JP2003200424A - Thermoplastic resin article, method for producing reclaimed thermoplastic resin and recycling system - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for producing a reclaimed thermoplastic resin. <P>SOLUTION: A thermoplastic resin article is provided with recycling data comprising at least retrieving data, sorting-out data and reclaiming data. Thermoplastic resin elements of the thermoplastic resin article comprise a plurality of elements having mutual affinity where an equivalent reclamation agent is added at least to a main element to allow equivalent reclamation. A waste of the thermoplastic resin article is retrieved and brought to a reclamation site according to the retrieving data attached to the article, the thermoplastic resin elements are selectively collected by sorting with the sorting-out data, and a reclaimed thermoplastic resin article is produced using the selectively collected thermoplastic resin elements according to the reclaiming data. In this way the waste can infallibly and easily be reclaimed equivalently as the necessary and reliable data are definitely available in any process at a user, a maker, a carrier or the reclamation site from the recycling data attached to the article itself. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a thermoplastic resin product that can be easily recycled, a method for producing a recycled thermoplastic resin, and a recycling system.

[0002]

2. Description of the Related Art Conventionally, various systems have been proposed for recycling products. For example, JP-A-7-3
No. 34583 is a product recycling system for judging a recycling process which is a product reuse method, and a reading means for reading information added to the product,
Storage means for storing a database of information for reuse of the product, which is associated with the information added to the product, and the storage based on the information added to the product read by the reading means. Recycling determination means for determining the recycling processing for the product by referring to information when reusing the product in the database stored in the means, and a result for the product determined by the recycling determination means are output. A product recycling system having an output means is provided, and in Japanese Patent Laid-Open No. 2000-126749, recycling applied to a recycling processing factory that performs a plurality of series of processing from receipt of a processing object to shipment. In the processing management system, when each of the plurality of processing is performed on the processing object, A recycling process including a data acquisition unit that acquires process data regarding an object to be processed, and an input unit that inputs the process data acquired by the data acquisition unit to a database each time the plurality of processes are performed. A management system is provided, and in Japanese Patent Laid-Open No. 2000-181958, a recycling system that comprehensively manages the recycling process of each component of a product from the material to the final disposal stage is under the control of the system. Products or parts manufactured or used in
Stored as recycling information is information on all reusable products, parts, and raw materials, including raw materials that have been disposed of, products and parts that have been discarded, and products, parts, and raw materials that are currently used in the market. Based on the recycling information storage means and the recycling information stored in the recycling information storage means, the time and amount at which the reusable product / part / raw material is collected as a recyclable product / part / raw material. And a recycling production plan setting means for setting a production plan for a recycled product using reusable products, parts, and raw materials based on the time and amount predicted by the recycling collection prediction means. A recycling system with is provided.

[0003]

However, since the above recycling information is used by manufacturers, recycling factories, etc., there is no information about how to recover waste thermoplastic resin products at the recycling site. There is. Such information is attached to the product, and if the collection from the product use site where a waste product is generated to the recycling site is not performed based on the above information, successful recycling cannot be performed.

[0004]

As a means for solving the above-mentioned conventional problems, the present invention provides a thermoplastic resin product having recycling information. It is desirable that the recycling information is composed of at least collection information, selection information, and reproduction information. Further, it is desirable that there are a plurality of thermoplastic resin elements of the thermoplastic resin product, and they have mutual affinity. Further, it is desirable that an equivalent regenerant is added to at least the main element of the thermoplastic resin elements so that the elements can be equivalently regenerated. Further, there is provided a method for producing a recycled thermoplastic resin, in which a waste thermoplastic resin product with recycling information is recycled based on the above recycling information. The recycling information attached to the thermoplastic resin product includes at least collection information, selection information, and reproduction information, and the waste product of the thermoplastic resin product is collected according to the collection information attached to the product and is sent to the reproduction site. At the recycling site, the waste products are sorted according to the sorting information to select and collect the thermoplastic resin elements, and the recycled thermoplastic resin products are collected by using the selected and collected thermoplastic resin elements based on the reproduction information. It is desirable to manufacture. Further, the thermoplastic resin product is provided with recycling information including at least collection information, selection information, and reproduction information, and the waste product of the thermoplastic resin product is collected according to the collection information attached to the product and is recycled at the recycling site. And a step of collecting the thermoplastic resin elements by sorting the waste products according to the sorting information at the recycling site, and a recycling heat using the thermoplastic resin elements sorted and collected based on the recycling information. It is intended to provide a recycling system including a process of manufacturing a plastic resin product.

[0005]

The waste product of the thermoplastic resin product generated by the user is collected based on the recycling information attached to the product and collected at the recycling site, and is recycled at the recycling site based on the recycling information. The collection of the waste product is performed by the collection information incorporated in the recycling information, and the reproduction at the reproduction site is performed by the selection information and the reproduction information incorporated in the recycling information.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION [Thermoplastic Resin Product] The thermoplastic resin product of the present invention (hereinafter simply referred to as a product) is a product containing one or more thermoplastic resin elements,
The products of the present invention also include products containing other elements such as metal elements, ceramic elements, wood elements, paper elements, and thermosetting resin elements, in addition to products comprising only thermoplastic resin elements. In addition to the resin molded product, a resin label attached to the resin molded product, a resin seal, a paint applied to the resin molded product, ink, child parts, and each element are joined to the thermoplastic resin element. The adhesive used, the welding rod, etc. are also included. Here, the child part refers to a seal (decal) and ink / adhesive used for the seal, a coating film, a printed ink film, and other plastic parts (for example, a lens and a handle of a housing).

The thermoplastic resin which is an element of the product of the present invention will be described below in detail, for example, polyethylene (PE), polypropylene (PP), ethylene-propylene copolymer, ethylene-vinyl acetate copolymer, polyvinyl chloride. , Polyvinylidene chloride, polystyrene, high impact polystyrene (HIPS), polyvinyl acetate, fluororesin, thermoplastic acrylic resin, thermoplastic polyester, polyphenylene ether (PPE), modified PPE, thermoplastic polyamide, thermoplastic polyamideimide, thermoplastic Polyetherimide, thermoplastic urethane resin, acrylonitrile-
Butadiene copolymer, styrene-butadiene copolymer,
Acrylonitrile-butadiene-styrene copolymer (A
BS), polyether ether ketone (PEEK), polyether ketone (PEK) ethylene-propylene copolymer, ethylene-propylene terpolymer, ethylene-vinyl acetate copolymer, polycarbonate resin (PC), polyethylene terephthalate (PET) ), Polybutylene terephthalate (PBT), polyethylene naphthalate (PEN), polyarylate (PAR) polyamide resin (PA) and the like, and also styrene-isoprene-styrene copolymer (SIS), styrene-ethylene-butylene-styrene copolymer. A thermoplastic resin of a thermoplastic elastomer such as a polymer (SEBS) or a styrene-ethylene-propylene-styrene copolymer (SEPS) can be used, and the thermoplastic resin can be used alone or in a mixture, or a polymer. Alloy, etc. Used.

[Equivalent Regenerating Agent] It is desirable that an equivalent regenerating agent is added to the thermoplastic resin. Equivalent regeneration means that the resin regenerated from the waste of the molded product made of virgin resin can be used as a molded product having the same value as the molded product, that is, a material of the equivalent molded product.
As such an equivalent regenerant, a rubber-like substance having an affinity with the thermoplastic resin can be used. As the rubber-like substance, there is a graft rubber having a graft chain having a trunk portion of a diene rubber, an olefin rubber or an acrylic rubber and having a compatibility with a thermoplastic resin constituting each thermoplastic resin element, for example, They are a diene rubber graft polymer, an olefin rubber graft polymer and an acrylic rubber graft polymer. Particularly, an olefin rubber graft polymer and an acrylic rubber graft polymer which are excellent in heat stability are preferable. Hereinafter, each rubber-like substance will be described.

(A: olefin rubber graft polymer)
The olefin-based rubber is a polymer of one or more kinds of α-olefin, or a copolymer of one or more kinds of the α-olefin and another monomer copolymerizable with the α-olefin. In particular, it is a copolymer of ethylene and one or more kinds of other α-olefins, or a copolymer of other monomers copolymerizable therewith, especially a non-conjugated diene compound. In the ethylene-α-olefin-based copolymer, the α-olefin used as a monomer to be copolymerized with ethylene has a carbon number of 3 to 12
.Alpha.-olefin, specifically, propylene, butene-1,4 methylpentene-1, hexene-1, octene-1 and the like.

Examples of the non-conjugated diene compound include dicyclopentadiene, tricyclopentadiene and 5-
Methyl-2,5-norbornadiene, 5-methylene-2
-Norbornene, 5-vinyl-2-norbornene, 5-
Ethylidene-2-norbornene, 5-isopropylidene-2-norbornene, 5-isopropenyl-2-norbornene, 5- (1-butenyl) -2-norbornene, 5
-(2-propenyl) -2-norbornene, 5- (5-
Hexenyl) -2-norbornene, 4,7,8,9-tetrahydro-indene, and isopropylidene tetrahydro-indene, cyclooctadiene, vinylcyclohexene, 1,5,9-cyclododecatluene, 6-methyl-4,7. , 8,9-Tetrahydroindene, 2,
2'-dicyclopentenyl, trans-1,2-divinylcyclobutane, 1,4-hexadiene, 2-methyl-
1,4 hexadiene, 1,6-octadiene, 1,7-
Octadiene, 1,8-nonadiene, 1,9-decadiene, 3,6-dimethyl-1,7-octadiene, 4,5
-Dimethyl-1,7-octadiene, 1,4,7-octatriene, 5-methyl-1,8-nonadiene and the like.

Among these non-conjugated diene compounds, preferred is 5-ethylidene-2-norbornene (EN
B), and / or dicyclopentadiene (DC
P), more preferably dicyclopentadiene.
A mixed resin of an olefin rubber graft polymer using 5-ethylidene-2-norbornene and AS or PS has a good appearance of a molded product. Further, in the olefin rubber graft polymer, E as the main rubber component
The impact strength of the thermoplastic resin for molding can be increased by using EPDM rather than PM.

The proportion of the ethylene-α-olefin and the non-conjugated diene compound used as necessary in the olefin rubber graft polymer is preferably a molar fraction of ethylene / α-olefin / non-conjugated diene. Compound = 0.2 to 1.0 / 0.2 to 0.8 / 0 to 0.2, more preferably 0.5 to 0.9 / 0.25 to 0.75
/ 0 to 0.1, and the ethylene / propylene molar ratio is 60/40 or more, preferably 65/35 or more, that is, the reproducibility of mechanical properties (impact resistance, etc.) of the obtained resin molded product (hereinafter, From the viewpoint of reproducibility, it is desirable to use ethylene-rich ethylene / propylene copolymer rubber (EPM) or ethylene / propylene / non-conjugated diene compound terpolymer rubber (EPDM).

The ethylene-α-olefin copolymer has a Mooney viscosity (ML1 + 4, 100 ° C.) of preferably 5 to 150, more preferably 10 from the viewpoint of reproducibility.
120, the optimum value is 20-80.

Typical of the above olefin rubbers are:
Ethylene / propylene copolymer rubber (EPM), ethylene / propylene / non-conjugated diene compound terpolymer rubber (E
PDM), ethylene / butene copolymer rubber (EBM), and ethylene / butene / non-conjugated diene compound terpolymer rubber (EBDM). The non-conjugated diene compound used in the EBDM is the same as in the case of EPDM described above.

The olefin rubber is graft-polymerized with a styrene monomer or a nitrile monomer in order to impart an affinity to the target thermoplastic resin. Examples of the styrene-based monomer to be graft-polymerized to the olefin-based rubber include styrene, α-alkylmonovinylidene aromatic monomer (eg, α-methylstyrene, α-ethylstyrene, α-methylvinyltoluene, α-methyl). Dialkylstyrene, etc.), ring-substituted alkylstyrene (eg, o, m, or p-vinyltoluene, o-ethylstyrene, p-ethylstyrene, 2,4-dimethylstyrene, p-tertiarybutylstyrene, etc.), ring-substituted Halostyrene (eg o-chlorostyrene, p-chlorostyrene, o-promostyrene, 2,4-dichlorostyrene etc.), ring-alkyl, ring halo-substituted styrene (eg 2-chloro-4-methylstyrene, 2,6). -Dichlorostyrene, etc.) of styrene-based monomers such as vinylnaphthalene, vinylanthracene, etc. One kind or a mixture thereof is used.

Alkyl substituents also generally have 1 to 4 carbon atoms and include both straight chain and branched alkyl groups.

Examples of the nitrile-based monomer to be graft-polymerized on the olefin-based rubber include acrylonitrile, methacrylonitrile, ethacrylonitrile, fumaronitrile and mixtures thereof.

In addition to the above-mentioned styrene-based monomer and nitrile-based monomer, other monomers may be copolymerized. The above-mentioned other monomer (third component) is not particularly limited as long as it is a monomer copolymerizable with the above-mentioned styrene-based monomer and nitrile-based monomer, but in general, methyl (meth) acrylate, ethyl (Meth) acrylates such as (meth) acrylate,
Examples include maleimides such as N-phenylmaleimide, maleimide, N-methylmaleimide, N-ethylmaleimide, (p-bromophenyl) maleimide methacrylate, and cyclohexylmaleimide, and unsaturated nitrile compounds such as maleic anhydride and methacrylonitrile. To be

The (meth) acrylates have 1 carbon atoms.
Alkyl esters of ~ 4, especially methacrylates, are preferred.

To graft-polymerize the above-mentioned monomer onto the above-mentioned olefin-based rubber, generally, the above-mentioned monomer is added in the presence of the above-mentioned olefin-based rubber to the above-mentioned oil-soluble or water-soluble initiator and / or ultraviolet ray, electron beam or the like. A polymerization method of polymerizing with high energy rays is used, and as the polymerization method, general methods such as bulk polymerization, suspension polymerization, solution polymerization, and emulsion polymerization are applied. The graft olefin-based rubber obtained by the graft polymerization is mainly composed of a graft polymer in a narrow sense having an olefin rubber as a trunk and a polymer chain of the above monomer as a branch. And / or a polymer comprising the above monomers is microblended.

The olefin rubber graft polymer is suitable, for example, for the following thermoplastic resins. (1) Graft polymer for styrenic resin For styrenic resin, particularly PS (or HIPS), one or more kinds of other styrenic monomers as styrene and / or a monomer similar to styrene. An olefin-based graft polymer obtained by graft-polymerizing styrene (which is a graft copolymer of styrene containing olefin-based rubber and / or a monomer similar to styrene, and is hereinafter referred to as a styrene-grafted olefin-based graft polymer) is used.
The styrene-grafted olefin-based graft polymer has a polymer chain of a styrene-based monomer having a solubility parameter substantially the same as that of the styrene-based resin, particularly PS, as a branch, and thus exhibits a good affinity for PS.

Styrenic resins, especially AS (or AB
For S), one or more of styrene (vinyl styrenated) and / or other styrenic monomers and one or more of acrylonitrile (vinyl cyanide) and / or other nitrile based monomers or Olefin-based graft polymer obtained by graft-polymerizing two or more kinds (styrene-containing olefin-based rubber and / or other styrene-based monomer, or monomer similar to styrene, and acrylonitrile and / or other nitrile-based monomer In the following, a styrene-nitrile graft olefin-based graft polymer, which is a graft copolymer with a polymer, is used. In addition to the above monomers, other monomers copolymerizable with the above monomers may be graft-copolymerized with the olefin rubber. Since the styrene-nitrile graft olefin-based graft polymer has a styrene-nitrile copolymer chain having a solubility parameter substantially the same as that of styrene-based resin, particularly AS (or ABS), it is good for AS (or ABS). Shows a good affinity.

In the above olefin rubber graft polymer, a single or a mixture of two or more rubbers may be used as the olefin rubber. The content of the olefin rubber is 10 to 80% by weight, preferably 15 to 75% by weight, and the total content of the monomers used for grafting (grafting rate) is 90 to 20% by weight, preferably 55. ~ 2
5% by weight, and in the case of a styrene-nitrile-grafted olefin-based rubber graft polymer, the styrene-based monomer is 5
˜95 wt% and nitrile monomer in the range of 95-5 wt% are desirable. Within this range, the affinity of the olefin-based rubber graft polymer for a thermoplastic resin and the effect of improving the reproducibility of the thermoplastic resin, that is, the effect of preventing a reduction in impact resistance during recycling are balanced.

The particle size of the above olefin rubber graft polymer is preferably 5.0 μm, and more preferably 0.001 to 2.0 μm, since they are mixed at the molecular level. In this particle size range, the effect of improving the reproducibility of the olefin rubber graft polymer becomes particularly large. The use of several kinds of olefin-based rubber graft polymers having different rubber particle diameters further improves the physical properties, so that the amount of the olefin-based rubber graft polymer added can be reduced.

Further, the above-mentioned olefin rubber graft polymer has a reduced viscosity η of the toluene-soluble component which is a measure of the molecular weight.
Sp / c (0.5 g / dl, toluene solution, measured at 30 ° C.) is preferably in the range of 0.30 to 1.00 g / dl, and is preferably in the range of 0.50 to 0.80 g / dl. More desirable.

Specific examples of the above-mentioned olefin-based rubber graft polymer include styrene-grafted EPM and / or EPDM obtained by graft-polymerizing styrene-based monomer on EPM and / or EPDM for PS or HIPS.
(St-g-EPM, St-g-EPDM, St-g-
EP for EPM / EPDM), AS or ABS
Acrylonitrile obtained by graft-copolymerizing M and / or EPDM with a nitrile monomer and a styrene monomer.
Styrene grafted EPM and / or EPDM (An
St-g-EPM, AnSt-g-EPDM, AnSt
-G-EPM / EPDM), ethylene / butene rubber (EBM) and / or ethylene / butene / PS for PS
Styrene-grafted EBM and / or EBDM (St-g-EBM, St-g-EBD) obtained by graft-polymerizing a styrene-based monomer on a diene three-dimensional copolymer (EBDM)
M, St-g-EBM / EBDM), AS or AB
Acrylonitrile obtained by graft copolymerizing EBM and / or EBDM for S with a nitrile monomer such as acrylonitrile and a styrene monomer such as styrene.
Styrene graft EBM and / or EBDM (An
St-g-EBM, AnSt-g-EBDM, AnSt
-G-EBM / EBDM).

(2) Graft polymer for PPE-based resin PPE is composed of a constitutional unit having a phenyl group as described above, and therefore, the above-mentioned S is used as a graft molecular body.
t-g-EPM, St-g-EPDM, St-g-EP
M ・ EPDM, St-g-EBM, St-g-EBD
It is desirable to select a styrene graft olefin type rubber graft polymer such as M, St-g-EBM.EBDM. The olefin rubber graft polymer is PP
Since it has a styrene polymer chain having a solubility parameter close to that of E as a branch and has a good affinity with the PPE resin, the olefin rubber graft polymer is stably mixed with the PPE resin without separation. Is
The reproducibility of the PPE resin is improved.

(3) Graft polymer for olefin resin For polyolefin resins such as polyethylene and polypropylene, since the olefin rubber is copolymerized with the same or similar monomers as the polyolefin resin, the above-mentioned polyolefin is used. Since it has a solubility parameter almost the same as that of the system resin, especially PP, it exhibits good affinity and can be used as it is as an equivalent regenerant. Ethylene as a recycle improver for olefin resins
The use ratio of the α-olefin and the non-conjugated diene compound used as necessary is preferably ethylene / α-olefin / non-conjugated diene compound = 0.2 in terms of mole fraction.
.About.1.0 / 0.2 to 0.8 / 0 to 0.2, and more preferably 0.5 to 0.9 / 0.25 to 0.75 / 0.
1 and the ethylene / propylene molar ratio is 60/40
As described above, preferably 65/35 or more, that is, from the viewpoint of reproducibility (hereinafter, reproducibility) of mechanical properties (impact resistance etc.) of the obtained resin molded product, ethylene-rich ethylene / propylene copolymer rubber ( EPM) or ethylene / propylene / non-conjugated diene compound terpolymer rubber (EPDM)
Is preferred.

The Mooney viscosity (ML1 + 4, 100) of the ethylene-α-olefin copolymer used in the present invention is also
From the viewpoint of reproducibility, the temperature is preferably 5 to 150, more preferably 10 to 120, and the optimum value is 20 to 80. In addition, St-g-EPM, St-g-EPDM,
Olefin-based rubber graft polymers such as AnSt-g-EPM and AnSt-g-EPDM also have good affinity for polyolefin-based resins and impart mechanical properties to polyolefin-based resins and are used as equivalent regenerants. You can also do it.

(B: Acrylic Rubber Graft Polymer) The acrylic rubber graft polymer is an acrylate having an alkyl group preferably having 2 to 8 carbon atoms, such as ethyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate. Homopolymers, copolymers of two or more of the above acrylates, or one or more of the above acrylates and non-conjugated diene compounds similar to those used in butadiene or EPDM, acrylonitrile, methyl methacrylate, vinyl acetate , Copolymers with one or more kinds of other monomers such as styrene, ethylene and propylene, and functional monofunctional compounds such as acrylic acid, methacrylic acid, β-hydroxyethyl methacrylate, acrylamide and dimethylaminoethyl methacrylate. There is a quantity The γ- methacryloxypropyl trimethoxy silane, vinyl triacetoxy silane, p-
Trimethoxysilylstyrene, p-triethoxysilylstyrene, p-trimethoxysilyl-α-methylstyrene, p-triethoxysilyl-α-methylstyrene, γ
-Acryloxypropyltrimethoxysilane, vinyltrimethoxysilane, N-β (N-vinylbenzylaminoethyl-γ-aminopropyl) trimethoxysilane.
It is a copolymer with a polymerizable silane coupling agent such as hydrochloride.

Examples of general-purpose acrylic rubbers include polyethyl acrylate, poly n-butyl acrylate, n-butyl acrylate-acrylonitrile copolymer, and n-butyl acrylate-butadiene copolymerized with some of the above functional monomers. Copolymer, n-butyl acrylate-ethylene copolymer, n-butyl acrylate-γ-methacryloxypropyltrimethoxysilane copolymer, n
-Butyl acrylate-vinyl trimethoxysilane copolymer and the like, and a preferable acrylic rubber is an n-butyl acrylate-butadiene copolymer having a molar ratio of n-butyl acrylate / butadiene of 30/70 or more.

The above acrylic rubber is usually produced by suspension polymerization, emulsion polymerization or the like. The acrylic rubber is graft-polymerized with a styrene-based monomer or a styrene-based monomer and a nitrile-based monomer in the same manner as the olefin-based rubber, and has an affinity with styrene-based resins, PPE-based resins and PC-based resins. Be imparted with sex. Similar to the olefin rubber graft polymer, the content of the acrylic rubber is 10 to 80% by weight, preferably 1 in view of the balance between the affinity and the effect of preventing the reduction of impact resistance during recycling.
5 to 75% by weight, and the total content (graft ratio) of the monomers used for grafting is 90 to 20% by weight, preferably 55 to 25% by weight, and a styrene / nitrile graft acrylic rubber graft polymer. In the case of, the styrene monomer is 5 to 95% by weight, and the nitrile monomer is 95 to 5%.
A weight% range is desirable. Within this range, the affinity of the acrylic rubber graft polymer for the thermoplastic resin and the effect of improving the reproducibility of the thermoplastic resin, that is, the effect of preventing reduction of impact resistance during recycling are balanced.

When the thermoplastic resin element is composed of two or more elements, each element is preferably made of a resin having mutual affinity. The two or more kinds of resins having mutual affinity are those which do not cause phase separation when the two or more kinds of resins are heated and melt mixed. Specifically, a resin having an affinity for a certain kind of resin is the same kind of resin or a resin having a similar chemical structure to the resin. There is a solubility parameter as an index of affinity, and when two or more kinds of melted mixture do not cause phase separation, the difference in solubility parameter is generally 3 or less, preferably 2 or less.

The combinations of resins having mutual affinity will be exemplified below. [Styrene-based resin] Typical examples of the styrene-based resin include polystyrene (PS) which is a styrene homopolymer, the above-mentioned diene rubber, acrylic rubber, and rubber-like polymer obtained by graft-polymerizing styrene to olefin rubber. High impact polystyrene (HIPS), which is a blend polymer of polymer and polystyrene, acrylonitrile / styrene copolymer (AS), styrene / butadiene copolymer, styrene / α-methylstyrene copolymer, styrene / maleic anhydride copolymer Polymers, styrene / methyl methacrylate copolymers, styrene / ethylene copolymers, styrene / ethylene / propylene / butadiene copolymers, graft polymers obtained by graft polymerizing acrylonitrile and styrene on butadiene rubber, and acrylonitrile / styrene copolymers Blend poly with -ABS, ACS which is a mixed resin of chlorinated polyethylene and acrylonitrile-styrene copolymer, and terpolymer of styrene and acrylonitrile containing olefin, which is obtained by graft-polymerizing acrylonitrile and styrene onto olefin rubber. A, which is a mixed resin of acrylonitrile / styrene copolymer
ES, terpolymer of acrylic rubber-containing acrylonitrile and styrene obtained by graft polymerization of acrylic rubber with acrylonitrile and styrene, and acrylonitrile
Examples include AAS, which is a mixed resin with a styrene copolymer, and ASiS, which is a mixed resin with an acrylonitrile / dimethylsiloxane / styrene copolymer and an acrylonitrile / butadiene / styrene copolymer resin. The styrenic resin may be a homopolymer of a styrenic monomer, a copolymer of two or more kinds of the styrenic monomer, a copolymer of the styrenic monomer and the styrenic monomer. Copolymer with one or more kinds of other monomers, graft copolymer obtained by graft-polymerizing styrene monomer alone or two or more kinds with rubber, microblend of styrene resin and rubber, or Polymer blends and the like are included.

As the resin having an affinity for the styrene resin (hereinafter referred to as an affinity resin), any of the styrene resins exemplified above, styrene-isoprene-styrene copolymer (SIS), styrene-ethylene can be used. -Butylene-styrene copolymer (SEBS), styrene-ethylene-propylene-styrene copolymer (SEP)
Examples thereof include styrene elastomers such as S) and PPE resins.

For the ink, paint, adhesive, welding rod, etc., it is desirable to use a styrene-modified acrylic resin in addition to the resin having the above-mentioned affinity. What is styrene-modified acrylic resin?
It is a copolymer of styrene and acrylic ester.
Examples of the acrylic ester include methyl acrylate, ethyl acrylate, n-propyl acrylate, iso
-Propyl acrylate, n-butyl acrylate, i
so-butyl acrylate, t-butyl acrylate,
Acrylate such as 2-ethylhexyl acrylate, cyclohexyl acrylate, tetrahydrofurfuryl acrylate is exemplified, and methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, i.
so-propyl methacrylate, n-butyl methacrylate, iso-butyl methacrylate, 2-ethylhexyl methacrylate, cyclohexyl methacrylate,
Methacrylates such as tetrahydrofurfuryl methacrylate, stearyl methacrylate, lauryl methacrylate may be used.

The above-mentioned styrene-modified acrylic resin is a vinyl ether such as methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl ether, n-butyl vinyl ether, iso-butyl vinyl ether, acrylonitrile, etc. to the extent that the affinity with the molded product is not impaired. Nitrile-based monomers such as methacrylonitrile, aliphatic vinyl such as vinyl acetate and vinyl propionate, halogen-containing monomers such as vinyl chloride, vinylidene chloride, vinyl fluoride and vinylidene fluoride, olefins such as ethylene and propylene , Isoprene, chloroprene, dienes such as butadiene, α, β-unsaturated carboxylic acids such as acrylic acid, methacrylic acid, itaconic acid, maleic acid, crotonic acid, atropic acid and citraconic acid, 2-hydroxyethyl methacrylate, 2 -Hi Droxyethyl acrylate, 2-
Hydroxy group-containing monomers such as hydroxypropyl methacrylate, 2-hydroxypropyl acrylate and allyl alcohol, amides such as acrylamide, methacrylamide, diacetone acrylamide, amino such as dimethylaminomethyl methacrylate, dimethylaminoethyl methacrylate and dimethylaminopropyl acrylate. Group-containing monomers, epoxy group-containing monomers such as glycidyl acrylate, glycidyl methacrylate, glycidyl allyl ether, γ-methacryloxypropyltrimethoxysilane, vinylacetoxysilane, p-trimethoxysilylstyrene, p-triethoxysilylstyrene , P-trimethoxysilyl-α-methylstyrene, p-triethoxysilyl-α-methylstyrene, γ-acryloxypropyltrimethoxystyrene And vinyltrimethoxysilane, N-β (N-vinylbenzylaminoethyl-γ-aminopropyl) trimethoxysilane, hydrochloride and other hydrolyzable silyl group-containing vinyl monomers and other monomers are copolymerized. May be done. The above monomers may be used alone or in combination.

Further, as the above-mentioned paint or ink, a fibrin derivative may be added for the purpose of improving coatability, printability, coating film strength, drying property and the like. Examples of the fibrin derivative include methyl cellulose (hydroxypropyl methyl cellulose), ethyl cellulose (Ethocel), hydroxyethyl cellulose, hydroxyethyl methyl cellulose, cellulose acetate (cotton acetate, fibrin acetate, cellulose acetate / acetyl cellulose),
It is desirable to use a non-yellowing type such as benzyl cellulose, cellulose or cellulose acetate butyrate (CAB).

[Case of PPE Resin] In the case of PPE resin, the same resin as the above-mentioned styrene resin or styrene elastomer is used as the affinity resin.

[In the case of polyolefin-based resin] As the polyolefin-based resin, one or more α-olefins are polymerized by using a radical initiator, a metal oxide-based catalyst, a Ziegler-Natta catalyst, a Kaminsky catalyst or the like. There is a resin or the like obtained by the above, and two or more kinds of the above resins may be mixed. The α-olefin is a linear / branched or cyclic olefin having a polymerizable double bond at the α-position, and usually has 2 to 8 carbon atoms. Specific examples of the α-olefin include ethylene and propylene. The polyolefin resin that is the subject of the present invention may be copolymerized with a monomer copolymerizable with α-olefin. Acrylic acid as other monomer,
Α-β unsaturated organic acids such as methacrylic acid, maleic acid, itaconic acid, methyl acrylate, ethyl acrylate, methyl methacrylate, maleic anhydride, aryl maleic acid imide, alkyl maleic acid imide or derivatives thereof;
Vinyl esters such as vinyl acetate and vinyl butyrate; aromatic vinyl compounds such as styrene and methylstyrene; vinyl silanes such as vinyltrimethylmethoxysilane and γ-methacryloyloxyprolyltrimethoxysilane, and 1,4-hexadiene and 4- A small amount of non-conjugated dienes such as methyl-1,4-hexadiene, 5-4-methyl-1,4-hexadiene, dicyclopentadiene and ethylidene norbornene (4-ethylidene-2-norbornene) may be copolymerized. Typical examples of the polyolefin resin include polyethylene, polypropylene, ethylene-vinyl acetate copolymer, ethylene-acrylic acid copolymer and the like.

As the affinity resin for such a polyolefin resin, any of the above-exemplified polyolefin resins, thermoplastic elastomer (TPE) such as urethane elastomer, styrene elastomer, vinyl elastomer, ester elastomer, etc. Is exemplified. In addition to polyolefin resins with affinity for inks, paints, adhesives, welding rods, etc., chlorinated PP
The use of halogenated PP such as Halogenated PP
Shows good solubility in a solvent.

[Recycling Information] The recycling information includes, for example, collection information, selection information and reproduction information. <Recovery Information> The recovery information is information about how to collect the waste products and transport them to the recycling site. The information is input to, for example, a two-dimensional barcode. Case 1 Waste products → Disposal site → Collection → Reproduction site Case 2 Waste products → Collection → Reproduction site

In the case of Case 1, the user conveys the waste to a predetermined disposal location designated by the recovery information. The designated disposal points include, for example, a courier service office, a convenience store, a post office, a liquor store, a manufacturer's service office, a dealership service office, etc. Is desirable. The waste products are collected by the carrier etc. specified in the collection information and transported to the recycling site.

In the case of Case 2, the waste products are picked up by a pick-up company, a leasing company, or a transportation organization dedicated to the recycling site, and transported to the recycling site. In this case, the user will contact the pick-up company, the leasing company, or the transporting agency by means of contact means such as a telephone, a fax machine, a telecommunication line, etc., as instructed in the collection information and have the user pick it up. Alternatively, the user may send the goods directly to the manufacturer by cash on delivery.

<Selection information> As the selection information, for example, a method of removing by removing screws and the like, a method of decomposing by breaking, a method of crushing and wind selecting, a paint, an adhesive, a melting rod, a label, a seal, an ink film, etc. In the case of, a method of removing by grinding, a method of dissolving insoluble matter and a soluble matter by dissolving in a solvent, an affinity between a coating film or an ink film and a thermoplastic resin of a molded article, or separation of the coating film or the ink film. Whether or not peeling is required, the components of the product, the coupling style of each component (for example, bonding, welding, screwing, etc.), the manufacturer name of each component, the property,
Information on precautions (eg, toxicity, corrosiveness, flammability, explosiveness, etc.), handling methods, and decomposition methods is input. These pieces of information are input to, for example, a two-dimensional barcode.

At the recycling site, the thermoplastic resin element is selected according to the above selection information. Furthermore, if there are two or more resin elements and they have mutual affinity, information to that effect is input, so that at the regeneration site, regeneration is performed without separating into resin elements. When some or all of the two or more resin elements do not have mutual affinity, the information to that effect is input, so each resin element is sorted at the regeneration site.

<Reproduction Information> In the reproduction information, information for manufacturing a resin product using the resin selected by the selection information is input. For example, the type of resin,
Input information such as the type and amount of additives (eg, pigments / dyes, antistatic agents added to restore color), hazard information of additives, legal regulations during manufacturing, and future trends To be done. It is also desirable to input information on the number of times the resin that constitutes the product is recycled, the presence / absence of mixing of the recycling improver, and the mixing amount. These pieces of information are input to, for example, a two-dimensional barcode.

As described above, when the resin elements have mutual affinity, information to that effect is input, and therefore each resin element is crushed and melted as it is without being separated based on the information, and pellets are formed if desired. It can be solidified, melted, and molded. In this case, since crushing conditions, melting conditions, pelletizing conditions, molding method and molding conditions, addition of recyclability improving material, etc. are input, at the recycling site, resin products can be easily and appropriately recycled based on this information.

The above-mentioned equivalent regenerant can be used as the recyclability improving material. Further, these recycled resins may be mixed with a virgin resin and molded to be recycled as a resin product. In this case, the mixing ratio, molding method, molding conditions, etc. are also input. If the resin elements do not have mutual affinity, information indicating that fact is input, so that the resin elements are sorted based on the information, and each resin element is regenerated. As the sorting method, the same method as that input to the selection information is input.

[Example 1] The recycling system of the present invention was applied to a printer (1) made of a thermoplastic resin. FIG. 1 shows the process flow of this embodiment. FIG. 2 shows an OA which is a thermoplastic resin product or a home printer (1). The exterior panel (11) of the printer (1) is a molded product of thermoplastic resin, and the thermoplastic resin contains 25% recycled material.
Glass fiber and talc are added to the BS resin as a phosphorus-based flame retardant and a reinforcing material. The exterior panel
Parts such as switches are mounted on the operation switch section (12) of (11), and various interior parts are provided inside the exterior panel. The switches and other interior parts are exterior panels (11)
It is composed of a thermoplastic resin and a metal part having the same or similar affinity. On the side surface of the exterior panel (11), a collection information label (decal) (2) and a selection information label shown in FIGS.
(3) and reproduction information label (4) are attached. Collection information, selection information, and reproduction information are printed on the collection information label (2), the selection information label (3), and the reproduction information label (4), respectively. The label (2,3,4) and the label
The ink and adhesive used in (2,3,4) are also made of a resin having an affinity with the thermoplastic resin of the exterior panel (11).
Further, the exterior panel (11) may be coated, and in this case, the coating material is preferably a resin having an affinity with the exterior panel (11).

As shown in FIG. 3, the collection information includes a convenience store and a post office as collection destinations, and contact information such as a manufacturer name and its telephone number, homepage address, and e-mail address as inquiries and delivery destinations. ing. Further, the bar code (2a), the two-dimensional bar code (2b), and the symbol (2c) consisting of alphabets and numbers are described.
In this case, it is necessary to make an arrangement with the convenience store and the post office in advance for collection and transportation.

The user carries in the waste products to the convenience store or the post office based on the written information. The introduced waste products are carried to the sorting / reproduction site, which is the destination of the input, described in the collection information by the delivery system of the convenience store, the collection / delivery system of the post office, or the carrier. The user can also contact the prescribed contact information to request the collection, can request the collection via the Internet, and can obtain the collection information.

The barcode (2a) and the two-dimensional barcode (2
In b), concrete and detailed information about the collection method such as collection points nationwide, locations of manufacturers' sales offices and factories, and contact information is input. Especially, a large amount of information can be input to a two-dimensional barcode. Therefore, detailed information can be obtained if the user or the collection company has the barcode reading means. Further, the symbol (2c) is a symbol for extracting the corresponding detailed collection information from the predetermined database.If the bar code reader is not provided, the user can, for example, access the predetermined server (for example, the manufacturer's website) via the Internet or the like. ) And enter the symbol (2c) to get more information.

As shown in FIG. 4, the selection information includes the model name,
The exterior material, interior material, and cartridge material are listed. Based on the sorting information, the manufacturer or the recycler to whom the waste product has been conveyed can know the material of the product, and can determine the necessity of separation / disassembly. Further, the bar code (3a) and the two-dimensional bar code (3b) are made of materials of all parts (including coating film, ink film, adhesive, label, etc.) that compose the product
Information on physical properties, added components, and affinity of constituent resins is input. Further, the symbol (3c) for extracting the corresponding detailed selection information from the predetermined database is described. Therefore, at the recycling site, it is possible to judge whether they can be mixed or decomposed and recycled separately based on the affinity of the resin constituting the product.

As shown in FIG. 5, the reproduction information includes information on the part name, material, additive, and reinforcing material. The material also describes the ratio of recycled materials. Bar code (4a)
And the two-dimensional bar code (4b), the type of resin of all parts (including coating film, ink film, adhesive, label, etc.), additives, reinforcing material recycling history, etc. Specific and detailed information such as pelletization conditions (temperature, screw rotation speed, cold cut or hot cut, etc.) is input. Also, a symbol (4c) for extracting the corresponding detailed reproduction information from a predetermined database is described. Based on the reproduction information, at the reproduction site, it is possible to accurately grasp the type of the resin constituting the product and the mixed components, and to appropriately recycle the resin.

Since all the resin materials constituting the printer (1) of the present embodiment have an affinity, the resin parts are crushed and melted on the basis of the information without sorting at the recycling site, and if desired, the equivalent reproduction is performed. Reagents may be added to prepare regenerated pellets. Note that it is difficult to strictly classify the collection information, the selection information, and the reproduction information, so it is sufficient to describe / input them in any one.

In the present invention, all the information necessary for recycling, including the product and the labels, inks, and adhesives attached to the product, is attached to the product itself, such as users, manufacturers, transporters, and recycling sites. In any of the steps, necessary and accurate information can be surely obtained.

[0058]

According to the present invention, a waste product can be reliably and easily equivalently regenerated, resources can be effectively used, and the amount of dust can be reduced.

[Brief description of drawings]

1 to 5 show an embodiment of the present invention.

[Figure 1] Process flow diagram of the recycling system

[Figure 2] Printer perspective view

[Figure 3] Collection information label

[Figure 4] Sorting information label

[Fig. 5] Playback information label

[Explanation of symbols]

1 Printer (molded with thermoplastic resin) 2 Collection information label 2a, 3a, 4a Bar code 2b, 3b, 4b Two-dimensional bar code 2c, 3c, 4c Symbol 3 Sorting information label 4 Reproduction information label

Claims (7)

[Claims] 1. A thermoplastic resin product having recycling information. 2. The thermoplastic resin product according to claim 1, wherein the recycling information comprises at least collection information, selection information, and reproduction information. 3. The thermoplastic resin product according to claim 1 or 2, wherein the thermoplastic resin product has a plurality of thermoplastic resin elements and has affinity for each other. 4. The thermoplastic resin product according to claim 3, wherein an equivalent regenerant is added to at least a main element of the thermoplastic resin elements to enable equivalent regeneration. 5. A method for producing a recycled thermoplastic resin, characterized in that waste thermoplastic resin products with recycling information are recycled based on the recycling information. 6. The recycling information attached to the thermoplastic resin product comprises at least collection information, sorting information, and reproduction information, and waste products of the thermoplastic resin product are collected based on the collection information attached to the product. Then, the waste products are sorted according to the sorting information and the thermoplastic resin elements are sorted and collected at the recycling spot, and further, the thermoplastic resin elements sorted and collected based on the recycling information are recycled. The method for producing a recycled thermoplastic resin according to claim 5, wherein a thermoplastic resin product is produced. 7. A thermoplastic resin product is provided with recycling information consisting of at least collection information, sorting information and reproduction information, and a waste product of the thermoplastic resin product is collected by the collection information attached to the product. And then transporting it to the recycling site, at the recycling site, sorting the waste products by sorting information according to the sorting information, and collecting the thermoplastic resin element, and using the thermoplastic resin element sorted and collected based on the recycling information. A recycling system comprising the steps of manufacturing a recycled thermoplastic resin product.