JPH08259747A - Reclaimed thermoplastic resin composition - Google Patents
Reclaimed thermoplastic resin compositionInfo
- Publication number
- JPH08259747A JPH08259747A JP9154395A JP9154395A JPH08259747A JP H08259747 A JPH08259747 A JP H08259747A JP 9154395 A JP9154395 A JP 9154395A JP 9154395 A JP9154395 A JP 9154395A JP H08259747 A JPH08259747 A JP H08259747A
- Authority
- JP
- Japan
- Prior art keywords
- epoxidized
- resin composition
- thermoplastic resin
- resins
- polymer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、再生熱可塑性樹脂組成
物に関し、より詳細には２種以上の熱可塑性樹脂を積層
してなる構造体の廃材を利用した樹脂組成物であり、優
れた流動性、強度特性、成形性等を有する再生熱可塑性
樹脂組成物に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a recycled thermoplastic resin composition, and more particularly to a resin composition utilizing a waste material of a structure formed by laminating two or more kinds of thermoplastic resins, which is excellent. The present invention relates to a recycled thermoplastic resin composition having fluidity, strength characteristics, moldability and the like.
【０００２】[0002]
【従来の技術】熱可塑性樹脂は軽量性、成形加工の容易
性、着色加工の容易性の他、錆びにくいことなどの種々
の優れた性質を有するため、各種工業用材料部品や包装
容器材料などに広範囲かつ大量に生産・消費されてい
る。これらの中には、２種以上の熱可塑性樹脂を積層し
た構造体も多方面に用いられている。例えば、ある熱可
塑性樹脂からなる繊維構造体やシート、フィルム、発泡
体などに他の熱可塑性樹脂を積層した構造体は、感触性
やクッション性、耐薬品性などが改良された素材とし
て、車両内装材、カバン材料、包装・容器材料まで様々
な用途に使用されている。2. Description of the Related Art Thermoplastic resins have various excellent properties such as light weight, easiness of molding and coloring, and resistance to rust. Widely produced and consumed in large quantities. Among these, a structure in which two or more kinds of thermoplastic resins are laminated is also used in various fields. For example, a fibrous structure made of a certain thermoplastic resin, a structure in which a sheet, a film, a foam or the like is laminated with another thermoplastic resin is used as a material having improved feel, cushioning property, chemical resistance, etc. It is used for various purposes such as interior materials, bag materials, and packaging / container materials.
【０００３】一方、資源の節約や環境保全の面から、資
源の再利用という社会的ニーズが高まっている。従っ
て、上記２種以上の熱可塑性樹脂を積層した構造体も、
その成分ごとに分離して回収したり、解重合法によって
中間原料として回収するなどの方法が提案されている。On the other hand, in order to save resources and protect the environment, social needs for resource reuse are increasing. Therefore, the structure in which two or more kinds of thermoplastic resins are laminated is also
Methods such as separating and recovering each of the components or recovering as an intermediate raw material by a depolymerization method have been proposed.
【０００４】[0004]
【発明が解決しようとする課題】しかし、一般に工業的
に用いられている２種以上の熱可塑性樹脂を積層した構
造体は、両者が強固に接着されていたり入り組んだ構造
になっていたりするものが多く、そのため成分ごとの分
離が困難であり、あるいは解重合成分が複雑であるため
解重合による再利用を工業的に実施するには問題が多
い。一方、かかる２種以上の熱可塑性樹脂の積層体の再
生方法として、それらの積層材料をなんら分離すること
なく混合し、多成分ポリマー材料として再利用しようと
する試みがなされている。しかし、単なる混合では、成
形材料として必要な流動性や強度特性を付与し、さらに
成形品の外観を優良なものとするのは容易でない。加え
て、一部の分野ではこれら廃材を再粉砕して製造工程な
どに再利用しているが、廃材の使用率は一般的に２０重
量％程度にとどまっているのが現状である。本発明は上
記した事情に鑑みて、２種以上の熱可塑性樹脂を積層し
てなる構造体の廃材をその成分毎に分離することなく再
利用することを目的とする。また、最終製品中に少なく
とも３０重量％、好ましくは５０重量％以上配合でき、
成形材料として必要な流動性や強度特性、外観特性など
を保持しうる再生熱可塑性樹脂組成物の提供を目的とす
る。However, the structure in which two or more kinds of thermoplastic resins which are generally used in industry are laminated has a structure in which both are firmly bonded or intricate. Therefore, it is difficult to separate the components from each other, or the depolymerization components are complicated, and there are many problems in industrially carrying out recycling by depolymerization. On the other hand, as a method for regenerating a laminate of such two or more thermoplastic resins, an attempt has been made to mix these laminate materials without separating them and reuse them as a multi-component polymer material. However, it is not easy to give the fluidity and strength characteristics required as a molding material and to make the appearance of the molded article excellent by simple mixing. In addition, in some fields, these waste materials are re-crushed and reused in the manufacturing process, etc., but the current usage rate of the waste materials is generally about 20% by weight. In view of the above-mentioned circumstances, the present invention has an object to reuse a waste material of a structure formed by laminating two or more kinds of thermoplastic resins without separating each component. Also, at least 30% by weight, preferably 50% by weight or more can be added to the final product,
It is an object of the present invention to provide a recycled thermoplastic resin composition that can retain the fluidity, strength characteristics, appearance characteristics and the like required as a molding material.
【０００５】[0005]
【課題を解決するための手段】本発明者らは、上記の課
題を解決するため鋭意検討の結果、２種以上の熱可塑性
樹脂を積層した構造体の廃材に、軟質のポリエチレン系
樹脂とエポキシ化（部分水添）ジエン系重合体とを配合
することにより流動性等の成形加工性に優れた再生熱可
塑性樹脂組成物を与えることを見いだし、本発明を完成
するに至った。Means for Solving the Problems As a result of intensive studies to solve the above problems, the present inventors have found that a waste material of a structure in which two or more kinds of thermoplastic resins are laminated is used as a soft polyethylene resin and an epoxy resin. It was found that a recycled thermoplastic resin composition excellent in molding processability such as fluidity can be provided by blending with a modified (partially hydrogenated) diene polymer, and the present invention has been completed.
【０００６】すなわち本発明は、（ａ）軟質のポリエチ
レン系樹脂２０〜６７重量％と、（ｂ）少なくとも２種
以上の熱可塑性樹脂を積層してなる構造体の廃材３０〜
７７重量％と、（ｃ）エポキシ化（部分水添）ジエン系
重合体３〜２０重量％からなる再生熱可塑性樹脂組成物
を提供するものである。また、（ｂ）成分の２種以上の
熱可塑性樹脂が、ポリアミド系樹脂、ポリエステル系樹
脂、ポリプロピレン系樹脂およびポリエチレン系樹脂よ
り選ばれる材料の組合せである前記再生熱可塑性樹脂組
成物を提供するものである。また、エポキシ化（部分水
添）ジエン系重合体（ｃ）が、共役ジエン化合物に由来
する二重結合を少なくとも１分子中１個エポキシ化した
ものである前記再生熱可塑性樹脂組成物を提供するもの
である。また、エポキシ化（部分水添）ジエン系重合体
（ｃ）がビニル芳香族化合物を主体とする重合体ブロッ
クと共役ジエン化合物を主体とする重合体ブロックとか
らなるブロック共重合体の共役ジエン化合物に由来する
二重結合を少なくとも１個エポキシ化したものである前
記再生熱可塑性樹脂組成物を提供するものである。さら
に、エポキシ化（部分水添）ジエン系重合体（ｃ）が共
役ジエン化合物に由来する二重結合を部分的に水素添加
し、さらに残存する共役ジエン化合物に由来する二重結
合の少なくとも１個をエポキシ化したものである前記再
生熱可塑性樹脂組成物を提供するものである。以下、本
発明を詳細に説明する。That is, according to the present invention, (a) 20 to 67% by weight of a soft polyethylene resin and (b) at least two kinds of thermoplastic resins are laminated to form a waste material 30 to 30
A recycled thermoplastic resin composition comprising 77% by weight and 3 to 20% by weight of (c) an epoxidized (partially hydrogenated) diene polymer is provided. Further, there is provided the regenerated thermoplastic resin composition, wherein the two or more thermoplastic resins of the component (b) are a combination of materials selected from polyamide resins, polyester resins, polypropylene resins and polyethylene resins. Is. Further, there is provided the regenerated thermoplastic resin composition, wherein the epoxidized (partially hydrogenated) diene polymer (c) is an epoxidized double bond derived from a conjugated diene compound in at least one molecule in one molecule. It is a thing. Further, a conjugated diene compound of a block copolymer in which the epoxidized (partially hydrogenated) diene polymer (c) is composed of a polymer block mainly containing a vinyl aromatic compound and a polymer block mainly containing a conjugated diene compound. The present invention provides the above-mentioned regenerated thermoplastic resin composition, wherein at least one double bond derived from is epoxidized. Furthermore, the epoxidized (partially hydrogenated) diene polymer (c) partially hydrogenates the double bond derived from the conjugated diene compound, and at least one double bond derived from the remaining conjugated diene compound is further added. The present invention provides the above-mentioned regenerated thermoplastic resin composition which is an epoxidized product. Hereinafter, the present invention will be described in detail.
【０００７】本発明における（ａ）軟質のポリエチレン
系樹脂としては、密度０．９２６ｇ／ｃｍ3（２３℃）
以下であり、高圧法低密度ポリエチレン、エチレンとα
−オレフィンとの共重合体である直鎖低密度ポリエチレ
ン、超低密度ポリエチレンおよび含量が３５重量％以下
のコモノマーとエチレンとの共重合体であるエチレン系
重合体から選ばれる１種または２種以上のポリエチレン
系樹脂が使用できる。エチレンと共重合させる前記コモ
ノマーとしては、エチレンと共重合可能な不飽和カルボ
ン酸またはその無水物、エステル誘導体、ビニルエステ
ルなど、たとえばアクリル酸、メタクリル酸、酢酸ビニ
ル、アクリル酸エチル、メタクリル酸メチル、メタクリ
ル酸の亜鉛塩、無水マレイン酸などが挙げられ、それら
の１種または２種以上の組み合わせを使用することがで
きる。The (a) soft polyethylene resin used in the present invention has a density of 0.926 g / cm 3 (23 ° C.)
Below, high pressure method low density polyethylene, ethylene and α
One or more selected from linear low-density polyethylene that is a copolymer with olefin, ultra-low-density polyethylene, and ethylene-based polymer that is a copolymer of ethylene with a comonomer content of 35% by weight or less Polyethylene resin can be used. As the comonomer to be copolymerized with ethylene, an unsaturated carboxylic acid copolymerizable with ethylene or an anhydride thereof, an ester derivative, a vinyl ester, etc., such as acrylic acid, methacrylic acid, vinyl acetate, ethyl acrylate, methyl methacrylate, Examples thereof include zinc salts of methacrylic acid and maleic anhydride, and one kind or a combination of two or more kinds thereof can be used.
【０００８】本発明の（ｂ）成分における熱可塑性樹脂
とは、たとえばポリアミド系樹脂、ポリエステル系樹
脂、塩化ビニル樹脂、ポリスチレン系樹脂、変性ポリフ
ェニレンエーテル、ポリカーボネート樹脂、ポリプロピ
レン系樹脂、低密度ポリエチレン樹脂、中密度ポリエチ
レン樹脂、高密度ポリエチレン樹脂等のポリエチレン樹
脂、ポリエチレンテレフタレート樹脂等の常用されてい
る各種合成樹脂や、スチレン系、オレフィン系、ウレタ
ン系、エステル系などの熱可塑性エラストマーなどから
選ばれる熱可塑性樹脂をいう。これら熱可塑性樹脂の積
層体とは、上記熱可塑性樹脂を２種以上を組み合わせて
押出成形法や射出成形法など公知の成形法でつくられた
多層構造体である。２種以上の組み合わせとしては、ポ
リアミド系樹脂、ポリエステル系樹脂、ポリプロピレン
系樹脂およびポリエチレン系樹脂より選ばれる材料の組
合せであることが好ましい。なお、上記例示した熱可塑
性樹脂は、それぞれ単一のポリマーからなるものでも、
ポリマーアロイなどの手法を用いて複合化されたもので
あってもよい。The thermoplastic resin in the component (b) of the present invention includes, for example, polyamide resins, polyester resins, vinyl chloride resins, polystyrene resins, modified polyphenylene ethers, polycarbonate resins, polypropylene resins, low density polyethylene resins, Thermoplastics selected from various commonly used synthetic resins such as polyethylene resin such as medium density polyethylene resin and high density polyethylene resin, polyethylene terephthalate resin, and thermoplastic elastomers such as styrene type, olefin type, urethane type and ester type Refers to resin. The laminated body of these thermoplastic resins is a multi-layer structure formed by a known molding method such as an extrusion molding method or an injection molding method by combining two or more kinds of the above thermoplastic resins. The combination of two or more kinds is preferably a combination of materials selected from polyamide resins, polyester resins, polypropylene resins and polyethylene resins. Incidentally, the thermoplastic resin exemplified above may be made of a single polymer,
It may be compounded using a method such as a polymer alloy.
【０００９】（ｂ）成分の熱可塑性樹脂を積層してなる
構造体としては、ポリアミド系樹脂、ポリエステル系樹
脂、ポリプロピレン系樹脂などの起毛状繊維をポリエチ
レン系樹脂や塩化ビニル樹脂などで裏打ちした車載用カ
ーペット、ポリプロピレン系樹脂シートに緩衡材として
の樹脂発泡層とさらに熱可塑性樹脂を主体とする織布な
どを積層して得た多層シート、発泡樹脂シートとフィル
ムや熱可塑性樹脂を主体とする不織布などとの積層体な
どが挙げられる。これら層構成体間の接着には接着剤が
使用される場合もあるが接着剤を含んだまま処理可能で
ある。上記熱可塑性樹脂を積層してなる構造体からなる
廃材は後述する混練機への投入と計量などの定量性の確
保を容易とするために、粉砕や裁断、熱処理などによる
減容化を行っておくことが好ましい。As the structure formed by laminating the thermoplastic resin as the component (b), a vehicle body in which raised fibers of polyamide resin, polyester resin, polypropylene resin, etc. are lined with polyethylene resin, vinyl chloride resin, etc. Carpet, polypropylene resin sheet, multilayer sheet obtained by laminating resin foam layer as cushioning material and woven cloth mainly made of thermoplastic resin, mainly made of foamed resin sheet and film or thermoplastic resin Examples include a laminate with a non-woven fabric and the like. An adhesive may be used for adhesion between these layer components, but it can be processed with the adhesive still contained. The waste material consisting of the structure formed by laminating the thermoplastic resin is subjected to volume reduction by crushing, cutting, heat treatment or the like in order to easily secure quantitativeness such as charging into a kneading machine and weighing described later. It is preferable to set.
【００１０】本発明に用いるエポキシ化（部分水添）ジ
エン系重合体（ｃ）とは、共役ジエン化合物を１成分と
する重合体、または共役ジエン化合物を１成分とする重
合体の部分水素添加したものの残存する共役ジエン化合
物に由来する二重結合を少なくとも１個エポキシ化した
ものが好ましい。共役ジエン化合物としては、たとえ
ば、ブタジエン、イソプレン、１，３−ペンタジエン、
２，３−ジメチル−１，３−ブタジエンなどの内から１
種または２種以上が選ばれ、中でもブタジエン、イソプ
レン、およびこれらの組み合わせが好ましい。また、ジ
エン系重合体はランダム共重合体、ホモポリマーまたは
ブロック共重合体でもよく、たとえばポリブタジエン、
ポリイソプレン、アクリロニトリル−ブタジエン共重合
体、天然ゴム、メチルメタアクリレート−スチレン−ブ
タジエン共重合体、スチレン−ブタジエン共重合体、ス
チレン−ブタジエン−スチレンブロック共重合体、スチ
レン−イソプレン−スチレン共重合体、スチレン−ブタ
ジエンブロック共重合体などが好ましい。また、これら
の共役ジエン化合物に由来する二重結合を部分的に水添
を行い、さらに残存する共役ジエン化合物に由来する二
重結合をエポキシ化したものも含まれる。The epoxidized (partially hydrogenated) diene polymer (c) used in the present invention means a polymer having a conjugated diene compound as a component or a partial hydrogenation of a polymer having a conjugated diene compound as a component. It is preferable that at least one double bond derived from the remaining conjugated diene compound is epoxidized. Examples of the conjugated diene compound include butadiene, isoprene, 1,3-pentadiene,
1 out of 2,3-dimethyl-1,3-butadiene
One kind or two or more kinds are selected, and among them, butadiene, isoprene, and a combination thereof are preferable. Further, the diene polymer may be a random copolymer, a homopolymer or a block copolymer, such as polybutadiene,
Polyisoprene, acrylonitrile-butadiene copolymer, natural rubber, methylmethacrylate-styrene-butadiene copolymer, styrene-butadiene copolymer, styrene-butadiene-styrene block copolymer, styrene-isoprene-styrene copolymer, A styrene-butadiene block copolymer and the like are preferable. Further, a double bond derived from these conjugated diene compounds is partially hydrogenated, and a double bond derived from the remaining conjugated diene compound is epoxidized.
【００１１】これらの（部分水添）ジエン系重合体のエ
ポキシ化はエポキシ化剤として、過酸、有機過酸化物を
用いて行うことができる。特に、過酢酸を用いると反応
制御がしやすいので好ましい。Epoxidation of these (partially hydrogenated) diene polymers can be carried out by using a peracid or an organic peroxide as an epoxidizing agent. Particularly, it is preferable to use peracetic acid because the reaction can be easily controlled.
【００１２】本発明で用いるエポキシ化（部分水添）ジ
エン系重合体（ｃ）には、エチレン−α−オレフィン共
重合体ゴム、エチレン−α−オレフィン−非共役ジエン
３元共重合体ゴム、ブチルゴム、スチレン系ゴム、ニト
リルゴム、フッ素ゴム、ウレタンゴムなどを添加するこ
とができる。これらの中でもエチレン−プロピレン、エ
チレン−ブテンなどのエチレン−α−オレフィン共重合
体ゴム、エチレン−プロピレン−（５−エチリデン−２
−ノルボルネン）、エチレン−プロピレン−ジシクロペ
ンタジエンなどのエチレン−α−オレフィン−非共役ジ
エン３元共重合体ゴム、（水添）スチレン−ブタジエン
ブロック共重合体、（水添）スチレン−イソプレンブロ
ック共重合体、水添スチレン−ブタジエンゴムなどのス
チレン系ゴムとのブレンド物でもよく、エポキシ化（部
分水添）ジエン系重合体（ｃ）を２０〜１００ｗｔ％含
有するものであればよい。The epoxidized (partially hydrogenated) diene polymer (c) used in the present invention includes ethylene-α-olefin copolymer rubber, ethylene-α-olefin-non-conjugated diene terpolymer rubber, Butyl rubber, styrene rubber, nitrile rubber, fluororubber, urethane rubber and the like can be added. Among these, ethylene-propylene, ethylene-α-olefin copolymer rubbers such as ethylene-butene, ethylene-propylene- (5-ethylidene-2)
-Norbornene), ethylene-α-olefin-non-conjugated diene terpolymer rubber such as ethylene-propylene-dicyclopentadiene, (hydrogenated) styrene-butadiene block copolymer, (hydrogenated) styrene-isoprene block copolymer A blend of a polymer and a styrene rubber such as hydrogenated styrene-butadiene rubber may be used as long as it contains 20 to 100 wt% of the epoxidized (partially hydrogenated) diene polymer (c).
【００１３】本発明における（ｃ）成分は（ｂ）成分を
構成する材料の組み合わせによってエポキシ化（部分水
添）ジエン系重合体の含有量、水素添加率および、また
はエポキシ当量を制御することが好ましい。すなわち、
本発明の樹脂組成物の上記（ａ）成分、（ｂ）成分およ
び（ｃ）成分の比率は、それぞれ２０〜６７重量％、３
０〜７７重量％、３〜２０重量％の範囲であり、好まし
くはそれぞれ３０〜６７重量％、３０〜７０重量％、３
０〜２０重量％の範囲より選ばれる。本発明においては
（ｃ）成分の配合量が再生熱可塑性樹脂組成物に対し３
重量％未満の場合は、柔軟性、耐衝撃性、耐寒性の改質
効果が少なく、２０重量％を超すと改質効果が飽和に達
する一方、耐熱変形温度の低下など好ましくない弊害が
現れる場合がある。また本発明の再生熱可塑性樹脂組成
物における（ｂ）成分と（ｃ）成分の比率も重要であ
り、例えば自動車用のポリアミド繊維と裏打ち材が低密
度ポリエチレン樹脂からなるタフトカーペットを（ｂ）
成分として用いた組成物を使用して、再生タフトカーペ
ット成分が５０重量％であるような低密度ポリエチレン
との再生熱可塑性樹脂組成物を製造する際には、（ｃ）
成分３０〜１０重量％に対してタフトカーペットの廃材
７０〜９０重量％の範囲（両者の合計１００重量％）で
あることが好ましい。In the component (c) of the present invention, the content of the epoxidized (partially hydrogenated) diene polymer, the hydrogenation rate, and / or the epoxy equivalent can be controlled by the combination of the materials constituting the component (b). preferable. That is,
The ratio of the above-mentioned component (a), component (b) and component (c) of the resin composition of the present invention is 20 to 67% by weight and 3 respectively.
The range is 0 to 77% by weight, 3 to 20% by weight, and preferably 30 to 67% by weight, 30 to 70% by weight, and 3 respectively.
It is selected from the range of 0 to 20% by weight. In the present invention, the compounding amount of the component (c) is 3 with respect to the recycled thermoplastic resin composition.
When it is less than 10% by weight, flexibility, impact resistance, and cold resistance are less effective in modifying, and when it exceeds 20% by weight, the modifying effect reaches saturation while unfavorable adverse effects such as reduction in heat distortion temperature appear. There is. Further, the ratio of the component (b) to the component (c) in the recycled thermoplastic resin composition of the present invention is also important, and for example, a tufted carpet in which a polyamide fiber for an automobile and a backing material are low density polyethylene resin is used (b).
When using the composition used as a component to produce a recycled thermoplastic resin composition with low-density polyethylene such that the recycled tuft carpet component is 50% by weight, (c)
It is preferable that the range is 70 to 90% by weight of the waste material of the tuft carpet with respect to 30 to 10% by weight of the component (total of 100% by weight of both).
【００１４】本発明の再生熱可塑性樹脂組成物には、熱
可塑性樹脂に通常使用される熱安定剤、光安定剤、紫外
線吸収剤、無滴剤、帯電防止剤、滑剤、ブロッキング防
止剤、難燃剤、着色剤、発泡剤、充填剤、補強材、軟化
剤などを添加することができ、これらは目的性能と樹脂
組成物に含まれるポリマー種への適性から選択される。The recycled thermoplastic resin composition of the present invention contains a heat stabilizer, a light stabilizer, an ultraviolet absorber, a non-dripping agent, an antistatic agent, a lubricant, an antiblocking agent, a hard stabilizer, which is usually used for thermoplastic resins. A flame retardant, a colorant, a foaming agent, a filler, a reinforcing material, a softening agent and the like can be added, and these are selected from the objective performance and suitability for the polymer species contained in the resin composition.
【００１５】本発明の再生熱可塑性樹脂組成物の製造方
法としては、（ｂ）成分である熱可塑性樹脂からなる廃
材と（ｃ）成分であるエポキシ化（部分水添）ジエン系
重合体とを、溶融または流動状態であらかじめ混合して
得た中間組成物を、（ａ）成分である軟質のポリエチレ
ン系樹脂で希釈して製造することができるが、各成分を
同時に混練機に投入して製造してもよい。また（ｃ）成
分の廃材のみを予め混練してペレット化し、次の工程で
（ａ）成分および（ｂ）成分を加えて混練することもで
きる。溶融温度は熱可塑性樹脂の組み合わせによって適
宜選択でき、目安としては成分（ｂ）の熱可塑性樹脂か
らなる廃材を構成する成分の中の最も高い融点または可
塑化温度を有する成分の該融点または可塑化温度より高
い温度条件が好ましい。たとえば、成分（ｂ）としてポ
リエチレンテレフタレート樹脂からなる不織布に植毛さ
れたタフトカーペットの廃材を用いるときには、２６０
〜２８０℃程度が適する。混合にはバンバリーミキサー
や加圧ニーダー、単軸押出機、二軸押出機、ミキシング
ロールなど熱可塑性樹脂の混練加工に常用される機器が
使用できる。As the method for producing the recycled thermoplastic resin composition of the present invention, a waste material comprising the thermoplastic resin as the component (b) and an epoxidized (partially hydrogenated) diene polymer as the component (c) are used. The intermediate composition obtained by previously mixing in a molten or fluid state can be prepared by diluting it with the soft polyethylene resin as the component (a). You may. It is also possible to knead only the waste material of the component (c) in advance and pelletize it, and then add the component (a) and the component (b) in the next step and knead. The melting temperature can be appropriately selected depending on the combination of the thermoplastic resins, and as a guide, the melting point or the plasticization of the component having the highest melting point or the plasticizing temperature among the components constituting the waste material composed of the thermoplastic resin of the component (b). Temperature conditions above the temperature are preferred. For example, when using a waste material of tuft carpet which is flocked to a nonwoven fabric made of polyethylene terephthalate resin as the component (b), 260
About 280 ° C is suitable. For mixing, a Banbury mixer, a pressure kneader, a single-screw extruder, a twin-screw extruder, a mixing roll, or other equipment commonly used for kneading thermoplastic resins can be used.
【００１６】かくして得られた本発明の再生熱可塑性樹
脂組成物は、各成分が緊密に混和しており、この組成物
のみあるいは未使用の成形用樹脂材料や本発明の組み合
わせの異なる組成物も包含する他の成形用再生材料で希
釈して各種樹脂成形品、たとえばフィルム、シート、パ
イプ、棒、植木鉢、パレット、パネル、ボードなどして
使用することができる。The regenerated thermoplastic resin composition of the present invention thus obtained is intimately mixed with each other, and this composition alone, an unused molding resin material or a composition having a different combination of the present invention may be used. It can be used as various resin molded products such as films, sheets, pipes, rods, flower pots, pallets, panels, boards, etc., after being diluted with other molding recycled materials.
【００１７】[0017]
【実施例】以下に実施例を示すが、本発明は、これらに
よって限定されるものではない。なお、以下の記述にお
ける比率および％は、特にことわらない限り重量基準で
あり、実施例および比較例における各種の評価に用いた
試験法は以下の通りである。EXAMPLES Examples will be shown below, but the present invention is not limited thereto. The ratios and% in the following description are based on weight unless otherwise specified, and the test methods used for various evaluations in Examples and Comparative Examples are as follows.
【００１８】（試験方法） （１）メルトフローレート（ｇ／１０分）：ＪＩＳ−Ｋ
６７６０−１９８１、１９０℃、２．１６ｋｇ荷重の条
件下で測定した。 （２）引張特性：引張降伏強さ（ｋｇｆ／ｃｍ2）、引
張破壊強さ（ｋｇｆ／ｃｍ2）および引張破壊伸び
（％）は、ＪＩＳ−Ｋ６７６０−１９８１に基づき、試
料は厚さ２ｍｍの圧縮成形シートから２号形試験片作成
し、試験速度２００ｍｍ／分で行った。 （３）耐寒性：厚さ２ｍｍの圧縮成形シートから１３ｍ
ｍ巾の短冊状試験片を切り出し、−３０℃の低温恒温槽
中で２時間保持した。所定時間経過後取り出し、直径１
０ｍｍの鉄棒に巻き付け、亀裂や折れの発生状況により
判定した。その判定は、◎は変化なし（優）、○は小さ
な（長さ１ｍｍ未満）亀裂の発生（良）、×は大きな
（長さ１ｍｍ以上）亀裂の発生または折れ（不可）とし
た。(Test method) (1) Melt flow rate (g / 10 minutes): JIS-K
6760-1981, 190 degreeC, it measured on the conditions of a 2.16 kg load. (2) Tensile properties: Tensile yield strength (kgf / cm 2 ), tensile fracture strength (kgf / cm 2 ) and tensile fracture elongation (%) are based on JIS-K6760-1981, and the sample has a thickness of 2 mm. A No. 2 type test piece was prepared from the compression-molded sheet, and the test speed was 200 mm / min. (3) Cold resistance: 13 m from a compression molded sheet with a thickness of 2 mm
A strip-shaped test piece having a width of m was cut out and held in a low temperature constant temperature bath at -30 ° C for 2 hours. Removed after a lapse of a predetermined time, diameter 1
It was wrapped around a 0 mm iron bar and judged by the occurrence of cracks and breaks. The evaluation was ⊚: no change (excellent), ◯: small (less than 1 mm in length) crack generation (good), x: large (1 mm or more in length) crack generation or breakage (impossible).
【００１９】（エポキシ化（部分水添）ジエン系重合体
（ｃ）の製造） （参考例１：重合体（１））部分水添ポリイソプレン
（粘度平均分子量２，５００、水添率９０％）をシクロ
ヘキサン溶媒中で３０ｗｔ％過酢酸酢酸エチル溶液とと
もに４０℃、４時間反応させ、得られたエポキシ化（部
分水添）ジエン系重合体溶液を水洗し、減圧乾燥により
溶媒を除去し、重合体（１）を得た（オキシラン酸素濃
度１．８２ｗｔ％）。(Production of Epoxidized (Partially Hydrogenated) Diene Polymer (c)) (Reference Example 1: Polymer (1)) Partially Hydrogenated Polyisoprene (Viscosity Average Molecular Weight 2,500, Hydrogenation Rate 90%) ) Was reacted with a 30 wt% ethyl peracetate solution in a cyclohexane solvent at 40 ° C. for 4 hours, the obtained epoxidized (partially hydrogenated) diene polymer solution was washed with water, and the solvent was removed by drying under reduced pressure. Coalescence (1) was obtained (oxirane oxygen concentration 1.82 wt%).
【００２０】（参考例２：重合体（２））部分水添スチ
レン−ブタジエンブロック重合体（数平均分子量６７，
０００、スチレン／ブタジエン重量比＝３／７、水添率
７９％）をシクロヘキサン溶媒中で５０℃、７時間、過
酢酸でエポキシ化し、水洗し、シクロヘキサンを含有す
る重合体を熱湯中に添加し重合体（２）を得た（オキシ
ラン酸素濃度３．５９ｗｔ％）。Reference Example 2: Polymer (2) Partially hydrogenated styrene-butadiene block polymer (number average molecular weight 67,
000, styrene / butadiene weight ratio = 3/7, hydrogenation rate 79%) in a cyclohexane solvent at 50 ° C. for 7 hours, epoxidized with peracetic acid, washed with water, and the polymer containing cyclohexane added to hot water. A polymer (2) was obtained (oxirane oxygen concentration 3.59 wt%).
【００２１】（参考例３：重合体（３））部分水添スチ
レン−イソプレン−スチレンブロック共重合体（数平均
分子量５６，８００、スチレン／イソプレン重量比＝３
／７、水添率７５％）をシクロヘキサン溶媒中で５０
℃、７時間、過酢酸でエポキシ化し、水洗し、メタノー
ル中で再沈し、さらに減圧乾燥機で残留する溶媒を除去
し、重合体（３）を得た（オキシラン酸素濃度３．８０
ｗｔ％）。(Reference Example 3: Polymer (3)) Partially hydrogenated styrene-isoprene-styrene block copolymer (number average molecular weight 56,800, styrene / isoprene weight ratio = 3)
/ 7, hydrogenation rate 75%) in cyclohexane solvent 50
The mixture was epoxidized with peracetic acid at 7 ° C. for 7 hours, washed with water, reprecipitated in methanol, and the residual solvent was removed by a vacuum dryer to obtain a polymer (3) (oxirane oxygen concentration 3.80).
wt%).
【００２２】（参考例４：重合体（４））スチレン−ブ
タジエン−スチレンブロック共重合体（数平均分子量６
９，２００、スチレン／ブタジエン重量比＝４／６）を
酢酸エチル溶媒中で過酢酸でエポキシ化し、水洗し、減
圧乾燥機で残量する溶媒を除去し、重合体（４）を得た
（オキシラン酸素濃度２．９８ｗｔ％）。Reference Example 4: Polymer (4) Styrene-butadiene-styrene block copolymer (number average molecular weight 6
9,200, styrene / butadiene weight ratio = 4/6) was epoxidized with peracetic acid in a solvent of ethyl acetate, washed with water, and the remaining solvent was removed by a vacuum dryer to obtain a polymer (4) ( Oxirane oxygen concentration 2.98 wt%).
【００２３】（参考例５：重合体（５））水添スチレン
−ブタジエンブロック共重合体（数平均分子量７８，５
００、スチレン／ブタジエン重量比＝３／７、水添率９
８％）をシクロヘキサン溶媒中で５０℃、７時間、過酢
酸でエポキシ化し、水洗し、減圧乾燥機で残量する溶媒
を除去し、重合体（５）を得た（オキシラン酸素濃度
０．３０ｗｔ％）。Reference Example 5 Polymer (5) Hydrogenated styrene-butadiene block copolymer (number average molecular weight 78,5)
00, styrene / butadiene weight ratio = 3/7, hydrogenation rate 9
8%) was epoxidized with peracetic acid in a cyclohexane solvent at 50 ° C. for 7 hours, washed with water, and the remaining solvent was removed by a vacuum dryer to obtain a polymer (5) (oxirane oxygen concentration 0.30 wt. %).
【００２４】（実施例１）本発明の（ｂ）成分として低
密度ポリエチレン樹脂が裏打ちされたポリプロピレン繊
維製ニードルパンチカーペット（熱可塑性樹脂の構成と
しては、ポリプロピレン樹脂：４５％、ポリエチレンテ
レフタレート樹脂：１０％、低密度ポリエチレン樹脂：
４０％、塩化ビニル樹脂：５％）の廃材を粉砕後加熱処
理によって減容化して得た小粒状のチップと、（ｃ）成
分として参考例１〜５で製造した重合体（１）〜（５）
を表−１に示す比率で、シリンダー温度２７０℃に設定
した２軸押出機に供給し混練して、本発明の樹脂組成物
の中間ペレットを得た。次に上記ペレットと（ａ）成分
として低密度ポリエチレン樹脂（宇部興産製、Ｆ２２
２，密度０．９２２）とをシリンダー温度２００℃に設
定した単軸押出機に供給し、ニードルパンチカーペット
由来の再生樹脂成分を３０％含有する本発明の再生熱可
塑性樹脂組成物のペレットとし、成形温度１６０℃で圧
縮成形法により厚さ２ｍｍのシートを得た。このシート
より各種試験片を作成し、その物性を測定した。結果を
表−１に示す。(Example 1) Needle punch carpet made of polypropylene fiber lined with low density polyethylene resin as the component (b) of the present invention (The thermoplastic resin composition is polypropylene resin: 45%, polyethylene terephthalate resin: 10) %, Low density polyethylene resin:
40%, vinyl chloride resin: 5%) waste material was pulverized and then heat-treated to reduce the volume, and small particles of the chips, and the polymers (1) to ((c) produced in Reference Examples 1 to 5). 5)
Was supplied to a twin-screw extruder having a cylinder temperature of 270 ° C. and kneaded at a ratio shown in Table 1 to obtain intermediate pellets of the resin composition of the present invention. Next, the above pellets and a low-density polyethylene resin (F22 manufactured by Ube Industries, Ltd.) as the component (a) are used.
2, a density of 0.922) and a cylinder temperature of 200 ° C. are supplied to a single-screw extruder to obtain pellets of the recycled thermoplastic resin composition of the present invention containing 30% of a recycled resin component derived from a needle punch carpet, A sheet having a thickness of 2 mm was obtained by a compression molding method at a molding temperature of 160 ° C. Various test pieces were prepared from this sheet and their physical properties were measured. The results are shown in Table 1.
【００２５】（比較例１）実施例１に使用したものと同
じニードルパンチカーペットの廃材を（ｂ）成分とし
て、低密度ポリエチレン樹脂を（ａ）成分として使用
し、実施例１と同じ手順と方法で表−１の比較例に示す
（ｃ）成分を含まない組成物および本発明の範囲外量の
（ｃ）成分を含む組成物を作り、その物性を測定した。
結果を表−１に示す。(Comparative Example 1) The same procedure and method as in Example 1 were carried out by using the same waste material of the needle punched carpet as that used in Example 1 as the component (b) and the low density polyethylene resin as the component (a). The composition containing no component (c) shown in Comparative Example in Table 1 and the composition containing the component (c) in an amount outside the range of the present invention were prepared, and their physical properties were measured.
The results are shown in Table 1.
【００２６】（実施例２）（ｂ）成分として低密度ポリ
エチレン樹脂が裏打ちされたポリアミド繊維製タフトカ
ーペット（熱可塑性樹脂の構成としては、ポリアミド樹
脂：４０％、ポリエチレンテレフタレート樹脂：１０
％、低密度ポリエチレン樹脂：５０％）の廃材を粉砕後
加熱処理によって減容化して得た小粒状のチップと、
（ｃ）成分として参考例１〜５で製造した重合体（１）
〜（５）を表−２に示す比率で、シリンダー温度２８０
℃に設定した２軸押出機に供給し混練して、本発明の樹
脂組成物の中間ペレットを得た。次にこのペレットと
（ａ）成分として低密度ポリエチレン樹脂（宇部興産
製、Ｆ２２２）とをシリンダー温度２００℃に設定した
単軸押出機に供給し、タフトカーペット由来の再生樹脂
成分を３０〜５０％含有する再生熱可塑性樹脂組成物の
ペレットとし、成形温度１６０℃で圧縮成形法により厚
さ２ｍｍのシートを得た。このシートより各種試験片を
作成し、その物性を測定した。結果を表−２に示す。Example 2 A tuft carpet made of polyamide fiber backed with a low-density polyethylene resin as the component (b) (The composition of the thermoplastic resin is polyamide resin: 40%, polyethylene terephthalate resin: 10)
%, Low-density polyethylene resin: 50%), and crushed waste material to reduce the volume by heat treatment
Polymer (1) produced in Reference Examples 1 to 5 as component (c)
~ (5) at the ratio shown in Table-2, cylinder temperature 280
The mixture was supplied to a twin-screw extruder set at ℃ and kneaded to obtain intermediate pellets of the resin composition of the present invention. Next, the pellets and a low-density polyethylene resin (F222, manufactured by Ube Industries, Ltd.) as the component (a) were supplied to a single-screw extruder set to a cylinder temperature of 200 ° C., and a recycled resin component derived from the tufted carpet was 30 to 50%. A pellet of the recycled thermoplastic resin composition contained was formed into a sheet having a thickness of 2 mm by a compression molding method at a molding temperature of 160 ° C. Various test pieces were prepared from this sheet and their physical properties were measured. Table 2 shows the results.
【００２７】（比較例２）実施例２に使用したものと同
じタフトカーペットの廃材を（ｂ）成分を使用し、実施
例２と同じ手順と方法で表−２の比較例に示す（ｃ）成
分を含まない組成物、及び範囲外の（ｃ）成分を含む組
成物を得た。次にこれを実施例１と同様にして（ａ）成
分として低密度ポリエチレン樹脂とを混合し、得られた
最終的組成物についてその諸特性を測定した。結果を表
−２に示す。(Comparative Example 2) A waste material of the same tuft carpet as that used in Example 2 is used as the component (b), and the same procedure and method as in Example 2 are shown in Comparative Example of Table-2 (c). A composition containing no components and a composition containing component (c) outside the range were obtained. Then, this was mixed with a low-density polyethylene resin as the component (a) in the same manner as in Example 1 and various properties of the final composition thus obtained were measured. Table 2 shows the results.
【００２８】実施例１より、本発明の各再生熱可塑性樹
脂組成物は、比較例１に比べ、降伏点強さから判断した
柔軟性、引張破断伸び、耐寒性ともに大巾に改良されて
いた。また、実施例２より、本発明の実施例２の再生熱
可塑性樹脂組成物は、本発明の範囲外の比較例２に比べ
柔軟性、引張破断伸び耐寒性とも著しく改良されてい
た。エポキシ化（部分水添）ジエン重合体の選択により
流動性の制御も可能となり、加工法に適した粘度特性を
有する組成物が得られた。From Example 1, each regenerated thermoplastic resin composition of the present invention was greatly improved in flexibility, tensile elongation at break and cold resistance as judged from the yield strength as compared with Comparative Example 1. . Further, from Example 2, the regenerated thermoplastic resin composition of Example 2 of the present invention was significantly improved in both flexibility and tensile elongation at break compared to Comparative Example 2 outside the scope of the present invention. The fluidity can be controlled by selecting the epoxidized (partially hydrogenated) diene polymer, and a composition having a viscosity characteristic suitable for the processing method was obtained.
【００２９】[0029]
【表１】 [Table 1]
【００３０】[0030]
【表２】 [Table 2]
【００３１】[0031]
【発明の効果】本発明によれば、２種以上の熱可塑性樹
脂を積層した構造体の廃材を、分離などの複雑な工程を
省略して再利用することができる。しかも、必要に応じ
減容化などの比較的簡易な前処理を行うだけで、良好な
流動性、強度特性、耐寒性等の諸特性を有する再生熱可
塑性樹脂組成物を得ることができる。特に、従来技術で
は困難であった廃材含量の高いレベルの再生熱可塑性樹
脂組成物の提供が可能となった。According to the present invention, the waste material of the structure in which two or more kinds of thermoplastic resins are laminated can be reused by omitting complicated steps such as separation. In addition, a recycled thermoplastic resin composition having various properties such as good fluidity, strength characteristics, and cold resistance can be obtained by simply performing a relatively simple pretreatment such as volume reduction as necessary. In particular, it has become possible to provide a recycled thermoplastic resin composition having a high level of waste material, which has been difficult with the prior art.
Claims (5)
６７重量％と、（ｂ）少なくとも２種以上の熱可塑性樹
脂を積層してなる構造体の廃材３０〜７７重量％と、
（ｃ）エポキシ化（部分水添）ジエン系重合体３〜２０
重量％からなる再生熱可塑性樹脂組成物。1. (a) Soft polyethylene resin 20 to
67% by weight, and (b) 30 to 77% by weight of a waste material of a structure formed by laminating at least two kinds of thermoplastic resins,
(C) Epoxidized (partially hydrogenated) diene polymer 3 to 20
Recycled thermoplastic resin composition consisting of wt%.
が、ポリアミド系樹脂、ポリエステル系樹脂、ポリプロ
ピレン系樹脂およびポリエチレン系樹脂より選ばれる材
料の組合せである請求項１記載の再生熱可塑性樹脂組成
物。2. The recycled thermoplastic resin according to claim 1, wherein the two or more thermoplastic resins as the component (b) are a combination of materials selected from polyamide resins, polyester resins, polypropylene resins and polyethylene resins. Resin composition.
（ｃ）が、共役ジエン化合物に由来する二重結合を少な
くとも１分子中１個エポキシ化したものである請求項１
記載の再生熱可塑性樹脂組成物。3. The epoxidized (partially hydrogenated) diene polymer (c) is one in which at least one double bond derived from a conjugated diene compound is epoxidized in one molecule.
The regenerated thermoplastic resin composition described.
（ｃ）がビニル芳香族化合物を主体とする重合体ブロッ
クと共役ジエン化合物を主体とする重合体ブロックとか
らなるブロック共重合体の共役ジエン化合物に由来する
二重結合を少なくとも１個エポキシ化したものである請
求項１記載の再生熱可塑性樹脂組成物。4. An epoxidized (partially hydrogenated) diene polymer (c) is a block copolymer composed of a polymer block containing a vinyl aromatic compound as a main component and a polymer block containing a conjugated diene compound as a main component. The regenerated thermoplastic resin composition according to claim 1, wherein at least one double bond derived from a conjugated diene compound is epoxidized.
（ｃ）が共役ジエン化合物に由来する二重結合を部分的
に水素添加し、さらに残存する共役ジエン化合物に由来
する二重結合の少なくとも１個をエポキシ化したもので
ある請求項１記載の再生熱可塑性樹脂組成物。5. The epoxidized (partially hydrogenated) diene polymer (c) partially hydrogenates a double bond derived from a conjugated diene compound, and further, a double bond derived from a conjugated diene compound remaining The regenerated thermoplastic resin composition according to claim 1, wherein at least one is epoxidized.
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9154395A JPH08259747A (en) | 1995-03-24 | 1995-03-24 | Reclaimed thermoplastic resin composition |
| PCT/JP1996/000595 WO1996028514A1 (en) | 1995-03-10 | 1996-03-11 | Reclaimed thermoplastic resin compositions and process for the production thereof |
| EP96905055A EP0761763A4 (en) | 1995-03-10 | 1996-03-11 | Reclaimed thermoplastic resin compositions and process for the production thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9154395A JPH08259747A (en) | 1995-03-24 | 1995-03-24 | Reclaimed thermoplastic resin composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH08259747A true JPH08259747A (en) | 1996-10-08 |
Family
ID=14029398
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP9154395A Pending JPH08259747A (en) | 1995-03-10 | 1995-03-24 | Reclaimed thermoplastic resin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH08259747A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2003087215A1 (en) * | 2002-04-12 | 2003-10-23 | Mba Polymers, Inc. | Compositions of materials containing recycled plastics |
| US7802685B2 (en) | 2002-04-12 | 2010-09-28 | Mba Polymers, Inc. | Multistep separation of plastics |
-
1995
- 1995-03-24 JP JP9154395A patent/JPH08259747A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2003087215A1 (en) * | 2002-04-12 | 2003-10-23 | Mba Polymers, Inc. | Compositions of materials containing recycled plastics |
| US7802685B2 (en) | 2002-04-12 | 2010-09-28 | Mba Polymers, Inc. | Multistep separation of plastics |
| US7884140B2 (en) | 2002-04-12 | 2011-02-08 | Mba Polymers, Inc. | Compositions of materials containing recycled plastics |
| US8450382B2 (en) | 2002-04-12 | 2013-05-28 | Mba Polymers, Inc. | Compositions of material containing recycled plastics |
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