Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
  • C08J5/12—Bonding of a preformed macromolecular material to the same or other solid material such as metal, glass, leather, e.g. using adhesives
  • C08J5/124—Bonding of a preformed macromolecular material to the same or other solid material such as metal, glass, leather, e.g. using adhesives using adhesives based on a macromolecular component
  • C08J5/128—Adhesives without diluent
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
  • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
  • C08L23/04—Homopolymers or copolymers of ethene
  • C08L23/08—Copolymers of ethene
  • C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing atoms other than carbon or hydrogen
  • C08L23/0869—Copolymers of ethene with unsaturated hydrocarbons containing atoms other than carbon or hydrogen with unsaturated acids, e.g. [meth]acrylic acid; with unsaturated esters, e.g. [meth]acrylic acid esters
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers

Definitions

• the invention relates to moldings which can be bonded to metal or plastic substrates and can serve, inter alia, for attaching pipes or pipes.
• moldings made of different materials are known.
• moldings based on polyamides are also known.
• EP 1 533 331 describes polyamides based on C 4 -Cis-dicarboxylic acids and diamines as a molding composition for the production of moldings by low-pressure injection molding.
• EP 0 586 450 is known. This describes hotmelt adhesives, among others made of polyamide, which have a certain melting range. With such melted hot melt adhesives then cables or connectors can be cast. These result in a glued and sealed enclosure of the connector.
• DE 102 16 948 describes a method for connecting two structural parts, wherein both structural parts are joined together with a connecting means, wherein the connecting means comprises an electrically conductive component, and a second component made of a thermoplastic material.
• the conductive connection can be heated by an induction coil and then leads to a connection of the two structural parts.
• an electrically conductive adhesive which consists of a thermoplastic binder and electrically conductive particles that serve to melt for the thermoplastic binder.
• thermoset moldings or metallic moldings which are to be glued, regularly leads to the problem that an adhesive must be chosen, which has good adhesion on both substrates. This must also remain under higher temperature load or under mechanical stress of the substrates, for example by vibration.
• gluing Another requirement for gluing is that the joining should be done in a short period of time, then a high adhesion should arise.
• hot melt adhesives are suitable which build up adhesion through crystallization. Reactive adhesives often have a longer reaction time before they produce a final bond.
• the object was to produce a molding as a fastener that allows rapid bonding to the substrates, which has no multiple adhesive surfaces of the adhesive to substrates, and which has sufficient elasticity to a strength even at elevated temperatures or to ensure at elevated mechanical stress.
• a molding which consists of hot melt adhesives having a high softening temperature.
• the hotmelt adhesive should have a high elasticity and a yield stress of 1 to 35 MPa.
• the invention further relates to a method for bonding molded parts made of hotmelt adhesives, which enables fast and safe application to various substrates.
• substrates As substrates, a variety of known substrates can be used. In particular, these substrates are made of plastic or metal, but other substrates such as e.g. Wood or wood materials, stone or concrete, glass or ceramics, are used. The substrates are essentially hard. Thin sheet metal or plastic substrates, e.g. Sheet metal or plastic parts as molded parts, but are particularly suitable. Usually, however, are not films.
• the moldings according to the invention can have any shape.
• One side should be shaped so that the moldings can be used as a fastening device.
• the molding contains at least one surface which is designed for bonding to the substrate surface. This must have a base area which is sufficient to allow a secure adhesion of the molding on the substrate.
• the connection surface can have different shapes, in particular it is flat. However, it can also be adapted to structured substrates of the shape of the substrate surface. Preferably, an adhesive surface is present. However, it is also possible to increase the adhesive surface or for structural reasons to provide two adhesive surfaces. These may be formed in adaptation to the substrate surfaces.
• the moldings according to the invention should consist of hotmelt adhesives. These may be reactive or non-reactive hot melt adhesives. Such hot melt adhesives may for example be based on polyesters, polyurethanes, polyolefins, polyacrylates or polyamides.
• Hot melt adhesives based on polyesters are described, for example, in EP 028687. These are reaction products of aliphatic, cycloaliphatic or aromatic dicarboxylic acids which can be reacted with aliphatic cyclic or aromatic polyols. By selecting the carboxylic acids and the polyols, crystalline or partially crystalline polyesters can be obtained. Usually, dicarboxylic acids and diols are reacted with each other. However, it is also possible that partially tricarboxylic acids or triols are used.
• thermoplastic polyurethanes are described as hot melt adhesives. These are reaction products of polyols with polyisocyanates, which may have an increased modulus.
• polyols the polyols known per se and based on polyethers, polyesters, polyacrylates, polybutadienes, polyols based on vegetable raw materials, such as oleochemical polyols, can be used.
• at least proportionally aromatic isocyanates are usually included.
• the properties of the prepolymer can be influenced, for example the melting point, the elasticity or the adhesion.
• reactive thermoplastic polyurethanes are also suitable, which may then also be permanently crosslinked after application.
• hot melt adhesives based on polymers are known, such as polyolefins. These are amorphous, crystalline or partially crystalline polyolefins. Examples of these are polypropylene or polyethylene copolymers. The properties of such polymers can be influenced by their molecular weight and by the copolymerized comonomers.
• Such hot melt adhesives are described, for example, in WO 2004/039907, which in this case is polymers prepared by metallocene catalysis.
• suitable hotmelt adhesives may be, for example, polyamides.
• Suitable polyamides are described, for example, in EP 749463. These are polyamide hot melt adhesives based on dicarboxylic acids and polyether diamines. Particularly suitable hotmelt adhesive compositions are described in EP 204 315. These are polyesteramides which are produced on the basis of polymer fatty acids and polyamines.
• polyamides which are suitable according to the invention are those based on dimer fatty acid-free polyamides. These are made from
• the dicarboxylic acids are preferably used in an up to 10% stoichiometric excess over the diamines, so that carboxyl-terminated polyamides are formed.
• the molecular weight of the polyamides to be used according to the invention is about 10,000 to 50,000, preferably 15,000 to 30,000.
• These polyamides suitable according to the invention have a viscosity between 5,000 and 60,000 mPas, preferably between 15,000 and 50,000 mPas (measured at 200 ° C.). Brookfield Thermosel RVT, EN ISO 2555).
• dicarboxylic acids for preparing the polyamides according to the invention are in particular adipic acid, azelaic acid, succinic acid, dodecanedioic acid, glutaric acid, suberic acid, maleic acid, pimelic acid, sebacic acid, undecanedioic acid or mixtures thereof.
• the diamine component consists essentially of one or more aliphatic diamines, preferably having an even number of carbon atoms, with the amino groups at the ends of the carbon chains.
• the aliphatic diamines may contain from 2 up to 20 carbon atoms, which aliphatic chain may be linear or slightly branched.
• ethylenediamine diethylenethamine, dipropylenethamine, 1, 4-diaminobutane, 1, 3-pentanediamine, methylpentanediamine, hexamethylenediamine, trimethylhexamethylenediamine, 2- (2-aminomethoxy) ethanol, 2-methypentamethylenediamine, Cn-neopentanediamine, diaminodipropylmethylamine, 1, 12-diaminododecane.
• the most preferred aliphatic diamines are C 4 -C 12 diamines having an even number of C atoms.
• the amino component may furthermore contain cyclic diamines or heterocyclic diamines, for example 1,4-cyclohexanediamine, 4,4'-diamino-dicyclohexylmethane, piperazine, cyclohexane-bis (methylamine), isophoronediamine, dimethylpiperazine, dipiperidylpropane, norbornanediamine or m-xylylenediamine.
• cyclic diamines or heterocyclic diamines for example 1,4-cyclohexanediamine, 4,4'-diamino-dicyclohexylmethane, piperazine, cyclohexane-bis (methylamine), isophoronediamine, dimethylpiperazine, dipiperidylpropane, norbornanediamine or m-xylylenediamine.
• polyoxyalkylenediamines for example polyoxyethylenediamines, polypropylenediamines or bis (diaminoprop
• aminocarboxylic acids or their cyclic derivatives may also be used.
• a further embodiment of the hot-melt adhesives suitable according to the invention contains as essential component a polyamide based on dimerized fatty acid. Dimerized fatty acids are obtained by coupling unsaturated long-chain monobasic fatty acids, eg, linolenic acid, oleic acid. The acids have long been known and are commercially available.
• the polyamides according to the invention are, for example, composed of 35 to 49.5 mol% of dimerized fatty acid and 0.5 to 15 mol% of monomeric fatty acid having 12 to 22 carbon atoms and 2 to 35 mol% of polyetherdiamines of the general formula
• R5 and R7 are identical or different aliphatic and / or cycloaliphatic hydrocarbon radicals with preferably 2 to 8 carbon atoms and R6 represents an optionally branched aliphatic hydrocarbon radical having 1 to 6 carbon atoms, and 15 to 48 mol% of aliphatic diamines having 2 to 40 carbon atoms, wherein the dimehs faced fatty acids up to 65% by aliphatic dicarboxylic acids can be replaced with 4 to 12 carbon atoms.
• Another suitable composition is obtainable from 20 to 49.5 mol% of dimerized fatty acid and 0.5 to 15 mol% of monomeric fatty acid having 12 to 22 carbon atoms and 20 to 55 mol% of an amine carrying at least 2 primary amino groups with From 2 to 40 carbon atoms, wherein the proportion of dimerized fatty acids may be replaced by up to 65% by aliphatic dicarboxylic acids having 4 to 12 carbon atoms.
• the amine components in the polyamides preference is given to polyether polyols having primary amino end groups, as already mentioned above. In this case, polyether polyols having amino end groups are preferred which are not or only slightly soluble in water.
• the polyether polyols having amino end groups used have in particular molecular weights between 700 and 2500 g / mol.
• a particularly suitable class of raw materials are, for example, the bis (3-aminopropyl) polytetrahydrofurans.
• primary alkylenediamines having 2 to 10 C atoms can be used, selected from the above-mentioned amines.
• Another suitable class of diamines is derived from the dimer fatty acids and contains primary amino groups instead of the carboxyl groups. Such substances are often called dimerdiamines. They are obtained by nitrile formation from the dimehs convinced fatty acids and subsequent hydrogenation.
• carboxylic acids the above-mentioned aliphatic dicarboxylic acids can be used.
• Suitable aliphatic carboxylic acids preferably have 4 to 12 C atoms. By means of these acids dimer fatty acid can be replaced up to 65% by mol. It is also possible to use long-chain aminocarboxylic acids such as 11-aminoundecanoic acid or else lauryl lactam.
• the melting point of the polyamides can be increased within certain limits by the addition of sebacic acid.
• the polyamide raw materials known in fiber chemistry such as, for example, caprolactam. These substances allow the skilled person to increase the melting point within certain limits.
• the amounts of the amine and the carboxylic acids are chosen so that the polyamides have carboxyl groups in an amount of 1-120 meq / kg of solids, in particular between 10 to 100 meq / kg.
• an amine content of between 1 and 140 meq / kg solids should be obtained, in particular between 10 and 100 meq / kg.
• the molecular weight (measured as number average molecular weight, as obtainable via GPC) can be between 30,000 and 300,000 g / mol, in particular between 50,000 and 150,000 g / mol.
• the viscosity of the polyamides should be between 5000 and 100,000 mPas (measured at 200 ° C.), in particular up to 50,000 mPas.
• a preferred embodiment uses as hot melt adhesive polyamides in an amount of 60 to 100 wt .-%.
• the further hot-melt adhesive polymers may be the abovementioned polyurethanes, polyacrylates or polyesters. These must also be compatible with the polyamide in the melt, i. form a stable homogeneous melt.
• 35 to 15 wt .-% of a poly (meth) acrylate polymers may be included. This may consist, for example, of alkyl acrylate monomers, if appropriate, further comonomers may be present, for example ethylene, propylene, styrene or functionalized monomers.
• these poly (meth) acrylates should have polar groups, for example OH, COOH groups or carboxylic anhydride groups.
• Another embodiment employs only polyamides as the hot melt adhesive base polymer.
• the hot melt adhesives suitable according to the invention may contain further customary additives.
• tackifying resins such as, for example, abietic acid, abietic acid esters, terpene resins, terpene-phenolic resins or carbonates. hydrogen resins; Fillers, for example silicates, talc, calcium carbonates, clays, carbon black or pigments; Antioxidants or stabilizers, for example of the type hindered phenols or aromatic amine derivatives; fibrous additives, such as natural fibers, plastic or glass fibers.
• the antioxidants can be used in amounts of up to 1.5% by weight, based on the polymer. In general, these additives should be included as a total not more than 10 wt .-% in a hot melt adhesive according to the invention.
• suitable hot melt adhesives are those that they must have high elasticity and high strength.
• This strength can be characterized by the yield stress (measured according to EN ISO 527-1). According to the invention, it is necessary that the yield stress (at room temperature) be between 1 and 35 MPa, in particular from 3 to 20 MPa.
• the tensile strength is higher, it should be between 1 to 50 MPa, in particular between 10 to 40 MPa.
• the elongation at break can be 200 to 1000%. If the tensile strength is too low, the mechanical (shape) stability of the molding according to the invention is insufficient. Thus, it is possible that under a mechanical load of the molded part by the part to be held this deformed or breaks.
• the hotmelt adhesive of the molding should have a softening temperature (measured according to ASTM E 28) of above 100 0 C, in particular above 150 0 C.
• the temperature may be up to 250 ° C, in particular to to 220 ° C.
• the selection of hot melt adhesives with corresponding softening temperature depends on the substrates to be bonded. If the substrates for the part to be bonded thermally less resilient, such as wood or plastic substrates, it is possible to use a hot melt adhesive with a lower softening temperature as a molded part. If a high load capacity of the substrate is given, it is favorable that the hotmelt adhesive has a higher softening point.
• the moldings of the invention can be prepared in a known manner. For example, these are produced by injection molding.
• the hot-melt adhesive can be injected into a suitable mold, which optionally has possible electrically conductive constituents on the surface intended for bonding, which are thus joined to the shaped body.
• the molded part additionally contains electrically conductive components on or in the surface formed for bonding to the substrate surface.
• these electrically conductive constituents include perforated metal foils, metal wires, metal powders, other conductive powder materials such as ferrite powders, cerium oxides or conductivity blacks.
• Such powders may consist of the known metals, for example Fe, Co, Ni, Cu, Al, Zn, Sn or their alloys.
• materials which are inductively heatable, especially metal or ferrite particles in the form of powders, wires or nets are suitable. In this case, such components should not be present in the entire molded part, only on the intended surfaces for bonding.
• One embodiment has incorporated these components into the surface intended for bonding, ie these metallic conductive particles are completely enveloped by the hotmelt adhesive. It should be the thickness of the layer with such Components approximately equal to the thickness of the adhesive layer to be melted. Another embodiment operates such that such conductive components as perforated metal foil, metal nets or metal wires are applied only to the surface of the adherend surface. In this case, the metallic parts are not completely enveloped by the hot melt adhesive. Such embedded to a small extent in the hot melt adhesive components should also be included under the definition that the shaped body consists entirely of the hot melt adhesive. These components do not contribute to the supporting structure of the moldings.
• Another embodiment has the advantageous for heating the molding parts in the vicinity or adjacent to the surface to be bonded.
• a wire, mesh or powder may be attached to the periphery of a pin-shaped adhesive surface.
• a net can cover the circumference completely or even partially.
• the hotmelt adhesive is heated and melted at the bond area and can then be bonded.
• the distance of the inductively heatable parts of the bonding surface is to be chosen so that a sufficient liquefaction of the hot melt adhesive is ensured at the bonding site.
• Another object of the invention is a method for bonding such moldings of hot melt adhesives on substrate surfaces. Due to the industrial requirements short cycle times for bonding are appropriate.
• the molded body is heated from the hot melt adhesive to the surface to be bonded, so that only at this point, a melting or softening takes place. Thereafter, the shaped body is pressed onto the substrate and firmly connected by solidification or recrystallization.
• An inventive method works in such a way that the molding is heated on the surface to be bonded to the substrate by methods known per se. This can be done for example by heating with hot gases, with infrared radiation or by contact with heated surfaces. It is invented Essential to the fact that the molded part is heated only on the surface to be bonded. Immediately after the heating, the molded part is pressed onto the substrate. In this case, the hot melt adhesive cools and forms a firm connection with the molded part.
• Another less preferred mode of operation of the invention operates to heat the substrate at least at certain points. On the thus heated points, the molding is pressed. It is important to ensure that the heating at the point to be bonded is sufficiently high to melt the molding on the surface to be bonded. This method is particularly suitable if the substrate can be heated to a sufficient temperature without destruction.
• a preferred embodiment operates in such a way that the molded part contains on or adjacent to the surface to be bonded metallically conductive powder or constituents. These can be heated inductively for bonding, i. be subjected to electromagnetic fields. This leads to heating and melting of the hot melt adhesive. The melted on the surface to be bonded adhesive of the molded part is then pressed onto the substrate. In general, the inductive heating is terminated so that the hot melt adhesive can cool and bond to the substrate. Optionally, however, it is possible to heat the hotmelt adhesive of the molded part on the surface to be bonded even after the compression for a short period of time.
• the hotmelt adhesive should be heated to such an extent that it can flow to the substrate. This can possibly be supported by mechanical pressure, such as pressing. For example, the heating should be at least 20 ° C., in particular 30 ° C., above the melting point of the adhesive.
• a particularly rapid cooling and rapid bonding is achieved, for example, by bonding metallic substrates.
• Devices for direct heating of the moldings, for inductive heating of the moldings and for applying the moldings to the substrate are known to the person skilled in the art. This can be adapted devices, depending on the required melting temperature of the molding, cycle time of the bonding, the shape of the substrates to be bonded, select.
• the material of the shaped body configured according to the invention has too low a melting point, a temperature-stable bonding is not possible. In particular, if additional mechanical stresses occur, such as vibrations, stable bonding is not achieved.
• the yield stress must be above preferably 3 MPa, otherwise there is no sufficient holding force of the fastening device. If the value is too high, the bond substrate / article to be fastened is too rigid, i. All mechanical stresses of the substrate are passed on to the object to be fastened.
• the method according to the invention is particularly suitable for bonding shaped parts as fastening devices to sheet-like substrates with automated working processes, which have a spatial form designed within wide limits.
• the method according to the invention is suitable bonding clips or bolts on metallic substrates, such as sheet metal substrates to glue.
• Such glued fastening clips can be used for example in the automotive industry, the aircraft industry, the general OEM industry or in the case of plastic or wooden substrates in the furniture industry, etc.
• a polyamide was prepared from 50 mol% sebacic acid, 24 mol% piperazine, 16.5 mol% Jeffamine D 400 and 9.5 mol% ethylenediamine.
• Key data Acid value: 8.2 mg KOH / g, melt viscosity: 17000 mPas at 200 ° C, softening points 75 ° C, tear strength 25 MPa.
• the bottom surfaces of the molded bodies were inductively heated and bonded to various flat substrates.
• the bottom surfaces of the moldings without the addition of conductive additives are heated with a hot air gun and glued.
• a molding is prepared. Around the bonding surface is applied to a copper net at half the circumference of the pin in a width of 0.5 cm. The molding is bonded as in Examples 1 and 2.
• the samples show good adhesion to the substrate.
• Plastic substrate up to 10 N / mm 2
• a polyamide resin (PA 6) is melted and pressed onto a metal substrate. There is no liability.

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• Organic Chemistry (AREA)
• Adhesives Or Adhesive Processes (AREA)

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• 2007
  • 2007-10-16 CA CA002671011A patent/CA2671011A1/en not_active Abandoned
  • 2007-10-16 WO PCT/EP2007/061007 patent/WO2008064950A1/de not_active Ceased
  • 2007-10-16 JP JP2009538659A patent/JP2010511082A/ja active Pending
  • 2007-10-16 EP EP07821373A patent/EP2094802B1/de not_active Not-in-force
• 2009
  • 2009-05-29 US US12/474,559 patent/US20090291288A1/en not_active Abandoned

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