JP2021523954A - 極性ポリマーとポリオールポリエステル及びポリヒドロキシアルカンとのブレンド - Google Patents
極性ポリマーとポリオールポリエステル及びポリヒドロキシアルカンとのブレンド Download PDFInfo
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- JP2021523954A JP2021523954A JP2020539049A JP2020539049A JP2021523954A JP 2021523954 A JP2021523954 A JP 2021523954A JP 2020539049 A JP2020539049 A JP 2020539049A JP 2020539049 A JP2020539049 A JP 2020539049A JP 2021523954 A JP2021523954 A JP 2021523954A
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Abstract
Description
態様1:
a)少なくとも1種の極性ポリマーと、
b)1モル当たり200グラムを超える分子量を持つ少なくとも1種の光沢度改良添加剤とを含み、
前記少なくとも1種の光沢度改良添加剤は、官能基含有直鎖アルカン、官能基含有分岐アルカン、官能基含有脂肪酸エステル及びそれらの混合物からなる群から選択され、
前記少なくとも1種の光沢度改良添加剤は、ビシナルジオール、ヒドロキシリン酸トリエステル、ヒドロキシエステル、ヒドロキシエーテル、ヒドロキシアミノ、ヒドロキシスルフィド、ヒドロキシニトリル、ヒドロキシアミン、末端アルコール、チイラン、ケトン及び環状カーボネートからなる群から選択される少なくとも1種の官能基を有する、組成物である。
態様2:
前記組成物は、少なくとも1種のビシナルジオール基を含む少なくとも1種の直鎖又は分岐ヒドロキシアルカンを有する、態様1に記載の組成物である。
態様3:
前記少なくとも1種の直鎖又は分岐ヒドロキシアルカンは、1,2−ジヒドロキシアルカンである、態様1又は2に記載の組成物である。
態様4:
前記組成物は、1モル当たり200グラムを超える平均分子量を有し、且つ少なくとも2つのヒドロキシル基を有する少なくとも1種の脂肪酸エステルを含み、
前記脂肪酸エステルは、動植物油から得られる、態様1〜3に記載の組成物である。
態様5:
前記動植物油から得られる少なくとも2つのヒドロキシル基を含む前記脂肪酸エステルは、エポキシ基含有動植物油と少なくとも1種の水性酸又は水性塩基との反応生成物である、態様1〜4に記載の組成物である。
態様6:
前記エポキシ基含有動植物油は、エポキシ基含有藻類油、エポキシ基含有キャノーラ油、エポキシ基含有ココナッツ油、エポキシ基含有ひまし油、エポキシ基含有トウモロコシ油、エポキシ基含有綿実油、エポキシ基含有フラックス油、エポキシ基含有魚油、エポキシ基含有ブドウ種子油、エポキシ基含有ヘンプ油、エポキシ基含有ジャトロファ油、エポキシ基含有ホホバ油、エポキシ基含有マスタード油、エポキシ基含有キャノーラ油、エポキシ基含有パーム油、エポキシ基含有パームステアリン、エポキシ基含有なたね油、エポキシ基含有サフラワー油、エポキシ基含有大豆油、エポキシ基含有ひまわり油、エポキシ基含有トール油、エポキシ基含有オリーブ油、エポキシ基含有獣脂、エポキシ基含有豚脂、エポキシ基含有鶏脂、エポキシ基含有亜麻仁油、エポキシ基含有桐油、エポキシ基含有亜麻仁油、エポキシ基含有桐油及びそれらの混合物からなる群から選択される、態様4又は5のいずれかに記載の組成物である。
態様7:
前記組成物は、前記極性ポリマーの質量基準で2〜40質量パーセントの前記光沢度改良添加剤を含む、態様1〜6に記載の組成物である。
態様8:
前記組成物を、BYKガードナーマイクロ−グロス75°グロスメータを用いて測定した場合、75°光沢度が53以上であり、且つBYKガードナーマイクロ−トリ−グロス20°/60°/85°グロスメータを用いて測定した場合、60°光沢度が12以上である、態様1〜7に記載の組成物である。
態様9:
衝撃性改良添加剤を更に含む、態様1〜8に記載の組成物である。
態様10:
前記衝撃性改良添加剤は、線状ブロックコポリマー、コアシェルポリマー及びそれらの混合物からなる群から選択される、請求項9に記載の組成物である。
態様11:
前記組成物は、前記極性ポリマーの質量基準で20〜60質量パーセントの前記衝撃性改良添加剤を含む、態様9又は10のいずれかに記載の組成物である。
態様12:
前記極性ポリマーは、アクリルポリマー、アクリロニトリルポリマー、ポリ塩化ビニル(PVC)、ポリカーボネート(PC)、ポリウレタン(PU)、熱可塑性ポリウレタン(TPU)、ポリエステル、ポリエチレンテレフタレート(PET)、ポリエチレンナフタレート(PEN)、ポリブチレンテレフタレート(PBT)、グリコール変性ポリエステル(PETG)、フルオロポリマー及びそれらのコポリマー、並びにそれらの混合物から選択される少なくとも1種のポリマーを含む、態様1〜11に記載の組成物である。
態様13:
前記少なくとも1種の極性ポリマーは、アクリルポリマー又はアクリロニトリルポリマーであり、且つホモポリマー、コポリマー、ターポリマー又はそれらの混合物を含む、態様1〜12に記載の組成物である。
態様14:
前記極性ポリマーは、メチルメタクリレート、メチルアクリレート、エチルアクリレート、エチルメタクリレート、ブチルアクリレート、ブチルメタクリレート、イソ−オクチルメタクリレート、イソ−オクチルアクリレート、ラウリルアクリレート、ラウリルメタクリレート、ステアリルアクリレート、ステアリルメタクリレート、イソボルニルアクリレート、イソボルニルメタクリレート、メトキシエチルアクリレート、メトキシエチルメタクリレート、2−エトキシエチルアクリレート、2−エトキシエチルメタクリレート、ジメチルアミノエチルアクリレート、ジメチルアミノエチルメタクリレート、アクリロニトリル、シアン化ビニル化合物、スチレンの極性誘導体、及びそれらの混合物からなる群から選択される少なくとも1種のモノマーを重合した形態で含む、態様1〜13に記載の組成物である。
態様15:
前記極性ポリマーは、メチルメタクリレートと2〜16質量パーセントの1種以上の炭素数1〜4のアクリレートとのコポリマーであるアクリルポリマーである、態様1〜14に記載の組成物である。
態様16:
多層複合構造体であって、
a)請求項1に記載の組成物を含む少なくとも1種のキャップストック層と、
b)少なくとも1種の基材層とを含み、
前記多層複合構造体は、外層及び内層を備え、
前記外層は、外表面を有し、
前記キャップストック層は前記外層であり、且つ前記基材層が前記内層である、多層複合構造体である。
態様17:
前記基材層は、アクリルポリマー、スチレンポリマー、ポリオレフィン、ポリ塩化ビニル(PVC)、ポリカーボネート(PC)、ポリウレタン(PU)、スチレン−アクリロニトリル(SAN)コポリマー、アクリロニトリルブタジエンスチレン(ABS)ポリマー、メチルメタクリレートアクリロニトリルブタジエンスチレン(MABS)コポリマー、アクリロニトリルスチレンアクリレート(ASA)コポリマー、耐衝撃性ポリスチレン(HIPS)、木材/ポリマー複合材、ポリエステル、又はそれらの混合物から選択される少なくとも1種のポリマーを含む、態様16に記載の多層複合構造体である。
態様18:
前記キャップストック層を、BYKガードナーマイクロ−グロス75°グロスメータを用いて測定した場合、75°光沢度が53以上であり、且つBYKガードナーマイクロ−トリ−グロス20°/60°/85°グロスメータを用いて測定した場合、60°光沢度が12以上である、態様16又は17に記載の多層複合構造体である。
態様19:
前記キャップストック層を、円錐型チップでガードナー衝撃性試験によって測定する場合、平均破損エネルギー(MFE)衝撃性強度は少なくとも0.7in−lb/milである、態様16〜18のいずれかに記載の多層複合構造体である。
態様20:
a)少なくとも1種の極性ポリマーと、
b)少なくとも1種の光沢度改良添加剤とを含み、
前記少なくとも1種の光沢度改良添加剤は、少なくとも2種のヒドロキシル基を含有し1モル当たり200グラムを超える分子量を持つヒドロキシアルカン、少なくとも2種のヒドロキシル基を含有し1モル当たり200グラムを超える分子量を持つポリオールポリエステル、及びそれらの混合物からなる群から選択される、組成物である。
一般に、好適な光沢度改良添加剤は、1モル当たり200グラムを超える分子量及び1分子当たり少なくとも1種、好ましくは少なくとも2つの極性官能基を有する化合物を含む。これらの化合物は、キャップストックポリマーの40質量%までの量でキャップストックポリマーに組み込みうる。
上記のような光沢度改良添加剤は、多層複合構造体の外側キャップストック層又はキャップ層として使用されることを意図する極性熱可塑性ポリマーと結合される。本開示の例示的態様によるとそのような構造体の非限定的な例は、内側(又は下側)基材層及び外側(又は上側)キャップストック層を含む押出形材である。キャップストック層の厚さは、好ましくは1mil厚〜100mil厚、好ましくは3mil厚〜25mil厚、より好ましくは4mil厚〜20mil厚である。
基材層は、5milから10cm超まで、10milから10cm超まで、好ましくは50milから10cm超まで、より好ましくは100milから10cm超までの厚さでありうる。多層複合構造体の基材層は、熱可塑性又は熱硬化性でよく複合物でよい。
多層複合構造体はまた、上記のような光沢度改良添加剤を含む外側ポリマー系キャップストック層と内側基材層との密着性を高めるために、任意の結合層を含んでよい。結合層として有用な材料としては限定されるものではないが、エチレン/アクリル酸エステル/無水マレイン酸コポリマーおよびエチレン/アクリル酸/メタクリル酸グリシジルコポリマー等の官能化ポリオレフィン;スチレンコポリマー(例えば、ArkemaからTacryl(登録商標)の商品名で販売されているスチレンコポリマーを含む);ポリアミド、又はポリアミドコポリマーが挙げられる。
ポリマーへの密着性を改善するために当技術分野で公知されているような表面処理はまた、多層複合構造を作製する際の本発明の実施に利用してよい。非限定的な例としては、コロナ処理若しくはプラズマ処理又は化学処理又は溶媒及びクレンジング剤を使用して、互いに密着して多層複合構造体を形成する各層の表面を準備することが挙げられる。
極性ポリマーキャップ層は本明細書に開示されている光沢度改良添加剤(また衝撃性改良特性を有してよい)に加え、極性ポリマーマトリックス基準で例えば20〜60質量パーセントの量で衝撃性改良添加剤(衝撃性改良剤)を含みうる。有用な衝撃性改良剤は、線状のブロックコポリマーを含み、当技術分野で公知されているように、好ましくはコアシェルポリマーである。ポリブタジエンゴムは、好適な衝撃性改良剤である。ハードコア、コアシェルの衝撃性改良剤が特に好ましい。
当技術分野で公知の任意の添加剤は、本明細書に開示されている多層複合構造体のいずれか又はすべての層での使用に好適である。添加剤の非限定的な例としては、フィラー、表面改良添加剤、抗酸化剤、光沢度改良添加剤、UV遮断剤及び加工助剤が挙げられる。
本明細書に開示されている多層複合構造体を作製する方法は、産業上知られているようなそのような典型的な方法でよい。
耐衝撃又は衝撃強さは円錐型チップでガードナー衝撃性テキスト(GIT)を用いて測定される(ASTM D4226 (2009))。結果は、in−lbs/milの単位で平均破損エネルギー(MFE)衝撃性強度として報告される。
下記のキャップストック層のポリマーブレンドを調製し、発明例Aに従って異なる光沢度改良添加剤をそれぞれ含んでいた。光沢度改良添加剤を含まない比較例のポリマーブレンドも準備した。これらのキャップストック層配合を表1に示す。
カスタムメイドの1インチ×4インチのダイと基材層押出機及びキャップストック層押出機の2つの押出機とでPVC基材上に例1に従って作製されたアクリルキャップストックブレンドを共押出しした。
熱分解温度は、材料が劣化し始める前にどのくらいの温度で押出されるかの目安を提供するという意味で、プラスチックの押出成形の熱操業ウィンドウを決定するのに便利な方法である。
本発明によれば、下記キャップストック層のポリマーブレンドを調製し、異なる量の光沢度改良添加剤をそれぞれ含んでいた。比較例では光沢度改良添加剤を含まないポリマーブレンドも調製した。これらのキャップストック配合は表5に示す。
Claims (20)
- a)少なくとも1種の極性ポリマーと、
b)1モル当たり200グラムを超える分子量を持つ少なくとも1種の光沢度改良添加剤とを含み、
前記少なくとも1種の光沢度改良添加剤は、官能基含有直鎖アルカン、官能基含有分岐アルカン、官能基含有脂肪酸エステル及びそれらの混合物からなる群から選択され、
前記少なくとも1種の光沢度改良添加剤は、ビシナルジオール、ヒドロキシリン酸トリエステル、ヒドロキシエステル、ヒドロキシエーテル、ヒドロキシアミノ、ヒドロキシスルフィド、ヒドロキシニトリル、ヒドロキシアミン、末端アルコール、チイラン、ケトン及び環状カーボネートからなる群から選択される少なくとも1種の官能基を有する、組成物。 - 前記組成物は、少なくとも1種のビシナルジオール基を含む少なくとも1種の直鎖又は分岐ヒドロキシアルカンを有する、請求項1に記載の組成物。
- 前記少なくとも1種の直鎖又は分岐ヒドロキシアルカンは、1,2−ジヒドロキシアルカンである、請求項2に記載の組成物。
- 前記組成物は、1モル当たり200グラムを超える重量平均分子量を有し、且つ少なくとも2つのヒドロキシル基を有する少なくとも1種の脂肪酸エステルを含み、
前記脂肪酸エステルは、動植物油から得られる、請求項2に記載の組成物。 - 前記動植物油から得られる少なくとも2つのヒドロキシル基を含む前記脂肪酸エステルは、エポキシ基含有動植物油と少なくとも1種の水性酸又は水性塩基との反応生成物である、請求項4に記載の組成物。
- 前記エポキシ基含有動植物油は、エポキシ基含有藻類油、エポキシ基含有キャノーラ油、エポキシ基含有ココナッツ油、エポキシ基含有ひまし油、エポキシ基含有トウモロコシ油、エポキシ基含有綿実油、エポキシ基含有フラックス油、エポキシ基含有魚油、エポキシ基含有ブドウ種子油、エポキシ基含有ヘンプ油、エポキシ基含有ジャトロファ油、エポキシ基含有ホホバ油、エポキシ基含有マスタード油、エポキシ基含有キャノーラ油、エポキシ基含有パーム油、エポキシ基含有パームステアリン、エポキシ基含有なたね油、エポキシ基含有サフラワー油、エポキシ基含有大豆油、エポキシ基含有ひまわり油、エポキシ基含有トール油、エポキシ基含有オリーブ油、エポキシ基含有獣脂、エポキシ基含有豚脂、エポキシ基含有鶏脂、エポキシ基含有亜麻仁油、エポキシ基含有桐油、エポキシ基含有亜麻仁油、及びそれらの混合物からなる群から選択される、請求項5に記載の組成物。
- 前記組成物は、前記極性ポリマーの質量基準で2〜40質量パーセントの間の前記光沢度改良添加剤を含む、請求項1に記載の組成物。
- 前記組成物を、BYKガードナーマイクロ−グロス75°グロスメータを用いて測定した場合、75°光沢度が53以上であり、且つBYKガードナーマイクロ−トリ−グロス20°/60°/85°グロスメータを用いて測定した場合、60°光沢度が12以上である、請求項1に記載の組成物。
- 衝撃性改良添加剤を更に含む、請求項1に記載の組成物。
- 前記衝撃性改良添加剤は、線状ブロックコポリマー、コアシェルポリマー及びそれらの混合物からなる群から選択される、請求項9に記載の組成物。
- 前記組成物は、前記極性ポリマーの質量基準で20〜60質量パーセントの間の前記衝撃性改良添加剤を含む、請求項10に記載の組成物。
- 前記極性ポリマーは、アクリルポリマー、アクリロニトリルポリマー、ポリ塩化ビニル(PVC)、ポリカーボネート(PC)、ポリウレタン(PU)、熱可塑性ポリウレタン(TPU)、ポリエステル、ポリエチレンテレフタレート(PET)、ポリエチレンナフタレート(PEN)、ポリブチレンテレフタレート(PBT)、グリコール変性ポリエステル(PETG)、フルオロポリマー若しくはそれらのコポリマー、又はそれらの混合物から選択される少なくとも1種のポリマーを含む、請求項1に記載の組成物。
- 前記少なくとも1種の極性ポリマーは、アクリルポリマー又はアクリロニトリルポリマーであり、且つホモポリマー、コポリマー、ターポリマー又はそれらの混合物を含む、請求項12に記載の組成物。
- 前記極性ポリマーは、メチルメタクリレート、メチルアクリレート、エチルアクリレート、エチルメタクリレート、ブチルアクリレート、ブチルメタクリレート、イソ−オクチルメタクリレート、イソ−オクチルアクリレート、ラウリルアクリレート、ラウリルメタクリレート、ステアリルアクリレート、ステアリルメタクリレート、イソボルニルアクリレート、イソボルニルメタクリレート、メトキシエチルアクリレート、メトキシエチルメタクリレート、2−エトキシエチルアクリレート、2−エトキシエチルメタクリレート、ジメチルアミノエチルアクリレート、ジメチルアミノエチルメタクリレート、アクリロニトリル、シアン化ビニル化合物、スチレンの極性誘導体、及びそれらの混合物からなる群から選択される少なくとも1種のモノマーを重合した形態で含む、請求項13に記載の組成物。
- 前記極性ポリマーは、メチルメタクリレートと2〜16質量パーセントの1種以上の炭素数1〜4のアクリレートとのコポリマーであるアクリルポリマーである、請求項14に記載の組成物。
- 多層複合構造体であって、
a)請求項1に記載の組成物を含む少なくとも1種のキャップストック層と、
b)少なくとも1種の基材層とを含み、
前記多層複合構造体は、外層及び内層を備え、
前記外層は、外表面を有し、
前記キャップストック層は前記外層であり、且つ前記基材層が前記内層である、多層複合構造体。 - 前記基材層は、アクリルポリマー、スチレンポリマー、ポリオレフィン、ポリ塩化ビニル(PVC)、ポリカーボネート(PC)、ポリウレタン(PU)、スチレン−アクリロニトリル(SAN)コポリマー、アクリロニトリルブタジエンスチレン(ABS)ポリマー、メチルメタクリレートアクリロニトリルブタジエンスチレン(MABS)コポリマー、アクリロニトリルスチレンアクリレート(ASA)コポリマー、耐衝撃性ポリスチレン(HIPS)、木材/ポリマー複合材、ポリエステル、又はそれらの混合物から選択される少なくとも1種のポリマーを含む、請求項16に記載の多層複合構造体。
- 前記キャップストック層を、BYKガードナーマイクロ−グロス75°グロスメータを用いて測定した場合、75°光沢度が53以上であり、且つBYKガードナーマイクロ−トリ−グロス20°/60°/85°グロスメータを用いて測定した場合、60°光沢度が12以上である、請求項16に記載の多層複合構造体。
- 前記キャップストック層を、円錐型チップでガードナー衝撃性試験によって測定する場合、平均破損エネルギー(MFE)衝撃性強度は少なくとも0.7in−lb/milである、請求項16に記載の多層複合構造体。
- a)少なくとも1種の極性ポリマーと、
b)少なくとも1種の光沢度改良添加剤とを含み、
前記少なくとも1種の光沢度改良添加剤は、少なくとも2種のヒドロキシル基を含有し1モル当たり200グラムを超える分子量を持つヒドロキシアルカン、少なくとも2種のヒドロキシル基を含有し1モル当たり200グラムを超える分子量を持つポリオールポリエステル、及びそれらの混合物からなる群から選択される、組成物。
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