EP3286000A1 - "organosheets" (plaques de composite thermoplastique renforcé de fibres) à base de polymère de styrène pour produits blancs - Google Patents

"organosheets" (plaques de composite thermoplastique renforcé de fibres) à base de polymère de styrène pour produits blancs

Info

Publication number
EP3286000A1
EP3286000A1 EP16721376.8A EP16721376A EP3286000A1 EP 3286000 A1 EP3286000 A1 EP 3286000A1 EP 16721376 A EP16721376 A EP 16721376A EP 3286000 A1 EP3286000 A1 EP 3286000A1
Authority
EP
European Patent Office
Prior art keywords
fiber composite
composite material
thermoplastic
thermoplastic molding
acrylonitrile
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP16721376.8A
Other languages
German (de)
English (en)
Inventor
Philipp Deitmerg
Norbert Niessner
Eike Jahnke
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Ineos Styrolution Group GmbH
Original Assignee
Ineos Styrolution Group GmbH
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Ineos Styrolution Group GmbH filed Critical Ineos Styrolution Group GmbH
Publication of EP3286000A1 publication Critical patent/EP3286000A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • 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
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/302—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising aromatic vinyl (co)polymers, e.g. styrenic (co)polymers
    • 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
    • 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
    • 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
    • B32B5/245—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 being a foam layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
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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
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/10—Interconnection of layers at least one layer having inter-reactive properties
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
    • C08J5/06—Reinforcing macromolecular compounds with loose or coherent fibrous material using pretreated fibrous materials
    • C08J5/08—Reinforcing macromolecular compounds with loose or coherent fibrous material using pretreated fibrous materials glass fibres
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/02—Fibres or whiskers
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    • B32B2250/00—Layers arrangement
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    • B—PERFORMING OPERATIONS; TRANSPORTING
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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
    • B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
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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
    • 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
    • B32B2260/02—Composition of the impregnated, bonded or embedded layer
    • B32B2260/021—Fibrous or filamentary layer
    • B32B2260/023—Two or more layers
    • 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
    • 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
    • B32B2262/0261—Polyamide fibres
    • B32B2262/0269—Aromatic polyamide 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
    • B32B2262/10—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
    • B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
    • B32B2262/10—Inorganic fibres
    • B32B2262/106—Carbon fibres, e.g. graphite 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
    • B32B2266/00—Composition of foam
    • B32B2266/02—Organic
    • B32B2266/0214—Materials belonging to B32B27/00
    • B32B2266/0221—Vinyl resin
    • B32B2266/0228—Aromatic vinyl resin, e.g. styrenic (co)polymers
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/738—Thermoformability
    • 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
    • B32B2509/00—Household appliances
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2433/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2435/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical, and containing at least one other carboxyl radical in the molecule, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L55/00—Compositions of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08L23/00 - C08L53/00

Definitions

  • the present invention relates to the use of a fiber composite material (also called organic sheet) in the field of white goods, the fiber composite material comprising a thermoplastic molding compound A and a reinforcing fiber B, wherein the layers of the Reinforcing fiber B are embedded in the matrix of the thermoplastic molding composition A, and wherein the thermoplastic molding compound A at least one chemically reactive functionality.
  • a fiber composite material also called organic sheet
  • Fiber composite materials or organic sheets usually consist of a multiplicity of reinforcing fibers which are embedded in a polymer matrix.
  • the fields of application of fiber composite materials are manifold.
  • fiber composite materials are used in the vehicle and aviation sectors.
  • fiber composite materials should prevent the tearing or other fragmentation of the matrix in order to reduce the risk of accidents caused by distributed component networks.
  • Many fiber composite materials are able to absorb relatively high forces under load before it comes to a total failure.
  • fiber composite materials are distinguished by high strength and rigidity, combined with low density and other advantageous properties, such as, for example, good aging and corrosion resistance, compared with conventional, non-reinforced materials.
  • the strength and rigidity of the fiber composite materials can be adapted to the loading direction and load type.
  • the fibers are primarily responsible for the strength and rigidity of the fiber composite material.
  • their arrangement determines the mechanical properties of the respective fiber composite material.
  • the matrix usually serves primarily to introduce the forces to be absorbed into the individual fibers and to maintain the spatial arrangement of the fibers in the desired orientation. Since both the fibers and the matrix materials are variable, numerous combinations of fibers and matrix materials come into consideration.
  • fiber-matrix adhesion In order to optimize the fiber-matrix adhesion and to compensate for a "low chemical similarity" between the fiber surfaces and the surrounding polymer matrix, reinforcing fibers are regularly pretreated by adding adhesion promoters to the so-called sizing agent on a regular basis ) is applied to the fiber at regular intervals during production in order to improve the further processability of the fibers (such as weaving, laying, sewing). If the sizing is undesirable for subsequent further processing, it must first be removed in an additional process step, such as by burning down In some cases, glass fibers are also processed without sizing.
  • a further adhesion promoter is applied in an additional process step for the production of the fiber composite material.
  • Sizing and / or adhesion promoters form on the surface of the fibers a layer which can substantially determine the interaction of the fibers with the environment.
  • a large number of different bonding agents are available.
  • the matrix to be used and the fibers to be used the person skilled in the art can select a suitable adhesion promoter which is compatible with the matrix and with the fibers.
  • a technical challenge is that the fiber composite material can suffer a brittle fracture when the total failure occurs. Consequently, for example, in the construction of elements that are exposed to high mechanical stress, a significant risk of accident of torn components arise.
  • WO 2008/058971 describes molding compositions which use two groups of reinforcing fibers.
  • the groups of reinforcing fibers are each provided with different adhesion promoter components which effect the different fiber matrix adhesions.
  • the second fiber-matrix adhesion is less than the first fiber-matrix adhesion, and the near-surface layers of reinforcing fibers of reinforcing fibers of the first group are formed with greater fiber matrix adhesion.
  • the matrix materials proposed are thermosetting plastics such as polyester and the thermoplastics polyamide and polypropylene.
  • WO 2008/1 19678 describes a glass fiber-reinforced styrene-acrylonitrile copolymer (SAN) which is improved in its mechanical properties by using maleic anhydride group-containing styrene copolymer and chopped glass fibers. It is therefore taught the use of short fibers. However, there is no indication of fiber composite materials.
  • SAN glass fiber-reinforced styrene-acrylonitrile copolymer
  • CN 102924857 describes mixtures of styrene-maleic anhydride copolymers which are mixed with chopped glass and then show relatively high strengths. However, the stress cracking resistance of such a material to solvents is too low. The strength compared to fiber optic connections is clearly too low.
  • CN 101555341 describes mixtures of acrylonitrile-butadiene-styrene (ABS), glass fibers, maleic anhydride-containing polymers and epoxy resins.
  • ABS acrylonitrile-butadiene-styrene
  • maleic anhydride-containing polymers acrylonitrile-butadiene-styrene
  • epoxy resins epoxy resins.
  • ABS and the maleic anhydride-containing polymer are initially charged to add the epoxy resin and then the glass fibers.
  • the fluidity of such a mixture containing a (thermoset) epoxy resin is very limited.
  • KR 100376049 teaches mixtures of SAN, maleic anhydride and N-phenyl maleimide-containing copolymer, chopped glass fibers and an aminosilane-based coupling agent.
  • the use of such a coupling agent leads to additional processing steps and thus increases the production costs.
  • PC polycarbonate
  • suitable additives such as hyperbranched polyesters, ethylene / (meth) acrylate copolymers or low molecular weight polyalkylene glycol esters.
  • EP-A 2 251 377 describes organo-sheets which have been treated with an aminosilane size. It is not taught to use organo sheets for the production of white goods.
  • Glass fibers are often treated in the prior art with a sizing, which protect each other especially the fibers. Mutual damage due to abrasion should be prevented. When mutual mechanical action should not come to the transverse fragmentation (fracture).
  • the cutting process of the fiber can be facilitated in order to obtain, above all, an identical staple length.
  • an agglomeration of the fibers are avoided.
  • the dispersibility of short fibers in water can be improved.
  • a sizing may help to produce improved cohesion between the glass fibers and the polymer matrix in which the glass fibers act as reinforcing fibers.
  • This principle is mainly used in glass fiber reinforced plastics (GRP). So far, the glass fiber sizes generally contain a large number of constituents, such as film formers, lubricants, wetting agents and adhesion promoters.
  • a film former protects the glass filaments from mutual friction and, in addition, can enhance an affinity for synthetic resins, thus promoting the strength and cohesion of a composite material.
  • Starch derivatives, polymers and copolymers of vinyl acetate and acrylic esters, epoxy resin emulsions, polyurethane resins and polyamides in a proportion of 0.5 to 12 wt .-%, based on the total size, are mentioned.
  • a lubricant gives the glass fibers and their products suppleness and reduces the mutual friction of the glass fibers, as well as in the production. Often, however, the adhesion between glass and resin is compromised by the use of lubricants. Fats, oils and polyalkyleneamines in an amount of 0.01 to 1 wt .-%, based on the total size, are mentioned.
  • a wetting agent causes a lowering of the surface tension and an improved wetting of the filaments with the size.
  • aqueous sizes for example, polyfatty acid amides in an amount of 0.1 to 1, 5 wt .-%, based on the total size to name.
  • organo-functional silanes such as aminopropyltriethoxysilane, methacryloxypropyltrimethoxysilane, glycidyloxypropyltrimethoxysilane and the like can be mentioned.
  • Silanes which are added to an aqueous sizing are usually hydrolyzed to silanols. These silanols can then react with reactive (glass) fiber surfaces and thus form an adhesive layer (with a thickness of about 3 nm).
  • low molecular weight functional agents can react with silanol groups on the glass surface, with these low molecular weight agents subsequently reacting further (for example, in epoxy resins), thereby providing chemical bonding of the glass fiber to the polymer matrix.
  • such a preparation is time-consuming and lasts until complete curing of the polymers (for example the abovementioned epoxy resins) approximately between 30 minutes to more than one hour. It therefore appears desirable to bring already polymerized melts in conjunction with glass fibers or other reinforcing fibers in an improved process.
  • a functionalization by reaction with polymers is also known.
  • PC polycarbonate
  • a technical object of the invention is to produce a fiber composite material (organogelc) which has suitable properties for the "white goods" sector.
  • the fiber composite material should be based on an easily processed, against conventional solvent largely inert, good stress crack resistant, solid composite material and have a smooth surface. Ideally, the fiber composite material comes without adhesion promoter.
  • a fiber composite material comprising at least one thermoplastic molding composition A as matrix, at least one reinforcing fiber B, and optionally at least one additive C, wherein the layers of reinforcing fiber B are embedded in the matrix, and wherein the thermoplastic molding composition A has at least one chemically reactive functionality, which reacts during the manufacturing process of the fiber composite material with chemical groups of the surface of component B, especially in the field of white goods, such as household appliances, is well suited.
  • the resulting fiber composite Material has good strength and is resistant to tearing and solvents and thus suitable for use in white goods.
  • thermoplastic fiber composite material comprising (or consisting of): a) at least one thermoplastic molding compound A as matrix,
  • thermoplastic molding compound A has at least one chemically reactive functionality which reacts with chemical groups of the surface of component B during the manufacturing process of the fiber composite material to produce white Goods, such as Household appliances.
  • the present invention also relates to a process for the production of white goods, e.g. Household appliances, comprising the following steps:
  • thermoplastic molding compound A as matrix
  • thermoplastic molding compound A has at least one chemically reactive functionality which reacts with chemical groups of the surface of component B during the manufacturing process of the fiber composite material;
  • the polymer matrix may be an amorphous plastic matrix in which the reinforcing fibers B are embedded as reinforcement and coupled to the matrix via fiber-matrix adhesion.
  • the fiber composite material has at least the components A and B.
  • the fibers B (reinforcing fibers) are embedded in a thermoplastic molding compound A.
  • a polymer may also be a copolymer (including a terpolymer, etc.). Accordingly, a polymer matrix can also be a copolymer matrix.
  • the invention particularly relates to the use of a thermoplastic fiber composite material as described above, containing (or consisting of): a) 30 to 95% by weight of the thermoplastic molding composition A,
  • thermoplastic molding composition A comprises at least one (co) polymer having at least one chemically reactive functionality which reacts with chemical groups on the surface of the reinforcing fiber component B during the manufacturing process of the fiber composite material
  • a (co) polymer comprises at least one functional monomer A-1 whose functionality reacts with chemical groups on the surface of the reinforcing fiber component B during the production process of the fiber composite material.
  • the (co) polymer comprising monomer A-1 is also referred to herein as polymer component (A-a).
  • the thermoplastic molding composition A may contain one or more (co) polymers which are optionally also free of such a chemically reactive functionality (therefore contain no functional monomer Al) and thus not with chemical groups on the surface during the manufacturing process of the fiber composite material the reinforcing fiber component B react.
  • a (co) polymer is also referred to herein as a polymer component (Ab).
  • the invention particularly relates to the use of a thermoplastic fiber composite material as described above, wherein the thermoplastic molding material A is amorphous.
  • the thermoplastic molding compound A is preferably selected from the group consisting of:
  • Polystyrene (clear or impact resistant), styrene-acrylonitrile copolymers, ⁇ -methylstyrene-acrylonitrile copolymers, toughened-modified styrene-acrylonitrile copolymers, in particular acrylonitrile-butadiene-styrene copolymers (ABS) and acrylonitrile-styrene-acrylic ester copolymers (ASA), and blends of said copolymers, in particular with polycarbonate or polyamide.
  • ABS acrylonitrile-butadiene-styrene copolymers
  • ASA acrylonitrile-styrene-acrylic ester copolymers
  • At least one of the (co) polymer components of the thermoplastic molding material A is a (co) polymer which has at least one chemically reactive functionality as described herein (polymer component (A-a)).
  • polymer component (A-a) each of the copolymer components mentioned in the preceding paragraph can accordingly also have, in addition to the explicitly mentioned monomers, a reactive functionality which can react with the surface of the fibers B during the production of the fiber composite material.
  • any of the above-mentioned (co) polymers may also be a polymer component (A-a).
  • polystyrene (AI) copolymer styrene-acrylonitrile (Al) copolymer, ⁇ -methylstyrene-acrylonitrile (Al) copolymer, impact-modified acrylonitrile-styrene (Al) copolymer, in particular acrylonitrile-butadiene-styrene (Al) copolymer (ABS (AI)) and acrylonitrile-styrene-acrylic ester (AI) copolymer (ASA (AI)).
  • blends of said copolymers with polycarbonate or polyamide are possible.
  • polymer component (A-a) may also additionally comprise a second monomer (or even a third monomer) which mediates the chemically reactive functionality.
  • polystyrene Maleic anhydride copolymer polystyrene Maleic anhydride copolymer
  • styrene-acrylonitrile-maleic anhydride copolymer o methylstyrene-acrylonitrile-maleic anhydride copolymer
  • impact-modified acrylonitrile-styrene-maleic anhydride copolymer in particular acrylonitrile-butadiene-styrene-maleic anhydride copolymer (ABS-MA) and acrylonitrile Styrene-acrylic ester-maleic anhydride copolymer (ASA-MA).
  • ABS-MA acrylonitrile-butadiene-styrene-maleic anhydride copolymer
  • ASA-MA acrylonitrile Styrene-acrylic ester-maleic anhydride copolymer
  • blends of said copolymers with polycarbonate or polyamide are possible. It will be understood that
  • any other (co) polymers without such functionality may be used in addition to the one or more polymer component (s) (A-a).
  • the abovementioned (co) polymers therefore polystyrene, styrene-acrylonitrile copolymers, ⁇ -methylstyrene-acrylonitrile copolymers, impact-modified acrylonitrile-styrene copolymers, in particular acrylonitrile-butadiene-styrene copolymers (ABS) and acrylonitrile Styrene-acrylic ester copolymers (ASA), as well as blends of said copolymers with polycarbonate or polyamide), but then without the functionality (therefore without reactive monomer Al) are used.
  • ABS acrylonitrile-butadiene-styrene copolymers
  • ASA acrylonitrile Styrene-acrylic ester copolymers
  • the polymer component (A-a) of the thermoplastic molding composition A is based on a SAN copolymer.
  • the SAN copolymer then additionally comprises a monomer A-1 which reacts with the surface of the fibers B during the manufacturing process.
  • thermoplastic molding composition A comprises (or consists of):
  • At least one polymer component (Aa) which has at least one chemically reactive functionality which reacts with chemical groups on the surface of the reinforcing fiber component B during the production process of the fiber composite material and is selected from the group consisting of: styrene-acrylonitrile Copolymers, ⁇ -methylstyrene-acrylonitrile copolymers, toughened acrylonitrile-styrene copolymers, in particular acrylonitrile-butadiene-styrene copolymers (ABS) and acrylonitrile-styrene-acrylic ester copolymers (ASA), each containing at least one functional group, and blends said copolymers with polycarbonate or polyamide; and optional at least one polymer component (Ab), having no such functionality, selected from the group consisting of: polystyrene, styrene-acrylonitrile copolymers, ⁇ -methylstyrene-acrylonitrile copolymers, impact-modified
  • thermoplastic molding composition A comprises (or consists of):
  • At least one polymer component (Aa) which has at least one chemically reactive functionality which reacts with chemical groups on the surface of the reinforcing fiber component B during the production process of the fiber composite material and is selected from the group consisting of: styrene-acrylonitrile Copolymers, ⁇ -methylstyrene-acrylonitrile copolymers, toughened acrylonitrile-styrene copolymers, in particular acrylonitrile-butadiene-styrene copolymers (ABS) and acrylonitrile-styrene-acrylic ester copolymers (ASA), each containing at least one functional group, and blends said copolymers with polycarbonate or polyamide; and optional
  • At least one polymer component (Ab) having no such functionality selected from the group consisting of: polystyrene, styrene-acrylonitrile copolymers, ⁇ -methylstyrene-acrylonitrile copolymers, impact-modified acrylonitrile-styrene copolymers, in particular acrylonitrile-butadiene Styrene copolymers (ABS) and acrylonitrile-styrene-acrylic ester copolymers (ASA), as well as blends of said copolymers with polycarbonate or polyamide.
  • ABS acrylonitrile-butadiene Styrene copolymers
  • ASA acrylonitrile-styrene-acrylic ester copolymers
  • At least one of the (co) polymer components of the thermoplastic molding compound A is a (co) polymer which has at least one chemically reactive functionality which, during the production process of the fiber composite material, has chemical groups on the surface of the polymer Reinforcing fiber component B reacts (polymer component (Aa)).
  • one or more other (co) polymers without such functionality can be used.
  • the invention relates to the use of a thermoplastic fiber composite material as described above, wherein the chemically reactive functionality of the thermoplastic molding composition A is based on components (Al) from the group: maleic anhydride, N-phenylmaleimide, tert-butyl ( meth) acrylate and glycidyl (meth) acrylate function, preferably selected from Group consisting of: maleic anhydride, N-phenylmaleimide and glycidyl (meth) acrylate function.
  • components (Al) from the group: maleic anhydride, N-phenylmaleimide, tert-butyl ( meth) acrylate and glycidyl (meth) acrylate function, preferably selected from Group consisting of: maleic anhydride, N-phenylmaleimide and glycidyl (meth) acrylate function.
  • the invention relates to the use of a fiber composite material as described above, wherein the thermoplastic molding composition A at least 0.1 wt .-%, often 0.15 to 0.5 wt .-%, monomers Al, based on the weight of component A, which have a chemically reactive functionality contains.
  • the invention relates to the use of a thermoplastic fiber composite material as described above, wherein the reinforcing fibers B consist of glass fibers which preferably contain as chemical-reactive functionality silane groups on the surface.
  • the invention relates to the use of a thermoplastic fiber composite material as described above, wherein the surface of the reinforcing fibers B contains one or more of the functions: hydroxyl, ester and amino groups.
  • the invention relates to the use of a thermoplastic fiber composite material as described above, wherein the reinforcing fibers B consist of glass fibers, which preferably contain as a chemically reactive functionality silanol groups on the surface.
  • the invention relates to the use of a thermoplastic fiber composite material as described above, wherein the reinforcing fibers B in the form of a mat, a fabric, a mat, a nonwoven fabric or a knitted fabric are used.
  • the invention relates to the use of a thermoplastic fiber composite material as described above, wherein the fiber composite material has a thickness of ⁇ 10 mm, preferably of ⁇ 2 mm, most preferably of ⁇ 1 mm.
  • the invention relates to the use of a thermoplastic fiber composite material as described above, wherein the fiber composite material has a ribbing or a sandwich construction.
  • the invention relates to the use of a thermoplastic fiber composite material as described above, wherein the fiber composite material is layered and contains more than two, often more than three layers.
  • the other layers may be the same or different in construction from those described above.
  • the invention relates to the use of a thermoplastic fiber composite material as described above, for the production of large or small appliances, in particular for the household.
  • the invention relates to the use of a thermoplastic fiber composite material as described above, for the production of coverings and side coverings. In one embodiment, the invention relates to large or small devices comprising thermoplastic fiber composite materials, consisting of the components A to C as described above.
  • the fiber composite material contains at least 20 wt .-%, usually at least 30 wt .-%, based on the total weight of the fiber composite material, the thermoplastic molding material A.
  • the thermoplastic matrix (M), which forms the molding material A, is in the fiber composite material preferably from 30 to 95 wt .-%, particularly preferably from 35 to 90 wt .-%, often from 35 to 75 wt .-% and in particular from 38 to 70 wt .-%, based on the fiber composite -Material, available.
  • the thermoplastic matrix M corresponds to the thermoplastic molding material A.
  • the thermoplastic molding material A consists mainly (more than 50%, preferably more than 90%) of styrene polymers such as polystyrene (clear "PS" or impact resistant “FIPS") or copolymer A. -1.
  • the thermoplastic molding composition A is at least 75 wt .-%, preferably at least 90 wt .-% of the copolymer A-1.
  • the thermoplastic molding compound A can also consist only of copolymer A-1.
  • thermoplastic molding material A for a fiber composite material according to the invention come as thermoplastic molding material A
  • any thermoplastics in question in particular however, PS or styrene copolymers, in particular HIPS, SAN, ABS and ASA, are used.
  • At least one of the (co) polymer components of the thermoplastic molding composition A is a (co) polymer having at least one chemically reactive functionality as described herein (polymer component (Aa)) , Accordingly, it is preferred that at least one of the abovementioned polymer components (therefore at least one (optionally modified) (HIPS) polystyrene and / or at least one copolymer A-1 (styrene copolymer, SAN, ABS and ASA)) at least one Monomer Al includes.
  • HIPS (optionally modified)
  • the polystyrene in the case of using maleic anhydride (MA) as the monomer Al, can therefore be a (HIPS) polystyrene-maleic anhydride copolymer (S-MA), the copolymer A-1 exemplified by styrene-acrylonitrile-maleic anhydride copolymer (SAN -MA), acrylonitrile-butadiene-styrene-maleic anhydride copolymer (ABS-MA), acrylate-styrene-acrylonitrile-maleic anhydride copolymer (ASA-MA).
  • HIPS polystyrene-maleic anhydride copolymer
  • SAN -MA styrene-acrylonitrile-maleic anhydride copolymer
  • ABS-MA acrylonitrile-butadiene-styrene-maleic anhydride copolymer
  • ASA-MA acrylate-styrene-acrylon
  • one or more further (co) polymers without such functionality can be used. It will be understood that this may optionally also be (HIPS) polystyrene, SAN, ABS and / or ASA (each comprising no monomer A-1).
  • thermoplastic molding composition A is a (co) polymer having at least one chemically reactive functionality as described herein (polymer component (A-a)).
  • polymer component (A-a) a polymer having at least one chemically reactive functionality as described herein
  • one or more optional (co) polymers without such functionality can be used.
  • thermoplastic molding compound A (component A) is preferably an amorphous molding compound, wherein amorphous state of the thermoplastic molding compound (thermoplastic) means that the macromolecules without regular arrangement and orientation, i. without constant distance, are arranged completely statistically.
  • the entire thermoplastic molding composition A has amorphous, thermoplastic properties, is therefore meltable and (largely) non-crystalline.
  • the shrinkage of the thermoplastic molding compound A, and therefore also of the entire fiber composite material comparatively low. It can be obtained particularly smooth surfaces in the moldings.
  • component A contains a partially crystalline fraction of less than 60% by weight, preferably less than 50% by weight, particularly preferably less than 40% by weight, based on the total weight of component A.
  • Partially crystalline thermoplastics form both chemically regular, as well as geometric areas, d. H. There are areas where crystallites form. Crystallites are parallel bundles of molecular segments or folds of molecular chains. Individual chain molecules can partially pass through the crystalline or the amorphous region. Sometimes they can even belong to several crystallites at the same time.
  • the thermoplastic molding compound A may be a blend of amorphous thermoplastic polymers and semi-crystalline polymers.
  • the thermoplastic molding compound A can be, for example, a blend of a styrene copolymer with one or more polycarbonate (s) and / or one or more semicrystalline polymers (such as polyamide), the proportion of partially crystalline mixed components in the entire component A being less than 50% by weight .-%, preferably less than 40 wt .-% should be.
  • the thermoplastic molding composition A used comprises polystyrene or at least one copolymer A-1 comprising monomers Al which form covalent bonds with the functional groups Bl of the embedded reinforcing fibers B.
  • the proportion of monomers Al in the thermoplastic molding composition A can be chosen variable. The higher the proportion of monomers A1 and the functional groups (B1), the stronger the bond between the thermoplastic molding compound A and the reinforcing fibers B can be.
  • Monomers Al may still be present as monomers in copolymer A-1 or may be incorporated into copolymer A-1. Preferably, the monomers Al are incorporated in the copolymer A-1.
  • the copolymer A-1 is constructed with a proportion of monomers A1 of at least 0.1 wt .-%, preferably of at least 0.5 wt .-%, in particular of at least 1 wt .-%, z. B.
  • the monomers Al which can form covalent bonds with the functional groups Bl of the fibers B, all monomers are suitable which have such properties.
  • monomers A1 preference is given to those which can form covalent bonds by reaction with hydroxyl or amino groups.
  • the monomers Al have:
  • the copolymer A-1 or another (co) polymer contained in the thermoplastic molding composition A may contain one or more further monomers capable of forming covalent or non-covalent bonds with the fibers B.
  • the monomers A-1 are selected from the group consisting of: maleic anhydride (MA),
  • the monomers A-1 are selected from the group consisting of maleic anhydride (MA), N-phenylmaleimide (PM) and glycidyl (meth) acrylate (GM).
  • two of these monomers A-1 may be contained in the copolymer A-1.
  • the copolymer A-1 of the molding compound A may optionally include further functional monomers A-II.
  • the matrix component M comprises at least one thermoplastic molding compound A, in particular one suitable for the production of fiber composite materials.
  • amorphous thermoplastics are used for the molding compound A.
  • styrene copolymers are used, such as styrene-acrylonitrile copolymers (SAN) or ⁇ -methylstyrene-acrylonitrile copolymers (AMSAN), impact-modified styrene-acrylonitrile copolymers, such as acrylonitrile-butadiene-styrene copolymers (ABS), styrene Methyl methacrylate copolymers (SMMA), methacrylate-acrylonitrile-butadiene-styrene copolymers (MABS) or acrylic ester-styrene-acrylonitrile copolymers (ASA).
  • ABS acrylonitrile-butadiene-styrene copolymers
  • SMMA styrene Meth
  • thermoplastic molding composition A at least one of the polymer components in the thermoplastic molding composition A is modified with monomer A-1 (polymer component (A-a)), preferably one or more of the abovementioned styrene copolymers is modified with monomer A-1.
  • Any other polymer components for example styrene copolymers, preferably those as mentioned above may optionally be additionally present in the thermoplastic molding composition A, which are not optionally modified with monomer A-1 (polymer component (A-b)).
  • Blends of the abovementioned copolymers (one or more polymer components (Aa) and optionally (Ab)) with polycarbonate or partially crystalline polymers such as polyamide are also suitable, provided that the proportion of partially crystalline mixed components in component A is less than 50% by weight .%.
  • SAN (M-1) copolymers (with modification by monomers A-1) as component of the thermoplastic molding composition A (optionally also as sole polymeric constituent).
  • Blends of the abovementioned copolymers with polycarbonate or partially crystalline polymers such as polyamide are also suitable, provided that the proportion of partially crystalline mixed components in component A is less than 50% by weight.
  • ABS copolymers as thermoplastic molding material A.
  • thermoplastic molding material A is prepared from, based on the (a-methyl) styrene-acrylonitrile copolymer, 60 to 85 wt %, preferably 65 to 80% by weight of ( ⁇ -methyl) styrene, 14.9 to 37% by weight, preferably 19.9 to 32% by weight of acrylonitrile and 0.1 to 5% by weight , preferably 0.1 to 3 wt .-% maleic anhydride. Mixtures of styrene-acrylonitrile copolymer with a-methyl-styrene-acrylonitrile copolymer may also be mentioned.
  • thermoplastic molding compound A is prepared from, based on the (a-methyl) styrene-methyl methacrylate copolymer, at least 50 wt. -%, preferably 55 to 95 wt .-%, particularly preferably 60 to 85 wt .-% (a-methyl) styrene and 5 to 45 wt .-%, preferably 15 to 40 wt .-% of methyl methacrylate.
  • the (a-methyl) styrene-methyl methacrylate copolymer may be random or a block polymer.
  • Component A can also be prepared from based on Component A, at least 50 wt .-%, preferably 55 to 95 wt .-%, particularly preferably 60 to 85 wt .-% vinyl aromatic monomer and 5 to 45 wt .-%, preferably 15 to 40 wt .-% of methyl methacrylate.
  • a modified copolymer used according to the invention (as polymer component (Aa)) of the thermoplastic molding composition A can be prepared from, based on the copolymer, 0.1 to 30% by weight maleic anhydride as component Al and 70-99.9% styrene, preferably 0 , 2 to 20% by weight of maleic anhydride as component Al and 80-99.8% of styrene, more preferably 0.3 to 10% by weight of maleic anhydride as component Al and 90-99.7% of styrene.
  • thermoplastic molding material A An inventive acrylonitrile-butadiene-styrene copolymer as thermoplastic molding material A is prepared by known methods from styrene, acrylonitrile, butadiene and a functional further monomer A-l, such as. For example, methyl methacrylate.
  • the modified ABS copolymer may, for. For example, up to 70% by weight (about 35 to 70% by weight) of butadiene, up to 99.9% by weight (about 20 to 50% by weight) of styrene and up to 38% by weight. % (about 9 to 38 wt%) of acrylonitrile and 0.1 to 20 wt%, preferably 0.1 to 10, more preferably 0.1 to 5, especially 0.1 to 3 wt% of a monomer A- I, such as maleic anhydride.
  • a monomer A- I such as maleic anhydride.
  • Component A can also be prepared from 3 up to 70% by weight (about 35 to 70% by weight) of at least one conjugated diene, up to 99.9% by weight (about 20 to 50% by weight) of at least one vinylaromatic monomer and up to 38% by weight (about 9 to 38% by weight) of acrylonitrile and 0.1 to 20% by weight, preferably 0.1 to 10, more preferably 0.1 to 5, especially 0.1 to 3% by weight, of a monomer Al, such as maleic anhydride.
  • a monomer Al such as maleic anhydride.
  • the modified ABS copolymer may contain: up to 70% by weight (about 35 to 70% by weight) of butadiene, 20 to 99.9% by weight (about 20 to 50% by weight) Styrene and up to 38 wt .-% (about 9.9 to 38 wt .-%) acrylonitrile and 0.1 to 5 wt .-%, preferably 0.1 to 3 wt .-% of a monomer Al, such as maleic anhydride.
  • a monomer Al such as maleic anhydride.
  • Component A can also be prepared from 35 to 70% by weight of at least one conjugated diene, 20 to 50% by weight of at least one vinylaromatic monomer and 9 to 38% by weight of acrylonitrile and 0.1 to 5% by weight, preferably 0.1 to 3% by weight of a monomer Al, such as maleic anhydride.
  • a monomer Al such as maleic anhydride.
  • the inventive component A is a styrene / butadiene copolymer such as impact polystyrene, a styrene-butadiene block copolymer such as Styrolux, styroflex, K-resin, clears, asaprene, a polycarbonate, an amorphous polyester or an amorphous Polyamide.
  • a styrene / butadiene copolymer such as impact polystyrene, a styrene-butadiene block copolymer such as Styrolux, styroflex, K-resin, clears, asaprene, a polycarbonate, an amorphous polyester or an amorphous Polyamide.
  • polymer component (Aa) a (co) polymer which has at least one chemically reactive functionality as described herein
  • This may also be a polymer component as described above, which contains at least one functional monomer Al
  • the matrix M can consist of at least two mutually different thermoplastic molding compositions A.
  • these various molding compound types may have a different melt flow index (MFI), and / or other co-monomers or additives.
  • the term molecular weight (Mw) in the broadest sense can be understood as the mass of a molecule or a region of a molecule (eg a polymer strand, a block polymer or a small molecule) which is in g / mol (Da) and kg / mol (kDa) can be specified.
  • the molecular weight (Mw) is the weight average which can be determined by the methods known in the art.
  • thermoplastic molding compositions A preferably have a molecular weight Mw of from 60,000 to 400,000 g / mol, particularly preferably from 80,000 to 350,000 g / mol, where Mw can be determined by light scattering in tetrahydrofuran (GPC with UV detector).
  • Mw can be determined by light scattering in tetrahydrofuran (GPC with UV detector).
  • the molecular weight Mw of the thermoplastic molding compositions A can vary within a range of +/- 20%.
  • the thermoplastic molding composition A contains a modified by a chemically reactive functionality styrene copolymer, which, except for the addition of the monomers Al, essentially composed of the same monomers as the "normal styrene copolymer", wherein the monomer content +/- 5 %, the molecular weight +/- 20% and the melt flow index (determined at a temperature of 220 ° C. and a loading of 10 kg according to ISO Method 1 133) +/- 20% ISO 1 133-1: 2012-03.
  • a chemically reactive functionality styrene copolymer which, except for the addition of the monomers Al, essentially composed of the same monomers as the "normal styrene copolymer", wherein the monomer content +/- 5 %, the molecular weight +/- 20% and the melt flow index (determined at a temperature of 220 ° C. and a loading of 10 kg according to ISO Method 1 133) +/- 20% ISO 1 133-1: 2012-03.
  • the melt volume rate (MVR) of the thermoplastic polymer composition used as polymer matrix is A reduction from 10 to 70 cm 3/10 min, preferably 12 to 70 cm 3/10 min, particularly 15 to 55 cm 3/10 min at 220 ° C / 10kg (measured according to IS01 133).
  • the melt flow rate is (Melt Volume rate, MVR) of the thermoplastic polymer composition used as the polymer matrix A 10 to 35 cm 3/10 min, preferably 12 to 30 cm 3/10 min, particularly 15 to 25 cm 3/10 min at 220 ° C / 10kg (measured according to IS01 133).
  • melt flow rate (melt volume rate MVR) of the thermoplastic polymer composition used as the polymer matrix A 35 to 70 cm 3/10 min, preferably 40 to 60 cm 3/10 min, in particular 45 to 55 cm 3/10 min at 220 ° C / 10kg (measured according to IS01 133).
  • the viscosity number is 55 to 75 ml / g, preferably 60 to 70 ml / g, in particular 61 to 67 ml / g.
  • the viscosity number is 60 to 90 ml / g, preferably 65 to 85 ml / g, in particular 75 to 85 ml / g.
  • component A Suitable preparation methods for component A are emulsion, solution, bulk or suspension polymerization, preference being given to solution polymerization (see GB 1472195).
  • component A is isolated after the preparation by processes known to those skilled in the art, and preferably processed into granules. Thereafter, the production of the fiber composite materials can take place.
  • Component B is isolated after the preparation by processes known to those skilled in the art, and preferably processed into granules. Thereafter, the production of the fiber composite materials can take place.
  • the fiber composite material contains at least 5 wt .-%, based on the fiber composite material, the reinforcing fiber B (component B).
  • the reinforcing fiber B is in the fiber composite material preferably from 5 to 70 wt .-%, particularly preferably from 10 to 65 wt .-%, often from 25 to 65 wt .-% and in particular from 29.9 to 61, 9 wt .-%, based on the fiber composite material included.
  • the reinforcing fiber B can be any fiber whose surface has functional groups Bl, which can form a covalent bond with the monomers Al of component A.
  • the functional groups Bl on the surface of the reinforcing fiber B are selected from hydroxy, ester and amino groups. Particularly preferred are hydroxy groups.
  • the reinforcing fibers B are glass fibers having hydroxyl groups in the form of silanol groups as chemically reactive functionality B-1 at the surface.
  • the reinforcing fibers B may be embedded in the fiber composite material in any orientation and arrangement.
  • the reinforcing fibers B are preferably present in the fiber composite material not (statistically) uniformly distributed, but in levels with higher and lower levels (therefore as more or less separate layers). Preferably, it is assumed that a laminate-like or laminar structure of the fiber composite material.
  • the reinforcing fibers B may be present, for example, as fabrics, mats, nonwovens, scrims or knitted fabrics.
  • Such laminar laminates formed in this way comprise laminations of sheet-like reinforcing layers (of reinforcing fibers B) and layers of the polymer matrix which wets and holds them together, comprising at least one thermoplastic molding compound A.
  • the fibers B are preferably present as fabrics (fabrics, mats, nonwovens, scrims or knits) and / or as continuous fibers (including fibers which are the product of a single fiber twist).
  • the fibers B are therefore preferably not chopped fibers and the fiber composite material is preferably not a short glass fiber reinforced material, wherein at least 50% of the fibers B preferably have a length of at least 5 mm, more preferably at least 10 mm or more than 100
  • the length of the fibers B also depends on the size of the molded part T made of the fiber composite material.
  • the fibers B are embedded in layers in the fiber composite material, preferably embedded as a fabric or scrim, in particular as a fabric, in the fiber composite material.
  • flat fabrics F differ from short fibers, since the former have coherent, larger structures, which as a rule will be longer than 5 mm. the.
  • the fabrics F are preferably present in such a way that they (largely) pass through the fiber composite material (and also the component T produced therefrom). Passing through substantially means here that the fabrics F pass through more than 50%, preferably at least 70%, in particular at least 90%, of the length of the fiber composite material. The length here is the largest extent in one of the three spatial directions.
  • the fabrics F pass through more than 50%, preferably at least 70%, in particular at least 90%, of the surface of the fiber composite material W.
  • the surface is the area of maximum expansion in two of the three spatial directions.
  • the fiber composite material is preferably a (largely) flat fiber composite material (therefore also the molding T preferably a flat molding T).
  • the reinforcing fibers B are embedded in layers in the fiber composite material.
  • the reinforcing fibers B are present as a flat structure F.
  • the fibers are ideally parallel and stretched.
  • Tissues are created by the interweaving of continuous fibers, such as rovings.
  • the interweaving of fibers inevitably involves an ondulation of the fibers.
  • the ondulation causes in particular a reduction of the fiber-parallel compressive strength.
  • Mats are usually made of short and long fibers, which are loosely connected by a binder. Through the use of short and long fibers, the mechanical properties of components made of mats are inferior to those of fabrics.
  • Nonwovens are structures of limited length fibers, filaments or cut yarns of any kind and of any origin which have been somehow joined together to form a nonwoven and joined together in some manner. Knitted fabrics are thread systems by stitching.
  • the fabric F is preferably a scrim, a fabric, a mat, a nonwoven or a knitted fabric. Particularly preferred as a fabric F is a scrim or a fabric.
  • the fiber composite material used optionally contains 0 to 40 wt .-%, preferably 0 to 30 wt .-%, particularly preferably 0.1 to 25 wt .-%, based on the buzzer of the components A to C, one or more, to the components A and B of different additives (auxiliaries and additives).
  • Particulate mineral fillers, processing aids, stabilizers, oxidation retarders, agents against heat decomposition and decomposition by ultraviolet light, lubricants and mold release agents, flame retardants, dyes and pigments and plasticizers are to be mentioned.
  • esters as low molecular weight compounds are mentioned. Also, according to the present invention, two or more of these compounds can be used.
  • the compounds are present with a molecular weight of less than 3000 g / mol, often less than 150 g / mol.
  • Particulate mineral fillers may be, for example, amorphous silica, carbonates such as magnesium carbonate, calcium carbonate (chalk), powdered quartz, mica, various silicates such as clays, muscovite, biotite, suzoite, tin malite, talc, chlorite, phlogopite, feldspar, calcium silicates such as wollastonite or kaolin, especially calcined kaolin.
  • carbonates such as magnesium carbonate, calcium carbonate (chalk), powdered quartz, mica, various silicates such as clays, muscovite, biotite, suzoite, tin malite, talc, chlorite, phlogopite, feldspar, calcium silicates such as wollastonite or kaolin, especially calcined kaolin.
  • UV stabilizers include, for example, various substituted resorcinols, salicylates, benzotriazoles and benzophenones, which can generally be used in amounts of up to 2% by weight.
  • oxidation inhibitors and heat stabilizers may be added to the thermoplastic molding compound.
  • lubricants and mold release agents which are usually added in amounts of up to 1 wt .-% of the thermoplastic composition.
  • these include stearic acid, stearyl alcohol, stearic acid alkyl esters and amides, preferably Irganox®, and esters of pentaerythritol with long-chain fatty acids.
  • ethylene oxide-propylene oxide copolymers can also be used as lubricants and mold release agents.
  • natural and synthetic waxes can be used.
  • Flame retardants can be both halogen-containing and halogen-free compounds. Suitable halogen compounds, with brominated compounds being preferred over the chlorinated ones, remain stable in the preparation and processing of the molding composition of this invention so that no corrosive gases are released and efficacy is not thereby compromised. Preference is given to using halogen-free compounds, for example phosphorus compounds, in particular phosphine oxides and derivatives of acids of phosphorus and salts of acids and acid derivatives of phosphorus.
  • Phosphorus compounds particularly preferably contain ester, alkyl, cycloalkyl and / or aryl groups. Likewise suitable are oligomeric phosphorus compounds having a molecular weight of less than 2000 g / mol, as described, for example, in EP-A 0 363 608.
  • pigments and dyes may be included. These are generally in amounts of 0 to 15, preferably 0.1 to 10 and in particular 0.5 to 8 wt .-%, based on the buzzer of components A to C, included.
  • the pigments for coloring thermoplastics are generally known, see, for example, R. Gumbleter and H. Müller, Taschenbuch der Kunststoffadditive, Carl Hanser Verlag, 1983, pp. 494 to 510.
  • white pigments such as zinc oxide, Zinc sulfide, lead white (2 PbC03.Pb (OH) 2), lithopone, antimony white and titanium dioxide.
  • the rutile form is used for the whitening of the molding compositions according to the invention.
  • Black color pigments which can be used according to the invention are iron oxide black (Fe304), spinel black (Cu (Cr, Fe) 204), manganese black (mixture of manganese dioxide, silicon oxide and iron oxide), cobalt black and antimony black, and particularly preferably carbon black, which is usually present in Form of Furnace- or gas black is used (see G. Benzing, Pigments for paints, Expert-Verlag (1988), p. 78ff).
  • inorganic color pigments such as chromium oxide green or organic colored pigments such as azo pigments and phthalocyanines can be used according to the invention to adjust certain hues. Such pigments are generally available commercially.
  • organic sheets are processed by injection molding or pressing.
  • a functional integration for example, the molding or pressing of Functional elements, a further cost advantage can be generated because of further assembly steps, such as the welding of functional elements can be dispensed with.
  • the process for producing a fiber composite material comprises the steps:
  • thermoplastic molding composition A as matrix M, containing (or consisting of) polystyrene or at least one copolymer A-1 containing monomers Al (and optionally one or more further (co) polymers (Aa) and / or (Ab ));
  • thermoplastic molding material A Melting the thermoplastic molding material A and bringing it into contact with at least one reinforcing fiber B from step (i);
  • the manufacturing process may include the phases of impregnation, consolidation and solidification (consolidation) common in the manufacture of composites, which process may be influenced by the choice of temperature, pressure and times employed.
  • the fiber composite material contains (or consists of): a) 30 to 95% by weight of at least one thermoplastic molding compound A, b) 5 to 70% by weight of at least one reinforcing fiber B, and
  • Step (ii) of the process melting the thermoplastic molding compound A and contacting this melt with the reinforcing fibers B, may be effected in any suitable manner.
  • the matrix M consisting of at least one thermoplastic molding compound A, can be converted into a flowable material. conditions are transferred and the reinforcing fibers B are wetted to form a boundary layer.
  • Steps (ii) and (iii) can also be performed simultaneously. Then, immediately upon bringing the thermoplastic molding composition A into contact with the reinforcing fibers B, a chemical reaction takes place in which the monomers Al form a covalent bond with the surface of the reinforcing fibers B (usually via a bond to the functional groups B1) , This may be, for example, an esterification (for example, the esterification of maleic anhydride monomers with silanol groups of a glass fiber). Alternatively, the formation of a covalent bond may also be initiated in a separate step (e.g., by temperature elevation, radical starter, and / or photo-initiation). This can be done at any suitable temperature. The steps (ii) and / or (iii) are carried out at a temperature of at least 200 ° C, preferably at least 250 ° C, more preferably at least 300 ° C, especially at 300 ° C-340 ° C.
  • the residence time at temperatures of> 200 ° C. is not more than 10 minutes, preferably not more than 5 minutes, more preferably not more than 2 minutes, in particular not more than 1 min. Often 10 to 60 seconds are sufficient for the thermal treatment.
  • the process in particular the steps (ii) and (iii), can in principle be carried out at any pressure (preferably atmospheric pressure or overpressure), with and without pressing of the components.
  • any pressure preferably atmospheric pressure or overpressure
  • the properties of the fiber composite material can be improved.
  • styrene copolymers provided with at least one chemically reactive functionality (A1), ie amorphous thermoplastic matrices, are used as thermoplastic molding material A.
  • the surface quality can be substantially increased compared to the semicrystalline thermoplastics for such cladding parts, because the lower shrinkage of the amorphous thermoplastics, the surface topology, due to the fiber-rich (intersection point in tissues) and fiber-poor regions significantly is improved.
  • thermoplastic molding compound A and reinforcing fiber B (particularly if it is layered reinforcing fibers B). It is preferred, after impregnation and consolidation, to obtain a (as far as possible) non-porous composite material.
  • first layers of reinforcing fibers B can be prepared with differently prepared reinforcing fibers B, wherein an impregnation of the reinforcing fibers B takes place with the matrix of thermoplastic molding material A. Thereafter, impregnated layers may be present with reinforcing fibers B with different fiber-matrix adhesion, which can be consolidated in a further step to form a composite material as fiber composite material. Before the layers of reinforcing fibers B are laminated with the matrix of thermoplastic molding material A, at least a part of the reinforcing fibers B may be subjected to a pretreatment in the course of which the subsequent fiber-matrix adhesion is influenced.
  • the pretreatment may include, for example, a coating step, an etching step, a heat treatment step or a mechanical surface treatment step.
  • a coating step for example, by heating a part of the reinforcing fibers B, an already applied adhesion promoter can be partially removed.
  • no adhesion promoter in particular no adhesion promoter from the group consisting of aminosilanes and epoxy compounds, is used in the production of the fiber composite material.
  • the reinforcement layers can be completely interconnected during the manufacturing process (laminating).
  • Such fiber composite material mats offer optimum mator strength and stiffness in the fiber direction and can be processed particularly advantageous.
  • the method may also include the production of a molded part T.
  • the method comprises, as a further step (iv), a three-dimensional shaping to form a molding T.
  • thermoplastic molding composition A is still (partially) melted present.
  • a cured fiber composite material can also be cold formed.
  • a (substantially) solid molding T is obtained at the end of the process.
  • the process comprises as a further step (v) the curing of the product obtained from one of the steps (iii) or (iv).
  • This step can also be called solidification.
  • the solidification which generally takes place with removal of heat, can then lead to a ready-to-use molded part T.
  • the molding T may be further finished (e.g., deburred, polished, colored, etc.).
  • the process can be carried out continuously, semicontinuously or discontinuously. According to a preferred embodiment, the process is carried out as a continuous process, in particular as a continuous process for producing smooth or three-dimensionally embossed films. Alternatively, it is also possible to produce shaped parts T semi-discontinuously or discontinuously.
  • the organic sheets have an amorphous thermoplastic matrix M. These can be applied by injection molding with a ribbing, laminated on a foamed thermoplastic core or on a honeycomb core as cover layers (welded).
  • the improvement of the component stiffness by a ribbing is justified by the increase of the area moment of inertia.
  • optimal rib dimensions include production, aesthetic and constructive aspects.
  • the reinforcing fibers B may be layer-wise impregnated and consolidated as layers of reinforcing fibers B in a single processing step with the matrix M containing a thermoplastic molding material A. The production of the fiber composite material can be done in this way in a particularly efficient manner.
  • the weight reduction is applied to all moving components, e.g. Washing drums, an advantage, since the weight reduction of the moving masses energy savings can be achieved (reducing the torque during acceleration).
  • styrene copolymers as amorphous thermoplastics (e.g., SAN) is the sometimes high scratch resistance of these materials. This has the advantage in the application examples described below that the trim parts do not scratch during assembly and later use.
  • thermoplastic molding compositions described here are non-polar surface, which enables direct painting, pasting and printing.
  • Another advantage of the use according to the invention of the organo-sheets for the production of white goods is the high rigidity and strength. Lids for washing machines and dryers must withstand high loads, for example, because the devices are often stacked for space reasons. The upper cover of the lower device must bear the static and dynamic loads of the upper device. The required rigidity and strength is ensured by an organic sheet in a sandwich composite or z. B. achieved by a ribbing.
  • the core material in the sandwich composite can be either a foam core (eg Rohacell from Evonik) or a honeycomb core (eg Honeycomps from EconCore).
  • the core consists of a chemically compatible thermoplastic in order to heat-weld and to facilitate lamination in the production process.
  • a preferred way to achieve sufficient rigidity for, for example, covering, is the injection molding or pressing back of a ribbing in the injection molding or in the pressing process.
  • a suitable thermoplastic molding composition in particular one of the abovementioned styrene copolymers, should be used become.
  • SAN, ABS or ASA-based thermoplastic molding composition is used.
  • styrene copolymer when used as the polymer component (Aa), may be about a M-containing styrene copolymer (exemplified by a maleic anhydride-containing styrene copolymer).
  • the present invention relates to the use of a thermoplastic fiber composite material, wherein component A (or a component thereof) is produced from
  • a monomer A-l which has a chemically reactive functionality, in particular maleic anhydride, and wherein the reinforcing fibers B in the form of a gel, a fabric, a mat, a nonwoven or a knitted fabric are used and
  • the fiber composite material has a ribbing or a sandwich construction
  • the fiber composite material is optionally layered and contains more than two layers and
  • the fiber composite material optionally has a thickness of ⁇ 10 mm.
  • the present invention relates to the use of a thermoplastic fiber composite material of a thickness of ⁇ 10 mm, containing: a) 30 to 95 wt .-% of a thermoplastic, amorphous molding material A, wherein component A is prepared from 35 bis 70 wt .-% of at least one conjugated diene, 20 to 50 wt .-% of at least one vinyl aromatic monomer and 9 to 38 wt .-% of acrylonitrile and 0.1 to 5 wt .-% of a monomer Al, which has a chemically reactive functionality , in particular maleic anhydride, and wherein b) from 5 to 70% by weight of a reinforcing fiber B, the surface of the reinforcing fibers B having one or more of the functions of hydroxyl-containing fibers B being in the form of a fabric, a woven fabric, a mat, a fleece or a knitted fabric. , Ester or amino
  • the fiber composite material preferably has a ribbing or sandwich construction and / or is layered and contains more than two layers. Even more preferably, the fiber composite material has one or more other features as described above.
  • the present invention also encompasses white goods, e.g. a domestic appliance containing (at least one component containing) a) at least one thermoplastic molding compound A as a matrix
  • thermoplastic molding compound A has at least one chemically reactive functionality which reacts with chemical groups of the surface of component B during the manufacturing process of the fiber composite material
  • the whiteness would have further properties as set forth herein.
  • the present invention relates to a household appliance comprising at least one component comprising
  • thermoplastic molding material A as a matrix, prepared from From 35 to 70% by weight of at least one conjugated diene,
  • a monomer A-l which has a chemically reactive functionality, in particular maleic anhydride, and
  • thermoplastic molding compound A has at least one chemically reactive functionality which reacts with chemical groups of the surface of component B during the manufacturing process of the fiber composite material
  • the fiber composite material optionally has a ribbing or a sandwich construction.
  • thermoplastic layer on the organic sheet and a nonwoven which has at least a grammage of 50 g / m 2 and is embedded between organic sheet and thermoplastic layer, a grain can be shaped by means of the tool wall, whereby the surface additionally can be functionalized (scratch resistance, concealment of sink marks).
  • the additional thermoplastic layer can be colored opaque, so that optically no organo sheet can be assumed, or you can deliberately create a "fiber look" by the use of a transparent layer.
  • organo sheets in the sandwich or by ribbing can be achieved a cost reduction and at the same time the weight can be reduced, which on the one hand facilitate the assembly of the component and the other of the device.
  • Side panels of household appliances often have to withstand high loads during assembly and abuse and therefore consist largely of metals, mainly of painted steel sheets.
  • the inventive use of organo sheets as a replacement of metals can be reduced because the density of the organic sheets is much lower and the lack of rigidity, compared to steel, can be compensated by a ribbing or sandwich construction.
  • the ribbing preferably consists of an injection molding material, which ensures a cohesive connection to the organic sheet and thus gives rise to a high moment of resistance.
  • the sandwich construction there is also a similarity, so that here, too, creates a cohesive bond.
  • Functional integration can add another cost advantage to the injection molding process. For example, assembly steps can be saved in the holder, guides, locks, snap hooks, etc. can be molded directly with.
  • organ sheets in the area of household panel covers can, in addition to a cost and weight advantage, also result in an aesthetic advantage.
  • a so-called "fiber-look" can be achieved Even with the use of glass fiber, which is naturally transparent, the fibers can be made visible by painting the fibers
  • Organic sheets according to the invention have the advantage that they can be used unpainted, wherein in comparison to the steel sheet of the painting can be saved.
  • the weight of mobile home appliances can be reduced. This has the advantage that the devices become more manageable or, with the same weight, a larger battery can be installed in order to generate a longer battery life.
  • the wall thickness is oversized, often due to inadequate flowability of the injection molding compound or too low a flow path / wall thickness ratio.
  • the organic sheets according to the invention can be produced, for example, with a thickness of ⁇ 1 mm, preferably ⁇ 0.7 mm, particularly preferred ⁇ 0.5 mm.
  • these thin organic sheets are provided with a ribbing and Umklamung, resulting in very rigid components, since the organic sheet is located in the edge fiber of the shell component, which has an increase in the resistance moment result. Due to the amorphous matrix A and thus low shrinkage, the moldings have a very smooth surface, which can still be painted or laminated as needed.
  • the organo-sheets can also achieve a large weight advantage. Again, with the help of a Ribbing the stiffening of the components are supported. In addition, a functional integration can save subsequent assembly steps and other components and thus provides a cost advantage in addition to the weight.
  • FIG. 1 shows the fiber composite materials W which have been tested according to test no. 1 were obtained.
  • FIG. 1A shows the visual documentation.
  • FIG. 1B shows the microscopic view of a section through the laminar fiber composite material W arranged in a horizontal orientation (left: 25-fold magnification, right: 50-fold magnification), the fibers clearly being horizontal extending dark layer between the light layers of thermoplastic molding material can be seen.
  • Figure 1 C shows the 200-fold magnification, it can be seen that the impregnation is not completed in some places.
  • FIG. 2 shows the fiber composite materials W which have been tested according to test no. 2 were obtained.
  • FIG. 2A shows the visual documentation.
  • FIG. 2B shows the microscopic view of a section through the laminar fiber composite material W arranged in a horizontal orientation (left: 25-fold magnification, right: 50-fold magnification), wherein the fibers clearly show extending dark layer between the light layers of thermoplastic molding material can be seen.
  • FIG. 2C shows a magnification of 200 times, whereby it can be seen that the impregnation is partly not completed.
  • FIG. 3 shows the fiber-composite materials W, which according to test no. 3 were obtained.
  • FIG. 3A shows the visual documentation.
  • FIG. 3 shows the visual documentation.
  • FIG. 3B shows a microscopic view of a section through the laminar fiber composite material W arranged in a horizontal orientation (left: 25-fold magnification, right: 50-fold magnification), with no layer of fibers being recognizable
  • FIG. 3C shows the 200-fold magnification, whereby it can be seen that the impregnation is largely completed.
  • FIG. 4 shows the fiber composite materials W which have been tested according to test no. 4 were obtained.
  • FIG. 4A shows the visual documentation.
  • FIG. 4B shows the microscopic view of a section through the laminar fiber composite material W arranged in a horizontal orientation (left: 25-fold magnification, right: 50-fold magnification), with no layer of fibers being recognizable ,
  • Figure 4C shows the 200-fold magnification, it can be seen that the impregnation is not completely completed at individual points.
  • FIG. 5 shows the fiber composite materials W which have been tested according to test no. 5 were obtained.
  • FIG. 5A shows the visual documentation.
  • FIG. 5 shows the visual documentation.
  • FIG. 5B shows a microscopic view of a section through the laminar fiber composite material W arranged in a horizontal orientation (left: 25-fold magnification, right: 50-fold magnification), wherein no layer of fibers can be recognized
  • Figure 4C shows the 200-fold magnification, it can be seen that the impregnation is not completely completed in a few places.
  • FIG. 6 shows the production of the fiber composite materials W (here: glass fiber fabric) in the press inlet V25-V28. It is clearly recognizable that such a production method allows continuous production. In addition, it can be seen from the imprinting of the pattern that the fiber composite material W can also be shaped in three dimensions.
  • FIG. 7 shows schematically the development of undesired formation of surface waves (texture).
  • Laminate thickness 0.2 to 9.0 mm
  • Laminate tolerances max. ⁇ 0.1 mm according to semi-finished product
  • Sandwich panel thickness max. 30 mm
  • Tool pressure Press unit 5-25 bar, infinitely variable for minimum and maximum tool size (optional)
  • Mold temperature control 3 heating and 2 cooling zones
  • Opening travel press 0.5 to 200 mm
  • Transparency was measured on 1 mm organo-sheet specimens in% of white daylight (100%) (Byk Haze gardi transparency meter (BYK-gardner, USA) according to ASTM D 1003 (eg ASTM D 1003-13)).
  • the described fiber composite materials (organic sheets), in particular with amorphous, thermoplastic matrix are particularly suitable for the production of household goods, such as large and small appliances. Some examples are shown below. Unless otherwise stated, the moldings are manufactured by injection molding. Example 1 Production of the fiber composite material M
  • thermoplastic molding composition A 40% by weight, based on the fiber composite material, of a styrene-acrylonitrile-maleic anhydride copolymer as thermoplastic molding composition A (prepared from: 75% by weight of styrene, 24% by weight of acrylonitrile and 1% by weight of maleic anhydride) is compounded with 60 wt .-%, based on the fiber composite material, a glass-based reinforcing fiber with chemically reactive functionality (silane groups) on the surface [GW 123-580K2 of PD Glasseiden GmbH].
  • thermoplastic molding composition A (ABS prepared from: 45 wt .-% butadiene, 30 wt .-% styrene, 24 wt .-% acrylonitrile and 1 wt .-% maleic anhydride) is with
  • Example A Large appliances: extractor hoods, electric cooker, freezer, freezer / freezer combinations, dishwasher, refrigerators, washing machines and tumble dryers, spin dryers, wine refrigerators
  • Example B Small appliances: bottle cooler, coffee grinder, blender, coffee machine, microwave oven, stirrers, immersion heater, toaster, kettle
  • the fiber composite materials M and N are suitable as replacement of metals in the range of panels for the household appliances mentioned in Examples A and B.
  • Example D moving parts: washing drums
  • Example E mobile appliances: hand vacuum cleaner
  • thermoplastic fiber composite material according to the invention containing the modified thermoplastic molding compound A, the layers of reinforcing fibers B and the additive C, both a lighter wall can be realized, so also more space indoors to be made in order to accommodate more space for z. B. to get a battery. It is also observed increased rigidity of the components. The difference to the rigidities of metal cladding can be compensated.
  • A1 (comparison): S / AN with 75% styrene (S) and 25% acrylonitrile (AN), viscosity number
  • A2 S / AN / maleic anhydride copolymer having the composition (wt%): 74/25/1, Mw of 250,000 g / mol (measured via gel permeation chromatography on standard columns with monodisperse polystyrene calibration standards)
  • B1 Bidirectional glass fiber substrate 0/90 ° (GF-GE) with basis weight
  • Matrix layer in top layer not visible on the roving
  • Impregnation Warp threads Central unimpregnated areas, all around slightly impregnated Impregnation Weft threads: in the middle clearly unimpregnated areas, all around slightly impregnated
  • Air inclusions little, only in roving
  • Matrix layer in middle position recognizable
  • Matrix layer in top layer little recognizable by the roving
  • Impregnation Warp threads Central unimpregnated areas visible, partially impregnated all around, partially unimpregnated
  • Impregnation Weft threads Central unimpregnated areas, all-round lightly impregnated
  • Matrix layer in middle position not recognizable
  • Matrix layer in top layer easily recognizable
  • Impregnation Warp threads hardly any unimpregnated areas visible, all-round well impregnated
  • Impregnation Weft threads hardly any unimpregnated areas visible, all-round well impregnated
  • Matrix layer in middle position hardly recognizable
  • Matrix layer in cover layer recognizable
  • Impregnation Warp threads Slightly unimpregnated areas visible, all-round well impregnated
  • Impregnation Weft threads unimpregnated areas visible, but impregnated all around
  • Matrix layer in middle position not recognizable
  • Matrix layer in cover layer recognizable
  • Impregnation warp threads little unimpregnated areas visible, all-round well impregnated
  • Impregnation Weft threads little unimpregnated areas recognizable, all-round well impregnated
  • SAN SAN-MA terpolymer, weight composition (% by weight): 73/25/2, Mw:
  • PA6 semi-crystalline, easy-flowing polyamide 6
  • Fibers (B3): glass fiber fabric twill 2/2 (GF-KG) with basis weight 300 g / m 2 ,
  • the described fiber composite materials are particularly suitable for the production of transparent and translucent molded bodies, films and coatings. Some examples are shown below. Unless otherwise stated, the moldings are made by injection molding. Production of molded parts from fiber composite materials M and N for washing machine windows
  • the components are as defined above.
  • the bending stress and the flexural modulus were determined according to DIN 14125: 201 1 -05.
  • Table 1 Compositions Comp. 1, Comp. 2, Comp. 10 and Comp. 15 and the compositions V3 to V9 according to the invention and V1 1 to V14.
  • Table 7 shows the conditions of the experiments carried out.
  • the pressing pressure was approximately 20 bar in all test series.
  • Table 8 Average values of the maximum bending stress of the warp and weft directions of the produced organic sheets according to the mixtures Cf. 2, V5, V7, V9, Vgl. 10, V12 to V14 and Cgl. 15, wherein the production temperature was at least 300 ° C.
  • S styrene
  • AN acrylonitrile
  • Laminate thickness 0.2 to 9.0 mm
  • Laminate tolerances max. ⁇ 0.1 mm according to semi-finished product
  • Sandwich panel thickness max. 30 mm
  • Tool pressure Press unit 5-25 bar, infinitely variable for minimum and maximum tool size (optional)
  • Mold temperature control 3 heating and 2 cooling zones
  • Opening travel press 0.5 to 200 mm
  • T [° C] temperature of the temperature zones * ( * The press has 3 heating zones and 2 cooling zones.
  • Construction / lamination 6-layer structure with melt middle layer; Production process: melt direct (SD)
  • M1 (SAN type): styrene-acrylonitrile-maleic anhydride (SAN-MA) terpolymer (S / AN / MA: 74/25/1) with an MA content of 1% by weight and an MVR of 22 cm 3 / 10 min at 220 ° C / 10kg (measured to IS01 133);
  • M1 b corresponds to the abovementioned component M1, the matrix additionally being admixed with 2% by weight of carbon black.
  • M2 (SAN type): styrene-acrylonitrile-maleic anhydride (SAN-MA) terpolymer (S / AN / MA: 73/25 / 2.1) with an MA content of 2.1% by weight and an MVR of 22 cm 3/10 min at 220 ° C / 10kg (measured according to IS01 133);
  • M2b corresponds to the abovementioned component M2, the matrix additionally being admixed with 2% by weight of carbon black.
  • M3 (SAN type): blend of 33% by weight of M1 and 67% by weight of the SAN copolymer Luuran VLN, therefore 0.33% by weight of maleic anhydrideMA) in the entire blend;
  • M3b corresponds to the abovementioned component M3, the matrix additionally being admixed with 2% by weight of carbon black.
  • PA6 semi-crystalline, easy-flowing polyamide Durethan B30S
  • Glass filament twill weave (short designations: GF-KG (LR) or LR), twill weave 2/2, basis weight 290 g / m 2 , roving EC9 68tex, finish TF-970, delivery width 1000 mm (type: 01 102 0800-1240; Manufacturer: Hexcel, obtained from: Lange + Ritter)
  • Glass filament twill weave (short designations: GF-KG (PD) or PD), twill weave 2/2, basis weight 320 g / m 2 , Roving 320tex, finish 350, delivery width 635 mm (type: EC14-320-350, manufacturer and supplier : PD Glasseide GmbH Oschatz) Glass filament scrim (short name: GF-GE (Sae) or Sae) 0 45 90 -45 °, basis weight 313 g / m 2 , main roving 300tex, finish PA size, delivery width
  • Sae ns glass filament scrim 300 g / m 2 , manufacturer's name: Saertex new sizing, + 457-457 + 457-45 °
  • Glass fiber fleece (short name: GV50), basis weight 50 g / m 2 , fiber diameter 10 ⁇ , delivery width 640 mm (Type: Evalith S5030, manufacturer and supplier: Johns Manville Europe)
  • All produced composite fiber materials could be produced as (large) flat Orga- nobleche in a continuous process, which could be cut to size (in laminatable, customary transport dimensions such as 1 m x 0.6 m).
  • the embedded fiber material was just recognizable when examined in detail against the light.
  • the embedded fiber material was not / hardly recognizable even under closer light in the backlight.
  • LSM confocal laser scanning microscopy
  • Fiber-composite materials with four embedded layers of the respective fabric of fibers (here GF-KG (PD) (4) or Sae (4)) were produced in the respective matrix.
  • a thin fiberglass mat (GV50, see above) was applied to the produced fiber composite materials on both sides. This had no noticeable influence on the mechanical properties.
  • the mean wave depth (MW Wt) and the spatial ration value (Ra) were determined for numerous fiber composite materials. It was found that the MW Wt for all fiber composite materials in which the matrix contains a functional component that can react with the fibers is clearly ⁇ 10 ⁇ m, whereas in composite fiber materials with comparable PA6 and PD (OD ) Matrices is clearly ⁇ 10 ⁇ .
  • the determined spatial values were also significantly lower for composite fiber materials according to the invention. By way of example, these are the measured values below.
  • the strength in the warp and weft directions was examined separately. It could be shown that the fiber composite materials are very stable in both warp and weft directions. In the warp direction, the fiber composite materials are usually even more stable than in the weft direction.
  • the matrix components A are as described above.
  • Fiber components B (unless described above)
  • FG290 glass filament fabric 290g / m 2 , manufacturer's name: Hexcel HexForce® 01202 1000 TF970
  • FG320 glass filament fabric 320g / m 2 , manufacturer's name: PD Glasseide GmbH Oschatz EC 14-320-350
  • Sae MuAx313, glass filament scrim 300g / m 2 , manufacturer's name: Saertex XE-PA-313-655
  • the following transparent fiber composite materials were produced, in each of which flat fiber material was introduced.
  • the produced fiber composite materials each had a thickness of about 1, 1 mm.
  • a thin fiberglass mat (GV50, see above) was applied to the produced fiber composite materials on both sides. This has no noticeable influence on the mechanical or optical properties.
  • the following bending strengths were determined according to DIN EN ISO 14125:
  • the following black-colored fiber composite materials were produced, in which 2% by weight of carbon black was added to the matrix and introduced into the respective flat fiber material.
  • the fiber composite materials produced each had a thickness of about 1, 1 mm.
  • a thin fiberglass mat (GV50, see above) was applied to the produced fiber composite materials on both sides. This has no noticeable influence on the mechanical or optical properties.
  • the following bending strengths according to DIN EN ISO 14125 were determined for the samples:
  • the fabrics used can be processed into fiber composites with particularly high flexural strength.
  • the fiber composite materials according to the invention in which the matrix contains a component which reacts with the fibers (here: maleic anhydride (MA)), have a significantly higher flexural strength than the comparative molding compositions without such a component, such as PC (OD) or PA6.
  • a component which reacts with the fibers here: maleic anhydride (MA)
  • the impact resistance and puncture behavior (Dart Test to ISO 6603) was determined for the fiber composite materials.
  • the fiber composite materials showed a high stability of Fm> 3000 N.
  • the resulting fiber composite materials could be formed into three-dimensional semifinished products, for example semi-shell-shaped semi-finished products. It was also found that the resulting fiber composite materials could be printed and laminated.
  • the evaluation of different fiberglass-based textile systems with different matrix systems to form a fiber composite material has shown that good fiber composite materials (as organic sheets and semi-finished products made from them) can be produced reproducibly. These can be made colorless or colored.
  • the fiber composite materials showed good to very good optical, haptic and mechanical properties (such as with regard to their flexural strength and puncture resistance). Mechanically, the tissues showed somewhat greater strength and rigidity than scrim.
  • the styrene copolymer-based matrices (SAN matrices) tended to result in better fiber composite materials in terms of mechanical properties than the alternative matrices such as PC and PA6.
  • the fiber composite materials according to the invention could be produced semi-automatically or fully automatically by means of a continuous process.
  • the fiber composite materials according to the invention (organic sheets) can be well converted to three-dimensional semi-finished products.

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Abstract

L'utilisation d'un matériau composite thermoplastique renforcé de fibres, qui contient a) au moins une matière à mouler thermoplastique A servant de matrice, b) au moins une couche de fibres de renfort B, et c) éventuellement au moins un additif C, ladite au moins une couche constituée des fibres de renfort B étant insérée dans la matrice formée par la matière à mouler thermoplastique, et la matière à mouler thermoplastique A possédant au moins une fonctionnalité chimiquement réactive qui, pendant le processus de fabrication du matériau composite renforcé de fibres, réagit avec des groupes chimiques de la surface du constituant B, dans la fabrication de produits blancs, tels que des appareils ménagers, permet d'obtenir des produits légers.
EP16721376.8A 2015-04-22 2016-04-22 "organosheets" (plaques de composite thermoplastique renforcé de fibres) à base de polymère de styrène pour produits blancs Withdrawn EP3286000A1 (fr)

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PCT/EP2016/058994 WO2016170104A1 (fr) 2015-04-22 2016-04-22 "organosheets" (plaques de composite thermoplastique renforcé de fibres) à base de polymère de styrène pour produits blancs

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EP3688071A1 (fr) * 2017-09-26 2020-08-05 INEOS Styrolution Group GmbH Composite renforcé par des fibres ayant une ondulation de surface réduite
CN111448243A (zh) * 2017-09-26 2020-07-24 英力士苯领集团股份公司 成型体及其制备方法
CN111406087A (zh) * 2017-09-26 2020-07-10 英力士苯领集团股份公司 具有改善的纤维-基质粘合性的纤维增强复合材料
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