JP3608893B2 - Abrasion-resistant elastic sheet, foamable sheet and elastic foam made therefrom - Google Patents
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Description
【０００１】
【発明の属する技術分野】
本発明は、特定のエチレン−酢酸ビニル共重合体と特定のポリウレタンエラストマーとを特定量配合してなる樹脂組成物から作った耐摩耗性弾性シート、上記樹脂組成物に更に化学発泡剤を配合し、それから作った発泡性シート、該発泡性シートから作った耐摩耗性弾性発泡体、並びに上記耐摩耗性弾性シートと上記発泡性シートから作った耐摩耗性表皮つき弾性発泡体に関する。
【０００２】
本発明は、更に、ポリオレフィン、熱可塑性エラストマー、合成ゴム、天然ゴム等と化学発泡剤から作った発泡性シートと上記耐摩耗性弾性シートから作った耐摩耗性表皮つき弾性発泡体に関する。
本発明は、更に、上記耐摩耗性弾性発泡体から作った靴底、靴等に関する。
本発明は、更に、上記耐摩耗性弾性シートと、織布又は不織布とからなる多層体及び、この多層体で作ったフレキシブルコンテナーに関する。
【０００３】
本発明の上記耐摩耗性弾性シート、耐摩耗性弾性発泡体、多層体等は靴底、フレキシブルコンテナー以外に、衣料品、家具、椅子、スポーツ用品、建築材料、自動車内装材、飛行機内装材、船舶内装材、列車内装材、フェンス、防音材、緩衝材、フィルター、農業用資材、レジャー用品、医療用品、包装資材、水産用資材、農業用資材等として利用される。特に、プールマット、浴室用マット、調理場マット、洗車場マット等水を使用する場所で使用するマットとして好適である。
又、馬、牛、豚、ニワトリ、アヒル、ガチョウ、七面鳥等家畜類の飼育場の床材として好適である。
【０００４】
【従来の技術】
本願出願人は、エチレン−酢酸ビニル共重合体（以降において、ＥＶＡと記載することもある。）に化学発泡剤を配合し、ＥＶＡ発泡体を作り、これから靴底材を作っているが、ＥＶＡ発泡体は、クッション性はよいものの、耐摩耗性が悪く、ＥＶＡ発泡体の表皮として、各種シートを貼合し、耐摩耗性の改良を計ってきた。各種シートのうち、耐摩耗性が一番よいものはポリウレタンエラストマーであるが、価格が非常に高く、又、ＥＶＡ発泡体との貼合には、接着力のつよい高価な接着剤を利用しなければならず、コストアップになり、解決が求められてきた。
【０００５】
本発明者等は、ＥＶＡとポリウレタンエラストマーからなるシートがよい結果を与えるのではないかと予想し、従来技術について調査を行ったが、ＥＶＡとポリウレタンエラストマーからなるシートについては、従来技術は見出せなかった。先行技術文献として存在していたのは、例えば、特公昭５８−４１３１０号において、熱可塑性ポリウレタン樹脂とエチレン−酢酸ビニル−塩化ビニル三元重合体とを７０〜９０重量％：３０〜１０重量％の割合で混合してなる樹脂配合物をエチレン−酢酸ビニル共重合樹脂５０〜９０重量％に対して５０〜１０重量％の割合で混合してなることを特徴とするターポリン被膜形成用合成樹脂組成物が示されており、エチレン−酢酸ビニル−塩化ビニル三元重合体の量が１０重量％より少ないと、ＥＶＡと熱可塑性ポリウレタンの相溶性が悪くなりブレンドが困難となると記載されている。
【０００６】
又、特開平６１−２１１４００号には、ポリウレタン樹脂とエチレン−酢酸ビニル共重合体樹脂との混合樹脂からなる塗膜層を天然皮革表面に有するとともに、該塗膜層が天然皮革内部にまで浸透していることを特徴とする皮革材料が示されているが、上記ポリウレタン樹脂は、エラストマーではなく、１液型、２液型あるいはプレポリマー型（明細書（２）ページ、右下欄上から１〜２行目）であり、液状ポリウレタン原料とＥＶＡの混合であり、本願発明とは、解決すべき課題が異るものである。
【０００７】
さらに、特開平１−１１７２０１号には、導体上に、ショアーＤ硬度７３以上のポリウレタン樹脂５０〜９０重量％と、エチレン−アクリル酸メチル共重合体、エチレン−アクリル酸共重合体、エチレン−酢酸ビニル共重合体の内、少なくとも１種の共重合体を１０〜５０重量％との混合樹脂組成物による０．３ｍｍ以下の薄肉絶縁層を設けたことを特徴とする絶縁電線が示されているが、ポリウレタン樹脂が５０重量％以上でＥＶＡが５０重量％以下であるので、混練物が得られたものと思われ、本願発明の様にＥＶＡが７０重量％以上でポリウレタンエラストマーが３０重量％以下の場合とは異なっており、特開平１−１１７２０１号の技術によって、本願発明の課題が解決できるものではない。
【０００８】
また、特開昭５０−７６１６５号には、２〜５重量％の下記のエチレン共重合体を混合した可溶性および／または熱可塑性のポリウレタンからなる組成物：７９〜９８．３モル％のエチレン、２０．５〜１．７モル％の脂肪酸の少なくとも一種の不飽和エステルでエステルは分子中に３〜８炭素原子を含むもの、および、１０〜０モル％の分子中に３〜７炭素原子をもつ不飽和酸類および該酸類の塩類および無水物からなる群から選ばれる少なくとも一種の化合物が示されているが、ＥＶＡの配合量が２〜５重量％と少ないこと、ポリウレタンとＥＶＡは溶液として配合すること、ＥＶＡの配合目的がポリウレタンのブロッキング防止であること等、本願発明と目的、構成が異なっている。
【０００９】
【発明が解決しようとする課題】
上述した様に、ＥＶＡとポリウレタンエラストマーとからなる耐摩耗性があり、低コストのシートを作ることを発明の第一の課題とし、このシートと他の素材（発泡体、織布、不織布）との多層体を作ることを発明の第二の課題とし、更にこれらの多層体で靴底、フレキシブルコンテナー等を作ることを発明の第三の課題とする。
【００１０】
【課題を解決するための手段】
本発明者等は、従来、ポリウレタンエラストマーとＥＶＡは、相溶化剤の存在なしには均一な樹脂組成物ができないという業界の常識に挑み、相溶化剤なしで、ＥＶＡが７０〜９０重量％、ポリウレタンエラストマーが１０〜３０重量％からなる均一な樹脂組成物を作ることに成功した。
文献上では、前述した様に、ポリウレタン樹脂が５０重量％以上でＥＶＡが５０重量％以下の配合例があるが、これは、極性の高いポリウレタン樹脂に、ＥＶＡを５０重量％以下配合したものであり、本願発明の配合比率とは異なっており、又、均一に配合されているか否かについては全く記載がない。不均一な配合ならば、いかなる樹脂同志であっても配合は可能であるが、機械的強度、耐久性、耐化学薬品性、耐熱性、耐低温脆化性、弾性等は発現しないものである。
【００１１】
本発明者等は、コスト低減、低温熱溶着性、高速加工性、耐ブロッキング性がよく、かつ、耐摩耗性がよいシートを開発するためには、ＥＶＡが主成分を占め、ポリウレタンエラストマーが少量の成分となる範囲で、各種のＥＶＡ、各種のポリウレタンを配合したところ、特定のＥＶＡ、特定のポリウレタンを、それぞれ特定量配合し、バンバリーミキサーで特定温度で混練した場合のみ、均一に配合された樹脂組成物が得られ、これから耐摩耗性弾性シートが得られることを実証し、本発明を完成させた。
【００１２】
すなわち、本発明の主題は、酢酸ビニル含有量１７〜２６重量％、メルトインデックス０．５〜５ｇ／１０分のエチレン−酢酸ビニル共重合体７０〜９０重量部、ビカー軟化点７０〜１００℃のポリウレタンエラストマー１０〜３０重量部からなる樹脂成分を加熱混練機で８０〜１３０℃の温度で少なくとも７分間混練し、次にチルロールによるカレンダー法で作った耐摩耗性弾性シートに関する。
【００１３】
本発明の他の主題は、酢酸ビニル含有量１７〜２６重量％、メルトインデックス０．５〜５ｇ／１０分のエチレン−酢酸ビニル共重合体７０〜９０重量部、ビカー軟化点７０〜１００℃のポリウレタンエラストマー１０〜３０重量部、化学発泡剤０．１〜２５重量部からなる樹脂組成物を加熱混練機で８０〜１３０℃の温度で少なくとも７分間混練し、次にチルロールによるカレンダー法で作った発泡性シートに関する。
【００１４】
本発明の他の主題は、前記の発泡性シートを所定の形状に裁断し、金型に入れ、化学発泡剤の分解温度以上に加熱し発泡させて得た耐摩耗性弾性発泡体、並びに前記の耐摩耗性弾性シートと前記の発泡性シートを重合し、所定の形状に裁断し、金型に入れ、化学発泡剤の分解温度以上に加熱し、発泡と貼合を行わせて得た耐摩耗性表皮付き弾性発泡体に関する。
【００１５】
さらに、本発明の主題は、ポリオレフィン、熱可塑性エラストマー、合成ゴム、天然ゴム等から選択された素材１００重量部と化学発泡剤０．１〜２５重量部からなる樹脂組成物から作った発泡性シートと前記の耐摩耗性弾性シートを重合し、所定の形状に裁断し、金型に入れ、化学発泡剤の分解温度以上に加熱し、発泡と貼合を行わせて得た耐摩耗性表皮付き弾性発泡体に関する。
【００１６】
本発明のさらに他の主題は、前記の弾性発泡体を裁断して得た靴底及びこの靴底を使用して作った靴又はサンダル、並びに前記の耐摩耗性弾性シートと、織布又は不織布とを貼合して作った多層体及びこの多層体から作ったフレキシブルコンテナーに関する。
更に、本発明は、前記の耐摩耗性弾性発泡体を裁断して得たプールマット、家畜用マット等に関する。
【００１７】
【発明の実施の形態】
本発明において、酢酸ビニル含有量１７〜２６重量％、メルトインデックス０．５〜５ｇ／１０分のエチレン−酢酸ビニル共重合体を７０〜９０重量部使用する。酢酸ビニル含有量が１７重量％未満であると、ポリウレタンエラストマーとの相溶性が悪くなり、均一な配合物が得られなく、２６重量％以上であると、溶融粘度、軟化点が低下し、ポリウレタンの溶融粘度、軟化点との差が大きすぎ、液体と固体を混合する様な状態となり、均一な配合物は得られない。
メルトインデックスが０．５ｇ／１０分未満であると、チルロールによるカレンダー法によるシート加工が困難となり、５ｇ／１０分以上であると、シートや発泡体の機械的強度が低下し、望ましくない。ＥＶＡの配合量が７０重量部未満であると、ポリウレタンエラストマーとの均一な配合が困難となり、価格の高いポリウレタンエラストマーの配合量が増加するので、コストアップとなり、また、他の基材との低温熱溶着性が悪くなり望ましくなく、９０重量部以上であると、シートや発泡体の耐摩耗性が発現しなくなり望ましくない。ポリウレタンエラストマーの軟化点は７０〜１００℃の範囲であり、７０℃未満であると分子中のソフトセグメントであるポリエーテル部分が増加し、極性が増すので、ＥＶＡとの極性の差がひらき、均一な配合物が得られなく、１００℃以上であると、ＥＶＡの軟化点との差がひらき、均一な配合物が得られない。
【００１８】
本発明においては、ＥＶＡとポリウレタンエラストマーは加熱混練機で８０〜１３０℃の温度で少なくとも７分間混練する。
バンバリーミキサーが最もＥＶＡとポリウレタンエラストマーとの混練効率がよく、８０℃未満ではＥＶＡは溶融するが、ポリウレタンエラストマーが均一に溶融しなく、均一な配合物が得られなく、１３０℃以上ではＥＶＡの溶融粘度が非常に低下し、混練効率が低下し、望ましくない。
混練時間は、少なくとも７分間必要であり、７分間未満であると、均一な配合物が得られない。
得られた均一な配合物は、チルロールによるカレンダー法で均一な厚さの耐摩耗性弾性シートが得られる。シートの厚さは、０．０５〜１０ｍｍの範囲が望ましい。
【００１９】
次に発泡性シートについて説明する。
上記耐摩耗性弾性シートの原料に化学発泡剤を０．１〜５重量部配合した点が異るのみで、あとは、同じである。
化学発泡剤は、８０〜１３０℃の温度では熱分解しないタイプのものが望ましい。
この様な化学発泡剤としては、アゾビスイソブチロニトリル、ジアゾカーボンアミド、ｐ−トルエンスルフォニルヒドラジド、４，４’−オキシビス（ベンゼンスルフォニルヒドラジド）、Ｎ，Ｎ’−ジニトロソペンタメチレンテトラミン等が望ましい。化学発泡剤の量は、０．１重量部未満では、発泡が十分おこらず、２５重量部以上であると過発泡がおき、コストアップとなり望ましくない。
【００２０】
前記発泡性シートは、エンドレスの幅２〜５ｍのものであるので、所定の形状、例えば、長方形、正方形等に裁断し、長方形、正方形の金型に入れ、化学発泡剤の分解温度以上、例えば１７０〜１９０℃で加熱し、発泡体として得られる。この発泡体は、裁断して、靴底、サンダル等各種製品に加工される。
【００２１】
次に、耐摩耗性表皮付き弾性発泡体について説明する。
前記の耐摩耗性弾性シートと発泡性シートを所定の形状に裁断し、金型に入れ、化学発泡剤の分解温度以上に加熱し、発泡性シートを発泡させ、同時に耐摩耗性弾性シートと発泡体を熱溶着させて、耐摩耗性表皮付き弾性発泡体を得る。
【００２２】
上記発泡性シートの原料としては、ＥＶＡとポリウレタンエラストマーについては先に説明したが、他の原料としては、ポリオレフィン、熱可塑性エラストマー、合成ゴム、天然ゴム等から選択されたものであってもよい。
【００２３】
ポリオレフィンの例としては、高圧法ポリエチレン（ＨＰ−ＬＤＰＥ）、高密度ポリエチレン（ＨＤＰＥ）、中密度ポリエチレン（ＭＤＰＥ）、直鎖状低密度ポリエチレン（ＬＬＤＰＥ）、超低密度ポリエチレン（ＶＬＤＰＥ）、メタロセンによるポリマー、エチレン−エチルアクリレート共重合体（ＥＥＡ）、アイオノマー、ポリプロピレン（ＰＰ）等が挙げられ、熱可塑性エラストマーの例としてはエチレン−プロピレンエラストマー（ＥＰＥ）、スチレン系エラストマー、ポリアミド系エラストマー、ウレタン系エラストマー、塩ビ系エラストマー、ポリエステル系エラストマー等が挙げられ、合成ゴムの例としては、スチレン−ブタジエンゴム（ＳＢＲ）、ブタジエンゴム（ＢＲ）、イソプレンゴム（ＩＲ）、エチレン−プロピレン−ジエンゴム（ＥＰＤＭ）、アクリロニトリル−ブタジエンゴム（ＮＢＲ）、クロロプレンゴム（ＣＲ）、ブチルゴム（ＩＩＲ）、シリコーンゴム、水素化ニトリルゴム、ポリエーテルゴム、フッ素ゴム、アクリルゴム、クロロスルホン化ポリエチレンゴム、エピクロロヒドリンゴム、プロピレンオキサイドゴム、エチレン−アクリルゴム等が挙げられる。
【００２４】
これらの耐摩耗性表皮付き弾性発泡体は、更に靴底の型に打ち抜き、靴底とし、更にこの靴底をはりつけた靴とする。この靴は、非常に軽く、クッション性にすぐれ、しかも耐摩耗性があるので耐久性がある。
【００２５】
また、本発明の耐摩耗性弾性シートは、織布又は不織布と貼合し、多層体とする。この多層体は、機械的強度、柔軟性、ゴム弾性、耐摩耗性、耐低温性、等にすぐれ、軽量であるので、フレキシブルコンテナーとして好適な素材である。
【００２６】
貼合は、熱溶着、接着剤、高周波加熱等によって行われる。
多層体からフレキシブルコンテナーを作るには、多層体を裁断し、熱溶着、接着剤、高周波加熱、縫製等により円形、４角形、５角形、６角形等のフレキシブルコンテナーにすることができる。
【００２７】
また、本発明の耐摩耗性弾性発泡体は、水に濡れても表面がすべらないので、水の存在する場所で使用しても、人や物体が発泡体の上に乗っても、すべって転倒することもなく、安全であるので、プールマット、浴室マット、調理場マット、洗車場マット、船舶用マット、ボート用マット等に適する。
また、本発明の耐摩耗性弾性発泡体は、保温性、断熱性、クッション性、遮水性等があり、すべらないので家畜飼育用の床マットとして好適である。
【００２８】
【実施例】
次に実施例によって本発明をさらに詳細に説明するが、本発明の要旨を逸脱しないかぎりこれらの実施例に限定されるものではない。
【００２９】
実施例１
耐摩耗性弾性シート（１）の製造
ＥＶＡの準備：酢酸ビニル含有量２５重量％、メルトインデックス４ｇ／１０分、密度０．９５ｇ／ｍｌ、ビカー軟化点４７℃のエチレン−酢酸ビニル共重合体（日本ユニカー製、ＮＵＣ−３１９５）。
ポリウレタンエラストマーの準備：密度１．１１ｇ／ｍｌ、硬度８７（ＪＩＳ Ａ）、ビカー軟化点８９℃のソフトセグメントがエーテル系のポリウレタンエラストマー（大日本精化工業製、レザミンＰ−２０４５）。
バンバリーミキサー：森山製作所製
製造条件：ＥＶＡ８０重量部、ポリウレタンエラストマー２０重量部を８５℃に設定されたバンバリミキサーに投入し、１０分間圧力をかけながら混練した。混練による発熱のため、混練物は１３０℃に昇温した。この混練物をチルロールによるカレンダー法で厚さ２ｍｍの長尺の耐摩耗性弾性シートとした。
【００３０】
得られた耐摩耗性弾性シートを下記の測定法で評価し、下記の結果を得た。
実施例２
耐摩耗性弾性シート（２）の製造
ＥＶＡの準備：酢酸ビニル含有量１８重量％、メルトインデックス１．５ｇ／１０分、密度０．９４ｇ／ｍｌ、ビカー軟化点５９℃のエチレン−酢酸ビニル共重合体（日本ユニカー製、ＮＵＣ−３７７０）。
ポリウレタンエラストマーの準備：密度１．２５ｇ／ｍｌ、硬度８６（ＪＩＳ Ａ）、ビカー軟化点７０℃のソフトセグメントがエーテル系のポリウレタンエラストマー（グッドリッチ社製、エステン５８２０２）。
バンバリーミキサー：森山製作所製
製造条件：ＥＶＡ９０重量部、ポリウレタンエラストマー１０重量部を８５℃に設定されたバンバリミキサーに投入し、１０分間圧力をかけながら混練した。混練による発熱のため、混練物は１３０℃に昇温した。この混練物をチルロールによるカレンダー法で厚さ５ｍｍの長尺の耐摩耗性弾性シートとした。
【００３２】
得られた耐摩耗性弾性シートを下記の測定法で評価し、下記の結果を得た。
実施例３
耐摩耗性弾性シート（３）の製造
ＥＶＡの準備：酢酸ビニル含有量１８重量％、メルトインデックス２．５ｇ／１０分、密度０．９４ｇ／ｍｌ、ビカー軟化点５７℃のエチレン−酢酸ビニル共重合体（日本ユニカー製、ＤＱＤＪ−１８６８）。
ポリウレタンエラストマーの準備：密度１．１１ｇ／ｍｌ、硬度８５（ＪＩＳ Ａ）、ビカー軟化点９７℃のソフトセグメントがエーテル系のポリウレタンエラストマー（日本ミラクトン製、ミラクトンＥ３８５）。
バンバリーミキサー：森山製作所製
製造条件：ＥＶＡ７１重量部、ポリウレタンエラストマー２９重量部を８５℃に設定されたバンバリミキサーに投入し、１０分間圧力をかけながら混練した。混練による発熱のため、混練物は１３０℃に昇温した。この混練物をチルロールによるカレンダー法で厚さ５ｍｍの長尺の耐摩耗性弾性シートとした。
【００３４】
得られた耐摩耗性弾性シートを下記の測定法で評価し、下記の結果を得た。
比較例１
実施例１において、ＥＶＡを酢酸ビニル含有量１５重量％、メルトインデックス１ｇ／１０分、密度０．９４ｇ／ｍｌ、ビカー軟化点６３℃（日本ユニカー製、ＮＵＣ−８４５２）に代えた以外は同様な実験を行ったところ、均一な混練物が得られなかった。
この原因は、ＥＶＡの酢酸ビニル含有量が１５重量％と低くなったので、ポリウレタンエラストマーとの相溶性が悪くなったからであると思われる。
【００３６】
比較例２
実施例１において、ＥＶＡを酢酸ビニル含有量２８重量％、メルトインデックス２０ｇ／１０分、密度０．９５ｇ／ｍｌ、ビカー軟化点４０℃（日本ユニカー製、ＤＱＤＪ−３２６９）に代えた以外は同様な実験を行ったところ、ＥＶＡが液体状となり、その中に固体状のポリウレタンエラストマーが存在し、混練操作が不十分となり、均一な混練物が得られなかった。
この原因は、ＥＶＡの酢酸ビニル含有量が２８重量％と高く、メルトインデックス２０ｇ／１０分、ビカー軟化点４０℃と溶融粘度が非常に低く、ポリウレタンエラストマーとの溶融粘度の差が大きすぎるためだと思われる。
【００３７】
比較例３
実施例１において、ポリウレタンエラストマーをビカー軟化点１０８℃のソフトセグメントがアジペートエステル系のポリウレタンエラストマー（大日本精化工業製、レザミンＰ−１０４５）に代えた以外は同様な実験を行ったところ、混練が十分に行われなかった。
この原因は、ポリウレタンエラストマーの軟化点が１０８℃と高いので、ＥＶＡの軟化点４７℃と差が大き過ぎ、液相と固相との混練となり、均一な混練物が得られなかったものと思われる。
【００３８】
比較例４
実施例１において、ポリウレタンエラストマーをビカー軟化点６５℃のソフトセグメントがアジペートエステル系のポリウレタンエラストマー（クラレ製、クラミロンＵ）に代えた以外は同様な実験を行ったところ、均一な混練物が得られなかった。従って、機械的特性、耐摩耗性等が悪化した。
この原因は、ポリウレタンエラストマーの極性が大きくなり、ＥＶＡの極性との差が大きすぎ両者が均一に相溶しないからであると思われる。
【００３９】
実施例４
発泡性シート（１）の製造
ＥＶＡの準備：酢酸ビニル含有量２５重量％、メルトインデックス４ｇ／１０分、密度０．９５ｇ／ｍｌ、ビカー軟化点４７℃のエチレン−酢酸ビニル共重合体（日本ユニカー製、ＮＵＣ−３１９５）。
ポリウレタンエラストマーの準備：密度１．１１ｇ／ｍｌ、硬度８７（ＪＩＳ Ａ）、ビカー軟化点８９℃のソフトセグメントがエーテル系のポリウレタンエラストマー（大日本精化工業製、レザミンＰ−２０４５）。
化学発泡剤の準備：アゾジカルボンアミド（永和化成製、ＡＺ−６０５）
化学架橋剤の準備：ジクミルパーオキサイド（日本油脂製、パークミルＨ）
バンバリーミキサー：森山製作所製
製造条件：ＥＶＡ８０重量部、ポリウレタンエラストマー２０重量部、アゾジカルボンアミド１０重量部、ジクミルパーオキサイド０．５重量部を８５℃に設定されたバンバリミキサーに投入し、１０分間圧力をかけながら混練した。混練による発熱のため、混練物は１３０℃に昇温した。この混練物をチルロールによるカレンダー法で厚さ３ｍｍ、巾１ｍの長尺シートを作成した。
【００４０】
実施例５
耐摩耗性弾性発泡体（１）の製造
実施例１で作った発泡性シートを１ｍ×１ｍの正方形に裁断し、金型に入れ、１８０℃に加熱し、厚さ１０ｍｍの発泡体を得た。
【００４１】
実施例６
サンダルの製造
実施例５で作った発泡体を足型に裁断し、はなおをつけサンダルを製造した。評価：このサンダルを履き、アスファルト舗装道路を１０，０００ｍ、分速８０ｍで歩いたが、クッション性はよく、足が疲労することはなく、サンダルはかかと部が最大１ｍｍ摩耗したが、割れたり、はなおのつけね部分が破れることはなかった。
【００４２】
実施例７
耐摩耗性表皮付き弾性発泡体（１）の製造
実施例１で製造した耐摩耗性弾性シート（１）と実施例４で製造した発泡性シート（１）とをそれぞれ１ｍ×１ｍの正方形に裁断し、発泡性シート（１）を中心とし、両側を弾性シート（１）でサンドイッチ構造とし、重ね合せ、金型に入れ、１８０℃で１０分間加熱し、発泡と、両シートの熱溶着を行わせ、１０ｍｍの厚さの発泡層、それぞれ２ｍｍの厚さの非発泡層が強固に熱溶着された耐摩耗性表皮付き弾性発泡体（１）を得た。
【００４３】
実施例８
靴底（１）及び靴（１）の製造
実施例７で作った耐摩耗性表皮付き弾性発泡体（１）を足形に裁断し、更に、発泡体層を傾斜して、２分割して、靴底とした。
皮製の甲部分と靴底を接着剤で接着後、縫製し、靴を作製した。
評価：この靴をはき、５０ｋｍ、分速８０ｍで、アスファルト舗道を歩いたが、クッション性はよく、履きごこちはよかった。５０ｋｍ歩行後、表皮部分は、かかと部分が最大０．６ｍｍ摩耗したのみで、耐摩耗性は十分あった。
【００４４】
実施例９
耐摩耗性表皮付き弾性発泡体（２）の製造
ビニル結合含有率９２％、結晶化度２８％、の１，２−ポリブタジエン（日本合成ゴム製、ＪＳＲ ＩＲ２２００）３０重量部、エチルアクリレート含有量１５重量％、メルトインデックス１．５ｇ／１０分、密度０．９３ｇ／ｍｌ、ビカー軟化点６１℃のエチレン−エチルアクリレート共重合体（日本ユニカー製、ＤＱＤＪ−６１８２）７０重量部、化学発泡剤アゾジカルボンアミド（永和化成製、ＡＺ−６０５）、化学架橋剤ジクミルパーオキサイド（日本油脂製、パークミルＨ）０．７重量部を８５℃に設定したバンバリーミキサーに投入し、１０分間圧力をかけながら混練した。混練による発泡のため、混練物は１３０℃に昇温した。
この混合物をチルロールによるカレンダー法で厚さ５ｍｍ、巾１ｍの長尺発泡性シートを作った。
この発泡性シートと実施例３で作った耐摩耗性弾性シート（３）を、両外層とし、上記発泡性シートを中層とし、重ね合せ１ｍ×１ｍの正方形に裁断し、金型に入れ、１８０℃で１０分間加熱し、発泡と両外側シートの熱溶着を行わせ、１０ｍｍの厚さの発泡層、それぞれ５ｍｍの厚さの非発泡層が強固に熱溶着された耐摩耗性表皮付き弾性発泡体（２）を得た。
【００４５】
実施例１０
靴底（２）及び靴（２）の製造
実施例９で作った耐摩耗性表皮付き弾性発泡体（２）を足形に裁断し、更に、発泡体層を傾斜して、２分割して、靴底とした。
皮製の甲部分と靴底を接着剤で接着後、縫製し、靴を作製した。
評価：この靴を履き、５０ｋｍ、分速８０ｍで、アスファルト舗道を歩いたが、クッション性はよく、履きごこちはよかった。５０ｋｍ歩行後、表皮部分は、かかと部分が最大０．３ｍｍ摩耗したのみで、耐摩耗性は十分あった。
【００４６】
実施例１１
多層体の製造
密度０．９１ｇ／ｍｌ、メルトフローレイト１ｇ／１０分（２３０℃）、引張降伏強度３６５ｋｇ／ｃｍ２ 、ビカー軟化点１５２℃のポリプロピレン（東燃化学製、Ｙ２０１）で偏平糸（９５０デニール）を作り、６×６本／インチに平織した織布を作り、これを中層として、これに実施例２で作った耐摩耗性弾性シートを両外層として重ね合せ、１ｍ×２ｍに裁断し、高周波溶着を行い一体化させ多層体を得た。
【００４７】
実施例１２
フレキシブルコンテナーの製造
実施例１１で作った多層体を４枚準備し、直方体の４つの側面用とし、別途１．２ｍ×１．２ｍの多層体を準備し、直方体の底面用とし、それぞれ工業用ミシンで縫製し、巾５ｃｍ、厚さ３ｍのナイロン糸で作った帯をつり上げ帯として２本用意し、底部を十字に支える様にして、側面に貼り付け上方に伸ばし、上方ではループを形成し、つり上げ部として、フレキシブルコンテナーを作成した。
【００４８】
評価：このフレキシブルコンテナーはミシン針による縫製時の穴から破れることなく、また、穴が収縮し、気密性がよいので、外部からのコンタミネーションを防ぎ、柔軟性、耐摩耗性、耐水性、耐衝撃性、耐薬品性、耐寒性、耐突き刺し性等にすぐれているので、合成樹脂ペレット、無機薬品粉体、肥料、穀物、小麦粉、等の輸送に好適である。
【００４９】
実施例１３
プールマットの製造
実施例７で得た耐摩耗性表皮付き弾性発泡体を１０個連絡し、表面を水色に染色し、プールマット材とした。
プールの周囲に敷きつめ、その上を濡れた素足で走ったがマットも人もすべることなく安全であった。
【００５０】
実施例１４
浴室用マットの製造
実施例５で得た耐摩耗性弾性発泡体を浴室用マットとした。マットに水をかけその上を素足で歩いたが、マットも人もすべることなく安全であった。
【００５１】
実施例１５
牛舎用飼育マット
実施例７で得た耐摩耗性表皮付き弾性発泡体を３０個、牛舎のコンクリート床に敷きつめた。屎尿の除去も容易で、保温性もあり、牛の発育が非常によかった。
【００５２】
【発明の効果】
本発明は、特定のエチレン−酢酸ビニル共重合体と特定のポリウレタンエラストマーを、特定の割合で配合した樹脂組成物で、耐摩耗性弾性シートをつくり、又、上記樹脂組成物に化学発泡剤を配合し、耐摩耗性弾性発泡シートとしているので、これら単独又は、これらの積層物シートは耐薬品性にすぐれ、機械的強度が強く、軽く、耐摩耗性があり、表面がすべらなく、印刷性もよく、靴底、靴、サンダル、フレキシブルコンテナー、ベルト、衣料品、家具、椅子、スポーツ用品、グリップ材、建築材料、自動車内装材、バンパー、飛行機内装材、船舶内装材、列車内装材、フェンス、防音材、緩衝材、フィルター、農業用資材、レジャー用品、医療用品、包装資材、水産用資材、農業用資材、プールマット、浴室用マット、調理場マット、洗車場マット、家畜類の飼育場の床材として好適である。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to an abrasion-resistant elastic sheet made from a resin composition comprising a specific amount of a specific ethylene-vinyl acetate copolymer and a specific polyurethane elastomer, and a chemical foaming agent added to the resin composition. The present invention also relates to a foamable sheet made therefrom, an abrasion-resistant elastic foam made from the foamable sheet, and an elastic foam with an abrasion-resistant skin made from the wear-resistant elastic sheet and the foamable sheet.
[0002]
The present invention further relates to a foamable sheet made from a polyolefin, thermoplastic elastomer, synthetic rubber, natural rubber and the like and a chemical foaming agent, and an elastic foam with a wear-resistant skin made from the above-mentioned wear-resistant elastic sheet.
The present invention further relates to shoe soles, shoes and the like made from the above abrasion-resistant elastic foam.
The present invention further relates to a multilayer body composed of the above abrasion-resistant elastic sheet and a woven or non-woven fabric, and a flexible container made of the multilayer body.
[0003]
The wear-resistant elastic sheet, wear-resistant elastic foam, multilayer body and the like of the present invention are not only shoe soles and flexible containers, but also clothing, furniture, chairs, sports equipment, building materials, automobile interior materials, airplane interior materials, Used as ship interior materials, train interior materials, fences, soundproof materials, cushioning materials, filters, agricultural materials, leisure products, medical supplies, packaging materials, marine products, agricultural materials, etc. In particular, it is suitable as a mat used in a place where water is used, such as a pool mat, a bathroom mat, a kitchen mat, and a car wash mat.
It is also suitable as a flooring material for livestock such as horses, cows, pigs, chickens, ducks, geese and turkeys.
[0004]
[Prior art]
The applicant of the present application blends a chemical foaming agent with an ethylene-vinyl acetate copolymer (hereinafter sometimes referred to as EVA) to produce an EVA foam, from which a shoe sole material is produced. Although the foam has good cushioning properties, the wear resistance is poor, and various sheets are bonded as the skin of the EVA foam to improve the wear resistance. Of the various sheets, the one with the best wear resistance is polyurethane elastomer, but the price is very high. For bonding to EVA foam, an expensive adhesive with high adhesive strength must be used. The cost has increased, and a solution has been demanded.
[0005]
The present inventors predicted that a sheet made of EVA and polyurethane elastomer would give good results, and investigated the prior art, but could not find the prior art for a sheet made of EVA and polyurethane elastomer. . For example, in Japanese Patent Publication No. 58-41310, there existed 70-90 wt%: 30-10 wt% of a thermoplastic polyurethane resin and an ethylene-vinyl acetate-vinyl chloride terpolymer. A synthetic resin composition for forming a tarpaulin film, characterized in that a resin composition obtained by mixing at a ratio of 50 to 90% by weight with respect to 50 to 90% by weight of an ethylene-vinyl acetate copolymer resin is mixed. When the amount of the ethylene-vinyl acetate-vinyl chloride terpolymer is less than 10% by weight, the compatibility between EVA and thermoplastic polyurethane is deteriorated, and it is described that blending becomes difficult.
[0006]
JP-A-61-211400 discloses that a coating layer made of a mixed resin of polyurethane resin and ethylene-vinyl acetate copolymer resin is provided on the surface of natural leather, and the coating layer penetrates into the inside of natural leather. Although the leather material characterized by the above is shown, the polyurethane resin is not an elastomer, but a one-component type, a two-component type or a prepolymer type (from specification (2) page, lower right column) 1st to 2nd line), which is a mixture of a liquid polyurethane raw material and EVA, and the problems to be solved are different from those of the present invention.
[0007]
Furthermore, JP-A-1-117201 discloses a polyurethane resin having a Shore D hardness of 73 or more of 50 to 90% by weight, ethylene-methyl acrylate copolymer, ethylene-acrylic acid copolymer, ethylene-acetic acid on a conductor. An insulated wire is shown in which a thin insulating layer of 0.3 mm or less is formed of a mixed resin composition of 10 to 50% by weight of at least one copolymer among vinyl copolymers. However, since the polyurethane resin is 50% by weight or more and EVA is 50% by weight or less, it seems that a kneaded product was obtained. Like the present invention, EVA is 70% by weight or more and the polyurethane elastomer is 30% by weight or less. However, the technique of Japanese Patent Application Laid-Open No. 1-1117201 cannot solve the problem of the present invention.
[0008]
JP-A-50-76165 discloses a composition comprising soluble and / or thermoplastic polyurethane mixed with 2 to 5% by weight of the following ethylene copolymer: 79 to 98.3 mol% of ethylene, 20.5-1.7 mol% of at least one unsaturated ester of fatty acid, the ester containing 3-8 carbon atoms in the molecule, and 3-7 carbon atoms in the molecule of 10-0 mol% Although at least one compound selected from the group consisting of unsaturated acids and salts of acids and anhydrides is shown, the amount of EVA is as low as 2 to 5% by weight, and polyurethane and EVA are formulated as a solution The purpose and configuration of the present invention are different from those of the present invention, such as that the purpose of EVA is to prevent polyurethane blocking.
[0009]
[Problems to be solved by the invention]
As described above, the first object of the invention is to make a low-cost sheet having wear resistance composed of EVA and polyurethane elastomer, and this sheet and other materials (foam, woven fabric, non-woven fabric) It is a second subject of the invention to make a multilayer body of the present invention, and a third subject of the invention is to make a shoe sole, a flexible container and the like from these multilayer bodies.
[0010]
[Means for Solving the Problems]
The present inventors have challenged the common knowledge of the industry that polyurethane elastomer and EVA cannot be made into a uniform resin composition without the presence of a compatibilizer, and EVA is 70 to 90% by weight without a compatibilizer. A uniform resin composition comprising 10 to 30% by weight of polyurethane elastomer was successfully produced.
In the literature, as described above, there is a blending example in which the polyurethane resin is 50% by weight or more and the EVA is 50% by weight or less. This is a product obtained by blending EVA with 50% by weight or less in a highly polar polyurethane resin. Yes, it is different from the blending ratio of the present invention, and there is no description as to whether or not it is blended uniformly. Any non-uniform compound can be blended with any resin, but it does not exhibit mechanical strength, durability, chemical resistance, heat resistance, low temperature embrittlement resistance, elasticity, etc. .
[0011]
In order to develop a sheet having good cost reduction, low-temperature heat-weldability, high-speed workability, blocking resistance, and good wear resistance, the inventors occupy the main component of EVA and a small amount of polyurethane elastomer. When various EVAs and various polyurethanes were blended within the range of components, specific EVAs and specific polyurethanes were blended in specific amounts, and were blended uniformly only when kneaded at a specific temperature with a Banbury mixer. A resin composition was obtained, from which it was demonstrated that an abrasion-resistant elastic sheet was obtained, and the present invention was completed.
[0012]
That is, the subject of the present invention is a vinyl acetate content of 17 to 26% by weight, an ethylene-vinyl acetate copolymer of 70 to 90 parts by weight with a melt index of 0.5 to 5 g / 10 min, and a Vicat softening point of 70 to 100 ° C. The present invention relates to an abrasion-resistant elastic sheet prepared by kneading a resin component comprising 10 to 30 parts by weight of a polyurethane elastomer with a heating kneader at a temperature of 80 to 130 ° C. for at least 7 minutes, and then making a calendar method using a chill roll.
[0013]
Another subject of the present invention is a vinyl acetate content of 17-26% by weight, an ethylene-vinyl acetate copolymer of 70-90 parts by weight with a melt index of 0.5-5 g / 10 min, a Vicat softening point of 70-100 ° C. A resin composition comprising 10 to 30 parts by weight of a polyurethane elastomer and 0.1 to 25 parts by weight of a chemical foaming agent was kneaded with a heating kneader at a temperature of 80 to 130 ° C. for at least 7 minutes, and then prepared by a calendar method using a chill roll. It relates to a foamable sheet.
[0014]
Another subject of the present invention is a wear-resistant elastic foam obtained by cutting the foamable sheet into a predetermined shape, placing it in a mold, and heating it to a temperature equal to or higher than the decomposition temperature of the chemical foaming agent, and the above-mentioned The wear-resistant elastic sheet and the foamable sheet are polymerized, cut into a predetermined shape, put into a mold, heated to a temperature higher than the decomposition temperature of the chemical foaming agent, and foamed and bonded to obtain the resistance. The present invention relates to an elastic foam with a wearable skin.
[0015]
Furthermore, the subject of the present invention is a foamable sheet made from a resin composition comprising 100 parts by weight of a material selected from polyolefin, thermoplastic elastomer, synthetic rubber, natural rubber and the like and 0.1 to 25 parts by weight of a chemical foaming agent. With the abrasion-resistant skin obtained by polymerizing the above-mentioned abrasion-resistant elastic sheet, cutting into a predetermined shape, putting it in a mold, heating it above the decomposition temperature of the chemical foaming agent, and performing foaming and pasting It relates to an elastic foam.
[0016]
Still another subject of the present invention is a shoe sole obtained by cutting the elastic foam, a shoe or a sandal made using the shoe sole, and the wear-resistant elastic sheet and a woven or non-woven fabric. And a flexible container made from this multilayer body.
Furthermore, the present invention relates to a pool mat, a livestock mat or the like obtained by cutting the wear-resistant elastic foam.
[0017]
DETAILED DESCRIPTION OF THE INVENTION
In the present invention, 70 to 90 parts by weight of an ethylene-vinyl acetate copolymer having a vinyl acetate content of 17 to 26% by weight and a melt index of 0.5 to 5 g / 10 min is used. When the vinyl acetate content is less than 17% by weight, the compatibility with the polyurethane elastomer is deteriorated, and a uniform blend cannot be obtained. When the vinyl acetate content is 26% by weight or more, the melt viscosity and the softening point are lowered. The difference between the melt viscosity and the softening point is too large, and the liquid and the solid are mixed, and a uniform blend cannot be obtained.
If the melt index is less than 0.5 g / 10 minutes, sheet processing by a calendar method using a chill roll becomes difficult, and if it is 5 g / 10 minutes or more, the mechanical strength of the sheet or foam is lowered, which is not desirable. When the blending amount of EVA is less than 70 parts by weight, uniform blending with the polyurethane elastomer becomes difficult, and the blending amount of the expensive polyurethane elastomer increases, resulting in an increase in cost and low temperature with other base materials. The heat weldability deteriorates and is not desirable, and if it is 90 parts by weight or more, the wear resistance of the sheet or foam is not exhibited, which is not desirable. The softening point of the polyurethane elastomer is in the range of 70 to 100 ° C. When the temperature is lower than 70 ° C., the polyether portion which is a soft segment in the molecule increases and the polarity increases, so that the difference in polarity from EVA opens and is uniform. If the temperature is 100 ° C. or higher, the difference from the softening point of EVA opens, and a uniform composition cannot be obtained.
[0018]
In the present invention, EVA and polyurethane elastomer are kneaded in a heating kneader at a temperature of 80 to 130 ° C. for at least 7 minutes.
The Banbury mixer has the best kneading efficiency between EVA and polyurethane elastomer. EVA melts below 80 ° C, but polyurethane elastomer does not melt uniformly and a uniform blend cannot be obtained, and EVA melts above 130 ° C. Viscosity is greatly reduced and kneading efficiency is lowered, which is undesirable.
The kneading time must be at least 7 minutes, and if it is less than 7 minutes, a uniform blend cannot be obtained.
The obtained uniform blend provides a wear-resistant elastic sheet having a uniform thickness by a calendar method using chill rolls. The thickness of the sheet is desirably in the range of 0.05 to 10 mm.
[0019]
Next, the foamable sheet will be described.
The only difference is that 0.1 to 5 parts by weight of a chemical foaming agent is blended with the raw material of the wear-resistant elastic sheet, and the rest is the same.
The chemical foaming agent is preferably of a type that does not thermally decompose at a temperature of 80 to 130 ° C.
Examples of such chemical blowing agents include azobisisobutyronitrile, diazocarbonamide, p-toluenesulfonyl hydrazide, 4,4′-oxybis (benzenesulfonyl hydrazide), N, N′-dinitrosopentamethylenetetramine, and the like. desirable. If the amount of the chemical foaming agent is less than 0.1 parts by weight, foaming does not occur sufficiently, and if it is 25 parts by weight or more, excessive foaming occurs, resulting in an increase in cost.
[0020]
Since the foamable sheet has an endless width of 2 to 5 m, it is cut into a predetermined shape, for example, a rectangle, a square, etc., put into a rectangular, square mold, and the decomposition temperature of the chemical foaming agent or higher, for example, It heats at 170-190 degreeC and is obtained as a foam. This foam is cut and processed into various products such as shoe soles and sandals.
[0021]
Next, an elastic foam with an abrasion resistant skin will be described.
The abrasion-resistant elastic sheet and the foamable sheet are cut into a predetermined shape, put into a mold, heated to a temperature higher than the decomposition temperature of the chemical foaming agent to foam the foamable sheet, and simultaneously the abrasion-resistant elastic sheet and foamed. The body is heat-welded to obtain an elastic foam with an abrasion-resistant skin.
[0022]
As the raw material of the foamable sheet, EVA and polyurethane elastomer have been described above. However, other raw materials may be selected from polyolefin, thermoplastic elastomer, synthetic rubber, natural rubber and the like.
[0023]
Examples of polyolefins include high pressure polyethylene (HP-LDPE), high density polyethylene (HDPE), medium density polyethylene (MDPE), linear low density polyethylene (LLDPE), very low density polyethylene (VLDPE), and polymers based on metallocene. , Ethylene-ethyl acrylate copolymer (EEA), ionomer, polypropylene (PP) and the like. Examples of thermoplastic elastomers include ethylene-propylene elastomer (EPE), styrene elastomer, polyamide elastomer, urethane elastomer, Examples of synthetic rubber include styrene-butadiene rubber (SBR), butadiene rubber (BR), isoprene rubber (IR), and ethylene-propylene. Diene rubber (EPDM), acrylonitrile-butadiene rubber (NBR), chloroprene rubber (CR), butyl rubber (IIR), silicone rubber, hydrogenated nitrile rubber, polyether rubber, fluoro rubber, acrylic rubber, chlorosulfonated polyethylene rubber, epichloro Examples include hydrin rubber, propylene oxide rubber, and ethylene-acrylic rubber.
[0024]
These elastic foams with abrasion-resistant skin are further punched into a shoe mold to form a shoe sole, and a shoe with the shoe sole attached thereto. This shoe is very light, cushioning, and wear resistant, so it is durable.
[0025]
Moreover, the abrasion-resistant elastic sheet of this invention is bonded with a woven fabric or a nonwoven fabric, and it is set as a multilayer body. This multilayer body is excellent in mechanical strength, flexibility, rubber elasticity, wear resistance, low temperature resistance, and the like, and is lightweight, and is therefore a material suitable as a flexible container.
[0026]
Bonding is performed by heat welding, an adhesive, high frequency heating, or the like.
In order to make a flexible container from a multilayer body, the multilayer body can be cut and formed into a flexible container such as a circular, quadrangular, pentagonal, hexagonal shape by heat welding, adhesive, high frequency heating, sewing, or the like.
[0027]
In addition, since the surface of the wear-resistant elastic foam of the present invention does not slip even when wet, even if it is used in a place where water exists, even if a person or an object gets on the foam, it will slip. Since it is safe without falling down, it is suitable for pool mats, bathroom mats, kitchen mats, car wash mats, marine mats, boat mats and the like.
Further, the wear-resistant elastic foam of the present invention is suitable as a floor mat for raising livestock because it has heat retention, heat insulation, cushioning, water shielding, etc. and does not slip.
[0028]
【Example】
EXAMPLES Next, although an Example demonstrates this invention further in detail, unless it deviates from the summary of this invention, it is not limited to these Examples.
[0029]
Example 1
Manufacture of wear-resistant elastic sheet (1)
EVA preparation: an ethylene-vinyl acetate copolymer having a vinyl acetate content of 25% by weight, a melt index of 4 g / 10 min, a density of 0.95 g / ml, and a Vicat softening point of 47 ° C. (NUC-3195, manufactured by Nippon Unicar Co., Ltd.).
Preparation of polyurethane elastomer: A polyurethane elastomer having a density of 1.11 g / ml, a hardness of 87 (JIS A), and a soft segment having a Vicat softening point of 89 ° C. (manufactured by Dainippon Seika Kogyo Co., Ltd., Resamine P-2045).
Banbury mixer: manufactured by Moriyama Seisakusho
Production conditions: 80 parts by weight of EVA and 20 parts by weight of polyurethane elastomer were put into a Banbury mixer set at 85 ° C. and kneaded while applying pressure for 10 minutes. Due to the heat generated by kneading, the temperature of the kneaded product was raised to 130 ° C. This kneaded product was formed into a long wear-resistant elastic sheet having a thickness of 2 mm by a calendar method using a chill roll.
[0030]
The obtained abrasion-resistant elastic sheet was evaluated by the following measurement method, and the following results were obtained.
Example 2
Manufacture of wear-resistant elastic sheet (2)
Preparation of EVA: ethylene-vinyl acetate copolymer having a vinyl acetate content of 18% by weight, a melt index of 1.5 g / 10 min, a density of 0.94 g / ml, and a Vicat softening point of 59 ° C. (NUC-3770, manufactured by Nippon Unicar Co., Ltd.) .
Preparation of polyurethane elastomer: Polyurethane elastomer having a soft segment having a density of 1.25 g / ml, a hardness of 86 (JIS A), and a Vicat softening point of 70 ° C. (Goodrich, Esten 58202).
Banbury mixer: manufactured by Moriyama Seisakusho
Production conditions: 90 parts by weight of EVA and 10 parts by weight of polyurethane elastomer were put into a Banbury mixer set at 85 ° C. and kneaded while applying pressure for 10 minutes. Due to the heat generated by kneading, the temperature of the kneaded product was raised to 130 ° C. This kneaded material was formed into a long wear-resistant elastic sheet having a thickness of 5 mm by a calendar method using a chill roll.
[0032]
The obtained abrasion-resistant elastic sheet was evaluated by the following measurement method, and the following results were obtained.
Example 3
Manufacture of wear-resistant elastic sheet (3)
EVA preparation: ethylene-vinyl acetate copolymer having a vinyl acetate content of 18% by weight, a melt index of 2.5 g / 10 min, a density of 0.94 g / ml, and a Vicat softening point of 57 ° C. (Nikka Unicar, DQDJ-1868) .
Preparation of polyurethane elastomer: A polyurethane elastomer having a density of 1.11 g / ml, a hardness of 85 (JIS A), and a soft segment having a Vicat softening point of 97 ° C. (manufactured by Nippon Milactone, Milactone E385).
Banbury mixer: manufactured by Moriyama Seisakusho
Production conditions: 71 parts by weight of EVA and 29 parts by weight of polyurethane elastomer were put into a Banbury mixer set at 85 ° C. and kneaded while applying pressure for 10 minutes. Due to the heat generated by kneading, the temperature of the kneaded product was raised to 130 ° C. This kneaded material was formed into a long wear-resistant elastic sheet having a thickness of 5 mm by a calendar method using a chill roll.
[0034]
The obtained abrasion-resistant elastic sheet was evaluated by the following measurement method, and the following results were obtained.
Comparative Example 1
In Example 1, EVA was replaced with a vinyl acetate content of 15% by weight, a melt index of 1 g / 10 minutes, a density of 0.94 g / ml, and a Vicat softening point of 63 ° C. (NUC-852 manufactured by Nihon Unicar). As a result of experiments, a uniform kneaded product was not obtained.
This is probably because the EVA vinyl acetate content was as low as 15% by weight, and the compatibility with the polyurethane elastomer deteriorated.
[0036]
Comparative Example 2
In Example 1, EVA was replaced with a vinyl acetate content of 28% by weight, a melt index of 20 g / 10 minutes, a density of 0.95 g / ml, and a Vicat softening point of 40 ° C. (Nihon Unicar, DQDJ-3269). As a result of the experiment, EVA became liquid and solid polyurethane elastomer was present therein, so that the kneading operation was insufficient and a uniform kneaded product could not be obtained.
This is because EVA has a high vinyl acetate content of 28% by weight, a melt index of 20 g / 10 min, a Vicat softening point of 40 ° C. and a very low melt viscosity, and the difference in melt viscosity from polyurethane elastomer is too large. I think that the.
[0037]
Comparative Example 3
In Example 1, a similar experiment was performed except that the polyurethane segment was replaced with an adipate ester-based polyurethane elastomer (Rezamin P-1045, manufactured by Dainippon Seika Kogyo Co., Ltd.) with a soft segment having a Vicat softening point of 108 ° C. Was not done enough.
The reason is that the softening point of polyurethane elastomer is as high as 108 ° C, so the difference from the softening point of EVA is 47 ° C is too large, and the liquid phase and the solid phase are kneaded, and a uniform kneaded product cannot be obtained. It is.
[0038]
Comparative Example 4
In Example 1, a similar kneaded product was obtained when the same experiment was performed except that the polyurethane segment was replaced with an adipate ester-based polyurethane elastomer (Kuraray, Kuramilon U) with a soft segment having a Vicat softening point of 65 ° C. There wasn't. Therefore, mechanical properties, wear resistance, etc. deteriorated.
The cause of this seems to be that the polarity of the polyurethane elastomer becomes large and the difference from the polarity of EVA is too large to be compatible with each other.
[0039]
Example 4
Manufacture of foamable sheet (1)
EVA preparation: an ethylene-vinyl acetate copolymer having a vinyl acetate content of 25% by weight, a melt index of 4 g / 10 min, a density of 0.95 g / ml, and a Vicat softening point of 47 ° C. (NUC-3195, manufactured by Nippon Unicar Co., Ltd.).
Preparation of polyurethane elastomer: A polyurethane elastomer having a density of 1.11 g / ml, a hardness of 87 (JIS A), and a soft segment having a Vicat softening point of 89 ° C. (manufactured by Dainippon Seika Kogyo Co., Ltd., Resamine P-2045).
Preparation of chemical foaming agent: Azodicarbonamide (manufactured by Eiwa Kasei Co., Ltd., AZ-605)
Preparation of chemical crosslinking agent: Dicumyl peroxide (Nippon Yushi Co., Ltd., Park Mill H)
Banbury mixer: manufactured by Moriyama Seisakusho
Production conditions: 80 parts by weight of EVA, 20 parts by weight of polyurethane elastomer, 10 parts by weight of azodicarbonamide and 0.5 parts by weight of dicumyl peroxide were put into a Banbury mixer set at 85 ° C. and kneaded while applying pressure for 10 minutes. . Due to the heat generated by kneading, the temperature of the kneaded product was raised to 130 ° C. A long sheet having a thickness of 3 mm and a width of 1 m was prepared from the kneaded product by a calendar method using a chill roll.
[0040]
Example 5
Production of wear-resistant elastic foam (1)
The foamable sheet prepared in Example 1 was cut into a 1 m × 1 m square, placed in a mold, and heated to 180 ° C. to obtain a foam having a thickness of 10 mm.
[0041]
Example 6
Sandal manufacturing
The foam made in Example 5 was cut into a foot shape and applied with a sandal. Evaluation: I wore this sandal and walked on an asphalt paved road at 10,000m at a speed of 80m / min, but the cushioning was good, the foot was not fatigued, the sandal was worn up to 1mm in the heel part, There was no tearing of the spear.
[0042]
Example 7
Manufacture of elastic foam with wear-resistant skin (1)
The abrasion-resistant elastic sheet (1) produced in Example 1 and the foamable sheet (1) produced in Example 4 were each cut into 1 m × 1 m squares, with the foamable sheet (1) as the center and both sides Made into a sandwich structure with elastic sheet (1), overlapped, put in a mold, heated at 180 ° C. for 10 minutes, foamed and thermally welded both sheets, 10 mm thick foam layer, 2 mm each An elastic foam with wear-resistant skin (1) was obtained in which the non-foamed layer having a thickness was firmly heat-welded.
[0043]
Example 8
Manufacture of soles (1) and shoes (1)
The elastic foam with abrasion-resistant skin (1) produced in Example 7 was cut into a foot shape, and the foam layer was further inclined and divided into two to form shoe soles.
The leather upper part and the shoe sole were bonded with an adhesive and then sewn to produce a shoe.
Evaluation: I wore these shoes and walked on an asphalt pavement at 50 km and a speed of 80 m / min. The cushioning was good and I was comfortable wearing them. After walking for 50 km, the heel portion was worn at a maximum of 0.6 mm, and the wear resistance was sufficient.
[0044]
Example 9
Manufacture of elastic foam with wear-resistant skin (2)
30 parts by weight of 1,2-polybutadiene (manufactured by Nippon Synthetic Rubber, JSR IR2200) having a vinyl bond content of 92% and a crystallinity of 28%, an ethyl acrylate content of 15% by weight, a melt index of 1.5 g / 10 minutes, and a density 0.93 g / ml, 70 parts by weight of ethylene-ethyl acrylate copolymer (Nikka Unicar, DQDJ-6182) having a Vicat softening point of 61 ° C., chemical foaming agent azodicarbonamide (manufactured by Eiwa Kasei, AZ-605), chemical crosslinking Dicumyl peroxide (Nippon Yushi Co., Ltd., Park Mill H) 0.7 parts by weight was put into a Banbury mixer set at 85 ° C. and kneaded while applying pressure for 10 minutes. Due to foaming by kneading, the kneaded product was heated to 130 ° C.
A long foam sheet having a thickness of 5 mm and a width of 1 m was prepared from this mixture by a calendar method using a chill roll.
This foamable sheet and the abrasion-resistant elastic sheet (3) prepared in Example 3 were used as both outer layers, the foamable sheet was used as an intermediate layer, cut into a 1 m × 1 m square, placed in a mold, 180 Heating at 10 ° C. for 10 minutes, foaming and thermal welding of both outer sheets are carried out, 10 mm thick foamed layer and 5 mm thick non-foamed layer are firmly heat welded elastic foam with wear-resistant skin Body (2) was obtained.
[0045]
Example 10
Manufacture of soles (2) and shoes (2)
The elastic foam with wear-resistant skin (2) prepared in Example 9 was cut into a foot shape, and the foam layer was further inclined and divided into two to form shoe soles.
The leather upper part and the shoe sole were bonded with an adhesive and then sewn to produce a shoe.
Evaluation: I wore these shoes and walked on an asphalt pavement at 50 km and a speed of 80 m / min. After walking for 50 km, the heel portion was worn at a maximum of 0.3 mm, and the wear resistance was sufficient.
[0046]
Example 11
Multi-layer manufacturing
Density 0.91 g / ml, melt flow rate 1 g / 10 min (230 ° C.), tensile yield strength 365 kg / cm2 A flat yarn (950 denier) is made with polypropylene having a Vicat softening point of 152 ° C. (manufactured by Tonen Chemical Co., Ltd., Y201), and a woven fabric plainly woven into 6 × 6 pieces / inch is formed. The produced abrasion-resistant elastic sheet was overlapped as both outer layers, cut into 1 m × 2 m, and integrated by high frequency welding to obtain a multilayer body.
[0047]
Example 12
Flexible container manufacturing
Prepare four multilayer bodies made in Example 11 for the four side surfaces of the rectangular parallelepiped, separately prepare a multilayer body of 1.2 m × 1.2 m, and for the bottom surface of the rectangular parallelepiped, and sew each with an industrial sewing machine. Prepare two straps made of nylon thread with a width of 5 cm and a thickness of 3 m as lifting bands, support the bottom part in a cross shape, stick it on the side and stretch it upward, form a loop above it, , Created a flexible container.
[0048]
Evaluation: This flexible container does not break from the hole when sewing with the sewing needle, and the hole shrinks and has good airtightness, preventing external contamination, flexibility, wear resistance, water resistance, Since it has excellent impact resistance, chemical resistance, cold resistance, puncture resistance, etc., it is suitable for transporting synthetic resin pellets, inorganic chemical powders, fertilizers, grains, wheat flour, and the like.
[0049]
Example 13
Pool mat manufacturing
Ten elastic foams with abrasion-resistant skin obtained in Example 7 were connected and the surface was dyed light blue to obtain a pool mat material.
It lay around the pool and ran with wet bare feet on it, but it was safe without any mats or people slipping.
[0050]
Example 14
Manufacture of bathroom mats
The abrasion-resistant elastic foam obtained in Example 5 was used as a bathroom mat. I dipped water on the mat and walked barefoot on it, but it was safe without any sliding.
[0051]
Example 15
Cattle breeding mat
Thirty elastic foams with abrasion-resistant skin obtained in Example 7 were laid on the concrete floor of the barn. The removal of manure was easy, it was warm, and the growth of the cow was very good.
[0052]
【The invention's effect】
The present invention provides a wear-resistant elastic sheet with a resin composition in which a specific ethylene-vinyl acetate copolymer and a specific polyurethane elastomer are blended at a specific ratio, and a chemical foaming agent is added to the resin composition. Since it is blended and made into an abrasion-resistant elastic foam sheet, these single sheets or these laminate sheets have excellent chemical resistance, high mechanical strength, light weight, wear resistance, non-slip surface, printability Shoe soles, shoes, sandals, flexible containers, belts, clothing, furniture, chairs, sports equipment, grip materials, building materials, automotive interior materials, bumpers, airplane interior materials, ship interior materials, train interior materials, fences , Soundproofing materials, cushioning materials, filters, agricultural materials, leisure products, medical supplies, packaging materials, marine products, agricultural materials, pool mats, bathroom mats, kitchen mats Car wash mats are suitable as farm flooring of livestock.
Claims (12)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP35667996A JP3608893B2 (en) | 1996-12-27 | 1996-12-27 | Abrasion-resistant elastic sheet, foamable sheet and elastic foam made therefrom |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP35667996A JP3608893B2 (en) | 1996-12-27 | 1996-12-27 | Abrasion-resistant elastic sheet, foamable sheet and elastic foam made therefrom |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH10195256A JPH10195256A (en) | 1998-07-28 |
| JP3608893B2 true JP3608893B2 (en) | 2005-01-12 |
Family
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP35667996A Expired - Fee Related JP3608893B2 (en) | 1996-12-27 | 1996-12-27 | Abrasion-resistant elastic sheet, foamable sheet and elastic foam made therefrom |
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| Country | Link |
|---|---|
| JP (1) | JP3608893B2 (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
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| JP4505865B2 (en) * | 1999-01-14 | 2010-07-21 | 東ソー株式会社 | Non-crosslinked foam molding resin composition and foam comprising the same |
| DE19953707B4 (en) * | 1999-11-08 | 2007-12-27 | 4P Folie Forchheim Gmbh | Process for producing a plastic film |
| EP2998346A1 (en) * | 2014-09-19 | 2016-03-23 | A.P.I. Applicazioni Plastiche Industriali S.P.A. | Compounds based on crosslinkable polyolefins and thermoplastic polyurethanes |
| CN108641171A (en) * | 2018-04-19 | 2018-10-12 | 东莞市森宏新材料科技有限公司 | A kind of expanded material and preparation method thereof |
| WO2020081675A1 (en) | 2018-10-17 | 2020-04-23 | Braskem America, Inc. | Blends of thermoplastic urethanes and ethylene vinyl acetate copolymers |
| CN112955046A (en) * | 2018-11-02 | 2021-06-11 | 持田商工株式会社 | Core material for clothing and method for manufacturing same |
| CN115176717A (en) * | 2021-08-27 | 2022-10-14 | 中祈科技(上海)有限公司 | Detachable pet house |
| CN115160682B (en) * | 2022-07-26 | 2023-11-28 | 安丹达工业技术(上海)有限公司 | EVA-containing composition, wear-resistant and low-temperature-resistant material and application thereof |
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1996
- 1996-12-27 JP JP35667996A patent/JP3608893B2/en not_active Expired - Fee Related
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| JPH10195256A (en) | 1998-07-28 |
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