molding. When the MFR is 1.0 g / 10 min or less, the shape of the molded product tends to be maintained.

[0029] <Inorganic layered double hydroxide> The blow-molded article, molded article, and pellets contain at least one selected from the group consisting of inorganic layered double hydroxides and zeolites. The presence of inorganic layered double hydroxides and zeolites in the blow-molded article, molded article, and pellets can be confirmed by measurement using a microscopic FT-IR.

[0030] Examples of inorganic layered double hydroxides include kaolin and mica, but compounds that are more effective and readily available include hydrotalcite compounds represented by the following general formula (1). The inorganic layered double hydroxide preferably contains a hydrotalcite compound. General formula (1): M ２＋ （１－Ｘ） M ３＋ Ｘ (OH) ２ A ｎ－ （Ｘ／ｎ） ・mH ２ O (where 0<X≦0.5, m≧0, M ２＋ ; Mg ２＋ , Zn ２＋ Divalent metal ions such as M ３＋ ; Al ３＋ , Fe ３＋ Trivalent metal ions such as A ｎ－ ;CO ３ ２－ , Cl － , NO ３ － n-valent anions such as , where n is an integer of 1 or more)

[0031] The hydrotalcite compound represented by the general formula (1) has a positively charged base layer [M ２＋ （１－Ｘ） M３＋ Ｘ (OH) ２ ] Ｘ＋ and the negatively charged intermediate layer [A ｎ－ （Ｘ／ｎ） ・mH ２ O] Ｘ－ It is a layered compound consisting of a basic layer and an intermediate layer inserted therein, and can be considered as an intercalation compound. Generally, intercalation compounds are known to exhibit unique chemical properties (reactivity). In the case of the hydrotalcite compound represented by the general formula (1), the anion (A ｎ－ It is known that the anions in the base layer are easily exchanged with anions (anion exchange). The mechanism of anion exchange is unclear, but it is presumed to involve a combination of factors such as the electrical interaction (attraction) between the base layer and anions, the size of the voids in the intermediate layer (thickness of the intermediate layer), and adsorption.

[0032] In the general formula (1), a divalent metal ion M ２＋ As for Mg ２＋ is a trivalent metal ion M ３＋ As for Al ３＋ Furthermore, the n-valent anion is preferably CO ３ ２－ , Cl － is preferred.

[0033] The content of the inorganic layered double hydroxide is preferably 0.09 to 1.2% by mass, and more preferably 0.1 to 1.0% by mass, based on the mass of the blow-molded article, molded article, or pellets. At 0.09% by mass or more, the wax can be more fully adsorbed, making it less likely for the wax to migrate to the bottle surface. At 1.2% by mass or less, the inorganic layered double hydroxide is less likely to become a starting point for rupture during blow molding. By setting the blending amount within the above range, it becomes easier to achieve both chemical attack suppression and blowability.

[0034] <Zeolite> Zeolite is a hydrous aluminosilicate containing alkali or alkaline earth metals, which is composed of a rigid anionic framework having regular channels (tubular pores) and cavities. There are no particular limitations, and either natural or artificial (synthetic) zeolites can be used.

[0035] The zeolite is preferably one having the following composition:

[0036] M Ｉ is Na ＋ is preferred. ＩＩ is Ca ２＋ is preferred. m is preferably 1 to 384. n is preferably 0 to 27. Zeolites having various skeletal structures exist. That is, zeolite skeletal structures include LTA type, FER type, MWW type, MFI type, MOR type, LTL type, FAU type, BEA type, etc., as recognized by the International Zeolite Society. In the present disclosure, zeolites of any skeletal structure can be used, but MFI type is preferred. MFI type (ZSM-5) has a unit lattice chemical formula of [Na ｍ Al ｍ Si ９６－ｍ O １９２ ・16H ２ O (0<m<27)], an aluminosilicate zeolite having a framework structure in which pentasil units are linked in a chain shape.

[0037] The zeolite content is preferably 0.09 to 1.2% by mass, and more preferably 0.1 to 1.0% by mass, based on the mass of the blow-molded product (molded product or pellets). At 0.09% by mass or more, wax can be more fully adsorbed, making it less likely for the wax to migrate to the bottle surface. At 1.2% by mass or less, the zeolite is less likely to become a starting point for rupture during blow molding. By setting the blending amount within the above range, it becomes easier to achieve both chemical attack suppression and blowability.

[0038] From the viewpoint of achieving both chemical attack suppression and blowability, the total content of the inorganic layered double hydroxide and the zeolite is preferably 0.09 to 1.2 mass%, and more preferably 0.1 to 1.0 mass%, based on the mass of the blow-molded article (molded article or pellets).

[0039] The inorganic layered double hydroxide and zeolite contents in a blow-molded product (molded article or pellets) can be measured by the following method. After measuring the mass of the blow-molded product, the blow-molded product is placed in a stainless steel container and placed in an oven at 480°C for one hour to burn off the resin in the blow-molded product. Ion-exchanged water is then added to the stainless steel container containing the residue, thoroughly stirred, and filtered through a nylon mesh with openings large enough to block the inorganic layered double hydroxide and zeolite. The opening size can be selected taking into consideration the size of materials other than the inorganic layered double hydroxide and zeolite. After filtration, the water is removed in an oven at 100°C, and the mass is measured. The contents can be determined by subtracting the mass of the nylon mesh. This method allows catalysts and carbon black contained in the resin to pass through the nylon mesh, enabling accurate determination of the inorganic layered double hydroxide and zeolite contents. If the inorganic layered double hydroxide and zeolite cannot be separated by filtration alone, the contents can be measured using a combination of known methods.

[0040] The number-average particle size of the inorganic layered double hydroxide and zeolite is preferably 0.05 to 2.00 μm, more preferably 0.10 to 1.50 μm. A number-average particle size of 0.05 μm or more improves dispersibility in the resin. A number-average particle size of 2.00 μm or less makes them less likely to become foreign matter during blow molding, and helps prevent the molded product from bursting.

[0041] <Wax> Examples of waxes include aliphatic hydrocarbon waxes such as low-molecular-weight polyethylene, low-molecular-weight polypropylene, polyolefin copolymers, polyolefin wax, microcrystalline wax, paraffin wax, and Fischer-Tropsch wax; oxides of aliphatic hydrocarbon waxes such as oxidized polyethylene wax; or block copolymers thereof; vegetable waxes such as candelilla wax, carnauba wax, Japan wax, and jojoba wax; animal waxes such as beeswax, lanolin, and spermaceti; mineral waxes such as ozokerite, ceresin, and petrolactam; ester waxes containing aliphatic esters as the main component such as Montan acid ester wax and castor wax; and partially or completely deoxidized aliphatic esters such as deoxidized carnauba wax.Further examples include saturated straight-chain fatty acids such as palmitic acid, stearic acid, montanic acid, or long-chain alkylcarboxylic acids having an even longer alkyl chain; unsaturated fatty acids such as brassidic acid, eleostearic acid, and valinaric acid; saturated alcohols such as stearyl alcohol, eicosyl alcohol, behenyl alcohol, carnaubyl alcohol, ceryl alcohol, melissyl alcohol, or alkyl alcohols having an even longer alkyl chain; polyhydric alcohols such as sorbitol; aliphatic amides such as linoleic acid amide, oleic acid amide, and lauric acid amide; saturated aliphatic bisamides such as methylene bisstearic acid amide, ethylene biscapric acid amide, ethylene bislauric acid amide, and hexamethylene bisstearic acid amide; ethylene bisoleic acid amide, and ethylene bisoleic acid amide. aromatic bisamides such as m-xylenebisstearamide and N,N'-distearylisophthalamide; fatty acid metal salts (commonly known as metal soaps) such as calcium stearate, calcium laurate, zinc stearate and magnesium stearate; waxes obtained by grafting an aliphatic hydrocarbon wax with a vinyl monomer such as styrene or acrylic acid; partial esters of fatty acids and polyhydric alcohols such as behenic acid monoglyceride; and methyl ester compounds having a hydroxyl group obtained by hydrogenating vegetable oils and fats.

[0042] In particular, it is preferable that the wax contains an ester wax. Ester wax is easily hydrolyzed and reduced in molecular weight during recycling and molding processes. Therefore, chemical attack may occur easily. Even in such cases, the blow-molded article of the present disclosure can sufficiently suppress chemical attack. The hydrolyzate of the ester wax may contain carboxyl groups, and the presence of the carboxyl groups makes the hydrolyzate more susceptible to ion adsorption by zeolite and the like, which is thought to sufficiently suppress chemical attack.

[0043] These waxes are preferably used in the form of waxes having a sharp molecular weight distribution obtained by the press sweating method, solvent method, recrystallization method, vacuum distillation method, supercritical gas extraction method, or melt crystallization method. Also preferably used are waxes from which low-molecular-weight solid fatty acids, low-molecular-weight solid alcohols, low-molecular-weight solid compounds, and other impurities have been removed. The presence of wax in blow-molded articles (molded articles or pellets) can be confirmed by GPC-FTIR.

[0044] Specific examples of waxes include Viscol (registered trademark) 330-P, 550-P, 660-P, and TS-200 (Sanyo Chemical Industries, Ltd.), Hiwax 400P, 200P, 100P, 410P, 420P, 320P, 220P, 210P, and 110P (Mitsui Chemicals, Inc.), Sasol H1, H2, C80, C105, and C77 (Schumann Sasol), HNP-1, HNP- Examples of waxes that can be used include HNP-3, HNP-9, HNP-10, HNP-11, and HNP-12 (Nippon Seiro Co., Ltd.), Unilin (registered trademark) 350, 425, 550, and 700, and Unicid (registered trademark) 350, 425, 550, and 700 (Toyo Petrolite Co., Ltd.), Japan wax, beeswax, rice wax, candelilla wax, and carnauba wax (available from Cerarica NODA Co., Ltd.).

[0045] The wax content in the blow-molded article (molded article or pellets) may be, for example, 0.001 to 0.100 mass%, 0.002 to 0.050 mass%, or 0.002 to 0.030 mass%, based on the mass of the blow-molded article (molded article or pellets). If the wax content is within the above range, it is possible to more reliably prevent the wax from affecting the blow moldability of the preform (or pellets). The presence and quantification of wax in the resin molded article can be determined, for example, by measurement using pyrolysis GC / MS.

[0046] In the blow molded article (molded article or pellets), the total content of the inorganic layered double hydroxide and the zeolite per 100 parts by mass of wax is preferably 400 to 5,000 parts by mass, more preferably 450 to 4,600 parts by mass.

[0047] The blow-molded article (molded article or pellets) may contain carbon black. For example, carbon black may be added to the blow-molded article for reasons of appearance. The carbon black content (blending amount) in the blow-molded article (molded article or pellets) is, for example, 0.01 to 0.20 mass %, or 0.02 to 0.10 mass %.

[0048] (Production of Blow Molded Articles) Next, one embodiment of a method for producing blow molded articles such as toner bottles by blow molding will be described below. The means of blow molding is not particularly limited, and known methods can be used. Examples of blow molding include direct blow molding and stretch blow molding.

[0049] Blow-molded articles can be obtained, for example, by blow-molding pellets, which are formed from a resin mixture containing at least one selected from the group consisting of inorganic layered double hydroxides and zeolites, polyethylene or polypropylene, and wax. When pellets are used for blow molding, direct blow molding is preferred. That is, a method for producing a blow-molded article preferably includes a step of preparing pellets containing at least one selected from the group consisting of inorganic layered double hydroxides and zeolites, polyethylene or polypropylene, and wax, and a molding step of blow-molding the pellets to obtain the blow-molded article.

[0050] Furthermore, when stretch blow molding is performed, the method for producing a blow-molded product includes a step of preparing a preform containing at least one selected from the group consisting of inorganic layered double hydroxides and zeolites, polyethylene or polypropylene, and wax, and a molding step of stretch blow molding the preform to obtain a blow-molded product.

[0051] First, an example of a method for producing pellets will be described. The pellets can also be used as a material for a preform used in biaxially stretching blow molding a blow-molded product. For example, in the pellet preparation step or preform preparation step, at least one selected from the group consisting of an inorganic layered double hydroxide and a zeolite, polyethylene or polypropylene, and a wax are melt-kneaded to form pellets. Pelletization homogenizes the material composition, facilitating molding. The wax may be a toner containing wax. More specifically, at least one selected from the group consisting of an inorganic layered double hydroxide and a zeolite, polyethylene or polypropylene, and an electrophotographic toner containing wax are melt-kneaded to form pellets. Alternatively, at least one selected from the group consisting of an inorganic layered double hydroxide and a zeolite may be mixed or melt-kneaded with polyethylene or polypropylene in advance to obtain a polyethylene composition or a polypropylene composition, and then a toner containing wax may be mixed or melt-kneaded therein.

[0052] Furthermore, a toner bottle containing polyethylene or polypropylene with an electrophotographic toner containing wax attached thereto may be used. That is, the step of preparing pellets preferably includes a step of pulverizing a recycled toner bottle with an electrophotographic toner attached thereto to obtain a pulverized material, and a step of melting and kneading the pulverized material with at least one selected from the group consisting of inorganic layered double hydroxides and zeolites to form pellets. It is also preferable that the electrophotographic toner contains wax, and the toner bottle contains polyethylene or polypropylene. The obtained pellets are subjected to blow molding, such as direct blow molding, to obtain a blow-molded product.

[0053] Furthermore, when molding a preform, the following steps are preferred. That is, the step of preparing a preform preferably includes a step of pulverizing a recycled toner bottle to which electrophotographic toner has adhered to obtain pulverized material, a step of melting and kneading the pulverized material with at least one selected from the group consisting of inorganic layered double hydroxides and zeolites to form pellets, and a step of forming the preform from the formed pellets. It is also preferred that the electrophotographic toner contains wax and the toner bottle contains polyethylene or polypropylene.

[0054] The amount of electrophotographic toner is preferably 0.100 to 1.000% by mass, and more preferably 0.150 to 0.500% by mass, based on the total amount of the toner bottle and the electrophotographic toner attached to the toner bottle.

[0055] The melt-kneading means is not particularly limited, and known means such as a twin-screw extruder can be used. The temperature during melt-kneading is not particularly limited as long as it can melt-knead polyethylene or polypropylene. For example, it is 120 to 300°C, preferably 180 to 240°C. The melt-kneading conditions are also not particularly limited. After melt-kneading, the mixture is cooled and molded into pellets that can be injection-molded using known means, such as a pelletizer.

[0056] On the other hand, when stretch blow molding is performed, the obtained pellets are used to form a test-tube-shaped preform 104 by injection molding, as shown in Figure 2. Specifically, a heating cylinder 105 heats the material fed into an injection molding machine 101 to make it molten, and an extrusion screw 207 injects the molten material into preform molds 102 and 103, and after cooling, the material is removed from the molds to obtain the preform 104. In the preform preparation step, it is preferable to obtain a preform by injection molding from the obtained pellets. It is also preferable that the preform has a test-tube shape.

[0057] Next, the molding process will be described. In the molding process, biaxial stretch blow (biaxial stretch molding) is performed on the preform 104 as shown in Figure 3. First, the preform 104 is placed in a heating furnace 107 and heated to a temperature at which it can be stretched. The heated preform 104 is removed from the heating furnace 107 and placed in the mouth of a blow mold 108, which has a cavity formed inside by combining a left mold 108-1 and a right mold 108-2.

[0058] It is preferable to place the heated preform in the mouth of the blow mold within a short time (for example, within 10 seconds) so that the temperature of the heated preform does not drop before the start of the biaxial stretching process. The heated preform placed in the blow mold 108 is stretched in the longitudinal direction using a stretching rod 109. This stretching is called primary stretching. In the primary stretching, it is preferable to inject gas so that the preform 104 does not come into contact with the stretching rod 109, and the pressure of the gas at this time is called primary blow pressure.

[0059] After the primary stretching, gas 110 is introduced through the preform opening 106 to expand the preform laterally (circumferentially). This is called secondary stretching. The gas pressure at this time is called secondary blow pressure. Examples of gases that can be blown include air, nitrogen, carbon dioxide, and argon.

[0060] By performing these primary and secondary stretching steps, the preform 104 expands in each direction indicated by the arrows 301, adheres to the inner wall of the blow mold 108, and is cooled and solidified in this state to become a blow-molded product 112. The molding process preferably includes a step of stretching the preform in the longitudinal direction of the preform using a stretching rod, and a step of injecting gas into the longitudinally stretched preform to stretch it in the circumferential direction of the preform. Next, the left mold 108-1 and the right mold 108-2 of the blow mold 108 are separated, and the blow-molded product 112 is removed from the blow mold 108. Because this blow-molded product 112 is stretched in both the longitudinal and lateral directions, it becomes a molded product with high strength.

[0061] Thus, it is preferable that the preform is in a non-crystallized state (non-crystalline, i.e., amorphous state) during the stretching step of injection stretch blow molding. If the preform is in an amorphous state and is at the blow molding temperature, blowing, i.e., biaxial stretch molding, stretches and crystallizes the resin in the stretched direction, making it possible to form a bottle with high strength.

[0062] Injection stretch blow molding methods include one-stage and two-stage methods. The one-stage method is a method in which the preform is stretch-blow molded directly or at a controlled temperature using the residual heat of the preform immediately after removal from the mold. The two-stage method is a method in which the preform is first cooled to room temperature and then stretch-blow molded again at a controlled temperature.

[0063] In the one-stage method, as shown in Figure 4, after injection molding a preform 104 from an injection molding machine 101, cooling is completed in a short time of 10 seconds or less during injection molding so that the preform 104 does not fall below the glass transition temperature of the polyethylene or polypropylene. The preform is then immediately heated and maintained at a blow molding temperature (for example, 130°C to 170°C) and blow-molded to obtain a blown bottle 112. An integrated injection molding device and blow molding device are used.

[0064] The two-stage method is a method in which a preform is injection-molded, cooled to below the glass transition temperature of the polyethylene or polypropylene, removed, and then heated to a blow molding temperature (e.g., 130°C to 170°C) in a separate blow molding machine for blow molding. Separate injection molding and blow molding machines are used. For example, after molding a preform in a preform preparation step, the preform is cooled to below the glass transition temperature of the polyethylene or polypropylene, and then the molding step is carried out.

[0065] The one-stage method is preferable in that the preform is not cooled below the glass transition temperature and therefore requires less energy for reheating than the two-stage method.

[0066] Next, a method using direct blow molding will be described as one embodiment of a method for producing a blow-molded product. There are no particular limitations on the means for direct blow-molding pellets, and known methods can be employed. A known direct blow molding machine can be used for direct blow molding. The extrusion temperature and other parameters can be appropriately set depending on the polyethylene or polypropylene being used. Specifically, the following method can be mentioned, for example: The pellets obtained by the above method are loaded into an injection molding machine 801. A heating cylinder 802 heats the material loaded into the injection molding machine 801 to melt it, and an extrusion screw 803 feeds the molten material into a head 804. The molten material then sags between the molds 805 under its own weight. The resin sagging under its own weight is then sandwiched between the molds 805 from both sides, and gas is introduced from a blow pin 806 to cause the resin to adhere to the inner wall of the mold 805. The resin is then cooled and solidified in this state, resulting in a blow-molded product.

[0067] Next, we will explain how to check for chemical attack in toner bottles obtained by blow molding, such as biaxial stretch blow molding and direct blow molding. Toner is placed in a blow-molded toner bottle. The toner bottle containing the toner is then left in a usage environment. For the chemical attack evaluation, the usage environment was set at 50°C for 72 hours, and the toner bottle was left in a test thermostatic chamber. The toner bottle exposed to the usage environment was removed, and the toner adhering to the inner surface of the bottle was removed. The toner was then removed by inverting the toner container opening and removing it. The toner adhering to the inner surface of the bottle was then easily removed by using adhesive tape or the like to remove it. When the removed toner was observed under an electron microscope or the like to observe the deformation of the toner particle surface, traces of deformation were observed on the contact surface with the toner bottle for toner particles that had been subjected to chemical attack.

[0068] (Image forming apparatus) The image forming apparatus will be described below with reference to the drawings. Fig. 1 is a schematic diagram illustrating the configuration of a four-color image forming apparatus using an electrophotographic system, with 80 representing the main body of the image forming apparatus. This image forming apparatus 80 is configured as a so-called intermediate transfer tandem type image forming apparatus, in which four color image forming units are arranged side by side on an intermediate transfer belt.

[0069] In this image forming apparatus 80, image formation is performed as follows. First, in this image forming apparatus 80, an electrostatic latent image is formed on a photosensitive drum 17 (17y, 17m, 17c, 17bk) by an exposure device 50 (50y, 50m, 50c, 50bk) based on print data. Then, in this image forming apparatus 80, the formed electrostatic latent image is developed by a developing device 21 (21y, 21m, 21c, 21bk) to form a toner image.

[0070] In this image forming apparatus 80, a toner image is transferred onto an intermediate transfer body 62 by a primary transfer device 60 (60y, 60m, 60c, 60bk), and then transferred onto a sheet material S supplied from a paper feed device 63 by a secondary transfer section 64 (64a, 64b). Next, in this image forming apparatus 80, the toner image transferred onto the sheet material S is fixed to the sheet material S by a fixing means 68, and then the sheet is discharged onto a paper discharge tray 70.

[0071] Furthermore, in this image forming apparatus 80, a toner image is formed in a developing device 21, and detachable toner bottles 3 (3Y, 3M, 3C, 3Bk) are used to supply toner to the developing device 21. A toner bottle according to at least one embodiment of the present disclosure is a toner bottle used in this manner. The toner bottle contains at least one selected from the group consisting of an inorganic layered double hydroxide and a zeolite, polyethylene or polypropylene, and wax.

[0072] The present disclosure will be described in detail below using examples and comparative examples. However, the present disclosure is not limited to these examples. In the following examples and comparative examples, "%" means "% by mass" unless otherwise specified.

[0073] <Production of toner bottle by stretch blowing> A one-stage blow molding machine (ASB-70DPH manufactured by Nissei ASB Machinery Co., Ltd.) was used to produce toner bottle 3 (total length 439.5 mm, diameter 101 mm) shown in FIG. 6 . The blow stretch ratio was set to "longitudinal ratio x lateral ratio = 6.7". The "longitudinal ratio" of the blow stretch ratio is a value calculated by dividing the "total length after stretching" by the "total length (before stretching) of the portion of the preform that reaches the stretching temperature (heated portion)". The "lateral ratio" of the blow stretch ratio is a value calculated by dividing the "diameter of the intermediate portion after stretching" by the "diameter of the intermediate portion of the preform (before stretching)".

[0074] First, the materials shown in Table 1 below were melt-kneaded and then pelletized to prepare a masterbatch having a carbon black concentration of 5% by mass.

[0075] Next, the masterbatch containing 5% by mass of carbon black prepared above and PP were mixed in the ratios shown in Table 2 below, melt-kneaded, and then pelletized to obtain pellets of a resin mixture.

[0076] <Stretch Blow Molding Conditions> The dried resin mixture pellets were loaded into an injection molding machine, a one-step stretch blow molding machine (product name: ASB-70DPH; manufactured by Nissei ASB Machinery Co., Ltd.), and biaxial stretch blow molding was performed to form a toner bottle. The one-step stretch blow molding machine is capable of continuously performing (one-stage method) a step of obtaining a test tube-shaped preform by injection molding and a step of biaxial stretch blow molding the preform to obtain a bottle-shaped molded product. The screw diameter of the injection molding machine in this molding machine was 54 mm.

[0077] First, a mold capable of molding a preform with an outer diameter of 30 mm, a wall thickness of 3.7 mm, and a length of 220 mm was prepared as a mold for molding a preform. Then, a preform was molded under the following molding conditions. Screw diameter: 54 mm Screw position before filling the resin mixture into the cavity: 95 mm Injection speed Until the screw advances 5 mm: 50% of the maximum speed Until the screw advances another 20 mm: 30% of the maximum speed Until the screw advances another 35 mm: 25% of the maximum speed PV switching position: 35 mm First stage of holding pressure: 30 MPa, 4 s Second stage of holding pressure: 20 MPa, 7.99 s Heating barrel temperature: 230 ° C. Cooling time: 10.0 seconds Mold temperature: 20 ° C.

[0078] After a cooling time of 10.0 seconds had elapsed, the preform was demolded and transported to the biaxial stretch blow station of the one-step stretch blow molding machine. The temperature of the preform during transport was controlled as follows: Preform heating temperature: 180°C at a position 10% of the total length of the preform from the top of the preform; 200°C at a position 25% of the total length of the preform from the top of the preform; 200°C at a position 50% of the total length of the preform from the top of the preform; and 140°C at a position 75% of the total length of the preform from the top of the preform. The preform adjusted to the above temperatures was then placed in a cylindrical mold adjusted to a temperature of 20°C and having a size corresponding to the size of a toner bottle, and biaxial stretch blow molding was performed to produce a blown bottle. The preform was heated during transport, so that the surface temperature of the center of the preform immediately before being placed in the cylindrical mold was 150°C.

[0079] First, the stretch bar was inserted from the retracted position into the preform through the opening and advanced until it contacted the top of the preform. The air pressure driving the stretch bar was then increased to 1.2 MPa, and the stretch bar was further advanced. Next, 0.5 seconds after the start of further advancement of the stretch bar, primary air was introduced into the preform through the opening. The pressure of the primary air was set to 0.4 MPa. Next, 0.7 seconds after the introduction of the primary air, secondary air was introduced. The pressure of the secondary air was set to 1.2 MPa. Air was then introduced into the preform over 2.7 seconds from the start of the introduction of the primary air. Next, the pressure inside the preform was returned to normal pressure over 0.5 seconds. In this manner, a toner bottle was produced by blow molding. This bottle was a toner bottle made from virgin PP that had not been recycled. Using the above method, 200 toner bottles made from virgin PP were produced.

[0080] (Example A1-1) <Preparation of Recycled Pellets> All 200 toner bottles containing virgin PP prepared above were filled with black toner contained in a toner cartridge (product name: Toner NPG-26, manufactured by Canon Inc.). The black toner contained ester wax. The openings of the virgin PP toner bottles were then turned vertically downward to discharge the black toner. Even after this operation, a small amount of black toner remained on the inner wall of each toner bottle. The average amount of black toner remaining in the toner bottles for the 200 toner bottles was 0.321% by mass, based on the mass of the toner bottle itself. Note that the mass of the toner bottle itself refers to the mass of the toner bottle and the toner remaining therein, with all supply components and other items removed from the toner bottle. The same meaning applies to the following examples. Next, each toner bottle was crushed into pieces approximately 5 to 10 mm square using a crusher to obtain crushed products (hereinafter also referred to as "flake products"). The wax content of the resulting flake products was measured using GPC and FT-IR, and was found to be 0.022 parts by mass per 100 parts by mass of the flake products. 0.5% by mass of a hydrotalcite compound (trade name: DHT-4C; manufactured by Kyowa Chemical Industry Co., Ltd.) was added to 99.5% by mass of the flake products as an inorganic layered double hydroxide. The mixture was melt-kneaded using a twin-screw extruder (PC-46 manufactured by Ikegai Corporation) at a temperature of 210°C, a screw rotation speed of 200 rpm, and a discharge rate of 50 kg / h, and then pelletized. The inorganic layered double hydroxide used here was in a filler form and had a number-average particle size of 0.38 μm. (This recycled material is referred to as MR-PP (1-1)).

[0081] <Preparation of Blow Bottle> MR-PP (1-1) was placed in the one-step stretch blow molding machine and biaxial stretch blow molding was carried out under the same blow molding conditions as above (the obtained toner bottle is referred to as toner bottle (A1-1)). Toner was placed in the toner bottle (A1-1), and a chemical attack confirmation test was carried out in an environment of 50°C for 72 hours. As a result, no deformation of the toner particle surface was confirmed when the toner adhering to the inner surface of the toner bottle was observed.

[0082] Blow molding was carried out in the same manner as in Example A1-1, except that the compounding ratio of the flake product and the inorganic layered double hydroxide (hydrotalcite compound) was changed as shown in Table 3, to obtain toner bottles (A1-2), (A1-3), and a comparative toner bottle (A1-4). Blow molding could be carried out for all toner bottles without any problems. For each of the obtained toner bottles, deformation of the toner particle surface was observed in the same manner as in Example A1-1.

[0083] Toner bottle (A1-2) When a preform was subjected to biaxial stretch blow molding with an inorganic layered double hydroxide added in an amount of 1.0 mass %, blow molding was possible. When this toner bottle (A1-2) was used to evaluate chemical attack, no deformation of the toner particle surface was confirmed even when the toner adhering to the inner surface of the toner bottle was observed.

[0084] Toner bottle (A1-3) When a preform was biaxially stretched and blow-molded with an inorganic layered double hydroxide added in an amount of 0.1% by mass, blow molding was possible without any problems. When this toner bottle (A1-3) was used to evaluate chemical attack, no deformation of the toner particle surface was confirmed even when the toner adhering to the inner surface of the toner bottle was observed.

[0085] Comparative toner bottle (A1-4) When a preform was biaxially stretched and blow-molded with an added amount of inorganic layered double hydroxide of 0.0% by mass, blow-molding was possible without any problems. When this comparative toner bottle (A1-4) was used to evaluate chemical attack, deformation was confirmed on the surface of the toner particles adhering to the inner surface of the toner bottle, and chemical attack had occurred. The reason for this is thought to be that if inorganic layered double hydroxide is not added, the wax, which causes chemical attack, is not adsorbed by the inorganic layered double hydroxide, and the wax migrates to the inner surface of the toner bottle, causing chemical attack.

[0086] Example A2-1 Preparation of Recycled Pellets 0.5% by mass of zeolite (product name: Silton MT-8000, manufactured by Mizusawa Industrial Chemicals) was added to 99.5% by mass of flakes prepared in the same manner as in Example A1-1, and the mixture was melt-kneaded using a twin-screw extruder (product name: PC-46, manufactured by Ikegai Corporation) at a temperature of 210°C, a screw rotation speed of 200 rpm, and a discharge rate of 50 kg / h, followed by pelletization. The zeolite used here was in filler form. (This recycled material is referred to as MR-PP (2-1)).

[0087] <Preparation of Blow Bottle> MR-PP (2-1) was placed in the one-step stretch blow molding machine and biaxial stretch blow molding was carried out under the same blow molding conditions as above (the obtained toner bottle is referred to as toner bottle (A2-1)). Toner was placed in the toner bottle (A2-1), and a chemical attack confirmation test was carried out in an environment of 50°C for 72 hours. As a result, no deformation of the toner particle surface was confirmed when the toner adhering to the inner surface of the toner bottle was observed.

[0088] Blow molding was carried out in the same manner as in Example A2-1, except that the compounding ratio of flakes and zeolite was changed as shown in Table 4, to obtain toner bottles (A2-2), (A2-3), and a comparative toner bottle (A2-4). Blow molding could be carried out without any problems for all of the toner bottles. For each of the obtained toner bottles, deformation of the toner particle surface was observed in the same manner as in Example A2-1.

[0089] Toner bottle (A2-2) When a preform was biaxially stretched and blow-molded with 1.0% by mass of zeolite added, blow molding was possible without any problems. When this toner bottle (A2-2) was used to evaluate chemical attack, no deformation of the toner particle surface was confirmed even when the toner adhering to the inner surface of the toner bottle was observed.

[0090] Toner bottle (A2-3) When a preform was biaxially stretched and blow-molded with 0.1% by mass of zeolite added, blow molding was possible without any problems. When this toner bottle (A2-3) was used to evaluate chemical attack, no deformation of the toner particle surface was confirmed even when the toner adhering to the inner surface of the toner bottle was observed.

[0091] Comparative toner bottle (A2-4) When a preform was biaxially stretched and blow-molded with 0.0% by mass of zeolite added, blow molding was possible without any problems. When this comparative toner bottle (A2-4) was used to evaluate chemical attack, deformation was confirmed on the surface of the toner particles adhering to the inner surface of the toner bottle, and chemical attack had occurred. The reason for this is thought to be that if zeolite is not added, the wax, which is the cause of chemical attack, is not adsorbed by the zeolite, and the wax migrates to the inner surface of the toner bottle, causing chemical attack.

[0092] <Production of toner bottle by direct blow molding> A direct blow molding machine (model name: MSE-55E / 54M-AP(E2); manufactured by Tahara Corporation) was used to produce the toner bottle 3 shown in Fig. 7. In Fig. 7, A was φ76 mm and B was 150 mm.

[0093] First, the materials shown in Table 1 below were melt-kneaded and then pelletized to prepare a masterbatch having a carbon black concentration of 5% by mass.

[0094] Next, the masterbatch containing 5% by mass of carbon black prepared above and PP were mixed in the ratios shown in Table 2 below, melt-kneaded, and then pelletized to obtain pellets of a resin mixture.

[0095] <Direct Blow Molding Conditions> The pellets of the resin mixture dried above were placed in a direct blow molding machine and molded into a toner bottle under the following conditions: The screw diameter of the molding machine was 50 mm.

[0096] Direct blow molding was performed under the following molding conditions: Screw diameter: 50 mm Cylinder temperature: 210°C Extrusion rate: 10 kg / h Blow pressure: 0.6 MPa Cooling time: 15 s Mold temperature: 15°C A toner bottle was produced by the above direct blow molding. This bottle is a toner bottle made from virgin PP that has not been recycled. 200 toner bottles made from virgin PP were produced using the above method.

[0097] (Example A3-1) <Preparation of Recycled Pellets> In the same manner as in Example A1-1, 200 toner bottles made of virgin PP with residual black toner inside were prepared. The average amount of black toner remaining in the toner bottles for the 200 toner bottles was 0.321% by mass, based on the mass of the toner bottle itself. Next, the 200 toner bottles with residual toner inside prepared above were crushed in a crusher to a size of approximately 5 to 10 mm square to obtain crushed products (hereinafter also referred to as "flake products"). The wax content of the obtained flake products was measured using GPC and FT-IR, and was found to be 0.022 parts by mass per 100 parts by mass of the flake products. To 99.5% by mass of this flake product, 0.5% by mass of a hydrotalcite compound (trade name: DHT-4C; manufactured by Kyowa Chemical Industry Co., Ltd.) was added as an inorganic layered double hydroxide. The mixture was melt-kneaded using a twin-screw extruder (manufactured by Ikegai Corporation, PC-46) at a temperature of 210°C, a screw rotation speed of 200 rpm, and a discharge rate of 50 kg / h, and then pelletized. The inorganic layered double hydroxide used here was in filler form and had a number-average particle size of 0.38 μm. (This recycled material is referred to as MR-PP (3-1)).

[0098] <Preparation of Blow Bottle> MR-PP (3-1) was placed in the above-mentioned direct blow molding machine and subjected to direct blow molding under the same blow molding conditions as those described above (the obtained toner bottle is referred to as toner bottle (A3-1)). Toner was placed in the toner bottle (A3-1), and a chemical attack confirmation test was carried out in an environment of 50°C for 72 hours. As a result, no deformation of the toner particle surface was confirmed when the toner adhering to the inner surface of the toner bottle was observed.

[0099] Blow molding was carried out in the same manner as in Example A3-1, except that the compounding ratio of the flake product and the inorganic layered double hydroxide (hydrotalcite compound) was changed as shown in Table 3, to obtain toner bottles (A3-2), (A3-3), and a comparative toner bottle (A3-4). Blow molding could be carried out without any problems for all of the toner bottles. For each of the obtained toner bottles, deformation of the toner particle surface was observed in the same manner as in Example A3-1.

[0100] Toner bottle (A3-2) When direct blow molding was performed with an inorganic layered double hydroxide added in an amount of 1.0% by mass, blow molding was possible without any problems. When this toner bottle (A3-2) was used to evaluate chemical attack, no deformation of the toner particle surface was confirmed even when the toner adhering to the inner surface of the toner bottle was observed.

[0101] Toner bottle (A3-3) When direct blow molding was performed with an inorganic layered double hydroxide added in an amount of 0.1% by mass, blow molding was possible without any problems. When this toner bottle (A3-3) was used to evaluate chemical attack, no deformation of the toner particle surface was confirmed even when the toner adhering to the inner surface of the toner bottle was observed.

[0102] Comparative toner bottle (A3-4) When direct blow molding was performed with an added amount of inorganic layered double hydroxide of 0.0% by mass, blow molding was possible without any problems. When chemical attack was evaluated using this comparative toner bottle (A3-4), deformation was confirmed on the surface of the toner particles adhering to the inner surface of the toner bottle, and chemical attack had occurred. The reason for this is thought to be that if inorganic layered double hydroxide is not added, the wax, which causes chemical attack, is not adsorbed by the inorganic layered double hydroxide, and the wax migrates to the inner surface of the toner bottle, causing chemical attack.

[0103] Example A4-1 Preparation of Recycled Pellets 0.5% by mass of zeolite (product name: Silton MT-8000, manufactured by Mizusawa Industrial Chemicals) was added to 99.5% by mass of flakes prepared in the same manner as in Example A3-1, and the mixture was melt-kneaded using a twin-screw extruder (PC-46, manufactured by Ikegai Corporation) at a temperature of 210°C, a screw rotation speed of 200 rpm, and a discharge rate of 50 kg / h, followed by pelletization. The zeolite used here was in filler form. (This recycled material is referred to as MR-PP (4-1)).

[0104] <Preparation of Blow Bottle> MR-PP (4-1) was placed in the above-mentioned direct blow molding machine and subjected to direct blow molding under the same blow molding conditions as those described above (the obtained toner bottle is referred to as toner bottle (A4-1)). Toner was placed in the toner bottle (A4-1), and a chemical attack confirmation test was carried out in an environment of 50°C for 72 hours. As a result, no deformation of the toner particle surface was confirmed when the toner adhering to the inner surface of the toner bottle was observed.

[0105] Blow molding was carried out in the same manner as in Example A4-1, except that the compounding ratio of flakes and zeolite was changed as shown in Table 8, to obtain toner bottles (A4-2), (A4-3), and a comparative toner bottle (A4-4). Blow molding could be carried out without any problems for all of the toner bottles. For each of the obtained toner bottles, deformation of the toner particle surface was observed in the same manner as in Example A4-1.

[0106] Toner bottle (A4-2) When direct blow molding was performed with an added amount of 1.0 mass % zeolite, blow molding was possible without any problems. When this toner bottle (A4-2) was used to evaluate chemical attack, no deformation of the toner particle surface was confirmed even when observing the toner adhering to the inner surface of the toner bottle.

[0107] Toner bottle (A4-3) When direct blow molding was performed with an added amount of 0.1% by mass of zeolite, blow molding was possible without any problems. When this toner bottle (A4-3) was used to evaluate chemical attack, no deformation of the toner particle surface was confirmed even when observing the toner adhering to the inner surface of the toner bottle.

[0108] Comparative toner bottle (A4-4) When direct blow molding was performed with an added amount of 0.0% by mass of zeolite, blow molding was possible without any problems. When chemical attack was evaluated using this comparative toner bottle (A4-4), deformation was confirmed on the surface of the toner particles adhering to the inner surface of the toner bottle, and chemical attack had occurred. The reason for this is thought to be that if zeolite is not added, the wax, which is the cause of chemical attack, is not adsorbed by the zeolite, and the wax migrates to the inner surface of the toner bottle, causing chemical attack.

[0109] <Production of toner bottle by direct blow molding> Toner bottle 3 shown in Fig. 7 was produced using a direct blow molding device. A was 76 mm in diameter, and B was 150 mm. KEIYO B5804 (product name) manufactured by Keiyo Polyethylene Co., Ltd. was used as the pellet material.

[0110] <Direct Blow Molding Conditions> The pellets of the resin mixture dried above were fed into a direct blow molding machine (model name: MSE-55E / 54M-AP(E2), Tahara Co., Ltd.) to mold a toner bottle. The screw diameter of the injection molding machine in this molding machine was 50 mm.

[0111] Direct blow molding was performed under the following molding conditions: Extruder screw diameter: 50 mm Extruder cylinder temperature: 182°C Extrusion rate: 10 kg / h Blow pressure: 0.6 MPa Cooling time: 15 s Mold temperature: 15°C A toner bottle was produced by the above direct blow molding. This bottle is a toner bottle made from virgin PE that has not been recycled. 200 toner bottles made from virgin PE were produced using the above method.

[0112] (Example B1-1) <Preparation of Recycled Pellets> All 200 toner bottles containing virgin PE prepared above were filled with black toner contained in a toner cartridge (product name: Toner NPG-26, manufactured by Canon Inc.). The black toner contained ester wax. Next, the openings of the toner bottles containing virgin PE were turned vertically downward to discharge the black toner inside. Even after this operation, a small amount of black toner remained on the inner wall of each toner bottle. At this time, the average amount of black toner remaining in the toner bottles for the 200 toner bottles was 0.321% by mass, based on the mass of the toner bottle itself. Note that the mass of the toner bottle itself refers to the mass of the toner bottle and the toner remaining inside it, with all supply components and other items removed (the same applies below).

[0113] Next, each toner bottle was crushed into pieces approximately 5 to 10 mm square using a crusher to obtain crushed products (hereinafter also referred to as "flake products"). The wax content of the resulting flake products was measured using GPC and FT-IR, and was found to be 0.022 parts by mass per 100 parts by mass of the flake products. 0.5% by mass of a hydrotalcite compound (trade name: DHT-4C; manufactured by Kyowa Chemical Industry Co., Ltd.) was added to 99.5% by mass of the flake products as an inorganic layered double hydroxide. The mixture was melt-kneaded using a twin-screw extruder (PC-46 manufactured by Ikegai Corporation) at a temperature of 200°C, a screw rotation speed of 200 rpm, and a discharge rate of 50 kg / h, and then pelletized. The inorganic layered double hydroxide used here was in a filler form and had a number-average particle size of 0.38 μm. (This recycled material is referred to as MR-PE(1-1)).

[0114] <Preparation of Blow Bottle> MR-PE (1-1) was placed in the above-mentioned direct blow molding machine and subjected to direct blow molding under the same blow molding conditions as those described above (the obtained toner bottle is referred to as toner bottle (B1-1)). Toner was placed in the toner bottle (B1-1), and a chemical attack confirmation test was carried out in an environment of 50°C for 72 hours. As a result, no deformation of the toner particle surface was confirmed when the toner adhering to the inner surface of the toner bottle was observed.

[0115] Blow molding was carried out in the same manner as in Example B1-1, except that the compounding ratio of the flake product and the inorganic layered double hydroxide (hydrotalcite compound) was changed as shown in Table 1, to obtain toner bottles (B1-2), (B1-3), and a comparative toner bottle (B1-4). Blow molding could be carried out without any problems for all of the toner bottles. For each of the obtained toner bottles, deformation of the toner particle surface was observed in the same manner as in Example B1-1.

[0116] Toner bottle (B1-2) When direct blow molding was performed with an inorganic layered double hydroxide added in an amount of 1.0 mass%, blow molding was possible without any problems. When this toner bottle (B1-2) was used to evaluate chemical attack, no deformation of the toner particle surface was confirmed even when the toner adhering to the inner surface of the toner bottle was observed.

[0117] Toner bottle (B1-3) When direct blow molding was performed with an inorganic layered double hydroxide added in an amount of 0.1% by mass, blow molding was possible without any problems. When this toner bottle (B1-3) was used to evaluate chemical attack, no deformation of the toner particle surface was confirmed even when the toner adhering to the inner surface of the toner bottle was observed.

[0118] Comparative toner bottle (B1-4) When direct blow molding was performed with an added amount of inorganic layered double hydroxide of 0.0% by mass, blow molding was possible without any problems. When chemical attack was evaluated using this comparative toner bottle (B1-4), deformation was confirmed on the surface of the toner particles adhering to the inner surface of the toner bottle, and chemical attack had occurred. The reason for this is thought to be that if inorganic layered double hydroxide is not added, the wax, which causes chemical attack, is not adsorbed by the inorganic layered double hydroxide, and the wax migrates to the inner surface of the toner bottle, causing chemical attack.

[0119] (Example B2-1) <Preparation of Recycled Pellets> 0.5% by mass of zeolite (product name: Silton MT-8000, manufactured by Mizusawa Industrial Chemicals, Ltd.) was added to 99.5% by mass of flakes prepared in the same manner as in Example B1-1, and the mixture was melt-kneaded using a twin-screw extruder (PC-46 manufactured by Ikegai Corporation) at a temperature of 200°C, a screw rotation speed of 200 rpm, and a discharge rate of 50 kg / h, followed by pelletization. The zeolite used here was in a filler form. (This recycled material is referred to as MR-PE (2-1)).

[0120] <Preparation of Blow Bottle> MR-PE (2-1) was placed in the above-mentioned direct blow molding machine and subjected to direct blow molding under the same blow molding conditions as those described above (the obtained toner bottle is referred to as toner bottle (B2-1)). Toner was placed in the toner bottle (B2-1), and a chemical attack confirmation test was carried out in an environment of 50°C for 72 hours. As a result, no deformation of the toner particle surface was confirmed when the toner adhering to the inner surface of the toner bottle was observed.

[0121] Blow molding was carried out in the same manner as in Example B2-1, except that the compounding ratio of flakes and zeolite was changed as shown in Table 2, to obtain toner bottles (B2-2), (B2-3), and a comparative toner bottle (B2-4). Blow molding could be carried out without any problems for all of the toner bottles. For each of the obtained toner bottles, deformation of the toner particle surface was observed in the same manner as in Example B2-1.

[0122] Toner bottle (B2-2) When direct blow molding was performed with an added amount of 1.0 mass % zeolite, blow molding was possible without any problems. When this toner bottle (B2-2) was used to evaluate chemical attack, no deformation of the toner particle surface was confirmed even when observing the toner adhering to the inner surface of the toner bottle.

[0123] Toner bottle (B2-3) When direct blow molding was performed with an added amount of 0.1% by mass of zeolite, blow molding was possible without any problems. When this toner bottle (B2-3) was used to evaluate chemical attack, no deformation of the toner particle surface was confirmed even when observing the toner adhering to the inner surface of the toner bottle.

[0124] Comparative toner bottle (B2-4) When direct blow molding was performed with an added amount of zeolite of 0.0% by mass, blow molding was possible without any problems. When chemical attack was evaluated using this comparative toner bottle (B2-4), deformation was confirmed on the surface of the toner particles adhering to the inner surface of the toner bottle, and chemical attack had occurred. The reason for this is thought to be that if zeolite is not added, the wax, which is the cause of chemical attack, is not adsorbed by the zeolite, and the wax migrates to the inner surface of the toner bottle, causing chemical attack.

[0125] The present disclosure is not limited to the above-described embodiments, and various modifications and variations are possible without departing from the spirit and scope of the present invention. Therefore, the following claims are appended to clarify the scope of the present disclosure. This application claims priority based on Japanese Patent Application No. 2023-172338 filed on October 3, 2023, Japanese Patent Application No. 2023-172343 filed on October 3, 2023, and Japanese Patent Application No. 2024-137903 filed on August 19, 2024, the entire contents of which are incorporated herein by reference.

[0126] 3: Toner bottle, 21: Developing device, 80: Image forming device, 60: Primary transfer device, 62: Intermediate transfer body, 63: Paper feeder, 64: Secondary transfer section, 68: Fixing means, 70: Paper discharge tray, 101: Injection molding machine, 102: Preform mold, 103: Preform mold, 104: Preform, 105: Heating cylinder, 106: Preform mouth, 107: Heating furnace, 108: Blow mold, 109: Stretching rod, 110: Gas, 112: Blow molded product, 201: PP resin, 202: Wax-derived component, 207: Extrusion screw

Claims

1. A blow-molded article, comprising: at least one selected from the group consisting of inorganic layered double hydroxides and zeolites; polyethylene or polypropylene; and wax.

2. The blow-molded article according to claim 1, wherein the total content of the inorganic layered double hydroxide and the zeolite is 0.09 to 1.2 mass % based on the mass of the blow-molded article.

3. The blow molded article according to claim 1 or 2, wherein the inorganic layered double hydroxide comprises a hydrotalcite compound.

4. The blow molded article according to any one of claims 1 to 3, wherein the polyethylene or polypropylene is material recycled polyethylene or material recycled polypropylene.

5. The blow molded article according to any one of claims 1 to 4, wherein the wax comprises an ester wax.

6. The blow molded article according to any one of claims 1 to 5, which is a toner bottle.

7. A toner bottle comprising: at least one selected from the group consisting of inorganic layered double hydroxides and zeolites; polyethylene or polypropylene; and wax.

8. A method for producing a blow molded article according to any one of claims 1 to 6, comprising the steps of: preparing a preform containing at least one selected from the group consisting of the inorganic layered double hydroxide and the zeolite, the polyethylene or polypropylene, and the wax; and stretch-blow molding the preform to obtain the blow molded article.

9. The method for producing a blow molded product according to claim 8, wherein the step of preparing the preform comprises: pulverizing a recycled toner bottle having electrophotographic toner attached thereto to obtain a pulverized material; melting and kneading the pulverized material with at least one selected from the group consisting of the inorganic layered double hydroxide and the zeolite to form pellets; and forming the preform from the formed pellets, wherein the electrophotographic toner contains the wax, and the toner bottle contains the polyethylene or polypropylene.

10. A method for producing a blow-molded article according to any one of claims 1 to 6, comprising the steps of: preparing pellets containing at least one selected from the group consisting of the inorganic layered double hydroxide and the zeolite, the polyethylene or polypropylene, and the wax; and blow-molding the pellets to obtain the blow-molded article.

11. The method for producing a blow molded product according to claim 10, wherein the step of preparing the pellets comprises: pulverizing a recycled toner bottle having electrophotographic toner attached thereto to obtain a pulverized material; and melting and kneading the pulverized material with at least one selected from the group consisting of inorganic layered double hydroxides and zeolites to form pellets, wherein the electrophotographic toner contains the wax, and the toner bottle contains the polyethylene or polypropylene.

12. A molded article, comprising: at least one selected from the group consisting of inorganic layered double hydroxides and zeolites; polyethylene or polypropylene; and wax.

13. A pellet comprising: at least one selected from the group consisting of inorganic layered double hydroxides and zeolites; polyethylene or polypropylene; and a wax.

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