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Publication numberCN101171114 A
Publication typeApplication
Application numberCN 200680015075
PCT numberPCT/FR2006/050404
Publication date30 Apr 2008
Filing date2 May 2006
Priority date4 May 2005
Also published asEP1877235A2, US7951317, US20080193757, WO2007000516A2, WO2007000516A3
Publication number200680015075.0, CN 101171114 A, CN 101171114A, CN 200680015075, CN-A-101171114, CN101171114 A, CN101171114A, CN200680015075, CN200680015075.0, PCT/2006/50404, PCT/FR/2006/050404, PCT/FR/2006/50404, PCT/FR/6/050404, PCT/FR/6/50404, PCT/FR2006/050404, PCT/FR2006/50404, PCT/FR2006050404, PCT/FR200650404, PCT/FR6/050404, PCT/FR6/50404, PCT/FR6050404, PCT/FR650404
InventorsJ·-P·加斯卡, L·奇奇格诺德, Y·巴诺德
Applicant法国圣戈班韦特罗特斯公司
Export CitationBiBTeX, EndNote, RefMan
External Links: SIPO, Espacenet
Method of producing a composite part from high-density glass granules
CN 101171114 A
Abstract  translated from Chinese
本发明涉及生产复合部件的方法,它是从被长的玻璃纤维增强的热塑性基质形成的。 The present invention relates to a method for the production of composite components, it is from the long glass fiber reinforced thermoplastic matrix formation. 本发明的方法包括注射或注射-压缩模塑步骤,该步骤通过包括被喂送原料和增强材料的单螺杆的设备来进行的。 The method of the present invention comprises injection or injection - compression molding step of feeding raw materials by including a reinforcing material and a single screw equipment to carry out. 该方法的特征在于该增强纤维是以长的切短纤维微粒形式被引入到设备中,该微粒具有在90和99.5%之间,优选在95和99%之间的玻璃密度,并且具有低于L的直径(L/D)比,用mm表示。 The method is characterized chopped fiber particles form the reinforcing fibers are long is introduced into the device, the particles have between 90 and 99.5%, preferably glass density between 95 and 99%, and has a lower L diameter (L / D) ratio, in mm. 本发明也涉及使用该方法获得的复合部件。 The present invention also relates to the use of a composite member obtained by this method.
Claims(11)  translated from Chinese
1.制造由被长玻璃纤维增强的热塑性基质的缔合所形成的复合部件的方法,该方法包括利用包含被喂送所述热塑性基质原料和增强材料的单螺杆挤出机的一种设备所进行的注塑或注射-压缩模塑步骤,该方法的特征在于该增强纤维是以长的切短玻璃丝束的微粒形式被引入到该设备中,其中玻璃的密度或玻璃含量是在90至99.5%,优选在95至99%,和长度/直径比L/D比是低于L,以mm表示。 1. The method of manufacturing a composite member made by the long glass fiber reinforced thermoplastic matrix formed by the association, the method includes the use of an apparatus comprising a thermoplastic matrix by feeding the raw material and the reinforcement of the single-screw extruder injection molding or injection performed - compression molding step, the method being characterized in that the reinforcing fibers are in particulate form long chopped glass strands are introduced into the apparatus, wherein the density of the glass or the glass content is 90 to 99.5% , preferably 95-99%, and the length / diameter ratio L / D ratio is less than L, in mm.
2. 根据权利要求l所要求的方法,其中L/D比是低于L的2/3,用mm 表示。 L 2. The method according to claim desired, wherein the L / D ratio is less than 2/3 L, in mm.
3. 根据权利要求1所要求的方法,其中L/D比是在L/4至L/2之间, L用mm表示。 3. The method as claimed in claim 1, wherein the L / D ratio is between L / 4 to L / 2, L in mm.
4. 根据权利要求1-3所要求的方法,其中增强纤维微粒是通过在水和任选地有粘结剂存在下,预先混合具有在6至30mm之间的长度的切断玻璃丝束来获得的。 4. The method as claimed in claim 1-3, wherein the reinforcing fiber particles through the water with an adhesive and optionally in the presence of a pre-mixed chopped glass strands having 6 to 30mm in length between the obtained .
5. 根据权利要求4所要求的方法,其中切短玻璃丝束由长丝组成, 长丝的直径是在5至24 nm之间,该长丝被施胶剂涂覆或粘结。 5. A method as claimed in claim 4, wherein the chopped strands of glass filaments by a filament diameter of between 5 and 24 nm, the filaments are coated with sizing agent or adhesive.
6. 根据权利要求5所要求的方法,其中使用具有比热塑性基质的熔点更低的熔点的施胶剂。 6. The method as claimed in claim 5, wherein a sizing agent having a melting point lower than the melting point of the thermoplastic matrix of the.
7. 根据权利要求6所要求的方法,其中在施胶剂的熔点与热塑性基质的熔点之间的差异是大于至少5。 7. The method as claimed in claim 6, wherein a difference between the melting point and the melting point of the thermoplastic matrix of the sizing agent is at least greater than 5. C,优选大于至少7t:和非常优选大于至少10°C。 C, preferably greater than at least 7t: and very preferably greater than at least 10 ° C.
8. 根据在前述权利要求中的一项所要求的方法,其中热塑性基质选自聚丙烯(PP),聚酰胺(PA),聚对苯二甲酸乙二醇酯(PET)或聚对苯二甲酸丁二醇酯(PBT),笨乙烯类树脂,如丙烯腈-丁二烯-苯乙烯(ABS),聚乙烯(PE),聚苯硫(PPS),聚碳酸酯(PC),和聚缩醛类,如聚氧化亚曱基(POM)。 In the method according to one of the preceding claims, wherein the thermoplastic matrix is selected from polypropylene (PP), polyamide (PA), polyethylene terephthalate (PET) or polyethylene terephthalate acid polybutylene terephthalate (PBT), ethylene-based resin stupid, such as acrylonitrile - butadiene - styrene (ABS), polyethylene (PE), polyphenylene sulfide (PPS), polycarbonate (PC), and poly acetals, such as polyoxymethylene Yue group (POM).
9. 根据前述权利要求中一项所要求的方法,其中热塑性基质是聚丙烯和其中施加液体按固体材料的重量百分数计包括至少:-10-99%的EVA(乙烯-乙酸乙烯酯)水乳液,它的共聚物具有50%或更高的乙烯含量,或EAA(乙烯-丙烯酸)的水乳液,它的共聚物具有50%或更高的乙烯含量;-1-30%的马来酸酐接枝聚丙烯的水乳液;和-1-40%的一种或多种有机硅烷,其中的至少一种属于氨基硅烷类型。 9. The method according to one of the preceding claims desired, wherein the thermoplastic matrix is polypropylene and wherein the liquid is applied by meter weight percent solid material comprises at least: -10-99% of EVA (ethylene - vinyl acetate) aqueous emulsion It copolymer having 50% or more of ethylene content, or EAA (ethylene - acrylic acid) aqueous emulsion, which copolymer has 50% or more of ethylene content; -1-30% maleic anhydride access branched polypropylene aqueous emulsion; and -1-40% of one or more organosilanes, wherein at least one aminosilane type belongs.
10. 根据权利要求9所要求的方法,其中施胶液体进一步包括: -配制剂的稳定剂,如N-丁基胺;-成膜聚合物如聚氨酯的水乳液;和-加工助剂,如表面活性剂和/或润滑剂和/或抗静电剂。 10. The method as claimed in claim 9, wherein the sizing liquid further comprises: - formulation stabilizers, such as N- butylamine; - film-forming polymers such as polyurethane aqueous emulsion; and - processing aids, e.g. surfactants and / or lubricants and / or antistatic agents.
11. 由根据权利要求6到IO中的任一项所要求的方法获得的复合部 11. The composite unit by the method according to claim 6 to IO in any one of claims received
Description  translated from Chinese

从高密度玻璃微粒生产复合部件的方法本发明涉及由注射模塑法或注射_压缩模塑法制造基本上从以长 Production of composite parts from high density glass particles by the method of the present invention relates to injection molding or injection compression molding _ manufactured substantially from a long

玻璃纤维(即具有典型地在6和30mm之间的切短玻璃纤维的初始长度) 增强的热塑性有机材料形成的复合产品或部件(pi^ce)的领域。 Glass fibers (i.e. typically having an initial length of chopped glass fibers of between 6 and 30mm) areas composite products or components (pi ^ ce) reinforced thermoplastic organic material formed. 更确切地说,根据本发明,描述了注塑方法或注射-压缩模塑方法,利用喂送热塑性有机材料和增强纤维的包括单螺杆的设备来进行,该纤维是通过切断玻璃丝束,例如在拉丝模(fil化re)之下或从粗纱,来获得的。 More specifically, according to the present invention, a method of injection molding or injection described - compression molding method using thermoplastic organic feed material and reinforcing fibers include single screw device carried by the fibers are chopped glass strands, for example in the drawing Under the mold (fil-based re) or from roving to obtain.

为了缩写,该术语"基质"在下面的文本中表示形成了最终获得的 For abbreviation, the term "substrate" in the following text represents the formation of a finally obtained

模塑复合材料的一部分的热塑性有机材料。 Thermoplastic organic material portion of the molding compound materials. 同样在下文中,该术语"注塑,,表示全部的注射模塑和注射-压缩模塑工艺和该术语"长纤维"表示如上所述的纤维。 Also in the following, the term "injection ,, represent all injection molding and injection - compression molding process and the term" long fiber "means fiber as described above.

在模具中由有机材料和增强丝束的注塑法制造由复合材料制成的物体将使得混合这些成分的难度得以解决; 一方面,需要在有机材料和增强材料之间获得最均匀的可能混合作用,在模塑操作之前增强的程度尽可能是常数,和另一方面,重要的是增强丝束为制造的复合产品赋予最佳机械性能。 Objects in a mold by the injection molding method tow manufactured by composite material reinforced organic material and the difficulty of mixing these components so resolved; on the one hand, the need to obtain the most uniform possible mixing between the organic material and reinforcing material prior to the molding operation as a constant degree of enhancement, and on the other hand, it is important for the production of reinforced composite strand product gives optimal mechanical properties. 为此,重要的是获得增强丝束在基质中的良好分散作用和尤其避免该丝束的过度段裂。 For this reason, it is important to obtain a good dispersion enhancing tow in the matrix and in particular to avoid excessive Fragmentation of the tow. 与热塑性基质混合的丝束越长,这些困难越大。 The longer mixed with the thermoplastic matrix tow, the greater these difficulties.

以筒单的方式,可以想象到通过使用包括加热的机筒来进行这一混合操作,在机筒中阿基米德螺杆或单螺杆在电动机的作用下旋转。 With single cylinder way imaginable to make this mixing operation including through the use of a heated cylinder, Archimedes screw or single screw rotation in the barrel under the action of a motor. 该机筒包括,在其一个末端的上部,至少一个进料斗,该进料斗的底部直接通向阿基米德螺杆。 The machine includes a tube, one end of the upper part of at least one feed hopper, the bottom of the hopper direct access to the Archimedes screw. 该设备利用该进料斗喂送有机材料和玻璃丝束。 The device utilizes the organic material into the feed hopper and glass strands.

通过使用计量设备将有机材料,呈现微粒和增强纤维形式的形式, 呈现切短玻璃丝束的形式,例如作为预掺混物被? By using an organic material metering device, showing the form of particles and reinforcing fibers in the form of chopped glass strands in the form of presentation, for example, as a pre-blend was? 1入到进料斗中或作为共混物被引入到进料斗中。 1 into a hopper or as a blend is introduced into the feed hopper.

然而,由申请人所进行的研究表明,该方法,虽然有可能和能够用于普通的短纤维,即具有大体上低于6 mm的长度的纤维,然而无法在较长纤维的引入时使用,鉴于以下理由: However, studies conducted by the applicant show that this method, although it is possible and can be used for ordinary staple fiber, which has a substantially less than the length of the fiber of 6 mm, but can not be used when introducing longer fibers In view of the following reasons:

a)在最终部件中的玻璃含量是不确定的和非恒定的。 a) glass content in the final part is uncertain and non-constant.

从长的切短玻璃丝束获得在注射模塑的复合部件中的规定玻璃含 Obtained from a predetermined length of chopped glass strand glass composite component injection molding-containing

量已经证明是不可能的,因为它们无法输送和它们不能计量,因为它们不流动。 Volume has proved to be impossible, because they can not be transported and which can not be measured, because they do not flow. 这一问题尤其在下列过程中会出现: This problem is particularly occur in the following procedures:

-长的切短玻璃丝束的(气动)输送: - Long chopped glass strands of (pneumatic) transport:

在切短玻璃丝束的生成过程中(制造过程),玻璃纤维长丝的切断导致微细物的出现。 Chopped glass strands in the generation process (manufacturing process), cutting the glass fiber filaments resulting in the fines. 这些微细物是萆毛形成和阻塞的渊泉,使得不可能将切短玻璃丝束直接输送到进料斗中。 These fines are castor Mao Yuan Quan formation and obstruction, making it impossible to chopped glass strands directly to the feed hopper. 另外,长的切短玻璃丝束的过分高的长度/直径比(L/D)比妨碍了它们的适当流动。 In addition, excessively high long-length chopped glass strands / diameter ratio (L / D) ratio impede their proper flow. 不可能在它们的特有包装中以及以正常使用的输送方式(它允许标准注塑设备的那些进料斗连在一起)获得长的切短玻璃丝束的适当流动。 Impossible in their unique packaging and to deliver normal use (which allows standard injection molding equipment that feed hopper together) to obtain long chopped glass strands of proper flow. 长的切短玻璃丝束的L/D比将由于掺杂而引起桥的形成,并最终妨碍纤维的任何运动;和 Long chopped glass strands of L / D ratio due to contamination caused by the formation of the bridge, and ultimately hinder any movement of the fibers; and

- 长的切短玻璃丝束的计量: - Long chopped glass strands of measures:

切断玻璃丝束是通过计量设备(例如称量加料器)根据物料的恒定流动来计量的,原料孔口打开的时间长度根据流动性来调节。 Cut glass strands are metered by the metering device (such as weighing feeder) According to the constant flow of material, the length of time the raw material according to the aperture open liquidity to adjust. 计量长的切短玻璃丝束已证明是不可能,因为桥的形成。 Metering long chopped glass strands has proved to be impossible, because the formation of the bridge.

b) 注射模塑复合部件的表面外观是不令人满意的: b) injection molding the composite part surface appearance is unsatisfactory:

纤维在复合部件的某些表面部分中集中。 Concentrated in certain surface portion of the fiber composite component.

用于由注塑工艺实现的转化中的单螺杆设备允许塑料基质被增塑但不允许,由于所产生的低剪切作用,获得玻璃纤维在基质内的均匀分散, 一些的纤维既不分散在基质中也不被该基质浸渍。 For the transformation of a single screw injection molding process implemented by the device allows the plastic substrate is plasticized but does not allow, due to the low shear generated, to obtain a uniform glass fiber dispersion within the matrix, some of the fibers are dispersed in the matrix either nor it is immersed in the matrix.

这一不良分散会导致所观察的表面缺陷也是在由注塑法获得的复合部件的机械性能上的损失的原因(参见以下c)点)。 The reason for this poor dispersion can cause surface defects is also observed in the mechanical properties of the composite components obtained by the injection molding method losses (see below c) points).

c) 所获得的复合部件的机械性能是差的; Mechanical properties of the composite component c) is obtained by difference;

玻璃丝束的不良分散作用或甚至有时非浸渍作用导致在注塑之后获得的复合材料的机械性能的显著下降,如拉伸强度,挠曲强度或却贝冲击强度的下降。 Adverse dispersion glass strands or even non-impregnated effects sometimes cause a significant decrease in the mechanical properties obtained after the injection of the composite material, such as tensile strength, flexural strength or Charpy impact strength decrease.

为了避免这些问题,对于以切断玻璃丝束为基础的热塑性复合材料,目前使用两步工艺: To avoid these problems, the chopped glass strands with a thermoplastic-based composites, the current two-step process:

-使用双螺杆挤出机、产生高剪切的第一步骤,以便允许纤维被热塑性基质的良好分散和浸渍。 - Using a twin screw extruder, to produce a first step of high shear, so as to allow the fibers to be well dispersed and impregnated with a thermoplastic matrix. 这一双螺杆挤出机使得切短玻璃丝束有可能处于高应力,以便通过剪切分离玻璃长丝和允许所获得的纤维被浸渍,同时确保它们被分散在基质内。 The twin-screw extruder so that the chopped glass strands may be in a high stress, so as to be separated by shearing glass filaments impregnated and allows the obtained fiber, while ensuring that they are dispersed within the matrix. 对于以切断玻璃丝束为基础的增强 In cutting the glass-based reinforcing strands

热塑性复合材料,所施加的这一高剪切作用具有大大减少基质中纤维的 Thermoplastic composites, the high shear applied has greatly reduced matrix fibers

长度的作用,该长度主要低于1 mm。 The role of length less than the length of the main 1 mm. 在离开口模时所获得的挤出物然后通过4吏用造粒扭4皮切粒成^:粒;和 Extrudate leaving the die obtained then twisted through four officials with a pelletizer into ^ 4 Peel tablets: tablets; and

-在第二步骤中,所获得的这些微粒用于单螺杆类型的普通注塑设备中。 - In the second step, these particles are obtained for conventional single-screw type injection molding apparatus. 该工艺的例子例如已描述在专利申请wo 96/40595, WO 98/43920, WO 01/05722或WO 03/097543中。 Examples of the process such as is described in the patent application wo 96/40595, WO 98/43920, WO 01/05722 or in WO 03/097543.

该方法因此包括两个单独的步骤,由挤出配制纤维增强微粒的步骤和形成微粒的步骤。 The method therefore comprises two separate steps, the step of preparation of a fiber-reinforced extruded particles and the step of forming microparticles. 第一步需要高花费的和不广泛使用的设备即双螺杆 The first step requires high cost and equipment that is not widely used in the twin-screw

在复合部件生产现场中进行的。 In composite parts production site conducted. y 、' A々'~ ' y, 'A々' ~ '

从前面可以看出很长时间以来需求一种比较简单、廉价和灵活性的 As can be seen from the front of a long time demand is relatively simple, inexpensive and flexible

工艺以使得长纤维形式的长玻璃丝束容易地插入到复合材料中。 Process so long fiber in the form of long glass strands easily inserted into the composite material. 该方法构成了本发明的主题。 This method forms the subject of the present invention.

本发明因此通过仅仅使用单螺杆类型的标准注塑设备,在满足工艺和所获得的复合材料的技术限制的同时,从长的切短玻璃丝束开始可以生产出由长纤维增强的热塑性部件。 The present invention thus by using only a single screw type of standard injection molding equipment, to meet the process and the obtained composite technical limitations, while from the beginning of the long chopped glass strands can be produced from long fiber-reinforced thermoplastic components. 尤其,这允许在复合部件上的玻璃含量,令人喜欢的表面外观和良好水平的机械性能的非常满意的控制。 In particular, it allows the glass content of the composite part, very good control pleasing surface appearance and a good level of mechanical properties.

更确切地说,本发明涉及制造由被长玻璃纤维增强的热塑性基质的締合所形成的复合部件的方法,该方法包括利用包含被喂送热塑性基质原料和增强材料的单螺杆挤出机的一种设备所进行的注塑或注射-压缩模塑步骤,该方法的特征在于该增强纤维是以长的切短玻璃丝束的微粒形式被引入到该设备中,它的密度或玻璃含量是在90至99.5%,优选在95至99%,和L/D比是低于L,以mm表示。 More particularly, the present invention relates to a method for manufacturing a composite part made by the long glass fiber reinforced thermoplastic matrix formed by the association, the method including the use of feed containing the thermoplastic matrix material is reinforcing materials and a single screw extruder An injection molding apparatus or injection performed - compression molding step, the method being characterized in that the reinforcing fibers are in particulate form long chopped glass strands are introduced into the apparatus, its density or the glass content is 90 to 99.5%, preferably 95-99%, and L / D ratio is less than L, in mm.

典型地,该L/D比对于长度L等于30 mm的微粒是低于30,对于24 mm微粒是低于24,和对于12 mm孩i粒是低于12。 Typically, the L / D ratio of the length L is equal to 30 mm is less than 30 particles, the particles are less than 24 24 mm, and 12 mm for the child particle i is less than 12.

优选地,该L/D比是低于L的2/3,用mm表示。 Preferably, the L / D ratio is less than 2/3 L, in mm. 例如,该比率对于30 mm长度的微粒是低于20,对于24 mm微粒是低于16和对于12 mm 微粒是低于8。 For example, the ratio of the particle 30 mm length is less than 20, for 24 mm particles are less than 16 and 12 mm for particles less than 8.

根据一个可能的实施方案,该L/D比是在L/4至L/2之间,L用mm 表示,例如该L/D比对于30 mm长度的微粒是在7.5至15之间,对于24 mm微粒是在6至12之间,和对于12 mm微粒是在3至6之间。 According to one possible embodiment, the L / D ratio is between L / 4 to L / 2, L in mm, such as the L / D ratio of the particle length of 30 mm is between 7.5 to 15, for 24 mm particles are between 6-12, and the 12 mm particles are between 3-6.

在本发明的上下文中,如果该微粒具有圆形截面,则对于该方法的 In the context of the present invention, if the particles have a circular cross section, then for the method of

应用所考虑的直径D等于该横截面的最小测量值。 Applications considered the minimum diameter D equal to the cross-section measurements.

根据本发明的高密度玻璃微粒例如通过使用描述在专利申请wo For example, by using the description in the patent application wo high density glass particles according to the present invention.

96/40595, WO 98/43920, WO 01/05722或WO 03/097543中的原理,工艺和装置来合成的,对于该合成的实施可以参考这些文献。 96/40595, WO 98/43920, WO 01/05722 or WO 03/097543 in principle, process and apparatus for synthesizing, for the implementation of the synthesis can refer to these documents.

例如,在本发明的上下文中使用的玻璃丝束一般通过使用下列相继的步骤来制造的: For example, in the context of the present invention, the glass strands are generally used by using the following successive steps of manufacturing:

-在潮湿气氛中通过拉丝模从熔化玻璃状将长丝进行纤维化 - From the molten glass filaments were fibrosis in a humid atmosphere by drawing die

■由施月交液体X于该长丝施月交; ■ monthly pay by the application of liquid X applied to the filament cross month;

-让该长丝收集成丝束;和 - Allow the collection into a filament tow; and

-切短该丝束形成具有在6至30mm之间的长度的玻璃丝束。 - Chopped glass strands forming the strand having a length of between 6 and 30mm.

在这一阶段,该切短玻璃丝束被润湿。 At this stage, the chopped glass strand is wetted. 它们一般包括5-25wt。 They generally include 5-25wt. /。 /. 的水, 例如5-15wt。 Water, for example 5-15wt. /o的水。 / O water. 一般来说,在它们被引入到混合步骤中之前不需要干燥它们,这从上述文献中本身已知,这一步骤需要在水和任选地在粘结剂存在下进行。 Generally, before they are introduced into the mixing step does not require drying them, which is known per se from the literature, this step requires water and, optionally, carried out in the presence of a binder. 因此,为该混合器增加例如在WO 03/097543中描述的那一类型的那些设备是为了获得被引入到混合器中质量的在10-25wt%范围的总水含量所需要的水的可能补充(相对于由纤维化步骤提供的水)。 Therefore, increase mixer such as those for which the type of equipment described in WO 03/097543 is to obtain the water is introduced into the mixer in mass 10-25wt% total water content in the range needed for possible supplementary (relative to water supplied by fibrosis step). 可以并且优选的是不需要添加补偿水(减少造粒机的结垢和提高产量)。 It can be and preferably is not necessary to add water to compensate (reduce fouling and increase production granulator). 为此,它足以在足够的湿度下纤维化而获得恰当的粒化。 For this purpose, it is sufficient under sufficient moisture fibrosis obtain proper granulation.

通常,该混合进行足够长的时间以使切短玻璃丝束的密度增高是相当大的并且通过使用一种混合器来如此进行,该混合器在每一瞬间为丝束或含有该丝束的所形成微粒赋予相同的混合频率,最终形成的微粒在干燥之后例如含有至少95%,优选至少97%和非常优选至少99%(按重量)的玻璃,可能的粘结剂在该混合操作的最后阶段与玻璃丝束接触。 Typically, the mixing is conducted for a time sufficient to allow higher density of chopped glass strands is quite large and by using a mixer to such conduct, in every moment of the mixer containing the tow or tow the forming particles are given the same mixing frequency, the formation of the final particles after drying, for example at least 95%, preferably at least 97% and very preferably at least 99% (by weight) of the glass, the binder may be in the final stages of the mixing operation contact with the glass strands.

根据一个可能的实施方案,在该混合操作之前,将要混合的掺混物的各成分被引入该混合器中。 According to one possible embodiment, prior to the mixing operation, the ingredients to be mixed blend is introduced into the mixer. 因此,下列成分被引入: Thus, the following ingredients are introduced:

-切断的施胶的丝束; - Sizing cut tow;

-:掺混物总质量的10-25wt。 -: The total mass of the blend 10-25wt. /。 /. 的水;和 Water; and

-任选的粘结剂。 - Optional binder.

根据一个可能的实施方案,该粘结剂可以选自在申请WO 03/097543 中列举的化合物,如: -聚酯; -聚氨酯;-环氧聚合物,例如双酚A的二缩水甘油醚的聚合物; -环氧-聚氨酯共聚物; -接枝聚丙烯。 According to one possible embodiment, the binder may be selected from the compounds in the application WO 03/097543 listed, such as: - polyester; - polyurethane; - epoxy polymer such as bisphenol A diglycidyl ether polymers; - epoxy - polyurethane copolymer; - grafted polypropylene.

根据一个可能的实施方案,该粘结剂可以选自EVA(乙烯-乙酸乙烯酯)和EEA(乙烯-丙烯酸),按照在说明书的后面部分中所述。 According to one possible embodiment, the binder may be selected from EVA (ethylene - vinyl acetate) and EEA (ethylene - acrylic acid), as described later in the specification. 该粘结剂一般根据所要增强的热塑性塑料的本性来选择。 The binder is generally based on the desired reinforced thermoplastic nature to choose.

切短玻璃丝束通过在混合过程中并列进行聚集而形成了微粒,没有它们长度的改变。 Chopped glass strands were gathered side by side in the mixing process and the formation of particles, they did not change the length. 因此,该微粒基本上呈现具有一定长度的圆柱形,该长度基本上等于在开始引入的最长丝束的长度。 Thus, the microparticles exhibit a substantially cylindrical shape having a length, the length is substantially equal to the length of the longest strands introduced.

可以使用具有从6到30 mm,例如8到24 mm和典型地9到15 mm 的长度和更特别具有约9 mm, 12 mm或15 mm的平均长度的切短3皮璃丝束。 It can be used with a 6 through 30 mm, for example, 8 到 24 mm and typical for nine 到 length of 15 mm and more particularly of about 9 mm, 12 mm shortened the average length of 15 mm or 3 skin glass tow.

还可使用具有不同长度的丝束的混合物作为丝束。 The mixture can also be used with different lengths of tow as the tow. 起始的切短玻璃丝束也可包括微细物,因为这些微细物通过聚结作用参与粒化,以便被插入到微粒中。 Starting chopped glass strands may also include fines, since these fines by coalescence granulated participation, so as to be inserted into the microparticles.

在丝束中所含的长丝可具有例如从5到24 ym的直径。 Contained in tow filaments may have, for example from 5 to 24 ym diameter. 该混合被混合足够的时间以便获得微粒的所需长度/直径比和/或所预期的密度增高。 The mixing time is sufficient to obtain mixed particles of a desired length / diameter ratio and / or the expected density increased. 根据本发明,所制备的微粒的密度一般比起始切短玻璃丝束的密度大了至少35%,甚至大了至少50%,甚至大了至少67%, 甚至大了至少80%,甚至大了至少100%,甚至大了至少130%,甚至大了至少200%。 According to the present invention, the density of the particles is generally prepared starting chopped glass strands than the density of at least 35%, or even at least 50% larger, or at least 67% larger, at least 80% or even larger, even larger at least 100%, even bigger at least 130%, even at least 200% larger.

根据本发明的高密度玻璃微粒一般具有严格地说低于2.0%和甚至低于1.5%,例如从0.5到1.5%,尤其从0.7到1.2%的烧失量。 From 0.5 to 1.5%, in particular from the loss on ignition in accordance with high-density glass fine particles of the present invention generally it has strictly less than 2.0% and even less than 1.5%, for example, of 0.7 to 1.2%.

根据本发明的最终微粒的例子包括具有5-24ym的单位直径的许多平行玻璃长丝,这些长丝全部具有相同的标称直径或具有不同的标称直径。 According to the present invention, examples of the final microparticle comprises a plurality of parallel glass filaments having a diameter 5-24ym units, which all have the same nominal filament diameter or having different nominal diameters. 在微粒中所含的长丝的数量尤其可以是1000 - 100 000,这取决于长丝的直径,例如2000到50 000。 The number of particles contained in the filaments can be especially 1000--100000, depending on the diameter of the filament, e.g., from 2000 to 50 000. 长丝在孩i粒中的堆叠最通常是压紧性质。 Filaments stacked on child i grain of most commonly pressing nature.

例如,热塑性基质可以选自聚丙烯(PP),聚酰胺(PA),聚对苯二甲酸乙二醇酯(PET)或聚对苯二曱酸丁二醇酯(PBT),苯乙烯类树脂,如丙烯腈-丁二烯-苯乙烯(AB S), 聚乙烯(PE), 聚苯硫(le polysulfure de ph6nyl^e, le polyph6nyl6ne Sulfide)(PPS),聚碳酸酯(PC),和聚缩醛类, 如聚氧化亚曱基(POM)。 For example, the matrix may be selected from a thermoplastic polypropylene (PP), polyamide (PA), polyethylene terephthalate (PET) or polyethylene terephthalate, polybutylene terephthalate Yue acid (PBT), styrene-based resin , such as acrylonitrile - butadiene - styrene (AB S), polyethylene (PE), polyphenylene sulfide (le polysulfure de ph6nyl ^ e, le polyph6nyl6ne Sulfide) (PPS), polycarbonate (PC), and poly acetals, such as polyoxymethylene Yue group (POM).

根据本发明的优选实施方案,还发现以上制造方法也能够通过使用熔点比热塑性基质的熔点更低的施胶剂来改进。 According to a preferred embodiment of the present invention, there can also be found in the above production method using a lower melting point than the melting point of the thermoplastic matrix to improve sizing. 在熔点之间的差异是尽 The difference between the melting point is to do

可能高的并且理想地大于5°C,优选大于7。 High as possible and ideally more than 5 ° C, preferably greater than 7. C和非常优选大于l(TC甚至2(TC或甚至25。C。术语"熔点"在本说明书的上下文中被理解为一种温度,在该温度下施胶剂的固体含量的至少50wt%,优选至少70wt。/。和非常优选至少90wt。/。处于熔化形式。 C and very preferably greater than l (TC or 2 (TC or even 25.C. term "melting point" in the context of this specification is understood to be a temperature of at least 50wt% at the temperature of the solid content of the sizing agent, preferably at least 70wt. /. and very preferably at least 90wt. /. in molten form.

例如,当使用聚丙烯(PP)基质时,适合于制造长的高密度玻璃纤维 For example, when using polypropylene (PP) matrix, suitable for the manufacture of high-density glass fiber length

-水性EVA(乙烯-乙酸乙烯酯)乳液,它的共聚物具有50%或更高的乙烯含量和在110。 - Aqueous EVA (ethylene - vinyl acetate) emulsion, which copolymer has 50% or more and an ethylene content in 110. C左右的熔点,或水性EAA(乙烯-丙烯酸)乳液,它的共聚物具有50%或更高的乙烯含量,和在ll(TC左右的熔点; The melting point of about C, or aqueous EAA (ethylene - acrylic acid) emulsion, which copolymer has 50% or more of ethylene content and melting point ll (TC or so;

-马来酸酐接枝的聚丙烯(MAH-g-PP)的水乳液,其中它的聚合物的熔点是165'C左右;和 - Maleic anhydride grafted polypropylene (MAH-g-PP) aqueous emulsion, wherein the polymer its melting point is about 165'C; and

- 一种或多种有机硅烷,其中至少一种氨基硅烷类型,和,任选: - One or more organic silane, wherein at least one aminosilane type, and, optionally:

-配制剂的稳定剂,如N-丁基胺(它在干燥过程中蒸发); - Formulation stabilizers, such as N- butylamine (which evaporate during drying);

-成膜聚合物如聚氨酯(PU)的水乳液;和 - Film-forming polymers such as polyurethane (PU) aqueous emulsion; and

-加工助剂,如表面活性剂和/或润滑剂和/或抗静电剂。 - Processing aids, such as surfactants and / or lubricants and / or antistatic agents.

这些施胶剂的固体含量是掺混物的初始重量的10wt。 The solids content of the sizing agent is a blend of the initial weight of 10wt. /。 /. 左右。 About. 表l总 Table l total

<table>table see original document page 9</column></row> <table> 典型的施胶配制剂是,例如,按固体(干)物质的百分数: <Table> table see original document page 9 </ column> </ row> <table> typical sizing formulations are, for example, as a solid (dry) percentage of:

<table>table see original document page 10</column></row> <table> <Table> table see original document page 10 </ column> </ row> <table>

在申请人进行的试验过程中使用的产品是以下列参考符号销售 Used in the testing process conducted by the applicant in the product based on the following reference symbols Sales

的: Of:

硅烷:Silquest A1100® (GE), AMEO® (Degussa); EVA: EVAX28® (Michelman); Silane: Silquest A1100® (GE), AMEO® (Degussa); EVA: EVAX28® (Michelman);

EAA: Michem Prime 4983® (Michelman), AC5120®在水中的铵盐(Honeywell); EAA: Michem Prime 4983® (Michelman), AC5120® salt in water (Honeywell);

MAH-g-PP: Michem 43040® (Michelman), Novacer 1800® (BYK Cera); MAH-g-PP: Michem 43040® (Michelman), Novacer 1800® (BYK Cera);

EU: Witcobond 290H® (C讓pton), Baybond PU401® (Bayer)。 EU: Witcobond 290H® (C let pton), Baybond PU401® (Bayer).

据本发明是在155。 According to the present invention is 155. C和120。 C and 120. C之间,即比PP基质的熔点低至少7°C。 Between C, namely a lower melting point than PP matrix of at least 7 ° C.

高密度玻璃微粒和长纤维的使用与如上所述的施胶剂的使用优选相结合使得可通过标准的注塑或注射-压缩模塑法直接获得复合部件; High-density glass particles and long fiber sizing agent described above is preferably used in combination so that through a standard injection molding or injection - compression molding of composite parts directly;

-确定的和恒定的^^璃含量; - Identify and constant ^^ glass content;

-均匀的表面外观; - Uniform surface appearance;

-增强的机械性能。 - Enhanced mechanical properties.

本发明体现特征于:单螺杆设备确保进行该部件的初始成分(即基质和纤维)的掺混步骤,和才莫塑步骤。 Embodying features of the invention is to: a single screw equipment to ensure the initial components of the components (ie matrix and fiber) blending step, and only Mo plastic steps.

尤其,玻璃含量的控制和在该方法中注射模塑的复合部件的纤维分散得到改进,这是由于: In particular, the control and the fibers in the injection molding process of the glass content of the composite member of the dispersion is improved, which is due to:

- 一方面,以提高其密度的量和恒定性,和因此提高在增强纤维的输送和计量步骤中它们的适当流动(有合适的L/D比)为目的将切断玻璃丝束粒化的步骤;和 - On the one hand, to increase its density and the amount of constant resistance, and thus increasing the step in the feeding and metering reinforcing fibers in their proper step flow (with the appropriate L / D ratio) for the purposes of the chopped glass strand granulation; and

-另一方面,施胶剂的性质,该施胶剂在这些同样的步骤中确保在纤维输送(常常借助于空气)到注塑机的过程中和在计量的过程中高密度 - On the other hand, the nature of the sizing, the sizing agent to ensure that the fiber feeding (often by means of air) to the injection molding machine in the same process steps and the high density of the measurement process

玻璃微粒的良好完整性和强度,和然后在注塑步骤中,纤维在热塑性基质中的良好分散作用。 Good integrity and strength of the glass particles, and then injection molding step, the fiber well dispersed in the thermoplastic matrix.

最终获得的复合产品此外显示出改进的机械性能,这可在下面的实施例中观察到。 In addition the final composite product obtained exhibits improved mechanical properties, which can be seen in the following examples.

图1举例说明了根据本发明的注塑方法的举例性实施方案。 Figure 1 illustrates the injection method according to the present exemplary embodiment of the invention. 热塑性 Thermoplastic

树脂,例如聚丙烯和高密度玻璃微粒,即例如具有大于95%的玻璃含量的那些,以掺混物8的形式被引入到用于复合部件的注塑加工的模塑设备1的进料斗2中。 Resins, such as polypropylene and high density glass particles, i.e., e.g., those having a glass content of greater than 95%, in the form of blend 8 is introduced into the injection molding process for the composite member of the molding apparatus 1 hopper 2 in. 风力输送设备(在图1中未显示)用来输送该高密度玻璃微粒到进料斗2中。 Pneumatically feeding device (not shown in FIG. 1) for conveying the glass particles to a high density in the hopper 2. 设备1,除进料斗2外,包括放入在机筒4中的单螺杆3,其中壁由环形的电阻器5加热,典型地在20CTC至30(TC之间的温度下。两种类型的微粒的各自性能通过使用已知的技术在上游进行调节,例如借助重量计量进料器。在由机筒4的壁上的加热电阻器5 产生的热量和在壁上摩擦的热量的联合作用下,热塑性树脂微粒被增塑并且施胶剂的熔化导致纤维在热塑性基质中的均匀分散。在标准的注塑设备中,单螺杆根据本方法实现两个功能: Device 1, in addition to outside the hopper 2, placed in a cylinder including a single screw 4 3, wherein the annular wall is heated by a resistor 5, to 30, typically at a temperature in the 20CTC (TC between. Two types their performance by fine particles is adjusted using known techniques in the upstream, e.g., by means of weight-feeder. In the heat generated by the combined action of the barrel wall of the heating resistor 4 and 5 to generate heat in the walls of friction , the thermoplastic resin particles are plasticized and sizing cause melting fibers are uniformly dispersed in the thermoplastic matrix in a standard injection molding equipment, a single screw performs two functions according to this method:

-通过旋转和退却,增塑功能,用于增塑该热塑性材料;和-通过在机筒4中滑动,在增塑后,填充模具6和反模具7系统的活塞功能。 - By rotating and retreat, plasticized function for plasticizing the thermoplastic material; and - by sliding in a cylinder 4, after the plasticized, filling the mold and counter mold 6 piston 7 system function.

最终得具有令人满意的表面外观和显示出良好机械性能的复合部件,它的玻璃含量在生产过程中基本上是恒定的。 Finally obtained having satisfactory surface appearance and exhibited good mechanical properties of the composite member, its content in the glass manufacturing process is substantially constant.

当然,本发明的以上实施方案决不将本发明限制于任一个的所述方面。 Of course, the above embodiments of the present invention is in no way to limit the invention to any one of the aspects. 尤其,在不脱离本发明的范围的情况下,热塑性树脂微粒和高密度玻璃微粒能够在该设备的不同点上进行注射模塑。 In particular, without departing from the scope of the present invention, the thermoplastic resin particles and high density glass particles can be injection molded at different points of the device. 更一般地说,任何已知的注塑设备可能用来实施该工艺。 More generally, any known injection molding equipment may be used to implement the process.

根据本发明的方法和它的优点例如将借助于以下非限制性的实施例来举例i兌明。 For example, by means of the following non-limiting embodiment of the method of the present invention and its advantages for example i against Ming.

实施例1: Example 1:

通过使用具有以下配方的包含以接枝了马来酸酐的聚丙烯为基础的水乳液的施力交液体来制备长的切短3皮璃丝束: Urging deposit liquid having the following formulation by using comprises polypropylene grafted with maleic anhydride based aqueous emulsion prepared long chopped glass strands 3 skin:

-70wt。 -70wt. /o的由Michelman公司以参考编号Michem 43040⑧销售的马来酸酐接枝聚丙烯水性乳液,它的接枝度是4wt。 / O by Michelman company MAH reference number Michem 43040⑧ sell polypropylene aqueous emulsion, its degree of grafting is 4wt. /。 /. ,酸值是45和重均分子量是9100; Acid value is 45 and the weight average molecular weight of 9100;

画10wto/o的由General Electric以参考编号"Silquest® A画1100"销售 Videos 10wto / o by General Electric reference number "Silquest® A 1100 painting" Sales

的y -氨基丙基三乙氧基硅烷(硅烷);和 The y - aminopropyl triethoxysilane (silane); and

-20wt。 -20wt. /。 /. 的由Bayer以参考编号"Baybond® PU401"销售的聚氨酯(PU)。 From Bayer with reference numeral "Baybond® PU401" selling polyurethane (PU).

施胶组合物的制备按照以下方法来进行: Sizing composition was prepared according to the following approach to:

硅烷的乙氧基在维持于搅拌状态的软化水中水解,然后添加其它成分,再次进行搅拌。 Ethoxy silane state maintaining stirring demineralized water hydrolysis, and then add the other ingredients, stirring again. 在施胶组合物中固体材料的重量含量等于10%。 In the sizing composition by weight of solid material content equal to 10%. 如下获得施胶的丝束: Obtained by sizing the tow:

施胶组合物用于以已知方式涂覆具有约17 的直径的E-型玻璃长丝,这些长丝是从拉丝模的孔流出的玻璃流股拉伸而成,然后组装成丝束,每一丝束有500根长丝。 Sizing compositions are used in a known manner E- glass coated with a filament diameter of about 17, which is stretching the filaments from glass streams flowing hole drawing dies, then assembled into a tow, Each strand has 500 filaments.

在纤维化和施胶步骤之后获得的该丝束被切短,以便获得具有12 mm± 1 mm的平均长度的长的切短玻璃丝束,扁平形状,即平均2 mm 宽度和0.5 mm厚度。 After the tow fibrosis and sizing step obtained is cut short in order to obtain long chopped glass strands having an average length of 12 mm ± 1 mm, flat shape, or an average of 2 mm width and 0.5 mm thickness. 该切短玻璃丝束的测量密度是0.40 g/cm3。 The chopped glass strands of measuring the density is 0.40 g / cm3.

实施例2: Example 2:

长的切短玻璃丝束通过使用普通方法来合成。 Long chopped glass strand synthesized by using conventional methods. 用于在纤维化之后将长丝组装成丝束的施胶液体含有以下百分数的下列成分,按干燥物质计: After fibrosis for the filament tow assembled sizing liquid containing the following percentages of the following ingredients, in the dry matter basis:

-70城%的由Michelman公司以参考编号EVAXM⑧销售的水性EVA(乙烯-乙酸乙烯酯)乳液,它的乙烯重量含量是82%和熔点是在110 r左右, -70% By Michelman City company sales reference number EVAXM⑧ aqueous EVA (ethylene - vinyl acetate) emulsion, which is an ethylene content of 82% by weight and a melting point of about 110 r,

-20wt。 -20wt. /。 /. 的由Michelman以参考编号Michem 43040⑧销售的马来酸 By Michelman reference number Michem 43040⑧ sales of maleic acid

酐接枝聚丙烯水性乳液,它的接枝度是4wt。 Anhydride-grafted polypropylene aqueous emulsion, its degree of grafting is 4wt. /。 /. ,酸值是45,重均分子量 Acid value 45, weight average molecular weight

是9100和聚合物的熔点是在165。 9100 and melting points are 165. C左右;和 C so; and

-10wt。 -10wt. /o的由General Electric以参考编号"Silquest® A-1100"销售 / O General Electric by the reference number "Silquest® A-1100" Sales

的y -氨基丙基三乙氧基硅烷(硅烷)。 The y - aminopropyl triethoxysilane (silane).

施胶组合物按照在实施例1中描述的方式类似的方式获得。 The sizing composition according to the manner described in Example 1 was obtained in a similar manner. 所获得的施胶剂(固体含量)的所测量熔点起始于约120 °C的温度和 Sizing obtained (solid content) measured at a temperature of about the melting point of initiation to 120 ° C and

连续提高到约150°C。 Continuous increase to about 150 ° C.

按照与实施例1中所述的方式类似的方式获得丝束和施月交。 In accordance with the manner described in Example 1 in a similar manner to get a tow and applied monthly pay. 所获得的丝束然后使用已知的技术被切短以获得具有12 mm±l The tow is then obtained using known techniques are chopped to obtain a 12 mm ± l

mm的平均长度的长的切短玻璃丝束,具有扁平形状(约2 mm宽度x约 The average length of chopped glass strands mm length, and has a flat shape (approximately 2 mm width x about

0.2 mm厚度)和0.40 g/cm"5的密度。 实施例3: . 0.2 mm thickness) and 0.40 g / cm "Density 5 Example 3:

通过使用在申请WO 03/097543中描述的方法和混合设备将在实施例2中获得的长的切短玻璃丝束致密化,直至获得具有接近于99%的玻璃密度的微粒为止,获得了具有12 mm土lmm的平均长度,基本上具有圆柱形和具有平均直径2.5 mm以及0.80 g/cm3密度的高密度玻璃微粒。 By using the long chopped glass method and mixing equipment described in the application WO 03/097543 obtained in Example 2 tow densification, until the particles have a density close to 99% of the glass is reached, obtained with 12 The average length of lmm mm soil, having a substantially cylindrical shape and having an average diameter of 2.5 mm and 0.80 g / cm3 density, high-density glass particles. 使用普通方法测量的微粒的烧失量低于1%。 Use common method of measuring microparticles less than 1% loss on firing.

实施例4: Example 4:

使用包含30wt。 Containing 30wt. /。 /. 被分散在PP基质中的已切短至12 mm ± 1 mm的玻璃纤维的、具有约2.5mm的直径和0.70g/cm3的密度的热塑性微粒。 Was dispersed in the PP matrix was chopped to 12 mm ± 1 mm of glass fiber, and thermoplastic particles having a diameter of 0.70g / cm3 density of approximately 2.5mm. 这些微粒由Ticona以参考编号Celstran⑧销售。 These particles produced by Ticona reference number Celstran⑧ sales. 该微粒通过使用众所周知的技术用聚丙烯基质浸渍玻璃粗纱来制备的,该基质的重量百分比是70%。 The fine particles by using well known techniques glass roving impregnated with a polypropylene matrix prepared, the weight percentage of the matrix is 70%.

实施例5: Example 5:

使用与在实施例3的规程相同的规程,将在实施例1中获得的长的切短玻璃丝束致密化,直至获得具有接近于99%的玻璃密度的微粒为止,获得了具有12 mm±l mm的平均长度,基本上具有圆柱形和具有平均直径2.5 mm以及0.83 g/cm3密度的高密度玻璃微粒。 In the procedure used in Example 3 with the same protocol implementation, in the implementation of the long chopped glass strands obtained in Example 1 densification, until a particle having a density of close to 99% of the glass is reached, obtained with 12 mm ± l mm in average length, having a substantially cylindrical shape and having an average diameter of 2.5 mm and 0.83 g / cm3 density, high-density glass particles. 使用普通方法测量的微粒的烧失量低于1%。 Use common method of measuring microparticles less than 1% loss on firing.

实施例6: Example 6:

进行流动试验,用于测试根据实施例1到5获得的纤维的微粒的流动性。 Flow test conducted for flowability test according to Example 1-5 of the fiber obtained microparticles. 这一试验可评价在预定条件下切短玻璃丝束或微粒的流动性。 This test can evaluate the flowability of chopped glass strands or particles under predetermined conditions. 这一能力是用秒表示。 This capability is indicated in seconds.

流动时间是对于5kg量的产物测量的。 Flow time is the amount of product for 5kg measured. 将产物放置于进料斗中,抽空空间或它的管道位于与以1 mm振幅振动的流动通道相距28.5 mm的地方。 The product was placed in a hopper, evacuated space or a pipe located in the flow path and the amplitude of vibration 1 mm 28.5 mm apart place.

表2总结了在每一种产物的流动试验中获得的结果。 Table 2 summarizes the results obtained in the flow test of each product.

表2 Table 2

<table>table see original document page 14</column></row> <table>根据实施例1到5合成的各种纤维或微粒的可运输性也可通过几种试验来评价: <Table> table see original document page 14 </ column> </ row> <table> Example 1-5 according to the synthesis of various fibers or particles transportability may also be evaluated by several tests:

1. 评价切短玻璃丝束和微粒的微细物的含量的试验(试验微细物) 该术语"微细物(fmes)"被理解为指在其运输过程中与初始产物分 1. Evaluation of chopped glass strands and the content of fine particles of the test material (test fines) the term "fines (fmes)" is understood to mean the process in which the initial product of the transport sub-

离的细玻璃棒条体或长丝。 Strip away the thin glass rod body or filaments. 微细物的含量被认为是利用抽吸作用,在下列条件下对于由截获阱中的500克产物组成的试样所收集到的微细物的量。 The content of fines is considered the use of suction, a sample from the capture trap for 500 g of product consisting of the collected amount of fines under the following conditions.

将所要试验的产物放置于进料斗中,它的出口位于与振动通道相距4 mm的地方,让产物均匀地流动和散布。 The product to be tested will be placed in a hopper, and its outlet is located at a distance of 4 mm vibration channel, let the product flow and spread evenly. 具有《設细物截获阱的抽吸系统位于这一振动通道以上,以便浮获全部的游离玻璃棒条体或长丝。 Have "set a fine was intercepted wells pumping system located above the vibrating channel to all of the free float is eligible for glass rod or bar form filaments.

微细物含量在表3中以mg/kg表达。 Fine content in Table 3 to mg / kg expression. 50或更低的值被认为是令人满意的。 Value of 50 or less is considered to be satisfactory.

2. 风力输送试验(传输试验) 2. Wind transport test (transmission test)

本试验在于^t拟切短玻璃丝束或ITi粒从储存区到注塑机(例如属于针对图1所述的类型)的进料斗的风力输送。 This test is to ^ t chopped glass strands intended ITi grain from a storage area or to the injection molding machine (e.g., below for the type described in Figure 1) of the pneumatically feeding hopper.

将两千克的所要试验的产物(切短玻璃丝束或微粒)放置于贮藏容器中,然后由普通技术的风动喷射进料斗进行抽吸,引起产物沿着临界回路通过,就是说促进玻璃丝束长丝的细纤维或萆毛的形成。 The product (chopped glass strands or particles) the two kilograms to be tested is placed in the storage container, and then moving by the wind of ordinary skill in the ejection suction hopper, along the critical loop by causing the product, that is to promote glass strands fine fibers or filaments hairy castor seed formation.

在该试验之后,测量在风力进料斗的过滤器上积聚的葺毛的量。 After this test, measuring the amount of thatch of hair on the wind into the hopper filter accumulation. 所获得的茸毛的量以mg/kg表示。 The amount of hair to get in mg / kg.

3. 在风力输送试^验之后进行的孩i细物试一验 Boy i was 3. wind transport of fine ^ test after test conducted a test trial

这一试验就其应用而言等同于在第l点所描述的试验,但是这一次是在风力输送试一验之后采用。 This test its applications equivalent test described in paragraph l point, but this time in the wind transport after a test using the test.

4. PSI试验(风力应力完整性试验)这一试验在于模拟在切短玻璃丝束或微粒的高压下的风力输送。 4. PSI test (wind stress integrity test) This test is to simulate the wind transport at high pressure chopped glass strands or microparticles. 这一试验-比我们在工业中所能见到的传输试验显著地更苛刻-让产物经受非常大的应力。 This test - is significantly more demanding than transmission test we can see in the industry - so that the product is subjected to great stress.

50克量的产物在密闭的不锈钢环路中在5巴(0.5 MP)的压力下旋转45秒。 50 g quantity of the product in a sealed stainless steel loop at a pressure of 5 bar (0.5 MP) rotating 45 seconds.

这一试验使得移动产物受到应力和它耐摩擦(产物与产物以及产物与不锈钢壁)的性能可以被评价。 This test enables the mobile product is subjected to stress and rubbing it (the product with the product as well as product and stainless steel walls) performance can be evaluated. 在试验之后,产物被回收和筛网,以便分离出葺毛。 After the test, the product is recovered and a screen to separate out the repair hair.

这一试验的结果在表3中表示为所形成萆毛的百分数与产物的初始质量的关系。 The results of this test shows the relationship between the quality of the initial formation of a percentage of gross product of castor seed in Table 3.

表3 TABLE 3

<table>table see original document page 15</column></row> <table>实施例8: <Table> table see original document page 15 </ column> </ row> <table> Example 8:

在最终获得的复合部件上获得的玻璃含量对于长的切短玻璃丝束和微粒进行测量,通过采用针对图1描述的设备,在进料斗中的掺混(量) 由称量获得,采用由Magmre销售的重力计量系统。 On the glass content of the finally obtained composite member obtained for long chopped glass strands and particles were measured by using the apparatus described for Figure 1, blending (volume) in the feed hopper weighing obtained by using the Magmre sales of gravity metering system. 纤维或微粒作为掺混物按比例引入到进料斗中,该比例经过调节以便在最终的复合部件上获得30wt。 Fibers or particles as a blend in proportion introduced into the feed hopper, the ratio regulated to obtain 30wt in the final composite part. /。 /. 的玻璃含量。 The glass content. 在使用根据实施例4的微粒的情况下,具有30% In the case of the use of microparticles of Example 4, with 30%

的早已预定玻璃含量的后者当然单独被引入到进料斗,就是说没有与玻 Already predetermined glass content of the latter course alone is introduced into the feed hopper, that is not with Bolivia

璃组分分量(vector)纟参混。 Glass constituent components (vector) Si reference mix.

分析在101个相继的注塑周期之后在部件的组成上的变化。 Analysis After 101 successive molding cycle changes in components of. 图2a, 2b和2c得到了与在相继的周期中制造的部件的数量有关的玻璃含量(GC),当根据实施例3的微粒(图2a),根据实施例4的微粒(图2b)或根据实施例1的长的切短玻璃丝束(图2c)分別用来为进料斗供应玻璃纤维时。 Figures 2a, 2b and 2c obtained in successive cycles and the number of parts relating to the manufacture of glass content (GC), when the microparticles according to Example 3 (FIG. 2a), according to microparticles (Fig. 2b) or Example 4 According to an embodiment of the long chopped glass strand of Example 1 (FIG. 2c) were used to feed the hopper when the supply of glass fibers. 图2c中的零值意指由于桥的形成,在相应的周期中切短玻璃丝束的流动不能发生。 Figure 2c zero value means that due to the formation of the bridge, chopped glass strands in the corresponding period in the flow can not occur.

因此需要指出的是,实施根据本发明的方法所获得的结果(图2a)基本上等同于根据现有技术所获得的那些(图2b)。 Therefore, to be noted that the implementation of the method according to the present invention results obtained (Figure 2a) substantially identical to those according to the prior art obtained (FIG. 2b). 实施例9: Example 9:

纤维在最终获得的复合部件内的分散是针对从实施例1, 3, 4和5 得到的产物测量的。 Fiber composite parts in the finally obtained dispersion is directed from Example 1, 3, 4 and 5 was measured product.

这一测量在于评价该部件的其中玻璃纤维没有足够地分散的表面部分。 This measurement is to evaluate the surface portion of the member wherein the glass fiber is not sufficiently dispersed.

为此,玻璃微粒或玻璃长丝在热塑性塑料基质中的分散是在掺混物被注塑加工成具有2mm的厚度和控制尺寸的^反之后评价的。 For this purpose, glass particles or glass filaments in the thermoplastic matrix is dispersed in the blend is injection molding to have a thickness of 2mm and control the size of the ^ anti After evaluation. 这一测量在于评价由未分散在板内的纤维的团块(mass)所占据的面积,未分散长丝有可能同时在实际的板中和在表面上,板的小厚度使得可通过将它对着光看出在板内的未分散长丝。 This measurement is to evaluate the area of the inner panel in undispersed clumps of fiber (mass) occupied, it is possible to simultaneously undispersed filaments in the actual plate and the upper surface, a small thickness of the plate such that it can be prepared by not seen against the light dispersed filaments in the inner panel.

在实践中,玻璃纤维借助于单螺杆设备与热塑性材料一起被注入到特定形状的模具/反模具中,有可能获得具有精确确定的尺寸的非常薄的板,对于后者进行测量以便比较玻璃纤维在所获得的各种产物上的分散。 In practice, the glass fiber by means of a single screw device with the thermoplastic material is injected into a specific shape along mold / counter-mold, it is possible to obtain a precise determination of the size of a very thin plate, for which glass fiber is measured for comparison dispersed in a variety of product was obtained. 将该板放置于照明系统上以使该板的某些区域(存在了由于不良分散所产生的纤维的凝块)被显示出来。 The plate was placed on the illumination system so that certain areas of the plate (due to the presence of the poor dispersion of the fibers produced clot) is displayed.

这一区域的结果表示为所分析部件的总面积的百分数。 Results are expressed as a percentage of the area of the total area of the analyzed components.

照相机的规定调节条件下或通过使用扫描仪拍取该板的数字照片。 Under the provisions of the regulation or the camera shot to take the plate of digital photos by using a scanner.

这一图^象由Mesurim⑧图像分析软件进行分析。 This diagram ^ image analyzed by Mesurim⑧ image analysis software. 该软件用来转换对于许多像素所进行的分析,得到了显示出纤维的不良分散的百分面积(相对于板的总面积)形式的结果。 The software is used to translate a number of pixels for the analysis carried out, the results obtained show that the percentage of poor dispersion fiber area (with respect to the board's total area) form.

纤维/基质掺混物在板中由单螺杆设备的注塑是按照两种不同的实 Fiber / matrix blend in the plate with a single screw injection molding apparatus in accordance with two different real

16 16

验模式进行的。 The test mode.

条件1:在注射螺杆上的0巴的回压和标准螺杆速度即130转/分左 Condition 1: 0 in the injection screw bar back pressure and screw speed standard that is 130 rev / min left

右的使用。 Right of use.

条件2:施加于注射螺杆上的120巴(12 MPa)的回压,在材料的掺混过程中,在计量和注射阶段中限制它的退缩,和在计量结束时比较緩慢的螺杆速度(80转/分)的使用。 Condition 2: applied to 120 bar (12 MPa) injection screw back pressure on the material in the mixing process, limiting its retreat in metering and injection stage, and the relatively slow speed at the end of the metering screw (80 rev / min) use. 这些条件允许在在实际注射之前在螺杆的末端对玻璃/基质掺混物施加压力并增加在螺杆中物料的混合时间,但没有改变周期时间,以便改进纤维的分散和浸渍。 These conditions allow before the actual injection pressure at the end of the screw on the glass / matrix blend mixing time and increase the material in the screw, but without changing the cycle time, in order to improve the impregnation and fiber dispersion.

表4对于在实施例1, 3, 4和5中所述的从用于引入玻璃的半成品 Table 4 for 1, 3, from semi-finished glass for introducing 4 and 5 as described in Example

所获得的部件给出了这两种模式获得的结果。 Part of the obtained results are given in both modes available.

表4 Table 4

<table>complex table see original document page 17</column></row> <table> <Table> complex table see original document page 17 </ column> </ row> <table>

实施例10: Example 10:

在这一实施例中,使用根据本发明的方法,从根据实施例l获得的长纤维或从根据实施例3或4获得的微粒制造的复合部件的机械性能在为了获得它们中每一种的最佳结果所需要的条件下进行评价。 In this embodiment, using the method of the present invention, the embodiment according to the long fiber obtained in Example l or the mechanical properties of fine particles from Example 3 or 4 to obtain a composite member manufactured in each of them in order to obtain the were evaluated under the conditions required for the best results.

挠曲强度和该Charpy和Izod冲击强度是在分别由标准ISO 178, ISO 179和ISO 180限定的条件下测量的。 Flexural strength and the Charpy and Izod impact strength was respectively by the standard ISO 178, ISO 179 and ISO 180 defined measurement conditions.

所获得的结果对于100的基础给出在表5中,归属于根据实施例4 的热塑性塑料/30%玻璃微粒。 The results obtained are given in respect to the base 100 of Table 5, according thermoplastics attributable to Example 4/30 percent glass particles. 该测量是对于在注塑条件1或2下获得的复合部件进行的,使得有可能实现它们的最佳机械性能。 The measurements for the composite component injection molding obtained under conditions 1 or 2 are carried out, it makes it possible to achieve their optimal mechanical properties.

表5 Table 5

<table>table see original document page 18</column></row> <table>从根据本发明的方法获得的复合部件的机械性能与从现有技术的热塑性微粒获得的复合部件的那些相当。 <Table> table see original document page 18 </ column> </ row> <table> from quite according to those mechanical properties of the composite parts of the method of the present invention obtained composite parts obtained from the thermoplastic particles prior art.

Classifications
International ClassificationB29C45/00, C03C25/26
Cooperative ClassificationY10T428/2964, B29C45/0005, C03C25/26, B29K2105/12
European ClassificationC03C25/26, B29C45/00D
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