CN1651513A - 成型材料及其制造方法 - Google Patents
成型材料及其制造方法 Download PDFInfo
- Publication number
- CN1651513A CN1651513A CNA2005100047634A CN200510004763A CN1651513A CN 1651513 A CN1651513 A CN 1651513A CN A2005100047634 A CNA2005100047634 A CN A2005100047634A CN 200510004763 A CN200510004763 A CN 200510004763A CN 1651513 A CN1651513 A CN 1651513A
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- China
- Prior art keywords
- polyamide
- resin combination
- based resin
- precursor
- fibre
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
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- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 13
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- XKZQKPRCPNGNFR-UHFFFAOYSA-N 2-(3-hydroxyphenyl)phenol Chemical compound OC1=CC=CC(C=2C(=CC=CC=2)O)=C1 XKZQKPRCPNGNFR-UHFFFAOYSA-N 0.000 description 1
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Images
Classifications
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- 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
- C08K7/00—Use of ingredients characterised by shape
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- C08K7/14—Glass
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- 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
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- C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- 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
- B29B15/00—Pretreatment of the material to be shaped, not covered by groups B29B7/00 - B29B13/00
- B29B15/08—Pretreatment of the material to be shaped, not covered by groups B29B7/00 - B29B13/00 of reinforcements or fillers
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- B29B15/12—Coating or impregnating independently of the moulding or shaping step of reinforcements of indefinite length
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- B29C70/04—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising reinforcements only, e.g. self-reinforcing plastics
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- B29C70/50—Shaping or impregnating by compression not applied for producing articles of indefinite length, e.g. prepregs, sheet moulding compounds [SMC] or cross moulding compounds [XMC]
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- 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
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- C08J5/0405—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres
- C08J5/042—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres with carbon fibres
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- 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
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
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Abstract
一种制造容易、且在进行注射成型等成型时增强纤维束在成型制品中分散良好的成型材料及其制造方法、具有良好流动性的至少由如下组成要素[D]和[E]构成的聚酰胺系树脂组合物以及由这些组合物制成的成型制品;其中对于该树脂组合物合计100重量份,配合的组成要素[D]占0.5~40重量份,[D]由苯酚或苯酚衍生物(前体a)与具有2个双键的脂肪族烃类(前体b)经缩合得到的低聚物[E]聚酰胺树脂。
Description
本案是申请号为97192729.4,申请日为1997年11月6日,发明名称为成型材料及其制造方法的申请的分案申请。
技术领域
本发明涉及一种长纤维增强热塑性树脂材料。更详细地说,本发明涉及一种制造容易且在进行注射成型等成型时增强纤维束在成型制品中的分散良好的成型材料及其制造方法、具有良流动性的树脂组合物以及由这些组合物获得的成型制品。
背景技术
众所周知纤维增强复合材料是将连续增强纤维束、纤维较长的不连续纤维作为增强纤维,以热塑性树脂作为基质。这种复合材料的特点是韧性高、回收容易、由于能够适用于注射成型或模压成型等成型方法而使成型周期缩短等,但到目前为止尚未被广泛地使用,
其理由如下。众所周知,熔融树脂向纤维束中的浸渍,树脂的熔融粘度越高就越困难。力学特性优良的热塑性树脂一般是高分子量的,熔融粘度非常高。将这种高分子量热塑性树脂作为基质的纤维增强复合材料,由于热塑性树脂难以浸渍到纤维束中,存在着生产率低、制造成本非常高的问题。另一方面,将易浸渍的低分子量(低粘度)热塑性树脂作为基质时,导致复合材料的力学特性大幅度降低,因此不能是该问题的解决策略。
作为使高粘度的热塑性树脂浸渍到连续纤维束中的方法,一般采用将浸渍在熔融树脂中的纤维束松开、捋平,再对树脂施加压力等进行机械浸渍的拉挤成型法等。采用这种方法的场合下,为了使例如超过500泊的高粘度树脂浸渍,必须使纤维束的牵引速度为10m/分以下的非常缓慢的速度。到目前为止,已知有几项关于这种机械浸渍手段的技术,但它们不能从根本上解决浸渍问题、不能使牵引速度达到每分钟几十米以上。
此外,还曾提出各种各样的浸渍方法,例如,将热塑性树脂用溶剂稀释成低粘度的溶液,将该溶液浸渍到连续纤维束中,在后续工序中除去溶剂的方法;将热塑性树脂制成乳液和分散液,使其浸渍到连续纤维束中,然后除去溶剂的方法;在流化床中使热塑性树脂粉末进入纤维束中,然后加热使其熔融浸渍的方法等,但是经过综合判断,不能不说它们仍然是生产率差的方法。
另一方面,也曾提出通过纤维表面的改性来改善该浸渍性问题的方法。也就是说,用胶粘剂、耦联剂等使纤维表面改性,由此改善了树脂浸渍时纤维与热塑性树脂的润湿性等。
作为这种方法,特开昭61-236832号公报中公开了这样一种复合材料,即,在标准的热塑性聚合物与纤维之间介入第2种热塑性聚合物来改善其润湿性,由此获得具有改良的力学特性的复合材料。但是,虽然该公报中公开了浸渍润湿性差的热塑性聚合物时力学特性得到改善,但是介入聚合物和纤维之间的第2种热塑性聚合物的具体处理量等不仅没有记载,而且也不清楚是否有浸渍促进效果。而且,虽然涉及到第2种热塑性聚合物的熔融粘度,但却没有示出与其有关的具体的分子量和熔融粘度的范围,不清楚实际上是否与提高材料的生产率有关系。而且,该方法虽然改善了纤维束与基质的润湿性,但完全没有涉及是否打算提高增强纤维在成型制品中的分散性。
另外,也曾试图在把制品成型为最终形状的工序中同时完成成型和增强纤维束与热塑性树脂的浸渍·纤维分散,在从原料制造到成型的整个工序中提高热塑性复合材料的生产率。使用热塑性成型材料的场合下,通常在成型时施加较高的温度和压力。例如在注射成型场合下的塑化工序中,成型材料在料筒内被加热,用螺杆混炼的同时被施以压力。模压成型中也施加很高的温度和压力。这对于使热塑性树脂浸渍到纤维束中是较合适的条件,以前曾有将增强纤维束和为基质的高分子量热塑性树脂分别加入成型机中,同时进行浸渍、纤维分散和成型的设想,例如直接注射成型。本发明者认为如果采用这种方法,由于不需要制造使树脂预先浸渍到纤维中的粒料那样的成型材料,因此可以大幅度地提高生产率。实际上,例如直接注射成型时,有时浸渍·纤维分散不充分,或者为了达到充分的浸渍·纤维分散,必须使用装有混炼效果极高的特殊形状螺杆的成型机。因此,不能使用通用的注射成型机,而且由于材料受到强烈的混炼,特意加入的长纤维被高剪切力折损成短纤维,使成型制品显示不出想要的高力学特性。如以上说明,长纤维增强热塑性复合材料中,不会存在着在材料制造工序或制品成型工序中,生产率非常高、且获得高力学特性的复合材料。
另外,已知用添加剂对热塑性树脂进行改性。特开平2~199164号公报、特开平7-11066号公报中公开了使用芳香族改性萜烯树脂作为添加剂,其目的在于,对于单体粘合性或涂装性差的聚苯醚或聚烯烃系树脂,在这些方面上对其进行改性。在聚酰胺系树脂的场合下,由于该树脂原本具有高的粘合性和涂装性,几乎不需要这种改性。但是,使用高分子量的聚酰胺树脂,或是为了提高弹性模量、赋予阻燃性而使用混有大量填料或阻燃剂的聚酰胺树脂时,成型时屡屡造成流动性不够。但是,作为不会大幅破坏聚酰胺树脂本来特性而使成型时流动性得到改善的添加剂,迄今为止还没有人使用一种结构类似于芳香族改性萜烯树脂的树脂。
本发明的目的在于,提供一种纤维增强热塑性树脂成型材料及其制造方法,该成型材料同时具有低分子量(低粘度)热塑性聚合物的易浸渍(生产率高)和高分子量热塑性树脂为基质时的高的力学特性这两个优点,在进行例如注射成型等成型时,在成型时的材料塑化阶段可以述到纤维与高粘度基质的浸渍,进一步使纤维在成型制品中分散良好。另外,本发明目的在于,提供一种具有良好流动性的树脂组合物以及用这些成型材料或树脂组合物制成的成型制品。
发明的公开
为了达到上述目的,本发明的成型材料由如下组成构成。
即,一种成型材料,其特征在于,至少由如下组成要素[A]、[B]和[C]构成,在组成要素[A]与组成要素[B]形成的复合体上接触地配置组成要素[C],
[A]连续的增强纤维束
[B]重均分子量为200~50,000,且熔融粘度低于组成要素[C]的热塑性聚合物
[C]重均分子量10,000以上的热塑性树脂。
另外,本发明成型材料的制造方法如下。
即,上述成型材料的制造方法,其特征在于,将组成要素[B]加热熔融,以使其粘度100泊以下,使其浸渍到组成要素[A]中形成复合体,接着,将熔融粘度500泊以上的组成要素[C]接触地配置到该复合体上,然后使整体冷却到常温。
另外,本发明的聚酰胺系树脂组合物由如下组成构成。
即,一种聚酰胺系树脂组合物,它是至少由如下组成要素[D]和[E]构成的树脂组合物,对于该树脂组合物合计100重量份来说,配合的组成要素[D]占0.5~40重量份,
[D]由苯酚或苯酚衍生物(前体a)与具有2个双键的脂肪族烃类(前体b)经缩合得到的低聚物
[E]聚酰胺树脂。
另外,本发明的成型制品是将上述成型材料或上述聚酰胺系组合物成型而获得。
另外,本发明的注射成型用粒料是由上述成型材料或上述聚酰胺系树脂组合物制成的。
另外,本发明成型制品的其他形式是将上述注射成型用粒料注射成型而制成的成型制品。
附图的简单说明
图1为本发明的成型材料复合体形态的一例的截面示意图。
图2为本发明的成型材料形态的一例的截面示意图。
图3为本发明的成型材料形态另一例的截面示意图。
图4为本发明的成型材料形态另一例的截面示意图。
图5为本发明的成型材料形态另一例的截面示意图。
图6为本发明的成型材料形态另一例的截面示意图。
图7为本发明的成型材料形态另一例的截面示意图。
附图中,1表示组成要素[A]的单纤维,2表示组成要素[B],3表示组成要素[A]与组成要素[B]形成的复合体,4表示组成要素[C]。
实施发明的最佳方案
以下更详细地说明本发明。
本发明的成型材料,至少由以下3种组成要素构成。组成要素[A]为连续的增强纤维束,作为复合材料的增强材料,将高的力学特性赋予成型制品。组成要素[C]是较高粘度的、如韧性等物性高的基质树脂。组成要素[C]在成型后浸渍到组成要素[A]中,与增强材料粘接,具有牢固地保持该复合体的作用。组成要素[B]是粘度较低的热塑性聚合物,与组成要素[A]共同形成复合体,同时,有助于成型时基质树脂(组成要素[C])浸渍到增强纤维束(组成要素[A])中,并有助于增强纤维分散在基质中,具有作为所谓浸渍助剂·分散助剂的作用。
组成要素[A]与组成要素[B]二者形成复合体。该复合体的形态如图1所示,在为连续纤维束的组成要素[A]的各个单纤维之间充满组成要素[B]。也就是说,处于组成要素[A]岛状地分散在组成要素[B]的海中的状态。具体地,通过使组成要素[B]热熔融来浸渍到组成要素[A]中形成复合体。
图2~图7模式地示出本发明成型材料的截面形状的例子。成型材料的截面形状,不限定于图中所示的在组成要素[A]与组成要素[B]形成的复合体上接触地配置组成要素[C],但优选的构成如图2~图5所示,被覆在复合体周围配置组成要素[C],或者优选如图6、图7所示,层状地配置复合体和组成要素[C]。如图4所示的被覆组成要素[C]地配置若干个复合体,在这种场合下,复合体的数目优选为2~6个左右。
优选使复合体与组成要素[C]的界面粘接。可以是部分组成要素[C]在界面附近进入到该复合体的一部分,形成与组成要素[C]相溶的状态,也可以形成在组成要素[A]中浸渍的状态。
成型材料可以在纵向连续保持大致相同的截面形状。也可以根据成型方法将这种连续的成型材料切断成某种长度。
本发明的成型材料可以采用例如注射成型或模压成型等方法,将组成要素[A]、[B]和[C]混合来制作最终的成型制品。从成型材料的可操作性方面考虑,重要的是各种组成要素直到被成型也不分离而保持上述那种形状。组成要素[B]是低分子量的,因此常温下通常为较脆而易破碎的固体,而且多数情况下为液体。因此,优选如保护复合体那样地配置高分子量的组成要素[C],直到成型时不会因材料的搬运、使用时的冲撞、擦蹭等造成组成要素[B]破碎和飞散等。
因此,优选如图2~图5中所示,对于由组成要素[A]和组成要素[B]形成的复合体,使组成要素[C]被覆在该复合体周围地配置,或是如图6~图7中所示,使复合体与组成要素[C]层状地配置。如果采用这样的配置,高分子量的组成要素[C]包裹住易破碎的组成要素[B],并被配置到易擦蹭的面上,因此,作为成型材料很容易保持形状。
以下更详细地说明本发明成型材料的各种组成要素。
组成要素[B]为重均分子量200~50,000,且熔融粘度低于组成要素[C]的热塑性聚合物,浸渍到组成要素[A]中形成复合体。组成要素[B]在将高粘度热塑性树脂基质浸渍到纤维束中时,有助于浸渍或纤维向基质中分散,显示出作为浸渍助剂·分散助剂的作用。增强纤维束(组成要素[A])被为低粘度物质的组成要素[B]预先浸渍,由此在例如注射成型或模压成型等成型为最终形状的工序中,当向成型材料施加温度、压力并进行混炼时,有助于使与基质形成的组成要素[C]浸渍到纤维束(组成要素[A])中,提高增强纤维在基质中的分散性。
其机理如下。构成增强纤维束的单纤维,碳纤维的直径为7~10μm,非常细,玻璃纤维的直径也20μm以下。换言之,纤维束具有比从外观上所预计的大得多的表面积,向纤维束中浸渍具有一定粘度的熔融物,就是将熔融物塞进单纤维之间的一点点间隙之间,将单纤维之间存在的空气赶出体系之外,并且全部地润湿宽广的纤维表面积,该难度(浸渍所要求的时间)被单纯看作与熔融物的粘度成比例。本发明中,用熔融粘度比最终浸渍物质(组成要素[C])还小的物质(组成要素[B])预先润湿纤维束,充满单纤维之间间隙的状态,也就是被浸渍,因此,最终使浸渍的熔融物(组成要素[C])即使为一定程度的高粘度,浸渍也变得容易得多。这是由于,被预先浸渍到纤维中的物质与其后被浸渍的物质仅仅采用置换或混合而达到浸渍,不需作将空气赶出体系之外的工作了,利用组成要素[B]对增强纤维束(组成要素[A])或对基质热塑性树脂(组成要素[C])的化学亲合性,其效果更好。特别是对组成要素[B]赋予表面活性剂作用的场合下,成型材料在成型时塑化的时候,增强纤维均匀良好地分散到成型制品中的效果极为明显。
应予说明,组成要素[B]所属概念一般不同于增强纤维表面处理中所用的耦联剂、胶粘剂。也就是说,耦联剂、胶粘剂的处理量很少,通常为纤维的0.05~10重量%左右,涂布在纤维的最表面部分,因此不是所说的预先浸渍到纤维束中的组成要素。可以预先对组成要素[A]进行公知的表面处理、赋予耦联剂和胶粘剂,使它们发挥出如以往的效果,但是,为了使为组成要素[B]这种热塑性聚合物浸渍到纤维束中,使用胶粘剂等的场合下,处理量可用必需的最低限量。
制作成型材料时,使组成要素[B]预先浸渍到组成要素[A]中。组成要素[B]受热熔融,可以容易地浸渍到连续的纤维束(组成要素[A])中,连续浸渍纤维束的工艺,可以实现例如速度10m/分以上的高速移动,生产率高。浸渍工艺不需使用复杂装置进行操作,即,一边将纤维大幅度松开,一边捋平因棒等摩擦而使纤维受到的损伤,一边向热塑性聚合物施加高压等。而且也不需要用溶剂稀释热塑性聚合物,使其粘度降低浸渍后而除去溶剂,或进行乳液、分散化,在浸渍之后除去溶剂之类复杂而生产率差的方法。通过使浸渍装置最优化,在熔融浸渍热塑性聚合物(组成要素[B])的工序中,完全可以使纤维束移动速度为每分钟几十米,在成型材料的生产中所具有的一大优点是树脂浸渍性不再成为其生产率的决定因素。
组成要素[B]的重均分子量小于200时,受热容易挥发等是成型制品产生孔隙等缺陷的原因,而且,使成型后的基质树脂的物性大幅度降低。相反,重均分子量大于50,000时,其结果是熔融粘度增高,向纤维束的浸渍变难,因此,使成型材料的生产率降低。较优选的组成要素[B]的重均分子量为200~14,000,更优选的范围为200~1,000。此处所述的重均分子量,其测定采用凝胶渗透色谱法(GPC),检测器使用利用激光的低角度光散射光度计(LALLS)。而且,熔融粘度的关系,在成型的温度下,组成要素[B]的熔融粘度小于组成要素[C]的熔融粘度为好。
组成要素[B]的熔融粘度优选100泊以下。更优选20泊以下,熔融粘度高于100泊时,向组成要素[A]的浸渍变难,成型材料的生产率降低。再有,组成要素[C]的熔融粘度优选500泊以上。此处所述的熔融粘度是在测定物质的维卡软化温度+30℃或者熔点+30℃的温度下的粘度,物质为结晶性、具有明确熔点的场合下,采用熔点+30℃的条件,除此之外,使用软化温度+30℃的条件。熔融粘度根据JIS K7199试验法,使用毛细管流变仪测定。测定时的剪切速度为103s-1,应予说明,维卡软化温度按照JIS K7206试验法测定,熔点用DSC测定。
在成型后的制品中组成要素[B]在基质组成要素[C]中发生混合、扩散。也就是说,如果组成要素[B]与组成要素[C]是更容易混合的组合,则组成要素[B]作为浸渍·分散助剂的作用优良。更具体地,如果组成要素[B]与组成要素[C]具有化学亲合性,优选是相溶的,则效果大,而且,即使是非相溶的组合,如果相互之间具有适度的化学亲合性和反应性,则组成要素[B]在组成要素[C]中进行微细分散等,实际上充分地发挥出作为浸渍·分散助剂的效果。组成要素[B]与组成要素[C]是否具有化学亲合性和易相溶的倾向,可以用溶解度参数在一定程度上进行判断。在秋山三郎、井上隆、西敏夫共同编写的“聚合物共混物”(PolymerBlends)(CMC)中记述了对溶解度参数的详细说明。已知聚合物的溶解度参数的测定方法有几种,为了进行比较,可以采用相同的测定方法。具体地说,优选采用计算容易的Hoy方法(参照上述参考书)。可以说,2种液体的溶解度参数值越接近,越是易相溶的组合。从这种观点看,当组成要素[B]的溶解度参数为δ1、组成要素[C]的溶解度参数为δ2时,溶解度参数值之差的绝对值|δ1-δ2|优选小于3.5。
低粘度的组成要素[B]与组成要素[C]的混合中,被选择的组成要素[B]不适于作为浸渍·分散助剂的场合下,有时特别是耐冲击性大幅度降低。从这种观点看,组成要素[B]在成型材料中的含量为10重量%时,将该成型材料成型而制成的成型制品与从该成型材料的组成要素中除去组成要素[B]而制成的成型制品,二者的Izod冲击值之比优选60%以上,更优选75%以上。Izod冲击值采用JIS K7110试验法测定。
组成要素[B]中,可以根据希望制得的成型制品所要求的特性添加阻燃剂、耐候性改良剂、其他抗氧化剂、热稳定剂、紫外线吸收剂、增塑剂、润滑剂、着色剂、相溶化剂、导电性填料等。
优选组成要素[A]被组成要素[B]完全浸渍,理论上说,纤维(组成要素[A])以六角形排列,处于最密集的填充状态,纤维间隙内浸渍组成要素[B]的这种状态是组成要素[B]最少的状态,假定纤维的截面为正圆且直径相同,则组成要素[A]的体积含量为90.7%(π/(2×31/2))。实际上,在技术上很难使这种体积含量达到无孔隙的程度。但是,即使存在一定孔隙的场合,或者在计算上产生未浸渍部分的体积含量高,本发明也具有浸渍纤维分散的促进效果。如果考虑到这些因素,为了防止被成型的复合材料的力学特性降低,复合体中的组成要素[A]的体积含量优选40%以上。而体积含量超过95%时,则单纤维之间间隙中组成要素[B]无法填充的部分增加,其结果促进浸渍的效果急剧降低,因此,组成要素[A]的体积含量优选95%以下。更优选的体积含量为80~95%。
如上所 述,优选组成要素[A]被组成要素[B]完全浸渍,但现实上这是困难的,组成要素[A]与组成要素[B]形成的复合体中存在一定程度的孔隙。特别是组成要素[A]含量大的场合下孔隙增多,但即使在存在一定程度的孔隙的场合下,本发明也显示出促进浸渍·纤维分散的效果。但是,孔隙率超过40%时,则促进浸渍·纤维分散的效果显著减小,因此,孔隙率优选为0~40%。更优选的孔隙率范围20%以下。孔隙率是按照ASTM D2734试验法测定复合体的一部分。
以下说明适于用作组成要素[B]的物质的化学组成。
考虑到组成要素[A]增强纤维的表面与基质树脂的粘合性等,通常对其进行表面处理,而且,通常涂布极性高的耦联剂和胶粘剂。因此,考虑到与该纤维表面的亲合性,组成要素[B]的热塑性聚合物优选具有极性基团。作为极性基团,可以举出例如氨基、羟基、羧基等,也可以考虑与纤维表面官能团等的亲合性来选择。当组成要素[C]基质树脂的极性象例如聚烯烃等那样低的场合下,组成要素[B]优选在具有极性基团的同时还具有低极性的脂肪族烃部分。由于组成要素[B]预先在纤维/基质界面处配置,因此,同时具有这种高极性部分和低极性部分的材料具有表面活性剂的作用,特别是有助于提高成型时的纤维分散性。
如上所述,组成要素[B]与组成要素[C]的相溶性是重要的因素。考虑到组成要素[B]与组成要素[C]的亲合性,通过适当地设定组成要素[B]中的高极性分子与低极性分子的构成比,可以获得与组成要素[A]的纤维表面和组成要素[C]的基质两者亲合性皆高的组成要素[B]。
特别地,作为组成要素[B]的优良材料,可以举出由苯酚或苯酚衍生物(前体a)与具有2个双键的脂肪族烃类(前体b)经过加成获得的低聚物。加成反应可以在强酸或路易斯酸的存在下进行。而且,组成要素[B]可以使前体a与在体系内生成前体b的化合物在同样的条件下反应而获得。
作为该前体a的苯酚衍生物,优选使用在苯酚的苯核上具有1~3个选自烷基(特别是碳原子数1~9的烷基)、卤原子(特别是氯和溴)、羟基的取代基的化合物。作为其具体实例,可以举出甲酚、二甲苯酚、乙基苯酚、丁基苯酚、叔丁基苯酚、壬基苯酚、3,4,5-三甲基苯酚、氯苯酚、溴苯酚、氯甲酚、对苯二酚、间苯二酚、5-甲基间苯二酚等
作为特别优选的前体a,可以举出苯酚和甲酚。
前体a也可以使用复数种。
前体b是具有2个双键的脂肪族烃类,也可以具有环状结构。
作为没有环状结构的前体b的实例,可以举出丁二烯、异戊二烯、戊二烯、己二烯等。作为具有环状结构的前体b的实例,可以举出单环性化合物环己二烯、乙烯基环己烯、环庚二烯、环辛二烯、以C10H16分子式表示的单环单萜烯(双戊烯、1,8-萜二烯、萜品二烯、萜品烯、二烯)等,双环性化合物2,5-降冰片二烯、四氢茚、以C15H24分子式表示的双环倍半萜烯(杜松烯、芹子烯、石竹萜烯等)等,三环性化合物双环戊二烯等。
而且,作为在体系内生成前体b的化合物,作为实例可以举出通过异构化生成双戊烯的蒎烯、莰烯。
作为前体b,优选碳原子数6~15的化合物,而且优选具有环状结构的,通过带有环状结构,使分子运动受到适当的限制,变得比较刚硬。将具有这种结构的组成要素[B]分散到组成要素[C]中获得成型制品时,成型制品的弹性模量不会大幅度降低。作为特别优选的前体b,可以举出以C10H16分子式表示的单环单萜烯和双环戊二烯。作为实例的单环单萜烯与苯酚的加成产物,其一般分子结构示于式[I]中。
前体b以及在体系内生成前体b的化合物可以使用复数种。
作为本发明成型材料的组成要素[B]特别优选的是由2分子前体a与1分子前体b加成而成的产物(以下表示为“2∶1的加成物”),在组成要素[B]中占40重量%以上。这是由于极性高的苯酚或苯酚衍生物与极性低的脂肪族烃类以2∶1的比例加成,整体的极性较高,与带有氨基等的高极性聚酰胺的亲合性优良。该2∶1加成物作为主要成分在组成要素[B]中可以含有40重量%以上,也可以与例如另外1∶1加成物或2∶2加成物或其他杂质混合。作为这种组成要素[B]的主要成分的实例,为单环单萜烯的双戊烯与苯酚的加成物,其分子结构示于式[II]中。
用作组成要素[A]的增强纤维束没有特别的限定。可以使用碳纤维、玻璃纤维、芳族聚酰胺纤维、氧化铝纤维、碳化硅纤维、硼纤维等高强度、高弹性模量纤维等。也可以2种以上混合使用。其中,碳纤维由于提高力学特性的效果优良,因而是优选的。
更优选的是,用X射线光电子分光法测定的、作为纤维表面的氧(O)与碳(C)原子数之比的表面官能团量(O/C)为0.05~0.4的连续的碳纤维。O/C小于0.05时,则意味着碳纤维表面上有助于与基质树脂粘合的官能团非常少。如果碳纤维与基质树脂的粘合性差,则不能期望成型制品具有高的力学特性。相反,O/C大于0.4时,则意味着碳纤维表面进行了高出所需的氧化处理等,碳的结晶结构被破坏,在纤维表面上形成脆弱层。该场合与O/C过低的场合相同,在纤维表层附近易发生破坏,因此不能期望成型制品具有高的力学特性。而且通过使O/C处于上述范围内,不仅在纤维/基质界面的粘合性方面,而且在使组成要素[B]浸渍时的素合性、纤维在成型时的分散性等方面都具有良好的效果。
表面官能团量(O/C)采用X射线光电子分光法,按如下次序求出。首先,将一束用溶剂除去了胶粘剂等的碳纤维(束)切断,展开排列在铜制试样支持台上,使光电子逃逸角为90°,X射线源使用MgKα1、2,使试样盒中保持1×10-8Torr。作为伴随测定时带电的峰的校正,C1S主峰的动能值(K.E.)合计为969eV。C1S峰面积是在K.E.为958~972eV的范围内画一条直的基线求出的。O1S峰面积是在K.E.为714~726eV的范围内画一条直的基线求出的。此处所说的表面官能团量(O/C)是从上述O1S峰面积与C1S峰面积之比,使用装置固有的灵敏度校正值作为原子数比计算出来的。
其次,用作组成要素[C]的热塑性树脂,其重均分子量10,000以上。重均分子量低于10,000时,则最终获得的复合材料成型制品的力学特性降低。组成要素[C]的重均分子量如果10,000以上,则没有特别的限定。作为组成要素[C],可以使用聚酰胺(尼龙6、尼龙66等)、聚烯烃(聚乙烯、聚丙烯等)、聚酯(聚对苯二甲酸乙二醇酯、聚对苯二甲酸丁二醇酯等)、聚碳酸酯、聚酰胺酰亚胺、聚苯硫醚、聚苯醚、聚砜、聚醚砜、聚醚醚酮、聚醚酰亚胺、聚苯乙烯、ABS、液晶聚酯或丙烯腈与苯乙烯的共聚物等。也可以是它们的混合物。而且,也可以是尼龙6与尼龙66的共聚尼龙那样的共聚物。另外,根据想要制得的成型制品所要求的特性,可以在组成要素[C]中添加阻燃剂、耐候性改良剂、其他抗氧化剂、热稳定剂、紫外线吸收剂、增塑剂、润滑剂、着色剂、相溶化剂、导电性填料等。
作为本发明成型材料的组成要素[C]特别合适的材料,可以举出聚酰胺、聚烯烃、聚碳酸酯。其中,尼龙6、尼龙66、或尼龙6与尼龙66的共聚物,与由上述苯酚或苯酚衍生物与具有2个双键的脂肪族烃类经缩合获得的低聚物(组成要素[B])的亲合性优良,即使将它们混合,力学特性等也很难降低,这方面是优良的。
本发明的成型材料,优选被切断成1~50mm的长度来使用。不连续的状态使成型材料产生流动性,而且被成型时的赋形性大幅度增加。切断长度越短,赋形性、流动性等成型性增加,但如果切断长度低于1mm时,则其结果使增强纤维长度变短,纤维增强效果急剧降低。如果切断长度超过50mm,则增强效果增加,但成型性大幅度降低。更优选的切断长度为3~12mm。
而且,即使本发明的成型材料是连续不断的,根据成型方法也可以使用。例如,作为热塑性线预浸渍制品,可以一边加热一边缠绕到心轴上,获得卷筒状成型物。而且,也可以将许多根本发明成型材料在同一方向拉齐,经加热使其熔融,制成单向热塑性预浸渍制品。这种预浸渍制品可以适用于要求高强度、高弹性模量的领域。
作为本发明成型材料的制造方法,可以举出这样一种方法:将组成要素[B]加热熔融,使其粘度100泊以下,将其浸渍到组成要素[A]中,形成复合体,接着,将熔融的粘度500泊以上的组成要素[C]接触地配置到该复合体上,然后将整体冷却至室温(15~25℃左右)。更具体地说,作为实例可以举出这样一种制造方法,包括3个工序:连续纤维束(组成要素[A])每单位长度上附着一定量的被加热熔融的组成要素[B]的工序(以下称为助剂赋予工序)、将赋予纤维束的组成要素[B]的粘度调整到100泊以下、使其浸渍到纤维束的内部、形成复合体的工序(以下称为助剂浸渍工序)、以及在连续复合体上接触地配置粘度在500泊以上的被加热熔融的组成要素[C]的工序(以下称为基质配置工序)。该3个工序优选连续地进行,但也可以采用不连续的制造方法,即,在助剂浸渍工序之后将复合体一次缠绕到线轴等上,然后采用脱机方式,喂入到基质配置工序。而且,助剂赋予工序和助剂浸渍工序如果在一个装置内能够同时实现则是更优选的。
助剂添加工序可以采用向纤维束添加油剂、胶粘剂、基质树脂的公知制造方法,作为更具体的实例,可以举出这样一种方法,即,在加热的旋转辊表面上,使熔融的组成要素[B]形成一定厚度的被膜(涂层),一边使纤维束(组成要素[A])与该辊表面接触一边使其移动,使纤维束的每单位长度上附着一定量的组成要素[B]。组成要素[B]在辊表面上的涂布,可以采用逆辊、正向旋转辊、单面上胶辊、喷涂、幕涂、挤出等公知的涂布装置这一概念来实现。原崎勇次著《涂布装置与操作技术入门》(综合技术中心)等详细论述了向辊上涂布的装置。
在这一应用中,可以不在辊表面上添加,而使用各种涂布机将加热熔融的组成要素[B]直接添加到移动着的纤维束上。更具体地说,可以举出一边从喷嘴挤出每单位时间一定量的组成要素[B],一边使以一定速度移动的纤维束与该喷嘴接触的工序。喷嘴与纤维束不一定必须完全接触,只要使纤维束在喷嘴附近移动就可以涂布。
助剂浸渍工序中,在组成要素[B]熔融的温度下,用棒去捋附着有组成要素[B]的组成要素[A],重复进行展开·集束的操作,采用施加压力或振动等操作,使组成要素[B]浸渍到为组成要素[A]的纤维束内部。作为更具体的实例,可以举出喂入纤维束,使其与被加热的若干个辊或棒的表面接触来进行展开等。此时,调节温度以使熔融的组成要素[B]的粘度100泊以下,如果不是这样,则不能高速度地实现使组成要素[B]浸渍到纤维束中的操作。
在基质配置工序中,在复合体上接触地配置熔融粘度500泊以上的组成要素[C]。更具体地说,可以举出使用挤出机和电线被覆法用涂布模头,连续地配置组成要素[C]以使其被覆复合体周围的方法,以及用辊等将复合体压扁,在扁平复合体的一面或两面,配置用挤出机和T型模头形成的熔融的薄膜状组成要素[C],用辊等使其形成一体的方法。
制造的成型材料,也可以用造粒机或丝束切断机等装置切断成一定长度来使用。该切断工序可以连续地设置在基质配置工序之后。成型材料为扁平状或片状的场合下,也可以纵切成细长条后切断。也可以使用同时进行纵切和切断的片材造粒机。
而且,制造上述热塑性纱线预浸渍制品的场合下,可以采用这样一
而且,制造上述热塑性纱线预浸渍制品的场合下,可以采用这样一种手段,即,基质配置工序之后,一边使配置的基质树脂(组成要素[C])熔融,使用加热辊压机等手段与组成要素[B]混合,一边使其连续地浸渍到组成要素[A]中,同时使截面扁平等。
以下说明本发明的聚酰胺系树脂组合物。本发明的树脂组合物至少由以下2种组成要素构成。组成要素[D]为由苯酚或苯酚衍生物(前体a)与具有2个双键的脂肪族烃类(前体b)经缩合获得的低聚物,组成要素[E]为聚酰胺树脂。该树脂组合物中可以加入增强纤维。
此处所说的组成要素[D]相当于上述组成要素[B]的一个优选方案。该组成要素[D]的分子量较低,由于粘度非常低,通过添加到组成要素[E]中,向被混合的树脂组合物提供高流动性。特别地,在向树脂中添加增强纤维等填料或阻燃剂等,使树脂流动性非常差的场合下,通过加入组成要素[D],可以改善热熔融时的流动性,提高成型性。一般地,如果将低分子量物质添加到树脂中,则有些场合树脂的力学特性等比添加之前大幅度降低,而本发明的树脂组合物的这种特性降低非常小。
对于本发明的树脂组合物合计100重量份来说,配合组成要素[D]0.5~40重量份。少于0.5重量份时,则改善流动性的效果小,超过40重量份时,则树脂组合物的力学特性大幅度降低。更优选的配合量为5~15重量份。
对于上述的树脂组合物100重量份,可以配合增强纤维5~200重量份。通过含有组成要素[D],即使树脂组合物含有增强纤维,其流动性也比较好。增强纤维的配合量小于5重量份时,则纤维增强效果小,而超过200重量份时,即使配合了组成要素[D],其流动性也很差,缺乏成型性。更优选的增强纤维的配合量为10~70重量份。
增强纤维的种类没有特别的限定。可以使用碳纤维、玻璃纤维、芳族聚酰胺纤维、氧化铝纤维、碳化硅纤维、硼纤维等高强度、高弹性模量纤维等。也可以2种以上混合使用。其中,碳纤维由于提高力学特性的效果优良,因而是优选的。
更优选的是,与上述相同,用X射线光电子分光法测定的、作为纤维表面的氧(O)与碳(C)原子数之比的表面官能团量(O/C)为0.05~0.4的碳纤维。
以下说明组成要素[D]。该组成要素[D]是由上述苯酚或苯酚衍生物(前体a)与具有2个双键的脂肪族烃类(前体b)经缩合反应获得的低聚物。
受热时易挥发等是成型制品上产生孔隙等缺陷的原因,或者防止树脂组合物的物性降低,从这种观点看,组成要素[D]的重均分子量优选200以上。另一方面,分子量增大,其结果熔融粘度提高,为了使树脂组合物有效地获得流动性改善效果,分子量优选为1000以下,此处所说的重均分子量,其测定使用凝胶渗透色谱法(GPC),检测器使用利用激光的低角度光散射光度计(LALLS)。
作为组成要素[E]的聚酰胺树脂,只要是由酰胺基重复单元构成主链的聚合物就没有特别的限定。可以使用尼龙6、尼龙66、尼龙11、尼龙610、尼龙612或以二聚酸为基础的聚酰胺等脂肪族聚酰胺、或者尼龙6T等芳香族聚酰胺等。也可以是它们的混合物或者尼龙6与尼龙66的共聚物等复数种聚酰胺的共聚物。而且,通过与酰胺基相关的加成反应或缩合反应,与亚甲基接枝的反应等,可以使聚酰胺连接上其他种类的分子。聚酰胺中,尼龙6或者尼龙66或者尼龙6与尼龙66的共聚物,由于力学特性优良,是特别适用的。
本发明的树脂组合物中,可以添加阻燃剂、耐候性改良剂、其他抗氧化剂、热稳定剂、紫外线吸收剂、增塑剂、润滑剂、着色剂、相溶化剂、导电性填料等。
而且,本发明的树脂组合物,如果是上述的配合比例,则其混合程度没有特别的规定。可以将各种组成要素混炼使其大致均匀地分散,或者例如使组成要素[D]浸渍到增强纤维中,与其接触地配置组成要素[E],即使是这种分离型的组合物也没有关系。这种场合下,组成要素[D]还具有这样一种作为助剂的功能,即,在使纤维增强树脂组合物成型时,使组成要素[E]容易地浸渍到增强纤维中。
以上说明的成型材料和树脂组合物,可以采用通常的成型方法来加工成最终形状的制品。作为成型方法,可以举出模压成型、传递模塑、注射成型或是这些方法的组合等,作为成型制品,可以举出汽缸罩盖、轴承保护架、进气歧管、踏板等汽车零件、活动扳手、扳手等工具类、齿轮等小物品。而且,本发明的成型材料,由于流动性优良,可以比较容易地获得要求成型制品厚度为0.5~2mm的薄壁成型制品。作为要求这种薄壁成型的物品,可以举出以如下物品为代表的电气·电子仪器用零件,例如个人电脑、移动电话中使用的外壳或作为个人电脑内部支持键盘零件的键盘支持体。这种电气·电子仪器用零件中,增强纤维中使用具有导电性的碳纤维的场合下,由于能够提供电磁波屏蔽性,因而是优选的。
而且,上述的成型材料和树脂组合物可以用作为注射成型用粒料。在注射成型中,使粒状的成型材料塑化时,由于施加了温度、压力和混炼,根据本发明,此时组成要素[B]或组成要素[D]作为分散·浸渍助剂发挥出很大的效果。这种场合下,可以使用通常的同轴螺杆型注射成型机,或者使用例如低压缩比形状的螺杆,并且将材料塑化时的背压设定为低压等,即使在螺杆混炼效果弱的场合下,增强纤维在基质树脂中的分散也很好,可以获得树脂在纤维中浸渍良好的成型制品。
实施例
实施例1
使萜烯苯酚聚合物(单环单萜烯与苯酚的加成物,YasuharaChemical(株)制YP90L,重均分子量460)的被加热熔融的液体在加热至130℃的辊上形成被膜。为了在辊上形成一定厚度的被膜,使用单面上胶辊。一边使连续的碳纤维束(Toray(株)制“Torayca”T700SC,碳纤维根数12,000根,单纤维细度0.6旦)与该辊接触,一边使其通过,使碳纤维束的每单位长度上附着一定量的萜烯苯酚聚合物。
在加热至180℃、以轴承自由旋转的、在一条直线上配置的10个直径为50mm的辊的上下,使附着聚合物的碳纤维交替地通过。该操作使聚合物浸渍到纤维束的内部,形成碳纤维与萜烯苯酚聚合物构成的连续复合体。该阶段中,聚合物的量占复合体总量的15重量%。碳纤维的比重为1.80、萜烯苯酚聚合物的比重为1.06,因此,碳纤维在整个复合体中的体积含量为76.8%。YP90L在130℃、剪切速度103s-1下的熔融粘度,用毛细管流变仪测定,约为10泊。
将该连续复合体喂入在直径40mm的单螺杆挤出机端部设置的电线被覆法用涂布模头中,将240℃下熔融的尼龙6树脂(Toray(株)制“Amilan”CM1017,重均分子量18,600)从挤出机出料到模头中,把复合体周围被覆起来那样地连续配置尼龙6树脂。尼龙6在240℃、剪切速度103s-1下的熔融粘度,用毛细管流变仪测定,约为2000泊。
将用尼龙6被覆该复合体的成型材料冷却至常温左右,然后用丝束切断机切成7mm长,制成注射成型用粒料。至此的成型材料的制造以连续的工序进行,碳纤维束的牵引速度为30m/分。
使用该粒料,用合模力100t的注射成型机制得外形为150mm×150mm、厚度1mm的平板状成型制品。该成型时,将喷嘴附近的料筒温度设定为250℃,模具温度设定为70℃。成型制品的表面平滑,没有纤维在成型制品中的分散性问题,用显微镜观察成型制品的截面,确认没有孔隙。
该成型制品的组成比为,碳纤维∶萜烯苯酚聚合物∶尼龙6树脂=35∶6∶59。
另外,该成型制品的Izod冲击值(有缺口)为21kg·cm/cm。
比较例1
将与实施例1中使用相同的连续碳纤维束喂入在直径40mm的单螺杆挤出机端部设置的电线被覆法用涂布模头,将240℃下熔融的尼龙6树脂(Toray(株)制“Amilan”CM1017)从挤出机出料到模头中,把复合体周围被覆起来那样地连续配置尼龙6树脂。
将用尼龙6被覆该碳纤维束的成型材料冷却至常温附近,然后用丝束切断机切成7mm长,制成注射成型用粒料。碳纤维束的牵引速度为30m/分。
使用该粒料,用合模力100t的注射成型机,制得外形为150mm×150mm、厚度1mm的平板状成型制品。如果使成型条件与实施例1相同时,则材料的流动性不足,成型制品在离开模具浇口的某一部分形成部分造型缺肉。而且成型制品的表面上露出未松开·未浸渍的纤维束,该部分形成弯曲的条纹状态。用显微镜观察成型制品的截面,观察到未松开·未浸渍的纤维束和孔隙。
该成型制品的组成比为,碳纤维∶尼龙6树脂=35∶65。
另外,该成型制品的Izod冲击值(有缺口)为25kg·cm/cm。
产业上的利用可能性
本发明的成型材料制造容易,采用注射成型等进行成型时,增强纤维束在成型制品中的分散良好。而且,本发明的聚酰胺系树脂组合物具有优良的流动性。另外,可以用这些树脂组合物提供品质优良的成型制品。
Claims (13)
1.一种聚酰胺系树脂组合物,它是至少由如下组成要素[D]和[E]构成的树脂组合物,对于该树脂组合物合计100重量份,配合的组成要素[D]占0.5~40重量份,
[D]由苯酚或苯酚衍生物(前体a)与具有2个双键的脂肪族烃类(前体b)经缩合得到的低聚物
[E]聚酰胺树脂。
2.权利要求1中所述的聚酰胺系树脂组合物,其中,前体b为6~15个碳原子的、具有2个双键的脂肪族烃类。
3.权利要求2中所述的聚酰胺系树脂组合物,其中,前体b具有环状结构。
4.权利要求3中所述的聚酰胺系树脂组合物,其中,前体b为双环戊二烯或以C10H16分子式表示的单环单萜烯。
5.权利要求1~4任一项中所述的聚酰胺系树脂组合物,其中,2分子前体a与1分子前体b的加成物在组成要素[B]中占40重量%以上。
6.权利要求1~4任一项中所述的聚酰胺系树脂组合物,其中,组成要素[D]的重均分子量为200~1000。
7.权利要求1~4任一项中所述的聚酰胺系树脂组合物,其中,组成要素[E]为尼龙6、尼龙66、或者尼龙6与尼龙66的共聚物。
8.一种纤维增强聚酰胺系树脂组合物,其特征在于,包括权利要求1~4任一项中所述的聚酰胺系树脂组合物100重量份和配合的增强纤维5~200重量份。
9.权利要求8中所述的纤维增强聚酰胺系树脂组合物,其中,增强纤维为碳纤维。
10.权利要求9中所述的纤维增强聚酰胺系树脂组合物,其中,增强纤维为用X射线光电子分光法测定的、纤维表面的氧浓度O/C为0.05~0.4的碳纤维。
11.一种将权利要求1~4任一项中所述的聚酰胺系树脂组合物成型而制成的成型制品。
12.一种由权利要求1~4任一项中所述的聚酰胺系树脂组合物制成的注射成型用粒料。
13.一种将权利要求12中所述的注射成型用粒料注射成型而制成的成型制品。
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- 1996-11-06 JP JP29363396A patent/JP3774959B2/ja not_active Expired - Lifetime
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- 1997-11-05 TW TW086116448A patent/TW360596B/zh not_active IP Right Cessation
- 1997-11-06 CN CNB2005100047634A patent/CN1325564C/zh not_active Expired - Lifetime
- 1997-11-06 EP EP97911471A patent/EP0872521B1/en not_active Expired - Lifetime
- 1997-11-06 WO PCT/JP1997/004049 patent/WO1998020076A1/ja active IP Right Grant
- 1997-11-06 ES ES97911471T patent/ES2273362T3/es not_active Expired - Lifetime
- 1997-11-06 KR KR1019980705169A patent/KR19990077036A/ko not_active Application Discontinuation
- 1997-11-06 DE DE69736802T patent/DE69736802T2/de not_active Expired - Lifetime
- 1997-11-06 CN CNB971927294A patent/CN1192062C/zh not_active Expired - Lifetime
- 1997-11-06 CA CA002241863A patent/CA2241863C/en not_active Expired - Fee Related
- 1997-11-06 US US09/101,251 patent/US6455143B1/en not_active Expired - Lifetime
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2001
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TWI586540B (zh) * | 2012-10-04 | 2017-06-11 | 樂金華奧斯有限公司 | 用於提高複合材料的浸漬性的功能性膜及利用上述膜的複合材料的製備方法 |
US10093080B2 (en) | 2012-10-04 | 2018-10-09 | Lg Hausys, Ltd. | Functional film for improving impregnation properties of composite material and method for manufacturing composite material using same |
TWI743015B (zh) * | 2015-10-20 | 2021-10-11 | 日商大賽璐塑膠股份有限公司 | 射出成形品 |
CN111727110A (zh) * | 2018-04-25 | 2020-09-29 | 旭化成株式会社 | 连续纤维增强树脂成型体、及其制造方法 |
CN111727110B (zh) * | 2018-04-25 | 2022-03-29 | 旭化成株式会社 | 连续纤维增强树脂成型体、及其制造方法 |
Also Published As
Publication number | Publication date |
---|---|
EP0872521A1 (en) | 1998-10-21 |
KR19990077036A (ko) | 1999-10-25 |
JPH10138379A (ja) | 1998-05-26 |
US6828374B2 (en) | 2004-12-07 |
CA2241863A1 (en) | 1998-05-14 |
US6455143B1 (en) | 2002-09-24 |
US20020019182A1 (en) | 2002-02-14 |
CN1325564C (zh) | 2007-07-11 |
WO1998020076A1 (fr) | 1998-05-14 |
CN1212719A (zh) | 1999-03-31 |
JP3774959B2 (ja) | 2006-05-17 |
CA2241863C (en) | 2008-07-29 |
DE69736802D1 (de) | 2006-11-23 |
EP0872521A4 (en) | 2000-01-19 |
DE69736802T2 (de) | 2007-01-18 |
ES2273362T3 (es) | 2007-05-01 |
TW360596B (en) | 1999-06-11 |
EP0872521B1 (en) | 2006-10-11 |
CN1192062C (zh) | 2005-03-09 |
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