DE10161155B4 - Deposit containing polyurethane composite components - Google Patents

Abstract

A method of making composite components comprising the steps
A) coating at least one insert with a polymer layer and inserting a film (i) into a mold,
B) applying at least one insert to the upper die, the inserts being coated with a polymer layer,
C) applying a layer of fiber-reinforced polyurethane (ii) to the film (i) and then
D) curing of the composite component with the mold closed.

Description

The The invention relates to composite components, composed of a film and a layer of fiber reinforced Polyurethane containing inserts, the inserts being coated with a polymer layer, and a process for their preparation and their use as Body parts.

EP 1 077 2 A2 and EP 995 667 A1 describe composite components, in particular roof modules for motor vehicles, which are produced by molding a thermoplastic film and then applying fiber-reinforced polyurethane to this film. The thermoplastic, colored film replaces the paint job. The composite components described are used, for example, in motor vehicles of the 'smart' type.

Around to improve the torsional stiffness of such composite components or the attachment of attachments such as handles to enable, It is necessary to have one or more depositors, preferably in shape profiled bows to incorporate into the composite component.

Out The prior art is well known that depositors or Bow by insertion into a mold and subsequent integration be incorporated into a polyurethane matrix in polyurethane components can. However, this method has composite components of film and Polyurethane matrix has the disadvantage that after cooling and Demoulding the component the geometry of the insert or bow on the film side of the component signs.

task It was therefore the object of the invention to provide a method for producing composite components, constructed of foil and fiber reinforced polyurethane, ready for where the composite components should contain inserts without that the geometry of the depositors on the film side of the composite components looming. Furthermore, it was an object of the invention corresponding To provide composite components.

The Task was solved be that the inserts, preferably profiled inserts, before the Introduction into the mold were coated with a polymer layer.

object The invention therefore composite components constructed of a film (i) and a layer of fiber-reinforced polyurethane (ii) containing Depositors, wherein the depositors coated with a polymer layer are.

• A) Beschichten mindestens eines Einlegers mit einer Polymerschicht und Einlegen einer Folie (i) in ein Formwerkzeug.
• B) Anbringen von mindestens einem Einleger am Werkzeugoberteil, wobei die Einleger mit einer Polymerschicht beschichtet sind,
• C) Aufbringen einer Schicht aus faserverstärktem Polyurethan (ii) auf die Folie (i) und anschließend
• D) Aushärten des Verbundbauteils bei geschlossener Form.

Furthermore, the subject matter of the invention is a process for the production of composite components, comprising the steps

• A) coating at least one insert with a polymer layer and inserting a film (i) in a mold.
• B) applying at least one insert to the upper die, the inserts being coated with a polymer layer,
• C) applying a layer of fiber-reinforced polyurethane (ii) to the film (i) and then
• D) curing of the composite component with the mold closed.

Further The invention relates to the use of inserts, with a polymer layer coated are, for improving the rigidity of composite components comprising a film and a layer of fiber reinforced polyurethane and use said composite components for the production of body parts.

The consist composite components according to the invention from two layers. Layer i) of the composite component according to the invention comprises a film, which is usually of metal, for example of aluminum, preferably aluminum coilcoating, or may consist of a thermoplastic material. As a thermoplastic Can slide generally known films are used, for example conventional films based on acrylonitrile-butadiene-styrene (ABS), polymethylmethacrylate (PMMA), acrylonitrile-styrene-acrylic ester (ASA), acrylonitrile-styrene-acrylic ester and polycarbonate blend (ASA-PC), polycarbonate (PC), thermoplastic Polyurethane, polypropylene, polyethylene, and / or polyvinyl chloride (PVC).

such Films are commercially available and their production is well known. The films usually have a thickness of 0.1 to 15 mm, preferably from 1 to 3 mm, on. Prefers be as thermoplastic film (i) one at least two layers used, wherein the one layer an ASA and / or Polycarbonate and / or ASA-PC blend material contains. Especially it is preferred to use an at least two-layer film, wherein the first layer is based on PMMA and the second layer on ASA and / or ASA PC and / or PC. If you use two-layer film, so the polyisocyanate polyaddition product preferably adheres to ASA and / or ASA / PC and / or PC.

Prefers a slide is used that creates a Class-A surface. Under Class-A surface does one understand a surface, which looks visually high-quality when viewed visually. In the Assessment of high quality can Long and short waviness, defects and / or gloss are taken into account become.

Layer ii) of the composite components according to the invention comprises fiber-reinforced polyurethane and serves as a carrier, which gives the composite component advantageous mechanical properties, such as high strength.

Under fiber reinforced Polyurethane is understood as polyurethane, which contains fibers for reinforcement, wherein these fibers are preferably such that they do not have a usual High-pressure mixing head are processable. The fibers can, for example by the LFI method known from the prior art (Long Fiber Injection) are introduced into the polyurethane and show generally a length of more than 5 mm, preferably of more than 10 mm, more preferably of 10 mm to 10 cm on.

Farther it is also possible To introduce the fibers in the form of mats in the polyurethane (mat insertion method).

at the fibers used may be glass fibers, natural fibers, such as flax, jute or sisal, synthetic fibers, such as Polyamide fibers, polyester fiber, carbon fibers or polyurethane fibers act. Preferably used are glass fibers.

The Fibers usually become in an amount of 0.1 to 90 wt .-%, preferably from 1 to 50, more preferably from 5 to 40 and more preferably from 10 to 30% by weight, based on the total weight of the layer ii) used.

The Layer ii) of the composite components according to the invention usually indicates a density of 0.1 to 1.3 kg / l, preferably 0.3 to 1.0 kg / l. To achieve this density are compact or cellular polyurethanes used, wherein polyurethane rigid foams are preferably used.

The Thickness of the layer ii) in the composite components according to the invention is usually 0.1 to 250 mm, preferably 0.5 to 100 mm, more preferably 1 to 50 mm, more preferably 1 to 10 mm.

at the composite components according to the invention is preferably adhesion between layer i) and layer ii), i.e. the adhesion between the layers is preferably greater than the cohesion within a layer. To increase the adhesion between The layers i) and ii) can be pretreated layer i) before the foam be, for example, by applying a primer, by flame treatment or mechanical roughening or irradiation with light (wavelength of the Radiation less than 800 nm) or particles (sandblasting). This pretreatment is optional.

The Layer ii) of the composite elements according to the invention includes polyurethanes. The term polyurethanes refers here on polyisocyanate polyaddition products obtained by reaction of a) polyisocyanates with b) compounds reactive with isocyanate, if appropriate in the presence of c) blowing agents, d) catalysts and e) auxiliary and additives available are.

When Isocyanates (a) can well-known (cyclo) aliphatic and / or in particular aromatic Polyisocyanates are used. For the preparation of the composite elements according to the invention Particularly suitable are aromatic or aliphatic diisocyanates, preferably diphenylmethane diisocyanate (MDI), tolylene diisocyanate (TDI) and hexamethylene diisocyanate (HDI). The isocyanates can be used in Form of pure compound or in modified form, for example in the form of urethdiones, isocyanurates, allophanates or biurethene, preferably in the form of urethane and isocyanate groups Reaction products, so-called isocyanate prepolymers used become.

Suitable compounds which are reactive towards isocyanates (b) are compounds which contain two or more reactive groups selected from OH groups, SH groups, NH groups, NH ₂ groups and CH-acidic groups, for example β-diketo groups. Groups, carry in the molecule.

Conveniently, are those having a functionality of 1.8 to 8, preferably 2 to 6, and a molecular weight of 300 to 8000, preferably used from 400 to 4000. proven have e.g. Polyether polyamines and / or preferably polyols, selected from the group of polyether polyols, polyester polyols, polythioether polyols, polyester amides, hydroxyl-containing polyacetals and hydroxyl-containing aliphatic polycarbonates or mixtures of at least two of mentioned polyols. Preferably used polyester polyols and / or polyether polyols. Particularly preferred are polyether polyols used, which have at least 10% primary hydroxyl groups. The hydroxyl number of the polyhydroxyl compounds is thereby usually 50 to 1000. Furthermore, the compounds (b) in a mixture with usual Chain extenders and / or crosslinkers be used.

When Propellant (c) can for the production of foamed Products generally known chemically or physically acting Connections are used. As a chemical blowing agent Water may preferably be used. Examples of physical Blowing agents are inert (cyclo) aliphatic hydrocarbons with 4 to 8 carbon atoms, which under the conditions of polyurethane formation evaporate. The amount of blowing agent used depends according to the desired density of the foams.

When Catalysts (d) can be conventional compounds are used, which is the reaction of component (a) with the component (b) accelerate. For example, tertiary amines and / or organic metal compounds. For example, the following may be used as catalysts Compounds are used: triethylenediamine, aminoalkyl and / or Aminophenylimidazoles, e.g. 4-chloro-2,5-dimethyl-1- (N-methylaminoethyl) imidazole, 2-Rminopropyl-4,5-dimethoxy-1-methylimidazole, 1-aminopropyl-2,4,5-tributylimidazole, 1-aminoethyl-4-hexylimidazole, 1-aminobutyl-2,5-dimethylimidazole, 1- (3-aminopropyl) -2-ethyl-4-methylimidazole, 1- (3-aminopropyl) imidazole and / or 1- (3-aminopropyl) -2-methylimidazole, Tin (II) salts of organic carboxylic acids, e.g. diacetate, tin (II), Tin (II) dioctoate, tin (II) diethylhexoate and tin (II) dilaurate and dialkyltin (IV) salts of organic carboxylic acids, e.g. Dibutyltin diacetate, dibutyltin dilaurate, dibutyltin maleate and Dioctyltin diacetate.

The If appropriate, reaction takes place in the presence of (g) auxiliary and / or Additives such as e.g. Cell regulators, release agents, pigments, surface-active Compounds and / or stabilizers against oxidative, thermal or microbial degradation or aging.

to Production of polyurethanes can the isocyanates (a) and the opposite Isocyanate-reactive compounds (b) in such amounts for the reaction brought that the equivalence ratio of NCO groups of (a) to the sum of the reactive hydrogen atoms of (b) is preferred 0.90 to 1.5: 1, more preferably 1 to 1.2: 1.

The Layer ii) of the composite components according to the invention contains Depositors. Depositor is understood to mean objects that are whole or partially in the fiber reinforced Polyurethane layer are foamed can. The inserts used are preferably made of plastic and / or Metal. examples for Preferred metals are steel, copper, zinc, aluminum or mixtures from that.

The Shape of the depositors may vary depending on the application. For improvement the torsional stiffness are preferred profiled inserts (bow) used. these can over the entire width or length of the composite component extend.

Further can as insert attachments such as screws or handles, for example for speakers, Lamps or antennas are incorporated into the PUR matrix.

1 illustrates a composite component containing coated inserts. The composite component has the shape of a roof module, which contains both an insert as a crossbeam and inserts for handles.

In 1 means:

1

roof module (Top view)

2

front

3

back

4

depositors for handholds

5

crossbeam

6

stiffening ribs

The Inserts used in this invention are coated with a polymer layer. This coating can be in general with all methods known in the art respectively. For example, the polymer layer as a spray on the inserts are applied. It is also possible that Deposit liner with a film of the corresponding polymer. It is also possible bring the depositors in a form that between form wall and Depositor a desired one Distance is present, in which space then the Polymer is introduced.

The Polymer layer generally has a thickness of 0.5 to 20 mm, preferably from 1 to 10 mm.

When Polymer is generally suitable for any plastic, the at the production of the composite component occurring in-mold pressure withstand. This internal mold pressure is generally from 2 to 15 bar.

Furthermore, it is advantageous to choose the type of polymer such that the linear expansion coefficients are adapted to the polymer layer surrounding the insert and the fiber-reinforced polyurethane layer. Linear expansion refers to the change in length dL which a solid body, in this case layer i), undergoes at a temperature change dT. It is described to a first approximation by dL / L = a · dT, wherein the linear expansion coefficient a is specified in the order of 10 ^-6 / K.

in the In general, layer ii) has a linear expansion coefficient from 0.1 to 65, preferably from 1 to 50, more preferably from 20 to 45 on. In a preferred embodiment, that for coating the insert used polymer layer has a coefficient of linear expansion on, for the applies: coefficient of linear expansion (Polymer layer) = coefficient of linear expansion (Fiber-reinforced Polyurethane) ± 50, preferably ± 30.

Examples for suitable Polymers are polyethylene, polypropylene, acrylic acid-butadiene-styrene copolymers (ABS), polyvinyl chloride (PVC), acrylate rubber, polyester, polyoxymethylene (POM), Polyamide (PA), polycarbonate (PC) and polyurethane, in particular compact Polyurethane, e.g. thermoplastic polyurethane (TPU) or rigid polyurethane foam. Preference is given to using compact polyurethanes under the Designation "coating systems" known in the art are.

The Production of the composite components according to the invention is preferably according to the following Method.

In a first step A) is in the lower mold part of a two-part Forming the layer i) of the composite component by inserting a film, optionally before, for example, by vacuum forming was preformed, introduced. The surface, which preferably class A surface later Composite component is facing the mold wall.

Subsequently, will in a second step B) one or more depositors, the or which are coated with a polymer layer, on the upper mold of the Mold attached. The fixation can for example by a clamping device or preferably by magnets. in the In general, step B) may also be before or at the same time as step A).

After that In a third step C), the layer ii) is made of fiber-reinforced polyurethane for example, by the known LFI method or mat insertion method applied to the film (layer i)). The application of the polyurethane matrix takes place preferably in open form.

After this the fiber reinforced Polyurethane layer is introduced is generally closed the mold and cured the composite component. Thereby become the inserts on the form top with the polyurethane matrix brought into contact. Depending on the application, the fixation the depositor chosen this way be that the depositors in the finished composite component completely from the fiber reinforced Polyurethane layer wrapped are, or that they only on one side to the fiber-reinforced polyurethane layer Have contact.

When Molds for the production of the products can be conventional and commercially available tools be used, the surface, for example made of steel, aluminum, enamel, teflon, epoxy resin or another polymeric material, the surface optionally chromed, For example, can be hard chrome. Preferably, the molds should tempered to adjust the preferred temperatures, lockable and preferred for exercise be equipped with a pressure on the product.

The Implementation of fiber-reinforced Polyurethane layer is usually at a mold temperature of 30 to 80 ° C and a temperature of the starting components of preferably 18 to 65 ° C for a duration from usually 0.5 to 10 minutes, preferably 0.5 to 5 minutes.

The have composite components according to the invention according to their preferred use as flat moldings, for example as replacement for Metallic sheets, preferably a flat structure on. The products have a thickness of 1 to 500 mm, preferably from 5 to 50 mm.

The Composite components according to the invention are preferably used as components in vehicle, aircraft or real estate construction, preferably as body parts for motor vehicles, especially as roofs or roof modules, doors, Hoods, trunk lids, end edge flaps, bumpers and Hardtops.

According to the present Invention find inserts which are coated with a polymer layer, Use for installation in composite components, comprising a film and a layer of fiber reinforced Polyurethane, for example, to improve the torsional stiffness. The use of these inserts is advantageous because of the geometry of the insert does not appear on the side of the film.

Claims (7)

Method for producing composite components, comprising the steps A) Coating of at least one depositor with a polymer layer and placing a film (i) in a mold, B) Attaching at least one insert on the upper tool, wherein the inserts are coated with a polymer layer, C) Applying a layer of fiber-reinforced polyurethane (ii) on the film (i) and then D) Harden of the composite component with the mold closed. Composite components, composed of a film and a Layer of fiber reinforced Polyurethane containing inserts, wherein the inserts are coated with a polymer layer are. Composite components according to claim 2, characterized that the polymer layer used to coat the depositors has a thickness of 0.5 mm to 20 mm. Composite components according to claim 2 or 3, characterized that the polymer layer used to coat the depositors a coefficient of linear expansion has, for the following applies: coefficient of linear expansion (Polymer layer) = coefficient of linear expansion (Fiber-reinforced Polyurethane) ± 50. Composite components according to one of claims 2 to 4, characterized in that it is at the for coating the insert used polymer layer around compact polyurethane is. Use of composite components according to claim 5 for the manufacture of body parts. Use of inserts coated with a polymer layer are, for incorporation into composite components, comprising a film and a Layer of fiber reinforced Polyurethane.