CN1910037A - 由基材和在任一侧上的至少一个覆盖层制成的多层产品；该多层产品的制造方法及着色的多层产品和使多层产品着色的方法 - Google Patents

由基材和在任一侧上的至少一个覆盖层制成的多层产品；该多层产品的制造方法及着色的多层产品和使多层产品着色的方法 Download PDF

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CN1910037A
CN1910037A CNA2005800024024A CN200580002402A CN1910037A CN 1910037 A CN1910037 A CN 1910037A CN A2005800024024 A CNA2005800024024 A CN A2005800024024A CN 200580002402 A CN200580002402 A CN 200580002402A CN 1910037 A CN1910037 A CN 1910037A
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M·I·比雷尔
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BI Group PLC
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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
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/22—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed
    • B32B5/24—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer
    • B32B5/26—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer another layer next to it also being fibrous or filamentary
    • 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
    • B29C70/06—Fibrous reinforcements only
    • 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
    • B29C70/081—Combinations of fibres of continuous or substantial length and short fibres
    • 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
    • B29C70/28—Shaping operations therefor
    • B29C70/40—Shaping or impregnating by compression not applied
    • B29C70/42—Shaping or impregnating by compression not applied for producing articles of definite length, i.e. discrete articles
    • B29C70/46—Shaping or impregnating by compression not applied for producing articles of definite length, i.e. discrete articles using matched moulds, e.g. for deforming sheet moulding compounds [SMC] or prepregs
    • 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
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • 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
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/22—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed
    • B32B5/24—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer
    • B32B5/28—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer impregnated with or embedded in a plastic substance
    • 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
    • B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
    • B32B2260/02—Composition of the impregnated, bonded or embedded layer
    • B32B2260/021—Fibrous or filamentary layer
    • 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
    • B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
    • B32B2260/04—Impregnation, embedding, or binder material
    • B32B2260/046—Synthetic resin
    • 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
    • B32B2305/00—Condition, form or state of the layers or laminate
    • B32B2305/07—Parts immersed or impregnated in a matrix
    • B32B2305/076—Prepregs
    • 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
    • B32B2305/00—Condition, form or state of the layers or laminate
    • B32B2305/08—Reinforcements
    • 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
    • B32B2305/00—Condition, form or state of the layers or laminate
    • B32B2305/10—Fibres of continuous length
    • 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
    • B32B2605/00—Vehicles
    • 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
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/249921—Web or sheet containing structurally defined element or component
    • Y10T428/249924—Noninterengaged fiber-containing paper-free web or sheet which is not of specified porosity
    • Y10T428/24994—Fiber embedded in or on the surface of a polymeric matrix
    • Y10T428/249942—Fibers are aligned substantially parallel

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Abstract

一种多层产品，由基材和在其每一侧的至少一层覆盖层制成，覆盖层完全或部分覆盖基材，基材是具有无规分布的纤维并且密度小于1.2g/cm3，优选小于1.0g/cm3的纤维增强热塑性产品，覆盖层是长或连续纤维增强的热塑性塑料膜，其中纤维彼此大致平行取向。

Description

由基材和在任一侧上的至少一个覆盖层制成的多层产品；该多层产品 的制造方法及着色的多层产品和使多层产品着色的方法
发明背景
玻璃纤维增强产品是广为人知的。它们用于各种用途。一类玻璃纤维增强产品由诸如具有嵌入热塑性树脂中的无规则分布纤维的产品的片材组成。取决于它们的制造方法，它们既可以相当紧密地堆积，得到具有大于1.00g/cm3，通常大于1.20g/cm3密度的片材，或得到具有小于1.20，通常小于1.00g/cm3密度的松散堆积片材结构。
本发明涉及具有由松散堆积片材结构制成的基材的产品。
所述松散堆积的片材结构具有优异的强度与重量比，使得它们适于很多应用。
然而，在一些应用中，希望进一步改进这些已知松散堆积结构的硬度和表面性质。
已知的是通过用不含任何纤维的热塑性薄膜或层覆盖片材来改进纤维增强片材的表面性质。当进一步处理所得的覆盖片材时，尤其是当加热它时，片材的纤维倾向于伸出覆盖层的表面，因此再次削弱表面性质。
为了增强用玻璃纤维增强的热塑性材料的机械性能，已经提出用含线形高性能纤维的材料层覆盖热塑性片材。
发明概述
本发明的多层产品包括玻璃纤维增强热塑性产品形式的基材和覆盖层，基材具有无规分布的纤维，并且密度小于1.20g/cm3，优选小于1.00g/cm3，覆盖层是长或连续纤维增强的热塑性塑料薄膜，其中长或连续纤维是彼此大致平行取向的。
本发明的产品具有良好机械性能和表面性质的最佳组合。更重要的是其热膨胀系数(CTE)很低。对于本发明的产品，其中基材用若干覆盖层覆盖在每一侧，其中在每个邻近覆盖层中的长或连续纤维的取向是不同的，可能获得用于实际目的时可以视为各向同性的产品。
基材以及覆盖层中的热塑性材料可以是相同或不同的。热塑性塑料可以从所有已知的热塑性材料中选择。
本发明的产品可以通过在具有所需形状的模具中加热多层产品并将其压制或真空固化而形成。
可以采用或不采用中间表面处理进行着色，例如使用底漆、阻燃处理等。
发明详述
本发明的多层产品包括在每一侧具有至少一个覆盖层的基材。
基材由具有无规分布纤维且密度小于1.20，优选小于1.00g/cm3的玻璃纤维增强热塑性产品形成。
覆盖层由长或连续纤维增强的热塑性薄膜形成，在每层中纤维彼此大致平行取向。
基材
上述种类的基材是已知的且为市售的产品。可以通过各种方法制造它们。可以通过类似造纸的方法来制造它们，其中增强纤维和热塑性材料一起混入水溶液，随后通过真空去除水。将如此获得的片状产品干燥并加热和最后压制，由此热塑性材料软化并在冷却时与纤维保持在一起。该方法的说明可见US4,734,321。
在制造适合基材的其它方法中，混合增强纤维和热塑性材料的纤维并针刺所得的结构。加热针刺结构并最终压制成中间产品。该方法例如在WO02/076711中描述。
基材中增强纤维的含量在较宽的范围内变化。增强纤维的含量通常为20-90重量％。
纤维平均长度为约7-200mm。
基材具有低密度且透气。基材通常厚度为1-10mm。
覆盖层
单层覆盖层或多层覆盖层由长或连续纤维增强的热塑性薄膜或者预浸料坯形成，长或连续纤维彼此是大致平行取向的。这种薄膜是市售的。
例如，所述薄膜可通过下述方法制得：从具有相对低的熔融粘度的热塑性聚合物熔体拉伸出许多连续长丝，同时保持长丝在拉紧状态下沿拉伸方向排列。所述方法例如已经在EP A-0 056 703中描述。长纤维的平均长度超过100mm。纤维单独地嵌入热塑性材料中。薄膜的厚度为0.1-1.0mm。
增强纤维
基材中和覆盖层中的增强纤维的材料可以是相同或不同的。纤维可以由玻璃(各种玻璃都适合)、碳、合成材料、矿物或天然材料制造。
热塑性材料
基材和覆盖层的热塑性材料可以是相同或不同的。但是应选择它们使得在高温加压加热它们时基材和覆盖层粘接在一起。例如合适的热塑性材料是聚烯烃、聚碳酸酯、乙烯基芳族均聚物、含乙烯基芳族化合物的共聚物，含乙烯基芳族化合物的接枝共聚物或含乙烯基芳族化合物的嵌段共聚物、热塑性聚酯、热塑性聚氨酯、聚醚酰亚胺、聚苯硫醚、聚苯醚、聚酰胺或包含至少一种上述热塑性材料的热塑性材料的共混物。
制造多层产品的方法
本发明的多层产品的制造方法相对简单。在如权利要求中所限定的基材的两侧上施加一层或多层膜。为防止本发明的多层产品的变形，最简单的是在基材每一侧施加相同数目的膜并具有平衡取向。当使用多于一层的膜时，膜通常施加成每个紧邻的层的长或连续纤维的方向不同于前一层的取向。通常以0°/90°层叠，但也可以是单一定向或准各向同性的叠层，这取决于应用。基材和膜在加压和一定温度下一起加热以确保基材和膜或预浸料坯之间良好的粘接。在这一过程期间或在随后的步骤中，多层产品可以通过在适合形状的模具中压制或真空固化而被模制成所希望的三维形状。也可能在覆盖层施加膜之前在加压加热的条件下对基材进行处理。
着色多层制品
多层产品可以用一或两层着色层来着色。为了获得最佳表面性质和着色层的良好粘着性，在多层产品的表面进行预处理是可取的。这种预处理可以由例如使用合适底漆层和或表面阻燃处理组成。
本发明产品的用途
本发明的产品可以用于许多应用。由于它们的低密度、高劲度、低CTE以及良好的表面性质，它们理想地适合用于汽车工业或户外交通工具的车身板。

Claims (17)

1、一种多层产品，其由基材和在其每一侧的至少一层覆盖层制成，覆盖层完全或部分覆盖基材，基材是具有无规分布的纤维并且密度小于1.2g/cm3，优选小于1.0g/cm3的纤维增强热塑性产品，覆盖层是长或连续纤维增强的热塑性薄膜，每个平衡层中纤维彼此大致平行取向。
2、权利要求1的多层产品，其中基材纤维的平均长度为约7-200mm。
3、权利要求1的多层产品，其中覆盖层的长或连续纤维的平均长度为至少100mm。
4、权利要求1的多层产品，其中覆盖层的长或连续纤维每个单独地嵌入热塑性材料中。
5、权利要求1的多层产品，其中基材和覆盖层中的塑料材料可以是相同或不同的，选自下述热塑性材料：聚烯烃、聚碳酸酯、乙烯基芳香族均聚物、含乙烯基芳族化合物的共聚物，含乙烯基芳族化合物的接枝共聚物或含乙烯基芳族化合物的嵌段共聚物、热塑性聚酯、热塑性聚氨酯、聚醚酰亚胺、聚苯硫醚、聚苯醚、聚酰胺或包含至少一种上述热塑性材料的热塑性材料的共混物。
6、权利要求1的多层产品，其中基材厚度为1.0-10.0mm。
7、权利要求1的多层产品，其中覆盖层厚度为0.1-5mm。
8、权利要求1的多层产品，其中基材和覆盖层的热塑性材料包括相容的热塑性材料。
9、权利要求1的多层产品，其中在基材的每一侧上有至少两层覆盖层，在基材每一侧上的至少两层覆盖层的长纤维具有长或连续纤维的不同取向。
10、权利要求1的多层产品，其中基材中的纤维由下述材料中的任何一种制得：玻璃、碳、合成材料、矿物或天然纤维。
11、权利要求1的多层产品，其中长纤维由下述材料中的任何一种制得：玻璃、碳、合成材料、矿物或天然纤维。
12、一种制造多层产品的方法，在基材的每一层上至少部分覆盖至少一层膜或预浸料坯层，基材是具有无规分布的纤维并且密度小于1.2g/cm3，优选小于1.0g/cm3的纤维增强热塑性产品，覆盖层是长或连续纤维增强的热塑性塑料，每个层中纤维彼此大致平行取向。
13、权利要求12的方法，包括至少一个附加步骤：在对应产品所需形状的模具中在加压条件下在高于基材中热塑性材料的玻璃化转变温度的温度加热覆盖有覆盖层的多层产品。
14、权利要求15的方法，包括在施加覆盖层之前在加压条件下加热基材的步骤。
15、一种着色的多层产品，由基材和在其每侧的至少一层覆盖层制得，基材是具有无规分布的纤维并且密度小于1.2g/cm3，优选小于1.0g/cm3的纤维增强热塑性产品，覆盖层是长或连续纤维增强的热塑性塑料，每层中纤维彼此大致平行取向，在至少一侧提供至少一层着色层。
16、一种权利要求17的着色的多层产品，其中在外覆盖层和一层或多层着色层之间具有底漆层。
17、一种为多层产品着色的方法，该多层产品由基材和在其每侧的至少一层覆盖层制得，基材是具有无规分布的纤维并且密度小于1.2g/cm3，优选小于1.0g/cm3的玻璃纤维增强热塑性产品，覆盖层是长或连续纤维增强的热塑性塑料膜，其中纤维彼此大致平行取向，该方法任选地提供由底漆着色的表面，以及任选地对待着色的表面进行表面处理，然后施加一层或多层着色层。
CN2005800024024A 2004-01-14 2005-01-03 多层产品、其制法、着色的多层产品和多层产品着色方法 Expired - Fee Related CN1910037B (zh)

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