CN1753948A - 低温－可热合聚酯薄膜及其生产方法 - Google Patents

低温－可热合聚酯薄膜及其生产方法 Download PDF

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Publication number
CN1753948A
CN1753948A CNA018229913A CN01822991A CN1753948A CN 1753948 A CN1753948 A CN 1753948A CN A018229913 A CNA018229913 A CN A018229913A CN 01822991 A CN01822991 A CN 01822991A CN 1753948 A CN1753948 A CN 1753948A
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Prior art keywords
film
multipolymer
homopolymer
temperature
blend
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CN100384935C (zh
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J·V·库里安
D·M·哈姆
B·A·斯米利
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EIDP Inc
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EI Du Pont de Nemours and Co
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
    • B29C48/07—Flat, e.g. panels
    • B29C48/08—Flat, e.g. panels flexible, e.g. films
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
    • B29C48/09—Articles with cross-sections having partially or fully enclosed cavities, e.g. pipes or channels
    • B29C48/10—Articles with cross-sections having partially or fully enclosed cavities, e.g. pipes or channels flexible, e.g. blown foils
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/88—Thermal treatment of the stream of extruded material, e.g. cooling
    • B29C48/911—Cooling
    • B29C48/9135—Cooling of flat articles, e.g. using specially adapted supporting means
    • B29C48/914—Cooling of flat articles, e.g. using specially adapted supporting means cooling drums
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B29C65/02—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B29C65/02—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure
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    • B29C66/7311—Thermal properties
    • B29C66/73117—Tg, i.e. glass transition temperature
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    • B29C66/70—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material
    • B29C66/73—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the intensive physical properties of the material of the parts to be joined, by the optical properties of the material of the parts to be joined, by the extensive physical properties of the parts to be joined, by the state of the material of the parts to be joined or by the material of the parts to be joined being a thermoplastic or a thermoset
    • B29C66/737—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the intensive physical properties of the material of the parts to be joined, by the optical properties of the material of the parts to be joined, by the extensive physical properties of the parts to be joined, by the state of the material of the parts to be joined or by the material of the parts to be joined being a thermoplastic or a thermoset characterised by the state of the material of the parts to be joined
    • B29C66/7377—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the intensive physical properties of the material of the parts to be joined, by the optical properties of the material of the parts to be joined, by the extensive physical properties of the parts to be joined, by the state of the material of the parts to be joined or by the material of the parts to be joined being a thermoplastic or a thermoset characterised by the state of the material of the parts to be joined amorphous, semi-crystalline or crystalline
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    • B29C66/73772—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the intensive physical properties of the material of the parts to be joined, by the optical properties of the material of the parts to be joined, by the extensive physical properties of the parts to be joined, by the state of the material of the parts to be joined or by the material of the parts to be joined being a thermoplastic or a thermoset characterised by the state of the material of the parts to be joined amorphous, semi-crystalline or crystalline the to-be-joined area of at least one of the parts to be joined being amorphous the to-be-joined areas of both parts to be joined being amorphous
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    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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    • B29C66/70—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material
    • B29C66/73—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the intensive physical properties of the material of the parts to be joined, by the optical properties of the material of the parts to be joined, by the extensive physical properties of the parts to be joined, by the state of the material of the parts to be joined or by the material of the parts to be joined being a thermoplastic or a thermoset
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    • C—CHEMISTRY; METALLURGY
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    • B29C65/82—Testing the joint
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Abstract

本发明提供一种无定形加工范围位于从约40℃～约70℃的Tg到约70℃～约150℃的Tcg的可热合聚酯组合物。该组合物优选包含聚对苯二甲酸乙二醇酯均聚物或共聚物和聚对苯二甲酸丙二醇酯均聚物或共聚物的混合物，或者作为物理共混物或者作为由各自单体制备的共聚聚酯低聚物或聚合物。制成的组合物可低温热合，保持其阻隔性能并且不走味。

Description

低温-可热合聚酯薄膜及其生产方法
技术领域
本发明涉及一种无定形加工范围位于从约40℃～约70℃的Tg到约70℃～约150℃的Tcg的可热合聚酯组合物，以及可热合聚酯薄膜的生产。本发明具体地涉及通过加入聚对苯二甲酸丙二醇酯均聚物或共聚物对聚对苯二甲酸乙二醇酯均聚物或共聚物进行改性，生产出低Tg和高Tcg的聚合物共混物或共聚聚酯，从而使之在较低温度可热合，却依然保持适中的阻隔性能。
背景技术
聚对苯二甲酸乙二醇酯，以下称2GT或PET，及其共聚聚酯(例如，与间苯二甲酸酯(I)或环己烷二甲醇(CHDM)的共聚聚酯以制造2GT-I、2G-CHDM/T或2G-CHDM/T-I)，已知适用于包装那些对风味散失或吸收周围气味和异味，即，走味，敏感的物品或食品。例如，可参见美国专利4,578,437。这些树脂还适合用来提供耐油脂的作用。另外，这些聚酯对氧气、二氧化碳和/或水蒸汽具有适中的阻挡作用。
在包装和其他应用领域，热合被用来连接各个热塑性零件。这是通过对要连接的表面加热使之软化或熔融，同时对需要它们连接在一起的地方施加一定压力完成的。最常见的加热是通过与待连接表面相反的表面与热物体相接触，例如与热棒，或者用热空气、红外线、超声波或感应加热达到加热这些表面的。能达到将待连接表面加热到适当温度以便连接的速度通常决定了能以多高的速度将表面热合。高速热合之所以重要是因为，许多此类操作乃是大量、连续操作，若这里采用慢速加热则势必大大增加成本。
若能采用热合设备以快热合速度来热合上面描述的聚酯同时又依然达到牢固密封的效果，那将是可心的。这在过去，对于2GT均聚物或共聚物来说一直难以实现，原因在于这些组合物的玻璃化转变温度(Tg)高，典型值大于约70℃。无定形(非晶)聚酯薄膜一般在两个密封成形表面的温度升高到超过玻璃化转变温度的范围时方才靠自身形成热合。
聚(对苯二甲酸1，3-丙二醇酯)，这里称3GT，亦称聚对苯二甲酸丙二醇酯或PPT，是通过1，3-丙二醇与对苯二甲酸的缩聚制成的聚酯。聚对苯二甲酸丙二醇也可通过1，3-丙二醇与对苯二甲酸二甲酯(DMT)在二-反应器方法中采用四异丙醇钛催化剂TyzorTPT(杜邦公司的一种注册商标)来制备。在酯交换釜中，熔融DMT加入到约185℃的1，3-丙二醇和催化剂中，然后温度升高到210℃，同时不断移出甲醇。所生成的中间体转移到缩聚釜中，在此，压力降低到1mbar(10.2kg/cm2)，温度升高到255℃。当达到要求的熔体粘度时，提高压力，将聚合物挤出、冷却并切粒。
3GT具有好于2GT的隔氧和隔气味性能，但玻璃化转变温度低得多，典型值为约50℃。遗憾的是，3GT不具有稳定的热合性能，因为其Tg低和无定形加工范围窄。就是说，Tg与Tcg之间的温度范围(即，玻璃化转变温度与自无定形状态结晶的峰值温度之间的ΔT)非常小，以致其无定形薄膜或零件在尚未热合之前往往就陈化或结晶了。一旦含3GT-薄膜或零件结晶，它就很难在熔融温度以下达到牢固的封合。
美国专利5,183,623描述一种利用热成形技术生产透明和耐热聚酯薄膜的方法。该片材由具有至少80mol％由1，3-丙二醇和对苯二甲酸或其成酯衍生物衍生的酯单元的熔融聚酯树脂生产。该聚酯树脂具有至少80mol％3GT，以聚合物链中全部重复单元为基准；这近似等于80wt％3GT。固体树脂片材具有低结晶度，在陈化后，该片材在特定条件下通过热成形，而制成一种高度结晶的容器。
美国专利5,989,665描述一种共聚聚酯，包含含有约85～100mol％1，3-丙二醇或约85.8～100wt％该丙二醇的二醇组分的反应产物。该共聚聚酯，据公开，可用于包装的用途。
美国专利5,627,236公开一种由共聚聚酯连续相与低模量不连续相组成的多相组合物。该不连续相可以是弹性体、非弹性体、交联、支化或直链。作为不连续相特别有用的是乙烯共聚物或三元共聚物。该组合物提供高温粘度稳定性和卓越的长期、热合以及阻隔性能。
日本公开的专利申请HEI 10[1998]-279707公开一种共聚聚酯薄膜，优选含有3～35wt％1，3-丙二醇作为二醇组分。该薄膜在100～180℃范围的温度进行热处理以提高薄膜防止随时间而变质的能力从而大大减少薄膜破裂的发生。制成的薄膜在40℃贮存5天后具有大于100％的伸长率，以及其他性能。
目前，需要一种具有2GT和3GT的最佳阻隔性能的聚合物，它能够在低热合棒温度下轻易和以快热合速度热合，同时又仍然产生高热合强度。尤其是用在包装中，此种聚合物若能生产出一种透明零件和薄膜则必将受到青睐。
发明公开
本发明提供一种可热合聚酯组合物，其无定形加工范围从约40℃～约70℃的Tg到约70℃～约150℃的Tcg。
本发明还提供一种可热合聚酯组合物，它包含聚对苯二甲酸乙二醇酯均聚物或共聚物以及约5％～约95wt％，优选20％～80wt％，更优选30％～70wt％聚对苯二甲酸丙二醇酯均聚物或共聚物，以聚对苯二甲酸乙二醇酯和聚对苯二甲酸丙二醇酯总重量为基准。
还提供一种降低聚对苯二甲酸乙二醇酯均聚物或共聚物的Tg的方法，包括下列步骤：
(a)将聚对苯二甲酸丙二醇酯均聚物或共聚物加入到结晶的聚对苯二甲酸乙二醇酯均聚物或共聚物中形成一种共混物；
(b)干燥该共混物：令该共混物在介于约120℃～约130℃的温度下暴露于至少0.028m3/min(1ft3/min)露点低于-20.5℃(-5°F)的干燥空气流中达至少约6h或直至达到足够干燥的程度；
(c)熔融掺混该共混物以形成Tg低于步骤(a)的聚对苯二甲酸乙二醇酯的聚合物。
本发明还提供一种制造低温-可热合聚酯薄膜的方法，包括下列步骤：
(a)将聚对苯二甲酸丙二醇酯均聚物或共聚物加入到结晶的聚对苯二甲酸乙二醇酯均聚物或共聚物中形成一种共混物；
(b)干燥该共混物：令该共混物在介于约120℃～约130℃的温度下暴露于至少0.028m3/min(1ft3/min)露点低于-20.5℃(-5°F)的干燥空气流中达至少约6h或直至达到足够干燥的程度；
(c)熔融掺混该共混物以形成Tg低于步骤(a)的聚对苯二甲酸乙二醇酯的聚合物。
本发明还提供两个热塑性塑料热合的方法，其中两个热塑性表面通过加热和加压彼此热合在一起，其中改进之处包括，所述热塑性塑料至少之一包含一种聚酯组合物，它包含聚对苯二甲酸乙二醇酯均聚物或共聚物与聚对苯二甲酸丙二醇酯均聚物或共聚物的共混物，或者由各自单体生成的共聚物。
本发明还提供一种制品，其中两个热塑性表面被热合在一起了，其中所述热塑性表面至少之一包含一种聚酯组合物，它包含聚对苯二甲酸乙二醇酯均聚物或共聚物与聚对苯二甲酸丙二醇酯均聚物或共聚物的共混物，或者由各自单体生成的共聚物。
本发明还提供一种生产可热合薄膜或片材的方法，包括下列步骤：
(a)挤出由两种截然不同聚酯部分构成的混合物，包含95～5重量份聚对苯二甲酸乙二醇酯均聚物或共聚物部分与5～95重量份聚对苯二甲酸丙二醇酯均聚物或共聚物部分，其中所述挤出是在聚合物在挤出机和模头中的停留时间介于1～15min、235～290℃温度的条件下进行的；
(b)对在步骤(a)中产生的挤出聚酯熔体实施骤冷；以及
(c)回收一种聚酯薄膜或片材，它具有从约40℃～约70℃的Tg到约70℃～约150℃自无定形状态的峰值结晶温度Tcg的无定形加工范围。
在该后一种方法中，两种截然不同聚酯部分优选包含聚对苯二甲酸乙二醇酯均聚物粒料、聚对苯二甲酸乙二醇酯共聚物粒料或其混合物作为一种截然不同聚酯部分，以及聚对苯二甲酸丙二醇酯均聚物粒料、聚对苯二甲酸丙二醇酯共聚物粒料或其混合物作为另一种截然不同聚酯部分。优选的是，这两个截然不同聚酯部分之一或二者在挤出之前通过将该一个或多个部分在介于约120℃～约130℃的温度暴露于至少0.028m3/min(1ft3/min)露点低于-20.5℃(-5°F)的干燥空气流中至少约6h以达到干燥。
按照本发明该后一种方法，现已发现，2GT/3GT均聚物/共聚物混合物在挤出温度下长时间停留期间的酯交换可由NMR(核磁共振)加以证实并有利地与生产的聚酯薄膜所要求的低温、可热合性相关。更具体地说，已观察到在tce-d2，氘化四氯乙烯中在120℃，500MHz和更高处，一个1H NMR谱的约8.038ppm的峰(位于与2GT和3GT相联系的两个主要均聚物NMR峰值之间)，与无定形聚酯薄膜可热合性的改善相关。
发明实施模式
图1是表示采用表6中的数据，无定形薄膜样品的第一遍加热的热性质的曲线图。
图2是表示无定形薄膜样品暴露于环境条件下一周后热合开始(温度)和强度的变化的曲线图。
图3是表示单层流延薄膜的氧和水蒸汽透过速率的曲线图。
图4是表示“原封制成”的三层吹胀薄膜，即，在防潮袋中保存并在薄膜制成的一天之内进行热合)的热合强度与棒温的关系的曲线图。
图5是表示薄膜在环境条件下预先陈化24h后的热合强度与热合棒设定温度之间关系的曲线图。
图6是比较在32mm(一又四分之一英寸)直径流延膜挤出机和模头中估计与测定的停留时间随螺杆转速(rpm)变化的曲线图。
图7是差示扫描量热仪DSC对实例A流延膜的第一遍扫描标绘，从-40～270℃，扫描速率10℃/min。
图8是实例A流延膜从270到-40℃以10℃/min扫描速率的DSC冷却曲线。
图9是实例A流延膜第二遍加热的DSC，从-40到270℃，扫描速率10℃/min。
图10是表示采用表17数据的单层流延膜样品首次加热热性质随110℃棒适度温度下平均热合强度(g/2.54cm)变化的曲线图。
图11是表示采用表17数据的单层流延膜样品冷却曲线Tg和第二遍加热热性质随110℃棒适度温度下平均热合强度(g/2.54cm)变化的曲线图。
图12是表示本发明方法生产的三层共挤出吹胀薄膜管(泡)的侧视透视图。
图13是表示估计停留时间，min，随螺杆转速(rpm)变化的曲线图，分别为根据图12所示共挤出吹胀膜A和C层几何参数计算的(停留时间)以及通过在A挤出机进料喉部投入着色粒料测定的。
图14～28是表示表21的实例N～Z、AA和AB共挤出薄膜制成的翼形封口平均热合强度(表示最大和最小值)随所采取的热合棒设定温度变化的曲线图。
图29是表示实例流延膜14和15在40℃调质前后的平均纵向(MD)断裂伸长的曲线图。
图30是表示实例流延膜14和15在40℃调质前后的平均横向(TD)断裂伸长的曲线图。
发明详述
为了下面公开的目的，给出以下定义：
在本公开中，“无定形加工范围”是指聚合物的玻璃化转变温度，Tg，与自无定形状态结晶的峰值温度，即，冷结晶温度，Tcg，之间的温度范围。
术语“共聚物”是指由三种或更多种单体聚合而成的聚合物，因此包括三元共聚物，或者更确切地说，包含二或更多种重复单元的聚合物。
术语“截然不同聚酯”树脂由这样一些单体制备的聚酯，其中在聚酯之间至少有一种单体不同。
术语“均聚物”是指由两种单体(例如，一种类型二醇和一种类型二酸(或二酸的甲酯)聚合而成的聚合物，或者更确切地说，包含一种重复单元的聚合物。
术语“物理共混物”是指二或更多种聚合物通过熔融掺混并任选地混炼而制成的均一、紧密混合物。Tg是指聚合物的玻璃化转变温度。就典型而言，这是采用差示扫描量热仪(DSC)根据ASTM D 3417以10℃/min的加热速率进行加热和冷却，并记录转折段的中点从而完成测定的。
还有，Tcg是指自无定形状态结晶的峰值温度，采用DSC根据ASTMD 3417以10℃/min的加热速率进行加热和冷却来测定。
本申请人发现一种可热合聚酯组合物，它表现出宽无定形加工范围，特别是由于该聚合物的Tg相对地低，无定形加工范围则更宽。由于可形成热合的温度的降低，此种聚合物的薄膜可以高热合速度进行加工，从而降低了生产成本并提高效率。另外，该聚酯薄膜表现出改进的气味阻隔性质、良好隔氧和/或二氧化碳的性质并且光学上透明。
具体地说，此种组合物的无定形加工范围从约40℃～约70℃，优选约48℃～约70℃的玻璃化转变温度Tg，到约70℃～约150℃，优选以84℃～约135℃的自无定形状态结晶的峰值温度。
该聚酯组合物的熔点介于约180℃～约240℃的范围，优选低于约240℃。当本发明聚酯组合物是一种物理共混物时，该组合物将极可能表现出至少两个截然不同的熔点，若采用DSC并按照ASTM D 3417测定的话。其特性粘度(IV)，当采用1∶1重量比二氯甲烷和三氟乙酸的溶液在19℃的温度如下面的实例中所述那样测定时，一般介于约0.4dl/g～约2.0dl/g，优选约0.80dl/g～1.5dl/g。
该聚酯组合物优选是2GT均聚物或共聚物，通过加入约5％～约95wt％3GT均聚物或共聚物，优选以20％～约80wt％，最优选约30％～约70wt％，以2GT和3GT总重量为基准，做了改性的产物。当该聚酯组合物是共聚聚酯时，3GT的用量优选介于约40％～约75wt％，以2GT和3GT总重量为基准。虽不拟囿于任何特定理论或解释，但本申请人相信，3GT聚合物在2GT聚合物中的加入拓宽了无定形加工范围，与加入前2GT聚合物相比主要通过降低Tg，和/或阻滞结晶起作用。该组合物或者是两种截然不同聚酯例如，2GT和3GT聚合物，的物理共混物或者是由各自单体，例如，对苯二甲酸、乙二醇、1，3-丙二醇以及任选地其他成酯单体，所制备的共聚聚酯低聚物或聚合物。如果组合物包含物理共混物，则其IV在物理掺混后至少为约0.4dl/g。
2GT均聚物是指一种基本上由乙二醇与对苯二甲酸的聚合衍生的或者替代地，由其成酯等价物(例如，任何可聚合并最终提供一种聚对苯二甲酸乙二醇酯聚合物的反应物)衍生的聚合物。2GT的共聚物是指任何包含至少约70mol％对苯二甲酸乙二醇酯(或由其衍生)的聚合物，而聚合物的其余部分则由除对苯二甲酸和乙二醇(或它们的成酯等价物)以外的单体衍生而来。
可用于本发明的2GT聚酯包括：(a)聚对苯二甲酸乙二醇酯均聚物；和(b)2GT共聚物，即，2GT聚合物通过加入除对苯二甲酸以外的二酸(例如，间苯二甲酸(I)、1，2，4-苯三酸酐、1，3，5-苯三酸、脂族二酸，包括己二酸、十二烷二酸、CHDA(环己烷二羧酸)或除乙二醇以外的二醇(例如，环己烷二甲醇(CHDM)、二甘醇)及其混合物而达到改性的产物。来自聚酯工艺循环物流的杂质是另一单体来源。
用于本发明的2GT聚酯应是热塑性和可结晶的，玻璃化转变温度(Tg)至少约60℃，并且熔点至少约150℃。更优选的聚酯的熔点至少是200℃。最优选的聚酯是具有约1％～15％间苯二甲酸的2GT共聚物。二甘醇(DEG)的含量优选最高约2wt％。无定形聚合物不那么受欢迎，因为它们较难干燥。
3GT均聚物是指基本上由1，3-丙二醇与对苯二甲酸的聚合衍生的，或者由其成酯等价物(例如，任何可聚合并最终提供聚对苯二甲酸丙二醇酯聚合物的反应物)衍生的聚合物。3GT的共聚物是指任何包含至少约70mol％对苯二甲酸丙二醇酯的聚合物，而聚合物其余部分则由除对苯二甲酸和1，3-丙二醇(或它们的成酯等价物)以外的单体衍生而来。从实际的角度，较高百分率对苯二甲酸丙二醇酯可保证聚合物是半结晶的，因此容易干燥。
该聚酯组合物应具有适当分子量以获得足够机械强性能。就其特性粘度(IV)而论，掺混后，组合物优选具有至少约0.4dl/g～约0.80dl/g，更优选至少约0.90gl/g，最优选约1.3～1.5dl/g，以在1∶1重量比二氯甲烷和三氟乙酸中的溶液测定，的IV。特性粘度是通过在19℃测定已知聚合物浓度的溶液在毛细管粘度计中的流动时间和聚合物溶剂的流动时间，正如ASTM D 2857.95所规定的那样来确定的。
制成的组合物基本为无定形(即，基本上不表现任何结晶性)且优选表现出介于约5～约12cm3-密耳/日-645cm2(100平方英寸)-大气压在23℃和干态的氧透过速率(OTR)，按照实施例中，类似于ASTMD3985-81的程序测定。该组合物还优选透明(尽管要求的话可加入着色剂)并表现出良好气味阻隔性能，即，低气味渗透，低走味和不给包装物引入异味或香味。最重要的是，该组合物通常在较低温度可热合，并具有良好热合强度和足以支持大多数包装应用的热-粘着强度。
本发明组合物可成形为薄膜(意指片材)或其他制品。薄膜可以是单层薄膜或在与其他薄膜层，包括聚烯烃、乙烯共聚物、离聚物、聚酰胺、聚碳酸酯、聚丙烯酸类、聚苯乙烯、粘合剂结合层、可再封合胶粘性乙烯-乙烯醇、PVDC等的共挤出中成形的多层薄膜。单层薄膜还可层合到其他薄膜或基材上。多层薄膜将具有二或更多层，优选表面层之一或二者都是这里所描述的可热合聚酯组合物。由于具有低温-可热合的性质，这里的本发明薄膜容易利用诸如乙烯-醋酸乙烯(EVA)或酸酐改性EMA之类的粘合剂结合层与聚烯烃共挤出到其他层上。此种多层薄膜拓展了本文所述本发明应用的可能，因为其他层能赋予附加的要求特性，如机械强度、韧性、附加阻隔性能、耐热、可印刷性以及其他诸如此类。
这里公开的本发明的薄膜尤其可用于包装领域，且可采用本领域技术人员已知的许多方法成形为包装。所谓术语“包装”是指任何容器，就是说，大多数时间将保持密封，尤其在所包装物使用之前，以隔绝环境条件如空气和/或湿气，和/或防止被包装物因蒸发而损失，还包括蒙罩用途(例如，用可揭去的蒙罩薄膜覆盖的托盘或容器)。包装可设计成当割开或撕开密封袋时隔绝环境条件的密封便永久地破坏，或者可做成使用期间仍保持为密封的形式，例如，凝胶袋，用于加热，然后作为加热垫敷用。这些包装优选由本文所公开的单-或多层薄膜制成，尤其是多层薄膜，其中这里的本发明可热合聚酯组合物构成“热合层”，即形成热合的层。此种包装对于包装食品极其有用，因为可成形为具有隔氧功能和良好香味/异味阻挡层，不走味和低放味而且透明。因此，它们尤其优选用来包装保持味道和气味很重要的场合。该包装可以是密封的柔性袋，例如固体或液体的容器、静脉滴注袋、口袋、干食品袋(谷物衬里、饼干盒内衬)、化学品口袋、直立口袋、谷物口袋、蒙罩膜、宠物食品袋以及诸如此类。
尽管不要求，但传统添加剂可以加入到本发明组合物、薄膜或制品中。此类添加剂包括颜料、着色剂、稳定剂、抗氧化剂、挤塑助剂、滑爽剂、碳黑、成核剂、阻燃剂、本领域技术人员已知的其他添加剂及其混合物。
由本发明组合物制成的薄膜肯定可用于许许多多与包装无关的其他用途。例如，一种可能的用途是消费者在衣服干燥机中使用的家用干洗袋。此种袋子通常沿三边热合，留出可再密封的第四边用于接受要干洗的衣服和清洗化学品。此种袋子必须具有在高温，例如高于200°F，下良好的尺寸稳定性，以及隔绝干洗化学品的能力。这里的可热合组合物可以2GT、3GT的粒料共混物(如本文所述)形式与尼龙(例如，尼龙6)粒料掺混，然后挤出涂布到流延或取向的(双轴或单轴取向)聚酰胺(尼龙-6或尼龙-6，6)或2GT薄膜上。制成的薄膜可用来制造干洗袋。还可想出许多其他用途。
本发明还提供一种降低2GT均聚物或共聚物的Tg的方法。该方法从结晶2GT均聚物或共聚物的干燥开始，既可与3GT均聚物或共聚物分别干燥，也可二者同时干燥。干燥过程是让聚合物在约120℃～约130℃的温度暴露于至少0.028m3/min(1ft3/min)露点低于-20.5℃(-5°F)的干空气中至少约6h或者直至达到充分干燥。如果分别干燥，则3GT均聚物或共聚物接着加入到2GT均聚物或共聚物中形成物理共混物。然而，优选的方法是先掺混3GT均聚物或共聚物粒料与2GT均聚物或共聚物粒料，然后再将它们如上所述地同时干燥。该物理共混物是通过熔融掺混制成的两种聚合物的均一、紧密混合物。熔融掺混可采用本领域技术人员已知的各种方法完成，包括：(1)上一段中所讨论的粒料共混物的干燥并挤出成形为聚合物熔体；(2)干燥的粒料共混物进行熔融混炼，然后制成薄膜或其他制品；以及任选地，在成形为薄膜或其他制品之前进行固态聚合。替代地，2GT与3GT各自的单体可彼此共聚以获得类似性质。不论物理共混物抑或共聚物，制成的聚合物/薄膜都具有低于原来2GT均聚物或共聚物的Tg。
本发明还提供一种制造低温-可热合聚酯薄膜的方法。第一步骤是2GT和3GT的干燥和混合(或替代地，混合，然后干燥)，以及熔融掺混形成物理共混物，如上所述。替代地，2GT和3GT各自的单体可进行共聚。获得的物理共混物或共聚物挤出成形为单层或多层薄膜。
本发明还提供一种将两个热塑性塑料热合的方法，其中两个热塑性表面借助加热和加压彼此热合在一起。改进之处在于热塑性表面至少之一包含一种含有2GT均聚物或共聚物和3GT均聚物或共聚物的聚酯组合物。上面有关本文公开的聚酯组合物的讨论同样地适用于此种表面。
本发明还提供一种制品，其中两个热塑性表面热合在一起了，所述热塑性表面至少之一包含一种含有2GT均聚物或共聚物和3GT均聚物或共聚物的聚酯组合物。待热合的两个制品表面可都具有本文描述的聚酯组合物的表面，尽管仅一个表面包含该聚酯组合物的情况也在考虑之列，例如，蒙罩的场合。上面有关本文公开的聚酯组合物的讨论同样地适用于此种热塑性表面。如果两个待热合表面都包含该聚酯组合物，则优选的是，这两个表面的组合物由相同单体制成，更优选这些表面由基本相同的聚合物制成。
两个以上表面可热合在一起，例如，三个表面可热合在一起，只要所有热合的表面由这里所描述的组合物构成。优选的是，待热合区域的加热借助从较热材料的热传导实现(例如，热合棒或辊)，利用微波加热、介电加热、超声波等)。
所采用的压力大小随着使两个(或更多个)待热合表面接触所需要的压力而不同，例如从手指压力到压机或辊筒施加的压力，例如，热合棒的最高约90磅每平方英寸。加热可在加压之前或者二者同时进行。尽管加压可在加热之前，但一般将等到加热时才加压。
可热合聚酯组合物热合表面的温度，当正在热合时，一般将高于Tg和低于Tcg。鉴于大量工业上实施的热合是在高速生产线上进行的，因此通常产生足够强度的热合所需要的温度越低，生产线运转得就越快，因为它将热合表面加热到要求温度需要的时间较短。
包含按本文公开的方法热合的两个热塑性表面的制品包括，注塑、压塑、热成形或吹塑零件；单层和多层表面以及片材以及由此制成的包装(也如上面所公开的)；涂布了这里的可热合聚酯组合物的箔、纸或预制板以及由它们制成的包装。
本发明将通过下面的实施例进一步加以阐明，然而这些实施例纯属举例说明而已。
实例1～6
实例1～6展示由3GT树脂与2GT/I树脂的共混物制成单层流延膜在“原封制成”的低温热合强度和热-粘着强度宽度上产生的惊人改善。
树脂干燥；
两种聚合物分别干燥。第一种是乙二醇、对苯二甲酸(T)和间苯二甲酸(I)，即，2GT/I，的聚酯共聚物，它具有约1.5wt％，以聚合物总重量为基准，的DEG含量，2mol％I，以酸的总摩尔数为基准，以及98mol％T，以酸的总摩尔数为基准，241℃的熔点和0.8dl/g的名义粘度IV。第二种聚合物是1，3-丙二醇和对苯二甲酸二甲酯(3GT)的均聚物，具有230℃的熔点和1.1dl/g的名义粘度。这两种聚合物分别在所描述的热空气干燥器(露点低于-20℃，干燥器设定点125℃)干燥过夜。
粒料/粒料共混物；
干燥后，通过两种树脂在20L体积提桶中混合制备2GT/I和3GT的粒料与粒料的共混物。
薄膜流延；
掺混的粒料立即喂入到氮气吹扫的32mm(一又四分之一英寸)直径30/1 L/D单螺杆挤塑机的料斗中，螺杆配备3/1压缩比、单螺棱螺纹，其熔融混合段为5L/D。挤塑机模头是152mm(6英寸)宽衣架型平膜模头，模口间隙0.03cm(0.012英寸)。挤塑机和模头由WayneMachine公司(100 Furler St.Totowa NJ 07512-1896)制造。熔融聚合物薄膜从模头出来被拉伸到名义上0.0015英寸厚，同时它连续流延到8英寸宽、8英寸直径双层壳螺旋挡板流延辊上，该流延辊配备温度受控冷却水系统。流延辊由Killion Extruders--DavisStandard(200 Commerce Road，Cedar Grove，新泽西07009)制造。
骤冷后的流延膜卷绕到3英寸直径纸芯上并贮存在聚乙烯袋中。共混物组成连同挤塑机和流延辊操作条件总括在表1和表2中。
                                        表1
  掺混说明实例号# 1 2 3 4 5 6
  树脂Wt.％树脂Wt.％挤出机条件机筒区     1℃机筒区     2机筒区     3机筒区     4过滤器法兰-模头1接套-模头2进料头-模头3端法兰-模头4扁平模头-模头5过滤器  熔体接套  熔体过滤器前压力(psi)过滤器后压力(psi)螺杆R.P.M.螺杆电流(A)   3GT100温度2602502402402402402402502502362401180450402.7   3GT802GT/I20温度2602502402402402402402502502362401780510402.7   3GT602GT/I40温度2702502502502502402402402502442401620590402.7   3GT402GT/I60温度2852652652602502502502602602482481260440402.5   3GT202GT/I80温度2852702652652602602602602602582601350520402.6 2GT/I100温度2852702702702702702702702702672601230450402.6
                                    表2
  流延单元实例号# 1 2 3 4 5 6
  流延辊Roll-F.P.M引出辊/流延辊速化曲面辊/流延辊速化边缘销-PSI引出辊隙PSI膜厚(密耳)平折(英寸)产量(gm/min)产量(lb/hr)水循环单元温度设定/实际℃   451.01.0YES-501.594.5951315.5   451.01.0YES501.784.5941215.5   451.01.0YES501.674.35911215.5   451.01.0YES501.594.5941215.5   451.01.0YES501.634.5951215.5   451.01.0YES501.54981315.5
薄膜分析；
该单层流延膜被用来测定热合性质。感兴趣的是能达到牢固热合的最低热合棒温度，因为低热合开始温度意味着产生密封所要求的热量较少。热量较少意味着可采用较低热合棒温度，这将延长热合钳口使用寿命(减少维护成本)并且还与较快生产线速度相关联，因为热合进行得较快。热合(强度)是按照ASTM程序F88测定的，其中采用12.5μm(0.5密耳)DuPont Mylar薄膜滑润垫片，276kPa(40psi)热合棒压力，0.64cm(0.25英寸)宽热合棒和1.0s停留时间。热量仅施加在上棒上。获得的热合强度是采用SP-102C-3m90 Slip/Peel试验机(由IMASS公司供应(Box 134 Accord MA 02018-0134)在25.4cm滑动横梁速度下沿着1.27cm(0.5英寸)宽的热合条测定的。
单层流延膜的热合强度总括在表3中。
表3.6种实例薄膜的热合强度。热合强度单位是gm/1.27cm(0.5英寸)
  棒设定温度℃  实例1  2   3   4   5   6
  90  0  0   0   0   0   0
  100  0  0   17   95   37   36
  110  0  0   164   939   570   127
  120  0  0   480   973   1400   995
  130  0  0   508   1070   1085   1077
  140  0  367   831   1273   1130   1780
实例薄膜1～6(分别为纯3GT和2GT/I)在热合棒设定温度为90、100和110℃下不是没有热合强度就是热合强度非常低(低于150g/1.27cm)。
令人惊奇的是，由包含40～20％3GT在2GT/I中的共混物(实例4和5)制成的薄膜在热合棒温度低至110℃的情况下就具有牢固的热合强度(大于500g/1.27cm)了。
该单层流延膜样品还被用于测定热-粘着强度。在热合试验中，让封口冷却至室温，然后再测定热合强度。而热-粘着试验则是趁热测定封口的密封强度。热-粘着强度是水平和垂直成形/充填(或灌注)的热合操作所要求的，因为此时载荷(被包装物)几乎在密封成形以后立即就加载到封口上了，要知道整个成形和充填操作就发生在数秒钟内。
JB热-粘着试验机，型号3000，第二版，荷兰制造，被用于测定热-粘着强度。机器条件和试验结果载于表4。
表4——6种单层流延膜的热-粘着强度。热-粘着强度的单位以克/英寸封口为单位给出。
条件
热合压力           热合                冷却                       剥离速度              样品
(N/mm2)            时间(sec)           时间(sec)                  (200mm/s)             宽度(mm)
0.10               1.00                0.20                       200                   25
  上和下棒设定温度℃  实例1  2   3   4   5   6
  90  205  837   953   1193   68   17
  100  74  483   950   1420   1503   362
  110  52  492   1013   791   1513   1349
  120  33  305   676   908   941   832
  130  106  258   532   1115   769   703
  140  89  297   593   681   660   849
实例薄膜1和6(纯3GT和纯2GT/I)依然在热合棒温度90或100℃下具有低热-粘着强度(300克/英寸或更低)。3GT与2GT/I共混物的热-粘着强度却令人惊奇地好，在热合棒设定温度90℃的条件下从40％3GT/60％2GT/I共混物(实例4)测得超过1000克/英寸的数值。还应当指出的是，实例薄膜3和4在整个试验的温度范围内的热-粘着强度都保持非常好。
测定了这6种单层薄膜样品的溶液粘度。样品的制备和分析载于表5。溶液粘度是估计分子量的一种手段。
表5.溶液粘度测定
分析：聚酯特性粘度，按ASTM D 2857.95
溶剂：50/50wt％三氟乙酸/二氯甲烷
样品浓度：0.4g/dL
温度：19℃
  实例   IV结果
  123456   1.0350.9830.9420.8970.8530.813
分析了这6种单层薄膜样品以测定热性能。测定热性能之前，诸薄膜样品首先干燥过夜，热合在255℃加热5min，随后立即在甲醇和干冰浴中冷却。获得的此种特殊调质的样品在加载到TA InstrumentsDifferential Scanning Calorimeter(德州仪器公司差示扫描量热仪，型号2920)上之前将基本上不具有结晶性(无定形)。样品从-40℃以10℃/min的加热速率加热至275℃(按照ASTM D3417)。
在表6中总括了从这6种薄膜样品的第一遍加热中获得的性质。Tg代表玻璃化转变温度，℃(记录弯折的中点)。Tcg代表无定形样品加热后结晶过程所对应的峰值温度，℃。ΔH Tcg代表样品因结晶放出的热量(J/g)。Tm是样品的峰值熔融温度，℃。ΔH Tm是样品在熔融期间消耗的热量，J/g。
表6.无定形薄膜样品第一遍加热的热性质
  Tg(℃)  Tcg(℃)   ΔH(Tcg)J/g   Tm(℃)  ΔH(Tm)J/g
 1   46.2  71.4   22   229.2  57
 2   48.0  83.9   ---   228.5  58
 3   52.4  99.8   25   225.6  49
 4   60.0  121.6   26   241.6  42
 5   70.1  135.1   27   244.6  28
 6   69.2  137.1   25   245.1  26
图1，图示地表示出表6中的数据。根据热合和热-粘着试验结果，48～70℃范围的Tg(80％～20％3GT；或约50℃～66℃按线性关联)与85～135范围的Tcg(或大约86℃～135℃，按线性关联)的组合可提供令人惊奇地好于光是2GT/I(Tg70，Tcg144)或3GT(Tg46，Tcg71)的热合和热-粘着(强度)。
实例薄膜2～5显示令人吃惊好的“原封制成”热-粘着强度(在低热合棒温度下)可由用3GT和2GT/I的共混物制成的薄膜达到。全部由3GT制成的实例1薄膜样品的“原封制成”的热合和热-粘着都很差。实例6薄膜，由2GT/I树脂制成，虽具有好的“原封制成”热合和热-粘着，但只有在提高热合棒温度的情况下如此。
无定形薄膜样品在暴露于环境温度和湿度条件之后，热合和热-粘着性能似乎都表现出恶化。图2展示，实例薄膜4在暴露于环境条件下一周后热合开始和强度的变化。
实例薄膜1～6也被用于测定氧透过和水蒸汽透过速率。氧透过是采用Oxtran2/20型号H，低透过速率试验仪(Mocon公司，Minneapolis，MN 55428，美国)在23℃和O％相对湿度采用100％氧气(不是空气)测定的。试验的理论概述于ASTM D 3985-81“氧气通过塑料膜和片材的透过速率采用电量敏感元件的标准试验方法”中。结果按每25μm厚(1密耳)给出。数值校正到101kPa(760mm汞柱)的大气压压力。样品在试验前经过4h的调质。
试验面积是50cm2。
试验时间是60min。
水蒸汽透过速率是采用PermatranW 3/31水蒸汽透过系统(Mocon公司)在38℃和90～100％RH.下测定的。该试验的理论概述于ASTM D 1249-90“水蒸汽通过塑料膜和片材的透过速率采用调制的红外敏感元件的标准试验方法”。结果按每25μm厚(1密耳)给出。
试验面积是50cm2。
相对湿度基本上是100％。
样品在试验前调质2h。
试验时间是30min。
试验温度是37.8℃。
氧透过速率和水蒸汽透过速率载于表A中。
                    表A
  实例薄膜   Cc O2*25μ/100in2/在23℃和干燥   gH2O*25μ/645cm2(100in2)/在38℃和90-100％RH
  123456   7.59.19.69.19.812.6   4.14.34.34.04.34.5
载于表A并图示于图3的试验结果指出，氧透过速率随在2GT-I中掺入3GT而增加。水蒸汽透过速率对于所有6种试验薄膜基本上保持一样。
实例薄膜1～6还被用于测定3GT/2GT-I聚合物共混物的香味渗透性。所用方法类似于ASTM E96。70mL(58.6g)d-萜二烯柑桔香精(由Aromachem公司供应)放在每个蒸发计量杯中，并借助O-形环将一块试验薄膜盖牢在杯口。每种试验薄膜测试5个样品，以保证结果的可靠性。杯子放在40℃的烘箱内，然后在27天期间每天测定以确定香精的重量损失。由这些结果计算出GMD值(克*密耳/(日*大气压*645cm2(100英寸2))。除了实例薄膜1～6之外，还包括了由尼龙6(联合信号公司)和线型低密度聚乙烯(Dow Dowlex 2045)制成的对比薄膜。表B总括了香味试验的结果。
               表B
  实例薄膜   透过值g*mil/(atm*d*645cm2(100in2))
  1   2.1
  2   2.5
  3   4.0
  4   3.6
  5   5.3
  6   9.7
  尼龙6   2.7
  LLDPE   36.1
表B中的试验结果表明3GT与2GT-I的共混物在香味隔绝方面提供比光是2GT/I或LLDPE(线型低密度聚乙烯)的显著改进。
实例7～10
为克服任何物理陈化现象(例如参见，《无定形聚合物和其他材料中的物理陈化》，Struik，L.C.E.，阿姆斯特丹；纽约；Elsevier科学出版公司，负责美国和加拿大的总经销，Elsevier North-Holland，1978)，较高分子量2GT/I和3GT的样品是通过原料3GT或2GT/I的固相聚合或通过2GT/I与3GT的熔融掺混生产的粒料的固相聚合制备的。下面的4种树脂样品展示较高分子量对维持热合开始和热合强度的好处。
用于制备实例薄膜1～6的两种树脂2GT/I和3GT再次进行干燥，陈化，然后通过1.56mm(1/16英寸)直径线料口型挤出并在水中骤冷，再切断为1/8英寸长的粒料。这4种粒料共混物的组成(实例树脂7～10)以及挤出条件载于表7。
随后，4组挤出的粒料在上述烘干的料斗干燥器系统中、120℃下结晶过夜，继而在202℃、在充填床固相聚合器中利用连续热氮气流进行26h的固相聚合。26h后，让树脂冷却。固相聚合的树脂进行分析以测定溶液粘度。固相聚合后的溶液粘度载于表8。
表7——3GT和2GT/I的熔融掺混和共混物的造粒
  薄膜模头尺寸   STRAND1.56mm Dia.   模唇尺寸
  网眼尺寸-   60-80-60/80-100-80
  实例号#   7   8   9   10
  树脂1   3GT   3GT   3GT   3GT
  ％WT   60   40   20   70
  树脂2   2GT-I   2GT-I   2GT-I   2GT-I
  ％WT   40   60   80   30
  挤出机条件   温度℃   温度   温度   温度
  机筒区1   260   285   285   260
  机筒区2   250   265   270   250
  机筒区3   240   265   265   240
  机筒区4   240   260   265   240
  过滤器法兰-模头1   240   250   265   240
  接套-模头2   240   250   265   240
  扁平模头-模头5   240   250   265   237
  过滤器  熔体   237   251   260   236
  接套  熔体   241   250   265   241
  过滤器-   3010   1370   1410   3010
  压力kPa
  接套-压力   4,830   3,720   3,960   3,640
  螺杆R.P.M.   42   42   42   42
  螺杆电流(A)   3.2   2.6   2.6   3.0
  产量(gm/min)   92   101   100   93
  产量(lb/hr)   12.2   13.3   13.3   12.3
表8——实例树脂7～10在202℃固相聚合26h后的溶液粘度测定结果。
  实例树脂   IV
  7   1.31
  8   1.22
  9   1.12
  10   1.38
为展示固相聚合熔融掺混的树脂7、8和10的效力，制备了三层吹胀薄膜，以这些实例树脂作为热合层，杜邦Bynel3861酸酐改性乙烯-醋酸乙烯树脂作为结合层，并以HDPE(高密度聚乙烯，Chevron9662)作为外结构层。层厚是
1.7密耳HDPE
0.3密耳Bynel3861
0.5密耳实例树脂
该2.5密耳厚的薄膜被用于测定热合强度并与光用3GT作为热合层的三层薄膜进行比较。热合条件是0.5s的停留时间，276kPa(40psi)的热合棒压力和2.54cm(1英寸)宽的热合棒。对于275°F和以上的热合温度采用一种滑润垫片。
图4标绘出该“原封制成的薄膜”的热合强度随热合棒温度的变化。
图5标绘出在24h环境暴露之后，热合薄膜的热合强度随热合棒温度的变化。
从图5可以看出，由高分子量3GT和2GT-I共混物制成的薄膜在24h暴露于环境条件之后其热合性质基本上保持不变。另一方面，由3GT对照树脂制成的薄膜则在所研究的温度范围具有很差的热合强度。
实例11
这些薄膜展示由3GT树脂与2GT/I树脂的共混物制成单层流延膜在“原封制成”的低温热合强度和热-粘着强度宽度上产生的惊人效果。实例薄膜11的制备：
熔融共混物的制备
树脂干燥；
两种聚合物分别干燥。第一种是乙二醇、对苯二甲酸二甲酯和间苯二甲酸的聚酯共聚物(2GT/I)，它具有217℃的熔点和0.68dl/g的名义粘度IV[SelarTM PT 8307聚酯共聚物]。第二种聚合物是1，3-丙二醇和对苯二甲酸二甲酯(3GT)的均聚物，具有230℃的熔点和1.1dl/g的名义粘度。这两种聚合物分别在所描述的热空气干燥器(露点低于-20℃，干燥器设定点125℃)干燥过夜。
粒料/粒料共混物；
干燥后，通过两种树脂在20L体积提桶中混合制备2GT/I和3GT的粒料与粒料的共混物。
熔融掺混；
干燥的粒料/粒料共混物喂入到32mm(一又四分之一英寸)直径、Wayne 30/1 L/D单螺杆挤塑机的料斗中，螺杆配备1.56mm(1/16英寸)直径线料口型和骤冷槽和切粒机。生产30％3GT/70％2GT-I的Wayne挤出机条件载于表9。
                   表9
  实例11的树脂
  树脂   PT 8307
  ％WT   70
  树脂   3GT
  ％WT   30
  挤出机条件   温度   温度
  ℃   Set   Act
  机筒区1   220   220
  机筒区2   240   241
  机筒区3   240   241
  机筒区4   240   240
  过滤器法兰-模头1   230   230
  接套-模头2   230   233
  STRAND Die 3   230   229
  过滤器  熔体   233
  接套  熔体   230
  过滤器-压力   1420
  接套-压力   790
  螺杆R.P.M.   42
  螺杆电流(A)   3.2
  产量(gm/min)   109.20
  产量(lb/hr)   14.414
随后，熔融掺混的树脂在上述烘干的料斗干燥器系统中、120℃下结晶过夜，继而在195℃在充填床固相聚合器中利用连续热氮气流进行5h的固相聚合。5h后，让树脂冷却。
薄膜分析；
该固态聚合的熔融共混物(由30wt％3GT和70wt％2GT-I组成)被用于流延名义厚度37μm(0.0015英寸)的薄膜，采用与上面所述相同的单层流延膜设备。在流延成为薄膜之前，固态聚合的树脂先在130℃下干燥过夜。用于制备实例薄膜11的薄膜流延条件载于表10。溶液粘度测定(采用上面描述的程序)测定了实例薄膜11的IV，结果等于0.985。
                           表10
  30wt％3GT/70wt％2GT-I的固态聚合熔融掺混物实例薄膜11
  挤出机条件   温度
  ℃   实际
  机筒区1   287
  机筒区2   280
  机筒区3   271
  机筒区4   271
  过滤器法兰-模头1   270
  模头接套-模头2   270
  供料头-模头3   273
  端法兰-模头4   271
  扁平模头-模头5   270
  过滤器熔体   262
  接套熔体   269
  过滤器-压力   2220
  接套-压力   840
  螺杆R.P.M.   40
  螺杆电流，(A)   2.7
  流延单元
  流延辊-F.P.M.   45
  引出辊-与流延辊的比值   1.0
  曲面辊-与流延辊的比值   1.0
  边缘销-PSI   有
  分切刀-PSI   无
  引出辊辊隙-PSI   50
  薄膜厚度(密耳)   2.70
  平折(英寸)   5.13
  产量(gm/min)   97.10
  产量(磅/小时)   12.817
  纸/制动PSI
  薄膜取样(是否)   是
  备注
  水循环单元
  温度设定/实际   60
  供水压力/温度   60
  回水压力/温度   25
  收卷机％psi   70
标为实例薄膜11的单层流延膜被用于测定热合性质。感兴趣的是能达到牢固封合的最低热合棒温度，因为低热合开始温度意味着产生密封所要求的热量较少。热量较少意味着可采用较低热合棒温度，这将延长热合钳口使用寿命(减少维护成本)并且还与较快生产线速度相关联，因为热合进行得较快。热合是按照ASTM程序F88测定的，其中采用12.5μm(0.5密耳)的DuPont Mylar薄膜滑润垫片，276kPa(40psi)的热合棒压力，0.64cm(0.25英寸)宽的热合棒和1.0s的停留时间。热量仅施加在上棒上。获得的热合强度是采用SP-102C-3m90Slip/Peel试验机(由IMASS公司供应(Box 134 Accord MA 02018-0134)在10″/分钟十字头速度下沿着1.27cm(0.5英寸)宽的热合条测定的。
实例薄膜11的热合强度总括在表11中。
表11.实例薄膜11的热合强度。热合强度单位是gm/1.27cm(0.5英寸)
棒设定温度        实例11
℃
 90   0
 100   13
 110   359
 120   1537
 130   2000
 140   2000
给出下面的添加实例，以便进一步说明本发明的具体特征和实施方案，包括第一组涉及流延膜的实例和第二组涉及共挤出薄膜的实例。因此，下面的实施例不应不恰当地理解为限制性的。
实例组A～M——可热合单层流延膜：
为了说明要制造无定形可热合聚酯薄膜需要提高熔融温度和延长停留时间，由包含至少一种用共聚单体1，3-丙二醇制造的共聚聚酯的粒料共混物制成若干种流延膜。在所有情况下，流延膜都在23±1℃和50％相对湿度(RH)下调质24h，此后，薄膜在各种不同热合棒温度下进行热合。测定封口的平均峰值热合强度。
薄膜由下列聚酯树脂的粒料共混物制成：
一种名义上0.91 IV的固态聚合共聚聚酯树脂，由1，2-乙二醇、对苯二甲酸和少量间苯二甲酸制成。该聚合物由杜邦聚酯树脂和中间体公司按照商品名MelinarTM N4009聚酯树脂销售。此种共聚聚酯的峰值熔点是244℃，它是在TA Instruments Differential ScanningCalorimeter(德州仪器公司差示扫描量热仪)(DSC)上按照ASTM D3417采用10℃/min加热速率并采用以铟、锡和锌的三点标定进行测定的。
一种名义上1.04 IV的固态聚合聚酯均聚物由1，3-丙二醇和对苯二甲酸二甲酯制成。该聚合物由杜邦公司按照SoronaTM 3GT聚酯销售。按上述DSC程序测定，该均聚物的峰值熔点是228℃。该聚合物将被称之为3GT(1.04 IV)。
一种名义上0.95 IV的聚酯均聚物，由1，2-乙二醇和对苯二甲酸二甲酯制成。该聚合物由杜邦公司按照SelarTM PT X295聚酯树脂销售。按上述DSC程序测定，该均聚物的峰值熔点是249℃。该聚合物将被称之为2GT(0.95 IV)。
流延成薄膜之前，树脂利用烘干的料斗干燥器系统干燥过夜，其中干燥器设定温度是121℃(250°F)。随后，干燥的树脂通过按比例称重到20L提桶中并用手剧烈混合2min从而掺混在一起成为3000g的批料。
掺混粒料被立即喂入到氮气吹扫的32mm(一又四分之一英寸)直径、30/1长径比L/D、单螺杆挤塑机的料斗中，螺杆配备3/1压缩比、单螺棱螺纹，其熔融混合段为5L/D。进料段螺棱深度是5.3mm(0.20英寸)。挤塑机模头是152mm(6英寸)宽衣架型平膜模头，模口间隙0.25cm(0.010英寸)。挤塑机和模头由Wayne Machine公司(100Furler St.Totowa NJ 07512-1896)制造。熔融聚合物薄膜从模头出来被拉伸到名义上38μm(0.0015英寸)厚，同时它连续流延到203mm(8英寸)宽、203mm(8英寸)直径旋转、双层壳螺旋挡板流延辊上，该流延辊配备温度受控冷却水。在所有情况下，一种80/100/80US目滤网组合，由Niagara Screen Products供应，被用于过滤聚合物熔体。过滤网由爆破板(breaker plate)定位。流延辊由Killion Extruders——Davis Standard制造(200 Commerce Road，Cedar Grove，新泽西07009)。薄膜流延到骤冷辊上。一股穿过喷射孔吹出的空气(534kPa供应压力)被用来将薄膜外边缘固定在流延辊上。
骤冷后的流延膜卷绕到76mm(3英寸)直径纸芯上并贮存在聚乙烯袋中。共混物组成总括在表12中。表13a、13b和13c总括了挤出机和流延辊的操作条件。在表13a～13c中，记载了2种熔体温度，过滤器前的聚合物熔体温度和接套中的聚合物熔体温度。过滤器熔体探头安装得与法兰中聚合物熔体流道边缘平齐，因此与其说它是聚合物熔体的指示倒更像是钢法兰的度量尺度。模头接套的熔体温度采用一种伸到这6.1mm(1/4英寸)直径接套熔体转移管线的中心的熔体探头记录。在表13a、13b和13c中，以g/min为单位给出的产量是通过30s取样时间挤出期间收集到的挤出薄膜样品的称重算出的。停留时间也是通过投入色母粒到几乎光的进料网的螺棱中，然后记录颜色刚一出现在挤出薄膜之前所过去的时间而算出的。此种技术就粒料究竟需要多少时间从进料喉部被推走而言存在着缺点。该技术假定粒料是瞬间运走的，但多半不可能。所记录到的停留时间很可能偏于高估了停留时间。图6是测定的停留时间和估计的停留时间(根据几何参数)与螺杆转速的标绘，采用的是32mm(一又四分之一英寸)直径、30/1 L/DWayne挤塑机，配备模头接套和152mm(6英寸)宽衣架型平膜模头。
表12——流延膜采用的共混物组成
 树脂共混物   3GT   g   2GT-I(0.91)   G   2GT(0.95)   g
 树脂共混物1   70％   2100   30％   900
 树脂共混物2   50％   1500   50％   1500
 树脂共混物3   50％   1500   50％   1500
表13a——单层膜流延操作条件
  O.I.#批号#实例薄膜日期   2699-0881A11/14/00   2699-0882B11/14/00   2699-0883C11/14/00   2699-0931D21-Nov-00
  树脂共混物挤出机条件机筒区1(℃)机筒区2机筒区3机筒区4过滤器法兰-模头1接套-模头2进料头-模头3端法兰-模头4扁平模头-模头5过滤器熔体(℃)接套熔体(℃)过滤器前压力(kPa)过滤器后压力(kPa)螺杆R.P.M.螺杆电流(A)流延辊线速度，m/min速比，引出/流延辊速比，曲面/流延辊平均膜厚(μm)   1温度实际27527026526526526523226026925926593084475502.619.81.02139.0   2温度实际275270265265265270257267265259270109195281502.718.31.02144.1   3温度实际27530030030026527026327026527527752812148252.313.71.02145.7   1温度实际27527026426526526625826526525926986823849502.718.31.02142.8
  产量(gm/min)骤冷辊温度实际(℃)停留时间   130182.3min 182.3min 184.2min   130132.3min
  Table 13b-单层膜流延操作条件
  O.I.#批号#实例薄膜日期树脂共混物挤出机条件机筒区1(℃)机筒区2机筒区3机筒区4过滤器法兰-模头1接套-模头2进料头-模头3端法兰-模头4扁平模头-模头5过滤器熔体(℃)接套熔体(℃)过滤器前压力(kPa)过滤器后压力(kPa)螺杆R.P.M.螺杆电流(A)流延辊线速度，m/min   2699-0932E21-Nov-001温度Act2752702642652652652632662652562664475985252.410.7   2699-0933F21-Nov-001温度Act27530029930026527126926927028228458182148502.418.3   2699-0934G21-Nov-001温度Act275300300300265270270270266276277277590262.212.2   2699-0935H21-Nov-002温度Act27530030030026527127027026928328369813133502.519.8
  速比，引出/流延辊速比，曲面/流延辊平均膜厚(μm)产量(gm/min)温度设定/实际(℃)停留时间(min)   1.02145.662134.2   1.02148.8142132.3   1.02-149.874134.2   1.02148.1136132.3
  Table 13c-单层膜流延操作条件
  O.I.#批号#实例薄膜日期树脂共混物挤出机条件机筒区1(℃)机筒区2机筒区3机筒区4过滤器法兰-模头1接套-模头2进料头-模头3端法兰-模头4扁平模头-模头5过滤器熔体(℃)接套熔体(℃)过滤器前压力(kPa)过滤器后压力(kPa)螺杆R.P.M.   2699-0936I21-Nov-002温度Act275300300300265270269270265276277358062725   2699-0937J21-Nov-002温度Act2753003013002652712702702722852899487537075   2699-1131K07-Dec-002温度Act27527026526526527026027026525927210919599750   2699-1138L07-Dec-002温度Act2753003003002652722652702682822837787429651   2699-1261M03-Jan-012温度Act27527026526526527025627026525927210024563950
  螺杆电流(A)流延辊线速度，m/min速比，引出/流延辊速比，曲面/流延辊平均膜厚(μm)产量(gm/min)温度设定/实际(℃)停留时间(min)   2.310.71.02152.676134.2   2.529.01.02144.3218131.4   2.918.31.03140.6128132.3   2.518.31.03142.0140132.3   2.619.81.03137.6106132.3
图6对比了估计的停留时间，分钟，与测定的停留时间随螺杆转速，rpm的关系，采用的是32mm(一又四分之一英寸)直径流延膜挤塑机和基本上10～100rpm的模头。
薄膜流延成形后立即贮存在80～100μm厚聚乙烯袋中并扭转打结密封或用胶粘带密封以备将来分析。
在样品薄膜A～J和M的情况下，在它们流延成膜的当天，从聚乙烯袋中取出约2m长薄膜并平放24h，暴露在温湿度控制室内(23±1℃和50％RH)。在样品薄膜K和L的情况下，它们在环境条件下贮存在该塑料袋中4天，热合样品从袋中取出以便在23±1℃和50％RH下调质24h。24h暴露以后，立即将薄膜热合在一起形成翼形封口。热合棒设定温度从90℃到130℃每隔10℃一档。热合是采用SencorpSystems(Hyannis MA USA 02601)的型号12ASL/1热合机制备的。热合条件是，12.5μm(0.5密耳)杜邦Mylar薄膜滑润垫片、358kPa(40psi)热合棒压力，2.5cm(1.0英寸)宽乘30.5cm(12.5英寸)长热合棒以及0.5s停留时间。仅加热上棒。下面的未加热棒包含一2.5cm宽×30.5cm长的红色橡胶，被夹在钢夹具中。按照ASTM程序F88，从热合的薄膜上模切一片25.4mm宽×70～100cm长的薄膜以测试热合强度。在所有情况下，翼形封口的取向都是沿着横向。该25.4mm宽的封条利用Instron试验机，型号4469在50.8mm(2英寸)初始夹具间距、25.4cm/min(10英寸/分钟)夹具张开速率和23±1℃及50％RH的条件下沿横向拉开。尾部用手扶着以保证尾部与拉开方向保持90°的取向。一般地，每一热合棒设定温度试验4个样品。样品A～M的平均峰值热合强度载于表14。
表14——平均“峰值”热合强度(g/2.54cm)
  热合棒设定温度(℃)
  实例薄膜   90   100   110   120   130
  A   0   0   0   0   0
  B   0   21   168   72   237
  C   0   77   1402   1700   2344
  D   0   0   0   0   0
  E   0   0   0   0   0
  F   0   0   0   0   357
  G   0   151   550   704   803
  H   0   0   1590   1880   2166
  I   0   157   1607   2651   2744
  J   0   55   1442   1232   1891
  K   0   325   422   1106   844
  L   0   536   1464   1419   2034
  M   0   0   0   0   133
表14所载平均峰值热合强度数值表明，13个试验的样品中没有一个在90℃热合棒设定温度时具有任何热合强度。样品中某些在100℃热合棒设定温度或更高时具有了热合强度。
为理解为什么某些热合的薄膜轻易地在110～130℃热合棒设定点之间产生大于1,000g/2.54cm(克/英寸)的结实封口，开发出一种工艺模型。利用例如薄膜A～J的表格式工艺条件(参见表15)和在100和120℃热合棒热合设定温度下的平均热合强度值，开发出一种工艺模型。
三个工艺因素是：
-x3GT——3GT在3GT/2GT或3GT/2GT-I共混物中所占分数
-HUT——挤出过程中的停留时间
-MT——挤出过程中模头接套熔体温度。
表15——薄膜A～J在110℃和120℃下的工艺和条件与热合强度
  实例薄膜   x3GT   MT   HUT   110℃gm/2.5cm   120℃gm/2.5cm
  A   0.7   265   2.3   0   0
  B   0.5   270   2.3   168   72
  C   0.5   277   4.2   1402   1700
  D   0.7   269   2.3   0   0
  E   0.7   266   4.2   0   0
  F   0.7   284   2.4   0   0
  G   0.7   277   4.2   550   704
  H   0.5   283   2.4   1590   1880
  I   0.5   277   4.2   1607   2651
  J   0.5   289   1.4   1442   1232
该模型指出在110℃和120℃下平均热合强度与三种因素之间存在强相关。
工艺模型；
上述三种因素利用以下关系被规格化为Wayne挤出工艺模型。
NX3GT＝(x3GT-0.6)/(.1)
NMT＝(MT-275.7)/12
NHUT＝(HUT-3)/1.4
该模型还包括交互因素
NX3GT*NMT
NX3GT*NHUT
NMT*NHUT
预测110℃棒温下的热合强度的工艺模型；
用于110℃下的热合强度，全参数模型是：
 NMT*NHUT   Nx3GT*NHUT   Nx3GT*NMT   NHUT   NMT   Nx3GT   B
 504   -10.9   -630   400   831   -395   557
相关系数＝0.99
热合强度的估计值的标准误差是92g/in
在几乎不影响精确度的情况下，110℃热合强度的模型可简化为只有5个参数。
110℃热合强度的简化五参数工艺模型是：
  x3GT*MT   HUT   MT   x3GT   b
  -417   382   556   -428   554
相关系数＝0.94
基于该110℃热合强度用的5-参数模型的热合强度估计值标准误差是250g/2.54cm。
预测120℃棒温下的热合强度的工艺模型；
用于120℃下的热合强度，全响应模型是：
  MT*HUT   x3GT*HUT   x3GT*MT   HUT   MT   x3GT   b
  701   -172   -759   689   1025   -493   703
相关系数＝0.94
热合强度的估计值的标准误差是400g/2.54cm。
为展示该模型的有效性，表5总括了所有13种实例薄膜A～M在110和120℃的强度的预测值、测定值以及预测和实际热合强度值之间的误差。负的热合强度没有意义，可能应解释为0。
表16  110和120℃热合棒设定温度下的实际与预测热合强度1的比较，基于3GT分数、接套熔体温度和挤出停留时间
  实例薄膜   实际110℃   预测110℃   误差110℃   实际120℃   预测120℃   误差120℃
  A   0   12   -12   0   26   -26
  B   168   174   -6   72   88   -16
  C   1402   1513   -111   1700   2198   -498
  D   0   -3   3   0   0   0
  E   0   -17   17   0   -47   47
  F   0   -9   9   0   -28   28
  G   550   567   -17   704   752   -48
  H   1590   1539   51   1880   1738   142
  I   1607   1513   94   2651   2198   453
  J   1442   1471   -29   1232   1312   -80
  K   422   376   46   1106   328   778
  L   1464   1488   -23   1419   1646   -227
  M   0   376   -376   0   328   -328
1.热合强度以g/2.54cm为单位表示。
工艺优化
凭借该工艺模型的较好预测能力，有可能界定出将产生最佳热合表现的工艺条件。
-提高熔体温度
-延长停留时间
-将3GT分数降低到50％
为说明诸关系，考虑，在270℃接套熔体温度下将要求长停留时间才能生产出具有牢固热合的薄膜。该模型预测，采用50％3GT分数和270℃接套熔体温度，将要求9min的停留时间以达到1,000g/2.5cm的平均峰值热合强度。通过将接套熔体温度提高到285℃，该模型预测，同样1,000g/2.5cm的热合可用1.1min的停留时间达到。在3GT/2GT共混物中，70％3GT分数和285℃接套熔体温度条件下，该模型预测将需要4.3min的停留时间达到1000g/2.5cm的热合强度。
停留时间和接套熔体温度存在着实际的约束。例如，就停留时间而论，存在着压力降、剪切速率和设备制造成本所施加的限制，可能不允许采用长转移管线和/或接套来实现超过10～15min的长停留时间。还有，聚酯树脂的热稳定性或者在多层共挤出薄膜的情况下，可能不允许熔体温度超过300℃。
单层流延膜的热分析：
所有这13种单层流延膜都采用DSC进行了分析，以确定峰值熔点(ASTM D3417)和玻璃化转变(ASTM D3418)。图7、8和9显示实例薄膜A的三遍DSC曲线。图7代表对实例薄膜A进行的第一遍DSC，从-40℃到270℃，10℃/min。在该热曲线中，感兴趣的转折和峰值是：
●Tg代表玻璃化转变温度。无定形(非晶)聚酯薄膜或制品将直至两个热合-生成表面的温度升高到超过玻璃化转变温度时它们之间才形成热合。在第一遍加热时，Tg表现出在维持薄膜恒定加热速率所需要的热量方面的转折(拐点)。将转折的中点记录下来。
●Tcg代表无定形聚合物或薄膜样品将从玻璃态开始结晶的峰值温度。表6中总括的Tcg是放热峰。ΔH Tcg代表样品在结晶期间释放的热量，通过测定结晶放热曲线下面的面积算出。
●Tm代表半结晶样品熔融的峰值温度。这是在第一遍加热时的吸热段。在13种实例薄膜中有10种，在第一遍加热中观察到2个熔融峰。ΔH Tm代表样品熔融所要求的额外热量，根据峰下的面积算出。
图8代表实例薄膜A从270℃～-40℃以10℃/min的速率(降温)的冷却曲线。在这一典型冷却曲线上，感兴趣的转折和峰值是：
●Tc是熔融聚合物在冷却和结晶的过程中表现出的峰值结晶温度，是感兴趣的。ΔH Tc是该峰下的面积，代表样品结晶期间从它释放的热量。
图9代表实例薄膜A从-40到270℃以10℃/min的速率第二遍加热。在图9所示第二加热曲线上，有一个Tg和一个Tm。在13种薄膜之一中，在第二遍加热上清楚地存在熔融峰。
表17总括了所有这13种实例薄膜的关键热性质。图10和11画出在110℃，关键热性质与热合强度之间的关联。图10标绘出第一遍加热时测定的Tg、Tcg和Tm随110℃下平均热合强度的变化。这样，图10就标绘出实例薄膜的热性质与110℃热合棒设定点下的平均峰值热合强度之间的关联。图11标绘出来自冷却曲线的Tcg，连同来自第二遍加热的Tg和Tm，与110℃热合棒设定点下的平均峰值热合强度之间的关系。热数据与平均热合强度之间的线性拟合也重叠地画在图10和11上，尽管可能存在某些线性关系，但相关系数(R2)一律都很差。总而言之，没有单一一个热性质可用来预测在110℃热合棒温度下将形成的热合强度。
表17总括13种单层薄膜的三遍DSC热测定的情况。
  第一遍加热   冷却   第二遍加热
  实例薄膜   Tg(℃)   Tcg(℃)   ΔHTcgJ/g   Tm℃   ΔHTmlJ/g   Tm℃   ΔH TmJ/g   Tcm℃   HtcmJ/g   Tg2nd℃   Tm2nd℃   ΔH Tm2J/g
  A   56   91   32   227   43   243   12   175   37   64   221   33
  B   60   111   30   225   28   244   23   169   31   67   219   33
  C   61   113   23   219   27   237   12   146   25   66   208   23
  D   55   92   30   226   43   241   9   168   36   64   219   32
  E   55   94   31   225   50   169   35   63   219   33
  F   56   95   30   225   51   172   37   63   220   35
  G   56   99   30   223   50   166   37   64   217   34
  H   58   114   28   223   33   240   16   159   31   68   215   32
  I   58   119   29   220   33   235   13   154   30   67   213   31
  J   59   111   29   225   34   241   16   165   30   68   217   30
  K   57   109   28   225   31   243   19   166   34   67   217   32
  L   58   113   28   224   50   243   NM   168   33   66   219   31
  M   54   106   26   226   31   244   20   169   32   66   219   32
NM＝未测定
实例组N～Z和AA及AB——可热合共挤出的聚酯薄膜：
单层样品薄膜A～M展示了，需要延长挤出机停留时间或提高熔体温度来制备含有共聚单体1，3-丙二醇的可热合单层流延膜。
从单层流延膜加工获悉对停留时间和/或提高熔体温度的需要，同样也适用于这样的共挤出薄膜，其中外层之一或二者被用于由包含共聚单体1，3-丙二醇的聚合物制造能热合的层。下列实例薄膜是采用Brampton Engineering(Brampton，安大略，加拿大)的三层吹胀膜挤出线制备的。一种具有三个截然不同层的薄膜管(泡)朝上挤出。图7试图描绘出由三层吹胀膜生产线生产出的管中的层排列。
该三层模头具有76mm(3英寸)直径环形模头本体，其上带有50mm(2英寸)环形唇和1650μm模隙。模头的每个层(A层、B层或C层)由相同的30/1长径比的32mm(一又四分之一英寸)直径挤出机进料。螺杆式样与前面在单层流延膜实例中所述的式样相同。每台挤出机由失重加料器供给树脂粒料。共挤出实例薄膜有一层(或者A或者C)由前面描述的共混物1或共混物2制成。所有情况下的芯层都由模头上的“B”层和B挤出机进料。所有情况下的芯层都是0.931g/cm3，2.8熔融指数(MI)的酸酐改性乙烯丙烯酸酯共聚物，由杜邦公司按商品名BynelTM 2174销售。三层结构中的第三层是
●0.962g/cm3密度，0.72MI的聚乙烯，由Nova化学公司按商品名SclairTM 19A销售。
或者
●0.958g/cm3密度，0.95MI的聚乙烯，由Nova化学公司按商品名SclairTM 19C销售。
熔融膜管一旦离开模头便受到Brampton Engineering供应的空气环的骤冷。从模头面到主夹辊的距离为约4.3m。所有共挤出实例薄膜都制成名义整体薄膜厚度61μm和夹瘪管平折(幅宽)210mm(2.7/1吹胀比)。在每种情况下，夹瘪管泡都沿直线纵切，从而生产出两片薄膜，它们被卷绕到76mm直径纸芯上，泡的内表面(A层)则卷绕在芯上。薄膜收卷机(型号DT 8366)由Macro Engineering(Mississauga，安大略，加拿大)制造。
树脂干燥和运输；
只有聚酯树脂在烘干的料斗干燥器系统中、121℃(250°F)下干燥过夜，然后再掺混和转移到氮气吹扫的失重加料斗中。聚乙烯和酸酐改性乙烯丙烯酸酯聚合物则直接由袋子或箱子加入到失重加料斗中；
表18总括了15种薄膜的名义结构。薄膜N～Z被制成膜泡内侧为该聚酯热合剂层的薄膜。薄膜AA和AB被制成膜泡外层是聚酯热合剂层。在所有情况下，酸酐改性乙烯丙烯酸酯聚合物都用作中间层。
表18——共挤出实例薄膜的名义结构
  实例薄膜   泡内A层   泡芯B层   泡外C层   各单层厚(μm)  总厚(μm)
  NOPQRSTUVWXYZAAAB   共混物2共混物2共混物2共混物1共混物1共混物2共混物2共混物1共混物1共混物2共混物2共混物2共混物1Sclair 19CSclair 19C   Bynel 2174Bynel 2174Bynel 2174Bynel 2174Bynel 2174Bynel 2174Bynel 2174Bynel 2174Bynel 2174Bynel 2174Bynel 2174Bynel 2174Bynel 2174Bynel 2174Bynel 2174   Sclair 19ASclair 19ASclair 19ASclair 19ASclair 19ASclair 19CSclair 19CSclair 19CSclair 19CSclair 19CSclair 19CSclair 19CSclair 19C共混物2共混物1   8/8/458/26/2715/8/388/8/4515/8/3815/8/3825/8/2825/8/2825/8/2825/8/2815/8/3815/8/3815/8/3838/8/1538/8/15  616161616161616161616161616161
图13显示根据在共挤出吹胀膜生产线上的A和C层的几何参数估计的停留时间。在这些曲线上重叠着根据投入到A挤出机进料喉中的着色粒料出现在膜唇处所需时间估计的停留时间。如同上一段关于单层薄膜所述，着色粒料偏于高估停留时间。
表19给出每种样品共挤出薄膜根据几何参数的停留时间估计值、测定的接套熔体温度(对于聚酯层)和共混物组合物中的3GT分数。在挤出机与模头之间穿过载有聚合物熔体的接套管壁平齐安装的探头估计出每层中聚合物的熔体温度。接套熔体温度是采用J型热电偶探头测定的，其中探头伸入到聚合物熔体中的深度可调。接套熔体流道的直径为约17mm。随着探头从壁向聚合物熔体流中心移动，测试确定的熔体温度最多升高3℃。
图13——根据几何参数的和利用着色粒料的A和C共挤出薄膜层的停留时间与螺杆转速的关系。
表19——共挤出薄膜的3GT分数、停留时间和接套熔体温度
  实例薄膜   x3GT   HUT(min)   MT℃   合计
  NOPQRSTUVWXYZAAAB   50％  +50％  +50％  +70％  -70％  -50％  +50％  +70％  -70％  -50％  +50％  +50％  +70％  -50％  +70％  -   5.5  +3.1  02.2  02.4  02.4  02.3  01.6  -1.5  -1.4  -1.4  -2.2  02.2  02.2  02.4  02.3  0   292  +292  +292  +291  +292  +272  -272  -271  -286  +293  +292  +292  +292  +280  0280  0   ++++0++0+-0+-0++0-+-------++-++0++0+-0++00-00
在表19中，
+标出那些对获得的热合强度应具有正影响的工艺因素。
-标出那些对获得的热合强度应具有负影响的工艺因素。
0标出那些代表高与低工艺条件之间中点的工艺因素。
根据表19中给各个实例薄膜上标出的+、0和-，并假定每种因素具有相等的重要性，一种三层以上的薄膜应表现得好于不足三层的薄膜。
实例薄膜N、U和AA的薄膜工艺条件载于表20。在每种情况下，沿边缘分切成两片，卷绕到分开的76mm直径纸芯上。
共挤出薄膜的分析；
薄膜卷被贮存在80～100μm厚聚乙烯袋中并扭转打结或用胶粘带密封。
共挤出样品薄膜贮存在处于环境条件中的塑料袋中长达7天，随后样品从袋子取出进行24h在23±1℃和50％RH下的调质。24h暴露后，薄膜热合在一起形成翼形封口。热合棒设定温度从90℃到130℃每隔10℃一档。热合是采用Sencorp Systems(Hyannis MA USA 02601)的型号12ASL/1热合机制备的。在90、100和110℃的热合棒设定点之下，不要求滑润垫片。在120和130℃，采用一种12.5μm(0.5密耳)杜邦Mylar薄膜滑润垫片以防止共挤出薄膜的聚乙烯外层粘连到热合棒上。Sencorp热合机调节在276kPa(40psi)的热合棒压力，2.5cm(1.0英寸)宽乘30.5cm(12.5英寸)长热合棒以及0.5s停留时间。仅加热上棒。下面的未加热棒包含一2.5cm宽×30.5cm长的红色橡胶，被夹在钢夹具中。按照ASTM程序F88，从热合的薄膜上模切一片25.4mm宽×70～100cm长的薄膜用以测试热合强度。该25.4mm宽的封条利用Instron试验机，型号4469在50.8mm(2英寸)初始夹具间距、25.4cm/min(10英寸/分钟)夹具张开速率和23±1℃及50％RH的条件下沿横向拉开。尾部用手扶着以保证尾部与拉开方向保持90°的取向。一般地，每一热合棒设定温度试验4个样品。样品N～AB的平均峰值热合强度，连同标准误差一并载于表10。另外，还给出试验条失效的模式。
表20实例薄膜N、U和AA的三层共挤出薄膜工艺条件
  实例薄膜 层A 层B 层C   空气环％   空气环内的空气℃   夹辊张力(kg)
  NUAANUAANUAANUAANUAA   共混物2共混物119C树脂产量A3.113.613.8层比例(％)A144065熔体压力(Bars)A2480256％马达负荷A114356   217421742174(kg/hr)B232.8B131214B296971B32927   19A19A共混物2C11.510.87.5C72.543.525.7C15421656C405425   41.939.439.3熔体温度A292271244层厚A8.925.638机筒压力A44136364rpmsA18.276.2148.3   232225℃B236233230B888B258485B6.226.424.3   3.63.63.7C236205280C452815C21028772C116.3109.546.3
  挤出机A   区1实际(℃)   区2实际(℃)   区3实际(℃)   区4实际(℃)   接套A实际(℃)   模头A实际(℃)
  NUAA   202243179   271246206   271246223   269246232   266247222   265257218
  挤出机B   区1实际(℃)   区2实际(℃)   区3实际(℃)   区4实际(℃)   接套B实际(℃)   模头B实际(℃)
  NUAA   152151149   221220222   219220220   220219218   221220219   234232228
  挤出机C   区1实际(℃)   区2实际(℃)   区3实际(℃)   区4实际(℃)   接套C实际(℃)   模头C实际(℃)
  NUAA   179178202   194195267   195197269   197198272   196196265   216218265
  模底实际(℃)   芯轴实际(℃)   外唇Lip实际(℃)   密度(g/cm3)A B C
  NUAA   245241223   241250234   235234235   1.331.330.96   0.930.930.93   0.960.961.33
  风机PcmH2O   霜白线高度Ht(cm) BUR DDR   Layflat(mm)   生产线速度(m/min)
  NUAA   121010   181822   2.72.62.8   10.010.010.1   208201219   10.615.915
表21平均热合强度(上标准误差)热合棒设定温度100，110，120和130℃
  实例薄膜   100℃   110℃   120℃   130℃
  N   865±375剥离   1,573±449脱层   1,542±209脱层   1,510±136脱层
  O   160±113剥离   1,424±289脱层   1,475±761脱层   1,309±504脱层
  P   143±62剥离   1,946±345脱层   2,216±513脱层   2,660±202脱层
  Q   1,074±90脱层   1,116±345脱层   817±171脱层   1,169±261脱层
  R   410±571剥离   2,086±120脱层   2,155±62脱层   2,257±552脱层
  S   0剥离   993±585剥离   1,341±243剥离   1,246±496剥离
  T   0剥离   1,604±1,062剥离   418±391剥离   1,149±1,106剥离
  U   1,484±785脱层   2,014±643脱层   1,600±827脱层   1,217±630脱层
  V   405±330剥离   764±484剥离   519±402剥离   528±360剥离
  W   2,207±432剥离   2,325±556脱层   2,466±383脱层   2,261±914脱层
  X   1,980±474脱层   1,678±334脱层   1,837±256脱层   1,800±460脱层
  Y   1,461±304脱层   2,539±651脱层   2,304±878脱层   2,054±492脱层
  Z   1,992±1,061脱层   2,383±415脱层   2,372±502脱层   2,408±747脱层
  AA   30±10   66±28   90±34   95±42
  剥离   剥离   剥离   剥离
  AB   217±122剥离   1,162±722脱层   960±700脱层   1,547±506脱层
在图14～28中，平均热合强度(包括误差线段(error bar))作为热合棒设定温度的函数进行标绘。误差线段代表用于计算平均值的4个样品中测得的热合强度最大和最小值。
这些数字显示，采用偏正一侧的工艺参数(3GT分数、HUT和熔体温度)或者至少负得最少的工艺参数制造的薄膜，往往具有最一致地牢固的热合效果(大于1000g/2.5cm封口)。
这15种共挤出实例薄膜中，薄膜S(+0-)、T(+--)、V(--+)和AA(+00)全都表现出在110、120和130℃的不可心的封口剥离失效模式。优选的是，结合层与热合层彼此脱层是主要失效模式。具有剥离失效模式的薄膜样品一般具有低于标准热合强度1000g/2.5cm的热合强度。实例薄膜U(---)虽具有不稳定的不可心热合强度但其失效模式却是脱层且平均值高于1000g/2.5cm封口。
实例29和30
实例薄膜29和30展示3GT共聚物作为低温热合层的有效性。实例薄膜29由一种共聚物制成，后者由对苯二甲酸、环己烷二甲醇和1，3-丙二醇制成，被称作3GT/CHDM。实例薄膜30由这样的共聚物制成，后者由对苯二甲酸二甲酯、乙二醇和1，3-丙二醇制成。3G与2G的比例基本上等于70/30的比例，被称作3GT/2GT。
由1，4-环己烷二甲醇(CHDM)/对苯二甲酸二甲酯和1，3-丙二醇制备3GT/CHMD(约10mol％)共聚物：
在25加仑反应器中加入120磅对苯二甲酸二甲酯、12.3磅CHDM、60磅1，3-丙二醇以达到1.4∶1的(1，3-丙二醇+CHDM)∶DMT的摩尔比，以及6.6g钛酸酯催化剂。温度升高到200℃，然后保持2h。产生的甲醇通过蒸馏作为液态凝结物移出。
甲醇的释放开始减少后，所生成的预聚物转移到不同的压热釜中并在250℃的温度和0.4mm汞柱的压力下聚合4h。获得的无规共聚物树脂造粒。聚合物的特性粘度是0.77dl/g。与实例29无定形薄膜的工艺条件有关的数据以及结果载于表22、23和24。
由对苯二甲酸二甲酯、1，3-丙二醇和乙二醇制备3GT/2GT(约30mol％)共聚物：
在25加仑反应器中加入120磅对苯二甲酸二甲酯、47.5磅3G、16磅2G以便达到1.4∶1的(3G+2G)∶DMT的摩尔比，以及18g Tyzor(R)TPT作为催化剂。温度升高到210℃，然后保持2h。产生的甲醇通过蒸馏作为液态凝结物移出。
甲醇的释放开始减少后，所生成的预聚物转移到一台压热釜中并在250℃的温度和0.4mm汞柱的压力下聚合3h。获得的共聚物3GT/2GT造粒。该无规聚合物的特性粘度是0.782dl/g。流延成薄膜之前，聚合物在氮气吹扫的烘箱内、130℃下结晶3h。该结晶的聚合物随后在182℃、充填床固相聚合器中利用连续热氮气流进行8h的固相聚合。
实例薄膜29和30的制备在与制备实例薄膜1～6和11所用相同的流延膜设备单元上进行。用于制备薄膜样品29和30的无定形树脂的热性质利用与测定实例薄膜1～6所用相同的DSC技术进行测定。实例薄膜29利用与实例薄膜1～6所用相同的热合条件和设备进行热合。同样地，同一slip-peel试验机被用于测定热合强度。用于制备实例薄膜29和30的无定形树脂的第一遍加热热性质总括在表23中。实例薄膜29和30的热合强度对热合棒设定温度的关系载于表24中。
表22无定形薄膜样品29和30的工艺条件
  实例#   29   30
  树脂   3GT/CHDM   3GT/2GT
  Wt.％   100   100
  挤出机条件   实际温度   实际温度
  机筒区1(℃)   240   260
  机筒区2   240   240
  机筒区3   240   240
  机筒区4   240   240
  过滤器法兰-模头1   240   241
  接套-模头2   240   238
  进料头-模头3   250   240
  端法兰-模头4   240   240
  扁平模头-模头5   240   240
  过滤器 熔体   234   235
  接套 熔体   240   246
  过滤器前压力(psi)   1510   2260
  过滤器后压力(psi)   750   1140
  螺杆R.P.M.   40   50
  螺杆电流(A)   2.8   3.4
  流延单元
  流延辊-F.P.M.   39   60
  引出辊与流延辊的比值   1.05   1.03
  曲面辊与流延辊的比值   1.0   1.0
  边缘销   有   有
  引出辊辊隙
  压力-PSI   50   50
  薄膜厚度(密耳)   1.5   1.4
  产量(gm/min)   90   125
  产量(lb/hr)   11.9   16.5
  水循环单元温度设定/实际°F   65   55
表23——无定形树脂样品3GT/CHDM和3GT/2GT的第一遍加热热性质
  实例   Tg(℃)  Tcg(℃)  ΔH Tcg(J/g)   Tm(℃)   ΔH Tm(J/g)
  3GT/CHDM   49.0  85.0  31.8   216.0   44.0
  3GT/2GT   54  85.4  30.4   212.4   49.2
表24——实例薄膜29和30的平均热合强度与热合棒设定温度热合强度单位是g/0.5in
  热合棒设定温度℃   实例薄膜12   实例薄膜13
  90   0   686
  100   0   1084
  110   180   1172
  120   1024   1364
  130   1124   1471
  140   1513   1177
实例31和32
在40℃和80％RH下调质4天后的伸长保持
在前面提到的日本专利JP 10279707中公开了一种共聚聚酯薄膜，它在40℃贮存5天后将具有100％伸长。在此将退火条件和随后薄膜的伸长试验描述如下：
伸长：在将薄膜放在40℃的温度和80％相对湿度下5天后，我们测定了10mm宽和50mm长的薄膜样品沿纵向和横向的断裂伸长(％)，所用拉伸试验机以300mm/min的拉伸速率拉伸，按照ASTM D-882-81(A)方法实施。每个方向试验的次数(n)是5，然后求平均值。
为展示本发明公开的典型薄膜将不保持所要求的100％伸长，我们测定了在调质4和7天前后实例薄膜31和32的伸长，调质条件基本如同日本专利JP10-279707所述，即，调质设备在7天时间内维持在40℃和RH＝80±10％。
薄膜制备：
实例薄膜31和32由实例9和10的固态聚合实例树脂流延成形。薄膜流延的条件载于表25中。
按照ASTM D882的抗张试验：
样品12.7mm(0.5英寸)宽×101.6mm(4英寸)长被从实例薄膜31和32上模切下来。一组样品以其长轴沿纵向(MD)切取；一组样品以其长轴沿横向(TD)切取。随后，从每种薄膜上切取的6个MD和6个TD取向的样品在50％RH和23℃(72°F)下调质2天。调质后，按照ASTM D882方法A采用Instron型号4469，将隔距调节在2英寸和XHS(按该日本专利)在300mm/min测定断裂伸长。另外从每种薄膜采取的MD和TD样品在40±5℃和80±10％RH下调质3.8和7天。经过提高条件的调质后，让样品在23℃和50％RHRH下重新平衡，随后再次测定断裂伸长。图29标绘出40℃下调质前后实例薄膜31和32的平均纵向断裂伸长。图30标绘出同样调质时间后TD断裂伸长的变化。
表15——无定形实例薄膜14和15的工艺条件
  实例薄膜#   14   15
  树脂   树脂9   树脂10
  20wt％3GT 80wt％2GT-I   70wt％3GT 30wt％2GT-I
  挤出机条件   实际温度   实际温度
  机筒区1℃   280   285
  机筒区2   270   270
  机筒区3   270   270
  机筒区4   270   270
  过滤器法兰-模头1   270   270
  接套-模头2   270   270
  进料头-模头3   270   270
  端法兰-模头4   270   270
  扁平模头-模头5   270   270
  过滤器熔体   264   254
  接套熔体   270   250
  过滤器前压力(psi)   1430   1800
  过滤器后压力(psi)   700   910
  螺杆R.P.M.   40   40
  螺杆电流(A)   2.9   2.8
  流延单元
  流延辊-F.P.M.   53   52
  引出辊与流延辊的比值   1.02   1.02
  曲面辊与流延辊的比值   1.00   1.00
  边缘销   有   有
  薄膜厚度(密耳)   96   94
  产量(gm/min)   96   94
  产量(lb/hr)   12.7   12.4
  水循环单元温度设定/实际°F   60   60

Claims (31)

1.一种包含两种不同聚酯的掺混物的组合物，具有从介于约40℃～约70℃范围的玻璃化转变温度Tg，到介于约70℃～约150℃范围的自无定形状态的峰值结晶温度Tcg的无定形加工范围。
2.权利要求1的组合物，其中无定形加工范围从介于约48℃～约70℃范围的Tg到介于约80℃～约135℃范围的Tcg。
3.权利要求1的组合物，其中两种不同聚酯至少之一包含聚对苯二甲酸丙二醇酯均聚物或共聚物。
4.权利要求1的组合物，其中熔点Tm介于约180℃～约240℃。
5.权利要求3的组合物，其中IV介于约0.4～约2.0dl/g。
6.一种聚酯组合物，包含聚对苯二甲酸乙二醇酯均聚物或共聚物和约5％～约95wt％聚对苯二甲酸丙二醇酯均聚物或共聚物，以聚对苯二甲酸乙二醇酯和聚对苯二甲酸丙二醇酯的总重量为基准。
7.权利要求6的组合物，包含约30％～约70wt％聚对苯二甲酸丙二醇酯均聚物或共聚物。
8.权利要求6的组合物，其中此种组合物是均聚物的物理共混物或每种组分的共聚物。
9.权利要求6的组合物，其中物理掺混后的最终IV至少为约0.80dl/g。
10.权利要求6的组合物，其中此种组合物是通过对苯二甲酸、乙二醇、1，3-丙二醇以及任选地其他成酯单体的缩聚生成的共聚物。
11.权利要求6～10中任何一项的组合物，其中无定形加工范围从介于约40℃～约70℃范围的玻璃化转变温度Tg，到介于约70℃～约150℃范围的自无定形状态的峰值结晶温度Tcg。
12.权利要求10的组合物，其中该组合物表现出至少是50℃的Tg，介于约5～约12cc/d-645cm2(100平方英寸)-atm在23℃的氧透过速率，并显示良好香味/异味阻隔性能。
13.由权利要求1～10中任何一项的组合物制成的制品。
14.由权利要求1～10中任何一项的组合物制成的薄膜。
15.由权利要求11的组合物制成的薄膜。
16.包含权利要求14的薄膜的多层薄膜。
17.包含权利要求15的薄膜的多层薄膜。
18.由权利要求16的薄膜制成的包装。
19.由权利要求17的薄膜制成的包装。
20.一种降低聚对苯二甲酸乙二醇酯均聚物或共聚物的Tg的方法，包括下列步骤：
(a)将聚对苯二甲酸丙二醇酯均聚物或共聚物加入到结晶的聚对苯二甲酸乙二醇酯均聚物或共聚物中形成一种共混物；
(b)干燥该共混物：令该共混物在介于约120℃～约130℃的温度下暴露于至少0.028m3/min(1ft3/min)露点低于-20.5℃(-5°F)的干燥空气流中达至少约6h或直至达到足够干燥的程度；
(c)熔融掺混该共混物以形成Tg低于步骤(a)的聚对苯二甲酸乙二醇酯的聚合物。
21.一种制造低温-可热合聚酯薄膜的方法，包括下列步骤：
(a)将聚对苯二甲酸丙二醇酯均聚物或共聚物加入到结晶的聚对苯二甲酸乙二醇酯均聚物或共聚物中形成一种共混物；
(b)干燥该共混物：令该共混物在介于约120℃～约130℃的温度下暴露于至少0.028m3/min(1ft3/min)露点低于-20.5℃(-5°F)的干燥空气流中达至少约6h或直至达到足够干燥的程度；
(c)熔融掺混该共混物以形成Tg低于步骤(a)的聚对苯二甲酸乙二醇酯的聚合物。
22.两个热塑性塑料的热合方法，其中这两个热塑性表面借助加热和加压彼此热合，其中改进之处在于热塑性塑料至少之一包含一种含有聚对苯二甲酸乙二醇酯均聚物或共聚物和聚对苯二甲酸丙二醇酯均聚物或共聚物的共混物或者由各自单体制成的共聚物的聚酯组合物。
23.权利要求21的方法，其中聚酯组合物包含聚对苯二甲酸乙二醇酯均聚物或共聚物和约20％～约80wt％聚对苯二甲酸丙二醇酯均聚物或共聚物，以聚对苯二甲酸乙二醇酯和聚对苯二甲酸丙二醇酯的总重量为基准。
24.权利要求22的方法，其中聚酯组合物表现出从介于约40℃～约70℃范围的玻璃化转变温度Tg，到介于约70℃～约150℃范围的自无定形状态的峰值结晶温度Tcg的无定形加工范围。
25.一种制品，其中两个热塑性表面被热合在一起了，其中所述热塑性表面至少之一包含一种含有聚对苯二甲酸乙二醇酯均聚物或共聚物和聚对苯二甲酸丙二醇酯均聚物或共聚物的共混物或者由各自单体制成的共聚物的聚酯组合物。
26.权利要求24的制品，其中聚酯组合物包含聚对苯二甲酸乙二醇酯均聚物或共聚物和约5％～约95wt％聚对苯二甲酸丙二醇酯均聚物或共聚物。
27.权利要求25的制品，其中聚酯组合物表现出从介于约40℃～约70℃范围的玻璃化转变温度Tg，到介于约70℃～约150℃范围的自无定形状态的峰值结晶温度Tcg的无定形加工范围。
28.一种生产可热合薄膜或片材的方法，包括下列步骤：
(d)挤出由两种不同聚酯部分构成的混合物，它包含95～5重量份聚对苯二甲酸乙二醇酯均聚物或共聚物部分与5～95重量份聚对苯二甲酸丙二醇酯均聚物或共聚物部分，其中所述挤出是在聚合物在挤出机和模头中的停留时间介于1～15min、在235～290℃温度的条件下进行的；
(e)对在步骤(a)中产生的挤出聚酯熔体实施骤冷；以及
(f)回收一种聚酯薄膜或片材，它具有从约40℃～约70℃的Tg到约70℃～约150℃自无定形状态的峰值结晶温度Tcg的无定形加工范围。
29.权利要求28的方法，其中两种不同聚酯部分的所述混合物包含聚对苯二甲酸乙二醇酯均聚物粒料、聚对苯二甲酸乙二醇酯共聚物粒料或其混合物作为一种截然不同聚酯部分，以及聚对苯二甲酸丙二醇酯均聚物粒料、聚对苯二甲酸丙二醇酯共聚物粒料或其混合物作为另一种截然不同聚酯部分。
30.权利要求28的方法，还包括，在挤出前，所述两种截然不同聚酯部分之一或二者通过所述部分或混合物在介于约120℃～约130℃的温度暴露于至少约0.028m3/min(1ft3/min)露点低于-20.5℃(-5°F)的干空气中至少约6h进行干燥的步骤。
31.权利要求28的方法，其中两种截然不同聚酯部分的混合物的挤出是与至少一种其他聚合物的挤出在多层薄膜或片材的共挤出过程中同时实施的。
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CN104650546B (zh) * 2013-11-18 2017-04-12 柯尼卡美能达株式会社 热塑性树脂组合物的制造方法
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CN109664587B (zh) * 2018-12-31 2020-08-25 金华威派包装有限公司 一种可重复使用的礼品包装复合塑料膜及制备方法

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US20020012807A1 (en) 2002-01-31
CN100384935C (zh) 2008-04-30
JP2004530000A (ja) 2004-09-30
US6902802B2 (en) 2005-06-07
EP1370608B1 (en) 2006-03-08
WO2002070606A1 (en) 2002-09-12
JP2012229447A (ja) 2012-11-22
EP1370608A1 (en) 2003-12-17
DE60117817D1 (de) 2006-05-04
US6663977B2 (en) 2003-12-16

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