CN1226512C - Frp制屋顶材料及其制造方法 - Google Patents
Frp制屋顶材料及其制造方法 Download PDFInfo
- Publication number
- CN1226512C CN1226512C CNB008000131A CN00800013A CN1226512C CN 1226512 C CN1226512 C CN 1226512C CN B008000131 A CNB008000131 A CN B008000131A CN 00800013 A CN00800013 A CN 00800013A CN 1226512 C CN1226512 C CN 1226512C
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- CN
- China
- Prior art keywords
- frp
- roof material
- resin
- system roof
- plate
- 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.)
- Expired - Fee Related
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- E—FIXED CONSTRUCTIONS
- E04—BUILDING
- E04D—ROOF COVERINGS; SKY-LIGHTS; GUTTERS; ROOF-WORKING TOOLS
- E04D3/00—Roof covering by making use of flat or curved slabs or stiff sheets
- E04D3/35—Roofing slabs or stiff sheets comprising two or more layers, e.g. for insulation
- E04D3/357—Roofing slabs or stiff sheets comprising two or more layers, e.g. for insulation comprising hollow cavities
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- 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
- B29C65/00—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor
- B29C65/48—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor using adhesives, i.e. using supplementary joining material; solvent bonding
- B29C65/50—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor using adhesives, i.e. using supplementary joining material; solvent bonding using adhesive tape, e.g. thermoplastic tape; using threads or the like
- B29C65/5007—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor using adhesives, i.e. using supplementary joining material; solvent bonding using adhesive tape, e.g. thermoplastic tape; using threads or the like characterised by the structure of said adhesive tape, threads or the like
- B29C65/5028—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor using adhesives, i.e. using supplementary joining material; solvent bonding using adhesive tape, e.g. thermoplastic tape; using threads or the like characterised by the structure of said adhesive tape, threads or the like being textile in woven or non-woven form
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B29C66/00—General aspects of processes or apparatus for joining preformed parts
- B29C66/01—General aspects dealing with the joint area or with the area to be joined
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- B29C66/10—Particular design of joint configurations particular design of the joint cross-sections
- B29C66/11—Joint cross-sections comprising a single joint-segment, i.e. one of the parts to be joined comprising a single joint-segment in the joint cross-section
- B29C66/112—Single lapped joints
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- B29C66/1142—Single butt to butt joints
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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- B29C66/00—General aspects of processes or apparatus for joining preformed parts
- B29C66/40—General aspects of joining substantially flat articles, e.g. plates, sheets or web-like materials; Making flat seams in tubular or hollow articles; Joining single elements to substantially flat surfaces
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B—PERFORMING OPERATIONS; TRANSPORTING
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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
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- B29C66/00—General aspects of processes or apparatus for joining preformed parts
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- 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
- B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
- 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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- B29C70/08—Fibrous reinforcements only comprising combinations of different forms of fibrous reinforcements incorporated in matrix material, forming one or more layers, and with or without non-reinforced layers
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- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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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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- B29C70/546—Measures for feeding or distributing the matrix material in the reinforcing structure
- B29C70/547—Measures for feeding or distributing the matrix material in the reinforcing structure using channels or porous distribution layers incorporated in or associated with the product
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract
本发明涉及一种FRP制屋顶材料,其特征在于,该FRP制屋顶材料是层状结构构造体,该层状结构构造体具有间隙地配置由FRP构成的一对板,其间隙中夹装着接合该一对板的加强肋构造体及FRP制屋顶材料的制造方法,该FRP制屋顶材料的制造方法使用RTM成形法,该RTM成形法使用具有贯通孔的核心材料,在RTM成形法中,在核心材料上设置沟槽,通过该沟槽扩散树脂并浸含在强化纤维内。
Description
技术领域
本发明涉及FRP(玻璃纤维增强塑料)制屋顶材料、制造方法、接合构造及其接合方法,特别涉及重量轻施工性优良、耐久性高、外观好并可接合的大面积的FRP制屋顶构件。
背景技术
以前用于构成屋顶本身或屋檐等部分的屋顶材料,一般是把折板等金属材料贴附在由钢筋构成的骨架上的材料或者是由混凝土形成的材料。但是,在为主要构成构件是金属时,存在着因生锈而变坏的问题。另外,由于用金属或混凝土构成,重量重,组装时的施工性差,当例如地震等情况发生时,对建筑物的耐震性不利。用金属、混凝土等材料做成轻量化的构件时,难以确保可靠的强度和刚性。
特别是需要大面积且无柱子的建筑物,例如,体育馆、大会厅等建筑物,需要做成无柱且大跨距。以前对于这样的用途,使用由钢筋增强混凝土形成的混凝土预制板。作为体育馆的屋顶,已熟知的方法是把例如长约24m的混凝土预制板作为屋顶材料的方法。但是,其问题在于,混凝土预制板的单位面积重量为250kg/m2,非常重,施工性非常差,地震时给予下部构造的影响非常大,建筑物需要结实的下部构造。
另外,在贴附由平板或折板构成的金属材料的构造中,难以形成曲面和立体形状,设计上的制约大,把屋顶材料形成所希望的形状并提高外观性也有界限。
另一方面,FRP以前虽然被用于船舶等大型构造体上,但是,作为建筑材料的应用的研究几乎没有进行,只是在作为内装修材料上进行了少量的研究,这是由于作为大型构造体的FRP的构造在用做建筑材料的形式方面没有被研究,并且,作为建筑材料的周边技术,例如,耐火性、接合构造等方面也没有进行充分地研究。
再有,用FRP形成大型的构造材料的方法,有以前所知道的手工铺叠法,但是该方法中,由于用手进行向强化纤维中浸含树脂,相对FRP中的强化纤维来说,树脂的比例非常高,所以,不能有效地利用强化纤维的物性。而且,在开放的情况下处理树脂,在环境方面也存在很大的问题。
作为解决上述问题的手段,也有例如向预先放置了强化纤维的成形模具内注入树脂的RTM法,但是,问题在于需要能向成形模具加压力的非常昂贵的成形模具。作为RTM法的改良,例如,在美国专利5,721,034中提出的方法是,在构成夹层状结构板的芯材料上切有剖面积不同的槽,在真空条件下,通过向核心材料的槽内注入树脂来有效地形成大面积的FRP。但是,在该方法中,由于在真空条件下注入,所使用的树脂必须是低粘度的,特别是对于适于建材用的酚醛树脂,用上述方法很难得到大型的整体成形品。
另一方面,在相互接合各FRP构件时,通常把同种材料的板或者金属板配置在FRP构件的上下面上,采用贯通FRP构件的螺栓等零件固接它们的所谓搭接方式。另外,作为其它方法,也有使用粘接剂接合FRP构件的方法。再有,也有用金属框架作基座,在其上面排列FRP构件的方法。
可是,在FRP构件相互接合的时候,在上述那样用配置在上下面上的板固接的方法中,必须在FRP构件上设置在其厚度方向上贯通的孔,存在FRP构件自身的强度降低、并且作为屋顶材料有可能漏雨的问题。
作为上述问题的例子,如特开平5-69487、特开平9-32914中所阐述的那样,是在FRP构件自身上设置贯通孔或者埋设金属套管进行接合。这些例子中的接合强度在机构上主要依赖FRP构件的表面压强和螺栓的抗断裂强度。一般情况下,FRP是基于纤维取向性上的各向异性材料,在纤维取向方向上具有非常高的抗拉强度,但是,抗压、抗断强度低。为此,在上述的接合方法中,接合强度受FRP的抗压、抗断裂强度的支配,不能支承大的负荷。
作为解决该问题的方法,在特开平8-333807中阐述的方法是,在开口部***FRP构件,再在***的FRP构件上设置金属制的套管,构件***后把轴贯通金属制的套管内。用该方法做成的构造缓和了在结合部位上产生的剪切力、弯矩。但是,在加上弯曲、拉伸荷重时,在开口部除了在FRP层上作用压缩力之外,有在埋设金属制套管的部位上产生剪切力和产生向着FRP构件的表面压力的情况,其结果,在该处的应力集中决定接合强度。
另一方面,在用粘接剂接合时,由于组装例如FRP制屋顶构造体用的接合作业一般都在屋外进行,所以,确实地实施那时的接合是非常困难的。
再有,如体育馆那样已建成的屋顶由于老朽需要修理时,由于各种气象条件,为了保护建筑物自身,必须设置临时屋顶,长时间施工中的临时屋顶的设置在技术上在成本上也存在问题。
如上所述,至今为止,对于作为特大型的构造体的屋顶材料来说,根本没有应用FRP材料。
本发明所要解决的课题在于,提供用于代替原有的金属制或混凝土制的屋顶构件的FRP构件的FRP制屋顶材料的构造及其制造方法、FRP制屋顶材料的接合构造及接合方法。
发明内容
为了解决上述课题,本发明基本上具有下述的构成。即,一种FRP制屋顶材料,对接接合2个或2个以上的层状结构构造体,该层状结构构造体具有间隙地配置由FRP构成的一对板,其间隙中夹装着接合该一对板的加强肋构造体,其特征在于,遍及该层状结构体的两端部的表面设置延伸的FRP连结层,并且在对接端面之间设置含树脂扩散介质的层。作为该FRP制屋顶材料的制造方法是,在上述对接端面之间配置树脂扩散介质和增强纤维,用气密材料覆盖树脂扩散介质和增强纤维的配置部而使内部成为真空状态,向树脂扩散介质部分注入树脂浸含在增强纤维中,使树脂硬化而使端部相互接合成一体。
附图说明
图1~8表示本实施例的FRP制屋顶材料的局部剖面图。
图9~11表示在与加强肋构造体的配置位置相对应的板的外面上安装了连结构件的例子。
图12、14表示在FRP制屋顶构件上形成开口部并安装窗构成构件的例子。
图13表示在FRP制屋顶材料的单面上设置耐火层的例子。
图15表示以任意的角度组合各面,具有更复杂形状的FRP制屋顶材料的例子,图16表示具有立体形状部分的FRP制屋顶材料的例子,该立体形状部分具有三维曲面图。
图17、18、19表示FRP制屋顶材料的别的实施例。
图20表示通过连结构件(例如螺栓)连结FRP制屋顶材料的例子。
图21表示用防水构件覆盖并做成防水构造的连结部。
图22是表示本发明的FRP制屋顶材料的一体成形的一个例子的图。
图23、24是表示核心构件的构造的例子的图。图24是设置贯通孔的例子。
图25表示FRP制屋顶材料的接合构造的剖面的一个例子。
图26表示通过由网状体构成的树脂扩散介质向两对接端面间扩散注入树脂的例子。
图27表示具有由块体构成的树脂扩散介质、树脂注入口、树脂流路的形状。
图28、29、30分别表示FRP连结层的例子。图30是把图28和图29的实施例组合起来的例子。
1、41~43、45:FRP制屋顶材料 2:间隙 3a~i:各种形状的FRP板(表皮层) 4:加强肋构造体 4a~e:各种形状的加强肋构造体 11:FRP制屋顶材料 12、51、65:芯材料 13:框架构造体 14、14a、14b:连结构件 14c:斜台 16、16a:万向接头 16b、16c:销 17:开口部 18:窗构成构件 19:窗玻璃构件 20:耐火层 44:三维曲面图 46:间隔 47:连结构件(例如螺栓) 48:连结部 49:防水构件 50模具 52:强化纤维基材 53:コ字形的帽状强化纤维基材54:沟槽 55:从沟槽分支出的多个沟槽 56:贯通孔 57:气密材料 58:真空泵 59:阀 60:液状的树脂 61、62:边缘通气孔 63:接合的FRP制屋顶材料 64:单个FRP制屋顶材料 66:FRP表皮板 67:FRP制屋顶材料的两端部 68:FRP连结层 69:FRP制屋顶材料的对接端面 70:含树脂扩散介质的层 71、72:树脂扩散介质 73:树脂注入口 74:树脂流路 75:FRP层76:凹部
具体实施方式
本发明的FRP制屋顶材料,由层状结构构造体构成。该层状结构构造体由一对FRP板和夹装在一对FRP板之间的加强肋构造体构成。作为一对FRP板的厚度来说,多厚都可以,但是,从FRP板的物性和重量的平衡来考虑,作为厚度来说,2mm至10mm之间的厚度最适当。作为加强肋构造体,可以使用FRP、金属、木材等。为了最大限度发挥加强肋构造体的效果,层状结构构造体的上下板和加强肋最好做成一体。
作为加强肋构造体的厚度,只要是能把应力传到上下层状结构板上的足够的厚度,多厚都可以,但是,太厚时,层状结构构造体的重量变重,损失了所谓轻量化的FRP的优点。最合适的厚度是1mm到3mm之间。
为了使层状结构构造体的上下板和加强肋成为一体,在加强肋使用木材或金属时,有予先把木材或金属等材料嵌入层状结构构造体中进行成型的方法。例如,首先把纤维基材置于成形模具内,在其上配置成为加强肋的木材或金属等材料,再在纤维基材中注入树脂,由此,可以得到与加强肋做成一体的层状结构构造体。这时,为了使树脂容易在木材或金属表面上流动,可以设置树脂流动的沟槽。
在用FRP做加强肋的情况下,例如用与上述同样的方法配置成为加强肋的强化纤维,然后注入树脂就可以做成一体。这时在加强肋中使用的强化纤维的形态怎样都可以,但是,在层状结构构造体被加上弯曲力时,在加强肋上会产生剪切力,最好使用纤维方向相对加强肋的纵向方向成45±10度角度的多轴织物。
作为形成上述层状结构构造体的上下板的间隔尺寸,在板延伸的方向上,实际上即可以是固定的,也可以是变化的。在屋顶材料的外观性重要的建筑物上,为了实现设计者希望的各种形状,上下板之间的间隔进行变化。
另外,关于板自身的形状,可以是简单的平板状,也可以形成例如至少一侧的板底交替地配置成山部和谷部的折板形状。该山部或/和谷部,除了在某个方向上做直线延伸而外,也可以形成立体的角锥状。
层状结构构造体的间隙,可以在其状态下形成为空间,也可以在间隙中配置比一对板的比重小的填充材料。关于填充材料,只要不加重层状结构构造体的重量,什么材料都可以,但最好使用重量轻的发泡体。关于发泡体种类,有重量轻的发泡混凝土和珍珠岩的成形体等的无机材料的发泡体和尿烷、聚氯乙烯树脂、聚乙烯、聚丙烯、聚苯乙烯、苯酚等的有机材料的发泡体。特别是在用做建筑材料时,理想的材料是抗燃烧性方面优越的材料,适合于使用的是无机材料的发泡体、苯酚发泡体、或者配有阻燃剂的有机的发泡体。
另外,可以做成至少在一侧的板的外面上安装用于连接其他构件的连接构件的构造。连接构件最好安装在与设置加强肋构造体的位置相对应的位置上。该连接构件用于防止连接构件和FRP制屋顶材料的扭曲,为了能够与位于各个方向上的其它构件进行连结,最好具有万向接头。
上述层状结构构造体的整体厚度与构成该一对板的各板的厚度之比,如果能满足作为屋顶材料的特性,什么比例都可以,但是,FRP层的厚度相对于全体厚度过分厚的话,层状结构构造体的重量加重,成为层状结构构造体的物性下降的原因。另外,使用的树脂的量也变多,成本也变高。相反,FRP层的厚度过薄时,表皮层的物性下降,结果层状结构构造体的物性也下降。理想的厚度比是在5∶1-25∶1之间。特别是在FRP表皮层中,由于由碳素纤维强化树脂构成的FRP在厚度比上含5%以上,所以层状结构构造体的全体厚度与构成该一对板的各板的厚度之比成为10∶1~20∶1,该层状结构构造体的重量成为30~65kg/m3,从而可以构成合适的尺寸稳定性优越的FRP屋顶材料。
对于FRP屋顶材料的重量,没有特别的限制,但是,为了充分发挥FRP的轻量化的优越性,本发明的FRP屋顶材料最好是单位重量在100kg/m3以下。由于重量轻,搬运和施工容易进行,同时,施工后加到建筑物上的负荷也大幅度地减轻。另外,由于屋顶全体可以大幅度地轻量化,所以,柱和梁的跨度也可以做得较长.再有,不需要大型的重型机械和和大的脚手架,施工期被缩短,同时可以减低施工费用.
本发明的FRP屋顶材料的剖面形状,由FRP的成形模具决定,基本上什么形状都可以.作为屋顶材料,常用的形状可以是平板型、箱型、反Y型、波浪型的任何一种形状。
另外,在实际上以一定的宽度在纵向方向延伸的材料中,为了有效地利用FRP的轻量性,发挥可以一气地进行大面积施工的优越性,理想的尺寸是长10m以上,宽度1.5m以上。但是在工厂成形再运到现场的情况下,由于存在运输的制约,最好是长度25m以下,宽度3.5m以下。
作为纵向方向的形状,什么形状都可以,但是为了做屋顶材料使用,最好附加上流雨水的坡度。为了有效地用屋顶材料所需要的物性,为了增加FRP自身的刚性,以便满足特别在积雪时的挠度要求,为了有效地利用形状的效果,长度方向的剖面形状最好是向上凸的圆弧状。作为圆弧的半径没有特殊的规定,但是从制造容易等方面出发,半径50m~250m是合适的。
另外,实质上以一定宽度向长度方向延伸的材料,特别在宽度方向可以容易地把几块材料连接起来,即使单个FRP制屋顶材料的宽度很小,通过连结也可以容易地构成大型的屋顶。因此,在搬运和施工时,既可以提高比较小尺寸的FRP屋顶材料的操作处理性,又可以最终实现所希望的形状的大面积的大型屋顶。其结果,不仅是新建筑,而且在屋顶更换时,作业也大幅度地简化。
再有,由于外面用FRP形成,基本上不存在生锈的问题,由于耐蚀性优良,耐久性有可大幅度提高,耐用年数也可以延长。
再有,对于FRP制屋顶材料的性能,通常规定加上雪负载或风负载时的挠度。在本发明的FRP制屋顶材料中,由于单位宽度(1mm)的抗弯刚度达到5×107kg·mm2以上,特别是在长度方向上单位宽度(1mm)的抗弯刚度达到5×107kg·mm2以上,所以,确保了作为屋顶构成构件的足够高的刚性,满足了规定的挠度。另外,由于满足上述的抗弯刚度要求,再由于FRP制屋顶材料的轻量性,在两端支持的屋顶材料中,在中间不需要支撑构件,可以做成10m以上跨距的屋顶材料来使用。另外,对于悬臂的屋顶材料来说,可以做成3m以上跨度的屋顶来使用。
上述加强肋构造,如后述实施例所述,可以采用各种剖面形状,但也可以构成桁架或者框架构造体。
另外,在本发明的FRP制屋顶构件上也可以设置沿厚度方向贯通的开口部。如果在开口部安装窗构成构件,可以在规定的地方设置可采光的窗户,留有规定形状的开口部,可以在开放构造的屋顶等处形成通风口等。
另外,在本发明的FRP制屋顶构件中,为了提高耐火性,最好至少一侧的板的基体树脂由酚醛树脂构成。这对确保屋顶材料的要求性能及确保对于燃烧的安全性(对来自建筑物外部的火的安全性)是必要的。发明者们发现,通过在屋顶表面上设置酚醛树脂的FRP层,表现出具有对作为评价燃烧的安全性的试验的跳火试验(ISO试验12468,Test method for external fire exposure to roofs)合格的性能。
作为FRP的强化纤维来说,通常使用玻璃纤维、芳族聚酰胺纤维、碳素纤维等。为了得到重量轻、强度高的FRP,最好使用碳素纤维成为CFRP。但是考虑与成本的平衡,做成与玻璃纤维的混合物是实用的。而作为被使用的纤维的形态,可以使用十字形、栅网等形态。特别对于碳素纤维,为了提高成形时的生产性,最好使用织物的形态。作为织物的形态,适合于使用平织或者绫织。为了充分发挥碳素纤维的高的物性,最好使用在织物的经线和纬线的交点上碳素纤维的弯曲少的所谓非卷曲织物。所用的碳素纤维的种类,只要能利用碳素纤维的高强度、高刚性,什么都可以,但是,为了以较低的成本做成成形品,也可以使用所谓粗纤维束(ラ-ヅトゥ)的碳素纤维。
如果再至少在平面上设置耐火材料层,其耐火性能就可以提高,就可以用做屋顶材料。对于屋顶材料的耐火性能,建设省告示第2999号等有所规定,发明者们发现,由于设置耐火材料层,试验可以顺利通过。使用于耐火材料层的物质,只要是具有耐火性的材料都可以,而做成为石棉纤维毡状的东西,用陶瓷纤维做成毡状的东西,或者它们的组合,由于它们对各种形状具有追随性,都可以使用,另外,也可以使用石棉的硬化板和酚醛泡沫塑料等。
例如,在根据建设省告示第2999号的试验方法进行1小时耐火试验的情况下,通过把厚度60mm以上、密度60kg/cm3以上的石棉层贴到厚度25mm以上、密度120kg/cm2以上的FRP制屋顶材料上,可以合格。在1小时耐火试验中,合格的其他的构成有,厚度30mm以上,密度80kg以上的酚醛泡沫塑料与厚度10mm以上,密度30kg以上的石棉硬化板的组合材料。
另外,在30分钟耐火试验的情况下,通过贴厚度40mm以上、密度60kg/cm3以上的石棉层,可以合格。满足30分钟耐火试验的其它的构成,还有厚度30mm以上密度60kg/cm3以上的酚醛泡沫塑料和厚度10mm以上,密度20kg以上的石棉硬化板的组合材料。
在贴耐火材料层的情况下,可以使用粘接剂、螺钉固定、或者两者并用的通常方法。在耐火层的表面上,为了提高表面的外观,可以设置化妆层,化妆层可以使用聚脂不织布或玻璃纤维织物等。
本屋顶材料的制造方法,可以使用FRP的一般的制造方法,例如,手铺法、RTM法、SMC法等。理想的是使用通过在核心材料上设置沟槽使树脂的扩散容易的RTM法。特大型的屋顶构件,例如,在层状结构构造体的表面积为10m2以上的情况下,可以在芯材料上设置沟槽的同时使用RTM法,该RTM成形法使用具有贯通孔的芯材料。
在芯材料上设置贯通孔,对于在短时间内把树脂很容易地浸含在形成层状结构板的上下的表皮板内是非常有效的。设置在核心材料上的贯通孔的大小,多大都可以,但是,最好是贯通孔的内径之和是芯材料上面或下面的面积的1/100~1/5000。贯通孔的面积过大时,树脂的贯通较顺利,但其缺点是,成形后的层状结构板全体的重量非常重,另一方面,贯通孔的面积过小时,妨碍树脂的贯通,在成形型面上有可能存在未浸含的部位。另外,贯通孔的数量,每1m2大约1个到50个为好。
特别做建筑材料用时,从其耐热性、难燃性的特点出发,适合于使用的酚醛树脂与一般的用于FRP成形的不饱和聚酯树脂、乙烯树脂等相比,粘度高难以进行树脂的扩散及难以向强化纤维中浸含,而且,也存在难以控制凝胶化时间的缺点。因此,在使用酚醛树脂成形时,需要尽可能快地把树脂浸含到强化纤维全体中。因此,上述那样的在核心材料上使用贯通孔的成形法是非常有效的,特别是想用酚醛树脂得到大型的FRP成形品时,可以说是必须的。
为了构成FRP制屋顶材料全体或者屋顶构造体,也可以使用层状结构板相互接合的形态。在屋顶材料的接合上,在金属制的屋顶的情况下,通常使用螺栓结合等机械的接合法,而本发明者们发现,在相互对接接合芯材料和配置在其两端面上的FRP板时,通过设置遍及两端部的表面的延伸的FRP层,同时,在对接的端面之间设置含有树脂扩散介质的层,就得到了FRP制屋顶材料的接合构造。
上述树脂扩散介质可以由例如网状体构成,可以有树脂注入口,同时,也可以由在表面上形成树脂流路的块体或者板状体构成。在该树脂扩散介质的周围最好再设置FRP层。
FRP连接层,也可以照其原样地使用在相邻的层状结构构造体的两端部的单面或者两面上用于接合,也可以配置在上述两端部的表面上形成的凹部内,邻近上述凹部的层状结构构造体的表面和FRP连结层的表面实际上形成为齐平面。
本发明的FRP制屋顶材料的接合方法,其特征在于,在芯材料的两表面上配置FRP表皮板的层状结构构造体的端部彼此相对接接合时,在对接端面之间配置树脂扩散介质,同时,沿两端部的整个表面配置增强纤维,用气密材料覆盖树脂扩散介质和增强纤维的配置部并使内部成为真空,向树脂扩散介质部分注入树脂并扩散到增强纤维部分,同时,浸含在增强纤维中,树脂硬化后,端部相互接合成一体。
在上述那样的本发明的层状结构构造体中,相邻的层状结构构造体的端部相互之间,通过由遍及两端的单面或者两面之间的延伸的FRP连结层和含有设置在对接端面之间的树脂扩散介质的层进行接合。由于不需要设置原有螺钉结合式那样的螺钉孔。所以不降低层状结构构造体的强度和刚性,另外,由于在没有螺钉孔的基础上基本上用同种材料结合,就避免了刚性急剧变化的应力集中。再由于在FRP表皮板上不需要增加强度,所以制造成本是廉价的。另外,由于没有螺钉头露出来,所以外观好,也不需要罩子等追加构件。
再有,在本发明的FRP制屋顶材料的接合方法中,由于通过树脂扩散介质,树脂迅速而有效地行进到需要的部位,浸含在增强纤维中,可以形成规定的接合部,所以,层状结构构造体的端部之间相互可以接合成牢固的一体。另外,在该接合方法中,可以只在接合部局部地使用,所以即使在现场也可以十分容易地施工。
实施例
下面参照附图说明本发明的最佳的实施例。
图1表示本发明的一个实施例的FRP制屋顶材料的局部剖面图。
在图1中,FRP制屋顶材料1具有接合具有间隙2地并行配置的一对FRP板(表皮层)3a、3b的加强肋构造体4。在本实施例中,加强肋构造体4也用FRP构成。但是,加强肋构造体4也可以由金属或木材等其它材料构成。无论加强肋构造体4由哪一种材料构成,最好与FRP板3a、3b的成形的同时进行配置和组装。
加强肋构造体的剖面形状可以取各种形状,图1中表示了只在上下方向延伸的剖面形状的加强肋构造体4,但是,也可以采用例如图2中所示的各种形状。在图2(A)所示的构造中,剖面形状做成I型或者H型的加强肋构造体4a,在图2(B)所示的构造中,表示剖面形状做成C型的加强肋构造体4b,在图2(C)所示的构造中,该C型的加强肋构造体做成背靠背配置的加强肋构造体4c,在图2(D)所示的构造中,表示剖面形状做成钩型或者连结构件型的加强肋构造体4d,在图2(E)所示的构造中,表示剖面形状做成盒型的加强肋构造体4e。另外,也可以与FRP制屋顶构件的部位相对应地选择、组合地采用这些不同剖面形状的加强肋构造体。
加强肋构造体4的配置位置和间距是决定本发明的FRP制屋顶材料的物性,特别是抗弯曲刚性的主要因素。为了适用于通常的屋顶材料,屋顶材料的每个单位宽度(1mm)的抗弯曲刚性最好是5×107kg·mm2以上。
在本发明的FRP制屋顶材料中,如图1、图2所示,形成在一对FRP板3a、3b之间的间隙2的尺寸(图中上下方向的尺寸)可以做成在板的延伸方向上实质上是一定的构造。另外,间隙尺寸也可以做成在板的延伸方向上是变化的。例如,如在图3的剖面上所见到的,由于一侧板3c以曲线变化,另一侧板3d以直线状延伸,所以,一对板3c、3d之间的间隙2a的尺寸可以进行连续地变化。
另外,作为屋顶材料,以前有时为了提高强度和刚性而使用折板形状的构件,在本发明中也可以同样采用。如在图4所示的剖面上见到的,可以把一侧的板3e交替地配置山部和谷部,形成锯齿状的折板形状,另一侧板3f做成直线延伸的形状。在上述图3中所表示的构造中,在图的下侧,板3d也可以形成曲线状变化的形状,在图4所示的构造中也可以把图下侧的板3f形成折板形状。
另外,如图5所示那样把一对板3g、3h形成折板状或者锯齿状,实际上在一对板之间也可以配置成保持一定的间隙2。
再有,由上述FRP构成的板的凹凸形状也可以扩展到3维形状。例如,如图6所示把FRP构成的板31鼓出或者凹下成角锥形,可以构成单独设置或多个配置该鼓出或凹下部5的构造。该鼓出部或凹下部5也可以形成曲面(三维曲面)。
由于用FRP构成的板来形成这样的屋顶材料的表面,所以,实质上可以形成自由地形状,有可能大幅度地缓和设计上的制约和大幅度地提高外观性,而且,可以廉价地实现所希望的自由的形状。
在上述各实施例中,可以把一对板之间的间隙2形成空间,在该空隙2内配置比一对板任何一个都比重小的填充材料。由于使用这样的比重小的填充材料,所以,在不损害屋顶材料全体的轻量性的情况下,既可以进一步提高强度和刚性,又可以提高隔热性。另外,可以更加确保规定的剖面形状。
该填充材料,例如如图7所示,具有构成层状结构构造体的FRP制屋顶材料11的芯材料12的功能。
另外,在本发明的FRP制屋顶材料中,可以配置作为加强肋构造体的桁架或者框架构造体。例如,在图8中,表示把框架构造体13配置在一对板3a、3b之间的间隙2内的构造。由框架构造体13极其牢固地接合一对板3a、3b,也抑制了板间尺寸的偏移。在该框架构造体13或桁架构造体中也可以使用FRP、金属及木材等材料。
在对FRP制屋顶材料进行施工时,最好在FRP制屋顶材料的至少一方的板的外面安装与其它构件(其它的建筑构件)相连接的连结构件。为了保持FRP制屋顶材料的规定的剖面形状,该连结构件最好安装在与设置加强肋构造体的位置相对应的位置上。
例如,如图9所示,在与加强肋构造体4a的配置位置相对应的板3a的外面和板3b的外面上安装连结构件14a、14b。安装方法可以是连接在板外面的方法,也可以是与板形成一体的方法,也可以用贯通螺栓等安装。
另外,如图10所示,为了防止连结构件14扭曲,最好带有不只在一方向而且能在多方向上旋转的万向接头16。由于万向接头16的使用,FRP制屋顶材料的安装和施工变得容易,同时可以防止弯曲应力等不希望的应力的产生和传递。再有,在图10所示的万向接头16上,由于回转范围稍微狭小些,所以辅助地使用斜台14c,但是根据使用的角度,也可以不使用斜台。
图11表示最佳实施例的一例,在该实施例中,使用了上述的万向接头16,同时,配置了与FRP制屋顶材料的部位相应形状的加强肋构造体4、4a(混合配置多个加强肋构造体),而且,使用了由发泡体构成的核心材料12。在图11所示的例子中,下侧的万向接头16a使用了具有在互相垂直的方向上延伸的2个销子16b、16c类型的接头。
另外,在本发明的FRP制屋顶材料中,为了形成窗或通风口,也可以设置在厚度方向上贯通的开口部。
例如,如图12所示,形成着沿FRP制屋顶构件1的厚度方向贯通的开口部17,在该开口部17上可以安装窗构成构件18。在窗构成构件18上,装入由丙烯、玻璃、聚碳酸酯等透光性材料构成的窗玻璃构件19。该窗构成构件18也可以使用与加强肋构造体相同的材质和进行相同的配置,也可以做成单体后与FRP制屋顶材料接合。
再有,在本发明的FRP制屋顶材料中,为了提高耐火性,可以做成至少在单面上设置耐火材料的构造。
例如,如图13所示,可以在FRP制屋顶材料1的单面上设置耐火层20。作为耐火材料,可以使用石棉纤维和陶瓷纤维等无机系列纤维的外壳状的材料、酚醛树脂发泡体、石棉的硬化板、或耐火涂料及发泡性的耐火性的塑料等。
上述那样的本发明的FRP制屋顶材料可以自由地形成各种立体形状。例如,如图14所示,可以形成多面体状(在图示例中,是四角锥状)的FRP制屋顶材料41,可以构成在所希望的面(在图示例中,是2面)上安装窗构成构件42的构造,如图15所示,也可以构成用任何角度组合各面的具有更复杂形状的FRP制屋顶材料43等。再有,也可以构成如图16所示的具有立体形状部的FRP制屋顶材料45等,该立体形状部具有三次元曲面图44。
另外,本发明的FRP制屋顶材料,其也可以采用图17、图18或剖面形状如图19(A)~(F)所示的构造。在这样的一个方向长的屋顶材料的情况下,也可以在宽度方向把多个连结起来构成屋顶材料。
作为连结构造,例如,可以如图20所示那样,使相邻FRP制屋顶材料具有规定的间隔46,通过适当的连结构件47(例如螺栓)进行连接。由于形成这样的间隔46,因此,可以容易地吸收单个FRP制屋顶材料的尺寸误差和组装时的误差,还可以容易地吸收由于有无太阳照射而引起的热膨胀、热收缩等的热变形。
上述连结部48,如图21所示,由于用由防水簿板等材料构成的防水构件49覆盖,所以,可以容易地实现防水构造,可以容易地防止漏雨等。
该本发明的FRP制屋顶材料,即使是大型的,通过使用规定的模具,通过下述的方法,也可以容易地一体成形。图22表示本发明的一体成形的一个例子,为了简化说明,表示成全体都是平板状的FRP制屋顶材料的情况,但是,通过变更成形模具,可以成形为自由形状。
在图22所示的方法中,在模具50内配置由发泡材料等构成的多个芯材料51,并在其两面上配置强化纤维基材52。在本实施例中,多个芯材料51从平面上看进行纵横排列。被排列的核心材料51的端部,可以排列成上述强化纤维基材52包住芯材料51,也可以如图22所示地配置コ字状的盖状的强化纤维基材53。
各芯材料如图23那样构成。该核心材料51具有成为树脂通道的沟槽54和从上述沟槽54分出的多个沟槽55。再有,也未必是上述情况,沟槽54和沟槽55的剖面积也可以没有差别,树脂通过这些沟槽54、55向强化纤维52的面方向扩散,扩散的树脂浸含在强化纤维52的厚度方向上,
再有,在树脂的浸含过程中,为了消除成形型面的未浸含部,也可以如图24所示那样在芯材上设置贯通孔56。这样,由于树脂直接注入到核心材料的下面,可以防止主要在成型面侧产生未浸含部,可以制造出品质好、物性稳定的FRP制屋顶材料。
上述强化纤维基材52的上面侧用气密材料57覆盖,内部由真空泵58吸引成真空状态。接下来,打开阀59把液状的树脂60注入到保持成真空状态的模具50内。注入通过例如由多孔质材料构成的边缘通气装置61进行,向泵58的吸引也同样通过边缘通气装置62进行。树脂的注入位置、吸引位置、边缘通气装置61、62的设置位置都可以适当变更。例如也可以从FRP制屋顶材料的中央部注入树脂。另外,在本实施例中,直接用气密材料覆盖强化纤维基材52的上面,根据需要也可以在它们之间夹装成形后剥离的离型材料。在上述实施例中,气密材料57本身具有离型材料的功能。根据需要设置的离型材料,最好是树脂能够通过并在树脂硬化后能从剥离的FRP构造上去除的离型材料(例如尼龙制的塔夫绸织物,聚酯制的塔夫绸织物等)。
注入的树脂,通过上述的例如芯材料51的沟槽54,55或者贯通孔56迅速向纤维强化基材52的表面的面方向扩散,同时,渐渐向强化纤维基材52的厚度方向浸含。与此同时,在形成加强肋构造体的コ字状强化纤维基材53内也浸含树脂并一体地形成加强肋构造体。
浸含的树脂在常温下,在某些情况下通过加热硬化而完成FRP制屋顶材料。硬化后,气密材料57被去除,硬化的FRP构造体从模具50中取出。这样就一体地形成FRP制屋顶材料。
下面用附图说明本发明的FRP制屋顶材料的实施例。图25表示FRP制屋顶材料的接合构造的剖面。63表示接合了的FRP制屋顶材料,64表示互相被接合的各个FRP制屋顶材料。各FRP制屋顶材料64是由把FRP表皮板66配置在芯材料65的两面上再把它们形成一体而构成的。在本实施例中,FRP表皮板66,在其端部,从一方的表面侧转向另一方的表面侧那样连续地连接。
在被对接且相邻的FRP制屋顶材料64的两端部67的表面上,设置遍及一方的端部67的表面地延伸的FRP连结层68,FRP连结层68和各FRP制屋顶材料64的FRP表皮板66一体地结合。在本实施例中,FRP连结层只设置在单侧,也可以如后述图30所示那样同样地设置在两面上。
在相邻的FRP制屋顶材料64的对接端面69之间设置含有树脂扩散介质的层70,该层70通过注入并硬化树脂,使两对接端面69相互一体地结合。
含在上述层70内的树脂扩散介质在树脂注入前的状态,如图26、27所示那样构成。在图26所示的例子中,通过由网状体构成的树脂扩散介质71可以使注入的树脂向两对接端面69之间及上述FRP连结层68的方向扩散。FRP连结层69在形成时,首先配置由增强纤维构成的层,通过树脂扩散介质71浸含扩散的树脂,成为FRP连结层69。
在图27所示的例子中,由块体构成树脂扩散介质72,该树脂扩散介质72具有树脂注入口73,在表面上具有由在纵横方向者/和圆周方向延伸的沟槽构成的树脂流路74。从树脂注入口73注入的树脂,通过树脂流路74扩散到规定的部位。该树脂扩散介质在图27中表示为块体,也可以是板状体。
另外,如图28所示,也可以在上述树脂扩散介质或者含树脂扩散介质的层的周围设置FRP层75。该FRP层75是在向上述树脂扩散介质注入前通过在树脂扩散介质的周围配置构成FRP层75的增强纤维,可以在树脂注入和接合时自然地构成。
另外,如图29所示,也可以在相邻的FRP制屋顶材料64的两端部67的表面上形成凹部76,遍及两凹部76地在凹部76内配置FRP连结层68。这样一来,如图所示,FRP制屋顶材料64的凹部76以外的表面和FRP连结层68的表面实际上可以构成为齐平。
假如采用在图29所示的凹部76内配置FRP连结层68的构造和图27所示的使用树脂扩散介质72的构造及在两面上配置FRP连结层68的构造,就成为图30所示的那样。
上述那样的本发明的FRP制屋顶接合构造63,例如,可以像下面那样制造。在FRP制屋顶材料64的端部67彼此相互对接接合之际,在对接端面69之间配置树脂扩散介质71(或者72),根据情况在树脂扩散介质71的周围绕缠上增强纤维。另外遍及FRP制屋顶材料64的两端部67的表面之间或者遍及在那里形成的两凹部76之间,在单面或者两面上配置增强纤维。该接合部分全体用可密封的气密材料覆盖,用真空泵吸引内部而形成为真空状态,向树脂扩散介质71部分注入树脂。由于形成真空状态,注入的树脂迅速地扩散,行进到对接的端面69之间,同时,也扩散到配置在表面上的上述增强纤维层,同时,浸含于增强纤维层中。在树脂扩散介质71的周围绕贴上增强纤维的情况下,在该增强纤维上也进行扩散和浸含。通过使注入的树脂硬化,用配置在表面上的增强纤维层和浸含的树脂构成FRP连结层68,在对接端面69之间硬化的树脂使两FRP制屋顶材料64接合成一体。
在由上述的接合方法得到的FRP制屋顶材料的接合构造中,由于在接合部上基本上不需要螺栓孔,所以,不会降低FRP制屋顶材料64本体的强度和刚性。另外,在FRP制屋顶材料64的表面部分和对接端面69之间的部分上,由于实际上可以用同种的FRP材料和同种的树脂接合,所以,接合性非常好,也没有刚性的急剧变化,也可以避免应力集中。
产业上利用的可能性
如上述说明的那样,根据本发明的FRP制屋顶材料,不用担心生锈,重量轻,又具有非常高的强度和刚性,可以发挥高的隔热性,可以进一步地提高建筑物的耐震性,同时,可以容易地形成任意的外观性高的形状,可以提供实用性非常高的屋顶材料。
如果作为FRP的基体树脂使用的是酚醛树脂,或者在表面设置耐火材料,就可以做成耐火性优良的屋顶材料。
另外,根据本发明的FRP制屋顶材料的制造方法,上述那样优良性能的FRP制屋顶材料即使是大型的,也可以实质上一体地成形,可以容易且廉价地制造所希望的FRP制屋顶材料。
再有,根据本发明的FRP制屋顶材料的接合构造,原有的接合构造的问题都可以一举解决,层状结构构造体的端部相互间可以容易地进行牢固且廉价地结合,可以确保接合部的高的强度和刚性,同时,可以形成优良的外观。
另外,根据本发明的接合方法,由于容易且廉价地进行接合,所以,现场的接合作业也变得容易。
Claims (35)
1.一种FRP制屋顶材料,对接接合2个或2个以上的层状结构构造体,该层状结构构造体具有间隙地配置由FRP构成的一对板,其间隙中夹装着接合该一对板的加强肋构造体,其特征在于,遍及该层状结构体的两端部的表面设置延伸的FRP连结层,并且在对接端面之间设置含树脂扩散介质的层。
2.如权利要求1所述的FRP制屋顶材料,其特征在于,该一对板的厚度分别是2~10mm。
3.如权利要求1所述的FRP制屋顶材料,其特征在于,加强肋构造体是FRP,并且与构成层状结构板的该一对板实质上是一体。
4.如权利要求1所述的FRP制屋顶材料,其特征在于,该加强肋的厚度是1~3mm。
5.如权利要求3所述的FRP制屋顶材料,其特征在于,由FRP构成的加强肋的增强纤维使用具有相对加强肋的纵向方向成45±10度的角度的纤维方向的多轴织物。
6.如权利要求1所述的FRP制屋顶材料,其特征在于,该FRP是CFRP。
7.如权利要求1所述的FRP制屋顶材料,其特征在于,该FRP是碳素纤维和玻璃纤维混合的FRP。
8.如权利要求1所述的FRP制屋顶材料,其特征在于,增强纤维的形态是织物。
9.如权利要求8所述的FRP制屋顶材料,其特征在于,该碳素纤维是平织或者斜纹织的。
10.如权利要求1所述的FRP制屋顶材料,其特征在于,该间隙的间隔在板延伸方向上实际上是一定的。
11.如权利要求1所述的FRP制屋顶材料,其特征在于,该间隙的间隔在板延伸方向上是变化的。
12.如权利要求1所述的FRP制屋顶材料,其特征在于,在该间隙中配置比该一对板的任一个板比重都小的填充料。
13.如权利要求1所述的FRP制屋顶材料,其特征在于,至少一方板形成为交替配置山部和谷部的折板形状。
14.如权利要求1所述的FRP制屋顶材料,其特征在于,在该间隙内配置框架构造体。
15.如权利要求1所述的FRP制屋顶材料,其特征在于,该层状结构构造体的整体厚度与构成该一对板的各板的厚度之比在5∶1~25∶1的范围中,同时,该层状结构构造体的重量是100kg/m3以下。
16.如权利要求1所述的FRP制屋顶材料,其特征在于,该层状结构构造体的每单位宽度的弯曲刚性是5×107kg·mm2以上。
17.如权利要求1所述的FRP制屋顶材料,其特征在于,实质上以一定的宽度沿长度方向延伸,长度方向上的每单位宽度(1mm)的弯曲刚性是5×107kg·mm2以上。
18.如权利要求1所述的FRP制屋顶材料,其特征在于,其剖面形状是平板形、V形、盒形、W形、倒Y形、波形、圆弧形的任何一个。
19.如权利要求1所述的FRP制屋顶材料,其特征在于,其实质上以一定的宽度在长度方向延伸,其尺寸是:长度10m~25m,宽度1.5m~3.5m。
20.如权利要求19所述的FRP制屋顶材料,其特征在于,长度方向的形状是圆弧状。
21.如权利要求1所述的FRP制屋顶材料,其特征在于,对接接合部用防水构件覆盖。
22.如权利要求1所述的FRP制屋顶材料,其特征在于,至少一方板的基体树脂是以酚醛树脂为主体的树脂。
23.如权利要求1所述的FRP制屋顶材料,其特征在于,至少在单面上设置耐火材料。
24.如权利要求23所述的FRP制屋顶材料,其特征在于,该耐火材料是含石棉的耐火材料。
25.如权利要求23所述的FRP制屋顶材料,其特征在于,该耐火材料是含苯酚泡沫塑料的耐火材料。
26.如权利要求16所述的FRP制屋顶材料,其特征在于,在该FRP板中,由碳素纤维构成的FRP层在厚度比上占5%以上。
27.一种FRP制屋顶材料的制造方法,该FRP制屋顶材料对接接合2个或2个以上的层状结构构造体,该层状结构构造体具有间隙地配置由FRP构成的一对板,其间隙中夹装着接合该一对板的加强肋构造体,其特征在于,在上述对接端面之间配置树脂扩散介质和增强纤维,用气密材料覆盖树脂扩散介质和增强纤维的配置部而使内部成为真空状态,向树脂扩散介质部分注入树脂浸含在增强纤维中,使树脂硬化而使端部相互接合成一体。
28.如权利要求27所述的FRP制屋顶材料的制造方法,其特征在于,在制造上述层状结构构造体时,在核心材料上设置沟槽,树脂通过该沟槽扩散并浸含在强化纤维中。
29.如权利要求27所述的FRP制屋顶材料的制造方法,其特征在于,设置在核心材料上的贯通孔的面积之和是核心材料上面或下面的面积的1/100至1/5000。
30.如权利要求27所述的FRP制屋顶材料的制造方法,其特征在于,该贯通孔每1m2设置1个至50个。
31.如权利要求1所述的FRP制屋顶材料,其特征在于,在该间隙内具有芯材料,在该核心材料上存在着从上面贯通到下面的贯通孔。
32.如权利要求1所述的FRP制屋顶材料,其特征在于,树脂扩散介质由网状体构成。
33.如权利要求1所述的FRP制屋顶材料,其特征在于,该树脂扩散介质具有树脂注入口,且由在表面上形成树脂流路的块状体或者板状体构成。
34.如权利要求1所述的FRP制屋顶材料,其特征在于,在该树脂扩散介质的周围设置FRP层。
35.如权利要求1所述的FRP制屋顶材料,其特征在于,FRP连结层配置在形成于该两端部的表面上的凹部内,与该凹部的层状结构构造体相邻的表面和FRP制连结层的表面形成为齐平面。
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2000
- 2000-03-16 US US09/700,060 patent/US6942915B1/en not_active Expired - Fee Related
- 2000-03-16 CN CNB008000131A patent/CN1226512C/zh not_active Expired - Fee Related
- 2000-03-16 KR KR1020007012980A patent/KR100699394B1/ko not_active IP Right Cessation
- 2000-03-16 EP EP00909665A patent/EP1081305A4/en not_active Withdrawn
- 2000-03-16 WO PCT/JP2000/001594 patent/WO2000056993A1/ja not_active Application Discontinuation
- 2000-03-16 CA CA002332442A patent/CA2332442C/en not_active Expired - Fee Related
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Publication number | Publication date |
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CN1293731A (zh) | 2001-05-02 |
KR20010071295A (ko) | 2001-07-28 |
EP1081305A1 (en) | 2001-03-07 |
CA2332442C (en) | 2008-01-15 |
US6942915B1 (en) | 2005-09-13 |
KR100699394B1 (ko) | 2007-03-27 |
CA2332442A1 (en) | 2000-09-28 |
EP1081305A4 (en) | 2005-03-16 |
WO2000056993A1 (fr) | 2000-09-28 |
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