EP2010387A2 - Élément composite à base de polyuréthanne et de polyoléfine - Google Patents

Élément composite à base de polyuréthanne et de polyoléfine

Info

Publication number
EP2010387A2
EP2010387A2 EP07712356A EP07712356A EP2010387A2 EP 2010387 A2 EP2010387 A2 EP 2010387A2 EP 07712356 A EP07712356 A EP 07712356A EP 07712356 A EP07712356 A EP 07712356A EP 2010387 A2 EP2010387 A2 EP 2010387A2
Authority
EP
European Patent Office
Prior art keywords
polyurethane
composite element
adhesive
groups
element according
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Withdrawn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
EP07712356A
Other languages
German (de)
English (en)
Inventor
Bernd Bruchmann
Hauke Malz
Ulrike Licht
Oliver Hartz
Karl-Heinz Schumacher
Andre Burghardt
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.)
BASF SE
Original Assignee
BASF SE
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 BASF SE filed Critical BASF SE
Priority to EP07712356A priority Critical patent/EP2010387A2/fr
Publication of EP2010387A2 publication Critical patent/EP2010387A2/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • 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
    • 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
    • B32B27/12—Layered products comprising a layer of synthetic resin next to a fibrous or filamentary layer
    • 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
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • 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
    • C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation 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
    • C08G18/28—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
    • C08G18/3225—Polyamines
    • C08G18/3253—Polyamines being in latent form
    • C08G18/3256—Reaction products of polyamines with aldehydes or ketones
    • 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
    • C08G18/34—Carboxylic acids; Esters thereof with monohydroxyl compounds
    • 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
    • C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
    • C08G18/3855—Low-molecular-weight compounds having heteroatoms other than oxygen having sulfur
    • C08G18/3857—Low-molecular-weight compounds having heteroatoms other than oxygen having sulfur having nitrogen in addition to sulfur
    • 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
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/4236—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups
    • C08G18/4238—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups derived from dicarboxylic acids and dialcohols
    • 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
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6633—Compounds of group C08G18/42
    • C08G18/6659—Compounds of group C08G18/42 with compounds of group C08G18/34
    • 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
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6666—Compounds of group C08G18/48 or C08G18/52
    • C08G18/6692—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/34
    • 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
    • C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
    • C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
    • C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
    • C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
    • C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
    • 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
    • C08J5/127—Aqueous adhesives
    • 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
    • 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
    • B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
    • B32B2262/02—Synthetic macromolecular fibres
    • B32B2262/0253—Polyolefin fibres
    • 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
    • B32B2419/00—Buildings or parts thereof
    • B32B2419/06—Roofs, roof membranes
    • 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
    • C08G2170/00—Compositions for adhesives
    • C08G2170/80—Compositions for aqueous adhesives
    • 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
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2323/10—Homopolymers or copolymers of propene
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31551—Of polyamidoester [polyurethane, polyisocyanate, polycarbamate, etc.]
    • Y10T428/31573—Next to addition polymer of ethylenically unsaturated monomer
    • Y10T428/31587—Hydrocarbon polymer [polyethylene, polybutadiene, etc.]
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
    • Y10T442/60—Nonwoven fabric [i.e., nonwoven strand or fiber material]
    • Y10T442/608—Including strand or fiber material which is of specific structural definition
    • Y10T442/614—Strand or fiber material specified as having microdimensions [i.e., microfiber]
    • Y10T442/626—Microfiber is synthetic polymer
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
    • Y10T442/60—Nonwoven fabric [i.e., nonwoven strand or fiber material]
    • Y10T442/674—Nonwoven fabric with a preformed polymeric film or sheet
    • Y10T442/678—Olefin polymer or copolymer sheet or film [e.g., polypropylene, polyethylene, ethylene-butylene copolymer, etc.]

Definitions

  • Composite elements are elements in which at least two substrates of different materials are interconnected.
  • Composite elements are important for a wide variety of uses. Frequently, in such composite elements polymer films or polymer films are bonded to non-woven fabrics.
  • Non-woven fabrics are textile fabrics made of fibers. Of particular importance are nonwoven nonwovens. In such nonwoven fibrous webs, the fibers adhere physically or chemically, e.g. B. by using a binder to each other.
  • Nonwovens come in the hygiene sector, z. B. for diapers and disposable washcloths, or in technical applications, such as filters, in medical applications, in civil engineering, especially as geotextiles and roof underlays, for use.
  • Nonwovens based on synthetic polymers are mainly produced in continuous processes. Here are especially the meltblown and the spunbond process called. In these processes, the polymer is melted on an extruder and conveyed by melt pumping to a spinneret.
  • melt pumping to a spinneret.
  • modern spunbonding processes work continuously at high throughputs with spinning beams of up to 5 m width to produce the spunbonded nonwovens.
  • nonwoven can also be made from staple fibers.
  • the staple fibers having a length of 25 mm to 400 mm, but preferably 40 to 60 mm and a titer c of 3.3-8 dtex are deposited either parallel or unsorted on a belt and then thermally or chemically bonded together.
  • PP nonwovens are used as roofing membranes. Due to the porosity of the PP nonwovens a very good rear ventilation of the roof is given. However, this is also a major disadvantage of PP nonwovens. For if the outer skin of the roof is leaking and water should penetrate, this water also penetrates through the porous nonwoven layer. For this reason, there are efforts to combine PP nonwovens with a film in order to obtain a dense composite on these. The nonwoven gives this composite the mechanical stability and tear strength, the film the desired tightness. However, even such a composite must possess the necessary breathability. A combination of PP nonwoven and PP-FoNe separates here z. B. due to the low water vapor permeability of the PP.
  • thermoplastic polyurethanes are polyurethanes that are thermoplastically processable.
  • thermoplastic is meant the property of the polyurethane. were repeatedly softened in the temperature between 150 ° C and 300 ° C for the polyurethane in the heat to soften and cool and in the softened state repeatedly be formed by flow as a molded part, extrudate or forming part to semifinished or articles.
  • thermoplastic polyurethanes based on polyether and polyesterols have a high monolithic water vapor permeability. For this reason, TPU films are often used where water vapor permeability and water resistance are important, eg. B. in functional clothing.
  • PP and TPU do not cling to each other.
  • a composite delaminates even under low load again.
  • the state of the art in processes such as injection molding is to hydrophilize the PP by means of plasma or corona treatment, and thus to produce adhesion.
  • PP nonwovens can be damaged, especially if they have a low basis weight.
  • Polypropylene nonwovens have no elastic character. In hygiene applications, z. B. in diapers, it is therefore necessary polypropylene nonwovens with elastic fibers, eg. B. spandex fibers to ensure the necessary comfort. However, this method is complicated and expensive. It would be better if the nonwoven itself was elastic.
  • TPU nonwovens have this desired elasticity.
  • TPU nonwovens have this desired elasticity.
  • the Bicomponentenverhahren is very expensive and therefore expensive. So you need all components of the system twice, i. two separate extruders, separate melt lines, pumps, etc.
  • the spinnerets are very expensive and therefore expensive.
  • the object of the invention was therefore a composite element which is easy to produce and has the properties required for the respective use.
  • the composite element or laminate When used as a roof underlay the composite element or laminate should in particular have good mechanical properties and possess the required breathability.
  • the laminate should be easy and environmentally friendly to manufacture and use.
  • the initially defined composite element was found. Also found were uses of the composite elements, in particular z. B. also as Dachund terspannbahn.
  • the composite element according to the invention comprises a substrate of a polyolefin and a substrate of polyurethane, which are joined together by an adhesive.
  • the polyurethane is preferably thermoplastic polyurethane (TPU).
  • Thermoplastic polyurethanes are polyurethanes which, after heating to temperatures at which the polyurethane is flowable, z. B. to temperatures of 150 to 300 ° C, and cooling remain ductile, d. H. made flowable again, can be brought into the desired shape and cooled. In the softened state, the polyurethane can be molded into any shape, extruded or otherwise processed.
  • TPU The preparation of TPU is carried out in particular by reacting diisocyanates with compounds having at least two isocyanate-reactive hydrogen atoms, preferably difunctional alcohols.
  • Suitable diisocyanates are customary aromatic, aliphatic and / or cycloaliphatic diisocyanates, for example diphenylmethane diisocyanate (MDI), tolylene diisocyanate (TDI), tri-, tetra-, penta-, hexa-, hepta- and / or octamethylene diisocyanate, 2-methyl pentamethylene diisocyanate 1, 5, 2-ethyl butylene diisocyanate 1, 4, 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethyl cyclohexane (isophorone diisocyanate, IPDI), 1, 4- and / or 1, 3-bis (isocyanatomethyl) cyclohexane (HXDI), 1,4-cyclohexane diisocyanate, 1-methyl-2,4- and / or 2,6-cyclohexane diisocyanate, 4,4'-, 2,4'- and
  • isocyanate-reactive compounds generally known polyhydroxy compounds having molecular weights of 500 to 8000, preferably 600 to 6000, in particular 800 to 4000, and preferably an average functionality of 1, 8 to 2.6, preferably 1, 9 to 2.2, in particular 2 are used, for example, polyesterols, polyetherols and / or polycarbonate. Preference is given to using (b) polyester diols obtainable by reacting butanediol and hexanediol as diol with adipic acid as dicarboxylic acid, the weight ratio of butanediol to hexanediol preferably being 2: 1. Also preferred is polytetrahydrofuran having a molecular weight of 750 to 2500 g / mol, preferably 750 to 1200 g / mol.
  • chain extenders it is possible to use generally known compounds, for example diamines and / or alkanediols having 2 to 10 C atoms in the alkylene radical, in particular ethylene glycol and / or butanediol-1, 4, and / or hexanediol and / or di- and / or Tri-oxyalkylenglykole having 3 to 8 carbon atoms in the oxyalkylene lenrest, preferably corresponding oligo-polyoxypropylene glycols, mixtures of the chain extenders can be used.
  • diamines and / or alkanediols having 2 to 10 C atoms in the alkylene radical in particular ethylene glycol and / or butanediol-1, 4, and / or hexanediol and / or di- and / or Tri-oxyalkylenglykole having 3 to 8 carbon atoms in the oxyalkylene lenrest, preferably corresponding oli
  • chain extenders it is also possible to use 1,4-bis (hydroxymethyl) benzene (1,4-BHMB), 1,4-bis (hydroxyethyl) benzene (1,4-BHEB) or 1,4-bis (2 -hydroxyethoxy) -benzene (1, 4-HQEE) are used.
  • chain extender butanediol 1, 4 ..
  • catalysts which accelerate the reaction between the NCO groups of the diisocyanates and the hydroxyl groups of the synthesis components, for example tertiary amines, such as triethylamine, dimethylcyclohexylamine, N-methylmorpholine, N, N'-dimethylpiperazine, 2- (dimethylaminoethoxy) - ethanol, diazabicyclo- (2,2,2) octane and the like, and in particular organic metal compounds such as titanic acid esters, iron compounds such as Iron (III) acetylacetonate, tin compounds such as tin diacetate, tin dilaurate or the tin dialkyl salts of aliphatic carboxylic acids such as dibutyltin diacetate, dibutyltin dilaurate or the like.
  • the catalysts are usually used in amounts of 0.0001 to 0.1 parts by weight per 100 parts by weight of polyhydroxyl compound.
  • auxiliaries to the structural components. Mention may be made, for example, of surface-active substances, flame retardants, nucleating agents, lubricants and mold release agents, dyes and pigments, inhibitors, stabilizers against hydrolysis, light, heat, oxidation or discoloration, protective agents against microbial degradation, inorganic and / or organic fillers, reinforcing agents and plasticizers.
  • the preparation of the TPU is usually carried out by conventional methods, such as by belt systems or reaction extruder. Films can also be made of TPU by conventional methods, for. B. be prepared by extrusion To the polyolefin
  • Suitable polyolefins are, for. B. homopolymers of monoolefins or copolymers of monoolefins with other monoolefins, diolefins or with other vinyl monomers.
  • Ethylene-propylene copolymers linear low density polyethylene (LLDPE) and blends thereof with low density polyethylene (LDPE), propylene-1-butene-1 copolymers, propylene-isobutylene copolymers, ethylene-butene-1 copolymers, Ethylene-hexene copolymers, ethylene-methylpentene copolymers, ethylene-heptene copolymers, ethylene-octene copolymers, propylene-butadiene copolymers, isobutylene-isoprene copolymers, ethylene-alkyl acrylate copolymers, ethylene-alkyl methacrylate copolymers, Ethylene-vinyl acetate copolymers and their copolymers with carbon monoxide, or ethylene-acrylic acid copolymers and their salts (ionomers), as well as terpolymers of ethylene with propylene and a
  • the polyolefin is polypropylene.
  • Polypropylene is to be understood as meaning homopolymers of propylene or propylene copolymers which consist of at least 50% by weight, in particular at least 70% by weight, more preferably at least 90% by weight and most preferably at least 95% by weight of propylene ,
  • the adhesive is a polyurethane adhesive.
  • Polyurethane adhesive is to be understood as meaning an adhesive which contains at least one polyurethane as binder.
  • the aqueous polyurethane adhesive preferably comprises an aqueous solution of a polyurethane or, particularly preferably, an aqueous dispersion of a polyurethane as binder.
  • the polyurethane adhesive in addition to the polyurethane further binders, for. B. also available by free-radical polymerization polymers such as polyacrylates, polyvinyl acetate or ethylene / acetate copolymers, or contain other additives.
  • the polyurethane adhesive preferably consists overall of at least 15% by weight, preferably at least 30% by weight, more preferably at least 50% by weight, in particular at least 70% by weight, or at least 90% by weight. of polyurethane, based on the sum of all components (solid, ie excluding water and solvents with a boiling point less than 150 ° C at 1 bar).
  • the adhesive contains only a polyurethane or a mixture of polyurethanes as a binder.
  • the polyurethanes preferably consist predominantly of polyisocyanates, in particular diisocyanates on the one hand and, on the other hand, as reactants, polyester diols, polyether diols or mixtures thereof.
  • the polyurethane is at least 40 wt .-%, more preferably at least 60 wt .-% and most preferably at least 80 wt .-% of diisocyanates, polyether diols and / or polyester diols constructed.
  • the polyurethane has a melting point in the range of -50 to 150 ° C, more preferably from 20 to 150, and most preferably from 30 to 100 ° C and especially from 50 to 80 ° C.
  • the polyurethane contains polyester diols in an amount of more than 10 wt .-%, based on the polyurethane.
  • the polyurethane is preferably composed of:
  • diisocyanates X (NCO) 2 wherein X is an aliphatic hydrocarbon radical having 4 to 15 carbon atoms, a cycloaliphatic or aromatic hydrocarbon radical having 6 to 15 carbon atoms or an araliphatic hydrocarbon radical having 7 to 15 carbon atoms
  • diisocyanates are tetramethylene diisocyanate, hexamethylene diisocyanate, dodecamethylene diisocyanate, 1,4-diisocyanatocyclohexane, 1-isocyanato-S. ⁇ . ⁇ -trimethyl-S-isocyanatomethylcyclohexane (IPDI), 2,2-bis (4-isocyanatocyclohexyl) propane , Trimethylhexandiisocyanat, 1, 4-diisocyanatobenzene, 2,4-diisocyanatotoluene, 2,6-diisocyanatotoluene
  • Such diisocyanates are available commercially.
  • mixtures of these isocyanates are the mixtures of the respective structural isomers of diisocyanatotoluene and diisocyanato-diphenylmethane; in particular, the mixture of 80 ⁇ mol 2,4-diisocyanatotoluene and 20 mol% 2,6-diisocyanatotoluene is suitable.
  • mixtures of aromatic isocyanates such as 2,4-diisocyanatotoluene and / or 2,6-diisocyanatotoluene with aliphatic or cycloaliphatic isocyanates such as hexamethylene diisocyanate or IPDI are particularly advantageous, the preferred mixing ratio of aliphatic to aromatic isocyanates being 4: 1 to 1: 4 is.
  • suitable diols (b) are primarily relatively high molecular weight diols (b1) which have a molecular weight of about 500 to 5000, preferably about 1000 to 3000 g / mol. This is the number average molecular weight Mn. Mn results from determining the number of end groups (OH number).
  • the diols (b1) may be polyester polyols, e.g. from Ullmann's Encyclopedia of Industrial Chemistry, 4th Edition, Volume 19, pp 62 to 65 are known. Preference is given to using polyesterpolyols which are obtained by reacting dihydric alcohols with dibasic carboxylic acids. Instead of the free polycarboxylic acids, it is also possible to use the corresponding polycarboxylic acid anhydrides or corresponding polycarboxylic acid esters of lower alcohols or mixtures thereof to prepare the polyesterpolyols.
  • the polycarboxylic acids may be aliphatic, cycloaliphatic, araliphatic, aromatic or heterocyclic and optionally, e.g.
  • halogen atoms substituted and / or unsaturated.
  • these include: suberic acid, azelaic acid, phthalic acid, isophthalic acid, phthalic anhydride. Tetrahydrophthalic anhydride, hexahydrophthalic anhydride, tetrachlorophthalic anhydride, endomethylenetetrahydrophthalic anhydride, glutaric anhydride, maleic acid, maleic anhydride, fumaric acid, dimer fatty acids.
  • dicarboxylic acids of the general formula HOOC- (CH 2) y -COOH, where y is a number from 1 to 20, preferably an even number from 2 to 20, e.g. Succinic acid, adipic acid, sebacic acid and dodecanedicarboxylic acid.
  • Ethylene glycol propane-1, 2-diol, propane-1, 3-diol, butane-1, 3-diol, butene-1, 4-diol, butyne-1, 4-diol, pentane-1, 5 diol, neopentyl glycol, bis (hydroxymethyl) cyclohexanes, such as 1,4-bis (hydroxymethyl) cyclohexane, 2-methylpropane-1,3-diol, methylpentanediols, furthermore diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, dipropylene glycol, Polypropylene glycol, dibutylene glycol and polybutylene glycols into consideration.
  • Alcohols of the general formula HO- (CH 2) x -OH are preferred, where x is a number from 1 to 20, preferably an even number from 2 to 20.
  • examples of these are ethylene glycol, butane-1, 4-diol, hexane-1, 6-diol, octane-1, 8-diol and dodecane-1, 12-diol. Further preferred is neopentyl glycol.
  • polycarbonate diols as they are, for. B. by reaction of phosgene with an excess of the mentioned as synthesis components for the polyester polyols low molecular weight alcohols, into consideration.
  • polyester-based lactone-based sols which are homopolymers or copolymers of lactones, preferably hydroxyl-terminated addition products of lactones to suitable difunctional starter molecules.
  • lactones are preferably those in Considerations derived from compounds of the general formula HO- (CH 2) z -COOH, where z is a number from 1 to 20 and an H atom of a methylene moiety may also be substituted by a C 1 to C 4 alkyl radical. Examples are e-caprolactone, ⁇ -propiolactone, g-butyrolactone and / or methyl-e-caprolactone and mixtures thereof.
  • Suitable starter components are for.
  • polyester polyols low molecular weight dihydric alcohols.
  • the corresponding polymers of e-caprolactone are particularly preferred.
  • Lower polyester diols or polyether diols can also be used as starters for the preparation of the lactone polymers.
  • the polymers of lactones it is also possible to use the corresponding, chemically equivalent polycondensates of the hydroxycarboxylic acids corresponding to the lactones.
  • Polyether diols are in particular by polymerization of ethylene oxide, propylene oxide, butylene oxide, tetrahydrofuran, styrene oxide or epichlorohydrin with itself, z. B. in the presence of BF3 or by addition of these compounds, optionally in admixture or in succession, to starting components with reactive hydrogen atoms, such as alcohols or amines, for.
  • reactive hydrogen atoms such as alcohols or amines
  • reactive hydrogen atoms such as alcohols or amines
  • water ethylene glycol, propane-1, 2-diol, propane-1, 3-diol, 2,2-bis (4-hydroxyphenyl) propane or aniline available.
  • Particularly preferred are polypropylene oxide, polytetrahydrofuran having a molecular weight of 240 to 5000, and especially 500 to 4500.
  • polyether diols which consist of less than 20 wt .-% of ethylene oxide.
  • Polyether diols containing at least 20% by weight are hydrophilic polyether diols which belong to monomers c).
  • polyhydroxyolefins may also be included, preferably those having 2 terminal hydroxyl groups, e.g. ⁇ , - ⁇ -Dihydroxypolybutadien, ⁇ , - ⁇ - Dihydroxypolymethacrylester or ⁇ , - ⁇ -Dihydroxypolyacrylester as monomers (c1).
  • ⁇ , - ⁇ -Dihydroxypolybutadien e.g. ⁇ , - ⁇ - Dihydroxypolymethacrylester or ⁇ , - ⁇ -Dihydroxypolyacrylester as monomers (c1).
  • Such compounds are known, for example, from EP-A 622 378.
  • Other suitable polyols are polyacetals, polysiloxanes and alkyd resins.
  • At least 30 mol%, more preferably at least 70 mol% of the diols b1) are polyesterdiols. Particular preference is given to using diols b1) exclusively polyesterdiols.
  • the hardness and modulus of elasticity of the polyurethanes can be increased if, as diols (b), low molecular weight diols (b2) having a molecular weight of from about 60 to 500, preferably from 62 to 200, g / mol are used in addition to the diols (b1).
  • the monomers (b2) used are, in particular, the synthesis components of the short-chain alkanediols mentioned for the preparation of polyesterpolyols, the unmodified branched diols having 2 to 12 carbon atoms and an even number of carbon atoms and pentane-1, 5-diol and neopentyl glycol are preferred.
  • diols b2) come z.
  • ethylene glycol propane-1, 2-diol, propane-1, 3-diol, butane-1, 3-diol, butene-1, 4-diol, butyne-1, 4-diol, pentane-1, 5 diol, neopentyl glycol, bis-
  • (hydroxymethyl) cyclohexanes such as 1, 4-bis (hydroxymethyl) cyclohexane, 2-methylpropane-1, 3-diol, methylpentanediols, furthermore diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, dipropylene glycol, polypropylene glycol, dibutylene glycol and polybutylene glycols consideration.
  • Alcohols of the general formula HO- (CH 2) x -OH are preferred, where x is a number from 1 to 20, preferably an even number from 2 to 20.
  • Examples of these are ethylene glycol, butane-1, 4-diol, hexane-1, 6-diol, octane-1, 8-diol and dodecane-1, 12-diol. Further preferred is neopentyl glycol.
  • the proportion of the diols (b1), based on the total amount of the diols (b) is 10 to 100 mol% and the proportion of the monomers (b2), based on the total amount of the diols (b) 0 to 90 mol%.
  • the ratio of the diols (b1) to the monomers (b2) is particularly preferably 0.1: 1 to 5: 1, particularly preferably 0.2: 1 to 2: 1.
  • the polyurethanes preferably contain components (a), (b) and (d) which are different from monomers (c) containing at least one isocyanate group or at least one isocyanate-reactive group and moreover at least one hydrophilic group or a group which can be converted into a hydrophilic group, carry as a structural component.
  • the term "hydrophilic groups or potentially hydrophilic groups” is abbreviated to "(potentially) hydrophilic groups”. The (potentially) hydrophilic groups react much more slowly with isocyanates than the functional groups of the monomers which serve to build up the polymer main chain.
  • the proportion of components with (potentially) hydrophilic groups in the total amount of components (a), (b), (c), (d) and (e) is generally such that the molar amount of (potentially) hydrophilic groups Groups, based on the amount by weight of all monomers (a) to (e), 30 to 1000, preferably 50 to 500 and particularly preferably 80 to 300 mmol / kg.
  • the (potentially) hydrophilic groups may be nonionic or, preferably, (potentially) ionic hydrophilic groups.
  • Suitable nonionic hydrophilic groups are, in particular, polyethylene glycol ethers of preferably 5 to 100, preferably 10 to 80, ethylene oxide repeat units.
  • the content of polyethylene oxide units is generally 0 to 10, preferably 0 to 6 wt .-%, based on the amount by weight of all monomers (a) to (e).
  • Preferred monomers having nonionic hydrophilic groups are polyethylene oxide diols containing at least 20% by weight of ethylene oxide, polyethylene oxide monools and the reaction products of a polyethylene glycol and a diisocyanate which carry a terminally etherified polyethylene glycol radical. Such diisocyanates and processes for their preparation are given in the patents US-A 3,905,929 and US-A 3,920,598.
  • Ionic hydrophilic groups are especially anionic groups such as the sulfonate, the carboxylate and the phosphate group in the form of their alkali metal or ammonium salts and cationic groups such as ammonium groups, in particular protonated tertiary amino groups or quaternary ammonium groups.
  • Potentially ionic hydrophilic groups are especially those which can be converted by simple neutralization, hydrolysis or quaternization into the above-mentioned ionic hydrophilic groups, ie, for. As carboxylic acid groups or tertiary amino groups.
  • cationic monomers (c) are especially monomers having tertiary amino groups of particular practical importance, for example: tris (hydroxyalkyl) - amines, N, N'-bis (hydroxyalkyl) -alkylamine, N-hydroxyalkyl-dialkylamines, tris - (aminoalkyl) -amines, N, N'-bis (aminoalkyl) -alkylamines, N-aminoalkyl-dialkylamines, wherein the alkyl radicals and alkanediyl moieties of these tertiary amines independently of one another consist of 1 to 6 carbon atoms.
  • polyethers having tertiary nitrogen atoms preferably having two terminal hydroxyl groups e.g. by the alkoxylation of two amine-containing hydrogen atoms, e.g. Methylamine, aniline or N, N'-dimethylhydrazine, in a conventional manner are accessible, into consideration.
  • Such polyethers generally have a molecular weight between 500 and 6000 g / mol.
  • tertiary amines are either with acids, preferably strong mineral acids such as phosphoric acid, sulfuric acid, hydrohalic acids or strong organic acids or by reaction with suitable quaternizing agents such as C1 to C6 alkyl halides or benzyl halides, eg. As bromides or chlorides, transferred to the ammonium salts.
  • acids preferably strong mineral acids such as phosphoric acid, sulfuric acid, hydrohalic acids or strong organic acids
  • suitable quaternizing agents such as C1 to C6 alkyl halides or benzyl halides, eg. As bromides or chlorides, transferred to the ammonium salts.
  • Suitable monomers having (potentially) anionic groups are usually aliphatic, cycloaliphatic, araliphatic or aromatic carboxylic acids and sulfonic acids which contain at least one alcoholic hydroxyl group or at least carry a primary or secondary amino group. Preference is given to dihydroxyalkylcarboxylic acids, especially those having 3 to 10 carbon atoms, as are also described in US Pat. No. 3,412,054. In particular, compounds of the general formula (d)
  • R1 and R2 is a C1 to C4 alkanediyl (unit) and R3 is a C1 to C4 alkyl (unit) and, in particular, dimethylolpropionic acid (DMPA) is preferred.
  • DMPA dimethylolpropionic acid
  • dihydroxysulfonic acids and dihydroxyphosphonic acids such as 2,3-dihydroxypropanephosphonic acid.
  • dihydroxyl compounds having a molecular weight above 500 to 10,000 g / mol with at least 2 carboxylate groups which are known from DE-A 39 11 827. They are obtainable by reacting dihydroxyl compounds with tetracarboxylic acid dianhydrides such as pyromellitic dianhydride or cyclopentanetetracarboxylic dianhydride in a molar ratio of 2: 1 to 1:05 in a polyaddition reaction. Particularly suitable dihydroxyl compounds are the monomers (b2) listed as chain extenders and also the diols (b1).
  • Suitable monomers (c) with isocyanate-reactive amino groups are amino carboxylic acids such as lysine, ⁇ -alanine or the adducts of aliphatic diprimary diamines mentioned in DE-A 20 34 479 to ⁇ , ⁇ -unsaturated carboxylic or sulfonic acids into consideration.
  • R 4 and R 5 independently represent a C 1 to C 6 alkanediyl unit, preferably ethylene
  • Particularly preferred compounds of the formula (c2) are N- (2-aminoethyl) -2-aminoethanecarboxylic acid and also N- (2-aminoethyl) -2-aminoethanesulfonic acid or corresponding alkali metal salts, with Na as the counterion being particularly preferred.
  • the sulfonate or carboxylate groups are particularly preferably present in the form of their salts with an alkali ion or an ammonium ion as the counterion.
  • monoalcohols which, in addition to the hydroxyl group, carry a further isocyanate-reactive group, such as monoalcohols having one or more primary and / or secondary amino groups, eg. B. monoethanolamine.
  • Polyamines having 2 or more primary and / or secondary amino groups are used especially when the chain extension or crosslinking is to take place in the presence of water, since amines usually react faster than alcohols or water with isocyanates. This is often required when aqueous dispersions of crosslinked polyurethanes or high molecular weight polyurethanes are desired. In such cases, the procedure is to prepare prepolymers with isocyanate groups, to rapidly disperse them in water and then to chain extend or crosslink them by adding compounds with a plurality of isocyanate-reactive amino groups.
  • Suitable amines for this purpose are generally polyfunctional amines of the molecular weight range from 32 to 500 g / mol, preferably from 60 to 300 g / mol, which contain at least two amino groups selected from the group of primary and secondary Amino groups, contained.
  • diamines such as diaminoethane, diamopropanes, diaminobutanes, diaminohexanes, piperazine, 2,5-dimethylpiperazine, amino-3-aminomethyl-3,5,5-trimethylcyclohexane (isophoronediamine, IPDA), 4,4'-diaminodicyclohexylmethane , 1, 4-diaminocyclohexane, aminoethylethanolamine, hydrazine, hydrazine hydrate or triamines such as diethylenetriamine or 1, 8-diamino-4-aminomethyloctane.
  • diamines such as diaminoethane, diamopropanes, diaminobutanes, diaminohexanes, piperazine, 2,5-dimethylpiperazine, amino-3-aminomethyl-3,5,5-trimethylcyclohexane (isophoronediamine, IPDA), 4,
  • the amines may also be in blocked form, for.
  • ketimines see, for example, CA-A 1 129 128)
  • ketazines see, for example, US-A 4,269,748) or amine salts (see US-A 4,292,226).
  • Oxazolidines such as are used, for example, in US Pat. No. 4,192,937, are blocked polyamines which can be used for the preparation of the polyurethanes according to the invention for chain extension of the prepolymers.
  • capped polyamines they are generally mixed with the prepolymers in the absence of water and this mixture is then mixed with the dispersion water or a portion of the dispersion water, so that the corresponding polyamines are hydrolytically released.
  • mixtures of di- and triamines particularly preferably mixtures of isophoronediamine (IPDA) and diethylenetriamine (DETA).
  • IPDA isophoronediamine
  • DETA diethylenetriamine
  • the polyurethanes preferably contain from 1 to 30, particularly preferably from 4 to 25, mol%, based on the total amount of components (b) and (d), of a polyamine having at least 2 isocyanate-reactive amino groups as monomers (d).
  • divalent isocyanates can also be used as monomers (d).
  • Commercially available compounds are, for example, the isocyanurate or the biuret of hexamethylene diisocyanate.
  • Monomers (e), which are optionally used, are monoisocyanates, monohydric alcohols and monoprimary and secondary amines. In general, their proportion is at most 10 mol%, based on the total molar amount of the monomers.
  • These monofunctional compounds usually carry further functional groups, such as olefinic groups or carbonyl groups, and serve to introduce functional groups into the polyurethane, which make possible the dispersion or crosslinking or further polymer-analogous reaction of the polyurethane.
  • Suitable for this purpose are monomers such as isopropenyl- ⁇ , ⁇ -dimethylbenzyl isocyanate (TMI) and esters of acrylic or methacrylic acid such as hydroxyethyl acrylate or hydroxyethyl methacrylate.
  • TMI isopropenyl- ⁇ , ⁇ -dimethylbenzyl isocyanate
  • esters of acrylic or methacrylic acid such as hydroxyethyl acrylate or hydroxyethyl methacrylate.
  • Coatings with a particularly good property profile are obtained especially when the monomers (a) used are essentially only aliphatic diisocyanates, cycloaliphatic diisocyanates or araliphatic diisocyanates.
  • This monomer combination is excellently supplemented as component (c) by diaminosulfonic acid-alkali salts; in particular by the N- (2-aminoethyl) -2-aminoethanesulfonic acid or its corresponding alkali metal salts, the Na salt being the most suitable, and a mixture of DETA / IPDA as component (d).
  • A is the molar amount of isocyanate groups
  • B is the sum of the molar amount of the hydroxyl groups and the molar amount of the functional groups which can react with isocyanates in an addition reaction
  • the ratio A: B is as close as possible to 1: 1.
  • the monomers (a) to (e) used carry on average usually 1.5 to 2.5, preferably 1.9 to 2.1, particularly preferably 2.0 isocyanate groups or functional groups which can react with isocyanates in an addition reaction ,
  • the polyaddition of components (a) to (e) for the preparation of the polyurethane is preferably carried out at reaction temperatures of up to 180 ° C, preferably up to 150 ° C under atmospheric pressure or under autogenous pressure.
  • the polyurethane adhesive can consist exclusively of the polyurethane as a binder (apart from water and solvent). But he can also other additives, eg. As fillers, thickeners, defoamers, etc. included.
  • crosslinkers for. B. compounds with carbodiimide groups, isocyanate groups or aziridine groups.
  • the crosslinkers may also be attached to polymers, e.g. Example, the above polymeric binder, be bound.
  • the polyurethane adhesive may be a one component (1K) or a two part (2K) adhesive.
  • Crosslinkers for 2K adhesives are z.
  • crosslinking agents Compounds with carbodiimide groups are preferred as crosslinking agents, since aqueous dispersions which contain such compounds or carbodiimide groups are storage-stable, ie can be used as 1 K adhesives.
  • polyurethane adhesives which are block-solid at room temperature (20 ° C) after drying, i. not sticky coatings.
  • the dried adhesive coatings can still be applied after several weeks, e.g. after more than 4 or more than 8 weeks with unchanged high strength are glued. When used later, these polyurethane coatings are heated and then sticky.
  • Polyurethane adhesives having these properties are, in particular, those which contain polyester partially or exclusively as diols b1 (see above), or those which have a melting enthalpy of more than 20 J / g in the temperature range from 20 to 150.degree. C., preferably 30 to 100.degree to have.
  • the measurement of the melting point and the enthalpy of fusion is carried out by the method of differential scanning calorimetry.
  • the measurement is carried out on polyurethane films of a thickness of 200 .mu.m, which were dried before the measurement in a circulating air T rocken Eat at 40 ° C for 72 hours.
  • To prepare the measurement about 13 mg of the polyurethane are filled in pans. The pans are sealed, the samples heated to 120 ° C, cooled at 20 K / min and annealed at 20 ° C for 20 hours.
  • the thus prepared samples become measured according to the DSC method according to DIN 53765, wherein the sample is heated at 20 K / min.
  • the melting point temperature is evaluated according to DIN 53765, the enthalpy of fusion is determined as in FIG. 4 of DIN 53765.
  • the composite element according to the invention contains a substrate made of a polyolefin (polyolefin substrate) and a substrate made of polyurethane (polyurethane substrate), which are joined together by an adhesive.
  • the composite elements may consist solely of these two substrates, but they may also contain any other substrates.
  • the polyolefin substrate and the polyurethane substrate may have any shape.
  • the substrates may be films, non-woven fabrics, sheets or other shaped articles of any desired shape.
  • the substrates are polymer films or non-woven fabrics.
  • the two substrates may be two polymer films, or two nonwoven fabrics, and may also be a nonwoven fabric and a polymer film which are bonded to one another.
  • the nonwoven may be either the polyolefin substrate or the polyurethane substrate, and accordingly the polymer film may also be the polyolefin substrate or the polyurethane substrate.
  • the composite element contains a nonwoven fabric, which is connected to a polymer film or another nonwoven fabric by an adhesive.
  • the polyolefin substrate is a nonwoven and the polyurethane substrate is a polymeric film.
  • both the polyolefin substrate and the polyurethane substrate are a nonwoven fabric.
  • the nonwoven fabric is preferably a nonwoven web of nonwoven fibers.
  • the production of the nonwovens can be made of two types.
  • a nonwoven nonwoven fabric fibers are, for example, combined to form a structure and according to different methods to form a coherent nonwoven fabric. Untitled.
  • the web is coated with an aqueous binder, e.g. As a polymer latex, treated and then, optionally after removal of excess binder, dried and optionally cured.
  • an aqueous binder e.g. As a polymer latex
  • the nonwovens are processed directly from the substrates to the fiber webs, these processes include the “meltblown process” or “spunbond process” known from the prior art. "Meltblown process” and “Spunbond processes” are known in the art and the resulting nonwoven webs generally differ in their mechanical properties and consistency, so nonwoven webs made by the spunbond process are particularly stable in both the horizontal and vertical directions but an open-pored structure.
  • Nonwovens produced by the meltblown process have a particularly dense network of fibers and thus provide a very good barrier to liquids.
  • a commercial plant for the production of nonwovens can be used.
  • the polymer substrate is usually melted in an extruder and fed to a spinning beam by means of customary auxiliaries, such as melt pumps and filters.
  • the polymer generally flows through nozzles and is stretched at the nozzle exit a thread.
  • the drawn threads are usually deposited on a drum or a belt and transported on.
  • a material is considered to be "nonwoven" within the meaning of this application if more than 50%, in particular 60 to 90%, of the mass of its fibrous constituent of fibers having a length to diameter ratio greater than 300, in particular more than 500.
  • the individual fibers of the nonwoven have a diameter of 50 .mu.m to 0.1 .mu.m, preferably from 10 .mu.m to 0.5 .mu.m, in particular from 7 .mu.m to 0.5 .mu.m.
  • the nonwoven webs have a thickness of 0.01 to 5 millimeters (mm), more preferably 0.1 to 2 mm, measured to ISO 9073-2.
  • the nonwovens have a basis weight of 5 to 2000 g / m 2 , more preferably from 5 to 500 g / m 2 , particularly preferably from 10 to 150 g / m 2 , measured according to ISO 9073-1.
  • the nonwoven fabric may additionally be mechanically consolidated.
  • the mechanical consolidation may be a one-sided or bilateral mechanical consolidation, preferably a two-sided mechanical consolidation.
  • the nonwoven fabric may additionally be thermally bonded.
  • a thermal consolidation can be carried out for example by a hot air treatment of the nonwoven fabric.
  • the polymer film preferably polyurethane film, generally following applies:
  • the polymer film preferably has a thickness of 1 micron prior to 1000 microns, preferably 10 ⁇ -100 microns or has a basis weight of 1g / m 2 -1000 g / m 2, preferably 10 g / m 2 to 100 g / m 2 , particularly preferably 10 g / m 2 to 30 g / m 2 .
  • the polyolefin substrate and the polyurethane substrate are bonded together by an adhesive, preferably a polyurethane adhesive.
  • an adhesive preferably a polyurethane adhesive.
  • This is in particular an aqueous polyurethane adhesive, preferably a polyurethane adhesive containing an aqueous polyurethane dispersion as a binder.
  • the adhesive can be applied to one of the two substrates to be bonded or to both substrates.
  • the coating can be carried out by customary application methods. After the coating, if appropriate, a drying, preferably at room temperature or temperatures up to 80 ° C, to remove water or other solvents.
  • the amount of adhesive used is preferably 0.5 to 100 g / m 2, more preferably 2 to 80 g / m 2, most preferably 10 to 70 g / m 2, regardless of whether only one substrate or both substrates have been coated.
  • the coated and dried substrates can be stored. If the substrates are flexible, they can be wound up on drums.
  • the two substrates for. B. the polypropylene nonwoven fabric and the polyurethane film joined together. This can also be done in a continuous process.
  • the substrates are pressed together.
  • the temperature in the adhesive layer is preferably 20 to 200 ° C, more preferably 30 to 180 ° C.
  • the adhesive coated substrate is heated to appropriate temperatures.
  • the bonding is preferably carried out under pressure, this can, for. B. the parts to be bonded are pressed together with a pressure of 0.05 to 5 N / mm2.
  • the resulting composite element is easy to produce and has the properties required for the particular use.
  • an electrostatic equipment by corona or plasma discharge can be dispensed with. It is also possible to dispense with a chemical pretreatment, eg. B. by using primers or primers.
  • the composite element is produced continuously "inline.” If the composite element is, for example, a composite element made of a polyolefin nonwoven and a TPU nonwoven, then the polyolefin nonwoven can be produced by a process described above, for example " Polymer-to-web "process, eg. B. produced by the spunbond process and stored on a continuous belt. Then the adhesive is applied to the polyolefin nonwoven. In a further step, the polyurethane nonwoven is applied directly to the polyolefin nonwoven containing the adhesive by a "polymer-to-web" process, eg a meltblown process.
  • a polymer-to-web eg. meltblown process
  • Example a composite element of a polyolefin nonwoven and a TPU film, so the polyolefin nonwoven fabric by a method described above, for. B is a "polymer-to-web" process, for example produced by the spunbond process and deposited on a continuous belt, then the adhesive is applied to the polyolefin nonwoven fabric Adhesive extruded.
  • Composite elements or laminates made of fiber webs, in particular polypropylene fiber webs, and polymer films, in particular polyurethane films, are very well suited as roof underlays.
  • the composite element or laminate When used as a roof underlay the composite element or laminate should in particular have good mechanical properties and possess the required breathability.
  • the laminate should be easy and environmentally friendly to manufacture and use.
  • the laminate obtained is characterized by high mechanical strength, in particular a high tensile strength, even at elevated temperatures (heat resistance) or under strongly changing climatic conditions (climatic resistance).
  • the laminate has a very good seal against liquid water, but at the same time the laminate has a high water vapor permeability.
  • the laminate, or the roof underlay sheet preferably has a total thickness of 1 .mu.m to 6 mm.
  • Roof underlays are used to seal roof trusses against penetrating water, but at the same time have to be permeable to water vapor and have the necessary mechanical tear resistance. Roof underlays are generally stretched over the timber construction of a roof truss.
  • Composite elements made of polyolefin fleece and TPU fleece. These laminates have an elastic character and a comfortable fit and are particularly suitable for hygienic articles, eg. Diapers and other incontinence products, for articles of clothing, e.g. Disposable underwear, T-shirts, and applications in the medical Seketor z. B. bandages and plasters.
  • the bolonate was added to the polyurethane dispersion in an amount of 2.5 parts by weight per 100 parts by weight of polyurethane (solid / solid).
  • the mixture can be used as a one-component (1 K) adhesive.
  • Luphen ®D 200A commercial aqueous polyurethane dispersion for adhesives, polyurethane made with a polyester diol
  • Basonat ® F 200WD polyisocyanate crosslinker
  • the bolonate was added to the polyurethane dispersion in an amount of 12.5 parts by weight per 100 parts by weight of polyurethane (solid / solid).
  • the mixture is a two component (2K) adhesive, i. the crosslinker is added just before processing
  • a polypropylene fiber fleece and a thermoplastic polyurethane (TPU) film were bonded together.
  • Dry / dry the coating was applied to both substrates with a 1mm squeegee. Thereafter, both substrates were dried for 1 hour at room temperature, with the polyester-containing adhesives 1 and 2 being block-solid at room temperature, i. not sticky coatings resulted. It was then pressed at 90 ° C and a pressure of 0.5 N / mm 2 for 30 seconds.
  • the peel strength of the laminates was determined.
  • the TPU film was peeled off at a 180 ° angle in a tensile testing machine and the force required was determined in N / 5 cm.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Medicinal Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Architecture (AREA)
  • Structural Engineering (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Civil Engineering (AREA)
  • Laminated Bodies (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

L'invention concerne un élément composite contenant un substrat à base d'une polyoléfine et un substrat de polyuréthanne assemblés au moyen d'un adhésif.
EP07712356A 2006-03-10 2007-02-28 Élément composite à base de polyuréthanne et de polyoléfine Withdrawn EP2010387A2 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP07712356A EP2010387A2 (fr) 2006-03-10 2007-02-28 Élément composite à base de polyuréthanne et de polyoléfine

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
EP06110923 2006-03-10
EP07712356A EP2010387A2 (fr) 2006-03-10 2007-02-28 Élément composite à base de polyuréthanne et de polyoléfine
PCT/EP2007/051867 WO2007104640A2 (fr) 2006-03-10 2007-02-28 Élément composite à base de polyuréthanne et de polyoléfine

Publications (1)

Publication Number Publication Date
EP2010387A2 true EP2010387A2 (fr) 2009-01-07

Family

ID=38293346

Family Applications (1)

Application Number Title Priority Date Filing Date
EP07712356A Withdrawn EP2010387A2 (fr) 2006-03-10 2007-02-28 Élément composite à base de polyuréthanne et de polyoléfine

Country Status (4)

Country Link
US (1) US20090170392A1 (fr)
EP (1) EP2010387A2 (fr)
CN (1) CN101484510A (fr)
WO (1) WO2007104640A2 (fr)

Families Citing this family (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2010509512A (ja) * 2006-11-10 2010-03-25 ビーエーエスエフ ソシエタス・ヨーロピア 熱可塑性ポリウレタンに基づく繊維、特に不織布
KR101463277B1 (ko) 2006-12-22 2014-11-26 바스프 에스이 카르보디이미드 기를 가지는 화합물을 포함하는 미세캡슐
CN101412297B (zh) * 2007-10-19 2011-05-04 财团法人工业技术研究院 共挤压防水透湿薄膜结构及纺织品
AU2015295542A1 (en) * 2014-08-01 2017-03-16 Basf Se Method for producing and using aqueous polyurethane dispersions and use of same in coating agents
CN105058932A (zh) * 2015-07-30 2015-11-18 广东天安新材料股份有限公司 一种表面装饰材料
DE102015012015A1 (de) * 2015-08-05 2017-02-09 Ewald Dörken Ag Mehrschichtverbundfolie, vorzugsweise für den Baubereich
CN110997312A (zh) * 2017-08-24 2020-04-10 巴斯夫涂料有限公司 由膜、固体粘合剂聚合物和聚氨酯层制得的复合材料的制备
US20190344539A1 (en) 2018-05-08 2019-11-14 Crypton, Inc. Treated fabrics and methods of forming same
EP3774322B1 (fr) * 2018-05-08 2022-12-21 Crypton, Inc. Tissus traités et leurs procédés de fabrication
US20190344550A1 (en) 2018-05-08 2019-11-14 Crypton, Inc. Treated fabrics and methods of forming same
DE102021103033A1 (de) * 2021-02-09 2022-08-11 Ewald Dörken Ag Alterungsstabile Dichtbahn

Family Cites Families (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2534281B2 (ja) * 1987-11-17 1996-09-11 大倉工業株式会社 耐薬品性に優れた多層ポリウレタンフイルム
US5036551A (en) * 1990-02-16 1991-08-06 W. L. Gore & Associates, Inc. Elastomeric composite fabric
DE29602475U1 (de) * 1996-02-13 1996-04-18 Spielau, Paul, Dipl.-Chem. Dr., 53844 Troisdorf Diffusionsoffene Dachunterspannbahn
US5883028A (en) * 1997-05-30 1999-03-16 Kimberly-Clark Worldwide, Inc. Breathable elastic film/nonwoven laminate
DE19754251C2 (de) * 1997-12-06 2003-04-17 Coronor Composites Gmbh Kunststoffolie, welche wasserdicht und wasserdampfdurchlässig ist
US6133400A (en) * 1999-01-20 2000-10-17 H. B. Fuller Licensing, Inc. High moisture vapor transmission hot melt moisture cure polyurethane adhesive with excellent hydrolysis resistance
FR2808470B1 (fr) * 2000-05-03 2003-04-11 Trioplanex France Film multicouche microporeux respirable a impermeabilite renforcee aux liquides et procede de production
DE10047685C2 (de) * 2000-09-25 2002-09-12 Doerken Ewald Ag Gebäudedach
DE102005038863A1 (de) * 2004-09-06 2006-03-23 Silu Verwaltung Ag Mehrschichtfolie mit einstellbarer Wasserdampfdurchlässigkeit
EP1632345A3 (fr) * 2004-09-06 2008-05-21 Silu Verwaltung AG Feuille multicouche à perméabilité ajustable à la vapeur d'eau

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO2007104640A3 *

Also Published As

Publication number Publication date
US20090170392A1 (en) 2009-07-02
WO2007104640A2 (fr) 2007-09-20
CN101484510A (zh) 2009-07-15
WO2007104640A3 (fr) 2008-11-20

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