U.S. patent application number 14/764392 was filed with the patent office on 2015-12-31 for fibre composite hybrid components.
This patent application is currently assigned to EVONIK DEGUSSA GMBH. The applicant listed for this patent is EVONIK INDUSTRIES AG. Invention is credited to Maximilian GRUHN, Karl KUHMANN, Martin RISTHAUS.
Application Number | 20150375478 14/764392 |
Document ID | / |
Family ID | 48578744 |
Filed Date | 2015-12-31 |
United States Patent
Application |
20150375478 |
Kind Code |
A1 |
GRUHN; Maximilian ; et
al. |
December 31, 2015 |
FIBRE COMPOSITE HYBRID COMPONENTS
Abstract
The invention relates to hybrid components comprising at least
one fibre composite material as material B and at least one
material A. Material A is selected from plastics, metals, ceramic
compositions, wood, glass, composite materials, textile fibres and
from prefabricated products produced from textile fibres. Material
A is bonded to material B by at least one coating of an adhesion
promoter composition comprising at least one copolyamide-based
hotmelt adhesive.
Inventors: |
GRUHN; Maximilian; (Marl,
DE) ; KUHMANN; Karl; (Duelmen, DE) ; RISTHAUS;
Martin; (Olfen, DE) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
EVONIK INDUSTRIES AG |
Essen |
|
DE |
|
|
Assignee: |
EVONIK DEGUSSA GMBH
Essen
DE
|
Family ID: |
48578744 |
Appl. No.: |
14/764392 |
Filed: |
January 29, 2014 |
PCT Filed: |
January 29, 2014 |
PCT NO: |
PCT/EP2014/051692 |
371 Date: |
July 29, 2015 |
Current U.S.
Class: |
442/286 ;
156/330.9; 428/221; 428/299.1; 428/435; 428/446; 428/458;
428/474.4 |
Current CPC
Class: |
B32B 2255/26 20130101;
C09J 177/00 20130101; B32B 27/06 20130101; B32B 21/10 20130101;
B32B 2605/18 20130101; B32B 21/04 20130101; B32B 15/14 20130101;
B32B 37/12 20130101; C09J 177/02 20130101; C09J 2463/00 20130101;
B32B 15/088 20130101; B32B 27/12 20130101; B32B 2451/00 20130101;
B32B 5/26 20130101; C08G 18/798 20130101; B29C 45/1671 20130101;
B32B 27/34 20130101; B32B 2607/00 20130101; B32B 2037/1215
20130101; B32B 2262/106 20130101; Y10T 428/31515 20150401; C09J
2477/00 20130101; C08L 63/00 20130101; B32B 17/064 20130101; C09J
177/06 20130101; B32B 2262/101 20130101; B32B 2605/08 20130101;
B29C 45/14311 20130101; B32B 7/12 20130101; B32B 2307/31 20130101;
B32B 21/08 20130101; B32B 2457/00 20130101; C08G 18/003 20130101;
B32B 15/08 20130101; B32B 2255/06 20130101; B32B 2255/28 20130101;
B29C 2045/14868 20130101; C09J 5/02 20130101; Y10T 428/31511
20150401; C08G 18/8061 20130101; B29K 2705/00 20130101; C09J 177/02
20130101; C08L 63/00 20130101; C09J 177/06 20130101; C08L 63/00
20130101; C09J 177/00 20130101; C08L 63/00 20130101 |
International
Class: |
B32B 7/12 20060101
B32B007/12; B32B 21/04 20060101 B32B021/04; C09J 177/00 20060101
C09J177/00; B32B 5/26 20060101 B32B005/26; B32B 27/12 20060101
B32B027/12; B32B 37/12 20060101 B32B037/12; B32B 15/14 20060101
B32B015/14; B32B 27/06 20060101 B32B027/06 |
Foreign Application Data
Date |
Code |
Application Number |
Jan 29, 2013 |
DE |
10 2013 201 388.4 |
May 29, 2013 |
EP |
13002778.2 |
Claims
1. A hybrid component comprising: at least one fibre composite
material as material B, and at least one material A, wherein
material A is selected from the group consisting of plastics,
metals, ceramic compositions, wood, glass, composite materials,
textile fibres and prefabricated products produced from textile
fibres, and wherein material A is bonded to material B by at least
one coating of an adhesion promoter composition containing at least
one copolyamide-based hotmelt adhesive.
2. The hybrid component according to claim 1, wherein the fibre
composite material of material B is a fibre-plastic composite.
3. The hybrid component according to claim 2, wherein the fibres of
the fibre-plastic composite are selected from the group consisting
of carbon fibres and glass fibres.
4. The hybrid component according to claim 1, wherein material A is
selected from the group consisting of plastics, metals and fibre
composite materials.
5. The hybrid component according to claim 1, wherein the hybrid
component further comprises at least one material C selected from
the group consisting of plastics, metals, ceramic compositions,
wood, glass, composite materials, textile fibres and prefabricated
products produced from textile fibres.
6. A process for producing a hybrid component according to claim 1,
wherein the adhesion promoter composition is at least partly
applied to or laid onto material A, material B or both materials,
and materials A and B are bonded to one another.
7. The process according to claim 6, wherein a material C is
applied to or laid onto the hybrid component and material C is
bonded to the hybrid component.
8. The process according to claim 6, wherein a material C is bonded
to materials A and B together.
9. A structural component, lightweight component, component having
a surface function or protective function, or as decorative
component that comprises the hybrid component according to claim
1.
10. A method for producing a hybrid component according to claim 1
comprising applying at least one copolyamide-based hotmelt adhesive
as an adhesion promoter between a fibre composite material B and a
material A.
Description
[0001] The present invention relates to hybrid components, to
processes for production thereof and to the use thereof, and to the
use of adhesion promoter compositions.
[0002] Prior art hybrid components made from plastic and metal are
components used inter alia in motor vehicle construction and in
aircraft construction and also in electronics and electrical
engineering and also in the sport and lifestyle sectors in the
field of loadbearing parts and of parts that absorb forces, or as
part of the housing, for example for decorative purposes. A
particular feature of these is that they comprise local
reinforcement systems which give the component particular
mechanical properties and/or provide the possibility of functional
integration. A feature requiring particular emphasis is increased
component stiffness with additional weight reduction in comparison
with components hitherto used in a conventional mode of
construction.
[0003] The abovementioned application sectors increasingly use
hybrid components in order to reduce mass and at the same time
obtain optimized mechanical properties. The disadvantage of these
hybrid components is lack of, or inadequate, adhesion between metal
and plastic. Mechanical methods have therefore hitherto been used
to anchor the plastic to the metal.
[0004] Adhesion between metal and plastic can be improved by using
adhesion promoters. EP-A-1808468 and EP-A-2435246 disclose hybrid
components where the bond between metal and plastic uses hotmelt
adhesives in the form of copolyamide-based adhesion promoters
additionally comprising isocyanate groups and epoxy groups.
[0005] The continuing trend toward ever more lightweight structures
with equal or increased stiffness is leading to enhanced use of
thermoplastic fibre composite materials ("composites") within the
established plastic and/or metal structures.
[0006] In the case of fibre composite materials too, typically
form- and/or force-fitting connecting elements are made, for
example through-moulding points, insert moulding operations,
rivets, screws, "hedgehog" structures (for example T-Igel) etc.
[0007] The disadvantage of form- and/or force-fitting connecting
elements with respect to cohesive elements is the local limitation
on introduction of forces. Moreover, the required apertures in the
material affect absorption and distribution of forces.
[0008] Improved transmission and introduction of forces between
materials can be accomplished through cohesive bonds. It is
possible here to dispense with apertures in the material, which
weaken it, as necessary, for example, for form-fitting. However, a
cohesive bond between fibre composite materials and a plastic can
be established in injection moulding only in the case of like or
particularly compatible material combinations, which greatly limits
the selection of potential bonding partners. The is quality of the
bond depends crucially on the process conditions used (temperature,
time and pressure). Alternatively, a cohesive bond can be created
by welding or by means of a suitable adhesion promoter, for example
one based on polyurethane.
[0009] The problem addressed by the present invention was therefore
that of providing a hybrid component which comprises at least one
fibre composite material and is obtainable by cohesive bonding. In
this way, a particularly high adhesion should be achieved between
the respective, typically unlike materials. A hybrid component
having increased stiffness and/or reduced weight combined with
adhesion at least to nearly as high a level as compared with the
known hybrid components composed of metal and plastic was to be
obtained.
[0010] A bond between like partners is, for example, a bond between
nylon-12 and nylon-12 or steel and steel. By contrast, a bond
between unlike partners is, for example, the combinations of steel
and aluminium, steel and nylon-6 or nylon-12 and nylon-6. The terms
"unlike" and "like" are known to those skilled in the art.
[0011] It has been found that, surprisingly, coating with an
adhesion promoter composition leads to the possibility of cohesive
bonding of the fibre composite material to materials A to obtain a
hybrid component.
[0012] The present invention accordingly provides a hybrid
component comprising at least one fibre composite material as
material B and at least one material A, wherein material A is
selected from plastics, metals, ceramic compositions, wood, glass,
composite materials, textile fibres and prefabricated products
produced from textile fibres. The materials are bonded to one
another by at least one coating of an adhesion promoter
composition, wherein the composition comprises at least one
copolyamide-based hotmelt adhesive.
[0013] Fibre composite materials as material B and materials A are
referred to collectively hereinafter as materials.
[0014] Composite materials may include particulate composite
materials, fibre composite materials, laminate composite materials
(laminates), penetration composite materials and structural
composite materials. The materials in a material composite may be
polymeric, metallic, ceramic or organic.
[0015] Particulate composite materials are regarded as being, for
example, grinding discs (ceramic particles in a polymeric or glass
matrix), cemented carbide (ceramic particles in a metallic matrix),
ceramic composites (ceramic particles in a ceramic matrix),
fibreboards (organic particles in polymeric matrix), concrete
(ceramic particles in ceramic matrix) or polymer concrete (mineral
particles in polymeric matrix).
[0016] The matrix is the material in the composite material into
which the other constituents are embedded.
[0017] Fibre composite materials in the context of the invention
are, for example, glass fibre-reinforced glass, metal matrix
composites (MMCs), fibre cement, carbon fibre-reinforced silicon
carbide, fibre-plastic composites or fibre-ceramic composites
(CMCs). Preferred fibre composite materials both as material A and
as material B are fibre-plastic composites.
[0018] The laminate composite materials include composite sheets,
composite tubes, TiGr composites (material composed of titanium,
carbon fibres and epoxy resin), glass fibre-reinforced aluminium,
sandwich sheets with a honeycomb core, bimetals and Hylites.
[0019] Preferred materials A are plastics, metals and fibre
composite materials. Accordingly, hybrid components are preferably
composed of fibre composite material, more preferably fibre-plastic
composites, as material B and a material A selected from plastics,
metals and fibre composite materials, more preferably fibre-plastic
composites.
[0020] If both material A and material B are a fibre-plastic
composite, material A may be the same as material B or
different.
[0021] The hybrid component of the invention, comprising the
adhesion promoter composition, material A and material B, may
additionally be bonded to one or more materials C which may be the
same as material A or different. The other materials C may have
been bonded to the hybrid component of the invention by means of a
form-fitting, force-fitting or cohesive bond, and it is optionally
possible here to use an adhesion promoter composition.
[0022] Material C may be selected from plastics, metals, ceramic
compositions, wood, glass, composite materials, textile fibres and
prefabricated products produced from textile fibres. Preferred
materials C are plastics, metals and fibre composite materials.
[0023] By appropriate preliminary tests, it is possible for the
person skilled in the art to determine whether an adhesion promoter
composition seems necessary for bonding of the hybrid component of
the invention to further materials, such that optimal adhesion
properties are obtained.
[0024] The invention further provides a process for producing an
above-described hybrid component. In this case, the adhesion
promoter composition is at least partly applied to or laid onto at
least one of materials A and/or B, and materials A and B are bonded
to one another. The adhesion promoter composition (also referred to
hereinafter as composition) can be applied to one of the materials
over the full area or part of the area.
[0025] To the extent that a material C is used for the production
of an extended hybrid component, it is possible to begin by
producing a hybrid component consisting of materials A and B.
Subsequently, material C can be applied or laid on analogously to
the methods for materials A and B and bonded to the hybrid
component composed of A and B. Alternatively, materials A, B and C
may be bonded together (in one step) for production of the extended
hybrid component.
[0026] During the production of the hybrid component or of the
extended hybrid component it is possible to combine various
manufacturing steps such as moulding or forming processes, or
machining, and to carry out these in a single process step
(integrated manufacture). If plastic as material B is to be bonded
to material A, preference is given to forming of the plastic and
moulding of material A.
[0027] The compositions may be applied or laid on as a film. The
application can be effected continuously or batchwise by means of
electrophoretic enamelling, electrostatic spray processes,
fluidized bed sintering, roll processes (for example coil coating),
casting, jet processes and spraying, bar coating, brush coating,
lamination, (hot) pressing, (co)extrusion or injection moulding,
preference being given here to spray processes and roll application
processes. The compositions here can be applied on one or both
sides, locally or over the entire area. The stoved layer
thicknesses (dry layer thicknesses) of the adhesion promoter
compositions may be from 10 to 1000 .mu.m, preferably 20 to 250
.mu.m, and more preferably 30 to 150 .mu.m. Preferred layer
thicknesses in roll processes are from 5 .mu.m to 250 .mu.m,
especially 10 .mu.m to 50 .mu.m.
[0028] The material with the applied adhesion promoter composition
can be crosslinked and/or dried thermally, advantageous object
temperatures here being from 120.degree. C. to 240.degree. C.,
preferably 150.degree. C. to 225.degree. C., more preferably
175.degree. C. to 200.degree. C., for a period of from 0.5 min to
30 min, preferably 1 min to 20 min, more preferably 3 min to 10
min. The person skilled in the art can determine suitable
time/temperature conditions via preliminary tests. In roll
processes, preferred peak metal temperatures (PMT) are from
180.degree. C. to 240.degree. C. The person skilled in the art will
set the system or belt speed accordingly so as to achieve the
PMT.
[0029] The compositions are thus cured thermally.
[0030] Preferred hybrid components are obtained as follows: [0031]
A) The metal (material A) coated with the composition is bonded to
the fibre composite material (material B) or [0032] B) the fibre
composite material (material B) coated with the composition is
bonded to the plastic (material A) or [0033] C) the fibre composite
material (material B) coated with the composition is bonded to the
metal (material A) or [0034] D) the plastic (material A) coated
with the composition is bonded to the fibre composite material
(material B) or [0035] E) the fibre composite material (material A)
coated with the composition is bonded to a fibre composite material
(material B).
[0036] In variants A to E, fibre-plastic composites are
particularly preferred fibre composite materials. The preferred
hybrid components can be extended to include the materials C.
Variant A
[0037] The fibre composite material (for the composite composed of
fibre composite material and metal) may be applied to the metal,
for example, by extrusion, pultrusion, pressing, laminating, tape
laying, winding, injection moulding or direct melt impregnation,
and the fibre composite material may be bonded physically and/or
chemically to the metal. Contact of the fibre composite material
with the coated metal surface produces a cohesive bond and adhesion
between the components.
Variant B
[0038] The plastic (for the composite composed of fibre composite
material and plastic) may be applied to the fibre composite
material, for example, by an injection moulding process including
injection-compression moulding, by extrusion or by hot pressing,
and the fibre composite material may be bonded physically and/or
chemically to the plastic. Injection moulding technology is
preferably used to inject the plastic. For this purpose, the coated
fibre composite material part is inserted into the injection mould
and, after closing of the mould, is coated in the mould with the
plastic. Contact of the plastics melt with the coated fibre
composite material surface produces a cohesive bond and adhesion
between the components. The cohesively bonded component can then be
demoulded from the injection mould and subjected to further
processing or further mechanical operations.
Variant C
[0039] The metal (for the composite composed of fibre composite
material and metal) may be applied to the fibre composite material,
for example, by pressing, and the metal may be bonded to the fibre
composite material and/or bonded by chemical means. Contact of the
metal with the coated fibre composite material surface produces a
cohesive bond and adhesion between the components.
Variant D
[0040] The fibre composite material (for the composite composed of
fibre composite material and plastic) may be applied to the
plastic, for example, by extrusion, pultrusion, pressing,
laminating, tape laying, winding, injection moulding or direct melt
impregnation, and the fibre composite material may be bonded
physically and/or chemically to the plastic. Contact of the fibre
composite material with the coated plastic surface produces a
cohesive bond and adhesion between the components.
Variant E
[0041] One fibre composite material (for the composite composed of
fibre composite material and fibre composite material) may be
applied to the other fibre composite material, for example, by
extrusion, pultrusion, pressing, laminating, tape laying, winding,
injection m moulding or direct melt impregnation, and the two fibre
composite materials may be bonded physically and/or chemically.
Contact of one fibre composite material with the coated surface of
the other fibre composite material produces a cohesive bond and
adhesion between the components.
[0042] By virtue of the cohesive bond between the fibre composite
material as material B and material A it is possible to achieve
markedly advantageous force distribution and consequently to
produce a stiffer overall design of the hybrid component. In
addition, it is possible to save on costs and time in the
production.
[0043] Another advantage resulting by virtue of the cohesive bond
is weight reduction, since the improved transmission and
introduction of forces enables use of a smaller amount of plastic
or metal than in the case of form- or force-fitting bonds.
[0044] The combination of material B and material A and optionally
material C can then be subjected to a heat treatment for from 2 min
to 90 min, preferably from 5 min to 60 min, at from 120.degree. C.
to 240.degree. C., in order to increase bond strength and degree of
crosslinking. Hybrid components produced in this way have a durable
bond between the material coated with the composition and the
plastic or the fibre composite material, and exhibit high
mechanical and dynamic strength.
[0045] The invention further provides for the use of the hybrid
components of the invention as structural components or lightweight
components, or components having surface or protective functions.
The hybrid components may additionally assume decorative
functions.
[0046] The resultant hybrid components may be used as a
semi-finished product in the form of sheets or profiles for further
processing to give components. These include, for example, sandwich
sheets comprising at least three layers, of which the two outer
layers may be the same or different. Sandwich sheets may have, for
example, a fibre composite material core and outer metal
layers.
[0047] The hybrid components may be used in mechanical engineering
and plant construction, as seats in motor vehicles or aircraft,
shock absorbers, bodywork and chassis parts such as front-end
bearings, door, roof, floor or chassis components, constituent
parts of boats such as the hull or interior fitting, decorative
strips in motor vehicles or aircraft, housings or components for
electronic or electrotechnical devices, for example computers or
telephones, bicycle components such as forks, frames, brakes,
gears, ortheses, prostheses, joints, constituent parts of robots
such as robot arms, handling and transport systems, receivers for
bearing seats, spectacle frames, helmets or seat-securing,
seat-reinforcing or seat-panelling elements in motor vehicle and
aircraft construction, pressure vessels such as gas bottles,
support structures for vessels, frames, oil tanks, electronic
components such as antennas or battery housing, components for
energy generation such as photovoltaic or wind energy plants,
machine elements such as cogs or racks. Equally suitable
application sectors are frames, profiles, facade elements or guide
strips for windows and doors in the field of house construction and
architecture.
[0048] The invention further provides for the use of a composition
comprising at least one copolyamide-based hotmelt adhesive as
adhesion promoter between a fibre composite material as material B
and a material A for production of a hybrid component of the
invention. In addition, the composition may be used for production
of an extended hybrid component.
Fibre Composite Material
[0049] A fibre composite material is a multiphase or mixed material
consisting of fibres and a matrix as main components. As a result
of interactions between the two components, this material has
higher-quality properties than either of the two components
involved individually.
[0050] Suitable fibres are, for example, inorganic fibres such as
basalt fibres, boron fibres, glass fibres, ceramic fibres or silica
fibres, metallic fibres such as steel fibres, organic fibres such
as aramid fibres, carbon fibres, polyester fibres, nylon fibres,
polyethylene fibres, polymethylmethacrylate fibres, polyimide
fibres or fibres made from polyaryl ether ketones, and natural
fibres such as wood fibres, flax fibres, hemp fibres or subtropical
and tropical fibres such as jute fibres, kenaf fibres, ramie fibres
or sisal fibres. Preferred fibres are selected from glass fibres
and carbon fibres.
[0051] The fibres can be divided as follows according to fibre
length:
[0052] The length of short fibres is about 0.1 to 1 mm. The term
long fibres is used for fibres with length about 1 to 50 mm. The
term continuous fibres is used when the length is more than 50 mm.
Length is defined as the number-average fibre length in the matrix
after production of the fibre composite material in accordance with
DIN ISO 22314.
[0053] Preferably, long or continuous fibres are used in material
B. More preferably, the fibres have a length of at least 1.5 mm,
more preferably at least 5 mm and most preferably at least 10 mm.
These materials B are most preferred for hybrid components or
extended hybrid components having metals as material A.
[0054] The dry fibres (without matrix) be be present in the form of
rovings or semi-finished products (semi-finished fibre products).
The semi-finished products can be produced, for example, by
weaving, braiding or stitching. The semi-finished fibre products
include, for example, woven fabrics, laid scrims including
multiaxial laid scrims, knitted fabrics, braids, mats, nonwoven
fabrics, fine-cut fabrics or spacer fabrics.
[0055] Rovings refer to a bundle, strand or multifilament yarn
composed of filaments (continuous fibres) arranged in parallel. The
filaments most commonly combined to form rovings are those made
from glass, aramid or carbon. The cross section of a roving is
usually elliptical or rectangular. However, there are also rovings
with a slight protective twist (e.g. 10 twists/m), which makes the
cross section rounder.
[0056] The fibre composite materials can be subdivided into
fibre-plastic composites in which polymers are used as matrix, and
other fibre composite materials.
[0057] The matrix of the other fibre composite materials is
typically selected from metals, ceramics and carbon.
[0058] Matrices selected for the fibre-plastic composites are
typically polymers such as thermosets, elastomers and
thermoplastics, preference being given to thermoplastics.
[0059] The polymers may comprise reinforcers or fillers such as
talc or chalk. The plastics may further comprise additives, for
example stabilizers, impact modifiers, flow aids and pigments.
[0060] Particularly preferred thermoplastics are, for example,
polybutylene terephthalates, polyaryl ether ketones such as
polyether ether ketones, polyolefins such as polypropylene,
polyphenylene sulphide, polycarbonates, polyetherimides,
polyurethanes, aliphatic or semiaromatic polyamides, plastics
mixtures comprising polyamides, styrene polymers such as
acrylonitrile-butadiene-styrene, polyalkyl(meth)acrylates such as
polymethylmethacrylate, and also mixtures of the abovementioned
plastics. Mixtures of polycarbonates and
acrylonitrile-butadiene-styrene are likewise suitable. Preference
is given to aliphatic or semiaromatic polyamides, plastics mixtures
comprising polyamides, polybutylene terephthalates, polyolefins,
and also mixtures of the abovementioned polymers, particular
preference being given here to polyamides.
[0061] Preferred polyamides (PA) are selected from the group
consisting of nylon-6, nylon-6,6, nylon-6,10, nylon-6,12,
nylon-6,13, nylon-6,14, nylon-10,6, nylon-10,10, nylon-10,12,
nylon-12,12, nylon-11, nylon-12, polyphthalamides, optically
transparent polyamides and mixtures based on these polyamides.
Particularly preferred polyamides are selected from nylon-6,
nylon-6,6, nylon-12, polyphthalamides, optically transparent
polyamides and mixtures of these. Suitable polyamides are available
by way of example as VESTAMID LX9012 from Evonik Industries.
[0062] Optically transparent polyamides include microcrystalline
polyamides comprising linear aliphatic dicarboxylic acids and
cycloaliphatic diamines, amorphous polyamides comprising linear
aliphatic dicarboxylic acids and cycloaliphatic diamines and
optionally lactams or aminocarboxylic acids, amorphous polyamides
comprising terephthalic acid and cycloaliphatic or branched
aliphatic diamines and optionally lactams or aminocarboxylic acids,
or amorphous polyamides comprising isophthalic acid and
cycloaliphatic or linear or branched aliphatic diamines and
optionally lactams or aminocarboxylic acids. Suitable optically
transparent polyamides are by way of example amides made of
dodecanedioic acid and of an isomer mixture of
4,4'-bis(aminocyclohexyl)methane, of terephthalic acid and of the
isomer mixture of 2,2,4- and 2,4,4-trimethylhexamethylenediamine,
of dodecanedioic acid and of the isomer mixture of
3,3'-dimethyl-4,4'-bis(aminocyclohexyl)methane, of laurolactam,
isophthalic acid and of the isomer mixture of
3,3'-dimethyl-4,4'-bis(aminocyclohexyl)methane or of
tetradecanedioic acid and of the isomer mixture of
3,3'-dimethyl-4,4'-bis(aminocyclohexyl)methane. Polyamides of this
type are described by way of example in DE-A-102007062063 or
WO-A-2008025729. Optically transparent polyamides are available by
way of example with trade names Trogamid (Evonik, Germany),
Grilamid (EMS-Chemie, Germany), or Durethan (Lanxess, Germany).
[0063] The fibre composite materials further comprise
thermoplastics with homogeneous reinforcement (polymer fibres in
polymer matrix of the same composition).
[0064] The aforementioned thermoplastic matrix polymers may
additionally be crosslinked. For example, the crosslinking can be
effected during the production of the fibre composite material or
in a subsequent step.
[0065] Suitable thermosets are, for example, epoxy resins,
unsaturated polyester resins, vinyl ester resins, phenacrylate
resins, phenol resins, methacrylate resins or isocyanate resins
(cf. G. Ehrenstein: Faserverbund-Kunststoffe [Fibre Composite
Plastics], Hanser-Verlag, 2nd edition 2006, page 53 ff., ISBN
978-3-446-22716-3).
[0066] Particularly preferred fibre composite materials are
selected from carbon fibre-reinforced plastics and glass
fibre-reinforced plastics.
[0067] The fibres can have orientation in the matrix or no
orientation, preferably having orientation. Examples of fibre
composite materials comprising oriented fibres are UD laid scrims,
UD tapes (UD=unidirectional) and woven fabrics. Unoriented fibres
are present by way of example in nonwovens.
[0068] The fibre-plastic composites can moreover take the form of
semifinished fibre-matrix products. These may have been
preimpregnated. Preimpregnated semi-finished fibre-matrix products
especially include thermoplastic and thermoset semi-finished
products. The preimpregnated semifinished fibre-matrix products may
take the form of sheets, of strips or of strands.
[0069] Among the semifinished thermoplastic products are by way of
example glass-mat-reinforced thermoplastics (GMT), or
long-fibre-reinforced thermoplastics (LFT) and thermoplastic
preimpregnated fibres (prepregs). Thermoplastic prepregs in the
form of sheets are also called organopanels (cf. Tagungsband zur
Fachtagung "Thermoplastische Faserverbundkunststoffe" [Proceedings
of the Conference on "Thermoplastic fibre composite materials"],
15.-16.05.2013 in Furth, Carl Hanser Verlag Munich 2013, ISBN
978-3-446-43864-4, pp. 5, 13 and 17).
[0070] Thermoset semi-finished products are, for example, sheet
moulding compounds (SMCs), bulk moulding compounds (BMCs) and
thermoset preimpregnated fibres (prepregs).
[0071] Before the application of material A, the fibre composite
material may be trimmed, formed or shaped. The forming process may
precede or follow the application of the adhesion promoter
composition.
[0072] The person skilled in the art is aware of the production of
fibre composite materials made of the fibres described above and of
the matrix.
Metals
[0073] Examples of suitable metals are iron-containing alloys such
as steel, aluminium, copper, magnesium, titanium, and also alloys
of the abovementioned metals. Preferred metals are steel, titanium,
aluminium, and also alloys of the abovementioned metals, particular
preference being given to steel and aluminium, and aluminium
alloys. The metals may also take the form of foam or can be present
in a honeycomb structure.
[0074] Preferred steels are unalloyed steels and stainless steels.
Steels with a protective coating are particularly preferred.
Suitable coatings are by way of example coatings made of zinc,
aluminium-silicon, aluminium-zinc, zinc-aluminium, zinc-iron or
zinc-magnesium, preference being given here to aluminium-silicon,
zinc-aluminium and zinc. The composition of the coatings is defined
by way of example in the brochure "Schmelztauchveredeltes Band and
Blech" [Hot-dip-coated Strip and Sheet] from the Steel Information
Centre in the Stahl-Zentrum, Dusseldorf, Germany, 2010 Edition.
[0075] Before the application of the fibre composite material
(material B), the metal may be trimmed, formed or shaped. The
forming process can take place before or after the application of
the adhesion promoter composition.
[0076] Before application of the adhesion promoter compositions, it
is possible to apply a conversion coat to all or some of the
surface of the metal, in order to pretreat the surface. The metal
may be cleaned before the pretreatment, or can already have
metallic protective coatings. The metal cleaning process is known
to the person skilled in the art.
[0077] The pretreatment may use converting agents. The converting
agents are usually used in the form of aqueous solutions.
Converting agents that can be used are commercially available
passivating agents and products for conversion treatment, for
example zinc phosphating agents, iron phosphating agents, and also
phosphoric acid solutions comprising titanates or zirconates. From
a technical point of view it is likewise possible to use chromating
agents, but these are less preferred because they are hazardous to
health.
[0078] It is moreover possible to obtain the conversion coat by
flame pyrolysis deposition of amorphous silicate on the surface of
the metal. The surface to be treated is passed through the
oxidizing region of a gas flame into which a silicon-containing
substance, the precursor, has been dosed. This is consumed by
combustion, and the residue deposits in the form of amorphous
silicate as firmly adhering layer in layer thicknesses of about 20
to 40 nm on the surface.
[0079] Treatment of a surface is achieved by using an operating gas
to produce a plasma jet or a combustion gas to produce a flame jet,
this being used to coat the surface, where at least one precursor
material is introduced into the operating gas and/or into the
plasma jet or into the combustion gas and/or into the flame jet,
and is reacted in the plasma jet or flame jet, where at least one
reaction product of at least one of the precursors is deposited on
the surface and/or on at least one layer arranged on the surface. A
process of this type is described by way of example in
DE-A-102009042103.
Plastic
[0080] The plastic can be applied to material B in a known manner,
for example by injection moulding, pressing, laminating, insert
moulding or (co-)extrusion, in which case the material should
already have been coated with the composition. Injection moulding
technology is preferably used to inject the plastic. Material B may
have been subjected to preconditioning in the range from 50.degree.
C. to 250.degree. C. in order to raise the temperature in the
region of contact with the plastic, for example in the case of
in-mould coating or in the case of co-extrusion, for good bonding
between the adhesion promoter and the plastic.
[0081] Alternatively, the plastic may already be present,
optionally having been coated with the composition, and may then be
bonded to material B.
[0082] Suitable plastics comprise by way of example polybutylene
terephthalates, polyolefins, polyetherimides, polycarbonates,
polyurethanes, aliphatic or semiaromatic polyamides, plastics
mixtures comprising polyamides, styrene polymers such as
acrylonitrile-butadiene-styrene, polyalkyl(meth)acrylates such as
polymethylmethacrylate, polymethacrylimide (for example Rohacell
from Evonik, Germany), and also mixtures of the abovementioned
plastics. Mixtures of polycarbonates,
acrylonitrile-butadiene-styrene or polyether-block-amides are
likewise suitable. Preference is given to aliphatic or semiaromatic
polyamides, plastics mixtures comprising polyamides, polybutylene
terephthalates, polyolefins, and also mixtures of the
abovementioned plastics, particular preference being given here to
polyamides. The plastics can comprise reinforcement (reinforcing
materials), preference being given here to glass fibre-reinforced
(GF) or carbon fibre-reinforced (CF) plastics. The plastics can
moreover comprise fillers such as talc powder or chalk. The
plastics may further comprise additives, for example stabilizers,
impact modifiers, flow aids and pigments. The reinforcers are
preferably distributed randomly in their matrix. In addition, the
reinforcers preferably have a length of less than 5 mm, preferably
less than 1 mm.
[0083] Preferred polyamides are selected from the group consisting
of nylon-6, nylon-6,6, nylon-6,10, nylon-6,12, nylon-6,13,
nylon-6,14, nylon-10,6, nylon-10,10, nylon-10,12, nylon-12,12,
nylon-11, nylon-12, polyphthalamides and mixtures based on these
polyamides. Particularly preferred polyamides are selected from
nylon-6, nylon-6,6, nylon-6,10, nylon-10,10, and mixtures of these.
Suitable polyamides are available by way of example as VESTAMID
LX9012 or LGF30 from Evonik Industries.
Adhesion Promoter Composition
[0084] The adhesion promoter composition comprises at least one
copolyamide-based hotmelt adhesive. The adhesion promoter
composition can be present in solution or in dispersion, or in the
form of solid.
[0085] The hotmelt adhesive comprises at least one copolyamide. The
copolyamide can be produced from amide monomers and from
comonomers. The comonomers are preferably used to obtain
copolyamides with a melting point from 95.degree. C. to 175.degree.
C.
[0086] The amide monomers are preferably selected from the group
consisting of laurolactam, aminoundecanoic acid and mixtures
thereof. Particular preference is given to copolyamides based on
laurolactam.
[0087] The comonomers are preferably selected from aliphatic or
cycloaliphatic diamines, aliphatic or cycloaliphatic dicarboxylic
acids, lactams and mixtures thereof. The comonomers preferably
comprise, mutually independently, from 4 to 18 carbon atoms.
Suitable dicarboxylic acids are by way of example adipic acid,
sebacic acid and dodecanedioic acid. Suitable diamines are by way
of example hexamethylenediamine, decamethylenediamine and
dodecamethylenediamine. Lactams such as caprolactam can likewise be
used as comonomer.
[0088] Preferred comonomers are caprolactam and a polymer made with
adipic acid and hexamethylenediamine, preferably in a ratio by mass
of 1:1.
[0089] An excess of amine groups in the diamines gives copolyamides
having reactive amino end groups.
[0090] The amine numbers of the copolyamides are preferably from 75
to 400 mmol/kg.
[0091] The weight-average molar mass of the copolyamides is
preferably in the range from 15 000 to 70 000 g/mol (measured by
means of gel permeation chromatography (GPC) against a polystyrene
standard). The relative solution viscosity is preferably from 1.2
to 1.8 (determined in accordance with ISO 307).
[0092] The copolyamides and the hotmelt adhesive can be used in the
compositions in solution, in dispersion or in powder form,
preference being given here to the powder form. A suitable solvent
is by way of example m-cresol.
[0093] The powder form can by way of example be obtained by
milling, the grain diameter here with preference being <200
.mu.m, more preferably <100 .mu.m and with particular preference
<70 .mu.m (sieve analysis).
[0094] In one preferred embodiment of the invention, at least one
epoxy component and at least one blocked polyisocyanate have been
added to the copolyamide, as other constituents of the hotmelt
adhesive.
[0095] The epoxy index of the epoxy component is typically from 1
to 2 eq/kg. The epoxy equivalent weight of the epoxy resins used
can be from 400 to 4000 g/mol, preferably from 700 to 3000 g/mol
and with preference from 875 to 1000 g/mol (determined in
accordance with SMS 2026).
[0096] The content of OH groups in suitable epoxy resins is
preferably from 2000 to 4500 mmol/kg, with preference from 2300 to
4000 mmol/kg (method of SMS 2367). Compounds based on diols or on
polyols or dicarboxylic acids can by way of example be used as
epoxy component, preference being given here to diols and
particular preference being given here to corresponding phenol-diol
derivatives. Very particularly preferred phenol-diol derivatives
are bisphenols, in particular bisphenol A. The epoxy component is
usually obtained by reaction with epichlorohydrin.
[0097] The density of suitable epoxy resins is from 1 to 1.3 kg/L,
preferably from 1.15 to 1.25 kg/L (25.degree. C.; determined in
accordance with ASTM D792). The glass transition temperature (Tg)
can be from 20.degree. C. to 100.degree. C., preferably from
25.degree. C. to 90.degree. C., with preference from 40.degree. C.
to 60.degree. C. and with particular preference from 45 to
55.degree. C. (determined in accordance with ASTM D3418). The
melting range is usually in the range from 45.degree. C. to
150.degree. C. (in accordance with DIN 53181). Suitable epoxy
resins are obtainable by way of example as EPIKOTE resin, for
example EPIKOTE Resin 1001 or 1009 from Hexion Specialty Chemicals,
Inc.
[0098] The hotmelt adhesive preferably comprises a proportion of
from 2.5 to 10% by weight of the epoxy component, more preferably
from 4 to 6% by weight, based in each case on the total weight of
the hotmelt adhesive.
[0099] The hotmelt adhesive may further comprise hardeners such as
dicyandiamide (DCD), preferably in proportions of from 3 to 6% by
weight, based on the total weight of the epoxy resin. To accelerate
curing, urea derivatives such as monuron or fenuron can be added,
and it is thus possible to lower the curing temperatures and/or
shorten the curing times.
[0100] The proportion of blocked polyisocyanate is preferably from
2.5 to 15% by weight, more preferably from 4 to 6% by weight, based
in each case on the total weight of the hotmelt adhesive.
[0101] The blocked polyisocyanate component can be aromatic,
aliphatic or cycloaliphatic, preference being given here to
aliphatic or cycloaliphatic polyisocyanates. Blocking agents for
isocyanates such as oximes, phenols or caprolactam are known to the
person skilled in the art. It is preferable that, for blocking
purposes, the polyisocyanate component takes the form of uretdione.
Typical examples are marketed as VESTAGON by Evonik Industries,
Germany.
[0102] The adhesion promoter composition can comprise
self-crosslinking or externally crosslinking binders (in relation
to the term "Bindemittel" [Binders] cf. Rompp Lexikon Lacke und
Druckfarben [Rompp's Encyclopaedia of Coating Materials and
Printing Inks], Georg Thieme Verlag, Stuttgart, N.Y., 1998,
Bindemittel, pp. 73 and 74). For the purposes of the present
invention, the term "self-crosslinking" denotes the property of a
binder of entering into crosslinking reactions with itself. A
precondition for this is that complementary reactive functional
groups are present in the binders and react with one another and
thus lead to crosslinking. Or else the binders comprise reactive
functional groups which react "with themselves". Binder systems
described as externally crosslinking are in contrast those in which
one type of the complementary reactive functional groups is present
in the binder and the other type is present in a hardener or
crosslinking agent. For additional information here, reference is
made to Rompp Lexikon Lacke und Druckfarben, Georg Thieme Verlag,
Stuttgart, N.Y., 1998, Hartung [Curing], pp. 274 to 276, in
particular lower part of p. 275.
[0103] The adhesion promoter composition can moreover comprise
electrically conductive substances selected from graphite, carbon
black, zinc dust and mixtures of these substances, thus giving
electrically conductive adhesion promoter compositions.
[0104] The metal-plastic composite comprising coatings of
electrically conductive adhesion promoter compositions may be
provided with a cathodic electrocoat (CEC).
[0105] The adhesion promoter compositions can moreover comprise
colorants, preferably pigments. Functional pigments such as
corrosion-protection pigments can moreover be present.
[0106] The adhesion promoter composition may further comprise
functionalized polyolefins in order to improve adhesion to
polyolefins. Compositions of this kind are described by way of
example in WO 2010/136241.
[0107] Suitable hotmelt adhesives are available by way of example
as VESTAMELT from Evonik Industries AG, Germany. Examples include
X1027-P1, X1038-P1, X1316 P1 and X1333-P1.
[0108] Other materials that can be present alongside the hotmelt
adhesive are graft copolymers made of polyamine and of
polyamide-forming monomers such as lactams and/or
.omega.-aminocarboxylic acids, as described in EP1065236A2:
[0109] The concentration of amino groups in the graft copolymer is
preferably in the range from 100 to 2500 mmol/kg.
[0110] Examples of substance classes that can be used as polyamine
are the following: [0111] polyvinylamines (Rompp Chemie Lexikon,
[Rompp's Chemical Encyclopaedia] 9th Edn. Vol. 6, p. 4921, Georg
Thieme Verlag Stuttgart 1992); [0112] polyamines that are produced
from alternating polyketones (DE-A 196 54 058); [0113] dendrimers,
for example [0114]
((H.sub.2N--(CH.sub.2).sub.3).sub.2N--(CH.sub.2).sub.3).sub.2--N(CH.sub.2-
).sub.2--N((CH.sub.2).sub.2--N((CH.sub.2).sub.3--NH.sub.2).sub.2).sub.2
(DE-A-196 54 179) or [0115] tris(2-aminoethyl)amine,
N,N-bis(2-aminoethyl)-N',N'-bis[2-[bis(2-aminoethyl)amino]ethyl]-1,2-etha-
nediamine, [0116]
3,15-bis(2-aminoethyl)-6,12-bis[2-[bis(2-aminoethyl)amino]ethyl]-9-[2-[bi-
s[2-bis(2-aminoethyl)amino]ethyl]amino]ethyl]-3,6,9,12,15-pentaazaheptadec-
ane-1,17-diamine (J. M. Warakomski, Chem. Mat. 1992, 4, 1000-1004);
[0117] linear polyethyleneimines which can be produced by
polymerization of 4,5-dihydro-1,3-oxazoles followed by hydrolysis
(Houben-Weyl, Methoden der Organischen Chemie [Methods for Organic
Chemistry]), vol. E20, pp. 1482-1487, Georg Thieme Verlag
Stuttgart, 1987); [0118] branched polyethyleneimines which are
obtainable by polymerization of aziridines (Houben-Weyl, Methoden
der Organischen Chemie), vol. E20, pp. 1482-1487, Georg Thieme
Verlag Stuttgart, 1987) and which generally have the following
amino group distribution: [0119] from 25 to 46% of primary amino
groups, [0120] from 30 to 45% of secondary amino groups and [0121]
from 16 to 40% of tertiary amino groups.
[0122] In the preferred case the number-average molar mass M.sub.n
of the polyamine is at most 20 000 g/mol, particularly at most 10
000 g/mol and in particular at most 5000 g/mol.
[0123] Lactams and .omega.-aminocarboxylic acids which can be used
as polyamide-forming monomers comprise from 4 to 19 carbon atoms,
in particular from 6 to 12. It is particularly preferable to use
.epsilon.-caprolactam and laurolactam or the relevant
.omega.-aminocarboxylic acids. The molar ratio of C12 to C6 unit is
preferably from 4:1 to 1:4. The ratio by mass of hotmelt adhesive
to graft copolymer is preferably from 19:1 to 1:1.
[0124] In the simplest case, the functionalized polyolefin is
polypropylene-based. However,
ethylene/C.sub.3-C.sub.12-.alpha.-olefin copolymers are also
suitable. An example of a C.sub.3-C.sub.12-.alpha.-olefin used is
propene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene or
1-dodecene. The ethylene/C.sub.3-C.sub.12-.alpha.-olefin copolymers
can moreover also comprise up to at most 10% by weight of olefin
dienes such as ethylidenenorbornene or 1,4-hexadiene.
Functionalization is preferably provided by acid anhydride groups,
these being introduced in a known manner through thermal or
free-radical reactions of the main-chain polymer with an
unsaturated dicarboxylic anhydride or with an unsaturated
dicarboxylic acid. Examples of suitable reagents are maleic
anhydride and itaconic anhydride. The quantity grafted onto the
material in this method is from 0.1 to 4% by weight, based on the
total weight of the functionalized polyolefins, and another monomer
such as styrene can also be used here.
[0125] Maleic-acid-grafted polyolefins are widely used for
industrial applications, in particular for impact modifications or
as compatibilizers in blends and mechanically reinforced systems
(Polymer, 2001, 42, 3649-3655 and literature cited). The source
mentioned also describes by way of example the production of
functionalized polyolefins of this type.
[0126] A typical functionalized polyolefin is the
polypropylene-based, acid anhydride-grafted material Admer QB 520 E
(Mitsui Chemicals). It is also possible in principle to use
maleic-acid-grafted polypropylenes from Kometra (e.g. SCONA TPPP
8012), these being more free-flowing.
[0127] Another possible functionalization method consists in the
mixing, in the melt, of unfunctionalized polyolefins with reactive
compatibilizers which comprise epoxy or carboxylic anhydride
groups. Typical examples are copolymers composed of ethylene and of
one or more unreactive acrylic monomers with maleic anhydride or
glycidyl methacrylate. Lotader AX8900 (Arkema) is a typical
representative material having glycidyl methacrylate units.
[0128] The ratio of polyamide component to polyolefin component is
from 9:1 to 2:3.
[0129] The present invention is explained in more detail below with
reference to examples. Alternative embodiments of the present
invention are obtainable analogously.
EXAMPLES
A) Hybrid Component Composed of Fibre Composite Material and
Metal
[0130] 1. Structure: Metal--Adhesion Promoter Coating--Fibre
Composite Material--Plastic (Extended Hybrid Component)
[0131] Unpretreated metal sheets (sheet thickness 1.5 mm) of ZSTE
800 steel to DIN EN 10142 were phosphated with converting agent.
Granodine 958 A from Henkel, Germany was used as converting agent,
comprising inter alia phosphoric acid and zinc
bis(dihydrogenphosphate), and Deoxylyte 54NC was used for
post-passivation.
[0132] The conversion solution was applied in accordance with
manufacturer's instructions by means of immersion into the
solutions and drying of the layers, and then the metal samples were
coated with an adhesion promoter composition. The composition
applied comprised [0133] H1: Solvent-containing spray coating
comprising about 30% by weight of a copolyamide-based hotmelt
adhesive comprising an epoxy component and a blocked polyisocyanate
and [0134] H2: Copolyamide-based hotmelt adhesive (Vestamelt
X1333-P1 from Evonik) comprising an epoxy component and a blocked
polyisocyanate in the form of powder coating.
[0135] The two compositions H1 and H2 comprise the same
copolyamide.
[0136] The coating system was applied by the spray process with a
layer thickness of from 50 to 70 .mu.m, and the powder coating was
applied electrostatically with a layer thickness of from 50 to 100
.mu.m. The spray coating was stoved for 5 min at 175.degree. C.,
and the powder coating was stoved for 5 min at 200.degree. C. For
this purpose, the coated metal sheets were placed in a preheated
autoclave (oven).
[0137] After the stoving procedure, guillotine shears were used to
cut the metal sheets into strips fitting the injection moulding
cavity with dimensions of 20.0 mm.times.50.0 mm (tolerance+0-0.2
mm).
[0138] Fibre composite material inserts used were continuous carbon
fibre-reinforced UD tapes having a matrix of nylon-12. The UD tapes
have a matrix of nylon-12. The UD tapes were likewise cut to size
with guillotine shears to dimensions fitting the injection moulding
cavity of about 20.0 mm.times.50.0 mm.
[0139] For production of the final hybrid components with and
without fibre composite inserts, the strips were then placed in a
temperature-controlled injection mould and in-mould-coated with a
thermoplastic. The fibre composite material insert was placed onto
the strip without fastening. The plastic component used was a
nylon-12 GF30 (VESTAMID L-GF30 from Evonik Industries AG,
Germany).
[0140] The plastic was processed in an Arburg V370 at a melt
temperature of 280.degree. C., a mould temperature of 120.degree.
C., and an injection rate of about 30 ccm/s. It was important here
to provide an injection delay of about 30 s, so that the metal
sheet strip and composite insert inserted could be preheated to
mould temperature, giving a favourable effect on adhesion. The
region of overlap between plastic and metal was about 20
mm.times.20 mm. The sample had a total length of about 100 mm. The
thickness of the insert-moulded plastic was about 6 mm, and in the
overlap region about 4 mm. After demoulding, the individual tensile
shear test samples were separated from the sprue.
[0141] The test samples thus produced were stored at 50% relative
humidity for at least 24 h at 23.degree. C. in order to ensure a
uniform state of conditioning. The test samples are then clamped
into a standard Zwick/Roell Z-020 tensile tester and tested with a
velocity of 5 mm/min at 23.degree. C. with a distance between the
clamps and the overlap region of about 15 mm/side.
TABLE-US-00001 Fibre composite Adhesion Example material promoter
Adhesion in MPa 1 without without 0 2 without H1 8.8 3 with without
0 4* with H1 8.5 5 without without 0 6 without H2 10.6 7 with
without 0 8* with H2 9.3 *inventive
[0142] The results show that it is possible through an adhesion
promoter coating of the metal component to achieve increased bond
strength between UD tape and metal in hybrid components compared to
systems without adhesion promoter. It is additionally demonstrated
that the use of the fibre composite material does not result in any
significant decrease in adhesion.
[0143] 2. Structure: Metal--Adhesion Promoter Coating--Fibre
Composite Material
[0144] Converting agents were used to phosphate or chromate metal
sheets (sheet thickness 1.0 mm) which have not been pretreated.
Granodine 958 A from Henkel, Germany, for galvanized steel sheets
DX56D Z140 to DIN EN 10346 (M1) was used as converting agent,
comprising inter alia phosphoric acid and zinc
bis(dihydrogenphosphate), and Deoxylyte 54NC was used for
post-passivation. For aluminium sheets AlMg3 EN AW-5754 H111 to DIN
EN 573-3 (M2), a conversion layer (chromation) of Alodine 1225 from
Henkel, Germany, was used.
[0145] The conversion solution was applied in accordance with
manufacturer's instructions by means of immersion into the
solutions and drying of the layers, and then the metal samples were
coated with an adhesion promoter composition. The composition
applied comprised: [0146] H1: Copolyamide-based hotmelt adhesive
(Vestamelt X1333-P1 from Evonik) comprising an epoxy component and
a blocked polyisocyanate in the form of powder coating and [0147]
H2: Solvent-containing spray coating comprising about 30% by weight
of a copolyamide-based hotmelt adhesive comprising an epoxy
component and a blocked polyisocyanate.
[0148] The two compositions H1 and H2 comprise the same
copolyamide.
[0149] The coating system was applied by the spray process with a
layer thickness of from 50 to 70 .mu.m, and the powder coating was
applied electrostatically with a layer thickness of from 50 to 100
.mu.m. The spray coating was stoved for 5 min at 175.degree. C.,
and the powder coating was stoved for 5 min at 200.degree. C. For
this purpose, the coated metal sheets were placed in a preheated
autoclave (oven).
[0150] After the stoving procedure, guillotine shears were used to
cut the metal sheets into strips appropriate for the pressing
operation with dimensions of about 60.0 mm.times.25.0 mm
(tolerance+0-0.2 mm).
[0151] Continuous fibre-reinforced fibre composite materials were
used as composite partner. The fibre composite materials were
likewise cut to size with guillotine shears to dimensions
appropriate for the pressing operation of about 60.0 mm.times.25.0
mm. The following fibre composite materials were used: [0152] C1:
Fibre composite material composed of VESTAMID L1600 (nylon-12) and
carbon fibre fabric having continuous fibres. The fabric has a
weight of about 285 g/m.sup.2 with an orientation of
0.degree./90.degree.. The fibre composite material sheets were
produced in a pressing process. [0153] C2: Fibre composite material
dynalite 102-FG290 (4)/45% type C (PA6) and glass fibre fabric
having continuous fibres from Bond-Laminates GmbH, Germany. The
fibre composite material has a fibre volume content of about 45% by
volume with an orientation of 0.degree./90.degree.. [0154] C3:
Fibre composite material composed of epoxy resin (Evonik product in
development) and carbon fibre fabric having continuous fibres. The
fabric has a weight of about 250 g/m.sup.2 with an orientation of
0.degree./90.degree.. The fibre composite material sheets were
produced in a pressing process. [0155] C4: Fibre composite material
composed of polyurethane resin (Evonik product in development) and
carbon fibre fabric having continuous fibres. The fabric has a
weight of about 200 g/m.sup.2 with an orientation of
0.degree./90.degree.. The fibre composite material sheets were
produced in a pressing process.
[0156] The bond between coated metal and fibre composite material
was obtained by a pressing operation in a hydraulic hot press
(manufacturer: Paul Weber, name: TEMPRESS). This is done by
inserting the coated metal sheet having dimensions of about
60.times.25.times.1 mm into a template in one half of the hot
press. A sheet of a fibre composite material having dimensions of
60.times.25.times.1 mm is positioned thereon. The half of the press
on the metal sheet side is heated to about 220.degree. C.
Thereafter, the fibre composite material and the coated metal sheet
are pressed at a pressure of about 32 bar with a hold time of about
5 min to give a composite body. The region of overlap between
plastic and metal was about 25 mm.times.25 mm. The sample had a
total length of about 130 mm.
[0157] The test samples thus produced were stored at 50% relative
humidity for at least 24 h at 23.degree. C. in order to ensure a
uniform state of conditioning. The test samples are then clamped
into a standard Zwick/Roell Z-020 tensile tester and tested with a
velocity of 5 mm/min at 23.degree. C. with a distance between the
clamps and the overlap region of about 15 mm/side.
TABLE-US-00002 Adhesion Fibre composite Adhesion Example Metal
promoter material in MPa 9 M1 without C1 2.8 10* M1 H1 C1 8.7 11*
M1 H2 C1 8.9 12 M2 without C1 3.6 13* M2 H1 C1 7.8 14* M2 H2 C1 7.8
15 M1 without C2 n.m. 16* M1 H1 C2 7.6 17* M1 H2 C2 8.5 18 M2
without C2 n.m. 19* M2 H1 C2 7.5 20* M2 H2 C2 8.0 21 M1 without C3
n.m. 22* M1 H1 C3 9.1 23 M2 without C3 n.m. 24* M2 H1 C3 8.6 25 M1
without C4 n.m. 26* M1 H1 C4 8.0 27 M2 without C4 n.m. 28* M2 H1 C4
6.0 *inventive; n.m. = not measurable (no adhesion)
B) Hybrid Component Composed of Fibre Composite Material and
Plastic
Structure: Fibre Composite Material--Adhesion Promoter--Plastic
[0158] For production of a composite body composed of a fibre
composite material and plastic by means of an adhesion promoter
composition, various fibre composite material sheets of thickness
1.0 mm were used: [0159] C1: Fibre composite material composed of
VESTAMID L1600 (nylon-12) and carbon fibre fabric having continuous
fibres. The fabric has a weight of about 285 g/m.sup.2 with an
orientation of 0.degree./90.degree.. The fibre composite material
sheets were produced in a pressing process. [0160] C2: Fibre
composite material composed of TROGAMID CX7323 (PACM 12) and glass
fibre fabric having continuous fibres. The fabric has a weight of
about 285 g/m.sup.2 with an orientation of 0.degree./90.degree..
The fibre composite material sheets were produced in a pressing
process. [0161] C3: Fibre composite material composed of epoxy
resin (Evonik product in development) and carbon fibre fabric
having continuous fibres. The fabric has a weight of about 250
g/m.sup.2 with an orientation of 0.degree./90.degree.. The fibre
composite material sheets were produced in a pressing process.
[0162] C4: dynalite fibre composite material (polybutylene
terephthalate PBT) and carbon fibre fabric having continuous fibres
from Bond-Laminates GmbH, Germany. The fibre composite material has
a fibre volume content of about 45% by volume with an orientation
of 0.degree./90.degree..
[0163] The sheets were each coated with an adhesion promoter
composition. The composition applied comprised [0164] H1:
Copolyamide-based hotmelt adhesive (Vestamelt X1333-P1 from Evonik)
comprising an epoxy component and a blocked polyisocyanate in the
form of powder coating and [0165] H2: Copolyamide-based hotmelt
adhesive (Vestamelt Z2366-P1 from Evonik) comprising an epoxy
component and a blocked polyisocyanate, and also a functionalized
polyolefin, as powder coating.
[0166] The two compositions H1 and H2 comprise the same
copolyamide.
[0167] The powder coating was applied electrostatically with a
layer thickness of 50-70 .mu.m and stoved at 160.degree. C. for 5
min. For this purpose, the coated metal sheets were placed in a
preheated autoclave (oven).
[0168] After the stoving procedure, guillotine shears were used to
cut the fibre composite material sheets into strips fitting the
injection moulding cavity with dimensions of 24.9 mm.times.59.8 mm
(tolerance.+-.0.2 mm).
[0169] For production of the final hybrid components, the fibre
composite material sheets were then placed in a
temperature-controlled injection mould and in-mould-coated with a
thermoplastic. The following moulding compositions were used as
plastics component: [0170] K1: Nylon-6 GF30 (Durethan BKV30 H2.0
from Lanxess, Germany) [0171] K2: Long glass fibre-reinforced
polypropylene LGF30 (CELSTRAN PP-GF30-05CNO1 from TICONA) [0172]
K3: PACM 12 (TROGAMID CX7323 from Evonik Industries AG) [0173] K4:
PA1010 GF65 (thermally stabilized polyamide reinforced with 65%
glass fibres from Evonik Industries AG)
[0174] The plastics were processed in an Arburg Allrounder 420 C
injection moulding machine at a melt temperature of 280.degree. C.,
a mould temperature of 80.degree. C. or 120.degree. C., and an
injection rate of about 30 ccm/s. For the polypropylene LGF30, a
melt temperature of 270.degree. C., a mould temperature of
70.degree. C. and then injection rate of about 30 ccm/s were used.
It was important here to provide an injection delay of about 15-30
s, so that the fibre composite material sheet inserted could be
preheated to mould temperature, giving a favourable effect on
adhesion. The region of overlap between plastic and fibre composite
material sheet was about 25 mm.times.25 mm. The sample had a total
length of about 130 mm. The thickness of the overmoulded plastic
was about 4 mm. After demoulding, the individual tensile shear test
samples were separated from the sprue.
[0175] The test samples thus produced were stored at 50% relative
humidity for at least 24 h at 23.degree. C. in order to ensure a
uniform state of conditioning. The test samples are then clamped
into a standard Zwick/Roell Z-020 tensile tester and tested with a
velocity of 5 mm/min at 23.degree. C. with a distance between the
clamps and the overlap region of about 25 mm/side.
TABLE-US-00003 Fibre Mould composite Adhesion temperature Adhesion
in Example Plastic material promoter in .degree. C. MPa 29 K1 C1
without 80 2.6 30 K1 C1 without 120 3.6 31* K1 C1 H1 80 9.3 32* K1
C1 H1 120 12.4 33 K2 C1 without 70 0.6 34* K2 C1 H2 70 5.2 35 K3 C2
without 80 n.r. 36* K3 C2 H1 80 2.3 37 K4 C3 without 80 material
fracture 38* K4 C3 H1 80 material fracture 39 K4 C4 without 80 n.m.
40* K4 C4 H1 80 5.8 *inventive; n.r.: no result; n.m.: not
measurable: (no adhesion)
[0176] The results show that the adhesion promoter variants can
achieve increased bond strength between fibre composite material
sheets and unlike plastic in hybrid components compared to systems
without adhesion promoter.
C) Hybrid Component Composed of Fibre Composite Material and
Metal
Structure: Fibre Composite Material--Adhesion Promoter--Metal
[0177] To obtain a composite composed of fibre composite material
and metal, various fibre composite material sheets of thickness 1.0
mm were used: [0178] C1: Fibre composite material composed of
VESTAMID L1600 (nylon-12) and carbon fibre fabric having continuous
fibres. The fabric has a weight of about 285 g/m.sup.2 with an
orientation of 0.degree./90.degree.. The fibre composite material
sheets were produced in a pressing process. [0179] C2: Fibre
composite material dynalite 102-FG290 (4)/45% type C (PA6) and
glass fibre fabric having continuous fibres from Bond-Laminates
GmbH, Germany. The fibre composite material has a fibre volume
content of about 45% by volume with an orientation of
0.degree./90.degree..
[0180] C3: Fibre composite material composed of TROGAMID CX7323
(PACM 12) and carbon fibre fabric having continuous fibres. The
fabric has a weight of about 250 g/m.sup.2 with an orientation of
0.degree./90.degree.. The fibre composite material sheets were
produced in a pressing process. [0181] C4: Fibre composite material
composed of epoxy resin (Evonik product in development) and carbon
fibre fabric having continuous fibres. The fabric has a weight of
about 250 g/m.sup.2 with an orientation of 0.degree./90.degree..
The fibre composite material sheets were produced in a pressing
process. [0182] C5: Fibre composite material composed of VESTAMID
HTplus M1000 (PA6T) and carbon fibre fabric having continuous
fibres. The fabric has a weight of about 285 g/m.sup.2 with an
orientation of 0.degree./90.degree.. The fibre composite material
sheets were produced in a pressing process.
[0183] The sheets were each coated with an adhesion promoter
composition. The composition applied comprised [0184] H1:
Copolyamide-based hotmelt adhesive (Vestamelt X1333-P1 from Evonik)
comprising an epoxy component and a blocked polyisocyanate in the
form of powder coating and [0185] H2: Solvent-containing spray
coating comprising about 30% by weight of a copolyamide-based
hotmelt adhesive comprising an epoxy component and a blocked
polyisocyanate.
[0186] The two compositions H1 and H2 comprise the same
copolyamide.
[0187] The powder coating was applied electrostatically with a
layer thickness of 70-100 .mu.m and stoved at 160.degree. C. for 5
min. The spray coating was applied electrostatically with a layer
thickness of 50-70 .mu.m and stoved at 160.degree. C. for 5 min.
For this purpose, the coated fibre composite materials were placed
in a preheated autoclave (oven).
[0188] After the stoving procedure, guillotine shears were used to
cut the sheets of fibre composite materials into strips appropriate
for the pressing operation with dimensions of 60.0 mm.times.25.0 mm
(tolerance+0-0.2 mm).
[0189] Metal sheets were used as composite partners and were
phosphated or chromated with converting agents. Granodine 958 A
from Henkel, Germany, for galvanized steel sheets DX56D Z140 to DIN
EN 10346 (M1) was used as converting agent, comprising inter alia
phosphoric acid and zinc bis(dihydrogenphosphate), and Deoxylyte
54NC was used for post-passivation. For aluminium sheets AlMg3 EN
AW-5754 H111 to DIN EN 573-3 (M2), a conversion layer (chromation)
of Alodine 1225 from Henkel, Germany, was used. The metal sheets
were likewise cut to size with guillotine shears to dimensions
appropriate for the pressing operation of about 60.0 mm.times.25.0
mm.
[0190] The bond between coated fibre composite material and metal
was obtained by a pressing operation in a hydraulic hot press
(manufacturer: Paul Weber, name: TEMPRESS). This is done by
inserting the uncoated metal sheet having dimensions of about
60.times.25.times.1 mm into a template in one half of the hot
press. A sheet of a fibre composite material having dimensions of
60.times.25.times.1 mm is positioned thereon. The press is heated
on the metal sheet side to about 230.degree. C. Thereafter, the
fibre composite material and the coated metal sheet are pressed at
a pressure of about 32 bar with a hold time of about 5 min to give
a composite body. The region of overlap between plastic and metal
was about 25 mm.times.25 mm. The sample had a total length of about
130 mm.
[0191] The test samples thus produced were stored at 50% relative
humidity for at least 24 h at 23.degree. C. in order to ensure a
uniform state of conditioning. The test samples are then clamped
into a standard Zwick/Roell Z-020 tensile tester and tested with a
velocity of 5 mm/min at 23.degree. C. with a distance between the
clamps and the overlap region of about 15 mm/side.
TABLE-US-00004 Fibre composite Adhesion Adhesion in Example
material promoter Metal MPa 41 C1 without M1 n.m. 42* C1 H1 M1 6.7
43* C1 H2 M1 7.2 44 C1 without M2 1.8 45* C1 H1 M2 7.3 46* C1 H2 M2
7.5 47 C2 without M1 0.6 48* C2 H1 M1 7.9 49* C2 H2 M1 8.1 50 C2
without M2 n.m. 51* C2 H1 M2 7.1 52* C2 H2 M2 6.4 53 C3 without M1
n.m. 54* C3 H1 M1 7.4 55 C3 without M2 n.m. 56* C3 H1 M2 7.9 57 C4
without M1 1.5 58* C4 H1 M1 7.1 59 C4 without M2 n.m. 60* C4 H1 M2
8.0 61 C5 without M1 0.7 62* C5 H1 M1 6.8 63 C5 without M2 n.m. 64*
C5 H1 M2 7.5 *inventive; n.m. = not measurable (no adhesion)
D) Hybrid Component Composed of Plastic and Fibre Composite
Material
Structure: Plastic--Adhesion Promoter--Fibre Composite Material
[0192] To obtain a composite composed of coated plastic and a fibre
composite material, various injection-moulded plastic sheets having
dimensions of about 60.times.25 mm and a thickness of about 4.0 mm
were used:
K1: Nylon-6 GF30 (Durethan BKV30 H2.0 from Lanxess, Germany) K2:
Polyphthalamide PA6T CF30 (VESTAMID HTPIus TGP3561 from Evonik
Industries AG)
[0193] A powder coating H1 composed of a copolyamide-based hotmelt
adhesive (Vestamelt X1333-P1 from Evonik) comprising an epoxy
component and a blocked polyisocyanate was applied to the plastics
sheets.
[0194] The powder coating was applied electrostatically with a
layer thickness of 50-70 .mu.m and stoved at 160.degree. C. for 5
min. For this purpose, the coated metal sheets were placed in a
preheated autoclave (oven).
[0195] Composite partners used were sheets of about
60.times.25.times.1 mm of a fibre composite material. The fibre
composite material consists of VESTAMID L1600 (nylon-12) and carbon
fibre fabric having continuous fibres. The fabric has a weight of
about 285 g/m.sup.2 with an orientation of 0.degree./90.degree..
The fibre composite material sheets were produced in a pressing
process.
[0196] Guillotine shears were used to cut the fibre composite
material sheets into a shape fitting the injection moulding cavity
with dimensions of 24.9 mm.times.59.8 mm (tolerance.+-.0.2 mm).
[0197] The bond between coated plastic and fibre composite material
was obtained by a pressing operation in a hydraulic hot press
(manufacturer: Paul Weber, name: TEMPRESS). This is done by
inserting the coated plastic into a template in one half of the hot
press. A sheet of a fibre composite material is positioned thereon.
Before the joining operation, the press is heated to about
200.degree. C. Thereafter, the fibre composite material and the
coated plastic are pressed at a pressure of about 32 bar with a
hold time of about 5 min to give a composite body. The region of
overlap between plastic and metal was about 25 mm.times.25 mm. The
test sample had a total length of about 130 mm.
[0198] The test samples thus produced were stored at 50% relative
humidity for at least 24 h at 23.degree. C. in order to ensure a
uniform state of conditioning. The test samples are then clamped
into a standard Zwick/Roell Z-020 tensile tester and tested with a
velocity of 5 mm/min at 23.degree. C. with a distance between the
clamps and the overlap region of about 15 mm/side.
TABLE-US-00005 Adhesion Adhesion in Example Plastic promoter MPa 65
K1 without 0.8 66* K1 H1 6.5 67 K2 without n.m. 68* K2 H1 8.0
*inventive; n.m. = not measurable (no adhesion)
E) Hybrid Component Composed of Fibre Composite Material and Fibre
Composite Material
Structure: Fibre Composite Material--Adhesion Promoter--Fibre
Composite Material
[0199] To obtain a composite composed of a coated fibre composite
material and an uncoated fibre composite material, suitable
pressing tests were conducted in a hot press. The following fibre
composite materials of thickness about 1.5 mm were used: [0200] C1:
Fibre composite material composed of VESTAMID L1600 (nylon-12) and
carbon fibre fabric having continuous fibres. The fabric has a
weight of about 285 g/m.sup.2 with an orientation of
0.degree./90.degree.. The fibre composite material sheets were
produced in a pressing process. [0201] C2: Fibre composite material
dynalite 102-FG290 (4)/45% type C (PA6) and glass fibre fabric
having continuous fibres from Bond-Laminates GmbH, Germany. The
fibre composite material has a fibre volume content of about 45% by
volume with an orientation of 0.degree./90.degree.. [0202] C3:
Fibre composite material composed of TROGAMID CX7323 (PACM 12) and
carbon fibre fabric having continuous fibres. The fabric has a
weight of about 250 g/m.sup.2 with an orientation of
0.degree./90.degree.. The fibre composite material sheets were
produced in a pressing process. [0203] C4: Fibre composite material
composed of polyurethane resin (Evonik product in development) and
carbon fibre fabric having continuous fibres. The fabric has a
weight of about 200 g/m.sup.2 with an orientation of
0.degree./90.degree.. The fibre composite material sheets were
produced in a pressing process.
[0204] C5: Fibre composite material composed of epoxy resin (Evonik
product in development) and carbon fibre fabric having continuous
fibres. The fabric has a weight of about 250 g/m.sup.2 with an
orientation of 0.degree./90.degree.. The fibre composite material
sheets were produced in a pressing process.
[0205] A powder coating H1 composed of a copolyamide-based hotmelt
adhesive (Vestamelt X1333-P1 from Evonik) comprising an epoxy
component and a blocked polyisocyanate was applied to a composite
partner composed of fiber composite material.
[0206] The powder coating was applied electrostatically with a
layer thickness of 50-70 .mu.m and stoved at 160.degree. C. for 5
min. For this purpose, the coated metal sheets were placed in a
preheated autoclave (oven).
[0207] After the stoving procedure, guillotine shears were used to
cut the coated and uncoated fibre composite materials into strips
appropriate for the pressing operation with dimensions of 60.0
mm.times.25.0 mm (tolerance+0-0.2 mm).
[0208] The bond between coated plastic and fibre composite material
was obtained by a pressing operation in a hydraulic hot press
(manufacturer: Paul Weber, name: TEMPRESS). This is done by
inserting the coated fibre composite material into a template in
one half of the hot press. A sheet of an uncoated fibre composite
material is positioned thereon. Before the joining operation, the
press is heated to about 230.degree. C. Thereafter, the coated
fibre composite material and the uncoated fibre composite material
are pressed at a pressure of about 32 bar with a hold time of about
5 min to give a composite body. The region of overlap was about 25
mm.times.25 mm. The test sample had a total length of about 130
mm.
[0209] The test samples thus produced were stored at 50% relative
humidity for at least 24 h at 23.degree. C. in order to ensure a
uniform state of conditioning. The test samples are then clamped
into a standard Zwick/Roell Z-020 tensile tester and tested with a
velocity of 5 mm/min at 23.degree. C. with a distance between the
clamps and the overlap region of about 15 mm/side.
TABLE-US-00006 Fibre Fibre composite Adhesion composite Adhesion in
Example material promoter material MPa 69 C1 without C2 2.9 70 C1
H1 C2 7.7 71 C1 without C3 8.8 72 C1 H1 C3 11.0 73 C4 without C5
n.r. 74 C4 H1 C5 13.0 75 C1 without C5 11.0 76 C1 H1 C5 15.0
*inventive; n.r.: no result; n.m. = not measurable: (no
adhesion)
* * * * *