WO2013102590A1

WO2013102590A1 - Fibre composite

Info

Publication number: WO2013102590A1
Application number: PCT/EP2012/076675
Authority: WO
Inventors: Herbert Börger
Original assignee: Thermoplast Composite Gmbh
Priority date: 2012-01-03
Filing date: 2012-12-21
Publication date: 2013-07-11
Also published as: DE102012200059A1

Abstract

A fibre composite has a fibre material (5) having filaments (6). Furthermore, the fibre composite has a polymer matrix (8) in which the fibre material (5) is embedded and a bonding agent (9) with which the filaments (6) of the fibre material (5) are coated. The fibre material (5) is selected from at least one of the following materials: glass, carbon, Armid, basalt, polyester, natural fibre. The polymer matrix (8) is a thermoplastic polymer. The bonding agent (9) is based on at least one of the following materials: silane, polypropylene (PP), titanate, aluminium, chromium, zirconium and boron. A materials combination of fibre material/polymer matrix/bonding agent which is particularly suitable for the production of a fibre composite, in particular for the production of tapes composed of the fibre composite, results.

Description

Fiber composite material

The content of German patent application DE 10 2012 200 059.3 is incorporated herein by reference.

The invention relates to a fiber composite material with a fiber material, a plastic matrix, in which the fiber material is embedded and with an adhesion promoter, are coated with the filaments of the fiber material.

Fiber composite materials are known from US 201 1/0070989 AI, WO 2009/109593 AI, DE 10 2005 023 420 AI, DE 10 2005 040 620 AI, DE 10 2010 023 879 AI, DE 10 2009 01 1 668 AI , JP 201 1-074381 A, US 2006/0049541 A1, WO 201 1/014638 A1, US 2007/01 17909 A1, US 201 1/0230615 A1 and JP 2006 016463 A.

It is an object of the present invention to provide material combinations fiber material / plastic matrix / adhesion promoter, which are in a special way for the production of a fiber composite material and in particular for the production of tapes of the fiber composite material.

This object is achieved according to the invention by the Materialkombinatio- NEN, which are specified in claim 1.

In the production of Faserverbundwerstoffen exists a complex interaction between the materials involved, ie between the fiber material, the material of the plastic matrix and the material of the Adhesion promoter. This interaction strongly depends on the processing conditions in the production of the fiber composite material. The material combinations according to the invention fiber material / plastic matrix / adhesion promoter are in particular optimized for a band production of a fiber composite material. The impregnated with the plastic matrix sliver can then be used as an intermediate, for example, for the production of moldings, for example plates or profiles, from the fiber composite material, which may be constructed in particular layer by layer. In sliver production, temperature and pressure as well as, if necessary, shearing forces are exerted on the material system fiber material / plastic matrix / adhesion promoter. It is important that the material combination of fiber material / plastic matrix / adhesion promoter not only tolerates these processing parameters, but that these processing parameters also ensure good wetting of the fiber material with the plastic matrix. Typical temperature ranges during processing can go up to or even exceed 250 ° C, up to 300 ° C, up to 380 ° C, up to 400 ° C. Shearing forces can be introduced into the material combination with frequencies in ranges between 1 Hz and 40 kHz. Pressure or shear forces can reach values in the range, for example, between 0.01 MPa and 2 MPa. In this case, both the temperature and the force is usually only briefly, for example, for several seconds or individual minutes. It has been found that combinations of materials lead to good results in terms of the fiber composite produced and in particular to a good and complete wetting of the fiber material with the plastic matrix, which were previously considered due to the prejudice lacking temperature resistance or too high viscosity. According to the invention, the various combinations of materials have been tested and their suitability for the production of the fiber Composite evaluated. It was found that among the material combinations according to the invention fiber material / plastic matrix / adhesion promoter are those which, contrary to expectation, are well suited to the construction of the fiber composite material. As far as the fibrous material is a glass fiber ser is used, this may be of the type TufRov ^® 4510, TufRov ^® 4575, TufRov ^® 4585, TufRov ^® 4588, TufRov ^® 4599 or TufRov ^® 4854th As far as the fiber material is a carbon fiber is used, these may be of type Grafil / Pyrofil® ^® TRH50 60k, Pyrofil® ^® 34-24k or Pyrofil® ^® TRW40 50k. The adhesion promoter can be used in the form of a copolymer or in the form of a blend with, for example, 0.5% by weight to 5% by weight of maleic anhydride. The plastic matrix can also be used in the form of a copolymer or in the form of a blend or in the form of a mixture. Fiber diameter according to claim 2 provide a fiber composite material with good wetting and correspondingly good stability. The fiber diameter can μηι at 6, can at 7 μηι, in the range of 10 μηι or can be 17 μηι. Fiber finenesses according to claim 3 also give a good wetting. The fiber fineness can be in the range of 1,200 tex and can be in the range of 2,400 tex.

Fiber material according to claim 4 leads to a stable fiber composite material. The fiber material can have a very high proportion of continuous or long fibers and can consist almost exclusively of endless or long fibers. The long fibers may have fiber lengths ranging between 12.5 mm and 50 mm. It can also long fibers with lengths up to 80 mm are used, which is particularly offset can be arranged parallel to each other. Endless fibers, in contrast, have a greater length. Depending on the requirements of the strength and / or the tensile modulus of elasticity, long fibers, isotropically and / or anisotropically arranged, and / or endless fibers can be used.

Fiber bundles or ovings lead to a stable fiber composite material. The fiber bundle can range from 10,000 single fibers, in the range of 12,000 individual fibers, in the range of 18,000 individual fibers, in the range of 20,000 individual fibers, in the range of 30,000 individual fibers, in the range of 40,000 individual fibers, in the range of 50,000 individual fibers and can in the range of 60,000 Have individual fibers.

A tensile strength according to claim 6 results in a tensile fiber composite material. The tensile strength may be in the range of 3 GPa, may be in the range of 4 GPa, may be 4.9 GPa, and may be more than 5 GPa.

A tensile modulus of elasticity according to claim 7 results in a stable fiber composite material. The tensile modulus of elasticity can be in the range of 60 GPa, 70 GPa or even in the range of even higher values, for example in the range of 100 GPa or 250 GPa.

Plastic materials according to claim 8 have been found to be particularly suitable. The specified materials can be used in the form of copolymers or in the form of blends. As far as the art is material-matrix used in the form of SAN or AMSAN in the form of the commercial type Luran ^® VLN, Luran ^® 358, Luran ^® 378 P can Luran ^® HH-120 are used. The Type Luran ^® 358 with a poly carbonate (PC) -Beimischung can be used. In a derar polycarbonate blend, a polycarbonate weight fraction of 20% to 60% can be used. In particular, a SAN / PC blend can be used. Another Luran ^® type can also be used. Additives can also be added to the plastic material, for example talc, which may be present for example at a level of 1% of the total weight. A fiber composite material with glass and / or carbon fibers and a plastic matrix based on SAN and / or AMSAN and / or SAN-PC results in a fiber composite material with balanced properties in terms of tensile and compressive stress.

Polyamide plastic matrices according to claim 9 have been found to be particularly suitable. As a PA 6i, the commercial grade Durethan ^® T40 can be used. The polyamide PA 6.6 T commercial type ultra- tramid ^® T 15 may be used. A combination of glass fiber PA 6.6 T, especially a combination of TufRov ^® 4510 with PA 6.6 T and can be processed, for example, at very high temperatures, which favors the wetting. For example, a combination of glass fiber and amorphous PA 6i leads to good wetting despite the high-viscosity plastic matrix.

A Vicat softening temperature according to claim 10 has been found to be particularly suitable for good wetting. The Vicat softening temperature may be in the range of 100 ° C and may in particular be 106 ° C or 107 ° C. The Vicat softening temperature may be in the range 120 ° C.

A melt volume flow rate according to claim 1 1 has been found to be advantageous for good wetting. The melt volume flow rate may, again measured at 220 ° C with 10 kg load mass, be in the range of 20 cm 3/10 min or in the range of 22 cm 3/10 min and may assume values up to 70 cm / 10 min or more. Adhesion promoters according to claim 12, for example at least one aminosilane, have proven to be suitable for achieving good wetting. The adhesion promoter can be prepared on the basis of at least one of the following silane compounds: aminopropyltrimethoxysilane, aminobutyltrimethoxysilane, aminopropyltriethoxysilane, aminobutyltriethoxysilane and also based on a silane having a glycidyl group as substituent.

A weight ratio according to claim 13 favors a good wetting. Shaped bodies according to claim 14 provide a particularly stable and matched to the particular material requirements fiber composite material. The fiber composite material can be manufactured as a fiber composite material band, in particular as an endless band. An embodiment of the invention will be explained in more detail with reference to the drawing. In this show:

Fig. 1 shows a section through a section of a flat shaped body of a fiber composite material;

Fig. 2 is a fragmentary enlargement of Figure 1 showing a fiber bundle; Fig. 3 is a partial enlargement of Figure 2, showing a single, coated with a primer fiber.

A fiber composite material is formed by a flat shaped body 1, which can be designed, for example, as a profile or as a plate. The molded body 1 has a plurality of layers 2, 3, 4 of the fiber composite material. The layers 2 to 4 may be portions of a fiber composite intermediate in the form of an endless belt of the fiber composite.

Part of the fiber composite material is a fiber material 5 with individual fibers or filaments 6, which are combined into fiber bundles or rovings 7. The fiber material 5 is embedded in a plastic matrix 8. The filaments 6 are coated with a bonding agent 9, which is also referred to as seizing.

Within the multi-layer structure of the molded body 1, the fibers of the fiber material 5 may be constructed and / or arranged and / or oriented differently in the individual layers. Within the layers 2 to 4, the fiber material 5 may be in the form of continuous fibers or in the form of a fiber fabric. Between the layers 2 to 4, the type and structure of the fiber material 5 may vary.

The fiber material 5 is selected from at least one of the following materials: glass, carbon, aramid, basalt, polyester or natural fiber.

The plastic matrix 8 is a thermoplastic. The adhesion promoter 9 is selected on the basis of at least one of the following materials: silane, aminosilane, polypropylene (PP), titanium, aluminum, chromium, zirconium or boron. The adhesion promoter may be at least partially copolymerized with, for example, 0.5% by weight to 5 wt .-% maleic anhydride are used.

As far as the fibrous material 5, a glass fiber is used a glass fiber of the type TufRov ^® 4510, TufRov ^® 4575, TufRov ^® 4585, TufRov ^® 4588, TufRov ^® 4599 or 4854 TufRov ^® can be used. It is also possible to use a glass fiber of the R glass type, ie a fiber with increased strength, for example the type 1 1 1A-1200 or 1 1 1A-2400 from the manufacturer "3B-Fiberglass", Belgium, according to the data sheet " 1 1 1A Direct Rovings ", available at www.3b-fibreglass.com. As far as a Polyfaser or polymer fiber is used as fibrous material 5 is used, a fiber of the type Grafil ^® / Pyrofil ^® TRH50 60k, Pyrofil ^® 34-24k, Pyrofil ^® are used TRW40 50k. Carbon fiber material 7 for the fiber material 5 can also be produced on the basis of cellulose or based on polyacrylonitrile (PAN). The diameter of the filaments 6 can be in the range between 5 μηι and 50 μηι and can in particular in the range of 6 μηι, 7 μηι, 10 μηι and 17 μηι lie.

The filaments 6 may have a fineness of 500 tex to 5,000 tex. A tex indicates a g / m. For example, subtleties in the range of 1,200 tex and 2,400 tex are possible.

The fibrous material 5 may comprise endless or long fibers and may be composed exclusively of such fibers. The Rovings 7 can have more than 1,000 individual fibers, for example 10,000 (10k) single fibers, 12,000 (12k) single fibers, 18,000 (18k) single fibers, 20,000 (20k) single fibers, 30,000 (30k) single fibers, 40,000 (40k) single fibers, 50,000 ( 50k) single fibers or 60,000 (60k) single fibers.

The fiber material 5 may have a tensile strength of more than 1 GPa. The tensile strength may be in the range of 3 GPa, in the range of 4 GPa, in the range of 4.5 GPa, in the range of 4.75 GPa, in the range of 4.9 GPa, or may be more than 5 GPa.

The fiber material 5 may have a tensile modulus of more than 60 GPa, for example 70 GPa or even 100 GPa. The tensile E modulus of the fiber material 5 may be in the range of 250 GPa.

The plastic matrix 8 may be selected from at least one of the following polymers: polyamide (PA), styrene-acrylonitrile copolymer (SAN), alpha-methylstyrene-acrylonitrile copolymer (AMSAN), styrene-acrylonitrile-polycarbonate copolymer (SAN-PC) , Polyethylene (PE), polypropylene PP), one or more other polyolefins, acrylic ester-styrene, acrylonitrile (ASA), polycarbonate (PC), polyethylene terephthalate (PBT), polyethylene terephthalate (PET), polyphenylene sulfide (PPF), polysulfone (PSU ), Polyethersulfone (PEF), polyetheretherketone (PEEK), thermopolymerstyrene / acrylonitrile / maleic anhydride, polymer based on acrylic and methacrylic acid esters, copolymer of hexamethylenediamine, terephthalic and isophthalic acid. In the AMSAN SAN and plastic types may be those having the trade designations Luran ^® VLN, Luran ^® 358, Luran ^® 378 P. Luran ^® H-120, Luran ^® 358 with PC admixture or to another Luran ^® - Type act. For the plastic matrix 8 it is also possible to select the polymer polyoxymethylene (POM) or a mixture of polyoxymethylene (POM) and thermoplastic polyurethane (PUR). These variants for the plastic matrix 8 lead to a stiff and tough matrix, which leads to a correspondingly high energy absorption capability of the fiber composite material.

The plastic matrix 8 can be selected from at least one of the following materials: PA 6.6 T, PA 6.6 i, PA 6, PA 6.6, PA 6/66, PA 66, PA 12, PA 6.10, PA 6 T / 6 I. In PA 6.6 i may be, it may be the type Ultramid ^® T 15 about the type You- rethane ^® T 40 and PA 6.6 T.

The plastic matrix 8 may have a Vicat softening temperature that is in the range of at least 75 ° C. The Vicat softening temperature may be in the range of 100 ° C, may be 106 ° C or 107 ° C, and may be in the range of 120 ° C.

The plastic matrix 8 may have a melt volume flow rate, measured at 220 ° C with 10 kg load mass, have greater than 10 cm ^3/10 min. This melt volume flow rate is a measure of the viscosity of the plastic matrix 8. The melt volume flow rate can be in the range of

20 cm 3/10 min, in the range of 22 cm 3/10 min and may have an amount of 70 cm / 10 min or even higher.

The coupling agent 9 can be selected on the basis of at least one of the following materials: triethoxysilane, vinyltris (β-methoxyethoxy) silane, γ-methacryloxypropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, N-β- (aminoethyl) - γ- aminopropyltrimethoxysilane, N-.beta .- (aminoethyl) -γ-aminopropyl-methyldimethoxysilane, .gamma.-aminopropyltriethoxysilane, N-phenyl-.gamma.-aminopropyltrimethoxysilane, .gamma.-mercaptopropyltrimethoxysilane and .gamma.-choloropropyltrimethoxysilane. The adhesion promoter 9 can be produced on the basis of an aminosilane. As aminosilane, γ-aminopropyltriethoxysilane or N-β- (aminoethyl) -y-aminopropyltrimethoxysilane can be used. The adhesion promoter 9 can be prepared on the basis of at least one of the following silane compounds: aminopropyltrimethoxysilane, aminobutyltrimethoxysilane, aminopropyltriethoxysilane, aminobutyltriethoxysilane and also based on a silane having a glycidyl group as substituent.

A weight ratio between the main promoter 9 and the filament 6, on which the adhesion promoter 9 is applied as a coating, can be in the range between 0.1 and 2%, for example in the range between 0.5% and 1%, and can especially at 0.7%.

In the production of the molded body 1, an endless belt is first produced from the fiber composite material. The endless sliver is then made up in sections, the band sections are layered and, in particular under the influence of pressure and temperature, molded into the molded body 1.

Claims

claims

1. fiber composite material

with a fiber material (5) with filaments (6),

- With a plastic matrix (8), in which the fiber material (5) is embedded, and

with a bonding agent (9), with which the filaments (6) of the fiber material (5) are coated,

wherein the fiber material (5) is selected from at least one of the following materials: glass, carbon, aramid, basalt, polyester, natural fiber,

wherein the plastic matrix (8) is designed as a thermoplastic,

wherein the adhesion promoter (9) is selected on the basis of at least one of the following materials: silane, polypropylene (PP), titanate, aluminum, chromium, zirconium and boron.

2. fiber composite material according to claim 1, characterized in that the fiber diameter of the filaments (6) in the range between 5 μηι and 50 μηι.

3. fiber composite material according to claim 1 or 2, characterized in that the filaments (6) have a fineness of 500 tex to 5,000 tex.

4. fiber composite material according to one of claims 1 to 3, characterized in that the fiber material (5) have endless or long fibers.

5. fiber composite material according to one of claims 1 to 4, characterized in that the fiber material (5) has fiber bundles (7) with more than 1,000 individual fibers.

6. fiber composite material according to one of claims 1 to 5, characterized in that the fiber material (5) has a tensile strength of more than 1 GPa.

7. fiber composite material, characterized in that the fiber material (5) has a tensile modulus of more than 50 GPa.

8. fiber composite material according to one of claims 1 to 7, characterized in that the plastic matrix (8) is selected from at least one of the following materials: polyamide (PA), styrene-acrylonitrile copolymer (SAN), alpha-methylstyrene-acrylonitrile

Copolymer (AMSAN), styrene-acrylonitrile-polycarbonate copolymer (SAN-PC), polyethylene (PE), polypropylene PP), one or more other polyolefins, acrylic ester-styrene, acrylonitrile (ASA), acrylonitrile-butadiene-styrene (ABS) , Polycarbonate (PC), polyethylene terephthalate (PBT), polyethylene terephthalate (PET), polyphenylene sulfide (PPF), polysulfone (PSU), polyethersulfone (PEF), polyetheretherketone (PEEK), theφyrolstyrol / acrylonitrile / maleic anhydride, polymer based on acrylic and Methacrylic acid ester, copolymer of hexamethylenediamine, terephthalic and isophthalic acid, polyoxymethylene (POM), mixture of polyoxymethylene (POM) and thermoplastic polyurethane (PUR).

9. fiber composite material according to claim 8, characterized in that the plastic matrix (8) from at least one of the following Ma is selected from: PA 6.6 T, PA 6.6 i, PA 6, PA 6.6, PA 6/66, PA 66, PA 12, PA 6.10, PA 6 T / 6 I.

10. fiber composite material according to one of claims 1 to 9, characterized in that the plastic matrix (8) a Vicat

Softening temperature, which is in the range of at least 75 ° C.

1 1. fiber composite material according to one of claims 1 to 10, characterized in that the plastic matrix (8) is a melt

Volume flow rate, measured at 220 ° C with 10 kg load mass, which is greater than 10 cm / 10 min.

12. fiber composite material according to one of claims 1 to 1 1, characterized in that the adhesion promoter (9) is selected from at least one of the following materials: triethoxysilane, vinyltris (.beta.-methoxyethoxy) silane, γ-methacryloxypropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, ß- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, N-β- (aminoethyl) -γ-aminopropyltrimethoxysilane, N-β- (aminoethyl) -γ-aminopropyl-methyldimethoxysilane, γ-aminopropyltriethoxysilane, N-phenyl-γ-amionopropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane and γ-chloropropyltrimethoxysilane, γ-aminopropyltriethoxysilane or N-β- (aminoethyl) -y-aminopropyltrimethoxysilane.

13. fiber composite material according to one of claims 1 to 12, characterized by a weight ratio between the bonding agent (9) and the filaments (6) of the fiber material (5) in the range of 0.1 wt .-% to 2 wt .-%.

14. fiber composite material according to one of claims 1 to 13, designed as a shaped body (1) of several layers (2 to 4) with fiber-reinforced plastic material.