CN103501984B - 可热塑性变形的复合材料 - Google Patents

可热塑性变形的复合材料 Download PDF

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CN103501984B
CN103501984B CN201280013247.6A CN201280013247A CN103501984B CN 103501984 B CN103501984 B CN 103501984B CN 201280013247 A CN201280013247 A CN 201280013247A CN 103501984 B CN103501984 B CN 103501984B
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CN103501984A (zh
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A.基尔巴赫
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Quadrant Plastic Composites AG
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    • 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
    • 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
    • B32B5/02—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 structural features of a fibrous or filamentary layer
    • B32B5/022—Non-woven fabric
    • 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
    • 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
    • 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
    • B29C70/50—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]
    • 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
    • B32B5/02—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 structural features of a fibrous or filamentary layer
    • B32B5/06—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 structural features of a fibrous or filamentary layer characterised by a fibrous or filamentary layer mechanically connected, e.g. by needling to another layer, e.g. of fibres, of paper
    • 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
    • B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
    • B32B2262/02—Synthetic macromolecular fibres
    • B32B2262/0253—Polyolefin fibres
    • 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
    • B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
    • B32B2262/02—Synthetic macromolecular fibres
    • B32B2262/0276—Polyester fibres
    • B32B2262/0284—Polyethylene terephthalate [PET] or polybutylene terephthalate [PBT]
    • 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
    • B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
    • B32B2262/10—Inorganic fibres
    • B32B2262/101—Glass fibres
    • 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
    • B32B2605/08—Cars
    • 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
    • Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
    • Y10T442/30—Woven fabric [i.e., woven strand or strip material]
    • Y10T442/3065—Including strand which is of specific structural definition
    • 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
    • Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
    • Y10T442/30—Woven fabric [i.e., woven strand or strip material]
    • Y10T442/3707—Woven fabric including a nonwoven fabric layer other than paper
    • 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
    • Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
    • Y10T442/30—Woven fabric [i.e., woven strand or strip material]
    • Y10T442/3707—Woven fabric including a nonwoven fabric layer other than paper
    • Y10T442/3724—Needled
    • Y10T442/3732—Including an additional nonwoven fabric
    • Y10T442/374—Additional nonwoven fabric comprises chemically different strand material than the first nonwoven fabric
    • 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
    • Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
    • Y10T442/30—Woven fabric [i.e., woven strand or strip material]
    • Y10T442/3707—Woven fabric including a nonwoven fabric layer other than paper
    • Y10T442/378—Coated, impregnated, or autogenously bonded
    • Y10T442/3789—Plural nonwoven fabric layers

Abstract

本发明涉及一种可热塑性变形的复合材料，该复合材料由具有玻璃纤维织物层片的核心层构成，该玻璃纤维织物层片的两面均结合包含聚丙烯纤维和玻璃纤维的纤维非织物层片。该核心层结合至少一层包含聚丙烯纤维和聚对苯二甲酸乙二醇酯纤维的覆盖层。本发明还涉及一种通过针织上述各层并且加热至熔融聚丙烯纤维来制造该材料的方法，并且还涉及该材料用于车辆部件的用途。

Description

可热塑性变形的复合材料
技术领域
本发明涉及一种可热塑性变形的复合材料，其由具有玻璃纤维织物层片的核心层构成，该玻璃纤维织物层片的两面均针织有纤维非织物层片，并且还包括至少一个覆盖层，此外，本发明还涉及这种复合材料的制造方法及其用途。
背景技术
WO2006/111037中描述了一种复合材料，该复合材料优选由两面均针织有纤维非织物层片A的玻璃纤维织物层片B构成。这种复合材料可以用于，例如，车辆领域。
WO2006/048304中描述了包含一层多孔核心层以及覆盖层的车辆衬里部件。核心层由以多孔纤维非织物(包括玻璃纤维和聚丙烯纤维)或者塑料泡沫构成，覆盖层由玻璃纤维增强的非织物聚丙烯纤维非织物构成，或者由以铝或高熔点聚合物形成的膜构成。该衬里部件还可包括由聚对苯二甲酸乙二醇酯非织物构成的薄覆盖层。
发明内容
本发明的一个目的是提供一种改善的复合材料，该复合材料尤其适合于发动机的封装，并且该复合材料具有高的声吸收、足够的碎石防护性、高的抗裂纹传播性、好的耐水和耐油性、以及防火性。
上述目的通过本发明的复合材料来实现。相应地，本发明的主题是可热塑性变形的复合材料，包括含玻璃纤维织物层片B的核心层，该核心层的两面均结合包含聚丙烯纤维(PPF)和玻璃纤维(GF)的纤维织物层片A。
该复合材料的特征在于它的核心层结合至少一层非织物形式的覆盖层D，该覆盖层D包含聚对苯二甲酸乙二醇酯(PETF)和PPF。
在一个具体的实施方式中，在核心层和覆盖层之间置入非织物形式的中间层C，其包含GF和PPF。
该玻璃纤维织物层片B优选具有200～1000g/m2、更优选400～800g/m2的定量。该纤维优选以纤度为30～3000特克斯的纤维束的形式存在。该织物可以具有纵向/横向的比值为4/1并且包含亚麻织物。该织物也可具有1/1的纵向/横向的比值。该玻璃织物使得上述的复合材料具有更高的抗冲击和抗裂纹传播性。
纤维非织物层A优选由30～60重量%GF和70～40重量%PPF构成，更优选由40～55重量%GF和60～45重量%PPF构成。它们的定量优选为200～2000g/m2，更优选为500～1000g/m2。根据梳理工艺或者Airlay工艺制备纤维非织物层A，由此得到循环带。该循环带的孔隙率优选为40～80体积%，更优选50～70体积%。
覆盖层D优选由20～60重量%PETF和80～40重量%PPF构成，更优选由30～50重量%PETF和50～70重量%PPF构成。该覆盖层D的定量优选为20～500g/m2，更优选30～300g/m2。优选该复合材料的两面均包含覆盖层D，但也可以只在一面上设置覆盖层D而在另一面上设置聚丙烯膜。该膜以粘附牢固的方式熔合在核心层上，并同时充当封闭密封层的作用。
覆盖层D优选具有0～20体积%、更优选1～15体积%的孔隙率。覆盖层D赋予复合材料以高的声吸收、好的碎石防护性和足够的耐水和耐油性。
在一个备选的实施方式中，置于核心层和覆盖层之间的中间层C优选包含5～40重量%GF和95～60重量%PPF，更优选10～30重量%GF和90～70重量%PPF。该中间层的孔隙率优选为5～50体积%，更优选10～30体积%。该任选的中间层C赋予复合材料以好的刚性和改善的声吸收。
上述各个层片或层通过热方式彼此结合，优选还额外地通过针织的方式彼此结合。该针织导致在z方向上玻璃纤维的部分取向，由此在后来的复合物材料加工过程中，当再次加热来制备完成部件时，该纤维的回复力在压制成型后可能会起作用。在这个优选的实施方式中，首先将非织物D、A和织物B连接在一起，也将非织物D和A也连接在一起，接着将由此得到的两个结构通过针织连接在一起。然后将该针织的结构体短暂的加热，例如30～360秒加热至180～210℃的温度，例如在连续式鼓风干燥箱中或者使用IR辐射，由此造成聚丙烯熔融，该熔融的聚丙烯浸透玻璃纤维并且由此将它们结合在一起。在备选的实施方式中，首先将非织物D、C和A连接在一起，也将非织物D和C连接在一起，以及将非织物A和织物B连接在一起，然后将由此得到的三个结构通过针织的方式连接在一起。然后，如上述的一样，加热该针织的结构体来熔融聚丙烯。
然后，在层压机中，例如，双带压力机或者层压设备，该多孔复合材料在低压条件下、优选在0.05～1bar压制5～60秒。由于z轴取向玻璃纤维的回复力，保留了大部分的空气孔。在EP-B1868796中详细描述了加热和压制期间的各个操作和步骤。在此处理期间，在层压机中，熔融的聚丙烯基质具有充足的时间来有效地结合增强纤维和覆盖层，由此造成在该复合材料中的空气孔和纤维的均匀分布。
如果作为覆盖层D的备选方案引入了聚丙烯膜，那么经过烘箱处理后，该聚丙烯膜可以插入至例如双带压力机中，在其中它可以在约180℃(换言之，高于熔点)熔融至仍然热的非织物核心上，或者可以在约150℃(换言之，低于熔点)通过加热(temperiert)双带压力机的方式熔融至外侧。
本发明中的幅状复合材料可以作为预切割件存储。其特别地适于生产车辆外部部件，主要适用于发动机封装和底部防护。为了这个目的，将该材料热塑性变形成完成件，例如在两箱铸型或者深拉的方式。经过压制后，在压力条件下，该模制品在施加的高温下由于增强纤维的回复力而再次扩张，从而在其中包含的空气孔会也在最终部件中发挥它们的声学效能。
在下表中列出了各个层及其结构、非织物的组成、其定量和空气孔含量。为了便于理解，将设置在两侧的层按系列编号，其中，例如，标号1可以理解为核心层B的上侧，序号2可以理解为核心层B的下侧。这些层彼此针织。
表：层结构
层 层结构 重量%GF或PETF 定量 孔隙率
D1 PP/PET非织物 30～50%PET 0～20%
C1* PP/GF非织物 10～30%GF 10～30%
A1 PP/GF非织物 40～55%GF 50～70%
B GF织物 100%GF 0
A2 PP/GF非织物 40～55%GF 50～70%
C2* PP/GF非织物 10～30%GF 10～30%
D2* PP/PET非织物 30～50%PET 0～20%
*层C1、C2和D2是任选的。
碎石防护(Steinschlagschutz)
根据ISO6603-2标准，在室温下进行刺穿试验(Durchstossprüfung)。为了试验的目的，分别使用厚度为2.0mm、4.0mm和6.0mm的试样，为了在统计学上进行证实，每次采用9个试样进行测试。根据本发明的试样具有如下的根据上述的标记(D1-A1-B-A2-D2)的结构：
层 层结构 重量% 定量 空气孔含量
D1 PP/PET非织物 30%PET 10%
A1 PP/GF非织物 40%GF 60%
B GF织物 100%GF 0
A2 PP/GF非织物 40%GF 60%
D2 PP/PET非织物 30%PET 10%
刺穿试验的结果总结如下*：
*括号中显示的是标准偏差。
上述的刺穿值，在完全加固状态(2.0mm)下以及4.0mm至6.0mm的厚度范围中均比那些不含增强层B的对比试样的超出40%。

Claims (11)

1.一种可热塑性变形的复合材料，其包括核心层，该核心层具有玻璃纤维织物层片B，玻璃纤维织物层片B在其两侧上结合有纤维非织物层片A，该纤维非织物层片A包含聚丙烯纤维(PPF)和玻璃纤维(GF)，其特征在于，所述核心层与至少一层非织物形式的覆盖层D热连接并且另外地针织在一起，该覆盖层D包含聚对苯二甲酸乙二醇酯纤维(PETF)和PPF，且该覆盖层D具有1～20体积％的孔隙率；任选地，在所述核心层和所述覆盖层之间置入包含GF和PPF的中间层C。
2.根据权利要求1所述的复合材料，其特征在于，所述的各层片或层具有以下组成：
A:30～60重量％GF和70～40重量％PPF；
B:100重量％的玻璃纤维织物；
任选地，C:5～40重量％GF和95～60重量％PPF；
D:20～60重量％PETF和80～40重量％PPF。
3.根据权利要求1的复合材料，其特征在于，所述的各层片或层具有以下的定量：
A:200～2000g/m2；
B:200～1000g/m2；
任选地，C:100～500g/m2；
D:20～500g/m2。
4.根据权利要求2的复合材料，其特征在于，所述的各层片或层具有以下的定量：
A:200～2000g/m2；
B:200～1000g/m2；
任选地，C:100～500g/m2；
D:20～500g/m2。
5.根据权利要求1至4中任一项所述的复合材料，其特征在于，所述的各层片或层具有以下的孔隙率：
A:40～80体积％；
任选地，C:5～50体积％；
D:1～15体积％。
6.根据权利要求1至4中任一项所述的复合材料，其特征在于，所述复合材料只在一侧上具有覆盖层D，并且在另一侧上设置有聚丙烯膜。
7.根据权利要求5所述的复合材料，其特征在于，所述复合材料只在一侧上具有覆盖层D，并且在另一侧上设置有聚丙烯膜。
8.一种用于制造根据权利要求1所述的复合材料的方法，其特征在于，首先将非织物D和A以及织物B连接在一起，同样也将非织物D和A连接在一起；然后将由此得到的两个结构针织在一起；最后将该针织结构体加热至180～210℃的温度，使得聚丙烯熔融并且所述纤维彼此结合。
9.一种用于制造根据权利要求1所述的复合材料的方法，其特征在于，首先将非织物D、C和A连接在一起，同样也将非织物D和C连接在一起，以及将非织物A和织物B连接在一起；然后将由此得到的三个结构体针织在一起；最后将该针织结构体加热至180～210℃的温度，使得聚丙烯熔融并且所述纤维彼此结合。
10.根据权利要求1至7中任一项所述的复合材料用于制造车辆部件的用途。
11.根据权利要求10所述的用途，其为用于发动机封装和作为底部保护。
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