JP2002338827A - Resin composition for recycling - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a resin composition for recycling excellent in mechanical properties and appearance from contaminated thermoplastic resin molded article. SOLUTION: The resin composition for recycling, composed of powder and granular materials of a thermoplastic resin molded article with a contaminant adhered thereto and a compatibilizer, is manufactured by reutilizing a contaminated thermoplastic resin molded article. The compatibilizer can be a compound containing an oxazoline group, an acid anhydride group, a carboxyl group, an epoxy group or the like (an oxazoline compound and an ionomer resin is particular) and the amount thereof is about 0.01-10 pts.wt. (particularly 0.05-5 pts.wt.) based on 100 pts.wt. of the thermoplastic resin molded article with a contaminant adhered thereto.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resin composition useful for reusing contaminated thermoplastic resin molded articles and a method for regenerating (recycling) contaminated thermoplastic resin molded articles.

[0002]

2. Description of the Related Art Conventionally, plastics (resins) used as materials for tools and containers in general households, offices, factories and the like are discarded as garbage in landfills or incinerated as combustible garbage. I was For example, various types of plastics (for example, ABS resin, polypropylene resin, etc.) are used for various devices and instruments, and these materials are not collected at the time of disposal or new replacement, but become waste. That is the current situation.

On the other hand, in recent years, problems such as environmental hormones have been pointed out as an adverse effect of plastic, and there is a concern that the global environment may be deteriorated due to disposal of plastic.
Therefore, active efforts have been made to recycle and reuse used plastics.

However, used plastics are contaminated by foreign substances in addition to deterioration of the materials themselves due to heat history, light rays, aging, and the like, and thus the properties and appearance of the recycled molded articles are deteriorated. In particular, the mixing of foreign matter significantly reduces the mechanical properties of the plastic and causes discoloration. For example, plastic parts that are exposed to contaminated environments (eg, cooked, molded parts installed around the kitchen)
Is heavily contaminated by a plurality of contaminants such as edible oil, seal members, sand, and cotton dust. In order to regenerate such a member, it is conceivable to remove contaminants by washing and re-mold the member, but it is not easy to economically and efficiently remove these contaminants. Even if contaminants are removed, it is difficult to obtain a molded article having the initial properties. Since there are many unclear points on the mechanism of plastic degradation and destruction, no effective solution for recycling has been found.

[0005] Incidentally, a method of alloying an aromatic polysulfone and a polyamide resin by using a compatibilizer (Japanese Patent Application Laid-Open No. Hei 3-273056), or a method of forming a bisoxazoline compound with a hydrophobic main chain and active hydrogen atoms. COMPATIBLE COMPOSITION CONTAINING COMPOUND HAVING COMPOUND AND PROCESS FOR PRODUCING THE SAME
No. 17, JP-A-9-51965, and the like, a method of improving the properties of a golf ball by alloying an ionomer resin and a diene rubber using a compatibilizer is known. However, there is no known method for effectively recycling plastic molded articles.

[0006]

Accordingly, an object of the present invention is to provide a resin composition having improved mechanical properties such as strength and elasticity even when a contaminated thermoplastic resin molded article is reused, and a method for regenerating the same. Is to provide.

[0007] Another object of the present invention is to provide a resin composition and a recycling method in which discoloration is suppressed even when a contaminated thermoplastic resin molded article is reused.

[0008] It is still another object of the present invention to provide a resin composition and a recycling method that can effectively reuse a thermoplastic resin molded article that is significantly contaminated with various contaminants.

[0009]

Means for Solving the Problems The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, when a compatibilizing agent is used, even if a highly contaminated thermoplastic resin molded product is used,
The present inventors have found that a molded article having excellent mechanical properties and suppressed discoloration can be regenerated, and thus completed the present invention.

That is, the resin composition for recycling according to the present invention is a resin composition obtained by reusing a contaminated thermoplastic resin molded article, which is compatible with the powdery particles of the thermoplastic resin molded article to which contaminants are attached. And a solubilizer. Examples of the compatibilizer include compounds having an oxazoline group, an acid anhydride group, a carboxyl group, an epoxy group, etc. (for example, a carboxyl group-containing olefin resin, an epoxy group-containing vinyl polymer, an oxazoline compound, etc.) and aromatic compounds. Examples thereof include a vinyl-diene copolymer and the like. In particular, a bisoxazoline compound represented by the following formula (I) or a reaction product of the bisoxazoline compound and a hydrophobic compound having a functional group containing an active hydrogen atom is preferable. preferable. The ratio of the compatibilizer is 0.01 to 10 parts by weight (particularly 0.05 to 5 parts by weight) based on 100 parts by weight of the thermoplastic resin molded article to which the contaminant is attached.
It is about.

[0011]

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(Wherein, X represents an alkylene group, a cycloalkylene group or an arylene group and may have a substituent. R ^{1 to} R ⁴ may be the same or different and each represents a hydrogen atom or a substituent. An alkyl group or an aryl group which may be present).

Examples of the contaminants include oils and fats, organic or inorganic dusts, stickers, coating films, and the like, and the ratio is 0.1 to 100 parts by weight of the thermoplastic resin molded article.
005 to 5 parts by weight (particularly 0.01 to 3 parts by weight). The thermoplastic resin constituting the molded body may be an aromatic resin, a chlorine-containing vinyl resin, an olefin resin, or the like.

[0014] The present invention also includes a molded article formed from the resin composition. The present invention also includes a method of mixing and molding a contaminated thermoplastic resin with a compatibilizer to regenerate the contaminated thermoplastic resin.

[0015]

BEST MODE FOR CARRYING OUT THE INVENTION [Thermoplastic Resin Molded Article] In the present invention, as a molded article used for recycling, various thermoplastic resin molded articles contaminated by use can be used. As the molded body, a resin molded member (for example, a housing, a casing, a part, or the like) constituting various containers, devices, instruments, and the like can be used.

As the thermoplastic resin constituting the molded article,
Various thermoplastic resins can be used. For example, styrene resins [polystyrene (GPPS), impact-resistant polystyrene (HIPS), acrylonitrile-styrene copolymer (AS resin), acrylonitrile-butadiene-styrene block copolymer (ABS) Resins), AXS resins using various rubbers X in place of butadiene, etc.], polyester resins (polyalkylene arylates such as polyethylene terephthalate and polybutylene terephthalate, or copolyesters thereof), polycarbonate resins (bisphenol A type polycarbonate) Etc.), acrylic resins (polymethyl methacrylate, methyl methacrylate-
Styrene copolymer), chlorine-containing vinyl resin (polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, vinylidene chloride-vinyl acetate copolymer, etc.), olefin resin [C _2-10 olefin alone or copolymer Polymers (eg, polyethylene, polypropylene, poly 1-butene, polyisobutene, polybutadiene, polyisoprene, ethylene-
Propylene copolymers), copolymers of olefins and copolymerizable monomers (eg, ethylene-vinyl acetate copolymers, ethylene- (meth) acrylate copolymers, etc.), modified polyolefins, etc.], Polyamide resin (nylon 6, nylon 66, nylon 610, nylon 6
12, nylon 11, nylon 12, etc.), polyacetal resin (polyoxymethylene, etc.), polysulfone resin (polysulfone, polyethersulfone, etc.), polyphenylene resin (polyphenylene oxide, polyphenylene sulfide, etc.), cellulose resin (cellulose acetate) Such as cellulose esters, ethyl cellulose,
Cellulose ethers such as carboxymethyl cellulose).

[0017] The molded article is made of these thermoplastic resins.
It may be formed of a single resin, or may be formed of two or more polymer alloys.

Among these thermoplastic resins, for example, aromatic resins (styrene resins such as ABS resin, polycarbonate resins, polyester resins, etc.), chlorine-containing vinyl resins (polyvinyl chloride, etc.), olefin resins It is useful to regenerate at least one resin selected from resins (such as polypropylene).

In the regeneration, it may be reproduced as a polymer alloy composed of a plurality of resins. For example, an aromatic resin and a non-aromatic resin (such as the olefin resin)
May be reproduced in combination. When the molded article is regenerated with a polymer alloy, the ratio between the aromatic resin and the non-aromatic resin (chlorine-containing vinyl resin or olefin resin) is (weight ratio), for example, the former / the latter = 90/10 -10
/ 90, preferably about 70/30 to 30/70.

[Contaminant] The compact is contaminated with attached contaminant. The type of the contaminant varies depending on the environment in which the molded article is used, and is not particularly limited. Examples of the contaminant include oils, organic or inorganic dusts, sticking seals, and coating films made of paints. These contaminants may adhere to the compact alone, but usually a plurality of contaminants adhere to the compact. For example, in a molded article used around a cooking place or a kitchen, fats and oils and organic or inorganic dusts are combined (for example, when fats and oils adhere to the molded article, organic matter is passed through the fats and oils). Or, inorganic dust adheres to the molded body), and the composite is often contaminated. In addition, sticking seals and coatings or coating films to be attached to a fresh molded product are difficult to peel off from the molded product during reuse,
When there are a large number of molded bodies, the peeling operation of the seal becomes enormous, and thus the molded bodies often remain unavoidably.

The oils include oils derived from edible oils (such as tempura oils and oils and fats foods) and industrial oils (such as lubricating oils). For example, edible oils and the like are volatilized by heating and adhere to molded articles. Often do. Examples of the oils include, specifically, vegetable oils and animal oils and the like, for example, straight chain or capronic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, and behenic acid. Linear or branched unsaturated C _10-22 fatty acids such as branched-chain saturated C _4-22 fatty acids (especially saturated C _12-18 fatty acids), myristoleic acid, palmitoleic acid, petroselinic acid, oleic acid, linoleic acid, and linolenic acid (Especially unsaturated C _16-20 fatty acids), monohydric or polyhydric alcohol esters of these fatty acids (for example, mono-, di-, or tri-glyceride), and complex lipids (phospholipid). The adhesion ratio of the fats and oils to the molded article depends on the environment in which the molded article is used, and is not particularly limited. For example, 0.001 to 3 parts by weight, preferably 0 to 100 parts by weight of the thermoplastic resin molded article. 0.005 to 1 part by weight, more preferably about 0.01 to 0.5 part by weight (particularly 0.05 to 0.3 part by weight).

The organic dust includes organic products (dust) and fine particles derived from fiber products (clothing, blankets, futons, carpets, carpets, etc.), industrial products, foods and the like. Examples of the organic dusts include fibrous dust (such as cotton dust) floating in the air, resin fine particles, and organic fine particles of powdered food (such as sugar, flour, and starch). The adhesion ratio of the organic dust to the molded body is not particularly limited, but is 0.0% to 100 parts by weight of the thermoplastic resin molded body.
It is about 0.01 to 1 part by weight, preferably about 0.005 to 0.5 part by weight, and more preferably about 0.01 to 0.1 part by weight.

The inorganic dust includes fine particles derived from natural minerals (sand and soil particles, etc.), soot (tar-like substances, soot, etc.),
Carbon-based fine particles (such as activated carbon particles) are included. The adhesion ratio of the inorganic dust to the molded body is not particularly limited,
0.001 to 100 parts by weight of the thermoplastic resin molding
To 1 part by weight, preferably 0.003 to 0.5 part by weight, and more preferably about 0.005 to 0.1 part by weight.

Examples of the stickers include various seals made of paper or a resin film and an adhesive.
The film may be a composite film of paper or a resinous film, metal (such as aluminum foil), cloth, or the like. The adhesion ratio of the adhesive seals to the molded article is not particularly limited, but is preferably 0.005 to 3 parts by weight, preferably 0.01 to 1 part by weight, and more preferably 100 parts by weight of the thermoplastic resin molded article. It is about 0.05 to 0.5 parts by weight. When the sticker is made of a resin film, it is preferable to use a resin seal having the same system or compatibility as the thermoplastic resin molded body. That is, for example, when a styrene-based resin seal is used for a thermoplastic resin molded body formed of an ABS resin, both are easily compatibilized, and a decrease in the physical properties of the resin composition is suppressed.

The coating film is usually composed of a binder resin, a pigment, a dispersant, a filler and the like. The adhesion ratio of the coating film to the molded product is not particularly limited, but is 0.005 to 50 parts by weight, based on 100 parts by weight of the thermoplastic resin molded product.
Preferably it is about 0.01 to 30 parts by weight, more preferably about 0.05 to 5 parts by weight.

In some cases, a conventional additive contained in the molded article itself may act as a contaminant that degrades the properties during reuse. Such additives include stabilizers (antioxidants (phenol-based, amine-based, phosphorus-based, sulfur-based antioxidants and the like), ultraviolet absorbers (salicylic acid-based, benzotriazole-based, benzophenone-based and the like). UV absorbers), heat stabilizers (phosphorus compounds, nitrogen-containing compounds, alkali or alkaline earth metal compounds, etc.)
Etc.), flame retardants (halogen-based, phosphorus-based, antimony-based flame retardants, etc.), lubricants (hydrocarbons, metal soaps, fatty acids, higher alcohols, etc.), mold release agents (waxes, silicone oil, etc.), Antiblocking agents (silicone particles, crosslinked or curable resin particles, inorganic fine particles, etc.), antistatic agents (cationic surfactants such as quaternary ammonium salts, nonionic surfactants having a polyoxyethylene chain, etc.), reinforcing fibers ( Carbon fiber, activated carbon fiber, glass fiber, aluminosilicate fiber, aluminum oxide fiber, silicon carbide fiber, metal fiber, boron fiber, inorganic fiber such as potassium titanate fiber, organic fiber such as aramid fiber, etc.),
Inorganic fillers (glass flake, mica, graphite,
Plate fillers such as various metal foils, powdered fillers such as metal oxides, sulfates, carbonates, glasses and silicates, etc., dyes and pigments (carbon black, titanium pigments, zinc pigments, iron) Coloring agents such as inorganic pigments such as pigments, azo pigments, anthraquinone pigments, and organic pigments such as phthalocyanine pigments),
Dispersants (various surfactants, protective colloids, etc.), plasticizers (phthalic acid-based, phosphoric acid-based, fatty acid-based, epoxy-based plasticizers, etc.) are included.

The proportion of these additives is not particularly limited, but is 0.005 to 100 parts by weight of the resin molded product.
It is about 50 parts by weight, preferably about 0.01 to 30 parts by weight, and more preferably about 0.05 to 10 parts by weight.

Further, elements or members firmly integrated with the molded body by chemical or physicochemical means such as adhesion or fusion, or by physical means such as caulking or screwing also act as contaminants. May be. Examples of such elements or members include metals (single metals such as iron, aluminum, copper, gold, and silver, alloys such as stainless steel and steel, etc.) and ceramics (alumina, zirconia, and the like) included in or coated on the molded body. , Inorganic fibers (such as the above-mentioned inorganic fibers such as carbon fibers and activated carbon fibers), and other resin materials.

The proportion of these elements or members is not particularly limited, but may be 0.0 to 100 parts by weight of the resin molding.
05 to 50 parts by weight, preferably 0.01 to 30 parts by weight,
More preferably, it is about 0.05 to 10 parts by weight.

The total proportion of contaminants also depends on the environment in which the molded article is used, and is not particularly limited. It is about 0.1 to 3 parts by weight, more preferably about 0.05 to 2 parts by weight (particularly 0.1 to 1 part by weight). In addition, 0.005 parts with respect to 100 parts by weight of the molded body.
Amounts of contaminants on the order of ５5 parts by weight are usually highly contaminated.

Contaminants that can be removed without excessive washing (for example, substances that can fall off such as sand) may be removed and used for regeneration, if necessary.

The compact contaminated with such a contaminant can be usually pulverized to be finely divided or melted to be prepared as powders (pellets) for recycling. The size of the granules and pellets can be selected from a range that does not impair the moldability, for example, an average diameter of 10 μm to 1 cm, preferably 100 μm to 5 mm, more preferably 1 to 3 m.
m.

[Compatibilizer] As the compatibilizer, a conventional compatibilizer can be used, and examples thereof include compounds having a functional group such as an oxazoline group, an acid anhydride group, a carboxyl group, an epoxy group, and the like. included. Examples of the compatibilizing agent containing these functional groups include a carboxyl group-containing monomer such as maleic anhydride and (meth) acrylic acid, and a copolymerizable monomer (styrene, methyl methacrylate, acrylonitrile, olefin, etc.). ), A copolymer of an epoxy group-containing monomer such as glycidyl (meth) acrylate and the above-mentioned copolymerizable monomer, an epoxidized diene polymer, a polyolefin and the above-mentioned carboxyl group monomer And a copolymer to which an epoxy group-containing monomer or the like is grafted. Further, the compatibilizer may be a thermoplastic elastomer (for example, styrene-butadiene block or random copolymer, styrene-ethylene-butadiene block or random copolymer, hydrogenated styrene-butadiene block or random copolymer, styrene-isoprene Or an aromatic vinyl-diene copolymer such as a block or random copolymer, a hydrogenated styrene-isoprene block or a random copolymer). The aromatic vinyl-diene copolymer is usually a block copolymer. The thermoplastic elastomer may include the functional group,
It may not be included. These compatibilizers can be used alone or in combination of two or more.

Among these compatibilizers, a carboxyl group-containing olefin resin, an epoxy group-containing vinyl polymer, an oxazoline compound, and particularly a bisoxazoline compound can be preferably used.

Examples of the carboxyl group-containing olefin resin include, for example, a copolymer of a carboxyl group-containing monomer and a C _2-4 olefin (ethylene, propylene, etc.) or a cross-linked metal ion thereof, a polymerizable carboxylic acid [ (Meta)
Acrylic acid, maleic acid, etc.] and modified polyolefins (graft copolymers) with carboxylic anhydrides (maleic anhydride, etc.). Specifically, ethylene-
(Meth) acrylic acid copolymer, propylene- (meth) acrylic acid copolymer, ethylene-maleic anhydride copolymer, ethylene- (meth) acrylic acid-maleic anhydride copolymer, (meth) acrylic acid Examples thereof include acid-modified polyethylene such as (anhydride) maleic acid, maleic acid-modified polypropylene, maleic anhydride-modified polypropylene, and crosslinked products of these metal ions. As the carboxyl group-containing olefin resin, an ionomer resin [for example, a crosslinked product of a metal ion (zinc, alkali metal ion, etc.) of an ethylene- (meth) acrylic acid copolymer] and an acid-modified polyethylene are preferable. The weight average molecular weight of the carboxyl group-containing olefin resin is 1000 to 250.
000, preferably 5,000 to 100,000, more preferably about 1,000 to 50,000.

Examples of the epoxy group-containing vinyl polymer include:
For example, a copolymer of a glycidyl group-containing vinyl monomer (such as glycidyl (meth) acrylate) and a copolymerizable monomer can be exemplified. As the copolymerizable monomer, C
_2-4 olefins (ethylene, propylene, etc.), acrylic monomers [(meth) acrylic acid C _1-4 alkyl esters such as (meth) acrylic acid, methyl methacrylate, (meth) acrylonitrile, etc.), aromatic vinyl Examples include a system monomer (styrene, divinylbenzene, etc.). Specific examples include a _C2-4 olefin-glycidyl (meth) acrylate copolymer and a _C2-4 olefin-glycidyl (meth) acrylate- (meth) acrylonitrile-styrene copolymer.

Examples of the oxazoline compound include oxazoline, a bisoxazoline compound represented by the formula (I), and a reaction product of the bisoxazoline compound and a hydrophobic compound having a functional group containing an active hydrogen atom.

In the formula (I), examples of the alkylene group X include C _1-10 alkylene groups such as methylene, ethylene, trimethylene, propylene, tetramethylene, pentamethylene, hexamethylene and the like. As the cycloalkylene group for X, 1,3-cyclopentylene, 1,1,
Examples thereof include a 3-cyclohexylene group and a 1,4-cyclohexylene group. Examples of the arylene group for X include 1,3-phenylene, 1,4-phenylene, 1,2-phenylene,
C _6-12 such as 1,5-naphthylene and 2,5-naphthylene group
An arylene group can be exemplified. X may have a substituent, for example, a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, etc.), an alkyl group (methyl, ethyl, propyl,
C _1-6 alkyl group such as butyl group, etc.), alkoxy group (C such as methoxy, epoxy, propoxy, butoxy, etc.)
_1-6 alkoxy group). As X,
Phenylene groups are preferred.

R¹~ R^FourExamples of the alkyl group include methyl,
C such as ethyl, propyl, butyl, etc. _1-6Examples are alkyl groups
Can be shown. As the aryl group, phenyl, 1-naphthyl
And a 2-naphthyl group. R¹~ R^FourSubstituents
Can be exemplified by the same substituents as those of X. R
¹~ R^FourAs a hydrogen atom or C_1-4Alkyl groups, especially water
Elementary atoms are preferred.

Preferred specific examples of the bisoxazoline compound (I) include, for example, 2,2 '-(1,3-phenylene) -bis (2-oxazoline), 2,2'-(1,
4-phenylene) -bis (2-oxazoline), 2,
2 '-(1,2-phenylene) -bis (2-oxazoline) and the like can be exemplified.

The bisoxazoline compound (I) binds to oils and fats (such as carboxyl groups of higher fatty acids) among the contaminants, and inactivates the active groups of the oils and fats, thereby recycling the resin composition. It is presumed that deterioration (discoloration) due to heating is suppressed. Furthermore, it is presumed that the bisoxazoline compound (I) acts more effectively as a compatibilizer by binding to the fats and oils (the fats and oils correspond to hydrophobic compounds described below).

Examples of the hydrophobic compound having a functional group containing an active hydrogen atom include C _10-30 aliphatic alcohols (higher alcohols such as lauryl alcohol, tetradecyl alcohol, cetyl alcohol and oleyl alcohol), saturated or unsaturated alcohols. C _6-30 fatty acids (higher fatty acids such as lauric acid, palmitic acid, stearic acid, oleic acid, linoleic acid, linolenic acid), saturated or unsaturated C _4-40 polycarboxylic acids (succinic acid, adipic acid, maleic acid) , Maleic anhydride, dimer acid, etc.), _C10-26 aliphatic amines (laurylamine, stearylamine, oleylamine, etc.), aromatic compounds (benzoic acid, phenol, aniline, etc.), and polymers having the functional groups introduced therein Etc. can be exemplified. Examples of the polymer include hydrophobic monomers such as C _2-6 olefins (ethylene, propylene, etc.), diene monomers (butadiene, isoprene, etc.), and aromatic vinyl monomers (styrene, etc.). Homo- or copolymers, hydrophobic monomers and copolymerizable monomers [acrylic monomers ((meth) acrylic acid, (meth) acrylic acid ester, (meth) acrylonitrile, etc.), vinyl esters And the like (vinyl acetate, vinyl propionate, etc.). Functional groups such as a carboxyl group, an amino group, and a hydroxyl group can be introduced by copolymerization or graft polymerization with a monomer having a functional group such as (meth) acrylic acid or maleic anhydride. The amount of the functional group to be introduced is 0.1 to 25% by weight, preferably 0.5 to 20%, in terms of a monomer having a functional group.
%, More preferably about 1 to 15% by weight.
The weight average molecular weight of the polymer is 1,000 to 25,000
0, preferably 5,000 to 100,000, more preferably about 1,000 to 50,000. Among these hydrophobic compounds, higher fatty acids (e.g., _C10-20 fatty acids), aromatic compounds (e.g., benzoic acid), polymers having the functional groups introduced therein (ethylene- (meth) acrylic acid copolymer, maleic anhydride, etc.) The above-mentioned carboxyl group-containing olefin resin such as acid-grafted polypropylene) is preferable.

The reaction product preferably has an oxazoline ring. Such a reaction product having an oxazoline ring may be prepared, for example, by using bisoxazoline compound (I) 0.7 to 1 to 1 mol of a functional group containing an active hydrogen atom.
It can be obtained by reacting using 1.5 mol, preferably about 0.8 to 1.2 mol.

The ratio of the compatibilizer is 0.01 to 10 parts by weight based on 100 parts by weight of the thermoplastic resin molded article to which the contaminant is attached.
Parts by weight, preferably about 0.05 to 5 parts by weight, more preferably about 0.1 to 1 part by weight.

[Resin Composition for Recycling] The resin composition for recycling of the present invention is obtained from a contaminated thermoplastic resin molded article, and comprises the resin particles containing contaminants and the compatibilizer. Have been. The resin particles can be obtained, for example, by pulverizing and compacting a molded article, or by melting and pelletizing.

The resin composition may be prepared by kneading the powder and the compatibilizer. For the kneading, a conventional method can be used.For example, both components can be fed to a conventional melt mixer such as a single-screw or twin-screw extruder, a Banbury mixer, a kneader, a mixing roll, or the like, and melt-kneaded. it can.

The composition further comprises a stabilizer (antioxidant, ultraviolet absorber, heat stabilizer, etc.), a flame retardant, a lubricant,
Conventional additives such as release agents, anti-blocking agents, antistatic agents, reinforcing fibers, inorganic fillers, coloring agents such as dyes and pigments, dispersants, plasticizers, and antistatic agents may be included.

The composition is molded by, for example, injection molding, extrusion molding, foam molding, blow molding, vacuum air pressure, or the like.
Can be played.

According to the present invention, the used molded product can be recycled by a simple method of simply adding the compatibilizing agent to the contaminated thermoplastic resin powder. In particular, even if highly contaminated or regenerated without removing contaminants, a resin composition having excellent mechanical properties and suppressed discoloration can be obtained. Further, a molded article (recycled molded article) formed from the recycled resin composition
Since it is excellent in various physical properties, it can be recycled as a material for various devices, instruments (housings, casings, parts, etc.), containers and the like.

[0050]

According to the present invention, a resin composition having improved mechanical properties such as strength and elasticity can be obtained even if a contaminated thermoplastic resin molded article is reused. Further, a resin composition in which discoloration is suppressed can be obtained. Further, even a thermoplastic resin molded article which is significantly contaminated by various contaminants can be effectively reused by a simple method. Since the molded article formed of the resin composition for recycling can be used effectively, it contributes to the reuse of resources and, furthermore, the prevention of pollution of the global environment.

[0051]

EXAMPLES The present invention will be described in detail below with reference to examples and comparative examples, but the present invention is not limited to these examples. The contents of the abbreviations of the compatibilizers used in Examples and Comparative Examples, and the contaminated thermoplastic resin molded product models are shown below. The tensile tests (tensile strength, elastic modulus and elongation at break) in Examples and Comparative Examples are based on JIS K7.
Izod impact strength is measured according to JIS K
It was measured according to 7110.

[Compatibilizer] io: ionomer (Himilan 1706 Zn, Mitsui
Ox-1: 2,2 '-(1,3-phenylene) -bis (2-oxazoline) ox-2: 2,2'-(1,3-phenylene) -bis (2-oxazoline) ) And a reaction product of benzoic acid ox-3: a reaction product of 2,2 ′-(1,3-phenylene) -bis (2-oxazoline) and a maleic acid-modified polypropylene oligomer PEW: acid-modified polyethylene wax (HI EGMA: ethylene-glycidyl methacrylate copolymer (Bond First 2E, manufactured by Sumitomo Chemical Co., Ltd.) EGAN: ethylene-glycidyl methacrylate / acrylonitrile-styrene copolymer (Modiper, Nippon Oil & Fats) SEB: Styrene-ethylene-butadiene copolymer (Toughtec, manufactured by Asahi Kasei Corporation) .

[Contaminated thermoplastic resin molded product model]
Among the gas leak alarms installed in the kitchens of ordinary households (Pokopoko, manufactured by Osaka Gas Co., Ltd.), the most dirty gas leak alarm was dismantled, and the pollutants were analyzed to form a molded body. Oils and fats 0.1 to 100 parts by weight of resin
11 parts by weight, organic particles 0.026 parts by weight, inorganic particles 0.008 parts by weight, paper seal 0.079 parts by weight, PE
0.144 parts by weight of a T seal was included. With reference to this, a thermoplastic resin molded article model to which contaminants adhered was prepared. The types and ratios of contaminants in this model (ratio to 100 parts by weight of resin constituting the molded body) are shown below. The resin constituting the molded article is a polymer alloy of ABS resin and polyvinyl chloride (PVC) (ABS resin / PVC = 50/50 (weight ratio), manufactured by Kanegafuchi Chemical Industry Co., Ltd., EMPLEX N-340). ).

Oleic acid: 0.1 parts by weight Ground cotton: 0.05 parts by weight Silica fine powder: 0.05 parts by weight Paper ground: 0.1 parts by weight PET flake: 0.5 parts by weight

Example 1 ABS / PVC polymer alloy (Emplex N-3)
40) 100 parts by weight of the composition containing the contaminants shown in Table 1 was melt-extruded at an extrusion pressure, an extrusion temperature of 200 ° C. and an extrusion time of 2 minutes as shown in Table 1 to obtain strand-shaped pellets. Was. The obtained pellet was visually evaluated. Table 1 shows the results. In addition, as a control, ABS / PV
Stranded pellets obtained by simply extruding C polymer alloy pellets were also evaluated.

[0056]

[Table 1]

From the results shown in Table 1, since yellowing was observed in the pellets formed of the composition containing oleic acid, a test was conducted to prevent thermal deterioration due to oleic acid.
In addition, the contaminants remain in the pellets formed of the composition containing the PET flakes, and the pellets are easily cut. PET flakes correspond to contaminants derived from a resin seal. However, it is preferable to suppress deterioration by replacing the resin seal with a styrene resin seal.

0.1 part by weight of oleic acid and 100 parts by weight of ABS / PVC polymer alloy (Emplex N-340) and a compatibilizer (ox-
The composition containing 1) was melt-extruded at the extrusion temperature and extrusion time shown in Table 2 and molded by injection molding to obtain a test piece (No. 1 test piece (JIS K-7113)). The mechanical properties of the obtained test specimen were measured, and the discoloration of the molded article was visually observed and evaluated. Table 2 shows the results. As a control, a test body was prepared and evaluated in the same manner as described above, using pellets of ABS / PVC polymer alloy and strand pellets obtained by simply extruding the pellets.

[0059]

[Table 2]

From the results shown in Table 2, the composition to which the compatibilizer (bisoxazoline) was added was prevented from being thermally degraded by oleic acid. In particular, in the composition to which the compatibilizer is added in an amount of 0.1 part by weight or more, both the mechanical properties and the discoloration are almost equal to those of the pellet before extrusion.

Example 2 ABS / PVC polymer alloy (Emplex N-3)
40) A kneaded product obtained by melt-extruding a composition prepared by mixing a contaminant in a ratio shown in Table 3 with respect to 100 parts by weight at an extrusion pressure and an extrusion temperature of 200 ° C. and an extrusion time of 2 minutes shown in Table 3 by injection molding. After molding, the test piece (No. 1 test piece (JIS K-71
13)) was obtained. The mechanical properties of the obtained specimen were evaluated. Table 3 shows the results. In addition, as a control, ABS / PV
Specimens were prepared and evaluated in the same manner as described above using C polymer alloy pellets and strand-shaped pellets obtained by simply extruding the pellets.

[0062]

[Table 3]

From the results shown in Table 3, since the mechanical properties of the composition containing pulverized cotton wool, paper pulverized material, and PET flakes were remarkably reduced, the reduction of mechanical properties due to the pulverized cotton wool and the pulverized paper was suppressed. A test was conducted to

With respect to 100 parts by weight of the ABS / PVC polymer alloy (Emplex N-340), 0.05 parts by weight of the crushed absorbent cotton or 0.1 parts by weight of the crushed paper, and Table 4
And the resulting composition was melt-extruded at an extrusion temperature and an extrusion time shown in Table 4 and injection-molded into a kneaded product to obtain a test piece (No. 1 test piece (JIS K- 71
13)) was obtained. The mechanical properties of the obtained specimen were measured. Table 4 shows the results. In addition, as a control, ABS / PV
Specimens were prepared and evaluated in the same manner as described above using C polymer alloy pellets and strand-shaped pellets obtained by simply extruding the pellets.

[0065]

[Table 4]

From the results in Table 4, it was found that the composition containing the crushed cotton wool had an ionomer content of 0.0% as a compatibilizer.
The addition of 5 parts by weight and 1 part by weight (particularly 1 part by weight) suppresses the decrease in mechanical properties, but the addition of 3 parts by weight does not suppress the decrease in mechanical properties. In the composition to which the bisoxazoline-based compound is added as a compatibilizer, the decrease in mechanical properties is suppressed by adding 0.1 parts by weight.

For the composition containing the pulverized paper, addition of an ionomer as a compatibilizer suppresses a decrease in mechanical properties. In addition, in any of the compositions to which a bisoxazoline-based compound is added as a compatibilizer, a decrease in mechanical properties is suppressed.

Example 3 For the most dirty gas leak alarm (recovery material) or 100 parts by weight of a contaminated thermoplastic resin molded model material excluding PET flakes (model material), see Table 5 A composition containing the bisoxazoline-based compound at the indicated ratio was melt-extruded at an extrusion temperature and an extrusion time shown in Table 5 to obtain a kneaded product, which was then subjected to injection molding to obtain a test piece (No. 1 test piece (J
IS K-7113)) was obtained. The mechanical properties of the obtained specimen were measured. Table 5 shows the results. As a control, a test body was prepared and evaluated in the same manner as described above, using pellets of ABS / PVC polymer alloy and strand pellets obtained by simply extruding the pellets.

[0069]

[Table 5]

From the results in Table 5, it is found that the addition of the bisoxazoline-based compound suppresses a decrease in mechanical properties of both the recovered material and the model material.

Example 4 A polypropylene resin (3522G, manufactured by Calp Industries, Ltd.)
To 100 parts by weight of a contaminant and a compatibilizer at a ratio shown in Table 6.
The mixture was melt-kneaded for 2 minutes at an extrusion temperature of 2 ° C., and the resulting kneaded material was molded by injection molding to obtain a test piece (No. 1 test piece (JIS K-7).
113)). The mechanical properties of the obtained specimen were evaluated. Table 6 shows the results. As a control, a test specimen was prepared and evaluated in the same manner as above using a polypropylene resin pellet.

In addition, a polypropylene resin seal (PP
Is a contaminant adhered to the molded body, oleic acid is a contaminant that adheres to the surface of the molded body as dirt, calcium carbonate is a contaminant contained in the molded body itself as a filler, and activated carbon fiber is dismantled from the molded body. It was selected as a model material for contaminants included as impossible.

[0073]

[Table 6]

From the results shown in Table 6, among the various contaminants,
In the composition containing oleic acid, calcium carbonate, and activated carbon fiber, the mechanical properties were significantly reduced.

With respect to the composition containing oleic acid, the addition of 1 part by weight of a bisoxazoline compound (ox-3) as a compatibilizer suppresses a decrease in tensile strength and impact strength. In addition, ethylene-
Even when 1 part by weight of the glycidyl methacrylate copolymer is added, the decrease in impact strength is suppressed.

For compositions containing calcium carbonate,
As a compatibilizer, a bisoxazoline compound (ox-
By adding 1 part by weight of 3), a decrease in impact strength is suppressed. Further, by adding 1 part by weight of an acid-modified polyethylene wax as a compatibilizer, a decrease in tensile elongation is suppressed. Further, the addition of 1 part by weight of an ethylene-glycidyl methacrylate copolymer as a compatibilizer suppresses a decrease in tensile elongation and impact strength.

As for the composition containing activated carbon fiber, bisoxazoline compound (ox-3),
Ionomer, or acid-modified polyethylene wax,
By adding 1 part by weight of each, a decrease in impact strength is suppressed.

Example 5 100 parts by weight of an acrylonitrile-butadiene-styrene (ABS) resin (GR2000, manufactured by Denki Kagaku Kogyo KK) were mixed with a contaminant and a compatibilizer in the proportions shown in Table 8 to obtain a mixture. The composition obtained was subjected to a temperature of 210 ° C. and an extrusion time of 2
For 1 minute, and the resulting kneaded material was molded by injection molding to obtain a test piece (No. 1 test piece (JIS K-7113)). The mechanical properties of the obtained specimen were evaluated. Table 8 shows the results. As a control, a test body was prepared and evaluated in the same manner as above, using ABS resin pellets.

The polypropylene resin seal is a contaminant adhered to the molded body, oleic acid is a contaminant adhering to the surface of the molded body as dirt, calcium carbonate is a contaminant contained in the molded body itself, and activated carbon fiber is a molded substance. It was selected as a model material for contaminants contained as non-dismantleable from the body.

[0080]

[Table 7]

From the results shown in Table 7, among the various contaminants,
In the composition containing the polypropylene seal, oleic acid, calcium carbonate, and activated carbon fiber, the mechanical properties were significantly reduced.

With respect to the composition containing the polypropylene resin seal, the drop in impact strength is suppressed by adding 1 part by weight of a bisoxazoline-based compound (ox-2) as a compatibilizer.

For the composition containing oleic acid, the addition of 1 part by weight of a bisoxazoline compound (ox-2) as a compatibilizer suppresses a decrease in tensile strength and impact strength. The addition of 1 part by weight of an ionomer or an ethylene-glycidyl methacrylate / acrylonitrile-styrene copolymer as a compatibilizer suppresses a decrease in impact strength and tensile elongation. Further, by adding 1 part by weight of a styrene-ethylene-butadiene copolymer as a compatibilizer, a decrease in tensile strength and impact strength is suppressed.

For compositions containing calcium carbonate,
By adding 1 part by weight of a styrene-ethylene-butadiene copolymer as a compatibilizer, a decrease in impact strength is suppressed.

For the composition containing activated carbon fibers, bisoxazoline-based compounds (ox-2),
By adding 1 part by weight of each of the ionomer and the styrene-ethylene-butadiene copolymer, a decrease in impact strength is suppressed.

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Shinichi Kawasaki 4-1-2 Hirano-cho, Chuo-ku, Osaka City Inside Osaka Gas Co., Ltd. (72) Inventor Masahiro Yamada 4-1-2, Hirano-cho, Chuo-ku, Osaka-shi Inside Osaka Gas Co., Ltd. (72) Inventor Mariko Kato 4-1-2, Hirano-cho, Chuo-ku, Osaka-shi Inside Osaka Gas Co., Ltd. Inventor Masayuki Ogoshi 1-19-29 Karasaki, Otsu City, Shiga Prefecture B-106 (72) Inventor Hiromi Yanase 1-26 Hirata, Kyotanabe City, Kyoto (72) Inventor Masahiro Sato 368-7F, Takashiro, Shiga-cho, Shiga-gun, Shiga Prefecture Term (reference) 4F301 AA02 AA13 AA14 AA15 AA17 AA20 AA25 AA27 AB01 AB03 BD03 BD05 CA07 CA11 4J002 AA011 AB011 BB001 BB011 BB031 BB051 BB082 BB121 BB142 BB171 BB212 BB232 BC021 BC061 BD03 101 BN151 CB001 CD192 CF061 CF071 CG011 CH071 CL001 CN031 EU216 EU226 FD202 FD206

Claims (9)

[Claims] Claims: 1. A resin composition obtained by reusing a contaminated thermoplastic resin molded article, comprising: a resin for recycling comprising a powdery thermoplastic resin molded article to which a contaminant adheres and a compatibilizer. Composition. 2. The composition according to claim 1, wherein the compatibilizer is a compound having at least one group selected from an oxazoline group, an acid anhydride group, a carboxyl group and an epoxy group. 3. The method according to claim 1, wherein the compatibilizer is at least one selected from a carboxyl group-containing olefin resin, an epoxy group-containing vinyl polymer, an oxazoline compound, and an aromatic vinyl-diene copolymer. Composition. 4. The thermoplastic resin molded article to which at least one contaminant selected from fats and oils, organic or inorganic dusts, sticking seals and a coating film is adhered, Of the thermoplastic resin molded article 100
The amount is 0.005 to 5 parts by weight with respect to parts by weight.
A composition as described. 5. The composition according to claim 1, wherein the thermoplastic resin constituting the molded article is at least one selected from an aromatic resin, a chlorine-containing vinyl resin, and an olefin resin. 6. The ratio of the compatibilizer is 0.01 to 1 part by weight based on 100 parts by weight of the thermoplastic resin molded article to which the contaminant has adhered.
The composition according to claim 1, which is 0 parts by weight. 7. A resin composition in which a contaminated thermoplastic resin molded article is reused, wherein the heat is contaminated with a plurality of contaminants selected from fats and oils, organic or inorganic dusts, and stickers. The granular material (A) of the molded article of the plastic resin and the following formula (I): (In the formula, X represents an alkylene group, a cycloalkylene group or an arylene group, and may have a substituent. R ¹
To R ⁴ are the same or different, a hydrogen atom, a functional including bisoxazoline compound represented by the substituted showing also an alkyl group or an aryl group), and the bisoxazoline compound and an active hydrogen atom And at least one compatibilizer (B) selected from a reaction product with a hydrophobic compound having a group, wherein the thermoplastic resin particles are selected from a styrene resin, a vinyl chloride resin and an olefin resin A recycling resin composition comprising at least one kind of the compatibilizer (B), wherein the proportion of the compatibilizer (B) is 0.05 to 5 parts by weight with respect to 100 parts by weight of the granular material (A) of the molded article. 8. A molded article formed from the resin composition according to claim 1. 9. A method of mixing and molding a contaminated thermoplastic resin with a compatibilizer to regenerate the contaminated thermoplastic resin.