JP3702654B2 - Soft polymer composition and method for producing the same - Google Patents
Soft polymer composition and method for producing the same Download PDFInfo
- Publication number
- JP3702654B2 JP3702654B2 JP16979698A JP16979698A JP3702654B2 JP 3702654 B2 JP3702654 B2 JP 3702654B2 JP 16979698 A JP16979698 A JP 16979698A JP 16979698 A JP16979698 A JP 16979698A JP 3702654 B2 JP3702654 B2 JP 3702654B2
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- JP
- Japan
- Prior art keywords
- chlorinated polyethylene
- soft polymer
- polymer composition
- coumarone
- crosslinking
- 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.)
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Description
【０００１】
【発明の属する技術分野】
本発明は、軟質エラストマー組成物に代表される軟質高分子組成物に関し、より詳しくは、可塑剤や軟化剤のブリードや分離がなく、かつ、優れた制振性を示す軟質高分子組成物、およびその製造方法に関する。制振性を有する軟質エラストマーは、制振性を必要とする軟質の接着剤、シ−ラント、制振材、玩具、電気製品などに好適に適用できる。
【０００２】
【従来の技術】
従来、軟質エラストマ−組成物は、ゴムあるいは樹脂成分に可塑剤や軟化剤を多量に配合して得られていた。塩素化ポリエチレンを用いた軟質エラストマー組成物の製造法としては、高分子量の塩素化ポリエチレンに可塑剤を多量に配合する方法（例えば、特開平５−２４７２８８号公報参照）が提案され、また、粉末状のゴムを用いた軟質エラストマーの製造法としては、粉末状のゴムに可塑剤および／または軟化剤を含浸させた後、全体を混練する方法（例えば、特開平２−２７２００２号公報参照）が提案されている。
【０００３】
他方、従来より、ロジンエステルやクマロン−インデンオイルは粘着付与剤として各種ゴムに少量添加され、また、ロジンエステルはホットメルト接着剤などの成分としてエチレン−ビニルアセテート共重合体やポリプロピレン樹脂などに配合されている。しかし、これらを塩素化ポリエチレンに配合した例はない。
【０００４】
【発明が解決しようとする課題】
上記従来技術では、ゴムあるいは樹脂成分に可塑剤や軟化剤を多量に配合するため、可塑剤や軟化剤が組成物からブリ−ドしたり分離したりすることがあった。可塑剤や軟化剤のブリードを少しでも抑えるために充填剤を多量に用いると、充填剤が組成物中で分散不良を来たす嫌いがあった。さらに、接着剤やシ−ラントの分野ではこれら配合物をトルエンなどの有機溶媒を用いて製造する場合が多く、溶剤による環境汚染や人体への影響が懸念された。
【０００５】
本発明の目的は、上記実状に鑑み、可塑剤や軟化剤のブリードや分離がなく、かつ、優れた制振性を示す軟質高分子組成物を提供することにある。
【０００６】
本発明のもう一つの目的は、溶剤による環境汚染や人体への影響の懸念がない方法で軟質高分子組成物を製造することができる製造方法を提供することにある。
【０００７】
【課題を解決するための手段】
本発明者らは、上記課題を解決すべく種々検討を重ねたところ、塩素含有量が１５〜５０重量％の塩素化ポリエチレンが、ロジンエステルおよびクマロン−インデンオイルと非常に高い相溶性を示すことを見いだし、また、上記塩素化ポリエチレンと、上記ロジンエステルおよび／またはクマロン−インデンオイルとを混合することにより、これら物質のブリードや分離のない軟質エラストマー組成物が得られることを見いだし、本発明を完成するに至った。
【０００８】
本発明による軟質高分子組成物は、すなわち、（Ａ）塩素含有量１５〜５０重量％の塩素化ポリエチレンと、（Ｂ）軟化温度６０℃以下のロジンエステルおよび／またはクマロン−インデンオイルからなり、重量比（Ａ）：（Ｂ）が５〜４０：９５〜６０であることを特徴とするものである。
【０００９】
以下、本発明の構成につき詳細に説明する。
【００１０】
本発明において使用される塩素化ポリエチレンは、ポリエチレン粉末または粒子を水性懸濁液中、もしくは有機溶媒中で塩素化することにより得られるものである。塩素化ポリエチレンの原料ポリエチレンの分子量が大きくなるほど得られる組成物の引張り強度が大きくなるが、それぞれに伴って加工性が低下するため、重量平均分子量４万〜７０万の範囲にあるポリエチレンが原料として好ましい。用いる塩素化ポリエチレンの塩素含有量は１５〜５０重量％の範囲であることが好ましい。塩素含有量が１５重量％未満では原料ポリエチレンの結晶が残り、塩素化ポリエチレンのロジンエステルおよびクマロン−インデンオイルに対し相溶性が劣る。また、塩素含有量が５０重量％を越えると、塩素の凝集力が強くなり過ぎ、ロジンエステルおよびクマロン−インデンオイルが分離したりブリ−ドしたりする傾向があるので好ましくない。さらに、塩素含有量が１５〜５０重量％の範囲内であっても、塩素化ポリエチレンの残存結晶量を多くすると、ロジンエステルおよびクマロン−インデンオイルに対する相溶性が劣る傾向があるので、示差走査型熱量分析計（ＤＳＣ）法で測定した融解熱量が５ｃａｌ／ｇ以下である塩素化ポリエチレンが、より好ましい。
【００１１】
本発明に使用されるロジンエステルとは、ウッドロジン、ガムロジン、トール油ロジンなどの天然ロジン、およびこれらの精製物、あるいはアビエチン酸、ビマル酸のカルボン酸部分を、メタノール、エタノール、ブタノールなどのモノアルコ−ル、あるいはエチレングリコール、ジエチレングリコール、グリセリンなどの多価アルコ−ルでエステル化したものであり、安定化のために不均化や水素添加したものがさらに好ましい。
【００１２】
また、本発明に用いられるクマロン−インデンオイルとは、コールタールなどの中に含まれている、クマロン、インデン、スチレンなどの混合物の重合体である。
【００１３】
これらロジンエステルおよびクマロン−インデンオイルは本発明の目的とする軟質高分子組成物を得るためには、軟化温度が６０℃以下のものを用いることが好ましい。また、これらロジンエステルおよびクマロン−インデンオイルの併用、あるいは軟化点の異なる複数のロジンエステルあるいはクマロン−インデンオイルの併用も適宜なし得る。
【００１４】
上記塩素化ポリエチレンと、上記ロジンエステルおよび／またはクマロン−インデンオイルの配合割合は、塩素化ポリエチレンとロジンエステルおよび／またはクマロン−インデンオイルの合計１００重量部に対し、塩素化ポリエチレンが５〜４０重量部の範囲にある。塩素化ポリエチレンが５重量部未満であると、組成物が流動性を示すため材料の形状保持ができず、所期の軟質高分子組成物が得られない。また、塩素化ポリエチレンが４０重量部を越えると、得られるエラストマーの制振性が損なわれる。塩素化ポリエチレンの割合が５〜２５重量部の範囲内にあれば、より軟質で、かつ制振性の優れたエラストマーが得られるので好ましい。
【００１５】
本発明による軟質高分子組成物は、塩素化ポリエチレンを架橋することにより機械的強度を改善することができる。用いる架橋剤は、塩素化ポリエチレンを架橋せしめ得るものであればいかなるものでも良く、例えば、有機過酸化物系の架橋剤、チオール系架橋剤、アミン系架橋剤などを挙げることができる。また、架橋剤と架橋助剤（架橋促進剤）を併用しても良い。有機過酸化物としてはジクミルパーオキシド、ジベンゾイルパーオキシド、ジ-t-ブチルパーオキシド、t-ブ チルクミルパーオキシド、1,3-ビス-t-（ブチルパーオキシイソプロピル）ベン ゼン、1,1-ビス（t-ブチルパーオキシ）-3,3,5-トリメチルシクロヘキサン、n- ブチル-4,4-ビス（t-ブチルパーオキシ）バレレートなどが挙げられる。架橋剤 として有機過酸化物を用いる場合の架橋助剤としてはエチレングリコールジメタクリレート、トリメチールプロパントリメタクリレート、多官能性（メタ）アクリレート、多価アルコール（メタ）アクリレート、N,N′-m-フェニレンジマレイミド、トリアリルイソシアヌレート、ジアリルフタレートなどが挙げられる。チオール系架橋剤としては2,4,6-トリメルカプトトリアジン、2-アニリノ-4,6-ジ メルカプトトリアジン、2-ジブチル-4,6-ジメルカプトトリアジン、ジメルカプ トチアジアゾール、2-メルカプトイミダゾリン、ジアルキルチオウレア、エチレンチオウレアなどが挙げられ、アミン系架橋剤としてはヘキサメチレンジアミンなどの脂肪族ジアミン類、トリエチレンテトラミン、ペンタエチレンヘキサミンなどの多官能性ポリアミン類、p-フェニレンジアミンなどの芳香族多官能性アミン類などが挙げられる。チオール系架橋剤、アミン系架橋剤においても、架橋助剤を用いることは任意であり、用いられる架橋剤に応じて架橋助剤として例えば2,4,6-トリメルカプトトリアジンと2-メルカプトベンゾチアゾールのジシクロヘキシルアミン塩、ジメルカプトチアジアゾールとアニリンおよびブチルアルデヒドの縮合物、エチレンチオウレアと硫黄などが適宜選択される。また、上記架橋剤および架橋助剤をそれぞれ２種以上併用することもできる。
【００１６】
また、架橋を行う際には、塩素化ポリエチレンの受酸剤（架橋促進助剤）として通常用いられている金属酸化物、金属水酸化物などを添加することが望ましい。受酸剤としては、例えば、酸化マグネシウム、水酸化カルシウム、酸化マグネシウム、水酸化マグネシウム、鉛白、鉛丹、リサージ、ハイドロタルサイトなどを挙げることができ、これらは用いられる架橋剤に応じて適宜選択される。
【００１７】
本発明による組成物に、通常塩素化ポリエチレンに使用されている可塑剤を併用することも可能であるが、可塑剤の添加量が多すぎるとブリードや分離を招く恐れがあるので、可塑剤の使用量は、塩素化ポリエチレンとロジンエステルおよび／またはクマロン−インデンオイルの合計１００重量部に対して０〜５０重量部の範囲から適時選択される。可塑剤の例としては、ジ−２−エチルヘキシルフタレート、ジ−ｎ−オクチルフタレート、ジイソデシルフタレート、ジブチルフタレート、ジヘキシルフタレート、ジヘキシルフタレートなどのフタル酸エステル系可塑剤；ジオクチルアジペート、ジオクチルセバケート等の直鎖二塩基酸エステル系可塑剤；トリメリット酸エステル系可塑剤；ポリエステル系高分子可塑剤；エポキシ化大豆油、エポキシ化アマニ油等の液状エポキシ系可塑剤；トリフェニルホスフェート、トリキシリルホスフェート、トリクレジルホスフェート等のリン酸エステル系可塑剤が挙げられ、これらは単独で若しくは２種以上の組合せで使用する。
【００１８】
本発明による組成物に充填剤を使用することも可能である。充填剤の非限定的な例として、カーボンブラック、炭酸カルシウム、酸化チタン、タルク、水酸化アルミニウム、ハイドロタルサイト、クレー、シリカ、ホワイトカボーン等を挙げることができる。充填剤の添加量は、塩素化ポリエチレンとロジンエステルおよび／またはクマロン−インデンオイルの合計１００重量部に対して好ましくは２００重量部以下である。この添加量が２００重量部を越えると本発明の目的とする軟質高分子組成物が得られにくくなる。
【００１９】
さらに、本発明による組成物に安定剤、滑剤、加工助剤、酸化防止剤、紫外線吸収剤、発泡剤、難燃剤、顔料、上述以外の当該技術分野で通常用いられる各種添加剤を、必要に応じて配合することは任意である。
【００２０】
本発明による軟質高分子組成物は、ロジンエステルおよび／またはクマロン−インデンオイル中に塩素化ポリエチレンを投入するか、または、塩素化ポリエチレン中にロジンエステルおよび／またはクマロン−インデンオイルを投入し、この配合物を加熱溶融させるか、または、バンバリーミキサー、加圧ニーダー、インテンシブミキサー、インターナルミキサーなどの密閉混合機中で塩素化ポリエチレンとロジンエステルおよび／またはクマロン−インデンオイルを実質的に均一に分散させることにより得られる。また、塩素化ポリエチレンとロジンエステルおよび／またはクマロン−インデンオイルの合計１００重量部に対し、塩素化ポリエチレンが５〜２５重量部の配合割合であれば、６０℃以上の温度で配合物を加熱溶融させる方法が簡便である。
【００２１】
本発明による軟質高分子組成物の架橋物を得るには、汎用の架橋手段が適用できる。例えば、熱プレス、スチーム、高周波加熱、熱空気などの加熱方式を用いる架橋方法が、用いられる架橋剤に応じて適宜選択される。さらに、架橋方法として、塩素化ポリエチレンとロジンエステルおよび／またはクマロン−インデンオイルを含む組成物と、塩素化ポリエチレンを架橋せしめ得る架橋剤とからなる配合物を、バンバリーミキサー、加圧ニーダー、インテンシブミキサー、インターナルミキサーなどの溶融混練が可能な加工機械中に供給し、塩素化ポリエチレンを動的に架橋する方法が、簡便であって好ましい。
【００２２】
【発明の実施の形態】
本発明を実施するための具体的な形態を以下に実施例を挙げて説明する。但し、本発明はその要旨を逸脱しない限り以下の実施例に限定されるものではない。
【００２３】
［実施例１］
塩素化ポリエチレン、不均化ロジンエステル、受酸剤としての酸化マグネシウム、架橋剤および架橋助剤を、表１に示す配合割合で、１００℃に設定した５０ｃｃの内容積を持つブラベンダーミキサー中に、塩素化ポリエチレンと不均化ロジンエステルの合計で４０ｇになるように入れ、配合物を３０分間６０ｒｐｍで混練した後、ミキサー温度を１５０℃に昇温し、さらに３０分間６０ｒｐｍで混練を続け、軟質エラストマー組成物を得た。
【００２４】
得られた組成物を、１５０℃に設定したプレス機中で、成形面をテフロンコ−トした金型を用いて５分間加熱加圧した後、冷却することにより、２ｍｍ厚のシ−ト状に成形した。
【００２５】
［実施例２〜９、比較例１〜４］
塩素化ポリエチレンまたはエチレン−ビニルアセテート共重合体、不均化ロジンエステルまたはクマロン−インデンオイル、受酸剤としての酸化マグネシウム、ジオクチルフタレート、架橋剤および架橋助剤を、表１および２に示す配合割合で用いた点を除いて、実施例１と同様の操作を行い、シ−ト状の軟質エラストマー組成物を得た。
【００２６】
【表１】
【表２】
なお、表１および表２中の配合剤は下記の通りである。
【００２９】
塩素化ポリエチレン１：ダイソ−社製「ダイソラックＨ−１３５」、塩素含量３５％、ＤＳＣによる融解熱量０ｃａｌ／ｇ
塩素化ポリエチレン２：ダイソ−社製「ダイソラックＧ−２２０」、塩素含量２２％、ＤＳＣによる融解熱量４ｃａｌ／ｇ
塩素化ポリエチレン３：ダイソ−社製「ダイソラックＧ−２４５」、塩素含量４５％、ＤＳＣによる融解熱量１ｃａｌ／ｇ
塩素化ポリエチレン４：ダイソ−社製「ダイソラックＵ−３０３」、塩素含量３０％、ＤＳＣによる融解熱量９ｃａｌ／ｇ
エチレン−ビニルアセテート共重合体１：東ソー社製「ウルトラセン６３４」、ビニルアセテート含量２６％
エチレン−ビニルアセテート共重合体２：日本合成化学社製「ソアレックスＣＨ」、ビニルアセテート含量６０％
不均化ロジンエステル：荒川化学工業社製「ス−パ−エステルＬ」
クマロン−インデンオイル：神戸油化学工業社製「クマロンインデンオイル１５Ｅ」
酸化マグネシウム：協和化学工業社製「キョーワマグ＃１５０」
架橋剤１：２，４，６−トリメルカプトトリアジン
架橋助剤１：２−メルカプトベンゾチアゾ−ルのジシクロヘキシルアミン塩
架橋剤２：ジクミルパーオキサイド
架橋助剤２：トリアリルイソシアヌレート
［性能評価］
１）シートの目視観察
上記実施例および比較例で得られた各シートを目視で観察して、エラストマー組成物の均質性を評価した。この評価結果を表３および表４に示す。
【００３０】
２）諸物性の測定
実施例２〜６、８、および比較例２で得られた各シートについて、ＪＩＳ Ｋ−６３０１に規定される方法に従って、引張り試験および硬度の測定を行った。引張り試験用試験片としては、厚さ２ｍｍのシートをＪＩＳ Ｋ−６３０１に規定される３号ダンベル状に打ち抜いたものを用いた。引っ張り試験は、引っ張り速度５００ｍｍ／ｍｉｎで行った。この測定結果を表３および表４に示す。
【００３１】
３）動的粘弾性測定
実施例１〜５、７、および比較例２で得られた各シートについて、動的粘弾性測定を行った。動的粘弾性測定用試験片としては、厚さ２ｍｍのシートを幅４ｍｍ、長さ５０ｍｍに打ち抜いたものを用いた。動的粘弾性測定は、各チャック間の距離を１０ｍｍとし、試験片に周波数１０Ｈｚ、振幅２０μｍの曲げ振動を加え、−５０℃から２℃／ｍｉｎの昇温速度で８０℃まで動的粘弾性を測定した。動的粘弾性測定から得られる損失係数Ｔａｎδの測定値が大きな値を示し、かつ大きな値を示す温度範囲が幅広いものほど、優れた制振性を示す材料である。
【００３２】
この測定結果を図１および図２に示す。
【００３３】
【表３】
【表４】
表３および表４のシート目視観察結果から判るように、各実施例で得られたシートは透明あるいは半透明のシ−トであり、これらは塩素化ポリエチレンとロジンエステルまたはクマロン−インデンオイルが均質に分散したものであった。可塑剤として一般的に用いられているジオクチルフタレートを添加して得られた比較例１のシートは可塑剤がブリードするため均質となっていなかった。低ビニルアセテート含量のエチレン−ビニルアセテート共重合体を用いた比較例３ではエチレン−ビニルアセテート共重合体が溶融せずシートが得られなかった。高ビニルアセテート含量のエチレン−ビニルアセテート共重合体を用いた比較例４では組成物は液状となった。
【００３６】
また、表３および表４の諸物性測定結果から判るように、各実施例のシートは軟質エラストマーとしての良好な引っ張り特性と硬度を示しているが、塩素化ポリエチレンとロジンエステルの配合割合が本発明の範囲内から逸脱する比較例２のシートは、硬度が高く、軟質高分子組成物となっていなかった。
【００３７】
さらに、動的粘弾性測定の結果を示す図１および図２から明らかなように、実施例の軟質エラストマーは優れた制振性能を示している。
【００３８】
【発明の効果】
本発明は以上のように構成されており、可塑剤や軟化剤のブリードや分離がない軟質高分子組成物を得ることができる。そして、この組成物は優れた制振性能を示しているので、制振性を必要とされる軟質の接着剤、シ−ラント、制振材、玩具、電気製品などの分野への同組成物の応用が期待される。
【００３９】
また、本発明による軟質高分子組成物は、塩素化ポリエチレンと、ロジンエステルおよび／またはクマロン−インデンオイルを、６０℃以上の温度にて溶融することにより、容易に製造することができる。したがって、溶媒を使う必要がなく、溶剤による環境汚染や人体への影響の懸念がない。
【００４０】
さらに、塩素化ポリエチレンと、ロジンエステルおよび／またはクマロン−インデンオイルとを含む組成物と、塩素化ポリエチレンを架橋せしめ得る架橋剤とからなる配合物を、溶融混練可能な加工機械中に供給し、塩素化ポリエチレンを動的に架橋することにより、容易に軟質高分子架橋物を製造することができる。
【図面の簡単な説明】
【図１】 温度と損失係数Ｔａｎδの関係を示すグラフである。
【図２】 温度と損失係数Ｔａｎδの関係を示すグラフである。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a soft polymer composition typified by a soft elastomer composition, and more specifically, a soft polymer composition that has no bleeding or separation of a plasticizer or a softener and exhibits excellent vibration damping properties, And a manufacturing method thereof. Soft elastomer having a vibration damping property, the adhesive soft that require vibration-damping properties, shea - Holland, damping material, toys, or the like can suitably be applied appliances.
[0002]
[Prior art]
Conventionally, soft elastomer compositions have been obtained by blending a large amount of plasticizers and softeners with rubber or resin components. As a method for producing a soft elastomer composition using chlorinated polyethylene, a method of blending a large amount of plasticizer with high molecular weight chlorinated polyethylene (for example, see JP-A-5-247288) has been proposed, and powder As a method for producing a soft elastomer using a rubber-like rubber, there is a method of impregnating a powdery rubber with a plasticizer and / or a softening agent and then kneading the whole (for example, see JP-A-2-272002). Proposed.
[0003]
On the other hand, rosin ester and coumarone-indene oil have been added to various rubbers as tackifiers, and rosin ester has been blended into ethylene-vinyl acetate copolymer and polypropylene resin as components such as hot melt adhesives. Has been. However, there is no example of blending these with chlorinated polyethylene.
[0004]
[Problems to be solved by the invention]
In the above prior art, a large amount of plasticizer or softener is blended in the rubber or resin component, so that the plasticizer or softener sometimes bleeds or separates from the composition. When a large amount of filler is used in order to suppress bleed of plasticizers and softeners, there is a disagreement that the filler causes poor dispersion in the composition. Furthermore, in the field of adhesives and sealants, these blends are often produced using an organic solvent such as toluene, and there has been concern about environmental pollution and effects on the human body due to the solvent.
[0005]
In view of the above circumstances, an object of the present invention is to provide a soft polymer composition that is free from bleeding and separation of plasticizers and softeners and exhibits excellent vibration damping properties.
[0006]
Another object of the present invention is to provide a production method capable of producing a soft polymer composition by a method which is free from concerns about environmental pollution and effects on the human body due to a solvent.
[0007]
[Means for Solving the Problems]
As a result of various studies to solve the above problems, the present inventors have found that chlorinated polyethylene having a chlorine content of 15 to 50% by weight exhibits very high compatibility with rosin ester and coumarone-indene oil. In addition, it was found that a soft elastomer composition free from bleeding and separation of these substances can be obtained by mixing the chlorinated polyethylene with the rosin ester and / or coumarone-indene oil. It came to be completed.
[0008]
The soft polymer composition according to the present invention comprises (A) a chlorinated polyethylene having a chlorine content of 15 to 50% by weight and (B) a rosin ester and / or coumarone-indene oil having a softening temperature of 60 ° C. or less. The weight ratio (A) :( B) is 5 to 40:95 to 60.
[0009]
Hereinafter, the configuration of the present invention will be described in detail.
[0010]
The chlorinated polyethylene used in the present invention is obtained by chlorinating polyethylene powder or particles in an aqueous suspension or in an organic solvent. The tensile strength of the resulting composition increases as the molecular weight of the raw material polyethylene of the chlorinated polyethylene increases. However, since the processability decreases with each, polyethylene having a weight average molecular weight in the range of 40,000 to 700,000 is used as the raw material. preferable. The chlorine content of the chlorinated polyethylene used is preferably in the range of 15 to 50% by weight. When the chlorine content is less than 15% by weight, the raw material polyethylene crystals remain, and the compatibility with the rosin ester of chlorinated polyethylene and coumarone-indene oil is poor. On the other hand, if the chlorine content exceeds 50% by weight, the cohesive strength of chlorine becomes too strong, and rosin ester and coumarone-indene oil tend to separate or bleed, which is not preferable. Furthermore, even if the chlorine content is in the range of 15 to 50% by weight, if the amount of residual crystals of chlorinated polyethylene is increased, the compatibility with rosin ester and coumarone-indene oil tends to be inferior. A chlorinated polyethylene having a calorie of fusion measured by a calorimeter (DSC) method of 5 cal / g or less is more preferable.
[0011]
The rosin ester used in the present invention is a natural rosin such as wood rosin, gum rosin, tall oil rosin, and purified products thereof, or a carboxylic acid portion of abietic acid or vimaric acid, and a monoalcohol such as methanol, ethanol or butanol. Or those esterified with polyhydric alcohols such as ethylene glycol, diethylene glycol, glycerin, etc., and more preferably disproportionated or hydrogenated for stabilization.
[0012]
The coumarone-indene oil used in the present invention is a polymer of a mixture of coumarone, indene, styrene and the like contained in coal tar and the like.
[0013]
These rosin esters and coumarone-indene oils are preferably those having a softening temperature of 60 ° C. or lower in order to obtain the intended soft polymer composition of the present invention. In addition, a combination of these rosin esters and coumarone-indene oil, or a combination of a plurality of rosin esters or coumarone-indene oils having different softening points can be used as appropriate.
[0014]
The blending ratio of the chlorinated polyethylene and the rosin ester and / or coumarone-indene oil is 5 to 40 weight percent of chlorinated polyethylene with respect to 100 parts by weight of the total of chlorinated polyethylene and rosin ester and / or coumarone-indene oil. In the range of the part. If the chlorinated polyethylene is less than 5 parts by weight, the composition exhibits fluidity, so that the shape of the material cannot be maintained, and the desired soft polymer composition cannot be obtained. On the other hand, when the amount of chlorinated polyethylene exceeds 40 parts by weight, the vibration damping property of the resulting elastomer is impaired. If the ratio of chlorinated polyethylene is in the range of 5 to 25 parts by weight, it is preferable because an elastomer that is softer and has excellent vibration damping properties can be obtained.
[0015]
The soft polymer composition according to the present invention can improve mechanical strength by crosslinking chlorinated polyethylene. Any crosslinking agent may be used as long as it can crosslink chlorinated polyethylene. Examples thereof include organic peroxide crosslinking agents, thiol crosslinking agents, and amine crosslinking agents. Moreover, you may use together a crosslinking agent and a crosslinking adjuvant (crosslinking accelerator). Examples of organic peroxides include dicumyl peroxide, dibenzoyl peroxide, di-t-butyl peroxide, t-butylcumyl peroxide, 1,3-bis-t- (butylperoxyisopropyl) benzene, 1 , 1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane, n-butyl-4,4-bis (t-butylperoxy) valerate and the like. When using organic peroxides as crosslinking agents, the crosslinking aids include ethylene glycol dimethacrylate, trimethyl propane trimethacrylate, polyfunctional (meth) acrylate, polyhydric alcohol (meth) acrylate, N, N'-m- Examples include phenylene dimaleimide, triallyl isocyanurate, diallyl phthalate and the like. Thiol-based crosslinking agents include 2,4,6-trimercaptotriazine, 2-anilino-4,6-dimercaptotriazine, 2-dibutyl-4,6-dimercaptotriazine, dimercaptothiadiazole, 2-mercaptoimidazoline, dialkyl Thiourea, ethylenethiourea, etc. are mentioned. As amine-based crosslinking agents, aliphatic diamines such as hexamethylenediamine, polyfunctional polyamines such as triethylenetetramine and pentaethylenehexamine, and aromatic polyfunctional such as p-phenylenediamine. Include functional amines. In the thiol-based crosslinking agent and amine-based crosslinking agent, it is optional to use a crosslinking aid, and 2,4,6-trimercaptotriazine and 2-mercaptobenzothiazole are used as the crosslinking aid depending on the crosslinking agent used. A dicyclohexylamine salt, a condensate of dimercaptothiadiazole and aniline and butyraldehyde, ethylenethiourea and sulfur, and the like are appropriately selected. Two or more of the above-mentioned crosslinking agents and crosslinking assistants can be used in combination.
[0016]
In addition, when performing crosslinking, it is desirable to add metal oxides, metal hydroxides, and the like that are commonly used as acid acceptors (crosslinking acceleration aids) for chlorinated polyethylene. Examples of the acid acceptor include magnesium oxide, calcium hydroxide, magnesium oxide, magnesium hydroxide, white lead, red lead, risurge, hydrotalcite, and the like, and these may be appropriately selected depending on the crosslinking agent used. Selected.
[0017]
Although it is possible to use a plasticizer usually used in chlorinated polyethylene in combination with the composition according to the present invention, too much added plasticizer may cause bleeding and separation. The amount used is appropriately selected from the range of 0 to 50 parts by weight based on 100 parts by weight of the total of chlorinated polyethylene and rosin ester and / or coumarone-indene oil. Examples of plasticizers include phthalate plasticizers such as di-2-ethylhexyl phthalate, di-n-octyl phthalate, diisodecyl phthalate, dibutyl phthalate, dihexyl phthalate, and dihexyl phthalate; direct dioctyl adipate, dioctyl sebacate, etc. Chain dibasic acid ester plasticizers; trimellitic acid ester plasticizers; polyester polymer plasticizers; liquid epoxy plasticizers such as epoxidized soybean oil and epoxidized linseed oil; triphenyl phosphate, trixylyl phosphate, tri Examples thereof include phosphate plasticizers such as cresyl phosphate, which are used alone or in combination of two or more.
[0018]
It is also possible to use fillers in the composition according to the invention. Non-limiting examples of fillers include carbon black, calcium carbonate, titanium oxide, talc, aluminum hydroxide, hydrotalcite, clay, silica, white cabbage and the like. The addition amount of the filler is preferably 200 parts by weight or less with respect to 100 parts by weight in total of chlorinated polyethylene and rosin ester and / or coumarone-indene oil. When this addition amount exceeds 200 parts by weight, it becomes difficult to obtain the intended soft polymer composition of the present invention.
[0019]
Further, the composition according to the present invention requires stabilizers, lubricants, processing aids, antioxidants, ultraviolet absorbers, foaming agents, flame retardants, pigments, and various additives usually used in the technical field other than those described above. It is optional to mix them accordingly.
[0020]
The soft polymer composition according to the present invention is charged with chlorinated polyethylene in rosin ester and / or coumarone-indene oil, or with rosin ester and / or coumarone-indene oil in chlorinated polyethylene. Heat-melt the compound or disperse the chlorinated polyethylene and rosin ester and / or coumarone-indene oil substantially uniformly in a closed mixer such as a Banbury mixer, pressure kneader, intensive mixer, internal mixer, etc. Is obtained. If the blending ratio of chlorinated polyethylene is 5 to 25 parts by weight with respect to a total of 100 parts by weight of chlorinated polyethylene and rosin ester and / or coumarone-indene oil, the blend is heated and melted at a temperature of 60 ° C. or higher. The method of making it easy is.
[0021]
In order to obtain a crosslinked product of the soft polymer composition according to the present invention, general-purpose crosslinking means can be applied. For example, a crosslinking method using a heating method such as hot pressing, steam, high-frequency heating, hot air or the like is appropriately selected according to the crosslinking agent used. Further, as a crosslinking method, a compound comprising a composition containing chlorinated polyethylene and rosin ester and / or coumarone-indene oil and a crosslinking agent capable of crosslinking chlorinated polyethylene is used as a Banbury mixer, a pressure kneader, an intensive mixer. A method of supplying the mixture into a processing machine capable of melt-kneading such as an internal mixer and dynamically cross-linking chlorinated polyethylene is simple and preferable.
[0022]
DETAILED DESCRIPTION OF THE INVENTION
Specific modes for carrying out the present invention will be described below with reference to examples. However, the present invention is not limited to the following examples without departing from the gist thereof.
[0023]
[Example 1]
Chlorinated polyethylene, disproportionated rosin ester, magnesium oxide as acid acceptor, crosslinking agent and crosslinking aid in a blending ratio shown in Table 1 in a Brabender mixer having an internal volume of 50 cc set at 100 ° C. Then, the total amount of chlorinated polyethylene and disproportionated rosin ester is 40 g, and the mixture is kneaded at 60 rpm for 30 minutes, then the mixer temperature is raised to 150 ° C., and further kneading is continued at 60 rpm for 30 minutes. A soft elastomer composition was obtained.
[0024]
The obtained composition was heated and pressed for 5 minutes in a press machine set at 150 ° C. using a mold having a Teflon-coated molding surface, and then cooled to form a sheet having a thickness of 2 mm. Molded.
[0025]
[Examples 2 to 9, Comparative Examples 1 to 4]
Chlorinated polyethylene or ethylene-vinyl acetate copolymer, disproportionated rosin ester or coumarone-indene oil, magnesium oxide as acid acceptor, dioctyl phthalate, cross-linking agent and cross-linking aid shown in Tables 1 and 2 A sheet-like soft elastomer composition was obtained by performing the same operation as in Example 1 except for the points used in 1.
[0026]
[Table 1]
[Table 2]
In addition, the compounding agents in Table 1 and Table 2 are as follows.
[0029]
Chlorinated polyethylene 1: “Daiisolac H-135” manufactured by Daiso Corporation, chlorine content 35%, heat of fusion by
Chlorinated polyethylene 2: “Daisolac G-220” manufactured by Daiso, Inc., chlorine content 22%, heat of fusion by DSC 4 cal / g
Chlorinated polyethylene 3: “Daisolac G-245” manufactured by Daiso, Inc., chlorine content 45%, heat of fusion 1 cal / g by DSC
Chlorinated polyethylene 4: "Daiisolac U-303" manufactured by Daiso Corporation, chlorine content 30%, heat of fusion by DSC 9 cal / g
Ethylene-vinyl acetate copolymer 1: "Ultrasen 634" manufactured by Tosoh Corporation, vinyl acetate content 26%
Ethylene-vinyl acetate copolymer 2: “Soarex CH” manufactured by Nippon Synthetic Chemical Co., Ltd., 60% vinyl acetate content
Disproportionated rosin ester: “Super Ester L” manufactured by Arakawa Chemical Industries, Ltd.
Coumarone-Inden Oil: “Coumarone Inden Oil 15E” manufactured by Kobe Oil Chemical Industries, Ltd.
Magnesium oxide: “Kyowa Mug # 150” manufactured by Kyowa Chemical Industry Co., Ltd.
Crosslinking agent 1: 2,4,6-trimercaptotriazine crosslinking aid 1: dicyclohexylamine salt crosslinking agent of 2-mercaptobenzothiazole 2: dicumyl peroxide crosslinking aid 2: triallyl isocyanurate [performance evaluation ]
1) Visual observation of sheet Each sheet obtained in the above Examples and Comparative Examples was visually observed to evaluate the homogeneity of the elastomer composition. The evaluation results are shown in Tables 3 and 4.
[0030]
2) Measurement of various physical properties The sheets obtained in Examples 2 to 6, 8 and Comparative Example 2 were subjected to a tensile test and a hardness measurement according to the method defined in JIS K-6301. As a test piece for a tensile test, a sheet having a thickness of 2 mm was punched into a No. 3 dumbbell shape defined in JIS K-6301. The tensile test was performed at a pulling speed of 500 mm / min. The measurement results are shown in Tables 3 and 4.
[0031]
3) Dynamic viscoelasticity measurement About each sheet | seat obtained in Examples 1-5, 7 and the comparative example 2, the dynamic viscoelasticity measurement was performed. As a test piece for measuring dynamic viscoelasticity, a sheet having a thickness of 2 mm punched into a width of 4 mm and a length of 50 mm was used. In the dynamic viscoelasticity measurement, the distance between each chuck is 10 mm, a bending vibration having a frequency of 10 Hz and an amplitude of 20 μm is applied to the test piece, and the dynamic viscoelasticity is increased from −50 ° C. to 80 ° C. at a temperature rising rate of 2 ° C./min. Was measured. The measured value of the loss coefficient Tanδ obtained from the dynamic viscoelasticity measurement shows a large value, and the wider the temperature range where the large value is shown, the more excellent the vibration damping property is.
[0032]
The measurement results are shown in FIGS.
[0033]
[Table 3]
[Table 4]
As can be seen from the results of visual observation of the sheets in Tables 3 and 4, the sheets obtained in each example are transparent or translucent sheets, and these are homogeneous chlorinated polyethylene and rosin ester or coumarone-indene oil. It was dispersed. The sheet of Comparative Example 1 obtained by adding dioctyl phthalate generally used as a plasticizer was not homogeneous because the plasticizer bleeds. In Comparative Example 3 using an ethylene-vinyl acetate copolymer having a low vinyl acetate content, the ethylene-vinyl acetate copolymer did not melt and a sheet was not obtained. In Comparative Example 4 using an ethylene-vinyl acetate copolymer having a high vinyl acetate content, the composition became liquid.
[0036]
Further, as can be seen from the measurement results of various physical properties in Tables 3 and 4, the sheets of each example show good tensile properties and hardness as a soft elastomer, but the blending ratio of chlorinated polyethylene and rosin ester is The sheet of Comparative Example 2 deviating from the scope of the invention had high hardness and was not a soft polymer composition.
[0037]
Furthermore, as is clear from FIGS. 1 and 2 showing the results of the dynamic viscoelasticity measurement, the soft elastomers of the examples show excellent vibration damping performance.
[0038]
【The invention's effect】
The present invention is configured as described above, and a soft polymer composition free from bleeding and separation of plasticizers and softeners can be obtained. Since this composition exhibits excellent vibration damping performance, the composition is used in the fields of soft adhesives, sealants, vibration damping materials, toys, and electrical products that require vibration damping. Is expected to be applied.
[0039]
The soft polymer composition according to the present invention can be easily produced by melting chlorinated polyethylene and rosin ester and / or coumarone-indene oil at a temperature of 60 ° C. or higher. Therefore, it is not necessary to use a solvent, and there is no concern about environmental pollution or influence on the human body due to the solvent.
[0040]
Further, a composition comprising a composition containing chlorinated polyethylene, rosin ester and / or coumarone-indene oil, and a cross-linking agent capable of cross-linking chlorinated polyethylene is supplied to a melt-kneaded processing machine, By dynamically cross-linking chlorinated polyethylene, a soft polymer cross-linked product can be easily produced.
[Brief description of the drawings]
FIG. 1 is a graph showing the relationship between temperature and loss coefficient Tanδ.
FIG. 2 is a graph showing the relationship between temperature and loss coefficient Tanδ.
Claims (6)
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