JP2022500287A - 金属層とポリアミド及びevaの層とを含有するラミネート - Google Patents
金属層とポリアミド及びevaの層とを含有するラミネート Download PDFInfo
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Abstract
Description
(A)少なくとも1種のポリアミド、
(B)少なくとも以下の成分:
(B1)少なくとも1種のC2〜C20−アルケン、及び
(B2)少なくとも1種のC2〜C18−アルケニルエステル
を重合することにより得ることができる少なくとも1種のコポリマー
を含む。
本発明によれば、ラミネートは、少なくとも1種の第1金属の少なくとも1つの第1層、及びポリマー組成物(PC)の少なくとも1つのさらなる層を含む。
本発明によれば、ポリマー組成物(PC)は、以下の成分:(A)少なくとも1種のポリアミド、並びに、(B)以下の成分の少なくとも1つ:(B1)少なくとも1種のC2〜C20−アルケン及び(B2)少なくとも1種のC2〜C18−アルケニルエステルを重合することにより得ることができる少なくとも1種のコポリマーを含む。
本発明によれば、ポリマー組成物(PC)は、成分(A)、少なくとも1種のポリアミドを含む。
PA 4 ピロリドン
PA 6 ε−カプロラクタム
PA 7 エナントラクタム(enantholactam)
PA 8 カプリロラクタム
PA 9 9−アミノペラルゴン酸
PA 11 11−アミノウンデカン酸
PA 12 ラウロラクタム
AA/BBポリマー:
PA 46 テトラメチレンジアミン、アジピン酸
PA 66 ヘキサメチレンジアミン、アジピン酸
PA 69 ヘキサメチレンジアミン、アゼライン酸
PA 610 ヘキサメチレンジアミン、セバシン酸
PA 612 ヘキサメチレンジアミン、デカンジカルボン酸
PA 613 ヘキサメチレンジアミン、ウンデカンジカルボン酸
PA 1212 ドデカン−1,12−ジアミン、デカンジカルボン酸
PA 1313 1,13−ジアミノトリデカン、ウンデカンジカルボン酸
PA 6T ヘキサメチレンジアミン、テレフタル酸
PA 9T ノニルジアミン、テレフタル酸
PA MXD6 m−キシリレンジアミン、アジピン酸
PA 6I ヘキサメチレンジアミン、イソフタル酸
PA 6−3−T トリメチルヘキサメチレンジアミン、テレフタル酸
PA 6/6T (PA 6及びPA 6Tを参照)
PA 6/66 (PA 6及びPA 66を参照)
PA 6/12 (PA 6及びPA 12を参照)
PA 66/6/610 (PA 66、PA 6及びPA 610を参照)
PA 6I/6T (PA 6I及びPA 6Tを参照)
PA PACM 12 ジアミノジシクロヘキシルメタン、ラウロラクタム
PA 6I/6T/PACM 例えばPA 6I/6T及びジアミノジシクロヘキシルメタン
PA 12/MACMI ラウロラクタム、ジメチルジアミノジシクロヘキシルメタン、イソフタル酸
PA 12/MACMT ラウロラクタム、ジメチルジアミノジシクロヘキシルメタン、テレフタル酸
PA PDA−T フェニレンジアミン、テレフタル酸。
(A1)カプロラクタム、
(A2)少なくとも1種のC4〜C40二酸、及び
(A3)少なくとも1種のC4〜C20ジアミン
を重合することにより得ることができる。
(A1)カプロラクタム、
(A2)少なくとも1種のC4〜C40二酸、及び
(A3)少なくとも1種のC4〜C20ジアミン
を重合することにより得ることができる。
(A1)カプロラクタム、
(A2)少なくとも1種のC4〜C40二酸、及び
(A3)少なくとも1種のC4〜C20ジアミン
を重合することにより得ることができる。
i)成分(A1)、(A2)及び(A3)を重合して、第1コポリアミドを得る工程と、
ii)工程i)で得られた第1コポリアミドをペレット化して、ペレット化コポリアミドを得る工程と、
iii)工程ii)で得られたペレット化コポリアミドを水で抽出して、抽出コポリアミドを得る工程と、
iv)工程iii)で得られた抽出コポリアミドを温度(TT)で乾燥させて、コポリアミドを得る工程と
を含む。
本発明によれば、成分(A1)はカプロラクタムである。カプロラクタムは、当業者に知られており、ε−カプロラクタム、ε−ラクタム、ヘキサノ−6−ラクタム又はヘキサヒドロ−2H−アゼピン−2−オンとも称される。カプロラクタムは、ε−アミノカプロン酸の環状アミドであり、CAS番号105−60−2を有する。
本発明によれば、成分(A2)は少なくとも1種のC4〜C40二酸である。
本発明によれば、成分(A3)は少なくとも1種のC4〜C20ジアミンである。
本発明によれば、ポリマー組成物(PC)は、少なくともの以下の成分:(B1)少なくとも1種のC2〜C20−アルケン及び(B2)少なくとも1種のC2〜C18−アルケニルエステルを重合することにより得ることができる少なくとも1種のコポリマーを成分(B)として含む。
本発明によれば、ポリマー組成物(PC)は、成分(C)、少なくとも1種のゴムを含むことができる。
(C1)40質量%〜100質量%の範囲、好ましくは55質量%〜79.5質量%の範囲の、2〜8個の炭素原子を有する少なくとも1種のα−オレフィン、
(C2)0質量%〜90質量%の範囲の少なくとも1種のジエン、
(C3)0質量%〜45質量%の範囲、好ましくは20質量%〜40質量%の範囲の、アクリル酸又はメタクリル酸の少なくとも1種のC1〜C18−アルキルエステル、
(C4)0質量%〜40質量%の範囲、好ましくは0.5質量%〜20質量%の範囲の、少なくとも1種のエチレン性不飽和モノカルボン酸及び/又はエチレン性不飽和ジカルボン酸、又は少なくとも1種のエチレン性不飽和モノカルボン酸及び/又はエチレン性不飽和ジカルボン酸の誘導体、
(C5)0質量%〜40質量%の範囲の、エポキシ基を含む少なくとも1種のモノマー、
(C6)0質量%〜5質量%の範囲の、他の遊離ラジカルで重合可能なモノマー
を重合することにより得ることができる、オレフィンをベースとするポリマーであり、
ただし、成分(C)はオレフィンホモポリマーではなく、
ここで、それぞれの質量パーセンテージは、成分(C1)、(C2)、(C3)、(C4)、(C5)及び(C6)の質量パーセンテージの合計に基づくものである。
65質量%〜99質量%の、
(C2)90質量%〜100質量%の範囲の少なくとも1種のジエン、及び0質量%〜10質量%のさらなる架橋可能なモノマー
を重合することにより得ることができるコア、及び
1質量%〜35質量%の、
(C7)1質量%〜30質量%の範囲の、スチレン、又は置換されたスチレン、又はそれらの混合物、及び
(C8)70質量%〜100質量%の範囲の少なくとも1種の不飽和ニトリル
を重合することにより得ることができるシェル、
から形成されるMBSゴム(メタクリレート/ブタジエン/スチレンゴム)である。
R1(R2OOC)C=C(COOR3)R4 II
mは、0〜20の整数であり、
nは、0〜10の整数である)。
50質量%〜98.9質量%、特に55質量%〜65質量%の、エチレン、
0.1質量%〜20質量%、特に0.15質量%〜10質量%の、グリシジルアクリレート及び/又はグリシジルメタクリレート、アクリル酸及び/又は無水マレイン酸、
1質量%〜45質量%、特に25質量%〜40質量%の、n−ブチルアクリレート及び/又は2−エチルヘキシルアクリレート、及び
0質量%〜10質量%、特に0.1質量%〜3質量%の、無水マレイン酸又はフマル酸又はそれらの混合物
を重合することにより得ることができるオレフィンポリマーであり、
ここで、質量パーセンテージは、それぞれ、重合に使用される成分の質量パーセンテージの合計に基づくものである。
a)70質量%〜90質量%、好ましくは75質量%〜85質量%の、
1)20質量%〜90質量%の、
アルキル基が、5〜12個の炭素原子、好ましくは5〜8個の炭素原子を有するn−アルキルアクリレート、又はアルキル基が、2〜12個の炭素原子、好ましくは4〜8個の炭素原子を有するアルキルアクリレートの混合物、
少なくとも1つのC−C二重結合を有する多官能性架橋剤であって、少なくとも1つのC−C二重結合がビニル基(CH2=C−基)である、多官能性架橋剤、及び、
任意に、少なくとも1つのC−C二重結合を有する多官能性グラフト剤であって、少なくとも1つのC−C二重結合がアリル基(CH2=CH−CH2−基)である、多官能性グラフト剤
を重合することにより得ることができるコポリマーからなるコアであって、このコアがコアの総量に基づいて、0.05〜5モル%のモル量、好ましくは0.5〜1.5モル%のモル量の、多官能性架橋剤及び任意の多官能性グラフト剤を含む、コア、
2)80質量%〜10質量%の、
アルキル基が、4〜12個の炭素原子、好ましくは4〜8個の炭素原子を有するn−アルキルアクリレート、又はアルキル基が、2〜12個の炭素原子、好ましくは4〜8個の炭素原子を有するアルキルアクリレートの混合物、及び
少なくとも1つのC−C二重結合を有する多官能性グラフト剤であって、少なくとも1つのC−C二重結合がアリル基(CH2=CH−CH2−基)である、多官能性グラフト剤、
を重合することにより得ることができるコポリマーからなるシェルであって、このシェルがシェルの総量に基づいて、0.05〜2.5モル%のモル量、好ましくは0.5〜1.5モル%のモル量のグラフト剤を含む、シェル
から構成される架橋エラストマーコア、並びに、
b)30質量%〜10質量%、好ましくは25質量%〜15質量%の、コアにグラフトされており、アルキル基が1〜4個の炭素原子を有するアルキルメタクリレートポリマー、又はアルキル基が1〜4個の炭素原子を有するアルキルメタクリレートとアルキル基が1〜8個の炭素原子を有するアルキルアクリレートとのランダムコポリマー(ここで、アルキルアクリレートが、ランダムコポリマーの総量に基づいて、5〜40モル%、好ましくは10〜20モル%のモル量で存在する)からなるシェル、
から形成されるアクリレートゴムである。
本発明のラミネートは、当業者に知られている任意の方法により製造することができる。
a)以下の成分:
(A)少なくとも1種のポリアミド、
(B)少なくとも以下の成分:
(B1)少なくとも1種のC2〜C20−アルケン、及び
(B2)少なくとも1種のC2〜C18−アルケニルエステル
を重合することにより調製される少なくとも1種のコポリマー、
を含むポリマー組成物(PC)のフィルムを提供する工程と、
b)少なくとも1種の第1金属の第1シートを加熱する工程と、
c)工程b)からの加熱された第1シートを工程a)で提供されたフィルムに押しつけて、ラミネートを得る工程と
を含む方法で製造される。
a)以下の成分:
(A)少なくとも1種のポリアミド、
(B)少なくとも以下の成分:
(B1)少なくとも1種のC2〜C20−アルケン、及び
(B2)少なくとも1種のC1〜C18−アルケニルエステル
を重合することにより調製される少なくとも1種のコポリマー、
を含むポリマー組成物(PC)のフィルムを提供する工程と、
b)少なくとも1種の第1金属の第1シートを加熱する工程と、
c)工程b)からの加熱された第1シートを工程a)で提供されたフィルムに押しつけて、ラミネートを得る工程と
を含む。
a)以下の成分:
(A)少なくとも1種のポリアミド、
(B)少なくとも以下の成分:
(B1)少なくとも1種のC2〜C20−アルケン、及び
(B2)少なくとも1種のC2〜C18−アルケニルエステル
を重合することにより調製される少なくとも1種のコポリマー、
を含むポリマー組成物(PC)のフィルムを提供する工程と、
b)少なくとも1種の第1金属の第1シートを加熱する工程と、
b1)少なくとも1種の第2金属の第2シートを加熱する工程と、
c)工程a)で提供されたフィルムを工程b)で加熱された第1シートと工程b1)で加熱された第2シートとの間に配置し、工程b)で加熱された第1シート及び工程b1)で加熱された第2シートを工程a)で提供されたフィルムに押しつけて、ラミネートを得る工程と
を含む。
a)以下の成分:
(A)少なくとも1種のポリアミド、
(B)少なくとも以下の成分:
(B1)少なくとも1種のC2〜C20−アルケン、及び
(B2)少なくとも1種のC2〜C18−アルケニルエステル
を重合することにより調製される少なくとも1種のコポリマー、
を含むポリマー組成物(PC)のフィルムを提供する工程と、
b)少なくとも1種の第1金属の第1シートを加熱する工程と、
b1)少なくとも1種の第2金属の第2シートを加熱する工程と、
c)工程a)で提供されたフィルムを工程b)で加熱された第1シートと工程b1)で加熱された第2シートとの間に配置し、工程b)で加熱された第1シート及び工程b1)で加熱された第2シートを工程a)で提供されたフィルムに押しつけて、ラミネートを得る工程と
を含む。
ポリアミド
P1:ナイロン−6(BASF SE製のUltramid B27E)
P2:30質量%のナイロン−6,36単位を有するナイロン−6/6,36
コポリマー
C1:LUWAX EAS 5(BASF SE製のエチレン−ビニルアセテート−ビニルアルコールコポリマー、25質量%〜29質量%のビニルアセテート、MVR(メルトボリュームフローレイト)(160℃/325g)8〜12g/10分)
C2:ESCORENE ULTRA FL 00309(Exxon Mobil製のエチレン−ビニルアセテート−ビニルアルコールコポリマー、9.4質量%のビニルアセテート、ASTM D 1238によるMVR(メルトボリュームフローレイト)(190℃/2.16kg)3g/10分)
C3:ESCORENE ULTRA FL 00328(Exxon Mobil製のエチレン−ビニルアセテート−ビニルアルコールコポリマー、27質量%のビニルアセテート、ASTM D 1238によるMVR(メルトボリュームフローレイト)(190℃/2.16kg)3g/10分)
C4:FLEXAREN 14003(Leuna製のエチレン−ビニルアセテート−ビニルアルコールコポリマー、14質量%のビニルアセテート、ISO 1133によるMVR(メルトボリュームフローレイト)(190℃/2.16kg)3g/10分)
ゴム
K1:Lupolen KR1270(BASF SE製のエチレン−アクリレート−無水マレイン酸コポリマー)
第1金属及び第2金属
鋼:HX260LADZ100MBOシート。
まずカプロラクタム、C36ダイマー酸(水素化した、Croda製のPripol 1009)、85質量%のヘキサメチレンジアミン水溶液、及び水を窒素で覆い、270℃の温度及び高圧で7時間撹拌し、次に水を減圧下でさらに4時間留去することにより、
ナイロン−6/6,36を調製した。得られたポリアミドを排出し、押し出し、ペレット化し、続いて熱水で抽出し、最後に乾燥させた。得られたポリアミドが30質量%のナイロン−6,36単位を含むような量で、出発化合物を使用した。
表1で特定されたポリマーを、表1で特定された量で、Haake CTW100押出機で250℃で配合し、直径3mmの丸型ダイを通して2kg/hのスループットで押し出して、ペレット状のポリマー組成物を得た。表1に記載されている量は、すべて質量%で表示するものである。
上記のようにペレット化したポリマー組成物を、215〜235℃で、Haake CTW100押出機で、100mmの幅を有するスロットダイを通して0.5〜1.0kg/hのスループットで押し出して、200μmの厚さを有するポリマー組成物のフィルムを得ることにより、ポリマー組成物のフィルムを製造した。
製造前に、ポリマー組成物のフィルムと鋼の第1シート及び第2シートの両方を80℃で7日間保存した。ラミネートを製造する前に、フィルムと鋼の両方を被着面の領域でn−ヘプタンで洗浄した。
i)室温(25℃)でサンプルを1時間保存し、
ii)試料ガード付きのInstron 10KN/Instron 150KNテスターでクランプし、10mm/分の速度で破損するまで引張力を加え、最大力は、当業者に知られている方法によって被着面に関する引張剪断力を決定するために使用され、
iii)ホルダーから被着部品を取り外し、破壊パターンを記録した。
Claims (15)
- 少なくとも1種の第1金属の少なくとも1つの第1層、及びポリマー組成物(PC)の少なくとも1つのさらなる層を含むラミネートであって、前記ポリマー組成物(PC)が、以下の成分:
(A)少なくとも1種のポリアミド、
(B)少なくとも以下の成分:
(B1)少なくとも1種のC2〜C20−アルケン、及び
(B2)少なくとも1種のC2〜C18−アルケニルエステル
を重合することにより得ることができる少なくとも1種のコポリマー
を含む、ラミネート。 - 前記ラミネートが少なくとも1種の第2金属の少なくとも1つの第2層をさらに含み、前記少なくとも1つの第1層が、前記少なくとも1つのさらなる層を介して、前記少なくとも1つの第2層と結合される、請求項1に記載のラミネート。
- 成分(A)が、以下の成分の少なくとも1つ:
(A1)カプロラクタム、
(A2)少なくとも1種のC4〜C40二酸、
(A3)少なくとも1種のC4〜C20ジアミン
を重合することにより得ることができる、請求項1又は2に記載のラミネート。 - 成分(B1)が、エテン、プロペン、1−ブテン及び2−ブテンからなる群から選択される、請求項1から3のいずれか一項に記載のラミネート。
- 成分(B2)が、ビニルアセテート、ビニルプロピオネート及びビニルブチレートからなる群から選択される、請求項1から4のいずれか一項に記載のラミネート。
- 成分(B)が、ポリエチレン−ビニルアセテート、ポリエチレン−ビニルアルコール及びエチレン−ビニルアセテート−ビニルアルコールのコポリマーからなる群から選択される、請求項1から5のいずれか一項に記載のラミネート。
- 前記ポリマー組成物(PC)が、成分(A)及び(B)の質量パーセンテージの合計に基づいて2質量%〜30質量%の範囲の成分(B)を含む、請求項1から6のいずれか一項に記載のラミネート。
- 前記ポリマー組成物(PC)が、成分(A)、(B)及び(C)の質量パーセンテージの合計に基づいて、1質量%〜30質量%の範囲の成分(C)、少なくとも1種のゴムをさらに含む、請求項1から7のいずれか一項に記載のラミネート。
- 前記ポリマー組成物(PC)が、無機充填剤、有機充填剤及び天然充填剤からなる群から選択される少なくとも1種の充填剤をさらに含む、請求項1から8のいずれか一項に記載のラミネート。
- 前記少なくとも1種の第1金属が、鉄、アルミニウム、銅、ニッケル及びマグネシウム、及びまたこれらの合金からなる群から選択される、請求項1から9のいずれか一項に記載のラミネート。
- 前記少なくとも1つの第1層が0.1mm〜0.6mmの範囲の厚さを有し、及び/又は前記少なくとも1つのさらなる層が0.02mm〜1.5mmの範囲の厚さを有する、請求項1から10のいずれか一項に記載のラミネート。
- 請求項1から11のいずれか一項に記載のラミネートを製造する方法であって、以下の工程:
a)以下の成分:
(A)少なくとも1種のポリアミド、
(B)少なくとも以下の成分:
(B1)少なくとも1種のC2〜C20−アルケン、及び
(B2)少なくとも1種のC1〜C18−アルケニルエステル
を重合することにより調製される少なくとも1種のコポリマー、
を含むポリマー組成物(PC)のフィルムを提供する工程と、
b)少なくとも1種の第1金属の第1シートを加熱する工程と、
c)工程b)からの加熱された前記第1シートを工程a)で提供された前記フィルムに押しつけて、ラミネートを得る工程と
を含む、方法。 - 工程b)が、前記第1シートを150℃〜350℃の範囲の温度に加熱することを含む、請求項12に記載の方法。
- 工程b)における第1シートの加熱が誘導手段によって行われる、請求項12又は13に記載の方法。
- 工程a)が、押出プロセスによって前記フィルムを提供することを含む、請求項12から14のいずれか一項に記載の方法。
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EP18194556 | 2018-09-14 | ||
EP18194556.9 | 2018-09-14 | ||
PCT/EP2019/074260 WO2020053296A1 (de) | 2018-09-14 | 2019-09-11 | Laminat enthaltend eine metallschicht und eine schicht aus einem polyamid und eva |
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JP2022500287A true JP2022500287A (ja) | 2022-01-04 |
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US (1) | US11958267B2 (ja) |
EP (1) | EP3849797B1 (ja) |
JP (1) | JP2022500287A (ja) |
KR (1) | KR20210057144A (ja) |
CN (1) | CN112585005A (ja) |
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WO2020053296A1 (de) | 2020-03-19 |
EP3849797B1 (de) | 2022-07-20 |
KR20210057144A (ko) | 2021-05-20 |
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CN112585005A (zh) | 2021-03-30 |
BR112021002594A2 (pt) | 2021-05-04 |
US11958267B2 (en) | 2024-04-16 |
US20210354427A1 (en) | 2021-11-18 |
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