EP3146007A1 - Thermoplastische elastomerenzusammensetzungen mit haftung zu metallischen oberflächen - Google Patents

Thermoplastische elastomerenzusammensetzungen mit haftung zu metallischen oberflächen

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Publication number
EP3146007A1
EP3146007A1 EP15723504.5A EP15723504A EP3146007A1 EP 3146007 A1 EP3146007 A1 EP 3146007A1 EP 15723504 A EP15723504 A EP 15723504A EP 3146007 A1 EP3146007 A1 EP 3146007A1
Authority
EP
European Patent Office
Prior art keywords
tpe
polar
compound according
adhesion
tps
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.)
Withdrawn
Application number
EP15723504.5A
Other languages
German (de)
English (en)
French (fr)
Inventor
Florian Vetter
Ernst Lifka
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Kraiburg TPE GmbH and Co KG
Original Assignee
Kraiburg TPE GmbH and Co KG
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Kraiburg TPE GmbH and Co KG filed Critical Kraiburg TPE GmbH and Co KG
Publication of EP3146007A1 publication Critical patent/EP3146007A1/de
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D151/00—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
    • C09D151/006—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to block copolymers containing at least one sequence of polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/06—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
    • C08K3/26—Carbonates; Bicarbonates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L21/00—Compositions of unspecified rubbers
    • 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
    • C08L23/16—Elastomeric ethene-propene or ethene-propene-diene copolymers, e.g. EPR and EPDM rubbers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/006—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to block copolymers containing at least one sequence of polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds

Definitions

  • the present invention relates to thermoplastic elastomer compositions which have excellent adhesion to metals and are extremely stable to the influence of acids and alkalis.
  • thermoplastic elastomers together ⁇ ratios according to the invention are characterized by a special stability to the influence of acids and alkalis at room temperature and at elevated temperatures. Important parameters such as swelling behavior, hardness, elongation at break and tensile strength show only minor changes.
  • the TPE compounds have a preferred, but not limited, Shore A hardness of 30 to 90 ShA, and consist of at least one mixture of a polar functionalized TPE of styrene-containing block copolymer (TPS) (A), an adhesion-promoting resin (B) and a process oil (C).
  • TPS styrene-containing block copolymer
  • B adhesion-promoting resin
  • C process oil
  • compounds according to the invention may contain further constituents.
  • Thermoplastic Elastomers combine the rubbery properties of elastomers with the advantageous processing properties of thermoplastics. This combination of properties opens up a variety of applications to the TPE materials, such as automotive interiors and exteriors, industrial equipment, industrial tools, home appliances, medical
  • TPE materials take on properties such as sealing,
  • thermoplastic elastomer In many of the abovementioned fields of application, there is a requirement for a thermoplastic elastomer to be permanently and materially bonded to another material class, such as thermoplastics, ceramic materials, glass or metal. At the same time the waiver of adhesives or primers, as well as the maximum possible design freedom of the component to be produced is required.
  • the aim is to combine rigid elements with flexible elements in a single assembly or finished part. This is often associated with a reduction in costs, for example by reducing production steps, weight reduction, shortening of production times and / or low structural complexity of the individual and finished parts.
  • TPE has advantages over vulcanized rubbers as a flexible element in processing because, like thermoplastics, they can be processed easily, inexpensively and using widely used technologies.
  • a method as described in DE 19938015 requires an additional vulcanization step, which prolongs cycle times.
  • the Vulcanization is carried out after the rubber or rubber-like plastic has been sprayed onto the metallic component. Only after completion of vulcanization can be removed from the mold.
  • the use of a TPV which has improved adhesion to polyamide.
  • the TPV consists of a polyolefin-based elastomer phase (preferably EPDM) and a thermoplastic phase, which is composed of at least 80% of one or a mixture of a plurality of functionalized polyolefins.
  • EPDM polyolefin-based elastomer phase
  • thermoplastic phase which is composed of at least 80% of one or a mixture of a plurality of functionalized polyolefins.
  • Triblockcopolymers can be used as elastomers or as admixtures to the polyolefin-based elastomers.
  • functional groups carboxylic acid, acid anhydride, acid chloride, isocyanate, oxazoline, amine, hydroxy and epoxy groups are mentioned. Preference is given to acid anhydride groups, particularly preferred
  • US 8193273 also describes the adhesion of TPE compounds to polyamides (PA). Also in this invention, polyamide is blended into a TPE compound. However, high molecular weight, maleated polystyrene-poly (ethylene-butylene) -polystyrene block copolymer (MAH-g-SEBS) is used here. Furthermore, in the examples, a MAH-grafted PP is used as a further adhesion component. Both the US 8193273 and the aforementioned US 8071220 is based on the idea that the admixed PA should build the actual adhesion to the PA substrate.
  • PA polyamides
  • MAH-g-SEBS high molecular weight, maleated polystyrene-poly (ethylene-butylene) -polystyrene block copolymer
  • MAH-g-SEBS maleated polystyrene-poly (ethylene-butylene) -polystyrene block copolymer
  • Patent EP 2610305 describes in detail the adhesion between TPE and polar surfaces of ceramics, metals or synthetic plastics. Furthermore, material combinations created are disclosed. Claimed is a mixture of a TPE, a polyvinyl acetal and a polypropylene with polar groups.
  • the TPE is based on block copolymers of vinylic aromatics (preferably styrene) and isoprene (SIS), butadiene (SBS), isoprene-butadiene mixtures (SIBS) and their hydrogenated variants (SEBS, SEEPS).
  • Other ingredients include plasticizer oils and tackifiers. Disadvantages of the compounds described are their limited processability and their stability to the influence of strong acids and alkalis.
  • Polyvinyl acetals are not resistant to hydrolysis with respect to acids and release corresponding aldehydes.
  • the vinyl acetal groups are converted into vinyl alcohol groups.
  • the splitting off of health-damaging and odor-causing aldehydes (in the preferred variant according to the invention, it is butyraldehyde) is undesirable.
  • the polyvinyl acetals according to the invention are preferably acetalated only to 55 to 88%, the remaining functional groups consist of either vinyl alcohol groups or vinyl acetate groups.
  • Vinyl acetates split off the acetate unit under the influence of lyes and acids as acetate ion or as acetic acid, resulting in polyvinyl alcohol.
  • the high solubility of polyvinyl alcohols in aqueous media again contributes adversely to the stability and adhesion of the described TPE compounds.
  • EP 2054227 describes a process for producing a composite product from a thermoplastic ("hard plastic”, preferably ABS) and a TPS based on styrene-based elastomer and polyolefin ("plastic", preferably SEBS). It is further described that this composite product subsequently undergoes a galvanizing step.
  • a thermoplastic preferably ABS
  • TPS styrene-based elastomer and polyolefin
  • NMT Nemo Molding Technology
  • This technology is used to pre-treat a metal, especially aluminum, to increase adhesion to thermoplastics NMT technology has been developed by Taisei plas Co. Ltd. in EP 1559542 and EP 1459882 or also published under www.taiseiplas.com.
  • aluminum or even other metals such as copper, magnesium, stainless steel, titanium, steel, galvanized steel, brass are pretreated (etched) in such a way that the surface finish allows direct adhesion of thermoplastic synthetic materials by means of injection molding.
  • the object of the invention was to provide TPE compounds which can form a permanent, cohesive material composite to metals and / or metallic surfaces, are stable against the influence of inorganic and / or organic acids and alkalis and are easy to apply.
  • TPE compounds according to the invention should have a certain hardness range and a corresponding elasticity. Furthermore, the compounds should be processable in particular by injection molding and require simple or no special pretreatment of the metallic surfaces. In order to ensure maximum process freedom in typical chemical, non-abrasive treatment methods of metal processing, TPE compounds should have high stability to inorganic and / or organic acids and alkalis after application. Both the adhesion to corresponding metallic substrates, as well as important parameters such as swelling behavior, hardness, elongation at break and tensile strength should remain as unchanged as possible after the action of acids and / or alkalis.
  • TPE compounds should have good adhesion to aluminum.
  • Another object was that the TPE compounds have good adhesion to aluminum and survive the conditions of anodic oxidation type II and III.
  • compounds to be tested were successively exposed to the following chemicals in accordance with DIN ISO 1817:
  • the test pieces were thoroughly rinsed with distilled water. After exposure to all chemicals, the TPEs were examined for their characteristics. If there were slight changes in the parameters for hardness ( ⁇ 5ShA), elongation at break ( ⁇ 20%), tensile strength ( ⁇ 30%) and swelling behavior ( ⁇ 2%), the material was considered stable. Resistance in this test is to be equated with chemical resistance. In addition to the chemical testing, the TPE compounds were tested for their adhesion. In addition to the mentioned
  • TPE has polar groups which are selected from the group consisting of carboxylic acid
  • the TPE compound has a Shore A hardness of 30 to 90 ShA.
  • the TPS is a triblock copolymer A-B-A.
  • the block A of the triblock copolymer is polystyrene and the B block of the triblock copolymer is selected from polybutadiene, polyisoprene and / or polyisobutene. It is furthermore preferred if, in the TPE compound according to the invention in the A block, the styrene monomers are partially or completely blocked by derivatives of styrene, preferably methylstyrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, 4-tert-butylstyrene, 4- Cyclohexylstyrene or vinylnaphthalenes, preferably 1-vinylnaphthalene and 2-vinylnaphthalene can be replaced.
  • the B block may contain mixtures of dienes. It is also possible that the B blocks are partially or completely hydrogenated.
  • compounds according to the invention may contain further constituents. These include further TPE, polar Functionalized TPE, thermoplastics, polar functionalized thermoplastics and additives.
  • the polymer composition has a preferred Shore A hardness of 30 to 90 ShA.
  • thermoplastic elastomers TPE
  • Thermoplast ic Elastomers Carl Hanser Verlag, 3rd ed., Kunststoff (2004) ", in the DIN EN ISO 18064 or at” http://en.wikipedia.org/wiki / Thermoplastic _elastomer "are described.
  • thermoplastic elastomers based on styrene block copolymers (TPS), polyesters (TPC), polyurethanes (TPU), polyamides (TPA), polyolefins (TPO) and crosslinked TPE (TPV), based on crosslinked elastomer particles dispersed in continuous thermoplastic phases available.
  • TPS styrene block copolymers
  • TPC polyesters
  • TPU polyurethanes
  • TPU polyamides
  • TPO polyolefins
  • TPV crosslinked TPE
  • the TPE compounds according to the invention consist at least of a mixture of a polar functionalized TPS (A), an adhesion-promoting resin (B) and a process oil (C) and are said to be stable to the influence of inorganic and / or organic acids and alkalis. It has also been shown that the substance classes TPU, TPC and TPA are little or not suitable. Comparing the adhesion to non-functionalized TPS metals, which are rather non-polar, and the polar TPU, TPA and TPC, it can be seen that the polar TPEs give better values. The disadvantage of these classes, however, is that they partially or sometimes even completely decompose under acid and / or alkali. For the fulfillment of the required task of chemical resistance, this is a hindrance.
  • TPS the substance classes of TPS show good resistance to inorganic and / or organic acids and alkalis.
  • TPS according to the invention must be polar functionally functionalized.
  • EP 2054227 teaches the good resistance of TPS to acid, however, said TPS can not be used for permanent, cohesive adhesion to metals due to the lack of polar groups.
  • Polarized TPS (A) show both good adhesion and good chemical resistance.
  • TPS are triblock copolymers ABA where the A block is usually polystyrene and the B block is usually composed of polybutadiene, polyisoprene or polyisobutene (SBS, SIS, SiBS).
  • the styrenic monomers can be partially or completely replaced by derivatives of styrene such as methylstyrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, 4-tert-butylstyrene, 4-cyclohexylstyrene or vinylnaphthalenes such as 1-vinylnaphthalene and 2-vinylnaphthalene.
  • the B block may alternatively contain mixtures of dienes such as SIBS (B block of mixture of butadiene and isoprene). Furthermore, TPS consisting of styrene and diene monomers can also be used as hydrogenated derivatives.
  • the units of the B blocks are partially or fully hydrogenated.
  • Polystyrene-block-poly (ethylene-co-butylene) -block-polystyrene (SEBS) and polystyrene-block-poly (ethylene-co- (ethylene-propylene)) -block-polystyrene (SEEPS) may be mentioned here.
  • TPS are composed of triblock copolymers ABA.
  • TPS-based TPEs according to the invention have a weight-average molecular weight (M w ) of 50,000 to 500,000 g / mol, preferably 100,000 to 400,000 g / mol.
  • block copolymers based on styrene which are used for pressure sensitive adhesives (PSA). Although their molecular structure is very similar, they have a different rheological behavior than TPE. Pressure-sensitive adhesives must build up adhesion to the substrate under light pressure (finger pressure) and at room temperature. In order to achieve this, block copolymers are used clearly below Mw 50,000 g / mol. TPE compounds according to the invention show no adhesion under these conditions and can not form films. There is also a significant difference to hotmelts, another important class of adhesives. Hotmelts must flow under the influence of temperature (usually> 100 ° C) without any further action and train films.
  • TPE and TPE compounds must be both heated and sheared for processing. A mere heating usually results in a decomposition of the material without noticeable melting or flow.
  • adhesives are formulated to be applied as thin layers. There is no requirement for a three-dimensional, shaping extension or structure. TPE and TPE compounds typically have a structural extension in three dimensions. TPE compounds according to the invention have not only structural expansion but also adhesive properties. But to call them adhesives is misleading. Surprisingly, it has been found that the combination of a polar functionalized TPS (A), an adhesion-promoting resin (B) and a process oil is sufficient to achieve the stated object of the present invention, namely metal adhesion with simultaneous chemical resistance and ease of processing to solve.
  • A polar functionalized TPS
  • B adhesion-promoting resin
  • a process oil is sufficient to achieve the stated object of the present invention, namely metal adhesion with simultaneous chemical resistance and ease of processing to solve.
  • Polar modification can be done by grafting.
  • Polar groups may be: carboxylic acid, carboxylic anhydride, epoxy, hydroxy, amine or amide.
  • Those skilled in the art are familiar with methods of radical grafting for the introduction of these polar groups.
  • peroxide initiators (meth) acrylic acid, MAH, glycidyl (meth) acrylate or acrylamide are reacted with corresponding TPS according to the invention.
  • the grafting can take place in a separate step or during the preparation of the compounds according to the invention. Preferably, a grafting takes place before the compounding.
  • Preferred graft levels are between 0.5 to 5.0%, more preferably 0.5 to 3.0%, and most preferably between 1.0 to 2.5%.
  • the preferred reagent for grafting is MAH, more preferably in the range of 0.5 to 3.0%.
  • Component (A) used according to the invention is very particularly suitable for TPS grafted with 1.0 to 2.5% MAH.
  • the determination of the degree of grafting can be carried out with all analytical methods known to those skilled in the art, both wet-chemically by titration of, for example, acid groups and by instrumental analysis (GC-MS, NMR, IR, UV-Vis, elemental analysis, etc.). These methods are known to the person skilled in the art.
  • MAH grafted TPS are mentioned in US 8193273, such as Kraton MD 6684CS, Kraton MD 6933, Septone 4077 or Septone 4099.
  • Another MAH grafted TPS for example, Kraton FG 1901GT is commercially available.
  • a TPE functionalized with acrylic acid or MAH groups should not react with free amino or amide functionalities of a polyamide or free hydroxy groups of a polyester.
  • rosin natural resins
  • Another disadvantage is the use of hydrolysis-sensitive alkyl silicate resins. These columns release alcohols, which in turn can react with, for example, MAH functionalized TPE.
  • the component (B) of the present invention is an adhesion-promoting resin.
  • This is also widely used as Tackifier designates and is found in various applications of adhesives or paints.
  • Various types of tackifiers are described in Chapter 10.2.2 of "AV Pocius, Adhesion and Adhesive Technology, Carl Hanser Verlag, 3rd Ed., Kunststoff (2012)", as well as in EP 2610305 and DE 102004063516.
  • Resins with carboxylic acid ester compounds such as rosin resins and their hydrogenated variants, are unsuitable for the purposes of the present invention.
  • Hydrolyzable alkyl silicone resins of DE 102004063516 are to be avoided, since cleavage products can be mixed with the polar units of Rather, synthetic resins based on cracker products are suitable and preferred, and a distinction is made between aromatic and aliphatic tackifiers
  • the adhesion-promoting resin is thus preferably selected from aliphatic and aromatic synthetic resins or mixtures thereof based on C5 sections of cracker fractions. V. Pocius will become more
  • Preferred adhesion promoting resins (B) have been found to be synthetic resins or mixtures of synthetic resins. Particularly preferred are aromatic, C 5 -based aliphatic resins or mixtures of aromatic and C 5 - based resins, which are preferably resistant to hydrolysis to acids and alkalis. Suitable commercially available resins are, for example, from the group of aromatic resins Endex types from Eastman such as Endx 155® or Norsolene® W140 from Cray Valley and from the group of aliphatic resins Eastotac types such as Eastotac H-130R®.
  • process oils (C) according to the invention it is possible to use all process oils customary for the production of TPE compounds, also called plasticizers. These include paraffinic, naphthenic or aromatic oils. White oils, both technical and medical, are among the paraffinic oils and are also named. Furthermore, process oils (C) according to the invention also include synthetic oils such as GTL oils or hydrogenation oils. Little or not suitable are hydrolysis-labile oils or plasticizers with ester bonds such as those based on phthalic acid esters (for example dioctyl or dibutyl phthalate), native oils (for example rapeseed or soybean oil), alkyl sulfonates or generally mono-, di- or higher alkyl esters. In addition to improving the processability, the oils essentially have the function of coordinating the final hardness of the compounds according to the invention.
  • TPE compounds according to the invention comprising or consisting of at least one mixture of a polar-functionalized TPS (A), an adhesion-promoting resin (B) and a process oil (C) may optionally contain further constituents.
  • polar-functionalized TPS A
  • adhesion-promoting resin B
  • process oil C
  • TPEs polar functionalized TPEs
  • thermoplastics thermoplastics
  • polar functionalized thermoplastics additives.
  • TPEs are selected for chemical resistance from the group of TPS, TPO and TPV. Preferred TPS and TPO. Most preferably, the optional selected TPE is from the same TPE grade as component (A).
  • TPO As TPO (A), different types of TPO can be used. Both those made from polyolefin-based Block copolymers exist, as well as mixtures of thermoplastic polyolefins and elastomeric rubbers. Examples which may be mentioned are block copolymers of olefins such as propylene and ethylene (for example PP-PE-PP or block PP-block (co-PE-PP) block PP) or hydrogenated block copolymers of butadiene and isoprene (BIB). Exemplary blends of thermoplastic polyolefins and elastomeric rubbers are those of isotactic PP and EPDM rubber. TPOs according to the invention are described in detail in Chapter 5 of "G.
  • TPO TPO according to DIN standard consists exclusively of "a mixture of a polyolefin with a common rubber, the rubber phase having little or no crosslinking in the mixture".
  • TPV differ from TPO in that the elastomeric phase is additionally crosslinked, usually dynamically.
  • TPOs are preferably composed of block copolymers of PP and PE and mixtures of PP and EPDM.
  • Very particularly preferred TPOs for the preparation of polar modified TPO (A) are PP and EPDM.
  • polar functionalized TPEs may be modified TPS or TPO, as already described as component (A), where either the polar group, the polar group content or the TPE class is different from that of component (A).
  • thermoplastics of the TPE compounds according to the invention are those which are compatible with TPS, TPO and polar-functionalized TPS and TPO according to the invention (A) and are hydrolytically resistant to alkalis and acids.
  • examples include PE, PP, polystyrene and PVC.
  • thermoplastics can be added to the compounds according to the invention.
  • the possible polar groups are selected from carboxylic, carboxylic anhydride, epoxy, hydroxy, amine or amide groups.
  • the polar groups can be introduced by grafting.
  • the person skilled in the methods are known. Particularly noteworthy is the radical grafting by means of peroxide initiators.
  • a grafting takes place before the compounding.
  • Preferred graft levels are between 0.5 to 5.0%, more preferably 0.5 to 2.0%.
  • As a preferred reagent for grafting MAH is to be mentioned as preferred thermoplastics PE and PP to be grafted.
  • compounds according to the invention may contain further additives. These include process auxiliaries, stabilizers or fillers.
  • antistatics As process auxiliaries and stabilizers there may be mentioned antistatics, anti-foaming agents, lubricants, dispersants, release agents, anti-blocking agents, radical scavengers,
  • foaming aids blowing agents
  • Flame retardants smoke suppressants
  • Schlagzähmodifika- factors adhesives
  • anti-fogging smodifikatoren aids dyes, color pigments ⁇ , color masterbatches, viscosity.
  • fillers are mentioned, for example, kaolin, mica, muscovite, phlogopite, calcium sulfate, calcium carbonate, silicates, silica, talc, carbon black, graphite or synthetic fibers.
  • the hardness of the TPE compounds according to the invention is in the range of 30 to 90 ShA, preferably 40 to 80 ShA, very particularly preferably 50 to 70 ShA.
  • the TPE compounds according to the invention comprise or consist of at least one mixture of a polar functionalized TPS (A), an adhesion-promoting resin (B) and a process oil (C).
  • a polar functionalized TPS A
  • B adhesion-promoting resin
  • C process oil
  • the process oil (C) is admixed with compounds according to the invention.
  • the softer the TPE compound the more (C) it will contain.
  • (C) is added in the range of 50-5 wt.%, Preferably 40-10 wt.% And particularly preferably 40-15 wt.%, Based on the final TPE compound.
  • TPE compounds according to the invention may contain, in addition to (A), (B) and (C), further constituents such as TPE, polar functionalized TPEs, thermoplastics, polar-functionalized thermoplastics and additives. It turns out that the total weight of (A), all other TPE and polar functionalized TPE in the weight ratio to the component (B) of 10: 1 to 1.5: 1 and preferably 5: 1 to 2: 1 is to choose ,
  • thermoplastics and polar functionalized thermoplastics is in total from 0 to 30% by weight, preferably 0 to 20% by weight and particularly preferably 0 to 10% by weight, based on the total weight of the TPE compounds.
  • TPE compounds from 0 to 30% by weight, preferably 0 to 20% by weight and in particular 0 to 15% by weight, are added from the list of possible additives.
  • UV stabilizers process stabilizers and antioxidants are in the range of 0 to 2 wt.%, Preferably 0 to 1 wt.%.
  • the percentages by weight of the optional additives are based on the respective total weight of the TPE compounds according to the invention.
  • TPE compounds of the invention show excellent, permanently cohesive adhesion to metals and metallic surfaces. To achieve the adhesion no elaborate pretreatment is necessary. Likewise, the use of primers or adhesives can be dispensed with.
  • TPE Compunds according to the invention provide significant advantages in terms of freedom of design and process freedom.
  • the TPE compounds, as well as components produced therefrom thus represent a significant advantage over the prior art.
  • composite materials of different classes of materials can be realized, for example, a component for consumer electronics made of metal (for example, a mobile phone), pretreated by NMT, which also contains thermoplastic elements for the threaded bushes in addition to TPE as a sealing material.
  • TPE compounds according to the invention can be processed inexpensively and by means of widely used technologies in order to produce material composites into metals and metallic surfaces. Metals are both base metals and precious metals to understand. Included are alloys of metals.
  • Examples include aluminum, copper, magnesium, titanium, steel, stainless steels (for example, V2A, V4A), galvanized steels, galvanized steels with coatings of copper, nickel, chromium or other metals. Furthermore, be Plastics and plastic called parts, which have coatings of metal by means of galvanic processes or are metallized. These are covered in the meaning of the invention with metallic surfaces. Preference is given to composite materials of the TPE according to the invention to metals, more preferably to aluminum, copper, titanium, stainless steels.
  • some compounds of the invention have very good adhesion to other surfaces such as glass, ceramics, engineering plastics, especially thermoplastics.
  • TPE compounds of the present invention after application and production of the composite with a metal or a metallic surface high stability to inorganic and / or organic acids and alkalis, have after contact with acids and / or alkalis continue very good adhesion to corresponding metallic substrates and show no or only slight changes in the important parameters such as swelling behavior, hardness, elongation at break and tensile strength.
  • This chemical resistance is advantageous if after the formation of the bond between TPE compound and metallic substrate, aftertreatments take place.
  • chemical aftertreatments and / or post-treatments taking place with the aid of chemicals. This includes, for example, the anodic oxidation of aluminum. Aftertreatments often serve to further refine the metallic surface for reasons of corrosion protection or a special one
  • the invention thus also provides a process for producing TPE compounds as described above using an extruder, internal mixer or kneader, preferably an extruder or a twin-screw extruder.
  • the invention further provides a process for the production of a composite material, wherein the composite material by injection molding, injection injection molding process, extrusion, compression molding, preferably by injection molding, injection molding and extrusion, most preferably by means of injection-injection method using a TPE Compounds as described above and another substance selected from metals, glass, ceramics, thermoplastics and mixtures of the mentioned, is produced
  • TPE compounds are carried out by means of conventional mixing units. Suitable units may be extruder, internal mixer or kneader. Ensure the homogeneous distribution of the individual raw materials of the respective compound. Preferred aggregates are extruders, in particular twin-screw extruders.
  • the TPE compounds of the invention are characterized by excellent flow and processing properties.
  • the TPEs can be applied in a variety of forms on the metallic substrates to create the composite product.
  • TPE rigid elements
  • thermoplastic thermoplastic
  • a significant advantage of the described method is that time-consuming and energy-intensive vulcanization steps can be dispensed with.
  • metal TPE Three- and multi-layered structures (sandwich construction) are also feasible, such as metal / TPE compound / metal.
  • composites between more than two classes of materials can be realized. This refers to those composites where the TPE compound is an adhesive component between at least two materials.
  • a composite metal / TPE compound / thermoplastic is listed.
  • the present invention also relates to the use of the TPE compounds according to the invention for the production of various components and finished products in which a metallic part or a part with metallic surface coating, partially or completely, with an elastic element made of TPE cohesively form a bond.
  • Typical fields of application include components, finished parts, molded parts, housings for electronic devices such as mobile phones, laptops, PCs, storage media.
  • Sports equipment or other items such as wristwatches or jewelry.
  • the present invention thus also provides the use of a TPE compound as described above for producing a composite material with metals, glass, ceramics, thermoplastics and mixtures of the above.
  • the metal is selected from aluminum, copper, titanium, steel and stainless steel and / or their alloys.
  • the material composites thus produced served as specimens and were initially fed to a minimum Kondit ionierzeit of 24h under standard conditions for subsequent tests. At least two samples of specimens of the same composite were made at least.
  • Test plates made of pure TPE compounds of Table 1 with the dimensions 125mm x 125mm x 2mm were produced for testing the other parameters. According to Table 2 hardness, density, tensile strength and elongation at break were measured. Hardness and density were determined on these test panels or parts thereof. For the determination of the tensile strength and elongation at break, S2 specimens with a thickness of 2 ⁇ 0.05 mm were used, which were punched out of the "pure TPE" test plates.
  • test specimens (specimens Figure 1 for adhesion test, S2 specimens for tensile strength and elongation at break, test plates or parts of hardness and density test plates mentioned under 5.) were successively exposed to the following chemicals: - Phosphoric acid 85% at 80 ° C for 3 minutes
  • test pieces were thoroughly rinsed with distilled water. After exposure to all chemicals, the samples were examined for their characteristics. If there were slight changes in the parameters for hardness ( ⁇ 5ShA), elongation at break ( ⁇ 20%), tensile strength ( ⁇ 30%) and swelling behavior ( ⁇ 2%), the material was considered stable. Resistance in this test is to be equated with chemical resistance. Table 3 shows the initial values of the TPE compounds of Table 1. Table 4 shows the changes in the characteristics after chemical resistance testing. In addition to the mentioned characteristic determinations, test specimens were assessed visually according to the gray scale (DIN EN 20105-A02 / ISO 150-A02). Resistance should be assumed if the specimens are not rated worse than gray scale grade 4/5.
  • Examples I, II and III are references.
  • the compound of Example I is resistant to the above but does not adhere to metals.
  • An exchange of the used, non-functionalized TPS towards lower molecular weights does not change the behavior either.
  • the Reference Compound III, a TPU adheres well to aluminum pretreated by NMT method, poorly on low pretreated metals, but is not resistant to chemicals.
  • pure TPU are at the top of the desired Shore A hardness. All other examples IV to VII according to the invention fulfill the objects of the present invention.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Laminated Bodies (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
EP15723504.5A 2014-05-19 2015-05-18 Thermoplastische elastomerenzusammensetzungen mit haftung zu metallischen oberflächen Withdrawn EP3146007A1 (de)

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DE102014007211.8A DE102014007211A1 (de) 2014-05-19 2014-05-19 Thermoplastische Elastomerenzusammensetzungen mit Haftung zu metallischen Oberflächen
PCT/EP2015/060906 WO2015177099A1 (de) 2014-05-19 2015-05-18 Thermoplastische elastomerenzusammensetzungen mit haftung zu metallischen oberflächen

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US11827787B2 (en) 2018-12-20 2023-11-28 Actega Ds Gmbh Thermoplastic elastomer composition

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JP2017516907A (ja) 2017-06-22
CN106795356A (zh) 2017-05-31
WO2015177099A1 (de) 2015-11-26
DE102014007211A1 (de) 2015-11-19
US20170190897A1 (en) 2017-07-06

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