JP5336130B2 - Recycled plastic material and molded body - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a recycled plastic material with improved compatibility and high physical properties, and a plastic molded item composed of the plastic material. <P>SOLUTION: This sheet type or film type molded item is constituted of the plastic material including a plurality of sorts of polymers, at least one of the sorts being used, and at least one sort of compatibilizers chosen from the group consisting of an oxazoline compatibilizer, an elastomer compatibilizer, a reactive compatibilizer, and a copolymer compatibilizer. <P>COPYRIGHT: (C)2009,JPO&amp;INPIT

Description

  The present invention relates to a plastic material using a compatibilizer selected from an oxazoline-based compatibilizer, an elastomer-based compatibilizer, a reactive compatibilizer, and a copolymer-based compatibilizer as a compatibilizer or modifier. The present invention relates to a recycled plastic material, and a plastic molded body composed of the plastic material.

In recent years, the reuse and reuse of plastic waste has become an important issue from the viewpoints of global environmental protection, effective use of resources, that is, recycling, and waste disposal problems.
However, the reuse of plastic products has a very large technical problem, and at present, the reuse is hardly performed except for the recycling of PET (PET) bottles. In other words, the conventional technology consists of a transparent single resin with no additives, such as PET bottles, and even if the contents at the time of use are extremely clean, avoid coloring and various physical properties due to reduced viscosity during reuse. I can't. As a result, a recycled product with sufficient performance as a product cannot be obtained. Considering the collection cost of used products and the appearance, quality, etc. of recycled products, even a plastic bottle is still a sufficiently practical recycling system. It is not.

  Furthermore, when reusing plastic products other than PET bottles, these plastic products contain a large amount of additives and are made of various resins, so coloring and deterioration of physical properties are inevitable. That is, for plastic products other than plastic bottles, the safety, productivity, and quality of recycled products are insufficient for practical use, and the recycling cost is high, and a recycling system has not yet been established.

  Complete separation and collection of waste plastics is difficult, and usually multiple types of polymers are mixed in the regeneration process. For this reason, the polymer physical properties of the recycled plastic are lowered. A large amount of plasticizer such as oil is blended during plastic regeneration to prevent deterioration of physical properties, but it is difficult to restore the original physical properties.

  Further, if the plurality of types of polymers mixed at the time of regeneration are incompatible with each other, uniform dispersion cannot be obtained, and the polymer properties of the recycled plastic are greatly reduced. Thus, since the polymer property of the recycled plastic is low, the recycled plastic can be used only for limited applications that can be used even if the property value is low.

  Under such circumstances, recycling of plastic waste remains at a very low level, which is a major cause of environmental and resource problems.

  On the other hand, various plastic products often require flame retardancy. In order to impart flame retardancy to a plastic molded body, it is generally considered to add a flame retardant to a plastic material. However, when a flame retardant is blended with a plastic material, physical properties of the plastic are likely to deteriorate. In particular, when different plastic polymers that are incompatible with each other are contained in the plastic material, uniform dispersion of the different polymers cannot be obtained, and the physical properties of the plastic are further greatly reduced by the addition of the flame retardant. The problem of deterioration of physical properties due to the blending of the flame retardant is greater in the case of recycled plastic material from waste plastic than in the case of unused plastic material.

  Various plastic products are often required to improve strength, heat resistance, water resistance, warm water resistance, moisture resistance, and other various performances and functions. In such a case, it can be considered that various inorganic fillers and / or organic fillers are blended into the plastic material according to various performances and functions. However, when an inorganic filler and / or an organic filler are added to the plastic material, the physical properties of the plastic are likely to be lowered as in the case of the flame retardant.

  Under such circumstances, there is a demand for the development of a technology that imparts flame retardancy without causing deterioration of the physical properties of the plastic even when a flame retardant is blended in the plastic material. In particular, when recycling waste plastics and recycling them, even when different polymers are mixed, especially when different polymers that are incompatible with each other are mixed, the physical properties of the polymer do not deteriorate and flame retardancy is reduced. There is a demand for development of technology to be granted. There is a demand for the development of a technology that does not cause deterioration of the physical properties of the plastic and imparts various performances and functions even when various inorganic fillers and / or organic fillers are blended into the plastic material.

Japanese Patent Laid-Open No. 2000-129099 JP 2001-220473 A

  Therefore, an object of the present invention is to use a compatibilizer selected from an oxazoline-based compatibilizer, an elastomer-based compatibilizer, a reactive compatibilizer, and a copolymer-based compatibilizer as a compatibilizer or modifier. Another object of the present invention is to provide a plastic material, a recycled plastic material, and a plastic molded body composed of the plastic material.

  Furthermore, an object of the present invention is to provide a flame-retardant plastic material having high physical properties, a flame-retardant recycled plastic material having high physical properties, and a flame-retardant plastic molded body composed of the plastic material. is there. Another object of the present invention is to provide a plastic material containing an inorganic filler and / or an organic filler, a recycled plastic material containing an inorganic filler and / or an organic filler, and an inorganic filler comprising the plastic material and / or The object is to provide a plastic molded body in which an organic filler is blended.

The present invention includes the following inventions.
(1) At least one polymer is selected from the group consisting of a plurality of used polymers, an oxazoline-based compatibilizer, an elastomer-based compatibilizer, a reactive compatibilizer, and a copolymer-based compatibilizer. A sheet-like or film-like molded body composed of a recycled plastic material containing at least one compatibilizing agent,
The plurality of types of polymers include used polyethylene terephthalate or polybutylene terephthalate to be recycled and polyolefin selected from unused polyethylene and polypropylene to be used or recycled.
The recycled plastic material includes 0.5 to 30 parts by weight of the compatibilizer with respect to 100 parts by weight of the plurality of types of polymers.
The sheet-shaped or film-shaped molded body has 2,000-8,000 fine convexes having a width of 1-10 μm and a height of 0.5-5 μm per 1 mm ² of the surface. .

(2) The sheet-like or film-like molded product according to the above (1), wherein an ionomer resin is further used as a compatibilizing agent .

The recycled plastic material includes 0.5 to 30 parts by weight of the compatibilizer with respect to 100 parts by weight of the plurality of types of polymers. Here, the compounding amount of the compatibilizer is at least one compatibilizer selected from the group consisting of an oxazoline-based compatibilizer, an elastomer-based compatibilizer, a reactive compatibilizer, and a copolymer-based compatibilizer, And, if used, the total amount of ionomer resin.

  According to the present invention, a plastic material having high physical properties, a recycled plastic material having high physical properties, and a plastic molded body composed of the plastic material are provided.

  The present invention can also be applied to different polymers that are compatible with each other, but particularly when it is desired to compatibilize different polymers that are incompatible with each other (for example, aliphatic polymers and aromatic polymers, polar polymers and nonpolar polymers). It is particularly effective.

  The present invention can be applied to both unused resins and used recovered resins, but since recycled plastic materials having high physical properties can be obtained even in the case of recovered resins, these recycled plastic materials can be used in a wide range of fields and applications. Is possible. Thus, the present invention greatly contributes to the recycling of waste plastic.

  In the present invention, the one or more kinds of polymers include, without limitation, materials including various thermoplastic polymers, thermosetting polymers, rubbers, and other polymer materials. preferable. A commercially available polymer or a newly synthesized polymer can be used as the thermoplastic polymer.

  Specific examples of the polymer material include polyethylene (PE), polypropylene (PP), ethylene-propylene copolymer, polybutadiene, acrylonitrile-butadiene-styrene copolymer (ABS), polystyrene (PS), acrylonitrile-chlorinated polyethylene. -Styrene copolymer resin (ACS), acrylonitrile-styrene copolymer resin (AS), polybutene resin, alkyd resin, amino resin, acrylonitrile-acrylic rubber-styrene copolymer resin (ASA), bismaleimide triazine resin, chlorine Polyether, chlorinated polyethylene, allyl resin, epoxy resin, ethylene-α-olefin copolymer, ethylene-vinyl acetate-vinyl chloride copolymer, ethylene-vinyl chloride copolymer, ethylene vinyl alcohol resin (EVA), Ionomer, methacryl-styrene copolymer, nitrile resin, polyester [polyethylene terephthalate (PET), polybutylene terephthalate (PBT), etc.], olefin vinyl alcohol copolymer, petroleum resin, phenol resin, polyacetal, polyacrylate, polyamide, poly Allyl sulfone, polybenzimidazole, polybutylene, polycarbonate, polyether ether ketone, polyether ketone, polyether nitrile, polyether sulfone, polyketone, methacrylic resin, polymethylpentene, polyphenylene ether, polyphenylene sulfide, polysulfone, butadiene-styrene resin , Polyurethane, polyvinyl acetal, polyvinyl alcohol, polyvinyl chloride, polyvinylidene chloride, Silicone resin, polyvinyl acetate, xylene resin, crosslinked polyolefin such as crosslinked polyethylene, crosslinked polystyrene, unsaturated polyester resin, urea resin, melamine resin, fluororesin, biodegradable resin, thermoplastic elastomer, ethylene-propylene-diene copolymer Examples include coalesced (EPDM), chloroprene rubber (CR), butadiene rubber (BR), nitrile rubber, natural rubber, acrylonitrile butadiene rubber, butyl rubber, and the like, and fiber reinforced products (FRP) of these polymer compounds. These are exemplary and include various other polymers.

  Among the above, most are thermoplastic types, and bismaleimide triazine resin, epoxy resin, FRP, phenol resin, unsaturated polyester resin, urea resin, and melamine resin are thermosetting types. In addition, polyurethane, silicone resin, and xylene resin include a thermoplastic type and a thermosetting type. For the thermosetting type, it is preferable to use a pulverized product. In addition, it is preferable to use a pulverized product for a crosslinked polyolefin such as a crosslinked polyethylene or a crosslinked polystyrene.

  In the present invention, the polymer may be an unused resin (Virgin resin) or a used recovered resin. That is, the present invention includes a form in which all of one or more kinds of polymers are unused polymers, and a form in which at least one of the one or more kinds of polymers is a used polymer. Also included are forms in which one or more of the polymers are all spent polymers.

  Although not particularly limited, the effects of the present invention can be obtained particularly when the recovered resin is included. The recovered resin is often in the form of a mixture of different types of resins, and in the past, good compatibility could not be obtained, but in the present invention, good compatibility is obtained by the inclusion of the compatibilizing agent described below, and the physical properties A recycled plastic material can be obtained without causing a decrease. When reusing the recovered resin, deterioration due to light, heat, or gas during use, or scratches or contamination due to contact with other objects can be considered. Therefore, chemical cleaning with water, acid / alkali, etc., or sand blasting in advance It is also preferable to perform physical cleaning of the surface by, for example, friction.

  In the present invention, at least one selected from the group consisting of an oxazoline-based compatibilizer (B), an elastomer-based compatibilizer (C), a reactive compatibilizer (D), and a copolymer-based compatibilizer (E). The compatibilizing agent is used.

Examples of the oxazoline-based compatibilizer (B) include the following types B1 to B3.
Examples of the B1 type include bisoxazoline / styrene / maleic anhydride copolymer (OXZ; manufactured by Mikuni Pharmaceutical Co., Ltd.).
Examples of the B2 type include bisoxazoline / maleic anhydride-modified polyethylene [a blend of OXZ (manufactured by Mikuni Pharmaceutical Co., Ltd.) and PE (manufactured by Sanyo Chemical Industries, Yumex 2000)].
Examples of the B3 type include bisoxazoline / maleic anhydride-modified polypropylene [a blend of OXZ (manufactured by Mikuni Pharmaceutical Co., Ltd.) and PP (manufactured by Sanyo Chemical Industries, Yumex 1010)].

Examples of the elastomer compatibilizer (C) include the following types of C1 to C4.
Examples of the C1 type include styrene ethylene butadiene copolymer (SEB; manufactured by Asahi Kasei Kogyo Co., Ltd., Tuftec).
Examples of the C2 type include styrene ethylene butadiene styrene copolymer (SEBS; manufactured by Asahi Kasei Kogyo).
Examples of the C3 type include hydrogenated styrene isopropylene styrene copolymer (H-SIS).
Examples of the C4 type include aromatic resins, petroleum resins (Neopolymer manufactured by Nippon Oil Corporation), and the like.

  The reactive compatibilizing agent (D) is a polymer having a double bond, a carboxyl group, an epoxy group, etc., and reacts with one or both of the polymers to be compatibilized in the molding process, thereby causing a graft or block structure. It functions as a compatibilizer by acting as a surfactant based on the above (reference: “Polymer Alloy” Fundamentals and Applications, edited by the Society of Polymer Science, published in 1993). Examples of the reactive compatibilizing agent (D) include the following types D1 to D5.

D1 type:
Ethylene glycidyl methacrylate copolymer (E-GMA; copolymer weight composition such as E / GMA = 100/6 to 12), ethylene glycidyl methacrylate-vinyl alcohol copolymer (E-GMA-VA; copolymer weight composition such as E / GMA / VA = 100/3 to 12/8 to 5), ethylene glycidyl methacrylate-methacrylate copolymer (E-GMA-MA; copolymer weight composition, for example, E / GMA / MA = 100/3 to 6 / 30). Specific examples include Sumitomo Chemical Co., Ltd., Bond First E, Bond First 2C; Nippon Polyolefin Co., Ltd., Lex Pearl RA, Lex Pearl ET, and Lex Pearl RC.

D2 type:
And ethylene maleic anhydride ethyl acrylate copolymer (E-MAH-EA; manufactured by Sumitomo Chemical Co., Ltd.).

D3 type:
Ethylene glycidyl methacrylate-acrylonitrile styrene (EGMA-AS; copolymer weight composition, eg EGMA / AS = 70/30), ethylene glycidyl methacrylate-polystyrene (EGMA-PS; copolymer weight composition, eg EGMA / PS = 70/30) And ethylene glycidyl methacrylate-polymethyl methacrylate (EGMA-PMMA, for example, EGMA / PMMA = 70/30). Specifically, the product made from Japanese fats and oils and a modiper are mentioned.

D4 type:
Examples include acid-modified polyethylene wax (APEW; manufactured by Mitsui Chemicals, high wax).

D5 type:
COOH-ized polyethylene graft polymer, COOH-ized polypropylene graft polymer and the like can be mentioned.

  Examples of the copolymer-based compatibilizer (E) include polyethylene-polyamide graft copolymer (PE-PA GP) and polypropylene-polyamide graft copolymer (PP-PA GP). Further, it contains at least one group selected from the group consisting of alkoxy groups, amino groups, mercapto groups, vinyl groups, epoxy groups, acetal groups, maleic acid groups, oxazoline groups and carboxylic acid groups, and has a melt flow rate of 1 or more Specifically, a low-viscosity copolymer polymer such as methyl methacrylate-butadiene-styrene resin, acrylonitrile-butadiene rubber, EVA / PVC / graft copolymer, vinyl acetate-ethylene copolymer resin, ethylene- Examples include α-olefin copolymers, propylene-α-olefin copolymers, hydrogenated styrene-isopropylene-block copolymers, and the like. Specific examples include Elvalloy manufactured by Mitsui DuPont Polychemical.

  In the present invention, the oxazoline-based compatibilizer (B), the elastomer-based compatibilizer (C), the reactive compatibilizer (D), and the co-polymer are selected according to the type of one or more polymers. One type of compatibilizer or two or more types of compatibilizers selected from the polymer-based compatibilizers (E) are used in combination.

  In the present invention, in addition to the compatibilizers (B) to (E), the ionomer resin (A) is further combined as a compatibilizer depending on the type of one or more polymers. It may be used.

  In the present invention, the ionomer resin (A) includes various types. A typical ionomer is (a) a side chain ionic group partially present in the main chain of the host polymer (side chain type). Another type of ionomer is (b) a polymer obtained by neutralizing a metal ion with a host polymer or oligomer having carboxylic acid groups at both ends (telechelic type). Another type of ionomer has (c) a cation in the main chain and an anion bound thereto (ionene).

Counter ions for the ionic group of the host polymer include alkali metal ions such as Li ⁺ , Na ⁺ and K ⁺ , alkaline earth metal ions such as Mg ²⁺ , Ca ²⁺ , Sr ²⁺ and Ba ²⁺ , Zn Transition metal ions such as ²⁺ , Cu ²⁺ , Mn ²⁺ , Ni ²⁺ , Co ²⁺ , Co ³⁺ , Fe ³⁺ , Cr ³⁺ are used. For the cation host polymer, anions such as Cl ⁻ , Br ⁻ and I ⁻ are used.

  The ionomer resin is not particularly limited, and examples thereof include ethylene-methacrylic acid copolymer ionomer, ethylene-acrylic acid copolymer ionomer, propylene-methacrylic acid copolymer ionomer, and propylene-acrylic acid copolymer ionomer. , Butylene-acrylic acid copolymer ionomer, ethylene-vinylsulfonic acid copolymer ionomer, styrene-methacrylic acid copolymer ionomer, sulfonated polystyrene ionomer, fluorine ionomer, telechelic polybutadiene acrylic acid ionomer, sulfonated ethylene-propylene -Diene copolymer ionomer, hydrogenated polypentamer ionomer, polypentamer ionomer, poly (vinylpyridium salt) ionomer, poly (vinyltrimethyl) Ammonium salt) ionomer, poly (vinylbenzylphosphonium salt) ionomer, styrene-butadiene acrylic acid copolymer ionomer, polyurethane ionomer, sulfonated styrene-2-acrylamido-2-methylpropane sulfate ionomer, acid-amine ionomer, aliphatic System ionene, aromatic ionene and the like.

  These ionomer resins have the effect of compatibilizing different polymers that are incompatible with each other. One of these ionomer resins may be used as a compatibilizing agent or a plastic recycling modifier, and two or more may be used in combination as necessary.

  Of these ionomer resins, ethylene-methacrylic acid copolymer ionomers and ethylene-acrylic acid copolymer ionomers are preferably used. These are particularly effective in improving the compatibility between the aliphatic polymer and the aromatic polymer and the compatibility between the polar polymer and the nonpolar polymer. More specifically, as an ethylene-methacrylic acid copolymer ionomer, High Milan 1554, High Milan 1555, High Milan 1557, High Milan 1601, High Milan 1605, High Milan 1650, High Milan 1652, High Milan 1652 SR, High Milan 1652 SB, High Milan 1702, High Milan 1705 HIMILAN 1706, HIMILAN 1707, HIMILAN 1855, and HIMILAN 1856 (Mitsui DuPont Polychemical Co., Ltd.).

  The compounding amount of the compatibilizer [(B) to (E), including (A) if used) is the type of plastic to be recycled, the type and amount of other types of polymers mixed therein, Or it is good to determine suitably according to the kind and quantity of other kinds of polymers which it wants to mix. If the other kind of polymer is a polymer of the same type as the main plastic to be recycled (that is, a polymer that is relatively compatible), the blending amount of the compatibilizing agent may be relatively small. On the other hand, if the other type of polymer is a polymer that is incompatible with the main plastic to be recycled, it is better to use a larger amount of the compatibilizing agent than in the case of the same type of polymer. Moreover, when the amount of other polymers mixed in the main plastic increases, it is generally necessary to increase the amount of the compatibilizer. The same applies when the polymer is not used.

  The blending amount of the compatibilizer [(B) to (E), including (A) when used in combination) is appropriately determined from the above viewpoint, but one or more (recycled) The total amount of the compatibilizer is usually from 0.1 to 100 parts by weight, preferably from 0.5 to 50 parts by weight, more preferably from 1 to 30 parts by weight, more preferably from 100 parts by weight of the polymer which should or should not be used. 1 to 15 parts by weight is blended. If the compatibilizer is less than 0.1 parts by weight, it is difficult to obtain a compatibilizing effect. On the other hand, if the compatibilizer exceeds 100 parts by weight, the compatibilizing effect is saturated, and the heat resistance is reduced and the cost is increased. In some cases, it is not preferable. In particular, it is necessary to determine the amount of the compatibilizer used for each application in consideration of productivity and the quality and performance of the object. When (A) is used in combination as a compatibilizing agent, the compatibilizing agents (B) to (E) are preferably 10% by weight or more of the total amount of the compatibilizing agent.

  In the present invention, specific examples of the polymer to which the compatibilizing agent is preferably applied include polyethylene terephthalate (PET), and a recycled plastic material of PET and a molded product therefrom are obtained.

  In the present invention, examples of the combination of incompatible different polymers to which the compatibilizer is preferably applied include, for example, a combination of an aliphatic polymer and an aromatic polymer, a polar polymer and a nonpolar polymer, and a polyolefin resin and an engineering plastic. A new or recycled plastic material mainly composed of these resins, and a molded product therefrom can be obtained.

  More specifically, the polyolefin-based resin mainly includes polypropylene, very low density polyethylene, low density polyethylene, linear low density polyethylene, medium density polyethylene, high density polyethylene, and the like, and mixtures thereof. Engineering plastics include ABS resin, polyamide, polycarbonate, modified polyphenylene oxide, polyethylene terephthalate, polybutylene terephthalate, polyetherimide, polysulfone, polyacetal polyarylate, polyetheretherketone, polystyrene, polyimide and the like and mixtures thereof.

  More specifically, for example, PE and PET, PP and PET, PE and ABS, PE and PBT, PE and PA, PP and ABS, PC and ABS, PET and ABS, PS and PE, PS and PP, and PS Examples include PET, PC and PE, PC and PP, PC and PET, and a combination of PA and PET. These polymers are sufficiently applicable to various polymers recovered after use. Of course, in addition to these, various combinations exist, and not only two kinds of different polymers but also a combination of three or more kinds of different polymers can be applied.

  In the present invention, the combination of the above polymers is not limited, but it is preferable to use the compatibilizer type shown in the following table.

  Conventionally, in these recyclings, since different types of polymers are mixed in waste plastics, molded products and materials from recycled plastics having sufficiently high physical properties cannot be obtained. According to the present invention, it is possible to achieve the compatibilization of waste plastics containing different polymers, and to obtain recycled plastic materials having sufficiently high physical properties and molded articles composed thereof.

  In the present invention, in addition to the compatibilizing agent, the plastic material may contain a flame retardant and / or filler as a plastic recycling modifier or additive, if necessary.

  A flame retardant is added as needed to impart excellent flame retardancy. The flame retardant is not particularly limited, and various types of flame retardants, that is, boric acid flame retardants, phosphorus flame retardants, boric acid flame retardants and other inorganic flame retardants other than the phosphorus flame retardants Various flame retardants selected from the group consisting of a flame retardant, a nitrogen flame retardant, a halogen flame retardant, an organic flame retardant, and a colloid flame retardant are included.

  Examples of the halogen-based flame retardant include tetrabromo bisphenol A derivative (TBA), tetrabromo bisphenol S derivative, hexabromobenzene, decabromodiphenyl ether, tetrabromoethane (TBE), butanetetrabromobutane (TBB), hexabromocyclo Brominated flame retardants such as decane (HBCD), and chlorinated flame retardants such as chlorinated paraffin, chlorinated polyphenyl, chlorinated diphenyl, perchloropentacyclodecane, and chlorinated naphthalene. These exhibit even better flame retardant effects when used in combination with antimony trioxide or the like.

  Examples of phosphorus-based flame retardant compounds include ammonium phosphate, melamine phosphate, red phosphorus, phosphate ester, tricresyl phosphate, tri (β-chloroethyl) phosphate, tri (dichloropropyl) phosphate, tri (dibromopropyl) Examples include phosphate, 2,3-dibromopropyl-2,3-dichloropropyl phosphate, and the like.

  Examples of other inorganic flame retardants include inorganic substances such as aluminum hydroxide, magnesium hydroxide, zirconium hydroxide, calcium hydroxide, barium hydroxide, basic magnesium carbonate, dolomite, tin oxide hydrate, and borax. Metal hydrates, zinc borate, barium metaborate, zinc carbonate, magnesium carbonate-calcium, barium carbonate, magnesium oxide, molybdenum oxide, zirconium oxide, tin oxide, red phosphorus, expanded graphite, and the like.

  These flame retardants can be used alone or in combination of two or more. In the present invention, the amount of the flame retardant added to one or more types of polymer material is not particularly limited because it varies depending on the target flame retardancy, but is usually difficult with respect to 100 parts by weight of the polymer material. By blending 0.1 to 200 parts by weight of the flame retardant, preferably 1 to 100 parts by weight, more preferably 5 to 80 parts by weight, good flame retardancy is often obtained.

  Inorganic fillers and / or organic fillers are used to improve strength, heat resistance, water resistance, warm water resistance, moisture resistance, etc., or to improve other various performances and functions as necessary. Added. For example, plastic materials contain various inorganic fillers selected from oxides, hydroxides, carbonates, sulfates, silicates, nitrides, carbons, metal powders, ceramic powders, food scraps, glass fibers, etc. Also good. More specifically, examples of the inorganic filler include magnesium oxide, aluminum oxide, zirconium oxide, titanium oxide, silicon carbide, and mica. Various organic fillers selected from wood flour, cotton flock, cotton and the like may be included in the plastic material. Of course, both inorganic fillers and organic fillers may be used, and fillers other than those exemplified above may be used.

  In the present invention, the amount of the inorganic filler added to one or more types of polymer material is not particularly limited because it varies depending on the intended physical properties, performance, function, and type of the inorganic filler. In the case where good physical properties, performance, and functions are obtained by blending 0.1 to 200 parts by weight, preferably 1 to 100 parts by weight, more preferably 1 to 50 parts by weight with respect to 100 parts by weight. There are many.

  In the present invention, when both the flame retardant and the inorganic filler are added, from the viewpoint of dispersibility in the polymer material, the total addition amount of the flame retardant and the inorganic filler with respect to one or more kinds of polymer materials is the polymer material 100. The total addition amount is preferably up to 200 parts by weight and more preferably up to 100 parts by weight with respect to parts by weight.

  In the present invention, the amount of the organic filler added to one or more types of polymer material is not particularly limited because it varies depending on the intended physical properties, performance, function, and type of the organic filler, but is usually a polymer material. By blending 0.1 to 200 parts by weight of the organic filler with respect to 100 parts by weight, good physical properties, performance, and functions are often obtained.

  In the present invention, the plastic material further includes other additives such as anti-blocking agents, crystallization accelerators, gas adsorbents, anti-aging agents (esters, amides, etc.), antioxidants, ozone degradation inhibitors, ultraviolet rays. Absorbers, light stabilizers, tackifiers, plasticizers (fatty acids such as stearic acid and oleic acid or their metal salts), softeners (mineral oil, wax, paraffins, etc.), stabilizers, lubricants, mold release You may mix | blend suitably additives, such as an agent, an antistatic agent, a modifier, a coloring agent, a coupling agent, antiseptic | preservative, and an antifungal agent.

  By using the compatibilizing agent, it is possible to compatibilize any plural kinds of polymers and, if necessary, to mix and disperse flame retardants and / or fillers. Advantages of applying the present invention when reclaiming strong polyolefin-based resins and engineering plastics and obtaining various molded products and materials with flame retardancy and / or other performance / functions Is big.

  The blending method is not particularly limited and can be carried out by an ordinary melt kneading method. For example, the polymer, the compatibilizing agent and other components may be kneaded with a kneader such as a roll kneader, a Banbury mixer, an intermix, a single screw extruder, or a twin screw extruder. Kneading may be performed using one kind of kneader selected from the kneaders, or may be performed using two or more kinds of kneaders. Regarding the blending of the compatibilizing agent, a method (compound method) in which a predetermined amount of the compatibilizing agent is blended with the polymer resin to be mixed to obtain a chip having a predetermined compatibilizing agent and polymer concentration may be used. A master chip having a certain compatibilizer concentration can be prepared, and a predetermined amount of resin can be added to the master chip and mixed to obtain a predetermined compatibilizer and polymer concentration (master batch method). . Alternatively, the resin and the compatibilizing agent to be mixed can be charged into an extruder or a molding machine for producing a target molded body.

  In the present invention, a plastic material containing one or more kinds of polymers and the compatibilizer is molded by a conventional method to obtain various molded products. Moreover, it is also possible to add an additive to the plastic material as necessary to form a coating material, a coating material, or an adhesive material.

  Various molded products from the plastic material can be produced by a conventional molding method. For example, hollow or solid extruded products having various cross-sectional shapes, such as circular shapes, rectangular shapes, various injection-molded products, blow-molded products, sheets or films extruded from T-die, inflation films, melt spinning Fiber structures such as multifilaments, monofilaments, flat yarns, staple fibers, spunbond nonwoven fabrics, flash spun nonwoven fabrics, and various foam-molded products can be obtained.

  As various materials from the plastic material, a coating material on an organic or inorganic linear material or a twisted string material, a metal plate, a plastic film or sheet, a coating material on at least one surface such as a fiber or pulp nonwoven fabric, etc. Or a coating material such as a laminate material, a powder paint, a water-dispersed paint or an organic paint can be obtained. In addition, an adhesive suitable for adhering metals, ceramics, organic structures, and the like to each other can be obtained.

  The present invention is not limited to these, and includes various molded articles and various materials obtained from a plastic material (resin composition) having good compatibility including one or more kinds of polymers and the compatibilizing agent. It is.

  When a fibrous structure is obtained by an extrusion method, the fibrous structure is composed of very thin fibers and the linear velocity during production is very high. Therefore, the mixed resin composition has a small phase separation shape. And it needs to be relatively excellent in fluidity. As a measure of the fluidity of the polymer, MFR (melt flow rate: measurement temperature 280 ° C., load 2.16 kg, unit g / 10 min) is usually used. In order to obtain good productivity, quality, and physical properties, the MFR is usually 1 to 100, more preferably 10 to 60, and preferably 20 to 50 at the molding temperature.

  The above MFR is usually used as a measure of polymer fluidity. However, the measurement of MFR is a constant load method, the shear rate at the time of measurement varies depending on the polymer, and the MFR is measured in a shear rate region different from the shear rate at the time of actual molding of the polymer. For example, in injection molding, a large shear rate is required during molding, but in extrusion molding, the shear rate during molding is smaller than that during injection molding. Therefore, the MFR may not always be an evaluation of the target moldability. Particularly in the case of blends of different polymers as in the present invention, the fluidity of the polymer varies greatly depending on the shear rate. Therefore, as an evaluation of formability in the present invention, a capillograph (Capillograph 1B manufactured by Toyo Seiki Co., Ltd., capillary size: L = 10 mm, D = 0.5 mm) was used to change the shear rate to 0.1 to 10,000. The flow viscosity in the shear rate region was measured. Here, the melt viscosity (η) at a shear rate of 100 (1 / sec) is used as a measure of the fluidity of the polymer. In the measurement of the capillograph, it is necessary to set the measurement temperature in consideration of the highest melting point among the melting points of the resins used for the mixed resin. For example, in PE / PET mixed resin, it measures at 280 degreeC. In order to obtain good moldability, quality and physical properties of the mixed resin, for example, in monofilament molding, η is usually at least 800 poise, preferably at least 1,000 poise, and more preferably 1,500 to 20,000 poise. Molding is possible depending on the condition setting. In multifilament molding, η is usually at most 5,000 poise, preferably 800 to 4,000 poise, more preferably 1,000 to 3,000 poise. Of course, molding can be performed outside this range depending on the setting of conditions.

  Even in this case, in the mixed polymer, the ratio of the island component η1 to the sea component η2 (η1 / η2) is 0.02 ≦ η1 / η2 ≦ 30, preferably 0.05 ≦ η1 / η2 ≦ 20, Preferably, 0.08 ≦ η1 / η2 ≦ 10. Outside this range, molding is possible depending on the condition setting.

  In addition, since the shape of the fiber is very small, the shape of the phase separation in the polymer mixture greatly affects the productivity, quality, and physical properties. The size of phase separation that does not reduce productivity, quality, and physical properties is such that the ratio (S1 / S) of the area (S1) of the minor component (island component) domain to the fiber cross-sectional area (S) is 0.3 or less. , Preferably 0.2 or less, more preferably 0.15 or less, particularly preferably 0.1 or less. When this ratio is more than 0.5, a decrease in productivity due to yarn breakage and a decrease in quality and physical properties due to yarn unevenness are extremely undesirable.

  For this purpose, the composition of the mixed resin is such that the ratio of the minor components is usually at most 40% by weight, preferably at most 35% by weight, more preferably at most 30% by weight, based on the mixed resin. If the minor component exceeds 40% by weight, the phase separation form of the resin mixture becomes large, and the fiber is likely to be cut or partially deformed, resulting in a decrease in productivity, quality and physical properties, which is not preferable.

  In the fiber structure by the combination of different polymers in the present invention, especially monofilament, multifilament, and staple, because of the structure having a stiffer component in addition to the harder fiber portion, the bending rigidity and knot strength of the fiber are high. There is also a feature having favorable physical properties. In addition, in non-woven fabrics such as spunbond and melt blow, combining sea components with a high melting point and island components with a low melting point or a low softening point significantly increases the fusion between fibers without reducing the heat resistance and strength of the nonwoven fabric. Can be improved.

  In injection molding, relatively high fluidity is required, and the MFR is usually 70 or less, preferably 0.1 or more and 60 or less, and more preferably 0.2 or more and 55 or less.

  In a sheet, film or bottle molded product, although depending on the thickness thereof, it is generally not necessary to make the phase separation shape as small as in the fiber, and the amount of minor components in the resin composition is preferably at most 40. % By weight. When the amount of the minor component exceeds 40% by weight, it is not preferred because tearing during molding tends to occur and the productivity decreases, and the thickness unevenness and strength unevenness of the film become remarkable.

  About the fluidity | liquidity of mixed resin, an optimum value changes with sheets, films, and bottles, respectively. In the bottle molding, it is necessary to adjust the resin composition so that the fluidity becomes relatively small. In bottle molding, the MFR of the resin composition is usually 10 or less, preferably 7 or less, and more preferably 0.1 to 5.

  In addition, the optimum fluidity differs depending on the production method for sheets and films. The fluidity of the polymer is relatively small in the production of sheets and films by the T-die method, and the fluidity is relatively large in the film production by the inflation method. It is preferable. The MFR of the resin composition in the inflation method is usually 30 or less, preferably 25 or less, more preferably 0.1 to 20. The η of the resin composition in the inflation method is usually at least 2,000 poise, preferably at least 3,000 poise, and more preferably 4,000 to 20,000 poise. Of course, molding outside this range is possible depending on the condition setting. The MFR of the resin composition by the T-die method is usually 30 or less, preferably 25 or less, more preferably 0.1 to 8. The η of the resin composition in the T-die method is usually at least 2,000 poise, preferably at least 3,000 poise, and more preferably 4,000 to 50,000 poise.

  When extrusion molding is performed by the T-die method, in the mixed polymer, the ratio of the island component η1 to the sea component η2 (η1 / η2) is 0.01 ≦ η1 / η2 ≦ 10, preferably 0.02 ≦ η1. / Η2 ≦ 5.

  If the size of the phase separation in the sheet or film is too large, tearing due to non-uniform stretching, thickness unevenness, or a decrease in physical properties is increased, which is not preferable. When the size of the phase separation of island components in the sheet and film is D1, and the thickness of the sheet or film is D, the ratio of D1 / D is usually at most 0.5, preferably 0.3 or less, more preferably Is 0.2 or less, particularly preferably 0.1 or less.

  For other molded products, various mixing ratios are possible, but considering the productivity, quality, and physical properties, the ratio of the minor components is preferably at most 45% by weight. Further, the size of the phase separation due to the mixing of different polymers is not necessarily eliminated, but if it is large, it adversely affects productivity, operability, quality, physical properties and the like. In addition, in a molded body that requires fusion, a softening point having a low softening point as a large component (for example, PE) is good, and in a molded body that is flexible and requires heat resistance with high surface hardness, the softening point is a large component. Higher ones (for example, PET) are preferable.

  For each molded article or material, the type of the compatibilizer resin is appropriately selected according to the type or blending amount of one or more polymers to be used, and the amount of the compatibilizer resin is determined according to the device characteristics or productivity. It is necessary to set the optimum range according to the target quality and physical properties.

  According to the present invention, good compatibilization of PET / PE can be obtained, so that the PET bottle can be collected without removing the PE lid with respect to the removal of the PE lid, which is a problem in the collection of the PET bottle. Thereby, the rationalization of the collection process and the further increase in waste can be suppressed, which is of great significance both industrially and socially.

EXAMPLES Hereinafter, although an Example demonstrates this invention further more concretely, this invention is not limited only to these Examples ( Examples 1-21 and Examples 26-39 are reference examples ).

The compatibilizer used in the examples is shown below.
Compatibilizer I: 1: 9.6 (weight ratio) mixture of bisoxazoline (manufactured by Mikuni Pharmaceutical Co., Ltd.) and maleic anhydride modified PE (Yumex 2000, manufactured by Sanyo Kasei) Compatibilizer II: styrene ethylene butadiene styrene copolymer ( SEBS, manufactured by Asahi Kasei Kogyo)
Compatibilizer III: ethylene (88% by weight) -glycidyl methacrylate (12% by weight) copolymer compatibilizer IV: Neopolymer L-90 (manufactured by Nippon Oil Corporation)
Compatibilizer V: Ethylene special copolymer resin (Elvalloy, Mitsui / DuPont Polychemical)
Compatibilizer VI: Equal weight mixture compatibilization of ethylene-methacrylic acid copolymer ionomer (Himiran 1707Na, manufactured by Mitsui DuPont Polychemical) and ethylene (88 wt%)-glycidyl methacrylate (12 wt%) copolymer Agent VII: Acid-modified polyethylene wax (High Wax 2203A, manufactured by Mitsui Chemicals)
Compatibilizer VIII: ethylene (94 wt%)-glycidyl methacrylate (6 wt%) copolymer compatibilizer IX: compatibilizer I and ethylene-methacrylic acid copolymer ionomer (Himiran 1707Na, Mitsui DuPont Polychemical) Equal weight mixture with

[Example 1]
In Example 1, a recycled plastic material was produced using used PET and PE gas pipe waste material.
(1) Used PET flakes Collected PET bottles are washed with water, crushed into flakes with a pulverizer, washed with water, and dried (manufactured by PET bottle recycling company). It was.
(2) Recycled pellets of PE gas pipe waste The waste gas from PE gas pipe was pulverized and washed, and then re-pelletized (manufactured by Osaka Resin Kogyo) was used.

80 parts by weight of used PET flakes (manufactured by Yono PET Bottle Recycling Co., Ltd.), 20 parts by weight of recycled pellets of PE gas pipes (manufactured by Osaka Resin Kogyo), and 5 parts by weight of compatibilizer I are mixed into a twin-screw extruder ( Using a plastic engineering laboratory, BT-30-L, L / D = 30), the mixture was melt-kneaded and extruded into a strand shape to obtain a chip.
<Extrusion conditions>
Temperature setting: Feed 260 ° C, Kneading part 280 ° C, Head 260 ° C
Rotation speed: 60rpm

The obtained chip was injection-molded (injection molding machine: N100BII, L / D = 22, manufactured by Nippon Steel Works Co., Ltd.), and a test piece according to JIS K-7113 width 1/2 inch × length 8.5 Inch x 1/8 inch thick (A) and 1/4 inch wide x 5 inches long x 1/2 inch thick (B) were prepared (Example 1-1).
<Injection molding conditions>
Temperature setting: Feed 260 ° C, Nozzle 280 ° C, Mold 60 ° C
Injection pressure: 35-40 kg / cm ²

[Examples 2 to 6]
In Examples 2 to 6, two types of test pieces were prepared in the same manner as in Example 1 except that the types and amounts of the compatibilizers shown in Table 2 were used.

(Evaluation of recycled plastic materials)
-Measurement of tensile properties For each of the obtained test pieces (A), the tensile strength (MPa), tensile elastic modulus (MPa), and tensile elongation (%) were measured according to JIS K-7113. Distance between chucks: 115 mm, tensile speed: 50 mm / min, measurement atmosphere: temperature 23 ° C., relative humidity 50%
-Measurement of Izod impact strength (notched) For each of the obtained test pieces (B), Izod impact strength (J / m) was measured according to JIS K-7113. Notch shape: 45 ° V notch

[reference]
For reference, the above-described used PET flakes and recycled pellets of PE gas pipes were each independently molded in the same manner as in Example 1 to produce two types of test pieces, and the same measurements were performed. . These results are summarized in Table 2.

  From Table 2, the recycled materials of Examples 1 to 6 have good physical properties and can be applied as materials for various uses.

[Example 7: Multifilament]
100 parts by weight of the same used PET flakes (manufactured by Yono PET Bottle Recycle Co., Ltd.) and 3 parts by weight of compatibilizer I used in Example 1 were twin-screw extruder (manufactured by Technobell, KZW15-30MG) Was melt-kneaded in a conventional manner at 280 ° C., extruded and solidified in water with a diameter of about 3 mm, and then cut into 3 mm lengths to obtain mixed resin chips. The chip was dried with dehumidified dry air (dew point: −35 ° C.) at 120 ° C. to a moisture content of 80 ppm by weight. After drying, the chip was melted and wound up at a speed of 1000 m / min while being solidified by being extruded through 24 fine holes into cooling air. Next, the film was stretched 4 times at 90 ° C., set at 150 ° C. for a constant length, and wound up as a continuous fiber of 75 dTex. As a result, there was no yarn breakage during spinning or drawing unevenness during drawing, and a fiber excellent in quality was obtained.

[reference]
On the other hand, for comparison, the same operation as described above was carried out except that no compatibilizing agent was added. However, single yarn breakage during spinning and winding around the drawing / heat treatment roller occurred frequently.

[Example 8: Monofilament]
The same used PET flakes as used in Example 1 (manufactured by Yono PET Bottle Recycle) and compatibilizer I were dry blended with a composition of PET / Compatibilizer I = 100/5 (parts by weight), Using a biaxial kneader (Plastics Engineering Laboratory Co., Ltd., BT-30-L, L / D = 30), melt-kneaded at 280 ° C., extruded and solidified in water as a strand, and 3 mm long Cut to obtain a mixed resin chip. The mixed resin chip was dried with dehumidified dry air at 120 ° C. (dew point: −35 ° C.), and the moisture content was adjusted to 100 ppm by weight.

  The dried chip was melted at 260 ° C. in a single-screw kneader, discharged directly from a spinneret with a nozzle diameter of 1.2 mm and 18 holes, passed through 30 mm in the air, and adjusted to 60 ° C. Cooled and solidified by passing through a cooling bath, then stretched 6 times in 98 ° C hot water and further stretched 1.25 times in air at 210 ° C to a diameter of 0.21 mm (480 dTex) Monofilament was obtained. There were no yarn breakage during spinning or drawing unevenness during drawing, and a fiber excellent in quality was obtained.

  On the other hand, for comparison, the same operation as described above was carried out except that no compatibilizing agent was added. However, single yarn breakage during spinning and winding around the drawing / heat treatment roller occurred frequently.

[Example 9: Multifilament]
6 parts by weight of PE (Nipolon Hard 2500, manufactured by Tosoh Corp.), 94 parts by weight of the same used PET flake (manufactured by Yono PET Bottle Recycle) as used in Example 1, and 1 part by weight of Compatibilizer I are biaxial. Using an extruder (manufactured by Plastic Engineering Laboratory Co., Ltd., BT-30-L, L / D = 30), it is melt-kneaded by a conventional method at 280 ° C., and extruded and solidified in water at a diameter of about 3 mm. Then, it was cut to a length of 3 mm to obtain a mixed resin chip. The chips were dried with dehumidified dry air (dew point: −35 ° C.) at 120 ° C. to a moisture content of 60 ppm by weight. After drying, the chip was melted and wound up at a speed of 1000 m / min while being solidified by being extruded through 24 fine holes into cooling air. Next, the film was stretched 4 times at 80 ° C., set to 150 ° C. for constant length, and wound up as a continuous fiber of 75 dTex. Thus, the multifilament was produced (Example 9-1).

  Except for changing the type of compatibilizer to compatibilizer III (Example 9-2) or compatibilizer VI (Example 9-3) as shown in Table 3, the procedure was the same as in Example 9-1. Multifilaments were prepared respectively.

[Example 10: Multifilament]
As shown in Table 3, the amount of compatibilizer I (Example 10-1), compatibilizer III (Example 10-2), or compatibilizer VI (Example 10-3) is 5 parts by weight. A multifilament was produced in the same manner as in Examples 9-1, 9-2, and 9-3, except that.

[Example 11: Multifilament]
As shown in Table 3, the blending amount of the polymer was 20 parts by weight of PE (Nipolon Hard 2500, manufactured by Tosoh), 80 parts by weight of the same used PET flakes (manufactured by Yono PET Bottle Recycling) as used in Example 1, and A multifilament was produced in the same manner as in Examples 9-1, 9-2, and 9-3, except that.

[Comparative Examples 1 and 2]
As shown in Table 3, multifilaments were prepared in the same manner as in Example 9-1 or Example 11-1, except that no compatibilizer was added.

[Comparative Example 3]
A multifilament was produced in the same manner as Example 9-1 using only PET pellets (Dianite PA-500, manufactured by Mitsubishi Rayon).

(Spinnability)
In each of Examples 9-1 to 3, Example 10-1 to Example 1-3, and Example 11-1 to Example 1-3, good spinnability was obtained with no yarn breakage during spinning or stretching unevenness during stretching. On the other hand, in Comparative Examples 1 and 2, single yarn breakage during spinning and winding around the drawing / heat treatment roller frequently occurred. In Comparative Example 3, the spinnability and stretchability were good, but stains were seen on the die surface.

(Evaluation of multifilament)
About each produced multifilament, tensile strength (g / dTex) and elongation (%) were measured. In Examples 9-1 to 3, Examples 10-1 to 1-3, and Examples 11-1 to 1-3, fibers excellent in strength and elongation were obtained.

Each multifilament was evaluated for dyeability as follows.
The multifilament was dyed with high pressure by blue staining (Dianix ACE Blue, 3% owf), and K / S (630 nm) was measured. The dyeability was evaluated according to the following criteria.
○: K / S is 25 or more Δ: K / S is 20 or more and less than 25 x: K / S is less than 20

Moreover, KS / DS ratio was evaluated as follows about each multifilament.
KS: Nodule strength (MPa)
DS: Tensile strength (MPa)
Tensile speed: 20 cm / min

(Fiber surface observation)
The fiber surface of each produced multifilament was observed with SEM (scanning electron microscope). As a representative example, an SEM photograph of the fiber surface of Example 11-1 is shown in FIG. As shown in FIG. 1, long concave grooves (streaks) extending in the fiber length direction due to phase separation of the PET / PE components constituting the fibers were observed. Similar streaks were observed on the surfaces of the fibers of other examples. Because of this streak, the fibers of the present invention have a mild luster, a soft texture, a smooth touch, and good dyeability.

  The surface of the fiber of Comparative Example 3 was observed with SEM (FIG. 2). As shown in FIG. 2, a very smooth fiber surface characteristic of normal PET fibers was observed. Due to the smooth surface, this PET fiber has a lustrous gloss, a hard and crisp texture. In order to eliminate such disadvantages, in the production of PET fibers, when the fiber surface is large due to alkali weight reduction treatment, several tens of weight percent has been removed. However, alkali weight loss treatment is only a waste of resources. In addition, the negative effect on the wastewater was great, and it was not favorable in terms of resources and environment.

  Since the fiber of the present invention has a soft and soft texture, it is not necessary to carry out the alkali weight loss treatment, or even if it is carried out, a slight weight loss is sufficient. In this sense, the fiber of the present invention can be said to be an environment-friendly fiber.

  The above results are shown in Table 3.

[Example 12: Multifilament]
95 parts by weight of recovered food container PP (polypropylene), 5 parts by weight of PET (Dianite PA-500, manufactured by Mitsubishi Rayon) and 5 parts by weight of compatibilizer III were mixed with a twin-screw extruder (manufactured by Plastic Engineering Laboratory Co., Ltd.) BT-30-L, L / D = 30), melted and kneaded in a conventional manner at 280 ° C., extruded and solidified into water with a diameter of about 3 mm, then cut into 3 mm lengths, mixed resin chips Got. The chip was dried with 120 ° C. dehumidified dry air (dew point: −35 ° C.) to adjust the moisture content to 30 ppm by weight. After drying, the chip was melted and wound up at a speed of 1000 m / min while being solidified by being extruded through 24 fine holes into cooling air. Next, the film was stretched 3 times at 75 ° C., set to constant length heat at 130 ° C., and then wound as a continuous fiber of 75 dTex. There were no yarn breakage during spinning or drawing unevenness during drawing, and a fiber excellent in quality was obtained.

  The recovered food container PP used here is a recovered PP food container washed with water, pulverized into flakes by a pulverizer, and re-pelletized.

  On the other hand, for comparison, the same operation as described above was carried out except that no compatibilizing agent was added. However, single yarn breakage during spinning and winding around the drawing / heat treatment roller occurred frequently.

[Example 13: Monofilament]
Here, monofilaments were produced from recycled resin using used PET and used PE.
(1) Used PET flakes (same as Example 1)
The collected PET bottle was washed with water, pulverized into flakes by a pulverizer, washed with water, and dried (manufactured by Yoyobo Bottle Recycling Co., Ltd.).
(2) Recycled pellets of used PE The collected PE container was washed with water and pulverized into flakes by a pulverizer. This was washed with water, dried, re-pelletized, and regenerated pellets were obtained.

  The same 2 as used in Example 1 was obtained by dry blending compatibilizer I with PET / PE / compatibilizer I = 90/10/5 (parts by weight) together with used PET flakes and PE recycled pellets. Using a shaft kneader, the mixture was melt-kneaded at 280 ° C., extruded and solidified in water as a strand, and then cut into 3 mm lengths to obtain mixed resin chips. The mixed chip was dried with dehumidified dry air (dew point: −35 ° C.) at 120 ° C. to adjust the moisture content to 150 ppm by weight.

  The dried chip was melted at 260 ° C. in a single-screw kneader, discharged directly from a spinneret with a nozzle diameter of 1.2 mm and 18 holes, passed through 30 mm in the air, and adjusted to 60 ° C. The mixture was cooled and solidified by passing through a cooling bath, and then stretched by one step 6 times in hot water at 98 ° C. and further stretched 1.25 times in air at 210 ° C. to obtain a monofilament. A fiber excellent in quality was obtained with no yarn breakage during spinning or drawing unevenness during drawing (Example 13-1).

  A monofilament was produced in the same manner as in Example 13-1, except that the blending amount was changed to PET / PE / Compatibilizer I = 80/20/1 (parts by weight). There were no stretch marks at the time, and a fiber excellent in quality was obtained (Example 13-2).

  A monofilament was produced in the same manner as in Example 13-1, except that the compatibilizer was changed to compatibilizer III (Example 13-3) or compatibilizer V (Example 13-4), respectively. There was no yarn breakage at the time and no stretch spots at the time of drawing, and a fiber excellent in quality was obtained.

  On the other hand, for comparison, the same operation as described above was carried out except that no compatibilizing agent was added. However, single yarn breakage during spinning and winding around the drawing / heat treatment roller occurred frequently.

[Example 14: Spunbond]
In the same manner as in Example 13-1, used PET flakes, PE recycled pellets and compatibilizer I were dry blended with a composition of PET / PE / compatibility agent I = 90/10/5 (parts by weight), A mixed resin chip was obtained. The mixed chip was dried with dehumidified dry air (dew point: −35 ° C.) at 120 ° C. to adjust the moisture content to 70 ppm by weight.

The dried chip was melted and extruded from a die having 2000 holes with a diameter of 0.35 mm into cooling air, cooled through an air ejector having a speed of 3600 m / min, and sprayed on a net conveyor moving forward. . The blown fibers were weakly fused together, resulting in a web with a soft texture. Then, it is pressed between a metal embossing roller (crimp area ratio: 19%) held at 130 ° C. and a flat roller held at room temperature, and partially pressurized and heated and melted. A spunbonded nonwoven fabric having a weight per unit area of 30 g / m ² having excellent wearing strength was obtained. The obtained non-woven fabric had a single yarn denier of 0.9 dTex, and had a soft texture, appropriate elongation, and sufficient strength (Example 14-1).

  Except for changing the type of the compatibilizer to compatibilizer III (Example 14-2) or compatibilizer V (Example 14-3), each of the spunbond nonwoven fabrics was the same as Example 14-1. Produced. Each of the obtained nonwoven fabrics had a single yarn denier of 0.9 dTex, and had a soft texture, moderate elongation, and sufficient strength.

  On the other hand, for comparison, the same operation as described above was carried out except that no compatibilizing agent was added. However, single yarn breakage occurred frequently during spinning, and a poor-quality web with a lot of fluff and unevenness was obtained. Therefore, the practicality was very low.

[Example 15: Flat yarn]
5 parts by weight of PE (Nipolon Hard 2500, manufactured by Tosoh Corp.), 95 parts by weight of the same used PET flake (manufactured by Yono PET Bottle Recycle Co.) as used in Example 1 and 5 parts by weight of Compatibilizer I are biaxial. Using an extruder (manufactured by Plastic Engineering Laboratory Co., Ltd., BT-30-L, L / D = 30), it is melt-kneaded by a conventional method at 280 ° C., and extruded and solidified in water at a diameter of about 3 mm. Then, it was cut to a length of 3 mm to obtain a mixed resin chip. The chip was dried with dehumidified dry air (dew point: −35 ° C.) at 120 ° C. to a moisture content of 80 ppm by weight. Using the obtained mixed resin chip (water content: 80 wt ppm), air was blown from the outside and inside from a melt extruder having a commonly used annular die, followed by cooling and ballooning to perform extrusion molding. The extruded cylindrical sheet is folded into a sheet, then cut to a width of 5 mm, then preheated at a constant length while in contact with a hot plate maintained at 70 ° C., and then on an 80 ° C. hot plate And stretched 3.5 times. Subsequently, while shrinking by 2% on a hot plate maintained at 160 ° C., it was heat-fixed and wound up on a predetermined arn to obtain a flat yarn (Example 15-1).

  A flat yarn was prepared in the same manner as in Example 15-1, except that the type of the compatibilizer was changed to Compatibilizer III (Example 15-2) or Compatibilizer V (Example 15-3). did.

  The flat yarn obtained from PET alone is relatively brittle and easy to break in the longitudinal direction due to the excessive orientation of PET when the draw ratio is large, but the flat yarn obtained in Examples 15-1 to 3 is a PET component. The brittleness was improved by the PE component dispersed therein, making it difficult to break, and durability in use was also improved.

  On the other hand, for comparison, the same operation as described above was performed except that no compatibilizing agent was added, but uniform extrusion from the die was not possible, and uneven resin was seen in the circumferential direction and flow direction. It was. For this reason, it cannot be sufficiently inflated with air, and non-uniform stretching or breakage in the middle occurs, resulting in poor productivity, quality and quality.

[Example 16: Tubular extruded product]
The same spent PET flakes used in Example 1 were used.
100 parts by weight of used PET flakes, 10 parts by weight of compatibilizer VI, and 1 part by weight of black PBF-640 (LDPE base, manufactured by Resinocolor Kogyo Co., Ltd.) as a colorant are melted at 290 ° C. in a twin-screw kneader. After kneading, it was extruded and solidified into a strand shape, and cut into 3 mm lengths to obtain colored chips. The obtained chip was dried to a moisture content of 200 ppm by weight with dehumidified dry air (dew point: −35 ° C.) at 120 ° C., and then melted in a uniaxial kneader with an inner diameter of 25 mm, an outer diameter of 25 mm, an inner diameter of 20 mm, A continuous pipe was obtained by extruding into a water from a circular die having a thickness of 2.5 mm. A pipe having a smooth and uniform appearance was obtained (Example 16-1).

  A continuous pipe was produced in the same manner as in Example 16-1, except that the amount of the compatibilizer VI was changed to 5 parts by weight. As a result, a smooth and uniform pipe was obtained (Example 16-). 2).

  On the other hand, for comparison, the same operation as described above was performed except that no compatibilizing agent was added, but due to non-uniformity due to phase separation, the appearance was slightly uneven, and hammering was performed. It was also insufficient in physical properties such as being easily damaged.

[Example 17: Tubular extruded product]
Here, a recycled resin molded body was produced using the same used PET flakes (manufactured by Yoko PET Bottle Recycle Co.) as used in Example 1 and recycled pellets of PE gas tubes (Osaka Resin Industry Co., Ltd.).

  60 parts by weight of used PET flakes, 40 parts by weight of recycled pellets of PE gas pipe, 15 parts by weight of compatibilizer I, and 1 part by weight of black PBF-640 (LDPE base, manufactured by Resino Color Industries Co., Ltd.) as a colorant After melt-kneading at 290 ° C. with a twin-screw kneader, it was extruded and solidified into a strand shape and cut into 3 mm lengths to obtain colored chips. The obtained chip was dried with dehumidified dry air (dew point: −35 ° C.) at 120 ° C. to adjust the moisture content to 200 ppm by weight. Thereafter, the chip was melted in a single-screw kneader having an inner diameter of 25 mm, and extruded from a circular die having an outer diameter of 25 mm, an inner diameter of 20 mm, and a thickness of 2.5 mm to obtain a continuous pipe. A pipe having a smooth and uniform appearance was obtained.

  On the other hand, for comparison, the same operation as described above was performed except that no compatibilizing agent was added, but due to non-uniformity due to phase separation, the appearance was slightly uneven, and hammering was performed. It was also insufficient in physical properties such as being easily damaged.

[Example 18: Steel sheet laminate compact]
In this example, a hot-dip galvanized steel sheet having a thickness of 0.35 mm, whose surface was previously coated with a urethane primer, was used as the substrate. The same used PET flakes as used in Example 1 (manufactured by Yono PET Bottle Recycle Co., Ltd.) and recycled pellets of PE gas pipes (manufactured by Osaka Resin Industry Co., Ltd.) were used.

  Add 1 part by weight of blue pigment (Nagase Sangyo, CROMOPHTAL (Blue 4GNP)) to a mixed chip of recycled pellets / compatibility agent IX = 85/15/5 (parts by weight) of a used PET / PE gas pipe Then, melt and knead at 290 ° C with a uniaxial extruder with an inner diameter of 25 mm, extrude from a T-die with a slit width of 0.2 mm and a width of 50 cm, and adjust the air gap to the substrate on the primer surface of the substrate. Lamination was followed by pressing and cooling with a press roller to obtain a steel plate / resin laminate decorative plate. The laminated resin layer had a thickness of about 0.17 mm and a uniform appearance with excellent gloss. Moreover, in order to evaluate the strength of adhesion (adhesion), JIS K5400 (cross-cut tape peeling test) was carried out, but there was no problem at all. Further, a bending test of JIS Z2204 was carried out, but no cracks were seen up to t = 3 mm, and the performance was good.

  On the other hand, for comparison, the same operation as described above was performed except that no compatibilizing agent was added, but the obtained laminate molded body had a dull gloss and slight unevenness on the surface, and the quality was low. It was a thing.

[Example 19: Film molded body]
In this example, the same recycled pellets (made by Osaka Resin Co., Ltd.) of PE gas pipes used in Example 1 were used. The recovered PBT (polybutylene terephthalate) is obtained by washing the recovered PBT case molded product with water, then pulverizing it with a pulverizer and re-pelletizing it.

  Recycled pellets of recovered PBT / PE gas pipes / mixing tips of compatibilizer VI = 85/15/5 (parts by weight) were melt-kneaded at 290 ° C. in a single screw extruder with an inner diameter of 25 mm, and a slit width of 0. The film was extruded from a T-die having a width of 2 mm and a width of 50 cm, and pressed and cooled with a press roller to obtain a film molded body. The obtained film had a thickness of about 0.15 mm and a uniform appearance excellent in gloss.

  On the other hand, for comparison, a film molded body was obtained in the same manner as above except that no compatibilizing agent was added. However, the obtained film molded body showed dull gloss and slight irregularities on the surface. The quality was low.

[Example 20: Film molded body]
In this example, the collected medical nylon PE laminated film (nylon: PE = 75: 25) was used. As the collected nylon PE laminated film for medical use, the collected nylon PE laminated film for medical use was washed with water and then pulverized by a pulverizer.

  A mixed chip of recovered nylon PE laminated film / compatibilizer V = 100/5 (parts by weight) was melt-kneaded at 290 ° C. with a single-screw extruder having an inner diameter of 25 mm, and a T-die having a slit width of 0.2 mm and a width of 50 cm. The film was further extruded and pressed and cooled with a press roller to obtain a film molded body. The resulting film exhibited a uniform appearance with excellent gloss.

  On the other hand, for comparison, an attempt was made to obtain a film molded body by the same operation as above except that no compatibilizer was added, but a film could not be obtained.

[Example 21: Film molded body]
In this example, the same used PET as used in Example 1 and the same recovered food container PP as used in Example 12 were used.

  A mixed chip of used PET / recovered food container PP / compatibilizer IX = 85/15/5 (parts by weight) was melt-kneaded at 290 ° C. with a single-screw extruder having an inner diameter of 25 mm and a slit width of 0.2 mm. The film was extruded from a T-die having a width of 50 cm and pressed and cooled with a press roller to obtain a film molded body. The obtained film had a thickness of about 0.15 mm and a uniform appearance excellent in gloss.

  On the other hand, for comparison, a film molded body was obtained in the same manner as above except that no compatibilizing agent was added. However, the obtained film molded body showed dull gloss and slight irregularities on the surface. The quality was low.

[Examples 22 to 25, Comparative Examples 4 to 7: Inflation film]
The same spent PET flakes used in Example 1 were used.
In these examples and comparative examples, used PET flakes, PE (Nipolon-L FS150, manufactured by Tosoh Corporation) and a compatibilizer were each dry blended at a blending weight ratio shown in Table 4, and a twin-screw kneader (Plastic Co., Ltd.). Kneaded at 260 ° C. with BT-30-L, L / D = 30) manufactured by Engineering Research Laboratory, then extruded and solidified in water with a diameter of about 3 mm, then cut into 3 mm lengths, and mixed resin chips I got each. Each chip was dried with dehumidified dry air (dew point: −35 ° C.) to adjust the moisture content to 100 ppm by weight or less.

  Using each of the dry chips, an inflation film was produced as usual. First, the chips were melt-kneaded by a single-screw kneader having a temperature gradient suitable for melting each chip and extruded from a circular die having a diameter of 85 mm. The BUR (blow ratio) was changed by adjusting the internal pressure. The film thickness was adjusted to 25 μm by adjusting the extrusion amount. In this way, each of the inflation films was produced.

  The results are shown in Table 4. In all the examples, the film formation state was good, and the obtained film was also good. The melt viscosity η (poise) is a value measured at 280 ° C. and a shear rate of 100 (1 / sec) using Capillograph 1B (capillary size: L = 10 mm, D = 0.5 mm) manufactured by Toyo Seiki Co., Ltd. With only the used PET of Comparative Example 4, the melt viscosity at the film forming temperature was not sufficient, and the film could not be lifted and blown. In Examples 22 to 25, melt viscosity was increased by blending PE with used PET using a compatibilizing agent and alloying, and the film startup and blow stretching were achieved uniformly and satisfactorily.

In Table 4, symbols for the film forming state are as follows.
○: Blowability is good.
Δ: Blowability failure.
X: The film could not be lifted.

In Table 4, symbols for the film state are as follows.
○: Slightly opaque, but soft, soft and smooth.
Δ: Film formation was possible, but foreign matter was observed in some places.
X: Film formation failure.

(Evaluation of film)
About each produced inflation film, the heat seal intensity | strength, the contact angle with respect to water, and surface property were evaluated as follows. The results are summarized in Table 4.

1. Heat seal strength Two strips of 10 mm × 100 mm strips were cut out from the obtained films. Two strip-shaped test pieces were overlapped, and a portion having a distance of 10 mm from one end was linearly fused with a desktop vacuum sealer (Saran Wrap Sales Co., Ltd., desktop sealed packaging machine). Thereafter, the other ends that were not fused were pulled using a tensile tester under the condition of a tensile speed of 100 mm / min, and the fracture load (kN) of the fused portion was measured.

  As shown in Table 4, it was confirmed that all of the films of the present invention were superior in heat seal strength to the PET single film of Comparative Example 4, and thus were suitable for bags.

  Conventionally, a film using PET as a raw material has a problem that heat seal strength is weak. In the present invention, one or a plurality of types of resins other than PET that are excellent in heat sealability with respect to PET (PE in this example) and a compatibilizing agent are mixed at an arbitrary ratio, and this mixed resin material is used. This problem was solved by forming a film.

2. Contact angle About each obtained film, the contact angle with respect to water was measured. As shown in Table 4, a high contact angle was obtained for any of the films of the present invention compared to the PET film.

  A film made of PET as a raw material has a small contact angle with water and is hydrophilic. However, in the present invention, one or more kinds of resins other than PET that are hydrophobic with respect to PET (PE in this example) and a compatibilizing agent are mixed in an arbitrary ratio, and this mixed resin material is mixed. By forming a film, a film having a high contact angle was obtained.

3. Surface properties It is preferable to optimize the properties of the film surface according to the application. For example, in the use of thin bags such as garbage bags and shopping bags, from the viewpoint of operability in the manufacturing stage and stability during packaging and storage, and from the viewpoint of gloss, appearance, slipperiness, opening, printability, etc. The film preferably has some surface irregularities.

For example, in this application, the film has at least 1,000, preferably 2,000 to 8,000, more preferably 3,000 to 5,000 convex shapes with a width of 1 to 10 μm and a height of 0.5 to 5 μm per 1 mm ² of the surface. Good. This degree of surface convexity provides the advantage of having smooth slipperiness and maintaining a stable shape when many are stacked, and being excellent in operability during use. Of course, even if it is not the surface convex number of this range, use is possible. If the convex height is lower than 0.5 μm, the effect is small, and if it is higher than 5 μm, physical properties such as the strength of the film tend to be lowered.

  In conventional HDPE (high density polyethylene) films, an anti-blocking agent is blended to ensure operability at the manufacturing stage and stability during packaging and storage. As a result, the anti-blocking agent migrates to the surface over time, causing film surface contamination and haze. Further, the anti-blocking agent was removed, and blocking was likely to occur.

  In the present invention, the unevenness of the film surface can be controlled by an appropriate combination of one or more resins and a compatibilizer, that is, the film has antiblocking properties due to the physical effect of the unevenness of the film surface. Can be granted. Therefore, the film surface is not contaminated by the antiblocking agent, is hygienic, and the antiblocking property can be maintained semipermanently. The convex portion is likely to be generated by lowering the film forming temperature, but if the forming temperature is too low, the film strength and the like are likely to be lowered. Therefore, the melt-kneading temperature at the time of film formation is preferably 220 to 280 ° C. For example, in the case of a PE rich film, 225 to 265 ° C. is preferable for improving the antiblocking property. In addition, the unevenness | corrugation of the surface of a film can be evaluated using SEM (scanning electron microscope), a laser microscope, AFM (atomic force microscope), a stylus type surface roughness meter, etc.

The number of convex shapes per 1 mm ^{2 of} each film surface obtained was determined as follows. Five locations on the film surface were arbitrarily selected, and the number of convex shapes having a height of 0.5 to 5 μm in a range of 50 μm in length was counted for each of the film MD direction and the TD direction using a laser microscope. The average value of the number of convex shapes in each of the MD direction and the TD direction was obtained. The number per 1 mm ^{2 of} the film surface was calculated by multiplying the average number of convex shapes in the MD direction and the TD direction, respectively.

As shown in Table 4, each of the films of the present invention had an appropriate number of convex surfaces and had excellent antiblocking properties. When the same measurement was performed on a commercially available polyethylene film containing an antiblocking agent molded only from HDPE (high density polyethylene), the number of protrusions per 1 mm ^{2 of} the film surface was 4600.

[Example 26: Alkali resistance of film molded product]
A film made of PET as a raw material has a problem that alkali resistance is weak. However, in the present invention, one or a plurality of other resins (for example, PE) that are excellent in chemical resistance than PET and a compatibilizer are mixed at an arbitrary ratio, and this mixed resin material is used as a film. When converted, a film excellent in alkali resistance can be obtained.

  The same used PET flakes as used in Example 1 and PE (Nipolon-L FS150, manufactured by Tosoh Corporation) were used.

  Spent PET / PE / Compatibilizer III = 70/30/3, 50/50/10, or 25/75/3 (parts by weight) of mixed chips were each 290 ° C. in a single screw extruder having an inner diameter of 25 mm. Were melt-kneaded, extruded from a T-die having a slit width of 0.2 mm and a width of 50 cm, pressed and cooled with a press roller, and three types of film molded bodies were obtained. Each of the obtained films was immersed in a 4 wt% aqueous sodium hydroxide solution at 23 ° C for 1 hour. There was no abnormality in any film.

  Further, six types of film molded bodies were prepared in the same manner as described above except that the type of the compatibilizer was changed to the compatibilizer V or the compatibilizer VI. Each of the obtained films was immersed in a 4 wt% aqueous sodium hydroxide solution at 23 ° C for 1 hour. There was no abnormality in any film.

  On the other hand, for comparison, a film molded body was obtained from PET pellets (Dianite PA-500, manufactured by Mitsubishi Rayon) only by the same operation as described above. When the PET film was immersed in a 4% by weight aqueous sodium hydroxide solution at 23 ° C. for 1 hour, cracks occurred.

[Example 27: Injection molded product]
The same spent PET flakes used in Example 1 were used.
100 parts by weight of used PET flakes and 3 parts by weight of compatibilizer I were melt-kneaded in a conventional manner at 280 ° C. using a twin-screw extruder (manufactured by Technobell, KZW15-30MG), about 3 mm Was extruded and solidified in water at a diameter of 3 mm, and then cut into 3 mm lengths to obtain mixed resin chips. The obtained chip was injection molded under the same conditions as in Example 1 to obtain an injection molded product. The obtained molded article was improved in tensile strength and elongation as compared with a molded article obtained only from used PET flakes without using a compatibilizing agent.

[Examples 28 to 30: Fiber-reinforced injection molded products]
The same used PET flakes used in Example 1 and recycled pellets of PE gas tubes were used.
In these examples, used PET flakes, recycled pellets of PE gas pipes, glass fibers (for PET PBT, 13 μm diameter, manufactured by Nittobo), and a compatibilizer are each dry blended at a blending weight ratio shown in Table 5. Kneading at 260 ° C. with a twin-screw kneader (Technobel Co., Ltd., KZW15-30MG), then extruding and solidifying in water with a diameter of about 3 mm, then cutting to 3 mm length, Obtained. Each chip was dried with a dehumidifying dryer until the moisture content in the chip became 150 ppm by weight or less.

  An injection-molded test piece according to JIS K-7054 was produced using each dry chip. About each obtained test piece, the tensile strength (MPa), the bending elastic modulus (MPa), and elongation (%) were measured according to JIS K-7054. The results are shown in Table 5. All the test pieces exhibited excellent physical property values.

[Example 31: Injection molded product containing wood powder]
The same spent PET flakes used in Example 1 were used.
The surface polishing litter wood powder of the South Sea wood veneer was sieved to obtain a mixture of 14 to 100 mesh fiber length of 70% by weight and 100 mesh or more fiber length of 30% by weight. This wood flour mixture was pre-dried and the moisture content was adjusted to 2% by weight. 55 parts by weight of this wood flour mixture, 8 parts by weight of PE resin (manufactured by JPO, AE089L), 32 parts by weight of used PET flakes, 0.5 parts by weight of compatibilizer I, 5 parts by weight of silica and 5 parts by weight of barium sulfate Were mixed and put into a super mixer at a time and stirred at high speed. This mixture was heat-kneaded using a twin-screw extruder and pelletized. The obtained pellets were dried to a moisture content of 0.3% by weight using a hot air circulating oven, and injection molded using an injection molding machine and a test mold. The injection temperature was set at 280 ° C. Of the molded specimens, 5 shots of 5th shot, 10th shot, 15th shot, 20th shot and 25th shot are extracted, and a tensile test and a bending test are performed to obtain an average value of the 5 test pieces. It was. The tensile strength was 37 MPa, the bending strength was 81 MPa, and the flexural modulus was 6170 MPa.

[Example 32: Injection molded product containing wood powder]
Instead of 8 parts by weight of PE resin (manufactured by JPO, AE089L), the same operation as in Example 31 was repeated except that 8 parts by weight of recycled pellets of the same PE gas pipe used in Example 1 were used. . The tensile strength was 33 MPa, the bending strength was 71 MPa, and the bending elastic modulus was 6450 MPa.

[Example 33: Masterbatch method and compound method]
(Master batch method)
A used PET chip obtained by re-pelletizing the same used PET flakes as used in Example 1 was used.
30 parts by weight of PE (T240E, manufactured by Tosoh) and 3 parts by weight of compatibilizing agent I were dry blended and mixed into a twin-screw kneader (manufactured by Plastic Engineering Laboratory Co., Ltd., BT-30-L, L / D = 30). The mixture was then kneaded at 260 ° C., then extruded and solidified in water with a diameter of about 3 mm, and then cut into 3 mm lengths to obtain master chips. 70 parts by weight of used PET chip and 33 parts by weight of the master chip are dry blended and dried with a dehumidifying dryer until the moisture content in the chip is 150 ppm by weight or less, and an injection molding test piece in accordance with JIS K-7054 Was made. In this way, the test piece No. M-1 was obtained.

  Further, except that the master chip formulation was changed to PE / Compatibilizer I = 75/3 parts by weight and 25 parts by weight of the used PET flakes and 78 parts by weight of the master chips were dry blended, the same as above, An injection molded test piece was produced. In this way, Specimen No. M-2 was obtained.

  Specimens No. M-3 to No. M-10 were prepared in the same manner as above except that the type of the compatibilizer was changed to Compatibilizer II, III, V, or VI as shown in Table 6. did.

(Compound method)
The same spent PET flakes used in Example 1 were used.
Used PET flakes, PE (T240E, manufactured by Tosoh Corporation) and a compatibilizing agent are each dry blended at a blending weight ratio shown in Table 6 and a biaxial kneader (manufactured by Plastic Engineering Laboratory Co., Ltd., BT-30-L, L / D = 30), and kneaded at 260 ° C., then extruded and solidified in water with a diameter of about 3 mm, and then cut into 3 mm lengths to obtain mixed resin chips, respectively. Each chip was dried with a dehumidifying dryer until the moisture content in the chip became 150 ppm by weight or less, and injection molded test pieces No. C-1 to No. C-10 according to JIS K-7054 were produced. .

  About each obtained test piece, the tensile strength (MPa) was measured according to JISK-7054. The results are shown in Table 6. If the composition was the same, the test specimens by both the master batch method and the compound method showed similar physical property values.

[Example 34: Inflation film by masterbatch method]
The same spent PET flakes used in Example 1 were used.
70 parts by weight of used PET flakes, 30 parts by weight of PE (T240E, manufactured by Tosoh) and 3 parts by weight of compatibilizer I were dry blended, and a twin-screw kneader (manufactured by Plastic Engineering Laboratory Co., Ltd., BT-30-L). , L / D = 30), kneaded at 260 ° C., and then extruded and solidified in water with a diameter of about 3 mm, and then cut into 3 mm lengths to obtain mixed resin chips. The chip was dried with a dehumidifying dryer until the moisture content in the chip became 150 ppm by weight or less. 50 parts by weight of used PET flakes were dry blended in a dry atmosphere to 100 parts by weight of the obtained dry chip, and an inflation film was produced as usual. First, the chips were melt-kneaded by a single-screw kneader having a temperature gradient suitable for melting each chip and extruded from a circular die having a diameter of 85 mm. The BUR (blow ratio) was changed by adjusting the internal pressure. The film thickness was adjusted to 25 μm by adjusting the extrusion amount. The film formation state was good and the film obtained was also good.

[Example 35: Inflation film by masterbatch method]
The same spent PET flakes used in Example 1 were used.
30 parts by weight of used PET flakes, 70 parts by weight of PE (T240E, manufactured by Tosoh) and 5 parts by weight of compatibilizer I were dry blended, and a twin-screw kneader (manufactured by Plastic Engineering Laboratory Co., Ltd., BT-30-L). , L / D = 30), kneaded at 260 ° C., and then extruded and solidified in water with a diameter of about 3 mm, and then cut into 3 mm lengths to obtain mixed resin chips. The chip was dried with a dehumidifying dryer until the moisture content in the chip became 150 ppm by weight or less. 50 parts by weight of PE (T240E, manufactured by Tosoh Corp.) was dry blended in a dry atmosphere to 100 parts by weight of the obtained dry chip, and an inflation film was produced as usual. First, the chips were melt-kneaded by a single-screw kneader having a temperature gradient suitable for melting each chip and extruded from a circular die having a diameter of 85 mm. The BUR (blow ratio) was changed by adjusting the internal pressure. The film thickness was adjusted to 25 μm by adjusting the extrusion amount. The film formation state was good and the obtained film was also good (Example 35-1).

  Inflation films were prepared in the same manner as in Example 35-1, except that the type of the compatibilizer was changed to Compatibilizer III (Example 35-2) or Compatibilizer VI (Example 35-3). did. In all cases, the film formation state was good, and the obtained film was also good.

[Example 36: Inflation film by masterbatch method]
The same spent PET flakes used in Example 1 were used.
50 parts by weight of used PET flakes, 50 parts by weight of PE (T240E, manufactured by Tosoh Corp.) and 10 parts by weight of compatibilizer I were dry blended, and 260 ° C. in a biaxial kneader (manufactured by Technovel, KZW15-30MG). After that, it was extruded and solidified in water with a diameter of about 3 mm, and then cut into a length of 3 mm to obtain a mixed resin chip. The chip was dried with a dehumidifying dryer until the moisture content in the chip became 150 ppm by weight or less. 100 parts by weight of PE (T240E, manufactured by Tosoh Corp.) was dry blended in a dry atmosphere to 100 parts by weight of the obtained dry chip, and an inflation film was produced as usual. First, the chips were melt-kneaded by a single-screw kneader having a temperature gradient suitable for melting each chip and extruded from a circular die having a diameter of 85 mm. The BUR (blow ratio) was changed by adjusting the internal pressure. The film thickness was adjusted to 48 μm by adjusting the extrusion amount. The film formation state was good, the resulting film was also good in appearance, and the slipperiness of the film was good even without using an antiblocking agent (Example 36-1).

  Inflation films were produced in the same manner as in Example 36-1, except that the type of the compatibilizer was changed to Compatibilizer III (Example 36-2) or Compatibilizer VI (Example 36-3). did. In any case, the film formation state was good, the obtained film had good appearance, and the slipperiness of the film was good even without using an antiblocking agent.

[Example 37: Multifilament by masterbatch method and compound method]
Using used PET, multifilaments were produced from materials having the same composition (PET / PE / compatibility agent = 90/10/1) by the masterbatch method and the compound method, respectively.

(Master batch method)
100 parts by weight of PE (Nipolon Hard 2500, manufactured by Tosoh) and 10 parts by weight of compatibilizer I were dry blended, and a twin-screw kneader (manufactured by Plastic Engineering Laboratory Co., Ltd., BT-30-L, L / D = 30) Was then kneaded at 200 ° C. and then extruded and solidified in water with a diameter of about 3 mm, and then cut into 3 mm lengths to obtain mixed resin chips. The chip was dried with a dehumidifying dryer until the moisture content in the chip reached 150 ppm by weight or less, and then further dried with dehumidified dry air at 110 ° C. (dew point: −35 ° C.) to a moisture content of 80 ppm by weight. 90 parts by weight of the same used PET chip as used in Example 33 was dry-blended in 11 parts by weight of the obtained dry chip in a dry atmosphere, and after drying, extruded into cooling air from 24 fine holes and solidified. However, it wound up at a speed of 1000 m / min. Next, the film was stretched 4 times at 85 ° C., and heat-set at a constant length at 150 ° C., and then wound as a continuous fiber of 75 dTex. In this way, a multifilament was produced (Example 37-1).

(Compound method)
100 parts by weight of the same used PET flakes as used in Example 1, 10 parts by weight of PE (Nipolon Hard 2500, manufactured by Tosoh Corp.) and 1 part by weight of compatibilizer I were dry blended, and a twin-screw kneader (Plastic Co., Ltd.) Kneaded at 260 ° C. with BT-30-L, L / D = 30) manufactured by Engineering Research Laboratory, then extruded and solidified in water with a diameter of about 3 mm, then cut into 3 mm lengths, and mixed resin chips Obtained. The chip was dried with a dehumidifying dryer until the moisture content in the chip reached 150 ppm by weight or less, and then further dried with dehumidified dry air at 110 ° C. (dew point: −35 ° C.) to a moisture content of 80 ppm by weight. After drying, the chip was melted and wound up at a speed of 1000 m / min while being solidified by being extruded through 24 fine holes into cooling air. Next, the film was stretched 4 times at 85 ° C., and heat-set at a constant length at 150 ° C., and then wound as a continuous fiber of 75 dTex. Thus, the multifilament was produced (Example 37-2).

  In any of the above Examples 37-1 and 37-2, the viscosity at the time of melting is improved as compared with the used PET used in [Reference] of Example 7, and the yarn breakage during spinning or stretching during stretching Good spinnability with no spots was obtained, and fibers excellent in strength and elongation were obtained. In Example 37-1, the tensile strength was 3.43 g / dTex and the elongation was 56.8%. In Example 37-2, the tensile strength was 3.65 g / dTex and the elongation was 55.0%.

  A multifilament was produced in the same manner as in Example 37-1, except that the compatibilizer was changed to compatibilizer III (Example 37-3) or compatibilizer V (Example 37-4), respectively. There was no yarn breakage during spinning or drawing irregularities during drawing, and good spinnability was obtained.

  Moreover, the multifilament was produced like Example 37-2 except having changed the compatibilizer into the compatibilizer III (Example 37-5) or the compatibilizer V (Example 37-6), respectively. However, there was no yarn breakage at the time of spinning and no drawing unevenness at the time of drawing, and good spinnability was obtained.

[Example 38: Recycled plastic material from various polymers]
In this example, recycled plastic materials from various polymers were made. The polymer materials used are as follows.

(1) Used PET flakes The same used PET flakes as used in Example 1 (manufactured by Yono PET Bottle Recycle) were used.
(2) Recycled pellets of PE gas pipe waste material The same recycled pellets of PE gas pipe waste material as used in Example 1 (manufactured by Osaka Plastic Industry Co., Ltd.) were used.
(3) Recycled pellets of PP food containers The same recovered pellets of PP food containers as used in Example 13 were used.
(4) Used PA (polyamide)
The collected nylon food packaging film was washed with water and pulverized with a pulverizer.
(5) Recycled pellets of used PS (polystyrene) The recovered polystyrene beverage cup was subjected to volume reduction treatment, washed with water, pulverized with a pulverizer, and re-pelletized.
(6) Recycled pellets of used PC (polycarbonate) The recovered polycarbonate outdoor transparent sheet was washed with water, pulverized with a pulverizer, and re-pelletized.

  In this example, a plurality of polymer materials and compatibilizers were blended in the blending weight ratios shown in Table 7 in the same manner as in Example 1. A twin-screw extruder (manufactured by Plastic Engineering Laboratory, BT-30-L, L / D = 30) is melt kneaded at 280 ° C., extruded into strands to obtain chips, and the obtained chips are injection-molded (injection molding machine: manufactured by Nippon Steel Works, N100BII, L / D D = 22), and a test piece (A) based on JIS K-7113 was produced. About each obtained test piece No. 38-1-No. 38-11, it carried out similarly to Example 1, and measured tensile strength (MPa) and tensile elongation rate (%).

  For comparison, test pieces (A) No. 38-R-1 to No. 38-R-3 containing no compatibilizer were prepared, and similarly, tensile strength (MPa) and tensile elongation were obtained. (%) Was measured. The results are shown in Table 7.

  From Table 7, the recycled materials of the examples have good physical properties and can be applied as materials for various uses.

[Example 39: Flame retardancy]
In this example, flame-retarded recycled resin molding using the same used PET flakes (Yono PET Bottle Recycling Co., Ltd.) and PE gas pipe recycled pellets (Osaka Resin Kogyo Co., Ltd.) used in Example 1 were used. The body was made. The flame retardants used were magnesium hydroxide (Kyowa Chemical, Kisuma 5A), expanded graphite (Sumikin Chemical, 8099M), red phosphorus (Nihon Chemical, Hishigard TP10), PET red phosphorus master batch (Nihon Chemical, red 15% PET masterbatch), brominated flame retardant SAYTEXBT-93 (Albemarle), brominated flame retardant SAYTEX 8010 (Albemarle), antimony trioxide (Nippon Seiko Co., Ltd., PATOX-M), boric acid Zinc (made by Nippon Seiko Co., Ltd.).

At each blending weight ratio shown in Table 8, used PET flakes, recycled pellets of PE gas pipes, compatibilizer III and various flame retardants were mixed into a twin-screw extruder (manufactured by Plastic Engineering Laboratory Co., Ltd., BT-30- L, L / D = 42) were melt-kneaded and extruded into strands to obtain chips (chips Nos. 39-1 to 39-6).
<Extrusion conditions>
Set temperature: Feed 180 ° C, Kneading part 210 ° C, Head 180 ° C
Rotation speed: 100rpm

Each obtained chip was injection molded (injection molding machine: N100BII, L / D = 22, manufactured by Nippon Steel Works, Ltd.), No. 1 test piece (A) based on JIS K-7113, JIS K-7201. Type I test piece (C) compliant with UL, and a test piece (D) of width 1/4 inch × length 5 inch × thickness 1/2 inch compliant with UL flame resistance test standard UL94V, respectively.
<Injection molding conditions>
Temperature setting: Feed 260 ° C, Nozzle 280 ° C, Mold 60 ° C
Injection pressure: 35-40 kg / cm ²

  The test piece (A) was measured for tensile strength (MPa), tensile elastic modulus (MPa), and tensile elongation (%).

(Flame retardancy test)
-Measuring method of flammability by oxygen index About the obtained test piece (C), the oxygen index (% (V / V)) was measured according to JIS K-7201.
-Combustion test method of plastic About the obtained test piece (D), flammability was determined according to UL flame-resistance test specification UL94V.

Table 8 shows the blending weight ratio of the plastic material and the evaluation results.
From Table 8, No. Nos. 39-1 to 3 showed a remarkably high oxygen index in the flame retardancy test, and good flame retardancy of V1 in the UL94V test. No. 39-1 to 3 showed higher oxygen index and good flame retardancy of V0. That is, a plastic material having excellent flame retardancy can be obtained by using a compatibilizing agent and a flame retardant in combination even though the materials are used and regenerated using different polymers that are incompatible with each other. It was.

  For comparison, as shown in Table 8, No. 1 was used except that no compatibilizer was added. Although test piece molding was performed in the same manner as in 39-2, the test piece could not be molded (No. 39-7).

It is a SEM photograph of the fiber surface of Example 11-1. 6 is a SEM photograph of the fiber surface of Comparative Example 3.

Claims (2)

At least one selected from the group consisting of a plurality of polymers, at least one of which is used, and an oxazoline-based compatibilizer, an elastomer-based compatibilizer, a reactive compatibilizer, and a copolymer-based compatibilizer. A sheet-like or film-like molded body composed of a recycled plastic material containing a compatibilizer of
The plurality of types of polymers include used polyethylene terephthalate or polybutylene terephthalate to be recycled and polyolefin selected from unused polyethylene and polypropylene to be used or recycled.
The recycled plastic material includes 0.5 to 30 parts by weight of the compatibilizer with respect to 100 parts by weight of the plurality of types of polymers.
The sheet-shaped or film-shaped molded body has 2,000-8,000 fine convexes having a width of 1-10 μm and a height of 0.5-5 μm per 1 mm ² of the surface. .   The sheet-like or film-like molded article according to claim 1, wherein an ionomer resin is further used as a compatibilizing agent.