CN101001739A - 型坯以及由该型坯形成的吹塑成型容器 - Google Patents

型坯以及由该型坯形成的吹塑成型容器 Download PDF

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Publication number
CN101001739A
CN101001739A CNA2005800273991A CN200580027399A CN101001739A CN 101001739 A CN101001739 A CN 101001739A CN A2005800273991 A CNA2005800273991 A CN A2005800273991A CN 200580027399 A CN200580027399 A CN 200580027399A CN 101001739 A CN101001739 A CN 101001739A
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China
Prior art keywords
parison
preform
neck ring
pet
blow
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Granted
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CNA2005800273991A
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CN101001739B (zh
Inventor
北野善扩
菊地淳
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Toyo Seikan Group Holdings Ltd
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Toyo Seikan Kaisha Ltd
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Publication of CN101001739A publication Critical patent/CN101001739A/zh
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    • 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
    • B29C43/00—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor
    • B29C43/02—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor of articles of definite length, i.e. discrete articles
    • B29C43/20—Making multilayered or multicoloured articles
    • B29C43/203—Making multilayered articles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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    • B29C49/00—Blow-moulding, i.e. blowing a preform or parison to a desired shape within a mould; Apparatus therefor
    • B29C49/02—Combined blow-moulding and manufacture of the preform or the parison
    • B29C49/0685—Compression blow-moulding
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    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B11/00—Making preforms
    • B29B11/06—Making preforms by moulding the material
    • B29B11/12—Compression moulding
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Abstract

本发明提供型坯，该型坯至少具有含有聚酯树脂的层，在通过压缩成型得到的口部具有颈环，其特征在于：上述聚酯层的底部中心或颈环下的下式所示温度差ΔTc为15℃以下：ΔTc＝Tc2－Tc1式中，Tc1表示通过差示扫描量热仪(DSC)对由型坯切取的聚酯层测定的升温结晶峰温度，Tc2表示进行了Tc1测定、熔融后骤冷测定的升温结晶峰温度。由此，可以得到成型变形小、口部结晶时的尺寸稳定性优异的型坯。并且，将上述型坯拉伸吹塑成型而得的成型品壁厚不会产生厚薄不均、或者划痕或皱纹，外观特性优异。

Description

型坯以及由该型坯形成的吹塑成型容器
技术领域
本发明涉及通过压缩成型制备型坯以及将该型坯拉伸吹塑成型而成的吹塑成型容器，更具体地说，本发明涉及尺寸稳定性优异的型坯以及具有均匀壁厚、同时外观特性也优异的拉伸吹塑成型容器。
背景技术
拉伸吹塑成型塑料容器、特别是双轴拉伸聚酯容器现今已经得到普及，由于其优异的透明性和适度的阻气性，被广泛应用在液体洗剂、香波、化妆品、酱油、汤汁等液体商品中，除此之外也用作啤酒、可乐、汽水等碳酸饮料或果汁、矿泉水等其它饮料的容器。
双轴拉伸聚酯容器成型时采用以下方法：通过聚酯树脂的注射成型，预先形成尺寸比最终容器小很多、且聚酯为非晶的有底型坯，将该型坯预加热至其拉伸温度，在吹塑模具中沿轴向牵引拉伸，同时沿圆周方向吹塑拉伸(例如日本特开平4-154535号公报)。
该有底型坯的形状具备相当于容器口颈部和可拉伸吹塑成型的有底筒状部，整体形状通常为试管状，口颈部形成与用于密封的开口端或盖相配合的结构。该底部需要注射成型，因此一定会形成由底部中心向外凸出的浇口部。
已知可通过树脂的压缩成型制备有底型坯，有人提出了一种型坯的制备方法，该方法包含：将由挤出机挤出的熔融树脂块切断并保持，供给阴模，然后将阳模压入上述阴模，在阴模内压缩成型(日本特开2000-280248号公报)。
发明内容
但是，通常在通过注射成型制备型坯时，熔融塑化树脂经由喷嘴、注料道、流道、浇口注入模腔内，因此树脂在注射成型机中的停留时间长，上述在成型机中的长时间停留是导致树脂劣化的原因。特别是聚酯树脂，因热分解而使特性粘度或分子量降低，因此出现无法获得满意的机械强度的问题。另外，通过注射成型制备的型坯中，在其特有的浇口部和其附近容易发白，而在将其拉伸吹塑成型而成的瓶中，会发生底部发白、细微裂纹等，外观特性差，同时耐冲击性也差。
与此相对，通过压缩成型制备的型坯中，不会发生上述注射成型的型坯所出现的问题，表面圆滑，可获得底部没有发白或细微裂纹的型坯，但是又会产生与注射成型不同的问题。
即，通过压缩成型进行的型坯成型中，由挤出机挤出的树脂局部性地温度降低，由此在压缩成型时发生型坯变形，该倾向在树脂流动距离比型坯的底部更长的口颈部附近更为显著。具有上述成型变形的型坯，特别是口颈部在结晶前后尺寸稳定性差，另外，将上述型坯进行双轴拉伸吹塑成型时，所得成型品的壁厚不均，并且可能会有划痕产生。
因此，本发明的目的在于提供成型变形低、尺寸稳定性优异的通过压缩成型得到的型坯。
本发明的另一目的在于提供壁厚均匀，没有划痕或皱纹发生的拉伸吹塑成型容器。
本发明可以提供一种型坯，该型坯是至少具有含有聚酯树脂的层，通过压缩成型制备，在口部具有颈环(颈嵌件)，其特征在于：上述聚酯层的底部中心或颈环下，下式(1)所示的温度差ΔTc为15℃以下：
ΔTc＝Tc2-Tc1    …  (1)
式中，Tc1表示通过差示扫描量热仪(DSC)测定由型坯切取的聚酯层得到的升温结晶峰温度，Tc2表示进行了Tc1测定、熔融后骤冷测定的升温结晶峰温度。
本发明的型坯中，由颈环下至底部的长度L和口部顶面外径D之比L/D优选小于3.5。
本发明还提供将上述型坯拉伸吹塑成型得到的吹塑成型容器。
本发明的型坯中，其重要的特征在于：聚酯层的底部中心或颈环下的上式(1)所示温度差ΔTc为15℃以下。
即，如上所述，在由通过压缩成型得到的型坯中，压缩成型时熔融树脂块局部性地温度降低、以及熔融树脂在压缩成型模内流动，由此产生成型变形。该成型变形特别是熔融树脂在压缩成型模内流动距离长的口颈部显著，所述部位进行结晶时，难以保持其尺寸，结晶前后的尺寸稳定性差。
由上述角度考虑，本发明的目的在于提供成型变形低的型坯，本发明人发现：型坯的聚酯层底部中心或颈环下，如果上式(1)所示温度ΔTc为15℃以下，则该型坯成型变形低，即使进行型坯的口颈部结晶，也无损尺寸稳定性。
另外，使用本发明的型坯进行拉伸吹塑成型而成的拉伸吹塑成型容器，没有壁厚不均，另外没有发白或划痕、皱纹等，外观特性优异。
即，本发明中，通过差示扫描量热仪(DSC)测定具有因压缩成型而产生的成型变形(流动取向)状态的型坯的升温结晶峰温度(Tc1)，然后使其熔融，使Tc1测定后的聚酯层的成型变形缓和，通过骤冷，消除其成型热程，再测定该聚酯树脂的特性升温结晶峰温度(Tc2)，则发现该差ΔTc明确地显示型坯的成型变形，同时发现该ΔTc为15℃以下的型坯，其成型变形小，不会因口部结晶或吹塑成型而产生壁厚不均，可提供尺寸稳定性和外观特性优异的型坯。
这由后述的实施例结果即可明了。即，ΔTc比15℃大的型坯中，在进行口部结晶时，口部先端的变形量为0.3mm以上，较大，口部先端的平面度差(比较例1-2)，而ΔTc为15℃以下的型坯中，变形量低于0.3mm，与比较例相比，尺寸稳定性明显优异(实施例1-7)。
附图简述
图1是表示本发明的型坯的一个例子的侧面图。
图2是表示在成型本发明的多层型坯时所使用的压缩成型装置的说明图。
实施发明的最佳方式
图1是表示本发明的型坯的一个例子，(A)是通常的PET瓶中使用的型坯，(B)是广口瓶中使用的广口浅型型坯。如图1所示，本发明的型坯20包含口颈部21、胴体部22和底部23，通常，口颈部21形成螺纹部24，在螺纹部24的下部形成颈环部25。本发明的上式(1)所示的ΔTc可以由从型坯的底部23的中心部26或颈环25的正下方27切取的聚酯层、或者从该型坯拉伸吹塑成型而成的拉伸吹塑容器分别对应的位置切取的聚酯层测定。
本发明中，以型坯的聚酯层底部中心或颈环下部分的升温结晶峰温度作为问题的提出，这是由于在通常的通过一步吹塑成型法拉伸吹塑成型得到的成型容器中，为了测定型坯的成型变形，通常，底部中心难以受拉伸或加热的影响，最接近型坯的状态，因此是最优选的位置，但是通过两步吹塑成型法拉伸吹塑成型时，在第一步吹塑步骤中，底部被拉伸，同时在之后的加热收缩步骤中被加热，成型容器底部中心的成型变形得到缓和，因此，成型容器的底部中心难以反应型坯的成型变形。因此，像两步吹塑成型法这样，如果底部中心的变形得到缓和，颈环下部分最不容易受拉伸或加热影响，是残留成型变形的位置，因此可由成型容器近似地求出型坯的聚酯层的升温结晶峰温度。
因此，本发明中，拉伸吹塑成型后的成型容器中，可测定型坯成型变形的位置规定为底部中心或颈环下部分，在通常的一步吹塑成型法的拉伸吹塑成型中，如果是底部中心和颈环下部分两个位置的聚酯层的ΔTc均为15℃以下，则毋庸置疑最好，其中一处的聚酯层的ΔTc为15℃以下即可。
另外，两步吹塑成型法的拉伸吹塑成型中，只要颈环下部分位置的聚酯层的ΔTc为15℃以下即可。
并且，对于具有聚酯层的多层型坯，可以从聚酯层切取试样，进行同样的测定。
(聚酯树脂)
本发明中使用的聚酯树脂可以使用以往通过压缩成型进行型坯成型时所使用的含有二羧酸成分和二醇成分的聚酯树脂。
二羧酸成分中，从机械性质或热学性质看，优选二羧酸成分的50％以上、特别是80％以上为对苯二甲酸，当然也可以含有对苯二甲酸以外的羧酸成分。对苯二甲酸以外的羧酸成分有：间苯二甲酸、萘二甲酸、对-β-羟乙氧基苯甲酸、联苯-4，4’-二甲酸、二苯氧基乙烷-4，4’-二甲酸、间苯二甲酸-5-磺酸钠、六氢对苯二甲酸、己二酸、癸二酸等。
作为二醇成分，从机械性质或热学性质看，优选二醇成分的50％以上、特别是80％以上为乙二醇，乙二醇以外的二醇成分有：1，4-丁二醇、丙二醇、新戊二醇、1，6-己二醇、二甘醇、三甘醇、环己烷二甲醇、双酚A的环氧乙烷加成产物、甘油、三羟甲基丙烷等。
从调节树脂的熔融挤出时的熔融粘度、熔融张力，防止下垂等的目的考虑，可以添加多官能成分，多官能成分是三官能以上的多元酸和多元醇，有偏苯三酸、均苯四甲酸、连苯三酸、1，1，2，2-乙烷四甲酸、1，1，2-乙烷三甲酸、1，3，5-戊烷三甲酸、1，2，3，4-环戊烷四甲酸、联苯-3，4，3’，4’-四甲酸等多元酸，或季戊四醇、甘油、三羟甲基丙烷、1，2，6-己三醇、山梨醇、1，1，4，4-四(羟甲基)环己烷等多元醇。
本发明中使用的聚酯树脂是通过压缩成型成型为型坯，因此优选具有0.70～0.90dL/g、特别是0.75～0.85dL/g(使用重量比1∶1的苯酚/四氯乙烷混合溶剂，在30℃下测定)的特性粘度。
并且，为了满足型坯或聚酯容器的耐热性、加工性等，聚酯树脂优选具有低于265℃、特别是220～255℃的熔点(Tm)。另外，玻璃化转变温度优选30℃以上，特别是50～120℃的范围。
可以在不损害最终成型品品质的范围内，按照公知的配方，向本发明使用的聚酯树脂中配合其本身为公知的树脂用配合剂，例如着色剂、抗氧化剂、稳定剂、各种抗静电剂、脱模剂、润滑剂、晶核剂等。
(型坯)
本发明的型坯只要是聚酯层的底部中心或颈环下的上式(1)所示温度差ΔTc为15℃以下即可，当然可以是只含有聚酯树脂的单层，也可以是除含有聚酯树脂的层之外还具有含其它热塑性树脂的层的多层型坯。
聚酯树脂以外的热塑性树脂只要是可拉伸吹塑成型和热结晶的树脂即可，可以使用任何树脂，没有限定，可以是聚乙烯、聚丙烯、乙烯-丙烯共聚物、乙烯-乙烯醇共聚物、环状烯烃聚合物等烯烃系树脂，或含有亚二甲苯基的聚酰胺等聚酰胺树脂等。还可以使用含亚二甲苯基的聚酰胺中配合有二烯系化合物、过渡金属系催化剂的吸氧性阻气树脂组合物，或再生聚酯(PCR(将使用后的瓶再生的树脂)、SCR(在生产工厂内产生的树脂)或它们的混合物)等。这些再生聚酯树脂优选按照上述方法测定的特性粘度(IV)在0.65～0.75dL/g的范围。
再生聚酯可以单独使用，也可以以与新聚酯的共混物的形式使用。再生聚酯具有较低的特性粘度时，优选与新聚酯共混使用，此时，再生聚酯∶新聚酯的配合比优选1∶5～5∶1的重量比。
为了使内层或外层与中间层粘合，可以经由粘合性树脂。粘合性树脂可以使用将马来酸等进行接枝聚合得到的酸改性烯烃系树脂或非晶态的聚酯系树脂或聚酰胺系树脂等。
除上述聚酯树脂以外的热塑性树脂中还可以与上述压缩成型用聚酯树脂同样地配合各种树脂用添加剂。
对本发明的多层型坯的层构成没有限定，可以例举以下构成。以下多层结构中的简略符号如下表示：PET：聚酯树脂，GBR：阻气性树脂，PCR：再生聚酯树脂，ADR：粘合性树脂，OAR：吸氧性树脂组合物，COC：环状烯烃共聚物。
三层结构：PET/GBR/PET、PET/PCR/PET
PET/(PET+PCR)/PET
PET/(PET+OAR)/PET
四层结构：PET/GBR/PCR/PET
PET/GBR/OAR/PET
PET/GBR/COC/PET
五层结构：PET/ADR/GBR/ADR/PET
PET/ADR/OAR/ADR/PET
PET/GBR/PCR/GBR/PET
PET/ADR/(GBR+OAR)/ADR/PET
PET/(PET+OAR)/PET/(PET+OAR)/PET
六层结构：PET/ADR/GBR/ADR/PCR/PET
PET/ADR/OAR/ADR/PCR/PET
七层结构：PET/PCR/ADR/GBR/ADR/PCR/PET
PET/ADR/GBR/ADR/OAR/ADR/PET
(型坯的成型)
本发明中，可使用上述聚酯树脂，通过压缩成型法成型型坯，重要的是为了降低型坯的成型变形，要使上述ΔTc的值为15℃以下。
图2是表示成型多层型坯时所使用的压缩成型装置的说明图，将全体用1表示的压缩成型装置是将含有本发明的压缩成型用聚酯树脂的内外层用树脂A由主挤出机2连续供给，将阻气性树脂等中间层用树脂B由副挤出机3间歇性供给，在多层模头4内合流，使树脂A密封树脂B，从设在多层模头4下方的喷嘴5进行熔融挤出，通过可沿水平方向移动的切断装置6，将挤出的复合熔融树脂7在不存在中间层的部分切断成规定尺寸。该切断的复合熔融树脂块8在切断后立即被夹具夹持，运输到由阴模9和阳模10构成的压缩成型装置的阴模9内。将在阴模9内的复合熔融树脂块8用阳模10进行压缩成型，成型为中间层被内层和外层密封的多层型坯。
本发明中，在上述成型法中，为了降低型坯的成型变形、使上述ΔTc的值在15℃以下，可采用以下手段。
即，如上所述，成型变形是由于熔融树脂块冷却而导致的，因此优选使由挤出机挤出的熔融树脂被切断后至压缩成型结束的时间(不包括冷却时间)(成型周期)缩短，防止熔融树脂的温度降低，或者除通过上述缩短时间来防止温度降低之外，还优选考虑到压缩成型的条件等，在成型相同树脂和相同形状的型坯时，优选以以往的成型周期的95～50％以下的成型周期进行压缩。当然这也根据型坯的形状而定。由此，由后述实施例6和比较例1可知，如果是相同树脂且为相同形状的型坯，与成型周期为20秒的情况相比，通过将其减为3秒(降低至15％)，则ΔTc的值在颈环下部降低63％，在底部降低69％左右。
型坯的形状不同则ΔTc的值不同，如后述实施例1和比较例3可知，如图1所示，由颈环下至底部的长度L和口部顶面的外径D之比L/D为0.47的型坯和L/D为4.4的型坯，其ΔTc的值显著不同。因此，本发明中，特别优选颈环下至底部的长度L和口部顶面的外径D之比L/D为小于3.5的型坯。
因此，为了制成本发明的型坯和吹塑成型容器，通过采用上述的缩短型坯的成型周期、改变型坯形状的其中一种或两种手段均可实现，但是上述型坯形状的L/D值大时，优选缩短型坯的成型周期。
并且，型坯的成型变形因加热而缓和，因此在压缩成型后，可以对型坯均匀加热0.1～1秒左右，使型坯的表面温度为200～250℃。
(聚酯容器)
本发明的吹塑成型聚酯容器可通过对上述型坯进行拉伸成型获得。
拉伸吹塑成型中，将本发明的型坯加热至拉伸温度，将该型坯沿轴向拉伸，同时沿圆周方向双轴拉伸吹塑成型，制备双轴拉伸容器。
型坯的成型及其拉伸吹塑成型除采用冷型坯方式之外，还可以采用型坯完全不冷却即进行拉伸吹塑成型的热型坯方式。
在拉伸吹塑之前，可以根据需要通过热风、红外线加热器、高频诱导加热等方式将型坯预加热至拉伸适宜温度。如果是聚酯树脂，则该温度范围在85～120℃，特别优选95～110℃的范围。
将该型坯供给其本身为公知的拉伸吹塑成型机中，安装在模具内，通过拉伸棒的压入，沿轴向牵引拉伸，同时通过通入流体，沿圆周方向拉伸成型。模具温度通常优选室温至190℃的范围，如后所述，在通过单模法进行热定型时，优选将模具温度设定为120～180℃。
最终的聚酯容器的拉伸倍率按照面积倍率计算，1.5～25倍较适宜，其中优选轴向拉伸倍率为1.2～6倍，圆周方向拉伸倍率为1.2～4.5倍。
本发明的吹塑拉伸聚酯容器可通过其本身为已知的方式进行热定型。热定型可按照在吹塑成型模具中进行的单模法进行，也可以以在与吹塑成型模具不同的热定型用模具中进行的双模法进行。热定型的温度在120℃～180℃的范围较为适宜。
作为其它拉伸吹塑成型方法，如本申请人申请的专利第2917851号公报中所举的例子，可以采用如下所述的两步吹塑成型法：使用1次吹塑模具，将型坯制成比最终成型品尺寸大的1次吹塑成型体，接着使该1次吹塑成型体加热收缩，然后使用2次吹塑模具进行拉伸吹塑成型，制成最终成型品。测定由该方法得到的聚酯容器的ΔTc时，如前所述，底部的成型变形得到缓和，因此必须测定颈环下部分的ΔTc。
实施例
通过以下例子进一步对本发明进行说明，但本发明并不受这些实施例的限定。
[型坯的成型]
由设定温度为270℃的模头下部的喷嘴挤出聚对苯二甲酸乙二醇酯，将挤出的聚对苯二甲酸乙二醇酯切断，将所得熔融树脂块运输到压缩成型装置中，以9mm/秒的压缩成型速度(压缩成型装置中阳模的移动速度)进行压缩成型，至压缩成型结束为一个成型周期。改变熔融树脂块在运送到压缩成型装置之后至压缩成型开始的时间，调节成型周期。
[DSC测定]
从成型的型坯和瓶中适当选择型坯和瓶的颈环下的部位、以及从底部中心沿厚度方向切取试样(8mg)，使用差示扫描量热仪(PERKIN ELMER公司制造DSC7)对该试样进行DSC测定。
试样温度
1.在20℃保持3分钟
2.以10℃/分钟由20℃升温至290℃
3.在290℃保持3分钟并融解
4.以300℃/分钟骤冷至20℃
5.在20℃保持3分钟
6.以10℃/分钟由20℃升温至290℃
按以上顺序扫描，以2中的升温结晶峰温度为Tc1，以6中的升温结晶峰温度为Tc2。
[口部结晶后口部端面的平滑度测定]
使口部结晶装置的红外线加热器的输出功率为1200W，加热时间为2分钟，使型坯的口部结晶。将口部结晶的型坯充分冷却，然后使用真圆度圆筒形状测定仪(RA-114D，Mitutoyo(株))，测定结晶后口部端面的平滑度，求出最大值和最小值的差。以该差作为口部端面的平滑度。
使用实施例、比较例中的各5个样品进行测定，平滑度为其平均值。
[双轴拉伸吹塑瓶的密封性评价]
将上述口部结晶后的型坯通过一步吹塑成型法进行双轴拉伸吹塑成型，接着在150℃、以1.5秒进行热定型，制作耐热PET瓶。利用二乙基-对苯二胺与氯气反应变色，按照以下顺序确认密封性。
1.将蒸馏水加温至93℃，与0.5％的二乙基-对苯二胺一起填充到PET瓶中
2.拧紧塑料盖
3.正立放置1分钟
4.在88℃、横倒放置5分钟的条件下进行热水煮沸灭菌
5.在1％次氯酸钠溶液中浸泡、冷却20分钟
6.确认是否因为吸入而导致变色
使用实施例、比较例中的各30个样品进行评价，即使其中1个因上述吸入而变色，则评价为×。
(实施例1)
使用聚对苯二甲酸乙二醇酯[RT543CTHP：日本ュニペツト(株)制备]作为聚酯树脂，将重量24.4g、全长45mm、颈环下至底部的长度L：23mm、口部顶面外径D：49mm、L/D为0.47的单层型坯用8秒的成型周期进行成型。由型坯的颈环下和底部沿厚度方向取样，进行DSC测定，测定Tc1和Tc2，求出ΔTc。将在相同条件下成型的型坯的口部结晶，然后进行平滑度测定，成型为双轴拉伸吹塑瓶，进行密封性评价。
(实施例2)
将型坯的成型周期改为13秒，除此之外与实施例1同样地成型单层型坯，进行DSC测定、口部结晶后的平滑度测定、以及双轴拉伸吹塑瓶的成型、密封性评价。
(实施例3)
将型坯的成型周期改为18秒，除此之外与实施例1同样地成型单层型坯，进行DSC测定、口部结晶后的平滑度测定、以及双轴拉伸吹塑瓶的成型、密封性评价。
(实施例4)
将型坯的成型周期改为28秒，除此之外与实施例1同样地成型单层型坯，进行DSC测定、口部结晶后的平滑度测定、以及双轴拉伸吹塑瓶的成型、密封性评价。
(实施例5)
使用聚对苯二甲酸乙二醇酯(J125T：三井化学(株)制备)作为聚酯树脂，制成重量为26.5g、全长79mm、颈环下至底部的长度L：58mm、口部顶面外径D：25mm、L/D为2.3的型坯，除此之外与实施例1同样地成型单层型坯，进行DSC测定、口部结晶后的平滑度测定、以及双轴拉伸吹塑瓶的成型、密封性评价。
(实施例6)
将型坯的成型周期改为3秒，制备重量为28.0g、全长96mm、颈环下至底部的长度L：78mm、口部顶面外径D：25mm、L/D为3.1的型坯，除此之外与实施例1同样地成型单层型坯，进行DSC测定、口部结晶后的平滑度测定、以及双轴拉伸吹塑瓶的成型、密封性评价。
(实施例7)
进行实施例6的双轴拉伸吹塑瓶的DSC测定和口部的平滑度测定、密封性评价。
(比较例1)
将型坯的成型周期改为20秒，除此之外与实施例6同样地成型单层型坯，进行DSC测定、口部结晶后的平滑度测定、以及双轴拉伸吹塑瓶的成型、密封性评价。
(比较例2)
将型坯的成型周期改为15秒，制成重量30.5g、全长106mm、颈环下至底部的长度L：88mm、口部顶面外径D：25mm、L/D为3.5的型坯，除此之外与实施例6同样地成型单层型坯，进行DSC测定、口部结晶后的平滑度测定、以及双轴拉伸吹塑瓶的成型、密封性评价。
(比较例3)
型坯的重量为90.0g、全长166mm、由颈环下至底部的长度L：140mm、口部顶面外径D：32mm、L/D为4.4，除此之外与实施例1同样地成型单层型坯，进行DSC测定、口部结晶后的平滑度测定、以及双轴拉伸吹塑瓶的成型、密封性评价。
(比较例4)
进行比较例1的双轴拉伸吹塑瓶的DSC测定和口部的平滑度测定、密封性评价。
表1
 PET树脂     颈环下     底部中心     L/D注2)(PF形状) 成型周期注1)(秒) 平滑度(mm) 密封性
Tc1(℃) Tc2(℃) ΔTc(℃) Tc1(℃) Tc2(℃) ΔTc(℃)
实施例1     RT543     148.6     154.3     5.7     150.6     155.3     4.7     0.47     8     0.13     ○
实施例2     RT543     148.6     155.8     7.2     150.8     155.8     5.0     0.47     13     0.15     ○
实施例3     RT543     148.0     155.8     7.8     150.1     155.6     5.6     0.47     18     0.16     ○
实施例4     RT543     145.6     155.8     10.1     149.4     155.8     6.4     0.47     28     0.21     ○
实施例5     J125T     151.6     157.1     5.5     152.8     156.6     3.8     2.3     8     0.11     ○
实施例6     RT543     150.8     156.8     6.0     150.8     155.8     5.0     3.1     3     0.14     ○
实施例7     RT543     148.6     155.6     7.0     148.6     155.6     7.0     3.1     3     0.14     ○
比较例1     RT543     138.8     155.1     16.3     138.6     154.9     16.3     3.1     20     0.35     ×
比较例2     RT543     140.0     155.5     15.5     140.1     155.4     15.3     3.5     15     0.36     ×
比较例3     RT543     140.4     155.6     15.2     140.5     155.6     15.1     4.4     8     0.41     ×
比较例4     RT543     138.5     155.0     16.5     138.8     154.9     16.1     3.1     20     0.35     ×
注1)PF的成型周期(秒)：由切断至压缩成型结束。(不包含冷却)
注2)PF：型坯

Claims (3)

1.型坯，该型坯至少具有含有聚酯树脂的层，在通过压缩成型得到的口部具有颈环，其特征在于：上述聚酯层的底部中心或颈环下的下式所示温度差ΔTc为15℃以下：
ΔTc＝Tc2-Tc1
式中，Tc1表示通过差示扫描量热仪(DSC)对由型坯切取的聚酯层测定的升温结晶峰温度，Tc2表示进行了Tc1测定、熔融后骤冷测定的升温结晶峰温度。
2.权利要求1的型坯，其中由颈环下至底部的长度L与口部顶面外径D之比L/D小于3.5。
3.吹塑成型容器，该吹塑成型容器是将权利要求1或2的型坯进行拉伸吹塑成型而得到的。
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