JP2021506630A - ポリカーボネート、タルクおよびワックスを含む基材層を有する多層体 - Google Patents
ポリカーボネート、タルクおよびワックスを含む基材層を有する多層体 Download PDFInfo
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- JP2021506630A JP2021506630A JP2020533659A JP2020533659A JP2021506630A JP 2021506630 A JP2021506630 A JP 2021506630A JP 2020533659 A JP2020533659 A JP 2020533659A JP 2020533659 A JP2020533659 A JP 2020533659A JP 2021506630 A JP2021506630 A JP 2021506630A
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- talc
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- PXZQEOJJUGGUIB-UHFFFAOYSA-N isoindolin-1-one Chemical compound C1=CC=C2C(=O)NCC2=C1 PXZQEOJJUGGUIB-UHFFFAOYSA-N 0.000 description 1
- 230000000873 masking effect Effects 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000001465 metallisation Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 125000005397 methacrylic acid ester group Chemical group 0.000 description 1
- 125000005395 methacrylic acid group Chemical class 0.000 description 1
- GRVDJDISBSALJP-UHFFFAOYSA-N methyloxidanyl Chemical group [O]C GRVDJDISBSALJP-UHFFFAOYSA-N 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000006082 mold release agent Substances 0.000 description 1
- 150000002763 monocarboxylic acids Chemical class 0.000 description 1
- 239000011858 nanopowder Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000002667 nucleating agent Substances 0.000 description 1
- NKBWPOSQERPBFI-UHFFFAOYSA-N octadecyl octadecanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCCCCCCCCCCCCCCCC NKBWPOSQERPBFI-UHFFFAOYSA-N 0.000 description 1
- FMJSMJQBSVNSBF-UHFFFAOYSA-N octocrylene Chemical compound C=1C=CC=CC=1C(=C(C#N)C(=O)OCC(CC)CCCC)C1=CC=CC=C1 FMJSMJQBSVNSBF-UHFFFAOYSA-N 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000005447 octyloxy group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])O* 0.000 description 1
- 230000036961 partial effect Effects 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 238000004375 physisorption Methods 0.000 description 1
- 229920002587 poly(1,3-butadiene) polymer Polymers 0.000 description 1
- 229920003207 poly(ethylene-2,6-naphthalate) Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920001707 polybutylene terephthalate Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 229920001195 polyisoprene Polymers 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- FBCQUCJYYPMKRO-UHFFFAOYSA-N prop-2-enyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC=C FBCQUCJYYPMKRO-UHFFFAOYSA-N 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- NHARPDSAXCBDDR-UHFFFAOYSA-N propyl 2-methylprop-2-enoate Chemical compound CCCOC(=O)C(C)=C NHARPDSAXCBDDR-UHFFFAOYSA-N 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000004945 silicone rubber Substances 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- 230000035882 stress Effects 0.000 description 1
- 150000003440 styrenes Chemical class 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 238000009757 thermoplastic moulding Methods 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 238000000427 thin-film deposition Methods 0.000 description 1
- 150000003918 triazines Chemical class 0.000 description 1
- XHGIFBQQEGRTPB-UHFFFAOYSA-N tris(prop-2-enyl) phosphate Chemical compound C=CCOP(=O)(OCC=C)OCC=C XHGIFBQQEGRTPB-UHFFFAOYSA-N 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
- 229920006163 vinyl copolymer Polymers 0.000 description 1
- 238000004846 x-ray emission Methods 0.000 description 1
- 229910052984 zinc sulfide Inorganic materials 0.000 description 1
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Abstract
Description
前記表面処理されていないタルク10重量部ごとに、0.10〜1.4重量部、好ましくは0.3〜1.0重量部の無水物変性α−オレフィンポリマーが使用される。好ましくは、前記組成物は、衝撃改質剤として文献に記載されることがある成分C)の無水物変性α−オレフィンポリマーを除いて、ポリエステルまたはグラフトポリマーを含まず、最も好ましくは衝撃改質剤を全く含まない。従来技術に対してポリカーボネート/タルク組成物の良好な加工性、高い剛性および良好な耐衝撃性等の特性を改善することが実際に可能であることが、基材材料の特徴である。これにより、表面処理されているB)のタルクまたはタルク混合物の前処理の追加工程を回避することが可能となり、したがって、より安価でより効率的な方法で製造され得る組成物を提供することが可能となる。
I)基材層(S)、
II)前記基材層に直接結合する金属層(M)および
III)任意に、前記金属層上の保護層(P)
を含む多層体であって、
前記基材層は、成分A)〜D)を混合することにより得られる組成物を含み、
A)ポリカーボネートであり、
B)は、中央粒径D50が0.01〜9.5μmである表面処理されていないタルクであり、前記粒径D50は沈降分析によって決定され、
C)は、DIN ISO 17025:2005に従ってアルコール性水酸化カリウム溶液を用いた電位差滴定によって決定される、少なくとも30mgKOH/gの酸価、および4000〜40000g/モルの平均分子量Mwを有する少なくとも1つの無水物変性α−オレフィンポリマーであり、前記平均分子量Mwは、ポリスチレン較正を伴うオルソジクロロベンゼンを用いた150℃におけるゲル浸透クロマトグラフィーによって決定され、
任意にD)成分B)の一部は、粒径D50が800μm未満である膨張黒鉛または該膨張黒鉛と非膨張黒鉛との混合物およびさらなる充填剤としての窒化ホウ素からなる群から選択される少なくとも1つの充填剤で置換されてもよく、黒鉛の場合、成分B)の量の8重量部までが置換されてもよく、窒化ホウ素の場合、成分B)の量の15重量部までが置換されてもよく、
前記成分C)と混合する前の前記成分B)およびC)の量は、成分B)の10重量部ごとに、0.10〜1.4重量部の成分C)が使用されるように互いに調整され、前記組成物はグラフトポリマーおよびポリエステルを含まない。本発明の文脈における成分C)は、文献において言及されるような「衝撃改質剤」ではない。
成分A)
成分A)は、少なくとも1つのポリカーボネートである。したがって、成分A)として混合物を使用することも可能である。本発明の目的のために、ポリカーボネートはホモポリカーボネートまたはコポリカーボネートのいずれかであり;ポリカーボネートは、知られているように、直線状または分岐状であり得る。好ましくは、少なくとも1つのポリカーボネートは芳香族ポリカーボネートである。コポリカーボネートはまた、シロキサン含有ポリカーボネートを意味すると理解される。
または、構造単位(1)は単位の混合物であり、R1は、二価の置換または非置換の芳香族基であるか、またはR1は、二価の直鎖状または環状の脂肪族基である。使用される式(3)のジフェノールの合計重量%に対する芳香族のR1基の割合は60%〜100重量%であり、脂肪族の基の割合は0%〜40重量%である]、
および、
R6およびR7は独立して、H、C1−〜C18−アルキル、C1−〜C18−アルコキシ、ClまたはBr等のハロゲン、またはそれぞれの場合において置換されたアリールまたはアラルキル、好ましくは独立して、HまたはC1−〜C12−アルキル、より好ましくはHまたはC1−〜C8−アルキル、最も好ましくは独立して、Hまたはメチルであり、かつ、
Xは、ヘテロ原子を有するさらなる芳香環と縮合していてもよい−CO−、−O−、−S−、C1−〜C6−アルキレン、C2−〜C5−アルキリデン、C6−〜C10−シクロアルキリデン、またはC6−〜C12−アリーレンである]。
nは、10〜400、好ましくは10〜100、より好ましくは15〜50の平均数であり、
kは0または1であり、
R3は独立して、以下の構造要素(5)または(6)を含む
eは0または2〜12、好ましくは2〜6の自然数であり、eが0の場合、kは1である];
または、式(6)の構造要素
R2、R3、nおよびkは、構造要素(4)についての上記で定義される通りである]。
R2はアリールまたはC1−〜C4−アルキル、好ましくはメチルであり、
Xは単結合、−SO2−、−CO−、−O−、−S−、C1−〜C6−アルキレン、C2−〜C5−アルキリデン、またはヘテロ原子を有するさらなる芳香環と縮合していてもよいC6−〜C12−アリーレンである]。
nは10〜400、好ましくは10〜100、より好ましくは10〜50の平均数であり、
mは1〜10、好ましくは1〜6、特に好ましくは1.5〜5の平均数である。シロキサンブロックの分子量は3000g/モル〜20000g/モル、好ましくは3500g/モル〜15000g/モルであり、上記のように、標準としてジフェノールとしてビスフェノールAからのポリカーボネートを用いて、ゲル浸透クロマトグラフィー(GPC)によって決定される。
本発明によれば、表面処理されていないタルクが成分B)として使用される。これは、タルクが成分A)と混合される前に表面処理されないことを意味する。
本発明の文脈における成分C)は、少なくとも30mgKOH/gの酸価および4000〜40000g/モルの平均分子量Mwを有する無水物変性α−オレフィンポリマーである。これは、成分C)の特徴を満たす様々なポリマーの混合物であってもよい。
Ca)90.0重量%〜98.0重量%、好ましくは92.0重量%〜97.5重量%、より好ましくは94.0重量%〜97.0重量%のα−オレフィンポリマー、および
Cb)2.0重量%〜10.0重量%、好ましくは2.5重量%〜8.0重量%、より好ましくは3.0重量%〜6.0重量%の無水物。
エチレン含有量が80.0重量%〜96.0重量%、好ましくは84.0重量%〜92.0重量%であり、
プロピレン含有量が2.0重量%〜10.0重量%、好ましくは4.0重量%〜8.0重量%であり、かつ、
オクテン含有量が2.0重量%〜10.0重量%、好ましくは4.0重量%〜8.0重量%であることにより特徴付けられる。
任意の成分D)として、有用なさらなる充填剤は、単独の膨張黒鉛、または非膨張黒鉛および/または窒化ホウ素との混合物である。
黒鉛は、成分Dとして、好ましくは単独の膨張黒鉛、または非膨張黒鉛との混合物として、より好ましくは単独の膨張黒鉛として使用される。
本発明によれば、使用される窒化ホウ素は、立方晶窒化ホウ素、六方晶窒化ホウ素、アモルファス窒化ホウ素、部分結晶窒化ホウ素、乱層(turbostratic)窒化ホウ素、ウルツ鉱型窒化ホウ素、菱面体窒化ホウ素および/またはさらなる同素形であり得、六方晶型が好ましい。
本発明の組成物において、成分A)〜C)を混合する前のB)およびC)の量は、成分B)の10重量部ごとに、0.10〜1.4重量部の成分C)が使用されるように互いに調整される。好ましくは、成分B)の10重量部ごとに、0.2〜1.2重量部、より好ましくは0.3〜1.1重量部の成分C)、最も好ましくは0.4〜1.0重量部の成分C)が使用される。
a.i)5〜95重量部、好ましくは30〜80重量部の、
a.i.1)50〜95重量部のスチレン、α−メチルスチレン、メチル環置換スチレン、C1−〜C8−アルキルメタクリレート、特にメチルメタクリレート、C1−〜C8−アルキルアクリレート、特にメチルアクリレート、またはこれらの化合物の混合物、
および
a.i.2)5〜50重量部のアクリロニトリル、メタクリロニトリル、C1−〜C8−アルキルメタクリレート、特にメチルメタクリレート、C1−〜C8−アルキルアクリレート、特にメチルアクリレート、無水マレイン酸、C1−〜C4−アルキルまたはフェニル−N−置換マレイミドまたはこれらの化合物の混合物
の混合物、
a.ii)5〜95重量部、好ましくは20〜70重量部のゴム含有グラフトベース
のグラフトポリマーである。
I.少なくとも1つの(メタ)アクリル酸エステル、またはアクリロニトリルまたは(メタ)アクリル酸エステルとスチレンとの混合物と、
II.グラフトベースとしてのブタジエンラジカルを有するブタジエンポリマー
とのグラフト反応により得られるものでもある。
(a)グラフトベースとしてのアクリレートゴム、および
(b)重合可能なエチレン性不飽和モノマー、およびグラフトモノマーとしてa)の非存在下で形成されるそのホモポリマーまたはコポリマー
のグラフトポリマーでもある。
本発明の多層体は、基材層I)に直接結合する金属層を有する。この金属層は、好ましくは、アルミニウム、銀、クロム、チタンおよびパラジウムからなる群から選択される少なくとも1つの金属を含む。より好ましくは、金属層は、銀またはアルミニウム、特に好ましくはアルミニウムを含む。
さらに、本発明の多層体は、保護層III)を有していてもよい。これは、好ましくは防食層であり、多層体の金属層が耐候性効果に曝される場合に存在することが好ましい。
さらなる実施形態において、少なくとも1つの追加の層(IV)が存在してもよい。これは、互いに直接結合している層I)とII)との間を除いて、多層体のどの点に存在していてもよい。
本発明のさらなる態様において、本発明の多層体を製造する方法が提供され、この方法は、
(a)成分A)〜D)および必要に応じて追加の添加剤を含む組成物の射出成形または押出しによって基材層(I)を、好ましくは射出成形操作において温度可変成形レジーム(variothermal mould regime)を用いて成形する工程、
(b)工程(a)で得られた層に、プラズマ加工により金属層(II)を適用する工程、
(c)任意に、少なくとも1つの追加の層(IV)を適用する工程、
(d)任意に、工程(b)または(c)で得られた複合材に保護層(III)を適用する工程
を含む。
さらなる態様において、本発明は、少なくとも30mgKOH/gの酸価、および4000〜25000g/モルの平均分子量Mwを有する少なくとも1つの無水物変性α−オレフィンポリマーC)の多層体の基材層の製造のための使用に関し、平均分子量Mwが、ポリスチレン較正を伴うオルトジクロロベンゼンを用いた150℃におけるゲル浸透クロマトグラフィーによって決定され、
多層体は、少なくとも1つの基材層、基材層に直接結合する金属層および任意に金属層の上の少なくとも1つの保護層を含み、
基材層は、少なくとも成分A)〜D)を混合することにより得られる組成物を含み、
A)少なくとも1つのポリカーボネートであり、かつ
B)は少なくとも一種のタルクである。
PC1:平均分子量Mwが約31000g/モル、軟化温度(VST/B 120〜ISO 306:2014−3)が150℃の、紫外線吸収剤を含まない、Covestro Deutschland AG社製の直鎖状ビスフェノールAポリカーボネート。ISO 1133:2012−03の300℃、1.2kg負荷でのメルトボリュームフローレート(MVR)は6.0cm3/(10分)であった。
Claims (15)
- I)基材層(S)、
II)前記基材層に直接結合する金属層(M)および
III)任意に、前記金属層上の保護層(P)
を有する多層体であって、
前記基材層は、成分A)〜D)を混合することにより得られる組成物を含み、
A)はポリカーボネートであり、
B)は、中央粒径D50が0.01〜9.5μmである表面処理されていないタルクであり、前記粒径D50は沈降分析によって決定され、
C)は、DIN ISO 17025:2005に従ってアルコール性水酸化カリウム溶液を用いた電位差滴定によって決定される、少なくとも30mgKOH/gの酸価、および4000〜40000g/モルの平均分子量Mwを有する少なくとも1つの無水物変性α−オレフィンポリマーであり、前記平均分子量Mwは、ポリスチレン較正を伴うオルトジクロロベンゼンを用いた150℃におけるゲル浸透クロマトグラフィーにより決定され、
任意にD)成分B)の一部は、粒径D50が800μm未満である膨張黒鉛または該膨張黒鉛と非膨張黒鉛との混合物およびさらなる充填剤としての窒化ホウ素からなる群から選択される少なくとも1つの充填剤で置換されてもよく、黒鉛の場合、成分B)の量の8重量部までが置換されてもよく、窒化ホウ素の場合、成分B)の量の15重量部までが置換されてもよく、
前記成分C)と混合する前の前記成分B)およびC)の量は、成分B)の10重量部ごとに、0.10〜1.4重量部の成分C)が使用されるように互いに調整され、前記組成物はグラフトポリマーおよびポリエステルを含まない、前記多層体。 - 前記B)の量が、全組成物を基準として12重量%〜45重量%である、請求項1に記載の多層体。
- 前記B)の量が、全組成物を基準として18重量%〜35重量%である、請求項1または2に記載の多層体。
- 前記混合する前の前記B)およびC)の量が、成分B)の10重量部ごとに、0.25〜1.4重量部の成分C)が使用されるように互いに調整される、請求項1〜3のいずれか一項に記載の多層体。
- 前記成分B)のタルクまたはタルク混合物が8〜10のpHを有し、該タルクまたはタルク混合物のpHがEN ISO 787−9:1995に従って決定される、請求項1〜4のいずれか一項に記載の多層体。
- 前記成分B)が0.5〜3.0μmの中央粒径D50を有し、該粒径D50が沈降分析により決定される、請求項1〜5のいずれか一項に記載の多層体。
- 前記成分B)が7.5〜20.0m2/gのBET表面積を有する、請求項1〜6のいずれか一項に記載の多層体。
- 前記基材層が0.1mm〜6.0mmの厚さを有し、前記金属層が10nm〜1000nmの厚さを有し、前記任意の保護層が5nm〜200nmの厚さを有する、請求項1〜7のいずれか一項に記載の多層体。
- 前記金属層が、アルミニウム、銀、クロム、チタンおよびパラジウムからなる群から選択される少なくとも1つの金属を含む、請求項1〜8のいずれか一項に記載の多層体。
- 前記金属層が銀またはアルミニウムを含む、請求項1〜9のいずれか一項に記載の多層体。
- 黒鉛が前記成分D)として存在する場合、成分B)の量の2〜7重量部が置換されており、窒化ホウ素が前記成分D)として存在する場合、成分B)の量の2〜12重量部が置換されている、請求項1〜10のいずれか一項に記載の多層体。
- 請求項1〜11のいずれか一項に記載の多層体を含む光源および熱源の反射体および構成要素。
- 請求項1〜11のいずれか一項に記載の多層体の製造方法であって、
(a)少なくとも成分A)〜C)を含み、任意に成分D)を含む、組成物の射出成形または押出しによって基材層を形成する工程、
(b)工程(a)で得られた層に、プラズマ加工により金属層を適用する工程、
(c)任意に、少なくとも1つの追加の層を適用する工程、および
(d)任意に、工程(b)または(c)で得られた層に保護層を適用する工程
を含む、前記製造方法。 - 少なくとも30mgKOH/gの酸価、および4000〜25000g/モルの平均分子量Mwを有する少なくとも1つの無水物変性α−オレフィンポリマーC)の多層体の基材層の製造のための使用であって、前記平均分子量Mwは、ポリスチレン較正を伴うオルトジクロロベンゼンを用いた150℃におけるゲル浸透クロマトグラフィーによって決定され、
前記多層体は、少なくとも1つの基材層、前記基材層に直接結合する金属層および任意に前記金属層の上の少なくとも1つの層を含み、
前記基材層は、少なくとも成分A)〜D)を混合することにより得られる組成物を含み、
A)はポリカーボネートであり、
B)は表面処理されていないタルクであり、
任意にD)成分B)の一部を、粒径D50が800μm未満である膨張黒鉛または該膨張黒鉛と非膨張黒鉛との混合物およびさらなる充填剤としての窒化ホウ素からなる群から選択される少なくとも1つの充填剤で置換されてもよい、前記使用。 - 前記混合する前の前記B)およびC)の量が、成分B)の10重量部ごとに、0.25〜1.4重量部の成分C)が使用されるように互いに調整される、請求項14に記載の使用。
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- 2018-12-17 TW TW107145407A patent/TW201936778A/zh unknown
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JP2016049629A (ja) * | 2014-08-28 | 2016-04-11 | 三菱化学株式会社 | 積層体 |
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Publication number | Publication date |
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EP3502306B1 (de) | 2022-03-02 |
CN111479948A (zh) | 2020-07-31 |
US20220135755A1 (en) | 2022-05-05 |
KR20200100638A (ko) | 2020-08-26 |
WO2019121256A1 (de) | 2019-06-27 |
CN111479948B (zh) | 2022-12-27 |
US12012494B2 (en) | 2024-06-18 |
EP3502306A1 (de) | 2019-06-26 |
TW201936778A (zh) | 2019-09-16 |
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