EP2028961A1

EP2028961A1 - Method and device for functionalising functionalising the surfaces of adhesive closing parts

Info

Publication number: EP2028961A1
Application number: EP07725605A
Authority: EP
Inventors: Konstantinos Poulakis
Original assignee: Gottlieb Binder GmbH and Co KG
Current assignee: Gottlieb Binder GmbH and Co KG
Priority date: 2006-06-22
Filing date: 2007-05-26
Publication date: 2009-03-04
Anticipated expiration: 2027-05-26
Also published as: EP2028961B1; PL2028961T3; CN101460073A; WO2007147479A1; US8895114B2; JP5727136B2; US20090311438A1; DK2028961T3; DE102006028581A1; CN101460073B; JP2009541081A

Abstract

The invention relates to a method for functionalising the surfaces of adhesive closing parts which form, with correspondingly formed adhesive closing parts, an adhesive closure that can be repeatedly opened and closed. The surface energy of the adhesive closing part is modified by means of a proton and/or electron exchanging medium, especially in the form of donors or collectors, using high energy in such a way that the physicochemical properties of the material of the adhesive closing part can be adjusted without a coating and with ageing resistance, by the attachment of functional groups of the exchanging medium to the adhesive closing part material. The invention also relates to a device for carrying out one such method.

Description

Gottlieb Binder GmbH & Co. KG, Bahnhofstr. 19, 71088 Holzgerlingen

Method and device for surface functionalization of

Sealing parts

The invention relates to a method and a device for surface functionalization of adhesive closure parts, which form a repeatedly open and closable adhesive closure with correspondingly formed adhesive closure parts.

EP 1 082 031 B1 discloses a method for producing adhesive closure parts comprising plastic materials having adhesive closure elements, wherein the adhesive closure part is at least partially provided with the adhesive closure elements with a coating whose layer thickness is chosen such that it does not impair the subsequent function of the adhesive closure impaired. The coating on the adhesive closure part is formed by a so-called sol-gel process, preferably based on SiO ₂ and / or TiO ₂ -modified SiO ₂ . The applied over said sol-gel process coating is foam-repellent, which brings advantages, if the known fastener part during foaming of seat cushion parts applies. Although the applied coating is nanocomposite, meaning that the layer thickness can be extremely low, in particular having only a few molecular strengths of the particular coating composition, the coating concerned is not resistant to abrasion and thus is not resistant to aging.

EP 1 077 620 B1 discloses an adhesive closure part, in particular for lathering upholstered parts of vehicle seats, during the production thereof, wherein an adhesive base agent is applied to one side of the adhesive closure part. If the known adhesive closure part consists of a polyamide material, the adhesive base agent is formed from resorcinol and / or at least one of its derivatives or, if the adhesive closure part consists of a polyolefin material, is used as primer polyurethane or a polymer which is via a post-crosslinking formed by curable resins. In this way, a kind of primer layer is formed on the adhesive closure part as an additional coating, which forms a high-strength connection with the respective foam material, even without the use of corresponding adhesive agents. The well-known solution of an application coating can also rub off.

In order to counter this, DE 101 23 205 A1 has already described a method for producing an adhesive closure part having a multiplicity of adhesive closure elements integrally formed with a carrier, in which interlocking heads of the adhesive closure elements are provided with a head part made of a filler to be hardened, in the form of a thermosetting molding composition, preferably in the form of an acrylate, more preferably in the form of a urethane diacrylate. If the pertinent urethane molding material has cured, an adhesive closure part is created, which on the one hand has high temperatures and mechanical properties. can withstand good stresses and on the other hand with appropriate design leads to improved adhesion and peel strength values. The applied thereto high-strength additional coating, however, builds on the fastener elements correspondingly large, which in turn precludes a desired miniaturization of fastener parts, which today attempts to accommodate several thousand fastener elements on a square centimeter of carrier material of the fastener part.

Based on this prior art, therefore, the invention is the

Object on to further improve the known methods and related devices to the effect that in a cost effective manner miniaturized adhesive fastener parts are functionalized in large flow quantities such that a variety of surface and structural properties of various kinds with only a basic concept of treatment steps can be produced. This object is achieved by a method having the features of patent claim 1, as well as a device according to the feature configuration of claim 12.

In the method according to the invention, the surface energy of the adhesive closure part is modified using high energy such that the chemical-physical properties of the adhesive closure material can be adjusted coating-free and age-resistant by means of a proton and / or electron exchange medium, in particular in the form of donors and collectors are by attaching functional groups of the exchange medium to the Haftverschlußteilmaterial. So-called Brönsted acids, which act as proton donors, and so-called Lewis bases, which can donate electrons to other materials as a donor, such as the plastic material of an adhesive closure part, have proven to be particularly versatile. Furthermore, there are protons and / or electrons collecting collectors in the plastic material of the adhesive closure part, which influence the surface energy of the adhesive closure part in a comparable manner to a redox effect, which in turn creates the possibility that function groups can interact with the adhesive closure part using high-energy functional groups of exchange media.

By attaching functional groups of the exchange medium to the adhesive fastener sub-material from the surface and intruding intrinsic material in the fastener part, a substantially coating-free structure is achieved, so that the Oberflächenfunktional ization is feasible in small scales, which in turn the desired miniaturization of the fastener parts together with their Adhesive closure elements accommodates. Since the functional groups are attached to the adhesive closure part in the molecular range and thus interact with the other plastic material of the same change, the pertinent mode of action proves to be resistant to aging, so that there is no fear that after a longer storage period for the adhesive closure parts prior to their use in the Production of the user the desired surface modification is lost. The chemical-physical properties to be set are defined in a broad framework. Thus, the adhesive closure part of its hardness or softness can be set as functional as with respect to a desired temperature resistance. Resistance to chemicals of any kind is then as functionally adjustable as a desired reaction pattern with third-party products, while For example, in the form of polyurethane foam, the starting material in the Sitzteilpolsterfertigung.

Due to the affiliation of chemical functional assemblies to the material of the adhesive closure part, a specific interaction with the respective component can be achieved insofar as the adhesive closure part is to be used. For example, it is possible to make the adhesive closure part flame resistant by affiliation of corresponding functional modules; an application criterion for the respective fastener part, as far as it is used in aerospace engineering applications. If the respective function module has parts to be used with phosphor, the respective adhesive closure part can be used well in the creative design sector, for example to allow luminous color designs. Due to the mentioned change in the surface energy, there is also the possibility of achieving an improved adhesion of corresponding adhesive closure parts to form the adhesive closure, for which capillary technologies (DE 102 07 194 C1) which are otherwise complicated to implement in the prior art are described.

Furthermore, electrical discharge properties of the adhesive closure part can be improved in the case of current or other information transport via the respective functional assemblies to be used. A large number of possible applications is currently not yet covered, and will be the subject of further technical development using the method according to the invention described above.

As preferred apparatus for performing the method is one according to the feature configuration of claim 12, wherein by means of a forming wire, the fastener elements of the adhesive closure part can be produced, wherein on one side of the forming wire, the plastic material for the closure elements in the form of openings of the screen can be fed, and wherein on the opposite side of the forming wire, preferably in situ, the exchange medium can be fed to the mold openings. The device in question allows in a particularly economical way

Carrying out the manufacturing method according to the invention and in particular allows a process-safe process sequence. With the pertinent device can quasi-continuous large quantities of fastener parts with surface modification produce production safe.

Further advantageous embodiments of the method according to the invention are the subject of the other dependent claims.

The single figure shows an example of a highly simplified schematic and partially cut drawn side view of an apparatus for performing the method according to the invention.

The figure shows a schematic representation of parts of a device for carrying out the method according to the invention, with an extruder head 1 as a feeder for in plastic or liquid state, in particular thermoplastic material, which corresponds to a strip whose width of that of the adhesive closure part corresponding to the gap between a pressure tool and a mold is supplied. As a pressure tool, a pressure roller 3 is provided. The molding tool is a molding roll designated as a whole by 5. Both rollers are driven in the direction indicated in the figure with curved arrows 7 and 9 directions of rotation, so that between them a conveying gap is formed, through which the plastic belt is conveyed in the transport direction, while at the same time in the gap as a shaping zone the plastic strip is formed to the carrier 10 of the adhesive fastener part and the carrier 10 is provided on the side adjacent to the forming roll 5 by the shaping elements of the forming roll 5 which are given the necessary shape to form interlocking means.

For this purpose, the forming roller 5 on the periphery of a screen 1 1, with individual mold cavities 12. A pertinent mold cavity 12, which is bounded on both sides by mold openings 12a, b respectively, with the other mold cavities 12 along the forming roller 5 with its wire first 1 outside the outer circumference preferably distributed regularly, the distribution and the number are freely selectable. The respective mold cavity is designed in the manner of a rotation hyperboloid, so that in this respect correspondingly shaped stem parts 13 are formed, which are connected with their respective foot ends integrally with the band-like carrier material 10 and the other free end in a circumferentially widened head part 15th opens. Both stem part 13 and head part 15 each form an adhesive closure element for the total adhesive closure part, which forms a repeatedly open and closable adhesive closure with correspondingly shaped corresponding closure parts of another, not shown fastener part. Closures generated to this effect have also become known under the brand name Kletten ^® -Zeilverschlüsse.

The shaping roller 5 is provided with perforations in the form of media channels 17, which are oriented from their longitudinal orientation to the center 19 as a rotational axis of the forming roller 5. Inside the forming roller 5 and in concentric arrangement with the same, 21 denotes a high energy source, which is symbolically represented. Further, between the outer sheathing of the high energy source 21 and the inner periphery of the forming roll, there is a void, the supply and the temporary storage the exchange medium is used, optionally additional physical parameters of the pertinent empty and working space are adjustable, for example in the form of pressure and temperature, humidity, etc .. Furthermore finds on the pertinent empty or working space 23, the possible supply of lhe gas and fluid media to carry out the process instead, for example, to accelerate the pertinent work progress. Rinsing media can be supplied via the media channels 17 as well as via the space 23 in order to clean off the overall production device from any residues in the process processing.

As a plastic material for each adhesive closure part to be produced, polyolefins have proven to be particularly suitable. The group includes, for example, polyethylenes, polypropylenes, polybutenes, as well as polyisobutenes and poly (4-methyl-1-pentene) s, polymers of the higher alpha-olefins, e.g. Poly (I-hexene), poly (i-octene) or polyd-octadecene). To the pertinent polyolefins also copolymers of different olefins, e.g. which are recognized by ethylene with propylene as belonging. Another good feedstock for the molded fastener parts is polyester.

The proton and / or electron exchange media used are substances and substance groups according to the following chemical overview list, where I denotes the so-called hard bases, Il the soft bases and III the limiting cases of bases. With IV the hard acids are designated, with V the soft acids and with VI the limiting cases of suitable acid materials. Il

H ₂ O OH ^" FR ₂ S RSH RS ^"

AcO ^" SO ₄ ^2" Cl - R ₃ P (RO) ₃ P

CO ₃ ^{2 "} NO ₃ - ROH CN RCN CO

RO ^" R ₂ O NH ₃ C ₂ H ₄ C ₆ H ₆

RNH ₂ SiOH H ^" R-

III IV

ArNH ₃ , C ₅ H ₅ NH ⁺ Li ⁺ Na ⁺

N ₃ -Br K ⁺ Mg ²⁺ Ca ²⁺

NO ₂ ^" Al ^{3 +} Cr ^{2 +} Fe ^{3 +} BF ₃ B (OR) ₃ AIMe ₃ AICI ₃ AIH ₃ SO ₃ RCO ⁺ CO ₂ HX

(hydrogen-binding molecules)

VI

Cu ⁺ Ag ⁺ Pd ²⁺ Fe ²⁺ Co ^{2 +} Cu ²⁺ Pt ^{2 +} Hg ²⁺ BH ₃ Zn ²⁺ Sn ²⁺ Sb ^{3 +} GaCl ₃ I ₂ Br ₂ Bi ³⁺ BMe ₃ SO ₂ CH ₂ carbenes R ₃ C ⁺ NO ⁺ GaH ₃ C ₆ H ₅ ⁺

The classification is based on the pattern that hard acids like to combine with hard bases, as well as soft acids with soft bases. The transitions between hard and soft media are fluent On the whole, the classification should give only a rough idea and information about the effect of the exchange medias. For example, the possible proton release that occurs in all Brönsted acid-base reactions is classified as a hard acid. The soft bases as so-called donors are again characterized by the fact that, in particular, a plurality of electrons or electron pairs can be emitted in order to be able to perform the surface functionalization for the adhesive closure part in this manner. Basically, so-called collectors are also available for influencing the surface functionalization of the adhesive closure part, which in the manner of a redox reaction can liberate electrons and / or protons from the plastic material of the adhesive closure part so as to exert influence; but the degree of functionalization that can be achieved in this way clearly recedes over the protons and / or electron donors.

The desired surface modification can be further optimized by the use of a high energy source. In addition to the use of microwave radiation or other high-frequency field, the use of plasmas is possible. As a possible plasma source DC glow discharges come as well as high-frequency discharges and those with microwave character. In order to reduce the heat load for the plastic material to be produced, the microwave discharge is particularly suitable since the expenditure for this is low, electrodeless coupling is possible, and due to the high degree of ionization of the plasma, short process times are ensured, which is in-situ production of the plasma Adhesive closure part is mandatory. A pertinent plasma source would then be the designated high energy source 21 according to the figure. By the substrate position of the adhesive closure member in the mold cavities 12 of the forming wire 11, a variety of imaginable plasma modification processes can be performed. Thus, the device shown in the figure, for example, for a so-called. In-plasma process in question, in which the surface to be functionalized is located directly in the plasma zone. Likewise, a so-called down-stream method would be conceivable in which a process gas is passed through a plasma zone and then fed to the substrate as a fastener part with its free head ends of adhesive fastener elements. In particular, by adjusting the distance over the drum diameter of the forming roller 5, the thermal load for the substrate in the form of the adhesive closure part can be adjusted so low.

If the process gas used in the plasma zone to implement too quickly or immediately completely, a so-called. After-glow method is possible, wherein an inert carrier gas, for example in the form of nitrogen gas is passed through the plasma zone and activates the process gas, which only after the Plasmazone can be supplied. The then indirectly activated working gas serves the desired surface modification.

Since the drum-type production device can be closed at the drum ends, the process gas guidance can be carried out and set in the empty or working space 23 via suitable inlets and outlets (not shown). For process acceleration, it may be advantageous to supply the process gas under a correspondingly high pressure in the space 23. Instead of the plasma generation source, a dielectric barrier discharge may also be provided for the production method according to the invention, with a modified field source as high energy source 21, which builds up a dielectric field from the center of the forming roller 5 in the direction of the substrate top side of the adhesive closure part. Further, a treatment gas mixture is quasi continuously introduced into the empty and working chamber 23, which preferably consists of a carrier gas and a reducing gas and / or an oxidizing gas, at a pressure which in the present case may be approximately equal to the atmospheric pressure. As oxidizing gases are here in particular CO ₂ or N ₂ O and as reducing gas H ₂ in question. Also, it has proved to be favorable to settle the content of the oxidizing gas in the mixture in a range of 50 to 2000 ppmv and the content of the reducing gas is preferably in a mixture in a value range of 50 to 30,000 ppmv.

Amino, amido, and / or imido groups and compounds can be used with the last-mentioned surface treatment method, in particular as basic electron donors, which, as a functional group, introduces an NH.sub.3 group on the upper side of the adhesive closure part, which forms the structure with further functional assemblies a so-called asymmetric urea bond allowed, which has a further reactive group to which the polyurethane of foam materials can settle in the upholstery foam area, which in such a way leads to a very good connection of the adhesive closure part in the molded foam. A corresponding cover material can then be releasably connected again via a corresponding adhesive closure part with the foamed-in adhesive closure part, which forms the asymmetric urea bond with said foam material.

In addition to the Herstelleinsatz a screen drum according to the figure, it is also possible to handle the Formsiebanordnung in a plane and the forming wire can then be passed through corresponding devices, which then generate the corresponding surface modification as described above. In particular, the sieve can then be formed in the manner of a conveyor belt via deflection rollers with upper and lower sections, the upper strand serving for the shaping and the lower strand for demoulding the adhesive closure part from the individual mold cavities.

Also, the fastener part does not need to be provided with circumferentially widened head ends, as shown in the figure, to provide such an interlocking opportunity. Rather, modern adhesion systems can thus obtain a surface modification. For example, DE 100 65 819 C1 shows a method for producing adhesive closure parts in which a carrier material is provided in at least one subregion of its surface with adhesive closure elements or adhesive elements protruding from its plane, in which a plastic material forming the elements is applied to the carrier element is applied as a support member 10, wherein the elements are formed free of mold at least in a partial area in which the plastic material is deposited by means of at least one applicator in successively dispensed droplets. Although the application device ejects the plastic material with a droplet volume of only a few picoliters via its nozzle, a fast process flow can be realized in this way, so that a fastener part is generated in a very short time. An adhesive closure part produced in this way can also be surface-modified with the described methods.

The device shown in the figure can also be miniaturized from the mold cavities 12 such that adhesive elements can be produced, their adhesion is predominantly by means of van der Waals forces. A pertinent closure system is exemplified in DE 10 2004 012 067 A1. Despite the degree of miniaturization achieved in this way, it is then possible with the pertinent inventive solution to also modify such nano-adhesive closure parts from the surface by default. The device described above is particularly suitable from the front-side head closure material side to influence the respective adhesive closure part. In principle, however, all components of the closing part can optionally be functionalized from their surface, if appropriate with different types of devices, which also applies in particular to the rear side of the carrier of the closure part facing away from the elements or to the upper side of the stem or stem material extending between extends the carrier and the underside of the closure head. For the pertinent surface functionalization, the adhesive closure part with the component or component side that is to be functionalized is thus exposed to the functionalization source, which can take place in closed systems but also in open systems in the passage for a quasi-continuous functionalization.

Claims

Patent claims

1 . Process for the surface functionalization of adhesive closure parts, which form a repeatedly openable and closable adhesive closure with correspondingly formed adhesive closure parts, characterized in that the surface energy of the adhesive closure part by means of a proton and / or electron exchange medium, in particular in the form of donors or collectors High energy is modified so that coating-free and aging resistant, the chemical-physical properties of the adhesive closure material are adjustable by attaching functional groups of the exchange medium to the adhesive closure material part.

2. The method according to claim 1, characterized in that the Anglie- tion process of the functional groups is supported by high energy influence, using

High frequency radiation such as microwave radiation,

- Electric fields, such as the dielectric barrier discharge and - plasma-assisted fields, such as those resulting from the use of a low-pressure or high-pressure plasma.

3. The method according to claim 1 or 2, characterized in that the affiliation process of the functional groups using inert and / or reaction gases is controllable.

4. The method according to any one of claims 1 to 3, characterized in that the affiliation process of the functional groups by means of temperature and / or pressure gradient is controllable.

5. The method according to any one of claims 1 to 4, characterized in that is used as to be functionalized plastic material of the adhesive closure part thermoplastic material, in particular polyolefins and / or polyester lyester.

6. The method according to any one of claims 1 to 5, characterized in that are used as the driving medium basic acting electron donors.

7. The method according to any one of claims 1 to 6, characterized in that are used as basic electron donors amino, amido and / or imido groups and compounds.

8. The method according to claim 7, characterized in that are formed using the basic electron donors asymmetric bonds with the starting material of the adhesive closure part, preferably asymmetric urea bonds arise.

9. The method according to claim 8, characterized in that the asymmetric urea bond by addition of the respective closure part of foam materials, such as polyurethane foam, is formed.

10. The method according to any one of claims 1 to 9, characterized in that the connection of the functional groups takes place on the adhesive closure part in situ.

11.A method according to any one of claims 1 to 10, characterized in that the respective adhesive closure part is manufactured by means of a Siebgebungsver- procedure.

12. Device for carrying out the method according to one of claims 1 to 1 1, characterized in that by means of a forming wire (11), the closure elements (13,15) can be produced, that on one side (12a) of the forming wire (11) Plastic material for the closure elements (13,15) in the form of openings (12) of the screen can be fed, and that on the opposite side of the forming wire (1 1), preferably in situ, the exchange medium the mold openings (12b) can be supplied.