JP6742428B2 - エチレンコポリマーを含む積層フィルム - Google Patents
エチレンコポリマーを含む積層フィルム Download PDFInfo
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- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
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- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
- B32B27/327—Layered products comprising a layer of synthetic resin comprising polyolefins comprising polyolefins obtained by a metallocene or single-site catalyst
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- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
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- B32B15/00—Layered products comprising a layer of metal
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- B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
- B32B15/082—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising vinyl resins; comprising acrylic resins
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- B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
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- B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
- B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
- B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
- B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
- B32B17/1055—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the resin layer, i.e. interlayer
- B32B17/10678—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the resin layer, i.e. interlayer comprising UV absorbers or stabilizers, e.g. antioxidants
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- B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
- B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
- B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
- B32B17/1055—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the resin layer, i.e. interlayer
- B32B17/10697—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the resin layer, i.e. interlayer being cross-linked
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- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
- B32B27/306—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising vinyl acetate or vinyl alcohol (co)polymers
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- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
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- B32B7/04—Interconnection of layers
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F30/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
- C08F30/04—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal
- C08F30/08—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal containing silicon
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- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/08—Copolymers of ethene
- C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
- C08L23/0892—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms containing monomers with other atoms than carbon, hydrogen or oxygen atoms
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- B32B2323/04—Polyethylene
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- C08F2500/00—Characteristics or properties of obtained polyolefins; Use thereof
- C08F2500/08—Low density, i.e. < 0.91 g/cm3
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Description
(A)10〜50wt%の、シラン基含有単位を有するエチレンのコポリマーと、
(B)少なくとも50wt%の、シラン基を含まない熱可塑性ポリオレフィンとを含み、
このポリマー組成物は、「テスト方法」に記載されるとおりに測定されるときに90℃にて1mm未満のクリープと、「テスト方法」に記載されるとおりに測定されるときに20N/cmより高い付着力とを有する。
R1SiR2 qY3−q (I)
ここで
R1はエチレン不飽和ヒドロカルビル、ヒドロカルビルオキシ、または(メト)アクリルオキシヒドロカルビル基であり、
各R2は独立に脂肪族飽和ヒドロカルビル基であり、
同じであっても異なっていてもよいYは加水分解性有機基であり、
qは0、1または2である。
1.中程度の伸長に伸びることができ、かつ応力を取り除いた際に元の形状に近いものに戻り得ること。
2.特定の温度より上では溶融物として加工可能であり、かつ冷却の際には固体状態に戻ること。
3.顕著なクリープがないこと。
a)メルトフローレート
メルトフローレート(melt flow rate)MFR2は、エチレンホモポリマーおよびコポリマーに対して190℃および2.16kgの荷重にてISO 1133に従って測定した。
ポリマー組成物中のポリマーのコモノマー含有量を定量化するために、定量的核磁気共鳴(NMR:nuclear−magnetic resonance)分光法を用いた。
VA=(I*VA−(IArBHT)/2)/1
MA=I1MA/3
BA=I4BA/2
VTMS=I1VTMS/9
BHT=IArBHT/2
E=(1/4)*[Ibulk−5*VA−3*MA−10*BA−3*VTMS−21*BHT]
fM=M/(E+VA+MA+BA+VTMS)
M[mol%]=100*fM
M[wt%]=100*(fM*MW)/((fVA*86.09)+(fMA*86.09)+(fBA*128.17)+(fVTMS*148.23)+((1−fVA−fMA−fBA−fVTMS)*28.05))
randall89
J.Randall,Macromol.Sci.,Rev.Macromol.Chem.Phys.1989,C29,201。
サンプルから厚さ0.45mmのフィルムを調製した。このフィルムから、30mm*120mmの2つのサンプルを切り取った。30mm*150mm*3.85mm厚さの2つの平面ガラススライドをイソプロパノールで洗浄して乾燥したものを調製した。100mm*15mmの孔を有するテフロン(登録商標)(0.1mm厚さ)の2つのマスクも調製した。
ポリマーサンプルから0.45mmのフィルムを調製した。標準的な仕様に従ってフィルムを調整した。
0.45mmの厚さを有する押出しフィルムを付着力測定に用いた。イソプロパノールで洗浄して乾燥した標準的な窓ガラスに対して、付着強度を測定した。付着力テスト測定のためにガラスとフィルムとの間にテフロン(登録商標)ストライプを伴って、ガラスプレート(寸法30×300×4mm(b*l*d))上に2つのフィルムを積層することによって、付着サンプルを調製した。積層の前に、2つのフィルムの頂部にバックシートも置いた。完全自動ラミネータP.Energy L036LABを用いて、150℃にて15分間および800mbarの圧力にて積層を行った。積層後、テフロン(登録商標)ストライプを除去した。剥離強度測定のために、15mmの幅を有する試料をサンプルガラスからスライスした。Alwetron TCT 25引張り機において、90℃の剥離角度および100mm/minの剥離速度によって、付着力を測定した。1kNの荷重セルによる剥離(peal)力を常時測定しながら、最大100mmの伸長まで剥離テストを行った。この測定から最大、最小、および平均の力(N)を取った。平均の力を試料の幅(15mm)で割ることによって、付着力(N/cm)を測定した。
0.45mmの厚さおよび200mmの長さを有する押出しフィルムに対して、水吸収測定を行った。調査するフィルムを23℃および50%のRHの恒温室内で3週間調整した。カールフィッシャー滴定によって、サンプル中の総水分含有量の水吸収判定を行った。用いた機器は、Mettler DL39 Coulometric KF Titratorである。総水分含有量測定のために、サンプルを180℃まで加熱した。
動的剪断測定によってポリマー溶融物を特徴付けることは、ISO規格6721−1および6721−10に準拠する。この測定は、25mm平行プレートジオメトリを備えるAnton Paar MCR501応力制御回転レオメータにおいて行った。窒素雰囲気を用いて、歪みを線形粘弾性領域内に設定して、圧縮成形プレートに対する測定を行った。振動剪断テストは190℃にて、0.01〜600rad/sの周波数範囲を適用し、1.3mmの間隙を設定して行った。
γ(t)=γ0sin(ωt) (1)
σ(t)=σ0sin(ωt+δ) (2)
ここで
σ0およびγ0はそれぞれ応力および歪みの振幅であり、
ωは角周波数であり、
δは位相シフト(加えられた歪みと応力応答との間の損失角)であり、
tは時間である。
EI(x)=(G’’=x kPa)に対するG’[Pa] (9)
[1] Rheological characterization of polyethylene fractions Heino, E.L., Lehtinen, A., Tanner J., Seppala, J., Neste Oy, Porvoo, Finland, Theor. Appl. Rheol., Proc. Int. Congr. Rheol, 11th (1992), 1, 360−362
[2] The influence of molecular structure on some rheological properties of polyethylene, Heino, E.L., Borealis Polymers Oy, Porvoo, Finland, Annual Transactions of the Nordic Rheology Society, 1995.).
[3] Definition of terms relating to the non−ultimate mechanical properties of polymers, Pure & Appl. Chem., Vol. 70, No. 3, pp. 701−754, 1998.
パイロット規模押出し機(Prism TSE 24TC)において、異なる化合物を配合した。得られた混合物を以下の表に与えた条件で溶融混合し、ストリング状に押出してペレット化した。
付着力および透過率測定のために、Collin teach−line E 20T押出し機において、50mmの幅および0.45mmの厚さの寸法を有するフィルム(テープ)を押出した。以下の設定温度によってテープを生産した。
150/150/150℃および50rpm。
EVS(1.9wt%):VTMS−エチレンコポリマーであって、高圧チューブ状リアクタによって従来の方式で従来の過酸化物イニシエータを用いて、最高温度285℃にて生成したものであり、ここではコポリマー中に1.9wt%のシラン含有量が得られるような量のビニルトリメトキシシラン(VTMS:vinyl trimethoxysilane)とエチレンモノマーとを反応させた。当業者に周知であるとおり、MFRを調節するためにCTAを用いた。ISO 1133(190℃、2.16kg)に従うメルトフローレート(MFR2@190℃)は1g/10minである。
表1は、より高い融解温度を有するEVS(1.9wt%)を加えたときのクリープ性能に対する影響を示す。20%のEVS(1.9wt%)をQueo 8201に加えることによって、サンプルは110℃におけるクリープテストに合格することになる。このテストにおける好ましい組成である20%EVS(1.9wt%)、80%Queo 8201は、クリープの問題を解決する一方で、光学性能に対する限定された影響を有する。
Claims (10)
- 一層の基体層と少なくとも一層を有する積層物品であって、
該少なくとも一層は、ポリマー組成物であって、
(A)25〜45wt%の、シラン基含有単位を有するISO1183Dによって測定した密度が920kg/m3より高いエチレンのコポリマーと、
(B)少なくとも50wt%の、ISO1183Dによって測定した密度が880kg/m 3 より高く、891kg/m3未満のプラストマー(E)とを含み、
前記ポリマー組成物は、150℃、300秒の排気時間、800mbar膜圧力による660秒のプレス時間にて真空積層したテスト試料において90℃にて48時間で1mm未満のクリープと、150℃にて15分間および800mbarの圧力にて積層した後20N/cmより高い付着力とを有する、積層物品。 - シラン基を含まない前記熱可塑性ポリオレフィン(B)は、前記ポリマー組成物の総重量に基づいて55〜75wt%の量で存在する、請求項1記載の積層物品。
- 前記ポリマー組成物中のシラン基の総量は1wt%未満である、請求項1または2記載の積層物品。
- 前記ポリマー組成物は、860〜910kg/m3の密度と、1〜10g/10minのMFR2とを有する、請求項1〜3のいずれか一項に記載の積層物品。
- 前記ポリマー組成物は過酸化物を含まない、請求項1〜4のいずれか一項に記載の積層物品。
- 前記ポリマー組成物は、前記ポリマー組成物の総重量に基づいて0.1〜5wt%の量で存在するUV安定剤および抗酸化剤を有する、請求項1〜5のいずれか一項に記載の積層物品。
- 前記ポリマー組成物は縮合触媒(F)を含む、請求項1〜6のいずれか一項に記載の積層物品。
- 縮合触媒(F)は、
− マスターバッチとして、
− またはポリマー組成物を含有する少なくとも一層と直接的または間接的に接触する別の層からの移動によって、
− または液体として、押出し機への直接注入によって、
− または前記縮合触媒を前記ポリマー組成物と混合し、混合物を押出し機に供給することによって加えられる、請求項7記載の積層物品。 - 前記基体層はガラス層である、請求項1〜8いずれか一項に記載の積層物品。
- 請求項1〜9のいずれか一項に記載の積層物品を生産するためのプロセスであって、前記ポリマー組成物は130℃から170℃にて積層される、プロセス。
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