TWI769156B - 用於使聚酯對水解穩定之組成物 - Google Patents
用於使聚酯對水解穩定之組成物 Download PDFInfo
- Publication number
- TWI769156B TWI769156B TW106114528A TW106114528A TWI769156B TW I769156 B TWI769156 B TW I769156B TW 106114528 A TW106114528 A TW 106114528A TW 106114528 A TW106114528 A TW 106114528A TW I769156 B TWI769156 B TW I769156B
- Authority
- TW
- Taiwan
- Prior art keywords
- polyester
- formula
- compound
- terephthalate
- polyester material
- Prior art date
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/10—Esters; Ether-esters
- C08K5/12—Esters; Ether-esters of cyclic polycarboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
- C07C69/76—Esters of carboxylic acids having a carboxyl group bound to a carbon atom of a six-membered aromatic ring
- C07C69/80—Phthalic acid esters
- C07C69/82—Terephthalic acid esters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
- C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
- C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
- C08J3/226—Compounding polymers with additives, e.g. colouring using masterbatch techniques using a polymer as a carrier
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
- C08K5/3477—Six-membered rings
- C08K5/3492—Triazines
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2467/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2467/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2469/00—Characterised by the use of polycarbonates; Derivatives of polycarbonates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/16—Applications used for films
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2310/00—Masterbatches
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
Description
本發明係關於抗水解聚酯膜(hydrolysis-resistant polyester film)。
聚酯膜為眾所周知的。然而,不穩定的聚酯膜的缺點是它們對水解的敏感性,特別是在高於特定聚酯的玻璃轉化溫度(glass transition temperature)的溫度。對水解的敏感性是聚酯在潮濕條件下水解降解的性質,這可以在例如IV值降低中看出。這是使用聚酯膜的限制因素,特別是在高溫應力應用中,例如在膜電容器、電纜護套,帶狀電纜,馬達保護膜,電池膜,地板膜,窗膜,光伏背板,亦在長期應用中,如玻璃窗(glazing)和戶外應用。
在脂肪族聚酯中觀察到特別顯著的水解敏感性,而且也與芳族聚酯如PBT和PET一起觀察到。當PET的水解趨勢對於應用來說太大時,必須訴諸於水解穩定的PEN或甚至其它聚合物如聚醚或聚亞醯胺。然而,它們比 PET貴得多,因而就經濟理由而言是不利的。
因此,已經提出藉由併入水解穩定劑以改良聚酯膜的水解穩定性。
已知藉由使用碳二亞胺(carbodiimide),獲得抗水解聚酯原料(US-A-5,885,709,EP-A-0838500,CH-A-621 135)。然而,由這種聚合物製備的膜傾向於在製造過程中以及後來應用中排出對黏膜有刺激性的異氰酸酯或者釋放其它有害的副產物和降解產物。以環氧基為基礎的水解穩定劑亦給予水解穩定化作用,並例如描述於EP-A-0 292 251或US-A-3,657,191。然而,這些化合物基於藉由表氯醇(epichlorohydrin)的環氧乙烷(oxirane)生成,但顯示出切割低分子量有毒化合物的傾向,因而產生與使用碳二亞胺(carbodiimide)相關的類似問題。再者,它們併入聚酯基質(polyester matrix)中不足,造成長反應時間與高濁度的定向聚酯膜。
再者,已知的水解穩定劑例如碳二亞胺(carbodiimide)與其他物質,如EP-A-0 292 251所述的那些,具有的缺點為它們有時導致聚合物在擠出(extrusion)過程中分子量強烈增加(黏度增加),從而使擠出(extrusion)過程不穩定並且難以控制。
因此,本發明之目的係提供一種可獲得之抗水解聚酯原料,其避免先前技術所述之缺點。
該目的令人意外地通過聚酯製品,較佳為含有基於對苯二甲酸酯(terephthalic acid ester)的水解穩定劑的膜來實現。
其中R1與R2為相同或是不同,並且代表C1-C10-烷基,較佳為C1-C6-烷基,更佳為C1-C4-烷基,最佳為C1-C2-烷基,作為聚酯材料中的水解穩定劑。
式(1)之化合物的例子為對苯二甲酸二甲酯(dimethylterephthalat)、對苯二甲酸二乙酯(diethylterephthalat)、對苯二甲酸二丙酯(dipropylterephthalat)、對苯二甲酸二丁酯(dibutylterephthalat)、對苯二甲酸二戊酯(dipentylterephthalat)、對苯二甲酸二己酯(dihexylterephthalat)、對苯二甲酸二庚酯(diheptylterephthalat)、對苯二甲酸二辛酯(dioctylterephthalat)、對苯二甲酸二壬酯(dinonylterephthalat)、或對苯二甲酸二癸酯(didecylterephthalat)。
藉由對二甲苯(p-xylene)上的甲基之氧化作用以及與甲醇反應形成甲酯而製造此分子,即對苯二甲酸二甲酯。
水解穩定劑的比例範圍以聚酯重量為基準計較佳為自0.1至20.0wt.%,更佳為1.0至10.0wt.%,以及特佳為1.5至5wt.%。
若併入母料(masterbatch)中,則水解穩定劑的比例各以母料總重量為基準計通常為自0.1至50.0wt.%,較佳為1.0至20.0wt.%。
合適的聚酯為例如聚對苯二甲酸乙二酯(polyethylene terephthalate,PET)、聚萘二甲酸乙二酯(polyethylene naphthalate,PEN)、聚對苯二甲酸丁二酯(polybutylene terephthalate,PBT)、聚對苯二甲酸丙二酯(polytrimethylene terephthalate,PTT)、二苯甲醯基聚對苯二甲酸乙二酯(dibenzoyl polyethylene terephthalate,PETBB)、二苯甲醯基聚對苯二甲酸丁二酯(dibenzoyl polybutylene terephthalate,PBTBB)、二苯甲醯基聚萘二甲酸乙二酯(dibenzoyl polyethylene naphthalate,PENBB)或其混合物。較佳為PET、PBT、PEN與PTT,以及其混合物與共聚酯。
合適的聚酯亦為脂肪族聚酯,例如聚羥基丁酸酯(polyhydroxybutyrate,PHB)以及其與聚羥基戊酸酯(polyhydroxyvalerate,PHV)、聚羥基丁酸酯-戊酸酯(polyhydroxybutyrate-valerate,PHBV)及聚(ε-己內酯)(poly(ε-caprolactone),PCL)、SP 3/6、4/6 SP(由1,3-丙二醇/己二酸酯或1,4-丁二醇/己二酸酯組成)、聚己內醯胺或一般己二酸聚酯以及其他脂肪族羧酸的酯類之共聚物。
本發明所使用的聚酯可另包含無機或有機顆粒,其需要用於調整表面形貌或光學性質,並且在本文後續內容中稱為聚酯組成物。該顆粒的量取決於用途及其顆粒尺寸。後者範圍通常為0.01至30.0,較佳為0.1至5.0,特別為0.3至3.0微米。
用於得到粗糙度的合適化合物例如碳酸鈣、硫酸鋇、磷灰石(apatite)、二氧化矽、二氧化鈦、氧化鋁、交聯的聚苯乙烯、交聯的PMMA、沸石(zeolite),以及其他矽酸鹽,例如矽酸鋁。這些化合物一般使用量為(以聚酯組成物總重量為基準計)0.05至5wt.%,較佳為0.1至0.6wt.%。
除了上述添加物之外,聚酯組成物可另含有其他成分,例如阻燃劑與/或自由基捕捉劑與/或其他聚合 物(例如聚醚醯亞胺(polyetherimide))、色素與染劑、穩定劑、抗氧化劑、抗菌劑、熱穩定劑、光穩定劑、中和劑、抗靜電劑、抗阻塞劑、增亮劑、重金屬去活化劑、疏水劑、過氧化物、水捕捉劑、酸捕捉劑、水滑石、彈性體、衝擊改質劑、雷射標記添加物、加工助劑、以及其混合物。
較佳係藉由母料技術添加式(1)的水解穩定劑。為達此目的,先將水解穩定劑分散於載體材料中。合適的支撐材料(support material)為聚酯本身,例如聚對苯二甲酸乙二酯或可與個別聚酯相容的其他聚合物。依照載體樹脂,母料可為固體或液體,較佳為固體。在將母料加入至聚酯材料中之後,母料的成分在擠出(extrusion)過程中熔化,並且溶解或細微分散於聚酯中。由於水解穩定劑物理性均質地分散於載體中,而母料與聚酯混合,水解穩定劑的局部較高濃度之可能性最小化。再者,當導入至成形(molding)設備中時,藉由增加熔化濃縮物所需的時間來防止在脫氣(let down)聚合物內的水解穩定劑的過早反應。此延遲的反應時間允許水解穩定劑完全分散在整個聚合物中。
式(1)的水解穩定劑可併入待穩定化的聚酯材料中,如下所述:將待生產的母料之載體材料與水解穩定劑饋入至擠壓器(extruder)中,較佳為雙螺桿擠壓器,熔化、混合,而後經由穿孔的模(die)擠出、淬火(quenched)以及 造粒。較佳的方法為在擠壓器中先熔化聚合物,並且在除氣之後,將水解穩定劑直接計量至熔化物(melt)中。
水解穩定化的聚酯材料有利加工成為聚合物製品,例如片、膜、容器、或纖維。特別較佳為片與膜。
有利的是,水解穩定化的聚酯製品(例如膜)包含其他習用的聚合物穩定劑,例如自由基捕捉劑、光穩定劑、或是熱穩定劑,有利的量為以製品總重量為基準計的50至15,000ppm,較佳為100至5,000ppm,更佳為300至1000ppm。所添加的聚合物穩定劑可選自於主要穩定劑的群組,例如空間阻礙酚(sterically hindered phenol)或二級芳香族胺,或是選自於次要穩定劑的群組,例如硫醚、膦酸酯(phosphonite)與二丁基二硫代胺甲酸鋅(zinc dibuthyl-dithio-carbamate),或是主要與次要穩定劑的混合物。較佳為酚類(phenolic)穩定劑。酚類穩定劑中特別較佳為空間阻礙酚、硫代雙酚(thiobisphenol)、亞烷基雙酚(alkylidenebisphenol)、烷基酚、羥苄基化合物、醯基-胺基(acyl-amino)以及羥基苯基丙酸酯(hydroxyphenylpropionate)。
在膜中亦有利地使用UV吸收劑,以苯并三氮唑(benzotriazole)為基礎,如Tinuvin 1577、Tinuvin 1600、Tinuvin 360、Tinuvin 234、Cyasob 3638、Cyasorb 1164,用於戶外應用。這些添加物所添加的量可以膜總重量為基準計之0.1至20.0wt.%,較佳為1.0至10.0wt.%,以及更佳為1.5至5wt.%。
除了添加母料形式的水解穩定劑之外,可在聚酯製品(例如膜)生產過程中,直接添加水解穩定劑。當使用雙螺桿擠出器且水解穩定劑直接計量於個別擠出器中的熔化物中時,得到特別良好的結果。
可藉由習知用於生產單層與多層膜的擠出製程而製備膜。水解穩定劑較佳存在於所有層中,實施例中並非以水解穩定劑修飾所有層也是可能的。
通常,經由平坦膜模(flat-film die)擠出個別熔化物,將在一或多個滾輪(冷卻軋輥(cooling roll)上用於固化之所得膜取出作為實質無定形預膜,並且淬火(quench),而後將該膜再加熱且雙軸拉伸(定向),以及將雙軸拉伸的膜熱定型(heat-set)。雙軸拉伸在機器方向(=MD)上依次進行,然後橫向地垂直於機器方向(=TD)。這形成分子鏈的定向(orientation)。
進行定向的溫度範圍可於相對廣的範圍變化,並且取決於所需要的膜性質。可任選地同時進行第一縱向拉伸與橫向拉伸(同時拉伸)。
相較於未改質的(unmodified)聚酯膜,以此方式產生的膜於室溫及達210℃之溫度二者水解的趨勢低得多。此穩定化作用主要與膜厚度與溫度無關。
特別令人驚訝的是在膜生產過程中,儘管良好長期水解,但在膜生產過程中,擠出器中未發生不想要的黏度增加,並且未觀察到增加的凝膠或斑點量。
以式(1)之水解穩定劑穩定化的膜對於生產包 含應具有長壽命(超過1年)的聚酯膜之產物是理想的,並且使用在處於高溫(超過80℃)與高濕度的應用中。
式(1)的穩定劑特別有用於膜電容器(較佳厚度範圍為0.3至12微米)的生產。關於電容器的製造,已經證實當膜在200℃的縱向收縮率小於4%,橫向收縮率小於1%時是有利的,它特別適合用於製造SMD電容器。
另一個應用是汽車中的帶狀電纜。
在以下的實施方案中,個別性質的量測係根據核准的標準方法。百分比為重量百分比,除非另有說明。
此種測試快速提供關於水解阻力係數(resistivity)的資訊。在高壓滅菌之前,將樣品切割,並在120℃和2巴(abs)下保存0、40、50小時。對於每個測試,量測五個測試樣品。
此種測試以長期程序提供關於水解阻力係數的資訊。在高壓滅菌之前,將樣品切割,並在85℃和正常 壓力下保存長達5000小時,在每500小時後,量測測試結果。
用符合ISO 527-1/2的100mm的鋁夾具進行抗拉測試,以得到斷裂伸長(elongation at break)與抗拉強度(tensile strength)。結果為五個量測的平均值。
測試速度:-ε<0.25%:1mm/min
-ε>0.25%:100mm/min
由於固有黏度為聚合物分子量的獨特功能,因而固有黏度(I.V.)的量測用以量測聚合物的分子量。藉由使用Davenport黏度計,偵測I.V.作為熔化物黏度量測,例如對於PET,在熔化狀態下使用高壓氮氣經由校準模(calibrated die)擠出。
標準黏度(Standard viscosity,S.V.)
標準黏度S.V.係基於DIN 53726。在25℃於Ubbelohde黏度計中藉由量測於二氯乙酸(dichloroacetic acid,DCA)中1%溶液之相對黏度ηrel。S.V.值定義如下:S.V.=(ηrel-1).1000 S.V.=(ηrel-1)×1000
使用以下材料:PET1:(XPURE 4004,Invista,I.V.0.63)
PET2:regranulat RT4027(Invista/Erema)
PET3:RAMAPET R 180 GR BB(Indorama Plastics)
PC(聚碳酸酯):(Trirex 3022PJ(01)Entec)
水解穩定劑:DMT(對苯二甲酸二甲酯)
使用雙螺桿擠出器Leistritz MASS技術(27mm/40D),製造兩種母料(Masterbatch,MB)。MBHS含有10%的DMT於PC上,用於水解穩定化作用。MBUV含有15%的UV吸收劑Tinuvin 1577於PET3上。
以ABA結構產生三層膜。核心層B的組成係由53% PET1、15% PET 2、2% MBHS、30% MBUV組成。外層A係由67% PET1、3% MBHS、30% MBUV組成。於100-170℃預先乾燥所使用的PET。主要擠出器配備~10mbar真空。共擠出器(coextruder)配備~20mbar真空。
不同區域的擠出溫度如表1所示。
熔化的聚合物從牽引輥(draw roller)的噴嘴排出。該膜以係數3.0沿機器方向拉伸,並且以係數3.4於交叉拉伸中拉伸。接著,於225℃將該膜熱定型,並且於220-180℃溫度下沿橫向方向鬆弛3%。最終膜厚度為50微米。
以ABA結構生產三層膜。核心層B的組成由45% PET1、25% PET 2、30% MBUV組成。外層A係由70% PET1、30% MBUV組成。於100-170℃預先乾燥所使用的PET。主要擠出器配備~10mbar真空。共擠出器(coextruder)配備~20mbar真空。
不同區域的擠出溫度如表2所示。
熔化的聚合物從牽引輥(draw roller)的噴嘴排出。該膜以係數3.0沿機器方向拉伸,並且以係數3.4於交叉拉伸中拉伸。接著,於225℃將該膜熱定型,並且於220-180℃溫度下沿橫向方向鬆弛3%。最終膜厚度為50微米。
實施例1的測試結果,其在所有模擬聚合物的 水解降解(hydrolysis degradation)之測試中含有抗水解添加物。在壓力鍋測試中,該膜比沒有抗水解添加物之膜保持明顯更長的穩定性。再者,在濕熱測試中,具有抗水解添加物的材料比未配備之膜抗性明顯更長。再者,熔化物黏度與標準黏度的量測顯示較穩定的材料是配備抗水解添加物的材料。實施例1的所有膜顯示高UV穩定性。
Claims (12)
- 如申請專利範圍第1項之方法,其中該式(1)之化合物為對苯二甲酸二甲酯(dimethylterephthalate)、對苯二甲酸二乙酯(diethylterephthalate)、對苯二甲酸二丙酯(dipropylterephthalate)、對苯二甲酸二丁酯(dibutylterephthalate)、對苯二甲酸二戊酯(dipentylterephthalate)、對苯二甲酸二己酯(dihexylterephthalate)、對苯二甲酸二庚酯(diheptylterephthalate)、對苯二甲酸二辛酯 (dioctylterephthalate)、對苯二甲酸二壬酯(dinonylterephthalate)、或對苯二甲酸二癸酯(didecylterephthalate)。
- 如申請專利範圍第1或2項之方法,其中該式(1)之化合物為對苯二甲酸二甲酯(dimethylterephthalate)。
- 如申請專利範圍第1項之方法,其中該聚酯材料中的聚酯為聚對苯二甲酸乙二酯(polyethylene terephthalate)、聚萘二甲酸乙二酯(polyethylene naphthalate)、聚對苯二甲酸丁二酯(polybutylene terephthalate)、聚對苯二甲酸丙二酯(polytrimethylene terephthalate)、二苯甲醯基聚對苯二甲酸乙二酯(dibenzoyl polyethylene terephthalate)、二苯甲醯基聚對苯二甲酸丁二酯(dibenzoyl polybutylene terephthalate)、二苯甲醯基聚萘二甲酸乙二酯(dibenzoyl polyethylene naphthalate)或其混合物。
- 如申請專利範圍第1項之方法,其中該聚酯材料中的該聚酯為聚對苯二甲酸乙二酯(polyethylene terephthalate)、聚對苯二甲酸丁二酯(polybutylene terephthalate)、聚萘二甲酸乙二酯(polyethylene naphthalate)、聚對苯二甲酸丙二酯(polytrimethylene terephthalate)、及其混合物與共聚酯。
- 如申請專利範圍第1項之方法,其中該聚酯材料中的 該聚酯為脂肪族聚酯,其選自於由聚羥基丁酸酯(polyhydroxybutyrate)以及其與聚羥基戊酸酯(polyhydroxyvalerate)、聚羥基丁酸酯-戊酸酯(polyhydroxybutyrate-valerate)及聚(ε-己內酯)(poly(ε-caprolactone))的共聚物所組成的群組。
- 如申請專利範圍第1項之方法,其中該式(1)之化合物的比例,以該經穩定化的聚酯材料之重量為基準計為1.0至10.0wt.%。
- 如申請專利範圍第1項之方法,其中該式(1)之化合物的比例,以該經穩定化的聚酯材料之重量為基準計為1.5至5.0wt.%。
- 如申請專利範圍第1項之方法,其中該式(1)之化合物係與其他添加物結合使用,該其他添加物選自於由自由基捕捉劑(radical scavenger)、光穩定劑、熱穩定劑、阻燃劑、色素、染劑、抗氧化劑、抗菌劑、中和劑、抗靜電劑、抗結塊劑(antiblocking agent)、光學增亮劑、重金屬去活化劑、疏水劑、過氧化物、水捕捉劑(water scavenger)、酸捕捉劑、水滑石(hydrotalcite)、彈性體、衝擊改質劑、雷射標記添加物、加工助劑(processing aid)、及其混合物所組成的群組。
- 如申請專利範圍第1項之方法,其中該式(1)之化合物 係與UV吸收劑結合使用。
- 如申請專利範圍第1項之方法,其中該式(1)之化合物係以母料(masterbatch)的形式使用。
- 如申請專利範圍第1項之方法,其中該聚酯材料係膜或片的形式。
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP16168305.7A EP3241866A1 (en) | 2016-05-04 | 2016-05-04 | Composition for polyester hydrolytic stabilization |
??16168305.7 | 2016-05-04 | ||
EP16168305.7 | 2016-05-04 |
Publications (2)
Publication Number | Publication Date |
---|---|
TW201811888A TW201811888A (zh) | 2018-04-01 |
TWI769156B true TWI769156B (zh) | 2022-07-01 |
Family
ID=55913508
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
TW106114528A TWI769156B (zh) | 2016-05-04 | 2017-05-02 | 用於使聚酯對水解穩定之組成物 |
Country Status (13)
Country | Link |
---|---|
US (1) | US10808101B2 (zh) |
EP (2) | EP3241866A1 (zh) |
JP (1) | JP7113759B2 (zh) |
KR (1) | KR102404837B1 (zh) |
CN (1) | CN109153816B (zh) |
BR (1) | BR112018070575B1 (zh) |
CA (1) | CA3022923A1 (zh) |
ES (1) | ES2861312T3 (zh) |
MX (1) | MX2018012428A (zh) |
RU (1) | RU2763499C2 (zh) |
SG (1) | SG11201808508TA (zh) |
TW (1) | TWI769156B (zh) |
WO (1) | WO2017190993A1 (zh) |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20130320594A1 (en) * | 2011-02-18 | 2013-12-05 | Keith Bechard | Methods for recycling post-consumer mixed rigid plastics |
Family Cites Families (22)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE1929149A1 (de) | 1969-06-09 | 1970-12-23 | Hoechst Ag | Verfahren zur Endgruppenmodifizierung von Polyestern |
CH621135A5 (en) | 1976-05-05 | 1981-01-15 | Inventa Ag | Process for improving the hydrolysis stability of fibre- and film-forming polyesters |
KR840000471A (ko) * | 1982-07-30 | 1984-02-22 | 이용철 | 재생 bhet의 정제방법 |
US4680372A (en) * | 1986-02-25 | 1987-07-14 | Celanese Corporation | In-situ end-capping melt prepared aromatic polyester with phenyl benzoate |
US4879328A (en) | 1987-05-18 | 1989-11-07 | Toray Industries | Aromatic polyester composition and process for producing the same |
JP3228977B2 (ja) | 1991-03-14 | 2001-11-12 | ジョーンズ・マンヴィル・インターナショナル・インコーポレーテッド | カルボジイミド変性ポリエステル繊維およびその製造方法 |
AU712542B2 (en) * | 1995-06-07 | 1999-11-11 | Nike Ihm, Inc. | Membranes of polyurethane based materials including polyester polyols |
US5763538A (en) | 1996-10-28 | 1998-06-09 | E. I. Du Pont De Nemours And Company | Process for making an oriented polyester article having improved hydrolytic stability |
DE10063497A1 (de) | 2000-12-20 | 2002-07-04 | Bayer Ag | Polyurethanelastomere mit verbesserter Hydrolysestabilität |
JP4220770B2 (ja) * | 2002-12-11 | 2009-02-04 | 三菱樹脂株式会社 | 印刷層を有する成形体、および、その製造方法 |
DE102004044326A1 (de) * | 2004-09-10 | 2006-03-16 | Mitsubishi Polyester Film Gmbh | Hydrolysebeständige Folie aus einem Polyester mit Hydrolyseschutzmittel sowie Verfahren zu ihrer Herstellung und ihre Verwendung |
US8372912B2 (en) * | 2005-08-12 | 2013-02-12 | Eastman Chemical Company | Polyvinyl chloride compositions |
AU2009204056A1 (en) * | 2008-01-09 | 2009-07-16 | Performance Materials Na, Inc. | Polyester composition resistant to hydrolysis |
CN101759961A (zh) * | 2008-11-24 | 2010-06-30 | 东丽纤维研究所(中国)有限公司 | 一种耐水解聚酯组合物及其制备方法 |
EP2221336A1 (en) * | 2009-02-19 | 2010-08-25 | Mitsubishi Plastics, Inc. | Biaxially oriented polyester film with favorable light shielding properties, having hydrolysis resistance |
EP2406319A2 (en) * | 2009-03-13 | 2012-01-18 | Basf Se | Stabilized blends of polyester and polyamide |
GB0915687D0 (en) * | 2009-09-08 | 2009-10-07 | Dupont Teijin Films Us Ltd | Polyester films |
US8658285B2 (en) * | 2010-06-09 | 2014-02-25 | Toray Plastics (America), Inc. | Optically clear UV and hydrolysis resistant polyester film |
GB2488787A (en) * | 2011-03-07 | 2012-09-12 | Dupont Teijin Films Us Ltd | Stabilised polyester films |
EP2738204B1 (en) * | 2012-11-29 | 2019-01-09 | Solvay Specialty Polymers USA, LLC. | Polyester compositions with improved crystallization rate |
CN103694655B (zh) * | 2013-12-09 | 2015-12-02 | 方万漂 | 耐湿热聚对苯二甲酸丁二醇酯 |
CN104045980B (zh) * | 2014-05-24 | 2016-01-27 | 池州万维化工有限公司 | 一种抗水解pet色母粒及其制备方法和用途 |
-
2016
- 2016-05-04 EP EP16168305.7A patent/EP3241866A1/en not_active Withdrawn
-
2017
- 2017-04-26 SG SG11201808508TA patent/SG11201808508TA/en unknown
- 2017-04-26 MX MX2018012428A patent/MX2018012428A/es unknown
- 2017-04-26 BR BR112018070575-6A patent/BR112018070575B1/pt active IP Right Grant
- 2017-04-26 CN CN201780027346.2A patent/CN109153816B/zh active Active
- 2017-04-26 ES ES17719586T patent/ES2861312T3/es active Active
- 2017-04-26 CA CA3022923A patent/CA3022923A1/en active Pending
- 2017-04-26 EP EP17719586.4A patent/EP3452542B1/en active Active
- 2017-04-26 US US16/098,467 patent/US10808101B2/en active Active
- 2017-04-26 WO PCT/EP2017/059848 patent/WO2017190993A1/en active Application Filing
- 2017-04-26 KR KR1020187035206A patent/KR102404837B1/ko active IP Right Grant
- 2017-04-26 JP JP2018557133A patent/JP7113759B2/ja active Active
- 2017-04-26 RU RU2018142568A patent/RU2763499C2/ru active
- 2017-05-02 TW TW106114528A patent/TWI769156B/zh active
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20130320594A1 (en) * | 2011-02-18 | 2013-12-05 | Keith Bechard | Methods for recycling post-consumer mixed rigid plastics |
Also Published As
Publication number | Publication date |
---|---|
RU2018142568A (ru) | 2020-06-04 |
RU2018142568A3 (zh) | 2020-08-26 |
EP3452542A1 (en) | 2019-03-13 |
TW201811888A (zh) | 2018-04-01 |
BR112018070575A2 (pt) | 2019-02-12 |
EP3452542B1 (en) | 2021-02-24 |
WO2017190993A1 (en) | 2017-11-09 |
CA3022923A1 (en) | 2017-11-09 |
KR20190005922A (ko) | 2019-01-16 |
JP2019515102A (ja) | 2019-06-06 |
RU2763499C2 (ru) | 2021-12-29 |
MX2018012428A (es) | 2019-03-01 |
KR102404837B1 (ko) | 2022-06-07 |
SG11201808508TA (en) | 2018-10-30 |
US20190153195A1 (en) | 2019-05-23 |
ES2861312T3 (es) | 2021-10-06 |
BR112018070575B1 (pt) | 2022-09-27 |
JP7113759B2 (ja) | 2022-08-05 |
EP3241866A1 (en) | 2017-11-08 |
CN109153816A (zh) | 2019-01-04 |
US10808101B2 (en) | 2020-10-20 |
CN109153816B (zh) | 2021-05-14 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP5972406B2 (ja) | 耐加水分解性ポリエステルフィルム | |
JP5036153B2 (ja) | ポリエステルフィルム及びその製造方法 | |
JP5036154B2 (ja) | ポリエステルフィルム及びその製造方法 | |
JP5280673B2 (ja) | 二軸延伸ポリエステルフィルム及びその製造方法 | |
JP5633255B2 (ja) | ポリエステル組成物 | |
EP2788427A1 (en) | Biopolyester composition with good transparency and sliding properties | |
TWI769156B (zh) | 用於使聚酯對水解穩定之組成物 | |
EP3452541B1 (en) | Composition for polyester hydrolytic stabilization |