EP3166791A1 - Pièces composites perméables à la vapeur d'eau - Google Patents

Pièces composites perméables à la vapeur d'eau

Info

Publication number
EP3166791A1
EP3166791A1 EP15734162.9A EP15734162A EP3166791A1 EP 3166791 A1 EP3166791 A1 EP 3166791A1 EP 15734162 A EP15734162 A EP 15734162A EP 3166791 A1 EP3166791 A1 EP 3166791A1
Authority
EP
European Patent Office
Prior art keywords
ethylenediamine
sheet
acid
composite part
linear
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Withdrawn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
EP15734162.9A
Other languages
German (de)
English (en)
Inventor
Govert Woeste
Franz-Heinrich HERMANNS
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.)
Covestro Deutschland AG
Original Assignee
Covestro Deutschland AG
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 Covestro Deutschland AG filed Critical Covestro Deutschland AG
Publication of EP3166791A1 publication Critical patent/EP3166791A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/40—Layered products comprising a layer of synthetic resin comprising polyurethanes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D1/00—Processes for applying liquids or other fluent materials
    • B05D1/30—Processes for applying liquids or other fluent materials performed by gravity only, i.e. flow coating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
    • B05D3/02—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by baking
    • B05D3/0254—After-treatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B9/00—Making granules
    • B29B9/02—Making granules by dividing preformed material
    • B29B9/06—Making granules by dividing preformed material in the form of filamentary material, e.g. combined with extrusion
    • B29B9/065—Making granules by dividing preformed material in the form of filamentary material, e.g. combined with extrusion under-water, e.g. underwater pelletizers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/022—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the choice of material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
    • B29C48/07—Flat, e.g. panels
    • B29C48/08—Flat, e.g. panels flexible, e.g. films
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/16—Catalysts
    • C08G18/22—Catalysts containing metal compounds
    • C08G18/24—Catalysts containing metal compounds of tin
    • C08G18/244—Catalysts containing metal compounds of tin tin salts of carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C08G18/3203—Polyhydroxy compounds
    • C08G18/3206—Polyhydroxy compounds aliphatic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
    • C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
    • C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
    • C08G18/7671—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups containing only one alkylene bisphenyl group
    • 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
    • C08J5/18—Manufacture of films or sheets
    • E—FIXED CONSTRUCTIONS
    • E04—BUILDING
    • E04B—GENERAL BUILDING CONSTRUCTIONS; WALLS, e.g. PARTITIONS; ROOFS; FLOORS; CEILINGS; INSULATION OR OTHER PROTECTION OF BUILDINGS
    • E04B1/00—Constructions in general; Structures which are not restricted either to walls, e.g. partitions, or floors or ceilings or roofs
    • E04B1/62—Insulation or other protection; Elements or use of specified material therefor
    • E04B1/625—Sheets or foils allowing passage of water vapor but impervious to liquid water; house wraps
    • E—FIXED CONSTRUCTIONS
    • E04—BUILDING
    • E04D—ROOF COVERINGS; SKY-LIGHTS; GUTTERS; ROOF-WORKING TOOLS
    • E04D12/00—Non-structural supports for roofing materials, e.g. battens, boards
    • E04D12/002—Sheets of flexible material, e.g. roofing tile underlay
    • E—FIXED CONSTRUCTIONS
    • E04—BUILDING
    • E04D—ROOF COVERINGS; SKY-LIGHTS; GUTTERS; ROOF-WORKING TOOLS
    • E04D5/00—Roof covering by making use of flexible material, e.g. supplied in roll form
    • E04D5/06—Roof covering by making use of flexible material, e.g. supplied in roll form by making use of plastics
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2075/00—Use of PU, i.e. polyureas or polyurethanes or derivatives thereof, as moulding material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2995/00—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds
    • B29K2995/0037—Other properties
    • B29K2995/0068—Permeability to liquids; Adsorption
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
    • B29L2007/00—Flat articles, e.g. films or sheets
    • B29L2007/008—Wide strips, e.g. films, webs
    • 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
    • C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
    • C08J2375/04—Polyurethanes
    • C08J2375/08—Polyurethanes from polyethers

Definitions

  • the invention relates to water vapor permeable, flat composite parts consisting of at least two layers, wherein at least one layer consists of a specific wax containing thermoplastic polyurethane, and their use.
  • Thermoplastic polyurethane elastomers are of industrial importance as they exhibit excellent mechanical properties and are cost-effective to process thermoplastically. By using different chemical components, their mechanical properties can be varied over a wide range. Summary representations of TPU, their properties and applications can be found in Plastics 68 (1978), pp 819-825 and rubber, rubber, plastics 35 (1982), pp 568-584.
  • TPUs are built up from linear polyols, usually polyester or polyether polyols, organic diisocyanates and short-chain diols (chain extenders).
  • catalysts can be added to accelerate the formation reaction.
  • the molar ratios of the constituent components can be varied over a wide range, which can adjust the properties of the product. Depending on the molar ratios of polyols to chain extenders products result in a wide Shore hardness range.
  • the structure of the thermoplastically processable polyurethane elastomers can be carried out either stepwise (prepolymer process) or by the simultaneous reaction of all components in one stage (one-shot process).
  • an isocyanate-containing prepolymer is formed from the polyol and the diisocyanate, which is reacted in a second step with the chain extender.
  • the TPUs can be produced continuously or discontinuously.
  • the best known technical production methods are the belt process and the extruder process.
  • auxiliaries and additives can also be added to the TPU building components.
  • examples include waxes, which take over important tasks both in the technical production of TPU as well as in their processing.
  • the wax acts as a friction-reducing internal and external lubricant and improves the flow properties of the TPU.
  • it is intended as a release agent to prevent the adhesion of the TPU to the surrounding material (eg the tool) and to act as a dispersant for other additives, for example pigments and antiblocking agents.
  • waxes to be used there are mentioned, for example, fatty acid esters such as stearic acid esters and montanic acid esters and their metal soaps, fatty acid amides such as stearylamides and oleic amides, and polyethylene waxes.
  • fatty acid esters such as stearic acid esters and montanic acid esters and their metal soaps
  • fatty acid amides such as stearylamides and oleic amides
  • polyethylene waxes polyethylene waxes.
  • substantially amide waxes are used which have a good release effect, in particular ethylene-bis-stearylamide.
  • Derivatives based on this e.g. Reaction products of alkylenediamines with 12-hydroxystearic acid, because of their particularly low tendency to migrate in EP-A 1826225 mention.
  • montan ester waxes are used which exhibit good lubricant properties with low volatility (EP-A 308 683, EP-A 670 339, JP-A 5 163 431). Ester and amide combinations (DE-A 19 607 870) and also special wax mixtures of montanic acid and fatty acid derivatives (DE-A 19 649 290) are also used.
  • the waxes mentioned exhibit good release agent properties and little deposit formation on the surface of the thermoplastic products containing these waxes.
  • the flat composite parts For the use of sheet-like composite parts or films of TPU in the construction sector or in high-quality textiles, the flat composite parts must in particular have a good water vapor permeability. In addition, the flat composite parts should have the longest possible life while maintaining the good water vapor permeability.
  • the object in the present application was to provide laminar composite parts which are not only permeable to water vapor, but whose good water vapor permeability is maintained over as long a period as possible, in particular under the external influences during the construction phase.
  • planar composite parts according to the invention comprising at least two layers, of which at least one layer consists of thermoplastic polyurethane which contains special waxes.
  • the invention relates to water vapor permeable, flat composite parts consisting of at least two layers, wherein at least one layer consists of a thermoplastic polyurethane, which is obtainable from the reaction of the components consisting of
  • component C) one or more components each having two hydroxyl groups and each having a number average molecular weight of 60 to 490 g / mol as a chain extender, C) one or more linear aliphatic hydroxyl-terminated polyether polyols having in each case number average molecular weights of 500 to 5000 g / mol and a number average functionality of component C) of 1.8 to 2.5,
  • polyester polyols each having number average molecular weights of 500-5000 g / mol and a number average functionality of component D) of 1.8 to 2.5, wherein the molar ratio of the NCO groups in A) to the isocyanate-reactive
  • thermoplastic polyurethane 0.02 to 3 wt .-%, preferably 0.02 to 1.0 wt .-%, based on the total thermoplastic polyurethane, at least one component selected from the group consisting of
  • maleic anhydride grafted polyolefins preferably maleic anhydride grafted polyethylenes
  • diesters of branched diols which may contain further hydroxyl groups, with mixtures of linear or branched, saturated or unsaturated mono- and dicarboxylic acids, wherein the linear or branched, saturated or unsaturated
  • Mono- and dicarboxylic acids are optionally used in stoichiometric excess, preferably diesters of adipic acid, oleic acid and pentaerythritol,
  • Hydroxystearic acid and one or more linear fatty acids preferably stearic acid,
  • the TPUs used according to the invention have very good water vapor permeabilities after aging, so that the composite parts according to the invention could thus be made available.
  • Suitable organic diisocyanates A) are preferably aliphatic, cycloaliphatic, araliphatic, heterocyclic and aromatic diisocyanates, as described in Justus Liebigs Annalen der Chemie, 562, pp. 75-136.
  • aliphatic diisocyanates such as 1,6-hexamethylene diisocyanate
  • cycloaliphatic diisocyanates such as isophorone diisocyanate, 1,4-cyclohexane diisocyanate, 1-methyl-2,4-cyclohexane diisocyanate and 1-methyl-2,6-diisocyanate.
  • 1,6-hexamethylene diisocyanate isophorone diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, 1,5-naphthylene diisocyanate and diphenylmethane diisocyanate isomer mixtures having a 4,4'-diphenylmethane diisocyanate content of> 96% by weight and in particular 4,4'-diphenylmethane - Diisoeyanat and 1,6-hexamethylene diisocyanate.
  • the diisocyanates mentioned can be used individually or in the form of mixtures with one another.
  • a polyisocyanate for example triphenylmethane-4,4 ', 4 "-triisocyanate or polyphenyl-polymethylene-polyisocyanate.
  • one or more diols having a number average molecular weight of 60 to 490 g / mol are used, preferably aliphatic diols having 2 to 14 carbon atoms, such as ethanediol, propanediol, butanediol, hexanediol, diethylene glycol, dipropylene glycol, in particular 1, 4- butanediol.
  • diesters of terephthalic acid with glycols having 2 to 4 carbon atoms such as, for example, terephthalic acid-bis-ethylene glycol or terephthalic acid bis-1,4-butanediol, hydroxyalkylene ethers of hydroquinone, such as 1,4-di (-betahydroxyethyl) hydroquinone and ethoxylated bisphenols, such as 1,4-di- (betahydroxyethyl) bisphenol A.
  • chain extenders are also possible to use mixtures of the abovementioned chain extenders are used, in particular two different, more preferably two different aliphatic chain extenders.
  • triols can be added.
  • linear aliphatic hydroxyl-terminated polyether polyols having a number average molecular weight of 500 to 5000 g / mol are used. Due to production, these often contain small amounts of nonlinear compounds. Therefore, one often speaks of "substantially linear polyols”.
  • Suitable polyether polyols for component C) can be prepared by reacting one or more alkylene oxides having 2 to 4 carbon atoms in the alkylene radical with a starter molecule containing two active hydrogen atoms bonded.
  • alkylene oxides e.g. called: ethylene oxide, 1, 2-propylene oxide, epichlorohydrin and 1, 2-butylene oxide and 2,3-butylene oxide.
  • ethylene oxide, 1, 2-propylene oxide and mixtures of 1, 2-propylene oxide and ethylene oxide are used.
  • the alkylene oxides can be used individually, alternately in succession or as mixtures.
  • Suitable starter molecules are, for example: water, amino alcohols, such as N-alkyl-diethanolamines, for example N-methyl-diethanolamine, and diols, such as ethylene glycol, 1,3-propylene glycol, 1,4-butanediol and 1,6-hexanediol , Optionally, mixtures of starter molecules can be used.
  • Further suitable polyether polyols are the hydroxyl-containing polymerization products of 1,3-propanediol and of tetrahydrofuran and also polyether polyols composed of ethylene oxide units and of propylene oxide units.
  • the substantially linear polyether polyols have number average molecular weights of 500 to 5000 g / mol. They can be used both individually and in the form of mixtures with one another.
  • One or more aliphatic polyether polyols are preferably used from the group consisting of poly (ethylene glycol), poly (l, 2-propylene glycol), poly (1,3-propylene glycol), poly (tetramethylene glycol) and polyether polyols composed of ethylene oxide units and of propylene oxide units.
  • Suitable polyester polyols for component D) can be prepared, for example, from dicarboxylic acids having 2 to 12 carbon atoms, preferably 4 to 6 carbon atoms, and polyhydric alcohols.
  • Suitable dicarboxylic acids are, for example: aliphatic dicarboxylic acids, such as succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid and sebacic acid, and aromatic dicarboxylic acids, such as phthalic acid, isophthalic acid and terephthalic acid.
  • the dicarboxylic acids can be used individually or as mixtures, for example in the form of an amber, glutaric and adipic acid mixture.
  • polyester polyols For the preparation of the polyester polyols, it may be advantageous, instead of the dicarboxylic acids corresponding dicarboxylic acid derivatives, such as carbonic acid diesters having 1 to 4 carbon atoms in the alcohol radical, carboxylic anhydrides or carboxylic acid chlorides to use.
  • dicarboxylic acids corresponding dicarboxylic acid derivatives, such as carbonic acid diesters having 1 to 4 carbon atoms in the alcohol radical
  • carboxylic anhydrides or carboxylic acid chlorides examples of polyhydric alcohols are glycols having 2 to 10, preferably 2 to 6 carbon atoms, such as ethylene glycol, diethylene glycol, 1, 4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1, 10-decanediol, 2,2- Dimethyl 1,3-propanediol, 1,3-propanediol and dipropylene glycol.
  • the polyhydric alcohols may be used alone or optionally mixed with each other.
  • esters of carbonic acid with the diols mentioned in particular those having 4 to 6 carbon atoms, such as 1, 4-butanediol or 1,6-hexanediol, condensation products of hydroxycarboxylic acids, for example hydroxycaproic acid and polymerization of lactones, for example optionally substituted caprolactones.
  • Ethanediol polyadipates, 1,4-butanediol polyadipates, ethanediol-1, 4-butanediol polyadipates, 1,6-hexanediol neopentyl glycol polyadipates, 1,6-hexanediol-1,4-butanediol polyadipates are preferably used as polyester polyols and poly-caprolactones.
  • the polyester polyols have number average molecular weights of 500 to 5000 g / mol and can be used individually or in the form of mixtures with one another. Aliphatic polyester polyols are preferably used.
  • Suitable catalysts E) for TPU preparation may be those known in the art and conventional tertiary amines, e.g. Triethylamine, dimethylcyclohexylamine, N-methylmorpholine, ⁇ , ⁇ '-dimethyl-piperazine, 2- (dimethylamino-ethoxy) -ethanol, diazabicyclo- (2,2,2) -octane, and preferably organic metal compounds, e.g. Titanic acid esters, iron compounds, tin compounds, e.g. Stannous diacetate, stannous dioctoate, stannous dilaurate or the tin dialkyl salts of aliphatic carboxylic acids, e.g. Dibutyltin diacetate or dibutyltin dilaurate.
  • Particularly preferred catalysts are organic metal compounds, in particular titanic acid esters, iron or tin compounds.
  • auxiliaries and / or additives F may also be added. Mention may be made, for example, of silicone compounds, antiblocking agents, inhibitors, stabilizers against hydrolysis, light, heat and discoloration, flame retardants, dyes, pigments, inorganic or organic fillers and reinforcing agents. Reinforcing agents are, in particular, fibrous reinforcing materials, such as inorganic fibers, which are produced according to the prior art and can also be treated with a sizing agent.
  • auxiliaries and additives can be found in the specialist literature, for example JH Saunders, KC Frisch: “High Polymers”, Volume XVI, Polyurethanes, Part 1 and 2, Interscience Publishers 1962 and 1964, R.Gumbleter, H. Müller (Ed.): Paperback of the plastic additives, 3rd edition, Hanser Verlag, Kunststoff 1989, or DE-A 29 01 774.
  • plasticizers such as phosphates, Adipates, sebacates and alkyl sulfonic acid esters.
  • customary monofunctional compounds in small amounts, for example as chain terminators or demolding aids.
  • the synthesis components if appropriate in the presence of catalysts, auxiliaries and additives, can be reacted in amounts such that the equivalence ratio of NCO groups to the sum of the NCO-reactive groups, in particular the OH groups of components B) , C) and D) is 0.9: 1.0 to 1.2: 1.0, preferably 0.95: 1.0 to 1.10: 1.0.
  • the TPU contain the component G) in an amount of 0.02 to 3 wt .-%, preferably 0.02 to 1.0 wt .-%, based on the total thermoplastic polyurethane. These are special waxes.
  • the water vapor permeability of the TPU used in the invention decreases after aging at 70 ° C for 24 hours not more than 10%.
  • Suitable components G) are, for example, maleic anhydride grafted polyolefins, preferably maleic anhydride grafted polyethylenes. Also suitable are diesters of branched diols, which may contain other hydroxyl groups, with mixtures of linear or branched, saturated or unsaturated mono- and dicarboxylic acids, wherein the linear or branched, saturated or unsaturated mono- and dicarboxylic acids are optionally contained in stoichiometric excess, wherein it is preferably diesters of adipic acid, oleic acid and pentaerythritol.
  • the components under G) are preferably mixtures of reaction products of ethylenediamine with stearic acid and of ethylenediamine with 12-hydroxystearic acid, mixtures of reaction products of ethylenediamine with stearic acid and of ethylenediamine with 12-hydroxystearic acid and stearic acid, mixtures of reaction products of ethylenediamine with 12-hydroxystearic acid and of ethylenediamine with 12-hydroxystearic acid and stearic acid, or mixtures of reaction products of ethylenediamine with stearic acid and of ethylenediamine with 12-hydroxystearic acid and ethylenediamine with 12-hydroxystearic acid and stearic acid.
  • the reaction can be carried out according to customary amidation methods of organic chemistry (compare Houben and Weyl, Methoden der organischen Chemie, 4th edition, Thieme since 1952, 8, 647-671).
  • the acids can be reacted together with an equimolar amount of ethylenediamine, or they are reacted individually and then mixes the resulting amides. It is also possible to use mixtures of the waxes mentioned.
  • no montan acid ester is used as component G).
  • nonwovens or textiles are preferably used as a further layer or layers of the composite part. These layers can be arranged on one side or on both sides on the layer of TPU.
  • the TPUs used may be continuous in the so-called extruder process, e.g. in a multi-screw extruder.
  • the dosage of TPU components A), B), C) and optionally D) may be concurrent, i. in the one-shot method, or sequentially, i. after one
  • the prepolymer can be initially introduced in batches or continuously in a part of the extruder or in a separate upstream prepolymer aggregate.
  • the waxes G) can be continuously metered into the TPU reaction in the extruder, preferably in the first extruder housing.
  • the dosage is carried out either at room temperature in the solid state or in liquid form.
  • they can be homogeneously mixed into the polyol component, preferably at temperatures of from 70 to 120 ° C., before the reaction and be metered together with it into the other components.
  • the TPUs used for producing the composite parts according to the invention have an excellent processing behavior.
  • films and films or coatings with high homogeneity can be produced from the melt. These films and films or coatings have a low tendency to adhere and a very good separation behavior.
  • the flat composite parts produced with the TPU can be used for the production of roof underlays and facade tensioning membranes.
  • the invention will be explained in more detail with reference to the following examples.
  • Comparative Examples 17 to 20 were prepared in a continuous TPU reaction in a tube mixer / extruder (extruder ZSK 120, Werner / Pfleiderer) by the known prepolymer driving, as described for example in Example 1 of EP-A 571 828: . 73.5 Parts by weight of poly-tetrahydrofuran (Terathane ® 2000 (OH number: 56 mg KOH / g, poly (tetrahydrofuran)), BASF SE, Ludwigshafen, DE)., 0.24 parts by weight Irganox ® 1010 ( BASF SE, Ludwigshafen, DE), 0.51 wt. parts by Tinuvin ® 328 (BASF SE, Ludwigshafen, DE), 0.3 wt.
  • Tethane ® 2000 OH number: 56 mg KOH / g, poly (tetrahydrofuran)
  • BASF SE Ludwigshafen, DE
  • Irganox ® 1010 BASF SE, Ludwigshafen, DE
  • Wax 1 Loxamid ® 3324 ( ⁇ , ⁇ '-ethylene-bis-stearylamide; Cognis Oleochemicals GmbH,
  • Wax 2 ® Licowax E (Montanklareester (C24-C34, 2-valent alcohol); Clariant,
  • Wax 3 Licolub ® FA6 (amide of ethylenediamine / 12-hydroxystearic acid /
  • Wax 4 Loxiol ® G78 (calcium soaps, and fatty acid ester (acid number ⁇ 12); Cognis
  • Wax 5 PU1747 (adipic acid / oleic acid / pentaerythritol ester (acid number ⁇ 2, OH number 51);
  • Wax 6 Licocene ® PEMA4221 (maleic anhydride grafted polyethylene; Clariant,
  • the TPU granules 1 to 20 were in each case in a single-screw extruder (single-screw extruder 30 / 25D Plasticorder PL 2100-6, Fa.Bender) melted (dosage about 3 kg / h, 185-215 ° C) and by a Slot die each extruded into a flat film.
  • the water vapor transmission rate (WDD) of the films produced was determined by the following two methods:
  • the films produced were first stored at 70 ° C. for 24 hours in an oven and then the WDD was determined by the methods described above.
  • Table 2 WDD and WDD after aging according to method B

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Architecture (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Mechanical Engineering (AREA)
  • Structural Engineering (AREA)
  • Civil Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Electromagnetism (AREA)
  • Physics & Mathematics (AREA)
  • Materials Engineering (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Laminated Bodies (AREA)

Abstract

L'invention concerne des pièces composites planes perméables à la vapeur d'eau, composées d'au moins deux couches, au moins une couche étant constituée d'un polyuréthane thermoplastique contenant des cires spécifiques, ainsi que leur utilisation.
EP15734162.9A 2014-07-11 2015-07-06 Pièces composites perméables à la vapeur d'eau Withdrawn EP3166791A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP14176711 2014-07-11
PCT/EP2015/065282 WO2016005298A1 (fr) 2014-07-11 2015-07-06 Pièces composites perméables à la vapeur d'eau

Publications (1)

Publication Number Publication Date
EP3166791A1 true EP3166791A1 (fr) 2017-05-17

Family

ID=51178746

Family Applications (1)

Application Number Title Priority Date Filing Date
EP15734162.9A Withdrawn EP3166791A1 (fr) 2014-07-11 2015-07-06 Pièces composites perméables à la vapeur d'eau

Country Status (5)

Country Link
US (1) US20170204218A1 (fr)
EP (1) EP3166791A1 (fr)
CN (1) CN106794686A (fr)
TW (1) TW201609395A (fr)
WO (1) WO2016005298A1 (fr)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106660341A (zh) * 2014-07-11 2017-05-10 科思创德国股份有限公司 水蒸气可透过的复合构件

Family Cites Families (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19651994A1 (de) * 1996-12-13 1998-06-18 Basf Ag Verfahren zur Herstellung von selbsttrennenden, kompakten oder zelligen, gegebenenfalls Verstärkungsmittel enthaltenden Formkörpern aus Polyisocyanat-Polyadditionsprodukten und innere Formtrennmittel hierfür
DE19706380A1 (de) * 1997-02-19 1998-08-20 Wolff Walsrode Ag Atmungsaktive Mehrschichtfolie
US6207752B1 (en) * 1997-12-10 2001-03-27 Advanced Elastomer Systems Lp Thermoplastic vulcanizates of carboxylated nitrile rubber and thermoplastic polyurethanes
JP4328988B2 (ja) * 1999-10-21 2009-09-09 Ｄｉｃ株式会社 粉末成形用熱可塑性ポリウレタン樹脂組成物及び成形材料
AU2002301252B2 (en) * 2001-10-12 2007-12-20 Bayer Aktiengesellschaft Photovoltaic modules with a thermoplastic hot-melt adhesive layer and a process for their production
JP3870124B2 (ja) * 2002-06-14 2007-01-17 キヤノン株式会社 画像処理装置及びその方法、並びにコンピュータプログラム及びコンピュータ可読記憶媒体
US8425929B2 (en) * 2004-04-30 2013-04-23 Allergan, Inc. Sustained release intraocular implants and methods for preventing retinal dysfunction
DE102005012796A1 (de) * 2005-03-19 2006-09-21 Hennecke Gmbh Verfahren zur Herstellung von faserverstärkten Verbundteilen
DE102006009096B4 (de) * 2006-02-28 2009-06-10 Bayer Materialscience Ag Thermoplastisch verarbeitbare Polyurethane, Verfahren zu ihrer Herstellung und ihre Verwendung
CN106660341A (zh) * 2014-07-11 2017-05-10 科思创德国股份有限公司 水蒸气可透过的复合构件
TWI676552B (zh) * 2014-07-11 2019-11-11 德商拜耳材料科學股份有限公司 水蒸氣可滲透性複合組件

Also Published As

Publication number Publication date
TW201609395A (zh) 2016-03-16
CN106794686A (zh) 2017-05-31
WO2016005298A1 (fr) 2016-01-14
US20170204218A1 (en) 2017-07-20

Similar Documents

Publication Publication Date Title
DE102006009096B4 (de) Thermoplastisch verarbeitbare Polyurethane, Verfahren zu ihrer Herstellung und ihre Verwendung
EP1338614B1 (fr) Procédé de production des elastomères de polyuréthane thermoplastiques, mous, facilement démoulables et à retrait minime
DE102005039933B4 (de) Verfahren zur Herstellung von thermoplastisch verarbeitbaren Polyurethanen
EP0845492B1 (fr) Polyuréthanes thermoplastiques contenant de mélanges spéciaux de cires
EP1069143B1 (fr) Films polyuréthane souples élastiques, leur procédé de préparation et leur utilisation
EP1967537A1 (fr) Procédé de fabrication de corps de moulage à mémoire de forme dotés d'une grande zone d'utilisation
EP0792917B1 (fr) Polyuréthanes thermoplastiques contenant de la cire
EP1055691B1 (fr) Méthode de fabrication en continu de polyuréthanes façonnables sous forme thermoplastique
EP1055692B1 (fr) Méthode de fabrication en continu de polyuréthanes façonnables sous forme thermoplastique
EP1153951B1 (fr) Pièce moulée à partir d'un polyuréthane thermoplastique ne donnant pas lieu à la formation de brouillard
EP3166792B1 (fr) Pièces composites perméables à la vapeur d'eau
EP2758444B1 (fr) Polyuréthane thermoplastique pour la fabrication de fibres hydrophiles
EP3612580B1 (fr) Polyuréthanes thermoplastiques aliphatiques, leur fabrication et leur utilisation
EP3589676B1 (fr) Polyuréthanes thermoplastiques résistant à l'impact à basse température
EP3166791A1 (fr) Pièces composites perméables à la vapeur d'eau
EP0111682A2 (fr) Elastomères de polyuréthane facilement démoulables, exempts de blocking, procédé pour leur fabrication et leur utilisation
EP0854158B1 (fr) Polyuréthanes thermoplastiques ayant des agents de démoulage incorporés
EP3166790A1 (fr) Pièces composites perméables à la vapeur d'eau
WO2021228715A1 (fr) Procédé de production de polyuréthanes thermoplastiques
DE4446332A1 (de) Thermoplastische Polyurethane mit verbessertem Schmelzefluß

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20170213

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

AX Request for extension of the european patent

Extension state: BA ME

DAV Request for validation of the european patent (deleted)
DAX Request for extension of the european patent (deleted)
17Q First examination report despatched

Effective date: 20171106

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION IS DEEMED TO BE WITHDRAWN

18D Application deemed to be withdrawn

Effective date: 20200603