CA2427037A1 - Sandwich elements and the use thereof - Google Patents
Sandwich elements and the use thereof Download PDFInfo
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- CA2427037A1 CA2427037A1 CA 2427037 CA2427037A CA2427037A1 CA 2427037 A1 CA2427037 A1 CA 2427037A1 CA 2427037 CA2427037 CA 2427037 CA 2427037 A CA2427037 A CA 2427037A CA 2427037 A1 CA2427037 A1 CA 2427037A1
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- sandwich element
- core layer
- element according
- fiber
- fibers
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- 230000032798 delamination Effects 0.000 claims description 21
- 239000010410 layer Substances 0.000 claims description 14
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- 241000264877 Hippospongia communis Species 0.000 claims description 10
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- 239000004033 plastic Substances 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 5
- 229910052751 metal Inorganic materials 0.000 claims description 5
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- 238000004519 manufacturing process Methods 0.000 claims description 4
- 241000531908 Aramides Species 0.000 claims description 2
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 2
- 229920003235 aromatic polyamide Polymers 0.000 claims description 2
- 239000004917 carbon fiber Substances 0.000 claims description 2
- 239000005337 ground glass Substances 0.000 claims description 2
- 239000002557 mineral fiber Substances 0.000 claims description 2
- 229920005594 polymer fiber Polymers 0.000 claims description 2
- 229920001169 thermoplastic Polymers 0.000 claims description 2
- 229920001187 thermosetting polymer Polymers 0.000 claims description 2
- 239000004416 thermosoftening plastic Substances 0.000 claims description 2
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- 239000002023 wood Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 239000004721 Polyphenylene oxide Substances 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
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- 239000003381 stabilizer Substances 0.000 description 3
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 2
- 239000004952 Polyamide Substances 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
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- 239000004793 Polystyrene Substances 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Natural products C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 101710137710 Thioesterase 1/protease 1/lysophospholipase L1 Proteins 0.000 description 2
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 2
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- LLAMAEIOZLEXMF-UHFFFAOYSA-N 3-methyl-3-azabicyclo[2.2.1]heptane Chemical compound C1CC2N(C)CC1C2 LLAMAEIOZLEXMF-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- 239000002390 adhesive tape Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000011111 cardboard Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 239000002657 fibrous material Substances 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920001228 polyisocyanate Polymers 0.000 description 1
- 239000005056 polyisocyanate Substances 0.000 description 1
- 229920005903 polyol mixture Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
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- 230000003313 weakening effect Effects 0.000 description 1
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Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B3/00—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form
- B32B3/10—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form characterised by a discontinuous layer, i.e. formed of separate pieces of material
- B32B3/12—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form characterised by a discontinuous layer, i.e. formed of separate pieces of material characterised by a layer of regularly- arranged cells, e.g. a honeycomb structure
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/04—Interconnection of layers
- B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/14—Layered products comprising a layer of metal next to a fibrous or filamentary layer
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/12—Layered products comprising a layer of synthetic resin next to a fibrous or filamentary layer
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B29/00—Layered products comprising a layer of paper or cardboard
- B32B29/02—Layered products comprising a layer of paper or cardboard next to a fibrous or filamentary layer
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
- B32B5/22—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed
- B32B5/24—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer
- B32B5/245—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer another layer next to it being a foam layer
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
- B32B5/22—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed
- B32B5/24—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer
- B32B5/26—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer another layer next to it also being fibrous or filamentary
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/04—Interconnection of layers
- B32B7/06—Interconnection of layers permitting easy separation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2250/00—Layers arrangement
- B32B2250/40—Symmetrical or sandwich layers, e.g. ABA, ABCBA, ABCCBA
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2605/00—Vehicles
- B32B2605/08—Cars
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
Landscapes
- Laminated Bodies (AREA)
- Vehicle Interior And Exterior Ornaments, Soundproofing, And Insulation (AREA)
- Battery Mounting, Suspending (AREA)
- Body Structure For Vehicles (AREA)
Abstract
The present invention relates to sandwich elements with at least one predetermined breaking-point at which the sandwich element breaks in the event of an impact. The present invention further relates to the use of such sandwich elements, particularly in the automotive field.
Description
Le A 36 OI7-US
_1..
SANDWIC»I ELEMENTS AND THE USE THEREOF
Field of the Invention The invention relates to sandwich elements with at least one predetermined breaking-point at which the sandwich element breaks in the event of an impact and also to their use in the automotive field.
Background of the Invention Sandwich elements can be employed, for example, in the automotive field as roof, bonnet, tailgate, door or floor-panel modules and also as load floors, rear parcel shelves or interior-trim components; an advantage in this connection is their high flexural rigidity with, at the same time, low area weight in comparison with structural elements of massive construction. In particular, structural elements that extend predominantly in a plane display high rigidity and strength values when loaded in that plane. However, in many structural elements these high strength values in the plane are disadvantageous.
For example, in the case of load floors of automobiles it car. happen that the load floors do not break in the event of a rear-end crash but pass on the energy of the crash to the passenger compartment and the occupants. This entails a high potential exposure to danger.
The load floors currently on the market are therefore provided, if necessary, with notches or slits. Such predetermined breaking-points weaken the load floors in the event of an accident. However, at the same time the load floors also always lose a large proportion of their flexural rigidity and flexural strength and diminish the working load.
Designs with articulations (hinges) in the load floors, at which the load floor collapses in the event of a crash, are possible but are technically very elaborate.
Le A 36 OI7-US .
_2_ Split load floors also exist. In this case it is disadvantageous that under unfavorable loading conditions the entire load rests on only one subsegment.
This requires an additional high flexural rigidity of the individual segments.
S
Furthermore, by virtue of special structural bearing elements it can be ensured that the Ioad floors rotate into a harmless position in the event of an accident.
But such very elaborate measures cannot be implemented in every vehicle.
I O Summary of the Invention The present invention therefore provides constructional elements that exhibit, on the one hand, a low weight and, on the other hand, a high flexural rigidity and flexural strength and that, in addition, in the event of an accident (a crash., in particular a rear-end crash) do not transmit the energy of the crash into the I5 passenger cell and hence endanger the occupants.
This is achieved by the introduction of at least one predetermined breaking-point into a sandwich element, whereby in the event of a rear-end collision the sandwich element breaks at the predetermined breaking-point, so that the energy of the crash 20 is not transmitted (reduced strength of the sandwich element in the plane), whereas the flexural strength and flexural rigidity under working load remain unchanged.
These and other advantages and benefits of the present invention will be apparent 2S from the Detailed Description of the Invention herein below.
Detailed Description of the Invention The present invention will now be described for purposes of illustration and not limitation.
I:e A 36 017-US
The present invention provides a sandwich element with at least one predetermined breaking-point, the sandwich element made of a) a core layer, preferably constructed from at least one ply, and b) two exterior outer layers firmly connected to the core Layer, which are preferably each constructed from at least one ply, c) optionally, one or more adhesive layers disposed between the core layer and the exterior layers, wherein at least one delamination means is included in at Least a portion of the sandwich element on a first (tension) side of the sandwich element, and wherein the delamination means is disposed between the exterior layer located on the first (tension) side and the core layer or contained in the outermost third of the core layer on the first (tension) side of the sandwich element.
The first (tension) side is that side of the sandwich element that is subjected to tensile stresses in the event of a flexural Load.
For the exterior layers in the present invention, use may be made of fibrous materials that are interspersed with plastics (such as, for example, polycarbonates, polyamides, polyurethanes, polyesters, polypropylene, polyethylene, polyvinyl chloride, polystyrene, polymethyl methacrylate, acrylonitrile/butadiene/styrene copolymers and blends thereof, epoxy resins, in particular polyurethane resin), such as glass-fiber mats, glass-fiber fleeces, glass-fiber random layers, glass-fiber cloth, cut or ground glass fibers and mineral fibers, natural-fiber mats, natural-fber knitted fabric, cut natural fibers and also fibrous mats, fibrous fleeces and fibrous knitted fabric based on polymer fibers, carbon fibers or aramide fibers and also mixtures thereof. Plastics such as, for example, polycarbonates, polyamides, polyurethanes, polyesters, polyethers, copolymers, polypropylene, polyethylene, polyvitryl chloride, polystyrene, polymethyl methacrylate, acrylonitrile/butadiene/styrene copolymers and blends thereof can also be Le A 36 017-US
employed. Furthermore, metal sheets, plastic sheets, wood panels or wood veneers can be employed. Glass-fiber mats with polyurethane resin applied to them preferably find application in the present invention.
As a core layer, thermoformable and also thermosetting polyurethane and thermo-plastic foamed materials, paper honeycombs, metal honeycombs or plastic honeycombs with honeycomb or corrugated structure may preferably be employed in the present invention.
As a delamination means, means having a decoupling effect (loosening the adhesion between exterior Layer and core layer or weakening the core layer on the tension side), which are introduced either (a) in situ in the course of manufacture of the sandwich elements or (b) subsequently, may preferably be disposed between the exterior layers and the core layer.
Suitable materials in case (a) include, but are not limited to, paper, cardboard, plastic foils and sheets or sheet-metal foils and plates, textile, plastic or metal foils provided with adhesive layers on one side, wood panels or wood veneers, impermeable textiles or naturally or synthetically based woven fabrics as well as solid or liquid films acting as separating agents as well as adhesive-free or coupling-agent-free zones. Where use is made of adhesive layers, an adhesive-free zone, for example, may act as delamination means. An adhesive-free zone or a zone with low adhesion or without adhesion can be produced by a delamination means which was inserted during the manufacture of the sandwich element being removed.
Suitable in case (b) are subsequent, mechanical or thermal, locally limited separation, such as sawing, cutting, splitting or losing, of the core layer and of the exterior layer on the tension side, so that a zone without adhesion is formed.
Le A 36 017-US
The decoupling is more preferably obtained by means of delamination means that are described in case (a).
The sandwich elements according to the present invention may fmd particular application in the automotive field as roof modules, bonnets, tailgate modules, door modules or floor-panel modules, more particularly as load floors, rear parcel shelves or interior-trim components.
The flexural strength is the limit of the flexural load, the exceeding of which results in failure of the structural element.
The flexural rigidity is the resistance of a structural element to flexure.
The invention will be elucidated in more detail on the basis of the following Examples.
Examples In Comparative Example l, a compression test was carried out in the plane of the sheet (crash direction) on samples without predetermined breaking-point, and in Example 2, on samples with predetermined breaking-points according to the invention. In Comparative Example 3, the flexural rigidity and flexural strength were determined on samples without predetermined breaking-point, and in Example 4, on samples with predetermined breaking-point according to the invention. Examples 5 and 6 show, on the basis of compression tests, how the breaking behavior can be controlled by modification of the type and geometry of the predetermined breaking-point according to the invention.
Initial materials:
Polyol 1: polyether polyol with an OH-value of 865, prepared by addition of propylene oxide onto trimethylolpropane as initiator.
Le A 36 017-US
Polyol 2: polyether polyol with an OH-value of 1000, prepared by addition of propylene oxide onto trimethylolpropane as initiator.
Polyol 3: polyether polyol with an OH-value of 42, prepared by addition of 86 % propylene oxide and I4 % ethylene oxide onto propylene glycol as initiator.
Polyisocya.nate: polymeric MDI with an isocyanate content of 31.5 wt.%
(DESIVIODUR 44V20L, Bayer AG).
Stabilizer: silicone stabilizer POL~'URAX SR242, Osi Crompton Witco Specialities, Frankfurt.
Catalyst: amine catalyst THANCAT AN10, Air Products GmbH, Hattingen.
Dyestuff: BAYDUR Schwarzpaste DN, Bayer AG, Leverkusen.
Polyurethane formulation 1:
Polyol 1 30 parts by weight Polyol 2 20 parts by weight Polyol 3 33 parts by weight catalyst 2.8 parts by weight stabilizer 1.3 parts by weight acetic acid 0.3 parts by weight dyestuff 3.3 parts by weight polyisocyanate 140 parts by weight The polyol mixture formed from Polyols 1 to 3 has an average OH-value of 568 mg KOH/g.
Comparative Example 1 (compression test on samples without predetermined breaking-point) Onto a flat core layer made of a paper honeycomb of corrugated-board type 5/5 Le A 36 017-US . .
having a thickness of 20 mm and an area weight of 1,600 g/m2 there were placed on both sides chopped glass-fiber mats having an area weight of 450 g/mZ which were treated at room temperature by spraying on 450 g/m2 of polyurethane formulation 1. This sandwich element was introduced into a flat tool heated to 130°C and subsequently press-molded to a thickness of 19.4 mm. After a pressing-time of 180 sec., the tool was opened and the finished sandwich element was taken out. The size of this sandwich element amounted to about 1,000 mm x 1,000 mm.
Three rectangular samples having a size of 400 mm x 180 mm (length x width) were sawn out of the sandwich element which was produced in this way, the longer edge of the sample being at right angles to the course of the paper corrugations of the core layer. These samples were subj ected to pressure uniaxially over the front faces in a universal tension/compression testing machine at a speed of 5 mm/min. The compressive stress consequently acted in the plane of the sheet in the direction of the longer dimension o.f the sample. The forces resulting in failure of the samples amounted to 14,173 N, 14,093 N and 15,928 N
(mean value: 14,731 N).
Example 2 (compression test on samples with predetermined breaking-point) A delamination means made of an aluminum strip coated with adhesive on one side, manufactured by Beiersdorf AG, brand TESA, designation TESAMETAL
4500, was applied onto a core layer as described above. The delamination means was cut to a width of 15 rnm and a length of 1,000 mm. and was stuck onto one side parallel to the course of the paper corrugations in the middle of the core layer.
Then there were placed on both sides chopped glass-fiber mats having an area weight of 450 g/m2 which were treated at room temperature by spraying.on 450 g/m2 of polyurethane formulation 1. This sandwich element was introduced into a flat tool heated to 130°C and subsequently press-molded to a thickness of Le A 36 017-US
-g-19.4 mm. After a pressing-time of 180 sec., the tool was opened and the finished sandwich element was taken out. The size of this sandwich element amounted to about 1,000 mm x 1,000 mm. Then three rectangular samples with a size of 400 mm x 180 mm were sawn-out of the sheet, the longer edge of the sample being at right angles to the course of the paper corrugations of the core layer. The samples were sawn out in such a way that the delamination means was located in the middle of the samples. With the exception of the delamination means, these samples were produced so as to be identical to those from Comparative Example 1.
The compression testing was effected in a manner analogous to Comparative Example 1. The forces (breaking-loads) resulting in failure of the samples amounted to 5,622 N, 5,106 N and 5,777 N (mean value: 5,502 N).
By virtue of the predetermined breaking-point in Example 2, the mean value of the breaking-load in comparison with sandwich elements without predetermined breaking-point (Comparative Example I) was reduced to 37 %.
Comparative Example 3 (flexural test on samples without predetermined breaking-point) Five samples each having a length of 240 mm and a width of 60 mm were taken from the sandwich element described in Comparative Example I . The orientation of the corrugated honeycomb was at right angles to the length of the sample.
The flexural test was carned out in accordance with DIN 53293. Effective flexural-rigidity values of 80.6 x 106 Nmm2, 82.1 x 106 Nmm2, 72.1 x 106 Nmm2, 75.4 x 106 Nmm2 and 77.5 x 106 Nmm2 (mean value: 77.5 x 106 Nmm2) were ascertained. The forces in the case of failure amounted to 853.6 N, 826.4 N, 828.7 N, 845.4 N and 820.6 N (mean value 834.9 N).
Example 4 (flexural test on samples with predetermined breaking-point) LeA36017-US ...
_g_ Five samples each having a length of 240 mm and a width of 60 mm were taken from the sandwich element described in Example 2. The orientation of the corrugated honeycomb was at right angles to the length of the sample, the delamination means was located in the middle of the sample. The flexural test was carried out in accordance with DIN 53293. The samples were inserted into.
the testing device in such a way that the delamination means was located on the tension side of the samples. Effective flexural-rigidity values of 84.3 x 106 NmmZ, 76.1 x 106 Nmm2, 74.6 x 106 Nmm2, 79.2 x 106 Nmm2 and 72.3 x 106 Nmm2 (mean value: 77.3 x 106 Nmm2) were ascertained. The forces in the case of failure amounted to 875.2 N, 864.8 N, 872.2 N, 849.1 N and 867.7 N (mean value 865.8 N).
In the case of an arrangement of the delamination means on the first (tension) side of the sandwich element, the effective flexural rigidity with and without delamination means did not change within the limits of the statistical variation of the measured values. The forces resulting in failure of the samples in the case with delamination means (Example 4) did not lie below the values for the case without delamination means (Comparative Example 3).
Example 5 (compression test on samples with predetermined breaking-point) In a manner analogous to Example 2, compression tests were carried out with the same delamination means (TESAMETAL 4500), this time cut to a width of 35 mm. The forces (breaking-loads) resulting in failure of the samples amounted to 1,838 N, 1,654 N and 1,735 N (mean value 1,742 N).
Example 6 (compression test on samples with predetermined breaking-point) In a manner analogous to Example 2, compression tests were carried out with Le A 3 G 017-US . .
another delamination means (adhesive tape manufactured by Beiersdorf AG, brand TESA, designation 4304; strip of paper coated with adhesive on one side).
The delamination means was cut to a width of 35 mm. The forces (breaking-loads) resulting in failure of the .samples amounted to x,146 N, 5,374 N and 4,712 N (mean value 5,077 N).
Although the invention has been described in detail in the foregoing for the purpose of illustration, it is to be understood that such detail is solely for that purpose and that variations can be made therein by those skilled in the art without departing from the spirit and scope of the invention except as it may be limited by the appended claims.
_1..
SANDWIC»I ELEMENTS AND THE USE THEREOF
Field of the Invention The invention relates to sandwich elements with at least one predetermined breaking-point at which the sandwich element breaks in the event of an impact and also to their use in the automotive field.
Background of the Invention Sandwich elements can be employed, for example, in the automotive field as roof, bonnet, tailgate, door or floor-panel modules and also as load floors, rear parcel shelves or interior-trim components; an advantage in this connection is their high flexural rigidity with, at the same time, low area weight in comparison with structural elements of massive construction. In particular, structural elements that extend predominantly in a plane display high rigidity and strength values when loaded in that plane. However, in many structural elements these high strength values in the plane are disadvantageous.
For example, in the case of load floors of automobiles it car. happen that the load floors do not break in the event of a rear-end crash but pass on the energy of the crash to the passenger compartment and the occupants. This entails a high potential exposure to danger.
The load floors currently on the market are therefore provided, if necessary, with notches or slits. Such predetermined breaking-points weaken the load floors in the event of an accident. However, at the same time the load floors also always lose a large proportion of their flexural rigidity and flexural strength and diminish the working load.
Designs with articulations (hinges) in the load floors, at which the load floor collapses in the event of a crash, are possible but are technically very elaborate.
Le A 36 OI7-US .
_2_ Split load floors also exist. In this case it is disadvantageous that under unfavorable loading conditions the entire load rests on only one subsegment.
This requires an additional high flexural rigidity of the individual segments.
S
Furthermore, by virtue of special structural bearing elements it can be ensured that the Ioad floors rotate into a harmless position in the event of an accident.
But such very elaborate measures cannot be implemented in every vehicle.
I O Summary of the Invention The present invention therefore provides constructional elements that exhibit, on the one hand, a low weight and, on the other hand, a high flexural rigidity and flexural strength and that, in addition, in the event of an accident (a crash., in particular a rear-end crash) do not transmit the energy of the crash into the I5 passenger cell and hence endanger the occupants.
This is achieved by the introduction of at least one predetermined breaking-point into a sandwich element, whereby in the event of a rear-end collision the sandwich element breaks at the predetermined breaking-point, so that the energy of the crash 20 is not transmitted (reduced strength of the sandwich element in the plane), whereas the flexural strength and flexural rigidity under working load remain unchanged.
These and other advantages and benefits of the present invention will be apparent 2S from the Detailed Description of the Invention herein below.
Detailed Description of the Invention The present invention will now be described for purposes of illustration and not limitation.
I:e A 36 017-US
The present invention provides a sandwich element with at least one predetermined breaking-point, the sandwich element made of a) a core layer, preferably constructed from at least one ply, and b) two exterior outer layers firmly connected to the core Layer, which are preferably each constructed from at least one ply, c) optionally, one or more adhesive layers disposed between the core layer and the exterior layers, wherein at least one delamination means is included in at Least a portion of the sandwich element on a first (tension) side of the sandwich element, and wherein the delamination means is disposed between the exterior layer located on the first (tension) side and the core layer or contained in the outermost third of the core layer on the first (tension) side of the sandwich element.
The first (tension) side is that side of the sandwich element that is subjected to tensile stresses in the event of a flexural Load.
For the exterior layers in the present invention, use may be made of fibrous materials that are interspersed with plastics (such as, for example, polycarbonates, polyamides, polyurethanes, polyesters, polypropylene, polyethylene, polyvinyl chloride, polystyrene, polymethyl methacrylate, acrylonitrile/butadiene/styrene copolymers and blends thereof, epoxy resins, in particular polyurethane resin), such as glass-fiber mats, glass-fiber fleeces, glass-fiber random layers, glass-fiber cloth, cut or ground glass fibers and mineral fibers, natural-fiber mats, natural-fber knitted fabric, cut natural fibers and also fibrous mats, fibrous fleeces and fibrous knitted fabric based on polymer fibers, carbon fibers or aramide fibers and also mixtures thereof. Plastics such as, for example, polycarbonates, polyamides, polyurethanes, polyesters, polyethers, copolymers, polypropylene, polyethylene, polyvitryl chloride, polystyrene, polymethyl methacrylate, acrylonitrile/butadiene/styrene copolymers and blends thereof can also be Le A 36 017-US
employed. Furthermore, metal sheets, plastic sheets, wood panels or wood veneers can be employed. Glass-fiber mats with polyurethane resin applied to them preferably find application in the present invention.
As a core layer, thermoformable and also thermosetting polyurethane and thermo-plastic foamed materials, paper honeycombs, metal honeycombs or plastic honeycombs with honeycomb or corrugated structure may preferably be employed in the present invention.
As a delamination means, means having a decoupling effect (loosening the adhesion between exterior Layer and core layer or weakening the core layer on the tension side), which are introduced either (a) in situ in the course of manufacture of the sandwich elements or (b) subsequently, may preferably be disposed between the exterior layers and the core layer.
Suitable materials in case (a) include, but are not limited to, paper, cardboard, plastic foils and sheets or sheet-metal foils and plates, textile, plastic or metal foils provided with adhesive layers on one side, wood panels or wood veneers, impermeable textiles or naturally or synthetically based woven fabrics as well as solid or liquid films acting as separating agents as well as adhesive-free or coupling-agent-free zones. Where use is made of adhesive layers, an adhesive-free zone, for example, may act as delamination means. An adhesive-free zone or a zone with low adhesion or without adhesion can be produced by a delamination means which was inserted during the manufacture of the sandwich element being removed.
Suitable in case (b) are subsequent, mechanical or thermal, locally limited separation, such as sawing, cutting, splitting or losing, of the core layer and of the exterior layer on the tension side, so that a zone without adhesion is formed.
Le A 36 017-US
The decoupling is more preferably obtained by means of delamination means that are described in case (a).
The sandwich elements according to the present invention may fmd particular application in the automotive field as roof modules, bonnets, tailgate modules, door modules or floor-panel modules, more particularly as load floors, rear parcel shelves or interior-trim components.
The flexural strength is the limit of the flexural load, the exceeding of which results in failure of the structural element.
The flexural rigidity is the resistance of a structural element to flexure.
The invention will be elucidated in more detail on the basis of the following Examples.
Examples In Comparative Example l, a compression test was carried out in the plane of the sheet (crash direction) on samples without predetermined breaking-point, and in Example 2, on samples with predetermined breaking-points according to the invention. In Comparative Example 3, the flexural rigidity and flexural strength were determined on samples without predetermined breaking-point, and in Example 4, on samples with predetermined breaking-point according to the invention. Examples 5 and 6 show, on the basis of compression tests, how the breaking behavior can be controlled by modification of the type and geometry of the predetermined breaking-point according to the invention.
Initial materials:
Polyol 1: polyether polyol with an OH-value of 865, prepared by addition of propylene oxide onto trimethylolpropane as initiator.
Le A 36 017-US
Polyol 2: polyether polyol with an OH-value of 1000, prepared by addition of propylene oxide onto trimethylolpropane as initiator.
Polyol 3: polyether polyol with an OH-value of 42, prepared by addition of 86 % propylene oxide and I4 % ethylene oxide onto propylene glycol as initiator.
Polyisocya.nate: polymeric MDI with an isocyanate content of 31.5 wt.%
(DESIVIODUR 44V20L, Bayer AG).
Stabilizer: silicone stabilizer POL~'URAX SR242, Osi Crompton Witco Specialities, Frankfurt.
Catalyst: amine catalyst THANCAT AN10, Air Products GmbH, Hattingen.
Dyestuff: BAYDUR Schwarzpaste DN, Bayer AG, Leverkusen.
Polyurethane formulation 1:
Polyol 1 30 parts by weight Polyol 2 20 parts by weight Polyol 3 33 parts by weight catalyst 2.8 parts by weight stabilizer 1.3 parts by weight acetic acid 0.3 parts by weight dyestuff 3.3 parts by weight polyisocyanate 140 parts by weight The polyol mixture formed from Polyols 1 to 3 has an average OH-value of 568 mg KOH/g.
Comparative Example 1 (compression test on samples without predetermined breaking-point) Onto a flat core layer made of a paper honeycomb of corrugated-board type 5/5 Le A 36 017-US . .
having a thickness of 20 mm and an area weight of 1,600 g/m2 there were placed on both sides chopped glass-fiber mats having an area weight of 450 g/mZ which were treated at room temperature by spraying on 450 g/m2 of polyurethane formulation 1. This sandwich element was introduced into a flat tool heated to 130°C and subsequently press-molded to a thickness of 19.4 mm. After a pressing-time of 180 sec., the tool was opened and the finished sandwich element was taken out. The size of this sandwich element amounted to about 1,000 mm x 1,000 mm.
Three rectangular samples having a size of 400 mm x 180 mm (length x width) were sawn out of the sandwich element which was produced in this way, the longer edge of the sample being at right angles to the course of the paper corrugations of the core layer. These samples were subj ected to pressure uniaxially over the front faces in a universal tension/compression testing machine at a speed of 5 mm/min. The compressive stress consequently acted in the plane of the sheet in the direction of the longer dimension o.f the sample. The forces resulting in failure of the samples amounted to 14,173 N, 14,093 N and 15,928 N
(mean value: 14,731 N).
Example 2 (compression test on samples with predetermined breaking-point) A delamination means made of an aluminum strip coated with adhesive on one side, manufactured by Beiersdorf AG, brand TESA, designation TESAMETAL
4500, was applied onto a core layer as described above. The delamination means was cut to a width of 15 rnm and a length of 1,000 mm. and was stuck onto one side parallel to the course of the paper corrugations in the middle of the core layer.
Then there were placed on both sides chopped glass-fiber mats having an area weight of 450 g/m2 which were treated at room temperature by spraying.on 450 g/m2 of polyurethane formulation 1. This sandwich element was introduced into a flat tool heated to 130°C and subsequently press-molded to a thickness of Le A 36 017-US
-g-19.4 mm. After a pressing-time of 180 sec., the tool was opened and the finished sandwich element was taken out. The size of this sandwich element amounted to about 1,000 mm x 1,000 mm. Then three rectangular samples with a size of 400 mm x 180 mm were sawn-out of the sheet, the longer edge of the sample being at right angles to the course of the paper corrugations of the core layer. The samples were sawn out in such a way that the delamination means was located in the middle of the samples. With the exception of the delamination means, these samples were produced so as to be identical to those from Comparative Example 1.
The compression testing was effected in a manner analogous to Comparative Example 1. The forces (breaking-loads) resulting in failure of the samples amounted to 5,622 N, 5,106 N and 5,777 N (mean value: 5,502 N).
By virtue of the predetermined breaking-point in Example 2, the mean value of the breaking-load in comparison with sandwich elements without predetermined breaking-point (Comparative Example I) was reduced to 37 %.
Comparative Example 3 (flexural test on samples without predetermined breaking-point) Five samples each having a length of 240 mm and a width of 60 mm were taken from the sandwich element described in Comparative Example I . The orientation of the corrugated honeycomb was at right angles to the length of the sample.
The flexural test was carned out in accordance with DIN 53293. Effective flexural-rigidity values of 80.6 x 106 Nmm2, 82.1 x 106 Nmm2, 72.1 x 106 Nmm2, 75.4 x 106 Nmm2 and 77.5 x 106 Nmm2 (mean value: 77.5 x 106 Nmm2) were ascertained. The forces in the case of failure amounted to 853.6 N, 826.4 N, 828.7 N, 845.4 N and 820.6 N (mean value 834.9 N).
Example 4 (flexural test on samples with predetermined breaking-point) LeA36017-US ...
_g_ Five samples each having a length of 240 mm and a width of 60 mm were taken from the sandwich element described in Example 2. The orientation of the corrugated honeycomb was at right angles to the length of the sample, the delamination means was located in the middle of the sample. The flexural test was carried out in accordance with DIN 53293. The samples were inserted into.
the testing device in such a way that the delamination means was located on the tension side of the samples. Effective flexural-rigidity values of 84.3 x 106 NmmZ, 76.1 x 106 Nmm2, 74.6 x 106 Nmm2, 79.2 x 106 Nmm2 and 72.3 x 106 Nmm2 (mean value: 77.3 x 106 Nmm2) were ascertained. The forces in the case of failure amounted to 875.2 N, 864.8 N, 872.2 N, 849.1 N and 867.7 N (mean value 865.8 N).
In the case of an arrangement of the delamination means on the first (tension) side of the sandwich element, the effective flexural rigidity with and without delamination means did not change within the limits of the statistical variation of the measured values. The forces resulting in failure of the samples in the case with delamination means (Example 4) did not lie below the values for the case without delamination means (Comparative Example 3).
Example 5 (compression test on samples with predetermined breaking-point) In a manner analogous to Example 2, compression tests were carried out with the same delamination means (TESAMETAL 4500), this time cut to a width of 35 mm. The forces (breaking-loads) resulting in failure of the samples amounted to 1,838 N, 1,654 N and 1,735 N (mean value 1,742 N).
Example 6 (compression test on samples with predetermined breaking-point) In a manner analogous to Example 2, compression tests were carried out with Le A 3 G 017-US . .
another delamination means (adhesive tape manufactured by Beiersdorf AG, brand TESA, designation 4304; strip of paper coated with adhesive on one side).
The delamination means was cut to a width of 35 mm. The forces (breaking-loads) resulting in failure of the .samples amounted to x,146 N, 5,374 N and 4,712 N (mean value 5,077 N).
Although the invention has been described in detail in the foregoing for the purpose of illustration, it is to be understood that such detail is solely for that purpose and that variations can be made therein by those skilled in the art without departing from the spirit and scope of the invention except as it may be limited by the appended claims.
Claims (9)
1. A sandwich element comprising:
a) a core layer; and b) two exterior outer layers firmly connected to the core layer, c) optionally, at least one adhesive layer disposed between the core layer and the exterior layers, wherein a delamination means is included in at least a portion of the sandwich element on a first (tension) side of the sandwich element, and wherein the delamination means is disposed between the exterior layer located on the first (tension) side and the core layer or contained in the outermost third of the core layer on the first (tension) side of the sandwich element.
a) a core layer; and b) two exterior outer layers firmly connected to the core layer, c) optionally, at least one adhesive layer disposed between the core layer and the exterior layers, wherein a delamination means is included in at least a portion of the sandwich element on a first (tension) side of the sandwich element, and wherein the delamination means is disposed between the exterior layer located on the first (tension) side and the core layer or contained in the outermost third of the core layer on the first (tension) side of the sandwich element.
2. In a process of making one of a roof module, bonnet, tailgate module, door module, floor-panel module, load floor, rear parcel shelf or interior-trim component, the improvement comprising including the sandwich element according to Claim 1.
3. One of a roof module, bonnet, tailgate module, door module, floor-panel module, load floor, rear parcel shelf or interior-trim component made according to the process of Claim 2.
4. The sandwich element according to Claim 1, wherein the core layer is constructed from at least one ply.
5. The sandwich element according to Claim 1, wherein the two exterior outer layers are each constructed from at least one ply.
6. The sandwich element according to Claim 1, wherein the two exterior outer layers are made of at least one material selected from the group consisting of glass-fiber mat, glass-fiber fleeces, glass-fiber random layers, glass-fiber cloth, cut or ground glass fibers, cut or ground mineral fibers, natural-fiber mats, natural-fiber knitted fabric, cut natural fibers and fibrous mats, fibrous fleeces and fibrous knitted fabric based on polymer fibers, carbon fibers or aramide fibers.
7. The sandwich element according to Claim 1, wherein the core layer is made of at least one material selected from the group consisting of thermoformable and/or thermosetting polyurethane, thermoplastic foamed materials, paper honeycombs, metal honeycombs and plastic honeycombs.
8. The sandwich element according to Claim 1, wherein the delaminating means is introduced during manufacture of the sandwich element.
9. The sandwich element according to Claim 1, wherein the delaminating means is introduced subsequent to manufacture of the sandwich element.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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DE10219711 | 2002-05-02 | ||
DE10219711.3 | 2002-05-02 |
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CA2427037A1 true CA2427037A1 (en) | 2003-11-02 |
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CA 2427037 Abandoned CA2427037A1 (en) | 2002-05-02 | 2003-04-29 | Sandwich elements and the use thereof |
Country Status (9)
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US (1) | US20030207116A1 (en) |
EP (1) | EP1359005B1 (en) |
JP (1) | JP2004001505A (en) |
KR (1) | KR20030086418A (en) |
CN (1) | CN1454772A (en) |
AT (1) | ATE316461T1 (en) |
CA (1) | CA2427037A1 (en) |
DE (1) | DE50302259D1 (en) |
ES (1) | ES2257615T3 (en) |
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DE20311028U1 (en) * | 2003-07-17 | 2003-09-25 | Webasto Vehicle Sys Int Gmbh | Tailgate for a motor vehicle |
DE10356547A1 (en) * | 2003-12-04 | 2005-07-07 | Benteler Automobiltechnik Gmbh | Floor of rear storage area in estate type car or small van, comprising alternating softer and harder segments for folding in case of impact |
DE102004030196A1 (en) * | 2004-06-22 | 2006-01-19 | Bayer Materialscience Ag | Process for the preparation of polyurethane moldings |
US7849643B2 (en) * | 2004-12-28 | 2010-12-14 | Intelligent Engineering (Bahamas) Limited | Structural step unit with run portion and rise portion |
US7690720B2 (en) * | 2008-01-31 | 2010-04-06 | Gm Global Technology Operations, Inc. | Energy absorbing vehicle hood assembly with asymmetric sandwich inner structure |
DE102009006130B4 (en) * | 2009-01-26 | 2011-09-15 | Daimler Ag | Composite component with cover layer |
DE102009048000A1 (en) * | 2009-10-01 | 2011-09-15 | Bayer Materialscience Ag | Composite made of open-cell rigid foam |
EP2504186B1 (en) * | 2009-11-25 | 2013-09-25 | Weber Automotive AG-Holding | Trunk lid made of fiber-reinforced thermoplastic plastic |
DK2595805T3 (en) | 2010-07-20 | 2017-05-01 | Hexcel Composites Ltd | IMPROVED COMPOSITION MATERIAL |
DE102010037817A1 (en) * | 2010-09-28 | 2012-03-29 | Thyssenkrupp Steel Europe Ag | Structural or chassis part of a motor vehicle |
WO2012167879A2 (en) * | 2011-06-06 | 2012-12-13 | Webasto Ag | Vehicle component |
DE102011118851A1 (en) * | 2011-11-18 | 2013-05-23 | Vpw Nink Gmbh | Layered composite profile plate for use as e.g. roof component, has upper, lower and middle layers, where one of layers is different from other two layers in toughness or rigidity or density around specific percent |
JP2015522441A (en) * | 2012-05-09 | 2015-08-06 | ディーエスエム アイピー アセッツ ビー.ブイ. | Plastic engine cover |
JP6020310B2 (en) * | 2013-04-02 | 2016-11-02 | トヨタ自動車株式会社 | Composite material and food panel using it |
EP3037259B1 (en) * | 2014-12-22 | 2019-03-20 | Magna Steyr Fahrzeugtechnik AG & Co KG | Sandwich component |
DE102016204624A1 (en) * | 2016-03-21 | 2017-09-21 | Bayerische Motoren Werke Aktiengesellschaft | Composite sandwich component for use as a loading floor or parcel shelf of a motor vehicle |
CN106184399B (en) * | 2016-08-23 | 2019-01-29 | 北京新能源汽车股份有限公司 | Roof panel for vehicle, and method for manufacturing roof panel for vehicle |
DE102020111721A1 (en) | 2020-04-29 | 2021-11-04 | Bayerische Motoren Werke Aktiengesellschaft | Partition wall element for a motor vehicle |
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AT296622B (en) * | 1967-07-04 | 1972-02-25 | Bayer Ag | Heavy-duty foam body |
US3909582A (en) * | 1971-07-19 | 1975-09-30 | American Can Co | Method of forming a line of weakness in a multilayer laminate |
US4025686A (en) * | 1975-06-26 | 1977-05-24 | Owens-Corning Fiberglas Corporation | Molded composite article and method for making the article |
US5049439A (en) * | 1990-05-25 | 1991-09-17 | Fibre Converters, Inc. | Thermoformable article |
DE4124951A1 (en) * | 1991-07-27 | 1993-01-28 | Basf Ag | LAMINATES |
US5338766A (en) * | 1993-03-26 | 1994-08-16 | The Procter & Gamble Company | Superabsorbent polymer foam |
KR100370309B1 (en) * | 1994-04-29 | 2003-06-19 | 멕네일-피피시, 인코포레이티드 | Absorbent hygiene products for women and manufacturing method thereof |
GB9411367D0 (en) * | 1994-06-07 | 1994-07-27 | Ici Composites Inc | Curable Composites |
US5510171A (en) * | 1995-01-19 | 1996-04-23 | Minnesota Mining And Manufacturing Company | Durable security laminate with hologram |
FR2779379B1 (en) * | 1998-06-05 | 2000-08-25 | Peguform France | PROCESS FOR PRODUCING A REINFORCED COMPOSITE STRUCTURE PANEL OF THE SANDWICH TYPE WITH AN ALVEOLAR CORE AND PANEL PRODUCED ACCORDING TO SUCH A PROCESS |
HUP0300893A2 (en) * | 2000-03-17 | 2003-08-28 | Tip Engineering Group | Process and apparatus for weakening an automotive trim piece for an airbag deployment opening |
US6893453B2 (en) * | 2002-12-17 | 2005-05-17 | Kimberly-Clark Worldwide, Inc. | Thermal therapy pad with variable heat control |
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2003
- 2003-04-22 DE DE50302259T patent/DE50302259D1/en not_active Expired - Fee Related
- 2003-04-22 ES ES03009120T patent/ES2257615T3/en not_active Expired - Lifetime
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- 2003-04-22 EP EP20030009120 patent/EP1359005B1/en not_active Expired - Lifetime
- 2003-04-22 AT AT03009120T patent/ATE316461T1/en not_active IP Right Cessation
- 2003-04-29 CA CA 2427037 patent/CA2427037A1/en not_active Abandoned
- 2003-05-01 KR KR20030027921A patent/KR20030086418A/en not_active Application Discontinuation
- 2003-05-01 JP JP2003126413A patent/JP2004001505A/en active Pending
- 2003-05-06 CN CN03124141A patent/CN1454772A/en active Pending
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JP2004001505A (en) | 2004-01-08 |
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CN1454772A (en) | 2003-11-12 |
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