JP3081511B2 - Extruded products - Google Patents
Extruded productsInfo
- Publication number
- JP3081511B2 JP3081511B2 JP07153216A JP15321695A JP3081511B2 JP 3081511 B2 JP3081511 B2 JP 3081511B2 JP 07153216 A JP07153216 A JP 07153216A JP 15321695 A JP15321695 A JP 15321695A JP 3081511 B2 JP3081511 B2 JP 3081511B2
- Authority
- JP
- Japan
- Prior art keywords
- weight
- component
- vinyl
- vinyl chloride
- chloride resin
- 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.)
- Expired - Fee Related
Links
Landscapes
- Laminated Bodies (AREA)
- Extrusion Moulding Of Plastics Or The Like (AREA)
- Compositions Of Macromolecular Compounds (AREA)
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 an extruded product made of synthetic resin having excellent heat resistance, moldability and deformation resistance, and more particularly 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材料が軟質材料として
使用されている。2. Description of the Related Art Conventionally, a soft synthetic resin such as a soft vinyl chloride resin or a crosslinked rubber material has been used as a soft material for a sealing material such as a packing or a gasket of a building, an automobile, a kitchen appliance or 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。[0003] Soft synthetic resins or crosslinked rubber materials are used alone as extrusion, injection and compression molded products. In addition, a metal and a resin are melted and integrated (hereinafter, referred to as coextrusion) in the same mold (hereinafter, referred to as a die) or adhered 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, a co-extruded sealing material made of metal is economically disadvantageous because it is necessary to separate resin and 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。[0005] As a countermeasure, coextrusion using a hard synthetic resin instead of metal has been studied. A co-extruded sealing material using a hard synthetic resin is processed and manufactured after co-extrusion molding of a hard synthetic resin and a soft material, or after bonding a hard synthetic resin and a soft material.
Examples of the hard synthetic resin include an ABS resin and a hard vinyl chloride resin. However, when the ABS resin is adhered or co-extruded with the soft vinyl chloride resin, cracks and the like are easily generated, which is not suitable for practical use.
【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。[0006] Therefore, as a hard material to be co-extruded with a soft material, a hard vinyl chloride resin is generally used.
【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は硬質材料との熱融
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。[0007] Examples of the soft material include soft vinyl chloride resin, olefin-based resin, and rubber. In the case of co-extrusion, in general, the heat-fusing property with the hard material and the workability are poor. Excellent 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 building,
Used for automobiles, kitchen appliances, etc.
【０００９】しかしながら、これらを屋外で使用した場
合には温度が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 can reach 70 ° C. or more, and when they are used for the interior of automobiles, the temperature inside the automobile can reach 90 ° C. at the maximum.
【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 a sealing material obtained by co-extrusion of a hard vinyl chloride resin and a soft vinyl chloride resin is exposed to a high-temperature atmosphere at 70 ° C., the hard vinyl chloride resin is deformed, and Since the deformation of the vinyl resin due to pressing and compression increases, the sealing and sealing effects are reduced during use, and a sealing material having good sealing performance cannot be obtained.
【００１１】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。In the case of a gasket using a heat-resistant vinyl chloride resin as a hard resin material and a soft vinyl chloride resin as a soft material in order to increase the heat resistance of the hard material, the heat resistance of the hard material is improved. The deformation of the vinyl chloride resin used as a soft material in a high-temperature atmosphere could not be prevented.
【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 a soft material, a product having excellent deformation resistance and good sealing performance can be obtained, but due to a difference in molding temperature from the rubber material and a crosslinking treatment of the rubber portion, the adhesive is required. Therefore, the co-extruded product with the hard synthetic resin could hardly be a product.
【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 provide an extruded product which solves the above-mentioned drawbacks, has good heat resistance, moldability and deformation resistance, and has excellent sealing and sealing effects. It is in. The present inventors have intensively studied the production of a co-extruded product by using a thermoplastic resin composition as a hard material and a soft resin composition as a soft material, and as a result, completed the present invention.
【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９０〜１０重量％、（ｂ）成分
０〜８０重量％及び（ｃ）成分１０〜８０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 （ｃ）成分 下記（イ）成分３０〜１００重量％及び
（ロ）成分０〜７０重量％からなる樹脂組成物 （イ）成分 α−メチルスチレン６５〜８５重量％、シ
アン化ビニル化合物１５〜３５重量％及びこれらと共重
合する他のビニル化合物０〜２０重量％からなるα−メ
チルスチレン系共重合体 （ロ）成分 芳香族ビニル化合物５０〜８０重量％、シ
アン化ビニル化合物１５〜３５重量％及びこれらと共重
合する他のビニル化合物０〜３０重量％からなる混合物
２０〜７０重量部をガラス転移温度（以下Ｔｇと略記）
が０℃以下のゴム３０〜８０重量部の存在下で共重合さ
せて得られるグラフト共重合体Means for Solving the Problems A first invention of the present invention is:
(1) a thermoplastic resin composition A comprising the following (a) component 90 to 10% by weight, (b) component 0 to 80% by weight, and (c) component 10 to 80% by weight, and (2) vinyl chloride-based Resin 5
It is an extruded product obtained by co-extrusion of a soft resin composition B consisting of about 75% by weight, 5-70% by weight of a partially crosslinked acrylonitrile-butadiene copolymer and 10-65% by weight of a plasticizer. (A) Component Chlorinated vinyl chloride resin having a chlorine content of 60 to 70% by weight (b) Component Vinyl chloride resin (c) Component 30 to 100% by weight of the following component (A) and 0 to 70% by weight of the component (B) % (A) 65-85% by weight of component α-methylstyrene, 15-35% by weight of a vinyl cyanide compound and 0-20% by weight of another vinyl compound copolymerized therewith Component (b) Component 20 to 70 parts by weight of a mixture comprising 50 to 80% by weight of an aromatic vinyl compound, 15 to 35% by weight of a vinyl cyanide compound and 0 to 30% by weight of another vinyl compound copolymerized therewith. Is the glass transition temperature (hereinafter abbreviated as Tg)
Graft copolymer obtained by copolymerization in the presence of 30 to 80 parts by weight of rubber having a temperature of 0 ° C. or less
【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。[0015] The second invention of the present invention is the extruded product according to the first invention, wherein the extruded product is a sealing material.
【００１６】以下本発明を詳細に説明する。本発明にお
いて熱可塑性樹脂組成物Ａとは、（ａ）成分、（ｂ）成
分及び（ｃ）成分からなる組成物である。Hereinafter, the present invention will be described in detail. In the present invention, the thermoplastic resin composition A is a composition comprising the component (a), the component (b), and the component (c).
【００１７】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
であり、（ｃ）成分はα−メチルスチレン系共重合体と
グラフト共重合体からなる樹脂組成物である。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. The component (c) is a resin composition comprising an α-methylstyrene copolymer and a graft copolymer.
【００１８】本発明の熱可塑性樹脂組成物Ａの（ａ）成
分、（ｂ）成分及び（ｃ）成分の重量比は、（ａ）成分
９０〜１０重量％、（ｂ）成分０〜８０重量％及び
（ｃ）成分１０〜８０重量％である。The weight ratio of the components (a), (b) and (c) of the thermoplastic resin composition A of the present invention is 90 to 10% by weight of the component (a) and 0 to 80% by weight of the component (b). % And 10 to 80% by weight of the component (c).
【００１９】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, for example, by chlorinating a vinyl chloride resin powder in a gas phase or in a state of being suspended in water or in a state of being dissolved in a solvent. Can be manufactured. Methods for chlorinating vinyl chloride resins are well known, and are described in detail, for example, in JP-B-36-888 and JP-B-45-30833.
【００２０】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％が好ましい。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 preferably from 60 to 70% by weight. If the chlorine content of the chlorinated vinyl chloride resin is less than 60% by weight, the heat resistance is not sufficiently improved, and if it exceeds 70% by weight, thermal decomposition is liable to occur.
【００２１】前記塩素化塩化ビニル系樹脂を製造するの
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。Examples of the vinyl chloride resin used for producing the chlorinated vinyl chloride resin include, in addition to polyvinyl chloride, a mixture of vinyl chloride and a vinyl compound copolymerized therewith, which is prepared by a suspension polymerization method. Bulk polymerization, those polymerized by ordinary methods such as fine suspension polymerization or emulsion polymerization, further ethylene-vinyl acetate copolymer, ethylene-
All materials such as an ethyl acrylate copolymer or a product obtained by graft copolymerizing vinyl chloride with chlorinated polyethylene or the like are used.
【００２２】前記塩素化塩化ビニル系樹脂を製造するの
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
２０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 for producing the chlorinated vinyl chloride resin, examples of the vinyl compound copolymerized with vinyl chloride include vinyl esters such as vinyl acetate and vinyl propionate, and methyl acrylate. And acrylates such as butyl acrylate, methacrylates such as methyl methacrylate and ethyl methacrylate, maleic esters such as butyl malate and diethyl malate, fumaric esters such as dibutyl fumarate and diethyl fumarate, vinyl methyl Vinyl ethers such as 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 Den and vinyl bromide,
In addition, phthalic acid esters such as diallyl phthalate are mentioned, and the content of these vinyl compounds is preferably 30% by weight or less, more preferably 20% by weight or less, of the components of the vinyl chloride resin. Of course, the vinyl compound is not limited to the above.
【００２３】又、本発明で使用される（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。Examples of the vinyl chloride resin (b) used in the present invention include, in addition to polyvinyl chloride,
Copolymers of vinyl chloride and the above-mentioned vinyl compounds copolymerized therewith can be exemplified.
【００２４】これらの塩化ビニル系共重合体に用いられ
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 copolymers is also preferably 30% by weight or less, more preferably 20% by weight or less, of the components of the vinyl chloride resin.
【００２５】また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 the vinyl chloride resin is J
An average degree of polymerization (hereinafter, referred to as degree of polymerization) measured by IS K-6721 is preferably from 500 to 1500. If the degree of polymerization is less than 500, the impact resistance becomes poor. If the degree of polymerization exceeds 1500, the melt viscosity during processing becomes extremely high, and processing becomes difficult.
【００２６】熱可塑性樹脂組成物Ａに使用される（ｃ）
成分は、（イ）成分のα−メチルスチレン系共重合体３
０〜１００重量％及び（ロ）成分のグラフト共重合体０
〜７０重量％からなる。(C) used in the thermoplastic resin composition A
Component is α-methylstyrene-based copolymer 3 of component (A)
0 to 100% by weight and the graft copolymer of the component (b) 0
-70% by weight.
【００２７】（イ）成分としては、α−メチルスチレン
系共重合体６５〜８５重量％、シアン化ビニル化合物１
５〜３５重量％及びこれらと共重合する他のビニル化合
物０〜２０重量％からなる共重合体が使用される。The component (a) comprises 65 to 85% by weight of an α-methylstyrene copolymer, a vinyl cyanide compound 1
Copolymers consisting of 5 to 35% by weight and 0 to 20% by weight of other vinyl compounds copolymerized with them are used.
【００２８】シアン化ビニル化合物としてはアクリロニ
トリル、メタクリロニトリル、α−クロロアクリロニト
リル等が挙げられるが、特にアクリロニトリル及び／又
はメタクリロニトリルが好ましい。Examples of the vinyl cyanide compound include acrylonitrile, methacrylonitrile, α-chloroacrylonitrile and the like, and acrylonitrile and / or methacrylonitrile are particularly preferable.
【００２９】又α−メチルスチレン及びシアン化ビニル
化合物と共重合するビニル化合物としては例えば、スチ
レン、ビニルトルエン、ｔ−ブチルスチレン、ハロゲン
置換スチレン、アセナフチレン、フマロニトリル、マレ
イミド、無水マレイン酸、Ｎ−置換マレイミド、メタク
リル酸、アクリル酸、メタクリル酸エステル及びアクリ
ル酸エステル等公知の各種ビニル化合物から選ばれた１
種以上のものが好ましく、特にスチレンが好ましい。Examples of the vinyl compound copolymerized with α-methylstyrene and a vinyl cyanide compound include, for example, styrene, vinyltoluene, t-butylstyrene, halogen-substituted styrene, acenaphthylene, fumaronitrile, maleimide, maleic anhydride, N-substituted 1 selected from various known vinyl compounds such as maleimide, methacrylic acid, acrylic acid, methacrylic acid ester and acrylic acid ester
More than one kind is preferable, and styrene is particularly preferable.
【００３０】（イ）成分の製造方法としては特に制限は
ないが例えば、水性乳化重合の方法等で行われる。水性
乳化重合における重合開始剤として例えば過硫酸カリウ
ム等の過硫酸塩等が使用される。The method for producing the component (a) is not particularly limited, but may be, for example, aqueous emulsion polymerization. As a polymerization initiator in the aqueous emulsion polymerization, for example, a persulfate such as potassium persulfate is used.
【００３１】乳化剤としては例えばドテシルベンゼンス
ルホン酸ソーダ塩、ステアリン酸ソーダ塩が使用され
る。又、ｔ−ドデシルメルカプタン等の分子量調節剤、
ナフタレンスルホン酸ソーダ等の乳化助剤、脂肪酸アミ
ド等の滑剤等通常に使用される添加剤を加えても良い。As the emulsifier, for example, sodium dodecylbenzenesulfonate and sodium stearate are used. A molecular weight regulator such as t-dodecyl mercaptan;
Usually used additives such as emulsifying aids such as sodium naphthalene sulfonate and lubricants such as fatty acid amides may be added.
【００３２】乳化重合の温度は３０〜１００℃が好まし
く、特に５０〜７５℃が好ましい。上記の方法により得
られた乳化重合液は通常の手段により例えば、塩化カル
シウム等の凝固剤で凝固させ、洗浄、脱水、乾燥して白
色粉末上の重合体として得られる。The temperature of the emulsion polymerization is preferably from 30 to 100 ° C., particularly preferably from 50 to 75 ° C. The emulsion polymerization liquid obtained by the above method is coagulated with a coagulant such as calcium chloride by usual means, washed, dehydrated and dried to obtain a polymer on a white powder.
【００３３】（ロ）成分としては、芳香族ビニル化合物
５０〜８０重量％、シアン化ビニル化合物１５〜３５重
量％及びこれらと共重合する他のビニル化合物０〜３０
重量％からなる混合物２０〜７０重量部をガラス転移温
度が０℃以下のゴム８０〜３０重量部の存在下で共重合
させて得られるグラフト共重合体が使用される。The component (b) includes 50 to 80% by weight of an aromatic vinyl compound, 15 to 35% by weight of a vinyl cyanide compound, and 0 to 30% of another vinyl compound copolymerized therewith.
A graft copolymer obtained by copolymerizing 20 to 70 parts by weight of a mixture consisting of 100% by weight in the presence of 80 to 30 parts by weight of a rubber having a glass transition temperature of 0 ° C. or less is used.
【００３４】（ロ）成分のグラフト共重合体を製造する
際に使用される芳香族ビニル化合物としては、前記のス
チレン、α−メチルスチレン、ビニルトルエン、ｔ−ブ
チルスチレン、ハロゲン置換スチレン及びそれらの混合
物が挙げられるが、特にスチレンが好ましい。The aromatic vinyl compound used for producing the graft copolymer of the component (b) includes styrene, α-methylstyrene, vinyltoluene, t-butylstyrene, halogen-substituted styrene, Although a mixture is mentioned, styrene is especially preferable.
【００３５】シアン化ビニル化合物としては、前記のア
クリロニトリル、メタクリロニトリル、α−クロロアク
リロニトリル等が挙げられるが、特にアクリロニトリル
及び／又はメタクリロニトリルが好ましい。Examples of the vinyl cyanide compound include the above-mentioned acrylonitrile, methacrylonitrile, α-chloroacrylonitrile and the like, and acrylonitrile and / or methacrylonitrile are particularly preferable.
【００３６】又芳香族ビニル化合物及びシアン化ビニル
化合物と共重合する他のビニル化合物としては例えば、
アセナフチレン、フマロニトリル、マレイミド、無水マ
レイン酸、Ｎ−置換マレイミド、メタクリル酸、アクリ
ル酸、メタクリル酸エステル、アクリル酸エステル等公
知の各種ビニル化合物から選ばれた１種以上のものが好
ましい。Other vinyl compounds copolymerized with an aromatic vinyl compound and a vinyl cyanide compound include, for example,
One or more selected from various known vinyl compounds such as acenaphthylene, fumaronitrile, maleimide, maleic anhydride, N-substituted maleimide, methacrylic acid, acrylic acid, methacrylic acid ester, and acrylic acid ester are preferable.
【００３７】（ロ）成分の製造に使用されるＴｇが０℃
以下のゴムとしては例えば、ブタジエン、イソプレン等
の共役ジエン化合物の重合体、更にこれらと共重合する
他のビニル化合物との共重合体等が挙げられるが、特に
ポリブタジエン又はブタジエンを５０重量％以上含有す
る共重合体が好ましい。グラフト共重合体の製造は通常
の方法で既知の重合条件下で行われる。(B) Tg used for producing the component is 0 ° C.
Examples of the following rubbers include, for example, polymers of conjugated diene compounds such as butadiene and isoprene, and copolymers with other vinyl compounds copolymerized with these. Particularly, polybutadiene or butadiene containing 50% by weight or more is contained. Is preferred. The production of the graft copolymer is carried out in a usual manner under known polymerization conditions.
【００３８】本発明に使用される（ｃ）成分の樹脂組成
物において、（イ）成分のα−メチルスチレン系共重合
体と（ロ）成分のグラフト共重合体との重量比は、
（イ）成分３０〜１００重量％と（ロ）成分０〜７０重
量％からなることが好ましく、特に（イ）成分５０〜１
００重量％と（ロ）成分０〜５０重量％からなることが
好ましい。（イ）成分が３０重量％未満の場合は耐熱性
の改良効果は殆ど得られない。In the resin composition of the component (c) used in the present invention, the weight ratio of the α-methylstyrene-based copolymer (a) to the graft copolymer (b) is as follows:
It is preferable that the component (A) comprises 30 to 100% by weight of the component (B) and 0 to 70% by weight of the component (B).
It is preferable that the composition comprises 00% by weight and 0 to 50% by weight of the component (ii). When component (a) is less than 30% by weight, the effect of improving heat resistance is hardly obtained.
【００３９】前記の（ａ）成分、（ｂ）成分及び（ｃ）
成分からなる本発明の（１）熱可塑性樹脂組成物Ａは、
ＪＩＳ Ｋ−７２０７ 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 above components (a), (b) and (c)
(1) The thermoplastic resin composition A of the present invention comprising the components:
The deflection temperature under load defined by JIS K-7207 A method is preferably 80 ° C. or more, particularly preferably 85 ° C. or more. When the deflection temperature under load is less than 80 ° C., the effect of improving the heat resistance is insufficient, and the film is easily deformed when exposed to a high-temperature atmosphere, which is not preferable.
【００４０】本発明の熱可塑性樹脂組成物Ａは、所要の
安定剤、加工助剤、強化剤、滑剤、充填剤及び顔料等を
適量含むものであっても良い。The thermoplastic resin composition A of the present invention may contain appropriate amounts of required stabilizers, processing aids, reinforcing agents, lubricants, fillers, pigments and the like.
【００４１】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.
【００４２】本発明の軟質樹脂組成物Ｂに使用される塩
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 flexible resin composition B of the present invention may be a mixture of polyvinyl chloride and a mixture of vinyl chloride and the above-mentioned vinyl compound copolymerized with the polyvinyl chloride. Any of those produced by ordinary methods such as fine suspension polymerization or emulsion polymerization can be used.
【００４３】塩化ビニルに共重合するビニル化合物とし
ては、前記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３０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。Examples of the vinyl compound copolymerized with vinyl chloride include the same compounds as described above. The amount of the vinyl compound used is preferably 30% by weight or less, more preferably 20% by weight, of the components of the vinyl chloride resin.
It is used in the following range.
【００４４】又、軟質樹脂組成物Ｂに使用される塩化ビ
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、硬質合成樹脂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 for the soft resin composition B is not particularly limited. However, when co-extrusion molding is performed, the difference in molding temperature between the resin and the hard synthetic resin material is reduced. In order to meet the object of the present invention of obtaining a suitable sealing material, it is preferable that the average degree of polymerization measured by JIS K-6721 is 2000 or more.
【００４５】本発明の軟質樹脂組成物Ｂに使用される部
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 flexible 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. Without, a method of obtaining by copolymerization with a polyfunctional compound such as divinylbenzene or ethylene glycol dimethacrylate, a method of increasing the reaction rate until a cross-linked acrylonitrile-butadiene copolymer insoluble in methyl ethyl ketone is generated, or a small amount of a cross-linking agent Any method can be used, such as a method of using an unvulcanized acrylonitrile-butadiene copolymer to crosslink it.
【００４６】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, for example, “Chemigum P83” (trade name, manufactured by Goodyear, Japan Synthetic Rubber Co., Ltd.)
Product name "JSR N201" and B.I. F. Goodrich Corporation, trade name “Hycar1421” and the like.
【００４７】又本発明の軟質樹脂組成物Ｂに使用される
可塑剤は塩化ビニル系樹脂の可塑剤として使用されるも
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 used as a plasticizer for the vinyl chloride resin. Examples thereof include dibutyl phthalate, diheptyl phthalate, and phthalic acid. Phthalic acid-based plasticizers such as di-2-ethylhexyl, diisononyl phthalate, and diisodecyl phthalate; trimellitic acid-based plasticizers such as tributyl trimellitate and tri-2-ethylhexyl trimellitate; Pyromellitic plasticizers such as octyl, phosphate plasticizers such as tricresyl phosphate and trioctyl phosphate, dioctyl adipate, fatty acid plasticizers such as dioctyl azelate and dioctyl sebacate, and
Examples include polyester-based plasticizers such as adipic acid polyester and sebacic polyester, and epoxy-based plasticizers such as alkyl epoxy stearate. These may be used alone or in combination of two or more. Also, a secondary plasticizer such as epoxidized soybean oil and chlorinated paraffin can be used in combination.
【００４８】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％の範囲にあることが好ましい。The soft resin composition B is 5 to 75% by weight of a vinyl chloride resin, 5 to 70% by weight of a partially cross-linked acrylonitrile-butadiene copolymer, and 10 to 65% of a plasticizer by weight.
Preferably it is in the range of weight%.
【００４９】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 content of the vinyl chloride resin is less than 5% by weight,
In extrusion molding, defective phenomena such as poor product appearance often occur, and when the content exceeds 75% by weight, the sealing portion of the obtained sealing material becomes hard, so that it is not suitable as a sealing material.
【００５０】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、７０
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, an appropriate molding temperature difference from a hard material at the time of coextrusion molding becomes large, and the obtained sealing material is deformed by pressing, compression and the like. Easy to receive. On the other hand, 70
Exceeding the weight percentage is unsuitable because defects such as poor product appearance tend to occur during extrusion molding.
【００５１】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 plasticizer is less than 10% by weight, the obtained sealing material is unsuitable as a sealing material because the sealing portion is hard, and if it exceeds 65% by weight, the hardness is excessively lowered, resulting in a high temperature atmosphere. It is easy to deform and unsuitable.
【００５２】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 can be added to the thermoplastic resin composition A and the soft resin composition B of the present invention in order to improve properties. 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 a 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, particularly preferably 0.03 μm to 7 μm.
μm to 5 μm are used. Among the fillers, calcium carbonate is preferred, and particularly preferred is calcium carbonate having an average particle size of 0.03 μm to 5 μm.
【００５３】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 no performance as a resin composition can be obtained.
【００５４】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 may contain, if necessary, stabilizers, processing aids, reinforcing agents, lubricants, pigments and the like used for general vinyl chloride resins. May be added.
【００５５】本発明において、（ａ）成分、（ｂ）成分
及び（ｃ）成分の混合順序等に制限はなく、一般的に
は、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, the order of mixing the components (a), (b) and (c) is not limited, and the mixing and pelletization are generally the same as in the case of ordinary vinyl chloride resins. Methods are used. Thermoplastic resin composition A,
For mixing with the soft resin composition B, for example, a mixer such as a high-speed mixer such as a Henschel mixer or a super mixer, or a ribbon blender is used. In the mixing method, it is preferable that the respective components are put into the above-mentioned mixer, and the components are uniformly blended at a temperature of, for example, 150 ° C. or less for a time appropriate for each mixer.
【００５６】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、押出機等の通常の塩化ビニル樹脂組
成物の製造に使用される常法により行われる。Granulation is performed by mixing the above mixture with a Banbury mixer,
It is carried out by a conventional method used in the production of ordinary vinyl chloride resin compositions such as a mixing roll and an extruder.
【００５７】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、使用され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 co-extrusion apparatus is not particularly limited.
Usually, a kneading and extruding apparatus A used for a hard material and a kneading and extruding apparatus B for a soft material are joined and integrated with the same mold C to obtain a co-extrusion apparatus D. Selection of A, B size, single-screw, twin-screw etc. and horizontal type, vertical type equipment etc. depends on the material used and the shape of co-extruded product,
It can be appropriately selected depending on the dimensions.
【００５８】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 surface design and the like, during extrusion molding, the surface may be extruded into a multilayer such as a vinyl chloride resin or an acrylic resin. In order to improve the strength and the like of the extruded product, a metal or the like may be co-extruded as necessary.
【００５９】[0059]
【実施例】以下、本発明を実施例により説明する。The present invention will be described below with reference to examples.
【００６０】実施例１〜６ 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 6 Each raw material shown in Table 1 was placed in a 75-liter Henschel mixer, mixed with stirring, and kneaded into pellets using a 90 m / m single screw extruder (manufactured by Ikegai Iron Works Co., Ltd.). 15 kg of each pellet of the thermoplastic resin composition A and the soft resin composition B were obtained. Using this, co-extrusion was performed with the following two extruders. Extruder A 65 m / m single screw extruder (Ikegai Iron Works Co., Ltd.) (for thermoplastic resin composition A) Extruder B 40 m / m vertical single screw extruder (Plastic Engineering Laboratory Co., Ltd.) (For soft resin composition B)
【００６１】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。The die for the co-extruded product was designed so as to have the composition of the thermoplastic resin composition A and the soft resin composition B.
【００６２】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 obtained co-extruded product had good moldability, and was cut into a length of 500 mm.
Heated in an atmosphere of ° C. for 48 hours. After removal, length L
Was measured and divided by the initial length of 500 mm to calculate a shrinkage ((500−L) / 500 × 100)%. A co-extruded product cut to a length of 500 mm is heated at 90 ° C.
Was evaluated in terms of deformation and warpage after heating for 48 hours in the atmosphere described above. Also, JIS for thermoplastic resin A part
The deflection temperature under load was measured by the K-7207 A method. The physical properties are shown in Table 1. As a result, the obtained co-extruded product was good and was practically usable as a sealing material.
【００６３】[0063]
【表１】 [Table 1]
【００６４】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 1-2 Each raw material shown in Table 2 was stirred, kneaded and pelletized in the same manner as in the above-mentioned Example, and co-extruded. The obtained co-extruded product was evaluated and measured, and the physical properties are shown in Table 2. As a result, it was not practical as a sealing material.
【００６５】[0065]
【表２】 [Table 2]
【００６６】（使用原材料）実施例１〜５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）（ａ）成分の塩素化塩化ビニル系樹脂 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(Raw Materials Used) Examples 1 to 5 and Comparative Example 1
Raw materials used in Nos. 1 to 2 are shown below. (1) Chlorinated vinyl chloride resin (a) component Nicatemp T241 (chlorine content 64.5% by weight) Nippon Carbide Industrial Co., Ltd.
【００６７】（２）（ｂ）成分の塩化ビニル系樹脂 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 as component (b) Vinyl chloride resin-1 Denkavinyl SS110 (degree of polymerization 1100) Vinyl chloride resin-2 manufactured by Denki Kagaku Kogyo Co., Ltd. Denkavinyl SH380 (degree of polymerization 3800) ) Made by Denki Kagaku Kogyo Co., Ltd.
【００６８】（３）（ｃ）成分の樹脂組成物 下記の（イ）成分６０重量％と（ロ）成分４０重量％を
混合して得られた樹脂組成物を使用した。(3) Resin composition of component (c) A resin composition obtained by mixing 60% by weight of the following component (A) and 40% by weight of the component (B) was used.
【００６９】（イ）成分のα−メチルスチレン系共重合
体 α−メチルスチレン２１０ｇ、スチレン１５ｇ、アクリ
ロニトリル４５ｇ及び開始剤を使用し乳化重合を開始し
た。途中でアクリロニトリル３０ｇを重合中に分添しな
がら、α−メチルスチレン系共重合体を得た。(A) α-Methylstyrene-based copolymer of the component Emulsion polymerization was started using 210 g of α-methylstyrene, 15 g of styrene, 45 g of acrylonitrile and an initiator. During the polymerization, 30 g of acrylonitrile was added during the polymerization to obtain an α-methylstyrene copolymer.
【００７０】（ロ）成分のグラフト共重合体 ポリブタジエンラテックス（ポリブタジエン固形分濃度
３５％、平均粒子径３５０μｍ：ゲル含量８７％）２８
６部及び開始剤を使用し、スチレン１０５部、アクリロ
ニトリル４５部を分添しながらグラフト乳化重合して、
グラフト共重合体を得た。(B) Graft Copolymer of Component Polybutadiene latex (polybutadiene solid content concentration 35%, average particle diameter 350 μm, gel content 87%) 28
Using 6 parts and an initiator, graft emulsion polymerization was performed while dispensing 105 parts of styrene and 45 parts of acrylonitrile.
A graft copolymer was obtained.
【００７１】（４）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(4) Partially crosslinked acrylonitrile-butadiene copolymer (abbreviated as NBR in the table) JSR N201 manufactured by Nippon Synthetic Rubber Co., Ltd.
【００７２】（５）可塑剤 フタル酸ジイソノニル （６）充填剤 平均粒径０．０８μｍの表面処理炭酸カ
ルシウム(5) Plasticizer Diisononyl phthalate (6) Filler Surface-treated calcium carbonate having an average particle size of 0.08 μm
【００７３】[0073]
【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。As described above, according to the present invention, an extruded product excellent in heat resistance, moldability and deformation resistance, specifically, a sealing material can be obtained.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.7 識別記号 ＦＩ // Ｂ２９Ｋ 25:00 27:06 Ｂ２９Ｌ 9:00 31:26 (56)参考文献 特開 平６−340038（ＪＰ，Ａ) 特開 平４−253786（ＪＰ，Ａ) 特開 平４−46944（ＪＰ，Ａ) 特開 平２−311547（ＪＰ，Ａ) 特開 昭62−59655（ＪＰ，Ａ) (58)調査した分野(Int.Cl.7，ＤＢ名) B29C 47/00 - 47/96 B32B 1/00 - 35/00 C08L 1/00 - 101/16 ──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. 7 Identification symbol FI // B29K 25:00 27:06 B29L 9:00 31:26 (56) References JP-A-6-340038 (JP, A) JP-A-4-253786 (JP, A) JP-A-4-46944 (JP, A) JP-A-2-311547 (JP, A) JP-A-62-259655 (JP, A) (58) Fields investigated (Int.Cl. 7 , DB name) B29C 47/00-47/96 B32B 1/00-35/00 C08L 1/00-101/16
Claims (2)
％、（ｂ）成分０〜８０重量％及び（ｃ）成分１０〜８
０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 （ｃ）成分 下記の（イ）成分３０〜１００重量％及び
（ロ）成分０〜７０重量％からなる樹脂組成物 （イ）成分 α−メチルスチレン６５〜８５重量％、シ
アン化ビニル化合物１５〜３５重量％及びこれらと共重
合する他のビニル化合物０〜２０重量％からなるα−メ
チルスチレン系共重合体 （ロ）成分 芳香族ビニル化合物５０〜８０重量％、シ
アン化ビニル化合物１５〜３５重量％及びこれらと共重
合する他のビニル化合物０〜３０重量％からなる混合物
２０〜７０重量部をガラス転移温度が０℃以下のゴム３
０〜８０重量部の存在下で共重合させて得られるグラフ
ト共重合体(1) 90 to 10% by weight of the following component (a), 0 to 80% by weight of component (b) and 10 to 8% of component (c) described below.
0% by weight of a thermoplastic resin composition A, (2) 5-75% by weight of a vinyl chloride resin, 5-70% by weight of a partially crosslinked acrylonitrile-butadiene copolymer, and a plasticizer 10
An extruded product obtained by co-extrusion with a soft resin composition B of up to 65% by weight. (A) Component Chlorinated vinyl chloride resin having a chlorine content of 60 to 70% by weight (b) Component Vinyl chloride resin (c) Component 30 to 100% by weight of the following component (A) and 0 to 70% of (B) component (B) 65-85% by weight of α-methylstyrene, 15-35% by weight of a vinyl cyanide compound and 0-20% by weight of another vinyl compound copolymerized therewith. Styrene-based copolymer (b) Component 20 to 70% by weight of a mixture composed of 50 to 80% by weight of an aromatic vinyl compound, 15 to 35% by weight of a vinyl cyanide compound and 0 to 30% by weight of another vinyl compound copolymerized therewith Rubber part whose glass transition temperature is 0 ° C or less
Graft copolymer obtained by copolymerization in the presence of 0 to 80 parts by weight
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 |
|---|---|---|---|
| JP07153216A JP3081511B2 (en) | 1994-07-25 | 1995-06-20 | Extruded products |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP17288794 | 1994-07-25 | ||
| JP6-172887 | 1994-07-25 | ||
| JP07153216A JP3081511B2 (en) | 1994-07-25 | 1995-06-20 | Extruded products |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0890629A JPH0890629A (en) | 1996-04-09 |
| JP3081511B2 true JP3081511B2 (en) | 2000-08-28 |
Family
ID=26481913
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP07153216A Expired - Fee Related JP3081511B2 (en) | 1994-07-25 | 1995-06-20 | Extruded products |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3081511B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06221853A (en) * | 1993-01-25 | 1994-08-12 | Agency Of Ind Science & Technol | Position detector |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101154792B1 (en) * | 2010-01-23 | 2012-06-18 | (주)한국Hpc | 3-layer type diaphragm for accumulator |
-
1995
- 1995-06-20 JP JP07153216A patent/JP3081511B2/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06221853A (en) * | 1993-01-25 | 1994-08-12 | Agency Of Ind Science & Technol | Position detector |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0890629A (en) | 1996-04-09 |
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