JPH0899343A - Extrusion molded product - Google Patents
Extrusion molded productInfo
- Publication number
- JPH0899343A JPH0899343A JP7153215A JP15321595A JPH0899343A JP H0899343 A JPH0899343 A JP H0899343A JP 7153215 A JP7153215 A JP 7153215A JP 15321595 A JP15321595 A JP 15321595A JP H0899343 A JPH0899343 A JP H0899343A
- Authority
- JP
- Japan
- Prior art keywords
- vinyl chloride
- resin composition
- chloride resin
- weight
- soft
- 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.)
- Granted
Links
Landscapes
- Extrusion Moulding Of Plastics Or The Like (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は耐熱性、成形性及び耐変
形性に優れた合成樹脂製の押出成形品に関し、更に具体
的にはシール材に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a synthetic resin extruded product having excellent heat resistance, moldability and deformation resistance, and more specifically to a sealing material.
【０００２】[0002]
【従来の技術】従来、建築、自動車、厨房器具等のパッ
キン、ガスケット等のシール材には、軟質塩化ビニル樹
脂等の軟質合成樹脂又は架橋ゴム等の軟質材料が使用さ
れている。2. Description of the Related Art Conventionally, a soft material such as a soft synthetic resin such as a soft vinyl chloride resin or a crosslinked rubber has been used as a sealing material such as a packing and a gasket for construction, automobiles, kitchen appliances and the like.
【０００３】軟質合成樹脂又は架橋ゴム材料は、それら
単独で押出、射出、圧縮成形された製品として使用され
る。又、金属と樹脂を同一金型（以下ダイと称する）内
で溶融一体化したり（以下共押出と称する）、又は金属
と接着したりしてシール材として使用される。The soft synthetic resin or the crosslinked rubber material is used alone as a product extruded, injected or compression molded. Further, a metal and a resin are melt-integrated in the same mold (hereinafter referred to as a die) (hereinafter referred to as co-extrusion) or bonded to a metal to be used as a sealing material.
【０００４】しかしながら、金属の共押出されたシール
材は、材料をリサイクルするためには、樹脂と金属を分
離する必要があり、経済的に不利であった。However, the metal co-extruded sealing material is economically disadvantageous because it is necessary to separate the resin and the metal in order to recycle the material.
【０００５】この対策として、金属の代わりに硬質合成
樹脂を使用し、共押出することが検討されている。硬質
合成樹脂を使用した共押出シール材は、硬質合成樹脂と
軟質材料を共押出成形したり、又は硬質合成樹脂と軟質
材料を接着したりした後に、加工及び製造されている。
硬質合成樹脂としては例えば、ＡＢＳ樹脂及び硬質塩化
ビニル樹脂等が挙げられるが、ＡＢＳ樹脂は軟質塩化ビ
ニル樹脂と接着又は共押出した場合にはクラック等を発
生しやすく、実用には適さなかった。As a countermeasure for this, coextrusion using a hard synthetic resin instead of metal has been studied. The co-extrusion sealing material using a hard synthetic resin is processed and manufactured after co-extruding a hard synthetic resin and a soft material or adhering a hard synthetic resin and a soft material.
Examples of the hard synthetic resin include ABS resin and hard vinyl chloride resin. However, ABS resin is not suitable for practical use because it easily causes cracks or the like when adhered or co-extruded with soft vinyl chloride resin.
【０００６】このため、軟質材料と共押出する硬質材料
としては、一般的に硬質塩化ビニル樹脂が使用される。Therefore, a hard vinyl chloride resin is generally used as the hard material coextruded with the soft material.
【０００７】又、軟質材料としては例えば、軟質塩化ビ
ニル樹脂、オレフィン系樹脂及びゴム等が挙げられる
が、共押出をする場合には一般的に硬質材料との熱融着
性及び加工性に優れる軟質塩化ビニル樹脂が使用され
る。The soft material includes, for example, soft vinyl chloride resin, olefin resin and rubber. When coextruding, it is generally excellent in heat fusion property with hard material and workability. Soft vinyl chloride resin is used.
【０００８】このようにして得られたシール材は建築、
自動車、厨房器具等に使用される。The sealing material thus obtained is used for construction,
Used in automobiles and kitchen appliances.
【０００９】しかしながら、これらを屋外で使用した場
合には、シール材の温度が７０℃以上にも達し、自動車
の内装用で使用した場合には自動車の内部の温度は最高
で９０℃にも達することがある。However, when these are used outdoors, the temperature of the sealing material reaches 70 ° C. or higher, and when used for the interior of automobiles, the maximum temperature inside the automobile reaches 90 ° C. Sometimes.
【００１０】硬質塩化ビニル樹脂と軟質塩化ビニル樹脂
との共押出で得られたシール材は７０℃の高温雰囲気下
に曝された場合には、硬質塩化ビニル樹脂は変形してし
まい、又軟質塩化ビニル樹脂も押圧、圧縮による変形が
大きくなってしまうため、シーリング、密閉効果が使用
途中で減少し、良好なシール性能を有するシール材を得
られなかった。When the sealing material obtained by coextrusion of the hard vinyl chloride resin and the soft vinyl chloride resin is exposed to a high temperature atmosphere of 70 ° C., the hard vinyl chloride resin is deformed and soft chloride is added. Since the vinyl resin also becomes largely deformed by pressing and compression, the sealing and sealing effects are reduced during use, and a sealing material having good sealing performance cannot be obtained.
【００１１】又、硬質材料の耐熱性を上げるために硬質
樹脂材料として耐熱塩化ビニル樹脂を使用し、軟質材料
として軟質塩化ビニル樹脂を使用したガスケットの場合
には、硬質材料の耐熱性は向上するが、高温雰囲気下で
軟質材料として使用している塩化ビニル樹脂が変形する
ことは防げなかった。Further, in the case of a gasket using a heat-resistant vinyl chloride resin as the hard resin material and a soft vinyl chloride resin as the soft material in order to increase the heat resistance of the hard material, the heat resistance of the hard material is improved. However, it was not possible to prevent deformation of the vinyl chloride resin used as the soft material in a high temperature atmosphere.
【００１２】一方、軟質材料として架橋ゴム材料を使用
する場合、耐変形性に優れ、シール性能は良好な製品が
得られるけれども、ゴム材料との成形温度の差異及びゴ
ム部分の架橋処理のために接着が必要なことから、硬質
合成樹脂との共押出製品は殆ど製品となり得なかった。On the other hand, when a crosslinked rubber material is used as the soft material, a product having excellent deformation resistance and good sealing performance can be obtained, but due to the difference in molding temperature with the rubber material and the crosslinking treatment of the rubber portion. Coextrusion products with hard synthetic resins could hardly be products because of the need for adhesion.
【００１３】[0013]
【発明が解決しようとする課題】本発明の目的は、前記
の欠点を解決し、良好な耐熱性、成形性及び耐変形性を
持ち、シーリング、密閉効果の優れた押出成形品を提供
することにある。本発明者等は、硬質材料として熱可塑
性樹脂組成物を、軟質材料として軟質樹脂組成物を使用
することにより、耐熱性、成形性及び耐変形性に優れた
共押出成形品をつくることを鋭意研究した結果、本発明
を完成するに至った。SUMMARY OF THE INVENTION An object of the present invention is to solve the above-mentioned drawbacks and to provide an extruded product having good heat resistance, moldability and deformation resistance, and excellent sealing and sealing effects. It is in. The present inventors are keen to make a coextrusion molded article excellent in heat resistance, moldability and deformation resistance by using a thermoplastic resin composition as a hard material and a soft resin composition as a soft material. As a result of research, the present invention has been completed.
【００１４】[0014]
【課題を解決するための手段】本発明の第１の発明は、
（１）下記の（ａ）成分１００〜５０重量％及び（ｂ）
成分０〜５０重量％からなる熱可塑性樹脂組成物Ａと、
（２）塩化ビニル系樹脂５〜７５重量％、部分架橋アク
リロニトリル−ブタジエン共重合体５〜７０重量％及び
可塑剤１０〜６５重量％からなる軟質樹脂組成物Ｂとを
共押出してなる押出成形品である。 （ａ）成分 塩素含有量６０〜７０重量％の塩素化塩化
ビニル系樹脂 （ｂ）成分 塩化ビニル系樹脂The first invention of the present invention is as follows:
(1) 100 to 50% by weight of the following component (a) and (b)
A thermoplastic resin composition A comprising 0 to 50% by weight of the component,
(2) Extruded product obtained by co-extruding a soft resin composition B comprising 5 to 75% by weight of a vinyl chloride resin, 5 to 70% by weight of a partially crosslinked acrylonitrile-butadiene copolymer and 10 to 65% by weight of a plasticizer. Is. Component (a) Chlorinated vinyl chloride resin having a chlorine content of 60 to 70% by weight (b) Component Vinyl chloride resin
【００１５】又、本発明の第２の発明は、押出成形品が
シール材である、第１の発明の押出成形品である。The second invention of the present invention is the extrusion-molded product of the first invention, wherein the extrusion-molded product is a sealing material.
【００１６】以下本発明を詳細に説明する。The present invention will be described in detail below.
【００１７】本発明において熱可塑性樹脂組成物Ａと
は、（ａ）成分及び（ｂ）成分からなる組成物である。In the present invention, the thermoplastic resin composition A is a composition comprising the component (a) and the component (b).
【００１８】本発明の熱可塑性樹脂組成物Ａに使用する
（ａ）成分は、塩素含有量６０〜７０重量％の塩素化塩
化ビニル系樹脂であり、（ｂ）成分は塩化ビニル系樹脂
である。The component (a) used in the thermoplastic resin composition A of the present invention is a chlorinated vinyl chloride resin having a chlorine content of 60 to 70% by weight, and the component (b) is a vinyl chloride resin. .
【００１９】本発明の熱可塑性樹脂組成物Ａの（ａ）成
分及び（ｂ）成分の重量比は、（ａ）成分１００〜５０
重量％及び（ｂ）成分０〜５０重量％である。The weight ratio of the component (a) and the component (b) of the thermoplastic resin composition A of the present invention is 100 to 50 for the component (a).
% By weight and 0 to 50% by weight of component (b).
【００２０】本発明で使用する（ａ）成分の塩素化塩化
ビニル系樹脂は、例えば塩化ビニル系樹脂粉末を気相中
若しくは水中に懸濁した状態又は溶媒に溶解した状態で
塩素化することにより製造できる。塩化ビニル系樹脂の
塩素化方法については良く知られており、例えば特公昭
３６−８８８号公報及び特公昭４５−３０８３３号公報
等に詳しく説明されている。The chlorinated vinyl chloride resin as the component (a) used in the present invention is obtained by chlorinating, for example, a vinyl chloride resin powder in a gas phase, in a state of being suspended in water or in a state of being dissolved in a solvent. Can be manufactured. The method of chlorinating vinyl chloride resin is well known and described in detail, for example, in Japanese Patent Publication No. 36-888 and Japanese Patent Publication No. 45-30833.
【００２１】本発明で使用する塩素化塩化ビニル系樹脂
の塩素含有量は６０〜７０重量％である。塩素化塩化ビ
ニル系樹脂の塩素含有量が６０重量％未満の場合には耐
熱性の改良が充分でなく、又７０重量％を越えると熱分
解し易くなり好ましくない。The chlorine content of the chlorinated vinyl chloride resin used in the present invention is 60 to 70% by weight. When the chlorine content of the chlorinated vinyl chloride resin is less than 60% by weight, the heat resistance is not sufficiently improved, and when it exceeds 70% by weight, thermal decomposition tends to occur, which is not preferable.
【００２２】前記塩素化塩化ビニル系樹脂の製造に使用
する塩化ビニル系樹脂の例としては、ポリ塩化ビニルの
ほかに、塩化ビニルとそれに共重合するビニル化合物の
混合物を懸濁重合法、塊状重合法、微細懸濁重合法又は
乳化重合法等の通常の方法によって重合したもの、更に
はエチレン−酢酸ビニル共重合体、エチレン−アクリル
酸エチル共重合体又は塩素化ポリエチレン等に塩化ビニ
ルをグラフト共重合したもの等全てが使用される。As an example of the vinyl chloride resin used in the production of the chlorinated vinyl chloride resin, in addition to polyvinyl chloride, a mixture of vinyl chloride and a vinyl compound copolymerized therewith is subjected to a suspension polymerization method, a bulk polymerization method. Polymerized by a conventional method such as a legal method, a fine suspension polymerization method or an emulsion polymerization method, and further, a vinyl chloride graft copolymer is added to an ethylene-vinyl acetate copolymer, an ethylene-ethyl acrylate copolymer or a chlorinated polyethylene. All of those polymerized are used.
【００２３】前記塩素化塩化ビニル系樹脂の製造に使用
する塩化ビニル系樹脂において、塩化ビニルと共重合す
るビニル化合物としては、例えば、酢酸ビニル及びプロ
ピオン酸ビニル等のビニルエステル類、メチルアクリレ
ート及びブチルアクリレート等のアクリル酸エステル
類、メチルメタクリレート及びエチルメタクリレート等
のメタクリル酸エステル類、ブチルマレート及びジエチ
ルマレート等のマレイン酸エステル類、ジブチルフマレ
ート及びジエチルフマレート等のフマル酸エステル類、
ビニルメチルエーテル、ビニルブチルエーテル及びビニ
ルオクチルエーテル等のビニルエーテル類、アクリロニ
トリル及びメタクリロニトリル等のシアン化ビニル類、
エチレン、プロピレン及びスチレン等のα−オレフィン
類、塩化ビニリデン及び臭化ビニル等の塩化ビニル以外
のハロゲン化ビニリデン及びハロゲン化ビニル類、並び
に、ジアリルフタレート等のフタル酸エステル類等が挙
げられ、これらビニル化合物は、塩化ビニル系樹脂の構
成成分中好ましくは３０重量％以下、特に好ましくは２
０重量％以下の範囲である。勿論ビニル化合物は上記の
ものに限定されるものではない。In the vinyl chloride resin used in the production of the chlorinated vinyl chloride resin, the vinyl compound copolymerized with vinyl chloride is, for example, vinyl ester such as vinyl acetate and vinyl propionate, methyl acrylate and butyl. Acrylic acid esters such as acrylates, methacrylic acid esters such as methyl methacrylate and ethyl methacrylate, maleic acid esters such as butyl maleate and diethyl malate, fumaric acid esters such as dibutyl fumarate and diethyl fumarate,
Vinyl ethers such as vinyl methyl ether, vinyl butyl ether and vinyl octyl ether, vinyl cyanides such as acrylonitrile and methacrylonitrile,
Α-olefins such as ethylene, propylene and styrene, vinylidene halides and vinyl halides other than vinyl chloride such as vinylidene chloride and vinyl bromide, and phthalic acid esters such as diallyl phthalate, and the like. The compound is preferably 30% by weight or less, and particularly preferably 2% by weight in the constituent components of the vinyl chloride resin.
It is in the range of 0% by weight or less. Of course, the vinyl compound is not limited to the above.
【００２４】又、本発明で使用する（ｂ）成分の塩化ビ
ニル系樹脂の例としては、ポリ塩化ビニルのほかに、塩
化ビニルとそれに共重合する前記のビニル化合物との共
重合体を挙げることができる。Further, as an example of the vinyl chloride resin as the component (b) used in the present invention, in addition to polyvinyl chloride, a copolymer of vinyl chloride and the above-mentioned vinyl compound to be copolymerized therewith may be mentioned. You can
【００２５】これらの塩化ビニル系共重合体に使用する
ビニル化合物の使用量も塩化ビニル系樹脂の構成成分中
好ましくは３０重量％以下、特に好ましくは２０重量％
以下の範囲である。The amount of the vinyl compound used in these vinyl chloride-based copolymers is also preferably 30% by weight or less, particularly preferably 20% by weight in the constituent components of the vinyl chloride-based resin.
The range is as follows.
【００２６】又、塩化ビニル系樹脂の平均重合度は、Ｊ
ＩＳ Ｋ−６７２１で測定される平均重合度（以下重合
度と称す）で、５００〜１５００のものが好ましい。重
合度が５００未満の場合には耐衝撃性が劣ることとな
り、又重合度が１５００を越えると加工時の溶融粘度が
著しく高くなり、加工が困難になる。The average degree of polymerization of vinyl chloride resin is J
The average degree of polymerization measured by IS K-6721 (hereinafter referred to as the degree of polymerization) is preferably from 500 to 1500. If the degree of polymerization is less than 500, the impact resistance will be poor, and if the degree of polymerization is more than 1500, the melt viscosity during processing will be remarkably high and processing will be difficult.
【００２７】前記の（ａ）成分及び（ｂ）成分からなる
本発明の熱可塑性樹脂組成物Ａは、ＪＩＳ Ｋ−７２０
７ Ａ法で規定される荷重たわみ温度が８０℃以上のも
のが好ましく、特に８５℃以上のものが好ましい。荷重
たわみ温度が８０℃未満の場合、耐熱性の改良効果が不
十分であり、高温雰囲気化に曝されると変形し易いため
に好ましくない。The thermoplastic resin composition A of the present invention comprising the above-mentioned components (a) and (b) is JIS K-720.
7 It is preferable that the deflection temperature under load as defined by Method A is 80 ° C or higher, and particularly preferably 85 ° C or higher. When the deflection temperature under load is less than 80 ° C., the heat resistance improving effect is insufficient, and when exposed to a high temperature atmosphere, it is easily deformed, which is not preferable.
【００２８】本発明において軟質樹脂組成物Ｂとは、塩
化ビニル系樹脂、部分架橋アクリロニトリル−ブタジエ
ン共重合体及び可塑剤からなる組成物である。In the present invention, the soft resin composition B is a composition comprising a vinyl chloride resin, a partially crosslinked acrylonitrile-butadiene copolymer and a plasticizer.
【００２９】本発明の軟質樹脂組成物Ｂに使用する塩化
ビニル系樹脂は、ポリ塩化ビニルのほかに、塩化ビニル
とそれに共重合する前記のビニル化合物の混合物を懸濁
重合法、塊状重合法、微細懸濁重合法又は乳化重合法等
通常の方法によって製造されたもの全てが使用される。The vinyl chloride resin used in the soft resin composition B of the present invention is, in addition to polyvinyl chloride, a suspension polymerization method, a bulk polymerization method, or a mixture of vinyl chloride and the above-mentioned vinyl compound copolymerized therewith. All those produced by ordinary methods such as the fine suspension polymerization method or the emulsion polymerization method are used.
【００３０】塩化ビニルに共重合するビニル化合物とし
ては、前記の熱可塑性樹脂組成物Ａに使用されたものと
同様なものを挙げることができる。これらビニル化合物
の使用量も塩化ビニル系樹脂の構成成分中好ましくは３
０重量％以下、特に好ましくは２０重量％以下の範囲で
使用される。As the vinyl compound copolymerized with vinyl chloride, the same compounds as those used in the thermoplastic resin composition A can be mentioned. The amount of these vinyl compounds used is preferably 3 in the constituent components of the vinyl chloride resin.
It is used in an amount of 0% by weight or less, particularly preferably 20% by weight or less.
【００３１】又、本発明の軟質樹脂組成物Ｂに使用する
塩化ビニル系樹脂の平均重合度は特に制限はないが、共
押出成形を行う場合、硬質材料との成形温度差を小さく
し、良好なシール材を得るという本発明の目的に合致す
るためには、ＪＩＳ Ｋ−６７２１で測定される平均重
合度が２０００以上であることが好ましい。The average degree of polymerization of the vinyl chloride resin used in the soft resin composition B of the present invention is not particularly limited, but when coextrusion molding is carried out, the molding temperature difference with the hard material is made small and good. In order to meet the purpose of the present invention to obtain a good sealing material, the average degree of polymerization measured by JIS K-6721 is preferably 2000 or more.
【００３２】本発明の軟質樹脂組成物Ｂに使用する部分
架橋アクリロニトリル−ブタジエン共重合体は、メチル
エチルケトンに不溶な架橋アクリロニトリル−ブタジエ
ン共重合体を含むものであれば、その製法を制限するも
のではなく、ジビニルベンゼンやエチレングリコールジ
メタクリレート等の多官能性化合物との共重合で得る方
法、メチルエチルケトンに不溶な架橋アクリロニトリル
−ブタジエン共重合体が生成するまで反応率を高める方
法、又は少量の架橋剤を使用して未加硫アクリロニトリ
ル−ブタジエン共重合体を架橋させて得る方法等いずれ
の方法でも差し支えない。The partially crosslinked acrylonitrile-butadiene copolymer used in the soft resin composition B of the present invention is not limited as long as it contains a crosslinked acrylonitrile-butadiene copolymer insoluble in methyl ethyl ketone. , A method obtained by copolymerization with a polyfunctional compound such as divinylbenzene or ethylene glycol dimethacrylate, a method of increasing the reaction rate until a crosslinked acrylonitrile-butadiene copolymer insoluble in methyl ethyl ketone is formed, or a small amount of a crosslinking agent is used. Then, any method such as a method of cross-linking the unvulcanized acrylonitrile-butadiene copolymer may be used.
【００３３】一般に入手できる部分架橋アクリロニトリ
ル−ブタジエン共重合体としては例えば、グッドイヤー
社製、商品名「ケミガムＰ８３」、日本合成ゴム社製、
商品名「ＪＳＲ Ｎ２０１」及びＢ．Ｆ．グッドリッチ
社製、商品名「Ｈｙｃａｒ１４２１」等が挙げられる。Examples of commonly available partially crosslinked acrylonitrile-butadiene copolymers include those manufactured by Goodyear, trade name "Chemic P83", manufactured by Nippon Synthetic Rubber Co., Ltd.
Product name "JSR N201" and B.I. F. A product name “Hycar 1421” manufactured by Goodrich Co., Ltd. may be mentioned.
【００３４】又、本発明の軟質樹脂組成物Ｂに使用する
可塑剤は、一般的に塩化ビニル系樹脂の可塑剤として使
用するものであれば制限はなく、例えば、フタル酸ジブ
チル、フタル酸ジヘプチル、フタル酸ジ２−エチルヘキ
シル、フタル酸ジイソノニル及びフタル酸ジイソデシル
等のフタル酸系可塑剤、トリメリット酸トリブチル及び
トリメリット酸トリ２−エチルヘキシル等のトリメリッ
ト酸系可塑剤、ピロメリット酸テトラブチル及びピロメ
リット酸テトラオクチル等のピロメリット酸系可塑剤、
リン酸トリクレジル及びリン酸トリオクチル等のリン酸
系可塑剤、アジピン酸ジオクチル、アゼライン酸ジオク
チル及びセバシン酸ジオクチル等の脂肪酸系可塑剤、並
びに、アジピン酸ポリエステル及びセバシン酸ポリエス
テル等のポリエステル系可塑剤アルキルエポキシステア
レート等のエポキシ系可塑剤等が挙げられ、これらは単
独又は２種以上混合して使用される。又エポキシ化大豆
油、塩素化パラフィン等の二次可塑剤を併用することも
できる。The plasticizer used in the soft resin composition B of the present invention is not limited as long as it is generally used as a plasticizer for vinyl chloride resins, and examples thereof include dibutyl phthalate and diheptyl phthalate. , Phthalic acid-based plasticizers such as di2-ethylhexyl phthalate, diisononyl phthalate and diisodecyl phthalate, tributyl trimellitate and trimellitic acid-based plasticizers such as tri-2-ethylhexyl trimellitate, tetrabutyl and pyromellitic acid Pyromellitic acid plasticizers such as tetraoctyl melitate,
Phosphoric acid plasticizers such as tricresyl phosphate and trioctyl phosphate, fatty acid plasticizers such as dioctyl adipate, dioctyl azelate and dioctyl sebacate, and polyester plasticizers such as polyester adipate and sebacate alkylepoxy Examples thereof include epoxy plasticizers such as stearate, and these may be used alone or in admixture of two or more. A secondary plasticizer such as epoxidized soybean oil and chlorinated paraffin can also be used in combination.
【００３５】軟質樹脂組成物Ｂは重量比で、塩化ビニル
系樹脂５〜７５重量％、部分架橋アクリロニトリル−ブ
タジエン共重合体５〜７０重量％及び可塑剤１０〜６５
重量％の範囲にある。The soft resin composition B comprises, by weight, 5 to 75% by weight of a vinyl chloride resin, 5 to 70% by weight of a partially crosslinked acrylonitrile-butadiene copolymer and 10 to 65 of a plasticizer.
It is in the range of% by weight.
【００３６】塩化ビニル系樹脂が５重量％未満の場合、
押出成形時、製品外観不良等の不良現象が発生する場合
が多く、また７５重量％を越えると得られたシール材の
シール部分が硬くなるため、シール材として不適当であ
る。When the vinyl chloride resin is less than 5% by weight,
During extrusion molding, a defective phenomenon such as a defective product appearance often occurs, and when the content exceeds 75% by weight, the sealing portion of the obtained sealing material becomes hard, which is unsuitable as a sealing material.
【００３７】又、部分架橋アクリロニトリル−ブタジエ
ン共重合体が５重量％未満の場合、共押出成形時に硬質
材料との適正成形温度差が大きくなり、又得られたシー
ル材は押圧、圧縮等による変形を受けやすい。一方、７
０重量％を越えると押出成形時に製品外観不良等の不良
現象が発生し易く不適当である。When the content of the partially crosslinked acrylonitrile-butadiene copolymer is less than 5% by weight, the appropriate molding temperature difference with the hard material during coextrusion molding becomes large, and the obtained sealing material is deformed by pressing, compression or the like. Easy to receive. On the other hand, 7
If it exceeds 0% by weight, a defective phenomenon such as a defective product appearance is likely to occur during extrusion molding, which is unsuitable.
【００３８】更に可塑剤が１０重量％未満の場合は得ら
れたシール材のシール部分が硬いためにシール材として
不適当であり、又６５重量％を越えると硬度が低下しす
ぎて高温雰囲気下で変形し易くなり不適当である。Further, if the amount of the plasticizer is less than 10% by weight, the sealing portion of the obtained sealing material is hard and unsuitable as a sealing material. It is not suitable because it easily deforms.
【００３９】本発明の熱可塑性樹脂組成物Ａと軟質樹脂
組成物Ｂには、特性の向上のため、充填剤を添加するこ
とができる。熱可塑性樹脂組成物Ａにおいては、充填剤
の添加により耐熱性及び成形性が向上する利点がある。
充填剤としては、塩化ビニル系樹脂に使用できる充填剤
が使用可能である。具体的には、炭酸カルシウム、シリ
カ、クレー、タルク、水酸化アルミ、酸化アンチモン等
が単独又は併用で用いられる。充填剤の平均粒径は、特
に制限はないが、通常、０．０１μｍ〜１０μｍ、好ま
しくは０．０３μｍ〜７μｍ、特に好ましくは０．０３
μｍ〜５μｍのものが用いられる。充填剤の中では、炭
酸カルシウムが好ましく、特に好ましくは、平均粒径
が、０．０３μｍ〜５μｍの炭酸カルシウムである。A filler may be added to the thermoplastic resin composition A and the soft resin composition B of the present invention in order to improve the characteristics. The thermoplastic resin composition A has an advantage that heat resistance and moldability are improved by adding a filler.
As the filler, a filler that can be used for vinyl chloride resin can be used. Specifically, calcium carbonate, silica, clay, talc, aluminum hydroxide, antimony oxide and the like are used alone or in combination. The average particle size of the filler is not particularly limited, but is usually 0.01 μm to 10 μm, preferably 0.03 μm to 7 μm, and particularly preferably 0.03.
Those having a size of μm to 5 μm are used. Among the fillers, calcium carbonate is preferable, and calcium carbonate having an average particle diameter of 0.03 μm to 5 μm is particularly preferable.
【００４０】熱可塑性樹脂組成物Ａへの充填剤の添加量
は、樹脂組成物１００重量部に対して４０重量部以下で
あり、好ましくは、１〜３０重量部である。充填剤が、
４０重量部を越えるとペレット化が不可能になり、樹脂
組成物としての性能が全く得られない。The amount of the filler added to the thermoplastic resin composition A is 40 parts by weight or less, preferably 1 to 30 parts by weight, based on 100 parts by weight of the resin composition. The filler is
If it exceeds 40 parts by weight, pelletization becomes impossible and the performance as a resin composition cannot be obtained at all.
【００４１】又本発明の熱可塑性樹脂組成物Ａと軟質樹
脂組成物Ｂには、必要に応じて安定剤、加工助剤、強化
剤、滑剤、顔料等一般の塩化ビニル系樹脂に使用するも
のを添加しても良い。The thermoplastic resin composition A and the soft resin composition B of the present invention are used for general vinyl chloride resins such as stabilizers, processing aids, reinforcing agents, lubricants and pigments, if necessary. May be added.
【００４２】本発明において、各使用原材料の添加、混
合の順序等に制限はなく、混合及びペレット化は通常の
塩化ビニル系樹脂の場合と同様な方法が使用される。熱
可塑性樹脂組成物Ａ、軟質樹脂組成物Ｂともに混合には
例えば、ヘンシェルミキサーやスーパーミキサーのよう
な高速ミキサー、リボンブレンダー等の混合機が使用さ
れる。混合方式は、上記混合機に各成分を投入し、例え
ば１５０℃以下の温度でそれぞれの混合機に見合った時
間、均一にブレンドするのが好ましい。In the present invention, there is no limitation on the order of addition and mixing of the raw materials used, and mixing and pelletization may be carried out in the same manner as in the case of ordinary vinyl chloride resins. For mixing the thermoplastic resin composition A and the soft resin composition B, for example, a high speed mixer such as a Henschel mixer or a super mixer, or a mixer such as a ribbon blender is used. As for the mixing method, it is preferable that the respective components are charged into the above mixer and uniformly blended at a temperature of, for example, 150 ° C. or less for a time corresponding to each mixer.
【００４３】造粒は上記混合物をバンバリーミキサー、
ミキシングロール、押出機等を使用し、通常の塩化ビニ
ル系樹脂の製造に使用される方法により行われる。Granulation is carried out by mixing the above mixture with a Banbury mixer,
A mixing roll, an extruder, etc. are used and it is performed by the method normally used for manufacture of vinyl chloride resin.
【００４４】共押出装置については特に制限はないが、
通常、硬質材料に使用する混練押出装置Ａ、軟質材料に
使用する混練押出装置Ｂを同一の金型Ｃで接合一体化し
て、共押出装置Ｄを得る方法が行われており、個々の押
出装置Ａ、Ｂの大きさ、単軸、二軸等及び横型、竪型装
置等の選定は、使用する材料及び共押出製品の形状、寸
法により適宜選定されうるものである。The coextrusion device is not particularly limited,
Usually, a kneading extrusion device A used for a hard material and a kneading extrusion device B used for a soft material are joined and integrated by the same mold C to obtain a coextrusion device D. The sizes of A and B, single-axis, twin-axis, etc. and horizontal type, vertical type devices, etc. can be appropriately selected depending on the material to be used and the shape and size of the coextrusion product.
【００４５】本発明において、表面意匠性等を賦与する
目的で、押出成形時、表面に塩化ビニル系樹脂、アクリ
ル樹脂等を多層に押出してもかまわない。また押出成形
品の強度等を向上させるために、必要に応じて金属等を
共押出しても良い。In the present invention, for the purpose of imparting a surface design property and the like, it is possible to extrude a vinyl chloride resin, an acrylic resin or the like in multiple layers on the surface during extrusion molding. In addition, in order to improve the strength of the extruded product, a metal or the like may be coextruded if necessary.
【００４６】[0046]
【実施例】以下、本発明を実施例により説明する。EXAMPLES The present invention will be described below with reference to examples.
【００４７】実施例１〜４ 表１に示す各原材料を７５リットルのヘンシェルミキサ
ーに入れ、撹拌混合後、９０ｍ／ｍ単軸押出機（池貝鉄
工（株）製）にて混練ペレット化を行い、熱可塑性樹脂
組成物Ａ及び軟質樹脂組成物Ｂの各ペレット１５ｋｇを
得た。これを使用し次の２台の押出機にて共押出を行っ
た。 押出機Ａ ６５ｍ／ｍ単軸押出機（池貝鉄工（株）製）
（熱可塑性樹脂組成物Ａ用） 押出機Ｂ ４０ｍ／ｍ竪型単軸押出機（（株）プラスチ
ック工学研究所製）（軟質樹脂組成物Ｂ用）Examples 1 to 4 The raw materials shown in Table 1 were put into a 75 liter Henschel mixer, and after stirring and mixing, kneading and pelletizing were performed using a 90 m / m single-screw extruder (made by Ikegai Tekko KK). 15 kg of each pellet of the thermoplastic resin composition A and the soft resin composition B was obtained. Using this, co-extrusion was performed with the following two extruders. Extruder A 65 m / m single screw extruder (made by Ikegai Tekko Co., Ltd.)
(For thermoplastic resin composition A) Extruder B 40 m / m Vertical single-screw extruder (manufactured by Plastic Engineering Laboratory Co., Ltd.) (For soft resin composition B)
【００４８】共押出成形品用のダイは、熱可塑性樹脂組
成物Ａと軟質樹脂組成物Ｂの構成となるよう設計された
ものを使用した。As the die for the coextrusion molded article, a die designed to have the thermoplastic resin composition A and the soft resin composition B was used.
【００４９】得られた共押出成形品は成形性が良好であ
り、これを５００ｍｍの長さに切断し９０℃及び１００
℃の雰囲気下で４８時間加熱した。取り出し後、長さＬ
を測定し、最初の長さ５００ｍｍで除して、収縮率
（（５００−Ｌ）／５００×１００）％を算出した。ま
た、５００ｍｍの長さに切断した共押出成形品を９０℃
の雰囲気下で４８時間加熱した後の変形、ソリについて
外観の評価を行った。又、熱可塑性樹脂組成物Ａ部分の
ＪＩＳ Ｋ−７２０７ Ａ法による荷重たわみ温度を測
定した。物性評価を表１に示した。その結果、得られた
共押出成形品は良好であり、シール材として実用可能で
あった。The coextrusion molded product obtained had good moldability and was cut to a length of 500 mm at 90 ° C. and 100 ° C.
It heated under the atmosphere of (degree C) for 48 hours. After taking out, length L
Was measured and divided by the initial length of 500 mm to calculate the shrinkage rate ((500-L) / 500 × 100)%. In addition, the coextrusion molded product cut into a length of 500 mm is 90 ° C.
The appearance of the deformation and warp after heating for 48 hours in the atmosphere was evaluated. In addition, the deflection temperature under load of the thermoplastic resin composition A portion was measured by the JIS K-7207 A method. The evaluation of physical properties is shown in Table 1. As a result, the obtained coextrusion molded article was good and was practically usable as a sealing material.
【００５０】[0050]
【表１】 [Table 1]
【００５１】比較例１〜２ 表２に示す各原材料を前記実施例に示したのと同一の方
法で撹拌、混練ペレット化を行い、共押出した。得られ
た共押出成形品の評価、測定を行い、物性を表２に示し
た。その結果、シール材として実用不可能であった。Comparative Examples 1 and 2 The raw materials shown in Table 2 were agitated, kneaded and pelletized by the same method as in the above Examples, and coextruded. The obtained coextrusion molded article was evaluated and measured, and the physical properties are shown in Table 2. As a result, it was not practical as a sealing material.
【００５２】[0052]
【表２】 [Table 2]
【００５３】使用原材料 実施例１〜３及び比較例１〜２に使用した使用原材料を
以下に示した。 （１）塩素化塩化ビニル系樹脂 塩素化塩化ビニル系樹脂−１ ニカテンプＴ２４１（塩素含有量６４．５重量％） 日
本カーバイト工業（株）製 塩素化塩化ビニル系樹脂−２ ニカテンプＴ２８１（塩素含有量６７．８重量％） 日
本カーバイト工業（株）製Raw Materials Used The raw materials used in Examples 1 to 3 and Comparative Examples 1 and 2 are shown below. (1) Chlorinated vinyl chloride resin Chlorinated vinyl chloride resin-1 Nikatemp T241 (chlorine content 64.5% by weight) Nippon Carbide Industries Co., Ltd. Chlorinated vinyl chloride resin-2 Nikatemp T281 (chlorine containing) 67.8% by weight) Made by Nippon Carbide Industry Co., Ltd.
【００５４】（２）塩化ビニル系樹脂 塩化ビニル系樹脂−１ デンカビニールＳＳ１１０（重合度１１００） 電気化
学工業（株）社製 塩化ビニル系樹脂−２ デンカビニールＳＨ３８０（重合度３８００） 電気化
学工業（株）社製(2) Vinyl chloride resin Vinyl chloride resin-1 Denka vinyl SS110 (polymerization degree 1100) Denki Kagaku Kogyo Co., Ltd. Vinyl chloride resin-2 Denka vinyl SH380 (polymerization degree 3800) Electrochemical industry ( Co., Ltd.
【００５５】（３）部分架橋アクリロニトリル−ブタジ
エン共重合体（表中ＮＢＲと略記） ＪＳＲ Ｎ２０１ 日本合成ゴム（株）社製(3) Partially cross-linked acrylonitrile-butadiene copolymer (abbreviated as NBR in the table) JSR N201 manufactured by Nippon Synthetic Rubber Co., Ltd.
【００５６】（４）可塑剤 フタル酸ジイソノニル （５）充填剤 平均粒径０．０８μｍの表面処理炭酸カ
ルシウム(4) Plasticizer Diisononyl phthalate (5) Filler Surface-treated calcium carbonate having an average particle size of 0.08 μm
【００５７】[0057]
【発明の効果】以上の通り、本発明により、耐熱性、成
形性、耐変形性に優れた押出成形品、具体的にはシール
材を得ることができる。INDUSTRIAL APPLICABILITY As described above, according to the present invention, it is possible to obtain an extruded product having excellent heat resistance, moldability and deformation resistance, specifically, a sealing material.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 庁内整理番号 ＦＩ 技術表示箇所 // Ｂ２９Ｋ 27:06 Ｂ２９Ｌ 9:00 31:26 ─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. 6 Identification code Office reference number FI technical display location // B29K 27:06 B29L 9:00 31:26
Claims (2)
量％及び（ｂ）成分０〜５０重量％からなる熱可塑性樹
脂組成物Ａと、（２）塩化ビニル系樹脂５〜７５重量
％、部分架橋アクリロニトリル−ブタジエン共重合体５
〜７０重量％及び可塑剤１０〜６５重量％からなる軟質
樹脂組成物Ｂとを共押出してなる押出成形品。 （ａ）成分 塩素含有量６０〜７０重量％の塩素化塩化
ビニル系樹脂 （ｂ）成分 塩化ビニル系樹脂1. A thermoplastic resin composition A comprising (1) 100 to 50% by weight of (a) component and 0 to 50% by weight of (b) component, and (2) 5 to 75% by weight of vinyl chloride resin. %, Partially crosslinked acrylonitrile-butadiene copolymer 5
An extruded product obtained by co-extruding a soft resin composition B comprising ˜70 wt% and a plasticizer of 10 to 65 wt%. Component (a) Chlorinated vinyl chloride resin having a chlorine content of 60 to 70% by weight (b) Component Vinyl chloride resin
載の押出成形品。2. The extruded product according to claim 1, wherein the extruded product is a sealing material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15321595A JP3508958B2 (en) | 1994-08-02 | 1995-06-20 | Seal material |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6-181524 | 1994-08-02 | ||
| JP18152494 | 1994-08-02 | ||
| JP15321595A JP3508958B2 (en) | 1994-08-02 | 1995-06-20 | Seal material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0899343A true JPH0899343A (en) | 1996-04-16 |
| JP3508958B2 JP3508958B2 (en) | 2004-03-22 |
Family
ID=26481912
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP15321595A Expired - Lifetime JP3508958B2 (en) | 1994-08-02 | 1995-06-20 | Seal material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3508958B2 (en) |
-
1995
- 1995-06-20 JP JP15321595A patent/JP3508958B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JP3508958B2 (en) | 2004-03-22 |
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