EP0101676B1 - Shoe insole and method of making the same - Google Patents
Shoe insole and method of making the same Download PDFInfo
- Publication number
- EP0101676B1 EP0101676B1 EP83890137A EP83890137A EP0101676B1 EP 0101676 B1 EP0101676 B1 EP 0101676B1 EP 83890137 A EP83890137 A EP 83890137A EP 83890137 A EP83890137 A EP 83890137A EP 0101676 B1 EP0101676 B1 EP 0101676B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- insole
- fleece
- dispersion
- impregnated
- hollow microspheres
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- 238000004519 manufacturing process Methods 0.000 title description 6
- 239000006185 dispersion Substances 0.000 claims abstract description 52
- 239000004005 microsphere Substances 0.000 claims abstract description 45
- 239000000839 emulsion Substances 0.000 claims abstract description 20
- 229920002635 polyurethane Polymers 0.000 claims abstract description 18
- 239000004814 polyurethane Substances 0.000 claims abstract description 18
- 230000003014 reinforcing effect Effects 0.000 claims abstract description 12
- 229920001577 copolymer Polymers 0.000 claims abstract description 9
- 238000011065 in-situ storage Methods 0.000 claims abstract description 9
- 229920002994 synthetic fiber Polymers 0.000 claims abstract description 8
- 239000002245 particle Substances 0.000 claims abstract description 7
- 238000005187 foaming Methods 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 claims description 13
- 239000004744 fabric Substances 0.000 claims description 10
- 239000000463 material Substances 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 5
- 239000011230 binding agent Substances 0.000 claims description 4
- 229920001169 thermoplastic Polymers 0.000 claims description 4
- 239000004416 thermosoftening plastic Substances 0.000 claims description 4
- 229920000877 Melamine resin Polymers 0.000 claims description 3
- 229920002125 Sokalan® Polymers 0.000 claims description 3
- 229920003180 amino resin Polymers 0.000 claims description 3
- 150000002148 esters Chemical class 0.000 claims description 3
- 238000005470 impregnation Methods 0.000 claims description 3
- 229920003023 plastic Polymers 0.000 claims description 3
- 239000004033 plastic Substances 0.000 claims description 3
- 239000004584 polyacrylic acid Substances 0.000 claims description 3
- 229920002689 polyvinyl acetate Polymers 0.000 claims description 3
- 239000011118 polyvinyl acetate Substances 0.000 claims description 3
- 239000004753 textile Substances 0.000 claims description 3
- 244000043261 Hevea brasiliensis Species 0.000 claims description 2
- 239000004952 Polyamide Substances 0.000 claims description 2
- 239000004743 Polypropylene Substances 0.000 claims description 2
- 239000000945 filler Substances 0.000 claims description 2
- 229920003052 natural elastomer Polymers 0.000 claims description 2
- 229920001194 natural rubber Polymers 0.000 claims description 2
- 229920002647 polyamide Polymers 0.000 claims description 2
- 229920000728 polyester Polymers 0.000 claims description 2
- -1 polypropylene Polymers 0.000 claims description 2
- 229920001155 polypropylene Polymers 0.000 claims description 2
- 229920003051 synthetic elastomer Polymers 0.000 claims description 2
- 239000005061 synthetic rubber Substances 0.000 claims description 2
- 238000009998 heat setting Methods 0.000 claims 2
- 239000003795 chemical substances by application Substances 0.000 claims 1
- 229920000642 polymer Polymers 0.000 claims 1
- 239000002759 woven fabric Substances 0.000 claims 1
- 238000009958 sewing Methods 0.000 abstract description 3
- 239000000835 fiber Substances 0.000 description 10
- 230000002787 reinforcement Effects 0.000 description 7
- 229920005830 Polyurethane Foam Polymers 0.000 description 5
- 239000011496 polyurethane foam Substances 0.000 description 5
- 239000012209 synthetic fiber Substances 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000003380 propellant Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 229920001187 thermosetting polymer Polymers 0.000 description 2
- 230000006378 damage Effects 0.000 description 1
- 239000004815 dispersion polymer Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
Images
Classifications
-
- A—HUMAN NECESSITIES
- A43—FOOTWEAR
- A43B—CHARACTERISTIC FEATURES OF FOOTWEAR; PARTS OF FOOTWEAR
- A43B13/00—Soles; Sole-and-heel integral units
- A43B13/02—Soles; Sole-and-heel integral units characterised by the material
- A43B13/10—Metal
-
- A—HUMAN NECESSITIES
- A43—FOOTWEAR
- A43B—CHARACTERISTIC FEATURES OF FOOTWEAR; PARTS OF FOOTWEAR
- A43B13/00—Soles; Sole-and-heel integral units
- A43B13/02—Soles; Sole-and-heel integral units characterised by the material
- A43B13/12—Soles with several layers of different materials
-
- A—HUMAN NECESSITIES
- A43—FOOTWEAR
- A43B—CHARACTERISTIC FEATURES OF FOOTWEAR; PARTS OF FOOTWEAR
- A43B13/00—Soles; Sole-and-heel integral units
- A43B13/38—Built-in insoles joined to uppers during the manufacturing process, e.g. structural insoles; Insoles glued to shoes during the manufacturing process
Definitions
- the invention relates to an insole for shoes, in particular for those in which, after the insole has been connected to the upper of the shoe, for example by means of a seam, a body made of polyurethane which forms the outsole and / or the footbed is foamed onto the underside of the insole, which consists of a nonwoven, preferably made of synthetic fibers, a binder and fillers is formed.
- the invention further relates to a method for producing such an insole.
- the insole In order to avoid that the polyurethane-forming material penetrates through the insole during the foaming process and then connects to the last, it is necessary to impregnate the insole with a hardenable binder so that the like between the fibers, threads or the like. existing gaps in the insole material are closed and passage of the polyurethane foam is prevented. As a result, however, the insole is strengthened in such a way that it becomes rigid and unyielding, so that an elastic support of the foot takes place in an inadequate manner despite the use of elastic, flexible polyurethane foam for the footbed and / or the outsole. The elastic properties of the polyurethane foam are undesirably largely rendered ineffective by the rigid, unyielding insole.
- the invention has for its object to provide an insole " which ensures elastic support of the foot or does not undesirably render the elastic support of the foot caused by the polyurethane body ineffective again, and which has a heat and cold insulation effect.
- the upper area of the fleece which is adjacent to the upper side of the insole on which the upper side rests, be impregnated with a dispersion or emulsion which contains at least 1% by weight, preferably 1 to 5% by weight.
- a dispersion or emulsion which contains at least 1% by weight, preferably 1 to 5% by weight.
- these hollow microspheres have a thin, elastic, closed shell and contain a gas, these hollow microspheres act like gas cushions, so that it becomes an elastic, resilient
- the sole of the foot is also supported by the insole according to the invention prevents an undesired passage of the polyurethane-forming material during the foaming process through the insole according to the invention as well as with the known rigid and rigid insoles.
- the gas enclosed in the hollow microspheres also has a thermally insulating effect, so that a comfortable fit is achieved when using the insole according to the invention.
- the weight of the insole according to the invention, in which the added hollow microspheres fill 6 to 36% of the total volume of the insole, is considerably reduced.
- the sewing on of the shoe upper is also made considerably easier with the insole according to the invention.
- hollow microspheres are known per se from AT-B-366 565, but only for an outsole. Therefore, the hollow microspheres do not coir here as a blockage against the penetration of the polyurethane foam forming the outsole, as is the case with the invention, since the balls themselves are embedded in the polyurethane foam in this prior art.
- a reinforcing insert is arranged in the fleece approximately parallel to the top and bottom of the insole, the fibers of the fleece preferably at least partially penetrating the reinforcing insert.
- the fleece forming the insole can be completely impregnated with the dispersion or emulsion having the hollow microspheres.
- an arrangement is expedient in which only the area of the fleece that is adjacent to the top of the insole, preferably up to the reinforcement insert, if one is provided, impregnated with the dispersion or emulsion, whereas the lower region of the fleece is anchored in the polyurethane body.
- the fleece expediently consists of polyester fibers or polyamide fibers or polyacrylic fibers, and mixtures of these fibers can also be used.
- the nonwoven has a basis weight between 120 and 360 g / m 2 , preferably between 140 and 200 g / m 2 , before it is impregnated.
- the fleece is expediently provided in an amount of 55 to 87% by weight.
- the reinforcement insert can be formed from a fabric, for example a lattice fabric or a ribbon fabric, or from a knitted fabric.
- the reinforcement insert advantageously consists of polypropylene fibers with a basis weight between 72 and 165 g / m 2 , preferably between 85 and 115 g / m2.
- a plastic dispersion preferably a polymer dispersion, is expediently used as the dispersion for impregnating the nonwoven, but the nonwoven can also be impregnated with a dispersion based on natural rubber or synthetic rubber.
- the diameter of the hollow microspheres is between 0.01 and 1 mm, preferably hollow microspheres of different diameters being provided.
- Hollow microspheres of the size mentioned provide a good, step-elastic support of the sole of the foot without the hollow hollow spheres at the top of the insole, which are perceived as disturbing. If hollow microspheres of different diameters are used, the hollow microspheres of smaller diameter fit into the spaces between the hollow microspheres of larger diameter, so that a uniform overall distribution of the hollow microspheres takes place in the insole.
- the top, on which the foot rests, the insole can optionally be provided with a cover, for example made of textile material.
- the procedure can be such that the nonwoven, which preferably consists of synthetic fibers, is at least partially impregnated with a dispersion or emulsion in which a propellant-containing compact particle of vinylidene chloride copolymer is contained, and that the nonwoven thus impregnated is then applied to a Temperature of more than 75 ° C is heated, whereby the hollow microspheres form from one.
- the fact that the hollow microspheres form the compact particles containing a propellant in situ as a result of the supply of heat ensures a uniformly distributed, closely spaced arrangement of the hollow microspheres of different diameters.
- the compact particles that form the hollow microspheres through the supply of heat are known under the trademark EXPANCEL and are available from Kema Nord in Sundsvall (Sweden).
- the formation of the hollow microspheres in situ can take place when an aqueous dispersion dries with simultaneous supply of heat.
- a dispersion with thermosetting properties for example a dispersion consisting of melamine resins or other aminoplasts, must be used.
- the hollow microspheres can only be formed in situ by heating to a temperature of more than 85 ° C. after the dispersion has dried. So that the hollow microspheres can still form after the dispersion has already dried, it is necessary to use a dispersion with thermoplastic properties, for example a dispersion consisting of polyacrylic acid ester or polyvinyl acetate.
- the nonwoven is at least partially impregnated with a dispersion or emulsion which already contains finished hollow microspheres, the thin shell of which consists of vinylidene chloride copolymer and whose hollow core contains a gas, after which the dispersion is allowed to dry.
- a dispersion or emulsion which already contains finished hollow microspheres, the thin shell of which consists of vinylidene chloride copolymer and whose hollow core contains a gas, after which the dispersion is allowed to dry.
- a dispersion or emulsion is expediently applied to the nonwoven using a doctor blade.
- the dispersion or emulsion is preferably heated and / or dried in a high-frequency field. This has the advantage that uniform heating takes place at all points of the nonwoven, so that the dispersion or emulsion also dries uniformly both on the surface and in the interior.
- the hollow microspheres are produced in situ, they are also formed simultaneously everywhere using a high-frequency field and are therefore evenly distributed in the fleece.
- Fig. 1 shows a longitudinal section through a shoe equipped with an insole according to the invention.
- Fig. 2 shows an enlarged view of an insole designed according to the invention with a foamed polyurethane body in section.
- Fig. 3 shows a further embodiment of the insole according to the invention with a foamed polyurethane body in section.
- the insole 1 consists of a fleece 9 made of synthetic fibers, in which, approximately in the middle between the upper side 4 and the lower side 6, a reinforcing insert 10 is arranged, which consists of a fabric, for example a ribbon fabric, or a knitted fabric made of synthetic fibers.
- the fibers of the fleece 9 run partially from the top 4 to the bottom 6 of the insole 1 and penetrate the reinforcement insert 10.
- the fleece 9 is completely impregnated with a dispersion or emulsion which contains at least 1% by weight of hollow microspheres 11, the thin shell of which consists of vinylidene chloride copolymer and the hollow core of which contains a gas.
- the polyurethane body 7 is foamed on the underside 6 of the insole 1.
- Hollow microspheres of the type mentioned are already known and are described, for example, in the reference Modern Plastics, August 1969, pages 55 to 57.
- the embodiment according to FIG. 3 differs from the embodiment according to FIG. 2 in that only that part of the fleece 9 which is adjacent to the upper side 4 is impregnated with a dispersion approximately up to the reinforcing insert 10 which has the hollow microspheres mentioned.
- the non-impregnated area of the fleece 9 located below the reinforcement insert 10 is embedded in the polyurethane portion 7 in this embodiment, which results in an even better connection between the insole and the polyurethane portion 7. .
- the procedure can be such that the fleece 9 is provided with the reinforcing insert 10 and is then impregnated with a dispersion in which a propellant-containing compact particle made of vinylidene chloride copolymer is contained.
- the impregnated fleece 9 is then heated to a temperature of more than 75 ° C., the hollow microspheres forming in situ.
- the formation of the hollow microspheres in situ can take place simultaneously with the drying of the aqueous dispersion by the application of heat.
- the heat is preferably supplied in the high-frequency field. This has the advantage that uniform heating takes place at all points of the nonwoven and as a result the hollow mirrors are simultaneously formed everywhere.
- thermosetting properties for example a dispersion consisting of melamine resins or other aminoplasts, must be used.
- the hollow microspheres can also be formed from the compact particles only after the dispersion has already dried.
- a dispersion with thermoplastic properties for example a dispersion consisting of a polyacrylic acid ester or polyvinyl acetate.
- the fleece 9 is impregnated with a dispersion which already contains finished hollow microspheres 11.
- the dispersion provided with finished hollow microspheres 11 is applied to the nonwoven, for example by means of a doctor, and left to dry. After drying, the insole thus formed is connected to the shoe upper 2 and then the polyurethane-forming material is foamed onto the underside of the insole 1, from which the part 7 is formed, which forms the footbed and / or the outsole.
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Footwear And Its Accessory, Manufacturing Method And Apparatuses (AREA)
- Laminated Bodies (AREA)
- Orthopedics, Nursing, And Contraception (AREA)
- Ropes Or Cables (AREA)
Abstract
Description
Die Erfindung betrifft eine Brandsohle für Schuhe, insbesondere für solche, bei welchen nach der Verbindung der Brandsohle mit dem Schuhoberteil, beispielsweise durch eine Naht, ein die Laufsohle und/oder das Fußbett bildender Körper aus Polyurethan an die Unterseite der Brandsohle angeschäumt wird, die aus einem, vorzugsweise aus synthetischen Fasern bestehenden, Vlies, einem Binder und aus Füllstoffen gebildet ist. Ferner betrifft die Erfindung ein Verfahren zur Herstellung einer solchen Brandsohle.The invention relates to an insole for shoes, in particular for those in which, after the insole has been connected to the upper of the shoe, for example by means of a seam, a body made of polyurethane which forms the outsole and / or the footbed is foamed onto the underside of the insole, which consists of a nonwoven, preferably made of synthetic fibers, a binder and fillers is formed. The invention further relates to a method for producing such an insole.
Es sind bereits Schuhe der sogenannten "California-Machart" bekannt, bei welchen die Herstellung derart erfolgt, daß zunächst eine Brandsohle aus textilem oder synthetischem Material mit dem Schuhoberteil, beispielsweise durch eine Naht, verbunden wird, worauf die Brandsohle mit dem damit verbundenen Schuhoberteil auf einen Leisten aufgespannt und in eine Form eingesetzt werden, und daß in diese Form polyurethanbildendes Material eingefüllt wird, welches an die Unterseite der Brandsohle anschäumt und einen Polyurethankörper bildet, der die Laufsohle und/oder das Fußbett bildet. Um zu vermeiden, daß das polyurethanbildende Material beim Schäumvorgang durch die Brandsohle hindurchdringt und sich dann mit dem Leisten verbindet, ist es erforderlich, die Brandsohle mit einem aushärtbaren Binder zu imprägnieren, damit die zwischen den Fasern, Fäden od.dgl. vorhandenen Zwischenräume im Brandsohlenmaterial geschlossen werden und ein Hindurchtreten des Polyurethanschaumes verhindert wird. Dadurch wird aber die Brandsohle derart verfestigt, daß sie starr und unnachgiebig wird, ao daß eine elastische Abstützung des Fußes trotz der Verwendung von elastischem, nachgiebigem Polyurethanschaum für das Fußbett und/oder die Laufsohle in unzureichender Weise erfolgt. Die elastischen Eigenschaften des Polyurethanschaumes werden nämlich durch die starre, unnachgiebige Brandsohle in unerwünschter Weise größtenteils unwirksam gemacht.Shoes of the so-called "California design" are already known, in which the manufacture takes place in such a way that an insole made of textile or synthetic material is first connected to the upper, for example by a seam, whereupon the insole with the upper part connected to it a last stretched and inserted into a mold, and that in this mold polyurethane-forming material is filled, which foams to the underside of the insole and forms a polyurethane body, which forms the outsole and / or the footbed. In order to avoid that the polyurethane-forming material penetrates through the insole during the foaming process and then connects to the last, it is necessary to impregnate the insole with a hardenable binder so that the like between the fibers, threads or the like. existing gaps in the insole material are closed and passage of the polyurethane foam is prevented. As a result, however, the insole is strengthened in such a way that it becomes rigid and unyielding, so that an elastic support of the foot takes place in an inadequate manner despite the use of elastic, flexible polyurethane foam for the footbed and / or the outsole. The elastic properties of the polyurethane foam are undesirably largely rendered ineffective by the rigid, unyielding insole.
Ein weiterer Nachteil der bekannten Brandsohlen besteht darin, daß das Annähen des Schuhoberteiles an die durch den Binder verfestigte, starre und harte Brandsohle schwierig durchzuführen ist und häufig zu Verletzungen der Finger der mit dieser Arbeit betrauten Personen führt bzw. das Tragen von Arbeitshandschuhen erforderlich macht. Schließlich besitzen die bekannten Brandsohlen nur ein unzureichendes Wärmeisoliervermögen.Another disadvantage of the known insoles is that the sewing of the shoe upper to the rigid and hard insole solidified by the binder is difficult to carry out and often leads to injuries to the fingers of the persons entrusted with this work or makes it necessary to wear work gloves. After all, the known insoles only have insufficient thermal insulation.
Der Erfindung liegt die Aufgabe zugrunde, eine Brandsohle zu schaffen"die eine elastische Abstützung des Fußes gewährleistet bzw. die durch den Polyurethankörper bewirkte elastische Abstützung des Fußes nicht in unerwünschter Weise wieder unwirksam macht, und die wärme-und kälteisolierend wirkt. Zur Lösung dieser Aufgabe wird vorgeschlagen, daß zumündest der obere Bereich des Vlieses, der der Oberseite der Brandsohle, auf welcher Oberseite der Fuß aufruht, benachbart ist, mit einer Dispersion oder Emulsion imprägniert ist, welche mindestens 1 Gew.%, vorzugsweise 1 bis 5 Gew.-%, Mikrohohlkugeln enthält, deren dünne Hülle aus einem Vinylidenchlorid-Copolymerisat besteht und die mit einem Gas gefüllt sind. Da diese Mikrohohlkugeln eine dünne, elastische, geschlossene Hülle aufweisen und ein Gas enthalten, wirken diese Mikrohohlkugeln wie Gaspolster, es wird somit eine elastische, nachgiebige Abstützung der Fußsohle auch durch die erfindungsgemäße Brandsohle gewährleistet. Trotzdem wird ein unerwünschtes Hindurchtreten des polyurethanbildenden Materiales beim Schäumvorgang durch die erfindungsgemäße Brandsohle ebenso wie bei den bekannten starren und steifen Brandsohlen verhindert.The invention has for its object to provide an insole " which ensures elastic support of the foot or does not undesirably render the elastic support of the foot caused by the polyurethane body ineffective again, and which has a heat and cold insulation effect. To solve this problem It is proposed that the upper area of the fleece, which is adjacent to the upper side of the insole on which the upper side rests, be impregnated with a dispersion or emulsion which contains at least 1% by weight, preferably 1 to 5% by weight. Contains hollow microspheres, the thin shell of which consists of a vinylidene chloride copolymer and which are filled with a gas. Since these hollow microspheres have a thin, elastic, closed shell and contain a gas, these hollow microspheres act like gas cushions, so that it becomes an elastic, resilient The sole of the foot is also supported by the insole according to the invention prevents an undesired passage of the polyurethane-forming material during the foaming process through the insole according to the invention as well as with the known rigid and rigid insoles.
Bei Verwendung der erfindungsgemäßen Brandsohle wird also die Elastizität des das Fußbett und/oder die Laufsohle bildenden Polyurethankörpers nicht aufgehoben, so daß der mit einer solchen Brandsohle versehene Schuh hervorragende druckelastische und trittelastische Eigenschaften besitzt.When using the insole according to the invention, the elasticity of the polyurethane body forming the footbed and / or the outsole is not eliminated, so that the shoe provided with such an insole has excellent pressure-elastic and wear-resisting properties.
Das in die Mikrohohlkugeln eingeschlossene Gas wirkt weiters thermisch isolierend, so daß bei Verwendung der er-findungsgemäßen Brandsohle ein angenehmes Tragegefühl erzielt wird. Schließlich wird auch das Gewicht der erfindungs- gemäßen Brandsohle, bei welcher die beigemengten Mikrohohlkugeln 6 bis 36 % des Gesamtvolumens der Brandsohle ausfüllen, beträchtlich reduziert. Das Annähen des Schuhoberteiles wird gleichfalls bei der erfindungsgemäßen Brandsohle wesentlich erleichtert.The gas enclosed in the hollow microspheres also has a thermally insulating effect, so that a comfortable fit is achieved when using the insole according to the invention. Finally, the weight of the insole according to the invention, in which the added hollow microspheres fill 6 to 36% of the total volume of the insole, is considerably reduced. The sewing on of the shoe upper is also made considerably easier with the insole according to the invention.
Die Verwendung entsprechender Mikrohohlkugeln ist zwar an sich aus der AT-B-366 565 bekannt, allerdings nur bei einer Laufsohle. Daher coirken hier die Mikrohohlkugeln auch nicht als Blockierung gegen das Eindringen des die Laufsohle bildenden Polyurethanschaumes, wie dies bei der Erfindung der Fall ist, da die Kugeln bei diesem Stand der Technik selbst im Polyurethanschaum eingebettet sind.The use of corresponding hollow microspheres is known per se from AT-B-366 565, but only for an outsole. Therefore, the hollow microspheres do not coir here as a blockage against the penetration of the polyurethane foam forming the outsole, as is the case with the invention, since the balls themselves are embedded in the polyurethane foam in this prior art.
Gemäß einer bevorzugten Ausführungsform der Erfindung ist im Vlies etwa parallel zur Ober-und Unterseite der Brandsohle eine Verstärkungseinlage angeordnet, wobei vorzugsweise die Fasern des Vlieses die Verstärkungseinlage zumindest teilweise durchsetzen. Dadurch wird die erfindungsgemäße Brandsohle extrem reißfest und dehnungsfest gemacht, so daß eine Zerstörung der Mikrohohlkugeln auch bei starken Beanspruchungen der Brandsohle nicht erfolgt.According to a preferred embodiment of the invention, a reinforcing insert is arranged in the fleece approximately parallel to the top and bottom of the insole, the fibers of the fleece preferably at least partially penetrating the reinforcing insert. As a result, the insole according to the invention is made extremely tear-resistant and stretch-resistant, so that the hollow microspheres are not destroyed even when the insole is subjected to heavy loads.
Das die Brandsohle bildende Vlies kann zur Gänze mit der die Mikrohohlkugeln aufweisenden Dispersion oder Emulsion imprägniert sein. Zweckmäßig ist jedoch eine Anordnung, bei welcher lediglich der der Oberseite der Brandsohle benachbarte Bereich des Vlieses, vorzugsweise etwa bis zur Verstärkungseinlage, soferne eine solche vorgesehen ist, mit der Dispersion oder Emulsion imprägniert, wogegen der untere Bereich des Vlieses in dem Polyurethankörper verankert ist. Dadurch wird eine hervorragende Verbindung zwischen der Brandsohle und dem Polyurethankörper beim Anschäumen desselben an die Unterseite der Brandsohle erzielt, vor allem dann, wenn sich einzelne Fasern des Vlieses durch die Verstärkungseinlage hindurcherstrecken, da dann diese Fasern teilweise in der verfestigten, die Mikrohohlkugeln enthaltenden Dispersion oder Emulsion verankert sind, teilweise in dem Polyurethankörper.The fleece forming the insole can be completely impregnated with the dispersion or emulsion having the hollow microspheres. However, an arrangement is expedient in which only the area of the fleece that is adjacent to the top of the insole, preferably up to the reinforcement insert, if one is provided, impregnated with the dispersion or emulsion, whereas the lower region of the fleece is anchored in the polyurethane body. This provides an excellent connection between the insole and the polyurethane body when it is foamed onto the underside of the insole, especially when individual fibers of the fleece extend through the reinforcement insert, since these fibers then partially in the solidified dispersion containing the hollow microspheres or Emulsion are anchored, partly in the polyurethane body.
Das Vlies besteht zweckmäßig aus Polyesterfasern oder Polyamidfasern oder Polyacrylfasern, wobei auch Mischungen dieser Fasern verwendet werden können.The fleece expediently consists of polyester fibers or polyamide fibers or polyacrylic fibers, and mixtures of these fibers can also be used.
Besonders günstige Resultate werden erzielt, wenn das Vlies vor seiner Imprägnierung ein Flächengewicht zwischen 120 und 360 g/m2, vorzugsweise zwischen 140 und 200 g/m2 aufweist. Zweckmäßig ist hiebei das Vlies in einer Menge von 55 bis 87 Gew.-% vorgesehen.Particularly favorable results are achieved if the nonwoven has a basis weight between 120 and 360 g / m 2 , preferably between 140 and 200 g / m 2 , before it is impregnated. The fleece is expediently provided in an amount of 55 to 87% by weight.
Die Verstärkungseinlage kann aus einem Gewebe, beispielsweise einem Gittergewebe oder einem Bändchengewebe, oder aus einem Gewirke gebildet sein, Zweckmäßig besteht die Verstärkungseinlage aus Polypropylenfasern mit einem Flächengewicht zwischen 72 und 165 g/m2, vorzugsweise zwischen 85 und 115 g/m2.The reinforcement insert can be formed from a fabric, for example a lattice fabric or a ribbon fabric, or from a knitted fabric. The reinforcement insert advantageously consists of polypropylene fibers with a basis weight between 72 and 165 g / m 2 , preferably between 85 and 115 g / m2.
Als Dispersion zur Imprägnierung des Vlieses wird zweckmäßig eine Kunststoffdispersion, vorzugsweise eine Polymerdispersion, verwendet, es kann aber auch das Vlies mit einer Dispersion auf der Basis Naturkautschuk oder synthetischer Kautschuk imprägniert sein.A plastic dispersion, preferably a polymer dispersion, is expediently used as the dispersion for impregnating the nonwoven, but the nonwoven can also be impregnated with a dispersion based on natural rubber or synthetic rubber.
Gute Resultate werden erzielt, wenn der Durchmesser der Mikrohohlkugeln zwischen 0,01 und 1 mm beträgt, wobei vorzugsweise Mikrohohlkugeln unterschiedlichen Durchmessers vorgesehen sind. Mikrohohlkugeln der genannten Größe bewirken eine gute trittelastische Abstützung der Fußsohle, ohne daß an der Oberseite der Brandsohle durch die Mikrohohlkugeln Erhebungen entstehen, welche als störend empfunden werden. Werden Mikrohohlkugeln unterschiedlichen Durchmessers verwendet, so fügen sich die Mikrohohlkugeln kleineren Durchmessers in die Zwischenräume zwischen den Mikrohohlkugeln größeren Durchmessers ein, so daß eine gleichmäßige Gesamtverteilung der Mikrohohlkugeln in der Brandsohle erfolgt.Good results are achieved when the diameter of the hollow microspheres is between 0.01 and 1 mm, preferably hollow microspheres of different diameters being provided. Hollow microspheres of the size mentioned provide a good, step-elastic support of the sole of the foot without the hollow hollow spheres at the top of the insole, which are perceived as disturbing. If hollow microspheres of different diameters are used, the hollow microspheres of smaller diameter fit into the spaces between the hollow microspheres of larger diameter, so that a uniform overall distribution of the hollow microspheres takes place in the insole.
Die Oberseite, auf welcher der Fuß aufruht, der Brandsohle kann gegebenenfalls mit einer Abdeckung beispielsweise aus textilem Material versehen sein.The top, on which the foot rests, the insole can optionally be provided with a cover, for example made of textile material.
Beim Herstellen der erfindungsgemäßen Brandsohle kann so vorgegangen werden, daß das vorzugsweise aus synthetischen Fasern bestehende Vlies zumindest teilweise mit einer Dispersion oder Emulsion imprägniert wird, in welcher ein Treibmittel enthaltende Kompaktteilchen aus Vinylidenclorid-Copolymerisat enthalten sind, und daß anschließend das so imprägnierte Vlies auf eine Temperatur von mehr als 75° C erwärmt wird, wobei sich die Mikrohohlkugeln aus den ein bilden. Dadurch, daß sich die Mikrohohlkugeln aus den ein Treibmittel enthaltenden Kompaktteilchen infolge der Wärmezufuhr in situ bilden, wird eine gleichmäßig verteilte, eng aneinanderliegende Anordnung der Mikrohohlkugeln verschiedenen Durchmessers gewährleistet.In the manufacture of the insole according to the invention, the procedure can be such that the nonwoven, which preferably consists of synthetic fibers, is at least partially impregnated with a dispersion or emulsion in which a propellant-containing compact particle of vinylidene chloride copolymer is contained, and that the nonwoven thus impregnated is then applied to a Temperature of more than 75 ° C is heated, whereby the hollow microspheres form from one. The fact that the hollow microspheres form the compact particles containing a propellant in situ as a result of the supply of heat ensures a uniformly distributed, closely spaced arrangement of the hollow microspheres of different diameters.
Die Kompaktteilchen, die durch Wärmezufuhr die Mikrohohlkugeln bilden, sind unter dem Warenzeichen EXPANCEL bekannt und von der Firma Kema Nord in Sundsvall (Schweden) zu beziehen.The compact particles that form the hollow microspheres through the supply of heat are known under the trademark EXPANCEL and are available from Kema Nord in Sundsvall (Sweden).
Die Bildung der Mikrohohlkugeln in situ kann bei der Trockung einer wässerigen Dispersion bei gleichzeitiger Wärmezufuhr erfolgen. In diesem Fall muß eine Dispersion mit duroplastischen Eigenschaften, beispielsweise eine aus Melaminharzen oder anderen Aminoplasten bestehende Dispersion verwendet werden.The formation of the hollow microspheres in situ can take place when an aqueous dispersion dries with simultaneous supply of heat. In this case, a dispersion with thermosetting properties, for example a dispersion consisting of melamine resins or other aminoplasts, must be used.
Es kann aber auch erst nach Trocknung der Dispersion die Bildung der Mikrohohlkugeln in situ durch eine Erwärmung auf eine Temperatur von mehr als 85°C erfolgen. Damit sich nach bereits erfolgter Trocknung der Dispersion die Mikrohohlkugeln noch bilden können, ist es erforderlich, eine Dispersion mit thermoplastischen Eigenschaften zu verwenden, beispielsweise eine aus Polyacrylsäureester oder aus Polyvinylacetat bestehende Dispersion.However, the hollow microspheres can only be formed in situ by heating to a temperature of more than 85 ° C. after the dispersion has dried. So that the hollow microspheres can still form after the dispersion has already dried, it is necessary to use a dispersion with thermoplastic properties, for example a dispersion consisting of polyacrylic acid ester or polyvinyl acetate.
Nach einem anderen Verfahren zur Herstellung der Brandsohle wird das Vlies zumindest teilweise mit einer Dispersion oder Emulsion imprägniert, welche bereits fertige Mikrohohlkugeln enthält, deren dünne Hülle aus Vinylidenchlorid-Copolymerisat besteht und deren hohler Kern ein Gas enthält, worauf die Dispersion trocknen gelassen wird. Eine solche Vorgangsweise empfiehlt sich vor allem dann, wenn nicht das gesamte Vlies, sondern nur der obere Bereich desselben etwa bis zur Mitte, wo sich vorzugsweise die Verstärkungseinlage befindet, imprägniert werden soll. Die Dispersion oder Emulsion wird in diesem Fall zweckmäßig mit einer Rakel auf das Vlies aufgebracht.According to another method of manufacturing the insole, the nonwoven is at least partially impregnated with a dispersion or emulsion which already contains finished hollow microspheres, the thin shell of which consists of vinylidene chloride copolymer and whose hollow core contains a gas, after which the dispersion is allowed to dry. Such a procedure is particularly recommended when not the entire fleece, but only the upper area thereof is to be impregnated approximately to the middle, where the reinforcement insert is preferably located. In this case, the dispersion or emulsion is expediently applied to the nonwoven using a doctor blade.
Die Erwärmung und/oder Trocknung der Dispersion oder Emulsion erfolgt vorzugsweise in einem Hochfrequenzfeld. Dadurch wird der Vorteil erzielt, daß an allen Stellen des Vlieses eine gleichmäßige Erwärmung stattfindet, so daß auch eine gleichmäßige Trocknung der Dispersion oder Emulsion sowohl an der Oberfläche als auch im Inneren erfolgt. Bei Herstellung der Mikrohohlkugeln in situ werden diese weiters bei Verwendung eines Hochfrequenzfeldes überall gleichzeitig gebildet und sind daher gleichmäßig im Vlies verteilt.The dispersion or emulsion is preferably heated and / or dried in a high-frequency field. This has the advantage that uniform heating takes place at all points of the nonwoven, so that the dispersion or emulsion also dries uniformly both on the surface and in the interior. When the hollow microspheres are produced in situ, they are also formed simultaneously everywhere using a high-frequency field and are therefore evenly distributed in the fleece.
Zweckmäßig ist es, das Vlies vor dem Imprägnieren zu verfestigen, beispielsweise dadurch, daß man dieses Vlies wenigstens einmal nadelt.It is expedient to solidify the fleece before impregnation, for example by needling this fleece at least once.
In der Zeichnung ist die Erfindung anhand von Ausführungsbeispielen schematisch veranschaulicht. Fig. 1 zeigt einen Längsschnitt durch einen mit einer erfindungsgemäßen Brandsohle ausgestatteten Schuh. Fig. 2 zeigt in vergrößer-ter Darstellung eine erfindungsgemäß ausgebildete Brandsohle mit daran angeschäumtem Polyurethankörper im Schnitt. Fig. 3 stellt eine weitere Ausführungsform der erfindungs-gemäßen Brandsohle mit daran angeschäumtem Polyurethankörper im Schnitt dar.In the drawing, the invention is illustrated schematically using exemplary embodiments. Fig. 1 shows a longitudinal section through a shoe equipped with an insole according to the invention. Fig. 2 shows an enlarged view of an insole designed according to the invention with a foamed polyurethane body in section. Fig. 3 shows a further embodiment of the insole according to the invention with a foamed polyurethane body in section.
Der in Fig. 1 dargestellte Schuh weist eine Brandsohle 1 auf, welche mit einem Schuhoberteil 2 durch eine Naht 3 verbunden ist. Die Oberseite 4 der Brandsohle, auf welcher der Fuß aufruht, kann durch eine Abdeckung 5 aus flächigem Material abgedeckt sein. An der Unterseite 6 der Brandsohle 1 ist ein das Fußbett bildender Polyurethankörper 7 angeschäumt, welcher an seiner Unterseite die Laufsohle 8 trägt. Die Laufsohle 8 kann auch einstückig mit dem Polyurethankörper 7 ausgebildet sein bzw. aus dem Polyurethankörper 7 bestehen.The shoe shown in FIG. 1 has an
Wie aus den Fig. 2 und 3 hervorgeht, besteht die Brandsohle 1 aus einem Vlies 9 aus synthetischen Fasern, in dem, etwa in der Mitte zwischen der Oberseite 4 und der Unterseite 6, eine Verstärkungseinlage 10 angeordnet ist, die aus einem Gewebe, beispielsweise einem Bändchengewebe, oder einem Gewirke aus synthetischen Fasern besteht. Die Fasern des Vlieses 9 verlaufen teilweise von der Oberseite 4 zur Unterseite 6 der Brandsohle 1 und durchsetzen hiebei die Verstärkungseinlage 10.As can be seen from FIGS. 2 and 3, the
Bei der Ausführungsform nach Fig. 2 ist das Vlies 9 zur Gänze mit einer Dispersion oder Emulsion imprägniert, welche mindestens 1 Gew.- % Mikrohohlkugeln 11 enthält, deren dünne Hülle aus Vinylidenchlorid-Copolymerisat besteht und deren hohler Kern ein Gas enthält. An der Unterseite 6 der Brandsohle 1 ist der Polyurethankörper 7 angeschäumt.In the embodiment according to FIG. 2, the
Mikrohohlkugeln der erwähnten Art sind bereits bekannt und beispielsweise in der Literaturstelle Modern Plastics, August 1969, Seiten 55 bis 57 beschrieben.Hollow microspheres of the type mentioned are already known and are described, for example, in the reference Modern Plastics, August 1969, pages 55 to 57.
Die Ausführungsform nach Fig. 3 unterscheidet sich von der Ausführungsform nach Fig. 2 dadurch, daß lediglich der der Oberseite 4 benachbarte Teil des Vlieses 9 etwa bis zur Verstärkungseinlage 10 mit einer Dispersion imprägniert ist, welche die erwähnten Mikrohohlkugeln besitzt. Der unterhalb der Verstärkungseinlage 10 befindliche, nicht imprägnierte Bereich des Vlieses 9 wird bei dieser Ausführungsform in den Polyurethanteil 7 eingebettet, wodurch sich eine noch bessere Verbindung zwischen der Brandsohle und dem Polyurethanteil 7 ergibt. . The embodiment according to FIG. 3 differs from the embodiment according to FIG. 2 in that only that part of the
Bei der Herstellung der Brandsohle kann so vorgegangen werden, daß das Vlies 9 mit der Verstärkungseinlage 10 versehen wird und anschließend mit einer Dispersion imprägniert wird, in der ein Treibmittel enthaltende Kompaktteilchen aus Vinylidenchlorid-Copolymerisat enthalten sind. An-schließend wird das imprägnierte Vlies 9 auf eine Temperatur von mehr als 75°C erwärmt, wobei sich die Mikrohohlkugeln in situ bilden.In the manufacture of the insole, the procedure can be such that the
Die Bildung der Mikrohohlkugeln in situ kann gleichzeitig mit der Trocknung der wässerigen Dispersion durch Wärmezufuhr erfolgen. Vorzugsweis erfolgt die Wärmezufuhr im Hochfrequenzfeld. Dies bringt den Vorteil mit sich, daß an allen Stellen des Vlieses eine gleichmäßige Erwärmung stattfindet und dadurch auch die Mirohohlkugeln überall gleichzeitig gebildet werden.The formation of the hollow microspheres in situ can take place simultaneously with the drying of the aqueous dispersion by the application of heat. The heat is preferably supplied in the high-frequency field. This has the advantage that uniform heating takes place at all points of the nonwoven and as a result the hollow mirrors are simultaneously formed everywhere.
Wenn die Bildung der Mikrohohlkugeln in situ gleichzeitig mit der Trocknung der wässerigen Dispersion erfolgt, so muß eine Dispersion mit duroplastischen Eigenschaften, beispielsweise eine aus Melaminharzen oder anderen Aminoplasten bestehende Dispersion verwendet werden.If the formation of the hollow microspheres takes place in situ simultaneously with the drying of the aqueous dispersion, then a dispersion with thermosetting properties, for example a dispersion consisting of melamine resins or other aminoplasts, must be used.
Es kann aber auch die Bildung der Mikrohohlkugeln aus den Kompaktteilchen erst nach bereits erfolgter Trocknung der Dispersion erfolgen. In diesem Fall ist es erforderlich, eine Dispersion mit thermoplastischen Eigenschaften zu verwenden, beispielsweise eine als Polyacrylsäureester oder Polyvinylacetat bestehende Dispersion.However, the hollow microspheres can also be formed from the compact particles only after the dispersion has already dried. In this case, it is necessary to use a dispersion with thermoplastic properties, for example a dispersion consisting of a polyacrylic acid ester or polyvinyl acetate.
Zweckmäßsig ist es, das Vlies 9 vor dem Imprägnieren zu verfestigen, beispielsweise dadurch, daß man dieses Vlies 9 wenigstens einmal nadelt.It is expedient to solidify the
Es kann aber auch so vorgegangen werden, daß das Vlies 9 mit einer Dispersion imprägniert wird, welche bereits fertige Mikrohohlkugeln 11 enthält. Dies ist beispielsweise bei der Ausführungsform nach Fig. 3 zweckmäßig, wo lediglich der ober Bereich des Vlieses 9 imprägniert wird. Die mit fertigen Mikrohohlkugeln 11 versehene Dispersion wird in diesem Falle beispielsweise mittels einer Rakel auf das Vlies aufgetragen und trochnen gelassen. Nach dem Trocknen wird die so gebildete Brandsohle mit dem Schuhoberteil 2 verbunden und anschließend an die Unterseite der Brandsohle 1 das polyurethanbildende Material angeschäumt, aus welchem der Teil 7 gebildet wird, welcher das Fußbett und/oder die Laufsohle bildet.However, it can also be done in such a way that the
Claims (24)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
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AT83890137T ATE18123T1 (en) | 1982-08-27 | 1983-08-26 | INSOLE FOR SHOES AND METHOD OF MAKING THE SAME. |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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DE19823231971 DE3231971A1 (en) | 1982-08-27 | 1982-08-27 | INSOLE FOR SHOES AND METHOD FOR THE PRODUCTION THEREOF |
DE3231971 | 1982-08-27 |
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EP0101676A1 EP0101676A1 (en) | 1984-02-29 |
EP0101676B1 true EP0101676B1 (en) | 1986-02-26 |
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Application Number | Title | Priority Date | Filing Date |
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EP83890137A Expired EP0101676B1 (en) | 1982-08-27 | 1983-08-26 | Shoe insole and method of making the same |
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US (2) | US4524529A (en) |
EP (1) | EP0101676B1 (en) |
AT (1) | ATE18123T1 (en) |
DE (2) | DE3231971A1 (en) |
ES (1) | ES525194A0 (en) |
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CO2016005772A1 (en) * | 2016-12-26 | 2018-07-19 | Moreno Munetones Enrique Alejandro | Knitted non-woven textile with expanded micro-spheres and manufacturing method |
US10806209B2 (en) | 2017-01-06 | 2020-10-20 | Under Armour, Inc. | Composite soles |
CN110831453A (en) * | 2017-01-13 | 2020-02-21 | 安娜·宝拉·佩雷拉·拉格 | Physiological footwear with dynamically constructed microparticles applied to insole and uneven arrangement applied to sole |
USD858968S1 (en) | 2017-01-19 | 2019-09-10 | Storelli Sports, Inc. | Insole |
USD899061S1 (en) | 2017-10-05 | 2020-10-20 | Adidas Ag | Shoe |
EP3836816A1 (en) * | 2018-10-19 | 2021-06-23 | NIKE Innovate C.V. | Footwear sole structure having a composite element and methods for manufacturing same |
US11382785B2 (en) * | 2019-07-15 | 2022-07-12 | Joyce MINOSH | Therapeutic vessel, related footwear, and method of manufacture and use |
WO2021016189A1 (en) | 2019-07-25 | 2021-01-28 | Nike Innovate C.V. | Article of footwear |
US11607009B2 (en) | 2019-07-25 | 2023-03-21 | Nike, Inc. | Article of footwear |
CN114727682A (en) | 2019-07-25 | 2022-07-08 | 耐克创新有限合伙公司 | Cushioning member for an article of footwear |
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DE1065344B (en) * | 1948-10-01 | |||
US2845640A (en) * | 1952-11-07 | 1958-08-05 | Alan E Murray | Process of producing a sole for shoes |
US2879197A (en) * | 1956-04-19 | 1959-03-24 | Fiber Bond Corp | Foamable pad and method of making same |
AT241799B (en) * | 1959-05-20 | 1965-08-10 | Tru Scale Inc | Method and device for the continuous production of sheets, webs or the like from foamable, thermoplastic material |
AT282204B (en) * | 1962-10-31 | 1970-06-25 | Bunzl & Biach Ag | Method and device for the production of form-stabilized bodies from polyurethane foam containing fiber material |
DE1504254B2 (en) * | 1964-06-23 | 1972-08-31 | Elbel, Karl, Dr., 7531 Büchenbronn | METHOD FOR PRODUCING FOAMED PLASTIC STRUCTURES WITH FIBER FIBER FIBER REINFORCEMENTS EVEN DISTRIBUTED IN THE FORMED |
US3407406A (en) * | 1965-06-14 | 1968-10-29 | Rosemount Eng Co Ltd | Conformable pad and material for use therein |
US3414988A (en) * | 1965-12-07 | 1968-12-10 | Marbill Company | Shoe having a cushioned insole |
GB1198552A (en) * | 1968-02-01 | 1970-07-15 | Monsanto Chemicals | Footwear. |
US3654065A (en) * | 1968-07-22 | 1972-04-04 | Goeppinger Raliko Und Kunstled | Flat-shaped articles of vinyl polymers and process of producing same |
DE1952954A1 (en) * | 1969-10-21 | 1971-05-06 | Sumitomo Bakelite Co | Reinforced foam products |
CA959722A (en) * | 1971-04-30 | 1974-12-24 | Silvio Vargiu | Poromeric materials |
US3791050A (en) * | 1972-01-19 | 1974-02-12 | Wolverine World Wide Inc | Shoe sole and heel |
US3962512A (en) * | 1972-05-22 | 1976-06-08 | Industrie Pirelli S.P.A. | Composite laminar structure and relative manufacturing process |
DE2456754A1 (en) * | 1973-12-05 | 1975-06-12 | Gen Electric | FOOTWEAR WITH A CORE ADAPTED TO THE FOOT |
IT1046801B (en) * | 1974-07-12 | 1980-07-31 | Pirelli | IMPROVED PADDING ITEMS AND PROCESS FOR THEIR PRODUCTION |
DE2548819A1 (en) * | 1975-10-31 | 1977-05-05 | Walter Dr Behr | Heat insulating soft PVC insole - with smooth side and fleecy or felt-like side |
AR208234A1 (en) * | 1976-05-28 | 1976-12-09 | Suilene Sa | NEW SPONGY PRODUCT CONSTITUTED BY A FOAMABLE SUBSTANCE CAPABLE OF PROVIDING A CELLAR MATERIAL AND A THREE-DIMENSIONAL FIBROUS RETICULAR STRUCTURE INCORPORATED THEREOF |
DE2728774C3 (en) * | 1977-06-25 | 1980-04-10 | Deutsche Gold- Und Silber-Scheideanstalt Vormals Roessler, 6000 Frankfurt | Inner shoe material, such as insole and midsole material, in sheet form or in cut-outs therefrom |
US4257176A (en) * | 1979-03-09 | 1981-03-24 | Scholl, Inc. | Insole with material released under foot loads |
AT366565B (en) * | 1979-11-08 | 1982-04-26 | Schaefer Philipp | MOLDED PART FROM POLYURETHANE AND METHOD FOR PRODUCING THE SAME |
EP0033448A1 (en) * | 1980-01-18 | 1981-08-12 | Ag Depharma | Foot protector |
DE8127504U1 (en) * | 1981-09-19 | 1982-04-15 | J.H. Benecke Gmbh, 3000 Hannover | Insole |
DE3148712A1 (en) * | 1981-12-09 | 1983-06-23 | Fa. Carl Freudenberg, 6940 Weinheim | SHOE INSERT |
-
1982
- 1982-08-27 DE DE19823231971 patent/DE3231971A1/en not_active Withdrawn
-
1983
- 1983-08-24 US US06/526,112 patent/US4524529A/en not_active Expired - Fee Related
- 1983-08-26 AT AT83890137T patent/ATE18123T1/en not_active IP Right Cessation
- 1983-08-26 EP EP83890137A patent/EP0101676B1/en not_active Expired
- 1983-08-26 DE DE8383890137T patent/DE3362311D1/en not_active Expired
- 1983-08-27 ES ES525194A patent/ES525194A0/en active Granted
-
1985
- 1985-01-25 US US06/695,095 patent/US4575446A/en not_active Expired - Fee Related
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ATE18123T1 (en) | 1986-03-15 |
US4575446A (en) | 1986-03-11 |
US4524529A (en) | 1985-06-25 |
ES8500730A1 (en) | 1984-11-01 |
ES525194A0 (en) | 1984-11-01 |
DE3231971A1 (en) | 1984-03-15 |
DE3362311D1 (en) | 1986-04-03 |
EP0101676A1 (en) | 1984-02-29 |
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